两亲性共聚物P(MMA-co-AMPS)对聚偏氟乙烯超滤膜性能的影响

以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为亲水单体,甲基丙烯酸甲酯(MMA)为疏水单体,偶氮二异丁腈(AIBN)为引发剂,采用自由基共聚合法制得了两亲性共聚物P(AMPS-co-MMA);以两亲性共聚物P(AMPS-co-MMA)与聚偏氟乙烯(PVDF)共混,通过相转变法制备PVDF/P(MMA-co-AMPS)超滤膜。利用傅里叶变换红外光谱、热失重法表征无规共聚物的组成和热稳定性能。并通过扫描电子显微镜,傅里叶变换红外光谱、吸水率测试、表面润湿性测试,探讨了不同单体摩尔比对PVDF/P(MMA-co-AMPS)超滤膜的结构及性能的影响。结果表明,单体AMPS与MMA间发生自由基聚合生成两亲性共聚物P(AMPS-co-MMA)。PVDF/P(MMA-co-AMPS)超滤膜表面多孔,内部有大孔,存在相对致密皮层和多孔的支撑层。当2-丙烯酰胺基-2-甲基丙磺酸和甲基丙烯酸甲酯的摩尔比为2∶1时,PVDF/P(MMA-co-AMPS)超滤膜吸水率和表面润湿性能最好。     

有机硅树脂合成及其共混改性研究

通过实验筛选出合成有机硅树脂的配方，讨论了原料配比、水解温度，介质酸度和溶剂组成对有机硅树脂的影响。采用傅里叶变换红外光谱表征了聚甲基丙烯酸丁酯(PBMA)共混改性有机硅树脂前后的结构特征；采用扫描电子显微镜分析了有机硅树脂、PBMA和PBMA共混改性有机硅树脂的微观结构，进而探讨，改性有机硅树脂室温同化机理，即有机硅树脂分子和PBMA分子之间的互相介入、互相贯穿使之形成网络，具有了自由基协同效应。     

PS-b-PEA嵌段共聚物的合成与表征

采用“活性”自由基聚合的方法合成了不同分子量的苯乙烯和甲基丙烯酸乙酯[polystyrene-block-poly(ethyl methacrylate),PS-b-PEA]嵌段共聚物。并用凝胶渗透色谱(GPC)和红外光谱(FTIR)对所合成的共聚物进行了表征,实验结果显示:在4-羟基-2,2,6,6-四甲基哌啶-1-氧化物自由基(HTEMPO.)和偶氮二异丁腈(AIBN)存在下,苯乙烯聚合反应所得到的聚苯乙烯分子量分布在1.18~1.2范围,分子量随聚合时间的延长而增大(7 200~69 300 g/mol);将该聚苯乙烯溶于甲基丙烯酸乙酯,在(130±2)℃时可以重新引发甲基丙烯酸乙酯的聚合反应,且甲基丙烯酸乙酯的聚合反应具有“活性”聚合的特征,共聚物的数均分子量及分布分别在57 800~107 800 g/mol和1.22~1.26范围,共聚物由FTIR表征显示:在聚苯乙烯接上聚甲基丙烯酸乙酯后,在1 158 cm-1及1 727 cm-1出现其甲基丙烯酸乙酯的特征吸收峰,说明共聚物为嵌段共聚物。     

MMA/N-对甲苯基马来酰亚胺乳液共聚的研究

通过乳液共聚得到N－对甲苯基马来酰亚胺（NPTMI），甲基丙烯酸甲酯（MMA）的二元共聚物，用扭辫分析，热重分析和维卡软化点测定仪研究了不同NPTMI含量对共聚物热性能的影响，以及共聚物的力学性能，流变性能，研究结果表明，共聚物初始分解温度（Tini)，失重50％时的温度，玻璃化转变温度（Tg)及维卡软化点（TViout)都随NPTMI的含量增加而提高，当NPTMI含量为15％时，Tg提高14．1℃，Tini提高23．2℃，TVicut提高8．9℃，工聚物熔体呈假塑性流体，同时共聚物熔体非牛顿指数随NPTMI含量的增加而增大。     

VAc／MMA半连续乳液共聚合的研究：Ⅰ种子乳液共聚合

以过硫酸铵为引发剂，十二烷基硫酸钠为乳化剂，于７０℃下进行了ＶＡｃ＝ＭＭＡ种子乳液共聚合。试验考察了组分和操作条件对体系稳定性，聚合速度及组成分布等的影响，同时，从理论上给出了加料速率与体系稳定性因子间的关系。     

A RIS treatment of the mean-square dipole moment of PMMA chains in consideration of the pendant ester group orientations

