Curing of unsaturated polyester resins: Effects of comonomer composition. II. High-temperature reactions

The effects of comonomer composition of the curing kinetics of unsaturated polyester (UP) resins at 100–120°C were investigated by differential scanning calorimetry (DSC) and infrared spectroscopy (IR) over the entire conversion range. One commercial UP resin, UP2821, with 6.82 unsaturated C?C bonds per polyester molecule, was used. For styrene/UP2821 reactions, experimental results of the initial and maximum reaction rates by DSC at 100–120°C revealed that the styrene content, as well as the reaction temperature, would affect the formation of microgel structures. As the initial molar ratio of styrene to polyester C?C bonds increased, the styrene swelling effect could enhance the intramicrogel crosslinking reactions, while the styrene dilution effect could diminish the intermicrogel crosslinking reactions. The competition between the two reactions would depend on the reaction temperatures. Finally, a microgel-based reaction mechanism was proposed for the high temperature reactions. © 1993 John Wiley & Sons, Inc.     

Some filler effects on cross-linking of unsaturated polyesters

The effect of five fillers on the cross-linking macro-and microcharacteristics of simple unsaturated polyester resins was investigated by differential scanning calorimetry (DSC), reactivity tests, and gel time tests. Glass beads and silica flour appeared to have little influence on the cross-linking reaction of the resin itself, their effect being comparable to mere dilution of the resin. Kaolin presented some interaction with the resin due to its absorption characteristics and acid groups. Reground polyester/glass fiber powder and especially wood flour appeared to present clear chemical interactions with the curing behavior of the resin. Wood flour, in particular, was shown by DSC analysis to strongly co-react with the resin during cross-linking and altered markedly the resin enthalpy change and energy of activation during curing. The wood flour component causing the altered behavior of the resin appears to be lignin. DSC analysis of resins filled with three different types of isolated lignins indicated that this wood flour component reacts in a heterogeneous phase reaction with the resin during cross-linking. It appears that it is the lignin unsaturated carbon–carbon double bonds at the polyester/wood flour and at the polyester/lignin interphases that are likely to co-react by heterogeneous phase radical cross-linking with the polyester resin and styrene unsaturation, markedly changing the resin curing behavior. © 1993 John Wiley & Sons, Inc.     

丁腈羟_丁二酸酐加成物与环氧树脂反应动力学的研究

用红外光谱仪和差示扫描量热计,研究了端羟基液体丁二烯-丙烯腈共聚物与丁二酸酐反应得到的加成物与环氧树脂的固化反应动力学。结果表明,在此固化反应体系中,反应前期主要是羧基与环氧基的反应,后期则主要是环氧基的聚合;树脂中仲羟基与环氧基的反应可以忽略。用DSC法测得的固化反应表观活化能为66.5 kJ/mol。     

High‐performance thermosets with tailored properties derived from methacrylated eugenol and epoxy‐based vinyl ester

A renewable chemical, eugenol, is methacrylated to produce methacrylated eugenol (ME) employing the Steglich esterification reaction without any solvent. The resulting ME is used as a low‐viscosity co‐monomer to replace styrene in a commercial epoxy‐based vinyl ester resin (VE). The volatility and viscosity of ME and styrene are compared. The effect of ME loading and temperature on the viscosity of the VE–ME resin is investigated. Moreover, the thermomechanical properties, curing extent and thermal stability of the fully cured VE–ME thermosets are systematically examined. The results indicate that ME is a monomer with low volatility and low viscosity, and therefore the incorporation of ME monomer in VE resins allows significant reduction of viscosity. Moreover, the viscosity of the VE–ME resin can be tailored by adjusting the ME loadings and processing temperature to meet commercial liquid molding technology requirements. The glass transition temperatures of VE–ME thermosets range from 139 to 199 °C. In addition, more than 95% of the monomer is incorporated and fixed in the crosslinked network structure of VE–ME thermosets. Overall, the developed ME monomer exhibits promising potential for replacing styrene as an effective low‐viscosity co‐monomer. The VE–ME resins show great advantages for use in polymer matrices for high‐performance fiber‐reinforced composites. This work is of great significance to the vinyl ester industry by providing detailed experimental support. © 2018 Society of Chemical Industry     

Theoretical and experimental conversion in the curing of unsaturated polyester resins with styrene as a crosslinking agent

The reaction of unsaturated polyester resin is a free radical copolymerization between the styrene monomer and the unsaturated polyester. Depending on the temperature and other processing conditions, some of the reacting molecular species remain, after curing, in the form of residual monomer and soluble polymer that do not contribute to the network structure. By means of DSC and gel permeation chromatography (G.P.C.) techniques, we have investigated the differences between theoretical and experimental reaction heats of unsaturated polyester samples with different styrene/polyester ratios, the residual species formed, and the conversion of reactive groups.     

