Synthesis of Novel Fluorinated Acrylate Co-polymers and Their Application on Cotton Fabrics

Two novel fluorinated acrylate monomers 4a and 4b containing perfluorohexyl group were designed and synthesized starting from 4-allylanisole and perfluorohexyl iodide.The monomers 4a and 4b were then copolymerized with octadecyl acrylate and 2-hydroxyethyl acrylate by emulsion polymerization to give copolymers PFA 1 and PFA 2 respectively.The co-polymers were characterized by FT-IR and their heat stability was measured by TGA.The surface properties of PFA 1 and PFA 2 were studied by applying on cotton fabrics.The treated cotton fabrics showed good water-repellent property,and the contact angles for water reached 142° for PFA 1 and 136° for PFA 2.

PREPARATION AND SURFACE PROPERTIES OF ACRYLIC COPOLYMERS CONTAINING FLUORINATED MONOMERS

A series of copolymers comprising butylmethacrylate, styrene, butylacrylate, hydroxypropyl acrylate and perfluoroalkyl methacrylate were synthesized by the free radical polymerization using BPO as an initiator. The surface property of the copolymer films was subsequently characterized. The contact angle measurements and energy dispersive analysis of X-ray （EDAX） show that the length and content of perfluoroalkyl side chains in the copolymers are crucial for the preparation of the film with low surface energy. At a given content of fluorinated monomers in the copolymers, the longer the perfluoroalkyl side chain, the larger the water contact angle of the copolymer films will be. On the other hand, the higher the content of fluorinated monomers, the lower the surface energy is. The water contact angle increases with the increase of the fluorinated monomer content and reaches a plateau at 3 wt% of fluorinated monomer content.

A Novel Fluorinated Acrylic Copolymer:Synthesis,Characterization,and Its Applications on Cotton Fabric

In order to prepare water-oil repellent and fire retardant textile finishing agent, 1H ,1H,2H,2H-perfluorooctyl acrylate （FA） and acryloyloxy-1, 3-his （ diethylphosphoramidate ） propan （BisDEAEPN） were copolymerized with 2-hydroxyethyl acrylate （ HEA ） and stearyl methacrylate （ SMA ） by emulsion polymerization to form fluorinated phosphorus-eantaining acrylate copolymer （PFPA）. The copolymer was characterized by Fourier transform infrared spectroscopy （FT.IR） and the thermal stability was investigated by thermogravimetric analysis （TGA）. The emulsion was applied on cotton fabric and the surface properties of treated fabric were studied. The treated surface showed good repellent properties as contact angle for water reached 145° and for n-dodecane 110° respectively. The surface also showed some flame retardant property with 22.5 % of limited oxygen index （LOI）.

Synthesis of a Novel Core-shell Type Acrylic-polyurethane Hybrid Emulsion Containing Siloxane and Fluorine as well as Water and the Oil Resistances of Cured Film

Siliconated polyurethane （Si-PU） was synthesized using isophorone diisocyanate （IPDI）, hydroxybutyl-terminated polydimethylsiloxane （PDMS）, polytetramethylene ether glycol （PTMG）, polypropylene glycol （PPG）, 1,6-hexanediol （HDO）, dimethylol propionic acid （DMPA） and triethylamine （TEA）. Based on butyl acrylate （BA）, 2, 2, 2-trifluoroethylmethacrylate （TFEMA） and Si-PU as a seed emulsion, a novel core-shell type acrylic-polyurethane hybrid emulsion, containing siloxane and fluorine （F-Si-PU）, was prepared by seeded emulsion polymerization. The contents of siloxane and fluorine were determined according to the feed ratio. Fourier transform infrared spectroscopy （FTIR） was used to identify the chain structures of Si-PU and F-Si-PU. Investigation of transmission electron microscopy （TEM） confirmed the core-shell structure of F-Si-PU emulsion. Measurement results of water contact angle and the swelling ratio in water and n-octane for cured film showed that the water and the oil resistances for F-Si-PU had been significantly improved at a suitable content of fluorine and siloxane.

