Curing of unsaturated polyester resins—effects of comonomer composition. III. Medium-temperature reactions

The effects of comonomer composition on the curing kinetics of unsaturated polyester (UP) resins at 70–90°C were studied by differential scanning calorimetry (DSC) and infrared (IR) spectroscopy over the whole conversion range. One commercial UP resin, UP2660PF2, with cobalt promoter added and with 8.85 unsaturated C?C bonds per polyester molecule, was used. It was found that a marked shoulder in the initial DSC rate profile, rather than that reported after the peak of rate profile for low-temperature and high-temperature reactions, appeared when the molar ratio of styrene to polyester C?C bonds was greater than 1. With the initiator system accelerated by cobalt promoter, the formation rate of microgel particles would be enhanced at the early stage of reaction, as supported by the much higher conversion of polyester C?C bonds than that of styrene by IR spectroscopy. Those relatively greater number of microgel particles tended to facilitate the intramicrogel crosslinking reactions, which would be independently identified from the initial DSC rate profile as a shoulder. Consequently, the reaction mechanism was elucidated by decomposing the reaction rate profile into two individual profiles accounting for the intramicrogel dominated and the intermicrogel dominated crosslinking reactions, respectively. © 1993 John Wiley & Sons, Inc.     

Curing of unsaturated polyester resins: Effects of comonomer composition. II. High-temperature reactions

The effects of comonomer composition of the curing kinetics of unsaturated polyester (UP) resins at 100–120°C were investigated by differential scanning calorimetry (DSC) and infrared spectroscopy (IR) over the entire conversion range. One commercial UP resin, UP2821, with 6.82 unsaturated C?C bonds per polyester molecule, was used. For styrene/UP2821 reactions, experimental results of the initial and maximum reaction rates by DSC at 100–120°C revealed that the styrene content, as well as the reaction temperature, would affect the formation of microgel structures. As the initial molar ratio of styrene to polyester C?C bonds increased, the styrene swelling effect could enhance the intramicrogel crosslinking reactions, while the styrene dilution effect could diminish the intermicrogel crosslinking reactions. The competition between the two reactions would depend on the reaction temperatures. Finally, a microgel-based reaction mechanism was proposed for the high temperature reactions. © 1993 John Wiley & Sons, Inc.     

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 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.     

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.     

Microgelation in the curing reaction of unsaturated polyester resins

A series of unsaturated polyesters were synthesized with various chemical structures and molecular weights. These unsaturated polyesters were used to study the curing reaction with styrene by using gel permeation chromatography and differential scanning calorimetry. The variation of the size of microgel particles during the curing reaction in unsaturated polyester–styrene resins was studied by using gel permeation chromatography. The size and structure of the microgels depend strongly on the polymer chain length and the number of vinyl groups on each unsaturated polyester chain. Using the differential scanning calorimetric method, the conversion of styrene and polyester vinyl groups during the reaction was measured. The experimental results of this study revealed that microgel formation has a great effect on the curing reaction of unsaturated polyester resins. © 1994 John Wiley & Sons, Inc.     

Effects of resin chemistry on redox polymerization of unsaturated polyester resins

Unsaturated polyester resins are the most widely used thermoset resins in the composite industry. In this study, three well‐defined unsaturated polyester resins were used. These resins have similar number‐average molecular weights, and they have different numbers of C?C bonds per molecule. The reaction kinetics of unsaturated polyester resins was studied using a differential scanning calorimeter (DSC) and a Fourier transform infrared (FTIR) spectrometer. The glass transition temperature of the isothermally cured resin was also measured. Trapped radicals were observed in the cured polyester resin from electron spin resonance (ESR) spectroscopy. Considering the diffusion‐limitation effect, a simple kinetic model was developed to simulate the reaction rate and conversion profiles of polyester vinylene and styrene vinyl groups, as well as the total reaction rate and conversion. Experimental results from DSC and FTIR measurements compare favorably with the model prediction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 211–227, 2002; DOI 10.1002/app.10317     

Solvent‐induced modifications in polyester yarns. II. Structural and thermal behavior

