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.     

Effect of nanoclay on shrinkage control of low profile unsaturated polyester (UP) resin cured at room temperature

The addition of a small amount of nanoclay (1-3 wt%) can provide excellent volume shrinkage control of unsaturated polyester (UP)/styrene (St)/poly(vinyl acetate) (PVAc) systems cured at room temperature. PVAc serves as the low profile additive (LPA). In this study, both temperature-induced phase separation of the uncured resin mixture and transmission electron microscopy (TEM) of the cured sample revealed that nanoclay resided in the LPA-rich phase, leading to a higher reaction rate and earlier onset of micro-cracking in the LPA-rich phase or at the interface of the LPA-rich and UP-rich phases. Consequently, an earlier volume expansion during curing was observed in reactive dilatometry, resulting in better shrinkage control. On-line measurement of the composite thickness change during vacuum-infusion liquid composite molding [e.g. the Seemann Composite Resin Infusion Molding Process (SCRIMP)] further proved excellent volume shrinkage control of nanoclay filled systems, leading to a smoother composite surface.     

Effect of dual-initiator on low temperature curing of unsaturated polyester resins

In low temperature composite manufacturing processes, a major concern is how to control the resin gel time and cure time and how to achieve a high resin conversion with low residual volatile organic chemicals. In this study, a cobalt promoter catalyzed dual-initiator system was used to control the reaction rate and resin conversion of unsaturated polyester resins. A mechanistic kinetic model was developed to predict the reaction kinetics with dual initiators. This model can be used to simulate the isothermal and dynamic reaction rate and conversion profiles. It can also be utilized to predict the effect of promoter concentration on UP resin cured at low temperatures. The dual-initiator system was applied in the vacuum-assisted resin transfer molding process at room temperature. The kinetic model, in conjunction with the heat transfer analysis, was able to successfully predict the temperature profiles during the molding processes.     

Characterization of unsaturated polyester resin cured with styrene

In this work, the curing kinetic of an unsaturated polyester resin, mixed with styrene as curing agent, was studied by means of diffential scanning calorimetry (DSC) and infrared (IR) spectroscopy. Investigations were made in situ during curing and post-curing periods. The enthalpy (ΔH_cop) characterizing the styrene homopolymerization and its copolymerization with the polyester chains was determined from isothermal DSC investigations. The residual enthalpy (ΔH_res) was determined from nonisothermal DSC measurements. We find that the quantity (ΔH_res + ΔH_cop) depends on the curing temperature (T_iso). Styrene homopolymerization and/or copolymerization lead to characteristic bonds modifications. The variations of the most characteristic bonds versus curing duration were studied from Fourier transform IR investigations. The data allow the determination of a relationship between transformation rate and curing duration using a time constant (τ) characteristic of each reaction involved during the liquid to solid-state transformation. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 695–703, 1998     

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     

A solid-state 13C nuclear magnetic resonance study of cured,unsaturated polyester resins

The styrene sequence distributions and amount of reacted fumarate units in cured, unsaturated polyester resins were studied by solid-state ¹³C nuclear magnetic resonance. Increasing the styrene content and molar ratio of styrene to the double bonds in the polyester chain increased the amount of diad and n-ad sequences and decreased the amount of monad sequences. At the same time, the amount of reacted fumarate units increased. The glass transition temperature was almost constant for resins with the same composition but different styrene contents. Changing the composition affected the glass transition temperature, which could not be detected for highly crosslinked resins. The mechanical properties were improved with increasing styrene content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 563–571, 1999     

Effects of chemical structure of polyurethane‐based low‐profile additives on the miscibility,curing behavior,volume shrinkage,glass transition temperatures,and mechanical properties for styrene/unsaturated polyester/low‐profile additive ternary systems. I: Miscibility,curing behavior,and volume shrinkage

