JP3421086B2 - Olefin polymerization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to an olefin polymerization method.
It is about. More specifically, the present invention provides
In the absence of a solvent, the olefin
When combined, an electron donating compound (external donor) during polymerization
With high polymerization activity and steric regulation regardless of the presence or absence of
Olefia can produce polymers with excellent regularity.
The present invention relates to a polymerization method for olefins. [0002] 2. Description of the Related Art Conventionally, titanium, magnesium, halogen
And an immobilization component containing an electron donating compound, if necessary.
Minutes and the organoaluminum compound and, if necessary, the electron
Higher olefin polymerization catalyst composed of donor compounds
High tacticity in yield (ie, high catalytic activity)
It is known that a polymer having
You. Recently, when molding polyolefin polymers,
Molding speed to improve molding cycle from the viewpoint of economy
Is required. To do so, the polymer
It is necessary that the molecular weight is small, but its molecular weight is small
At times, conventional high stereoregularity is required. High solid
If it is not a regular polyolefin polymer,
Because it is difficult to obtain the necessary and sufficient performance, for example, rigidity.
You. However, conventionally known catalysts have a molecular weight of
Of relatively large (eg, MFR = 1) polymers
Sometimes a polymer with high stereoregularity is obtained,
Manufacturing small amount (for example, MFR = 50 or more)
When it is difficult to obtain a highly stereoregular polymer under the conditions
There are many. In particular, for gas-phase polymerizations that do not substantially use solvents,
Therefore, the stereoregularity of the produced polymer is lower than that of slurry polymerization.
In many cases, it decreases. Therefore, the above problems were solved
For example, electron donating compounds as external donors
A method of using a large amount of things is conceivable, in which case,
Problems such as a large drop in activity and an increase in catalyst cost are inevitable.
No. [0003] SUMMARY OF THE INVENTION Substantially no solvent is used.
Olefin polymerization in the presence of Ziegler-type catalyst
Sometimes high activity and relatively low molecular weight polymer
For example, MFR of 50 or more, sometimes stereoregularity
A high polymer can be produced. [0004] The present invention solves the above problems.
Investigate various catalyst components for the purpose of giving a decision
And completed the present invention. That is, the present invention comprises the following components
Substantially in the presence of a catalyst comprising (A), (B) and (C)
Polymerizes olefins in the absence of any solvent.
It is a sign. Component (A): The following component (A)₁) And (A_TwoA) contact
Solid component obtained by Ingredient (A₁): Titanium, magnesium and halogen
Contains as an essential component and is represented by the following general formula
Olefium containing a silicon compound substantially in its form
Solid catalyst component for stereoregular polymerization of General formula R¹R^Two _3-nSi (OR^Three)_n (Where R¹Is a branched aliphatic hydrocarbon residue or alicyclic
The hydrocarbon residue is represented by R^TwoIs R¹Same or different carbonization as
A hydrogen residue is represented by R^ThreeRepresents a hydrocarbon residue, and n represents 1 ≦ n ≦ 3
Number, respectively), Ingredient (A_Two): Vinyl silane represented by the following general formula
Compound, General formula (CH_Two= CH)_nSiR^Four _mX_4-mn (Where R^FourRepresents a hydrocarbon residue, X represents hydrogen or halo
M is 0 ≦ m ≦ 3, n is 1 ≦ n ≦ 2 and 1
≦ m + n ≦ 4, respectively), Component (B): an organic aluminum represented by the following general formula
Compound General formula AlR^Five _Three (Where R^FiveIs hydrogen or a hydrocarbon having 1 to 20 carbon atoms
A residue, ^FiveMay be the same or different
I), Component (C): alumoxane. [0005]Detailed description of the invention Olefin polymerization catalyst used in the method of the present invention, a specific
It consists of components (A), (B) and (C). This
Here, “consisting of” means that the ingredients are listed,
That is, only (A), (B) and (C)
It does not imply that a co-existence of a third component is appropriate.
