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We have prepared semi-interpenetrating polyacrylate networks (PA/BA-m s-IPNs) through rapid photopolymerization of a triacrylate monomer (TMPTA) in the presence of a photoinitiator (I184), a tetramercaptane transfer agent (4SH), and N-methyl-bisbenzoxazine (BA-m). Next, we prepared novel fully interpenetrating polyacrylate (PA) and polybenzoxazine (PBZ) networks (PA/PBZ f-IPNs) through thermal polymerization of the BA-m monomer at 180 °C for 4 h. For the PA/BA-m s-IPNs, the BA-m monomers can be frozen and dispersed in the UV-cured PA network within 5 min to inhibit macrophase separation. After thermal polymerization, the phenol units of the ring-opened PBZ segments can form a hydrogen-bonding interface with the carbonyl groups to improve the compatibility between the PBZ microdomains and the PA networks. From an analysis using Kissinger's method, the non-isothermal kinetics of the thermal polymerization for the PA/BA-m s-IPNs indicate that an increase in the PA content increased the steric hindrance of PBZ polymerization. We used DSC, TGA, and contact angle analyses to determine the glass transition temperature, thermal stability, and surface free energy, respectively, of the PA/PBZ f-IPNs. The thermal stability and surface free energy of these PA/PBZ f-IPNs display linear relationships with respect to the PBZ content.

We have generated porous polybenzoxazine (PBZZ) materials by using a B-a type PBZZ as the matrix and various molecular weights of poly(e-caprolactone) (pa-PCL) as the labile constituent. The slight degree of hydrogen bonding that exists between the two polymers results in micro-phase separation without an excess degree of aggregation occurring. The porous structures form after hydrolysis of the PCL domains; we characterized them using a variety of techniques, including FT-IR spectroscopy, DSC, TGA, FE-SEM, and DEA. At 298 K and 10 5 Hz, we obtained a thin, transparent, and nanoporous film that has a very low dielectric constant (1.95).

β-Cyclodextrin (β-CD) forms inclusion complexes (ICs) with adamantane-modified benzoxazines (2 benzoxazine and 3 benzoxazine). These benzoxazines can readily penetrate into the CD's hydrophobic cavity, causing turbidity of their solutions, from which fine crystalline powders are obtained. We characterized these complexes by powder X-ray diffraction, 13C and 13C CP/MAS NMR spectroscopies, DSC, and TGA. The X-ray diffraction and solid-state 13C CP/MAS NMR spectroscopy indicate that the IC domains of the polypseudorotaxanes maintain their channel-type structures after the ring-opening curing reactions have occurred. Furthermore, DSC measurements indicate that complexing the adamantane-modified benzoxazine units with β-CDs result in stiffer main chains and, thus, higher glass transition temperature. TGA also indicates that the inclusion complexes have enhanced its thermal stability.

We have successfully synthesized a novel benzoxazine ring-containing polyhedral oligomeric silsesquioxane (BZ-POSS) monomer by two routes: (1) hydrosilylation of a vinyl-terminated benzoxazine using the hydro-silane functional group of a polyhedral oligomeric silsesquioxane (H-POSS) and (2) reaction of a primary amine-containng POSS (Amine-POSS) with phenol and formaldehyde. The benzoxazine-containing POSS (BZ-POSS) monomer can be copolymerized with other benzoxazine monomers through ring-opening polymerization under conditions similar to that used for polymerizing pure benzoxazines. Thermal properties of these POSS-containing organic/inorganic polybenzoxazine nanocomposites have been improved over the pure polybenzoxazine analyzed by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The BZ-POSS monomer is poorly miscible with the benzoxazine monomer and tends to aggregate and forms its own domains, both before and after polymerization. At a higher BZ-POSS content, gross aggregation occurs and results in a lower than expected improvement in the thermal properties.

We have prepared polystyrene/clay nanocomposites using an emulsion polymerization technique. The nanocomposites were exfoliated at up to a 3 wt% content of pristine clay relative to the amount of polystyrene (PS). We used two different surfactants for the montmorillonite: the aminopropylisobutyl polyhedral oligomeric silsesquioxane (POSS) and the ammonium salt of cetylpyridinium chloride (CPC). Both surfactants can intercalate into the layers of the pristine clay dispersed in water prior to polymerization. Although the d spacing of the POSS-intercalated clay is relatively smaller than that of the CPC-intercalated clay, PS more easily intercalates and exfoliates the POSS-treated clay than the CPC-treated clay. IR spectroscopic analysis further confirms the intercalation of POSS within the clay layers. We used X-ray diffraction (XRD) and transmission electron microscopy (TEM) to characterize the structures of the nanocomposites. The nanocomposite prepared from the clay treated with the POSS containing surfactant is exfoliated, while an intercalated clay was obtained from the CPC-treated surfactant. The molecular weights of polystyrene (PS) obtained from the nanocomposite is slightly lower than the virgin PS formed under similar polymerization conditions. The value of Tg of the PS component in the nanocomposite is 8 °C higher than the virgin PS and its thermal decomposition temperature (21 °C) is also higher significantly. The presence of the POSS unit in the MMT enhances the thermal stability of the polystyrene.

