SU477630A1 - Method of producing olefin copolymers - Google Patents

Description

The present invention relates to methods for producing copolymers based on a diolefin and unsaturated compounds containing functional groups by copolymerizing these monomers in the presence of Ziegler-Natta type catalysts.

The proposed method can be used in the synthetic rubber industry, in the manufacture of tires and rubber products, for the production of adhesives and various household items.

A known method for producing olefin copolymers by copolymerizing ethylene, another α-olefin and an acrylic acid derivative (for example, acrylonitrile or ethyl acrylate) in a mass or inert solvent medium at a temperature of from -50 to 80 ° C in the presence of Ziegler-Natta catalysts, consisting, for example, of halogen-containing vanadium compounds such as vanadium VOClg oxychloride and aluminum organic compounds, for example ethyl aluminum sesquichloride,

The resulting copolymers may be cured by peroxides. However, copolymers obtained using ethyl acrylate or acrylonitrile have low molecular weight, which limits their field of application. They also do not have cohesive strength and have low physical and mechanical properties in soot and oil filled with vulcanizates. In addition, a large consumption of catalyst components (2 mmol / l VOCl, kQ mmol / l A1 () C 1 h) 1 is required, which makes it difficult to wash and isolate copolymers. The purpose of the invention, the elimination of these disadvantages, is achieved by using the norbornene derivatives of the general formula as the third comonomer: where R, -R7 is hydrogen or alkyl {Rg. C-C5-alkylene; - X - halogen, complex. Ether or carboxyl group / such as, carbobutoxynorbornene (CBNB), methylnorbornene chloride, norbornene and methylnorbornene acid. The concentration of the norbonon derivative in the polymerization mixture is 0.2 100 mmol / l. The norbornene derivative can be supplied either separately from the components of the catalytic system or together with one of them, preferably. with organoaluminium bonding. The copolymerization is carried out in the presence of catalytic systems consisting of halogen-containing compounds of variable valence metals of the IVVI groups of the Periodic System, for example TiCl, TiCl4, VCl-3, VCl, VOGlz. valence in the polymerization mixture is 0.05-1, preferably 0.1-0.5 mmol / l. The concentration of organoaluminum compounds 0, preferably 1-20 mmol / l. The molar ratio of the organoaluminum compound: the variable valence metal compound is 2: 1-100: 1, preferably 5; 1 30: 1. The copolymerization can be carried out in an oi-olefin medium, in an inert solvent, and also in a chlorinated hydrocarbon. Aliphatic, cyclic, aromatic hydrocarbons, gasoline, etc. can be used as inert solvents. Of chlorinated hydrocarbons, ethyl chloride, methyl chloride, methylene chloride, etc. can be used. The copolymerization temperature is (-50) - 80, preferably (-20) - tO C. The reaction can be carried out both periodically and in a continuous way. The resulting copolymer is recovered from the polymerization mixture either. alcohol, for example ethyl, isopropyl, or water degassing, after which the polymer is dried. The characteristic viscosity is measured in tetralin at 135 ° C, and the propylene content is determined by PC-spectroscopy. Solubility in hexane is determined at room temperature. The content in the copolymer of norbornene derivatives with a carboxyl group is determined by radiometric method using monomer labeled in C or by infrared spectroscopy by absorption band 1715; in the case of using methylnorbornene chloride - by chlorine content in the copolymer according to Scheniger, in the case of using norbornene with ester group - by IR spectroscopy using a bandwidth of cm or by a specified radiometric method. Examples 1-3. 170 ml of heptane are fed to a 300 ml reactor filled with vacuum and heated with argon and heated with a mixture of ethylene and propylene (1: 1.5). The mixture of gases at saturation and the reaction is fed at a rate of 60 l / h. After saturation without stopping the supply of the mixture of gases, 1 mmol fil (), 0.057 mmol VOC13 and CBNB in 10 ml of heptane are fed in one pass through tubes connected to the dispensers to the reactor. The copolymerization is carried out at. After 15 min, the reaction was terminated with ethyl alcohol (1 ml) and the copolymer was precipitated with ethyl alcohol. The number of CBNB and characteristics of the obtained copolymers are given in table. 1. Example i. Copolymerization is carried out as in Examples 1-3, but -20 ° C. 170 ml of heptane are saturated with an equimolar mixture of ethylene propylene, which is passed at a rate of 60 l / h. After saturation, mmol: 0.3 A1 () ClO, 0.02 VOCl, - and 0.15 are supplied to the reactor; CBNB labeled in C 2.5 g of a copolymer are obtained containing 0.1 May D CBNB and A3. , 2ma propylene, J 5,1. Example 5. The copolymerization was carried out in a 1CCOhm reactor at. 700 ml of heptane are saturated with a mixture of ethylene and propylene (1: 2) supplied at a rate of 60 l / h. Teptanov solutions of the components to the talizator and CBNB are uniformly fed every 5 minutes for 120 minutes. Spent, mmol 10, i Al, () 501.5, 0.6 VOCl-} and 5.2 CBNB. Get 32 g of the copolymer is completely soluble in hexane p 20 ° C. The copolymer contains 1.05 wt. CBNB, 43., 2 wt. propylene, 123 1, 39 Mooney viscosity 13.5 at 100 ° C. The copolymer is mixed on rollers with soot and ingredients according to the following recipe, m / m .: Copolymer100 Soot Vulcan-350 Sulfur0.4 Dicumyl peroxide 3.0 Zinc oxide3.0 Vulcanization is carried out at 150 ° C for 30 minutes Physical-mechanical Vulcanizate indicators: Module at growth KGS / CM291 Tensile strength, kgf / cm 206 Relative elongation, 1530 Residual elongation,% 24 Example 6. Example 5 is repeated, but the solvent is saturated and copolymerized at 0 ° C. Received +5 g of copolymer completely soluble in hexane at 20 C. The copolymer contains 1.2 wt.