含规整 PMMA支链的 PBA合成及其力学性能

研究了聚甲基丙烯酸甲酯大单体与丙烯酸丁酯在苯中的共聚，该大单体由甲基丙烯酸甲酯在巯基乙酸链转移剂存在下聚合，用甲基烯酸缩不甘油酯封端，研究了共聚速率、大单体相对分子质量、大单体与小单体投料比、引发剂用量、单体浓度及共聚温度对接枝效率及共聚物相对分子质量的影响。用分级沉淀法精制共聚物。用凝胶渗透色谱法、红外光谱法及差示扫描量热法对共聚物进行表征，用蒸汽压式渗透压力计及膜渗透压测定了结构参数，结果表明，平均接枝数随转化率增加而降低，在一定的组成范围内，共聚物呈热塑性弹性体行为。     

含规整PMMA支链的共聚物及其离聚体的力学性能

研究了用聚甲基丙烯酸甲酯（ＰＭＭＡ）大单体与丙烯酸丁酯（ＢＡ）共聚制得的接枝共聚物及其与ＢＡ及丙烯酸（ＡＡ）共聚并中和制得的离聚体的力学性能与支链分子量、支链含量、共聚物分子量、羧基含量、中和度及离子种类的关系．结果表明这二种产物均呈现较好的热塑性弹性体行为，而离聚体的性能更为优越。     

聚苯乙烯大单体/丙烯酸辛酯规整接枝共聚物的结构、性能与增容作用

用傅里叶变换红外光谱、透射电子显微镜和差示扫描量热仪表征了聚苯乙烯大单体和丙烯酸辛酯规整接枝共聚物(POA-g-PS)的结构,测定了其物理机械性能,并研究了POA-g-PS作为聚苯乙烯/丙烯酸酯橡胶体系的共混增容剂时,共混物组成、接枝物用量及接枝物组成对共混物物理机械性能的影响。结果表明,POA-g-PS属于两相态,存在微观相分离结构;当聚苯乙烯大单体的质量分数在40%左右时,POA-g-PS是一种具有较大拉伸强度、较大扯断伸长率及较小永久变形的热塑性弹性体;扫描电镜和差示扫描量热分析表明接枝共聚物促进了聚苯乙烯/丙烯酸酯橡胶共混体系的互容,起到了增容剂的作用。     

聚乳酸-聚乙二醇-聚乳酸/聚(N-乙烯基吡咯烷酮)交联共聚物膜的制备与性能

在制备聚乳酸-聚乙二醇-聚乳酸(PLA-PEG-PLA)嵌段共聚物的基础上,以丙烯酸酯封端制备了PLA-PEG-PLA大分子单体。PLA-PEG-PLA大分子单体作为交联剂与N-乙烯基吡咯烷酮(NVP)单体经光聚合制备了系列PLA-PEGPLA/PVP交联共聚物膜。核磁共振测试结果表明了大分子单体的成功合成;随着NVP投料量的增加,交联共聚物膜的亲水性增强,水解降解性加快,而储能模量(E’)及玻璃化转变温度(Tg)下降;NVP与PLA-PEG-PLA大分子单体的投料量由0.25/1.68(质量比)增至1.55/1.68时,共聚膜的拉伸强度由32.7 MPa降为17.1 MPa,而断裂伸长率由82%增至387%,说明共聚物膜的韧性较好。     

IPDI/HEMA/PEG大单体的合成及其聚合物的制备

利用异佛尔酮一二异氰酸酯(IPDI)、甲基丙烯酸-β羟乙酯(HEMA)、聚乙二醇(PEG)合成了一种聚氨酯丙烯酸酯类大分子单体,并将其固化交联得到一种新型透明材料。研究了预聚温度、预聚反应时间、催化剂等对大单体合成的影响,并就聚乙二醇含量对聚合物的力学性能、透明性能、维卡软化温度的影响进行了分析探讨。该类透明高分子材料与有代表性的透明材料PMMA相比,在透光率基本相同的情况下,其软化温度是PMMA的2．3倍左右,硬度提高48％左右,具有优越的综合性能,可用于高温、高冲击的光学领域。     

Transparent organic materials made from copolymerization of styrene with urethane‐methacrylate macromer. I. Monomacromer system

Urethane macromers were prepared by reacting tolylene diisocyanate with various glycols, followed by end capping with 2‐hydroxyethyl methacrylate in the presence of dibutyltin dilaurate as the catalyst. Various proportions of styrene to the urethane‐methacrylate macromer were adopted to cure at 70°C for 7–8 h. The effect of the composition on the properties was systematically studied. These transparent materials exhibited excellent mechanical and optical properties and heat deflection temperature. All of the copolymer sheets had a transmittance similar to the poly(methyl methacrylate) sheet and had a rather high refractive index. The mechanical and thermal properties varied with the ratio of styrene to macromer and with the kind of glycol used in the synthesis of the macromer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 348–357, 2001     

