U.S. patent application number 10/992001 was filed with the patent office on 2005-04-28 for supported group 8-10 transition metal olefin polymerization catalysts.
This patent application is currently assigned to Eastman Chemical Company. Invention is credited to Killian, Christopher Moore, Lavoie, Gino Georges, Mackenzie, Peter Borden, Moody, Leslie Shane.
Application Number | 20050090630 10/992001 |
Document ID | / |
Family ID | 46279682 |
Filed Date | 2005-04-28 |
United States Patent
Application |
20050090630 |
Kind Code |
A1 |
Mackenzie, Peter Borden ; et
al. |
April 28, 2005 |
Supported group 8-10 transition metal olefin polymerization
catalysts
Abstract
Methods for preparing olefin polymers, and catalysts for
preparing olefin polymers are disclosed. The polymers can be
prepared by contacting the corresponding monomers with a Group 8-10
transition metal catalyst and a solid support. The polymers are
suitable for processing in conventional extrusion processes, and
can be formed into high barrier sheets or films, or low molecular
weight resins for use in synthetic waxes in wax coatings or as
emulsions.
Inventors: |
Mackenzie, Peter Borden;
(Kingsport, TN) ; Moody, Leslie Shane; (Johnson
City, TN) ; Killian, Christopher Moore; (Gray,
TN) ; Lavoie, Gino Georges; (Kingsport, TN) |
Correspondence
Address: |
BURNS DOANE SWECKER & MATHIS L L P
POST OFFICE BOX 1404
ALEXANDRIA
VA
22313-1404
US
|
Assignee: |
Eastman Chemical Company
Kingsport
TN
|
Family ID: |
46279682 |
Appl. No.: |
10/992001 |
Filed: |
November 19, 2004 |
Related U.S. Patent Documents
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Application
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Patent Number |
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10992001 |
Nov 19, 2004 |
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09984680 |
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09984680 |
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09579793 |
May 26, 2000 |
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6660677 |
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09579793 |
May 26, 2000 |
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09177099 |
Oct 22, 1998 |
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6103658 |
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09579793 |
May 26, 2000 |
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09088223 |
Jun 1, 1998 |
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09088223 |
Jun 1, 1998 |
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09030058 |
Feb 24, 1998 |
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10992001 |
Nov 19, 2004 |
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09984620 |
Oct 30, 2001 |
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6822062 |
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60062609 |
Oct 22, 1997 |
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60040363 |
Mar 10, 1997 |
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60041542 |
Mar 25, 1997 |
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60042925 |
Apr 4, 1997 |
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60043406 |
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60044691 |
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60059372 |
Sep 18, 1997 |
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Current U.S.
Class: |
526/131 ;
502/167; 526/172; 526/348.6; 526/352 |
Current CPC
Class: |
C08F 110/02 20130101;
C08F 210/16 20130101; C07D 285/10 20130101; C08F 110/06 20130101;
C08F 210/02 20130101; C08F 210/16 20130101; C07F 15/025 20130101;
C07F 15/02 20130101; C08F 10/00 20130101; C07D 319/12 20130101;
C07C 257/14 20130101; C07F 15/006 20130101; C07D 233/56 20130101;
C08F 110/02 20130101; C08F 210/02 20130101; C08F 110/14 20130101;
C07C 251/36 20130101; C08F 2500/03 20130101; C08F 2500/02 20130101;
C08F 2500/10 20130101; C08F 220/10 20130101; C08F 2500/09 20130101;
C08F 2500/03 20130101; C08F 210/02 20130101; C07F 15/045 20130101;
C07D 249/08 20130101; C07D 231/12 20130101; C08F 110/06 20130101;
C08F 2500/03 20130101; C08F 2500/10 20130101; C08F 2500/10
20130101; C08F 218/00 20130101; C08F 210/18 20130101; C08F 4/7006
20130101; C08F 2500/09 20130101; C08F 2500/20 20130101; C08F
2500/04 20130101; C08F 2500/10 20130101; C08F 2500/10 20130101;
C08F 2500/10 20130101; C08F 2500/20 20130101; C08F 2500/02
20130101; C08F 2500/03 20130101; C08F 2500/10 20130101; C08F 210/14
20130101; C08F 2500/10 20130101; C08F 2500/03 20130101; C08F 4/26
20130101; C08F 2500/20 20130101; C08F 2500/03 20130101; C07D 339/08
20130101; C08F 10/00 20130101; C08F 10/00 20130101; C07D 233/96
20130101; C08F 110/02 20130101; C07F 9/5022 20130101; C07D 265/30
20130101; C07F 9/5031 20130101; C08F 110/02 20130101; C08F 210/14
20130101; C08F 236/20 20130101; C08F 2500/10 20130101; C08F 2500/05
20130101; C08F 2500/20 20130101; C08F 2500/03 20130101; C07F 15/04
20130101; C07D 513/04 20130101; C08F 110/14 20130101; C08F 110/02
20130101; C07D 241/06 20130101; C08F 210/16 20130101; C07F 15/065
20130101; C08F 210/02 20130101; C07F 15/06 20130101; C08F 210/02
20130101; C07F 15/0066 20130101 |
Class at
Publication: |
526/131 ;
526/172; 526/348.6; 526/352; 502/167 |
International
Class: |
C08F 004/44; B01J
031/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 28, 1999 |
WO |
PCT/US99/12074 |
Claims
1-47. (canceled)
48. A compound of formula VI: 25wherein R.sup.1 and R.sup.6 each,
independently, represent a sterically hindered aryl; and R.sup.2
and R.sup.3 each, independently, represent a hydrogen, hydrocarbyl,
substituted hydrocarbyl, or silyl, and, in addition, may
collectively form a bridging hydrocarbyl, bridging substituted
hydrocarbyl, or a substituted silicon atom.
49. A compound of formula IX 26wherein R.sup.1 and R.sup.6 each,
independently, represent a sterically hindered aryl; and R.sup.2
and R.sup.3 each, independently, represent a hydrogen, hydrocarbyl,
substituted hydrocarbyl, or silyl, and, in addition, may
collectively form a bridging hydrocarbyl, bridging substituted
hydrocarbyl, or a substituted silicon atom.
50. A compound of formula XVII 27wherein R.sup.1 and R.sup.6 each,
independently, represent a sterically hindered aryl; and R.sup.2,
R.sup.3, and R.sup.4 each, independently, represent a hydrogen,
hydrocarbyl, substituted hydrocarbyl, or silyl, and, in addition,
any two of R.sup.2, R.sup.3, and R.sup.4 may collectively form a
bridging group.
51. A compound of formula XVIII: 28wherein R.sup.1 and R.sup.6
each, independently, represent a sterically hindered aryl; and
R.sup.2 and R.sup.5 each, independently, represent a hydrogen,
hydrocarbyl, substituted hydrocarbyl, or silyl.
52. A composition comprising an ethylene homopolymer with greater
than 125 alkyl branches per 1000 carbon atoms.
53. A polyethylene composition comprising a blend of polyethylene
polymers, wherein said blend has an average degree of branching of
from 5 to 120 alkyl branches per 1000 carbon atoms, wherein any
individual component of said blend has a degree of branching of
from 0 to 150 alkyl branches per 1000 carbon atoms, wherein said
polymers are prepared in one reaction vessel, solely from ethylene,
and wherein said polymers are prepared utilizing a Group 8-10
transition metal catalyst supported on a solid support which has
been pre-treated with a compound Y selected from the group
consisting of methylaluminoxane and other aluminum sesquioxides
having the formulas R.sup.7.sub.3Al, R.sup.7.sub.2AlCl, and
R.sup.7AlCl.sub.2 ,wherein R.sup.7 is alkyl.
54. The composition of claim 53, wherein the transition metal
catalyst is a Ni catalyst.
55. The composition of claim 54, wherein the compound Y is
methylaluminoxane.
56. A polyethylene composition comprising a blend of polyethylene
polymers, wherein said blend has an average degree of branching of
from 5 to 120 alkyl branches per 1000 carbon atoms, wherein any
individual component of said blend has a degree of branching of
from 0 to 150 alkyl branches per 1000 carbon atoms, wherein said
polymers are prepared in one reaction vessel, solely from ethylene,
and wherein said polymers are prepared utilizing a Group 8-10
transition metal catalyst which has been reacted with a solid
support and a compound Y, in any order, wherein Y is selected from
the group consisting of methylaluminoxane and other aluminum
sesquioxides having the formulas R.sup.7.sub.3Al,
R.sup.7.sub.2AlCl, and R.sup.7AlCl.sub.2 wherein R.sup.7 is
alkyl.
57. The composition of claim 56, wherein the transition metal
catalyst is a Ni catalyst.
58. The composition of claim 57, wherein the compound Y is
methylaluminoxane.
59. A polymer derived from essentially ethylene alone that has
greater than 30 branches per 1000 carbon atoms and a melt
transition (endothermic maximum) in the DSC of greater than about
110.degree. C.
60. The polymer of claim 59, which is a free flowing polymer.
61. A polymer derived from ethylene alone that has a broad
composition distribution and a molecular weight distribution of
less than 6 and greater than 2.5, wherein said polymer has an
average degree of branching of from 5 to 120 alkyl branches per
1000 carbon atoms, and wherein any individual component of said
polymer has a degree of branching of from 0 to 150 alkyl branches
per 1000 carbon atoms.
62. The polymer of claim 61, wherein an individual component of the
polymer has between about 40 and 100 branches per 1000 carbon
atoms, another component has between about 30 and 90 branches per
1000 carbon atoms, another component has between about 30 and 80
branches per 1000 carbon atoms, another component has between about
20 and 60 branches per 1000 carbon atoms, another component has
between about 10 and 50 branches per 1000 carbon atoms, another
component has between about 10 and 40 branches per 1000 carbon
atoms, another component has between about 5 and 35 branches per
1000 carbon atoms, another component has between about 0 and 25
branches per 1000 carbon atoms, another component has between about
0 and 30 branches per 1000 carbon atoms, another component has
between about 0 and 20 branches per 1000 carbon atoms.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit under 35 U.S.C. .sctn.
119 of PCT/US99/12074 filed May 28, 1999, which claims the benefit
under 35 U.S.C. .sctn. 119(e) of Provisional Application Ser. No.
60/062,609 filed Oct. 22, 1997, and which is a continuation-in-part
application of U.S. application Ser. No. 09/088,223 filed on Jun.
1,1998, which is a continuation-in-part of U.S. application Ser.
No. 09/030,058 filed on Feb. 24, 1998, incorporated herein by
reference, which claims the benefit under 35 U.S. C. .sctn. 119(e)
of Provisional Application Ser. No. 60/040,363 filed Mar. 10, 1997;
Provisional Application Ser. No. 60/041,542 filed Mar. 25, 1997;
Provisional Application Ser. No. 60/042,925 filed Apr. 4, 1997;
Provisional Application Ser. No. 60/043,406 filed Apr. 4, 1997;
Provisional Application Ser. No. 60/044,691 filed Apr. 18, 1997,
and Provisional Application Ser. No. 60/059,372 filed Sep. 18,
1997.
BACKGROUND OF THE INVENTION
[0002] The present invention is directed to Group 8-10 transition
metal-containing complexes, their use in olefin polymerizations,
and to novel olefin polymers produced thereby.
[0003] Olefin polymers are used in a wide variety of products, from
sheathing for wire and cable to film. Olefin polymers are used, for
instance, in injection or compression molding applications, in
extruded films or sheeting, as extrusion coatings on paper, for
example photographic paper and digital recording paper, and the
like. Improvements in catalysts have made it possible to better
control polymerization processes, and, thus, influence the
properties of the bulk material. Increasingly, efforts are being
made to tune the physical properties of plastics for lightness,
strength, resistance to corrosion, permeability, optical
properties, and the like, for particular uses. Chain length,
polymer branching and functionality have a significant impact on
the physical properties of the polymer. Accordingly, novel
catalysts are constantly being sought in attempts to obtain a
catalytic process for polymerizing olefins which permits more
efficient and better controlled polymerization of olefins.
[0004] Conventional polyolefins are prepared by a variety of
polymerization techniques, including homogeneous liquid phase, gas
phase, and slurry polymerization. Certain transition metal
catalysts, such as those based on titanium compounds (e.g.
TiCl.sub.3 or TiCl.sub.4) in combination with organoaluminum
cocatalysts, are used to make linear and linear low density
polyethylenes as well as poly-.alpha.-olefins such as
polypropylene. These so-called "Ziegler-Natta" catalysts are quite
sensitive to oxygen and are ineffective for the copolymerization of
nonpolar and polar monomers.
[0005] Recent advances in non-Ziegler-Natta olefin polymerization
catalysis include the following.
[0006] L. K. Johnson et al., WO Patent Application 96/23010,
disclose the polymerization of olefins using cationic nickel,
palladium, iron, and cobalt complexes containing diimine and
bisoxazoline ligands. This document also describes the
polymerization of ethylene, acyclic olefins, and/or selected cyclic
olefins and optionally selected unsaturated acids or esters such as
acrylic acid or alkyl acrylates to provide olefin homopolymers or
copolymers.
[0007] European Patent Application Serial No. 381,495 describes the
polymerization of olefins using palladium and nickel catalysts
which contain selected bidentate phosphorous containing
ligands.
[0008] L. K. Johnson et al., J. Am. Chem. Soc., 1995, 117, 6414,
describe the polymerization of olefins such as ethylene, propylene,
and 1-hexene using cationic .alpha.-diimine-based nickel and
palladium complexes. These catalysts have been described to
polymerize ethylene to high molecular weight branched polyethylene.
In addition to ethylene, Pd complexes act as catalysts for the
polymerization and copolymerization of olefins and methyl
acrylate.
[0009] G. F. Schmidt et al., J. Am. Chem. Soc. 1985, 107,1443,
describe a cobalt(III) cyclopentadienyl catalytic system having the
structure [C.sub.5Me.sub.5(L)COCH.sub.2CH.sub.2-.mu.-H].sup.+,
which provides for the "living" polymerization of ethylene.
[0010] M. Brookhart et al., Macromolecules 1995, 28, 5378, disclose
using such "living" catalysts in the synthesis of
end-functionalized polyethylene homopolymers.
[0011] U. Klabunde, U.S. Pat. Nos. 4,906,754, 4,716,205, 5,030,606,
and 5,175,326, describes the conversion of ethylene to polyethylene
using anionic phosphorous, oxygen donors ligated to Ni(II). The
polymerization reactions were run between 25 and 100.degree. C.
with modest yields, producing linear polyethylene having a
weight-average molecular weight ranging between 8K and 350 K. In
addition, Klabunde describes the preparation of copolymers of
ethylene and functional group containing monomers.
[0012] M. Peuckert et al., Organomet. 1983, 2(5), 594, disclose the
oligomerization of ethylene using phosphine, carboxylate donors
ligated to Ni(II), which showed modest catalytic activity (0.14 to
1.83 TO/s). The oligomerizations were carried out at 60 to
95.degree. C. and 10 to 80 bar ethylene in toluene, to produce
.alpha.-olefins.
[0013] R. E. Murray, U.S. Pat. Nos. 4,689,437 and 4,716,138,
describes the oligomerization of ethylene using phosphine,
sulfonate donors ligated to Ni(II). These complexes show catalyst
activities approximately 15 times greater than those reported with
phosphine, carboxylate analogs.
[0014] W. Keim et al., Angew. Chem. Int. Ed. Eng. 1981, 20,116, and
V. M. Mohring, et al., Angew. Chem. Int Ed. Eng. 1985, 24, 1001,
disclose the polymerization of ethylene and the oligomerization of
.alpha.-olefins with aminobis(imino)phosphorane nickel catalysts;
G. Wilke, Angew. Chem. int. Ed. Engl. 1988, 27, 185, describes a
nickel allyl phosphine complex for the polymerization of
ethylene.
[0015] K. A. O. Starzewski et al., Angew. Chem. Int. Ed. Engl.
1987, 26, 63, and U.S. Pat. No. 4,691,036, describe a series of
bis(ylide) nickel complexes, used to polymerize ethylene to provide
high molecular weight linear polyethylene.
[0016] WO Patent Application 97/02298 discloses the polymerization
of olefins using a variety of neutral N, O, P, or S donor ligands,
in combination with a nickel(0) compound and an acid.
[0017] Brown et al., WO 97/17380, describes the use of Pd
.alpha.-diimine catalysts for the polymerization of olefins
including ethylene in the presence of air and moisture.
[0018] Fink et al., U.S. Pat. No. 4,724,273, have described the
polymerization of .alpha.-olefins using aminobis(imino)phosphorane
nickel catalysts and the compositions of the resulting
poly(.alpha.-olefins).
[0019] Recently Vaughan et al. WO 9748736, Denton et al. WO
9748742, and Sugimura et al. WO 9738024 have described the
polymerization of ethylene using silica supported .alpha.-diimine
nickel catalysts.
[0020] Additional recent developments are described by Sugimura et
al., in JP96-84344, JP96-84343, by Yorisue et al., in JP96-70332,
by Canich et al. WO 9748735, McLain et al. WO 9803559, Weinberg et
al. WO 9803521 and by Matsunaga et al. WO 9748737.
[0021] Notwithstanding these advances in non-Ziegler-Natta
catalysis, there remains a need for efficient and effective Group
8-10 transition metal catalysts for effecting polymerization of
olefins. In addition, there is a need for novel methods of
polymerizing olefins employing such effective Group 8-10 transition
metal catalysts. In particular, there remains a need for Group 8-10
transition metal olefin polymerization catalysts with both improved
temperature stability and functional group compatibility. Further,
there remains a need for a method of polymerizing olefins utilizing
effective Group 8-10 transition metal catalysts in combination with
a Lewis acid so as to obtain a catalyst that is more active and
more selective.
BRIEF DESCRIPTION OF THE DRAWING
[0022] FIG. 1 is a plot of weight fraction and cumulative weight
fraction versus temperature in degree Celsius for four samples of
polyethylene.
[0023] The following general procedure was used to generate this
plot:
[0024] This data was collected using a Polymics.TM. CAP-TREF
(Temperature Rising Elution Fractionation) system, by first
preparing a one percent polymer solution in 1,2,4-trichlorobenzene.
The samples were dissolved at 150.degree. C. over two hours. An
appropriate amount of CHROMASORB.TM. P was added to the solution,
placed in a temperature-controlled oven and cooled at a rate of
2.degree. C. per hour from 150.degree. C. to 30.degree. C. The TREF
analysis was performed by heating the material at 200.degree. C.
per hour at a solvent (1,2,4-trichlorobenzene) flow rate of 20 mL
per minute.
[0025] The weight fraction was determined by percent transmittance
of an infrared beam of light (3.41 .mu.m).
[0026] Curve 1 is the weight fraction as a function of temperature
of a polyethylene made in solution using the catalyst XXVII, at
80.degree. C. and 600 psig (ethylene), as per Example 196. Average
branching of 45 branches/1000 carbon atoms, as determined by
.sup.1H NMR.
[0027] Curve 2 is the weight fraction as a function of temperature
of a polyethylene made in solution using the catalyst XXVII, at
80.degree. C. and 600 psig (ethylene), as per Example 197. Average
branching of 45 branches/1000 carbon atoms, as determined by
.sup.1H NMR.
[0028] Curve 3 is the weight fraction as a function of temperature
of a polyethylene made in the gas phase using the silica-supported
catalyst XXVII, at 100.degree. C. and 100 psig (ethylene), as per
Example 136. Average branching of 45 branches/1000 carbon atoms, as
determined by .sup.1H NMR.
[0029] Curve 4 is the weight fraction as a function of temperature
of a polyethylene made in the gas phase using the silica-supported
catalyst XXVII, at 100.degree. C. and 100 psig (ethylene), as per
Example 150. Average branching of 47 branches/1000 carbon atoms, as
determined by .sup.1H NMR.
[0030] Curve 1a is the cumulative weight fraction as a function of
temperature for a polyethylene prepared in solution using the
catalyst XXVII, at 80.degree. C. and 600 psig (ethylene), as per
Example 196. Average branching of 45 branches/1000 carbon atoms, as
determined by .sup.1H NMR.
[0031] Curve 2a is the cumulative weight fraction as a function of
temperature for a polyethylene prepared in solution using the
catalyst XXVII, at 80.degree. C. and 600 psig (ethylene), as per
Example 197. Average branching of 45 branches/1000 carbon atoms, as
determined by .sup.1H NMR.
[0032] Curve 3a is the cumulative weight fraction as a function of
temperature for a polyethylene prepared in gas phase using the
silica-supported catalyst XXVII, at 100.degree. C. and 100 psig
(ethylene), as per Example 136. Average branching of 45
branches/1000 carbon atoms, as determined by .sup.1H NMR.
[0033] Curve 4a is the cumulative weight fraction as a function of
temperature for a polyethylene prepared in gas phase using the
silica-supported catalyst XXVII, at 100.degree. C. and 100 psig
(ethylene), as per Example 150. Average branching of 47
branches/1000 carbon atoms, as determined by .sup.1H NMR.
[0034] FIG. 1 illustrates the unique compositions prepared in the
gas phase using supported catalysts of the present invention. The
polymers prepared using a homogeneous catalyst in solution (i.e., 1
and 2) dissolve over a relatively narrow temperature range, while
those prepared using a supported catalyst in the gas phase (i.e., 3
and 4) dissolve over a much wider temperature range. Thus, the
comparison of curves 1 and 2 versus curves 3 and 4 indicates the
existence of a narrow composition distribution range for the
polyethylenes made in solution, in sharp contrast to the
polyethylenes prepared using gas phase polymerization while using
the same transition metal complex when attached to a solid support.
As can be seen in FIG. 1, curves 3 and 4 depict dissolution over a
much larger temperature range, evidence of a much broader
composition distribution.
[0035] In this regard, such polymer compositions provide a unique
blend of properties, i.e., a balance of impact, toughness,
elasticity, tear-resistance, and puncture resistance, which are
particularly desired for such end uses as film, packaging,
sheeting, etc.
DETAILED DESCRIPTION OF THE INVENTION
[0036] In one embodiment, the present invention provides a catalyst
for the polymerization of olefins comprising a complex comprising
(a) a ligand of the formula X, (b) a group 8-10 transition metal,
and optionally (c) a Bronsted or Lewis acid, 1
[0037] R.sup.1 and R.sup.6 are each, independently, hydrocarbyl,
substituted hydrocarbyl, or silyl; N represents nitrogen; and
[0038] A and B are each, independently, a heteroatom connected
mono-radical wherein the connected heteroatom is selected from
Group 15 or 16; in addition, A and B may be linked by a bridging
group; wherein the complex is attached to a solid support, and
wherein the solid support, the optional Bronsted or Lewis acid, and
the complex are combined in any order to form said catalyst.
[0039] In the above catalyst, it should be appreciated that the
Group 8-10 transition metal has coordinated thereto a bidentate
ligand having the formula X and that the Bronsted or Lewis acid is
optionally reacted with this metal-ligand complex. In addition, the
Bronsted or Lewis acid may be optionally combined with the ligand X
prior to complexation to the Group 8-10 transition metal.
[0040] In one embodiment, the invention provides a catalyst for the
polymerization of olefins comprising the reaction product of a
compound of formula XII, a compound Y and a solid support: 2
[0041] R.sup.1 and R.sup.6 each, independently, represent
hydrocarbyl, substituted hydrocarbyl, or silyl;
[0042] A and B are each, independently, a heteroatom connected
mono-radical wherein the connected heteroatom is selected from
Group 15 or 16; in addition, A and B may be linked by a bridging
group;
[0043] Q represents an alkyl, chloride, iodide or bromide;
[0044] W represents an alkyl, chloride, iodide or bromide;
[0045] N represents nitrogen; and
[0046] M represents Ni(II), Pd(II), Co(II), or Fe(II);
[0047] and Y is selected from the group consisting of a neutral
Lewis acid capable of abstracting Q.sup.- or W.sup.- to form a
weakly coordinating anion, a cationic Lewis acid whose counterion
is a weakly coordinating anion, and a Bronsted acid whose conjugate
base is a weakly coordinating anion.
[0048] As a further aspect of the invention, there is provided a
process for the preparation of supported catalysts comprising
contacting a group 8-10 transition metal complex of a ligand of the
formula X, a solid support, and optionally a Bronsted or Lewis
acid, 3
[0049] wherein R.sup.1 and R.sup.6 are each, independently,
hydrocarbyl, substituted hydrocarbyl, or silyl; N represents
nitrogen; and
[0050] A and B are each, independently, a heteroatom connected
mono-radical wherein the connected heteroatom is selected from
Group 15 or 16; in addition, A and B may be linked by a bridging
group; wherein the complex is attached to a solid support, and
wherein the solid support, the optional Bronsted or Lewis acid, and
the complex are combined in any order to form said supported
catalyst.
[0051] In a further embodiment, there is provided a process for the
preparation of supported catalysts comprising the reaction product
of a compound of formula XII, a compound Y and a solid support:
4
[0052] R.sup.1 and R.sup.6 each, independently, represent
hydrocarbyl, substituted hydrocarbyl, or silyl;
[0053] A and B are each, independently, a heteroatom connected
mono-radical wherein the connected heteroatom is selected from
Group 15 or 16; in addition, A and B may be linked by a bridging
group;
[0054] Q represents an alkyl, chloride, iodide or bromide;
[0055] W represents an alkyl, chloride, iodide or bromide;
[0056] N represents nitrogen; and
[0057] M represents Ni(II), Pd(II), Co(II), or Fe(II);
[0058] and Y is selected from the group consisting of a neutral
Lewis acid capable of abstracting Q.sup.- or W.sup.- to form a
weakly coordinating anion, a cationic Lewis acid whose counterion
is a weakly coordinating anion, and a Bronsted acid whose conjugate
base is a weakly coordinating anion.
[0059] In a further embodiment, there is provided a process for the
polymerization of olefins, comprising contacting one or more
monomers of the formula RCH.dbd.CHR.sup.8 with a catalyst
comprising a group 8-10 transition metal complex of a ligand of the
formula X and optionally a Bronsted or Lewis acid, 5
[0060] wherein R and R.sup.8 each, independently, represent a
hydrogen, a hydrocarbyl, or a fluoroalkyl, and may be linked to
form a cyclic olefin;
[0061] R.sup.1 and R.sup.6 are each, independently, hydrocarbyl,
substituted hydrocarbyl, or silyl; N represents nitrogen; and
[0062] A and B are each, independently, a heteroatom connected
mono-radical wherein the connected heteroatom is selected from
Group 15 or 16; in addition, A and B may be linked by a bridging
group; wherein the complex is attached to a solid support, and
wherein the solid support, the optional Bronsted or Lewis acid, and
the complex are combined in any order.
[0063] In a further embodiment, the present invention provides a
process for the polymerization of olefins, comprising contacting
one or more monomers of the formula RCH.dbd.CHR.sup.8 with the
reaction product of a compound of formula XII, a compound Y and a
solid support: 6
[0064] wherein R and R.sup.8 each, independently, represent a
hydrogen, a hydrocarbyl, or a fluoroalkyl, and may be linked to
form a cyclic olefin;
[0065] R.sup.1 and R.sup.6 each, independently, represent
hydrocarbyl, substituted hydrocarbyl, or silyl;
[0066] A and B are each, independently, a heteroatom connected
mono-radical wherein the connected heteroatom is selected from
Group 15 or 16; in addition, A and B may be linked by a bridging
group;
[0067] Q represents an alkyl, chloride, iodide or bromide;
[0068] W represents an alkyl, chloride, iodide or bromide;
[0069] N represents nitrogen; and
[0070] M represents Ni(II), Pd(II), Co(II), or Fe(II);
[0071] and Y is selected from the group consisting of a neutral
Lewis acid capable of abstracting Q.sup.- or W.sup.- to form a
weakly coordinating anion, a cationic Lewis acid whose counterion
is a weakly coordinating anion, and a Bronsted acid whose conjugate
base is a weakly coordinating anion.
[0072] In a further embodiment, the present invention provides a
process for the polymerization of olefins, comprising contacting
one or more monomers of the formula RCH.dbd.CHR.sup.8 with a
supported catalyst formed by combining a compound of formula XII:
7
[0073] with a solid support which has been pre-treated with a
compound Y,
[0074] wherein R and R.sup.8 each, independently, represent a
hydrogen, a hydrocarbyl, or a fluoroalkyl, and may be linked to
form a cyclic olefin;
[0075] R.sup.1 and R.sup.6 each, independently, represent
hydrocarbyl, substituted hydrocarbyl, or silyl;
[0076] A and B are each, independently, a heteroatom connected
mono-radical wherein the connected heteroatom is selected from
Group 15 or 16; in addition, A and B may be linked by a bridging
group;
[0077] Q represents an alkyl, chloride, iodide or bromide;
[0078] W represents an alkyl, chloride, iodide or bromide;
[0079] N represents nitrogen; and
[0080] M represents Ni(II), Pd(II), Co(II), or Fe(II);
[0081] and Y is selected from the group consisting of a neutral
Lewis acid capable of abstracting Q.sup.- or W.sup.- to form a
weakly coordinating anion, a cationic Lewis acid whose counterion
is a weakly coordinating anion, and a Bronsted acid whose conjugate
base is a weakly coordinating anion.
[0082] In a further embodiment, a process for the copolymerization
of one or more olefin monomers of the type RCH.dbd.CHR.sup.8 with
one or more functional olefin monomers of the formula
CH.sub.2.dbd.CH(CH.sub.2).sub.n- J comprising a catalyst, in an
olefin polymerization reaction which comprises combining a complex
of the formula XII, a solid support, and optionally a compound Y,
prior to the utilization of said catalyst in said olefin
polymerization reaction.
