橡胶技术网

合成橡胶工业
CHINA SYNTHETIC RUBBER INDUSTRY
2010 Vol.33 No.6 P.475-481

橡胶技术网

新癸酸钕体系对丁二烯聚合活性及产物结构的影响

张旭  肖力光  蔡洪光  张学全 

摘 要:综述了新癸酸钕(NdV3)/烷基铝/氯化合物三元催化体系催化丁二烯聚合的一般规律,分析了烷基铝结构及用量、氯化合物的品种及用量对催化活性和聚合物结构,包括活性中心的成因、单体插入方式、分子量分布及顺式-1,4-结构含量的影响.
关键词:新癸酸钕;烷基铝;氯化合物;丁二烯;聚合活性;聚合物;结构;综述
分类号:TQ331.4+99  文献标识码:A

文章编号:1000-1255(2010)06-0475-07

Effects of neodymium-versatate-based catalysts on polymerization activity of 1,3-butadiene and structure of polymer

Zhang Xu  Xiao Liguang  Cai Hongguang  Zhang Xuequan 

基金项目:国家科技支撑计划资助项目(20 BAE 14 B 00).
作者简介:张旭(1983-),女,硕士研究生.已发表论文2篇.
作者单位:张旭(吉林建筑工程学院,材料科学与工程学院,吉林,长春,130021) 
     肖力光(吉林建筑工程学院,材料科学与工程学院,吉林,长春,130021) 
     蔡洪光(中国科学院,长春应用化学研究所,吉林,长春,130022) 
     张学全(中国科学院,长春应用化学研究所,吉林,长春,130022) 

参考文献:

[1]Cabassi F,Italia S,Giarrusso A.The homopolymerization of 2,3-dimethyl-1,3-butadiene and the copolymerization of 1,3-butadiene/2,3-dimethyl-1,3-butadiene using the catalyst system AlEt2Cl-CO(ACAC)2:A structural investigation of the products[J].Macromol Chem,1986,187(4):913-921.
[2]Wilson D J.Recent advances in the neodymium catalyzed polymerization of 1,3-dienes[C].International SYMP on advances in olefin cycloolefin and diolefin polymerization.France:Macromol Chem Macromol Symp,1993:273-288.
[3]Carbonaro A,Ferraro D,Bruzzone M.Process for polymerizing conjugate diolefins,and means suitable for this purpose:US,4444903[P].1984-04-24.
[4]Monakov Y B,Marina N G,Duvakina N V,et al.Characteristics of the copolymerization of butadiene and isoprene in the presence of catalytic systems based on neodymium salts[J].Doklady Akademii Nauk SSSR,1977,236(3),617-619.
[5]Sylvester G,Witte J,Marwede G.Polymerisation of conjugated dienes in solution:Eur,0007027[P].1980-01-23.
[6]Wilson D J.A rare earth catalyst system for the polymerization of 1,3-butadiene:The effect of different carboxylates[J].Polymer,1993,34(16):3504-3508.
[7]Witte J.Progress on homopolymerization of diolefens by organometallic catalysts[J].Angew Macromol Chem,1981,94(5):119-146.
[8]Wilson D J.A Nd-carboxylate catalyst for the polymerization of 1,3-butadiene:The effect of alkylaluminums and alkylaluminum chlorides[J].Journal of Polymer Science (part A):Polymer Chemistry,1995,33 (14):2505-2513.
[9]Rocha T C J,Coutinho F M B,Soares B G.Effect of alkylaluminum structure on Ziegler-Natta catalyst systems based neodymium for producing high-cis polybutadiene[J].Poly Bull,2009,62(1):1-10.
[10]Marina N G,Gadeleva K K,Monakov I B,et al.Organo-aluminum component structure and the activity of the lanthanide-containing catalytic systems[J].Doklady Akademiinauk SSSR,1984,274(3):641-644.
[11]Shen Zhiquan.Progress in coordination polymerization by rare-earth catalysts[J].Inorganica Chimica Acta,1987,140 (1/2):7-14.
[12]杨彩云,郑玉莲,龚志,等.不同配位基团稀土化合物在异戊二烯本体聚合中的催化活性[J].合成橡胶工业,1990,13(5):326-329.
[13]Li Yuliang,Ouyang Jun.Characterization of polymer-supported rare-earth-metal complexes and their catalytic behavior in polymerization of conjugated diene[J].Macromol Sci Chem,A 24(3/4):227-242.
[14]Ricci G,Italia S,Cabbassi F,et al.Neodymium catalysts for 1,3-diene polymerization:influence of the preparation conditions on activity[J].Polym Commun,1987,28(8):223-226.
[15]Friebe L,Windisch H,Nuyken O,et al.Polymerization of 1,3-butadiene inititated by neodymium versatate/triisobutylaluminum/ethylaluminum sesquichloride:Impact of the alkylaluminum cocatalyst component[J].Macromol Chem,2004,A 41(3):245-256.
[16]Kozlov V G,Sigaieva N N,Nefediev K V,et al.The effect of the nature of organoaluminum compound and the catalytic system preparation procedure on molecular characteristics of cis-1,4-polybutadiene[J].Polym Sci(part A):Polym Chem,1994,32(7):1237-1243.
[17]Throckmorton M C.Comparison of cerium and other transition metal catalyst systems for preparing very high cis-1,4-polybutadiene[J].Kaut UGummi Kunstst,1969,22(6):293-297.
[18]Friebe L,Nuyken O,Obrecht W.Neodymium-based Ziegler-Natta catalysts and their application in diene polymerization.Neodymium based Ziegler catalysts-fundamental chemistry:Advances in polymer science[M].Berlin:Springer-Verlag Berlin,2006:1-154.
[19]Friebe L,Nuyken O,Windisch H,et al.Polymerization of 1,3-butadiene initiated by neodymium versatate/diisobutylaluminium hydride/ethylaluminium sesquichloride:Kinetics and conclusions about the reaction mechanism[J].Macromol Chem Phys,2002,203(8):1005-1064.
[20]Quirk R P,Kells A M.Polymerization of butadiene using neodymium cersatate-basedcatalyst systems:Preformed catalysts with SiCl4 as halide source[J].Polym Int,2000,49(7):751-756.
[21]Coutinho F M B,Rocha T C J,Mello I L,et al.Effect of electron donors on 1,3-butadiene polymerization by a Ziegler-Natta catalyst based on neodymium[J].Appl Polym Sci,2004,98(6):2539-2543.
[22]Maiwald S,Sommer C,Muoller G,et al.On the 1,4-cis-polymerization of butadiene with the highly active catalyst systems Nd(C3H5)(2)Cl center dot 1.5 THF/hexaisobutylaluminoxane (HIBAO),Nd(C3H5)Cl-2 center dot 2 THF/HIBAO and Nd(C3H5)Cl-2 center dot 2 THF/methylaluminoxane (MAO) -degree of polymerization,polydispersity,kinetics and catalyst formation[J].Macromol Chem Phys,2001,202(8):1446-1456.
[23]Maiwald S,Sommer C,Muoller 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.
[24]Quirk R P,Kells A M,Yunlu K,et al.Butadiene polymerization using neodymium versatate-based catalysts:Catalyst optimization and effects of water and excess versatic acid[J].Polymer,2000,41(15):5903-5908.
[25]Porri L,Giarrusso A,Ricci G.The polymerization of conjugated dialkenes to isotactic and syndiotactic polymers:Effect of ligands on the stereospecificity[J].Macromol Symp,1991,48/49:252-293.
[26]黄宝琛,史雨田,方旺喜,等.Nd(OR)3对异戊二烯聚合的催化活性[J].合成橡胶工业,1992,15(1):23-27.
[27]Hsieh H L,Yeh H C.Polymerization of butadiene and isoprene with lanthanide catalysts-characterization and properties of homopolymers and copolymers[J].Rubber Chem Technol,1985,58(1):117-145.
[28]Nickaf J B,Burford R P,Chaplin R P,Kinetics and molecular-weights distribution study of neodymium-catalyzed polymerization of 1,3-butadiene[J].Polym Sci(part A):Polym Chem,1995,33(7):1125-1132.
[29]Pross A,Marquardt P,Reichert K H,et al.Modeling the polymerization of 1,3-butadiene in solution with a neodymium catalyst[J].Angew Markromol Chen,1993,211:89-101.
[30]Oehme A,Gebauer U,Gehrke K,et al.The influence of the catalyst preparation on the homopolymerization and copolymerization of butadiene and isoprene[J].Macromol Chem Phys,1994,195(12):3773-3781.
[31]Wilson D J,Jenkins D K.Butadiene polymerization using ternary neodymium-based catalyst systems:The effect of Nd-halide radio and halide type[J].Polym Bull,1995,34(3):257-264.
[32]Gehrke K,Boldt D,Gebauer U,et al.Influence of conditions of synthesis on molecular properties of polybutadiene[J].Kautschuk Gummi Kunststoffe,1996,49(7/8):510-513.

收稿日期:2010年1月28日

修稿日期:2010年8月16日

出版日期:2010年11月15日