JPH0780953B2 - Titanium trichloride composition for producing olefin polymer and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a titanium trichloride composition for producing an olefin polymer and a method for producing the same. More specifically, the present invention relates to a titanium trichloride composition for producing an olefin polymer, which is suitable as a transition metal compound catalyst component for producing an olefin polymer having excellent transparency, and a method for producing the same.

[Conventional technology and its problems]

The crystalline olefin polymer such as crystalline polypropylene is
A so-called Ziegler-comprising a transition metal compound of group IV to VI and an organometallic compound of group I to III of the periodic table
It is well known that it can be obtained by polymerizing an olefin with a Natta catalyst, and among them, various titanium trichloride compositions are widely used as a transition metal compound catalyst component.

Of these titanium trichloride compositions, those obtained by reducing titanium tetrachloride with an organoaluminum compound and then heat-treating it, many improved production methods have been investigated because the shape of the obtained polymer is good. There is. For example, titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound is treated with an electron donor and titanium tetrachloride to increase the catalytic activity and reduce the production of an amorphous polymer ( Japanese Patent Publication No. 53-3356).

The present applicant has already made many proposals in this field. Among them, a solid obtained by reacting a reaction product of an organoaluminum compound and an electron donor with titanium tetrachloride is an electron donor and an electron acceptor. And a method for producing an olefin polymer using a titanium trichloride composition obtained by reacting with a compound (Japanese Patent Publication No. 59-28,573) and titanium tetrachloride as a reaction product of an organoaluminum compound and an electron donor. A method for producing an olefin polymer using a titanium trichloride composition obtained by reacting an electron donor with an electron acceptor after subjecting a solid obtained by the reaction to a polymerization treatment with an olefin (Japanese Patent Application Laid-Open No. S60-187242). 58-17,104), a proposal was made that the storage stability of the titanium trichloride composition, the polymerization activity, the crystallinity of the obtained olefin polymer, etc. were significantly improved as compared with the conventional method. There.

However, although these improved methods have the advantages as described above, the obtained polyolefin is translucent, which may impair the commercial value in the application field, and improvement in transparency has been desired. .

On the other hand, attempts have been made to improve the transparency of olefin polymers, such as aluminum salts of aromatic carboxylic acids (Japanese Patent Publication No. 40-1,652) and benzylidene sorbitol derivatives (Japanese Patent Publication No. 51-22,740). There is a method of adding a nucleating agent such as) to polypropylene, but when an aluminum salt of an aromatic carboxylic acid is used, the dispersibility is poor and the effect of improving transparency is insufficient. ,
When a benzylidene sorbitol derivative is used,
Although some improvement was seen in transparency, there were problems such as strong odor during processing and bleeding of the additive (embossing).

In order to improve the above-mentioned problems when adding a nucleating agent, there is provided a method for carrying out multi-stage polymerization of styrene, pt-butylstyrene, allyltrimethylsilane and the like and a composition thereof (Japanese Patent Publication No. 62-1,738). JP-A-62-227,911, JP-A-63-15,803, JP-A-63-15,804, JP-A-63-68,648, etc.) have been proposed,
According to the method proposed by the present inventors, when polypropylene is produced, not only the polymerization activity of propylene is decreased in any method, but also a lumpy polymer is produced, so that industrial long-term continuous production is possible. This method cannot be used in a polymerization method, particularly in a gas phase polymerization method in which olefin polymerization is carried out in a gas phase. Furthermore, many voids were generated in the film produced using the obtained polypropylene, which impaired the commercial value.

As a similar technique, a method of polymerizing propylene using the catalyst component obtained by adding a pt-butylstyrene polymer, an allyltrimethylsilane polymer or the like during the production of a transition metal catalyst component for propylene polymerization (JP-A-63-69,
No. 809) has been proposed, but the proposed method involves a step of separately producing a pt-butylstyrene polymer, an allyltrimethylsilane polymer, etc., and therefore has an industrial disadvantage. In addition to the above-mentioned prior art, there was a problem of void formation in the film.

The present inventors, when producing an olefin polymer having improved transparency, have keenly studied a method for solving the problems such as the generation of a bulk polymer and the occurrence of voids in a film due to poor dispersion, which the conventional technology has. did.

As a result, a titanium trichloride composition containing a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer was found by a specific method, and this titanium trichloride composition was combined with an organoaluminum compound. When a catalyst is used, an olefin polymer having excellent transparency and crystallinity can be obtained, which solves the above-mentioned problems in producing an olefin polymer of the prior art and has good dispersibility and extremely few voids. Not only is there a significant effect on the storage stability of the titanium trichloride composition at high temperatures of 35 ° C. or higher, and on the attrition resistance in the production equipment during the large-scale production of the titanium trichloride composition. The inventors have come to the present invention by knowing that.

The present invention provides a titanium trichloride composition for producing an olefin polymer capable of producing an olefin polymer having extremely high transparency and extremely high crystallinity, which is extremely low in void generation with extremely high productivity, and a method for producing the same. The purpose is.

[Means for Solving the Problems] The present invention has the following configurations.

(1) Solid product (II) obtained by reacting an organoaluminum compound or a reaction product (I) of an organoaluminum compound and an electron donor (B ₁ ) with titanium tetrachloride.
Is obtained by polymerizing dialkyldiallylsilane and / or trialkylsilylstyrene, and further reacting the electron donor (B ₂ ) with a halide of an element of Group III to VI of the periodic table after the polymerization. The final solid product (III) is a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer in an amount of 0.01% by weight to 99% by weight, and a titanium trichloride composition 99.99% by weight to 1% by weight. A titanium trichloride composition for producing an olefin polymer, which comprises a weight percentage.

(2) Solid product (II) obtained by reacting an organoaluminum compound or a reaction product (I) of an organoaluminum compound and an electron donor (B ₁ ) with titanium tetrachloride.
Is obtained by polymerizing dialkyldiallylsilane and / or trialkylsilylstyrene, and further reacting the electron donor (B ₂ ) with a halide of an element of Group III to VI of the periodic table after the polymerization. The final solid product (III) is a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer in an amount of 0.01% by weight to 99% by weight, and a titanium trichloride composition 99.99% by weight to 1% by weight. A method for producing a titanium trichloride composition for producing an olefin polymer, the method comprising a weight percentage of the composition.

