Effect of lanthanide (La(III))‐containing ionomer on thermal stabilization of poly(vinyl chloride)

A type of lanthanide (La(III))‐containing ionomer based on acrylate processing aid (ACR) for poly (vinyl chloride) (PVC) was synthesized, and influence of the ionomer on thermal stabilization of PVC was investigated with visual color comparison and Congo red methods. Results revealed that the ionomer with a suitable La(III) content behaved as a good costabilizer to PVC. It was able to extend static stabilization time of PVC and postpone “zinc burning.” The stabilizing efficiency of the ionomer to PVC depended on ion content, which was discussed in terms of Eisenberg–Hird–Moore model. Moreover, Fourier transform infrared test verified that this ionomer can react with zinc stearate (ZnSt₂) to form some new structures, which is responsible for postponing “zinc burning.” The ionomer and epoxidized soybean oil exhibited a synergistic effect on the stabilizing efficiency of calcium stearate (CaSt₂)/ZnSt₂ stabilizer to PVC compounds. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

哌嗪基单丁酰胺酸钙/锌的合成及对PVC热稳定性研究

以丁二酸酐、哌嗪、氯化钙、氯化锌为原料,通过两步反应制备了哌嗪基单丁酰胺酸钙/锌（PSACa/Zn）热稳定剂。采用元素分析、电感耦合等离子体原子发射光谱仪（ICP?OES）和傅里叶变换红外光谱仪（FTIR）对产品结构进行表征,通过刚果红试纸法、转矩流变仪法、热失重法考察了PSACa/Zn对PVC的热稳定性能,并筛选了PSACa和PSAZn的最佳配比。结果表明,PSACa和PSAZn对PVC的静态热稳定时间分别可达74.5、41.5 min,优于硬脂酸钙（CaSt₂）、硬脂酸锌（ZnSt₂）热稳定剂;PSACa和PSAZn复配使用时,以m_PSACa∶m_PSAZn=1∶1时性能最佳,对PVC静态热稳定时间可达92 min,动态热稳定时间可达905 s;发现PSACa/Zn对PVC的长期热稳定性良好。     

Effect of lanthanum cyanurate as novel organic thermal stabilizers for polyvinyl chloride

Lanthanum cyanurate was synthesized by reacting cyanuric acid and lanthanum nitrate at basic condition and was characterized by elemental analysis and Fourier transform infrared spectroscopy. Its application as thermal stabilizer for poly(vinyl chloride) (PVC) was investigated by Congo red test and discoloration test. In comparison with other heat stabilizers, including lanthanum stearate, calcium stearate, and zinc stearate, lanthanum cyanurate exhibits high stabilizing effect with excellent initial color of PVC. The stability time reaches the maximum (80 min) when the percentage of lanthanum cyanurate in PVC is 2.5%. The combination stabilizers (LaC₃N₃O₃/Zn(St)₂ obviously increase the complete discoloration time of PVC in comparison with the stabilizer of Zn(St)₂. The stability time of PVC increases from 14 min (stabilized by zinc stearate) to 26 min (stabilized by LaC₃N₃O₃/Zn(St)₂). LaC₃N₃O₃ also shows a slightly stronger effect on tensile strength of PVC than La(St)₃. Therefore, the LaC₃N₃O₃ can be used to replace La(St)₃ and serve as a costabilizer to improve stabilization efficiency of calcium/zinc stabilizers for PVC. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

氰尿酸镧的协同作用及其复合稳定剂的研究

以氰尿酸、硝酸镧、氢氧化钠为原料合成了氰尿酸镧,通过刚果红试纸法研究了氰尿酸镧与硬脂酸钙、硬脂酸锌、季戊四醇、β-二酮对PVC热稳定性的协同作用;以协同作用为依据,合成了3组复合稳定剂,并且研究了这3组稳定剂的热稳定性、变色性。结果表明:氰尿酸镧与硬脂酸钙、硬脂酸锌、季戊四醇之间有明显的协同作用,但与β-二酮协同作用不明显;复合稳定剂a在热稳定性试验中比另外两组效果好,而复合稳定剂c在变色性方面比另外两组效果都好。     