The effects of chemical structure and molecular weight of three series of thermoplastic polyurethane‐based (PU) low‐profile additives (LPA) on the miscibility of styrene (ST)/unsaturated polyester (UP) resin/LPA ternary systems prior to reaction were investigated by using the Flory‐Huggins theory and group contribution methods. The reaction kinetics during the cure at 110°C and the cured sample morphology were also studied by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM), respectively. The phase‐separation characteristics of ST/UP/LPA systems during the cure, as revealed by the cured‐sample morphology, and the DSC reaction‐rate profile, could be generally predicted by the calculated upper critical solution temperature for the uncured ST/UP/LPA systems. Finally, based on the measurements for volume change and microvoid formation, volume shrinkage characteristics for the cured ST/UP/LPA systems have been explored. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 543–557, 2000     

Dynamic mechanical analysis of segmental relaxation in unsaturated polyester resin networks: Effect of styrene content

The effect of styrene content on non-exponential and non-Arrhenius behavior of the α-relaxation of cured unsaturated polyester resins (UPR) was investigated by dynamic mechanical analysis (DMA). To compare the temperature dependence of the relaxation times, the Angell fragility concept was applied to samples with different crosslink densities. Furthermore, the number of structural units per cooperatively rearranging region (CRR) was estimated using random walk model and the modified Adam-Gibbs theory. The results showed that rising styrene content enhanced the crosslink density of the networks, which altered the intensity and broadness of the α-relaxation. The fragility index, a measure of temperature dependence of relaxation time, and the average size of CRR at glass transition region was also increased by styrene content. Therefore, the segmental relaxation in networks with higher crosslink density could be associated with stronger intermolecular coupling. In addition, it was observed that the mean required energy for internal rearrangement of structural units within the CRR decreased as the fragility index increased, while the mean barrier height for repositioning of a CRR in cooperation to its local environment was nearly constant.     

Microscopy of the morphology in low styrene emission glass fiber/unsaturated polyester laminates

Low styrene emission (LSE) unsaturated polyester resins are of interest in the context of increasing environmental concerns in the society. LSE resins have been developed to decrease styrene emission during the processing of composites based on unsaturated polyesters. In this article we applied a microscopy methodology to study morphology effects in laminates based on LSE polyesters. The study connects to the longer term objective to improve the understanding of how additives reduce styrene emission without imparting delamination resistance in composite laminates based on LSE polyesters. The major morphology differences between laminates made from different polyesters are discussed, including birefringent layers present as an interphase between different layers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1555–1562, 1999     

季戊四醇磷酸酯蜜胺盐阻燃剂的合成及应用

以磷酸、季戊四醇和三聚氰胺合成了无卤膨胀型阻燃剂季戊四醇磷酸酯蜜胺盐,并对产物进行了差热和热失重及红外分析。结果显示,该阻燃剂在266℃有一吸热分解峰,显示出较好的稳定性;根据残炭率确定的合成最佳条件为:n(磷酸)∶n(季戊四醇)∶n(三聚氰胺)=2~2.5∶1∶1.8~2.2;合成温度100~110℃;反应时间4~6 h;以此阻燃剂添加到不饱和聚酯里,添加18份时阻燃级别可达UL-V0级。该阻燃剂具有分解温度适中,阻燃效率高等优点。     

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.     

Comparison of unsaturated polyester and vinylester resins in low temperature polymerization

Many composite products are produced at low temperatures in processes such as resin transfer molding (RTM), vacuum infusion molding (e.g., Seemann Composite Resin Infusion Molding Process—SCRIMP), and hand lay‐up. These processes are widely used for marine, civil infrastructure, transportation and defense applications. Unsaturated polyester and vinylester resins are two major resins used in these processes due to their low cost, good performance, and processibility. In this study, the reaction kinetics and rheological changes of these two resins cured at low temperatures were studied. Effects of resin type, initiator, promoter, inhibitor and retarder on the reaction kinetics and rheological behaviors were examined using a Differential Scanning Calorimeter (DSC) and a Rheometrics Dynamic Analyzer (RDA). A model was developed to quantify the effects of resin type, temperature, and different curing agents on the gel time for both polyester and vinylester resins cured at low temperatures. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1230–1242, 2001     

