15 – Thermal Degradation

Thermal degradation begins to be important when polymers are processed and fabricated for use. The threshold temperature for breakdown determines the upper limit of temperature in fabrication and the volatile products of degradation must be known in order to guarantee the safety of workers. These same properties are relevant to the potential use of a polymeric material and, in the extreme case, to the hazards presented by the polymer in a fire situation. However, there are also some useful aspects of thermal degradation. Examination of the breakdown products from polymers is increasingly used as a method of analysis. In a limited number of cases, controlled thermal degradation is important in recycling of plastics waste and in the special case of carbon fibre production, degradative reactions are an essential part of the manufacturing process.

[1]  D. H. Richards,et al.  Thermal degradation of vinyl polymers I—Thermal degradation of polystyrene-poly(α-methylstyrene) mixtures , 1967 .

[2]  N. Grassie,et al.  Thermal degradation of bromine-containing polymers—I: Poly(2-bromoethyl methacrylate) , 1981 .

[3]  G. Camino,et al.  The rôle of chain ends in the thermal degradation of anionic polystyrene , 1982 .

[4]  N. Grassie.  The thermal degradation of polyvinyl acetate. I. Products and reaction mechanism at low temperatures , 1952 .

[5]  Daniel W. Brown,et al.  The Pyrolysis of Poly-α-methylstyrene , 1958 .

[6]  R. H. Boyd.  Theoretical Depolymerization Kinetics in Polymers Having an Initial , 1959 .

[7]  A. Guyot,et al.  Thermal degradation of graft copolymers of PVC prepared by mastication with styrene and methyl methacrylate, and of further PVC mixtures and vinyl chloride copolymers , 1971 .

[8]  M. Zulfiqar,et al.  Analysis of degradation products by thermal volatilization analysis at subambient temperatures , 1977 .

[9]  I. C. Mcneill,et al.  Thermal degradation of poly(vinyl bromide), vinyl bromide‐methyl methacrylate copolymers, and poly(vinyl bromide)‐poly(methyl methacrylate) blends , 1980 .

[10]  G. Geuskens,et al.  Kinetic study of anhydride formation during thermal degradation of isotactic and atactic polymethacrylic acid , 1971 .

[11]  J. Brandrup,et al.  On the Chromophore of Polyacrylonitrile. II. The Presence of Ketonic Groups in Polyacrylonitrile , 1968 .

[12]  I. C. Mcneill,et al.  Degradation studies of some polyesters and polycarbonates—1. Polylactide: General features of the degradation under programmed heating conditions , 1985 .

[13]  N. Grassie,et al.  Thermal degradation of polyether-urethanes: Part 2—Influence of the fire retardant, ammonium polyphosphate, on the thermal degradation of poly(ethylene glycol) , 1985 .

[14]  S. Straus,et al.  Pyrolysis of Anionic and Thermally Prepared Polystyrenes. , 1973, Journal of research of the National Bureau of Standards. Section A, Physics and chemistry.

[15]  M. Zulfiqar,et al.  Preparation and degradation of salts of poly(methacrylic acid)—Part II: Magnesium, calcium, strontium and barium salts , 1979 .

[16]  N. Grassie,et al.  Thermal degradation of bromine-containing polymers. Part 7—Poly(2,3-dibromopropyl methacrylate) and poly(2,3-dibromopropyl acrylate) , 1986 .

[17]  I. C. Mcneill,et al.  The thermal degradation of copolymers of methyl methacrylate with methacrylic acid , 1974 .

[18]  N. Grassie,et al.  Chemistry of high polymer degradation processes , 1956 .

[19]  W. Stevenson,et al.  The structure and stability of oxidised polybutadiene , 1985 .

[20]  W. W. Wright,et al.  Heat-resistant polymers : technologically useful materials , 1983 .

[21]  S. Straus,et al.  Pyrolysis of polyolefins , 1960 .

[22]  W. Hawkins.  Polymer Degradation and Stabilization , 1984 .

[23]  N. Grassie,et al.  The thermal degradation of polysiloxanes—I. Poly(dimethylsiloxane) , 1978 .

[24]  N. Grassie,et al.  Thermal degradation of copolymers of methyl methacrylate and n‐butyl acrylate. I. Thermal analysis , 1972 .

[25]  I. C. Mcneill.  Thermal volatilization analysis: A new method for the characterization of polymers and the study of polymer degradation , 1966 .

[26]  S. L. Madorsky,et al.  Pyrolysis of styrene, acrylate, and isoprene polymers in a vacuum , 1953 .

[27]  N. Grassie,et al.  Thermal degradation of poly(alkyl acrylates). I. Preliminary investigations , 1971 .

[28]  W. Schnabel.  Polymer Degradation: Principles and Practical Applications , 1981 .

[29]  G. M. Burnett,et al.  Dehydrochlorination of polymers—IV. Polyvinylidene chloride copolymers , 1968 .

[30]  V. Braun,et al.  Zum mechanismus der thermischen chlorwassmtoffabspaltung aus polyvinylchlorid. 3. Mitt. Über die länge der polyensequenzen in partiell dehydrohalogenierten poiyvinylchloriden, polyvinylbromiden und vinylchlorid‐copolymeren , 1966 .

