Effects of poly(vinyl acetate) and poly(methyl methacrylate) low-profile additives on the curing of unsaturated polyester resins. I. Curing kinetics by DSC and FTIR

The effects of two low-profile additives (LPA), poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) on the curing kinetics during the cure of unsaturated polyester (UP) resins at 110°C were investigated by using a differential scanning calorimeter (DSC) and a Fourier transform infrared spectrometer (FTIR). The effects of temperature, molar ratio of styrene to polyester CC bonds, and LPA content on phase characteristics of the static ternary systems of styrene–UP–PVAc and styrene–UP–PMMA prior to reaction were presented. Depending on the molar ratio of styrene to polyester CC bonds, a small shoulder or a kinetic-controlled plateau in the initial portion of the DSC rate profile was observed for the LPA-containing sample. This was due to the facilitation of intramicrogel crosslinking reactions since LPA could enhance phase separation and thus favor the formation of clearly identified microgel particles. FTIR results showed that adding LPA could enhance the relative conversion of polyester CC bonds to styrene throughout the reaction. Finally, by use of a microgel-based kinetic model and static phase characteristics of styrene–UP–LPA systems at 25°C, the effects of LPA on reaction kinetics regarding intramicrogel and intermicrogel crosslinking reactions, relative conversion of styrene to polyester CC bonds, and the final conversio have been explained. © 1995 John Wiley & Sons, Inc.     

Effects of low-profile additives on the curing reaction of unsaturated polyester resins

The effect of low-profile additives (LPA), i.e., poly(vinyl acetate) (PVAC) and poly(methyl methacrylate) (PMMA), on the curing reaction of unsaturated polyester (UPE) resins was studied by gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The curing reaction profiles were determined by DSC, while GPC was used to investigate the variation of the sizes of microgel particles during the early stage of curing reaction in UPE–styrene resins. The DSC experimental results indicated that the curing reaction rate decreased as the concentration of LPA increased. At a fixed LPA concentration, the curing reaction rate was slower for resins mixed with LPA possessing worse compatibility with UPE resins. During the early stage of curing reaction, the size and structure of the UPE microgels formation strongly depended on the concentration of LPA and also on the compatibility of the components in the curing system. The experimental results of this study revealed that the concentration of LPA and the compatibility of LPA with UPE resins had a strong influence on the polyester microgel formation and the curing behavior. © 1995 John Wiley & Sons, Inc.     

Effects of thermoplastic additives on the cure of unsaturated polyester resins

Thermoplastic additives tend to promote the phase separation during the reaction of unsaturated polyester resins. Consequently, they reduce the amount of shrinkage during curing. Several thermoplastic additives which resulted in significant different microstructure of cured resins were investigated. The effects of microstr acture formation on the sol-gel transition, reaction kinetics, and gelation time were studied. The mechanism of microstructure formation and causes of macro-gelation were explained by the influence of thermoplastic additives on the particle formation rate and inter-particle reaction rate during curing.     

Effects of poly(vinyl acetate) and poly(vinyl chloride‐co‐vinyl acetate) low‐profile additives on properties of cured unsaturated polyester resins. II. glass‐transition temperatures and mechanical properties

Three series of self‐synthesized poly(vinyl acetate)‐based low‐profile additives (LPAs), including poly(vinyl acetate), poly(vinyl chloride‐co‐vinyl acetate), and poly(vinyl chloride‐co‐vinyl acetate‐co‐maleic anhydride), with different chemical structures and molecular weights were studied. Their effects on the glass‐transition temperatures and mechanical properties for thermoset polymer blends made from styrene, unsaturated polyester, and LPAs were investigated by an integrated approach of the static phase characteristics, cured sample morphology, reaction kinetics, and property measurements. Based on Takayanagi mechanical models, the factors that control the glass‐transition temperature in each phase region of the cured samples and the mechanical properties are discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3347–3357, 2003     

