CS221805B2 - Method of stereocopic polymeration of the alpha-olefine - Google Patents

Abstract

PURPOSE:To prepare the title polymer having high stereo-regularity, by polymerizing alpha-olefins in the presence of a highly active catalyst comprising an active titanium component treated with an aromatic ortho-carboxylic acid ester, an organo- aluminum compound, and an electrodonative compound. CONSTITUTION:A catalyst system for the polymerization of alpha-olefines, comprising (A) an active titanium component obtained by treating a co-crushed product of (a) a magnesium halide, (b) an aluminum halide, and (c) an aromatic ortho-carboxylic acid ester (pref. a compound II where R<1> is aromatic hydrocarbon, R<2> to R<4> are hydrocarbons, e.g. orthobenzoic acid methyl ester, etc.), (B) an organo-aluminum compound I (R is hydrocarbon; X is alkoxy, halogen, etc.; m is 1.5-3), and (C) an electron donor (e.g. organic acid ester, etc.).

Description

The invention relates to a process for the stereospecific polymerization of alpha-olefins.

It is known, and is now commercially, that alpha-olefins, such as propylene and butene, are polymerized in the presence of a so-called Ziegler-Natta carboxylator containing titanium tetrachloride and an organoaluminum compound to form a stureospecific poly-alpha-olefin.

To date, methods have been developed using the Ziegler-Natta titanium catalyst component. carriers to improve catalytic efficiency and are generally used for the polymerization of ethylene.

In the case of the polymerization of alpha-olefins such as propylene and butane, a usable crystalline polymer cannot be obtained until the polymer chain also has an isotactic structure in which the alkyl groups, such as methyl methyl, are specifically controlled. Therefore, catalysts improved only in the polymerization of ethylene can not be considered as a useful catalyst for the polyolefin and olefins and for which the regulation of the stereospecificity of the polymer is an important task.

Therefore, a method has been provided in which the electron donating compound is added as a third component to a carrier-type titanium compound having a titanium compound deposited on a magnesium halide and a aluminum compound, thereby improving the stereospecificity of the polymer.

For example, British patent <387 890 discloses catalysts comprising a mixture of titanium halide, organoaluminum and electron donating compounds, a titanium halide mixture prepared by grinding a magnesium halide with a titanium halide or grinding a titanium halide complex and an electron donating compound together with a magnesium halide.

However, these catalysts are still insufficient in terms of both the polymerization activity and the crystallinity of the polymers obtained.

It is an object of the invention to provide a process for stereospecific polymerization of alpha olefins, obtaining polymers of high stereospecificity with high polymerization activity. It is a further object of the invention to provide a carrier-type titanium component as a catalyst, to provide poly-alpha-olefins with improved polymerization activity and stereospecificity.

A process for the stereospecific polymerization of alpha-olefins using a supported catalyst consisting of a supported titanium compound, 1 to 500 moles of an organoaluminum compound and 0.5 to 200 moles of an electron donating compound, relative to one Ti atom of the titanium compound, is characterized as on the support, an activated titanium compound obtained by grinding magnesium halide, an aromatic orthocarboxylic acid ester of the formula

0R _o

I ² C-R-I ^J orn ¹ or ₄ wherein R is an aromatic hydrocarbon radical having 6 to 12 carbon atoms and R _2, R and R, which may be the same effort different, represent an aliphatic hydrocarbon radical having 1 to 10 carbon atoms, an aluminum halide and an organosilicon compound having at least one alkoxy group of the formula ^{a '0R} ₅ Wp where R₁ is an alkyl group having 1 to 6 carbon atoms, X and Ϊ is an aliphatic, alicyclic or aromatic hydrocarbon radical 3 1-6 carbon atoms , halogen or carbonyloxy group RCO,

Wherein R is an alkyl group having 1 to 6 carbon atoms, m is an integer of 1 to -4, n and p is 0 to 3, and the total of m, n and p is 4, and contacting the comminuted product with a thioan halide.

The magnesium halide which may be used in the preparation of the titanium component of the carrier type is preferably substantially anhydrous magnesium halide, and magnesium chloride is particularly preferred.

As esters of aromatic-ortho-carboxylic acids, derivatives of orthobenzoic acid esters or orthonaphthoic acid esters can be used. P ^ i ^ ^ i ^ architrave m meeylorthobenzooá these compounds, etylorthobenzooá, meeyyoothooolLuryát e ^; ^: ^ hotolu Lort ^]. Etylorthoanisát to ₉ and propylorthoaiisát.

