Zinc maleate and calcium stearate as a complex thermal stabilizer for poly(vinyl chloride)

Zinc maleate (ZnMA) and calcium maleate (CaMA) were synthesized by reaction of maleic acid with the corresponding metal oxides and were characterized by X‐ray diffraction, thermal analysis, and Fourier‐transform infrared (FTIR) spectroscopy. The thermal stabilizing effects of ZnMA and CaMA on poly(vinyl chloride) (PVC) were investigated at 180°C in air by a static stability test. The stabilization mechanism of ZnMA and the synergism of ZnMA/CaSt₂ (St = stearate) were also studied by UV‐visible and FTIR spectroscopies, as well as a thermal stability test. The PVC with the ZnMA stabilizer exhibited good thermal and color stability caused by the ability of ZnMA to replace the labile chlorine atoms in PVC chains, absorb hydrogen chloride, and react with the polyene intermediates via a Diels–Alder mechanism. The gel content of the PVC/ZnMA samples reached 31% after 2 min of heating and 44% after 10 min, thereby indicating that crosslinking could easily occur with ZnMA, probably owing to catalysis by Zn species. The static and dynamic stability results showed that the synergistic effect of the ZnMA/CaSt₂ stabilizer was greater than that of ZnSt₂/CaSt₂. J. VINYL ADDIT. TECHNOL., 20:1–9, 2014. © 2014 Society of Plastics Engineers     

Study on pentaerythritol–zinc as a novel thermal stabilizer for rigid poly(vinyl chloride)

Pentaerythritol–zinc (penzinc) was prepared by a solid‐phase reaction technique. The principal volatile products of the reaction between pentaerythritol and ZnO were analyzed with a coupled thermogravimetry—mass spectrometery system. The results indicated that a large amount of water was formed at the reaction temperature. Scanning electron microscopy (SEM) results showed the appearance of penzinc as flaky particles. Accordingly, the penzinc obtained through the dehydration between pentaerythritol and ZnO is likely to be a monopentaerythritol complex, such as zinc monoglycerolate. The thermal stability of poly(vinyl chloride) (PVC) with penzinc as a thermal stabilizer was investigated by a Congo Red test, Oven aging test and thermal gravimetric analysis (TGA). The Congo Red test showed the thermal stability time of PVC with penzinc was 38 min, longer than those with commercial thermal stabilizers. TGA indicated that the penzinc had little impact on the thermal degradation of PVC, but could increase the mass of residues. Oven aging test showed that the penzinc could significantly retard the discoloration during the long‐term decomposition of PVC. Meanwhile, no “zinc burning” was observed in the PVC with penzinc. These results indicate that the penzinc is an excellent thermal stabilizer for rigid PVC. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

N′‐acryloyl benzhydrazide as a thermal stabilizer for rigid poly(vinyl chloride)

N′‐Acryloyl benzhydrazide (ABH) was examined as a thermal stabilizer and costabilizer for rigid poly(vinyl chloride) (PVC) in air at 180°C. Its high stabilizing efficiency was shown by its high thermal stability value (T_s) when compared with those of two common reference stabilizers used industrially, dibasic lead carbonate (DBLC) and a calcium–zinc soap. Blending this organic stabilizer with the reference stabilizers in different ratios had synergistic effects on both the thermal stability and the extent of discoloration of the PVC. The Ni²⁺ complex of ABH gave better thermal stability and lesser discoloration than the parent organic stabilizer. Also, blending that complex with DBLC in different ratios gave better stability and lower discoloration. Thermogravimetric analysis confirmed the improved stability of PVC in the presence of the ABH stabilizer. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers.     

Yttrium fumaropimarat as a novel heat stabilizer for poly(vinyl chloride)

Yttrium fumaropimarat (YFPA) was synthesized with fumaropimaric acid and yttrium acetate as raw materials. The structure of the product was analyzed and characterized by Fourier transform infrared spectrometer, scanning electron microscope, energy dispersive X‐ray microanalysis, and X‐ray diffraction. The results showed that the product was amorphous state, three‐dimensional reticulation compound by the ionic bond of COO^? and Y³⁺. The effect of YFPA on poly(vinyl chloride) (PVC) thermal stability was researched by means of Congo red method and heat oven aging method. The experimental results showed that YFPA was a good long‐term PVC thermal stabilizer and could greatly improve PVC thermal stability and initial stage stainability mixing calcium stearate, zinc stearate, and pentaerythrite. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45015.     

