JPH0280407A - Polymerization of olefin - Google Patents

Abstract

PURPOSE:To prepare a highly stereospecific polymer with a high yield by polymerizing olefins in the presence of a catalyst contg. a solid catalytic component contg. Ti, Mg and a halogen and a specified siloxane compd. CONSTITUTION:A catalyst for olefin polymerization is prepared from a solid catalytic component contg. Ti, Mg and a halogen as the essential component, an organoaluminum compd. and a siloxane compd. of the formula (wherein R<1>-R<4> are each a hydrocarbon residue; 0<=k<3; 0<=l<3; n is 0-20) (e.g., 1,3- dimethoxy-1,1,3,3tetraisopropyldisiloxane). A highly stereospecific olefinic (co)polymer can be prepd. with a remarkably high yield by using said catalyst.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a high-performance catalyst that exhibits a highly active action when used for the polymerization of olefins, and particularly for the polymerization of α-olefins having 3 or more carbon atoms. applied to. #A match.

The present invention relates to an olefin polymerization method using an olefin polymerization catalyst that allows highly stereoregular polymers to be obtained in high yields.

[Conventional technology]

Conventionally, esters (e.g., JP-A-48-16986) or 7-mer-type organosilicon compounds (e.g., JP-A-54-945) have been used as cocatalysts for supported Ziegler-type catalysts.
90, 55-:1620:l, 57-6:1312
) is well known.

However, according to our knowledge, in compounds where the number of 10-C bonds bonded to the silicon atom is one,
Only a significantly lower effect has been observed. Therefore, when trying to obtain high stereospecificity using such a compound, it is necessary to use a significantly large amount of the above-mentioned organosilicon compound, resulting in a significant decrease in polymerization activity and its steric properties. The regularity also had to remain at an insufficient value.

Halogen, which is one of the solid catalyst components, has the disadvantage of promoting corrosion of molding machines and the like during polymer processing. Therefore, in order to suppress the corrosive effect as much as possible, it is required to develop a catalyst that has high activity and high stereospecificity to the extent that the influence of halogen can be ignored even if the catalyst removal step is omitted.

(Problems to be Solved by the Invention) When attempting to obtain high specificity of the ketone by using an organosilicon compound as a cocatalyst of a supported Cheekler-type catalyst,
The above-mentioned organosilicon compound had to be used in a significantly large amount, resulting in a significant decrease in polymerization activity and the stereoregularity had to remain at an insufficient value. The purpose of the present invention is to solve this problem.

(Means for Solving the Problems) In light of the above, the present inventors have conducted intensive studies on co-catalysts to be used in supported Cheekler-type catalysts in order to obtain olefin polymers that solve these problems. In the method of producing an olefin (co)polymer by (co)polymerizing olefins in the presence of a catalyst, the catalyst used is (A) a solid catalyst component containing titanium, magnesium, and halogen as essential components; B) an organoaluminum compound, and (C) general formula (1).

(R'0)3-kl12bSi-0(SiOhandrl
SiR21(OR')ff-+ (1) (in the formula 11~
R' is a hydrocarbon residue. (These need not all be the same, and may be all or partially the same or all different.) k and l are O≦k<3 and 0≦, respectively.
1<3. n is.

It is a number from 0 to 20. As a result of olefin polymerization using a polymerization catalyst formed from a siloxane compound represented by

This effect is obtained through the use of a specific siloxane compound as a cocatalyst, especially an external donor, but it was unexpected that this specific siloxane compound would have such an effect.

The present invention will be specifically explained below.

Magnesium compounds used in the present invention include magnesium halides such as magnesium chloride and magnesium bromide; alkoxymagnesiums such as ethoxymacnesium and isopropoxymagnesium; magnesium laurate.

Examples include carbon # salts of magnesium such as stearinated magnesium; alkylmagnesiums such as butylethylmagnesium; Moreover, a mixture of two or more of these compounds may be used. Preferably, magnesium halide is used or magnesium halide is formed during catalyst formation. More preferably, it is the above-mentioned halogen or chlorine.

Examples of the titanium compound used in the present invention include those represented by the following general formula.

TiX'a(OR')J where x1 is a halogen, R5 represents a hydrocarbon group (generally having 36 or less carbon atoms), m and j are 0 to 4
, and 1+j is K to 4.

Specifically, titanium halides such as titanium tetrachloride, titanium trichloride, and titanium tetrabromide; titanium alkoxides such as titanium butoxide and titanium ethoxide.

