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。     

聚合工艺条件对含氟涂膜表面性能的影响

运用种子乳液聚合法制备了较高性价比的含氟乳液。FTIR光谱和DSC测试表明,含氟单体参与了聚合反应。运用KrussK12型动态表面能分析仪,测定聚合工艺中以不同用量的乳化剂、引发剂、含氟单体、N 羟甲基丙烯酰胺(N MA)在不同的单体滴加速度下合成的乳液涂膜对水和十六烷的接触角,结果表明,w(乳化剂)=3 5%、w(引发剂)=0 45%、w(N MA)=4%、聚合物中x(F)=14%时,乳液涂膜对水和十六烷的接触角较佳,对水的接触角达115°,涂膜表现出良好的表面性能。     

丙烯酸酯化学改性含氟聚合物涂料的新进展

评述了两类丙烯酸酯化学改性含氟聚合物涂料的新进展,即氟化丙烯酸酯单体与不含氟单体的共聚物以及丙烯酸酯单体对含氟共聚物的改良物.指出今后的研究方向为提高高耐候性含氟聚合物涂膜的防粘污性能,发展可以在较短时间内有效预测此类涂料服务年限的方法,确定乳胶粒结构与单体间比率的关系.     

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。     

核壳型含氟丙烯酸酯乳液的合成及表征

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、甲基丙烯酸六氟丁酯(HFMA)等为主要原料,采用多步乳液聚合法,合成了具有核壳结构的含氟丙烯酸酯乳液。实验结果表明,主要单体质量比m(MMA)∶m(BA)=45∶55,核壳单体质量比为6∶4,含氟单体质量分数为7%,乳化剂质量分数为3%~4%时,制备得到的含氟丙烯酸乳胶粒子具有软核/硬壳结构,粒径为120 nm,乳胶膜吸水率为7%。通过傅里叶红外光谱法(FTIR)对乳液结构进行表征,结果表明,含氟单体参与了有效聚合;差示量热扫描(DSC)和热重分析法(TG)分析结果表明,聚合物存在两个玻璃化温度(-10.2℃和58.4℃),且热分解温度比不含氟的聚合物提高了59℃;接触角测试结果表明,当w(HFMA)≥7%时,乳胶膜正面与水的接触角为98.2,°说明所合成的核壳结构含氟丙烯酸酯乳液中有机氟富集于壳层,涂膜的耐热、疏水性良好。     

含氟丙烯酸酯共聚物的合成及其涂膜表面疏水、疏油性能研究

以单体甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、含氟(甲基)丙烯酸酯为原料,通过改变氟碳链长度、氟单体含量以及添加方式等因素,合成了一系列的含氟丙烯酸酯共聚物。利用表面接触角测试仪、红外光谱仪和多功能光电子能谱仪表征了共聚物涂膜的表面疏水、疏油性能以及表面化学成分,探讨了其影响因素。结果表明,共聚物涂膜表面疏水、疏油性能与其表面化学成分密切相关;使用长氟碳链的氟单体、增加氟单体用量以及采用在反应后期一次性加入氟单体的方法均有利于提高涂膜表面的疏水、疏油性能;当全氟辛基乙基甲基丙烯酸酯的质量分数为25%时,所得涂膜表面的氟元素质量分数达到44.284%,对水、对正十六烷的接触角分别达到127°和65°。     

含氟丙烯酸酯乳液的合成工艺研究

研究了工艺条件对含氟改性丙烯酸酯乳液的单体转化率的影响并优选出制备该改性乳液的最优方案。利用红外(FTIR)对涂膜进行了表征。结果表明,w(复合乳化剂)=4%,w(引发剂)=0.6%,w(有机氟)=6%,n(BA)/n(MMA)=46︰51,聚合温度为80℃时单体转化率最高,稳定性最好,乳胶膜疏水性好,具有较好的综合性能。     

