苯丙水溶胶的合成与性能研究(I) 聚合工艺和反应组分对聚合稳定性和胶体性能的影响

用一次投料法、半连续滴加法和单体预乳化法三种聚合工艺，合成了苯丙乳液聚合物，并加氨微细化，转化成水溶胶，考察了聚合工艺和反应组分（乳化剂，功能单体等）对苯丙乳液及其水溶胶反应稳定性和粒子大小及分布等胶体性能的影响。     

铬系乙烯齐聚和聚合催化剂

综述了近年来国内外铬系催化剂的最新研究进展。介绍了该类催化剂齐聚和合的性能研究和应用，讨论了该催化剂长期引起争议的活性中心，活性价态，以及反应机理，并同时预测了铬系催化剂在工业和纳米技术方面的发展趋势。     

超高分子量聚苯乙烯的合成和聚合反应动力学

杯芳烃钕与Mg(n Bu) 2 、HMPA所组成的三元络合催化剂用于苯乙烯配位聚合能以高收率制得超高分子量聚苯乙烯 .以甲苯为溶剂 ,在一定条件下制成三元配位催化剂 ,当 [Nd]=8× 10 - 4mol L ,[St]=4 .0mol L ,Mg Nd =2 0 .0 (摩尔比 ) ,HMPA Mg =1.0 (摩尔比 ) ,5 0℃聚合 4 5min ,聚合转化率可达到 80 %左右 .所得聚苯乙烯的重均分子量高达 2 10× 10 4 ,分子量分布指数为 1.6 1.间规聚苯乙烯含量为 81% .动力学研究表明 ,聚合反应速率与单体和主催化剂 杯 [6 ]芳烃钕的浓度分别呈 1次方关系 ,聚合反应的表观活化能为 4 1.7kJ mol     

电化学聚合漆酚铜配合物催化引发醋酸乙烯酯聚合的研究

将电化学聚合方法得到的聚合漆酚 (EPU)与氯化铜异丙醇溶液作用生成电化学聚合漆酚铜配合物(EPU Cu2 + ) .采用顺磁共振波谱 (ESR)、红外光谱 (FT IR)、XPS光电子能谱、原子发射光谱 (AES)、元素分析及AES等手段进行表征 ,确定该配合物的结构即每个铜离子与EPU分子中二个链节单元的羟基发生配位 .配合物中铜含量达 8 6 3% .实验表明 ,电化学聚合漆酚铜 (EPU Cu2 + )配合物膜在室温下的Na2 SO3水体系 (pH =7)中能催化引发醋酸乙烯酯 (VAc)按自由基加聚反应历程进行聚合 .讨论了温度、Na2 SO3浓度、VAc浓度和EPU Cu2 + 膜用量对聚合速率、诱导时间的影响 ,求得聚合速率的表达式Rp=0 0 7e- 2 82 5 RT[VAc]1 54[Na2 SO3]0 5,实验结果表明 ,EPU Cu2 + 配合物膜催化引发醋酸乙烯酯 (VAc)聚合的诱导期为 12 2s ,反应 2 4h后PVAc得率为79% , Mw =1 2 6× 10 6 , Mn=2 6 3× 10 5,多分散性系数为 4 79.     

六甲氧基甲基三聚氰胺-多元醇-丙烯酸酯混杂聚合过程热互补效应的研究

六甲氧基甲基三聚氰胺（HMMM）－多元醇－丙烯酸酯－酸催化剂的混合体系在较高温度下同时进行缩聚和自由基聚合并表现出协同效应，DSC研究结果表明，丙烯酸酯在HMMM和酸的催化作用下可在较低温度下发生自由基聚合反应，并把反应释放出来的大量的热量有效地传递给缩聚发反应，满足缩聚反应吸热的要求，从而节省固化所需要的能量，为了提高储存稳定性。本文以潜酸催化剂作为酸的来源，对该混杂聚合体系进行了研究，仍有明显的热互补效应。     

(Imido)vanadium(V)‐alkyl,Alkylidene Complexes Exhibiting Unique Reactivities towards Olefins,Phenols, and Benzene via 1,2‐C‐H Bond Activation

