U.S. patent application number 16/250677 was filed with the patent office on 2019-08-15 for ethylene-a-olefin-diene elastomers and methods of making them.
The applicant listed for this patent is ExxonMobil Chemical Patents Inc.. Invention is credited to Crisita Carmen H. Atienza, Sudhin Datta, John R. Hagadorn, Rhutesh K. Shah, Ron Walker.
Application Number | 20190248934 16/250677 |
Document ID | / |
Family ID | 67540852 |
Filed Date | 2019-08-15 |
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United States Patent
Application |
20190248934 |
Kind Code |
A1 |
Atienza; Crisita Carmen H. ;
et al. |
August 15, 2019 |
Ethylene-a-olefin-diene Elastomers and Methods of Making Them
Abstract
A process to produce a branched ethylene-.alpha.-olefin diene
elastomer comprising combining a catalyst precursor and an
activator with a feed comprising ethylene, C3 to C12
.alpha.-olefins, and a dual-polymerizable diene to obtain a
branched ethylene-.alpha.-olefin diene elastomer; where the
catalyst precursor is selected from pyridyldiamide and
quinolinyldiamido transition metal complexes. The branched
ethylene-.alpha.-olefin diene elastomer may comprise within a range
from 40 to 80 wt % of ethylene-derived units by weight of the
branched ethylene-.alpha.-olefin diene elastomer, and 0.1 to 2 wt %
of singly-polymerizable diene derived units, 0.1 to 2 wt % of
singly-polymerizable diene derived units, and the remainder
comprising C3 to C12 .alpha.-olefin derived units, wherein the
branched ethylene-.alpha.-olefin diene elastomer has a weight
average molecular weight (M.sub.w) within a range from 100 kg/mole
to 300 kg/mole, an average branching index (g'.sub.avg) of 0.9 or
more, and a branching index at very high M.sub.w (g'.sub.1000) of
less than 0.9.
Inventors: |
Atienza; Crisita Carmen H.;
(Houston, TX) ; Shah; Rhutesh K.; (Katy, TX)
; Walker; Ron; (Pearland, TX) ; Hagadorn; John
R.; (Houston, TX) ; Datta; Sudhin; (Houston,
TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ExxonMobil Chemical Patents Inc. |
Baytown |
TX |
US |
|
|
Family ID: |
67540852 |
Appl. No.: |
16/250677 |
Filed: |
January 17, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62628420 |
Feb 9, 2018 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01J 2531/49 20130101;
C08F 210/06 20130101; B01J 2531/0297 20130101; B01J 31/1835
20130101; B01J 31/146 20130101; C08F 210/18 20130101; C08F 2800/20
20130101; C08F 210/18 20130101; C08F 4/64113 20130101; B01J 2540/22
20130101; B01J 2231/12 20130101; C08F 236/20 20130101; B01J 31/183
20130101; C08F 210/16 20130101; C08F 236/04 20130101; C08F 210/02
20130101; B01J 2531/0241 20130101; C08F 4/64113 20130101 |
International
Class: |
C08F 210/16 20060101
C08F210/16; C08F 210/02 20060101 C08F210/02; C08F 210/06 20060101
C08F210/06; C08F 236/04 20060101 C08F236/04; C08F 236/20 20060101
C08F236/20; B01J 31/18 20060101 B01J031/18; C08F 4/64 20060101
C08F004/64 |
Claims
1. A process to produce a branched ethylene-a-olefin diene
elastomer (b-EDE) comprising combining a catalyst precursor and an
activator with a feed comprising ethylene, C3 to C12
.alpha.-olefins, and a dual-polymerizable diene to obtain a b-EDE;
where the catalyst precursor is selected from pyridyldiamide and
quinolinyldiamido transition metal complexes.
2. The process of claim 1, combining at a temperature within a
range from 80.degree. C. to 160.degree. C. and a pressure within a
range from 0.5 MPa to 8 MPa.
3. The process of claim 1, combining in a solution process.
4. The process of claim 1, also combining a singly-polymerizable
diene.
5. The process of claim 1, wherein the .alpha.-olefins comprise
propylene.
6. The process of claim 1, wherein hydrogen is present to less than
5 sccm (standard cubic centimeter per min.).
7. The process of claim 1, wherein the b-EDE comprises within a
range from 40 to 80 wt % of ethylene-derived units by weight of the
b-EDE, 0.05 to 2 wt % of the dual-polymerizable diene derived units
by weight of the b-EDE, and 0 to 15 wt % of the
singly-polymerizable diene derived units by weight of the b-EDE,
the remainder comprising C3 to C12 .alpha.-olefin derived
units.
8. The process of claim 1, wherein the b-EDE has a weight average
molecular weight (Mw) within a range from 100 kg/mole to 750
kg/mole.
9. The process of claim 1, wherein the b-EDE has a g'.sub.avg of
0.9 or more, and a g'.sub.1000 of less than 0.9.
10. The process of claim 1, wherein the pyridyldiamido and
quinolinyldiamido transition metal complexes are selected from one
of the following structures: ##STR00004## wherein M is titanium,
hafnium or zirconium, most preferably hafnium; R.sup.1 and R.sup.10
are independently selected from the group consisting of
hydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, and
silyl groups; R.sup.2 and R.sup.9 are each, independently, divalent
hydrocarbyls or a chemical bond; R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, and R.sup.8 are independently selected from the
group consisting of hydrogen, hydrocarbyls, substituted
hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and
wherein adjacent R groups may be joined to form a substituted or
unsubstituted hydrocarbyl or heterocyclic ring, where the ring has
5, 6, 7, or 8 ring atoms and where substitutions on the ring can
join to form additional rings; X is an anionic leaving group, where
the X groups may be the same or different and any two X groups may
be linked to form a dianionic leaving group; and Z is
--(R.sup.11).sub.pQj(R.sup.12).sub.q--, wherein Q is carbon,
oxygen, nitrogen, or silicon, and where J is carbon or silicon, p
is 1 or 2; and q is 1 or 2; and R.sup.11 and R.sup.12 are
independently selected from the group consisting of hydrogen,
hydrocarbyls, and substituted hydrocarbyls, and wherein adjacent
R.sup.11 and R.sup.12 groups may be joined to form an aromatic or
saturated, substituted or unsubstituted hydrocarbyl ring, where the
ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on
the ring can join to form additional rings.
11. A branched ethylene-.alpha.-olefin diene elastomer (b-EDE)
comprising within a range from 40 to 80 wt % of ethylene-derived
units by weight of the b-EDE, 0.05 to 2 wt % of dual-polymerizable
diene derived units by weight of the b-EDE, and 0.1 to 2 wt % of
singly-polymerizable diene derived units by weight of the b-EDE,
the remainder comprising C3 to C12 .alpha.-olefin derived units,
wherein the b-EDE has a weight average molecular weight (Mw) within
a range from 100 kg/mole to 750 kg/mol, wherein the b-EDE has a
g'.sub.avg of 0.90 or more, and a g'.sub.1000 of less than 0.9.
12. The branched ethylene-a-olefin diene elastomer of claim 11,
wherein the b-EDE has a gel content of less than 5 wt %.
13. The branched ethylene-.alpha.-olefin diene elastomer of claim
11, wherein the branched ethylene-.alpha.-olefin diene elastomer is
formed in a process comprising combining a catalyst precursor and
an activator with a feed comprising ethylene, C3 to C12
.alpha.-olefins, and a dual-polymerizable diene to obtain a b-EDE;
where the catalyst precursor is selected from pyridyldiamide and
quinolinyldiamido transition metal complexes.
14. The branched ethylene-.alpha.-olefin diene elastomer of claim
13, wherein the pyridyldiamido and quinolinyldiamido transition
metal complexes are selected from one of the following structures:
##STR00005## wherein M is titanium, hafnium or zirconium, most
preferably hafnium; R.sup.1 and R.sup.10 are independently selected
from the group consisting of hydrocarbyls, substituted
hydrocarbyls, heterohydrocarbyls, and silyl groups; R.sup.2 and
R.sup.9 are each, independently, divalent hydrocarbyls or a
chemical bond; R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and
R.sup.8 are independently selected from the group consisting of
hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy,
halogen, amino, and silyl, and wherein adjacent R groups may be
joined to form a substituted or unsubstituted hydrocarbyl or
heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and
where substitutions on the ring can join to form additional rings;
X is an anionic leaving group, where the X groups may be the same
or different and any two X groups may be linked to form a dianionic
leaving group; and Z is --(R.sup.11).sub.pQj(R.sup.12).sub.q--,
wherein Q is carbon, oxygen, nitrogen, or silicon, and where J is
carbon or silicon, p is 1 or 2; and q is 1 or 2; and R.sup.11 and
R.sup.12 are independently selected from the group consisting of
hydrogen, hydrocarbyls, and substituted hydrocarbyls, and wherein
adjacent R.sup.11 and R.sup.12 groups may be joined to form an
aromatic or saturated, substituted or unsubstituted hydrocarbyl
ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where
substitutions on the ring can join to form additional rings.
Description
PRIORITY CLAIM
[0001] This application claims the benefit of priority from U.S.
Provisional Application No. 62/628,420, filed Feb. 9, 2018, which
is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention(s) relate in general to
ethylene-.alpha.-olefin diene elastomers and methods of making
them, and more particularly to branched ethylene-.alpha.-olefin
diene elastomers and a process to make them using pyridyldiamido
and quinolinyldiamido transition metal complexes in a solution
polymerization process.
BACKGROUND
[0003] The dual-polymerizable diene 5-vinyl-2-norbornene (VNB) is
used in the production of ethylene-propylene-diene elastomer (EPDM)
for peroxide curing and can also be utilized to prepare long-chain
branched EPDM (b-EPDM). A major challenge in the production of
b-EPDM is gel formation, which results from the high reactivity of
the vinyl group in the VNB.
[0004] To mitigate gelation, a catalyst must have high endocyclic
alkene/vinyl selectivity which minimizes hyperbranching via
insertion of the pendant vinyl. Using high-throughput
experimentation, the inventors have identified unique catalysts as
suitable catalysts and methods for polymerization using VNB as a
comonomer.
[0005] Relevant publications include U.S. Pat. Nos. 8,962,761;
8,058,373; 8,013,082; 7,956,140; 7,829,645; 7,511,106; 6,545,088;
6,329,477; 6,124,413; 5,698,651; 5,229,478; EP 2221323A1; EP
2115018A1; JP H1160841; JP 09048823; WO 2017/048448; WO
2011/002199; WO 2010/012587; WO 2005/005496; WO 2008/095687; WO
97/32946; and WO 95/16716.
