Synthesis of vinyl phenyl acetate and an evaluation of vinyl chloride/vinyl phenyl acetate copolymers

The synthesis of vinyl phenyl acetate, by an ester interchange reaction between phenyl acetic acid and vinyl acetate and utilizing a catalyst, is described. Copolymerization with vinyl chloride, in a suspension system and using a peroxide catalyst, is described on a laboratory and pilot plant scale. Monomer/copolymer compositions, for an initial charge consisting of vinyl chloride/vinyl phenyl acetate (80/20 by weight) are presented over a range of conversions, as an indication of reactivity ratios. Discs, molded from unstabilized copolymers, show very good clarity and color stability, which improve with increased comonomer loading. Some retention of unpolymerized vinyl phenyl acetate monomer occurred, and some increase in softening points resulted following two reprecipitations from acetone into excess methanol. Compound from a 96/4 vinyl chloride/vinyl phenyl acetate copolymer has better color stability than does an equivalent vinyl chloride/vinylidene chloride copolymer compound. The enhanced color and heat stability of the copolymers is attributed to the aromatic character of the comonomer vinyl phenyl acetate.     

Plastification of poly(vinyl chloride) by polymer blending

Blends of poly(vinyl chloride) (PVC) with different copolymers have been studied to obtain a plasticized PVC with improved properties and the absence of plasticizer migration. The copolymers used as plasticizers in the blends were acrylonitrile butadiene rubber, ethylene vinyl acetate (EVA), and ethylene-acrylic copolymer (E-Acry). Blends were studied with regard to their processing, miscibility, and mechanical properties, as a function of blend and copolymer composition. The results obtained were compared with those of equivalent compositions in the PVC/dioctyl phthalate (DOP) system. Better results than PVC/DOP were obtained for PVC/acrylonitrile butadiene rubber blends. The plasticizing effect on PVC of EVA and E-Acry copolymers was similar to that of DOP. It is shown that crosslinking PVC/E-Acry blends or increasing the vinyl acetate content in PVC/EVA blends, are alternatives that can increase the compatibility and mechanical properties of these blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1303–1312, 2000     

The rheological properties of vinyl chloride–vinyl acetate copolymers

Copolymers of vinyl chloride–vinyl acetate have been prepared with different vinyl acetate contents and molecular weights and under different polymerization conditions. A rheological study of these copolymers indicates that they behave in some ways like externally plasticized PVC. For instance, as the vinyl acetate content increases, the melt viscosity decreases, the flow activation energy decreases, and the copolymer becomes more Newtonian. However, the critical shear rate for melt fracture increases, resembling the addition of elastic polymers to PVC. An increase in copolymer molecular weight has a similar effect on the rheological behavior as in PVC, except that the flow activation energy is observed to increase rather than decrease. Decreasing the polymerization temperature affects the flow properties of the copolymer, probably due to changes in degree of branching and crystallinity. A copolymer made by the delayed addition of vinyl chloride, having a more random structure than one made by the conventional batch method, exhibited quite different flow behavior. It had a lower melt viscosity, higher critical shear rate, and lower flow activation energy.     

Polyblends. I. Mechanical properties of polyblends of butadiene–acrylonitrile elastomers and copolymers of vinyl stearate and vinyl chloride

Several nitrile rubber elastomers were polyblended, across the composition range, with selected polymeric compositions containing vinyl chloride. The compositions incorporated were (a) bulk poly(vinyl chloride) (PVC); (b) copolymers of vinyl stearate and vinyl chloride containing, respectively, 0.21, 0.36, and 0.47 weight fraction of the vinyl ester; and (c) mixtures containing the same weight fractions of di-2-ethylhexyl phthalate (DOP) with PVC. Mechanical, viscoelastic, optical, and volatility properties were studied on all blends in this first paper. To accurately compare the mechanical properties of polyblends of different systems, a criterion of mechanical equivalence was taken as the observance of similar stresses at break for compositions selected to have identical 100% moduli. Optimum mechanical equivalence, therefore, occurred at the largest ratios of 100% modulus to break stress for all systems compared. Optimum mechanical property equivalence was observed for NBR blends with PVC and for similar blends of both internally and externally plasticized systems containing 0.21 weight fraction of plasticizer. However, considerably more nitrile rubber was needed for PVC blends to acquire the properties of the plasticized systems. Mechanical equivalence was observed, but was not optimum for systems having more plasticizer because tensile strengths were lower. Polyblending with NBR improved the toughness and low-temperature properties of starting vinyl stearate copolymers. Improved toughness was indicated by the expansion of areas under stress–strain curves. Refractive index matching appeared to explain the transparency of the best films and their relative freedom from haze. On heating at 85°C, poly(vinyl chloride) and the copolymer polyblends suffered no volatility loss. Volatility of DOP from the blends was 1.5 times greater than for PVC–DOP mixtures. Because modulus–temperature curves and mechanical T_g values of the filler component shifted with composition, the mechanical behavior of these blends was in harmony with an accepted standard of interdomain compatibility.     