[0083] R and R.sup.8 each, independently, represent a hydrogen, a
hydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclic
olefin;
[0084] n is an interger between 1-20;
[0085] J is a group selected from ester, acyl, acid halide,
aldehyde, alkyl amide, aryl, alkylamine, aryl amine, alkyl amido,
aryl amido, alkyl imido, aryl imido, ether, nitrile, alcohol, keto,
amino, amido, imido, alkoxy thiol, thioalkoxy, acid, urea,
sulfonamido, and sulfoester; 8
[0086] R.sup.1 and R.sup.6 each, independently, represent
hydrocarbyl, substituted hydrocarbyl, or silyl;
[0087] A and B are each, independently, a heteroatom connected
mono-radical wherein the connected heteroatom is selected from
Group 15 or 16; in addition, A and B may be linked by a bridging
group;
[0088] Q represents an alkyl, chloride, iodide or bromide;
[0089] W represents an alkyl, chloride, iodide or bromide;
[0090] N represents nitrogen; and
[0091] M represents Ni(II), Pd(II), Co(II), or Fe(II);
[0092] and Y is selected from the group consisting of a neutral
Lewis acid capable of abstracting Q.sup.- or W.sup.- to form a
weakly coordinating anion, a cationic Lewis acid whose counterion
is a weakly coordinating anion, and a Bronsted acid whose conjugate
base is a weakly coordinating anion.
[0093] In a further preferred embodiment, the present invention
provides a process for the copolymerization of ethylene and a
comonomer of the formula
CH.sub.2.dbd.CH(CH.sub.2).sub.nCO.sub.2R.sup.1 which comprises
contacting ethylene and a comonomer of the formula
CH.sub.2.dbd.CH(CH.sub.2).sub.nCO.sub.2R.sup.1 with a supported
catalyst formed by combining silica with a compound of the formula
XII and optionally a compound Y; 9
[0094] wherein R.sup.1 is hydrogen, hydrocarbyl, substituted
hydrocarbyl, fluoroalkyl or silyl;
[0095] n is an integer greater than 3;
[0096] R.sup.1 and R.sup.6 each, independently, represent
hydrocarbyl, substituted hydrocarbyl, or silyl;
[0097] A and B are each, independently, a heteroatom connected
mono-radical wherein the connected heteroatom is selected from
Group 15 or 16; in addition, A and B may be linked by a bridging
group;
[0098] Q represents an alkyl chloride, iodide or bromide;
[0099] W represents an alkyl chloride, iodide or bromide;
[0100] N represents nitrogen; and
[0101] M represents Ni(II), Pd(II), Co(II), or Fe(II);
[0102] and Y is selected from the group consisting of a neutral
Lewis acid capable of abstracting Q.sup.- or W.sup.- to form a
weakly coordinating anion, a cationic Lewis acid whose counterion
is a weakly coordinating anion, and a Bronsted acid whose conjugate
base is a weakly coordinating anion.
[0103] In a further preferred embodiment, there is provided the
above process wherein the compound of formula XII is substituted
for the compound represented by formula XXIV. 10
[0104] wherein R.sup.2 and R.sup.3 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, or silyl, or may collectively
form a bridging hydrocarbyl, bridging substituted hydrocarbyl, or a
substituted silicon atom;
[0105] Q is alkyl, chloride, iodide or bromide;
[0106] W is alkyl, chloride, iodide or bromide;
[0107] N is nitrogen;
[0108] Z is sulfur or oxygen; and
[0109] M is Ni(II).
[0110] In a further preferred embodiment, there is provided a
supported catalyst comprising the reaction product of a compound of
formula V, VIII, or XV: 11
[0111] wherein R.sup.1 and R.sup.6 each, independently, represent a
sterically hindered aryl;
[0112] R.sup.2, R.sup.3 and R.sup.4 each, independently, represent
a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, and, in
addition, may collectively form a bridging hydrocarbyl, bridging
substituted hydrocarbyl, or a substituted silicon atom;
[0113] Q represents a hydrocarbyl, chloride, iodide or bromide;
[0114] W represents a hydrocarbyl, chloride, iodide or bromide;
[0115] N represents nitrogen; and
[0116] M represents Ni(II), Pd(II), Co(II), or Fe(II);
[0117] with a solid support which has been pre-treated with a
compound Y, wherein Y is selected from the group consisting of a
neutral Lewis acid capable of abstracting Q.sup.- or W.sup.- to
form a weakly coordinating anion, a cationic Lewis acid whose
counterion is a weakly coordinating anion, and a Bronsted acid
whose conjugate base is a weakly coordinating anion.
[0118] In an especially preferred embodiment, the compound of
formula XII is selected from the group consisting of 12
[0119] wherein R.sup.1 and R.sup.6 are 2,6-dimethylphenyl; 13
[0120] wherein R.sup.1 and R.sup.6 are 2,6-diisopropylphenyl;
14
[0121] wherein R.sup.1 and R.sup.6 are 2,6-dimethylphenyl; 15
[0122] wherein R.sup.1 and R.sup.6 are 2,6-diisopropylphenyl;
16
[0123] wherein R.sup.1 and R.sup.6 are 2,6-dimethylphenyl; and
17
[0124] wherein R.sup.1 and R.sup.6 are 2,6-diisopropylphenyl.
[0125] The catalysts used in the processes of the present invention
readily convert ethylene and .alpha.-olefins to high molecular
weight polymers, and allow for olefin polymerizations under various
conditions, including ambient temperature and pressure, including
gas phase and slurry (e.g., slurry loop).
[0126] As noted herein, it is preferred that the compounds of the
present invention be attached to a solid support which has been
pre-treated with a compound Y, for example, MAO, or mixed with Y in
any order. We have discovered that when such supported catalysts
are used in slurry and gas phase ethylene polymerizations, novel
polymer compositions are provided insofar as such compositions are
blends of different polyolefin polymers. It is believed that when
such catalysts are attached to a solid support, such as silica,
olefin polymerizations using such supported catalysts provide a
polymer composition which possesses a broad compositional
distribution. This is believed to be due at least in part to both
the creation of unique reaction sites, and the sensitivity of these
catalysts to ethylene concentration. These unique reaction sites
are believed to result from the unique microenvironments created by
the location of the catalyst on the support. The resulting polymer
composition, which can be prepared solely from ethylene as an
olefin feedstock, is one which is actually a blend or plurality of
polymers having a variety of alkyl branched distributions with some
catalyst sites giving less branched high density polymer and other
sites giving more branched lower density polymer.
[0127] The present invention also provides novel polyalkene
compositions. Thus, in one embodiment, the present invention
provides polyethylene composition comprising a blend of
polyethylene polymers, wherein said blend has an average degree of
branching of from 5 to 120 alkyl branches per 1000 carbon atoms,
wherein any individual component of said blend has a degree of
branching of from 0 to 150 alkyl branches per 1000 carbon atoms,
wherein said polymers are prepared in one reaction vessel, solely
from ethylene, and wherein said polymers are prepared utilizing a
Group 8-10 transition metal catalyst supported on a solid support
which has been pre-treated with a compound Y selected from the
group consisting of methylaluminoxane and other aluminum
sesquioxides having the formulas R.sup.7.sub.3Al,
R.sup.7.sub.2AlCl, and R.sup.7AlCl.sub.2, wherein R.sup.7 is alkyl.
The transition metal is preferably Ni and the compound Y is
methylaluminoxane
[0128] A further embodiment of the invention provides a
polyethylene composition comprising a blend of polyethylene
polymers, wherein said blend has an average degree of branching
from 5 to 120 alkyl branches per 1000 carbon atoms, wherein any
individual component of said blend has a degree of branching of
from 0 to 150 alkyl branches per 1000 carbon atoms, wherein said
polymers are prepared in one reaction vessel, solely from ethylene,
and wherein said polymers are prepared utilizing a Group 8-10
transition metal catalyst which has been reacted with a solid
support and a compound Y, in any order, wherein Y is selected from
the group consisting of methylaluminoxane and other aluminum
sesquioxides having the formulas R.sup.7.sub.3Al,
R.sup.7.sub.2AlCl, and R.sup.7AlCl.sub.2, wherein R.sup.7 is
alkyl.
[0129] Further, the catalysts of this invention when supported in
this fashion and utilized in a gas or slurry phase process provide
polymers having a broad composition distribution while having an
intermediate molecular weight distribution, thus providing certain
processing advantages. When fractionated based on solubility using
supercritical propane by isothermal increasing profiling and
critical, isobaric, temperature rising elution fractionation, into
ten fractions, an analysis of such fractions provides data on the
distribution of the relative branching of the components of said
composition.
[0130] Thus, in a further embodiment, there is provided a
polyolefin which when fractionated based on solubility using
supercritical propane by isothermal increasing profiling and
critical, isobaric, temperature rising elution fractionation, into
ten fractions between about 40 and about 140.degree. C., wherein a
first fraction taken at about 40.degree. C. has between about 40
and about 100 branches per 1000 carbon atoms, wherein between about
50 to about 90% are methyl branches, about 5 to about 15% are ethyl
branches, about 1 to about 10% are propyl branches, about 0 to
about 15% are butyl branches, and between about 5 and about 15% are
pentyl or longer branches; a second fraction taken between about
40-60.degree. C. has between about 30 and about 90 branches per
1000 carbon atoms, wherein between about 50 to about 90% are methyl
branches, about 5 to about 15% are ethyl branches, about 1 to about
10% are propyl branches, about 0 to about 15% are butyl branches,
and between about 5 and about 15% are pentyl or longer branches; a
third fraction taken between about 60-65.degree. C. has between
about 30 and about 80 branches per 1000 carbon atoms, wherein
between about 50 to about 90% are methyl branches, about 5 to about
15% are ethyl branches, about 1 to about 10% are propyl branches,
about 0 to about 15% are butyl branches, and between about 5 to
about 15% are pentyl or longer branches; a fourth fraction taken
between about 65-70.degree. C. has between about 20 and about 60
branches per 1000 carbon atoms, wherein between about 50 to about
90% are methyl branches, about 5 to about 15% are ethyl branches,
about 1 to about 10% are propyl branches, about 0 to about 15% are
butyl branches, and between about 5 to about 15% are pentyl or
longer branches; a fifth fraction taken between about 75-85.degree.
C. has between about 10 and about 50 branches per 1000 carbon
atoms, wherein between about 50 to about 90% are methyl branches,
about 5 to about 15% are ethyl branches, about 0 to about 10% are
propyl branches, about 0 to about 15% are butyl branches, and
between about 5 to about 15% are pentyl or longer branches; a sixth
fraction taken between about 85-95.degree. C. has between about 10
and about 40 branches per 1000 carbon atoms, wherein between about
50 to about 90% are methyl branches, about 5 to about 15% are ethyl
branches, about 0 to about 10% are propyl branches, about 0 to
about 15% are butyl branches, and between about 5 and about 15% are
pentyl or longer branches; a seventh fraction taken between about
95-100.degree. C. has between about 5 and about 35 branches per
1000 carbon atoms, wherein between about 50 to about 90% are methyl
branches, about 5 to about 15% are ethyl branches, about 0 to about
10% are propyl branches, about 0 to about 15% are butyl branches,
and between about 0 and about 15% are pentyl or longer branches; an
eighth fraction taken between about 100-110.degree. C. has between
about 0 and about 25 branches per 1000 carbon atoms, wherein
between about 50 to about 90% are methyl branches, about 5 to about
15% are ethyl branches, about 0 to about 10% are propyl branches,
about 0 to about 15% are butyl branches, and between about 0 and
about 15% are pentyl or longer branches; a ninth fraction taken
between about 110-140.degree. C. has between about 0 and about 30
branches per 1000 carbon atoms, wherein between about 50 to about
90% are methyl branches, about 5 to about 15% are ethyl branches,
about 0 to about 10% are propyl branches, about 0 to about 15% are
butyl branches, and between about 0 to about 15% are pentyl or
longer branches; a tenth fraction taken between about
140-150.degree. C. has between about 0 and about 20 branches per
1000 carbon atoms, wherein between about 50 to about 90% are methyl
branches, about 5 to about 15% are ethyl branches, about 0 to about
10% are propyl branches, about 0 to about 15% are butyl branches,
and between about 0 to about 15% are pentyl or longer branches; and
a tenth fraction has between about 0 and about 20 branches per 1000
carbon atoms.
[0131] In contrast to a polymer prepared by solution
polymerization, where the melting temperature as defined by the
endothermic maximum is inversely correlated with the average degree
of branching of said polymer, the polymers prepared from the
supported catalysts of the present invention exhibit a relatively
constant melting temperature (endothermic maximum) over a
relatively wide range of average branching. In certain cases, this
also provides a free flowing powder which is again, a significant
processing advantage in the gas phase.
[0132] In a further embodiment, there is provided a polymer derived
from essentially ethylene alone that has greater than 30 branches
per 1000 carbon atoms and a melt transition (endothermic maximum)
in the DSC of greater than about 110.degree. C. Preferably, the
polymer is a free flowing polymer.
[0133] In a further embodiment, there is provided a polymer derived
from ethylene alone that has a broad composition distribution and a
molecular weight distribution of less than 6 and greater than 2.5,
wherein said polymer has an average degree of branching of from 5
to 120 alkyl branches per 1000 carbon atoms, and wherein any
individual component of said polymer has a degree of branching of
from 0 to 150 alkyl branches per 1000 carbon atoms. In such polymer
compositions, it is preferred that an individual component of the
polymer has between about 40 and 100 branches per 1000 carbon
atoms, another component has between about 30 and 90 branches per
1000 carbon atoms, another component has between about 30 and 80
branches per 1000 carbon atoms, another component has between about
20 and 60 branches per 1000 carbon atoms, another component has
between about 10 and 50 branches per 1000 carbon atoms, another
component has between about 10 and 40 branches per 1000 carbon
atoms, another component has between about 5 and 35 branches per
1000 carbon atoms, another component has between about 0 and 25
branches per 1000 carbon atoms, another component has between about
0 and 30 branches per 1000 carbon atoms, another component has
between about 0 and 20 branches per 1000 carbon atoms.
[0134] We have also recognized that by attaching a Group 8-10
polymerization catalyst to a solid support one can improve its
functional group compatibility over that observed in the homogenous
solution polymerization. In other words, the rate for the
co-polymerization of one or more olefin monomers of the type
RCH.dbd.CHR.sup.8 with one or more functional olefin monomers of
type CH.sub.2.dbd.CH(CH.sub.2).sub.nJ is increased over the
homogeneous solution polymerization run under otherwise identical
conditions. In particular, we have found that by utilizing a
supported Group 8-10 catalyst that monomers of the general formula
CH.sub.2.dbd.CH(CH.sub.2).sub.nJ are copolymerized with other
olefins (e.g. ethylene) at rates several orders of magnitude
greater than that observed for corresponding homogeneous systems.
In this regard, examples of Group 8-10 catalysts useful in this
process include those described in U.S. Pat. Nos. 5,866,663;
5,886,224; 5,891,963; 5,880,323; 5,880,241 are incorporated herein
by reference, along with WO9623010, WO9910391, WO 9905189, WO
9856832, WO 9803559, WO 9847934, WO9702298, WO 9830609, WO 9842665,
WO 9842664, WO 9847933, WO 9840420, WO 9840374.
[0135] Thus, in a further embodiment, there is provided a Group
8-10 transition metal catalyst having an improved rate for the
co-polymerization of one or more olefin monomers of the type
RCH.dbd.CHR.sup.8 with one or more functional olefin monomers of
the formula CH.sub.2.dbd.CH(CH.sub.2).sub.nJ, in an olefin
polymerization reaction which comprises combining said catalyst
with a solid support, and optionally a Bronsted or Lewis acid in
any order, prior to the utilization of said catalyst in said olefin
polymerization reaction.
[0136] R and R.sup.8 each, independently, represent a hydrogen, a
hydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclic
olefin;
[0137] n is an interger between 1-20;
[0138] J is a group selected from ester, acyl, acid halide,
aldehyde, alkyl amide, aryl, alkylamine, aryl amine, alkyl amido,
aryl amido, alkyl imido, aryl imido, ether, nitrile, alcohol, keto,
amino, amido, imido, alkoxy thiol, thioalkoxy, acid, urea,
sulfonamido, and sulfoester. Preferably, the compound of the
formula CH.sub.2.dbd.CH(CH.sub.2).sub.nJ is a compound of the
formula CH.sub.2.dbd.CH(CH.sub.2).sub.nCO.sub.2R.sup- .1, wherein
R.sup.1 is hydrogen, hydrocarbyl, substituted hydrocarbyl,
fluoroalkyl or silyl; and
[0139] n is an integer greater than 3;
[0140] In a further embodiment, the present invention provides an
ethylene homopolymer with a CDBI of less than 50 %, preferably less
than 40%, and more preferably less than 30%.
[0141] In a further embodiment, the present invention provides a
polyalkene with a CDBI of less than 50%, which contains about 80 to
about 150 branches per 1000 methylene groups, and which contains
for every 100 branches that are methyl, about 30 to about 90 ethyl
branches, about 4 to about 20 propyl branches, about 15 to about 50
butyl branches, about 3 to about 15 amyl branches, and about 30 to
about 140 hexyl or longer branches. Further preferred is a
polyalkene of with a CDBI of less than 40%, more preferably less
than 30%. Further preferred are those polyalkenes which contain
about 100 to about 130 branches per 1000 methylene groups, and
which contains for every 100 branches that are methyl, about 50 to
about 75 ethyl branches, about 5 to about 15 propyl branches, about
24 to about 40 butyl branches, about 5 to about 10 amyl branches,
and about 65 to about 120 hexyl or longer branches.
[0142] In a further embodiment, there is provided a polyalkene with
a CDBI of less than 50% which contains about 20 to about 150
branches per 1000 methylene groups, and which contains for every
100 branches that are methyl, about 4 to about 20 ethyl branches, 1
to about 12 propyl branches, 1 to about 12 butyl branches, 1 to
about 10 amyl branches, and 0 to about 20 hexyl or longer branches.
Further preferred are the polyalkenes with a CDBI of less than 40%,
more preferably less than 30%. Further preferred embodiments
include the polyalkenes which contains about 40 to about 100
branches per 1000 methylene groups, and which contains for every
100 branches that are methyl, about 6 to about 15 ethyl branches,
about 2 to about 10 propyl branches, about 2 to about 10 butyl
branches, about 2 to about 8 amyl branches, and about 2 to about 15
hexyl or longer branches.
[0143] The polymers of the present invention include homopolymers
of olefins, such as polyethylene, polypropylene, and the like, and
olefin copolymers, including functional-group containing
copolymers. As an example, ethylene homopolymers can be prepared
with strictly linear to highly branched structures by variation of
the catalyst structure, cocatalyst composition, and reaction
conditions, including pressure and temperature. The effect these
parameters have on polymer structure is described herein. These
polymers and copolymers have a wide variety of applications,
including use as packaging material and in adhesives.
[0144] In this disclosure certain chemical groups or compounds are
described by certain terms and symbols. These terms are defined as
follows:
[0145] Symbols ordinarily used to denote elements in the Periodic
Table take their ordinary meaning, unless otherwise specified.
Thus, N, O, S, P, and Si stand for nitrogen, oxygen, sulfur,
phosphorus, and silicon, respectively.
[0146] Examples of neutral Lewis acids include, but are not limited
to, methylaluminoxane (hereinafter MAO) and other aluminum
sesquioxides, R.sup.7.sub.3Al, R.sup.7.sub.2AlCl, R.sup.7AlCl.sub.2
(where R.sup.7 is alkyl), organoboron compounds, boron halides,
B(C.sub.6F.sub.5).sub.3, BPh.sub.3, and
B(3,5-(CF.sub.3).sub.2C.sub.6H.sub.3).sub.3. Examples of ionic
compounds comprising a cationic Lewis acid include:
R.sup.9.sub.3Sn[BF.sub.4], (where R.sup.9 is hydrocarbyl),
MgCl.sub.2, and H.sup.+X.sup.-, where X.sup.- is a weakly
coordinating anion.
[0147] The term "weakly coordinating anion" is well-known in the
art per se and generally refers to a large bulky anion capable of
delocalization of the negative charge of the anion. Suitable weakly
coordinating anions include, but are not limited to,
PF.sub.6.sup.-, BF.sub.4.sup.-, SbF.sub.6.sup.-, (Ph).sub.4B.sup.-
wherein Ph=phenyl, .sup.-BAr.sub.4 wherein
.sup.-BAr.sub.4=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. The
coordinating ability of such anions is known and described in the
literature (Strauss, S. et al., Chem. Rev. 1993, 93, 927).
[0148] Examples of neutral Lewis bases include, but are not limited
to, (i) ethers, for example, diethyl ether or tetrahydrofuran, (ii)
organic nitrites, for example acetonitrile, (iii) organic sulfides,
for example dimethylsulfide, or (iv) monoolefins, for example,
ethylene, hexene or cyclopentene.
[0149] A "hydrocarbyl" group means a monovalent or divalent,
linear, branched or cyclic group which contains only carbon and
hydrogen atoms. Examples of monovalent hydrocarbyls include the
following: C.sub.1-C.sub.20 alkyl; C.sub.1-C.sub.20 alkyl
substituted with one or more groups selected from C.sub.1-C.sub.20
alkyl, C.sub.3-C.sub.8 cycloalkyl or aryl; C.sub.3-C.sub.8
cycloalkyl; C.sub.3-C.sub.8 cycloalkyl substituted with one or more
groups selected from C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.8
cycloalkyl or aryl; C.sub.6-C.sub.14 aryl; and C.sub.6-C.sub.14
aryl substituted with one or more groups selected from
C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.8 cycloalkyl or aryl; where
the term "aryl" preferably denotes a phenyl, napthyl, or
anthracenyl group. Examples of divalent (bridging) hydrocarbyls
include: --CH.sub.2--, --CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2CH.sub.2--, and 1,2-phenylene.
[0150] A "silyl" group refers to a SiR.sub.3 group wherein Si is
silicon and R is hydrocarbyl or substituted hydrocarbyl or silyl,
as in Si(SiR.sub.3).sub.3.
[0151] A "heteroatom" refers to an atom other than carbon or
hydrogen. Preferred heteroatoms include oxygen, nitrogen,
phosphorus, sulfur, selenium, arsenic, chlorine, bromine, silicon
and fluorine.
[0152] A "substituted hydrocarbyl" refers to a monovalent or
divalent hydrocarbyl substituted with one or more heteroatoms.
Examples of monovalent substituted hydrocarbyls include:
2,6-dimethyl-4-methoxyphenyl- , 2,6-diisopropyl-4-methoxyphenyl,
4-cyano-2,6-dimethylphenyl, 2,6-dimethyl-4-nitrophenyl,
2,6-difluorophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl,
4-methoxycarbonyl-2,6-dimethylphenyl, 2-tert-butyl-6-chlorophenyl,
2,6-dimethyl4-phenylsulfonylphenyl,
2,6-dimethyl-4-trifluoromethylphenyl,
2,6-dimethyl-4-trimethylammoniumphe- nyl (associated with a weakly
coordinated anion), 2,6-dimethyl-4-hydroxyph- enyl,
9-hydroxyanthr-10-yl, 2-chloronapth-1-yl, 4-methoxyphenyl,
4-nitrophenyl, 9-nitroanthr-10-yl, -CH.sub.2OCH.sub.3, cyano,
trifluoromethyl, or fluoroalkyl. Examples of divalent (bridging)
substituted hydrocarbyls include: 4-methoxy-1,2-phenylene,
1-methoxymethyl-1,2-ethanediyl,
1,2-bis(benzyloxymethyl)-1,2-ethanediyl, or
1-(4-methoxyphenyl)-1,2-ethanediyl.
[0153] A "sterically hindered aryl" means (i) a phenyl ring with
hydrocarbyl, substituted hydrocarbyl, F, Cl, Br or silyl
substituents at both the 2- and 6-positions, optionally substituted
elsewhere with hydrocarbyl, substituted hydrocarbyl, F, Cl, Br,
silyl, hydroxy, methoxy, nitro, cyano, phenylsulfonyl, CO.sub.2Me,
CO.sub.2H, C(O)CH.sub.3, CF.sub.3, or fluoroalkyl substituents,
(ii) a 2-substituted napth-1-yl ring, optionally substituted
elsewhere with hydrocarbyl, substituted hydrocarbyl, F, Cl, Br,
silyl, hydroxy, methoxy, nitro, cyano, phenylsulfonyl, CO.sub.2Me,
CO.sub.2H, C(O)CH.sub.3, CF.sub.3, or fluoroalkyl substituents,
(iii) an 9-anthracenyl or 1,2,3,4,5,6,7,8-octahydro-9-anthracenyl
ring, optionally substituted elsewhere with hydrocarbyl,
substituted hydrocarbyl, F, Cl, Br, silyl, hydroxy, methoxy, nitro,
cyano, phenylsulfonyl, CO.sub.2Me, CO.sub.2H, C(O)CH.sub.3,
CF.sub.3, or fluoroalkyl substituents, or (iv) an aromatic
substituted hydrocarbyl with steric properties functionally
equivalent (in the context of this invention) to one or more of the
following sterically hindered aryls: 2,6-dimethylphenyl,
2,4,6-trimethylphenyl, 2,6-diisopropylphenyl,
2,6-dimethyl-4-nitrophenyl, 2,6-dimethyl-4-phenylsulfonylphenyl,
2-isopropyl-6-methylphenyl, 2,6-bis(trifluoromethyl)phenyl,
2,6-dimethyl-4-methoxyphenyl, 2-methylnapth-1-yl, 9-anthracenyl,
1,2,3,4,5,6,7,8-octahydro-9-anthraceny- l, 2,6-diclorophenyl,
2,6-dibromophenyl, 2-tert-butyl-6-methylphenyl,
2-trimethylsilylnapth-1-yl, 2-chloro-6-methylphenyl,
4-cyano-2,6-dimethylphenyl, 2,6-diisopropyl-4-methoxyphenyl,
2,4,6-tri-tert-butylphenyl, and 2-chloro-6-tert-butylphenyl.
[0154] A "heteroatom connected mono-radical" refers to a
mono-radical group in which a heteroatom serves as the point of
attachment. Examples include: NH(2,6-dimethylphenyl) and SPh, where
Ph is phenyl. Numerous other examples are given herein.
[0155] A "substituted silicon atom" refers to a --SiR.sup.9.sub.2--
group, wherein R.sup.9 is a hydrocarbyl or substituted
hydrocarbyl.
[0156] A "substituted phosphorous atom" refers to a
--P(O)(OR.sup.9)-- group, wherein R.sup.9 is a hydrocarbyl or
substituted hydrocarbyl.
[0157] A "substituted sulfur atom" refers to a --S(O)--,
--SO.sub.2--, or --S(NR.sup.9).sub.2-- group, wherein R.sup.9 is a
hydrocarbyl or substituted hydrocarbyl.
[0158] A "bridging group" refers to a divalent hydrocarbyl,
divalent substituted hydrocarbyl, --C(O)--, --C(S)--, substituted
silicon atom, substituted sulfur atom, substituted phosphorous
atom, --CH.sub.2C(O)--, --C(O)C(O)--, or
3,4,5,6-tetrafluoro-1,2-phenylene.
[0159] In certain cases, the bridging group, together with groups A
and B, may collectively form a divalent heteroatom substituted
heterocycle; examples include: 18
[0160] A "mono-olefin" refers to a hydrocarbon containing one
carbon-carbon double bond.
[0161] A "suitable metal precursor" refers to a Group 8-10
transition metal compound, preferably Ni, Co, Pd, and Fe compounds,
which may be combined with compound X (preferably, compound III,
VI, IX, XVII or XVIII, described below), and optionally a Lewis or
Bronsted acid, to form an active olefin polymerization catalyst.
Examples include: (1,2-dimethoxyethane)nickel(II) dibromide,
bis[(.mu.-chloro)(1,2,3-.eta..- sup.3-2-propenyl)nickel(II)],
bis[(.mu.-chloro)(1,2,3-.eta..sup.3-2-propen- yl)palladium(II)],
bis[(.mu.-chloro)(1,2,3-.eta.3-1-trimethylsilyloxy-2-pr-
openyl)nickel(II)], CoBr.sub.2, FeBr.sub.2,
bis(acetylacetonate)Ni(II), and
[tetrakis(acetonitrile)Pd(II)][BF.sub.4].
[0162] A "suitable nickel precursor" refers to a suitable metal
precursor wherein the metal is nickel.
[0163] A "suitable nickel(0) precursor" refers to a suitable metal
precursor which is a zerovalent nickel compound.
[0164] The term "fluoroalkyl" as used herein refers to a
C.sub.1-C.sub.20 alkyl group substituted by one or more fluorine
atoms.
[0165] The term "polymer" as used herein is meant a species
comprised of monomer units and having a degree of polymerization
(DP) of ten or higher.
[0166] The term ".alpha.-olefin" as used herein is a 1-alkene with
from 3 to 40 carbon atoms.
[0167] A ".pi.-allyl" group refers to a monoanionic group with
three sp.sup.2 carbon atoms bound to a metal center in a
.eta..sup.3-fashion. Any of the three sp.sup.2 carbon atoms may be
substituted with a hydrocarbyl, substituted hydrocarbyl, heteroatom
connected hydrocarbyl, heteroatom connected substituted
hydrocarbyl, or O-silyl group. Examples of .pi.-allyl groups
include: 19
[0168] The term .pi.-benzyl group denotes an .pi.-allyl group where
two of the sp.sup.2 carbon atoms are part of an aromatic ring.
Examples of .pi.-benzyl groups include:
[0169] A polymer with a "broad composition distribution" refers to
a polymer that comprises a plurality of compositions (preferably
>5) having varying levels of branching. The polymers can be
fractionated and the fractions have levels of branching/1000
carbons that range from about 0 to about 100 branches/1000
carbons.
