SU235662A1 - - Google Patents

Description

METHOD FOR OBTAINING A SYNTHETIC RUBBER A method is known for producing synthetic rubber by co-polymerizing ethylene with Ci-Co-olefins and dicyclopentadienes in the presence of an organometallic coordinating catalyst consisting of vanadium compounds and organo-aluminum compounds. The proposed method, which involves the use of nonconjugated monocyclic dienes such as cyclooctadiene-1, 5, instead of dicycloentadiene, makes it possible to obtain rubber, which has a high resistance to aging in the vulcanized state. In the copolymerization process of the proposed method, in addition to cyclooctadiene-1.5, the following non-conjugated cyclic polyenes are used: cyclohexadiene-1,4, cycloheptadiene-1, 4, cyclooctadiene-1,4, cyclodecadienene-1, 6, cyclodecadien-1.7, cyclododecatriene -1, 5.9. In addition, alkyl cyclonolienes are used, and in particular, nonconjugated alkyl cyclodiolefins, for example, 1-methylcyclohexadien-2, 5, 1,2-dimethylcyclohexadien2, 5, 1-ethylcyclohexadien-2,5, 1-methylcyclooctadien-1, 5, 4- methylcyclooctadiene-1,5. Olefins, which are used together with ethylene in the preparation of copolymers, consist of α-olefins of the general formula -R, CH2 CH2, where R is alkyl containing 1-6 carbon atoms, preferably propylene and butene-1. Particularly interesting results are obtained in the preparation of ethylene copolymers with ethylene, propylene and cyclooctadium-1.5, or with butene-1 and cyclooctadiene-1.5. A crude product of copolymerization is obtained, consisting of macromolecules, each of which contains monomeric compounds formed from ethylene, propylene or butene-1 and cyclooctadiene-1.5. Each of the monomer units resulting from the polymerization of cyclodiolophia contains a free non-clumping bond. This means that double bonds, contents, and cyclodelef-1 compounds do not behave differently, i.e. if one of the double bonds is involved in the process, the other becomes inert and relative to it, so that the growth of macromolecules does not affect this free double bond. The resulting macromolecules are mostly linear and contain unsaturated cyclic lines. The resulting copolymers are homogeneous, which is confirmed by the ease of producing well-cured products using mixtures and prints commonly used to cure unsaturated rubbers, preferably with a low content of unsaturation, such as butyl rubber. The ease with which well-cured products are obtained also indicates that non-spilled compounds are well distributed throughout the chain.

Vulcanized products obtained in a tzkim way as opposed to unvulcanized polymers, which are mostly boiled with n-heptane, are completely insoluble in organic solvents and have the ability to swell only to a limited extent in some organic solvents, such as aromatic hydrocarbons.

The vulcanized rubbers obtained in this way have very good mechanical resistance and very low residual deformations after rupture.

The catalysts used in the inventive method are dispersed like a colloidal solution or completely dissolved in hydrocarbons, which are used as copolymer media, for example in n-heptane, benzene, or toluene, or in mixtures thereof. The catalysts are organo-aluminum compounds, for example trialkyls, dialkyl monohalides or monoalkyldihalides of aluminum, alkenyl and alkylene compounds of aluminum, or complexes of the above-mentioned organometallic compounds, with Lewis bases; and organic vanadium compounds.

In the preparation of the catalyst, it is preferable to use vanadium compounds soluble in hydrocarbons, which are used as a copolymerization medium.

The following organometallic compounds are listed which can be used to prepare the catalysts: triethyl, trigeobyl, triethyl monochloride, DIETHYLMONOID, diethyl monofluoride, diisobutyl monochloride, mono ethyl ethyl dichloride, diethyl monofluoride, diisobutyl monochloride, mono ethyldiochloride, ethyloxyfluoride, oxymethyl, and dihydroxyethylene. -1,4- (diisobutylaluminum) -butane or a complex of aluminum diisobutyl monochloride with anisole.

Vanadium compounds soluble in hydrocarbons that can be used in the preparation of a catalyst are halides and oxyhalides (VC14, VOClg, VBr) and such compounds in which at least one of the metal valences is saturated with a heteroatom (in particular, oxygen or nitrogen ) combined with an organic group, such as, for example, triacetylacetonate-, tribenzoyl acetonate-, diacetylacetonate- and haloacetylacetonate-vanadium; vanadyl trialkogol and haloalogol; tetrahydrofuranates, ethers or aminates of vanadium hydrochloride or tetrachloride oxychloride, pyridates of hydrochloride, vanadium tri- and tetrachloride.

tovenlen catalysts include, for example, triacetate-, tribenzoate- and tristearathanadium.

Although the preparation of the catalyst with vanadium halides and oxyhalides can use all the above-mentioned aluminum-organic compounds, it has been found that using such vanadium compounds in which at least one of the metallic valences is saturated with an oxygen or nitrogen atom combined with an organic group results are achieved in the preparation of the catalyst using halogen containing, their organometallic compounds.

The copolymerization process is carried out at temperatures ranging between -80 ° and + 125 ° C.