Recent examples for synthesis and reaction chemistry with (imido)vanadium(V)‐alkyl, ‐alkylidene complexes have been briefly summarized. (Arylimido)vanadium(V) dichloride complexes especially containing aryloxo ligands exhibited notable activities for ethylene polymerization, and the reacition pathways for the polymerization/dimerization using (imido)vanadium(V) dichloride complexes containing (2‐anilidomethyl)pyridine ligands can be tuned by modification of the steric bulk in the imido substituents; the adamantylimido analogues exhibited exceptionally high both activity and selectivity in the dimerization. These vanadium(V)‐alkyl complexes showed unique reactivity toward phenols; the reaction proceeds via coordination of phenols to the vanadium. The vanadium(V)‐alkylidene complexes were generated by α‐hydrogen elimination from the dialkyl analogues in the presence of PMe₃ etc.; the subsequent 1,2‐C‐H bond activation of benzene with (arylimido)vanadium(V)‐alkylidene containing 1,3‐(2′,6′‐diiso‐propylphenyl)imidazolin‐2‐iminato (Im^DIPPN) ligand took place cleanly.     

Halonickel 2,4-di-t-butyl-6-(quinolin-8-yliminomethyl)phenolates: Synthesis, characterization and ethylene reactivity

A series of nickel halides bearing 2,4-di-t-butyl-6-(quinolin-8-yliminomethyl) phenolate ligands was synthesized and characterized by IR spectroscopy and elemental analysis.Molecular structures of C1(R = H,X = Br) and C2(R = H,X = Cl) were further confirmed by single-crystal X-ray crystallographic studies,and revealed a distorted square planar geometry at nickel.Upon activation with diethylaluminum chloride(Et 2 AlCl),all nickel pre-catalysts displayed good catalytic activity [up to 9.3 × 10 5 g mol 1(Ni) h 1 ] for ethylene oligomerization with major dimerization.In the presence of methylaluminoxane(MAO),the nickel complex C1 was capable of ethylene polymerization under 3 MPa,and produced polyethylene products with narrow polydispersity(1.16 1.73) and molecular weights in the range of 2.6 4.95 kg/mol.     

真空导入成型阴离子聚合尼龙6聚合体系及性能

通过测量不同聚合体系下的阴离子聚合尼龙6(APA-6)反应过程中转化率随时间的变化, 结合真空导入成型的特点, 研究了适合于真空导入成型的APA-6的聚合体系. 研究发现, 己内酰胺钠盐/双酰化内酰胺-1,6-己二胺(C10/C20)(100℃)和己内酰胺钠盐/甲苯二异氰酸酯(C10/TDI)体系反应初期均存在一个转化率线性缓慢增长期, 随后, 聚合体系开始快速反应, 转化率呈指数增长, 反应很快达到平衡. 初步判定这两种体系是适合真空导入成型APA-6复合材料的聚合体系. 在转化率测试的基础上, 利用DSC热分析从活性中心的形成机理进一步分析了C10/TDI体系更适合于较大、 较厚和结构复杂制品的整体成型的原因. 此外, 与普通PA6相比, 真空导入成型APA-6的结晶度、 模量和T_g显著提高, 并且在2种理想体系下聚合的APA-6的性能也有差别, 从活化剂的封端和解封端机理上进行了初步探讨.     

One- and two-dimensional NMR studies of methyl acrylate/vinyl acetate/N-vinyl carbazole terpolymers

Terpolymers of methyl acrylate/vinyl acetate/N-vinyl carbazole (M/A/C) with different compositions were synthesized by solution polymerization using AIBN as an initiator. Composition of terpolymers was determined from quantitative ¹³C{¹H} NMR spectrum. Two-dimensional heteronuclear single quantum correlation (HSQC) and total correlated spectroscopy (TOCSY) were used to assign the methylene and methine carbon resonances by analyzing two and three bond order couplings. Various resonance signals were assigned to different compositional and configurational sequences with the help of one- and two-dimensional NMR spectra. Three and four bond order coupling between carbonyl carbon and other neighboring protons have been investigated with the help of 2D heteronuclear multiple bond correlation (HMBC) spectra. The complex and overlapped ¹H NMR spectrum of terpolymer was analyzed completely with the help of 2D HSQC and TOCSY spectra.     

Titanium complexes with modifiable pyrazolonato and pyrazolonato-ketimine ligands: Synthesis, characterization and ethylene polymerization behavior

Six titanium complexes bearing pyrazolonato and pyrazolonato-ketimine ligands have been synthesized and characterized. It was found that the ligand structure of the synthesized complexes has a significant effect on the catalytic performance of the complexes. The synthesized complexes were activated with MAO and their activities varied from negligible to high (up to 612 kg_PE/(mol_Ti h bar). The pyrazolonato-ketimine complex with a phenyl substituent in the imine part was the most active in the series and it was the only one producing polyethylenes with relatively narrow molecular weight distribution (M_w/M_n from 1.6 to 2.2).