橡胶籽油基复合型环保增塑剂用于PVC的研究

将自制的橡胶籽油基环氧脂肪酸甲酯（EFAME）与对苯二甲酸二辛酯（DOTP）混合后,与聚氯乙烯（PVC）共混成型,考查EFAME在软质PVC中的增塑性能及其对DOTP的替代效果。利用拉力试验机、差示扫描量热仪、动态热力学分析仪及热老化烘箱对塑化体系的力学性能、加工性能、耐热性及耐久性进行分析。结果表明,复合型增塑剂可有效改善PVC制品的柔韧性、耐磨性、热性能及加工流变性;EFAME用量为20份时,PVC制品的玻璃化转变温度由0.32 ℃降低至-4.63 ℃,质量损失10 % 和50 %时的温度得到提高,热老化整体变色时间提高了4倍。     

Synthesis and evaluation of epoxidized vegetable oleic acid as a novel environmental benign plasticizer for polyvinyl chloride

A bio-based plasticizers, acetyl-oleate triethylene glycol (AOT), was successfully synthesized by using oleic acid as a raw material through esterification, epoxidation, and acetylation. Its structure was analyzed by Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance. The plasticizing performances of this plasticizer was compared with those of two commercial ones: dioctyl terephthalate (DOTP) and dioctyl adipate (DOA). This was done by blending these plasticizers with PVC, respectively. Thermal gravimetric analysis results showed that the 5% weight loss temperature of PVC with AOT was 53°C higher than that of DOA and 36°C higher than that of DOTP. The tensile results showed that the AOT plasticized PVC had excellent stretchability: its elongation at break with 50 phr AOT reached 697.7%. Furthermore, its transmittance was as high as 90%, showing better compatibility of ATO with PVC.     

Plasticizers derived from cardanol: synthesis and plasticization properties for polyvinyl chloride(PVC)

Two natural plasticizers derived from cardanol (CD), cardanol acetate (CA) and epoxidized cardanol acetate (ECA), were synthesized and characterized by ¹H NMR and ¹³C NMR. The plasticizing effects of the obtained plasticizers on semi-rigid polyvinylchloride (PVC) formulations were also investigated. Two commercial phthalate ester plasticizers, dioctyl terephthalate (DOTP) and diisononyl phthalate (DINP), were used as controls. Mechanical and thermal properties, compatibility, thermal stability, microstructure, and workability were assessed by dynamic mechanical analysis (DMA), mechanical analysis, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and dynamic stability analysis, respectively. Results indicated that the natural plasticizer ECA had overallsuperior flexibility, compatibility, thermal stability, and workability comparable to both controls. The obtained CA and ECA have lower volatility resistance and similar extraction and exudation resistance than that of DOTP and DINP. The CA was further blended with DOTP in soft PVC films. Results of DMA, TGA and mechanicalanalysis indicated that CA can serve as a secondary plasticizer to improve the related properties of soft PVC formulations. These CD derived plasticizers show promise as an alternative to fully or partially replace petroleum-based plasticizers.     

固体酸S_2O_8~(2-)/ZnO-WO_3催化涤纶废料制取增塑剂DOTP

介绍了由涤纶废丝和异辛醇在催化剂作用下,一步合成增塑剂DOTP,筛选了几种固体酸作为催化剂,研究了以S2O28-/ZnO-WO3为催化剂,最佳反应条件为:n(PET)∶n(2-EH)=1∶4.0,反应温度210~220℃,催化剂用量1.0 g(PET 8.4 g),反应时间4 h,产物DOTP颜色较浅,产率可达96.5%。     

90℃环保PVC护套料的研制

通过研究基础树脂、复合稳定剂、增塑剂、填充剂等对电线电缆用环保聚氯乙烯(PVC)护套料性能的影响,确定了电线电缆用环保PVC护套料配方:PVC为100.0 phr,Ca/Zn复合稳定剂为8.0 phr,邻苯二甲酸二异癸酯为40.0 phr,对苯二甲酸二辛酯为10.0 phr,重质CaCO3为35.0 phr.对产物性能的表征表明,整个配方体系不含对人和环境有害的Pb、Cd、Hg、Cr6 等重金属及多溴联苯及其醚类,护套料性能完全满足90℃环保PVC护套料的标准性能要求,挤出工艺性能优良.     

