CS221804B2 - Method of sterescopic polymeration of the alpha-olefine - Google Patents

Abstract

PURPOSE:To polymerize an alpha-olefin having a high stereoregularity, by using a highly active catalyst comprising a specific active titanium component and an organoaluminum compound. CONSTITUTION:A magnesium halide and an aromatic orthocarboxylic ester of the formula (R<1> is aromatic hydrocarbon residue; R<2>; R<3>, and R<4> are the same or different hydrocarbon residues) are pulverized at 0-80 deg.C for 2-100 hr simultaneouely suspend in TiCl4 or its inert solution, and subjected to contact reaction at 0-135 deg.C. Free TiCl4 is then removed from the reaction mixture to give an active titanium component (A). An alpha-olefin is polymerized in the presence of a catalyst comprising the component (A) and an organoaluminum compound of the formula Al R3 X3-m (R is hydrocarbon residue; X is alkoxy group; H, or halogen; 1.5<=m<=3) at 0-100 deg.C and a pressure of normal one to 50 atm.

Description

The present 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 either, are polymerized with the presence of a so-called Zlegler-Natta catalyst containing titanium (III) -tride and an organo-compound to form a stereospecific gas. -olefin.

So far, methods have been developed using! In the case of the polymerization of alpha-olefins such as propylene and butane, it is not possible to obtain a rechargeable, crystalline polymer until the polymer chain has an istectic structure in which The alkyl groups, such as methyl or ethyl, are substituted. Then, the catalysts can not only improved the polymerization activity of ethylene píulyraeracr considered e ^<ouUítrlný catalyst for the polymerization of alpha - oL ^ ii ^ '10 d. ^. For tn, the regulation of the polymer sterility is important.

Therefore, a method has been provided in which the electron withdrawing compound is added as a third component to the team mixture. - of the carrier type having a muzzle compound deposited on magnesium halide and organoH1; compound, thereby improving the stereo-sensitivity of the polymer.

For example, British Patent No. 1 387 890 discloses catalysts containing a mixture of a tungsten halide, a compound of the compound and a dispensing electron, a tium halide mixture is prepared by grinding magnesium halide with a thiahal halide or grinding the thiol complex. the compounds redden the electron together with the magnesium halide.

however, these catalysts are still inadequate in terms of the activity and crystallinity of the polymers obtained.

It is an object of the present invention to provide a process for the structuring of polymers of .alpha.-olefins, obtaining polymers of high stereo-opacity with high polymerization activity. It is another object of the present invention to provide a carrier component of the carrier type as a catalyst, to provide ethers of ethoxy-olefins with improved polymerization activity and stereolpecificity,

The process of the steroidal polymerization of alpha-olefins, with the aid of a catalyst consisting of a muzzle compound deposited on it, between 1 and 500 moles of the organo-compound and between 0.5 and 200 moles of the compound yields an electron relative to it. The Ti atom of the clan compound is characterized in that an activated muzzle compound obtained by the comminuted magnesium tetrachloride and the armatic β-octuboxylic acid ester of the formula

Rj-C-ORj where R, is an aromatic hydrocarbon radical having from 6 to 12 carbon atoms, and R 6, R 6 and R 6, which may be the same or different, denote an aiphatic hydrocarbon radical having 1 to 10 carbon atoms, and contacting the comminuted product with the muzzle halide.

The magnesium halide which can be encountered in the preparation of the carrier-type thiol component is preferably a substantially anhydrous magnesium halide, and in particular, magnesium hydroxide is preferred.

As aromatic orthocarboxylic acid esters, derivatives of orthobenzoic acid or orthonaphthonic acid ester may be used. Examples of these compounds. It is melyl orthobenzoate, ethyl orthobenzoate, methyl orthotholuyate, ethyl orthotuluylate, ethyl orthoanisate and propyl acetate.

