SYNTHESIS AND CHARACTERIZATION OF POLYDIMETHYLSILOXANE/POLYSTYRENE SEMIINTERPENETRATING POLYMER NETWORKS

The synthesis of pseudo- and semi-interpenetrating polymer networks (IPNs) based on poly-dimethylsiloxane (PDMS) and polystyrene (PS) is described. IPNs were obtained by simultaneous and in situsequential synthesis procedure. The preliminary studies on IPNs properties such as transition temperature,microphase separation and mechanical behaviors have been carried out by using differential scanningcalorimetry (DSC) and scanning electron microscopy (SEM). The experimental evidence clearly showed thatsemi-IPNs obtained by sequential synthesis procedure have higher interpenetrating extent than pseudo-IPNssynthesized by simultaneous procedure. Over the full composition, the PDMS/PS IPNs are immiscible. Thepseudo-IPNs microphase separation can be greatly subdued through the formation of grafting bonds betweentwo networks as well as the kinetic rate-matching of the individual network crosslinking.     

SYNTHESIS AND PROPERTIES OF POLYURETHANE ACRYLATE/EPOXY RESIN INTERPENETRATING POLYMER NETWORKS

In this paper, a series of interpenetrating polymer networks (IPNs) based on polyurethane acrylate and epoxy resin was prepared by simultaneous photoinitiating by both free-radical and cationic polymerization. The effects of the polyurethane acrylate prepolymer's molecular weight, various components ratio and polymerization methods on IPN's dynamic mechanical and mechanical properties were investigated.     

PVA-PAMPS-PAA三元互穿网络型水凝胶的合成及其性能研究

以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、丙烯酸(AA)以及聚乙烯醇(PVA)为原料,制备了PVA-PAMPS-PAA三元互穿网络型(T-IPN)水凝胶.红外分析表明,PVA与PAA以及PAMPS之间形成了较强的氢键,使得PVA分子上的C—O伸缩震动吸收峰移向了低波数处.X射线衍射以及电镜分析表明,当PVA用量较低时,PVA能均匀的穿插于凝胶网络中,形成完善的互穿网络结构,当PVA用量过高时,部分的PVA结晶而使得凝胶出现相分离.研究了该三元互穿网络型水凝胶的溶胀性能,结果表明,该水凝胶的平衡溶胀比在200至340之间,并且随着AA以及AMPS用量的增加,凝胶的溶胀速率以及平衡溶胀比均升高.该三元互穿网络型水凝胶在酸性溶液中和在碱性溶液中表现出截然不同的消溶胀性能;并且随着溶液pH的升高,凝胶在pH=9.0附近出现体积突变,表现出pH敏感性.通过研究T-IPN水凝胶的抗压缩性能发现,利用线型高分子、柔性高分子网络以及刚性高分子网络制备的三元互穿网络型水凝胶能在高溶胀比下保持较高的强度.溶胀比为180的T-IPN水凝胶,其最大抗压缩强度可达12.1 MPa.进一步研究发现,凝胶的组成以及溶胀比均对凝胶的抗压缩强度和压缩应变均存在较大的影响.     

聚(N-异丙基丙烯酰胺)/聚丙烯酰胺无机/有机互穿网络水凝胶的制备及表征

通过紫外引发聚合方法制备了无机交联的聚(N-异丙基丙烯酰胺)(PNIPAAm)/有机交联的聚丙烯酰胺(PAAm)互穿网络(IPN)水凝胶.利用FTIR和SEM分别表征了凝胶的化学结构和内部形态;测定了凝胶在高温(50℃)时的退溶胀性能;利用DMA和DSC分别研究了凝胶的储能模量随温度的变化及热相转变行为.研究表明,该IPN凝胶具有温度敏感性;与未互穿的无机交联PNIPAAm凝胶相比,IPN凝胶具有多孔的网络结构和超快的响应速率,如10min内失去90%的水;其储能模量增加了3～4倍,相转变行为变弱,而最低临界溶解温度(LCST)提高了1.4℃.     

AN EPOXY/(METHYL METHACRYLATE)INTERPENETRATING POLYMER NETWORK FOR NONLINEAR OPTICS*

An interpenetrating polymer networks (IPN) consisting of an epoxy-based polymer network and apolymethyl methacrylate network were synthesized and characterized. The IPN showed only one T_g, andhence a homogeneous-phase morphology was suggested. The second-order nonlinear optical coefficient (d_(33))of the IPN was measured to be 1.72×10~(-7) esu. The study of NLO temporal stability at room temperature andelevated temperature (100℃) indicated that the IPN exhibits a high stability in the dipole orientation due tothe permanent entanglements of two component networks in the IPN system. Long-term stability of secondharmonic coefficients was observed at room temperature for more than 1000 h.     

