等离子体引发HEMA的RAFT接枝聚合改性聚丙烯多孔膜

采用等离子体引发的可逆加成-断裂链转移(RAFT)接枝聚合法,以甲基丙烯酸羟乙酯(HEMA)为单体,对聚丙烯(PP)多孔膜表面作了亲水改性.研究了接枝聚合动力学,并以FT-IR、SEM、压汞、水通量等方法研究了改性膜的表面结构形态及孔结构.结果表明,等离子体引发的RAFT接枝聚合速率显著低于普通等离子体引发的接枝聚合速率.表面接枝率随着接枝聚合时间的延长呈线性增长趋势,同时改性膜的孔径和水通量随之减小.     

RAFT链转移剂存在下凹凸棒土表面甲基丙烯酸甲酯接枝聚合

将γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPS)接枝到凹凸棒土(AT)表面,制得表面带有可聚合碳碳双键的改性粒子AT-MPS;以二硫代苯甲酸氰基异丙酯(CPDB)为链转移剂,采用可逆加成断裂链转移(RAFT)聚合技术,在AT表面进行甲基丙烯酸甲酯(MMA)接枝聚合.通过红外(FTIR)、热失重(TGA)等方法进行了表征,考察了引发剂以及RAFT链转移剂用量对聚合反应动力学和AT表面接枝聚合接枝率的影响.结果表明,PMMA通过RAFT聚合成功接枝在AT表面;基于RAFT过程的接枝聚合比传统自由基接枝聚合具有更长的反应时间和较高的接枝率.本体系相对适宜条件:温度为70℃,[MMA]/[CPDB]/[AIBN]为400/1/0.5.此条件下聚合反应具有很好的可控性,溶液中的聚合物分子量分布指数为1.2~1.3,AT表面PMMA接枝率为16.33%.引发剂和RAFT链转移剂用量过大均会造成接枝率降低.     

RAFT聚合法合成聚丙烯酰胺基偶氮苯的研究

以二硫代苯甲酸苄酯(BDTB)为链转移剂,偶氮二异丁腈(AIBN)为引发剂,丙烯酰胺基偶氮苯(AAAB)为单体,DMF为溶剂,利用可逆加成-断裂链转移(RAFT)聚合法合成了聚丙烯酰胺基偶氮苯(PAAAB),并考察了聚合温度和链转移剂浓度对聚合反应的影响。通过FT-IR、1 H-NMR、GPC等对链转移剂和聚合物结构进行了表征。结果表明:聚合反应动力学曲线呈良好的线性关系,分子量分布窄;随着[BDTB]/[AIBN]比例的增大,聚合速率和分子量下降,分子量分布变窄。     

等离子体挥发性产物引发甲基丙烯酸甲酯聚合反应动力学

本文发现甲基丙烯酸甲酯等离子体挥发性产物能够有效地引发单体聚合,获得超高分子量聚合物。其聚合过程属于瞬时引发、向单体链转移的活性自由基聚合机理。     

Ce(Ⅳ)盐引发丙烯酰胺在聚乙烯醇微球表面接枝聚合的研究

以硫酸铈铵为引发剂,采用水溶液聚合体系,在酸性介质中实施了丙烯酰胺(AM)在聚乙烯醇交联微球(CPVA)表面的接枝聚合,制备了接枝微粒CPVA-g-PAM,重点研究了各种因素对接枝聚合的影响规律,探讨了铈盐引发接枝聚合的机理.实验结果表明,在Ce(Ⅳ)盐的氧化作用下,在含有大量羟基的CPVA微球表面会产生自由基,顺利地实现丙烯酰胺的自由基接枝聚合反应.PAM的接枝度首先取决于水介质中硫酸的浓度,接枝度随硫酸浓度的增大呈现先增大后减小的变化规律,当H+离子浓度为0.36mol/L时,PAM的接枝度最高,酸浓度对接枝度的影响反映了铈盐引发接枝聚合的微观机理.引发剂Ce4+盐的浓度过大,将会促进氧化终止过程,降低接枝度,适宜的Ce4+盐浓度为5.98×10-3mol/L.在接枝聚合过程中,单体丙烯酰胺浓度和反应温度也会对接枝聚合产生影响.在本研究所确定的适宜条件下,可制得PAM接枝度为27.13g/100g的接枝微粒CPVA-g-PAM.     

