JPH04296304A - Production of olefinic polymer - Google Patents

Abstract

PURPOSE:To stably and efficiently obtain the title polymer by using a catalyst comprising a solid component for Ziegler type catalyst composed of Ti, Mg and a halogen, a vinylsilane and a granular organic silicone resin in a solventless state while suppressing formation of coarse particles. CONSTITUTION:An alpha-olefin (e.g. propylene) is catalytically polymerized in the absence of a solvent by using a catalyst system prepared by blending (A) a catalytic component for olefin polymerization prepared by bringing a solid component for Ziegler type catalyst containing titanium (e.g. titanium tetrachloride), magnesium (e.g. magnesium chloride) and a halogen as essential components into contact with a vinyl silane compound (e.g. trimethylvinylsilane) to give a contact product and combining the contact product with an organic silicone resin having 0.5-20mu average particle diameter with (B) an organoaluminum compound (e.g. triethylaluminum) to give the objective polymer stably and efficiently while preventing clogging of catalyst feed pipe, adhesion of polymer to polymerizer, formation of coarse polymer particles, etc.

Description

[Detailed description of the invention]

[Background of the invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst and a polymerization method capable of producing highly active and stable olefin polymers under conditions substantially free of solvents.

0002

BACKGROUND OF THE INVENTION Methods for polymerizing olefins include slurry methods and solution methods that use solvents, gas phase methods that do not use solvents, and bulk methods. Among these methods, methods that do not use solvents, such as gas phase methods, are effective methods because they are inexpensive in producing polymers, but they often have problems with operational stability. Various proposals have been made to solve these problems, but it is still difficult to say that they are at a fully satisfactory level.

0003

[Problems to be Solved by the Invention] The problems to be solved by the present invention are caused by various operational troubles during the production of olefin polymers, such as blockage of the catalyst introduction pipe when introducing the catalyst, and catalyst adhesion within the polymerization tank. The aim is to solve problems such as polymer adhesion.

0004

[Means for solving the problem] [Summary of the invention] <Summary>
According to studies conducted by the present inventors, it has been found that the above problem is greatly affected by the properties of the solid component of the catalyst.

The present invention aims to provide a catalyst component which has good catalytic properties and does not cause the various troubles mentioned above, and a method for producing an olefin polymer using the same.

Therefore, the catalyst component for olefin polymerization according to the present invention comprises the following component (A1) and component (A2).
It is characterized by consisting of a combination of. Component (A1) A contact product of the following component (a1) and component (a2), Component (a1) A solid component for a Ziegler type catalyst containing titanium, magnesium and halogen as essential components, Component (a2) A vinyl silane compound, Component (A2) Organic silicone resin with an average particle size of 0.5 to 20 μm.

[0007] Furthermore, the method for producing an olefin polymer according to the present invention involves contacting an α-olefin with a catalyst consisting of a combination of the following components (A) and (B) in substantially the absence of a solvent. It is characterized by polymerization. Component (A) A catalyst component for olefin polymerization consisting of a combination of the following components (A1) and (A2), Component (A1) A contact product of the following components (a1) and (a2), Component (a1) Titanium , a solid component for a Ziegler type catalyst containing magnesium and halogen as essential components, component (a2) a vinyl silane compound, component (A2) an organic silicone resin with an average particle size of 0.5 to 20 μm, component (B) an organic aluminum compound.

<Effects> The catalyst according to the present invention has good catalytic properties and has many effects such as clogging of the catalyst introduction pipe when introducing the catalyst, prevention of polymer adhesion due to catalyst adhesion in the polymerization tank, and prevention of the formation of coarse polymer particles. This makes it possible to solve operational problems that have traditionally been a problem in solventless polymerization methods.

[Detailed Description of the Invention] [I] Catalyst component for olefin polymerization The catalyst component according to the present invention consists of a combination of the following components (A1) and (A2). Here, "consisting of a combination" means the listed components (i.e. (
In addition to combinations of A1) and (A2)), combinations with appropriate auxiliary components are also meant. This catalyst component is an organoaluminum compound (component (B) (
(described in detail later)) to form a catalyst for olefin polymerization. Hereinafter, this catalyst component may be referred to as catalyst component (A) in comparison with organoaluminum compound component (B).

<Component (A1)> Component (A1) is a contact product of components (a1) and (a2). Here, "contact product" refers to the listed components, i.e. component (a
1) and component (a2) alone, and does not exclude the coexistence of other components for a purpose.

<Component (a1)> Essential component Component (a1) is a solid component containing titanium, magnesium and halogen as essential components. here"
"Contained as an essential component" means that in addition to the three listed components, other elements may be included for a purpose, and each of these elements may exist as an arbitrary compound for a purpose. This indicates that the elements are good and that these elements may exist in combination with each other. The solid components, including titanium, magnesium and halogens, are known per se. In the present invention, known solid components can be used as such solid components. For example, JP-A-53
-45688, 54-3894, 54-310
No. 92, No. 54-39483, No. 54-94591, No. 54-118484, No. 54-131589,
No. 55-75411, No. 55-90510, No. 55
-90511, 55-127405, 55-1
No. 47507, No. 55-155003, No. 56-18
No. 609, No. 56-70005, No. 56-72001
No. 56-86905, No. 56-90807, No. 56-155206, No. 57-3803, No. 57-
No. 34103, No. 57-92007, No. 57-121
No. 003, No. 58-5309, No. 58-5310,
No. 58-5311, No. 58-8706, No. 58-2
No. 7732, No. 58-32604, No. 58-3260
No. 5, No. 58-67703, No. 58-117206, No. 58-127708, No. 58-183708,
Those described in Publications No. 58-183709, No. 59-149905, and No. 59-149906 are used.

