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.     

Curing reaction of saturated aliphatic polyester modified unsaturated polyester resins

Two series of unsaturated polyesters (UPE from isophthalic acid, fumaric acid, and propylene glycol) were prepared. In series-A resins, UPEs wee thickened with isocyanate-terminated saturated aliphatic polyestes, i.e., an isocyanate-terminated polycaprolactone diol (PE-di-OL), through reaction of the isocyanate group with the hydroxyl group of the UPE. In series-B resins, the UPEs were mixed with saturated aliphatic polyesters i.e., PE-di-OL. The curing reaction of these two series of UPEs with styrene was studied by using differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). The DSC data show that for a fixed PE-di-OL molecular weight, the curing reaction rate of series-A UPE is faster than that of series-B UPE. The variation of microgel size during curing ws studied by GPC. These results revealed that microgel formation has a great effect on the kinetics of cure for the unsaturated polyester-styrene system. The curing of these two series of UPEs is found to strongly depend on the compatibility of the components in the curing system.     

MAP-POSS改性不饱和聚酯树脂的固化反应

为改进不饱和聚酯（UP）树脂的性能,用非等温差示扫描量热法（DSC）研究了甲基丙烯酰氧丙基笼形倍半硅氧烷（MAP-POSS）与通用UP树脂的共同化反应。UP、苯乙烯和MAP—POSS有较好的相容性,可共同固化,MAP-POSS可均匀分散在UP基体中形成原位纳米分子复合材料。测定了固化动力学参数,建立了固化反应动力学数学模型。     

Rheology of unsaturated polyester resins. II. Thickening behavior of unsaturated polyester and vinyl ester resins

The rheological properties of mixtures of unsaturated polyester resin and viscosity thickener were determined as thickening progressed. Two commercially available resins were used: (1) general purpose unsaturated polyester resin (Ashland Chemical, Aropol 7030), and (2) vinyl ester resin (Dow Chemical, XD-7608.05). As thickening agent, a magnesium oxide (MgO) paste dispersed in styrene monomer was used. No fillers, pigments, or other additives were used. During thickening, the following measurements were also made: (1) acid number by titration and (2) molecular weights by gel permeation chromatography (GPC). For the Ashland Chemical polyester resin, it was found that, over a period of 300 h, the titration method indicated that the number-average molecular weight (M _n) increased by a factor of 2 and the weight-average molecular weight (M _w) increased by a factor of 3. The GPC measurements, however, showed that M _n increased very little whereas M _w increased by a factor of about 2. Over the same period, the viscosity of the Ashland Chemical polyester resin increased from 0.9 N·s/m² (9 P) to 10⁴ N·s/m² (10⁵ P), and the viscosity of the Dow Chemical vinyl ester resin increased from 0.7 N·s/m² (7 P) to 2 × 10³ N·s/m² (2 × 10⁴ P). Such a large increase in viscosity cannot be explained by the existing molecular theory, in view of the fact that the molecular weights increased relatively little. We speculate that the exceedingly large increase in viscosity during thickening is attributable primarily to ionic associations between the carboxylic anions and the magnesium ions, rather than to the formation of chain branching suggested in the literature. It was found further that mixtures of polyester resins and viscosity thickener exhibit normal stress effects, increasing with thickening time and following the behavior of a second-order fluid when the first normal stress difference was plotted against shear rate. Interestingly enough, however, plots of first normal stress difference vs. shear stress yield a correlation which becomes independent of thickening time. An explanation is offered to the correlation obtained.     

Curing of unsaturated polyester resins with low exotherm peak

The curing behavior of an unsaturated polyester resin with low exotherm peak was studied by a standard procedure and by differential scanning calorimetry (DSC). A copper salt and α-methylstyrene were used as the polymerization retarders. The influence of the retarders on the exotherm peak temperature, gelation time, exothermic heat and the polymerization kinetics was investigated.     

