JPH0291103A - Titanium trichloride composition for preparation of polyolefin and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain the title composition for the preparation of a highly crystallize polyolefin excellent in transparency by subjecting a reaction product of an organoaluminum compound with TiCl4 to polymerization treatment, for example, with allyltoluene, and reacting the product with an electron acceptor and an electron donor, thereby incorporating an allyltoluene, etc., thereinto. CONSTITUTION:An organoaluminum compound (e.g., diethylaluminum monochloride) or a reaction product of an organoaluminum compound with an electron donor (e.g., diisoamyl ether) is reacted with TiCl4 to produce a solid product. The product is subjected to polymerization treatment with allyltoluene and/or allylxylene, and the resulting product is reacted with an electron donor and an electron acceptor (e.g., TiCl4) to produce a solid product. The product is mixed with 0.01-99wt.% crystalline allyltoluene and/or crystalline allylxylene to produce the title composition. The composition can be used as a transition metal compound catalyst component for producing with extremely high productivity a polyolefin polymer which has less voids and is extremely high in transparency and crystallinity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a titanium trichloride composition for producing polyolefins and a method for producing the same. More specifically, the present invention relates to a titanium trichloride composition for producing a polyolefin, which is suitable as a monometallic compound catalyst component for producing a highly crystalline polyolefin with excellent transparency, and a method for producing the same.

[Conventional technology and its sections! ! Crystalline polyolefins such as crystalline polypropylene are produced by polymerizing olefins using a so-called Ziegler-Natsuta catalyst, which consists of transition metal compounds of groups IV to VI of the periodic table and organometallic compounds of metals of groups 1 to III of the periodic table. Among them, various titanium trichloride compositions are widely used as transition metal compound catalyst components.

Among these titanium trichloride compositions, many improved manufacturing methods have been investigated for the type obtained by reducing titanium tetrachloride with an organoaluminum compound and then heat-treating it because the resulting polymer has a good shape. There is. 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 ( Special Publication No. 53-3,356)
etc.

The present applicant has already made many proposals in this field, and among them, the solid obtained by reacting the reaction product of an organoaluminum compound and an electron donor with titanium tetrachloride has an electron donor and an electron donor. A method for producing a polyolefin using a titanium trichloride composition obtained by reacting it with a receptor (Japanese Patent Publication No. 59-28,573), and a method for producing a polyolefin using a titanium trichloride composition obtained by reacting it with a receptor, A method for producing a polyolefin using a titanium trichloride composition obtained by polymerizing a solid obtained by reacting titanium with an olefin and then reacting an electron donor and an electron acceptor (Japanese Patent Application Laid-Open No. No. 58-17,104), they proposed a method that significantly improved the storage stability of titanium trichloride compositions, polymerization activity, and crystallinity of the obtained polyolefin, as compared to conventional methods.

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. For example, aluminum salts of aromatic carboxylic acids (
Japanese Patent Publication No. 40-1.852) and benzylidene sorbitol derivatives (Japanese Patent Publication No. 51-22.740, etc.)
There is a method of adding nucleating agents such as to polypropylene, but
When aluminum salts of aromatic carboxylic acids are used, the dispersibility is poor and the transparency improvement effect is insufficient, and when benzylidene sorbitol derivatives are used, the transparency remains constant. Although improvements were seen in this process, it still had Li2 problems such as a strong odor during processing and a bleed phenomenon (embossment) of additives.

Styrene, 0-methylstyrene, pt-butylstyrene,
Methods for carrying out multi-stage polymerization of l-vinylnaphthalene and propylene and compositions thereof (JP-A-62-1,738, JP-A-62-227,911, JP-A-63
However, when the present inventors produced polypropylene according to the proposed method, propylene This method not only lowers the polymerization activity of the polymer, but also produces bulky polymers, so this method cannot be used in industrial long-term continuous polymerization methods, especially in gas phase polymerization methods in which olefin polymerization is carried out in the gas phase. Furthermore, the film produced using the obtained polypropylene had many voids, which impaired its commercial value.

A similar technique is a method in which propylene is polymerized using a transition metal catalyst component for propylene polymerization, which is obtained by adding a pt-butylstyrene melon aggregate during the production of the catalyst component (Japanese Patent Application Laid-open No. 6:111). -69,809 has been proposed, but since the proposed method requires a separate process to produce pt-butylstyrene polymer, it not only has industrial disadvantages. However, this method had the same problem as the prior art described above in that voids were generated in the film.

The present inventors have conducted intensive research on methods to solve the problems faced by conventional technology, such as the formation of lumpy polymers and the generation of voids in the film due to poor dispersion, when producing polyolefins with improved transparency. did.

As a result, a titanium trichloride composition containing a crystalline allyltoluene polymer and/or a crystalline allylxylene polymer was discovered using a specific method, and a catalyst in which this titanium trichloride composition was combined with an organoaluminum compound was used. Not only can this solve the problems of the prior art polyolefin production as described above, but also provide a polyolefin polymer with good dispersibility, very little void generation, and excellent transparency and crystallinity. Storage stability of the titanium trichloride composition at high temperatures of 35°C or higher,
The present invention was developed based on the knowledge that the titanium trichloride composition has a significant effect on the resistance to abrasion within the production equipment during large-scale production.