[0012] Also included are those treated with tungsten or molybdenum compounds.

Examples of the magnesium compound used as a magnesium source in the present invention include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate, and the like. can give. Among these magnesium compounds, magnesium halides, dialkoxymagnesiums, and alkoxymagnesium halides are preferred. The halogen of the halide is typically chlorine and bromine, and the alkoxy is typically lower alkoxy.

The titanium compound serving as a titanium source has the general formula Ti(OR1)4-nXn (where R1 is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, and X is (represents a halogen, and n represents a number of 0≦n≦4). Specific examples include TiCl4, TiBr4, Ti(OC2H5)Cl3
, Ti(OC2H5)2Cl2, Ti(OC2H5)3
Cl, Ti(O-iC3H7)Cl3, Ti(O-nC
4H9) Cl3, Ti(O-nC4H9)2Cl2, T
i(OC2H5)Br3, Ti(OC2H5)(OC4
H9)2Cl, Ti(O-nC4H9)3Cl, Ti(
O-C6H5)Cl3, Ti(O-iC4H9)2Cl
2, Ti(OC5H11)Cl3, Ti(OC6H13
)Cl3, Ti(OC2H5)4, Ti(O-nC3H
7) 4, Ti(O-nC4H9)4, Ti(O-iC4
H9)4, Ti(O-nC6H13)4, Ti(O-n
C8H17)4, Ti[OCH2CH(C2H5)C4
H9]4 etc.

[0015] Furthermore, a molecular compound obtained by reacting TiX'4 (here, X' represents a halogen) with an electron donor described later can also be used. Specific examples of such molecular compounds include TiCl4・CH3COC2H5, TiC
l4・CH3CO2C2H5, TiCl4・C6H5N
O2, TiCl4・CH3COCl, TiCl4・C6
H5COCl, TiCl4・C6H5CO2C2H5,
TiCl4・ClCOC2H5, TiCl4・C4H4
Examples include O.

Among these titanium compounds, preferred are TiCl4, Ti(OC2H5)4, Ti(OC2H5)4, and Ti(OC2H5)4.
4H9)4, Ti(OC4H9)Cl3, etc.

[0017] Furthermore, the general formula Ti(OR2)3-p Xp
(Here, R2 is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, X represents a halogen, and p
indicates a number of 0<p≦3. ) can also be used. Specific examples of such titanium compounds include TiCl3, TiBr3, Ti(OCH3)C
12, Ti(OC2H5)Cl2, etc.

Furthermore, it is also possible to use titanocene compounds such as dicyclopentadienyldichlorotitanium, dicyclopentadienyldimethyltitanium, and bisindenyldichlorotitanium.

The halogen source is usually supplied from the above-mentioned magnesium and/or titanium halogen compounds, but other halogen sources such as aluminum halides, silicon halides, and phosphorous halides can also be used. It can also be supplied from known halogenating agents such as. It is also possible to use an ester as an electron donor (details below) in the form of its acyl halide (eg phthaloyl chloride) and utilize the halogen as a halogen source. The halogen contained in the catalyst component may be fluorine, chlorine, bromine, iodine or mixtures thereof, with chlorine being particularly preferred.

Optional Components (Part 1) As mentioned above, the solid component (a1) used in the present invention may further contain various optional components in addition to the above-mentioned essential components. Thus, for example, when producing this solid component (a1), it can be produced using an electron donor as an internal donor.

Electron donors (internal donors) that can be used in the production of this solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, and acid amides. kind,
Examples include oxygen-containing electron donors such as acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

More specifically, (a) methanol, ethanol, propanol, pentanol, hexanol,
Alcohols with 1 to 18 carbon atoms such as octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, (b) phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol , nonylphenol, naphthol, etc., which may have an alkyl group with 6 carbon atoms
(3) Ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, (d) acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, etc. Aldehydes having 2 to 15 carbon atoms, methyl (ho)formate, methyl acetate, ethyl acetate,
Vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate,
Ethyl crotonate, ethyl cyclohexanecarboxylate,
Methyl benzoate, ethyl benzoate, propyl benzoate,
Butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate,
Amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, γ-butyrolactone, α-valerolactone, coumarin, phthalide, ethylene carbonate, etc. organic acid esters having 2 to 20 carbon atoms, (f) inorganic acid esters such as silicic acid esters such as ethyl silicate, butyl silicate, phenyltriethoxysilane, (g) acetyl chloride, benzoyl chloride, toluyl Acid halides having 2 to 15 carbon atoms such as acid chloride, anisyl chloride, phthaloyl chloride, and isophthaloyl isochloride; (3) carbon such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether; Ethers of numbers 2 to 20, (li) acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, (nu) methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, Examples include amines such as picoline and tetramethylethylenediamine, and nitriles such as (l)acetonitrile, benzonitrile, and tolnitrile. Two or more types of these electron donors can be used. Preferred among these are organic acid esters and organic acid halides, and particularly preferred are phthalate esters, cellosolve acetate, and phthalate halides.

