JPH01282203A - Titanium trichloride composition for olefin polymerization and production thereof - Google Patents

Abstract

PURPOSE:To obtain a composition capable of producing polyolefin in good productivity, having excellent transparency and crystallinity and a slight generation of void in using of polymerization of olefin, containing a specific amount of alkenylsilane polymer composing a specific repeating unit. CONSTITUTION:An organic Al compound (e.g., trimethylaluminum, methylaluminumsesquichloride), or a reaction product of organic Al compound and electron donor (e.g., diethylether) is reacted with TiCl4 to obtain a solid product. Next, the product is polymerization treated with alkenylsilane compound expressed by formula I [n is 0-2; R<1>, R<2>, R<3> is (cyclo)alkyl or aryl], then mixed with 0.1-99wt.% alkenylsilane polymer obtained by a reaction of electron donor and electron acceptor (e.g., TiCl4) and having a repeating unit expressed by formula II to afford the aimed composition.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a titanium trichloride composition for olefin polymerization and a method for producing the same.More specifically, it relates to a titanium trichloride composition for olefin polymerization and a method for producing the same. A titanium trichloride composition for olefin polymerization suitable as a compound catalyst component and a method for producing the same are described.

(Prior art and its problems) Crystalline polyolefins such as crystalline polypropylene are so-called Ziegler-Natsuta compounds, which are composed of transition metal compounds of groups ■ to vr of the periodic table and organometallic compounds of metals of groups I to III of the periodic table. It is well known that titanium trichloride can be obtained by catalytically polymerizing olefins, and among them, various titanium trichloride compositions are widely used as transition metal compound catalyst components. Among these titanium trichloride compositions, the type obtained by converting titanium tetrachloride into organic aluminium, reducing it with metal, and then heat-treating it has a good shape of the resulting polymer, so many improved manufacturing methods are being considered. has been done. For example, a method in which 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 formation of amorphous polymers ( Tokuko Showa 5
3-3J58), etc.

The present applicant has already made many proposals in this field.1. Among them, a titanium trichloride composition obtained by reacting an electron donor and an electron acceptor with a solid obtained by reacting titanium tetrachloride with a reaction product of an organoaluminum compound and an electron donor is used. A method for producing polyolefin (Japanese Patent Publication No. 59-28,573) and a solid obtained by reacting titanium tetrachloride with the reaction product of an organoaluminum compound and an electron donor are polymerized with α-olefin. Later, in a method for producing polyoffins using a titanium trichloride composition obtained by reacting an electron donor and an electron acceptor (Japanese Patent Application Laid-open No. 17,104/1982), compared to the conventional method, , have proposed significant improvements in the storage stability, polymerization activity, and crystallinity of the resulting polyolefin of titanium trichloride compositions.

However, although these improved methods have the above-mentioned advantages, the polyolefins obtained are translucent, which may impair commercial value in the field of application, and improvements in transparency have been desired. .

On the other hand, attempts have been made to improve the transparency of polyolefins. There is a method of adding a nucleating agent to polypropylene (e.g., Japanese Patent Publication No. 1, No. 1, No. 2003-2012), but 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 benzylidene sorbitol conductors are used, although some improvement can be seen in transparency, there are problems such as strong odor during processing and additive bleed phenomenon (embossment). had.

Propylene, an α-olefin having 4 to 18 carbon atoms, and 3
- Method for copolymerizing methylbutene-1 or 3-methylpentene-1 (Japanese Patent Publication No. 32.43G of 1983)
Another method has been proposed (Japanese Unexamined Patent Application Publication No. 139/1983) in which polymerization of vinylcyclohexane and propylene are carried out in multiple stages. However, in both methods, not only the polymerization activity decreases but also bulky polymers are produced. was a method that could not be adopted. Furthermore, the film produced using the obtained polypropylene had many voids, which impaired its commercial value.

In addition, a similar method is used to produce highly crystalline polypropylene by polymerizing a small amount of trialkylvinylsilane or trialkylarylsilane such as vinyltrimethylsilane, and then polymerizing propylene (Japanese Patent Laid-Open No. 83 15,804), but the specification of said publication does not provide any data on the transparency of the obtained polypropylene, and even with this method, there is a decrease in polymerization activity, a lumpy polymer However, there were problems with the formation of film and voids in the film.

Furthermore, as a method for improving these multi-stage copolymerization techniques, a method of selectively using aluminum compounds in multiple stages (Japanese Unexamined Patent Publication No. 6
Publication No. 2-275,110, JP-A-63-37.104
(Japanese Unexamined Patent Publication No. 1983-37,105) and a method in which a small amount of propylene is polymerized batchwise before the main polymerization of propylene (Japanese Patent Application Laid-open No. 1983-37,105) suppress a decrease in polymerization activity and a decrease in boiling n-heptane extraction residue. However, none of the improvement methods could suppress the formation of lumpy polymers and the generation of voids in the film.

The present inventors have discovered that when producing polyolefins with improved transparency, the conventional techniques using the above-mentioned copolymerization techniques are all performed by multi-stage polymerization in the presence of an already formed catalyst system. This causes the formation of lumpy polymers and poor dispersion, and as a result, there are problems not only in manufacturing but also in the quality of the obtained products. In view of this, we conducted intensive research on methods to solve the problems of the conventional technology at the transition metal compound catalyst component stage.

As a result, we discovered a titanium trichloride composition containing an alkenylsilane polymer and a method for producing the same, and when using a catalyst in which this titanium trichloride composition is combined with an organoaluminum compound, it is possible to use a catalyst that combines the titanium trichloride composition with an organoaluminum compound. It not only solves the problems in polyolefin production and provides a polyolefin with extremely few voids and excellent transparency and crystallinity, but also the titanium trichloride composition.
The present invention was made based on the knowledge that the titanium trichloride composition has a remarkable effect on storage stability at high temperatures above .degree. C. and on resistance to abrasion in manufacturing equipment during large-scale production of the titanium trichloride composition.

