Investigation of lanthanum trioxypurine with zinc stearate and pentaerythritol as complex thermal stabilizers for poly(vinyl chloride)

Lanthanum trioxypurine (LaTr) was triumphantly synthesized by reacting trioxypurine and lanthanum nitrate at neutral condition and was characterized by elemental analysis, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The thermal stability effect of LaTr with its assistant thermal stabilizers about zinc stearate (ZnSt₂) and pentaerythritol (Pe) on poly(vinyl chloride) (PVC) was investigated by Congo red test, discoloration test, UV–vis spectroscopy test, and thermal decomposition kinetics. The results showed that the addition of LaTr as thermal stabilizer could significantly enhance static stability time and long‐term stability of PVC. It could be mainly attributed to the anions in the structure of LaTr, could efficiently absorb the hydrogen chloride released by PVC, and have ability to replace unstable chlorine atoms on structure of PVC. Moreover, the mixing of LaTr, Pe, and ZnSt₂ could reveal an excellent synergistic effect and both promote the initial color and the long‐term thermal stability of PVC. The thermal stability of PVC reached the optimal state when the ratio of LaTr/Pe/ZnSt₂ was 1.8/0.6/0.6. In addition, compared with the reaction energy E_a and UV–vis spectroscopy test's result of PVC samples, the order of PVC's thermal stability was PVC/LaTr/Pe/ZnSt₂ > PVC/LaTr/Pe > PVC/LaTr. The result was further ascertained that LaTr/Pe/ZnSt₂ showed excellent synergistic effect and could be used as an excellent complex thermal stabilizer for PVC. J. VINYL ADDIT. TECHNOL., 25:347–358, 2019. © 2019 Society of Plastics Engineers     

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.     

Zinc glycerolate with lanthanum stearate to inhibit the thermal degradation of poly(vinyl chloride)

Zinc glycerolate (ZnGly) was prepared and used as a poly(vinyl chloride) (PVC) thermal stabilizer in this work. ZnGly was characterized by Fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), thermogravimetry (TGA), and transmission electron microscopy (TEM). Visual color evolution and thermal stability time at 180°C were used to examine the stabilizing efficiency of the samples. The thermal stability of PVC was significantly enhanced through adding ZnGly or ZnGly with lanthanum stearate (LaSt₃). Compared with zinc stearate (ZnSt₂), it was demonstrated the initial color stability was markedly improved and the thermal stability time was obviously extended by adding ZnGly. The thermal stability time of ZnGly was threefold than ZnSt₂. In comparison with CaSt₂/ZnSt₂, the extent of coloration of PVC samples was significantly inhibited though adding LaSt₃/ZnGly. It was verified that the appropriate percents of ZnGly in the mixture were between 25 and 50%. A possible mechanism for the stabilizing efficiency of ZnGly was also proposed. The stabilizing efficiency was attributed to the stabilizer's ability to absorb hydrogen chloride and replace the labile chlorine atoms on PVC chains. Moreover, the dynamic thermogravimetric analysis was used to confirm that combination of LaSt₃ with ZnGly presented an obvious improvement of stability on thermal degradation of PVC. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

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.     

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.     

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     

Effect of zinc maleate/zinc oxide complex on thermal stability of poly(vinyl chloride)

In this study, zinc maleate (ZnMA) and zinc oxide (ZnO) complex (ZnMA/ZnO) was prepared by two methods, namely, by the reaction of maleic acid (MAH) with excess ZnO in aqueous solution and by direct mixing of ZnMA and ZnO at 180°C. The chemical structure of the complex was analyzed by X‐ray diffraction, thermogravimetric analysis (TGA), and Fourier transform infrared (FTIR) spectroscopy. The thermal stabilizing effect of the complex on poly(vinyl chloride) (PVC) was evaluated through static and dynamic stability methods. Compared to calcium and zinc soaps and ZnMA alone, the complex exhibited better thermal stabilizing effect on PVC. The stabilization mechanism was also investigated by ultraviolet–visible spectrometer, FTIR, TGA, and gel content analysis. The results indicated that the complex which involved the replacement of labile chlorine atoms hindered the formation of conjugated double bonds in PVC chains via Diels–Alder reaction, and ZnMA/ZnO complex also exhibited the ability to absorb hydrogen chloride. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41464.     

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.     

Influence of nano‐CeO2 as Co‐stabilizer on the thermal stabilization efficiency of novel calcium/Zinc soap stabilizers for poly(vinyl chloride)

The novel organic calcium (Ca)/zinc (Zn) stabilizer of poly(vinyl chloride) (PVC) was synthesized from poly (zinc methylacrylate) and Ca adipate. The influences of Zn/Ca soap weight ratios and nano‐CeO₂ as co‐stabilizer on the thermal stability of PVC were investigated. Congo red testing, thermogravimetric analysis, dynamic rheology, and dynamic mechanical analysis of the mixtures were performed. The results show that the novel stabilizer has good stabilization efficiency on PVC. When 5 phr (parts by weight per hundred parts of resin) of novel stabilizer (weight ratio of Zn/Ca soap is 6/4) in 100 phr of PVC is used as stabilizer, the Congo red time can reach 192 min, which is 131 min longer than 5 phr of the mixture of 3 phr of Zn stearate and 2 phr of Ca stearate as stabilizer. If 3 phr of mixture of Zn methylacrylate with Ca adipate (weight ratio of Zn/Ca soap is 4/6) and 2 phr of nano‐CeO₂ are used as co‐stabilizers, the Congo red time is 205 min. The combination of nano‐CeO₂ with Ca/Zn soap stabilizer shows an obvious improvement for the thermal stability of the PVC. J. VINYL ADDIT. TECHNOL., 20:243–249, 2014. © 2014 Society of Plastics Engineers     

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     

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.     