In the process according to the invention, aromatic ortho-tricyclic acid esters are used, with the use of esters of a α-aliphatic ortho-trichloric acid, no effect can be achieved, as shown in Comparative Example 3. advantageous mn ^ sv! 0.05 to 0.3 mol per 1.0 mol of magnesium halide.

To prepare the activated muzzle component of the catalyst, a pulverulent product is first formed by combining magnesium halide and an aromatic ester of the first acid.

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

The comminution to a powder may be carried out under vacuum or under an inert gas atmosphere and should be carried out essentially in the absence of oxygen and vltkorsi. Stands 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 shredder, but normally ranges from 2 to 100 hours.

Next, the powdered product thus obtained is contacted with the tium halide. An example of a titanium halide that can be used is titanium tetrachloride, titanium bromide and the like. Titanium tetrachloride is particularly preferred.

This contact is carried out suitably suspension of the above powder-th product of the pontine ^d u Шепш Neto Jato rosettes in ^and inert, ^m rrzpru ⁱⁿ T ^E by ^at te ^ OTE within the range of ^{0 to} 135 ° C and then separating the solid, followed by drying, or removing the free thiium halide by washing with an inert solvent to obtain the activated muzzle component of the catalyst. By inert solvent is meant alpha-aromatic, tlcilic or arubbic hydrocarbons or their emmision.

According to the invention, the above activated activated component is admixed with an oxygen-containing compound and an electron-reducing compound to form a high efficiency catalyst for the polymerization of alpha-olefins.

The other compound which may be used has the general formula wherein R is a hydrocarbon radical, X * is an alkoxy group, hydrogen or a halogen atom and m is

1.5 to 3.0.

Typical examples include, but are not limited to, r, ^^, Уyayaiumiumiumiumiumiumiumium^^iumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumiumium ^{d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d} . They can be used alone or in bulk. The molar ratio of the active compound to the muzzle of the activated muzzle component is not limited, but the preferred range is 1 to 500.

Electron donating compounds which may be ingested include phosphorus, oxygen or nitrogen containing compounds. Ub8tariící phosphorus compound may vyjáddit formula ^p <ww ₃ - _or

Where Zj is hydrogen, a hydrocarbon radical, an amino or an alkylamino group, Y ^ is oxygen or sulfur and m is 0 to 3;

The oxygen-containing compound may be represented by the formula

or

Z ₂ (COOZ ₃ ) _K where Z ₂ and Z ₃ is a hydrocarbon residue or together may form a ring and k is 1 to 3 ·

An example of a nitrogen-containing compound is amines or derivatives thereof. Preferably, organic acid esters and aromatic orthocarboxylic acid esters having the above formula are used as electron delivery compounds. Typical examples of an organic acid ester are methyl formate, ethyl acetate, amyl acetate, methyl acrylate, methyl methacrylate, methyl benzoate, ethyl benzoate, methyl toluylate, methylanisate and others.

The electron delivery compound can be contacted with the other components at any time during the preparation of the catalyst. The electron donor compound may also be added when polymerizing alpha-olefins. Generally, the electron donor compound is added after contacting the activated titanium component with the organoaluminum compound, the activated titanium component, and adding the organoaluminum compound to the electron donating compound after contacting the organoaluminum compound. titanium components with the electron donating compound or all three components are added simultaneously. It is particularly preferred that some or all of the electron delivery compound is added upon contact of the activated titanium component with the organoaluminum compound to polymerize the polymerizable monomers. The amount of electron delivery compound is preferably in the range of 0.1 to 0.5 mol per 1.0 mol of the organoaluminum compound. When the amount exceeds 0.5 moles, the polymerization activity suddenly decreases without further increasing the stereospecificity.

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

R 1 -CH 2 CH 8 wherein R 1 is an alkyl group of 1 to 10 carbon atoms, or copolymerization of the above alpha-olefin with ethylene.

Examples of alpha-olefin are propylene, butene-1, hexene-1,4-methylpentene-1 and the like.

