U.S. patent application number 15/590559 was filed with the patent office on 2018-11-15 for olefin polymerization catalyst components and process for the production of olefin polymers therewith.
The applicant listed for this patent is Formosa Plastics Corporation, USA. Invention is credited to Chih-Jian Chen, Yiqun Fang, Gapgoung Kong, Demin Xu, Lei Zhang.
Application Number | 20180326407 15/590559 |
Document ID | / |
Family ID | 64050700 |
Filed Date | 2018-11-15 |
United States Patent
Application |
20180326407 |
Kind Code |
A1 |
Kong; Gapgoung ; et
al. |
November 15, 2018 |
Olefin polymerization catalyst components and process for the
production of olefin polymers therewith
Abstract
The present invention relates to a Ziegler-Natta catalyst
component for olefin polymerization containing an amide element in
combination with one or more internal electron donors. The catalyst
components, according to the present invention, are able to produce
polypropylene polymers with higher stereo-regularity. The present
invention also provides a phthalate-free catalyst system capable of
producing polypropylene with an isotacticity that is equal to or
higher than catalyst systems containing phthalate derivatives.
Inventors: |
Kong; Gapgoung; (Sugarland,
TX) ; Zhang; Lei; (Port Lavaca, TX) ; Xu;
Demin; (Port Lavaca, TX) ; Fang; Yiqun; (Port
Lavaca, TX) ; Chen; Chih-Jian; (Port Lavaca,
TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Formosa Plastics Corporation, USA |
Livingston |
NJ |
US |
|
|
Family ID: |
64050700 |
Appl. No.: |
15/590559 |
Filed: |
May 9, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08K 3/08 20130101; C08K
2003/2217 20130101; B01J 21/063 20130101; C08K 2003/0881 20130101;
Y02P 20/52 20151101; C08K 3/16 20130101; C08F 110/06 20130101; B01J
37/009 20130101; C08K 3/22 20130101; B01J 23/02 20130101; B01J
27/24 20130101; C08F 110/06 20130101; C08F 4/6548 20130101; C08F
110/06 20130101; C08F 4/651 20130101; C08F 110/06 20130101; C08F
2500/12 20130101; C08F 2500/15 20130101 |
International
Class: |
B01J 27/24 20060101
B01J027/24; B01J 35/00 20060101 B01J035/00; B01J 37/00 20060101
B01J037/00; C08F 210/00 20060101 C08F210/00; C08K 3/22 20060101
C08K003/22; C08K 3/16 20060101 C08K003/16; C08K 3/08 20060101
C08K003/08 |
Claims
1. A solid catalyst component for the polymerization or
co-polymerization of alpha-olefins comprising: titanium, magnesium,
halogen, one or more internal electron donors, and one or more
amide compounds selected from the compound represented by the
formula: ##STR00003## wherein R is an aliphatic hydrocarbon having
1 to 20 carbon atoms and contains a carbonyl or carbonyl ester
group; wherein R.sup.1 is alkyl group having 1 to 20 carbon atoms;
and wherein R.sup.2 is hydrogen, alkyl group having 1 to 20 carbon
atom, phenyl, carbonyl or alkoxy carbonyl.
2. (canceled)
3. The component of claim 1, wherein the one or more amide
compounds are selected from cyclic amide compounds, wherein two or
more of R, R.sup.1, and R.sup.2 are linked to form one or more
saturated or unsaturated monocyclic or polycyclic rings.
4. The component of claim 1, wherein the one or more amide
compounds are non-cyclic amide compounds.
5. The component of claim 1, wherein the one or more amide
compounds are selected from 3-ethoxycarbonyl-2-piperidone,
n-methyl-2-piperidone, 2-piperidone, 2-pyrrolidinone,
n-tert-butoxycarbonyl-2-piperidone, n-methyl-2-pyridone,
1-cyclohexyl-2-pyrrolidone, 1-benzyl-2-piperidone,
1-phenyl-2-pyrrolidinone, n,n-dimethylpropionamide,
n,n-dimethylisobutyramide, n,n-dimethylacetamide,
n,n-dimethylpentanamide, n,n-dimethylhexanamide, and their
derivatives.
6. The component of claim 1, wherein at least one of the one or
more internal electron donors is selected from a 1,3 diether
compound.
7. The component of claim 6, wherein the 1,3 diether compound is
selected from 9,9-bis(methoxymethyl)fluorene;
9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorene;
9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene;
9,9-bis(methoxymethyl)-2,3-benzofluorene;
9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorene;
9,9-bis(methoxymethyl)-2,7-diisopropylfluorene;
9,9-bis(methoxymethyl)-1,8-dichlorofluorene;
9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene;
9,9-bis(methoxymethyl)-1,8-difluorofluorene;
9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene;
9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene; and
9,9-bis(methoxymethyl)-4-tert-butylfluorene.
8. The component of claim 6, wherein the 1,3 diether compound is
selected from 2-(2-ethylhexyl)-1,3-dimethoxypropane,
2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane,
2-sec-butyl-1,3-dimethoxypropane,
2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-diethoxypropane,
2-cumyl-1,3-diethoxypropane,
2-(2-phenylethyl)-1,3-dimethoxypropane,
2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)
1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane,
2-(1-naphthyl)-1,3-dimethoxy propane,
2,2-fluorophenyl)-1,3-dimethoxypropane,
2-(1-decahydronaphthyl)-1,3-dimethoxypropane,
2-(p-t-butylphenyl)-1,3-dimethoxypropane,
2,2-dicyclohexyl-1,3-dimethoxypropane,
2-isopentyl-2-isopropyl-1,3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxypropane; 2-isopropyl
2-isopentyl-1,3-dimethoxypropane; and
2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane,
9. The component of claim 1, wherein at least one of the one or
more internal electron donors is selected from esters of phthalic
acid.
10. The component of claim 1, wherein at least one of the one or
more internal electron donors is selected from malonate
compounds.
11. The component of claim 1, wherein at least one of the one or
more internal electron donors is selected from esters of succinic
acid compounds.
12. The component of claim 1, wherein at least of the one or more
internal electron donors is selected from esters of diol
compounds.
