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°。     

不同粒径含氟丙烯酸酯共聚乳液的合成及膜表面疏水性能研究

采用半连续种子乳液聚合的方式,以丙烯酸丁酯、甲基丙烯酸甲酯和甲基丙烯酸六氟丁酯为原料制备了粒径分别为30nm、75nm、210nm左右的含氟丙烯酸酯共聚物乳液。通过乳胶粒核壳结构设计与大小粒径乳液机械共混改性2种方法研究了如何在较少含氟单体用量的情况下达到较好的表面疏水性能。利用X射线光电子能谱、动态光散射仪、接触角测定仪等分析手段,研究了共聚物膜的表面性能和共聚物乳液粒径的大小及分布,测试结果表明,核壳结构乳液成膜后壳层含氟量较高,膜表面接触角大于90,°疏水性能强;而大小粒径乳液共混物成膜后表面含氟量较低,却仍能得到90°以上的接触角,表明乳胶膜表面具有粗糙结构,具有一定的仿荷叶效应。     

核壳型纳米SiO2/含氟聚丙烯酸酯复合乳液的合成与表征

采用原位乳液聚合法,在可聚合阴离子乳化剂/非离子乳化剂复配体系下,以γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH-570)改性的纳米SiO2、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、丙烯酸(AA)等为核相组成,以MMA、BA及甲基丙烯酸十二氟庚酯(DFMA)为壳相单体,合成纳米SiO2/含氟聚丙烯酸酯复合乳液.考察了纳...     

Manipulation of chain transfer agent and cross-linker concentration to modify the performance of fluorinated acrylate latex pressure sensitive adhesive

Abstract

n-Dodecyl mercaptan (DDM) chain transfer agent and 1,6-hexanediol diacrylate (HDDA) cross-linker were used to manipulate latex properties in a monomer-starved seeded semi-continuous emulsion polymerization of butyl acrylate (BA), fluorine monomer dodecafluoroheptyl methacrylate (DFMA) together with acrylic acid (AA) and 2-hydroxyethyl acrylate (HEA). The influences of both DDM and HDDA on the particle size of the latex, as well as on the gel content, thermostability (differential scanning calorimeter and thermal gravimetric analysis), surface properties (X-ray photoelectron spectra (XPS), contact angle analysis and atomic force microscopy), and viscoelasticity (N,N-dimethylacrylamide) of the polymer films were investigated. The results showed that the introduction of DDM and HDDA has no significant effects on the final particle size of the fluorinated pressure-sensitive adhesives (PSA) latexes. XPS analysis indicated that the fluoroalkyl groups had the tendency to enrich on the surface of the film. However, this enrichment of fluorine on the film surface was reduced after the introduction of HDDA, while increased with the addition of DDM. It was also found that the gel content, glass transition temperature (T_g), thermal stability, surface roughness, and modulus (G′, G?) of the fluorinated latex PSA were all increased with the introduction of HDDA. Nevertheless, opposite trends were observed for the latex after the addition of DDM. Finally, the effects of DDM and HDDA on the adhesive properties (i.e. loop tack, peel strength and shear strength) of the fluorinated latex PSA were also evaluated.     

Preparation of fluorinated polyacrylate composite latex with in situ generated nano-silica dispersion and film durability