Intercalated hydrotalcite‐like materials and their application as thermal stabilizers in poly(vinyl chloride)

The preparation of hydrotalcites with traditional materials is often based on the corresponding salts and alkali solutions. In this study, to facilitate industrial synthesis and take advantage of the lower cost during the process, a Ca–Al–HPO₃–layered double hydroxide (LDH) was directly synthesized with calcium hydroxide, aluminum hydroxide, and sodium phosphite powders. X‐ray diffraction, Fourier transform infrared, and scanning electron microscopy analyses confirmed the successful synthesis of the phosphite‐intercalated hydrotalcite. Compared with Ca–Al–CO₃–LDH, Ca–Al–HPO₃–LDH enhanced the heat stability of poly(vinyl chloride) (PVC) in terms of both short‐term and long‐term stability because phosphite replaced the allyl chloride and reacted with the conjugated double bonds in PVC; this was deduced through a thermal aging test. The composites of Ca–Al–HPO₃–LDH, zinc stearate, and calcium stearate had a synergetic effect when added to PVC and exhibited excellent thermal stability. In addition, the phosphite reacted with ZnCl₂ in case of the phenomenon of zinc burning. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44896.     

N-acryloyl,N′-cyanoacetohydrazide as a thermal stabilizer for rigid poly(vinyl chloride)

N-Acryloyl,N′-cyanoacetohydrazide (ACAH) and its complexes with some metal ions have been investigated as thermal stabilizers for rigid poly(vinyl chloride) (PVC). Their stabilizing efficiencies have been measured by the continuous potentiometric determination of the evolved hydrogen chloride gas from the degradation process and by the extent of discoloration of the degraded samples compared with some conventional thermal stabilizers. The efficiency of blending ACAH with conventional thermal stabilizers has been investigated. A probable mechanism for the stabilizing action of ACAH is also proposed. © 1998 SCI.     

Photostabilizing efficiency of ultraviolet light stabilizers for rigid poly(vinyl chloride) against photo‐oxidation

The photostabilizing efficiency of different light stabilizers in poly(vinyl chloride) (PVC) was investigated by discoloration, ultraviolet (UV) reflection experiment, Fourier transform infrared spectrum (FTIR), and scanning electron microscopy (SEM). The results show that the addition of light stabilizers can slow down discoloration of PVC. The UV reflection results verify that this change is due to the distribution of light stabilizers on irradiated surfaces, which can absorb (such as organic stabilizers) or reflect (such as titanium dioxide) UV light differently. The order of stabilizers that can slower the extent of discoloration is titanium dioxide (TiO₂) > Tinuvin 234 (U4) > XT 833 (H2), U4 > Tinuvin 531 (U3) > Chimassorb 944 (H1), phenyl salicylate (U1). FTIR results show that the carbonyl group of pure PVC, TiO₂, and H1‐doped PVC increases significantly, indicating that the photo‐oxidation reactions of these irradiated samples are relatively serious. The SEM results show that the surface damages of PVC doped with U2, U4, and H2 are somehow slighter, with only small holes or cavities on the surface, whereas the surfaces of pure PVC and H1‐doped PVC are full of big and deep holes and some holes or cavities of 10 μm are detected. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Insights into the use of zinc–mannitol alkoxide as a novel thermal stabilizer for rigid poly(vinyl chloride)

Zinc–mannitol alkoxide (Zn–Man) was synthesized through alcohol exchange reaction, and investigated by means of Fourier transform infrared spectroscopy and elemental analysis. The thermal stability of Zn–Man for rigid poly(vinyl chloride) (PVC) was evaluated by Congo red testing, conductivity measurements, thermal aging testing, thermogravimetric analysis (TGA), and ultraviolet–visible (UV–vis) spectroscopy test. The experimental results demonstrate that the addition of Zn–Man not only apparently prolonged the static thermal stability time to approximately 96.5 min but also evidently improved the initial color of PVC. More importantly, the color of the PVC sheets stabilized with Zn–Man did not change to black within 180 min; this showed that no zinc‐burning phenomenon occurred. In addition, the results of TGA reveal that Zn–Man raised the initial degradation temperature of PVC to about 273.4°C. UV–vis testing indicated that the presence of Zn–Man decreased the content and shortened the length of the conjugated double bonds of PVC. The possible thermal stability mechanism is discussed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42038.     

