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…     

Precise Synthesis of Ultra‐High‐Molecular‐Weight Fluoropolymers Enabled by Chain‐Transfer‐Agent Differentiation under Visible‐Light Irradiation

Ultra‐high‐molecular‐weight (UHMW) polymers display outstanding properties and hold potential for wide applications. However, their precise synthesis remains challenging. Herein, we developed a novel reversible‐deactivation radical polymerization based on the strong and selective fluorine–fluorine interaction, allowing chain‐transfer agents to spontaneously differentiate into two groups that take charge of the chain growth and reversible deactivation of the growing chains, respectively. This method enables dramatically improved livingness of propagation, providing UHMW polymers with a surprisingly narrow molecular weight distribution (?≈1.1) from a variety of fluorinated (meth)acrylates and acrylamide at quantitative conversions under visible‐light irradiation. In situ chain‐end extensions from UHMW polymers facilitated the synthesis of well‐defined block copolymers, revealing the excellent chain‐end fidelity achieved by this method.     

Precise Synthesis of Ultra-High-Molecular-Weight Fluoropolymers Enabled by Chain-Transfer-Agent Differentiation under Visible-Light Irradiation

Ultra-high-molecular-weight (UHMW) polymers display outstanding properties and hold potential for wide applications. However, their precise synthesis remains challenging. Herein, we developed a novel reversible-deactivation radical polymerization based on the strong and selective fluorine–fluorine interaction, allowing chain-transfer agents to spontaneously differentiate into two groups that take charge of the chain growth and reversible deactivation of the growing chains, respectively. This method enables dramatically improved livingness of propagation, providing UHMW polymers with a surprisingly narrow molecular weight distribution (Đ≈1.1) from a variety of fluorinated (meth)acrylates and acrylamide at quantitative conversions under visible-light irradiation. In situ chain-end extensions from UHMW polymers facilitated the synthesis of well-defined block copolymers, revealing the excellent chain-end fidelity achieved by this method.     

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.     

Synthesis,UV-curing behavior and surface properties of fluorine-containing vinyl ether polymers

Five fluorine-containing vinyl ether monomers were prepared by the reaction between 2-vinyloxy ethanol, a fluorinated alcohol and hexafluorobenzene in the presence of sodium hydride in dimethylformamide. Two representative properties of these monomers, UV-curing behavior initiated by a cationic photo-initiator PAG 201 and surface free energy of coating films, were investigated. Photo-polymerization proceeded both rapidly and completely with a high double-bond conversion （〉 90%） and a fast curing rate （maximum curing time 〈 21 s） for three monomers. The surface energies of the monomers and the resulting polymer films were then investigated. The minimum surface free energy of the UV-cured homopolymer films reaches 7.1 mJ/m2. X-ray photoelectron spectroscopy data show that the low surthce tension is influenced by fluorine content in the soft segments and fluorinated chains＇ migration to the surface. The five monomers exhibit low viscosity, low surface energy, good thermal stability and good photo-polymerization properties, which make them great candidates for UV coating and photoresist applications.     

Langmuir monolayers and the transferred films of fluorinated amphiphiles containing vinyl groups

The monolayer behavior of long-chain esters of acrylic and methacrylic acids containing perfluoro or partially fluorinated carbon chains at the air/water interface was studied by surface pressure-area isotherm measurements and Brewster angle microscopy. It has been found that a minor change in the chemical structures of these fluorinated amphiphiles, such as a hydrogen substituted at the omega-position of the hydrophobic fluorocarbon tails instead of a fluorine as well as hydrophilic vinyl ester groups inserted between acrylates and methacrylates, induces a drastic change in the isotherms for the monolayers, suggesting different molecular orientation and packing in the films. The monolayers were transferred by horizontal lifting, Langmuir-Blodgett, and surface-lowering methods to give the X-, Y-, and Z-type films, respectively. These films were characterized by scanning probe microscopy, to clarify the mesoscopic surface structures of the molecular films exposed with the hydrophilic or hydrophobic moieties in air, depending upon the dipping methods. The Z-type films with the outermost surface of the fluorinated substituents were examined in relation to the frictional properties that strongly depend upon the fluorine and the hydrogen atoms at the end of the hydrophobic fluorocarbon chains, which is controllable at the atomic level.     

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.     