Composition ratio of component (a1) (Part 1) The amount of each of the above components used may be arbitrary as long as the effects of the present invention are observed, but it is generally preferable to fall within the following range.

[0024] The amount of the titanium compound used is 1 x 10-4 to 1 x 10-4 in molar ratio to the amount of the magnesium compound used.
It is preferably within the range of 1000, preferably within the range of 0.01 to 10. When using a compound for that purpose as a halogen source, the amount used is 1 x 10 molar ratio to the amount of magnesium used, regardless of whether the titanium compound and/or magnesium compound contains a halogen. -2 to 1000, preferably 0.1 to 1
00, within the range.

[0025] When using the electron donating compound, the amount used is within the range of 1 x 10-3 to 10, preferably 0.01 to 5, in molar ratio to the amount of the above magnesium compound used. .

Production of component (a1) (Part 1) Component (a
The solid component 1) is produced using the above-mentioned titanium source, magnesium source and halogen source, and further, if necessary, other components mentioned above or described later, such as an electron donor, for example, by the following production method. (a) A method of bringing magnesium halide and, if necessary, an electron donor and a titanium-containing compound into contact. (b) A method of treating alumina or magnesia with a halogenated phosphorus compound and contacting it with a magnesium halide, an electron donor, and a titanium/halogen-containing compound. (c) A solid component obtained by contacting magnesium halide with titanium tetraalkoxide and a specific polymeric silicon compound is added with a titanium halide compound and (
or) method of contacting silicon with halogen compounds.

As this polymeric silicon compound, those represented by the following formula are suitable.

[Chemical formula 1] (Here, R3 is a hydrocarbon residue having about 1 to 10 carbon atoms,
q indicates the degree of polymerization such that the viscosity of the polymeric silicon compound is approximately 1 to 100 centistokes. )

00
28] Among these, methylhydrogenpolysiloxane, ethylhydrogenpolysiloxane, phenylhydrogenpolysiloxane, cyclohexylhydrogenpolysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 ,7,9-
Pentamethylcyclopentasiloxane, etc. are preferred. (d) A method in which a magnesium compound is dissolved in a titanium tetraalkoxide and an electron donor, and the titanium compound is brought into contact with a solid component precipitated with a halogenating agent or a titanium halogen compound. (e) A method in which an organomagnesium compound such as a Grignard reagent is reacted with a halogenating agent, a reducing agent, etc., and then an electron donor and a titanium compound are brought into contact with the compound as necessary. (f) A method of contacting an alkoxymagnesium compound with a halogenating agent and/or a titanium compound in the presence or absence of an electron donor. (g) In any of the above methods, a method in which an optional component described below is present.

[0029] The contact temperature is about -50 to 200°C, preferably about 0 to 100°C. As for the contact method,
Examples include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a media agitation pulverizer, etc., and a method of contacting by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons, halohydrocarbons, and polysiloxanes.

[0030] During these contacts, other components other than the above-mentioned components, such as methylhydrogenpolysiloxane, ethyl borate, aluminum triisopropoxide, aluminum trichloride, and silicon chloride, tetravalent titanium compound,
It is also possible to coexist with trivalent titanium compounds, etc. (
Details below).

In this way, a solid component (a1) for a Ziegler catalyst containing titanium, magnesium and halogen as essential components is obtained.

Optional component (part 2) The component (a1) used in the present invention is the essential component (T
i, Mg, and a halogen), it may contain an electron donor as an optional component, as described above, but the following can be further used as an optional component.

That is, component (a1) is SiCl4
, silicon compounds such as CH3SiCl3, polymeric silicon compounds such as methyl hydrogen polysiloxane, Al
(OiC3H7)3, AlCl3, AlBr3, Al(
Aluminum compounds such as OC2H5)3, Al(OCH3)2Cl, and B(OCH3)3, B(OC2H5)
3, boron compounds such as B(OC6H5)3, WCl6,
Tungsten compounds such as WCl5, WI5, MoCl5
It is possible to use other components such as molybdenum compounds such as MoBr5 in combination with silicon, aluminum, boron,
It may also remain in the solid component as components such as tungsten and molybdenum.

[0034] In addition to the above silicon compounds, organosilicon compounds of the following general formula can be mentioned. R4R53-r Si(OR6)r (However, R4 is a branched hydrocarbon residue, R5 is R4
R6 is a hydrocarbon residue that is the same as or different from , R6 is a hydrocarbon residue, and r is a number of 1≦r≦3.