[0170] "Composition Distribution Breadth Index" or CDBI is defined
as the weight percent of the polymer molecules having a branching
content within 50% (that is, 25% on each side of the average total
branching) of the average total branching of the bulk sample as
determined by .sup.1H NMR. The CDBI is readily determined using
well known fractionation techniques such as temperature rising
elution fractionation (TREF). (See also WO 97/48735 and WO
93/03093).
[0171] Sample calculation:
[0172] bulk polymer has 40 branches/1000 carbon atoms
[0173] 30-40-50 (degree of branching within 50% of the average
branching for bulk sample)
[0174] fractionate polymer using TREF or other technique
[0175] calculate the weight percent of the total polymer that has
total branches as determined by NMR between 30 and 50. e.g. 5 grams
of the total 10 grams charged when fractionated and analyzed has
branching between 30 and 50 branches/1000 carbon atoms. CDBI for
this polymer would be 50%.
[0176] A "free flowing polymer" refers to a non-tacky polymer that
can be transported without significant agglomeration. In this
context, this lack of significant agglomeration refers to polymer
products which are useful under commercial gas phase reactor
conditions.
[0177] As used herein, the terms "monomer" and "olefin monomer"
refer to the olefin or other monomer compound before it has been
polymerized; the term "monomer units" refers to the moieties of a
polymer that correspond to the monomers after they have been
polymerized.
[0178] In some cases, a compound Y is required as a cocatalyst.
Suitable compounds Y include a neutral Lewis acid capable of
abstracting Q.sup.- or W.sup.- to form a weakly coordinating anion,
a cationic Lewis acid whose counterion is a weakly coordinating
anion, or a Bronsted acid whose conjugate base is a weakly
coordinating anion. Preferred compounds Y include:
methylaluminoxane (hereinafter MAO) and other aluminum
sesquioxides, R.sup.7.sub.3Al, R.sup.7.sub.2AlCl, R.sup.7AlCl.sub.2
(wherein R.sup.7 is alkyl), organoboron compounds, boron halides,
B(C.sub.6F.sub.5).sub.3, R.sup.9.sub.3Sn[BF.sub.4] (wherein R.sup.9
hydrocarbyl), MgCl.sub.2, and H.sup.+X.sup.-, wherein X.sup.- is a
weakly coordinating anion. Examples of H.sup.+X.sup.- are the ether
solvate of hydrogen tetrakis[3,5-bis(trifluoromethyl)phenyl]borate
and montmorillinite clay.
[0179] Examples of "solid support" include inorganic oxide support
materials, such as: talcs, silicas, titania, silica/chromia,
silica/chromia/titania, silica/alumina, zirconia, aluminum
phosphate gels, silanized silica, silica hydrogels, silica
xerogels, silica aerogels, montmorillonite clay and silica co-gels
as well as organic solid supports such as polystyrene and
functionalized polystyrene. (See, for example, Roscoe, S. B.;
Frechet, J. M. J.; Walzer, J. F.; Dias, A. J.; "Polyolefin Spheres
from Metallocenes Supported on Non-interacting Polystyrene", 1998,
Science, 280, 270-273 (1998).) An especially preferred solid
support is one which has been pre-treated with Y compounds as
described herein, most preferably with MAO. Thus, in a preferred
embodiment, the catalysts of the present invention are attached to
a solid support (by "attached to a solid support" is meant ion
paired with a component on the surface, adsorbed to the surface or
covalently attached to the surface) which has been pre-treated with
a compound Y. Alternatively, the catalyst, the compound Y, and the
solid support can be combined in any order, and any number of Y
compounds can be utilized; in addition, the supported catalyst thus
formed, may be treated with additional quantities of compound(s) Y.
In an especially preferred embodiment, the compounds of the present
invention are attached to silica which has been pre-treated with
MAO. Such supported catalysts are prepared by contacting the
transition metal compound, in a substantially inert solvent--by
which is meant a solvent which is either unreactive under the
conditions of catalyst preparation, or if reactive, acts to
usefully modify the catalyst activity or selectivity--with MAO
treated silica for a sufficient period of time to generate the
supported catalysts. Examples of substantially inert solvents
include toluene, mineral spirits, hexane, CH.sub.2Cl.sub.2 and
CHCl.sub.3.
[0180] It is known to those skilled in the art that a variety of
protocols may be used to generate active polymerization catalysts
comprising transition metal complexes of various nitrogen,
phosphorous, oxygen and sulfur donor ligands. Examples of such
protocols include (i) the reaction of a Group 8-10 metal dihalide
complex of a bidentate N-donor ligand with an alkylaluminum
reagent, (ii) the reaction of a bidentate N-donor ligand with
nickel( 1,5-cyclooctadiene).sub.2 and
HB(3,5-bis(trifluoromethyl)phe- nyl).sub.4, and (iii) the reaction
of a Group 8-10 metal dialkyl complex of a bidentate N-donor ligand
with MAO or HB(3,5-bis(trifluoromethyl)phen- yl).sub.4. In some
cases, it is also possible to react a bidentate N-donor ligand with
nickel(1,5-cyclooctadiene).sub.2 and B(C.sub.6F.sub.5).sub.3 to
obtain an active catalyst. Cationic (ligand)M(.pi.-allyl) complexes
with weakly coordinating counteranions, where M is a Group 8-10
transition metal, are often suitable as catalyst precursors,
requiring only exposure to olefin monomer and in some cases
elevated temperatures (40-200.degree. C.) or added Lewis acid, or
both, to form an active polymerization catalyst.
[0181] Isolable
[(ligand)Ni(methyl)(O(CH.sub.2CH.sub.3).sub.2)][B(3,5-bis(-
trifluoromethyl)phenyl).sub.4] and
[(ligand)Pd(methyl)(O(CH.sub.2CH.sub.3)-
.sub.2)][B(3,5-bis(trifluoromethyl)phenyl).sub.4] salts may also
serve as one component catalyst systems. More generally, a variety
of (ligand)M(Q)(W) complexes, where "ligand" refers to a compound
of formula X, M is a divalent Group 8-10 transition metal, and Q
and W are univalent groups, or may be taken together to form a
divalent group, may be reacted with one or more compounds,
collectively referred to as compound Y, which function as
co-catalysts or activators, to generate an active catalyst of the
form [(ligand)M(T)(L)].sup.+X.sup.-, where T is a hydrogen atom or
hydrocarbyl, L is an olefin or neutral donor group capable of being
displaced by an olefin, and X.sup.- is a weakly coordinating
anion.
[0182] When Q and W are both halide, examples of suitable compounds
Y include: methylaluminoxane (hereinafter "MAO") and other aluminum
sesquioxides, R.sup.0.sub.3Al, R.sup.0.sub.2AlCl, and
R.sup.0AlCl.sub.2 (wherein R.sup.0 is alkyl). When Q and W are both
alkyl, examples of suitable compounds Y include: MAO and other
aluminum sesquioxides, R.sup.0.sub.3Al, R.sup.0.sub.2AlCl,
R.sup.0AlCl.sub.2 (wherein R.sup.0 is alkyl),
B(C.sub.6F.sub.5).sub.3, R.sup.16.sub.3Sn[BF.sub.4],
H.sup.+X.sup.-, wherein X.sup.- is a weakly coordinating anion, for
example, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and Lewis
acidic or Bronsted acidic metal oxides, for example,
montmorillonite clay. In some cases, for example, when Q and W are
both halide or carboxylate, sequential treatment with a metal
hydrocarbyl, followed by reaction with a Lewis acid or Bronsted
acid, may be required to generate an active catalyst. Suitable
examples of metal hydrocarbyls include: MAO, other aluminum
sesquioxides, R.sup.0.sub.3Al, R.sup.0.sub.2AlCl, R.sup.0AlCl.sub.2
(wherein R.sup.0 is alkyl), Grignard reagents, organolithium
reagents, and diorganozinc reagents. Examples of suitable Lewis
acids or Bronsted acids include: MAO, other aluminum sesquioxides,
R.sup.0.sub.3Al, R.sup.0.sub.2AlCl, R.sup.0AlCl.sub.2 (wherein
R.sup.0 is alkyl), B(C.sub.6F.sub.5).sub.3,
R.sup.16.sub.3Sn[BF.sub.4], H.sup.+X.sup.-, wherein X.sup.- is a
weakly coordinating anion, for example,
tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and Lewis acidic or
Bronsted acidic metal oxides, for example, montmorillonite
clay.
[0183] While not wishing to be bound by theory, the present
inventors believe that the Lewis acid may be acting to further
activate the catalysts provided herein via coordination to one or
more of those heteroatoms which are not directly bound to the
transition metal M, but which are .pi.-conjugated to the nitrogens
which are bound to the transition metal M. Substituents which
contain additional Lewis basic groups, including, but not limited
to, methoxy groups, positioned so as to further promote the binding
of the Lewis acid at such .pi.-conjugated heteroatoms, are also
included in this invention. A nonlimiting example of secondary
Lewis acid binding would include the following: 20
[0184] wherein R.sup.1, R.sup.2, R.sup.5, and R.sup.6 are
2,6-dimethylphenyl; and X.sup.- is a weakly coordinating anion.
[0185] The polymerizations may be conducted as solution
polymerizations, as non-solvent slurry type polymerizations, as
slurry polymerizations using one or more of the olefins or other
solvent as the polymerization medium, or in the gas phase. One of
ordinary skill in the art, with the present disclosure, would
understand that the catalyst could be supported using a suitable
catalyst support and methods known in the art. Substantially inert
solvents, such as toluene, hydrocarbons, methylene chloride and the
like, may be used. Propylene and 1-butene are excellent monomers
for use in slurry-type copolymerizations and unused monomer can be
flashed off and reused.
[0186] Temperature and olefin pressure have significant effects on
polymer structure, composition, and molecular weight. Suitable
polymerization temperatures are preferably from about -100.degree.
C. to about 200.degree. C., more preferably in the 20.degree. C. to
150.degree. C. range.
[0187] After the reaction has proceeded for a time sufficient to
produce the desired polymers, the polymer can be recovered from the
reaction mixture by routine methods of isolation and/or
purification.
[0188] In general, the polymers of the present invention are useful
as components of thermoset materials, as elastomers, as packaging
materials, films, compatibilizing agents for polyesters and
polyolefins, as a component of tackifying compositions, and as a
component of adhesive materials.
[0189] High molecular weight resins are readily processed using
conventional extrusion, injection molding, compression molding, and
vacuum forming techniques well known in the art. Useful articles
made from them include films, fibers, bottles and other containers,
sheeting, molded objects and the like.
[0190] Low molecular weight resins are useful, for example, as
synthetic waxes and they may be used in various wax coatings or in
emulsion form. They are also particularly useful in blends with
ethylene/vinyl acetate or ethylene/methyl acrylate-type copolymers
in paper coating or in adhesive applications.
[0191] Although not required, typical additives used in olefin or
vinyl polymers may be used in the new homopolymers and copolymers
of this invention. Typical additives include pigments, colorants,
titanium dioxide, carbon black, antioxidants, stabilizers, slip
agents, flame retarding agents, and the like. These additives and
their use in polymer systems are known per se in the art.
[0192] The molecular weight data presented in the following
examples is determined at 135.degree. C. in 1,2,4-trichlorobenzene
using refractive index detection, calibrated using narrow molecular
weight distribution poly(styrene) standards.
EXAMPLES
[0193] Other features of the invention will become apparent in the
course of the following descriptions of exemplary embodiments which
are given for illustration of the invention and are not intended to
be limiting thereof.
Example 1
Preparation of N,N'-bis(2,6-dimethylphenyl)oxalamide
[0194] 2,6-dimethylaniline, triethylamine, and dichloromethane were
dried by passage through basic alumina. A 1 L round bottom flask,
equipped with a magnetic stir bar and a 125 mL pressure-equalizing
dropping funnel capped by a nitrogen inlet adapter, was charged
with 53.38 g of 2,6-dimethylaniline, 250 mL of dichloromethane, and
44.76 g of triethylamine. A solution of 25.34 g of oxalyl chloride
in 80 mL of dichloromethane was added dropwise under nitrogen with
stirring and ice-bath cooling over 1.2 hours to give a thick paste
which had to be occasionally swirled by hand to effect mixing. The
mixture was allowed to stir at room temperature for 14 hours, then
transferred to a separatory funnel, washed 3 times with water,
separated and concentrated under reduced pressure (10 mm Hg) to
give 63 g of crude solid. The crude product was dissolved in a
boiling mixture of 1.30 L of toluene and 2.85 L of absolute
ethanol, cooled to room temperature (about 23.degree. C.) and
diluted with 260 mL of water, then allowed to crystallize for 16
hours. The resultant precipitate was isolated by vacuum filtration,
washed with methanol (3.times.100 mL) and dried to give 39.1 g
(66%) as white crystals. An additional 9.5 g (16.1%) was recovered
from the filtrate by further dilution with approximately 500 mL of
water. Field desorption mass spectrometry showed a parent ion peak
at 296 m/z. .sup.1H NMR (300 MHz, CDCl.sub.3, chemical shifts in
ppm relative to TMS at 0 ppm): 2.29 (12 p, s), 7.15 (6 p, m), 8.86
(2 p, br s).
Example 2
Preparation of N,N'-bis(2,6-diisopropylphenyl)oxalamide
[0195] 2,6-Diisopropylaniline, triethylamine, and dichloromethane
were dried by passage through basic alumina. A 1 L round bottom
flask, equipped with a magnetic stir bar and a 125 mL
pressure-equalizing dropping funnel capped by a nitrogen inlet
adapter, was charged with 34.73 g of 2,6-diisopropylaniline
(previously distilled), 180 mL of dichloromethane, and 18.30 g of
triethylamine. A solution of 10.57 g oxalyl chloride in 43 mL of
dichloromethane was added dropwise under nitrogen with stirring and
ice-bath cooling over 38 minutes to give a thick paste which had to
be occasionally swirled by hand to effect mixing. The mixture was
allowed to stir at room temperature (about 23.degree. C.) for 60
hours, then diluted with 700 mL of water to precipitate the
product, which was isolated by filtration, washed with water and
recrystallized from boiling isopropanol (4 L) to afford 22.38 g
(66%) of white needles. Field desorption mass spectrometry showed a
parent ion peak at 408 m/z. .sup.1H NMR (500 MHz, CD.sub.2Cl.sub.2,
chemical shifts in ppm relative to TMS at 0 ppm): 1.22 (24 p, d,
6.8 Hz), 3.08 (4 p, septet, 6.8 Hz), 7.25 (4 p, d, 7.5 Hz), 7.37 (2
p, t, 7.5 Hz), 8.86 (2 p, br s).
Example 3
Preparation of N,N'-bis (4-methoxy-2,6-dimethylphenyl)oxalamide
[0196] Triethylamine and dichloromethane were dried by passage
through basic alumina. A 50 mL round bottom flask, equipped with a
magnetic stir bar and a small pressure-equalized dropping funnel
capped by a nitrogen inlet adapter, was charged with 1.5 g of
4-methoxy-2,6-dimethylphenylamin- e, 8 mL of dichloromethane, and
1.38 g of triethylamine. A solution of 0.39 of oxalyl chloride in 2
mL of dichloromethane was added dropwise under a nitrogen
atmosphere with stirring and ice-bath cooling over 35 min. The
mixture was allowed to stir at room temperature for 14 hours, then
transferred to a separatory funnel, washed with water, separated
and concentrated under reduced pressure (10 mm Hg) to give 1.75 g
solids. The crude product was dissolved in 150 mL of boiling
absolute ethanol and crystallized upon cooling to room temperature
(about 23.degree. C.). The resultant precipitate was isolated by
vacuum filtration, and dried to give 1.39 g (86%) as white
crystals. Field desorption mass spectrometry showed a parent ion
peak at 356 m/z.
Example 4
Preparation of N.sup.1/
N.sup.2-bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride
[0197] A 1 L round bottom flask was charged with 30.0 g of
N,N'-bis(2,6-dimethylphenyl)oxalamide, 58.8 g of phosphorous
pentachloride and 150 mL of dry toluene, and equipped with a
magnetic stir bar and a reflux condenser capped by a nitrogen inlet
adapter connected to a bubbler. The mixture was heated to reflux
over 30 minutes, then maintained at reflux under nitrogen for
another 95 minutes to give a yellow solution. Heating was
discontinued and the mixture was allowed to cool to room
temperature (about 23.degree. C.). A short path distillation
adapter and receiving flask was attached in place of the condenser
and the volatiles were removed under reduced pressure (1 mm Hg),
initially at room temperature, then at 100.degree. C., to give 20.1
g (60%) of a granular yellow solid. Field desorption mass
spectrometry showed a parent ion peak at 332 m/z. .sup.1H NMR (300
MHz, C.sub.6D.sub.6, chemical shifts in ppm relative to TMS at 0
ppm): 2.04 (12 p, s), 6.91 (6 p, s).
Example 5
Preparation of
N.sup.1,N.sup.2-bis(2,6-diisopropylphenyl)oxalodiimidoyl
dichloride
[0198] A 500 mL round bottom flask equipped with a magnetic stir
bar and a reflux condenser capped by a nitrogen inlet adapter
connected to a bubbler was charged with 2.50 g of
N,N'-bis(2,6-diispropylphenyl)-oxalami- de, 3.58 g of phosphorous
pentachloride and 36 mL of dry toluene. The mixture was heated to
reflux over 30 minutes, then maintained at reflux under nitrogen
for another 210 minutes to afford a clear yellow solution. Heating
was discontinued and the mixture was allowed to cool to room
temperature (about 23.degree. C.). A short path distillation
adapter and receiving flask were attached in place of the condenser
and the volatiles were removed under reduced pressure (1 mm Hg),
initially at room temperature, then at 100.degree. C., to give a
yellow oil, which slowly crystallized upon complete cooling. The
product was purified by column chromatography (SiO.sub.2, Merck
Grade 9385 230-400 mesh, 60 .ANG.; 3 v % ethyl acetate in hexane)
to afford 1.49 g (55%) yellow crystals. Field desorption mass
spectrometry showed a parent ion peak at 444 m/z.
Example 6
Preparation of
N.sup.1,N.sup.2-bis(4-methoxy-2,6-dimethylphenyl)oxalodiimi- doyl
dichloride
[0199] A 50 mL round bottom flask was charged with 1.37 g of
N,N'-bis(4-methoxy-2,6-dimethylphenyl)oxalamide 1.88 g of
phosphorous pentachloride and 15 mL of dry toluene, and equipped
with a magnetic stir bar and a reflux condenser capped by a
nitrogen inlet adapter connected to a bubbler. The mixture was
heated, with stirring, at about 100.degree. C. until the evolution
of HCl ceased. Then, another 0.22 g PCl.sub.5 was added and the
mixture was heated another 30 min at 80.degree. C. After cooling to
room temperature the mixture was transferred to a separatory
funnel, and some crystallization occurred upon transfer. Complete
transfer and re-dissolution of the product was accomplished by the
addition of dichloromethane. The organic layer was washed with
saturated aqueous sodium bicarbonate, then concentrated in vacuo to
afford 1.44 g crystalline yellow solid. Field desorption mass
spectrometry showed a parent ion peak at 392 m/z.
Example 7
Preparation of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane
[0200] A 50 mL round bottom flask equipped with a magnetic stir bar
and a reflux condenser capped by a nitrogen inlet was charged with
504 mg of N.sup.1,N.sup.2-bis(2,6-dimethylphenyl)oxalodiimidoyl
dichloride, 136 mg of sodium hydride (60% mineral oil dispersion),
4.0 mL of dry tetrahydrofuran and 0.140 mL of 1,2-ethanedithiol.
The mixture was heated at reflux for 2 hours, after which another
66 mg of sodium hydride dispersion was added and the mixture was
refluxed for an additional hour. After cooling, the mixture was
diluted with water and diethyl ether, and the ether layer was
separated, washed again with water, and dried with magnesium
sulfate to afford a yellow-orange oil. Column chromatography
(SiO.sub.2, Merck Grade 9385 230-400 mesh, 60 .ANG.; 15 v % of
ethyl acetate in hexane) afforded 296 mg of a yellow oil which was
crystallized by addition of hexane and collected by vacuum
filtration to give 219 mg of yellow granular crystals. Field
desorption mass spectrometry showed a parent ion peak at 354 m/z.
.sup.1H NMR (300 MHz, CDCl.sub.3, chemical shifts in ppm relative
to TMS at 0 ppm): 2.17 (12p, s), 3.27 (4p, br s), 6.4-7.12 (6 p,
m).
Example 8
Preparation of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane
[0201] A 250 mL round bottom flask equipped with a magnetic stir
bar and a reflux condenser capped by an argon inlet was
sequentially charged with 0.69 g of a 60% dispersion of sodium
hydride in mineral oil, 3.34 g of
N.sup.1,N.sup.2-bis(2,6-diisopropylphenyl)oxalodiimidoyl
dichloride, 20 mL of dry tetrahydrofuran, and 0.70 mL of
1,2-ethanedithiol. The mixture was heated under argon at reflux for
3 hours, after which another 0.25 g of sodium hydride dispersion
was added and the mixture was refluxed for an additional 2.5 hours.
After cooling, the mixture was diluted with water and diethyl
ether, and the ether layer was separated, washed with water, and
dried with magnesium sulfate to afford a yellow-orange oil. Column
chromatography (SiO.sub.2, Merck Grade 9385 230-400 mesh, 60 .ANG.;
10 v % ethyl acetate in hexane) afforded 3.14 g of a yellow-orange
glass. Field desorption mass spectrometry showed a parent ion peak
at 466 m/z. .sup.1H NMR (500 MHz, CD.sub.2Cl.sub.2, chemical shifts
in ppm relative to TMS at 0 ppm): 1.10-1.22 (12 p, m), 1.22-1.40
(12 p, m), 2.78-3.05 (4 p, m), 3.30 (4 p, br s), 7.05-7.25 (6 p,
m).
Example 9
Preparation of 2,3-bis(phenylimino)-[1,4]dithiane
[0202] A 250 mL round bottom flask equipped with a magnetic stir
bar and a reflux condenser capped by an argon inlet was
sequentially charged with 0.69 g of a 60% dispersion of sodium
hydride in mineral oil, a freshly prepared solution of 2.08 g
N',N.sup.2-diphenyloxalodiimidoyl dichloride in 20 mL of dry
tetrahydrofuran, and 0.70 mL of 1,2-ethanedithiol. The mixture was
heated under argon at reflux for 2 hours, after which another 0.30
g of sodium hydride dispersion was added and the mixture refluxed
for an additional 3 hours. After cooling, the mixture was diluted
with water and diethyl ether, and the ether layer was separated,
washed with water, and dried with magnesium sulfate to afford a
yellow-orange gummy solid. Column chromatography (SiO.sub.2, Merck
Grade 9385 230400 mesh, 60 .ANG.; 10 v % ethyl acetate in hexane)
afforded 296 mg of a yellow oil which was crystallized by addition
of hexane to give 0.161 g of yellow-orange granular crystals. Field
desorption mass spectrometry showed a parent ion peak at 298 m/z.
.sup.1H NMR (300 MHz, CDCl.sub.3, chemical shifts in ppm relative
to TMS at 0 ppm): 3.27 (4p, br s), 7.02 (4p, apparent d, 8.1 Hz),
7.19 (2p, apparent t, 7.2 Hz), 7.40 (4p, apparent t, 7.8 Hz).
Example 10
Preparation of
2,3-bis(2,6-dimethylphenylimino)-2,3-dihydrobenzo[1,4]dithi-
ine
[0203] A 100 mL round bottom flask equipped with a magnetic stir
bar and a reflux condenser capped by an argon inlet was
sequentially charged with 0.294 g of a 60% dispersion of sodium
hydride in mineral oil, 4 mL of dry tetrahydrofuran, and 0.253 g of
1,2-benzenedithiol. After the bubbling had subsided, 0.600 g of
N.sup.1,N.sup.2-bis(2,6-dimethylphenyl)oxalodiim- idoyl dichloride
was added. The mixture was stirred at 25.degree. C. for 45 minutes,
then heated to reflux over 15 minutes and held at reflux for 1
hour. After cooling, the mixture was diluted with water and diethyl
ether, and the ether layer was separated, washed with water, and
dried with magnesium sulfate, and concentrated in vacuo to give a
yellow-orange oil. Column chromatography (SiO.sub.2, Merck Grade
9385 230-400 mesh, 60 .ANG.; 2 v % ethyl acetate in hexane)
afforded 0.412 g of a yellow-orange glass. Field desorption mass
spectrometry showed a parent ion peak at 402 m/z. .sup.1H NMR (300
MHz, CDCl.sub.3, chemical shifts in ppm relative to TMS at 0 ppm):
2.16 (12 p, s), 7.01-7.24 (10 p, m).
Example 11
Preparation of
2,3-bis(4-methoxy-2,6-dimethylphenylimino)-[1,4]dithiane
[0204] A 50 mL round bottom flask equipped with a magnetic stir bar
and a reflux condenser capped by a nitrogen inlet was charged with
420 mg of
N.sup.1,N.sup.2-bis(4-methoxy-2,6-dimethylphenyl)oxalodiimidoyl
dichloride. To a 50 mL pear flask was added 171 mg of sodium
hydride (60% mineral oil dispersion), 1.75 mL of dry
tetrahydrofuran, and, cautiously, 0.11 mL ethane dithiol. The
resulting mixture was syringed into the
N.sup.1,N.sup.2-bis(4-methoxy-2,6-dimethylphenyl)oxalodiimidoyl
dichloride solution using 5 mL dry THF to complete the transfer.
The reaction flask was heated at reflux for 3 hours, after which
another 45 mg of sodium hydride dispersion and another 20 .mu.L
ethane dithiol was added and the mixture was refluxed for an
additional hour. After cooling, the mixture was diluted with water
and diethyl ether, and the ether layer was separated, washed again
with water, dried with magnesium sulfate, and concentrated to
afford a yellow-orange solid. Column chromatography (SiO.sub.2,
Merck Grade 9385 230-400 mesh, 60 .ANG.; 15 v % ethyl acetate in
hexane) afforded 147 mg of a yellow powder. Field desorption mass
spectrometry showed a parent ion peak at 414 m/z.
Example 12
Preparation of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane
[0205] A 50 mL round bottom flask equipped with a magnetic stir bar
and a reflux condenser capped by a nitrogen inlet was charged with
504 mg of N.sup.1,N.sup.2-bis(2,6-dimethylphenyl)oxalodiimidoyl
dichloride, 66 mg of sodium hydride (60% mineral oil dispersion),
5.0 mL of dry tetrahydrofuran, 0.230 mL of triethylamine (dried by
passage through alumina) and 0.093 mL of dry ethylene glycol. The
mixture was heated at reflux for 105 minutes, after which another
66 mg of sodium hydride dispersion was added and the mixture was
refluxed for an additional hour. After cooling, the mixture was
diluted with water and diethyl ether, and the ether layer was
separated, washed again with water, dried with magnesium sulfate,
and concentrated to afford a yellow oil. Crystallization from
heptane gave rosettes of off-white crystals (225 mg, 1 st crop).
Field desorption mass spectrometry showed a parent ion peak at 322
m/z. .sup.1H NMR (300 MHz, CDCl.sub.3, chemical shifts in ppm
relative to TMS at 0 ppm): 2.20 (12 p, s), 4.35 (4 p, s), 6.94 (2
p, m), 7.05 (4 p, m).
Example 13
Preparation of
5-methoxymethyl-2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxa- ne
[0206] A 50 mL round bottom flask equipped with a magnetic stir bar
and a reflux condenser capped by an argon inlet was charged with
504 mg of N.sup.1,N.sup.2-bis(2,6-dimethylphenyl)oxalodiimidoyl
dichloride, 155 mg of sodium hydride (60% mineral oil dispersion),
3.5 mL of dry tetrahydrofuran and 188 mg of
3-methoxy-1,2-propanediol. The mixture was heated to reflux over 10
min and held at reflux for 2 hours. After cooling, the mixture was
diluted with diethyl ether, and washed with water (2.times.100 mL),
and dried with magnesium sulfate and concentrated in vacuo to
afford 329 mg of a yellow oil. Column chromatography (SiO.sub.2,
Merck Grade 9385 230-400 mesh, 60 .ANG.; 20 v % of ethyl acetate in
hexane) afforded 216 mg of a glassy yellow solid. Field desorption
mass spectrometry showed a parent ion peak at 366 m/z. .sup.1H NMR
(300 MHz, CDCl.sub.3, chemical shifts in ppm relative to TMS at 0
ppm): 2.18 (12 p, s), 3.31 (3 p, s), 3.45-3.65 (2 p, m), 4.20-4.40
(2 p, m), 4.40-4.55 (1 p, m), 6.80-7.15 (6 p, m).
Example 14
Preparation of 2,3-bis(benzyloxymethyl)-5,6-bis(2
6-dimethylphenylimino)-[- 1,4]dioxane
[0207] A 100 mL round bottom flask equipped with a magnetic stir
bar and a reflux condenser capped by an argon inlet was charged
with 265 mg of sodium hydride (60% mineral oil dispersion), 7.5 mL
of dry tetrahydrofuran, 1.0 g of 3-methoxy-1,2-propanediol and 1.0
g of N.sup.1,N.sup.2-bis(2,6-dimethylphenyl)oxalodiimidoyl
dichloride. The yellow mixture was heated to reflux over 15 min and
became very viscous. More tetrahydrofuran (5 mL) was added and the
mixture was stirred with a glass rod, then heated for another 30
min. Next, an additional 220 mg of sodium hydride (60% mineral oil
dispersion) and an additional 10 mL tetrahydrofuran were added.