氰尿酸钙/锌的制备及其在PVC制品中的应用

以氰尿酸、氢氧化钙和氧化锌为原料,去离子水为溶剂,分别合成了聚氯乙烯(PVC)用热稳定剂氰尿酸钙、氰尿酸锌。采用元素分析仪(EA)、傅里叶变换红外光谱仪(FTIR)、热失重分析仪(TG)以及扫描电镜(FESEM)对氰尿酸钙/锌进行了表征分析。通过烘箱热老化和刚果红测试考察了氰尿酸钙/锌对PVC制品热稳定性能的影响,并对热稳定机理进行了探究。结果表明,单独加入PVC质量1%的氰尿酸钙或氰尿酸锌,PVC制品的热稳定性要优于加入等量的硬脂酸钙或硬脂酸锌;氰尿酸钙/锌复配后表现出良好的协调作用,氰尿酸钙/锌最佳质量比为3∶1,热稳定时间达28 min,PVC试片在70 min完全锌烧;并且,环氧大豆油(ESBO)是一种非常适合氰尿酸钙/锌体系的辅助稳定剂,能够进一步提高PVC体系的热稳定性能。     

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     

异烟酸镧的合成及对PVC热稳定作用的影响

以异烟酸、硝酸镧、氢氧化钠等为原料合成了异烟酸镧,并对合成的产物进行了分析与表征,通过刚果红试纸法和高温老化箱实验研究了异烟酸镧对聚氯乙烯（PVC）的热稳定作用及变色情况的影响,并与硬脂酸镧、硬脂酸锌、硬脂酸钙和季戊四醇等热稳定剂对PVC的稳定性进行了比较,同时将异烟酸镧与其他稳定剂进行了复配。结果表明,异烟酸镧单独作为PVC稳定剂的稳定性效果不佳,长期稳定性一般,抗变色能力也不好;当异盐酸镧∶硬脂酸锌∶季戊四醇/份=3∶1∶1（质量份数比）,总用量为PVC的2.5 %时,PVC的稳定时间达到22 min;异烟酸镧的稳定机理为：PVC分解释放出的HCl被异烟酸镧吸收生成了LaCl3,减少了HCl对PVC降解的催化作用,抑制PVC的降解。     

壳聚糖对PVC热稳定性能影响研究

选择价格低廉的多种多羟基化合物,利用刚果红试纸法比较各多羟基化合物的静态热稳定性,发现壳聚糖对聚氯乙烯（PVC）的静态热稳定性最好。通过刚果红试纸法进一步研究壳聚糖与常见主热稳定剂硬脂酸钙、硬脂酸锌及硬脂酸镧的静态热稳定性能,利用热老化烘箱法比较研究壳聚糖与常见主热稳定剂的抗变色能力。采用转矩流变仪测试比较壳聚糖和常见主稳定剂对PVC的动态热稳定性能,并采用热失重分析壳聚糖对PVC热降解过程的影响。结果表明：壳聚糖对PVC的热稳定能较好,静、动态热稳定性时间分别为4 020 s和1 355 s。     

氰尿酸镧的合成及其对PVC热稳定作用的研究

以氰尿酸、硝酸镧、氢氧化钠为原料合成了氰尿酸镧,利用红外光谱分析、元素分析等方法对合成产物进行了表征,通过刚果红试纸法研究了氰尿酸镧对聚氯乙烯(PVC)的热稳定作用及变色情况的影响,并与硬脂酸镧、硬脂酸钙、硬脂酸锌等热稳定剂进行了比较。结果表明:氰尿酸根和镧离子发生了配位作用,使得氰尿酸镧具有良好的热稳定作用,当氰尿酸镧用量为PVC的2.5%时,PVC的热稳定时间可达到80 min;氰尿酸镧与硬脂酸锌之间有明显的协同作用,二者复配可以有效改善氰尿酸镧的初期着色性,当氰尿酸镧/硬脂酸锌=1/3、总用量为PVC的2.5%时,PVC的热稳定时间可达到26 min。     

Tensile properties,thermal stability,and the mechanism of PVC stabilized with zinc and calcium oxolinic complexes

