Flame retardant epoxy resins based on diglycidyloxymethylphenylsilane

Silicon‐containing epoxy resins were prepared from diglycidyloxymethylphenyl silane (DGMPS) and diglycidylether of bisphenol A (DGEBA) by crosslinking with 4,4′‐diaminodiphenylmethane (DDM). Several DGMPS/DGEBA molar ratios were used to obtain materials with different silicon contents. Their thermal, dynamomechanical, and flame‐retardant properties were evaluated and related to the silicon content. The weight loss rate of the silicon‐containing resins is lower than that of the silicon free resin. Char yields under nitrogen and air atmospheres increase with the silicon content. The LOI (limited oxygen index) values increased from 24 for a standard commercial resin to 36 for silicon‐containing resins, demonstrating improved flame retardancy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5580–5587, 2006     

Novel flame‐retardant thermosets: Diglycidyl ether of bisphenol A as a curing agent of boron‐containing phenolic resins

Boron‐containing novolac resins were synthesized by the modification of a commercial novolac resin with different contents of bis(benzo‐1,3,2‐dioxaborolanyl)oxide. These novolac resins were crosslinked with diglycidyl ether of bisphenol A (DGEBA), and their thermal, thermodynamomechanical, and flame‐retardant properties were evaluated. The boron‐containing novolac resins were less thermally stable than the unmodified novolac resin. Their modification degree and DGEBA content were related to the crosslinking density of the materials. The boron‐containing novolac resins generated boric acid at high temperatures and gave an intumescent char that slowed down the degradation and prevented it from being total. They also showed good flame‐retardant properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1701–1710, 2006     

Reporter resins for solid-phase chemistry

[reaction: see text] An analytical construct resin, designed to aid the analysis of solid-phase chemistry, has been mixed in a small proportion with a conventional resin. The analytical construct ("reporter resin") contains two orthogonal linkers that allow cleavage of either the synthetic intermediates (at linker 2) or their analytically enhanced derivatives (at linker 1). The convenient and rapid monitoring of each step in the syntheses of representative library compounds was possible using small resin aliquots.     

Samarium enolate on crosslinked polystyrene beads. II. An anionic initiator for the well‐defined synthesis of poly(allyl methacrylate) on a solid support

A samarium enolate, supported on a crosslinked polystyrene resin, successfully initiated the living anionic polymerization of allyl methacrylate (AMA) to afford the corresponding poly(AMA) with well‐controlled molecular weights. Diblock, triblock, and tetrablock copolymerizations with methyl methacrylate (MMA) were also successfully performed. The formed polymers, supported on the resin by a benzyl ester linker, were quantitatively isolated from the resin by selective cleavage of the linker with trifluoroacetic acid (TFA). Allyl ester in the side chain was not affected by this isolation step. The allyl group of the immobilized poly(AMA‐b‐MMA) on the resin was transformed into a 2,3‐dihydroxypropyl group by osmium oxidation. The resulting copolymer was isolated by TFA treatment of the resin, and it showed amphiphilicity. In both the polymerization and side‐chain modification, the formed polymers were easily washed from excess reagents only by filtration, and this demonstrated the feasibility of the automated synthesis of functional polymers based on this solid‐supported polymerization technique. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 853–860, 2003     

First synthesis of the bismole‐containing conjugated polymer

We successfully synthesized the first conjugated polymer containing a bismuth atom in the conjugated main chain by incorporating a bismuth atom into the cyclopentadiene framework (bismole), which was constructed by a polymer reaction. A synthetic procedure and characterization of the obtained polymers were discussed. This bismole‐containing conjugated polymer exhibited moderate bluish green photoluminescence in solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4857–4863, 2006     

Investigation of fracture mechanism on liquid crystalline epoxy networks arranged by a magnetic field

A liquid crystalline epoxy resin was cured under non‐ and 10T‐magnetic fields, and polydomain and monodomain networks were obtained, respectively. The fracture toughness of these systems was evaluated and it was clarified that the toughness of the magnetic field system showed a higher value. To investigate the toughening mechanism, polarized micro FTIR measurements were carried out. As a result, it was clarified that their mechanisms were quiet different. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1406–1412, 2006     

Convenient Preparation of 4-Formyl-3,5-dimethoxyphenol and Its Incorporation into Linkers and Resins for Solid-Phase Synthesis

4-Formyl-3,5-dimethoxyphenol (1) is a key synthetic intermediate used to prepare the BAL family (backbone amide linker) of acid-labile linkers and resins. The utility of these linkers and resins for solid-phase synthesis of both peptides and non-peptides has been amply demonstrated. In this article we report a simple and scalable procedure for preparation of isomerically pure 4-formyl-3,5-dimethoxyphenol (1) and its subsequent incorporation into a representative BAL linker and functionalized resin: 4-(4-formyl-3,5-dimethoxyphenoxy)butanoic acid and 4-formyl-3,5-dimethoxyphenoxy-polystyrene, respectively. The procedures are reproducible, are readily scalable, and require no chromatography.     