The sol–gel process was used to prepare a photosensitive inorganic–organic composite, silica/poly(2-hydroxymethyl methacrylate). Its nanoscale morphology was observed with field emission scanning electron microscopy at high magnifications (e.g., 160,000×). The size of the particles in the nanocomposite synthesized under various preparation conditions fell in the range of 20–50 nm. The effects of the pH, reactant composition, and solvent content in the reaction mixture on the thermal and mechanical properties of the nanocomposite were studied with thermogravimetric analysis, dynamic mechanical analysis, and thermomechanical analysis. The thermal stability of the synthesized nanocomposite could generally be improved by an increase in the molar ratio of the inorganic component, a reduction in the reaction pH, or an increase in the solvent content. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1927–1935, 2004

The structure of benzoxazines is similar to that of phenolic resin through thermal self-curing of the heterocyclic ring opening reaction that neither requires catalyst nor releases any condensation byproduct. These polybenzoxazine resins have several outstanding properties such as high thermal stability and high glass transition temperature. To better understand the curing kinetics of this copolybenzoxazine thermosetting resin, dynamic and isothermal differential scanning calorimetry measurements were performed. Three models, the Kissinger method, the Flynn–Wall–Osawa method, and the Kamal method, were used to describe the curing process. Dynamic kinetic activation energies based on Kissinger and Flynn–Wall–Osawa methods are 72.11 and 84.06 KJ/mol, respectively. The Kamal method based on an autocatalytic model results in a total order of reaction between 2.66 and 3.03, depending on curing temperature. Its activation energy and Arrhenius preexponential are 50.3 KJ/mol and 7959, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 730–737, 2005

Two novel structures of adamantane-modified benzoxazines were synthesized from 4-(1-adamantyl)-phenol through the incorporation of adamantane as a pendant group into the polybenzoxazine backbone. Both 1H-NMR and Fourier transform infrared spectra were used to characterize these structures. The rigid structure of the adamantane tended to hinder the chain mobility (boat anchor effect) and substantially enhanced the thermal properties, including the glass-transition temperature and decomposition temperature, especially for poly(6-adamantyl-3-methyl-3,4-dihydro-2H-1,3-benzoxazine). In the poly(6-adamantyl-3-phenyl-3,4-dihydro-2H-1,3-benzoxazine) system, however, the opposite result for the glass-transition temperature was observed and it was interpreted as lower crosslinking density. The phenyl group was bulkier than the methyl group, and the movement of the molecular chain was hindered between bridging points during the curing process; this resulted in a lower crosslinking density and a lower glass-transition temperature than those of poly(6-adamantyl-3-methyl-3,4-dihydro-2H-1,3-benzoxazine). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 932–940, 2004

It is well-known that low dielectric materials are used as insulating materials, and the incorporation of fluorinated substitutes into polymer is able to decrease its dielectric constant because of small dipole and the low polarizability of the C–F bond. In this study, a novel structure of the fluorinated benzoxazine (F-1 benzoxazine) has been synthesized by incorporating the trifluoromethyl groups into the monomer, and its structure has also been characterized by 1H NMR, 19F NMR and FT-IR. Further, we have prepared the fluorinated copolybenzoxazine (B-a/F-1=1/1) with substantially reduced dielectric constant at K=2.36. In addition, this fluorinated copolybenzoxazine possesses high glass transition temperature and high thermal stability, which is suitable for high temperature operation for certain special processes of interlayer dielectrics.

The thermal properties and hydrogen bonding behavior of B-a type polybenzoxazine (PBZZ)/PVP blends were investigated by DSC and FTIR. The DSC result shows a single Tg over the entire compositions and a large positive deviation based on Kwei equation was observed in the Tg versus composition diagram, implying that strong hydrogen bonding interaction exists between PBZZ and PVP segments. The strength of hydrogen bonding interaction is in the order of inter-association between the hydroxyl group of PBZZ and the carbonyl group of PVP (K A =594 L mol −1 ) >self-association between the hydroxyl group of pure PBZZ (K B =72.6 L mol −1 ) >inter-association between the hydroxyl and the Mannich-based bridge of pure PBZZ (K C L mol −1 ). Good correlation between DSC and FTIR analysis were observed.

The sol–gel method was employed to prepare an inorganic–organic hybrid, silica/poly(HEMA). The chemical structure of this material was analyzed by means of FTIR and solid 29Si-NMR. Using TEM and low voltage FESEM imaging at high magnifications (e.g., 300 KX), the hybrid was found to comprise nano-particles whose sizes fall largely over the range 20–30 nm.