Lanthanum histidine with pentaerythritol and zinc stearate as thermal stabilizers for poly(vinyl chloride)

Lanthanum histidine [La(His)₂·(NO₃)·2H₂O or La(His)₂] was synthesized via the reaction of histidine and lanthanum nitrate, and it was investigated as a stabilizer for poly(vinyl chloride) (PVC). The results show that La(His)₂ exhibited a stabilizing effect on PVC as a long‐term stabilizer because it prolonged the stability time of PVC to 76 min, which was about 24 times longer than the stability time of the pure PVC. The stabilizing effect of La(His)₂ as a costabilizer with pentaerythritol (Pe) and zinc stearate (ZnSt₂) was also studied. The results show that the use of La(His)₂ with Pe or Pe/ZnSt₂ improved the stability time of PVC. La(His)₂/Pe/ZnSt₂ provided PVC with a good initial color and long‐term stability, and when it was prepared at mass ratios of 0.8:2.4:0.8 and 1.6:1.6:0.8, the stability times of PVC were improved to 86 and 88 min, respectively. As a nontoxic stabilizer, La(His)₂/Pe/ZnSt₂ has the potential to replace the toxic stabilizers widely used in PVC manufacturing. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42878.     

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     

Influence of additional thermal stabilizers on the reprocessing of postconsumer poly(vinyl chloride) bottles

The addition of heat stabilizers is essential for preventing the degradation of poly(vinyl chloride) (PVC) during its processing. The heat stabilizers consumed in the first run have to be made up before the reprocessing of recycled PVC. In this study, solvent‐cast films, which were prepared from granulated postconsumer PVC bottles mixed with plasticizers and thermal stabilizers, were used. The films were subjected to various heat treatments. No considerable structural change upon heat treatments at 140–160°C was found in IR and differential scanning calorimetry analyses. Polyene formation observed through ultraviolet analysis was not severe, indicating that the added stabilizers worked well in preventing degradation. The weight loss during the heat treatments was attributed partly to the decomposition of PVC and the evaporation of volatile components and mainly to the removal of the solvent upon heating. Although this study was conducted with water bottles that were to be recycled, it may be equally well applied to other similarly formulated PVC‐based materials, such as packaging films. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3994–3999, 2003     

Basic principles of thermal degradation and thermal stabilization of poly(vinyl chloride). Synergism of stabilizer action

Changes in the quantities of active stabilizing components during thermal aging of plasticized poly(vinyl chloride) containing a mixture of calcium and zinc stearates were analyzed. A mathematical model of the stabilization process by using the stabilizer mixture and a computer program for analyzing the process of PVC thermal degradation after the beginning of HCl evolution are given.     

Property improvement of plasticized poly(vinyl chloride) by nano‐TiO2 and poly(methyl methacrylate)–encapsulated nano‐TiO2

To improve the physical properties of plasticized poly(vinyl chloride) (p‐PVC), the p‐PVC nanocomposites filled with four loading levels (3, 5, 7, and 9 parts per hundred of PVC resin) of either nanosized titanium dioxide (nTiO₂) or poly(methyl methacrylate)–encapsulated nTiO₂ (PMMA‐nTiO₂) were prepared by melt mixing on a two‐roll mill, followed by compression molding. The PMMA‐nTiO₂ used in this study was synthesized via in situ differential microemulsion polymerization. The resulting PMMA‐nTiO₂ exhibited core‐shell morphology (nTiO₂ core and PMMA shell) with an average diameter of 42.6 nm. The effects of nTiO₂ and PMMA‐nTiO₂ on the tensile properties, hardness, morphology, and thermal stability of the as‐prepared p‐PVC nanocomposites were then investigated and compared. The inclusion of either nTiO₂ or PMMA‐nTiO₂ nanoparticles increased the tensile strength, Young's modulus, hardness, and thermal stability of the nanocomposites in a dose‐dependent manner and reduced the elongation at break. However, the elongation at break was still higher than that for the neat p‐PVC. Moreover, the PMMA‐nTiO₂ nanocomposites had a higher enhancement of the tensile strength, Young's modulus, hardness, and thermal stability than the nTiO₂ nanocomposites at a similar loading level. Hence, the PMMA grafted on the nTiO₂ surface played an important role in toughening and increasing the thermal stability of the nanocomposites owing to the improved miscibility and interfacial adhesion between the encapsulated nanofiller and PVC matrix. J. VINYL ADDIT. TECHNOL., 22:433–440, 2016. © 2015 Society of Plastics Engineers     

