四功能引发剂引发的苯乙烯自由基本体聚合速度的测定和模拟

介绍一种新型的四功能引发剂LuperoxJWEB50，利用它引发苯乙烯自由基本体聚合，引发剂效率随引发剂浓度降低和聚合湿度的增加而增加，当湿度增加到－145℃时，引发剂效率在不同的引发剂深度下几乎相同，约0.78-0.8。实验表明，在湿度范围125－145℃时，采用该四功能引发剂引发的苯乙烯本体聚合的凝胶效应并不明显，并介绍一种单体转化率的测定方法，建立了考虑渗透和热引发的动力学模型来模拟聚合进程，模拟结果表明，即使单体转化率很高，此模型也能令人满意地预测聚合反应的进展。     

甲基丙烯酸甲酯的光引发聚合研究

本文探讨了光引发剂的种类与浓度、光照强度、光聚合组合物体系粘度及光聚合体系氛围对甲基丙烯酸甲酯(MMA)光引发聚合硬化时间、产率、重均分子量及分子量分布的影响。结果表明,体系初始粘度或引发剂含量的增加均有利于加快光聚合速度以及提高产率,产物具有良好的实用价值。PMMA的重均分子量Mw随着光引发剂浓度的增加而降低,但对紫外(UV)光强不敏感。     

苯乙烯聚合动力学(Ⅰ)热引发聚合机理的研究

在120～200℃内,对热引发苯乙烯本体聚合的速率及平均分子量进行了研究,得到聚合速率与单体浓度二次幂有关,据此可以推论引发速率也和单体二次幂有关。     

本体法合成ABS中引发剂对产品性能的影响

采用本体法合成了(丙烯腈/丁二烯/苯乙烯)共聚物(ABS),探讨了引发剂活性及用量对产品性能的影响.结果表明,在撤热和设备条件允许的前提下,使用高活性的引发剂体系及适当提高引发剂的用量有利于提高本体ABS的综合性能.     

树状分子引发苯乙烯的原子转移自由基聚合

从第2代端羟基树状聚芳醚出发,合成了2－溴异丁酸聚芳醚酯（G2－Br),并用红外,核磁,MALDI－TOF质谱和元素分析对其进行了表征,以C2-Br为大分子引发剂,在CuBr/2,2′－联吡啶催化作用下引发苯乙烯的原子转移自由基聚合。考察了聚合时间,单体和引发剂配比,聚合温度等因素对聚合的影响,合成了结构规整,分子量分布较窄的树状－线型嵌段共聚物。     

双硫酯作为链转移剂的苯乙烯本体聚合研究

研究了二硫代苯甲酸苄基酯（BDB）、二硫代苯甲酸苯乙基酯（PEDB）及二硫代苯甲酸异丙苯基酯（CDB）三种RAFT试剂作为链转移剂的苯乙烯本体聚合。动力学研究表明,当BDB及PEDB浓度和偶氮二异丁腈（AIBN）浓度同时增大时,AIBN浓度提高所导致的聚合反应速率提高起主导作用：当CDB和AIBN浓度同时提高时,CDB浓度提高所导致的聚合速率降低作用影响更显著。对CDB体系,随转化率提高分子量分布变宽。对BDB体系,当其浓度较高时,随转化率提高分子量分布变窄;当其浓度较低时,不利于实现可控,活性聚合,反应后期分子量分布变宽。动力学和GPC分析均表明以BDB为链转移剂时苯乙烯本体聚合的可控性最好。在同时考虑链转移剂和引发剂作用的基础上,提出了修正的聚合物分子量预测模型,该模型可有效预测以双硫酯为链转移剂的苯乙烯RAFT聚合体系的分子量。     

苯乙烯热引发本体聚合的动力学研究 Ⅱ 数均分子量

基于提出的自由基本体聚合三段聚合模型以及双分子热引发机理,进一步导得了苯乙烯热引发本体聚合时数均分子量的计算方程。同时,通过对已有文献中的数据进行关联,获得了不同聚合温度条件下聚苯乙烯数均分子量的通用计算方程。分析获得的方程,可以认为,对于自由基本体聚合,由低转化阶段至凝胶效应阶段,链增长反应速率常数kp和向单体的链转移反应速率常数krt.m或向单体的链转移常数Cm维持不变,且Cm与聚合反应温度无关。此外,结果表明,在低转化阶段,数均分子量不随转化率改变,仅与聚合反应温度有关。但在凝胶效应阶段,分子量随转化率改变而变化,且反应温度越高,变化越显著。     

茚基钠/甲苯体系引发丙烯腈聚合的研究

本文采用茚基钠作为引发剂,对丙烯腈在甲苯中的聚合进行了研究,考察了引发剂用量、单体浓度、反应时间及反应温度对丙烯腈聚合的影响。发现茚基钠/甲苯体系对丙烯腈聚合反应具有一定的引发活性,且随着引发剂用量增加聚合反应转化率增大,聚合产物的分子量下降;延长聚合反应时间,转化率和分子量都增大;温度对聚合反应转化率影响不大,但对聚合产物分子量有明显影响。用粘度法对聚合产物的粘均分子量进行了表征。     

