JPS5840563B2 - Olefin polymerization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for polymerizing or copolymerizing ethylene or α-olefin, and more specifically to an activated titanium trichloride composition obtained by a special activation treatment and an organoaluminum compound. The present invention relates to a method for obtaining an ethylene or α-olefin polymer or copolymer with high crystallinity and a low content of fine particles using a novel highly active catalyst consisting of the following.

It is known to use a so-called Ziegler-Natsuta catalyst, which is a combination of a transition metal halide such as titanium trichloride, titanium tetrachloride, etc., and an organometallic compound when polymerizing or copolymerizing ethylene or α-olefin.

In the known polymerization of ethylene or α-olefin, particularly in the polymerization of propylene, a composite catalyst of titanium trichloride and an organoaluminum compound is generally used.

As the titanium trichloride used in this case, various types of titanium trichloride are used, which differ depending on the manufacturing method.

However, depending on the type of titanium trichloride used, there are large differences in the activity of the catalyst, the crystallinity of the obtained polymer, and the content of fine particles, and a satisfactory catalyst that has all three effects has not yet been recognized. do not have.

For example, various methods have been reported for improving the stereoregularity of the resulting polymer by simply adding various organic compounds to the polymerization catalyst system.

For example, a method of adding tetrahydrofuran or thiobutyl ether (Japanese Patent Publication No. 39-5455), a method of adding a phosphine oxide compound (Japanese Patent Publication No. 392-470)
3) A method of adding lower oxygen acid organic esters or organic thioesters containing phosphorus, sulfur, etc. (Japanese Patent Publication No. 42-2
2052) etc.

However, these methods often reduce the polymerization activity, and as a result of increasing the amount of catalyst used, the ash content of the polymer increases, causing quality problems such as coloring of the polymer.

In particular, when an organic sulfur compound or an organic phosphorus compound is used, a bad odor remains in the polymer.

In addition, there are drawbacks such as causing poor separation of washing water during polymer purification, and many difficulties are involved in industrially utilizing catalysts to which organic compounds such as those mentioned above are added.

In addition, a catalyst containing a titanium trichloride composition and an organoaluminum compound obtained by co-pulverizing ketones or ethers in the presence or absence of titanium tetrachloride on titanium trichloride or the titanium trichloride composition A method of polymerizing propylene in a system is known from Japanese Patent Publication No. 43-10065 and Japanese Patent Publication No. 43-15620.

This catalyst system is intended to reduce the fine particle content and improve the stereoregularity of polypropylene obtained by polymerization, but the polymerization activity is low and the stereoregularity cannot be said to be sufficient.

On the other hand, for the purpose of obtaining a polymerization catalyst for α-olefins with a large proportion of stereoregular polymer formation and higher polymerization activity, the various organic compounds described above and aluminum halide, or a reaction product of both, are added as additives. A method of washing with a solvent after co-pulverization has been reported.

For example, a method using an organic oxygen-containing compound and an aluminum halide or a reaction product of both as an additive (Japanese Patent Publication No. 49-2021), a method using an organic sulfur-containing compound and an aluminum halide (Japanese Patent Publication No. 49-33597), an organic Method using phosphorus-containing compound and aluminum halide (
Special Publication No. 5O-17112) etc.

These catalysts are highly active, and after the additives are added and co-pulverized, they are washed with a solvent, so unnecessary additives other than those that are coordinated or adsorbed to the active sites are removed by washing. Therefore, the various disadvantages observed in the known methods of simply adding the various additives to the polymerization catalyst system or the known methods of adding and co-pulverizing are not observed.

However, since the polymer polymerized using this catalyst system still has a large particulate content, the fluidity of the polymer slurry or polymer powder is poor, causing problems in industrial production.

The present inventors conducted various studies and arrived at the present invention with the aim of creating a highly active catalyst that can obtain a highly crystalline polymer with a small particle content and uniform particle size by employing a special activation treatment.

That is, the present invention provides titanium trichloride or a titanium trichloride composition and the following (a) in the presence or absence of titanium tetrachloride.
~(/An organic compound containing an oxygen atom, a sulfur atom, and a phosphorus atom (hereinafter referred to as an organic compound containing a heteroatom).

), (a) An organic oxygen-containing compound selected from ethers, ketones, and esters.

(b) Organic sulfur-containing compounds selected from thioethers, thiophenols, and thioalcohols.

(/→ Organic phosphorus-containing compound.

The activated titanium trichloride that has undergone the first pulverization step of co-pulverizing the activated titanium trichloride is further mixed with at least one additive selected from the following (a) to (c): (a) aluminum halide;

(b) at least one type of organic compound containing a heteroatom and an aluminum halide.

(c) A complex or reaction product with a compound aluminum halide selected from organic compounds containing a heteroatom.

The titanium trichloride composition that has gone through the second pulverization step of adding and co-pulverizing is washed with a solvent and the soluble materials are extracted using a catalyst consisting of an activated titanium trichloride composition and an organoaluminum compound. This is an olefin polymerization method in which ethylene or α-olefin is polymerized or copolymerized.