Effects of chemical structure of polyurethane‐based low‐profile additives on the miscibility,curing behavior,volume shrinkage,glass transition temperatures,and mechanical properties for styrene/unsaturated polyester/low‐profile additive ternary systems. II: Glass transition temperatures and mechanical properties

The effects of three series of thermoplastic polyurethane‐based (PU) low‐profile additives (LPA) with different chemical structures and molecular weights on the glass transition temperatures and mechanical properties for thermoset polymer blends made from styrene (ST), unsaturated polyester (UP), and LPA have been investigated by an integrated approach of static phase characteristics‐cured sample morphology‐reaction conversion‐property measurements. The three series of PU used were made from 2,4‐tolylene di‐isocyanate (2,4‐TDI) and varied diols, namely polycaprolactone diol (PCL), poly(diethylene adipate) diol (PDEA), and poly(propylene glycol) diol (PPG), respectively, while the two UP resins employed were synthesized from maleic anhydride (MA) and 1,2‐propylene glycol (PG) with and without modification by phthalic anhydride (PA). Based on the Takayanagi mechanical models, factors that control the glass transition temperature in each phase region of cured samples, as identified by the method of thermally stimulated currents (TSC), and mechanical properties will be discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 558–568, 2000     

Chemorheology of thermosetting resins. I. The chemorheology and curing kinetics of unsaturated polyester resin

The rheological properties and curing kinetics of a general-purpose polyester resin have been determined during isothermal cure. Both steady and oscillatory shearing flow properties were determined using a cone-and-plate rheometer, and the curing kinetics were determined using a differential scanning calorimeter (DSC). It was found that, as cure progresses, the steady shear viscosity increases very rapidly with cure time at all shear rates investigated, and normal forces show negative values at low shear rates and positive values at high shear rates. The observed negative normal forces are believed to result from material shrinkage during cure, and positive normal forces from the deformation of large molecules, formed by crosslinking reactions during cure. Note that, in a cone-and-plate rheometer, the shrinkage force acts in the direction opposite to that of normal forces. It is, therefore, concluded that extreme caution is needed in the interpretation of normal force measurements with thermosetting resins, subjected to steady shearing flow. Dynamic measurements seem to offer some insight on the onset of gel formation. More specifically, we have found that, when the unsaturated polyester resin was cured at a fast rate, the time at which a maximum in the loss modulus G” occurs coincides reasonably well with the time t_η∞ at which the steady shear viscosity η approaches infinity. However, at a slow rate of cure, the time at which tan δ equals unity agrees fairly well with t_η∞. DSC measurement has permitted us to determine the degree of cure as a function of cure time and the kinetic parameters in an empirical expression for the curing kinetics advanced by Kamal and co-workers. By combining the rheological and DSC measurements, we have constructed plots describing how the viscosity increases with the degree of cure, at various values of isothermal curing temperature.     

Effects of chemical composition and structure of unsaturated polyester resins on the miscibility, cured sample morphology and mechanical properties of styrene/unsaturated polyester/low-profile additive ternary systems: 2. Mechanical properties

The effects of three series of unsaturated polyester (UP) resins with different chemical composition or structure on the mechanical properties of three low-shrink UP resins containing thermoplastic polyurethane, poly(vinyl acetate) and poly(methyl methacrylate) respectively have been investigated by an integrated approach of static phase characteristics–cured sample morphology–reaction conversion–property measurements. The three series of UP resins synthesized include: maleic anhydride (MA)–neopentyl glycol (NPG)–diethylene glycol (DEG) types, with various molar ratios of NPG and DEG; MA–1,2-propylene glycol (PG) types with and without modification by a saturated dibasic aromatic anhydride or acid, such as phthalic anhydride (PA) or isophthalic acid; and MA–PA–PG types modified by a second glycol, such as DEG, 2-methyl-1,3-propanediol or NPG, to partially replace PG. Based on the Takayanagi mechanical models, the effects of glycol ratios, saturated dibasic aromatic acid modification, second glycol modification, C=C unsaturation of UP and molecular weight of UP on the mechanical properties will be discussed.     

