Synthesis, characterization and properties of a novel fluorinated polyurethane

A novel fluorinated polyurethane (FPU) was prepared by fluorinated polyether glycol (PTMG-g-HFP) as a soft segment, 1,6-hexamethylene diisocyanate (HDI) or toluene diisocyanate (TDI) as a hard segment and 1,4-butanodiol (BDO) as a chain extender. Fourier transform infrared spectroscopy (FTIR), ¹H NMR, ¹³C NMR and gel permeation chromatography (GPC) were used to characterize the structure of the fluorinated polyurethane. The thermal stabilities of the fluorinated polyurethane and the corresponding hydrogenated polyurethane were studied by thermogravimetric analysis (TGA). X-ray photoelectron spectroscopy (XPS) analysis at two different sampling depths for the fluorinated polyurethane was used to investigate the surface compositions of FPU. And the mechanical properties of the fluorinated polyurethane and the corresponding hydrogenated polyurethane were also measured. Chemical resistance of polyurethane films was estimated through spot tests with different solvents. The results showed that FPU had high thermal stability, strain-hardening property and good chemical resistance. The XPS measurements showed the fluorine enrichment on the surface of FPU.     

A novel approach to fluorinated polyurethane by macromonomer copolymerization

For the first time, through macromonomer radical copolymerization, a novel fluorinated polyurethane (FPU) was synthesized based on partly acrylate-endcapped polyurethane macromonomers with hexafluorobutyl acrylate (HFBA). Partly acrylate-endcapped polyurethane (PU) macromonomers were synthesized using isophronediisocyanate (IPDI), dimethylol propionic acid (DMPA), polyethylene adipate glycols (PEA) etc. The novel fluorinated polymer, which bore PU side chains and fluorinated side chains, was confirmed by F¹⁹ NMR spectroscopy, X-ray photoelectron spectroscopy (XPS), elemental analysis, scanning electron spectroscopy (SEM) etc. Copolymerization of polyurethane macromonomers with hexafluorobutyl acrylate (HFBA) was briefly investigated. The surface tension of FPU solution was measured and showed sharply decrease compared to that of pure polyurethane. Results from SEM showed a uniform size distribution of phase micro-domains on the fracture surface of FPU.     

Synthesis and characterization of fluorinated polyurethane containing carborane in the main chain: Thermal,mechanical and chemical resistance properties

In this study, two fluorinated polyurethanes(FPU) containing carborane groups in the main chains were firstly designed and synthesized via the reaction of hexamethylene diisocyanate trimer(HDI trimer) with fluorinated polyesters(CFPETs) having hydroxyl-terminated carborane groups at room temperature. The structures of carborane fluorinated polyesters(CFPETs) and polyurethanes(CFPUs) were characterized by gel permeation chromatography(GPC), Fourier transform infrared(FTIR) spectroscopy and nuclear magnetic resonance(NMR) measurements. The thermal stability, mechanical properties, Shore A hardness, solvent resistance and acid-alkali resistance of the carborane fluorinated polyurethane films were also studied. Thermogravimetric analysis(TGA) tests manifested that the introduction of carborane groups into the main chain of fluorinated polyurethane endowed the obtained fluorinated polyurethane with excellent thermal stability. The thermal decomposition temperature of carborane fluorinated polyurethane(CFPU) increased by 190 °C compared with that of the carborane-free fluorinated polyurethane(FPU). Even at 800 °C, CFPU showed the char yield of 66.5%, which was higher than that of FPU(34.3%). The carborane-containing fluorinated polyurethanes also showed excellent chemical resistance and prominent mechanical property even after the cured films being immersed into Jet aircraft oil or 37% HCl for 168 h or at high temperature(700 °C). It is found that the structural characteristics of carborane group and the compacted structure of CFPU effectively improve the thermal stability, mechanical property, solvent resistance and acid-alkali resistance of the carborane-free fluorinated polyurethane. These excellent properties make CFPU as the useful raw materials to prepare the high temperature resistant coatings or adhesives for automotive engines, engine or fuel tank of aircraft and other equipment working in high-temperature or high concentrations of acid-alkali environments.     

