Synthesis of metal-containing cured resins from divalent metal salts of mono(hydroxyethyl) phthalate,anhydrides, and bisepoxides

Synthesis of novel metal-containing cured resins based on divalent metal salts of mono(hydroxyethyl) phthalate were investigated by the metal salt–anhydride–bisepoxide reactions. As the anhydrides, maleic anhydride (MA) and hexahydrophthalic anhydride (HPA) were used, and hexahydrophthalic acid diglycidyl ester (HPDG), bisphenol A diglycidyl ether (BADG), and ethylene glycol bis(glycidyl phthalate) (EBGP) were the bisepoxides used. The reactions were further studied in model reactions using the Ca salt of monoethyl phthalate. The metal carboxylate groups of the metal salts catalyzed the reactions. The reactivity of the bisepoxides decreased in the order HPDG ? BADG > EBGP, and MA was more reactive than HPA. Some of the metal-containing cured resins obtained showed excellent physical properties. Resistance to chemical attack and boiling water, thermal behavior, and electrical resistance are also discussed.     

Enzyme‐catalyzed copolymerization of oxiranes with dicarboxylic acid anhydrides

Ring‐opening copolymerizations of the oxiranes glycidyl phenyl ether (GPE) and diglycidyl ether of bisphenol A (DGEBA) with a dicarboxylic acid anhydride [methyl hexahydrophthalic anhydride, nadic anhydride, maleic anhydride (MA), or itaconic anhydride (IA)] were carried out with the lipases Candida cylindracea (CCL), Lipozyme TL‐IM (LIM), and Novozyme 435 (N435) as catalysts. The CCL‐catalyzed reaction of DGEBA with MA or IA (at a 1:2 molar ratio) at 80°C resulted in only partial curing. We monitored the reactions by Fourier transform infrared spectroscopy and by following the changes in the intensities of carbonyl stretching frequencies of the anhydride and ester groups. The reactivity of the oxirane group in GPE was higher than that in DGEBA; this may have been due to the higher viscosity of DGEBA. The reactivities of the enzymes for the copolymerization of the oxiranes and dicarboxylic acid anhydride were in the order LIM > CCL > N435. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 697–704, 2005     

Alkyd resins synthesized from postconsumer PET bottles

Simultaneous glycolysis and neutral hydrolysis of waste PET flakes obtained from grinding postconsumer bottles was carried out in the presence of xylene and an emulsifier at 180 °C. The product was separated from EG, water and xylene by filtration and was extracted by water at boiling point three times. The remaining solid was named water insoluble fraction (WIF). The filtrate was cooled to 4 °C and the crystallized solid obtained by filtration was named water-soluble crystallizable fraction (WSCF). These fractions were characterized by acid value (AV), hydroxyl value (HV) determinations. WSCF and WIF were used for preparation of the alkyd resins. Three long oil alkyd resins were prepared from phthalic anhydride (PA) (reference alkyd resin) or depolymerization product of the waste PET (PET-based alkyd resin), glycerin (G), sunflower oil fatty acids (SOFA) and glycol (EG) (reference alkyd resin) or depolymerization product of the waste PET (PET-based alkyd resin). Film properties and thermal degradation stabilities of these alkyd resins were investigated. Physical properties (drying times, hardness and abrasion resistance) and thermal degradation stabilities of the PET-based alkyd resins are better than these properties of the reference alkyd resin.     