双重改性耐高温丙烯酸酯压敏胶的制备

以丙烯酸酯单体为原料、KH-570(γ-甲基丙烯酰氧基丙基三甲氧基硅烷)和GH(水性多异氰酸酯)固化剂为改性剂,制备了高性能的耐高温丙烯酸酯PSA(压敏胶)乳液,并考察了KH-570掺量、GH掺量对PSA各项性能的影响。研究结果表明:随着KH-570掺量的不断增加,PSA乳液的粒径增大、凝胶率增多且储存稳定性变差,PSA胶膜的表面粗糙度和耐热性呈递增趋势;此外,随着GH掺量或KH-570掺量的不断增加,PSA的高温持粘力增大,但180°剥离强度和初粘力下降。当w(KH-570)=0.3%(相对于总单体质量而言)、w(GH)=0.7%(相对于PSA乳液质量而言)时,PSA的综合性能相对最好。     

丙烯酸酯乳液胶粘剂的合成及性能研究

以丙烯酸丁酯(BA)为软单体、甲基丙烯酸甲酯(MMA)为硬单体、丙烯酸(AA)为功能单体、过硫酸铵(APS)为引发剂、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)为改性剂和十二烷基硫酸钠(SDS)/烷基酚聚氧乙烯醚(OP-10)为阴/非离子型复合乳化剂,采用半连续种子乳液聚合法合成了丙烯酸酯乳液胶粘剂;然后采用单因素试验法优选出制备该胶粘剂的最优方案。研究结果表明:当m(BA)∶m(MMA)=4∶1、w(APS)=0.4%～0.5%、w(AA)=2%～3%和w(KH-570)=1.0%(均相对于共聚单体总质量而言)时,相应胶粘剂的粘接强度(剥离强度为123.4 N/m、拉伸剪切强度为0.49 MPa)相对最大、耐水性(吸水率为18.91%)相对较好。     

阳离子型丙烯酸/醇酸树脂乳液的制备及性能

以醇酸树脂(BTS-SZ)为原料,甲基丙烯酸二甲胺基乙酯(DM)、甲基丙烯酸甲酯(MMA)、丙烯酸正丁酯(BA)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)为单体,偶氮二异丁腈(AIBN)为引发剂,采用溶液转相乳液聚合法,制备了丙烯酸酯聚合物/醇酸树脂乳液(WPAARSi)。探讨了单体滴加时间、聚合温度、单体配比、BTS-SZ用量对WPAARSi涂膜光泽度及耐水性的影响。采用FTIR、TEM、GPC、TGA及镜向光泽度计等对聚合物进行了结构表征与性能测试。结果表明:当单体滴加时间为2 h、聚合温度为85℃、w(DM)=6%、m(MMA)∶m(BA)=18∶2、w(BTS-SZ)=55%、w(KH570)=0.62%、w(AIBN)=1.62%时,涂膜的光泽度为116%,吸水率为2.8%。GPC测试表明,改性后醇酸树脂的数均分子质量由1413提高到了2945,分布指数(PDI)由3.646提高至6.741;TGA测试表明,改性后醇酸树脂的热稳定性提高;流变行为分析表明,乳液具有良好的触变性。     

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.     

Synthesis of core‐shell fluoroacrylate copolymer latex via emulsion polymerization and its application in ink‐jet ink

Core‐shell fluoroacrylate copolymer latex was synthesized via semicontinuous seed emulsion polymerization, in which ethyl acrylate was utilized to prepare core, and methyl methacrylate, butyl acrylate, methacrylate acid, and hexafluorobutyl methacrylate were employed to constitute the shell. So the yielded latex particles had the soft core and hard shell. Multifunction and low viscosity of the latex had been applied as the binder of latex inks. The ζ potential showed that the latex particles had high thermodynamic stability. The latex and latex inks exhibited viscosity plateau of Newtonian fluid behaviors. Rheological tests revealed that viscous behaviors dominated in the latex and latex inks. However, there was some interaction among the latex and pigment particles. The hydrophobicity of the cast films of the latex increased with the amount of the fluoroacrylate monomer. Fluorine tended to migrate to the interface between the cast film and air. Therefore, the hydrophobicity was derived from the fluorine enrichment phenomena on the top side of the cast films. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