Most of the yellow color was discharged with the second addition of
sodium hydride, rendering the very viscous reaction mixture light
brown. Heating was continued for about 15 min more, and after
cooling, the mixture was diluted with diethyl ether and washed with
water to remove the sodium chloride. Column chromatography
(SiO.sub.2, Merck Grade 9385 230-400 mesh, 60 .ANG.; 2 v % of ethyl
acetate in hexane) afforded a beige gummy solid. Field desorption
mass spectrometry showed a parent ion peak at 562 m/z. .sup.1H NMR
(300 MHz, CDCl.sub.3, chemical shifts in ppm relative to TMS at 0
ppm): 2.17 (12 p, s), 3.63 (4 p, br s), 4.38 (2 p, d, 12.6 Hz),
4.47 (2 p, d, 12.6 Hz), 4.56 (2 p, br s), 6.85-7.4 (16 p, m).
Example 15
Preparation of 2,3-bis(2,6-diisopropylphenylimino)-[1,4]dioxane
[0208] A 50 mL round bottom flask equipped with a magnetic stir bar
and a reflux condenser capped by a nitrogen inlet was charged with
1.0 g of N.sup.1,N.sup.2-bis(2,6-diisopropylphenyl)oxalodiimidoyl
dichloride, 268 mg of sodium hydride (60% mineral oil dispersion),
4.0 mL of dry tetrahydrofuran, and 212 mg of dry ethylene glycol.
Under an argon atmosphere, the mixture was heated to 65.degree. C.
held at that temperature for 90 minutes. The mixture was then
quickly heated to reflux and held at reflux for 30 minutes more.
After cooling, the mixture was diluted with 50 mL diethyl ether,
and washed with water, dried with magnesium sulfate, and
concentrated in vacuo to afford a light straw-yellow oil (903 mg).
Column chromatography (SiO.sub.2, Merck Grade 9385 230-400 mesh, 60
.ANG.; 8 v % ethyl acetate in hexane) afforded 257 mg of a pale
green glass. Field desorption mass spectrometry showed a parent ion
peak at 434 m/z. .sup.1H NMR (300 MHz, CDCl.sub.3, chemical shifts
in ppm relative to TMS at 0 ppm): 1.24 (24 p, d, 6.6 Hz), 3.00 (4p,
septet, 6.6 Hz), 4.31 (4 p, br s), 7.04-7.20 (6 p, m).
Example 16
Preparation of
2,3-bis(2,6-dimethylphenylimino)-4-methylmorpholine
[0209] A 50 mL round bottom flask equipped with a magnetic stir bar
and a reflux condenser capped by a nitrogen inlet adapter was
charged with 503 mg of
N.sup.1,N.sup.2-bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride,
346 mg triethylamine, 4 mL dry, deoxygenated toluene, and 0.135 mL
2-(methylamino)ethanol. The mixture was heated to reflux under
nitrogen over 30 minutes and maintained at reflux for another 4.25
hours. After cooling, the mixture was diluted with 45 mL diethyl
ether and washed three times with water (110 mL total). The ether
extract was dried with magnesium sulfate, filtered and concentrated
under reduced pressure (10 mm Hg) to give a light-colored solid
(512 mg). Recrystallization from heptane/dichloromethane gave 138
mg pale off-white crystals (first crop). Field desorption mass
spectrometry showed a parent ion peak at 335 m/z. .sup.1H NMR (300
MHz, CDCl.sub.3, chemical shifts in ppm relative to TMS at 0 ppm):
1.73 (6 p, s), 2.10 (6 p, s), 3.27 (3 p, s), 3.55-3.65 (2 p, m),
4.16-4.26 (2 p, m), 6.65-6.95 (6 p, m).
Example 17
Preparation of
2,3-bis(2.6-diisopropylphenylimino)-4-methylmorpholine
[0210] A 50 mL round bottom flask equipped with a magnetic stir bar
and a reflux condenser capped by a nitrogen inlet adapter was
charged with 725 mg of
N.sup.1,N.sup.2-bis(2,6-diisopropylphenyl)oxalodiimidoyl
dichloride, 143 mg of sodium hydride (60% mineral oil dispersion),
4 mL dry tetrahydrofuran, and 0.144 mL 2-(methylamino)ethanol. The
mixture was stirred at room temperature for 4 hours, and allowed to
stand at room temperature for another 5 days. The mixture was
diluted with diethyl ether and washed water. The ether extract was
concentrated under reduced pressure (10 mm Hg) to give a yellow oil
which partially crystallized over several hours). Column
chromatography (SiO.sub.2, Merck Grade 9385 230-400 mesh, 60 .ANG.;
12 v % of ethyl acetate in hexane) afforded 156 mg light yellow
crystalls. Field desorption mass spectrometry showed a parent ion
peak at 447 m/z. .sup.1H NMR (300 MHz, CDCl.sub.3, chemical shifts
in ppm relative to TMS at 0 ppm): 0.86 (6 p, d, 7.2 Hz), 1.04 (6 p,
d, 7.2 Hz), 1.15 (6 p, d, 7.2 Hz), 1.18 (6 p, d, 7.2 Hz), 2.27 (2
p, apparent septet, 7.2 Hz), 2.97 (2 p, apparent septet, 7.2 Hz),
3.28 (3 p, br s), 3.55-3.65 (2 p, m), 4.144.22 (2 p, m), 6.80-7.02
(6 p, m).
Example 18
Preparation of
1,3-bis-(2,6-dimethyl-phenyl)-4,5-bis-(2,6-dimethyl-phenyli-
mino)-imidazolidin-2-one
[0211] In a 250 mL round bottom flask, 1.0 g of
N.sup.1,N.sup.2,N.sup.3,N.-
sup.4-tetrakis(2,6-dimethylphenyl)oxalamidine was dissolved in 35
mL dry, deoxygenated dichloromethane while stirring under an argon
atmosphere. 0.67 mL dry triethylamine was added, followed by 240 mg
triphosgene. With the addition of the triphosgene, the color
shifted from pale yellow to chrome yellow. The mixture was allowed
to stir for 16 h at room temperature, after which time an
additional 460 mg of triphosgene was added. After about 15 min, 10
mg dimethylamino pyridine and an additional 240 mg triphosgene were
added. After about 15 min more, another 220 mg triphosgene and
about 0.5 g dimethylamino pyridine were added. The mixture was
washed with saturated aqueous sodium bicarbonate, then with water,
and then concentrated in vacuo to afford a yellow powder. Column
chromatography (SiO.sub.2, Merck Grade 9385 230-400 mesh, 60 .ANG.;
4 v % ethyl acetate in hexane) afforded 763 mg of a chrome yellow
powder. Field desorption mass spectrometry showed a parent ion peak
at 528 m/z. .sup.1H NMR (300 MHz, CDCl.sub.3, chemical shifts in
ppm relative to TMS at 0 ppm): 2.01 (12 p, s), 2.32 (12 p, s),
6.4-7.3 (12 p, m).
Example 19
Preparation of
1,3-bis(4-methoxy-2,6-dimethylphenyl)-4,5-bis-(4-methoxy-2,-
6-dimethylphenylimino)imidazolidin-2-one
[0212] A 100 mL round bottom was equipped with a magnetic stirrer
and charged with 0.75 mL dry triethylamine, 6 mL dry and
deoxygenated dichloromethane, and 0.335 g
N.sup.1,N.sup.2,N.sup.3/N.sup.4-tetrakis(4-m-
ethoxy-2,6-dimethylphenyl)oxalamidine. With stirring, 178 mg
triphosgene was added, and the flask was quickly capped with a
septum. A precipitate formed and the color shifted from yellow to
orange. After 2.5 days another 78 mg triphosgene was added, and the
reaction left to stir another 2 hours. 150 mg more triphosgene was
added, and the reaction left to stir for another 16 hrs. The
reaction mixture was diluted with 50 mL diethyl ether and washed
with water (2.times.50 mL). The aqueous washings were
back-extracted with dichloromethane. The organic layers were
combined and dried over magnesium sulfate, and concentrated in
vacuo to afford an orange oil. Upon addition of diethyl ether to
the oil, small orange crystals formed. The compound was isolated on
a vacuum filter and washed with diethyl ether to afford 216 mg
yellow-orange microcrystalline powder. Field desorption mass
spectrometry showed a parent ion peak at 648 m/z. .sup.1H NMR (500
MHz, CD.sub.2Cl.sub.2, chemical shifts in ppm relative to TMS at 0
ppm): 1.98 (12 p, broad hump), 2.25 (12 p, broad hump), 3.63 (6 p,
broad hump), 3.75 (6 p, broad hump), 6.32 (4 p, broad hump), 6.59
(4 p, broad hump).
Example 20
Preparation of
N.sup.1,N.sup.2,N.sup.3,N.sup.4-tetrakis(2,6-dimethylphenyl-
)oxalamidine
[0213] A 1 L round bottom flask equipped with a magnetic stir bar
and a reflux condenser capped by a nitrogen inlet was charged with
5.6 g of N.sup.1,N.sup.2-bis(2,6-dimethylphenyl)oxalodiimidoyl
dichloride, 43 mL of dry toluene and 32.7 g of 2,6-dimethylaniline
(dried by passage through alumina). The mixture was heated to
reflux under nitrogen over 30 minutes, then maintained at reflux
another 3 hours. After cooling, the mixture was diluted with 206 g
of absolute ethanol and 45 g of water to produce copious amounts of
precipitate. Isolation by vacuum filtration, with ethanol (600 mL)
and heptane (600 mL) washes, and subsequent drying, gave 6.1 g
(72%) as pale yellow crystals. Field desorption mass spectrometry
showed a parent ion peak at 502 m/z. .sup.1H NMR (300 MHz,
CDCl.sub.3, chemical shifts in ppm relative to TMS at 0 ppm): 2.16
(24 p, s), 6.75 (12 p, s), 8.6 (2 p, br s).
Example 21
Preparation of
N.sup.1,N.sup.2,N.sup.3,N.sup.4-tetrakis(4-methoxy-2,6-dime-
thylphenyl)oxalamidine
[0214] A 500 mL round bottom flask equipped with a magnetic stir
bar and a reflux condenser capped by a nitrogen inlet was charged
with 1.0 g of
N.sup.1,N.sup.2-bis(4-methoxy-2,6-dimethylphenyl)oxalodiimidoyl
dichloride, 24 mL of dry toluene and 854 mg of
4-methoxy-2,6-dimethylphen- ylamine, and 0.90 mL triethylamine
(dried by passage through alumina). The mixture was heated to
reflux under nitrogen over 30 minutes, then maintained at reflux
another 14 hours. After cooling, the mixture was diluted with
dichloromethane and washed with water. The impure compound was
adsorbed onto SiO.sub.2, and column chromatography (SiO.sub.2,
Merck Grade 9385 230-400 mesh, 60 .ANG.; 12.5 v % ethyl acetate in
hexane) afforded 340 mg of a yellow powder. Field desorption mass
spectrometry showed a parent ion peak at 622 m/z.
Example 22
Preparation of
1,4-dimethyl-2,3-bis(2,6-dimethylphenylimino)piperazine
[0215] A 25 mL round bottom flask equipped with a magnetic stir bar
and a reflux condenser capped by a nitrogen inlet adapter was
charged with 0.50 g of
N.sup.1,N.sup.2-bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride,
1.1 mL of N,N'-dimethylethylenediamine and 4.0 mL of dry toluene.
The mixture was heated to reflux under nitrogen over 15 minutes and
maintained at reflux for another 30 minutes. After cooling, the
mixture was diluted with diethyl ether and washed three times with
water. The ether extract was dried with magnesium sulfate, filtered
and concentrated under reduced pressure (10 mm Hg) to give a yellow
solid (0.50 g). Recrystallization from heptane gave pale yellow
crystals. Field desorption mass spectrometry showed a parent ion
peak at 348 m/z. .sup.1H NMR (300 MHz, CDCl.sub.3, chemical shifts
in ppm relative to TMS at 0 ppm): 1.83 (br s, 12 p), 2-3.4 (two
very broad humps, 4 p), 3.42 (br s, 6 p), 6.66 (t, 2p), 6.84 (d,
4p).
Example 23
Preparation of the nickel dibromide complex of
2,3-bis(2,6-dimethylphenyli- mino)-[1,4]dithiane
[0216] A 50 mL Schlenk flask equipped with a magnetic stir bar and
capped with a septum was charged with 100 mg of
2,3-bis(2,6-dimethylphenylimino)- -[1,4]dithiane and 79 mg of
(1,2-dimethoxyethane)nickel(II) dibromide under an inert
atmosphere. Dry, deoxygenated dichloromethane (5 mL) was added and
the mixture was stirred under an argon atmosphere, turning
red-brown within about 5 minutes and slowly producing a red-brown
crystalline precipitate. After 1 hour, another 5 mL of
dichloromethane was added. The mixture was stirred another 21 hours
at 21.degree. C., then diluted with 10 mL of dry, deoxygenated
hexane and stirred another 8 hours. The supernatant was removed via
a filter paper-tipped cannula, and the residue dried in vacuo at 1
mm Hg to afford 116 mg of red-brown crystals.
Example 24
Preparation of the nickel dibromide complex of
2,3-bis(2,6-diisopropylphen- ylimino)-[1,4]dithiane
[0217] A Schlenk flask equipped with a magnetic stir bar was
charged with 79 mg of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane (0.17 mmol) and
49 mg of (1,2-dimethoxyethane)nickel(II) dibromide (0.16 mmol)under
an argon atmosphere. Dry, deoxygenated dichloromethane (15 mL) was
added and the mixture was stirred under an argon atmosphere,
turning red-brown within about 10 minutes. After 2 hours, the
CH.sub.2Cl.sub.2 was removed in vacuo. The resulting red-brown
solid was washed with 2.times.10 mL of hexane and the solid was
dried in vacuo for several hours affording 76 mg of a brown
solid.
Example 25
Preparation of the nickel dibromide complex of
2,3-bis(phenylimino)-[1,4]d- ithiane
[0218] A 50 mL Schlenk flask equipped with a magnetic stir bar and
capped with a septum was charged with 151 mg of
2,3-bis(phenylimino)-[1,4]dithia- ne and 123 mg of
(1,2-dimethoxyethane)nickel(II) dibromide under an inert
atmosphere. Dry, deoxygenated dichloromethane (10 mL) was added and
the mixture was stirred under an argon atmosphere, turning dark
brown within about 5 minutes and slowly producing a red-brown
crystalline precipitate. After 80 minutes, the mixture was
concentrated to apparent dryness under a stream of argon, then
further dried in vacuo for 1 hour at 50 mTorr to afford a red-brown
powder.
Example 26
Preparation of the nickel dibromide complex of
2,3-bis(2,6-dimethylphenyli-
mino)-2,3-dihydrobenzo[4,1]dithiine
[0219] A 50 mL Schlenk flask equipped with a magnetic stir bar and
capped with a septum was charged with 110 mg of
2,3-bis-(2,6-dimethylphenylimino- )-2,3-dihydrobenzo[1,4]dithiine
and 71 mg of (1,2-dimethoxyethane)nickel(I- I) dibromide under an
inert atmosphere. Dry, deoxygenated dichloromethane (8 mL) was
added and the mixture was stirred under an argon atmosphere,
quickly turning red-brown. The mixture was stirred for 1 hour,
concentrated to dryness under a stream of argon, then further dried
in vacuo for 1 hour at 50 mTorr to yield a red-brown crystalline
powder.
Example 27
Preparation of the nickel dibromide complex of
2,3-bis(4-methoxy-2,6-dimet- hylphenylimino)-[1,4]dithiane
[0220] A 50 mL Schlenk flask equipped with a magnetic stir bar and
capped with a septum was charged with 147 mg of
2,3-bis(4-methoxy-2,6-dimethylph- enylimino)-[1,4]dithiane and 93
mg of (1,2-dimethoxyethane)nickel(II) dibromide under an inert
atmosphere. Dry, deoxygenated dichloromethane (10 mL) was added and
the mixture was stirred under an argon atmosphere, turning dark
brown almost immediately, and producing a brown precipitate. After
2 hours, 10 mL dry and deoxygenated hexane was added to complete
the precipitation. The supernatant was removed via filter
paper-tipped cannula, the residue dried in vacuo (0.5 mm Hg) for 14
h to obtain the product as a brown microcrystalline solid.
Example 28
Preparation of the nickel dibromide complex of
2,3-bis(2,6-dimethylphenyli- mino)-[1,4]dioxane
[0221] A 50 mL Schlenk flask equipped with a magnetic stir bar and
capped with a septum was charged with 100 mg of
2,3-bis(2,6-dimethylphenylimino)- -[1,4]dioxane and 87 mg of
(1,2-dimethoxyethane)nickel(II) dibromide under an inert
atmosphere. Dry, deoxygenated dichloromethane (5 mL) was added and
the mixture was stirred under an argon atmosphere, slowly producing
a brown crystalline precipitate. After 1 hour, another 5 mL of
dichloromethane was added. The mixture was stirred another 21 hours
at 21.degree. C., then diluted with 10 mL of dry, deoxygenated
hexane and stirred another 8 hours. The supernatant was removed via
a filter paper-tipped cannula, and the residue dried in vacuo at 1
mm Hg to afford 117 mg of brown crystals.
Example 29
Preparation of the nickel dibromide complex of
2,3-bis(benzyloxymethyl)-5,-
6-bis(2,6-dimethylphenylimino)-[1,4]dioxane
[0222] A 50 mL Schlenk flask equipped with a magnetic stir bar and
capped with a septum was charged with 172 mg of
2,3-bis(benzyloxymethyl)-5,6-bis-
(2,6-dimethylphenylimino)-[1,4]dioxane and 85 mg of
(1,2-dimethoxyethane)nickel(lI) dibromide under an inert
atmosphere. Dry, deoxygenated dichloromethane (12 mL) was added and
the mixture was stirred under an argon atmosphere, almost
immediately turning red-brown. After 1.75 hours, the mixture was
concentrated dryness under a stream of argon for 16 h, then further
dried in vacuo to afford 182 mg of a red-brown crystalline
powder.
Example 30
Preparation of the nickel dibromide complex of
2,3-bis(2,6-dimethylphenyli- mino)-4-methylmorpholine
[0223] A 25 mL Schlenk flask equipped with a magnetic stir bar and
capped with a septum was charged with 100 mg of
2,3-bis(2,6-dimethylphenylimino)- -4-methylmorpholine and 84 mg of
(1,2-dimethoxyethane)nickel(II) dibromide under an inert
atmosphere. Dry, deoxygenated dichloromethane (5 mL) was added and
the mixture was stirred under an argon atmosphere for 1 hour, after
which another 5 mL dichloromethane was added. After 16 hours, the
mixture was diluted with 10 mL hexane, and the supernatent was
removed via a filter paper tipped cannula, and the residue was
dried in vacuo to obtain 139 mg green crystals.
Example 31
Reaction of
1,3-bis-(2,6-dimethyl-phenyl)-4,5-bis-(2,6-dimethyl-Phenylimin-
o)-imidazolidin-2-one, (1,2-dimethoxyethane)nickel(II) dibromide,
and silver tetrafluoroborate
[0224] In an argon filled glove box, a flame-dried Schlenk flask
equipped with a magnetic stir bar was charged with 159.6 mg of
1,3-bis-(2,6-dimethyl-phenyl)-4,5-bis-(2,6-dimethyl-phenylimino)-imidazol-
idin-2-one and 92.7 mg of (1,2-dimethoxyethane)nickel(II) dibromide
and 59.4 mg silver tetrafluoroborate. The flask was wrapped in
aluminum foil, and on the Schlenk line, under an argon atmosphere,
10 mL dry tetrahydrofuran was added. A white precipitate
immediately separated. The mixture was stirred for 25 min, then the
supernatant was transferred via filter paper-tipped cannula to a
dry septum-capped vial. The supernatant was concentrated to dryness
under a stream of dry argon for 16 h to afford 256 mg of a yellow
crystalline powder.
Example 32
Preparation of the nickel dibromide complex of
1,3-bis(4-methoxy-2,6-dimet-
hylphenyl)-4,5-bis(4-methoxy-2,6-dimethylphenylimino)imidazolidin-2-one
[0225] A 50 mL Schienk flask equipped with a magnetic stir bar and
capped with a septum was charged with 101 mg of
1,3-bis(4-methoxy-2,6-dimethylph-
enyl)-4,5-bis(4-methoxy-2,6-dimethylphenylimino)imidazolidin-2-one
and 40 mg of (1,2-dimethoxyethane)nickel(II) dibromide under an
inert atmosphere. Dry, deoxygenated dichloromethane (10 mL) was
added and the mixture was stirred under an nitrogen atmosphere,
slowly turning dark red-brown over 3 hours. After 2 more hours, the
supernatant was removed to a flame-dried Schlenk flask via a filter
paper-tipped cannula, diluted with 10 mL dry, deoxygenated hexane,
and concentrated to dryness under a stream of nitrogen to give a
mixture of a tan microcrystalline powder and large, well-defined
dark brown crystals. The latter were separated and used without
further purification.
Example 33
Preparation of the nickel dibromide complex of
1,4-dimethyl-2,3-bis(2,6-di- methylphenylimino)piperazine
[0226] A 50 mL Schlenk flask equipped with a magnetic stir bar and
capped with a septum was charged with 48 mg of
1,4-dimethyl-2,3-bis(2,6-dimethyl- phenylimino)piperazine and 35 mg
of (1,2-dimethoxyethane)nickel(II) dibromide under an inert
atmosphere. Dry, deoxygenated dichloromethane (5 mL) was added and
the mixture was stirred under an argon atmosphere, turning green
within about 5 minutes and slowly producing a green precipitate.
After a total of 7 hours, the volatiles were removed under reduced
pressure (1 mm Hg) and the residue was washed with 2.times.5 mL of
dry, deoxygenated diethyl ether. The resultant green solid was
dried under reduced pressure (1 mm Hg).
Example 34
[0227] Synthesis of: 21
[0228] In the glove box, a Schlenk flask was charged with 500 mg of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane and 250 mg
(1,5-cyclooctadiene)palladium methyl chloride. The flask was
removed form the box and placed under an argon atmosphere. To the
solid mixture was added 20 ml of methylene chloride resulting in an
orange solution. The mixture was left to stir for 4 hours. After 4
hours, 20 ml of hexane was added resulting in the precipitation of
an orange solid. The solvent was removed via filter cannula leaving
a red/orange solid. The solid was subsequently washed 3.times.10 ml
of hexane and dried in vacuo resulting in 490 mg of the complex (83
% yield). .sup.1H NMR is consistent with the proposed
structure.
Example 35
[0229] Synthesis of: 22
[0230] In the glove box, a Schlenk flask was charged with 490 mg of
2,3-bis(2,6-diisopropylphenylimino)[1,4]dithiane palladium methyl
chloride and 738 mg of NaBAr.sub.4 where
Ar=3,5-bis-trifluromethylphenyl. The flask was removed form the box
and placed under an argon atmosphere. To the solid mixture was
added 25 ml of methylene chloride and 0.2 ml of acetonitrile
resulting in an orange solution. The mixture was left to stir for 3
hours. After 3 hours, the solution was transfered via filter
cannula leaving a gray solid (NaCl). The solvent was subsequently
removed in vacuo resulting in a orange glass (1.1 g of the complex,
90% yield). .sup.1H NMR is consistent with the proposed
structure.
Example 36
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of
MAO
[0231] A 200 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar and capped with a septum was charged with 5.3 mg of the
nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane. The flask was
evacuated and refilled with ethylene, then charged with 75 mL of
dry, deoxygenated toluene. The resultant suspension was cooled to
0.degree. C. and allowed to equilibrate with 1 atmosphere ethylene
for 15 minutes, then treated with 4.0 mL of a 10 wt % solution of
MAO in toluene and stirred under 1 atmosphere ethylene. A white
polyethylene precipitate (with a faint red-brown tinge) was
observed within minutes. After 10 minutes, the mixture was quenched
by the addition of acetone (50 mL), methanol (50 mL) and 6 N
aqueous HCl (100 mL). The swollen polyethylene which separated was
isolated by vacuum filtration and washed with water, methanol and
acetone, then dried under reduced pressure (0.05-0.1 mm Hg) for 48
hours to give 2.5 g of a white polyethylene. A similar reaction at
21.5.degree. C. using 0.104 mg of the nickel complex (100 .mu.L of
a 1.04 mg/mL stock solution in o-difluorobenzene) gave 426 mg
polyethylene after 14 minutes reaction (359,000 Turnovers per hour
(TO/h)). .sup.1H NMR: 24 branches/1000 carbon atoms. GPC:
M.sub.n=810,000; M.sub.w/M.sub.n=2.3.
Example 37
Polymerization of ethylene using a catalyst generated in situ from
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane,
bis(1,5-cyclooctadiene)ni- ckel(0) and HB(Ar).sub.4
(Ar=3,5-bis(trifluoromethyl)phenyl)
[0232] A 250 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar and capped with a septum was charged with 20 mg of
bis(1,5-cyclooctadiene)nickel(0), 33 mg of
2,3-bis(2,6-dimethylphenylimin- o)-[1,4]dithiane, and 83 mg of the
ether solvate HB(Ar).sub.4. The flask was evacuated and refilled
with ethylene, then charged with 75 mL of dry, deoxygenated
toluene. The deep violet solution which resulted was stirred under
ethylene at 25.degree. C. for 30 minutes, then quenched by addition
of acetone (50 mL), and methanol ( 50 mL). The polyethylene which
separated was isolated by vacuum filtration and washed with
acetone, then dried under reduced pressure (0.5 mm Hg) for 18 hours
to give 339 mg of white polyethylene (332 TO/h). .sup.1H NMR: 47
branches/1000 carbon atoms. GPC: M.sub.n=180,000;
M.sub.w/M.sub.n=2.4.
Example 38
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of
MAO
[0233] A 200 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar was charged with 0.5 mL of a stock solution (10 mg in 10
mL CH.sub.2Cl.sub.2) of the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane. The flask was
evacuated and refilled with ethylene, and charged with 75 mL of
dry, deoxygenated toluene. The reaction flask was placed in a water
bath (23.degree. C.) and treated with 1.0 mL of a 10 wt % solution
of MAO in toluene and stirred under 1 atmosphere ethylene. A white
polyethylene precipitate was observed within seconds. After 5
minutes, the mixture was quenched by the addition of acetone,
methanol and 6 N aqueous HCl. The swollen polyethylene which
separated was isolated by vacuum filtration and washed with
acetone. The resulting polymer was dried for several hours in a
vacuum oven at 80.degree. C. 580 mg of a white rubbery solid was
isolated (285,000 TO/h). DSC: (2nd heat) broad melt with an
endothermic maximum at 87.degree. C. .sup.1H NMR, 37 branches/1000
carbon atoms. GPC: M.sub.n=186,000; M.sub.w/M.sub.n=2.06.
Example 39
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane in the presence
of MAO
[0234] A 200 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar was charged with 0.5 mL of a stock solution (10 mg in 10
mL CH.sub.2Cl.sub.2) of the nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane. The flask was
evacuated and refilled with ethylene, and charged with 75 mL of
dry, deoxygenated toluene. The reaction flask was placed in a water
bath and treated with 1.0 mL of a 10 wt % solution of MAO in
toluene and stirred under 1 atmosphere ethylene. After 10 minutes,
the mixture was quenched by the addition of acetone, methanol and 6
N aqueous HCl. The swollen polyethylene which separated was
isolated by vacuum filtration and washed with acetone. The
resulting polymer was dried for several hours in a vacuum oven at
80.degree. C. 210 mg of a white rubbery amorphous polymer was
isolated (63,000 TO/h). DSC: (2nd heat) broad melt with an
endothermic maximum at 6.degree. C. .sup.1H NMR: 92 branches/1000
carbon atoms. GPC: M.sub.n=146,000; M.sub.w/M.sub.n=1.85.
Example 40
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of
MMAO (modified methylaluminoxane; 23% iso-butylaluminoxane)
[0235] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under high vacuum to ensure that the reactor was
dry. The reactor was cooled and purged with argon. Under an argon
atmosphere, the autoclave was charged with 150 mL of toluene and
0.3 mL of a stock solution (10 mg in 10 mL CH.sub.2Cl.sub.2) of the
nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane. The autoclave was
heated to 40.degree. C. and 2 mL of MMAO in heptane (6.42 wt %
aluminum) was added. The reactor was rapidly pressurized to 100
psig with ethylene and the temperature ramped up to 50.degree. C.
After 10 minutes at 50.degree. C., the reaction was quenched by the
addition of acetone, and methanol. The swollen polyethylene which
separated was isolated and dried for several hours in a vacuum oven
at 80.degree. C. 4.8 g of a white rubbery solid was isolated
(2,000,000 TO/h). DSC: (2nd heat) broad melt with an endothermic
maximum at 97.degree. C. .sup.1H NMR: 28 branches/1000 carbon
atoms. GPC: M.sub.n=155,000; M.sub.w/M.sub.n=2.10.
Example 41
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of
MMAO (23% iso-butylaluminoxane)
[0236] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under high vacuum to ensure that the reactor was
dry. The reactor was cooled and purged with argon. Under an argon
atmosphere, the autoclave was charged with 150 mL of toluene and
0.3 mL of a stock solution (10 mg in 10 mL CH.sub.2Cl.sub.2) of the
nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane. The autoclave was
cooled to 15.degree. C. and 2 mL of MMAO in heptane (6.42 wt %
aluminum) was added. The reactor was rapidly pressurized to 100
psig with ethylene and the temperature ramped up to 25.degree. C..
After 10 minutes at 25.degree. C., the reaction was quenched by the
addition of acetone, and methanol. The swollen polyethylene which
separated was isolated and dried for several hours in a vacuum oven
at 80.degree. C. 4.4 g of a white rubbery polyethylene was isolated
(1,800,000 TO/h). DSC: (2nd heat) melt with an endothermic maximum
at 125.degree. C. .sup.1H NMR: 6 branches/1000 carbon atoms. GPC:
M.sub.n=598,000; M.sub.w/M.sub.n=2.12.
