U.S. patent application number 15/662976 was filed with the patent office on 2017-12-14 for olefin polymerization catalyst carrier, solid catalyst component and use thereof.
The applicant listed for this patent is Renqiu Lihe Technology Ltd.. Invention is credited to Jinsong Dai, Le Hu, Huashu Li, Shuhang Li, Qingli Ma, Jingyu Wang, Zhiwu WANG, Hui Zhang, Junwei Zhang.
Application Number | 20170355792 15/662976 |
Document ID | / |
Family ID | 53118516 |
Filed Date | 2017-12-14 |
United States Patent
Application |
20170355792 |
Kind Code |
A1 |
WANG; Zhiwu ; et
al. |
December 14, 2017 |
OLEFIN POLYMERIZATION CATALYST CARRIER, SOLID CATALYST COMPONENT
AND USE THEREOF
Abstract
Provided is an olefin polymerization catalyst carrier with a
general structure formula of Mg(OR.sup.I).sub.n(OR.sup.II).sub.2-n,
wherein: 0.ltoreq.n.ltoreq.2, and R.sup.I and R.sup.II can be the
same or different and are each independently selected from a
C.sub.1-C.sub.20 hydrocarbon group. In the X-ray diffraction
pattern of the catalyst carrier, there are a set of diffraction
peaks in the range of a 2.theta. diffraction angle of
5.degree.-15.degree., and the set of diffraction peaks contain 1-4
main diffraction peaks. Also disclosed is an olefin polymerization
solid catalyst component which is prepared from the carrier
Mg(OR.sup.I).sub.n(OR.sup.II).sub.2-n, a titanium compound, and at
least one electron donor compound. In addition, also disclosed is
an olefin polymerization catalyst containing the solid catalyst
component, at least one organic aluminum compound, and optionally,
an external electron donor compound.
Inventors: |
WANG; Zhiwu; (Renqiu,
CN) ; Li; Shuhang; (Renqiu, CN) ; Li;
Huashu; (Renqiu, CN) ; Zhang; Junwei; (Renqiu,
CN) ; Zhang; Hui; (Renqiu, CN) ; Hu; Le;
(Renqiu, CN) ; Dai; Jinsong; (Renqiu, CN) ;
Ma; Qingli; (Renqiu, CN) ; Wang; Jingyu;
(Renqiu, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Renqiu Lihe Technology Ltd. |
Renqiu |
|
CN |
|
|
Family ID: |
53118516 |
Appl. No.: |
15/662976 |
Filed: |
July 28, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/CN2015/077242 |
Apr 22, 2015 |
|
|
|
15662976 |
|
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C 29/70 20130101;
C08F 4/6425 20130101; C08F 4/6492 20130101; C07C 31/28 20130101;
C01F 5/00 20130101; C08F 4/6094 20130101; C08F 4/6224 20130101;
C08F 4/646 20130101; C08F 2500/15 20130101; C08F 4/651 20130101;
C08F 10/00 20130101; C08F 10/06 20130101; C08F 4/645 20130101; C08F
110/06 20130101; C08F 4/02 20130101; C08F 4/6294 20130101; C08F
110/06 20130101; C08F 4/6024 20130101; C08F 10/02 20130101; C08F
110/06 20130101; C08F 4/651 20130101; C08F 4/6494 20130101; C08F
4/6465 20130101 |
International
Class: |
C08F 110/06 20060101
C08F110/06; C08F 4/609 20060101 C08F004/609; C08F 4/629 20060101
C08F004/629; C08F 4/622 20060101 C08F004/622; C08F 4/02 20060101
C08F004/02; C08F 4/602 20060101 C08F004/602; C08F 4/642 20060101
C08F004/642; C07C 29/70 20060101 C07C029/70; C08F 4/649 20060101
C08F004/649; C07C 31/28 20060101 C07C031/28 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 28, 2015 |
CN |
201510043331.8 |
Claims
1. An olefin polymerization catalyst carrier, having a general
formula of Mg(OR.sup.I).sub.n(OR.sup.II).sub.2-n, wherein
0.ltoreq.n.ltoreq.2, and R.sup.I and R.sup.II are same or
different, and are each independently selected from a
C.sub.1-C.sub.20 hydrocarbon group; and wherein in the X-ray
diffraction pattern of the catalyst carrier, there are a set of
diffraction peaks in the range of a 2.theta. diffraction angle of
5.degree.-15.degree., and the set of diffraction peaks contain 1-4
main diffraction peaks.
2. The catalyst carrier according to claim 1, wherein in the
catalyst carrier Mg(OR.sup.I).sub.n(OR.sup.II).sub.2-n, R.sup.I and
R.sup.II are the same or different, and are each independently
selected from a C.sub.1-C.sub.8 hydrocarbon group.
3. The catalyst carrier according to claim 1, wherein in the X-ray
diffraction pattern of the catalyst carrier
Mg(OR.sup.I).sub.n(OR.sup.II).sub.2-n, there are a set of
diffraction peaks in the range of a 2.theta. diffraction angle of
7.degree.-13.degree., and the set of diffraction peaks contain 1-4
main diffraction peaks.
4. The catalyst carrier according to claim 1, wherein in the X-ray
diffraction pattern of the catalyst carrier
Mg(OR.sup.I).sub.n(OR.sup.II).sub.2-n, there are a first set of
diffraction peaks containing 1-4 main diffraction peaks in the
range of a 2.theta. diffraction angle of 5.degree.-15.degree., and
there are a second set of diffraction peaks containing 1-3 main
diffraction peaks in the range of a 2.theta. diffraction angle of
20.degree.-30.degree..
5. The catalyst carrier according to claim 4, wherein in the X-ray
diffraction pattern of the catalyst carrier
Mg(OR.sup.I).sub.n(OR.sup.II).sub.2-n, the highest diffraction peak
is within the range of the first set of peaks.
6.-11. (canceled)
12. An olefin polymerization solid catalyst component comprising
the catalyst carrier according to claim 1, further comprising a
titanium compound with a general formula TiX.sub.n(OR).sub.4-n,
wherein R is a C.sub.1-C.sub.20 hydrocarbon group, X is a halogen,
n=0-4, and at least one electron donor compound.
13. The solid catalyst component according to claim 12, wherein the
titanium compound is selected from the group consisting of titanium
tetrachloride, titanium tetrabromide, titanium tetraiodide and
alkoxy titanium halide, and is preferably titanium
tetrachloride.
14. The solid catalyst component according to claim 12, wherein the
electron donor compound is selected from Lewis base containing one
or more electronegative groups in which the electron donor atom is
selected from the group consisting of N, O, S, P, As or Sn.
15.-17. (canceled)
18. An olefin polymerization catalyst comprising the following
components or the reactants of the following components: a) a solid
catalyst component according to claim 12; b) at least one
organoaluminum compound with a general formula
AlR.sub.nX.sub.(3-n), wherein R is a hydrogen, a hydrocarbon group
having 1-20 carbon atoms; X is a halogen, n is an integer of
0.ltoreq.n.ltoreq.3; and, optionally, c) at least one external
electron donor compound.
19. The catalyst according to claim 18, wherein the at least one
organoaluminum compound is selected from the group consisting of
trialkylaluminum compound, trialkylaluminum and alkyl aluminum
halide, alkyl aluminum cyanide, and alkyl aluminum
sesquichloride.
20. The catalyst according to claim 18, wherein the external
electron donor is selected from siloxane compounds with a general
formula R.sub.nSi(OR.sub.1).sub.4-n, wherein R and R.sub.1 are
C.sub.1-C.sub.18 hydrocarbon groups, and optionally have
heteroatoms; n is an integer of 0.ltoreq.n.ltoreq.3.
21.-22. (canceled)
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of International patent
application No. PCT/CN2015/077242 filed Apr. 22, 2015, which claims
priority to Chinese Application No. 201510043331.8 filed Jan. 28,
2015, the disclosure of each of which is incorporated by reference
herein in its entirety.
TECHNICAL FIELD
[0002] The present invention relates to an olefin polymerization
catalyst carrier, a solid catalyst component and use thereof, and
more particularly to an olefin polymerization catalyst carrier and
solid catalyst component prepared by use of
Mg(OR.sup.1).sub.n(OR.sup.2).sub.2-n, having a specific chemical
composition and physical properties, preparation method and use
thereof.
BACKGROUND ART
[0003] With the continuous development of polyolefin industry,
various types of polyolefin catalyst were developed, but widely
used effective carrier catalysts for olefin polymerization mainly
use magnesium halide as a carrier which are loaded with a
heterogenous catalyst of tetravalent titanium compound, and use
alkyl aluminum as a co-catalyst.
[0004] For the most commonly used polypropylene Ziegler-Natta
catalyst, although the final solid catalyst components prepared by
different preparation processes are similar, but their differences
in microscopic structure can be significant, causing the number of
active centers and the distribution of various active centers to
vary, therefore the difference in the performance of the catalysts
can be significant. The improvement of the catalyst preparation
processes mainly involves the use of different Mg source carriers,
different preparation processes and optimization of preparation
conditions. The carrier plays a key role in controlling the
isotacticity and morphology of the polypropylene. On the one hand,
the carrier can make TiCl4 dispersed to increase the number of
active centers. On the other hand, the carrier can make the active
center relatively fixed in position by bonding with the active
center and therefore improve the activity of the catalyst.
[0005] Over the years, people have paid more attention to the use
of different magnesium sources to prepare a magnesium carrier.
Common magnesium sources for preparing magnesium carriers mainly
include Mg powder, organic magnesium compounds (MgR.sub.2,
Mg(OR).sub.2, RMgCl, etc.) and inorganic magnesium compounds (such
as anhydrous MgCl.sub.2). The performance of the catalysts prepared
with different magnesium sources can vary. A polyalkene catalyst
having a dialkoxymagnesium as the carrier has many distinct
advantages (EP 1 209 172 A1, EP 1 270 604 A1, EP 1 260 524A1, EP 1
061 088 A1), the resulting propylene polymers have excellent
particle morphology, high stereoregularity, and other desirable
properties. In order to obtain this catalyst component for olefin
polymerization, it is necessary to prepare a dialkoxymagnesium
carrier with excellent properties first. Generally, the
Ziegler-Natta catalyst carrier with excellent performance needs to
meet the following conditions: a good morphology (e.g., shape,
particle size and its distribution), wherein the morphology of the
catalyst can be controlled by controlling the particle morphology
of the carrier to in turn control the morphology of the polymer; a
porous structure and high specific surface area; possessing active
groups for loading active catalyst components; and having an
appropriate mechanical strength.
[0006] Alkoxymagnesium carriers and their use in the preparation of
catalyst components for olefin polymerization are well known in the
art. CN1810843A describes a method of preparing a catalyst
component for olefin polymerization reaction by reacting an
alkoxymagnesium carrier with a halogenated transition metal
compound. But there is no report about the use of X-ray diffraction
pattern to analyze alkoxymagnesium carrier-related crystal material
microstructure.
[0007] As further described herein, Applicant has found that the
Mg(OR.sup.I).sub.n(OR.sup.II).sub.2-n carrier having a specific
chemical composition and physical properties can be used in a
special method to make an olefin polymerization solid catalyst
component by reacting the carrier with a titanium compound. The
catalyst component may contain at least one electron donor
compound. The olefin polymerization catalyst component prepared by
using a Mg(OR.sup.I).sub.n(OR.sup.II).sub.2-n carrier with specific
chemical composition and physical properties can be used to obtain
a catalyst with an activity higher than that of the carrier of the
prior art, and can be particularly suitable for use in the
preparation of olefin polymerization catalysts, which can have
better activity than that of the catalyst prepared by the prior
art.
SUMMARY OF THE INVENTION
[0008] The present invention was made in view of the
above-mentioned background art, and an object of the present
invention is to provide an olefin polymerization catalyst carrier
with a general formula Mg(OR.sup.I).sub.n(OR.sup.II).sub.2-n.
[0009] It is another object of the present invention to provide a
method for the preparation of said carrier.
[0010] It is also an object of the present invention to provide an
olefin polymerization solid catalyst component comprising said
carrier.
[0011] It is a further object of the present invention to provide a
method for the preparation of said olefin polymerization solid
catalyst component.
[0012] It is a still further object of the present invention to
provide a use of the olefin polymerization solid catalyst component
in the olefin polymerization.
[0013] In order to achieve the object of the present invention, the
present invention provides an olefin polymerization catalyst
carrier with a general formula
Mg(OR.sup.I).sub.n(OR.sub.II).sub.2-n (wherein 0.ltoreq.n.ltoreq.2,
and R.sup.I and R.sup.II can be the same or different, and are
C.sub.1-C.sub.20 hydrocarbon groups). In the X-ray diffraction
pattern of the catalyst carrier, there are a set of diffraction
peaks in the range of a 2.theta. diffraction angle of
5.degree.-15.degree., and the set of diffraction peaks contain 1-4
diffraction peaks. Preferably, there are a set of diffraction peaks
in the range of a 2.theta. diffraction angle of
7.degree.-13.degree., and the set of diffraction peaks contain 1-4
main diffraction peaks.
[0014] Preferably, R.sup.I and R.sup.II can be the same or
different, and are C.sub.1-C.sub.8 hydrocarbon groups.
[0015] More preferably, the carrier
Mg(OR.sup.I).sub.n(OR.sup.II).sub.2-n is selected from the group
consisting of dimethoxy magnesium, diethoxymagnesium,
dipropoxymagnesium, dibutoxymagnesium, ethoxypropoxymagnesium or
butoxyethoxymagnesium, etc. More preferably, the carrier is
diethoxymagnesium or dipropoxymagnesium.
[0016] In the X-ray diffraction pattern of the catalyst carrier,
preferably, there are a set of diffraction peaks in the range of a
2.theta. diffraction angle of 5.degree.-15.degree., and the set of
diffraction peaks contain 1-4 diffraction peaks and there are a
second set of diffraction peaks in the range of a 2.theta.
diffraction angle of 20.degree.-30.degree., and the second set of
diffraction peaks contain 1-3 diffraction peaks.
[0017] In the X-ray diffraction pattern of the catalyst carrier,
preferably, the highest peak of the first set of diffraction peaks
corresponds to 2.theta. diffraction angle of 8.degree.-13.degree.,
and the highest peak of the second set of diffraction peaks
corresponds to 2.theta. diffraction angle of
21.degree.-28.degree..
[0018] Further preferably, the highest peak of the first set of
diffraction peaks corresponds to 2.theta. diffraction angle of
9.degree.-12.degree., and the highest peak of the second set of
diffraction peaks corresponds to 2.theta. diffraction angle of
22.degree.-26.degree..
[0019] Still further preferably, the highest peak of the first set
of diffraction peaks corresponds to 2.theta. diffraction angle of
10.degree.-11.degree., and the highest peak of the second set of
diffraction peaks corresponds to 2.theta. diffraction angle of
22.degree.-24.degree..
[0020] More preferably, the highest peak of the first set of
diffraction peaks corresponds to 2.theta. diffraction angle of
10.4.degree..+-.0.2.degree., and the highest peak of the second set
of diffraction peaks corresponds to 2.theta. diffraction angle of
23.1.degree..+-.0.2.degree.. Among them, the highest diffraction
peak of all peaks is within the range of the first set of
peaks.
[0021] It is possible, but not strictly necessary, that the carrier
of the present invention can also be measured for its particle
morphology by electron microscopy. The morphology by electron
microscope shows the appearance is a non-spherical solid that is a
solid with clear edges and corners.
