聚4-乙烯吡啶基碱性膜的制备及性能分析

采用自由基聚合制备聚4-乙烯吡啶(P4VP)。引入溴乙醇(BE)对制备的P4VP进行季铵化处理,合成一系列不同季铵化取代度的季铵化聚4-乙烯吡啶(QPVPE),最后,引入戊二醛(GA)与QPVPE进行交联,制备得到适合燃料电池使用的交联型聚4-乙烯吡啶基碱性膜。实验过程中,借助傅里叶变换红外光谱(FTIR)、紫外光谱(UV)、扫描电子显微镜(SEM)、热重分析(TGA,DTG)及力学性能测试等分析手段,对得到的导电膜结构及其理化性能进行分析,并对其导电性能进行性能测试。结果表明,QPVPE77.6%-GA16.87%膜综合性能最佳,该膜的电导率为10.48 mS/cm、含水率(WU)86.4%、溶胀率(SR)66.8%、拉伸强度为23.97 MPa。在25℃条件下,于1 mol/L的KOH溶液中浸泡192 h后,电导率损失为19%。因此,该膜具有较好的耐碱性能。     

Effect of the Type of Base and Number of Reaction Steps on the Degree of Quaternization and Molecular Weight of N-Trimethyl Chitosan Chloride

N-Trimethyl chitosan chloride (TMC), a chemically modified derivative of chitosan, is the first chitosan derivative shown to be an effective absorption enhancer for peptide and protein drugs across mucosal epithelia. TMC is synthesized by reductive methylation with methyl iodide in the presence of a strong base such as sodium hydroxide. In this reaction, the primary amino group on the C-2 position of chitosan is changed to a quaternary amino group. The charge density, as determined by the degree of quaternization, and probably also the molecular weight of TMC are important factors that influence the absorption enhancement effect and toxicity of this polymer. The molecular weight of the starting polymer decreases during the synthesis procedure due to factors such as the strong alkaline environment and elevated experimental temperatures. This study investigated the effects of two different bases, sodium hydroxide and dimethyl amino pyridine, together with a varying number and duration of reaction steps, on the degradation and the degree of quaternization of TMC polymers. ¹H-NMR (nuclear magnetic resonance) spectra showed a major increase in the degree of quaternization (21%–59%) of TMC with an increase in the number of reaction steps when sodium hydroxide was used as the base. Intrinsic viscosity values indicated that the use of dimethyl amino pyridine did not cause polymer degradation to the same extent as sodium hydroxide, but that the degree of quaternization of TMC stayed low (7.3%–9.6%) even when the number of reaction steps was increased. A combination of the two bases did not reduce polymer degradation, while the degree of quaternization was limited to relatively low values (12.5%–34.4%).     

Grafting of vinyl acetate onto chitosan and biocidal activity of the graft copolymers

The reaction process of polycarbosilane (PCS) fiber cured by cyclohexene vapor has been studied and compared with that of PCS fiber cured by air. The influence of curing temperature on Si? H bond reaction degree and gel content, the structure and composition of PCS were investigated by FTIR, EA, TGA, NMR, and GC‐MS. The results showed that, Si? H bond in the molecular structure of PCS reacted during cyclohexene curing process and the reaction degree increased when the curing temperature increases. Simultaneously, gel content of PCS fiber rapidly increased till PCS fiber became infusible. Si? H radical and Si? CH₂ radicals formed Si? CH₂? Si crosslinking of PCS molecules through the agency of cyclohexene. Some cyclohexyls linked to principal chain of PCS, which was proven by ¹³C‐CPMAS‐NMR, and broke off, and cyclohexane and some monosilane are generated as byproducts when temperature increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

自交联季铵化聚乙烯亚胺纸张增湿强剂的制备及应用

利用2,3-环氧丙基三甲基氯化铵（GTA）和γ-缩水甘油醚氧丙基三甲氧基硅烷（KH560）对聚乙烯亚胺（PEI）进行改性,制得自交联季铵化聚乙烯亚胺（MPEI）。结果表明,最佳制备条件（GTA和KH560质量分数分别为2%和1%（相对于PEI总质量）、反应温度50℃、反应时间3 h）下制得的MPEI固含量为12%、黏度为482.1 mPa·s、平均粒径为119.6 nm,稳定性良好,室温下放置90天无凝胶现象。利用傅里叶变换红外光谱（FT-IR）仪、热重分析（TG）仪、黏度仪、粒径分析仪及溶液稳定性分析仪等对MPEI进行结构和性能表征,探讨不同GTA质量分数的MPEI对纸张物理性能的影响,并利用扫描电子显微镜（SEM）观察纸张表面形貌。结果表明,向纸浆内添加质量分数为1.6%（相对于绝干浆质量）的MPEI并进行抄纸,与原纸相比,MPEI纸张的干抗张指数、湿抗张指数、耐折度和撕裂指数分别提高了34%、300%、515%和12%。本课题制得的MPEI不含有机氯,是一种新型环保的纸张增湿强剂。     