The present invention provides a titanium trichloride composition for olefin polymerization that can produce a polyolefin with extremely high productivity, extremely low void generation, and extremely high transparency and crystallinity, and a method for manufacturing the titanium trichloride composition. The purpose is to provide the following.

[Means for Solving the Problems and Effects of the Invention] The present invention has the following configuration.

(1) The following formula, ÷C) I2-CH÷ (C1+21n R'-5i-R'' (where n is an integer from 0 to 2, R1, R2, R
3 represents an alkyl group, a cycloalkyl group, or an aryl group. A titanium trichloride composition for olefin polymerization containing 0.1i1% by weight to 9g11% by weight of an alkenylsilane polymer consisting of a repeating unit represented by ).

(2) Organoaluminum compound or reaction product of organoaluminum compound and electron donor (B1) (1)
A solid product obtained by reacting titanium tetrachloride with titanium tetrachloride (wherein the general formula is C)+2-CH-(CH2), -5t-82 (in the formula,
n is an integer from 0 to 2, and R1, R2, and R3 represent an alkyl group, a cycloalkyl group, or an aryl group. A method for producing a titanium trichloride composition for olefin polymerization containing 0.1% to 991% by weight of an alkenylsilane polymer, the composition being obtained by reacting an alkenylsilane polymer with an electron acceptor.

(3) As an organoaluminum compound, the general formula is AIR'
, R'1Xs-(+++*m'L (wherein, R4, R
'Gf 7 represents a hydrocarbon group or alkoxy group such as a group, a cycloalkyl group, or an aryl group; The manufacturing method according to item 2 above, using an organoaluminum compound represented by , ).

The configuration and effects of the present invention will be explained in detail below.

The titanium trichloride composition for olefin polymerization of the present invention is a titanium trichloride composition containing an alkenylsilane polymer, and a method for producing the titanium trichloride composition will be explained.

The titanium trichloride composition is produced as follows. first,
A solid product (II) obtained by reacting an organoaluminum compound and an electron donor (Bl) to obtain a reaction product (I) and reacting this (r) with titanium tetrachloride, or an organoaluminum A solid product (11) obtained by reacting a metal compound and titanium tetrachloride is prepared by - formula is CH, -CH-(CH2) n-5l-R" (in the formula, n
is an integer from O to 2, and R1, R2, and R1 represent an alkyl group, a cycloalkyl group, or an aryl group.

) After polymerization with an alkenylsilane compound represented by (B2), an electron donor (B2) and an electron acceptor are further reacted to obtain a titanium trichloride composition.

In the present invention, "to polymerize" means to polymerize the alkenylsilane compound by bringing it into contact with the solid product (If) under polymerizable conditions. II) is coated with a polymer.

The reaction between the above-mentioned organoaluminum compound and the electron donor (Bl) is carried out in the solvent (D) at -20°C to 200°C, preferably -10°C to 100°C for 30 seconds to 5 hours. There is no restriction on the order of addition of (B1) and (D), and the ratio of the amounts used is 0.1 mol to 8 mol, preferably 1 to 4 mol, of the electron donor (B,) to 1 mol of the organoaluminum compound, and the solvent. 0.5 L to 5 L, preferably 0.5 L to 2 L.

In this way, reaction product (I) is obtained. Reaction product (I
) is sometimes referred to as a liquid state where the reaction has completed without separation (reaction product liquid CI). ) for the next reaction.

As a method for treating this reaction product (solid product (II) obtained by reacting titanium tetrachloride with titanium tetrachloride or an organoaluminum compound and titanium tetrachloride) with an alkenylsilane compound, (I), or a method of polymerizing the solid product (II) by adding an alkenylsilane compound in any process of the reaction between the organoaluminum compound and titanium tetrachloride, ■Reaction product (■), or organoaluminum After the reaction between the compound and titanium tetrachloride is completed, an alkenylsilane compound is added to polymerize the solid product (II), and
), or after the reaction between the organoaluminum compound and titanium tetrachloride, the liquid part is separated and removed by filtration or decantation, and the obtained solid product (1) is suspended in a solvent, and then the organoaluminum compound is further removed. There is a method in which an alkenylsilane compound is added and polymerized.

The reaction between the reaction product (or organoaluminum compound) and titanium tetrachloride can be carried out at -10°C to
The reaction is carried out at 200° C., preferably from 0° C. to 100° C. for 5 minutes to 10 hours. It is preferable not to use an i11 medium, but an aliphatic or aromatic hydrocarbon can be used. (I) The organoaluminum compound, titanium tetrachloride, and the solvent may be mixed in any order, and the alkenylsilane compound may be added at any stage. It is preferable that the mixing of all the amounts of the solvent and the solvent be completed within 5 hours, and the reaction is also carried out during the mixing.It is preferable to continue the reaction within 5 hours after the mixing of all the amounts. For 1 mole of titanium chloride, the amount of solvent is 0 to 3.
OOOmj2, the ratio of the number of AI atoms in the reaction product (1) or the organoaluminum compound to the number of T1 atoms in titanium tetrachloride (^1/Ti) of 0.05 to 10. Preferably 0
406 to 0.3.

