聚甲基丙烯酸甲酯/聚丙烯酸乙酯互穿网络体系相逆转、相态结构与性能的研究

本文研究了聚甲基丙烯酸甲酯/聚丙烯酸乙酯互穿网络体系(PMMA/PEALIPN)相分离和组分配比对其相逆转、相态结构及动态力学性能的影响.同时,对LIPN与其相应的混合乳液体系的结构和阻尼特性进行比较.结果表明,LIPN体系由于存在网络的相互贯穿,与混合体系相比其相分离程度低,出现精细结构,密度较高.当丙烯酸乙酯(EA)含量低时,PEA呈细胞结构分散在PMMA连续相中,随EA量的增加,体系出现相逆转并在EA体积含量为48％至86％范围内呈两相连续,各种性能发生突变和具有高阻尼特性.实数模量的实验点服从用Halpin-Tsai-Nielsen模量上、下限方程和描述两相连续的对数混合律三个方程结合计算的理论曲线.     

聚醋酸乙烯酯/聚丙烯酸甲酯互穿网络聚合物的研究——1.聚合条件对体系相容性的影响

用分步法合成了聚醋酸乙烯酯/聚丙烯酸甲酯互穿网络聚合物(PVAc/PMA-IPN),PVAc和PMA的交联剂分别是丁二酸二烯丙酯(DAS),和二乙烯基苯(DVB)。当DAS用量较小时,VAc聚合时的接枝反应较明显,PVAc网络的交联密度高于化学当量的计算值。动态力学的实验结果表明,丙烯酸甲酯的聚合温度和聚合过程中的溶胶-凝胶转变对PVAc/PMA-IPN体系的相容性有很大影响。     

聚醋酸乙烯酯/聚丙烯酸甲酯互穿网络聚合物的研究——4.橡胶态模量和网络间的互穿缠结

用动态粘弹谱仪测定了分步法互穿网络聚合物,聚醋酸乙烯酯/聚丙烯酸甲酯(PVAc/PMA-IPN)的橡胶态模量。实验值与从方程E_R=φ_Ⅰ~1/3·E_(R,Ⅰ)~0+φ_(Ⅱ)E_(R,Ⅱ)~0所得理论值的比较,表明网络问有明显的互穿缠结,网络Ⅰ交联程度对其的影响大于网络Ⅱ。并结合实验结果对Binder-Frisch理论中,ΔS_(ent)∝N_(c,Ⅰ)~(-1)·N_(c,Ⅱ)~(-1/2)关系的合理性进行了讨论。     

COMPATIBILITY IN POLYMER BLENDS OF POLY (VINYL ACETATE) AND POLY (METHYL METHACRYLATE)STUDIED BY NMR

Compatibility of poly (vinyl acetate) (PVAc) with poly (methyl methacrylate) (PMMA) mixtures has been studied by using nuclear magnetic relaxation, differential scanning calorimeter and small-angle X-ray scattering techniques. The nuclear magnetic relaxation time T_1's were measured as a function of composition in blends of PMMA and PVAc prepared from chloroform solution. The results show that the system is miscible for casting from chloroform solution.     

聚醋酸乙烯酯/聚丙烯酸甲酯互穿网络聚合物的研究——1.聚合条件对体系相容性的影响

 用分步法合成了聚醋酸乙烯酯/聚丙烯酸甲酯互穿网络聚合物(PVAc/PMA-IPN),PVAc和PMA的交联剂分别是丁二酸二烯丙酯(DAS),和二乙烯基苯(DVB)。当DAS用量较小时,VAc聚合时的接枝反应较明显,PVAc网络的交联密度高于化学当量的计算值。动态力学的实验结果表明,丙烯酸甲酯的聚合温度和聚合过程中的溶胶-凝胶转变对PVAc/PMA-IPN体系的相容性有很大影响。     

EFFECT OF SURFACTANTS ON FILM FORMATION OF POLY (VINYL ACETATE) AND POLY (VINYL ACETATE-BUTYL ACRYLATE) LATEXES

Effect of ethoxylated nonyl phenol type non-ionic and alkyl sulfate type anionic surfactants on the film formation process of poly (vinyl acetate) and poly (vinyl acetate-acrylate) latexes are discussed. HLB value of non-ionic surfactant is shown to affect glass transition temperature, minimum film formation temperature and rate of film coalescence of vinyl acrylic latexes. Higher HLB non-ionic surfactant appears to be more compatible than the lower HLB ones with the fairly polar vinyl acrylic latex and form a well coalesced film. Presence of sodium lauryl sulfate in the latex is observed to result in incompatible regions on the latex film surface, typical of two phase morphology. Influences of surfactants on the film formation process in the polar vinyl acrylic latexes are compared and contrasted with the available data on the effects of surfactants in styrene butadiene latexes. The findings are discussed in terms of adsorption and interaction behavior of surfactants at polar vinyl acrylic latex surfaces and current theories of latex film formation mechanisms.     