Effects of poly(vinyl acetate) and poly(vinyl chloride‐ co‐vinyl acetate) low‐profile additives on properties of cured unsaturated polyester resins. I. Volume shrinkage characteristics and internal pigmentability

Three series of self‐synthesized poly(vinyl acetate)‐based low‐profile additives (LPAs) with different chemical structures and molecular weights, including poly(vinyl acetate), poly(vinyl chloride‐co‐vinyl acetate), and poly(vinyl chloride‐co‐vinyl acetate‐co‐maleic anhydride), were studied. Their effects on the volume shrinkage characteristics and internal pigmentability for low‐shrink unsaturated polyester (UP) resins during cure were investigated. The experimental results were examined with an integrated approach involving measurements of the static phase characteristics of the ternary styrene/UP/LPA system, the reaction kinetics, the cured sample morphology, and microvoid formation by using differential scanning calorimetry, scanning electron microscopy, optical microscopy, and image analysis. Based on the Takayanagi mechanical model, factors leading to both good volume shrinkage control and acceptable internal pigmentability for the molded parts were explored. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3336–3346, 2003     

Effect of curing temperature on the morphology of unsaturated polyester resin blended with poly(vinyl acetate)

Phase separation of unsaturated polyester/styrene (UPE/styrene) resin blended with 5 and 10 wt% of poly(vinyl acetate) (PVAc) cured at various temperatures ranging from 75°C to 150°C was studied using low angle laser light scattering (LALS) and scanning electron microscopy (SEM). For UPE/styrene resin blended with 5 wt% PVAc cured at a temperature below 90°C, a discrete phase‐separated structure was observed. As curing temperature was raised above 90°C, SEM micrographs revealed that more and more cured UPE globules fused together with increasing curing temperature. The LALS intensity profile became broader with increasing curing temperature, indicating a less discrete phase‐separated structure at a higher curing temperature. As PVAc content was increased to 10 wt%, SEM micrographs revealed a co‐continuous phase‐separated structure. The LALS intensity decayed slowly from the center of the scattering pattern to a high scattering angle without the appearance of maximum scattering peak intensity. The morphology of the cured sample did not change too much with curing temperature for UPE/styrene resin blended with 10 wt% of PVAc.     

Analysis of volumetric changes of unsaturated polyester resins during curing

Two models were proposed to predict the volume changes that occur during the cure of unsaturated polyester resin/styrene systems. These models are able to account for both thermal expansions/contractions and polymerization shrinkage during processing. One model, which is based on coversion, was developed by combining experimental results from differential scanning calorimetry and dilatometry. The second model is based on radical concentration, and was developed using results from electron spin resonance spectroscopy and dilatometry. Predictions obtained from both models were compared with experimental results and reasonable agreement was obtained.     

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.     

Effects of poly(methyl methacrylate)‐based low‐profile additives on the properties of cured unsaturated polyester resins. II. Volume shrinkage characteristics and internal pigmentability

The effects of three series of self‐synthesized poly(methyl methacrylate) (PMMA)‐based low‐profile additives (LPAs), including PMMA, poly(methyl methacrylate‐co‐butyl acrylate), and poly(methyl methacrylate‐co‐butyl acrylate‐co‐maleic anhydride) with different chemical structures and MWs on the volume shrinkage characteristics and internal pigmentability for low‐shrink unsaturated polyester (UP) resins during curing were investigated by an integrated approach of static phase characteristics of the ternary styrene (ST)/UP/LPA system, reaction kinetics, cured‐sample morphology, microvoid formation, and property measurements. The relative volume fraction of microvoids generated during the cure was controlled by the stiffness of the UP resin used, the compatibility of the uncured ST/UP/LPA systems, and the glass‐transition temperature of the LPAs used. On the basis of the Takayanagi mechanical model, the LPA mechanism on volume shrinkage control, which accounted for phase separation and microvoid formation, and factors leading to both a good volume shrinkage control and acceptable internal pigmentability for the molded parts are discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3388–3397, 2004     

Effects of poly(methyl methacrylate)‐based low‐profile additives on the properties of cured unsaturated polyester resins. I. Miscibility,curing behavior,and glass‐transition temperatures