Examples include alkoxytitanium halides such as phenoxytitanium chloride. Moreover, a mixture of two or more of these compounds may be used. Preferred are tetravalent titanium compounds in which x' is chlorine. Specifically, titanium tetrachloride, butoxytrichlorotitanium, tetrabutoxytitanium, etc. are mentioned.

The halogen used in the present invention is fluorine, chlorine, bromine, iodine, preferably chlorine, and the specific compounds actually exemplified include titanium tetrachloride, titanium tetrabromide, etc., depending on the catalyst yJ manufacturing method. Typical examples include silicon halides such as titanium halides, silicon tetrachloride, and silicon tetrabromide, and phosphorus halides such as phosphorus trichloride and phosphorus pentachloride, but depending on the preparation method, halogenated hydrocarbons, Halogen molecules, hydrohalic acids (e.g. HC, HBr,
old etc.) may be used.

These may be common to titanium compounds and magnesium compounds.

When producing the solid catalyst component (A) used in the present invention, various electron donors (internal toners) may be added.

Examples of electronic annual leave include oxygen-containing compounds and nitrogen-containing compounds. More specifically, (a) methanol 2
Ethanol, propatool, phthanol, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, 2-ethyl-hexyl alcohol, benzyl alcohol, cumyl alcohol, diphenylmethanol, triphenylmethanol, etc. with 1 carbon number
to 20 alcohols, (b) phenols with carbon fi 6 to 25 which may have an alkyl group such as phenol, cresol, ethylphenol, propylphenol, cumylphenol, nonylphenol, naphthol, (c) acetone, methyl ethyl ketone, Ketones having 3 to 15 carbon atoms, such as methyl isotutyl ketone, acetophenone, benzophenone, and cyclohexanone.

(d) Charcoal such as acetaldehyde, propionaldehyde, tolualdehyde, naphthaldehyde, and aldehydes of number 2 to 15, (e) Methyl formate, ethyl formate,
Methyl acetate, ethyl acetate, propyl acetate, octyl acetate, cyclooctyl acetate, methyl cellosolve acetate, cellosolve acetate, butyl cellosolve acetate, ethyl propionate 2 n-methyl butyrate, ethyl isoacetate, ethyl isoacetate, isopropyl isobutyrate, ethyl valerate , butyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl methacrylate,
Ethyl crotonate, ethyl cyclohexanecarboxylate,
Ethyl phenylacetate, ethyl phenyl acetate, propyl phenyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, ammonium,
Cyclohexyl 9oate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate phthalate diisobutyl phthalate, diheptyl phthalate, cineobentyl phthalate, γ-phthyrolactone.

γ-valerolactone, coumarin, phthalide, diethyl carbonate, orthotrimethyl, ethyl orthoformate and other organic acid esters of carbon a2 to 2o, methyl borate, ethyl borate, ethyl silicate, butyl silicate, Inorganic acid esters such as butyl titanate, butyl phosphate, triethyl phosphite, diethyl phosphite, di(2-phenylphenyl) phosphorochlororizoite, (t)methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol dimethyl ether 4 ethylene glycol diethyl ether,
Ethers having 2 to 25 carbon atoms such as ethylene glycol diphenyl ether and 2,2-dimethoxypropane, (th) amides having 2 to 20 carbon atoms such as acetic acid amide, benzoic acid amide, and toluic acid amide, and (su) acetyl. Acid halides having 2 to 20 carbon atoms such as chloride, benzoyl chloride, toluic acid chloride, anisyl chloride, phthaloyl pentachloride, and phthaloyl isochloride; acid anhydrides having 2 to 20 carbon atoms such as acetic anhydride and phthalic anhydride; monomethylamine, monoethylamine, diethylamine.

Tributylamine, piperidine, tribenzylamine,
Amines having 1 to 20 carbon atoms, such as aniline, pyridine, picoline, and tetramethylethylenediamine;
Nitriles having 2 to 20 carbon atoms such as acetonitrile, benzonitrile, and trinitrile; (i) thiols having 2 to 20 carbon atoms such as ethylthioalcohol, butylthioalcohol, and phenylthiol; (c) diethylthioether, diphenylthioether, etc. carbon number 4
to 25 thioethers, (yo)dimethyl sulfate.

