Organotin Leachates in Drinking Water from Chlorinated Poly(vinyl chloride) (CPVC) Pipe

A solid-phase extraction method, using a phenyl-bonded silica sorbent, was developed for the isolation of mono- and di-methyltin, -butyltin and -octyltin from drinking water. Recoveries averaged 92% over two tested sample weights and spiking levels. Ethyl derivatives were made by Grignard reaction for determination by gas chromatography–atomic absorption spectrometry (GC–AAS). Static and repetitive extraction studies were conducted at 24 and 65°C. Butyltins rapidly leached into drinking water kept in chlorinated poly(vinyl chloride) (CVPC) pipe samples. Monobutyltin and dibutyltin levels reached 19.8 (13.4 as Sn) and 197 (100.4 as Sn) ng g⁻¹ respectively in water samples collected from CPVC pipe heated to 65°C. Butyltins were still leached from CPVC pipe after 20 repetitive extractions, suggesting that new CPVC water systems would contaminate water with organotins for some time after installation. © 1997 John Wiley & Sons, Ltd.     

用DSC研究线形多嵌段聚氨酯与聚氯乙烯、氯化聚氯乙烯共混相容性

用示差扫描量热法（DSC）研究了线形多嵌段聚氨酯（PU）与聚氯乙烯（PVC）、氯化聚氯乙烯（CPVC）共混相容性，说明了PU／VC、PU／CPVC的相容是由于共混物中形成了新的氢键的缘故．聚酯型聚氨酯与PVC、CPVC的相容性要好子聚酸型聚氨酯，CPVC与PU的相容性又要好于PVC．聚氨酯中硬段的引入不利于PU／PVC、PU／CPVC的相容性．     

用FTIR研究线形多嵌段聚氨酯与聚氯乙烯、氯化聚氯乙烯共混相容性

用溶液法得到线形多嵌段聚氨酯（PU）与聚氯乙烯（PV）、氯化聚氯乙烯（CPVC）的共混物。用FTIR研究PU/PVC、PU／CPVC共混物的相容性，发现PVC、CPVC的加入破坏了PU中原来的氢键，并且PU中的炭基（C=0）与PVC、CPVC中的α－H形成了新的氢键，因而说明了PU／PVC、PU／CPVC共混物具有良好的相容性。     

Thermal and radiation-induced dehydrochlorination of poly(vinyl chloride). II. Head-to-head structures

The mechanism of dehydrochlorination of 2,3-dichlorobutane and chlorinated polybutadiene which are model compounds of head-to-head poly(vinyl chloride) has been investigated by pyrolysis, thermal, and ultraviolet-induced decomposition. The activation energy of dehydrochlorination for head-to-head poly(vinyl chloride) in nitrogen was 23 kcal/mole at temperatures of 150–190°C, which is slightly smaller than that (29 kcal/mole) for head-to-tail poly(vinyl chloride). The conjugated double bonds were formed by thermal and radiation decomposition of head-to-head poly(vinyl chloride), similar to head-to-tail poly(vinyl chloride). The probability of polyene formation by radiation-induced dehydrochlorination is larger than that by thermal decomposition and is affected by the conformation and the molecular motion of the main chain. This may be due to the alternative mechanism of dehydrochlorination in the thermal and radiation decomposition. The amount of head-to-head linkage of poly(vinyl chloride) samples prepared with various catalysts is dependent on polymerization temperature rather than the kinds of catalyst. Commercial poly(vinyl chloride) has 6–7 head-to-head linkages per 1000 monomeric units.     

Structure of chlorinated poly(vinyl chloride). V. Molecular parameters of chlorinated poly(vinyl chloride)

The molecular parameters of samples of chlorinated poly(vinyl chloride) (CPVC) and chlorinated β,β-dideuterated poly(vinyl chloride) (β,β-d₂-CPVC) were determined by gel permeation chromatography (GPC), light scattering, osmometry, and viscometry. Comparison of GPC, light scattering, osmometric, and viscometric data resulted in a discussion of the possibility of degradation and the causes of changes in the solution properties in chlorination of PVC and ββ-dideuterated poly(vinyl chloride) (ββ-d₂-PVC). The results obtained are discussed in relation to the mechanism of chlorination of PVC.     

