核—壳结构聚丙烯酸酯—聚氨酯微乳液膜的相行为

用动态力学、红外光谱和差热分析方法研究了非交联核－壳结构聚丙烯酸酯－聚氨酯（ＰＡＣ－ＰＵ）微乳液膜的相行为．结果表明：核壳间的氢键增强了壳层软硬段间的相分离，同时破坏了硬段相中的短程有序结构，但增强了核壳相容性     

氟化聚氨酯的合成和表征

综述了各种不同结构的氟化聚醚《型和氟化聚酯型聚氨酯的合成并对产物的化学性能进行了描述。对各种表征方法的结果讨论表明,由于结构的特殊性,氟化聚氨酯有其不同于非氟化聚氨酯的特性。     

环氧基磁性离子交换树脂的合成与表征

用r—三氧化二铁—二乙烯三胺—双酚A环氧树脂首次合成了环氧基磁性离子交换树脂。实验结果表明,磁性树脂微球尺寸和吸附容量决定于树脂制备过程中的各种因素。一批典型的环氧基磁性树脂平均直径为0.15mm、吸附容量为3.3meq/g—R,磁化率为8.2emu/g—R,在酸性或碱性介质中稳定。实验数据也证实了这是一类优良的螯合树脂,对Zn~(2+)、Cd~(2+)、Hg~(2+)、Co~(2+)、Ni~(2+)、Pb~(2+)和其他二价阳离子有适当的螯合能力。但不吸附碱土金属离子,这和聚多胺树脂相同。     

水性涂料用聚丙烯酸酯微乳液的合成及其表征

低污染、低能耗的乳液涂料在建筑涂料中得到了广泛应用,具有核壳结构的聚合物乳液对胶膜的力学性能有较大的改善[1],微米(或纳米)级乳液具有优异的成膜性能,两者均是近年来高分子材料科学中发展十分迅速的新领域[2]。但微乳液聚合时乳化剂用量大,单体含量少。本文采用阴非离子复合乳化剂体系,单体预乳化工艺,种子乳液聚合法,通过正交实验优化聚合工艺参数及体系配方,合成了纳米级聚丙烯酸酯微乳液。并对乳液聚合物的粒径及分布、热性能、分子量及分布、结构等进行了表征。1　实验部分1 1　主要原料及乳液表征苯乙烯(St)、甲基丙烯酸甲…     

聚氨酯一聚丙烯酸酯共聚乳液的合成研究

以甲基丙烯酸β－羟乙酯封端的聚氨酯大分子单体与丙烯酸酯类单体进行乳液共聚，合成了以聚丙烯酸酯（PA）为主链、聚氨酯（PU）为侧链的接枝共聚物（PA－g－PU）乳液，用IR光谱和^1H NMR光谱对该聚氨酯大分子单体及PA－g－PU接枝共聚物进行了表征，并对影响聚氨酯－聚丙烯酸酯共聚合的因素进行了探讨。结果表明：聚氨酯大分子单体的加入对乳液聚合的速率造成较大的影响。该体系的表观活化自由能为99.39KJ/mol,Rp∝[I]^0.87,Rp∝[S]^0.12。     

聚苯乙烯二乙醇胺树脂的合成与表征

用氯甲基化聚苯乙烯与二乙醇胺反应合成了聚苯乙烯 二乙醇胺树脂，并利用元素分析、溶胀性能和 Ｉ Ｒ 对其进行表 征，研 究了该树脂的可能结构及某些性质。     

聚丙烯酸型弱酸阳离子交换树脂111生产工艺的研究

通过控制生产过程中引发剂，互贯方式，溶胀温度，解决了弱酸性阳离子交换树脂小生产工艺的稳定性和耐使用问题。     

丙烯酸铜树脂的合成及其表征

以偶氮二异丁腈为引发剂,调整硬段(甲基丙烯酸甲酯)和软段(丙烯酸乙酯、丙烯酸丁酯)的含量,通过自由基聚合反应制备了丙烯酸树脂。然后通过中和反应把氢氧化铜引入到丙烯酸树脂侧链中,最终制备了四种丙烯酸铜树脂。采用IR和GPC对树脂进行结构分析,IR发现碳碳双键吸收峰完全消失,GPC证实树脂的平均分子量在1.1~1.3万之间,表明聚合反应已经完全;DSC和TGA分析了树脂的热性能,发现玻璃化转变温度(Tg)随甲基丙烯酸甲酯含量的增加而线性增加,热稳定性随硬段含量的递增而逐渐下降。通过SEM发现铜离子在树脂体系中分散均匀,XRD分析表明树脂为无定形晶态结构。对树脂进行理化性能分析,发现四种树脂的附着力均为一级,粘度随着硬段含量的增加而适度增大。     

