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.     

Thermal degradation studies in poly(vinyl chloride)/poly(methyl methacrylate) blends

The miscibility, morphology, and thermal properties of poly(vinyl chloride) (PVC) blends with different concentrations of poly(methyl methacylate) (PMMA) have been studied. The interaction between the phases was studied by FTIR and by measuring the glass transition temperature (T_g) of the blends using differential scanning calorimetry. Distribution of the phases at different compositions was studied through scanning electron microscopy. The FTIR and SEM results show little interaction and gross phase separation. The thermogravimetric studies on these blends were carried out under inert atmosphere from ambient to 800 °C at different heating rates varying from 2.5 to 20 °C/min. The thermal decomposition temperatures of the first and second stage of degradation in PVC in the presence of PMMA were higher than the pure. The stabilization effect on PVC was found most significant with 10 wt% PMMA content in the PVC matrix. These results agree with the isothermal degradation studies using dehydrochlorination and UV-vis spectroscopic results carried out on these blends. Using multiple heating rate kinetics the activation energies of the degradation process in PVC and its blends have been reported.     

Thermal stability and thermal aging of poly(vinyl chloride)/MgAl layered double hydroxides composites

MgAl-LDH(layered double hydroxides) were prepared with CO(NH_2)_2, NH_4 Cl and NH_3·H_2O by the coprecipitation method, respectively. Corresponding composite membranes were prepared by the coating method. LDHs were characterized by WAXS, CO_2-TPD and SEM. The morphology of the PVC/LDHs composite membranes were characterized by means of SEM. The thermal stability of the membranes was analyzed by air aging box and TGA-FTIR. The SEM results show that nano-particles can be compatible with poly(vinyl chloride)(PVC) matrix homogeneously by the stirring-ultrasound blend method with two steps. Furthermore, the air aging box results proved that MgAl-CO(NH_2)_2-LDH has the best effect on thermal stability of PVC. TGA-FTIR results show that MgAl-CO(NH_2)_2-LDH could adsorb more HCl that resulted from the degradation of PVC and improve the pyrolysis temperature of the first degradation stage by 15 K compared with PVC.     

Organic thermal stabilizers for rigid poly(vinyl chloride). Part XI: Anthraquinone derivatives

Anthraquinone and 1-aminoanthraquinone derivatives have been examined as thermal stabilizers or co-stabilizers for rigid PVC in air, at 180 °C. Their high stabilizing efficiency is detected by their high induction period values (Ts) when compared with some of the common reference stabilizers used industrially such as dibasic lead carbonate, calcium-zinc soap and octyl tin mercaptide. Blending these organic stabilizers with some of the reference stabilizers in different ratios had synergistic effect on both the induction period and the dehydrochlorination rate.A probable mechanism for the stabilizing mode of these derivatives has been proposed. The stabilizing efficiency is attributed partially to the stabilizers' ability to intervene in the radical chain degradation process of PVC and to the replacement of the labile chlorine atoms on PVC chains by a relatively more stable moiety of the organic stabilizer.     

Mechanical and thermal properties of nanosized titanium dioxide filled rigid poly(vinyl chloride)

Nano-sized rod-like titanium dioxide (TiO2) filled rigid poly(vinyl chloride) (PVC) nanocomposites were prepared by using injection-molding method. Vicat, Charpy impact and tensile tests as well as thermogravimetric and dynamic mechanical analyses were used to characterize the structure and properties of the nanocomposites. The results showed that nano-TiO2 could improve Vicat softening temperature and also improve thermal stability of PVC during the stages of dehydrochlorination and formation of carbonaceous conjugated polyene sequences, which can be ascribed to restriction of the nanoparticles on the segmental relaxation as being evidenced by raises in glass transition and β-relaxation temperatures of PVC upon filling TiO2. Addition of TiO2 nanoparticles less than 40 phr (parts per hundreds of resin) could significantly improve impact strength of the composites while the TiO2 agglomeration at high contents leads to a reduction in impact toughness.     

Kinetics of the dehydrochlorination of poly(vinyl chloride) in the presence of NaOH and various diols as solvents

The dehydrochlorination of PVC in the presence of NaOH was investigated in different diols. Diethylene glycol (DEG), triethylene glycol (TEG), and propylene glycol (PG) were found to be effective in accelerating the dechlorination of PVC. The dehydrochlorination was promoted in the order TEG > DEG > PG, which was in agreement with the compatibility between PET and the diol. Compatibility resulted in an improved penetration of the PVC particle by the solvent, leading to the acceleration of the dehydrochlorination. The dehydrochlorination of PVC in NaOH/diol followed first-order kinetics, confirming the progress of the reaction under chemical reaction control. The apparent activation energies were 82 kJ mol⁻¹, 109 kJ mol⁻¹, and 151 kJ mol⁻¹ for TEG, DEG, and PG, respectively. The lower the activation energy became the faster the dehydrochlorination of PVC proceeded.     

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.     

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.     

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.     

