SU451333A1 - Method of preparing carbochain copolymers - Google Patents

Description

where is hydrogen or an alkyl group; Kg - alkylene with carbon number O-5;

X is a halogen or complex ester group, if Rs-Ci- € 5 is alkylene, or a carboxylp group.

The essence of the proposed method consists in carrying out the copolymerization of ethylene, propylene, ethylidenenorbornene and a norbornene derivative of the indicated formula in the presence of a catalyst consisting of vanadium trichloroxide and ethylaluminum sesquichloride.

Carbotoxinorbornene, carbobutoxinorbornene, methyl nororbornene chloride, norborienoic acid, or methyl nororbornene acid can be used as a derivative of norbornene.

The norborne derivative can be supplied to the reaction mixture either separately from the catalyst components and the diene, or together with one of these compounds, preferably a diene or an aluminum compound. Its concentration in the reaction mixture is 0.2-300 mmol / l and depends on the type of functional group included in the molecule and the desired content of this monomer in the copolymer.

Copolymerization can be carried out in the presence of other halogen derivatives of vanadium, as well as halogen derivatives of titanium, such as JOC, TiCl4, TiCla, or mixtures of halides V and T1.

Among the organic compounds of aluminum, in addition to ethyl aluminum sesquichloride, trialkyl aluminum, mono- or dichlorides of aluminum alkyl derivatives, for example, aluminum triethyl, diisobutyl aluminum chloride, diethyl aluminum chloride, etc., can be used.

The concentration of vanadium trichloroxide in the reaction mixture may be 0.05-1 mmol / L, preferably 0.1-0.5 mmol / L.

Ethylaluminum sesquichloride is used when its concentration in the reaction mixture is 0.5-40 mmol / L, preferably 1-20 mmol / L.

The molar ratio of the aluminum compound and the vanadium compound is maintained at a copolymerization of 2: 1-100: 1, preferably 5: 1-30: 1.

As an α-olefin, in addition to propylene, compounds of the general formula SpNzp can be used, where.

The molar ratio between ethylene and propylene in the gas phase is 1: 0.25-1: 5, preferably 1: 0.5-1: 4, to obtain amorphous copolymers.

Linear, cyclic, bicyclic compounds, such as hexadiene-1, 4, cyclooctadiene, dicyclopentadiene, methyltetrahydroindene, etc. can be used as a diene with non-conjugated double bonds, in addition to ethylidenenorbornene. The concentration of these compounds in the reaction mixture and their content in the polymer is frozen m from the type of diene used and do not differ from the values of these parameters used to obtain ethylene, propylene and diene copolymers.

The copolymerization can be carried out in the medium of propylene or another α-olefin used in the reaction, in an inert solvent, and also in chlorinated hydrogen.

When the reaction is carried out in an inert solvent, aliphatic, cyclic, aromatic hydrocarbons, gasoline, etc. can be used as the latter.

Methyl chloride, methylene chloride, etc. can be used as chlorinated hydrocarbons.

The copolymerization is carried out in the temperature range from -50 to + 80 ° C, preferably from -10 to + 40 ° C. The reaction can be carried out in a batch or continuous manner.

The resulting copolymer is recovered from the reaction mixture either by precipitation with an alcohol, for example ethyl, yzo-nropyl, or water degassing, after which it is dried. The cured polymers are characterized by a characteristic viscosity, determined in tetralin at 135 ° C, a propylene and diene content, determined by infrared spectroscopy (IR) and a content of norbornene derivative. The content in the polymer of a derivative of norbornene with an ester group is determined by the X-ray method by the absorption band of 1740 cm. The content of methyl nororbornene chloride is determined by the method of Scheniger (by the amount of chlorine in the copolymer), the content of the derivative of norbornene with a carboxyl group is determined by a radiometric method ) or by the X-ray method using the 1715 cM-i absorption band.