Sulfuric acid esters having 2 to 20 carbon atoms such as diethyl sulfate, sulfonic acids having 2 to 20 carbon atoms such as phenylmethylsulfone and diphenylsulfone, (c) phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxy. Silane, vinyltriethoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, phenyldimethylmethoxysilane, phenyldimethylmonoethoxysilane, triphenylmethoxysilane, hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, Examples include silicon-containing compounds having 2 to 24 carbon atoms, such as trimethylsilanol, phenyldimethylsilanol, triphenylsilanol, diphenylsilanediol, and lower alkyl silicate (especially ethyl silicate).

Two or more types of these electron-donating compounds can be used. Among these, preferred are organic acid esters, No 41! ! These include acid esters.

Although the catalyst 1JJtA method used in the present invention is not particularly limited, the following examples can be given.

A method of obtaining a catalyst component by bringing magnesium halide, titanium halide, and the above electron-donating compound into contact with each other by co-pulverization or by dispersing or dissolving in a solvent.

A method of obtaining a catalyst component by making a composite of magnesium halide and an organic or inorganic compound (which may include the above-mentioned electron-donating compound), and contacting this with titanium halide or a complex of it and the above-mentioned electron-donating compound. .

A complex of magnesium halide and an organic or inorganic compound (which may include the above electron donating compound) is made, and the above electron donating compound and titanium compound are sequentially contacted with the complex (the order may be changed). ) to obtain the catalyst component.

A method of obtaining a catalyst component by contacting the magnesium compound eJ (or further containing a titanium compound) with the electron-donating compound, and simultaneously or at a subsequent stage contacting with a titanium compound and/or carrying out a halogenation treatment (either step containing the use of titanium compounds).

The above catalyst component may be produced by supporting or impregnating it on a material commonly used as a catalyst carrier, such as silica or alumina.

The quantitative relationship of each component in component <A) is arbitrary as long as the effect of the present invention is recognized, but - quantitatively, the following range is preferable. The content may be in the range of 0.1-1000 in molar ratio to titanium, preferably in the range of 2 to 200, and the content of halogen may be in the range of 1 to 10 in molar ratio to titanium. When a compound is used, its content may be in the range of IO or less, preferably in the range of 0.1 to 5, in molar ratio to titanium.

The organoaluminum compound in the present invention is represented by the following formulas (2) to 4) as typical general formulas.

A or R9R6R?・・・・・・・・・(2) R'R'Across-〇-A sentence) 110R11・・・・・・・・・
...(3) In formulas (2), (3) and (4), Is, R6 and R7 may be the same or different, and are hydrocarbon groups, halogen atoms or hydrogen atoms having at most 12 carbon atoms. However, at least one of them is a hydrocarbon group R6, f+9. RlG and R1 may be the same or different, and are hydrocarbon groups having at most 12 carbon atoms.

Further, R12 is a hydrocarbon group having at most 12 carbon atoms, and n is an integer of 1 or more.

Typical organoaluminum compounds represented by formula (2) include trialkylaluminum such as triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum and trioctylaluminum, as well as diethylaluminum hydride and diisobutylaluminum. Mention may be made of alkyl aluminum hydrides such as aluminum hydrite and alkyl aluminum halides such as diethylaluminum chloride, diethylaluminum furomite and ethylaluminum sesquichloride.

Further, among the organoaluminum compounds represented by the formula (3), representative examples include alkylalumoxanes such as tetraethylsialumoxane and tetrabutyldialumoxane.

Further, formula (4) represents aluminoxane, which is a polymer of an aluminum compound. R12 is methyl, ethyl,
It includes propyl, butyl, pentyl, etc., but methyl and ethyl groups are preferred. n is preferably 1 to IO.

Among these organoaluminum compounds, trialkylaluminum, alkylaluminum hydride and alkylalumoxane are preferred because they give particularly favorable results.

In the polymerization of olefins, the amount of organic aluminum used in the polymerization system is generally 10 mmol/or more, preferably 10-' mmol/or more. Furthermore, the molar ratio of the titanium atoms used in the solid catalyst component is generally 0.5 or more, preferably 2 or more,
In particular, 10 or more is preferred. In addition, if the amount of organoaluminium used is too small, it will lead to a significant decrease in 1 polymerization activity.Please note that if the amount of organoaluminum used in the polymerization system is 20 mmol or more and the ratio to titanium atoms or 1 molar ratio is In the case of 1000 or more, even if these values are further increased, no further improvement in catalyst performance is observed.

Component (C) of the catalyst used in the present invention is - large amount (1)
It is a siloxane compound having a structure represented by the formula.

