SU1452809A1 - Isoprene polymerization catalyst - Google Patents

Abstract

The invention relates to the preparation of catalysts for the polymerization of isoprene. The invention allows to increase the stereospecificity of the catalyst (the content of 1,4-cis-units in the polymer is from 96.5-98,%) and the cohesive strength of the polymer from 2.5-3 to 7.6-8 kg / cm due to its use as polymer carrier dp of titanium tetrachloride (TiCl4) 1,4-cis-polyisoprene (PI) containing a non-deactivating catalyst of previous polymerization cycles, as well as the additional introduction of diphenyloxide in the following ratio of TiCl: triisobutyl aluminum: diphenyloxide: 1,4-cis-PI 1: 1: (0.02-1) :( O, 0001- 0.0004). 2 tab. S

Description

1452809

related to receipt

pr T zhi pr +9 P1

cis-1,4 polyisoprene (PI) polymerization catalysts.

The aim of the invention is to increase the stereospecificity of the catalyst and the cohesive strength of the polymer obtained in its presence.

The catalyst is prepared as follows .I

The flask in an inert gas (nitrogen, argon) was added with the required amount of polymerizate with non-deactivated catalyst, four. Example 1 (control). To 2 g TicC with 0.9 g DFO in 20 ml toluene at -15 ° C was added 2.085 g TIBA in 20 ml toluene. The molar ratio of TiCl4: CHIBA: DFO 1; 1: 0.5. The mixture is kept at this temperature for 1 hour. 6.1 ml of a catalyst containing 0.28 g of TiCl2 are introduced into a solution of isoprene in isopentane (100 ml of isoprene + +900 ml of isopentane). Polymerization P1e is carried out for 1 h at 25 s.

Output Ш1 8800 r / r ii. The content of 1, 4-cis-structure is 96.5%. Titanium chloride (TiCl4) and diphenyl-5 is hesion strength of raw rubber seed (DFO) in toluene with the necessary mixtures of 2.5 kg / cm, the composition is as follows, molar ratio to T1C1d DFO / po20

thirty

limer (PI). The mixture was kept under stirring for 20 minutes at room temperature, cooled to -15 ° C and triisobutylaluminum (TIBA) was introduced in a molar ratio to TiCl 1: 1, the mixture was kept for 1 hour at -15 ° C, the temperature was raised to room temperature and stand for 7-8 hours. A 25-fold red-brown catalyst of a high degree of dispersion is obtained, which is re-exfoliated during long-term storage.

The polymerization of isoprene, freshly distilled over metallic sodium or over a catalyst; a torus (0.1 ml of the catalyst per 100 ml of isoprene) is carried out in isopentane of the polymerization frequency. The amount of catalyst 0.41% TiCl by weight of isoprene. Isoprene content a. in charge of 10-15 wt7%. At the end of the polymerization, the polymerizate is discharged into the alcohol and removed from the catalyst residues. The catalyst activity is determined in grams of the obtained polymer per gram of titanium.

The content of units with the configuration of cis-154 is determined by the NMR spectrum on the instrument With the sensitivity of the scale

35

40

May h.-:

Rubber SKI-3

Soot IM-5O

Soot DG-100

Zno

Stearin

Rubrax

Neozon D

Santokur

Altax

Sulfur

PR ri mep 2

100 30 15 5.0 1.0 2.0 1.0 0.8 0.8 0.2 2.5 (control).

50 ml of toluene, 0.8 g (0.000001 mol) PI, previously freed from antioxidant by reprecipitation in alcohol, with a content of 1.4 cis units of 97% and a mean mass of 800000, are introduced into the flask under a nitrogen atmosphere. dissolved (after 4–10 hours) 2 g (0.01 mol) of TiClfl are introduced into the flask. in 20 ml of toluene, incubated with stirring for 20 minutes at room temperature. Then the contents of the flask are cooled to -15 ° C and at this temperature 2.0 g of TIVA are introduced into 20 ml of toluene, kept for 1 hour. Then the temperature is raised to room temperature and allowed to stand for 7-8 hours.