丙烯酸松香蔗糖聚氨酯/聚丙烯酸酯IPN的合成与性能

丙烯酸松香蔗糖聚氨酯/聚丙烯酸酯IPN的合成与性能     

Convenient synthesis of novel fluorinated polyurethane hybrid latexes and core-shell structures via emulsion polymerization process with self-emulsification of polyurethane

Novel fluorinated polyurethane hybrid latexes in the size range of 40–50 nm, fluoroalkyl acrylate as fluorinated monomers, with various fluorine content (F% = 9∼26 wt%) were successfully prepared via emulsion polymerization process without traditional emulsifier. The waterborne polyurethane, which was synthesized by using isophronediisocyanate, dimethylol propionic acid, polyethylene glycols, etc., served not only as copolymerizable macromonomer but also as polymeric high molecular weight emulsifier. The structures of polyurethane macromonomer and fluorinated polyurethane were characterized by Fourier transform infrared and H¹-NMR. Particle size, zeta potential, micromorphology of the latex par.ticles, and surface properties were investigated by dynamic light scattering, potential particle size analyzer, transmission electron microscopy, and contact angle measurement, respectively. Results illustrated that the advantage of this process is that the size of fluorinated polyurethane hybrid particle is less sensitive to the composition. Furthermore, it was showed that fluorinated polyurethane latex particles had core-shell structures, especially when the content of fluorine was 26.08 wt%. Moreover, there was an obvious migration of fluorinated groups to the surface during the formation of fluorinated polymer films, although fluorinated groups were covered by polyurethane in latex particles.     

Study of Soap-free Waterborne Polyurethane-acrylic Emulsion by Polymerization in situ

以二羟甲基丙酸（DMPA）、甲基丙烯酸甲酯（MMA）、异佛尔酮-二异氰酸酯（IPDI）、聚乙二醇（PEG1000）、丙烯酸丁酯（BA）、丙烯酸羟乙酯（HEA）等为基本原料,三乙胺（TEA）作为中和剂,采用原位乳液聚合法合成了水性聚氨酯一丙烯酸酯复合乳液（PUA）。较详细地研究了DMPA的加入量、NCO／OH的比值、固含量、引发剂的种类及加入量、乳化剂种类及加入量等对PUA复合乳液性能以及外观的影响。通过傅立叶变换红外光谱、激光粒度分析仪、凝胶渗透色谱等对合成的PUA复合乳液进行了分析和表征。     

Polymer mediated peptide immobilization onto amino-containing N-isopropylacrylamide-styrene core-shell particles

Monodisperse cationic core-shell latex particles have been prepared using a shot polymerization process, with N-(3-aminopropyl)-methacrylamide-hydrochloride (APMH) as the functional monomer. The final latexes were characterized with respect to final polymerization conversion, water soluble polymer formation, particle size and size distribution, surface charge density and electrokinetic properties. Then the covalent grafting of maleic anhydride-alt-methyl vinyl ether (MAMVE) copolymer onto aminated latex particles was investigated. The most efficient conditions to obtain derivatised particles with no alteration of the colloidal stability were to control both polymer amount/latex particles concentration ratio and the mixing method of the two species. The charge inversion of the hydrolysed MAMVE functionalized particles was demonstrated by measuring the electrophoretic mobility as a function of pH. Finally, the covalent binding approach was implemented with peptide-MAMVE conjugates, confirming the great potential of this promising methodology for the preparation of reactive latex particles bearing peptides.     

核／壳型聚硅氧烷丙烯酸酯复合乳液的制备

采用种子乳液聚合的方法制备了具有核／壳结构的聚硅氧烷丙烯酸酯复合乳液，考察了乳化剂、单体的加入方式及配比对产生乳液粒子的影响。结果表明，乳化剂在核阶段和壳阶段的单体聚合中都起着很重要的作用，当乳化剂分子在乳液粒子上的覆盖率低于４０％时，可制得较理想的核／壳型复合乳液。     

Preparation and surface properties of latexes with fluorine enriched in the shell by silicon monomer crosslinking