13. A catalyst system for the polymerization or co-polymerization
of alpha-olefins comprising: a) a solid catalyst component
according to claim 1; and b) a co-catalyst component comprising an
organoaluminum compound represented by the general formula:
R.sub.nAlQ.sub.3-n, wherein R represents an alkyl group having 1 to
6 carbon atoms, Q represents a hydrogen or a halogen atom, and n
represents a real number that satisfies 0<n.ltoreq.3.
14. The catalyst system of claim 13, further comprising: (c) one or
more external electron donor components.
15. (canceled)
16. The catalyst system of claim 13, wherein the one or more amide
compounds of the solid catalyst component are selected from cyclic
amide compounds, wherein two or more of R, R.sup.1, and R.sup.2 are
linked to form one or more saturated or unsaturated monocyclic or
polycyclic rings.
17. The catalyst system of claim 13, wherein the one or more amide
compounds of the solid catalyst component are non-cyclic amide
compounds.
18. The catalyst system of claim 13, wherein at least one of the
one or more internal electron donors of the solid catalyst
component is selected from a 1,3 diether compound.
19. The catalyst system of claim 13, wherein at least one of the
one or more internal electron donors of the solid catalyst
component is selected from esters of phthalic acid.
20. The catalyst system of claim 13, wherein at least one of the
one or more internal electron donors of the solid catalyst
component is selected from malonate compounds.
21. The catalyst system of claim 13, wherein at least one of the
one or more internal electron donors of the solid catalyst
component is selected from esters of succinic acid compounds.
22. The catalyst system of claim 13, wherein at least one of the
one or more internal electron donors of the solid catalyst
component is selected from esters of diol compounds.
23. A solid catalyst component for the polymerization or
co-polymerization of alpha-olefins comprising: titanium, magnesium,
halogen, one or more internal electron donors, and one or more
amide compounds selected from 3-ethoxycarbonyl-2-piperidone,
n-methyl-2-piperidone, 2-piperidone, 2-pyrrolidinone,
n-tert-butoxycarbonyl-2-piperidone, n-methyl-2-pyridone,
1-cyclohexyl-2-pyrrolidone, 1-benzyl-2-piperidone,
1-phenyl-2-pyrrolidinone, n,n-dimethylpropionamide,
n,n-dimethylisobutyramide, n,n-dimethylacetamide,
n,n-dimethylpentanamide, n,n-dimethylhexanamide, and their
derivatives.
24. The component of claim 23, wherein at least one of the one or
more internal electron donors is selected from a 1,3 diether
compound.
25. The component of claim 24, wherein the 1,3 diether compound is
selected from 9,9-bis(methoxymethyl)fluorene;
9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorene;
9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene;
9,9-bis(methoxymethyl)-2,3-benzofluorene;
9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorene;
9,9-bis(methoxymethyl)-2,7-diisopropylfluorene;
9,9-bis(methoxymethyl)-1,8-dichlorofluorene;
9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene;
9,9-bis(methoxymethyl)-1,8-difluorofluorene;
9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene;
9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene; or
9,9-bis(methoxymethyl)-4-tert-butylfluorene.
26. The component of claim 24, wherein the 1,3 diether compound is
selected from 2-(2-ethylhexyl)-1,3-dimethoxypropane,
2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane,
2-sec-butyl-1,3-dimethoxypropane,
2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-diethoxypropane,
2-cumyl-1,3-diethoxypropane,
2-(2-phenylethyl)-1,3-dimethoxypropane,
2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)
1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane,
2-(1-naphthyl)-1,3-dimethoxy propane,
2,2-fluorophenyl)-1,3-dimethoxypropane,
2-(1-decahydronaphthyl)-1,3-dimethoxypropane,
2-(p-t-butylphenyl)-1,3-dimethoxypropane,
2,2-dicyclohexyl-1,3-dimethoxypropane,
2-isopentyl-2-isopropyl-1,3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxypropane; 2-isopropyl
2-isopentyl-1,3-dimethoxypropane; aor
2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane,
27. The component of claim 23, wherein at least one of the one or
more internal electron donors is selected from esters of phthalic
acid.
28. The component of claim 23, wherein at least one of the one or
more internal electron donors is selected from malonate
compounds.
29. The component of claim 23, wherein at least one of the one or
more internal electron donors is selected from esters of succinic
acid compounds.
30. The component of claim 23, wherein at least of the one or more
internal electron donors is selected from esters of diol
compounds.
31. A catalyst system for the polymerization or co-polymerization
of alpha-olefins comprising: a) a solid catalyst component
according to claim 23; and b) a co-catalyst component comprising an
organoaluminum compound represented by the general formula:
R.sub.nAlQ.sub.3-n, wherein R represents an alkyl group having 1 to
6 carbon atoms, Q represents a hydrogen or a halogen atom, and n
represents a real number that satisfies 0<n.ltoreq.3.
32. The catalyst system of claim 31, further comprising: (c) one or
more external electron donor components.
33. The catalyst system of claim 31, wherein at least one of the
one or more internal electron donors of the solid catalyst
component is selected from a 1,3 diether compound.
34. The catalyst system of claim 31, wherein at least one of the
one or more internal electron donors of the solid catalyst
component is selected from esters of phthalic acid.
35. The catalyst system of claim 31, wherein at least one of the
one or more internal electron donors of the solid catalyst
component is selected from malonate compounds.
36. The catalyst system of claim 31, wherein at least one of the
one or more internal electron donors of the solid catalyst
component is selected from esters of succinic acid compounds.
37. The catalyst system of claim 31, wherein at least one of the
one or more internal electron donors of the solid catalyst
component is selected from esters of diol compounds.
Description
BACKGROUND
1. Field of the Invention
[0001] This invention relates (1) to Ziegler-Natta catalyst
components for olefin polymerization employing specific forms of
amide compounds as an element of the solid catalyst composition in
conjunction with one or more internal donor compounds, (2) to
methods of making such polymerization catalyst systems, and (3) to
polymerization processes for producing polyolefins, particularly
polypropylene, that exhibit substantially higher stereo-regularity
and activity.
2. Description of the Related Art
[0002] Ziegler-Natta catalyst systems for polyolefin polymerization
are well known in the art. Commonly, these systems are composed of
a solid Ziegler-Natta catalyst component and a co-catalyst
component, usually an organoaluminum compound, and/or an external
electron donor to be used in conjunction. The Ziegler-Natta
catalyst components have included magnesium, halide, titanium and
internal electron donor compounds which have been widely employed
to increase the activity and stereo-specificity of polymerization
catalyst system.
