Copolymerization of vinyl chloride with 1-olefins. Part IV. Investigation of rheological and mechanical properties of copolymers

Copolymers of vinyl chloride with propene, 1-butene, and 1-pentene having the same content of 1-olefin (4.0 ± 0.5 mol%) and various molar mass and copolymers with a comparable molar mass and the same composition were prepared. By measuring rheological and mechanical properties of this assembly of samples, which also included the reference vinyl chloride homopolymer, it was possible to estimate the effect of molar mass and of the individual comonomers. The copolymers under investigation possessed improved processing properties and did not suffer any deterioration of important mechanical properties.     

Copolymerization of vinyl chloride with 1-olefins. III. An investigation of the copolymerization reaction of vinyl chloride with 1-butene and 1-pentene

Series of suspension copolymerization of vinyl chloride with various contents of 1-butene and 1-pentene (5–30 mass%) were carried out under the same reaction conditions. By applying a method which utilizes periodic sampling of heterogeneous reaction mixture from the reactor during the reaction and a gas chromatographic determination of unreacted vinyl chloride in the sample, the conversion curves of vinyl chloride were determined and the initial reaction rates were compared.     

Structural and mechanistic aspects of the thermal degradation of poly(vinyl chloride)

A critical review of the title subject supports the following major conclusions. Thermal dehydrochlorination of poly(vinyl chloride) (PVC) begins with internal allylic chloride and tertiary chloride structural defects formed during polymerization. The tertiary chloride is associated with 2,4-dichloro-n-butyl, 1,3-di(2-chloroethyl), and chlorinated long branches. Mechanisms for the formation of all of the labile defects are well established. ‘Carbonylallyl’ structures and certain isotactic conformers of ordinary monomer units are unimportant as initiators of thermal dehydrochlorination. Both the initiation and the subsequent formation of conjugated polyene sequences occur via carbenium chloride ion pairs or by a closely related concerted four-center quasi-ionic route. Six-center concerted processes, pathways involving free radicals, and other mechanistic schemes suggested recently are not involved in polyene elongation. However, during thermal degradation, ordinary monomer units are converted into internal allylic chloride defects by a mechanism that may include the abstraction of hydrogen by triplet cation diradicals derived from polyene intermediates. Cyclization reactions seem likely to contribute to the termination of polyene growth. When PVC is thermolyzed in blends with other polymers, unusual kinetic phenomena are detected that remain to be fully explained.     

Structural heterogeneities of suspension poly(vinyl chloride). II. Formation of compact glassy particles and the cause of their difficult processing

By modifying the polymerization process of suspension polymerization of vinyl chloride, poly(vinyl chloride) (PVC) samples were prepared containing various amounts of compact glassy particles. It was found that these particles probably arise by a different polymerization mechanism than usual suspension particles, namely, as a result of the nonhomogeneous distribution of initiator in vinyl chloride drops of the polymerization system. It was proved experimentally that the lower heat stability of difficultly processible particles is due to a side reaction between the initiator radical and the PVC polymer chain which causes dehydrochlorination of PVC already under polymerization conditions. This reaction may also explain the yet unknown mechanism of formation of internal double bonds in PVC produced by the radical polymerization of vinyl chloride. In conclusion, the difficult processibility of compact glassy particles is discussed as a consequence of the insufficient drying of these particles in the usual drying process.     

Continuous dosing of fast initiator during vinyl chloride suspension polymerization: Thermal stability of PVC resin

Thermal stability of poly(vinyl chloride) (PVC) produced using continuous dosages of a fast initiator method was investigated in terms of morphological and microstructural characteristics. The results were compared with the properties of the PVC prepared by conventional polymerization method. The Brabender^® Plastograph and DSC results showed a lower fusion time, higher stable time, and greater degree of fusion for PVC obtained by polymerization using initiator continuous dosage method. Also, chemical analysis indicated that the PVC produced under an initiator continuous dosage system have lower structural defects, that is, branch numbers, internal double bonds, labile chlorine, and tacticity index, thereby improving the thermal stability of PVC resin. The results obtained from dehydrochlorination and thermogravimetry analysis confirm the improvement of thermal stability of PVC chains synthesized with continuous dosages of a fast initiator. Moreover, it was found that the concentration of microstructural defects and the dehydrochlorination rates of the PVC samples prepared by both processes increase with monomer conversion, particularly after critical conversion. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44480.     