羟基偶氮酯引发剂合成双端羟基聚苯乙烯

以偶氮二异丁腈 ,乙二醇为原料合成双 ( 2 -羟乙基 ) 2 ,2′ -偶氮二异丁酸酯。将其作为引发剂 ,合成了遥爪型羟端基聚苯乙烯 ,其分子量为 3 .0× 10 3～ 6 .5× 10 3。讨论了单体浓度、引发剂浓度、聚合反应温度及反应时间对聚合转化率和产物分子量的影响。结果表明 ,聚合转化率和产物分子量随着单体浓度的增加而增加 ;而引发剂浓度增加 ,则聚合转化率明显提高 ,分子量却随之下降 ;温度升高 ,聚合转化率增加 ,产物分子量下降 ;而反应时间主要影响聚合转化率 ,对分子量影响不大。     

引发剂AIBN对高性能炭纤维PAN原丝聚合反应影响

以丙烯腈(AN)为主单体,丙烯酸甲酯(MA)、甲叉丁二酸(IA)为二三单体,偶氮二异丁腈为引发剂,进行溶液自由基聚合。考察了引发剂浓度和加入方式对三元共聚合的影响。研究得出,温度为61℃,引发剂浓度为0.75%,升温前加入引发剂,合成了数均分子量为15.5万,重均分子量为33.6万,并且分子量分布指数小于3.0,单体转化率高于90%,增比黏度为1.39的高性能炭纤维用原丝纺丝液。     

Kinetic model for short-cycle bulk styrene polymerization through bifunctional initiators

A model describing the kinetics of bulk styrene polymerization through bifunctional initiators has been developed. The diffusion-controlled propagation and termination reactions at high monomer conversions are modeled with the free volume theory for polymer solutions. Three different commercially available bifunctional initiators were experimentally evaluated for a wide range of polymerization conditions to study the effect of the reaction rate on the molecular weight and molecular weight distribution. The model predictions for the same polymerization conditions show excellent agreement with the experimental data, for the whole range of conversions, for both reaction rate and molecular weight distribution development, under all the conditions tested. It is demonstrated throughout this study that high molecular weights, very high reaction rates, and narrow molecular weight distributions can be achieved simultaneously by using bifunctional initiators. A comparison between monofunctionally initiated systems with the bifunctionally initiated ones shows that short-cycle reactions with reductions in polymerization time of up to 75% may be achieved with the bifunctional initiators for a wider range of conditions without significantly affecting the molecular weight and molecular weight distribution of the final product.     

氧化还原体系引发苯乙烯乳液聚合

以不同的过氧化物引发剂分别与硫酸亚铁组成氧化还原引发体系,引发苯乙烯的乳液聚合,研究反应温度和还原剂用量等对聚合的影响.采用气相色谱、三检测体积排除色谱、动态光散射对单体转化率、聚苯乙烯的相对分子质量及其分布和乳胶粒径进行了分析.结果表明:升高温度或增加还原剂用量均会使聚合物的相对分子质量增大,聚合反应速率加快,与常规...     

Free-radical polymerization of styrene with a binary mixture of symmetrical bifunctional initiators

The kinetics of bulk styrene polymerization catalyzed by a binary mixture of symmetrical bifunctional initiators has been investigated. When the bifunctional initiators having different thermal stabilities are mixed, an unsymmetry in the initiator functions is formed in situ via propagation, chain transfer, and termination reactions. For the quantification of the polymerization kinetics, a kinetic model has been developed using the molecular species modeling technique. For various polymerization conditions, good agreements between the model predictions and experimental data have been obtained. It is shown that polymerization rate and molecular weight can be easily regulated under isothermal reaction condition by changing the initiator composition. A comparison of the detailed kinetic model with a simple kinetic model for monofunctional initiators has also been made to illustrate the molecular weight increasing effect of the bifunctional initiator system. © 1992 John Wiley & Sons, Inc.     

Synthesis of polystyrene with mixtures of mono- and bifunctional initiators

This work studies the bulk and nonisothermic polymerization of styrene (S) using mixtures of mono- and bifunctional initiators. The effects on polymerization rate and on molecular weight averages after changes in the global initiator concentration and in the nature of the initiator mixtures were experimentally and theoretically analyzed. The mathematical model was adapted from the literature to admit initiator mixtures and to simulate the applied temperature profiles. Compared to the standard use of monofunctional initiators, the use of initiator mixtures that include bifunctional initiators presents the advantage of reducing the polymerization time, while not deteriorating the final polymer quality. The simulation program accurately describes the evolution of conversion, but exhibits some deviations with the average molecular weights. © 1996 John Wiley & Sons, Inc.     