SUMMARY
[0006] Disclosed is a process to produce a branched
ethylene-.alpha.-olefin diene elastomer (b-EDE) comprising (or
consisting essentially of, or consisting of) combining a catalyst
precursor and an activator with a feed comprising ethylene, C3 to
C12 .alpha.-olefins, and a dual-polymerizable diene to obtain a
b-EDE; where the catalyst precursor is selected from pyridyldiamide
and quinolinyldiamido transition metal complexes.
[0007] Also disclosed is a branched ethylene-.alpha.-olefin diene
elastomer (b-EDE) comprising (or consisting of, or consisting
essentially of) within a range from 40, or 45 to 65, or 70, or 75,
or 80 wt % of ethylene-derived units by weight of the b-EDE, and
0.1 to 0.8, or 1, or 1.4, or 1.8, or 2 wt % of singly-polymerizable
diene derived units by weight of the b-EDE, within a range from 0.1
to 0.5, or 0.8, or 1, or 1.4, or 1.8, or 2 wt % of a
singly-polymerizable diene derived units by weight of the b-EDE,
and the remainder comprising C3 to C12 .alpha.-olefin derived units
(preferably propylene derived units), wherein the b-EDE has a
weight average molecular weight (Mw) within a range from 100
kg/mole to 200, or 240, or 280, or 300, or 400, or 600, or 750
kg/mole, and wherein the b-EDE has a g'.sub.avg of 0.90 or more,
and a g'.sub.1000 of less than 0.9, or 0.85, or 0.8 (or within a
range from 0.4, or 0.6, or 0.65 to 0.8 or 0.85 or 0.9).
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is a gel permeation chromatogram and mass balance of
inventive branched ethylene-.alpha.-olefin diene elastomer of
Sample 3.
[0009] FIG. 2a is a plot of phase angle versus complex modulus for
the inventive branched ethylene-.alpha.-olefin diene elastomer from
the PDA catalyst.
[0010] FIG. 2b is a plot of phase angle versus complex modulus for
the inventive branched ethylene-.alpha.-olefin diene elastomer from
the QDA catalyst.
[0011] FIG. 3 is an extensional viscosity trace at various rates
for Sample 1 elastomer (no VNB) at 150.degree. C.
[0012] FIG. 4 is an extensional viscosity trace at various rates
for the inventive branched ethylene-.alpha.-olefin diene elastomer
(0.2 wt % VNB) of Sample 3.
DETAILED DESCRIPTION
[0013] The pyridyldiamido and quinolinyldiamido transition metal
complexes described herein were tested for terpolymerization
capability at increasing VNB feed rates and a target ethylene
content of approximately 60%. Analytical techniques such as gel
permeation chromatograph (GPC), dynamic shear rheology, and
extensional viscosity analyses of the resulting polymers were all
consistent with higher long-chain branching (LCB) levels as the VNB
content was increased. Performing the same experiments with ENB as
the diene resulted in, for instance, 0.8 wt % ENB incorporation,
indicating that approximately 75% of the vinyl group of VNB in the
polymer was reacted to form long chain branches. GPC-4D analysis of
the VNB-EPDM samples resulted in 100% recovery, which suggested
negligible gel content in the material. However, in-reactor gel was
obtained upon opening the reactor, albeit at a lower amount
compared with those observed using metallocene-type polymerization
catalysts. Thus, the inventors have found an improved method of
forming ethylene-.alpha.-olefin diene elastomers, as set forth more
particularly herein.
[0014] In any embodiment, the "dual-polymerizable dienes" are diene
monomers selected from vinyl substituted strained bicyclic and
unconjugated dienes, and alpha-omega linear dienes where both sites
of unsaturation are polymerizable by a polymerization catalyst
(e.g., Ziegler-Natta, vanadium, metallocene, etc.); and more
preferably from vinyl norbornenes and C7 to C12 alpha-omega linear
dienes (e.g., 1,7-heptadiene and 1,9-decadiene), and is most
preferably 5-vinyl-2-norbornene (VNB). The b-EDE formed therefrom
comprises "dual-polymerizable diene derived monomer units".
[0015] In any embodiment, the "singly-polymerizable dienes" are
diene monomers in which only one of the double bonds is activated
by a polymerization catalyst and is selected from cyclic and linear
alkylenes, non-limiting examples of which include an unconjugated
diene (and other structures where each double bond is two carbons
away from the other), 5-ethylidene-2-norbornene,
4-vinylcyclohexeneand other strained bicyclic and unconjugated
dienes, and dicyclopentadiene. More preferably, the
singly-polymerizable diene is selected from C7 to C30 cyclic
singly-polymerizable dienes. Most preferably the
singly-polymerizable diene is 5-ethylidene-2-norbornene (ENB). The
b-EDE formed therefrom comprises "singly-polymerizable diene
derived monomer units".
[0016] In any embodiment, a "branched" ethylene-.alpha.-olefin
diene elastomer (b-EDE) has a branching index value at a molecular
weight of 1.times.10.sup.6 g/mol, g'.sub.1000, of less than or
equal to 0.860 as calculated using the output of the GPC-IR5-LS-VIS
method as follows. The average intrinsic viscosity, [n.sub.avg], of
the sample is calculated by:
[ .eta. ] avg = c i [ .eta. ] i c i , ##EQU00001##
where the summations are over the chromatographic slices, "i",
between the integration limits. The branching index g'.sub.avg is
defined as:
g avg ' = [ .eta. ] avg kM v .alpha. . ##EQU00002##
[0017] In any embodiment, the branched polymer has minimal gel
content. As used herein, the "gel content" refers to an insoluble
portion (in hydrocarbon solvent) of polymer determined by
extraction of a sample of the b-EDE in a hydrocarbon solvent such
as cyclohexane, toluene or isohexane, which are typically used to
dissolve b-EDE. In any embodiment, the gel content of the inventive
b-EDE is less than 5, or 1, or 0.1 wt %.
[0018] In any embodiment, the "pyridyldiamido and quinolinyldiamido
transition metal complexes" include organometallic complexes of a
transition metal ion, especially titanium, zirconium or hafnium,
with one or more ligands that include at least one pyridyl and/or
quinolinyl group and at least two other alkylamine ligands, and at
least one leaving group, preferably a halogen or alkyl group, that
is reactive towards the appropriate boron and/or aluminum-based
activator.
[0019] In any embodiment, the pyridyldiamido and quinolinyldiamido
transition metal complexes are selected from one of the following
structures:
##STR00001##
wherein M is titanium, hafnium or zirconium, most preferably
hafnium; R.sup.1 and R.sup.10 are independently selected from the
group consisting of hydrocarbyls (such as alkyls, aryls),
substituted hydrocarbyls (substituents pendant to the hydrocarbyl),
heterohydrocarbyls (non-carbon atoms within the hydrocarbyl), and
silyl groups; most preferably R.sup.1 and R.sup.1 comprise an
aniline structure that may be substituted with C1 to C5 alkyls;
R.sup.2 and R.sup.9 are each, independently, divalent hydrocarbyls
or a chemical bond; R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7,
and R.sup.8 are independently selected from the group consisting of
hydrogen, hydrocarbyls (e.g., alkyls and aryls), substituted
hydrocarbyls (e.g., heteroaryl), alkoxy, aryloxy, halogen, amino,
and silyl, and wherein adjacent R groups may be joined to form a
substituted or unsubstituted hydrocarbyl or heterocyclic ring,
where the ring has 5, 6, 7, or 8 ring atoms and where substitutions
on the ring can join to form additional rings; X is an anionic
leaving group, where the X groups may be the same or different and
any two X groups may be linked to form a dianionic leaving group;
and Z is --(R.sup.11).sub.pQj(R.sup.12).sub.q--, q.sup.-, wherein Q
is carbon, oxygen, nitrogen, or silicon (preferably nitrogen), and
where J is carbon or silicon (preferably carbon), p is 1 or 2; and
q is 1 or 2; and R.sup.11 and R.sup.12 are independently selected
from the group consisting of hydrogen, hydrocarbyls (preferably
alkyls), and substituted hydrocarbyls, and wherein adjacent
R.sup.11 and R.sup.12 groups may be joined to form an aromatic or
saturated, substituted or unsubstituted hydrocarbyl ring, where the
ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on
the ring can join to form additional rings; most preferably Z forms
a bicyclic hydrocarbyl comprising a C6 cyclic portion and a C4 to
C6 cyclic portion, where an example of Z is a divalent
tetrahydroindenyl or divalent tetrahydronaphthalene.
[0020] In any embodiment, the pyridyldiamido and quinolinyldiamido
transition metal complexes are selected from one of the following
structures:
##STR00002##
wherein the "Me" represents "methyl" and "iPr" represents
"iso-propyl", and wherein these groups could also variously be any
C1 to C10 alkyl (normal, iso, and/or tertiary), and the saturated
ring may variously be a 4 to 6 membered ring, interchangeably
between the two structures.
[0021] Thus in any embodiment is a process to produce a branched
ethylene-.alpha.-olefin diene elastomer (b-EDE) comprising (or
consisting essentially of, or consisting of) combining a catalyst
precursor and an activator with a feed comprising ethylene, C3 to
C12 .alpha.-olefins, and a dual-polymerizable diene to obtain a
b-EDE; where the catalyst precursor is selected from pyridyldiamide
and quinolinyldiamido transition metal complexes.
[0022] The catalyst or catalyst precursor must also be combined
with at least one "activator" to effect polymerization of the
cyclic olefin monomers and ethylene, wherein the activator
preferably comprises a non-coordinating borate anion and a bulky
organic cation. In any embodiment, the non-coordinating borate
anion comprises a tetra(perfluorinated C6 to C14 aryl)borate anion
and substituted versions thereof; most preferably the
non-coordinating borate anion comprises a
tetra(pentafluorophenyl)borate anion or
tetra(perfluoronaphthyl)borate anion.
[0023] Preferably the bulky organic cation is selected from the
following structures (a) and (b):
##STR00003##
wherein each R group is independently hydrogen, a C6 to C14 aryl
(e.g., phenyl, naphthyl, etc.), a C1 to C10 or C20 alkyl, or
substituted versions thereof; and more preferably at least one R
group is an C6 to C14 aryl or substituted versions thereof.
[0024] In any embodiment, the bulky organic cation is a reducible
Lewis Acid, especially a trityl-type cation (wherein each "R" group
in (a) is aryl) capable of extracting a ligand from the catalyst
precursor, where each "R" group is an C6 to C14 aryl group (phenyl,
naphthyl, etc.) or substituted C6 to C14 aryl, and preferably the
reducible Lewis acid is triphenyl carbenium and substituted
versions thereof.
