Preparation and degradation of head-to-head PVC

The course of the chlorination reaction of cis-1,4-polybutadiene is dependent on the choice of solvent. When methylene chloride is used, a pure addition reaction of chlorine leads to a polymer with the structure of head-to-head, tail-to-tail PVC. The thermal stability of the head-to-head PVC polymer has been studied by thermal volatilization analysis, thermogravimetry, and evolved gas analysis for hydrogen chloride, and the changes in the ultraviolet (UV) spectrum of the polymer during degradation have been investigated. The head-to-head polymer has a lower threshold temperature of degradation than normal PVC, but reaches its maximum rate of degradation at a higher temperature for powder samples of the polymer under programmed heating conditions. Blends of head-to-head PVC with poly(methyl methacrylate) have also been degraded, and the presence of the head-to-head polymers, like that of normal PVC, results in depolymerization of the PMMA as soon as the dehydrochlorination reaction commences. The mechanism of degradation of head-to-head PVC is discussed.     

Thermo-oxidative dehydrochlorination of rigid and plasticised poly(vinyl chloride)/poly(methyl methacrylate) blends

The aim of this work was to study the thermo-oxidative dehydrochlorination of rigid and plasticised poly(vinyl chloride)/poly(methyl methacrylate) blends. For that purpose, blends of variable compositions from 0 to 100 wt% were prepared in the presence (15, 30 and 50 wt%) and in the absence of diethyl-2-hexyl phthalate as plasticiser. Their miscibility was investigated by using differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). Their thermo-oxidative degradation at 180 ± 1 °C was studied and the amount of HCl released from PVC was measured by a continuous potentiometric method. Degraded samples were characterised, after purification, by FTIR spectroscopy and UV-visible spectroscopy. The results showed that the two polymers are miscible up to 60 wt% of poly(methyl methacrylate) (PMMA). This miscibility is due to a specific interaction of hydrogen bonding type between carbonyl groups (CO) of PMMA and hydrogen (CHCl) groups of PVC as shown by FTIR analysis. On the other hand, PMMA exerted a stabilizing effect on the thermal degradation of PVC by reducing the zip dehydrochlorination, leading to the formation of shorter polyenes.     

Thermal degradation of graft copolymers of PVC prepared by mastication with styrene and methyl methacrylate,and of further PVC mixtures and vinyl chloride copolymers

Graft copolymers prepared by mastication of PVC in the presence of styrene or of a styrene/ methyl methacrylate mixture, have been studied by thermogravimetry, estimation of hydrogen chloride, thermal volatilization analysis, and flash pyrolysis/g.l.c. The degradation behaviour of PVC/ polystyrene mixtures, vinyl chloride/styrene random copolymers, a random copolymer of methyl methacrylate and styrene, and PVC/poly-α-methylstyrene mixtures has also been studied. The graft copolymers resemble the PVC/methacrylate graft copolymers previously studied in showing retardation of the dehydrochlorination reaction, but contrast with them in yielding chain fragments but no monomer during HCl production. Some stabilization of the second component at higher temperatures is also found. PVC/polystyrene mixtures behave in the same way as the corresponding graft copolymers, but vinyl chloride/styrene copolymers show reduced stability towards both dehydrochlorination and monomer production compared with the homopolymers. PVC/poly-α-methylstyrene mixtures yield some monomer concurrently with HCl loss, and display marked retardation of the latter reaction. Stabilization of the second polymer at higher temperatures is again observed. Many of these results add further strong support to the view that chlorine atoms are involved as chain carriers in the thermal dehydrochlorination of PVC.     

Study of the miscibility and the thermal degradation of PVC/PMMA blends

The aim of this paper is to study the miscibility and the thermal degradation of PVC/PMMA blends. For that purpose, blends of variable compositions from 0 to 100 wt% were prepared with and without plasticizer. Their physico-chemical characterization was carried out by differential scanning calorimetric analysis (DSC) and Fourier transform infrared spectroscopy (FTIR). Their thermal degradation under nitrogen at 185°C was studied and the HCl evolved from PVC was measured by the pH method. Degraded samples were characterized, after purification, by FTIR and UV-visible spectroscopy. The DSC analysis showed polymer miscibility up to 60 wt% of PMMA. This miscibility is due to a specific interaction of hydrogen bonding type between carbonyl groups (C=O) of PMMA and hydrogen from (CHCl) groups of PVC as evidenced by FTIR analysis. On the other hand, it was found that PMMA exerted a stabilizing effect on the thermal degradation of PVC by reducing the zip dehydrochlorination and by leading to the formation of short polyenes.     