Example 42
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of
MMAO (23% iso-butylaluminoxane)
[0237] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under high vacuum to ensure that the reactor was
dry. The reactor was cooled and purged with argon. Under an argon
atmosphere, the autoclave was charged with 150 mL of toluene and
1.0 mL of a stock solution (10 mg in 10 mL CH.sub.2Cl.sub.2) of the
nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane. The autoclave was
heated to 55.degree. C. and 2 mL of MMAO in heptane (6.42 wt %
aluminum) was added. The reactor was rapidly pressurized to 100
psig with ethylene and the temperature ramped up to 65.degree. C.
After 10 minutes at 65.degree. C., the reaction was quenched by the
addition of acetone, and methanol. The swollen polyethylene which
separated was isolated and dried for several hours in a vacuum oven
at 80.degree. C. 5.3 g of a white rubbery solid was isolated
(640,000 TO/h). DSC: (2nd heat) melt with an endothermic maximum at
78.degree. C. .sup.1H NMR: 47 branches/1000 carbon atoms. GPC:
M.sub.n=86,000; M.sub.w/M.sub.n=1.95.
Example 43
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of
MMAO (23% iso-butvlaluminoxane)
[0238] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under high vacuum to ensure that the reactor was
dry. The reactor was cooled and purged with argon. Under an argon
atmosphere, the autoclave was charged with 150 mL of toluene and
1.0 mL of a stock solution (10 mg in 10 mL CH.sub.2Cl.sub.2) of the
nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane. The autoclave was
heated to 70.degree. C. and 2 mL of MMAO in heptane (6.42 wt %
aluminum) was added. The reactor was rapidly pressurized to 100
psig with ethylene and the temperature ramped up to 80.degree. C.
After 10 minutes at 80.degree. C., the reaction was quenched by the
addition of acetone, and methanol. The swollen polyethylene which
separated was isolated and dried for several hours in a vacuum oven
at 80.degree. C. 3.5 g of a white rubbery solid was isolated
(440,000 TO/h). DSC: (2nd heat) melt with an endothermic maximum at
67.degree. C. .sup.1H NMR: 53 branches/1000 carbon atoms. GPC:
M.sub.n=87,000; M.sub.w/M.sub.n=1.66.
Example 44
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane in the presence
of MMAO (23% iso-butylaluminoxane)
[0239] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under high vacuum to ensure that the reactor was
dry. The reactor was cooled and purged with argon. Under an argon
atmosphere, the autoclave was charged with 150 mL of toluene and
0.5 mL of a stock solution (10 mg in 10 mL CH2Cl2) of the nickel
dibromide complex of
2,3-bis(2,6-di-iso-propylphenylimino)-[1,4]dithiane. The autoclave
was heated to 40.degree. C. and 2 mL of MMAO in heptane (6.42 wt %
aluminum) was added. The reactor was rapidly pressurized to 100
psig with ethylene and the temperature ramped up to 50.degree. C.
After 10 minutes at 50.degree. C., the reaction was quenched by the
addition of acetone, and methanol. The swollen polyethylene which
separated was isolated and dried for several hours in a vacuum oven
at 80.degree. C. 2.4 g of a white rubbery solid was isolated
(700,000 TO/h). DSC: (2nd heat) melt with an endothermic maximum at
46.degree. C. 1H NMR: 75 branches/1000 carbon atoms. GPC:
M.sub.n=966,000; M.sub.w/M.sub.n=1.70.
Example 45
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane in the presence
of MMAO (23% iso-butylaluminoxane
[0240] The procedure described in example 44 was followed except
the polymerization was conducted at 80.degree. C. 1.4 g of a white
rubbery solid was isolated (400,000 TO/h). DSC: (2nd heat) melt
with an endothermic maximum at 0.degree. C. .sup.1H NMR: 95
branches/1000 carbon atoms. GPC: M.sub.n=406,000;
M.sub.w/M.sub.n=2.05.
Example 46
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane in the presence
of MMAO (23% iso-butylaluminoxane)
[0241] The procedure described in Example 44 was followed except
the polymerization was conducted at 65.degree. C. 2.15 g of a white
rubbery solid was isolated (630,000 TO/h). DSC: (2nd heat) melt
with an endothermic maximum at 15.degree. C. .sup.1H NMR: 89
branches/1000 carbon atoms. GPC: M.sub.n=502,000;
M.sub.w/M.sub.n=1.78.
Example 47
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane in the presence
of MMAO(23% iso-butylaluminoxane
[0242] The procedure described in Example 44 was followed except
the polymerization was conducted at 25.degree. C. 1.9 g of a white
rubbery solid was isolated (560,000 TO/h). DSC: (2nd heat) melt
with an endothermic maximum at 90.degree. C. .sup.1H NMR: 33
branches/1000 carbon atoms. GPC: M.sub.n=839,000;
M.sub.w/M.sub.n=1.37.
Example 48
Oligomerization of ethylene to .alpha.-olefin with the nickel
dibromide complex of 2,3-bis(phenylimino)-[1,4]dithiane in the
presence of MAO
[0243] A 1 L Fischer-Porter bottle was assembled onto a pressure
head equipped with a mechanical stirrer and gas and liquid
feed-through ports, then pressurized to 75 psig of ethylene and
relieved to ambient pressure seven times. The bottle was immersed
in a 21.5.degree. C. water bath, then 50 mL of dry, deoxygenated
toluene was added via syringe, followed by 100 .mu.L of a stock
solution of 15.3 mg of the nickel dibromide complex of
2,3-bis(phenylimino)-[1,4]dithiane in 15.0 mL of dichloromethane,
followed by another 50 mL of toluene. The mixture was stirred at
300 rpm under 75 psig ethylene for 5 minutes to saturate the
solution with ethylene, then the pressure was relieved, and 4.0 mL
of a 10 wt % solution of MAO in toluene was quickly added. The
flask was immediately re-pressurized to 75 psig ethylene and
stirred at 300 rpm. After 30 minutes, the pressure was relieved and
the reaction quenched by addition of 10 mL of methanol. After
disassembling the apparatus, another 40 mL of methanol, 50 mL of 6
N aqueous HCl, and 10 mL acetone were added and the mixture was
stirred to complete hydrolysis of the MAO. The resultant organic
layer was separated, washed with 6 N aqueous HCl (1.times.25 mL),
and water (2.times.50 mL), then concentrated under reduced pressure
(15 Torr) at 40.degree. C. to obtain an oil. This was treated with
toluene (50 mL) and re-concentrated twice, then treated with
acetone (50 mL) and re-concentrated, to obtain a waxy white
polyethylene solid. Drying in vacuo at 100.degree. C., 250 mm Hg
for 14 hours gave 0.180 g of polymer, approximate M.sub.n=517,
containing approximately 85% .alpha.-olefin and 15% internal
olefin.
Example 49
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-2,3-dihydrobenzo[4]dithiine in the
presence of MAO
[0244] A 200 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar and capped with a septum was charged with 100 mL of dry,
deoxygenated toluene. The flask was placed in a water bath and
allowed to equilibrate with I atmosphere ethylene for 10 minutes,
then 0.25 mL of a stock solution prepared from 10.2 mg of the
nickel dibromide complex of
2,3-bis-(2,6-dimethylphenylimino)-2,3-dihydrobenzo[1,4]dithiine in
13.11 g dry, deoxygentated dichloromethane was added. The reaction
mixture was then treated with 4.0 mL of a 10 wt % solution of MAO
in toluene and stirred under 1 atmosphere ethylene. Ethylene uptake
and formation of a polyethylene precipitate were observed. After
6.5 minutes, the mixture was quenched by the addition of acetone
(50 mL), methanol (50 mL) and 6 N aqueous HCl (100 mL). The swollen
polyethylene which separated was isolated by vacuum filtration,
then dried at 80.degree. C. in vacuo for several hours. 287 mg of a
white powdery polyethylene was isolated (236,000 TO/h). DSC: (2nd
heat) melt with an endothermic maximum at 88.degree. C. .sup.1H NMR
showed this material to contain approximately 36 branches/1000
carbon atoms. GPC: M.sub.n=145,000; M.sub.w/M.sub.n=2,35.
Example 50
Polymerization of ethylene using a catalyst formed in situ from
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane and
[Pd(NCCH.sub.3).sub.4][BF.sub.4].sub.2.
[0245] A 200 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar and capped with a septum was charged with 0.022 g of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane and 0.019 g
[Pd(NCCH.sub.3).sub.4][BF.sub.4].sub.2. The flask was evacuated and
refilled with ethylene, then 100 mL of dry, deoxygenated
dichloromethane was added via syringe and the resultant mixture was
stirred under 1 atmosphere of ethylene at 25.degree. C. Very little
ethylene uptake was observed. After 10 minutes, 0.412 g
B(C.sub.6F.sub.5).sub.3 was added, resulting in an increased rate
of ethylene uptake. After a total of 84 minutes, the reaction was
worked up by evaporating the dichloromethane under a stream of
nitrogen, washing the residue with methanol repeatedly to extract
the B(C.sub.6F.sub.5).sub.3, and drying the residue in vacuo to
obtain 0.57 g of amorphous polyethylene, approximate
M.sub.n=17,000; Mn/M.sub.w=1.3. .sup.1H NMR showed approximately
105 branches per 1000 carbons.
Example 51
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(4-methoxy-2,6-dimethylphenylimino)-[1,4]dithiane in the
presence of MAO
[0246] A 500 mL round bottom flask fitted with a Schlenk adapter
and equipped with a magnetic stir bar and capped with a septum was
evacuated, flame-dried, then refilled with ethylene. The flask was
provided with a room temperature (ca. 23.degree. C.) water bath,
then charged with 100 mL of dry, deoxygenated toluene and allowed
to equilibrate with 1 atmosphere ethylene for 30 minutes. The
reaction mixture was then treated with 4.0 mL of a 10 wt % solution
of MAO in toluene and stirred under 1 atmosphere ethylene, then
0.10 mL of a stock solution (prepared from 6.3 mg of the nickel
dibromide complex of 2,3-bis(4-methoxy-2,6-dimethylphenylimino)-[1-
,4]dithiane and 6.5 mL dichloromethane) was added. After 10
minutes, the reaction mixture was quenched by the addition of
acetone, methanol and 6 N aqueous HCl. The polyethylene which
separated was isolated by vacuum filtration and washed with water,
methanol and acetone, dried on the filter for 2 h, then further
dried 13 days in a vacuum oven at 80.degree. C. 182 mg of a white
polyethylene was isolated (254,000 TO/h). DSC: (2nd heat) melt with
an endothermic maximum at 124.degree. C. .sup.1H NMR: 13
branches/1000 carbon atoms. GPC: M.sub.n=145,600;
M.sub.w/M.sub.n=2,6.
Example 52
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane in the presence
of (CH.sub.3CH.sub.2).sub.2AlCl
[0247] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under high vacuum to ensure the reactor was dry. The
reactor was cooled and purged with argon. Under an argon
atmosphere, the autoclave was charged with 150 mL of toluene and
0.5 mL of a stock solution (10 mg in 10 mL CH.sub.2Cl.sub.2) of the
nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-(1,4]dithiane. The autoclave
was heated to 45.degree. C. and 2 mL of
(CH.sub.3CH.sub.2).sub.2AlCl (5000 equiv.) in toluene was added.
The reactor was rapidly pressurized to 100 psig and the temperature
ramped up to 50.degree. C. After 10 minutes at 50.degree. C., the
reaction was quenched by the addition of acetone, and methanol. The
swollen polyethylene which separated was isolated by filtration and
dried for several hours in a vacuum oven at 80.degree. C. resulting
in 1.9 g of a white rubbery solid (560,000 TO/h). DSC: (2nd heat)
broad melt with an endothermic maximum at 30.degree. C. .sup.1H
NMR: 87 branches/1000 carbon atoms. GPC: M.sub.n=557,000;
M.sub.w/M.sub.n=1.82.
Example 53
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane in the presence
of (CH.sub.3CH.sub.2).sub.2AlCl
[0248] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under high vacuum to ensure the reactor was dry. The
reactor was cooled and purged with argon. Under an argon
atmosphere, the autoclave was charged with 150 mL of toluene and
0.5 mL of a stock solution (10 mg in 10 mL CH.sub.2Cl.sub.2) of the
nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane. The autoclave
was heated to 45.degree. C. and 0.2 mL of
(CH.sub.3CH.sub.2).sub.2AlCl (500 equiv.) in toluene was added. The
reactor was rapidly pressurized to 100 psig and the temperature
ramped up to 50.degree. C. After 10 minutes at 50.degree. C., the
reaction was quenched by the addition of acetone, and methanol. The
swollen polyethylene which separated was isolated by filtration and
dried for several hours in a vacuum oven at 80.degree. C. resulting
in 2 g of a white rubbery solid (590,000 TO/h). DSC: (2nd heat)
broad melt with an endothermic maximum at 30.degree. C. .sup.1H
NMR: 85 branches/1000 carbon atoms. GPC: M.sub.n=515,000;
M.sub.w/M.sub.n=1.81.
Example 54
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane in the presence
of (CH.sub.3CH.sub.2).sub.2AlCl
[0249] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under high vacuum to ensure the reactor was dry. The
reactor was cooled and purged with argon. Under an argon
atmosphere, the autoclave was charged with 150 mL of toluene and
0.5 mL of a stock solution (10 mg in 10 mL CH.sub.2Cl.sub.2) of the
nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane. The autoclave
was heated to 45.degree. C. and 0.04 mL of
(CH.sub.3CH.sub.2).sub.2AlCl (100 equiv.) in toluene was added. The
reactor was rapidly pressurized to 100 psig and the temperature
ramped up to 50.degree. C. After 10 minutes at 50.degree. C., the
reaction was quenched by the addition of acetone, and methanol. The
swollen polyethylene which separated was isolated by filtration and
dried for several hours in a vacuum oven at 80.degree. C. resulting
in 1.5 g of a white rubbery solid (440,000 TO/h). DSC: (2nd heat)
broad melt with an endothermic maximum at 29.degree. C. .sup.1H
NMR: 80 branches/1000 carbon atoms. GPC: M.sub.n=422,000;
M.sub.w/M.sub.n=1.97.
Example 55
Copolymerization of ethylene and ethyl undecenoate with the nickel
dibromide complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane
in the presence of MMAO (23% iso-butylaluminoxane).
[0250] A flame dried Schlenk flask equipped with a stir bar and a
rubber septum was charged with 50 ml of toluene and 5 mg of the
nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane. The flask was
cooled to 0.degree. C. in an ice-water bath and filled with
ethylene (1 atmosphere). To the flask was added 2.0 ml of MMAO in
heptane (6.42 wt % aluminum). Within 5 seconds, 5 ml of ethyl
undecenoate was added to give a purple solution. The mixture was
left to stir for 16 hours. Acetone, methanol and 6M HCl were added
to quench the reaction and precipitate the polymer. The polymer was
collected by suction filtration and washed with copious amounts of
acetone to ensure all of the ethyl undecenoate comonomer was
removed resulting in 100 mg of white powdery polymer. NMR
spectroscopic analysis is consistent with the preparation of an
ester group containing copolymer. In addition, ethylene
homopolymer, which resulted from the short reaction time prior to
addition of the ethyl undecenoate, was present. .sup.1H NMR: 7.5 wt
% ethyl undecenoate incorporated. GPC: M.sub.n=9500,
M.sub.w/M.sub.n=16.6. DSC: T.sub.m=128.degree. C.
Example 56
Co-polymerization of ethylene and 1,13-tetradecadiene with the
nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of
MAO
[0251] A 200 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar and capped with a septum was flame-dried under vacuum,
refilled with ethylene, and then sequentially charged with 50 mL of
dry, deoxygenated toluene, 6.0 mL of deoxygenated
1,13-tetradecadiene, and 1.0 mL of a stock solution of 11.8 mg of
the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in 10.0 mL of dry,
deoxygenated dichloromethane. The flask was placed in a 23.degree.
C. water bath and allowed to equilibrate with 1 atmosphere of
ethylene for 5 minutes, then 4.0 mL of a 10 wt % solution of MAO in
toluene was added and the mixture was stirred under 1 atmosphere of
ethylene. Ethylene uptake was observed and the mixture rapidly
became more viscous. After 7 minutes, the reaction was quenched by
the addition of acetone (50 mL), methanol (50 mL) and 6 N aqueous
HCl (100 mL). The co-polymer which separated was isolated by vacuum
filtration and dried in vacuo at 100.degree. C. for 24 hours to
obtain 0.72 g of a rubbery white polymer, which formed a gel upon
attempted re-dissolution in hot o-dichlorobenzene.
Example 57
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane in the presence of
MAO
[0252] A 200 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar and capped with a septum was charged with 3.4 mg of the
nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane. The flask was
evacuated and refilled with ethylene, then charged with 75 mL of
dry, deoxygenated toluene. The resultant suspension was cooled to
0.degree. C. and allowed to equilibrate with 1 atmosphere ethylene
for 15 minutes, then treated with 4.0 mL of a 10 wt % solution of
MAO in toluene and stirred under 1 atmosphere ethylene. A white
polyethylene precipitate (with a faint yellow-orange tinge) was
observed within minutes. After 38 minutes, the mixture was quenched
by the addition of acetone (50 mL), methanol (50 mL) and 6 N
aqueous HCl (100 mL). The swollen polyethylene that separated was
isolated by vacuum filtration and washed with water, methanol and
acetone, then dried under reduced pressure (0.05-0.1 mm Hg) for 18
hours to give 6.0 g of a white polyethylene (54,000 TO/h). .sup.1H
NMR: 19 branches/1000 carbon atoms. GPC: M.sub.n=504,000;
M.sub.w/M.sub.n=2,3.
Example 58
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(benzyloxymethyl)-5,6-bis(2,6-dimethylphenylimino)-[1,4]dioxane
in the presence of MAO
[0253] A 500 mL round bottom flask was fitted with a Schlenk
adapter and equipped with a magnetic stir bar and capped with a
septum was charged with 100 mL of dry, deoxygenated toluene. The
flask was placed in a water bath and allowed to equilibrate with 1
atmosphere ethylene for 19 minutes, then 0.25 mL of a stock
solution prepared from 10.0 mg of the nickel dibromide complex of
2,3-bis(benzyloxymethyl)-5,6-bis(2,6-dimethyl-
phenylimino)-[1,4]dioxane and 10.0 mL dichloromethane was added.
The reaction mixture was then treated with 4.0 mL of a 10 wt %
solution of MAO in toluene and stirred under 1 atmosphere ethylene.
Ethylene uptake and formation of a polyethylene precipitate were
observed. After 6.5 minutes, the mixture was quenched by the
addition of acetone, methanol and 6 N aqueous HCl. The swollen
polyethylene which separated was isolated by vacuum filtration,
then dried at 80.degree. C. in vacuo for several hours. 392 mg of
white polyethylene was isolated (404,000 TO/h). DSC: (2nd heat)
melt with an endothermic maximum at 120.degree. C. .sup.1H NMR: 16
branches/1000 carbon atoms. GPC: M.sub.n=125,000;
M.sub.w/M.sub.n=2.8.
Example 59
Polymerization of ethylene with the nickel dibromide complex of
5-methoxymethyl-2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane in
the presence of MAO
[0254] A 200 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar and capped with a septum was charged with 3.8 mg of the
nickel dibromide complex of
5-methoxymethyl-2,3-bis(2,6-dimethylphenylimino)-[1,- 4]dioxane.
The flask was evacuated and refilled with ethylene, then charged
with 75 mL of dry, deoxygenated toluene. The resultant suspension
was cooled to 0.degree. C. and allowed to equilibrate with 1
atmosphere ethylene for 15 minutes, then treated with 4.0 mL of a
10 wt % solution of MAO in toluene and stirred under 1 atmosphere
ethylene. After 10 minutes, the mixture was quenched by the
addition of acetone (50 mL), methanol (50 mL) and 6 N aqueous HCl
(100 mL). The swollen polyethylene which separated was isolated by
vacuum filtration and washed with water, methanol and acetone, then
dried under reduced pressure (0.05-0.1 mm Hg) for 48 hours to give
1.04 g of a white, powdery polyethylene. A similar reaction, also
at 0.degree. C., was conducted using 0.655 g (equivalent to 0.57 mg
of the nickel complex) of a stock solution of 11.6 mg nickel
dibromide complex of
5-methoxymethyl-2,3-bis-(2,6-dimethylphenylimino)-[1- ,4]dioxane in
13.238 g dichloromethane to obtain 291 mg white, powdery
polyethylene after 15 minutes reaction.
Example 60
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane in the presence of
MMAO (23% iso-butylaluminoxane)
[0255] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under high vacuum to ensure the reactor was dry. The
reactor was cooled and purged with argon. Under an argon
atmosphere, the autoclave was charged with 150 mL of toluene and
0.3 mL of a stock solution (10 mg in 10 mL CH.sub.2Cl.sub.2) of the
nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane. The autoclave was
heated to 60.degree. C. and 2 mL of MMAO in heptane (6.42 wt %
aluminum) was added. The reactor was rapidly pressurized to 100
psig and the temperature ramped up to 65.degree. C. After 10
minutes at 65.degree. C., the reaction was quenched by the addition
of acetone, and methanol. The swollen polyethylene which separated
was isolated by filtration and dried for several hours in a vacuum
oven at 80.degree. C. 1.3 g of a white rubbery solid was isolated
(480,000 TO/h). DSC: (2nd heat) melt with an endothermic maximum at
76.degree. C. .sup.1H NMR: 33 branches/1000 carbon atoms. GPC:
M.sub.n=42,000; M.sub.w/M.sub.n=1.82.
Example 61
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane in the presence of
MMAO (23% iso-butylaluminoxane)
[0256] The procedure described in example 60 was followed except
the polymerization was conducted at 25.degree. C. resulting in 0.59
g of polyethylene (226,000 TO/h). DSC: (2nd heat) melt with an
endothermic maximum at 125.degree. C. .sup.1H NMR: 9 branches/1000
carbon atoms. GPC: Mn=237,000; Mw/Mn=2.15.
Example 62
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane in the presence of
MMAO (23% iso-butylaluminoxane)
[0257] The procedure described in example 60 was followed except
the polymerization was conducted at 80.degree. C. resulting in 0.29
g of polyethylene (110,000 TO/h). .sup.1H NMR: 69 branches/1000
carbon atoms. GPC: Mn=23,000; Mw/Mn=1.65.
Example 63
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane in the presence of
MMAO (23% iso-butylaluminoxane)
[0258] The procedure described in example 60 was followed except
the polymerization was conducted at 50.degree. C. resulting in 3.1
g of polyethylene (1,200,000 TO/h). DSC: (2nd heat) melt with an
endothermic maximum at 95.degree. C. .sup.1H NMR: 48 branches/1000
carbon atoms. GPC: Mn=63,000; Mw/Mn=1.92.
Example 64
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dioxane in the presence of
MMAO (23% iso-butylaluminoxane)
[0259] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under high vacuum to ensure the reactor was dry. The
reactor was cooled and purged with argon. Under an argon
atmosphere, the autoclave was charged with 150 mL of toluene and
0.5 mL of a stock solution (10 mg in 10 mL CH.sub.2Cl.sub.2) of the
nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dioxane. The autoclave was
heated to 60.degree. C. and 2 mL of MMAO in heptane (6.42 wt %
aluminum) was added. The reactor was rapidly pressurized to 100
psig and the temperature ramped up to 65.degree. C. After 10
minutes at 65.degree. C., the reaction was quenched by the addition
of acetone, and methanol. The swollen polyethylene which separated
was isolated by filtration and dried for several hours in a vacuum
oven at 80.degree. C. 2.5 g of a white rubbery solid was isolated
(660,000 TO/h). DSC: (2nd heat) broad melt with an endothermic
maximum at 30.degree. C. .sup.1H NMR: 82 branches/1000 carbon
atoms. GPC: Mn=147,000; Mw/Mn=1.91.
Example 65
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dioxane in the presence of
MMAO (23% iso-butylaluminoxane)
[0260] The procedure described in example 64 was followed except
the polymerization was conducted at 50.degree. C. resulting in 3.4
g of polyethylene (900,000 TO/h). DSC: (2nd heat) melt with an
endothermic maximum at 50.degree. C. .sup.1H NMR: 65 branches/1000
carbon atoms. GPC: Mn=219,000; Mw/Mn=1.85.
Example 66
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dioxane in the presence of
MMAO (23% iso-butylaluminoxane)
[0261] The procedure described in example 64 was followed except
the polymerization was conducted at 25.degree. C. resulting in 1.22
g of polyethylene (320,000 TO/h). DSC: (2nd heat) melt with an
endothermic maximum at 112.degree. C. .sup.1H NMR: 17 branches/1000
carbon atoms. GPC: Mn=476,000; Mw/Mn=2.02.
Example 67
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dioxane in the presence of
MMAO (23% iso-butylaluminoxane)
[0262] The procedure described in example 64 was followed except
the polymerization was conducted at 80.degree. C. resulting in 0.9
g of polyethylene (240,000 TO/h). DSC: (2nd heat) melt with an
endothermic maximum at -10.degree. C. .sup.1H NMR: 99 branches/1000
carbon atoms. GPC: Mn=98,800; Mw/Mn=1.81.
Example 68
Copolymerization of ethylene and ethyl undecenoate with the nickel
dibromide complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane
in the presence of MMAO (23% iso-butylaluminoxane)
[0263] A flame dried Schlenk flask equipped with a stir bar and a
rubber septum was charged with 50 ml of toluene and 6 mg of the
nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane. The flask was cooled
to 0.degree. C. in an ice-water bath and filled with ethylene (1
atmosphere). To the flask was added, 2.0 ml of MMAO in heptane
(6.42 wt % aluminum). Within 15 seconds 2.5 ml of ethyl undecenoate
was added to give a purple solution. The mixture was left to stir
for 16 hours. Acetone, methanol and 6M HCl were added to quench the
reaction and precipitate the polymer. The polymer was collected by
suction filtration and washed with copious amounts of acetone to
ensure all of the ethyl undecenoate comonomer is removed resulting
in 510 mg of white powdery polymer. NMR spectroscopic analysis is
consistent with the preparation of an ester group containing
copolymer. In addition, ethylene homopolymer, which resulted from
the short reaction time prior to addition of the ethyl undecenoate,
was present. IR: CO stretch at 1742 cm.sup.-1. .sup.1H NMR: 1.0 wt
% ethyl undecenoate incorporated. GPC: M.sub.n=61,000,
M.sub.w/M.sub.n=6.4. DSC: T.sub.m=125.degree. C.
Example 69
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-4-methylmorpholine in the
presence of MAO
[0264] A 1 L Fischer-Porter bottle was assembled onto a pressure
head equipped with a mechanical stirrer and gas and liquid
feed-through ports, then pressurized to 75 psig of ethylene and
relieved to ambient pressure seven times. The bottle was immersed
in a 54.degree. C. water bath, then 100 mL of dry, deoxygenated
toluene was added via syringe. The mixture was re-pressurized with
ethylene at 75 psig and stirred at 300 rpm for 5 minutes to
saturate the solution with ethylene, then the pressure was again
relieved, and 4.0 mL of a 10 wt % solution of MAO in toluene was
quickly added. The apparatus was again re-pressured to 75 psig
ethylene and stirred at 300 rpm for another 5 min to ensure
saturation with ethylene. The pressure was once again relieved to
ambient pressure and 0.5 mL of a stock solution prepared from 10.0
mg of the nickel dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-4-methylmorpholine and 10 mL
dichloromethane was quickly added and the system quickly
pressurized once again with ethylene to 75 psig. After 7 min the
pressure was relieved to atmospheric and the reaction was quenched
by addition of 5 mL methanol. After the apparatus was disassembled,
an additional 50 mL methanol, 50 ml aqueous 6N HCl and 20 mL
acetone was added. The resultant organic layer was separated,
washed with 6 N aqueous HCl (1.times.25 mL), and water (2.times.50
mL), then concentrated by rotary evaporation under reduced pressure
(10 Torr) at 40.degree. C. The residue was then treated with
toluene (50 mL) and re-concentrated to afford 134 mg of a very
rubbery, clear polyethylene (55,000 TO/h). .sup.1H NMR: 134
branches/1000 carbon atoms. GPC: M.sub.n=169,000;
M.sub.w/M.sub.n=1.4.
Example 70
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-dimethyl-phenylimino)-4-methylmorpholine in the
presence of MMAO
[0265] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under high vacuum to ensure the reactor was dry. The
reactor was cooled and purged with argon. Under an argon
atmosphere, the autoclave was charged with 1510 mL of toluene and 1
mL of a stock solution (10 mg in 20 mL CH.sub.2Cl.sub.2) of the
nickel dibromide complex of
2,3-bis(2,6-dimethyl-phenylimino)-4-methylmorpholine. The autoclave
was heated to 45.degree. C. and 3 mL of MMAO in heptane (6.42 wt %
aluminum) was added. The reactor was rapidly pressurized to 100
psig and the temperature ramped up to 50.degree. C. After 10
minutes at 50.degree. C., the reaction was quenched by the addition
of acetone, and methanol. The swollen polyethylene which separated
was isolated by filtration and dried for several hours in a vacuum
oven at 80.degree. C. resulting in 0.87 g of a white rubbery solid
was isolated (138,000 TO/h). .sup.1H NMR: 97 branches/1000 carbon
atoms.