The structural and thermal behaviors of polyester yarns treated with trichloroacetic acid–chloroform (TCAC) mixture were investigated by differential scanning calorimetric analysis (DSC), wide‐angle X‐ray scattering (WAXS), infrared spectroscopy (IR), and scanning electron microscopy (SEM). The effects of TCAC treatment on original fine filament (FFP) and microdenier (MDP) polyester yarns and on heat‐set polyester yarns were studied. It was found that the glass transition temperature of TCAC‐treated polyester yarns decreases with an increase in treatment concentration due to the plasticization effect, which is remarkable even at lower treatment concentration. The TCAC treatment on polyester yarns resulted in the formation of new crystallites in the extended noncrystalline domains of PET as well as growth and perfection of these new crystallites and the preexisting crystals. Further, the DSC thermograms revealed that TCAC treatment with 3% concentration could be able to overcome the structural changes in PET produced by heat setting at 180°C. The substantial changes in noncrystalline and crystalline domains observed were related to the mechanical properties of yarns. From the WAXS studies, an increase in crystal size and lateral order of TCAC‐treated polyester yarns was noted. The most distinct changes brought about by TCAC treatment include overall orientation determined by the trans–gauche ratio from IR measurements. The removal of oligomers and smoothening out of the fiber surface by TCAC treatment were observed from SEM studies. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1555–1566, 2003     

聚癸二酸甘油单月桂酸酯的合成及对聚氯乙烯增塑性能的研究

以甘油单月桂酸酯和癸二酸为原料,以钛酸正丁酯为催化剂,在180℃下合成了高分子量聚酯产品：聚癸二酸甘油单月桂酸酯。采用红外光谱、核磁共振仪和凝胶渗透色谱仪对豆油聚酯的结构和分子量进行了表征;并将该聚酯作为增塑剂与聚氯乙烯热塑共混成型后,采用热重分析仪、差示扫描量热仪和万能拉力试验机对共混物的热性能和力学性能进行了表征。结果显示：通过甘油单月桂酸和癸二酸的直接缩聚反应得到了高分子量聚癸二酸甘油单月桂酸酯,该聚酯产品能够提高聚氯乙烯的热稳定性,降低聚氯乙烯的玻璃化转变温度,可以与邻苯类增塑剂复配,得到热性能与力学性能兼顾的聚氯乙烯产品。     

热塑性聚酯弹性体的研究

通过缩聚反应,合成了具有一定软、硬段比例的热塑性聚酯弹性体。应用凝胶渗透色谱、红外光谱以及差示扫描量热法对该热塑性聚酯弹怀体结构进行了研究,并测定出其主要的力学性能基本达到进口同类产品Ｄ６３５６的水平。     

Curing reaction of saturated aliphatic polyester modified unsaturated polyester resins

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

Some filler effects on cross-linking of unsaturated polyesters

The effect of five fillers on the cross-linking macro-and microcharacteristics of simple unsaturated polyester resins was investigated by differential scanning calorimetry (DSC), reactivity tests, and gel time tests. Glass beads and silica flour appeared to have little influence on the cross-linking reaction of the resin itself, their effect being comparable to mere dilution of the resin. Kaolin presented some interaction with the resin due to its absorption characteristics and acid groups. Reground polyester/glass fiber powder and especially wood flour appeared to present clear chemical interactions with the curing behavior of the resin. Wood flour, in particular, was shown by DSC analysis to strongly co-react with the resin during cross-linking and altered markedly the resin enthalpy change and energy of activation during curing. The wood flour component causing the altered behavior of the resin appears to be lignin. DSC analysis of resins filled with three different types of isolated lignins indicated that this wood flour component reacts in a heterogeneous phase reaction with the resin during cross-linking. It appears that it is the lignin unsaturated carbon–carbon double bonds at the polyester/wood flour and at the polyester/lignin interphases that are likely to co-react by heterogeneous phase radical cross-linking with the polyester resin and styrene unsaturation, markedly changing the resin curing behavior. © 1993 John Wiley & Sons, Inc.     

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     

Polyurethane powder coatings containing polysiloxane

In this study, blocked polyisocyanate crosslinkers (PIC) for powder coatings were synthesized using isophorone diisocyanates (IPDI), formic acid, poly(dimethylsiloxane), ?-caprolactam, dibutyltin dilaurate as well as triethylamine as catalysts. The chemical structures of these compounds were confirmed by means of IR and NMR spectroscopy and the molecular weight distributions were investigated using gel permeation chromatography (GPC). Polyurethane powder coating systems consisting of polyester resin and synthesized polyisocyanate were examined. The surface structure of powder coatings was investigated with confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM) equipped with energy dispersive spectrometer (EDS) and X-ray photoelectron spectroscopy (XPS). The surface structure was correlated with the chemical structure of the coatings and macroscopic surface behavior: contact angle, surface free energy, gloss, abrasion and scratch resistance, hardness as well as adhesion to steel surface.     