Thermal degradation studies in poly(vinyl chloride)/poly(methyl methacrylate) blends

The miscibility, morphology, and thermal properties of poly(vinyl chloride) (PVC) blends with different concentrations of poly(methyl methacylate) (PMMA) have been studied. The interaction between the phases was studied by FTIR and by measuring the glass transition temperature (T_g) of the blends using differential scanning calorimetry. Distribution of the phases at different compositions was studied through scanning electron microscopy. The FTIR and SEM results show little interaction and gross phase separation. The thermogravimetric studies on these blends were carried out under inert atmosphere from ambient to 800 °C at different heating rates varying from 2.5 to 20 °C/min. The thermal decomposition temperatures of the first and second stage of degradation in PVC in the presence of PMMA were higher than the pure. The stabilization effect on PVC was found most significant with 10 wt% PMMA content in the PVC matrix. These results agree with the isothermal degradation studies using dehydrochlorination and UV-vis spectroscopic results carried out on these blends. Using multiple heating rate kinetics the activation energies of the degradation process in PVC and its blends have been reported.     

Structure of reactively extruded rigid PVC/PMMA blends

A novel route for producing polymer blends by reactive extrusion is described, starting from poly (vinyl chloride)/methyl methacrylate (PVC/MMA) dry blend and successive polymerization of MMA in an extruder. Small angle X‐ray scattering (SAXS) measurements were applied to study the monomer's mode of penetration into the PVC particles and to characterize the supermolecular structure of the reactive poly(vinyl chloride)/poly(methyl methacrylate) (PVC/PMMA) blends obtained, as compared to the corresponding physical blends of similar composition. These measurements indicate that the monomer molecules can easily penetrate into the PVC sub‐primary particles, separating the PVC chains. Moreover, the increased mobility of the PVC chains enables formation of an ordered lamellar structure, with an average d‐spacing of 4.1 nm. The same characteristic lamellar structure is further detected upon compression molding or extrusion of PVC and PVC/PMMA blends. In this case the mobility of the PVC chains is enabled through thermal energy. Dynamic mechanical thermal analysis (DMTA) and SAXS measurements of reactive and physical PVC/PMMA blends indicate that miscibility occurs between the PVC and PMMA chains. The studied reactive PVC/PMMA blends are found to be miscible, while the physical PVC/PMMA blends are only partially miscible. It can be suggested that the miscible PMMA chains weaken dipole–dipole interactions between the PVC chains, leading to high mobility and resulting in an increased PVC crystallinity degree and decreased PVC glass transition temperature (T_g). These phenomena are shown in the physical PVC/PMMA blends and further emphasized in the reactive PVC/PMMA blends. Copyright © 2005 John Wiley & Sons, Ltd.     

Δχ effects on the miscibility of polymer blends

The Δχ effect on the miscibility of polymer blends prepared by solution-casting has been investigated using the mixture of poly(methyl methacrylate)(PMMA) with poly(vinyl acetate) (PVAc). The PMMA/PVAc blends have been prepared by casting from eleven different solutions. The Δχ effect of the solution–cast PMMA/PVAc blends was discussed in terms of Hansen's specified solubility parameters. It was found that the miscibility of the blends could be defined mainly by the solubility parameter contributed by the hydrogen–bonding of a solvent.     

Degradation of polymer mixtures. IV. Blends of poly(vinyl acetate) with poly(vinyl chloride) and other chlorine-containing polymers

The degradation of the binary polymer blends, poly(vinyl acetate)/poly(vinyl chloride), poly(vinyl acetate)/poly(vinylidene chloride) and poly(vinyl acetate)/polychloroprene has been studied by using thermal volatilization analysis, thermogravimetry, evolved gas analysis for hydrogen chloride and acetic acid, and spectroscopic methods. For the first two systems named, strong interaction occurs in the degrading blend, but the polychloroprene blends showed no indication of interaction. In the PVA/PVC and PVA/PVDC blends, hydrogen chloride from the chlorinated polymer causes substantial acceleration in the deacetylation of PVA. Acetic acid from PVA destabilizes PVC but has little effect in the case of PVDC because of the widely differing degradation temperatures of PVA and PVDC. The presence of hydrogen chloride during the degradation of PVA results in the formation of longer conjugated sequences, and the regression in sequence length at high extents of deacetylation found for PVA degraded alone is not observed.     

