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。     

A facile strategy for the fabrication of highly stable superhydrophobic cotton fabric using amphiphilic fluorinated triblock azide copolymers

Amphiphilic triblock azide copolymers containing poly(ethylene glycol) (PEG) and poly(2,2,3,4,4,4-hexafluorobutyl acrylate) blocks have been synthesized through room temperature RAFT polymerization using redox initiation and were successfully used to fabricate superhydrophobic cotton fabric by a facile approach. The copolymers were covalently attached to the surface of the cotton fabric by the reaction of azide groups with the cotton fibres based on nitrene chemistry via UV irradiation. Due to introducing the fluorinated polymer chains, the cotton fabric was transformed from hydrophilicity to superhydrophobicity with a water contact angle of 155°. Since the fluorinated polymer chains were covalently attached on the surface of the cotton fabric, the superhydrophobic cotton fabric possessed high stability and chemical durability.     

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°。     

Synthesis of Bis(1H, 1H, 2H, 2H‐perfluoro‐octyl)methylenesuccinate copolymers and their application on cotton fabrics

Bis(1H, 1H, 2H, 2H‐perfluoro‐octyl)methylenesuccinate (FOM)/ethyl acrylate (EA)/methyl methacrylate (MMA) copolymer (FOME) latexes, FOM/butyl acrylate (BA)/MMA copolymer (FOMB) latexes, and FOM/octyl acrylate (OA)/MMA copolymer (FOMO) latexes were synthesized by continuous emulsion polymerization. Solution polymerization was also carried out to prepare FOMB. The influences of fluorine content and curing conditions on the surface properties of polymer films were discussed. The water and oil repellency of cotton fabrics treated with the FOM copolymers was better than that of conventional poly(fluoroalkyl acrylate)s containing the same fluorinated chain. The polymer films or the treated fabrics were characterized by Fourier transform infrared, scanning electron microscope, atomic force microscopy, thermogravimetric analysis, x‐ray photoelectron spectrometry, and wide angle x‐ray diffraction. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci, 2013     

Phase separation structure and interfacial properties of lattice‐patterned liquid crystal–polymer composites prepared from multicomponent prepolymers

Lattice‐patterned liquid crystal (LC)–polymer composites are representative candidates for the practical application of LC materials in high‐quality flexible displays. In this work, multicomponent prepolymers are used for the fabrication of lattice‐patterned LC–polymer composites via photoinduced phase separation. Phase separation behavior between LC and polymer is closely related to the solubility parameter of acrylate monomers in the prepolymers. The lattice structure of polymer walls formed by photoinduced phase separation between LC and polymers is stoichiometrically controlled by the composition of acrylate monomers with various solubility parameters. However, unlike the polymer wall structure, it is impossible to control the LC–polymer wall interfacial properties just by altering the composition of the acrylate monomers. The interfacial properties are found to be predominantly affected by a specific component, a fluorinated acrylate monomer, in the prepolymers, and thus the anchoring energy of polymer walls is controlled by incorporation of the fluorinated acrylate monomer. By selecting an appropriate combination of acrylate monomers in the prepolymers, both the phase separation structure and driving properties of lattice‐patterned LC–polymer composites can be controlled simultaneously. © 2013 Society of Chemical Industry     

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。     

Synthesis and photosensitivity of acryloylmorpholine copolymers with a pendant (meth)acryloyl group

We have developed new photopolymers that have superior waterproof properties and that can easily interact with polyfunctional acrylate compounds, thus serving as hydrophobic photocrosslinking reagents. Acryloylmorpholine monomers whose homopolymers were less moisture absorbing than the usual water‐soluble polymers but were still water soluble to a good degree, were copolymerized with other acryloyl monomers. We then introduced the photosensitive (meth)acryloyl group to side chains of the resulting polymers. Among six copolymers examined, the copolymers composed of acryloyl morpholine, hydroxyethyl acrylate, ethyl, or methyl methacrylate, and methacryloyl isocyanate were found to have nicely balanced hydrophilicity and waterproof properties, in addition to good compatibility with hydrophobic photocrosslinking reagents. The composite polymers thus obtained were confirmed to be promising photopolymers usable even in a highly humid environment. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 684–692, 2003     

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。     

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。     

Synthesis and characterization of thienyl‐ and terthienyl‐group‐bearing methacrylic polymers as precursors for grafting reactions of thiophene side‐chains

Acrylic and methacrylic monomers bearing pyrrolyl, thienyl and terthienyl groups, were synthesized and copolymerized with various amounts of butyl acrylate and butyl methacrylate. In the resulting copolymers the heterocycle side‐groups behaved as initiators in the oxidative polymerization of thiophene, allowing the polythiophene chains to grow from the side‐groups and leading therefore to graft copolymers. These last were collected mostly as insoluble fractions after extraction with chloroform. Processible polymers with polythiophene side‐chains were obtained when in the precursor polymer the heterocycle side‐group content was very low. The presence in the graft copolymers of a significant number of stiff polythiophene side‐chains was responsible for the rise in Tg values in comparison with the precursor polymers. The average number of grafted thiophene units, evaluated in the range 2–7.5, did not relate directly to measured conductivity values that were in the range 5.9 × 10⁻⁵–6.2 × 10⁻² S cm⁻¹. © 1999 Society of Chemical Industry     

