Synthesis of new hyperbranched urethane-acrylates and their evaluation in UV-curable coatings

Three series of hyperbranched urethane-acrylates (HB-UA), based on aliphatic hyperbranched polyesters and polyethyleneglycol acrylate, were prepared and evaluated for use in UV-curable coatings. UV-curing kinetics were monitored by FT-IR spectroscopy. The thermal and mechanical properties of UV-cured HB-UA were investigated by means of differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) and correlated to the mechanical properties of coatings (hardness and flexibility). These new HB-UA's are very reactive and did not show oxygen inhibition. Obtained coatings have good mechanical properties and solvent resistance.     

Preparation and characterization of UV-curable epoxy/silica nanocomposite coatings

To enhance the interfacial interaction in silica nanoparticles filled polymer composites, the silica surface was firstly treated with glycidoxypropyl trimethoxysilane (GPTMS), and its structure was analyzed by ¹³C NMR and FTIR spectrophotometry. Then a series of GPTMS-modified silica/cycloaliphatic epoxy nanocomposite coatings with 0–6 wt% silica content were prepared by UV-induced cationic polymerization in the presence of a diaryliodonium photoinitiator and thioxanthone photosensitizer. The physical and mechanical properties such as hardness, adhesion, gloss, impact as well as tensile strength were examined. As a result, these composites demonstrated superior tensile strength and tensile modulus with increasing proportion of modified silica up to a certain level. An increase in abrasion resistance of nanocomposites with the addition of modified silica was observed. The thermal stability of nanocomposites was not enhanced with the addition of silica particles. SEM studies indicate that silica particles were dispersed homogenously through the polymer matrix.     

Preparation and properties of novel high performance UV-curable epoxy acrylate/hyperbranched polysiloxane coatings

Novel high performance UV-curable coatings based on epoxy acrylate (EA) oligomer and hyperbranched polysiloxane (HPSi) were prepared, the effect of HPSi on the processing of uncured EA/HPSi system and integrated performance of cured resins is evaluated. Results show that a small addition of HPSi can greatly decrease the viscosity of EA oliogmer, while the viscosity almost does not reduces as the content of HPSi continuously increases owing to the interaction between HPSi and EA oligomer. The integrated performance of cured resins is closely related with the content of HPSi, those resins with suitable contents of HPSi have significantly improved toughness and stiffness as well as thermal and moisture resistance. The origin of all these changes in macro-performance are investigated and proved to be resulted from the variety in the chemical structure and crosslinking density induced by the addition of HPSi. These attractive features of EA/HPSi resins suggest that HPSi is an effective multi-functional diluent for UV-curable EA resin, and the method proposed herein is a new approach to develop high performance UV-curable coatings, solvent-free resins, etc., for cutting-edge industries.     

Synthesis and characterization of ZnS/hyperbranched polyester nanocomposite and its optical properties

The ZnS/hyperbranched polyester nanocomposite with higher refractive index was prepared by incorporating the acrylated 2-(2-mercapto-acetoxy)-ethyl ester-capped ZnS nanoparticles into the acrylated Boltorn™ H20 (H20). The acrylated 2-(2-mercapto-acetoxy)-ethyl ester-capped colloidal ZnS nanoparticles were synthesized by the reaction of zinc acetate with thioacetamide in N,N-dimethylformamide. The acrylated hyperbranched polyester was obtained by reacting acryloyl chloride with hydroxyl group of H20. The acrylated H20 plays an important role in stabilizing and dispersing ZnS nanoparticles with a diameter of 1-4 nm. The refractive indices of ZnS/hyperbranched polyester nanocomposites, depending on ZnS content, were determined to be in the ranges of 1.48-1.65.     