In cases where catalysts prepared from vanadyl triacetylacetonate, vanadyl diadethylacetonate, vanadyl haloacetylacetonates or even from a vanadium compound in the presence of dialkyl monohalides of aluminum are used, it is advantageous to conduct high copolymer production per weight unit of the catalyst used for catalyst preparation or copolymerization at temperatures between 0 ° and -80 ° C, preferably between -10 ° and -50 ° C.

Catalysts prepared under these conditions exhibit much higher activity than those prepared at higher temperatures, and moreover, the activity of the catalysts remains practically unchanged at the end of a long cycle.

In cases where catalysts prepared from vanadyl triacetylacetonate, vanadyl trialkolts, or vanadyl haloalkolts are used, at temperatures ranging between 0 ° and 125 °, special reagents that can be complexed are advantageous for obtaining high copolymer yields. selected from esters, thioesters, tertiary amines or trisubstituted phosphines containing at least one chain group or an aromatic nucleus.

The amount of reagent that can be complexed is preferably used in the range between 0.05 and 1 mol per 1 mol of alkyl halo alumina. The activity of the catalysts used in the process described here varies by the different molar ratios between the compounds used in the preparation of the catalyst.

When using a catalytic system consisting of, for example, trialkyl aluminum and vanadium halides or o, vanadium xyhalides, the ratio in mol between the trialkyl aluminum and the vanadium compound is in the range between 1 and 5, preferably between 2 and 4.

The w «x results are achieved with a molar ratio of A1 (C2H3) 2C1: UAAsz in the range between 2 and 20, preferably between 4 and 10.

. When using diethyl monofluoride aluminum instead of diethyl monochloride aluminum alumina, the highest activity occurs at a molar ratio between diethyl monofluoride aluminum and a vanadium compound of the order of 20.

The copolymerization process is dried in the presence of a hydrocarbon solvent such as butane, pentane, n-heptane, toluene, OR xylene, or their mixtures.

Especially high copolymer yields are achieved when carrying out the copolymerization process in the absence of an inert solvent using the monomers themselves in the liquid state, i.e. in the presence of an ethylene solution in the polymerized sb-olefin and cyclic polyene mixtures, which are in the liquid state.

To obtain copolymers with high compositional homogeneity, the ratio between the concentrations of the copolymerizable monomers, which takes place in the liquid phase of the reactants, is allowed to remain constant or at least possibly constant during the copolymerization process.

For this purpose, it is useful to carry out continuous copolymerization by continuously injecting and releasing a mixture of monomers with a constant composition and operating at high spatial rates.

The catalytic system used is prepared in the absence of monomers, or else by displacing the catalytic components with each other in the presence of copolymerizable monomers. The components of the catalyst can flow continuously in the polymerization process.

The composition of the copolymers can be modified by varying the mixture of monomers. If it is required to obtain amorphous copolymers of cyclic polyene with hylene and propylene, the molar ratio between ethylene and propylene in the liquid phase of the reactants should be less than or equal to 1: 4. In the case when butene is used instead of propylene, the ratio between ethylene and butene should be lower than or equal to 1:25.

It is generally desirable to introduce into the terpolymer from economic considerations also some amount of cyclic polyene (less than 20%).

The co-polymers, as such, of the present invention, delineate the qualities of unvulcanized elastomers in the sense that they have a low initial modulus of elasticity and exhibit very high final elongations.

The presence of unsaturated bonds in macromolecules is manifested in the fact that they can be vulcanized by means of methods.

commonly used for unsaturated rubbers, especially those with a low content of unsaturated bonds.

Vulcanized products exhibit high reversible elastic extensions, and when reinforcing fillers such as carbon black are used in the mixture, these products also exhibit good resistance to stresses.

Example 1. The reaction apparatus is a glass cylinder, equipped with a bifurcation and feed and discharge tubes for gases, which is immersed in a thermostatic bath at -20 ° C. The gas inlet tube reaches the bottom of the cylinder and ends in a porous diaphragm.

350 lgl anhydrous n-heptane and

15 ml of cyclooctadiene-1.5. A gaseous mixture of propylene and ethylene with a molar ratio of 2: 1 is injected through a tube intended to introduce gas, which is forced to circulate at a spatial velocity of about 200 m / h.

Previously, in a small flask with a capacity of 100 ml, the catalyst was prepared at a temperature of -20 ° C by reaction in 50 ml of n-geitane with 0.8 mmol of vanadium tetrachloride and 4 mmol of aluminum dpethyl monochloride. The catalyst thus formed in advance is introduced into the reactor through a siphon with nitrogen pressure. The polymerization reaction starts immediately, as evidenced by an increase in viscosity of the reaction mass.

The input and output of the propylene ethylene mixture is carried out at a spatial rate of about 400 nl per hour. 10 minutes after the start, the reaction is stopped by adding

20 ml of methanol containing 0.2 g of phenyl-rnaftilamine. The polymer is purified in a separator funnel in a nitrogen atmosphere by repeated treatments with dilute hydrochloric acid and then water.

followed by coagulation with acetone. After drying in vacuo, 13.5 g of solid amorphous product (as confirmed by X-rays), having the appearance of an unvulcanized elastomer, are obtained.