The kinetics and mechanism of cure of an amino-glycidyl epoxy resin by a co-anhydride as studied by FT-Raman spectroscopy

The thermal curing behavior of tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM) and a co-anhydride mixture consisting of maleic anhydride (MA) and hexahydrophthalic anhydride (HHPA) was studied from 55 to 100 °C by real-time FT-Raman spectroscopy. The quantitative changes in concentrations of anhydride, epoxy, and new-formed ester were measured and empirical reaction rate curves were constructed reflecting the kinetics of the curing process. After an induction period a simple kinetic scheme that is first order in both epoxy and anhydride monomer consumption described the reaction profile until the reaction was influenced by chemo-rheological changes due to vitrification transition.FT-Raman analysis revealed that curing propagation mainly occurs by polyesterification between epoxide and anhydride. Possible side reactions including the homopolymerization of MA are considered. The main side reaction is decarboxylation of MA that may produces some autocatalysis, but this is a minor contribution to the kinetics of cure. No conclusive evidence has been found for homopolymerization of MA or initiation of the curing reaction by the reaction product of TGDDM and MA, compared to the polyesterification.     

N-(2-biphenylenyl)-4-[2′-phenylethynyl]phthalimide—new monomer synthesis, cure and thermal properties of resulting high temperature polymer

A synthetic route is described to a new monomer, N-(2-biphenylenyl)-4-[2′-phenylethynyl]phthalimide (BPP), which contains both phenylethynyl and biphenylene reactive functional groups. The monomer can be made either from N-(2-biphenylene)acetamide or 2-aminobiphenylene, by reaction with the phenylethynyl-containing anhydride. The monomer was characterised fully and the thermal cure of the material was studied by infrared (IR) spectroscopy and differential scanning calorimetry (DSC). The IR spectra showed that the phenylethynyl group reacted completely within 1 h at 370 °C. DSC showed the polymerisation exotherm of BPP centred at 379 °C, lower than two NASA-developed phenylethynyl-terminated imide (PETI) resins. In comparison with the PETI systems, the T_g of cured BPP was ca. 100 °C higher, making it a candidate for possible high temperature applications.     

Reactively compatibilised polyamide6/ethylene-co-vinyl acetate blends: mechanical properties and morphology

Mechanical properties and morphological studies of compatibilised blends of PA6/EVA-g-MA and PA6/EVA/EVA-g-MA were studied as functions of maleic anhydride content (MA) and dispersed phase (EVA-g-MA) concentrations, respectively at blending composition of 20 wt% dispersed phase (EVA-g-MA or combination of EVA and EVA-g-MA). The maleic anhydride (MA) was varied from 1 to 6 wt% in the PA6/EVA-g-MA blend, whereas MA concentration was fixed at 2 wt% in the ternary compositions with varying level of EVA-g-MA. ATR-IR spectroscopy revealed the formation of in situ copolymer during reactive compatibilisation of PA6 and EVA-g-MA. It was found that notched Izod impact strength of PA6/EVA-g-MA blends increased significantly with MA content in EVA-g-MA. The brittle to tough transition temperature of reactively compatibilised blends was found to be at 23 °C. The impact fractured surface topology reveals extensive deformation in presence of EVA-g-MA whereas; uncompatibilised PA6/EVA blend shows dislodging of EVA domains from the matrix. Tensile strength of the PA6/EVA-g-MA blends increased significantly as compared to PA6/EVA blends. Analysis of the tensile data using predictive theories showed an enhanced interaction of the dispersed phase and the matrix. It is observed from the phase morphological analysis that the average domain size of the PA6/EVA-g-MA blends is found to decrease gradually with increase in MA content of EVA-g-MA. A similar decrease is also found to observe in PA6/EVA/EVA-g-MA blends with increase in EVA-g-MA content, which suggest the coalescence process is slower in presence of EVA-g-MA. An attempt has been made to correlate between impact strength and morphological parameters with regard to the compatibilised system over the uncompatibilised system.     

Dynamic oscillatory shear properties of potentially melt processable high acrylonitrile terpolymers

Polyacrylonitrile (PAN) terpolymers consisting of acrylonitrile/methyl acrylate (AN/MA) systems with added amounts of a termonomer (acid based) were synthesized in an effort to generate melt spinnable carbon fiber precursors. The complex viscosity was measured as a function of time in the temperature range of 200-220 °C, and was found to be dependent on both, the amount, as well as the nature of the termonomer. For the different acid termonomers studied, the cyclization/crosslinking reactions occurring during stabilization as evidenced by the increase in viscosity over time of the PAN system ranged in the order, itaconic acid>acrylamide>methyl acrylic acid>acrylic acid (IA>AM>MAA>AA). Dynamic shear experiments indicated that an AN/MA system containing 3 mol% IA seemed well suited for melt spinning and stabilization. A chemorheological correlation was used to describe the viscosity variation in the PAN system as a function of IA content, temperature and time.     