[0025] Also, in any embodiment, the bulky organic cation is a
Bronsted acid capable of donating a proton to the catalyst
precursor, wherein at least one "R" group in (b) is hydrogen.
Exemplary bulky organic cations of this type in general include
ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof;
preferably ammoniums of methylamine, aniline, dimethylamine,
diethylamine, N-methylaniline, diphenylamine, trimethylamine,
triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine,
p-bromo-N,N-dimethylaniline, and p-nitro-N,N-dimethylaniline;
phosphoniums from triethylphosphine, triphenylphosphine, and
diphenylphosphine; oxoniums from ethers, such as dimethyl ether
diethyl ether, tetrahydrofuran, and dioxane; and sulfoniums from
thioethers, such as diethyl thioethers and tetrahydrothiophene, and
mixtures thereof.
[0026] The catalyst precursor preferably reacts with the activator
upon their combination to form a "catalyst" or "activated catalyst"
that can then effect the polymerization of monomers. The catalyst
may be formed before combining with monomers, after combining with
monomers, or simultaneous therewith.
[0027] In any embodiment, the combining takes place at a
temperature within a range from 80, or 90.degree. C. to 120, or
140, or 160.degree. C. and a pressure within a range from 0.5 MPa
to 4, or 6, or 8 MPa. Most preferably the combining in a solution
process, meaning that all components in the polymerization are
soluble in the medium (diluent and/or monomers) or at least 80, or
90 wt % of the components are soluble and dissolved in the
medium.
[0028] In any embodiment, the solution process can be carried out
in one or more single-phase, liquid-filled, stirred tank reactor
with continuous flow of feeds to the system and continuous
withdrawal of products under steady state conditions. When more
than one reactor is used, the reactors may be operated in a serial
or parallel configuration making essentially the same or different
polymer components. Advantageously, the reactors would produce
polymers with different properties, such as different molecular
weights, or different monomer compositions, or different levels of
long-chain branching, or any combinations thereof. All
polymerizations can be performed in a system with a solvent
comprising any one or more of C4 to C12 alkanes, using soluble
metallocene catalysts or other single-site catalysts and discrete,
non-coordinating borate anion as co-catalysts. A homogeneous dilute
solution of tri-n-octyl aluminum or other aluminum alkyl in a
suitable solvent may be used as a scavenger in concentrations
appropriate to maintain reaction. Chain transfer agents, such as
hydrogen, can be added to control molecular weight.
[0029] Polymerizations can be at high temperatures described above
and high conversions to maximize macromer re-insertions that create
long chain branching, if so desired. This combination of a
homogeneous, continuous, solution process helped to ensure that the
products had narrow composition and sequence distributions.
[0030] In any embodiment the process also comprises further
combining a singly-polymerizable diene. Also in any embodiment the
.alpha.-olefins comprise (or consist of) propylene. Finally,
hydrogen is preferably present to less than 5, or 1, or 0.8, or
0.4, or 0.2 sccm (standard cubic centimeter per min.) from the
feed; and most preferably hydrogen is absent from the feed. When
referring to the "feed", this components that are combined include
only those substances in the feed.
[0031] Produced from the process is a branched
ethylene-.alpha.-olefin diene elastomer (b-EDE) comprising (or
consisting of, or consisting essentially of) within a range from
40, or 45 to 65, or 70, or 75, or 80 wt % of ethylene-derived units
by weight of the b-EDE, 0.1 to 0.8, or 1, or 1.4, or 1.8, or 2 wt %
of singly-polymerizable diene derived units by weight of the b-EDE,
within a range from 0.1 to 0.5, or 0.8, or 1, or 1.4, or 1.8, or 2
wt % of a singly-polymerizable diene derived units by weight of the
b-EDE, and the remainder comprising C3 to C12 .alpha.-olefin
derived units (preferably propylene derived units), wherein the
b-EDE has a weight average molecular weight (Mw) within a range
from 100 kg/mole to 200, or 240, or 280, or 300, or 400, or 600, or
750 kg/mole, and wherein the b-EDE has a g'.sub.avg of 0.9 or more,
and a g'.sub.1000 of less than 0.9, or 0.85, or 0.8 (or within a
range from 0.4, or 0.6, or 0.65 to 0.8 or 0.85 or 0.9).
[0032] The inventive b-EDEs may be useful in any number of
applications such as rubber profiles (like automotive solid and
sponge profiles, building profiles), hoses, mechanical goods, films
(cast and/or blown) and sheets of material, such as for roofing
applications, as well as thermoformed articles, blow molded
articles, rotomolded articles, and injection molded articles.
Particularly desirable end uses include automotive components and
gaskets. Any of these articles may be foamed articles which are
formed by means known in the art. Foamed or not, some specific uses
of the inventive b-EDEs include weather stripping, heat insulation,
opening trim, and car trunk or car hood seals.
[0033] The various descriptive elements and numerical ranges
disclosed herein for the inventive process and b-EDE therefrom can
be combined with other descriptive elements and numerical ranges to
describe the invention(s); further, for a given element, any upper
numerical limit can be combined with any lower numerical limit
described herein, including the examples in jurisdictions that
allow such combinations. The features of the inventions are
demonstrated in the following non-limiting examples.
EXAMPLES
[0034] The synthesis of the catalyst precursor is described here,
as well as the polymerization examples.
[0035] Proton (.sup.1H) Nuclear Magnetic Resonance Catalyst
characterization was accomplished using proton NMR, wherein the
.sup.1H NMR data was collected at 23.degree. C. in a 5 mm probe
using a Varian spectrometer with a .sup.1H frequency of at least
400 MHz. Data was recorded using a maximum pulse width of
45.degree., 8 sec between pulses and signal averaging 120
transients. All NMR spectra were referenced using the peak
corresponding to the deuterated solvent.
[0036] Starting Reagents Sodium hydride (NaH),
8-bromoquinolin-2(1H)-one, t-butyldimethylsilylchloride,
n-butyllithium, t-butyllithium, Pd.sub.2(dba).sub.3,
2-Dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos),
K.sub.2CO.sub.3, dichloromethane, methanol, POCl.sub.3, n-hexane,
1,2,3,4-tetrahydronaphthalen-1-ol, N,N,N',N'-tetramethylethylene
diamine (TMEDA), pentane, 1,2-dibromotetrafluoroethane,
Na.sub.2SO.sub.4, triethylamine, acetic anhydride,
4-(dimethylamino)pydridine (DMAP), ethyl acetate, Na.sub.2CO.sub.3,
potassium hydroxide (KOH), pyridinium chlorochromate (PCC),
aniline, toluene, TiCl.sub.4, NaBH.sub.3CN, acetic acid,
CDCl.sub.3, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,
1,4-dioxane, cesium carbonate, Pd(PPh.sub.3).sub.4, benzene,
Hf(NMe.sub.2).sub.4, Me.sub.3Al, 6-bromopyridine-2-carboxaldehyde,
2,6-diisopropylaniline, indan-1-ol and
2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane were purchased
from commercial sources and used as received.
Hf(NMe.sub.2).sub.2Cl.sub.2, 1,2-dimethoxyethane (DME), and
dimethylmagnesium were prepared following published procedures
(Erker et al., in 19 ORGANOMETALLICS 127 (2000); Coates and Heslop,
in J. CHEM. SOC. A 514 (1968); Andersen et al., in J. CHEM. SOC.,
DALTON TRANS. 809 (1977)). Tetrahydrofuran (THF, Merck) and diethyl
ether (Merck) were freshly distilled from benzophenone ketyl were
used for organometallic synthesis and catalysis.
[0037] 8-(2,6-Diisopropylphenylamino)quinolin-2(1H)-one To a
suspension of NaH (5.63 g of 60 wt % in mineral oil, 140 mmol) in
tetrahydrofuran (1000 mL) was added 8-bromoquinolin-2(1H)-one (30.0
g, 134 mmol) in small portions at 0.degree. C. The obtained
reaction mixture was warmed to 23.degree. C. (room temperature),
stirred for 30 min, then cooled to 0.degree. C. Then
t-butyldimethylsilylchloride (20.2 g, 134 mmol) was added in one
portion. This mixture was stirred for 30 min at 23.degree. C. and
then poured into water (1 L). The protected
8-bromoquinolin-2(1H)-one was extracted with diethyl ether
(3.times.400 mL). The combined extracts were dried over
Na.sub.2SO.sub.4 and then evaporated to dryness. Yield 45.2 g
(quant., 99% purity by GC/MS) of a dark red oil. To a solution of
2,6-diisopropylaniline (27.7 mL, 147 mmol) and toluene (1.5 L) was
added n-butyllithium (60.5 mL, 147 mmol, 2.5 M in hexanes) at
23.degree. C. The obtained suspension was heated briefly to
100.degree. C. and then cooled to 23.degree. C. To the reaction
mixture was added Pd.sub.2(dba).sub.3 (dba=dibenzylideneacetone)
(2.45 g, 2.68 mmol) and XPhos (2.55 g, 5.36 mmol) followed by the
addition of the protected 8-bromoquinolin-2(1H)-one (45.2 g, 134
mmol). The obtained dark brown suspension was heated at 60.degree.
C. until lithium salt precipitate disappeared (ca. 30 min). The
resulting dark red solution was quenched by addition of water (100
mL), and the organic layer was separated, dried over
Na.sub.2SO.sub.4 and then evaporated to dryness. The obtained oil
was dissolved in a mixture of dichloromethane (1000 mL) and
methanol (500 mL), followed by an addition of 12 M HCl (50 mL). The
reaction mixture was stirred at 23.degree. C. for 3 hr., then
poured into 5% K.sub.2CO.sub.3 (2 L). The product was extracted
with dichloromethane (3.times.700 mL). The combined extracts were
dried over Na.sub.2SO.sub.4, filtered, and then evaporated to
dryness. The resulting solid was triturated with n-hexane (300 mL),
and the obtained suspension collected on a glass frit. The
precipitate was dried in vacuum. Yield 29.0 g (67%) of a
marsh-green solid. Anal. calc. for C.sub.21H.sub.24N.sub.2O: C,
78.71; H, 7.55; N, 8.74. Found: C, 79.00; H, 7.78; N, 8.50. .sup.1H
NMR (CDCl.sub.3): .delta. 13.29 (br.s, 1H), 7.80-7.81 (d, 1H, J=9.5
Hz), 7.35-7.38 (m, 1H), 7.29-7.30 (m, 3H), 6.91-6.95 (m, 2H),
6.58-6.60 (d, 1H, J=9.5 Hz), 6.27-6.29 (m, 1H), 3.21 (sept, 2H,
J=6.9 Hz), 1.25-1.26 (d, 6H, J=6.9 Hz), 1.11-1.12 (d, 6H, J=6.9
Hz).