Thermal properties and fracture toughness of a liquid‐crystalline epoxy resin cured with an aromatic diamine crosslinker having a mesogenic group

A mesogenic‐type curing agent was synthesized to introduce a mesogenic group not only into epoxy resin backbones but also into the crosslink units. In the mesogenic curing agent system, the domain size became larger, and the network arrangement in each domain existed to a greater extent than that in a system cured with the ordinary diamine curing system according to the evidence from polarized optical micrographs and polarized Fourier transform infrared mapping measurements. Moreover, the fracture toughness of the system was considerably improved. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2486–2494, 2006     

Nonaqueous synthesis of nanosilica in epoxy resin matrix and thermal properties of their cured nanocomposites

Nonaqueous synthesis of nanosilica in diglycidyl ether of bisphenol‐A epoxy (DGEBA) resin has been successfully achieved in this study by reacting tetraethoxysilane (TEOS) directly with DGEBA epoxy matrix, at 80 °C for 4 h under the catalysis of boron trifluoride monoethylamine (BF₃MEA). BF₃MEA was proved to be an effective catalyst for the formation of nanosilica in DGEBA epoxy under thermal heating process. FTIR and ²⁹Si NMR spectra have been used to characterize the structures of nanosilica obtained from this direct thermal synthetic process. The morphology of the nanosilica synthesized in epoxy matrix has also been analyzed by TEM and SEM studies. The effects of both the concentration of BF₃MEA catalyst and amount of TEOS on the diameters of nanosilica in the DGEBA epoxy resin have been discussed in this study. From the DSC analysis, it was found that the nanosilica containing epoxy exhibited the same curing profile as pure epoxy resin, during the curing reaction with 4,4′‐diaminodiphenysulfone (DDS). The thermal‐cured epoxy–nanosilica composites from 40% of TEOS exhibited high glass transition temperature of 221 °C, which was almost 50 °C higher than that of pure DGEBA–DDS–BF₃MEA‐cured resin network. Almost 60 °C increase in thermal degradation temperature has been observed during the TGA of the DDS‐cured epoxy–nanosilica composites containing 40% of TEOS. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 757–768, 2006     

Synthesis of a new diglycidylic Meldrum acid derivative and study of the curing with lanthanide triflates as initiators

A new epoxy resin derived from Meldrum acid (DGMA) was synthesized by a two steps synthetic procedure and structurally characterized by the usual spectroscopic techniques and elemental analysis. Ytterbium and lanthanum triflates were tested as cationic initiators to cure this resin and its mixtures with diglycidylether of bisphenol A (DGEBA) in several proportions. By FTIR‐ATR spectroscopy the evolution of the groups, which participate in the curing was followed. The evolution of the curing and the T_g of the materials were studied by differential scanning calorimetry and the kinetic parameters were calculated applying isoconversional procedures. Ytterbium triflate led to a quicker curing than lanthanum. The thermal stability of the materials obtained was evaluated by thermogravimetry and the higher thermal degradability of the materials containing DGMA was confirmed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3088–3097, 2008     

Development of novel flame‐retardant thermosets based on boron‐modified phenol–formaldehyde resins

Boron‐containing novolac resins were prepared through the modification of a commercial novolac resin with different contents of bis(benzo‐1,3,2‐dioxaborolanyl) oxide. Their thermal and flame‐retardant properties were measured. Then, they were crosslinked with hexamethylenetetramine, and their thermal, thermodynamomechanical, and flame‐retardant properties were evaluated. Their modification degree was related to the segmental motion of the materials. The crosslinking of the boron‐modified novolac resins with hexamethylenetetramine was slower and not as extensive as that of commercial novolac resins because the nitrogen from intermediate species coordinated with boron. The thermal degradation of the boron‐containing novolac resins generated boric acid at high temperatures and gave an intumescent char that slowed the degradation and prevented it from being complete. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3503–3512, 2006     