(3) As the organoaluminum compound, the general formula is AlR ¹ _m R
² _{m ′ X3− (m + m ′)} (wherein R ¹ and R ² represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, X represents a halogen, and m and m ′ represent 0
<M + m ′ ≦ 3 represents an arbitrary number. The manufacturing method of the said 2nd item which uses the organoaluminum compound represented by these.

The structure of the present invention will be described in detail below.

The titanium trichloride composition for producing an olefin polymer of the present invention comprises a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer (hereinafter,
It may be a specific silicon-containing polymer. ) Is contained in the titanium trichloride composition, the production method thereof will be described.

The titanium trichloride composition is manufactured as follows. First,
A solid product (II) obtained by reacting an organoaluminum compound with an electron donor (B ₁ ) to obtain a reaction product (I), and reacting this (I) with titanium tetrachloride, or organoaluminum A solid product (II) obtained by reacting a compound with titanium tetrachloride was polymerized with dialkyldiallylsilane and / or trialkylsilylstyrene (hereinafter sometimes referred to as a specific silicon-containing monomer). After that, the titanium trichloride composition of the present invention is produced as the final solid product (III) obtained by further reacting the electron donor (B ₂ ) with the electron acceptor.

In the present invention, "polymerizing" means that a specific silicon-containing monomer is brought into contact with the solid product (II) to polymerize the specific silicon-containing monomer. By this polymerization treatment, the solid product (II) is in a state of being coated with the polymer.

The reaction between the above-mentioned organoaluminum compound and the electron donor (B ₁ ) is carried out in the solvent (D) at -20 ° C to 200 ° C, preferably -1.
It is carried out at 0 ° C to 100 ° C for 30 seconds to 5 hours. The order of addition of the organoaluminum compound, (B ₁ ) and (D) is not limited, and the amount ratio used is 0.1 mol to 8 mol, preferably 1 to 4 mol of the electron donor (B ₁ ) per 1 mol of the organoaluminum compound. Mol, solvent 0.5 L to 5 L, preferably 0.5 L to 2 L.

Thus, the reaction product (I) is obtained. The reaction product (I) can be used for the next reaction in a liquid state as it is after completion of the reaction (sometimes referred to as the reaction product liquid (I)) without separation.

As a method for polymerizing the reaction product (I) with titanium tetrachloride or the solid product (II) obtained by reacting an organoaluminum compound with titanium tetrachloride with a specific silicon-containing monomer, , A reaction product (I), or a method for polymerizing a solid product (II) by adding a specific silicon-containing monomer in any step of the reaction between an organoaluminum compound and titanium tetrachloride, a reaction product (I), or a method of polymerizing the solid product (II) by adding a specific silicon-containing monomer after the reaction between the organoaluminum compound and titanium tetrachloride, and the reaction product (I), or After completion of the reaction between the organoaluminum compound and titanium tetrachloride, the liquid product is separated and removed by filtration or decantation, and the obtained solid product (II) is obtained.
Is suspended in a solvent, an organoaluminum compound and a specific silicon-containing monomer are further added, and a polymerization treatment is performed.

The reaction of the reaction product (I) or the organoaluminum compound with titanium tetrachloride is carried out at −10 ° C. or higher regardless of the addition or non-addition of the specific silicon-containing monomer in any process of the reaction.
It is carried out at 200 ° C., preferably 0 ° C. to 100 ° C. for 5 minutes to 10 hours.

Although it is preferable not to use a solvent, an aliphatic or aromatic hydrocarbon can be used. The mixing of (I) or the organoaluminum compound, titanium tetrachloride, and the solvent may be performed in any order, and the addition of the specific silicon-containing monomer may be performed at any stage.

It is preferable that the mixing of (I) or the organoaluminum compound, titanium tetrachloride, and the solvent is completed within 5 hours, and the reaction is performed during the mixing. After mixing all
It is preferable to continue the reaction within 5 hours.

The amount of each used in the reaction is 1 to 1 mol of titanium tetrachloride, the solvent is 0 to 3,000 ml, and the ratio of the number of Al atoms in the reaction product (I) or the organoaluminum compound to the number of Ti atoms in titanium tetrachloride ( Al / Ti) 0.05 to 10, preferably 0.06
~ 0.3.

The polymerization treatment with the specific silicon-containing monomer is carried out when the specific silicon-containing monomer is added at any stage of the reaction between the reaction product (I) or the organoaluminum compound and titanium tetrachloride and the reaction product (I Or when a specific silicon-containing monomer is added after the reaction between the organoaluminum compound and titanium tetrachloride, the reaction temperature is 0 ° C to 90 ° C for 1 minute to 10 hours, and the reaction pressure is atmospheric pressure to 10 kgf / Using 100 g of the specific silicon-containing monomer per 100 g of the solid product (II) under the condition of cm ² G, the final solid product (II
I), that is, the polymerization is performed so that the content of the specific silicon-containing monomer in the titanium trichloride composition of the present invention is 0.01% by weight to 99% by weight.

When the content of the specific silicon-containing monomer is less than 0.01% by weight, the effect of improving transparency and crystallinity of the olefin polymer produced using the titanium trichloride composition obtained is insufficient, and When it exceeds 99% by weight, the improvement effect is not remarkable and it is economically disadvantageous.

After the reaction of the reaction product (I) or the organoaluminum compound with titanium tetrachloride is completed by the polymerization treatment with the specific silicon-containing monomer, the liquid portion is separated and removed by filtration or decantation, and then the solid obtained When the product (II) is suspended in a solvent, the solid product (II) 10
To 0 g, 100 ml to 5,000 ml of solvent and 0.5 g to 5,000 g of organoaluminum compound were added, and the reaction temperature was 0 ° C to 90 ° C for 1 minute to 10 minutes.
Time, reaction pressure is from atmospheric pressure to 10 Kgf / cm ² G, 0.01 g to 100 Kg of the specific silicon-containing monomer per 100 g of the solid product (II) is used, and the final solid product (III ), And the content of the specific silicon-containing polymer therein is 0.01% by weight to 99% by weight.