Do not remove. Component (A): Component (A) used in the present invention comprises the following components
(A₁) And component (A) _Two) Is contacted with
Minutes.Ingredient (A ₁ ) : Titanium, magnesium and halogen
Contains as an essential component and is represented by the following general formula
Olefium containing a silicon compound substantially in its form
Solid catalyst component for stereoregular polymerization of General formula R¹R^Two _3-nSi (OR^Three)_n (Where R¹Is a branched aliphatic hydrocarbon residue or alicyclic
The hydrocarbon residue is represented by R^TwoIs R¹Same or different carbonization as
A hydrogen residue is represented by R^ThreeRepresents a hydrocarbon residue, and n represents 1 ≦ n ≦ 3
Number, respectively), Ingredient (A_Two): Vinyl silane represented by the following general formula
Compound, General formula (CH_Two= CH)_nSiR^Four _mX_4-mn (Where R^FourRepresents a hydrocarbon residue, X represents hydrogen or halo
M is 0 ≦ m ≦ 3, n is 1 ≦ n ≦ 2 and 1
≦ m + n ≦ 4, respectively). The component (A) used in the present invention₁)of
Magnesium compounds serving as magnesium sources include
Gnesium dihalide, dialkoxymagnesium,
Lucoxy magnesium halide, magnesium oxyhalide
Ride, dialkyl magnesium, magnesium oxide,
Magnesium hydroxide, magnesium carboxylate, etc.
can give. Among these, magnesium dihalide
preferable. The component (A)₁) Titanium as a titanium source
The compound has the general formula Ti (OR⁶) _4-rX_r(Where R
⁶Is a hydrocarbon residue, preferably one having about 1 to 10 carbon atoms.
X represents a halogen, and r is a number satisfying 0 ≦ r ≦ 4.
Is shown. )). Specific examples and
As a result, TiCl_Four, TiBr_Four, Ti (OC_TwoH _Five)
Cl_Three, Ti (OC_TwoH_Five)_TwoCl_Two, Ti (OC_TwoH
_Five)_ThreeCl, Ti (O-iC_ThreeH₇) Cl_Three, Ti (O
-NC_FourH₉) Cl_Three, Ti (O-nC_FourH ₉)_TwoCl
_Two, Ti (OC_TwoH_Five) Br_Three, Ti (OC_TwoH_Five)
(OC_FourH₉) _TwoCl, Ti (O-nC_FourH₉)_ThreeC
1, Ti (OC₆H_Five) Cl_Three, Ti (O-iC_FourH
₉)_TwoCl_Two, Ti (OC_FiveH₁₁) Cl_Three, Ti (OC
₆H₁₃) Cl_Three, Ti (OC_TwoH_Five)_Four, Ti (On-
C_ThreeH₇)_Four, Ti (O-nC_FourH ₉)_Four, Ti (O-
iC_FourH₉)_Four, Ti (O-nC₆H₁₃)_Four, Ti (O
-NC₈H₁₇)_Four, Ti [OCH_TwoCH (C_TwoH_Five) C
_FourH₉]_FourAnd the like. Of these titanium compounds
Among them, TiCl_Four, Ti (OC_FourH₉)_Four, Ti (OC
_TwoH_Five) Cl_ThreeAre preferred. The component (A)₁Halogen contained in the above)
Halogenation of magnesium and / or titanium as described above
Compounds, but usually other halogens
Sources such as aluminum halides and silicon
Well-known titanium such as halides and phosphorus halides
Supplied from halogenating agents other than halogen compounds
Can also be. Halogen contained in the catalyst component is
Hydrogen, chlorine, bromine, iodine or mixtures thereof
And chlorine is particularly preferred. The component (A) according to the present invention is specified
The silicon compound represented by the general formula is also substantially in the form
It is contained in. Here, "substantially the shape
Means that the component (A) is gas chromatographed.