Curing studies on modified epoxy and unsaturated polyester resins

Experimental studies were carried out on the curing behavior of unsaturated polyester and epoxy resins. The latter were modified with three different fillers (CaCO₃, CaSiO₃, and glass powder) and their curing behaviors studied. Polyesters exhibited faster cure rates than the epoxy resins. The gel time of the epoxy resins decreased with the addition of fillers. Data indicated that the peak exotherm of these thermosetting resins increased when filled with glass powder. The hardness of the curing mass increased with curing time. The use of gel-hardness number as a quality control parameter has been suggested.     

Curing of unsaturated polyester resins: Effect of surface treatment of particulates

The effect of surface treatment of particulates on the curing kinetics of unsaturated polyester resin has been investigated using a differential scanning calorimeter. Two coupling agents, γ-methacryloxy propyltrimethoxy silane (γ-MPS) and phenyltriethoxy silane (PTS), were employed. The former reacted with the resin; the latter did not. A kinetic model of free radical addition polymerization was used. A correction factor was used to represent the effective free radical concentration in order to account for the formation of charge transfer complex between the glass beads and the free radicals in the resin. The results indicate that (1) the resin with treated particulates showed generally faster reaction rate and conversion than the resin with untreated particulates; (2) no obvious difference on the curing kinetics was observed between these two coupling agents; the primary role of coupling agent is to inhibit the influence of particulates on the curing kinetics of the resin by effective surface coverage; and (3) a minimum aqueous concentration of 0.05 wt% was suggested for surface treatment of particulates; the reaction rate of the resin was slightly improved when the concentration of the coupling agent was 0.01 wt%; this might possibly be due to insufficient coverage of the particulate surface.     

Control of volume shrinkage and residual styrene of unsaturated polyester resins cured at low temperatures. II. Effect of comonomer

The effect of a comonomer, methyl methacrylate (MMA), on volume shrinkage and residual styrene content of an unsaturated polyester (UP) resin with low profile additives (LPAs) cured at low temperature was investigated by an integrated reaction kinetics-morphology-property analysis. MMA affects the volume shrinkage and residual styrene content differently depending on MMA to styrene (St) CC bond molar ratio. At low MMA/St ratio, residual styrene decreases and the volume shrinkage of the resin system remains unchanged. At high MMA/St ratio, residual styrene can be substantially reduced, but the resin system suffers poor volume shrinkage control. Reactivity of the comonomer MMA and its compatibility to other components in the resin system can explain the observed results. A series of Seemann composites resin infusion molding process (SCRIMP) were conducted to study the relationship among materials, processing, and properties of molded composites in low temperature curing processes.     

Curing of unsaturated polyester resins: Viscosity studies and simulations in pre-gel state

The curing of styrene-unsaturated polyester (UP) resins was studied until gelation. The viscosity and gel points were measured during curing and were correlated with curing temperature, initiator concentration, and accelerator concentration. A gelation model concerning the formation of intra-crosslinked polymer coils, called microgels, was proposed. The model describes the gelation mechanism in four stages: induction, microgel formation, transition, and macro-gelation. The kinetic and gelation parameters of the model were experimentally obtained. The gel points and viscosities in the pre-gel state were simulated by the gelation model for isothermal and nonisothermal curings. Comparisons of the simulation results with experimental data showed good agreement.     

Waterborne unsaturated polyester resins

The transformation of solvent soluble unsaturated polyester resins into resins able to form stable water dispersion is presented in this paper. The methods of modification are discussed, consisting of the introduction of polar hydrophilic groups such as carboxylic and sulfonic ones (sodium 5‐sulfonatoisophthalic acid) into the resin molecule, which ensure good tolerance with water. Instead of styrene, glycerol monoethers of allyl alcohol and unsaturated fatty alcohols were used as reactive built‐in crosslinking monomers for resin modification. The influence of the resin composition and method of synthesis on the dispersion stability and properties of photocurable lacquer coatings obtained from the waterborne resins were investigated.     

