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。     

Effects of MgAlCe‐CO3 layered double hydroxides on the thermal stability of PVC resin

MgAlCe‐CO₃ layered double hydroxides (LDHs) with different Ce/Al molar ratios were prepared by the constant pH coprecipitation method. The synthesized materials were characterized by XRD and FTIR, and the results showed that the hydrotalcite‐like materials have a layered structure. Different LDHs as stabilizers were mixed with PVC resin. The tests of thermal aging and Congo red for the PVC composites were carried out at 180 ± 1°C, respectively. The results showed when MgAlCe‐CO₃‐LDHs were added into PVC as single thermal stabilizers, 3 phr (parts per hundred PVC resin) MgAlCe‐CO₃‐LDH with Ce/Al (molar ratio) = 0.075 has a better stabilizing effect on PVC than others. Compared with single thermal stabilizers (LDHs or Ca/Zn systems), the composite thermal stabilizers including 0.3 g calcium stearate (Cast₂), 1 g zinc stearate (Znst₂), and 3 g MgAlCe‐CO₃‐LDH have significantly enhanced the thermal stability of PVC sample, and the thermal stable time was over 190 min. The main reason could be concluded to the special structure of Ce element and the synergistic reaction among MgAlCe‐CO₃‐LDHs, Cast₂, and Znst₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

含有机氮的钙辟复合稳定剂在PVC电缆料中的应用

研究了有机氮热稳定剂的制备、常用品种及其对PVC的稳定机理,刚果红试验及热老化试验结果均表明,添加有机氮稳定剂的钙/锌皂复合热稳定剂对PVC电缆料的稳定效果优于未加有机氮稳定剂的钙/锌皂复合热稳定剂。     

姜黄素作为PVC热稳定剂的应用研究

采用刚果红法和红外光谱分析研究了姜黄素对聚氯乙烯（PVC）的热稳定作用,并与常用的热稳定助剂进行复配。以市售铅盐和钙/锌复合稳定剂为对比组,利用转矩流变仪、电子万能试验机等研究了复合体系的流变性能和力学性能。结果表明,3份姜黄素添加到100份PVC的静态热稳定时间为14 min;姜黄素可缓解PVC的氧化降解;姜黄素与月桂酸镧、硬脂酸钙存在明显的协同效应,复配比例约为1:0.8:0.5时静态及动态热稳定时间为50、47 min;其流变性能和力学性能与添加铅盐（添加量均为3份）基本一致,优于钙/锌复合稳定剂,其中动态热稳定时间远高于两者。     

绿色环保硬质PVC基料的开发及应用

通过正交试验优化了硬质PVC的配方,研究了钙锌稳定剂、DOP、ACR、硬脂酸钙4种组分对PVC共混体系流变性能及试样力学性能的影响,结果表明：①绿色环保硬质PVC基料的最佳配方为：PVC100份、钙锌稳定剂5份、DOP4份、硬脂酸钙0．5份、ACR2份、PE蜡0．7份、硬脂酸0．3份;②影响PVC共混体系流变性能的最主要因素是钙锌稳定剂,其次为DOP,影响最小的是ACR;影响试样力学性能的最主要因素是DOP,其次是钙锌稳定剂,影响最小的是ACR。     

Phosphate ester groups‐containing ricinoleic acid‐based Ca/Zn: Preparation and application as novel thermal stabilizer for PVC

Phosphate ester groups containing ricinoleic acid‐based Ca/Zn (LPPRA‐Ca and LPPRA‐Zn) stabilizer was successfully synthesized from ricinoleic acid (RA) and used as thermal stabilizers for poly(vinyl chloride) (PVC). These thermal stabilizers were characterized by Fourier transform infrared spectrometry, ¹H nuclear magnetic resonance, and inductively‐coupled plasma atomic emission spectroscopy. The effects of LPPRA‐Ca/LPPRA‐Zn, CaSt₂/ZnSt₂, and other stabilizers on the thermal stability of PVC were studied through Congo Red test, discoloration tests, thermogravimetric analysis (TGA), TGA–infrared, and TGA–mass spectrometry. The thermal stability tests show that LPPRA‐Ca/LPPRA‐Zn displays the best initial color stability and long‐term thermal stability for PVC. The superior performance is attributed to the synergistic effect of LPPRA‐Ca and LPPRA‐Zn. Moreover, a lower Zinc content of LPPRA‐Zn in PVC helps to decrease the “zipper dehydrochlorination” of the product, which contributes to a better initial thermal stability. Except for the better stabilization performance, LPPRA‐Ca/LPPRA‐Zn also displays better plasticization performance for PVC compared with other stabilizers. A possible stabilizing mechanism of PVC/LPPRA‐Ca/LPPRA‐Zn system was presented. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45940.     

