The way to obtain cis-1,4-polybutadiene

 

(57) Abstract:

The invention relates to techniques for the polymerization of butadiene - 1,3 and can be used in the synthetic rubber industry, and the obtained product is in the tire, rubber industries, in the production of high impact polystyrene and other purposes. The essence of the invention: process for the polymerization of butadiene - 1,3, carried out in toluene at 20-40oC under the action of a catalytic system consisting of compounds of cobalt (II) stearate, octoate, naphthenate, 2-ethylhexanate, acetylacetonate, taken in an amount of 0.03 to 0.2 mol/l, alyuminiiorganicheskikh compounds selected from the range: diisobutylaluminium chloride, diethylaluminium, isobutyltrimethoxysilane, ethylaminoethanol, based molar ratio of aluminum: cobalt in the range from 20 to 150 and water collected in the amount of 0,0008 - of 0.003 wt.% for the solvent, and optionally in the system enter polylooks formula

where R is ethyl, isobutyl, n is at least 2 of the calculation of its molar ratio to the compound of cobalt in the range of 2 to 30. The method allows to regulate the molar mass, microstructure, drastically reduce the amount of by-product - butenolide while maintaining a high RMSE is used in the synthetic rubber industry, and the obtained product in tire, rubber industries, in the production of high impact polystyrene and other purposes.

Known methods for producing high molecular weight CIS-polybutadiene by polymerization of 1,3 butadiene in a hydrocarbon solvent in the presence of compounds of cobalt (for example: octout, stearate, naphthenate, acetylacetonate, etc.,), alkylhalogenide (for example: diethylaluminium, sibutraminegeneric, ethylaminoethanol, etc.,) and water. As regulators of molecular weight and gelation use different connections: olefins, alcohols, ethers, etc. for a Review of these methods see [1]

The disadvantages of this method include the necessity of using an additional two or three components, and their further retrieval, and decrease the efficiency of the process in toluene, the expansion of the molecular mass distribution, reducing the strength properties of vulcanizers.

Known methods for producing polybutadiene by successively added to a solution of butadiene with an adjustable amount of water galogensoderjasimi aluminum organic compounds, followed by exposure for 2 h at 10-50oC and sa dichloride cobalt, diisobutylaluminium and water and adding triisobutylaluminum to 30 mol. in a mixture elyuminirovanie [3]

However, these methods are characterized by high costs of the components of the catalytic system, the change of molecular parameters of the final polymer, depending on the amount of additional substances or exposure time, reducing the speed of the process.

The closest in technical essence and the achievable result, to this invention and the base object is a method for bezgolovogo CIS-1,4-polybutadiene by conducting the polymerization of butadiene - 1,3 in an inert hydrocarbon solvent containing water and a monomer, cooled to (-8) (-78)oC and then adding to them coalitionism connection (naphthenate, octoate, stearate, etc.,) and aluminum (diisobutylaluminium, diethylaluminium, isobutyltrimethoxysilane and so on), the temperature increase up to 20-30oC and process at the same temperature. The solvent accept toluene in a ratio of components: Al/Co 10-1000; H2O/Co 1-60; [C4H6] 10-12 wt. [Co] 1,3 10-310-5mmol/l, [H2O] 0,0009 0.005 wt. The polymerization of 10-150 min, the conversion of the e large number butenolide, the speed reduction process in the case of regulating molecular weight.

The technical task of the present invention is the regulation of the microstructure, molecular weight, reduction of by-products while maintaining the high speed of the polymerization process.

This technical result is achieved in that the polymerization of 1,3 butadiene is carried out in toluene at 20 to 40oC under the action of a catalytic system consisting of compounds of cobalt: stearate, octoate, naphthenate, 2-ethylhexanate, acetylacetonate, taken in an amount 0,030 0.2 mmol/l, the organic aluminum compounds selected from the range: diisobutylaluminium chloride, diethylaluminium, isobutyl(ethyl)aluminiumanschlag, based molar ratio of aluminum: cobalt in the range from 20 to 150 and water collected in the amount of 0,00080 of 0.003 wt. the solvent and optionally in the system enter poliglumex (PSC) of the formula where R is ethyl or isobutyl, and n is 2 or more, taken from the calculation of the molar ratio to the compound of cobalt in the range of 2 to 30. The water in the reaction mass is introduced together with the solvent, and other components of the catalytic system or after holding the mixture for 0.5 h and Bo is polyaluminum to the content of cobalt is associated with the absence of the desired effect (lower values) and inexpediency of further expenditure of this product, etc. at higher values, the decrease of the molecular weight and the speed of the process.

After the process, the resulting solution of polybutadiene (polymerized) to introduce alcohol-toluene solution of the antioxidant Agidol-2 (NG-2246) in an amount of 0.6 wt. and was isolated by known methods by water degassing and drying in the mill.