短链含氟聚丙烯酸酯功能整理剂的制备及应用

为制备耐水洗性能优良的三防整理剂,以丙烯酸十三氟辛酯(Tridecooctyl acrylate,C6F)和丙烯酸十八酯(Octaglycidyl acrylate,SA)为主要单体,甲基丙烯酸缩水甘油酯(Glycidyl methacrylate,GMA)为交联单体,通过细乳液聚合法制备了一种短链含氟丙烯酸酯共聚物细乳液,并将其作为整理剂应用在棉织物上;通过红外光谱分析、粒径分析和热重分析对乳液进行表征,采用场扫描电镜和X射线光电子能谱仪对棉织物表面结构进行分析,探究C6F和SA的用量对该共聚物薄膜表面能的影响。结果表明:当C6F质量分数为50%,SA质量分数为25%时,共聚物薄膜的表面能低至9.16mN/m;整理后棉织物的水接触角为150.8°,橄榄油接触角为141.2°,拒水等级4级,拒油等级4级,耐沾污等级5级;整理后棉织物经过20次水洗后水接触角仍有135.7°,橄榄油接触角为124.8°,表现出良好的耐水洗性能。该文可为制备短链C6型含氟丙烯酸酯共聚物提供数据参考。

水性丙烯酸涂层改性研究进展

简单阐述了水性丙烯酸树脂的单体结构、聚合方法以及应用现状;较为系统地总结了根据不同材料改性水性丙烯酸树脂的研究进展,改性材料可归纳为纳米材料、有机硅、有机氟、聚氨酯和环氧树脂以及一些新型材料等。重点论述了改性材料对水性丙烯酸树脂进行改性的反应机理、相应的微观结构及性能提高情况。展望了水性丙烯酸涂料发展的方向。

含氟丙烯酸酯聚合物结构对性能的影响分析

将含氟基团引入丙烯酸酯合成的丙烯酸聚合物,不仅具有丙烯酸酯原有的各种性能优势,还可以赋予其更多含氟化合物的特性。介绍了含氟丙烯酸酯类聚合物的主要种类(均聚物、共聚物)及其典型的合成方法,总结分析了影响含氟丙烯酸酯类聚合物性能的关键因素,指出合成更加环保、成本低廉、性能媲美长链氟丙烯酸酯等优异表面性能的含氟丙烯酸酯类聚合物是未来研发方向。

含氟单体改性丙烯酸树脂的合成及性能研究

用不同的有机氟单体对丙烯酸树脂进行了改性,通过对聚合工艺、改性单体种类及用量等因素的考察,选择全氟乙基辛基丙烯酸酯为改性单体,合成了具有高接触角、低表面能的有机氟改性丙烯酸树脂;对树脂进行了红外光谱、相对分子质量及其分布和玻璃化转变温度测定,证明含氟单体参与了丙烯酸酯类单体的共聚合反应。研究了含氟丙烯酸酯共聚物涂料表面性能的影响因素,结果表明,含有17个氟原子的全氟乙基辛基丙烯酸酯对丙烯酸树脂改性效果显著,当全氟乙基辛基丙烯酸酯用量占单体总量的6%~8%时,漆膜的表面张力、疏水性(水接触角和吸水率)、耐候性等都有显著改善,水接触角可以达到105°左右。

水性氟碳涂料研究进展

通过水性氟碳树脂在水中的溶解度不同和固化温度不同两方面介绍了水性氟碳涂料的分类和各类别的优缺点、实际生产过程中常用的制备方法工艺流程、水性氟碳涂料自身的优异性能并举例通过改性如何进一步提高产品性能及现阶段的发展进程。水性氟碳涂料因其突出的化学性质和优异的环保性能,是符合当今时代发展要求的产品并对其提出了未来如何对含氟丙烯酸酯乳液发展的期望。