可逆加成-断裂链转移聚合制备聚氯乙烯-b-聚乙二醇-b-聚氯乙烯共聚物

合成了含黄原酸酯端基的聚乙二醇（X-PEG-X）大分子链转移剂,并以其为可逆加成-断裂链转移试剂调控氯乙烯（VC）溶液和悬浮聚合,合成聚氯乙烯-b-聚乙二醇-b-聚氯乙烯（PVC-b-PEG-b-PVC）三嵌段共聚物。X-PEG-X调控VC溶液聚合得到的共聚物的分子量随聚合时间增加而增大,分子量分布指数小于1.65。X-PEG-X具有水/油两相分配和可显著降低水/油界面张力的特性,以X-PEG-X为链转移剂和分散剂,通过自稳定悬浮聚合也可合成PVC-b-PEG-b-PVC共聚物,共聚物颗粒无皮膜结构,分子量随聚合时间增加而增大;由于VC悬浮聚合具有聚合物富相和单体富相两相聚合特性,共聚物分子量分布指数略大于溶液聚合共聚物。通过乙酸乙烯酯（VAc）扩链反应进一步证实了PVC-b-PEG-b-PVC的“活性”,并合成PVAc-b-PVC-b-PEG-b-PVC-b-PVAc共聚物。水接触角测试表明PVC-b-PEG-b-PVC的亲水性优于PVC。     

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.     

Poly(vinyl chloride)‐b‐poly(hydroxypropyl acrylate)‐b‐Poly(vinyl chloride): Understanding the synthesis of an amphiphilic PVC block copolymer on a pilot scale

The aim of this work was to develop an understanding of the major difficulties associated with the scale‐up of the technology for the synthesis of poly(vinyl chloride) (PVC) block copolymers that contain hydrophilic segments, thus providing important directions to be followed in order to produce such new materials on the industrial scale. The synthesis was carried out in a two‐step process. First, the macroinitiator α,ω‐di(iodo)poly(hydroxypropyl acrylate) was synthesized in an aqueous medium by (single electron transfer)/(degenerative chain transfer) living radical polymerization (SET‐DTRP) catalyzed by Na₂S₂O₄. The block copolymer was then prepared by SET‐DTRP of vinyl chloride (VC) from the iodine‐terminal active chain ends of the macroinitiator, thereby leading to the formation of the block copolymer poly(vinyl chloride)‐b‐poly(hydroxypropyl acrylate)‐b‐poly(vinyl chloride). This report covers important aspects related to the characterization of the block copolymer produced and to the identification of the major limitations that must be overcome in order to produce this new material on the industrial scale. The results clearly show the differences between the theoretical predictions and the block copolymer compositions obtained by using a suspension polymerization method, which is the most‐used polymerization process in the PVC industry. J. VINYL ADDIT. TECHNOL., 19:94–104, 2013. © 2013 Society of Plastics Engineers     

Quaternarized cationic poly[(vinyl chloride)-co-(vinyl chloroacetate)] binary copolymer as non-migration antibacterial additive in PVC matrix

Antibacterial polyvinyl chloride (PVC) materials have drawn considerable attention since their wide application in medical devices. The objective of this study is to develop a novel quaternary ammonium cationic vinyl chloride copolymer, which can be potentially used as antibacterial additive in PVC matrix. Initially, the low average-number molecular weight poly[(vinyl chloride)-co-(vinyl chloroacetate)] (PVC-co-PVCA) is synthesized by precipitation copolymerization. Subsequently, quaternary ammonium cationic moieties with different lengths of alkyl chains are introduced into the copolymers via quaternization reaction between alkyl-dimethyl tertiary amines with acyl chloride groups. The successful synthesis of PVC-co-PVCA and quaternarized copolymers are carefully confirmed by Fourier transform infrared spectroscopy, nuclear magnetic resonance (1H NMR), and x-ray photoelectron spectroscopy. The antibacterial behaviors of the quaternarized copolymers and its blends with PVC are investigated. The results reveal that all the PVC blends containing at least 5% by weight of quaternarized copolymer have superior bacteriostasis ratio (>99.6%) against both Escherichia coli (E.coli) and Staphylococcus aureus (S. aureus) due to the incorporation of quaternary ammonium groups. Meanwhile, the cationic copolymer exhibits excellent antifouling and much lower migration rate (<0.4%). These interesting consequences endow the quaternarized copolymers as alternative antibacterial agents possess a great deal of potential for use in PVC materials.     

