原子转移自由基聚合在聚合物分子设计中的应用

原子转移自由基聚合反应 ( ATRP)是一种新的活性自由基聚合方法 ,自 1995年提出后 ,引起高分子合成化学及工业界的关注。本文详细介绍了 ATRP在端功能基聚合物、大分子单体、嵌段共聚物、接枝共聚物、星形聚合物、梯度共聚物、超支化聚合物等聚合物分子设计中的应用     

水性聚合物乳液及使用该乳液的化妆品

聚合物乳液由硅烷偶联剂单体和亲油性自由基聚合型单体及亲水性自由基聚合型单体经乳液聚合而得。／CN 1457346A     

原子转移自由基聚合在合成接枝共聚物中的应用

本文综述了采用原子转移自由基聚合（ATRP）法合成接枝共聚物的研究进展。主要从大分子引发剂法和大分子单体法两方面介绍了原子转移自由基聚合在合成接枝聚合物中的应用。     

PS-PMMA-PBMA三嵌段聚合物的ATRP合成及表征

以氯化亚铜(CuCl)/2,2’-联吡啶(bpy)为催化体系,苄基氯为引发剂,采用本体原子转移自由基聚合(ATRP)方法,引发苯乙烯(St)聚合,合成出大分子引发剂聚苯乙烯(PS-Cl)。用此大分子引发剂在溶液体系下引发第二单体甲基丙烯酸甲酯(MMA)聚合,合成出PS-PMMA-Cl二嵌段聚合物。再以此二嵌段聚合物为大分子引发剂引发甲基丙烯酸丁酯(BMA)聚合,合成出三嵌段聚合物PS-PMMA-PBMA。运用凝胶色谱、红外光谱、核磁共振氢谱及差示扫描量热技术等对三嵌段聚合物进行表征。     

中国专利

原子转移自由基聚合制备聚甲基丙烯酸叔丁酯大分子单体,一种消除聚合物中残留单体N-乙烯基吡咯烷酮的方法，用于气相烯烃聚合的负载型催化剂，用于烯烃聚合的组分和催化剂,制备用于皮肤和头发组合物的乙烯基酰胺聚合物的方法[编者按]     

有机低分子物在聚合物中的渗透

一、前言在聚合物的制造、加工及应用过程中,常常涉及到分子的渗透和扩散,特别是有机低分子物在聚合物中的渗透和扩散。最常见的渗透和扩散现象可以归纳为以下几个方面: (1) 由扩散控制的聚合过程。在聚合过程中,特别是聚合后期,聚合速率受单体、引发剂、长链自由基、死的大分子及低     

阴离子型丙烯酸酯类两亲接枝聚合物的合成、溶液性质及其与阳离子表面活性剂的相互作用研究

通过催化链转移聚合（CCTP）技术可以一步得到末端带有可聚合碳碳双键的大分子单体P（MMA-CO-t-BMA）,并进一步接枝聚合得到阴离子型两亲接枝聚合物。采用滴形分析法、动态光散射以及透射电镜（TEM）系统研究了所得接技聚合物的水溶液性质（表面张力、聚集体大小及形貌等）,详细研究了合成的阴离子两亲聚合物与阳离子表面活性剂CTAB之间的相互作用。     

接枝型水性聚合物分散剂的催化链转移聚合制备及其炭黑分散能力研究

应用催化链转移聚合技术合成末端带有可聚合双键的大分子单体,然后大分子单体进一步与主链单体共聚制备接枝聚合物,并通过定量酸性水解得到支链亲水、主链疏水的两亲接枝聚合物。同时系统研究了该聚合物的主链与侧链的分子量大小、主链锚定基团种类与浓度等因素对其在水性体系中炭黑分散能力的影响,为分散剂的结构优化奠定基础;所优选结构的分散剂其炭黑分散能力与进口分散剂Disperbyk-190相当。     

来自原子转移自由基聚合的大分子单体的梳形聚合物

本发明涉及基于通过ATRP(原子转移自由基聚合)方法制备的丙烯酸酯的梳形聚合物和大分子单体。这些聚合物具有改进的在给定溶剂中分散颜料的能力。本发明还涉及包含梳形聚合物和大分子单体可分散无机或有机颜料粒子的组合物。通过将它们涂敷到任何合适基材上，例如涂敷到金属、木材、塑料或陶瓷材料上，而使用该组合物。     