An object of the present invention is to provide a titanium trichloride composition for producing a polyolefin and a method for producing the same, which can produce a polyolefin with extremely high transparency and crystallinity, with very little void generation even at extremely high productivity. That is.

[Means to solve problems]

The present invention has the following configuration.

(1) Crystalline allyltoluene polymer and/or crystalline allylxylene polymer o, oi% by weight to 99% by weight
and titanium trichloride composition 99.99% by weight to 1.0%
% by weight of a titanium trichloride composition for producing a polyolefin.

(2) The crystalline allyltoluene polymer and/or the crystalline allylxylene polymer is a crystalline 0-allyltoluene polymer, a crystalline p-allyltoluene polymer, a crystalline 2-
Allyl-p-xylene polymer, crystalline 4-allyl-0-
The titanium trichloride composition according to item 1 above, which is a crystalline polymer of 1 ft11 or more selected from xylene polymers and crystalline 5-allyl-m-xylene polymers.

(3) Organoaluminum compound, more specifically reaction product of organoaluminum compound and electron donor (8,) (1)
A solid product obtained by reacting titanium tetrachloride with
1) is polymerized with allyltoluene and/or allylxylene, and the electron donor (B2) is further reacted with the electron acceptor to obtain a solid product (Ill), in which crystalline allyltoluene and/or crystalline 1. A method for producing a titanium trichloride composition for producing a polyolefin, comprising containing 0.011i% to 99fi% of an allylxylene polymer.

(4) As an organoaluminum compound, the general formula is AIR
',,R'1xs-+m*s・+ (wherein, R1, R2
represents a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, or an alkoxy group; X represents a halogen;
Further, m1■° represents an arbitrary number of O<m◆1≦3. )
The third method using an organoaluminum compound represented by
The manufacturing method described in section.

(5) As allyltoluene and/or allylxylene, o-allyltoluene, p-allyltoluene, 2-
1 ff selected from allyl-p-xylene, 4-allyl-O-xylene, and 5-allyl-■-xylene
The manufacturing method according to item 3 above, using a monomer having fi or more.

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

The titanium trichloride composition for polyolefin production of the present invention is
A titanium trichloride composition containing a crystalline allyltoluene polymer and/or a crystalline allylxylene polymer (hereinafter sometimes referred to as a specific allyl polymer),
The manufacturing method will be described in detail below.

The titanium trichloride composition is manufactured as follows. First,
A solid product (11) obtained by reacting an organoaluminum compound and an electron donor (B2) to obtain a reaction product (I), and reacting this (1) with titanium tetrachloride, or an organoaluminum A solid product obtained by reacting a compound with titanium tetrachloride (allyl toluene and/or allyl xylene (hereinafter referred to as a specific allyl
There is something called the body. ), the electron donor (B2) is further reacted with an electron acceptor to obtain a titanium trichloride composition in which the solid product (Ill) contains a specific allyl m combination.

In addition, in the present invention, "r, ffi synthesis treatment" means to produce a solid product (II) under conditions that allow specific allyl monomers to be polymerized.
In this polymerization process, the solid product (:I) is coated with the polymer.

The above-mentioned organoaluminum compound and electron donor (BI) are reacted in a solvent (D) at 0°C to 2°C.

C., preferably -10.degree. C. to 100.degree. C. for 30 seconds to 5 hours. There is no restriction on the order of addition of the organoaluminum compound (B1) and (D), and the ratio of the amount used is 0.1 mol or more of the electron donor (B+) per 1 mol of the organoaluminum compound.
8 mol, preferably 1-4 mol, tfJ'140.5L
~SL, preferably 0.5L to 2L.

In this way, the reaction product N) obtained (sometimes referred to as a liquid state (reaction product liquid H) in which the reaction has been completed without separation) can be used for the next reaction.

The method of polymerizing the reaction product (II) obtained by reacting the reaction product with titanium tetrachloride or the organoaluminum compound and titanium tetrachloride with a specific furyl monomer is as follows: A specific allyl monomer is added in any step of the reaction between the reaction product (I) or the organoaluminum compound and titanium tetrachloride to produce a solid product (II).
2) After the reaction of the reaction product (I) or the organoaluminum compound with titanium tetrachloride, a specific allyl monomer is added to form a solid product (II).
After the reaction of the 0 reaction product (I) or an organoaluminum compound with titanium tetrachloride, the liquid part is separated and removed by filtration or decantation, and the obtained solid product ( There is a method of suspending !1) in a solvent, further adding an organoaluminum compound and a specific allyl monomer, and carrying out polymerization treatment.

The reaction of the reaction product (■) or the organoaluminum compound with titanium tetrachloride has a -10
°C to 200 °C, preferably 0 °C to 100 °C for 5 minutes to I
Do it for O hours.

Although it is preferred not to use a solvent, aliphatic or aromatic hydrocarbons can be used. (1) Alternatively, the organic aluminum compound, titanium tetrachloride, and solvent may be mixed in any order, and the specific furyl monomer may be added at any stage.

It is preferable that the mixing of the total amount of (1) or the organoaluminum compound, titanium tetrachloride, and solvent is completed within 5 hours, and the reaction is carried out even during the mixing. It is preferable to continue the reaction for another 5 hours after mixing the entire amount.