Rco(R'O):+-bR"hSi-0[SiO]n
5iR''+(OR')i-+ (+) In the formula, R1 is a hydrocarbon residue, preferably an aliphatic hydrocarbon residue having 1 to 6 carbon atoms, and more preferably a straight chain aliphatic residue having 1 to 3 carbon atoms. Specifically, examples include methyl, ethyl, propyl groups, etc. All R's do not have to be the same, and they may be all or partially the same or all different. Good too.

R2 is a hydrocarbon residue having 1 to 20 carbon atoms, preferably a hydrocarbon residue having 4 to 20 carbon atoms, more preferably aromatic,
It is a substituted aromatic, aliphatic or alicyclic hydrocarbon residue or a branched hydrocarbon residue. The substituent of the substituted aromatic group described in (g) is selected from an alkyl group, a halogen group, an alkoxy group, and the like. Specific examples include phenyl, 2-methylphenyl, 4-fluorophenyl, 2.6-dimethylphenyl, 4-methoxyphenyl cyclohexyl, 2-methylcyclohexyl, methyl, ethyl, propyl, isopropyl,
These include butyl, isobutyl, secondary butyl, tertiary butyl, neopentyl, norbornyl norbornane. All R2s do not have to be the same, and they may be all or partially the same or all different.

R3 and R4 are a hydrocarbon residue having 1 to 20 carbon atoms or a hydrogen atom, preferably a hydrocarbon residue having 1 to 8 carbon atoms or a hydrogen atom. Specific examples include phenyl, cyclohexyl, methyl, ethyl, propyl, isopropyl, butyl,
These include isobutyl, secondary butyl, tertiary butyl, and hydrogen atoms. R' and R' do not need to be all the same, and may be all or partially the same or all different.

n is a number from 0 to 20, preferably from 0 to 1
It is the number of 0.

, I is a number with 0≦k<3 and 0≦1<3, respectively, preferably 0≦≦2 and 0≦1, respectively
The number is ≦2.

Conventional 100-mer type organosilicon compounds exhibit extremely low stereospecificity in structures corresponding to a k value of 2, but the siloxane compounds of the present invention exhibit extremely high stereospecificity. .

Specific examples of such compounds are those shown by the structural formula below.

(CIlzO):+SiO5i(QC:H:
+)z(C211,0)z Si O5i(OC
2tls): +The amount of component (C) used is 1 molar ratio of component (
C)/component (B) =0. old ~5, preferably 0.02
~l.

The olefin used for polymerization is generally an olefin having at most 12 carbon atoms.

Typical examples are ethylene, propylene, butene.
Examples include 1,4-methylpentene-1, hexene-1, and octene-1. In carrying out the polymerization, these olefins may be homopolymerized, but two or more types of olefins may be copolymerized (for example, ethylene and propylene are copolymerized). The solid catalyst component, the organoaluminum compound, or these and the silicon compound may be introduced individually into the polymerization vessel, or two or all of them may be mixed in advance.

Polymerization can be carried out either in an inert solvent, in a liquid olefin, or in the gas phase. Also,
In order to obtain a polymer having a practical melt flow, a molecular weight regulator (generally hydrogen) may be present.

The polymerization temperature is generally from -10°C to 180°C, and practically from 20°C to 130°C.

Pre-(#Polymerization 1) Regarding the shape and condition of the polymerization reactor, polymerization control method, post-treatment method, etc.

There are no limitations inherent to this catalyst system, and all known methods can be applied.

(Example〕 Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, in the examples and comparative examples, the heptane index (i.e., 11.R,) is mn-hebutane,
The amount remaining after extracting the obtained polymer for 6 hours is expressed in %.

In each example, all of the compounds (organic solvent, olefin, hydrogen, titanium compound, magnesium compound, silicon compound, etc.) used in the production and polymerization of the solid catalyst component were substantially free of moisture.

Furthermore, the manufacturing method and polymerization of the solid catalyst component were carried out in the absence of substantial moisture and in a nitrogen atmosphere.

(Example 1) Preparation of solid Ti catalyst component (A) 1.17 g of anhydrous magnesium chloride, 9 tan of decane and 8.411 n of 2-ethylhexyl alcohol were mixed into 13
After heating and reacting at 0°C for 2 hours to obtain a homogeneous solution, 0°39g of anhydrous phthalate was added to this solution.