[0022] The present invention also provides a method for preparing
an olefin polymerization catalyst carrier comprising reacting an
alcohol (A) with a metal magnesium powder (B) in the presence of a
halogen or a halogen-containing compound (C) to form a magnesium
compound (D), i.e., the carrier. Preferably, the dried or non-dried
magnesium compound (D) after the reaction is treated at high
temperature and high pressure to obtain a carrier.
[0023] Alternatively, an alcohol (A) is reacted with a metal
magnesium powder (B) in the presence of a halogen or a
halogen-containing compound (C), and is subjected to a high
temperature and high pressure continuous treatment to obtain a
carrier.
[0024] The specific preparation method comprises the following
steps:
[0025] 1) an alcohol (A) is reacted with a metal magnesium powder
(B) in the presence of a halogen or a halogen-containing compound
(C) to form a magnesium compound (D), the molar ratio of (A) and
(B) is from 3 to 5, and the molar ratio of (C) and (B) is from
0.002 to 0.01;
[0026] 2) when the viscosity of the reaction solution rises
sharply, (A) or the inert organic solvent (E) or a mixed solution
of (A) and (E) is added, the molar ratio of added amount and (B) is
from 2 to 7;
[0027] 3) after the above reaction is complete, a solid suspension
is obtained, or the solvent is filtered off under pressure to give
a solid dry powder (D).
[0028] Preferably, a step 4) is further comprised: the
above-mentioned suspension is added to an autoclave directly, or
the above-mentioned dry powder is formulated with the alcohol (A)
or the inert organic solvent (E) or a mixture of (A) and (E) into a
suspension with a dry powder content of 5% to 80%, and then is
added to an autoclave, the reaction was carried out at a
temperature higher than 80.degree. C. and a pressure higher than
atmospheric pressure, and finally the resulting solid product is
dried to obtain a carrier (S).
[0029] Alternatively, an alcohol (A) is reacted with a metal
magnesium powder (B) in the presence of a halogen or a
halogen-containing compound (C) to form a magnesium compound (D),
the molar ratio of (A) to (B) is from 3 to 5, and the molar ratio
of (C) and (B) is from 0.002 to 0.01; when the viscosity of the
reaction solution rises sharply, (A) or an inert organic solvent
(E) or the mixture of (A) and (E) is added, the molar ratio of
added amount and (B) is from 2 to 7; the above-mentioned reaction
system is subjected to a reaction at a temperature higher than
80.degree. C. and a pressure higher than atmospheric pressure, and
finally the resulting solid product is dried to obtain a carrier
(S).
[0030] The alcohol (A) is a lower alcohol having 1 to 6 carbon
atoms, which can be used alone or in combination of two or more. In
one preferred embodiment, the alcohol is ethanol, so that an olefin
polymerization solid catalyst with better polymerization activity,
better polymer particle size distribution, and better particle
morphology can be obtained. The invention has no strict requirement
on the purity of the alcohol, and the water content in the alcohol
is generally controlled below 2000 ppm.
[0031] The particle size of the metal magnesium powder (B) is
preferably 350 .mu.m or less, preferably in the range of 80 to 350
.mu.m, the active magnesium content is more than 98%, and the shape
of the metal magnesium powder may be spherical or in other
form.
[0032] The halogen in the halogen or halogen-containing compound
(C) is chlorine, bromine or iodine, and iodine is preferred; the
halogen atom of the halogen-containing compound is chlorine,
bromine or iodine; in the halogen-containing compound,
metal-containing compound is preferred, such as MgCl.sub.2,
MgBr.sub.2, MgI.sub.2, Mg (OEt) Cl, Mg (OEt) I, CaCl.sub.2, NaCl,
KBr; particularly preferably MgCl.sub.2. The morphology, particle
size and the like of these compounds are not particularly limited.
These halogen or halogen-containing compounds may be used alone or
in combinations.
[0033] The inert organic solvent (E) is a liquid aromatic
hydrocarbon or alkane at room temperature, where the aromatic
hydrocarbon is benzene, toluene, xylene, ethylbenzene,
propylbenzene or trimethylbenzene, preferably toluene or xylene,
and the alkane is hexane, heptane or cyclohexane; the aromatic
hydrocarbon and alkane can be used alone or in combination.
[0034] The dried suspension of the prepared carrier (S) or the
suspension itself is subjected to a particle morphology test by an
electron microscope or a laser particle size tester, the result
shows that the magnesium compound carrier (S) prepared by the
method of the present invention is non-spherical, which is a
square-like shaped carrier with clear edges and corners.
[0035] The particle size of the carrier (S) particles is from 1 to
200 .mu.m, preferably 5 to 150 .mu.m, more preferably 10 to 100
.mu.m. Particles less than 5 .mu.m in the particles should not
exceed 20%, preferably not more than 10%; particles greater than
100 .mu.m should not exceed 10%, preferably not more than 5%. These
particles preferably have a narrow particle size distribution, the
more compact the better, the lower content of coarse particles the
better.
[0036] The conditions in the preparation method according to the
present invention are given below:
[0037] In step 1), the order of addition of (A), (B) and (C) may be
arbitrary, wherein (A) can contact (C) first, and then contact (B);
(A), (B) and (C) can be added individually or simultaneously or in
batches or continuously, wherein adding in batches or continuously
is preferred; the contact temperature of the (A), (B) and (C) is
from 30.degree. C. to 90.degree. C., preferably from 40.degree. C.
to 80.degree. C.
[0038] In step 2), when the viscosity of the reaction solution
rises sharply, (A) or an inert organic solvent (E) or a mixed
solution of (A) and (E) is added, the molar ratio of added amount
and (B) is from 2 to 7; when the mixed solution of (A) and (E) is
used, the ratio of (A) and (E) may be arbitrary; when (A) or (E) or
the mixture of (A) and (E) is added the temperature is from
30.degree. C. to 90.degree. C., preferably from 40.degree. C. to
80.degree. C.
[0039] 3) After the above reaction is complete, the resulting solid
may be washed with (E), or not be washed to obtain a solid
suspension, or the solvent is filtered off under pressure to give a
solid dry powder (D).
[0040] Preferably, the method further includes a step 4): the
above-mentioned suspension is directly added to an autoclave, or
the above-mentioned dry powder is formulated with an alcohol (A) or
an inert organic solvent (E) or a mixture of (A) and (E) into a
suspension with a dry powder content of 5% to 80%, after the
resulting suspension is added to an autoclave, the reaction was
carried out at a temperature higher than 80.degree. C. and a
pressure higher than atmospheric pressure, and finally the
resulting solid is dried to obtain a carrier (S).
[0041] The reaction pressure is from 0.2 MPa to 5.0 MPa, preferably
from 0.3 MPa to 3.0 MPa, most preferably from 0.5 MPa to 2.0
MPa.
[0042] The reaction temperature is from 80.degree. C. to
200.degree. C., preferably from 100.degree. C. to 180.degree. C.,
most preferably from 120.degree. C. to 160.degree. C.
[0043] The reaction time is from 2 minutes to 6 hours, preferably
from 5 minutes to 5 hours, most preferably from 10 minutes to 4
hours.
[0044] The reaction can be carried out with or without
stirring.
[0045] The carrier has a particle diameter of 1 to 200 .mu.m,
preferably 5 to 150 .mu.m, and most preferably 10 to 100 .mu.m.
These particles preferably have a narrow particle size
distribution, and the smaller amount of large particles the better.
Particles having a size less than 5 .mu.m should not exceed 20%,
preferably not more than 10%.
[0046] The carrier has a non-spherical shape, a cube-like shape
with clear edges and corners, and the carrier has a smooth surface
and a dense structure. The carrier (D) that has not been subjected
to a high temperature and high pressure is spherical, with a crisp
surface.
[0047] In order to achieve another object of the present invention,
provided is an olefin polymerization solid catalyst component which
is the reaction product of the above-mentioned carrier
Mg(OR.sup.I).sub.n(OR.sup.II).sub.2-n with a titanium compound, in
which at least one electron donor compound may be contained,
wherein 0.ltoreq.n.ltoreq.2, and R.sup.I and R.sup.II can be the
same or different, and are C.sub.1-C.sub.20 hydrocarbon groups. In
the X-ray diffraction pattern of the carrier, there are a set of
diffraction peaks in the range of a 2.theta. diffraction angle of
5.degree.-15.degree., and the set of diffraction peaks contain 1-4
main diffraction peaks.
[0048] In the carrier Mg(OR.sup.I).sub.n(OR.sup.II).sub.2-n,
R.sup.I and R.sup.II can be the same or different, and are
preferably C.sub.1-C.sub.8 hydrocarbon groups.
Mg(OR.sup.I).sub.n(OR.sub.II).sub.2-n is selected from the group
consisting of dimethoxy magnesium, diethoxymagnesium,
dipropoxymagnesium, dibutoxymagnesium, ethoxypropoxymagnesium or
butoxyethoxymagnesium, etc, preferably diethoxymagnesium or
dipropoxymagnesium.
[0049] In the X-ray diffraction pattern of the carrier
Mg(OR.sup.I).sub.n(OR.sup.II).sub.2-n, preferably, there are a set
of diffraction peaks in the range of a 2.theta. diffraction angle
of 7.degree.-13.degree., and the set of diffraction peaks contain
1-4 main diffraction peaks.
[0050] In the X-ray diffraction pattern of the carrier
Mg(OR.sup.I).sub.n(OR.sup.II).sub.2-n, alternatively preferably,
there are a set of diffraction peaks in the range of a 2.theta.
diffraction angle of 5.degree.-15.degree., and the set of
diffraction peaks contain 1-4 main diffraction peaks; and there are
a second set of diffraction peaks in the range of a 2.theta.
diffraction angle of 20.degree.-30.degree., and the second set of
diffraction peaks contain 1-3 main diffraction peaks. Still further
preferably, the highest peak of the first set of diffraction peaks
corresponds to 2.theta. diffraction angle of 8.degree.-13.degree.,
and the highest peak of the second set of diffraction peaks
corresponds to 2.theta. diffraction angle of 21.degree.-28.degree..
Still further preferably, in the X-ray diffraction pattern of the
carrier Mg(OR.sup.I).sub.n(OR.sup.II).sub.2-n, the highest peak of
the first set of diffraction peaks corresponds to 2.theta.
diffraction angle of 9.degree.-12.degree., and the highest peak of
the second set of diffraction peaks corresponds to 2.theta.
diffraction angle of 22.degree.-26.degree.. More preferably, the
highest peak of the first set of diffraction peaks corresponds to
2.theta. diffraction angle of 10.degree.-11.degree., and the
highest peak of the second set of diffraction peaks corresponds to
2.theta. diffraction angle of 22.degree.-24.degree.. Most
preferably, the highest peak of the first set of diffraction peaks
corresponds to 2.theta. diffraction angle of
10.4.degree..+-.0.2.degree., and the highest peak of the second set
of diffraction peaks corresponds to 2.theta. diffraction angle of
23.1.degree..+-.0.2.degree..
[0051] In the various above embodiments, the highest diffraction
peak is within the range of the first set of peaks.
[0052] The titanium compound of the present invention has a general
formula TiX.sub.n(OR).sub.4-n wherein R is a hydrocarbon group
having 1 to 20 carbon atoms, X is a halogen, n=0-4, preferably
titanium tetrachloride, titanium tetrabromide, titanium tetraiodide
and alkoxy titanium halide, alkyl titanium halide such as methoxy
titanium trichloride, ethoxy titanium trichloride, propoxy titanium
trichloride, n-butoxy titanium trichloride, dimethoxy titanium
dichloride, diethoxy titanium dichloride, dipropoxy titanium
dichloride, di-n-butoxy dichloride titanium, trimethoxy titanium
chloride, triethoxy titanium chloride, tripropoxy titanium chloride
or tri-n-butoxy titanium chloride. These titanium halides can be
used alone or in combination. Titanium tetrachloride is most
preferably used.
[0053] The electron donor compound of the present invention may be
selected from Lewis bases containing one or more electronegative
groups in which the electron donor atom may be selected from the
group consisting of N, O, S, P, As or Sn, preferably from the group
consisting of the electron donor compounds such as diethers,
esters, diketones and diamine, most preferably selected from the
group consisting of: phthalates; or 1,3-diethers; or succinates; or
1,3-diol esters; or a compound containing one or more ether groups
or an ester group; these electron donor compounds may be used alone
or in combination.
[0054] Specifically, one of the electron donor compounds of the
present invention is preferably a monocarboxylic acid ester or a
polycarboxylic acid ester compound, and specific examples are an
aromatic dicarboxylic acid compound and an aliphatic chain
dicarboxylic acid ester compound:
[0055] Diesters of the aromatic dicarboxylic acids include examples
such as phthalic acid diesters or terephthalic acid diesters.
Phthalic acid diesters include: dimethyl phthalate, diethyl
phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl
phthalate, diisobutyl phthalate, methyl ethyl phthalate, methyl
isopropyl phthalate, methyl n-propyl phthalate, ethyl n-butyl
phthalate, ethyl isobutyl phthalate, di-n-pentyl phthalate,
diisopentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate,
di-n-octyl phthalate, diisooctyl phthalate, di(2,2-dimethylhexyl)
phthalate, di(2-ethylhexyl) phthalate, di-n-nonyl phthalate,
diisodecyl phthalate, di(2,2-dimethylheptyl) phthalate, n-butyl
isohexyl phthalate, n-butyl (2-ethylhexyl) phthalate, n-pentyl
n-hexyl phthalate, n-pentyl isononyl phthalate, isopentyl n-decyl
phthalate, n-pentyl undecyl phthalate, isopentyl isohexyl
phthalate, n-hexyl (2-methylhexyl) phthalate, n-hexyl
(2-ethylhexyl) phthalate, n-hexyl isononyl phthalate, n-hexyl
(n-decyl) phthalate, n-heptyl (2-ethylhexyl) phthalate, n-heptyl
(isononyl) phthalate, n-heptyl neononyl phthalate and 2-ethylhexyl
(isononyl) phthalate. These esters may be used alone or in
combination. Terephthalic acid diesters include: dimethyl
terephthalate, diethyl terephthalate, di-n-propyl terephthalate,
diisopropyl terephthalate, di-n-butyl terephthalate, diisobutyl
terephthalate, ethyl methyl terephthalate, methyl isopropyl
terephthalate, ethyl (n-propyl) terephthalate, ethyl (n-butyl)
terephthalate, ethyl (isobutyl) terephthalate, di-n-pentyl
terephthalate, diisopentyl terephthalate, dihexyl terephthalate,
di-n-heptyl terephthalate, di-n-octyl terephthalate, diisooctyl
terephthalate, di(2,2-dimethylhexyl) terephthalate,
di(2-ethylhexyl) terephthalate, di-n-nonyl terephthalate,
diisononyl terephthalate, diisodecyl terephthalate,
di(2,2-dimethylethylheptyl) terephthalate, n-butyl isohexyl
terephthalate, n-butyl (2-ethylhexyl) terephthalate, n-pentyl
n-hexyl terephthalate, n-pentyl isohexyl terephthalate, isopentyl
(heptyl) terephthalate, terephthalic acid, n-pentyl (2-ethylhexyl)
terephthalate, n-pentyl (isononyl) terephthalate, isopentyl
(n-decyl) terephthalate, n-pentyl undecyl terephthalate, isopentyl
isohexyl terephthalate, n-hexyl (2-ethylhexyl) terephthalate,
n-hexyl isononyl terephthalate, n-hexyl (n-decyl) terephthalate,
n-heptyl (2-ethylhexyl) terephthalate, n-heptyl (isononyl)
terephthalate, n-heptyl (neodecyl) terephthalate and 2-ethylhexyl
(isononyl) terephthalate. These esters may be used alone or in
combination.