Here, R4 is preferably branched from the carbon atom adjacent to the silicon atom. In that case, the branching group is an alkyl group, a cycloalkyl group, or an aryl group (e.g., a phenyl group or a methyl-substituted phenyl group).
It is preferable that More preferred R4 is one in which the carbon atom adjacent to the silicon atom, ie, the α-position carbon atom, is a secondary or tertiary carbon atom. Particularly preferred are those in which the carbon atom bonded to the silicon atom is tertiary. The number of carbon atoms in R4 is usually 3 to 20, preferably 4 to 20.
10. R5 has 1 to 20 carbon atoms, preferably 1
It is usually a branched or straight-chain aliphatic hydrocarbon group of ~10. R6 is usually an aliphatic hydrocarbon group, preferably a chain aliphatic hydrocarbon group having 1 to 4 carbon atoms. This silicon compound may be a mixture of multiple types of compounds of the above formula.

Specific examples of the silicon compounds used in the present invention are as follows. (CH3)3CSi(CH3)(
OCH3)2, (CH3)3CSi(CH(CH3)2
)(OCH3)2, (CH3)3CSi(CH3)(O
C2H5)2, (C2H5)3CSi(CH3)(OC
H3)2, (CH3)(C2H5)CH-Si(CH3
)(OCH3)2, ((CH3)2CHCH2)2Si
(OCH3)2, (C2H5)(CH3)2CSi(C
H3) (OCH3)2, (C2H5) (CH3)2CS
i(CH3)(OC2H5)2, (CH3)3CSi(
OCH3)3, (CH3)3CSi(OC2H5)3,
(C2H5)3CSi(OC2H5)3, (CH3)(
C2H5)CHSi(OCH3)3, (C2H5)(C
H3)2CSi(OCH3)3, (C2H5)(CH3
)2CSi(OC2H5)3,

[0037]

[Chemical 2]

[0038]

[C3]

[0039]

[C4]

[0040]

[Image Omitted] Among these, preferable are branched hydrocarbon residues in which the carbon at the α position of R4 is secondary or tertiary and has 3 to 20 carbon atoms, especially those where the carbon at the α position of R4 is tertiary. It is a silicon compound having a branched hydrocarbon residue having 4 to 10 carbon atoms.

Furthermore, in the present invention, in the production of component (a1), organometallic compounds of metals from groups I to III of the periodic table may be used, if necessary.

Being an organometallic compound, this compound has at least one organic group-metal bond. In that case, the organic group has about 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
A hydrocarbyl group of about 6 is typical. Typical metals in this compound are lithium, magnesium, aluminum and zinc, especially aluminum.

The remaining valences (if any) of the metal of an organometallic compound in which at least one of the valences is filled with an organic group are hydrogen atoms, halogen atoms, hydrocarbyloxy groups (hydrocarbyl groups are (about 1 to 10 carbon atoms, preferably about 1 to 6 carbon atoms), or the metal via an oxygen atom (specifically, -O-Al(CH3)- in the case of methylalumoxane), and others. .

Specific examples of such organometallic compounds include (a) organolithium compounds such as methyllithium, n-butyllithium, and tert-butyllithium; (b) butylethylmagnesium, dibutylmagnesium, hexylethylmagnesium; , butylmagnesium chloride,
Organomagnesium compounds such as tert-butylmagnesium bromide, (c) organozinc compounds such as diethylzinc and dibutylzinc, (d) trimethylaluminum, triethylaluminum, triisobutylaluminum, trin-
Examples include organoaluminum compounds such as hexylaluminum, diethylaluminum chloride, diethylaluminum hydride, diethylaluminum ethoxide, ethylaluminum sesquichloride, ethylaluminum dichloride, and methylaluminoxane. Among these, organoaluminum compounds are particularly preferred. Further specific examples of organoaluminum compounds can be found in the examples of organoaluminum compounds given below as component (B).

Composition ratio and production of component (a1) (Part 2) The amounts of silicon, aluminum, boron, tungsten and molybdenum compounds to be used are in a molar ratio of 1 x 10-3 to the amount of the above magnesium compound used. 100, preferably within the range of 0.01 to 10.

[0046] Special mention is made of the above alkoxy silicon compounds and organometallic compounds as follows.

That is, the amounts of the alkoxy silicon compounds and organometallic compounds used may be arbitrary as long as they are effective, but the following ranges are generally preferred.

The amount of silicon compound used is as follows: component (a1)
The atomic ratio of silicon to the titanium component (silicon/titanium) is preferably in the range of 0.01 to 1000, preferably 0.1 to 100.

The amount of the organometallic compound used is determined by the amount of the component (a1
) The metal atomic ratio (metal/titanium) of the organometallic compound to the titanium component constituting the composition is in the range of 0.01 to 100, preferably 0.1 to 30.

These optional components (part 2) are component (a
1) It can be introduced into component (a1) at any stage of the production, one of which is the above-mentioned component from the essential components of component (a1) and optionally the electron donor (optional component (part 1)). In the process of preparing a solid composition by a method such as
As mentioned above, the method of introducing the optional component (Part 2) is to introduce the optional component (Part 2) after preparing the above-mentioned solid composition. Become. The contact conditions are as described above.

