钯-稀土催化一氧化碳和苯乙烯交替共聚反应  

Copolymerization of Carbon Monoxide and Styrene Catalyzed by Palladium-Rare Earth Catalyst

作　　者：郭锦棠[1] 刘冰[1] 李伶[1] 王新英[1] 孙经武[1] 

机构地区：[1]天津大学化工学院,天津300072

出　　处：《催化学报》2004年第3期231-237,共7页

摘　　要：利用稀土钇盐或钕盐和乙酸钯组成的催化体系催化一氧化碳和苯乙烯共聚 ,合成了聚 (1 氧代 2 苯基丙撑 ) .用元素分析、红外光谱、示差扫描量热、热重分析及X射线光电子能谱 (XPS)等方法对共聚产物进行了表征 .测试结果表明 ,共聚物为一氧化碳和苯乙烯的线性交替共聚产物 ,其玻璃化温度为 2 35℃ ,熔点为 2 5 0℃ ,分解温度为 32 5℃ ,且用XPS未检测到聚合物中含有残留的金属 .同时考察了催化剂组分 2 ,2′ 联吡啶、对甲苯磺酸和对苯醌及溶剂甲醇等的用量对共聚反应的影响 ,并对聚合反应条件进行了优化 .在优化的反应条件下稀土与钯组成的复合催化剂对一氧化碳和苯乙烯交替共聚的催化活性可达 12 0 0 g/(g·h) .The copolymerization of carbon monoxide and olefin represents a very attractive field of research due to the ready availability of the raw materials and the unique combination of performance properties of the products, but the palladium catalyst always makes the industrialization of this process difficult because of its high cost. In this paper, a new homogeneous catalytic system is reported to improve the productivity of polyketone. Poly(1-oxo-2-phenyltrimethylene) was synthesized by copolymerization of carbon monoxide and styrene in the presence of the palladium-rare earth catalyst formed in situ from palladium acetate, yttrium acetate or neodymium acetate, 2,2′-bipyridyl, p-toluenesulfonic acid, and p-benzoquinone in methanol solvent. The copolymer was characterized by elemental analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetry, and X-ray photoelectron spectroscopy (XPS). The results indicated that the copolymer is a linear alternating copolymer of carbon monoxide and styrene and its glass transition temperature, melting point, and decomposition temperature are 235, 250, and 325 ℃, respectively. There is no metal in the copolymer according to the XPS results. The effects of components including 2,2′-bipyridyl, p-toluenesulfonic acid, p-benzoquinone, and methanol on the copolymerization were investigated. Polymerization conditions were optimized and under the optimum conditions the catalytic activity of the Pd-RE composite catalyst was about 1?200 g/(g·h) for the copolymerization of carbon monoxide and styrene.

关 键 词：钯 稀土 钇 钕 一氧化碳 苯乙烯 交替共聚 聚酮 

分 类 号：O643.3[理学—物理化学]