Reactions of unsaturated fatty alcohols. V. Preparation and properties of some copolymers of unsaturated fatty vinyl ethers with lower alkyl vinyl ethers

Summary Soybean vinyl ethers derived from soybean alcohols were copolymerized with lower alkyl vinyl ethers,e.g., ethyl, butyl, isobutyl, 2-chloroethyl, 2-methoxyethyl, and 2-ethylhexyl, in methylene chloride at −30°C., using boron trifluoride etherate catalyst. Molecular weights ranging from 2,000 to 4,000 were obtained on these copolymers by cryoscopic measurements in cyclohexane. An analytical method, using infrared spectroscopy, was employed to determine the composition of the copolymers. The properties of each alkyl-soybean vinyl ether copolymer were studied at three molar compositions,e.g., 3∶1, 1∶1, and 1∶3. The products were water-white to amber viscous liquids and were soluble in aromatic, chlorinated, and gasoline type of solvents. Copolymers films were prepared under conditions that were shown to produce extensive degradation of some homopolymer films in order to magnify small differences in properties. These films were hard, wrinkle-free, and resistant to most common solvents, also were 20 to 500 times more resistant to 5% aqueous alkali than soybean vinyl ether polymer prepared under the same conditions. Copolymer films were baked on silver chloride plates and examined in the infrared. Oxidative degradation of the C−O−C ether linkage was observed in all copolymer films; however the 2-chloroethyl-soybean copolymer series was least susceptible to this degradation.     

Synthesis of random and block copolymers of vinyl chloride and vinyl acetate by RAFT miniemulsion polymerizations mediated by a fluorinated xanthate

Reversible addition–fragmentation chain transfer miniemulsion (co)polymerizations of vinyl acetate (VAc) and vinyl chloride (VC) are conducted in the presence of a fluorinated xthanate (X1). VAc miniemulsion polymerization can be well controlled by X1, and PVAc with small polydispersity index (PDI, <1.20) are obtained. X1 also shows well mediative effect to VC‐VAc miniemulsion copolymerization, while the PDI of VC‐VAc copolymer is greater than that of PVAc since a chain transfer rate to VC is greater than that to VAc. PVAc‐b‐PVC copolymers are synthesized by VC miniemulsion polymerizations mediated by X1‐terminated PVAc. PDIs of PVAc‐b‐PVC copolymers are greater than that of PVAc and VC‐VAc random copolymers with close monomer compositions, and increase with the increase of VC conversion. This is caused by the increased chain transfer to monomer and the formation of monomer‐rich and polymer‐rich phases during the VC polymerization stage. As‐prepared PVAc‐b‐PVC copolymers exhibit a micro‐phase separated morphology. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45074.     

Polyblends of poly(vinyl chloride) with ethylene/vinyl acetate copolymers: Practical properties and morphology

Five to 15 percent of ethylene/vinyl acetate copolymers was compounded into rigid polyvinyl chloride, with the copolymers dispersed as discrete micro-domains, produced very efficient synergistic improvement of impact strength; as the vinyl acetate content of the copolymer increased from 28 to 60 percent, the synergistic peak moved to higher copolymer content and became higher and broader. Copolymer content correlated directly with melt flow and thermal stability, and inversely to modulus, strength, and heat-deflection temperature. The vinyl acetate content of the copolymer correlated directly with elongation, impact strength, and thermal stability, but inversely to modulus, heat-deflection temperature, low-temperature flexibility, and melt flow. When the copolymer content reached 25 percent, it formed a second continuous-phase, interpenetrating the polymer network structure and acting as a polymeric plasticizer, producing thermoplastic elastoplastics.     

