SU413790A1 - Method of producing cys-1,4-polybutadiene rubber - Google Patents

Abstract

METHOD FOR OBTAINING CIS-1,4-DIEN RUBBER POLYBUTH Polymer-butadiene Polymer in Hydrocarbon Solvent The solvent at that, in order to increase the rate of polymerization and monomer conversion, as well as to simplify the process technology and its regulation, oligomeric or polymeric compounds having an elementary unit of the general formula are used as aluminiumorganic compounds. 5A1-KA (\ 1-K-AG ^ > & V ^ R "^ where k is a bivalent radical — flHj-CHj-W = <; n-CH-CH ^ -fJHjCH, i or (L" Is-CHg-CHg-Tj- CHj-CHj-

Description

00

) The invention relates to the production of stereoregular synthetic rubbers, in particular the production of cis-1,4-polybutadiene rubber. There is a known method for producing cis-1, 4-polybutadiene rubber by polymerizing butadiene in a hydrocarbon solvent at 0-50 ° C in the presence of a catalyst consisting of . Of titanium tetrahalides and aluminum trialkyls, for example, triisobutyl aluminum. However, catalysts containing lower aluminum trialkyls are not resistant to air and water oxygen, which creates a fire and explosion hazard of the process. In addition, due to the rapid course of the redox process between the catalyst components, it is difficult to control the process, which also reduces the polymerization efficiency. In order to increase the rate of polymerization and monomer conversion, as well as to simplify the process technology and its regulation, it was proposed that oligomeric or polymeric compounds having an elementary unit of the general formula (A1-R-A1 Al-R-Al R) be used as organo-aluminum compounds. divalent radical - CH2 - (; H2-BHCN-CH2-1H2-E2 or -dHj-CHj-YipCHj-CHj) They are used in an amount corresponding to wearing in the catalyst from 3: 1 to 15: 1, preferably from 5: 1 to 10: 1. The polymerization process takes 1-4 hours with a conversion of butadiene, close to quantitative, the polymer yield 580-790 g per 1 g of catalyst, containing at least 91% cis-1,4-units in the polymer. The use of organo-aluminum polymer or oligomeric compounds as a catalyst component ensures the fire and explosion safety of the process due to the resistance of these compounds to water and oxygen, increases the conversion of butadiene and speeds up the process, reduces expenses of the main category recuperators (titanium halide) based on the same conversion value. In addition, due to the insignificant sensitivity of the rate of polymerization to a change in the ratio of the components of the catalyst, the process can be easily controlled. In Examples 1-3, a polymer compound of the following structure is used as the organo-aluminum component of the catalyst:

 radical

Where

- (1H2-CH2-CH C11-H-CH2-CH2CH3

Example 1. In a 13 l autoclave pour 6 l of 10% toluene solution of butadiene and - 5

Initially, 40.5 ml of a toluene solution of the organo-aluminum compound is given a concentration of 0.166 g / ml, and then 32.4 ml of a toluene solution of the mixed titanium halide concentration of 0.066 mol / l so that the AI: Ti molar ratio is 8: 1 at the dosage of titanium component 0/45 mmol per 100 g of butadiene. At the polymerization temperature, the conversion in 3.5 hours is 96%; Muni rubber viscosity 27; plasticity of 0.70; cold fluidity 100. Example 2. A 13 l autoclave is charged with 6 l of an 11.4% toluene solution of butadiene and 21.3 ml of a toluene solution of the indicated organoaluminum compound, a concentration of 0.166 g / ml, and then 34 ml of a toluene solution are fed first a mixed titanium halide concentration of 0.068 mol / l so that the molar ratio AE: Ti is 4: 1 at a dosage of titanium halide 0.45 mmol per 100 g of butadiene Polymerization temperature yield 94.4% for 30 minutes; rubber contains 91.4% of CIS-, 3.5% trans-, 4.5% of 1.2 units; viscosity according to .Muni 50; plasticity cold fluidity 30. Elasticity of rubber 52; modulus of strength 91; strength 191 kg / cm;

sc

СНз- З

A1-OH, -CH2-H-CH2-CHg L1-CH2-CK ;, -j-S-CHz-CHfh

SLJen, Example 4. In a 13 l autoclave, pour 6 l of a 10% toluene solution of butadiene and add 27.2 ml of a toluene solution of an organo-aluminum compound with a concentration of 0.175 g / ml and then 32.4 toluene of a mixed titanium halide concentration of 0.068 mol / l to a molar ratio AB: Ti was equal to 5: 1 at the dosage of the titanium component 0.45 mmol per 100 g of butadiene. Polymerization temperature of conversion for 2 hours is 89.3%; Mooney Viscosity 114; plasticity of 0.35; cold flow 1. Rubber contains 92% 1.4., 2.7% 1,4-trans and 5.3% 1.2. Example 5. A 13 l autoclave is filled with 6 l of a 10% toluene solution of butadiene and 34.8 ml of a toluene solution of organoaluminum compound at a concentration of 0.175 g / ml and then 32.4 ml of a toluene solution are mixed in; mixed titanium halide the concentration of 0.071 mol / l so that the molar ratio AR: T1 is

SNS

I CH

SNZHI

CHz CH2 elongation 660; residual elongation of 6%. Example 3. A 13 l autoclave is poured with 6 l of a 10.5% toluene solution of butadiene and 17.6 ml of a toluene solution of an organoaluminum compound with a concentration of 0.166 g / ml and then 27.6 mp of a toluene solution of smegta; titanium concentration., 0.071 mol / l so that the molar ratio AE: Ti was 4: 1 at a concentration of the titanium component of 0.35 mmol per 100 g of butadiene. Polymerization temperature -. Polymerization time 40 minutes; Conversion 93%; Mooney viscosity 64; plasticity of 0.54; cold fluidity 15. Content of 1,4-cis-units is 92.1%, 1,4-trans-units is 3.5%; 1,2-units 4.4%. In Examples 4-6, the aluminum oxide of the catalysis ± optic is ± 1, a polymer compound of the following structure lO is used: l at a dosage of the titanium component 0.45 mmol per 100 g of butadiene. Polymerization temperature conversion for 30 minutes 92%; Mooney viscosity 51; plasticity of 0.59; cold fluidity 22; elasticity 52; modulus of strength 70; strength 200 kg / cm, an elongation of 685%; residual elongation of 10%. Example 6. In a 13 l autoclave, 6 l of 10% toluene solution of butadiene is poured, 26.6 ml of the indicated organo-aluminum compound is added first with a concentration of 0.178 g / ml, and then 25.2 ml of a toluene solution of mixed titanium halide with a concentration of 0.071 mol / l at the dosage of the titanium component of 0.35 mmol per 100 g of butadiene. Polymerization temperature conversion for 40 min 86%; Mooney viscosity 57; 1st layer -0.57; cold fluidity 25. Thus, the polymerization of 1,3-butadiene on polymeric organo-aluminum compounds allows the process to be carried out with wider S413790

loads of Ag: T ± and wider physico-mechanical and technical, and dosing intervals of titanium with composite indicators and micro-. nta. In this case, the rubber is obtained with the structure.

Claims (1)

METHOD FOR PRODUCING CIS-1,4- - POLYBUTE OF DIENE RUBBER by polymerization of butadiene in a hydrocarbon solvent at 0-50 ° C in the presence of a catalyst consisting of · titanium tetrahalides and organoaluminum compounds, characterized in that, in order to increase the polymerization rate and conversion of the monomer, as well as simplify the process technology and its regulation, oligomeric or polymeric compounds having an elementary unit of the general formula are used as organoaluminum compounds: where 1? - divalent radical! R