[0003] Common internal electron donor compounds, which are
incorporated in the solid Ziegler-Natta catalyst component during
preparation of such component, are known in the art and include
ethers, ketones, amines, alcohols, heterocyclic organic compounds,
phenols, phosphines, and silanes. It is well known in the art that
polymerization activity, as well as stereoregularity, molecular
weight, and molecular weight distribution of the resulting polymer
depend on the molecular structure of the internal electron donor
employed. Therefore, in order to improve the polymerization process
and the properties of the resulting polymer, there has been an
effort and desire to develop various internal electron donors.
Examples of such internal electron donor compounds and their use as
a component of the catalyst system are described in U.S. Pat. Nos.
4,107,414; 4,186,107; 4,226,963; 4,347,160; 4,382,019; 4,435,550;
4,465,782; 4,522,930; 4,530,912; 4,532,313; 4,560,671; 4,657,882;
5,208,302; 5,902,765; 5,948,872; 6,048,818; 6,121,483; 6,281,301;
6,294,497; 6,313,238; 6,395,670; 6,436,864; 6,605,562; 6,716,939;
6,770,586; 6,818,583; 6,825,309; 7,022,640; 7,049,377; 7,202,314;
7,208,435; 7,223,712; 7,351,778; 7,371,802; 7,491,781; 7,544,748;
7,674,741; 7,674,943; 7,888,437; 7,888,438; 7,935,766; 7,964,678;
8,003,558; 8,003,559; 8,088,872; 8,211,819; 8,222,357; 8,227,370;
8,236,908; 8,247,341; 8,263,520; 8,263,692; 8,288,304; 8,288,585;
8,288,606; 8,318,626; 8,383,540; 8,536,290; 8,569,195; 8,575,283;
8,604,146; 8,633,126; 8,692,927; 8,664,142; 8,680,222; 8,716,514;
and 8,742,040, which are incorporated by reference herein.
[0004] In the utilization of Ziegler-Natta type catalysts for
polymerizations involving propylene or other olefins for which
isotacticity is a possibility, it may be desirable to utilize an
external electron donor, and acceptable external electron donors
include organic compounds containing O, Si, N, S, and/or P. Such
compounds include organic acids, organic acid esters, organic acid
anhydrides, ethers, ketones, alcohols, aldehydes, silanes, amides,
urea, amines, amine oxides, thiols, various phosphorus acid esters
and amides, etc. Preferred external electron donors are
organosilicon compounds containing Si--O--C and/or Si--N--C bonds,
having silicon as the central atom. Such compounds are described in
U.S. Pat. Nos. 4,472,524; 4,473,660; 4,560,671; 4,581,342;
4,657,882; 5,106,807; 5,407,883; 5,684,173; 6,228,961; 6,362,124;
6,552,136; 6,689,849; 7,009,015; 7,244,794; 7,276,463; 7,619,049;
7,790,819; 8,247,504; 8,648,001; and 8,614,162, which are
incorporated by reference herein. U.S. Pat. No. 6,271,310 listed
urea as a potential external donor that may be used for propylene
polymerization.
[0005] Most commercial propylene polymerization catalysts currently
employ alkyl phthalate esters as an internal electron donor. But
still there is a need to further improve stereo-regularity of
catalyst components employing alkyl phthalate esters as an internal
donor for the application of polypropylene polymer to impact
copolymer area. Moreover, certain environmental issues have been
recently raised concerning the continued use of phthalate
derivatives in human contact applications. As a result, the
employment of a phthalate-free propylene polymerization catalyst or
a catalyst system that employs a reduced amount of phthalate is now
necessary for the production of polypropylene to remedy these
issues.
[0006] U.S. Pat. No. 6,323,150 describes the use of a propylene
polymerization catalyst which contains a reduced amount of
phthalate as an internal electron donor. However, the resultant
polypropylene product was found to exhibit low isotacticity and
productivity. This reference further taught a polymerization
catalyst consisting of a polyether compound combined with the
phthalate derivative as internal electron donors. The resultant
polypropylene product exhibits lower isotacticity than that of a
catalyst containing only the phthalate derivative.
[0007] U.S. Pat. No. 7,491,781 teaches the use of an internal
electron donor in a propylene polymerization catalyst component
which does not contain a phthalate derivative. However the
resultant propylene polymerization catalyst produced polypropylene
with lower isotacticity than that of a catalyst containing a
phthalate derivative.
[0008] U.S. Pat. No. 7,276,463 teaches the use of compound
containing a C(.dbd.O)N bond, such as amide or urea, as an external
donor in the polymerization process, in combination with a silicon
compound and an organoaluminum compound that enables the production
of olefin polymer with improved stereo-regularity. However urea was
never employed as an element of a solid catalyst composition in the
catalyst preparation process, and never enabled production of
phthalate-free catalyst system with stereo-regularity that is equal
to or better than phthalate catalyst systems.
[0009] Recently, U.S. Patent Publ. No. 2016/0115260 A1 teaches the
use of an oxalic acid amide compound as a modifier in the
composition of solid catalyst components to improve
stereo-regularity that enables the production of phthalate-free
catalyst system with stereo-regularity that is equal to or better
than phthalate catalyst systems.
[0010] As such, there is still a need of development for a catalyst
system that can produce polypropylene with further higher
isotacticity, hydrogen response, and activity. Even more desirable
is the development of phthalate free catalyst system producing
polypropylene with even higher isotacticity and activity.
SUMMARY OF THE INVENTION
[0011] It is therefore an object of present invention to provide a
method of preparing Ziegler-Natta catalyst components for producing
polypropylene with enhanced isotacticity and activity, where the
catalyst components comprise magnesium, titanium, halide, one or
more internal electron donors, and an amide compound selected from
the compound represented by Formula I:
##STR00001##
wherein R is an aliphatic hydrocarbon having 1 to 20 carbon atoms
that may or may not contain a carbonyl or carbonyl ester group,
wherein R.sup.1 is an alkyl group having 1 to 20 carbon atoms,
wherein R and R.sup.1 may be linked to form a cyclic ring, and
R.sup.2 is hydrogen, alkyl group having 1 to 20 carbon atom,
phenyl, carbonyl or alkoxy carbonyl.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0012] In accordance with certain embodiments of the present
invention, a class of urea compound employed as an element of solid
Ziegler-Natta catalyst components in conjunction with one or more
internal donors, for the production of polyolefins, particularly
polypropylene, are disclosed. The urea compounds of the present
invention may be used in combination with one or more internal
electron donors that are typically employed in Ziegler-Natta
polypropylene catalyst systems such as 1,3-diethers, malonates,
succinates, phthalic acid esters, esters of aliphatic or aromatic
diols, or their derivatives.
