氟表面活性剂和氟聚合物(Ⅶ)——含氟织物整理剂概述

含氟织物"三防"整理剂是一类具有含氟烷基的织物整理剂,它能赋予织物防水、防油和防污的功能,整理后的织物还可保持原有的手感、透气性、色泽、穿着舒适等特点。本文从含氟织物整理剂的类型、结构、"三防"原理、整理机制、生产、使用工艺、评价方法以及性能要求等几个方面进行介绍。     

氟表面活性剂和氟聚合物(VII)——含氟织物整理剂概述

含氟织物“三防”整理剂是一类具有含氟烷基的织物整理剂，它能赋予织物防水、防油、防污的功能，整理后的织物又可保持原有的手感、透气性、色泽、穿着舒适等特点。本文从含氟织物整理剂的类型、结构、“三防”原理、整理机制、生产及使用工艺、评价方法以及性能要求等几个方面进行介绍。     

友刊链接

表面预处理对环氧树脂-铝粘接强度的影响;环境对环氧胶粘剂粘接老化的影响;关于禁用和限用纺织化学品中的几个问题（二）;纺织浆料的现状与发展趋势;含氟“三防”纺织助剂的合成方法及发展前景.     

聚氨酯在织物上的应用及其特性

织物用聚氨酯处理,除赋予柔软性外,还使织物具有透湿、防水、防缩、防绉、抗起球、抗静电、有弹性及光泽好等多种性能,早在50年代,线型和交联的聚氨酯纺织助剂已开始工业规模生产,当时绝大部分是溶剂型的聚氨酯。到70年代中期,水溶性聚氨酯得到迅速发展,同时它在纺织工业方面的应用也十分广泛。从目前对织物高档次的需求来看,聚氨酯作为织物的加工助剂具有广阔的发展     

含氟织物整理剂

本文综述了含氟织物整理剂的功能、发展简史、品种、特殊结构和性能、合成方法以及它们在纺织领域的特殊用途；阐述了含氟增水增油剂的机理并介绍了其性能测试方法；简述了借水增油、防污和易去污整理剂及它们的整理工艺以及羊毛织物的整理方法。最后对产品进行了市场分析，展望了产品前景。     

有机硅类纺织助剂

有机硅助剂适应性好、用途广泛,是一种性能优良的功能性表面活性剂。有机硅类纺织助剂因其独特的结构和性能,用于纺织品整理可赋予织物柔软、滑爽、抗静电、疏水、耐热等多种优异性能。介绍了纺织用有机硅助剂的特点、分类及有机硅在纺织品中做为柔软剂及各种整理剂方面的应用,其作用是无可比拟的,并对有机硅类纺织助剂应用前景进行了展望。     

电解氟化及其下游精细氟化工产品(续1)

叙述了含氟改性剂及PFOS的主要品种、国内外研制发展概况,介绍了他们的生产工艺、成本估算、售价分析,以及在织物三防整理剂、电镀铬雾抑制剂和消防用水成膜泡沫灭火剂等应用情况;对不含PFOS含氟改性剂、氟气和氟化石墨未来5a的市场需求进行了预测。     

XSF—1织物整理剂的研制

研究了ＸＳＦ—１织物整理剂的制备方法。讨论了有关因素对产品质量的影响,同时对产物的热稳定性、耐酸碱性、与纺织助剂的配伍性、织物的整理效果进行了测试。结果表明：ＸＳＦ—１织物整理剂热稳定性、耐酸碱性好;与纺织助剂配伍性好;对织物整理效果佳。     

XSF—1织物整理剂的研制

研究了ＸＳＦ－１织物整理剂的制备方法。讨论了有关因素对产品质量的影响,同时对产物的热稳定性、耐酸碱性、与纺织助剂的配伍性、织物的整理效果进行了测试。结果表明：ＸＳＦ－１织物整理剂热稳定性、耐酸碱性好;与纺织助剂配伍性好;对织物整理效果佳。     

纳米硅溶胶在防反射薄膜中的应用研究

采用辐射聚合法制备了防反射涂覆液,低折材料采用含氟单体和纳米硅溶胶,涂覆液中加入了溶剂、UV固化单体、引发剂、流平剂等助剂,在三醋酸纤维素基材上用丝棒涂布制备了防反射薄膜。研究了纳米硅溶胶的分散介质、粒径大小及其用量对防反射薄膜雾度、折射率、反射率等性能的影响。     

