U.S. patent application number 10/975814 was filed with the patent office on 2005-03-17 for alpha-olefin polymerization catalyst and process for producing alpha-olefin polymer.
This patent application is currently assigned to Sumitomo Chemical Company, Limited. Invention is credited to Fujiwara, Yasuki, Imai, Akio, Satoh, Makoto.
Application Number | 20050059542 10/975814 |
Document ID | / |
Family ID | 15466140 |
Filed Date | 2005-03-17 |
United States Patent
Application |
20050059542 |
Kind Code |
A1 |
Satoh, Makoto ; et
al. |
March 17, 2005 |
Alpha-olefin polymerization catalyst and process for producing
alpha-olefin polymer
Abstract
An .alpha.-olefin polymerization catalyst comprising (A) a solid
catalyst component containing a titanium compound obtained by
treating a solid product having a titanium content of 1.5% by
weight or less obtained by reducing Ti(OR.sup.1).sub.aX.sub.4-a
(R.sup.1 represents a hydrocarbon group having 1 to 20 carbon
atoms, X represents a halogen atom and a represents a number
satisfying 0<a.ltoreq.4.) with an organomagnesium compound in
the presence of an organosilicon compound having an Si--O bond and
an ester compound, with an ester compound, and treating the
ester-treated solid with a mixture of an ether compound and
titanium tetrachloride or a mixture of an ether compound, titanium
tetrachloride and an ester compound, (B) an organoaluminum compound
and (C) an electron donative compound, and a process for producing
an .alpha.-olefin polymer with said .alpha.-olefin polymerization
catalyst.
Inventors: |
Satoh, Makoto;
(Ichihara-shi, JP) ; Fujiwara, Yasuki;
(Sodegaura-shi, JP) ; Imai, Akio; (Ichihara-shi,
JP) |
Correspondence
Address: |
STEVENS DAVIS MILLER & MOSHER, LLP
1615 L STREET, NW
SUITE 850
WASHINGTON
DC
20036
US
|
Assignee: |
Sumitomo Chemical Company,
Limited
Osaka
JP
|
Family ID: |
15466140 |
Appl. No.: |
10/975814 |
Filed: |
October 29, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10975814 |
Oct 29, 2004 |
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10282181 |
Oct 29, 2002 |
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6838412 |
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10282181 |
Oct 29, 2002 |
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08664267 |
Jun 11, 1996 |
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Current U.S.
Class: |
502/103 ;
502/102; 502/114; 502/115; 502/118; 502/122; 502/126; 502/127;
526/125.3; 526/128; 526/153 |
Current CPC
Class: |
C08F 4/6565 20130101;
C08F 10/00 20130101; C08F 10/00 20130101 |
Class at
Publication: |
502/103 ;
502/102; 502/114; 502/115; 502/118; 502/126; 502/127; 502/122;
526/125.3; 526/128; 526/153 |
International
Class: |
B01J 031/00; C08F
004/44 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 15, 1995 |
JP |
7-149030 |
Claims
1-8. (Cancelled)
9. A process for producing an .alpha.-olefin polymer which
comprises polymerizing an .alpha.-olefin with an .alpha.-olefin
polymerization catalyst comprising: (A) a solid catalyst component
obtained by treating a solid product having a titanium content of
1.5% by weight or less obtained by reducing
Ti(OR.sup.1).sub.aX.sub.4-a (R.sup.1 represents a hydrocarbon group
having 1 to 20 carbon atoms, X represents a halogen atom and a
represents a number satisfying 0<a.ltoreq.4.) with an
organomagnesium compound in the presence of an organosilicon
compound having an Si--O bond and an ester compound, with an ester
compound, and treating the ester-treated solid with a mixture of an
ether compound and titanium tetrachloride or a mixture of an ether
compound, titanium tetrachloride and an ester compound; (B) an
organoaluminum compound; and (C) an electron donative compound.
10. A process for producing an .alpha.-olefin polymer according to
claim 9, wherein the organosilicon compound used in the reducing
reaction is a member selected from the group consisting of
organosilicon compounds represented by the general formulae:
Si(OR.sup.2).sub.mR.sup.3.sub.4-m;
R.sup.4(R.sup.5.sub.sSiO).sub.pSiR.sup.6.sub.3; and
(R.sup.7.sub.2SiO).sub.qwherein R.sup.2 is a hydrocarbon group
having 1 to 20 carbon atoms, each R.sup.3, R.sup.4, R.sup.5,
R.sup.6 and R.sup.7 is a hydrocarbon group having 1 to 20 carbon
atoms or hydrogen, m is a number satisfying 0<m.ltoreq.4, p is
an integer of 1 to 1000 and q is an integer of 2 to 1000.
11. A process for producing an .alpha.-olefin polymer according to
claim 9, wherein the organomagnesium is a member selected from the
group consisting of organomagnesium compound represented by the
general formulae: R.sup.8MgX; and R.sup.9R.sup.10Mgwherein each
R.sup.8, R.sup.9 and R.sup.10 represents a hydrocarbon group having
1 to 20 carbon atoms and X represents a halogen.
12. A process for producing an .alpha.-olefin polymer according to
claim 10, wherein the ester compound used in the treatment of the
reduced solid or used as the mixture of the ether compound,
titanium tetrachloride and the ester compound, is a member selected
from the group consisting of saturated aliphatic carboxylates,
unsaturated aliphatic carboxylates, alicyclic carboxylates and
aromatic carboxylates.
13. A process for producing an .alpha.-olefin polymer according to
claim 9, wherein the ester compound is a member selected from the
group consisting of dialkyl ethers, the each alkyl having 2 to 10
carbon atoms and being the same or different each other.
14. A process for producing an .alpha.-olefin polymer according to
claim 9, wherein the amount of the ether compound used in the
treatment of the solid product is 0.1 to 50 mol per 1 mol of the
titanium atom contained in the solid product, and 0.01 to 1.0 mol
per 1 mol of the magnesium atom contained in the solid product.
15. A process for producing an .alpha.-olefin polymer according to
claim 9, wherein the organoaluminum compound is a member selected
from the group consisting of organoaluminum compounds represented
by the general formulae: R.sup.11.sub..gamma.AlY.sub.3-.gamma.; and
R.sup.12R.sup.13Al--O--ALR.sup.14R.sup.15wherein each of R.sup.11
to R.sup.15 represents a hydrocarbon group having 1 to 20 carbon
atoms, Y represents a halogen, hydrogen or an alkoxy group and
.gamma. is a number satisfying 2.ltoreq..gamma..ltoreq.3.
16. A process for producing an .alpha.-olefin polymer according to
claim 9, wherein the amount of the organoaluminum compound used is
0.5 to 1000 mol per 1 mol of the titanium atoms contained in the
solid catalyst component.
17. A process for producing an .alpha.-olefin polymer according to
claim 9, wherein the electron donative compound is a member
selected from the group consisting of alcohols, phenols, ketones,
aldehydes, carboxylic acids, esters of organic acids and inorganic
acids, ethers, acid amides, acid anhydrides, ammonias, amines,
nitrites and isocyanates.
18. A process for producing an .alpha.-olefin polymer according to
claim 17, wherein the electron donative compound is a member
selected from the group consisting of esters of inorganic acids
represented by the general formula:
R.sup.16.sub.nSi(OR.sup.17).sub.4-nwherein R.sup.16 is a
hydrocarbon group having 1 to 20 carbon atoms or hydrogen, R.sup.17
is a hydrocarbon group having 1 to 20 carbon atoms, R.sup.16 and
R.sup.17 each may be different in the same molecule, and n is a
number satisfying 0.ltoreq.n<4, and ethers represented by the
general formula: 2wherein R.sup.18 to R.sup.21 are independently a
straight chain or branched chain alkyl, alicyclic, aryl, alkylaryl
or arylalkyl group having 1 to 20 carbon atoms, and R.sup.18 or
R.sup.19 may be hydrogen.
19. A process for producing an .alpha.-olefin polymer according to
claim 9, wherein the amount of the electron donative compound (C)
is 0.1 to 1000 mol per 1 mol of the titanium atoms contained in the
solid catalyst component (A).
20. A process for producing an .alpha.-olefin polymer according to
claim 9, wherein a preliminary polymerization has been carried out
prior to the polymerization of the .alpha.-olefin.
21. A process for producing an .alpha.-olefin polymer according to
claim 9, wherein the polymerization is carried out in the form of a
slurry polymerization, a solution polymerization, a bulk
polymerization or a gas phase polymerization.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an .alpha.-olefin
polymerization catalyst and a process for producing an
.alpha.-olefin polymer. Particularly, the present invention relates
to an .alpha.-olefin polymerization catalyst giving a highly
stereoregular .alpha.-olefin polymer containing an extremely little
catalyst residue and amorphous polymer and having excellent
mechanical properties and processability, and having an extremely
high catalytic activity per a solid catalyst and per a titanium
atom, and a process for producing a highly stereoregular
.alpha.-olefin polymer with said catalyst.