The polymer is characterized by a Mooney viscosity, microstructure, molecular weight distribution, the number of oligomers butenolide in polymerizate. The process conditions and properties of polybutadiene all experiments presented in the table.

Example 1 (the prototype). In a glass 2-liter flask through a siphon enter 1123 g (1295 ml) of toluene containing 0,0024 wt. water and 126 g (194 ml) of 1,3 butadiene and cooled to -18oC. Then add a solution of cobalt naphthenate in toluene (initial concentration of 0.02 mol/l) and ethylaminoethanol (initial concentration of 0.5 mol/l), i.e. the concentration of cobalt in the mixture 5 10-5mol/l and the molar ratio of A1/Co 50. Next, the resulting mixture perelavlivaet 3-litre metal reactor equipped with a device for loading and unloading reagents, measurement of temperature and pressure, stirring and those who syshestvyut in a current of inert nitrogen gas. The duration of polymerization of 100 min, the degree of conversion of monomer (polymer yield) 65,9 wt. content butenolide in polymerizate is 0.07 wt.

Absolute process conditions and properties of the polybutadiene of this and other examples are presented in the table.

Example 2. Carried out as described in example 1.

In a glass 2-liter flask enter 1019 g (1175 ml) of toluene containing 0,0008 wt. water, and 186 g (286 ml) of 1,3 butadiene, cooled to (-10oC), incubated for 60 minutes Then add a solution of octoate cobalt ( concentration 0.02 m) 8 10-5mol/l and isobutyltrimethoxysilane (concentration 0.5 mol/l) calculated molar ratio of Al/Co 20 1. The resulting reaction mixture is poured into a metal reactor and when the stirrer is injected toluene solution polyalkyloxy (concentration of 0.25 mol/l, and the exact composition specified in the table) from the calculation of the molar ratio of PJSC/Co 30, is heated to 25oC and at the same temperature conducting the polymerization of 1,3 butadiene for 60 min, the polymer yield is 77,9 wt. content butenolide in polymerizate of 0.04 wt.

Example 3. Carried out as described in example 1.

In a glass 2-microborrower within 30 minutes Then add a solution of cobalt naphthenate concentration of 0.022 mol/l in 12 10-5mol/l and diisobutylaluminium (concentration of 0.61 mol/l) calculated molar ratio of Al/Co 60.

The resulting reaction mixture is poured into metal 3-liter reactor with the agitator enter solution polyaluminum (concentration 0,026 mol/l) calculated molar ratio of PJSC/Co 2, is heated to 20oC and at the same temperature conducting the polymerization of 1,3 butadiene for 90 min, the polymer yield is 87,4 wt. content butenolide in polymerizate 0.01 wt.

Example 4. Carried out as described in example 1.

In a glass 2-liter flask enter 1117 g (1289 ml) of toluene containing of 0.003 wt. water, 126 g (194 ml) of 1,3 butadiene zakolerovat to -15oC, incubated for 40 minutes Then add a solution of 2-ethylhexanate cobalt (concentration 0.01 mol/l) in an amount of 3 to 10-5mol/l, and diethylacetanilide (concentration of 0.61 mol/l) calculated molar ratio of Al/Co 150. The resulting reaction mixture is poured into metal 3-liter reactor, and when the agitator enter solution polyaluminum (concentration of 0.22 mol/l) based on 1,3 for 60 min, the polymer yield is 97,2 wt. and the content butenolide in polymerizate 0.005 wt.

Example 5. Carried out as described in example 1.

A 2-liter glass flask enter 1022 g (1179 ml) of toluene containing about 0.001 wt. water, 174 g (267 ml) of 1,3 butadiene, zakolerovat to (-12)oC, incubated for 30 minutes Then add the solutions acetylacetonate cobalt (concentration of 0.025 mol/l) 20 10-5mol/l, and ethylaminoethanol (concentration 0.5 mol/l) calculated molar ratio of Al/Co 20. The resulting reaction mixture and when the stirrer enter solution polyaluminum (concentration of 0.15 mol/l) calculated molar ratio of PJSC/Co=15, heated to 30oWith and at the same temperature conducting the polymerization of 1,3 butadiene for 90 min, the polymer yield is 86,3 wt. and the content butenolide in polymerizate 0,008 wt.

The way to obtain CIS-1,4-polybutadiene by the polymerization of butadiene-1,3 in a hydrocarbon solvent under the action of a catalytic system consisting of uglevodorodyonogo compounds of cobalt, alkylhalogenide and water, wherein the process is carried out in toluene in the presence of compounds of the formula

< / BR>is abalta in the range of 2 to 30.

 

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