摘要
长链全氟烷烃氟碳化合物(CnF2n+n≥8)因其突出的低表面自由能被广泛应用于制备拒水拒油整理剂。然而,越来越多的事实表明,长氟碳链化合物存在环境和生物积累或毒性。近十年来,对环境友好的含短氟碳链(CnF2n+1,n≤6)的织物整理剂倍受关注,但其拒油性不是很令人满意。而氟碳化合物家族中另一重要成员,全氟聚醚化合物(PFPE)因其出色的物理化学性能,如,耐化学腐蚀性,优良的润滑性,低表面自由能及低毒性,有望在拒水拒油整理剂方面取代长链全氟烷烃氟碳化合物。
本论文以固体表面疏水疏油理论为指导,以2,5-二(三氟甲基)-3,6-二氧杂-全氟壬酰氟(THPF)为重要含氟原料,设计合成了几类的含氟硅杂化聚合物,并将其作为整理剂应用于棉织物表面改性,对整理后织物的润湿性能进行了测试。研究工作由以下几部分组成。
(1)采用3种设计思路制备了4种不同微观结构的二氧化硅有机衍生物：Rf-SiO2-1、RrSiO2-2、RrSiO2-3(1)及RrSiO2-3(2)。其中具有微米/纳米二元微观结构(MNBS)的RrSiO2-3(2),具有超疏水性及高度疏油性。RrSi02-3(2)在玻片上成膜,水静态接触角为157°,正十四烷和正十二烷接触角分别达到132°和113°。采用FT-IR、XPS、SEM、AFM及元素分析等测试手段对杂化材料的化学组成和表面形态进行了表征。研究了碱性条件下溶胶-凝胶法制备不同粒径纳米SiO2的影响因素；氨基化纳米二氧化硅(APES-SiO2)的制备条件及APES-SiO2的酰胺化反应对杂化材料的疏水疏油性的影响。研究发现,酰胺化反应时间长短影响杂化材料疏水疏油性。热重分析表明,杂化材料RrSiO2-3(2)的初始分解温度大于200℃,最大分解速率所在温度大于300℃,满足一般外墙涂料和织物整理对聚合物热稳定性的要求。将Rf-SiO2-3(2)与聚甲基丙烯酸卿旨共混物整理到棉织物上,Rf-SiO2-3(2)可有效提高绵织物的疏水油性。
(2)采用原位反应法,应用SiO2前驱体正硅酸四乙酯(TEOS)在棉织物上引入不同粒径的SiO2粒子,并合成两种含氟单体,分别对棉织物进行氟化处理,制备了4种疏水/疏油棉织物S1、S2、S3及S4。研究了原位反应引入SiO2粒子过程中,SiO2粒子大小、TEOS用量对处理后棉织物疏水性的影响。利用FT-IR、NMR表征了含氟单体化学结构,SEM、XPS等分析了处理后棉织物的表面元素组成和表面微观形态。研究表明,在具有微米-亚微米微观结构的棉织物上引入全氟醚链,制得S3与S4,具有高度疏油性和超疏水性。S3与S4比较,S4具有更好的疏水疏油性,水接触角可达到160°,色拉油接触角可达到146°,拒水拒油等级分别为90,4。
(3)采用乳液聚合方法,应用种子乳液半连续乳液聚合工艺,合成以甲基丙烯酰氧基丙基三甲氧基硅烷修饰过的纳米SiO2为核,含氟丙烯酸酯聚合物为壳的含氟硅聚合物(FSP)。以对环境友好的脂肪醇聚氧乙烯醚代替普遍使用但对环境有害的烷基酚类聚氧乙烯醚为非离子乳化剂,并与阴离子表面活性剂复配,研究了复配乳化剂HLB值(hydrophilic-lipophilic balance value,亲水亲油平衡值)对乳液聚合反应的影响。同时,还研究了复配乳化剂用量、引发剂用量、反应温度、单体浓度、聚合反应工艺等对乳液聚合反应的影响。在最佳工艺条件下,制得FSP具有很好的热稳定性,经FSP乳液整理过的棉织物,具有超疏水性能,且拒油性良好,水接触角可达到154°,正十六烷接触角达到107°。
(4)采用溶液聚合方法,制备了两个系列POSS基含氟聚合物P(POSS-MMA-(HFPO)3MA)系列和P(POSS-MMA-StRf)系列,并应用NMR、FT-IR、GPC、XRD、DSC及TG等分析测试手段对其进行了表征。TGA, DSC研究表明,POSS基含氟聚合物的热稳定性因POSS单元的引入而显著提高。将两个系列聚合物整理在棉织物表面,研究了聚合物中POSS含量对处理后织物疏水疏油性的影响。对于P(POSS-MMA-(HFPO)3MA)系列,当POSS含量为13.4%时,水和色拉油的接触角分别可达到152°和144°,而对于P(POSS-MMA-StRf)系列,当POSS含量为7.1%时,水和色拉油的接触角分别可达到163°和141°。POSS基含氟聚合物拒油等级可达到5级。通过XPS、SEM及元素分析等测试手段,分析了POSS含量影响其疏水疏油性的原因。此外,POSS基含氟聚合物、含氟聚合物/POSS共混物整理的棉织物的氧极限值结果及燃烧后的SEM图像表明,在我们这个研究体系,POSS以共聚物单元形式存在于聚合物中时,燃烧产生的Si02与有机残碳能形成热辐射和空气的“屏蔽层”,能降低棉织物的易燃性；而Ov-POSS与含氟聚合物共混,不能形成“屏蔽层”,不能降低棉织物易燃性。最后,我们制得的POSS基含氟聚合物中,POSS单元上存在未反应乙烯基,这为该聚合物进一步引入其它官能团,开发其它功能提供了可能。