[0003] 2. Prior Art
[0004] As a process for producing the polymer of .alpha.-olefin
such as propylene, butene-1 or the like, it is well known that the
so-called Ziegler-Natta catalyst comprising a transition metal
compound of the 4th to 6th Groups and an organometallic compound of
the 1st, 2nd or 13th Group in the Periodic Table is used.
[0005] In the production of -olefin polymers, an amorphous polymer
is formed as by-product in addition to a highly stereoregular
.alpha.-olefin polymer having a high value in industrial
application. This amorphous polymer has little value in industrial
application and effects largely a bad influence on mechanical
properties, when the .alpha.-olefin polymer is molded to a molded
article, a film, a fiber and other fabricated goods to be used. The
formation of the amorphous polymer causes the loss of a raw
material monomer and at the same time, an apparatus for removing an
amorphous polymer becomes necessary to cause an extremely large
disadvantage from an industrial viewpoint. Therefore, it is
necessary that a catalyst for producing an .alpha.-olefin polymer
forms no amorphous polymer or forms rarely little.
[0006] In the .alpha.-olefin polymer obtained, a residue of
catalyst comprising a transition metal compound and an
organometallic compound remains. As this catalyst residue causes
problems in the various points such as stability, processability
and the like of the .alpha.-olefin polymer, an apparatus for
removing the catalyst residue and stabilizing the polymer becomes
necessary. As this defect can be improved by increasing a catalyst
activity represented by the weight of the .alpha.-olefin polymer
produced per the unit weight of a catalyst, the above-mentioned
apparatus for removing the catalyst residue becomes unnecessary and
the reduction of the manufacturing cost of .alpha.-olefin polymer
also becomes possible.
[0007] It is known that highly stereoregular and highly active
polymerization of .alpha.-olefin can be realized to a certain
extent by using a Ti--Mg complex type solid catalyst obtained by
reducing a tetra-valent titanium compound with an organomagnesium
compound in the presence of an organosilicon compound thereby
forming the magnesium-titanium eutectic mixture, in combination
with an organoaluminum compound of a promotor and an organosilicon
compound as a third component in polymerization. (Japanese Patent
Publication (Examined) Nos. Hei 3-43283 (1991), Hei 1-319508
(1989))
[0008] In any case, a non-extraction and non-deashing process is in
a possible level, but furthermore, a more improvement is desired.
In the concrete, in order to produce an .alpha.-olefin polymer of
high quality, the realization of further highly stereoregular
polymerization without sacrificing a particle size distribution and
the like is desired. Particularly, in a use such as a field for
molding wherein it is desired to make a polymer be in high
rigidity, a highly stereoregular polymer brings directly out the
quality of a high rigidity, and therefore, the appearance of a
catalyst having a further highly stereoregular polymerizability and
a narrow particle size distribution is acutely desired.
SUMMARY OF THE INVENTION
[0009] An object of the present invention is to provide an
.alpha.-olefin polymerization catalyst having a narrow particle
size distribution and a high catalytic activity enough to be
unnecessary for removing a catalyst residue and an amorphous
polymer and giving an .alpha.-olefin polymer of high
stereoregularity, and a process for producing an .alpha.-olefin
polymer of high quality having a high stereoregularity.
[0010] According to the present invention, there are provided an
.alpha.-olefin polymerization catalyst comprising:
[0011] (A) a solid catalyst component containing a titanium
compound obtained by treating a solid product having a titanium
content of 1.5% by weight or less obtained by reducing
Ti(OR.sup.1).sub.aX.sub.4-a (R.sup.1 represents a hydrocarbon group
having 1 to 20 carbon atoms, X represents a halogen atom and a
represents a number satisfying 0<a.ltoreq.4.) with an
organomagnesium compound in the presence of an organosilicon
compound having an Si--O bond and an ester compound, with an ester
compound, and successively, with a mixture of an ether compound and
titanium tetrachloride or a mixture of an ether compound, titanium
tetrachloride and an ester compound;
[0012] (B) an organoaluminum compound; and
[0013] (C) an electron donative compound, and a process for
producing an .alpha.-olefin polymer which comprises polymerizing an
.alpha.-olefin with said catalyst.
[0014] By using the present catalyst, the fore-mentioned object and
particularly, the highly stereoregular polymerization of an
.alpha.-olefin is attained. The present invention is explained in
detail below.
BRIEF DESCRIPTION OF THE DRAWING
[0015] FIG. 1 is a flow-chart for facilitating the understanding of
the present invention. The flow-chart is a representative of
embodiments of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0016] (a) Titanium Compound
[0017] As the titanium compound used for the synthesis of the solid
catalyst component (A) in the present invention, titanium compounds
represented by the general formula Ti(OR.sup.1).sub.aX.sub.4-a
(R.sup.1 represents a hydrocarbon group having 1 to 20 carbon
atoms, X represents a halogen atom and a represents a number
satisfying 0<a.ltoreq.4.) are illustrated. The example of
R.sup.1 includes an alkyl group such as methyl, ethyl, propyl,
isopropyl, butyl, isobutyl, tert-butyl, amyl, iso-amyl, tert-amyl,
hexyl, heptyl, octyl, decyl, dodecyl and the like; an aryl group
such as phenyl, cresyl, xylyl, naphthyl and the like; an alkenyl
group such as propenyl and the like; an aralkyl group such as
benzyl and the like; and the like. Among these, an alkyl group
having 2 to 18 carbon atoms and an aryl group having 6 to 18 carbon
atoms are preferred. Particularly, a straight chain alkyl group
having 2 to 18 carbon atoms is preferred. Titanium compounds having
2 or more different OR.sup.1 groups each other can be used.
[0018] Examples of the halogen atom represented by X can include
chlorine, bromine and iodine. Among these, particularly chlorine
gives a preferable result.
[0019] The value of a in the titanium compound represented by the
general formula Ti(OR.sup.1).sub.aX.sub.4-a is a number satisfying
0<a.ltoreq.4, preferably 2.ltoreq.a.ltoreq.4 and particularly
preferably a=4.
[0020] As a synthetic method of the titanium compound represented
by the general formula Ti(OR.sup.1).sub.aX.sub.4-a, a well-known
method can be used. For example, a method reacting
Ti(OR.sup.1).sub.4 with TiX.sub.4 in the predetermined ratio or a
method reacting TiX.sub.4 with the predetermined amount of a
corresponding alcohol (R.sup.1OH) can be used. These titanium
compounds may be used as solution diluted with a hydrocarbon
compound or a halogenated hydrocarbon compound.
[0021] The examples include alkoxytitanium trihalide compounds such
as methoxytitanium trichloride, ethoxytitanium trichloride,
butoxytitanium trichloride, phenoxytitanium trichloride,
ethoxytitanium tribromide and the like; dialkoxytitanium dihalide
compounds such as dimethoxytitanium dichloride, diethoxytitanium
dichloride dibuthoxytitanium dichloride, diphenoxytitanium
dichloride, diethoxytitanium dibromide and the like;
trialkoxytitanium monohalide compounds such as trimethoxytitanium
chloride, triethoxytitanium chloride, tributoxytitanium chloride,
triphenoxytitanium chloride, triethoxytitanium bromides and the
like; tetraalkoxytitanium compounds such as tetramethoxytitanium,
tetraethoxytitanium, tetrabutoxytitanium, tetraphenoxytitanium and
the like.
[0022] (b) Organosilicon Compound Having Si--O Bond
[0023] Examples of the organosilicon compound having an Si--O bond
in its molecule used in the synthesis of the solid catalyst
component in the present invention, include the ones represented by
the following general formulae
Si(OR.sup.2).sub.aR.sup.3.sub.4-m;
R.sup.4(R.sup.5.sub.2SiO).sub.pSiR.sup.6.sub.3; and
(R.sup.7.sub.2SiO).sub.q
[0024] wherein R.sup.2 is a hydrocarbon group having 1 to 20 carbon
atoms, each R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 is a
hydrocarbon group having 1 to 20 carbon atoms or hydrogen, m is a
number satisfying 0<m.ltoreq.4, p is an integer of 1 to 1000 and
q is an integer of 2 to 1000.
[0025] Examples of the organosilicon compound include
tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane,
triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane,
tetraisopropoxysilane, diisopropoxydiisopropylsilane,
tetrapropoxysilane, dipropoxydipropylsilane, tetrabuthoxysilane,
dibuthoxydibutylsilane, dicyclopentoxydiethylsilane,
diethoxydiphenylsilane, cyclohexyloxytrimethylsilane,
phenoxytrimethylsilane, tetraphenoxysilane, triethoxyphenylsilane,
hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane,
octaethyltrisiloxane, dimethylpolysiloxane, diphenylpolysiloxane,
methylhydropolysiloxane, phenylhydropolysiloxane and the like.