Molecular dynamics simulations of vinyl ester resin monomer interactions with a pristine vapor-grown carbon nanofiber and their implications for composite interphase formation

A molecular dynamics simulation study was performed to investigate the role of liquid vinyl ester (VE) resin monomer interactions with the surface of pristine vapor-grown carbon nanofibers (VGCNFs). These interactions may influence the formation of an interphase region during resin curing. A liquid resin having a mole ratio of styrene to bisphenol-A-diglycidyl dimethacrylate VE monomers consistent with a commercially available 33 wt.% styrene VE resin was placed in contact with both sides of two pristine graphene sheets overlapped like shingles to represent the outer surface of a pristine VGCNF. The relative monomer concentrations were calculated in a direction away from the graphene sheets. At equilibrium, the styrene/VE monomer ratio was higher in a 5 Å thick region adjacent to the nanofiber surface than in the remaining liquid volume. The elevated concentration of styrene near the nanofiber surface suggests that a styrene-rich interphase region, with a lower crosslink density than the bulk matrix, could be formed upon curing. Furthermore, styrene accumulation in the immediate vicinity of the nanofiber surface might, after curing, improve the nanofiber–matrix interfacial adhesion compared to the case where the monomers were uniformly distributed throughout the matrix.     

Low temperature cure of vinyl ester resins

Vinyl ester resins are well known for their versatility as a composite matrix. With the development of a promising room temperature molding technology, vacuum-assisted resin transfer molding, e.g. Seemann Composite Resin Infusion Molding Process (SCRIMP), the processability of vinyl ester resins at low temperatures has attracted considerable attention from the composite industry. The objective of this paper is to provide a better understanding of the reaction kinetics of this resin system at low temperatures. In this study, a differential scanning calorimeter (DSC) coupled with a Fourier transform infrared (FTIR) spectrometer was employed to measure the reaction profile of a vinyl ester resin with different promoter and styrene contents. A kinetic model based on the free radical co-polymerization mechanism was developed for simulating the reaction rates and conversions of styrene vinyl and vinyl ester vinylene groups. The model parameters were determined from several FTIR experiments under isothermal conditions. This model, in conjunction with heat transfer analysis, was able to successfully predict the temperature profiles during curing in two SCRIMP molding cases based on groove type resin distribution system.     

Das Copolymerisationsverhalten von Diallylmaleinat gegenüber Akzeptor-Donor-Monomeren

The copolymerisation behaviour of diallylmaleate (DAM) with methyl methacrylate (MMA), N-phenylmaleimide (NPI), and styrene (S) in radical polymerisation was studied under the aspect of interaction of monomers with high and low electron density vinyl groups. The system DAM/S showed some indications for interaction. Generally, the strong control of degradative chain transfer could be recognised in polymerisation. A huge increase of the molecular mass is observed at low parts of DAM in the monomer composition.     

活性稀释剂对T700/BMI复合材料力学性能的影响

本文采用苯乙烯作改性BMI树脂的活性稀释剂以降低树脂粘度,并对该树脂体系进行了DSC测试和IR光谱分析。实验表明,加入苯乙烯后,树脂体系的反应活性极大提高,固化温度降低。实验还研究了苯乙烯的用量对T700/BMI复合材料力学性能的影响,结果表明,随着苯乙烯用量的增加,T700/BMI复合材料的拉伸强度、弯曲强度及层间剪切强度逐渐增大,但苯乙烯用量超过15%(W%)时,拉伸强度呈下降趋势,而弯曲强度和层间剪切强度则继续增大,直到苯乙烯用量超过25%(W%)时,才呈下降趋势。因此,苯乙烯的用量控制在15%～25%(W%)较为合适。     

改性不饱和聚酯固化反应的研究

本文通过对环氧丙烯酸酸（ＶＥ）树脂改性不饱和聚酯（ＵＰ）树脂的固化过程的研究，制定了合理的树脂蜞体固化制度，并且求解了固化反应的动力学参数。通过对该树脂基体模压料流变性特性的研究，确定了较为合理的模压成型工艺参数。     

Kinetic analysis and mechanical properties of nanoclay reinforced unsaturated polyester (UP) resins cured at low temperatures