Synthesis and Characterization of Fluorinated Acrylic Polymer and the Properties of Epoxy Thermosets Modified With It

A novel fluorinated acrylic polymer poly(2,2,3,4,4,4-hexafluorobutyl methacrylate)-r-poly(glycidyl methacrylate) (PHFMA-r-PGMA) was synthesized and used to modify the general performances of epoxy resin. Fourier transform infrared spectroscopy (FTIR) and ¹H nuclear magnetic resonance spectroscopy (¹H-NMR) successfully verified the synthesis of PHFMA-r-PGMA. In order to study the effect of epoxy groups in PHFMA-r-PGMA on the properties of modified epoxy resin, corresponding fluoropolymer without epoxy group (PHFMA) was also prepared, and the properties of epoxy thermosets modified by two kinds of fluoropolymers were comparatively studied. The contact angle measurements indicated that the PHFMA-r-PGMA and PHFMA modified thermosets both showed considerable hydrophobicity and lipophobicity. For further comparison, it was also found that the thermosets modified by PHFMA-r-PGMA had a little worse hydrophobicity and lipophobicity but better surface stability than which modified by PHFMA because the epoxy groups in PHFMA-r-PGMA “locked” more fluoropolymers in the bulk matrix of the thermosets, but PHFMA was more freely able to migrate to the surface of the thermosets. SEM images of the fracture surface of PHFMA-r-PGMA and PHFMA modified epoxy thermosets displayed “irregular ripples” or “protuberant island” structures, which suggesting both of these two copolymers could significantly toughen epoxy resin. The results of differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) showed that the thermosets modified by PHFMA-r-PGMA had better thermal stability than which modified by PHFMA due to the higher crosslinking density between PHFMA-r-PGMA and epoxy resin because of the epoxy groups in PHFMA-r-PGMA. The mechanical properties were investigated by tensile testing and impact testing. Although the tensile strength of the PHFMA-r-PGMA and PHFMA modified epoxy thermosets both declined slightly with growing the content of fluoropolymers, the elongation at break and impact strength both increased first and then decreased in the meantime, which indicated that the two kinds of modified thermosets had better toughness than pure epoxy resin. It may be because the macro-phase separation between the long fluorine carbon chain segments and epoxy resin during curing could absorb the impact energy effectively.     

软段含离子的含氟水性聚氨酯的制备

以单羟基氟碳链一元醇为有机氟改性剂,将含氟基团引入聚氨酯主链中,通过分子设计的方法制备出软段含有离子基团的有机氟阴离子型水性聚氨酯。 比较了传统水性聚氨酯、硬段含氟的水性聚氨酯和软段含氟的水性聚氨酯在合成方法、耐水性、 热稳定性以及结晶性方面的差异;实验证明了软段含氟聚氨酯的水性聚氨酯的性能最为优良。 通过红外光谱的表征确定了氟化聚氨酯的结构,并证明了含氟基团的引入对聚氨酯软硬段间氢键作用的影响;水接触角由73°增加至107°,吸水溶胀率降低了66%,胶膜耐水性提高;热重分析结果表明,含氟聚氨酯的最大热失重温度提高了30 ℃,热稳定性增加;广角X射线衍射结果表明,胶膜的结晶度增加,结晶形式发生了微小程度的转变;扫描电子显微镜结果证明存在不均匀的多相结构。     

Fluorinated comblike homopolymers: The effect of spacer lengths on surface properties

A series of polyacrylate monomers with F‐alkylalkyl [F(CF₂)_n(CH₂)_n′] side groups were prepared by free‐radical polymerization. The effect of the chemical structure on the surface properties of poly(ethylene terephthalate)s was evaluated by variations in the relative length of the fluorocarbon and hydrocarbon units in the side group. The resulting polymers were quite surface‐active in the solid state. The surface and bulk organization was investigated by X‐ray photoelectron spectroscopy analysis. A strong correlation between the bulk organization and surface properties of the polymers was established. The outmost layer, formed from trifluoromethyl groups and some ester functions, suggests that the side chain is arranged irregularly in the polymer–air interface. The length of the lateral chain governs this organization: long fluorinated chains and short hydrocarbon spacers are essential elements of the molecular design for such low‐surface‐energy materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3737–3747, 2005     

Synthesis and surface properties of novel fluorinated polyurethane base on F‐containing chain extender

