Preparation,Morphology and Properties of Waterborne-Polyurethane/Silica

A series of waterborne-polyurethane/silica (WPU/SiO₂) were prepared from isophoronediisocyanate, polyester polyol, dimethylolpropionic acid, tetraethoxysilane and 3-glycidyloxypropyl trimethoxysilane. The WPU/SiO₂ dispersion had narrower particle size distribution than the pure WPU. The mechanical properties of WPU/SiO₂ films were improved than the pure WPU. WPU/SiO₂ films were characterized by FT-IR spectroscopy, SEM, TEM, AFM, XRD and UV-Vis spectroscopy. The results showed that WPU/ SiO₂ hybrid films were found to be smooth morphology, and had good thermal stability and tunable transparence with the silica fraction in the film. Through suitable adjustment of silica content, some thin films have potential applications as the specialty materials.     

Abrasion resistance of waterborne polyurethane films incorporated with PU/silica hybrids

We describe polyurethane (PU)/silica hybrids (PSHs) prepared through hydrolysis and condensation reactions of tetraethoxysilane (TEOS) with or without methyltriethoxysilane (MTES) in the presence of polyurethane dispersion, which were subsequently incorporated into waterborne polyurethane (WPU) to prepare composites. The effects of the solid mass ratio of PSHs/WPU on the particle size of composite emulsions, the dispersion of silica nanoparticles in composite films, and the hardness and abrasion resistance of the corresponding films were examined. Composite emulsions possess a nanoscale particle size when incorporated with PSHs prepared using TEOS and MTES as precursors, and are superior to those with PSHs prepared using TEOS alone. Transmission electron microscopy revealed that silica nanoparticles had a uniform distribution in the polymer matrix and agglomerates could be almost completely avoided through in situ modification of silica with Si-CH₃ groups in the polyurethane dispersion. Composite films prepared with this method exhibited a superior hardness and abrasion resistance even at a lower silica content compared with that containing unmodified silica. In particular, optical microscopy and scanning probe microscopy observations demonstrated wear behavior differences among these composite films from the macro- and nanoscale viewpoints, respectively. It is proved that abrasive wear occurs, and surface morphology studies are in accordance with the results of abrasion resistance tests.     

Synthesis and characterization of nanosilica/waterborne polyurethane end‐capped by alkoxysilane via a sol‐gel process

A novel method was used to synthesis nanosilica/waterborne polyurethane (WPU) hybrids by in situ hydrolysis and condensation of tetraethyl orthosilicate (TEOS) and/or 3‐aminopropyltriethoxylsilane bonding at the end of the WPU molecular chain. The hybrid was characterized by scanning electron microscopy, energy dispersive spectroscopy (EDS), transmission electron microscopy, Fourier transform infrared spectroscopy (FTIR), and X‐ray photoelectron spectroscopy (XPS). The results showed that the nanosilica/WPU hybrids with well‐dispersed nanosilica particles were synthesized, in which the particles had typical diameters of about 50 nm. In addition, XPS and FTIR analyses demonstrated that chemical interaction occurred between WPU and silica. The effects of TEOS on surface wettability, water resistance, mechanical strength, and thermal properties of the hybrid were also evaluated by contact angle measurements, water absorption tests, mechanical tests, and differential scanning calorimetry, respectively. An increase in advancing contact angles, water resistance, and tensile strength, as well as decrease in elongation at break and glass transition temperature, were obtained with the addition of TEOS. Water absorption decreased from 17.3 to 5.5%. The tensile strength increased to a maximum of 29.7 MPa, an increase of about 34%. Elongations at break of the hybrids decreased 191%. These results were attributed to the effects of the nanosilica and the chemical interaction between WPU and silica. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Hybrid ternary organic-inorganic films based on interpolymer complexes and silica

