JPH0780955B2 - Titanium trichloride composition for producing α-olefin polymer - Google Patents

Description

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

[Conventional technology and its problems]

A crystalline α-olefin polymer such as crystalline polypropylene is an α-olefin produced by a so-called Ziegler-Natta catalyst composed of a transition metal compound of groups IV to VI of the periodic table and an organometallic compound of a metal of groups I to III. It is well known that it can be obtained by polymerizing
Various titanium trichloride compositions have been widely used as transition metal compound catalyst components.

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 titanium tetrachloride with a reaction product of an organoaluminum compound and an electron donor is an electron donor and an electron acceptor. And a method for producing an α-olefin polymer using a titanium trichloride composition obtained by reacting with a compound (Japanese Patent Publication No. 59-28,573) or a reaction product of an organoaluminum compound and an electron donor with tetrachloride. A solid obtained by reacting titanium is subjected to a polymerization treatment with α-olefin, and then a titanium trichloride composition obtained by reacting an electron donor and an electron acceptor is used to produce an α-olefin polymer. Method (JP-A-58-17,104), the storage stability of the titanium trichloride composition, the polymerization activity, the crystallinity of the obtained α-olefin polymer, etc. are significantly improved as compared with the conventional method. To And it has carried out a proposal.

However, although these improved methods have the advantages as described above, the obtained α-olefin polymer is translucent, which may impair the commercial value in the field of use, resulting in improved transparency. Was wanted.

On the other hand, attempts have also been made to improve the transparency of α-olefin polymers, for example, aluminum salts of aromatic carboxylic acids (Japanese Patent Publication No. 40-1,652) and benzylidene sorbitol derivatives (Japanese Patent Publication No. 51-22,740). However, when an aluminum salt of an aromatic carboxylic acid is used, the dispersibility is poor and the effect of improving transparency is insufficient. In addition, when a benzylidene sorbitol derivative is used, there is a certain improvement in transparency, but there are problems such as strong odor during processing and bleeding of additives (embossing). It was

Styrene, o-methyl styrene, p-t-butyl styrene,
Method for carrying out multi-stage polymerization of 1-vinylnaphthalene and propylene and its composition (JP-A-62-1738, JP-A-62-227,911, JP-A-63-15,803, JP-A-63-15,803) 63-68,648 gazette), the inventors of the present invention produced polypropylene according to the method proposed by the present inventors. Since a polymer is produced, this method cannot be adopted in an industrial long-term continuous polymerization method, particularly in a gas phase polymerization method in which the polymerization of α-olefin 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 during the production of a transition metal catalyst component for propylene polymerization (Japanese Patent Laid-Open No. 63-69,809). No. gazette) has been proposed,
Since the proposed method requires a separate step of producing a pt-butylstyrene polymer, it is not only industrially disadvantageous, but also has the same problem of void formation in the film as in the above-mentioned prior art. Had.

The inventors of the present invention, when producing an α-olefin polymer with improved transparency, have a void in the film due to generation of a bulk polymer or poor dispersion, which is a problem of the prior art using a polymer of styrenes. We have studied earnestly how to solve problems such as occurrence.

As a result, a titanium trichloride composition containing a crystalline polymer of halogen-substituted styrene was found by a specific method, and when using a catalyst in which this titanium trichloride composition and an organoaluminum compound were combined, as described above. To solve the problems in the production of various conventional α-olefin polymers,
And not only is it possible to obtain an α-olefin polymer excellent in transparency and crystallinity, which has good dispersibility and extremely few voids, and also the storage stability of the titanium trichloride composition at a high temperature of 35 ° C or higher. Further, the present invention has been made by knowing that it has a remarkable effect also on the abrasion resistance in a production apparatus during the large-scale production of the titanium trichloride composition.

The present invention relates to a titanium trichloride composition for producing an α-olefin polymer capable of producing an α-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. It is intended to provide.

[Means for solving the problem]

 The present invention has the following configurations.

(1) The following equation, (Wherein X represents halogen, R ¹ represents hydrogen or an alkyl group), and contains 0.01% to 99% by weight of a halogen-substituted styrene crystalline polymer composed of a repeating unit represented by the following formula. The final solid product (II
A titanium trichloride composition for producing an α-olefin polymer, which is I).