水滑石在钙锌复合体系中的热稳定性研究

以普通的碱性物质为参比，用刚果红、转矩流变仪等方法测试了水滑石在钙锌体系协同作用下对PVC树脂静态和动态热稳定时间的影响。试验结果表明。水滑石改善PVC树脂的热稳定性效果明显优于在Ca／Zn体系中用的辅助组分弱碱A，在PVC中的适宜用量为2份左右。并简单探讨了水滑石的热稳定机理。     

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     

亚磷酸酯和季戊四醇对聚氯乙烯热稳定作用的研究

通过热老化法、白度测试、电导法及热重分析法,研究并对比了亚磷酸-苯二异辛酯(PDOP)和季戊四醇(PER)作为辅助稳定剂对PVC的热稳定作用。结果表明:PDOP能有效抑制锌烧,当PDOP/Zn比例为4:2时抑制效果最好;硬脂酸钙与硬脂酸锌存在协同效应,最佳Ca/Zn配比是2:1;三元热稳定剂的热稳定效果明显好于二元热稳定剂,且PDOP与Ca/Zn较PER与Ca/Zn有更优良的协同效应,PER/Ca/Zn体系在加热25min时出现泛黄现象P,DOP/Ca/Zn体系在加热45min时仍保持较高白度;证明PER有吸收氯化氢的作用。     

硬脂酸根插层水滑石的合成及应用

采用离子交换法制备了硬脂酸根插层水滑石,运用红外光谱对其进行了表征。通过Haake流变仪、颜色测定仪研究了硬脂酸根插层水滑石与钙/锌热稳定剂并用时的热稳定性,重点考察了水滑石的结构对PVC稳定性能的影响。结果表明,硬脂酸根插层水滑石与钙皂/锌皂复配显著改善了PVC热老化过程中的初期着色性。     

Improvement of the processability and thermal stability of poly(vinyl chloride) with 5,6-diamino-1,3-dimethyluracil

Uracil derivatives are potential nontoxic thermal stabilizers of poly(vinyl chloride) (PVC) and have a better stabilization effect. 5,6-diamino-1,3-dimethyluracil (DDU) was investigated as a thermal stabilizer for PVC. The stabilization effect of DDU was measured by thermogravimetric analysis, thermal aging test, and recording the time of the color change of the Congo red paper (Congo red test). Meanwhile, the processability of PVC stabilized by DDU was investigated through dynamic performance test. The results showed a better stabilizing effect compared with calcium stearate (CaSt₂) and zinc stearate (ZnSt₂). To explain the stabilization of DDU, the probable mechanism was suggested that DDU absorbed and chemically bonded with hydrogen chloride. Therefore, DDU could be used as a thermal stabilizer of PVC.     

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     

碳酸根基水铝钙石的制备及其在PVC中的应用研究

利用氢氧化钙[Ca(OH)2]和氢氧化铝[Al(OH)3]以及无水碳酸钠（Na2CO3）为原料,以去离子水作溶剂,制备了碳酸根基水铝钙石（Ca4Al2(OH)12CO3·5H2O）,通过傅里叶红外光谱、X射线衍射和扫描电子显微镜表征其结构。并将其作为热稳定剂应用于聚氯乙烯（PVC）中,通过热老化、刚果红、电导率和热失重分析等方法检测其热稳定性能。结果表明,Ca4Al2(OH)12CO3·5H2O具有长期型热稳定剂的特性,当其添加量为3份时,热稳定时间可达70 min,静态热稳定时间可达52 min;当Ca4Al2(OH)12CO3?5H2O/ZnSt2/DMAU复配体系的添加量为3份,并且Ca4Al2(OH)12CO3?5H2O:ZnSt2:DMAU在3：0.5：1.5~3：0：2之间时,复配体系的初期白度可达60 min左右,即使到110 min左右也未观察到“锌烧”现象发生。     