0,, 5 abs.%.

Cohesive strength mixtures determined at break.

Rubber Composition

Rubber SKI-3

Soot IM-5O

Soot DG-100

Zno

Stearin

Rubrax

Neozon D

Santoyor

Altax -

Sulfur

Example 1 (control). To 2 g TicC with 0.9 g DFO in 20 ml toluene at -15 ° C was added 2.085 g TIBA in 20 ml toluene. The molar ratio of TiCl4: CHIBA: DFO 1; 1: 0.5. The mixture is kept at this temperature for 1 hour. 6.1 ml of a catalyst containing 0.28 g of TiCl2 are introduced into a solution of isoprene in isopentane (100 ml of isoprene + +900 ml of isopentane). Polymerization P1e is carried out for 1 h at 25 s.

Output Ш1 8800 r / r ii. The content of 1, 4-cis-structure is 96.5%. The cohesive strength of raw rubber compounds is 2.5 kg / cm, the composition is as follows,

5 hesion strength of raw rubber mixtures 2.5 kg / cm, the composition is as follows

0

five

May h.-:

Rubber SKI-3

Soot IM-5O

Soot DG-100

Zno

Stearin

Rubrax

Neozon D

Santokur

Altax

Sulfur

PR ri mep 2

100 30 15 5.0 1.0 2.0 1.0 0.8 0.8 0.2 2.5 (control).

0

five

0

five

0

five

50 ml of toluene, 0.8 g (0.000001 mol) PI, previously freed from antioxidant by reprecipitation in alcohol, with a content of 1.4 cis units of 97% and a mean mass of 800000, are introduced into the flask under a nitrogen atmosphere. dissolved (after 4–10 hours) 2 g (0.01 mol) of TiClfl are introduced into the flask. in 20 ml of toluene, incubated with stirring for 20 minutes at room temperature. Then the contents of the flask are cooled to -15 ° C and at this temperature 2.0 g of TIVA are introduced into 20 ml of toluene, kept for 1 hour. Then the temperature is raised to room temperature and allowed to stand for 7-8 hours.

A brown, finely divided, non-layered catalyst is obtained. 1 ml of catalyst contains 5.4 mg of Ti (0.0215 g of TiCl).

The polymerization is carried out in a flask under an inert gas atmosphere. To a mixture containing 100 ml (68 g) of freshly distilled isoprene and 900 ml (558 g) of isopentane of polymerization purity, 12.8 ml (0.272 g of TiCl) catalyst are added. The polymerization is carried out for 1.5 h at 25-30 C, Get PI 32.4 g

The content of 1,4-cis structures is 97jO%. The output of polymeps 1 g of Ti

1452809

SHOOO g. Cohesive strength raw

P

rubber mixtures of the composition according to example 1 3.0 kg / cm.

PRI me R 3 (control). The catalyst was prepared under the conditions of Example 2, but together with Ti, 0.9 g of DFO was introduced (molar ratio TiCl: DFO 1: 0.5).

The polymerization is carried out according to example 2, get PI with a content of 1, A - dis-structure of 97.5%. The output of PI is 8200 g / rTi. The cohesive strength of raw rubber compounds is 3.0 kg / cm.

An example. In a flask with 16 g of polymerizate (0.8 g of 1,4-dis-PI) with a non-deactivated catalyst (0.007 g of catalyst), 2 g of TiCl4 (0.01 mol) and 0.9 DFO (0.005 mol) in 50 ml of toluene. Amount ratio, 0001; ,five. Stand under stirring for 20 minutes at room temperature. The mixture is cooled to -15 ° C and 2.085 g of TIBA are introduced into 20 ml of toluene. The mixture is incubated for 1 h at -15 C. The temperature is raised to room temperature and incubated for 7-8 hours.

A red-brown catalyst is obtained that does not delaminate at

The output PI 9600 g / g Ti. The 1,4-cis form content is 98.6%. Cohesive strength is 7.6 kg / cm.