When ethylene or α-olefin is polymerized by the method of the present invention, the activity of the catalyst is high, the stereoregularity of the polymer produced is high, the amount of polymer produced per unit catalyst is increased, and the production of by-products is reduced. Since the amount is small, not only the basic unit of catalyst and monomer is improved, but also the content of fine particles is significantly reduced, which brings about the following advantages in industrial production.

(1) Good fluidity of polymer slurry or powder.

(2) Less leakage during solid-liquid separation and drying.

(3) Fewer troubles occur during pneumatic transport of powder, and collection efficiency is high.

Furthermore, when used as a catalyst for copolymers, the slurry properties during polymerization are particularly good compared to known catalysts.

The reasons for this are that, of course, the fine particle content is low, the catalyst system provides a higher crystalline polymer than known catalysts, the amorphous polymer has a structure that makes it difficult to dissolve in the polymerization solvent, and the monomer content is low. This may be because the reactivity ratio of the catalyst is different from that of known catalysts.

Furthermore, since the catalyst system according to the present invention has high polymerization activity, the ash content in the polymer is low and there are no quality problems such as coloring.
Since the catalyst is washed with a solvent, problems such as bad odor remaining in the polymer and poor separation of washing water and polymer slurry during polymer purification do not occur.

As described above, the method according to the present invention is an excellent catalyst for the polymerization of homopolymers and copolymers, and it is possible to simplify the polymerization equipment and post-processing method, which is extremely beneficial for industrial production. .

The catalyst in the method of the present invention requires a first pulverization step, a second pulverization step, and a cleaning step with a solvent, and the time required for the second pulverization time must be less than or equal to the first pulverization time.

If one or more steps in the combination of these three steps are omitted, the order of the three steps is changed, or the second grinding time is made longer than the first grinding time, the effects of the present invention will not be achieved, and the grinding conditions as in the present application will not be achieved. It is possible to obtain a catalyst that yields a polymer with high activity, high crystallinity, and particularly a low content of fine particles.

Titanium trichloride or titanium trichloride composition as used in the present invention is titanium trichloride obtained by reducing titanium tetrachloride with hydrogen, or a eutectic of titanium trichloride and metal halide obtained by reducing titanium tetrachloride with a metal. , a titanium trichloride composition obtained by reducing titanium tetrachloride with a compound having a 5i-H bond or an organic aluminum compound.

Further, the effect of the present application can be obtained even if titanium tetrachloride is not included in titanium trichloride, and although the content of titanium tetrachloride is not limited, it is usually 0.5 to 10 weight φ, preferably 1 to 5 It is advantageous to include titanium chloride by weight.

In the method of the present invention, the following compounds may be mentioned as the organic compound containing a petro atom that is used as an additive or as a component of the additive in the first pulverization step.

(a) Ethers, ketones, and esters are used as organic oxygen-containing compounds.

As ethers, the general formula R'-0R2 (however, R',
R2 is an alkyl group, an aralkyl group, a cycloalkyl group,
It is an aryl group or a halogen substituent thereof.

), saturated or unsaturated ethers, cyclic ethers, or polyethers are used.

For example, diethyl ether, di-n-furoyl ether, dibenzyl ether, dicyclohexyl ether, diphenyl ether, ditolyl ether, methyl phenyl ether, diallyl ether, futhinyl ether, di(
4-'70 ruphenyl) ether 2-chlorophenyl ether tetrahydrofuran, propylene oxide,
Examples include diethylene glycol, dimethyl ether, diethylene glycol dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol diphenyl ether, and ethylene glycol ditolyl ether.

(However, R3 and R4 represent an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen substituent thereof.

), cyclic ketones, and ester ketones, such as acetone, diethyl ketone, methyl isobutyl ketone, methyl benzyl ketone, acetophenone, diphenyl ketone,
Examples include cyclohexanone, acetylacetone allyl phenyl ketone, P-chlorophenyl methyl ketone, methyl tolyl ketone, and the like.

(However, R5 and R6 represent an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen substituent thereof.

) and cyclic esters such as methyl acetate, methyl acetoacetate, ethyl acetate, cyclohexyl acetate, benzyl acetate, methyl benzoate, ε-caprolactone, and ethyl chloroacetate.

Among these, diethyl ether, diphenyl ether, ditolyl ether, 2-chlorophenyl ether, diethyl ketone, diphenyl ketone, methyl acetate and the like are preferred.

(b) As the organic sulfur-containing compound, thioethers, thiophenols, and thioalcohols are used.

The thioether has the general formula R7-8-R8 (where R?, B8. is an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen substituent thereof).

) Saturated or unsaturated thioethers or cyclic thioethers are used, such as diethyl thioether,
Examples include dicyclohexylthioether, diphenylthioether, ditolylthioether, methylphenylthioether, ethylphenylthioether, propylphenylthioether, dibenzylthioether, diallylthioether, allyl phenylthioether, ethylene sulfide, propylene sulfide, and tetramethylene sulfide.