Poly(styrene‐co‐glycerol dimethacrylate): Synthesis,characterization, and application as a resin for gel‐phase peptide synthesis

An efficient cross‐linked polymer support for solid‐phase synthesis was prepared by introducing glycerol dimethacrylate cross‐linker to polystyrene network using free radical aqueous suspension polymerization. The support was characterized by various spectroscopic methods. Morphological feature of the resin was analyzed by microscopy. The polymerization reaction was investigated with respect to the effect of amount of cross‐linking agent, which in turn vary the swelling, loading, and the mechanical stability of the resin. The solvent uptake of the polymer was studied in relation to cross‐linking and compared with Merrifield resin. The stability of the resin was tested in different synthetic conditions used for solid‐phase peptide synthesis. Hydroxy group of the support was derivatized to chloro and then amino groups using different reagents and reaction conditions. Efficiency of the support was tested and compared with TentaGel? resin by following different steps involved in the synthesis of the 65–74 fragment of acyl carrier protein. The results showed that the poly(styrene‐co‐glycerol dimethacrylate) (GDMA‐PS) is equally efficient as TentaGel resin in peptide synthesis. The purity of the peptides was analyzed by HPLC and identities were determined by mass spectroscopy and amino acid analysis. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4382–4392, 2005     

Star polystyrenes by anionic star–star coupling reactions with divinylbenzene

The incremental addition of divinylbenzene was used to generate star polystyrenes in a nearly full conversion of a living polystyrenyl anion. The dramatic increase in the molecular weight of the star polystyrenes with a limited supply of the living polystyrene supported the formation of gradient‐star polystyrenes through star–star coupling. The stoichiometric analysis of the star polymers revealed that their connection polymer had a shorter length than their branch polymer. The measured solution viscosity of the gradient‐star polymers greatly deviated from a linear correlation with the molecular weight and was in parallel to a theoretical simulation based on a highly branched structure of the gradient‐star polymer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2579–2586, 2006     

Sizing effects on main relaxation process of cyanate ester glass fiber composites using dynamic mechanical and microthermal analyses

The influence of sizing/polymer interaction or interphase on dynamic mechanical relaxation properties of cyanate ester composites was investigated by means of dynamic mechanical analysis. The dynamic mechanical behavior of different samples (three types of composites with different sizing and neat resin) was analyzed by using two phenomenological models (TFV and WLF). Related coefficients such as C₁, C₂, and T_∞ (Vogel temperature) were evaluated. Results have shown that these parameters were strongly dependent on sizing state, therefore, on interphase. In addition, the frequency dependence of the molecular relaxation process was well described by the Cole‐Cole plot. These results were confirmed by the sizing extract/resin blend study. Microthermal analysis has shown that partial miscibility existed between resin and sizing extract. Local thermal analyses were carried out by positioning the probe over selected regions: bulk resin and sizing/resin blend. A decrease in resin glass‐transition temperature was observed in the sizing resin blend. The different results have shown that a local plasticization of resin by sizing occurred with crosslink density modification. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 205–214, 2006     

Oligomeric aliphatic–aromatic ether containing phthalonitrile resins

A versatile synthetic method has been developed for oligomeric aliphatic–aromatic ether containing phthalonitrile (PN) resins and applied to the preparation of three unique resin systems. The oligomeric PN monomers were prepared from the reaction of an excess amount of bisphenol A with a dihalo‐aliphatic containing compound in the presence of K₂CO₃ in dimethylsulfoxide, followed by end‐capping with 4‐nitrophthalonitrile in a two‐step, one‐pot reaction. These PN resin systems exhibited excellent viscosities for molding various shaped articles after thermal curing to yield crosslinked polymers. These polymers offered more mechanical flexibility, when compared with an all aromatic backbone, while still maintaining good thermal stability, dielectric properties, and low water absorption. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2186–2191     

Improved synthesis of oligomeric phthalonitriles and studies designed for low temperature cure

An improved synthetic method has been developed for oligomeric aromatic ether ketone‐based phthalonitrile (PN) resins. A new curing additive was studied that lowers the cure temperature of the PN resin to around 150 °C and compared to the traditional high‐temperature aromatic diamine. Mechanical and thermo‐oxidative analyses of polymeric samples from both systems were determined and compared under various curing conditions. The PN polymer exhibited low water absorption regardless of the chosen cure system. Published 2014. This article is a U.S. Government work and is in the public domain in the USA. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1662–1668     

Synthesis and cationic photopolymerization of new silicon‐containing oxetane monomers