[0013] According to certain aspects of the present invention, the
amide compounds that may be employed as an element of a solid
catalyst composition are represented by Formula I:
##STR00002##
wherein R is an aliphatic hydrocarbon having 1 to 20 carbon atoms
that may or may not contain carbonyl or a carbonyl ester group,
wherein R.sup.1 is alkyl group having 1 to 20 carbon atoms, wherein
R and R.sup.1 may be linked to form a cyclic ring, and R.sup.2 is
hydrogen, alkyl group having 1 to 20 carbon atom, phenyl, carbonyl,
or alkoxy carbonyl.
[0014] Preferred embodiments of the amide compounds of Formula I
include, but not limited to cyclic amide compounds, such as:
n-methyl-2-piperidone, n-ethyl-2-piperidone, n-propyl-2-piperidone,
n-butyl-2-piperidone, n-phenyl-2-piperidone, 2-piperidone,
2-pyrrolidinone, n-methyl-2-pyrrolidinone, n-ethyl-2-pyrrolidinone,
n-propyl-2-pyrrolidinone, n-butyl-2-pyrrolidinone,
n-phenyl-2-pyrrolidinone, n-methyl-caprolactam, or their
derivatives. Also, preferred embodiments of Formula I include
cyclic amide compounds containing carbonyl ester groups, such as:
3-ethoxycarbonyl-2-piperidone, 3-methoxycarbonyl-2-piperidone,
3-propoxycarbonyl-2-piperidone, 3-phenoxycarbonyl-2-piperidone,
n-tert-butoxycarbonyl-2-piperidone, n-ethoxycarbonyl-2-piperidone,
n-propoxycarbonyl-2-piperidone, n-phenoxycarbonyl-2-piperidone, or
their derivatives.
[0015] Other suitable amide compounds of Formula I include, but are
not limited to, non-cyclic amide compounds, such as
n,n-dimethylpropionamide, n,n-dimethylisobutyramide,
n,n-dimethylacetamide, n,n-dimethylpentanamide,
n,n-dimethylhexanamide n,n-diethylpropionamide, n-ethyl-n-(3-methyl
phenyl)propionamide, n,n-dimethyl-benzamide, or their
derivatives.
[0016] Acceptable Ziegler-Natta type catalyst systems that may be
used in accordance with the present invention comprise (a) a solid
Ziegler-Natta type catalyst component containing urea compound as a
modifier in conjunction with internal donors, (b) a co-catalyst
component, and optionally (c) one or more external electron donors.
Preferred solid Ziegler-Natta type catalyst component (a) include
solid catalyst components comprising a titanium compound having at
least a Ti-halogen bond and an amide compound in combination with
internal electron donor compound supported on an anhydrous
magnesium-dihalide support.
[0017] Acceptable internal electron donor compounds for the
preparation of solid Ziegler-Natta type catalyst component (a) are
not generally limited and include, but are not limited to, one or
more internal electron donors that are typically employed in
Ziegler-Natta polypropylene catalyst system, such as 1,3-diethers,
malonates, succinates, phthalic acid esters, esters of aliphatic or
aromatic diols, or their derivatives.
[0018] Examples of phthalic acid esters that may be used in
conjunction with Formula I compounds include, but are not limited
to: diethylphthalate, di-n-propylphthalate, di-n-butylphthalate,
di-n-pentylphthalate, di-i-pentylphthalate,
bis(2-ethylhexyl)phthalate, ethylisobutylphthalate,
ethyl-n-butylphthalate, di-n-hexylphthalate,
di-isobutylphthalate.
[0019] Examples of 1,3-diethers that may be used in conjunction
with Formula I compounds include, but are not limited to:
2-(2-ethylhexyl)1,3-dimethoxypropane,
2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane,
2-sec-butyl-1,3-dimethoxypropane,
2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane,
2-tert-butyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane,
2-(2-phenylethyl)-1,3-dimethoxypropane,
2,2-diethyl-1,3-diethoxypropane,
2,2-dicyclopentyl-1,3-dimethoxypropane,
2,2-dipropyl-1,3-diethoxypropane, 2,2-dibutyl-1,3-diethoxypropane,
2-methyl-2-ethyl-1,3-dimethoxypropane,
2-methyl-2-propyl-1,3-dimethoxypropane,
2-methyl-2-benzyl-1,3-dimethoxypropane,
2,2-diphenyl-1,3-dimethoxypropane,
2,2-dibenzyl-1,3-dimethoxypropane,
2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane,
2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane,
2,2-diisobutyl-1,3-diethoxypropane,
2,2-diisobutyl-1,3-dibutoxypropane,
1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)indene,
1,1-bis(methoxymethyl)-7-trimethyisilylindene;
1,1-bis(methoxymethyl)-7-trifluoromethylindene,
1,1-bis(methoxymethyl)-4,7-dimethyl-4,5,6,7-tetrahydroindene,
1,1-bis(methoxymethyl)-7-methylindene,
1,1-bis(methoxymethyl)-1H-benz[e]indene,
1,1-bis(methoxymethyl)-1H-2-methylbenz[e]indene,
9,9-bis(methoxymethyl)fluorene,
9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorene,
9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene,
9,9-bis(methoxymethyl)-2,3-benzofluorene,
9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorene,
9,9-bis(methoxymethyl)-2,7-diisopropylfluorene,
9,9-bis(methoxymethyl)-1,8-dichlorofluorene,
9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene,
9,9-bis(methoxymethyl)-1,8-difluorofluorene,
9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene,
9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene,
9,9-bis(methoxymethyl)-4-tert-butylfluorene.