Fluorocarbons with long perfluoroalkyl chain (CnF2n+1, n≥8) were widely used as water and oil repellent due to their outstanding low surface free energy. However, there are increasing evidences for bioaccumulation and/or toxicity of compounds containing the long perfluoroalkyl chains. Environmental benign finishing reagents containing short fluorocarbon chains (CnF2n+1, n≤6) are highly regarded in recent decade, whereas its oleophobicity is still undesirable. Perfluoropolyether (PFPE) seem to be the promising substitute for long-chain perfluoroalkane due to their excellent physical and chemical properties such as high chemical resistance, high lubricating ability, low surface energy and low toxicity.
In this study, on the basis of the theory for hydrophobic/oleophobic solid surface, we used 2,3,3,3-tetrafluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)propanoyl fluoride (THPF) as fluorine-containing monomer to synthesize several classes of hybrid fluorine-and silicon-containing polymers and applied the polymers as surface modifying agents on cotton fabrics. Wetting properties of the treated cotton fabrics were measured. The main work is described as follows:
(1) Four types of silica grafted with PFPE (RrSiO2-1, Rf-Si02-2, Rf-Si02-3(1) and RrSi02-3(2)) were prepared. Hybrid material Rf-SiO2-3(2) with micro-nano scale binary structure (MNBS) achieved superhydrophobicity and highly oleophobicity. The chemical composite and surface micromorphology of the hybrid materials were characterized by FT-IR, XPS、SEM、AFM and element analysis. Nano SiO2 was prepared by sol-gel method in alkaline condition. Factors affecting the size of the nano SiO2 were investigated. Preparation of amino SiO2 (APES-SiO2) and the effects of the amidation reaction on hydrophobicity and oleophobicity of the hybrid materials were also studied. It was found that the reaction time for preparing the fluorinated silica from amino nano-silica and THPF plays an important role in water and oil repellency of the coated surface. On the surface of glass substrate coated with RrSi02-3(2), water contact angle could achieve 157°, while for n-tetradecane and n-dodecane contact angle,132°and 113°, respectively. Thermogravimetric analysis showed that the onset decomposition temperature of RrSiO2-3(2) was more than 200℃and the maximum decomposition rate temperature was more than 300℃, which was suitable for common application such as construction coating and textile finishing. The wetting properties of the cotton fabrics changed greatly before and after treated with RrSiO2-3(2)/PMMA blend. Hydrophobicity and oleophobicity of the treated cotton fabrics could be improved by increasing the content of RrSiO2-3(2).