Nano-silica dispersion was generated in situ through the hydrolysis and condensation of tetraethyl orthosilicate with methyl methacrylate and butyl acrylate in micelles as dispersing media, hydrochloric acid as catalyst and methacryloxypropyl trimethoxysilane as modifier. Then, the nano-silica/fluorinated polyacrylate composite latexes were prepared via emulsion polymerization directly using the in situ generated nano-silica dispersion as seeds. Dodecafluoroheptyl methacrylate (DFHMA) as functional monomer was incorporated into shell layer of the composite particles by semi-continuous starved condition at the second stage. Fourier transform infrared spectroscopy indicated that silica was generated in situ and DFHMA took part in the copolymerization. Transmission electron microscopy showed uniform composite latex particle morphology and obvious core–shell structure. Dynamic light scattering demonstrated that DNS-86 could control the composite latex particle size ranging from 90 to 180 nm. DFHMA had an important effect on the particle size. Zeta potential (ζ) revealed that the composite latex had good stability. The resulted composite films were characterized by angle-resolved X-ray photoelectron spectroscopy, contact angle measurements and thermo-gravimetric analysis. The well-tailored composite latex particle structure of nano-silica core and fluorinated polyacrylate can effectively improve the hydrophobicity of the resultant films. Water contact angle could reach 123.5° when 6 wt% DFHMA was incorporated in the film. Moreover, water contact angles remained 106° after water immersion in the range of the experimental sample films. In addition, the incorporation of fluorinated monomer and nano-silica contributed to the improvement of thermal stability of the composite film.     

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。     

Synthesis and characterization of fluorinated polyacrylate latex emulsified with novel surfactants

The fluorinated polyacrylate latex were successfully prepared with semi- continuous seeded emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA) and hexafluorobutyl methacrylate (HFMA) which was initiated with potassium persulfate (KPS) initiator and emulsified with the novel mixed surfactants of sodium lauryl glutamate (SLG) and alkylphenol ethoxylates (OP-10). The structure of the resultant latex was confirmed by Fourier transform infrared spectroscopy (FTIR). The particle size of the latex was measured by Zetatrac dynamic light scattering detector. The film of latex was tested by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and contact angle (CA). The optimum conditions of preparing the novel fluorinated polyacrylate latex are optimized and the results are as follows: the amount of emulsifiers is 4.0%; mass ratio of SLG to OP-10 is 1:1, the amount of the initiator is 0.6%. The mass ratio of MMA to BA is 1:1 and the amount of HFMA is 7.0%. In this case, the conversion is high and the polymerization stability is good. In addition, the water resistance and thermal properties of the latex films were improved significantly in comparison with the film of the latex prepared without the fluorinated monomer.     

Surface immobilisation of fluorinated polystyrene‐acrylate latex nanoparticles with core–shell structure by crosslinking

Fluorinated polystyrene‐acrylate (PSA) latex nanoparticles with core–shell structure were synthesised by two‐stage seeded emulsion polymerisation method in the presence of reactive emulsifier DNS‐86. Diallyl phthalate (DAP) and Vinyltriethoxysilicone (VTES) were used as crosslinking agent to immobilise the fluorinated copolymer on the surface of the latex film. Fourier transform infrared spectroscopy (FTIR) spectra show that fluorine and siloxane monomers were effectively involved in the emulsion copolymerisation. Transmission electron microscope (TEM) observation shows that the prepared emulsion particles had a core–shell structure with fluorinated copolymer in the shell. X‐ray photoelectron spectroscopy (XPS) analysis reveals that fluorine atom has the tendency of migrating to the film–air interface and the incorporation of VTES helps the migration of fluorine atom towards the film–air interface. Water contact angle (WCA) test proved that DAP and VTES as crosslinking agent can immobilise the fluorinated copolymer on the surface of the latex films. © 2011 Canadian Society for Chemical Engineering     

一种含氟共聚物乳液的制备及其性能

通过制备一种含有全氟壬烯基的含氟共聚物乳液,并考察其性能,研究了含氟单体对共聚物乳液性能的影响。以K2S2O8为引发剂,丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)和全氟壬烯基烯丙基醚(PFNAE)为共聚单体,采用半连续乳液聚合的方法,制备了带蓝色荧光的含氟乳液。用傅里叶红外(FT-IR)、接触角、差示量热扫描(DSC)和热重(TG)分析等手段对制备的PFNAE-BA-MMA共聚物(PBM)结构和性能进行表征。结果表明:引入含氟单体后,聚合物的疏水性、热稳定性、玻璃化温度(Tg)都有提高。水在含氟共聚物上的接触角随含氟单体用量的增加而增大,当PFNAE占单体总质量的25%时,水的接触角为94.9°;当PFNAE占单体总质量的20%时,共聚物在221℃开始分解,429.5℃分解完全,该共聚物Tg为8.5℃。PFNAE-BA-MMA共聚物具有一定的拒水性和良好的热稳定性。     