丙烯酰胺基偶氮苯的RAFT聚合反应动力学

以丙烯酰胺基偶氮苯(AAAB)为单体,二硫代苯甲酸异丙苯酯(CDB)为链转移剂,偶氮二异丁腈(AIBN)为引发剂,N,N-二甲基甲酰胺(DMF)为溶剂,利用可逆加成-断裂链转移(RAFT)聚合法合成了侧链含有偶氮苯基团的聚丙烯酰胺基偶氮苯(PAAAB),同时考察了反应温度、引发剂浓度、链转移剂浓度等因素对聚合反应的影响。利用FT-IR、1H NMR、GPC等对其结构进行了表征。结果表明,聚合反应动力学曲线呈良好的线性关系,分子量分布窄;随着[CDB]/[AIBN]比例的增大,聚合速率、分子量和分子量分布均下降。     

聚丙烯酰胺/聚L-谷氨酸苄酯接枝共聚物的合成及其胶束制备

以聚丙烯酰胺(PAM)为大分子引发剂, 采用开环聚合方法, 在N,N-二甲基甲酰胺(DMF)中引发L-谷氨酸苄酯环内酸酐(BLG-NCA)聚合合成了两亲性聚丙烯酰胺/聚L-谷氨酸苄酯接枝共聚物(PAM-g-BLG), 采用IR, 1H NMR和GPC方法对共聚物结构进行了表征; 用芘作荧光探针, 研究了共聚物胶束的形成及其临界胶束浓度(cmc), 利用动态光散射(DLS)和透射电镜(TEM)研究了胶束的粒径分布和形态. 结果表明, PAM能够引发BLG-NCA开环聚合得到接枝共聚物, 在一定条件下接枝共聚物能够形成球形的稳定胶束, cmc值和胶束粒径随着共聚物中疏水性聚L-谷氨酸苄酯(PBLG)链段含量的增加而减小.     

甲基丙烯酸己磺酸钠的等离子体射发聚合与嵌段共聚合

等离子体引发聚合是七十年代发展起来新的聚合方法。其特点是获得超高分子量的聚合物,且在许多情况下是活性聚合,因此,可用于合成嵌段共聚物,和接枝共聚物以及一些特殊性能的高聚物材料,如絮凝剂、固定化酶等。但并不是所有的单体都能进行等离子体引发聚合,因此,对于此种聚合的活性和反应机理的研究引起了极大的兴趣。前文报道了甲基丙烯酸己磺酸钠(SSHMA)水溶液等离子体引发聚合动力学条件以及所得聚合物的结晶形态。本文对在SSHMA固相单体中加入少量水时等离子     

烯类单体与可溶性淀粉的接技共聚

甲基丙烯酸与可溶性淀粉在硝酸铈氨(CAN)、高锰酸钾及Fenton’。试剂(Fe~(2+)—H_2O_2)引发下的接枝反应,经历了不同的反应历程。对可溶性淀粉而言,采用Fenotn‘s试剂为引发剂,水—丙酮混合液为介质,可以有效地控制反应,并获得高转化率和高接枝率的最佳效果。通过溶解度参数估算及拟均相反应设计,选择二甲基亚砜(DMSO)为中介溶剂,通过链转移引发完成了油溶性单体苯乙烯与可溶性淀粉间的有效接枝共聚,确定了转化率高、接枝率高、均聚物含量少的最佳反应条件,突破了多年来用相类似化学引发体系引发在苯乙烯与淀粉接枝时转化率低下及均聚物含量高的局限。在上述研究基础上,对反应介质与条件对油溶性烯类单体与可溶性淀粉接枝聚合之接枝参数的影响进行了探讨。     

SiO2表面RAFT接枝聚合苯乙烯

基于纳米SiO2表面羟基与7-甲基丙烯酰氧基丙基三甲氧基硅烷间的偶联反应,在纳米SiO2表面引入可聚合双键。采用可逆加成断裂链转移（RAFT）聚合技术,以偶氮二异丁腈为引发剂,使SiO2表面接枝聚合苯乙烯。考察了二硫代苯甲酸异丁腈酯、二硫代苯甲酸苄酯、（1,2,4-三氮唑）基二硫代甲酸苄酯和二硫代新戊酸苄酯等对SiO2表面接枝聚合苯乙烯速率的影响。结果表明,SiO2表面接枝聚合苯乙烯的速率决定于RAFT试剂的Z基团结构。二硫代新戊酸苄酯调控的SiO2表面接枝聚合苯乙烯的速率最高。     

Kinetic study of the nitroxide‐mediated controlled free‐radical polymerization of n‐butyl acrylate in aqueous miniemulsions