In the process according to the invention, the aromatic orthocarboxylic acid esters are concealed, and no effects can be achieved with the use of the aliphatic orthocarboxylic acid esters; The amount of the aromatic ortho-octhoxyxylic acid ester is not limited, but a quantity of 0.05 to 0.3 mol per 1.0 mol of magnesium halides is preferred.

The aluminum halide that can be used in the preparation of the activated ttam catalyst component is preferably substantially anhydrous aluminum halide, and especially aluminum chloride is preferred.

The amount of halides is not aluminum, although 0.5-2.0 moles per 1.0 moles of the aromatic ortho-tetric acid ester is preferred.

An example of an organophosphorus compound is S ^ OC ^^ Cl, - Si (OC ₂ H ₅ ) ₂ Cl _2>

Si (OCOCH 3) (OC ₂ H 5) Cl ₂ , Si (OC ₂ H ₅ ) ₄ , Si (C ₂ H ₅ ) 2 (OC ₂ H 5) ₂ , Si (C ₆ H 5) (O ^ 5) 3 and the like are preferred such compounds that mmaí least two alkoxy groups such as HO ^ SiC ^^ JSB ^) ^ or Si (l ₆ H ₅₎ (θl2H5) з '

In particular, the organo-silicon compounds are non-critical, but a quantity of 0.05 to 0.15 mol per 1.0 mol of magnesium halide is preferred.

In order to prepare the activated tannin catalyst component, a powdered product is first formed by the cormination of magnesium halides, thiyl halides, an aromatic orthotarboxylic acid ester and an organo-silicon compound having at least one alkoxy group.

In this case, a preformed aluminum halide complex with an aromatic ortho-tricylic acid ester or a preformed reaction product of a halide precipitated with an aromatic ortho-trioxylic acid ester can be used instead of separately adding each component.

The change to powder can be carried out under vacuum or under an inert gas atmosphere and should be carried out in a substantially non-oxygen and moisture-free manner. The conditions are not particularly limited, but generally the temperature is in the range of 0 to 80 ° C. The grinding time depends on the type of grinding but normally ranges from 2 to 100 hours.

The powdered product thus obtained is then contacted with the halide. Examples of muzzle halides that may be used are titanium tetrachloride, titanium bromide and the like. Titanium tetrachloride is particularly preferred.

This contact is conveniently effected by suspending the above powdered product in a halide or as a solution in an inert solvent, at a temperature in the range of 0 to 135 ° C and then separating the solid, further drying or removing the free hetogenic pro221805. washing with an inert solvent to obtain the activated titanium component of the catalyst. By inert solvent is meant aliphatic) alicyclic or aromatic hydrocarbons or mixtures thereof.

According to the invention, the activated muzzle component obtained above is mixed with an organic carbon compound and an electron scavenger compound to form a high efficiency catalyst for alpha polymerization.

The inorganic compound which may be ingested has the general formula ^A1 MU wherein R is a hydrocarbon radical, X * is an alkoxy trace, hydrogen or a halogen atom, and m is

1.5 to 3.0.

Typical examples include tree extracts, tin-butylamine, trichloroaluminium, diethylmallium, diethylaluminiumoxide, diethylaluminum ethoxide, and the like. They can be used alone or in a mixture. The molar ratio of the carbonic compound to the thio-activated muzzle component is not limited, but the preferred range is 1 to 500.

Electron-doping compounds which may be used include phosphorus, oxygen or nitrogen containing compounds. The phosphorous-inhibiting compound can be represented by the general formula

P ^<Z 1>«<W3- neb0 wherein Z is hydrogen, hydrocarbyl, amino or quick match alkylíminhltopina, Ϊι kyssík is am or sulfur is 0 through 3.

The oxygen-containing compound may be represented by the formula

or z ₂ (coo ^z ₃ ) _K wherein ^z ₂ and Z 1 is a hydrocarbon radical or together may form a ring and K is 1 to 3.

The nitrogen containing compounds are amines or derivatives thereof. Preferably, organic acid esters and aromatic heptocarboxylic acid esters having the aforementioned formula are useful as electron-stabilizing compounds. Typical examples of an organic acid ester are methyl formate, ethyl acetate, ammonium acetate, methyl acrylate, methyleneearylate, methyl benzoate, ethyl benzyl, methyl methyl, and the like.

