Pt‐catalyzed chemical modification of α,ω‐bis(hydrido)polydimethylsiloxanes and copoly(methylhydridosiloxane/dimethylsiloxane) with vinylheptaphenylcyclotetrasiloxane

Pt‐catalyzed hydrosilylation between vinylheptaphenylcyclotetrasiloxane and a series of α,ω‐bis(hydrido)polydimethylsiloxanes and copoly(methylhydridosiloxane/dimethylsiloxane) was used to prepare chemically modified materials. These modified polymers were characterized by IR, UV, and ¹H, ¹³C, and ²⁹Si NMR spectroscopy and gel permeation chromatography (GPC). The molecular weights, determined by GPC, UV, and NMR end‐group analysis, showed the anticipated increases. The thermal properties of the polymers were characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The crystallinity, determined by DSC, was either reduced or completely eliminated for the modified polymers. The thermal stabilities, measured in both air and nitrogen by TGA, were slightly higher than the thermal stability of α,ω‐bis(trimethylsiloxy)polydimethylsiloxane. Significantly increased bulk viscosities were observed for all the modified polymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3007‐3017, 2005     

Synthesis and thermal crosslinking of benzophenone‐modified poly(dimethylsiloxane)s

Dihydridocarbonyltris(triphenylphosphine)ruthenium catalyzes the regiospecific anti‐Markovnikov addition of an ortho C? H bond of benzophenone across the C? C double bonds of α,ω‐bis(trimethylsilyloxy)copoly(dimethylsiloxane/vinylmethylsiloxane) (99:1), α,ω‐bis(vinyldimethylsilyloxy)poly(dimethylsiloxane), and 1,3‐divinyltetramethyldisiloxane to yield α,ω‐bis(trimethylsilyloxy)copoly[dimethylsiloxane/2‐(2′‐benzophenonyl)ethylmethylsiloxane]), α,ω‐bis[2‐(2′‐benzophenonyl)ethyldimethylsilyloxy]poly(dimethylsiloxane), and 1,3‐bis[2‐(2′‐benzophenonyl)ethyl]tetramethyldisiloxane, respectively. These materials have been characterized with ¹H, ¹³C, and ²⁹Si NMR and IR spectroscopy. Their molecular weight distributions have been determined by gel permeation chromatography. The thermal stability of the polymers has been measured by thermogravimetric analysis, and their glass‐transition temperatures (T_g's) have been determined by differential scanning calorimetry. The molecular weight distribution, thermal stability, and T_g's of the modified polysiloxanes are similar to those of the precursor polymers. The molecular weights of these materials can be significantly increased via heating to 300 °C for 1 h. This may be due to crosslinking, by pyrocondensation, of pendant anthracene groups, which are produced by the pyrolysis of the attached ortho‐alkyl benzophenones. UV spectroscopy of the pyrolysate of 1,3‐bis[2‐(2′‐benzophenonyl)ethyl]tetramethyldisiloxane has confirmed the presence of pendant anthracene groups. Thermal crosslinking by the pyrocondensation of pendant anthracene groups has been verified by the pyrolysis of α,ω‐bis(trimethylsilyloxy)copoly[dimethylsiloxane/2‐(9′‐anthracenyl)ethylmethylsiloxane] (97:3). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5514–5522, 2004     

Lipidic polyols using thiol‐ene/yne strategy for crosslinked polyurethanes

Oleic acid and α,ω‐diacid were converted into propargylic esters followed by thiol‐ene/yne coupling (TEC/TYC) functionalization in presence of mercaptoethanol. The multiradical addition on fatty esters leads to the formation of lipidic polyols (OH1 and OH2), as judged by ¹H NMR and mass spectroscopies as well as by size exclusion chromatography. The crosslinking reaction between TEC/TYC‐based polyols and 4,4′‐methylene bis(phenylisocyanate) isocyanate reactant was monitored by FTIR experiment and reaction parameters were optimized. By differential scanning calorimetry, relatively high glass transitions are measured corresponding to structure with little or without dangling chain. Moreover, the thermal stability of the resulting plant oil‐based polyurethane materials (PU1 and PU2) were found to be fully consistent with that of other lipidic PUs respecting a three‐step process. Thanks to TYC methodology, fatty α,ω‐diacid produces lipidic polyol without dangling chain and lipidic thermoset PU with relatively high T_g. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1597–1606     