The effects of three series of self‐synthesized poly(methyl methacrylate) (PMMA)‐based low‐profile additives (LPAs), including PMMA, poly(methyl methacrylate‐co‐butyl acrylate), and poly(methyl methacrylate‐co‐butyl acrylate‐co‐maleic anhydride), with different chemical structures and MWs on the miscibility, cured‐sample morphology, curing kinetics, and glass‐transition temperatures for styrene (ST)/unsaturated polyester (UP) resin/LPA ternary systems were investigated by group contribution methods, scanning electron microscopy, differential scanning calorimetry (DSC), and dynamic mechanical analysis, respectively. Before curing at room temperature, the degree of phase separation for the ST/UP/LPA systems was generally explainable by the calculated polarity difference per unit volume between the UP resin and LPA. During curing at 110°C, the compatibility of the ST/UP/LPA systems, as revealed by cured‐sample morphology, was judged from the relative magnitude of the DSC peak reaction rate and the broadness of the peak. On the basis of Takayanagi's mechanical models, the effects of LPA on the final cure conversion and the glass‐transition temperature in the major continuous phase of ST‐crosslinked polyester for the ST/UP/LPA systems was also examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3369–3387, 2004     

Phase separation in styrenated polyester resin containing a poly(vinyl acetate) low-profile additive

Scanning electron microscopy has been used to observe morphology in styrenated polyester resins containing poly(vinyl acetate) (PVA). Resins containing 8% PVA form composite spherical particles which occupy 35 vol% of the total material. It is concluded that these particles consist of resin sub-inclusions embedded in the continuous matrix of polyester resin. Increasing the PVA content to 16% results in a phase inversion: PVA forms the matrix, and the resin is present as spherical particles. These observations are interpreted with the aid of a ternary diagram.     

Microgelation of unsaturated polyester resins in the presence of poly(vinyl acetate) by static and dynamic light scattering

The partially cured unsaturated polyester (UPE)/styrene resins with various degrees of conversion lower than gel conversion blended with PVAc and 2‐fluorotoluene solvent were investigated using both static and dynamic light scattering (SLS and DLS). The solvent (i.e., 2‐fluorotoluene) is isorefractive with PVAc; thus, one sees only primary and partially cured UPEs in light‐scattering experiments. DLS was used to follow the variations of primary UPE and UPE microgel particle sizes, and SLS was used to follow the variations of UPE molecular weight, second virial coefficient (A₂), anisosymmetry (ρ_v), and differential index refraction (dn/dC) with degree of UPE conversion and PVAc concentration. The experimental data showed that, at a fixed degree of UPE/styrene conversion, increasing PVAc concentration in the UPE/styrene system caused decreases in dn/dC, A₂, ρ_v, and particle sizes of UPE microgels. These results suggest that mixing PVAc into UPE/styrene resins causes an increase in the compactness of UPE coils and favors intramolecular UPE/styrene cyclization in the early stage of curing. Thus A₂, ρ_v, and particle sizes of microgels decreased with increasing PVAc concentration. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1439–1449, 2001     

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.     

Refractive index of solutions containing poly(vinyl acetate) and poly(methyl methacrylate)

Refractive index measurements can be used successfully for on-line evaluation of extent of reaction in solution polymerization reactors. For this reason, the refractive index of solutions containing tert-butanol (TBOH), methyl methacrylate (MMA), vinyl acetate (VA), poly(methyl methacrylate) (PMMA), and poly(vinyl acetate) (PVA) were measured and a mathematical correlation was developed to fit the experimental data. The correlation can be extended to fit published data obtained with different solvents.     