环氧乳液与含氟乳液的拼混研究

运用种子乳液聚合法制备了固含量(固体质量分数)为45%的含氟乳液;运用后乳化法制得了环氧乳液。ATR-FTIR测试表明环氧乳液与含氟乳液进行了有效的拼混。运用KrussK12型动态表面能分析仪测试了含氟涂膜对水和十六烷的接触角,对影响拼混乳液涂膜性能的因素如环氧树脂及其固化剂的比例、氟原子含量、成膜基材材质、成膜温度等进行了探讨研究。结果表明制备的含氟拼混乳液性能良好。     

阳离子型含氟丙烯酸酯共聚乳液的微波辐射制备

在微波辐射下,以十八烷基三甲基氯化铵为乳化剂,2,2-偶氮2甲基丙基脒-二盐酸盐（AIBA）为引发剂,将丙烯酸丁酯（BA）、甲基丙烯酸甲酯（MMA）、甲基丙烯酸十二氟庚酯（GO-4）以及甲基丙烯酰氧乙基三甲基氯化铵（DMC）进行乳液聚合,成功制备了Zeta电位在315mV左右、粒径为55~75nm的阳离子型含氟丙烯酸酯乳液。通过测定乳胶膜中氟元素含量,发现微波辐射能提高含氟单体共聚效率,使乳胶膜中氟元素含量增加。用固含量1％的阳离子型含氟丙烯酸酯共聚物乳液处理棉布织物,结果发现,棉布对水和正十六烷的接触角可分别达到111．3°、60．6°,表面自由能降至1581mJ／m2,棉布的静态吸水时间可以超过4h。     

纳米SiO2/聚氨酯-含氟丙烯酸酯杂化乳液的合成与表征

采用种子乳液聚合法,以聚氨酯（PU）乳液为种子（在聚合过程中为壳相）,甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）、甲基丙烯酸十二氟庚酯（DFMA）和γ-甲基丙烯酰氧丙基三甲氧基硅烷（KH-570）改性的纳米SiO₂组成的混合物为核相,合成了具有核壳结构的纳米SiO₂/聚氨酯-含氟丙烯酸酯（SiO₂/FPUA）复合乳液。考察了纳米SiO₂和DFMA用量对乳液聚合过程及乳胶膜性能的影响。通过傅里叶红外光谱（FT-IR）、接触角（CA）、透射电子显微镜（TEM）、热重（TG）、差示扫描量热仪（DSC）和力学性能测试（MPT）等表征乳液的结构形态、乳胶膜的表面性能和综合性能。结果表明：乳胶粒子呈现“反相核壳”结构,以聚丙烯酸酯（PA）相为核,PU相为壳;由于纳米SiO₂和DFMA的协同作用,涂膜的疏水性和综合性能得到了较大的提高。     

Role of fluorinated monomer for simple demolding in nanoimprint lithography

In this study, we explored the effect of a fluorinated monomer on nanoimprint lithography (NIL) and determined the optimum amount of fluorinated monomer required in the formulation for better NIL. To estimate the role of the fluorinated monomer for demolding, NIL was conducted using copolymers of nonfluorinated silane monomers and fluorinated silane monomers. Epoxy ring‐opening photopolymerization based on the cationic polymerization mechanism was utilized for the NIL process. The physical properties of the photopolymerized copolymeric materials, such as tensile strength, elongation, modulus, and impact strength, as well as surface characteristics such as the contact angle were reported. Aluminum deposition on the nanoimprinted pattern, which is instrumental in fabricating a wire grid polarizer, was also conducted. According to the study results, the use of a copolymer containing 20 mol % of the fluorinated monomer in NIL proved to be the best formulation for easy demolding and for ensuring optimum levels of the physical properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41317.     