Effect of soft segment length on properties of fluorinated polyurethanes

The effects of soft segment length on the variations in morphology, surface composition, and hydrophilicity have been studied in fluorinated polyurethanes (FPUs) and correlated with their preliminary blood compatibility as evidenced by in vitro platelet adhesion experiments. The fluorinated polyurethanes were obtained using hexamethylene diisocyanate (HDI) and chain extender of 2,2,3,3-tetrafluoro-1,4-butanediol (TF) as the hard segment as well as various soft segments—polytetramethyl oxides (PTMO) with molecular weights of 650, 1000, 1400, and 2000. The increased phase separation in hard-segment domains with lengthening soft segment was observed by FT-IR, which is believed to result in enhanced strength of hydrogen bonds and good hard-segment order arrangement. Thin-film XRD results indicate at least three lateral distances existing between adjacent hard segments in the crystallized hard segment. Their distribution depends strongly on the length of soft segment. Lengthening soft segment promotes the formation of dense arrangement of crystallized hard segments. Compared with the effect of phase separation, surface composition was found to exert a major influence on the preliminary blood compatibility of fluorinated polyurethanes. Increasing fluorine content by decreasing soft segment length promotes reduction in platelet adhesion and activation on polyurethane surfaces.     

Effect of soft segment length on the thermal behaviors of fluorinated polyurethanes

Differential scanning calorimetry (DSC) and temperature modulated DSC (MDSC) have been applied to investigate the thermal behaviors of fluorinated polyurethanes (FPU), which were obtained using 2,2,3,3-tetrafluoro-1, 4-butanediol as the chain extender and based on various soft segments—polytetramethyl oxides (PTMO) with molecular weights of 650, 1000, 1400 and 2000. An exothermic peak and/or multiple melting endotherms were observed during the heating to melting temperature of soft and hard segments. Attributed to the simultaneous recrystallization and melting processes during heating, these features have been confirmed via MDSC, where an endotherm and an exotherm were noted in reversing and non-reversing components of the heat flow. Separating the non-reversing components from the reversing curves, the dependencies of polyurethane morphology on the length of the soft segment could be clarified using MDSC analysis. Soft segment lengthening significantly influences the morphology of soft segment domains in FPUs. The phase separation and crystallinity of the soft segment increased with its length. However, soft segment length exerted a minor influence on the dissociation temperature of the short-range ordered hard segment domain and on the melting temperature of hard segment crystals. Examination of the heats of melting based on the quasi-isothermal MDSC experiments indicated that the crystallinity of hard segment domains declined with increasing soft segment length.     

Convenient synthesis of novel fluorinated polyurethane hybrid latexes and core-shell structures via emulsion polymerization process with self-emulsification of polyurethane

Novel fluorinated polyurethane hybrid latexes in the size range of 40–50 nm, fluoroalkyl acrylate as fluorinated monomers, with various fluorine content (F% = 9∼26 wt%) were successfully prepared via emulsion polymerization process without traditional emulsifier. The waterborne polyurethane, which was synthesized by using isophronediisocyanate, dimethylol propionic acid, polyethylene glycols, etc., served not only as copolymerizable macromonomer but also as polymeric high molecular weight emulsifier. The structures of polyurethane macromonomer and fluorinated polyurethane were characterized by Fourier transform infrared and H¹-NMR. Particle size, zeta potential, micromorphology of the latex par.ticles, and surface properties were investigated by dynamic light scattering, potential particle size analyzer, transmission electron microscopy, and contact angle measurement, respectively. Results illustrated that the advantage of this process is that the size of fluorinated polyurethane hybrid particle is less sensitive to the composition. Furthermore, it was showed that fluorinated polyurethane latex particles had core-shell structures, especially when the content of fluorine was 26.08 wt%. Moreover, there was an obvious migration of fluorinated groups to the surface during the formation of fluorinated polymer films, although fluorinated groups were covered by polyurethane in latex particles.     