Example 71
Polymerization of ethylene with the nickel dibromide complex of
1,3-bis(4-methoxy-2,6-dimethylphenyl)-4,5-bis(4-methoxy-2,6-dimethylpheny-
limino)imidazolidin-2-one in the presence of MAO
[0266] A 500 mL round bottom flask fitted with a Schienk adapter
and equipped with a magnetic stir bar and capped with a septum was
evacuated, flame-dried, then refilled with ethylene. The flask was
provided with a room temperature (ca. 23.degree. C.) water bath,
then charged with 100 mL of dry, deoxygenated toluene and allowed
to equilibrate with 1 atmosphere ethylene for 30 minutes while
stirring at 1000 rpm. The reaction mixture was then treated with
4.0 mL of a 10 wt % solution of MAO in toluene and stirred under 1
atmosphere ethylene, then 0.10 mL of a stock solution prepared from
6.0 mg of the nickel dibromide complex of
1,3-bis(4-methoxy-2,6-dimethylphenyl)-4,5-bis(4-methoxy-2,6-dimethylpheny-
limino)imidazolidin-2-one and 6.0 mL dichloromethane was added.
After about 7 min and 20 seconds an additional 0.25 mL of the stock
solution was added. After 15 more minutes, the reaction mixture was
quenched by the addition of acetone, methanol and 6 N aqueous HCl.
The polyethylene which separated was isolated by vacuum filtration
and washed with water, methanol and acetone, then dried on the
filter for 2 h, then further dried 13 days in a vacuum oven at
80.degree. C. to obtain 172 mg white polyethylene. DSC: (2nd heat)
melt with an endothermic maximum at 124.degree. C. .sup.1H NMR
showed this material to contain approximately 18 branches/1000
carbon atoms. GPC: M.sub.n=56,500; M.sub.w/M.sub.n=3.55.
Example 72
Polymerization of ethylene with the reaction product of
1,3-bis-(2,6-dimethyl-phenyl)-4,5-bis-(2,6-dimethyl-phenylimino)-imidazol-
idin-2-one, (1,2-dimethoxyethane)nickel(II) dibromide, and silver
tetrafluoroborate in the presence of MAO
[0267] A 500 mL round bottom flask fitted with a Schlenk adapter,
capped with a septum, and equipped with a magnetic stir bar was
charged with 100 mL of dry, deoxygenated toluene. The flask was
placed in a water bath and allowed to equilibrate with 1 atmosphere
ethylene for 10 minutes, then 0.10 mL of a stock solution (freshly
prepared from 240 mg of the reaction product of
1,3-bis-(2,6dimethylphenyl)-4,5-bis-(2,6-dimethylphenylimino)--
imidazolidin-2-one, (1,2-dimethoxyethane)nickel(lI) dibromide, and
silver tetrafluoroborate in 10 mL dry, deoxygentated
dichloromethane) was added. The reaction mixture was then treated
with 4.0 mL of a 10 wt % solution of MAO in toluene and stirred
under 1 atmosphere ethylene. Ethylene uptake and formation of a
polyethylene precipitate were observed. After 6.33 minutes, the
mixture was quenched by the addition of acetone (50 mL), methanol
(50 mL) and 6 N aqueous HCl (100 mL). The swollen polyethylene
which separated was isolated by vacuum filtration, then dried at
80.degree. C. in vacuo for several hours. 860 mg of a white powdery
polyethylene was isolated (87,000 TO/h). .sup.1H NMR: 15
branches/1000 carbon atoms. GPC: M.sub.n=76,000;
M.sub.w/M.sub.n=2.6
Example 73
Polymerization of ethylene using a catalyst generated in situ from
tetrakis(2,6-dimethylphenyl)oxalamidine,
bis(1,5-cyclooctadiene)nickel(0) and HB(Ar).sub.4
(Ar=3,5-bis(trifluoromethyl)phenyl)
[0268] A 250 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar and capped with a septum was charged with 8.0 mg of
bis(1,5-cyclooctadiene)nickel(0), 19 mg of
N.sup.1,N.sup.2,N.sup.3,N.sup.-
4-tetrakis(2,6-dimethylphenyl)oxalamidine, and 33 mg of the ether
solvate of HB(Ar).sub.4.
[0269] The flask was evacuated and refilled with ethylene, then
charged with 75 mL of dry, deoxygenated toluene. The yellow
solution which resulted was stirred under ethylene at 0.degree. C.
for 30 minutes, then warmed to 25.degree. C. and stirred for
another 30 minutes under ethylene before being quenched by addition
of acetone (50 mL), and methanol ( 50 mL). The polyethylene which
separated was isolated by vacuum filtration and washed with water,
methanol and acetone, then dried under reduced pressure (0.5 mm Hg)
for 14 hours to give 0.70 g of an elastic white polyethylene
(average 860 TO/h). .sup.1H NMR: 83 branches/1000 carbon atoms.
GPC: M.sub.n=173,000; M.sub.w/M.sub.n=2.8.
Example 74
Polymerization of ethylene with the nickel dibromide complex of
1,4-dimethyl-2,3-bis(2,6-dimethylphenylimino)piperazine in the
presence of MAO
[0270] A 250 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar and capped with a septum was charged with 10.4 mg of the
nickel dibromide complex of
1,4-dimethyl-2,3-bis(2,6-dimethylphenylimino)piperaz- ine. The
flask was evacuated and refilled with ethylene, then charged with
75 mL of dry, deoxygenated toluene. The resultant suspension was
cooled to 0.degree. C. and allowed to equilibrate with 1 atmosphere
ethylene for 15 minutes, then treated with 4.0 mL of a 10 wt %
solution of MAO in toluene. The yellow solution which resulted was
stirred under ethylene at 0.degree. C. for 1 hour, and then
quenched by the addition of acetone (50 mL), methanol (50 mL) and 6
N aqueous HCl (100 mL). The swollen polyethylene which separated
was isolated by vacuum filtration and washed with water, methanol
and acetone, then dried under reduced pressure (0.5 mm Hg) for 14
hours to give 1.3 g of a clear elastic polyethylene (2531 TO/h).
.sup.1H NMR: 91 branches/1000 carbon atoms. GPC: M.sub.n=127,000;
M.sub.w/M.sub.n=1.3.
Example 75
Ethylene polymerization using complex XXXV
[0271] A flame dried Schlenk flask equipped with a stir bar and a
rubber septum was charged with 50 ml of methylene chloride and 50
mg of the palladium complex XXXV. The flask was placed under an
ethylene atmosphere (1 atmosphere). The mixture was left to stir
for 20 hours. Acetone and methanol were added to quench the
reaction and precipitate the polymer. The polymer was collected and
dried in vacuo resulting in 2,6 g of tacky polymer. NMR
spectroscopic analysis is consistent with the preparation of an
ethylene homopolymer. .sup.1H NMR: highly branched polyethylene.
GPC: M.sub.n=34,000, M.sub.w/M.sub.n=2.5. DSC: T.sub.m=-39.degree.
C., T.sub.g=-69.degree. C.
Example 76
Propylene Polymerization using complex XXXV
[0272] A flame dried Schlenk flask equipped with a stir bar and a
rubber septum was charged with 50 ml of methylene chloride and 50
mg of the palladium complex XXXV. The flask was placed under a
propylene atmosphere (1 atmosphere). The mixture was left to stir
for 20 hours. Acetone and methanol were added to quench the
reaction and precipitate the polymer. The polymer was collected and
dried in vacuo resulting in 580 mg of tacky polymer. .sup.1H NMR:
192 branch points/1000 carbon atoms. GPC: M.sub.n=17,000,
M.sub.w/M.sub.n=2.08. DSC: T.sub.g=-53.degree. C.
Example 77
Ethylene/vinyl ethylene carbonate copolymerization using complex
XXXV
[0273] A 200 mL flame dried pear-shaped Schlenk flask equipped with
a magnetic stir bar and capped with a septum was charged with
(2,6-di-isopropylphenylimino)-[1,4]dithiane Pd(II) catalyst XXXV
(100 mg) in an argon filled glove box. Upon removal from the glove
box, the flask was evacuated and backfilled with ethylene. The
catalyst was dissolved in CH.sub.2Cl.sub.2 (25 mL) and immediately
treated with vinyl ethylene carbonate (5mL). The resulting orange
solution was stirred at 23.degree. C. under an ethylene atmosphere
(1 atm) for 20 hours. A small amount of polymer had precipitated
out of solution. The polymerization was quenched with MeOH and
acetone leaving gray oil adhering to the walls of the flask. The
polymer was washed several times with acetone and MeOH to remove
any remaining monomer. The polymer was dissloved in
CH.sub.2Cl.sub.2 and transferred to a storage jar. The solvent was
left to evaporate and the resulting oily polymer was dried in vacuo
at .about.80.degree. C. for 3 days to afford a tacky solid (2.15 g,
1100 TO). .sup.1H NMR was consistent with a copolymer containing
approximately 96.5 weight % ethylene and 3.5 weight % vinyl
ethylene carbonate monomer units.; M.sub.n 40,200 .sup.g/.sub.mol;
M.sub.w 92,100 .sup.g/.sub.mol; DSC T.sub.g-68.degree. C.,
T.sub.m-38.degree. C.
Example 78
Ethylene/vinyl ethylene carbonate copolymerization using complex
XXXV.
[0274] A 200 mL flame dried pear-shaped Schlenk flask equipped with
a magnetic stir bar and capped with a septum was charged with
(2,6-di-isopropylphenylimino)-[1,4]dithiane Pd(II) catalyst XXXV
(100 mg) in an argon filled glove box. Upon removal from the glove
box, the flask was evacuated and backfilled with ethylene. The
catalyst was dissolved in CH.sub.2Cl.sub.2 (20 mL) and immediately
treated with vinyl ethylene carbonate (10 mL). The resulting orange
solution was stirred at 23.degree. C. under an ethylene atmosphere
(1 atm) for 28 hours. A small amount of polymer had precipitated
out of solution. The polymerization was quenched with MeOH and
acetone leaving gray oil adhering to the walls of the flask. The
polymer was dissloved in CH.sub.2Cl.sub.2 and transferred to a
storage jar. The solvent was left to evaporate and the resulting
oily polymer was washed several times with acetone and MeOH to
remove any remaining monomer and dried in vacuo at
.about.80.degree. C. for 1 day to afford a tacky solid (1 .15 g,
613 TO). .sup.1H NMR was consistent with a copolymer containing
approximately 95.5 weight % ethylene and 4.5 weight % vinyl
ethylene carbonate monomer units.; M.sub.n 15,400 .sup.g/.sub.mol;
M.sub.w 96,000 .sup.g/.sub.mol; DSC T.sub.g-64.degree. C.,
T.sub.m-31.degree. C.
Example 79
Preparation of the nickel dibromide complex of
2,3-bis(2,6-diisopropylphen- ylimino)-[1,4]dioxane
[0275] A Schlenk flask equipped with a magnetic stir bar was
charged with 100 mg of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dioxane (0.25 mmol) and 71
mg of (1,2-dimethoxyethane)nickel(II) dibromide (0.23 mmol) under
an argon atmosphere. Dry, deoxygenated dichloromethane (15 mL) was
added and the mixture was stirred under an argon atmosphere,
turning red-brown within about 10 minutes. After 2 hours, the
red/orange solution was transferred via filter cannula to a new
flame dried Schlenk to remove trace amount of unreacted
(1,2-dimethoxyethane)nickel(II) dibromide. The CH.sub.2Cl.sub.2 was
removed in vacuo. The resulting red-brown solid was washed with
2.times.10 mL of hexane and the solid was dried in vacuo for
several hours affording 80 mg of a brown solid.
Example 80
Preparation of
2,3-bis(2,6-dimethylphenylimino)-2,3-dihydroimidazo[2,1-b]t-
hiazole
[0276] A 50 mL round bottom flask equipped with a magnetic stir bar
and a reflux condenser capped by a nitrogen inlet was charged with
752 mg of N.sup.1,N.sup.2-bis(2,6-dimethylphenyl)oxalodiimidoyl
dichloride, 200 mg of sodium hydride (60% mineral oil dispersion),
5.0 mL of dry tetrahydrofuran, and 250 mg of 2-mercaptoimidazole.
The mixture was heated at reflux for 120 minutes. After cooling,
the mixture was diluted with water and dichloromethane, and the
organic layer was separated and concentrated to afford a
yellow-orange oil. Column chromatography (SiO.sub.2, Merck Grade
9385 230-400 mesh, 60 .ANG.; 12 v % ethyl acetate in hexane)
afforded 487 mg of a yellow-orange solid. Recrystallization from
heptane gave 366 mg yellow-orange prisms. Field desorption mass
spectrometry showed a parent ion peak at 360 m/z.
Example 81
Preparation of
N.sup.1,N.sup.2-bis(2,6-dimethylphenyl)ethanediimidoselenoi- c acid
diphenyl ester
[0277] A 50 mL round bottom flask equipped with a magnetic stir bar
and a reflux condenser capped by a nitrogen inlet was charged with
961 mg of N.sup.1,N.sup.2-bis(2,6-dimethylphenyl.)oxalodiimidoyl
dichloride, 287 mg of sodium hydride (60% mineral oil dispersion),
8.2 mL of dry tetrahydrofuran, and 0.068 mL of benzeneselenol. The
mixture was heated at reflux for 45 minutes. After cooling, the
mixture was diluted with water and diethyl ether. The ether layer
was separated and washed again with water, then concentrated in
vacuo to afford a yellow-orange crystalline solid. The solid was
dissolved in hot hexane, then filtered, and then reconcentrated.
Recrystallization from heptane afforded 745 mg orange prisms,
1.sup.st crop. Field desorption mass spectrometry showed a parent
ion cluster of peaks from 570-578 m/z. .sup.1H NMR (300 MHz,
CDCl.sub.3, chemical shifts in ppm relative to TMS at 0 ppm): 1.95
(12 p, s), 6.75 (6p, app s), 7.02-7.20 (6p, m), 7.39-7.48 (4p,
m).
Example 82
Polymerization of ethylene using a catalyst generated in situ from
N.sup.1,N.sup.2-bis(2,6-dimethylphenyl)ethanediimidoselenoic acid
diphenyl ester, bis(1,5-cyclooctadiene)nickel(0) and HB(Ar).sub.4
(Ar=3,5-bis(trifluoromethyl)phenyl)
[0278] A 250 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar and capped with a septum was charged with 5 mg of
bis(1,5-cyclooctadiene)nickel(0), 10 mg of
N.sup.1,N.sup.2-bis(2,6-dimeth- ylphenyl)ethanediimidoselenoic acid
diphenyl ester, and 25 mg of the ether solvate of HB(Ar).sub.4. The
flask was evacuated and refilled with ethylene, then charged with
45 mL of dry, deoxygenated toluene. The yellow solution which
resulted was stirred under ethylene at 21.degree. C. for 10
minutes, then quenched by addition of methanol (50 mL). The
polyethylene which separated was isolated by vacuum filtration and
washed with methanol, then dried under reduced pressure (0.5 mm Hg)
for 14 hours to give 0.060 g of an elastic blue-green polyethylene.
.sup.1H NMR: 24 branches/1000 carbon atoms. GPC: M.sub.n=181,000;
M.sub.w/M.sub.n=3.5.
Example 83
Preparation of the nickel dibromide complex of
2,3-bis(2,6-dimethylphenyli-
mino)-2,3-dihydroimidazo[2,1-b]thiazole
[0279] A 50 mL Schienk flask equipped with a magnetic stir bar and
capped with a septum was charged with 141 mg of
2,3-bis(2,6-dimethylphenylimino)-
-2,3-dihydroimidazo[2,1-b]thiazole and 110 mg of
(1,2-dimethoxyethane)nick- el(II) dibromide under an inert
atmosphere. Dry, deoxygenated dichloromethane (5 mL) was added and
the mixture was stirred under an argon atmosphere. After 1 hour,
another 5 mL of dichloromethane was added. The mixture was stirred
another 16 hours at 21.degree. C., then diluted with 10 mL of dry,
deoxygenated hexane and stirred another 3 hours. The supernatant
was removed via a filter paper-tipped cannula, and the residue
dried in vacuo at 1 mm Hg to afford 66 mg of a brown
microcrystalline solid.
Example 84
Polymerization of ethylene with the nickel dibromide complex
2,3-bis(2,6-dimethylphenylimino)-2,3-dihydroimidazo[2,1-b]thiazole
in the presence of MAO
[0280] A 200 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar and capped with a septum was charged with 2.5 mg of the
nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-2,3-dihydroimidazo[-
2,1-b]thiazole. The flask was evacuated and refilled with ethylene,
then charged with 75 mL of dry, deoxygenated toluene. The resultant
suspension allowed to equilibrate with 1 atmosphere ethylene at
21.degree. C. for 15 minutes, then treated with 200 .mu.L of a 10
wt % solution of MAO in toluene and stirred under 1 atmosphere
ethylene. After 21 min, the reaction was quenched by the addition
of acetone (50 mL), methanol (50 mL) and 6 N aqueous HCl (100 mL).
The swollen polyethylene which separated was isolated by vacuum
filtration and washed with water, methanol and acetone, then dried
under reduced pressure (0.05-0.1 mm Hg) for 24 hours to give 198 mg
of a white polyethylene. .sup.1H NMR: 13 branches/1000 carbon
atoms. GPC: bimodal, with M.sub.n=23,000; M.sub.p=366,000;
M.sub.w/M.sub.n=13.5.
Example 85
Preparation of the nickel dibromide complex of
N.sup.1,N.sup.2,N.sup.3,N.s-
up.4-tetrakis(2,6-dimethylphenyl)oxalamidine
[0281] A 50 mL Schlenk flask equipped with a magnetic stir bar and
capped with a septum was charged with 100 mg of
N.sup.1,N.sup.2,N.sup.3,N.sup.4--
tetrakis(2,6-dimethylphenyl)oxalamidine and 55 mg of
(1,2-dimethoxyethane)nickel(II) dibromide under an inert
atmosphere. Dry, deoxygenated dichloromethane (5 mL) was added and
the mixture was stirred under an argon atmosphere. After 1 hour,
another 5 mL of dichloromethane was added. The mixture was stirred
another 16 hours at 21.degree. C., then diluted with 10 mL of dry,
deoxygenated hexane and stirred another 3 hours. The supernatant
was removed via a filter paper-tipped cannula, and the residue
dried in vacuo at 1 mm Hg to afford 95 mg of light green
crystals.
Example 86
Polymerization of ethylene with the nickel dibromide complex of
N.sup.1,N.sup.2,N.sup.3,N.sup.4-tetrakis(2,6-dimethylphenyl)oxalamidine
in the presence of MAO
[0282] A 200 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar and capped with a septum was charged with 2.4 mg of nickel
dibromide complex of
N.sup.1,N.sup.2,N.sup.3,N.sup.4-tetrakis(2,6-dimethylphenyl)ox-
alamidine. The flask was evacuated and refilled with ethylene, then
charged with 75 mL of dry, deoxygenated toluene. The resultant
suspension allowed to equilibrate with 1 atmosphere ethylene at
21.degree. C. for 15 minutes, then treated with 4.0 mL of a 10 wt %
solution of MAO in toluene and stirred under 1 atmosphere ethylene.
After 30 min, the reaction was quenched by the addition of acetone
(50 mL), methanol (50 mL) and 6 N aqueous HCl (100 mL). The swollen
polyethylene which separated was isolated by vacuum filtration and
washed with water, methanol and acetone, then dried under reduced
pressure (0.05-0.1 mm Hg) for 24 hours to give 743 mg of a white
polyethylene. .sup.1H NMR: 112 branches/1000 carbon atoms. GPC:
M.sub.n=330,000; M.sub.w/M.sub.n=1.4.
Example 87
Copolymerization of ethylene and 1-pentene with the nickel
dibromide complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane
in the presence of MAO
[0283] A 200 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar and capped with a septum was charged with 0.5 mL of a
stock solution of 12.4 mg of the nickel dibromide complex of
2,3-bis(2,6-dimethylphenyli- mino)-[1,4]dithiane in 10.0 mL
dichloromethane. The flask was evacuated and refilled with
ethylene, then charged with 100 mL of dry, deoxygenated toluene,
and 5.0 mL 1-pentene. The resultant suspension was cooled to
0.degree. C. and allowed to equilibrate with I atmosphere ethylene
for 15 minutes, then treated with 4.0 mL of a 10 wt % solution of
MAO in toluene and stirred under 1 atmosphere ethylene. After 45
minutes, the mixture was quenched by the addition of acetone (50
mL), methanol (50 mL) and 6 N aqueous HCl (100 mL). The swollen
copolymer which separated was isolated by vacuum filtration and
washed with water, methanol and acetone, then dried under reduced
pressure (255 mm Hg) at 100.degree. C. for 24 hours to obtain 2.0 g
of white coploymer. .sup.1H NMR: 24 branches/1000 carbon atoms.
.sup.13C NMR: 7.6 methyl branches/1000 carbons, 1.2 ethyl
branches/1000 carbons, 9.1 propyl branches/1000 carbons, 2.1 butyl
branches/1000 carbons, 3.4 pentyl and higher alkyl branches/1000
carbons. GPC: M.sub.n=274,000; M.sub.w/M.sub.n=2,3.
Example 88
Copolymerization of ethylene and 1-heptene with the nickel
dibromide complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane
in the presence of MAO
[0284] A 200 mL pear-shaped Schlenk flask equipped with a magnetic
stir bar and capped with a septum was charged with 0.5 mL of a
stock solution of 12.4 mg of the nickel dibromide complex of
2,3-bis(2,6-dimethylphenyli- mino)-[1,4]dithiane in 10.0 mL
dichloromethane. The flask was evacuated and refilled with
ethylene, then charged with 100 mL of dry, deoxygenated toluene,
and 5.0 mL 1-heptene. The resultant suspension was cooled to
0.degree. C. and allowed to equilibrate with 1 atmosphere ethylene
for 15 minutes, then treated with 4.0 mL of a 10 wt % solution of
MAO in toluene and stirred under 1 atmosphere ethylene. After 33
minutes, the mixture was quenched by the addition of acetone (50
mL), methanol (50 mL) and 6 N aqueous HCl (100 mL). The swollen
copolymer which separated was isolated by vacuum filtration and
washed with water, methanol and acetone, then dried under reduced
pressure (255 mm Hg) at 100.degree. C. for 24 hours to obtain 1.25
g of white coploymer. .sup.1H NMR: 19 branches/1000 carbon atoms.
.sup.13C NMR: 5.9 methyl branches/1000 carbons, less than 1 ethyl
branch/1000 carbons, less than 1 propyl branch/1000 carbons, 1.8
butyl branches/1000 carbons, 11.5 pentyl and higher alkyl
branches/1000 carbons. GPC: M.sub.n=223,000;
M.sub.w/M.sub.n=2,3.
Example 89
Polymerization of 1-hexene with the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of
MAO
[0285] A 22 mL vial equipped with a magnetic stir bar and capped by
a septum was sequentially charged with 1.8 mg of the nickel
dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane, 4.0 mL 1-hexene,
and 2.0 mL of a 10 wt % solution of MAO in toluene, under Ar. The
resultant violet mixture thickened noticably within minutes. After
34 min, the reaction was quenched with acetone, methanol and 6 N aq
HCl, and the polyhexene which separated was filtered off and dried
in vacuo (0.4 mm Hg) to obtain 428 mg of an elastic polyhexene.
.sup.1H NMR: 173 branches/1000 carbon atoms. GPC: M.sub.n=92,000;
M.sub.w/M.sub.n=2.0.
Example 90
Polymerization of 1-hexene with the nickel dibromide complex
2,3-bis(2,6-dimethylphenylimino)-2,3-dihydroimidazo[2,1-b]thiazole
in the presence of MAO
[0286] A 22 mL vial equipped with a magnetic stir bar and capped by
a septum was sequentially charged with 2.1 mg of the nickel
dibromide complex
2,3-bis(2,6-dimethylphenylimino)-2,3-dihydroimidazo[2,1-b]thiazol-
e, 4.0 mL 1-hexene, and 2.0 mL of a 10 wt % solution of MAO in
toluene, under Ar. The resultant dark purple-brown mixture
thickened noticably within 10-20 minutes. After 53 min, the
reaction was quenched with acetone, methanol and 6 N aq HCl, and
the polyhexene which separated was filtered off and dried in vacuo
(0.4 mm Hg) to obtain 283 mg of an elastic polyhexene. .sup.1H NMR:
110 branches/1000 carbon atoms. GPC: M.sub.n=91,000;
M.sub.w/M.sub.n=1.9.
Example 91
Polymerization of 1-hexene with the nickel dibromide complex of
1,4-dimethyl-2,3-bis(2,6-dimethylphenylimino)piperazine in the
presence of MAO
[0287] A 22 mL vial equipped with a magnetic stir bar and capped by
a septum was sequentially charged with 2.1 mg of nickel dibromide
complex of 1,4-dimethyl-2,3-bis(2,6-dimethylphenylimino)piperazine,
4.0 mL 1-hexene, and 2.0 mL of a 10 wt % solution of MAO in
toluene, under Ar. The resultant clear yellow solution was stirred
at 23.degree. C. for 400 min, then the reaction was quenched with
acetone, methanol and 6 N aq HCl, and the polyhexene which
separated was filtered off and dried in vacuo (0.4 mm Hg) to obtain
408 mg of an elastic polyhexene. .sup.1H NMR: 90 branches/1000
carbon atoms. GPC: M.sub.n=47,000; M.sub.w/M.sub.n=1.7.
Example 92
Synthesis of the supported nickel complex of
2,3-bis(2,6-dimethylphenylimi- no)-[1.4]dithiane
[0288] A flame dried pear-shaped flask equipped with a stir bar and
a septum was charged with 30 mg (52 .mu.mol) of the nickel
dibromide complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane
and 1 g of MAO treated silica (purchased from Witco TA
02794/HL/04). The solid mixture was cooled to 0.degree. C. in an
ice bath and 25 mL of the CH.sub.2Cl.sub.2 was added. The reaction
was rapidly stirred at 0.degree. C. for 1 hour. After 1 hour the
solvent was removed in vacuo. The resulting purple solid was washed
with CH.sub.2Cl.sub.2 using a filter cannula and dried under
dynamic vacuum.
Example 93
Synthesis of the supported nickel complex of
2,3-bis(2,6-dimethylphenylimi- no)-[1,4]dithiane
[0289] A flame dried pear-shaped flask equipped with a stir bar and
a septum was charged with 15 mg (26 .mu.mol) of the nickel
dibromide complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane
and 1 g of MAO treated silica (purchased from Witco TA
02794/HL/04). The solid mixture was cooled to 0.degree. C. in an
ice bath and 20 mL of toluene was added. The reaction was rapidly
stirred at 0.degree. C. for 1 hour. After 1 hour the solid was
allowed to settle and the solvent was removed via filter cannula.
The resulting purple solid was washed with toluene using a filter
cannula. The resulting purple silica support material was dried
under dynamic vacuum giving 916 mg of supported catalyst
material.
Example 94
Synthesis of the supported nickel complex of
2,3-bis(2,6-dimethylphenylimi- no)-[1,4]dithiane
[0290] A flame dried pear-shaped flask equipped with a stir bar and
a septum was charged with 30 mg (52 .mu.mol) of the nickel
dibromide complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane
and 1 g of MAO treated silica (purchased from Witco TA
02794/HL/04). The solid mixture was cooled to 0.degree. C. in an
ice bath and 20 mL of toluene was added. The reaction was rapidly
stirred at 0.degree. C. for 1 hour. After 1 hour the solid was
allowed to settle and the solvent was removed via filter cannula.
The resulting purple solid was washed with toluene using a filter
cannula and was dried under dynamic vacuum giving 900 mg of
supported catalyst material.
Example 95
Synthesis of the supported nickel complex of
2,3-bis(2,6-diisopropylphenyl- imino)-[1,4]dithiane
[0291] A flame dried pear-shaped flask equipped with a stir bar and
a septum was charged with 34 mg (50 .mu.mol) of the nickel
dibromide complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane and 1 g of MAO
treated silica (purchased from Witco TA 02794/HL/04). The solid
mixture was cooled to 0.degree. C. in an ice bath and 20 mL of
CH.sub.2Cl.sub.2 was added. The reaction was rapidly stirred at
0.degree. C. for 1 hour. After 1 hour the solvent was removed in
vacuo. The resulting red brown solid was washed with
CH.sub.2Cl.sub.2 using a filter cannula and dried under dynamic
vacuum giving 780 mg of supported catalyst.
Example 96
Synthesis of the supported nickel complex of
2,3-bis(2,6-dimethylphenylimi- no)-[1,4]dithiane
[0292] A flame dried pear-shaped flask equipped with a stir bar and
a septum was charged with 15 mg (26 .mu.mol) of the nickel
dibromide complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane
and 1 g of MAO treated silica (purchased from Witco TA
02794/HL/04). The solid mixture was cooled to 0.degree. C. in an
ice bath and 20 mL of CH.sub.2Cl.sub.2 was added. The reaction was
rapidly stirred at 0.degree. C. for 1 hour. After 1 hour the
solvent was removed in vacuo resulting in 940 mg of a purple
solid.
Example 97
Polymerization of ethylene using the supported nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane Prepared in example
92
[0293] A flame dried pear-shaped flask equipped with a stir bar and
a septum was charged with 100 mg of the nickel /MAO treated silica
supported catalyst system prepared in example 92. The flask was
placed under an ethylene atmosphere and 50 mL of toluene was added
giving a red/brown suspension. The polymerization was left to stir
for 1 hour at 23.degree. C. After 60 minutes at 23.degree. C., the
reaction was quenched by the addition of acetone, 6M HCl and
methanol. The swollen polyethylene was isolated by filtration and
dried for several hours in a vacuum oven at 100.degree. C.
resulting in 1.6 g of a white rubbery solid (11,000 TO/h based on
100% active catalyst). DSC: (2nd heat) melt with an endothermic
maximum at 118.degree. C. .sup.1H NMR: 30 branches/1000 carbon
atoms. GPC: Mn=208,000; Mw/Mn=2.45.
Example 98
Polymerization of ethylene using the supported nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared in example
92
[0294] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under dynamic vacuum to ensure the reactor was dry.
