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纸质出版日期:1965-6-20,
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沈之荃, 龚仲元, 欧阳均. 希土化合物在定向聚合中的催化活性——Ⅱ.希土螯合物与三烷基铝组成的均相体系对丁二烯定向聚合的催化活性[J]. 高分子学报, 1965,7(3):193-200.
SHENG TSE-CHUAN, GUNG CHUNG-YUAN, Ouyang Chun. CATALYTIC ACTIVITY OF RARE EARTH COMPOUNDS IN THE STEREOSPECIFIC POLYMERIZATION Ⅱ. THE STEREOSPECIFIC POLYMERIZATION OF BUTADIENE WITH HOMOGENEOUS SYSTEMS COMPOSED OF CHELATES OF RARE EARTH ELEMENTS AND TRIALKYL ALUMINIUM[J]. Acta Polymerica Sinica, 1965,7(3):193-200.
沈之荃, 龚仲元, 欧阳均. 希土化合物在定向聚合中的催化活性——Ⅱ.希土螯合物与三烷基铝组成的均相体系对丁二烯定向聚合的催化活性[J]. 高分子学报, 1965,7(3):193-200. DOI:
SHENG TSE-CHUAN, GUNG CHUNG-YUAN, Ouyang Chun. CATALYTIC ACTIVITY OF RARE EARTH COMPOUNDS IN THE STEREOSPECIFIC POLYMERIZATION Ⅱ. THE STEREOSPECIFIC POLYMERIZATION OF BUTADIENE WITH HOMOGENEOUS SYSTEMS COMPOSED OF CHELATES OF RARE EARTH ELEMENTS AND TRIALKYL ALUMINIUM[J]. Acta Polymerica Sinica, 1965,7(3):193-200. DOI:
本工作研究了β-二酮类希土螯合物与三烷基铝组成的均相体系对丁二烯定向聚合的催化活性及一些聚合规律。实验结果表明下列希土螯合物与三乙基铝组合时都具有使丁二烯进行顺式-1
4定向聚合的催化活性:NdB3;NdB;NdBTA;NdTTA;PrB3;PrB;PrBTA;PrTTA;YB3;YBTA 以及 LaBTA 等。这些均相催化体系的活性远比非均相希土氯化物体系的高。在一定的催化剂浓度范围内
催化活性随着Al/希土及希土/丁(克分子比)的增高而增大。聚合反应速率对单体浓度呈一级关系
对希土螯合物浓度也近似呈 一级关系
并呈现一诱导期。丁二烯在 NdB3-Al(C2H5)3体系中聚合的总活化能为 13±0.5千卡/克分子。研究不同希土元素的这些螯合物表明同一元素的不同螯合物体系的聚合反应速率和聚合物链结构都没有显著的差别。但不同希土元素的同一整合物体系的聚合活性相差较大
含有镨和钕螯合物体系的活性比其他体系大。由这些均相催化体系所得聚丁二烯的1
2链节含量不超过1%
都不含或含很少量凝胶
聚合物的[η]随着Al/希土(克分子比)以及希土/丁(克分子比)的增大而降低
[η]可以从 4—5降至 1以下。Al(i-C4H9)3也能与这些螯合物组成活性催化体系,但活性很低,Al(C2H5)2Cl则不能与这些螯合物构成活性催化体系。
The stereospecific polymerization of butadiene catalysed by homogeneous systems formed by combination of trialkyl aluminium with β-diketone chelates of rare earth ele-ments has been studied.It has been shown that combinations of the following rare earth chelates with triethyl aluminium could induce cis-1,4 stereospecific polymerization of butadiene: NdB3(B=benzoylacetonate),NdB,NdBTA(BTA=benzoyltrifluoroacetonate),NdTTA(TTA=thenoyltrifIuoroacetonate),PrB3,PrB,PrBTA,PrTTA,YB3,YBTA,and LaBTA.These homogeneous systems appear to possess much higher catalytic activity than those of the heterogeneous systems formed by combination of triethyl aluminium with halides of lanthanons studied earlier.Up to a certain extent of catalyst concentration,the catalytic activities of these systems increase with increasing ratio of Al/chelate or chelate/butadiene (molar ratio).The polymerization has an induction period and it is found that the rate of polymerization is of first order with respect to the monomer concentration and approximately of first order to the chelate concentration.With the NdB3-Al(C2H5)3 system.the activation energy of polymerization has been determined tO be 13.0±0.5 kcal/mole.Both polymerization rate and microstructure of polybutadiene depend upon the nature of the rare earth metal in the chelates rather than that of the ligands in various chelates,and the praseodymium and neodymium chelate systems gave higher catalytic activity.It is interesting tO note that polybutadienes obtained with these homo-geneous systems always have a 1,2-structure content less than 1%,with 1ittle or even no geI formation.The intrinsic viscosities of the polymers obtained varying from 4一5 to 1,depend on the Al/chelate and chelate/butadiene ratios.Variation in alkyl groups on the aluminium component results in a marked difference in catalytic activity.The Al(i-C4H9)3 system exhibits low activity and Al(C2H5)2Cl system is inactive.
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