核壳型短链含氟丙烯酸酯乳液的合成及表征

该文研究了核壳型短链含氟丙烯酸酯乳液的合成与表征。以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)的共聚体为核,短氟碳链2-(全氟己基)乙基甲基丙烯酸酯(FMA6)和非氟烷基丙烯酸酯的共聚体为壳,采用多步乳液聚合法,合成系列具有核壳结构的含氟丙烯酸酯乳液,研究了壳相中氟单体用量和非氟烷基丙烯酸酯的烷基链长度n(链长n=4、8、12、16、18)对产物疏水疏油性能的影响,并对产物进行表征。结果表明:当采用氟单体用量为总单体质量的8.5%,甲基丙烯酸十六酯(CMA)的共聚体为壳层时,由合成乳液制得的乳胶膜的疏水疏油性最佳,对水接触角为124.67°,对二碘甲烷接触角为112.76°。FTIR、TEM和DSC/TGA表征表明,原料单体均参加了反应;乳液颗粒具有明显的核壳结构;聚合物存在两个玻璃化温度(-18.87℃和32.08℃),热分解温度比不含氟的聚合物提高了近20℃。由此说明,用合成的核壳型短链含氟丙烯酸酯乳液制得的涂膜具有优异的疏水疏油性和耐热性能。     

含氟丙烯酸酯乳液高疏水性与低氟含量的平衡探索

为了研究含氟丙烯酸酯乳液涂膜的疏水性与氟含量的平衡关系,以甲基丙烯酸十二氟庚酯(DFHM)为含氟单体,双丙酮丙烯酰胺(DAAM)和己二酸二酰肼(ADH)为交联单体,采用半连续核壳乳液聚合的方法合成了一系列自交联含氟丙烯酸酯共聚物乳液。研究表明:含氟单体含量为12%(即氟含量为6.84%,均以聚合单体的总质量计,下同)时,含氟基团在涂膜表面可以达到饱和,乳液固含量可达38.2%;再添加4%交联单体,涂膜的水接触角为116.6°。当含氟单体含量降为4%(氟含量2.28%)时,通过提高成膜温度或添加成膜助剂,也可使涂膜表面的水接触角达到104.2°,具有较好的疏水性能。     

含氟丙烯酸酯共聚物结晶与涂膜表面润湿性能研究

以全氟辛基乙基甲基丙烯酸酯(FMA)分别和不同侧碳链长度(烷烃链长n=4,8,12,16,18)的丙烯酸酯为原料,合成一系列含氟丙烯酸酯共聚物。用红外光谱仪(FT-IR)和多功能光电子能谱仪(XPS)对共聚物化学结构与涂膜表面化学成分进行表征,结合表面接触角测试仪测定相应涂膜表面接触角并分析了其表面自由能;同时也用示差扫描量热法(DSC),X射线衍射(XRD)和偏光显微镜(POM)对含氟丙烯酸酯共聚物的结晶行为进行分析比较。结果表明,当非氟单体的烷烃链长n=4、8、12时,聚合物在常温下各向同性,不具有结晶性;当n=16、18时在常温下即可结晶,得到近晶A相的层状纹影织构。特别是当n=16时,烷烃侧链排列更紧密,聚合物的结晶具有更好协同作用,表现出优异的结晶规整性和低表面能,从而提高了聚合物涂膜的疏水疏油稳定性。     

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。     

含环氧和长氟碳链的丙烯酸酯的制备及其改性环氧树脂涂料性能研究

采用两步法合成了可聚合含氟丙烯酸酯预聚物(FM),并将其与甲基丙烯酸缩水甘油酯(GMA)共聚合成了含环氧和长氟碳链的丙烯酸酯共聚物(CFPA)。采用GPC、1H NMR对该聚合物的结构进行表征。将CFPA与环氧树脂E51共混得到改性环氧树脂涂料。对涂膜的表面性能以及本体性能进行了研究。结果表明:加入少量CFPA(0.5%)便可使涂膜的疏水性大幅度提高(水接触角97.8°,二碘甲烷接触角66.0°,表面能25.16 m N/m)。X射线光电子能谱(XPS)研究发现,含氟丙烯酸酯聚合物添加量为4%时,CFPA改性的环氧树脂涂膜表面氟原子含量是无规含氟含环氧丙烯酸酯(RFPA)改性的环氧树脂涂膜的8.39倍,氟原子富集于改性涂膜表面,使得材料疏水性得到提高。对改性涂膜的本体性能进行研究,结果表明:改性涂膜具有高凝胶含量、高硬度(4H)、优异的附着力(0级)和低吸水率。     

