含氟“三防”纺织助剂的合成方法及发展前景

目前所合成的含氟聚合物主要是含氟丙烯酸酯类共聚物,特别是含氟共聚物乳液,是将含氟单体与丙烯酸酯类单体或其它乙烯类单体通过乳液共聚而制得。该合成方法的条件简单、操作易控,可制得稳定的共聚物乳液,产物防水性、防油性、耐候性及耐腐蚀性都较好。     

含氟丙烯酸酯聚合物的制备及应用研究

以含氟丙烯酸酯为主要单体制备了含氟丙烯酸酯聚合物,利用红外光谱和扫描电镜对制备的含氟丙烯酸酯聚合物进行了表征,研究了氟单体、链转移剂和功能单体的含量对含氟丙烯酸酯聚合物性能的影响,并用于石材表面防护,对防护后石材表面性能进行了测试,研究结果表明,经过含氟丙烯酸酯聚合物处理后石材表面具有优异的防水、防油和耐沾污、耐酸碱性能。     

含氟丙烯酸酯共聚乳液的制备及在织物上的应用

用139.21 g端基含氢的含氟醇、47.52 g丙烯酸和一定量的对甲苯磺酸和对苯二酚,回流反应10~12 h,得到含氟丙烯酸酯。含氟丙烯酸酯在复合乳化剂存在下进行乳液共聚,得到稳定的泛蓝光的三元共聚乳液。将其应用于纯棉、涤棉及电力纺3种织物的防水防油处理,防油性能得到明显改善,等级可达90~130。     

钛氟聚丙烯酸酯乳液的性能及应用

以纳米TiO_2(nano-TiO_2)、γ-甲基丙烯酰氧乙基三甲氧基硅烷(KH570)、全氟辛基乙基丙烯酸酯(FM)为主要原料,通过KH570改性纳米TiO_2后,与丙烯基单体共聚制得活性纳米TiO_2改性含氟聚丙烯酸酯复合乳液。通过FTIR、AFM及接触角测量仪表征共聚物的结构,测定了其性能。结果表明:改性纳米TiO_2、含氟单体均成功引入到聚丙烯酸酯共聚物中;乳胶粒呈球形分布,表面光滑且呈单分散状态,平均粒径为184 nm;与丙烯酸酯聚合物相比,改性后涂膜的粗糙度提高,有利于防水防油性能的提升。氟硅单体的加入使涂膜的接触角增大,对水和二碘甲烷的接触角分别为125°及110°,复合乳液用作表面施胶剂对纸张进行测试后,纸张对水接触角为147°,对二碘甲烷接触角为133°,纸张防水防油性随着氟单体的引入而显著增加。     

活性纳米TiO2改性含氟聚丙烯酸酯复合乳液的性能及应用

以纳米TiO2 (Nano-TiO2)、-甲基丙烯酰氧乙基三甲氧基硅烷(KH570)、全氟辛基乙基丙烯酸酯（FM）等为主要原料,通过KH570改性纳米TiO2后,与丙烯基单体共聚制得了活性纳米TiO2改性含氟聚丙烯酸酯复合乳液。通过红外光谱（FT-IR）、原子力显微镜（AFM）及接触角测量仪等手段研究了共聚物的结构及性能。结果表明：改性纳米TiO2、含氟单体均成功引入到聚丙烯酸酯共聚物中;乳胶粒呈球形分布,表面光滑且呈单分散状态,平均粒径为184nm;与丙烯酸酯聚合物相比,改性后涂膜的粗糙度提高,有利于防水防油性能的提升。氟硅单体的加入使涂膜的接触角大大增加,对水和二碘甲烷的接触角分别为125°及110°, 复合乳液用作表面施胶剂对纸张进行测试后,纸张对水接触角为147°,对二碘甲烷接触角为133°,纸张防水防油性随着氟单体的引入而显著增加。     

含氟聚丙烯酸酯皮革涂饰剂的制备及性能

以丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯为原料,甲基丙烯酸十三氟辛酯为含氟单体,过氧化苯甲酰为引发剂,通过自由基溶液聚合法合成了含氟聚丙烯酸酯,并研究了其涂膜的表面性能。结果表明:氟单体质量分数为25%,引发剂质量分数为1.0%,在反应后期一次性加入含氟单体,所制含氟聚丙烯酸酯于150℃固化20 min,其涂膜表面与水和油(正十六烷)的接触角分别为114.1°,63.5°;将其涂在皮革表面可使皮革表面的防水等级从1级提升至8级,防油等级从0级提升至5级,且涂膜在250℃以下具有良好的热稳定性。     