Analyzed by chromatography, siliconization contained in it
The compound is substantially of the structure represented by the general formula
Means that you can confirm that. Now, the present invention
Compounds used to produce component (A) in
Is General formula R¹R^Two _3-nSi (OR^Three)_n (Where R¹Is a branched aliphatic hydrocarbon residue or alicyclic
The hydrocarbon residue is represented by R^TwoIs R¹Same or different carbonization as
A hydrogen residue is represented by R^ThreeRepresents a hydrocarbon residue, and n represents 1 ≦ n ≦ 3
The numbers are respectively shown). This
An iodine compound is a mixture of a plurality of compounds of the formula
Is also good. Here, R¹Is a branched aliphatic hydrocarbon residue
In some cases, branching from the carbon atom adjacent to the silicon atom
Are preferred. The branching group in that case is alkyl
Group, a cycloalkyl group or an aryl group (eg,
Phenyl or methyl-substituted phenyl).
Good. More preferred R¹Is adjacent to the silicon atom
Carbon atom, that is, α-position carbon atom is secondary or tertiary
Is the carbon atom of In particular, for silicon atoms
A tertiary carbon atom is preferable. R¹But
When it is a branched aliphatic hydrocarbon residue, the number of carbon atoms is usually 3 to
20, preferably 4 to 10. Also, R¹Is alicyclic
When the compound is a formula hydrocarbon residue, it usually has 5 to 20 carbon atoms,
Preferably it is 5-10. R^TwoIs R¹Same as or
Branching with different carbon numbers 1-20, preferably 1-10
Or a linear saturated aliphatic hydrocarbon residue.
It is. R^ThreeIs an aliphatic hydrocarbon residue, preferably carbon
Usually 1 to 10 aliphatic hydrocarbon residues
It is. Specific examples of the silicon compound usable in the present invention
Is as follows. (CH_Three)_ThreeCSi (CH_Three)
(OCH_Three)_Two, (CH_Three)_ThreeCSi (CH (CH_Three)
_Two) (OCH_Three)_Two, (CH_Three)_ThreeCSi (CH_Three)
(OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (CH_Three)
(OCH_Three)_Two, (CH_Three) (C_TwoH_Five) CHSi (C
H_Three) (OCH_Three)_Two, ((CH_Three)_TwoCHCH_Two)_Two
Si (OCH_Three)_Two, (C_TwoH_Five) (CH_Three)_TwoCSi
(CH_Three) (OCH_Three)_Two, (C_TwoH_Five) (CH_Three)_Two
CSi (CH_Three) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCS
i (OCH_Three)_Three, (CH_Three)_ThreeCSi (OC_TwoH_Five)
_Three, (C_TwoH_Five)_ThreeCSi (OC_TwoH_Five)_Three, (C
H_Three) (C_TwoH_Five) CHSi (OCH_Three)_Three, (C
H_Three)_TwoCH (CH_Three)_TwoCSi (CH_Three) (OC
H_Three)_Two, ((CH_Three)_ThreeC)_TwoSi (OCH_Three)_Two,
(C_TwoH_Five) (CH_Three)_TwoCSi (OCH_Three)_Three, (C
_TwoH_Five) (CH_Three)_TwoCSi (OC_TwoH_Five)_Three, (CH
_Three)_ThreeCSi (O-tC_FourH₉) (OCH_Three)_Two, (IC_ThreeH₇)_TwoSi (OCH_Three)_Two,
(IC_ThreeH₇)_TwoSi (OC_TwoH_Five)_Two, (IC
_FourH₉)_TwoSi (OCH_Three)_Two, (C_FiveH₉)_TwoSi
(OCH_Three)_Two, (C_FiveH₉)_TwoSi (OC
_TwoH_Five)_Two, (C_FiveH₉) (CH_Three) Si (OCH_Three)
_Two, (C_FiveH₉) (IC_FourH₉) Si (OCH_Three)_Two,
(C₆H₁₁) Si (CH_Three) (OCH_Three)_Two, (C₆H
₁₁)_TwoSi (OCH_Three)_Two, (C₆H₁₁) (IC
_FourH₉) Si (OCH_Three)_Two, (IC_FourH₉) (Sec
C_FourH₉) Si (OCH_Three)_Two, (IC_FourH₉) (IC
_ThreeH₇) Si (OC_FiveH₁₁)_Two, HC (CH_Three)_TwoC
(CH_Three)_TwoSi (CH_Three) (OCH_Three)_Two, HC (C
H_Three)_TwoC (CH_Three)_TwoSi (OCH_Three)_Three, HC (C
H_Three)_TwoC (CH_Three)_TwoSi (OC_TwoH_Five)_Three, [0012] Embedded imageFurther, this solid component, component (A), is produced
Known electron donors as internal donors.