含氟硅丙烯酸酯核壳乳液及涂膜表面性能

在可聚合阴离子乳化剂体系下,以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)为主要单体,甲基丙烯酸十二氟庚酯(DFMA)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)为功能单体,采用半连续种子乳液聚合法合成了含氟硅丙烯酸酯核壳乳液。考察了DFMA和KH-570用量对乳液聚合过程和乳胶膜表面疏水性能的影响,并对乳胶膜的表面自由能进行了估算。采用傅里叶红外光谱(FT-IR)、差示扫描量热仪(DSC)、热重(TG)、接触角(CA)及X射线光电子能谱(XPS)对氟硅丙乳液及乳胶膜进行了表征。研究结果表明,氟硅单体有效地参与了聚合,乳胶膜中氟硅元素呈梯度分布,当氟硅丙乳液中DFMA和KH-570用量分别为16%和5%（质量分数）时,涂膜-空气界面与去离子水的接触角为110.6°,涂膜的表面能低至15.4 mN·m^-1,其疏水性和耐热性有较大幅度提高。     

硅烷偶联剂表面改性二氧化钛粒子超疏水性能研究

针对无机二氧化钛（TiO2）粒子在有机体系中的分散性问题,采用硅烷偶联剂KH-570对无机填料钛白粉（二氧化钛,TiO2）的表面进行有机化改性;并通过红外光谱（FT-IR）、接触角测试、沉降实验、扫描电子显微镜（SEM）等手段表征表面改性TiO2粒子的结构,测试其超疏水性能,分析超疏水表面形成的机理。结果表明,经KH-570表面改性的TiO2粒子的疏水性和分散性得到明显改善,当KH-570质量分数达到15%时,表面改性的TiO2涂层与水的静态接触角达152.5˚,表现出良好的超疏水性能。     

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.     

Polymerization of fluoroacrylate and guar gum copolymer as a new pretreatment paste for ink‐jet printing of polyester

A novel pretreatment paste containing fluoroacrylate copolymer and modified Guar Gum was carried out on the polyester fabric to provide partial water repellency and printability after inkjet printed with water‐based disperse dye inks. The stable fluorinated pastes were prepared via miniemulsion polymerization of fluoroalkyl acrylates, styrene, 2‐ethylhexyl acrylate, and modified guar gum in the presence of AIBN as initiator, CTAB and polyoxyethylene polyaryl ether as surfactants under suitable reaction conditions. In the analysis of monomer conversion and particle size, the highest polymerization rate with smallest particle size was obtained with increasing concentration of surfactants and initiator but the decreasing degree of substitution of guar gum to imply stronger interactions between fluoroacrylate monomers, hydroxyl groups of modified guar gum and EO units of nonionic surfactants. The 30% of stock fluorinated paste with urea concentration of 6% provided the prints with highest K/S value, satisfactory edge acuity and least color difference between front and back sides of the fabric to show more transparency. The rating 80 of water repellency tested on the best treated polyester fabric demonstrated stain proof properties after sprayed with water and dried. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

硅烷改性丙烯酸酯乳液性能研究

在水解抑制剂(YZ-1)的作用下,通过乳液聚合实现甲基丙烯酸甲酯(MMA),丙烯酸丁酯(BA)和γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)共聚,合成了硅丙乳液。研究了YZ-1和KH570用量对聚合过程和聚合物性能的影响。结果显示,当YZ-1用量2%,硅单体质量分数9%时,聚合过程稳定,共聚物具有较好的相容性,乳胶膜的吸水性由8.33%降至2.64%。     

含全氟壬烯基单体的合成与聚合

制备了1种含有全氟壬烯基的单体,与其他单体聚合得到含氟共聚物乳液.全氟壬烯(Ⅰ)和烯丙基(p-羟甲基苯基)醚(Ⅱ),在催化剂存在下得到含氟单体p-全氟壬烯基氧基苯酚烯丙基醚(Ⅲ)；以K2S2O8为引发剂,丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)和Ⅲ为共聚单体,采用乳液聚合的方法,制备了带蓝色荧光的含氟乳液.用傅立叶...     

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%。