Optimization of a UV-curable acrylate-based protective coating by experimental design

The influence of composition and processing parameters controlling the properties of UV-cured films was studied by the screening and quantification tools of experimental design methodology. Various formulations including acrylated prepolymers based on a polyurethane or a bis-phenol A core were blended with mono- and difunctional reactive diluents, isobornyl acrylate and hexanediol diacrylate, respectively. The influence of photo-initiator content and UV-dose were examined in experiments combining the different factors. The approach allowed formulating on rational bases a reactive blend yielding a coating exhibiting sufficient elasticity without exhibiting tackiness by blending the two types of prepolymers. An optimal domain of composition was defined by implementing a Scheffé's mixture design.     

A view from inside onto the surface of self-assembled nanocomposite coatings

Hybrid organic–inorganic (O–I) nanocomposite coatings with an O–I matrix and inorganic nanofillers were synthesized by two consecutive and independent processes: sol–gel process (build-up of inorganic structures with epoxide-functions in situ) and polyaddition reaction (epoxy network formation with amines). Two O–I matrices were prepared: the GTMS–D400 type exhibits a high degree of regularity and self-ordering in the bulk (inorganic domains separated by elastic D400 chains) while in the GMDES–T403 type a linear inorganic polyepoxide is homogeneously mixed with the amino component without any separated inorganic domains. Inorganic nanofillers (natural or chemically modified montmorillonites and colloidal silica) differing in size and shape, were added to the matrices. Core properties of the composite products, on sub-micrometer and micrometer levels were studied by solid-state NMR spectroscopy, transmission electron microscopy, and wide-angle X-ray scattering. Macroscopic, bulk properties of the materials were investigated by static and dynamic mechanical analysis. The gas transport properties of the prepared coatings were tested with hydrogen and oxygen. The surface morphology of the coatings with and without nanofillers was determined by atomic force and scanning electron microscopy. A high degree of self-organization existing already in the O–I matrix was observed in some cases, which obviously influences the self-assembly behaviour of the nanofillers in the O–I matrix and on the surface of the hybrid coatings.     

Synthesis and characterization of new polysiloxane bearing vinylic function and its application for the preparation of poly (silicone-co-acrylate)/montmorillonite nanocomposite emulsion

A new silicone containing acrylic monomer, methacryloxyethyl polymethylhydrosiloxane ether (MEPMHSE), based on polymethylhydrosiloxane (PMHS) and 2-hydroxyethyl methacrylate (HEMA) has been synthesized for formulation of nanocomposite emulsion. Then Poly (silicone-co-acrylate)/montmorillonite (PSAM)/nanocomposite emulsion were prepared by in situ intercalative emulsion polymerization of methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA) and MEPMHSE, in the presence of organic modified montmorillonite (OMMT) with different OMMT contents (0, 0.5, 1.0, 1.5 and 2 wt%) and auxiliary agents in the presence of potassium persulphate (KPS) as initiator. Alkylphenol ethersulphate and Arkupal N-300 were used as anionic and non-ionic emulsifiers, respectively. The resulting monomer was characterized by Fourier transformer infrared spectroscopy (FTIR), proton (¹H NMR), and carbon (¹³C NMR) nuclear magnetic resonance spectroscopes. The OMMT was characterized by FTIR and X-ray diffraction (XRD). The nanocomposite emulsions were characterized by using Fourier transform infrared spectroscopy (FTIR), laser light scattering and surface tension. Thermal properties of the copolymers were studied by using thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA) and then the effects of OMMT percent on the water absorption ratio and drying speed were examined. Results showed that OMMT could improve the properties of emulsion, in other words, the properties of nanocomposite emulsion were better when compared with those of the silicone–acrylate emulsion. The property of nanocomposite emulsion containing 1 wt% OMMT was the best one, and the following advantages were obtained: smaller particle size, faster drying speed, smaller surface tension, and improved resistant water by the incorporation of OMMT.     