The amount of each solvent used in the reaction is 0 to 3.0 mol per mol of titanium tetrachloride. OOOmjl, reaction product (1)
Or the ratio of the number of ^1 atoms in the organoaluminum compound to the number of Ti atoms in titanium tetrachloride (AI/Ti) is 0.0
5 to 1O1, preferably 0.06 to 0.3.

Polymerization treatment with specific allyl monomer produces reaction product (1)
Alternatively, when adding a specific amount of allyl in any process of the reaction between the organoaluminum compound and titanium tetrachloride, and after the reaction product (1) or the reaction between the organoaluminum compound and titanium tetrachloride is completed, dimethylstyrene is added. When the reaction temperature is 0°C to 90°C for 1 minute to 10 hours, the reaction pressure is atmospheric pressure to 10 kgf/cm'G, and 0.01 g per 100 g of solid product (II).
~100 kg of the specific allyl monomer is used to achieve a content of the specific allyl polymer in the final titanium trichloride composition of 0.
Polymerization is carried out so that the amount is 01% to 99% by weight.

When the content of the specific allyl polymer is less than 0.01% by weight, the effect of improving the transparency and crystallinity of the polyolefin produced using the obtained titanium trichloride composition is insufficient, and If the amount exceeds %, the improvement effect will not be significant and it will be economically disadvantageous.

Polymerization treatment with a specific allyl monomer produces a reaction product (1
) or after the reaction between the organoaluminum compound and titanium tetrachloride is completed, the liquid portion is separated and removed by filtration or decantation, and the obtained solid product (II) is suspended in a solvent. Solid product (II
) 100a+fl~5 of solvent per 100g. OOO
mIl, organoaluminum compound 5g to 5,000g
was added, and the reaction temperature was 0°C to 90°C for 1 minute to 10 hours, and the reaction pressure was atmospheric pressure to 10 kgf/ca+'G.
00 kg of the specific allylic monomer, the content of the specific allylic polymer in the final titanium trichloride composition is 0.01
Polymerization is carried out so that the amount is from 99% to 99% by weight.

The solvent is preferably an aliphatic hydrocarbon, and the organoaluminum compound is the one used to obtain the reaction product (1) or the one used directly in the reaction with titanium tetrachloride without reacting with the electron donor (B+). It may be the same or different.

After the reaction is completed, the liquid portion is separated and removed by filtration or decantation, and then washed with a solvent repeatedly.
The obtained polymerized solid product (hereinafter sometimes referred to as solid product (II-A)) may be used in the next step while suspended in a solvent, or it may be further dried to form a solid product. You may take it out and use it as an object.

The solid product (II-A) is then reacted with an electron donor (B2) and an electron acceptor (F).

This reaction can be carried out without using a solvent, but
Preferable results are obtained using aliphatic hydrocarbons.

The amounts used are: (Ih) 0.1 g N1,000 g, preferably 0.5 g to 200 g, (F) O, 1 g -1,00
0g, preferably 0.2g to 500g% solvent O to 3,0
00mJ2, preferably 100-1. It is OOOml.

The reaction methods include: (1) reacting the solid product (II-A) with an electron donor (B2) and an electron acceptor (F) at the same time, (2) reacting (F) with (n-A), and then Method of reacting (B2), ■(II-A) with (
Method of reacting (F) after reacting B2), ■(
There is a method of reacting B2) with (F) and then reacting with (II-A), but any method may be used.

The reaction conditions are 40°C to
It is desirable to react at 200°C, preferably from 50°C to 100 t for 30 seconds to 5 hours.
After reacting I-A) and (lh)(D at 0° C. to 50° C. for 1 minute to 3 hours, (F) is reacted under the same conditions as in (1) and (2) above.

In addition, in method (■), (B2) and (F) are 10t to 1
After reacting at 00°C for 30 minutes to 2 hours, cooling to 40°C or lower, adding (II-A), and reacting under the same conditions as in (1) and (2) above.

After the reaction of the solid products (II-A), (B2), and (F) is completed, the liquid portion is separated and removed by filtration or decantation, and washing with a solvent is repeated to obtain the crystalline allyltoluene of the present invention. Solid product containing polymer and/or crystalline allylxylene polymer (II+)
That is, a titanium trichloride composition for polyolefin production is obtained.

The titanium trichloride composition of the present invention thus obtained contains 0.01% to 99% by weight of a crystalline allyltoluene polymer and/or a crystalline allylxylene polymer, and is a transition metal compound for polyolefin production. It is used as a catalyst component in the production of polyolefins in combination with at least an organoaluminum compound.

The organoaluminum compound used in the production of the titanium trichloride composition of the present invention has a general formula of AIR'@n', X5-
(+++*s'+ (where n1%a2 represents a hydrocarbon group or alkoxy group such as 771/kyl group, cycloalkyl group, aryl group, X represents a halogen, and Jff
l' represents an arbitrary number of Ohm◆m°≦3. ).

Specific examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, trimybutylaluminum, tri-n-hexylaluminum, trimyhexylaluminum, tri-2-methylpentylaluminum,
Trialkylaluminums such as tri-n-octylaluminum and tri-n-decylaluminum, diethylaluminum monochloride, di-n-propylaluminum monochloride, di-i-butylaluminum monochloride, diethylaluminium monofluoride, diethylaluminium mosbromide, Dialkyl aluminum monohalides such as diethyl aluminum monoiodide, dialkyl aluminum hydrides such as diethyl aluminum hydride, alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, i-butyl aluminum dichloride, etc. Examples include monoalkylaluminum cybarides, and alkoxyalkylaluminums such as monoethoxydiethylaluminum and jetoxymonoethylaluminum can also be used.