Polymerization treatment with alkenylsilane compounds produces reaction products (
1) Or when adding an alkenylsilane compound during any process of the reaction between the organoaluminum compound and titanium tetrachloride, and after the reaction product (I) or the reaction between the organoaluminum compound and titanium tetrachloride, the alkenylsilane compound is added. When adding, the reaction temperature is 0°C to 90°C.
for 1 minute to 10 hours, reaction pressure is atmospheric pressure to 10 kgf/c
m'G conditions, using 0.1 g to +00 g of alkenylsilane compound per 100 g of solid product (II), the content of alkenylsilane polymer in the final titanium trichloride composition is 0.1 g to +00 g. Polymerization is carried out so that the amount is 11% by weight to 99% by weight. The content of the alkenylsilane polymer is 0.1
If the titanium trichloride composition is ungrooved by weight, the effect of improving the transparency, consistency, and quality of the polyolefin produced using the obtained titanium trichloride composition will be insufficient, and if the amount exceeds 99%, the improvement effect will be insufficient. It becomes less noticeable and becomes economically disadvantageous.

After the polymerization treatment with the alkenylsilane compound is completed, the reaction product (1) or the organoaluminum compound and titanium tetrachloride is separated and removed by filtration or decantation, and the obtained solid product (II
) is suspended in a solvent, a solid product (
+? ) 1[For IQg, solvent 100mfL~S,
000mft, organoaluminum compound 5g~5,00
Add 0 g, react at a reaction temperature of 0°C to 90°C for 1 minute to IO time,
The reaction pressure is atmospheric pressure to 10 kgf/cm2G,
0.1 g to 10 per 100 g of solid product (II)
Using 0.0 J of alkenylsilane compound, the content of alkenylsilane polymer in the final titanium trichloride composition is 0.0J.
Polymerization is carried out to a concentration of 1% to 99% by weight. The solvent is preferably an aliphatic hydrocarbon, and the organoaluminum compound is the one used to obtain the reaction product (r) or the one used directly in the reaction with titanium tetrachloride without reacting with the electron donor (81). It may be the same or different. After the reaction is complete, the liquid part is separated and removed by filtration or decantation, and the resulting polymerization treatment is carried out after repeated washing with a solvent. The solid product (hereinafter sometimes referred to as the solid product (II-^)) may be used in the next step while suspended in the solvent, or it may be further dried and taken out as a solid for use. good.

The solid product (II-^) is then reacted with an electron donor (B, ) and an electron acceptor (F). Although this reaction can be carried out without using a solvent, preferable results are obtained using an aliphatic hydrocarbon. The amount used is (B) per 100g of solid product (11-A).
z) 0.1g to 1.000g, preferably 0.5g to 2
00g, (F) 0.1g to 1,000g, preferably 0.2g to 500g, solvent 0 to 3,000ml
, preferably 100-1, OOO+aJ2. The reaction method is as follows: ■ Adding an electron donor (
B2) and the electron acceptor (F) are reacted simultaneously, ■ (I[-A) is reacted with (F) and then (B2) is reacted, ■ (II-^) is reacted with (B2) There are two methods: reacting (B2) and (F) and then reacting (II-^); and (B2) and (F) and then reacting (II-^). In the methods (1) and (2) above, the temperature is 40°C to 200°C, preferably 50°C to
It is desirable to react at 100°C for 30 seconds to 5 hours,
In method (2), the reaction between (II-A) and (B2) is 0.
After reacting for 1 minute to 3 hours at 50°C to 50°C, the reaction mixture is reacted with (F) under the same conditions as in ① above. In the method (2), (B2) and (F) are reacted at 10°C to 100°C for 30 minutes to 2 hours, and then cooled to 40°C or lower.

After adding (II-^), the reaction is carried out under the same conditions as in (1) and (2) above. Solid product (II-A), (B2)
After the reaction of , and (F) is completed, the liquid portion is separated and removed by filtration or decantation, and washing with a solvent is repeated to obtain an olefin-type combined titanium trichloride containing the alkenylsilane polymer of the present invention. .

The titanium trichloride composition of the present invention thus obtained has the following formula: %: 2) (where n is an integer from 0 to 2, R1, R2, R
8 represents an alkyl group, a cycloalkyl group, or an aryl group, and contains an alkenylsilane polymer consisting of repeating units represented by 0.1% to 99% by mass, and is a transition metal compound for olefin polymerization. As a catalyst component,
It is used in the polymerization of olefins in combination with at least an organoaluminium compound.

The organoaluminum compound used in the production of the titanium trichloride composition of the present invention has the formula: AIR'J'1Xs-t
m+s'+ (wherein R4 and R11 represent a hydrocarbon group such as an alkyl group, cycloalkyl group, or aryl group or an alkoxy group, X represents a halogen, and ■ and m' represent 0<
m◆represents an arbitrary number of 1≦3), and specific examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum,
Trialkylaluminum such as tri-n-butylaluminum, tri-l-butylaluminum, tri-n-hexylaluminum, tri-hexylaluminum, tri-2-methylpentylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, diethylaluminum Dialkyl aluminum monohalides such as monochloride, di-n-propyl aluminum monochloride, di-l-butyl aluminum monochloride, diethylaluminum monofluoride, diethylaluminum monobromide, diethylaluminum monoiodide, dialkyl aluminum such as diethyl aluminum hydride Examples include hydrides, alkylaluminum sesquihalides such as methylaluminum sesquichloride and ethylaluminum sesquichloride, and monoalkylaluminum cybalides such as ethylaluminum dichloride and 1-butylaluminum dichloride. Alkoxyalkylaluminums such as toxymonoethylaluminum can also be used.

These organic aluminums can also be used in combination of two or more types.