氧杂含氟单体类聚合物织物防水防油剂的合成与应用

以氧杂含氟单体1,1-二氢-2,5-二(三氟甲基)-3,6-二氧杂-全氟-1-壬醇丙烯酸酯和1,1-二氢-2,5-二(三氟甲基)-3,6-二氧杂-全氟-1-壬醇烯丙基醚为防水防油功能单体,采用预乳化-均质-细乳液聚合的工艺制备了防水防油剂.测试结果表明,乳液稳定、性能优良,防水可达4.5级,防油可达3级;染整工厂应用试验表明,使用过程中无恶性泡沫与粘滚现象,用量少、成本低.该乳液不会产生持久性污染物,清洁、环保,符合防水防油剂乳液的发展方向.     

含氟丙烯酸酯共聚物乳液的制备及复配研究

溶液型含氟丙烯酸酯共聚物在使用中会产生环境污染，近年来人们更加重视乳液型含氟丙烯酸酯共聚物的开发和应用，常采用的方法有2种：通过乳液聚合将含氟丙烯酸酯单体和其他烯类单体共聚，以及将含氟丙烯酸酯聚合物乳液和其他乳液通过共混和偶联进行复配，本文对这2种方法进行了综述。     

含氟聚丙烯酸酯防水防油剂的合成及性能研究

以全氟辛酸和全氟辛基磺酰氟为原料，合成了六种含氟丙烯酸酯单体，并进行了溶液聚合和乳液聚合。研究了聚合反应中各种因素对产品性能的影响，测试了产品的防水防油性，与国外同类产品性能进行了比较，提出了含氟单体与非氟单体共聚时降低含氟单体用量，从而降低有机氟防水防油剂成本的途径。     

含氟聚（甲基）丙烯酸酯乳液的研究进展

含氟聚(甲基)丙烯酸酯乳液具有合成简便和性能易调等优点,所得涂膜表面能低、耐污性能好、化学稳定性优异,因而在水性氟碳涂料领域受到广泛关注。含氟聚(甲基)丙烯酸酯单体的化学组成对乳液和涂膜性能影响很大。该文分类总结了含氟核心单体包括含氟烷基(甲基)丙烯酸酯、含氟杂原子(甲基)丙烯酸酯、含氟芳香(甲基)丙烯酸酯、含氟(甲基)丙烯酰胺和含氟磺酰胺(甲基)丙烯酸酯等的结构与乳液和涂膜性能的关系,然后对含氟聚(甲基)丙烯酸酯单体和乳液的合成方法进行归纳,最后简要介绍含氟聚(甲基)丙烯酸酯乳液的应用,并对乳液研究存在的问题和未来的发展方向进行展望。     

含氟丙烯酸酯共聚物的制备及性能

自制含氟丙烯酸酯单体与其他丙烯酸酯分别以溶液聚合和乳液聚合制得含氟丙烯酸酯溶液共聚物(Ⅰ)和乳液共聚物(Ⅱ),并与不含氟的丙烯酸酯共聚物(Ⅲ)性能进行了对比:Ⅰ在水中浸泡96h后涂膜完好,Ⅲ剥离;Ⅱ在水中浸泡24h后吸水率为12 01%～13 65%,Ⅲ为24 87%;Ⅰ、Ⅱ分别在丙酮和w(NaOH)=5%的水溶液中浸泡24h,涂膜基本完好,Ⅲ则剥离、破裂或溶解;w(氟单体)=5%时以KH-570改性Ⅰ并按上述方法测试性能,涂膜完好,硬度由HB提高到H;Ⅰ与水的平均接触角为62 1°～68 4°,Ⅱ为53 9°～61 0°,Ⅲ为29 1°～30 5°,KH-570改性Ⅰ后为63 4°～67 3°。上述结果表明:含氟共聚物涂膜的耐水性、耐碱性、耐溶剂性和自洁性均优于不含氟的共聚物,且含氟单体与KH-570具有良好的协同作用。     

Preparation and characterization of silica sol/fluoroacrylate core–shell nanocomposite emulsion