A series of core-shell acrylic copolymer latexes containing fluorine enriched in the shell have been prepared by emulsion polymerization of a variety of hydrocarbon monomers with (perfluoroalkyl)methyl methacrylate and vinyltriethoxysilicone. In the presence of a reactive anionic and a long chain anionic-nonionic emulsifier, the core-shell latexes were prepared and characterized by transmission electron microscopy (TEM) and tapping-mode atomic force microscopy (AFM). From AFM and contact angle measurements, it was observed that the resulting fluorine and silicon-containing acrylic copolymers with surface energy as low as 15.5 mN/m formed a dense and gradient film containing a surface layer with high a fluorine content, and that the fluorinated particles can be fixed on the surface due to the crosslinking reaction of multi-functional silicon monomer even though the fluorinated carbon number was not enough to crystallize.     

Preparation of Covalently‐colored Polymer Latex via Batch Emulsion Polymerization

Covalently‐colored polymer latex was synthesized via batch emulsion copolymerization of styrene, butyl acrylate and methacrylic acid in the presence of red polymerizable dye monomer consisting of anthraquinone chromophore, alkyl spacer and acryloyl group, and the influences of the initiator, surfactant and polymerizable dye on the polymerization and the latex properties were investigated. Results showed that the initiator amount was a determinative factor for the monomer conversion, and a high conversion of the polymerizable dye could be achieved when the ammonium persulfate amount was equal to or more than 1 wt% to the total monomers. Most of the chromophores were covalently bonded to the polymer chains if the polymerizable dye was used in the range of 0–1.5 wt%. The light fastness of the resulting latex film was much better than that of the noncovalently‐colored polymer film.     

种子乳液聚合物胶粒形态及胶膜结构研究

以醋酸乙烯酯和丙烯酸丁酯为单体，用乳液聚合方法，以极性小的ＰＢＡ为种子进行了ＶＡ种子聚合，用透射电镜染色及皂液滴定方法对胶粒形态进行了表征，结果，上述聚合反应能形成ＰＢＡ／ＰＶＡ核壳结构的胶粒，而以ＰＶＡ为种子对ＰＢＡ进行聚合，则不能形成ＰＶＡ／ＰＢＡ核壳结构的胶粒，其胶粒亦具有类似ＰＢＡ／ＰＶＡ核壳结构或半包囊结构，将胶乳制成胶膜，其耐水性能测试表明成膜后胶粒基本保持了其分散阶段的形态。     

丙烯酸丁酯-醋酸乙烯酯共聚物胶乳粒子的结构和性能

电镜观察表明,丙烯酸丁酯-醋酸乙烯酯共聚物胶乳粒子均为核-壳结构,若配料比不同,含量大者为核,而加料方式不同,则先加者先聚合成核.微观结构不同,可明显地影响胶膜的力学性能、T_g和耐水性.根据胶乳粒子微观结构的观察结果,认为当醋酸乙烯酯>50mol%时,共聚的引发和成核是在水相中进行的.     

Synthesis and characterization of random or gradient butadiene-p-methylstyrene copolymers via anionic polymerization

Copolymers of 1,3-butadiene and p-methylstyrene （p-MS） were synthesized via anionic polymerization. A benzophenone-potassium complex was added to tune the reactivity ratio of the two monomers, leading to random and gradient composition alonglthe copolymer chain. The overall composition and microstructure could be controlled and well characterized by GPC and H-NMR. The p-MS was distributed from gradient to random with increasing the content of the benzophenone-potassium complex, and the 1,2-microstrucmre in the polybutadiene sequence increased at the same time. The hydrogenation of the copolymer of 1,3-butadiene and p-MS resulted in the corresponding saturated copolymer with well- defined structure and narrow molecular weight distribution.     

活性聚甲基丙烯酸甲酯活性链和溴甲基化聚苯乙烯偶合反应制备接枝共聚物

采用基团转移聚合、阴离子聚合以及高分子偶合反应的方法，合成了一种结构明确、链长均匀、分子量可控的聚苯乙烯接枝聚甲基丙烯酸甲酯。主链聚苯乙烯由阴离子聚合得到，并进行溴甲基化。支链活性聚甲基丙烯酸甲酯由基团转移聚合制备。经偶合反应后得到分子量为３×１０４～７×１０４、多分散性指数Ｄ为１．２～１．４的接枝共聚物。用１ＨＮＭＲ，ＧＰＣ和ＤＳＣ表征接枝产物。和均聚物相比，共聚物的玻璃化温度较低。