Phase separation of unsaturated polyester resin blended with poly(vinyl acetate)

The behavior of phase separation during the curing reaction of unsaturated polyester (UPE) resin in the presence of low profile additive, that is, poly(vinyl acetate) (PVAc), was studied by low-angle laser light scattering (LALS) and scanning electron microscopy (SEM). The experimental results revealed that the PVAc-rich phase was regularly dispersed in the cured styrene–UPE matrix for styrene–UPE resin blended with 5 wt % of PVAc. As the PVAc content was increased higher than 10 wt %, a cocontinuous PVAc and cured styrene–UPE phase was observed for the cured systems. The LALS observations were carried out in situ at a curing temperature of 100°C; thus, the effect of the rate of exothermic heat released from curing reaction on the morphology of curing system was investigated and reported in this work. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2413–2428, 1999     

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.     

Effect of tacticity of poly(methyl methacrylate) on the miscibility with poly(vinyl acetate)

The results of the miscibility between the chemically similar polymers poly(methyl methacrylate) (PMMA) and poly(vinyl acetate) (PVAc) published so far show inconsistent statements concerning miscibility. The problems may be due to differences in molecular weights, tacticity, and preparation methods of the polymers. This investigation was carried out by using either chloroform or tetrahydrofuran (THF) as solvent to prepare the blends, because to our knowledge, nobody has reported any tacticity effect of PMMA on the miscibility with PVAc. Therefore, in this article, different tactic PMMAs were used to mix with PVAc and their miscibility was studied calorimetrically. The results showed little effect of solvent and tacticity. PMMA and PVAc were determined to be almost completely immiscible because of the observation of two T_g's. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 35–39, 2004     

Comparison of the phase behaviour of the liquid-crystalline polymer/poly(methyl methacrylate) and poly(vinyl acetate)/poly(methyl methacrylate) blends

The phase behaviour of blends of a liquid-crystalline polymer (LCP) and poly(methyl methacrylate) (PMMA), as well as the phase state of blends of PMMA and poly(vinyl acetate) (PVA) has been investigated using light scattering and phase-contrast optical microscopy. The blends of LCP and PMMA have been obtained by coagulation from ternary solutions. The cloud point curves were determined. It was established that both pairs demix upon heating, ie have an LCST. In the region of intermediate composition, the phase separation proceeds according to a spinodal mechanism; however for LCP/PMMA blends, the decomposition proceeds according to a non-linear regime from the very onset. In the region of small amounts of LCP, the phase separation follows a mechanism of nucleation and growth. For PMMA/PVA blends, the spinodal decomposition proceeds according to a linear regime, in spite of the molecular mobility that PVA chains develop at lower temperatures. Only after prolonged heat treatment does the process transit to a non-linear regime. The data show a similarity between the phase behaviour of blends of liquid-crystalline and of flexible amorphous polymers. The distinction consists of the absence of a linear regime of decomposition for LCP-PMMA blends. © 1999 Society of Chemical Industry     

Chemorheology of thermosetting resins. III. Effect of low-profile additive on the chemorheology and curing kinetics of unsaturated polyester resin

An experimental study was conducted to investigate the effect of low-profile thermoplastic additives on the rheological behavior during cure and the curing kinetics of unsaturated polyester resin. For the study, a general-purpose polyester resin was used and two different types of thermoplastic additive, poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA), were used as low-profile additives. It has been found that, during cure, the resin/PMMA system exhibits shearthinning behavior even before the cure time reaches the critical value tη∞ whereas the resin/PVAc system does not. Also, both PVAc and PMMA help reduce the shrinkage of the resin during cure. However, our study shows that shrinkage control becomes effective only when the shear rate is greater than a certain critical value. The curing behavior determined with the aid of differential scanning calorimetry (DSC) shows that the rate of cure and the final degree of cure are decreased when the amount of low-profile additive is increased.     

Fractal characterization of the fissures occuring during polymerization of low-profile unsaturated polyester resins

Blends of unsaturated polyester resin and polyvinylacetate (PVAc) were cured between two glass slides. In this case, the low-profile effect arises by fissuring with a fractal geometry. This paper shows how the fractal dimension of the fissures depends on the PVAc amount and on the cure temperature. These results are discussed with the present knowledge about the polyester network morphology in two phases more or less co-continuous.