[0038] 2-Chloro-N-(2,6-diisopropylphenyl)quinolin-8-amine 29.0 g
(90.6 mmol) of 8-(2,6-diisopropylphenylamino)quinolin-2(1H)-one was
added to 400 mL of POCl.sub.3 in one portion. The resulting
suspension was heated for 40 hrs. at 105.degree. C., then cooled to
23.degree. C., and poured into 4000 cm.sup.3 of a crushed ice. The
crude product was extracted with 3.times.400 mL of diethyl ether.
The combined extract was dried over K.sub.2CO.sub.3 and then
evaporated to dryness. The resulting solid was triturated with 30
mL of cold n-hexane, and the formed suspension was collected on a
glass frit. The obtained solid was dried in vacuum. Yield 29.0 g
(95%) of a yellow-green solid. Anal. calc. for
C.sub.21H.sub.23N.sub.2Cl: C, 74.43; H, 6.84; N, 8.27. Found: C,
74.68; H, 7.02; N, 7.99. .sup.1H NMR (CDCl.sub.3): .delta.
8.04-8.05 (d, 1H, J=8.6 Hz), 7.38-7.39 (d, 1H, J=8.5 Hz), 7.33-7.36
(m, 1H), 7.22-7.27 (m, 4H), 7.04-7.06 (d, 1H, J=8.1 Hz), 6.27-6.29
(d, 1H, J=7.8 Hz), 3.20 (sept, 2H, J=6.9 Hz), 1.19-1.20 (d, 6H,
J=6.9 Hz), 1.10-1.11 (d, 6H, J=6.9 Hz).
[0039] 8-Bromo-1,2,3,4-tetrahydronaphthalen-1-ol To a mixture of
78.5 g (530 mmol) of 1,2,3,4-tetrahydronaphthalen-1-ol, 160 mL
(1.06 mol) of N,N,N',N'-tetramethylethylenediamine, and 3000 mL of
pentane cooled to -20.degree. C. 435 mL (1.09 mol) of 2.5 M
.sup.nBuLi in hexanes was added dropwise. The obtained mixture was
refluxed for 12 hrs. then cooled to -80.degree. C., and 160 mL
(1.33 mol) of 1,2-dibromotetrafluoroethane was added. The obtained
mixture was allowed to warm to 23.degree. C. and then stirred for
12 hrs. at this temperature. After that, 100 mL of water was added.
The resulting mixture was diluted with 2000 mL of water, and the
organic layer was separated. The aqueous layer was extracted with
3.times.400 mL of toluene. The combined organic extract was dried
over Na.sub.2SO.sub.4 and then evaporated to dryness. The residue
was distilled using the Kugelrohr apparatus, b.p. 150-160.degree.
C./l mbar. The obtained yellow oil was dissolved in 100 mL of
triethylamine, and the formed solution was added dropwise to a
stirred solution of 71.0 mL (750 mmol) of acetic anhydride and 3.00
g (25.0 mmol) of 4-dimethylaminopyridine in 105 mL of
triethylamine. The formed mixture was stirred for 5 min, then 1000
mL of water was added, and the obtained mixture was stirred for 12
hrs. After that, the reaction mixture was extracted with
3.times.200 mL of ethyl acetate. The combined organic extract was
washed with aqueous Na.sub.2CO.sub.3, dried over Na.sub.2SO.sub.4,
and then evaporated to dryness. The residue was purified by flash
chromatography on silica gel 60 (40-63 .mu.m, eluent: hexane-ethyl
acetate=30:1, vol.). The isolated ester was dissolved in 1500 mL of
methanol, 81.0 g (1.45 mol) of KOH was added, and the obtained
mixture was heated to reflux for 3 hrs. The reaction mixture was
then cooled to 23.degree. C. and poured into 4000 mL of water. The
title product was extracted with 3.times.300 mL of dichloromethane.
The combined organic extract was dried over Na.sub.2SO.sub.4 and
then evaporated to dryness. Yield 56.0 g (47%) of a white
crystalline solid. .sup.1H NMR (CDCl.sub.3): .delta. 7.38-7.41 (m,
1H, 7-H); 7.03-7.10 (m, 2H, 5,6-H); 5.00 (m, 1H, 1-H), 2.81-2.87
(m, 1H, 4/4'-H), 2.70-2.74 (m, 1H, 4'/4-H), 2.56 (br.s., 1H, OH),
2.17-2.21 (m, 2H, 2,2'-H), 1.74-1.79 (m, 2H, 3,3'-H).
[0040] 8-Bromo-3,4-dihydronaphthalen-1(2H)-one To a solution of
56.0 g (250 mmol) of 8-bromo-1,2,3,4-tetrahydronaphthalen-1-ol in
3500 mL of dichloromethane was added 265 g (1.23 mol) of pyridinium
chlorochromate (PCC). The resulting mixture was stirred for 5 hrs.
at 23.degree. C., then passed through a pad of silica gel 60 (500
mL; 40-63 .mu.m), and finally evaporated to dryness. Yield 47.6 g
(88%) of a colorless solid. .sup.1H NMR (CDCl.sub.3): .delta. 7.53
(m, 1H, 7-H); 7.18-7.22 (m, 2H, 5,6-H); 2.95 (t, J=6.1 Hz, 2H,
4,4'-H); 2.67 (t, J=6.6 Hz, 2H, 2,2'-H); 2.08 (quint, J=6.1 Hz,
J=6.6 Hz, 2H, 3,3'-H).
[0041] (8-Bromo-1,2,3,4-tetrahydronaphthalen-1-yl)phenylamine To a
stirred solution of 21.6 g (232 mmol) of aniline in 140 mL of
toluene was added 10.93 g (57.6 mmol) of TiCl.sub.4 over 30 min at
23.degree. C. under argon atmosphere. The resulting mixture was
stirred for 30 min at 90.degree. C. followed by an addition of 13.1
g (57.6 mmol) of 8-bromo-3,4-dihydronaphthalen-1(2H)-one. This
mixture was stirred for 10 min at 90.degree. C., then cooled to
23.degree. C., and poured into 500 mL of water. The product was
extracted with 3.times.50 mL of ethyl acetate. The combined organic
extract was dried over Na.sub.2SO.sub.4, evaporated to dryness, and
the residue was re-crystallized from 10 mL of ethyl acetate. The
obtained crystalline solid was dissolved in 200 mL of methanol,
7.43 g (118 mmol) of NaBH.sub.3CN and 3 mL of acetic acid were
added in argon atmosphere. This mixture was heated to reflux for 3
h, then cooled to 23.degree. C., and evaporated to dryness. The
residue was diluted with 200 mL of water, and crude product was
extracted with 3.times.100 mL of ethyl acetate. The combined
organic extract was dried over Na.sub.2SO.sub.4 and evaporated to
dryness. The residue was purified by flash chromatography on silica
gel 60 (40-63 .mu.m, eluent: hexane-ethyl
acetate-triethylamine=100:10:1, vol.). Yield 13.0 g (75%) of a
yellow oil. Anal. Calc. for C.sub.16H.sub.16BrN: C, 63.59; H, 5.34;
N, 4.63. Found: C, 63.82; H, 5.59; N, 4.49. .sup.1H NMR
(CDCl.sub.3): .delta.7.44 (m, 1H), 7.21 (m, 2H), 7.05-7.11 (m, 2H),
6.68-6.73 (m, 3H), 4.74 (m, 1H), 3.68 (br.s, 1H, NH), 2.84-2.89 (m,
1H), 2.70-2.79 (m, 1H), 2.28-2.32 (m, 1H), 1.85-1.96 (m, 1H),
1.76-1.80 (m, 1H), 1.58-1.66 (m, 1H).
[0042]
N-Phenyl-8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4-te-
trahydronaphthalen-1-amine To a solution of 13.0 g (43.2 mmol) of
(8-bromo-1,2,3,4-tetrahydronaphthalen-1-yl)phenylamine in 250 mL
tetrahydrofuran (THF) was added 17.2 mL (43.0 mmol) of 2.5 M
.sup.nBuLi at -80.degree. C. Further on, this mixture was stirred
for 1 hr. at this temperature, and 56.0 mL (90.3 mmol) of 1.6 M
.sup.tBuLi in pentane was added. The resulting mixture was stirred
for 1 hr. at the same temperature. Then, 16.7 g (90.0 mmol) of
2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added.
After that the cooling bath was removed, and the resulting mixture
was stirred for 1 hr. at 23.degree. C. Finally, 10 mL of water was
added, and the obtained mixture was evaporated to dryness. The
residue was diluted with 200 mL of water, and crude product was
extracted with 3.times.100 mL of ethyl acetate. The combined
organic extract was dried over Na.sub.2SO.sub.4 and then evaporated
to dryness. Yield 15.0 g (98%) of a yellow oil. Anal. Calc. for
C.sub.22H.sub.28BNO.sub.2: C 75.65; H 8.08; N 4.01. Found: C 75.99;
H 8.32; N 3.79. .sup.1H NMR (CDCl.sub.3): .delta.7.59 (m, 1H),
7.18-7.23 (m, 4H), 6.71-6.74 (m, 3H), 5.25 (m, 1H), 3.87 (br.s, 1H,
NH), 2.76-2.90 (m, 2H), 2.12-2.16 (m, 1H), 1.75-1.92 (m, 3H), 1.16
(s, 6H), 1.10 (s, 6H).
[0043]
2-(8-Anilino-5,6,7,8-tetrahydronaphthalen-1-yl)-N-(2,6-diisopropylp-
henyl)quinolin-8-amine To a solution of 13.8 g (41.0 mmol) of
2-chloro-N-(2,6-diisopropylphenyl)quinolin-8-amine in 700 mL of
1,4-dioxane were added 15.0 g (43.0 mmol) of
N-phenyl-8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4-tetrahyd-
ronaphthalen-1-amine, 35.0 g (107 mmol) of cesium carbonate and 400
mL of water. The obtained mixture was purged with argon for 10 min
followed by an addition of 2.48 g (2.15 mmol) of
Pd(PPh.sub.3).sub.4. The formed mixture was stirred for 2 hrs. at
90.degree. C., then cooled to 23.degree. C. To the obtained
two-phase mixture 700 mL of n-hexane was added. The organic layer
was separated, washed with brine, dried over Na.sub.2SO.sub.4, and
then evaporated to dryness. The residue was purified by flash
chromatography on silica gel 60 (40-63 .mu.m, eluent: hexane-ethyl
acetate-triethylamine=100:5:1, vol.) and then re-crystallized from
150 mL of n-hexane. Yield 15.1 g (70%) of a yellow powder. Anal.
calc. for C.sub.37H.sub.39N.sub.3: C 84.53; H 7.48; N 7.99. Found:
C 84.60; H 7.56; N 7.84. .sup.1H NMR (CDCl.sub.3): .delta.