<Component (a2)> Component (a2) is a vinylsilane compound. Specifically, at least one hydrogen atom in monosilane (SiH4) is replaced with vinyl (CH2=CH-), and some of the remaining hydrogen atoms are replaced with halogen (preferably Cl), alkyl (preferably has 1 to 12 carbon atoms,
More preferably, those having 1 to 4 carbon atoms), alkoxy (preferably those having 1 to 12 carbon atoms, more preferably 1 to 4 carbon atoms), aryl (preferably phenyl),
Others, which show structures replaced by, more specifically CH2=CH-SiH3, CH2=CH-SiH2
(CH3), CH2=CH-SiH(CH3)2, CH
2=CH-Si(CH3)3, CH2=CH-SiCl
3, CH2=CH-SiCl2(CH3), CH2=C
H-SiCl(CH3)H, CH2=CH-SiCl(
C2H5)2, CH2=CH-Si(C2H5)3, C
H2=CH-Si(CH3)(C2H5)2, CH2=
CH-Si(C6H5)(CH3)2, CH2=CH-
Si(CH3)2(C6H4CH3), CH2=CH-
Si(OCH3)3, CH2=CH-Si(OC2H5
)3, CH2=CH-Si(C2H5)(OCH3)2
, CH2=CH-Si(OC2H5)2H,

0052
]

[C6]

[0053]

embedded image (CH2=CH)(CH3)2-Si-O-Si(CH
3) 2(CH=CH2), (CH2=CH)2SiCl
2, (CH2=CH)2Si(CH3)2, etc. can be exemplified. Among these, oxygen-free vinylsilanes are preferred, and vinylalkylsilanes are more preferred.

<Production of component (A1)> Component (A1)
is the contact product of component (a1) and component (a2) above. The contact conditions between component (a1) and component (a2) may be arbitrary as long as the effects of the present invention are observed, but are generally preferably within the following range.

[0055] The contact temperature is about -50 to 200°C, preferably about 0 to 100°C. As for the contact method,
Examples include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a media agitation pulverizer, etc., and a method of contacting by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons, halohydrocarbons, and polysiloxanes. The amount of component (a2) to be used may be within the range of 0.001 to 1000 in molar ratio of Si/Ti to the titanium compound constituting component (a1), preferably 0.
．． It is within the range of 01-100.

Optional Component (Part 3) During or after the preparation of component (A1) of the present invention, it is also possible to use ethylenically unsaturated compounds such as olefins and diene compounds as an optional component. Specific examples of such ethylenically unsaturated compounds include ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1- Butene, 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 3-
Methyl-1-pentene, 4-methyl-1-pentene, 2
-Methyl-2-pentene, 3-methyl-2-pentene,
4-methyl-2-pentene, 2-ethyl-1-butene,
2,3-dimethyl-1-butene, 3,3-dimethyl-1
-butene, 2,3-dimethyl-2-butene, 1-heptene, 1-octene, 2-octene, 3-octene, 4-
octene, 1-nonene, 1-decene, 1-undecene,
1-dodecane, 1-tridecane, 1-tetradecane, 1
-Pentadecane, 1-hexadecane, 1-heptadecane, 1-octadecane, 1-nonadecane, styrene, α-
Methyl-styrene, divinylbenzene, 1,2-butadiene, isoprene, hexadiene, 1,4-hexadiene, 1,5-hexadiene, 1,3-pentadiene, 1
, 4-pentadiene, 2,3-pentadiene, 2,6-
Octadiene, cis-2, trans 4-hexadiene, trans 2, trans 4-hexadiene, 1,2-heptadiene, 1,4-heptadiene, 1,
5-heptadiene, 1,6-heptadiene, 2,4-heptadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, cyclopentadiene, 1,3-cycloheptadiene, 1,3-butadiene , 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,9-decadiene, 1,
Examples include 13-tetradecadiene. These components (a1
), the component (A1) produced in this way usually undergoes so-called prepolymerization.

These ethylenically unsaturated compounds contain the component (
It is thought that it polymerizes during the preparation of A1). The amount used is 0.01 to 100 times, preferably 0.1 to 10 times by weight, the weight of component (A1) before use of these compounds.

<Component (A2)> Component (A2) used in the present invention is an organic silicone resin having an average particle size of 0.5 to 20 μm. The average particle size was measured using "Spica II" manufactured by Nippon Avionics. The organic silicone resin used in the present invention is a silicone resin having a three-dimensional network structure due to siloxane bonds, and the organic groups bonded to silicon include aliphatic hydrocarbon groups such as methyl groups and ethyl groups, phenyl groups, etc. Examples include aromatic hydrocarbon groups such as A-1, and unsaturated hydrocarbon groups having a vinyl group. Among them, methyl group is preferred. In addition, various modified silicone resin powders can also be used as long as they do not impair the effects of the present invention.

[0059] The organic silicone resin used in the present invention is mainly (here, R7 has about 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms).
10, especially 1 to 6 hydrocarbon residues, especially alkyl groups or aryl groups), the degree of polymerization is preferably 100 or more, and the molecular weight is several It ranges from hundreds of thousands to millions.

The organosilicone resin as component (A2) should be capable of existing as a solid at the polymerization temperatures employed in the polymerization of olefins according to the invention. Therefore, the degree of polymerization as the organopolysiloxane, the size and number of carbon atoms of the organic residue bonded to the silicon atom, and the presence or absence of crosslinking if necessary should be selected from this viewpoint.