It can also be manufactured using. Useful for the production of this solid component
Alcohol as an electron donor (internal donor) that can be used
Phenols, ketones, aldehydes, carbo
Acids, esters of organic or inorganic acids, ethers
Donation of oxygen-containing electrons such as amides, acid amides and acid anhydrides
Of body, ammonia, amine, nitrile, isocyanate
Such nitrogen-containing electron donors can be exemplified.
Two or more of these electron donors can be used.
Of these, preferred are organic acid esters and acid halides.
And particularly preferred are phthalic acid esters and acetic acid.
Cellosolve esters and phthalic halides. The above optional components (a) and (b) may be used alone or in combination.
Can be used in combination of two or more. these
The effect of the present invention is greater when optional ingredients are used.
You.Production of component (A ₁ ) Ingredient (A₁) Is the component (A)₁)
The above optional components can be phased or
Contact each other, intermediate and / or finally organic
Medium, such as hydrocarbons or halohydrocarbons.
And can be manufactured by In that case, Ti,
First, a solid product containing Mg and halogen as essential components
Producing and contacting it with a silicon compound of the above general formula
Method (a two-stage method), Ti, M
Make solid products with g and halogen as essential components
By already having this silicon compound in the process
Components (A)₁) Manufacturing method (a one-step method)
It is also possible. The preferred scheme is the former. Up
Component (A₁The contact conditions for each component that constitutes
It can be anything as long as the effect of Ming is recognized,
Generally, the following conditions are preferred. Contact temperature is -50 ~
The temperature is about 200 ° C, preferably 0 to 100 ° C. contact
Methods include rotating ball mill, vibratory mill, jet mill
, Mechanical method using media stirring and crushing machine, inert diluent
For example, there is a method of contacting by stirring in the presence of a diluent.
It is. The inert diluent used at this time is an aliphatic diluent.
Or aromatic hydrocarbons and halohydrocarbons, polysilo
Xane and the like. Component (A)₁)
Any one can be used as long as the effects of the present invention are recognized.
However, generally, the following range is preferable. Titanium compound
The amount used is based on the amount of magnesium compound used.
1 × 10 in molar ratio^-FourGood within the range of ~ 1000
Or within the range of 0.01 to 10. As a halogen source
When using a compound for that purpose, the amount
Halo compound and / or magnesium compound
Magnesium to be used with or without Gen
1 × 10^-2~ 1000
Within the range, preferably within the range of 0.1 to 100
You. The amount of the silicon compound used depends on the amount of the component (A)₁Make up)
Atomic ratio of silicon to titanium component (silicon / titanium)
Of 0.01 to 1000, preferably 0.1 to 100
Within range. When using electron donating compounds
The amount used is based on the amount of magnesium compound used.
1 × 10 in molar ratio^-3It is preferably in the range of 10 to 10, preferably
It is in the range of 0.01 to 5. Component (A)₁) Is the above titanium source, magne
Cium source, halogen source and silicon compound, and necessary
By using other components such as an electron donor, for example,
It is manufactured by such a manufacturing method. (B) Magnesium halide and electron donation as needed
Contacting the body, silicon compound and titanium-containing compound
Law. (B) Alumina or magnesia is converted to phosphorus halide
Material, magnesium halide, electron donation
Body, silicon compound and titanium halide containing compound
How to let. (C) Magnesium halide and titanium tetraalkoxy
By contacting Cid and a specific polymeric silicon compound
Titanium halides and (also
A) need silicon halide and silicon compound
And contacting an electron donor accordingly. This polymer silicon
As the elementary compound, a compound represented by the following formula is suitable. [0017] Embedded image (Where R⁷Is a hydrocarbon residue having about 1 to 10 carbon atoms,
q is the viscosity of the polymer silicon compound is 1 to 100 centimeters.
