【作者】 黄继庆；

【导师】 卿凤翎；

【作者基本信息】 东华大学 ， 纺织化学与染整工程， 2009， 博士

【摘要】 含氟聚合物织物整理剂研究是有机氟化学的一个重要研究分支,含氟聚合物织物整理剂不仅能赋予织物优异的拒水拒油性,而且能保有织物原有的色泽、手感、透气性、穿着舒适性等,从而成为当今拒水拒油整理剂的主流。本文设计合成了几种新型的含氟聚合物,并对其作为织物整理剂的性能进行了研究。全文主要包括以下四个方面的工作。第一部分,设计合成了具有疏水/疏油基团的氟代环氧丁烷单体34FOx和具有亲水基团的环氧丁烷单体EtOx,并通过此二单体的阳离子开环共聚合成了具有不同组分比例的聚醚二元醇P（34FOx:EtOx）。然后以聚醚二元醇P（34FOx:EtOx-1:1）为软段,以异佛尔酮二异氰酸酯（IPDI）和扩链剂1,4-丁二醇为硬段合成了具有疏水疏油—亲水智能表面的聚氨酯PU3。液态石蜡在以玻璃板和棉织物为基质的PU3表面上的接触角分别可达到85°和119°,表现出良好的疏油性;水在以玻璃板为基质的PU3表面刚开始时的接触角较大,为108°,这表明聚氨酯PU3在与水刚接触时表现出疏水性。随着时间的延长,水在样品上的接触角逐渐减小,在25分钟内由108°降低到25°,表现出亲水性,实现了由疏水/疏油性表面到亲水性表面的转换。第二部分,设计合成了短氟碳链修饰的环氧丁烷6FOx和溴代环氧丁烷BrOx,并以这两种环氧丁烷为单体通过阳离子开环聚合制备了聚醚二元醇P（6FOx:BrOx）。以P（FOx:BrOx）为软段,以异佛尔酮二异氰酸酯（IPDI）和扩链剂1,4-丁二醇为硬段合成了具有疏水链段（-CF₃）和反应基团（-Br）的聚氨酯FBr-PU。此类聚合物不仅可以赋予织物优良的疏水性能（WCA=133°）,而且其包含的反应基团（-Br）为聚合物的进一步改性以获得更广泛的功能提供了可能。此外从全氟丁基磺酰氟出发设计合成了短氟碳链环氧丁烷FSOx。并以5,5-二甲基海因为原料,先通过N-烷基化合成了带有羟基的中间体,再通过Williamson醚化合成了带海因侧基的环氧丁烷单体HyBrOx。以FSOx与HyBrOx的共聚物作为软段,IPDI和1,4-丁二醇作为硬段得到的聚氨酯FHy-PU将可能具有疏水、透气、抗菌、易去污等复合功能。但是,受时间限制,本文目前只完成了FSOx、FBrOx和HyBrOx单体的合成,正在积极探索FSOx与HyBrOx的共聚反应条件。第三部分,设计合成了含短氟碳链水性聚氨酯WFPU。其以水为分散介质,不仅具有不燃、无毒、无污染、节约能源以及易加工等优点,而且应用短氟碳链（-CF₃）提供功能改性,不会产生由长氟碳链化合物所引起的环境污染和生物累积问题,是一种绿色环保型拒水拒油剂。WFPU在玻璃板上成膜后,对水的接触角可达111°,具有良好的疏水性能。第四部分,疏水/疏油性的表面可以通过化学改性来降低表面能。以往的研究主要是通过应用长全氟链C_nF_2n+1（n≥8）来降低表面自由能。但是有许多证据表明,长全氟链化合物存在生物积累和对环境的污染等问题,虽然应用短氟碳链化合物可以避免此类问题,但其拒油性不佳,因此人们开始探索怎样合成一种合适的化合物,使其既拥有优异的拒水拒油性能,又不存在长全氟碳链的污染问题。基于这一指导思想,本文设计合成了含氟丙烯酸酯3a-d,并通过乳液聚合成功合成了对应的三元共聚物4a-d。通过传统的轧-烘-焙过程,合成的产物4a-d被应用到棉织物上。其中含-CH₂CF₂-片段的含氟碳链丙烯酸酯共聚物4b、4c赋予了织物优异的拒水拒油性能,对十四烷的接触角均为116°,拒油级别分别达到6级和5级;对水的接触角分别为140°和138°,拒水级别均达到6级,与传统的长全氟链丙烯酸酯共聚物4a的拒水拒油性能相当。并与含相同碳链长度的短氟碳链丙烯酸酯共聚物4d做对比,4d只有5级拒水性,而没有拒油性能。因此,含-CH₂CF₂-片段的含氟聚丙烯酸酯作为环保型拒水拒油剂,具有可替代目前使用的长全氟碳链拒水拒油剂的潜在价值。更多还原

