An investigation of the thermal and thermo‐oxidative degradation of polybenzoxazines with a reactive functional group

The thermal behavior of a series of polybenzoxazines based on 3‐aminophenylacetylene has been investigated. The effect of reactive amine on the thermal cleavage of the Mannich base is examined under both inert and oxidative environments. It has been shown that the thermal stability of polybenzoxazines is substantially improved by the reactive amine. Various biphenols are found to have insignificant effect on the thermal stability of this series of polybenzoxazines. These nitrogen containing phenolic resins are nonflammable polymers. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 647–659, 1999     

Improved thermal and mechanical properties of polybenzoxazines based on alkyl‐substituted aromatic amines

The thermal and mechanical properties of polybenzoxazine thermoset networks containing varying amounts of phenolic Mannich bridges, arylamine Mannich bridges, and methylene bridges have been investigated. In materials based on m‐toluidine and 3,5‐xylidine, the onset of thermal degradation is delayed until around 350 °C with no significant effect on the final char yield. The first of the three weight‐loss events usually seen in aromatic amine‐based polybenzoxazines is absent in these two materials. Materials with additional amounts of arylamine Mannich bridges and methylene bridges show improved mechanical properties, including higher crosslink densities and rubbery plateau moduli. Correlations between the observed mechanical properties and network structures are established. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3289–3301, 2000     

Thermal stability of polybenzoxazines with lanthanum chloride and their crosslinked structures

Lanthanum chloride (LaCl₃) was incorporated into five kinds of benzoxazines by different preparation methods. The thermal stability and the structures of polybenzoxazines were characterized by thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy. The evolved gases from the degradation process of polybenzoxazines were analyzed by FTIR. The results showed that the thermal stability and char yields of three kinds of polybenzoxazines containing LaCl₃ can be improved obviously. LaCl₃ has an important effect on the polymerization reactions of benzoxazines. More stable arylamine Mannich bridges were observed in the chemical structures of the polybenzoxazines. It is these structures that can effectively retard the volatilization of aniline derivatives and result in the improvement of the thermal stability of the polybenzoxazines.     

High performance benzoxazine monomers and polymers containing furan groups

Furan‐containing benzoxazine monomers, 3‐furfuryl‐3,4‐dihydro‐2H‐1,3‐benzoxazine (P‐FBz) and bis(3‐furfuryl‐3,4‐dihydro‐2H‐1,3‐benzoxazinyl)isopropane (BPA‐FBz), were prepared using furfurylamine as a raw material. The chemical structures of P‐FBz and BPA‐FBz were characterized with FTIR, ¹H NMR, elemental analysis, and mass spectrometry. Formation of furfurylamine Mannich bridge networks in the polymerizations of P‐FBz and BPA‐FBz increased the cross‐linking densities and thermal stability of the resulting polybenzoxazines. P‐FBz‐ and BPA‐FBz‐based polymers also exhibited high glass transition temperatures above 300 °C, high char yields, and low flammability with limited oxygen index values of 31. The dielectric (D_k = 3.21–3.39) and mechanical properties (high storage modulus of 3.0–3.9 GPa and low coefficient of thermal expansion of 37.7–45.4 ppm) of the P‐FBz‐ and BPA‐FBz‐based polymers were superior or comparable to other polybenzoxazines. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5267–5282, 2005     

Shape memory polybenzoxazines based on a siloxane‐containing diphenol

A siloxane‐containing diphenol is synthesized from 1,1,3,3‐tetramethyldisiloxane and o‐allylphenol, followed by the Mannich condensation with aniline, methylamine, and formaldehyde yielding two siloxane‐containing benzoxazines. The onset polymerization temperature of aniline‐based benzoxazine is higher than that of the methylamine counterpart. The dynamic mechanical properties of the polybenzoxazines depend on the structure of the starting primary amines. Both polybenzoxazines exhibit one‐way dual‐shape memory behavior in response to changes in temperature, and they show excellent shape fixity ratios in bending, tension, and tensile stress–strain tests, high shape recovery ratios in bending and tension tests, but relatively low shape recovery ratios in tensile stress–strain test. The network chain segments including the alkylsiloxane units serve as a thermal control switch based on the glass transition temperatures (39 and 53 °C) for the polybenzoxazines. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1255–1266     