The solvent is preferably an aliphatic hydrocarbon, and the organoaluminum compound was used for obtaining the reaction product (I) or used for the reaction with titanium tetrachloride directly without reacting with the electron donor (B ₁ ). It may be the same as or different from the one.

After completion of the reaction, the liquid portion is separated and removed by filtration or decantation, and after further washing with a solvent,
The obtained solid product subjected to the polymerization treatment (hereinafter sometimes referred to as solid product (II-A)) may be used in the next step as it is in a suspended state in a solvent, and further dried to give a solid. You may take it out and use it.

The solid product (II-A) is then reacted with an electron donor (B ₂ ) and an electron acceptor (F). This reaction can be carried out without using a solvent, but using an aliphatic hydrocarbon gives preferable results.

The amount used is (B ₂ ) based on 100 g of the solid product (II-A).
0.1 g to 1,000 g, preferably 0.5 g to 200 g, (F) 0.1 g to 1,
000 g, preferably 0.2 g to 500 g, solvent 0 to 3,000 ml, preferably 100 to 1,000 ml.

As the reaction method, a solid product (II-A) is reacted with an electron donor (B ₂ ) and an electron acceptor (F) at the same time. After reacting (II-A) with (F), ( B ₂ ) is reacted, (II-A) is reacted with (B ₂ ),
There are a method of reacting (F) and a method of reacting (B ₂ ) with (F) and then reacting with (II-A), but either method may be used.

The reaction conditions are 40 ° C. to 20 ° C. in the above method.
It is desirable to react at 0 ° C, preferably 50 ° C to 100 ° C for 30 seconds to 5 hours. In the method of (II-A) and (B ₂ )
After reacting the reaction (1) at 0 ° C to 50 ° C for 1 to 3 hours, (F)
And are reacted under the same conditions as above.

In the other method, (B ₂ ) and (F) are heated at 10 ℃ to 100 ℃.
After reacting for 30 minutes to 2 hours, cool to 40 ° C or lower (II
After adding -A), the reaction is carried out under the same conditions as above.

After the reaction of the solid products (II-A), (B ₂ ) and (F) is completed, the liquid portion is separated and removed by filtration or decantation, and the washing with a solvent is repeated to obtain the crystalline dialkyl of the present invention. A solid product (III), which is a titanium trichloride composition for producing an olefin polymer, containing a diallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer is obtained.

The solid product (III) thus obtained, that is, the titanium trichloride composition of the present invention, contains 0.01% to 99% by weight of a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer. As a transition metal compound catalyst component for producing an olefin polymer, it is used in combination with at least an organoaluminum compound to polymerize an olefin.

The organoaluminum compound used in the production of the titanium trichloride composition of the present invention has a general formula of AlR ¹ _m R ² _{m ′} X _3-
( M _{+ m ′)} (wherein R ¹ and R ² represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, X represents a halogen, and m and m ′ are 0 <m +
It represents an arbitrary number of m ′ ≦ 3. ).

Specific examples thereof include trimethyl aluminum, triethyl aluminum, tri n-propyl aluminum, tri n-butyl aluminum, tri i-butyl aluminum, tri n-hexyl aluminum, tri i-hexyl aluminum, tri 2-methylpentyl aluminum,
Trialkylaluminums such as tri-n-octylaluminum and tri-n-decylaluminum, diethylaluminum monochloride, di-n-propylaluminum monochloride, di-butylaluminium monochloride, diethylaluminum monofluoride, diethylaluminum monobromide, Dialkyl aluminum monohalides such as diethyl aluminum monoiodide, dialkyl aluminum hydrides such as diethyl aluminum hydride, alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, i-butyl aluminum dichloride, etc. Monoalkyl aluminum dihalides of Monoethoxy diethylaluminum, alkoxyalkyl aluminum such as diethoxy monoethyl aluminum can also be used to.

Two or more kinds of these organoaluminum compounds may be mixed and used.

As the electron donor used in the present invention, various ones shown below are shown. As (B ₁ ) and (B ₂ ), ethers are mainly used, and other electron donors are shared with ethers. Is preferred.

What is used as an electron donor is an organic compound having any atom of oxygen, nitrogen, sulfur and phosphorus, that is, ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines. And amides, urea or thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, hydrogen sulfide or thioethers, and thioalcohols.

Specific examples include diethyl ether, di-n-propyl ether, di-n-butyl ether, diisoamyl ether, di-n-pentyl ether, di-n-hexyl ether, di-hexyl ether, di-n-octyl ether, di-i-. Ethers such as octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, tetrahydrofuran, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol,
Alcohols such as cresol, xylenol, ethylphenol, naphthol, or phenols, methyl methacrylate, ethyl acetate, butyl formate, amyl acetate,
Vinyl butyrate, vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, toluyl 2-ethylhexyl, methyl anisate,
Ethyl anisate, propyl anisate, ethyl cinnamate,
Methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, esters such as ethyl phenylacetate, aldehydes such as acetaldehyde and benzaldehyde, formic acid,
Aliphatic acids such as acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, and maleic acid; aromatic acids such as benzoic acid; ketones such as methyl ethyl ketone, methyl isobutyl ketone and benzophenone; nitrile acids such as acetonitrile; methyl amine , Diethylamine, tributylamine, triethanolamine, β (N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline,
Amine such as 2,4,6-trimethylpyridine, N, N, N ′, N′-tetramethylethylenediamine, aniline, dimethylaniline, formamide, hexamethylphosphoric triamide, N, N, N ′, N ′, N ″ -pentamethyl-N′-β-dimethylaminomethylphosphoric acid triamide, amides such as octamethylpyrophosphoramide, ureas such as N, N, N ′, N′-tetramethylurea, phenyl isocyanate, toluyl Isocyanates such as isocyanate, azo compounds such as azobenzene, ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, phosphines such as triphenylphosphine oxide, dimethylphosphite, di-n- Octyl phosphite, triethyl phosphite, tri-n-butyl Sufaito, phosphites such as triphenyl phosphite, ethyl diethyl phosphinite, ethyl butyl phosphinite, phosphinite such as phenyl diphenylphosphinite, diethyl thioether, diphenyl thioether,
Methyl phenyl thioether, ethylene sulfide,
Examples thereof include thioethers such as propylene sulfide, thioalcohols such as ethylthioalcohol, n-propylthioalcohol and thiophenol.