As the electron donor used in the present invention, various ones are shown below, but it is preferable to mainly use ethers as (Bl) and (B2), and to use ethers as the other electron donor. Preferably used as an electron donor are organic compounds having an atom of oxygen, nitrogen, sulfur, or phosphorus, such as ethers, alcohols, esters, aldehydes, fatty acids, ketones, and nitriles. , amines, amides, ureas or thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, hydrogen sulfide or thioethers, thioalcohols, and the like. Specific examples include diethyl ether, moro-propyl ether, di-n-butyl ether, diisoamyl ether, moro-pentyl ether, moro-hexyl ether, cytohexyl ether, di-n-octyl ether, diisoamyl ether, di-n-
Ethers such as dodecyl ether, diphenyl ether, ethylene glycol diethyl ether, and tetrahydrofuran; alcohols such as methanol, ethanol, propatool, butanol, pentanol, hexanol, octatool, phenol, cresol, xylenol, ethylphenol, and 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 toluyl,
Methyl anisate, ethyl anisate, propyl anisate,
Esters such as ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, and ethyl phenylacetate, aldehydes such as acetaldehyde and benzaldehyde, formic acid, acetic acid, propionic acid, Fatty acids such as butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, aromatic acids such as benzoic acid, ketones such as methyl ethyl ketone, methyl isobutyl ketone, benzophenone, nitrile acids such as acetonitrile, methylamine, diethylamine, tributylamine , triethanolamine, β(N,
N-dimethylamino) ethanol, lysine, quinoline, a-picoline, 2,4J-trimethylpyridine, N,
N.

N', N'-Tetramethylhexaneethylenediamine, aniline, dimethylaniline and other amines, formamide, hexamethylphosphoric acid triamide, N, N, N'
, N',N''-pentamethyl-No-β-dimethylaminomethylphosphoric acid triamide, amides such as octamethylpyrophosphoramide, ureas such as N,N,N',N'-tetramethylurea, phenyl Isocyanates such as isocyanate and tolyl isocyanate, azo compounds such as azobenzene, phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxyto, dimethyl phosphine , moro-octyl phosphite, triethyl phosphite, tri-n-butyl phosphite, triphenyl phosphite, and other phosphites; ethyl diethyl phosphite, ethyl butyl phosphinite, phenyl diphenyl phosphite, and other phosphites; , diethylthioether, diphenylthioether,
Methylphenylthioether, ethylene sulfide,
Other examples include thioethers such as propylene sulfide, thioalcohols such as ethylthioalcohol, n-propylthioalcohol, and thiophenol. These electron donors can also be used in mixtures. Electron donors (B+
), each of (B, ) reacted with the solid product (II-^) may be the same or different.

The electron acceptors (F) used in the present invention are shown in the periodic table ■~■
It is represented by the halides of group elements. Specific examples include anhydrous aluminum chloride, silicon tetrachloride, stannous chloride, stannic chloride, titanium tetrachloride, zirconium tetrachloride,
Examples include phosphorus trichloride, phosphorus pentachloride, vanadium tetrachloride, and antimony pentachloride, and these can also be used in combination. Most preferred is titanium tetrachloride.

The following solvents are used. Examples of aliphatic hydrocarbons include n-pentane, n-hexane, n-hebutane, n-octane, I-octane, etc. In addition, instead of or together with aliphatic hydrocarbons, carbon tetrachloride,
Chloroform, dichloroethane, trichlorethylene,
Halogenated hydrocarbons such as tetrachlorethylene can also be used.

As aromatic compounds, aromatic hydrocarbons such as naphthalene,
and its derivatives such as alkyl substituted products such as mesitylene, durene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene, and l-phenylnaphthalene, and halogens such as monochlorobenzene, chlorotoluene, chloroxylene, chloroethylbenzene, dichlorobenzene, and bromobenzene. Chemical substances, etc. are shown.

The alkenylsilane compound used in the polymerization treatment has the formula (where n is an integer from 0 to 2, Hl, R2, R
"3 represents an alkyl group, a cycloalkyl group, or an aryl group," and specific examples include:
Vinyltrimethylsilane, vinyltriethylsilane, vinyltri-n-butylsilane, vinyldimethylcyclohexylsilane, vinyldimethylphenylsilane, allyltrimethylsilane, allyltriethylsilane, allyltripropylsilane, 3-butenyltrimethylsilane, 3-
Examples include butenyltriethylsilane.

The titanium trichloride it product of the present invention obtained as described above can be used as a catalyst in combination with at least an organoaluminum compound in the polymerization of olefins according to a conventional method, or more preferably, it can be preactivated by reacting with olefins. It is used as a catalyst in the polymerization of olefins. As the organoaluminum compound used in the polymerization of the olefin, the same organoaluminum compound as that used in producing the titanium trichloride composition of the present invention described above can be used. The organoaluminum compound may be the same as or different from the one used when producing the titanium trichloride composition, and the olefin used for preactivation may include ethylene, propylene, butene-1, Penten
These include straight chain monoolefins such as 11hexene-11hebutene-1, and branched chain monoolefins such as 4-methyl-hexene-1,2-methyl-pentene-1.

These olefins may be the same as or different from the olefin to be polymerized, or a mixture of two or more olefins may be used.

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

For slurry polymerization or bulk polymerization, a catalyst combining a titanium trichloride composition and an organoaluminum compound is sufficiently effective, but for gas phase polymerization, a catalyst preactivated by reacting with an olefin is preferable. Alternatively, when bulk polymerization is followed by gas phase polymerization, even if the catalyst initially used is the former, it will be the same catalyst as the latter because the olefin reaction has already taken place during the gas phase polymerization. Excellent effects can be obtained.

For preactivation, 0.1 to 500 g of organoaluminum, 0 to 50 g of solvent, 0 to 5 L of hydrogen, 0 to 5 L of QOQijL, and 0.05 to 5 g of olefin, per 1 g of titanium trichloride composition.
000g, preferably Q, 05g to 3.00011 is used. The olefin was reacted at a temperature of 0° C. to 100° C. for 1 minute to 20 hours, and 0.00% was added per 1 g of titanium trichloride composition. O2
2,000g of N.

