Peroxide crosslinking of a styrene‐free unsaturated polyester

Thermoset unsaturated polyesters are usually obtained by the crosslinking of unsaturated polyester chains dissolved in an unsaturated, reactive, monomeric diluent, which is usually styrene. This article describes a new approach in which styrene‐free unsaturated polyester chains are intrinsically cured into a crosslinked matrix. The gel time, gel content, swelling degree, glass‐transition temperature, dynamic mechanical properties, tensile properties, and molecular weight between crosslinks (calculated according to both the Flory–Rehner equation and the theory of rubber elasticity) of the crosslinked polymer are studied as a function of the peroxide concentration. All properties change considerably upon the addition of small amounts of peroxide (between 1 and 2 wt %) and change to a lesser extent with higher peroxide concentrations (up to 6 wt %). The thermal properties of the isolated gel fraction are studied as a function of the peroxide concentration. The sol fraction demonstrates a plasticizing effect on the crosslinked network, affecting the glass‐transition temperature and stress–strain behavior of the crosslinked polymer. In light of the crosslink densities derived from swelling experiments, a molecular structure and crosslinking mechanism are suggested for the gel fractions of 1 and 6 wt % peroxide crosslinked unsaturated polyester chains. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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.     

Studies on suspension and emulsion. XLVI. Emulsifier-free emulsion polymerization of styrene in acetone–water

Emulsifier-free emulsion polymerization of styrene in acetone–water medium was carried out using potassium persulfate as initiator. Below acetone content of 40 vol %, stable emulsion was prepared and polymerizations were remarkably fast compared with those in pure water. The particle size decreased from 0.5 to 0.17 μm with an increase in acetone content in the range 0–40 vol %, and the distributions were very sharp. The optimum polymerization for the preparation of the stable emulsion was: styrene, 20 vol %; acetone/water, 40/60 (v/v); KPS, 3.4 × 10^?3 mole/l; temp., 90°C.     

Monodispersed thermoresponsive hydrogel microspheres with a volume phase transition driven by hydrogen bonding

We report the synthesis and characterization of monodispersed thermoresponsive hydrogel microspheres with a volume phase transition driven by hydrogen bonding. The prepared microspheres, composed of poly(acrylamide-co-styrene) (poly(AAM-co-St)) cores and poly(acrylamide)/poly(acrylic acid) (PAAM/PAAC) based interpenetrating polymer network (IPN) shells, were featured with high monodispersity and positively thermoresponsive volume phase transition characteristics with tunable swelling kinetics, i.e. the particle swelling was induced by an increase rather than a decrease in temperature. The monodisperse poly(AAM-co-St) seeds were prepared by emulsifier-free emulsion polymerization, the PAAM or poly(acrylamide-co-butyl methacrylate) (poly(AAM-co-BMA)) shells were fabricated on the seeds by free radical polymerization, and the core-shell microspheres with PAAM/PAAC based IPN shells were finished by a method of sequential IPN synthesis. The microsphere size increased with increasing both AAM and BMA dosages. The increase of hydrophilic monomer AAM dosage resulted in a better monodispersity, but the increase of hydrophobic monomer BMA dosage led to a worse monodispersity. With increasing the crosslinker methylenebisacrylamide (MBA) dosage, the mean diameter of the microspheres decreased and the monodispersity became better. An equimolar composition of AAC and AAM in the IPN shells of the microspheres resulted in a more complete shrinkage for the microspheres at temperatures lower than the upper critical solution temperature. Both BMA and MBA additions depressed the swelling ratio of the hydrodynamic diameter of the microspheres.     

Sorption/diffusion of aqueous mixtures of 1,4‐dioxane/tetrahydrofuran through blend membranes of poly(vinyl alcohol) and sodium alginate: Their compatibility and pervaporation separation studies