[0026] Among these organosilicon compounds, the alkoxysilane
compounds represented by the following general formula
Si(OR.sup.2).sub.mR.sup.3.su- b.4-m are preferred,
1.ltoreq.m.ltoreq.4 is preferred and tetraalkoxysilane compounds of
m=4 are particularly preferred.
[0027] (c) Ester Compound
[0028] As the ester compound used in the present invention, mono-
and polyvalent carboxylates are used, and the examples can include
saturated aliphatic carboxylates, olefinic carboxylates, alicyclic
carboxylates and aromatic carboxylates. Concrete examples include
methyl acetate, ethyl acetate, phenyl acetate, methyl propionate,
ethyl propionate, ethyl butyrate, ethyl valerate, methyl acrylate,
ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl
benzoate, methyl toluate, ethyl toluate, ethyl methoxybenzoate,
diethyl succinate, dibutyl succinate, diethylmalonate, dibutyl
malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate,
dibutyl itaconate, monoethyl phthalate, dimethyl phthalate,
methylethyl phthalate, diethylphthalate, di-n-propyl phthalate,
diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate,
di-n-octyl phthalate, diphenyl phthalate and the like.
[0029] Among these ester compounds, unsaturated aliphatic
carboxylates such as methacrylates, maleates and the like and
phthalates are preferred, and diesters of phthalic acid are more
preferred.
[0030] (d) Organomagnesium Compound
[0031] As the organomagnesium compound used in the present
invention, any organomagnesium compounds having an Mg-carbon bond
in its molecule can be used.
[0032] Particularly, a Grignard compound represented by the general
formula R.sup.8MgX (wherein R.sup.8 represents a hydrocarbon group
having up to 20 carbon atoms and X represents a halogen) and
dialkyl magnesium compounds and diaryl magnesium compounds
represented by the general formula: R.sup.9R.sup.10Mg (wherein each
R.sup.9 and R.sup.10 represents a hydrocarbon group having up to 20
carbon atoms) are preferably used. R.sup.8, R.sup.9 and R.sup.10
may be the same or different and the examples include one such as
alkyl groups, aryl groups, aralkyl groups and alkenyl groups having
up to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl,
butyl, sec-butyl, amyl, isoamyl, hexyl, octyl, 2-ethylhexyl,
phenyl, benzyl and the like.
[0033] Examples of the Grignard compound include methylmagnesium
chloride, ethylmagnesium chloride, ethylmagnesium bromide,
ethylmagnesium iodide, propylmagnesium chloride, propylmagnesium
bromide, butylmagnesiumchloride, butylmagnesium bromide,
sec-butylmagnesium chloride, sec-butylmagnesium bromide,
t-butylmagnesium chloride, t-butylmagnesium bromide, amylmagnesium
chloride, isoamylmagnesium chloride hexylmagnesium chloride,
phenylmagnesium chloride, phenylmagnesium bromide and the like, and
the compounds represented by the general formula R.sup.9R.sup.10Mg
include dimethylmagnesium, diethylmagnesium, dipropylmagnesium,
diisopropylmagnesium, dibutylmagnesium, di-sec-butylmagnesium,
di-tert-butylmagnesium, butyl-sec-butylmagnesium, diamylmagnesium,
dihexylmagnesium, diphenylmagnesium, butylethylmagnesium and the
like.
[0034] As a solvent for synthesizing the above-mentioned
organomagnesium compound, an ether solvent such as diethyl ether,
dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether,
diamyl ether, diisoamyl ether, dihexyl ether, dioctyl ether,
diphenyl ether, dibenzyl ether, phenetole, anisole, tetrahydrofuran
or the like can be used. A hydrocarbon solvent such as hexane,
heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene,
xylene or the like, or a mixed solvent of the ether and the
hydrocarbon may be used.
[0035] It is preferred to use the organomagnesium compound in the
state of an ether solution and as the ether solution, an ether
compound having 6 or more carbon atoms in its molecule or a cyclic
ether compound is used. A Grignard compound represented by the
general formula R.sup.8MgX is preferably used as an ether solution
from the point of a catalyst ability. Further, the complex of the
above-mentioned organomagnesium compound and an organometallic
compound other than Mg soluble in a hydrocarbon can be used. As the
example of the organometallic compound, the organic compound of Li,
Be, B, Al or Zn is mentioned.
[0036] (e) Ether Compound
[0037] As the ether compound used in the present invention, dialkyl
ethers such as diethyl ether, dipropyl ether, diisopropyl ether,
dibutyl ether, diisobutyl ether, diamyl ether, diisoamyl ether,
dineopenyl ether, dihexyl ether, dioctyl ether, methylbutyl ether,
methylisoamyl ether, ethylisobutyl ether and the like are
mentioned. Among these, dibutyl ether and diisoamyl ether are
particularly preferred.
[0038] (f) Synthesis of Solid Catalyst
[0039] The solid catalyst of the present invention is synthesized
by treating a solid product obtained by reducing the titanium
compound by the organomagnesium compound in the presence of the
organosilicon compound and the ester compound, with the ester
compound and successively, with the mixture of the ether compound
and titanium tetrachloride or the mixture of the ether compound,
titanium tetrachloride and the ester compound. All these synthetic
reactions are carried out under the atmosphere of an inert gas such
as nitrogen, argon or the like.
[0040] As the method of the reduction of the titanium compound by
the organomagnesium compound, either a method adding the
organomagnesium compound to the mixture of the titanium compound,
the organosilicon compound and the ester compound, or a method
adding inversely the mixture of the titanium compound, the
organosilicon compound and the ester compound to the mixture of the
organomagnesium compound solution is adopted. Between the two, the
method adding the organomagnesium compound to the mixture of the
titanium compound, the organosilicon compound and the ester
compound is preferred from the viewpoint of the catalyst
activity.
[0041] The titanium compound, the organosilicon compound and the
ester compound are preferably used in the solution in or dilution
with a suitable solvent. Such a solvent includes aliphatic
hydrocarbons such as hexane, heptane, octane, decane and the like;
aromatic hydrocarbon atoms such as toluene, xylene and the like;
alicyclic hydrocarbon atoms such as cyclohexane, methylcyclohexane,
decalin and the like; ether compounds such as diethyl ether,
dibutyl ether, diisoamyl ether, tetrahydrofuran and the like.
[0042] The reduction temperature is preferably -50 to 70.degree.
C., more preferably -30 to 50.degree. C. and particularly
preferably -25 to 35.degree. C. When the reduction temperature is
too high, the catalyst activity becomes low.
[0043] In the synthesis of the solid product according to the
reduction, it is possible to let a porous material such as an
inorganic oxide, an organic polymer or the like coexist and to
impregnate the solid product in the porous material. The porous
material preferably has a micropore volume of 0.3 ml/g or more in a
micropore radius of 20 to 200 nm and an average particle diameter
of 5 to 300 .mu.m.
[0044] The porous inorganic oxide includes SiO.sub.2,
Al.sub.2O.sub.3, MgO, TiO.sub.2, ZrO.sub.2,
SiO.sub.2.Al.sub.2O.sub.3 complex oxide, MgO.Al.sub.2O.sub.3
complex oxide, MgO.SiO.sub.2.Al.sub.2O.sub.3 complex oxide and the
like. The porous polymer includes polystyrenes, polyacrylates,
polymethacrylates, polyacrylonitriles, polyvinyl chlorides,
polyolefins and the like. Concrete examples of the porous polymer
include polystyrene, styrene-divinylbenzene copolymer,
styrene-N,N'-alkylene dimethacrylamide copolymer,
styrene-ethyleneglycol methyldimethacrylate copolymer,
polymethylacrylate, polyethylacrylate,
methylacrylate-divinylbenzene copolymer,
ethylacrylate-divinylbenzene copolymer, polymethylmethacrylate,
methylmethacrylate-divinylbenzene copolymer, polyethyleneglycol
dimethylmethacrylate, polyacrylonitrile,
acrylonitrile-divinylbenzene copolymer, polyvinyl chloride,
polyvinyl pyroridine, polyvinyl pyridine,
ethylvinylbenzene-divinylbenzene copolymer, polyethylene,
ethylene-methyl acrylate copolymer, polypropylene and the like.
Among these porous material, SiO.sub.2, Al.sub.2O.sub.3 and
styrene-divinylbenzene copolymer are preferred.
[0045] The dropwise addition time is not specifically restricted
and usually about 30 minutes to 12 hours. After completion of the
reduction, the post reaction may be carried out at a temperature of
20 to 120.degree. C.
