The effect of barium and cadmium stabilizers on the thermal dehydrochlorination of poly(vinyl chloride): A resonance Raman spectroscopic study

A laser Raman spectroscopic study has been made of the effect of barium and cadmium stabilizers on the thermal dehydrochlorination of poly(vinyl chloride) (PVC). The results obtained indicate that, in terms of the total level of dehydrochlorination, cadmium stearate is not as superior to barium stearate as the visual appearance of the polymer suggests. Also, the level of dehydrochlorination produced in the presence of a mixed stabilizer is not significantly lower than that produced in the presence of barium stearate alone, while samples of the latter exhibit much stronger color. It has also been shown that cadmium stearate can reduce the length of long polyene sequences, presumably by a reaction near the center of such a sequence.     

Zum Mechanismus der thermischen Abspaltung von Chlorwasserstoff aus Polyvinylchlorid. 8. mitt.: Copolymere aus Vinylchlorid und 2-Chlorpropen als polymere Modelle für tertiäre Chloratome in PVC

As polymer model compounds for branched poly (vinyl chloride) with tertiary chlorine atoms copolymers of vinylchloride and 2-chloropropene were prepared. The copolymerization was carried out in bulk at 25°C with acetylcyclohexane sulfonylperoxide. The rate of the thermal degradation of the copolymers in ethyl benzoate increases with growing content of 2-chloropropene monomer units in the polymers. In the same manner, the relative frequency distribution of polyene sequences shifts in favour of shorter sequences. The experimental results can be explained by an increased number of starting points for the dehydrochlorination due to the increasing content of tertiary chlorine atomes.     

Effect of polymerization initiator on early colour of poly(vinyl chloride)

The development of early colour and the dehydrochlorination rate were compared for poly(vinyl chloride) samples obtained by suspension polymerization using two different initiators, dicetylperoxydicarbonate and butylperoxyneodecanoate. The degree of discolouration was measured on pressed plates and expressed as yellowness index (YI), the polyene sequence distribution was monitored by UV/Vis-spectroscopy, and the degradation rate was determined by measuring evolved HCI conductometrically. The PVC sample initiated by dicetylperoxydicarbonate exhibited more extensive early colour and a higher dehydrochlorination rate as compared to the sample obtained with butylperoxyneodecanoate as initiator. The UV/Vis-spectra showed that the early colour originates from polyene sequences. After extraction of the PVC resins with heptane: acetone (85 : 15) the early colour turned out to be almost the same for the two samples. From ¹³C-NMR measurements it was found that the extract of the sample polymerized with dicetylperoxydicarbonate contains unreacted initiator. We suggest that the radicals formed when the remaining initiator decomposes initiate dehydrochlorination. Our results also indicate that radicals from dicetylperoxydicarbonate may cause long-chain branches during polymerization. The radicals formed from butylperoxyneodecanoate, on the other hand, do not seem to react with the polymer molecules. © 1993 John Wiley & Sons, Inc.     

Catalytic effect of hydrogen chloride on the degradation of poly(vinyl chloride)

The distribution of polyenes which results from the chemical dehydrochlorination of poly(vinyl chloride) has been studied in dichloromethane (DCM) and tetrahydrofuran (THF) solvents. A higher percentage of longer polyenes is formed in DCM than in THF. On the addition of trifluoroacetic acid to DCM solutions of the polyenes, new species are formed with strong absorptions in the region 500–800 nm. The absorptions are probably due to polyenylic ions formed by protonation of the polyenes, and the interrelated changes in their intensities can be explained by the migration of short polyene sequences along the polymer chain with the formation of longer sequences. The species are extremely photosensitive and are bleached in a few seconds with light from a medium-pressure mercury lamp. The relevance of these experiments to the effect of HCl on the polyene distribution and on the rate of photocrosslinking is discussed.     

Partially dehydrochlorinated PVC. II. Reactions with dienophiles and hydroxylating agents

Samples of poly(vinylchloride) containing polyene sequences were made by partial dehydrochlorination by alkali in tetrahydrofuran solution, by alkali in dioxane, and thermally in dimethyl-formamide. The reactions of polyene PVC were followed by UV spectrophotometry. Dienophiles were found to have relative reactivities similar to those found in reactions with low molecular-weight dienes. The reaction with maleic anhydride yielded polymers which after hydrolysis contained carboxyl groups. Hydroxylation was made with osmium tetraoxide and performic acid. With the latter reagent the reaction proceeded to complete disappearance of the UV-absorption peaks from trienes and higher polyenes: Gel permeation chromatography analysis showed that hydroxylation could be made with only minor changes in molecular-weight distribution. The formation of gel upon thermal dehydrochlorination in DMF was shown to be due to physical cross linking probably arising by crystallization of polyene segments. The adhesion of the hydroxylated and carboxylated polymers to glass and stainless-steel surfaces was investigated. Films adhered stronger as the degree of dehydrochlorination of the polyene PVC used to make the derivative increased. Samples with long sequences adhered much stronger than those containing short sequences of corresponding degrees of total substitution.     

Effect of thermal decomposition on dielectric relaxation process of poly(vinyl chloride)

Dielectric absorption caused by the molecular relaxation of thermally decomposed poly(vinyl chloride) in air was studied on samples in the form of thin films. It was found that, with the progress of thermal decomposition, the magnitude of α dielectric absorption changes in three stages: (1) initial decrease in magnitude corresponding to the process of the formation of polyene sequences caused by dehydrochlorination; (2) ensuing increase corresponding to the deformation of polyene sequences attributed to oxidation; (3) final decrease corresponding to the formation of crosslinks.     

Structural changes of chlorinated paraffins at processing conditions of particulate filled polypropylene

Structural changes of chlorinated paraffin (CP) have been studied using UV-visible absorption spectroscopy in the 180 to 220°C temperature range. Formation and further reaction of conjugated polyene sequence with and without MgO is of major concern. It was found that CP dehydrochlorinated at normal processing temperatures of polypropylene in the absence of MgO. A mixture of various polyene sequences was formed. Unlike a stabilizing effect on poly(vinyl chloride), MgO showed a catalytic effect for dehydrochlorination of CP. As a result, longer conjugation was formed with MgO at the same conditions except for the absence of MgO. The longer polyenes were selectively reacted at the conditions studied. A possible chemical bond formation at the particulate filler/polypropylene matrix interface was suggested as one of the reinforcement mechanisms of the composite.     

On the thermal degradation of poly(vinyl chloride). IV. Initiation sites of dehydrochlorination

A set of poly(vinyl chloride) samples were investigated with respect to their thermal stability. The dehydrochlorination rates were measured in nitrogen at 190°C by use of a very accurate, conductometric method. For all polymers studied, a significant molecular weight increase was observed after 0.4% conversion. With only one exception, samples exhibiting higher degradation rates showed higher absorptions (350–450 nm) after 0.4% dehydrochlorination. In addition, the relative amount of short polyene sequences was found to be higher for polymers with higher degrees of branching. The dehydrochlorination reaction was predominantly initiated at sites of internal unsaturation (allylic chlorines), but an initiation at tertiary chlorines and unstable end-groups could not be completely omitted. Head-to-head units, extraneous impurities, and syndiotactic sequences were found to be of minor importance in this respect.     

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     

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 gamma-irradiated poly(vinyl chloride) by epoxy compounds. III. Conjugated double bonds and degree of unsaturation in gamma-irradiated PVC–stabilizer mixtures

The concentration of conjugated polyene sequences was studied in γ-irradiated PVC with 4% admixture of four epoxy stabilizers: diglycidyl ether of 2,2-bis(4-hydroxy-3-methylphenyl)propane (I), styrene oxide (1,2-epoxy ethyl benzene) (IV), epoxidized ricinus oil (VI), and epoxidized soybean oil (Drapex 6.8) (VII). As in the former investigations (Papers I and II), the process of the formation of the polyenes occurs in two stages. The concentration of polyene sequences with n double bonds, H_n the total amount of polyene sequences, ∑H_n, the average length of the polyene sequence, n , and the two extents of reaction x and p, were computed. The stabilizing effect of all compounds used agrees with the increasing content of epoxy groups. The addition of stabilizers diminishes the value of n . The decrease of the fraction of long sequences and the increase of short ones occurs. Apart from the binding of evolved HCl, the protective effect towards the macromolecules of PVC consists mainly in the inhibition of growth of chain dehydrochlorination by the epoxy groups.     

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.     

Kinetics and mechanism of the thermal degradation of poly(vinyl chloride)

The kinetics of the thermal degradation of solid powdered poly(vinyl chloride) (PVC) under nitrogen was studied by thermogravimetry, rate of hydrogen chloride evolution, and rate of polyene sequence formation. These results are accommodated by a chain mechanism involving initiation by random dehydrochlorination at normal monomer residues of PVC, and a series of intermediates, each leaking to a stable conjugated polyene sequence. Structural irregularities such as allylic and tertiary chlorine are responsible for a fast initiation process at the very beginning of the degradation. Mean rate constants and activation parameters for random initiation, propagation, and termination reactions of the PVC degradation chain were calculated by simulation. Activation enthalpy/entropy correlations for the experimental data available for dehydrochlorination of chloroalkanes and chloroalkenes in the gas and in the liquid phase or nonpolar solvents and elementary reactions of PVC degradation show that initiation is an HCl elimination through a transition state of four centers requiring a synperiplanar conformation of the >CH–CCl< group, whereas propagation is a dehydrochlorination through a transition state of six centers requiring a cis configuration of the double bond.     

Üuber den thermischen Abbau von Polyacrylnitril und Poly-α-chloracrylnitril

During thermal dehydrochlorination of poly (α-chloro-acrylonitrile) polyene sequences are formed which can be identified via their electron spectra. By spectroscopic comparison of degraded poly (α-chloro-acrylonitrile) with degraded poly acrylonitrile it can be shown, that no conjugated double bonds are formed along the main chain during the thermal treatment of poly acrylonitrile.     

The effect of syndiotacticity of the structure and properties of dehydrochlorinated poly(vinyl chloride) films

The dehydrochlorination of a syndiotacticity-enriched poly(vinyl chloride) (s-PVC) gave polyene materials and the structure and properties of dehydrochlorinated specimens were studied. The results were compared with those obtained for polyene materials formed from a commercial poly(vinyl chloride) (c-PVC). The crystallinity of the s-PVC was higher than that of the c-PVC as revealed by the infrared analysis and X-ray diffraction studies. The dehydrochlorinated specimens from the s-PVC were crystalline to some extent while those from the c-PVC were amorphous. The molecular orientation in the original films was preserved in the dehydrochlorinated specimens. The polyene films from the s-PVC had larger conductivities and showed better doping properties as compared with those from the c-PVC. These results were explained in terms of the larger crystallinity and the increased structural regularity of the s-PVC as compared with those of the c-PVC.     

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.     

Synergistic combination of metal stearates and β‐diketones with hydrotalcites in poly(vinyl chloride) stabilization

A synergistic effect of synthetic hydrotalcites as long term stabilizer with metal soaps (the mixture of calcium and zinc stearate) and metal acetylacetonates on dehydrochlorination of PVC has been studied. A proper balance between color stabilization and HCl scavenging capacity has been obtained. Hydrotalcite was prepared by hydrothermal treatment and characterized by EDX, XRD, FTIR, TGA, and SEM techniques. The material is reasonably crystalline and suggests a relatively well ordered sheet arrangement with crystallite size 24.87 nm. The interlayer water content was calculated from the TGA curves and the suggested formula is Mg_0.76 Al_0.24(OH)₂(CO₃)_0.12·0.5H₂O. Synergism in PVC stabilization has been studied by measuring the HCl evolution during the processing at 180°C. Oven aging method was used to study the color stabilization at higher temperature. PVC sheet with different formulation was prepared using Labcoater and subjected to oven for different time interval. The color development (polyene formation) on oven ageing was recorded using UV–visible spectroscopy. UV–visible studies shows that an average sized polyene gives pale yellow color, whereas red or brown color was developed due to long range polyene (n = 10–14) sequences. Hence, the HCl evolution depends on the rate of dehydrochlorination but color depends on the kind of polyene formed. Mechanism of stabilization suggests that adsorption and ion exchange, both phenomenon, are responsible for hydrotalcites as long term stabilizers. The acetylacetonate complex too substitute allylic chlorides and inhibit formation of long polyene responsible for darkening. A clear effect of synergism has been observed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Kinetics and Mechanism of the Polyene Formation during Dehydrochlorination of Poly(Vinyl Chloride) in the Solid State

Abstract

In investigating the thermal, photolytical and chemical dehydrochlorination of poly(vinyl chloride) (PVC) it is shown that the formation of polyenes proceeds independently of the kind of initiation in a fast zip reaction and by the same mechanism. The sequence length distribution of the formed polyenes depends mainly on the conformation of the PVC chains. A strong correlation between this distribution and the conformation equilibrium of the polymer chains as well as the physical structure of the polymer solid is demonstrated.     

On the influence of HCl on the thermal degradation of poly(vinyl chloride)

The thermal degradation of PVC was studied at 190°C in pure nitrogen and nitrogen containing 10, 20, and 40% HCl (by volume). The rate of dehydrochlorination was determined by gravimetry. Degradations in nitrogen were followed with conductometry in addition. Changes in molecular weight distribution and degree of long-chain branching (LCB) were determined by gel permeation chromatography–viscometry and polyene sequence distribution by UV spectroscopy. The rate of dehydrochlorination increases with the HCI content of the atmosphere. The rate of molecular enlargement also increases but only as a result of the increased dehydrochlorination rate. The increase in M _w and LCB are thus related to the extent of conversion only. Changes in the UV spectra indicate that the increase in rate of dehydrochlorination is mainly due to increased propagation rate in atmospheres containing less than 10% HCI. At higher HCI contents an increase in initiation rate is noted. It is suggested that this, at least in part, is due to the fact that HCI, by forming a cyclic transition state, catalyzes the random elimination of HCI. This process, in turn, is promoted by the presence of polyene sequences.     

铅盐稳定剂对低卤阻燃PVC/PNBR热稳定性的影响

采用刚果红法研究了铅盐热稳定剂对低卤阻燃聚氯乙烯/粉末丁腈橡胶热塑性弹性体脱氯化氢热降解性的影响。结果表明:铅盐类热稳定剂在低卤阻燃PVC/PNBR热塑性弹性体中单独使用时,热稳定效果总体是三盐基硫酸铅>二盐基亚磷酸铅。当二盐基亚磷酸铅、三盐基硫酸铅并用时可提高体系的初始变色温度。