含POSS含氟杂化丙烯酸酯共聚物的制备及其涂膜疏水性

以甲基丙烯酸甲酯(MMA)、丙烯酸正丁酯(BA)、甲基丙烯酸-β-羟乙酯(HEMA)、2-(全氟辛基)乙基甲基丙烯酸酯(FMA)、甲基丙烯酸酯基异丁基八面低聚倍半硅氧烷(MAPOSS)为单体,偶氮二异丁腈(AIBN)为引发剂,采用自由基溶液聚合法合成了含POSS含氟杂化丙烯酸酯共聚物。然后用二甲苯与三氟三氯乙烷的混合溶剂溶解该共聚物,将玻璃片和不锈钢滤网浸入其中,通过浸渍提拉法得到一层疏水涂膜。研究了POSS的含量对涂膜疏水性的影响。采用场发射扫描电子显微镜(SEM)、原子力显微镜(AFM)和X射线光电子能谱仪(XPS)对涂膜的表面形貌和元素进行了表征。结果表明,杂化共聚物中的POSS能够自发聚集在玻璃片和滤网表面,形成特定的粗糙结构,而随POSS含量增多,其聚集带来的表面粗糙度增加,导致涂膜的水接触角更大。当POSS质量分数为20%时,POSS聚集表面的平均粗糙度(Ra)达到209 nm,同时低表面能的氟在涂膜表面的质量分数为25.70%,结合滤网本身的微米孔结构,三者共同作用造就了涂膜滤网表面良好的疏水性,其水接触角达到144°。     

环氧基-含氟丙烯酸酯共聚物的制备与其在钢板上的应用

用十三氟辛醇、丙烯酸、烯丙基缩水甘油醚(AGE)为功能单体合成了环氧基-含氟丙烯酸酯共聚物涂覆剂。将上述共聚物涂覆剂和γ-缩水甘油醚氧丙基三甲氧基硅烷(Z-6040)复配喷涂在处理过的钢板上制备涂层。研究了共聚物和复配剂的用量对钢板涂层疏水疏油及耐盐水性的影响。结果表明,质量分数为5%的共聚物涂覆于钢板上,其涂层的水和正十六烷初始接触角分别为113.6°和66.9°;将共聚物(5%)-Z-6040(3%)复配涂覆于钢板上,其涂层在摩擦200次后的水和正十六烷接触角分别为108°和60.1°,说明涂层具有良好的疏水疏油性、耐磨擦性;盐水浸泡试验表明,涂层具有良好的耐盐水腐蚀性,对钢材有良好的保护作用。     

聚酯粉末涂料的耐久性评价及其性能改进

介绍了通过佛罗里达曝晒试验评价各类聚酯粉末涂料的耐久性。采用十二氟庚烷基长链氟碳烷基的聚酯树脂粉末涂料,较大改善涂膜表面疏水性和疏油性,为改进聚酯粉末涂料耐久性作了有益的探索。     