Demonstrates the degree of polymerization to be about Chistokes)
Means methylhydrogenpolysiloxane, ethyl high
Dorodiene polysiloxane, phenylhydrodienepo
Polysiloxane, cyclohexylhydrogenpolysilo
Xane, 1,3,5,7-tetramethylcyclotetracy
Loxane, 1,3,5,7,9-pentamethylcyclope
Preferred are n-siloxane and the like. (D) The magnesium compound is titanium tetra
Dissolved in an alkoxide and an electron donor to form a halogen
Solid component precipitated with an agent or a titanium halide
A titanium compound and a silicon compound. (E) Organic magnesium compounds such as Grignard reagents
After reacting with halogenating agent, reducing agent, etc.
The electron donor, silicon compound and titanium compound
How you can touch it. (F) A halogenating agent is added to the alkoxy magnesium compound.
And / or titanium compound with or without electron donor
Is a method of contact in the absence. Among these production methods, (a), (c) and (d)
preferable. [0019]Ingredient (A ₂ ): Component used in the present invention
(A_TwoSpecific examples of the vinylsilane compound of the above) include CH
_Two= CH-SiH_Three, CH_Two= CH-SiH_Two(C
H_Three), CH_Two= CH-SiH (CH_Three)_Two, CH_Two=
CH-Si (CH_Three)_Three, CH_Two= CH-SiCl_Three,
CH_Two= CH-SiCl_Two(CH_Three), CH_Two= CH-
SiCl (CH_Three) H, CH_Two= CH-SiCl (C_Two
H_Five)_Two, CH_Two= CH-Si (C_TwoH_Five)_Three, CH_Two
= CH-Si (CH_Three) (C_TwoH_Five)_Two, CH_Two= CH
-Si (C₆H_Five) (CH_Three)_Two, CH_Two= CH-Si
(CH_Three)_Two(C₆H_FourCH_Three), (CH_Two= CH)
(CH_Three)_Two-Si-O-Si (CH_Three)_Two(CH = C
H_Two), (CH_Two= CH)_TwoSiCl_Two, (CH_Two= C
H)_TwoSi (CH_Three)_TwoEtc. can be exemplified.
Of these, vinyl silanes containing no oxygen,
Are divinylsilane, that is, vinyls in which n = 2 is 0 ≦ m ≦ 2.
A silane compound is preferred. Particularly preferably, (CH_Two
= CH)_TwoSi (CH_Three)_Two, (CH_Two= CH)_TwoSi
(CH_Three) Cl, (CH_Two= CH)_TwoSiCl_Two, (C
H_Two= CH)_TwoSi (C_TwoH_Five)_TwoIt is. Production of component (A): Component used in the present invention
(A) is the component (A)₁) And component (A)_TwoA) contact
It is a solid component obtained by drying. Ingredient (A₁) And component (A)
_TwoThe contact conditions in ()) are arbitrary as long as the effects of the present invention are recognized.
In general, the following conditions are preferred:
No. The contact temperature is about −50 to 200 ° C., preferably 0 ° C.
１００100 ° C. The contact method is
Tools, vibratory mills, jet mills, medium agitation mills, etc.
Mechanical method, by stirring in the presence of an inert diluent
And a method of contacting. In this case,
Active diluents include aliphatic or aromatic hydrocarbons and
And halohydrocarbons and polysiloxanes. Success
Minutes (A_Two)), The amount of the vinylsilane compound is
₁) In a molar ratio to the titanium component of 0.001)
To 1,000, more preferably 0.01 to 1,000.
It is in the range of -100. Silicon, aluminum and
When using boron compounds, the amount
1 × 10^-3~ 1
Within the range of 00, preferably within the range of 0.01 to 1.