100 weight. parts of the polymer are mixed in a laboratory roller mixer with 1 part of phenyl-naphthylamine, 2 parts of sulfur, 5 parts of zinc oxide, 2 parts of lauroic acid, 1 part of tetramethylthiouramdisulfide and 0.5 parts of mercaptobenzothiazole.

The resulting mixture is subjected to vulcanization in the press for 30 minutes at a temperature of 150 ° C.

The result is a small vulcanized plate with the following characteristics:

Critical load 26 kg / cm

Final elongation 500%

Module LRI ZOOz / on lengthening 12 KV / c. Residual deformation after

When added to the above ingredients 50 wt. Part of carbon black carbon with subsequent vulcanization proceeding under the same conditions, a plate is obtained with the following characteristics:

Ultimate load 210 kg / sls2

Final elongation540%

Module at 300J / o elongation 80 kg / cm

Residual deformation after

gap15%.

Example 2. The process is carried out under the same conditions as described in example 1, but using 50 ml of cyclooctadiene-1.5 (instead of 15 ml). The catalyst is prepared in advance in the same way as in the previous example, but instead of diethyl monochloride aluminum

2 mmol trihexylaluminum.

After 4 minutes of polymerization, 7.5 g of a solid product are obtained, the amorphism of which is confirmed by X-ray research, and which in its appearance is similar to that of a vulcanized elastomer. The product is vulcanized with a mixture similar to the one mentioned above. The vulcanized product exhibits the following characteristics:

Critical load 40.7 kg / cm

Final lengthening520 / about

The modulus at 300% elongation is 14.2 / sg / s. And the residual deformation after breaking 4v / o.

Example 3. The process is carried out in the same way as described in example I, but using 2 mmol of 2-methyl-1,4-di - (diisobutyl aluminum) - butane instead of diethyl monochloro-aluminum in the preparation of the catalyst.

After 4 minutes of polymerization, 8.5 g of solid product is obtained, the amorphism of which is confirmed by X-ray research and which looks like an unvulcanized elastomer.

The resulting product is then vulcanized with a mixture similar to that mentioned in Example 1. The vulcanized product exhibits the following characteristics:

Critical load 51,5 kg / cm

Final elongation540%

Modzl at 300% elongation of 8.9 kg / cm

Residual strain and after

gap15%.

Example 4. In the reaction apparatus described in example 1, in which the temperature is maintained at -20 ° C, 350 ml of anhydrous n-geitane and 15 ml of cyclooctadiene-1.5 are introduced. A gaseous mixture is circulated in the apparatus, containing propylene and ethylene in a molar ratio of about 4: 1, at a rate of 400 liters / hour. The catalyst was previously prepared at a temperature of -20 ° C by dissolving 1.4 mmol of vanadium triacetylacetonate in 30 ml of anhydrous toluene by adding 7 mmol of diethyl monochloro-aluminum to the thus obtained solution.

The resulting catalyst is introduced into the reactor through a siphon. The inlet and outlet of the gaseous mixture is carried out at a speed in the order of 400 liters / hour.

After 9 minutes, the reaction is stopped. The result is 7.5 g of a solid amorphous product, in appearance similar to unvacanized elastomer, which is subjected to vulcanization with the same mixture as in example 1.

In conclusion, receive a small vulcanized plate with the following characteristics:

Critical load 25.7 kg / cm

Final elongation 600%

Iri modulus 300% elongation 12 kg / cMZ Residual deformi d after

rupture17 / o.

Cyrmer 5. The process is similar to that described in Example 1, but catalyst preparation and polymerization proceed at 24 ° C instead of -20 ° C.

After 15 minutes, 45 g of a solid amorphous product are obtained, the appearance of which is similar to the uncured elastomer and which is then subjected to vulcanization, just as described in Example 1. The vulcanized product has the following characteristics:

Critical load 40 kg / cm

Final elongation520%

Module at an elongation of 15 kg / cm Residual deformation after rupture 10%.

Example 6. A terpolymer prepared as in Example 1, consisting of ethylene, propylene and cyclooctadiene, containing 50 wt. o / o propylene and 3 wt. % cyclooctadiene and having a viscosity of 80 (measured at 100 ° C according to Monay ML 1 + 4), vulcanized for 60 minutes at a temperature of 150 ° C. The resulting vulcanized plate has the following properties upon aging. 910

The subject matter of the invention of organo-mineral compounds, which differs in the method of producing synthetic rubber in a vulcanized state by the copolymerization of ethylene with Ci - Ce-a-olefi-aging, in quality.

we and cyclodiene in the presence of metallo-5 cyclodiene used nonconjugated organoorganic coordination catalytic cyclic dienes, for example, cyclooctara, consisting of vanadium compounds and alu-diene-1.5.

235662 so that, in order to obtain rubbers, about