氯化聚氯乙烯／环氧树脂共混体的流变性质及形态

氯化聚氯乙烯(CPVC)具有优良的物理性能。但须严格控制加工温度,加工熔体粘度较大。近年,作者曾对CPVC与氯化聚乙烯(CPE)和丙烯酸酯共聚物(ACR)共混体的流变性质进行了研究。本文首次研究CPVC与环氧树脂(EP)共混体的流变性质与形态。     

Metallocene based polyolefin: a potential candidate for the replacement of flexible poly (vinyl chloride) in the medical field

A comparative assessment of the performance properties of metallocene polyolefin (m‐PO) with those of plasticized poly (vinyl chloride) (pPVC) and ethylene vinyl acetate (EVA) copolymer having 18% vinyl acetate content (EVA‐18), the two common polymers used for flexible medical products, is carried out. The preliminary evaluation of the processability, mechanical properties, and thermal stability of the new material, m‐PO is described. The processability parameters like mixing torque and melt viscosity of m‐PO are found to be comparable with those of pPVC and EVA‐18. Mechanical properties such as tensile strength, elongation at break, and tear strength (TS) of m‐PO are much higher than that of pPVC and EVA‐18. Thermo gravimetric analysis (TGA) indicates that the thermal degradation of m‐PO takes place only at temperatures above 340°C and can be processed at 170°C without much damage. Oxygen and carbon dioxide permeabilities of m‐PO at three different temperatures (10, 25, and 40°C) are evaluated and compared with those of pPVC and EVA‐18. It could be seen that the permeabilities of both the gases for m‐PO at three temperatures were lower than those of pPVC and EVA. Biological evaluation of m‐PO is carried out by assessing its cytotoxicity, hemolytic property, and blood clotting initiation. The cytotoxicity studies indicate that m‐PO is non‐toxic to the monolayer of L929 mammalian fibroblast cell lines on direct contact or the exposure of its extract. Non‐hemolytic property of m‐PO by direct contact as well as test on extract is revealed both in static and in dynamic conditions. Blood clotting time experiments indicate that the initiation of blood clotting due to m‐PO is faster than that of pPVC and EVA‐18. Copyright © 2009 John Wiley & Sons, Ltd.     

A study of polymer blends by nonradiative energy transfer fluorescence spectroscopy

The nonradiative energy transfer (NRET) method has been used to study the miscibility of polymer blends in the solid state. This can be done by labeling the polymers with fluorescence donor and acceptor chromophores. The efficiency of energy transfer, which reveals the interpenetration of the chains, is measured by following changes in the fluorescence intensity ratio of the donor and acceptor as a function of the concentration of the polymer mixture and by comparison with reference values corresponding to totally miscible and totally immiscible systems. It is shown that the reference ratio corresponding to the absence of energy transfer must be determined by using donor-labeled and acceptor-labeled polymer films, instead of making measurements in chromophore solutions in organic solvents, as has usually been done. It is also shown that fluorescence quenching is important in such studies, since it can lead to variations of the fluorescence intensity ratio by more than an order of magnitude; this factor varies with blend concentration and is particularly sensitive to the presence of halogen atoms. The NRET technique has been applied to several PVC/CPVC binary blends and to PCL/PVC/CPVC ternary blends in which PVC and CPVC were labeled by naphthalene and anthracene, respectively [PCL is poly(ε-caprolactone), PVC is poly(vinyl chloride), and CPVC is chlorinated PVC]. For binary blends, the measured intensity ratios indicate the immiscibility of PVC with CPVC, although there is nonnegligible energy transfer between the two phases. For ternary blends, the intensity ratios indicate that the addition of up to 40 wt % of PCL to the immiscible PVC/CPVC binary system leads to the formation of two coexisting PCL/PVC and PCL/CPVC phases.     

Henry's law and diffusion constants of vinyl chloride in poly(vinyl chloride) at high temperature

The Henry's law and diffusion constants of vinyl chloride in poly(vinyl chloride) were determined at temperatures of 24, 90, 120, 150, and 170°C for weight fractions of vinyl chloride between 0.2 × 10^?3 and 0.8 × 10^?3. Above 90°C, Henry's law applies; values of the constant increase with temperature from 1.8 × 10² to 5.5 × 10² atm per unit weight fraction of dissolved vinyl chloride. The heat of desorption is about 15 kJ/mole. At 24°C, the nominal Henry's law constant was smaller than would have been obtained by extrapolating the values found at higher temperature. The diffusion constants increase with temperature from about 2 × 10^?13 to 3 × 10^?7 cm²/sec. The activation energy for diffusion is about 110 kJ/mole between 90 and 170°C. Although all values were determined in the absence of air, it is likely that they apply to polymer in air. They may, therefore, be used to calculate the vinyl chloride content in the gas above poly(vinyl chloride) under specific processing conditions.     