These organoaluminums can also be used in combination with all or more Z fffi types.

As the electron donor used in the present invention, various ones are shown below, but (81), it is preferable to mainly use ethers as nil, and to share the other electron donors with ethers. .

Those used as electron donors are organic compounds having any of oxygen, nitrogen, sulfur, and phosphorus atoms, that is,
Ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, urea or thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, sulfides Hydrogen, thioethers, thioalcohols, etc.

Specific examples include diethyl ether, moro-propyl ether, moro-butyl ether, diisoamyl ether, di-n-pentyl ether, moro-hexyl ether,
Diisoamyl ether, Moro-octyl ether, Diisoamyl ether, Moro-dodecyl ether, Diphenyl ether, Ethylene glycol monoethyl ether,
Ethers such as tetrahydrofuran, methanol, ethanol, propatool, butanol, pentanol, hexanol, octatool, phenol, cresol,
Alcohols such as 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, anisic acid Esters such as propyl, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenylacetate, aldehydes such as acetaldehyde and benzaldehyde, formic acid, acetic acid, propion acids, 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, pyridine, quinoline, α-picoline, 2,4.6
-trimethylpyridine, N,N.

Amines such as N',N'-tetramethylethylenediamine, aniline, dimethylaniline, formamide, hexamethylphosphoric triamide, N,N,N''.

Amides such as N',N''-pentamethyl-No-β-dimethylaminomethylphosphate triamide and octamethylpyrophosphoramide, ureas such as N,N,N',N'-tetramethylurea, phenyl isocyanate , isocyanates such as tolyl isocyanate, azo compounds such as azobenzene, phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxyto, dimethylphosphite, Phosphites such as moro-octyl phosphite, triethyl phosphite, tri-n-butyl phosphite, and triphenyl phosphite; phosphinites such as ethyl diethyl phosphinite, ethyl butyl phosphinite, and phenyl diphenyl phosphinite; Thioethers such as diethylthioether, diphenylthioether, methylphenylthioether, ethylene sulfide and propylene sulfide, and thioalcohols such as ethylthioalcohol, n-propylthioalcohol and thiophenol can also be mentioned.

These electron donors can also be used in combination.

electron donor (81) for obtaining the reaction product (1),
Each of (B2) reacted with the solid product (n-A) may be the same or different.

The electron acceptor (F) used in the present invention is found in periodic table III.
-Represented by halides of group Vl elements.

Specific examples include anhydrous aluminum chloride, silicon tetrachloride, stannous chloride, stannic chloride, titanium tetrachloride, zirconium tetrachloride, phosphorus trichloride, phosphorus pentachloride, vanadium tetrachloride, and antimony pentachloride. , 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. Aromatic compounds include aromatic hydrocarbons such as naphthalene, and their derivatives such as mesitylene, durene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene, 1-phenylnaphthalene, and other alkyl HtA bodies, monochlorobenzene, chlorotoluene, and chloroxylene. , chloroethylbenzene, dichlorobenzene, bromobenzene, and other halides.

The furyltoluene and/or allylxylene used in the m-combination treatment are selected from 0-allyltoluene, p-allyltoluene, 2-allyl-p-xylene, 4-allyl-0-xylene, and 5-allyl-m-xylene. One or more selected S-mers.

The titanium trichloride composition 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 olefins. It is used as a catalyst for the polymerization of olefins.

The organoaluminum compound used for olefin polymerization is
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 that used in producing the titanium trichloride composition.

In addition, the olefins used for preactivation include ethylene, propylene, butene-1, pentene-11, hexene-1, heptene-1, and other straight-starting monoolefins;
-Methyl-pentene-1,2-methyl-pentene-1 and other branched chain monoolefins.

These olefins may be the same as or different from the olefin to be polymerized, or 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 containing a combination of a titanium trichloride composition and an organoaluminum compound is sufficiently effective, but for gas phase polymerization, a catalyst that has been preactivated by reacting with an olefin is preferable. When performing gas phase polymerization following slurry polymerization or bulk polymerization, even if the catalyst initially used is the former, it is the same as the latter catalyst because the olefin reaction has already occurred during gas phase polymerization. You can get excellent results.

Preactivation is performed by adding 1g to 500g% of organic aluminum O, 0 to 50iL of solvent, 0 to 1.0001ft of hydrogen, and 0.05g to olefin per 1g of titanium trichloride composition.
S, 000g, preferably 0.05g to 3,000g is used. The olefin was reacted at a temperature of 0°C to 100°C for 1 minute to 20 hours, and the titanium trichloride composition was 0.0
It is desirable to react 1 to 2.000 g, 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, n-hebutane, benzene, toluene, etc., and even in liquefied olefins such as liquefied propylene, liquefied butene-1, etc. of 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 to 5,000g.

The solvent or olefin used in the preactivation can be removed by vacuum removal or filtration during or after the preactivation, and the solid product can be removed by removing 1 g of the solid product.
A solvent may also be added for suspension in an amount of solvent that does not exceed 80°C per hour.