Blend membranes of poly(vinyl alcohol) (PVA) and sodium alginate (NaAlg) were prepared by solution casting and crosslinked with glutaraldehyde (GA). Polymer blend compatibility was studied in water by measuring solution viscosity at 30°C. From the viscosity data, interaction parameters were determined to find the blend compatibility. Thickness of the membranes ranged between 35 and 40 μm. Circular disc‐shaped samples were cut from the thin membranes to perform gravimetric sorption experiments in water + 1,4‐dioxane and water + tetrahydrofuran mixtures at 30°C. Diffusion coefficients were calculated using Fick's equation. Concentration profiles of liquids were computed by solving Fick's equation under suitable boundary conditions. Diffusion coefficients show a dependence on the composition of the blends as well as composition of binary mixtures. A correlation was attempted between concentration profiles and diffusion coefficients of the transporting liquids. Degree of swelling and sorption coefficients were calculated from the gravimetric sorption data. Sorption kinetics was studied using an empirical equation to understand the nature of sorption–diffusion anomalies. Membrane selectivity for water + 1,4‐dioxane and water + tetrahydrofuran mixtures were calculated from the pervaporation experiments. A correlation between sorption and membrane selectivity was attempted. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 178–188, 2005     

Copolymerization of unsaturated polyester with styrene in inverted emulsion

Copolymerization of unsaturated polyester with styrene in water-in-oil (W/O) type emulsion was carried out with the use of various basic compounds as emulsifiers. It was found that a stable, gellike W/O type emulsion of unsaturated polyester resin is formed only when pK_a's of the bases are above 6 and their concentrations are higher than some critical value. In these conditions, water can be dispersed in emulsion up to 900% to the resin. By polymerization, the stable W/O type emulsion is transformed to a white solid copolymer which is dry to the touch and which contains 90–95% of initially added water. It was confirmed that the basic compounds react with the carboxylic group of the polyester to form at the water-resin interface polyester salts, which act as true emulsifying agents. The stabilization mechanism of the emulsion at various concentrations of the polyester salt was investigated, mainly by microscopic observations, and an interpretation of the critical value of emulsifier concentration is proposed.     

Syntheses of hydroxypropyl methylcellulose phthalate gels in organic solvents by radiation crosslinking

Cellulose gels were prepared through the crosslinking of hydroxypropyl methylcellulose phthalate (HPMCP) with electron‐beam irradiation in concentrated organic solvent solutions. The effects of the solvent species, polymer concentration, and irradiation dose on the formation of the gels were investigated. Some organic solvents, such as alcohols with short alkyl chains, alkyl acetates, and ketones, were found to be suitable as media for the radiation crosslinking of the polymer. The prepared HPMCP gels showed excellent swelling in various organic solvents with medium hydrogen‐bonding abilities, such as pyridine, cresol (meta), acetic acid, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, 1,4‐dioxane, acetone, methyl ethyl ketone, methyl acetate, and chloroform. In an acetone/water mixture, the swelling ratio was significantly dependent on the solvent composition because of the coexistence of both hydrophilic and hydrophobic moieties in HPMCP. These results suggest that HPMCP gels have the potential to be superabsorbents for various kinds of organic solvents. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3002–3007, 2004     

Molecular weight distribution of an unsaturated polyester

A precipitation fractionation was carried out by the nonsolvent addition method of 60 g of an unsaturated polyester. The polyester was prepared by the generally known melt condensation of maleic anhydride, phtalic anhydride, ethylene glycol, and cyclohexanol. Number-average molecular weights of fractions were determined by vapor pressure osmometry in acetone at 36°C. Polydispersities of fractions were evaluated by gelpermeation chromatography (GPC) measurements with tetrahydrofuran as solvent. They seem to be wider for fractions of higher molecular weights. By infrared spectroscopy the fractions were found not to have marked differences in chemical compositions. The obtained molecular weight distribution curve of the unsaturated polyester was found to be in good agreement with that expected from the theory of polycondensation kinetics. The small differences appear only in the low molecular weight range.     

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.     

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     

Preparation and reticulation of styrene acrylic/epoxy complex latex

The styrene acrylic/epoxy (SA/EP) complex latex with high content of epoxy resin was successfully prepared through emulsion polymerization initiated by both water-soluble and oil-soluble initiators. The resulting complex latex demonstrated regular spherical morphology with a diameter ranging 150–300 nm and with a narrow size distribution. The compatibility between epoxy and styrene acrylic improved due to the styrene acrylic grafting epoxy formation during grafting copolymerization. The factors influencing the structure and storage time of the complex latex were investigated and the corresponding mechanism was revealed. The SA/EP complex latex can form crosslinking structure with epoxy curing agent at room temperature. The crosslinked complex latex film shows good mechanical properties and excellent chemical resistance. These SA/EP complex latexes show great potential in developing high-performance aqueous paints and adhesive.     