The reaction between unsaturated polyester (UP) resin and styrene (St) is a heterogeneous free‐radical chain‐growth cross‐linking copolymerization. Curing of the UP/St system in the presence of organically‐modified nanoclay was studied by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. A mechanistic kinetic model based on the free radical copolymerization mechanism was developed to simulate the reaction rate and conversion profiles of UP/St resin mixtures with various nanoclay contents cured at low temperatures. The model parameters were determined from several DSC experiments under isothermal conditions. The model, in conjunction with heat transfer analysis, was able to successfully predict the temperature and conversion profiles during curing in two vacuum‐infusion liquid composite molding (e.g., the Seemann composite resin infusion molding process [SCRIMP]) experiments. The presence of nanoclay particles enhanced the tensile modulus, but reduced the tensile strength of the UP nanocomposites. The fracture toughness parameter K_IC was improved by 30% with the addition of 5 wt% nanoclay. The system with mixed nanoclay and calcium carbonate was found to possess the highest K_IC without sacrificing the tensile strength. POLYM. ENG. SCI., 45:496–509, 2005. © 2005 Society of Plastics Engineers     

Curing of unsaturated polyester resins—effects of comonomer composition. III. Medium-temperature reactions

The effects of comonomer composition on the curing kinetics of unsaturated polyester (UP) resins at 70–90°C were studied by differential scanning calorimetry (DSC) and infrared (IR) spectroscopy over the whole conversion range. One commercial UP resin, UP2660PF2, with cobalt promoter added and with 8.85 unsaturated C?C bonds per polyester molecule, was used. It was found that a marked shoulder in the initial DSC rate profile, rather than that reported after the peak of rate profile for low-temperature and high-temperature reactions, appeared when the molar ratio of styrene to polyester C?C bonds was greater than 1. With the initiator system accelerated by cobalt promoter, the formation rate of microgel particles would be enhanced at the early stage of reaction, as supported by the much higher conversion of polyester C?C bonds than that of styrene by IR spectroscopy. Those relatively greater number of microgel particles tended to facilitate the intramicrogel crosslinking reactions, which would be independently identified from the initial DSC rate profile as a shoulder. Consequently, the reaction mechanism was elucidated by decomposing the reaction rate profile into two individual profiles accounting for the intramicrogel dominated and the intermicrogel dominated crosslinking reactions, respectively. © 1993 John Wiley & Sons, Inc.     

Effect of α-methyl styrene on curing behaviour and interfacial properties of glass fibre-reinforced vinyl ester resins

The curing behaviour of bismethacryloyl derivative of diglycidyl ether of bisphenol A (vinyl ester VE resin) containing styrene and α-methyl styrene (MS) as reactive diluents was studied. Delayed curing was observed in samples containing increasing proportions of MS. Interfacial shear stress of untreated as well as γ-methacryloyloxy-propyl trimethoxy silane (MTS) treated, glass fibre-reinforced VE resin composites were measured by single fibre technique. In comparison to untreated glass fibres, a 30 – 50% increase in interfacial shear stress was observed in composites based on MTS treated glass fibres. Addition of up to 5 wt.-% MS to VE resin did not affect the interfacial shear strength (ILSS). This behaviour was observed by using ILSS measurement of both glass fabric-reinforced composites as well as single fibre specimens. Further increase in MS to 15 wt.-% resulted in an increase in ILSS and bending stiffness as well as flexural strength.     

Synthesis of unsaturated polyester resins based on rosin acrylic acid adduct for coating applications

Unsaturated polyester, UP, resins were obtained by reacting the propylene or ethylene glycol, PG or EG, with different acrylopimaric adducts APA, maleic anhydride as a source of double bond, phthalic anhydride and adibic acid as dibasic acids. The molecular weights of UP were determined by end group analysis. The chemical structures of the resulting UP resins were confirmed by ¹H NMR analysis. The curing exotherm of UP, vinyl ester resins (VE) and styrene was evaluated at temperatures from 35 to 55 °C using free radical initiator and accelerator. The curing behaviors of cured UP resins with styrene were evaluated by DSC measurements. The prepared UP curable resins were evaluated in the field of steel coating by measuring their mechanical properties and chemical resistance.     

木质素酚醛树脂的固化动力学及机理研究

通过差示扫描量热法（Dsc）和红外光谱（IR）分别研究了木质素酚醛树脂（LPF）的固化动力学及机理。DSC分析表明,LPF的固化反应起始温度比酚醛树脂高,终止温度及活化能比酚醛树脂低,因此,LPF凝胶点比酚醛树脂高,贮存稳定性比酚醛树脂好,固化速度比酚醛树脂快;IR分析表明,LPF的固化机理与酚醛树脂相似,都是羟基之间及羟基与芳环上的氢之间的缩合反应。不同的是LPF固化后仍有部分醚键结构。     