It is. Component (B): having the following general formula:
Aluminum compound. General formula AlR^Five _Three (Where R^FiveIs hydrogen or carbon number 1-20, preferably
Represents 2 to 10 hydrocarbon residues;^FiveAre the same
But they may be different). Preferred organoaluminization
Compounds include trialkylaluminum
You. As a specific example, Al (CH_Three)_Three, (Al (C_Two
H_Five)_Three, Al (nC_ThreeH₇)_Three, Al (iC_ThreeH₇)
_Three, Al (nC_FourH₉)_Three, Al (iC_FourH₉)_Three, A
l (nC₆H₁₃)_Three, Al (nC₈H₁₇)_Three, Al (n
C_TenH_{twenty one})_Three, Al (C_TwoH_Five)_TwoH, Al (iC_FourH
₉)_TwoH, Al (C_TwoH_Five)_Two(C_ThreeH₇), Al (C
_TwoH_Five)_Two(T-C_FourH₉), Al (C₆H₁₃)_TwoH,
And the like. Of these, Al (C_Two
H_Five)_Three, Al (iC_FourH₉)_Three, Al (nC_ThreeH₇)
_Three, Al (nC_ThreeH₁₃) _Three, Etc. Component (C): Component (C) is alumoxane
is there. Alumoxane is a type of trialkylaluminum
Or two or more trialkylaluminums and water
Is a product obtained by the reaction of Specifically, one type
Almo obtained from Trialkyl Aluminum
Xane, ethylalumoxane, butylalumoxane, a
Sobutylalumoxane and two kinds of trialkyl
Methyl ethyl armoxide obtained from aluminum and water
Sun, methylbutylalumoxane, methylisobutyla
Lumoxane and the like are exemplified. These alumoxanes are combined
Several types of trimethylaluminum can be used in combination.
Aluminum, triethyl aluminum, triisobutyl aluminum
And other alkyls such as dimethylaluminum chloride
It is also possible to use together with aluminum. Also, two kinds
Alumoxanes or one alumoxane and another
By reacting with an organoaluminum compound,
It is also possible to use the formed alumoxane. this
Among them, preferred are methylalumoxane, isobutane
Tylalumoxane, methylisobutylalumoxane and
Of these alumoxanes and trialkylaluminum
A mixture is used. Particularly preferred is methylalumoki
Sun, ethylalumoxane, methylisobutylalumoki
San, isobutylalumoxane. These alumoxanes can be used under various known conditions.
It can be prepared below. Specifically, the following method
Can be exemplified. (A) Trialkylaluminum is converted to toluene and benze
Directly reacts with water using suitable organic solvents such as
Method of (b) Trialkylaluminum and water of crystallization
Salt hydrates, such as copper sulfate, aluminum sulfate
Method to react with hydrate, (c) Trialkylaluminum
Reacting aluminum with water impregnated in silica gel, etc.
Method, (d) trimethylaluminum and triisobutyla
Luminium mixed, toluene, benzene, ether, etc.
A method of directly reacting with water using a suitable organic solvent of
(E) Trimethylaluminum and triisobutylal
Salt hydrate with water of crystallization, for example, sulfur
Heat reaction with copper acid and aluminum sulfate hydrate
Method, (f) impregnate silica gel with water
After treatment with chilled aluminum, trimethylaluminum
(G) methylalumoxane and
And isobutylalumoxane by a known method,
A method of mixing a predetermined amount of these two components and causing a heat reaction. Alumoxane of component (C) used in the present invention
Is preferably one having a low degree of polymerization, specifically,
About 2 to 10, more preferably 2 to 6
Are preferred. Use of each of the components (A) to (C)
The dose is arbitrary as long as the effect of the present invention is observed.
Although possible, in general the following ranges are preferred. component
The amount of (B) and component (C) used relative to component (A)
Is 0.1 to 1000, preferably 1 to 10 by weight.
0. In addition, the components (B) and (C)
The amount used is the weight ratio of component (C) to component (B).
It may be in the range of 0.01 to 100, especially 0.1 to 10
Within the range is preferred. [0025]polymerization: The polymerization method in the present invention is substantially
This is a method of polymerizing an olefin in the absence of a solvent. Heavy
As a combination method, continuous polymerization, batch polymerization, semi-batch polymerization
In this case, any method such as multi-stage polymerization may be used. Polymerization temperature
From room temperature to about 120 ° C., preferably from 50 ° C. to 10 ° C.