Impregnation of white pine wood with unsaturated polyesters to produce wood–plastic combinations

Two unsaturated polyester resins based on poly(1,2 propylene–maleate–phthalate) (PE1), and poly(oxy–diethylene–maleate–phthalate) (PE2) were used for the impregnation of oven-dried white pine wood samples in admixture with styrene (S). Curing was affected by the initiator-heat technique by either using 0.1–0.2% by weight of benzoyl peroxide (Bz₂O₂), or 1% by weight of methyl ethyl ketone peroxide (MEK). It was found that the use of PE1/S mixture resulted in the formation of wood–plastic combinations (wpc) with higher percent retention and higher percent polymer loadings than those obtained by the impregnation of wood samples with PE2/S imxtures. The use of different swelling solvents including ethanol, acetone or chloroform, did not influence the percent retention or polymer loadings of wpc for either PE1/S or PE2/S mixtures. Physical tests performed on wpc showed that compression, hardness, static bending were generally enhanced, water absorption was decreased, and dimensional change was retarded to different extents for both polyesters used, but no permanent stabilization was attained.     

Preparation of poly(acrylamide) grafted onto crosslinked poly (HEMA-MMA-EGDMA) beads for the removal of phenol

ABSTRACT

Poly(acrylamide) (PAAM) was grafted onto crosslinked poly(hydroxy ethyl methacrylate) (HEMA)-based beads for the removal of phenol from aqueous solution. A beaded polymer with a PAAM surface shell was prepared in two steps: synthesis of crosslinked poly (HEMA (50% mol) - MMA (40% mol) - EGDMA (10% mol)) terpolymers spherical beads (200–420 µm) (resin 1) via the suspension polymerization method; and the grafting of PAAM was carried out by redox initiation from hydroxyl groups on resin1 by using cerium (IV) ammonium nitrate as the initiator.

The resulting polymeric sorbent (resin 2) with about 82 wt.% grafted PAAM has been demonstrated to be efficient to remove phenol from water. Moreover, phenol sorption capacities of resin 1 and resin 2 were compared and sorption experiments were performed depending on the initial phenol concentration and pH. Kinetic measurements and models were studied for resin 1 and resin 2.     

Preparation and properties of unsaturated polyester–montmorillonite intercalated hybrid

An unsaturated polyester–organophilic montmorillonite hybrid was prepared by dispersing polymerizable quaternary ammonium‐modified montmorillonite in an unsaturated polyester resin, followed by cross‐linking reaction. The purpose of this investigation was to discover the role of the polymerizable group of quaternary ammonium in improving interfacial interaction between the silicate layers and polymer chains and the mechanical properties of unsaturated polyester–montmorillonite hybrids. It is found that when the content of organophilic montmorillonite is between 2 and 5%, the tensile strength, impact strength, heat resistance, and swelling resistance of the hybrid are obviously enhanced and are better than that of the composites prepared with pristine or nonpolymerizable quaternary ammonium‐modified montmorillonite. Results of X‐ray diffraction and transmission electron microscopy show that unsaturated polyester and styrene in the resin can be intercalated into the interlayer space of organophilic montmorillonites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2038–2044, 2004     

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.     

Preparation and permeability of solutes through acrylic acid-g-methylcellulose copolymer membranes

Graft copolymer membranes from the methylcellulose and the acrylic acid were prepared and their properties and the permeability of four solutes were estimated. Acrylic acid-g-methylcellulose (AA-g-MC) copolymer dissolved in aqueous acetone solvent was cast to prepare membranes followed by the subsequent crosslinking either with aluminium potassium sulfate or by the thermal-curing method. The equilibrium water content in the membrane increased with the volume fraction of acetone in the aqueous acetone solvent system. Membrane, the ionically crosslinked with the aluminum potassium sulfate, showed the water content in the range of 38.5 and 58.4% and 0.25–0.33 kg/mm² of the tensile strength in the wet state. Compared with ionically crosslinked membranes, thermally dried membranes exhibited a more dense structure, resulting in lower water contents and higher mechanical strength. Experimental results on the permeation of four small and midsize solutes through the graft copolymer membranes revealed the molecular weight dependence of the permeability coefficient. The higher the degree of swelling, the greater the permeability coefficient. Ionically crosslinked membranes had higher solute permeability than the commercial Cuprophane membrane had. © 1993 John Wiley & Sons, Inc.     