The average particle size of this component (A2) is 0.5 to 20 μm, preferably 1 to 10 μm. Although various shapes can be used, spherical shapes, particularly spherical shapes are generally preferred. Since some of such granular polysilicone resins are commercially available, an appropriate one can be selected and used.

<Production of catalyst component (A)> As described above, the catalyst component (A) of the present invention consists of component (A1) and component (A2). Such catalyst component (A) can be obtained by mixing components (A1) and (A2). The mixing method of component (A1) and component (A2) may be any method as long as the effect of the present invention is recognized, but mixing under an inert gas (preferably sufficiently purified), for example, nitrogen gas atmosphere may be used. There are methods of mixing in the presence of an inert solvent, for example, a hydrocarbon solvent such as hexane or heptane. In addition, the amounts of component (A1) and component (A2) used vary depending on the properties of component (A1) and component (A2) used, but generally speaking, the amount of component (A2) used is
The weight ratio to A1) is preferably 0.01/1 to 1
Within the range of 0.00/1, more preferably 0.05/1 to 1
It is within the range of 0/1.

<Component (B)> Component (B) is an organic aluminum compound. As a specific example, R83-t A
lXt or R93-u Al(OR10)u (where R8 and R9 may be the same or different and have a carbon number of 1
~20 hydrocarbon residues or hydrogen atoms, R10 is a hydrocarbon residue having about 1 to 20 carbon atoms, X is a halogen, t and u are numbers of 0≦t≦3 and 0<u<3, respectively. . ). Specifically, (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., (b) diethylaluminum monochloride, diisobutylaluminum monochloride, ethyl Examples include alkyl aluminum halides such as aluminum sesquichloride and ethyl aluminum dichloride, (c) alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride, and (d) aluminum alkoxides such as diethyl aluminum ethoxide and diethylaluminum phenoxide. .

[0064] In addition to these organoaluminum compounds (a) to (d), other organometallic compounds, such as R103-v
Use together with an alkyl aluminum alkoxide represented by Al(OR11)v (where 1≦v≦3, R10 and R11 are hydrocarbon residues having about 1 to 20 carbon atoms, which may be the same or different). You can also do it. For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum diethoxide, a combination of triethylaluminum, diethylaluminum ethoxide, and diethylaluminum chloride are used. can give.

The amount of component (B) to be used is the weight ratio of component (B).
)/component (A) is 0.1 to 1000, preferably 1 to 1
The range is 00.

[II] Production of olefin polymer The method for producing an olefin polymer according to the present invention involves applying a catalyst consisting of a combination of components (A) and (B) to the catalyst under conditions substantially in the absence of a solvent. It consists of contacting and polymerizing α-olefins.

<Formation of catalyst> The catalyst used in the present invention is
The above components (A) and (B), or these components and optionally a third component (for example, a so-called external donor), in the coexistence or absence of an olefin to be polymerized in a polymerization tank, or It can be formed by contacting at once, in stages, or several times in divided contact in the presence or absence of the olefin to be polymerized outside the polymerization tank.

[0068] There are no particular restrictions on the method of supplying components (A) and (B) to the contact site, but each may be dispersed in an aliphatic hydrocarbon solvent such as hexane or heptane and added separately to the polymerization tank. Alternatively, it is common to bring them into contact with each other beforehand and then add them to the polymerization tank.

<Polymerization mode> The method for producing the polymer according to the present invention can be carried out by any of the batch, continuous and semi-batch methods. There are methods in which polymerization is carried out using the monomer itself as a medium, methods in which polymerization is carried out in a gaseous monomer without using a medium, and methods in which polymerization is carried out in combination.

A preferred method of polymerization is a method in which the polymerization is carried out in a gaseous monomer without using a medium, for example, a method in which the produced polymer particles are fluidized with a monomer air stream to form a fluidized bed, or a method in which the produced polymer particles are carried out using a stirrer. This is a method of stirring in a reaction tank.

<Olefin monomer and polymer produced> Olefins polymerized by the catalyst system of the present invention have the general formula R12
-CH=CH2 (here, R12 is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and may have a branched group). Specifically, ethylene,
Propylene, butene-1, pentene-1, hexene-1
, 4-methylpentene-1, and other olefins. Preferred are ethylene and propylene. In the case of these polymerizations, up to 50% by weight, preferably up to 20% by weight, based on ethylene, of the abovementioned olefins can be copolymerized with ethylene, and up to 30% by weight, based on propylene, of the abovementioned olefins, In particular, ethylene and propylene can be copolymerized. Further, copolymerization with other copolymerizable monomers (eg, vinyl acetate, diolefin, etc.) can also be carried out.

Typical examples of polymers obtained by the present invention are:
(a) Homopolymers such as ethylene and propylene, (b)
These include random copolymers of ethylene and propylene, ethylene and butene-1, ethylene and propylene, propylene and hexene-1, and (c) block copolymers of propylene and ethylene or propylene and ethylene/propylene.

