氟硅油合成工艺与应用性能研究进展

该文总结了氟硅油的制备方法,包括硅氢加成法、水解法、开环聚合法,并讨论了分子结构对性能的影响,包括氟硅油多种界面功能的作用机理、氟-硅协同效应等。此外,该文还综述了氟硅油作为润滑剂、消泡剂、整理剂、超疏水材料的研究应用现状。氟硅油应用过程中,以有机磷化合物、硅醇铁等为添加剂能有效地提升氟硅油的抗剪切性、抗氧化性;在分子链中引入聚醚或氨基等制备共改性硅油,能够有效地提升氟硅油的表面性能。最后,对于氟硅油的发展方向和应用前景进行了展望。     

氟硅油合成工艺与应用性能研究进展（特约稿件）

氟硅油结合了氟碳材料与有机硅各自的优点,具有优异的耐温、润滑等表面性能,在石油化工、纺织、机械等众多领域中得到广泛应用。本文总结了氟硅油的制备方法,包括硅氢加成法、水解法、开环聚合法,并讨论了分子结构对性能的影响,包括氟硅油多种界面功能的作用机理、氟-硅协同效应等。此外,文章还介绍了氟硅油作为润滑剂、消泡剂、整理剂、超疏水材料的研究应用现状。氟硅油应用过程中,以有机磷化合物、硅醇铁等为添加剂能有效提升氟硅油的抗剪切性、抗氧化性;在分子链中引入聚醚或氨基等制备共改性硅油,能够有效的提升氟硅油的表面性能。最后对于氟硅油的的发展方向和应用前景进行了展望。     

三氟丙基甲基硅油的乳化研究

通过采用转相乳化法,以较低黏度的三氟丙基甲基硅油为原料,以自制的FGM-661为乳化剂,成功制得了甲基氟硅油乳液,质量比为甲基氟硅油30％,FGM-661为15％,经离心实验证明乳液具有良好的稳定性,有一定应用价值.     

杂多酸催化法制备低摩尔质量羟基封端氟硅油

采用杂多酸催化1,3,5-三(3’,3’,3’-三氟丙基)-1,3,5-三甲基环三硅氧烷的开环聚合反应,分别合成了低摩尔质量的羟基封端三氟丙基硅油、羟基封端三氟丙基甲基-二甲基硅油、羟基封端三氟丙基甲基-乙烯基甲基硅油。对3种羟基封端氟硅油的结构进行了表征,讨论了氟硅油的摩尔质量与黏度的关系。通过1H NMR谱图计算出3种氟硅油的平均摩尔质量分别为642、613、657 g/mol,黏度分别为0.16、0.12和0.08 Pa.s。即在相近摩尔质量的情况下,三氟丙基的含量直接影响了氟硅油的黏度,同时甲基与乙烯基空间结构的不同也对氟硅油的黏度产生一定影响。     

二甲基硅油及其衍生物在消泡帮领域的研究进展

二甲基硅油由于其良好的化学惰性和低表面张力,广泛应用于消泡剂领域。聚醚改性硅油和氟改性硅油作为二甲基硅油的两种主要衍生产物,具有更强的消、抑泡能力。本论文重点介绍了二甲基硅油消泡剂、聚醚改性硅油消泡剂、氟改性硅油消泡剂的特性、制备方法及应用。     

二甲基硅油及其衍生物在消泡剂领域的研究进展

二甲基硅油由于其良好的化学惰性和低表面张力,广泛应用于消泡剂领域。聚醚改性硅油和氟改性硅油作为二甲基硅油的两种主要衍生产物,具有更强的消、抑泡能力。本论文重点介绍了二甲基硅油消泡剂、聚醚改性硅油消泡剂、氟改性硅油消泡剂的特性、制备方法及应用。     

3，3，3-三氟丙烯-氟硅材料的桥梁

介绍了3，3，3-三氟丙烯的物理化学性质、制备方法和在氟硅橡胶、氟硅油合成中的应用。     

3，5-双（三氟甲基）苯基硅油的合成及性能研究

以3,5-双(三氟甲基)溴苯和甲基三甲氧基硅烷为原料,通过格氏反应和取代反应制备了一种含氟有机硅单体3,5-双(三氟甲基)苯基甲基二甲氧基硅烷;然后将其与二甲基二甲氧基硅烷共水解、平衡聚合制得3,5-双(三氟甲基)苯基硅油.通过FT-IR、1H NMR、19F NMR和元素分析等对含氟有机硅单体和氟硅油进行了表征.含氟硅油的表面张力为20.5 mN/m,大于二甲基硅油(19.0 mN/m).以硅油质量损失10%时的热分解温度来表征材料的热稳定性,二甲基硅油为232.3 ℃,含氟苯基硅油为265.2 ℃,表明含氟苯基硅油的热稳定性比二甲基硅油优越.     

