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研究了氯化钕异丙醇合物/三异丁基铝催化剂的配制方式对异戊二烯聚合和聚合产物特性的影响.将催化剂的悬浊液分离得到清液和沉淀,分别进行聚合,并对沉淀进行了拉曼光谱表征.结果表明,(Nd+Al)配制方式在室温和70℃下所得催化剂的清液均无活性,并且70℃下所得催化剂的沉淀也无活性.(Nd+IP+ Al)配制方式在任何条件下所得催化剂的各组分均有活性,推测该配制方式所得催化剂可能形成的是2种活性中心:(isoprenyl)2NdCl和(isoprenyl)NdCl2.配制方式对聚异戊二烯的微观结构没有影响(96%左右),分离前的悬浮催化剂和沉淀催化剂所得聚异戊二烯均为高分子量(Mn> 100×104)和窄分子量分布(Mw/Mn <2.0)的聚合物,但是分离后清液所得聚合物的分子量较低(Mn<30×104),分子量分布很宽(Mw/Mn>5.0).

参考文献

[1] WANG Fosong,PANG Deren,SHAN Renyu,et al.Rare Earth Catalysis Synthetic Rubber Anthology[M].Beijing:Science Press,1980:100-112(in Chinese).王佛松,庞德仁,沙人玉,等.稀土催化合成橡胶文集[M].北京:科学出版社,1980:100-112.
[2] Wilson D J,Jenkins D J.Butadiene Polymerization Using Ternary Neodymium-Based Catalyst Systems[J].Polym Bull,1992,27:407-411.
[3] YANG Jihua,HU Jingyu,PANG Shufen,et al.Orientation of Conjugated Diene Polymerization Catalyst with Higher Activity of Rare Earth Chloride[J].Sci China,1980,2:127-135(in Chinese).杨继华,扈晶余,逢束芬,等.对共轭双烯定向聚合活性较高的氯化稀土催化剂[J].中国科学,1980,2:127-135.
[4] Friebe L,Nuyken O,Obrecht W.Neodymium-Based Ziegler/Natta Catalysts and Their Applicationin Diene Polymerization[J].Adv Polym Sci,2006,204:1-80.
[5] Ricci G,Italia S,Cabassi F.Neodymium Catalysts for 1,3-Diene Polymerization:Influence of the Preparation Conditions on Activity[J].Polym Commun,1987,28:223-226.
[6] Yakovlev V A,Vollershtein E L,Cherezova L S,et al.Formation and Decomposition of Organometallic Compounds of Neodymium and Praseodymium in Oxidative Addition of Benzyl Chloride to Metals[J].Dokl Akad Nauk,SSSR,1983,268(6):1422-1425.
[7] SHAN Chengji,LIN Yonghua,WANG Mingyi,et al.The Nd-Al Bimetallic Complex Crystal with Catalytic Polymerization Activity[J].Chinese Sci Bull,1986,(2):123-125(in Chinese).单成基,林永华,王明义,等.有催化聚合活性的Nd-Al双金属络合物单晶[J].科学通报,1986,(2):123-125.
[8] SUN Tao,LI Yuliang,PANG Shufen,et al.Composition and Stereospecific Polymerization Acitivity of Nd-Al Bimetallic Complex Obtained from Rare Earth Chloride System[J].Chinese J Catal,1989,10(4):416-421(in Chinese).孙涛,李玉良,逢束芬,等.氯化稀土体系获得的Nd-A1双金属活性体的组成及其定向聚合活性[J].催化学报,1989,10(4):416-421.
[9] Barbotin F,Spitz R,Boisson C.Polymerization of Butadiene with a New Catalyst Based on a Neodymium Amide Precursor[J].Macromol Chem Phys,1999,200(5):1163-1166.
[10] LI Guilian,DONG Weimin,JIANG Liansheng,et al.Homogeneous Nd(vers)3/Al(i-Bu)2H/Al(i-Bu)2Cl Catalyst for Isoprene Polymerization[J].Chinese Synth Rub Ind,2006,29(3):181-186(in Chinese).李桂连,董为民,姜连升,等.均相Nd(vers)3/Al(i-Bu)2H/M(i-Bu)2Cl催化聚合异戊二烯[J].合成橡胶工业,2006,29(3):181-186.
[11] LI Guilian,YIN Weidong,DONG Weimin,et al.Crystallizable Polyisoprene under Strain Prepared by Nd-Based Catalyst[J].Chinese Synth Rub Ind,2009,32(3):249.(in Chinese)李桂连,尹卫东,董为民,等.用钕系催化剂合成具有拉伸结晶特点的聚异戊二烯[J].合成橡胶工业,2009,32(3):249.
[12] Mehrotra R C,Misra S N,Misra T N.Organic Compounds of Lanthanide Elements.Part Ⅳ.Alcoholates of Praseodymium and Neodymium Chlorides[J].J Indian Chem Soc,1965,42(6):351-358.
[13] LI Guilian.Study on Rare Earth Catalysts for Produce Polyisoprene with Narrow Molecular Weight Distribution[D].Changchun:Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,2008:91-93(in Chinese).李桂连.稀土催化剂合成窄分子量分布聚异戊二烯的研究[D].长春:中国科学院长春应用化学研究所,2008:91-93.
[14] Ren C Y,Li G L,Dong W M,et al.Soluble Neodymium Chloride 2-Ethylhexanol Complex as a Highly Active Catalyst for Controlled Isoprene Polymerization[J].Polymer,2007,48(9):2470-2474.
[15] REN Changyou,LI Guilian,DONG Weimin,et al.Polymerization of Isoprene with Neodymium Chloride Ethylhexanolate/Alkylaluminum Catalyst System[J].Chinese Synth Rub Ind,2006,29(6):472(in Chinese).任长友,李桂连,董为民,等.氯化稀土异辛醇配合物/烷基铝催化剂聚合异戊二烯[J].合成橡胶工业,2006,29(6):472.
[16] Kwag G,Lee H,Kim S.First in-situ Observation of Pseudoliving Character and Active Site of Nd-based Catalyst for 1,3-Butadiene Polymerization Using Synchrotron X-ray Absorption and UV-Visible Spectrascopies[J].Macromolecules,2001,34(16):5367-5369.
[17] JIN Yingtai,LI Xingmin,LIN Yonghua,et al.Synthesis,Characterization of Bimetallic Rare Earth Complexes and the Insertion Mechanism of Diene Polymerization[J].Chinese Sci Bull,1988,16:1234-1238(in Chinese).金鹰泰,李兴民,林永华,等.双金属稀土配合物的合成、结构表征及其聚合双烯烃插入机理的研究[J].科学通报,1988,16:1234-1238.
[18] Maiwad S,Sommer C,Müller G,et al.Highly Active Single-site Catalysts for the 1,4-cis Polymerization of Butadiene from Allylneodymium(Ⅲ) Chlorides and Trialkylaluminiums:a Contribution to the Activation of Tris(allyl) neodymium(Ⅲ)and the Further Elucidation of the Structure-activity Relationship[J].Macromol Chem Phys,2002,203(7):1029-1039.
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