There are various methods of preactivation, for example: (1) A method in which an olefin is brought into contact with a catalyst that combines a titanium trichloride composition and an organoaluminium, and a slurry reaction, a bulk reaction, or a gas phase reaction is carried out. ■ A method of combining a titanium trichloride composition and an organic aluminum in the coexistence of an α-olefin, A method of coexisting a polyolefin with the method of ■■, ■, A method of coexisting hydrogen with a method of ■■, ■, ■ There are several ways to do this. 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 combined titanium trichloride composition and an organoaluminum compound, or a catalyst further preactivated with an olefin, is used in the production of polyolefins, but as in normal olefin polymerization, stereoregular For the purpose of improving properties, an electron donor is used as the third component of the catalyst.
It is also possible to further add it and use it for polymerization.

The amounts of each catalyst component used are the same as in normal olefin polymerization, but specifically, 0.01 g to 5 QOg of the organoaluminum compound and 200 g of the electron donor are used per 1 g of the titanium trichloride composition.

As mentioned above, the polymerization format for polymerizing olefins is ■Lopentane, n-hexane, n-heptane, n
-Slurry polymerization carried out in hydrocarbon solvents such as octane, benzene or toluene; -Bulk polymerization carried out in liquefied olefin monomers such as liquefied propylene and liquefied butene-1; For phase polymerization, there is a method of stepwise combining two or more of (1) to (2) above. In either case, the polymerization temperature was room temperature (20℃) to 200℃, and the polymerization pressure was normal pressure (Ok
g/cm"G) ~50kg/cm"G, usually 5 minutes~
The program will last approximately 20 hours.

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 olefins to be subjected to polymerization include ethylene, propylene, straight chain monoolefins such as butene-11hexene-11octene-1, and branched chain monoolefins such as 4-methylpentene-1,2-methyl-pentene-1. and diolefins such as butadiene, isoprene, and chlorobrene, and not only can each of these be polymerized individually, but also in combination with other olefins, such as propylene and ethylene, butene-1 and ethylene, A combination such as propylene and butene-1, or propylene, ethylene,
Copolymerization can be performed by combining three components like butene-1, or block copolymerization can be performed by changing the type of olefin fed in multistage polymerization.

(Function) The polyolefin obtained using the titanium trichloride composition of the present invention contains a highly stereoregular specific allyl polymer in an extremely dispersed manner, so that the specific allyl polymer is dispersed during melt molding. exhibits a nucleation effect, thereby reducing the spherulite size of the polyolefin and promoting crystallization, thereby increasing the transparency and crystallinity of the polyolefin as a whole.

Further, as mentioned above, the specific allyl polymer introduced into the polyolefin by using the titanium trichloride composition of the present invention is a stereoregular high molecular weight polymer, so that it does not bleed onto the surface.

〔Effect 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 transmuted metal compound catalyst component for polyolefin production in the polymerization of olefins, the production of voids is extremely low with extremely high productivity. It is possible to produce a polyolefin polymer with extremely high transparency and crystallinity.

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 does not contain any specific allyl polymer.
The transparency is approximately 1/4 to 3/7 that of polyolefins obtained using titanium trichloride compositions, and has extremely high transparency.

In addition, the crystallization temperature is also about 5 to 9 degrees higher than when the specific allyl polymer is not contained, and the crystallinity is significantly improved and the flexural modulus is also significantly higher (
Examples 1 to 9, Comparative Examples 15 to LO6). Furthermore, it is clear that the number of voids generated is significantly smaller than in polyolefins into which styrene polymers were introduced by methods other than the present invention (see Examples 1 to 9 and Comparative Examples 2.3).

The second effect of the present invention is that with extremely high polymerization activity,
A polyolefin with good particle shape and high stereoregularity can be obtained. Therefore, the catalyst removal step and the atactic polymer removal step can be omitted, and polyolefins can be produced by a long-term continuous polymerization method using simpler processes 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 producing polyolefin 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 storage 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 producing a polyolefin of the present invention has excellent attrition resistance. The titanium trichloride composition is not susceptible to attrition during its use, ie, during the polyolefin polymer manufacturing process as well as during the catalyst manufacturing process. This means that the formation of a finely divided catalyst and, in turn, the formation of a finely divided polyolefin is prevented.