Synthesis and thermal properties of polyamide 6 (A)-polyimide (B) block copolymers of ABA type

Summary Polyimides (PI) having different molecular weights were prepared by condensation of oxydiphthalic anhydride with 9,9-bis-(4-aminophenyl)fluorene in nitrobenzene solution at 180°C. These polyimides carried two amino chain ends which allowed us to fix polycaprolactam chains (PA6) to obtain PA6-PI-PA6 type copolymers. The elemental analysis and infrared spectroscopic determination gave the proportion of PA6 (or PI) in the copolymers. The studies of thermal properties-DSC and TGA-allowed us to characterize the copolymers.     

Toughening of polyamide 6 with a maleic anhydride functionalized acrylonitrile–butadiene–styrene copolymer

Maleic anhydride functionalized acrylonitrile–butadiene–styrene (ABS‐g‐MA) copolymers were prepared via an emulsion polymerization process. The ABS‐g‐MA copolymers were used to toughen polyamide 6 (PA‐6). Fourier transform infrared results show that the maleic anhydride (MA) grafted onto the polybutadiene phase of acrylonitrile–butadiene–styrene (ABS). Rheological testing identified chemical reactions between PA‐6 and ABS‐g‐MA. Transmission electron microscopy and scanning electron microscopy displayed the compatibilization reactions between MA of ABS‐g‐MA and the amine and/or amide groups of PA‐6 chain ends, which improved the disperse morphology of the ABS‐g‐MA copolymers in the PA‐6 matrix. The blends compatibilized with ABS‐g‐MA exhibited notched impact strengths of more than 900 J/m. A 1 wt % concentration of MA in ABS‐g‐MA appeared sufficient to improve the impact properties and decreased the brittle–ductile transition temperature from 50 to 10°C. Scanning electron microscopy results show that the shear yielding of the PA‐6 matrix was the major toughening mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Reactive compatibilizer precursors for LDPE/PA6 blends. II: maleic anhydride grafted polyethylenes

Several home made and commercially available polyethylene (PE) samples grafted with maleic anhydride (MA) (PE-g-MA) were used as compatibilizer precursors (CPs) for the reactive blending of low density PE (LDPE) with polyamide-6 (PA). Scope of the work was to compare the effectiveness of these CPs with that of a number of ethylene-acrylic acid copolymers (EAA), which had been employed in a previous study for the reactive compatibilization of the same blends, and to get a deeper insight into the coupling reactions producing the PA-g-CP copolymers that are thought to act as the true compatibilizers in these systems. To this end, binary CP/LDPE and CP/PA and ternary LDPE/PA/CP blends were prepared with a Brabender mixer and were characterized by DSC, SEM and solvent fractionation. The results show that the PE-g-MA copolymers react more rapidly with PA than the EAA copolymers and that their CP effectiveness depends critically on the microstructure and the molar mass of their PE backbones. In particular, the CPs produced by functionalization of LDPE were shown to be miscible with this blend component and to be scarcely available at the interface where reaction with PA is expected to occur. Conversely, the CPs prepared from the HDPE grades were immiscible with LDPE and showed better CP performance. Whereas the effectiveness of the EAA copolymers studied earlier had been shown to increase with an increase in the concentration of the carboxyl groups, the concentration of the succinic anhydride groups of the PE-g-MA CPs studied in this work was found to play a minor role, at least in the investigated range (0.3-3.0 wt% MA).     