Thermotropic liquid crystal behavior on PBLG‐PDMS‐PBLG triblock copolymers

In this contribution, the preparation of rod‐coil‐rod triblock copolymers based on polydimethylsiloxane and polypeptide [poly(γ‐benzyl‐L ‐glutamate)] is reported. Firstly, self‐assembly in rod‐like structures was demonstrated via polarized optical microscopy and small‐angle light scattering. Further structuration details were obtained using X‐ray scattering and AFM imaging to establish the formation of a double‐hexagonal structure and to accurately define the morphological dimensions of the rodlike structures. The thermal behavior of these structures was investigated using dynamic mechanical analysis and differential scanning calorimetry. We conclude by addressing an unexpected reversible thermal transition within the 130–150 °C temperature range and the ensuing associated organizational modifications. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4668–4679, 2006     

Synthesis and characterization of alt‐copoly(carbosiloxane)s containing oligodiphenylsiloxane segments

Novel α,ω‐divinyloligodiphenylsiloxanes (1,9‐divinyldecaphenylpentasiloxane, 1,7‐divinyloctaphenyltetrasiloxane, 1,5‐divinylhexaphenyltrisiloxane, and 1,3‐divinyltetraphenyldisiloxane) were prepared and copolymerized by Pt‐catalyzed hydrosilylation with α,ω‐dihydridopentasiloxanes. The molecular weights of the copolymers were measured with gel permeation chromatography, and their thermal properties were characterized with differential scanning calorimetry and thermogravimetric analysis. The polymers had high thermal stability in air and nitrogen. The oligomer and polymer structures were determined with ¹H, ¹³C, ¹⁹F, and ²⁹Si NMR and IR spectrometry. The molecular weights of the oligomers were measured with high‐resolution mass spectrometry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2155–2163, 2005     

Poly(siloxane‐urethane) crosslinked structures obtained by sol‐gel technique

Poly(siloxane‐urethane) crosslinked structures were prepared from isophorone diisocyanate, α,ω‐bis(hydroxybutyl)oligodimethylsiloxane and a new hybrid diol containing hydrolysable Si? OC₂H₅ groups besides OH groups. The latest was synthesized by the acid‐catalyzed reaction between 1,3‐bis(3‐glycidoxypropyl)tetramethyldisiloxane and 3‐aminopropyltriethoxysilane. The formations of the urethane groups along the polymer backbone as well as the formation of the silica domains were first confirmed by the presence of the specific bands in Fourier transform infrared spectra. The resulted materials were characterized using differential scanning calorimetry, thermogravimetric analysis and scanning electron microscopy. The results of the dynamic mechanical analysis (DMA) performed at various frequencies revealed shape memory capabilities for some of the obtained structures. The silica formed because of the hydrolysis‐condensation reactions proved to have reinforcing effect upon siloxane‐urethane structure also evidenced by DMA and increasing water vapor sorption capacity as was measured by dynamic vapor sorption. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and properties of thermosetting polymers from a phosphorous‐containing fatty acid derivative

A new phosphorous‐containing fatty acid diepoxide was obtained from 10‐undecenoyl chloride and 10‐(2′,5′‐dihydroxyphenyl)‐9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and crosslinked with 4,4′‐diaminodiphenylmethane and bis(m‐aminophenyl)methylphosphine oxide. The properties of the thermosetting materials were evaluated by differential scanning calorimetry, dynamic mechanical thermal analysis, thermogravimetric analysis, and limiting oxygen index (LOI). Thermal and thermooxidative degradation was studied by gas chromatography/mass spectrometry, FTIR, ³¹P magic angle spinning NMR spectroscopy, and scanning electron microscopy. LOI values indicate good flame‐retardant properties that are related to the formation of a protective phosphorous‐rich layer that slowed down the degradation and prevented it from being total. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5630–5644, 2006     