Example7 (control). The catalyst was prepared under the conditions of Example 4, but 2.64 g DFO (0.016 mol) was added. The molar ratio of TiCl4: DFO is 1: 1.6; , 0001. The yield of PI is 7600 g. 10 Content of 1,4-cis-units is 98%. Cohesive strength 3.0 kg / cm.

EXAMPLE 8 Prepare the catalyst of Example 4 with the addition of 1.7 g (0.01 mol) DFO. The molar ratio of TiCl4: PI is 1: 0.0001. The polymerization is carried out under the conditions of Example 4. The yield of PI is 9600 g / rTi. The content of 1,4-cis-structure links is 98.8%. Cohesive strength raw materials 20 rubber mixtures 8.0 kg / cm.

PRI me R 9 (control). The catalyst was prepared according to Example 4, using 160 g of the polymer of Example 4. Molar ratio, 5; 25 TiCl4., 001.

The output PI 8900 g / g Ti. The content of 1,4-cis form is 98%. Cohesive strength 4.5 kg / cm.

PRI me R 10. Catalyst ready35

long storage. 1 ml of the catalyst of example 4, using 8 g of pore contains 5.07 mg of Ti (0.0201 g of limerizate of Example 4. Molar co-TiCl4).

By polymerization on the resulting catalyst under the conditions of Example 2, cis-polyisoprene (9600 g per 1 g of titanium) is obtained. The content of 1.4 cis-forms is 98.8%. The cohesive strength of raw rubber mixtures of a composition according to Example 1 is 8 kg / cm,

il p and mep 5 (control). Kata-40 is given in table. one.

The lyser was prepared according to Example 4, using 32 g of the polymer as Example 4 with the addition of 0.017 g DFO in toluene as a polymer carrier using vol.

TiCl4 ratio, 5; TiCUinU 1: 0,00005. The output PI 8900 g / g Ti. The content of 1,4-cis-form is 97.0%. Cohesive strength 3.5 kg / cm.

Dependence of the polymer yield, the content of 1,4-cis-units in it and the cohesive strength of the molar ratio of the ratio of catalyst components

kanizat presented in table 2.

The magnitude of the cohesive strength in terms of shape retention is the molar ratio, where the breaker mixture is reached, 0002. The polymerization of the limits of the proposed method according to Example 4 is limited.

7-8 kg / cm reduces the relative elongation of the raw mixtures at break to 800-900%, while at 2.5-4 kg / cm it is 1800-1600%.

The output PI 8800 g / g Ti. The content of cis-1,4-structure units is 98.5%. Cohesive strength 3.5 kg / cm.

Example 6 A catalyst was prepared under the conditions of Example 4 using 64 g of polymerizate and 0.034 g DFO (0.0002 mol). Molar ratio TiCl4: PI 1: 0.0004; TiCl4: DFO 1: 0.02.

The polymerization is carried out according to the example.

The output PI 9600 g / g Ti. The 1,4-cis form content is 98.6%. Cohesive strength is 7.6 kg / cm.

Example7 (control). The catalyst was prepared under the conditions of Example 4, but 2.64 g DFO (0.016 mol) was added. The molar ratio of TiCl4: DFO is 1: 1.6; , 0001. The yield of PI is 7600 g. The content of 1,4-cis-units is 98%. Cohesive strength 3.0 kg / cm.

EXAMPLE 8 Prepare the catalyst of Example 4 with the addition of 1.7 g (0.01 mol) DFO. The molar ratio of TiCl4: PI is 1: 0.0001. The polymerization is carried out under the conditions of Example 4. The yield of PI is 9600 g / rTi. The content of 1,4-cis-structure links is 98.8%. Cohesive strength raw materials rubber mixtures of 8.0 kg / cm.

PRI me R 9 (control). The catalyst was prepared according to Example 4, using 160 g of the polymer of Example 4. Molar ratio, 5; TiCl4., 001.

The output PI 8900 g / g Ti. The content of 1,4-cis form is 98%. Cohesive strength 4.5 kg / cm.