The electron detecting compound can be contacted with the other components at any time during the preparation of the catalyst. The electron-decomposing compound is formed. it may also add to the polymerization of alpha-olefins. Generally, the electron deflecting compound is added after contacting the activated muzzle component with the compound, the activated muzzle component is added after contacting the activated carbon component with the electron donor compound, hrgmihlinitt compound is added after contacting the activated muzzle component with the electron donating compound, or all three components are added. at the same time. It is particularly preferred that some or all of the electron-annealing compound is added upon contact of the activated titanium component with the organo-compound in the polymerization of the polymerizable monomers. The amount of the electron-doping compound is preferably in the range of 0.1 to 0.5 mol per 1.0 mol of the aluminum compound. When the amount exceeds 0.5 molar, the polymerization becomes difficult. alkalinity without further enhancing stereosepeificity.

The invention may be applied to the homopolymerization or copolymerization of the OLfa-olefins of the general formula

R 1 -CH = CH ₂ wherein R 1 is an alkyl group having 1 to 10 carbon atoms,. or copolymmeacC of the above alpha-olefin with ethylene.

Alpha-olefin is propylene, butene-1, hexene-1,4-ethylpentene-1 and the like.

The polymerization of the invention may be carried out in conventional manner under conventional conditions pooUiii polymerization te ^ OTA is ECN ^{b of} between ⁰ and ^{of the 100} ° C, preferably ²⁰ and ^{from 90} ° C and the pressure is in the range from normal pressure to 4.90 MPa , preferably in the range of non-linear pressure to 3.92 MPa.

In the polymerization reaction, a solvent such as an aliphatic, alicyclic or anemic hydrocarbon or a mixture thereof, such as propane, butane, pantane, hexane, heptane, cyclohexane, benzene, toluene, or a mixture thereof, may be used.

Block polymeran can also be used to kill liquid monomers as a solvent.

Alternatively, the gas phase polymerization reaction can be carried out, wherein the gaseous monomers are first contacted with the catalyst without using a solvent.

The molecular weight of the polymers produced by the process of the invention varies depending on the reaction method, type of catalyst, and polymerization conditions. Optionally, the monocular mortality can be controlled by adding, for example, hydrogen, an alkyl halide and a dialkylzinc to the reaction system.

The invention will be further elucidated in the following examples and comparative example.

Example a d 1

(a) 20 g of magnesium chloride, 5,6 g of CLCl 3, 4 ml of ethyl orthobenzate and 2 ml of tetraethyl chloride are placed in a vibratory OLin equipped with a 600-liter pot containing 80 0 mm steel balls and grinding for 40 hours .

g of the obtained pulverized product and 100 ml NaCl-thia niδtthhρ was charged to a 200 ml round bottom flask and stirred for 2 ^hours at ⁸⁰ ° C s and the ^ · ^ is poveto каладоо. ^P rt with ^{s p} o iedmináipbném repetition variables iooPívajíc MV 100 Ol stirring, n-heptane at 80 ° C for 15 einut ndáseddUící dekkaitaai and add another 100 el n-heptane to the / ivoHla slurry aktivovené tiannovt component.

a portion of the activated thiante component was sampled and analyzed after n-heptane was removed. The thioane content was 2.23 heeo. %. ^J

b) 65 mg of the above-mentioned muzzle component, 0.375 ml of trisodium chloride, 0.24 ml of diethyl chloro-thiociloride and 0.14 ml of ethyl betzoate are charged under nitrogen to aq. 3.0 liters of stainless steel fluid. After nitrogen gas from a vacuum pump is cut, hydrogen gas is introduced until the pressure is about 10,000 psi, and the pressure is then indicated. n until the vapor pressure is 0.196 MPa. The autoclave was removed and after 5 minutes the internal temperature was raised to 70 ° C.

The polymer was continued at 70 ° C for 1 hour, while maintaining the pressure at 50 psi. .

After cooling the autoclave, unreacted proplene is blown and the contents are separated, filtered and dried at 60 ° C under reduced pressure.

The results are shown in Table 1.

Example 2

Using the activated titno component obtained in Example 1a), the polymerization was carried out in the same manner as in Example 1b) except that 0.08 ml of methyl orthobenzoate and 0.18 ml of diethyl alimonyl chloride were used instead of 0.14 ml of ethyl benzoate and 0.24 ml of diethylamine amino chloride. .

The results are shown in Table 1.