Effect of curing conditions on the properties of multivesiculated polyester particle dispersions

Multivesiculated polyester particles were synthesized from a double emulsion system comprising water and a solution of unsaturated polyester in styrene. A suspension of solid micro‐particles containing multiple water‐filled vesicles is obtained after curing (i.e., crosslinking) the dispersed organic phase. These have several applications, like opacifying agents in paint formulations. The effects of curing time and temperature on relevant properties of the final product (particle size distribution, dry film opacity, dispersion viscosity, and stability) were investigated. Results showed that more than 1 h was necessary when curing at room temperature, in order to avoid coalescence and loss of opacity upon drying. On the other hand, well‐individualized particles were obtained within a few minutes when curing above 60°C, and the internal alveolar structure was preserved after drying. Furthermore, high curing temperatures enhanced not only the final dry film opacity, but also originated less viscous and more stable particle dispersions. POLYM. ENG. SCI., 54:396–403, 2014. © 2013 Society of Plastics Engineers     

Laboratory studies into how glass-reinforced plastic (GRP) vat surfaces can be repaired without causing migration of styrene into foodstuffs

Glass–fiber-reinforced plastic (GRP) vats are used widely for the storage of foodstuffs and potable water. As the inner surfaces deteriorate during decades of use, they need to be repaired. The unsaturated polyester resins that are used for recoating are crosslinked with styrene which can cause taint and odor problems. This article describes some coating parameters that affect the content of residual styrene and its subsequent migration. The influences of cure temperature and duration, along with the effect of washing with warm detergent solution, were investigated. Cured specimens were tested for their residual styrene content and for styrene migration into the food simulants, distilled water, 3% acetic acid, and 15% ethanol. The dominant factor in reducing the amount of residual styrene is the temperature. The resin self-heats as it cures, typically up to 50°C. Thus, any further lowering of the styrene content requires a higher cure temperature than this. A 3-h cure at 80°C reduced both the residual content and the migration levels by about 100-fold. At lower cure temperatures, the heating effect of washing at 60°C is more important than the washing effect of the detergent. When less catalyst was used the residual styrene levels rose dramatically, from 70 to 360 to 1300 mg/kg for the normal dose, half and quarter the normal dose, respectively. There was a linear relationship between residual content in the GRP and the migration levels. This correlation could be used for monitoring the quality of vats repaired in situ, using styrene-based coating resins.     

Swelling behavior of poly(α-hydroxy acrylic acid) gel in water/organic solvent mixtures

Summary Swelling behavior of poly(α -hydroxy acrylic acid) (PHA) gel was investigated in water/organic solvent mixtures (acetone, dioxane, dimethyl sulfoxide: DMSO) in comparison with poly(acrylic acid) (PAA) gel. The swelling degrees of PHA and PAA gels significantly decreased with increasing acetone or dioxane content in the mixed solvents, while the deswelling in aqueous DMSO was less apparent. The deswelling region was dependent on the dissociation state of the carboxyl group; when the carboxyl group in the gels was dissociated (-COO), significant deswelling occurred in 30–60 vol.% of acetone or dioxane for PHA gel and in 40–80 vol.% for PAA gel. When the carboxyl group was in an acid form (-COOH) or only slightly dissociated, the deswelling region was 0–30 vol.% for PHA and 80-100 vol.% for PAA. The unique swelling behavior of PHA gel was ascribed to intermolecular hydrogen bonding. Effects of dielectric constant on the swelling are also discussed. Received: 6 December 1999/Revised version: 17 January 2000/Accepted: 28 January 2000     

Influence of swelling solutions on the behavior of cholesteric networks

The swelling behavior of an ethyl‐cyanoethyl cellulose/crosslinked poly(acrylic acid) cholesteric network in different swelling solutions was studied. The swelling behavior of the cholesteric network was reversible in acid or neutral solutions and was irreversible in basic solutions. The cholesteric network retained the cholesteric structure during the swelling process in NaCl aqueous solutions, and the swelling behavior was incompletely reversible. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 724–729, 2005