Polymerization of vinyl chloride catalyzed by a titanium complex with an anionic oxygen tripod ligand

Poly(vinyl chloride) (PVC) was prepared using a titanium complex with an anionic oxygen tripod ligand [CpCo{P(O)(OEt)₂}₃]⁻ () as catalyst and methyl aluminoxane (MAO) as cocatalyst. The polymerization behavior was compared with that of pentamethyl cyclopentadienyl titanium trichloride (Me₅CpTiCl₃). It is observed that L_OEtTiCl₃ can polymerize vinyl chloride with activity comparable to that of Me₅CpTiCl₃. The PVC samples prepared with L_OEtTiCl₃/MAO exhibit bimodal molecular weight distribution and the fraction of high molecular weight peak decreases with polymerization temperature. The microstructure and thermal decomposition of the PVC obtained were studied. Five types of structural defect were detected by ¹H-NMR. Only saturated structural defects are found at low polymerization temperature, but at high polymerization temperature unsaturated structural defects, possibly resulting from dehydrochlorination of the saturated structural defects, appear as well. No head-to-head structural defect is observed. ¹³C-NMR shows that the PVC prepared by L_OEtTiCl₃ has an atactic stereostructure. Compared with the PVC from radical polymerization and anionic polymerization, the PVC samples prepared with L_OEtTiCl₃ show improved thermal stability.     

Degradation of PVCs obtained by controlled chemical dehydrochlorination

Thermal and thermo-oxidative degradation of poly(vinyl chloride)s (PVCs) containing increased concentrations of allylic chlorines, PVC(A)s, prepared by controlled chemical dehydrochlorination with potassium-t-butoxide (t-BuOK) have been studied. The introduction of small amounts of internal allylic chlorines into PVC significantly decreases the thermal and thermo-oxidative stability of the resin. A linear relationship exists between the initial rates (V_HCl)₀ of thermal and thermooxidative dehydrochlorination of solid PVC(A)s and the concentration S of internal allylic chlorines. Both the slope and the intercept of the thermo-oxidative (V_HCl)₀ vs. S plot are higher in oxygen than those obtained in nitrogen at the same temperature; this finding is attributed to fast oxidation of polyenes, and to peroxy radicals formed during polyene oxidation, which initiate subsequent HCl loss by attacking normal repeat units in PVC. The extent of HCl loss as a function of time during thermal degradation of PVC(A)s in intert solvent shows a rapid initial phase followed by a slower stationary phase. The first phase is due to dehydrochlorination involving the labile chlorines, while the stationary phase indicates random initiation of HCl loss at normal? CH₂? CHCl? repeat units. Initial rates of HCl loss increase with S, while the rates of HCl loss during the stationary phase are independent of S. The rate constant of initiation of HCl loss at internal allylic chlorines is almost four orders of magnitude higher than that of random initiation; however, the former is still orders of magnitude lower than that of chain propagation. Quantitative analysis of UV-visible spectra of PVC(A)s degraded in solution suggests geometric polyene distribution. The average length of polyenes decreases as the extent of HCl loss increases and reaches a constant value of ca. 3 at ca. 1% HCl loss for all the investigated PVC(A) samples.     

Investigation of stabilizing action of mixtures of organic phosphites with trialkyl(aryl)tin isocyanates in the thermal degradation of poly(vinyl chloride)

Investigation was made on the effects of mixtures of organic phosphites (tributyl-, trioctyl-, diphenylisooctyl) with isocyanates (triethyl-, tributyl-, triphenyl-, tribenzyltin) upon the rate of dehydrochlorination and crosslinking, and on the absorption spectrum of PVC during degradation in evacuated ampoules at 180°. The effectiveness of stabilizing action of these synergistic mixtures depends on the chemical structures of both phosphite and isocyanate. The activity of isocyanates in mixtures with phosphites decreases in the order: Bz₃SnNCO, Ph₃SnNCO > Bu₃SnNCO > Et₃SnNCO. At 180°. triphenyltin isocyanate decomposes with formation of tetraphenyltin and diphenyltin diisocyanate; parallel with disproportionation, decarboxylation of triphenyltin isocyanate occurs, during which carbon dioxide and N,N′-bis(triphenyltin)carbodiimide are generated. N,N′-bis(triphenyltin)carbodiimide is a stabilizer for PVC in thermal degradation and gives synergistic mixtures with organic phosphites.     

The effect of Zn, Al layered double hydroxide on thermal decomposition of poly(vinyl chloride)

Poly(vinyl chloride)/layered double hydroxide (LDH) composite was prepared by mixing 4 wt% Zn₂Al-CO₃-LDH with PVC and fluxing at 180 °C. The thermal decomposition behaviour of the LDH + PVC composite in air and nitrogen environments was systematically investigated. We found that mixing Zn₂Al-CO₃-LDH into PVC facilitates dehydrochlorination from ca. 300 to 270 °C but reduces the reaction extent to leave more chlorine on the polyene backbones both in air and N₂. We have also found that at 400-550 °C, both in air and N₂, LDH assists the formation of char-like materials and decreases the release of volatile hydrocarbons. From 550 to 800 °C, the char-like materials are mostly retained in N₂ while they are almost completely thermo-oxidized (burned) in air. Thus, addition of Zn₂Al-CO₃-LDH to PVC does not increase the thermal stability, but does promote charring to retard the generation of flame. The influence of LDH on PVC thermal properties has been also addressed mechanically.     

