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     

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     

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 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     

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     

Hydroxyalkyl derivatives of phenyldiamine as modifiers for unsaturated polyester resins. II. derivatives of phenyl-1,3-diamine

The results are presented on the synthesis of new modifiers and on functioning of these modifiers in unsaturated polyester (UP) resins. The modifiers were obtained by reacting ethylene oxide or propylene oxide with phenyl-1,3-diamine. The effect of the modifiers and cobalt accelerator on the reactivity of resins was studied. When used in the amount of up to 1.50 wt %, the amines substantially (several times) reduced the gelation time of modified UPs. The reactivity of resins, however, improved in expense of their stability. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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

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

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 the addition of depolymerised ethylene vinyl acetate on the mechanical,thermal, chemical and shrinkage properties of cured unsaturated polyester resins

Unsaturated polyester resins (UPRs) are versatile compounds. However, their major drawback is the high shrinkage exhibited on curing. An attempt was made to reduce the shrinkage of UPRs without affecting other properties. In the present study a commonly used iso‐reactive UPR was modified by the addition of ethylene–vinyl acetate (EVA; subjected to controlled depolymerisation to obtain samples of various molecular weights), and was cured at room temperature. The peak exotherm temperature and gel time were both observed to decrease with an increase in EVA content. The composition incorporating 0.5% of depolymerised EVA1 (highest degree of branching) showed maximum improvement in tensile and flexural properties with the heat deflection temperature and impact properties remaining almost unaffected. A uniform dispersion for the UPR containing 0.5% of EVA1 was observed. Addition of EVA reduced the percentage shrinkage in the modified matrix. Incorporation of depolymerised EVA can be an attractive option for the reduction of shrinkage in UPRs. The advantage of using depolymerised EVA is that generated waste EVA can be depolymerised and reused for this application making it cost effective. Copyright © 2010 Society of Chemical Industry     

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     

Kinetics of the curing reaction of unsaturated polyester resins catalyzed with new initiators and a promoter

In this article, the curing of unsaturated polyester resins catalyzed with a promoter [cobalt(II) octoate] and free‐radical initiators is presented. The new initiators were formed by the oxidation process of ethyl methyl ketone or cyclohexanone with hydrogen peroxide and the mixture of solvents containing hydroxyl groups. As a reference, a typical curing system containing ethyl methyl ketone hydroperoxide (Luperox) and the promoter was used. The differential scanning calorimetry runs were performed at different heating rates. The experimental data were fitted with the empirical kinetic model. First, the kinetic parameters (activation energy, frequency factor, and reaction order) were obtained with a single reactive process and with the nth‐order reaction f(α), the nth‐order reaction f(α) with autocatalysis, and the first‐order reaction f(α) with autocatalysis. Second, two or three different reactive processes with the nth‐order reaction f(α) for each step were used. The obtained values of the activation energies for the curing of the unsaturated polyester resins with the free radical initiator–cobalt(II) salt catalytic system were in the range 40–60 kJ/mol for the polymerization initiated by the redox decomposition of the initiators and 80–90 kJ/mol for the polymerization initiated by the thermal decomposition of the initiators at high temperatures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1870–1876, 2006     

废弃PET化学回收及制备不饱和聚酯树脂的研究进展

随着聚对苯二甲酸乙二醇酯（PET）材料用量的大幅增长,大量废弃PET制品堆积造成的环境污染问题日益突出,其回收利用技术也随之广受关注。在不同的PET回收方法中,将PET降解为单体或低聚物的化学回收是效率最高、产物利用价值最大的方法,但也存在反应条件苛刻、产物收率低等问题。本文详细梳理了水解法、甲醇醇解法、二元醇醇解法、胺解法和氨解法等化学回收方法的主要特点以及微波加热、离子液体、纳米技术等新兴技术在PET化学回收过程中的应用概况。通过对各种化学回收工艺的比较,文中得出二元醇醇解法是最具商业应用价值方法的结论。在此基础上,文中重点介绍了PET的二元醇解以及进一步制备不饱和聚酯树脂的化学过程、发展现状、制约因素和改进措施。分析表明,由PET二元醇解产物制备不饱和聚酯树脂是提高废弃PET资源化效率、丰富原料供给、推动产品升级的重要途径,开发高效、廉价、环保的新型催化剂或酶催化技术是废弃PET回收领域今后主要的发展方向。