The use of aminolysis,aminoglycolysis, and simultaneous aminolysis–hydrolysis products of waste PET for production of paint binder

This work is concerned with the use of aminolysis, aminoglycolysis, and simultaneous aminolysis–hydrolysis products of waste PET for production of paint binder based on alkyd resin. For this purpose, first, aminolysis, aminoglycolysis, and simultaneous hydrolysis–aminolysis reactions of waste PET were carried out in the presence of different chemical agents in xylene medium at high pressures. Reactions of waste PET flakes obtained from grinding postconsumer water bottles were carried out in an autoclave at higher temperatures. Then, four alkyd resins, formulated to have oil content 40–50%, were prepared using these depolymerization products. One of resins is “reference alkyd resin” which was prepared by using soybean oil fatty acid, phthalic anhydride, glycerine, and ethylene glycol for comparison. Other three alkyds are “depolymerization product‐based alkyd resins” in which depolymerization products is used instead of ethylene glycol. Then, the physical and chemical surface coating properties and thermal behaviors of alkyd resins films were investigated comparatively. As a result, we concluded that aminolysis, aminoglycolysis, and simultaneous aminolysis‐hydrolysis products of waste PET are suitable for manufacturing both air drying and oven curing paint binder based on alkyd resins. The film prepared from alkyd resin based on simultaneous aminolysis‐hydrolysis product showed extremely good surface coating properties and thermal stability. POLYM. ENG. SCI., 54:2272–2281, 2014. © 2013 Society of Plastics Engineers     

Dry‐peelable temporary protective coatings from waterborne self‐crosslinkable sulfourethane–silanol dispersions

Novel temporary protective coatings were prepared by the addition of release additives to waterborne polyurethane dispersions. New types of self‐crosslinkable sulfourethane–silanol (SUS) dispersions were utilized as the peelable coatings. These dispersions are stable, low‐volatility organic chemical (VOC) waterborne dispersions that spontaneously crosslink upon drying without extra additives or processing steps. Tensile strengths up to 6000 psi with elongations between 300–600% were obtained for the crosslinked films. The adhesion of the films to a variety of substrates can be controlled by the addition of hydrophilic additives, including glycerol, oligomers of glycerol, and poly(ethylene glycol) derivatives. Alternatively, hydrophobic additives that are water dispersible, such as paraffin waxes and sulfated castor oil, can also be used to control adhesion. In addition, this technique can be utilized for the release of films derived from a wide variety of waterborne urethane dispersions, including carboxylated polyurethane ureas. The removable coatings are useful for the temporary protection of plastic surfaces during thermoforming processes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1443–1449, 2004     

Bamboo tar‐based polyurethane wood coatings

Bamboo tar is a natural resource of aromatic polyol obtained from a residue of by setting or distilling crude bamboo vinegar. In this study, the two‐packed polyurethane (PU) coatings were prepared by blending bamboo tar and castor oil varying with different weight ratios and polymeric toluene diisocyanate (PTDI) was used as a hardener at the NCO/OH molar ratio of 1.0. Six kinds of PU coatings were formulated and the viscosity, pot‐life, drying time, mechanical properties (hardness, tensile strength, impact resistance, adhesion, and abrasion resistance), gel content, durability, lightfastness, FTIR, thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA) were characterized. The results indicated that the bamboo tar containing PU film appearance is semitransparent yellow‐brown color and the wood texture could be kept after finishing. All PU films possessed excellent adhesion as well as durability. The increase in bamboo tar content led to shorten drying time of coatings and to increase in hardness, tensile strength, lightfastness, and thermal stability of films. From these results and due to a light smell flavor, it is suggested that the bamboo tar‐based PU coatings is suitable to be used as an exterior wood coatings. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study of nanoreinforced shape memory polymers processed by casting and extrusion

Multi‐walled carbon nanotubes (CNTs) and cellulose nanofibers (CNFs) reinforced shape memory polyurethane (PU) composite fibers and films have been fabricated via extrusion and casting methods. Cellulose nanofibers were obtained through acid hydrolysis of microcrystalline cellulose. This treatment aided in achieving stable suspensions of cellulose crystals in dimethylformamide (DMF), for subsequent incorporation into the shape memory matrix. CNTs were covalent functionalized with carboxyl groups (CNT‐COOH) and 4,4′‐methylenebis (phenylisocyanate) (MDI) (CNT‐MDI) to improve the dispersion efficiency between the CNT and the polyurethane. Significant improvement in tensile modulus and strength were achieved by incorporating both fillers up to 1 wt% without sacrificing the elongation at break. Electron microscopy was used to investigate the degree of dispersion and fracture surfaces of the composite fibers and films. The effects of the filler (type and concentration) on the degree of crystallinity and thermal properties of the hard and soft segments that form the PU sample were studied by calorimetry. Overall, results indicated that the homogeneous dispersion of nanotubes and cellulose throughout the PU matrix and the strong interfacial adhesion between nanotubes and/or cellulose and the matrix are responsible for the enhancement of mechanical and shape memory properties of the composites. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Impact of the coating process on the molecular structure of starch‐based barrier coatings

