超支化聚(胺酯)的合成及其光固化性能研究

采用甲基丙烯酸酐直接改性和先以丁二酸酐或邻苯二甲酸酐酯化再以甲基丙烯酸缩水甘油酯改性所得到的甲基丙烯酸酯化超支化聚 (胺 酯 )齐聚物在光引发剂存在时紫外光辐照下发生快速聚合反应 ;反应速率和双键转化率随超支化分子的结构不同而变化 ;高度交联的涂膜具有较好的热学性能     

Visible-Light-Curable Solvent-Free Acrylic Pressure-Sensitive Adhesives via Photoredox-Mediated Radical Polymerization

Owing to their excellent properties, such as transparency, resistance to oxidation, and high adhesivity, acrylic pressure-sensitive adhesives (PSAs) are widely used. Recently, solvent-free acrylic PSAs, which are typically prepared via photopolymerization, have attracted increasing attention because of the current strict environmental regulations. UV light is commonly used as an excitation source for photopolymerization, whereas visible light, which is safer for humans, is rarely utilized. In this study, we prepared solvent-free acrylic PSAs via visible light-driven photoredox-mediated radical polymerization. Three α-haloesters were used as additives to overcome critical shortcomings, such as the previously reported low film curing rate and poor transparency observed during additive-free photocatalytic polymerization. The film curing rate was greatly increased in the presence of α-haloesters, which lowered the photocatalyst loadings and, hence, improved the film transparency. These results confirmed that our method could be widely used to prepare general-purpose solvent-free PSAs—in particular, optically clear adhesives for electronics.     

High flow addition curing polyimides

A new series of high flow PMR-type addition curing polyimides was developed, which employed the substitution of 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (BTDB) for p-phenylenediamine (p-PDA) in a PMR-II formulation. These thermoset polyimides, designated as 12F resins, were prepared from BTDB and the dimethyl ester of 4,4′-(hexafluoroisopropylidene)-diphthalic acid (HFDE) with either nadic ester (NE) or p-aminostyrene (PAS) as the endcaps for addition curing. The 12F prepolymers displayed lower melting temperatures in DSC analysis, and higher melt flow in rheological studies than the corresponding PMR-II polyimides. Long-term isothermal aging studies showed that BTDB-based 12F resins exhibited comparable thermo-oxidative stability to p-PDA based PMR-II polyimides. The noncoplanar 2- and 2′-disubstituted biphenyldiamine (BTDB) not only lowered the melt viscosities of 12F prepolymers, but also retained reasonable thermal stability of the cured resins. The 12F polyimide resin with p-aminostyrene endcaps showed the best promise for long-term, high-temperature application at 343°C (650°F). © 1994 John Wiley & Sons, Inc.     

Influence of photoinitiator and curing conditions on polymerization kinetics and gloss of UV-cured coatings

Polymerization kinetics and gloss of different formulations of coatings at different UV curing conditions were studied. The results showed that the photoinitiator type, its concentration, sample coating thickness, as well as the UV light intensity were the most significant factors affecting the polymerization course and the gloss of UV-cured films. The increasing concentration of the photoinitiator and the UV light intensity significantly decreased the gloss of the cured surface. The influence of the sample coating thickness on the kinetics and final gloss was also considerable.     

Synthesis of metal/polymer nanocomposite by UV-radiation curing

Nanocomposite polymers containing bismuth nanoparticles (2 wt%) have been obtained by photopolymerization of acrylic resins. The bismuth nanoparticles have been synthesized by reduction of BiCl₃ with t-BuONa activated sodium hydride. In situ t-BuONa stabilization protects the metallic particles against aggregation. Transmission electron microscopy (TEM) analysis has shown that the bismuth nanoparticles are well dispersed in the acrylic resin. The curing process was followed quantitatively by infrared spectroscopy through the decrease upon UV exposure of the IR bands characteristic of the functional groups. The bismuth nanoparticles were found to have no detrimental effect on the photopolymerization kinetics. Dynamic mechanical analysis (DMA) has shown that the viscoelastic properties of the nanocomposite photopolymer are significantly modified in comparison with corresponding UV-cured polymer. The addition of metal nanoparticles was found to greatly reduce the gloss of UV-cured coatings.     