Synthesis and evaluation of poly(dioctyltin maleate‐styrene‐methyl acrylate) as a stabilizer for poly(vinyl chloride)

A novel thermal stabilizer poly(dioctyltin maleate‐styrene‐methyl acrylate) [P(DOTM‐St‐MA)] was synthesized by radical solution polymerization with benzene as the solvent and 2,2‐azobisisobutyronitrile as the initiator. The structure of terpolymer was characterized by FTIR and ¹H‐NMR spectra, and thermal stability of the stabilizer was measured by thermogravimetric analysis (TGA). Evaluation of [P(DOTM‐St‐MA)] as thermal stabilizer for poly(vinyl chloride) (PVC) was measured by acidimeter, and the extent of changing color of PVC was measured by thermal aging method. Compatibilities of four stabilizers with PVC were characterized by scanning electron microscope (SEM). The results showed that, with the same tin content in PVC mixtures, [P(DOTM‐St‐MA)] exhibited better performance as a PVC stabilizer compared with other stabilizers,such as poly(dibutylin maleate‐styrene‐methyl acrylate), DOTM, and dibutylin maleate (DBTM). Furthermore, [P(DOTM‐St‐MA)] had better compatibility with PVC in PVC processing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly(ethylene glycol)–polyhedral oligomeric silsesquioxane as a novel plasticizer and thermal stabilizer for poly(vinyl chloride) nanocomposites

The plasticizing and thermostabilizing effect of poly(ethylene glycol)–polyhedral oligomeric silsesquioxane (PEG‐POSS) on poly(vinyl chloride) (PVC) is discussed thoroughly in this work. As PEG‐POSS content increases, PVC becomes more flexible and the decomposition temperature of PVC increases slightly. Meanwhile, the temperature of maximum HCl emission is elevated from 265.3 °C in neat PVC to 285.7 °C in PVC nanocomposites, with the peak intensity of HCl emission decreased by 30.8%, and a new lower intensity of HCl emission peak appearing at much higher temperature (around 370 °C), which is in accordance with the maximum degradation temperature of PEG‐POSS. Thereby, a possible dehydrochlorination mechanism is suggested according to the fact that the electron donor effect of ether groups would stabilize the C? Cl bonds by means of more electron cloud stacked in those bonds, which agrees with Fourier transform infrared and X‐ray photoelectron spectroscopy experiments in terms of hydrogen bonds. © 2016 Society of Chemical Industry     

Phenyl urea derivatives as organic stabilizers for rigid poly(vinyl chloride) against photo‐degradation

Phenyl urea derivatives have been prepared and investigated as photostabilizers for rigid PVC by measuring the extent of weight loss (%), the amount of gel formation as well as the intrinsic viscosity of the soluble fractions of the degraded polymer. Moreover, the efficiency of these stabilizers was evaluated from the extent of discoloration of the degraded polymer in their presence. The results indicated a reasonable stabilizing effect of these derivatives when compared with the commercially used UV stabilizers: phenyl salicylate (Salol) and methanone, 2‐hydroxy‐4‐(octyloxy)‐phenyl‐benzophenone. A synergistic effect is achieved when the phenyl urea derivatives are mixed with the UV absorbers in the ratio (75 : 25%), respectively. A radical mechanism is proposed to account for the stabilizing action of the products investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2217–2226, 2007     

Effect of relatively nontoxic thermal stabilizers on photodegradation of poly(vinyl chloride)

