SU660982A1 - Method of obtaining copolymers - Google Patents

Description

one

The invention relates to the synthetic rubber industry, in particular, to a process for the preparation of unsaturated elastomers vulcanizable with sulfur.

A known method for producing ethylene-propylene-diene copolymers using dicyclopentadiene (DCPD) 1 as a diene hydrocarbon, however, DCPD used as the third component has a number of disadvantages. First, ethylene-propylene-dicyclopentadiene rubber contains cross-linked structures, it is poorly soluble in boiling i-heptane and has a low vulcanization rate (60 min. These drawbacks do not make it possible to widely apply DCPD as the third component.

The closest to the proposed method is to obtain copolymers by copolymerizing ethylene, propylene, cC-dodecene and dicyclopentadiene in the presence of a catalyst consisting of the reaction product of vanadyl sulfate and sodium diisopropyl salicylate and an organo-aluminum compound in an inert organic solvent medium 2. Process

carried out at a ratio of ethylene to propylene from 1 $ 4 to 2i3,

According to a known method, the process is carried out in an environment of inert solvents such as hexane, isooctane, cyclohexane, benzene, toluene, dichlorethylene, ortho-dichlorobenzene. The copolymerization is carried out using gaseous mixtures of ethylene with

0 propylene.

The disadvantage of this method is the use of a complex catalytic system, requiring a special preparation method, using the difficult-to-reach dodecene-1 as a ci-olefin: production of a copolymer with a low yield and insufficiently high physicomechanical properties.

0

The purpose of the invention is to simplify the process technology, increase the yield and improve the physical and mechanical properties of the final product.

This goal is achieved by copolymerizing 3.5-7.0 mol.% Of ethylene, 42.2-76.5 mol.% Of propylene, 18.0-50.0 mol.% Of CA - Cgci-olefin and 0.8-2.0 mol% of Dicyclopentadiene in propylene or Cd - Cg cC-ole0 Fina medium. This ratio provides

the content of ethylene in the copolymer is in the range of 50.0-75.0 mol. % and oL-olefin in the range from 6.0 to 12.0 mol. propylene from 39.3 to 18.0 mol.% and DCPD - from 0.8 to 2.0 mol. %

In the process of copolymerization, the amount of ethylene and o (, - olefins fed in, is kept at a certain level. So, the ethylene content in the reaction zone is 4.0 mol.%, And 20.0-50.0 mol.% With α-olefin. monomers in the reaction zone provide a more stable rate and increase the conversion of dicyclopentadiene. With a stable speed, the distribution of monomer units along the macromolecular chain of the copolymer improves, which improves the physical and mechanical properties of the latter. Tilenau reaction zone avoids the formation of crosslinked polymer in struture.

The catalytic system used in the process is a well-known catalytic system consisting of vanadium triacetylacetonate and diisobutylaluminum chloride, which, unlike the catalytic system of the known method, does not require a special preparation method. It is used as b-olefin butene-1, pentene-1 and hexene-1 are more available than that used in the well-known method as the fourth component of dodecene-1. With an increase in the molecular weight of the geC-olefin {butene-1, pentene and hexene-1) used, the properties of the resulting ethylene-propylene-6-olefin diene elastomers are significantly improved.

Example 1. Into an autoclave purified from traces of moisture and oxygen, 300 IAJI liquid propylene, 200 ml of liquid butene-1 and 1.8 g / l of dicyclopentadiene are charged (DGD1D is fed to the reaction zone as a 1 wt.% Solution prepared in cC-olefin The temperature in the autoclave is adjusted to. At this temperature, the pressure in the autoclave is adjusted to 4.5 times the addition of ethylene. Then, 0.05 g of vanadium triacetylacetonate (AC) and 0.20 g of diisobutylaluminum chloride (DIBAH) are fed to the autoclave. for 40 minutes. As the pressure decreases, fresh ethyl is fed to the autoclave. 55 g of a copolymer with the following characteristics is obtained:

Solubility in n-heptane,

weight,% 100

Neighborhood,

mol / kg0,22

Characteristic

viscosity, dl / g2,2

Based on the obtained copolymer. After its drying in vacuum, it is prepared

rubber mixture according to the following recipe, weight. including:

Copolymer100

Soot50

Zinc Oxide5

2-Mercapto-6-ethylethazole, (captax) 0.5 Tetrathiuram disulfide (thiuram) 1. 5 Sulfur 1,5

Vulcanization is carried out at within 15.30, 45 minutes. Optimum vulcanization is reached at .150 ° C for 30 minutes.