Photoinitiators for UV and visible curing of coatings: Mechanisms and properties

The radiation curing industry is one of the most rapidly developing fields in the entire coatings industry. The low toxicity, cheapness, speed, control and ease of formulation and operation are some of the main advantages of this growing technology. UV and/or visible light radiation is used to induce photochemical polymerization or crosslinking of a monomer, oligomer or prepolymer formulation containing a certain type of unsaturation, such as an acrylic group, and an appropriate initiator. The latter is used to absorb the light energy and transform it into active species, such as radicals or ions, capable of inducing such reactions. Applications extend to general coatings for paper, board, wood, tapes, compact discs and holograms, inks, photoresists for imaging processes and adhesives for welding and sealing in electronic circuit boards. The photoinitiator is the key to the control of these processes and, in recent years, has seen many new developments. These include the need for water-soluble, co-reactive and polymeric structures with low migration rates, as well as cheaper UV/ visible sensitizers with enhanced speed. New and effective cationic systems are also on the scene and, although expensive, are attracting significant academic and commercial interest.     

UV curing polymer materials for making laser glass

Epoxy acrylate was synthesized by reacting epoxy resin with acrylic acid in the presence of quaternary ammonium salt. The effects of photoinitiators on the curing rate have been studied. UV curing polymer materials for making laser glass have been selected. The laser glass thus manufactured is a new decorative building material. Copyright © 1999 John Wiley & Sons, Ltd.     

Using Ozawa method to study the curing kinetics of electrically conductive adhesives

In this paper, we fabricated electrically conductive adhesives using vinyl ester resin and micro silver flakes, and then cured the adhesives by heat without any catalysts or initiators. The curing temperature was above 200 °C, and the curing time about 30 min. Under these heat curing conditions, the double bonds in the adhesives reached a high conversion (α) around 98.88 % calculated from the Fourier transform infrared spectroscopy analysis. The curing kinetics of heat curing products was studied using Ozawa method and deduced by assuming a constant activation energy (E). The curing kinetic equation was obtained as dα/dt = e^17.70(1 ? α)^1.19 α ^0.41e^(?94.32)/RT) with E = 94.32 kJ mol^?1. The heat curing followed the shrinking core model from the resin-particle system. The data calculated from the kinetic equation agreed well with the experimental data, showing that the Ozawa method could evaluate the curing kinetics effectively. Furthermore, a comprehensive and in-depth understanding of the curing kinetics of heat curing electrically conductive adhesives has been achieved with this Ozawa method.     

Dual curing systems based on UV curing and alkoxysilane group condensation

A study was performed on dual curing systems based on UV curing of reactive unsaturations (acrylic double bonds) and successive alkoxysilane group condensation. The systems were obtained by mixing a typical epoxy acrylic resin with different amounts of monomers containing alkoxysilane groups (3-methacryloyloxypropyltrimethoxysilane, MEPTS, and 3-mercaptopropyltrimethoxysilane, MPTS) in the presence of a photoinitiator and a condensation catalyst. After UV curing, the kinetics of the alkoxysilane group condensation was followed by Fourier Transform Infrared Spectroscopy (FTIR) analysis at different temperatures and water vapour pressures. Higher condensation rates were obtained in the systems containing MPTS with respect to the MEPTS system. Also the adhesion on glass sheets was better in the presence of MPTS with respect to MEPTS. These results were attributed to the different structures and to the different crosslinking density obtained in the presence of the two monomers. Wetting tension, Attenuated Total Reflectance (ATR-FTIR) and X-Ray Photoelectron Spectroscopy (XPS) measurements are in agreement with these conclusions.     

Ultraviolet curing of acrylic systems: Real‐time Fourier transform infrared,mechanical, and fluorescence studies

The photopolymerization of acrylic‐based adhesives has been studied by Fourier transform infrared and fluorescence analysis in real time. Real‐time infrared spectroscopy reveals the influence of the nature of the photoinitiator on the kinetics of the reaction. Furthermore, the incident light intensity dependence of the polymerization rate shows that primary radical termination is the predominant mechanism during the initial stages of the curing of the acrylic system with bis(2,4,6‐trimethylbenzoyl) phenyl phosphine oxide (TMBAPO) as a photoinitiator. The fluorescence intensity of selected probes increases during the ultraviolet curing of the adhesive, sensing microenvironmental viscosity changes. Depending on the nature of the photoinitiator, different fluorescence–conversion curves are observed. For TMBAPO, the fluorescence increases more slowly during the initial stage because of the delay in the gel effect induced by primary radical termination. Mechanical tests have been carried out to determine the shear modulus over the course of the acrylic adhesive ultraviolet curing. In an attempt to extend the applications of the fluorescence probe method, we have undertaken comparisons between the fluorescence changes and shear modulus. Similar features in both curves confirm the feasibility of the fluorescence method for providing information about microstructural changes during network formation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4236–4244, 2002     