Mathematical modeling of molecular weight distribution in miniemulsion polymerization with oil‐soluble initiator

A mathematical model for the study of reaction kinetics and molecular weight distributions in miniemulsion polymerization systems with oil‐soluble initiators is presented. The mathematical model allows the computation of the evolution of the complete molecular weight distribution with chain lengths of up to 10⁵ mers in miniemulsion polymerization by direct integration in reasonable computational time. Also, no restriction in the kinetic regime is needed, as the model is able to represent both compartmentalized and pseud‐bulk systems. The model was validated with experimental results for methyl methacrylate and styrene homopolymerizations, with two different oil‐soluble initiators, and adequately represented both the kinetics and molecular weight distributions of these systems. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2128–2140, 2017     

Atom transfer radical polymerizations of methyl methacrylate and styrene with an iniferter reagent as the initiator

Three novel iniferter reagents were synthesized and used as initiators for the polymerizations of methyl methacrylate (MMA) and styrene (St) in the presence of copper(I) bromide and N,N,N′,N″,N″‐pentamethyldiethylenetriamine at 90 and 115°C, respectively. All the polymerizations were well controlled, with a linear increase in the number‐average molecular weights during increased monomer conversions and relatively narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight ≤ 1.36) throughout the polymerization processes. The polymerization rate of MMA was faster in bulk than that in solution and was influenced by the different polarities of the solvents. A slight change in the chemical structures of the initiators had no obvious effect on the polymerization rates of MMA and St. The initiator efficiency toward MMA was lower than that toward St. The results of ¹H‐NMR, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrum analysis, and chain‐extension experiments demonstrated that well‐defined poly(methyl methacrylate) and polystyrene bearing photolabile groups could be obtained via atom transfer radical polymerization (ATRP) with three iniferter reagents as initiators. The polymerization mechanism for this novel initiation system was a common ATRP process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Free radical polymerization engineering—II: Modeling of homogeneous polymerization of styrene in a batch reactor,influence of initiator

A “tendency” model of free radical polymerization is used to re-investigate batch polymerization of styrene in solution in cyclohexane with slow and fast decomposing initiators. It is impossible to account for experimental data when a conventional mechanism involving only transfer to the monomer is assumed. In order to sucessfully represent mononer consumption and average molecular weights by number and by weight as a function of time for both initiators, two additional processes are required, i.e. transfer to and induced decomposition of the initiator (if transfer sites are available). The coresponding set of rate constants was determined. When a fast initiator is used, this polymerization is sensitive to mixing effects and could be utilized as a test reaction in polymer reactors. The elucidation of the role of the initiator is a good example of the usefulness of the “tendency” model for studying complex polymerization mechanisms.     

Copolymerization and addition of styrene and N‐phenylmaleimide in the presence of nitroxide

The copolymerization and addition reaction of styrene (S) with N‐phenylmaleimide (PMI), either neat or in xylene, have been found to proceed at 125°C in the presence of 2,2,6,6‐tetramethylpiperidin‐1‐yloxy (TEMPO) radicals. TEMPO‐terminated alternating S‐PMI copolymers and comonomer adducts were obtained. The amounts of the low molecular weight compounds increased with the increasing content of PMI in the initial mixture. The reaction suggests formation of monofunctional unimolecular initiators. In the autopolymerization of neat comonomers, a mediating role of TEMPO was observed. The synthesized copolymers containing TEMPO end groups were used as macroinitiators to initiate polymerization of styrene. The molecular weight distributions of resulting poly(styrene‐alt‐N‐phenylmaleimide)‐block‐polystyrene copolymers indicated the presence of both low molecular weight termination products and some copolymer precursor. The copolymers and comonomer adducts were characterized using the nitrogen analysis, size‐exclusion chromatography (SEC), and NMR spectroscopy. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1093–1099, 2000     

负离子溶液聚合法高苯乙烯橡胶的合成及其性能

以环己烷为溶剂、苯乙烯和丁二烯为单体、n-BuLi为引发剂、二乙二醇二甲醚(2 G)为结构调节剂,通过活性负离子溶液聚合合成了高苯乙烯橡胶,研究了引发剂种类、聚合温度、2 G/n-BuLi(摩尔比)、苯乙烯/丁二烯(质量比)、相对分子质量及其分布对共聚橡胶力学性能的影响。结果表明,当苯乙烯/丁二烯为60/40、2 G/n-BuLi为1.0时,在(65±2)℃下可聚合得到力学性能较好的高苯乙烯橡胶,其数均分子量为15×104~20×104、分子量分布为1.40左右。     

聚己内酯多元醇的合成与表征

分别以乙二醇、三羟甲基丙烷和季戊四醇为起始剂,经ε-己内酯开环聚合制备了一系列聚己内酯多元醇。探讨了反应温度、时间和催化剂等因素对合成反应的影响,并采用红外光谱(FTIR)、羟值滴定、凝胶渗透色谱(GPC)对聚己内酯多元醇进行了表征。结果表明,以无水乙酸锌为催化剂,且用量为己内酯单体摩尔分数的0.2%,在温度120℃条件下反应3~4 h,制备的多元醇为理想的聚己内酯多元醇,相对分子质量与设计值一致,而且具有相对分子质量分布窄、成本低的特点。