氟单体改性丙烯酸树脂的研究

用不同有机氟单体对丙烯酸树脂进行改性,通过对聚合工艺、改性单体种类及用量等因素的考察,选择全氟乙基辛基丙烯酸酯为改性单体,合成了具有大接触角、低表面能的氟单体改性丙烯酸树脂。对树脂进行了红外光谱、相对分子质量及分布、玻璃化转变温度进行测定,证明含氟单体参与了丙烯酸酯类单体的共聚合反应。研究了含氟丙烯酸酯共聚物涂料表面性能的影响因素,结果表明,全氟乙基辛基丙烯酸酯对丙烯酸树脂改性效果显著,当其用量占单体总量的6%~8%时,漆膜的表面张力、疏水性(水接触角和吸水率)、耐候性等均得到改善,水接触角可以达到105°左右,漆膜保光率为82.5%,无生锈、起泡、开裂、粉化等问题,变色≤1级。

氟硅改性丙烯酸树脂的制备及其防污性能研究

研究了有机硅及有机氟改性丙烯酸酯单体对防污性能的影响。以甲基丙烯酸聚二甲基硅氧烷基酯、全氟己基乙基丙烯酸酯、甲基丙烯酸、甲基丙烯酸甲酯、4-羟丁基丙烯酸酯、甲基丙烯酸月桂酸酯为原料,通过分布投料法,中和水转制备侧链含有有机硅、有机氟及长链烷烃结构的丙烯酸改性树脂。固定有机硅及有机氟单体的含量。当有机氟单体增加时,接触角增大,同时耐溶剂性能提高;增加有机硅单体时,耐污性能提高,尤其是油性笔擦拭性能优异。增加交联基团可以使涂层硬度达到2H。

Effect of cationic monomer on properties of fluorinated acrylate latex

Cationic fluorinated acrylate latex was prepared via semi-continuous emulsion copolymerization of cationic monomer and other monomers. The resultant latex and its film were characterized with dynamic light scattering detector and contact angle meter. Influences of amount of DMDAAC on the properties of resultant latex and its film were investigated in detail. Results show that the particle size of the latex has the minimum value knd the zeta potential of the latex is increased when the amount of DMDAAC is increased. In addition, the particle size of the latex is unimodal distribution when the amount of DMDAAC is not more than 2.5%. However, the particle size of the latex is bimodal distribution when the amount of DMDAAC is more than 2.5%. The contact angle is varied slightly with the increase of amount of DMDAAC when it is not more than 2.5%. Nevertheless, the contact angle is decreased with the increase of the amount of DMDAAC when it is more than 2.5%.

Synthesis and Characterization of Novel UV-curable Fluorinated Polyurethane-acrylate Copolymer

A series of UV-curable fluorinated polyurethane-acrylate（PUA） has been developed by incorporating octafluoropentyl alcohol into the segment of UV-curable polyurethane-acrylate to improve the thermal property and surface property of the copolymer material. The structures of the synthesized polymers were characterized by Fourier transform infrared（FTIR） spectrometry. In order to find out the effect of incorporated fluorine on the UV-cured films, the properties of the UV-cured films were tested through contact angle, water absorption, and thermogravimetric analysis （TGA）. The fractured-surface morphologies of the UV-cured coatings were investigated by scanning electron microscopy（SEM）. With increasing the content of fluorine segments, the contact angle of the UV-cured films increased and the water absorption decreased, suggesting the fluorine segments migrated and formed a fluorine-covered surface to avoid water penetration. The observation of the fractured-surface morphology through SEM test showed that the fluori- nated UV-cured films gained rough fractured-surface compared with the pure UV-cured polyacrylate film, demonstrating the migrating of the fluorine segments. The TGA curves show that the fluorinated UV-cured films gained higher thermal degradation temperature than the virgin UV-cured polyacrylate film. And as increasing the fluorine content, the thermal degradation temperature increased. These phenomena could be reasonably explained by the enrichment of fluorinecontained segment on the surface of the film and the high thermal property due to fluorine atom.