Differential scanning calorimetry and thermogravimetric analysis investigation of the thermal properties and degradation of some radiation‐grafted films and membranes

The influence of irradiation and grafting on the crystallinity of three base polymers has been investigated with differential scanning calorimetry. Grafting has the largest effect on the base polymer crystallinity and results in a reduction of the crystallinity. The thermal degradation of the base polymers and grafted films has been investigated with thermogravimetric analysis. The extent of the fluorination of the base polymer, the irradiation method, and the graft level all influence the thermal degradation and its activation energy. It is proposed that the variation of the chain lengths of the grafted polystyrene chains is actually a primary underlying factor responsible for the influence of these various parameters on the degradation process. The first results of a comparative thermal analysis of some fuel‐cell membranes are also presented, and the promise and shortcomings of this method are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2612–2624, 2004     

Methylol‐functional benzoxazines as precursors for high‐performance thermoset polymers: Unique simultaneous addition and condensation polymerization behavior

A new class of high‐performance resins of combined molecular structure of both traditional phenolics and benzoxazines has been developed. The monomers termed as methylol‐functional benzoxazines were synthesized through Mannich condensation reaction of methylol‐functional phenols and aromatic amines, including methylenedianiline (4,4′‐diaminodiphenylmethane) and oxydianiline (4,4′‐diaminodiphenyl ether), in the presence of paraformaldehyde. For comparison, other series of benzoxazine monomers were prepared from phenol, corresponding aromatic amines, and paraformaldehyde. The as‐synthesized monomers are characterized by their high purity as judged from ¹H NMR and Fourier transform infrared spectra. Differential scanning calorimetric thermograms of the novel monomers show two exothermic peaks associated with condensation reaction of methylol groups and ring‐opening polymerization of benzoxazines. The position of methylol group relative to benzoxazine structure plays a significant role in accelerating polymerization. Viscoelastic and thermogravimetric analyses of the crosslinked polymers reveal high T_g (274–343 °C) and excellent thermal stability when compared with the traditional polybenzoxazines. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Polybenzoxazine resins: Aspects of interaction and adsorption behavior

The technique of inverse gas chromatography (IGC) has been used to evaluate the acid–base interaction potential of two polybenzoxazines. One of these, prepared from bisphenol‐A monomer, was shown to be a net base. Another based on dihydroxybenzophenone registered as a net acid. The bisphenol‐A version was adsorbed at controlled thicknesses on α‐alumina, on fumed silica and on boron nitride, all three solids with acidic surfaces as shown by IGC data. Thin layers of the adsorbed polymer near monolayer coverage were strongly perturbed by the underlying substrate, the polymer surface now behaving as a net acid. Thicker layers of the adsorbed polymer revert to basicity, but fail to attain the acid–base interaction constants of the pure polymer. The presence of strongly interactive substrates leads to the creation of a substantial interphase, the interaction properties of the adsorbed polymer varying through the thickness of this layer. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1441–1447, 1999     

Spectroscopic investigations of polyacrylonitrile thermal degradation

PAN undergoes chemical decomposition in stages on thermal treatment. In the literature, several mechanisms were proposed for the degradation process. However, the decomposition pathway and the structural rearrangement of solid residue in relation to the loss of volatile products are not fully understood. The degradation process has therefore received further attention in this work by employing a combination of FT-IR, high-resolution solid-state ¹³C-NMR, pyrolysis GC-MS, and microelemental analysis. These investigations have established that PAN decomposes to gaseous and volatile products over a range of temperatures (150–590°C) with concurrent stabilization of the structure of residual matter occurring on a parallel course. While linear polymerization of nitrile group is the principal reaction in the decomposition process, cyclization followed by extended conjugation is the notable exothermic process. No evidence has been obtained for the formation of oxygen-containing chromophores either as intermediates or as part of the chemical structure of the residue. Temperature sensitivity of oligomer formation has been established through pyrolysis–GC-MS studies. The overall decomposition profile of PAN has thus been established. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2503–2512, 1998     