Structure of chlorinated poly(vinyl chloride). I. Determination of the mechanism of chlorination from infrared and NMR spectra

Infrared and NMR spectra of chlorinated poly(vinyl chloride) (CPVC) and of chlorinated α-deuterated poly(vinyl chloride) (α-d-CPVC) have been measured. It was found that the CDCl unit of α-d-PVC does not undergo chlorination. By assuming an analogous mechanism of chlorination in normal PVC, the populations of all the three possible types of two-carbon sequences (? CH₂? CHCl? , ? CHCl? CHCl, ? CHCl? CCl₂) in CPVC could be determined. The mechanism of chlorination of PVC is discussed from the viewpoint of the previous findings on the conformational structure of this polymer. Differences in structure between suspension- and solution-chlorinated PVC have been established.     

Structure and Dehydrochlorination of Poly(vinyl Chloride)

The wide applicability of poly(vinyl chloride) (PVC), a tough thermoplastic resin, is due to a combination of moderate cost with the following characteristics [1]: (i) good general properties as a plastic material: (ii) great variation in properties, e.g., increase in heat distortion temperature, resistance to hot melt flow, improvement in mechanical, electrical properties, and processability of unplasticized PVC through external plasticization, block and graft copolymerization (internal plasticization), and chemical modification, e.g., chlorination, Friedel-Crafts, and cross-linking reactions: and (iii) processing versatility including injection molding, extrusion, blow molding, calendering, and lamination to produce many products of potential uses.     

Polymerization of vinyl chloride with organolithium compounds. V. Flow behavior of concentrated solutions of high molecular weight poly(vinyl chloride) in cyclohexanone

The flow behavior of 10, 15, and 25% solutions of high molecular weight, thermally stable poly(vinyl chloride) in cyclohexanone was studied in the temperature range 50–140°C with respect to fiber-forming properties. The flow behavior of such solutions at shear rates ranging from 1–10³ sec^?1 is pronouncedly non-Newtonian with the exception of the 10% solution at 70°C. It can be adequately described by known empirical linear relationships. The apparent viscosities and activation energies are considerably higher than those for the usual types of poly(vinyl chloride), but vary within limits acceptable for the preparation and spinning of solutions.     

Retardation of discoloration of poly(vinyl chloride) and decolorization of discolored poly(vinyl chloride) with diimide

Retardation of discoloration of poly(vinyl chloride) with diimide was studied in dimethylformamide at 130°C. with the use of p-toluenesulfonylhydrazide (PSH) as a source of diimide. A process was proposed that involved prolonging the induction periods of discoloration by inhibiting the development of conjugated polyene structure. The optimum proportion of PSH was one fourth of the poly(vinyl chloride), the best results. Furthermore, poly(vinyl chloride) discolored by thermal degradation in o-dichlorobenzene or gamma-ray irradiation under vacuum was decolorized in solution at 130°C. by addition of PSH. The decolorized poly(vinyl chloride) thus obtained was thermally stable compared with that obtained by oxidative methods.     

Microcrystalline and three-dimensional network structure of plasticized poly(vinyl chloride)

Three-dimensional networks can be formed in plasticized poly(vinyl chloride) by chain entanglements and crystallites introduced in the system during the fusion and annealing processes. The fusion conditions influence the mechanical stability of the plasticized polymers, by establishing regions where one-phase systems are observed. During annealing at temperatures of between 170 and 190 °C, for up to 9 minutes, maximum degree of crystallinity of 0.079 was detected for samples plasticized with 20 wt% di-2-ethyl-hexyl-phthalate. Experimental analysis of mechanical properties and analysis of stress relaxation experiments showed that rubber elasticity theories could be applied with some approximation to plasticized PVC to analyze the structure of the three-dimensional networks formed.     

The structure of chlorinated poly(vinyl chloride). VI. Comparison of the chlorination of poly(vinyl chloride) and β,β-d2-poly(vinyl chloride) with 1H-NMR and 13C-NMR spectroscopy

Samples of chlorinated poly(vinyl chloride) (CPVC) and chlorinated β,β-dideuterated poly(vinyl chloride) (β,β-d₂-CPVC) were prepared under identical reaction conditions. The microstructure of CPVC and β,β-d₂-(CPVC) was characterized by a combination of ¹H-NMR, ¹³C-NMR spectroscopy, and analytically determined chlorine content. A difference was observed in the reaction rates of chlorination of PVC and β,β-d₂-PVC, and, in their thermal chlorination in solution, also in the structure of the chlorinated products. It was proved that in the chlorination of β,β-d₂-PVC a new chlorine atom can also enter the original? CHCl? group. The results are discussed from the standpoint of the chlorination mechanism.     

