An effective route for the synthesis of cationic palladium complexes of general formula [(Acac)PdLL]A

A series of palladium complexes of general formula [(Acac)PdL¹L²]⁺A⁻, where L¹, L² = phosphines and A = BF₄, CF₃SO₃, were synthesized. Preliminary studies show that the complexes are active in selective dimerization of styrene and addition polymerization of norbornene.     

Copolymerization of(10-oxo-10-hydro-9-oxa-10λ~5-phospha-phenanthrene-10-yl)-methyl acrylate with styrene

A phosphorus-containing monomer(10-oxo-10-hydro-9-oxa-10λ~5-phosphaphenanthrene-10-yl)-methyl acrylate(M_1) was copolymerized with styrene to give a potential flame retardant copolymer of high thermal stability.The structures of monomer and copolymer were characterized by FT-IR and ~1H NMR measurements.The reactivity ratios for free-radical of the monomer(M_1) and styrene(M_2) were studied.The calculated results are as follows:r_1=0.225,r_2=0.503;Q_1=0.413,e_1= 0.476;azeotropic point = 0.37.TGA and DTG c...     

A comprehensive Monte Carlo simulation of styrene atom transfer radical polymerization

<正>An optimized and high-performance Monte Carlo simulation is developed to take thorough account of four different cases of termination in styrene ATRP.According to the simulation results,the bimolecular termination rate constant sharply drops throughout the polymerization when either chain-length dependency of termination rate constant,gel effect,or both together is applied to the simulation.In addition,as expected,the initiator is quickly decomposed at the early stages of the polymerization.The concentration of the catalyst in lower oxidation state decreases at first and then plateaus at higher conversion;furthermore,the steady concentration of M_t~nY/L in the polymerization is the highest when the chain-length-dependent diffusion-controlled termination rate constant is employed in the simulation.The rates of deactivation and chain end degradation reactions are also smaller in this case.Therefore,the fraction of dormant chains is higher throughout the reaction and consequently the portion of dead polymers decreases.Besides,molecular weight increases linearly with conversion;however,when neither gel effect nor chain-length dependency of termination rate constant is considered,the molecular weight deviates from linearity at the end of the reaction.The peak of chain length distribution shifts toward higher molecular weight too during the reaction.Finally,the molecular weight distribution broadens at higher conversion;however, the chain length distribution of polymers produced under conditions of applying chain-length-dependent diffusion-controlled termination rate constant is narrower.     

GMA和共单体对聚乙烯木塑复合材料的直接反应增容

通过甲基丙烯酸缩水甘油酯(GMA)、聚乙烯(PE)、木粉和其它助剂的熔融挤出,实现了GMA及GMA与共单体对PE和木粉的直接反应增容.通过扫描电镜(SEM)观测了PE基木塑复合材料(WPC)的冲击断面形貌.测试了WPC经抽提后所得木粉的傅立叶变换红外光谱(FTIR)和WPC的力学性能及热变形温度(HDT).研究了共单体苯乙烯(St)和抑交联剂亚磷酸三苯酯(TPP)对反应增容的影响.结果显示,经GMA和引发剂反应增容后,有部分PE分子键合到了木粉粒子上,从而增强了木塑两相的结合力;St的加入有利于提高GMA的接枝率,导致更多PE分子键合到了木粉粒子上,而TPP的加入则使GMA的接枝率有所下降.经GMA和引发剂直接反应增容后,WPC的力学性能和HDT均明显改善;St的加入有助于抑制PE的交联,但并未造成WPC力学性能和HDT的明显劣化;同时加入St和TPP后,WPC的HDT有所下降,而断裂伸长率和冲击强度则明显提高.     

本体聚合反应全过程苯乙烯增长自由基的ESR谱的研究

本文对苯乙烯本体聚合全过程增长自由基ESR谱进行了研究,对全过程ESR谱的模拟和分析及构象能的计算表明:反应初期12线谱由产生6线谱构象R_1和8线谱的构象R_2叠加而成,其相对含量R_1>R_2。反应中期4线谱和6线的ESR谱的模拟结果为:R_1相似文献   

橡胶接枝苯乙烯本体共聚合全程动力学研究(Ⅰ)--接枝行为

橡胶接枝苯乙烯本体聚合的研究目前主要集中于预聚阶段接枝动力学和聚合条件对相转变的影响[1]. 对于后聚阶段, 即相转变后的接枝行为, 尤其是接枝率与橡胶相内包容物的关系、接枝率与高转化率聚合动力学的关系, 接枝率与橡胶相结构的关系等则研究很少. 这些因素对最终聚合物的性能起着至关重要的作用, 因此, 研究橡胶接枝苯乙烯本体聚合相转变以后接枝率的变化, 并找出橡胶相形态演绎过程的规律很有意义.     

硅氢加成反应高选择性合成甲基苯乙基二氯硅烷

研究了硅胶负载聚乙二醇铂催化苯乙烯与甲基二氯氢硅的硅氢加成反应,β-加成产物甲基苯乙基二氯硅烷的选择性为100%,10℃下反应8h苯乙烯转化率为96.0%.反应存在一个诱导期,温度等反应参数对诱导期有重要影响,40℃下反应的诱导期不到1h,并探讨催化剂的催化机理和目标产物高选择性的原因.     

REVERSE ATOM TRANSFER RADICAL POLYMERIZATION OF STYRENE WITH COPPER-BASED CATALYST

 "Living"/controlled radical polymerization of styrene was carried out with diethyl 2,3-dicyano-2,3-diphenylsuccinate (DCDPS)/CuCl₂/bipyridine (bipy) initiation system at 120℃. The molecular weights of resultant PSt increased with the monomer conversion and the polydispersities were in the range of 1.37 ～ 1.52. A linear ln([M]o/[M])versus time plot was also obtained indicating the constant concentration of growing radicals during the polymerization with this initiation system. End group analysis by ¹H-NMR spectroscopic studies showed that the end groups of the polymer obtained is cω-functionalized by a chlorine group from the catalyst and a-functionalized by a (carbethoxy-cyano-phenyl)methyl group from the fragments of the initiator. Having C1 atom at the chain end, the PSt obtained can be used as a macroinitiator to promote a chain-extension reaction with fresh St and block copolymerization reaction with a second monomer, such as methyl methacrylate, in the presence of CuC1/bipy catalyst via a conventional ATRP process.     

苯乙烯/N-苯基马来酰亚胺共聚物分子量测定和模型

从内聚能的角度建立了含共聚组成、序列不均匀性的共聚物分子量及分布理论,导出其计算式.将凝胶渗透色谱(GPC)与紫外吸收光谱(UV)和示差折光仪(DR)串接,测定苯乙烯(St)/N-苯基马来酰亚胺(PMI)共聚物的分子量.根据St/PMI共聚合原理,对St-PMI共聚物的分子量进行模型化,该模型能较好地预测引发剂、单体配比、转化率对共聚物分子量的影响.     

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