聚氨酯/蒙脱土纳米复合材料的制备与性能研究

纳米复合材料由于其纳米尺寸效应 ,表面效应以及纳米粒子与基体界面间强的相互作用 ,具有优于相同组分常规复合材料的力学 ,热学等性能 ,引起了人们的广泛关注 .用纳米材料改性聚合物 ,制备纳米复合材料是获得高性能高分子复合材料的重要方法 ,采用较多的是插层复合法 ,可分为两类 ,一是单体预先插层于层状结构填料的晶片层间 ,然后聚合 ;二是聚合物溶液或熔体直接插层于层状结构填料的晶片层间 .聚氨酯 (PU)是由多异氰酸酯与多元醇通过加聚反应而形成的高聚物 ,其重复结构单元是氨基甲酸酯链段( R2 OCONHR1NHCOO) .PU弹性体具有耐磨…     

SYNTHESIS AND PROPERTIES OF POLYSTYRENE／LAPONITE NANOCOMPOSITES

Exfoliated polystyrene (PS)/laponite nanocomposites were prepared successfully. The characteristic doo1 diffraction peak of organo-laponite disappeared in the XRD patterns of nanocomposites, indicating that the laponite layers were exfoliated and the ordered crystal structure of laponite was destroyed because of the styrene polymerization. TEM observations showed that the exfoliated laponite primary particles were dispersed randomly in the PS matrix with lateral dimensions from 1 nm to 10 rim. SEM results showed that the PS/laponite nanocomposite particles were almost monodispersed spheres with the size of about 120 rim. Because of the interaction between PS and laponite nanolayers, the nanocomposites exhibited higher thermal stability and glass transition temperature when compared to pure PS.     

蓖麻油型聚氨酯IPN的结构与性能研究

本文用蓖麻油,甲苯二异氰酸酯和甲基丙烯酸β-羟乙酯组成的加聚型网络(Ⅰ)和蓖麻油,甲苯二异氰酸酯和聚丙二醇组成的缩聚型聚氨酯(Ⅱ),以同步法形成了一组新型的IPN。用动态力学法和固体核磁共振法研究了它们的结构和性能,形成IPN后,力学数据显示出机械强度的提高,动态力学损耗谱上表现出,tanδ的增宽,固体核磁共振谱计算的结果是界面层的比例增高,但界面层比例并不随配比的改变而变化,它揭示出此IPN可能具有壳核结构。     

SYNTHESIS, STRUCTURE AND PROPERTIES OF INTERPENETRATING SULFONIC ACID RESINS WITH HIGH CAPACITY

Two series of interpenetrating sulfonic acid resins (ISAR), 10×n and n×10, were prepared by means of the wet method, and the physicochemical, thermodynamic and kinetic properties of the ISAR were measured. The results show: 10×n resins exhibit better properties than n×10 ones, mainly in higher apparent degree of crosslinking and larger conformational entropy effect, among which, 10×1 resin exhibits the best thermodynamic and kinetic properties. In the DTA graphs of n×10 resins, there are two T_g and two T_(ox), but in those of 10×n, only one T_g and one T_(ox). This result well supports the conclusion that 10×n resins have much better interpenetrating structural aspects.     

羧甲基纤维素钠/蒙脱土纳米复合膜的制备及性能

用溶液插层法制备出了剥离型羧甲基纤维素钠 蒙脱土纳米复合物 .X射线衍射结果中蒙脱土d0 0 1 峰的消失证实了纳米复合物的生成 ,透射电镜观察表明硅酸盐片层在羧甲基纤维素钠基体中达到了纳米级的分散 .红外测试表明 ,羧甲基纤维素钠分子上的醚键和蒙脱土分子上的硅氧键、铝氧键之间强的作用力是插层的驱动力 .加入蒙脱土后 ,提高了羧甲基纤维素钠膜的拉伸强度、热稳定性 ,降低了其水蒸汽透过系数 .     

聚苯乙烯/聚丙烯酸丁酯乳胶互穿聚合物网络的动态力学性能研究

<正> 互穿聚合物网络(IPN)是一种新型聚合物共混物.自Sperling在1969年合成聚丙烯酸乙酯/聚苯乙烯异步IPN(Sequential IPN)后,该领域进展很快.乳胶IPN(latex IPN)是用改进的乳液聚合法合成的一种微观互穿IPN.在前文中,我们报道了聚苯乙烯/聚丙烯酸丁酯(PS/PBA)乳胶IPN的合成,本文研究一些因素对PS/PBA乳胶IPN动态力学性能的影响.     