新型PVC用液体钙锌复合热稳定剂的合成与应用

对环氧油酸钙、锌皂的合成工艺,以及聚氯乙烯(PVC)用钙锌复合液体热稳定剂的配方进行研究,并探究了复合热稳定剂的协同效应。通过刚果红法、热老化烘箱法等,考察了钙/锌比、金属皂含量、亚磷酸酯、β-二酮、抗氧剂等对复合热稳定剂热稳定性能的影响,确定了这种液体复合热稳定剂配方。目前两种液体钙锌复合热稳定剂已经中试。     

自制环保稳定剂在增塑PVC制品中应用性能的评价

通过刚果红热稳定性实验、热老化实验、流变、力学性能以及黄色指数测定等实验,对比研究了自制钙/锌稳定剂与国外知名钙/锌稳定剂对增塑PVC热稳定性能、加工性能、热老化性能和力学性能的影响。研究发现:自制钙/锌稳定剂在增塑PVC制品方面各种性能几乎与该国外知名钙/锌稳定剂没有差别,在热老化性能和力学性能方面还优于该国外知名钙/锌稳定剂。     

Development of a PVC Waterproofing Sheet

Stabilizer and plasticizer systems were studied for a PVC waterproofing sheet formulation to be processed by calendering. Combinations of stabilizer-lubricant systems that contained (Ba, Cd, Zn), dibasic lead phosphite, epoxidized soybean oil, barium stearate, calcium stearate, and stearic acid were evaluated. Oven aging tests showed that the system that contained 2 phr (Ba, Cd, Zn) stabilizer, 0.5 phr barium stearate, 5 phr epoxidized soybean oil, and 0.25 phr stearic acid was satisfactory. Combinations of diisodecylphthalate (DIIP), tricresyl phosphate (TCP), polybutylene adipate (PBA), and NBR were evaluated as the plasticizer system. Tensile properties in the machine and the transverse directions, cold flex temperature, loss of volatile matter content, and aging properties were studied as functions of the DIIP and PBA contents. A plasticizer system of 35 phr DIIP and 18 phr PBA was found to be satisfactory. The final formulation was processed at industrial scale and the product was characterized for its tensile properties, cold flex temperature, tear resistance, weldability, permeability to water, shrinkage, and its resistance to heat, light, acid, and water.     

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.     

钙／锌复合热稳定剂在硬质PVC中的应用研究

自制了高效、无毒的钙锌复合热稳定剂,利用静态热老化法、刚果红法及脱氯化氢法等研究方法,研究了自制钙锌稳定剂、进口钙锌稳定剂及复合铅盐稳定剂在硬质聚氯乙烯（PVC）中的热稳定性能。结果表明：自制钙锌的初期着色性与复合铅盐稳定剂及进口钙锌稳定剂相当,长期热稳定性优于进口钙锌。自制钙锌稳定剂的降解活化能介于进口钙锌稳定剂与复合铅盐稳定剂之间,降解活化能的差值为1～2kJ／mol,其热稳定性达到了复合铅盐的水平,PVC硬制品加工的要求。     

PVC给水管材用钙锌复合热稳定剂的研制

将硬脂酸锌、硬脂酸钙与稀土热稳定剂硬脂酸镧及辅助热稳定剂复配成钙锌复合热稳定剂。通过动态热稳定试验,确定了最佳钙／锌复合热稳定剂与稀土热稳定剂质量比。通过动态热稳定试验及刚果红热稳定试验,确定辅助热稳定剂β-二酮的最佳用量,用研制的钙锌复合热稳定荆与国外同类产品进行了对比试验。结果表明,自制的热稳定剂具有热稳定时间长、塑化时间短的优点,将此热稳定剂用于PVC给水管材中,管材性能检测结果表明,管材质量符合国标GB／T10002．1-2006的要求。