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 represented by the following formula: (In the formula, X is halogen, R ¹ is hydrogen or an alkyl group.) Polymerization treatment is carried out with halogen-substituted styrenes, and further, an electron donor (B ₂ ) and an element of Group III to VI of the periodic table. To the final solid product (III) obtained by reacting with a halide of (Wherein X represents halogen and R ¹ represents hydrogen or an alkyl group). A titanium trichloride composition containing 0.01% to 99% by weight of a crystalline polymer of a halogen-substituted styrene having a repeating unit represented by the formula: Method of manufacturing things.

(2) As the organoaluminum compound, the general formula is AlR ² _m R
³ _{m ′} X _{3- (m + m ′)} (wherein R ² and R ³ 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, m ′ Represents an arbitrary number of 0 <m + m ′ ≦ 3). The titanium trichloride composition according to the above item 1, wherein the organoaluminum compound represented by the formula is used.

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

The titanium trichloride composition for producing an α-olefin polymer of the present invention has the following formula: (In the formula, X represents halogen and R ¹ represents hydrogen or an alkyl group.) A crystalline polymer of halogen-substituted styrenes (hereinafter, abbreviated as halogen-substituted styrene polymer). The present invention is a titanium trichloride composition containing a).

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 A solid product (II) obtained by reacting an organoaluminum compound with titanium tetrachloride is represented by the following formula: (In the formula, X is halogen and R ¹ is hydrogen or an alkyl group.) After the polymerization treatment with halogen-substituted styrenes (hereinafter sometimes abbreviated as halogen-substituted styrenes), The titanium trichloride composition of the present invention is produced as the final solid product (III) obtained by reacting the electron donor (B ₂ ) with the electron acceptor.

In the present invention, "polymerizing" means that the halogen-substituted styrenes are polymerized by contacting the solid product (II) with the halogen-substituted styrenes under a polymerizable condition. The product (II) is covered 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 9.5 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 of polymerizing the reaction product (I) with titanium tetrachloride or the solid product (II) obtained by reacting an organoaluminum compound with titanium tetrachloride with halogen-substituted styrenes, reaction generation (I) or a method of polymerizing the solid product (II) by adding halogen-substituted styrenes at any stage of the reaction between the organoaluminum compound and titanium tetrachloride, the reaction product (I), or the organic product. After completion of the reaction between the aluminum compound and titanium tetrachloride, a method of polymerizing the solid product (II) by adding halogen-substituted styrenes, and a reaction product (I), or an organoaluminum compound and titanium tetrachloride After the reaction was completed, the liquid portion was separated and removed by filtration or decantation, and the obtained solid product (II)
Is suspended in a solvent, an organoaluminum compound and a halogen-substituted styrene 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 halogen-substituted styrenes 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 carried out in any order, and the halogen-substituted styrenes may be added 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 halogen-substituted styrenes is carried out by adding halogen-substituted styrenes at any stage of the reaction between the reaction product (I) or the organoaluminum compound and titanium tetrachloride, and the reaction product (I) or the organoaluminum compound. When halogen-substituted styrenes are added after completion of the reaction with 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 / cm ² G under solid conditions. Using 0.01 g to 100 kg of halogen-substituted styrenes per 100 g of product (II), the final solid product (II
I), that is, the polymerization is carried out so that the content of the halogen-substituted styrene polymer in the titanium trichloride composition of the present invention is 0.01% by weight to 99% by weight.

The content of the halogen-substituted styrene polymer is less than 0.01 wt%, the effect of improving the transparency and crystallinity of the α-olefin polymer produced using the titanium trichloride composition obtained is insufficient, On the other hand, if 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 and titanium tetrachloride is completed by the polymerization treatment with halogen-substituted styrenes, the liquid portion is separated and removed by filtration or decantation, and the obtained solid product ( Solid product (II) when it is carried out after suspending II) in a solvent.
To 100 g, 100 ml to 5,000 ml of solvent and 0.5 g to 5,000 g of organic aluminum compound are added, and the reaction temperature is 0 ° C to 90 ° C for 1 minute to
In the final solid product (III), the reaction pressure is from atmospheric pressure to 10 kgf / cm ² G for 10 hours, using 0.01 g to 100 kg of halogen-substituted styrenes per 100 g of solid product (II). Polymerization is carried out so that the content of the halogen-substituted styrene polymer 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 any 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 of 0 ° C. to 50 ° C. for 1 minute to 3 hours,
(F) is reacted under the same conditions as described 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 the addition of -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 halogen-substituted styrene of the present invention. Solid product (III) which is a titanium trichloride composition for producing an α-olefin polymer containing a polymer
Is obtained.