Curing process of phenol-urea-formaldehyde-tannin (PUFT) adhesives

Summary Phenol-urea-formaldehyde-tannin (PUFT) adhesives have been prepared by copolymerization at room temperature of pine bark tannins with phenol-urea-formaldehyde (PUF) prepolymers prepared under varying operating conditions. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) have been used to analyse the curing of prepolymers and adhesives. DSC curves were obtained at three different heating rates and, by means of the Model Free Kinetics isoconversional method, chemical conversion vs. time at a given temperature was obtained. Mechanical conversion was calculated from DMA storage modulus data for those adhesives which gave the best results for plywood and MDF boards.     

Reactive adhesives on the basis of (meth)acrylic oligomers

A review of works carried out at the Academician V.A. Kargin Research Institute of Polymers and literature data on applications and properties of anaerobic, UV-, and thermo-curable, aerobic and modified acrylic adhesives is presented. The primary attention is paid to the possibility of preparation of thermally stable adhesive acrylic materials, modifying an oligomeric backbone and using viscosifiers and additives. Data on the use of efficient stabilizers and curing accelerators are presented. Curing mechanisms of acrylic adhesives are considered.     

Effect of substituents on the curing of liquid crystalline epoxy resin

The synthesis of an aromatic ester based liquid crystalline epoxy resin (LCE) with a substituent in the mesogenic central group is described. Chlorine and methyl groups were introduced as substituents. The curing behaviors of three epoxy resins were investigated using diaminodiphenyl ester as the curing agent. The curing rate and heat of curing of LCE were measured with dynamic and isothermal DSC. The chlorine substituent accelerated the curing of LCE, while the methyl substituent decelerated the curing of LCE. The heat of curing of substituted LCE was diminished compared to LCE with no substituent. Glass transition temperature and elastic modulus of LCE decreased with increasing the size of the substituent. Three liquid crystalline epoxy resins based on aromatic ester mesogenic groups formed a liquid crystalline phase after curing, and the liquid crystalline phase was stable up to the decomposition temperature. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 911–917, 1998     

Enhanced properties of phthalonitrile resins under lower curing temperature via complex curing agent

High curing temperature has been restricting the application and development of phthalonitrile resin. A complex curing agent containing melamine (ME) and ZnCl₂ was developed to promote the curing reaction of resorcinol‐based phthalonitrile resin (DPPH). The thermal stability of ME can be significantly enhanced via adding ZnCl₂, which was due to the interaction between ZnCl₂ and amino group in ME. Moreover, the activities of pristine ZnCl₂ and ME were improved via mixing, especially, the curing temperature for DPPH can be effectively reduced. Even at a curing temperature of 300°C, the 5% weight loss temperature of the resulting resin cured with complex curing agent still exceeded 500°C, which was much higher than those with pristine curing agents. In addition, the good long‐term oxidation stability and relatively low water absorption can also be obtained in the resins cured with novel curing agent. This work affords a facile route for designing high‐performance curing agent to improve the curing process of phthalonitrile resin.     

Hyperbranched Polyurethane Acrylate Applied to UV Curable Flame Retardant Coatings

UV curable hyperbranched prepolymers based on amine-ester, ester-amide and ether-amide started with AB_2-type monomers have been prepared by the authors. A series of work on allyl ether maleate hyperbranched polyesters for UV curing coatings by Hult and his colleagues has been reported. However, the UV cured films from those materials are all flammable when attached to fire without addition of flame retardants. In this work, a new kind of hyperbranched polyurethane acrylate containing phosphorus     

Synthesis and hydrolysis behaviour of poly(ester anhydrides) from polylactone precursors containing alkenyl moieties

Hydroxyl-group functional polylactones were prepared and converted to acid- terminated polyesters in a reaction with a series of alkenylsuccinic anhydrides containing 8, 12, or 18 carbons in their alkenyl chains. These polyester precursors were then linked into higher molecular weight poly(ester anhydrides) containing alkenyl moieties in their polyester blocks. The hydrolysis behaviour of the poly(ester anhydrides) was found to depend on the thermal properties of the polyester precursors. For poly(ester anhydrides) prepared from low molecular weight prepolymers with thermal transitions below 37 degrees C, the presence of hydrophobic alkenyl chains in the polyester precursors slowed the rate of weight loss. Poly(ester anhydrides) prepared from higher molecular weight prepolymers showed the opposite weight-loss behaviour; i.e., the crystallinity and thermal transitions of the alkenyl chain-containing poly(ester anhydrides) were low, and the weight loss was faster than for poly(ester anhydrides) without the alkenyl chains. The differences in length of the alkenyl chain, as such, had little effect on the hydrolysis behaviour and thermal properties of the poly(ester anhydrides).     

