Thermal Degradation of Poly(Vinyl Chloride)/Polyaniline Conducting Blends

A series of blends of poly(vinyl chloride) (PVC) and polyaniline (PANI) was prepared by solution casting and investigated by methods of thermal analysis, namely thermogravimetric analysis (TG), coupled with Fourier transform infrared spectroscopy (TG-FT/IR) and differential scanning calorimetry (DSC). It was found that the thermal stability of this polymer system depends on the composition of blend; the main product of prevailing PVC decomposition process — hydrogen chloride — seems to play specific role during degradation since it can react with PANI structures, characterized by different protonation degree. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal Degradation Behavior of Vinyl Ketone Polymers and Copolymers with Styrene

Thermal degradation behavior of six alkyl vinyl ketone (RVK) polymers and copolymers with styrene was investigated by means of infrared spectrometry (IR), thermogravimetry (TG), derivative TG (DTG), and differential scanning calorimetry (DSC). The observed TG curves of the RVK polymers changed with both structure of their substituents and initiators used, and the temperature of the beginning of weight loss for the radical polymers increased in the order: poly(methyl isopro-penyl ketone) < poly(methyl vinyl ketone) < poly(ethyl vinyl ketone) < poly(isopropyl vinyl ketone) < poly(tert-butyl vinyl ketone). From the infrared spectral determination of thermally degraded polymers, the formation of a cyclized structure was observed. It was also found from the results of thermal degradation of the RVK copolymers with styrene at 210° C that the formation of such a cyclized unit tended to increase in the order: tert-butyl vinyl ketone < isopropyl vinyl ketone < ethyl vinyl ketone < methyl vinyl ketone.     

Thermal Behavior of Bismaleimide-Amine/Vinyl Ester Resin-Styrene Blends

Abstract

Curing of 4,4′-bismaleimido-diphenyl methane-4,4′ -diaminodi-phenyl methane (1:0.3 molar ratios) (BM-A) was carried out in the presence of vinyl ester-styrene resin. The BM-A could be cured at lower temperatures. The char yields of the cured resins depended on the percentage of bismaleimide-amine in the blend.     

Thermal Degradation of Blends of PVC with Other Polymers

The thermal degradation behavior of blends of polyvinyl chloride) with polyacrylonitrile, poly(n-butyl methacrylate), poly-acrylamide, poly(N-butyl methacrylamide) and poly(methyl acrylate) is discussed, and the results for these blends and five other binary polyblends containing PVC previously studied are compared. The various types of interactions which can occur in these heterogeneous systems are considered, and the mechanisms of degradation are compared with those of each polymer when degraded alone. The most important interactive effects result when a small reactive species produced in the degradation of one of the two polymers in the blend diffuses into the domains of the other polymer in the two-phase system and reacts with that polymer.     

TG/FT-IR Studies of Poly(Vinyl Chloride) Blends

Thermogravimetry coupled with Fourier transform infrared spectroscopy (TG/FT-IR) was used to investigate the stabilizing action of 3-(2,4-dibromophenylazo)-9-(2,3-epoxypropane)carbazole on the degradation of poly(vinyl chloride) (PVC). It was found that this secondary stabilizer increases the initial temperature of hydrogen chloride evolution (the main process responsible for PVC decomposition), thereby allowing its application for novel PVC systems with enhanced thermal stability. The application of TG/FT-IR technique for study of the thermal properties of polymeric materials offers additional characterization options in comparison with thermogravimetry, if used alone. This revised version was published online in July 2006 with corrections to the Cover Date.     

聚β—羟基丁酸酯／聚醋酸乙烯酯共混体系的相容性与结晶行为

研究了制样过程聚β－羟基丁酸酯／聚醋酸乙烯酯共混体系的相容性和结晶行为的影响。ＤＳＣ、ＳＡＸＳ、ＰＯＭ等实验结果表明，ＰＨＢ／ＰＶＡｃ共混物经溶液成膜后处于分相的状态，ＰＶＡｃ对ＰＨＢ的结晶能力影响不大；而经融处理后，ＰＨＢ／ＰＶＡｃ共混物则处于相容的均相状态，随ＰＶＡｃ的含量含量的增加。     

High-Molecular-Weight Compounds and Related Materials Cross-Linking of Macrochains in Thermal Degradation of Poly(Vinyl Chloride)

Macrochain cross-linking in thermal degradation of PVC was studied. The onset time of gelation was determined as a function of the content of oxoallyl groups in the polymer.     