These electron donors can also be used as a mixture.
The electron donor (B ₁ ) for obtaining the reaction product (I) and the solid product (II-A) reacted (B ₂ ) may be the same or different.

The electron acceptor (F) used in the present invention is represented by the periodic table III to V.
It is represented by Group I element halides. Specific examples include anhydrous aluminum chloride, silicon tetrachloride, stannous chloride, stannic chloride, titanium tetrachloride, zirconium tetrachloride, phosphorus trichloride, phosphorus pentachloride, vanadium tetrachloride, antimony pentachloride and the like. These can also be used as a mixture. Most preferred is titanium tetrachloride.

The following solvents are used. Examples of the aliphatic hydrocarbon include n-pentane, n-hexane, n-heptane, n-octane, i-octane and the like, and carbon tetrachloride, chloroform instead of or together with the aliphatic hydrocarbon. It is also possible to use halogenated hydrocarbons such as dichloroethane, trichloroethylene, and tetrachloroethylene. As aromatic compounds, aromatic hydrocarbons such as naphthalene, and mesitylene which is a derivative thereof,
Durene, ethylbenzene, isopropylbenzene, 2
-Alkyl-substituted compounds such as ethylnaphthalene and 1-phenylnaphthalene, and halides such as monochlorobenzene, chlorotoluene, chlorxylene, chloroethylbenzene, dichlorobenzene and bromobenzene are shown.

The dialkyldiallylsilane and / or trialkylsilylstyrene used in the polymerization treatment has the general formula (C
H ₂ = CH-CH ₂ ) ₂ SiR ³ R ⁴ or (In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are the same or different and each represents an alkyl group having 1 to 6 carbon atoms.), Which is a specific monomer containing silicon. . Specifically, dimethyldiallylsilane, ethylmethyldiallylsilane, diethyldiallylsilane, p-trimethylsilylstyrene, m-trimethylsilylstyrene, p-triethylsilylstyrene, m-triethylsilylstyrene,
Examples include p-ethyldimethylsilylstyrene and the like.

The titanium trichloride composition of the present invention obtained as described above is used in combination with at least an organoaluminum compound as a catalyst according to a conventional method to polymerize an olefin, or more preferably by reacting an olefin with a preliminary activity. It is used for the polymerization of olefins as a converted catalyst.

The organoaluminum compound used for the polymerization of olefins is
The same organoaluminum compound as that used when the titanium trichloride composition of the present invention described above is produced can be used. The organoaluminum compound may be the same as or different from the one used in producing the titanium trichloride composition.

As the olefin used for pre-activation, linear monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and heptene-1
-Methyl-pentene-1, 2-methyl-pentene-1 and other branched chain monoolefins.

These olefins may be the same as or different from the olefin to be polymerized, or two or more olefins may be mixed and used.

The olefin polymerization method using the above catalyst is not limited, and in addition to liquid phase polymerization such as slurry polymerization and bulk polymerization,
It can also be suitably carried out by gas phase polymerization.

A catalyst obtained by combining a titanium trichloride composition and an organoaluminum compound is also sufficiently effective for slurry polymerization or bulk polymerization, but in the case of gas phase polymerization, a catalyst obtained by reacting an olefin and preactivating it is desirable. When performing gas phase polymerization following slurry polymerization or bulk polymerization, even if the catalyst initially used is the former, it is the same as the latter catalyst because the olefin reaction has already been carried out during gas phase polymerization. And an excellent effect is obtained.

Pre-activation is performed by adding 0.005 g to 500 g of an organoaluminum compound, 0 to 50 l of a solvent, and 0 to hydrogen for 1 g of the titanium trichloride composition.
1,000 ml and olefin 0.05 g to 5,000 g, preferably 0.05
Use g to 3,000 g. The temperature is 0 ° C to 100 ° C for 1 minute to 20 hours, and the olefin is allowed to react with 1 g of the titanium trichloride composition.
It is desirable to react 0.01 to 2,000 g, preferably 0.05 to 200 g of olefin.

It can also be carried out in a hydrocarbon solvent such as pre-activated propane, butane, n-pentane, n-hexane, n-heptane, benzene, toluene, etc., and among liquefied olefins such as liquefied propylene and liquefied butene-1, gaseous ethylene It can be carried out also in propylene, and hydrogen may be allowed to coexist during the preliminary activation.

Polymer particles obtained by slurry polymerization, bulk polymerization or gas phase polymerization in advance may be allowed to coexist during the preliminary activation. The polymer may be the same as or different from the olefin polymer to be polymerized. Polymer particles that can coexist are 0 g per 1 g of the titanium trichloride composition.
It is in the range of ~ 5,000g.

The solvent or olefin used in the pre-activation can be removed during the pre-activation or after completion of the pre-activation by distillation under reduced pressure or by filtration, etc. Solvents can also be added for suspension in an amount that does not exceed.

There are various embodiments of the pre-activation method, for example, a method in which an olefin is brought into contact with a catalyst obtained by combining a titanium trichloride composition and an organoaluminum to carry out a slurry reaction, a bulk reaction or a gas phase reaction, and the coexistence of α-olefin. There are a method of combining a titanium trichloride composition and an organic aluminum below, a method of coexisting an olefin polymer, a method of coexisting hydrogen with a method of. There is essentially no difference between making the catalyst in the slurry state or making it into a granular material.