Application of Macromonomers for Pressure Sensitive Adhesives I. Adhesive and Surface Properties

Adhesive and surface-chemical properties of poly(styrene macromer-butyl acrylate) copolymers, poly (styrene-butyl acrylate macromer) copolymers and poly (styrene-butyl acrylate) random copolymers were investigated. The results were as follows:

(1) The adhesive properties of the copolymers which were prepared by the macromer-technique were different from the random copolymers.

(2) It was found that there were differences in the surface and molecular structure between the copotymers which were prepared by the macromer technique and the random copolymers. These differences were evident from the results of measurements of the surface free energy of the copolymers and of the interfacial tension of water/toluene in the presence of the copolymers.

(3) The reason why there were differences in the surface and molecular structure seemed to be that the copolymers which were prepared by the macromer technique had graft chains and a different inner-structure from the random copolymers. Therefore, it was suggested that the graft copolymers which were prepared by the macromer technique had a phase-separated structure.     

含氟"三防"纺织助剂的研究进展

含氟"三防"纺织助剂是一种能明显改变织物的表面性能,使织物具有防水、防油、防污性能的助剂系列。综述了含氟"三防"纺织助剂的发展过程、研究现状,对该系列助剂的合成工艺进行了总结,并对该系列助剂国内发展进行展望。     

Synthesis,characterization, and thermal behavior study of methyl methacrylate polymers containing 4‐carbazole substitutes

A new polymerizable monomer, [4‐(9‐ethyl)carbazolyl]methyl methacrylate ( 2 ), was synthesized by reacting of methacrylic acid and 4‐hydroxymethyl‐9‐ethyl carbazole ( 1 ) by esterification procedure in the presence of N,N′‐dicyclohexylcarbodiimide. The resulting monomer was then polymerized free‐radically to form the poly(methyl methacrylate) containing 4‐(9‐ethyl)carbazolyl pend ent groups. Also, copolymerization of monomer 2 with various acrylic monomers such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, and n‐butyl acrylate by azobisisobutyronitrile as a free radical polymerization initiator gave the related copolymers in high yields. The structure of all the resulted compounds was characterized and confirmed by FTIR and ¹H NMR spectroscopic techniques. The average molecular weight of the obtained polymers was determined by gel permeation chromatography using tetrahydrofurane as the solvent. The thermal gravimetric analysis and differential scanning calorimeter instruments were used for studying of thermal properties of polymers. It was found that, with the incorporation of bulky 4‐(9‐ethyl)carbazolyl substitutes in side chains of methyl methacrylate polymers, thermal stability and glass transition temperature of polymers are increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4989–4995, 2006     

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.     

Fluorinated epoxides as surface modifying agents of UV‐curable systems

Two commercially available epoxy‐fluorinated monomers, 3‐(perfluorooctyl)‐1,2‐propenoxide and 3‐(1H, 1H, 9H‐hexadecafluorononyloxyl)‐1,2 propenoxide, were used as modifying additives for UV curable systems. These two fluorinated monomers were mixed, in small amounts (less than 1% w/w) with a hydrogenated epoxy monomer 1,4‐cyclohexanedimethanol‐diglycidyl ether. The mixtures were coated on glass substrate and UV‐cured, giving rise to transparent films. Notwithstanding their very low concentrations, the fluorinated monomers caused a change in the surface properties of the films, without changing their curing conditions and their bulk properties. The air side of the coatings became highly hydrophobic, while the substrate side was unmodified. As shown by XPS measurements, the fluorinated monomers were able to concentrate selectively on the air side of the films, forming a fluorinated layer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1524–1529, 2003     

(Meth)acrylate liquid crystalline polymers for membrane applications

Synthesis and characterization of a series of linear copolymers with liquid crystalline side chains is reported. Methacrylate monomers containing cyanobiphenyl as a mesogenic group were prepared. These monomers were then copolymerized with 2‐ethylhexyl acrylate in varying molar ratios. The structure and composition of the monomers and corresponding polymers were determined by ¹H‐NMR, elemental analysis and size‐exclusion chromatography. Thermal properties of the polymers were studied using differential scanning calorimetry, polarized optical microscopy, and X‐ray scattering techniques. Increasing mesogen content resulted in an increase of the glass transition temperature of the copolymers. In addition, above a threshold mesogen content the copolymers exhibited smectic mesophases. Using a solution casting technique, a membrane was fabricated to study single gas transport behaviors. Permeabilities, were in the order of CO₂ > propylene > O₂ > N₂ > CH₄ > propane. Diffusion coefficients correlated well to Lenard–Jones Diameter. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42694.     