[0020] Examples of malonates that may be used in conjunction with
Formula I compounds include, but are not limited to:
diethyl2-isopropylmalonate, diethyl2-phenylmalonate, dineopentyl
2-isopropylmalonate, diisobutyl 2-isopropylmalonate, di-n-butyl
2-isopropylmalonate, diethyl 2-dodecylmalonate, diethyl
2-t-butylmalonate, diethyl 2-(2-pentyl)malonate, diethyl
2-cyclohexylmalonate, dineopentyl 2-t-butylmalonate, dineopentyl
2-isobutylmalonate, diethyl 2-cyclohexylmethylmalonate, dimethyl
2-cyclohexylmethylmalonate, diethyl 2,2-dibenzylmalonate, diethyl
2-isobutyl-2-cyclohexylmalonate, dimethyl
2-n-butyl-2-isobutylmalonate, diethyl 2-n-butyl-2-isobutylmalonate,
diethyl 2-isopropyl-2-n-butylmalonate, diethyl
2-methyl-2-isopropylmalonate, diethyl
2-isopropyl-2-isobutylmalonate, diethyl
2-methyl-2-isobutylmalonate, diethyl 2-isobutyl-2-benzylmalonate,
diethyldiisobutylmalonate.
[0021] Examples of succinates that may be used in conjunction with
Formula I compounds include, but are not limited to: diethyl
2,3-bis(trimethylsilyl)succinate, diethyl
2,3-bis(2-ethylbutyl)succinate, diethyl 2,3-dibenzylsuccinate,
diethyl 2,3-diisopropylsuccinate, diisobutyl
2,3-diisopropylsuccinate, diethyl
2,3-bis(cyclohexylmethyl)succinate, diethyl
2,3-diisobutylsuccinate, diethyl 2,3-dineopentylsuccinate, diethyl
2,3-dicyclopentylsuccinate, diethyl 2,3-dicyclohexylsuccinate.
[0022] Examples of esters of aliphatic or aromatic diols that may
be used in conjunction with Formula I compounds include, but are
not limited to: 1,3-propylene-glycol dibenzoate,
2-methyl-1,3-propylene-glycol dibenzoate,
2-ethyl-1,3-propylene-glycol dibenzoate,
2-propyl-1,3-propylene-glycol dibenzoate,
2-butyl-1,3-propylene-glycol dibenzoate,
2,2-dimethyl-1,3-propylene-glycol dibenzoate,
(R)-1-phenyl-1,3-propylene-glycol dibenzoate,
(S)-1-phenyl-1,3-propylene-glycol dibenzoate,
1,3-diphenyl-1,3-propylene-glycol dibenzoate,
2-methyl-1,3-diphenyl-1,3-propylene-glycol dibenzoate,
1,3-diphenyl-1,3-propylene-glycol dipropionate,
2-methyl-1,3-diphenyl-1,3-propylene-glycol dipropionate,
2,4-pentanediol dibenzoate, 3-methyl-2,4-pentanediol dibenzoate,
3-ethyl-2,4-pentanediol dibenzoate, 3-propyl-2,4-pentanediol
dibenzoate, 3-butyl-2,4-pentanediol dibenzoate,
3,3-dimethyl-2,4-pentanediol dibenzoate,
(2S,4S)-(+)-2,4-pentanediol dibenzoate, (2R,4R)-(+)-2,4-pentanediol
dibenzoate, 2,4-pentanediol di(p-chlorobenzoate), 2,4-pentanediol
di(m-chlorobenzoate), 2,4-pentanediol di(p-bromobenzoate),
2,4-pentanediol di(o-bromobenzoate), 2,4-pentanediol
di(p-methylbenzoate) 2,4-pentanediol di(p-tert-butylbenzoate),
2,4-pentanediol di(p-butylbenzoate), 2,4-pentanediol dicinnamate,
2-methyl-1,3-pentanediol dibenzoate, 2-methyl-1,3-pentanediol
di(p-chlorobenzoate), 2-methyl-1,3-pentanediol
di(p-methylbenzoate), 2-butyl-1,3-pentanediol di(p-methylbenzoate),
2-methyl-1,3-pentanediol di(p-tert-butylbenzoate)
[0023] Acceptable anhydrous magnesium dihalides forming the support
of the solid Ziegler-Natta type catalyst component (a) are the
magnesium dihalides in active form that are well known in the art.
Such magnesium dihalides may be preactivated, may be activated in
situ during the titanation, may be formed in-situ from a magnesium
compound, which is capable of forming magnesium dihalide when
treated with a suitable halogen-containing transition metal
compound, and then activated. Preferred magnesium dihalides are
magnesium dichloride and magnesium dibromide. The water content of
the dihalides is generally less than 1% by weight.
[0024] The solid Ziegler-Natta type catalyst component (a) may be
made by various methods. One such method consists of co-grinding
the magnesium dihalide and the internal electron donor compound
until the product shows a surface area higher than 20 m.sup.2/g and
thereafter reacting the ground product with the Ti compound. Other
methods of preparing solid Ziegler-Natta type catalyst component
(a) are disclosed in U.S. Pat. Nos. 4,220,554; 4,294,721;
4,315,835; 4,330,649; 4,439,540; 4,816,433; and 4,978,648. These
methods are incorporated herein by reference.
[0025] In a typical modified solid Ziegler-Natta type catalyst
component (a), the molar ratio between the magnesium dihalide and
the halogenated titanium compound is between 1 and 500, the molar
ratio between said halogenated titanium compound and the internal
electron donor is between 0.1 and 50, and the molar ratio between
said internal electron donor and the oxalic acid diamide modifier
is between 0.1 and 100.
[0026] Preferred co-catalyst component (b) includes aluminum alkyl
compounds, which can be represented by the formula II;
R.sub.nAlQ.sub.3-n [Formula II]
wherein R.sub.n represents an alkyl group having 1 to 6 carbon
atoms, Q represents a hydrogen or a halogen atom, and n represents
a real number that satisfies 0<n.ltoreq.3. Acceptable aluminum
alkyl compounds include aluminum trialkyls, such as aluminum
triethyl, aluminum triisobutyl, and aluminum triisopropyl. Other
acceptable aluminum alkyl compounds include aluminum-dialkyl
hydrides, such as aluminum-diethyl hydrides. Other acceptable
co-catalyst component (b) includes compounds containing two or more
aluminum atoms linked to each other through hetero-atoms, such
as:
(C.sub.2H.sub.5).sub.2Al--O-A(C.sub.2H.sub.5).sub.2
(C.sub.2H.sub.5).sub.2Al--N(C.sub.6H.sub.5)--Al(C.sub.2H.sub.5).sub.2;
and
(C.sub.2H.sub.5).sub.2Al--O--SO.sub.2--O--Al(C.sub.2H.sub.5).sub.2.