Homogeneous transparent hybrid films consisting of chitosan (CHI), poly(monomethyl itaconate) (PMMI) and silica were obtained indicating the absence of microphase separation. These ternary hybrid materials are very interesting since materials with high functionality can be obtained presenting different properties from those of the starting materials but with the advantage of preserving the inherent property of each component. The inorganic phase was prepared by sol-gel process of tetraethoxysilane (TEOS). Most of the amine groups from CHI (pK_b 7.7) are quaternized in the acidic medium used in the preparations (pH=2), where a physical crosslinking via hydrogen bonding could occur through carboxyl groups from PMMI. Silica gel obtained from TEOS has been intercalated as a very fine dispersion in the polymer complex formed between CHI and PMMI. Transmission electron microscopy and atomic force microscopy was used to examine the homogeneity of the ternary polymer hybrids (CHI/PMMI/SiO₂), obtained as self-supported films. The results support the nanometer scale dispersion of the phases. Porous silica films with high BET area were obtained by calcination of the hybrid films. The mean pore diameter of these silica films corresponds to the dimension of the polymer domains observed in the pristine hybrid films. Moreover, it was found that the swelling behavior of the samples was influenced by the organic and inorganic phases, where the inorganic phase tends to diminish the swelling.     

乙醇对溶胶-凝胶法制备SiO_2溶胶性能的影响

以HNO3为催化剂,用正硅酸乙酯(TEOS)溶胶-凝胶工艺制备纳米多孔二氧化硅薄膜。较详细地研究了工艺参数乙醇/TEOS摩尔比对溶胶性能的影响.结果表明,随着乙醇/TEOS摩尔比的增大,溶胶粘度减小,凝胶时间变长,胶体粒径有变小趋势。     

水性聚氨酯包封原生SiO2纳米复合材料的制备及表征

主要研究了SiO2 /水性聚氨酯 (WPU)无机 -有机纳米复合物的制备方法。TEM和动态光散射分析表明 ,SiO2 /WPU纳米复合物粒子分散于WPU胶束内部 ,粒径在 60nm左右 ,具有核 -壳型结构的纳米级微粒。体系有着良好的稳定性和透光性 ,并且其随着SiO2 含量的增加而降低。胶束良好的包覆作用 ,抑制了纳米粒子的团聚 ,是保持其良好的稳定性和较小粒径的原因     

Sol–gel incorporation of silica nanofillers for tuning the anti-corrosion protection of acrylate-based coatings

The aim of the present work is to synthesize through sol–gel approach new hybrid polymeric nanocomposites to be used as coating materials. An acrylic-based polymer was prepared by free-radical copolymerization of two monomers widely used for coatings, namely 2-ethylhexylacrylate (EHA) and glycidyl methacrylate (GMA) bearing epoxy moieties, in which silica nanoparticles were incorporated by in situ acid hydrolysis and subsequent condensation of tetraethoxysilane (TEOS). Glycidoxypropyl trimethoxysilane (GPTS) was used as coupling agent to fine-tune the compatibility between organic and inorganic phases. The morphology, mechanical properties and corrosion resistance of thin films applied on aluminum alloys were optimized by varying the content of silica nanoparticles whose properties were strongly affected by the TEOS/GPTS ratios. Performances of the obtained hybrid materials were scrutinized by atomic force microscopy (AFM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), and electrochemical impedance spectroscopy (EIS). Thus it was evidenced that an optimum amount of silica nanoparticles with a precise morphology and composition in term of TEOS/GPTS ratio is needed to maintain good coating barrier properties. Outstanding anti-corrosion protection was reached by using optimized hybrid films.     

Preparation and characterization of cellulose acetate organic/inorganic hybrid films

A series of organic/inorganic hybrid (OIH) films were prepared using cellulose acetate (CA) as the organic component and tetraethyl orthosilicate (TEOS) as the inorganic component. The chemical, morphological, and mechanical properties of these films were evaluated with a variety of analytical techniques. The results of these evaluations showed that crosslinked CA OIH films were formed during the sol-gel reactions. The structure of OIH films was very sensitive to the CA/TEOS ratio and film formation conditions. All of the films with added TEOS were two phase on a molecular level, i.e., inorganic TEOS domains surrounded by a CA matrix. Under some film formation conditions the presence of TEOS, a nonsolvent for CA, led to solvent/nonsolvent phase separation on the micron scale. © 1995 John Wiley & Sons, Inc.     