含氟丙烯酸酯橡胶的合成及性能

以丙烯酸乙酯、丙烯酸丁酯、含氟丙烯酸酯为单体,采用半连续乳液聚合法合成了含氟丙烯酸酯橡胶(ACM),用傅里叶变换红外光谱表征了其微观结构,考察了含氟单体种类及用量对含氟ACM亲水性、玻璃化转变温度及硫化特性的影响,以及交联剂二乙烯基苯(DVB)用量对含氟ACM硫化胶拉伸性能的影响。结果表明,丙烯酸六氟丁酯或丙烯酸十二氟庚酯(简称G 05)的转化率均超过90%;随着含氟单体用量的增加,ACM乳液涂膜的接触角逐渐增大,当加入质量分数为5%的G 05时,涂膜变为疏水性表面;含氟ACM只有1个玻璃化转变温度,且随着含氟单体用量的增加而逐渐下降;含氟ACM的操作安全性高,在硫化初期具有良好的流动性能;当DVB质量分数为3%时,含氟ACM的拉伸强度达到11.2 MPa。     

有机硅改性含氟(甲基)丙烯酸酯聚合物乳液的制备及其性能研究

先合成了聚硅氧烷阴离子乳液以及链中含硅烷偶联剂和含氟单体的(甲基)丙烯酸酯聚合物乳液,并且利用羟基缩合反应,将2种乳液混合反应,通过乳液接枝共聚的方法合成了一种高硅含量的有机硅改性氟代(甲基)丙烯酸酯聚合物乳液,并采用了红外光谱对聚合物乳液分子进行了表征。测试结果表明:有机硅质量分数为20%、有机氟质量分数为12%的聚合物乳液涂膜综合性能最佳,较不含有机硅氟的聚合物乳液涂膜,其水表面接触角由77.5°增加到96°,24 h吸水率由5.3%下降到2.3%,耐水性大大增加;玻璃化转变温度由8.53℃下降到-2.74℃,聚合物分子链的柔顺性有所提高;同时乳液涂膜的初始分解温度提高了77～92℃,热稳定性也明显提高,说明此方法合成的高硅含量硅丙乳液可作为一类具有优良疏水性及低表面能的功能材料得以应用。     

环氧丙烯酸酯共聚物复合乳液研究

通过核壳乳液聚合工艺引入环氧树脂,对丙烯酸醋乳液进行改性,制备了水性环氧/丙烯酸醋杂化乳液.通过接触角、极化曲线测试以及傅里叶变换红外光谱(FT-IR)、热重分析(TGA)、电化学阻抗谱(EIS)等方法对改性前后的丙烯酸醋进行了表征.结果表明,以12%环氧树脂改性的丙烯酸醋与改性前的丙烯酸酣相比,其疏水性、热稳定性和耐...     

自制反应性乳化剂制备的含氟核壳乳液及性能

采用烷基酚聚氧乙烯醚（OP-10）与顺丁烯二酸酐反应,制得反应性乳化剂;以甲基丙烯酸甲酯（MMA）和丙烯酸丁酯（BA）为核,甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）和甲基丙烯酸十二氟庚酯（DFMA）为壳,采用半连续种子乳液聚合方式制备核壳型含氟丙烯酸酯乳液。对反应性乳化剂的性能进行了初步探究,并通过红外光谱、TEM、DSC、CA、TGA等对体系进行了研究。结果表明,自制的反应性乳化剂性能优异,合成的乳胶粒具有典型的核壳结构,乳液性能稳定;反应性乳化剂的引入使涂层具有较低的表面能,有效地提高了乳胶膜的疏水性能。     

Properties of (meth)acrylate copolymer grafted with long fluorinated side chain prepared by “graft onto” strategy

A (meth)acrylate copolymer grafted with long fluorinated side chains (AGLF) was synthesized successfully through a two‐step procedure. First, a carboxyl terminated fluoropolymer, poly(2,2,3,4,4,4‐hexafluorobutyl methacrylate) was synthesized by conventional radical polymerization in the presence of 3‐mercaptopropionic acid as chain transfer agent. And then the fluoropolymer was grafted to the in‐house synthesized polyacrylate (MMA‐r‐BA‐r‐GMA). Fourier transform infrared spectroscopy and ¹H‐nuclear magnetic resonance spectroscopy were employed to verify the synthesis of AGLF. Moreover, the surface properties were investigated by contact angle measurement and X‐ray photoelectron spectroscopy. The results proved that a small amount of poly(2,2,3,4,4,4‐hexafluorobutyl methacrylate) addition can create a hydrophobic surface effectively. Furthermore, the X‐ray photoelectron spectroscopy results showed that it is the AGLF grafted with longer fluorinated side chain that have more fluorine atoms enriched on the surface and thus performed better hydrophobicity and lipophobicity. Testified by thermogravimetric analysis and differential scanning calorimetry, it was found that AGLF films have excellent thermal properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45894.     