Synthesis and properties of novel conjugated poly(silylacetylene silazane)s

A series of novel conjugated polymers, poly(silylacetylene silazane)s having different substituents, were prepared by ammonolysis of the corresponding α,ω‐dichlorosilyleneacetylene oligomers. The structures and properties of the poly(silylacetylene silazane)s were characterized by Fourier transform infrared, ¹H, ¹³C, ²⁹Si NMR, and elemental analyses, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, and spectrofluorophotometry. The resulting polymers had good thermal properties and were moderately fluorescent. Their thermal stability was improved, and obvious red shift was observed when a phenyl substituent was attached on a silicon atom of polymers in the emission spectra. These polymers have the potential to be used as light‐emitting materials with good thermal stability. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2897–2903, 2004     

Synthesis,self‐assembly,and thermosensitivity of amphiphilic POEGMA‐PDMS‐POEGMA triblock copolymers

In this article, the synthesis and self‐assembly of a novel well‐defined biocompatible amphiphilic POEGMA‐PDMS‐POEGMA triblock copolymer were studied. The copolymer was synthesized by atom transfer radical polymerization of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) using α,ω‐dibromo polydimethylsiloxane macroinitiator (Br‐PDMS‐Br). Br‐PDMS‐Br was synthesized through the esterification of α,ω‐hydroxypropyl polydimethylsiloxane and 2‐bromoisobutyryl bromide. The structures of the copolymers were confirmed by proton nuclear magnetic resonance spectroscopy, and gel permeation chromatography. The copolymers showed reversible aggregation in response to temperature cycles with a lower critical solution temperature (LCST) between 61 and 66 °C, as determined by ultraviolet‐visible spectrophotometry and dynamic light scattering. The LCST values increased in proportion to the length of the hydrophilic block and were lower than that of the POEGMA homopolymer. The self‐assembly behavior of the copolymers in aqueous solution was investigated by fluorescence spectroscopy and transmission electron microscopy. The critical micelle concentration value (1.08–0.26 10^?6 mol L^?1) decreased as the length of the POEGMA chain increased. The POEGMA‐PDMS‐POEGMA copolymers can easily self‐assemble into spherical micelles in aqueous solution. Such biocompatible block copolymers may be attractive candidates as ‘‘smart'' thermo‐responsive drug delivery systems. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2684‐2691     

Development of novel phosphorus‐containing epoxy resins from renewable resources

Novel biobased epoxy resins were prepared from two fatty acid derivatives; epoxidized 10‐undecenoyl triglyceride and epoxidized methyl 3,4,5‐tris(10‐undecenoyloxy)benzoate, with 4,4′‐diaminodiphenylmethane as a crosslinking agent. The flame retardancy of these epoxy resins was improved by the addition of 10‐[2′, 5′‐bis(9‐oxiranyl‐nonayloxy)phenyl]‐9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and by crosslinking with a phosphorus‐containing curing agent, bis(m‐aminophenyl)methylphosphine oxide. The thermal, thermomechanical, and flame‐retardant properties of the cured materials were measured with differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, and the limiting oxygen index. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6717–6727, 2006     

Synthesis and properties of Q‐silicon crosslinked siloxane networks: H3PO4‐catalyzed sol–gel dehydration/crosslinking of α,ω‐bis(hydroxy)oligodimethylsiloxanes with tetrakis(hydroxydimethylsiloxy)silane