Terpolymers. III. Isochronal viscoelastic parameters for terpolymers of vinyl stearate,vinyl acetate,and vinyl chloride

Isochronal viscoelastic parameters were collected for many of the copolymers, terpolymers, and diluent mixtures whose mechanical properties at ambient temperatures were reported in the preceding paper. In the polymeric systems, vinyl stearate, acting as the primary internal plasticizer, was introduced into terpolymers by displacing vinyl acetate from base copolymers of vinyl acetate and vinyl chloride, across the range of composition. In the diluent mixtures, poly(vinyl chloride) was plasticized by di-2-ethylhexyl phthalate across the range of compositions. For direct comparison with the mixtures, vinyl chloride was plasticized by copolymerization with vinyl stearate across the same range of compositions. Moduli for the co- and terpolymers reached the low values characteristic of soft materials at room temperature only through a short range of vinyl stearate composition. At higher internal plasticizer compositions, side-chain crystallization stiffened the samples and raised their moduli. In contrast, moduli for the mixtures decreased steadily with increase in diluent at ambient temperature. The effective use temperature ranges were narrow for the co- and terpolymers but broad for the mixtures. Curve broadening was similar for both types of systems, but reached a maximum at about 40 weight-% plasticizer for the diluent mixtures. The slopes of the glassy modulus with decreasing temperature at 50°C below T_g for the vinyl stearate copolymers were relatively large. However, moduli close to that of poly(vinyl chloride) were reached only near the temperature range associated with the γ-transition. Consequently, this behavior was attributed to motions of the side chains in the glassy matrix. Room temperature moduli, which could be obtained before the onset of melting, were correlated with the fractional side-chain crystallinity for polymers having a high vinyl stearate content. From this relation, the modulus for the hexagonal crystal form of the side-chain crystallites of poly(vinyl stearate) was estimated to be 1.2×10¹⁰ dynes/cm². Moduli for the glassy amorphous phase of this same polymer appeared to have one sixth of this value at 40°C below the glass transition. The glass transition temperature occurred about 10° below the inflection temperature at 10⁹ dynes/cm², as an average for all of the systems studied.     

Effect of polymerization conditions on the melt rheological properties of vinyl chloride–vinyl acetate copolymers

Mathematical models have been developed which predict the composition, molecular weight, and melt rheological properties for vinyl chloride/vinyl acetate copolymers of inherent viscosity range 0.4–0.7 dL/g and bound vinyl acetate levels of 3.8–17.4%. The effect of polymer long chain branching on the viscous/elastic moduli ratio is discussed as well as the comparison of Tinius–Olsen melt index measurements vs. mechanical spectrometer results. The reactivity ratio for vinyl chloride/vinyl acetate comonomer pairs was remeasured and found to be significantly different from literature values.     

Grafting of vinyl acetate onto poly(vinyl chloride) in solution

Radiation-induced grafting of vinyl acetate (VAc) onto poly(vinyl chloride) (PVC) was performed in solution with dimethylformamide (DMF). Grafting was studied as a function of dose, dose rate, and VAc/PVC ratio. The amount of grafting was measured by IR spectroscopy on the graft copolymer fraction insoluble in hot methanol. The homopolymerization of VAc was also studied in the same conditions, in order to check the influence of the solvent on radiochemical reactions leading to graft copolymers. The results show that the grafting can be easily obtained and the graft copolymer will be tested for the preparation of ultrafiltration membranes.     

Gel permeation chromatography in the study of the molecular weight distribution of the copolymer vinyl chloride–vinyl acetate. II. Influence of copolymer chemical composition

A set of statistical vinyl chloride–vinyl acetate copolymers of various vinyl acetate content was prepared. The samples were fractionated by preparative gel permeation chromatography (GPC), and the fractions were characterized by analytical GPC, light scattering, and viscometry. The original samples were characterized also by osmometry and chemical analysis. The molecular parameters calculated from GPC analysis using the universal calibration were correlated with those of light scattering measurements and viscometry. It was found that in the range of chemical compositions and molecular weights studied, the chemical composition does not significantly influence the results of GPC analysis.     