硬段侧链含有氟化双季铵盐的聚氨酯表面性能及抗菌性能分析

研究了硬段侧链含有氟化双季铵盐的系列聚氨酯(FQPUs)的表面性能和抗菌性能. 水接触角测试和表面自由能测试结果表明, 加入少量氟化双季铵盐扩链剂, 可以使聚氨酯表面富集氟碳链, 氟化双季铵盐聚氨酯表面自由能很低, 具有很好的抗黏附性能. 迁移到表面的两条氟碳链在常温下不会发生链反转, 使材料的抗黏附性能得以保持. 同时, 使材料表面形成一层疏水层, 减小材料的吸水率. XPS研究结果表明, 氟碳链的-CF₃位于材料的最外层, 材料的次表面是具有良好杀菌性能的双季铵盐, 这样形成了具有多重抗菌性能的表面. 另外, XPS研究结果表明, 材料表面化学结构与材料本体的微相分离结构相关. 抗菌性能测试结果表明, 氟化双季铵盐聚氨酯抗金黄色葡萄球菌的能力很强, 对于大肠杆菌的抗菌效果有所下降, 但相对于单季铵盐聚氨酯的抗菌效果有一定提高.     

Synthesis and properties of fluorine-containing polyurethane based on long chain fluorinated polyacrylate

For the first time, a novel fluorine-containing polyurethane (FPU) was prepared by introducing long chain fluorinated polyacrylate into PU. The FPU was prepared from dodecafluoroheptyl methacrylate (DFMA), β-mercaptoethanol (β-ME), methacryloyloxyethyl isocyanate(MOI), hydroxyethyl methylacrylate (HEMA), iso-butyl acrylate(I-BA), polyether diol (N220) and toluene diisocyanate (TDI). The structure of product for every step was confirmed by Fourier transform infrared (FT-IR) spectroscopy and proton nuclear magnetic resonance (¹H-NMR) spectra. It was found that when the DFMA content increased from 0 to 12%, thermal stability was improved in some degree; the hardness, the adhesion and the tensile strength increased; the swelling degree in water, NaOH solution and HCl solution decreased; the solvent resistance in hexane and butanone improved to some degree; the contact angle of water and ethylene glycol increased; the surface free energy decreased. XPS tests indicated fluorine migrated to surface.     

SURFACE STRUCTURE AND BULK PROPERTIES OF FLUORINATED POLY(ETHER URETHANE)S AND POLY(ETHER URETHANE) BLENDS

INTRODUCTIONPolyurethanes (PU) have been widely used for manufacturing medical devices because of their excellentmechanical properties and moderate biocompatibility[1]. Although polyurethanes used in applications requiringall of the above properties have been successful for short-term use, the problems of long-term thromboresistanceand biostability in a biological environment still remain unsolved[2,3]. A legitimate approach to improving theproperties of polyurethanes is introduction of f…     

含氟聚氨酯的研究进展

综述了溶剂性、水性含氟聚氨酯的合成及研究，并进行了讨论。     

Preparation,characterization, and properties of fluorinated polyurethanes

Novel fluorinated polyurethanes (FPUs) were prepared by living radical polymerization of polyurethanes and hexafluorobutyl acrylate. The structures of the FPUs were characterized by FTIR, ¹H NMR, GPC, DSC, and XPS. The fluorinated polyurethane polymerization was investigated and showed monomer conversion, and molecular weight increased with increasing reaction time. In this way, the fluorine content in polyurethane could be easily adjusted by controlling the content of the fluorinated acrylate monomer. The mechanical evaluation shows that FPUs exhibit good mechanical properties. Morphology of FPU films was observed by scanning electron spectroscopy. The effects of the fluorine content on the surface properties and oxidative stability of FPUs were investigated. FPUs films were devoid of significant surface degradation after immersion in 20% H₂O₂ and 0.1 M CoCl₂ at 37 °C for 5 weeks. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3248–3256, 2009     