The controlled free‐radical homopolymerization of n‐butyl acrylate was studied in aqueous miniemulsions at 112 and 125 °C with a low molar mass alkoxyamine unimolecular initiator and an acyclic β‐phosphonylated nitroxide mediator, N‐tert‐butyl‐N‐(1‐diethylphosphono‐2,2‐dimethylpropyl) nitroxide, also called SG1. The polymerizations led to stable latices with 20 wt % solids and were obtained with neither coagulation during synthesis nor destabilization over time. However, in contrast to latices obtained via classical free‐radical polymerization, the average particle size of the final latices was large, with broad particle size distributions. The initial [SG1]₀/[alkoxyamine]₀ molar ratio was shown to control the rate of polymerization. The fraction of SG1 released upon macroradical self‐termination was small with respect to the initial alkoxyamine concentration, indicating a very low fraction of dead chains. Average molar masses were controlled by the initial concentration of alkoxyamine and increased linearly with monomer conversion. The molar mass distribution was narrow, depending on the initial concentration of free nitroxide in the system. The initiator efficiency was lower than 1 at 112 °C but was very significantly improved when either a macroinitiator was used at 112 °C or the polymerization temperature was raised to 125 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4410–4420, 2002     

混杂聚合

混杂聚合是指同一体系内有两种或两种以上不同类型的聚合反应同时进行的过程,如自由基聚合与阳离子聚合,自由基聚合与缩聚等。混杂聚合能够在原位形成高分子合金,并有可能得到互穿网络结构（ＩＰＮ）,从而使聚合产物具备较好的综合性能。     

含糖聚合物可控合成研究进展

活性聚合技术的进步,使设计合成结构可控的含糖聚合物成为可能.本文介绍了阴离子聚合、阳离子聚合、原子转移自由基聚合、可逆加成断裂链转移聚合、硝基氧介导聚合、开环聚合和开环易位聚合等一系列可控/"活性"聚合技术在合成含糖聚合物中的应用,并对这一领域所取得的研究进展及现状进行了综述.     

可控自由基聚合与其它活性聚合方法结合制备嵌段共聚物

可控自由基聚合与其它聚合方法结合,可以制备多种类型的嵌段共聚物,因此得到了广泛关注。本文着重介绍可控自由基聚合与离子开环聚合、阴离子聚合、烯类单体的阳离子聚合及其它活性聚合方法结合制备嵌段共聚物的研究现状和进展。     

由可控聚合反应直接制备不同形貌的聚集体

由可控聚合,包括活性阴离子和自由基聚合直接制备不同形貌纳米材料,是近几年来合成化学领域的一个重要研究成果.与两亲性嵌段共聚物在选择性溶剂中自组装方法不同,在选择性溶剂中进行的分散聚合,首先生成两亲性嵌段共聚物,并逐渐增加第二段聚合物的链长,以实现相分离,形成球形胶束;聚合物链继续增长,实现形貌转变,从而制备预期的聚合物形貌,包括球形胶束、纳米棒、纳米线、囊泡和复合囊泡等.本文综述了乳液聚合法制备球形胶束等形貌;描述了不同聚合体系形成的形貌以及它们的性质和应用,讨论了形貌的形成机理和控制方法,同时指出了存在的问题.     

Simple polymerization through oxygen at reduced volumes using oil and water

An enduring question is: what is the simplest and easiest way to obtain tailored polymers? This communication explores a robust photoiniferter polymerization with only two active ingredients that requires no prior deoxygenation and can be performed on the milliliter scale or sub-milliliter scale. Rather than leaving headspace in the polymerization vessel or scaling reactions up to fill the vessel, this approach fills the headspace of the reaction vessel with mineral oil or inert solvents. This approach can also be applied to polar monomers in aqueous media, using oil as the inert solvent, or to hydrophobic monomers with water as the inert solvent. This method removes enough ambient oxygen that the photoiniferter reaction proceeds with no deoxygenation step, and achieves high conversion and good molecular weight control in 10–20 h in both aqueous and organic solvents. Complex polymer architectures such as multiblock copolymers and gradient polymers were successfully synthesized by this approach.     

Kinetic aspects of styrene minisuspension polymerization using a mixture PVA-SDS as stabilizer: Effect of the time of addition of SDS

The styrene minisuspension polymerization at 70 °C using AIBN as initiator and Polyvinil alcohol (PVA) and mixture PVA-sodium dodecil sulfate (SDS) as stabilizers was studied focusing on the kinetic behavior of the process after the SDS was added (PVA is present from the beginning and SDS is added at a given time t_SDS). It was confirmed that the addition of SDS to the system initially stabilized with PVA highly enhances the colloidal stability of the polymer particles because of the association formed between SDS and PVA molecules. It was observed that when SDS is added the rate of polymerization, the average molecular weight and final latex viscosity increase. The earlier the addition of SDS the more marked these increments. This behavior is explained in terms of the colloidal stability of the particles formed via emulsion polymerization and its effect on kinetic aspects such as the evolution of molecular weight and particle size distributions during the minisuspension polymerization.