[0046] The amount of the organosilicon compound used is preferably
1 to 50, more preferably 3 to 30 and particularly preferably 5 to
25 in terms of an atomic ratio of the silicon atom to the titanium
atom in the titanium compound (Si/Ti). The amount of the ester
compound used is preferably 0.05 to 10, more preferably 0.1 to 6
and particularly preferably 0.2 to 3 in terms of molar ratio of the
ester compound to the titanium atom of the titanium compound (ester
compound/Ti). Furthermore, the amount of the organomagnesium
compound used is preferably 0.1 to 10, more preferably 0.2 to 5.0
and particularly preferably 0.2 to 2.0 in terms of the atomic ratio
of the sum of the silicon atom and the titanium atom to the
magnesium atom (Ti+Si/Mg).
[0047] The solid product obtained by the reduction is subjected to
solid-liquid separation and washed several times with an inert
hydrocarbon solvent such as hexane, heptane or the like. The solid
product thus obtained contains a tri-valent titanium, magnesium and
a hydrocarbyloxy group and indicates usually a non crystallinity or
an extremely low crystallinity. From the point of the catalyst
ability, an amorphous structure is particularly preferred.
[0048] The first characteristic of the present invention is that
the titanium content of the solid product obtained by the reduction
is 1.5% by weight or less, more preferably 0.01 to 1.4% by weight
and most preferably 0.1 to 1.3% by weight. When the titanium
content exceeds 1.5% by weight, the amount of the cold xylene
soluble part which is an amorphous polymer having a little value
for an industrial application, increases. Besides, at the same
time, a polymerization activity decreases and a productivity
deteriorates.
[0049] Next, the solid product obtained by the above-mentioned
method is treated with the ester compound. The amount of the ester
compound used is preferably 0.1 to 150 mol, more preferably 0.3 to
60 mol and particularly preferably 0.5 to 30 mol per 1 mol of the
titanium atom contained in the solid product. The amount of the
ester compound used per 1 mol of the magnesium atom contained in
the solid product is preferably 0.01 to 1.0 mol and more preferably
0.03 to 0.5 mol. When the amount of the ester compound is
excessively much, the particles intends to degradation.
[0050] The treatment of the solid product with the ester compound
can be carried out by any of well-known methods capable of
contacting the solid product with the ester compound such as a
slurry method or a mechanical pulverization means by a ball-mill or
the like. However, when the mechanical pulverization is applied,
finely ground particles from the solid catalyst component are
formed in a large amount, and the particle size distribution
becomes broad, and it is not preferable from the industrial point
of view. Accordingly, it is preferred to contact both in the
presence of a diluent.
[0051] As the diluent, aliphatic hydrocarbons such as pentane,
hexane, heptane, octane or the like, aromatic hydrocarbons such as
benzene, toluene, xylene or the like, alicyclic hydrocarbons such
as cyclohexane, cyclopentane or the like, halogenated hydrocarbons
such as 1,2-dichloroethane, monochlorobenzene or the like can be
used. Among these, aromatic hydrocarbons and halogenated
hydrocarbons are particularly preferred.
[0052] The amount of the diluent used is preferably 0.1 ml to 1000
ml and more preferably 1 ml to 100 ml per 1 g of the solid product.
The treatment temperature is preferably -50 to 150.degree. C. and
more preferably 0 to 120.degree. C. The treatment time is
preferably 5 minutes or more and more preferably 15 minutes to 3
hours. After completion of the treatment, the treated solid is
allowed to stand to separate the solid from the liquid and
successively, washed several times with an inert solvent to obtain
an ester-treated solid.
[0053] Subsequently, the ester-treated solid is treated with the
mixture of the ether compound and titaniumn tetrachloride. This
treatment is preferably carried out in the state of the slurry. The
solvent used for slurring includes aliphatic hydrocarbons such as
pentane, hexane, heptane, octane, decane and the like, aromatic
hydrocarbons such as toluene, xylene and the like, alicyclic
hydrocarbon such as cyclohexane, methylcyclohexane, decalin,
halogenated hydrocarbons such as dichloroethane, trichloroethylene,
monochlorobenzene, dichlorobenzene, trichlorobenzene and the like.
Among these, the halogenated hydrocarbon and the aromatic
hydrocarbon are preferred.
[0054] The slurry concentration is preferably 0.05 to 0.7 g
solid/ml-solvent and more preferably 0.1 to 0.5 g solid/ml-solvent.
The reaction temperature is preferably 30 to 150.degree. C., more
preferably 45 to 135.degree. C. and particularly preferably 60 to
120.degree. C. The reaction time is particularly not restricted.
However, a period of about 30 minutes to 6 hours is usually
preferred.
[0055] As the method feeding the ester-treated solid, the ether
compound and titanium tetrachloride, either of a method adding the
ether compound and titanium tetrachloride to the ester-treated
solid, or a method inversely adding the ester-treated solid to the
solution of the ether compound and titanium tetrachloride may be
effected. In the method adding the ether compound and titanium
tetrachloride to the ester-treated solid, a method adding titanium
tetrachloride after adding the ether compound, or a method adding
the ether compound and titanium tetrachloride at the same time is
preferred, and particularly, a method adding the mixture of the
ether compound and titanium tetrachloride previously prepared to
the ester-treated solid is preferred.
[0056] The reaction of the ester-treated solid with the ether
compound and titanium tetrachloride may be repeated twice or more.
From the view point of catalyst activity and stereoregularity, it
is preferable to repeat at least two times the reaction with the
mixture of the ether compound and titanium tetrachloride.
[0057] The amount of the ether compound used is preferably 0.1 to
100 mol, more preferably 0.5 to 50 mol and particularly preferably
1 to 20 mol per 1 mol of the titanium atom contained in the solid
product. The amount of titanium tetrachloride used is preferably 1
to 1000 mol, more preferably 3 to 500 mol and particularly
preferably 10 to 300 mol per 1 mol of a titanium atom contained in
the solid product. The amount of titanium tetrachloride used is
preferably 1 to 100 mol, more preferably 1.5 to 75 mol and
particularly preferably 2 to 50 mol per 1 mol of the ether
compound.
[0058] In the treatment of the ester-treated solid with the mixture
of the ether compound and titanium tetrachloride, an ester compound
may coexist. The amount of the ester compound used is preferably 30
mol or less, more preferably 15 mol or less and particularly
preferably 5 mol or less per 1 mol of the titanium atom contained
in the solid product.
[0059] The ester is a member selected from the esters described
above.
[0060] The solid catalyst containing a titanium compound obtained
by the above method is subjected to solid-liquid separation and
successively, washed several times with an inert solvent such as
hexane, heptane or the like to be used for polymerization. From the
view point of catalytic activity and stereoregularity, it is
preferable that after solid-liquid separation, the solid catalyst
was washed once or more at a temperature of 50 to 120.degree. C.
with a large amount of a halogenated hydrocarbon solvent such as
monochlorobenzene or the like or an aromatic hydrocarbon solvent
such as toluene or the like, then further washed several times with
an aliphatic hydrocarbon solvent such as hexane, heptane or the
like, and thereafter used in polymerization.
[0061] (g) Organoaluminum Compound (B)
[0062] The organoaluminum compound (B) used in the present
invention has at least one Al-carbon bond in its molecule. The
representatives thereof are organoaluminum compounds represented by
the general formulae:
R.sup.11.sub..gamma.AlY.sub.3-.gamma.; and
R.sup.12R.sup.13Al--O--AlR.sup.14R.sup.15
[0063] wherein R.sup.11 to R.sup.15 represent a hydrocarbon group
having 1 to 20 carbon atoms, Y represents a halogen, hydrogen or an
alkoxy group having 1 to 20 carbon atoms and .gamma. is a number
satisfying 2.ltoreq..gamma..ltoreq.3.
[0064] Examples of the organoaluminum compound include
trialkylaluminums such as triethylaluminum, triisobutylaluminum,
trihexylaluminum and the like; dialkylaluminum hydrides such as
diethylaluminum hydride, diisobutylaluminum hydride and the like;
dialkylaluminum halides such as diethylaluminum chloride and the
like; the mixtures of a trialkylaluminums and a dialkylaluminum
halide such as a mixture of triethylaluminum and diethylaluminum
chloride; alkylalumoxanes such as tetraethyldialumoxane,
tetrabutyldialumoxane and the like.
[0065] Among these organoaluminum compounds, trialkylaluminums,
mixtures of a trialkylaluminum and a dialkylaluminum halide and
alkylaluminoxanes are preferred, and particularly,
triethylaluminum, triisobutylaluminum, the mixture of
triethylaluminum and diethylaluminum chloride, and
tetraethyldialumoxane are preferred.
[0066] The amount of the organoaluminum compound used can be
selected in a wide range as 0.5 to 1000 mol per 1 mol of the
titanium atom contained in the solid catalyst, and the range of 1
to 600 mol is particularly preferred.