Synthesis and properties of semi-crystalline hyperbranched poly(ester-amide) grafted with long alkyl chains used for UV-curable powder coatings

A series of semi-crystalline hyperbranched poly(ester-amide)s by modifying hydroxyl end groups of hyperbranched poly(ester-amide) (HP) with IPDI-C18 and IPDI-HEA in different ratios were synthesized and characterized by FTIR, NMR and GPC. Their crystallization behaviors and thermal properties determined by X-ray diffraction (XRD) and differential scanning calorimetry (DSC) showed that the high substitution degree of hydroxyl groups of hyperbranched poly(ester-amide) (HP) with IPDI-C18 resulted in higher degree of crystallization and thus glass transition temperature (T_g) up to 43 °C. The photopolymerization kinetics investigated by photo-DSC showed that the obtained semi-crystalline hyperbranched resins have high photopolymerization rate and final unsaturation conversion, which is very promising for UV-curable powder coating applications.     

Novel waterborne hyperbranched acrylated-maleinized alkyd resins

Different waterborne hyperbranched acrylated-maleinized alkyd resins (HBRAAM) were synthesized by modifying a hyperbranched alkyd resin (HBRA) with three different butylmethacrylate–maleic anhydride copolymers (BMA–MA) in the presence of p-toluenesulfonic acid (PTSA). The HBRAAM resins were characterized by using infrared analysis, iodine value, hydroxyl value, vapor pressure osmometry (VPO), dynamic light scattering (DLS), acid value, rheological analysis, differential scanning calorimetry, adhesion, flexibility, drying time, gloss, hardness and chemical resistance to solvents. The iodine value and hydroxyl value decreased with the amount of BMA–MA copolymer employed in the synthesis. Infrared analysis, VPO, and hydroxyl values allowed us to conclude that the reaction between HBRA resins and BMA–MA copolymers occurred. The viscosity of the HBRAAM resins was between 50.5 and 468 Pa s. All HBRAAM resins presented good properties of adhesion, flexibility, drying time, gloss, hardness and chemical resistance.     

Flame retardancy and thermal property of novel UV-curable epoxy acrylate coatings modified by melamine-based hyperbranched polyphosphonate acrylate

A novel melamine-based hyperbranched polyphosphonate acrylate (MHPA), successfully synthesized via the Michael addition polymerization of 2-(2-amino-ethylamino)-4,6-bisethylamino-1,3,5-triazine with tri(acryloyloxyethyl) phosphate, was blended with the epoxy acrylate (EA) to prepare UV-cured flame retardant coatings. The study of their flammability revealed that MHPA can improve the flame retardancy and the sample with 45 wt% MHPA (EA3) showed a good intumescent behavior when combusted. The results of their thermal degradation displayed that MHPA had a dual effect on the thermal stability of EA: leading to its earlier degradation catalyzed by acidic species from the relatively weak phosphorus-bearing parts, but improving the thermal stability of the char layer at high temperature due to the formed intumescent phosphorus–carbon compounds. Besides, the total release amount of gas products of EA3 was much lower than that of pure EA and various flammable gases like hydrocarbons and highly toxic CO were also reduced     

Synthesis of UV-curable acrylate polymer containing sulfonic groups for anti-fog coatings

A series of UV curable hydrophilic acrylate polymers containing sulfonic acid group was prepared via free radical copolymerization using 2-acrylamido-2-methyl propane sulfonic acid (AMPS) as hydrophilic monomer, which were used as prepolymers for anti-fog coatings. The expected structures were confirmed by FT-IR, ¹H NMR and gel permeation chromatography (GPC). These UV-curable acrylate polymers were then mixed with reactive diluents and photoinitiator to form coating formulas. Various substrates were coated with these formulas and cured under UV exposure to obtain transparent coatings with good adhesion and hardness. The anti-fog properties of UV-cured coating were measured by contact angle test and anti-fog test. The results showed that the AMPS content in prepolymer had a great influence on the anti-fog properties of UV-cured coating. The formula was optimized and the corresponding UV-curing anti-fog coating was manufactured. The test results indicated that the coatings showed good mechanical properties, great optical transparency and excellent anti-fog performance.     