【Abstract】 The research of fluoropolymer textile finishing agent is an important branch of organofluorine chemistry because fluoropolymer textile finishing agents provide textile with optimum performance in terms of both water- and oil- repellency without impairing the textile’s permeability to air, comfort ability, color or hand feel. They have been becoming the leading finishing agents for achieving water- and oil- proof. In this dissertation, several classes of novel fluoropolymer textile finishing agents were designed, synthesized, characterized and evaluated. The whole dissertation consists of the following four parts.Part 1: Fluorooxetane monomer 34FOx containing oleophobic/hydrophobic groups and oxetane monomer EtOx containing hydrophilic groups were designed and synthesized. Polyoxetanes P（34FOx:EtOx） were synthesized through cationic ring opening polymerization by using 34FOx and EtOx as starting materials. Then polyurethane PU3 which can form oleophobic/hydrophobic- hydrophilic smart surface was prepared by employing isophorone diisocyanate （IPDI） and 1,4-butanediol （BD） as the hard segments and P（34FOx:EtOx-1:1） as the soft segments. The static contact angle for olefin liquid on PU3 treated glass and cotton fabric reached to 85°and 119°, respectively. The initial maximum static water contact angle was 108°when the water was dropped on the PU3 treated glass plate which indicated that the polyurethane surface was hydrophobic, however, a significant decrease of WCA from 108°to 25°within 25 minutes was observed which indicated the surface of PU3 coating has switched from hydrophobic to hydrophilic.Part 2: Fluorooxetane 6FOx containing short fluoroalkyl groups and 3,3-bisbromomethyloxetane BrOx were designed and synthesized. Starting from these two monomers, Polyoxetanes P（6FOx:BrOx） were synthesized through cationic ring opening polymerization. Then, polyurethanes FBr-PU bearing hydrophobic groups （-CF₃） and reactive groups （-Br） were prepared by employing isophorone diisocyanate （IPDI） and 1,4-butanediol （BD） as the hard segments and P（6FOx:BrOx） as the soft segments. The fabrics treated with FBr-PU showed good hydrophobicity （WCA =133°） and could be further modified via substitution reaction of the reactive bromomethyl groups.In addition, monomer FSOx was also designed and synthesized by using perfluorobutyl sulfuryl fluoride as starting material. The hydantoin-oxetane monomer HyBrOx was synthesized via N-alkylation and Williamson etherification reaction with 5,5-dimethylhydantoin as starting material. Polyurethane FHy-PU would be prepared from copolymerization by using copolymer of FSOx and HyBrOx as soft segments, and isophorone diisocyanate （IPDI） and 1,4-butanediol （BD） as the hard segments. FHy-PU would impart unique properties to the fabrics, such as water-repellency, breathability, antibiosis and easy decontamination. However, in this dissertation, we only finished the synthesis of monomers FSOx, FBrOx and HyBrOx due to time limitation, and further intensive efforts would be made to accomplish the following polymerizations.Part 3: A novel waterborne polyurethane WFPU containing short fluoroalkyl groups was designed and synthesized by using water as dispersive medium, which had advantages in fire safety, innocuity, environmental pollution, energy conservation and workability etc. WFPU with short perfluoroalkyl group （-CF₃） could avoid the environmental and bioaccumulative problems caused by long perfluoroalkyl groups. It was an environmental benign textile friendly finishing agent. The contact angle of water for WFPU treated glass reached to 111°, which indicated good water repellency.Part 4: The lowering of surface energy through chemical modification can enhance the hydrophobicity/oleophobicity of a surface. Previous studies have been focused on the use of long perfluoroalkyl chains C_nF_2n+1（n≥8） to lower the surface energy. However, there are some evidences concerning possible persistence, bioaccumulation, and/or toxicity of these types of fiuorochemicals in the environment. The new strategies are concerning how to synthesize suitable chemicals that have excellent water and oil repellency without the need for long perfluoroalkyl groups. Fluorinated acrylates 3a-d were designed and synthesized. Then, fluorinated polyacrylates 4a-d were prepared by using emulsion polymerization. Copolymers 4a-d were used for finishing of cotton fabrics by a pad-dry-cure process. Polymers 4b and 4c containing partially fluorinated alkyl groups （-CH2CF2-） showed comparable water and oil repellent properties to conventional polymer 4a which containing long perfluoroalkyl groups. The contact angles of n-tetradecane for 4b and 4c treated fabrics were reached to 116°and oil repellency rating was six and five, respectively. The contact angles of water for 4b and 4c treated fabrics was 140°and 138°, respectively, and water repellency rating were six. Polymer 4d containing the same length carbon chain with C4F9- group provided the treated cotton fabrics with water repellency rating at five but no oil repellency. Thus, polyacrylates containing vinylidene fluoride units showed promising value as the alternatives to the currently used water and oil repellent agents which contain long perfluorocarbon chains.更多还原