For thiophenols and thioalcohols, general formula H
-8-R' (where R9 is an alkyl group, an aralkyl group,
It is a cycloalkyl group, an aryl group, or a halogen substituent thereof.

) Saturated or unsaturated thiophenols,
These are thioalcohols, such as ethylthioalcohol, n-propylthioalcohol, n-butylthioalcohol, n-hexylthioalcohol, n-dodecylthioalcohol, cyclohexylthioalcohol, benzylthioalcohol, allylthioalcohol, thiophenol O-methylthiophenol P -Methylthiophenol Examples include 2-chloroethylthioalcohol P-chlorothiophenol.

Among these, particularly preferred are diethylthioether, di-n-propylthioether, dibenzylthioether, dipheni/I/f-J ether, methylphenylthioether ethylphenylthioether, tetramethylene sulfide, n-dodecylthioalcohol thiophenol, and the like. .

(/→ The organic phosphorus-containing compound has the following general formula CI
) to (xVE) are used.

(a) Phosphines represented by the general formula PRA0(I) (RIO in the general formula is hydrogen or an alkyl group, an aralkyl group, a cycloalkyl group, or an aryl group) such as ethylphosphine, diethylphosphine, phenylphosphine, diphenylphosphine, triethylphosphine tri-n-butylphosphine, )'J-n-decylphosphine, tribenzylphosphine, tricyclohexylphosphine, tritolylphosphine diethyl n-
Examples include butylphosphine, ethyldiphenylphosphine, n-propyl-n-furphenylphosphine, and ethylbenzylphenylphosphine.

(b) Phosphine halides represented by the general formula PR R41X (II) (R11 in the general formula represents an alkyl group, a cycloalkyl group, and an aryl group, and X represents a halogen atom.

) Examples include dimethylphosphinas bromide, diethylphosphinas chloride, diisopropylphosphinas chloride, methylethylphosphinas chloride, diphenylphosphinas chloride, and ethylphenylphosphinas chloride.

(c) Phosphonous cybalides represented by the general formula PR12X2 (I[D) (R12 in the general formula is an alkyl group, an aralkyl group, a cycloalkyl group, or an aryl group, and X represents a halogen atom.

) Examples include methylphosphonas dichloride, methylphosphonas dibromide, ethylphosphonas dibromide, butylphosphonas dichloride, benzylphosphonas dichloride, cyclohexylphosphonas dichloride, phenylphosphonas dichloride, phenylphosphonas dichloride, and the like.

(d) R13 in the general formula, B
14 represents an alkyl group and an aryl group.

) For example, ethyl diethyl phosphinite, ethyl dipropyl phosphinite, ethyl dibutyl phosphinite
Phenyldiphenylphosphinite, ethyldiphenylphosphinite, phenyldibenzylphosphinite
Examples include ethylmethylphenylphosphinite.

(e) Phosphonites represented by the general formula P R'' (OR16)2(V) (R15 in the general formula, R
16 represents an alkyl group, an aralkyl group, and an aryl group.

) Examples include dimethylethylphosphonite, diethyl ethylphosphonite, diethylbutylphosphonite, diethylbenzylphosphonite, diethylphenylphosphonite, diphenylmethylphosphonite, diphenylethylphosphonite, and the like.

(f) Phosphites represented by the general formula P(OR17)3(Vl) (R17 in the general formula represents a hydrogen atom, an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, and its halogen substituent.

) For example, dimethyl phosphite, diphenyl phosphite, dioctyl phosphite, trimethyl phosphite, tri(2chloroethyl) phosphite, tri(n-butyl) phosphite, tribenzyl phosphite, tricyclohexyl phosphite, triphenyl phosphite, tri (P-H) phosphite, tri-β-naphthyl phosphite, diphenylcyclohexyl phosphite, diphenylpropyl phosphite, and the like.

(g) Halogenophosphites represented by the general formula P(OR18)2Xura (R18 in the general formula is an alkyl group, cycloalkyl group, or aryl group, and X represents a halogen atom.

) For example, dimethylchlorophosphite, diethylchlorophosphite, di-n-butylchlorophosphite,
Examples include dicyclohexylchlorophosphite, diphenylchlorophosphite, diP-tolylchlorophosphite, and the like.

(h) Dihalogenophosphites represented by the general formula P(OR19)X2(vllD) (R19 in the general formula
represents an alkyl group, an aryl group, or a halogen-derived group thereof, and X represents a halogen atom.

) For example, methyldichlorophosphite, methylchlorofluorophosphite, ethyldichlorophosphite, allyldichlorophosphite, n-butyldichlorophosphite, phenyldichlorophosphite, P-chlorophenyldichlorophosphite, 2-chloroethyldichlorophosphite, etc. can give.