两种氟硅油的乳液配方研究

研究了八氟戊氧丙基甲基硅油和八氟戊氧丙基氨基硅油的乳化工艺和配方,考察了乳化剂配方、HLB值、乳化剂用量以及助乳化剂用量等因素对含氟硅油乳液的贮存稳定性、离心稳定性、乳液粒径和乳液Zeta电位等的影响,确定出两种含氟硅油乳化的较佳条件为:在八氟戊氧丙基甲基硅油的乳化过程中,加入助乳化剂可以获得稳定的乳液;由八氟戊氧丙基氨基硅油配制乳液时,随着八氟氨基硅油氟用量的增加,乳化剂的最佳HLB值降低。制备八氟戊氧丙基甲基硅油乳液的较佳条件为:以Span 20和SDS为复合乳化剂,其最佳质量分数15%(相对于氟硅油质量),助乳化剂月桂醇的最佳用量是1.5 g/L,最佳HLB值为10,可以得到固体质量分数为10 g/L、澄清透明的稳定乳液;八氟戊氧丙基氨基硅油以AEO-9和SDS为复配乳化剂,乳化剂的最佳质量分数为12%,随着氟含量提高,八氟戊氧丙基氨基硅油的表面张力下降,所对应的复配乳化剂的亲疏平衡值相应下降,氟硅油对应的最佳乳化HLB值也下降。氟的质量分数分别为25%、30%、35%,氨基质量分数为1%的三种氟硅油对应的最佳乳化剂的HLB值分别为23、18和14。     

国产共聚氟硅橡胶耐油性探讨

试验了结构控制剂种类、硫化剂种类及其用量对国产共聚氟硅橡胶耐油性能的影响。结果表明,羟基硅油比羟基氟硅油控制结构化效果好,但耐3#标准油性能羟基氟硅油比羟基硅油要好。硫化剂双二五在共聚氟硅橡胶中耐3#油最佳。用量范围为0.6～0.8份,耐3#标准油性能依次为氟硅胶〉共聚氟硅橡〉耐油硅橡胶。     

Enzymatic synthesis of silicone fluorinated aliphatic polyesteramides

The enzymatic synthesis of silicone fluorinated aliphatic polyesteramides (SFAPEAs) is reported. These materials were synthesized by incorporating both the fluorinated aliphatic segments and the dimethylsiloxane segments into the same linear chain backbone. Immobilized lipase B from Candida antarctica (Novozym-435) was used to catalyze the reactions to prepare fluorosilicones containing both amide and ester linkages. Simultaneous reactions of an amidation between α,ω-aminopropyl terminated poly(dimethylsiloxane) (APDMS) and diethyl adipate (DEA) and a transesterification between diethyl adipate and four different fluorinated alkanediols (FADs), respectively were conducted. The condensation reactions were carried out in the bulk, in the temperature range 70-90 °C and under reduced pressure (50 mmHg vacuum gauge). The molar masses of the synthesized fluorosilicones were determined by GPC analysis. The effect of the chain length of the FADs on the molar mass build up of the respective polymers was investigated. The highest molar mass fluorosilicones were obtained with the 3,3,4,4,5,5,6,6-octafluoro 1,8-octanediol (OFOD) monomer, which has an additional methylene (-CH₂-) spacer between the fluorocarbon chain (-CF₂-)_n and the hydroxyl end groups (-OH) when compared to the other three FAD monomers namely - 2,2,3,3-tetrafluoro 1,4-butanediol (TFBD), 2,2,3,3,4,4-hexafluoro 1,5-pentanediol (HFPD) and 2,2,3,3,4,4,5,5-octafluoro 1,6-hexanediol (OFHD). The formation of amide and ester linkages during the polymerization was confirmed by FTIR and ¹H NMR spectroscopy. A series of copolymers were synthesized by varying the feed ratios of FAD to APDMS. Fluorinated polyesters (FPEs) and silicone polyamides (SPAs) were also enzymatically synthesized under similar reaction conditions. The DSC analysis revealed that the fluorosilicones were semi-crystalline, principally due to the presence of the FPE segments. The FPEs were found to be white solids at room temperature. However, the SFAPEA’s were found to be viscous materials due to the presence of highly flexible silicone segments in the backbone chain. The crystallinity was seen to disappear completely for the SFAPEA’s with greater than 15 mol% of silicone content. The TGA analysis revealed that thermal degradation/depolymerization characteristics of the fluorosilicones improved with increased silicone content. We envisage that these new fluorosilicones have potential for a variety of low surface energy applications.     