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 polyolefin 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: Indicates polymerization activity, polymer yield per gram atom of titanium (unit: kg/Durham atom) ■■: Indicates stereoregularity, residue extracted with n-hexane at 20°C
(Unit: double weight %) BD: Bulk specific gravity
(11th place: g/mIt) MFR: Melt flow index according to STM D-1238 (L),
(Unit: g710 minutes) Internal haze: This is the haze inside the film excluding surface effects. Polyolefin powder is made into a 150μ thick film using a press at a temperature of 200℃ and a pressure of 2QOkg/cm"G. After coating both sides of the film with liquid paraffin, the haze was measured in accordance with JIS 7105.
(Unit: %) Crystallization temperature: Measured using a differential scanning calorimeter at a cooling rate of 10° C./min. (WL position: °C) Flexural modulus: Tetrakis[methylene-3-
(3°-15°-di-t-butyl-4°-hydroxyphenyl) propionate cometa (20.1 parts by weight) and calcium stearate (0.1 parts by weight) were mixed, and the mixture was extruded into granules using a screw diameter of 40 mm. It was granulated using a machine. Then, the granulated material was heated to a temperature of 23°C using an injection molding machine.
A JIS type test piece was created at 0°C and a mold temperature of 50°C, and the test piece was left in a room with a humidity of 50% and a room temperature of 23°C for 72 hours, and then the flexural modulus was measured in accordance with JIS K 7203. did. (!# rank: kg
f/cm') Void: Polyolefin was granulated in the same manner as in the previous section, and the resulting granules were extruded using a T-die type film forming machine at a molten resin temperature of 250°C, and then extruded with a cooling roll at 20°C. A sheet with a thickness of 1 mm was created. 15 sheets
The film was heated with hot air at 0° C. for 70 seconds, and then stretched by a factor of 7 in both length and width directions using a biaxial stretching machine to obtain a biaxially stretched film with a thickness of 20 μm. The film was observed with an optical microscope, and the number of voids with a diameter of lθμ or more was measured.
Less than 0 pieces are shown as ○, 20 or more but less than 50 pieces are shown as △, and 50 or more pieces are shown as X.

Example 1 (1) Production of titanium trichloride composition n-hexane 6Il diethylaluminum monochloride (DEAC) 5.0 mol, diisoamyl ether 12
．． 0 mol was mixed at 25°C for 5 minutes and reacted at the same temperature for 15 minutes to form reaction product solution (1) (diisoamyl ether/
A DEAC molar ratio of 2.4) was obtained.

Put 40 moles of titanium tetrachloride into a reactor purged with nitrogen,
It was heated to 35°C, and the entire amount of the reaction product liquid (1) was added dropwise thereto over 180 minutes, and then kept at the same temperature for 60 minutes, and heated to 80°C.
The temperature was raised to ℃ and reacted for another 1 hour, cooled to room temperature, the supernatant liquid was removed, 20 ρ of n-hexane was added, and the supernatant liquid was removed by decantation, which was repeated 4 times to obtain a solid product (I
I) was obtained.

The entire amount of (II) was suspended in 30 IL of n-hexane, 400 g of diethylaluminum monochloride was added, and 22 kg of 4-allyl-0-xylene was added at 40°C, followed by polymerization treatment at 40°C for 2 hours. After the treatment, the temperature was raised to 50°C, the supernatant liquid was removed, n-hexane 3GIl was added, and the supernatant liquid was removed by decantation, which was repeated four times to obtain a polymerized solid product (n-A). I got it.

While the entire amount of this solid product was suspended in 9 L of n-hexane, 3.5 kg of titanium tetrachloride was added at room temperature for about 10 minutes, and after reacting at 80°C for 30 minutes, diisoamyl 1.6 kg of ether was 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 4-allyl-0-xylene polymer content in the obtained titanium trichloride composition was 33 Jli%, and the titanium content was 16.8% by weight.

(2) Preparation of preactivated catalyst After purging a stainless steel reactor with inclined blades with internal volume aOit with nitrogen gas, 40 ρ of n-hexane, 28.5 g of diethylaluminum monochloride, the uninvented product obtained in (1) After adding 340 g of the titanium trichloride composition at room temperature, 0.7N+a3 of ethylene was supplied at 30°C for 2 hours to cause a reaction (2.0 g of ethylene reacted per 1 g of the titanium trichloride composition). Remove ethylene, n-
After washing with hexane and drying, a preactivated catalyst was obtained.

(3) L/D equipped with a stirrer with an internal volume of 801 cm and replaced with olefin polymerization nitrogen.
After charging 20 kg of polypropylene powder with an MFR of 2.0 into the horizontal polymerization vessel in Step 3, n-hexane was added to the preactivated catalyst obtained in (2) above to form a 4.0% by weight hexane suspension. The suspension was continuously supplied from the same pipe at a rate of 6.45 milligram atoms/hr in terms of titanium atoms, and diethylaluminium monochloride at a rate of 3.8 g/hr.

In addition, hydrogen was supplied so that the concentration in the gas phase of the polymerization reactor was maintained at 1.0% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg/cm2G.
The test was carried out continuously for 120 hours at ℃.

During the polymerization period, the polymer retention level in the polymerization vessel is 50%.
Continuously lok the polymer from the polymerization vessel so that the volume %
It was extracted at a rate of g/hr. The extracted polymer was then contacted with nitrogen gas containing 0.2% by volume of propylene oxide at 95° C. for 15 minutes, and then 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 0°C for 4 months, propylene was polymerized in the same manner as in (1) and (2).

(5) After connecting a circulation line equipped with a circulation pump to the reactor used in the attrition resistance test (2), the mixture was heated with n-hexane at 20°C under a nitrogen atmosphere, and in the same manner as in (1) above. 340 g of the obtained titanium trichloride composition was added. Subsequently, the circulation pump is activated, and the suspension in the reactor is controlled to a flow rate of 10 using the circulation line.
After circulating for 4 hours under the conditions of J2/min and a temperature of 25°C,
Polymerization of propylene was carried out in the same manner as in (2) and (3).

Comparative Example 1 (1) Except for making the solid product (o-A) equivalent without polymerizing the solid product (!I) with 4-allyl-0-xylene in (1) of Example 1. A titanium trichloride composition was obtained in the same manner.