含氟丙烯酸酯共聚物的合成及其涂膜表面疏水、疏油性能研究

以单体甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、含氟(甲基)丙烯酸酯为原料,通过改变氟碳链长度、氟单体含量以及添加方式等因素,合成了一系列的含氟丙烯酸酯共聚物。利用表面接触角测试仪、红外光谱仪和多功能光电子能谱仪表征了共聚物涂膜的表面疏水、疏油性能以及表面化学成分,探讨了其影响因素。结果表明,共聚物涂膜表面疏水、疏油性能与其表面化学成分密切相关;使用长氟碳链的氟单体、增加氟单体用量以及采用在反应后期一次性加入氟单体的方法均有利于提高涂膜表面的疏水、疏油性能;当全氟辛基乙基甲基丙烯酸酯的质量分数为25%时,所得涂膜表面的氟元素质量分数达到44.284%,对水、对正十六烷的接触角分别达到127°和65°。     

含氟丙烯酸酯共聚乳液的合成与性能研究

由甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)和丙烯酸六氟丁酯合成了含氟三元共聚乳液.采用正交方法设计实验条件,并对实验结果以及乳液成膜性能进行探讨.FTIR、1H-NMR对共聚物的组成进行了定量分析,计算得出了共聚物中各组分的摩尔百分数.对三元含氟共聚物乳液涂膜的表面性能进行测量表明,共聚物氟含量直接影响着膜的表面性能.     

Synthesis and application properties of fluorinated aromatic copolymers

Aromatic monomers with different fluorine concentrations and structural distribution patterns were synthesized. A series of copolymers based on methyl methacrylate, acrylate, and perfluorooctylalkyl acrylate were prepared by emulsion polymerization and were subsequently used as functional coatings to prepare water‐ and oil‐repellent cotton fabrics. The composition and structure of the outmost layer of the treated cotton surface were analyzed. A strong surface segregation of fluorinated segments was found for the treated samples, as shown by X‐ray photoelectron spectroscopy analysis. The basis for an in‐depth appreciation of the relationship between the molecular structure of the monomers and the properties of corresponding copolymer‐treated materials was provided (especially with regarding to their hydrophobic and oleophobic properties). The wetting characteristics of the fluorinated copolymers were found to be dependent on the density (number of side chains per constitutional repeat unit) and regularity of the fluorinated side chains. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4410–4418, 2013     

一种含氟共聚物乳液的制备及其性能

通过制备一种含有全氟壬烯基的含氟共聚物乳液,并考察其性能,研究了含氟单体对共聚物乳液性能的影响。以K2S2O8为引发剂,丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)和全氟壬烯基烯丙基醚(PFNAE)为共聚单体,采用半连续乳液聚合的方法,制备了带蓝色荧光的含氟乳液。用傅里叶红外(FT-IR)、接触角、差示量热扫描(DSC)和热重(TG)分析等手段对制备的PFNAE-BA-MMA共聚物(PBM)结构和性能进行表征。结果表明:引入含氟单体后,聚合物的疏水性、热稳定性、玻璃化温度(Tg)都有提高。水在含氟共聚物上的接触角随含氟单体用量的增加而增大,当PFNAE占单体总质量的25%时,水的接触角为94.9°;当PFNAE占单体总质量的20%时,共聚物在221℃开始分解,429.5℃分解完全,该共聚物Tg为8.5℃。PFNAE-BA-MMA共聚物具有一定的拒水性和良好的热稳定性。     

Synthesis and characterization of rubbery highly fluorinated siloxane–imide segmented copolymers

The synthesis and characterization of a series of poly(siloxane–imide) block (or segmented) copolymers obtained by copolymerization of amine‐terminated polydimethylsiloxane with fluorinated aromatic compounds containing anhydride and amine functionality are reported. New fluorinated block copolymers have been synthesized to obtain organophilic polyimides potentially interesting for molecular membrane separations. The new aspects of this work relative to the literature are (1) a comparison of solution and solid‐state approaches in the imidization step to generate the target poly(siloxane–imide) copolymers and (2) exploration of new compositions involving fluorinated aromatic polymers derived from added diamine compounds. It is shown that the copolymer properties can be tailored from glassy to rubbery materials by varying the amount and the type of oligosiloxane used; the transition between glassy and rubbery properties is characterized at a siloxane content of 60 wt%. As a main result, it is shown that the solid‐state approach for inducing the cyclo‐imidization step is the more efficient one for synthesizing polymers with good mechanical properties, when the amount of siloxane block is increased in the copolymer series. Physical and chemical methods (thermogravimetric analysis, Fourier transform infrared spectroscopy, viscosity measurements) were used to characterize the copolymer properties obtained according to the two different synthesis routes. The obtained siloxane–imide copolymers are well soluble in a large variety of moderately polar solvents and exhibit very good thermal stability up to 400 °C. Hence the prepared copolyimides would seem to be promising candidates as organophilic membranes as well as gas permeation membranes. © 2012 Society of Chemical Industry     