Alcoholysis of copolymers of vinyl acetate with itaconic acid

We studied alcoholysis of vinyl acetate and itaconic acid (up to 8.5 mol %) copolymers. We obtained the copolymers both by single and continuous addition of the second comoner, and carried out the alcoholysis in methanol and methanol-gasoline medium at temperature 30°C using sodium hydroxide as catalyst. We established that the presence of itaconic sequences in the vinyl acetate polymer chain in an amount of 1.5–2 mol % causes significant reduction in the viscosity of methanol solutions without greatly affecting the molecular weight of the copolymer. The alcoholysis of random copolymers, containing not more than 4 mol % itaconic sequences takes place at a higher rate. The vinyl acetate-vinyl alcohol copolymer, containing groups of itaconic acid has better surface activity. This is more clearly expressed in the case of random copolymers.     

Investigation of the compatibility of butadiene—acrylonitrile copolymers with poly(vinyl chloride)

Various methods were used to study the compatibility of butadiene-acrylonitrile copolymers with poly(vinyl chloride). These blends were investigated by phase contrast microscopy, differential scanning calorimetry and torsion pendulum analysis. We conclude that the copolymers are compatible with poly(vinyl chloride) in all PVC compositions within the range 23–45% acrylonitrile. These blends exhibit a single T_g in the torsion pendulum studies and differential scanning calorimetry studies and follow a Fox expression in the variation of T_g with composition. Experimental densities are also higher than those calculated assuming volume additivity, implying better packing and a negative heat of mixing leading to molecular compatibility.     

Thermal behavior of cellulosic graft copolymers. II. Cotton grafted with binary mixtures of vinyl acetate and methyl acrylate

Thermal degradation of cotton, mercerized cotton, cotton grafted with vinyl acetate-methyl acrylate mixtures at different compositions, and mercerized cotton grafted with vinyl acetate–methyl acrylate mixture at a composition of 60 : 40 has been investigated using the techniques of thermogravimetric analysis (TGA) and differential thermal analysis (DTA) in nitrogen. The kinetic parameters E, n, and A have been obtained following several methods of thermogravimetric analyses. The mercerization shows a little effect upon thermic properties of cotton cellulose, making cotton thermally more stable. Graft copolymerization of vinyl acetate-methyl acrylate mixture makes cotton thermally less stable if the composition of the copolymer grafted is 100, 90, and 70 mol % VA, while in the case of cellulose graft copolymers with compositions of VA–MA of 80 : 20, 20 : 80, 5 : 95, and 0 : 100 the thermal stability is higher than that of original cotton. The thermal stability of the mercerized cotton grafted with vinyl acetate-methyl acrylate mixture with a composition of 60 : 40 depends on the percent grafting yield. The thermal stability of mercerized cotton grafted with the monomer mixture is higher than that of cotton grafted with that monomer mixture. The degradation of cellulose and cellulose graft copolymers is complex as is shown by DTA thermograms and kinetic parameters.     

The copolymerization of vinyl chloride with 1-olefins. V. Heat stability of copolymers of vinyl chloride with propene, 1-butene,and 1-pentene

Copolymers of vinyl chloride with propene, 1-butene, and 1-pentene containing 2–15 mol % of 1-olefinic structural units were prepared. The copolymers were dehydrochlorinated at 180°C in an inert atmosphere; the amount of hydrogen chloride split off was determined by continuous potentiometry. The results show that the heat stability of propene, 1-butene, and 1-pentene copolymers containing the same amount of 1-olefinic structural units does not differ significantly. Compared with the homopolymer of vinyl chloride, it is favorably affected by the presence of 1-olefinic structural units in poly(vinyl chloride) (PVC) chains. On the other hand, however, the heat stability of copolymers is impaired by the higher content of structural defects able to initiate the dehydrochlorination reaction. These structural defects, probably represented by chloroallyl groups, are formed in the copolymers during their synthesis. At the beginning of heating, structural defects produce intensive dehydrochlorination and, therefore, copolymers of vinyl chloride with 1-olefins if processed appear to be less thermally stable than does PVC.     

Electrical properties of poly(vinyl chloride) compositions

A sample of poly(vinyl chloride) (PVC) and a polar plasticizer consisting of dioctyl phthalate (DOP) and dibutyl phthalate (DBP) was prepared and found to possess inconvenient electrical properties (permittivity, dielectric loss, and conductivity). Different samples of PVC compositions were formulated from the PVC–DOP–DBP system and also variable proportions of a copolymer of 1-octadecene-maleic anhydride or its hexadecylester. Lead stearate as a heat stabilizer and kaolin as a filler were added. The effect of copolymer structure on the electrical properties of the PVC–DOP–DBP system was studied to obtain a plasticized PVC of good electrical insulation character. © 1993 John Wiley & Sons, Inc.