(i) General formula P(NR,0)B(DOP(NR lid l
) X(X)・P (NRj2) Aminophosphine represented by X2(XI) (R20 in the general formula,
R21 and R22 represent an alkyl group or an aryl group, and X represents a halogen atom.

) For example, tris(dimethylamino)phosphine, tris(diethylamino)phosphine, tris(di-n-butyl-amino)phosphine, phosphorustri(N-methylanilide), bis(dimethylamino)chlorophosphine, dimethylaminodifluorophosphine, diethylaminodichloro Examples include phosphine and (di-n-butylamino)dichlorophosphine.

(j) General formula PO) (OR23) 3a [l) R23 in the general formula represents hydrogen, an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen-derived group thereof.

) For example, methyl dihydrodiene phosphate, ethyl dihydrodiene phosphate, n-butyl dihydrodiene phosphate, cyclohexyl dihydrodiene phosphate, phenyl dihydrogen phosphate, P-'70 lophenyl dihydrodiene phosphate, diethyl phosphate, Di-n-propyl phosphate dibenzyl phosphate diphenyl phosphate
Di-alpha naphthyl phosphate, diphenyl phosphite, triethyl phosphate, tri(n-butyl) phosphate, tri(n-amyl) phosphate, tricyclohexyl phosphate, tri(0-chlorophenyl) phosphate, triphenis phosphate, tritolyl phosphate, trin-)lyl phosphate,
Examples include tri-4-biphenyl phosphate and tri-(α-naphthyl) phosphate.

(k) General formula P(0) (OR24) 2 X (
Phosphorohalogenates represented by X[II] (R24 in the general formula represents an alkyl group, a cycloalkyl group, or an aryl group, and X represents a halogen atom.

) Examples include dimethylphosphorochloridate, diethylphosphorochloridate, diisopropylphosphorochloridate, dicyclohexylphosphorochloridate, diphenylphosphorochloridate, and the like.

(1) General formula P(0(OR25) X2(XIV)
Phosphorodihalogenates represented by (in the general formula, R25 represents an alkyl group and an aryl group, and X represents a halogen atom.

) Examples include methylphosphorodichloridate, ethylphosphorodichloridate, ethylphosphorochloride fluoridate, n-butylphosphorodichloridate, P-tolylphosphorodichloridate, phenylphosphorodichloridate, and the like.

(e) General formula R16P=0 (XV), (Ri7N)
Phosphine oxytos and derivatives thereof represented by 3P=0(XVI) (R26 and R2? in the general formula represent an alkyl group, an aralkyl group, a cycloalkyl group, and an aryl group.

) For example, trimethylphosphine oxide, tri-n-butylphosphine oxide, tribenzylphosphine oxide, tricyclohexylphosphine oxide, triphenylphosphine oxide, diallylphenylphosphine oxide, diphenylbenzylphosphine oxide, diphenyl-D-)IJ lphosph inoxide, tris-
Examples include N,N-dimethylphosphoramide, tris-N,N-diethylphosphoramide, and the like.

(n) General formula R38P = S (XVII) Phosphine sulfides represented by the general formula (R2 in the general formula
8 represents an alkyl group, an aralkyl group, and an aryl group.

) For example, trimethylphosphine sulfide, triethylphosphine sulfide, tri-n-propylphosphine sulfide, tri-n-butylphosphine sulfide,
Examples include triphenylphosphine sulfide, diethylphenylphosphine sulfide, and diphenylbenzylphosphine sulfide.

Among these organic phosphorus-containing compounds, triphenylphosphine, triphenylphosphite, triphenylphosphine oxyto, triphenylphosphate, tri-P-tolylphosphate, and the like are particularly preferred.

On the other hand, the aluminum halide used as an additive in the second pulverization step of the present invention includes aluminum trichloride, aluminum tribromide, aluminum trifluoride, and aluminum misawadide, with aluminum trichloride being particularly preferred.

Further, in the second pulverization step in the present invention, aluminum halide and the organic compound containing the hetero atom can be used together.

Further, in the method of the present invention, a complex or a reaction product of an organic compound containing a heteroatom and aluminum halide can be used, but in this case, particularly preferred are diphenyl ether/aluminum trichloride complex,
Diphenyl ether/aluminum tribromide complex, diethyl ether/aluminum trichloride complex, diethyl ketone/aluminum trichloride complex, diphenylthioether/
Aluminum trichloride complex, phenylmethylthioether/aluminum trichloride complex, thiophenol/aluminum trichloride reaction product, diethylthioether/aluminum trichloride reaction product, triphenylphosphine/aluminum trichloride complex, triphenylphosphite/trichloride Examples include aluminum complexes, triphenyl phosphate/aluminum trichloride complexes, tritolyl phosphate/aluminum trichloride complexes, tris-N,N-dimethylphosphoramide, and aluminum trichloride complexes.

The above complex can be synthesized by known methods, but most commonly, aluminum trihalide and the above-mentioned heteroatom-containing organic compound are mixed at room temperature, or
Alternatively, it can be easily synthesized by heating a mixture.

