SU1168095A3 - Method of obtaining polypropylene - Google Patents

Abstract

A process for preparing highly stereoregular polyolefins in the presence of a catalyst which comprises (A) a titanium-containing solid catalyst component composed of an organic complex derived from (i) a magnesium halide (ii) an organo polysiloxane of the formula Q(Q2SiO)n SiQ3, (Q2SiO)n and/or x(Q2siO)nSiQ2X, (iii) an organic carboxylic acid ester, and (iv) a titanium compound of the formula Ti(OR)?x4-? and (B) an organoaluminum catalyst component of the formula R'mAl(OR')3-m .

Description

This invention relates to the industrial plastics, in particular to the production of polypropylene. The aim of the invention is to improve the physico-mechanical properties and the purity of the final product. The invention is illustrated by the following examples. Example 1. Obtaining a catalytic component (A). A stainless steel ball mill with a capacity of 800 ml with an inner diameter of 100 mm is placed on 100 stainless steel maps, each of which has a diameter of 15 mm, then 20 g of anhydrous magnesium chloride, 6.0 ml of ethyl benzoate and 3.0 mi are loaded into it methylpolysiloxane (having a viscosity of 20 cP at 25 ° C) in a nitrogen atmosphere and contacting during spraying and rotation speed of 125 rpm is carried out. The resulting solid is suspended in 150% titanium tetrachloride and the suspension is stirred at 80 ° C for 2 hours. Then, the solid component is filtered and washed with pure hexane until the ethyl chloride is contained in the wash water. The resulting component contains 4.1 wt.% Titanium and 58.2 wt.% Chlorine. Polymerization. A 0.05 ml (0.375 mmol) or 43.8 mg (0.0375 mmol, calculated per titanium atom) titanium-containing solid component (A) prepared above and 750 ml purified from oxygen and moisture kerosene are loaded into a 2 liter autoclave. The polymer saturation system is heated and when the temperature reaches the propylene is introduced. The polymerization of propylene begins at a pressure of 7.0 kg / cm. After carrying out the polymerization at 70 ° C for 3 i, the introduction of propylene is stopped. The contents of the autoclave are cooled to room temperature and decomposed by adding methanol to the catalyst. The solid component is separated by filtration, washed with methanol and substantial, yielding 410.3 g of polypropylene as a white powder. The residue after boiling H-heptane (P) of this powder is 94.5%, and its apparent density is 0 , 30 g / ml. On the other hand, in the liquid phase, 15.1 g of solvent soluble polymer are contained. The average specific activity in the polymerization based on the titanium atom of the catalyst used above is 540 g / mmol Ti t.atm. Comparative example 1. The preparation of the titanium-containing catalyst component. A ball mill of the same type as described in example 1 is loaded with 20 g of anhydrous magnesium chloride and 17.8 g of an adduct having an average composition of the formula CE C COOSOO N., these components are contracted under spraying under the conditions described in example 1, for 100 h with a speed of 125 rpm The resulting solid catalytic component (corresponding to component (A) of Example 1) is substantially agglomerated in a ball mill and / therefore it is difficult to obtain it in a powder form. A portion of the solid component was washed with 1 L of purified hexane to the same extent as in Example 1, and dried to obtain a titanium catalyst component. The titanium catalyst component contains 4.2 wt.% Titanium and 6.30 wt.% Chlorine. Polymerization. Propylene is polymerized under the same conditions as in Example 1, using 114 mg of the titanium catalyst component obtained above. You get only 8.8 g of polypropylene in the form of a white powder and 1.7 g of polymer, soluble in the solvent. Examples 2-4. For each experiment, the titanium catalyst component (A) was prepared according to the procedure of Example 1, with the exception that each of the polysiloxanes described in Table 2 was used. 1. Propylene is polymerized under the same conditions as in Example 1, using the obtained titanium catalyst components in the amounts indicated in Table. 1. The results obtained are summarized in table. 1. Examples 5-7. For each experiment, the catalytic component (A) of Example 1 was prepared, with the difference that each of the substituted benzoic acid esters shown in Table 2 was used. Propylene is polymerized according to example 1, using the catalytic component 3 (A) in the amounts shown in the table. 2 .. The results are shown in Table. 2. Example 8. Preparation of the catalytic component (A). The solid component is prepared by treatment in a ball mill of anhydrous magnesium chloride, ethyl benzoate and methyl hydropolysiloxane using the procedure of Example 1. The resulting solid component is suspended in 100 MP of kerosene containing 50 ml of titanium tetrachloride. and then treated for 2 hours at 100 ° C. with stirring. The solid component is separated by filtration and washed with purified hexane until titanium tetrachloride is present in the washings. The resulting catalytic component (A) contains 3.0 wt.% Titanium and 61.2 wt.% Chlorine. Polymerization. 750 ml of purified kerosene, 0.095 ml (0.0375 mmol of triisobutylaluminum and 59.5 ml (0.0375 mmol), counted as an atom of titanium, the catalytic component (A), are loaded into a 2 l autoclave with bone. The polymerization system is heated to 70 ° C and propylene is introduced. Polymerization of propylene is started at a total pressure of 7.0 kg / cm. Polymerization is carried out under stirring for 5 hours at 70 ° C., after which propylene is stopped. The contents of the autoclave are cooled to room temperature and the solid is filtered, washed with methanol. and dried to obtain 390.4 g of polypro white powder and 12.1 g of polymer, soluble solvent. The residue after extraction of the powdered polymer in boiling n-heptane is 96.4% and the apparent density is 0.31 g / ml. The average specific activity during polymerization this catalyst constitutes 306 g of polymer / mmol Ti tatm. Examples 9-13. For each experiment, the catalytic component (A) of example 1 is prepared, with the difference that each of the polysilokes listed in Table 1 . 3. Propylene is polymerized according to the method of Example 1, using catalytic K 95. 4 items (A) in the quantities given in Table. 3. The results are summarized in table. 3. Example 14. Preparation of cataptic component (A). A 800-mm stainless steel ball mill with an inner diameter of 100 mm, equipped with 100 stainless steel balls, each with a diameter of 15 mm, is loaded with 20 g of anhydrous magnesium chloride, an ester and polysiloxane (see Table 4). under nitrogen, then the mixture is ground for 100 hours at a rotational speed of 125 rpm. The resulting solid is suspended in 150 ml of titanium tetrachloride and the suspension is stirred at 2 hours. The solid component is then collected on a filter and washed with purified hexane until free titanium tetrachloride is present. Polymerization. In a 2-liter autoclave load 0.375 mmol of triethylaluminum, 0.0375 mmol (based on the atom of titanium) titanium-containing solid component (A), obtained above, and 750 ml of kerosene, free from oxygen and moisture. The polymerization system is heated, and when the temperature reaches 70 ° C, propylene is fed. The polymerization of propylene begins at a full davlenin of 7.0 kg / cm. After 3 h, the supply of propylene is stopped, the contents of the autoclave are cooled to room temperature and the addition of methyl. alcohol decompose catalyst. The solid component is collected on a filter, washed with methyl alcohol and dried to obtain polypropylene as a white powder. The results are summarized in table. 4 and 5. Example 15. Polymerization. Experience. 1. A 2 l autoclave is charged with 50 g of practically dry polypropylene in the form of a powder, which serves as a dispersing medium for the catalyst, after which it is charged, 58.4 mg (0.05 mmol per titanium atom) of the catalytic component are loaded into it. (A) prepared according to Example 1, and 0.067 ml (0.5 mmol) of aluminum triethyl. Then, propylene is immediately introduced into the autoclave, as a result of which the pressure inside the autoclave rises to 20 kg / cm and the temperature reaches 60 ° C. The gas phase polymerization was carried out at 60 ° C for 2 hours, resulting in 278 polypropylene. As a result of extracting the rest of the powder with boiling n-heptane, a yield of 92.8% is obtained (the amount of polypropylene taken as catalyst dispersion medium is not taken into account). Accordingly, the average specific catalytic activity per atom of titanium is 139 g of polypropylene (mmol Ti t.atm.).