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     

Synthesis and characterization of crosslinking waterborne fluorinated polyurethane‐acrylate with core‐shell structure

Crosslinking core‐shell emulsions of waterborne fluorinated polyurethane‐acrylate (WFPUA) were successfully synthesized using a solvent‐free method. The crosslinkers of diacetone acrylamide and adipic dihydrazide were introduced into the WFPUA emulsions. The physical properties of hybrid emulsions such as the average particle size, stability, and viscosity were characterized. The core‐shell of crosslinking WFPUA emulsion synthesized in this study was observed by transmission electron microscopy. Then, the results of Fourier transform infrared spectroscopy, atomic force microscopy, and X‐ray photoelectron spectroscopy indicated that the fluorinated monomer (FA) had been polymerized into the crosslinking waterborne polyurethane‐acrylate polymer, and the fluorinated groups have evident enrichment on the film‐air surface with the increase of FA content. At the same time, the thermal properties, water repellent/antifouling properties, and mechanical properties were measured. Moreover, the thermal properties and the elongation are raised but tensile stress and shore hardness are decreased with the increase of FA content. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40970.     

Preparation and characterization of fluorinated polypropylene by reactive extrusion with fluorinated acrylate

The fluorinated polypropylene (PP) was prepared by reactive extrusion, in which PP was grafted with fluorinated acrylate, acrylic acid 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-nonyl ester (HFNAE). The Fourier transformed spectroscopy results confirmed the graft polymerization on PP backbone by the reactive extrusion. The surface tension of these polymer materials and the influence of HFNAE on the crystalline behavior had been investigated with static contact angles apparatus, wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC) and the polarized optical microscope (POM). The surface tension of fluorinated PP was found to be less than that of the untreated polypropylene. The results showed that the fluorinated acrylate (HFNAE) might induce β form crystals when being grafted into PP from the result of WAXD and DSC. The spherule configuration difference between PP and fluorinated PP could be observed with POM photos. The result from the isothermal crystallization kinetic analyses indicated that the speed of the forming nuclear for the regular PP was smaller than that of the fluorinated PP. In addition, the addition HFNAE improved impact strength and thermal stability of PP, but the tensile tension decreased slightly.     

水溶性含氟丙烯酸酯乳液的合成研究进展

含氟丙烯酸酯类聚合物因具有突出的成膜性能及耐老化性能而成为优良的成膜材料。其中,水溶性含氟丙烯酸酯乳液的合成研究,具有广泛的单体种类,聚合方式简单多样,在涂料领域受到了广泛的应用和关注。选择合适的乳液共聚单体及聚合工艺,不仅能够根据实际需要调节含氟聚合物的分子结构,而且可以获得最佳含氟量,以满足特殊性能需要的含氟丙烯酸酯乳液。综述了水溶性含氟丙烯酸酯乳液的聚合方法、常用含氟单体和非氟单体以及改性研究进展。     

Colloidal and polymer properties difference of fluorinated acrylate latex prepared with different fluorinated monomers

Fluorinated acrylate latex was prepared by copolymerizing fluorinated monomer, butyl acrylate, and methyl methacrylate, which was initiated by potassium persulfate in the water. The resultant fluorinated latex and its film were characterized with contact angle determinator, dynamic light scattering detector, and differential scanning calorimetry, respectively. Influence of type of fluorinated monomers on colloidal and polymer properties of fluorinated acrylate latex was studied. Results show that the coagulation rate, particle size, contact angle, glass transition temperature, and chemical resistance are increased with the increase of the number of fluorine atom in the fluorinated monomer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012