纳米TiO2/UPR复合体系的固化动力学及固化工艺研究

采用动态差示扫描量热法（DSC）对纳米TiO2／UPR复合体系的固化过程进行研究，得出不同升温速率下纳米TiO2／UPR复合体系固化过程中的DSC曲线；并根据动态DSC曲线求出固化反应的表观活化能、固化反应级数及动力学方程中的指前因子等参数；建立了复合体系固化反应动力学的数学模型并且确定了分阶段变温固化新工艺。     

Exploratory experiments on the fast anionic polymerisation of styrene

The limitations in the rates of polymerisation associated with the free radical process do not arise when styrene is polymerised by an anionic catalyst such as butyl lithium. However, if anionic catalysts are directly applied to pure styrene a thermal explosion follows. Some experiments are described in which sufficient low molecular weight polystyrene resin was added to the styrene to prevent boiling and the polymerisation was completed with butyl lithium. In spite of the dilution by low viscosity polymer, average molecular weights were obtained approaching those required for commercial polymer. Although purification criteria would have to be met there seems to be no fundamental obstacle to the development of small, high output polymerisation plants for making polystyrene.     

Curing kinetics of divinyl ester resins with styrene

The curing reaction of a divinyl ester resin with different proportions of styrene—4, 20, and 40% by weight—was investigated by differential scanning calorimetry (DSC) using isothermal and dynamic modes. The different constraints on the reaction rate was globally considered, taken the reaction as divided in two regimens: below the vitrification regimen and during the vitrification regimen. Below the vitrification regimen, the autocatalytic model developed by Kamal was used to perform the analysis of the curing kinetics of divinyl ester resin with styrene. Experimental data from dynamic and isothermic runs, at a fixed composition, were simultaneously considered, while the actual temperature records (measured during the DSC runs) were also taken into account. The adjusted kinetic parameters took into account the gel effect on the radicals' termination rate and the structure constraints on the reactivity of pendant vinyls groups, present during this stage. During the vitrification stage, the diffusion control due to the low mobility of the reactive groups and molecules was incorporated into the overall rate constant according to the Rabinowitch model, which considers the two regimen contributions to the overall reaction rate kinetic. The Vogel–Fulcher relationship was adopted to express the temperature dependence of the rate constant during the vitrification stage. The method presented here has been satisfactorily applied to dynamic and isothermal curing reactions, allowing a simple and general kinetic expression useful in the design, optimization, and control of the processing of composites based on these thermoset polymers to be obtained. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1044–1053, 1999     

邻苯二甲酸二烯丙基酯树脂固化特性的研究

运用示差扫描量热(DSC)法研究了邻苯二甲酸二烯丙基酯(DAP)树脂的固化反应历程。讨论了引发剂对DAP固化特性的影响,并由DSC曲线得到了DAP树脂的固化工艺和动力学参数。通过固化度、FT-IR的测试对DAP树脂在中温条件下的固化情况进行了研究。结果表明:在过氧化二异丙苯(DCP)固化体系中引入BPO可以使DAP树脂在更低温度下引发固化;在BPO、DCP用量均为2%的条件下,确定了体系的凝胶温度、固化温度、后处理温度分别为:100.5℃,124.3℃,137.8℃,表观活化能为129.3 kJ/mol,反应级数为0.950。固化度、FTIR的测试结果表明:DAP树脂在中温条件下可以固化得较完全。     

Effect of oxirane groups on curing behavior and thermal stability of vinyl ester resins

The effects of oxirane groups in vinyl ester (VE) resin and reactive diluent on curing characteristics and thermal behavior of cured resins are described. Stoichiometric (0.5:1, sample A) as well as nonstoichiometric (0.5:0.85, sample B) ratios of the diglycidyl ether of bisphenol-A (DGEBA) and methacrylic acid (MA) were used for the synthesis of VE resins. Resin sample B had more residual epoxy groups because of the stoichiometric imbalance of the reactants. VE resins thus obtained were diluted with methyl methacrylate (MMA; 1:1, w/w), and controlled quantities of epoxy groups were introduced by partial replacement of MMA with glycidyl methacrylate (GMA), keeping the overall ratio of resin and reactive diluent constant. Increase of GMA content in resin A or B resulted in a decrease in gel time, indicating that the curing reaction is facilitated by the presence of epoxy groups. An increase in initiator content also reduced the gel time. In the differential scanning calorimetry (DSC) scans, a sharp curing exotherm was observed in the temperature range 107 ± 3–150 ± 1 °C. The onset temperature (T_onset) and peak exotherm temperature (T_exo) decreased with increase in GMA content. Heat of curing (ΔH) also increased with increase in GMA content. A broad exotherm was observed after the initial sharp exotherm that was attributed to the etherification reaction. Cured VE resins were stable up to 250–260 °C, and started losing weight above this temperature. Rapid decomposition was observed in the temperature range 400–500 °C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 416–423, 2001