[0027] Acceptable external electron donor component (c) is organic
compounds containing O, Si, N, S, and/or P. Such compounds include
organic acids, organic acid esters, organic acid anhydrides,
ethers, ketones, alcohols, aldehydes, silanes, amides, amines,
amine oxides, thiols, various phosphorus acid esters and amides,
etc. Preferred component (c) is organosilicon compounds containing
Si--O--C and/or Si--N--C bonds. Specific examples of such
organosilicon compounds are, without limitation,
trimethylmethoxysilane, diphenyldimethoxysilane,
cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane,
dicyclopentyldimethoxysilane, isobutyltriethoxysilane,
vinyltrimethoxysilane, dicyclohexyldimethoxysilane,
3-tert-Butyl-2-isobutyl-2methoxy-[1,3,2]oxazasilolidine,
3-tert-Butyl-2-cyclopentyl-2-methoxy-[1,3,2]oxazasilolidine,
2-Bicyclo[2.2.1]hept-5-en-2-yl-3-tert-butyl-2-methoxy-[1,3,2]oxazasilolid-
ine, 3-tert-Butyl-2,2-diethoxy-[1,3,2]oxazasilolidine,
4,9-Di-tert-butyl-1,6-dioxa-4,9-diaza-5-sila-spiro[4.4]nonane, and
bis(perhydroisoquinolino)dimethoxysilane. Mixtures of organic
electron donors may also be used. Finally, the oxalic acid diamides
of the present invention may also be employed as an external
electronic donor.
[0028] The olefin polymerization processes that may be used in
accordance with the present invention are not generally limited.
For example, the catalyst components (a), (b) and (c), when
employed, may be added to the polymerization reactor simultaneously
or sequentially. It is preferred to mix components (b) and (c)
first and then contact the resultant mixture with component (a)
prior to the polymerization.
[0029] The olefin monomer may be added prior to, with, or after the
addition of the Ziegler-Natta type catalyst system to the
polymerization reactor. It is preferred to add the olefin monomer
after the addition of the Ziegler-Natta type catalyst system. The
molecular weight of the polymers may be controlled in a known
manner, preferably by using hydrogen. With the catalysts produced
according to the present invention, molecular weight may be
suitably controlled with hydrogen when the polymerization is
carried out at relatively low temperatures, e.g., from about
30.degree. C. to about 105.degree. C. This control of molecular
weight may be evidenced by a measurable positive change of the Melt
Flow Rate.
[0030] The polymerization reactions may be carried out in slurry,
liquid or gas phase processes, or in a combination of liquid and
gas phase processes using separate reactors, all of which may be
done either by batch or continuously. The polyolefin may be
directly obtained from gas phase process, or obtained by isolation
and recovery of solvent from the slurry process, according to
conventionally known methods.
[0031] There are no particular restrictions on the polymerization
conditions for production of polyolefins by the method of this
invention, such as the polymerization temperature, polymerization
time, polymerization pressure, monomer concentration, etc. The
polymerization temperature is generally from 40-90.degree. C. and
the polymerization pressure is generally 1 atmosphere or
higher.
[0032] The Ziegler-Natta type catalyst systems of the present
invention may be pre-contacted with small quantities of olefin
monomer, well known in the art as prepolymerization, in a
hydrocarbon solvent at a temperature of 60.degree. C. or lower for
a time sufficient to produce a quantity of polymer from 0.5 to 3
times the weight of the catalyst. If such a prepolymerization is
done in liquid or gaseous monomer, the quantity of resultant
polymer is generally up to 1000 times the catalyst weight.
[0033] The Ziegler-Natta type catalyst systems of the present
invention are useful in the polymerization of olefins, including
but not limited to homopolymerization and copolymerization of alpha
olefins. Suitable .alpha.-olefins that may be used in a
polymerization process in accordance with the present invention
include olefins of the general formula CH.sub.2.dbd.CHR, where R is
H or C.sub.1-10 straight or branched alkyl, such as ethylene,
propylene, butene-1, pentene-1, 4-methylpentene-1 and octene-1.
While the Ziegler-Natta type catalyst systems of the present
invention may be employed in processes in which ethylene is
polymerized, it is more desirable to employ the Ziegler-Natta type
catalyst systems of the present invention in processes in which
polypropylene or higher olefins are polymerized. Processes
involving the homopolymerization or copolymerization of propylene
are preferred.
EXAMPLES
[0034] In order to provide a better understanding of the foregoing,
the following non-limiting examples are offered. Although the
examples may be directed to specific embodiments, they are not to
be viewed as limiting the invention in any specific respect. The
activity values (AC) are based upon grams of polymer produced per
gram of solid catalyst component used.
[0035] The following analytical methods are used to characterize
the polymer.
[0036] Heptane Insolubles (% HI): The weight percent (wt %) of
residuals of polypropylene sample after extracted with boiling
heptane for 8 hours.
[0037] Melt Flow rate (MI): ASTM D-1238, determined at 230.degree.
C. under the load of 2.16 kg.
[0038] T.sub.m: ASTM D-3417, determined by DSC (Manufacturer: TA
Instrument, Inc.; Model: DSC Q1000).
[0039] Determination of Isotactic Pentads Content: Place 400 mg of
polymer sample into 10 mm NMR tube. 1.7 g TCE-d2 and 1.7 g o-DCB
were added into the tube. .sup.13C NMR spectra were acquired on a
Bruker AVANCE 400 NMR (100.61 MHz, 90.degree. pulse, 12 s delay
between pulse). About 5000 transients were stored for each
spectrum; mmmm pentad peak (21.09 ppm) was used as reference. The
microstructure analysis was carried out as described in literature
(Macromolecules, 1994, 27, 4521-4524, by V. Busico, et al.).
