N—苯基马来酰亚胺与苯乙烯共聚合的研究

对Ｎ－苯基马来酰亚胺与苯乙烯悬浮聚合体系作了系统的研究，找到适合该体系的最佳反应温度，单体用量化，引发剂用量，搅拌速度以及水油比。通过采用聚乙烯醇，ＣＭＣ－Ｎａ盐，无机粉末混合分散剂，得到稳定的悬浮体系，产物为颗粒起先均匀分布在０．５－０．７ｍｍ范围内的ＩＰ树脂。     

Thermal Polymerization of Styrene,Part 1 – Bulk Polymerization

The thermal bulk polymerization of styrene is critically reviewed. There is still no generally accepted kinetic model for the thermal radical formation process, but ideal second‐ or third‐order models are widely used for modeling bulk systems. Since initiation and chain transfer reactions cannot be treated independently from one another as long as the same species is considered to be involved, it is concluded that non‐ideal kinetics, possibly in form of a (micro‐)viscosity dependency of the Mayo mechanism, are likely to be present. A mathematical model is presented that keeps the predictive capabilities of the Hui‐Hamielec model, but allows facile implementation of reaction specific modifications. Part 2 of this paper will focus on the effect of compartmentalization on the thermal polymerization of styrene.

     

Living Radical Polymerization of Styrene Derivatives Containing Trialkylmetal Groups

Fourteenth group oganometallic styrene derivatives were synthesised by nitroxide-mediated controlled radical polymerization using di-tert butyl nitroxide (A-T) as initiator. This is the first time that nitroxide-controlled radical polymerization has been successfully adapted for the synthesis of new polystyrenes bearing organometallic species with controlled molecular weights and narrow polydispersities. Monomer reactivity ratios were determined in controlled nitroxide-mediated radical copolymerization between styrene and substituted styrene. All experiments permitted the synthesis of new organometallic polymers that will be used for the development of a polymer capsule for Inertial Confinement Fusion Experiments.     

红外光谱法研究苯乙烯原子转移自由基聚合反应动力学

利用红外光谱法测定反应转化率研究原子转移自由基聚合反应动力学。在环己酮溶液中,以卤代烃为引发剂,过渡金属卤化物与配位剂２,２‘－联吡啶为催化体系,进行了苯乙烯聚合。分别就反应温度,反应物浓度和引发体系对苯乙烯聚合速率的影响进行了动力学测定,证实了原子转移自由基聚合具有活性聚合的特征,同时计算并讨论了苯乙烯原子转移自由基聚合反应的动力学数据。     

Simulation of Styrene Polymerization by Monomolecular and Bimolecular Nitroxide‐Mediated Radical Processes over a Range of Reaction Conditions

Simulations of polymerization rate, molecular weight development and evolution of the concentrations of species participating in the reaction mechanism over a range of operating conditions, and a parameter sensitivity analysis showing the effects of temperature, activation/deactivation equilibrium constant and initial concentrations of controller and initiator (if present) on these variables are presented for the nitroxide‐mediated radical polymerization of styrene. The simulations were performed with a computer program based on a detailed reaction mechanism. The simulated profiles of conversion, number average molecular weight ( ), and polydispersity agree well with experimental data. Previously unknown activation energies for reactions involved in the mechanism are estimated. The temperature dependence of the kinetic rate constants obtained in this study will be useful for future modeling and optimization studies.

     

用稳定自由基聚合及光引发聚合制备嵌段共聚物

介绍了稳定自由基聚合的反应原理、引发剂设计，以及用稳定自由基聚合制备嵌段共聚物的几种方法：连续加料法、双官能团引发剂法和一步法。对于光引发聚合的原理及硫自由基的稳定性对聚合反应的影响也进行了讨论。     

Atom‐Transfer Radical Batch and Semibatch Polymerization of Styrene

Batch and semibatch styrene polymerizations are carried out using a heterogeneous ATRP catalyst system that provides excellent molecular‐weight control. The observed initiator efficiency is lower for semibatch operation due to the high initiator concentrations required to make a low‐MW polymer. Experiments verified that the insoluble metal complex does not participate in the polymerization and that Cu(I) solubility is an order of magnitude higher than that of Cu(II). A mechanistic model, using kinetic coefficients from literature and the solubility data from this study, provides a good representation of the experimental results.