亲水性高分子磁性微球的合成和应用研究

对近年来国内外有关亲水性高分子磁性微球的研究成果和发展现状进行了综述,具体讨论了包埋法、单体聚合法及原位法等常用的合成制备方法及其优缺点,指出反相(微)乳液聚合是制备亲水性聚合物微球的有效方法。分析了亲水性高分子磁性微球在酶固定化和实现靶向给药等方面的应用及存在的问题,对磁性微球的发展前景进行了展望。     

Solid polymer electrolytes with stable electrochemical properties

In order to build solid-state ambient-temperature batteries with stable electrochemical performances over a period of months, the crystallization process in polymer electrolytes can be suppressed by the addition of an elastomer and a styrenic macromonomer of PEO to a PEO-lithium salt electrolyte. Complex impedance measurements and X-ray diffraction studies were carried out in an attempt to understand the effect of the macromonomer on the electrochemical behaviour. The conductivity was found to increase with macromonomer content and values as high as 10^?5S cm^?1 at room temperature can be obtained. X-ray, diffraction patterns have shown that addition of the elastomer and the macromonomer does not alter the monoclinic unit cell of the crystallized PEO. During ageing, the diffraction lines were found not to vary appreciably over a period of 15 months. Similarly, no appreciable change in the conductivity level was noticed within the same period. The observed behaviour was explained as a suppression of the crystallization process.     

Preparation of polymer microspheres with a rosin moiety from rosin ester,styrene and divinylbenzene

Rosin was reacted with hydroxyethyl methacrylate to produce a macromonomer. This macromonomer was used to partly replace styrene for the novel preparation of polymer microspheres with divinylbenzene via suspension polymerization. Orthogonal experiments were conducted to analyze the factors influencing the particle size, particle size distribution, swelling ratio and degree of crosslinking of the polymer microspheres. Fourier transform IR spectroscopy, thermogravimetry and scanning electron microscopy were used to examine the structures, thermal properties and morphologies, respectively, of the polymer microspheres. The results showed that the amount of dispersant had the greatest influence on particle size and distribution. On the other hand, the monomer ratio greatly influenced the swelling ratio and degree of crosslinking of the polymer microspheres. The decomposition temperature of the polymer microspheres increased upon introduction of the rosin moiety into the product. Open pores were abundant on the surface of the polymer microspheres due to the existence of the porogen, which provided a base for adsorption and separation. The present study opens a novel route for using naturally occurring rosin. Copyright © 2012 Society of Chemical Industry     

Segmented polymer networks containing amino‐dendrimers

Polymer networks in which poly(propylene imine) dendrimers (Astramol?) are connected to each other by linear polytetrahydrofuran (polyTHF) segments, were prepared by two methods. The first method was a one‐step procedure in which bifunctionally living polyTHF, obtained by initiation of the THF polymerization with trifluoromethane sulfonic anhydride (triflic anhydride), was reacted with an amino‐dendrimer. This reaction was very fast but did not allow formation of the end products. The second method was a two‐step procedure. In a first step, living polyTHF, prepared with acryloyloxybutyl triflate as initiator, was grafted on an amino‐dendrimer, to form a star‐like, acrylate‐terminated polyTHF multi‐macromonomer with the dendrimer as core. In a second step, networks were obtained by Michael addition between the acrylate end‐groups and unreacted amino‐groups of the dendrimer. This cross‐linking reaction occurred spontaneously upon heating of the solution of the multi‐macromonomer with gelation times varying from a few minutes to a few hours, depending on the temperature and the composition of the prepolymers. With this method it was possible to prepare networks in the form of coatings or films. © 2003 Society of Chemical Industry     

Bulk and emulsion copolymerizations of n-butyl acrylate and poly(methyl methacrylate) macromonomer

Bulk and emulsion copolymerizations of an ω-unsaturated poly(methyl methacrylate) (PMMA) macromonomer with n-butyl acrylate (n-BA) were investigated. The reactivity of PMMA macromonomer in bulk copolymerization with n-BA was found to be lower than that of methyl methacrylate monomer with n-BA. The incorporation of PMMA macromonomer into poly(butyl acrylate) (PBA) latex particles by miniemulsion copolymerization was proved by high performance liquid chromatography-silica adsorption spectroscopy. Dynamic mechanical studies showed that PMMA macromonomer was grafted to the PBA backbone, and the degree of grafting increased as the ratio of PMMA macromonomer to n-BA increased. Microphase separation of the PMMA macromonomer grafts was observed at higher ratio of macromonomer (higher or equal to 10% weight of macromonomer based on total polymer phase). The n-BA/PMMA macromonomer copolymer behaved completely differently from the physical blend of PBA and PMMA macromonomer particles of the same composition. © 1996 John Wiley & Sons, Inc.     