It is desirable to react preferably 0.05 to 200 g of olefin.

Preactivation can also be carried out in a hydrocarbon solvent such as propane, butane, n-pentane, n-hexane, rhohebutane, benzene, toluene, etc., and even in liquefied olefins such as liquefied propylene, liquefied butene-1, etc. ethylene,
It can be carried out in propylene, and hydrogen may also be present in the preliminary activation.

At the time of preactivation, polymer particles previously obtained by slurry polymerization, bulk polymerization, or gas phase polymerization can also be made to coexist. The polymer may be the same as or different from the olefin polymer to be polymerized. The polymer particles that can be made to coexist are as follows:
It is in the range of 0-5.000g.

The solvent or olefin used in the preactivation can be removed by distillation under reduced pressure or filtration during or after the preactivation, and the solid product can be removed by distillation under reduced pressure or filtration.
A solvent may also be added to suspend in an amount of not more than 80 parts per portion of solvent.

There are various aspects of the preactivation method, such as: (1) A method in which an olefin is brought into contact with a catalyst that combines a titanium trichloride composition and an organoaluminium to perform a slurry reaction, a bulk reaction, or a gas phase reaction, (2) A method in which an olefin is coexisted. There are methods such as combining a titanium trichloride composition and organoaluminium as described below, methods (1) and (2) in which an olefin polymer coexists, methods (2), (2), and (3) in which hydrogen is coexisting. . There is no difference in the quality of the wood whether the catalyst is in a slurry state or in powder form.

As described above, a catalyst consisting of a titanium trichloride composition and an organoaluminum compound in combination, or a catalyst further preactivated with an olefin, is used for the production of olefin polymers, but as in normal olefin polymerization, It is also possible to further add an electron donor as a third component of the catalyst for use in polymerization for the purpose of improving stereoregularity. The polymerization format for polymerizing olefins is ■n-pentane, n
- Slurry polymerization carried out in a hydrocarbon solvent such as hexane, n-hebutane, low octane, benzene or toluene; - Bulk polymerization carried out in a liquefied olefin monomer such as liquefied propylene or liquefied butene-1; - Olefins such as ethylene and propylene. There is a method of vapor phase polymerization in which the above is polymerized in the gas phase, or a method of stepwise combining two or more of (1) to (2) above. In either case, the polymerization temperature is room temperature (20℃) ~ 2
00℃, polymerization pressure is normal pressure (Okg/c@”G) ~5
It is usually carried out for about 5 minutes to 20 hours at 0 kg/cm'G.

During polymerization, steps such as adding an appropriate amount of hydrogen to control the molecular weight are the same as in conventional polymerization methods. The method of the present invention can also be used for multi-stage polymerization of olefins, including gas phase polymerization, slurry polymerization, and bulk polymerization, in which 2 to 10 polymer reactors are connected in series, and the polymerization phase is changed in each reactor. It is also possible to change the catalyst, olefin, and hydrogen used.

The olefin subjected to polymerization in the method of the present invention is
Straight chain monoolefins such as ethylene, propylene, butene-11hexene-1, octene-1, branched chain monoolefins such as 4-methylpentene-1,2-methyl-pentene-1, butadiene, isoprene, chlorobrene and styrene, and the method of the present invention not only polymerizes each of these individually, but also mutually combines them with other olefins, such as propylene and ethylene, butene-1 and ethylene, propylene, etc. Butene-1
Propylene, ethylene, butene-1
Copolymerization can also be carried out by combining three components as shown in
Moreover, block copolymerization can also be performed by changing the type of olefin fed in multistage polymerization.

[Effects of the Invention] The main effects of the present invention are that when the titanium trichloride composition of the present invention is used as a transition metal compound catalyst component for olefin polymerization, void generation is prevented with significantly high productivity. It is possible to produce a polyolefin with extremely high transparency and crystallinity with very little amount.

The effects of the present invention will be explained in more detail.

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

As is clear from the examples shown below, the internal haze of the polyolefin press film obtained using the titanium trichloride composition of the present invention is lower than that obtained using the titanium trichloride composition containing no alkenylsilane polymer. The transparency is approximately 178 to 1/4 compared to that of the polyolefins used in this study, and has extremely high transparency.

In addition, the crystallization temperature is approximately 8°C to 12°C higher than in the case where no alkenylsilane polymer is contained, and the crystallinity is significantly improved, and the flexural modulus is also significantly higher (Examples 1 to 3). 9, Comparative Example 1.3.5-1O),
Furthermore, it is clear that the number of voids generated is significantly smaller than in polyolefins into which alkenylsilane polymers are introduced by methods other than the present invention (Examples 1 to 9).
, see Comparative Example 2).

The second effect of the present invention is that with extremely high polymerization activity,
A polyolefin with good particle shape and high stereodiscipline can be obtained. Therefore, the catalyst removal step and the atactic polymer removal step can be omitted, and polyolefin can be produced by a long-term continuous method using a simpler process such as gas phase polymerization, which is extremely advantageous in industrial production. It is.

The third effect of the present invention is that the titanium trichloride composition for olefin polymerization of the present invention has excellent storage stability and thermal stability. It is extremely important industrially to be able to store products stably for long periods of time regardless of the outside temperature. The preservation can be carried out either in powder form or in suspended form in an inert hydrocarbon solvent.

Furthermore, the fourth effect of the present invention is that the titanium trichloride composition for olefin polymerization of the present invention has excellent attrition resistance. The titanium trichloride composition is not susceptible to attrition during its use, i.e., not only during the olefin polymer production process, but also during the catalyst production process, which prevents the formation of finely divided catalyst and, in turn, prevents the formation of finely divided olefin polymer. It means to prevent. As a result, it is extremely effective in preventing line blockage troubles in the gas phase polymerization process, and in preventing compressor troubles caused by the mixing of finely divided olefin polymers into circulating gas.