[0040] Molecular weight (Mn and Mw): The weight average molecular
weight (Mw), number average molecular weight (Mn), and molecular
weight distribution (Mw/Mn) of polymers were obtained by gel
permeation chromatography on Water 2000GPCV system using Polymer
Labs Plgel 10 um MIXED-B LS 300.times.7.5 mm columns and
1,2,4-trichlorobenzene (TCB) as mobile phase. The mobile phase was
set at 0.9 ml/min, and temperature was set at 145.degree. C.
Polymer samples were heated at 150.degree. C. for two hours.
Injection volume was 200 microliters. External standard calibration
of polystyrene standards was used to calculate the molecular
weight.
[0041] Magnesium ethoxide (98%), anhydrous toluene (99.8%),
TiCl.sub.4 (99.9%), anhydrous n-heptane (99%), diisobutyl phthalate
(99%), cyclohexyl(dimethoxy)methylsilane (C-donor, .gtoreq.99%) and
triethylaluminum (93%) were all purchased from Sigma-Aldrich Co. of
Milwaukee, Wis., USA.
[0042] Diisopropyldimethoxysilane (P-donor) and
dicyclopentyldimethoxysilane (D-donor) were purchased from Gelest,
Inc. of Morrisville, Pa., USA.
[0043] Unless otherwise indicated, all reactions were conducted
under an inert atmosphere.
Example 1
(A) The Preparation of a Solid Catalyst Component
[0044] To a three-neck 250 ml flask equipped magnetic bar, which is
thoroughly purged with anhydrous nitrogen, 7.5 g of magnesium
ethoxide, and 70 ml of anhydrous toluene was introduced to form a
suspension. 20 ml of TiCl4 was added. The temperature of the
mixture was gradually raised to 90.degree. C., and 7.0 mmol of
9,9-bis(methoxymethyl)fluorene and 2.0 mmol of
3-ethoxycarbonyl-2-piperidone were charged. The temperature of the
mixture was increased to 110.degree. C., and maintained for 2 hours
with stirring. The resulting solid was precipitated and supernatant
liquid was decanted. The solid was washed twice with 100 ml of
anhydrous toluene at 90.degree. C., and then 80 ml of fresh
anhydrous toluene and 20 ml TiCl.sub.4 was added to the filtered
solid. Temperature of the mixture was heated to 110.degree. C., and
stirred for 2 hours. The solid was precipitated and supernatant
liquid was decanted and residual solid was washed with heptane 7
times at 70.degree. C. The final catalyst was collected and dried
under vacuum to obtain a solid catalyst component (A1).
(B) Propylene Slurry Polymerization
[0045] Propylene polymerization was conducted in a bench scale
2-liter reactor per the following procedure. The reactor was first
preheated to at least 100.degree. C. with a nitrogen purge to
remove residual moisture and oxygen. The reactor was thereafter
cooled to 50.degree. C. Under nitrogen, 1 liter dry heptane was
introduced into the reactor. When reactor temperature was about
50.degree. C., 4.3 ml of triethylaluminum (0.58M, in hexanes),
0.8-1.6 ml of dicyclopentyl(dimethoxy)silane (D-donor) (0.5 M in
heptane), and then 30 mg of the solid catalyst component (A1)
prepared above were added to the reactor. The temperature of the
reactor was heated to 50.degree. C. and 8 psi hydrogen in a 150 ml
vessel was flushed into the reactor with propylene.
[0046] The reactor temperature was then raised to 70.degree. C. The
total reactor pressure was raised to and controlled at 90 psig by
continually introducing propylene into the reactor and the
polymerization was allowed to proceed for 1 hour. After
polymerization, the reactor was vented to reduce the pressure to 0
psig and the reactor temperature was cooled to 50.degree. C.
[0047] The reactor was then opened. 500 ml methanol was added to
the reactor and the resulting mixture was stirred for 5 minutes
then filtered to obtain the polymer product. The obtained polymer
was vacuum dried at 80.degree. C. for 6 hours. The polymer was
evaluated for melt flow rate (MFR), and heptane insoluble (% HI).
The activity of catalyst (AC) was also measured. The results are
summarized in TABLE 1 & 2.
Example 2
[0048] A solid catalyst component (A2) was prepared in the same
manner as in Example 1, except that 2.0 mmol of
n-tert-buthoxycarbonyl-2-piperidone was used instead of
3-ethoxycarbonyl-2-piperidone. Propylene polymerization was carried
out in the same manner as described in Example 1, except that solid
catalyst component (A2) was charged instead of solid catalyst
component (A1). The results are summarized in TABLE 1 & 2.
Example 3
[0049] A solid catalyst component (A3) was prepared in the same
manner as in Example 1, except that 2.0 mmol of n-methylpiperidone
was used instead of 3-ethoxycarbonyl-2-piperidone. Propylene
polymerization was carried out in the same manner as described in
Example 1, except that solid catalyst component (A3) was charged
instead of solid catalyst component (A1). The results are
summarized in TABLE 1 & 2.
Example 4
[0050] A solid catalyst component (A4) was prepared in the same
manner as in Example 1, except that 2.0 mmol of
n,n-dimethylpropionamide was used instead of
3-ethoxycarbonyl-2-piperidone. Propylene polymerization was carried
out in the same manner as described in Example 1, except that solid
catalyst component (A4) was charged instead of solid catalyst
component (A1). The results are summarized in TABLE 1 & 2.
Example 5
[0051] A solid catalyst component (A5) was prepared in the same
manner as in Example 1, except that 2.0 mmol of 2-piperidone was
used instead of 3-ethoxycarbonyl-2-piperidone. Propylene
polymerization was carried out in the same manner as described in
Example 1, except that solid catalyst component (A5) was charged
instead of solid catalyst component (A1). The results are
summarized in TABLE 1 & 2.
Example 6
[0052] A solid catalyst component (A6) was prepared in the same
manner as in Example 1, except that 2.0 mmol of 2-pyrrolidinone was
used instead of 3-ethoxycarbonyl-2-piperidone. Propylene
polymerization was carried out in the same manner as described in
Example 1, except that solid catalyst component (A6) was charged
instead of solid catalyst component (A1). The results are
summarized in TABLE 1&2.