Considerations of functional fluoropolymer structure in the design of acrylic–fluorine hybrid PSAs: Graft versus telechelic cooligomers

The objectives of this present article are to design and compare novel acrylic‐fluorine networks as the replacement of fluorinated polyacylate for adhesives application. Firstly, two effective strategies have been developed to achieve functional poly(VDF‐co‐HFP) copolymers based on commercial fluoropolymers. The first approach extensively involved the facile chemical degradation of commercial poly(VDF‐co‐HFP) copolymers to obtain telechelic cooligomers. The second route dealt with the preparation of functional fluoropolymers grafted by multiplex acrylate. Then these two functional and original products were applied as precursors of acrylic‐fluorine hybrid networks in situ polymerization with acrylic monomers. In contrast to original fluoropolymers, functional poly(VDF‐co‐HFP) copolymers exhibited better compatibility with acrylic chain, especially after crosslinking by aluminium acetylacetonate. Additionally, the surface properties of acrylic‐fluorine hybrid networks were discussed based on the SEM and contact angle test. Finally, the peel strength and shear holding power measurements indicated that acrylic‐fluorine hybrid networks can find their potential applications in low surface energy fluorinated PSAs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46038.     

Preparation of water-repellent cotton fabrics from fluorinated diblock copolymers and evaluation of their durability

Two fluorinated diblock copolymers were prepared, characterized, and used to coat cotton fabrics. These copolymers included poly[2-(perfluorohexyl)ethyl acrylate]-block-poly[(triisopropyloxysilyl)propyl methacrylate] (PFHEA-b-PIPSMA) and poly[2-(perfluorohexyl)ethyl acrylate]-block-poly(glycidyl methacrylate) (PFHEA-b-PGMA). The PFHEA block provided the coatings with a low surface tension to help impart water-repellency, while the PIPSMA or PGMA blocks (bearing alkoxysilane or epoxide groups, respectively) allowed the anchoring of the copolymers onto the cotton fibers. A simple coating procedure was used to yield water-repellent cotton fabrics. Water contact angles were measured to evaluate the durability of the treated cotton fabrics after they had been subjected to extraction, washing and laundry tests. These results revealed that cotton fabrics coated with PFHEA-b-PIPSMA were rendered hydrophobic, but their stability was relatively poor. Meanwhile, cotton fabrics coated with PFHEA-b-PGMA exhibited water contact angles higher than 150° and retained their water-repellency even under harsh test conditions.     

Theoretical modeling coupled with experimental study on the preparation and characterization comparison of fluorinated copolymers: Effect of chain structure on copolymer properties

Theoretical modeling coupled with an experimental study is presented for the preparation and characterization comparison of the amphiphilic copolymers of 2, 2, 3, 3, 4, 4, 4‐heptafluorobutyl methacrylate (HFBMA) and 2‐hydroxyethyl methacrylate (HEMA) to achieve a multiscale generalization of the polymeric system. A series of amphiphilic copolymers having different chain structures with HFBMA as the hydrophobic component and HEMA as the hydrophilic component was first synthesized through atom transfer radical copolymerization (ATRcoP) or model‐based semibatch ATRcoP. Theoretical modeling is used to optimize the macromolecular structure and experimental approaches that are used to prepare copolymers of HFBMA and HEMA with some tailor‐made polymer properties. Furthermore, a systematic comparison of major properties (i.e., thermal, micellization, and surface properties) of these fluorinated copolymers (i.e., random, block, linear gradient, and inverse linear gradient copolymers) was carried out. The results show that these fluorinated copolymers with different chain structures have dissimilar properties. The results also demonstrate that the approach of coupling theoretical modeling with an experimental study can be used to guide a multiscale generalization of the polymeric system for practical application. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3019–3033, 2013     

Modification of the surface of chemical fibres with fluorine-containing copolymers (review)

Modification of chemical fibres with copolymers of 1,1-dihydroperfluoro-heptyl acrylate (PFHA) to decrease their wettability was systematically investigated and some characteristics of this process were established. It was shown that the effectiveness of modification is determined by the method of treating the fibres with the copolymer modifiers, the molecular composition of these copolymers, and the colloid chemical properties of the latexes based on them. Treatment of the fibres with copolymers with functionally active groups capable of reacting with the macromolecule of the fibre-forming polymer and cross-linking on the surface of the fibre is the most effective method of modification. Substitution of incomplete fluorinated alcohols or unfluorinated monomers for the acrylates in the PFHA copolymer reduces their effectiveness in modification. Copolymers of PFHA with hydrophilic monomers capable of being orientedly sorbed by the fibre due to its amphiphilic nature and forming surfaces with low energy are an exception. For effective use of the copolymer modifier, the latexes of these copolymers should have certain colloid chemical properties: the particle charge, adsorption saturation, and aggregate stability should be optimum, which will ensure their stability during preparation, storage, and use.Translated from Khimicheskie Volokna, No. 5, pp. 27–30, September–October, 1995.