Method for preparing liquid polybutadiene rubber by sulfoacid rare earth catalyst

A technology of liquid polybutadiene and rare earth catalyst, which is applied in the field of preparing liquid polybutadiene rubber with sulfonic acid rare earth catalyst, which can solve the problems of operator and environmental pollution and injury, difficulty in recycling, increase of production cost, etc., and achieve reduction Harm to human body and environment, mild polymerization process, effect of reducing production cost

Inactive Publication Date: 2012-05-16
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI +1
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

According to the catalytic system of liquid polybutadiene rubber, it is generally divided into sodium series, lithium series, transition metal (iron, cobalt, nickel, chromium) system and rare earth system; sodium series catalytic system synthesizes liquid polybutadiene rubber, In addition to the low catalytic efficiency, there are also the problems of complex catalyst composition, cumbersome process, and high content of 1 and 2 structures in the obtained rubber; the preparation method of the existing medium and low molecular weight liquid polybutadiene rubber is the most mature method of the lithium system. The system is a ternary system, with n-butyl lithium as the main catalyst, diethoxy dimethyl ether as the 1,2 structure regulator; tert-butoxide potassium as the molecular weight regulator; generally, the 1,2 structure can be controlled at 40% or so, and the weight average molecular weight can be adjusted to within 1000; but the method of preparing liquid polybutadiene rubber in this system also has insurmountable shortcomings: First, the large-scale polymerization production of this system is greatly affected by temperature and humidity , the production process parameters are not easy to control; secondly, the solvent used for the polymerization of this system is xylene, and the polymer obtained from the polymerization is miscible in xylene, and finally the xylene needs to be separated by a flash evaporation process. In addition to increasing the production cost, it is also easy to Pollution and injury to operators and the environment; (US Patented Dec.27, 1966)
[0004] Patents US2008182954-A1 and JP2008163338-A report a method for preparing liquid polybutadiene using a rare earth system, but this method requires methylaluminoxane (MAO) as a cocatalyst in the catalyst preparation process, and requires Toluene is used as a solvent, which not only increases the cost of catalyst preparation, but also pollutes the environment and is not easy to recycle
[0005] Other catalytic systems such as the use of transition metal cobalt, nickel, chromium compounds or complexes as catalytic active centers, although they can be prepared as binary systems, the polymerization solvent is still limited to benzene, toluene or xylene, which is not environmentally friendly. problem still unresolved

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] Example 1 Under the protection of nitrogen, in a dry catalyst reactor, 0.25 mmol of neodymium dodecylbenzenesulfonate and 15 mmol of diisobutylaluminum hydride Al(i -Bu) 2 H, add 2.33ml hexane again, be mixed with dodecylbenzenesulfonate neodymium rare earth catalyst solution, make the mole of rare earth neodymium in dodecylbenzenesulfonate neodymium in dodecylbenzenesulfonate neodymium rare earth catalyst solution The concentration is 5×10 -5 mol / ml; aged at -20°C for 24 hours to obtain a rare earth dodecylbenzenesulfonate neodymium catalyst.

[0017] The steps and conditions of the method for utilizing the above-mentioned catalyst to prepare liquid polybutadiene rubber are as follows: under nitrogen protection, add 50 g of butadiene monomer to an anhydrous and oxygen-free polymerization kettle, then add 21.39 ml of hexane, and then add 2.0 ml of the above-mentioned neodymium dodecylbenzenesulfonate catalyst, the molar ratio of catalyst neodymium dodecylbenzenesulfon...

Embodiment 2

[0019] Example 2 Under the protection of nitrogen, 0.25 mmol of neodymium dodecylbenzenesulfonate and 12.5 mmol of diethylaluminum hydride AlEt were added to the dry catalyst reactor according to the molar ratio of 1:50. 2 H, add 3.65ml hexane again, be mixed with dodecylbenzenesulfonate neodymium rare earth catalyst solution, make the rare earth neodymium in dodecylbenzenesulfonate neodymium in dodecylbenzenesulfonate neodymium rare earth catalyst solution The molar concentration is 5×10 -5 mol / ml; aging for 10 hours at a temperature of 20°C to obtain a neodymium rare earth dodecylbenzenesulfonate catalyst.

[0020] Utilize sulfonic acid rare earth catalyst to prepare the method step and the condition of liquid polybutadiene rubber as follows: under nitrogen protection, add 10g butadiene monomer in anhydrous and oxygen-free polymerization still, add 84.18ml hexane again, then Add 2.0ml of the above-mentioned neodymium dodecylbenzenesulfonate catalyst, the molar ratio of cata...

Embodiment 3

[0022] Example 3 Under the protection of nitrogen, 0.25 mmol of neodymium dodecylbenzenesulfonate compound and 10 mmol of diethylaluminum hydride AlEt were added to the dry catalyst reactor according to the molar ratio of 1:40. 2 H, add 4.92ml hexane again, be mixed with dodecylbenzenesulfonate neodymium rare earth catalyst solution, make the rare earth neodymium in dodecylbenzenesulfonate neodymium in dodecylbenzenesulfonate neodymium rare earth catalyst solution The molar concentration is 5×10 -5 mol / ml; aged at 10°C for 20 hours to obtain a rare earth dodecylbenzenesulfonate neodymium catalyst.

[0023] Utilize sulfonic acid rare-earth catalyst to prepare the method step and the condition of liquid polybutadiene rubber as follows: under nitrogen protection, add 5g butadiene monomer in the anhydrous oxygen-free polymerization still, add 92.04ml hexane again, Then add the above-mentioned neodymium dodecylbenzenesulfonate catalyst of 2.0ml, the mol number of catalyst dodecylb...

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Abstract

The invention relates to a method for preparing liquid polybutadiene rubber by a sulfoacid rare earth catalyst. The catalyst is formed by dual components and comprises the main catalyst of rare earth organic sulfoacid compound and the auxiliary catalyst of aluminum alkyl. A third component does not need to be added in the process for confecting the catalyst, thereby improving the production efficiency; hexane substitutes the solvents of benzene, toluene, dimethybenzene, and the like, thereby lowering damage of toxic solvent to the human body and the environment and reducing the product cost caused by recycling solvent; besides, the polymerization process is temperate and steady without adding a heat relieving device; and the liquid polybutadiene rubber with the monomer conversion rate of more than 90 percent, the weight-average molecular weight of 8800-22000 and the molecular weight distribution index of 4-6 can be obtained via polymerization.

Description

technical field [0001] The invention belongs to a method for preparing liquid polybutadiene rubber by using a sulfonic acid rare earth catalyst. Background technique [0002] Liquid polybutadiene rubber is usually widely used in adhesives, coating sealing materials, protective materials, modifiers, casting and molding products and other fields. According to the catalytic system of liquid polybutadiene rubber, it is generally divided into sodium series, lithium series, transition metal (iron, cobalt, nickel, chromium) system and rare earth system; sodium series catalytic system synthesizes liquid polybutadiene rubber, In addition to the low catalytic efficiency, there are also the problems of complex catalyst composition, cumbersome process, and high content of 1 and 2 structures in the obtained rubber; the preparation method of the existing medium and low molecular weight liquid polybutadiene rubber is the most mature method of the lithium system. The system is a ternary sy...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F136/06C08F4/52
Inventor 蔡洪光张旭白晨曦王硕王勋章代全权张春雨那丽华毕吉福张学全
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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