The solid product (III) thus obtained, that is, the titanium trichloride composition of the present invention, contains a halogen-substituted styrene polymer.
It is contained in an amount of 0.01% by weight to 99% by weight, and is used as a transition metal compound catalyst component for producing an α-olefin polymer in combination with at least an organoaluminum compound for the polymerization of α-olefin.

The organoaluminum compound used for producing the titanium trichloride composition of the present invention has a general formula of AlR ² _m R ³ _{m ′} X _3-
( M _{+ m ′)} (wherein R ² and R ³ 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 Monoalkyl aluminum dihalides, etc. 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, 2-ethylhexyl toluate, 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, acetic acid , Fatty acids such as propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, aromatic acids such as benzoic acid, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as benzophenone, nitrile acids such as acetonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β (N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline, 2,4,6-trimethyl Amines such as pyridine, N, N, N ′, N′-tetramethylethylenediamine, aniline, dimethylaniline, formamide, hexamethylphosphoric triamide, N, N, N ′, N ′, N ″ -pentamethyl-N ′ -Β
Amides such as dimethylaminomethylphosphoric triamide, octamethylpyrophosphoramide, ureas such as N, N, N ′, N′-tetramethylurea, phenyl isocyanate,
Isocyanates such as toluyl isocyanate, azo compounds such as azobenzene, ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-
Phosphines such as octylphosphine, triphenylphosphine and triphenylphosphine oxide, dimethylphosphite, di-n-octylphosphite, triethylphosphite, tri-n-butylphosphite, triphenylphosphite and other phosphites, ethyldiethyl Phosphinite, ethylbutylphosphinite,
Examples include phosphinites such as phenyldiphenylphosphinite, thioethers such as diethyl thioether, diphenyl thioether, methylphenyl thioether, ethylene sulfide and propylene sulfide, thioalcohols such as ethyl thioalcohol, n-propyl thioalcohol and thiophenol. You can also

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 halides of Group I elements. 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 halogen-substituted styrenes used in the polymerization treatment have the following formula: (In the formula, X is any halogen of Cl, Br, F and I,
R ¹ represents hydrogen or an alkyl group having 1 to 4 carbon atoms. ) Is a specific monomer. Specific examples include 2-ethyl-4-chlorostyrene, 2-methyl-4-fluorostyrene, o-fluorostyrene, p-fluorostyrene 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 α-olefin, or more preferably, an α-olefin is reacted. The thus-prepared catalyst is used for the polymerization of α-olefin.

As the organoaluminum compound used for the polymerization of α-olefin, 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.

Further, as the α-olefin used for pre-activation, ethylene, propylene, butene-1, pentene-
1, linear olefins such as 1, hexene-1, heptene-1, 4-methyl-pentene-12-methyl-pentene-
1 and the like branched chain monoolefins.

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

The polymerization mode of the α-olefin using the above catalyst is not limited, and it can be suitably carried out not only in liquid phase polymerization such as slurry polymerization and bulk polymerization but also in gas phase polymerization.

A catalyst obtained by combining a titanium trichloride composition and an organoaluminum compound is sufficiently effective for slurry polymerization or bulk polymerization, but in the case of gas phase polymerization, a catalyst pre-activated by reacting an α-olefin is preferable. When performing gas phase polymerization following slurry polymerization or bulk polymerization,
Even if the catalyst initially used is the former, since the reaction of the α-olefin has already been carried out during the gas phase polymerization, it becomes the same as the latter catalyst and an excellent effect can be 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 α-olefin 0.05 g to 5,000 g, preferably
Use 0.05g to 3,000g. Temperature is 0 ℃ to 100 ℃, 1 minute to 20
Titanium trichloride composition by reacting α-olefin for a period of time
It is desirable to react 0.01-2,000 g, preferably 0.05-200 g of α-olefin per 1 g.

The pre-activation can also be carried out in a hydrocarbon solvent such as propane, butane, n-pentane, n-hexane, n-heptane, benzene and toluene, and even in liquefied α-olefins such as liquefied propylene and liquefied butene-1, It can be carried out in gaseous ethylene or 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 α-olefin polymer to be polymerized. The polymer particles that can coexist are in the range of 0 to 5,000 g per 1 g of the titanium trichloride composition.

The solvent or α-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, filtration or the like, or the solid product
Solvents can also be added to suspend them in amounts not exceeding 80 l / g.