7.85-7.87 (d, J=7.98 Hz, 1H), 7.56 (br.s, 1H), 7.43-7.45 (d, J=8.43
Hz, 1H), 7.21-7.38 (m, 6H), 7.12 (t, J=7.77 Hz, 1H), 6.87-6.89 (d,
J=7.99 Hz, 1H), 6.74 (t, J=7.99 Hz, 1H), 6.36 (t, J=7.32 Hz, 1H),
6.14-6.21 (m, 3H), 5.35 (br.s, 1H), 3.56 (br.s, 1H), 3.20-3.41 (m,
2H), 2.83-2.99 (m, 2H), 2.10-2.13 (m, 1H), 1.77-1.92 (m, 3H),
1.13-1.32 (m, 12H).
[0044] Complex of quinolinyldiamido (QDA) Benzene (50 mL) was added
to
2-(8-anilino-5,6,7,8-tetrahydronaphthalen-1-yl)-N-(2,6-diisopropylphenyl)-
quinolin-8-amine (2.21 g, 4.20 mmol) and Hf(NMe.sub.2).sub.4 (1.58
g, 4.45 mmol) to form a clear orange solution. The mixture was
heated to reflux for 16 hrs. to form a clear red-orange solution.
Most of the volatiles were removed by evaporation under a stream of
nitrogen to afford a concentrated red solution (ca. 5 mL) that was
warmed to 40.degree. C. Then hexane (30 mL) was added and the
mixture was stirred to cause orange crystalline solid to form. This
slurry was cooled to -40.degree. C. for 30 min. then the solid was
collected by filtration and washed with additional cold hexane
(2.times.10 mL). The resulting quinolinyldiamide hafnium diamide
was isolated as an orange solid and dried under reduced pressure
(2.90 g, 3.67 mmol, 87.4% yield). This solid was dissolved in
toluene (25 mL) and Me.sub.3Al (12.8 mL, 25.6 mmol) was added. The
mixture was warmed to 40.degree. C. for 1 hr. then evaporated under
a stream of nitrogen. The crude product (2.54 g) was about 90% pure
by .sup.1H NMR spectroscopy. The solid was purified by
recrystallization from CH.sub.2Cl.sub.2-hexanes (20 mL-20 mL) by
slow evaporation to give pure product as orange crystals (1.33 g,
43.2% from ligand). The mother liquor was further concentrated for
a second crop (0.291 g, 9.5% from ligand). (Solvent:
CD.sub.2Cl.sub.2 (ca. 10 mg sample/mL solvent))(Reference
peak=CHDCl.sub.2.delta. 5.32 ppm).
[0045] Preparation of
N-[(6-bromopyridin-2-yl)methyl]-2,6-diisopropylaniline A solution
of 85.0 g (457 mmol) of 6-bromopyridine-2-carbaldehyde and 80.9 g
(457 mmol) of 2,6-diisopropylaniline in 1000 mL of ethanol was
refluxed for 8 hrs. The obtained solution was evaporated to
dryness, and the residue was re-crystallized from 200 mL of
methanol. In argon atmosphere, to thus obtained 113.5 g (329 mmol)
of N-[(1E)-(6-bromopyridin-2-yl)methylene]-2,6-diisopropylaniline
were added 33.16 g (526 mmol) of NaBH.sub.3CN, 9 mL of acetic acid
and 1000 mL of methanol. This mixture was refluxed for 12 h, then
cooled to 23.degree. C., poured into 1000 mL of water, and crude
product was extracted with 3.times.200 mL of ethyl acetate. The
combined extract was dried over sodium sulfate and evaporated to
dryness. The residue was purified by flash chromatography on silica
gel 60 (40-63 .mu.m, eluent: hexane-ethyl acetate=10:1, vol.).
Yield 104.4 g (66%) of a yellow oil. Anal. calc. for
C.sub.18H.sub.23BrN.sub.2: C, 62.25; H, 6.68; N, 8.07. Found: C,
62.40; H, 6.87; N, 7.90. .sup.1H NMR (CDCl.sub.3): .delta. 7.50 (m,
1H, 4-H in Py), 7.38 (m, 1H, 5-H in Py), 7.29 (m, 1H, 3-H in Py),
7.05-7.12 (m, 3H, 3,4,5-H in 2,6-iPr.sub.2C.sub.6H.sub.3), 4.18 (s,
2H, CH.sub.2NH), 3.94 (br.s, 1H, NH), 3.33 (sept, J=6.8 Hz, 2H,
CHMe.sub.2), 1.23 (d, J=6.8 Hz, 12H, CHMe.sub.2).
[0046] Preparation of 7-bromoindan-1-ol To a mixture of 100 g (746
mmol) of indan-1-ol, 250 mL (1.64 mol) of
N,N,N',N'-tetramethylethylenediamine, and 3000 mL of pentane cooled
to -20.degree. C., 655 mL (1.64 mol) of 2.5M nBuLi in hexanes was
added. The reaction mixture was then refluxed for 12 hrs. and then
cooled to -80.degree. C. Then, 225 mL (1.87 mol) of
1,2-dibromotetrafluoroethane was added, and the resulting mixture
was allowed to warm to 23.degree. C. This mixture was stirred for
12 h, and then 100 mL of water was added. The resulting mixture was
diluted with 2000 mL of water, and the organic layer was separated.
The aqueous layer was extracted with 3.times.400 mL of toluene. The
combined organic extract was dried over Na.sub.2SO.sub.4 and
evaporated to dryness. The residue was distilled using a Kugelrohr
apparatus, b.p. 120-140.degree. C./1 mbar. The resulting yellow oil
was dissolved in 50 mL of triethylamine, and the obtained solution
added dropwise to a stirred solution of 49.0 mL (519 mmol) of
acetic anhydride and 4.21 g (34.5 mmol) of
4-(dimethylamino)pyridine in 70 mL of triethylamine. The resulting
mixture was stirred for 5 min, then 1000 mL of water was added, and
stirring was continued for 12 hrs. Then, the reaction mixture was
extracted with 3.times.200 mL of ethyl acetate. The combined
organic extract was washed with aqueous Na.sub.2CO.sub.3, dried
over Na.sub.2SO.sub.4, and evaporated to dryness. The residue was
purified by flash chromatography on silica gel 60 (40-63 .mu.m,
eluent: hexane-ethyl acetate=30:1, vol.). The resulting ester was
dissolved in 1000 mL of methanol, 50.5 g (900 mmol) of KOH was
added, and this mixture was refluxed for 3 hrs. The reaction
mixture was then cooled to 23.degree. C. and poured into 4000 mL of
water. Crude product was extracted with 3.times.300 mL of
dichloromethane. The combined organic extract was dried over
Na.sub.2SO.sub.4 and evaporated to dryness. Yield 41.3 g (26%) of a
white crystalline solid. Anal. Calc for C.sub.9H.sub.9BrO: C 50.73;
H 4.26. Found: C 50.85; H 4.48. .sup.1H NMR (CDCl.sub.3): .delta.
7.34 (d, J=7.6 Hz, 1H, 6-H); 7.19 (d, J=7.4 Hz, 1H, 4-H); 7.12 (dd,
J=7.6 Hz, J=7.4 Hz, 1H, 5-H); 5.33 (dd, J=2.6 Hz, J=6.9 Hz, 1H,
1-H), 3.18-3.26 (m, 1H, 3- or 3'-H), 3.09 (m, 2H, 3,3'-H); 2.73 (m,
2H, 2,2'-H).
[0047] Preparation of 7-bromoindan-1-one to a solution of 37.9 g
(177 mmol) of 7-bromoindan-1-ol in 3500 mL of dichloromethane 194 g
(900 mmol) of pyridinium chlorochromate was added. The resulting
mixture was stirred at 23.degree. C. for 5 hrs., then passed
through a silica gel pad (500 mL), and the elute was evaporated to
dryness. Yield 27.6 g (74%) of a white crystalline solid. Anal.
Calc for C.sub.9H.sub.7BrO: C 51.22; H 3.34. Found: C 51.35; H
3.41. .sup.1H NMR (CDCl.sub.3): .delta. 7.51 (m, 1H, 6-H);
7.36-7.42 (m, 2H, 4,5-H); 3.09 (m, 2H, 3,3'-H); 2.73 (m, 2H,
2,2'-H).
[0048] Preparation of 7-bromo-N-phenyl-2,3-dihydro-1H-inden-1-amine
To a stirred solution of 10.4 g (112 mmol) of aniline in 60 mL of
toluene 5.31 g (28.0 mmol) of TiCl.sub.4 was added for 30 min at
23.degree. C. in argon atmosphere. The resulting mixture was
stirred at 90.degree. C. for 30 min followed by an addition of 6.00
g (28.0 mmol) of 7-bromoindan-1-one. The resulting mixture was
stirred for 10 min at 90.degree. C., poured into 500 mL of water,
and crude product was extracted with 3.times.100 mL of ethyl
acetate. The organic layer was separated, dried over
Na.sub.2SO.sub.4, and then evaporated to dryness. The residue was
crystallized from 10 mL of ethyl acetate at -30.degree. C. The
resulting solid was separated and dried in vacuum. After that it
was dissolved in 100 mL of methanol, 2.70 g (42.9 mmol) of
NaBH.sub.3CN and 0.5 mL of glacial acetic acid was added. The
resulting mixture was refluxed for 3 hrs. in argon atmosphere. The
resulting mixture was cooled to 23.degree. C. and then evaporated
to dryness. The residue was diluted with 200 mL of water, and crude
product was extracted with 3.times.50 mL of ethyl acetate. The
combined organic extract was dried over Na.sub.2SO.sub.4 and
evaporated to dryness. The residue was purified by flash
chromatography on silica gel 60 (40- 63 .mu.m, eluent: hexane-ethyl
acetate-triethylamine=100:10:1, vol.). Yield 5.50 g (68%) of a
yellow oil. Anal. calc. for C.sub.15H.sub.14BrN: C, 62.52; H, 4.90;
N 4.86. Found: C, 62.37; H, 5.05; N 4.62. .sup.1H NMR (CDCl.sub.3):
.delta. 7.38 (m, 1H, 6-H in indane); 7.22 (m, 3H, 3,5-H in phenyl
and 4-H in indane); 7.15 (m, 1H, 5-H in indane); 6.75 (m, 1H, 4-H
in indane); 6.69 (m, 2H, 2,6-H in phenyl); 4.94 (m, 1H, 1-H in
indane); 3.82 (br.s, 1H, NH); 3.17-3.26 (m, 1H, 3- or 3'-H in
indane); 2.92-2.99 (m, 2H, 3'- or 3-H in indane); 2.22-2.37 (m, 2H,
2,2'-H in indane).