利用废感光胶片合成DOTP的工艺研究

利用废感光胶片回收得到对苯二甲酸二(2 乙基己)酯(DOTP)。在单丁基氧化锡催化作用下,将废感光胶片在170～220℃降解,最佳温度为190℃,然后与2 乙基己醇反应置换出乙二醇,并不断蒸出乙二醇,蒸出过量2 乙基己醇后可得到DOTP,所得产品的酯含量达99%,当单丁基氧化锡催化剂用量为0.25%,2 乙基己醇与废感光胶片的摩尔配比为3.0时,DOTP的回收率可达90%。     

增塑剂在软质PVC中的发展

概述了增塑剂的品种和相关应用,并展望了高分子增塑剂在软质PVC中的发展趋势。提出利用PET废料制备（DOTP）,它是一种优良的PVC增塑剂。     

酯化反应合成对苯二甲酸二异辛酯的研究进展

对苯二甲酸二异辛酯（DOTP）是近年发展起来的聚氯乙烯新型绿色增塑剂,酯化反应合成DOTP是最常见的方法之一．本文介绍几种从对苯二甲酸酯化合成对苯二甲酸二异辛酯的常用催化剂,比较其优缺、点,着重综述酯化反应合成对苯二甲酸二异辛酯的最新研究进展,并指出非均相反应是制约反应速率的直接因素,其中离子液体是最有可能实现均相反应的催化剂,从而可望缩短反应时间。     

Epoxidized dimeric acid methyl ester derived from rubber seed oil and its application as secondary plasticizer

A novel plasticizer epoxidized dimeric acid methyl ester (EDAMe) based on rubber seed oil was synthesized. Chemical structure of EDAMe was characterized by Fourier transform infrared (FTIR) and gel permeation chromatography (GPC). Effects of EDAMe as secondary plasticizer and its substitution of commercial plasticizer dioctyl terephthalate (DOTP) in soft poly(vinyl chloride) (PVC) films were studied. The thermal properties, mechanical properties and migration stabilities of PVC films were explored with DMA, TG, TG–FTIR, dynamic thermal stability analysis, tensile and migration tests. The results indicated that the epoxidized rubber seed oil based ester has significantly higher thermal stability than DOTP. When DOTP was substituted with 20% (m/m) EDAMe, the results of initial decomposition temperature (T_i), 10% and 50% mass loss temperatures (T₁₀ and T₅₀), and the first maximum weight‐loss temperature rate (T_P1) reached 267.2 °C, 263.5 °C, 307.3 °C and 298.9 °C, respectively. Furthermore, flexibility of the obtained PVC films enhanced significantly with the adding of EDAMe. The migration stabilities of EDAMe was also investigated and showed good migration resistance. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43668.     

由聚酯废料合成DOTP的研究

介绍了由聚酯废料为原料,用直接酯交换法合成ＤＯＴＰ增塑剂的反应原理,合成方法及产品应用。     

Chemical conversion of PET waste using ethanolamine to bis(2-hydroxyethyl) terephthalamide (BHETA) through aminolysis and a novel plasticizer for PVC

Poly(ethylene terephthalate) (PET) recycling has been carried out by various methods, e.g., mechanical recycling, chemical recycling and energy recovery method. In this study, chemical recycling of PET was carried out by aminolysis using ethanolamine and converted into bis(2-hydroxyethyl) terephthalamide (BHETA). The reaction was performed by varying the PET:ethanolamine ratio, reaction time and catalyst used for waste medical grade bottles of PET. Yield of about 81 % was obtained for PET:ethanolamine ratio of 1:4 (w/w), with 3 h reaction time, at 160 °C with zinc acetate as a catalyst. BHETA was characterized with FTIR, ¹H NMR, and DSC analysis. BHETA was further reacted with heptanoic acid at a molar ratio of 1:2.5. The product obtained was used as a plasticizer for PVC at 5, 10, 15 and 20 parts per hundred (phr) concentration. Thermal and mechanical tests were carried out and the result obtained was compared with the virgin PVC without plasticizer and with conventional plasticizer of PVC, i.e., dioctyl phthalate at 15 phr concentration since new plasticizer showed excellent properties at 15 phr concentration. This newly synthesized plasticizer was completely fused with PVC and in tensile testing helped in increasing the elongation, which was an indication of the plasticization effect shown by this developed material. Glass transition temperature also decreased with an incorporation of the new plasticizer as compared to virgin PVC.     