Thermal degradation of poly(vinyl bromide), vinyl bromide-methyl methacrylate copolymers,and poly(vinyl bromide)-poly(methyl methacrylate) blends

Degradation behavior has been compared for PVB, five VB-MMA copolymers which span the composition range, PMMA, and PVC by using thermogravimetry in dynamic nitrogen and thermal volatilization analysis (TVA) under vacuum for programmed heating at 10°C/min. Volatile products have been separated by subambient TVA and identified. PVB is substantially less stable than PVC but shows inmost respects analogous degradation behavior. The introduction of VB into the PMMA chain leads to intramolecular lactonization with release of methyl bromide at temperatures a little above 100°C; after this reaction is complete, however, the polymer is more stable toward volatilization than PMMA. Copolymers with moderate and high VB contents also lose hydrogen bromide. Carbon dioxide is a significant product at intermediate compositions. The variation of product distribution with copolymer composition is discussed in relation to the several reactions involved and comparisons are made with VC-MMA copolymers. PVB-PMMA blends snow some features of degradation behavior in common with the PVC-PMMA system but also very important differences. The effect of PVB is only to stabilize the PMMA; the mechanism is discussed. The role of PVB as an additive and VB as a comonomer for fire-retardant PMMA compositions is briefly considered in relation to earlier studies.     

The asymmetrical orientational behavior of compatible blends of PMMA and PVC

The orientation and relaxation behavior of compatible blends of poly(methyl methacrylate) (PMMA) and poly(vinyl chloride) (PVC) was investigated. The deformation was performed at 9 K above the glass transition temperature. Based on birefringence and IR-dichroic measurements, it was found that the orientation of PMMA is strongly increased in the blends as compared to pure PMMA at identical draw ratios.The orientation of PVC, on the other hand, is not changed by blending. The results are discussed in terms of friction coefficients and their enhancement by molecular interactions.Dedicated to Prof. E. W. Fischer on the occasion of his 665th birthday     

Poly(styrene-co-p-(hexafluoro-2-hydroxy-2-propyl)-styrene) blends with syndiotactic and/or isotactic poly(methyl methacrylate)

A modified polystyrene, poly(styrene-co-p-(hexafluoro-2-hydroxy-2-propyl)styrene) (FPS), was blended with syndiotactic and/or isotactic poly(methyl methacrylate) (PMMA) in toluene. Blends were prepared under different conditions to control the self-aggregation of the PMMA segments. The formation of hydrogen bonding and the attendant changes in the aggregation or crystallization of PMMA segments were determined in the solid state by means of FTIR and DSC. The results indicate that for the binary blends, the aggregation of PMMA segments is diminished by hydrogen bonding interaction with either s-PMMA or i-PMMA, and that the interaction is stronger with the s-PMMA blends. For the ternary blends, FPS/s-PMMA/i-PMMA, the preference for stereocomplexation in the system with hydrogen bonding may be attributed to the “kink-nucleated” mechanism, which needs relatively short chain lengths of PMMA segments. Regardless of the order of addition of the components, the formation of crystalline stereocomplexes of s- and i-PMMA could be readily detected. Therefore, the miscibility of the polymer blends is dependent on the competition between the self-aggregation of the s- or i-PMMA segments, stereocomplexation and the hydrogen bonding interaction of PMMA segments with FPS.     