水性含氟丙烯酸酯核壳乳液的制备及性能研究

采用半连续乳液聚合法合成了以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)为成核单体,甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)和丙烯酸六氟丁酯(HF)为成壳单体的核壳型微乳液。通过TEM、SEM、FT-IR对乳液及乳液固化膜性能进行了表征;对乳液的稳定性做了测试,用接触角法对乳液固化膜表面性能进行了研究。结果表明:当含氟单体质量分数为19.34%时,核壳型结构粒子呈球形分布,乳液稳定性良好,成膜性较好,乳液固化膜的表面能为24.26 mJ/m2,与之相对应的无氟乳液固化膜的表面能为52.73 mJ/m2。根据本研究得出的原料、配方及工艺方法制备的乳液及其膜有较优的性能。     

聚氨酯改性氟代聚丙烯酸酯的合成及应用

将丙烯酸十二氟庚酯(FA),丙烯酸羟丙酯(HpAA)为单体,偶氮二异丁腈(AIBN)为引发剂在聚氨酯预聚体中进行聚丙烯酸酯自由基聚合,然后用丁酮肟(EtAO)进行完全封端,制得新型易去污整理剂聚氨酯改性氟代聚丙烯酸酯(FPUA).FPUA附着在纤维表面时纤维与空气的界面上富集着疏水的含氟链段,能使整理后棉织物与水的接触角达到146.5°,与油的接触角达到132°;当FPUA用量为1.5 g/100 mL H_2O,使用100℃烘5 min后180℃高温焙烘2 min的工艺时,疏水性达到95分,疏油等级6级,易去污可达到5级.     

Preparation and characterization of novel self cross‐linking fluorinated acrylic latex

Self crosslinking fluorinated acrylic latex (SCLFAL) has been successfully prepared via starved seeded semibatch emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA), 2‐(perfluoro‐(1,1‐bisisopropyl)‐2‐propenyl)oxyethyl methacrylate (POMA), and N‐methylolacrylamide (NMA). The resultant SCLFAL is characterized by Fourier transform infrared (FTIR) spectrometry and nuclear magnetic resonance (NMR). Influences of the added amount of NMA on the crosslinking degree, contact angle, particle size, and glass transition temperature (T_g) of the film are investigated. Results show that the crosslinking degree, contact angle, and T_g of the film can be improved when the moderate amount of NMA is introduced into the mixed monomers. However, the added amount of NMA has no marked effect on the particle size of SCLFAL. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of poly(fluorinated acrylate)/silica hybrid nanocomposites

The nanocomposite particles (NPs) with inorganic silica as core and fluorinated polymer shell have been in situ synthesized via emulsion polymerization. The chemical composition and core‐shell structure were characterized by Fourier‐transform infrared spectrometry and transmission electron microscopy. The results showed that silica nanoparticles were encapsulated in latex particles, with single‐ and multicore morphologies coexisting. Thermal gravimetric analysis also suggested the successful encapsulation of silica into NPs with enhanced thermal stability. The surface properties of the latex films produced from the core‐shell particles were also investigated by contact angle method and water absorption measurement. Both fluorinated polymer and silica contributed to less water absorption ratio and lower surface‐free energy, which was composed of larger polar component and smaller disperse component, just reversed as usual. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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。     

含氟丙烯酸酯共聚乳液合成及性能研究

以甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）和全氟烷基丙烯酸酯等为主要原料,丙二醇为分子量调节剂,采用非离子阴离子复合乳化剂、氧化还原引发体系、超声微乳化技术,不同的加料方式制备出系列含氟丙烯酸酯乳液,并利用衰减全反射红外光谱（ATR-FTIR）对含氟丙烯酸酯共聚乳液胶膜进行了表征。采用接触角测定方法研究了含氟共聚乳液对织物整理后的表面性能变化,结果显示：乳液整理后的纯棉无纺布的拒水拒醇性大大提高,对水的接触角达到127o左右,对醇的最大接触角达到112o。乳液整理后的PP无纺布拒醇性明显改善,接触角达到101o左右。但拒水性能未见明显提高。