It is about 0 ° C. The polymerization pressure is from normal pressure to 50 kg / cm^Two
Degree. Liquid volatility to remove heat of polymerization
Hydrocarbons such as propane, butane, isopentane, etc.
May be supplied and vaporized in the polymerization zone. [0026]Olefin: Α polymerized with the catalyst system of the present invention
-Olefins have the general formula R-CH = CH_Two(Where R
Is a hydrocarbon residue having 1 to 10 carbon atoms and has a branched group
You may. ). Specifically,
Ropylene, butene-1, pentene-1, hexene-1,
Α-olefins such as 1,4-methylpentene-1
is there. In addition to the homopolymerization of these α-olefins,
Polymerization, for example up to 30% by weight relative to propylene
Copolymerize with the olefin and / or ethylene
be able to. Particularly preferred copolymers are propylene and
It is a random or block copolymer of styrene. [0027] 【Example】 Example-1 [Production of component (A)] Remove into a flask which is sufficiently purged with nitrogen.
200 ml of water and deoxygenated n-heptane
And then MgCl_Two0.4 mol, Ti (On
C_FourH₉)_FourAnd reacted at 95 ° C for 2 hours
I let it. After the reaction is completed, the temperature is lowered to 40 ° C.
Lehydropolysiloxane (20 centistoke
Was introduced and reacted for 3 hours. Raw
The solid component formed was washed with n-heptane. Then enough
Into a flask purged with nitrogen as described above.
50 ml of butane was introduced, and the solid synthesized above
The components were introduced in an amount of 0.24 mol in terms of Mg atoms. Then n
-SiCl in 25 ml of heptane_Four  0.4 mol
And introduced into the flask at 30 ° C. for 30 minutes.
The reaction was carried out at 3 ° C. for 3 hours. After the reaction, wash with n-heptane
Was cleaned. Then phthalate was added to 25 ml of n-heptane.
0.024 mol of acid chloride was mixed at 70 ° C., 30
The reaction mixture was introduced into the flask in 90 minutes and reacted at 90 ° C. for 1 hour.
After the completion of the reaction, the resultant was washed with n-heptane. Then SiCl
_Four  Introduce 10 ml and react at 80 ° C for 6 hours
I let you. After the completion of the reaction, the components were thoroughly washed with n-heptane, and the components were removed.
It was a solid component for producing (A). This thing
The tan content was 1.24% by weight. Sufficient purification in a flask that has been sufficiently purged with nitrogen
50 ml of n-heptane was introduced, and then
5 g of the solid component obtained above was introduced, and di
0.5 ml of vinyldimethoxysilane, silicon
(T-Bu) (nPr) Si (OMe) as a compound_Two
1.2 ml, AlEt_Three1.7 g each was introduced,
Add 10 g of divinylbenzene to this at 50 ° C for 2 hours.
Contact. After contact, wash thoroughly with n-heptane
This was designated as component (A). [Vapor phase polymerization of propylene] JP-A-57-7
Gas phase disclosed in Example-1 described in Japanese Patent No. 3011
Using a polymerization device, fully purified polypropylene
And then triethylene as component (B).
Aluminum 50mg, Tet as component (C)
Laethylalumoxane [Al (Et)_TwoOAl (Et)
_Two] To 150 mg of the component (A) produced above.
60 milligrams each were introduced. Then hydrogen gas
Introduce 500 ml and introduce propylene at 75 ° C
Start, total pressure 7kg / cm^Two Polymerization at 75 ° C for 3 hours
went. The result is 296 grams of polymer,
MFR = 96g / 10min, by boiling heptane extraction test
I. I = 97.5 wt%, polymer bulk specific gravity = 0.4
It was 1 g / cc. Embodiment-2 [Production of component (A)] The internal volume of which was sufficiently replaced by nitrogen 0.4
Liter ball mill with 1.6mm inner diameter steel
23 balls were introduced and anhydrous MgCl_Two20 grams
(T-Bu) (nPr) (Ome)_Two3.8 ml, T
iCl_Four1.5 ml each, and the atmosphere at 20 ° C.