Behavior of a bisphenol‐A‐based polybenzoxazine exposed to ultraviolet radiation

An interaction mechanism for a bisphenol‐A‐based polybenzoxazine resin exposed to ultraviolet radiation is proposed. Fourier transform infrared spectroscopy indicated that a carbonyl‐containing species was formed when cured 6,6′‐bis(2,3‐dihydro‐3‐methyl‐4H‐1,3‐benzoxazinyl)isopropylidene (BA‐m) resin was exposed to ultraviolet radiation (λ > 290 nm) in the presence of ambient air at room temperature. The isopropylidene linkage was the reactive site of cleavage and oxidation. It was apparent from model compound studies that this structure was severed, resulting in the formation of a 2,6‐disubstituted benzoquinone. Model compound studies also demonstrated that the BA‐m polymer backbone structure, the Mannich bridge, which was present in and characterized all the polybenzoxazines, neither cleaved nor oxidized in the presence of ultraviolet radiation in a detectable manner under the conditions of this study. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2687–2701, 2000     

Dynamic mechanical and thermal characterization of high-performance polybenzoxazines

Two polybenzoxazines are cured in an autoclave from the polyfunctional benzoxazine monomers, 8,8′-bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) and 6,6′-bis(2,3-dihydro-3-phenyl-4H-1,3-benzoxazinyl) ketone. The density and tensile properties of these polybenzoxazines are measured at room temperature. Dynamic mechanical tests are performed to determine the T_g, crosslink density, and the activation enthalpy of the glass-transition process for these two polybenzoxazines. The effect of postcure temperature on the T_g of the polymers is investigated and discussed in terms of crosslink density. Fourier transform infrared (FTIR) spectroscopy is also applied for the molecular characterization of the curing systems. Thermal properties of these polybenzoxazines are studied in terms of isothermal aging and decomposition temperature via thermogravimetric analysis. These two polybenzoxazines show mechanical and thermal properties similar to or better than bismaleimides and some polyimides. They also show very high char yield after being carbonized in a nitrogen atmosphere. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3257–3268, 1999     

Thermal behavior of Mannich base N,N′-tetra(4-antipyrylmethyl)-1,2 diaminoethane (TAMEN) and its binuclear complexes

The thermal decomposition of Mannich base N,N′-tetra(4-antipyrylmethyl)-1,2-diaminoethane (TAMEN), and its Ni(II), binuclear complex, Ni₂(TAMEN)Cl₄, in air and in nitrogen atmosphere, were investigated. X-ray powder diffractometry, infrared spectroscopy and simultaneous thermogravimetry-differential thermal analysis (TG-DTA), have been used to characterize and to study the thermal behavior of these compounds. The results provided information concerning the stoichiometry, crystallinity, thermal stability and decomposition mechanism of the compound.     

Synthesis and analysis of thermal characteristics of polybenzoxazine based on phenol and 3‐Amino phenyl boronic acid

In this work, 3‐amino phenyl boronic acid (AB) was used as an aniline derivative in the preparation of polybenzoxazine based on phenol. In order to investigate the effect of boronic acid on thermal characteristics, polybenzoxazines based on pure aniline and 50% aniline and AB mixture were also prepared and analyzed. Significant improvements in thermal characteristics, increase in thermal stability and char yield, was recorded for the polymers based on AB or its mixture. This behavior was associated with crosslinked structures generated by condensation reactions of B? OH groups. Morphologic and thermal characteristics of polybenzoxazines samples were investigated by NMR, FTIR, DSC, TGA, and direct pyrolysis mass spectrometry (DP‐MS) techniques. Application of DP‐MS technique also supplied additional information on crosslinked structures produced by boronic acid units. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1711–1716     

