摘要
含氟聚合物具有极佳的耐热和耐化学稳定性、极低的表面能、优异的拒水拒油和自清洁性，在织物整理、功能涂层、生物医用、航空航天以及微电子领域已得到广泛的应用。含氟聚丙烯酸酯既有丙烯酸树脂优异的粘结性能，又有含氟聚合物的耐热、化学稳定性，耐老化，低表面能和防水防油性能，因而备受关注。随着人们资源与环保意识的逐步加强，在水体系中如何高效地合成理想结构和性能的含氟聚丙烯酸酯具有十分重要的理论和现实意义。而常规乳液聚合法所制备的含氟聚丙烯酸酯乳液，体系中含有大量物理吸附的小分子乳化剂，对膜的性能(光、电、表面性能、疏水、粘附力)及环境会产生不良影响。同时，含氟单体的价格昂贵，性能独特，人们希望在满足性能要求的前提下，尽量减少其用量。
鉴于此，本文采用无皂乳液聚合方法、设计并合成了3种新颖分子结构与粒子形态的含氟丙烯酸酯共聚物无皂乳液，系统地研究了乳液聚合稳定性的影响因素、乳液及其乳胶膜的相关性能；然后，将所制备的乳液应用于织物后整理，并对织物表面的微观膜形貌、化学成分及应用性能进行了深入地研究。论文的研究内容主要包括以下三部分：
（1）以顺丁烯二酸–乙酯撑基（三甲基氯化铵）–十八烷基聚氧乙烯(20)醚酯（R303）为阳离子可聚合乳化剂，偶氮二异丁基脒盐酸盐（VA-50）为引发剂，利用预乳化半连续种子乳液聚合法将甲基丙烯酸十二氟庚酯（DFMA）、甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）及阳离子单体甲基丙烯酸二甲氨基乙酯（DM）进行自由基共聚制得了蓝色荧光的P（DFMA-co-MMA-co-BA-co-DM）阳离子核壳无皂乳液（CFMBD）。同时，以1831/AEO-9复合乳化体系代替R303进行常规乳液聚合，制得了P（DFMA-co-MMA-co-BA-co-DM）阳离子乳液（GFMBD）。研究了可聚合乳化剂R303用量、引发剂用量及含氟单体用量对乳液聚合稳定性、乳胶粒粒径及乳胶膜性能的影响。当R303用量和VA-50用量分别为3%和0.8%（基于总单体质量），DFMA用量为8g，可以制得稳定无凝胶、粒径为136.8nm且分散均匀的CFMBD。
用透射电子显微镜（TEM）、扫描电子显微镜（SEM）、热重分析仪(TGA)、原子力显微镜（AFM）、X射线光电子能谱仪（XPS）、傅里叶红外光谱仪（FT-IR）及核磁共振谱仪对乳液和乳胶膜性能进行了表征。TEM证实乳胶粒具有核壳结构。CFMBD的表面张力在63.7~67.2mN/m之间，与水的表面张力(72.0mN/m)相近；而GFMBD的表面张力为36.9mN/m，与复合乳化体系（1831/AEO-9）的表面张力(35.6mN/m)很相近。这可说明了CFMBD中的R303分子大部分被键合在共聚物链节中；而1831/AEO-9则物理吸附在乳胶粒表面，容易脱离乳胶粒形成自由态乳化剂分子，使体系表面张力下降。随引入的DFMA量的增加，CFMBD膜的热稳定性增强，表面自由能和吸水率下降，表面水和二碘甲烷的接触角则升高。当DFMA为10g时，CFMBD膜对水和二碘甲烷的接触角分别可达108.5°及91.5°；此时，CFMBD膜的表面能和吸水率分别为12.65mN/m和7.6%。XPS结果表明CFMBD膜中的氟烷基向膜/空气界面迁移并富集，它对膜微观形貌及其疏水性的影响至关重要。AFM研究表明无氟丙烯酸酯膜相对平滑；常温干燥的CFMBD膜（DFMA占总单体27.5wt%）表面仅有少量小乳突，粗糙度略微增加；经热处理后，CFMBD膜表面有大量乳突和小山峰，粗糙度大大增加。这三种膜表面的水接触角也分别为62.5°，102.5°和108.5°。分析上述乳突和山峰应是CFMBD中的氟烷基链节的相分离所致。这也进一步印证了含氟基团具有向表面迁移的趋势和说明了热处理有利于含氟基团向表面的迁移。
再以CFMBD处理的棉纤维织物作应用研究对象，用CA、白度仪、柔软度测定仪、AFM、FESEM等对CFMBD的应用性能及其在织物表面的成膜形貌进行了研究。用1.0g/100ml H2O的CFMBD处理棉织物后，可使其具有良好的疏水性；不影响织物的白度。但CFMBD用量太大时，可使处理后的棉织物手感变差。耐水洗实验表明，受GFMBD中小分子乳化剂对膜粘附力的不利影响，洗涤后GFMBD处理的棉织物防水性差于CFMBD处理的棉织物。FESEM和AFM研究表明，处理后的棉织物表面明显覆盖有一层膜，织物表面变得较为光滑。
（2）以烯丙氧基壬基酚聚氧乙烯(10)醚硫酸铵（DNS-86）为阴离子可聚合乳化剂，过硫酸钾（KPS）为引发剂，N-羟甲基丙烯酰胺（NMA）为自交联功能单体，DFMA、MMA、BA为共聚单体，采用预乳化半连续种子乳液聚合法制得了带蓝色荧光的P（DFMA-co-MMA-co-BA-co-NMA）自交联核壳无皂乳液（FMBN）。研究了可聚合乳化剂DNS-86用量、含氟单体DFMA用量及功能单体NMA用量对乳液聚合稳定性、乳胶粒粒径及乳胶膜性能的影响。当DNS-86用量为3%（基于总单体质量），NMA和DFMA用量分别为1.5g和8g时，可以制得稳定的、粒径为116.3nm且分散均匀的FMBN。