聚醋酸乙烯酯/聚丙烯酸甲酯互穿网络聚合物的研究——4.橡胶态模量和网络间的互穿缠结

 用动态粘弹谱仪测定了分步法互穿网络聚合物,聚醋酸乙烯酯/聚丙烯酸甲酯(PVAc/PMA-IPN)的橡胶态模量。实验值与从方程E_R=φ_Ⅰ^1/3·E_R,Ⅰ0+φ_ⅡE_R,Ⅱ⁰所得理论值的比较,表明网络问有明显的互穿缠结,网络Ⅰ交联程度对其的影响大于网络Ⅱ。并结合实验结果对Binder-Frisch理论中,ΔS_ent∝N_c,Ⅰ^-1·N_c,Ⅱ(-1/2)关系的合理性进行了讨论。系的合理性进行了讨论。     

THE COMPATIBILITY OF BLENDS OF POLY(VINYL CHLORIDE) OR CHLORINATED POLY(VINYL CHLORIDE) WITH POLY(METHYL METHACRYLATE)

IR spectral shifts of carbonyl vibrational absorption for ethyl acetate, which acts analogically as the structural unit of poly(methyl methacrylate), in cyclohexane, chloroform, chlorinated paraffins, poly(vinyl chloride) and chlorinated poly(vinyl chloride) were measured. The results suggest that there are specific interactions between the carbonyl groups and the chlorinated hydrocarbons which could be responsible for the apparent compatibility of poly(vinyl chloride)—poly(methyl methacrylate) and chlorinated poly(vinyl chloride)—poly(methyl methacrylate) blends. Additionally, the effects of the preparation mode of blend films on phase separation and observed compatibility are discussed.     

聚乙烯醇/聚乙烯基吡咯烷酮共混体系的结晶行为

用DSC、WAXD和SAXS研究了聚乙烯醇(PVAl)/聚乙烯基吡咯烷酮(PVP)共混体系的结晶行为.PVAl的结晶度随PVP含量增加而减少,并存在结晶度为零的组成(PVAl)的重量分数约为50％.与纯PVAl相比,共混物的温度区间T_m-T_g减小,表明PVP对PVAl的结晶起抑制作用.共混物中PVAl的结晶速度下降,具体表现为PVAl过冷区随PVP含量增加而扩大,动力学速度常数减小,球晶增长速度下降.纯PVAl和共混体系的等温结晶速率均遵循Avrami方程.退火样品的长周期、片晶厚度和过渡层厚度大于相同组成未退火样品.两者长周期随PVP含量增长加显著增大,片晶厚度增长次之,过渡层厚度变化不大.     

聚乙烯醇/聚乙烯基吡咯烷酮共混体系相容性研究

用DSC、FTIR、SAXS和测定Flory-Huggins相互作用参数等方法对聚乙二醇(PVA1)/聚乙烯基吡咯烷酮(PVP)共混体系的研究。结果表明,该体系具有完全互容的性质。共混物只有一个玻璃化转变温度。用DMSO作溶剂浇铸的膜光学透明。PVA1的长周期和片晶厚度均随PVP含量增加而增大,但后者增大的幅度比前者小得多,表明PVP和PVA1的非晶部分形成均相并夹入到球晶内部。共混物中PVP羰基吸收峰和PVA1的羟基吸收峰与相应均聚物相比,在红外光谱图中皆向低频方向迁移,迁移波数随第二组分含量的增加而增大。表明二者间有氢键生成。用平衡熔点计算的Flory-Huggins相互作用参数为-0.88。     

聚甲基丙烯酸甲酯/(苯乙烯-丙烯腈)共聚物混合体系的早期分离

本文用激光光散射技术研究了高分子混合体系聚甲基丙烯酸甲酯/(苯乙烯-丙烯腈)共聚物(PMMA/PSAN)不稳相分离(Spinodal decomposition)过程,结果指出,相分离前期符合Cahn理论预言的结果;首次用光散射技术在高分子混合体系相分离研究中得到了不稳相分离增长速率最大值R(q_m);只(q)的实验结果与理论值相吻合;证实了界面自由能对相分离增长速率的影响是不可忽略的。     

聚甲基乙烯基酮的不对称还原反应

聚甲基乙烯基酮的不对称还原反应李弘姚金水何炳林（吸附与分离功能高分子材料国家重点实验室南开大学高分子化学研究所天津３０００７１）关键词对称硅氢化，聚甲基乙烯基酮，手性噻唑烷，铑近年来手性过渡金属络合物催化的前手性酮和烯的不对称硅氢化反应已在国际上受...     