Polydispersity Effects on the Demixing Behavior of Poly(Vinyl Methyl Ether)/Polystyrene Blends

Phase equilibrium calculations for solutions or mixtures of synthetic polymers become considerably more difficult when there is polydispersity of the polymers. To simplify the calculations, polydispersity is often neglected in the calculations or accounted for in a summary way only, and often only relatively simple free energy relations are applied. For example, Halary et al. published experimental demixing data on poly(vinyl methyl ether)/polystyrene blends. In evaluating the data the following assumptions were made: 1) the minimum of the demixing curve equals the critical point, 2) the X-parameter is independent of concentration and molecular weight, 3) the polydispersity may be roughly taken into account by using the formulas for monodisperse polymers and using the weight-average molecular weight. Continuous thermodynamics proves to be a suitable method to overcome the difficulties caused by polydispersity. Therefore, this method permits one to obtain detailed information on the phase equilibria in polymer solutions and in polymer blends in a relatively easy way. To show this, the data of Halary et al. are reanalyzed by means of continuous thermodynamics. In this way, more profound knowledge may be obtained from the experimental material, e.g., a more precise determination of the critical point and a more correct location of the spinodal.     

Thermal Degradation and Fire Behavior of High Performance Polymers

Abstract

High performance and high temperature polymers are a class of polymeric materials exhibiting high thermal stability and their resistance to fire makes them valuable assets for many applications. Those applications include as typical examples high temperature gas separation membranes, automotive and aerospace industry as well as the construction industry. The high performance polymers have been synthesized since the early 1960s, and have developed rapidly over the past few decades. Most high performance polymers comprise a highly aromatic backbone, linear chains, and strong inter-chain interactions. This review deals mostly with commercial polymeric materials. Studies regarding their thermal behavior, degradation mechanism and their reaction to fire have been synthetically combined in order to bring out potential insight concerning the effect of the thermal decomposition and thermal behavior on the fire properties of those polymers.     

Ultrasonic Degradation and Copolymerization of Poly (Vinyl Alcohol) with Acrylonitrile

The ultrasonic degradation of poly(vinyl alcohol) (PVA) in aqueous solution and copolymerization of PVA with acrylonitrile (AN) were studied. It is confirmed that the rate of degradation of PVA follows the kinetic equation suggested by Baramboim. Both water-soluble and water-insoluble copolymer can be obtained by changing the irradiation time or the amount of AN added to the aqueous solution of PVA. The structure of the copolymer was identified by IR, MS, PGC, and x-ray diffraction. The copolymer prepared is mainly a block one. By irradiating 2% PVA/AN (1/1.6, w/w) at 20 ± 1°C and 21. 5 kHz with 490 W for 28 min, the yield of water-soluble copolymer is 25.49%, the AN content in which is 13.98%. After 100 min, with the weight ratio between PVA and AN 1/4, the yield of the water-insoluble copolymer amounted to 296.01%, the AN content in which is 75.56%.     

IR Laser‐Induced Degradation of Poly(vinyl acetate): Novel Thermal Reactions in Solid Polymers

Summary: Pulsed‐IR laser‐induced decomposition of poly(vinyl acetate) (PVAC) differs remarkably from its conventional pyrolysis, which results in the formation of acetic acid and non‐polar carbonaceous residue. In contrast, the products in the former case are (i) vinyl acetate (low energy channel), (ii) products of cleavage in the acetate group, and (iii) an ablatively deposited polar polymeric film containing roughly half of the acetoxy groups initially present.

Schematic of the different routes of poly(vinyl acetate) degradation.     

Dynamic and Isothermal Thermogravimetric Degradation of Poly(vinyl Chloride)/Chlorinated Poly(ethylene) Blends

The thermal degradation of poly(vinyl chloride)/chlorinated poly(ethylene) (PVC/CPE) blends of different compositions was investigated by means of dynamic and isothermal thermogravimetric analysis in flowing atmosphere of nitrogen. Kinetic parameters (the apparent activation energy E, and pre-exponential factor Z) were calculated after Flynn-Wall-Ozawa method for the first stage of dynamic degradation of PVC/CPE blends, and after Flynn method for the isothermal degradation. In both cases, there is the compensation dependence between the values E and logZ. The values of compensation ratios as well as the characteristics of TG and DTG curves, confirm the stabilizing effect of CPE on PVC dehydrochlorination. This revised version was published online in July 2006 with corrections to the Cover Date.     

