Effect of co-promoter and secondary monomer on shrinkage control of unsaturated polyester (UP)/styrene (St)/low-profile additive (LPA) systems cured at low temperatures

The shrinkage of unsaturated polyester (UP)/styrene (St) resins cured at low temperatures can be reduced by the presence of low-profile additives (LPAs). It is believed that the reaction-induced phase separation and the polymerization shrinkage in both the LPA-rich and UP-rich phases result in the formation of microvoids, which partially compensates the resin shrinkage. The relative reaction rate in the two phases plays an important role in shrinkage control. In this study, secondary monomers [such as divinylbenzene (DVB) and trimethylopropane trimethacrylate (TMPTMA)] and a co-promoter, 2,4-pentandione (2,4-P), were added into the UP/St/LPA resin systems to investigate their effect on the shrinkage control of resins cured at low temperatures. Dilatometery results showed that the addition of both TMPTMA and 2,4-P resulted in an earlier volume expansion during curing and better shrinkage control. The phase separation, reaction kinetics, and viscosity changes in the LPA-rich and UP-rich phases during curing were also investigated. The results confirmed that the increased reaction rate in the LPA-rich phase led to an earlier formation of microvoids and, consequently, less volume shrinkage of the cured resin. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 738–749, 2001     

Effects of reactive low‐profile additives on the volume shrinkage and internal pigmentability for low‐temperature cure of unsaturated polyester

The effects of reactive poly(vinyl acetate)‐block‐poly(methyl methacrylate) (PVAc‐b‐PMMA) and poly(vinyl acetate)‐block‐polystyrene (PVAc‐b‐PS) as low‐profile additives (LPA) on the volume shrinkage characteristics and internal pigmentability for low‐shrink unsaturated polyester resins (UP) during the cure at 30°C were investigated. These reactive LPAs, which contained peroxide linkages in their backbones, were synthesized by suspension polymerizations, using polymeric peroxides (PPO) as initiators. Depending on the LPA composition and molecular weight, the reactive LPA could lead to a reduction of cyclization reaction for UP resin during the cure, and would be favorable for the decrease of intrinsic polymerization shrinkage after the cure. The experimental results have been explained by an integrated approach of measurements for the static phase characteristics of the styrene (ST)/UP/LPA system, reaction kinetics, cured sample morphology, and microvoid formation by using differential scanning calorimetry (DSC), scanning electron microscopy (SEM), optical microscopy (OM), and image analysis. Based on the Takayanagi mechanical model, factors leading to both a good volume shrinkage control and acceptable internal pigmentability for the molded parts have been explored. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 967–979, 2006     

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     

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     

Effects of reactive low‐profile additives on the properties of cured unsaturated polyester resins. I. Volume shrinkage and internal pigmentability

The effects of reactive poly(methyl methacrylate) (PMMA) and poly(vinyl acetate)‐block‐PMMA as low‐profile additives (LPAs) on the volume shrinkage characteristics and internal pigmentability for low‐shrink unsaturated polyester (UP) resins during curing at 110°C were investigated. These reactive LPAs, which contained peroxide linkages in their backbones, were synthesized by suspension polymerization with polymeric peroxides as initiators. Depending on the LPA composition and molecular weight, the reactive LPAs led to a considerable volume reduction or even to a volume expansion after the curing of styrene (ST)/UP/LPA ternary systems; this was attributed mainly to the expansion effects of the LPAs on the ST‐crosslinked polyester microgel structures caused by the reduction in the cyclization reaction of the UP resin during curing as well as to the repulsive forces between the chain segments of UP and LPAs within the microgel structures. The experimental results were explained by an integrated approach of measurements for the static phase characteristics of the ST/UP/LPA system, reaction kinetics, cured sample morphology, and microvoid formation with differential scanning calorimetry, scanning electron microscopy, optical microscopy, and image analysis. With the aid of the Takayanagi mechanical model, the factors leading to both a good volume shrinkage control and acceptable internal pigmentability for the molded parts were also explored. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 264–275, 2005     