[0049] Preparation of
N-phenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,3-dihydro-1H-i-
nden-1-amine To a solution of 2.50 g (8.70 mmol) of
7-bromo-N-phenyl-2,3-dihydro-1H-inden-1-amine in 50 mL THF 3.50 mL
(8.70 mmol) of 2.5M .sup.nBuLi in hexanes was added at -80.degree.
C. in argon atmosphere. The reaction mixture was then stirred for 1
hr. at this temperature. Then, 11.1 mL (17.8 mmol) of 1.7M
.sup.tBuLi in pentane was added, and the reaction mixture was
stirred for 1 hr. Then, 3.23 g (17.4 mmol) of
2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added.
Then, the cooling bath was removed, and the resulting mixture was
stirred for 1 hr. at 23.degree. C. To the formed mixture 10 mL of
water was added, and the resulting mixture was evaporated to
dryness. The residue was diluted with 200 mL of water, and the
title product was extracted with 3.times.50 mL of ethyl acetate.
The combined organic extract was dried over Na.sub.2SO.sub.4 and
evaporated to dryness. Yield 2.80 g (96%) of a light yellow oil.
Anal. calc. For C.sub.21H.sub.26BNO.sub.2: C 75.24; H 7.82; N 4.18.
Found: C 75.40; H 8.09; N 4.02. .sup.1H NMR (CDCl.sub.3): .delta.
7.63 (m, 1H, 6-H in indane); 7.37-7.38 (m, 1H, 4-H in indane);
7.27-7.30 (m, 1H, 5-H in indane); 7.18 (m, 2H, 3,5-H in phenyl);
6.65-6.74 (m, 3H, 2,4,6-H in phenyl); 5.20-5.21 (m, 1H, 1-H in
indane); 3.09-3.17 (m, 1H, 3- or 3'-H in indane); 2.85-2.92 (m, 1H,
3'- or 3-H in indane); 2.28-2.37 (m, 1H, 2- or 2'-H in indane);
2.13-2.19 (m, 1H, 2'- or 2-H in indane); 1.20 (s, 6-H, 4,5-Me in
BPin); 1.12 (s, 6H, 4',5'-Me in BPin).
[0050] Preparation of
7-(6-(((2,6-diisopropylphenyl)amino)methyl)pyridin-2-yl)-N-phenyl-2,3-dih-
ydro-1H-inden-1-amine A solution of 2.21 g (21.0 mmol) of
Na.sub.2CO.sub.3 in a mixture of 80 mL of water and 25 mL of
methanol was purged with argon for 30 min. The obtained solution
was added to a mixture of 2.80 g (8.40 mmol) of
N-phenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,3-dihydro-1H-i-
nden-1-amine, 2.90 g (8.40 mmol) of
N-[(6-bromopyridin-2-yl)methyl]-2,6-diisopropylaniline, 0.48 g
(0.40 mmol) of Pd(PPh.sub.3).sub.4, and 120 mL of toluene. This
mixture was stirred for 12 hrs. (h) at 70.degree. C., then cooled
to 23.degree. C. The organic layer was separated, the aqueous layer
was extracted with 3.times.50 mL of ethyl acetate. The combined
organic extract was washed with brine, dried over Na.sub.2SO.sub.4
and evaporated to dryness. The residue was purified by flash
chromatography on silica gel 60 (40-63 .mu.m, eluent: hexane-ethyl
acetate-triethylamine=100:5:1, vol.). Yield 2.00 g (50%) of a
yellow oil. Anal. calc. For C.sub.33H.sub.37N.sub.3: C 83.33; H
7.84; N 8.83. Found: C 83.49; H 7.66; N 8.65. .sup.1H NMR
(CDCl.sub.3): .delta. 7.56-7.61 (m, 3H, 6-H in indane and 4.5-H in
Py); 7.46-7.51 (m, 2H, 3,5-H in phenyl); 7.14-7.16 (m, 1H, 4-H in
indane); 7.08-7.12 (m, 5H, 3-H in Py, 3,4,5-H in
2,6-diisopropylphenyl and 5-H in indane); 6.65 (m, 1H, 4-H in
phenyl); 6.53 (m, 2H, 2,6-H in phenyl); 5.21-5.22 (m, 1H, 1-H in
indane); 3.95-4.15 (m, 4H, CH.sub.2NH and NH-phenyl and
NH-2,6-diisopropylphenyl); 3.31 (sept, J=6.8 Hz, 2H, CH in
2,6-diisopropylphenyl); 3.16-3.24 (m, 1H, 3- or 3'-H in indane);
2.91-2.97 (m, 1H, 3'- or 3-H in indane); 2.21-2.37 (m, 2H, 2,2'-H
in indane); 1.19-2.21 (m, 12H, CH.sub.3 in
2,6-diisopropylaniline).
[0051] Preparation of pyridyldiamide catalyst precursor (PDA)
Toluene (5 mL) was added to
7-(6-(((2,6-diisopropylphenyl)amino)methyl)pyridin-2-yl)-N-phenyl-2,3-dih-
ydro-1H-inden-1-amine (0.296 g, 0.623 mmol) and
Hf(NMe.sub.2).sub.2Cl.sub.2(dme) (0.267 g, 0.623 mmol) to form a
clear colorless solution. The mixture was loosely capped with
aluminum foil and heated to 95.degree. C. for 3 hrs. The mixture
was then evaporated to a solid and washed with Et.sub.2O (5 mL) to
afford 0.432 g of the presumed (pyridyldiamide) HfCl.sub.2 complex.
This was dissolved in CH.sub.2Cl.sub.2 (5 mL) and cooled to
-50.degree. C. An Et.sub.2O solution of dimethylmagnesium (3.39 mL,
0.747 mmol) was added dropwise and the mixture was allowed to warm
to ambient temperature. After 30 min. the volatiles were removed by
evaporation and the residue was extracted with CH.sub.2C.sub.12 (10
mL) and filtered. The solution was concentrated to 2 mL and pentane
(4 mL) was added. Cooling to -10.degree. C. overnight afforded
colorless crystals that were isolated and dried under reduced
pressure. Yield=0.41 g, 92%. .sup.1H NMR (CD.sub.2Cl.sub.2, 400
MHz): 8.00 (t, 1H), 6.85-7.65 (13H), 5.06 (d, 1H), 4.91 (dd, 1H),
4.50 (d, 1H), 3.68 (sept, 1H), 3.41 (m, 1H), 2.85 (m, 1H), 2.61
(sept, 1H), 2.03 (m, 1H), 1.85 (m, 1H), 1.30 (m, 2H), 1.14 (d, 3H),
1.06 (d, 3H), 0.96 (d, 3H), 0.68 (3, 3H), -0.48 (s, 3H), -0.84 (s,
3H).
[0052] Polymerization In particular, all examples were produced
using a solution polymerization process in a 1.0-liter continuous
stirred-tank reactor (autoclave reactor). The autoclave reactor was
equipped with a stirrer, a water-cooling/steam-heating element with
a temperature controller, and a pressure controller. Solvents and
monomers were purified by passing through purification columns
packed with mol sieves. Isohexane (solvent) was passed through four
columns in series whereas ethylene, propylene, and toluene were
each purified by passing through two columns in series.
Purification columns are regenerated periodically (about
twice/year) or whenever there is evidence of low catalyst activity.
5-ethylidene-2-norbornene (ENB) was purified in a glove box by
passing through a bed of basic alumina under a steady nitrogen gas
purge. 5-vinyl-2-norbornene (VNB) was purified by stirring the
diene with sodium-potassium alloy (NaK) then filtering through a
bed of basic or neutral alumina. Tri-n-octylaluminum (TNOAL,
available from Sigma Aldrich, Milwaukee, Wis.) solution was diluted
to a concentration of 1.84.times.10.sup.-6 using isohexane.
[0053] Catalyst used for examples 1-12 was the PDA catalyst
described above (MW 720.0 g/mol). The activator used was
N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate. Catalyst
solution was prepared daily and used on the same day. The solution
was prepared by dissolving 40.0 mg of the catalyst and 45.4 to 47.9
mg of the activator in 450 mL toluene (catalyst concentration=1.24
to 1.30.times.10.sup.-07 mol/mL, catalyst/activator (molar ratio)
about 0.98). This solution was pumped into the reactor through a
designated dip-tube at a desired rate using an Isco pump.
[0054] The PDA catalyst precursor was fed at a rate of
9.26.times.10.sup.-8 mol/min for samples 1-6; and
9.77.times.10.sup.-8 mol/min for samples 7-12; and activator was
fed at a rate of 9.45.times.10.sup.-8 mol/min for samples 1-6; and
9.97.times.10.sup.-8 mol/min for samples 7-12. TNOAL was fed at a
rate of 7.37.times.10.sup.-6 mol/min.
[0055] For examples 13-20, the catalyst used was the QDA catalyst
described above (732.2 g/mol). The QDA catalyst precursor was fed
at a rate of 1.82.times.10.sup.-7 mol/min; and the activator
(N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate) was fed
at a rate of 1.86.times.10.sup.-mol/min. TNOAL was fed at a rate of
7.37.times.10.sup.-6 mol/min.
[0056] Composition was controlled by adjusting the feed ratio of
the monomers. Ethylene and propylene feed rates were held constant
for all examples listed in Table 1 while the diene feed rate was
varied. No hydrogen was added. All the reactions were carried out
at a gauge pressure of about 2.2 MPa and a temperature of
110.degree. C. The collected samples were first placed on a
boiling-water steam table in a hood to evaporate a large fraction
of the solvent and unreacted monomers, and then, dried in a vacuum
oven at a temperature of about 90.degree. C. for about 12 hours.
The vacuum oven dried samples were weighed to obtain yields.
Ethylene, ENB, and VNB (VNB incorporated only through the
endocyclic double bond) content of the polymers were determined by
FTIR (ASTM D3900, ASTM D6047). Monomer conversions were calculated
using the polymer yield, composition and the amount of monomers fed
into the reactor. Catalyst activity (also referred as to catalyst
productivity) was calculated based upon the yield and the feed rate
of catalyst. Mooney measurements were made to gauge molecular
weight and long-chain branching of the EPDM terpolymers. Samples
were later analyzed using GPC as described below to determine the
molecular weight distribution as well as g' values.