Example 1. The copolymerization of ethylene, propylene, ethylidenenorbornene and carbobutoxinorbornene is carried out at 20 ° C in a 1000 ml reactor. 700 ml of heptane are fed to the pre-heated vacuum-heated and filled with argon and the solvent is saturated with a mixture of ethylene and propylene, taken in a 1: 2 ratio (by volume).

A mixture of gases at saturation and carrying out the reaction is served at a rate of 60 l / h. After saturation, without interrupting the flow of the gas mixture, the solutions from headers connected to the tubes are introduced in 60 portions in uniform portions every 5 minutes to the solutions in hectane VOCls, A12 (C2H5) CCl, ethylidene norbornene, and carbobutoxynorbornene.

A total of 0.6 mmol of VOCls, 10.4 mmol of (C2H5) 2Cl2, 10.0 mmol of ethylidenenorbornene and 5.2 mmol of carbobutoxynorbornene are used for the reaction.

The polymer is separated from the reaction mixture by precipitation with a large amount of ethyl alcohol and dried on a roll mill.

Get 30 g of the copolymer, completely soluble in hexane at 20 ° C. Characteristics of the copolymer: Content, weight. %: Carbutoxinorborien 0.98

propylea43,0

Ethyl Adenylorbena4,2

Characteristic viscosity 1.35 Mooney viscosity at 100 ° C 32.0 Stiffness430

To prepare the rubber mixture, the copolymer is mixed by the rollers with the ingredients according to the following recipe, wt. including:

Copolymer100

Soot "Volcano-3 (kiln, finely dispersed) 50 Stearic acid1.0 Zinc oxide 5.0 Tetramethylthiuram disulfide

(thiuram) 1.5

Mercaptobenzothiazole (Captax) 0.5

Sulfur2.0

Vulcanization is carried out at 143 ° C for 20 minutes.

The resulting vulcanizate has the following physico-mechanical properties: Tensile strength, kgf / cm 220

Relative lengthening,% 353

Residual elongation,% 20

Example 2. The procedure and experimental conditions are the same as in Example 1, except that the copolymerization is carried out at 2 ° C and to saturate the solvent and during the reaction, a mixture of gases is used at a ratio of ethylene to propylene of 1: 1.5 (v / v). Get 40 g of the copolymer, completely soluble in hexane at 20 ° C. Characteristics of the copolymer: Maintenance, weight. %: Carbutoxinorbornene0.95

propylene45

ethylidenenorbornene3.8

Characteristic viscosity 2.42 Mooney viscosity at 100 ° C 89.5 Stiffness 1150

For the preparation of rubber compound 100 weight. including copolymer shift from 50 weight. h oil "Nikton 60, then the oil-filled polymer is mixed with the ingredients according to the recipe given in example 1.

Vulcanization is carried out at 143 ° C for 20 minutes.

Physico-mechanical properties of an vulcanizate based on an oil-filled polymer: Mooney viscosity at 100 ° C

oil-filled copolymer 25.5 Modulus at 300% stretch,

kgf / cm 64

Tensile strength, kgf / cm 195

Relative lengthening,% 725

Residual elongation,% 19

Example 3. The copolymerization of ethylene, propylene, ethylidenenorbornene and carbethoxynorbornene is carried out in a manner analogous to example 1.

For the reaction, 0.17 mmol of VOCls, 3.11 mmol of A12 (C2H5) CCl, 5.0 mmol of ethylidenenorbornene and 1.50 mmol of carbethoxynorbornene are taken. A mixture of ethylene and propylene in a 1: 1 ratio (by volume) is used to saturate the solvent and carry out the copolymerization. After aqueous degassing and drying, 14 g of copolymer are obtained.

Characteristics of the copolymer: Content, weight. %:

carbethoxyporbornene0.4

propylene41,0

ethylidenenorbornene4,4

Characteristic viscosity 1.95

Solubility in hexane at 20 ° С 94.4

Polymer tensile strength of 60 kgf / cm, elongation of 1050%.