[0056] Among these diesters, one or more of the following is
preferred: diethyl phthalate, dipropyl butyl phthalate, diisopropyl
terephthalate, di-n-butyl phthalate, diisobutyl phthalate,
di-n-octyl phthalate, diisooctyl phthalate, di-n-butyl
terephthalate, diisobutyl terephthalate, di-n-octyl terephthalate,
diisooctyl terephthalate, di(2-ethylhexyl) terephthalate, or
diisodecyl phthalate.
[0057] In the aliphatic chain dicarboxylic acid ester compounds,
succinate compounds with the general formula (I) are particularly
preferred:
##STR00001##
wherein the groups R.sup.1 and R.sup.2 are the same or different
from each other and are C.sub.1-C.sub.20 linear or branched alkyl,
alkenyl, cycloalkyl, aryl, aralkyl or alkaryl groups, optionally
containing heteroatoms; at least two groups of R.sup.3-R.sup.6 are
different from hydrogen and are selected from C.sub.1-C.sub.20
linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or
alkylaryl groups, optionally containing heteroatoms, and the groups
R.sup.3-R.sup.6 may be linked together to form a ring.
[0058] R.sup.1 and R.sup.2 are preferably C.sub.1-C.sub.8 alkyl,
cycloalkyl, aryl, aralkyl and alkaryl groups. Particularly
preferred are compounds in which R.sup.1 and R.sup.2 are selected
from primary alkyl groups, especially branched primary alkyl
groups. Examples of suitable R.sup.1 and R.sup.2 are methyl, ethyl,
n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Particularly
preferred are ethyl, isobutyl and neopentyl.
[0059] One of the preferred compound classes described in general
formula (I) is such that R.sup.3 to R.sup.5 are hydrogen and
R.sup.6 is a branched alkyl, cycloalkyl, aryl, aralkyl, and aralkyl
groups having 3 to 10 carbon atoms alkylaryl groups. Particularly
preferred are compounds in which R.sup.6 is a branched primary
alkyl group or a cycloalkyl group having 3 to 10 carbon atoms.
Specific examples of suitable mono-substituted succinate compounds
are diethyl sec-butylsuccinate, diethyl hexyl succinate, diethyl
cyclopropylsuccinate, diethyl norbornyl succinate, diethyl
perhydrosuccinate, diethyl trimethyl succinate, diethyl
methoxysuccinate, diethyl p-methoxyphenylsuccinate, diethyl
p-chlorophenyl succinate, diethyl phenyl succinate, diethyl
cyclohexyl succinate, diethyl benzyl succinate, diethyl cyclohexyl
methyl succinate, diethyl t-butyl succinate, diethyl isobutyl
succinate, isopropyl succinate, diethyl neopentyl succinate,
diethyl isopentyl succinate, diethyl (1-trifluoromethyl ethyl)
succinate, diethyl fluorenyl succinate, phenyl succinic acid
1-(ethoxycarbo diisobutyl) phenylsuccinate, diisobutyl sec-butyl
succinate, diisobutyl hexylsuccinate, diisobutyl
cyclopropylsuccinate, diisobutyl norbornyl succinate, diisobutyl
perhydrosuccinate, diisobutyl trimethylsilyl succinate, diisobutyl
methoxysuccinate, diisobutyl p-methoxyphenylsuccinate, diisobutyl
p-chlorophenoxy succinate, diisobutyl cyclohexyl succinate,
diisobutyl benzyl succinate, diisobutyl cyclohexylmethyl succinate,
diisobutyl t-butyl succinate, diisobutyl isobutyl succinate,
diisobutyl isopropyl succinate, diisobutyl neopentylsuccinate,
diisobutyl isopentyl succinate, diisobutyl (1-trifluoromethyl
ethyl) succinate, diisobutyl fluorenyl succinate, diisobutyl
sec-butylsuccinate, di-neopentyl hexyl succinate, di-neopentyl
cyclopropyl succinate, di-neopentyl norbornyl succinate,
di-neopentyl perhydrosuccinate, di-neopentyl trimethylsilyl
succinate, di-neopentyl p-methoxyphenyl succinate, di-neopentyl
p-chlorophenyl succinate, di-neopentyl phenylsuccinate,
di-neopentyl cyclohexyl succinate, di-neopentyl benzyl succinate,
di-neopentyl cyclohexylmethyl succinate, di-neopentyl t-butyl
succinate, di-neopentyl isobutyl succinate, di-neopentyl isopropyl
succinate, di-neopentyl neopentyl succinate, di-neopentyl isopentyl
succinate, di-neopentyl (1-trifluoromethyl ethyl) succinate, and
di-neopentyl fluorenyl succinate.
[0060] Other preferred compounds among the compounds with general
formula (I) include those compounds that at least two groups of
R.sup.3 to R.sup.6 are different from hydrogen and are selected
from C.sub.1-C.sub.20 linear or branched alkyl, alkenyl,
cycloalkyl, aryl, aralkyl or alkaryl groups, optionally containing
heteroatoms. Particularly preferred are compounds in which two
non-hydrogen groups are attached to the same carbon atom. Specific
examples of suitable disubstituted succinates are: diethyl
2,2-dimethylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl
2-benzyl-2-isopropyl succinate, diethyl
diiso-2-cyclohexylmethyl-2-isobutyl succinate, diethyl
2-cyclopentyl-2-n-butylsuccinate, diethyl 2,2-diisobutyl succinate,
diethyl 2-cyclohexyl-2-ethylsuccinate, diethyl
2-isopropyl-2-methylsuccinate, diethyl 2-tetradecyl-2-ethylhexyl
succinate, diethyl 2-diisobutyl-2-ethyl succinate, diethyl
2-(1-trifluoromethyl ethyl)-2-methylsuccinate, diethyl
2-isopentyl-2-isobutylsuccinate, diethyl
2-phenyl-2-n-butylsuccinate, diisobutyl 2,2-dimethyl succinate,
diisobutyl 2-ethyl-2-methyl succinate, diisobutyl
2-benzyl-2-isopropylsuccinate, diisobutyl
2-cyclohexylmethyl-2-isobutylsuccinate, diisobutyl
2-cyclopentyl-2-n-butylsuccinate, diisobutyl
2,2-diisobutylsuccinate, diisobutyl 2-cyclohexyl-2-ethylsuccinate,
diisobutyl 2-isopropyl-2-methylsuccinate, diisobutyl
2-tetradecyl-2-ethylsuccinate, diisobutyl
2-isobutyl-2-ethylsuccinate, diisobutyl 2-(1-trifluoromethyl
ethyl)-2-methylsuccinate, diisobutyl
2-isopentyl-2-isobutylsuccinate, diisobutyl
2-phenyl-2-n-butylsuccinate, di-neopentyl 2,2-dimethyl succinate,
di-neopentyl 2-ethyl-2-methylsuccinate, di-neopentyl
2-benzyl-2-isopropylsuccinate, di-neopentyl
2-cyclohexylmethyl-2-isobutylsuccinate, di-neopentyl
2-cyclopentyl-2-n-butylsuccinate, di-neopentyl
2,2-diisobutylsuccinate, di-neopentyl
2-cyclohexyl-2-ethylsuccinate, di-neopentyl 2-diisopropyl-2-methyl
succinate, di-neopentyl 2-tetradecyl-2-ethylsuccinate, di-neopentyl
2-isobutyl-2-ethylsuccinate, di-neopentyl 2-(1-trifluoromethyl
ethyl)-2-methylsuccinate, di-neopentyl
2-isopentyl-2-isobutylsuccinate, di-neopentyl
2-phenyl-n-butylsuccinate.
[0061] In addition, such compounds are particularly preferred in
which at least two non-hydrogen groups are attached to different
carbon atoms, i.e., R.sup.3 and R.sup.5 or R.sup.4 and R.sup.6.
Specific examples of suitable compounds are diethyl
2,3-bis(trimethylsilyl) succinate, diethyl
2-sec-butyl-3-methylsuccinate, diethyl
2-(3,3,3-trifluoropropyl)-3-methylsuccinate, diethyl
2,3-bis(2-ethylbutyl) succinate, diethyl 2,3-diethyl-2-isopropyl
succinate, diethyl 2,3-diisopropyl-2-methylsuccinate, diethyl
2,3-dicyclohexyl-2-methylsuccinate, diethyl 2,3-dibenzylsuccinate,
diethyl 2,3-diisopropylsuccinate, diethyl 2,3-di(cyclohexylmethyl)
succinate, diethyl 2,3-di-tert-butylsuccinate, diethyl
2,3-diisobutylsuccinate, diethyl 2,3-di-neopentylsuccinate, diethyl
2,3-diisopentylsuccinate, diethyl 2,3-bis(1-trifluoromethyl ethyl)
succinate, diethyl 2,3-di(tetradecyl) succinate, diethyl
2,3-difluorenyl succinate, diethyl
2-tert-butyl-3-isopropylsuccinate, diethyl
2-isopropyl-3-cyclohexylsuccinate, diethyl 2-isopentyl-3-cyclohexyl
succinate, diethyl 2-tetradecyl-3-cyclohexylsuccinate, diethyl
2-cyclohexyl-3-cyclopentylsuccinate, diethyl
2,2,3,3-tetramethylsuccinate, diethyl 2,2,3,3-tetraethylsuccinate,
diethyl 2,2,3,3-tetrapropylsuccinate, diethyl
2,3-diethyl-2,3-diisopropyl succinate, diethyl
2,2,3,3-tetrafluorosuccinate, diisobutyl 2,3-bis(trimethylsilyl)
succinate, diisobutyl 2-sec-butyl-3-methylsuccinate, diisobutyl
2-(3,3,3-trifluoropropyl)-3-methylsuccinate, diisobutyl
2,3-di(2-ethylbutyl) succinate, diisobutyl 2,3-diethyl-2-isopropyl
succinate, diisobutyl 2,3-diisopropyl-2-methylsuccinate, diisobutyl
2,3-dicyclohexyl-2-methylsuccinate, diisobutyl 2,3-dibenzyl
succinate, diisobutyl 2,3-diisopropyl succinate, diisobutyl
2,3-di(cyclohexylmethyl) succinate, diisobutyl
2,3-di-tert-butylsuccinate, diisobutyl 2,3-diisobutylsuccinate,
diisobutyl 2,3-di-neopentyl succinate, diisobutyl 2,3-diisopentyl
succinate, diisobutyl 2,3-bis(1-trifluoromethyl ethyl) succinate,
diisobutyl 2,3-di(tetradecyl) succinate, diisobutyl 2,3-difuorenyl
succinate, diisobutyl 2-isopropyl-3-isobutylsuccinate, diisobutyl
2-tert-butyl-3-isopropylsuccinate, diisobutyl
2-isopropyl-3-cyclohexyl succinate, diisobutyl
2-isopentyl-3-cyclohexylsuccinate, diisobutyl
2-tetradecyl-3-cyclohexylmethylsuccinate, diisobutyl
2-cyclohexyl-3-cyclopentylsuccinate, diisobutyl 2,2,3,3-tetramethyl
succinate, diisobutyl 2,2,3,3-tetraethylsuccinate, diisobutyl
2,2,3,3-tetrapropyl succinate, diisobutyl
2,3-diethyl-2,3-dipropylsuccinate, diisobutyl
2,2,3,3-tetrafluorosuccinate, di-neopentyl 2,3-bis(trimethyl silyl)
succinate, di-neopentyl 2-sec-butyl-3-methylsuccinate, di-neopentyl
2-(3,3,3-trifluoropropyl)-3-methylsuccinate, di-neopentyl
2,3-di(2-ethylbutyl)succinate, di-neopentyl
2,3-diethyl-2-isopropylsuccinate, di-neopentyl
2,3-diisopropyl-2-methylsuccinate, di-neopentyl
2,3-dicyclohexyl-2-methylsuccinate, di-neopentyl 2,3-dibenzyl
succinate, di-neopentyl 2,3-diisopropylsuccinate, di-neopentyl
2,3-bis(cyclohexylmethyl) succinate, di-neopentyl
2,3-di-t-butylsuccinate, di-neopentyl 2,3-diisobutylsuccinate,
di-neopentyl 2,3-di-neopentylsuccinate, di-neopentyl
2,3-(1-trifluoromethyl ethyl) succinate, di-neopentyl
2,3-di(tetradecyl)succinate, di-neopentyl 2,3-difluorenyl
succinate, di-neopentyl 2-isopropyl-3-isobutylsuccinate,
di-neopentyl 2-tert-butyl-3-isopropyl succinate, di-neopentyl
2-isopropyl-3-cyclohexyl succinate, di-neopentyl
2-isopentyl-3-cyclohexyl succinate, di-neopentyl
2-tetradecyl-3-cyclohexylmethylsuccinate, di-neopentyl
2-cyclohexyl-3-isopentyl succinate, di-neopentyl
2,2,3,3-tetramethyl succinate, di-neopentyl
2,2,3,3-tetraethylsuccinate, di-neopentyl
2,2,3,3-tetrapropylsuccinate, di-neopentyl
2,3-diethyl-2,3-diisopropylsuccinate, di-neopentyl
2,2,3,3-tetrafluorosuccinate.
[0062] As mentioned above, the compounds represented by the general
formula (I) in which two or four groups R.sup.3 to R.sup.6 bonded
to the same carbon atom are bonded together to form a ring are also
preferred. Specific examples of suitable compounds are
1-(ethoxycarbonyl)-1-(ethoxyacetyl)-2,6-dimethylcyclohexane,
1-(ethoxycarbonyl)-1-(ethoxyacetyl)-2,5-dimethylcyclopentane,
1-(ethoxycarbonyl)-1-(ethoxyacetylmethyl)-2-methylcyclohexane,
1-(ethoxycarbonyl)-1-(ethoxyacetylcyclohexyl)cyclohexane.
[0063] The above-mentioned compounds may be used in the form of
pure isomers or in the form of mixtures of enantiomers, or in the
form of mixtures of positional isomers and enantiomers. When pure
isomers are used, they are generally isolated using conventional
techniques known in the art. In particular, some of the succinic
acid esters of the present invention may be used in pure racemic or
meso form, or alternatively in both forms of mixtures.
[0064] The electron donor compound of the present invention may
also be selected from 1,3-propanediether compounds represented by
the general formula (II):
##STR00002##
wherein R, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be
the same or different and represent a H or a linear or branched
alkyl, cycloalkyl, aryl, alkaryl or aralkyl group having from 1 to
18 carbon atoms; R.sup.6 and R.sup.7 may be the same or different
and represent linear or branched alkyl groups having 1 to 20 carbon
atoms, cycloalkyl groups having 3 to 20 carbon atoms, aryl groups
having 5 to 20 carbon atoms, alkylaryl groups and aralkyl groups
having 7-20 carbon atoms; one or more groups in R--R.sup.7 may be
linked to form a ring structure, and may comprise one or more
heteroatoms selected from the group consisting of halogen, N, O, S,
P and Si.