As described above, a catalyst comprising a combined titanium trichloride composition and an organoaluminum compound, or a catalyst pre-activated with an olefin is used in the production of an olefin polymer. For the purpose of improving stereoregularity, an electron donor may be further added as a third component of the catalyst and used for polymerization.

The amount of each catalyst component used is the same as in the usual olefin polymerization, but specifically, to 1 g of the titanium trichloride composition, 0.01 g to 500 g of an organoaluminum compound and 0 to 200 g of an electron donor.
To use.

As a polymerization method for polymerizing an olefin, as described above, n-pentane, n-hexane, n-heptane, n
-Slurry polymerization performed in a hydrocarbon solvent such as octane, benzene or toluene, bulk polymerization performed in a liquefied olefin monomer such as liquefied propylene or liquefied butene-1, vapor phase polymerization in which an olefin such as ethylene or propylene is polymerized in a gas phase Alternatively, there is a method of stepwise combining two or more of the above items. In either case, the polymerization temperature is room temperature (20 ℃) to 200 ℃, and the polymerization pressure is normal pressure (0kg / cm
² G) to 50 kg / cm ² G, and usually 5 minutes to 20 hours.

At the time of polymerization, addition of an appropriate amount of hydrogen for controlling the molecular weight is the same as in the conventional polymerization method.

The olefins used for the polymerization are ethylene, propylene,
Linear monoolefins such as butene-1, hexene-1, octene-1, branched chain monoolefins such as 4-methylpentene-1, 2-methyl-pentene-1, diene such as butadiene, isoprene, chloroprene Olefins and the like, and not only homopolymerization of each of these, but also combinations with other olefins such as propylene and ethylene, butene-1 and ethylene, propylene and butene-1. Propylene, ethylene,
Copolymerization can be carried out by combining three components such as butene-1, and block copolymerization can also be carried out by changing the kind of olefin fed in multistage polymerization.

[Function] The olefin polymer obtained by using the titanium trichloride composition of the present invention contains a specific silicon-containing polymer having high stereoregularity in an extremely dispersed state. Since the silicon-containing polymer exhibits a nucleating action, the spherulite size of the olefin polymer is reduced and crystallization is promoted. As a result, the transparency and crystallinity of the entire olefin polymer are enhanced.

Further, the specific silicon-containing polymer introduced into the olefin polymer by using the titanium trichloride composition of the present invention, as described above, is a stereoregular high molecular weight polymer, so that the surface bleeds. There is no.

[Effects of the Invention] The main effects of the present invention are that when the titanium trichloride composition of the present invention is used in the polymerization of olefins as a transition metal compound catalyst component for the production of olefin polymers, voids are formed with remarkably high productivity. That is, it is possible to produce an olefin polymer having extremely low transparency and extremely high transparency and crystallinity.

The effects of the present invention will be described more specifically.

The first effect of the present invention, when used in olefin polymerization,
Both the transparency and crystallinity of the obtained olefin polymer are improved, and the number of generated voids is extremely small.

As will be apparent from the examples shown below, the internal haze of the press film of the olefin polymer obtained using the titanium trichloride composition of the present invention does not contain a specific silicon-containing polymer, the titanium trichloride composition. Compared with the olefin obtained by using, it is about 1/8 to 1/4, and has extremely high transparency.

In addition, the crystallization temperature is increased by about 8 ° C to 12 ° C as compared with the case where the specific silicon-containing polymer is not contained, and the crystallinity is remarkably improved and the flexural modulus is also remarkably increased. 1-9, Comparative Examples 1, 5-10). Further, it is clear that the number of voids generated is significantly smaller than that of an olefin polymer into which a polymer of styrenes or silanes is introduced by a method other than the present invention (Examples 1 to 9,
See Comparative Examples 2 and 3).

The second effect of the present invention is an extremely high polymerization activity,
That is, an olefin polymer having a good particle shape and high stereoregularity can be obtained. Therefore, the catalyst removal step and the atactic polymer removal step can be omitted, and the olefin polymer can be produced by a continuous polymerization method for a long period by a simpler process such as a gas phase polymerization method. It is extremely advantageous.

The third effect of the present invention is that the titanium trichloride composition for producing an olefin polymer of the present invention is excellent in storage stability and thermal stability. It is extremely important industrially to be able to store stably for a long period of time regardless of whether the outside temperature is high or low. The storage can be carried out in a powder state or in a state of being suspended in an inert hydrocarbon solvent.

Further, the fourth effect of the present invention is that the titanium trichloride composition for producing an olefin polymer of the present invention is excellent in abrasion resistance. The titanium trichloride composition is not susceptible to attrition during its use, that is, not only in the olefin polymer production process but also in the catalyst production process. This means preventing the formation of finely divided catalyst and thus the formation of finely divided olefin polymer. As a result, it is extremely effective in preventing line blockage troubles in the gas phase polymerization process, and preventing compressor troubles due to mixing of the finely divided olefin polymer into the circulating gas.

[Examples] Hereinafter, the present invention will be described with reference to Examples. The definitions of terms used in Examples and Comparative Examples and the measuring methods are as follows.