Kinetics of polyesterification: modelling and simulation of unsaturated polyester synthesis involving 2-methyl-1,3-propanediol

The kinetics of the individual key reactions involved in the formation of unsaturated polyester resins have been studied using the very reactive glycol, 2-methyl-1,3-propanediol (MPD). This diol has been reacted in turn with maleic anhydride (MA), phthalic anhydride (PA) and isophthalic acid (IA) under isothermal conditions in the temperature range 180-210 °C and the kinetic constants for the following reactions have been obtained MA+MPD, PA+MPD, IA+MPD, MA+PA+MPD and MA+IA+MPD. The relative reactivities of MPD with MA and PA measured by monitoring the loss of carboxyl groups at 180 and 200 °C were found to be 2.26 and 1.70, respectively. At 200 °C PA is more reactive than IA (ratio approximately 1.31) in homopolyesterification. In the copolyesterifications involving PA and IA where cross catalysis can occur, the PA reacted approximately 1.25 times faster than IA at 200 °C. The differences in reactivity might be expected to have a significant effect on the coreactant sequence lengths in prepolymers formed by the concurrent reaction of PA, IA and MPD particularly at low conversions thus on the final properties of the cured resins in which they are employed. The properties of the products are not examined in this paper.     

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     

含癸二酰胺的共聚酰胺固化剂的合成及性能

用癸二酸和二聚酸与多胺共缩聚合成了含癸二酰胺的共聚酰胺固化剂,研究了癸二酸加入量对合成固化剂胺值、粘度的影响,及对固化剂与环氧树脂E-44混合体系力学性能的影响。加入癸二酸后,树脂粘度有大幅度的下降,但癸二酸的加入量超过5%以后,合成的共聚酰胺固化剂粘度逐渐增加;产物的胺值与E-44的固化体系的固化度、拉伸强度和剪切强度都随癸二酸加入量的提高而提高。其凝胶时间缩短,比较发现,当癸二酸加入量为二聚酸加入量的20%时,与四乙烯五胺合成的固化剂各方面性能较好,其体系的粘度为二聚酸性聚酰胺的80%左右。在酸组分不变的情况下,混合体系的裂解温度随胺分子质量的增加而下降,失重率则相反。     

Comparative study by DSC and FTIR techniques of an unsaturated polyester resin cured at different temperatures

The polymerization of a commercial polyester resin was investigated by differential scanning calorimetry (DSC). The conversion profiles were obtained in the temperature range 60–80°C. The autocatalytic model satisfactorily describes the experimental data. Fourier transform infrared spectroscopy (FTIR) measurements were also made in order to obtain both the styrene and polyester unsaturations conversions, which were compared to the overall conversion obtained by DSC. Overall conversion measured by DSC lies between styrene and polyester C=C bond conversion obtained by FTIR. © 1998 SCI.     

Chemorheology of thermosetting resins. II. Effect of particulates on the chemorheology and curing kinetics of unsaturated polyester resin

The effect of particulates on both the rheological properties during cure and the curing kinetics of unsaturated resin has been investigated. For the investigation, a general-purpose unsaturated polyester resin was used, with calcium carbonate and clay as inorganic particulates and high-density polyethylene powder as organic particulates. It has been found that, as the particulate content increases, the resin/particulate mixture gives rise to shear-thinning behavior and the rate of cure increases. It has also been found that the CaCO₃ particles helped control shrinkage during cure when the material was subjected to steady shear deformation and that the gel time tη∞ is shorter for mixtures of resin and particulates than for the neat resin alone. Differential scanning calorimetry (DSC) is found useful for determining the curing kinetics of resin/particulate mixtures. We have combined rheological and DSC measurements to obtain a correlation between viscosity and the degree of cure during isothermal curing operations.