Synthesis and application of novel UV-curable hyperbranched methacrylates from renewable natural tannic acid

With a view to developing high performance UV curable coatings with high renewable contents, acrylated epoxidized soybean oil (AESO) was combined with a novel kind of biorenewable tannic acid-based hyperbranched methacrylates (TAHAs). The TAHAs were synthesized by ring-opening reaction of glycidyl methacrylate (GMA), glycidyl ester of Versatic acid (CE10) and natural tannic acid (TA). The epoxy groups of GMA and CE10 were involved in the ring-opening reaction with the hydroxyl groups of TA while residual methacrylate groups can carry out photopolymerization. By controlling the ratio of GMA and CE10, TAHAs with varying degree of methacrylate groups have been prepared. The synthesized TAHAs were formulated into acrylated epoxidized soybean oil (AESO) based UV curable coatings to produce the biorenewable materials based UV curable coatings. The effects of TAHAs on AESO coated film properties of pendulum hardness, flexibility and adhesion were investigated. Mechanical properties, thermal properties and biodegradability of the cured films were also evaluated. With the incorporation of TAHAs, the hardness, adhesion, tensile strength of the cured coating films were remarkably improved, which were attributed to the unique structure of hyperbranched methacrylates. Meanwhile, the biorenewable content was not greatly decreased due to the biorenewable character of tannic acid in TAHAs. These results showed that TAHAs as efficient toughening agents could produce UV-curable coatings of balanced coating performance with reasonably high biorenewable content. Moreover, the environment degradability of AESO-based cured films was also enhanced after the addition of TAHAs.     

Effect of silane functionalization of montmorillonite on epoxy/montmorillonite nanocomposite

Mechanical and dynamic mechanical properties of various montmorillonite (MMT)/epoxy nanocomposites were investigated. 3-aminopropyltriethoxysilane functionalized MMT was compared with commercial pristine MMT and ammonium salt substituted MMT. Qualitative evidence of silane functionalization was confirmed by FT-IR. XRD and TEM were used to characterize the degree of intercalation of MMT in epoxy nanocomposite. Tensile stress and elongation of MMT/epoxy nanocomposite were improved significantly by the silane functionalization of MMT. Dynamic mechanical analysis showed that silane functionalization of MMT resulted in active interactions between MMT and epoxy.     

UV-radiation curing of waterbased urethane–acrylate coatings

A kinetic study of the drying and UV-curing of waterbased urethane–acrylate formulation was conducted by means of infrared spectroscopy. The water release upon heating of the dispersion was shown to depend on the temperature and on the film thickness. The drying of a 30 μm thick coating was completed in <2 min upon heating in an oven at 80°C. The influence of a number of critical factors on the polymerization kinetics has been investigated, namely the type of photoinitiator, the sample temperature, the chemical structure of the functionalized oligomer and its acid content. As expected, the latter factor has a strong effect on the properties of the UV-cured coatings, in particular their hardness and their hydrophilic character. The water uptake and the softening of coatings placed in a wet atmosphere was found to be directly related to the carboxylic acid content of the urethane–acrylate polymer. This phenomenon is fully reversible and does not affect the long term properties of the UV-cured coatings.     

Strengthening and toughening effects of layered double hydroxide and hyperbranched polymer on epoxy resin

The effects of organically modified layered double hydroxide (O-LDH) and epoxy functionalized hyperbranched aliphatic polyester (E1), on the mechanical strength, thermal property and toughness of diglycidyl ether of bisphenol A (DGEBA) epoxy resin were studied in detail. The crystalline structure and morphology of the nanocomposites composed of DGEBA/O-LDH and DGEBA/E1/O-LDH were investigated by wide angle X-ray diffraction analysis and transmission electron microscopy observation. Both results showed that the LDH nanosheets were sufficiently exfoliated and randomly dispersed in the epoxy matrix. The thermal and mechanical properties were compared with the corresponding neat polymer matrix. The enhancement in strength and toughness was achieved by the addition of O-LDH and E1, respectively, and confirmed in terms of fracture surface analysis by scanning electron microscopy.     