In order to synthesize the above-mentioned complex or reaction product, it is preferable to synthesize the above-mentioned heteroatom-containing organic compound and aluminum halide under conditions in which the molar ratio is close to 1=1, but if either one is in excess , an excess of which is present in free form may be used as a complex or reaction product.

The amount of the additive to be added and co-pulverized to titanium trichloride or the titanium trichloride composition in the first pulverization step of the method of the present invention varies depending on the type of additive, etc., but generally titanium trichloride or titanium trichloride is used. 0.1-5 for the composition
The 0 weight/multi weight type or the range of 1 to 25 weight φ.

Additives are usually added before the pulverization operation, but they may also be added during the pulverization process or in several parts, and when two or more additives are used together, two or more types of additives may be added. The two components may be added and co-pulverized at the same time, or one component may be added and co-pulverized, and then the other component may be further added and crushed.

In addition, the amount of the additive to be added and co-pulverized in the second pulverization step of the method of the present invention varies depending on the type of additive, etc., but is generally O01 to 50% by weight based on titanium trichloride or titanium trichloride composition. φ is preferably in the range of 1 to 25 weight range.

Additives are added after the first pulverization step, but the second
It may be added in several batches after entering the pulverization process, or if two or more additives are used together, they may be added at the same time and co-pulverized, or one component may be added. After co-pulverizing, other components may be added and co-pulverizing.

The mill used is a common mill used for milling powder, such as a ball mill, an aeroform mill, a vibration mill, a jet mill, a ring mill, an impact mill, and the like.

The grinding operation is carried out in a vacuum or inert gas atmosphere,
It must be carried out in conditions where moisture and oxygen are almost completely excluded.

There is no particular restriction on the temperature during crushing, but it is between 0°C and 15°C.
A range of 0°C is common.

The grinding time varies depending on the type of grinder, the type and amount of additives used in the first and second grinding steps, etc.
The pulverization time of the first pulverization step is usually in the range of 2 to 100 hours, preferably 5 to 60 hours, and the pulverization time of the second pulverization step is required to be less than or equal to the pulverization time of the first pulverization step.

By adding the above-mentioned additive to titanium trichloride or a titanium trichloride composition in the presence or absence of titanium tetrachloride as described above, co-pulverizing in the first and second stages, and washing with a solvent. , it is possible to obtain a highly active catalyst with a low content of fine particles.

The solvent used for cleaning is preferably aliphatic, alicyclic, aromatic, hydrocarbons or their halogen derivatives, or mixtures thereof, such as Eva, hexane,
Examples include heptane, benzene, toluene, xylene, and monochlorobenzene.

Washing is carried out at a rate of 1 to 50% for the above co-ground titanium trichloride composition.
The reaction is carried out at 0°C to 200°C by adding 0 times (by weight) amount of solvent.

After washing, remove the solvent by decantation or filtration.

After performing this washing operation several times, the slurry can be used as a polymerization catalyst component as it is.

After washing, the solvent is removed by decantation or filtration, a small amount of solvent is removed at normal pressure or reduced pressure, and the temperature is further increased to room temperature or higher, preferably at 50°C.
It is also possible to use one that has been heat-treated at a temperature of 200°C to 200°C and dried.

The organoaluminum compound used in combination with the activated titanium trichloride component as a catalyst component in the method of the present invention may be any known organoaluminum compound used as an olefin polymerization catalyst in combination with titanium trichloride; It is also effective to add a third component known as an aluminum compound-third component catalyst.

In particular, the method of the present invention uses a compound of the general formula AlR3 (where R represents an alkyl group or an aryl group and X is a halogen atom).

), for example, diethylaluminum monochloride, triethylaluminum, di-n-propylaluminum monochloride, tri-n-butylaluminum diisobutylaluminum monochloride, triisobutylaluminum, or a mixture thereof.

The molar ratio of organic aluminum to activated titanium trichloride is usually 1:0.3 to 1:100. Preferably,
The ratio is generally 1:0.5 to 1:50.

The monomers from which the polymer can be produced by the method of the present invention are ethylene and α-olefins, including ethylene, propylene, butene-1, pentene-1-hexene-
Examples include 14-methylpentene-1 and mixtures thereof, and these monomers or mixtures thereof can be efficiently
It can be polymerized into a polymer or copolymer.

The polymerization reaction according to the method of the present invention is carried out under conditions conventional in the art.

The polymerization temperature at that time is in the range of 20°C to 200°C, preferably 50°C to 100°C, and the pressure can be in the range of normal pressure to 200 atm.
Generally, it is preferable to carry out the polymerization under a pressure of normal pressure to 100 atm.

In the polymerization reaction, generally aliphatic, alicyclic, aromatic hydrocarbons or a mixture thereof can be used as a solvent.

For example propane, butane, hexane heptane benzene toluene sodium are generally preferred.