Molecular analysis of starch structure can be used to explain and predict changes in physical properties, such as water vapor and oxygen barrier properties in packaging materials. Solution casting is a widely used technique to create films from starch formulations. This study compared the molecular properties of these standard films with those of experimental coatings applied to paper in laboratory‐scale and pilot‐scale trials, with all three techniques using the same starch formulation. The results revealed large differences in molecular structure, i.e., cross‐linking and hydrolysis, between films and coatings. The main differences were due to the shorter drying time allowed to laboratory‐scale coatings and the accelerated drying process in pilot trials owing to the high energy output of infrared dryers. Furthermore, surface morphology was highly affected by the coating technique used, with a rougher surface and many pinholes occurring in pilot‐scale coatings, giving lower water vapor permeability than laboratory‐scale coatings. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41190.     

Graft polymerization of acrylonitrile onto starch‐coated polyethylene film surfaces

Starch‐coated polyethylene (PE) films were prepared by immersing PE in a hot, jet cooked solution of starch. They were allowed to react with acrylonitrile (AN) in the presence of ceric ammonium nitrate initiator, and the graft polymerization that occurred produced starch‐g‐polyacrylonitrile (PAN) coatings that contained about 25 wt % grafted PAN. The starch‐g‐PAN coatings tightly adhered to the PE film surfaces. When grafted starch coatings were wetted with water and the surfaces vigorously rubbed, less than 20% of the coating was removed. The fact that PAN‐grafted coatings were not removed with boiling water provided further evidence for their strong adherence. When starch was removed from the coating by acid hydrolysis, the residual grafted PAN still remained adsorbed on the PE surface. Because the grafted coating was completely removed by treatment with refluxing 0.7N sodium hydroxide, there is apparently no chemical bonding between starch‐g‐PAN and PE. The dimensional changes associated with the evaporation of water from these PAN‐grafted coatings caused the films to curl during drying. Because the final shape of these coated films depends upon the presence or absence of water in the surrounding environment, these films may be considered to be a type of stimulus‐responsive polymer. Attempts to graft polymerize methyl methacrylate and methyl acrylate onto starch‐coated PE surfaces, under conditions similar to those used with AN, were unsuccessful. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3323–3328, 2003     

Surface properties of polyurethane powder lacquers modified with polysiloxane‐methacrylic core‐shell nanoparticles

Non‐ and core‐shell nanoparticles‐containing polyurethane‐based powder coating systems, crosslinked with allophanate bonds containing polyisocyanates were examined. The surface structure of the powder coatings were investigated with a confocal microscopy and polarized optical microscopy (POM) using reflected light. The three‐dimensional surface topography and the values of surface roughness were determined. The surface structure was correlated with the chemical structure of the coatings and macroscopic surface behavior: surface free energy and gloss. These experimental results led to a better understanding of the development of surface topography and morphology and provide valuable information for the development of new polyurethane powder coating systems. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Strong resistance of poly (ethylene glycol) based L‐tyrosine polyurethanes to protein adsorption and cell adhesion

Biofouling that involves protein adsorption, cell and bacteria adhesion, and biofilm formation between a surface and biological entities is a great challenge for biomedical and industry applications. In this work, L ‐tyrosine‐derived polyurethanes (L ‐polyurethane) with different molecular weights of poly(ethylene glycol) (PEG) were synthesized, characterized and coated on gold surfaces using spin‐coating. The non‐fouling activity of different L ‐polyurethane films was evaluated by protein adsorption and cell adhesion. Surface plasmon resonance and cell assay results demonstrate that the PEG content in these L ‐polyurethanes contributes excellent resistance to protein adsorption and cell attachments. This work provides alternative and effective biomaterials for potential applications in blood‐contacting devices. Copyright © 2011 Society of Chemical Industry     

Structure and composition of the surface of urethane/acrylic composite latex films