固载杂多酸催化剂PW12／SiO2复相催化酯化合成DOTP

用１：１２钨磷杂多酸（ＰＷ１２）和硅酸钠通过凝胶法制备了固载杂多酸催化剂ＰＷ１２／ＳｉＯ２并以其为固相催化剂，用对苯二甲酸（ＴＰＡ）和２－乙基己醇（２－ＥＨ）复相催化酯化合成了增塑剂－对苯二甲酸二辛酯（ＤＯＴＰ），该方法具有催化活性和选择性高，合成工艺简单，催化剂容易回收率重复使用以及无废酸液排放等优点。     

废涤纶制取增塑剂DOTP

本文介绍了由废涤纶用间接法和直接法两种方法制取DOTP增塑剂的反应原理、实验流程、产品质量及存在问题与解决办法。     

不同度数白酒介质中PVC制品增塑剂迁移行为研究

采用高效液相色谱仪测定聚氯乙烯（PVC）制品中传统增塑剂邻苯二甲酸二辛脂（DOP）、对苯二甲酸二辛脂（DOTP）和环保增塑剂柠檬酸三丁酯（TBC）、乙酰柠檬酸三丁酯（ATBC）,在42 °、46 °、55 °白酒中的迁移规律,并用Gaussian 03程序对其结构进行模拟计算,探讨了分子结构影响增塑剂迁移行为的机理。结果表明,随着与介质接触时间的延长、白酒度数的增大,增塑剂的迁移率逐渐增大;不同种类分子结构的增塑剂的迁移能力有较大的差异性,增塑剂分子的偶极矩越大,其分子极性越强,增塑剂与PVC相容性就越好,其迁移率越小;几种增塑剂中,迁移率大小为：TBC＞ATBC＞DOP＞DOTP。     

Assessment of degradation of plasticized poly(vinyl chloride) films through polyene formation under isothermal conditions

The aim of this work is to assess the degradation of flexible poly(vinyl chloride) (PVC) films produced using orthophthalate based and recently introduced nonorthophthlate plasticizers which have compliance with recent environmental regulations. The plasticized PVC films were subjected to several heat treatments at 85–160 °C up to 420 min. Ultraviolet–visible spectroscopy was utilized to follow polyene formation upon dehydrochlorination of PVC. The amount of polyenes formed exhibited difference amongst the films those plasticized with diethyl hexylphthalate, diisodecyl phthalate, dioctyl terephthalate (DOTP), and diisononyl 1,2‐cyclohexanedicarboxylic acid (DINCH). The order of polyene concentration formed at the utmost level severe heat treatment is in line with the molecular weight ranking from highest to lowest, as the films with diisodecyl phthalate > DINCH > DOTP > diethyl hexylphthalate. Discoloration assessed in terms of yellowness index revealed that the films having recently introduced plasticizers as DOTP and DINCH were competing well with the films having orthophthalate based plasticizers. Scanning electron microscopy images revealed that the longer times for gelation during their production would improve the maturation of the films although they are already coherent and strong. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46092.     

低挥发环保增塑剂对苯二甲酸二（2⁃丙基庚）酯的应用研究

以对苯二甲酸和2?丙基庚醇为原料,在钛酸异丙酯为催化剂的条件下制备对苯二甲酸二（2?丙基庚）酯（DPHTP）,并将DPHTP作为增塑剂用于制备聚氯乙烯（PVC）柔性薄膜,与市售DOP和DOTP进行应用性能的比较。通过傅里叶变换红外光谱和核磁共振氢谱对产物进行结构分析;通过热失重分析、拉伸测试、耐迁移测试和耐挥发性测试等比较DPHTP、DOP以及DOTP增塑的PVC薄膜在力学性能等方面的差异。结果表明,相比DOP和DOTP,DPHTP具有更低的挥发性,其增塑的薄膜有着更优异的热稳定性以及更高的体积电阻率;其中,DPHTP的加热减量为0.031 90 %,DPHTP增塑的薄膜的热失重5 %的温度为272 ℃,体积电阻率为6.5×10⁹ Ω·m;DPHTP具有更低的挥发性且可以赋予PVC材料优异的电绝缘性能,在包装材料和电线电缆行业具有广阔的开发前景。     