[0065] Specific examples of ethers which can be advantageously used
include 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-phenyl ethyl) 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-dimethoxypropane,
2(p-fluorophenyl)-1,3-dimethoxypropane, 2
(1-decahydronaphthyl)-1,3-dimethoxypropane,
2(p-tert-butylphenyl)-1,3-dimethoxypropane,
2,2-dicyclohexyl-1,3-dimethoxypropane,
2,2-diethyl-1,3-dimethoxypropane,
2,2-dipropyl-1,3-dimethoxypropane,
2,2-dibutyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-diethoxypropane,
2,2-dicyclopentyl-dimethoxypropane,
2,2-dipropyl-1,3-diethoxypropane, 2,2-dibutyl-1,3-diethoxyropane,
2-methyl-2-ethyl-1,3-dimethoxypropane,
2-methyl-2-propyl-1,3-dimethoxypropane,
2-methyl-benzyl-1,3-dimethoxypropane,
2-methyl-2-phenyl-1,3-dimethoxypropane,
2-methyl-2-cyclohexyl-1,3-dimethoxypropane,
2-methyl-2-methylcyclohexyl-1,3-dimethoxypropane,
2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane,
2,2-bis(2-phenylethyl)-1,3-dimethoxypropane,
2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane,
2-methyl-2-isobutyl-1,3-dimethoxypropane,
2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane,
2,2-bis(2-ethylhexyl)-1,3-dimethoxypropane,
2,2-bis(p-methylphenyl)-1,3-dimethoxypropane,
2-methyl-2-isopropyl-3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxypropane,
2,2-diphenyl-1,3-dimethoxypropane, 2,2-benzyl-1,3-dimethoxypropane,
2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane,
2,2-bis(cyclohexylmethyl)-1,3 dimethoxypropane,
2,2-diisobutyl-1,3-di ethoxypropane,
2,2-diisobutyl-1,3-dibutyloxypropane,
2-isobutyl-2-isopropyl-1,3-dimethoxypropane,
2,2-di-sec-butyl-1,3-dimethoxypropane,
2,2-di-t-butyl-1,3-dimethoxypropane,
2,2-neopentyl-1,3-dimethoxypropane,
2-isopropyl-2-isopentyl-1,3-dimethoxypropane,
2-phenyl-2-benzyl-1,3-dimethoxypropane,
2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane.
1,1-bis(methoxymethyl) cyclopentadiene;
1,1-bis(methoxymethyl)-2,3,4,5-tetramethylcyclopentadiene;
1,1-bis(methoxymethyl)-2,3,4, 5-tetraphenylcyclopentadiene;
1,1-bis(methoxymethyl)-2,3,4,5-tetrafluorocyclopentadiene;
1,1-bis(methoxymethyl)-3,4-dicyclopentylcyclopentadiene;
1,1-bis(methoxymethyl)indene;
1,1-bis(methoxymethyl)-2,3-dimethylindene;
1,1-bis(methoxymethyl)-4,5,6,7-tetrahydroindene;
1,1-bis(methoxymethyl)-2,3,6,7-tetrafluoroindene;
1,1-bis(methoxymethyl)-4,7-dimethylindene;
1,1-bis(methoxymethyl)-3,6-dimethylindene;
1,1-bis(methoxymethyl)-4-phenylindene;
1,1-bis(methoxymethyl)-4-phenyl-2-methylindene;
1,1-bis(methoxymethyl)-4-cyclohexylindene;
1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl) indene;
1,1-bis(methoxymethyl)-7-trimethylsilylindene;
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)-7-cyclopentylindene;
1,1-bis(methoxymethyl)-7-isopropylindene;
1,1-bis(methoxymethyl)-7-cyclohexylindene;
1,1-bis(methoxymethyl)-7-tert-butylindene;
1,1-bis(methoxymethyl)-7-tert-butyl-2-methylindene;
1,1-bis(methoxymethyl)-7-phenylindene;
1,1-bis(methoxymethyl)-2-phenylindene;
1,1-bis(methoxymethyl)-1H-benzo[e]indene;
1,1-bis(methoxymethyl)-1H-2-methylbenzo[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-difluorfluorene; 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.
[0066] A further preferred compound of the electron donor compound
of the present invention is a diol ester compound with the general
formula (III):
##STR00003##
wherein R.sup.3 to R.sup.6 and R.sup.1 to R.sup.2 are the same or
different hydrogen, halogen or a substituted or unsubstituted
linear or branched C.sub.1-C.sub.20 alkyl group, a C.sub.3-C.sub.20
cycloalkyl group, a C.sub.6-C.sub.20 aryl group, a C.sub.7-C.sub.20
alkaryl group, a C.sub.7-C.sub.20 aralkyl group, a C.sub.2-C.sub.10
alkenyl group or a C.sub.10-C.sub.20 fused ring aryl group; but
when R.sup.1 and R.sup.2 are not hydrogen, one or more of
R.sup.3-R.sup.6 and R.sup.1-R.sup.2 optionally form a ring or
not.
[0067] Specific examples of the diol ester compounds include
1,3-propanediol dibenzoate, 2-methyl-1,3-propanediol dibenzoate,
2-ethyl-1,3-propanediol dibenzoate, 2-propyl-1,3-propanediol
dibenzoate, 2-butyl-1,3-propanediol dibenzoate,
2,2-dimethyl-1,3-propanediol dibenzoate,
2-ethyl-2-butyl-1,3-propanediol dibenzoate,
2,2-diethyl-1,3-propanediol dibenzoate,
2-methyl-2-propyl-1,3-propanediol dibenzoate,
2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate, 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, 2-methyl-1,3-pentanediol
dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate,
2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol
dibenzoate, 2-methyl-1,3-pentanediol dibenzoate,
2-ethyl-1,3-pentanediol dibenzoate, 2-propyl-1,3-pentanediol
dibenzoate, 2-butyl-1,3-pentanediol dibenzoate,
2,2-dimethyl-1,3-pentanediol dibenzoate, 2-methyl-1,3-pentanediol
dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate,
2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol
dibenzoate, 2,2,4-trimethyl-pentanediol dibenzoate,
3-methyl-3-butyl-2,4-pentanediol dibenzoate,
2,2-dimethyl-1,5-pentanediol dibenzoate, 3,5-heptanediol
dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate and the like.
Preferred are pentanediol esters and heptanediol esters.
[0068] A further preferred compound of the electron donor compound
of the present invention is a ring-substituted compound containing
an ether group and an acid ester group selected from the group
consisting of the compounds represented by the general formula
(IV):
##STR00004##
[0069] Wherein, A, B, C, D, and E are each carbon atoms, or are
selected from N, O and S heteroatoms; W, X, Y, Z, and m are 0, 1 or
2; with the proviso that
[0070] when n is equal to 0:
[0071] I) B is a nitrogen atom, A, C and D are each carbon atoms, X
is 1, W, Y and Z are each 2; or
[0072] II) C is a nitrogen atom, A, B and D are each carbon atoms,
Y is 1, W, X and Z are each 2; or
[0073] III) C is an oxygen atom, A, B, and D are each carbon atoms,
Y is 0, W, X and Z are each 2; or
[0074] IV) A and C are each oxygen atoms, W and Y are each 0, X and
Z are each 2; or
[0075] V) B is an oxygen atom, A, C and D are each carbon atoms, X
is 0, W, Y and Z are each 2; or
[0076] VI) A, B, C and D are each carbon atoms and bonded to each
other through a single bond, W, X, Y and Z are each 2; or
[0077] VII) A, B, C and D are each carbon atoms, B and C are bonded
through a double bond, X and Y are each 1, W and Z are each 2;
or
[0078] VIII) A, B, C and D are each carbon atoms, A and D, B and C,
respectively, are bonded through a double bond, W, X, Y and Z are
each 1;
[0079] when n is equal to 1:
[0080] i) D is a nitrogen atom, A, B, C, and E are each carbon
atoms, Z is 1, W, X, Y, and m are each 2; or
[0081] ii) E is a nitrogen atom, A, B, C and D are each carbon
atoms, m is 1, W, X, Y and Z are each 2; or
[0082] iii) E is an oxygen atom, A, B, C and D are each carbon
atoms, m is 0, W, X, Y and Z are each 2; or
[0083] iv) C and D are each oxygen atoms, A, B and E are each
carbon atoms, Y and Z are each 0, W, X, and m are each 2; or
[0084] v) D is an oxygen atom, A, B, C, and E are each carbon
atoms, Z is 0, W, X, Y, and m are each 2; or
[0085] vi) B is an oxygen atom, A, C, D, and E are each carbon
atoms, X is 0, W, Y, Z, and m are each 2;
[0086] vii) A, B, C, D, and E are each carbon atoms, W, X, Y, Z,
and m are each 2;
[0087] viii) A, B, C, D, and E are each carbon atoms, B and C are
bonded through a double bond, X and Y are each 1, W, Z, and m are
each 2; or
[0088] ix) A, B, C, D, and E are each carbon atoms, A and D, B and
C, respectively, are bonded through a double bond, W, X, Y and Z
are each 1, m is 2;
[0089] when n is equal to 2:
[0090] A and B are each carbon atoms, W and X are each 2, C and D
are each a carbon atom, sulfur atom, oxygen atom or nitrogen atom,
Y and Z are each 2 or 0, E represents two carbon atoms bonded
through a single bond or a double bond, where when the two carbon
atoms of E are bonded through a double bond, m is equal to 1, and
when the two carbon atoms of E are bonded through a single bond, m
is equal to 2;
[0091] R.sup.1 and R.sup.4 are same or different C.sub.1-C.sub.20
hydrocarbon groups, such as C.sub.1-C.sub.20 linear or branched
alkyl, alkenyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20 aryl,
C.sub.7-C.sub.20 alkaryl and C.sub.7-C.sub.20 aralkyl group;
R.sup.2, R.sup.3, R.sup.5-R.sup.9 are same or different, and are
each selected from a hydrogen atom, halogen atom, oxygen atom,
sulfur atom and C.sub.1-C.sub.20 hydrocarbon group, such as
C.sub.1-C.sub.20 linear or branched alkyl, C.sub.3-C.sub.20
cycloalkyl, C.sub.6-C.sub.20 aryl, C.sub.7-C.sub.20 alkaryl and
C.sub.7-C.sub.20 aralkyl group;
[0092] Said R.sup.1-R.sup.9 each may optionally contain one or more
R atoms as a substituent of a carbon atom or hydrogen atom, or
both, where R is a heteroatom, a linear or branched
C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20 cycloalkyl,
C.sub.6-C.sub.20aryl, C.sub.7-C.sub.20 alkaryl and C.sub.7-C.sub.20
aralkyl group; wherein any two groups of R.sup.1-R.sup.9 may be
bonded to each other to generate one or more spiro ring or fused
ring structures.
[0093] The examples of the compounds included in the general
formula (IV) are listed as follows:
[0094] Ethyl 1-(1,1-vinyldioxyethyl)cyclopentane-1-carboxylate;
ethyl 2-(1-methoxycyclopentane)-2-methoxy acetate; methyl
1-(methoxymethyl)cyclopentane carboxylate; methyl
1-(benzyloxymethyl)cyclohexyl carboxylate; ethyl
1-(4,4,6-trimethyl-[1,3]azapyran-2-yl)-cyclopentyl carboxylate;
methyl 2-chloro-methoxyethyl-1-cyclopentyl carboxylate;
bi(cyclohexyl carboxylic acid methyl ester)methyl methyl ether;
ethyl 2-benzyloxy-(1,1-vinyldioxyethyl)cyclopentyl carboxylate;
dimethyl-1-methoxybicyclo[2.2.2]oct-8-ene-2,6-dicarboxylic acid
methyl ester; 1-methoxybicyclo[2.2.2]oct-9-ane,
trimethyl-1-methoxybicyclo[2.2.1]heptane-2,6, 10-tricarboxylate;
1-methoxy-1-cyclopentane carboxylic acid ethyl
ester-3-phenyl-propylene;
2-benzyloxymethyl-2-ethoxycarbonyl-1-(tetrahydropyran-2-oxy)oxocyclopenta-
ne; 2-benzyl oxy-2-ethoxycarbonyl-cyclopentanol; methyl
1-(1-methoxyethyl)cyclopentane carboxylate;
2-methyl-2-(1-cyclopentyl carboxylic acid ethyl
ester-1-yl)-4-methylene-1,3-oxopropane;
methyl-(3,4-dihydro-1H-isopyran-1-yl) cyclopentyl carboxylate;
ethyl 1-(methoxymethyl)cyclopentane carboxylate;
methyl-1-(ethoxymethyl)cyclopentane carboxylate;
2-benzyloxymethyl-1-cyclopentanonecarboxylic acid ethyl ester;
methyl 1-benzyloxymethyl-pyrrolidine-2-carboxylate;
methyl-hexahydro-2,2, 7-trimethyl-6-oxo
[1,3]dioxo[5,4-b]pyrrole-4a-carboxylate;
methyl-2-benzyloxymethyl-5-carbonylpyrrolidine-2-carboxylate;
methyl-1-(4-chlorophenyl)-3-(methoxymethyl)-4,5-dicarbonylpyrrole-3-carbo-