Co-continuous and encapsulated three phase morphologies in uncompatibilized and reactively compatibilized polyamide 6/polypropylene/polystyrene ternary blends using two reactive precursors

Phase morphology development in ternary uncompatibilized and reactively compatibilized blends based on polyamide 6 (PA6), polypropylene (PP) and polystyrene (PS) has been investigated. Reactive compatibilization of the blends has been performed using two reactive precursors; maleic anhydride grafted polypropylene (PP-g-MA) and styrene maleic anhydride copolymer (SMA) for PA6/PP and PA6/PS pairs, respectively. For comparison purposes, uncompatibilized and reactively compatibilized PA6/PP and PA6/PS binary blends, were first investigated. All the blends were melt-blended using a co-rotating twin-screw extruder. The phase morphology investigated using scanning electron microscope (SEM) and selective solvent extraction tests revealed that PA6/PP/PS blends having a weight percent composition of 70/15/15 is constituted from polyamide 6 matrix in which are dispersed composite droplets of PP core encapsulated by PS phase. Whereas, a co-continuous three-phase morphology was formed in the blends having a composition of 40/30/30. This morphology has been significantly affected by the reactive compatibilization. In the compatibilized PA6/(PP/PP–MA)/(PS/SMA) blends, PA6 phase was no more continuous but gets finely dispersed in the PS continuous phase. The DSC measurements confirmed the dispersed character of the PA6 phase. Indeed, in the compatibilized PA6/(PP/PP–MA)/(PS/SMA) blends where the PA6 particle size was smaller than 1 μm, the bulk crystallization temperature of PA6 (188 °C) was completely suppressed and a new crystallization peak emerges at a lower temperature of 93 °C as a result of homogeneous nucleation of PA6.     

Effect of reactive group types on the properties of core-shell modifiers toughened PA6

Summary  Reactive monomers such as acrylic acid (AA), maleic anhydride (MA) and glycidyl methacrylate (GMA) were grafted onto acrylonitrile-butadiene-styrene core-shell copolymer (ABS) by emulsion polymerization method. These functionalized ABS were used to toughen PA6. FTIR and Molau tests showed that these monomers were introduced onto ABS copolymers and compatibilization reactions took place between PA6 and the AA, MA and GMA grafted ABS. TEM result showed that the modified ABS copolymer dispersed in PA6 matrix uniformly and no obvious difference could be found between the different PA6 blends. However, mechanical test showed that GMA and MA modified ABS achieved much better toughening effect than the AA grafted ABS copolymer due to the stronger interfacial reactions. Fracture characterization indicated that PA6 toughened with GMA and MA modified ABS showed higher G_ivalues according to the Vu-Khanh approach and much obvious shear yielding in the deformed zone could be found.     

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.     

Fluorescent‐tagged maleic anhydride‐allylpolyethoxy carboxylate copolymer as an environmentally benign inhibitor for calcium phosphate in industrial cooling systems

Allyloxy polyethoxy ether (APEG) and succinic anhydride were used to prepare allyloxy polyethoxy carboxylate (APEL). 8‐hydroxy‐1,3,6‐pyrene trisulfonic acid trisodium salt (PY) was reacted with allyl chloride to produce fluorescent monomer 8‐allyloxy‐1,3,6‐pyrene trisulfonic acid trisodium salt (PA). APEL and PA were copolymerized with maleic anhydride (MA) to synthesize PA tagged no phosphate and nitrogen‐free calcium phosphate inhibitor POLY(MA–APEL–PA). Structures of PA, APEG, APEL, and POLY(MA–APEL–PA) were carried out by FTIR and ¹H‐NMR. Different MA : APEL mole ratios were employed for the manufacture of POLY(MA–APEL–PA) to study the effect of mole ratio on performance of POLY(MA–APEL–PA). Relationship between POLY(MA–APEL–PA)'s fluorescent intensity and its dosage was studied. The results indicate that capability of POLY(MA–APEL–PA) is heavily depended on the mole ratio of MA : APEL. Correlation coefficient r of POLY(MA–APEL–PA)'s fluorescent intensity and its dosage is 0.9999, and detection limit of POLY(MA–APEL–PA) is 0.86 mg/L. POLY(MA–APEL–PA) can be used to accurately measure polymer consumption on line besides providing excellent calcium phosphate inhibition. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Amidification of poly(styrene-co-maleic anhydride) with amines in tetrahydrofuran solution: A kinetic study