Development and characterization of reactive extruded PVC/polyacrylate blends

This paper describes a method to obtain polymer blends by the absorption of a liquid solution of monomer, initiator, and a crosslinking agent in suspension type porous poly(vinyl chloride) (PVC) particles, forming a dry blend. These PVC/monomer dry blends are reactively polymerized in a twin‐screw extruder to obtain the in situ polymerization in a melt state of various blends: PVC/poly(methyl methacrylate) (PVC/PMMA), PVC/poly(vinyl acetate) (PVC/PVAc), PVC/poly(butyl acrylate) (PVC/PBA) and PVC/poly(ethylhexyl acrylate) (PVC/PEHA). Physical PVC/PMMA blends were produced, and the properties of those blends are compared to reactive blends of similar compositions. Owing to the high polymerization temperature (180°C), the polymers formed in this reactive polymerization process have low molecular weight. These short polymer chains plasticize the PVC phase reducing the melt viscosity, glass transition and the static modulus. Reactive blends of PVC/PMMA and PVC/PVAc are more compatible than the reactive PVC/PBA and PVC/PEHA blends. Reactive PVC/PMMA and PVC/PVAc blends are transparent, form single phase morphology, have single glass transition temperature (T_g), and show mechanical properties that are not inferior than that of neat PVC. Reactive PVC/PBA and PVC/PEHA blends are incompatible and two discrete phases are observed in each blend. However, those blends exhibit single glass transition owing to low content of the dispersed phase particles, which is probably too low to be detected by dynamic mechanical thermal analysis (DMTA) as a separate T_g value. The reactive PVC/PEHA show exceptional high elongation at break (～90%) owing to energy absorption optimized at this dispersed particle size (0.2–0.8 µm). Copyright © 2005 John Wiley & Sons, Ltd.     

DSC and p-V-T Study of PVC/PMMA Blends

Poly(vinyl chloride)/Poly(methyl methacrylate) — PVC/PMMA — blends were investigated by comparative p-V-T and differential scanning calorimetry (DSC) measurements. The study was concentrated on the glass transition range of the blends, and it was found that the blends are characterized by a single glass transition temperature suggesting miscibility of the blend components. It is shown that the glass temperature of the blends increases with both increasing heating rate and pressure. In parallel hereto one observes a decrease in the volume expansion coefficients, which is more accentuated for the polymeric melts than for the polymeric glasses. The dependence of the glass temperature on the composition of the polymer blends shows a sigmoidal behaviour which is due to the fact that positive deviations of the glass temperature from values predicted by additivity rules are observed in the high PVC concentration range, whereas in the high PMMA range negative deviations occur. This suggests a denser packing of the blends and thus a stronger interaction between the blend components in the high PVC concentration range. These packing differences increase with increasing pressure and decreasing heating rate and are generally more accentuated for the glass temperatures evaluated from p-V-T measurements.This revised version was published online in November 2005 with corrections to the Cover Date.     

Understanding the Miscibility and Morphology of Poly(methyl methacrylate) and Styrenic Copolymer Blends of Tunable Domain Sizes

In the present study, we have investigated the miscibility, morphology and mechanical behavior of poly(methyl methacrylate) (PMMA) blends with a series of poly(styrene-co-maleic anhydride) (SMA) copolymers containing varying amounts of maleic anhydride (MA) content (from 8 to 26%). The experimental findings have been substantiated by the modeling studies to gain fundamental understanding of the observed phenomena with respect to the miscibility of the PMMA and SMA blends of a given MA content. The morphological differences, molecular weights, domain sizes and mechanical behavior of the blends at a given ratio of PMMA and copolymers have been investigated and a correlation has been made between the morphological understanding to the molecular weights and mechanical properties. The results indicate that the PMMA/SMA blends are miscible only at a certain MA content providing transparent PMMA/SMA blends without affecting any of the enabling properties of PMMA that are of commercial interest through a facile melt mixing process. The surface hardness and % recovery (nano-indentation) of these blends were evaluated as well to gain fundamental understanding of the surface characteristics and mechanicals of the blends.     

The effect of zinc bromide on the thermal degradation of poly(methyl methacrylate): Part 1—Thermal analysis studies and general nature of the interaction

The degradation behaviour of several different blends of poly(methyl methacrylate) (PMMA) and zinc bromide, under programmed heating to 500°C, has been studied using thermal volatilisation analysis and spectroscopic investigation of the volatile degradation products. The samples were in the form of films cast from a common solution of the components in acetone; these films are found to be transparent, indicating compatibility of PMMA and ZnBr₂. From studies of the visible spectra of cobalt bromide, PMMA and blends of PMMA with CoBr₂, it has been argued that complex formation occurs between the polymer and the transition metal halides: structures are suggested.When degraded alone, PMMA gives only monomer as the degradation product. In the blends with ZnBr₂ (or with CoBr₂), the polymer becomes considerably less stable and the pattern of degradation becomes very complex, with a range of volatile products, of which methyl bromide, carbon dioxide and methanol are the major constituents; carbon monoxide and methane are also formed. It is proposed that complex formation facilitates the release of methyl bromide as the first stage of breakdown, with the formation of zinc methacrylate units in the polymer chain; depolymerisation is prevented or severely inhibited, depending on the amount of ZnBr₂ present.     