Sodium Alginate and Poly(ethylene glycol) Blends: Thermal and Morphological Behaviors

Sodium alginate (SA) was blended with varying amounts of poly(ethylene glycol) (PEG) viz., 10, 20, 30, 40 and 50 wt % by using water as a solvent. The obtained SA/PEG blends have been characterized for thermal behavior by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) and surface morphology by scanning electron microscopic (SEM) methods. DSC analysis indicates the increase in glass transition temperature (T_g) of the blends with an increase in PEG content in the blend, which is due to chain entanglement. TGA results reveal the enhancement of thermal stability of SA/PEG blends in terms of the onset of degradation and percentage of weight loss. SEM photomicrographs shows the two phase morphology. This result indicates the immiscible nature of the SA/PEG blends.     

Haloaldehyde Polymers. XIX. Degradation Behavior of Chloral Polymers

Thermal stability of samples of polychloral prepared with different initiators and treated with various endcapping agents was studied using differential thermogravimetric analysis (DTG). Four temperature regions at which maxima of DTG curves occur were identified. On the basis of the known mechanism of initiation and the possible mechanism of termination, the structures of both initial and terminal endgroups of individual polychloral samples were elucidated which enabled the identification of the specific temperature region of thermal degradation of polychloral molecules having a specific type of endgroup. These results were confirmed by studies of the DTG curves of chloral-isocyanate copolymers containing stable terminal fragments with a high content of urethane linkages.     

Synthesis and Characterization of a Branched Poly(Methacrylamide): Thermal Stability and Molecular Simulation Studies of Their Blends With Vinylic Polymers

The synthesis of a poly(diethylaminoethyl methacrylamide) (BP), based on a lineal methacrylamide with diethylaminoethyl branches was carried out. Thermal behavior was studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Relatively high thermal stability is found. Blends with poly(methylmethacrylate) (PMMA), poly(acrylic acid) (PAA) and poly(monomethyl itaconate) (PMMI) were prepared. Their thermal properties in blends were studied together with miscibility, in order to improve thermal properties of vinylic polymer blends. An increase of thermal stability was found for certain blend compositions. By FTIR analysis, higher band displacements were found for low BP compositions. AFM and molecular simulation analysis were carried out in order to elucidate the structural origin leading to thermal stability and miscibility increases. Hydrophobic interactions among methyl end groups of BP and methylene groups of vinylic polymers should be the responsible of miscibility and thermal stability increases.     

Thermal Behavior of Poly（trimethylene-co-ethylene terephthalate）

Poly (trimethylene-co-ethylene terephthalate) with various compositions of diol has been synthesized. The crystallization of copolyesters with high comonomer content was observed by both wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). It was found that the copolyesters become less crystallizable with the involvement of the comonomer, the crystals of crystallizable copolyesters come from PIT or PET homopolymers. The glass transition temperature (Tg) of the copolyester increases with increasing PET component in the copolyester, and the relationship between Tg and composition obey both Fox equation and additiv elaw, the former is better in describing this relationship.     

聚氯乙烯和EVA树脂共混体系相容性的研究

用扭摆分析研究了EVA树脂和PVC共混体系中,VA含量和共混物组成对其相容性的影响.共混的两组分的分子间相互作用对其相容性有关键的影响.用FTIR测定羰基伸缩振动谱带的位移,可表征EVA-PVC分子链间的相互作用.     

Polymeric Matrix Nanocomposites: Influence of Cadmium Sulfide Nanostructure on the Thermal Degradation of Poly(Vinyl Alcohol) and Cellulose Acetate

In this work cadmium sulfide-thioglycolic acid (CdS-Organic) nanostructures were added to the poly(vinyl alcohol) and cellulose acetate polymeric matrixes. The influence of CdS-Organic (CdS-Org) content on the thermal degradation of polymeric matrixes was studied using thermogravimetric analysis. Thermal decomposition of the nanocomposites shifted towards higher temperature in the presence of the CdS-Org nanostructures. Nanostructures were characterized by scanning electron microscopy, atomic force microscopy, Ultraviolet–Visible and Fourier transform infrared spectroscopy.