[0057] In Table 1, the reactor conditions for polymerization are
set forth, and additionally include a reactor temperature of
110.degree. C.; reactor pressure of 320 psig; where the activator
was N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate; the
catalyst feed was 9.2-9.8.times.10.sup.-8 mol/min for PDA and
1.8.times.10.sup.-7 for QDA; an tri-n-octylaluminum feed was
7.4.times.10.sup.-6 mol/min; and an isohexane feed of 60-65
g/min.
TABLE-US-00001 TABLE 1 Reactor Conditions for polymerization
Reactor Input FT-IR data Ethylene Propylene ENB VNB Ethylene Feed
Feed Feed Feed H.sub.2 (wt %) ENB VNB Sample Catalyst (g/min)
(g/min) (g/min) (g/min) (SCCM) uncorrected (wt %) (wt %) 1 PDA 2.0
8.0 -- 0.00 -- 51.1% -- -- 2 PDA 2.0 8.0 -- 0.03 -- 57.2% -- 0.1% 3
PDA 2.0 8.0 -- 0.04 -- 58.4% -- 0.2% 4 PDA 2.0 8.0 -- 0.00 -- 56.6%
-- 0.0% 5 PDA 2.0 8.0 -- 0.03 -- 64.5% -- 0.1% 6 PDA 2.0 8.0 --
0.04 -- 63.6% -- 0.2% 7 PDA 2.0 8.0 0.00 -- 45.2% -- -- 8 PDA 2.0
8.0 0.04 -- 54.4% 0.8% -- 9 PDA 2.0 8.0 -- 0.00 -- 48.2% -- -- 10
PDA 2.0 8.0 -- 0.04 -- 58.3% -- 0.2% 11 PDA 2.0 8.0 -- 0.07 --
64.3% -- 0.4% 12 PDA 2.0 8.0 -- 0.11 -- 65.0% -- 0.6% 13 QDA 2.5
5.0 0.04 -- 41.6% 0.6% -- 14 QDA 2.5 5.0 0.04 2.0 43.9% 0.5% -- 15
QDA 2.5 5.0 0.07 2.0 49.3% 0.8% -- 16 QDA 2.5 5.0 0.11 2.0 57.0%
1.0% -- 17 QDA 2.5 5.0 0.14 2.0 58.0% 1.3% -- 18 QDA 2.5 5.0 --
0.04 2.0 48.1% -- 0.2% 19 QDA 2.5 5.0 -- 0.07 2.0 55.0% -- 0.4% 20
QDA 2.5 5.0 -- 0.11 2.0 55.3% -- 0.7%
TABLE-US-00002 TABLE 2 Polymer Collection and Mooney Data Cat
Collection Efficiency Sample Time (g poly/g Sample ML MLRA quantity
(g) (min) cat) 1 -- -- 37.3 15 37300 2 -- -- 24.5 15 24500 3 -- --
20.7 15 20700 4 -- -- 29.4 15 29400 5 -- -- 24.0 20 18000 6 -- --
39.3 30 19650 7 56.1 48.9 31.5 10 47250 8 53.0 55.7 69.1 30 34550 9
32.5 55.2 28.6 10 42900 10 23.1 50.8 44.2 30 22100 11 20.8 62.9
33.5 30 16750 12 16.6 77.1 26.1 30 13050 13 70.5 159.9 78.0 20
29250 14 42.3 60.9 66.5 15 33250 15 54.8 58.7 58.1 15 29050 16 64.9
85.7 44.1 15 22050 17 54.1 59.4 53.5 20 20063 18 48.9 250.8 59.3 15
29650 19 53.9 339.6 48.2 15 24100 20 27.2 154.7 45.6 15 22800
TABLE-US-00003 TABLE 3 Gel Permeation Chromatography Data Mn (LS),
Mw (LS), Sample kg/mol kg/mol g'.sub.Avg g'.sub.1000 wt % C2 units
1 64 131 1.032 -- 51.09 2 51 121 0.999 0.860 60.99 3 48 120 0.981
0.823 62.67 4 64 128 1.021 -- 57.75 5 47 104 0.995 0.785 64.46 6 48
118 0.990 0.810 63.29 7 105 220 1.029 -- 42.85 8 87 197 0.990 0.870
52.87 9 83 175 1.028 -- 46.00 10 54 142 0.992 0.881 60.44 11 42 145
0.934 0.758 63.85 12 41 145 0.781 0.686 65.99 13 130 258 1.029
1.009 40.29 14 96 193 1.021 1.057 43.73 15 102 201 1.039 1.048
49.39 16 108 207 1.032 0.912 57.91 17 96 188 1.027 0.897 59.39 18
82 230 0.906 0.746 47.95 19 75 222 0.874 0.709 55.36 20 52 165
0.826 0.602 56.20
[0058] IR Spectrometry Total ethylene content of the elastomers was
determined using a Nicolet 6700 FTIR (ASTM D3900, ASTM D6047). The
granular elastomers from the reactor was first extruded and
pelletized. Pellet samples were compression molded into a 10 mil
thick pad. The pressed pad was placed in the instrument such that
the IR beam passes through the pad and then measures the remaining
signal on the other side. Methyl groups from the propylene affect
the absorption, so the machine was calibrated to a range of
ethylene content.
[0059] Mooney Viscosity and Mooney Relaxation Area Mooney viscosity
is a property used to monitor the quality of both natural and
synthetic rubbers. It measures the resistance of rubber to flow at
a relatively low shear rate. The highly branched polymers have a
Mooney viscosity ML (1+4) at 125.degree. C. of 30 to 100 MU
(preferably 40 to 80, preferably 45 to 70, preferably 50 to 65),
where MU is Mooney Units.
[0060] While the Mooney viscosity indicates the plasticity of the
rubber, the Mooney relaxation area (MLRA) provides a certain
indication of the effects of molecular weight distribution and
elasticity of the rubber. The highly branched compositions also
have a MLRA of 30 to 100 MU (preferably 40 to 80, preferably 45 to
70).
[0061] Another indication of melt elasticity is the ratio of
MLRA/ML (1+4). This ratio has the dimension of time and can be
considered as a "relaxation time." A higher number signifies a
higher degree of melt elasticity. Long chain branching will slow
down the relaxation of the polymer chain, hence increasing the
value of MLRA/ML (1+4). In the present compositions, the MLRA/ML is
1 or less, and as low as 0.9, or 0.8.
[0062] Mooney viscosity and Mooney relaxation area are measured
using a Mooney viscometer, operated at an average shear rate of
about 2 s.sup.-1 according to the following modified ASTM D1646: A
square of sample is placed on either side of the rotor. The cavity
is filled by pneumatically lowering the upper platen. The upper and
lower platens are electrically heated and controlled at 125.degree.
C. The torque to turn the rotor at 2 rpm is measured by a torque
transducer. The sample is preheated for 1 min. after the platens
was closed. The motor is then started and the torque is recorded
for a period of 4 min. Results are reported as ML (1+4) at
125.degree. C., where M is Mooney viscosity number, L denotes the
large rotor, "1" is the sample preheat time in min., "4" is the
sample run time in min. after the motor starts, and 125.degree. C.
is the test temperature.
[0063] The MLRA data is obtained from the Mooney viscosity
measurement when the rubber relaxed after the rotor is stopped. The
MLRA is the integrated area under the Mooney torque-relaxation time
curve from 1 to 100 secs. The MLRA can be regarded as a stored
energy term which suggests that, after the removal of an applied
strain, the longer or branched polymer chains can store more energy
and require longer time to relax. Therefore, the MLRA value of a
bimodal rubber (the presence of a discrete polymeric fraction with
very high molecular weight and distinct composition) or a long
chain branched rubber are larger than a broad or a narrow molecular
weight rubber when compared at the same Mooney viscosity
values.
[0064] Mooney viscosity values greater than about 100 cannot
generally be measured using ML (1+4) at 125.degree. C. In this
event, a higher temperature is used (e.g., 150.degree. C.), with
eventual longer shearing time (i.e., 1+8 at 125.degree. C. or
150.degree. C.), but more preferably, the Mooney measurement is
carried out using a non-standard small rotor as described below.
The non-standard rotor design is employed with a change in Mooney
scale that allows the same instrumentation on the Mooney machine to
be used with higher Mooney rubbers. This rotor is termed MST,
Mooney Small Thin, in contrast with ML.
[0065] Molecular Weight Determinations The distribution and the
moments of molecular weight (Mw, Mn, Mz, and Mw/Mn) in Table 1 were
determined by using a high temperature Gel Permeation
Chromatography (Polymer Char GPC-IR) equipped with a
multiple-channel band-filter based Infrared detector IRS, an
18-angle light scattering detector and a viscometer (not used
here). The GPC trace and mass balance traces are for Sample 3 are
shown in FIG. 1. Three Agilent PLgel 10 .mu.m Mixed-B LS columns
were used to provide polyolefin separation through size exclusion.
Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) with 300 ppm of
the antioxidant butylated hydroxytoluene was used as the mobile
phase. The TCB mixture was filtered through a 0.1 .mu.m
polytetrafluoroethylene filter and degas sed with an online degas
ser before entering the GPC instrument. The nominal flow rate was
1.0 mL/min and the nominal injection volume was 200 .mu.L. The
whole system including transfer lines, columns, detectors were
contained in an oven maintained at 145.degree. C. A given amount of
polyolefin sample was weighed and sealed in a standard vial with 80
.mu.L flow marker (heptane) added to it. After loading the vial in
the auto-sampler, polyolefin was automatically dissolved in the
instrument with 8 mL added TCB solvent. The polyolefin was
dissolved at 160.degree. C. with continuous shaking for about 1 hr.
for most polyethylene samples or 2 hrs. for polypropylene samples.
The TCB densities used in concentration calculation were 1.463 g/mL
at 23.degree. C. and 1.284 g/mL at 145.degree. C. The sample
solution concentration was from 0.2 to 2.0 mg/mL, with lower
concentrations being used for higher molecular weight samples.
[0066] The concentration "c" at each point in the chromatogram was
calculated from the baseline-subtracted IR5 broadband signal
intensity "I" using the following equation:
c=.beta.I,
where .beta. is the mass constant determined with polyethylene or
polypropylene standards. The mass recovery was calculated from the
ratio of the integrated area of the concentration chromatography
over elution volume and the injection mass which is equal to the
pre-determined concentration multiplied by injection loop
volume.