蓖麻油酸基聚酯多元醇的合成研究

以可再生资源蓖麻油制备的蓖麻油甲酯、己二酸、乙二醇为原料,钛酸四正丁酯为催化剂,经酯化、缩聚合成蓖麻油酸基聚酯多元醇,考察了反应时间、催化剂、蓖麻油甲酯对聚酯多元醇热稳定性能的影响,采用凝胶色谱(GPC)、红外光谱仪(IR)、示差扫描量热仪(DSC)对蓖麻油酸基聚酯多元醇的相对分子质量、结构、热稳定性进行了系统的表征。实验表明,在醇酸(己二酸∶乙二醇)比为1.15、催化剂质量分数0.04%～0.05%、温度180℃,真空缩聚2h的条件下,制得相对分子质量为2600～3800、分布指数(PDI)为1.89～2.44的不同蓖麻油酸含量的聚酯多元醇,蓖麻油酸基聚酯多元醇的熔点随着蓖麻油酸含量的增加而降低。     

Characterization and charge transfer mechanism of PIN–cdse nanocomposites

This paper reports structural, thermal, and temperature‐dependent dielectric properties of polyindole–cadmium selenide (PIN–CdSe) nanocomposites. PIN and its nanocomposites were synthesized via in situ chemical oxidative polymerization method. Samples were characterized by Fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), scanning electron microscopy with energy dispersive X‐ray (SEM/EDX), atomic force microscope, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Dielectric properties were analyzed as a function of temperature. FT‐IR spectroscopy indicated that both N H and aromatic CC bonds were affected more by doping process. Significant structural differences were observed in XRD and SEM analyses of PIN and its nanocomposites. Both XRD and DSC measurements revealed that crystallinity of the PIN increases to a certain degree with increasing doping level. Thermogravimetric analysis showed that addition of CdSe decreased degradation temperature of the PIN. Conductivity measurements investigated by universal power law indicated that the charge transport mechanism of all the samples is consistent with correlated barrier hopping model. POLYM. COMPOS., 37:3057–3065, 2016. © 2015 Society of Plastics Engineers     

Study on the modification of epoxy resin by a phosphorus‐ and silica‐containing hybrid

A novel phosphorus‐ and silica‐containing hybrid (DPS) was synthesized by the reaction between diethyl phosphate (DEP) and polyhedral oligomeric siloxanes (POS) formed by hydrolysis condensation of 3‐glycidoxypropyltrimethoxysilane (GPTMS). The novel phosphorus‐ and silica‐containing hybrid was characterized by the flourier transform infrared spectroscope (FT‐IR), silicon nuclear magnetic resonance, and gel permeation chromatography (GPC). Then, the determination of the activation of the reaction between epoxy resin and phosphorus‐, and silica‐containing hybrids was studied by differential scanning calorimeter (DSC). In the presence of catalyst, the activation energies of the curing reaction were 63.3 and 66.7 kJ/mol calculated by Kissinger model and Ozawa model respectively. The thermal and flame retardant properties of the cured epoxy modified by DPS were determined by differential scanning calorimeter (DSC), thermal gravimetric analysis (TGA), and limited oxygen index (LOI). The results revealed that those properties were improved in comparison with unmodified epoxy resin. In addition, scanning electron microscopy (SEM) was used to investigate the morphology of the cured epoxy resin modified by DPS. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Solvent-deficient synthesis of cerium oxide: Characterization and kinetics

