镍系胶体催化丁二烯聚合反应动力学的研究

Butadiene Polymerization Kinetics in Persence of Nickel Catalyst System

已证明在加氢汽油介质中ＺｉｅｇｌｅｒＮａｔａ型镍体系［Ｎｉ（ｎａｐｈ）２～Ａｌ（ｉＢｕ）３～（ＢＦ３ＯＥｔ２＋Ｃ８Ｈ１７ＯＨ）］为胶体催化剂。本工作按多相催化反应动力学理论处理胶体催化丁二烯聚合反应体系，提出了催化机理；认为链引发反应是催化剂各组份相互作用，在胶粒表面形成的活性位，再与单体反应形成活性种的过程，且后者为速率控制步骤；在链增长反应中，丁二烯在胶粒表面服从Ｌａｎｇｍｕｉｒ吸附规律，且插入反应为速率控制步骤。据此，导出的引发与增长速率方程式同实验结果相符合，得到的快引发时恒速率表示式为：ＲＰ，Ｃ＝ｋ［Ｃ］，并引入恒速期，表征活性种的稳定性。在链转移反应，主要链转移剂在活性位上按Ｌａｎｇｍｕｉｒ规律吸附，则导出的方程式与键谷勤等人给出的聚合度转化率公式相类似。

It is proved that OEt2+C8H17OH)]isacolloidaldispersesysteminhydrogasoline.Themechanismofcatalysisisdiscussedonthebasisofheterogenouscatalytictheory.Chaininitiationistheprocedureinwhichthecomponentsofthecatalystsysteminteractwitheachothertoformactivesiteswhichreactwiththemonomer,andtherateisdeterminedaccordingtothereaction.Inchainpropagation,butadieneisadsordedonthesurfaceofthecolloidparticleswhichobeytheLangmuirrule,andtheinsertionreactionisthegoverningequation.Theinitialpolymerizationrateandthepropagationratequiteagreetoexperimentalresults.Astochaintransfer,aconclusion,similartotherelationbetweennumberaveragedegreeofpolymerizationandpercentconversionproposedbyT.Kagiya,isdrawnwhenthemaintransferagentalsohasaLangmuirtypeadsorptiononthecolloid.