The influence of relatively nontoxic thermal stabilizers including different types of organic calcium complex (Ca/Zn system of liquid stabilizers) and organotin on photodegradation of poly(vinyl chloride) (PVC) was investigated by color difference measurement, viscosity‐average molecular weight determination, UV–vis spectroscopy, Fourier transform infrared (FTIR), and thermogravimetric (TG) analysis. PVC films containing relatively nontoxic thermal stabilizers were prepared by solution casting and then exposed to xenon‐arc light source with the irradiance of 0.51 W/(m²·nm) at 65°C. Two major chain processes, photodehydrochlorination and photo‐oxidation, occur simultaneously during photodegradation of PVC. It has been confirmed by both color difference and UV–vis spectra that during the former 300 h of irradiation, organic calcium complex stabilizers retard photodehydrochlorination as well as initial color development of PVC films while organotin stabilizers remarkably accelerate photodehydrochlorination after 100 h. Relative carbonyl index (RCI) is first introduced to the analysis of FTIR results, which implies that organotin has a better ability to inhibit photo‐oxidation than organic calcium complex and ensures longer stabilization time. The antioxidation of mercaptan organotin has been observed because it is an effective decomposer of peroxides and hydroperoxides. TG analysis reveals that some unstable structures generated due to the irradiation of ultraviolet can easily split away off from PVC macromolecular backbones under relatively low temperature. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Ways of poly (vinyl chloride) stabilization

Main results of research on poly (vinyl chloride) (PVC) stabilization are discussed. Stabilization is viewed from the standpoint of the modern notions of the reasons for PVC low thermal stability, the complicated nature of its dehydrochlorination, and the kinetics of its degradation. The internal unsaturated oxygen-containing groups of ～C(O)? CH?CH? CHCl～ type are regarded as the main source of the polymer instability. Typical processes resulting in PVC stabilization, such as the substitution of labile chlorine atoms and the destruction of initial active sites during reactions with various chemical agents, as well as the kinetic aspects of stabilizers' effect on HCl elimination and PVC macromolecules crosslinkage are considered. The influence of additives on the polymer coloration is estimated.     

A zinc Schiff base complex as high-efficiency stabilizer for flexible poly(vinyl chloride) against thermal degradation

A high-efficiency zinc chelate stabilizer, Zn-(2-hydroxybenzylidene) aspartic acid (Zn-HBAPA), has been synthesized. From dehydrochlorination and discoloration tests conducted at 180°C, Zn-HBAPA has shown to be an excellent thermal stabilizer for flexible poly(vinyl chloride) (PVC) when compared with industrially used cadmium-zinc soap stabilizer. Blending CaSt₂ derivatives and costabilizer THAM (tris[hydroxymethyl]aminomethane) with synthesized Zn-HBAPA stabilizer in different ratios substantially improved the thermal stability of PVC while maintaining the initial color of the PVC. The thermal stability time and the induction time were 55.5 and 52 min, respectively. The initial color of PVC samples held for more than 70 min, and the time to turn the PVC samples completely black took 160 min. Results also showed that not only did the Zn-HBAPA stabilizer show a good synergistic effect when combined with CaSt₂ and THAM, but it also exhibited good compatibility with PVC.     

Effect of base‐deposited graphene oxide on the thermal stabilization of poly(vinyl chloride)

Graphene oxide was deposited in a base solution to form base‐deposited graphene oxide (bd‐GO) particles. The structure and properties of the bd‐GO particles were evaluated using transmission electron microscopy, powder X‐ray diffraction and X‐ray photoelectron, Fourier transform infrared, UV‐visible and fluorescence spectroscopies. The effect of the bd‐GO particles on the thermal stabilization of poly(vinyl chloride) (PVC) was investigated using the Congo red test and thermogravimetric analysis. The results showed that the thermal stability of PVC was greatly improved by the bd‐GO particles. Furthermore, this stabilization mechanism was investigated using UV‐visible spectroscopy and nitrogen adsorption–desorption isotherm analysis. It was found that the improvement of thermal stability was mainly related to the deactivation of thermally labile structural defects in the PVC chains by the carboxylate and alkoxide moieties of the basic groups in the bd‐GO particles, and the highly efficient adsorption of the bd‐GO particles with hydrogen chloride produced during PVC degradation. © 2015 Society of Chemical Industry