[Example] The present invention will be explained below with reference to Examples. Definitions of terms used in Examples and Comparative Examples and measurement methods are as follows.

TY: Shows monomerization activity, polymer yield per 1 gram atom of titanium (8/Durham atom at 1st position) II: Shows stereoregularity, residual amount extracted with n-hexane at 20°C
(411th place 11%) BD: Bulk specific gravity
(Unit: g/1ail>MFR: Melt flow index ASTM D-1238 (L),
(Unit: g/u+min) Internal haze: This is the haze inside the film excluding surface effects. Using a press machine, polyolefin powder is heated to a thickness of 150μ at a temperature of 200℃ and a pressure of 200kg/c+a'G. After forming a film and coating both sides of the film with liquid paraffin,
Haze was measured in accordance with IS 7105.
(Unit: %) Crystallization temperature: Measured using a differential scanning calorimeter at a cooling rate of 10° C./min.
(Unit: 2°C) Flexural modulus: Tetrakis [methylene-3
-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate 0.5 parts by weight of comethane and 0.51 parts by weight of calcium stearate were mixed, and the mixture was extruded through a screw diameter of 40+am. It was granulated using a granulator. Then, the granulated material is heated to a melt resin temperature of 2 with an injection molding bridge.
A JIS type test piece was prepared at 30°C and a mold temperature of 50°C, and the test piece was kept at a humidity of 50% and a room temperature of 23°C.
After being left indoors for 72 hours, the flexural modulus was determined according to JIS K 7203. Measurement 1. f. (41st place:
kgf/am2) Void: Polyolefin is granulated in the same manner as in the previous section, and the resulting granules are extruded using a T-die type film forming machine at a molten resin temperature of 250°C. A sheet with a diameter of 1 mm was prepared.

The sheet was heated with hot air at 150° C. for 70 seconds, and then stretched 7 times in the longitudinal and lateral directions using a bi-stretching bridge to obtain a biaxially stretched film with a thickness of 20 μm. The film was observed with an optical microscope, the number of voids with a diameter of 10μ or more was measured, and fc
20 end grooves per m'0120 or more 50 end grooves Δ,
50 or more pieces were marked with an x.

Example 1 (1) Production of titanium trichloride composition The reaction product solution (I) (molar ratio of diisoamyl ether/DEAC: 2.4) was obtained by reacting at high temperature. 40 mol of titanium tetrachloride was placed in a reactor purged with nitrogen and heated to 35°C.
After adding the entire amount of the reaction product solution (r) dropwise over 180 minutes, the temperature was kept at the same temperature for 60 minutes, the temperature was raised to 80°C, the reaction was continued for another hour, the temperature was cooled to room temperature, and the supernatant liquid was removed. ,n
The operation of adding -hexane 201 and removing the supernatant liquid by decantation was repeated four times to obtain a solid product (II).

The entire amount of (11) was suspended in 30j2 of n-hexane, 400 g of diethylaluminum monochloride was added,
Add 9.5 kg of allyltrimethylsilane at 40°C,
Polymerization treatment was performed at 40°C for 2 hours. After the treatment, the temperature was raised to 50°C, the supernatant liquid was removed, n-hexane 301 was added, and the supernatant liquid was removed by decantation, which was repeated four times to obtain the polymerized solid product (II-A). Obtained. The entire amount of this solid product was suspended in 9λ of n-hexane, and 3.5 kg of titanium tetrachloride was added at N temperature for about 10 minutes.
After reacting at 80°C for 30 minutes, 1.6 kg of diisoamyl ether was further added and reacted at 80°C for 1 hour.
After the reaction was completed, the operation of removing the supernatant liquid was repeated five times, and then dried under reduced pressure to obtain a titanium trichloride composition. The polyallyltrimethylsilane content in the obtained titanium trichloride composition was ao, ol amount%, and the titanium content was 1001% by weight.

(2) Preparation of preactivated catalyst The present invention obtained in (1) after replacing a stainless steel reactor with inclined blades with an internal volume of 80ρ with nitrogen gas, 40IL of n-hexane, and 11.4g of diethylaluminum monochloride. After adding 450 g of titanium trichloride catalyst component at room temperature, 0.9 Nd of ethylene was supplied at 30°C for 2 hours to cause a reaction (2.0 g of ethylene reacted per 1 g of titanium trichloride composition). Reacted ethylene was removed to obtain a preactivated catalyst.

(3) Olefin polymerization L/D- with an internal volume of 80°C and a stirrer, with nitrogen substitution
After charging 20 kg of polypropylene powder with an MFR of 2.0 into the horizontal polymerization reactor in Step 3, the above preactivated catalyst was added at 6.32 mg/h in terms of titanium atoms, and a 30 wt% n-hexane solution of diethyl aluminum monochloride was added to the diethyl aluminum monochloride. 3.8g/as aluminum monochloride
It was fed continuously at hr.

In addition, hydrogen was supplied so that the concentration in the gas phase was maintained at 0.01% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg/cm2G, and the gas phase polymerization of propylene was carried out at 70°C.
This was done continuously for 20 hours. During this period, polymer was continuously extracted from the polymerization vessel at a rate of 10 kg/hr so that the polymer retention level in the polymerization vessel was 50% by volume. The extracted polymer was then treated with 0.0% propylene oxide.
After contact treatment with nitrogen gas containing 2% by volume at 95° C. for 30 minutes, a product powder was obtained.

(4) Thermal stability test The titanium trichloride composition obtained in the same manner as in (1) above was
After storing at ℃ for 4 months, propylene was polymerized in the same manner as in (2) and (3).