层状硅酸盐累托石/环氧树脂纳米复合材料的结构和性能研究

用有机改性的层状累托石与环氧树脂复合制备出纳米复合材料 .通过改变累托石含量发现在很低含量 (0 5W % )时纳米复合材料具有最佳力学和热学性能 ,冲击强度增加 12 0 % ,断裂伸长率增加 330 %玻璃化转变温度提高 2 8℃ .用X衍射、透射电镜和红外吸收光谱研究了材料的微观结构 ,结果表明层状累托石和环氧树脂发生了化学反应 ,观测到了层状累托石完全剥离和插层两种结构形态 ,且累托石含量较低时容易形成剥离型 .具有大的比表面积、高的反应活性的累托石片层分散于环氧基体中形成剥离型为主的结构有利于改善复合材料的力学性能并增加其热稳定性 .     

含三氟甲基聚酰亚胺的合成与性能研究

通过在4,4′-二氨基二苯醚(4,4-′ODA)单体中引入三氟甲基合成了一种新型二胺单体2-三氟甲基-4,4′-二氨基二苯醚(3FODA),该单体具有良好的溶解性和高的反应活性,使用3FODA替代4,4′-二氨基二苯甲烷(MDA)制备了PMR热固性聚酰亚胺树脂.树脂溶液高浓度低粘度,具有室温下良好的储存稳定性;树脂具有很好的加工性能,成型后的模压件显示了优异的热性能和耐热氧化稳定性,玻璃化转变温度在336~379℃之间;此外树脂具有较好的电性能和较低的吸水率.     

Effects of organophilic montmorillonite on hydrogen bonding, free volume and glass transition temperature of epoxy resin/polyurethane interpenetrating polymer networks

Epoxy resin nanocomposites containing organophilic montmorillonite (oM) and polyurethane were prepared by adding oM to interpenetrating polymer networks (IPNs) of epoxy resin and polyurethane (EP/PU). The dispersion degree of oM in EP/PU matrix was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Fourier transform infrared spectrometry (FT-IR) showed that strong interactions existed between oM and EP/PU matrix, and oM had some effect on hydrogen bonding of these EP/PU IPNs nanocomposites. Positron annihilation spectroscopy (PALS) and differential scanning calorimetry (DSC) measurements were used to investigate the effect of oM and PU contents on free volume and glass transition temperature (T_g) of these nanocomposites. The PALS and DSC results clearly showed that the presence of oM led to a decrease in the total fractional free volume, which was consistent with increasing T_g upon addition of oM, ascribed to increasing hydrogen bonding in interfacial regions of oM and EP/PU matrix and enhancing the miscibility between EP phase and PU phase. In addition, with increasing PU content, the total fractional free volume increased, corresponding to decreasing T_g.     

基于互穿网络结构的pH/温度双重刺激响应性微凝胶的研究

室温下采用氧化-还原引发体系,以低交联密度的聚(N-异丙基丙烯酰胺)(PNIPAM)微凝胶为种子,通过种子乳液聚合法合成由PNIPAM和聚丙烯酸(PAA)形成的具有互穿聚合物网络结构的微凝胶.傅立叶变换红外光谱分析结果表明微凝胶由PNIPAM和PAA两种聚合物组成,透射电镜表征结果证实微凝胶中PNIPAM和PAA两种聚合物形成了互穿网络结构.用动态激光光散射测试不同温度或pH值水介质中微凝胶的粒径,结果发现微凝胶具有良好的pH/温度双重刺激响应性.在水介质pH值大于5.5的情况下,PAA组分对微凝胶的体积相转变温度没有影响;而在水介质pH值为4.0的情况下,由于PAA与PNIPAM之间的氢键作用,微凝胶的体积相转变温度稍微降低.微凝胶中PAA组分含量越高,其pH刺激响应性越显著.     

