Structural heterogeneities of suspension poly(vinyl chloride). I. Compact glassy particles

By using the modified suspension polymerization of vinyl chloride, samples of poly(vinyl chloride) (PVC) were prepared with a high content of unprocessible particles which were isolated and subjected to a morphological investigation. Their structure was examined viscometrically, by the light-scattering method, GPC, IR spectroscopy, and X-ray analysis; the specific surface area of the particles was measured, and their heat stability was determined. The results lead to a conclusion that the unprocessibility of the particles compared with the usual particles of suspension PVC is not caused by differences on the level of molecular structure, but ensues from the difference in their morphology.     

Structural heterogeneity of suspension poly(vinyl chloride) resins

Morphology of poly(vinyl chloride) resin particles formed by suspension polymerization was investigated by a combination of several techniques. Significant differences were found in the internal structure of resins obtained under different polymerization conditions. Five main types of resin particles with different porosity and absorptivity were identified by scanning electron microscopy. Three methods were employed to characterize porosity and structural heterogeneity of resin particles: density fractionation of resin particles in mixtures of methanol and carbon tetrachloride; absorption of silicone oil and dioctyl phthalate by resin particles; and examination of fractured particles embedded in epoxy resins. All three methods gave consistent results and can be used for semiquantitative characterization of resin structural heterogeneity. Different particle structure and degree of resin heterogeneity: can profoundly affect compounding and processing operations.     

Modification of poly(vinyl chloride). XIX. Electroplating of poly(vinyl chloride)

As a preliminary treatment in the PVC-electroplating procedure, treatment with dimethylformamide followed by sensitization leads to a finely roughened and a highly hydrophilic surface with reducing power. This is caused by the formation of an ionic complex compound between dimethylformamide and tin(II) chloride absorbed in the PVC surface. A much more finely and deeply etched surface which exhibits higher adhesion through the mechanical interlocking effect is obtained with the PVC blends containing the plasticizer with a low value of interaction parameter and with a solubility parameter approximate to that of PVC. Adhesion of the metal layer to the PVC surface thus obtained is improved about 1.5 times by thermal aging at 120°C for 20 min.     

Preparation and application of low-molecular-weight poly(vinyl chloride). V. Preparation and characteristics of blended poly(vinyl chloride) by two-step suspension polymerization

Poly(vinyl chloride) (PVC) with relatively broader molecular weight distribution (BMD-PVC) was prepared by two-step suspension polymerization: (1) preparation of poly(vinyl chloride) with relatively higher molecular weight (HMW-PVC) and (2) successive preparation of poly(vinyl chloride) with relatively lower molecular weight (LMW-PVC) in the presence of the resultant HMW-PVC and 2-mercaptoethanol as a chain transfer agent. Some properties of BMD-PVC were investigated: fusion time, melt viscosity, discoloration time, tensile strength at yield, tensile modulus in tension, and elongation at break. © 1994 John Wiley & Sons, Inc.     

Preparation and application of low molecular weight poly(vinyl chloride). II. Thermal stability of blended poly(vinyl chloride)

The blending effect of poly(vinyl chloride) (PVC) with relatively higher molecular weight (HMW-PVC) and relatively lower molecular weight (LMW-PVC) has been investigated by measuring various thermal stability and fusion times. The thermal stability of the blended PVC is improved when the small amount of LMW-PVC obtained using mercapto compounds as a chain-transfer agent is blended into PVC with HMW-PVC. At the LMW-PVC content from about 5–30 wt %, the thermal stability of the blended PVC is much more improved. Furthermore, the blended PVC with LMW-PVC, obtained using mercapto compounds, exhibits significant improvement in the discoloration time. The fusion time of the blended PVC is related to the weight-average polymerization degree of LMW-PVC and the LMW-PVC content. © 1994 John Wiley & Sons, Inc.     

Modification of poly(vinyl chloride). XXXIV. Crosslinked poly(vinyl chloride) via paste-processing

A novel PVC-crosslinking technique using 6-dibutylamino-1,3,5-triazine-2,4-dithiol (DB) was applied for a paste processing to produce a crosslinked PVC product. The paste formulation recommended in the present study consisted of 100 parts of PVC (Zeon 121), 60 parts of dioctyl phthalate, 0.2 parts of MgO, and 6 parts of a 50% solution of DB-Na in butylcarbitol, which gave a highly crosslinked and transparent sheet with an excellent stability for thermal discolouring. The increasing viscosity behaviour of the paste during storage is explained by the effect of interparticle attracting forces of DB-Na which coordinates to the ether oxygen atoms in the glycol derivatives adsorbed on the surface of PVC particles. The increased viscosity can be reduced by addition of 3 parts of N-butyl-benzene-sulfonamide. The tension-distortion properties at elevated temperatures were remarkably improved at the crosslinked product compared with the uncrosslinked. The mechanical properties of the two crosslinked products produced via paste processing and roll-blending are compared in regard to the differences of the uniformity of crosslinking units.     

Influences of initiator addition methods in suspension polymerization of vinyl chloride on poly(vinyl chloride) particles properties

Vinyl chloride suspension polymerization was carried out in a pilot‐scale reactor to study the effects of different methods of initiator addition on poly(vinyl chloride) (PVC) resin properties. The experiments used different arrangements for adding the initiator to the reactor, whereas other reaction conditions were the same: (i) initiator was added to the continuous aqueous phase and then monomer was dispersed in it (conventional method); (ii) initiator was predissolved in monomer before dispersing in the continuous aqueous phase; and (iii) suspending agents along with initiator were added to the monomer before polymerization. The PVC resin prepared by method of (i) had a higher monomer conversion and a higher Sauter mean diameter of grains with a narrow particle size distribution comparable to that of PVC resins by other methods. Scanning electron microscopy showed more uniform particles and fused primary particles in the grains, which confirms lower porosity and lower cold plasticizer absorption (CPA) for PVC grains produced by procedure of (ii). The results showed that when the suspending agents were also predispersed in monomer along with initiator (iii), CPA increases dramatically due to internal porosity of the grains. Simultaneously, a marked decrease in Sauter mean diameter was apparent. Scanning electron microscopy micrographs show that primary particles in the interior of PVC grains prepared by the latter method are looser, and there is more free volume between primary particles resulting the high internal porosity and consequently higher CPA. Mercury porosimetry analysis also confirms these results. K value as a molecular weight characteristic for all methods was the same . J. VINYL ADDIT. TECHNOL., 24:116–123, 2018. © 2016 Society of Plastics Engineers     

The degradation of poly(vinyl chloride). II. Oxidative degradation in solution

The results of studies on the oxidative degradation of poly(vinyl chloride) in a solvent, triphenyl phosphate, are described and compared with results previously reported for the oxidative degradation of bulk polymer samples. A range of chain-breaking and peroxide-decomposing antioxidants of the type commonly used to stabilize polyolefins were not effective in reducing the rate of dehydrochlorination of poly(vinyl chloride).     

On the thermal degradation of poly(vinyl chloride). II. The effect of atmosphere

The early stages of the thermal degradation of PVC were studied. Two commercial, suspension-polymerized resins were thermally treated at different temperatures and oxygen contents. Dehydrochlorination kinetics were followed by conductometric measurements and the formation of polyene sequences by ultraviolet-visible spectroscopy. Crosslinking and chain scission were followed by gel chromatography (GPC) and viscometry. No chain scission was observed in nitrogen atmosphere and no crosslinking in oxygen. Degradation in air proceeded by both reactions. The rate of dehydrochlorination for one of the investigated polymers increased linearly with the logarithm of the oxygen pressure. In nitrogen, an increasing degradation temperature was found to give both an increasing crosslinking and less discoloration. In oxygen, chain scission reactions showed a slight temperature dependence. The temperature effect on the discolorations was similar to that in nitrogen. The main difference between the investigated resins was the amount of internal doubled bonds in the original polymers, the ratio being 2:1. The higher amount resulted in a higher rate of dehydrochlorination, a larger extent of chain scission in oxygen, and a lower extent of crosslinking in nitrogen. Both in oxygen and nitrogen, the obtained results are consistent with allylic mechanisms. In nitrogen, the polyene formation supposedly proceeds by a unimolecular reaction and crosslinking by an intermolecular nonradical dehydrochlorination. In oxygen, radical reactions are superposed and may lead to chain rupture via β-scissions of alkoxy radicals.     

Compatibility study of waste poly(ethylene terephthalate) with poly(vinyl chloride). II

In this study, exploration of possibilities for use of recycled poly(ethylene terephthalate) (PET) in powder form as a filler in the PVC matrix was made. Powdered PET surfaces were modified by plasma to enhance the degree of interaction and, hence, the compatibilities. For modification, a series of different chlorine-containing monomers at two plasma operational conditions selected were used, in addition to the direct use of an oligomer of vinyl chloride. A series of mechanical, thermal, and surface energy analyses made with the composite samples prepared showed that it is possible to improve the properties by employing proper surface modification, which, in some cases, can even lead to synergestic results. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:765–774, 1998     

Retrostructural analysis of poly(vinyl chloride) particles

A poly(vinyl chloride) (PVC) matrix of final particles is investigated by means of quasi-elastic light scattering (QELS) and high resolution porosimetry (HRP). It is demonstrated that the QELS method is a powerful tool for the detection of various higher organized structures in particle interiors, which in all likelihood will be a difficult-to-process fraction of the resin. Measurements of common PVC grades revealed that the QELS records are usually composed of three distinctly separated size distributions, which were assigned to the size distribution of single macromolecules dissolved (maximum at ca. 10 nm), associates of macromolecules (primary particles, the maximum at ca. 100–200 nm), and microglobules (the maximum at ca. 0.8–1 (μm)). The properties of primary particles are presented, as well as the correlation between QELS and HRP records. Based on this correlation, it can be suggested that the pore size distribution is in fact a morphological fingerprint of individual PVC resins. Some consequences of the results obtained for the evaluation of the processsing properties of PVC are discussed.     

Stabilization of poly(vinyl chloride). V. Synergism between metal soaps and polyols upon stabilization of poly(vinyl chloride)

The marked discolorations observed on aged poly(vinyl chloride) (PVC) containing synergetic metal soaps, in the early heating stage, were due to the excessive coloration of π complex of metal chloride and double bonds in the polyene chain. These excessive colorations were inhibited by masking the excessive metal chloride with some masking agents, thereby slowing down the abrupt discoloration of PVC. In this paper, the masking effect of various alcohols such as 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, hexylene glycol, glycerol, 1,2,4-butanetriol, trimethylolethane, trimethylolpropane, meso-erythritol, pentaerythritol, sorbitol, and dipentaerythritol is investigated. The polyhydric alcohols, except dihydric alcohols, showed superior masking effect and markedly improved the thermal stabilization effects of synergetic metal soaps. The mechanism for the synergetic effects between polyols and metal soaps should be based on the masking effect of polyols, owing to the formation of the colorless complex of polyols with excess metal chlorides obtained from the metal soap.     

Spectroscopic observations on nonequilibrium glassy poly(vinyl chloride) and polystyrene

The relationship of valence-coordinate deformation to the temperature dependence of some infrared peak-absorption frequencies in Poly(vinyl chloride) (PVC) and polystyrene (PS) is stated. A skeletal band and a CH₂ rocking band in PVC and a ring-mode band in PS were studied in two kinds of experiments: steady heating and cooling of a quenched (nonequilibrium, glassy) sample through its glass-transition temperature, T_g, and long-term annealing of quenched samples below T_g, followed by steady heating and cooling. The results, a slope discontinuity, ΔM, in the v(T) relation at T_g and a frequency shift, Δv_iso, during isothermal annealing below T_g, are analyzed in two theoretical approaches. Interchain and intrachain contributions to the observed frequency shifts are expected to occur with a differing relative significance in different kinds of molecular vibrations, leading to one possible method of distinguishing valence-coordinate deformation (chain strain) from other effects.     

On the thermal degradation of poly(vinyl chloride). III. Structural changes during degradation in nitrogen

The structural changes in poly(vinyl chloride) during thermal degradation in nitrogen at 190°C have been investigated. From gel permeation chromatography analyses no chain scission, but only crosslinking reactions were observed. An increase in the molecular weight was measured even at 0.3% conversion. For longer polyene sequences and at higher conversions, a crosslinking reaction competed with the “zipper” propagation. The secondary reactions, were more extensive at longer polyene sequence lengths. The growing polyene sequences can be terminated not only by branching reactions but also at existing pendent chloromethylene groups. A decrease in the amount of short chain branching with conversion also indicated other types of secondary reactions. Such a decrease was also observed during thermomechanical degradation in a Brabender Plastograph. The average polyene sequence length was calculated to be around 10, depending somewhat on the type of analysis used. Although allylic chlorine atoms seem to be the main points of initiation, other sites cannot be excluded as the number of initiation points increases appreciably during the early stages of the degradation. Such an increase is, of course, also consistent with a radical mechanism.     

Stabilization of poly(vinyl chloride). X. Synergisms between epoxidized polybutadienes and metal soaps on the stabilization of poly(vinyl chloride)

Effects of epoxidized 1,2- or 1,4-polybutadienes on the zinc stearate/calcium stearate synergetic soap-induced thermal stabilization of poly(vinyl chloride) (PVC) were investigated by colorimetry. The remarkable stabilization effects of epoxidized polybutadienes could not be observed on the PVC films without synergetic soaps, while the stabilization of PVC was markedly enhanced by combined use of epoxidized polybutadienes with synergetic soaps. Excessive coloration of cool color-producing zinc chloride-polyene complexes that were the source of abrupt discoloration of stabilized PVC was retarded by using epoxidized polybutadienes together with synergetic soap. The synergism of epoxidized polybutadienes was enhanced with increasing epoxy contents. Moreover, the effect is also clearly dependent on degree of dispersion of epoxidized polybutadienes in PVC. Further colorimetries, infrared (IR), and X-ray photoelectron spectroscopies on the various PVC-containing epoxidized polybutadienes and zinc chloride indicated that the epoxy groups capture the zinc chloride. The synergistic effect between epoxidized polybutadienes and metal soap was ascribed to epoxidized polybutadienes serving as acceptors for the excessive cool color-producing zinc chloride produced by zinc stearate to retard the abrupt discoloration of stabilized PVC. The plate-out phenomenon appeared during the molding process of PVC-containing epoxy compounds was considerably retarded by epoxidized polybutadienes which modified polyols. The polyol-modifying epoxidized polybutadienes also exhibited a marked effect on PVC stabilization with metal soap.     

Stabilization of poly(vinyl chloride). III. Synergism between metal soaps and masking agents on the stabilization of poly(vinyl chloride)

The stabilization mechanism by synergetic metal soaps containing complementary colors was previously reported. With increased heating times, the color of heated poly(vinyl chloride) (PVC) films containing Cd/Ba and Zn/Ca synergetic soaps markedly deviated from the polyene color. These color deviations usually decreased the thermal stability of PVC. Discoloration from polyene color to blue appeared especially on PVC films containing Zn/Ca synergetic soap and was concomitant with a marked decrease in thermal stability. The stabilization of PVC containing synergetic metal soaps can be improved by masking or removing the excessive color. In this work, the addition of various masking agents, such as ethylenediaminetetraacetic acid, o-phenanthroline, triethanolamine, urea, N,N′ -dimethylolurea, melamine, stearylamide, and lactams, to PVC containing synergetic metal soaps was investigated. It was shown that these masking agents do markedly slow down the discoloration of PVC.     

Physico-chemical characterization of poly(vinyl chloride). I. Solution properties

Poly(vinyl chloride) was fractionated and its solution properties were studied. Calibration of the gel permeation chromatograph was carried out using poly(vinyl chloride) and polystyrene. Empirical correlations were established for the calibration plots.     

Stabilization of poly(vinyl chloride). I. Change in color of poly(vinyl chloride) compounded with some metal soaps

Poly(vinyl chloride) (PVC) with one or more metal salts added was colored by the action of heat to investigate the stabilization mechanism. The coloration and the color difference of heated PVC compound films varied according to the metal salt added. The decoloration of the colored compound films was advanced markedly in THF, DMF, acetone, and ammonia. On the other hand, the heated achromatic PVC film containing Cd/Ba soaps underwent an opposite change, from colorless to yellow orange, in the above materials. This means that the coloration of heated compound films may result from the formation of some complex (for example, π complex of the polyene with the metal chloride). Furthermore, the colored film with cadmium stearate was decolored by roll mixing with the colored film containing barium stearate. These results indicate that the stabilization with metal soaps may be founded on a physical phenomenon such aa an effect of complementary color.