Two novel thermal stabilizers, zinc and calcium oxolinic complexes (Zn(Oxo)₂ and Ca(Oxo)₂), with superior tensile properties and notable thermal stability effect for polyvinyl chloride (PVC) are reported here. The complexes are synthesized without any organic solvents, and the structures are confirmed as Zn(C₁₃H₁₀NO₅)₂·H₂O and Ca(C₁₃H₁₀NO₅)₂·3H₂O by Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray fluorescence spectrometry, and elemental analysis. The PVC samples stabilized with the complexes show superior tensile strength and elongation at break compared with zinc and calcium stearates by tensile test. The results of Congo red test, dehydrochlorination test, and discoloration test show that: (1) Zn(Oxo)₂ is better than zinc stearate as thermal stabilizer for PVC; (2) Zn(Oxo)₂ and Ca(Oxo)₂ show notable synergistic effect with calcium stearate and zinc norfloxacin respectively. The mechanism of the superior tensile properties and notable thermal stability effect is due to the ability of the complexes to absorbing HCl and reacting with PVC chains, which result in the special chain extension of PVC and the delay of autocatalytic effect and zipper-like dehydrochlorination. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47004.     

Synthesis of Bismuth(III)Neodecanoate and Its Application to Poly(Vinyl Chloride) as a Thermal Stabilizer

The bismuth(III)neodecanoate (Bi(Ne)₃) was synthesized via the method of co-reaction of bismuth oxide, neodecanoic acid, and acetic anhydride and then characterized by Fourier transform infrared spectroscopy (FTIR) and elemental analysis (EA). The effect of Bi(Ne)₃ as a thermal stabilizer on poly(vinyl chloride) (PVC) was assessed by thermal aging test, Congo red test, conductivity measurement, and thermogravimetric analysis, respectively. The results showed that Bi(Ne)₃ significantly provided PVC with a good initial color and long-term stability. Bi(Ne)₃ played a role in improving the stabilizing efficiency of PVC through absorbing hydrogen chloride (HCl) and displacing labile chlorine atoms in PVC molecular chains.     

油酸⁃苯甲酸钙/锌液体复合热稳定剂的制备与表征

以油酸、苯甲酸、氢氧化钙和氧化锌为主要原料,氧化植物油为溶剂,一锅化反应制备了油酸?苯甲酸钙/锌液体复合热稳定剂。采用刚果红试纸法和热老化法考察了其对聚氯乙烯（PVC）的静态热稳定性能及与辅助热稳定剂β?二酮、亚磷酸苯二异辛酯、季戊四醇间的协同作用。通过转矩流变仪、紫外光谱仪、场发射扫描电子显微镜测试了最优样品对PVC热稳定性能。结果表明,油酸?苯甲酸钙/锌液体复合热稳定剂对PVC的静态热稳定时间可达50 min,与亚磷酸苯二异辛酯具有最好的协同作用,最优样品对PVC的静态热稳定时间可达71 min,动态热稳定时间可达970 s,平衡扭矩37.3 N·m;紫外分析表明其具有较强地抑制共轭数3以上的共轭多烯生成的能力;其与PVC间的相容性较好,能均匀的分散在PVC颗粒表面,60 min前具有较好地抑制PVC降解的能力。     

硬脂酸镧/己二酸钙/己二酸锌复合热稳定剂对聚氯乙烯性能的影响

为提高聚氯乙烯加工热稳定剂的功能,合成并复配制成一种新型硬脂酸镧/己二酸钙/己二酸锌复合热稳定剂。利用热重分析仪、平板流变仪、动态力学谱仪等对聚氯乙烯热稳定性（刚果红法）、力学性能、流变性能、动态力学性能等进行了研究。结果表明,当己二酸钙与己二酸锌的质量比为1∶4 时,聚氯乙烯的热稳定时间最长;当加入硬脂酸镧且己二酸钙与己二酸锌的质量比为2∶3时,聚氯乙烯的热稳定时间由原来的86 min提高到135 min,冲击强度提高了30 %;加入硬脂酸镧降低了聚氯乙烯的储能模量、损耗模量和损耗因子。     

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.     