TY: Polymerization activity, polymer yield per gram atom of titanium (unit: kg / gram atom) II: Stereoregularity, 20 ° C n-hexane extraction residual amount (unit: wt%) BD: Bulk specific gravity (Unit: g / ml) MFR: Melt Flow Index According to ASTM D-1238 (L). (Unit: g / 10 minutes) Internal haze: The internal haze excluding the effect of the surface, using a press machine at a temperature of 200 ° C and a pressure of 200 kg / cm ² G
Under the conditions, the olefin polymer powder was formed into a film having a thickness of 150 μ, liquid paraffin was applied to both surfaces of the film, and then the haze was measured according to JIS K 7105. (unit:
%) Crystallization temperature: measured with a differential scanning calorimeter at a temperature decrease rate of 10 ° C./min. (Unit: ° C) Flexural modulus: Tetrakis [methylene-3- (3 ', 5'-di-t] based on 100 parts by weight of olefin polymer powder
-Butyl-4'-hydroxyphenyl) propionate] methane 0.1 part by weight, and calcium stearate
0.1 parts by weight were mixed, and the mixture was granulated using an extruder having a screw diameter of 40 mm. Then, the granulated product is made into a JIS type test piece at a molten resin temperature of 230 ° C. and a mold temperature of 50 ° C. with an injection molding machine, and the humidity of the test piece is 50%
After being left for 72 hours in a room at room temperature of 23 ° C., the flexural modulus was measured according to JIS K 7203. (Unit: kgf / cm ² ) Void: The olefin polymer was granulated in the same manner as in the previous section, and the obtained granulated product was extruded at a molten resin temperature of 250 ° C. using a T-die type film forming machine. A sheet having a thickness of 1 mm was prepared with a cooling roll at ℃. The sheet is heated with hot air at 150 ° C. for 70 seconds and stretched 7 times in the machine and transverse directions using a biaxial stretching machine,
A biaxially stretched film having a thickness of 20 μ was obtained. The film is observed with an optical microscope to measure the number of voids having a diameter of 10 μ or more, and less than 20 per 1 cm ² is ○, 20 to less than 50 is Δ, 5
Zero or more are shown by x.

Example 1 (1) Production of titanium trichloride composition 25 parts of n-hexane (6 l), diethylaluminum monochloride (DEAC) 5.0 mol, and diisoamyl ether 12.0 mol were added.
Mix for 5 minutes at ℃, and react for 15 minutes at the same temperature to produce reaction product (I) (diisoamyl ether / DEAC molar ratio 2.4)
Got

Put 40 mol of titanium tetrachloride in a reactor purged with nitrogen and
It is heated to ℃, and the total amount of the above reaction product liquid (I) is added to
After dripping in minutes, keep at the same temperature for 60 minutes, raise to 80 ° C and react for 1 hour, cool to room temperature, remove the supernatant liquid, add 20 liters of n-hexane and decant the supernatant liquid. The operation except for was repeated 4 times to obtain a solid product (II).

The whole amount of this (II) was suspended in 30 liters of n-hexane, 400 g of diethylaluminum monochloride was added, 15 kg of dimethyldiallylsilane was added at 40 ° C, and a polymerization treatment was performed at 40 ° C for 2 hours. After the treatment, raise the temperature to 50 ℃ and remove the supernatant.
The operation of adding 30 liters of hexane and removing the supernatant liquid by decantation was repeated 4 times to obtain a solid product (II-A) subjected to polymerization treatment.

With the total amount of this solid product suspended in 9 liters of n-hexane, 3.5 kg of titanium tetrachloride was added at room temperature for about 10 minutes and reacted at 80 ° C for 30 minutes, and then diisoamyl ether was added. 1.6 kg was added and the reaction was carried out at 80 ° C for 1 hour. After the completion of the reaction, the operation of removing the supernatant was repeated 5 times and then dried under reduced pressure to obtain a solid product (III), which was used as the titanium trichloride composition of the present invention. The crystalline dimethyldiallylsilane polymer content in the titanium trichloride composition was 50.0% by weight, and the titanium content was 12.6% by weight.

(2) Preparation of pre-activated catalyst After replacing a stainless steel reactor with an inclined blade with an internal volume of 80 liters with nitrogen gas, 40 liters of n-hexane, 28.5 g of diethylaluminum monochloride, (3) of the present invention obtained in (1) After heating 450 g of the titanium chloride composition at room temperature, 0.9 Nm ^{3 of} ethylene was supplied at 30 ° C. for 2 hours to cause reaction (reaction of 2.0 g of ethylene per 1 g of the titanium trichloride composition), and then unreacted ethylene was removed. It was removed, washed with n-hexane, and dried to obtain a preactivated catalyst.

(3) Polymerization of olefins 20 kg of polypropylene powder of MFR2.0 was put into a horizontal polymerization vessel of L / D = 3 equipped with a stirrer with an internal volume of 80 liter, and the pre-activated catalyst obtained in (2) above. N-hexane was added to prepare a 4.0 wt% n-hexane suspension, and the suspension was converted into titanium atom at 6.3 mg atom / hr, and diethylaluminum monochloride at 3.8 g / hr from the same pipe. It was fed continuously.

Hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was maintained at 1.0% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg / cm ² G.
It was carried out continuously for 0 hours. During the polymerization period, the polymer was continuously withdrawn from the polymerization vessel at 10 kg / hr so that the retention level of the polymer in the polymerization vessel was 50% by volume. The polymer extracted was subsequently obtained as a product powder after being contact-treated with nitrogen gas containing 0.2% by volume of propylene oxide at 95 ° C. for 15 minutes.

(4) Thermal stability test A titanium trichloride composition obtained in the same manner as in (1) above was tested at 40 ° C.
After being stored for 4 months in (4), propylene was polymerized in the same manner as (2) and (3).

(5) Attrition resistance test The reactor used in (2) was connected with a circulation line equipped with a circulation pump, and then obtained in the same manner as in (1) above with 20 l of n-hexane under a nitrogen atmosphere. 450 g of titanium trichloride composition was added. Then, the circulation pump was operated, and the suspension in the reactor was circulated for 4 hours under the conditions of a flow rate of 10 l / min and a temperature of 25 ° C using the circulation line, and then (2) and (3).
Polymerization of propylene was carried out in the same manner as in.

Comparative Example 1 (1) In the same manner as in (1) of Example 1, except that the solid product (II) was converted to the solid product (II-A) equivalent without being polymerized with dimethyldiallylsilane. A titanium chloride composition was obtained.

(2) A preactivated catalyst was prepared in the same manner as in (2) of Example 1 except that the titanium trichloride composition obtained in (1) above was used as the titanium trichloride composition.

(3) Polymerization of propylene was carried out in the same manner as in Example 1 (3) except that the preliminary activation catalyst obtained in the above (2) was used as the preliminary activation catalyst.

(4) Polymerization of propylene was carried out in the same manner as in (4) of Example 1 except that the titanium trichloride composition obtained in the same manner as in (1) above was used as the titanium trichloride composition.