氟化丙烯酸酯共聚乳液的研究进展

氟化丙烯酸酯共聚乳液具有优异的表面性能如耐污性、自清洁性等，因此受到国内外很多科研人员的关注；本文综述了近10年来通过在聚合物链中引入含氟基团得到氟化丙烯酸酯聚合物乳液的制备方法及相关性能特征的研究进展，并对国内氟化丙烯酸酯聚合物乳液的研究及在涂料等领域的应用提出了几点建议。     

Tailoring the swelling and glass‐transition temperature of acrylonitrile/hydroxyethyl acrylate copolymers

Novel polyacrylonitrile (PAN)‐co‐poly(hydroxyethyl acrylate) (PHEA) copolymers at three different compositions (8, 12, and 16 mol % PHEA) and their homopolymers were synthesized systematically by emulsion polymerization. Their chemical structures and compositions were elucidated by Fourier transform infrared, ¹H‐NMR, and ¹³C‐NMR spectroscopy. Intrinsic viscosity measurements revealed that the molecular weights of the copolymers were quite enough to form ductile films. The influence of the molar fraction of hydroxyethyl acrylate on the glass‐transition temperature (T_g) and mechanical properties was demonstrated by differential scanning calorimetry and tensile test results, respectively. Additionally, thermogravimetric analysis of copolymers was performed to investigate the degradation mechanism. The swelling behaviors and densities of the free‐standing copolymer films were also evaluated. This study showed that one can tailor the hydrogel properties, mechanical properties, and T_g's of copolymers by changing the monomer feed ratios. On the basis of our findings, PAN‐co‐PHEA copolymer films could be useful for various biomaterial applications requiring good mechanical properties, such as ophthalmic and tissue engineering and also drug and hormone delivery. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Terpolymers. I. The mechanical properties and transition temperatures of terpolymers of n-octadecyl acrylate,ethyl acrylate,and acrylonitrile

Earlier work revealed that the internal plasticization of polyacrylonitrile by the higher n-alkyl acrylates or N-n-alkylacrylamides yielded only brittle copolymers. This difficulty was circumvented in the present work by starting with copolymers of acrylonitrile and ethyl acrylate, over the range of compositions, and further modifying these by incrementally displacing the ethyl acrylate in each recipe by n-octadecyl acrylate through terpolymerization. In this way, the stepwise small reduction in T_g for the base ethyl acrylate–acrylonitrile copolymers was greatly increased for each of the terpolymers. Compositions were obtained ranging from glassy, brittle terpolymers, with glass transitions above room temperature, to soft plasticized polymers having sufficient polar networks retained from the nitrile to confer useful properties. The decline in the glass temperature was shown to be dependent on the free volume conferred by the side-chain methylene groups of each acrylate ester. In contrast, the decline in tensile and flexural strengths and moduli for the terpolymers having glass transitions above room temperature was produced entirely by the presence of the methylene groups of the 18-carbon ester. The glass transition region corresponded to room temperature when the acrylonitrile content of the base copolymer had been reduced to 50 mole-%. Terpolymers of this nitrile content and lower had the low moduli and large elongations of plasticized compositions. An equation was developed which correlated empirically the glass transitions and the mechanical properties with the weight fraction of the acrylate esters for the glassy terpolymers.     

含氟丙烯酸酯共聚乳液合成及性能研究

以甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）和全氟烷基丙烯酸酯等为主要原料,丙二醇为分子量调节剂,采用非离子阴离子复合乳化剂、氧化还原引发体系、超声微乳化技术,不同的加料方式制备出系列含氟丙烯酸酯乳液,并利用衰减全反射红外光谱（ATR-FTIR）对含氟丙烯酸酯共聚乳液胶膜进行了表征。采用接触角测定方法研究了含氟共聚乳液对织物整理后的表面性能变化,结果显示：乳液整理后的纯棉无纺布的拒水拒醇性大大提高,对水的接触角达到127o左右,对醇的最大接触角达到112o。乳液整理后的PP无纺布拒醇性明显改善,接触角达到101o左右。但拒水性能未见明显提高。     

含氟丙烯酸酯共聚物涂膜表面润湿性的研究

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、甲基丙烯酸β–羟乙酯(HEMA)、(甲基)丙烯酸高级酯(AAs)、含氟(甲基)丙烯酸酯(Fs)等单体为原料,HDI三聚体为固化剂,通过改变共聚物组成、氟碳链长、(甲基)丙烯酸高级酯烷烃链长等因素,合成了一系列的含氟丙烯酸酯共聚物。采用水、煤油和液压油接触角以及水滴滚动距离,表征了共聚物涂膜的表面润湿性,并探讨了其影响因素。结果表明,共聚物组成和结构、烷烃链长对水的接触角影响不大,而对水的滚动性能具有较大影响;氟碳链长以及氟单体的添加方式对油水接触角和水的滚动性能有较大影响;烷烃侧链的柔顺性对油的接触角影响较大,而对水几乎没有影响。