xylate; methyl 3-methoxymethyl-pyrrolidine-3-carboxylate;
1-tert-butoxycarbonylmethyl-3-methoxymethyl-pyrrolidine-3-carboxylate;
methyl 1-benzyl-3-methoxymethyl-pyrrolidine-3-carboxylate;
2-ethoxymethyl-pyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester
2-methyl ester; 2-isopropoxymethyl-pyrrolidine-1,2-dicarboxylic
acid 1-tert butyl ester 2-ethyl ester; methyl
3-methoxymethyl-1-(3-methylphenyl)-4,
5-dicarbonylpyrrolidine-3-carboxylate; methyl
3-methoxy-1-(4-fluorophenyl)-4,
5-dicarbonylpyrrolidine-3-carboxylate; methyl
3-methoxymethyl-1-(4-bromophenyl)-4,
5-dicarbonylpyrrolidine-3-carboxylate; methyl
1-(4-hydroxyphenyl)-3-methoxymethyl-4,
5-dicarbonylpyrrolidine-3-carboxylate; ethyl
3-ethoxymethyl-1-phenyl-4,5-dicarbonylpyrrolidine-3-carboxylate;
ethyl 3-ethoxymethyl-1-(3-methylphenyl)-4,
5-dicarbonylpyrrolidine-3-carboxylate; ethyl
3-methoxymethyl-2-carbonyl-tetrahydrofuran-3-carboxylate; ethyl
3-isopropoxymethyl-2-carbonyl-tetrahydrofuran-3-carboxylate; ethyl
1-(4,4,6-trimethyl-[1,3] oxazin-2-yl)-cyclopentyl carboxylate;
methyl-3-ethyl-2-[(2-trimethylsilylethoxy)
methoxymethyl]1,4-dioxaspiro[4.4]nonane-2-carboxylate; methyl
5-oxo-phenyl-2-deoxy-4-methoxycarbonyl-D-pentofuranoside;
2-benzyloxymethyl-3-(2-methoxyvinyl)-2-methoxycarbonyl-1,4-oxaspiro[4.4]n-
onane;
4-pentenyl-5-O-benzyl-2-deoxy-4-methoxycarbonyl-D-pentofuranoside;
methyl
5-O-benzyl-3-O-(t-butyldimethylsilane)-2-deoxy-4-methoxycarbonyl-D-
-pentofuranoside;
1-(2-benzyloxymethyl-3-hydroxy-2-methoxycarbonyl-5-tetrahydrofuran)thymin-
e;
4-N-acetyl-1-(2-benzyloxymethyl-3-hydroxy-2-methoxycarbonyl-5-tetrahydr-
ofuran)cytosine;
4-N-acetyl-5-O-benzyl-2-deoxy-4-methoxycarbonyl-cytosine;
methyl-3,3-dimethyl-8-[5-methyl-2(1-H),
4-(3H)-dioxopyridine-1-yl]-2,4-dioxabicyclo
[4.3.0]non-6-carboxylate;
methyl-1-(4-methoxybenzyl)-2-benzyloxymethyl-3-hydroxy-3-methyl-4-methyle-
ne-5-pyrrolidin-2-carbaldehyde; methyl 2-(hydroxymethoxymethyl)
1-methoxy-5-carbonylpyrrolidin-2-carboxylate; ethyl
(2-cyclopentyl-[1,3]dioxolan-2-)-1-ethyl-2-oxa-2,3-dihydro-1H-indole-3-ca-
rboxylate; benzyloxycarbonyl-thioprolyl-thioproline diethyl acetal;
benzyloxycarbonyl-thioprolyl-thioproline dibutyl acetal;
benzyloxycarbonyl-thiprolyl-thioproline dimethyl acetal;
methyl-2-(benzyloxymethyl)-3-hydroxy-4-methylene-5-carbonylpyrrolidine-2--
carboxylate;
1-tert-butyl-2-methyl-2-(benzyloxymethyl)-5-oxo-pyrrolidine-1,2-dicarboxy-
late;
methyl-2-benzyloxymethyl-3-tertbutyldimethylsilyloxy-4-methyl-5-carb-
onylpyrrolidine-2-carboxylate;
1-tert-butyl-2-methyl-2(benzyloxymethyl)-3-hydroxy-4-methylene-5-oxopyrro-
lidine-1,2-dicarboxylate;
5-tert-butyl-6-methyl-6-(benzyloxymethyl)-2-methyl-4-oxohexahydro-5H-pyrr-
olo[3,4-d]oxazole-5,6-dicarboxylate;
methyl-1-(3,4-dihydro-1H-isobenzo-1-yl)cyclopentane carboxylate;
tert-butyl-1-(1-ethoxy-3-phenyl-allyl)-2-carbonylcyclopentane
carboxylate; 1-tert-butyl-2-methyl-2
(benzyloxymethyl)pyridine-1,2-dicarboxylate;
N-(t-butoxycarbonyl)-.alpha.-(methoxymethyl) proline ethyl ester;
N-(t-butoxycarbonyl)-.alpha.-(t-butylmethyl)proline ethyl ester;
1-tert-butyl-2-methyl-2-(benzyloxymethyl)pyrrolidine-1,2-dicarboxylate;
methyl
3-benzyloxymethyl-1-(2,6-dimethylphenyl)-5-oxo-pyrrolidine-3-carbo-
xylate; ethyl 1-benzyl-2-(diethoxymethyl)pyrrolidine-2-carboxylate;
methyl 2-benzyloxymethyl-1-methyl-pyrrolidine-2-carboxylate;
[0095] 9-methoxymethyl-fluorene carboxylic acid-(9)-methyl ester;
9-ethoxymethyl-fluorene carboxylic acid-(9)-methyl ester;
9-methoxymethyl-fluorene carboxylic acid-(9)-ethyl ester;
9-methoxymethyl-fluorene carboxylic acid-(9)-n-butyl ester;
9-methoxymethyl-fluorene carboxylic acid-(9)-isobutyl ester;
9-methoxymethyl-fluorene carboxylic acid-(9)-isopropyl ester;
9-ethoxymethyl-fluorene carboxylic acid-(9)-ethyl ester;
9-ethoxymethyl-fluorene carboxylic acid-(9)-n-butyl ester;
9-ethoxymethyl-fluorene carboxylic acid-(9)-isobutyl ester;
9-ethoxymethyl-fluorene carboxylic acid-(9)-isopropyl ester;
bi(9-methoxy carbonyl-fluoren-9-yl)-ether; methyl
3-[1-[2-(indol-3-yl)-1-oxo-ethyl]]-2-methoxy-3-azabicyclo[3.2.1]oct-6-ene-
-7-ethyl-1-carboxylate;
methyl-2-methoxydibenzobicyclo-[3.2.1]octadien-1-carboxylate;
methyl-benzyloxymethyl-2-cyclopent-2-ene-1-carboxylate;
methyl-4-[(tert-butoxycarbonyl)amino]-1-ethoxymethyl-cyclopent-2-ene-1-ca-
rboxylate; 8-benzyl
oxy-1-ethoxycarbonyl-5,7,7-trimethyl-2-(propan-2-ylidene)bicyclo[3.3.0]oc-
t-2-ene; methyl-1,1-bis(hydroxymethyl)-3-methoxy-1,2,
3,3a,6,6a-hexahydropentene-3a-carboxylate;
methyl-1-(t-butyldimethyl
siloxymethyl)-1-di(hydroxymethyl)-3-methoxy-1,2,3,3a,6,6a-hexahydropenten-
e-3a-carboxylate; methyl
1,1-bis(benzyloxymethyl)-3-methoxy-1,2,3,3a,6,6a-hexahydropentene-3a-carb-
oxylate; 1,2,3,4,5-pentamer (methoxycarbonyl)-5-(methoxy
methyl)cyclopentadiene;
[0096] Methyl benzyloxymethyl-cyclohexyl carboxylate; ethyl
8-benzyloxymethyl-1,4-dioxo-spiro[4, 5]decane-8-carboxylate;
2-benzyloxymethyl-2-ethoxycarbonylcyclohexanol;
2-benzyloxymethyl-2-ethoxycarbonyl-1-(tetrahydrofuran-2-yl)
oxycyclohexane; methyl
4-(1,3-dioxolane-2-yl)-(1,1'-dicyclohexyl)-4-carboxylate;
ethyl-1-(benzyloxymethyl)-4,4-difluorocyclohexanecarboxylate; ethyl
6-methoxymethyl-1,4-dioxa-spiro [4.5]decane-6-carboxylate;
2-methoxymethyl-2-ethoxycarbonyl-6-methylcyclohexanol; ethyl
1-diethoxymethyl-cyclohexyl carboxylate; methyl
methoxymethyl-cyclohexylcarboxylate; methyl
spiro<bicyclo<3.3.1>nonane-2,2'-<1.3>dioxa-2,2'-[1.3]dioxo-
lane>1-butyrate; ethyl
1-benzyloxymethyl-4-dimethoxycyclohexyl-carboxylate; ethyl
benzyloxymethyl-4-methoxycyclohexyl-carboxylate;
ethyl-4-methyl-1-methoxymethyl-4-trimethylsilyloxycyclohexylcarboxylate;
methyl 1-methoxymethyl-cyclohexyl carboxylate; methyl
1-(3,4-dihydro-1-hydro-isobenzo-1-yl) cyclopentylcarboxylate;
tert-butyl-4-hydroxy-1-(methoxymethyl) cyclohexanecarboxylate;
tert-butyl-4-(tert-butyldimethyl siloxy)-1-(methoxymethyl)
cyclohexanecarboxylate;
tert-butyl-4-(5-aminopyridin-2-oxo)-1-(methoxymethyl)
cyclohexanecarboxylate; tert-butyl-1-methoxymethyl
4-(5-nitropyridine 2-oxo) cyclohexanecarboxylate; ethyl
1-(2-methoxy-ethoxymethyl)-cyclohexanecarboxylate,
ethyl-4,4-difluoro-1-(methoxymethyl)cyclohexanecarboxylate;
4-benzyl oxymethyl-piperidine-1,4-dicarboxylic acid 1-tert-butyl
ester-4-ethyl ester; ethyl
4-benzyloxymethyl-piperidine-4-carboxylate; ethyl
1-((benzyloxymethyl)methyl)2-oxocyclohexanecarboxylate;
2-benzyloxymethyl-2-ethoxycarbonylcyclohexanol;
2-benzyloxymethyl-2-ethoxycarbonyl-1-(tetrahydropyran-2-yl)-oxo-cyclohexa-
ne; ethyl 4-methoxymethylpiperidine-4-carboxylate; methyl
5-methoxyethyl-2-phenyl-[1.3] dioxane-5-carboxylate; ethyl
2-oxahexa-oxo-furo-[1.3]dithiahexa-2-carboxylate;
diethyl-3-phenyl-6,6-(ethylenedioxy)-2-oxo-3-azabicyclo[3.3.1>nonane-1-
,5-dicarboxylate; methyl
tetrahydro-(3,4-dihydro-1H-isobenzo-1-yl)-2H-pyran-4-carboxylate;
methyl
tetrahydro-(3,4-dihydro-1H-isobenzo-1-yl)-2H-pyran-4-carboxylate;
methyl 1-(3,4-dihydro-1H-isobenzo-1-yl)cyclohexanecarboxylate;
methyl
tetrahydro-3,4-dihydro-5-methyl-1H-isobenzo-1-yl)-2H-pyran-4-carboxylate;
ethyl 4,4-difluoro-1-(methoxymethyl)cyclohexanecarboxylate; ethyl
2-(methoxymethyl) tetrahydro-2H-pyran-2-carboxylate;
3-methoxymethyl-3-ethoxycarbonyl-1-methyl-cyclohexene (1); methyl
2,3,3a,
4,5,7a-hexahydro-3,3a-dimethyl-1,5-di-(2-trimethylsilylethoxy-oxo)inden-7-
a-carboxylate;
1-benzyloxymethyl-1-methoxycarbonyl-2,5-cyclohexene;
[0097] Methyl
4-benzyl-7-methoxy-3-oxo-3,4-dihydro-2H-1,5-benzothia-4-carboxylate;
methyl
4-benzyloxymethyl-3-(4-methoxybenzyl)-5-methyl-7-oxo-6-oxa-3-aza-b-
icyclo[3.2.0]heptane-4-carboxylate.
[0098] Among the compounds with the general formula (IV), examples
of specific suitable compounds are listed as follows:
9-methoxymethyl-fluorene carboxylic acid-(9)-methyl ester;
9-ethoxymethyl-fluorene carboxylic acid-(9)-methyl ester;
9-methoxymethyl-fluorene carboxylic acid-(9)-ethyl ester;
9-methoxymethyl-fluorene carboxylic acid-(9)-n-butyl ester;
9-methoxymethyl-fluorene carboxylic acid-(9)-isobutyl ester;
9-methoxymethyl-fluorene carboxylic acid-(9)-isopropyl ester;
9-ethoxymethyl-fluorene carboxylic acid-(9)-ethyl ester;
9-ethoxymethyl-fluorene carboxylic acid-(9)-n-butyl ester;
9-ethoxymethyl-fluorene carboxylic acid-(9)-isobutyl ester;
9-ethoxymethyl-fluorene carboxylic acid-(9)-isopropyl ester;
Bis<9-methoxycarbonyl-fluoren-9-yl-diethyl ether;
1,2,3,4,5-penta(methoxycarbonyl)-5-(methoxymethyl)
cyclopentadiene.
[0099] Another preferred compound of the electron donor compound of
the present invention is an unsaturated ring-substituted diacid
ester compound selected from the compounds represented by the
general formula (V):
##STR00005##
[0100] Wherein A, B, C, D and E are each selected from carbon atoms
or heteroatoms selected from N, O and S; W, X, Y, Z and m are 0 or
1;
[0101] When n is equal to 0:
[0102] I) A, B, C and D are each carbon atoms, X, Y, Z and W are 1;
or
[0103] II) A is a nitrogen atom, B, C and D are each carbon atoms,
W is 0, X, Y and Z are 1; or
[0104] III) A and D are nitrogen atoms, B and C are carbon atoms, W
and Z are 0, X and Y are 1; or
[0105] IV) D is a nitrogen atom, A, B and C are each carbon atoms,
Z is 0, W, X and Y are 1; or
[0106] When n is equal to 1:
[0107] i) A, B, C, D and E are each carbon atoms, m is 2, W, X, Y
and Z are 1; or
[0108] ii) E is a nitrogen atom, A, B, C and D are each carbon
atoms, m is 1, W, X, Y and Z are 1; or
[0109] iii) E is an oxygen atom, A, B, C and D are each carbon
atoms, m is 0, W, X, Y and Z are 1; or
[0110] iv) E is a sulfur atom, A, B, C and D are each carbon atoms,
m is 0, W, X, Y and Z are 1; or
[0111] v) D and E are nitrogen atoms, A, B and C are each carbon
atoms, m is 1, W, X and Y are 1 and Z is O.
[0112] R.sup.1 and R.sup.2 are same or different C.sub.1-C.sub.20
hydrocarbon groups, such as C.sub.1-C.sub.20 linear or branched
alkyl, alkenyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20 aryl,
C.sub.7-C.sub.20 alkaryl and C.sub.7-C.sub.20 aralkyl group;
R.sup.3-R.sup.7 are same or different, and are each selected from a
hydrogen atom, halogen atom, oxygen atom, sulfur atom and
C.sub.1-C.sub.20 hydrocarbon group, such as C.sub.1-C.sub.20 linear
or branched alkyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20
aryl, C.sub.7-C.sub.20 alkaryl and C.sub.7-C.sub.20 aralkyl
group;
[0113] Said R.sup.1-R.sup.7 each may optionally contain one or more
R atoms as a substituent of a carbon atom or hydrogen atom, or
both, where R is a heteroatom, a linear or branched
C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20 cycloalkyl,
C.sub.6-C.sub.20aryl, C.sub.7-C.sub.20 alkaryl and C.sub.7-C.sub.20
aralkyl group; wherein any two groups of R.sup.1-R.sup.7 may be
bonded to each other to generate one or more spiro ring or fused
ring structures.