Thermal and photodegradation of vinyl chloride/vinyl bromide copolymers

Vinyl chloride/vinyl bromide (VC/VBr) copolymers have been synthesized by radical copolymerization in bulk. Conversion increases and molecular weight of the copolymers decreases with increasing VBr in the feed. This indicates that VBr is a chain transfer agent in VC/VBr copolymerization systems. In accordance with the lower thermal stability of the vinylbromide homopolymer (PVBr), thermal degradation experiments show that the stability of the copolymers significantly decreases with increasing VBr content. It has been found that the initial rate of dehydrohalogenation is an exponential function of VBr content during thermal degradation of VC/VBr copolymers. In separate experiments, HBr evolved during degradation has been determined by a bromide selective electrode. The initial dehydrobromination rates of VC/VBr copolymers containing higher fractions of VBr are markedly higher than the initial dehydrochlorination rates. This clearly indicates the lower thermal stability of VBr monomer units compared with VC units. UV and visible spectra of degraded VC/VBr copolymers show that the absorption and the average length of polyenes are higher for samples with higher VBr content. Dehydrohalogenation curves obtained during photodegradation of VC/VBr copolymers show a faster initial phase followed by a slower stationary phase. The initial rate of dehydrohalogenation is higher for copolymers containing higher fractions of VBr, whereas these copolymers reach the slower stationary phases at lower extents of dehydrohalogenation.     

Stabilization of poly(vinyl chloride). IV. Color changes on heating poly(vinyl chloride)–dye systems

The stabilization of poly(vinyl chloride) (PVC) involving complementary colors has been previously reported. Obliterating polyene color with various dyes containing complementary colors with the polyene color is studied on the basis of colorimetry. The changes in the color of heated PVC containing Thren Blue IRN, Ceres Blue GN, Oplas Violet 730, Macro-Lex Violet 3R, Macro-Lex Green 5B, or Macro-Lex Red 5B were investigated using a differential colorimeter. When the PVCs containing various dyes were heated, the discoloration from the color of each dye to the color mixture of each dye and polyene color was observed with increased heating times for all systems. In particular, an achromatic color has been observed, during the heat treatments, in PVC containing blue dyes such as Thren Blue IRN or Ceres Blue GN, which set up complementary color relationship with the polyene color. Thus the color of polyenes, which appears with advancing dehydrochlorination of PVC, is masked by the blue dyes. It is also apparent that the obliteration of polyene color does not depend on the chemical influences of the dyes added, but by color mixing of polyenes and the dyes. Cool-color dyes markedly slow down the appearance of polyene colors.     

Thermal dehydrochlorination of poly(vinyl chloride). I. Effect of iron oxide on the rate of dehydrochlorination

The thermal degradation of poly(vinyl chloride) (PVC) was studied by following the rates of dehydrochlorination at temperatures between 180°C in pure nitrogen and air flow. Iron oxide accelerates the elimination of hydrogen chloride from PVC. The accelerating effect depends on the concentration of the oxide, and it has a maximum. This work tried to explain these behaviors. A mechanism of dehydrochlorination is suggested for polymer containing iron oxide.     

Cross-linking of unplasticised poly(vinyl chloride) with peroxide

Abstract

The peroxide cross-linking of poly(vinyl chloride) (PVC) with trimethylolpropane trimethacrylate (TMPTMA) has been investigated. The degree of cross-linking was measured in terms of the gel content of the material, i.e. the insoluble residue remaining after soxhlet extraction in tetrahydrofuran. Cross-linking gave rise to significant improvements in high temperature tensile strength, but at higher levels of peroxide, dehydrochlorination of PVC was found to compete with grafting and cross-linking reactions. The results have been analysed to predict the optimum amount of TMPTMA and peroxide to maximise gel content and strength while maintaining thermal stability.     

Terpolymers. II. Mechanical properties and transition temperatures of terpolymers of vinyl stearate,vinyl acetate,and vinyl chloride

Vinyl stearate was studied as a major internal plasticizer in terpolymers containing vinyl acetate and vinyl chloride. The terpolymers were prepared by systematically replacing vinyl acetate by close increments of vinyl stearate starting with combinations of vinyl acetate and vinyl chloride, in increments, over all compositions. For comparison of properties, a complete range of copolymers of vinyl stearate and vinyl chloride, as well as mixtures of poly(vinyl chloride) and di-2-ethylhexyl phthalate (DOP) were also made. The external plasticizer was more efficient in reducing the glass temperature than was vinyl stearate. The decline in T_g with weight fraction of plasticizer was linear for the copolymers and terpolymers but concave downward with the liquid diluent. The linear decline was shown to involve mere additivity of the free volume contributed by each side-chain methylene (or methyl) group in both vinyl esters to reducing T_g. The mechanism of the diluent system was more complex. However, the magnitude of the reduction of tensile modulus at a given weight fraction of DOP could be equaled or exceeded by the same amount of vinyl stearate, by increasing the vinyl acetate content of the base copolymer to 40 mole-% or more. Unfortunately, the ultimate strengths and elongations of internally plasticized systems were reduced more than those of the mixtures at comparable compositions. Vinyl stearate was found to markedly retard photolytic degradation compared to both vinyl acetate and the external plasticizer in unstabilized samples having nearly the same thermal treatment. The effect was greater than could be ascribed to dilution by the long alkyl group. The production of a stearoyl radical more stable than the radicals initiating dehydrochlorination is suggested as a possible mechanism.     