Six silicate‐crosslinked oligodimethylsiloxane thin films were prepared by the phosphoric acid (1 mol %) catalyzed condensation of α,ω‐bis(hydroxy)oligodimethylsiloxane (P) and tetrakis(hydroxydimethylsiloxy)silane (Q). Other acid catalysts were evaluated. P and Q were prepared by the Pd‐catalyzed oxidation of the corresponding Si? H compounds with water. The starting materials were characterized by IR and ¹H, ¹³C, and ²⁹Si NMR. A thermal cure was achieved with H₃PO₄ in 24 h and with poly(phosphoric acid) in 3 h at 110–120 °C. Dynamic mechanical analysis was used to determine the glass‐transition temperatures and to evaluate the mechanical properties of the films. Their thermal stabilities (≥300 °C) in air and N₂ were determined by thermogravimetric analysis. Small amounts of non‐crosslinked P were recovered from the films by Soxhlet extractions with CH₂Cl₂ and analyzed by IR, gel permeation chromatography, and ²⁹Si NMR. The crosslink densities were evaluated by the CH₂Cl₂ absorption capacities of the films. The surface properties of the films were determined by static and dynamic contact‐angle measurements. Electrochemical impedance spectroscopy was carried out to evaluate the corrosion‐protective properties of the coatings on mild steel as a function of the exposure time to 0.5 N NaCl. The biofoul‐release properties of the films were evaluated with sporelings from mature Ulva linza plants and barnacles. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2237–2247, 2006     

Synthesis and characterization of alt‐copoly [oligosiloxane/1,4‐bis(ethylenediphenylsilyl)benzene]s

1,4‐Bis(vinyldiphenylsilyl)benzene ( I ) has been prepared and copolymerized by Pt‐catalyzed hydrosilylation with 1,9‐dihydridodecamethylpentasiloxane ( II ), 3,5,7‐tris(3′,3′,3′‐trifluoropropyl)‐1,1,3,5,7,9,9‐heptamethylpentasiloxane ( III ) and two different α,ω‐bis(hydrido)polydimethylsiloxanes (PDMS). The monomers and polymers were fully characterized by IR, UV, ¹H, ¹³C, ¹⁹F, and ²⁹Si‐NMR spectroscopy. The starting PDMS polymers and the product copolymers were further characterized by GPC, DSC, and TGA. The polymers showed thermal transitions characteristic to thermoplastic elastomers. The 1,4‐bis(ethyldiphenylsilyl)benzene moieties displayed melting transitions above room temperature while copolymer glass transition temperatures were below room temperature. Fluorescence spectra and quantum efficiencies of I and copolymers have been determined. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4825–4831, 2006     

Novel organic–inorganic hybrid materials from renewable resources: Hydrosilylation of fatty acid derivatives

Novel hybrid organic–inorganic materials were prepared from 10‐undecenoyl triglyceride and methyl 3,4,5‐tris(10‐undecenoyloxy)benzoate via hydrosilylation. 1,4‐Bis(dimethylsilyl)benzene, tetrakis(dimethylsilyloxy)silane, and 2,4,6,8‐tetramethylcyclotetrasiloxane were used as crosslinkers. The hydrosilylation reaction was catalyzed by Karstedt's catalyst [Pt(0)–divinyltetramethyldisiloxane complex]. The networks were structurally characterized by Fourier transform infrared spectroscopy, ¹³C NMR, and ²⁹Si magic‐angle‐spinning NMR. The thermal properties of these hybrids were studied with differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis. The obtained materials showed good transparency and promising properties for optical applications. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6295–6307, 2005     