用TEM、SEM、TGA、差示扫描量热仪(DSC)、AFM、XPS、FT-IR及核磁共振谱仪对乳液和乳胶膜性能进行了表征。TEM和DSC研究表明乳胶粒具有核壳结构，而每个FMBN膜都有两个对应于壳相和核相的玻璃化转变温度（Tg）。随引入的DFMA量的增加，FMBN膜的热稳定性增强，壳相Tg升高，膜表面自由能下降，表面水和二碘甲烷的接触角则升高。当DFMA为10g时，FMBN膜对水和二碘甲烷的接触角分别可达117.5°及92.8°；此时，FMBN膜的表面能可达11.47mN/m。XPS、AFM和膜疏水性相关研究表明FMBN膜中的氟烷基有向膜/空气界面迁移的趋势，而经过热处理后这种趋势尤为明显。自交联无皂乳胶膜的疏水性要好于自交联常规乳胶膜和非交联无皂乳胶膜。
然后，以FMBN处理的棉纤维织物作应用研究对象，用CA、白度仪、柔软度测定仪、AFM、FESEM等对FMBN的应用性能及其在织物表面的成膜形貌进行了研究。用1.0g/100ml H2O的FMBN处理棉织物后，可使其具有良好的疏水性；不影响处理织物的白度；而使织物手感变差。FESEM和AFM研究表明，处理后棉织物表面明显覆盖一层膜，织物表面变得较为光滑。
（3）以氢氧化钠（NaOH）为催化剂，DNS-86为乳化剂，将甲基丙烯酰氧丙基三甲氧基硅烷（KH-570）于水相中进行水解缩聚先制成聚倍半硅氧烷（PSQ）乳液；再以DNS-86为可聚合乳化剂，KPS为引发剂，PSQ为种子乳液，采用预乳化半连续种子乳液聚合方法使DFMA、MMA、BA及PSQ进行自由基共聚制得了带蓝色荧光的P（DFMA-co-MMA-co-BA-co-PSQ）杂化核壳无皂乳液（FPSQ）。考察了NaOH浓度、DNS-86用量及KH-570用量对PSQ乳液粒径大小的影响。当NaOH浓度为20mmol/L，DNS-86和KH-570用量分别为0.3g和10g，在100g水中经水解缩聚反应制得的PSQ乳液，其平均粒径为66.7nm。
利用TEM、SEM、TGA、AFM、XPS及FT-IR对乳液和膜的性能进行了表征。FPSQ乳胶粒具有核壳结构。由于引入的PSQ增加了FPSQ膜的微观粗糙度，再辅以低表面能的氟烷基基团的作用，FPSQ膜具有比CFMBD及FMBN更好的疏水性。FPSQ膜的表面自由能随引入的PSQ量的增加先减小后略增加；随引入的DFMA用量的增加呈单调递降趋势。FPSQ膜的热稳定性则随引入的PSQ量的增加而增强。XPS分析表明FPSQ膜中的氟烷基有向膜/空气界面迁移的趋势。AFM研究表明FPSQ膜比PSQ膜粗糙。FTIR证实了合成产物具有预期的结构。
再以FPSQ处理的棉纤维织物作应用研究对象，用CA、白度仪、柔软度测定仪、FESEM等对FPSQ的应用性能及其在织物表面的成膜形貌进行了研究。用1.0g/100ml H2O的FPSQ处理棉织物后，可使其防水性比CFMBD和FMBN处理后的织物更好；由于引入的硬性PSQ微球，使处理后织物的白度略增加而手感变差。FESEM研究表明，处理后棉织物表面明显覆盖有一层膜且膜下方有纳米微球的存在。
Owing to their low surface free energy, outstanding water-andoil-repellency and self-cleaning properties, high thermal and chemical resistance,etc., fluorine-containing polymers have been widely used in textile finishing,functional coatings, biomedical materials, and aerospace as well asmicroelectronics fields. Fluorinated acrylate copolymers possess both thefavorable adhesion property of acrylate resin and the inherent characteristics offluorine-containing polymers, such as high thermal, chemical, and agingresistance; low surface energy; excellent oil-and water-repellency. Hence, ithas attracted much concern. On basis of the reinforcement of the people’sresource and environmental awareness, how to synthesize fluorinated acryliccopolymers emulsion with anticipated macromolecular structure and propertiesin dispersed phase systems has proved to be a challenge in theoretical researchand products development. Common fluorinated polyacrylate emulsionprepared with traditional emulsion polymerization method contains lots of lowmolecule emulsifiers