Synthesis and thermal stability of hybrid fluorosilicone polymers

Aromatic hybrid fluorosilicones, such as perfluorocyclobutane aromatic polyethers, have higher thermal stability than typical polysiloxanes. While these polyethers decompose by homolytic cleavage of the oxygen-perfluorocyclobutane bond, the enhanced thermal stability of the polyethers may, in part, arise from this oxygen through the anomeric effect. To determine the effect of the ether oxygen on thermal stability, two perfluorocyclobutane aromatic units, one with and one without the oxygen, were modeled. To confirm the results experimentally, a series of hybrid fluorosilicones based on the latter were synthesized by thermocyclodimerization of 1-bromo-4-(trifluorovinyl)benzene, metal-halogen exchange, and condensation with one of 1,3-dichlorotetramethyldisiloxane; 1,7-dichlorooctamethyltetrasiloxane; or chlorine-terminated poly(dimethylsiloxane). The degradation temperature (T_1%) was lower (∼240 °C) than the comparable polyethers (∼430 °C). These results demonstrate the importance of the ether oxygen to the stability of perfluorocyclobutane aromatic polyethers through a number of effects including the anomeric effect and enhancing the strength of the silicon-aromatic bond.     

梯度共聚物的最新进展

阐述了梯度共聚物的概念及梯度共聚物的研究意义,介绍了梯度共聚物分类及特点,以及与这些特点相对应的各种用途。重点综述了近年来各种梯度共聚物的制备方法如常规乳液聚合、原子转移自由基聚合(ATRP)、可逆加成-断裂链转移聚合(RAFP)和氮氧调控自由基聚合(NMCRP)等,以及梯度共聚物的各种表征方法,如红外光谱(FT-IR)、核磁共振(NMR)、薄层色谱(TLC)以及X射线光电子能谱(XPS),并进一步分析了梯度共聚物的研究方向和研究重点。     

聚芳酯的研究进展

综述了聚芳酯的国内外研究现状和聚芳酯的发展,介绍了聚芳酯的三种合成工艺即熔融聚合、溶液聚合和界面聚合的实施方法,指出了各种方法存在的优缺点.另外,对聚芳酯的应用和未来的发展前景进行了简要的阐述.     

复合纳米二氧化硅的制备进展

全面地综述了复合纳米二氧化硅的制备方法,重点介绍了溶胶-凝胶法、水解-沉淀法、表面接枝法、乳液聚合法、微乳液聚合法、原位聚合法。对制备方法进行了概括和评价,并简述了复合纳米二氧化硅在应用领域的进展。     

水性含硅聚合物涂料的制备与应用

介绍了种子乳液聚合、核/壳乳液聚合、无皂乳液聚合、微乳液聚合、互穿网络聚合等制备水性含硅聚合物的方法,探讨了水性含硅聚合物涂料的应用。     

聚L-乳酸的研究进展与产业化进程

随着资源的减少和白色污染的加剧，作为生物可降解材料的聚L-乳酸（PLLA）引起了世人的广泛关注。综述了近年来PLLA的合成方法如一步聚合法、两步聚合法、酶催化开环聚合法等，介绍了PLLA在医用、纺织、塑料等领域的专利情况及其应用现状，认为随着LLA的大批量生产和利用，PLLA的生产成本将大幅度下降，必将得到巨大的发展。     

光引发体系研究进展

光引发聚合作为区别于热引发聚合的一种合成手段，具有许多优越性和实用性。笔者从光引发的定义出发，对光引发体系的分类、引发机理、合成研究及其在聚合反应中的引发聚合、引发接枝、引发交联、引发转移终止等应用作了归纳总结。     

Research progress on the preparation and application of monodisperse cationic polymer latex particles

This review is focused on the features, preparation and applications of uniform cationic polymer latex particles, as well as on the formation mechanism of uniform latex particles. Substantial progress in the size and shape control of polymer latex particles has been made using several methods such as dispersion polymerization, conventional emulsion polymerization, surfactant‐free emulsion polymerization and seeded emulsion polymerization. Uniform cationic polymer latex particles have wide applications such as drug carriers, diagnostics, templates and additives. However, two major problems are the inhomogeneous size and low surface charge density, which limit further functionalization and the application of cationic polymer latex particles. Finally, the future trends and perspectives are described. Copyright © 2012 Society of Chemical Industry     

壳聚糖接枝改性及其在生物医学领域的应用

壳聚糖作为重要的天然生物材料,其改性与应用得到了广泛关注.综述了近年来壳聚糖的化学接枝改性方法,包括开环聚合法(ROP)、原子转移自由基法(ATRP)、可逆加成断裂链转移聚合法(RAFT)、以及氮氧稳定自由基聚合法(NMP)等.并进一步综述了壳聚糖接枝共聚物在药物控释栽体、基因载体、组织工程材料等生物医学领域的应用.