The reactor was then purged with argon. The 600 mL Parr.RTM.
autoclave was charged in the glove box with 200 mg of the supported
catalyst prepared in example 92. Upon removing the autoclave from
the box, 150 mL of toluene was added and the reactor was heated to
60.degree. C. The reactor was rapidly pressurized to 90 psig
ethylene. After 60 minutes at 60.degree. C., the reaction was
quenched by the addition of acetone, 6M HCl and methanol. The
swollen polyethylene was isolated by filtration and dried for
several hours in a vacuum oven at 100.degree. C. resulting in 22.5
g of a white rubbery solid (80,000 TO/h). .sup.1H NMR: 31
branches/1000 carbon atoms. GPC: Mn=128,000; Mw/Mn=2.58.
Example 99
Polymerization of ethylene using the supported nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared in example
92
[0295] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under dynamic vacuum to ensure the reactor was dry.
The reactor was then purged with argon. The 600 mL Parr.RTM.
autoclave was charged in the glove box with 100 mg of the supported
catalyst prepared in example 92. Upon removing the autoclave from
the box, 150 mL of toluene was added and the reactor was heated to
100.degree. C. The reactor was rapidly pressurized to 90 psig
ethylene and the temperature ramped up to 140.degree. C. After 60
minutes at 140.degree. C., the reaction was quenched by the
addition of acetone, 6M HCl and methanol. The swollen polyethylene
was isolated by filtration and dried for several hours in a vacuum
oven at 100.degree. C. GPC: Mn=56,000; Mw/Mn=7.19.
Example 100
Polymerization of ethylene using the supported nickel complex of
2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane prepared in
example 95
[0296] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under dynamic vacuum to ensure the reactor was dry.
The reactor was then purged with argon. The 600 mL Parr.RTM.
autoclave was charged in the glove box with 100 mg of the supported
catalyst prepared in example 95. Upon removing the autoclave from
the box, 150 mL of toluene was added and the reactor was heated to
50.degree. C. The reactor was rapidly pressurized to 90 psig
ethylene. After 30 minutes at 50.degree. C., the reaction was
quenched by the addition of acetone, 6M HCl and methanol. The
swollen polyethylene was isolated by filtration and dried for
several hours in a vacuum oven at 100.degree. C. resulting in 1.25
g of a white rubbery solid (18,000 TO/h). .sup.1H NMR: 62
branches/1000 carbon atoms. GPC: Mn=336,000; Mw/Mn=2.22.
Example 101
Polymerization of ethylene using the supported nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared in example
93
[0297] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under dynamic vacuum to ensure the reactor was dry.
The reactor was then purged with argon. The 600 mL Parr.RTM.
autoclave was charged in the glove box with 100 mg of the supported
catalyst prepared in example 93. Upon removing the autoclave from
the box, 150 mL of toluene was added and the reactor was heated to
50.degree. C. The reactor was rapidly pressurized to 90 psig
ethylene. After 60 minutes at 50.degree. C., the reaction was
quenched by the addition of acetone, 6M HCl and methanol. The
swollen polyethylene was isolated by filtration and dried for
several hours in a vacuum oven at 100.degree. C. resulting in 2.13
g of a white rubbery solid (30,000 TO/h). DSC: 2.sup.nd heat showed
an endothermic maximum at 120.degree. C. .sup.1H NMR: 17
branches/1000 carbon atoms. GPC: Mn=119,000; Mw/Mn=2.93.
Example 102
Polymerization of ethylene using the supported nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared in example
94
[0298] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under dynamic vacuum to ensure the reactor was dry.
The reactor was then purged with argon. The 600 mL Parr.RTM.
autoclave was charged in the glove box with 100 mg of the supported
catalyst prepared in example 94. Upon removing the autoclave from
the box, 150 mL of toluene was added and the reactor was heated to
50.degree. C. The reactor was rapidly pressurized to 90 psig
ethylene. After 60 minutes at 50.degree. C., the reaction was
quenched by the addition of acetone, 6M HCl and methanol. The
swollen polyethylene was isolated by filtration and dried for
several hours in a vacuum oven at 100.degree. C. resulting in 5.97
g of a white rubbery solid (41,000 TO/h). DSC: 2.sup.nd heat showed
an endothermic maximum at 120.degree. C. GPC: Mn=138,000;
Mw/Mn=2.95. .sup.1H NMR: 17 branches/1000 carbon atoms.
Example 103
Polymerization of ethylene using the supported nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared according
to the procedure described in example 92
[0299] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under dynamic vacuum to ensure the reactor was dry.
The reactor was then purged with argon. The 600 mL Parr.RTM.
autoclave was charged in the glove box with 100 mg of supported
catalyst. Upon removing the autoclave from the box, 150 mL of
toluene was added and the reactor was heated to 65.degree. C. The
reactor was rapidly pressurized to 100 psig ethylene. After 60
minutes at 65.degree. C., the reaction was quenched by the addition
of acetone, 6M HCl and methanol. The swollen polyethylene was
isolated by filtration and dried for several hours in a vacuum oven
at 100.degree. C. resulting in 9.0 g of a white rubbery solid
(62,000 TO/h). DSC: 2.sup.nd heat showed an endothermic maximum at
116.degree. C. GPC: Mn=83,500; Mw/Mn=4.71. .sup.1H NMR: 35
branches/1000 carbon atoms.
Example 104
Polymerization of ethylene using the supported nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared in example
96
[0300] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under dynamic vacuum to ensure the reactor was dry.
The reactor was then purged with argon. The 600 mL Parr.RTM.
autoclave was charged in the glove box with 100 mg of the supported
catalyst prepared in example 96. Upon removing the autoclave from
the box, 150 mL of toluene was added and the reactor was heated to
50.degree. C. The reactor was rapidly pressurized to 100 psig
ethylene. After 60 minutes at 50.degree. C., the reaction was
quenched by the addition of acetone, 6M HCl and methanol. The
swollen polyethylene was isolated by filtration and dried for
several hours in a vacuum oven at 100.degree. C. resulting in 6.5 g
of a white rubbery solid (88,000 TO/h). DSC: 2.sup.nd heat showed a
broad melt transition with an endothermic maximum at 119.degree. C.
GPC: Mn=182,600; Mw/Mn=3.01. .sup.1H NMR: 19 branches/1000 carbon
atoms.
Example 105
Polymerization of ethylene using the supported nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared in example
96
[0301] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under dynamic vacuum to ensure the reactor was dry.
The reactor was then purged with argon. The 600 mL Parr.RTM.
autoclave was charged in the glove box with 100 mg of the supported
catalyst prepared in example 96. Upon removing the autoclave from
the box, 150 mL of toluene was added and the reactor was heated to
50.degree. C. The reactor was rapidly pressurized to 100 psig
ethylene. After 60 minutes at 50.degree. C., the reaction was
quenched by the addition of acetone, 6M HCl and methanol. The
swollen polyethylene was isolated by filtration and dried for
several hours in a vacuum oven at 100C resulting in 5.4 g of a
white rubbery solid (74,000 TO/h). DSC: 2.sup.nd heat showed abroad
melt transition with an endothermic maximum at 120.degree. C. GPC:
Mn=186,500; Mw/Mn=2,66. .sup.1H NMR: 18 branches/1000 carbon
atoms.
Example 106
Polymerization of ethylene using the supported nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared in example
96
[0302] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under dynamic vacuum to ensure the reactor was dry.
The reactor was then purged with argon. The 600 mL Parr.RTM.
autoclave was charged in the glove box with 100 mg of the supported
catalyst prepared in example 96. Upon removing the autoclave from
the box, 150 mL of toluene was added and the reactor was heated to
30.degree. C. The reactor was rapidly pressurized to 100 psig
ethylene. After 60 minutes at 30.degree. C., the reaction was
quenched by the addition of acetone, 6M HCl and methanol. The
swollen polyethylene was isolated by filtration and dried for
several hours in a vacuum oven at 100.degree. C. resulting in 11.5
g of a white rubbery solid (160,000 TO/h). DSC: 2.sup.nd heat
showed an endothermic maximum at 127.degree. C. GPC: Mn=279,000;
Mw/Mn=2.73. .sup.1H NMR: 7 branches/1000 carbon atoms.
Example 107
Synthesis of the supported nickel complex of
2,3-bis(phenylimino)-[1,4]dit- hiane
[0303] A 500 mL flame-dried pear-shaped flask equipped with a
magnetic stir bar and capped by a septum was charged with 27 mg (52
mol) of the nickel dibromide complex of
2,3-bis(phenylimino)-[1,4]dithiane and 1.0 g of MAO treated silica
(Witco TA 02794/HL/04). The solid mixture was cooled to 0.degree.
C. in an ice bath and 25 mL of dry, deoxygenated CH.sub.2Cl.sub.2
was added. The reaction was stirred at 0.degree. C. for 50 min,
then the volatiles were removed by evaporation under reduced
pressure (0.2 torr) at 0.degree. C. for 40 min to afford the
supported catalyst as a light green-grey powder which was stored
under nitrogen at -25.degree. C.
Example 108
Synthesis of the supported nickel complex of
2,3-bis(2-tert-butylphenylimi- no)-[1,4]dithiane
[0304] A 500 mL flame-dried pear-shaped flask equipped with a
magnetic stir bar and capped by a septum was charged with 34 mg (56
mol) of the nickel dibromide complex of
2,3-bis(2-tert-butylphenylimino)-[1,4]dithian- e and 1.0 g of MAO
treated silica (Witco TA 02794/HL/04). The solid mixture was cooled
to 0.degree. C. in an ice bath and 25 mL of dry, deoxygenated
CH.sub.2Cl.sub.2 was added. The reaction was stirred at 0.degree.
C. for 50 min, then the volatiles were removed by evaporation under
reduced pressure (0.2 torr) at 0.degree. C. for 40 min to afford
the supported catalyst as a light brown powder which was stored
under nitrogen at -25.degree. C.
Example 109
Synthesis of the supported nickel complex of
2,3-bis(2,6-dimethylphenylimi- no)-1,4]dioxane
[0305] A 500 mL flame-dried pear-shaped flask equipped with a
magnetic stir bar and capped by a septum was charged with 30 mg (55
mol) of the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane and 1.01 g of MAO
treated silica (Witco TA 02794/HL/04). The solid mixture was cooled
to 0.degree. C. in an ice bath and 25 mL of dry, deoxygenated
CH.sub.2Cl.sub.2 was added. The reaction was stirred at 0.degree.
C. for 65 min, then the volatiles were removed by evaporation under
reduced pressure (0.2 torr; 20 min at 0.degree. C., 75 min at
25.degree. C.) to afford the supported catalyst as a brown powder
which was stored under nitrogen at -25.degree. C.
Example 110
Polymerization of ethylene using the supported nickel complex of
2,3-bis(phenylimino)-[1,4]dithiane
[0306] A 500 mL flame-dried pear-shaped flask equipped with a
magnetic stir bar and capped by a septum was charged with 100 mg of
the supported nickel complex of 2,3-bis(phenylimino)-[1,4]dithiane
prepared in Example 107. The flask was evacuated and refilled with
ethylene, then treated with 50 mL of dry, deoxygenated toluene and
stirred under 1 atm ethylene at 23.degree. C. for 14 h. The
reaction was quenched by the addition of methanol, acetone and 6 N
HCl. The polymer which separated was isolated by filtration and
dried in vacuo to afford 0.177 g of white, powdery polyethylene.
DSC: (2nd heat) melt endothermic maxima at ca. 100, 106 and
127.degree. C. GPC: M.sub.n=1,100 g/mol; M.sub.w/M.sub.n=15.5.
Example 111
Polymerization of ethylene using the supported nickel complex of
2,3-bis(2-tert-butylphenylimino)-[1,4]dithiane
[0307] A 500 mL flame-dried pear-shaped flask equipped with a
magnetic stir bar and capped by a septum was charged with 100 mg of
the supported nickel complex of
2,3-bis(2-tert-butylphenylimino)-[1,4]dithiane prepared in Example
108. The flask was evacuated and refilled with ethylene, then
treated with 50 mL of dry, deoxygenated toluene and stirred under 1
atm ethylene at 23.degree. C. for 125 min. The reaction was
quenched by the addition of methanol, acetone and 6 N HCl. The
polymer which separated was isolated by filtration and dried in
vacuo to afford 0.529 g of white, powdery polyethylene. DSC: (2nd
heat) melt endothermic maxima at 96 and 110.degree. C. .sup.1H NMR
(o-dichlorobenzene): 36 branches/1000 carbon atoms. GPC:
M.sub.n=120,000; M.sub.w/M.sub.n=2.46.
Example 112
Polymerization of ethylene using the supported nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane
[0308] A 500 mL flame-dried pear-shaped flask equipped with a
magnetic stir bar and capped by a septum was charged with 106 mg of
the supported nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane prepared in Example
109. The flask was evacuated and refilled with ethylene, then
treated with 50 mL of dry, deoxygenated toluene and stirred under 1
atm ethylene at 23.degree. C. for 255 min. The reaction was
quenched by the addition of methanol, acetone and 6 N HCl. The
polymer which separated was isolated by filtration and dried in
vacuo to afford 3.2 g of white, powdery polyethylene. .sup.1H NMR
(o-dichlorobenzene): 20 branches/1000 carbon atoms. DSC: (2nd heat)
melt endothermic maximum at 118.degree. C. GPC: M.sub.n=150,000;
M.sub.w/M.sub.n=3.10.
Example 113
Copolymerization of ethylene and ethyl undecenoate using the
supported nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared as
described in example 92
[0309] A flame dried pear-shaped flask equipped with a stir bar and
a septum was charged with 100 mg of the nickel /MAO treated silica
supported catalyst system. The flask was placed under an ethylene
atmosphere, and 45 mL of toluene and 2.5 mL of ethyl undecenoate
was added, giving a purple suspension. The polymerization was left
to stir for 5 hours at 0.degree. C. After 5 hours at 0.degree. C.,
the reaction was quenched by the addition of acetone, 6M HCl and
methanol. The white copolymer was isolated by filtration, washed
with copious amounts of acetone and dried for several hours in a
vacuum oven at 100.degree. C. resulting in 1.3 g of a white powdery
solid (1800 TO/h based on 100% active catalyst). .sup.1H NMR
indicates 1 wt % of ethyl undecenoate incorporated into the
copolymer.
Example 114
Copolymerization of ethylene and ethyl undecenoate using the
supported nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared as
described in example 92
[0310] A flame dried pear-shaped flask equipped with a stir bar and
a septum was charged with 100 mg of the nickel/MAO treated silica
supported catalyst system. The flask was placed under an ethylene
atmosphere, 45 mL of toluene and 2.5 mL of ethyl undecenoate was
added giving a purple suspension. The polymerization was left to
stir for 3.5 hours at 23.degree. C. After 3.5 hours at 23.degree.
C., the reaction was quenched by the addition of acetone, 6M HCl
and methanol. The white copolymer was isolated by filtration,
washed with copious amounts of acetone and dried for several hours
in a vacuum oven at 100.degree. C. resulting in 1.4 g of a white
powdery solid (2700 TO/h based on 100% active catalyst). .sup.1H
NMR indicates 1 wt % ethyl undecenoate incorporated into the
copolymer.
[0311] Obviously, numerous modifications and variations of the
present invention are possible in light of the above teachings. It
is therefore to be understood that within the scope of the appended
Claims, the invention may be practiced otherwise than as
specifically described herein.
Example 115
Synthesis of the supported nickel complex of
2,3-bis(2,6-dimethylphenylimi- no)-[1,4]-dithiane
[0312] A flame dried pear-shaped flask equipped with a stir bar and
a septum was charged with 9 mg (16 .mu.mol) of the nickel dibromide
complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane and 3 g
of MAO treated silica (purchased from Witco TA 02794/HL/04). The
solid mixture was cooled to 0.degree. C. in an ice bath and 25 ml
of toluene was added. The reaction was rapidly stirred at 0.degree.
C. for 1 hour. After 1 hour, the solvent was removed in vacuo
giving 2.8 g of supported catalyst material.
Example 116
Synthesis of the supported nickel complex of
2,3-bis(2,6-dimethylphenylimi- no)-[1,4]-dithiane
[0313] A flame dried pear-shaped flask equipped with a stir bar and
a septum was charged with 6 mg (10 .mu.mol) of the nickel dibromide
complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane and 1 g
of MAO treated silica (purchased from Witco TA 02794/HL/04). The
solid mixture was cooled to 0.degree. C. in an ice bath and 20 ml
of CH.sub.2Cl.sub.2 was added. The reaction was rapidly stirred at
0.degree. C. for 1 hour. After 1 hour, the solvent was removed in
vacuo giving a brown supported catalyst material. The supported
catalysts was then suspended in 20 ml of hexane followed by
addition of 2 ml (4 mmol) of trimethylaluminum (TMA). The mixture
was stirred at 0.degree. C. for one hour. The solvent was removed
in vacuo along with excess TMA leaving the supported catalyst
system.
Example 117
Synthesis of the supported nickel complex of
2,3-bis(2,6-dimethylphenylimi- no)-[1,4-dithiane
[0314] A flame dried pear-shaped flask equipped with a stir bar and
a septum was charged with 15 mg (26 .mu.mol) of the nickel
dibromide complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane
and 1 g of silica (Grace Davison XPO-2402). The solid mixture was
cooled to 0.degree. C. in an ice bath and 20 ml of toluene and 7 ml
of a MAO solution in toluene was added. The reaction was rapidly
stirred at 0.degree. C. for 1 hour. After 1 hour, the solvent was
removed in vacuo giving 1.3 g of supported catalyst.
Example 118
Synthesis of the supported nickel complex of
2,3-bis(2,6-dimethylphenylimi- no)-[1,4]-dithiane
[0315] A flame dried pear-shaped flask equipped with a stir bar and
a septum was charged with 18 mg (31 .mu.mol) of the nickel
dibromide complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane
and 3 g of MAO treated silica (purchased from Witco TA
02794/HL/04). The solid mixture was cooled to 0.degree. C. in an
ice bath and 25 ml of CH.sub.2Cl.sub.2was added. The reaction was
rapidly stirred at 0.degree. C. for 1 hour. After 1 hour, the
solvent was removed in vacuo giving a brown supported catalyst
material. The supported catalysts was then suspended in 20 ml of
hexane followed by addition of 0.5 ml of MAO. The mixture was
stirred at 0.degree. C. for one hour. The solvent was removed in
vacuo leaving 2.9 g of the supported catalyst.
Example 119
Synthesis of the supported nickel complex of
2,3-bis(2,6-dimethylphenylimi- no)-[1,4]-dithiane
[0316] A flame dried pear-shaped flask equipped with a stir bar and
a septum was charged with 6 mg (10 .mu.mol) of the nickel dibromide
complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane and 1 g
of silica (Grace Davison XPO-2402). The solid mixture was cooled to
0.degree. C. in an ice bath and 20 ml of hexane and 2 ml of a TMA
solution in toluene was added. The reaction was rapidly stirred at
0.degree. C. for 1 hour. After 1 hour, the solvent was removed in
vacuo giving 0.94 g of supported catalyst.
[0317] Gas Phase Polymerization 23
[0318] Catalysts Preparation
[0319] A--XXVII/MAO on Silica (Witco)/0.3 mg of XXVII per gram
silica.
[0320] See example 115 as a representative example.
[0321] B--XXVII/MAO on Silica (Witco)/3 mg of XXVII per gram
silica. See example 92 as a representative example.
[0322] C--XXVII/MAO on Silica (Witco)/0.3 mg of XXVII per gram
silica/extra MAO added. See example 118 as a representative
example.
[0323] D--XXVII/Silica (Grace Davison XPO-2402)/MAO solution/1.5 mg
of XXVII per gram silica. See example 117 as a representative
example.
[0324] E--XXVII/MAO on Silica (Witco)/0.6 mg of XXVII per gram
silica/extra MAO added. See example 118 as a representative
example.
[0325] F--XXVII/MAO on Silica (Witco)/0.6 mg of XXVII per gram
silica/extra TMA added. See example 116 as a representative
example.
[0326] G--XXVII/Silica (Grace Davison XPO-2402)/TMA solution/0.6 mg
of XXVII per gram silica. See example 117 as a representative
example.
[0327] H--XXVII/MAO on Silica (Witco)/0.6 mg of XXVII per gram
silica.
[0328] See example 115 as a representative example.
[0329] Gas Phase Polymerization Procedure
[0330] The basic procedure involves loading a 600 ml Parr.RTM.
stirred autoclave with 300 g of NaCl (dried in a vacuum oven at
100.degree. C. for 24 hours) and a known amount of supported XXVII
catalyst. The ethylene homopolymerization reactions summarized
below were run between 50.degree. C. and 80.degree. C. and 100 and
1000 psig ethylene. The resulting polyethylene was isolated by
dissolving the NaCl in a blender and collecting the remaining
polymer by filtration. The polyethylene was washed with 6M HCl,
water and actetone. The polymer was then dried in a vacuum oven at
100.degree. C.
[0331] A--80.degree. C./800 psig ethylene/20 min reaction time/200
mg of supported catalyst.
[0332] B--65.degree. C./400 psig ethylene/60 min reaction time/200
mg of supported catalyst.
[0333] C--65.degree. C./200 psig ethylene/60 min reaction time/200
mg of supported catalyst.
[0334] D--65.degree. C./100 psig ethylene/60 min reaction time/200
mg of supported catalyst.
[0335] E--80.degree. C./100 psig ethylene/60 min reaction time/200
mg of supported catalyst.
[0336] F--80.degree. C./200 psig ethylene/60 min reaction time/200
mg of supported catalyst.
[0337] G--80.degree. C./400 psig ethylene/60 min reaction time/200
mg of supported catalyst.
[0338] H--80.degree. C./400 psig ethylene/60 min reaction time/100
mg of supported catalyst.
[0339] I--80.degree. C./100 psig ethylene/60 min reaction time/50
mg of supported catalyst.
[0340] J--80.degree. C./100 psig ethylene/60 min reaction time/100
mg of supported catalyst.
[0341] K--100.degree. C./100 psig ethylene/60 min reaction time/100
mg of supported catalyst.
[0342] L--80.degree. C./200 psig ethylene/60 min reaction time/100
mg of supported catalyst.
[0343] M--100.degree. C./200 psig ethylene/60 min reaction time/100
mg of supported catalyst.
[0344] N--100.degree. C./400 psig ethylene/60 min reaction time/100
mg of supported catalyst.
[0345] O--80.degree. C./200 psig ethylene/15 min reaction time/100
mg of supported catalyst.
[0346] P--80.degree. C./200 psig ethylene/30 min reaction time/100
mg of supported catalyst.
1 Gas Phase Polymerization Ex- Pro- Mass Branches/ am- ce- Polymer
Total 1000C T.sub.m ple Catalyst dure (g) TO M.sub.n PDI
(.sup.1HNMR) (.degree. C.) 120 A A 11.5 395K 164K 3.21 8 128 121 A
B 8.5 293K 174K 3.59 9 124 122 A C 6.5 224K 124K 4.14 14 120 123 A
D 4.7 160K 126K 4.01 21 117 124 A E 3.5 121K 91K 3.67 28 119 125 A
F 4.3 110K 94K 3.33 27 118 126 A G 9.8 336K 121K 3.51 13 121 127 H
B 13.5 231K 133K 3.22 10 122 128 H G 12 206K 117K 3.39 13 121 129 H
E 9.4 161K 106K 3.57 26 115 130 H H 7.8 267K 195K 3.16 9 123 131 B
E 14 48K 60K 4.42 48 114 132 B I 3 41K 94K 3.2 36 114 133 B J 6.8
47K 88K 3.49 36 119 134 C J 9 61K 89K 3.94 34 119 135 B K 4.4 30K
48K 4.14 53 113 136 C K 5.6 38K 63K 3.63 45 116 137 B L 8 55K 93K
3.57 28 118 138 C L 12 82K 91K 3.79 30 119 139 B M 7 48K 57K 4.61
43 115 140 C M 7 48K 79K 3.77 48 116 141 B H 13.8 94K 106K 3.84 24
120 142 B H 12.7 87K 99K 3.63 26 120 143 D J 4 54K 69K 5.53 35 112
144 D K 3 41K 45K 4.11 56 112 145 D L 5 68K 117K 3.48 28 115 146 D
M 3.6 50K 70K 3.74 37 115 147 D H 5 68K 107K 3.24 18 118 148 D N
5.9 80K 76K 4.2 25 116 149 E J 3.8 129K 65K 4.86 36 113 150 E K 1.5
51K 43K 4.4 47 114 151 E L 4 137K 74K 4.6 28 119 152 F H 4.7 161K
106K 3.77 14 120 153 G H 0.35 12K 81K 4.32 23 119 154 G H 0.25 9K
57K 5.64 27 118 155 F H 3.8 130K 94K 3.46 18 120 156 A O 1.8 123K
71K 4.70 29 117 157 A P 2.1 145K 80K 4.09 33 117 158 A L 2.3 157K
78K 4.72 30 117 159 B O 4.9 34K 58K 4.50 38 117
[0347] The polymer made in the gas phase in example 131 (10.57
grams) was fractionated using supercritical propane by isothermal
increasing pressure profiling and critical, isobaric, temperature
rising elution fractionation to give the following data. (See, B.
Folie, et al., "Fractionation of Poly(ethylene-co-vinyl acetate) in
Supercritical Propylene: Towards a Molcular Understanding of a
Complex Macromolecule", J. Appl. Polym. Sci., 64, 2015-2030,1997,
and publicly available literature from Phasex Corporation, 360
Merrimack St., Lawrence, Mass. 01843, and at www.Phasex.com):
2 Temperature Weight of Collected Fraction Branching T.sub.m
Fraction (.degree. C.) (g) M.sub.n PDI (.sup.1H NMR) (.degree. C.)
1 40 1.43 29,500 2.76 72.2 50 2 40-60 0.43 28,600 3.02 62.3 55 3
60-65 0.74 49,400 2.37 57.5 79 4 65-75 0.52 83,100 2.14 45.9 92 5
75-85 0.80 80,900 2.22 36.5 99 6 85-95 0.50 77,400 2.40 34.3 102 7
95-100 0.61 93,200 2.26 26.3 108 8 100-110 0.47 116,000 2.15 19.3
117 9 110-140 0.41 125,000 2.23 16.7 122 10 140-150 0.15 184,000
2.96 14.3 124 residue -- 3.85 -- -- <5 -- Bulk -- -- 59,900 4.42
48 114 Sample
[0348] The polymer made in the gas phase in example 138 (12 grams)
was fractionated using supercritical propane by isothermal
increasing pressure profiling and critical, isobaric, temperature
rising elution fractionation to give the following data. (See, B.
Folie, et al., "Fractionation of Poly(ethylene-co-vinyl acetate) in
Supercritical Propylene: Towards a Molecular Understanding of a
Complex Macromolecule", J. Appl. Polym. Sci., 64, 2015-2030, 1997,
and publicly available literature from Phasex Corporation, 360
Merrimack St., Lawrence, Mass. 01843, and at www.Phasex.com):
3 Temperature Weight of Collected Fraction Branching T.sub.m
Fraction (.degree. C.) (g) M.sub.n PDI (.sup.1H NMR) (.degree. C.)
1 40 0.38 20,500 3.12 71 64 2 40-65 0.60 30,200 3.10 57 70 3 65-75
0.73 43,600 2.73 47 87 4 75-85 0.82 49,900 3.16 35 98 5 85-90 0.54
63,200 2.58 30 106 6 90-95 0.62 81,200 2.42 25 109 7 95-100 0.60
79,700 2.51 22 114 8 100-105 0.89 77,900 3.04 18 118 9 105-110 0.81
117,600 2.30 16 121 10 110-115 0.65 115,000 2.59 13 124 11 115-120
0.39 116,500 2.61 11 126 12 120-125 0.16 139,500 2.43 11 125 13
125-150 0.25 151,300 2.43 -- 123 residue -- 2.2 141,000 5.29 -- --
Bulk -- 12 90,700 3.79 30 119 Sample
Solution Phase Polymerization
[0349] 24
[0350] Solution Phase Polymerization Procedure
[0351] A 600 mL Parr.RTM. autoclave was first heated to about
100.degree. C. under high vacuum to ensure the reactor was dry. The
reactor was cooled and purged with argon. Under an argon
atmosphere, the autoclave was charged with 150 mL of toluene and a
stock solution (CH.sub.2Cl.sub.2) of the nickel dibromide complex
of 2,3-bis(2,6-dimethyl-phenylimino)[1,4]-dithiane. The autoclave
was heated to the desired temperature and a cocatalyst was added.
The reactor was rapidly pressurized to the desired pressure. After
the desired reaction time, the polymerization was quenched by the
addition of acetone, and methanol. The swollen polyethylene which
separated was isolated by filtration and dried for several hours in
a vacuum oven at 80.degree. C. As used herein, Et.sub.2AlCl refers
to diethyl aluminum chloride.
[0352] A--cocatalyst=Et.sub.2AlCl; mol cat.=8.7.times.10.sup.-7;
solvent=mineral spirits; temperature=80.degree. C.; ethylene
pressure=600 psig; reaction time=20min.
[0353] B--cocatalyst=Et.sub.2AlCl; mol cat.=8.7.times.10.sup.-7;
solvent=mineral spirits; temperature=65.degree. C.; ethylene
pressure=600 psig; reaction time=20 min.
[0354] C--cocatalyst=Et.sub.2AlCl; mol cat.=8.7.times.10.sup.-7;
solvent=mineral spirits; temperature=65.degree. C.; ethylene
pressure=800 psig; reaction time=20 min.
[0355] D--cocatalyst=Et.sub.2AlCl; mol cat.=17.5.times.10.sup.-7;
solvent=toluene; temperature=80.degree. C.; ethylene pressure=600
psig; reaction time=20 min.