A novel fluorinated chain extender, (1‐(ethyl(2‐hydroxyethyl)amino)‐3‐ ((3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctyl)oxy)propan‐2‐ol) (FPO), was synthesized and characterized by nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR), and elemental analysis. Poly (ether urethane)s containing various amounts of the chain extender with fluorinated side chains (FPUs) were prepared by isophorone diisocyanate (IPDI), polytetra‐methylene‐ether‐glycol (PTMG), 3‐aminopropyltriethoxysilane (KH‐550), and 1,4‐butandiol (BDO). Films of FPUs were investigated by water absorption, contact angle, pencil hardness, adhesive force, and thermal analysis. Coating FPUs on micro‐nano concave‐convex structure plate realizes superhydrophobic performance. Scanning electron microscope (SEM) and atomic force microscopy (AFM) demonstrated that there is a lot of irregular concave‐convex structure, which forms a typical air cushion model. X‐ray photoelectron spectroscopy (XPS) analysis showed that surface fluorine content is 165% more than that of film average fluorine content. The superhydrophobic plate with 10% or higher F‐containing FPUs coating is of outstanding chemical corrosion resistance, excellent solvent resistance, and wear resistance.     

Synthesis and Surface Properties of Polybutadiene Chains End-Capped with Two Types of Fluorosilicon Groups

Abstract

Polybutadiene diol chains were end-capped, using two highly fluorinated monochlorosilanes, specifically di(4-fluorophenyl)-methylchlorosilane and di[3,5-bis(trifluoromethyl) phenyl]methyl-chlorosilane. The resulting chains, with one and three fluorine atoms at their ends, respectively, were characterized using contact angle measurements, X-ray photoelectron spectroscopy (XPS), and Time-of-flight secondary ionization mass spectroscopy (TOFSIMS). The observed lowered surface tensions and results from the chemical analyses were consistent with migration of the fluorosilicon end groups to the polymer surfaces.

     

Fluorinated alcohols as surface‐active agents in cationic photopolymerization of epoxy monomers

Fluorinated alcohols were used as surface modifying agents, through chain transfer mechanism in cationic UV curing of an epoxy system. The fluorinated alcohols were able to induce surface modification already at very low concentration (below 1 wt %). It has been shown that the surface modification depended on the concentration of the fluoroalcohols, on the length of the fluoroalkyl chain, and on the length of the methylene spacer between the fluorinated chain and the OH group. The strong increase on hydrophobicity in the presence of the synthesized fluorinated alcohol, CF₃(CF₂)₉(CH2)₁₀OH, was attributed to the higher fluorocontent of the chain as well as to a self‐organization effect. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4144–4150, 2005     

PREPARATION AND SURFACE PROPERTIES OF ACRYLIC COPOLYMERS CONTAINING FLUORINATED MONOMERS

A series of copolymers comprising butylmethacrylate, styrene, butylacrylate, hydroxypropyl acrylate and perfluoroalkyl methacrylate were synthesized by the free radical polymerization using BPO as an initiator. The surface property of the copolymer films was subsequently characterized. The contact angle measurements and energy dispersive analysis of X-ray （EDAX） show that the length and content of perfluoroalkyl side chains in the copolymers are crucial for the preparation of the film with low surface energy. At a given content of fluorinated monomers in the copolymers, the longer the perfluoroalkyl side chain, the larger the water contact angle of the copolymer films will be. On the other hand, the higher the content of fluorinated monomers, the lower the surface energy is. The water contact angle increases with the increase of the fluorinated monomer content and reaches a plateau at 3 wt% of fluorinated monomer content.     

Influence of fluorinated acids bonding on surface properties of crosslinked epoxy-based polymers

Two series of crosslinked fluorinated epoxy-based materials containing variable fluorine contents (from 0 to 6 wt.% F) were prepared using formulations based on a fluorinated acid (FA), epoxy monomer and a diamine. The epoxy monomer was based on diglycidyl ether of bisphenol A (DGEBA) while the curing agent was propyleneoxide diamine (Jeffamine D-230). The selected FA were: 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptanoic acid (FA1), perfluoro-heptanoic acid (FA2), and perfluoro-nonanoic acid (FA3). One of the series synthesized, FA-DGEBA/Jeffamine, is characterized by covalent attachment of the FA to the polymer by an ester bond. The other series, FA-Jeffamine/DGEBA, is characterized by ionic interaction between FA and polymer chains. The influence on thermal and surface properties of the architecture and chain-length of FA, and the nature of the linkage between FA and network precursors, was analyzed and discussed. It was found that both series showed high oleophobicity, but depending on the linkage between the fluorinated acid and the network, it was possible to develop hydrophobic or hydrophilic materials. The fluorine enrichment with the perfluoroalkyl substitutions was proved by XPS. By this technique it was possible also to analyze the concentration of ammonium groups at the surface.     