1: Stirring and mixing is further performed at 10° C. for 1 hour to dissolve phthalic anhydride into the homogeneous solution. After the homogeneous solution thus obtained was cooled to room temperature, the entire amount was dropped into titanium tetrachloride 72 tan maintained at -20°C over 1 hour. After charging, the temperature of this mixture was increased to 1 over 4 hours.
The temperature was raised to 10°C, and when it reached 110°C, 0.96 tan of diisobutyl phthalate was added, and the mixture was stored at the same temperature for 2 hours with stirring. After 2 hours of reaction, the solid portion was collected by 8 filtration, and this solid portion was collected with 72 × TiC! ; After resuspending in L4, heating reaction is performed again at 110°C for 2 hours.

After the reaction was completed, the solid portion was collected again by hot filtration and heated to 110°C.
After thorough washing with decane and hexane until no free titanium compounds are detected in the washing solution.

Dry under reduced pressure.

(Polymerization) In a 1.52 stainless steel autoclave, 20 mg of the solid component produced by the above method, 22.2 mg of 1,3-dimethoxy-1,1,:l,:I-tetraisopropyldisiloxane, and triethyl were added. Aluminum 91IIg
then 340 g of propylene and 0.0:I
g of hydrogen was added.

The temperature of the autoclave was raised and the internal temperature was maintained at 70°C. 1
After a period of time, the content gas was released to terminate the polymerization. Result 1
15.8 g of polypropylene powder was obtained with 0 polymerization activity of 5790 g/g solids content/hour. The hebutane extraction residue (H, R,) of this polypropylene powder is
It was 95.8%.

(Comparative Example 1, Examples 2 to 4) Catalyst preparation and polymerization were carried out in the same manner as in Example 1, except that the type of catalyst component (C) used and the amount used were changed as shown in Table 1. .

The results are shown in Table-1.

(Left below) (Example 5) Production of solid catalyst component (8) 20 g of anhydrous magnesium chloride and 7 g of benzoyl chloride were placed in 11 cylindrical containers filled with a 10 m5 diameter porcelain ball at an apparent 50% capacity. Co-pulverization was carried out for 12 hours using a vibrating mill with a vibration width of 9 mm.

Separately, in a flask containing 500 ann, 120 layers of toluene, 83 g of titanium tetrachloride, and 65 g of di(2
-phenylphenyl) phosphorochlororizoite was added and reacted, and heated to 60°C to form a homogeneous container. The above-mentioned co-pulverized solid material was added to this solution and stirred at a temperature of 60°C for 2 hours.

After the solid content was separated in a furnace, it was washed with toluene and dried at 30°C under reduced pressure to obtain a solid.

(Polymerization) Using the above solid component (A), 1,3-dimethoxy-1,
1,:l,:l-tetraisopropyldisiloxane (C
), 22.2 g of triethylaluminum (B)
When propylene was polymerized under the same conditions as in Example 1 using 91 g of the above solid component (A) and 20 mg of the above solid component (A),
Polymerization activity is 4530g/g solid component/time, 11.
R, 94.8%.

(Example 6) 7 mg of the solid component obtained in Example 5 and 1 part of triimbutylaluminum were placed in a 1.5N stainless steel autoclave.
50■gt 1. :l-dimethoxy-1,1,3,3
15.5 g of -tetraisopropyldisiloxane was added, followed by 400 g of isobutane, and the mixture was stirred at 70°C.

Hydrogen was added to this solution at a partial pressure of 2 kg/crIT'. Furthermore, ethylene was added to the reactor so that the partial pressure was 5 kg/cm', and ethylene was continued to be supplied to maintain this pressure.

After 1 hour, the content gas was purged to complete the polymerization.

158 g of white odorless polyethylene was obtained. Activity is 225
The solid content was 71g/g/time.

〔Effect of the invention〕

As described above, it can be seen that by the method of the present invention, olefin (co)polymers with extremely high stereoregularity can be obtained in extremely high yields. It enables manufacturing.

[Brief explanation of the drawing]

FIG. 1 is a flowchart for preparing the catalyst according to the present invention.

Claims (1)

[Claims] In the method for producing an olefin polymer by polymerizing olefins in the presence of a catalyst, the catalyst used is (A
) a solid catalyst component containing titanium, magnesium, and halogen as essential components; (B) an organoaluminum compound;
and (C) General formula (1), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R^1 to R^4 are hydrocarbon residues. (These must all be the same. ) k and l are each 0≦
k<3 and 0≦l<3. n is a number from 0 to 20. ) A method for polymerizing an olefin, characterized in that it is formed from a siloxane compound represented by