Polyurethane dispersions were prepared and urethane/acrylic composite latices were synthesized with polyurethane dispersions as the seed, and core‐shell emulsion polymerization. Fourier‐transform infrared spectroscopy coupled with attenuated total reflectance (FTIR‐ATR) analyses showed that the films obtained from the composite latices were rich in polyurethane component or segments at air‐facing and substrate‐facing surfaces, in comparison with their average composition. Moreover, the substrate‐facing surface contained even more polyurethane component or segments than the air‐facing surface. X‐ray photoelectron spectroscopy (XPS) detection also indicated that the polyurethane component or segments preferentially migrated to the surface layer of the films from the bulk, and that the films from blend latices displayed more polyurethane component or segments near the surface layer. Both FTIR‐ATR and XPS analyses suggested that some reorientation had happened in synthesizing the composite latices and/or after film formation. This structure and composition endow urethane/acrylic composite films with both surface properties (such as mar‐resistance, adhesion, wettability) from pure polyurethane, and film hardness from acrylic copolymers. © 2001 Society of Chemical Industry     

The influence of ageing of epoxy coatings on adhesion of polyurethane topcoats and protective properties of coating systems

The dependence of adhesion and protective properties of coating systems on surface properties of epoxy intermediate coatings, aged and non-aged before an application of polyurethane topcoats, were examined. The intermediate coatings were aged 500 h in UV chamber. The surface free energy and polar groups were estimated after ageing. After applying polyurethane topcoats on aged and non-aged epoxy coatings, resistance to salt spray and thermal shocks were tested as well as internal stresses were measured before and after corrosion tests.The results showed that adhesion in coating systems with polyurethane topcoats applied on aged epoxy coatings depends strongly on the degradation degree of epoxy intermediate coatings and the value of generated internal stresses. Coatings with good adhesion retention in corrosion environments have good protective properties even when temporary blistering has occurred.     

Investigation of the effect of ZnO nanoparticles on the thermomechanical and microbial properties of hyperbranched polyurethane‐urea hybrid composites

Hybrid coatings of hyperbranched polyurethane‐urea (HBPUU) containing ZnO nanoparticles were prepared by mixing the hyperbranched polyurethane with the nanoparticles. The films were stored at room temperature and laboratory humidity conditions for one week to yield completely cured hybrid films. The ZnO nanoparticles were found to be well dispersed in the polymer up to 3 wt%. The structure–property relationship of various HBPUU–ZnO hybrid coatings was analysed using a Fourier transform infrared peak deconvolution technique with a Gaussian curve‐fitting procedure, while their viscoelastic, thermomechanical and surface morphology were studied using X‐ray diffraction, dynamic mechanical thermal analysis, thermogravimetric analysis, a universal testing machine, scanning electron microscopy, atomic force microscopy and contact angle instruments. The thermal stability and mechanical properties of the hybrid composite films improved with increasing ZnO content, which was believed to be due to thermal insulation in the presence of nanoparticles. Water contact angle data suggested that the hydrophobic character of the hybrid composites increased with increasing nanoparticle concentration. The antimicrobial property of the HBPUU–ZnO hybrid coatings was studied using the disc diffusion method. HBPUU–ZnO hybrid coatings showed good antimicrobial properties compared to HBPUU. Copyright © 2012 Society of Chemical Industry     

Effects of ultraviolet irradiation treatment on the surface properties and adhesion of moso bamboo (Phyllostachys pubescens)

The poor adhesion of bamboo coatings is a serious issue in the bamboo industry. To overcome this problem it is necessary to modify the actual surface of the bamboo before finishing. A study on the surface properties and adhesion of moso bamboo (Phyllostachys pubescens) were investigated with various UV irradiation conditions including irradiation time and dose using different UV lamps. Two types of wood coatings, i.e., solvent‐borne nitrocellulose (NC) lacquer and waterborne polyurethane (PU) coating, were used in the study, and 180° peel strength and shear strength tests for measuring adhesion of films were conducted. The results revealed that the wettability and the carbonyl group concentration of the bamboo surface were increased. This was particularly apparent for an irradiation time less than 15 s with a mercury UV lamp (H‐lamp), rated at an intensity of 100 W/cm kept at a distance of 15 cm. In all the treatments, the greenish appearance of moso bamboo was retained and the adhesion was improved. Especially, using solvent‐borne NC lacquer finishing, the higher‐dose (under a mercury UV lamp combined with metal halide lamp; H + M‐lamps) irradiated bamboo had the best adhesion, while, for waterborne PU coating, the H‐lamp irradiated one showed the best improvement. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Coatings prepared from waterborne polyurethane dispersions obtained with polycarbonates of 1,6-hexanediol of different molecular weights