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     

PS-b-PMMA对PVC/SBS共混体系界面结构的影响

在两种不相容的聚合物组成的共混体系中加入增容剂，可以显著提高共混体系的力学性能．目前的理论解释是嵌段共聚物在不相容的聚合物间形成界面层，通过降低组分间的界面张力、增强界面粘接力达到增容目的［‘－‘1．但是这一假设缺乏直接的实验证据．本文利用透射电子显微镜，     

Miscible blends of amorphous polymers

Thirty-five polymethacrylate/chlorinated polymer blends were investigated by differential scanning calorimetry. Poly(ethyl), poly(n-propyl), poly(n-butyl), and poly(n-amyl methacrylate)s were found to be miscible with poly(vinyl chloride) (PVC), chlorinated PVC, and Saran, but immiscible with a chlorinated polyethylene containing 48% chlorine. Poly(methyl) (PMMA), poly(n-hexyl) (PHMA), and poly(n-lauryl methacrylate)s were found to be immiscible with the same chlorinated polymers, except the PMMA/PVC, PMMA/Saran, and PHMA/Saran blends, which were miscible. A high chlorine content of the chlorinated polymer and an optimum CH₂/COO ratio of the polymethacrylate are required to obtain miscibility. However, poly(methyl), poly(ethyl), poly(n-butyl), and poly(n-octadecyl acrylate)s were found to be immiscible with the same chlorinated polymers, except with Saran, indicating a much greater miscibility of the polymethacrylates with the chlorinated polymers as compared with the polyacrylates.     

Cyclopentadienylation of PVC: Characterization and thermal and thermooxidative degradation studies

PVC has been cyclopentadienylated by two conventional basic, LiCp and NaCp, and a new acidic, Me₂CpAl, cyclopentadienylating agent. PVCs treated with basic cyclopentadienylating agents undergo severe random dehydrochlorination and exhibit a significant decrease in thermal and thermooxidative stability. In contrast, according to ozonization and degradation experiments, Me₂CpAl does not cause dehydrochlorination during cyclopentadienylation. The thermal stability of PVC treated with relatively high concentrations of Me₂CpAl and Me₃Al at 25°C markedly increases due to substitution of labile chlorines in PVC with methyl groups. Initial thermal dehydrochlorination behavior of virgin PVC and samples treated with Me₂CpAl at ?30°C are similar. In contrast, thermooxidative stability decreases on Me₂CpAl treatment at ?30°C; this is attributed to ease of oxidation of pendant cyclopentadienyl groups; that is, the formation of peroxy radicals that may initiate dehydrochlorination by attacking unchanged repeat units in PVC. Acceleration of thermal dehydrochlorination disappears and the length of polyene sequences is reduced on Me₂CpAl and Me₃Al treatment. These observations are attributed to differences in rates of protonation-deprotonation; that is, rates of reinitation of zipping of treated and untreated PVCs during thermal degration. The effect of traces of aluminum residues on degradation of modified PVCs, however, cannot be neglected.     

Natural weathering,photo and thermal degradation of the two-phase system poly(vinyl chloride) and poly(isobutylene)

Natural weathering, photo-oxidative and thermo-oxidative degradation have been compared for poly(vinyl chloride) (PVC) and poly(isobutylene) (PIB) and nine of their blends covering the entire composition range. The degradation techniques used include heating in an air oven at 100°, u.v. irradiation and natural weathering. Studies on the morphology of the blends show that the state and mode of dispersion of the elastomer in films of the blend are influenced by composition. PIB is substantially less stable than PVC and does not act as a good modifier for PVC in freshly prepared samples. Considerably improved mechanical properties were obtained when the polyblends were partially degraded presumably because of the interactions between the polymers. The changes in the chemical properties were monitored by i.r. measurements. The presence of PIB in PVC up to 20% gave optimum stabilization to PVC whereas small amounts of PVC in PIB destabilized PIB considerably. The presence of PIB in a PVC-PIB blend leads to considerable suppression of dehydrochlorination at 100°. The blends became more stable than the homopolymers. The effect of PIB is chiefly to stabilize PVC; a mechanism is proposed. Equations have been developed to allow evaluation of the role of PIB as an effective stabilizer for PVC.