in physically adsorbed state, which have high mobility andan undesirable effect on the environment and the performance properties of thefilm like optics, electricity, surface property, hydrophobicity, and adhesion.Meanwhile, the relatively high market prices of the fluorinated monomers limittheir use, so researchers always hope to exploit possible polymerization strategyto minimize dose of the fluorinated monomers and simultaneously preserve theexcellent properties.
Therefore, the soap-free emulsion polymerization method was utilized inthis context to design and synthesize three sorts of fluorine-containing acrylate copolymers soap-free latexes with novel molecular structure and particlemorphology. Some factors influencing the stability of emulsion polymerization,relevant properties of the latexes and their films were systematicallyinvestigated later. Then, the as-prepared latexes were applied in the textilefinishing, and also film morphology and chemical compositions on the cottonsurface as well as its performance properties were researched in depth. Themain research contents are listed as following:
(1) Cationic fluorinated polyacrylate soap-free latexes (CFMBD) withcore-shell structure and blue fluorescence were synthesized by semi-continuousseeded emulsion polymerization of dodecafluoroheptyl methacrylate (DFMA)with methyl methacrylate (MMA), butyl acrylate (BA), anddimethylaminoethyl methacrylate (DM), maleic acid double ester-octadecylpoly(ethyleneoxy)20ether-ethylene trimethyl ammonium chloride (R303) as thecopolymerisable emulsifier and2,2′-azobis(2-methylpropionamidine)dihydro-Chloride (VA-50) as an initiator. Meanwhile, cationic fluorinated polyacrylatetraditional latex (GFMBD) was also fabricated as control with the sameprocedure and formulas except substituting R303for the1831/AEO-9mixedemulsifying system. Effects of the R303, VA-50and DFMA doses wereinvestigated on the stability of emulsion polymerization, the particle size andproperties of the latex film. The optimal condition for emulsion polymerizationwas that the R303and VA-50doses were3%and0.8%based on the totalmonomers weight, respectively, and the DFMA amount was8g in our recipe.Stable CFMBD latex with the average particle size of136.8nm could beobtained.