Chemical and electrochemical grafting of polyaniline onto poly(vinyl chloride): synthesis,characterization, and materials properties

We have designed and developed a new strategy for the chemical and electrochemical graft copolymerization of aniline onto poly(vinyl chloride). For this purpose, first phenylamine groups were incorporated into poly(vinyl chloride) via a nucleophilic substitution reaction in the presence of a solvent composed of 4‐aminophenol, potassium carbonate, and dry N,N‐dimethylformamide at room temperature, in order to avoid cross‐linking. The macromonomer obtained was used in chemical and electrochemical oxidation copolymerization with aniline monomer to yield a poly(vinyl chloride)‐g‐polyaniline (PVC‐g‐PANI) graft copolymer. The chemical structures of samples as representatives were characterized by means of Fourier transform infrared and ¹H nuclear magnetic resonance spectroscopies. The electroactivity behaviors of the synthesized samples were verified under cyclic voltammetric conditions. The electrical conductivity and electroactivity measurements showed that the PVC‐g‐PANI graft copolymer has lower electrical conductivity as well as electroactivity than those of the pure PANI. However, the lower electrical conductivity and electroactivity levels in this material can be improved at the price of solubility and processability. Moreover, the thermal behavior and chemical composition of the synthesized graft copolymer were investigated. Copyright © 2016 John Wiley & Sons, Ltd.     

Radiolysis of poly(vinyl chloride)

Allyl free-radical intermediates are detected by ultraviolet absorption at 255 mu in poly(vinyl chloride) irradiated at ?196°C and stored at 25°C. In vacuum at 25°C, allyl radicals are converted into polyenyl free radicals and polyenes. From the nature of allyl radical decay in vacuum, radical chain transfer between polyenyl radicals and poly(vinyl chloride) is inferred. Allyl and polyenyl free radicals are scavenged by oxygen on post-irradiation storage in air.     

Synthesis of ABA‐triblock and star‐diblock copolymers with poly(2‐adamantyl vinyl ether) and poly(n‐butyl vinyl ether) segments: New thermoplastic elastomers composed solely of poly(vinyl ether) backbones

ABA‐type triblock copolymers and AB‐type star diblock copolymers with poly(2‐adamantyl vinyl ether) [poly(2‐AdVE)] hard outer segments and poly(n‐butyl vinyl ether) [poly(NBVE)] soft inner segments were synthesized by sequential living cationic copolymerization. Although both the two polymer segments were composed solely of poly(vinyl ether) backbones and hydrocarbon side chains, they were segregated into microphase‐separated structure, so that the block copolymers formed thermoplastic elastomers. Both the ABA‐type triblock copolymers and the AB‐type star diblock copolymers exhibited rubber elasticity over wide temperature range. For example, the ABA‐type triblock copolymers showed rubber elasticity from about ?53 °C to about 165 °C and the AB‐type star diblock copolymer did from about ?47 °C to 183 °C with a similar composition of poly(2‐AdVE) and poly(NBVE) segments in the dynamic mechanical analysis. The AB‐type star diblock copolymers exhibited higher tensile strength and elongation at break than the ABA‐type triblock copolymers. The thermal decomposition temperatures of both the block copolymers were as high as 321–331 °C, indicating their high thermal stability. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Colorimetric analysis of thermal degradation of plasticized poly(vinyl chloride): Potentials and limitations

The kinetics of formation and consumption of polyenes is studied by measuring the change in color coordinates and color difference during the thermal aging of plasticized poly(vinyl chloride) at a temperature of 60–130°С under vented conditions and in a closed volume. It is shown that the initial rate of accumulation and the quasi-stationary concentration of polyenes at 100–130°С grow with temperature. The energy of activation of dehydrochlorination is 70 ± 3 kJ/mol. At a lower temperature (60–80°С), the intensity of color of the samples that are preliminarily aged at increased temperatures decreases. The reduction in the rate of this process with temperature in the range of 60–80°С and the presence of the quasi-stationary level at 100–130°С are related to competition of the processes of formation and oxidation of polyenes.     

A novel approach to synthesis of functional CPVC and CPE or graft copolymers—in situ chlorinating graft

A new process of graft copolymerization of poly(vinyl chloride) (PVC) and polyethylene (PE) with other monomers was developed. The grafted chlorinated poly(vinyl chloride) (CPVC) and chlorinated polyethylene (CPE) were synthesized by in situ chlorinating graft copolymerization (ISCGC) and were characterized. Convincing evidence for grafting and the structure of graft copolymers was obtained using FT‐IR, ¹H‐NMR, gel permeation chromatography (GPC), and the vulcanized curves. Their mechanical properties were also measured. The results show that the products have different molecular structure from those prepared by other conventional graft processes. Their graft chains are short, being highly branched and chlorinated. The graft copolymers have no crosslinking structure. The unique molecular structure will make the materials equipped with special properties. Copyright © 2007 John Wiley & Sons, Ltd.