Synthesis and properties of novel water‐dispersible polyisocyanates

A series of novel water‐dispersible polyisocyanates (WDPs) were synthesized with hexamethylene diisocyanate isoxyanurates (HDI trimer), dimethylol butanoic acid (DMBA), polyethylene glycol monomethyl ether (MPEG‐600) and 1,4‐cyclohexanedimethanol (CHDM) as materials. Two‐component waterborne polyurethane (2K‐WPU) films based on WDPs were prepared and characterized by ultraviolet‐visible spectrophotometer, thermogravimetric analyzer (TGA), scanning electron microscopy (SEM), and surface contact angle measurement. The effects of molar ratios of DMBA/MPEG and CHDM/MPEG and their amounts on properties of WDPs including the water dispersibility, storage stability, films hardness, and water resistance were also investigated. The results showed that the introduction of CHDM could efficiently improve the storage stability, the hardness and water resistance of 2K‐WPU films due to the rigid cyclic structure and hydrophobicity property of CHDM. It was found that WDPs had excellent storage stability, and the 2K‐WPU displayed short tack‐free times, high hardness, good water resistance, excellent surface appearance and gloss with 3:7:3 of the molar ratio of DMBA/MPEG/CHDM. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44735.     

原位交联聚乙烯醇/二氧化硅杂化功能膜的制备与性能

以正硅酸乙酯（TEOS）为前驱体,戊二醛（GA）为交联剂,利用溶胶凝胶法和原位化学交联法相结合的方法,制备了交联的聚乙烯醇/二氧化硅（PVA/SiO2）杂化功能膜。通过FTIR、SEM、溶胀和拉伸实验研究了二氧化硅和原位化学交联对杂化膜结构和性能的影响。结果表明,制备的膜是具有梯度交联结构的有机/无机杂化体系,原位化学交联对膜断面形貌影响不大。二氧化硅的引入和戊二醛原位交联都能有效地降低杂化膜的平衡溶胀度,两种因素在提高杂化膜耐水性方面具有互补作用。     

Surface and mechanical properties of hydrophobic silica contained hybrid films of waterborne polyurethane and fluorinated polymethacrylate

The surface and mechanical properties of hybrid films of waterborne polyurethane (WPU) and fluorinated polymethacrylate (FPMA), and high-hydrophobic silica (SiO₂) contained hybrid films of FPMA/WPU were investigated. X-ray photoelectron spectroscopy confirmed that the surfaces of hybrid films exhibited notable fluorine enrichment. Scanning electron microscopy observation demonstrated that micro-scale rough structures consisted of sub-micro papillae and micro-scale wrinkles formed on the surfaces of FPMA/WPU. This was attributed to the enhanced phase separation of WPU and the incompatibility of low-surface-energy FPMA and WPU. Colloidal SiO₂ was modified by polydimethylsiloxane and the modified SiO₂ was reactive and high-hydrophobic. After the addition of reactive SiO₂, the rough structures became micro-scale striped wrinkles studded with nano- and sub-micro papillae formed by the high-hydrophobic SiO₂. The combination of the fluorine enrichment and the rough structures accounted for the high hydrophobic FPMA/WPU film and superhydrophobic SiO₂/FPMA/WPU film.     

Self-healing waterborne polyurethane coating by pH-dependent triggered-release mechanism

In this study, effect of high-loaded silica capsules with corrosion inhibitor on thermal degradation and self-healing properties of waterborne polyurethane (WPU) was investigated. Silica capsules were synthesized using an oil in water (O/W) microemulsion and WPU was prepared via the prepolymer method. Assembled capsules demonstrated pH dependent release of their core. Incorporating silica capsule as an inorganic component resulted to improve thermal and barrier properties of WPU coatings. WPU coating with 1% silica capsules demonstrated better barrier quality in corrosive media and adding more than that resulted a rapid deterioration in barrier properties. Furthermore, such coatings possess an excellent adhesive strength with steel substrate. Electrochemical impedance spectroscopy was used in corrosion monitoring and healing procedure. Moreover, capsule morphology and thermal degradation of the WPU coating has been investigated separately by scanning electron microscopy and thermal gravimetric analysis. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47082.     

双酚A环氧树脂改性水性聚氨酯的合成及性能研究

以环氧树脂(EP)、异佛尔酮二异氰酸酯(IPDI)、聚酯二元醇和二羟甲基丙酸(DMPA)等为原料,合成了一系列不同EP含量的水性聚氨酯(WPU)分散体,讨论了EP、亲水基团含量对EP改性WPU分散体的储存稳定性、胶膜力学性能等影响。结果表明:当u(EP)≤3%、w(羧基)=1.6%时,EP改性WPU分散体及其胶膜的综合性能良好;利用WPU中残留的-NCO与EP中羟基反应,使EP被包覆在PU链段中,乳化后EP可稳定存在于WPU中,并且具储存稳定性、耐水性、耐溶剂性及力学性能等俱佳。     