Chlorinated poly(vinyl chloride) and plasticized chlorinated poly(vinyl chloride)—thermal decomposition studies

The thermal decomposition of chlorinated poly(vinyl chloride) and three plasticized chlorinated poly(vinyl chloride) systems has been investigated. The routes of decomposition of these systems have been elucidated by investigating char formation and by using a combination of thermogravimetric analysis (TGA) and prolysis/gas chromatography/mass spectroscopy methods (Py/GC/MS). The effects of the charforming/smoke‐suppressing iron(III) compound FeOOH in these polymer systems has also been investigated. The structure of both CPVC polymer and plasticzer determine the path of thermal decomposition and also the quantity and nature of the decomposition compunds formed. Changes in oxygen index and the formation of smoke during burning in these systems have been related to the char that is formed and also to the chemical nature of the decomposition products.     

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     

Polycaprolactone as a permanent plasticizer for poly(vinyl chloride)

Polycaprolactone at moderate usage levels has been determined to provide desirable modifications of both rigid and plasticized poly(vinyl chloride). In rigid PVC it effected significant improvement in melt processing as well as good modulus, tensile strength, and kerosene resistance. Impact strength was not measurably altered, but heat-distortion temperature was appreciably lowered. In flexible PVC, polycaprolactone contributed increased tensile strength and ultimate elongation, reduced volatility, and kerosene extraction. Lowering of modulus and flex temperatures were similar to conventional liquid polymeric plasticizers, but melt processability was not as good as lower-molecular-weight plasticizers.     

Kinetic model for thermal dehydrochlorination of poly(vinyl chloride)

In this paper, a novel method for calculating degradation kinetics is presented. The method has been applied to the thermal dehydrochlorination of two different samples of PVC. It has been observed that this dehydrochlorination is complex and involves two different processes. A model that accounts for the entire dehydrochlorination is proposed. This model involves nucleation and growth and diffusion controlled mechanisms. The kinetic parameters are obtained from linear heating rate, isothermal and sample controlled thermal analysis experiments. Kinetic results obtained from the macroscopic thermal analysis measurements demonstrate the correlation between the kinetics of the thermal dehydrochlorination of PVC and the structure of this macromolecule.     

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.     

Heat stabilizers for poly (vinyl chloride). I. Synergistic systems based on calcium/zinc stearate

Synergism in poly(vinyl chloride) stabilization was studied by the determination of the dynamic and static stability of 34 different formulations. Nine ratios of Ca/Zn stearate were tested. Both the static and the dynamic stability increased almost linearly with the calcium stearate content, but unfortunately the initial discoloration increased as well. Melt viscosity decreased with an increasing content of calcium stearate. This was mainly caused by the difference in lubrication effect between calcium stearate and zinc stearate. Several co-stabilizers (synergists) for the Ca/Zn system were also evaluated. Among these, polyols were found to be the most effective. The addition of Polyol T 34, which was prepared through a coprecipitation of trimethylol propane and pentaerythritol, resulted in excellent initial color and improved transparency. Trimethylol propane and di-trimethylol propane were also powerful in this respect. The best static stability was observed for compounds containing mannitol and sorbitol, although these formulations were slightly discolored. Pentaerythritol and di-pentaerythritol were very effective in extending the static stability, but they were not useful for the improvement of initial color. Well-known complexing agents like EDTA and dimethylglyoxime were surprisingly ineffective as synergists. The addition of tris(nonylphenyl) phosphite resulted in a somewhat higher thermal stability, but not in any significant color improvement.     

Tin dioxide coated calcium carbonate as flame retardant for semirigid poly(vinyl chloride)

The flame retardant and smoke suppressant properties of semirigid PVC treated with calcium carbonate (CaCO₃), tin oxide (SnO₂), the mixture of CaCO₃/SnO₂ and SnO₂‐coated CaCO₃ have been studied through the limiting oxygen index, char yield, and smoke density rating (SDR) methods. The thermal degradation in air of the treated semirigid PVC was studied by thermogravimetry (TG) and differential thermal analysis (DTA) from ambient temperature to 1073 K. The morphologies of the additives and the char formation were studied through SEM. The mechanical property was also studied. The results showed that the semirigid PVC treated with SnO₂‐coated CaCO₃ has a higher limiting oxygen index and char yield, lower SDR and MSDR, a more compact structure of char formation than the semirigid PVC without flame retardant and the semirigid PVC with the equivalent CaCO₃, or SnO₂, or the mixture of CaCO₃/SnO₂, a similar tensile property and greatly improved impact strength compared with that of the semirigid PVC without flame retardant. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 731–738, 2006