Comparative Example 1
[0053] A solid catalyst component (C1) was prepared in the same
manner as in Example 1, except that 10.0 mmol of
9,9-bis(methoxymethyl)fluorene was used instead of
diisobutylphthalate. Propylene polymerization was carried out in
the same manner as described in Example 1, except that solid
catalyst component (A8) was charged instead of solid catalyst
component (C2). The results are summarized in TABLE 1 & 2.
Example 7
(A) The Preparation of a Solid Catalyst Component
[0054] To a three-neck 250 ml flask equipped with fritted filter
disc and mechanical stirrer, which is thoroughly purged with
anhydrous nitrogen, 9.2 g of magnesium ethoxide, and 80 ml of
anhydrous toluene was introduced to form a suspension. 20 ml of
TiCl4 was added through a stainless steel cannula. The temperature
of the mixture was gradually raised to 90.degree. C., and 10.0 mmol
of diisobutylphthalate and 2.0 mmol of
3-ethoxycarbonyl-2-piperidone were charged. The temperature of the
mixture was increased to 110.degree. C., and maintained for 2 hours
with stirring. The resulting solid was filtered and washed twice
with 100 ml of anhydrous toluene at 90.degree. C., and then 80 ml
of fresh anhydrous toluene and 20 ml TiCl.sub.4 was added to the
filtered solid. Temperature of the mixture was heated to
110.degree. C., and stirred for 2 hours. The solid was filtered and
residual solid was washed with heptane 7 times at 70.degree. C. The
final catalyst was collected and dried under vacuum to obtain a
solid catalyst component (A7).
(B) Propylene Slurry Polymerization
[0055] Propylene polymerization was carried out in the same manner
as described in Example 1, except that solid catalyst component
(A7) was charged instead of solid catalyst component (A1).
[0056] The results are summarized in TABLE 1 & 2.
Comparative Example 2
(A) The Preparation of a Solid Catalyst Component (C2)
[0057] A solid catalyst component (C2) was prepared in the same
manner as in Example 7, except that of
3-ethoxycarbonyl-2-piperidone was not added.
(B) Propylene Slurry Polymerization
[0058] Propylene polymerization was carried out in the same manner
as described in Example 1, except that solid catalyst component
(C2) was charged instead of solid catalyst component (A1). The
results are summarized in TABLE 1 & 2.
TABLE-US-00001 TABLE 1 Amide element & internal donor
composition in solid Catalyst Components Catalyst Internal Example
components Donor (mmol) amide element (mmol) Ex. 1 A1 1,3-diether**
3-ethoxycarbonyl-2- (7.0) piperidone (2.0) Ex. 2 A2 1,3-diether**
n-tert-butoxycarbonyl-2- (7.0) piperidone (2.0) Ex. 3 A3
1,3-diether** n-methyl-2-piperidone (7.0) (2.0) Ex. 4 A4
1,3-diether** n,n-dimethylpropionamide (7.0) (2.0) Ex. 5 A5
1,3-diether** 2-piperidone (7.0) (2.0) Ex. 6 A6 1,3-diether**
2-pyrrolidinone (7.0) (2.0) Comp. Ex 1 C1 1,3-diether** Without
amide element (7.0) Ex. 7 A7 DiBP* (10.0) 3-ethoxycarbonyl-2-
piperidone (2.0) Comp. Ex 2 C2 DiBP* (10.0) Without amide element
*DiBP = Diisobutylphthalate **1,3 diether =
9,9-bis(methoxymethyl)fluorene
TABLE-US-00002 TABLE 2 Polymerization Summary Ext. Donor H2 MFR
Activity HI Example Catalyst (mmol) (psi) (g/10 min) (g/g cat.) (%)
Ex. 1 A1 P (0.4) 8 11.8 3470 98.6 Ex 2 A2 P (0.4) 8 9.7 3566 98.5
Ex. 3 A3 P (0.4) 8 9.6 3010 98.6 Ex. 4 A4 P (0.4) 8 7.6 4280 98.4
Ex. 5 A5 P (0.4) 8 9.4 2883 98.4 Ex. 6 A6 P (0.4) 8 10.5 2903 98.1
Comp. Ex 1 C1 P (0.4) 8 7.0 3533 97.2 Ex 7. A7 D (0.4) 8 1.3 7614
99.6 Comp. Ex 2 C2 D (0.4) 8 1.2 6907 99.1
[0059] As shown from the above results, the catalyst component (Ex.
1-Ex. 6) according to present invention employing amide compounds
in combination with internal donors of 1,3-diether
(9,9-bis(methoxymethyl)fluorene) as an element of catalyst
composition, produce polypropylene with an isotacticity and
activities much higher than the comparative catalyst components
(C1) that does not contain the urea element in its solid catalyst
composition. For example, for a given loading of 7.0 mmol of
1,3-diether (9,9-bis(methoxymethyl)fluorene), Catalyst component
A1-A6 containing amide element in its catalyst composition produced
polypropylene of 98.1-98.6% HI (Example 1-Example 6) with
activities of 2883-4280 gPP/gcat in the presence of 0.4 mmol P
donor, which is much higher than % HI 97.2% with activity of 3533
gPP/gcat by comparative catalyst components (C1) that does not
contain amide element in its solid catalyst composition.
[0060] The same trend has been observed in combination with
diisobutylphthalate donors. For example, in the preparation
equipped with mechanical stirrer and fritted filter disc and higher
loading of 10.0 mmol of diisobutylphthalate, catalyst component A7
containing the amide element produced polypropylene with % HI of
99.6 (Example 7), which is much higher than 99.1% for the
comparative catalyst component C2, which does not contain an amide
element in its solid catalyst composition.
[0061] As such, the present invention is well adapted to attain the
ends and advantages mentioned as well as those that are inherent
therein. The particular embodiments disclosed above are
illustrative only, as the present invention may be modified and
practiced in different but equivalent manners apparent to those
skilled in the art having the benefit of the teachings herein.
Furthermore, no limitations are intended to the details of
construction or design herein shown, other than as described in the
claims below. It is therefore evident that the particular
illustrative embodiments disclosed above may be altered or modified
and all such variations are considered within the scope and spirit
of the present invention. Whenever a numerical range with a lower
limit and an upper limit is disclosed, any number falling within
the range is specifically disclosed. Moreover, the indefinite
articles "a" or "an", as used in the claims, are defined herein to
mean one or more than one of the element that it introduces.
* * * * *