Radiation effects on the thermal degradation of poly(vinyl chloride) and poly(vinyl alcohol)

Radiation effects on the formation of conjugated double bonds in the thermal degradation of poly(vinyl chloride) (PVC) and poly(vinyl alcohol) (PVA) were investigated. Thin films of PVC and PVA were either irradiated with γ-rays at ambient temperature (pre-irradiation) and then subjected to thermal treatment, or irradiated at elevated temperatures (in situ irradiation). An extensive enhancement of the thermal degradation was observed for the pre-irradiation of the PVC films, which was more effective than the effect of the in situ irradiation at the same absorption dose. For the PVA degradation, however, the effect of the in situ irradiation was larger than that of the pre-irradiation. The results were explained and related mechanisms were discussed based on radiation-induced chemical reactions and their individual contributions to the thermal degradation behaviors of the two polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3089–3095, 1998     

Chemical reactions occurring in the thermal treatment of PC/PMMA blends

The chemical reactions occurring in the thermal treatment of bisphenol-A polycarbonate (PC) and poly(methyl methacrylate) (PMMA) blends have been investigated by nuclear magnetic resonance (NMR), mass spectrometry (MS), size exclusion chromatography (SEC), and thermogravimetry (TG). Our results suggest that in the melt-mixing of PC/PMMA blends, at 230°C, no exchange reactions occur and that only the depolymerization reaction of PMMA has been observed. In the presence of an ester-exchange catalyst (SnOBu₂), an exchange reaction was found to occur at 230°C, but no trace of PC/PMMA graft copolymer has been observed. Instead, an exchange reaction between the monomer methyl methacrylate (MMA), generated in the unzipping of PMMA chains, and the carbonate groups of PC has been suggested. This is due to the diffusion of MMA at the interface or even into the PC domains, where it can react with PC producing low molar mass PC oligomers bearing methacrylate and methyl carbonate chain ends and leaving the undecomposed PMMA chains unaffected. The TG curves of PC/PMMA blends prepared by mechanical mixing and by casting from THF show two separated degradation steps corresponding to that of homopolymers. This behavior is different from that of a transparent film of PC/PMMA blend, obtained by solvent casting from DCB/CHCl₃, which shows a single degradation step indicating that the degradation rate of PC is increased by the presence of PMMA in the blend. The thermal degradation products obtained by DPMS of this blend consist of methyl methacrylate (MMA), cyclic carbonates arising from the degradation of PMMA and PC, respectively, and a series of open chain bisphenol-A carbonate oligomers with methacrylate and methyl carbonate terminal groups. The presence of the latter compounds suggests a thermally activated exchange reaction occurring above 300°C between MMA and PC. The presence of bisphenol-A carbonate oligomers bearing methyl ether end groups, generated by a thermally activated decarboxylation of the methyl carbonate end groups of PC, has also been observed among the pyrolysis products. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1873–1884, 1998     

Improved thermal stability of polybenzoxazines by transition metals

The incorporation of various transition metal salts increases the char formation of polybenzoxazines. It is shown that the effect of the transition metal salt is not simply additive and is independent of the amine and phenol structures. While the metal salts have an insignificant effect on the polymerization, their presence in benzoxazine favors the formation of carbonyl functional groups. It is proposed that reduced flammability of polybenzoxazines is achieved through the evolution of CO₂ during thermal degradation.     