SYNTHESIS AND CHARACTERIZATION OF A NOVEL FLUORINE-CONTAINING HYDROPHOBICALLY ASSOCIATING POLYMER

In this article, the synthesis and characterization of a novel fluoromonomer and its copolymer with acrylamide is reported. 2-perfluoroamyl-4-hydroxylquinoline 2 was synthesized from ethyl 2, 2-dihydroperfluoroheptanoate in high yields. The monomer 4 was then synthesized from 2 in two steps readily in high yields. Synthesis and characterization of copolymers of acrylamide (AM) and the fluoromonomer were investigated. The composition and intrinsic viscosity of these copolymers were studied. It was found that the rheological properties of aqueous solutions of polyacrylamide were modified significantly when a small proportion of the fluoromonomer 4 was incorporated on investigating the viscosity-concentration profiles, pseudoplasticity of these solutions and the effect of the presence of surfactant. These results could be explained by the hydrophobic association of the fluorocarbon segments in the aqueous solutions of these copolymers.

含氟聚氨酯二甲基丙烯酸酯为芯材的微胶囊制备及自修复性能

首先自制了含氟聚氨酯二甲基丙烯酸酯(TFXPUA)大单体,然后采用界面聚合法制备了以TFXPUA、1,6-己二醇二丙烯酸酯(HDDA)、2-羟基-2-甲基-1-苯基-1-丙酮(HMPP)为芯材,聚氨酯为壁材的含氟聚氨酯微胶囊(MTFXPUA),再将其添加到水性聚氨酯中制备自修复涂膜及涂层。通过红外光谱(FTIR)、凝胶渗透色谱(GPC)、扫描电镜(SEM)、粒度分析(PSA)、接触角测试、拉伸试验、耐盐水浸泡实验以及电化学阻抗测试表征了TFXPUA以及MTFXPUA的化学结构、微观形貌、自修复及力学等性能。结果表明:含氟聚氨酯二甲基丙烯酸酯(TFXPUA)大单体成功制备,其数均分子量为14275。基于TFXPUA为芯材制得的含氟聚氨酯微胶囊(MTFXPUA)平均粒度为24.05μm,SEM结果表明MTFXPUA微胶囊在聚氨酯涂层中对微裂纹进行了良好自修复,随着TFXPUA中四氟对苯二甲醇(TFB)用量增加,MTFXPUA的修复处接触角、拉伸强度、在低频处阻抗值、Nyquist曲线半径呈现增大的趋势;当TFB用量超过6%时,增加趋势变缓。TFB用量为6%时,修复处的接触角可达96.80°,修复后涂膜拉伸强度由17.94MPa增加到25.21MPa,基于含氟聚氨酯二甲基丙烯酸酯(TFXPUA)大单体制备的微胶囊对聚氨酯涂层具有良好的自修复性能,实现了对修复后材料的二次保护。

食品包装用水性丙烯酸酯防油剂的制备及应用性能研究

以淀粉、甲基丙烯酸甲酯、丙烯酸丁酯和甲基丙烯酸为主要原料,通过自由基聚合法进行接枝共聚制备了水性丙烯酸酯无氟防油剂,对其化学结构、粒径、Zeta电位和成膜性进行了分析。将水性丙烯酸酯防油剂涂布在原纸上制得食品包装用防油纸,对防油纸的动态油接触角、防油防水性能、耐高温性能、抗冷冻性能和再制浆性能进行了研究。结果表明,合成的水性丙烯酸酯防油剂粒径分布均匀,稳定性良好,平均粒径和Zeta电位分别为254.2 nm和-39.74 mV;防油剂可赋予纸张优良的防油性和防水性,当涂布量为7.5 g/m^(2)时,防油等级可达10.2级,Cobb值从原纸的24.2 g/m^(2)降低至1.9 g/m^(2);且防油纸具有良好的耐高温性能、抗冷冻性能和可再制浆性能。

复合型无氟聚丙烯酸酯乳液的制备及其防水性能

针对含氟拒水整理剂存在生物毒性、耐久性较差等问题,合成了一种聚丙烯酸酯型无氟防水剂。将丙烯酸十八酯(SA)分别与丙烯酸乙基己酯(2-EHA)和甲基丙烯酸环己酯(TMCHMA)进行细乳液聚合,制备了成膜等性能不同的2种SA共聚物胶乳;2种胶乳经复合后用于织物的无氟防水整理,借助原子力显微镜观察了复合胶乳涂膜的表面形貌,研究了复合比例及用量对整理织物表面结构以及防水性的影响。结果表明:与2-EHA共聚可提高胶乳的成膜性,而TMCHMA的引入则可增强胶乳的保形性;2种胶乳复合后,在整理后的织物表面形成微纳疏水结构,整理织物的防水性能显著提升,其静态接触角最高可达152°,防水等级达到5级,经50次耐磨损测试后仍保持良好的疏水性能。