Improving glass transition temperature of unsaturated polyester thermosets: Conventional unsaturated polyester resins

Highly crosslinkable unsaturated polyester resins (UPR) have attracted many interests in the application as reinforced matrix materials. Here, we present a systematical study of the influence of different curing conditions and styrene concentrations on resin viscosity and dynamic-mechanical properties of the thermoset. The pure maleic Palapreg® P18-03 was selected as model UPR because of its broad industrial use. By applying newly developed thermal curing profiles (without thermal initiators) and by raising the styrene content, the T_g of the network could be increased up to 206/215°C (1/10 Hz). For the first time, a fast curable UPR based on propylene glycol and neopentyl glycol with a T_g of up to 215°C is described. A partial substitution of problematic styrene with methylmethacrylate, tert-butylacrylate, and maleic anhydride (MA) was studied as well. MA leads to significantly improved resin reactivity. A resin containing 42 wt% styrene and 8 wt% MA yields thermosets with remarkably improved mechanical properties and with a narrower glass transition range compared to the original P18-03.     

不饱和聚酯树脂微乳液的研究(Ⅰ)不饱和聚酯树脂的微乳化

合成了不同磺酸盐含量的三种不饱和聚酯，通过拟三元相图分析磺酸盐含量、苯乙烯、不同正构醇和水组成的体系对微乳区域的影响。研究结果表明，磺酸盐不饱和聚酯同苯乙烯互溶的前提下，磺酸盐含量越大，其微乳液增溶的水量越大；磺酸盐含量一定时，苯乙烯含量越小，其微乳液增溶的水量越大；正构醇质量分数为在2％～10％范围内，其微乳液增溶的水量最多；三种醇相比较，正丁醇体系的微乳区是W／O型向O／W型过渡的连续区域，正丙醇体系的O／W型微乳液区明显不同于正丁醇体系，正戊醇体系不能形成水包油型的微乳区。     

不饱和聚酯树脂的粗化工艺

介绍了不饱和聚酯树脂的粗化工艺流程及各工艺规范通过正交试验确定了最佳粗化工艺条件：粗化液的体积分数为400ml／L温度为80～85℃,粗化时间为20min。讨论了粗化液用量、粗化温度和时间对粗化效果和镀层质量的影响经检测表明,该金属镀层与基体结合力良好目前该工艺已应用于生产中。     

Effects of post-curing of unsaturated polyester resins in various media

Experimental studies were performed on the effects of postcuring of' styrenated, unsaturated polyesters in nitrogen gas, water or its vapor, hexane vapor, dimethyl sulfoxide (DMSO), and dirnethyl formamide (DMF) all at 100°C It was found that, nitrogen gas and water are inactive, hexane acts as a chain transfer agent, and DMF and DMSO behave as solvents which extract residual styrene monomer and anhydrides from the resins. Post-treatment in inert media can result in further reaction leading to more complete cure as free radicals and residual monomer continue to react. The post-curing reaction is a radical copolymerization. Further condepgation polymerisation does not occur. Post-curing in, hexane vapor1eads to a transfer of the active sites from the radicals to the hexane and to no further radical polymerization.     

Effect of resin composition on curing kinetic of nanoclay-reinforced unsaturated polyester resins

Curing behavior of two resins of different unsaturated polyesters [FARAPOL 101 (UF) and Bushpol 81715 (UB)] containing 3 wt % organically modified clay (OMC), catalyzed with methyl ethyl ketone peroxide as initiator and promoted by cobalt naphtenate accelerator was investigated by dynamic differential scanning calorimetry (DSC) and gel time test methods. Chemical structures of UF and UB resins were characterized by ¹H NMR, XRD and TEM techniques were used for morphology characterization of nanocomposites. DSC results showed that after adding OMC, the redox reaction rate of UF increased less than that of UB resin. Measurements of cloud-point temperature (T _c) indicated that the miscibility of styrene/UB alkyd chains was more than that of styrene/UF alkyd chains. Therefore, the alkyd/styrene ratio inside the platelets in UB would be more than that in the platelets in UF nanocomposite. Among the three factors in redox reaction rate of UB/OMC and UF/OMC systems namely: (1) decreasing alkyd-styrene copolymerization share among platelets of OMC, (2) decreasing the activation energy, (3) decreasing the number of collisions, the first one was more effective in UF/OMC system than in UB/OMC system. Consequently, the difference between redox reaction rates of UF/OMC and neat UF was negligible compared with the corresponding difference for UB/OMC and neat UB system.     