The silica sol/fluoroacrylate core?Cshell nanocomposite emulsion was successfully synthesized via traditional emulsion polymerization through grafting of KH-570 onto silica particles. Comparing the performance of the polyacrylate copolymer, the fluorinated polyacrylate copolymer and the silica sol/fluoroacrylate core?Cshell nanocomposite emulsion, we can come to a conclusion that the silica sol/fluoroacrylate core?Cshell nanocomposite emulsion presents significantly excellent performance in all aspects. The products were characterized by Fourier transform infrared (FTIR), photon correlation spectroscopy (PCS), transmission electron microscopy (TEM), thermogravimetry (TGA), Contact angle and UV?Cvis analyses techniques. The chemical structure of polyacrylate copolymer, fluorinated polyacrylate copolymer and silica sol/fluoroacrylate nanocomposite were detected by FTIR. The size and stability of emulsion latex particles were determined by PCS technique. TEM analysis confirmed that the resultant latex particle has the core?Cshell structure, obviously. The water absorption and contact angle data also showed that the silica sol/fluoroacrylate nanocomposite film has good hydrophobic performance. TGA analysis indicated the weight loss of the silica sol/fluoroacrylate nanocomposite film begins at around 350?°C which testifies its good thermal stability. The UV?Cvis spectroscopy analysis showed that the silica sol/fluoroacrylate nanocomposite film possess UV?Cvis shielding effect when the added volume amount of KH570 modified silica sol is up to 5?mL. Therefore, the excellent properties of hydrophobicity, thermodynamics and resistance to ultraviolet provide the silica sol/fluoroacrylate nanocomposite film with potential applications in variety fields. In addition, the formation mechanism of core?Cshell structure silica sol/fluoroacrylate nanocomposite latex particles was speculated.     

改性苯乙烯-丙烯酸酯防水防油剂的研究

以甲基丙烯酸十二氟庚酯(FM)、丙烯酸丁酯(BA)、苯乙烯(St)、甲基丙烯酰氧乙基三甲基氯化铵(DAC)、丙烯酸十八酯(ODA)为原料,采用无皂乳液聚合,制得了阳离子含氟丙烯酸酯多元共聚物乳液,并对聚合物的结构、组成进行了表征,研究了引发剂、FM的用量对乳液耐水性和稳定性的影响。单独使用含氟乳液对纤维类织物进行表面涂敷,水和油滴在织物上所成的接触角最大可分别达到135°和87°,同时织物的抗张强度、耐折度、平滑度分别提高13.45%、15.38%和60.52%。     

甲基丙烯酸甲酯-甲基丙烯酸三氟乙酯共聚物细乳液的合成及其表征

以甲基丙烯酸甲酯(MMA)和甲基丙烯酸三氟乙酯(TFEMA)为反应单体进行细乳液聚合,制得了MMA-co-TFEMA共聚物乳液。利用FTIR和GPC表征了共聚物的结构和分子量,采用激光光散射法及透射电镜对乳胶粒子的粒径大小及形貌进行了表征,并通过接触角法对共聚物膜的表面性能进行了研究。结果表明,与常规乳液相比,以细乳液方法制得的MMA-co-TFEMA共聚物乳液稳定性好,粒径分布窄,聚合物的分子量分布窄,并且共聚物膜随着氟含量的增加疏水疏油性增强,表面能降低。     

高抗水水性丙烯酸酯乳液的合成、表征及其在工业滤纸中的应用

以十二烷基硫酸钠(SDS)和OP-10为复合乳化剂,丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)、甲基丙烯酸十二氟庚酯(FA)为主要原料,采用预乳化半连续种子聚合法制备具有核壳结构的高抗水性丙烯酸共聚乳液。利用红外光谱、扫描电子显微镜、透射电子显微镜、接触角仪等对乳液及浸渍滤纸进行了表征;同时,讨论了核壳单体配比、乳化剂用量、引发剂用量以及含氟单体用量对反应与浸渍滤纸耐水性能的影响。结果表明,优化反应条件后,硬单体MMA配以适量FA单体为壳,制备的共聚乳液稳定性好,粒度均匀,具有明显球状和核壳结构。乳胶膜表面能随着含氟量的增加大幅度降低,当氟单体含量为16.3%时,其表面能降至19.9 m N/m。利用功能氟单体包覆于核层外表,当氟单体含量为4.7%时,原乳胶表面能从37.7 m N/m降至24.6 m N/m,所浸渍滤纸耐水性能明显优于不含氟乳液浸渍滤纸,达到"低氟高效"的效果。     

