David D. Jiang

TGA/FTIR studies on the thermal degradation of some polymeric sulfonic and phosphonic acids and their sodium salts

The thermal degradation of poly(vinyl sulfonic acid) and its sodium salt, poly(4-styrenesulfonic acid) and its sodium salt, and poly(vinylphosphonic acid) was studied by a combination of techniques, including TGA/FTIR, to identify the volatile products which were evolved during the degradation as well as analysis of the residues which were obtained in order to propose a mechanism for the degradation. The motivation for the work was to attempt to identify new monomers which could be graft copolymerized onto a polymer in order to improve the thermal stability of that polymer.

Poly(methyl methacrylate), polypropylene and polyethylene nanocomposite formation by melt blending using novel polymerically-modified clays

Two new organically-modified clays that contain an oligomeric styrene or methacrylate have been prepared and used to produce nanocomposites of poly(methyl methacryate), polypropylene and polyethylene. Intercalated nanocomposites and, in some cases, exfoliated or mixed intercalated/exfoliated nanocomposites of all of these polymers have been produced by melt blending in a Brabender mixer. The use of the styrene-containing clay permits the direct blending of the clay with polypropylene, without the usual need for maleation, to produce the nanocomposites. The systems have all been characterized by X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, cone calorimetry and the measurement of mechanical properties. These novel new clays open new opportunities for melt blending of polymers with clays to obtain nanocomposites with important properties.

Novel polymerically-modified clays permit the preparation of intercalated and exfoliated nanocomposites of styrene and its copolymers by melt blending

Abstract Two new organically-modified clays have been made and used to produce nanocomposites of polystyrene, high impact polystyrene and acrylonitrile–butadiene–styrene terploymer. At a minimum, intercalated nanocomposites of all of these polymers have been produced by melt blending in a Brabender mixer and, in some cases, exfoliated nanocomposites have been obtained. The systems have all been characterized by X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, cone calorimetry and the measurement of mechanical properties. These novel new clays open new opportunities for melt blending of polymers with clays to obtain nanocomposites with important properties.

Thermal Degradation of Polystyrene, Poly(1,4-butadiene) and Copolymers of Styrene and 1,4-butadiene Irradiated Under Air or Argon with 60Co-γ-rays

Abstract 60 Co- γ -irradiated samples of polystyrene (PSt), poly(1,4-butadiene), (PBD), and two poly(styrene-co-butadiene)s containing 25 and 75% BD were subjected to thermogravimetric analysis (TGA), in the presence and absence of O 2 . In the case of PSt the irradiation caused a significant shift in T onset , the onset temperature for mass loss, to higher temperatures, whereas in the cases of the BD-containing polymers irradiation caused a decrease in T onset (oxic irradiation) or had little or no effect on T onset (anoxic irradiation). The amount of non-volatile residue formed in the cases of BD-containing polymers was augmented by γ -irradiation. The improved thermal stability of PSt is attributed to radiation-generated unsaturations acting as depolymerization retardants and/or agents in thermal crosslinking. Radiation-induced crosslinks do not affect the thermal behavior of PSt. In the cases of BD-containing polymers the thermal behavior is predominated by reactions of the carbon–carbon double bonds (crosslinking and cyclization). Radiation-induced chemical alterations, therefore, play a minor role during the thermal decomposition.

Thermal degradation of cross-linked polyisoprene and polychloroprene

Polyisoprene and polychloroprene have been cross-linked either in solution or in solid state using free radical initiators. In the comparable experimental conditions higher cross-linking density was observed in the solid state process. Independent of the cross-linking method, polychloroprene tended to give a higher gel content and cross-link density than does polyisoprene. Infrared characterization of the cross-linked materials showed cis-trans isomerization occurred in the polyisoprene initiated by benzoyl peroxide, whereas no isomerization was found in the samples initiated by dicumyl peroxide. Polyisoprene does not cross-link by heating in a thermal analyzer, whereas polychloroprene easily undergoes cross-linking in such conditions. Infrared spectroscopy showed that in the case of polyisoprene, rearrangements occur upon heating which lead to the formation of terminal double bonds, while polychloroprene loses hydrogen chlorine which leads to a conjugated structure. There is apparently some enhancement of the thermal and thermal oxidative stability of polyisoprene because of the cross-linking. Cross-linked polychloroprene is less thermally stable than the virgin polymer. Cross-linking promotes polymers charring in the main step of weight loss in air, which leads to enhanced transitory char.

Graft Copolymerization of Methacrylic Acid, Acrylic Acid and Methyl Acrylate onto Styrene–Butadiene Block Copolymer

Abstract Methyl acrylate, methacrylic acid, and acrylic acid have been graft copolymerized onto styrene–butadiene block copolymer. All three monomers react through the macroradical interacting with the double bond of butadiene. The site of reaction has been established by infrared spectroscopy. For methyl acrylate every unit of the styrene–butadiene block copolymer is grafted but only a small fraction is grafted when the acids are used. The difference apparently lies in the fact that the reaction with the ester is homogeneous while with the acids the reactions are heterogeneous.

Chemical initiation of graft copolymerization of methyl methacrylate onto styrene–butadiene block copolymer

When a solution containing both styrene–butadiene block copolymer (SBS) and methyl methacrylate is treated with an initiator both homopolymerization of the methyl methacrylate and graft copolymerization of the methyl methacrylate onto the SBS occur. The amount of graft copolymerization depends upon the time and temperature of the reaction, the concentrations of all species, and the identity of the solvent and initiator. The combination of benzoyl peroxide in chloroform gives the highest graft yield and the reaction occurs by removal of an allylic hydrogen from the SBS by the initiator radical and subsequent addition of monomer units to that site; there is a significant solvent effect. Both AIBN and BPO function by the removal of an allylic hydrogen atom from SBS; BPO is able to effect this reaction relatively easily while AIBN can remove the hydrogen atom only with great difficulty and to a limited extent.

Cross-linking of polystyrene by Friedel–Crafts chemistry to improve thermal stability

Abstract Copolymers which contain either alcohol or chloride functionalized polystyrene units have been prepared and they participate in Friedel–Crafts chemistry to give cross-linked polymers by the evolution of either hydrogen chloride or water. Proof of cross-linking comes from the identification of the evolved gas, the insolubility of the product, and the thermal resistance of the newly formed polymer. The onset temperature for the degradation is raised by about 100°C relative to that of polystyrene and the fraction which is not volatile at 800°C ranges from 10% for the alcohol copolymers to 20% for the chloride copolymers.

Further Studies on Fire Retardant Polystyrene by Friedel–Crafts Chemistry

Abstract The combination of a copolymer of 4-vinylbenzyl alcohol and styrene with 2-ethylhexyldiphenylphosphate (DPP) and with metal chlorides has been studied by TGA, radiative gasification, Cone Calorimetry, and oxygen index measurements. Evidence is presented in support of a cross-linking reaction with the additives and the copolymer, which proceeds through a Friedel–Crafts mechanism. This approach reduces the peak heat release rate (HRR) by 60% as measured in the Cone Calorimeter. There is a significant reduction in the mass loss rate during the thermal degradation, and evidence of char formation is observed in the radiative gasification experiments.