[0067] (h) Electron Donative Compound
[0068] As the electron donative compound (C) used for
polymerization in the present invention, electron donors containing
oxygen such as alcohols, phenols, ketones, aldehydes, carboxylic
acids, esters of organic acids and inorganic acids, ethers, acid
amides, acid anhydrides and the like; electron donors containing
nitrogen such as ammonias, amines, nitrites, isocyanates and the
like; and the like can be illustrated. Among them, esters of
inorganic acids and ethers are preferred.
[0069] The esters of inorganic acids are preferably organosilicon
compounds represented by the general formula
R.sup.16.sub.nSi(OR.sup.17).- sub.4-3 in which R.sup.16 is a
hydrocarbon group having 1 to 20 carbon atoms or hydrogen, R.sup.17
is a hydrocarbon group having 1 to 20 carbon atoms, R.sup.16 and
R.sup.17 each may be different in the same molecule, and n is a
number satisfying 0.ltoreq.n<4. The example includes
tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane,
tetraphenoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane,
butyltrimethoxy silane, isobutyltrimethoxysilane,
tert-butyltrimethoxysil- ane, isopropyltrimethoxysilane,
cyclohexyltrimethoxysilane, phenyltrimethoxysilane,
vinyltrimethoxysilane, dimethyldimethoxysilane,
diethyldimethoxysilane, dipropyldimethoxysilane,
propylmethyldimethoxysil- ane, diisopropyldimethoxysilane
dibutyldimethoxysilane, diisobutyldimethoxysilane,
di-tert-butyldimethoxysilane, butylmethyldimethoxysilane,
butylethyldimethoxysilane, tert-butylmethyldimethoxysilane,
tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane,
isobutylisopropyldimethoxysilane,
tert-butylisopropyldimethoxysilane,
tert-butyl-n-butyldimethoxysilane,
tert-butylisobutyldimethoxysilane,
tert-butyl-sec-butyldimethoxysilane, hexylmethyldimethoxysilane,
hexylethyldimethoxysilane, dodecylmethyldimethoxysilane,
dicyclopentyldimethoxysilane, cylcopentylmethyldimethoxysilane,
cylcopentylethyldimethoxysilane,
cylcopentylisopropyldimethoxysilane,
cylcopentylisobutyldimethoxysilane,
cylcopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane,
cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane,
cyclohexylisopropyldimethoxysilane,
cyclohexylisobutyldimethoxysilane,
cyclohexyl-tert-butyldimethoxysilane,
cyclohexylcyclopentyldimethoxysilan- e,
cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane,
phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane,
phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane,
phenylcylcopentyldimethoxysilane, vinylmethyldimethoxysilane,
methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane,
isobutyltriethoxysilane, tert-butyltriethoxysilane,
isopropyltriethoxysilane, cyclohexyltriethoxysilane,
phenyltriethoxysilane, vinyltriethoxysilane,
dimethyldiethoxysilane, diethyldiethoxysilane,
dipropyldiethoxysilane, propylmethyldiethoxysilane- ,
diisopropyldiethoxysilane, dibutyldiethoxysilane,
diisobutyldiethoxysilane, di-tert-butyldiethoxysilane,
butylmethyldiethoxysilane, butylethyldiethoxysilane,
t-butylmethyldiethoxysilane, hexylmethyldiethoxysilane,
hexylethyldiethoxysilane, dodecylmethyldiethoxysilane,
dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane,
cyclohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane,
diphenyldiethoxysilane, phenylmethyldiethoxysilane,
vinylmethyldiethoxysilane, ethyltriisopropoxysilane,
vinyltributoxysilane, phenyltri-tert-butoxysilane,
2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane,
2-norbornanemethyldimethoxysilane, trimethylphenoxysilane,
methyltriaryloxysilane and the like.
[0070] The ethers are preferably dialkyl ethers and diether
compounds represented by the general formula: 1
[0071] wherein R.sup.18 to R.sup.21 are independently a straight
chain or branched alkyl, alicyclic, aryl, alkylaryl or arylalkyl
group having up to 20 carbon atoms and R.sup.18 or R.sup.19 may be
hydrogen. The examples include diethyl ether, dipropyl ether,
diisopropyl ether, dibutyl ether, diamyl ether, diisoamyl ether,
dineopenyl ether, dihexyl ether, dioctyl ether, methylbutyl ether,
methylisoamyl ether, ethylisobutyl ether,
2,2-diisobutyl-1,3-dimethoxypropane,
2-isopropyl-2-isopentyl-1,3-dimethox- ypropane,
2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane,
2-isopropyl-2-3,7-dimethyloctyl-1,3-dimethoxypropane,
2,2-diisopropyl-1,3-dimethoxypropane,
2-isopropyl-2-cyclohexylmethyl-1,3-- dimethoxypropane,
2,2-dicyclohexyl-1,3-dimethoxypropane,
2-isopropyl-2-isobutyl-1,3-dimethoxypropane,
2,2-diisopropyl-1,3-dimethox- ypropane,
2,2-dipropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3--
dimethoxypropane, 2-isopropyl-2-cylcopentyl-1,3-dimethoxypropane,
2,2-dicyclopentyl-1,3-dimethoxypropane,
2-heptyl-2-pentyl-1,3-dimethoxypr- opane and the like.
[0072] Among these electron donative compounds, organosilicon
compounds represented by the general formula
R.sup.22R.sup.23Si(OR.sup.24).sub.2 are particularly preferred.
(Wherein R.sup.22 is a hydrocarbon group having 3 to 20 carbon
atoms in which the carbon adjacent to Si is secondary or tertiary,
and the example includes branched alkyl groups such as isopropyl
group, sec-butyl group, t-butyl group, tert-amyl group and the
like, cycloalkyl groups such as cyclopentyl group, cyclohexyl group
and the like, cycloalkenyl groups such as cyclopentenyl group and
the like, aryl groups such as phenyl group, tolyl group and the
like. R.sup.23 is a hydrocarbon group having 1 to 20 carbon atoms
and the example includes straight chain alkyl groups such as methyl
group, ethyl group, propyl group, butyl group, pentyl group and the
like, branched alkyl groups such as isopropyl group, sec-butyl
group, tert-butyl group, tert-amyl group and the like, cycloalkyl
groups such as cyclopentyl group, cyclohexyl group and the like,
cycloalkenyl groups such as cyclopentenyl group and the like, aryl
groups such as phenyl group, tolyl group and the like. R.sup.24 is
a hydrocarbon group having 1 to 20 carbon atoms and preferably a
hydrocarbon group having 1 to 5 carbon atoms.
[0073] Examples of the organosilicon compound used as such electron
donative compound include diisopropyldimethoxysilane,
diisobutyldimethoxysilane, di-tert-butyldimethoxysilane,
tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane,
tert-butyl-n-propyldimethoxysilane,
isobutylisopropyldimethoxysilane,
tert-butylisopropyldimethoxysilane,
tert-butyl-n-butyldimethoxysilane,
tert-butylisobutyldimethoxysilane,
tert-butyl-sec-butyldimethoxysilane dicyclopentyldimethoxysilane,
cylcopentylisopropyldimethoxysilane,
cylcopentylisobutyldimethoxysilane,
cylcopentyl-tert-butyldimethoxysilane- ,
dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane,
cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane,
cyclohexylisobutyldimethoxysilane,
cyclohexyl-tert-butyldimethoxysilane,
cyclohexylcyclopentyldimethoxysilane,
cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane,
phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane,
phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane,
phenylcylcopentyldimethoxysilane, diisopropyldiethoxysilane,
diisobutyldiethoxysilane, di-tert-butyldiethoxysilane,
tert-butylmethyldiethoxysilane, dicyclopentyldiethoxysilane,
dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane,
cyclohexylethyldiethoxysilane, diphenyldiethoxysilane,
phenylmethyldiethoxysilane, 2-norbornanemethyldimethoxysilane and
the like.
[0074] (i) Process for Polymerizing Olefin
[0075] The .alpha.-olefin applied to the present invention is an
.alpha.-olefin having 3 or more carbon atoms and the examples
include straight chain mono-olefins such as propylene, butene-1,
pentene-1, hexene-1, heptene-1, octene-1, decene-1 and the like;
branched mono-olefins such as 3-methylbutene-1,3-methylpentene-1,
4-methylpentene-1 and the like; vinylcyclohexane and the like.
These .alpha.-olefins may be used alone or in combination of two or
more. In other words, the present invention includes
homopolymerization of an .alpha.-olefin, copolymerization of an
.alpha.-olefin with another .alpha.-olefin and the like. Among
these .alpha.-olefins, it is preferred to homopolymerize propylene
or butene-1 or copolymerize a mixed olefin comprising propylene as
the main component and it is particularly preferred to
homopolymerize propylene or copolymerize the mixed olefin
comprising propylene as the main component. In the copolymerization
of the present invention, the mixture of ethylene and at least one
.alpha.-olefin selected from the above .alpha.-olefins can be used.