The reaction mechanism and kinetics of CeO₂ synthesis using a solvent-deficient method are investigated by simultaneous thermogravimetric analysis (TGA)/differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The decomposition process of the cerium(III) nitrate hexahydrate and ammonium bicarbonate precursor mixture with four observed stages is monitored using TGA/DSC measurements in a nonisothermal regime with heating rates of 5, 10, 15 and 20?°C min^?1. The proposed mechanism indicates a complex synthesis with several parallel reactions, some of which occur at room temperature. A detailed kinetic analysis is performed using isoconversional (expanded Friedman, modified Coats-Redfern and Kissinger) and model fitting (N^th order and nucleation and growth models) methods. The first three stages are best described by the N^th order model with activation energy values of 21, 53 and 90?kJ?mol^?1. The last stage, during which ammonium nitrate decomposition occurs, is best fit by the nucleation and growth model and has an activation energy of 129?kJ?mol^?1. The proposed mechanism, supported by the kinetic analysis in our study, indicates that CeO₂ has already formed before the reaction reaches 200?°C. The average crystallite size of CeO₂ synthesized at 300?°C, which was calculated from the XRD measurements and observed in the SEM and TEM data, is between 10 and 20?nm.     

Morphology and properties of PET/PA-6/E-44 blends

Polymer blends incorporating poly (ethylene terephthalate) (PET), polyamide-6 (PA-6), and a reactive compatibilizer (low molecular weight bisphenol-A epoxy resin—E-44) were prepared with the following E-44 weight percent concentrations: 0, 0.3, 0.6, 1, 3, 5, and 10. The samples was studied by a scanning electron microscope (SEM), a polarizing microscope (PLM), dynamic mechanical thermal analysis (DMTA), wide-angle X-ray diffraction (WAXD), a differential scanning calorimeter (DSC), infrared spectroscopy (IR), and mechanical testing. SEM and PLM showed noticeable changes in both the amorphous region and the crystalline region of the blends. The changes indicated better compatibility between the dispersed phase (PA-6) and the matrix (PET), which was further confirmed by the DMTA test. The WAXD showed that PET and PA-6 crystallized separately and no cocrystallite was found. The melting and crystallization data, obtained by DSC, suggested that the crystallization of the blend was blocked, although the hindered mechanism for the effect of E-44 on PET was different from that on PA-6. The notched impact strength and flexural strength of the PET/PA-6 blends were significantly improved when the content of E-44 was 5 wt % (improved about 500 and 400%, respectively). IR was used to study the reaction among E-44, PET, and PA-6. The result indicated that the grafting reaction and the crosslinking reaction occurred during melt blending. The obvious increase of mechanical properties and the reinforcing and toughening effect were attributed to the formation of the crosslinking net in the blend. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1505–1515, 1998     

The effect of the chemical structure of low-profile additives on the curing behavior and chemorheology of unsaturated polyester resin

An experimental study was conducted to investigate the effect of the chemical structure of low-profile additives on the curing behavior and chemorheology of unsaturated polyester resin during isothermal cure. For the study a general-purpose unsaturated polyester resin was cured in the presence of t-butyl perbenzoate as Initiator. The curing behavior of the resin was investigated using differential scanning calorimetry (DSC). Three different thermoplastic low-profile additives were used, namely poly(vinyl acetate) (PVAc), poly(styrene-co-butadiene), which is also known as KRATON DX-1300, and dehydrochlorinated Isobutylene/isoprene copolymer, often referred to as conjugated diene butyl (CDB) rubber. Each of the these additives, about 30 weight percent, was first dissolved in styrene. The solution was then mixed with unsaturated polyester resin and CaCO₃. The CaCO₃ particles helped stabilize the emulsions consisting of resin and KRATCN, and of resin and CDB. For each resin formulation, a series of isothermal DSC runs were made at various levels of cure pressure. It was found that for all three low-profile resins investigated, the final degree of cure went through a maximum as cure pressure was increased from atmospheric to 6.21 MPa (900 psi). We have observed evidence that in the presence of an initiator generating free radicals, the unsaturated double bonds in the KRATON and CDB undergo grafting reactions with the styrene monomers and unsaturated polyester resin, increasing the glass transition temperature of KRATON and CDB, to an extent which varies with the cure conditions employed. Both steady and oscillatory shearing flow properties were determined using a cone-and-plate rheometer. The rheological measurements indicate that the resin/CaCO₃/KRATON and resin/CaCO₃/CDB systems give rise to gel times shorter than the resin/CaCO₃/PVAc system. It is concluded that both KRATON and CDB are more effective, both for enhancing the rate of cure of unsaturated polyester resin and imparting impact properties to the cured composites, than those thermoplastic low-profile additives that contain neither unsaturated double bonds nor a chemical structure that has rubber-like properties in the solid state.