Synthesis and characterization of hybrid films from hyperbranched polyester using a sol–gel process

Hybrid organic/inorganic materials were prepared by an in situ sol–gel process using tetraethoxysilane (TEOS) in the presence of hyperbranched polyester. The influences of hyperbranched polyester molar mass as well as the amount of TEOS were examined. The condensation degree was characterized by solid state ²⁹Si NMR. The combination of solubility tests, calcination tests, SAXS and dynamic mechanical analysis allowed us to investigate the hybrid material nanostructure. The results show high compatibility between the inorganic silica phase and the organic polymer phase, due to the spherical shape of the hyperbranched polymer and its numerous hydroxyl groups. As a consequence, a continuous inorganic phase was formed even with a low silica precursor content without any macroscopic phase separation. These hybrid materials have a high T_g and high storage modulus even at an elevated temperature combined with improved thermal stability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39830.     

Linseed polyurethane/tetraethoxyorthosilane/fumed silica hybrid nanocomposite coatings: Physico-mechanical and potentiodynamic polarization measurements studies

The work presents the physico-mechanical properties and potentiodynamic polarization measurements studies of linseed oil based polyurethane/tetraethoxyorthosilane [LPU/TEOS] hybrid and polyurethane/tetraethoxyorthosilane/fumed silica NC [LPU/TEOS/FS] hybrid nanocomposite coatings. The best coating performance was obtained by the inclusion of 2 wt% FS in 2-LPU/TEOS hybrid. 2-LPU/TEOS/FS produced glossy, transparent, flexibility retentive, scratch-resistant and impact resistant coatings at ambient temperature relative to LPU/TEOS coatings. 2-LPU/TEOS/FS showed good scratch hardness (5.5 kg), impact resistance (250 lb/in.), flexibility (1/8 in.) as investigated by standard methods with corrosion rate obtained as 3.567 × 10⁻⁴ mm/year and 4.05 × 10⁻⁴ mm/year and inhibition efficiency as 99.816% and 99.710% in 3.5% NaOH and 3.5% HCl, respectively.     

表面改性硅溶胶粒子增强聚甲基硅树脂薄膜材料

以甲基三甲氧基硅烷（MTMS）水解聚合产物作为主要成膜物质,经甲基丙烯酰氧基丙基三甲氧基硅烷（MEMO）表面改性的正硅酸乙酯（TEOS）水解产物硅胶作为无机增强物,利用两者羟基之间的共缩聚反应在聚碳酸酯（PC）板表面制备有机/无机复合透明耐磨薄膜;采用TG/DTA、FTIR、UV-vis、金相显微镜及SEM等测试手段对不同含量MEMO改性硅胶对薄膜结构及性能的影响进行表征.研究结果表明,MTMS和TEOS的水解聚合产物通过共缩聚反应在PC板表面形成带有机基团的无机交联网络结构,基本骨架由Si—O—Si组成;在150～250℃之间,MEMO所带的C=C会发生热引发自由基聚合反应;随MEMO含量的增加,薄膜的柔韧性提高;薄膜对PC板有一定的增透作用,MEMO含量的改变对其增透性能影响不大;薄膜能显著提高PC板的硬度,随着MEMO含量的增加,能制备厚膜而不易开裂.     

不同聚醚二元醇软段对光固化水性聚氨酯乳液性能的影响

以不同聚醚二元醇、异佛尔酮二异氰酸酯、2,2-双羟甲基丙酸、甲基丙烯酸-2-羟基乙酯为主要原料,通过丙酮法合成光固化水性聚氨酯(WPU)乳液,讨论了不同聚醚软段对光固化WPU乳液性能的影响.结果表明,由聚四氢呋喃醚二元醇PTMG1000和PTMG2000制备的光固化WPU乳液具有较小的粒径和粘度,其交联后的膜具有较高储...     