Performance properties of the latex and its film were characterized bytransmission electron microscopy (TEM), scanning electron microscopy (SEM),thermogravimetry analysis (TGA), atomic force microscopy (AFM), X-rayphotoelectron spectroscopy (XPS), contact angle goniometer (CA), Fouriertransform infrared (FTIR) spectrometry, and nuclear magnetic resonancespectrum, etc. Results showed that the latex particles possessed the apparentcore-shell structure by TEM observation. Surface tensions of the CFMBDlatexes were among63.7-67.2mN/m and very close to that of water; whereassurface tension of the control fluorine-containing latex was36.9mN/m and almost equal to that of the mixed emulsifiers system (1831/AEO-9). Theaforesaid facts illustrate that R303copolymerizes with other monomers and isincorporated into the copolymer main chains, however,1830/AEO-9areadsorbed onto the latex particle surface and prone to separate from the body,finally it will freely disperse in water which should heavily lower the surfacetension of the system. Those latex films showed the increasing thermal stabilitybut the decline of surface tension and water absorption with augment of DFMAamount in polymer. When the DFMA dose was employed as10g, CA of wateron latex films could maximally attain108.5°and that of diiodomethane was91.5°while the surface free energy and water absorption were12.65mN/m and7.6%, respectively. XPS analysis indicated the fluoroalkyl groups had thetendency to enrich at the film-air interface, which plays a crucial role in thehydrophobicity and micro-morphology of the latex films. The fluorine-free latexfilm showed the relatively smooth surface morphology in its AFM image,however, there were numerous little protuberances on the film surface of theCFMBD latex from the polymer containing27.5wt%DFMA in total monomersweight dried at room temperature. Especially, after the annealing process, somepeaks and lots of protuberances on that film appeared and the surface roughnesswas greatly increased. Water contact angles (WCAs) of fluorine-free latex film,those of CFMBD film dried at room temperature and after the annealing processcould attain62.5°,102.5°and108.5°, respectively.Those would further confirmthat the fluoroalkyl groups tended to enrich at the film-air interface and theannealing process would be in favor of this tendency.
Then CFMBD was utilized to treat the cotton fabric, and performanceproperties and surface morphology of the treated fabric were characterized byCA, whiteness meter, flexibility tester, AFM and FESEM. The treated cottonfabric by using the concentration of CFMBD as1.0g/100ml H2O had thefavorable water repellency. CFMBD didn’t influence whiteness of the treatedfabric but would make it slightly stiff at high doses. However, washingdurability of the treated fabric by CFMBD showed improvement compared tothe general emulsion resulting from the disadvantage effect of low molecularemulsifier on the film adhesion. CFMBD could form a smooth resin film on thetreated fabric/fiber surface under FESEM and AFM observations.
(2) Self-crosslinking fluorinated polyacrylate soap-free latexes (FMBN)with core-shell structure and blue fluorescence were synthesized bysemi-continuous seeded emulsion polymerization of DFMA with MMA, BA,and N-methylolamide (NMA) as self-crosslinkable monomer, ammoniumallyloxtmethylate nonylphenol ethoxylates sulfate (DNS-86) as thecopolymerisable emulsifier and potassium persulphate (KPS) as an initiator.Impacts of the DNS-86, DFMA and NMA doses were investigated on thestability of emulsion polymerization, the particle size and properties of the latexfilm. The optimal condition for emulsion polymerization was that the DNS-86dose was3%based on the total monomers weight, the DFMA and NMAamounts were8g and1.5g in our recipe, respectively. Stable FMBN latex withthe average particle size of116.3nm could be acquired.