Chemical recycling of poly(vinyl chloride): Application of partially dehydrochlorinated poly(vinyl chloride) for producing a chemically modified polymer

Poly(vinyl chloride) (PVC) pipes were chemically modified to produce a sulfonated polymer with dehydrochlorinated PVC samples as intermediates. Two intermediates were formed: (1) partially dehydrochlorinated PVC with long sequences of conjugated double bonds and (2) the product of the partial dehydrochlorination of PVC and the nucleophilic substitution of chlorine by hydroxyl groups. The IR spectra showed that the dehydrochlorinated samples were heterogeneous materials, showing different proportions of elimination products, hydroxyl substitution, and partial oxidation. Samples dehydrochlorinated with poly(ethylene glycol) with a molecular weight of 400 g/mol for 24 h and 15 min showed the highest sulfonation yield, which was related to the sulfonation mechanism occurring predominantly because of the presence of hydroxyl groups in a mixture of vinyl alcohol and vinyl chloride units. The sulfonation was confirmed by the presence of a medium‐intensity band at 1180 cm^?1, assigned to sulfonic groups. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Investigation of the effects of nonisothermal suspension polymerization of vinyl chloride on the fusion and degradation behavior of poly(vinyl chloride)

Thermal stability of poly(vinyl chloride) (PVC) samples polymerized under a temperature trajectory was studied from the point of view of morphological and microstructural characteristics. The results are compared with those of the PVC samples obtained by polymerization at constant temperature having the same K value. The Brabender^® plastograph data indicated that the final PVC synthesized with the temperature trajectory showed lower fusion time and higher thermal stability time. The nonisothermal condition also increased the degree of fusion of the final PVC resin, reflecting lower temperature/time required to process it. It was found that the thermal stability of nonisothermally produced PVC as characterized by dehydrochlorination rate decreased (improved) with the increasing monomer conversion until a minimum value was reached that corresponded to the conversion at the pressure drop. However, the dehydrochlorination rate remains almost constant with conversion for an isothermal grade PVC resin. Although the evolution of the number of internal double bonds as well as extent of discoloration of PVC with conversion shows a decreasing trend, the labile chlorine concentration exhibits a maximum at early conversion. The reason for the former can be explained by the temperature dependence of reactions forming defect structures, which are kinetically controlled and thus favored at higher temperatures. The latter, however, can be explained because of the increasing importance of transfer reactions to polymer with increasing polymer concentration. Finally, the results from differential thermogravimetry verify an improvement in thermal stability of the final PVC prepared by using a temperature trajectory during vinyl chloride monomer suspension polymerization. J. VINYL ADDIT. TECHNOL., 23:259–266, 2017. © 2015 Society of Plastics Engineers     

Graft copolymerization of poly(vinyl chloride) with styrene. II. Thermal behavior

Thermal behavior of graft copolymers of polyvinyl chloride with polystyrene prepared by using a cationic initiator (AlCl₃) was evaluated by measurement of rates of dehydrochlorination in nitrogen atmosphere. With increase in the extent of grafting the rates were found to decrease. Dynamic thermogravimetric analysis revealed an overall improvement in thermal stability of copolymers. Development of polyene sequences in degraded polymer samples was evaluated by measurement of electronic absorption spectra. In comparison to PVC, graft copolymer samples had fewer conjugated double bonds.     

The copolymerization of vinyl chloride with 1-olefins. II. An investigation of the copolymerization reaction of vinyl chloride and propene

The conversion curve of the copolymerization of vinyl chloride with propene and the conversion curves of both monomers were determined, their initial reaction rates compared, and the copolymerization parameters determined by a method which utilizes periodical sampling of a heterogeneous reaction mixture from the reactor during the reaction and gas-chromatographic determination of unreacted monomers contained in the sample. The agreement between the final conversion values determined chromatographically and gravimetrically was evaluated by using results of a series of copolymerizations of vinyl chloride containing various amounts of propene in the initial monomeric mixture (5–30 wt %) carried out under the same conditions.     

