文献类型：专利

英文题名：New (P,O) type ligand comprising substituted 2-(diphenylphosphino)benzenesulfonic acid, useful for forming (P,O) type ligand and palladium acetate containing catalyst system for ethylene polymerization

作者：FAN S;FU Y;LI S;ZHANG D;DENG X

机构：[1]UNIV EAST CHINA SCI&TECHNOLOGY

申请号：CN102584896-A

申请日：2011-12-21

公开日：2012-07-18

语种：英文

收录：DERWENT

摘要：NOVELTY - (P, O) Type ligand comprising substituted 2-(diphenylphosphino)benzenesulfonic acid is new. USE - For forming (P, O) type ligand and palladium acetate containing catalyst system, which is useful for ethylene polymerization; methyl acrylate polymerization; and methyl acrylate and ethylene polymerization (claimed). ADVANTAGE - The catalytic system comprising the (P, O) type ligand and palladium acetate has high catalytic activity, raw materials are easy to obtain, and is convenient to prepare. In catalytic system, adjusting of sulfonic acid substituents of the (P, O) type ligand, results in oligomerization of ethylene, or ethylene and methyl acrylate copolymerization, such that in the polymer molecular weight and molecular weight distribution can be adjusted and controlled. DETAILED DESCRIPTION - (P, O) Type ligand comprising substituted 2-(diphenylphosphino)benzenesulfonic acid of formula (I) is new. R1=H, or 1-12C alkyl; R2=H, 1-12C alkyl, or 1-12C alkoxy. INDEPENDENT CLAIMS are included for the following: (1) method for preparation of the (P, O) type ligand (I), involving: reacting aryl sulfonic acid and lithium hydroxide at molar ratio of 1:0.85 to 1:1 to produce aryl lithium sulfonate; under protection of inert gas, dissolving aryl lithium sulfonate in tetrahydrofuran, adding N-butyl lithium at molar ratio of 1.05-1.5, and reacting for 6-16 hours at 0-25 degrees C followed by adding tetrahydrofuran solution of diaryl phosphorus compound, and reacting for 16 hours at 0-25 degrees C; adding ammonium chloride to de-gas the water solution, extracting organic layer, washing with ether, adding hydrochloric acid, extracting by dichloromethane, drying by anhydrous magnesium sulfate, pumping solvent to obtain crude product; subjecting thick crude product to re-crystallization purification method, where organic solvent is prepared by methylene dichloride and alcohol compound selected from 1-4C alcohol (preferably methanol or ethanol), in which dichloromethane and alcohol compound volume ratio is 50-100:1; (2) method for forming (P, O) type ligand and palladium acetate containing catalyst system for ethylene polymerization in high pressure kettle comprising ethylene atmosphere, involving: adding to kettle water having dissolved in it the (P, O) type ligand (I), and acetic acid solvent containing palladium as palladium acetate in mol ratio of 1:1-2:1, stirring, continuously introducing ethylene gas where ethylene pressure is (20-60, preferably 30-40) atm at 80-100 degrees C, reacting for (5-24, preferably 10-24) hours, stopping inletting ethylene gas, releasing product after adding 5% hydrochloric acid methanol solution to stop the reaction, filtering, and drying to obtain the polymer; (3) method for forming catalytic system formed by (P, O) type ligand and palladium acetate for methyl acrylate polymerization, involving: to Schlenk bottle adding the (P, O) type ligand (I) and palladium as palladium acetate in acetic acid solvent at mol ratio of 1:1-2:1, after pumping argon gas for several times adding solvent (10 ml), stirring uniformly, adding methyl acrylate monomer (5 ml), keeping in 80-100 degrees C oil bath for 5-24 hours, adding 5% hydrochloric acid methanol solution to stop reaction, filtering, and drying to obtain the polymer; and (4) method for forming catalytic system formed by (P, O) type ligand and palladium acetate for methyl acrylate and ethylene polymerization, involving: to high pressure kettle having ethylene atmosphere, adding water dissolved in it the (P, O) type ligand (I) and acetic acid solvent having palladium as palladium acetate, in mol ratio of 1:1-2:1, after stirring, continuing ethylene saturation, adding methyl acrylate, continuing filling ethylene gas and keeping pressure at (20-60, preferably 30-40) atm, at 80-10 degrees C, reacting for (5-24, preferably 10-24) hours, stopping inletting ethylene gas, then adding 5% hydrochloric acid methanol solution to stop reaction, filtering, and drying to obtain the copolymer.