% CBNB, 15.8 ac .: propylene, 1.98, Mooney viscosity 1 at 100 ° C, stiffness 2bO. Physico-mechanical properties of black-filled vulcanizate, Module at 300% tensile strength, kgf / cm. Tensile strength, kgf / cm Elongation ,; Residual elongation,% Examples 7 and 8. Analogously to Example 5, copolymerization was carried out using a mixture of ethylene and propylene (1: 1: 5) and CBNB. Solutions of the catalyst components and CBNB are introduced within 60 minutes. Serve 0.1 i) h mmol VOCIj. The amount of A12. (C2H5) 3 used and the characteristics of the copolymers obtained are listed in Table 2. Example 9. The copolymerization is carried out analogously to examples 7 and 8. Giving, mmol: 1.025 Al (C .. 0.115 VOCl3 and 0.409 CBNB. After aqueous degassing of the solution and drying, 15, g of copolymer, completely soluble in hexane at 20 C, M3, are obtained. , 15, Mooney viscosity 35 at 100 ° C. Copolymer contains 0.25 May, CBNB Vulcanizate is prepared from the copolymer according to the following recipe, w.ch .: Oil-filled copolymer (WHA oil, 100 wt.h.) Zinc oxide Soot Vulkan-3 Dicumyl peroxide Vulcanization temperature, vulcanization time 60 min, Vulcanizate properties: Module at 300% elongation, CGS / CM293 4 Other tensile strength, kgf / cm2 Relative elongation,% Residual elongation,% Elasticity by rebound at 20 ° C. Hardness by TM-251 Example 10. The copolymer obtained in the form of a fine suspension is separated from filtering the reaction mixture. Then the copolymer chips are washed with ethyl alcohol and dried on rollers; After drying, 63 g of copolymer are obtained,. completely soluble in hexane at 20 ° C, containing 1j25 wt. CBNB, 7 wt.% Propylene j j 1.36, Mooney viscosity 32 at, rigidity 250 g. Example 11. Using chlorinated methyl norbornene, the experiment was carried out as in example 9. Using mmol: 0.228 VOC13, 5.18 A1g (C2H5), C1z, 31.5 of methyl norbornene chloride. After isolation and drying, 22.5 g of a white amorphous copolymer containing 5 wt.% Propylene, 3.1 wt.% Chlorine, Q 1.3, Example 12 are obtained. Using norbornenic acid labeled in the same manner as Example 5 sopol gauging. Served, mmol: 2.08 A1 (C4H5), .5C1, 5, 0.11 VOC13, 1.0 of norbornenic acid. At the end of the reaction, 20 ml 6 N are introduced into the reactor. HCl to destroy possible complexes of the carboxyl groups of the copolymer and the organoaluminum compound and the polymer is precipitated with ethyl alcohol. 6 g of a white rubber-like copolymer, completely dissolved in hexane at 20 ° C, are obtained. The copolymer contains 5% by weight of norbornenic acid. propylene, DM 1.9 The presence of a carboxyl group in the copolymer Confirmed by the method of IR-spectroscopy by the presence of the absorption band 1715. -8 Example 13. Using 1 mmol of ethyl norbornenic acid labeled with C dissolved in toluene, copolymerization is carried out, as in example 12. 5, g of a white amorphous polymer, completely soluble in hexane at 20 C, is obtained. The copolymer soderite 0.33 wt. . methylnorbornornoic acid, 46 wt. propylene,. The presence of the carboxyl group in the polymer was confirmed by IR spectroscopy based on the presence of the 1715 absorption band in the spectrum. Example 14. The copolymerization is carried out analogously to example 5, using norbornenic acid. . Giving, mmol: 1b, 2 A1 (C2H $), 0,69 VOClj, 7 | 3 norbornornovy acid. 27 g of a rubbery copolymer containing O, 5% by weight of norbornenic acid, 1 1.35, Mooney viscosity 35 are obtained. The copolymer is mixed on rollers from May 10, hours. MgO and vulcanized in a mold at 150 ° C for 40 minutes. Physical and mechanical properties of the vulcanizate: Tensile strength, kgf / cm 28 Relative elongation,% 475 Residual elongation,% 35 Thus, the use as a third monomer in the copolymerization of ethylene and oi-olefin of norbornene derivatives, for example CBNB, methyl nororbornene chloride, norbornene and methyl norbornene derivatives acids, makes it possible to obtain ternary copolymers of oi-olefins containing functional groups in the polymer chain, with a low consumption of catalyst. The resulting copolymers have an increased cohesiveness In general, fillers (soot and oil) are well dispersed, vulcanized using conventional vulcanization, canization systems for ethylene and propylene double copolymers and their soot- and carbon-coated aulcanizates have high physical and mechanical properties.

Using s as a third IM weight without using its special monomer functional function of molecular weight regulators derived from norbornene of this type allows one to obtain copolymers with radially larger than given pV77630 molecules.

used in the preparation of double and ternary copolymers of ethylene and propylene by known methods.

Table 1

X-44

CBNB labeled by C.

Determined by the radiometric method.

Obtained in terms of at least 7.

table 2

Claims (1)

METHOD FOR PRODUCING OLEPHIC COPOLYMERS by copolymerization of ethylene, another ob-olefin and a monomer containing functional groups in a mass or inert solvent medium at a temperature of from •• 50 to 80 ° С in the presence of Ziegler-Natta catalysts, which involves what, with the aim