微波消解预处理碱木质素制备阳离子型表面活性剂

以碱木质素（AL）为原料,采用微波消解预处理AL,随后采用季胺化反应制备得到木质素基离子型表面活性剂。探究H₂O₂用量、微波功率、微波时间对产物性能的影响,并利用电位滴定、傅里叶变换红外光谱仪、紫外-可见分光光度计和光学接触角测量仪等对AL及其季铵化产物（ALG）、微波消解预处理木质素（ALM）及其季铵化产物（即木质素基阳离子型表面活性剂,ALMG）进行表征。结果表明,微波消解预处理的最佳反应条件是：H₂O₂用量8.4 wt%、微波时间7 min、微波功率140 W。经微波消解预处理后,ALM的酚羟基含量明显提高（由AL的1.29 mmol/g提高至ALM的2.39 mmol/g）。经季铵化接枝后,ALMG具有较低的表面张力,相同质量浓度（0.1 g/L）下,ALMG溶液的表面张力为36 mN/m,显著低于ALG溶液的表面张力（47 mN/m）;ALMG临界胶束浓度值为0.6 g/L,可用作润湿剂。     

氯甲基化/季铵化新型聚芳醚砜酮超滤膜的研制

本文对含二氮杂萘结构聚芳醚砜酮进行改性制得氯甲基化聚芳醚砜酮。选用N-甲基一2-吡咯烷酮作制膜溶剂，依据正交设计方法制得了一系列氯甲基化聚芳醚砜酮超滤膜。考察了聚合物浓度、添加剂种类和添加量以及制膜蒸发时间等对膜性能的影响。将氯甲基化聚芳醚砜酮超滤膜浸入三甲胺溶液进行季铵化反应，得季铵化聚芳醚砜酮超滤膜。并考察了膜的抗污染性。     

N-甲基咪唑季铵化反应动力学研究

在50℃下,以异丙醇为反应溶剂,研究了N-甲基咪唑与卤代烷的反应动力学,得到反应总级数为二级,分反应级数各为一级;测得N-甲基咪唑与溴丁烷在50℃、55℃和60℃时的反应速率常数分别为0.092 4 L.mol-1.h-1、0.169 2 L.mol-1.h-1和0.322 8 L.mol-1.h-1,进而计算出反应的活化能为2.18×105J.mol-1;同时,测得N-甲基咪唑与溴乙烷、溴丁烷的反应速率常数分别为0.292 6 L.mol-1.h-1和0.169 2 L.mol-1.h-1,说明溴乙烷与N-甲基咪唑的季铵化较溴丁烷易于进行。     

Novel AB crosslinked polymer networks based on 1‐vinylimidazole‐ terminated polyurethane and poly(methyl methacrylate)

1‐Vinylimidazole‐terminated telechelic polyurethanes were prepared from 1‐vinylimidazole and bromine‐terminated polyurethane. This vinyl‐terminated telechelic polyurethane (VTPU) and methyl methacrylate were polymerized in the presence of benzoyl peroxide to prepare novel AB crosslinked polymer networks (ABCPs). These were characterized by spectral, thermal and mechanical studies. The absence of the characteristic peak of vinyl group in infrared spectra of ABCP films confirms the occurrence of crosslinking. Static mechanical testing showed that the tensile strength of ABCP increases with increasing poly(methyl methacrylate) content. Dynamic mechanical studies revealed that ABCPs, at equal compositions of VTPU and methyl methacrylate, show good damping properties. Copyright © 2006 Society of Chemical Industry     

Synthesis of novel poly 2‐vinylpyridine‐mixed metal complexes and studying their effect as antitumor chemotherapeutic agents,part 2

The poly2‐vinylpyridine and cationic polymer‐mixed metal complexes (P2VPMC) have been prepared and characterized by analytical measurement such as: molecular weight, elemental analysis, IR‐spectroscopy, NMR‐spectroscopy, XRD, and UV. The degree of N‐alkylation of poly vinyl pyridine (P‐2VP) was 10% determined by chlorine content according to elemental microanalysis. Through ICP instrument the complexation between P‐2VPC and the mixed metal chlorides was proven. The structure of the samples was characterized using X‐ray diffraction. It was found that the complexes have amorphous properties. The antitumor activity of this compound was examined in vitro on cell lines. The results reflect pronounced cytotoxicity of P‐2VPMC against animal experimental EAC cells line, and human, HeLa, HCT116 and Hep‐G2, cell lines. Antitumor activity of the novel compound as applied on mice bearing Ehrlich solid carcinoma, revealed delays tumor growth compared with untreated animals and decreases tumor volume. The antitumor activity of the P2VPMC might be due to its ability to pass through the membrane and interact with, DNA causing cross‐linking action which might be the key factor for great antitumor activity of the P2VPMC compound. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

聚甲基丙烯酸-N,N-二甲氨基乙酯中空纤维复合纳滤膜的制备与性能表征

以聚甲基丙烯酸-N,N-二甲氨基乙酯(PDM)作为交联预聚物,利用双苄基试剂在聚砜中空纤维超滤膜表面进行季铵化反应(界面聚合),制得荷正电复合中空纤维复合纳滤膜.研究了PDM浓度、外加碱、溶剂、交联剂和交联温度等制备条件的影响.所制备的中空纤维纳滤膜对2g/L MgSO4的截留率≥98%,通量19.5L/(m2·h),界面聚合时间为3.5h.