Curing studies of epoxy resins with phosphorus‐containing amines

The curing system of diglycidyl ether of bisphenol A (DGEBA) with two phosphorus‐containing amine compounds—bis(3‐aminophenyl)methyl phosphine oxide and bis(4‐aminophenyl)‐bis(9,10‐dihydro‐9‐oxa‐10‐oxide‐10‐phosphaphenanthrene‐10‐yl)methane—was studied with differential scanning calorimetry under isothermal and nonisothermal conditions and compared with the DGEBA/diamino diphenyl methane system. The isoconversional method was used to evaluate the dependence of the effective activation energy on the extent of conversion. Modulated differential scanning calorimetry and dynamic mechanical thermal analysis were used to study the phenomena of vitrification and gelation. The thermal and flame‐retardant properties were evaluated, and the limiting oxygen index values of the phosphorylated resins, above 30, confirmed that phosphorus‐containing epoxy resins are effective flame retardants. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1676–1685, 2006     

Block copolymer materials from the organocatalytic ring‐opening polymerization of a pentaerythritol‐derived cyclic carbonate

9‐Phenyl‐2,4,8,10‐tetraoxaspiro[5,5]undecanone (PTO) was synthesized from pentaerythritol via the acid‐catalyzed acetal formation reaction with benzaldehyde and subsequent ring closure with ethyl chloroformate. The cyclic carbonate monomer was subsequently polymerized by ring‐opening polymerization (ROP) initiated from 1,4‐butanediol (1,4‐BDO) using the 1‐(3,5‐bis(trifluoromethyl)phenyl)‐3‐cyclohexylthiourea and 1,8‐diazabicyclo[5.4.0]undec‐7‐ene dual organocatalytic system. It was found that the organocatalyst allowed for the synthesis of well‐defined polymers with minimal adverse side reactions and low dispersities. This system was then employed in the ROP of PTO initiated from an α,ω‐dihydroxy poly(caprolactone) (PCL) macroinitiator, with varying molecular weights, to yield a series of A‐B‐A block copolymers. These materials were characterized by ¹H NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry, thermogravimetric analysis and tensile analysis. It was found that the chain extension from PCL with poly(PTO) (PPTO) blocks yielded a thermoplastic material with superior tensile properties (elongation and Young's modulus) to that of the PCL homopolymer. Furthermore, it was noted that the addition of PPTO could be employed to alter the crystallization properties (crystallization temperature (T_c), and percentage crystallization) of the central PCL block. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2279–2286     

Synthesis of a novel hybrid liquid‐crystalline rod–coil diblock copolymer

A series of novel rod–coil diblock copolymers on the basis of mesogen‐jacketed liquid‐crystalline polymer were successfully prepared by atom transfer radical polymerization from the flexible polydimethylsiloxane (PDMS) macroinitiator. The hybrid diblock copolymers, poly{2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene}‐block‐polydimethylsiloxane, had number‐average molecular weights (M_n's) ranging from 9500 to 30,900 and relatively narrow polydispersities (≤1.34). The polymerization proceeded with first‐order kinetics. Data from differential scanning calorimetry validated the microphase separation of the diblock copolymers. All block copolymers exhibited thermotropic liquid‐crystalline behavior except for the one with M_n being 9500. Four liquid‐crystalline diblock copolymers with PDMS weight fractions of more than 18% had two distinctive glass‐transition temperatures. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1799–1806, 2003     

Synthesis and characterization of poly(methyl methacrylate)‐block‐poly(methylphenylsilane)‐ block‐poly(methyl methacrylate) by atom transfer radical polymerization

ABA block copolymers of methyl methacrylate and methylphenylsilane were synthesized with a methodology based on atom transfer radical polymerization (ATRP). The reaction of samples of α,ω‐dihalopoly(methylphenylsilane) with 2‐hydroxyethyl‐2‐methyl‐2‐bromoproprionate gave suitable macroinitiators for the ATRP of methyl methacrylate. The latter procedure was carried out at 95 °C in a xylene solution with CuBr and 2,2‐bipyridine as the initiating system. The rate of the polymerization was first‐order with respect to monomer conversion. The block copolymers were characterized with ¹H NMR and ¹³C NMR spectroscopy and size exclusion chromatography, and differential scanning calorimetry was used to obtain preliminary evidence of phase separation in the copolymer products. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 30–40, 2003     