<Polymerization conditions> Polymerization temperature is 30°C to 100°C
, preferably about 50°C to 90°C, and the polymerization pressure is usually within the range of 1 to 50 kg/cm 2 G. In addition,
During polymerization, it is also possible to control MFR using a molecular weight regulator such as hydrogen, if necessary.

[0074]

[Example 1] [Production of component (A1)] 300 ml of dehydrated and deoxygenated n-heptane was introduced into a flask that had been sufficiently purged with nitrogen, and then 0.2 mol of MgCl2 and Ti(O
-nC4H9)4 was introduced in an amount of 0.4 mol and reacted at 95°C for 2 hours. After the reaction was completed, the temperature was lowered to 40° C., and then 30 ml of methylhydropolysiloxane (20 centistoke) was introduced, and the reaction was allowed to proceed for 3 hours. The solid components formed were washed with n-heptane.

Next, 100 ml of n-heptane purified in the same manner as described above was introduced into a flask that had been sufficiently purged with nitrogen, and the solid component synthesized above was converted to 0.0 ml in terms of Mg atoms.
1 mol was introduced. Next, 25 ml of n-heptane was mixed with 40.15 mol of SiCl, and the mixture was introduced into the flask at 30°C for 30 minutes, followed by a reaction at 90°C for 3 hours. After the reaction was completed, it was washed with n-heptane.

Next, 0.09 mol of phthaloyl chloride was mixed with 25 ml of n-heptane and heated at 90°C for 3.
The mixture was introduced into the flask for 0 minutes and reacted at 95°C for 1 hour. After the reaction was completed, it was washed with n-heptane. Then WCl
6 and 80 ml of heptane were introduced and reacted at 90° C. for 4 hours. After the reaction is complete, n-
Component (A1) was obtained by thorough washing with heptane. The titanium content in the produced solid was 0.72 weight percent.

[Mixing of component (A1) and component (A2)] In a flask that has been sufficiently purged with nitrogen, sufficiently purified n-
50 ml of heptane was introduced, 5 grams of component (A1) and 5 grams of organic silicone resin (average particle size 45 μm, Tospar 145 (trade name) manufactured by Toshiba Silicone Co., Ltd.) were added as component (A2), and the mixture was heated at room temperature. The mixture was stirred and mixed. After stirring, heptane was removed and dried to obtain component (A). When the properties of the obtained component (A) were examined, the angle of repose was 35 degrees, and the fluidity was 2. .5 seconds/5 grams, and had very good properties.

[Polymerization of propylene] In a stainless steel autoclave with an internal volume of 1.5 liters equipped with a stirring and temperature control device, 30 grams of a sufficiently dehydrated and deoxidized polymer carrier (polyethylene with an average particle size of 500 μm) and triethylaluminum were added. 75 milligrams of (component (B)), 16 milligrams of diphenyldimethoxysilane, and 60 milligrams of component (A) synthesized above were introduced through a catalyst introduction tube having an inner diameter of 2 mm. Then add H2 to 120
ml was introduced, the temperature and pressure were increased, and the polymerization pressure = 5Kg/
Polymerization was carried out under the following conditions: cm2G, polymerization temperature = 90°C, and polymerization time = 2 hours. After the polymerization was completed, the polymerized polymer was collected. As a result, 97 grams of polymer was obtained. MFR = 23.6 (g/10 min), polymer bulk specific gravity =
It was 0.46 (g/cc).

After the polymerization was completed, there was no catalyst residue adhering to the catalyst introduction pipe, and no polymer adhesion was observed inside the polymerization tank. Further, although the same catalyst introduction and polymerization operations were repeated 10 times, no adhesion was observed in the catalyst introduction pipe or the polymerization tank.

<Comparative Example 1> [Production of catalyst component (A)] In the production of component (A) in Example 1, component (A1) was used as it was as component (A). The properties were very poor, with an angle of repose of 65 degrees and no flowability. [Polymerization of propylene] Polymerization was carried out under exactly the same conditions as in Example 1. However, the amount of component (A) used was 30 milligrams. As a result, 93.5 grams of polymer was obtained, MFR=20.8 (g/10 min), and polymer bulk specific gravity=0.45 (g/cc). Incidentally, a small amount of catalyst residue was observed adhering to the catalyst introduction tube. In addition, similar catalyst introduction and polymerization operations were repeated, but 6
In the third attempt, the catalyst introduction tube was blocked and polymerization was impossible.

<Example 2> [Production of component (A1)] In the same manner as in Example 1, MgCl2
was reacted with Ti(O-nC4H9)4 and methylhydropolysiloxane, and the resulting solid component was washed with n-heptane. Next, 50 ml of n-heptane purified in the same manner as above was introduced into a flask that had been sufficiently purged with nitrogen, and 0.1 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 50 ml of n-heptane was mixed with 39 ml of SiCl4,
The mixture was introduced into a flask at 30°C for 30 minutes, and reacted at 90°C for 1 hour. After the reaction was completed, it was washed with n-heptane to obtain a solid component.