Performance properties of the latex and its film were characterized byTEM, SEM, TGA, differential scanning calorimeter (DSC), AFM, XPS, CA,FTIR, and nuclear magnetic resonance spectrum, etc. Results indicated that thelatex particles possessed the uniform core-shell structure by TEM observation.The films formed from the FMBN latices thus had two Tg. Their thermalstability and Tgof the shell phase increased gradually with the augment of theDFMA amount in polymer. CAs of water and diiodomethane on latex films rosewith the increasing amount of DFMA. When the amount of the DFMA was10g,CA of water on latex film could maximally attain117.5°and that ofdiiodomethane was90.5°while the surface free energy and water absorptionwere11.47mN/m. XPS, AFM and hydrophobicity analyses indicated thefluoroalkyl groups had the tendency to enrich at the film-air interface. Thisenrichment of fluorine at the film-air interface was more evident after theannealing process. Meanwhile, hydrophobicity of the self-crosslinking soap-freelatex film showed some improvement compared to the general one and thenon-crosslinked one.
Then FMBN was utilized to treat the cotton fabric, and performanceproperties and surface morphology of the treated fabric were characterized byCA, whiteness meter, flexibility tester, AFM and FESEM. The treated cottonfabric by using the concentration of FMBN as1.0g/100ml H2O had thefavorable water repellency. FMBN didn’t influence whiteness of the treated fabric but would make it slightly stiff. FMBN could form a smooth resin film onthe treated fabric/fiber surface under FESEM and AFM observations.
(3) Polysilsesquioxane (PSQ) emulsions were firstly prepared by thehydrolysis and condensation reaction of methacryloxy propyl trimethoxyl silane(KH-50) in the aqueous phase, sodium hydroxide (NaOH) as catalyst andDNS-86as the emulsifier. Then fluorinated polyacrylate/PSQ hybrid soap-freelatexes (FPSQ) with core-shell structure and blue fluorescence were synthesizedby semi-continuous seeded emulsion polymerization of DFMA with MMA, BA,and PSQ as the seeded latex, DNS-86as the copolymerisable emulsifier andKPS as an initiator. Influences of the catalyst concentration, the DNS-86andKH-570doses were discussed on the particle size of the PSQ latexes. PSQemulsion with the average particle size of66.7nm could be acquired in100gaqueous solution while the concentration of the NaOH, the doses of the DNS-86and the KH-570were controlled as20mmol/L,0.3g and10g, respectively.
Performance properties of the latex and its film were characterized byTEM, SEM, TGA, AFM, XPS, and FTIR, etc. Results demonstrated that thelatex particles possessed the core-shell structure by TEM observation. TheFPSQ film showed more excellent hydrophobicity than those of CFMBD andFMBN since the micro-roughness of the FPSQ had been enlarged due to theimported PSQ besides the role of the fluoroalkyl groups with low surface freeenergy. Their surface free energies decreased firstly and increased slightly withthe increasing amount of the imported PSQ amounts but showed a unilaterallydecreased trend with augment of the DFMA dose. Thermal stability of the FPSQfilms increased gradually with augment of PSQ amount in polymer. XPSanalysis indicated the fluoroalkyl groups had the tendency to enrich at thefilm-air interface. FTIR confirmed the structure of the as-prepared product.AFM results indicated that the hybrid latex film was coarser than the PSQ latexfilm.
Then FPSQ was utilized to treat the cotton fabric, and performanceproperties and surface morphology of the treated fabric were characterized byCA, whiteness meter, flexibility tester, and FESEM. The treated cotton fabric byusing the concentration of FPSQ as1.0g/100ml H2O had more favorablehydrophobicity than those treated by CFMBD and FMBN. The treated fabrics became slightly whiter but its handle became worse. FPSQ could form a hybridfilm on the treated fabric/fiber surface under FESEM observation. There weresome nanospheres beneath the hybrid film.
引文
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