Carefully milled for 48 hours. After grinding, remove from mill
And used as a solid component for component (A). Then enough
In a 500 ml flask purged with purified nitrogen,
100 ml of purified n-heptane, and the above solid component
5 grams and 0.5 ml of vinyltrichlorosilane
And contacted at 50 ° C. for 2 hours. After contact, n-hep
This was thoroughly washed with a tan to obtain the component (A). This is the component
As a result of analysis, titanium content = 2.1 wt%, (t-B
u) (nPr) Si (OMe)_TwoContent = 9.6 wt%
there were. [Polymerization of propylene]
In the above case, the amount of component (A) used was 45 mg,
(B) 25 mg of triisobutylaluminum
Ram, hexaisobutylalumoxane as component (C)
175 milligrams, the polymerization temperature was 70 ° C.
Except that the amount of raw gas introduced was 1000 ml,
Polymerization of propylene was carried out in exactly the same manner as in Example-1. So
Resulted in 206 grams of polymer, MFR = 3
3 g / 10 min. I = 96.3 wt%, polymer bulk ratio
Weight = 0.40 g / cc. Comparative Example-1 Under the polymerization conditions of Example 1, the tetrae of component (C)
Exactly the same, except that tilalumoxane was not used
Polymerization was performed. The result is 257 grams of polymer.
MFR = 98 g / 10 min. I = 95.9wt
%, Polymer bulk specific gravity = 0.42 g / cc. Comparative Example 2 Under the polymerization conditions of Example 2, the isobutyric component (C) was used.
Exactly the same except that no rualumoxane was used.
Was performed. The result was 173 grams of polymer.
MFR = 34 g / 10 min. I = 95.0wt
%, Polymer bulk specific gravity = 0.40 g / cc. Examples 3 to 6 [Production of component (A)] For production of component (A) of Example-1
The type and amount of silicon compound used
Except that it was changed as shown in FIG.
The production of the component (A) was carried out. [Polymerization of propylene]
Here, using each component (A) obtained above,
Table 1 shows the amounts and types of the components (B) and (C) used.
The conditions were exactly the same as in Example 1 except that
Was polymerized. Table 1 shows the results. [0035] [Table 1][0036] According to the present invention, the olefin is substantially free of solvent.
When the polymerization is carried out, it has high activity and relatively
Small, for example, 50 or more in MFR,
Highly ordered polymers can be produced.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart for assisting understanding of the technical contents of the present invention relating to a Ziegler catalyst.

Claims (1)

(57) [Claims] 1. From the following components (A), (B) and (C)
Olefin in the presence of a catalyst
An olefin polymerization method for polymerizing olefins. Component (A): The following component (A)₁) And (A_TwoA) contact
Solid component obtained by Ingredient (A₁): Titanium, magnesium and halogen
Contains as an essential component and is represented by the following general formula
Olefium containing a silicon compound substantially in its form
Solid catalyst component for stereoregular polymerization of General formula R¹R^Two _3-nSi (OR^Three)_n (Where R¹Is a branched aliphatic hydrocarbon residue or alicyclic
The hydrocarbon residue is represented by R^TwoIs R¹Same or different carbonization as
A hydrogen residue is represented by R^ThreeRepresents a hydrocarbon residue, and n represents 1 ≦ n ≦ 3
Number, respectively), Ingredient (A_Two): Vinyl silane represented by the following general formula
Compound, General formula (CH_Two= CH)_nSiR^Four _mX_4-mn (Where R^FourRepresents a hydrocarbon residue, X represents hydrogen or halo
M is 0 ≦ m ≦ 3, n is 1 ≦ n ≦ 2 and 1
≦ m + n ≦ 4, respectively), Component (B): an organic aluminum represented by the following general formula
Compound General formula AlR^Five _Three (Where R^FiveIs hydrogen or a hydrocarbon having 1 to 20 carbon atoms
A residue, ^FiveMay be the same or different
I), Component (C): alumoxane.