Effects of poly(vinyl acetate) and poly(methyl methacrylate) low-profile additives on the curing of unsaturated polyester resins. II. Morphological changes during cure

The effects of two low-profile additives (LPA), poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA), on the morphological changes during the cure of unsaturated polyester (UP) resins at 110°C were investigated by an approach of integrated reaction kinetics-morphology-phase separation measurements by using a differential scanning calorimeter (DSC), scanning electron microscopy (SEM), optical microscopy (OM), and a low-angle laser light-scattering appartus (LALLS). For the UP resins cured at 110°C, adding LPA could facilitate the phase separation between LPA and crosslinked UP phases early in the reaction, and discrete microgel particles were thus allowed to be identified throughout the reaction. Microvoids and microcracks responsible for the volume shrinkage control could also be observed evidently at the later stage of reaction under SEM. Depending on the types of LPA and the initial molar ratios of styrene to polyester C?C bonds, the morphological changes during the cure varied considerably. The progress of microstructure formation during reaction has been presented. Static ternary phase characteristics for the styrene–UP–LPA system at 25°C have also been employed to elucidate the resulting morphology during the cure in both the continuous and the dispersed phases. © 1995 John Wiley & Sons, Inc.     

Control of shrinkage and residual styrene of unsaturated polyester resins cured at low temperatures: I. Effect of curing agents

In low temperature molding processes, control of resin shrinkage and residual monomer is an important concern. The presence of low profile additives (LPAs) can reduce the shrinkage of unsaturated polyester (UP)/styrene (St) resins under proper processing conditions but may increase the residual styrene content. A systematic study was carried out to investigate the effect of the initiator system and reaction temperature on sample morphology, final resin conversion, and resin shrinkage of UP resins with LPA. It was found that the final conversion of the resin system could be improved by using dual initiators. The effect is more obvious at low temperatures. Volume shrinkage measurements of the resin system initiated with dual initiators revealed that good LPA performance was achieved at low (e.g. 35 °C) and high (e.g. 100 °C) temperatures but not at intermediate ones. This can be explained by how temperature affects phase separation, reaction kinetics in the LPA-rich and UP-rich phases, micro-void formation, and thermal expansion.     

Low‐profile mechanisms in a PVAc/polyester blend

The different steps associated with the curing of a PVAc/polyester blend are identified and correlated to the mechanism of shrinkage control in the presence of a low‐profile additive (LPA). Poly(vinyl acetate) (PVAc) is used as a LPA and is shown to induce a phase separation upon curing that leads to an interconnected globule morphology. This morphology strongly modifies the rheokinetics of the blend compared to that of the neat polyester resin. In particular, the presence of PVAc delays the cure kinetics and the gel time. A comparison between these delays, called shift times, demonstrates an increase in the gel conversion of polyester in the presence of PVAc. This, coupled to the thermal expansion of PVAc at the early stages of curing, contributes to the low‐profile effect. Microvoids in the LPA‐rich phase, which are believed to play a key role in the mechanism of shrinkage control, are efficient at the later stages of curing and during cooling and complete the low‐profile effect. However, it is also shown that the formation of microvoids may indirectly induce macroscopic voids that could be at the origin of pinholes at the surface of the parts molded with this material. POLYM. ENG. SCI. 46:303–313, 2006. © 2006 Society of Plastics Engineers     

Dynamics of migration and phase selective localization of nanoclay in HNBR/ENR blends