Organic thermal stabilizers for rigid poly(vinyl chloride). Part XII: N-phenyl-3-substituted-5-pyrazolone derivatives

N-phenyl-3-substituted-5-pyrazolone derivatives have been examined as thermal stabilizers or co-stabilizers for rigid PVC in air, at 180 °C. Their high stabilizing efficiency is detected by their high induction period values (T_s) when compared with some of the common reference stabilizers used industrially, such as dibasic lead carbonate, calcium-zinc soap and n-octyl tin mercaptide. Blending these derivatives with some of the reference stabilizers in different ratios had a synergistic effect on both the induction period and the dehydrochlorination rate.A probable mechanism for the stabilizing mode of N-phenyl-3-substituted-5-pyrazolone derivatives has been proposed. The stabilizing efficiency is attributed at least partially to the ability of the organic stabilizer to be incorporated in the polymeric chains, thus disrupting the chain degradation.     

热稳定剂对PVC紫外光老化过程中微观结构及宏观性能演变的影响

通过UV-Vis、FTIR、DSC、以及色差、力学性能的测试表征,实时追踪分析了在紫外光老化过程中,含Pb、Sn以及Ca-Zn热稳定剂的PVC体系微观结构和宏观性能的演变过程.结果表明,在相同光老化条件下,PVC/Pb、PVC/Sn和PVC/Ca-Zn体系的微观结构变化规律基本一致,过程中主要的化学反应是,大分子吸收光能后,发生脱HCl生成共轭双键的反应、生成羰基的氧化反应、交联反应和降解反应;不同热稳定剂的作用,主要表现在对于微观结构变化的幅度和动力学过程的影响不同.相应地,3种体系的外观色差和力学性能的变化规律也相似,但色差的变化程度和速度以及老化后力学性能的保持率因所含热稳定剂的不同而不同,其中含Sn体系的颜色稳定性最好,含Pb体系的力学性能保持率最高。     

Kinetics of thermal decomposition of PVC/fly ash composites

In this study, the kinetics and mechanisms of thermal degradation of Poly Vinyl Chloride (PVC) composites reinforced with class-F fly ash are studied experimentally and numerically using Flynn–Wall model. The addition of fly ash to the polymer matrix results in a decrease in the primary degradation temperature and an increase in the secondary degradation temperature. The metal oxides in the fly ash act as acid absorbers, which results in the destabilization of PVC during its dehydrochlorination process. However, they also react with the chlorine free radicals, which prevents the formation of HCl during degradation. In addition, it is observed that calcium and iron oxides, present in fly ash, are more reactive to the chlorine radicals rather than the silicon and aluminum oxides. The effect of fly ash chemical composition on the degradation of PVC composites was studied by comparing the thermal properties of composites containing two different classes of fly ashes, class-F and class-C, at similar levels. Thermal stability of the composites is found to be dependent on the chemical composition of fly ash. Higher dehydrochlorination rate is observed in the case of composites filled with class-F fly ash than those reinforced with class-C fly ash.     

Effect of montmorillonite treatment on the thermal stability of poly(vinyl chloride) nanocomposites

The aim of this research was to study the effect of different intercalants on the thermal degradation/dehydrochlorination of poly(vinyl chloride) (PVC). PVC nanocomposites were prepared containing 2 phr of montmorillonite clay. The montmorillonite was treated with different organic intercalants and analysed by thermogravimetric analysis and X-ray diffraction. All intercalants were found to intercalate the clay. The nanocomposites were prepared on a two-roll mill and pressed into 0.7 mm thick plates. The degradation was analysed by yellowness index, Congo red test and UV–visible spectroscopy. All cationic intercalants were found to accelerate the dehydrochlorination of PVC whereas the non-ionic did not affect thermal degradation. On the other hand, some non-ionic intercalants showed poor dispersion.     

Organic thermal stabilizers for rigid poly(vinyl chloride). Part XIII: Eugenol (4-allyl-2-methoxy-phenol)

Eugenol (4-allyl-2-methoxy-phenol) has been examined as a thermal stabilizer and co-stabilizer for rigid PVC in air, at 180 °C. Its high stabilizing efficiency is detected by its high thermal stability value (Ts) when compared with some of the common reference stabilizers used industrially such as dibasic lead carbonate, calcium-zinc soap and octyl tin mercaptide.Blending this organic stabilizer with some of the reference stabilizers in different ratios had synergistic effect on both the induction period and the dehydrochlorination rate together with the longer extent of discolouration of PVC stabilized by eugenol as compared with the blank and the samples stabilized with reference commercial stabilizers.A probable mechanism for the stabilizing action of eugenol has been proposed. The stabilizing efficiency is attributed partially to the stabilizer's ability to intervene in the radical chain degradation process of PVC and to the replacement of the labile chlorine atoms on PVC chains by a relatively more stable moiety of the organic stabilizer.     

氯化天然橡胶的等速升温热降解动力学

天然胶乳;氯化天然橡胶的等速升温热降解动力学