Synthesis and characterization of poly(dimethylsiloxane‐urethane) elastomers: Effect of hard segments of polyurethane on morphological and mechanical properties

A series of poly(dimethylsiloxane‐urethane) elastomers based on hexamethylenediisocyanate, toluenediisocyanate, or 4,4′‐methylenediphenyldiisocyanate hard segment and polydimethylsiloxane (PDMS) soft segment were synthesized. In this study, a new type of soft‐segmented PDMS crosslinker was synthesized by hydrosilylation reaction of 2‐allyloxyethanol with polyhydromethylsiloxane, using Karstedt's catalyst. The synthesized soft‐segmented crosslinker was characterized by FT‐IR, ¹H, and ¹³C NMR spectroscopic techniques. The mechanical and thermal properties of elastomers were characterized using tensile testing, thermogravimetric analysis, differential scanning calorimetry (DSC), and dynamical mechanical analysis measurements. The molecular structure of poly(dimethylsiloxane‐urethane) membranes was characterized by ATR‐FTIR spectroscopic techniques. Infrared spectra indicated the formation of urethane/urea aggregates and hydrogen bonding between the hard and soft domains. Better mechanical and thermal properties of the elastomers were observed. The restriction of chain mobility has been shown by the formation of hydrogen bonding in the soft and hard segment domains, resulting in the increase in the glass‐transition temperature of soft segments. DSC analysis indicates the phase separation of the hard and soft domains. The storage modulus (E′) of the elastomers was increasing with increase in the number of urethane connections between the hard and soft segments. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2980–2989, 2006     

Synthesis,characterization, and thermal properties of a novel pentaerythritol‐initiated star‐shaped poly(p‐dioxanone)

A novel star‐shaped poly(p‐dioxanone) was synthesized by the ring‐opening polymerization of p‐dioxanone initiated by pentaerythritol with stannous octoate as a catalyst in bulk. The effect of the molar ratio of the monomer to the initiator on the polymerization was studied. The polymers were characterized with ¹H NMR and ¹³C NMR spectroscopy. The thermal properties of the polymers were investigated with differential scanning calorimetry and thermogravimetric analysis. The novel star‐shaped poly(p‐dioxanone) has a potential use in biomedical materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1245–1251, 2006     

Synthesis of a novel bis‐spiroorthoester containing 9,10‐dihydro‐9‐oxa‐10‐phosphaphenantrene‐10‐oxide as a substituent: Homopolymerization and copolymerization with diglycidyl ether of bisphenol A

A new bis‐spiroorthoester‐containing monomer, bis[(1,4,6‐trioxaspiro‐[4.4]‐nonan‐2‐yl)‐methyl] 2‐[10‐(9,10‐dihydro‐9‐oxa‐10‐phosphaphenantrene‐10‐oxide‐10‐yl)] maleate (SOE‐DOPOMA), was synthesized with good yields by an esterification reaction with a hydroxylated spiroorthoester (2‐hydroxymethyl‐1,4,6‐trioxaspiro‐[4.4]‐nonane) and a phosphorus‐containing diacid {2‐[10‐(9,10‐dihydro‐9‐oxa‐10‐phosphaphenantrene‐10‐ oxide‐10‐yl)] maleic acid}, both of which were previously synthesized. SOE‐DOPOMA was characterized with ¹H, ¹³C, and ³¹P NMR spectroscopy. This new spiroorthoester was crosslinked with ytterbium triflate as a cationic initiator. A mixture of SOE‐DOPOMA and diglycidyl ether of bisphenol A was also crosslinked under the same conditions. The curing was studied with differential scanning calorimetry and monitored with Fourier transform infrared spectroscopy. The materials were characterized with differential scanning calorimetry, thermogravimetric analysis, and thermodynamomechanical analysis. The shrinkage effect on cationic crosslinking was assessed with gas pycnometry, and the flame‐retardant properties were determined with limiting oxygen index measurements. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1980–1992, 2007.