The cationic photopolymerization of oxetane‐based systems containing silicon monomers was investigated. For this purpose, three new silicon‐containing oxetane monomers were synthesized through a simple and straightforward synthetic method. The silicon‐containing monomers were added to a typical oxetane resin, 3,3′‐[oxydi(methylene)]bis(3‐ethyloxetane), in concentrations of 1–5 wt %. They exploited a certain surface tension effect without affecting the rate of polymerization. Enrichment only on the air side was achieved, which induced hydrophobicity in the photocured films, depending on the monomer structure and concentration. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1415–1420, 2004     

Elaboration of well‐defined Rasta resins and their use as supported catalytic systems for atom transfer radical polymerization

New supported catalytic systems based on the immobilization of a ligand onto supported (co)polymers were prepared, allowing copper immobilization onto a solid support during the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). These supported catalysts were elaborated by the ATRP of 2‐vinyl‐4,4‐dimethyl‐5‐oxazolone and/or styrene onto a Wang resin initiator. Two different approaches were used, involving well‐defined architectures synthesized by ATRP. First, a supported electrophilic homopolymer [Wang‐g‐poly(2‐vinyl‐4,4‐dimethyl‐5‐oxazolone)] was synthesized to obtain an azlactone ring at each repetitive unit, and a supported statistical copolymer [Wang‐g‐poly(2‐vinyl‐4,4‐dimethyl‐5‐oxazolone‐stat‐styrene)] was synthesized to introduce a distance between the azlactone rings. The azlactone‐based (co)polymers were then modified by a reaction with N,N,N′,N′‐tetraethyldiethylenetriamine (TEDETA) to create supported complexing sites for copper bromide. The ATRP of MMA was studied with these supported ligands, and a first‐order kinetic plot was obtained, but high polydispersity indices of the obtained poly(methyl methacrylate) were observed (polydispersity index > 2). On the other hand, the supported ATRP of styrene was performed, followed by the nucleophilic substitution of bromine by TEDETA (Wang‐g‐polystyrene–N,N,N′,N′‐tetraethyldiethylenetriamine) at the chain end of the grafted polystyrene chains. This strategy led the ligand away from the core bead, depending on the length of the polystyrene block (number‐average molecular weight determined by size exclusion chromatography = 1100–2250 g/mol). These supported complexes mediated a controlled polymerization of MMA, yielding polymers with controlled molar masses and low polydispersity indices. Moreover, after the polymerization, 96% of the initial copper was kept in the beads. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5316–5328, 2006     

Similarities between polyelectrolyte gels and biopolymer solutions

Small angle neutron scattering (SANS) measurements and osmotic swelling pressure measurements are reported for polyelectrolyte gels and solutions under nearly physiological conditions. A synthetic polymer (sodium-polyacrylate) and three biopolymers (DNA, hyaluronic acid, and polyaspartic acid) are studied. The neutron scattering response of these anionic polyelectrolytes is closely similar, indicating that at larger length scales the organization of the polymer molecules is not significantly affected by the fine details of the molecular architecture (e.g., size and chemical structure of the monomer unit, type of polymer backbone). The results suggest that specific interactions between the polyelectrolyte chains and the surrounding monovalent cations are negligible. It is found that the osmotic compression modulus of these biopolymer solutions determined from the analysis of the SANS response decreases with increasing chain persistence length. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3679–3686, 2006     

Poly(methyl methacrylate‐co‐pentaerythritol tetraacrylate‐co‐butyl methacrylate)‐g‐polystyrene: Synthesis and high oil‐absorption property

Well‐defined high oil‐absorption resin was successfully prepared via living radical polymerization on surface of polystyrene resin‐supported N‐chlorosulfonamide group utilizing methyl methacrylate and butyl methacrylate as monomers, ferric trichloride/iminodiacetic acid (FeCl₃/IDA) as catalyst system, pentaerythritol tetraacrylate as crosslinker, and L ‐ascorbic acid as reducing agent. The polymerization proceeded in a “living” polymerization manner as indicated by linearity kinetic plot of the polymerization. Effects of crosslinker, catalyst, macroinitiator, reducing agent on polymerization and absorption property were discussed in detail. The chemical structure of sorbent was determined by FTIR spectrometry. The oil‐absorption resin shows a toluene absorption capacity of 21 g g^?1. The adsorption of oil behaves as pseudo‐first‐order kinetic model rather than pseudo‐second‐order kinetic model. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013