硅溶胶/含氟聚丙烯酸酯复合乳液的制备与表征

采用经典的St(o)ber法在常温下制备纳米级硅溶胶,用3-(甲基丙烯酰氧)丙基三甲氧基硅烷对其改性.在阴离子乳化剂和非离子乳化剂共同存在下,通过乳液聚合制备了硅溶胶/含氟聚丙烯酸酯复合乳液.表征了乳胶粒形貌,测试了共聚物组成及性能、乳液稳定性和乳胶膜性能.结果表明:乳胶粒有明显的核壳结构,乳液有良好的储存稳定性、稀释稳定性、高温和低温稳定性;硅溶胶/含氟聚丙烯酸酯复合乳胶膜吸水率达12.50％,对水的接触角为93 5°;复合物的热稳定性高于普通聚丙烯酸酯共聚物和含氟聚丙烯酸酯共聚物.     

Convenient method for removing and concentrating hydrophobic organic compounds from water with amphiphilic polymers

A stable fluoroacrylate copolymer emulsion was successfully prepared by miniemulsion polymerization with fluoroacrylate, lauryl methylacrylate, and methyl methacrylate as monomers. Extremely hydrophobic fluoroacrylate, instead of conventional cosurfactants, was used as a reactive cosurfactant to stabilize the miniemulsions. The results indicated that fluoroacrylate retarded Ostwald ripening and allowed the production of stable miniemulsions. The chemical compositions of the copolymer were studied with Fourier transform infrared and ¹H‐NMR. The average composition of the copolymers prepared with miniemulsions was in good agreement with the feed ratio according to ¹H‐NMR from the integration ratios corresponding to typical protons of the individual monomers. The particle size distribution and morphology of the latex particles were determined with laser particle analysis and transmission electron microscopy. The particle size of the latex underwent no change in the process of miniemulsion polymerization, but the particle size distributions were broader than those of conventional emulsion polymerization. The effects of various reaction parameters, including the temperature and concentrations of the emulsifier and initiator, on the miniemulsion polymerization were also investigated, and the polymerization rate and conversion increased with increasing concentrations of nonylphenol polyethoxylate (with an average of 40 ethylene oxide units per molecule), cetyltrimethylammonium, and 2,2′‐azobisisobutyronitrile. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 641–647, 2007     

Synthesis and analysis of properties of a new core–shell silicon‐containing fluoroacrylate latex

BACKGROUND: Silicon‐containing fluoroacrylate copolymers are potential materials for use in the protection of ancient stone buildings. In the work reported in this paper, a new core–shell silicon‐containing fluoroacrylate latex was prepared through grafting of a fluoroacrylate copolymer latex with polysiloxane. RESULTS: The core–shell silicon‐containing fluoroacrylate latex was successfully synthesized by seed emulsion polymerization and octamethylcyclotetrasiloxane (D₄) ring‐opening polymerization in the presence of a mixed emulsifier consisting of a non‐ionic emulsifier and a novel fluorine‐containing anionic emulsifier sodium perfluoro‐octane sulfonate. Transmission electron microscopy, X‐ray photoelectron spectroscopy, static contact angle measurements and scanning electron microscopy‐energy dispersive X‐ray analysis showed that when the D₄ content was controlled at 2.84–4.36 wt%, the silicon‐containing fluoroacrylate latex presented a uniform sphere core‐shell structure and had strong hydrophobic and oleophobic characters due to the association of both fluorine and silicon atoms on the latex film surface. The film cross‐section exhibited uniform and dense microstructure without any phase segregation. Additionally, thermogravimetric analysis and tensile test results indicated that all the silicon‐containing fluoroacrylate copolymers displayed better thermal stability and higher flexibility. CONCLUSION: The synthetic core–shell silicon‐containing fluoroacrylate latex showed excellent surface properties, thermal stability and flexibility, and has encouraging prospects in application as a protective coating. Copyright © 2009 Society of Chemical Industry     

反相乳液法淀粉丙烯酰胺接枝共聚反应的研究

以木薯淀粉为主要原料,研究了淀粉/丙烯酰胺单体/乳化剂/油/水反相乳液体系的接枝共聚反应规律,考察了反应温度、引发剂和乳化剂浓度、淀粉单体比、油水比等因素对淀粉接枝丙烯酰胺共聚反应过程的影响,并对反应机理进行了探讨.结果显示：在本实验考察范围内引发剂浓度、单体淀粉比、反应温度影响显著;乳化剂用量和油水比对反相乳液体系的形成及稳定有重要的影响;淀粉与亲水性单体丙烯酰胺的接枝共聚反应为淀粉团粒表面控制.