The results are shown in Table 1.

Example 2. The experiments are carried out analogously to example 1. The concentration of DCPD in the reaction zone varies from

1 to 3 g / l. Optimum vulcanization is achieved during

30 min. The results are shown in Table. 2Examples The experiments were carried out analogously to example 1. The temperature of the experiment was varied from -10 to -20 ° C. 1.8 g / l of DCPD was fed to the reaction zone.

The results are shown in Table. 3. Optimum vulcanization is achieved within 30 minutes at a temperature of 150 ° C.

Example 4: The experiments were carried out analogously to Example 1. Pentene-1 was used as di-olefin. In the reaction zone serves 0.4 g DIBAH and

2g / l DCPD. 600 g of unsaturated copolymer are obtained.

According to the results obtained, see Table 4. Optimum vulcanization at ISO-C is achieved within 25-30 mich

Examples 5-6. The experiments were carried out as in Examples 1-5. Hexene-1 is used as an oC-olefin. The content of 1-hexene in the reaction zone varies from 20 to 30 mol. % 0.1 g, 0.4 g DIBAH are fed to the reactor. and 2 g / l DCPD. 60 g of copolymer are obtained. The results are shown in Table. five,

Examples 7-8. The experiments were carried out as in Examples 1-6. Hexene-1 is used as the cC-olefin. The ethylene core in the reaction zone is varied from 3.5 to 7 mol. % 0.1 g ACjV, 0.4 g DIBAH and 2 g / l DCPD are fed to the reactor.

Get in npj-iMepe 7 40 g of copolymer, in example 8-60 g. The results are shown in Table. 6. Optimum vulcanization when achieved within 20-30 minutes.

EXAMPLE 9 Experiments are carried out analogously to Example 1. A) butene-1, b) butene-1, c) hexene-1 are used as o6 olefin. The results are shown in Table. 7

Example 10. The experiments are carried out in a tax manner of Example 1. Hexene-1 is used as obolofin. The obtained results are shown in Table. 8. Thus, the proposed method allows to obtain a copolymer with a high yield and better than

6609826

a known method of physicomechanical indicators g-li. The method is simple in hardware design due to the absence of a solvent regeneration unit.

Table

-10 100.0 -62

Table 2

T a b l and c a 3

131446608071

30240 44020120

4519340014132

6018038012143

SzN 52

 4.0

CjH 5.2 35.0

95

-20

 39.4

31H, PD -1,4: DCPD -1.3

4.0 52 64.3 C, Hg, 38.0

-62

100

0.2

cC-CgH 30.2 8.8 DCPD 1.50, DCPD 1.2

15 30

45 60

Table. four

720 650

155 60 480. 18,245,108

2.0

14 8

450

240 120 350

175 148

a b l and c a 5.

,, 0515.3: 5.5: 0.4.

16.5 3.6

DTSPD 2, O

Table

112

290

192

Claims (2)

45. The invention The method of obtaining copolymers by copolymerization of ethylene, propylene, czb of lefine and dicyclopentadiene in the presence of a catalyst consisting of a vanadium compound and an organoaluminum compound, is characterized in that, in order to simplify the process technology, increase the yield and improve the physical and mechanical properties of the final product copolymerized Table B 3.5-7.0 mol. % ethylene, 42.2 76, 5 mol. % propylene, 18.0 50.0 mol. % С - С оС-olefin and 0.82, 0 mol. % Dicyclopentadiene in the environment of propylene or C-Cg-d, α-olefin. Sources of information taken into account in the examination 1.Patent of France No. 1473938, CL 08i, 1967. 2. The patent of Germany No. 1520758, cl. 39 b 3/04, 1972.