Summary The kinetics of the reaction between a styrene-maleic anhydride copolymer (SMA) and amines was investigated in tetrahydrofuran solution between 0°C and 40°C. This reaction converts the maleic anhydride (MA) into the corresponding amide-acid, while the consecutive reaction of the generated acid with amine forming a diamide or transformation of the acid-amide into the imide was not observed. The amine reactivity follows the order: 1-octylamine> >1-methyl hexylamine> >1,1-dimethyl propylamine or dibutylamine, demonstrating that the amine reactivity depends, to a large extent, upon its steric hindrance. This reaction is reversible as shown by IR at high temperatures, but the reverse reaction was undetectable between 0 and 40°C. The overall reaction involves spontaneous and autocatalytic reactions, and the overall reaction rate can be written as:-d[MA]/dt=k₀[MA][-NH₂]+k₁[MA][-NH₀]². In the case of 1-octylamine below 0.02 M, the spontaneous reaction dominates (i.e, k₀> >k₁[-NH₂]).     

Styrene‐assisted grafting of maleic anhydride onto polypropylene by reactive processing

The grafting of maleic anhydride (MA) onto polypropylene (PP) was performed in the presence of the electron‐donating monomer styrene (ST) according to a central composite experimental design, in which the initial MA and ST concentrations were varied. The grafting of MA onto PP in the absence of ST was also performed. All reactions were carried out in the molten state in a Haake rheometer. The amount of reacted MA and the extent of degradation in PP were determined by means of Fourier transform infrared spectroscopy and melt flow index (MFI) measurements, respectively. The results showed that the presence of ST in the reactive processing caused a reduction in MFI and an increase in the level of reacted MA when the initial MA concentration equaled the initial ST concentration. An increase in the initial MA concentration presented distinct behavior that depended on the ST content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of well-defined block copolymers and star-branched polymers by using terminal 1,3-butadiene functionalized polymers as reactive building blocks

Terminal 1,3-buadiene (Bd) functional polymers are stoichiometrically reacted with living anionic polymers in a monoaddition manner in THF at ?78 °C, but neither polymerization nor oligomerization occurs under the conditions. By utilizing this reactive but non-polymerizable character of the Bd function toward living anionic polymers, a variety of block copolymers and regular and asymmetric star-branched polymers were successfully synthesized. In these syntheses, the terminal Bd functionalized polymers work effectively as reactive building blocks, namely polymeric efficient linking agents, to construct such architectural polymers. Since all the polymer segments used for the syntheses were derived from living anionic polymers and the linking reactions quantitatively proceeded, the architectural polymers herein synthesized were well-defined in structure and were precisely controlled in chain length. A new protocol based on iterative approach by repeating a two reaction sequence involving linking reaction and re-introduction of Bd group was proposed and developed to successively synthesize asymmetric star-branched polymers up to a 6-arm ABCDEF type. The terminal Bd functionalized polymers were readily and quantitatively converted to anhydride or diepoxide functionalized polymers by Diels–Alder or oxidation reactions. Because of their high reactive termini, the resulting polymers are also usable as reactive building blocks to synthesize the core-functionalized star-branched polymers with carboxylic acids or hydroxyl groups. The reactions between terminal anhydride and amine functionalized polymers were carried out in bulk at 180 °C to examine the synthetic possibility of star-branched polymers under such conditions.     