In addition, this polymerization method uses conditions in which a solvent is substantially absent, i.e., gas phase polymerization in which ethylene and α-olefins are polymerized in the gas phase, and α-olefins are polymerized in liquefied α-olefin monomers. Ethylene or α-olefin polymers and copolymers can be produced by bulk polymerization.

In the method of the present invention, the polymerization activity of the catalyst used is extremely high, so when the polymer is produced by high-pressure gas phase polymerization or bulk polymerization, the amount of polymerization per titanium trichloride is much larger than in the known method. The processing method can be simplified, and since the particle sonic rate is low, the powder can be easily handled, and is extremely advantageous industrially.

The molecular weight of the polymer obtained by the method of the present invention varies depending on the reaction mode, catalyst system, and polymerization conditions, but can be controlled, if necessary, by adding hydrogen, alkyl halides, zinc dialkyl, etc., for example.

EXAMPLES In order to more fully explain the present invention, Examples are shown below, but the scope of the present invention is not limited by these in any way.

The polymerization activity of the catalyst was expressed as the polymerized amount of monomer per unit weight of titanium trichloride component per hour.

Example 1 The composition obtained by reducing titanium tetrachloride with aluminum in the presence of aluminum chloride in a nitrogen atmosphere in a vibration mill with an internal volume of 500 mm containing 1.2 kg of steel balls with a diameter of 12 mm was approximately 3 T. I C1l s・AlC1, 30 g of titanium trichloride/aluminum trichloride eutectic (hereinafter referred to as AA type ring titanium chloride) containing 3 parts by weight of titanium tetrachloride and 3.85 g of diphenyl ether (1 part by weight for titanium trichloride).
5 mol φ) was added thereto, and the first pulverization was carried out at 30° C. for 55 hours.

Then aluminum trichloride 1. stg (7.5 moles more than titanium trichloride) was added and second pulverization was performed at 30° C. for 5 hours.

The pulverized contents were separated from the steel balls under a nitrogen atmosphere to obtain a titanium trichloride composition.

This titanium trichloride composition 2El was mixed in a nitrogen atmosphere with a volume of 30
0 in a vertical four-eye flask, add 200 ml of heptane bubbled with nitrogen, and stir for 30 minutes at the boiling point, then 5
The washing process of allowing the mixture to stand for a minute and removing the supernatant by decanting was repeated four times, and finally, 200-heptane was added and the activated titanium trichloride composition slurry was stored.

In a 5US-27 autoclave with an internal volume of 21 cm, 11 cm of heptane, 460 cm of the above activated titanium trichloride composition, and 0.9 cm of diethylaluminum monochloride were added under a nitrogen atmosphere.
3rnl was charged.

Purge the nitrogen in the autoclave with propylene to 0.2
Charge propylene up to kg/C/L gauge.

Hydrogen was then charged to 0.8 to 9/crA gauge.

Heat the autoclave contents and bring the internal temperature to 7 after 5 minutes.
The temperature was raised to 0°C, and polymerization was continued at 70°C.

During polymerization, propylene is continuously pressurized to raise the internal pressure to 5 kg.
/crA gauge was maintained.

After 2.5 hours, the introduction of propylene is stopped, the autoclave is rapidly cooled, and unreacted propylene is discharged.

Add 290 TL of methanol and raise the temperature to 60°C.
Deactivation and decalcification were performed for 0 minutes.

Cool the autoclave, remove the contents and add heptane 5
001nI! was added, washed three times with 500 mA' of water at 60°C, filtered, and dried under reduced pressure at 60°C to obtain 487 g of white powdery polypropylene.

The intrinsic viscosity of the obtained powdered polypropylene was 1.64 (
Measured at 135°C in tetralin solvent, the same applies hereinafter.

) The bulk specific gravity was 0.43 g/mA', and the n-hebutane extraction residue was 98.3.

In addition, the fine particle content of powdered polypropylene of 200 mesh or less (hereinafter referred to as 200 mesh or less) is 2.1
It was heavy weight.

On the other hand, 7 g of non-quality polypropylene was obtained by evaporation of the filtrate.

Polymerization activity of the catalyst in the main polymerization reaction (expressed as the weight of polymerized monomer per hour per unit weight of titanium trichloride composition).

same as below. ) was 430.9/ghr. Example 2 Polymerization of propylene was carried out in the same manner as in Example 1 except that the first pulverization time was 40 hours and the second pulverization time was 20 hours.
The results are shown in Table 1.

Comparative Example 1 Propylene was polymerized in the same manner as in Example 1, except that the first pulverization time was 20 hours and the second pulverization time was 40 hours. The results are shown in Table 1.

Comparative Example 2 Diphenyl ether was added to 30 g of AA type titanium trichloride. s
Add sg (15 morda to titanium trichloride) and heat at 30°C.
The polymerization of propylene was carried out in the same manner as in Example 1 except that the mixture was pulverized for 60 hours and the second pulverization step was omitted. The results are shown in Table 1.