There are various embodiments of the pre-activation method, for example, a method in which an α-olefin is brought into contact with a catalyst in which a titanium trichloride composition and an organoaluminum are combined to carry out a slurry reaction, a bulk reaction or a gas phase reaction, an α-olefin. The method of combining the titanium trichloride composition and the organoaluminum under the coexistence of, the method of coexisting the α-olefin polymer by the method of, and the coexistence of hydrogen by the 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, the catalyst composed of the titanium trichloride composition and the organoaluminum compound combined with each other, or the catalyst pre-activated with α-olefin is used for the production of α-olefin polymer, but it is usually used for olefin polymerization. Similarly to the above, 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 ordinary α-olefin polymerization, but specifically, to 1 g of the titanium trichloride composition,
Organoaluminum compound 0.01g-500g, electron donor 0-2
Use 00g.

As the polymerization method for polymerizing the α-olefin, as described above, slurry polymerization carried out in a hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, n-octane, benzene or toluene, liquefied propylene and liquefied butene. There are a bulk polymerization carried out in a liquefied α-olefin monomer such as −1, a gas phase polymerization in which an α-olefin such as ethylene and propylene is polymerized in a gas phase, or a method of stepwise combining two or more of the above. In either case, the polymerization temperature is room temperature (20 ° C.) to 200 ° C., the polymerization pressure is normal pressure (0 kg / cm ² G) to 50 kg / cm ² G, and the polymerization is usually performed for about 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 α-olefin used for the polymerization includes linear monoolefins such as ethylene, propylene, butene-1, hexene-1, and octene-1, 4-methylpentene-1, 2,
-Branched monoolefins such as -methyl-pentene-1,
Diolefins such as butadiene, isoprene, chloroprene, etc., and not only homopolymerization of each of these, but also in combination with each other α-olefin, for example, propylene and ethylene, butene-1 and ethylene, Copolymerization can be carried out by combining propylene and butene-1, or by combining three components such as propylene, ethylene, and butene-1.
It is also possible to carry out block copolymerization by changing the type of olefin.

[Action]

The α-olefin polymer obtained by using the titanium trichloride composition of the present invention contains a highly stereoregular halogen-substituted styrene polymer in an extremely dispersed state, so that the halogen-substituted styrene polymer is melt-molded. The nucleating action of the homologous polymer reduces the spherulite size of the α-olefin polymer and promotes crystallization, and as a result, the transparency and crystallinity of the entire α-olefin polymer are increased.

In addition, the halogen-substituted styrene polymer introduced into the α-olefin polymer by using the titanium trichloride composition of the present invention is, as described above, a stereoregular high molecular weight polymer, and thus bleeds on the surface. There is nothing to do.

〔The invention's effect〕

The main effect of the present invention is that when the titanium trichloride composition of the present invention is used as a transition metal compound catalyst component for producing an α-olefin polymer for the polymerization of α-olefin, the generation of voids is extremely high. It is possible to produce an α-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 is that, when used for α-olefin polymerization, both transparency and crystallinity of the obtained α-olefin polymer are improved and the number of voids is extremely small.

As is apparent from the examples shown below, the internal haze of the press film of the α-olefin polymer obtained by using the titanium trichloride composition of the present invention does not contain a halogen-substituted styrene polymer, titanium trichloride. Compared with the α-olefin polymer obtained by using the composition, the ratio is about 1/4 to 3/7, which is extremely high transparency.

In addition, the crystallization temperature was increased by about 6 ° C to 9 ° C as compared with the case where the halogen-substituted styrene polymer was not contained, and the crystallinity was remarkably improved and the flexural modulus was 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 the α-olefin polymer into which the styrene polymer 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 α-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 α-olefin polymer can be produced by a long-term continuous polymerization method by a simpler process such as a gas phase polymerization method. It is extremely advantageous in production.

The third effect of the present invention is that the titanium trichloride composition for producing an α-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.

Furthermore, the fourth effect of the present invention is that the titanium trichloride composition for producing an α-olefin polymer of the present invention is excellent in abrasion resistance.
The titanium trichloride composition is not susceptible to grinding during use, that is, not only in the α-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 α-olefin polymer. As a result, prevention of line blockage troubles in the gas phase polymerization process, fine powder α- in the circulating gas
It is extremely effective in preventing compressor troubles resulting from the mixture of olefin polymers.

〔Example〕

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 conditions of α-olefin polymer powder thickness 150μ
After coating liquid paraffin on both surfaces of the film, 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-butyl-4'-hydroxyphenyl) propionate] methane per 100 parts by weight of α-olefin polymer powder 0.1 parts by weight, and 0.1 parts by weight of calcium stearate are mixed, and the mixture is screw diameter 40 mm.
It granulated using the extrusion granulator of. Then, the granulated product was made into a JIS type test piece at a molten resin temperature of 230 ° C and a mold temperature of 50 ° C by an injection molding machine, and the humidity of the test piece was 50%.
%, The flexural modulus was measured according to JIS K 7203 after being left for 72 hours at room temperature of 23 ° C.