Test 2. Polymerization of propylene was carried out according to Example 1, but ethyl benzoate was used in amounts of 1.5 ml (MgCEj / ethyl benzoate ratio 1.0: 0.5).

The result is given in table. 6

Experiment 3. The polymerization of propylene was carried out according to Example 1, but 30 ml of ethyl acetate (ratio MgCEj / 110 4 - 1/87) were used.

The result is given in table. 6

Test 4. Powdered magnesium chloride, ethyl benzoate and methyl polysiloxane prepared according to Example 1 are suspended in 50 ml of kerosene containing 25 ml of titanium tetrachloride (MgC2j / TiC 4 ratio - 1 / 0.11), after which the contacting is continued for 4 h under temperature and stirring. Then the solid components are separated by filtration and

beam solid catalyst.

The polymerization of propylene is carried out according to Example 1, but using the previously obtained solid catalyst

The result is given in table. 6

Test 5. Polymerization of propylene was carried out according to Example 2, except that 45 ml of 2,4,6-trimethylcyclotrisiloxane was taken,

which corresponds to the ratio of MgC j / Si compound - 1.0 / 1.15.

The result is given in table. 6

Example 16. Experience 1. When cooking component of the catalyst.

20 g of magnesium chloride 5 g of ethyl benzoate and 5 g of hexamethyldisiloxane are crushed together.

0 in a ball mill according to example 1. Powder obtained by joint grinding (containing 17.0 wt.% Mg, 3.8 wt.% Cu) is suspended in a solution containing 50 ml of 44.1 g

5 hexamethyldisiloxane and 20 ml of kerosene, and the reaction is carried out at 100 ° C for 2 hours with stirring. The solid component is collected on a filter and washed with purified hexane until no free Iict4 is detected. Component (A) obtained contains 3.2 wt.% Of titanium and 62.1 wt.% Of chlorine (calculated on atoms).

five

Polymerization. The polymerization of propylene is carried out as in example 1, but instead of the solid component (A) containing titanium, the component obtained as indicated above is used

0 catalyst.