Furthermore, it is possible to use a compound having 2 or more
unsaturated bonds such as a conjugated diene or a non-conjugated
diene in the copolymerization. A hetero-block copolymerization
which comprises two or more polymerization steps can be easily
carried out.
[0076] The feeding of each catalyst component to a polymerization
vessel is not particularly restricted except feeding in the
water-free state under an inert gas such as nitrogen, argon or the
like.
[0077] The solid catalyst component (A), the organoaluminum
compound (B) and the electron donative compound (C) may be fed
separately or either two of them are previously contacted and then
fed.
[0078] In the present invention, it is possible to polymerize
olefins in the presence of the above-mentioned catalyst but a
preliminary polymerization described below may be performed before
carrying out the above polymerization (hereinafter, referred to as
"polymerization" or "main polymerization").
[0079] The preliminary polymerization is carried out in the
presence of the solid catalyst component (A) and the organoaluminum
compound (B) by feeding a small amount of an olefin and is
preferred to carried out in the slurry state. As a solvent used for
slurring, an inert hydrocarbon such as propane, butane, isobutane,
pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene
or toluene can be used. In the formation of slurry, a part or the
all part of the inert hydrocarbon may be replaced with a liquid
olefin.
[0080] The amount of the organoaluminum compound used in the
preliminary polymerization can be selected from wide range as from
0.5 to 700 mol per 1 mol of the titanium atom in the solid catalyst
component, and the amount is preferably 0.8 to 500mol, more
preferably 1 to 200 mol per 1 mol of the titanium atom in the solid
catalyst component. The amount of the olefin to be preliminarily
polymerized is usually 0.01 to 1000 g, preferably 0.05 to 500 g and
particularly preferably 0.1 to 200 g per 1 g of the solid catalyst
component.
[0081] The slurry concentration in the preliminary polymerization
is preferably 1 to 500 g--the solid catalyst
component/liter--solvent and particularly preferably 3 to 300
g--the solid catalyst component/liter--solvent. The temperature of
the preliminary polymerization is preferably -20 to 100.degree. C.,
more preferably 0 to 80.degree. C. The partial pressure of the
olefin in the gas phase in the preliminary polymerization is
preferably 0.01 to 20 kg/cm.sup.2 and particularly 0.1 to 10
kg/cm.sup.2 is preferred, but this does not applied to the olefin
being liquid at the pressure and temperature of the preliminary
polymerization. Furthermore, the preliminary polymerization time is
not particularly restricted and 2 minutes to 15 hours is usually
preferred.
[0082] In carrying out the preliminary polymerization, the feeding
of the solid catalyst component (A), the organoaluminum compound
(B) and the olefin may be adopted either by a method for feeding
the olefin after contacting the solid catalyst component (A) with
the organoaluminum compound (B), or a method for feeding the
organoaluminum compound (B) after contacting the solid catalyst
component (A) with the olefin. The feeding of the olefin may be
adopted either by a method for feeding the olefin successively or
continuously while keeping a fixed pressure in the polymerization
vessel, or by a method for feeding all of a predetermined amount of
olefin at the start. A chain transfer agent such as hydrogen can be
added in order to control the molecular weight of a polymer to be
obtained.
[0083] Furthermore, in the preliminary polymerization of a small
amount of the olefin in the presence of solid catalyst component
(A) and the organoaluminum compound (B), the electron donative
compound (C) may, if necessary, coexist. The electron donative
compound used is a part or the all part of the above electron
donative compound (C). The amount used is preferably 0.01 to 400
mol, more preferably 0.02 to 200 mol and particularly preferably
0.03 to 100 mol per 1 mol of the titanium atom contained in the
solid catalyst component (A), and preferably 0.003 to 5 mol, more
preferably 0.005 to 3 mol and particularly preferably 0.01 to 2 mol
per the organoaluminum compound (B).
[0084] The feeding method of the electron donative compound (C) in
the preliminary polymerization is not particularly restricted. It
may be fed separately from the organoaluminum compound (B) and
after contacting with the organoalaminum compound (B), it may be
fed. The olefin used in the preliminary polymerization may be the
same or different from the olefin used in the main
polymerization.
[0085] After the preliminary polymerization was carried out as
mentioned above, or without performing the preliminary
polymerization, the main polymerization of .alpha.-olefins can be
carried out in the presence of the .alpha.-olefin polymerization
catalyst comprising the above-mentioned solid catalyst component
(A), the organoaluminum compound (B), and the electron donative
compound (C).
[0086] The amount of the organcaluminum compound used in the main
polymerization can be selected from such a wide range as from 1 to
1000 mol per 1 mol of the titanium atom contained in the solid
catalyst component (A), and the range of 5 to 600 mol per 1 mol of
the titanium atom contained in the solid catalyst component (A) is
particularly preferred.
[0087] The amount of the electron donative compound (C) used in the
present polymerization is preferably 0.1 to 2000 mol, more
preferably 0.3 to 1000 mol and particularly preferably 0.5 to 800
mol per 1 mol of a titanium atom contained in the solid catalyst
component (A), and preferably 0.001 to 5 mol, more preferably 0.005
to 3 mol and particularly preferably 0.01 to 1 mol per the
organoaluminum compound (B).
[0088] The main polymerization can be carried out at a temperature
of -30 to 300.degree. C. and preferably 20 to 180.degree. C. There
is particularly no restriction on the polymerization pressure.
However, from industrial and economical viewpoints, the pressure is
preferably a normal pressure to 100 kg/cm.sup.2 and more preferably
about 2 to 50 kg/cm.sup.2. As the polymerization form, either of a
batchwise polymerization and a continuous polymerization are
possible. A slurry polymerization or a solution polymerization in
an inert hydrocarbon such as propane, butane, isobutane, pentane,
hexane, heptane or octane, a bulk polymerization in which liquid
olefins at the polymerization temperature is used a medium, or a
gas phase polymerization may be adopted.
[0089] In the main polymerization, it is possible to add a chain
transfer agent such as hydrogen or the like in order to control the
molecular weight of the polymer to be produced.
EXAMPLE
[0090] The present invention is explained in detail by Examples and
Comparative Examples as follows but the present invention is not
particularly limited thereto. The evaluating methods of various
material properties of the polymer in Examples are as follows:
[0091] (1) Xylene-soluble Part at 20.degree. C. (hereinafter,
abbreviated as "CXS")
[0092] After dissolving 1 g of the polymerization powder in 200 ml
of boiling xylene, the obtained solution was slowly cooled to
50.degree. C. and successively cooled to 20.degree. C. with
stirring. After allowed to stand for 3 hours at 20.degree. C., the
polymer precipitated is separated by filtration. Xylene is
evaporated from the filtrate under vacuum at 60.degree. C. thereby
drying and a polymer soluble in xylene at 20.degree. C. is
recovered. and weighed to determine % by weight to the total
polymer. When the value of CXS is the smaller, an amorphous polymer
is the less and it indicates a high stereoregularity.
[0093] (2) Intrinsic Viscosity (hereinafter, abbreviated as
[.eta.])
[0094] It was measured in tetralin solvent at 135.degree. C.
Example 1
[0095] (a) Synthesis of Solid Product
[0096] After a 500 ml flask equipped with a stirrer and a dropping
funnel was substituted with nitrogen, 290 ml of hexane, 2.4 ml of
tetrabuthoxytitanium (2.4 g, 7.1 mmol), 2.5 ml (2.6 g, 9.3 mmol) of
diisobutyl phthalate, and 76.4 ml of tetraethoxysilane (71.4 g, 342
mmol) were thrown into the flask to obtain a homogeneous solution.
Next, while keeping a temperature in the flask at 5.degree. C., 181
ml of the n-butyl ether solution of n-butylmagnesium chloride
(manufactured by YUKI GOSEI YAKUHIN Company Ltd. and the
concentration of n-butylmagnesium chloride is 2.1 mmol/ml) was
gradually dropped into the flask taking 3.3 hour from the dropping
funnel.
[0097] After completion of dropping, it was further stirred for 30
minutes at 5.degree. C. and successively, further stirred for 1
hours at room temperature. Thereafter, after the resulting mixture
was subjected to solid-liquid separation, thus obtained solid was
washed repeatedly three times with 180 ml of toluene and then 155
ml of toluene was added thereto.
[0098] A portion of the solid product slurry was sampled and the
composition analysis was carried out. The titanium atom of 0.87% by
weight, no phthalate, the ethoxy group of 33.1% by weight and the
butoxy group of 1.6% by weight were contained in the solid product.
The slurry concentration was 0.196 g/ml.