硅烷交联聚氯乙烯的研究

研究了硅烷的种类,增塑剂,交联时间等因素对PVC交联的影响,结果表明,通过调节硅烷的用量可以制备不同交联度的PVC,交联后的PVC其力学性能,尺寸稳定性,体积电阻率,热主为形温度得到提高。     

Thermal stability of blends of poly(vinyl chloride) with polyester elastomer

The thermal stability of poly(vinyl chloride) (PVC) under air atmosphere was improved by blending with PETE (polyester elastomer). Its enhanced stability could be explained by a reaction between the ester component of PETE and HCl from dehydrochlorination of PVC, which was identified by IR- and ¹H-NMR spectroscopy. The best result of thermal stability was shown at a composition of 100 parts of PVC with 4 parts of PETE. By surveys of glass transition temperatures, it was found that all PVC/PETE blends were ununiformly distributed. During processing, the fusion time and torque at fusion decreased as the quantity of PETE increased. The mechanical properties of the blends were also changed; as the quantity of PETE increased, tensile strength of the blends decreased, while impact strength increased.     

Thermal Decomposition of Polymer Mixtures Containing Poly(vinyl chloride)

Thermal decomposition of a series of 1 : 1 mixtures of typical polymer waste materials [polyethylene (PE), poly(propylene) (PP), polystyrene (PS), polyacrylonitrile (PAN), polyisoprene, poly(methyl methacrylate) (PMMA), polyamide‐6 (PA‐6), polyamide‐12 (PA‐12), polyamide‐6,6 (PA‐6,6), and poly(1,4‐phenylene terephthalamide) (Kevlar)] with poly(vinyl chloride) (PVC) was examined using thermal analysis and analytical pyrolysis techniques. It was found that the presence of polyamides and PAN promotes the dehydrochlorination of PVC, but PVC has no effect on the main decomposition temperature of polyamides. The hydrogen chloride evolution from PVC is not altered when other vinyl polymers or polyolefins are present. The thermal degradation of PAN is retarded significantly, whereas that of the other vinyl polymers is shifted to a slightly higher temperature in the presence of PVC. Among the pyrolysis products of PAN‐PVC mixture methyl chloride was found in comparable amount to the other gaseous products at 500°C pyrolysis temperature.     

Mechanism of action and effectiveness of ester thiols as thermal stabilizers for poly(vinyl chloride)

Organic thiols containing at least one carboxylate ester group (ester thiols) are excellent thermal stabilizers for both rigid and plasticized poly(vinyl chloride) (PVC). Their mechanism of action is shown to involve the deactivation of unstable structural defects by nucleophilic chloride displacement, the retardation and removal of coloration through thiol additions to polyene double bonds, and the prevention of autoacceleration during thermal dehydrochlorination through polyene shortening reactions and the scavenging of free radicals formed from polyenes and HCl. An unusually facile displacement of labile chloride that is favored by thiol acidity can account, at least in part, for the relatively high effectiveness of dipentaerythritol hexakis(mercaptoacetate) as a stabilizer. J. VINYL ADDIT. TECHNOL., 13:170–175, 2007. © 2007 Society of Plastics Engineers     

Studies in the thermal degradation of poly(vinyl chloride)

Thermal degradation of poly(vinyl chloride) (PVC) was studied in nitrogen atmosphere in the presence of rubber seed oil and epoxidized rubber seed oil, barium and lead soaps of rubber seed oil, and epoxidized seed oil at various temperatures. The rate of dehydrochlorination at 1% degradation and the time required to attain 1% degradation were used to assess the effect of the thermal susceptibility of PVC to dehydrochlorination. It was found that epoxidized rubber seed oil, the metal soaps of rubber seed oil, and epoxidized rubber seed oil markedly enhance the thermal stability of PVC. The order of increasing stabilizing influence was metal soaps of epoxidized rubber seed oil > metal soaps of rubber seed oil > epoxidized rubber seed oil > rubber seed oil. © 1993 John Wiley & Sons, Inc.     

Recent research advances in the chemistry of poly(vinyl chloride)

Summarized briefly here are some new observations that relate to the polymerization chemistry of vinyl chloride (VC) and to the thermal degradation, thermal stabilization, fire retardance, and smoke suppression of poly(vinyl chloride) (PVC). During polymerization, head-to-head VC emplacement leads to β-chloroalkyl radicals that can transfer chlorine atoms directly to VC. Another mechanism for transfer to monomer is responsible, however, for the polymer molecular-weight reductions that occur at high VC conversions. This transfer process involves the abstraction of methylene hydrogen from the polymer by an ordinary macroradical and the subsequent bimolecular donation of a chlorine atom to VC. The propagation steps of the polymerization do not become diffusion-controlled at VC conversions near 90%, and hydrogen abstraction from the polymer by ordinary macroradicals leads to the structural defects that cause thermal instability. The thermal dehydrochlorination of PVC involves ion pairs or four-center concerted transition states that are highly polarized. Reversible thermal stabilization of the polymer by organic metal salts occurs by the Frye-Horst process, and the reductive coupling of PVC chains may suppress both smoke and flame. This coupling can result from reactions of the polymer with zero- or low-valent transition-metal species that are formed in situ from appropriate additives.