The polymerization temperature is generally in the range of 0 to 100 ° C, preferably 20 to 90 ° C and the pressure is in the range of normal pressure to 4.90 MPa, preferably in the range of normal pressure up to 3.92 MPa.

A solvent such as an aliphatic, alicyclic or aromatic hydrocarbon or a mixture thereof, for example propane, butane, pentane, hexane, heptane, cyclohexane, benzene, toluene or mixtures thereof may be used in the polymerization reaction.

Block polymerization using liquid monomers as solvent can also be used.

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

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

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

Example 1

(a) 20.0 g of magnesium chloride and 6 ml of methyl orthobenzoate shall be charged under a nitrogen atmosphere into a vibratory mill equipped with a 600 ml pot containing 80 mm balls of 12 mm diameter and crushed for 20 hours .

g of the powdery product thus obtained and 200 ml of titanium tetrachloride are filled into a 300 ml round-bottom flask and stirred at 80 ° C for 2 hours and then decanted.

Then, after seven washes of 30 ml mixing with 200 ml of n-heptane at room temperature and then decantation, an additional 200 ml of n-heptane is added to obtain a slurry of activated titanium component · a portion of the slurry is sampled and analyzed after evaporation of n-heptane. The titanium content of the activated titanium component was 1.50 wt.

(b) 1.01 n-heptane, 0.1 g of the above activated titanium component, 0.375 ml of triisobutylaluminum, 0.18 ml of diethylaluminum chloride and 0.08 ml of methylorthobenzoate are charged to a 3.0 L stainless steel autoclave under nitrogen. · After suction of nitrogen gas from the autoclave by means of a vacuum pump, hydrogen gas is introduced until the partial pressure is 0.0098 MPa and then propylene is introduced until the vapor pressure is 0.196 MPa. The autoclave was heated and after 5 minutes the internal temperature was raised to 70 ° C.

The polymerization was continued for one hour at 70 ° C while propylene was introduced to maintain the pressure at 400 psig.

After cooling the autoclave, unreacted propylene is purged and the contents are removed, filtered and dried at 60 ° C under reduced pressure.

85.4 g of white powdered polypropylene is obtained. Viscosity Limit Number (135 ° C, tetralin): 1.98; bulk density: 0.33 g / ml; extraction residue of boiling n-heptane polymer (hereinafter referred to as "powder II"): 92,7% ·

On the other hand, 4.8 g of n-heptane-soluble polymer are obtained. The ratio of the boiling n-heptane boiling polymer residue to total polymer (hereinafter referred to as "whole II") is 87.8%.

The polymerization activity of the catalyst in this example was 60 kg / g.Ti.h (polymer formation rate per gram of activated titanium per hour).

Comparative Examples 1 and 2

Using 26.4 g of magnesium chloride and 3.6 g of titanium tetrachloride, the titanium component is prepared by grinding in the same manner as in Example 1a).

The polymerization was repeated in the same manner as in Example 1b) except that 0.2 g of the titanium component obtained above, 0.1 ml of trithylaluminum and ethyl benzoate were used as the third component. The results are shown in Table 1.

Comparative example

According to the procedure described in Example 1a), the mouth component is obtained. content Шети

2,5 hmoo. 20 g of magnesium chloride and 6 ml of ethyl orthoacetate are then ground, followed by reaction with thialium lithium followed by n-heptide.

Using the above-mentioned thiawi component, 0.375 ml of trisoobutyl aluminum, 0.18 ml of diethyl aluminum chloride and 0.08 ml of methyl orthobenzoate, polymerization is carried out in the same manner. as in Example 1b) for 2 hours.

Comparative Example 4

A titanium component having a mole content of 3.0% by weight was prepared by grinding 23.6 g of magnesium chloride and 6.4 g of the lithium chloride ethyl ethyl benzoate complex as described in Example La).

Using the above tannin component and 0.1 ml of triethylamine, the polymerization is carried out in the same manner as in Example 1b).