The phase specific selective localization and dynamics of migration of nanoclay in hydrogenated acrylonitrile butadiene rubber (HNBR)/epoxidized natural rubber (ENR) blend systems is investigated. The phase specific dispersion of clay particles is monitored through measuring the online measured electrical conductance (OMEC) during mixing by means of a sensor system installed inside the chamber of an internal mixer. The results of different characterization techniques, such as atomic force microscopy, transmission electron microscopy, and small angle X‐ray scattering have been used to understand and interpret the OMEC behaviors of nanoclay‐filled rubber compounds individually (HNBR and ENR) and their blend systems. The observed online conductance is ionic in nature that arises due to the release of surfactant molecules from the clay galleries. It is observed that the OMEC behavior depends mainly on two factors: the localization of nanoclay in specific phase of the blend system and on the gradual development of blend morphology. The OMEC behavior and the supported data from the microscopic methods, clearly reveal the migration of organoclay from the ENR to HNBR phase during the mixing process, particularly localizing near the interface of the blend. Further, the localization of organoclay is also evaluated by applying the surface tension measurements based model, which also predicts the favorable localization of organoclay in HNBR phase of the blend. The work clearly suggests the OMEC method to be a powerful online tool to monitor and control the nanoclay dispersion and localization in rubber based nanocomposites during the melt mixing process. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44074.     

Influence of Nanoclay on the Adhesive and Physico-Mechanical Properties of Liquid Polysulfide Elastomer

Addition of Cloisite 30B nanoclay particles to a typical ammonium dichromate cured liquid polysulfide elastomeric adhesive leads to very dramatic increase in the aluminum–aluminum joint strength measured by 180° peel test. The increase in adhesive strength could be explained in terms of higher cohesive strength of the nanocomposite adhesives, which has been derived from good interaction between the nanoclay and the polysulfide elastomer. The addition of nanoclay also facilitates the adhesive to dissipate greater amount of energy (by fibrils formation) during the debonding process of the peel test. In addition, the nanoclay aids the low polarity polysulfide elastomer to achieve better molecular contact with the aluminum substrate. The nanoclay particles are very well dispersed (mostly exfoliated) in the polymer matrix even at 8 wt% of nanoclay concentration. X-ray diffraction (XRD) and transmission electron microscopy (TEM) studies provide evidences for the excellent dispersion of the nanoclay platelets in the polymer matrix. The results of the mechanical and dynamic mechanical studies confirm the excellent interaction between the nanoclay and the polysulfide elastomer.     

热固性PF/PU复合体系的收缩性能

将端羟基封端和端羧基封端的聚氨酯 (PU)预聚物分别与酚醛树脂 (PF)固化 ,制备了两种体系的复合物。通过测试其体系收缩率 ,结果表明 :随着聚氨酯预聚物加入量的增加 ,PF/PU共混物的体积收缩率明显变小 ,并能达到负值。端羧基PU的低收缩性能更为显著 ,当其加入量在 5 相似文献   

Phase separation,cure kinetics,and morphology of epoxy/poly(vinyl acetate) blends

Epoxy based on diglycidyl ether of bisphenol A + 4,4′diaminodiphenylsulfone blended with poly(vinyl acetate) (PVAc) was investigated through differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and environmental scanning electron microscopy (ESEM). The influence of PVAc content on reaction induced phase separation, cure kinetics, morphology and dynamic‐mechanical properties of cured blends at 180°C is reported. Epoxy/PVAc blends (5, 10 and 15 wt % of PVAc content) are initially miscible but phase separate upon curing. DMTA α‐relaxations of cured blends agree with T_g results by DSC. The conversion‐time data revealed the cure reaction was slower in the blends than in the neat system, although the autocatalytic cure mechanism was not affected by the addition of PVAc. ESEM showed the cured epoxy/PVAc blends had different morphologies as a function of PVAc content: an inversion in morphology took place for blends containing 15 wt % PVAc. The changes in the blend morphology with PVAc content had a clear effect on the DMTA behavior. Inverted morphology blends had low storage modulus values and a high capability to dissipate energy at temperatures higher than the PVAc glass‐transition temperature, in contrast to the behavior of neat epoxy and blends with a low PVAc content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1507–1516, 2007     

Addition of unmodified nanoclay to improve the performance of unsaturated polyester resin coating on natural stone