[0114] The examples of the compounds included in the general
formula (V) are listed as follows:
[0115] diethyl 3,5-diphenyl 2H pyrrole-2,2-dicarboxylate; diethyl
3-(3-chlorophenyl)-5-methyl-pyrrole-2,2-dicarboxylate; diethyl
3-(3-bromophenyl)-5-methyl-pyrrole-2,2-dicarboxylate;
diethyl-3-(p-chlorobenzene)-5-phenyl-2H-pyrrole-2,2-dicarboxylate;
dimethyl fluorene-9,9-dicarboxylate; diethyl
fluorene-9,9-dicarboxylate; di-n-propyl fluorene-9,9-dicarboxylate;
di-isopropyl di-n-butyl fluorene-9,9-dicarboxylate; diisobutyl
fluorene-9,9-dicarboxylate; di-n-pentyl fluorene-9,9-dicarboxylate;
di-n-hexyl fluorene-9,9-dicarboxylate; di-n-heptyl
fluorene-9,9-dicarboxylate; di-n-octyl fluorene-9,9-dicarboxylate;
dibenzyl fluorene-9,9-dicarboxylate; dihexadecyl
fluorene-9,9-dicarboxylate; dibenzyl fluorene-9,9-dicarboxylate;
dipropenyl fluorene-9,9-dicarboxylate; 9-methyl carboxylate-9-ethyl
carboxylate-fluorene; 9-methyl carboxylate-9-n-propyl
carboxylate-fluorene; 9-methyl carboxylate-9-isopropyl
carboxylate-fluorene; 9-methyl carboxylate-9-n-butyl
carboxylate-fluorene; 9-methyl carboxylate-9-isobutyl
carboxylate-fluorene;
dimethyl-4H-benzo<g>thio<2,3-e>indazole-4,4-dicarboxylate;
diethyl-5-phenyl-3 (p-toluene)-2H-pyrrole-2,2-dicarboxylate;
diethyl-3 (p-methoxybenzene)-5-phenyl-2H-pyrrole-2,2-dicarboxylate;
diethyl 5-(p-nitro)-3-phenyl-2H-pyrrole-2,2-dicarboxylate;
diethyl-2,3-diphenyl-1H-indene-1,1-dicarboxylate;
diethyl-2-phenyl-1H-indene-1,1-dicarboxylate;
diethyl-2-(4-chlorobenzene)-1H-indene-1,1-dicarboxylate;
diethyl-2-(4-methoxyphenyl)-1H-indene-1,1-dicarboxylate; dimethyl
3-(4-methylbenzene)-2-phenyl-1H-indene-1,1-dicarboxylate;
dimethyl-3-(4-nitrobenzene)-1H-indene-1,1-dicarboxylate; dimethyl
amino-4-pentamethoxycarbonyl-1,2,3,5,5-pentamethoxycarbonylcyclopentadien-
e; 3-phenyl-indene-1,1-dicarboxylate; dimethyl-5-(p-chlorobenzene)
3-phenyl-2H-pyrrole-2,2-dicarboxylate; dimethyl
3-(p-nitrobenzene)-5-phenyl-2H-pyrrole-dicarboxylate; dimethyl
3-(m-nitrobenzene)-5-phenyl-2H-pyrrole-2,2-dicarboxylate; dimethyl
5-(m-nitrobenzene) 5-phenyl-2H-pyrrole-2,2-dicarboxylate; dimethyl
5, 6-dimethyl-5H, 6H-cyclopentadienindole-11,11-dicarboxylate;
1-(2-nitrophenylthio)-2,3,4,5,5-methyl carboxylate-cyclopentadiene;
1-(2,4-dinitrobenzene)-2,3,4,5,5-methyl
pentacarboxylate-cyclopentadiene;
methyl-2-tert-butyl-3-methyl-1H-indene-1,1-dicarboxylate; dimethyl
3-methyl-2-trimethylsilyl-indene-1,1-dicarboxylate; dimethyl
3-methyl-2-phenyl-indene-1,1-dicarboxylate;
diethyl-2,3-di-n-propyl-1H-indene-1,1-dicarboxylate;
dimethyl-3-hydroxymethyl-2-phenyl-1H-indene-1,1-dicarboxylate;
dimethyl-2-tert-butyl-5,6-dimethoxy-3-methyl-1H-indene-1,1-dicarboxylate;
dimethyl-2-phenyl-3-(thia-2-yl) 1H-indene-1,1-dicarboxylate;
dimethyl-3-(2-methylbenzene)2-phenyl-1H-indene-1,1-dicarboxylate;
dimethyl
3-(2-methoxycarbonylphenyl)-2-phenyl-1H-indene-1,1-dicarboxylate- ;
dimethyl 3-(4-trifluoromethylbenzene)
2-phenyl-1H-indene-1,1-dicarboxylate; dimethyl 3-(4-acetylbenzene)
2-phenyl-1H-indene-1,1-dicarboxylate;
dimethyl-2-(2-cyclohex-1-ene)-3-(4-acetylbenzene)-1H-indene-1,1-dicarboxy-
late; dimethyl
2-[(ethoxycarbonyl)methyl]-1H-indene-1,1-dicarboxylate;
1,1-diethyl-1H-indene-1,1-dicarboxylate; ethyl 7-chloro-5
methyl-pyrazolo[4,3-d] pyrimidine-3,3-dicarboxylate;
ethyl-amino-7-methyl-pyrazolo[4,3-d] pyrimidine-3,3-dicarboxylate;
ethyl
7-methoxy-5-methyl-pyrazolo[4,3-d]pyrimidine-3,3-dicarboxylate;
1-p-tolyl amino-2,3,4,5,5-pentamethoxycarbonylcyclopentadiene;
dimethyl-3H-phenanthro<9,10-c>pyrazole-3,3-dicarboxylate;
3,3-bis(methoxycarbonyl)-3H-indazole;
3,3-bis(ethoxycarbonyl)3H-indazole; 1-trichloromethyl-1,3,5,
5-pentamethoxycarbonylcyclopentadiene;
1-(2-methyl-4-nitrobenzene)-pentamethoxycarbonylcyclopentadiene;
1-(2-iodo-4-nitrobenzene)-pentamethoxycarbonylcyclopentadiene;
2-(2-iodo-4-nitrobenzene)-1,3,4,5,5-pentamethoxycarbonylcyclopentadiene;
1-(2,4-dinitrobenzene)-2,3,4, 5,5-pentamethoxycarbonyl
cyclopentadiene;
4-benzyl-1,2,3,5,5-penta(methoxycarbonyl)cyclopentadiene;
3-benzyl-1,2,4,5,5-penta (methoxycarbonyl)cyclopentadiene;
2-(trifluoromethyl)-5-carbonyl-3,3-bis (methoxycarbonyl)-3H-indole;
2-(trifluoromethyl)-5-carbonyl-7-methyl-3,3-bis
(methoxycarbonyl)-3H-indole;
3-(trifluoromethyl)-5-hydroxy-7-methoxy-3,3-bis
(methoxycarbonyl)-3H-indole; diethyl-3-phenyl-5(p-toluene)
2H-pyrrole-2,2-dicarboxylate;
diethyl-2-(4-chlorobenzene)-5-morpholine-4H-imidazole-4,4-dicarboxylate;
4,5,5-methyl tricarboxylate-1,2,3-trichlorocyclopentadiene;
methyl-3-methyl-4-trimethylsilyl-cyclopenta-2,4-diene-1,1-dicarboxylate;
diethyl-2,5-diphenyl-4H-imidazole-4,4-dicarboxylate;
diethyl-3-benzyl-2-phenyl-1H-indene-1,1-dicarboxylate;
diethyl-3-(4-(methoxycarbonyl)phenyl)
2-phenyl-1H-indene-1,1-dicarboxylate; diethyl-3-(4-acetylbenzene)
2-phenyl-1H-indene-1,1-dicarboxylate;
diethyl-2-methoxymethyl-1H-indene-1,1-dicarboxylate;
diethyl-2-tert-butyl-1H-indene-1,1-dicarboxylate; dimethyl
2-n-butyl-1H-indene-1,1-dicarboxylate; diethyl
2-n-butyl-1H-indene-1,1-dicarboxylate; diethyl
2-n-hexyl-1H-indene-1,1-dicarboxylate;
diethyl-2-(3-cyano-1-propyl)-1H-indene-1,1-dicarboxylate;
diethyl-2-di ethoxymethyl-1H-indene-1,1-dicarboxylate;
diethyl-2-(4-methoxyphenyl)-1H-indene-1,1-dicarboxylate;
diethyl-2-(1-cyclohexene)-1H-indene-1,1-dicarboxylate;
diethyl-2-(1-cyclohexyl)-1H-indene-1,1-dicarboxylate;
diethyl-3-(3-toluene)-2-phenyl-1H-indene-1,1-dicarboxylate;
diethyl-3-(3-nitrobenzene)-2-phenyl-1H-indene-1,1-dicarboxylate;
diethyl 13H-indeno[1,2-e]-phenanthrene-13,13-dicarboxylate;
diethyl-2-hexyl-3-(4-methoxyphenyl)1H-indene-1,1-dicarboxylate;
ethyl cyclopenta[c]thia-5,5-dicarboxylate; 4-[4-[4-(methylsulfonic
acid)benzene]1,1-bis (methyloxy)cyclopenta-2,4-di en-3-yl]pyridine;
fluorene-4,9,9-dicarboxylic acid-4-tert-butyl-9,9-dicarboxylate;
4-(4-amino-pyridin-3-ylcarbamoyl)-fluoren-9,9-dicarboxylate;
4-(3-amino-pyridin-4-ylcarbamoyl)-fluoren-9,9-dicarboxylate;
diethyl-3-iodo-2-phenyl-1H-indene-1,1-dicarboxylate;
diethyl-3-iodo-2-n-pentyl-1H-indene-1,1-dicarboxylate;
diethyl-3-iodo-2-(3-methoxyphenyl)-1H-indene-1,1-dicarboxylate;
diethyl-3-iodo-2-(naphthalen-2-yl)-1H-indene-1,1-dicarboxylate;
di-n-hexyl-fluorene-9,9-dicarboxylate;
di-n-heptyl-fluorene-9,9-dicarboxylate;
diethyl-2-benzene-3H-indene-3,3-dicarboxylate;
diethyl-2-bromo-1H-indene-1,1-dicarboxylate;
[0116] 1-ethyl-1-methyl-cyclohexa-2, 5-diene-1,1-dicarboxylate; N,
4,4-triethoxycarbonyl-1,4-dihydro-pyridine;
2,6-diphenyl-4,4-dimethoxycarbonyl-4H-pyrane;
2,6-diphenyl-4,4-dimethoxycarbonyl-1,4-dihydropyridine;
2,6-bis(4-chlorobenzene)-4,4-dimethoxycarbonyl-4H-pyrane;
2,6-bis(4-methoxyphenyl)-4,4-dimethoxycarbonyl-4H-pyrane;
2,6-bis(4-chlorobenzene)-4,4-dimethoxycarbonyl-1,4-dihydropyridine;
2,6-bis(4-methoxyphenyl)-4,4-dimethoxycarbonyl-1,4-dihydropyridine;
1-cyclopentyl-4,4-bis(methoxycarbonyl)-1,4-dihydropyridine;
1-n-hexyl-4,4-bis(methoxycarbonyl)-1,4-dihydropyridine;
1-methoxy-6, 6-dicarboxyloxymethyl-cyclohexa-1,4-diene; dimethyl
1,4-dihydronaphthalene-1,1-dicarboxylate;
2,6-bis(4-chlorobenzene)-4,4-dimethoxycarbonyl-4H-thiopyrane;
diethyl-3-bromo-1,4-dihydro-1-methyl
pyridazino[3,4-b]quinoxaline-4,4-dicarboxylate;
diethyl-5-bromo-3-phenyl-1,4-dihydropyridazine-4,4-dicarboxylate;
trihexyl-3-phenyl-1,4-dihydropyridazine-4,4,5-tricarboxylate;
1-phenylethyl-bis (methoxycarbonyl) 1,4-dihydropyridine;
diethyl-2-methyl-6-benzene(4H-pyran) 4,4-dicarboxylate;
1-(2-naphthylmethyl)-4,4-bis(methoxycarbonyl)-1,4-dihydropyridine;
dimethyl-3-acetyl-1-methyl quinoline-4,4 (1H)-dicarboxylate.
[0117] Examples of suitable specific compounds with the general
formula (V) in the electron donor compounds of the present
invention are: dimethyl fluorene-9,9-dicarboxylate; diethyl
fluorene-9,9-dicarboxylate; di-n-propyl fluorene-9,9-dicarboxylate;
diisopropyl fluorene-9,9-dicarboxylate; di-n-butyl
fluorene-9,9-dicarboxylate; diisobutyl fluorene-9,9-dicarboxylate;
di-n-pentyl fluorene-9,9-dicarboxylate; di-n-hexyl
fluorene-9,9-dicarboxylate; di-n-heptyl fluorene-9,9-dicarboxylate;
di-n-octyl fluorene-9,9-dicarboxylate; diphenyl
fluorene-9,9-dicarboxylate; dihexadecyl fluorene-9,9-dicarboxylate;
dibenzyl fluorene-9,9-dicarboxylate; dipropenyl
fluorene-9,9-dicarboxylate; 9-methyl carboxylate-9-ethyl
carboxylate-fluorene; 9-methyl carboxylate-9-n-propyl
carboxylate-fluorene; 9-methyl carboxylate-9-isopropyl
carboxylate-fluorene; 9-methyl carboxylate-9-n-butyl
carboxylate-fluorene; 9-methyl carboxylate-9-isobutyl
carboxylate-fluorene; 9-ethyl carboxylate-9-n-propyl
carboxylate-fluorene; 9-ethyl carboxylate-9-isopropyl
carboxylate-fluorene; 9-ethyl carboxylate-9-n-butyl
carboxylate-fluorene; 9-ethyl carboxylate-9-isobutyl
carboxylate-fluorene.
[0118] The present invention also provides a method for preparing
the olefin polymerization solid catalyst component by contacting
the olefin polymerization catalyst carrier with a titanium compound
and an electron donor compound to obtain a solid catalyst
component.
[0119] The specific preparation method comprises the following
steps: firstly, an olefin polymerization catalyst carrier of the
invention is contacted with a titanium compound and then is reacted
with an electron donor compound for 1 to 3 hours; after the
reaction, the solid product is treated with a solution of a
titanium compound or with a mixture of an inert organic solvent and
a titanium compound for 1 to 4 times, the solid is washed with an
inert organic solvent for 1 to 7 times and then dried to obtain a
solid catalyst component.
[0120] Preferably, the inert organic solvent (E) and the olefin
polymerization catalyst carrier are formulated into a suspension,
then contacted with the titanium compound and reacted with the
electron donor compound for 1 to 3 hours. When the suspension is
formulated, the titanium compound is contacted with the suspension,
where the suspension may be added to the titanium compound or the
titanium compound may be added to the suspension, the addition may
be either rapid or slow/dropwise. The contact temperature is
-30.degree. C. to 150.degree. C., preferably -15.degree. C. to
80.degree. C. The contact temperature of the electron donor
compound with the suspension and the titanium compound is 0.degree.
C. to 150.degree. C., preferably 20.degree. C. to 100.degree. C.
The molar ratio of the inert organic solvent to the titanium
compound is from 0 to 100, preferably from 0.5 to 40. The treatment
temperature is from 0.degree. C. to 150.degree. C., preferably from
80.degree. C. to 120.degree. C. The solid is washed with an inert
organic solvent for 1 to 7 times and then dried to obtain a solid
catalyst component. The temperature is 0.degree. C. to 150.degree.
C., preferably 20.degree. C. to 100.degree. C. for the first
washing with the inert organic solvent, and the second washing
temperature is 0.degree. C. to 150.degree. C., preferably
40.degree. C. to 80.degree. C.
[0121] The present invention is to provide a catalyst for olefin
CH.sub.2.dbd.CHR polymerization, wherein R is hydrogen or a
hydrocarbon group having 1-12 carbon atoms, the catalyst comprising
the reaction product of the following materials:
[0122] a) an olefin polymerization solid catalyst component of the
present invention;
[0123] b) at least one organic aluminum compound of the general
formula AlR.sub.nX.sub.(3-n), wherein R is hydrogen, hydrocarbon
group having 1-20 carbon atoms; X is halogen, n is an integer of
0.ltoreq.n.ltoreq.3; and optionally,
[0124] c) at least one external electron donor compound.
[0125] Preferably, the organoaluminum compound (b) is selected from
the group consisting of trialkylaluminum compound such as
trimethylaluminum, triethylaluminum, triisobutylaluminum,
tri-n-butyl aluminum, tri-n-hexyl aluminum, trioctyl aluminum. It
is also possible to use trialkylaluminum and alkylaluminum halide,
or a mixture of alkylaluminum sesquichloride such as AlEt.sub.2Cl
and Al.sub.2Et.sub.3Cl.sub.3; alkylalumoxanes can also be used.
[0126] For applications where good isotacticity is required, an
external electron donor compound can be used. The external electron
donor is selected from siloxane compounds represented by general
formula R.sub.nSi(OR.sub.1).sub.4-n, wherein R and R.sub.1 are
C.sub.1-C.sub.18 hydrocarbon group, which may optionally be
substituted by heteroatoms; n is an integer of
0.ltoreq.n.ltoreq.3.