Comparative Example 3,4 Diphenyl ether was added to 30 g of AA type titanium trichloride. s
sg (15 molφ for titanium trichloride) and aluminum trichloride i, 5B (7.5 m for titanium trichloride)
Example 1 except that 4.57.9 (10 mol φ relative to titanium trichloride) or diphenyl ether/aluminum trichloride complex (1%) or diphenyl ether/aluminum trichloride complex was added and the mixture was ground at 30°C for 60 hours and the second grinding step was omitted. Polymerization of propylene was carried out in the same manner as above, and the results are shown in Table 1.

Comparative Example 5 Propylene polymerization was carried out in the same manner as in Example 1 except that the washing step was omitted, and the results are shown in Table 1.

Comparative Example 6 In Example 1, the additives added in the first pulverization step and the second pulverization step were replaced, that is, AA type titanium trichloride 3
Add 3.02 g of aluminum trichloride (15 mol based on titanium trichloride) to 0 g, grind at 30°C for 55 hours, then add 2.57 g of diphenyl ether (10 mol based on titanium trichloride), It was ground for 5 hours.

Polymerization of propylene was carried out in the same manner as in Example 1 except for this, and the results are shown in Table 1.

Comparative Example 7 Propylene was polymerized in the same manner as in Example 1 except that the order of the second pulverization step and the washing step was changed, and the results are shown in Table 1.

Examples 3 to 8 In Example 1, 1.68 g of ethyl ether (15 moles φ based on titanium trichloride) was used instead of diphenyl ether.
, or 2.16 g of methyl ethyl ketone (20 moles relative to titanium trichloride), or **2.0 g of ethyl acetate
(15 moles relative to titanium trichloride), or diethylthioether 2.049 (15 moles more than titanium trichloride), or diphenylthioether 3.37 g (2 moles more than titanium trichloride), or for nolphenyl phosphite 4.939C titanium trichloride, 10
Propylene polymerization was carried out in the same manner as in Example 1 except for adding molar ratio), and the results are shown in Table 2.

Examples 9 and 10 In Example 1, the amount of aluminum trichloride added in the second pulverization step was 2.01 g (1 g per titanium trichloride).
0 mole φ) or 3. o2g (1 for titanium trichloride
Propylene was polymerized in the same manner as in Example 1 except that the amount was changed to 5 mol@), and the results are shown in Table 3.

Example 11 In Example 1, aluminum trichloride-diphenyl ether complex 4.6. was used instead of aluminum trichloride added in the second grinding step. ! Propylene was polymerized in the same manner as in Example 1 except that 9 (10 moles more than titanium trichloride) was added, and the results are shown in Table 3.

Example 12 In Example 1, the amount of diphenyl ether added in the first pulverization step was 2.569 (l based on titanium trichloride).
0 molar ratio), and instead of the aluminum trichloride added in the second grinding step, 1.51 g of aluminum trichloride and 1.92 g of diphenyl ether (each 7 g for titanium trichloride) were used.
．． Polymerization of propylene was carried out in the same manner as in Example 1 except that a mixture of 5 moles of mol) was added, and the results are shown in Table 3.

Examples 13 to 15 Cleaning solvent used in the cleaning step in Example 1 * Polymerization of propylene was carried out in the same manner as in Example 1 except that benzene, toluene, or xylene was used instead of heptane, and the results are shown in Table 4. Ta.

However, washing was performed at the boiling point of the solvent used.

Example 16 The composition obtained by reducing titanium tetrachloride with aluminum in the presence of aluminum trichloride in Example 1 is approximately:
3 A titanium trichloride/aluminum trichloride eutectic containing titanium tetrachloride, which is TiCl a AlCl3, was dried at 200°C for 24 hours under reduced pressure (miHg), and the analysis value of titanium tetrachloride was a trace. Propylene was polymerized in the same manner as in Example 1, except that a titanium trichloride/aluminum trichloride eutectic containing no titanium tetrachloride was used.

The yield of powdered polymer was 448 g, the intrinsic viscosity was 1.73,
Bulk specific gravity 0.4297ml! The n-heptane extraction residue had a weight φ of 97.4, and the weight of amorphous polypropylene in the filtrate was 11.

The hebutane extraction residue of the total polymer was 94.9 weight φ.

In addition, the content of fine particles under 200 meshes in the polymer is 4
．． It was excellent by 1 weight.

The polymerization activity of the catalyst in the main polymerization reaction is 440 g/g・hr
Met.

Example 17.18 In Example 1, instead of the AA type titanium trichloride, titanium trichloride obtained by reducing titanium tetrachloride with hydrogen (hereinafter referred to as hydrogen-reduced titanium trichloride) was used.

) or titanium trichloride obtained by reducing titanium tetrachloride with diethylaluminum monochloride (hereinafter referred to as Hoechst type titanium trichloride).

) Polymerization of propylene was carried out in the same manner as in Example 1 except that the following was used, and the results are shown in Table 5.