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 and characterization of core–shell polyacrylate latex containing fluorine/silicone in the shell and the self-stratification film

A series of core–shell polyacrylate latexes with different fluorine/silicone monomer concentrations were prepared successfully by seeded emulsion polymerization. Dodecafluoroheptyl methacrylate and perfluorooctyl methacrylate with different fluorinated side chains were employed as fluorinated monomers, and γ-methacryloxypropyl triisopropoxidesilane (MAPTIPS) was used as a silicone-containing monomer as well as a self-cross-linking agent. The morphology and chemical structure of the latexes were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, and differential scanning calorimetry, and the self-stratification properties of the latex film were verified by X-ray photoelectron spectroscopy and static contact angle measurement. The results showed that the fluorine/silicone-containing polyacrylate latexes presented a uniformly spherical core–shell structure, and the latex films displayed a preferential distribution of fluorinated composition near the surface, which was more remarkable with the synergism effect between the fluorine monomer and MAPTIPS. Additionally, the hydrophobicity and oleophobicity of the latex films exhibited high relevance with the fluorine/silicone monomer concentrations as well as the fluorinated side-chain structure.     

正离子光固化聚硅氧烷的合成及其环氧树脂复合固化膜的性能

以含氢聚硅氧烷(PMHS)分别与甲基丙烯酸六氟丁酯(HFMA)和烯丙基缩水甘油醚(AGE),经氯铂酸催化硅氢加成反应将甲基丙烯酸六氟丁酯和烯丙基缩水甘油醚引入聚硅氧烷的侧链,合成了3种含氟量不同的含氟代烃侧基/环氧侧基聚硅氧烷(EFPS),用FTIR、1H-NMR和13C-NMR进行了结构表征,将这类聚硅氧烷与环氧树脂...     

Synthesis and properties of novel fluorinated epoxy resins based on 1,1-bis(4-glycidylesterphenyl)-1-(3′-trifluoromethylphenyl)-2,2,2-trifluoroethane

A novel fluorinated epoxy resin, 1,1-bis(4-glycidylesterphenyl)-1-(3′-trifluoromethylphenyl)-2,2,2-trifluoroethane (BGTF), was synthesized through a four-step procedure, which was then cured with hexahydro-4-methylphthalic anhydride (HMPA) and 4,4′-diaminodiphenyl-methane (DDM). As comparison, a commercial available epoxy resin, bisphenol A diglycidyl ether (BADGE), cured with the same curing agents was also investigated. We found that the BGTF gave the exothermic starting temperature lower than BADGE no mater what kind of curing agents applied, implying the reactivity of the former is higher than the latter. The fully cured fluorinated BGTF epoxy resins have good thermal stability with glass transition temperature of 170-175 °C and thermal decomposition temperature at 5% weight loss of 370-382 °C in nitrogen. The fluorinated BGTF epoxy resins also showed the mechanical properties as good as the commercial BADGE epoxy resins. The cured BGTF epoxy resins exhibited improved dielectric properties as compared with the BADGE epoxy resins with the dielectric constants and the dissipation factors lower than 3.3 and dissipation 2.8 × 10⁻³, respectively, which is related to the low polarizability of the C-F bond and the large free volume of CF₃ groups in the polymer. The BGTF epoxy resins also gave low water absorption because of the existence of hydrophobic fluorine atom.     

Studies on the effects of the alkyl group on the surface segregation of poly(n-alkyl methacrylate) end-capped 2-perfluorooctylethyl methacrylate films

The effects of the alkyl group on the surface segregation of poly(n-alkyl methacrylate) end-capped with various numbers of units of 2-perfluorooctylethyl methacrylate (FMA) (PnAMA-ec-PFMA) were investigated by differential scanning calorimetry, angle-resolved XPS analysis, contact angle measurements, and X-ray diffraction (XRD). The results show that with similar numbers of FMA units at the polymer chain end the extent of fluorine segregation (Q) increased with increasing the number of carbon atoms in the side n-alkyl chains of poly(n-alkyl methacrylate). The surface fluorine content within 5 nm deep of the film of poly(n-octadecyl methacrylate) end-capped with one FMA unit (PODMA(160)-ec-PFMA(1.0)) was 208-fold higher than that of the bulk level. These observed differences in Q values were found due to the aggregate structure of the end-capped polymers in the solution, the flexibility, and the crystallinity of the n-alkyl side chains. When the nonfluorinated block was completely amorphous, the molecular aggregate structure of the end-capped polymers in the solution played an important role in the surface segregation of the fluorinated moieties on the resulting film. However, when the nonfluorinated block was crystalline, crystallinity would enhance greatly the segregation of the fluorinated moieties.