     

Synthesis of Molecularly Imprinted Polymer Particles by Suspension Polymerization in Silicon Oil

Molecular imprinting is a method to prepare polymers with recognition site of desired and predetermined selectivity1. Molecularly imprinted polymers (MIP) are prepared by copolymerizing functional and cross-linking monomers in the presence of a molecular …     

引发剂结构对原子转移自由基聚合反应的影响

研究了三种不同结构的引发剂,溴代乙酸乙酯（EBrA)、α-溴代丁乙酯（EBrB)、α－溴代异丁酸乙酸（EBriB)引发的苯乙烯的原子转移自由基聚合反应（ATRP）。发现EBrA引发的苯乙烯的ATRP不是“活性”聚合。EBriB引发的苯乙烯的ATRP引发效率不够高,也不是典型的“活性”聚合。EBrB引发的苯乙烯的ATRP是较为典型的“活性”聚合：聚合物的分子量可以通过调节单体／引发剂的投料量及反应时间来控制,所得聚合物的分子量分布很窄,且有随转化率的增加而逐渐变窄的趋势。     

Magnetic Molecularly Imprinted Polymer Particles Synthesized by Suspension Polymerization in Silicone Oil

Summary: Magnetic nanoparticles have been prepared by a co‐precipitation method and modified with methacryloxypropyltrimethoxysilane. Magnetic molecularly imprinted polymer particles have been prepared by suspension polymerization in silicone oil. The particles possess a high affinity to the template molecules and are rapidly separated under a magnetic field.

SEM photograph of magnetic MIP particles.     

Influence of Cyclodextrin on the Styrene Polymerization

Cyclodextrin (CD) are oligosaccharides consisting of 6( α ), 7( β ), 8( γ ) units of1,4-linked glucose. Due to their polar hydrophilic outer shell and relatively hydrophobic cavity, theyare able to build up host-guest complexes by inclusion of suitable hydrophobic molecules. Theformation of these complexes leads to significant changes of the solubility and reactivity of the guestmolecules, but without any chemical modification. Thus, water insoluble molecules may becomecompletely water soluble simply by mixing with an aqueous solution of native CD or CD-derivatives.Hydrogen bonds or hydrophobic interactions are responsible for the stability of the complexes and itturned out that the complexed monomers could be successfully polymerized by free radicalpolymerization in water.In our present work, using styrene as monomer, potassium peroxodisulfate as radical initiator thatreacted in water in the presence ofβ-CD but without any additional surfactant, the effect ofcyclodextrin on the polymerization was described. Additionally, the acceleration mechanism ofcyclodextrin in the polymerization was also explained based on dynamic study.Table 1 Effect of CD on the monomer reactivityIt is found that β -CD could greatly accelerate the polymerization, enhance the final conversion ofmonomer. And the more the amount of β-CD was introduced, the faster the polymerization wasobtained. From Figure 1, after 5 hours reaction at 80℃, the monomer conversion in the presence of1.0g cyclodextrin reached to 95%. However, that in absence of cyclodextrin was only 60%. And themonomer conversion was not to exceed 75% even reacted for 8 hours when no CD in reactionsystem.In order to describe the acceleration of CD in the polymerization quantitatively, based onCD and without CD. As shown in Table 1, CD produced significant effect on the monomer reactivity.The relative relativities of monomer were greatly increased with the increase of the amount of CD.     

TEM研究苯乙烯微乳液聚合机理

用透射电镜(TEM)对苯乙烯(St)/十二烷基硫酸钠(SDS)/正戊醇/水的O/W微乳液体系在反应前、聚合过程中和反应结束后等不同时间里进行观察,并测定苯乙烯微乳液聚合前后粒径的大小,根据粒径大小的变化研究苯乙烯微乳液聚合成核机理,发现其成核位置主要是在胶束和单体微珠滴里。此外,还发现SDS/St的质量比越大,相对分子质量越低。     

Kinetics of Nitroxide Mediated Radical Polymerization of Styrene with Unimolecular Initiators

Summary: This study examined the kinetics of nitroxide-mediated radical polymerization of styrene with unimolecular (alkoxyamine) initiators. Control of polymerization rate and polymer molecular weight in unimolecular nitroxide-mediated radical polymerization was studied by looking at the effects of the three main factors: initiator concentration, temperature, and initiator molecular weight on polymerization rate, molecular weight and polydispersity. In addition, the behavior of the unimolecular initiating systems was compared to that of the corresponding bimolecular system. The effective TEMPO concentration and degree of self-initiation of styrene were proved to be significant in dictating magnitudes of molecular weight averages and widths of molecular weight distribution.     