(2) Four kinds of hydrophobic and oleophobic treated cotton fabrics (S1, S2, S3 and S4) were prepared. The superhydrophobic and highly oleophobic cotton fabrics S3 and S4 were obtained by applying particle-based in situ fabrication procedure with two synthesized fluorinating agent and the silica particles precursor tetraethyl orthosilicate (TEOS). The effects of SiO2 particle size and TEOS dosage during in situ procedure on the hydrophobicity of the treated cotton fabrics were investigated. The chemical composite of the synthesized fluorinating agents were characterized by FT-IR and NMR. The surface composite and micromorphology of the treated cotton fabrics were analyzed by XPS and SEM. The results showed that introduction PFPE chains into cotton fabrics with micro/sub-micro surface structure could improve hydrophobicity and oleophobicity greatly. Compared with S3, S4 is possessed of higher water and oil repellency. The water and salad oil contact angle on S4 surface could achieve 160°,146°respectively, moreover, water and oil repellency ratings were 90 and 4.
(3) The core-shell polyacrylate emulsion (FSP) containing perfluoropolyether (PFPE) in the shell and 3-(methacryloxy) propyltrimethoxy silane modified nano-silica in the core was synthesized by semi-continuous seeded emulsion polymerization in the presence of anion/nonionic emulsifier. Environmental friendly fatty alcohol-polyoxyethylene ether was applied as nonionic emulsifier rather than alkylphenol ethoxylates which are harm to human and environment. The effects of the HLB value of the anion/nonionic emulsifier on the emulsion were studied, as well as the effects of emulsifier dosage, initiator dosage, reaction temperature, monomer concentration and emulsion polymerization technology. Compared with fluorinated polyacrylate (FP) without nano silica, FSP showed better thermal stability. The cotton fabrics treated with FSP emulsion achieved excellent water and oil repellency. The contact angle reached 154°for water and 107°for n-hexadecane.
(4) Two series of polyhedral oligomeric silsesquioxane (POSS) based hybrid terpolymers P(POSS-MMA-(HFPO)3MA) and P(POSS-MMA-StRf) were synthesized via solution polymerization and characterized by NMR, FT-IR, GPC, XRD, TGA and DSC. TGA and DSC results showed that the thermal properties of these terpolymers were improved by the introduction of POSS cage. Effects of POSS content on the hydrophobicity and oleophobicity of the cotton fabrics treated with P(POSS-MMA-(HFPO)3MA) and P(POSS-MMA-StRf) were studied. Water and oil repellency of the treated cotton fabrics were improved by the polymer incorporation of POSS unit. For P(POSS-MMA-(HFPO)3MA), water and salad oil contact angle could achieve 152°and 144°, respectively, as POSS content in terpolymer is 13.4 wt.%. For P(POSS-MMA-StRf), water and salad oil contact angle could achieve 163°and 141°, respectively, as POSS content in terpolymer is 7.1 wt.%, and oil repellency rating of the treated cotton fabric was 5. The affecting mechanism of POSS content on the water and oil repellency of the treated cotton fabrics was discussed based on the results of XPS, SEM and elemental analysis. Moreover, the POSS segment in the terpolymer mitigated the burning of the coated cotton fabrics in air to some extent by formation the protective char layer, while the POSS/fluorinated polymer blend didn't reduce the flammability of the cotton fabrics. Finally, the terpolymers is potential to be endowed other functional groups from the unreacted vinyl groups in the POSS segments, and thus to be developed for various potential applications.
引文
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