Effect of organoclay on the curing reactions in bismaleimide/diallyl bisphenol a resin

4,4′‐Bismaleimidodiphenyl methane (BMPM)/2,2′‐diallyl bisphenol A (DBA)/organoclay nanocomposites were synthesized. The effects of organoclays on the curing reactions in the BMPM/DBA system at low temperatures (ene reaction) and high temperatures (Diels–Alder reaction, homopolymerization of BMPM, and alternative copolymerization) were investigated with differential scanning calorimetry and Fourier transform infrared techniques. The results showed that these reactions were affected to different extents in the presence of organoclays. The ene reaction was accelerated to different degrees depending on the acidity of the modifier and the accessibility of the organoclays used. The exfoliation degree of organoclays in the prepolymers showed great effects on the curing behavior of BMPM/DBA. When an organoclay was less intercalated, the curing behavior of the system was different from that of neat BMPM/DBA. On the other hand, when the organoclay was better exfoliated in prepolymers, the curing behavior of the system was similar to that of the neat BMPM/DBA system. However, even in this case, the reactions at high temperatures occurred in different ways in the presence of an organoclay. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 994–1006, 2005     

Effect of epoxy and filler concentrations on curing behaviour of isotropic conductive adhesives

Isotropic conductive adhesives (ICAs) are considered as the most promising replacement to lead-based solders due to relatively low melting point, simple processing and fine pitch capability. The study reports on the effect of volume fractions of silver flakes and particles on the curing reaction of ICAs. In addition, the thermal behavior of ICAs formulated with two types of polymeric adhesives: diglycidylether of bisphenol-A (DGEBA) and polyurethane (PU) was also investigated in this work. The increase in silver flakes concentration seem to reduce the melting temperature of the DEGBA and PU-based ICAs, which could be due to retardation of cross-linking of polymers due to silver flakes acting as barrier within the polymer matrix. In addition, the formulation of ICAs containing silver flakes and particles yielded a much higher reaction compared to conventional ICAs. The study showed that use of polyurethane (PU) as opposed to conventional Diglycidylether of bisphenol-A (DGEBA) showed a more stable system.     

Polymerization shrinkage of (meth)acrylate determined by reflective laser beam scanning

The real‐time study of the shrinkage during UV‐curing of (meth)acrylate monomers is limited due to the very fast curing rate, their thin sample geometry (<100 μm), and low viscosity. We report a reflective laser scanning system for direct measurement of UV‐curing shrinkage. A low‐power laser beam at a wavelength of 650 nm, different from the polymerization wavelength (395 nm), was used. This noncontact method of measurement makes it possible to analyze the thin liquid monomer with a very low shrinkage (measuring accuracy 0.02 μm), and very fast curing rate (fast sampling speed of 50 KHz). Eight different kinds of UV monomers were tested using 2–5 mg specimens, and the shrinkage process was examined. The results proved that this new method was accurate and precise, and could be applied to different kinds of (meth)acrylates. Furthermore, the shrinkage capability of acrylic double bonds was determined as 23.98 mL/mol using this novel method. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Reaction kinetics and microgel particle size characterization of ultraviolet‐curing unsaturated polyester acrylates

The free‐radical reaction kinetics and microgel formation of UV‐curing unsaturated polyester acrylates were studied in terms of the effects of internal maleic and terminal acrylate unsaturations. A triacrylate‐functional monomer, trimethylolpropane triacrylate, was used as the reactive diluent. A time‐resolved Fourier transform infrared technique was used to evaluate the consumption of double bonds and showed that internal (maleic) double bonds were involved in microgel formation at a rate similar to that of the more reactive terminal (acrylic) double bonds. Dynamic light scattering was used to measure the microgel particle size. The introduction of internal unsaturations caused smaller microgels, whereas terminal acrylate unsaturations resulted in larger particle sizes. These results were attributed to the higher tendency of the internal maleic double bonds toward intramolecular cyclization reactions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6544–6557, 2006