Method of preparing stereospecific isoprene polymerization catalyst

FIELD: polymerization catalysts.

SUBSTANCE: catalyst is prepared by mixing hydrocarbon solutions of titanium tetrachloride, triisobutylaluminum-diphenyl oxide complex, and 1,3-pentadiene at Al/Ti molar ratio from 0.9:1 to 1.2:1 and at temperature form -70 to +20°C, after which mixture of paraffin, aromatic, and naphthene hydrocarbons is added, in particular industrial or transformer oil in amount 0.05 to 2% on the weight of catalyst suspension.

EFFECT: increased catalytic activity and reduced dosage of catalyst in polymerization process, which allows production of rubber with reduced titanium compound level without increasing intensity of washing away titanium compounds.

2 cl, 1 tbl, 11 ex

 

The present invention relates to the field of synthetic isoprene rubber and can be used in the petrochemical industry.

A known catalyst for the polymerization of isoprene produced by the interaction of titanium tetrachloride, triisobutylaluminum, diphenyloxide and 1,4-CIS-polyisoprene with previous cycles of polymerization, containing nediscriminatoriu catalyst, taken in a molar ratio of 1:1:0,02:0.0001 to 1:1:1:0,0004 (A.S. 1452809 the USSR. MKI408 F 4/64, 136/08, 1989).

The disadvantage of this catalyst and method of its production is the presence of a large number of gel-fraction in the polyisoprene obtained in his presence (up to 50-80%), which complicates the processing of the polymer. In addition, this catalyst has a low activity in the polymerization reaction of isoprene.

A known catalyst for stereospecific polymerization of isoprene consisting of titanium tetrachloride, triisobutylaluminum, diphenyloxide and isoprene, taken in a molar ratio of from 1:1:0,4:0,5 to 1:1:1:3, obtained by mixing the components at a temperature of from minus 45 to 20°C (Patent 94861 Romania, MKI408 F 36/08, 1988). The disadvantage of this catalyst is low activity in the polymerization reaction of isoprene.

The closest to the distinctive characteristics and the achieved effect is pic is b obtain catalyst for stereospecific polymerization of isoprene, described in the copyright certificate 106198 the USSR - the prototype.

The prototype catalyst is obtained by mixing the hydrocarbon solutions of complex triisobutylaluminum with diphenyloxide and titanium tetrachloride in a molar ratio of Al:Ti is from 0.3:1 to 1.2:1 in the presence of a conjugated diene, which is injected into the reaction of interaction between the components of the catalyst is carried out at a temperature of from +10 to -70°C at a molar ratio of the conjugated diene and triisobutylaluminum from 0.02:1 to 2:1. As the conjugated diene using 1-alkyl-butadiene-1,3 (pentadien-1,3 or piperylene) and other homologs of butadiene-1,3.

The disadvantage of this method is not sufficiently high activity of the resulting catalyst in the polymerization of isoprene.

To improve the activity of the catalyst and reduce its dosage in the polymerization of isoprene suggest the following method thereof.

When the temperature is 70 to+20°C is mixed hydrocarbon solutions of titanium tetrachloride, complex triisobutylaluminum with diphenyloxide and pentadiene-1,3 at a molar ratio of Al:Ti is from 0.9:1 to 1.2:1, the product of the interaction add mineral oil, such as transformer brand TCH GOST 10121-76, industrial grades I-40A,-20A, AND-12A GOST 20799-88 in the amount of 0.05-2% by weight suspension of the catalyst.

The essential characteristic of which is the input stood in the catalyst of mineral oil. The specified feature makes it possible to increase the catalyst activity and reduce dosage by 50% in the process of obtaining CIS-1,4-polyisoprene, which, in turn, allows to obtain CIS-1,4-polyisoprene with a lower content of titanium compounds without increasing the intensity of his washing from these compounds.

Industrial applicability of the proposed method is confirmed by the following examples.

Example 1 (prototype).

In a glass reactor with a volume of 100 ml, heated to 180-200°C in vacuum, followed by purging with dry argon, in a stream of argon contribute to 0.92 g of concentrated TiCl4then 8 g of toluene. The temperature of preparation of supported catalyst to about minus 40°C. When operating the mixer after 15 minutes add 7,58 g of the solution of epirate CHIBA in toluene containing 0,987 g CHIBA, 0,245 g DFO and 0,048 g piperylene. The resulting suspension of catalyst is stirred for 10 minutes.

In the apparatus with stirrer, 6 liter load 2200 g of a 15% solution of isoprene in isopentane at a temperature of 45°C is injected 16.5 g of a suspension of the catalyst. The polymerization is carried out at 45°C. After 30 minutes to inactivate the catalyst and the polymer stabilized methanol-toluene solution of diphenyl-para-phenylenediamine (DFFL). The polymer allocate method for water degasification and dried in a drying Cabinet at a temperature of 80°C with forced hot without the ha. Obtain 165 g of polyisoprene. The conversion of monomer is 50%.

Example 2.