[31]  G. G. Cameron,et al.  The thermal degradation of poly(methyl acrylate). Part II. The mechanism of chain breaking , 1967 .

[32]  N. Grassie,et al.  Thermal degradation of copolymers of methyl methacrylate and methyl acrylate. I. Products and general characteristics of the reaction , 1968 .

[33]  R. H. Boyd.  Theoretical depolymerization kinetics. IV. Effect of a volatile fraction on the degradation of an initial “most probable” polymer , 1967 .

[34]  I. C. Mcneill,et al.  The thermal degradation of copolymers of vinyl acetate with methyl methacrylate and other monomers , 1976 .

[35]  I. C. Mcneill,et al.  Degradation of polymer blends—Part XI. Blends of polystyrene with polyisoprene , 1980 .

[36]  I. C. Mcneill,et al.  The thermal degradation of poly(methyl vinyl ketone) and poly(methyl isopropenyl ketone) , 1971 .

[37]  I. C. Mcneill.  Polymer degradation and characterization by thermal volatilization analysis with differential condensation of products , 1970 .

[38]  N. Grassie,et al.  Thermal degradation of polyether-urethanes: Part 1—Thermal degradation of poly(ethylene glycols) used in the preparation of polyurethanes , 1984 .

[39]  G. G. Cameron,et al.  The thermal degradation of poly(methyl acrylate) V. Relative rates of crosslinking and chain scission , 1971 .

[40]  M. Asahina,et al.  On the Dehydrochlorination and the Stabilization of Polyvinyl Chloride , 1969 .

[41]  Alain Guyot,et al.  Recent developments in the thermal degradation of polystyrene—A review , 1986 .

[42]  N. Grassie,et al.  Thermal degradation of polymethacrylonitrile. Part II. The coloration reaction , 1958 .

[43]  I. C. Mcneill,et al.  The thermal degradation of polyisobutene , 1968 .

[44]  M. Zulfiqar,et al.  Preparation and degradation of salts of poly(methacrylic acid). I. Lithium, sodium, potassium, and caesium salts , 1978 .

[45]  G. G. Cameron,et al.  The thermal degradation of poly(benzyl acrylate) , 1968 .

[46]  M. Neǐman,et al.  The thermal degradation of polypropylene , 1961 .

[47]  P. C. Uden,et al.  Polymer reactions—Part VII: Thermal pyrolysis of polypropylene , 1980 .

[48]  W. Stevenson,et al.  Thermal degradation of styrene-butadiene diblock copolymer: Part 1—Characteristics of polystyrene and polybutadiene degradation , 1985 .

[49]  N. Grassie,et al.  Thermal degradation of vinyl chloride-vinyl acetate copolymers — I. Bulk degradation studies by thermal volatilization analysis , 1970 .

[50]  S. Bywater,et al.  Molecular weight distribution changes during the thermal breakdown of poly‐α‐methylstyrene , 1961 .

[51]  B. Dodson,et al.  Thermal degradation of chlorinated rubber: Evidence for an alternative cyclic structure for chlorinated rubber , 1974 .

[52]  I. C. Mcneill,et al.  The effect of zinc bromide on the thermal degradation of poly(methyl methacrylate): Part 2—Reaction products, structural changes and degradation mechanism , 1984 .

[53]  J. Wypych.  Polyvinyl chloride degradation , 1985 .

[54]  I. C. Mcneill,et al.  Degradation studies of some polyesters and polycarbonates: Part 4—Poly(ethylene oxalate) , 1986 .

[55]  G. M. Burnett,et al.  Dehydrochlorination of polymers—I. Polyvinylidene chloride , 1967 .

[56]  G. Camino,et al.  Thermal degradation of polymer - fire retardant mixtures. Part II: Mechanism of interaction in polypropylene - chlorinated paraffin mixtures , 1982 .

[57]  G. Zaikov,et al.  The reason for the low stability of poly (vinyl chloride) ― a review , 1986 .

[58]  D. Garozzo,et al.  Primary thermal fragmentation processes in poly(lactic acid) investigated by positive and negative chemical ionization mass spectrometry , 1986 .

[59]  I. C. Mcneill,et al.  Degradation of synthetic polymers: Application of some pyrolysis methods in an investigation of the degradation behaviour of ionomers containing methacrylate salt units , 1987 .

[60]  Hirotaro Kambe,et al.  Thermoanalytical Studies of the Thermal Stability of High Polymers. II. The Differential Thermal Analysis and Thermogravimetric Analysis of Some Polyethylenes , 1964 .

[61]  N. Grassie,et al.  Pyrolysis of polyacrylonitrile and related polymers—I. Thermal analysis of polyacrylonitrile , 1970 .

[62]  R. S. Roche,et al.  The thermal degradation of polyoxymethylene , 1968 .

[63]  I. C. Mcneill,et al.  Thermal degradation of mixtures of poly(methyl methacrylate) and silver acetate , 1978 .

[64]  I. C. Mcneill,et al.  Degradation studies of some polyesters and polycarbonates: 3—Polyglycollide , 1985 .