In this study, an unsaturated polyester resin (UPR) thin coating containing styrene monomer has been used to consolidate Brown Emperor natural stone pieces. Different amounts (0.5-2 wt%) of nanoclay was added to reduce shrinkage during cure and to impart both stiffness and toughness. The uncured UPR-nanoclay hybrids were characterized by rotational rheology, the gelation was monitored by means of a texture analyzer and the viscoelastic and thermal properties were determined in the cured UPR-nanoclay films. Transmission electron microscopy (TEM) was used to establish the degree of dispersion of the nanoclay in the UPR-nanoclay composites. The mechanical performance of the UPR-nanoclay thin coated natural stone pieces was measured by means of 3-points bending and impact strength tests.Addition of nanoclay (0.5 and 1 wt%) increased noticeably the viscosity to the UPR resin. The gel time of the UPR resin was significantly decreased by adding small amounts of nanoclay due to the interactions between the filler and the styrene in the UPR resin. Moreover, addition of nanoclay decreased the shrinkage degree during curing of UPR resin. In the cured composites, improved thermal properties in UPR were reached by adding nanoclay due to the creation of a network between the filler and the polymer matrix. Bundle nanometric size nanoclay agglomerates were observed which did not affect the glass transition temperature but increased the viscoelasticity of the UPR-nanoclay composites. Furthermore, the improved properties of UPR by adding nanoclay produced enhanced impact strength to coated natural stone pieces, as both stiffness and toughness were improved by nanoclay addition. Finally, good adhesion of nanoclay filled UPR to the surface of natural stone was reached.     

Permeation characteristics of poly(vinyl alcohol)–poly(vinyl acetate) composite porous membranes

Poly(vinyl alcohol) (PVAc) composite porous membrane has been prepared from PVAc latex film by extraction with acetone. The PVAc latex was prepared by emulsion polymerization of vinyl acetate in the presence of PVA, employing the hydrogen peroxide–tartaric acid systemm as an initiator. The extraction degree of PVAc could be controlled in a wide range by changing the addition method of the initiator, and, acoordingly, PVA–PVAc omposite porous membranes which had variosu void volumes were obtained. The maximum void volume attained was ca. 90%. Permation characteristics of organic solvents wre investigated on the membranes whose extraction degrees were 95.6% and 80.7%. Thge feeds were benzene, n-hexane, cyclohexane, and their mixtures. neither swelling nor shrinkage in tje appearance size of the while benzene hardly permeated even at 20 kg/cm². The grafted PVAc in the mebrane was removed or converted into grafted PVA by treatment with sodium methylate, and then the depression of benzene permeation was lost. The grafted PVAc was suggested to be localizd on the cell wall and was found to function as a valve which closes with nenzene or a good solvent for PVAc and opens with n-haxane or a poor solvent for PVAc.     

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.     

Effect of succinic acid on the shrinkage of unsaturated polyester resin

Succinic acid was presented as a small molecule low shrinkage additive (LSA) in unsaturated polyester resin (UPR). The effects of succinic acid on the volume shrinkage and the flexural strength of UPR cured at 80 ± 1°C were investigated and compared with those of macromolecule LSAs, including polyvinyl acetate (PVAc), polymethyl methacrylate (PMMA), and polystyrene (PS). The results indicated that the volume shrinkage of succinic acid/UPR specimen was significantly lower than those of specimens with macromolecule LSAs. The flexural strength of succinic acid/UPR specimen was improved. The optimal time of pre‐esterification between succinic acid and the excess dihydric alcohol in UPR was 3.0 h, and the optimal addition of succinic acid was 20 g per 100 g UPR. Compared with 2,2‐dimethyl malonic acid we put forward before, succinic acid was a cheaper and more commercial LSA, which obviously accelerated the pre‐esterification process and presented excellent antishrinkage effect. DSC showed that with the addition of succinic acid, the polymerization of UPR was distinctive. The two‐stage polymerization of UPR glue including the cross‐polymerization of UPR and the homopolymerization of polyester was changed to a one‐stage polymerization with lower exotherm and slower polymerization rate, which was optimal for UPR. FTIR and high resolution magic angle spinning nuclear magnetic resonance (HR/MAS NMR) were applied for the quantitative characterization of pre‐esterification caused by succinic acid. Succinic acid performed better effects on the polymerization of UPR as compared to previous LSAs, and finally the homogeneous micro‐structure of cured succinic acid/UPR formed and was demonstrated by SEM. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41276.     