(5) After connecting the circulation piping equipped with a circulation pump to the reactor used in the attrition resistance test (2), the
0A and 4.5 kg of a titanium trichloride composition obtained in the same manner as in (1) above were added. Subsequently, the circulation pump is activated and the suspension in the reactor is controlled to a flow rate of 100 using the circulation line.
After circulating for 4 hours under the conditions of ρ/min and 25°C, (
Polymerization of propylene was carried out in the same manner as in 2) and (3).

Comparative Example 1 (1) Three samples were prepared in the same manner as in (1) of Example 1, except that the solid product (II) was not polymerized with allyltrimethylsilane to obtain a solid product (II-8) equivalent. A titanium chloride composition was obtained.

(2) 1.8k of the titanium trichloride composition obtained in the above (1) as the titanium trichloride composition in (2) of Example 1
A preactivated catalyst was prepared in the same manner except that g was used.

(3) Propylene was polymerized in the same manner as in (3) of Example 1 except that the preactivated catalyst obtained in (2) above was used as the preactivated catalyst.

(4) Propylene was polymerized 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) Propylene was polymerized in the same manner as in (5) 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.

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

(2) After adding 200 IL of n-hexane, 300 g of diethylaluminum monochloride, and 1.8 kg of the titanium trichloride composition obtained in (1) above to the reactor used in (2) of Example 1 at room temperature. , 7.2 kg of allyltrimethylsilane was added and reacted at 40°C for 2 hours (1.4 kg of allyltrimethylsilane was added per 1 g of titanium trichloride composition).
g reaction).

(3) Propylene polymerization was carried out in the same manner as in (3) of Example 1 except that the catalyst slurry reacted with nalyltrimethylsilane obtained in (2) above was used instead of the preactivated catalyst. 14 hours after the start of polymerization because the lumpy polymer blocked the powder extraction pipe.
Production had to be stopped at some point.

Comparative Example 3 In Example 1 (1), 3.6 kg of propylene was used instead of allyltrimethylsilane to produce a solid product (■
Polypropylene content 60. A titanium trichloride composition having an OIl amount of % and a titanium content of 1O91% by weight was obtained. Polymerization of propylene was carried out in the same manner as in Example 1 (2+, (3)) except that this titanium trichloride composition was used.

Comparative Example 4 and Example 2.3 By changing the amount of allyltrimethylsilane used in (1) of Example 1, the polyallyltrimethylsilane content was 0.001% by weight, 8.3% by weight, and 33% by weight, respectively. 3
A titanium trichloride composition with an amount of fi% was obtained. Next, Example 1
Polymerization of propylene was carried out in the same manner as in +2) and (3).

Example 4 A reaction solution obtained by reacting n-heptane 4λ, diethylaluminum monochloride 5.0 mol, diisoamyl ether 9.0 mol, and moro-butyl ether 5.0 mol at 18° C. for 30 minutes was converted into titanium tetrachloride 27 40 in .5 mole
After dropping at ℃ for 300 minutes, keep at the same temperature for 1.5 hours to react, then raise the temperature to 65℃, react for 1 hour, remove the supernatant, add 20 fl of n-hexane, and decant. The operation of removing with 1 liter of water was repeated 6 times, and 1.8 kg of the obtained solid product (II) was suspended in 40 λ of n-hexane, and diethyl aluminum monochloride 5008 was suspended in 40 λ of n-hexane.
was added, 7.6 kg of allyltrimethylsilane was added at 50°C, and reacted for 1 hour to produce a polymerized solid product (
II-^) was obtained.

After the reaction, the supernatant was removed, and the operation of adding 2i n-hexane and removing by decantation was repeated twice, and the solid product (■-^) subjected to the above polymerization treatment was added with 7J of n-hexane.
2, 1.8 kg of titanium tetrachloride and 1.8 kg of n-butyl ether were added, and the mixture was reacted at 60°C for 3 hours. After the reaction was completed, the supernatant was removed by decantation, 20J2 of n-hexane was added, stirred for 5 minutes, allowed to stand, and the supernatant was removed three times.
i. A titanium trichloride composition was obtained by drying, and (2) of Example 1 was obtained.
), (3) Propylene polymerization was carried out in the same manner as in (3).

Comparative Example 5 Solid product (II) was converted into solid product (II-^) without the single treatment with allyltrimethylsilane in Example 4.
) A titanium trichloride composition was obtained in the same manner except that the equivalent was used, and propylene was polymerized.

Example 5 Instead of using 50 moles of diethylaluminium monochloride, 4.0 moles of moro-butyl aluminum monochloride was used to obtain a reaction product solution (1), and titanium tetrachloride was mixed with 45 moles of monochloride.
A titanium trichloride composition was obtained and propylene was polymerized in the same manner as in Example 1, except that the composition was added dropwise at .degree.

Comparative Example 6 Propylene was polymerized in the same manner as in Example 5, except that a titanium trichloride composition was obtained without performing the polymerization treatment with allyltrimethylsilane.

Example 6 In Example 1 (1), a mixture of 1.8 J of silicon tetrachloride and 2.0 kg of titanium tetrachloride was used instead of titanium tetrachloride, and the amount of diisoamyl ether was 2.2 kg to produce a solid product. A titanium trichloride composition was obtained in the same manner except that it was reacted with (II-A).