Example 4. The methodology and experimental conditions are similar to those described in example 3,

with the exception that carbobutoxinorbornene is used as a derivative of norbornene. 16 g of copolymer are obtained. Characteristics of the copolymer: Content, weight. %:

carbobutoxinorbornene0.33

nropylene40,0

ethylidenenorbornene4,2

Characteristic viscosity2.04

Solubility in hexane at 20 ° С is 92.4. The strength of a polymer is a gap of 47 kgf / cm, an elongation of 1330%.

Example 5. Ethylene, propylene, ethylndenorbornene and methylnororbentine chloride are copolymerised by a procedure similar to Example 1.

To conduct the experiment, 500 ml of heptane, 0.228 mmol of YOCIa, 5.18 mmol of A12 (C.9H5) CCl3, 5.0 mmol of ethnlngnorbornene and 31.5 mmol of methylnorbornene chloride are used. 17.5 g of copolymer, completely soluble in hexane at 20 ° C, are obtained. Characteristics of the copolymer: Content, wt. %:

chlorine3.9

propylene 43,0

ethylidenenorbornene4.0

Characteristic viscosity 1.5

Example 6. The procedure and conditions of the experiment: 1 is similar to that shown in Example 5, except that gas is used at a 1: 0.5 ratio (by volume) of ethylene to propylene to saturate the solvent and BO.

23 g of polymer are obtained, which is 95% soluble in hexane at 20 ° C. Characteristics of the polymer: Content, weight. %:

4.05

chlorine 35 4.1 propylene ethylidenenorbornene

Characteristic viscosity1,14

The strength of the crude polymer pa break 100 kgf / cm, relative elongation of 800%. Example 7. Norbornornic acid is used as a derivative of norbornore.

labeled by. The copolymerization reaction is carried out at 20 ° C.

To conduct the reaction, 170 ml of heptane are fed to the reactor and the solvent is saturated with a mixture of ethylene and propylene, taken in the ratio 1: 1.5 (by volume). The feed rate of the gas mixture during the saturation and reaction time is maintained at 60 l / h. 14.15 MMOL A12 (C2H5) sC1z are used for the reaction,

0.23 mmol VOCls, 3 mmol ethylidene norbornene and 2 mmol norbornene acid.

The reagents in the form of solutions in 10 ml of heptane are fed into the reactor from the dosers in one step in the following sequence: А12 (С2Н5) sС1з, norbornenic acid, ethylidene norbornene and UOS1.

After 15 minutes, 20 ml of 6N are fed to the reactor at the start of the reaction. HCl for termination of the reaction and destruction of possible comlexes of the carboxyl groups of the copolymer and the organoaluminum compound. The polymer is precipitated with ethyl alcohol. Obtain 5.7 g of a white rubber-like copolymer, completely soluble in hexane at 20 ° C.

Characteristics of the copolymer:

Content, weight. %: norbornenic acid 0,52

propylene42,3

ethylidenenorbornene6.0

Characteristic viscosity1,89

The presence of carboxyl groups in the copolymer was confirmed by the X-ray method by the presence in the spectrum of the 1715 cm absorption band characteristic of this group. The copolymer is shifted on the rolls from 10 wt. h. MgO and vulcanized in the mold at 150 ° C for 40 minutes

Physico-mechanical properties of vulcanizate:

Tensile strength, kgf / cm 40

Relative elongation,% 425

Residual elongation,% 33

Claims (1)

Invention Formula The method of producing carbon-chain copolymers by copolymerizing ethylene, a-olefin, a non-conjugated diene and a unsaturated compound containing a functional group in a mass or medium of an inert hydrocarbon solvent at a temperature of from -50 to 80 ° C in the presence of Ziegler-Natta catalysts, characterized in that in order to obtain copolymers of predetermined molecular weight, with increased cohesive strength and high physicomechanical characteristics of soot- and oil-filled mixtures vulcanizates, as well as reduced and the consumption of the catalyst components, as a unsaturated compound containing a functional group, the norbornene derivatives of the general formula are used. Rr is hydrogen or alkyl; Rs-alkylene with a carbon number of 0-5; X is a halogen or ester group if Rs-Ci-Cs is alkylene, or a carboxyl group.