Curing polyester resins with visible light

Radiation curing of unsaturated polyester resin-based compositions offers a number of significant advantages over the use of peroxides and similar free-radical polymerisation initiators; the cure process can be closely controlled, is usually much faster, and the fabricator is not required to measure out, add, and blend-in small quantities of catalyst. However most forms of radiation including ultra violet (UV) involve heavy initial expense and the need to provide shielding to protect personnel. Furthermore UV radiation will not usually penetrate deeply into thick glassfibre-containing compositions owing to the absorption of UV light by both resin and glass. Photoinitiator systems which need only visible light have now been developed however. Using these systems almost any available light source including fluorescent tubes, tungsten filament bulbs and of course natural sunlight and daylight will cause the resin to cure rapidly and completely. By controlling the intensity of the incident light continuous close control of the cure process is easily achieved. The advantages of reduced energy requirements, fast cure,‘one pot’ chemistry and built-in indicators of degree of cure have already led to a number of special applications for visible light curable polyester resins.     

Rheology of unsaturated polyester resins. III. Effects of filler and low-profile additive on the thickening behavior of unsaturated polyester resin

An investigation was made of the rheological behavior of unsaturated polyester resin during thickening in the presence of filler or low-profile additive alone and, also, in the presence of both filler and low-profile additive. For the study, two different types of filler (CaCO₃ and clay) and two different types of low-profile additive (PMMA and PVAc) were evaluated. Compared to the resin/thickener system, the resin/filler/thickener system exhibits shear-thinning behavior as thickening progresses, and gives rise to smaller normal stress effects. On the other hand, the resin/low-profile additive/thickener system exhibits two distinct Newtonian regimes in the viscosity-shear stress curves and gives rise to larger normal stress effects. The viscosity behavior of the resin/filler/low-profile additive/thickener system was found to be very similar to that of the resin/low-profile additive/thickener system. In all cases, when the first normal stress difference was plotted against the shear stress, a correlation was obtained which was independent of thickening period. This behavior was exactly the same as for thickening polyester resin alone, as discussed in Part II of this series.     

Rheology of unsaturated polyester resins. I. Effects of filler and low-profile additive on the rheological behavior of unsaturated polyester resin

Measurements were taken of the bulk rheological properties of concentrated suspensions of particulates in unsaturated polyester resins, using a cone-and-plate rheometer. The particulates used were clay, calcium carbonate, and milled glass fiber. With clay and milled glass fibers, shear-thinning behavior of suspensions was observed at low shear rates or low shear stresses as the concentration of particulates was increased, whereas concentrated suspensions of calcium carbonate exhibited Newtonian behavior over the range of shear stresses or shear rates investigated. The cone-and-plate rheometer was also used for measurements of the bulk rheological properties of various mixtures of polyester resin and low-profile additives. For low-profile additives, solutions, in styrene, of poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) were used. It was found that the bulk viscosities of all mixtures of polyester resin and PVAc solution lie between those of the individual components, whereas the bulk viscosities of some mixtures of polyester resin and PMMA solution go through a minimum and a maximum, depending on the composition of the mixture. While all mixtures of polyester resin and PVAc solution exhibited negligible normal stress, some mixtures of polyester resin and PMMA solution exhibited noticeable normal stresses. It should be mentioned that polyester resin follows Newtonian behavior. It turned out that all mixtures of polyester resin and PVAc solution exhibited clear, homogeneous solutions, whereas mixtures of polyester resin and PMMA solution exhibited optical heterogeneity, i.e., turbidity. When polyethylene powders were used as low-profile additives, suspensions of polyester resin and polyethylene powders exhibited negative values of normal stress as the concentrations of suspension reached a critical value. When both filler and low-profile additive were put together in polyester resin, the rheological behavior became quite complex, indicating that some interactions exist between the filler and the low-profile additive.     

Cure of polyester resins. II

The copolymerization reaction between unsaturated polyesters and styrene has been studied by a torsional pendulum. The accuracy of the dynamic-mechanical measurements obtained is discussed briefly, and the results are compared with those of previous work on the change of hardness during cure.