(Unit: kgf / cm ² ) Void: The α-olefin polymer was granulated in the same manner as in the previous section, and the resulting granulated product was extruded at a molten resin temperature of 250 ° C. using a T-die type film forming machine. , 1mm thick with 20 ℃ cooling roll
Created a sheet of. The sheet was 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 to obtain a biaxially stretched film having a thickness of 20 μm. The film was observed with an optical microscope and the number of voids having a diameter of 10 μm or more was measured. Less than 20 per 1 cm ² was indicated by ◯, 20 or more and less than 50 by Δ, and 50 or more 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 entire amount of this (II) was suspended in 30 liters of n-hexane, 400 g of diethylaluminum monochloride was added, and 2
19 kg of -methyl-4-fluorostyrene was added, and a polymerization treatment was carried out at 40 ° C for 2 hours. After the treatment, the temperature was raised to 50 ° C, the supernatant was removed, 30 l of n-hexane was added, and the operation of removing the supernatant by decantation was repeated 4 times to obtain a solid product (II-A) subjected to polymerization treatment. Obtained.

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 reacted 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. Crystalline 2- in the titanium trichloride composition
The content of methyl-4-fluorostyrene polymer was 33.3% by weight, and the content of titanium was 16.8% by weight.

(2) Preparation of preactivated catalyst component After replacing a stainless steel reactor with an inclined blade with an internal volume of 80 l with nitrogen gas, 40 l of n-hexane, 28.5 g of diethylaluminum monochloride, (1) of the present invention obtained After 340 g of the titanium trichloride composition was added at room temperature, 0.7 Nm ^{3 of} ethylene was supplied at 30 ° C. for 2 hours to cause a reaction (reaction of 2.0 g of ethylene per 1 g of the titanium trichloride composition), and then unreacted ethylene Was removed, washed with n-hexane and then dried to obtain a preactivated catalyst component.

(3) Polymerization of α-olefin After introducing 20 kg of polypropylene powder of MFR 2.0 into a horizontal polymerization vessel of L / D = 3 equipped with a stirrer having an internal volume of 80 liter and substituted with nitrogen, the preliminary activation obtained in the above (2) After n-hexane was added to the catalyst component to prepare a 4.0 wt% n-hexane suspension, the suspension was converted into titanium atoms at 6.45 mg atom / h.
r, and 3.8 g of diethylaluminum monochloride
It was continuously supplied from the same pipe for hr.

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 retained 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. 340 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) The solid product (II) in Example 1 (1) was mixed with 2
A titanium trichloride composition was obtained in the same manner, except that the solid product (II-A) was used as the equivalent without the polymerization treatment with -methyl-4-fluorostyrene.

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

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

(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) 20 l of n-hexane, 30 g of diethylaluminum monochloride, and 180 g of the titanium trichloride composition obtained in (1) above were added to the reactor used in (2) of Example 1 at room temperature, and then p 165 g of -t-butylstyrene was added and reacted at 40 ° C. for 2 hours (0.5 g reaction per 1 g of titanium trichloride composition). After completion of the reaction, the catalyst component was washed with n-hexane, filtered and dried to obtain a catalyst component preactivated with pt-butylstyrene.

(3) Polymerization of propylene is carried out in the same manner as in Example 1 (3) except that the catalyst component pre-activated with pt-butylstyrene obtained in (2) above is used as the pre-activated catalyst component. After the polymerization started, the lumpy polymer formed blocked the powder extraction pipe.
The production had to be stopped in 11 hours.

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 1.45 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, washed with methanol and dried. In the same manner as above except that 0.95 kg of pt-butyl styrene polymer was crushed in a vibrating mill having a capacity of 10 l at room temperature for 5 hours and then suspended in the above titanium tetrachloride. 33.3% by weight of styrene polymer
The contained titanium trichloride composition was obtained.

(2) A preactivated catalyst component 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) The total pressure of the pre-activated catalyst component obtained in (2) above as the pre-activated catalyst component in (3) of Example 1 was 23 kg.
Polymerization of propylene was carried out in the same manner except that the supply was performed so as to keep / cm ² G, to obtain polypropylene.