Synthesis and properties of reactively compatibilized polyester and polyamide blends

The functionalization of poly(butylene terephthalate) (PBT) has been accomplished in a twin screw extruder by grafting maleic anhydride (MA) using a free radical polymerization technique. The resulting PBT‐g‐MA was successfully used as a compatibilizer for the binary blends of polyester (PBT) and polyamide (PA66). Enhanced mechanical properties were achieved for the blend containing a small amount (as low as 2.5 %) of PBT‐g‐MA compared to the binary blend of unmodified PBT with PA66. Loss and storage moduli for blends containing compatibilizer were higher than those of uncompatibilized blends or their respective polymers. The grafting and compatibilization reactions were confirmed using FTIR and ¹³C NMR spectroscopy. The properties of these blends were studied in detail by varying the amount of compatibilizer, and the improved mechanical behaviour was correlated with the morphology with the help of scanning electron microscopy. Morphology studies also revealed the interfacial interaction in the blend containing grafted PBT. The improvement in the properties of these blends can be attributed to the effective interaction of grafted maleic anhydride groups with the amino group in PA66. The results indicate that PBT‐g‐MA acts as an effective compatibilizer for the immiscible blends of PBT and PA66. © 2000 Society of Chemical Industry     

Preparation of the HIPS/MA graft copolymer and its compatibilization in HIPS/PA1010 blends

The graft copolymer of high‐impact polystyrene (HIPS) grafted with maleic anhydride (MA) (HIPS‐g‐MA) was prepared with melt mixing in the presence of a free‐radical initiator. The grafting reaction was confirmed by infrared analyses, and the amount of MA grafted on HIPS was evaluated by a titration method. 1–5% of MA can be grafted on HIPS. HIPS‐g‐MA is miscible with HIPS. Its anhydride group can react with polyamide 1010 (PA1010) during melt mixing of the two components. The compatibility of HIPS‐g‐MA in the HIPS/PA1010 blends was evident. Evidence of reactions in the blends was confirmed in the morphology and mechanical behavior of the blends. A significant reduction in domain size was observed because of the compatibilization of HIPS‐g‐MA in the blends of HIPS and PA1010. The tensile mechanical properties of the prepared blends were investigated, and the fracture surfaces of the blends were examined by means of the scanning electron microscope. The improved adhesion in a 15% HIPS/75% PA1010 blend with 10% HIPS‐g‐MA copolymer was detected. The morphology of fibrillar ligaments formed by PA1010 connecting HIPS particles was observed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2017–2025, 1999     

Effects of maleated syndiotactic polystyrene on the morphology,mechanical properties,and crystallization behavior of syndiotactic polystyrene/polyamide 6 blends

The compatibilization of syndiotactic polystyrene (sPS)/polyamide 6 (PA‐6) blends with maleic anhydride grafted syndiotactic polystyrene (sPS‐g‐MA) as a reactive compatibilizer was investigated. The sPS/PA‐6 blends were in situ compatibilized by a reaction between the maleic anhydride (MA) of sPS‐g‐MA and the amine end group of PA‐6. The occurrence of the chemical reaction was substantiated by the disappearance of a characteristic MA peak from the Fourier transform infrared spectrum. Morphology observations showed that the size of the dispersed PA‐6 domains was significantly reduced and that the interfacial adhesion was much improved by the addition of sPS‐g‐MA. As a result of reactive compatibilization, the impact strengths of the sPS/PA‐6 blends increased with an increase in the sPS‐g‐MA content. The crystallization behaviors of the blends were affected by the compatibilization effect of sPS‐g‐MA. A single melting peak of sPS in the noncompatibilized blend was gradually split into two peaks as the amount of the compatibilizer increased. A single crystallization peak of PA‐6 in the noncompatibilized blend became two peaks with the addition of 3 wt % sPS‐g‐MA. The new peak was a result of the fractionation crystallization. As the amount of sPS‐g‐MA increased, the intensity of the new peak increased, and the original peak nearly disappeared. Finally, the crystallization peak of PA‐6 disappeared with 20 wt % sPS‐g‐MA in the blend. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2502–2506, 2003