[65]  N. Grassie,et al.  Thermal degradation of polymethacrylonitrile. IV. Formation and decomposition of ketene‐imine structures , 1958 .

[66]  N. Grassie,et al.  The thermal decomposition of poly(t-butyl methacrylate) , 1960 .

[67]  J. Chien,et al.  Resist polymers: Part VII—Thermolysis of fluoroalkyl methacrylates , 1986 .

[68]  N. Grassie,et al.  The thermal degradation of polyvinyl compounds IV. The thermal degradation of the methyl methacrylate copolymers with glycol dimethacrylate and acrylonitrile , 1949, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[69]  H. Gilbert,et al.  Vinylidene Cyanide. III1 , 1954 .

[70]  H. Jellinek,et al.  Degradation of vinyl polymers , 1955 .

[71]  R. Conley.  Thermal stability of polymers , 1970 .

[72]  A. Guyot,et al.  Thermal degradation of graft copolymers of PVC with methacrylates, and comparisons with the behaviour of random copolymers and polymer mixtures , 1971 .

[73]  G. Camino,et al.  Mechanism of thermal degradation of urea-formaldehyde polycondensates , 1983 .

[74]  A. Whitehead,et al.  Thermal degradation of polymers. XV. Vacuum pyrolysis studies on poly(p-methoxystyrene) and poly(p-hydroxystyrene) , 1977 .

[75]  M. Guaita,et al.  Molecular mass changes in the thermal degradation of poly-α-methylstyrene , 1985 .

[76]  S. L. Madorsky,et al.  Thermal degradation of polymers as a function of molecular structure , 1954 .

[77]  Investigations of thermal elimination reactions of polymers by thermal volatilization analysis and ultraviolet spectroscopy , 1969 .

[78]  I. C. Mcneill,et al.  Degradation of polymer mixtures. IX. Blends of polystyrene with polybutadiene , 1978 .

[79]  N. Grassie,et al.  Thermal degradation of polymethacrylonitrile. Part V. The mechanism of the initiation step in coloration reactions , 1959 .

[80]  I. C. Mcneill,et al.  Degradation of polymer mixtures. VIII. Blends of poly(vinyl acetate) with poly(methyl methacrylate) , 1976 .

[81]  L. Costa,et al.  Changes in degree of polymerization in the thermal degradation of polystyrene , 1985 .

[82]  I. C. Mcneill,et al.  Degradation of polymer mixtures—II: Poly(vinyl chloride)-poly(methyl methacrylate) mixtures, studied by thermal volatilization analysis and other techniques. The effect of mixing on the thermal stability of each polymer and the general nature of their interaction , 1970 .

[83]  S. L. Madorsky.  Thermal Degradation of Organic Polymers , 1964 .

[84]  W. C. Geddes.  The thermal decomposition of polyvinylchloride—I. Kinetics of dehydrochlorination , 1967 .

[85]  G. Camino,et al.  The effect of the chemical structure of chain ends on the thermal degradation of polystyrene , 1986 .

[86]  I. C. Mcneill.  Thermal volatilization analysis of high polymers , 1967 .

[87]  G. G. Cameron,et al.  Thermal Degradation of Polystyrene. 3. A Reappraisal , 1978 .

[88]  J. Golden,et al.  Stability of Polycarbonate , 1969 .

[89]  C. Bamford,et al.  The thermal degradation of polyvinyl chloride , 1969 .

[90]  J. N. Hay,et al.  Thermal coloration and insolubilization in polyacrylonitrile , 1962 .

[91]  C. F. Cullis,et al.  The combustion of organic polymers , 1981 .

[92]  N. Grassie,et al.  Thermal Degradation of Blends of PVC with Other Polymers , 1978 .

[93]  M. Zulfiqar,et al.  Thermal degradation of ammonium polymethacrylate and polymethacrylamide , 1978 .

[94]  N. Grassie,et al.  The thermal degradation of copolymers of α-chloroacrylonitrile with styrene and methyl methacrylate , 1966 .

[95]  A. Michel,et al.  Structural defects in polyvinylchloride—I. Internal unsaturation as initiation sites for dehydrochlorination , 1981 .

[96]  Yoshio Tsuchiya,et al.  Thermal decomposition products of polypropylene , 1969 .

[97]  Y. Tsuchiya,et al.  Thermal decomposition products of polyisobutylene , 1969 .

[98]  M. Zulfiqar,et al.  Thermal degradation of zinc polymethacrylate and a zinc methacrylate/methyl methacrylate copolymer , 1984 .

[99]  S. A. Liebman,et al.  Thermal decomposition of poly(vinyl chloride) and chlorinated poly(vinyl chloride). I. ESR and TGA studies , 1971 .

[100]  G. Camino,et al.  Influence of the fire retardant ammonium polyphosphate on the thermal degradation of poly(methyl methacrylate) , 1978 .

[101]  N. Grassie,et al.  The thermal degradation of copolymers of styrene and methyl methacrylate , 1967 .

[102]  G. Camino,et al.  ‘Weak links’ in polystyrene , 1981 .