Example 3

The activated mouthpiece was prepared in the same manner as in Example 1a) with the difference that 2 ml of ethyltetrahydrate was used instead of a tetrtetuxystem for pulverization. The tiaar content was 2.20 lmoo. %.

The polymerization was carried out in the same manner as in Example 1b) with the difference that 58 mg of the above-mentioned activated Uton component was offered.

The results are shown in Table 1.

Example 4

The active muzzle component was prepared in the same manner as in Example 1a) except that 4.0 µl of ethylorioobenzoate was used instead of meeylorhobenzoate to be pulverized.

Za pcou ^.! of the aforementioned muzzle component, the polymerization is carried out in the wall manner as in Example 1b). .

The results are shown in Table 1.

Example 5

The activated muzzle component was prepared via the wall as in Example 1a) except that 2 ml of methyl orthobenzoate and 6 mL of tetraetoKystlan were used to pulverize. The content of the printer was 3.2 lmoo. %.

The polymerization was carried out in the same manner as in Example 1b) except that 61 mg of the above-mentioned muzzle component was used.

The results are shown in Table 1.

Example a d 6

Using the thiam component obtained in Example 1 (a), a wall polymerization is carried out. as in Example 1b) with the difference that 0.25 mL of ttylbenzate was killed.

The results are shown in Table 1.

OJ м гЧ ti ХЗ со н

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Titanium component in the mouth. 3.48 wt. % was prepared in the same manner as in Example 1 by grinding 20 g of magnesium chloride and 6 ml of tetraethoxysilene and reacting with titanium tetrachloride and subsequent wicker with n-heptime.

Comparative example

Using 58 mg of the above muzzle component, 0.20 ml of ethyl benzoate and 0.5 ml of triethylaluminum, the polymerization was carried out in the same manner as in Example 1b) for one hour. '

69 g of powdered polypropylene and 2.1 g of n-heptane soluble polypropylene are obtained.

Powder XI (polymer extraction residue with boiling n-heptane): 95.8%

Sypná hmoUnnut: 0.30 g / mi Viscosity Limit Number: 1, 89 A ^^ ita: 35 kg / g TiH Unit II: 93.0%

Examples 7 and 8

Using the activated muzzle component obtained in Example 1a), the polymerization is carried out in the same manner as in Example 1b) except that the ratios of the catalyst components are varied.

The results are shown in Table 2.

Table 2

Ex. vaná Ti aluminum- Meeyltoiuyiát ml Tietylaluminim ml AActivity kg / g Ti.h (x) Total 11 XX) Bulk density g / mi Limit viscosity number mg chloride ml 7 30 0.24 0.12 0.20 240 94.0 0.34 1.82 8 300 0.03 0.01 0.02 25 95.1 0.35 1.79

In the tables above it means:

(x) polymerization activity of the catalyst (rate of polymer formation per g of activated titanium per hour); (xx) ratio of the extraction residue of boiling n-heptane polymer to total polymer.

Claims (2)

SUBJECT OF THE INVENTION CLAIMS 1. A process for the stereosphere-specific polymerization of .alpha.-olefins using a catalyst consisting of a muzzle compound supported on a carrier, from about 1 to about 500 moles of an organic compound, and from about 0.5 to about 200 moles of a compound having an airfoil. The electron relative to one atom of the Ti compound of the mouthpiece compound, characterized in that an activated mouthpiece compound obtained by grinding magnesium halide, an aromatic ester of an aromatic orthocarboxylic acid of the formula O1R I ² R, -C-OR., I ^J R ₄ where R 1 is an aromatic hydrocarbon radical having 6 to 12 carbon atoms and R 8, R 8 and R 8, which may be the same or different, denotes an aliphatic hydrocarbon radical having 1 to 10 carbon atoms, an aluminum halide and an organolkeinite compound having at least one alkoxy group of the formula Si _<5 ° ^R) _m Vp where R is an alkyl group having 1 to 6 carbon UH-magnesium, and X I is an aliphatic O-icyklický arommaický or hydrocarbon radical having 1 to 6 carbon UH-magnesium, halogen or carbonyloxy Wherein R is C 1 -C 6 alkyl, m is an integer from 1 to 4, n and p are 0 to 3, and the total of m, n and p is 4, and contacting the comminuted product with a thiohalide. 2. Process according to claim 1, characterized in that magnesium chloride is used as magnesium halide and aluminum chloride as aluminum halide.