Synthesis of well‐defined poly(vinyl ether)‐based macromonomers having pendant glycerols via living cationic polymerization and their application to the preparation of core−shell polymer particles

A new vinyl ether monomer bearing a glycerol pendant moiety protected with an isopropylidene group (2‐(2,2‐dimethyl‐[1,3]dioxolan‐4‐ylmethoxy)‐ethyl vinyl ether, IpGEVE) was designed as the precursor of a novel type of hydrophilic poly(vinyl ether) containing glycerol pendants. It was found that the polymerization of IpGEVE proceeded in a controlled manner, and the protecting groups of isopropylidene moieties could be cleaved with trifluoroacetic acid. Living cationic polymerization of IpGEVE with an initiator bearing a methacryloyl group (VEM‐HCl) and subsequent deprotection of the pendant isopropylidene groups of the resultant precursor afforded a glycerol‐substituted hydrophilic macromonomer MA‐PGEVE. Nearly monodispersed polymer particles in the submicron size range were successfully obtained via dispersion copolymerization of MA‐PGEVE with styrene.© 2013 Society of Chemical Industry     

Preparation and characterization of magnetic amphiphilic polymer microspheres

Magnetic amphiphilic polymer microspheres were prepared by copolymerization of styrene with poly(ethylene oxide) macromonomer (MPEO) in the presence of Fe₃O₄ magnetic fluid in ethanol/water medium. Magnetic microsphere size, size distribution, and surface morphology were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The structure of copolymer was determined by infrared spectroscopy. With increasing MPEO used in the polymerization, the resulting microsphere size decreased. Magnetic amphiphilic polymer microspheres containing 0.02–0.2 mmol/g hydroxyl groups could be prepared by using different MPEO concentration. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1847–1851, 2001     

Simultaneous interpenetrating network silicone hydrogels prepared by free radical/cationic hybrid polymerization

Simultaneous interpenetrating polymer network silicone hydrogels have been prepared by UV‐initiated polymerization of a mixture of methacrylate monomer 2‐methacryloyloxyethyl phosphorylcholine (MPC) and vinyl ether terminated polydimethylsiloxane (VESi) macromonomer. The consumption of each (macro)monomer upon UV‐irradiation was monitored in situ by real‐time infrared spectroscopy. The methacrylate monomer MPC was shown to polymerize faster and more extensively than the vinyl ether terminated macromonomer VESi. Curing experiments performed in the presence of air and under air diffusion‐free conditions indicated that the free radical polymerization of MPC was affected by the oxygen inhibition effect, while the cationic polymerization of VESi was influenced by the atmosphere humidity. The results of the transmission electron microscope studies indicated that the silicone hydrogels were heterogeneous with phase domain sizes less than 10 nm. The physicochemical properties of the silicone hydrogels, such as water content, ion permeability, oxygen permeability, and contact angle were also investigated. The results showed that water content and ion permeability increased with the MPC content in the formulation, and the silicone hydrogels exhibited excellent oxygen permeability with the highest Dk of 255 barrer. The contact angle measurements indicated that the silicone hydrogels possessed hydrophilic surfaces with the lowest water contact angle of 20°. The result of the protein resistance revealed that the amount of protein adsorbed was significantly reduced with the MPC content in the formulation. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of isopropenylbenzyl‐terminated macromonomers and preparation of polymer brushes by anionic homopolymerization

Isopropenylbenzyl‐terminated polystyrene (PS) macromonomers were synthesized by anionic addition in a two‐stage process using styrene and 1,4‐diisopropenylbenzene (DIPB) in benzene. The reaction products of polystyryl anions with DIPB provided PS macromonomer possessing less than two isopropenylbenzyl groups at the propagating end under the condition of being in hydrocarbon solvent at 25°C (ceiling temperature) because of the anionic equilibrium nature. Subsequently, anionic homopolymerization of such macromonomers was carried out in tetrahydrofuran (THF) at ?78°C using anionic initiators to prepare the polymer brushes. The conversion of polymer brushes was very low (ca. 5%). Moreover, the degree of polymerization (DP) was less than 50. The low concentration of propagating chain ends seemed to affect the formation of polymer brushes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87:1790–1793,2003