PRI me R 10. The catalyst is ready

  Example 4, using 8 g of polymer in Example 4. The molar co

TiCl4 ratio, 5; TiCUinU 1: 0,00005. The output PI 8900 g / g Ti. The content of 1,4-cis-form is 97.0%. Cohesive strength 3.5 kg / cm.

Dependence of the polymer yield, the content of 1,4-cis-units in it and the cohesive strength of the molar ratio of the ratio of catalyst components

 Physical and mechanical properties of vol-

kanizat presented in table 2.

The magnitude of the cohesive strength in terms of preserving the shape of the Delhi from the breaker mixture is within the limits achieved by the proposed method.

50

7-8 kg / cm reduces the relative elongation of the raw mixtures at break to 800-900%, while at 2.5-4 kg / cm it is 1800-1600%.

F o rmula of the invention

Isoprene polymerization catalyst, including titanium tetrachloride, 55 1 4-cis-polyisoprene as a carrier and triisobutyl aluminum, is due to the fact that, in order to increase the stereospecificity of the catalyst and cohesion strength 5 of 14528096

The dNmer obtained in its presence contains diphenyloxide at

VII, as a carrier, includes a molar ratio of Ti1 4-cis-polyisoprene tetrachloride from the previous cyctan: triisobutylaluminum: diphenol & in polymerization, containing undezed: carrier from 1: 1; 0.02: 0.0001a1 | steved catalyst, and added-to: 1: 1: 0.0004.

 :: Table 1

Control.

Physical and mechanical properties

Conditional voltage at

300% elongation, MPa

Conventional tensile strength, MPa:

at

at 100 C

Relative extension

at break,%

Table 2

Indicators for example.,

known proposed

At:

10.0

29.0 20.0

565

Physical and mechanical properties

Residual elongation,%

Tear resistance, kN / M

Processability of breaker mixes (on the Brabender plastograph)

Indicators for example

ilbtfV 1

known proposed

10 110

120

0.03-0.04 0.05-0.07

Claims (1)

Claim Isoprene polymerization catalyst, including titanium tetrachloride, 1.4-cis-polyisoprene as a carrier and triisobutipaluminium, characterized in that, in order to increase the stereospecificity of the catalyst and cohesive strength, it significantly contains diphenyl oxide at a molar ratio of titanium tetrachloride: triisobutylaluminum: diphenyloxide: carrier from 1: 1; 0, 02: 0.0001 to): 1: 1: 0,0004. Table! of the polymer obtained in his presence, as a carrier, it includes 1) 4-cis-polyisoprene from previous polymerization cycles, containing an inactive catalyst, and additional experience Molar ratio PI yield, g / g Ti Content 1,4- Cohesive Cis-links,% strength, kg / cm ² 1 (invest- *, ny) 1 1 0.5 - 8800 96.5 2,5 2 (famous) 1 1 - 0.0001 6000 1 97.0 s oh 3 * 1 1 0.5. 0.0001 8200 97.5. s oh 4 1 1 0.5 0.0001 9600 98.8 8.0 5* 1 1 0.01 0,0002 8800 97.8 3,5 6 1 1 0.02 0,0004 9600 98.6 7.6 7 * 1 1 1,6 0.0001 7600 98.0 3.0 8 1 1 1,0 0.0001 9600 98.8 8.0 9* 1 1 0.5 0.001 8900 98.0 4,5 10* 1 1 0.5 0,0005 8900 97.0 3, U *Control. Table 2 Physical and mechanical properties Conditional stress at 300% elongation, MPa Conditional tensile strength, MPa: at 20 ° С at 100 ° С Indicators for example famous ^ proposed 9.0 10.0 28.5 29.0 19.5 20,0 Elongation at break,% 580 565 Continuation of Table 2 Physical and mechanical properties Indicators for example - famous proposed Residual elongation,% 10 8 Tear resistance, kN / M 110 120 Processing ratio bridge mixtures (on the plastograph Braben- der) 0.03-0.04 0.05-0.07