[0067] The conventional molecular weight (IR molecular weight "M")
was determined by combining universal calibration relationship with
the column calibration which was performed with a series of
mono-dispersed polystyrene (PS) standards ranging from 700 g/mole
to 10,000,000 g/mole. The molecular weight "M" at each elution
volume was calculated with following equation:
log M = log ( K PS / K ) a + 1 + a PS + 1 a + 1 log M PS ,
##EQU00003##
where the variables with subscript "PS" stands for "polystyrene"
while those without a subscript are for the test samples. In this
method, a.sub.PS=0.67 and K.sub.PS=0.000175 while "a" and "K" are
calculated from a series of empirical formula established in the
literature (T. Sun, P. Brant, R. R. Chance, and W. W. Graessley,
34(19) MACROMOLECULES 6812-6820 (2001)). Specifically, the value of
a/K is 0.695/0.000579 for polyethylene and 0.705/0.0002288 for
polypropylene. Molecular weight is expressed in g/mole or kg/mole.
The values for Mw are determined .+-.500 g/mole, and for Mn .+-.100
g/mole.
[0068] The comonomer composition is determined by the ratio of the
IRS detector intensity corresponding to CH.sub.2 and CH.sub.3
channel calibrated with a series of PE and PP homo/copolymer
standards whose nominal value are predetermined by NMR or FTIR such
as an ExxonMobil Chemical Company commercial grade of LLDPE,
polypropylene, etc.
[0069] The LS detector is the 18-angle Wyatt Technology High
Temperature Dawn Heleosii.TM.. The LS molecular weight "M" at each
point in the chromatogram is determined by analyzing the LS output
using the Zimm model for static light scattering (W. Burchard &
W. Ritchering, "Dynamic Light Scattering from Polymer Solutions,"
in 80 PROGRESS IN COLLOID & POLYMER SCIENCE, 151-163
(Steinkopff, 1989)):
K o c .DELTA. R ( .theta. ) = 1 MP ( .theta. ) + 2 A 2 c ,
##EQU00004##
here, .DELTA.R(.theta.) is the measured excess Rayleigh scattering
intensity at scattering angle .theta., "c" is the polymer
concentration determined from the infrared analysis, A.sub.2 is the
second virial coefficient. P(.theta.) is the form factor for a
monodisperse random coil, and K.sub.o is the optical constant for
the system:
K o = 4 .pi. 2 n 2 ( dn / dc ) 2 .lamda. 4 N A , ##EQU00005##
where N.sub.A is Avogadro's number, and (dn/dc) is the refractive
index increment for the system. The refractive index, n=1.500 for
TCB at 145.degree. C. and .lamda.=665 nm.
[0070] A high temperature Agilent (or Viscotek Corporation)
viscometer, which has four capillaries arranged in a Wheatstone
bridge configuration with two pressure transducers, is used to
determine specific viscosity and branching. One transducer measures
the total pressure drop across the detector, and the other,
positioned between the two sides of the bridge, measures a
differential pressure. The specific viscosity, .eta..sub.S, for the
solution flowing through the viscometer is calculated from their
outputs. The intrinsic viscosity, [.eta.], at each point in the
chromatogram is calculated from the following equation:
[.eta.]=.eta..sub.S/c,
where c is concentration and was determined from the infrared (IR5)
broadband channel output. The viscosity "M" at each point is
calculated from the below equation:
M=K.sub.PSM.sup..alpha.PS+1/[.eta.].
[0071] The branching index (g'.sub.avg) is calculated using the
output of the GPC-IR5-LS-VIS method as follows. The average
intrinsic viscosity, [.eta..sub.avg], of the sample is calculated
by:
[ .eta. ] avg = c i [ .eta. ] i c i , ##EQU00006##
where the summations are over the chromatographic slices, "i",
between the integration limits. The branching index g'.sub.avg is
defined as:
g avg ' = [ .eta. ] avg kM v .alpha. . ##EQU00007##
[0072] The M.sub.v is the viscosity-average molecular weight based
on molecular weights determined by LS analysis. Also, as used
herein the g'.sub.1000 is the value of g' at a molecular weight of
1,000,000 g/mole, thus a measure of the amount of branching on the
high molecular weight component of the polymer. Branching data for
inventive Sample 3 is shown in FIG. 1.
[0073] Phase Angle Dynamic shear melt rheological data was measured
with an Advanced Rheometrics Expansion System (ARES) using parallel
plates (diameter=25 mm) in a dynamic mode under nitrogen
atmosphere. For all experiments, the rheometer was thermally stable
at 190.degree. C. for at least 30 min. before inserting
compression-molded sample of resin onto the parallel plates. To
determine the samples viscoelastic behavior, frequency sweeps in
the range from 0.01 to 385 rad/s were carried out at a temperature
of 190.degree. C. under constant strain. Depending on the molecular
weight and temperature, strains of 10% and 15% were used and
linearity of the response was verified. A nitrogen stream was
circulated through the sample oven to minimize chain extension or
cross-linking during the experiments. All the samples were
compression molded at 190.degree. C. and no stabilizers were added.
A sinusoidal shear strain is applied to the material. If the strain
amplitude is sufficiently small the material behaves linearly. It
can be shown that the resulting steady-state stress will also
oscillate sinusoidally at the same frequency but will be shifted by
a phase angle .DELTA. with respect to the strain wave. The stress
leads the strain by .DELTA.. For purely elastic materials
.DELTA.=0.degree. (stress is in phase with strain) and for purely
viscous materials, .DELTA.=90.degree. (stress leads the strain by
90.degree. although the stress is in phase with the strain rate).
For viscoelastic materials, 0<.DELTA.<90. The shear thinning
slope (STS) was measured using plots of the logarithm (base ten) of
the dynamic viscosity versus logarithm (base ten) of the frequency.
The slope is the difference in the log(dynamic viscosity) at a
frequency of 100 s.sup.-1 and the log(dynamic viscosity) at a
frequency of 0.01 s.sup.-1 divided by 4. Dynamic viscosity is also
referred to as complex viscosity or dynamic shear viscosity.
[0074] Rheological data may be presented by plotting the phase
angle versus the absolute value of the complex modulus (G*) to
produce a van Gurp-Palmen plot. The plot of conventional
polyethylene polymers shows monotonic behavior and a negative slope
toward higher G* values. Conventional LLDPE polymer without long
chain branches exhibit a negative slope on the van Gurp-Palmen
plot. For branched modifiers, the phase angels shift to a lower
value as compared with the phase angle of a conventional ethylene
polymer without long chain branches at the same value of G*. The
van Gurp-Palmen plots of some embodiments of the branched modifier
polymers described in the present disclosure exhibit two slopes--a
positive slope at lower G* values and a negative slope at higher G*
values. Such a plot is presented in FIG. 2a and FIG. 2b.
[0075] Sentmanat Extensional Rheology Extensional Rheometry was
performed on an Anton-Paar MCR 501 or TA Instruments DHR-3 using a
SER Universal Testing Platform (Xpansion Instruments, LLC), model
SER2-P or SER3-G. The SER (Sentmanat Extensional Rheometer) Testing
Platform is described in U.S. Pat. Nos. 6,578,413 and 6,691,569. A
general description of transient uniaxial extensional viscosity
measurements is provided, for example, in "Strain hardening of
various polyolefins in uniaxial elongational flow," 47(3) THE
SOCIETY OF RHEOLOGY, INC., J. RHEOL., 619-630 (2003); and
"Measuring the transient extensional rheology of polyethylene melts
using the SER universal testing platform," 49(3) THE SOCIETY OF
RHEOLOGY, INC., J. RHEOL., 585-606 (2005). Strain hardening occurs
when a polymer is subjected to uniaxial extension and the transient
extensional viscosity increases more than what is predicted from
linear viscoelastic theory. Strain hardening is observed as abrupt
upswing of the extensional viscosity in the transient extensional
viscosity versus time plot. A strain hardening ratio (SHR) is used
to characterize the upswing in extensional viscosity and is defined
as the ratio of the maximum transient extensional viscosity over
three times the value of the transient zero-shear-rate viscosity at
the same strain. Strain hardening is present in the material when
the ratio is greater than 1. The SER instrument consists of paired
master and slave windup drums mounted on bearings housed within a
chassis and mechanically coupled via intermeshing gears. Rotation
of the drive shaft results in a rotation of the affixed master drum
and an equal but opposite rotation of the slave drum which causes
the ends of the polymer sample to be sound up onto the drums
resulting in the sample stretched. The sample is mounted to the
drums via securing clamps in most cases. In addition to the
extensional test, samples are also tested using transient steady
shear conditions and matched to the extensional data using a
correlation factor of three. This provides the linear viscoelastic
envelope (LVE). Rectangular sample specimens with dimensions
approximately 18.0 mm long.times.12.70 mm wide are mounted on the
SER fixture. Samples are generally tested at three Hencky strain
rates: 0.01 s.sup.-1, 0.1 s.sup.-1 and 1 s.sup.-1. The testing
temperature is 150.degree. C. The polymer samples were prepared as
follows: the sample specimens were hot pressed at 190.degree. C.,
mounted to the fixture, and equilibrated at 150.degree. C. Such
plots are presented in FIG. 3 for a comparative elastomer and FIG.
4 for an inventive Sample 3 elastomer.
[0076] With respect to a composition or polyolefin, "consisting
essentially of" means that the claimed polyolefin, composition
and/or article includes the named components and no additional
components that will alter its measured properties by any more than
.+-.1, 2, 5, or 10%, and most preferably means that "additives" are
present, if at all, to a level of less than 5, or 4, or 3, or 2 wt
% by weight of the composition. Such additional additives can
include, for example, inorganic fillers (such as talc, glass, and
other minerals), carbon black, nucleators, clarifiers, colorants
(soluble and insoluble), foaming agents, antioxidants,
alkyl-radical scavengers (preferably vitamin E or other tocopherols
and/or tocotrienols), anti-ultraviolet light agents, acid
scavengers, curatives and cross-linking agents, mineral and
synthetic oils, aliphatic and/or cyclic containing oligomers or
polymers (and other "hydrocarbon resins"), and other additives well
known in the art.
[0077] With respect to a process or apparatus, the phrase
"consisting essentially of" means that the claimed process does not
include any other process steps (or apparatus features/means) that
change the nature of the overall claimed process, such as an
additional polymerization step, or additional olefin/polyolefin
separation step, or additional re-directing of polymerization
medium flow, heating, cooling, pressurizing, and/or depressurizing
that impart a change in the final polyolefin product by any more
than .+-.1, 2, or 5% from a measured chemical properties.
[0078] For all jurisdictions in which the doctrine of
"incorporation by reference" applies, all of the test methods,
patent publications, patents and reference articles are hereby
incorporated by reference either in their entirety or for the
relevant portion for which they are referenced.
* * * * *