According to the six-state scheme proposed by Vacatello and Flory, the mean-square dipole moments 〈M²〉/x (x: number of monomeric units) of poly(methyl methacrylate) (PMMA) chains and their temperature dependence were calculated by the matrix algebra method of rotational isomeric state theory. To take account of the orientation effect of polar ester groups, the statistical weight matrices, U′ and U″, were recast into an expanded form. A Bernoullian probability λ introduced to measure the preference between the two alternative orientations (χ=0 and χ=π) of the side ester groups was found to give rise to a large effect on the mean-square dipole moment of polymers. When the skeletal bonds of a meso dyad are both in trans, an exceptionally strong dipole-dipole interaction may take place. If the two adjacent ester groups adopt the same orientation, the dipoles must be situated nearly parallel to each other in a close proximity. Such repulsive interactions may be alleviated by taking a staggered conformation, i.e. (χ,χ′)=(0,π) or (π,0). Such neighbor-dependent correlation inherent to the meso dyad is considered by assigning a parameter λ′ to the proper element of the U_m″ matrix. The values of 〈M²〉/x observed at 30 °C were satisfactorily reproduced by adopting λ=0.270 and λ′=0.865. The thermal coefficients were found to be reconciled with the available experimental data by allowing the orientation parameters λ and λ′ to be slightly temperature dependent. The stereochemical characteristics of the chain terminals were examined in order to extend the treatment to include the dipole moment of PMMA oligomers.     

Synthesis,characterization, and in vitro drug‐release properties of 2‐hydroxyethyl methacrylate copolymers

2‐Hydroxyethyl methacrylate was copolymerized with acrylamide, N‐vinyl‐2‐pyrrolidone, and n‐butyl methacrylate by free‐radical solution polymerization with α,α′‐azobisisobutyronitrile as an initiator at 70 ± 1°C. The average molecular weights and molar compositions of the resultant copolymers were determined with gel permeation chromatography and ¹H‐NMR spectroscopy data, respectively. Diclofenac or 2‐[(2,6‐dichlorophenyl)amino]benzene acetic acid, a nonsteroidal anti‐inflammatory drug, was chemically attached to the copolymers by transesterification reaction in the presence of N,N′‐dicyclohexylcarbodiimide to give macromolecular prodrugs. All the synthesized polymers were characterized with Fourier transform infrared, ¹H‐, and ¹³C‐NMR spectroscopy techniques. The polymer–drug conjugates were hydrolyzed in cellophane member dialysis bags containing aqueous buffered solutions (pH 8) at 37°C, and the hydrolysis solutions were detected by UV spectrophotometer at selected intervals. The results showed that the drug could be released by selective hydrolysis of the ester bond from the side chain of the drug moiety. The release profiles of the drug indicated that the hydrolytic behavior of polymeric prodrugs strongly depends on the hydrophilicity of the polymer. The results suggest that the synthesized copolymers could be useful carriers for the release of diclofenac in controlled‐release systems. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2403–2409, 2007     

硅丙乳液的合成及其吸水性的研究

以丙烯酸丁酯、甲基丙烯酸甲酯、丙烯酸、乙烯基三乙氧基硅烷(VTES)为原料,分别采用半连续法、种子预乳化法和后添加VTES法制得了硅丙乳液。研究了聚合工艺对硅丙乳液的吸水率、冻融稳定性、钙离子稳定性等的影响。结果表明,采用半连续法和种子预乳化法制得的硅丙乳液,冻融稳定性比较好,经过冻融循环后可以复原;采用半连续法制得的乳胶膜的吸水率随着乙烯基三乙氧基硅烷的用量的增加而降低;采用后添加VTES法制得的硅丙乳液,其吸水率则随VTES用量的增加而升高,冻融循环后发生破乳。     

甲基丙烯酸缩水甘油酯熔融接枝聚丙烯研究

利用双螺杆挤出机研究甲基丙烯酸缩水甘油酯(GMA)接枝改性聚丙烯,探讨了停留时间、单体组成、引发剂用量等因素对接枝反应的影响。结果表明,通过工艺条件的控制在双螺杆挤出上可制备出接枝率高、流动性、色泽度良好的接枝产物。     

甲基丙烯酸全氟辛基乙酯-甲基丙烯酸丁酯乳液共聚动力学

采用十二烷基硫酸钠和OP-10混合乳化剂，将甲基丙烯酸全氟辛基乙酯-甲基丙烯酸丁酯进行乳液共聚，研究了反应温度、引发剂浓度、乳化剂浓度、全氟单体浓度等因素对聚合速率(RP)的影响。结果表明，聚合速率随着引发剂浓度、乳化剂浓度的增加而增加；随着全氟单体浓度的增加而降低，该体系的表现活化自由能为106．27kJ／mol，RP∝[I]^.68，RP∝[S]^0.88，RP∝[FMA8]^0.33