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Abstract  

The non-oxidative thermal degradation of poly (di-2-chloroethyl itaconate) (PD2CEI) was studied by TG and by analysing the thermal products. The major processes occurring during thermal analysis are crosslinking, depolymerisation and carbonisation. The thermal degradation activation energy increased with increasing sample mass loss. The thermal degradation of PD2CEI was compared to that of the structurally similar poly(2-chloroethyl methacrylate) (P2CMA).

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Abstract  

The thermal stability of poly(methyl methacrylate) (PMMA) photopolymerised using colloidal cadmium sulphide as the photoinitiator was studied by thermogravimetry (TG) and differential TG (DTG). The thermal stability of the CdS initiated PMMA was greater than that of conventional radically polymerised PMMA and approached that of anionically prepared PMMA. The DTG curve of the CdS initiated PMMA was a composite of four peaks, three of which correspond to the three peaks observed in the DTG curve of standard radically prepared PMMA. It is suggested that the additional peak arises from a new mode of depolymerisation initiation, that is, from chain end unsaturation introduced into the polymer chain during polymerisation initiation with the colloidal CdS.

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Abstract  

The free radical copolymerization of phenyl methacrylate (PhMA) witho-methylphenyl-methacrylate(o-MPhMA) ando-ethylphenyl methacrylate (o-EPhMA) was carried out and the enthalpies of copolymerization, overall rate constants and copolymerization parameters were determined for different molar ratios of comonomers in the temperature range 353–373 K.

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Abstract  

Glass transition temperatures of blends of (1) poly-(phenyl methacrylate) and poly(2,3-xylenyl methacrylate), (2) poly-(phenyl methacrylate) and poly(2,6-xylenyl methacrylates and (3) poly-(2,3-xylenyl-) and poly(2,6-xylenyl methacrylate) were measured. The data obtained suggest the existance of compatibility for blends of poly(xylenyl methacrylates) mentioned and incompatibility for both poly(phenyl methacrylate)/poly(xylenyl methacrylate) systems.

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The non-oxidative thermal degradation kinetics of poly(di-n-alkyl itaconates), ranging from the methyl to then-octyl derivatives, were studied by non-isothermal and isothermal TG. The thermal degradation activation energy and characteristic mass loss temperatures were found to decrease with increasing substituent size. The shapes of the DTG curves were dependent on the size of the alkyl substituent. The different DTG maxima were ascribed to various modes of initiation of depolymerisation. The thermal stability of poly(di-n-hexyl itaconate) was found to be independent of the initial molar mass of the sample in the range ofM w from 104 to 107 g/mol.

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Journal of Thermal Analysis and Calorimetry
Authors:
L. Katsikas
,
K. Jeremic
,
S. Jovanovic
,
J. Velickovic
, and
I. Popovic

Abstract  

The effect of molar mass and, in the case of dextran, of the degree of branching on the thermal degradation kinetics of dextran and pullulan was studied in the presence and absence of oxygen. Although the initial mass loss of the dextran samples occurred at higher temperatures than that of the pullulan samples, the overall thermal degradation activation energies were lower for dextran than for pullulan. In the case of dextran the thermal stability was found to decrease with molar mass and degree of branching. The molar mass of pullulan, in the range of 104 to 105 g/mol, appeared to have no significant influence on the thermal characteristics of the samples.

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Journal of Thermal Analysis and Calorimetry
Authors:
J. M. Filipovic
,
D. M. Petrovic-Dakov
,
Lj. P. Vrhovac
, and
J. S. Velickovic

The course and kinetics of free radical polymerization in bulk ofp-alkylphenyl methacrylates with AIBN initiator were studied by DSC, in the temperature range 348–373 K. The enthalpy of polymerization, the residual monomer content, as well as the overall reaction rate constants and the activation energies were determined. The similar values of the overall rate constants indicate that the relatively small alkyl substituents inp-position of the phenyl ring affect the polymerization rate to a very small, if any, extent.

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Poly(dialkoxyethyl itaconates)

II. The thermal degradation of some poly(dialkoxyethyl itaconates)

Journal of Thermal Analysis and Calorimetry
Authors:
L. Katsikas
,
T. A. Djakov
,
J. M. Filipović
,
J. S. Veličković
, and
I. G. Popovic

The oxidative and non-oxidative degradation of poly(di-methoxy-), poly(di-ethoxy-), poly(di-iso-propoxy-) and poly(di-n-butoxyethyl itaconate) were investigated by thermogravimetry. Characteristic degradation temperatures and apparent activation energies of degradation were determined for the non-oxidative degradation of all the investigated polymers. It was not possible to determine these characteristics in the presence of oxygen as the degradation was accompanied by a secondary exothermic reaction. Based on examination of the monomers, it is supposed that the exothermic reaction is a repolymerisation of the monomers released during the earlier stages of polymer degradation.

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The kinetics of the AIBN-initiated free radical bulk polymerization of fiveo-alkylphenyl methacrylates was studied by means of DSC in the temperature range 353–373 K, and the enthalpy of polymerization, the overall reaction rate constant and the activation energy were determined. The results were compared with those published recently on correspondingp-alkylaryl methacrylates. All measured reaction rate constants were found to increase with increasing temperature and to decrease with increasingo-alkyl substituent mass and size. It was shown thato-substituents influence the rates of polymerization to a greater extent thanp-substituents. At about 373 K, all differences in rate, most probably resulting from steric hindrance caused by the alkyl groups, disappear in both series, a phenomenon earlier observed for dimethyl phenyl methacrylates.

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