[0099] (b) Synthesis of Ester-Treated Solid
[0100] After a 50 ml flask equipped with a stirrer and a dropping
funnel was substituted with nitrogen, 30 ml of the slurry
containing the solid product obtained in the above (a) was thrown
into the flask, and furthermore, 4.2 ml of toluene was added. The
temperature was elevated to 105.degree. C. and stirred for 30
minutes. Next, 5.0 ml (18.7 mmol: 0.85 ml of diisobutyl phthalate/1
g of the solid product) of diisobutyl phthalate was added and
reacted at 105.degree. C. for 30 minutes. After the reaction, the
resulting reaction mixture was subjected to solid-liquid
separation. Thus obtained solid was washed twice with 30 ml of
toluene.
[0101] (c) Synthesis of Solid Catalyst Component (activating
treatment)
[0102] After washing in the above (b), 7.4 ml of toluene, 0.33 ml
of diisobutyl phthalate, 0.59 ml (3.49 mmol) of di-n-butyl ether
and 9.4 ml (0.086mol ) of titanium tetrachloride were added to the
flask and reacted for 3 hours at 105.degree. C. After the
completion of the reaction, the resulting mixture was subjected to
solid-liquid separation at the same temperature. The obtained solid
was washed twice with 30 ml of toluene at the same temperature.
Next, 7.4 ml of toluene, 0.59 ml (3.49 mmol) of di-n-butyl ether
and 4.7 ml (0.043 mol) of titanium tetrachloride were added to the
washed solid and reacted for 1 hour at 105.degree. C. After
completion of the reaction, the obtained mixture was subjected to
solid-liquid separation at the same temperature and successively,
after washing the separated solid three times with 30 ml of toluene
at the same temperature, the washed solid was washed further three
times with 30 ml of hexane and dried under vacuum to obtain 4.1 g
of the solid catalyst component.
[0103] In the solid catalyst component, a titanium atom of 1.64% by
weight, the phthalate of 9.45% by weight, ethoxy group of 0.5% by
weight and butoxy group of 0.2% by weight were contained. In
observation of the solid catalyst component using a microscope, it
had an excellent particle property containing no fine particle.
[0104] (d) Polymerization of Propylene
[0105] A 3-liter stirring type stainless autoclave was substituted
with argon, and 2.6 mmol of triethylaluminum, 0.26 mmol of
cyclohexylethyldimethoxysilane and 7.2 mg of the solid catalyst
component synthesized in (c) were fed in the autoclave and hydrogen
corresponding to a partial pressure of 0.33 kg/cm.sup.2 was
added.
[0106] Subsequently, 780 g of liquid propylene was fed in to the
autoclave, the temperature of the autoclave was elevated to
80.degree. C. and the polymerization was carried out for 1 hour at
80.degree. C. After the polymerization, an unreacted monomer was
purged. The polymer produced was dried under vacuum for 2 hours at
60.degree. C. to obtain 333 g of the polypropylene powder.
[0107] Therefore, the yield of the polypropylene per 1 g of the
solid catalyst component (hereinafter, abbreviated as PP/Cat) was
46,300 (g/g). The ratio of the xylene-soluble part at 20.degree. C.
(CXS) contained in the total yield was 0.66 (wt %), the intrinsic
viscosity of the polymer [.eta.] was 1.88 dl/g. The polymerization
conditions and the polymerization results are shown in Table 1.
Comparative Example 1
[0108] (a) Synthesis of Solid Product
[0109] It was reacted in the same manner as in (a) of Example 1
except that the amounts of the reagents used were 7.5 ml (7.5 g, 22
mmol) of tetrabutoxytitanium, 2.5 ml (2.6 g, 9.3 mmol) of
diisobutyl phthalate, 74.8 ml (70.3 g, 338 mmol) of
tetraethoxysilane and 173 ml of the organomagnesium compound
solution. After the solid product obtained by solid-liquid
separation was repeatedly washed three times by 300 ml of hexane
and three times by 300 ml of toluene, 270 ml of toluene was added.
When a portion of the solid product slurry was sampled and a
composition analysis was performed, the titanium atom of 1.80% by
weight, the phthalate of 0.1% by weight, the ethoxy group of 35.0%
by weight and the butoxy group of 3.2% by weight were contained in
the solid product.
[0110] (b) Synthesis of Ester-Treated Solid
[0111] After a 200 ml flask equipped with a stirrer, a dropping
funnel and a thermometer was substituted with nitrogen, 84 ml of
the slurry containing the solid product obtained in the above (a)
was thrown into the flask, furthermore, 12.1 ml of the supernatant
was taken out, 7.8 ml (29 mmol) of diisobutyl phthalate was added
and they were reacted at 95.degree. C. for 30 minutes. After the
reaction, the resulting mixture was subjected to solid-liquid
separation and the obtained solid was washed twice by 59 ml of
toluene.
[0112] (c) Synthesis of Solid Catalyst Component (activating
treatment)
[0113] After the washing in the above (b), 15.3 ml of toluene, 0.66
ml (2.5 mmol) of diisobutyl phthalate, 1.2 ml (7.1 mmol) of
di-n-butyl ether and 23.4 ml (0.213 mol) of titanium tetrachloride
were added to the flask and reacted for 3 hours at 105.degree. C.
After completion of the reaction, the resulting mixture was
subjected to solid-liquid separation at the same temperature and
successively, the obtained solid was washed twice by 59 ml of
toluene at the same temperature. Next, 12.0 ml of toluene, 1.2 ml
(7.1 mmol) of di-n-butyl ether and 11.7 ml (0.106 mol) of titanium
tetrachloride were added and reacted for 1 hour at 105.degree. C.
After completion of the reaction, the obtained mixture was
subjected to solid-liquid separation at the same temperature and
successively, after washed three times with 59 ml of toluene at the
same temperature, the solid was washed three times with 59 ml of
hexane and dried further under vacuum to obtain 8.1 g of the solid
catalyst component.
[0114] In the solid catalyst component, the titanium atom of 1.5%
by weight, the phthalate of 8.9% by weight, the ethoxy group of
0.4% by weight and the butoxy group of 0.1% by weight were
contained.
[0115] (d) Polymerization of Propylene
[0116] The polymerization of propylene was carried out in the same
manner as in Example 1 (d) except using 4.0 mg of the solid
catalyst component obtained in the above (c). As the result, The
catalyst activity (PP/Cat) was low as 30,000 (g/g), the
stereoregularity was low at CXS=0.74 (wt %) and the [.eta.] was
2.01 dl/g. The polymerization conditions and the polymerization
results are shown in Table 1.
Example 2
[0117] (a) Synthesis of Solid Product
[0118] The synthesis of the solid product was performed in the same
manner as in (a) of Example 1 except that the amounts of the
reagents used were 4.8 ml (4.8 g, 14 mmol) of tetrabutoxytitanium,
2.5 ml (2.6 g, 9.3 mmol) of diisobutyl phthalate and 75.0 ml (70.1
g, 336 mmol) of tetraethoxysilane.
[0119] The portion of the solid product slurry was sampled and
subjected to composition analysis. As results, the titanium atom of
1.22% by weight, the ethoxy group of 33.4% by weight and the butoxy
group of 2.32% by weight were contained in the solid product and no
phthalate was detected. The slurry concentration was 0.208
g/ml.
[0120] (b) Synthesis of Ester-treated Solid
[0121] The synthesis of the ester-treated solid was performed in
the same manner as in (b) of Example 1 except that the amount of
the slurry containing the solid product obtained in the above (a)
was 25 ml and the amount of diisobutyl phthalate was 3.5 ml.
[0122] (c) Synthesis of Solid Catalyst Component (activating
treatment)
[0123] After the washing in the above (b), 6.5 ml of toluene, 0.29
ml (1.08 mmol) of diisobutyl phthalate, 0.52 ml (3.07 mmol) of
di-n-butyl ether and 10.4 ml (0.095 mol) of titanium tetrachloride
were added to the flask and reacted for 3 hours at 105.degree. C.
After completion of the reaction, the resulting mixture was
subjected to solid-liquid separation at the same temperature and
successively, washed twice with 25 ml of toluene at the same
temperature. Next, 6.5 ml of toluene, 0.52 ml (3.07 mmol) of
di-n-butyl ether and 5.2 ml (0.048 mol) of titanium tetrachloride
were added and reacted for 1 hour at 105.degree. C. After the
completion of the reaction, it was subjected to solid-liquid
separation at the same temperature and successively, after washed
three times with 25 ml of toluene at the same temperature, the
solid was washed three times with 25 ml of hexane and dried further
under vacuum to obtain 3.4 g of the solid catalyst component.
[0124] In the solid catalyst component, the titanium atom of 1.42%
by weight, the phthalate of 7.92% by weight, the ethoxy group of
0.64% by weight and the butoxy group of 0.10% by weight were
contained. In the observation by a microscope, the solid catalyst
component had an excellent particle property containing no fine
particle.