(5) Polymerization of propylene was carried out in the same manner as in Example 1 (5) except that the titanium trichloride composition obtained in the same manner as in (1) above was used as the titanium trichloride composition.

Comparative Example 2 (1) A titanium trichloride composition was obtained in the same manner as in (1) of Comparative Example 1.

(2) To the reactor used in (2) of Example 1, 20-liter of n-hexane, 30 g of diethylaluminum monochloride, and 180 g of the titanium trichloride composition obtained in (1) above were added at room temperature, and then allyl was added. After 515 g of trimethylsilane was added and reacted at 40 ° C. for 2 hours (1.0 g reaction per 1 g of titanium trichloride composition), after completion of the reaction, it was washed with n-hexane, filtered and dried, and preactivated with allyltrimethylsilane. A catalyst was obtained.

(3) Propylene was polymerized in the same manner as in (3) of Example 1 except that the catalyst preactivated with the allyltrimethylsilane obtained in (2) above was used as the preactivated catalyst. Since the lump polymer blocked the powder extraction pipe, the production had to be stopped 14 hours after the start of the polymerization.

Comparative Example 3 (1) A titanium trichloride composition obtained in the same manner as in Comparative Example 1 (1) when the reaction product liquid (I) was reacted with titanium tetrachloride in Comparative Example 1 (1). The product was obtained by polymerizing pt-butylstyrene added with 2.9 kg in 100 l of n-hexane at 60 ° C for 2 hours using 500 g of the product and 120 g of diethylaluminum monochloride as a catalyst, followed by washing with methanol and drying. 1.9 kg of pt-butyl styrene polymer was pulverized in a vibrating mill with a capacity of 10 l for 5 hours at room temperature and then suspended in titanium tetrachloride as described above. A titanium trichloride composition containing 50.0% by weight of a styrene polymer was obtained.

(2) A preactivated catalyst was obtained in the same manner as in (2) of Example 1 except that the titanium trichloride composition obtained in (1) above was used as the titanium trichloride composition.

(3) In the same manner as in (3) of Example 1, except that the pre-activated catalyst obtained in (2) above was fed as the pre-activated catalyst so that the total pressure was maintained at 23 Kg / cm ² G. Polymerization was performed to obtain polypropylene.

Comparative Example 4 and Examples 2 and 3 By changing the amount of dimethyldiallylsilane used in (1) of Example 1, the crystalline dimethyldiallylsilane polymer contents were 0.001% by weight, 4.8% by weight and 28.6% by weight, respectively.
A titanium trichloride composition was obtained. Subsequently, propylene was polymerized in the same manner as in (2) and (3) of Example 1.

Example 4 4 L of n-heptane, diethylaluminum monochloride
The reaction solution obtained by reacting 5.0 mol, 9.0 mol of diisoamyl ether and 5.0 mol of di-n-butyl ether at 18 ° C. for 30 minutes was added dropwise to 27.5 mol of titanium tetrachloride at 40 ° C. for 300 minutes. After reacting at the temperature for 1.5 hours, the temperature was raised to 65 ° C and the reaction was continued for 1 hour. The supernatant was removed and n-hexane was added.
The operation of adding 20 l and removing by decantation was repeated 6 times, and 1.8 kg of the obtained solid product (II) was added to 40 l of n-hexane.
Suspended in diethyl aluminum monochloride 50
Add 0 g, and add 15 kg of dimethyldiallylsilane at 50 ° C 1
The reaction was carried out for a time to obtain a solid product (II-A) which had been subjected to a polymerization treatment.

After the reaction, the supernatant liquid was removed, 20 l of n-hexane was added, and the operation of removing by decantation was repeated twice. The solid product (II-A) subjected to the above polymerization treatment was suspended in 7 l of n-hexane. Muddy, 1.8 kg titanium tetrachloride, n-butyl ether 1.8
kg was added and reacted at 60 ° C. for 3 hours. After the reaction was completed, the supernatant was removed by decantation, 20 l of n-hexane was added, and the mixture was stirred for 5 minutes and allowed to stand, and the operation of removing the supernatant was repeated 3 times, followed by drying under reduced pressure to produce a solid. Get (III),
Polymerization of propylene was performed in the same manner as in (2) and (3) of Example 1 except that the solid product (III) was used as the final titanium trichloride.

Comparative Example 5 A titanium trichloride composition was obtained in the same manner as in Example 4, except that the solid product (II) was used as the solid product (II-A) equivalent without the polymerization treatment with dimethyldiallylsilane. , Propylene was polymerized.

Example 5 Instead of using 5.0 moles of diethyl aluminum monochloride, di-n-butyl aluminum monochloride 4.0
The reaction product solution (I) is obtained by using the moles of titanium tetrachloride
A titanium trichloride composition was obtained in the same manner as in (1) of Example 1, except that dropwise addition was carried out at 0 ° C. and 5.3 kg of p-trimethylsilylstyrene was used instead of using dimethyldiallylcin, followed by (2) Polymerization of propylene was carried out in the same manner as in (3).

Comparative Example 6 Polymerization of propylene was carried out in the same manner as in Example 5 except that the titanium trichloride composition was obtained without performing the polymerization treatment with p-trimethylsilylstyrene.

Example 6 In (1) of Example 1, instead of titanium tetrachloride, a mixed solution of 1.8 kg of silicon tetrachloride and 2.0 kg of titanium tetrachloride was used.
A solid product (III) was obtained in the same manner except that the amount of diisoamyl ether used was 2.2 kg and the reaction was carried out with the solid product (II-A). A titanium chloride composition was used.

Subsequently, n-hexane was added to the above titanium trichloride composition in a polymerization vessel equipped with a stirrer equipped with a two-stage turbine blade having an internal volume of 200 l to prepare a 4.0 wt% n-hexane suspension, and then the suspension was prepared. In terms of titanium atom, 10.0 mg atom / hr, and diethylaluminum monochloride at 6.0 g / hr from the same pipe, and n-hexane at 21 kg / hr from another pipe. Furthermore, hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was maintained at 1.5% by volume, and propylene was supplied so that the total pressure was maintained at 10 kg / cm ² G, and slurry polymerization of propylene was performed at 70 ° C. for 120 hours. , Went continuously.