Aliphatic polycarbonate resins for radiation curable powder coatings

Thermosetting resins based on semi-crystalline poly(dimethyl trimethylene carbonate) (PDTC) were synthesised and characterised. Polymers with linear and branched architectures were synthesised through cationic ring opening polymerisation (CROP) of dimethyl trimethylene carbonate (DTC) using a series of polyols as initiators and fumaric acid as catalyst. The best powders were stable during storage at 45 °C for one week and could subsequently form films at temperatures between 100 and 115 °C. Functionalisation of the resins with methacrylic anhydride enabled curing by UV-initiated radical polymerisation. Rheology measurements showed that the architecture had a significant effect on the melt viscosity, which shows that the rheological properties can be tuned for use as low temperature curing powder coatings.     

Ethoxysilyl-modified hyperbranched polyesters as mulitfunctional coupling agents for epoxy-silica hybrid coatings

Partially ethoxysilyl-modified hyperbranched aliphatic-aromatic polyesters (HBPs) were effectively used as toughening as well as multi-site coupling agents in the preparation of organic-inorganic UV-thermal dual-cured epoxy/TEOS coatings. Through chain transfer reaction of the phenolic terminal units of the HBPs effective incorporation in the epoxy resin is achieved in the photo-initiated cationic polymerization whereas the ethoxysilane groups allow effective formation of a strongly interconnected inorganic-organics network during the in-situ sol-gel process with TEOS by binding the organic to the inorganic phase. Under those conditions, the addition of the inorganic precursor to the epoxy/HPB (20 wt%) system induced an increase of the storage modulus and more important, an improvement of the viscoelastic properties by extending the performance of the elastic modulus to higher temperatures. Thus, highly transparent hybrid coatings with enhanced thermal-mechanical and surface hardness properties resulted by the use of the partially ethoxysilyl-modified HBPs as multifunctional coupling agents.     

Epoxy coatings containing clays and organoclays: Effect of the filler and its water content on the UV-curing process

UV-cured coatings were prepared by photoinitiated cationic ring-opening polymerisation of epoxides in the presence of natural montmorillonite and different organically modified clays (5 wt%). The curing was monitored by FTIR in real time while irradiating the formulations by UV light. Significant changes of both the rate of curing and the final conversion were found. Only in the presence of a suitable montmorillonite and after a suitable pre-treatment, the process showed the same polymerisation rate, guaranteed a higher conversion than the neat epoxide and the formation of intercalated nanostructured coatings.     

Investigation of polymer and nanoclay orientation distribution in nylon 6/montmorillonite nanocomposite

A method to determine the orientation distribution function of montmorillonite clay in nylon 6 nanocomposite films by a combination of infrared (FTIR) trichroic analysis and transmission electron microscopy (TEM) image analysis is described. The structural absorbance of the nanoclay Si-O vibrations was obtained by the sample tilting method described by Schmidt [Schmidt PG. J Polym Sci: Part A 1963;1:1271-1292]. A nonlinear least squares regression was performed to extract the absorbance of individual peaks. The montmorillonite clay orientation in spun cast nylon 6 films can be described by a Gaussian function having a standard deviation of 15° i.e. 95% of the clay platelets are tilted at an angle of within ±30° of the plane of the film. The transition dipole moment angles of the 1018 and 1046 cm⁻¹ clay vibrations are determined to be 18 and 16° relative to the clay surface, respectively. The orientation of nylon 6 in the nanocomposite was also investigated based on the NH stretching mode. The NH bonds are found to be less preferentially oriented along the plane of the film surface compared to pure nylon 6 film.