聚环氧氯丙烷聚氨酯／聚甲基丙烯酸甲酯互穿网络聚合物的相容性与力学性能

用同步法合成了聚环氧氯丙烷聚氨酯／聚甲基丙烯酸甲酯互穿网络聚合物［ＰＵ（ＰＥＣＨ）／ＰＭＭＡＩＰＮ］，调节ＩＰＮ中两组分组成比制备出由完全弹性体、增强弹性体、增韧塑料到脆性塑料多种高聚物合金材料．用ＤＳＣ、动态力学谱、ＴＥＭ对ＩＰＮ的研究结果表明，ＰＵ（ＰＥＣＨ）／ＰＭＭＡＩＰＮ的两组分是完全相容的；同时对各种组成比的ＩＰＮ材料进行力学性能测试，用相容性ＩＰＮ中互穿、缠结结构解释其力学行为，并用ＳＥＭ对断面形貌进行了观察解释．     

STUDIES OF THE CRYSTALLIZATION BEHAVIOR IN THE CRYSTALLINE/AMORPHOUS POLYMER BLENDS: POLY(ETHYLENE OXIDE)/POLY(METHYL METHACRYLATE) AND POLY(ETHYLENE OXIDE)/POLY(VINYL ACETATE)

The crystallization process of poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA)and PEO/poly(vinyl acetate) (PVAc) blends has been characterized by Fourier Transform Infrared(FTIR) spectra in conjunction with Differential Scanning Calorimeter (DSC) measurements. Thecrystallinity of PEO varies consistently with PEO content in PEO/PVAc blends and the PEO/PMMAblends containing 50 wt% or less PMMA. For the PEO/PMMA blends containing 60 wt% ormore PMMA, the crystallinity of PEO decreases more than PEO content but develops with crystal-lization time. These results can be explained in terms of difference between the crystallization tem-perature (T_c) and glass transition temperature (T_g) of the blends as a function of content of amorphouscomponent.     

因子分析法和FTIR光谱法研究聚甲基丙烯酸正十八酯和聚醋酸乙烯酯的共混

聚甲基丙烯酸正十八酯[P(n-OMA)]是梳状聚合物,玻璃化温度很低(173K),与其他聚合物共混的热行为的研究需在液氮下进行.本文应用Koenig的因子分析法和FTIR光谱法,在常温下判别了P(n-OMA)与聚醋酸乙烯酯(PVA)的共混相容性,用分峰技术准确定量了它们的相互作用,讨论了影响相互作用的因素。并用DTA谱验证了所得的结论.     

聚乙烯醇水凝胶溶胀特性研究

在前文对聚乙烯醇水溶液冰冻凝胶化浓度依赖性研究基础上，对接触浓度（Ｃ）以上聚乙烯醇水溶液通过冰冻－融化处理，制得了一种含水率高达９５～９８％的水凝胶．系统研究了该水凝胶在蒸馏水中的溶胀及溶解特性．得到了一个与实验结果相吻合的溶胀动力学方程：Ｑ１＝Ｑｅ－（Ｑｅ－ＱＯ）／ｅｋｔ，及平衡溶胀比Ｑｅ与浓度之间的定量关系：Ｑｅ＝６０．３－４．４５×１０２Ｃ．发现当冰冻－融化次数Ｎ≤５时，平衡溶胀比Ｑｅ及溶解量Ｗ与冰冻－融化次数（Ｎ）间满足幂函数关系：Ｑｅ。Ｗ通过对聚乙烯醇水凝胶平衡溶胀比与经冰冻处理的聚乙烯醇水溶液特性粘数进行比较，发现反映链间氢键凝聚缠结效应与反映链内氢键凝聚缠结效应的定量指标具有等效性．     

PVA/PVP共混物的SAXS研究

聚乙烯醇(PVA)/聚吡咯烷酮(PVP)共混物的小角X-射线散射(SAXS)研究表明,PVA/PVP共混物的结构参数与共混物组分比及热历史密切相关。按Vonk一维电子密度相关函数法,得到PVA/PVP共混物的长周期,过渡层厚随PVP组分含量增加而增加;结晶片层厚和比内表面积却随PVP含量增加而降低。热处理可提高共混物的结晶性。     

SYNTHESIS AND CHARACTERIZATION OF A NEW COMBLIKE POLYMER BASED ON POLY (VINYL METHYL ETHER-ALT-MALEIC ANHYDRIDE) BACKBONE

A new comblike polymer host for polymer electrolyte was synthesized by reactingmonomethyl ether of poly (ethylene glycol) with poly (vinyl methyl ether alt-maleic anhydride)and endcapping the residual carboxylic acid with methanol. Butanone was selected as a solventfor the esterification in order to obtain a completely soluble product. The synthesis processwas traced through by IR. Compared with the model compounds, the presumed structure ofthis comblike polymer has been proved to be valid by ~(13)C NMR. The comb polymer is a whiterubbery solid. It can be dissolved in butanone and THF, and manifests good film formingability.