聚含氟丙烯酸酯/聚氨酯共聚物细乳液的制备及表征

以甲苯二异氰酸酯(TDI)和甲基丙烯酸羟乙酯(HEMA)为原料,合成了丙烯酸酯/聚氨酯(PUA)预聚体;采用细乳液聚合法,合成了聚含氟PUA细乳液。使用红外光谱(FT-IR)和核磁共振(1H-NMR)表征了PUA预聚体及共聚物的结构组成,用激光光散射粒度仪(PCS)分析了乳胶粒的粒径及其分布,并考察了氟单体用量对乳胶膜的吸水率和表面性能的影响。研究结果表明,乳胶粒的粒径随着PUA预聚体用量的增加而增大;当氟单体质量分数由0增至20%时,乳胶膜的吸水率由10.3%降至4.2%,表面自由能由34.89mJ/m2降至15.66mJ/m2,说明氟单体的加入较好地改善了乳胶膜的表面性能。     

细乳液聚合制备含氟丙烯酸酯聚氨酯共聚物

采用细乳液聚合法,制备了稳定的含氟丙烯酸酯聚氨酯细乳液。用FT-IR表征了丙烯酸酯聚氨酯预聚体及其共聚物的结构组成;考查了细乳液的稳定性;用透射电子显微镜(TEM)观察了乳胶粒的形态;用接触角法表征了乳胶膜对水和正十六烷的接触角。     

细乳液聚合法制备含氟丙烯酸酯共聚物乳液的研究

通过细乳液聚合法制备含氟丙烯酸酯共聚物（FPA）乳液,采用红外光谱（ FT-IR）、透射电镜（TEM）、原子力显微镜（AFM）、热重分析仪（ TG）、扫描电镜和表面能谱（ SEM-EDS）等对聚合物进行表征,并考察了乳化剂与助乳化剂的物质的量比,氟单体用量和超声时间对乳液粒径的影响。结果表明,甲基丙烯酸六氟丁酯（ 6FA）、丙烯酸丁酯（ BA）、苯乙烯（ St）3种单体成功聚合,乳化剂与助乳化剂的物质的量比为 1.5∶1,超声时间为 60 min,氟单体用量为 10%时,乳液粒径最小且分布较窄,表面张力从 45.028 mN/m降至 33.399 mN/m,且乳胶膜粗糙度增加,热稳定性提高。     

PVA作用下含氟丙烯酸酯共聚乳液的制备与表征

以聚乙烯醇(PVA)为乳化剂,采用Fe2+-H2O2引发体系,以全氟烷基乙基甲基丙烯酸酯(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(DMC)、丙烯酸羟乙酯(HEA)为主要单体进行乳液聚合,制得了阳离子含氟丙烯酸酯多元共聚物乳液。通过FTIR、1HNMR、透射电镜(TEM)、示差扫描量热(DSC)及接触角测试对共聚物结构、乳胶粒径及形态、乳胶膜表面性能进行了研究。结果表明,该乳液的粒子形态呈球形,单分散性良好,平均粒径为90～100nm;随着共聚物中含氟单体质量分数的增加,乳胶膜的表面自由能显著降低;退火处理有助于含氟基团迁移到乳胶膜表面,乳胶膜表面自由能进一步降低。     

含氟丙烯酸酯共聚乳液的制备及表征

以甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）等为主要单体,丙烯酸全氟烷基酯（Zonyl TM）为含氟单体,甲基丙烯酸羟乙酯（HEMA）为交联单体,采用种子乳液聚合法制备了含氟丙烯酸酯共聚物乳液。研究了Zonyl TM、HEMA、引发齐（APS）用量、复合乳化剂（SDS/OP—10）、聚合温度、聚合时间和搅拌速度等因素对聚合反应最终转化率、耐水性和乳液稳定性的影响。制备的乳液单体总转化率高,乳液凝聚率低,聚合反应稳定,涂膜的综合性能优良。此外,含氟乳胶膜对水的接触角及TG分析结果表明,Zonyl TM有效参与了共聚反应,提高了涂膜的耐水性及耐热性。     