[0356] E--cocatalyst=Et.sub.2AlCl; mol cat.=17.5.times.10.sup.-7;
solvent=toluene; temperature=75.degree. C.; ethylene pressure=600
psig; reaction time=20 min.
[0357] F--cocatalyst=Et.sub.2AlCl; mol cat.=17.5.times.10.sup.-7;
solvent=toluene; temperature=75.degree. C.; ethylene pressure=800
psig; reaction time=20 min.
[0358] G--cocatalyst=Et.sub.2AlCl; mol cat.=17.5.times.10.sup.-7;
solvent=toluene; temperature=80.degree. C.; ethylene pressure=400
psig; reaction time=20 min.
[0359] H--cocatalyst=Et.sub.2AlCl; mol cat.=17.5.times.10.sup.-7;
solvent=toluene; temperature=65.degree. C.; ethylene pressure=400
psig; reaction time=20 min.
[0360] I--cocatalyst=Et.sub.2AlCl; mol cat.=17.5.times.10.sup.-7;
solvent=toluene; temperature=100.degree. C.; ethylene pressure=800
psig; reaction time=20 min.
4 Solution Phase Polymerization Ex- Pro- Mass Branches/ am- ce-
Polymer Total 1000C T.sub.m ple Catalyst dure (g) TO M.sub.n PDI
(.sup.1HNMR) (.degree. C.) 160 XXVII A 6 247K 83K 2.42 33 94 161
XXVII B 9 370K 135K 2.61 26 113 162 XXVII C 6 245K 144K 2.30 24 113
163 XXVII D 5.7 116K 66K 1.85 47 80 164 XXVII E 6.3 129K 58K 2.18
44 75 165 XXVII F 7.8 159K 63K 2.43 37 95 166 XXVII G 3.8 78K 52K
1.85 -- 55 167 XXVII H 5.5 112K 78K 1.93 45 78 168 XXVII I 1.5 31K
32K 1.85 63 55
Example 169
Preparation of MAO supported on silica (Grace Davison XPO-2402),
MAO/2402
[0361] A 500-mL pear-shaped flask, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with silica (Grace Davison XPO-2402; 3.08 g)
under a nitrogen inert atmosphere. The flask was equipped with a
magnetic stirring bar and a septum cap. Upon stirring, anhydrous
toluene (80 mL) was then added, followed by 19.0 mL of a 10 wt % of
MAO in toluene. The suspension was heated to 80.degree. C. for 4
hours, cooled to room temperature and then transferred via canula
onto a filter funnel. The solid was washed with toluene (3.times.50
mL) and dried in vacuo to give 3.64 g solid. BET surface area:
300.9 m.sup.2 g.sup.-1. Pore volume: 1.19 cm.sup.3 g.sup.-1.
Average Pore Diameter: 7.3 .ANG.. Obsd wt % Al: 6.8.
Example 170
Preparation of diethylaluminum chloride (DEAC) supported on silica
(Grace Davison XPO-2402), DEAC/2402
[0362] A 500-mL pear-shaped flask, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with silica (Grace Davison XPO-2402; 3.87 g)
under a nitrogen inert atmosphere. The flask was equipped with a
magnetic stirring bar and a septum cap. Upon stirring, anhydrous
toluene (80 mL) was then added, followed by 20.0 mL of a 1.8 M of
DEAC in toluene. The suspension was heated to 80.degree. C. for 4
hours, cooled to room temperature and then transferred via canula
onto a filter funnel. The solid was washed with toluene (5.times.50
mL) and dried in vacuo to give 4.21 g solid. BET surface area: 280
m.sup.2 g.sup.-1. Pore volume: 1.0 cm.sup.3 g.sup.-1. Average Pore
Diameter: 132 .ANG.. Obsd wt % Al: 2.7.
Example 171
Preparation of triethylaluminum (TEAL) supported on silica (Grace
Davison XPO-2402), TEAL/2402
[0363] A 500-mL pear-shaped flask, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with silica (Grace Davison XPO-2402; 6.15 g)
under a nitrogen inert atmosphere. The flask was equipped with a
magnetic stirring bar and a septum cap. Upon stirring, anhydrous
toluene (50 mL) was then added, followed by 100 mL of a 1.9 mL of
TEAL in toluene. The suspension was heated to 80.degree. C. for 4
hours, cooled to room temperature and then transferred via canula
onto a filter funnel. The solid was washed with toluene (1.times.50
mL+4.times.25 mL) and dried in vacuo to give 6.34 g solid.
Example 172
Preparation of DEAC supported on silica (Grace Davison SyloPol
2212), DEAC/2212
[0364] A 500-mL pear-shaped flask, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with silica (Grace Davison Sylopol 2212; 3.08
g) under a nitrogen inert atmosphere. The flask was equipped with a
magnetic stirring bar and a septum cap. Upon stirring, anhydrous
toluene (80 mL) was then added, followed by 16 mL of a 10 wt %
solution of MAO in toluene. The suspension was heated to 80.degree.
C. for 4 hours, cooled to room temperature and then transferred via
canula onto a filter funnel. The solid was washed with toluene
(1.times.50 mL+6.times.25 mL+1.times.50 mL) and dried in vacuo to
give 3.35 g solid. Obsd wt % Al: 2,6.
Example 173
Preparation of MAO supported on silica (Grace Davison SyloPol
2212), MAO/2212
[0365] A 500-mL pear-shaped flask, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with silica (Grace Davison Sylopol 2212; 6.27
g) under a nitrogen inert atmosphere. The flask was equipped with a
magnetic stirring bar and a septum cap. Upon stirring, anhydrous
toluene (50 mL) was then added, followed by 54 mL of a 10 wt %
solution of MAO in toluene. The suspension was heated to 80.degree.
C. for 5 hours, cooled to room temperature and then transferred via
canula onto a filter funnel. The solid was washed with toluene
(1.times.50 mL+4.times.25 mL) and dried in vacuo to give 6.88 g
solid.
Example 174
Preparation of the nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4- 1-dithiane supported on
MAO/2402, XXVII/MAO/2402
[0366] A 50-mL pear-shaped flask, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with MAO/2402 (1.62 mg) and the nickel complex
of 2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane (46.7 mg; 81.2
.mu.mol) under a nitrogen inert atmosphere. The flask was equipped
with a magnetic stirring bar and a septum cap. The solid was cooled
to 0.degree. C. and dichloromethane (20 mL) was added under
vigorous stirring. The volatiles were removed in vacuum. The
residual solid was dried in vacuo to give 1.40 g.
Example 175
Preparation of the nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4- ]-dithiane supported on
DEAC/2402, XXVII/DEAC/2402
[0367] A 50-mL pear-shaped flask, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with DEAC/2402 (637 mg) and the nickel complex
of 2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane (18.0 mg; 31.3
.mu.mol) under a nitrogen inert atmosphere. The flask was equipped
with a magnetic stirring bar and a septum cap. The solid was cooled
to 0.degree. C. and dichloromethane (25 mL) was added under
vigorous stirring. After 1 hour, the mixture was filtered by
canula. The residual solid was then rinsed with 10 mL
dichloromethane and filtered by canula a second time. The solid was
dried in vacuo and stored at -30.degree. C. Yield: 213.4 mg.
Loading of Ni complex/g support: 43 .mu.mol (based on Ni analysis)
and 37 .mu.mol (based on S analysis). Ni complex:Al ratio: 22
(based on Ni analysis) and 26 (based on S analysis).
Example 176
Preparation of the nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4- ]-dithiane supported on
DEAC/2212, XXVII/DEAC/2212.
[0368] A 100-mL pear-shaped flask, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with DEAC/2212 (758 mg) and the nickel complex
of 2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane (22.1 mg; 38.4
.mu.mol) under a nitrogen inert atmosphere. The flask was equipped
with a magnetic stirring bar and a septum cap. The solid was cooled
to 0.degree. C. and dichloromethane (25 mL) was added under
vigorous stirring. After 1 hour, the mixture was filtered by
canula. The residual solid was then rinsed with 10 mL
dichloromethane and filtered by canula a second time. The solid was
dried in vacuo and stored at -30.degree. C. Yield: 718 mg. Loading
of Ni complex/g support: 49 .mu.mol (based on Ni analysis) and 34
.mu.mol (based on S analysis). Ni complex:Al ratio: 20 (based on Ni
analysis) and 28 (based on S analysis).
Example 177
Treatment of the nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]-- dithiane supported on
DEAC/2212 with trimethylaluminum (TMAL), TMAL/XXVII/DEAC/2212
[0369] A 200-mL pear-shaped flask, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with the nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]- -dithiane supported on
DEAC/2212, XXVII/DEAC/2212 (81.5 mg; 3.4 .mu.mol Ni) under a
nitrogen inert atmosphere. The flask was equipped with a magnetic
stirring bar and a septum cap. The solid was cooled to 0.degree. C.
and toluene (25 mL) was added under vigorous stirring. After 15
min, the volatile materials were removed in vacuo at 0.degree. C.
The resulting solid was further used to evaluate activity towards
ethylene polymerization.
Example 178
Treatment of the nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]-- dithiane supported on
DEAC/2212 with MAO, MAO/XXVII/DEAC/2212
[0370] A 50-mL pear-shaped flask, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with the nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]- -dithiane supported on
DEAC/2212, XXVII/DEAC/2212 (113.6 mg; 4.8 .mu.mol Ni) under a
nitrogen inert atmosphere. The flask was equipped with a magnetic
stirring bar and a septum cap. The solid was cooled to 0.degree. C.
and toluene (25 mL) was added under vigorous stirring. After 2 min,
the suspension was transferred via canula onto a filter funnel. The
resulting solid was dried in vacuo (89 mg) and used to evaluate
activity towards ethylene polymerization.
Example 179
Polymerization of ethylene using XXVII/MAO/2402
[0371] A 50-mL pear-shaped flask was charged with 152.5 mg
XXVIIIMAO/2402 (38 .mu.mol Ni/g; 5.8 .mu.mol) under a nitrogen
inert atmosphere. The inert atmosphere was replaced by 1 atm
ethylene and toluene (25 mL) was added. The suspension was stirred
for 2 hours at room temperature. The reaction was then quenched
with acetone and 6M HCl. The mixture was filtered. The resulting
solid was collected and dried in vacuo at 100.degree. C. to give
626.5 mg (where 152.5 mg of XXVII/MAO/2402 was used):
M.sub.n=95.5K, M.sub.w=467.7K, M.sub.w/M.sub.n=4.9; 27
branches/100.degree. C. (by 1H NMR); T.sub.m=118.degree. C.
Example 180
Polymerization of ethylene using XXVII/MAO/2402
[0372] A 1000-mL Parr.RTM. stirred reactor was charged with 169.3
mg (38 .mu.mol Ni/g; 6.4 .mu.mol Ni) under a nitrogen inert
atmosphere. Toluene (250 mL) was added and the reactor pressurized
with ethylene (800 psig). The mixture was stirred at 40.degree. C.
for 60 min. The vessel was vented and the catalyst quenched with
methanol and 6 M HCl The mixture was filtered and the collected
solid dried in vacuo at 100.degree. C. to give 18.60 g polymer.
Example 181
Polymerization of ethylene using XXVII/MAO/2402
[0373] A 200-mL pear-shaped flask was charged with 79.3 mg
XXVII/MAO/2402 (38 .mu.mol Ni/g; 3.0 .mu.mol) under a nitrogen
inert atmosphere. The inert atmosphere was replaced by 1 atm
ethylene and toluene (50 mL) was added, followed by 2.0 mL MAO (10
wt % in toluene). The suspension was stirred for 11 min at room
temperature and then quenched with methanol and 6M HCl. The mixture
was filtered. The resulting solid was collected and dried in vacuo
at 100.degree. C. to give 643 mg. M.sub.n=100.5K, M.sub.n=325.3K,
M.sub.w/M.sub.n=3.2; 41 branches/100.degree. C. (by .sup.1H NMR);
T.sub.m=83.degree. C. (by DSC).
Example 182
Polymerization of ethylene using XXVII/MAO/2402
[0374] A 600-mL Parr.RTM. stirred reactor was charged with 72.1 mg
XXVII/MAO/2402 (38 .mu.mol Ni/g; 2.7 .mu.mol Ni) under a nitrogen
inert atmosphere. The reactor was then charged with 150 mL
anhydrous toluene and heated to 50.degree. C. I then added 2.0 mL
of a 10 wt % solution of MAO in toluene. The vessel was pressurized
with 100 psig ethylene and further heated to 69.degree. C. The
slurry agitated for 45 min. The mixture was quenched at elevated
pressure by addition of methanol through an injection loop. The
vessel was depressurized and the mixture treated with 6M HCl. The
polymer was isolated by filtration and dried in vacuo at
100.degree. C. to give 4.21 g polymer. M.sub.n=55.7K,
M.sub.w=651.5K, M.sub.w/M.sub.n=11.7; 32 branches/1000.degree. C.
(by .sup.1H NMR); T.sub.m=113.degree. C. (by DSC).
Example 183
Polymerization of ethylene using XXVII/MAO/2402
[0375] A 200-mL pear-shaped flask was charged with 57.5 mg
XXVII/MAO/2402 (38 .mu.mol Ni/g; 2.2 .mu.mol) and 645 mg of
MAO-treated silica (purchased from Witco TA 02794/HL/04). The
nitrogen inert atmosphere was replaced by 1 atm ethylene, and 50 mL
anhydrous toluene was then added. The suspension was stirred for 1
hour at room temperature before being quenched with acetone and 6M
HCl. The mixture was filtered and the collected solid dried in
vacuo at 100.degree. C. to give 478 mg. M.sub.n=195.5K,
M.sub.w=840.5K, M.sub.w/M.sub.n=4.3; 16 branches/100.degree. C.;
T.sub.m=116.degree. C. (by DSC).
Example 184
Polymerization of ethylene using XXVII/MAO/2402
[0376] A 600-mL Parr.RTM. stirred reactor was charged with 65.0 mg
XXVII/MAO/2402 (38 .mu.mol Ni/g; 2.5 .mu.mol Ni), 170 mg solid MAO
and 214 g sodium chloride under a nitrogen inert atmosphere. The
reactor was heated to 60.degree. C., and subsequently pressurized
with 100 psig ethylene. The mixture was further heated to
65.degree. C. and stirred for an additional 45 min. The vessel was
vented and the solid mixed with water. The mixture was filtered and
the solid washed with water, 6M HCl and methanol. The collected
polymer was dried in vacuo at 100.degree. C. to give 2.38 g
polymer. M.sub.n=65.7K, M.sub.w=487.0K, M.sub.w/M.sub.n=7.4; 29
branches/100.degree. C. (by .sup.1H NMR); T.sub.m=118.degree. C.
(by DSC).
Example 185
Polymerization of ethylene using XXVII/DEAC/2402
[0377] A 200-mL pear-shaped flask was charged with 82 mg
XXVII/DEAC/2402 (40 .mu.mol Ni/g; 3.3 .mu.mol) under a nitrogen
inert atmosphere. Toluene (30 mL) was added. The inert atmosphere
was then replaced by 1 atm ethylene. The suspension was stirred for
2 hours at room temperature. The reaction was then quenched with
acetone and 6M HCl. The mixture was filtered. The resulting solid
was collected and dried in vacuo at 100.degree. C. to give 418 mg.
M.sub.n=114.0K, M.sub.n=264.7K, M.sub.w/M.sub.n=2,3; 65
branches/1000.degree. C. (by .sup.1H NMR); T.sub.m=110.degree. C.
(by DSC).
Example 186
Polymerization of ethylene using XXVII/DEAC/2402
[0378] A 600-mL Parr.RTM. stirred reactor was charged with 80.2 mg
(40 .mu.mol Ni/g; 3.2 .mu.mol Ni) under a nitrogen inert
atmosphere. Toluene (150 mL) was added and the reactor pressurized
with ethylene (800 psig). The mixture was stirred at 40.degree. C.
for 58 min. The vessel was vented and the catalyst quenched with
methanol and 6 M HCl The mixture was filtered and the collected
solid dried in vacuo at 100.degree. C. to give 0.56 g polymer.
M.sub.n=246.5K, M.sub.w=524.4K, M.sub.w/M.sub.n=2.1; 9
branches/1000.degree. C. (by .sup.1H NMR); T.sub.m=127.degree. C.
(by DSC).
Example 187
Polymerization of ethylene using XXVII/DEAC/2212
[0379] A 200-mL pear-shaped flask was charged with 89.1 mg
XXVII/DEAC/2212 (42 .mu.mol Ni/g; 3.7 .mu.mol) under a nitrogen
inert atmosphere. The inert atmosphere was replaced by 1 atm
ethylene and toluene (50 mL) was added, followed by 2.0 mL MAO (10
wt % in toluene). The suspension was stirred for 10 min at room
temperature. Temperature was controlled with a water bath. The
reaction was then quenched with acetone and 6M HCl. The mixture was
filtered. The resulting solid was collected and dried in vacuo at
100.degree. C. to give 1.80 g. M.sub.n=132.8K, M.sub.w=272.1K,
M.sub.w/M.sub.n=2.0; 52 branches/1000.degree. C. (by .sup.1H NMR);
T.sub.m=57.degree. C. (by DSC).
Example 188
Polymerization of ethylene using XXVII/DEAC/2212
[0380] A 200-mL pear-shaped flask was charged with 81.2 mg
XXVII/DEAC/2212 (42 .mu.mol Ni/g; 3.4 .mu.mol) under a nitrogen
inert atmosphere. The inert atmosphere was replaced by 1 atm
ethylene and toluene (50 mL) was added, followed by 2.0 mL DEAC
(1.8 M in toluene). The suspension was stirred for 6 min at room
temperature. Temperature was controlled with a water bath. The
reaction was then quenched with acetone and 6M HCl. The mixture was
filtered. The resulting solid was collected and dried in vacuo at
100.degree. C. to give 857 mg. M.sub.n=179.2K, M.sub.w=444.7K,
M.sub.w/M.sub.n=2.5; 32 branches/1000.degree. C. (by .sup.1H NMR);
T.sub.m=110.degree. C. (by DSC).
Example 189
Polymerization of ethylene using TMAL/XXVII/DEAC/2212
[0381] A suspension of TMAL/XXVII/DEAC/2212 (3.4 .mu.mol Ni) in
toluene (50 mL) was then prepared at 0.degree. C. The reaction
flask was evacuated and backfilled with 1 atm ethylene. The mixture
was stirred at room temperature for 2 hours and then quenched with
methanol and 6M HCl. The mixture was filtered. The resulting solid
was collected and dried in vacuo at 100.degree. C. to give 212 mg.
M.sub.n=215.9K, M.sub.w=910.6K, M.sub.w/M.sub.n=4.2; 15
branches/100.degree. C. (by .sup.1H NMR); T.sub.m=117.degree. C.
(by DSC).
Example 190
Polymerization of ethylene using MAO/XXVII/DEAC/2212
[0382] A 200-mL pear-shaped flask was charged with
MAO/XXVII/DEAC/2212 (2.9 .mu.mol) and toluene (50 mL) under a
nitrogen inert atmosphere. The flask was evacuated and backfilled
with 1 atm ethylene. The suspension was stirred for 2.5 hours
before it was quenched with methanol and 6 M HCl. The mixture was
filtered and the collected solid dried at 100.degree. C. to give
304 mg. M.sub.n=59.9K, M.sub.w=487.3K, M.sub.w/M.sub.n=8.1;
T.sub.m=125.degree. C. (by DSC).
Example 191
Preparation of MAO supported on silica (Grace Davison XPO-2402)
using incipient wetness, MAO.sup.IW/2402
[0383] A 50-mL pear-shaped flask, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with silica (Grace Davison XPO-2402; 3.33 g)
under a nitrogen inert atmosphere. The flask was equipped with a
magnetic stirring bar and a septum cap. While agitating the content
of the flask, 4 mL of MAO (Aldrich, 10 wt % in toluene) was added
dropwise. The flask was then placed in vacuo for 2 h, then stored
at room temperature under nitrogen for two days. The flask was then
heated to 80.degree. C. for 1 h and evacuated. MAO was further
added in 4 mL fractions until a total of 24 mL of MAO had been
added. Volatiles were removed at room temperature under vacuum
between each addition. After additions were complete, the solid was
further dried in vacuo for 90 min, yielding 4.80 g solid.
Example 192
Preparation of the nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4- ]-dithiane supported on
MAO.sup.IW/2402 by incipient wetness impregnation,
XXVII.sup.IW/MAO.sup.IW/2402
[0384] A 50-mL pear-shaped flask, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with MAO.sup.IW/2402 (784.9 mg) and cooled to
0.degree. C. A solution of the nickel complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]-- dithiane in
dichloromethane (10.4 mg in 1.2 mL) was then added dropwise under a
nitrogen inert atmosphere. The solid readily turned purple. The
solid was dried in vacuo at 0.degree. C. and stored at -30.degree.
C. Yield: 615 mg. Calculated Loading of Ni complex/g support: 23
.mu.mol/g.
Example 193
Polymerization of ethylene using XXVII.sup.IW/MAO.sup.IW/2402
[0385] A 1000-mL Parr.RTM. stirred reactor was charged with 75.2 mg
XXVII.sup.IW/MAO.sup.IW/2402 (5 .mu.mol Ni/g; 0.38 .mu.mol Ni)
under a nitrogen inert atmosphere. Toluene (300 mL) was added and
the reactor pressurized with ethylene (300 psig). The mixture was
stirred at 30.degree. C. for 60 min. The vessel was vented and the
catalyst quenched with methanol and 6 M HCl. The mixture was
filtered and the collected solid dried in vacuo at 100.degree. C.
to give 470.3 mg polymer. M.sub.n=268.1 K, M.sub.w=832.1 K,
M.sub.w/M.sub.n=3.1; 3 branches/1000.degree. C. (by .sup.1H NMR);
T.sub.m=132.degree. C.
Example 194
Treatment of XXVII.sup.IW/MAO.sup.IW/2402 with 1-Hexene by
incipient wetness, Hexene.sup.IW/XXVII.sup.IW/MAO.sup.IW/2402
[0386] A 20-mL scintillation vial, previously heated to 200.degree.
C. for several hours and allowed to cool to room temperature under
vacuum, was charged with XXVII.sup.IW/MAO.sup.IW/2402 (410.6 mg)
and cooled to -30.degree. C. 1-Hexene (0.5 mL) was then added
dropwise with vigorous agitation. A fraction of the resulting solid
was stored at -30.degree. C. and another at room temperature.
Example 195
Polymerization of ethylene using
Hexene.sup.IW/XXVII.sup.IW/MAO.sup.IW/240- 2
[0387] Under a nitrogen inert atmosphere, a 1000-mL Parr.RTM.
stirred reactor was charged with 55.3 mg
Hexene.sup.IW/XXVII.sup.IW/MAO.sup.IW/24- 02 (12 .mu.mol Ni/g; 0.66
.mu.mol Ni) that had been stored at room temperature for 28 days.
Toluene (300 mL) was added and the reactor pressurized with
ethylene (300 psig). The mixture was stirred at 30.degree. C. for
55 min. The vessel was vented and the catalyst quenched with
methanol and 6 M HCl. The mixture was filtered and the collected
solid dried in vacuo at 100.degree. C. to give 1.41 g polymer.
M.sub.n=347.0, M.sub.w=1077.0, M.sub.w/M.sub.n=3.1; 5
branches/1000.degree. C. (by .sup.1H NMR); T.sub.m=134.degree.
C.
Example 196
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of
Et.sub.2AlCl
[0388] A 600-ml Parr.RTM. autoclave was first heated to about
100.degree. C. under high vacuum to ensure the reactor was dry. The
reactor was cooled and purged with argon. Under an argon
atmosphere, the autoclave was charged with 150 ml of mineral
spirits and 1 ml of Et.sub.2AlCl. The autoclave was heated to
80.degree. C. and 2.0 ml of a stock solution (0.25 mg in 1 ml
CH.sub.2Cl.sub.2) of the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane was added via a
high-pressure sample loop. The reactor was rapidly pressurized to
600 psig ethylene. After 20 minutes at 80.degree. C., the reaction
was quenched by the addition of methanol. The swollen polyethylene
was isolated by filtration and dried for several hours in a vacuum
oven at 80.degree. C. 3.3 g of a white rubbery solid was isolated
(405,000 TO/h). DSC: (2nd heat) melt with an endothermic maximum at
51.degree. C. .sup.1H NMR: 45 branches/1000 carbon atoms. GPC:
Mn=60,900; Mw/Mn=1.90.
Example 197
Polymerization of ethylene with the nickel dibromide complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of
Et.sub.2AlCl
[0389] A 600 ml Parr.RTM. autoclave was first heated to about
100.degree. C. under high vacuum to ensure the reactor was dry. The
reactor was cooled and purged with argon. Under an argon
atmosphere, the autoclave was charged with 150 ml of toluene and 2
ml of Et.sub.2AlCl. The autoclave was heated to 75.degree. C. and
pressurized to 500 psig ethylene and 2.0 ml of a stock solution
(0.25 mg in 1 ml CH.sub.2Cl.sub.2) of the nickel dibromide complex
of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane was added via a
high pressure sample loop. The reactor was rapidly pressurized to
600 psig ethylene and the temperature ramped to 80.degree. C. After
20 minutes at 80.degree. C., the reaction was quenched by the
addition of methanol. The swollen polyethylene was isolated by
filtration and dried for several hours in a vacuum oven at
80.degree. C. 3.0 g of a white rubbery solid was isolated (368,000
TO/h). DSC: (2nd heat) melt with an endothermic maximum at
77.degree. C. .sup.1H NMR: 45 branches/1000 carbon atoms. GPC:
Mn=52,300; Mw/Mn=2.18.
Example 198
Synthesis of the Ni[.eta..sup.3-(H.sub.2CC(CO.sub.2Me)CH.sub.2)]
complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane
[0390] A flame dried Schlenk flask equipped with a stir bar and a
rubber septum was charged with 75 mg
[.eta..sup.3-(H.sub.2CC(CO.sub.2Me)CH.sub.2- ) Ni (.mu.-Br)].sub.2
(0.159 mmol), 293 mg (0.318 mmol) sodium
tetra[3,5-(trifluoromethylphenyl)]borate and 113 mg (0.318 mmol) of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane. The solid mixture
was dissolved in 10 ml of Et.sub.2O. The solution was stirred for 3
hours at room temperature while under an argon atmosphere. After 2
hours, the reaction mixture was filtered and the solvent removed in
vacuo giving the desired product (328 mg, 75% yield).
[.eta..sup.3-(H.sub.2CC(CO.sub.2Me)C- H.sub.2) Ni (.mu.-Br)].sub.2
was synthesized according to the procedure described in Wilke, G.
et. al. Angew. Chem., Int. ed. Engl. 1966, 5, 151.
Example 199
Ethylene polymerization using the
Ni[.eta..sup.3-(H.sub.2CC(CO.sub.2Me)CH.- sub.2)] complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane
[0391] A 600 ml Parr.RTM. autoclave was first heated to about
100.degree. C. under high vacuum to ensure the reactor was dry. The
reactor was cooled and purged with argon. Under an argon
atmosphere, the autoclave was charged with 200 mL of toluene and 2
ml of MAO (10% weight solution in toluene). The autoclave was
heated to 25.degree. C. and pressurized to 100 psig ethylene and
2.0 ml of a stock solution (1 mg in 1 ml toluene) of the
Ni[.eta..sup.3-(H.sub.2CC(CO.sub.2Me)CH.sub.2)] complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane was added via a high
pressure sample loop. The reactor was rapidly pressurized to 400
psig ethylene. After 60 minutes at 25.degree. C., the reaction was
quenched by the addition of methanol. The swollen polyethylene was
isolated by filtration and dried for several hours in a vacuum oven
at 80.degree. C. 1.1 g of a powdery white solid was isolated. DSC:
(2nd heat) melt with an endothermic maximum at 133.degree. C.
.sup.1H NMR: 2 branches/1000 carbon atoms.
Example 200
Synthesis of the silica supported
Ni[.eta..sup.3-(H.sub.2CC(CO.sub.2Me)CH.- sub.2)] complex of 2
3-bis(2,6-dimethylphenylimino)-[1,4]dithiane
[0392] A flame dried Schlenk flask equipped with a stir bar and a
rubber septum was charged with 30 mg (22 .mu.mol)
Ni[.eta..sup.3-(H.sub.2CC(CO.s- ub.2Me)CH.sub.2)]complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane and 1 g of MAO
treated silica (Witco TA02794/HL/04). The solid mixture was cooled
to 0.degree. C. and 20 ml of CH.sub.2Cl.sub.2 was added to the
flask and stirred for 45 minutes. After 45 minutes, the solvent was
removed in vacuo giving the supported catalyst.
Example 201
Ethylene Polymerization using the silica supported
Ni[.eta..sup.3-(H.sub.2- CC(CO.sub.2Me)CH.sub.2)] complex of
2,3-bis(2,6-dimethylphenylimino)-[1,4]- dithiane
[0393] A 600 ml Parr.RTM. stirred autoclave with 300 g of NaCl
(dried in a vacuum oven at 100.degree. C. for 24 hours) and 100 mg
of the supported catalyst prepared in example 200 was heated to
50.degree. C. and pressurized rapidly to 400 psig ethylene. The
temperature ramped up to 60.degree. C. and the gas phase
polymerization was agitated for 1 hour. After 1 hour, the reactor
was vented and the contents poured in to a beaker. The polyethylene
that resulted was isolated by dissolving the NaCl in a blender and
collecting the remaining polymer by filtration. The polyethylene
was washed with 6M HCl, water and acetone. The polymer was then
dried in a vacuum oven at 100.degree. C. giving 4.7 grams of free
flowing polyethylene. DSC: (2nd heat) melt with an endothermic
maximum at 122.degree. C. .sup.1H NMR: 22 branches/1000 carbon
atoms.
* * * * *
References