α-酮戊二酸镧的制备、复配及对PVC热稳定性能

以α-酮戊二酸、硝酸镧、氢氧化钠为原料，水为溶剂，经两步法制备了α-酮戊二酸镧。采用元素分析、ICP-OES和FTIR对产物结构进行了表征。通过刚果红试纸法测试产品对PVC的静态热稳定性，转矩流变仪法测试产品对PVC的动态热稳定性，TGA研究产品对PVC热降解动力学的影响，并将产品与β-二酮、PDOP、PER、ESO等辅助热稳定剂复配，考察其协同性能，采用SEM观察热降解不同时间的PVC的微观表面形貌。结果表明，α-酮戊二酸镧对PVC具有较好的热稳定作用，添加3 wt%时，静态热稳定时间可达13min，动态热稳定时间可达1820s，可将PVC热降解过程的平均活化能提高15.78 KJ/mol，其与PER之间协同作用最佳，复合热稳定剂对PVC的静态热稳定时间达37min，动态热稳定时间达3480s。SEM观察发现复合热稳定剂能较好的抑制PVC团聚。     

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     

氰乙酰脲对聚氯乙烯的热稳定作用

以三盐基硫酸铅（TLS）及N,N-二甲基-6-氨基尿嘧啶（DMAU）为参照,通过刚果红法和烘箱热老化法研究了N,N-二甲基氰乙酰基脲（DMCAU）对聚氯乙烯（PVC）的热稳定作用。结果表明,DMCAU的热稳定特性与DMAU类似, 单独使用时,刚果红试纸变色时间在较低用量条件下长于TLS,但随添加量的增加变化不如TLS明显,抗着色性亦不比TLS强;与硬脂酸钙(CaSt)并用对烘箱热老化没有明显效果,但在刚果红试验中有协同效应,最佳配比为1∶1。     

Design of nitrogen-containing organic thermal stabilizer with resistance to “zinc burning” and its application

Using maleic anhydride and 6-amino-1,3-dimethyluracil as raw materials, by adding zinc oxide and introducing metal ions, the aminouracil zinc maleate (AM-Zn) was synthesized. The structure of the product was analyzed by Fourier transform infrared spectroscopy and ¹H NMR spectroscopy. The molecule contains ester group, carbon–carbon double bond, carboxylate and diazo group, which can be used as the main thermal stabilizer for poly(vinyl chloride) (PVC). The thermal stability and excellent resistance to zinc burning of AM-Zn were characterized by Congo red method, thermal aging method, thermal weight loss method, electrical conductivity, and other detection methods. In addition, the compound use of AM-Zn and CaSt₂ could further improve the thermal stability performance, which was excellent compared with the commercially available CaSt₂/ZnSt₂. The thermal stabilization effect was the best when CaSt₂/AM-Zn = 2:1, the initial whiteness could reach 50 min, and it was not completely blackened and aged within 80 min. The static stabilization time was 65 min, and the thermal stabilization time is increased by 40 min compared with CaSt₂/ZnSt₂. The thermal stabilization mechanism was analyzed, and the designed and synthesized AM-Zn, a multifunctional molecular structure, had a strong potential as a thermal stabilizer for PVC.     

Design of green zinc‐based thermal stabilizers derived from tung oil fatty acid and study of thermal stabilization for PVC

In this study, a new type of mixed calcium (Ca) and zinc (Zn) thermal stabilizers was prepared and evaluated for poly(vinyl chloride) (PVC) thermal stabilization. The mixed stabilizers were based on the Ca and Zn salts of polycarboxylic acid derived from eleostearic acid—the dominant fatty acid of tung oil fatty acids. Eleostearic acid was converted to a 21‐carbon diacid (C21DA) and a 22‐carbon triacid (C22TA), respectively, which were subsequently turned into calcium (Ca) and zinc (Zn) salts. Thermal stability of PVC compounds was examined by thermogravimetric analysis (TGA), discoloration test, Congo red test, and thermal decomposition kinetics. In comparison, commercial mixed Ca/Zn thermal stabilizers composed of stearate salts (CaSt₂/ZnSt₂), were employed as controls. Because the salts of C21DA, C22TA and stearate have different metal contents, thermal stabilization effects were compared on the basis of both equal salt weight and equal metal ion content. It was noted that under both cases the long‐term thermal stability of the PVC samples followed the order of C21DA‐Ca/C21DA‐Zn > C22TA‐Ca/C22TA‐Zn > CaSt₂/ZnSt₂. The results suggest that the mixed Ca/Zn salts based on tung oil‐derived polycarboxylic acids have higher metal ion contents and cycloaliphatic structures and can effectively improve the thermal stability of PVC. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44679.