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。     

自交联含氟丙烯酸酯共聚物乳液的制备

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)等为主要单体,甲基丙烯酸六氟丁酯(HFMA)为含氟单体,N-羟甲基丙烯酰胺(NMA)为交联单体,采用种子乳液聚合法制备了自交联含氟丙烯酸酯共聚物乳液。研究了HFMA、NMA、复合乳化剂(SDS OP-10)、引发剂(KPS)用量、聚合温度、聚合时间和搅拌速度等因素对聚合反应最终转化率和乳液稳定性的影响,结果表明在m(MMA)∶m(BA)=1∶1及搅拌速率210 r/min条件下,HFMA、NMA、SDS OP-10和KPS加入量分别为总单体量的7%、3%、3%和0.5%(均为质量分数),以及聚合温度75℃、反应时间4 h时,制备得到的乳液单体总转化率高,乳液凝聚率低,聚合反应稳定,涂膜的综合性能优良。此外,含氟乳胶膜的FT-IR及TG-DSC分析结果表明,HFMA有效地参与了共聚反应,提高了涂膜的耐热性。     

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。     

浅谈含氟丙烯酸酯共聚乳液研究进展

介绍了含氟丙烯酸酯的性能和用途,对含氟丙烯酸酯共聚乳液常规乳液聚合以及最新共聚方法进行了简单的介绍,总结出几种改进含氟丙烯酸酯体系表面性能的方法,并展望氟丙烯酸酯发展。     

AGET-ATRP制备三元含氟丙烯酸酯乳液及表征

用电子活化再生原子转移自由基聚合(AGET ATRP)方法,在乳液体系下合成了设定化学结构的甲基丙烯酸甲酯(MMA)-丙烯酸丁酯(BA)-甲基丙烯酸三氟乙酯(TFEMA)的三元共聚物;并通过GPC、FTIR及1H-NMR谱表征了共聚物相对分子质量和结构组成;系统研究了聚合条件对含氟丙烯酸酯共聚合物产率的影响.结果表明:含氟丙烯酸酯可以用AGET ATRP体系实现乳液体系的聚合;目标产物符合AGET ATRP的反应机理,所合成的聚合物分子结构可控且相对分子质量分布较窄(PDI=1.42).     

Preparation of fluoroacrylate nanocopolymer by miniemulsion polymerization used in textile finishing

Latex based on fluoroacrylate (TAN) and other comonomers was prepared via miniemulsion polymerization in the presence of stearyl trimethyl ammonium chloride (STAC) and 2, 2′‐azobis (2‐amidinopropane) dihydrochloride (ABAP) as a water soluble initiator. Light transmittance studies demonstrated that the light transmittance of prepared emulsions increases with the amount of TAN, STAC, cosolvent DPM, and hydrophobe DM. Given suitable reaction temperature and quantities of TAN, STAC, DPM, and DM, a copolymer emulsion of fluoroacylate with a particle size of 50 nm was produced. The water repellency tested on polyester fabrics displayed greater effectiveness than that of commercial products with higher fluorine content. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1466–1472, 2004     

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。     

细乳液聚合制备聚丙烯酸酯共聚细乳液的研究

以正十六烷为助稳定剂,十二烷基硫酸钠为乳化剂,采用细乳液聚合法合成了聚丙烯酸酯共聚乳液.研究结果表明,当乳化剂质量分数为3%,助稳定剂质量分数为2%时,乳液粒子平均粒径为89.5 nm,乳液稳定性好.成膜后综合性能优异.此外,在聚合体系中引入2%的交联剂N-羟甲基丙烯酰胺,胶膜的耐水性和拉伸强度有显著的提高.     

通过细乳液聚合方法制备自交联型有机硅乳液

苯乙烯与甲基丙烯酸-3-三甲氧基硅丙酯(M PS)经细乳液聚合,制得了稳定的自交联型的水分散涂料,用透射电子显微镜(TEM)、动态光散射仪(DLS)和红外光谱(IR)表征了乳胶粒的形态和结构。发现与传统乳液聚合相比,细乳液聚合法可显著提高乳液的稳定性,且M PS加入量的增加会导致乳液稳定性降低。     