[0127] Said specific silane compounds may be:
trimethylmethoxysilane, trimethylethoxysilane,
tri-n-propylmethoxysilane, tri-n-propylethoxysilane,
tri-n-butylmethoxysilane, triisobutylethoxysilane,
trihexylmethylsilane, trihexylethoxysilane,
dimethyldimethoxysilane, dimethyldiethoxysilane,
di-n-propyldimethoxysilane, diisopropyldimethoxysilane,
di-n-propyldiethoxysilane, diisopropyldiethoxysilane,
di-n-butyldiethoxysilane, diisobutyldiethoxysilane,
di-tert-butyldimethoxysilane, di-tert-butyldimethoxysilane,
di-n-butyldimethoxysilane, diisobutyldimethoxysilane,
di-tert-butyldiethoxysilane, di-n-butyldiethoxysilane,
n-butylmethyldimethoxysilane, di(2-ethylhexyl)dimethoxysilane,
di(2-ethylhexyl)diethoxysilane, dicyclohexyldimethoxysilane,
dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane,
dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane,
cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane,
cyclohexylisopropyldimethoxysilane, cyclohexylethyldiethoxysilane,
cyclopentylmethyldimethoxysilane, cyclopentylethyldiethoxysilane,
cyclopentylisopropyldiethoxysilane,
cyclopentylisobutyldimethoxysilane,
cyclohexyln-propyldimethoxysilane,
cyclohexyln-propyldiethoxysilane, cyclohexyln-butyldiethoxysilane,
pentylmethyldimethoxysilane, pentylmethyldiethoxysilane,
pentylethyldimethoxysilane, pentylethyldiethoxysilane,
cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane,
cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane,
2-ethylhexyltrimethoxysilane, cyclohexyldimethoxysilane,
cyclohexyldiethoxysilane, 2-ethylhexyltriethoxysilane,
ethyltrimethoxysilane, ethyltriethoxysilane,
n-propyltrimethoxysilane, n-propyltriethoxysilane,
isopropyltrimethoxysilane, isopropyltriethoxysilane,
n-butyltrimethoxysilane, isobutyltrimethoxysilane,
tert-butyltrimethoxysilane, n-butyltriethoxysilane,
cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane,
cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane,
vinyltrimethoxysilane, vinyltriethoxysilane,
2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane,
pentyltrimethoxysilane, pentyltriethoxysilane, tetramethoxysilane,
tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane,
cyclohexylcyclopentyldiethoxysilane,
cyclohexylcyclopentyldipropoxysilane,
3-methylcyclohexylcyclopentyldimethoxysilane,
4-methylcyclohexylcyclopentyldimethoxysilane, 3,
5-dimethylcyclohexylcyclopentyldimethoxysilane,
3-methylcyclohexylcyclohexyldimethoxysilane, di(3-methyl
cyclohexyl)dimethoxysilane,
4-methylcyclohexylcyclohexyldimethoxysilane, di(4-methyl
cyclohexyl)dimethoxysilane, 3,
5-dimethylcyclohexylcyclohexyldimethoxysilane,
di(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane,
tetrabutoxysilan. The preferable compound among these organosilicon
compounds are: di-n-propyldimethoxysilane,
diisopropyldimethoxysilane, di-n-butyldimethoxysilane,
diisobutyldimethoxysilane, di-tert-butyl dimethoxysilane,
di-n-butyldiethoxysilane, tert-butyltrimethoxysilane,
dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane,
cyclohexylmethyldimethoxysilane, cyclohexylethyldiethoxysilane,
cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane,
cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane,
cyclopentylethyldimethoxysilane,
cyclohexylcyclopentyldimethoxysilane,
cyclohexylcyclopentyldiethoxysilane,
3-methylcyclohexylcyclopentyldimethoxysilane,
4-methylcyclohexylcyclopentyldimethoxysilane and
3,5-dimethylcyclopentyldimethoxysilane, etc. These compounds C can
be used alone or in combination.
[0128] Preferred examples of silane compounds are cyclohexylmethyl
dimethoxysilane; diisopropyl dimethoxysilane; di-n-butyl
dimethoxysilane; diisobutyl dimethoxysilane; diphenyl
dimethoxysilane; phenyltriethoxysilane; methyl tert-butyl
dimethoxysilane; dicyclopentyl dimethoxysilane;
2-ethylpiperidin-2-t-butyl-dimethoxysilane and
(1,1,1-trifluoro-2-propyl)-2-ethylpiperidine dimethoxysilane and
(1, 1,1-trifluoro-2-propyl)-methyldimethoxysilane, cyclohexyl
trimethoxysilane; tert-butyl trimethoxysilane and tert-hexyl
trimethoxysilane.
[0129] In order to use the catalysts of the present invention for
olefin polymerization, the catalyst prepared by component a, b, c
can be used for both homo-polymerization and co-polymerization.
Typically, the molar ratio of component b to component a is 1-1000
mol per mol of titanium atom contained in the component a,
preferably 50-800 mol per mol of titanium atom contained in the
component a; and the molar ratio of component c to component a is
0.002-10, preferably 0.01-2, more preferably 0.01-0.5.
[0130] The order of the components can be added in any order.
Preferably, component b is firstly added to the polymerization
system, and then component c, and component a is added last.
[0131] The polymerization process of the present invention can be
carried out in the presence or absence of a solvent. Olefin
monomers may be gaseous or liquid phase. Hydrogen can be further
added as a molecular weight modifier. Of course, the polymerization
can also be carried out in the absence of molecular weight
modifier. The polymerization temperature should not be greater than
200.degree. C., preferably is between 20-100.degree. C., and more
preferably between 40-80.degree. C. The polymerization pressure
should not be more than 10 MPa, and is preferably between 1-5 MPa.
Both continuous polymerization and batch polymerization process can
be used. The polymerization reaction can be done in one step or
divided into two or more stages.
[0132] The olefins to be homopolymerized or copolymerized using the
catalyst of the present invention include linear olefins (such as:
ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,
1-nonene, 1-decene, 1-octene); branched olefins (such as:
3-methyl-1-butene and 4-methyl-1-pentene); dienes (such as:
butadiene, vinyl cyclopentene and vinyl cyclohexene). The catalyst
of the present invention is preferably used for polymerization of
polyethylene and polypropylene. These olefins may be used alone or
in combination.
[0133] In terms of the olefin polymerization conducted by using the
catalyst component a, b, c of the present invention (hereinafter
referred to as the main polymerization), prepolymerization is
recommended to increase the activity of the catalysts as well as
the isotacticity, particle properties and of the productpolymers.
The prepolymerization can also be used for styrene
homopolymerization.
[0134] In the prepolymerization process, the addition order of each
component and monomer is arbitrary. Preferably the component b is
firstly added to the system containing an inert gas or olefins to
be polymerized, and then one or more olefins to be polymerized are
added after addition of component a. In the process of olefin
prepolymerization using organosilane, it is recommended that
component b is added to the polymerization system of an inert gas
or olefins to be polymerized, followed by the addition of component
c, which is then followed by the addition of component a, and the
olefins are added last.
[0135] The olefin polymerization catalyst carrier and the solid
catalyst component of the present invention have the following
advantages: [0136] 1) The carrier of the present invention has a
specific chemical composition and physical properties, and can be
obtained by reacting alcohol and magnesium in the presence of
halogen. In particular, the carrier obtained by treating the
reaction product of the alcohol and magnesium-alkoxymagnesium solid
(D) under high temperature and high pressure is converted from a
spherical solid having a loose and roughened surface to a cube-like
shape with a smooth surface. The carrier is then reacted with a
titanium compound to obtain a solid catalyst component which may
contain at least one electron donor compound. [0137] 2) The size
and morphology of the carrier of the invention can be adjusted by
changing the temperature and pressure of the treatment. The
particle size of the carrier after high temperature and high
pressure treatment can be significantly smaller than that before
treatment, the structure is more compact and the mechanical
strength is better, In the course of operation, the carrier can
maintain its basic shape without hindering the polymer chain
growth, so that the catalyst particles is not broken in the effect
of polymer chain growth. [0138] 3) In the present invention, the
distribution of the carrier particles after high temperature and
high pressure treatment is narrower, the content of the fine powder
is small, the stacking density is high, and since the catalyst and
the polymer replicate the structure and morphology of the carrier,
the direct result is that the particle size distribution of the
solid catalyst component, the catalyst and the polymer is
concentrated, the content of the fine powder is small and the
stacking density is high. [0139] 4) The olefin polymerization
catalyst prepared by the carrier and the solid catalyst component
has high activity, which is clearly higher than the activity of the
catalyst prepared by the carrier of the prior technology. In
particular, the carrier which is subjected to high temperature and
high pressure treatment has an activity 10% greater than that of
the catalyst prepared without high temperature and pressure, and
can be generally 20% greater than the activity of the catalyst
prepared by the prior art carriers. [0140] 5) When using the olefin
polymerization catalyst prepared by the carrier, the obtained
polymer has a regular morphology, a compact structure and a high
stacking density.
BRIEF DESCRIPTION OF THE DRAWINGS
[0141] FIG. 1 shows XRD (X-ray diffraction) patterns of various
catalyst carriers of the present invention.
DETAILED DESCRIPTION OF EMBODIMENTS
[0142] Hereinafter, the present invention will be described in
detail by way of examples, but the present invention is not limited
thereto.
[0143] The operation of preparing the catalyst in the examples was
carried out under high purity nitrogen protection.
Example 1
[0144] In a four-necked flask equipped with a stirrer, a reflux
condenser was installed and a cumulative gas meter was connected to
the reflux condenser. After the whole reaction apparatus was fully
purged with nitrogen, 50 mL of anhydrous oxygen free ethanol and
0.55 g of iodine were added to the vessel and dissolved, 6 g of
metallic magnesium was added thereto, and the temperature was
raised to the reflux temperature of ethanol under stirring. 90 mL
of anhydrous ethanol and 9 g of magnesium powder were added every
10 minutes from the start of reflux, for three times in total. The
viscosity of the liquid began to rise sharply at about 1-2 hours
after the completion of the third addition (at this time, the
reaction rate was about 85% as determined by the amount of hydrogen
produced). Then, 150 mL of ethanol was added to the reaction
system, the reaction continued until no hydrogen was produced. The
reaction time was about 6 hours, and a suspension containing a
white solid powder was obtained. The suspension was added to an
autoclave, stirred at 145.degree. C. and 1.4 MPa for 3 hours, and
then filtered under pressure and dried to obtain a carrier Mg
(OEt).sub.2.
Example 2
[0145] The preparation steps of the carrier were the same as those
of Example 1 except that the reaction temperature in the autoclave
was changed from 145.degree. C. to 140.degree. C., the reaction
pressure was changed from 1.4 MPa to 1.0 MPa, and the carrier Mg
(OEt).sub.2 was obtained after 2 hours of reaction time.
Example 3
[0146] To an autoclave fully purged with nitrogen, 40 mL of
anhydrous oxygen free ethanol and 0.33 g of iodine were added and
dissolved. 3 g of metallic magnesium was added thereto, and the
temperature was raised to the reflux temperature of ethanol under
stirring. 40 mL of anhydrous ethanol and 6 g of magnesium powder
were added every 10 minutes from the start of reflux, for three
times in total. The viscosity of the liquid began to rise sharply
at about 1-2 hours after the completion of the third addition (at
this time the reaction rate was about 85% as determined by the
amount of hydrogen produced), then 80 mL of ethanol was added to
the reaction system, the reaction continued until no hydrogen was
produced. The entire reaction time was about 6 hour. After
completion of the reaction, the mixture was heated at 140.degree.
C. and 0.8 MPa for 3 hours, and then filtered under pressure and
dried to obtain a carrier Mg(OEt).sub.2.
Example 4 Catalyst Component
[0147] To a 500 ml of fully nitrogen-purged five-necked flask
equipped with a stirrer were added 10 g of carrier prepared in the
Example 1 and 80 mL toluene to prepare a suspension, and then 20 mL
of titanium tetrachloride was added dropwise at -15.degree. C.,
after addition was completed the system was slowly warmed to
10.degree. C., and was added 60 mL of titanium tetrachloride
dropwise, then the system temperature was slowly raised to
80.degree. C. and then, 12 mmol of dibutyl phthalate was added, and
then the temperature of the system was raised up to 120.degree. C.
and maintained constant for 2 hours, then the liquid was cleaned by
filter pressing and filtered, the resulting solid was washed 3
times with 120 mL titanium tetrachloride at 125.degree. C. The
resulting solid was washed two times at 60.degree. C. and two times
at room temperature with 150 mL of hexane; after removal of the
liquid by filtration and drying the solid, solid powder, i.e. solid
catalyst component, was obtained. Analytical results of the solid
showed that the titanium content was 2.83 (wt) %, dibutyl phthalate
content was 11.24 (wt) %.
Example 5
[0148] The catalyst component was prepared in the same manner as in
Example 4 except that di-n-butyl phthalate was changed to
9,9-methoxymethyl fluorene.
Example 6
[0149] The catalyst component was prepared in the same manner as in
Example 4 except that di-n-butyl phthalate was changed to
2-isopropyl-2-isopentyl-1,3-dimethoxypropane.
Example 7
[0150] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was
replaced with the carrier prepared in Example 2.
Example 8
[0151] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was
replaced with the carrier prepared in Example 2 and di-n-butyl
phthalate was changed to 9,9-methoxymethyl fluorene.
Example 9
[0152] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was changed
to the carrier prepared in Example 2 and the di-n-butyl phthalate
was changed to 2-isopropyl-2-Isopentyl-1,3-dimethoxypropane.
Example 10
[0153] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was
replaced with the carrier prepared in Example 3.
Example 11
[0154] In a four-necked flask equipped with a stirrer, a reflux
condenser was installed and a cumulative gas meter was connected to
the reflux condenser. After the whole reaction apparatus was fully
purged with nitrogen, 50 mL of anhydrous oxygen free ethanol and
0.55 g of iodine were added to the vessel and dissolved, 6 g of
metallic magnesium was added thereto, and the temperature was
raised to the reflux temperature of ethanol under stirring. 90 mL
of anhydrous ethanol and 9 g of magnesium powder were added every
10 minutes from the start of reflux, for three times in total. The
viscosity of the liquid began to rise sharply at about 1-2 hours
after the completion of the third addition (at this time, the
reaction rate was about 85% as determined by the amount of hydrogen
produced). Then, 150 mL of ethanol was added to the reaction
system, the reaction continued until no hydrogen was produced. The
total reaction time was about 6 hours, and a suspension containing
a white solid powder was obtained and then dried to obtain a white
solid powder.
Example 12
[0155] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was changed
to the carrier prepared in Example 11.
Example 13
[0156] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was
replaced with the carrier prepared in Example 11 and di-n-butyl
phthalate was changed to 9,9-methoxymethyl fluorene.
Example 14
[0157] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was changed
to the carrier prepared in Example 11 and the di-n-butyl phthalate
was changed to 2-isopropyl-2-isopentyl-1,3-dimethoxypropane.
Example 15
[0158] The catalyst component was prepared in the same manner as in
Example 4 except that di-n-butyl phthalate was changed to ethyl
2,3-diisopropylsuccinate.
Example 16
[0159] The catalyst component was prepared in the same manner as in
Example 4 except that di-n-butyl phthalate was changed to
9-methoxymethyl-fluorenylcarboxylic acid-(9) ethyl ester.
Example 17
[0160] The catalyst component was prepared in the same manner as in
Example 4 except that di-n-butyl phthalate was changed to diethyl
fluorene-9,9-dicarboxylate.
Example 18
[0161] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was changed
to the carrier prepared in Example 11 and the di-n-butyl phthalate
was changed to ethyl 2,3-diisopropylsuccinate.