The results of the polymerization are given in table. 7

Experience 2. Preparation of the catalyst component.

10 g of powder, obtained by combined grinding, as in Test 1, is suspended in 300 ml of TiCL and then 25 g of ethyl benzoate is added to the solution at 80 ° C. Thereafter, the reaction is carried out at 90 ° C for 2 hours.

0 The solid component is collected on a filter and washed with purified hexane until free TiCE is detected. The resulting catalyst component contains 3.7 May. 7 Ti5 tane and 57.1 wt.% Chlorine.

Polymerization. The polymerization of propylene was carried out as in experiment 1.

The results are given in table. 7

Table 1

2 Methylhydropolyoliloxane (3) 40.4 58.0 Hexamethyldisiloxane (3) 37.4 59.5 3-Hydroheptamethyltrisilok-san (3) 30.2 61.2 375 Hereinafter, the average activity in g of propylene). . .

4.50 54.6 39.9 40119.2 94.2

4.03 59.0 44.6 42514.1 94.6

3.64 59.2 49.3 410 25.0 93.2

330 18.0 93.9 0.29 442 395

table 2

0.28533

0.29560

I

0.28552 17.6 93, .5 0.28 524 15.1 93.9 0.29 495 polypropylene (mmol Ti ppm atm 9 Octaphenyl trisiloxane (3) 3.35 59.7 282.6 102.4.6- Trimethylcyclotrisiloxane (3) 3.43 60.2 291.1 11Octamethylcyclotetrasiloxane (3) 3.55 59.5 298.8 12 Dekamethylcyclopentasiloxane (3) 3.00 61.0 292.5 13 Octaphenylcyclotetrasiloxane (3) 3.04 60, 0 280.7

1 Benzyl Butyrate (6.23)

2Benzyl benzoate (8.90)

3Octyl benzoate (9.82)

Propyl p-butyl benzoate (9.82)

Table 3

(CH3) 2810 (2.12) 2.661.0

2.562.0

2,963,0

2.365.0

The same 16.7 93.4 0, -29 380 16.0 94.0 0.29 390 18.6 93.8 0.28 403 15.7 93.7 0.29 366 13.8 93.9 0 , 28 374

Etilenizat (4.72) Allyl acetate (1.61)

Ethyl Hexahyrobenzoate (8.18)

 Ethyl M-Toluate (8.61)

Ethyl p-toluene (7.93)

Iso-butyl naphthoate (6.84)

/

Ethylbutyrate (8.11)

P-chlorobenzyl benzoate (17,24)

Ethyl benzoate (5.25) Tic 4 -cyclohexyl acetate complex (9.36)

Ethyl benzoate (3.15) T1C 4-cyclohexyl benzoate (5.51)

Methylcyclopentanecarboxylate (1.34)

Tic 4-ethyl benzoate complex (10,19)

Butylcaprylate (7.00)

16I-Pentylbenzoate (4.03) Butylcrotonate (2.98)

17 Allyl benzoate (6.80).

2.5

61.0 2.1 67.0

an

2.5

62.0 2.2 68.0 62.0 2.5 2.4 63.0

) a

2.7

61.0 2.8 62.0 3.0 62.5

60.0

2.9

En 2.3 66.0

2, -5

61.0

60.0 3.1

Table 5

Table 6

Table 7

Claims (1)

METHOD FOR PRODUCING POLYPROPYLENE by polymerization of propylene in a hydrocarbon solvent in the presence of a catalyst based on a titanium compound on a magnesium-containing support and trialkylaluminium, characterized in that, in order to increase the physicomechanical properties and purity of the final product, an anhydrous halide interaction product is used as a titanium compound on a magnesium-containing carrier organopolysiloxane of the general formula Q ^{ (Q ₂ SiO) _h Si0 ₃ or (QQ * Si0) _p , where Q ⁽ is hydrogen, alkyl, cycloalkyl or aryl, with at least Q or Q is alkyl, cycloalkyl or aryl; P = 1 1000; p = 2 - 1000, an ester based on saturated or unsaturated C <~ Cd aliphatic or halogen-containing aliphatic acid, C ₇ -C ^ aromatic monocarboxylic acid and a primary saturated or unsaturated C | -Cu-alicyclic alcohol or ester selected from the group consisting of methylcyclopentanecarboxylate, methylhexahydrobenzoate, ethylhexahydrobenzoate and ethylhexahydrotoluate, as well as magnesium chloride rganopolysiloxane. ester and titanium tetrachloride from 1.0: 0.01: 0.05: 0.11 to 1.0: 1.15: 1.46: 87.0, respectively.