细乳液聚合纳米乳胶荧光颜料的制备

采用细乳液聚合法制备了纳米乳胶荧光颜料,研究了溶剂黄43用量,乳化剂、助乳化剂种类和用量,引发剂用量和超声波处理时间对纳米乳胶荧光颜料性能的影响。结果表明,纳米乳胶荧光颜料较佳的制备工艺为:溶剂黄43、十六烷(HD)和过硫酸铵(APS)的质量分数分别为1.5%、1.5%和0.8%(以单体质量计),乳化剂1-烯丙氧基-3-(4-壬基苯酚)-2-丙醇聚氧乙烯(10)醚硫酸铵(DNS-86)用量为0.019 11 mol/L,超声波处理时间9 min,在该条件下制备的纳米乳胶荧光颜料的粒径为162.1 nm,具有较高的耐热和离心稳定性,纳米乳胶荧光颜料的最大荧光发射波长517 nm,最大吸收波长425 nm。     

Preparation and characterization of trilayer core–shell polysilsesquioxane–fluoroacrylate copolymer composite emulsion particles

Polysilsesquioxane–fluoroacrylate copolymer [poly(methyl methacrylate)–butyl acrylate–dodecafluoroheptyl methacrylate)] (FPSQ) composite latex particles with a trilayer core–shell morphology were manufactured by seeded emulsion polymerization, where PSQ latex particles bearing reactive methacryloxypropyl moieties were first produced by the hydrolysis‐condensation of (3‐methacryloxypropyl)trimethoxysilane, and then they were utilized as seeds, with methyl methacrylate, butyl acrylate, and dodecafluoroheptyl methacrylate as the inner and outer shell monomers. Fourier‐transform infrared spectra and ¹H‐NMR confirm the structure of the FPSQs. Transmission electron microscopy and scanning electron microscopy demonstrate that the obtained composite emulsion particles emerge with the trilayer core–shell pattern. Due to the anchoring of PSQ nanoparticles, the thermal stabilities of the FPSQ films are strengthened, and the resistance to heat is gradually improved along with the increase of the fluoroacrylate dose in the polymer matrix composite. X‐ray photoelectron spectroscopy, atomic force microscopy (AFM), and hydrophobicity investigations indicate that the fluorinated chain segments tend to concentrate at the film–air two‐phase interface. In addition, the AFM result denotes that importing more fluorine into the FPSQ hybrid material will engender greater phase separation and enrichment of the fluoroalkyl segments and a rougher morphology. Thus, the water contact angle of the FPSQ film can ultimately reach 121.4°. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44845.     

Preparation of nanocomposite dispersions based on cellulose whiskers and acrylic copolymer by miniemulsion polymerization: Effect of the silane content

A one‐step method was used to prepare stable aqueous nanocomposite dispersions based on cellulose whiskers extracted from the rachis of the date palm tree and a poly(styrene‐co‐2‐ethyl hexylacrylate) copolymer via miniemulsion polymerization. A reactive silane, i.e., methacryloxypropyl triethoxysilane was added to stabilize the dispersion and favor the anchoring of the whiskers on polymer particles. Dynamic light scattering was used to study the effect of the silane and whiskers contents on the average particle size of the polymer. Nanocomposites materials were prepared from these dispersions using a casting/evaporation method. The effect of the silane and whiskers contents on the thermal and mechanical properties were studied using differential scanning calorimetry and dynamic mechanical analysis. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Molecular characterization of alkyd/acrylic latexes prepared by miniemulsion polymerization

The molecular characterization of alkyd/acrylic hybrid latexes produced by miniemulsion polymerization was characterized in terms of the resin degree of grafting, acrylic degree of grafting, reacted double bonds in the alkyd, gel content, and molecular weight distribution of the sol part. A simple method based on conventional size exclusion chromatography measurements was developed to estimate the fraction of alkyd resin grafted to the acrylic polymer. The method could be applied to completely soluble hybrids and to hybrids containing gel. Also, the limits of the extraction method used in the literature to estimate the fraction of acrylic polymer grafted to the alkyd was investigated; we found that this technique only provided accurate results at high values of the acrylic degree of grafting. The combination of this information with the reacted double bonds of the alkyd (determined by iodine titration) and the molecular weight distribution of the sol polymer provided a detailed characterization of the alkyd–acrylic hybrid polymer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009