[0125] (d) Polymerization of Propylene
[0126] The polymerization of propylene was performed in the same
manner as in the polymerization of propylene of Example 1 (d)
except using the solid catalyst component obtained in the above
(c). As results, the PP/Cat was 43,900 (g/g), the CXS was 0.68 (wt
%) and the [.eta.] was 1.82 dl/g. The polymerization conditions and
the polymerization results are shown in Table 1.
Example 3
[0127] (a) Synthesis of Solid Product
[0128] The synthesis of the solid product was performed in the same
manner as in (a) of Example 1 except that the amounts of the
reagents used were 267 ml of hexane, 3.0 ml (3.0 g, 8.8 mmol) of
tetrabutoxytitanium, 2.5 ml (2.6 g, 9.3 mmol) of diisobutyl
phthalate, 71.6 ml (66.9 g, 321 mmol) of tetraethoxysilane and 170
ml of di-n-butyl ether solution of n-butylmagnesium chloride. When
a portion of the solid product slurry was sampled and subjected to
a composition analysis, the titanium atom of 0.74% by weight, the
phthalate of 0.099% by weight, the ethoxy group of 33.9% by weight
and the butoxy group of 1.67% by weight were contained in the solid
product.
[0129] (b) Synthesis of Ester-Treated Solid
[0130] The synthesis of the solid treated with the ester was
performed in the same condition as in (b) of Example 1.
[0131] (c) Synthesis of Solid Catalyst Component (activating
treatment)
[0132] The synthesis of the solid catalyst component was performed
in the same manner as in (c) of Example 2. In the solid catalyst
component, the titanium atom of 1.40% by weight, the phthalate of
9.13% by weight, the ethoxy group of 0.59% by weight and the butoxy
group of 0.15% by weight were contained. In the observation by a
microscope, the solid catalyst component had an excellent particle
property containing no fine particle.
[0133] (d) Polymerization of Propylene
[0134] The polymerization of propylene was performed in the same
manner as in the polymerization of propylene of Example 1 (d)
except using the solid catalyst component obtained in the above
(c). As results, the PP/Cat was 43,800 (g/g), the CXS was 0.58 (wt
%) and the [.eta.] was 1.70 dl/g. The polymerization conditions and
the polymerization results are shown in Table 1.
Example 4
[0135] (a) Synthesis of Solid Product
[0136] The synthesis of the solid product was performed in the same
manner as in (a) of Example 1 except that the amount of the reagent
used was 3.2 ml (3.2 g, 9.4 mmol) of tetrabutoxytitanium, 7.5 ml
(7.8 g, 28 mmol) of diisobutyl phthalate, 76.0 ml (71.0 g, 341
mmol) of tetraethoxysilane and 186 ml of di-n-butyl ether solution
of n-butylmagnesium chloride. When a portion of the solid product
slurry was sampled and subjected to a composition analysis, the
titanium atom of 0.39% by weight, the ethoxy group of 27.1% by
weight and the butoxy group of 1.66% by weight were contained in
the solid product and no phthalate was detected. The slurry
concentration was 0.180 g/ml.
[0137] (b) Synthesis of Ester-Treated Solid
[0138] After a 200 ml flask equipped with a stirrer, a dropping
funnel and a thermometer was substituted with nitrogen, 28 ml of
the slurry containing the solid product obtained in the above (a)
was thrown into the flask, and furthermore, 1 ml of toluene was
added thereto. The temperature was elevated to 105.degree. C. and
stirred for 30 minutes. Next, 3.35 ml (3.48 g, 12.5 mmol) of
diisobutyl phthalate was added and they were reacted at 105.degree.
C. for 30 minutes. After the reaction, the resulting mixture was
subjected to solid-liquid separation and the obtained solid washed
twice by 25 ml of toluene.
[0139] (c) Synthesis of Solid Catalyst Component (activating
treatment)
[0140] After the end of the washing in the above (b), 7 ml of
toluene, 0.28 ml (0.29 g, 1.05 mmol) of diisobutyl phthalate, 0.5
ml (0.39 g, 3.0 mmol) of di-n-butyl ether and 10 ml (17.3 g, 0.091
mol) of titanium tetrachloride were added to the flask and reacted
for 3 hours at 105.degree. C. After completion of the reaction, the
resulting mixture was subjected to solid-liquid separation at the
same temperature and successively, washed twice with 25 ml of
toluene at the same temperature. Next, 7 ml of toluene, 0.5 ml
(0.39 g, 3.0 mmol) of di-n-butyl ether and 5.0 ml (8.7 g, 0.046
mol) of titanium tetrachloride were added and reacted for 1 hour at
105.degree. C. After completion of the reaction, it was subjected
to solid-liquid separation at the same temperature and
successively, after washed three times with 25 ml of toluene at the
same temperature, washed three times with 25 ml of hexane and dried
further under vacuum to obtain 3.1 g of the solid catalyst
component. In the solid catalyst component, the titanium atom of
1.63% by weight, the phthalate of 7.75% by weight, the ethoxy group
of 0.66% by weight and the butoxy group of 0.14% by weight were
contained. when the solid catalyst component was observed by a
microscope, it had an excellent particle property containing no
fine particle.
[0141] (d) The Polymerization of Propylene
[0142] The polymerization of propylene was performed in the same
manner as in the polymerization of propylene of Example 1 (d)
except using the solid catalyst component obtained in the
above-mentioned (c).
[0143] As results, the PP/Cat was 38,200 (g/g), the CXS was 0.77(wt
%) and the [.eta.] was 1.79 dl/g. The polymerization conditions and
the polymerization results are shown in Table 1.
Example 5
[0144] (d) Polymerization of Propylene
[0145] The polymerization of propylene was performed in the same
manner as in the polymerization of propylene of Example 1 (d)
except using tert-butyl-n-propyldimethoxysilane in place of
cyclohexylethyldimethoxysi- lane.
[0146] As results, the PP/Cat was 57,200 (g/g), the CXS was 0.61
(wt %) and the [.eta.] was 2.36 dl/g. The polymerization conditions
and the polymerization results were shown in Table 1.
Comparative Example 2
[0147] (a) Synthesis of Solid Product
[0148] After the synthesis of the solid product was performed in
the same manner as in (a) of Comparative Example 1 except that the
amounts of the reagents used were 7.5 ml (7.5 g, 22 mmol) of
tetrabutoxytitanium, 2.5 ml (2.6 g, 9.3 mmol) of diisobutyl
phthalate, 73.8 ml (68.9 g, 331 mmol) of tetraethoxysilane and 168
ml of the organomagnesium compound solution, it was heated for 1
hour at 105.degree. C.
[0149] When a portion of the solid product slurry was sampled and
subjected to a composition analysis, the titanium atom of 1.9% by
weight, the phthalate of 0.2% by weight, the ethoxy group of 35.6%
by weight and the butoxy group of 2.7% by weight were contained in
the solid product.
[0150] (b) Synthesis of Ester-Treated Solid
[0151] After a 100 ml flask was substituted with nitrogen, 6.5 g of
the solid product synthesized in (a), 16.2 ml of toluene and 5.5 ml
(21 mmol) of diisobutyl phthalate were added and reacted at
95.degree. C. for 1 hour. After the reaction, the resulting mixture
was subjected to solid-liquid separation and the obtained solid was
washed three times with 33 ml of toluene.
[0152] (c) Synthesis of Solid Catalyst Component (activating
treatment)
[0153] The synthesis of the solid catalyst component was performed
in the same manner as in (c) of Comparative Example 1. In the solid
catalyst component, the titanium atom of 1.9% by weight, the
phthalate of 12.3% by weight, the ethoxy group of 0.4% by weight
and the butoxy group of 0.2% by weight were contained.
[0154] (d) Polymerization of Propylene
[0155] The polymerization of propylene was performed in the same
manner as in the polymerization of propylene of Example 5 (d)
except using the solid catalyst component obtained in the above
(c).
[0156] As results, the PP/Cat was 45,000 (g/g), the CXS was 0.61
(wt %) and the [.eta.] was 2.42 dl/g. The polymerization conditions
and the polymerization results are shown in Table 1.
1 TABLE 1 Titanium content of Electron Polymerization result the
solid product donative PP/Cat CXS [.eta.] (wt %) compound (g/g) (wt
%) (dl/g) Example 1 0.87 CHEDMS 46300 0.66 1.88 Comparative 1.80
CHEDMS 30000 0.74 2.01 Example 1 Example 2 1.22 CHEDMS 43900 0.68
1.82 Example 3 0.74 CHEDMS 43800 0.58 1.70 Example 4 0.39 CHEDMS
38200 0.77 1.79 Example 5 0.87 tBnPDMS 57200 0.61 2.36 Comparative
1.90 tBnPDMS 45000 0.61 2.42 Example 2 CHEDMS:
cyclohexylethyldimethoxysilane tBnPDMS:
tert-butyl-n-propyldimethoxysilane
* * * * *