Waterborne polyurethane dispersions (PUDs) were synthesized with polycarbonates of 1,6-hexanediol of different molecular weight (500–3000 Da) and their properties, adhesion (Hatch adhesion) and coatings on stainless steel properties (Pencil hardness, Persoz hardness, gloss at 60°, chemical resistance, yellowness index) were characterized. The hatch adhesion of the polyurethane coatings to stainless steel was very good and decreased slightly by increasing the molecular weight of the polycarbonate of 1,6-hexanediol. Both the Pencil and Persoz hardness values of the coatings increased by increasing the hard segments content in the polyurethane, i.e. by decreasing the molecular weight of the polycarbonate of 1,6-hexanediol, whereas the gloss and the yellowness index were lower for the coatings obtained with the polycarbonate of 1,6-hexanediol of molecular weight of 500 Da. Very good chemical resistance against ethanol for all polyurethane coatings on stainless steel plates was obtained but for long time of ethanol in contact with the coating surface the chemical resistance decreased, more markedly for the polyurethane coating obtained with the polycarbonate of 1,6-hexanediol of higher molecular weight. In summary, the segmented structure of the waterborne polyurethane dispersion determined the properties of the polyurethane coatings obtained from them.     

聚氨酯改性环氧树脂耐磨涂料的研制

以2,4-甲苯二异氰酸酯和蓖麻油为原料,合成了聚氨酯预聚体。使用该聚氨酯预聚体对环氧树脂进行了改性。对各种固化剂进行了筛选。最后研制了一种双组分常温固化耐磨涂料。通过正交实验和单因素实验确定了涂料的最佳配方:聚氨酯5 g,环氧树脂10 g,填料3 g,固化剂2．3 g。由此获得的耐磨性优良的涂膜性能为:表干时间10 h,实干时间不到40 h;耐磨性实验中,磨痕弦长5．4 mm;附着力0级,硬度5 H。     

Novel oxidatively drying urea resin. II. Surface coating properties of N,N′-bis(methoxymethyl) urea-based air-drying resins

The surface coating properties of the air-drying urea resins prepared by polycondensating N,N′-bis(methoxymethyl) urea (BMMU) with trimethylolpropane diallylether (TMPDA) and 2-ethylhexanol (2EH) were studied. It was found that the thinnability of the ethanolic resin solutions with water decreased with increasing molecular weight and the degree of modification of the resins with TMPDA and 2EH. The viscosity of the ethanolic resin solutions increased with the molecular weight but was independent on the resin's degree of modification. The drying performance was improved with increasing molecular weight and decreasing modification with 2EH. The hardness of the paint films was proportional to the modification of the resins with TMPDA and the molecular weight. 2EH led to the plasticization of the coatings. The water resistance of the paint films was improved with increasing modification with 2EH and molecular weight of the resin. The analysis of the elastic properties of the hardened films was not possible due to the scatter of the experimental data. The comparison of the amino resin paints to some commercial paint products indicated that BMMU-based resins having good drying performance and adequate water resistance at the same time can be prepared. Neutral ethanolic and aqueous ethanolic resin solutions were found to have a good storage stability as determined by following the viscosities of the solutions and the hydrolysis resistance of the resins.     

Anionic waterborne polyurethane dispersions based on hydroxyl‐terminated polybutadiene and poly(propylene glycol): Synthesis and characterization

Nonpolluting systems based on anionic polyurethane aqueous dispersions were obtained. The prepolymer based on hydroxyl‐terminated polybutadiene (HTPB), isophorone diisocyanate (IPDI), poly(propylene glycol) (PPG), and dimethylolpropionic acid (DMPA) were synthesized in bulk. After neutralization with triethylamine (TEA), the anionomer prepolymer was dispersed in water, followed by a chain‐extension reaction with ethylenediamine (EDA). The prepolymers were characterized by Fourier transform infrared spectrometry (FTIR) and the average particle size of the aqueous dispersions was determined by laser light scattering (LLS). The mechanical behavior of polyurethane‐cast films and the adhesive properties of the aqueous dispersions as coatings for wood were evaluated. It was observed that an increase in the HTPB content provoked an increase in the viscosity and in the particle size of the dispersions. The tensile strength and the modulus values of the films and the adhesiveness of the coatings in wood were also increased by increasing the HTPB content. On the other hand, the elongation of the polyurethane‐cast films and the tackness of the surface coatings decreased as the HTPB was increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 566–572, 2001     