Synthesis and characterization of saturated and unsaturated polysulfide polymers and their thermal degradation processes investigated by flash pyrolysis–gas chromatography/mass spectrometry

The synthesis of polysulfide polymers with unsaturated and saturated units in the backbone and their characterization by Fourier transform infrared, NMR, gel permeation chromatography, thermogravimetric analysis, and differential scanning calorimetry are reported. This is the first report on an analysis of the thermal degradation of an unsaturated polysulfide polymer [poly(2‐butene sulfide)] carried out by pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS). A unique phenomenon of exothermic degradation has been detected by differential thermal analysis and has been attributed to the energetics of the unsaturated polysulfide linkage during degradation. The thermal degradation products studied by Py–GC/MS indicate that the formation of sulfur‐containing products is more favored than the formation of non‐sulfur‐containing products. Furthermore, a comparative study of the thermal degradation of unsaturated and saturated polysulfide polymers has been conducted with thermogravimetry and Py–GC/MS analyses. These analyses have shown that the mechanisms of degradation of these polymers are different, and the lower number of pyrolysis products indicates a selective cleavage of the polymer during degradation in the saturated polysulfide polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 638–649, 2005     

Characterization and degradation of the poly(methylphenylsiloxane)–poly(methyl methacrylate) graft copolymer

Poly(methylphenylsiloxane)–poly(methyl methacrylate) graft copolymers (PSXE-g-PMMA) were prepared by condensation reaction of poly(methylphenylsiloxane)-containing epoxy resin (PSXE) with carboxyl-terminated poly(methyl methacrylate) (PMMA), and they were characterized by gel permeation chromatography (GPC), infrared (IR), and ²⁹Si and ¹³C nuclear magnetic resonance (NMR). The microstructure of the PSXE-g-PMMA graft copolymer was investigated by proton spin–spin relaxation T₂ measurements. The thermal stability and apparent activation energy for thermal degradation of these copolymers were studied by thermogravimetry and compared with unmodified PMMA. The incorporation of poly(methylphenylsiloxane) segments in graft copolymers improved thermal stability of PMMA and enhanced the activation energy for thermal degradation of PMMA. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2521–2530, 1998     

Synthesis,characterization, and properties of new thermally curable polyetheresters containing benzoxazine moieties in the main chain

High molecular weight polyetheresters (PEE) containing thermally curable benzoxazine units in the main chain have been synthesized. For this purpose, first the diol functional monomer is synthesized through the Mannich reaction of 4,4′‐isopropylidenediphenol (bisphenol A), formaldehyde, and 2‐(2‐aminoethoxy)ethanol. Polycondensation of the resulting benzoxazine dietherdiol with adipoyl chloride and terephthaloyl dichloride in the presence of triethyl amine yields the corresponding PEE with the molecular weights of 34.000 Da. The structures of the precursor diol monomer and the resulting PEEs are confirmed by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance spectroscopy (¹H‐NMR) analysis. Curing behavior of both the monomer and polymers has also been studied by differential scanning calorimetry (DSC). Flexible free standing transparent films of the PEEs are obtained by solvent casting from dichloromethane solution on Teflon plates. The films preserve shape and, to some extent, toughness after thermal curing between 140 and 220 °C. Thermal properties of the cured polymers are also investigated by thermogravimetric analysis (TGA). © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 414–420, 2008     

Base‐amplifying silicone resins with photobase‐generating side chains and their application to negative‐working photoresists

To accomplish high photosensitivity of resist systems including photobase generators, we have proposed the concept of base‐proliferation reactions that generate base molecules in a nonlinear manner by the action of a catalytic amount of base; however, excessive diffusion of generated base molecules is still a problem. We have designed novel functional silicone resins bearing both base‐amplifying units and photobase‐generating units, and synthesized resins with various composition ratios. The synthesized resins are decomposed autocatalytically after UV irradiation and subsequent heating at 100 °C, which indicates progression of base‐proliferation reactions. High photosensitivity (8.1 mJ cm^?2) was recorded, and it was found that the photosensitivity is about 490 times enhanced by replacing a base‐catalytic reaction system with the base‐proliferation reaction system. Furthermore, a 4 × 10 µm line‐and‐space pattern has been successfully fabricated using the silicone resin. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1205–1212