Example 19 The activated titanium trichloride composition synthesized in Example 1 was used to carry out bulk polymerization of propylene.

A 5US-27 autoclave having an internal volume of 61 cm was charged with 0.2 g of the activated titanium trichloride composition suspended in 301 rLl of heptane and 0.8 yd of diethylaluminium monochloride under a nitrogen atmosphere.

After evacuating the nitrogen inside the autoclave using a vacuum pump, hydrogen was pumped out at 211. 2.5 kg of propylene was charged to the autoclave.

The contents of the autoclave were heated and after 10 minutes, the internal temperature was raised to 60°C and polymerization was carried out at 60°C.

After 5 hours, 20 TLl of methanol was added and stirred for 10 minutes to decompose the catalyst.

The autoclave was cooled with a fan, and the contents were taken out and dried under reduced pressure at 60°C to obtain 1038 g of polypropylene.

The intrinsic viscosity of the obtained polypropylene was 2.05, the bulk specific gravity was 0.429/cc, and the butane extraction residue was 93.8.
It was excellent.

Further, the fine particle content under 200 mesh was 19.

The polymerization activity of the catalyst in this polymerization reaction was 1038.9/! L
It was hr.

Example 20 46.4 g of the activated titanium trichloride composition synthesized in Example 1 and 72.3.9 g of diethylaluminum monochloride were charged into a 5US-27 autoclave with an internal volume of 2001 and 1001 heptane under a nitrogen atmosphere. was loaded.

Purge the nitrogen in the autoclave with propylene,
Propylene was charged to kg/c IIL gauge.

Next, hydrogen was charged up to 2.2 kg/cvi gauge.

After heating the contents of the autoclave for 30 minutes, the internal temperature reached 7
The temperature was raised to 0°C, and propylene polymerization was continued at 70°C for 2 hours.

During polymerization, propylene is continuously pressurized to maintain an internal pressure of 5 kg/
-Kept at gauge.

The gas phase hydrogen concentration during polymerization was 4.5 volumes.

Next, the internal temperature was lowered to 60°C, and after polymerization was carried out under residual pressure until the pressure reached 1 kg/i gauge, ethylene was charged and polymerization of ethylene was carried out at 60°C for 1 hour.

The internal pressure during polymerization was maintained at 1 kg/-gauge.

After the polymerization was completed, 241 ml of methanol was added and stirred for 60 minutes to decompose the catalyst, and the contents were washed with water.

The filterability in this case was very good.

The polymer was dried under reduced pressure at 60''C and the yield was 35.9 kg.

Intrinsic viscosity 2.0%, bulk specific gravity 0.40. The n-heptane extraction residue was 96.1%, and the concentration of valve-shaped polymer in the p liquid was 21g.
, #heptane.

The hebutane extraction residue of all the polymers was 92.5φ.

Further, the sound modulus of fine particles under 200 mesh in the polymer was 1.4.

Comparative Example 7 Propylene-ethylene nofloc copolymerization was carried out in the same manner as in Example 20, except that the titanium trichloride component of Comparative Example 3 was used as the titanium trichloride component in Example 19.

In this case, the filterability was very poor and the furnace cloth was replaced twice to complete the process.

The yield of powdered polymer was 36.6 kg.

The powder polymer had an intrinsic viscosity of 2.11, a bulk specific gravity of 0.39, an n-heptane extraction residue of 95.3%, and an amorphous polymer concentration in the p liquid of 26 g/7 tohepetane.

The hebutane extraction residue of all the polymers was 90.4.

Further, the fine particle content under 200 mesh of the polymer was 19.7.

Example 21.22 In Example 1, diisobutylaluminum monochloride was substituted for diethylaluminum monochloride.1.
46ml or 10TIL of triethyl aluminum
Polymerization of propylene was carried out in the same manner as in Example 1 except that the following was used, and the results are shown in Table 6.

Claims (1)

[Scope of Claims] 1. Titanium trichloride or a titanium trichloride composition in the presence or absence of titanium tetrachloride and at least one of the organic compounds containing a heteroatom shown in (a), (b), or (c) below.
(a) an organic oxygen-containing compound selected from ethers, ketones, and esters; (b) Organic sulfur-containing compounds selected from thioethers, thiophenols, and thioalcohols. G/→ Organic phosphorus-containing compound. Furthermore, at least one of aluminum halides, aluminum halide compositions, and complexes or reaction products shown below (aXbXc) is added and re-pulverized.
(a) aluminum halide; (b) at least one compound among organic compounds containing a heteroatom; and aluminum halide. (c) A complex or reaction product of a compound selected from organic compounds containing a heteroatom and aluminum halide. The pulverization time in the second pulverization step is shorter than the pulverization time in the first pulverization step. A method for polymerizing olefins, which comprises polymerizing or copolymerizing ethylene or α-olefin in the presence of a catalyst consisting of a titanium chloride composition and an organoaluminum compound.