Subsequently, the above titanium trichloride composition was added to a 20% by weight n-hexane solution of diethylaluminium monochloride at a rate of 9.8 mg atoms/hr in terms of titanium atoms, into a polymerization vessel equipped with a stirrer and having an internal volume of 200 Il and a two-stage turbine blade. (Diethylaluminum chloride/hr and n-hexane were continuously supplied at a rate of 21 kg/hr. Hydrogen was also supplied so that the concentration in the gas phase was maintained at 0.1% by volume, and the total pressure was 10 kg/hr.
Slurry polymerization of propylene was carried out continuously at 70°C for 120 hours by supplying propylene so as to maintain cm"G. During the polymerization period, the slurry retention level in the polymerization vessel was kept at 75% by volume. The slurry was continuously extracted from the polymerization vessel into a flash tank with an internal volume of 501 cm.In the flash tank, unreacted propylene was removed under reduced pressure, while methanol was supplied at a rate of t kg/hr and contact treatment was carried out at 70°C. Subsequently, the slurry was centrifuged to separate the solvent, and then dried in a drier to obtain a product powder at 10 kg/hr.

Comparative Example 7 Solid product (11) was converted into solid product (I) without the polymerization treatment with allyltrimethylsilane in Example 6.
Slurry polymerization of propylene was carried out in the same manner as in Example 6 using a titanium trichloride composition obtained in the same manner except that it was equivalent to I-A).

Example 7 Adding 270 mol of titanium tetrachloride to n-hexane ILQ,
After cooling to 1°C, 12.5 L of n-hexane containing 27.0 mol of diethylaluminium monochloride was added.
The mixture was added dropwise over 4 hours at ℃. After the dropwise addition was completed, the temperature was kept at the same temperature for 15 minutes to react, and then the temperature was raised to 65°C over 1 hour.
The reaction was further continued at the same temperature for 1 hour. Next, remove the supernatant and
-Add 10 volumes of hexane and remove by decantation 5 times to obtain a solid product (II) 5
．． Of the 7kg, 1.8kg is n-hexane 5111J
Suspended in 2 and diethylaluminum monochloride 3
Add 50g of allyltrimethylsilane 38K at 40℃.
After further adding g, polymerization treatment was performed at 40°C for 2 hours.

After the polymerization treatment, after removing the supernatant, adding 30p of n-hexane and removing by decantation, the operation was repeated twice, and the resulting solid product subjected to polymerization tA31 (II-
The entire amount of ^) was suspended in 1111 n-hexane, and 1.6 j2 of di-isoamyl ether was added thereto. After stirring this suspension at 35°C for 1 hour,
A treated solid was obtained by washing twice. The obtained treated solid was suspended in an n-hexane solution 61 containing 40% by volume of titanium tetrachloride.

this! ! ! The temperature of the suspension was raised to 65°C, and the reaction was allowed to proceed at the same temperature for 2 hours. After the reaction was completed, the resulting solid was washed three times using n-hexane 20J2 each time, and then dried under reduced pressure to obtain a titanium trichloride composition. Comparative Example 8 Using the obtained titanium trichloride composition, gas phase polymerization of propylene was carried out in the same manner as in (2) and (3) of Example 1. In Example 7, the polymerization treatment with allyltrimethylsilane was omitted. After obtaining the titanium trichloride composition, the rest is Example 9
Gas phase polymerization of propylene was carried out in the same manner as described above.

Example 8 In (1) of Example 1, 3-butenyltrimethylsilane was used instead of allyltrimethylsilane5. A polymerized solid product (II-A) was obtained using Okg, and then 8 was added to 30 of titanium tetrachloride in 10λ of n-hebutane. ), add the whole amount,
The reaction was carried out at 80°C for 30 minutes. After the reaction is completed, it becomes even more
2.8 kg of pentyl ether was added and reacted at 80° C. for 1 hour to obtain a titanium trichloride composition. Using the obtained titanium trichloride composition, steps (2) and (1) of Example 1 were carried out.
) Gas-phase polymerization of propylene was carried out in the same manner as in (1).

Comparative Example 9 Propylene was polymerized in the same manner as in Example 8, except that a titanium trichloride composition was obtained without performing the polymerization treatment with 3-butenyltrimethylsilane.

Example 9 In Example 6, when obtaining the titanium trichloride composition, the amount of allyltrimethylsilane used was 8.3 kg, and during propylene polymerization, ethylene was further added so that the concentration in the gas phase was maintained at 0.2% by volume. Propylene-ethylene copolymerization was carried out in the same manner as in Example 6 except for the supply.

Comparative Example 10 Propylene-ethylene copolymerization was carried out in the same manner as in Example 9, except that a titanium trichloride composition was obtained without performing the polymerization treatment with allyltrimethylsilane.

[Brief explanation of the drawing]

FIG. 1 is a flow sheet for explaining the method for producing the titanium trichloride composition of the present invention. that's all

Claims (3)

[Claims] (1) The following formula, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, n is an integer from 0 to 2, R^1, R^2
, R^3 represents an alkyl group, a cycloalkyl group, or an aryl group. ) A titanium trichloride composition for olefin polymerization containing 0.1% to 99% by weight of an alkenylsilane polymer consisting of repeating units represented by: (2) Organoaluminum compound or reaction product of organoaluminium compound and electron donor (B_1) (
The solid product (II) obtained by reacting titanium tetrachloride with I) has the general formula ▲Mathematical formula, chemical formula, table, etc.▼ (In the formula, n is an integer from 0 to 2, R ^1, R^2
, R^3 represents an alkyl group, a cycloalkyl group, or an aryl group. 0.1% to 99% by weight of an alkenylsilane polymer, which is obtained by polymerizing with an alkenylsilane compound represented by ) and further reacting an electron donor (B_2) with an electron acceptor. A method for producing a titanium trichloride composition for olefin polymerization containing the titanium trichloride composition. (3) As an organoaluminum compound, the general formula is AlR
^4_mR^5_m・X_3_-_(_m_+_m'_
) (In the formula, R^4 and R^5 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 the number of benevolence. ) The manufacturing method according to claim 2, using an organoaluminum compound represented by: