Heat Degradation of PVC Stabilized by Treatment with Alkylaluminum Compounds

Thermal degradation of PVC treated with alkylaluminum compounds has been studied. Four PVC samples of different molecular weights have been treated with Me₃Al, and Et₃A₁, and the dehydrochlorination rates of the polymers were determined at 190 and 220°C under a nitrogen atmosphere. The alkylaluminum-treated low molecular weight samples show marked increase in thermal stability, i. e., slower rate of dehydrochlorination right from the beginning of degradation, whereas with the higher molecular weight samples stabilization becomes pronounced only after a few percent of dehydrochlorination. The color of R₃Al-treated samples was much lighter (yellowish) than those of controls (dark brown) at 1% HCl loss. The average polyene sequence lengths formed during the early stages of dehydrochlorination are found to be much shorter with RsAl-treated PVC than with virgin samples. It appears as though polyene sequences which arose by zipping- initiation from allylic and/or tertiary chlorine sites are longer than those which form by random initiation along the chain. The autocatalytic (i. e., HC1-catalyzed) dehydrochlorination observed with virgin PVC disappears after treatment with R3A1. The HCl-catalyzed dehydrochlorination is minimized when thin films are used instead of powdery samples, which may be due to higher rates of HC1 diffusion through thin films. Autocatalysis of dehydrochlorination is affected by the concentrations of double bonds and HCl and the length of polyene sequences. Interaction between polyenes and HC1 by hydrogen transfer may lead to the re-initiation of unzipping, thus lengthening the polyene sequences.     

Characterization of polychloroprenes and cationically modified polychloroprenes by thermal dehydrochlorination

Thermal dehydrochlorination of polychloroprenes and modified polychloroprenes was studied and was found to be rapid, readily reproducible, and reliable for the characterization of these rubbers. The rates of thermal dehydrochlorination of polychloroprenes and modified polychloroprenes are first order at 190°C under nitrogen. Significantly, the plot of dehydrochlorination rate (V_HCl) versus dehydrochlorination extent (ζHCl) for polychloroprenes shows three regions. These data may be attributed to three dehydrochlorination regimes associated with four contributing repeat structures that have been identified by ¹³C-NMR spectroscopy: In contrast to polychloroprene, V_HCl vs. ζ_HCl plots for modified (cyclopentadienylated and grafted) polychloroprenes, i.e., polychloroprenes that do not contain allylic chlorines, exhibit only one region suggesting only one dehydrochlorination mechanism in these materials. The slopes of the V_HCl vs. ζ_HCl plots of the modified polychloroprenes are virtually identical. Moreover, the slopes of the V_HCl vs. ζ_HCl plots for modified polychloroprenes and that of the latest of the three regions for unmodified polychloroprene are indistinguishable. This similarity in the V_HCl vs. ζ_HCl curves suggests dehydrochlorination by a fundamentally similar mechanism in these materials, most likely one involving the ? CH₂? C(Cl)?CH? CH₂? structure common to all of them. Concentration of labile chlorines in polychloroprene may be estimated by the differences in the dehydrochlorination kinetics of polychloroprene and modified polychloroprenes.     

Degradation of poly(vinyl chloride) by U.V. radiation—I. Kinetics and quantum yields

The kinetics of the photodegradation of films of poly(vinyl chloride) (PVC) has been studied both in the presence and in the absence of oxygen. The value of the quantum yield of hydrogen chloride evolved, φ_HCl = 0.011, indicates that only one in every 100 photons absorbed induces the dehydrochlorination of PVC, with formation of polyenes. The independence of φ_HCl on the irradiation time and on the initial amount of unsaturation in the polymer argues in favour of an alkene-photosensitized degradation process. The low rate of degradation observed when Pyrex-filtered light is used results primarily from both low absorbance of the PVC film in the 300–400 nm region and photobleaching of the polyenes by the hydrogen chloride evolved. The decrease of φ_HCl for extended irradiation times is attributed to the formation of a highly absorbing surface layer consisting of totally degraded PVC. Competitive chain scission and crosslinking processes develop in the PVC film photolyzed either in nitrogen or in oxygen, with a limiting value of 0.5 for the gel fraction.     

Controlled introduction of allylic chlorines into poly(vinyl chloride)

Colorless poly(vinyl chloride)s (PVC) containing up to 1.6 allylic chlorines per molecule have been prepared by controlled random dehydrochlorination with a strong base. The effect of temperature in the ?50 to +24°C range on the number of allylic chlorines and color of PVC has been investigated by ozonization experiments and UV–visible spectroscopy. A two-parameter kinetic model has been developed which quantitatively accounts for the observations and points the way for further research.     

Degradation of poly(vinyl chloride) by u.v. radiation—II: Mechanism

The mechanism of the light-induced degradation of solid poly(vinyl chloride) (PVC) has been investigated, and an overall reaction scheme has been developed, based on values of the quantum yields for the primary photoproducts. Only a very small fraction (0.2%) of the excited polyenes induces the degradation of PVC, primarily by photocleavage of the allylic CCl bond. The high instability of β-chloroalkyl radicals is responsible for the chain dehydrochlorination that leads to formation of polyenes. In the absence of O₂, chain scissions and crosslinking are postulated to originate mainly from α-chloroalkyl radicals through β-cleavage of CC bonds and radical coupling, respectively. In the presence of O₂, the chain dehydrochlorination still proceeds, together with an oxidative chain process which yields, via peroxy and alkoxy radicals, hydroperoxides, ketones and peroxide crosslinks. Cleavage of the polymer backbone results most probably from the decomposition of tertiary alkoxy radicals by a carbon-carbon β-scission process.     

Cyclopentadienylation of PVC: Characterization and thermal and thermooxidative degradation studies

PVC has been cyclopentadienylated by two conventional basic, LiCp and NaCp, and a new acidic, Me₂CpAl, cyclopentadienylating agent. PVCs treated with basic cyclopentadienylating agents undergo severe random dehydrochlorination and exhibit a significant decrease in thermal and thermooxidative stability. In contrast, according to ozonization and degradation experiments, Me₂CpAl does not cause dehydrochlorination during cyclopentadienylation. The thermal stability of PVC treated with relatively high concentrations of Me₂CpAl and Me₃Al at 25°C markedly increases due to substitution of labile chlorines in PVC with methyl groups. Initial thermal dehydrochlorination behavior of virgin PVC and samples treated with Me₂CpAl at ?30°C are similar. In contrast, thermooxidative stability decreases on Me₂CpAl treatment at ?30°C; this is attributed to ease of oxidation of pendant cyclopentadienyl groups; that is, the formation of peroxy radicals that may initiate dehydrochlorination by attacking unchanged repeat units in PVC. Acceleration of thermal dehydrochlorination disappears and the length of polyene sequences is reduced on Me₂CpAl and Me₃Al treatment. These observations are attributed to differences in rates of protonation-deprotonation; that is, rates of reinitation of zipping of treated and untreated PVCs during thermal degration. The effect of traces of aluminum residues on degradation of modified PVCs, however, cannot be neglected.     

Mathematical models of the initial stage of the thermal degradation of poly(vinyl chloride). II. The thermal degradation of poly(vinyl chloride) with effective removal of HCl

The dehydrochlorination of different samples of PVC under vacuum with continuous removal of HCl by freezing, has been studied at 180–210°C. The comparison of the kinetic curves of the dehydrochlorination of various samples of PVC which were obtained by us and other investigators, with the theoretical curves for the thermal degradation of idealized PVC in the absence of HCl has been carried out. This had made it possible to evaluate the influence of unstable fragments present in the original polymer on the initial rate of PVC degradation quantitatively. It has been shown that the distinction between the stationary rates of the dehydrochlorination of various samples of PVC is determined by the difference of the values of the average length of dehydrochlorination chain, l_av. The most probable interval of the values of l_av has been ascertained to be 4–12. It is established that the most probable value of the constant of the rate of dehydrochlorination of normal links of PVC, k₀, is 2.1 × 10^?7?2.5 × 10^?7 s^?1 at 200°C. © 1993 John Wiley & Sons, Inc.     

Initiated oxidation of polyenes formed in the thermal degradation of PVC

Polyenes formed in the thermal degradation of PVC are readily oxidized in the liquid phase in the presence of a radical initiator. In pure oxygen at a constant rate of initiation, different length polyenes are consumed by a first-order reaction: the rate of consumption is proportional to the polyene length and to the square root of initiator concentration. Applying the relationships given by the theory of chain reactions, we determined the ratio of the rate constant of chain propagation calculated for one double bond k₂ to the square root of the chain-termination rate constant k₄. The value obtained, which is relatively high in comparison to other unsaturated hydrocarbons, reflects very well the high reactivity of polyenes of the degraded PVC sample towards oxidation. Intramolecular chain propagation steps are also likely to play a role in the oxidation of polyenes.     

Thermo-oxidative dehydrochlorination of rigid and plasticised poly(vinyl chloride)/poly(methyl methacrylate) blends

The aim of this work was to study the thermo-oxidative dehydrochlorination of rigid and plasticised poly(vinyl chloride)/poly(methyl methacrylate) blends. For that purpose, blends of variable compositions from 0 to 100 wt% were prepared in the presence (15, 30 and 50 wt%) and in the absence of diethyl-2-hexyl phthalate as plasticiser. Their miscibility was investigated by using differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). Their thermo-oxidative degradation at 180 ± 1 °C was studied and the amount of HCl released from PVC was measured by a continuous potentiometric method. Degraded samples were characterised, after purification, by FTIR spectroscopy and UV-visible spectroscopy. The results showed that the two polymers are miscible up to 60 wt% of poly(methyl methacrylate) (PMMA). This miscibility is due to a specific interaction of hydrogen bonding type between carbonyl groups (CO) of PMMA and hydrogen (CHCl) groups of PVC as shown by FTIR analysis. On the other hand, PMMA exerted a stabilizing effect on the thermal degradation of PVC by reducing the zip dehydrochlorination, leading to the formation of shorter polyenes.     

Mechanism of action of some stabilizers in the thermal degradation of poly(vinyl chloride)

The dehydrochlorination of PVC under vaccum has been studied at 170–200°C by a volumetric method. The accelerating effect of HCl is related to its interaction with the forming polyene units of macromolecules. A mechanism is proposed. The effects of various stabilizers, such as organic salts of Ca, Ba, Cd, trialkyl- and dialkyltin, trialkyl phosphites, and mixtures of phosphites with metal salts upon the rate of dehydrochlorination, polymer crosslinking, and electron absorption spectra of PVC during degradation in evacuated ampoules were investigated. The stabilizing activity of these compounds depends primarily on the effectivity of absorption of HCl and destruction of polyene units by these compounds.     

Thermal degradation of poly(vinyl chloride) synthesized with a titanocene catalyst

PVC was synthesized using a trichloroindenyltitanium-methylaluminoxane catalyst at room temperature, and its degradation was monitored along with a commercial sample at 160, 170 and 180 °C under air or nitrogen atmosphere. The process was followed by HCl evolution, yellowing index, colour formation and thermogravimetric analysis. The produced polymer had a lower molecular weight and higher surface area, compared with a commercial PVC, while ¹H NMR and T_g values show minimal differences between materials. The HCl evolution degradation studies indicate that produced PVC has a lower thermal resistance than commercial PVC, while TGA reveals the opposite behaviour. Yellowing index and colour evaluation give evidence that nitrogen atmosphere and high surface area in produced PVC allow the polyene growth, whereas low surface area and air atmosphere generate shorter polyenes and chromophoric species. Differences in degradation performance are thought to be due to chemical origin, inherent morphology and differences in instrumentation.     

Dehydrochlorination of Poly(vinyl Chloride) in Pyridine. 1. Effect of Conditions

Poly(viny1 chloride) (PVC) was dehydrochlorinated thermally in pyridine solution under N₂ atmosphere and the effect of variation of reaction time, temperature, and concentration of PVC in pyridine was studied. The extent of dehydrochlorination (or conversion, x%) increases with an increase in reaction time and temperature, and with a decrease in the concentration of PVC. Incomplete precipitation of dehydrochlorinated PVC (DHPVC) occurs by nonsolvent (methanol). During dehydrochlorination there is no HCl evolution as it forms a pyridine hydrochloride complex which is supposed to act as a catalyst for dehydrochlorination. A possible mechanism has been proposed. Chain scission and cross-linking reactions are responsible for the molecular weight changes that take place during the reaction.     

Photodegradation and photo-oxidation of poly(vinyl chloride) in solution

Quantum yields of dehydrochlorination and of main chain scission were determined for photolysis of PVC in solution in tetrahydrofuran and 1,2-dichloroethane. The observed auto-accelerated degradation results from an increased absorption of light by the growing polyene structures. The presence of oxygen enhances the efficiency of dehydrochlorination, chain scission and crosslinking processes. From the constant quantum yields, it is inferred that energy transfer occurs from the absorbing polyenes and that initially present unsaturations are responsible for initiation of the degradation.     