Into a flask that had been sufficiently purged with nitrogen, 50 ml of sufficiently purified n-heptane was introduced, and then 5 grams of the solid component obtained above was introduced, and then (CH3)3CSi(CH3)(OCH3 )
2.0ml of SiCl4 was introduced, and then 5ml of SiCl4 was introduced.
．． 8 ml, plus 4.5 triethyl aluminum
grams each were introduced and left in contact for 2 hours at 20°C. Then 5.5 grams of divinylbenzene was introduced and the temperature was increased to 30°C.
for 1 hour. After the contact was completed, the product was thoroughly washed with n-heptane to obtain component (A1).

[Mixing of component (A1) and component (A2)] In the mixing of Example 1, component (A2) with an average particle size of 1.0 μm (Toray Silicone Co., Ltd. "Tolfill R-930") was used. Component (A) was prepared in exactly the same manner except for the following. Angle of repose is 39 degrees, fluidity =
It was 3.1 seconds.

[Copolymerization of propylene] Japanese Patent Publication No. 61-33
Propylene was copolymerized by the method disclosed in Japanese Patent No. 721 using a horizontal twin-axial gas phase polymerization tank having an internal volume of 13 liters. After the inside of the polymerization tank was purged with sufficiently purified nitrogen, 400 grams of a sufficiently dehydrated and deoxidized polymer carrier (polypropylene with an average particle size of 600 μm) was added. Next, component (B) triethylaluminum 5
00 milligrams and 160 milligrams of component (A) synthesized above were introduced through a catalyst introduction tube having an inner diameter of 2 mm. In the first stage polymerization step (1), after introducing 1000 ml of hydrogen, the temperature was raised to 75°C, and 1 ml of propylene was added.
．． It was introduced at a constant rate of 3 grams/min. Note that the stirring rotation speed of the polymerization tank was 350 r. p. It was m. Polymerization temperature 7
The temperature was maintained at 5° C., and after 3 hours and 30 minutes, the introduction of propylene was stopped. Polymerization was continued at 75℃, and the polymerization pressure was 1Kg/cm2G.
A portion of the polymerization sample was taken at the point when the temperature reached .

Thereafter, 500 ml of H2 was added to start the polymerization step (2). In the second stage polymerization, propylene was added at 0.59 g/min and ethylene was added at 0.40 g/min.
The mixture was introduced at a constant rate of 1 hour and 50 minutes at 70° C., respectively. The introduction of propylene and ethylene was stopped, and residual pressure polymerization was carried out until the polymerization pressure reached 1 Kg/cm2G. After the polymerization was completed, the reactor was purged and the polymer was taken out. 384 grams of polymer was obtained. The MFR of the produced polymer is 7.1
g/10 minutes, and the polymer bulk density (B.D.) is 0.
44 (g/cc), and the polymer falling speed was 5.6 seconds. The weight of the rubbery copolymer was 29.3 weight percent.

[0086] There was no polymer adhesion in the polymerization tank, and the MFR of the intermediate sample was 17.6 g/10 minutes. In addition,
The polymer falling speed is 1.3c for 50 grams of polymer.
m2 means the time required to fall from the inner hole.

[0087] Also, if catalyst residue is attached to the catalyst introduction pipe,
I was not able to admit. The same catalyst introduction and polymerization operations were repeated 10 times, but no catalyst residue was observed on the catalyst introduction tube.

<Comparative Example 2> [Production of catalyst component (A)] In the production of component (A) in Example 2, component (A1) was used as it was as component (A). The angle of repose was 56 degrees, and the flowability was 10.9 seconds. [Copolymerization of propylene] Polymerization was carried out under exactly the same conditions as in Example 2. However, the amount of component (A) used was 80 milligrams. The polymerization resulted in 382 grams of polymer. MFR=7.2g/10min, Polymer B. D=
0.42 (g/cc), and the polymer falling rate is 5.
It was 8 seconds. The weight of the rubbery copolymer was 29.2 weight percent. Incidentally, a small amount of catalyst was observed to be attached to the catalyst introduction tube. The same catalyst introduction and polymerization operations were repeated, but the catalyst introduction tube was completely blocked at the seventh time, making polymerization impossible.

[Brief explanation of drawings]

FIG. 1 is a flowchart to help understand the technical content of the present invention regarding a Ziegler catalyst.

Claims (2)

[Claims] Claim 1: The following component (A1) and component (A2)
) A catalyst component for olefin polymerization, characterized by comprising a combination of the following. Component (A1) A contact product of the following component (a1) and component (a2), Component (a1) A solid component for a Ziegler type catalyst containing titanium, magnesium and halogen as essential components, Component (a2) A vinyl silane compound, Component (A2) Organic silicone resin with an average particle size of 0.5 to 20 μm. [Claim 2] A catalyst comprising a combination of the following components (A) and (B) is treated with α
- A method for producing an olefin polymer, which comprises bringing olefins into contact and polymerizing them. Component (A) A catalyst component for olefin polymerization consisting of a combination of the following components (A1) and (A2), Component (A1) A contact product of the following components (a1) and (a2), Component (a1) Titanium , a solid component for a Ziegler type catalyst containing magnesium and halogen as essential components, component (a2) a vinyl silane compound, component (A2) an organosilicone resin with an average particle size of 0.5 to 20 μm, component (B) an organoaluminum compound.