核壳型含氟丙烯酸酯共聚物的合成及性能

采用饥饿态半连续种子乳液聚合方法, 在十二烷基硫酸钠(SDS)/辛基苯基聚氧乙烯醚(TX-10)复合乳化剂的作用下, 分别选用甲基丙烯酸三氟乙酯(TFEM)、甲基丙烯酸六氟正丁酯(HFBM)和甲基丙烯酸十二氟庚酯(DFHM)为含氟单体, 合成以丙烯酸正丁酯(BA)、甲基丙烯酸甲酯(MMA)和含氟单体为原料的核壳型结构含氟丙烯酸酯共聚物乳液. FTIR, 1H NMR, TEM和DSC分析结果显示, 获得了BA/MMA/含氟单体的共聚物乳液, 且乳液具有明显的核壳结构. DSC, TGA和SEM-EDX的分析显示, 核壳型结构的共聚物具有优异的热力学稳定性能和成膜性能; 长侧链或短侧链含氟单体对共聚物的热稳定性影响不明显, 但侧链较长的含氟单体所获得的聚合物在成膜过程中更易向表面迁移, 更能体现含氟聚合物的优点.     

水性含氟聚氨酯的研究进展

水性含氟聚氨酯具有低的VOC排放,同时由于氟元素的引入,解决了传统水性聚氨酯耐水、耐油性差的缺点,大大拓展了其在涂料、皮革、油墨等领域的应用范围,因此受到广泛关注.本文综述了近年来国内外水性含氟聚氨酯的主要研究进展,综合比较了两种合成水性含氟聚氨酯主要方法,即核壳乳液聚合法和缩聚共聚法的各自特点,并对由两种不同方法制备的水性含氟聚氨的性能进行了讨论.     

氟硅改性聚氨酯自组装膜的合成及性能

以甲苯二异氰酸酯、聚酯二元醇、2,2-二羟甲基丙酸和十三氟-1-辛醇等为原料合成了氟醇封端的聚氨酯预聚体(FPU)。 通过FPU侧链含有的羧基官能团与异氰酸酯基硅烷偶联剂(Si-NCO)反应制备了含硅氧烷官能团功能性树脂(FPUSi)。 采用红外光谱(FT-IR) 对产物结构进行了表征,用TGA和水接触角等测试了自组装薄膜的表面性能。 结果表明,在N2气氛围下,FPU和FPUSi的热失重温度（T5％）均为178 ℃;硅基表面经FPUSi自组装膜修饰后,其表面水接触角达到81°。 微摩擦测试结果表明,当载荷为400 mN时,FPUSi自组装薄膜的稳定摩擦系数达到0.09。     

UV-curable low-surface-energy fluorinated poly(urethane-acrylate)s for biomedical applications

Novel UV-curable fluorinated poly(urethane-acrylate) (FPUA) oligomers have been synthesized from 1H,1H,12H,12H-perfluoro-1,12-dodecanediol (PFDDOL), either 1,6-hexamethylene diisocyanate (HDI) or 4,4′-diphenylmethane diisocyanate (MDI), and 2-hydroxyethyl methacrylate (HEMA) for end-capping with photo-crosslinkable methacrylate groups. The fluorine content and the nature of the isocyanate were investigated to determine their effects on the physical properties, surface properties, and blood compatibilities of the polymers. The introduction of hydrophobic fluorocarbon chains led to phase separation and a low total surface energy, which reduced the adhesion of blood platelets onto the materials. The HDI-type UV-curable, fluorinated poly(urethane-acrylate) exhibited a low-surface-energy and superior blood compatibility (as determined from RIPA values).     

Synthesis of a fluoro-diol and preparation of fluorinated waterborne polyurethanes with high elongation at break

In this study, a fluoro-diol, trifluoroethyl-2-methylpropanoate-β-dihydroxy ethylamine (TFMDA), was successfully synthesized by Michael Addition reaction between trifluoroethyl-2-methacrylate (TFEMA) and diethanolamine (DEA). The chemical structures were characterized by FT-IR and ¹H NMR methods. And then by the reaction of dicyclohexylmethylmethane-4,4′- diisocyanate (HMDI), poly(propylene glycol) (PPG), 2,2-dimethylolbutanoic acid (DMBA), diethylene glycol (DEG) and trifluoroethyl-2-methylpropanoate-β-dihydroxyethylamine (TFMDA), fluorinated waterborne polyurethane emulsions with different content of COOH and TFMDA were successfully prepared. It was demonstrated that all the polyurethane emulsions exhibited enhanced storage stability and all the polyurethane films possessed high elongation at break and exceeded 1000%. Addition of organic fluorine obviously improved the water-resistance property of the waterborne polyurethane films.     