FT-RAMAN SPECTROSCOPIC STUDY OF THE FORMATION OF POLYENES DURING THERMAL DEGRADATION OF POLY(VINYL CHLORIDE) AND POLY (N-VINYL-2-PYRROLIDONE) BLENDS

In situ degradation of poly(vinyl chloride)/poly (N-vinyl-2- pyrrolidone) (PVC/PVP) blends has been studied by Fourier-transform Raman spectroscopy. PVP acts as a destabilizer in the thermal degradation of PVC as manifested by the reduction of temperature for the onset of degradation and the time the polymer is held at a particular temperature for this onset. Increasing the amount of PVP in the blends decreases the dehydrochlorination temperature and time. In blends containing high PVP concentrations, polyene bands dominate over nondegraded PVC bands. Maximum polyene lengths of around 35 were achieved. High PVP ratios and prolonged degradation at higher temperatures resulted in a decrease in mean polyene length due to crosslinking and oxidative scission.     

Thiol-s-triazine as a Stabilizer for Thermal Discoloration

The formation of longer polyene chains (thermal discoloration) has been found to be avoidable by using thiol-s-triazines, such as 2-anilino-4,6-dithiol-s-triazine (AF), which hardly reacts with the original chlorine atoms but tends to replace the activated chlorine (allylic chloride) that plays an important role in triggering zipperlike dehydrochlorination. The optimum stabiliizing system is: PVC, 100; DOP, 50; AF, 0.18; Zn stearate, 0.5; Ba stearate, 1.5 parts.     

The simplest mathematical model of the process of the thermal dehydrochlorination of poly(vinyl chloride)

The dehydrochlorination of PVC under vacuum (～ 10^?4 mm Hg), with continuous removal of volatile products by freezing out, has been studied at 180–250°. The equation has been deduced and solved to describe the thermal degradation of PVC. The rate constants of separate steps of polymer dehydrochlorination and the dependence of concentrations of polyenes on time of degradation are calculated.     

Hydrazide‐Catalyzed Polyene Cyclization: Asymmetric Organocatalytic Synthesis of cis‐Decalins

Polyene cyclizations offer rapid entry into terpenoid ring systems. Although enantioselective cyclizations of (E)‐polyenes to form trans‐decalin ring systems are well precedented, highly enantioselective cyclizations of (Z)‐polyenes to form the corresponding cis‐decalins have not been reported. Here, we describe the first application of iminium catalysis to the initiation of polyene cyclizations. Ethyl 1,2‐diazepane‐1‐carboxylate catalyzes the cyclization of polyenes bearing enal initiators. Moreover, chiral bicyclic hydrazides catalyze the cyclizations of (Z)‐polyene substrates to form cis‐decalins with enantioselectivities of up to 97:3 er. DFT calculations suggest the catalysts promote the reaction by stabilizing positive charge as it develops during the bicyclization.     

The influence of tacticity on the thermal degradation of PVC

Based on experimental results on the kinetic zip length of polyene formation and on the polyene distribution in degraded PVC it is deduced, using quantitative model conceptions, that both the configuration and the conformation of the PVC macromolecule may influence the initiation, propagation and termination of thermal dehydrochlorination. In this way it is possible to explain the low ‘basic’ stability of PVC as being determined by the tacticity.     

Effect of stabilizers in the thermal treatment of PVC—VIII. An investigation of double bonds in PVC in the presence of Ba and Cd stearates

Thermal degradation of PVC at 180° in air in the presence of Ba and Cd sterarates and of their combination has been studied. In the presence of Cd stearate, dehydrochlorination proceeds at many sites giving rise to relatively short polyenes. In the presence of Ba stearate, the number of degradation sites is smaller, but long polyene sequences are formed, causing the colouration of the polymer. In synergistic combinations of Ba/Cd stearates, both these mechanisms may operate.     

Etude de la stabilisation du polychlorure de vinyle avec des molecules modeles—II: Action des phosphites et des phosphines sur la degradation du Chloro-4-hexene-2

Phosphines are inhibitors of thermal degradation of 4-chloro-2-hexene because they form strong complexes with either HCl or ZnCl₂, which cause catalysis of the dehydrochlorination. Aliphatic phosphines are more efficient than aromatic phosphines. Aliphatic phosphites also act as stabilizers; they react with HCl, and may be substituted for allylic chlorine in the presence of ZnCl₂ as catalyst; the resulting phosphonate may be destroyed by HCl if phosphite is not in excess. Aromatic phosphites do not react at 60°; they only form a complex with HCl and, in the presence of ZnCl₂, they cause an increase of the dehydrochlorination rate. This effect is due to the reverse reaction, catalysed by a complex HCl-hexadiene, being slowed down because of the competing phosphite-HCl complex.