The method of preparation of the catalyst and the conditions of the polymerization are similar to those described in example 1 with the difference that in the finished catalyst of the same composition at a temperature cooking -40°C to increase its activity is introduced 0,0165 g transformer oil brand TCH (0,1% by weight suspension of the catalyst in the form of a 50% solution in isopentane.

Get 300 grams of polyisoprene, which is 91% of the mass of the loaded isoprene.

Example 3.

The method of preparation of the catalyst and the conditions of the polymerization are similar to those described in example 2 with the difference that the catalyst is introduced transformer oil brand TCH in the number 0,165 g (1% by weight suspension of catalyst).

Obtain 330 g of polyisoprene, which is 100% by weight of a loaded isoprene.

Example 4.

The method of preparation of the catalyst and conditions of the polymerization process similar to that described in example 2 with the difference that the catalyst is introduced transformer oil brand TCH in the amount of 0.33 g (2% by weight suspension of catalyst).

Get 314 g of polyisoprene, which is 95% of the mass of the loaded isoprene.

Example 5.

The method of preparation of the catalyst and conditions of the polymerization process similar to OPI the data in example 2 with the difference, in the catalyst is introduced transformer oil brand TCH in the number 0,495 g (3% by weight suspension of catalyst).

Obtain 135 g of polyisoprene, which is 41% by weight of a loaded isoprene.

Example 6.

The method of preparation of the catalyst and conditions of the polymerization process similar to that described in example 1 with the difference that the catalyst of the same composition at a temperature of -10°C is introduced industrial grade oil AND 40A in the number 0,0017 g (0,01% by weight suspension of the catalyst in the form of a 20%solution in toluene.

Obtain 165 g of polyisoprene, which is 50% wt. per loaded isoprene.

Example 7.

The method of preparation of the catalyst and conditions of the polymerization process similar to that described in example 6 with the difference that industrial oil brand AND 40A entered number 0,00837 g (0.05% by weight suspension of catalyst).

Obtain 198 g of polyisoprene, which is 60% wt. per loaded isoprene.

Example 8.

The method of preparation of the catalyst and the conditions of the polymerization are similar to those described in example 1 with the difference that the catalyst of the same composition at -40°C as an additive that increases the activity of the catalyst, is introduced industrial grade oil I-20A in the number 0,0165 g (0.1% by weight suspension of the catalyst in the form of 50-aqueous solution in isopentane.

Get 295 g of polyisoprene, which is 89% by weight of a loaded isoprene.

Example 9.

The method of preparation of the catalyst and conditions of the polymerization process similar to that described in example 8 with the difference that the industrial grade oil I-20A entered number 0,165 g (1% by weight suspension of the catalyst in the form of a 50%solution in toluene.

Obtain 310 g of polyisoprene, which is 94% wt. per loaded isoprene.

Example 10.

The method of preparation of the catalyst and the conditions of the polymerization are similar to those described in example 1 with the difference that the catalyst of the same composition at a temperature of -70°C as an additive that increases the activity of the catalyst, is introduced industrial grade oil AND 12A in the amount of 0.33 g (2% by weight suspension of catalyst).

Obtain 330 g of polyisoprene, which is 100% by weight of a loaded isoprene.

Cornered 11.

The method of preparation of the catalyst and the conditions of the polymerization are similar to those described in example 10 with the difference that the addition of industrial oil brand AND 12A is introduced into the suspension of the catalyst in the amount of 0,495 g (3% by weight suspension of catalyst).

Obtain 115 g of polyisoprene, which is 35% wt. per loaded isoprene.

The data show that the catalyst for the polymerization of isoprene is, obtained by the present method and containing 0.05-2% wt. mineral oils (examples 2-4, 7-10), has a higher activity compared with the prototype. The activity of the catalyst when the content of mineral oil is less than 0.05% wt. (example 6) or more than 2% wt. (examples 5, 11) is not higher than the activity of the catalyst obtained by a known method.

Properties of polyisoprene obtained in examples 1-11 and its vulcanizates shown in the table.

As shown, the properties of polyisoprene obtained with the use of a catalyst containing mineral oil, as well as physical and mechanical properties of filled vulcanizates are at the level of the relevant parameters of the prototype.

Thus, the inventive method allows to obtain a catalyst for stereospecific polymerization of isoprene with increased activity.

1. The method of producing catalyst for stereospecific polymerization of isoprene mixing of hydrocarbon solutions of titanium tetrachloride, complex triisobutylaluminum with diphenyloxide and 1,3-pentadiene at a molar ratio of AL:Ti is from 0.9:1 to 1.2:1 and then adding the product of the interaction of a mixture of paraffinic, aromatic and naphthenic hydrocarbons, characterized in that to increase activity rolled atora as a mixture of paraffin, aromatic and naphthenic hydrocarbons used mineral oil, which is industrial or transformer, in the amount of 0.05-2% by weight suspension of the catalyst, the mixing is carried out at -70 ÷ +20°C.

2. The method according to claim 1, characterized in that the mineral oil in the form of a solution in a hydrocarbon solvent or without solvent is introduced into the reaction of interaction of the catalyst components at a temperature of from -70 to -10°C.



 

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15 cl, 5 tbl, 18 ex

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