After 2 hours of polymerization, it is obtained. 110 g powdered polypropylene ·

Prážek II: 70.3%

Viscosity Limit Number: 1,80

Bulk density: 0.22 g / ml

On the other hand, 30.5 g of non-crystalline polypropylene are obtained from the filtrate

Unit II ·

Polymerization activity:

Polymer yield:

55.0%

11.7 kg / g of Ti, h

23.4 kg / g Ti

Comparative example

Following the procedure of Example 1a), a ternal component of 1.21 hmo ·% muzzle was obtained by grinding 24.7 g of magnesium chloride and 5.3 g of ethylbenzorium, followed by reaction with chloride 1 1 (01x6 0 0 followed by n-heptern flushing). ·

Polymerization was carried out in the same manner as in the example, with 0.20 g of the above-obtained muzzle component and 0.07 ml of triethylallinite. 1b) for 2 hours. 218 g of powdered polypropylene and 25 g of n-heptane soluble polypropylene are obtained.

Prážek II:

Loose hmoOnott:

Viscosity Limit Number: Polymerization Activity: Whole II:

%

0.28 g / ml

1.98

1 kg / g Ti.h

85.2%

Table 1

Comparative example number Ethyl benzoate 8 Polymerization time h Polypropylene powder 8 Nekrys- Activity Yield Total II Limit viscosity number Bulk density g / ml talc kg / g Ti poly- propylene yield g kg / g Ti % 1 0.02 2 62 5 5,6 11.2 83.2 1.55 0.20 2 0.05 2 30 3 2,8 5.5 82.8 1 »71 0.22

Example 2

Using the catalyst component obtained in Example 1a), the polymerization was carried out in the same manner as in Example 1b) except that ethyl benzoate was used instead of methylopthobenzoate as the third component added in the polymerization.

The results are shown in Table 2 ·

Examples 3 to 6

The activated titanium component was prepared using different aromatic orthocarboxylic acid esters instead of the methyl orthobenzoate used to prepare the activated titanium component in Example 1a).

Using the activated titanium component thus obtained, propylene polymerization is carried out in the same manner as in Example 1b).

The results are shown in Table 2.

^EXAMPLE 1 к _AD7

Using 0.1 g of the activated titanium component obtained in Example 1a), 0.1 ml of ethyl benzoate and 0.3 ml of diethyl aluminum ethoxide, the polymerization was carried out in the same manner as in Example 1b).

The results are shown in Table 2.

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Aromatic orthocarboxylic acid esters added to prepare the activated Ti component

221604

Examples 8 and 9

Using the activated muzzle component obtained in Example 1a), 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 3.

Table 3

К ⁴ . C. Activated Ti component mg DiethylaluminiumclhLurtd Meeyitoluviát Trietylaluminiím Activity kg / g Ti h Total 11% Bulk density g / m. Limit Attention Number 8 30 0.24 0.12 0.20 130 86.1 0.36 2.01 9 300 0.03 0.01 0.02 21 89.9 0.36 1.86

SUBJECT OF THE INVENTION

Claims (2)

CLAIMS 1. A process for the stereospecific polymerization of alpha-olefins with a catalyst consisting of a muzzle compound deposited on a noocyte, 1 to 500 moles of an orgaoofinous compound and 0.5 to 200 moles of an electron-depleting compound relative to one atom of the Ti compound. an activated titanium compound obtained by grinding magnesium halides and an aromatic ester of formula OR ₉ I ² R.-C-OR i J OR 4 wherein R 1 is an aromatic hydrocarbon radical having from 6 to 12 carbon atoms and R 8, R 8 and R 8, which may be the same or different, denote an α-tertiary hydrocarbon radical having 1 to 10 carbon atoms, and contacting the comminuted product with a halide tianu · 2. A method according to claim 1, characterized in that as. the magnesium halide is magnesium magnesium chloride.