在低压力下含高氯酸钠的互穿网络高分子固体电解质的电导行为

研究了含ＮａＣｌＯ４的ＰＥＯ４００与环氧树脂所形成的完全无定形的互穿聚合物网络（ＩＰＮ）固体电解质的电导率与压力和温度的关系．在室温至７０℃和压力０—４０ＭＰａ的范围内，这类ＩＰＮ的电导率在６ＭＰａ左右出现极大值，超过６ＭＰａ以后，电导率随压力的增加而减小．计算了在不同压力下的激活体积．与含ＬｉＣｌＯ４的同类ＩＰＮ体系进行了比较．从离子偶极作用原理出发对结果进行了讨论．实验表明离子通道畸变受运动离子的大小影响．离子半径越小，对离子通道影响越大，因而电导率改变也大．     

SYNTHESIS AND NMR CHARACTERIZATION OF PRECURSORS OF EPOXY NETWORK AS POLYMER HOST FOR SOLID ELECTROLYTE

To raise the room temperature ionic conductivity and improve the mechanical strength of a PEO-based polymer electrolyte, a noncrystalline two-component epoxy electrolyte system has been prepared. The diglycidyl ether of polyethylene glycols as precursors of the system were synthesized by a two-step process. The presumed structure of the product was characterized, by ~(13)C, ~1H NMR and IR spectroscopy. It was found that a side-reaction occurred between the secondary hydroxyl group of PEG-chlorohydrin and epichlorohydrin in some degree, resulting in a by- product containing—CH_2Cl side group. By selecting a characteristic signal, which is undistorted by the increase in the length of CH_2 CH_2—O segment, a ~1H NMR approach of determining the equivalent epoxy weight (EEW) was proposed. The method is valid to specimens even though the EEW is as high as 2,000. The examination of the specimens by DSC showed that epoxidation greatly depressed the crystallinity of the PEG's, whereas the T_g was raised.     

互贯型螯合树脂的研究．Ⅱ．IPN型含偕胺肟基螯合树脂的合成与性能研究

以交联聚苯乙烯－聚丙烯腈树脂为骨架，经功能基化反应制备出含偕胺肟基团的互贯型螯合树脂。对功能基化反应条件和螯合树脂对金的吸着性能，吸着选择性和吸着机理进行了研究。互贯型螯合树脂的吸着性能与互贯树脂的结构有关，而螯合树脂的选择吸着性则与互贯网络无关．     

环氧树脂/氧化石墨纳米复合物的等温固化行为研究

用示差扫描分析仪(DSC)研究了氧化石墨(GO)对N,N,N',N'-四缩水甘油基-4,4'-二氨基二苯基甲烷环氧树脂(TGDDM)/4,4'-二氨基二苯基砜(DDS)体系的等温固化反应的影响,用X射线光电子能谱仪(XPS)和傅里叶变换红外光谱仪(FTIR)研究了GO上存在的官能团及其对TGDDM/DDS体系固化行为的影响,用热失重分析仪(TGA)研究了天然石墨和GO的热力学稳定性.XPS、FTIR和TGA结果表明,GO上存在的大量羟基、羧基、环氧基等官能团能够影响环氧树脂的固化行为.DSC研究发现,环氧树脂/氧化石墨纳米复合物的固化反应属于自催化类型,随着GO含量的增加,达到最大反应速率的时间不断减小,初始反应速率不断增大,这说明GO对环氧树脂的固化反应有促进作用.Kamal模型计算得到的结果表明,随着GO含量的增加自催化反应初期阶段表观活化能E1先减小再增大,而自催化反应结束后表观活化能E2略微减小.经Kamal模型扩散控制函数修正后,整个固化过程中拟合得到的结果与实验数据相当吻合.以上结果说明,少量的GO对TGDDM/DDS体系的固化反应起着催化作用.     

室温固化蓖麻油聚氨酯/乙烯基聚合物互穿网络材料的一些规律及其性能

研究了蓖麻油与甲苯二异氰酸酯及丙烯酸酯或苯乙烯等乙烯基单体在室温下生成的互穿网络聚合物(IPN)的一些规律及其性能.用红外光谱追踪表明,聚氨酯的生成快于甲基丙烯酸甲酯的聚合.研究IPN凝胶点指出.凝胶点时间随聚氨酯含量增加及聚苯乙烯含量减少而缩短.丙烯酸甲酯在生成IPN过程中凝胶的生成速度要比苯乙烯的场合快.丙烯酸丁酯、丙烯腈或丙烯酸甲酯与蓖麻油聚氨酯生成的IPN的抗张强度在聚氨酯占一半时呈现最大值.透射电镜观察表明,生成速率较快的聚氨酯的微区存在于聚丙烯酸甲酯中.聚丙烯酸甲酯与蓖麻油聚氨酯形成的IPN在tanδ-T,曲线上呈现一个宽的玻璃化转变温度.