Atom Transfer Radical Polymerization of Styrene Using a Bifunctional Initiator

A bifunctional alkyl halide, namely l, 2-bis(2′-bromobutyryl) ethane (BBrBE), was synthesized and used to initiate the bulk atom transfer radical polymerization (ATRP) of styrene (St) at 110°C in the presence of CuBr/2,2′-bipyridyl. The narrow polydispersity of polystyrene (PSt) with precisely two arms could be synthesized. The initiate ability of the two active bromide functional groups at both sides of BBrBE for St and the propagation ability of the two arms were confirmed to be similar by the characterization of the individual arms obtained upon hydrolysis of the ester link between the core and the branches.     

二价芳氧钐配合物催化苯乙烯聚合

二价芳氧钐配合物催化苯乙烯聚合齐贵中扈晶余＊沈琪（中国科学院长春应用化学研究所稀土化学与物理开放实验室长春１３００２２）（苏州大学化学系苏州）关键词钐配合物，苯乙烯，聚合１９９６－０５－１８收稿，１９９６－１０－３０修回国家科委攀登计划及国家自然科学...     

原子转移自由基聚合制备聚酯二元醇接枝聚苯乙烯

聚酯二元醇经氯甲基化制备了聚酯二元醇大分子引发剂,通过原子转移自由基聚合技术,合成了聚酯二元醇－ｇ－聚苯乙烯接枝聚合物。用＾１Ｈ－ＮＭＲ、ＦＴ－ＩＲ和ＧＰＣ表征了接枝聚合物,结果表明分子量与转化率呈线性关系,且分子量分布较窄,接枝聚合反应是一个可控过程。     

稳定自由基存在下苯乙烯聚合的加速剂

研究了稳定自由基存在下苯乙烯的活性聚合,发现在β－酮酸酯－乙酰乙酸乙酯,乙二酸二乙酯,1,3－二酮－乙酰丙酮的少量存在下,苯乙烯聚合速率显著增加,分子量可控,分子量在布较窄。而乙酰丙酮较大量存在下,聚苯乙烯分散性稍微变宽。     

Copolymerization of 2-Hydroxy.(2,3-epoxypropoxy)benzophenone with Phthalanhydride Catalyzed by Tertiary Amine

The copolymerization of an epoxide, 2-hydroxy-4-(2,3-epoxy-propoxy)benzophenone, with cyclic anhydride catalyzed by tertiary amine in different solvents was studied. The copolymerization curves are sigmoidal in character with an induction period. In the region following the induction period, the loss in epoxide or anhydride may be correlated with the kinetic equation of the first order reaction provided the monomers are present in equimolar ratio or anhydride is in excess with respect to epoxide. The rate constant found experimentally after the induction period depends on the first power of the concentrations of amine, epoxide, and anhydride. The activation energy of copolymerization in o-xylene is 58.2 kJ/mole (13.9 kcal/mole) and log A = 3.6. The rate of copolymerization depends on polarity of the solvent and increases with dielectric constant. A reaction scheme has been proposed for the copolymerization of epoxides with cyclic anhydrides catalyzed by tertiary amines which involves the formation of a catalytic center of ionic character by isomerization of epoxide into a derivative of allyl alcohol and its subsequent interaction with tertiary amine and anhydride in equilibrium reactions, In this way, an active center of the carboxylic anion type is formed which reacts with epoxide to give alkoxide anion. This alkoxide anion reacts with anhydride to yield carboxylic anion. By interchange of these reactions, an alternating copolymer-polyester arises. The termination involves the decay of the active center into tertiary amine and carboxylic or hydroxylic endgroups. The kinetic solution of this scheme is in agreement with the experimental results of kinetic measurements and the rate of copolymerization is governed by the equation: -d[epoxide] /dt = k_p [amine] ₀ [epoxide]₀ [anhydride]₀ [epoxide].     

稳定自由基存在下苯乙烯聚合的加速剂

研究了稳定自由基存在下苯乙烯的活性聚合，发现在β－酮酸酯[乙酰乙酸乙酯（AAE），乙二酸二乙酯（DEM）]，1，3－二酮[乙酰丙酮（AAT）]及强酸酐[三氟乙酸酐（TFA）]的少量存在下，苯乙烯聚合速率显著增加，分子量可控，分子量分布较窄。而有机强酸[氯乙酸（CAA），溴乙酸（BAA），2，4，6－三硝基苯酚（TNP）]并不提高聚合速率。