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

(3) 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 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 Comparative Example 1 (1).

(2) Into the reactor used in Example 1 (2), add n-hexane 20J1. Diethyl aluminum monochlorite 3
0g, and titanium trichloride composition 18 obtained in (1) above.
After adding 0 g at room temperature, pt-butylstyrene 165
g was added and reacted at 40°C for 2 hours. (0.5g reaction per 1g of titanium trichloride composition) After the reaction was completed, the mixture was washed with n-hexane, filtered and dried to obtain a catalyst preactivated with pt-butylstyrene.

(3) Polymerization of propylene was carried out in the same manner as in (3) of Example 1 except that the catalyst preactivated with pt-butylstyrene obtained in (2) above was used as the preactivated catalyst. The produced bulk polymer blocked the powder extraction pipe, so we had to stop production 11 hours after the start of polymerization.

Comparative Example 3 (1) In (1) of Comparative Example 1, when reacting the reaction product liquid (1) with titanium tetrachloride, (1) of Comparative Example 1 was separately added.
) Using 500 g of titanium trichloride composition obtained in the same manner as above and 120 g of diethylaluminium monochloride as a catalyst, 1.45 kg 1 was added to n-hexane 100 JZ.
After polymerizing the added p-t-butylstyrene at 60°C for 2 hours, the resulting p-t-butylstyrene was washed with methanol and dried.
A pt-butylstyrene polymer was prepared in the same manner except that 0.95 kg of t-butylstyrene polymer was ground for 5 hours at room temperature in a vibration mill with a capacity of A titanium trichloride composition containing 33.3 mff of 1% was obtained.

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

(3) In (3) of Example 1, the preactivated catalyst obtained in (2) above was used as the preactivated catalyst at a total pressure of 23 kg/c.
Polypropylene was obtained by polymerizing propylene in the same manner except that it was supplied so as to maintain m2G.

Comparative Example 4 and Example 2.3 By changing the amount of 4-allyl-0-xylene used in the polymerization treatment in (1) of Example 1, the crystalline 4-allyl-0-xylene polymer content was 11 and 011 respectively
13n view%, 48 heavy H%, 18.71 amount% no three kn
A titanium oxide composition was obtained. Next, (2) of Example 1, (
Polymerization of propylene was carried out in the same manner as in 3).

Example 4 Kanoheptane 41, diethylaluminum monochloride
5.0 mol, diisoamyl ether 9.0 mol, Moro-
The reaction solution obtained by reacting 5.0 mol of butyl ether at 18°C for 30 minutes was added dropwise to 27.5 mol of titanium tetrachloride at 40°C over 300 minutes, and then kept at the same temperature for 1.5 hours to react. After that, the temperature was raised to 65°C, reacted for 1 hour, and the upper iT1? The operation of adding 201 ml of n-hexane and removing by decantation was repeated 6 times, and 1.8 kg of the obtained solid product (++) was added with 4 ml of n-hexane.
Suspended in diethylaluminum monochloride 5
00g and 20k of 2-allyl-p-xylene at 50℃
g was added and reacted for 1 hour to obtain a polymerized solid product (o-A).

After the reaction, after removing the supernatant liquid, adding ■-hexane 2 (In) and removing by decantation, repeating the procedure twice to obtain the solid product (II-A) subjected to the above polymerization treatment.
1.8 kg of titanium tetrachloride suspended in hexane 7J2
, n-butyl ether (1.8 kg) was added, and the mixture was reacted at 60° C. for 3 hours. After the reaction was completed, the supernatant was removed by decantation, 20 fl of n-hexane was added, stirred for 5 minutes, allowed to stand, and the supernatant was removed three times, then dried under reduced pressure and trichlorinated. A titanium composition was obtained and the titanium composition of Example 1 (
Polymerization of propylene was carried out in the same manner as in 2) and (3).

Ratio (・2 Example 5 In Example 4, the solid product (1■) was converted into the solid product (II) without the polymerization treatment with 2-allyl-p-xylene.
-A') 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 5.0 mol of diethylaluminum monochloride, 4.0 mol of moro-butylaluminum monochloride was used to obtain a reaction product solution (1), which was added dropwise to titanium tetrachloride at 45°C, and A titanium trichloride composition was obtained and propylene was polymerized in the same manner as in Example 1, except that 9.7 kg of 0-allyltoluene was used instead of 4-allyl-0-xylene.

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 0-allyltoluene.

Example 6 In place of titanium tetrachloride in +1) of Example 1, 1.8 kg of silicon tetrachloride and 2.0 kg of titanium tetrachloride were used.
The mixture of 2. and diisoamyl ether.
A titanium trichloride composition was obtained in the same manner except that 2 kg of the titanium trichloride composition was reacted with a solid product (o-A).

Subsequently, n-hexane was added to the titanium trichloride composition in a polymerization vessel equipped with a stirrer and equipped with a two-stage turbine blade having an internal volume of 200 Il to form a 4.0% by weight rhohexane suspension. The liquid is converted into titanium atoms by 10. i milligram atoms/hr, and diethylaluminum monochloride [i, Og/hr from the same pipe and from a separate pipe n
-Hexane was continuously fed 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/c+n'G, and slurry polymerization of propylene was carried out at 70°C. The test was carried out continuously for 120 hours.