Transmission electron microscopic observations of the multilevel microstructure of crosslinked copolymers with methacrylates and siloxane macromers by a radically polymerizable tuning approach

We investigated by Transmission Electron Microscopy (TEM) the morphologies of crosslinked copolymers from methacrylate monomers from methylmethacrylate (MMA) and trifluoroethylmethacrylate (TFEMA), polydimethylsiloxane (PDMS) macromers with molecular weight (Mn) of 1,700 and 4,700 g/mol, and crosslinker. Depending on the PDMS content, we observed, spherical PMMA islands in which small PDMS domains were dispersed, PMMA continuous phase, closely packed PTFEMA islands, and homogeneously dispersed PDMS domains were observed with low or middle magnification. Fine observation at 100,000‐fold magnification revealed the “fundamental” common size domain, which was determined by the M_n value of the PDMS macromer. Thus we found two microstructure types: (1) a “fundamental domain” due to the M_n of the PDMS macromer, and (2) an aggregated domain. The former was constant under all conditions, but the latter was affected by the comonomer and its ratio. The present results are essential in understanding the chemical and physical characteristics of crosslinked copolymers from PDMS macromers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of copolymerizing fluorine‐bearing monomers on the relationship among internal structure,gas permeability,and transparency in copolymer networks composed of methacrylates and siloxane macromers

To clarify the effect of the type of acrylic monomer and the molecular weight (M_n) of polydimethylsiloxane (PDMS) on the relationship among the internal structure, oxygen permeability coefficient [P(O₂)] and transparency, crosslinked copolymers were prepared with two different acrylic monomers : methyl methacrylate (MMA) and trifluoroethyl methacrylate (TFEMA). PDMS macromers with M_n of 1700, 3300, 4700, and 7800 g/mol were used. DSC measurements suggested that all constituent phases were insoluble with each other. The M_n of PDMS affected both the light transmittance and P(O₂). The relationship between the M_n and P(O₂) over the low M_n range (1700 and 3300 g/mol), and the calculated PDMS domain size ratio, were found to support the [M_n]^2/3 rule into the crosslinked copolymer. Furthermore, a 3300 g/mol M_n copolymer became transparent when the amount of PDMS was greater than PMMA. In addition, copolymerization with TFEMA drastically affected those properties, and this effect was much greater than the effect of the PDMS M_n. To clarify the mechanism of P(O₂) improvement induced by TFEMA copolymerization, calculations on the relationship among the P(O₂), PDMS volume fraction, and morphology model were performed, and some properties such as solubility parameters should play important roles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

磷元素杂化大单体VOPP接枝聚苯乙烯共聚物的合成及阻燃性能

以二氯磷酸苯酯(PDCP)、乙二醇(EG)、甲醇、甲基丙烯酸-β羟乙酯(HEMA)为原料,经逐步聚合得到端乙烯基低聚磷酸酯的磷元素杂化大单体(VOPP),VOPP与苯乙烯(St)通过接枝共聚制备磷元素杂化大单体接枝聚苯乙烯共聚物(VOPP-co-St)。利用FTIR和凝胶渗透色谱(GPC)表征VOPP的结构及平均分子量,通过TGA、氧指数测定仪和微型量热仪研究VOPP-co-St的热稳定性及阻燃性能,SEM和XPS表征炭层形貌及成分,利用Flynn-Wall-Ozawa(FWO)法计算VOPP-co-St的热降解活化能(Ea)。结果表明,随着VOPP含量的增加,VOPP-co-St的最大分解速率温度升高,残重率提高,极限氧指数(LOI)上升,热释放速率峰值(PHRR)降低,总热释放量(THR)减小,熔滴现象消失,Ea随降解转化率增大而增大。     

一种双离子梳状聚合物电解质的合成与性能研究

以端基含有烯丙基侧链含有氯甲基的不饱和聚醚 (UPEO)与苯乙烯 (St)共聚 ,得到以聚烯烃为主链、PEO为侧链、侧链挂载氯甲基的梳状聚合物 (CPPC) ,CPPC与亚硫酸锂反应 ,合成了一种新型单离子梳状聚合物电解质 (CPPL)。研究发现该梳状聚合物电解质的玻璃化温度 (θg)取决于苯乙烯的配比和磺化反应效率。对比研究了CPPL和CPPL复合LiClO4而成的双离子梳状聚合物电解质(CPPL2 )的θg、热稳定性、电化学窗口和电导率。测定结果表明 :CPPL和CPPL2的室温电导率分别为1.3× 10 -4s/cm和 7.8× 10 -4s/cm。