Microstructural and mold resistant properties of environment‐friendly oil‐modified polyurethane based wood‐finish products containing polymerized whey proteins

Environmental concerns associated with the level of volatile organic compounds used in surface coatings have stimulated increased scientific research toward novel methods of developing environment‐friendly coatings. Prototype wood finish products containing polymerized whey proteins (PWP) were formulated. The microstructural characteristics of dry films prepared from environment‐friendly wood finishes containing PWP were examined using atomic force microscopy (AFM) and confocal laser scanning microscopy (CLSM). The susceptibility of the coatings to microbial degradation was also examined using an accelerated mold test. AFM analysis revealed that increased addition of PWP resulted in films with increased surface roughness, decreased number of voids, and increased void size due to excessive aggregation among polymer components. CLSM analysis showed that the PWP distribution in the films is enhanced by homogenization of the coating mixes. There was no significant increase (P > 0.05) in mold growth between panels coated with finish containing PWP and those without PWP. Test panels coated with formulation containing PWP and low levels of biocide (0.3%) resulted in a significant decrease in mold growth in comparison to commercially available water‐based polyurethane coatings (P < 0.05). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3519–3530, 2006     

Influence of MA‐g‐HDPE compatibilizer content on quality and adhesion/bending strength of polyethylene/O‐MMT coating films

High density polyethylene/organo‐modified montmorillonite composites whit various concentrations of maleic anhydride grafted high density polyethylene (MA‐g‐HDPE) as compatibilizer (5–20 wt %) have been prepared by melt process. The extruded composite powders are applied on the treated steel surfaces using spray electrostatic powder technique, followed by oven curing at various temperatures (180°C–220°C) and times (15–45 min). The surface uniformity of produced coating films is studied by scanning electron microscopy. Comparison of micrographs of the coatings shows the composite coating films are measured using standard methods. The uniformity, adhesion, and bending strength of the coating films are compared to select high performance coatings. The results indicate that the presence of 15 wt % MA‐g‐HDPE in the coatings shows the highest properties (adhesion and bending strength) and more surface uniformity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40926.     

HDI三聚体改性聚氨酯水分散体的合成与性能

采用己二异氰酸酯(HDI)三聚体(HT)合成交联改性聚氨酯水分散体(HPUD),考察了HT添加量对HPUD涂膜的耐水性、耐溶剂性、表干时间、硬度、光泽以及交联度的影响。通过粒径分布仪、热重分析仪(TGA)和傅立叶变换红外光谱仪(FTIR)分别对HPUD乳液贮存过程中粒径的变化、涂膜热稳定性与分子结构进行表征,结果发现,引入质量分数5%～10%的HT可提高聚氨酯涂膜的表干速率和交联度,当w(HT)=10%时,HPUD涂膜具有最佳的综合性能,涂膜表干时间为45min,交联度为80%,吸醇率为78%,吸水率为7%。同时还发现,HPUD涂膜硬度上升速率较快,但最终硬度较未改性聚氨酯水分散体(PUD)有所降低;粒径分析表明,当w(HT)≥20%时,HPUD贮存过程中乳液粒径增大,贮存稳定性下降;TGA分析表明,HPUD涂膜具有较好的热稳定性。     

Optical and surface properties of whey protein isolate coatings on plastic films as influenced by substrate,protein concentration,and plasticizer type

Composite film structures of common plastic polymers including polypropylene (PP) or poly(vinyl chloride) (PVC) with whey protein isolate (WPI) coatings may be obtained by a casting method. Optical and surface properties of the resulting WPI‐coated plastic films, as affected by protein concentration and plasticizer type, were investigated to examine the biopolymer coating effects on surface modification with polymeric substrates of opposite polarity. The measured properties involved specular gloss, color, contact angle, and critical surface energy. Regardless of the substrates, WPI‐coated films possessed excellent gloss and no color, as well as good adhesion between the coating and the substrate when an appropriate plasticizer was added to the coating formulations. The protein concentration did not significantly affect gloss of WPI‐coated plastic films. Among five plasticizers applied, sucrose conferred the most highly reflective and homogeneous surfaces to the coated films. The WPI coatings were very transparent and the coated films with various protein concentrations and plasticizers showed no noticeable changes in color. Experimental results suggest that WPI coatings formulated with a proper plasticizer can improve the visual characteristics of the polymeric substrate and enhance water wettability of the coated plastic films. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 335–343, 2004