During the polymerization period, the slurry retention level in the polymerization vessel is 75%.
The slurry was continuously drawn out from the polymerization vessel into a flash tank having an internal volume of 501 % by volume. While the pressure was reduced in a flash tank to remove unreacted propylene, methanol was supplied at a rate of 1 kg/hr and contact treatment was carried out at 70°C. Subsequently, the slurry is separated from the solvent by a centrifuge and then dried to form a product powder.
obtained at okg/hr.

Comparative Example 7 Solid product (II) was converted into solid product (II) without performing the polymerization JA process using 4-allyl-O-xylene in Example 6.
-A) 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 for using the equivalent product.

Example 7 27.0 mol of titanium tetrachloride was added to n-hexane + 2IL, and after cooling to 1°C, n-hexane 1251 containing 27.0 mol of diethylaluminium monochloride was added dropwise at 1°C over 4 hours. did. After the dropwise addition was completed, the temperature was kept at the same temperature for 15 minutes to react, then the temperature was raised to 65° C. over 1 hour, and the reaction was further continued at the same temperature for 1 hour.

Next, the supernatant liquid was removed, 10 ft of n-hexane was added, and the operation of removing by decantation was repeated 5 times. Of the 5.7 kg of solid product (II) obtained, 1.8 kg was
Suspend in hexane at 50°C, add 350g of diethylaluminium monochloride, and heat to 40°C to dissolve 5-allyl-
After adding an additional 15.6 kg of m-xylene, the
A time polymerization treatment was performed.

After the polymerization treatment, after removing the supernatant liquid, 0-hexane 3 (If
After repeating the operation of adding t and removing by decantation twice, the resulting polymerized solid product (II-
The entire amount of A) was suspended in 11λ of n-hexane, and 1.6°C of di-isoamyl ether was added thereto. This suspension was stirred at 35° C. for 1 hour and then washed five times with n-hexane 3J2 to obtain a treated solid. The resulting treated solid was suspended in a solution of 40 volume % titanium tetrachloride in n-hexane and 6 volumes.

This suspension was heated to 65°C and reacted at the same temperature for 2 hours. After the completion of the reaction, the resulting solid was washed three times using 20 ft of n-hexane each time, and then dried under reduced pressure. A titanium trichloride composition was obtained by smoking. Using the obtained titanium trichloride composition, slurry polymerization of propylene 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 5-allyl-m-xylidine in Example 7, and slurry polymerization of propylene was then carried out in the same manner as in Example 7.

Example 8 Using 3.5 kg of p-allyltoluene in place of 4-allyl-O-xylene in (1) of Example 1, a solid product (n-A) was obtained by polymerization, and then After adding 3.0 kg of titanium tetrachloride to 10 fL of n-hebutane, the entire amount of the above solid product (II-A) was added and reacted at 80°C for 30 minutes. After the completion of the reaction, further di-n
- 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, the following steps were carried out in Example 1 (
Gas phase polymerization of propylene was carried out in the same manner as in 2) and (3).

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 p-allyltoluene.

Example 9 Propylene-ethylene copolymerization was carried out in the same manner as in Example 6, except that during propylene polymerization, ethylene was further supplied so that the concentration in the gas phase was maintained at 0.2% by volume. .

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 4-allyl-0-xylene.

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

[Brief explanation of the drawing]

Figure 1 shows A manufacturing process diagram explaining the invention in detail It is. that's all

Claims (5)

[Claims] (1) 0.01% to 99% by weight of crystalline allyltoluene polymer and/or crystalline allylxylene polymer
and titanium trichloride composition 99.99% by weight to 1.0%
% by weight of a titanium trichloride composition for producing a polyolefin. (2) The crystalline allyltoluene polymer and/or the crystalline allylxylene polymer is a crystalline o-allyltoluene polymer, a crystalline p-allyltoluene polymer, a crystalline 2-
Allyl-p-xylene polymer, crystalline 4-allyl-o-
The titanium trichloride composition according to claim 1, which is one or more crystalline polymers selected from xylene polymers and crystalline 5-allyl-m-xylene polymers. (3) Organoaluminum compound or reaction product of organoaluminum compound and electron donor (B_1) (
A solid product obtained by reacting titanium tetrachloride with I) (
II) is polymerized with allyltoluene and/or allylxylene, and the electron donor (B_2) is further reacted with the electron acceptor to obtain a solid product (III), which is crystalline allyltoluene and/or crystalline 1. A method for producing a titanium trichloride composition for producing a polyolefin, comprising containing 0.01% to 99% by weight of an allylxylene polymer. (4) As an organoaluminum compound, the general formula is AlR
^1_mR^2_m・X_3_-_(_m_+_m_'
_) (In the formula, R^1 and R^2 represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, or an aryl group, or an alkoxy group, X represents a halogen, and m and m' represent 0<m+m
′≦3. ) The manufacturing method according to claim 3, using an organoaluminum compound represented by: (5) As allyltoluene and/or allylxylene, o-allyltoluene, p-allyltoluene, 2-
The manufacturing method according to claim 3, which uses one or more monomers selected from allyl-p-xylene, 4-allyl-o-xylene, and 5-allyl-m-xylene.