PF用低收缩添加剂的研究

通过调整物料配比合成了端羟基封端和端羧基封端的聚氨酯 (PU)预聚物 ,并分别与酚醛树脂 (PF)固化 ,制备了两种低收缩体系的复合物 ,利用红外光谱对其结构进行表征。通过测试固化物的体系收缩率表明 :随着聚氨酯预聚物加入量的增加 ,PF/PU共混物的体积收缩率明显变小 ,并能达到负值。端羧基PU的低收缩性能更为显著 ,当其加入量在 5 相似文献   

Control of shrinkage and final conversion of vinyl ester resins cured in low‐temperature molding processes

Vinyl ester resin is a major thermoset polymer used in low‐temperature composite manufacturing processes such as the Seemann composite resin infusion‐molding process (SCRIMP). Volume shrinkage and residual styrene are important concerns for composites produced in such processes. A low‐shrinkage additive (LSA) is a typical agent added to control the volume shrinkage of vinyl ester resins during molding. In this study, the effects of LSA content and the temperature profile (the temperature gradient and peak temperature) on the volume shrinkage control of a vinyl ester resin were investigated. The reaction kinetics of the resin system were also studied. We achieved good volume shrinkage control if we raised the curing temperature slowly to allow sufficient time for phase separation and if the curing temperature reached a high value after phase separation to allow microvoid formation. On the basis of experimental results, we designed an improved SCRIMP to increase resin conversion, reduce resin shrinkage, and produce composites with better properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1486–1496, 2003     

Influence of processing conditions on shrinkage behavior of low profile unsaturated polyester resins. I: Systems without fillers

Blends of unsaturated polyester resin and polyvinylacetate (PVAc) were molded with a new instrument called the Plastoreactomat (PRM). The shrinkage and exothermic peak of polymerization were recorded during moding, and the influence of the processing conditions (pressure and temperature) on these phenomena and on the morphology was investigated for various PVAc contents. Within the limits of this study, it was found that shrinkage increases as the temperature and pressure increase. These results are discussed in terms of a competition between the phase separation and the reaction rates. In addition, it was verified that a co-continuous two-phase system consisting of the PVAc and the polyester network enhances the low-profile behavior.     

Viscoelastic Properties of Montmorillonite Clay/Polyimide Composite Membranes and Thin Films

Montmorillonite clay, cloisite 30B (nanoclay), was successfully dispersed in a polyimide (PI) matrix by in situ condensation polymerization followed by solution casting and thermal imidization. Wide angle X-ray diffraction, WAXD, test was used to study the structure of cloisite 30B clay powder and nanoclay/polyimide composites. The WAXD spectra of nanoclay powder and the composites show one major diffraction peak at 4.76° and 6°, respectively, suggesting that the d-spacing of nanoclay was decreased by about 26% after composite film processing. The viscoelastic property of polyimide and nanoclay/polyimide composite was studied by using dynamic mechanical spectrometer. The storage modulus and glass–rubber transition temperature of nanoclay/polyimide composites increases with increasing volume fraction of clay. The storage modulus of the composites in the rubbery plateau region, (T > 400 °C) increased remarkably with increasing volume fraction of clay. A modulus enhancement, (E_C/E_M) of about three orders of magnitude, (E_C/E_M ~1,440) was obtained for nanoclay/polyimide composite containing 6.8 vol% of nanoclay. The tangent of the loss angle (tan δ) for the composites, decreased with increasing volume fraction of nanoclay. The observed decrease in tan δ with increasing volume fraction of clay is consistent with the established trend of increasing storage modulus and glass–rubber transition temperature with increasing volume fraction of nanoclay. The phenomenal increase in the rubbery plateau storage modulus and glass–rubber transition temperature with increasing volume fraction of clay is believed to be due to increased restriction of chain motion with increasing nanoclay volume fraction.