During the polymerization period, the slurry has a continuous internal volume from the polymerization vessel so that the retained level of the slurry in the polymerization vessel is 75% by volume.
It was extracted into a 50 l flash tank. While unpressurized propylene was removed by depressurization in the flash tank, methanol was supplied at 1 Kg / hr and contact treatment was performed at 70 ° C. Subsequently, the slurry was separated from the solvent by a stretching separator and then dried to obtain a product powder at 10 Kg / hr.

Comparative Example 7 Titanium trichloride composition obtained in the same manner as in Example 6 except that the solid product (II) was used as the solid product (II-A) equivalent without the polymerization treatment with dimethyldiallylsilane. Was used to carry out slurry polymerization of propylene in the same manner as in Example 6.

Example 7 Titanium tetrachloride (27.0 mol) was added to n-hexane (12 l), and the temperature was 1 ° C.
After cooling to 1, 22.5 l of n-hexane containing 27.0 mol of diethylaluminum monochloride was further added dropwise at 1 ° C over 4 hours. After completion of the dropping, the reaction was carried out at the same temperature for 15 minutes, then the temperature was raised to 65 ° C. over 1 hour, and the reaction was further performed at the same temperature for 1 hour.

Next, the supernatant liquid was removed, 10 l of n-hexane was added, and the operation of removing by decantation was repeated 5 times. Of 5.7 kg of the obtained solid product (II), 1.8 kg was suspended in 50 l of n-hexane, Add diethyl aluminum monochloride 350g,
After further adding 19 kg of dimethyldiallylsilane at 40 ° C,
Polymerization was performed at 2 ° C. for 2 hours.

After the polymerization treatment, the supernatant was removed, 30 l of n-hexane was added, and the operation of removing by decantation was repeated twice.
The whole amount of the obtained solid product (II-A) subjected to the polymerization treatment was suspended in n-hexane 11, to which 1.6 l of di-isoamyl ether was added. This suspension was stirred at 35 ° C. for 1 hour and then washed 5 times with 3 l of n-hexane to obtain a treated solid. The treated solid obtained was suspended in 6 l of a 40% by volume titanium tetrachloride solution in n-hexane.

This suspension was heated to 65 ° C. and reacted at the same temperature for 2 hours. After the reaction was completed, 20 l of n-hexane was used once and 3
The solid obtained was washed and then dried under reduced pressure to obtain a solid product. Using the solid product (III) as the final titanium trichloride composition, propylene slurry polymerization was carried out in the same manner as in Example 6.

Comparative Example 8 A titanium trichloride composition was obtained by omitting the polymerization treatment with dimethyldiallylsilane in Example 7, and the subsequent Example 7 was performed.
Slurry polymerization of propylene was carried out in the same manner as.

Example 8 Using 3.0 kg of P-trimethylsilylstyrene instead of dimethyldiallylsilane in (1) of Example 1,
Polymerized solid product (II-A) was obtained, followed by n-
After adding 3.0 kg of titanium tetrachloride to 10 l of heptane, the whole amount of the solid product (II-A) was added and reacted at 80 ° C for 30 minutes. After the reaction was completed, 2.8 kg of di-n-pentyl ether was added.
Was added and reacted at 80 ° C for 1 hour to give a solid product (III)
Got Using the solid product (III) as the final titanium trichloride composition, vapor phase polymerization of propylene was carried out in the same manner as in (2) and (3) of Example 1.

Comparative Example 9 Polymerization of propylene was performed in the same manner as in Example 8 except that the titanium trichloride composition was obtained without performing the polymerization treatment with P-trimethylsilylstyrene.

Example 9 In Example 6, 12 kg of dimethyldiallylsilane was used when the solid product (III) was obtained, and ethylene was further fed during propylene polymerization so that the concentration in the gas phase was kept at 0.2% by volume. Other than the above, propylene-ethylene copolymerization was performed in the same manner as in Example 6.

Comparative Example 10 Propylene-ethylene copolymerization was performed in the same manner as in Example 9 except that the titanium trichloride composition was obtained without performing the polymerization treatment with dimethyldiallylsilane.

The titanium trichloride compositions of the above Examples and Comparative Examples, polymerization results and evaluation results are shown in the table.

[Brief description of drawings]

FIG. 1 is a flow sheet for explaining the manufacturing process of the present invention.

Claims (3)

[Claims] 1. A solid product (II) obtained by reacting an organoaluminum compound, or a reaction product (I) of an organoaluminum compound and an electron donor (B ₁ ) with titanium tetrachloride is treated with a dialkyldiamine. Polymerization treatment with allylsilane and / or trialkylsilylstyrene, and after the polymerization treatment, the final solid product obtained by reacting an electron donor (B ₂ ) with a halide of an element of Group III to VI of the periodic table (III) containing 0.01% to 99% by weight of a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer, and 99.99% to 1% by weight of a titanium trichloride composition. And a titanium trichloride composition for producing an olefin polymer. 2. A solid product (II) obtained by reacting an organoaluminum compound, or a reaction product (I) of an organoaluminum compound and an electron donor (B ₁ ) with titanium tetrachloride is treated with a dialkyldiamine. Polymerization treatment with allylsilane and / or trialkylsilylstyrene, and after the polymerization treatment, the final solid product obtained by reacting an electron donor (B ₂ ) with a halide of an element of Group III to VI of the periodic table (III) containing 0.01% to 99% by weight of a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer, and 99.99% to 1% by weight of a titanium trichloride composition. A method for producing a titanium trichloride composition for producing an olefin polymer, comprising: 3. An organoaluminum compound having the general formula
AlR ¹ _m R ² _{m ′} X _{3 − (m + m ′)} (wherein R ¹ and R ² represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, and X represents a halogen; m,
m ′ represents an arbitrary number of 0 <m + m ′ ≦ 3. The manufacturing method of Claim 2 which uses the organoaluminum compound represented by these.