Example 19
[0162] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was
replaced with the carrier prepared in Example 11 and the di-n-butyl
phthalate was changed to 9-methoxymethyl-fluorene carboxylic
acid-(9)-ethyl ester.
Example 20
[0163] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was changed
to the carrier prepared in Example 11 and the di-n-butyl phthalate
was changed to diethyl fluorene-9,9-dicarboxylate.
Example 21
[0164] The carrier was prepared in the same manner as the same as
in Example 1 except that the alcohol was changed to a mixed alcohol
of ethanol and n-butanol in a volume ratio of 5:1. The carrier
Mg(OEt).sub.n(O.sup.nBu).sub.2-n (0.ltoreq.n.ltoreq.2) was
obtained.
Example 22
[0165] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier of Example 1 was changed to the
carrier of Example 21.
Example 23
[0166] The carrier was prepared in the same manner as in Example 1
except that the ethanol was changed to n-propanol. The carrier Mg
(O.sup.nPr).sub.2 was obtained.
Example 24
[0167] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier of Example 1 was changed to the
carrier of Example 23.
Example 25
[0168] To an autoclave fully purged with nitrogen, 40 mL of
anhydrous oxygen free ethanol and 0.33 g of iodine were added and
dissolved. 3 g of metallic magnesium was added thereto, and the
temperature was raised to the reflux temperature of ethanol under
stirring. 40 mL of anhydrous ethanol and 6 g of magnesium powder
were added every 10 minutes from the start of reflux, for three
times in total. The viscosity of the liquid began to rise sharply
at about 1-2 hours after the completion of the third addition (at
this time the reaction rate was about 85% as determined by the
amount of hydrogen produced), then 80 mL of ethanol was added to
the reaction system, the reaction continued until no hydrogen was
produced. The entire reaction time was about 6 hour. After
completion of the reaction, the mixture was heated at 160.degree.
C. and 2 MPa for 1 hours, and then filtered under pressure and
dried to obtain a carrier Mg(OEt).sub.2.
Example 26
[0169] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was changed
to the carrier prepared in Example 25.
Example 27
[0170] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was changed
to the carrier prepared in Example 25 and the di-n-butyl phthalate
was changed to 9,9-methoxymethylfluorene.
Example 28
[0171] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was changed
to the carrier prepared in Example 25 and the di-n-butyl phthalate
was changed to 2-isopropyl-2-isopentyl-1,3-dimethoxypropane.
Example 29
[0172] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was changed
to the carrier prepared in Example 25 and the di-n-butyl phthalate
was changed to ethyl 2,3-diisopropylsuccinate.
Example 30
[0173] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was
replaced with the carrier prepared in Example 25 and the di-n-butyl
phthalate was changed to 9-methoxymethyl-fluorenylcarboxylic
acid-(9)-ethyl ester.
Example 31
[0174] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was
replaced with the carrier prepared in Example 25 and the di-n-butyl
phthalate was changed to diethyl fluorene-9,9-dicarboxylate.
Example 32
[0175] To an autoclave fully purged with nitrogen, 40 mL of
anhydrous oxygen free ethanol and 0.33 g of iodine were added and
dissolved. 3 g of metallic magnesium was added thereto, and the
temperature was raised to the reflux temperature of ethanol under
stirring. 40 mL of anhydrous ethanol and 6 g of magnesium powder
were added every 10 minutes from the start of reflux, for three
times in total. The viscosity of the liquid began to rise sharply
at about 1-2 hours after the completion of the third addition (at
this time the reaction rate was about 85% as determined by the
amount of hydrogen produced), then 80 mL of ethanol was added to
the reaction system, the reaction continued until no hydrogen was
produced. The entire reaction time was about 6 hour. After
completion of the reaction, the mixture was heated at 80.degree. C.
and 2.5 MPa for 1 hours, and then filtered under pressure and dried
to obtain a carrier Mg(OEt).sub.2.
Example 33
[0176] The catalyst component was prepared in the same manner as in
Example 4 except that the carrier prepared in Example 1 was
replaced with the carrier prepared in Example 32.
Comparative Example 1
[0177] To a 1000 mL of flask fully purged with nitrogen, 400 mL of
white oil, 46 mL of anhydrous ethanol and 20 g of magnesium
chloride were added, stirred and heated to 130.degree. C. at which
the reaction was continued for 3 hours. The reactant was
transferred to an emulsifier for emulsification at 5000 rpm for 20
min and then transferred to 5000 mL of hexane at -20.degree. C.,
stirred at low temperature for 5 hours and then washed with hexane
for 3 to 6 times. The white powder was filtered, followed by
removing hexane after drying to obtain a spherical carrier.
Comparative Example 2
[0178] To a 500 mL of 5-necked flask fully purged with nitrogen and
equipped with a stirrer, 10 g of the spherical carrier prepared in
Comparative Example 1 and 150 mL of titanium tetrachloride were
added to produce a suspension, maintained at -15.degree. C. for 1
hour, and slowly raised to 80.degree. C., 3.5 g of di-n-butyl
phthalate was added, the temperature was raised to 110.degree. C.
for 1 hour, and then the liquid was filtered off under pressure.
The resulting solid was washed with 120 mL of titanium
tetrachloride at 125.degree. C. three times. The resulting solid
was washed with 150 mL of hexane at 60.degree. C. four times,
followed by filtering the liquid and drying to obtain a solid
powder as a solid catalyst component.
Comparative Example 3
[0179] The catalyst component was prepared in the same manner as in
Comparative Example 2 except that di-n-butyl phthalate was changed
to 9,9-methoxymethyl fluorene.
Comparative Example 4
[0180] The catalyst component was prepared in the same manner as in
Comparative Example 2 except that di-n-butyl phthalate was changed
to 2-isopropyl-2-isopentyl-1,3-dimethoxypropane.
Comparative Example 5
[0181] The carrier was prepared in the same manner as in Example 1
except that the ethanol was changed to a mixed alcohol solution of
methanol, ethanol and isopropanol in a volume ratio of 1:7.5:1.5.
The carrier Mg(OMe).sub.x(OEt).sub.y(O.sup.iPr).sub.z (x+y+z=2) was
obtained.
Comparative Example 6
[0182] The catalyst was prepared in the same manner as in Example 4
except that the carrier of Example 1 was changed to the carrier of
Comparative Example 5.
Comparative Example 7
[0183] The carrier was prepared in the same manner as in Example 1
except that the ethanol was changed to a mixed alcohol solution of
methanol, ethanol and n-butanol in a volume ratio of 1:5:1. The
carrier Mg(OMe).sub.x(OEt).sub.y(O.sup.nBu).sub.z (x+y+z=2) was
obtained.
Comparative Example 8
[0184] The catalyst was prepared in the same manner as in Example 4
except that the carrier of Example 1 was changed to the carrier of
Comparative Example 7.
[0185] As can be seen from FIG. 1, the two sets of diffraction
angles 2.theta. of the carrier obtained in Example 1 are in the
range of 10-11.degree. and 23-25.degree., and there are two main
diffraction peaks in each set, the corresponding diffraction angle
2.theta. values of the highest peaks are 10.4566.degree. and
23.1095.degree..
[0186] The carrier prepared in Example 2 has the above
characteristics, and the corresponding diffraction angles 2.theta.
of the highest peaks in each set are 10.4904.degree. and
23.1433.degree., respectively.
[0187] The carrier obtained in Example 11 has three diffraction
peaks in the range of 5-15.degree. of the diffraction angle
2.theta., and the corresponding diffraction angle 2.theta. of the
highest peak is 10.8660.degree., and there is only one shoulder
peak in the range of 20-30.degree. and no main diffraction
peak.
[0188] The carrier of Comparative Example 1 is a magnesium chloride
alcoholate carrier, there are two diffraction peaks in the range of
5 to 15.degree. of 2.theta., and the corresponding 2.theta. value
of the highest peak is slightly smaller than that of the
above-mentioned ethoxymagnesium carrier.
[0189] The diffraction peaks of the carrier obtained in Example 3
were tested to be characterized in that the corresponding
diffraction angles 2.theta. of the highest peaks in each set are
10.4852.degree. and 23.1045.degree., respectively.
[0190] The diffraction peaks of the obtained carrier of Example 21
are characterized in that the corresponding diffraction angles
2.theta. of the highest peaks in each set are 9.3805.degree. and
21.0952.degree., respectively.
[0191] The diffraction peaks of the obtained carrier of Example 23
are characterized in that the corresponding diffraction angles
2.theta. of the highest peaks in each set are 8.9458.degree. and
24.1983.degree., respectively.
[0192] The diffraction peaks of the obtained carrier of Example 25
are characterized in that the corresponding diffraction angles
2.theta. of the highest peaks in each set are 10.4570.degree. and
23.1842.degree., respectively.
[0193] The diffraction peaks of the obtained carrier of Example 32
are characterized in that the corresponding diffraction angles
2.theta. of the highest peak in each set are 10.4445.degree. and
23.1350.degree., respectively.
Propylene Polymerization
[0194] Propylene polymerization evaluation was made by using the
solid catalyst components prepared in the Examples and comparison
Examples 2-4:
[0195] To a 5 L of stainless steel reactor fully purged with
nitrogen were added 5 mL of solution of triethylaluminum in hexane
at a concentration of 0.5 mol/L and 1 mL of solution of methyl
cyclohexyl dimethoxy silane (CMMS) in hexane at a concentration of
0.1 mol/L and 10 mg of prepared catalyst, 10 mL of hexane was added
to rinse the feed lines, and then 2 L of hydrogen (standard state)
and 2.5 L of purified propylene were added, the reaction was
controlled at 20.degree. C. to prepolymerize for 5 minutes, the
temperature was raised to 70.degree. C., and at this temperature
the polymerization reaction was carried out for 1 hour. After the
reaction, the reactor was cooled and the stirring was stopped, the
reaction product was discharged and dried to obtain a polymer.
(Stacking density of the polymer measured by JB/T 2412-2008 method,
isotacticity measured by JB/T 3682-2000 method). The polymerization
activity was shown in Table 1.
TABLE-US-00001 TABLE 1 Catalyst performance activity isotac-
stacking internal electron donor titanium Kg/ ticity density
Example No. type Wt % Wt % gCat h.sup.-1 % g/cm.sup.3 Example 4
di-n-butyl phthalate 11.24 2.83 5.4 98.6 0.41 Example 5
9,9-methoxymethylfluorene 15.09 3.69 6.8 99.1 0.42 Example 6
2-isopropyl-2-isopentyl- 16.54 3.17 6.9 99.1 0.40
1,3-dimethoxypropane Example 7 di-n-butyl phthalate 13.10 3.33 5.2
98.5 0.40 Example 8 9,9-methoxymethylfluorene 20.34 3.19 6.6 98.9
0.41 Example 9 2-isopropyl-2-isopentyl- 10.89 3.14 6.7 99.3 0.39
1,3-dimethoxypropane Example 10 di-n-butyl phthalate 13.14 3.16 5.0
98.4 0.41 Example 12 di-n-butyl phthalate 11.16 2.54 4.6 99.0 0.40
Example 13 9,9- 20.42 2.84 5.8 99.1 0.39 methoxymethylfluorene
Example 14 2-isopropyl-2-isopentyl- 10.89 3.14 5.5 98.9 0.40
1,3-dimethoxypropane Example 15 ethyl 2,3- 15.55 2.74 4.8 99.1 0.41
diisopropylsuccinate Example 16 9-methoxymethyl- 15.80 3.05 5.5
98.3 0.42 fluorenylcarboxylic acid (9)-ethyl ester Example 17
diethyl fluorene- 13.46 3.32 6.3 98.8 0.42 9,9-dicarboxylate
Example 18 ethyl 2,3- 16.51 2.97 4.2 98.7 0.40 diisopropylsuccinate
Example 19 9-methoxymethyl- 16.24 3.64 5.0 98.2 0.39
fluorenylcarboxylic acid (9)-ethyl ester Example 20 diethyl
fluorene- 14.23 3.45 5.6 98.6 0.41 9,9-dicarboxylate Example 22
di-n-butyl phthalate 11.54 2.74 4.9 98.7 0.40 Example 24 di-n-butyl
phthalate 12.10 2.47 4.7 98.4 0.41 Example 26 di-n-butyl phthalate
12.50 2.71 5.2 98.5 0.40 Example 27 9,9- 18.34 2.50 6.4 98.9 0.40
methoxymethylfluorene Example 28 2-isopropyl-2-isopentyl- 12.20
2.84 6.4 98.4 0.41 1,3-dimethoxypropane Example 29 ethyl 2,3- 14.55
2.58 4.5 98.1 0.42 diisopropylsuccinate Example 30 9-methoxymethyl-
16.24 3.04 5.6 98.1 0.39 fluorenylcarboxylic acid-(9)-ethyl ester
Example 31 diethyl fluorene- 17.32 2.94 5.9 98.3 0.40
9,9-dicarboxylate Example 33 di-n-butyl phthalate 13.56 2.85 5.1
98.4 0.39 Comparative di-n-butyl phthalate 16.59 2.16 4.1 98.6 0.43
Example 2 Comparative 9,9- 19.23 2.51 5.5 99.3 0.43 Example 3
methoxymethylfluorene Comparative 2-isopropyl-2-isopentyl- 18.45
2.78 5.1 99.2 0.44 Example 4 1,3-dimethoxypropane Comparative
di-n-butyl phthalate 12.10 2.92 4.9 98.7 0.42 Example 6 Comparative
di-n-butyl phthalate 13.62 2.85 5.0 98.5 0.42 Example 8
[0196] It can be seen from the polymerization results in Table 1
that the activity of the catalyst prepared by the alkoxymagnesium
carrier is higher than that of the catalyst prepared by the
magnesium chloride ethanol carrier. The activity centers of the
catalyst prepared by the carrier of the examples obtained under
high temperature and high pressure are distributed evenly, the
catalyst activity is high and the polymer made using the catalyst
has a higher stacking density. The propylene polymerization
activity is substantially improved compared to the catalyst
prepared using the carrier of the comparative example which has not
been subjected to high temperature and high pressure treatment,
particularly compared to the catalyst prepared by the magnesium
chloride alcoholate carrier. By changing the reaction temperature,
reaction pressure and reaction time of the high temperature and
high pressure treatment step, the particle size and morphology of
the obtained carrier particles can be adjusted to improve the
performance of the catalysts.
[0197] Although the present invention has been generally described
and in more detail with the specific embodiments, on the basis of
the present invention, it would be obvious for those skilled in
this art to make certain modifications or improvements. Therefore,
these modifications or improvements made without departing from the
spirit of the present invention fall in the scope of the invention
as claimed.
INDUSTRIAL APPLICABILITY
[0198] The present invention relates to an olefin polymerization
catalyst carrier and an olefin polymerization solid catalyst
component prepared from said carrier, a titanium compound, at least
one electron donor compound. For the olefin polymerization catalyst
carrier of the present invention, the distribution of the carrier
particles is concentrated, the content of the fine powder is small,
the stacking density is high, and since the catalyst and the
polymer replicate the structure and morphology of the carrier, the
direct results show that the particle distribution of the solid
catalyst component, the catalyst and the polymer is concentrated,
the content of the fine powder is small and the stacking density is
high. The olefin polymerization catalyst prepared by the carrier
and the solid catalyst component has high activity, and the
obtained polymer has a regular morphology, a compact structure and
a high stacking density. The present invention has industrial
applicability.
* * * * *