Synthesis and characterization of phosphorus‐containing waterborne polyurethanes: Effects of the organophosphonate content on the flame retardancy,morphology, and film properties

A series of waterborne polyurethanes (WPUs) with different contents of reactive organophosphonate were well prepared. Their structures were characterized by Fourier transform infrared and ¹H‐NMR spectroscopy. Thermogravimetry and derivative thermogravimetry revealed that the WPU films containing phosphorus possessed lower onset and maximum degradation temperatures but higher char yields. Differential scanning calorimetry analysis suggested phase mixing of the hard and soft domains. The mechanical properties decreased with increasing amount of organophosphonate, whereas the limiting oxygen index results of the WPU films indicate that the flame retardancy was improved significantly by the incorporation of organophosphonate. The water uptake values of the organophosphonate‐containing WPU films were higher than those of the phosphorus‐free ones, whereas the static contact angles of the films indicated that the surface hydrophilic properties were not affected by segmenting in this phosphorus‐containing oligomer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Waterborne polyurethane-silica nanocomposite adhesives based on castor oil-recycled polyols: Effects of (3-aminopropyl)triethoxysilane (APTES) content on properties

Waterborne castor oil-recycled polyol based polyurethane-silica nanocomposite adhesives (WPU) with polymer matrix and silica nanoparticles chemically bonded have been successfully prepared through a sol-gel process. A series of waterborne polyurethane adhesives with hard segment contents from 71.3 to 74.5 wt%, were synthesized using an isophorone diisocyanate, 2-bis(hydroxymethyl) propionic acid, recycled castor oil-based as soft segments and (3-aminopropyl)triethoxysilane (APTES) as chain extender. The depolymerized oligoester obtained from glycolysis of poly(ethylene terephthalate) (PET) waste using triethylene glycol (TEG), was transesterified with castor oil (CO) which resulted in the formation of hydroxyl-functional polyester polyol, with hydroxyl value of 414 mgKOH g⁻¹. The molecular structures and mass of glycolyzed PET oligoesters, castor oil-based polyol and castor oil-based polyurethane-silica nanocomposite adhesives were estimated by Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The structure and properties of the resulting films were investigated by FTIR, wide angle X-ray diffraction measurement (XRD), thermogravimetry (TG) and differential scanning calorimetry (DSC). TG analysis indicated that APTES can improve the thermal stability of WPU. XRD showed that the crystallinity of WPU decreased with the increase alkoxysilane content. The extent of crosslinking was investigated to show a dependence on silica concentration, which increased the glass transition temperature and particle size of polyurethane nanocomposites with increasing alkoxysilane content due to the condensation of the alkoxysilane groups. The hardness, adhesion and gloss quality of the polyurethane films were also determined considering the effect of APTES content, so this paper confirmed the suitability of using these castor oil-based waterborne polyurethane-silica nanocomposites as new adhesive materials with high performance coatings materials. The experimental results reveal that the APTES and the hard segment content play a key role in controlling the structure and properties of the PU cast films based on castor oil-recycled polyols.     

Polyamide-6,6/in situ silica hybrid nanocomposites by sol-gel technique: synthesis, characterization and properties

The organic-inorganic hybrid nanocomposites comprising of poly(iminohexamethyleneiminoadipoyl), better known as Polyamide-6,6 (abbreviated henceforth as PA66), and silica (SiO₂) were synthesized through sol-gel technique at ambient temperature. The inorganic phase was generated in situ by hydrolysis-condensation of tetraethoxysilane (TEOS) in different concentrations, under acid catalysis, in presence of the organic phase, PA66, dissolved in formic acid. Infrared (IR) spectroscopy was used to monitor the microstructural evolution of the silica phase in the PA66 matrix. Wide angle X-ray scattering (WAXS) studies showed that the crystallinity in PA66 phase decreased with increasing silica content. Atomic force microscopy (AFM) of the nanocomposite films revealed the dispersion of SiO₂ particle with dimensions of <100 nm in the form of network as well as linear structure. X-ray silicon mapping further confirmed the homogeneous dispersion of the silica phase in the bulk of the organic phase. The melting peak temperatures slightly decreased compared to neat PA66, while an improvement in thermal stability by about 20 °C was achieved with hybrid nanocomposite films, as indicated by thermogravimetric analysis (TGA). Dynamic mechanical analysis (DMA) exhibited significant improvement in storage modulus (E′) for the hybrid nanocomposites over the control specimen. An increase in Young's modulus and tensile strength of the hybrid films was also observed with an increase in silica content, indicating significant reinforcement of the matrix in the presence of nanoparticles. Some properties of the in situ prepared PA66-silica nanocomposites were compared with those of conventional composites prepared using precipitated silica as the filler by solution casting from formic acid.