Synthesis and characterization of novel environmentally friendly shape memory polyurethanes based on poly(epsilon-caprolactone) diol/castor oil mixtures

A new category of polyurethane plastics (PUs) was obtained from poly (ε-caprolactone) diol/castor oil mixture as a dual-component of their soft segment and hexamethylene diisocyanate (HDI) as the hard segment. The main aim of this study was to explore the effect of castor oil on content chemical structure, dynamic and mechanical properties and low temperature heat induced shape memory of the obtained polyurethane system. The chemical structure of samples was confirmed by Fourier transforms infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. Differential scanning calorimetry (DSC) was carried out to study thermal transitions of synthesized polyurethanes. At 50 mol % of oil, the polyurethane showed the highest enhancement in tensile strength (54%) and Young’s modulus (23%) compared to PU-0. The PU containing 50 mol % of oil was nearly recovered by 99%.     

沉淀聚合制备荧光聚脲微球及Fe3+检测

以异氟尔酮二异氰酸酯为单体, 以氨基功能化的1.8-萘二甲酰亚胺(AABD)为荧光基团, 在水/丙酮质量比为3/7的混合溶剂中, 通过沉淀聚合制备了表面洁净的高度单分散荧光聚脲微球(FPU). 通过FTIR及¹H NMR对AABD及FPU的化学结构进行了表征; 通过UV-Vis光谱确定FPU中嵌入的AABD荧光单元的含量; 通过荧光光谱研究了FPU固体粉末分散在水中及溶解在N-甲基吡咯烷酮中的荧光特性以及FPU分散在不同Fe³⁺浓度水溶液中的荧光变化. 结果表明, FPU的平均粒径(D_n)为5.24 μm, 粒径分布(D_w/D_n)为1.004, 具有强烈的绿色荧光(激发波长为420 nm, 最大发射波长为522 nm); FPU分散在水中不发生荧光自猝灭, 其荧光强度随着Fe³⁺浓度的增加(10^-4 ~10^-3 mol/L)呈线性降低.     

Chiral side-chain liquid crystalline polysiloxanes bearing fluorinated mesogens and cholesteryl groups

A series of chiral side-chain liquid crystalline (LC) polysiloxanes bearing fluorinated mesogens were synthesized with a cholesteric LC monomer and a fluorinated nematic LC monomer. They were characterized by use of various experimental techniques, and effect of fluorinated mesogens on characteristic of LC polysiloxanes was studied as well. In photoluminescence spectra, a narrow and a broad peak occur at around 270-317 nm, originated, respectively, from fluorinated phenyl groups and the conjugated xenene structure. The specific rotation analysis of all polymers showed negative values, but absolute values were lower than those of the chiral monomers. All polymers showed smectic LC phase with very wide temperature ranges on heating and cooling cycles. Especially, only polymers bearing more fluorinated component exhibited smectic-cholesteric phase transition when they were heated. As the polymers contained more fluorinated mesogens, segregation of the fluorinated segment to the surface should occur at mesomorphic temperature. The highly ordered lamellar mesogen-siloxane matrix systems should be disturbed severely by separation of fluorinated mesogens, suggesting mesogenic orders transition from lamellar smectic to cholesteric phase.     

Synthesis and properties of fluorinated thermoplastic polyurethane elastomer

A series of fluorinated thermoplastic polyurethane elastomers (FTPU) based on self-synthesized fluorinate polyether diol (PFGE) were prepared by two-step polymerization. For the purpose of improving the molecular weight and mechanical property of FTPU, polybutylene adipate (PBA) was used to be compounded with PFGE as the soft-segment of FTPU. Effects of the mass ratio of PFGE/PBA and the mass fraction of hard-segment on the mechanical property of FTPU were investigated. The structure and morphology of FTPU were characterized by FTIR, GPC, DMA, surface tension and AFM analysis.