对苯二甲酸二辛酯(DOTP)研制浅析

通过对对苯二甲酸二辛酯(DOTP)两种生产工艺的实验对比、浅析,结和生产实际最后选择采用对苯二甲酸(TPA)法(直接酯化法)生产DOTP。DOTP是聚氯乙烯(PVC)塑料用的一种性能优良的主增塑剂,它与目前常用的邻苯二甲酸二辛酯(DOP)相比,具有耐热、耐寒、难挥发、抗抽出、柔软性和电绝缘性能好等优点。由于(DOTP)不含邻苯二甲酸盐,不在欧盟及其他国家限制使用的16种含邻苯二甲酸增塑剂范围内,是一种优良的环保型增塑剂。     

Synthesis and characterization of polymeric plasticizer from PET waste and its applications in nitrile rubber and nitrile–PVC blend

Polyethylene terephthalate (PET) waste is not biodegradable; thus, it will create environmental hazards if disposed in landfills. Therefore, the only way of addressing the problem of disposal of post-industrial and post-consumer PET wastes is through recycling. The polyester plasticizer for polyacrylonitrile butadiene rubber (NBR) and polyacrylonitrile butadiene–polyvinylchloride rubber blend (NBR–PVC) was obtained by the depolymerization of PET waste with 2-ethyl-1-hexanol. The PET waste was depolymerized until a polymeric plasticizer with the average molecular weight in the range of 450–900 g/mol was obtained. The polymeric plasticizer was characterized for acid and hydroxyl numbers, viscosity, density, FTIR, NMR and TGA/DTA thermogram. The prepared polymeric plasticizer was used in the preparation of nitrile rubber and nitrile–PVC rubber blend rubber sheets, where these sheets were tested for compatibility, tensile strength, elongation-at-break, hardness and ageing properties. Nitrile rubber and nitrile–PVC blend sheets were also prepared using DOP as a plasticizer and a comparative study with the synthesized polymeric plasticizer was made. It was observed that synthesized polymeric plasticizer provides excellent tensile properties and ageing resistance for high-performance applications as compared to that obtained from DOP. The end uses for nitrile rubber and nitrile–PVC rubber blend compounds are quite diverse, but they can be loosely categorized as being either general performances or higher performance applications. Each of these performance categories requires a different set of considerations in terms of compounding with plasticizers.     

Mechanical,thermal, and structural characterization of poly(ethylene terephthalate) and poly(butylene terephthalate) blend systems by the addition of postconsumer poly(ethylene terephthalate)

The focus of this study was mainly on the use of scrap poly(ethylene terephthalate) (PET) in poly(butylene terephthalate)‐rich blend systems. A good combination of tensile and impact properties was observed in the newly formed blend system with scrap PET. The morphology depicted controlled and well‐dispersed phases. The thorough mixing of the constituents was observed in the thermal study. For this innovative blend system, an attempt to correlate the mechanical, thermal, structural, morphological properties and the chemistry of the blend system seemed to be technoeconomical. This study contributed to the recycling of waste material. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of a secondary plasticizer for poly(vinyl chloride) by recycling of poly(ethylene terephthalate) bottle waste through aminolytic depolymerization

This study focuses on the synthesis and application of didecanoate of bis(3‐hydroxypropyl) terephthalamide (DD‐BHPTA) as a secondary plasticizer in poly(vinyl chloride) (PVC) compounding. DD‐BHPTA was synthesized from poly(ethylene terephthalate) bottle waste through aminolysis followed by condensation reaction with decanoic acid. Synthesized DD‐BHPTA was characterized by Fourier‐transform infrared spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance. Plasticized PVC was prepared by compounding PVC in different ratios with DD‐BHPTA and dioctyl phthalate (DOP) using a two‐roll mill. This newly synthesized plasticizer completely fused with PVC. The mechanical, thermal, and rheological properties like glass transition temperature, tensile strength, % elongation, dynamic mechanical analysis, solvent resistance, accelerated ultraviolet weathering test for color stability, differential scanning calorimetry, and thermal gravimetric analysis of plasticized PVC were investigated. DD‐BHPTA along with DOP plasticizer demonstrated plasticization efficiency similar to that of DOP alone, with the same plasticizer loading. DD‐BHPTA was found to be the more efficient plasticizer when used in combination with DOP. Thus, DD‐BHPTA can be used as a secondary plasticizer for DOP and can substitute DOP up to 50% of plasticizer loading. J. VINYL ADDIT. TECHNOL., 23:152–160, 2017. © 2015 Society of Plastics Engineers