基于羟基含氟丙烯酸树脂的防腐抗菌涂层的制备与性能研究

以丙烯酸羟丙酯(HPAA)、丙烯酸(AA)及甲基丙烯酸十二氟庚酯(G04)为原料,制备了一种溶液共聚型全氟羟基丙烯酸树脂(PFHA),用傅立叶变换红外光谱仪(FT-IR)对PFHA进行了结构表征。以PFHA、油水两用型钛白粉和季铵基硅溶胶包覆纳米银(QAg-SiO_(2))等为主要成分配制了溶剂型含氟丙烯酸涂料,分别考察了树脂羟基含量、纳米二氧化钛和QAg-SiO_(2)含量对涂层性能的影响。结果表明:当树脂羟基含量为3.3%、涂料中TiO_(2)和QAg-SiO_(2)的含量分别为25%和10%时(均为质量分数),涂层的水接触角为114°,硬度为3H,附着力为1级,且经硫酸盐还原菌浸泡168 h后无腐蚀,具有优良的物理性能与防腐抗菌性能。

TiO_(2)/有机硅溶胶改性含氟苯丙乳液的制备及性能表征

为改善含氟苯丙乳液的疏水性、热稳定性及力学性能,以钛酸丁酯(TBT)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)为原料,通过溶胶-凝胶法制备出TiO_(2)/有机硅溶胶(TS),并将其与丙烯酸丁酯(BA)、苯乙烯(ST)、甲基丙烯酸十二氟庚酯(G04)及其他丙烯酸类功能单体作为主要原料,通过半连续加料法及种子乳液聚合,制备出一种TiO_(2)/有机硅溶胶改性的含氟苯丙乳液(TS-BHSAG)。探讨了不同TS含量对乳液转化率的影响,利用FTIR、纳米粒度仪、稳定性分析仪、XPS、XRD、SEM、AFM、TGA表征研究了乳液及乳胶膜的结构组成及应用性能。结果表明,当TS含量逐渐增加时,乳液转化率及稳定性呈持续下降趋势;随着TS含量增加,乳液平均粒径从55.58 nm增至106.16 nm;FTIR及XPS结果显示,TS-BHSAG乳胶膜中形成了Si-O-Si、Si-O-Ti、CF2键,证实TS被初步合成,且其与G04一起被引入聚合物中;XRD结果表明,TS是以无定形相分散于丙烯酸树脂基体中;通过SEM与AFM观察到,TS纳米粒子在乳胶膜表面构成峰状粗糙结构,增强了乳液的疏水性能;TGA结果表明,在热失重为10%及50%时,TS-BHSAG的热分解温度分别为380.59℃、415.39℃,在600℃时,乳胶膜的残余质量分数从4.78%增加到8.56%;当TS添加量为3%时,TS-BHSAG乳胶膜的接触角为121°,附着力为1级,耐冲击性能为50 cm,硬度为2H,吸水率为6.1%。

有机硅改性丙烯酸酯无氟防水剂的合成与应用

以丙烯酸十八酯、氯乙烯和单末端丙烯酸酯基有机硅单体为原料,通过乳液聚合法制备了有机硅改性丙烯酸酯无氟防水剂,并用于不同织物的整理。研究了有机硅单体用量对防水剂乳液稳定性、处理织物耐久防水性、手感和缝线滑移性能的影响;通过红外光谱和EDS能谱分析对无氟防水剂和整理后的织物进行表征。结果表明,有机硅单体对丙烯酸酯防水剂成功进行了化学改性,质量分数为5%时,制备的无氟防水剂具有很好的乳液稳定性,整理后织物的初期防水和耐久防水性以及手感得到明显改善,手感由3.5级提升至2.5级,缝线滑移性能有所下降,滑移量由10 mm增大至16 mm。