Comparative Example 4 and Examples 2 and 3 In (1) of Example 1, the amount of 2-methyl-4-fluorostyrene used was changed to give crystalline 2-methyl-4-methyl-4-.
Fluorostyrene polymer content is 0.001% by weight,
4.8 wt% and 16.7 wt% 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
2-methyl-4-fluorostyrene 16 was added at 50 ° C.
kg was added and the reaction was carried out for 1 hour 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. (III) was obtained, and propylene was polymerized 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 composition.

Comparative Example 5 Titanium trichloride was prepared in the same manner as in Example 4, except that the solid product (II) was replaced with the solid product (II-A) without the polymerization treatment with 2-methyl-4-fluorostyrene. The composition was obtained and 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 to obtain titanium tetrachloride.
A titanium trichloride composition was obtained in the same manner as in (1) of Example 1, except that the mixture was added dropwise at 45 ° C. and 15 kg of o-fluorostyrene was used instead of using 2-methyl-4-fluorostyrene. Subsequently, propylene was polymerized in the same manner as (2) and (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 the polymerization treatment with o-fluorostyrene.

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.
Further, 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. Was converted to 10.1 mg atom / hr in terms of titanium atom, and 6.0 g / hr of diethylaluminum monochloride was continuously supplied from the same pipe, and n-hexane was continuously supplied from another pipe at 21 kg / hr. 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 the pressure was reduced in the flash tank to remove unreacted propylene, methanol was supplied at 1 kg / hr and subjected to contact treatment at 70 ° C. Subsequently, the slurry was separated from the solvent by a centrifuge and then dried to obtain a product powder at 10 kg / hr.

Comparative Example 7 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 2-methyl-4-fluorostyrene. Using the titanium trichloride composition, slurry polymerization of propylene was carried out 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, and 1.8 kg of 5.7 kg of the obtained solid product (II) was suspended in 50 l of n-hexane. , 350 g of diethylaluminum monochloride, and further 19 kg of o-fluorostyrene at 40 ° C.,
Polymerization was carried out at 40 ° 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 thus obtained was washed and then dried under reduced pressure to obtain a solid product (III). 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 o-fluorostyrene in Example 7, and thereafter slurry polymerization of propylene was performed in the same manner as in Example 7.

Example 8 Using 4.7 kg of p-fluorostyrene instead of 2-methyl-4-fluorostyrene in (1) of Example 1, a polymerized solid product (II-A) was obtained. After adding 3.0 kg of titanium tetrachloride to 10 l of n-heptane,
All of the solid product (II-A) was added and reacted at 80 ° C. for 30 minutes. After completion of the reaction, di-n-pentyl ether 2.
8 kg was added and reacted at 80 ° C for 1 hour to give a solid product (II
I) 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 carried out in the same manner as in Example 8 except that the titanium trichloride composition was obtained without performing the polymerization treatment with p-fluorostyrene.

Example 9 In Example 6, the amount of 2-methyl-4-fluorostyrene used in obtaining the solid product (III) was 17 kg, and the concentration in the gas phase was maintained at 0.2% by volume during propylene polymerization. Propylene-ethylene copolymerization was performed in the same manner as in Example 6 except that ethylene was further supplied.

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 2-methyl-4-fluorostyrene.

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 process diagram (flow chart) for explaining the method for producing the composition of the present invention.

Claims (2)

[Claims] 1. The following equation, (Wherein X represents halogen, R ¹ represents hydrogen or an alkyl group), and contains 0.01% to 99% by weight of a halogen-substituted styrene crystalline polymer composed of a repeating unit represented by the following formula. The final solid product (II
A titanium trichloride composition for producing an α-olefin polymer, which is I). 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 represented by the following formula: (In the formula, X is halogen, R ¹ is hydrogen or an alkyl group.) Polymerization treatment is carried out with halogen-substituted styrenes, and further, an electron donor (B ₂ ) and an element of Group III to VI of the periodic table. To the final solid product (III) obtained by reacting with a halide of (Wherein X represents halogen and R ¹ represents hydrogen or an alkyl group). A titanium trichloride composition containing 0.01% to 99% by weight of a crystalline polymer of a halogen-substituted styrene having a repeating unit represented by the formula: Method of manufacturing things. 2. An organoaluminum compound having the general formula
AlR ² _m R ³ _{m ′} X _{3 − (m + m ′)} (wherein R ² and R ³ represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, and X represents a halogen; The titanium trichloride composition according to claim 1, wherein an organoaluminum compound represented by m and m'represents an arbitrary number of 0 <m + m'≤3).