一步合成邻苯二甲酸丁苄酯

1 前言 随着我国PVC制品的产量迅速增加,对增塑剂的需求增长很快,使主要增塑剂邻苯二甲酸二异辛酯(DOP)处于长期供不应求的状态中,而邻苯二甲酸二丁酯(DBP)国外已开始逐步陶汰,邻苯二甲酸丁苄酯(BBP)在增塑剂中所占的比重一直很低。因此发展特殊性能的BBP已经是势在必行。2 性质 邻苯二甲酸丁苄酯,分子式C_(19)H_(20)O_4结构式     

国外有关塑料助剂研究的期刊文摘（增塑剂）

己二酸二异辛酯和乙酰枸橼酸三丁酯增塑剂从食品级PVC膜向异辛烷的迁移：伽马辐射的作用；高分子增塑剂部分取代邻苯二甲酸二异辛酯用作聚氯乙烯增塑剂对气体渗透性和迁出性的作用；增塑剂对大豆基生物塑料的热性能、机械性能和形貌的影响；增塑剂对Metolose甲基纤维素膜老化的作用；增塑剂（DOP和CNSL）对SBS／聚阴离子共混物的机械性能和电性能的影[编者按]     

欧盟禁限儿童塑料玩具使用6种增塑剂

欧洲议会投票禁止在儿童塑料玩具中使用邻苯二甲酸二乙基己酯（DEHP）、邻苯二甲酸二丁酯（DBP）和邻苯二甲酸丁二卞酯（BBP）3种增塑剂，并限制邻苯二甲酸二异壬酯（DINP）、邻苯二甲酸二异癸酯（DIDP）和邻苯二甲酸二正辛酯（DNOP）3种增塑剂用于可放入口腔的儿童塑料玩具和用品中。     

气相色谱–质谱法测定玩具涂层中6种邻苯二甲酸酯增塑剂

建立了气相色谱–质谱法测定玩具涂层中邻苯二甲酸二丁酯(DBP)、邻苯二甲酸丁苄酯(BBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、邻苯二甲酸二正辛酯(DNOP)、邻苯二甲酸二异壬酯(DINP)、邻苯二甲酸二异癸酯(DIDP)等6种邻苯二甲酸酯类增塑剂的分析方法,确定了适宜的微波辅助萃取条件为:以二氯甲烷为萃取剂,萃取温度60°C,萃取时间25 min。在试验选定的条件下,以该方法测定玩具涂层中6种邻苯二甲酸酯类增塑剂,以峰面积对质量浓度线性回归,线性范围在0.5~50 mg/L,则相关系数大于0.999,最低检出限为0.5~1.0 mg/L,加标回收率在83.5%~105.6%之间,相对标准偏差小于5.8%。该方法操作简便快速,准确度和灵敏度高,适合于玩具涂层中6种邻苯二甲酸酯类增塑剂含量的同时测定。     

新型增塑剂DPHP的应用性能评述

介绍了增塑剂DOP的替代产品邻苯二甲酸二(2-丙基庚)酯(DPHP)的物性、力学性能、加工性、电性能、耐候性等应用性能,并提出国内发展DPHP的建议。     

加快无毒增塑剂开发

最近一段时间，欧盟和俄罗斯先后对从中国进口的塑料玩具发出警告，原因是在原产于中国的一些塑料玩具中发现含有有毒的聚氯乙烯增塑剂——邻苯二甲酸二异壬酯（DINP）和邻苯二甲酸二乙基己酯（DEHP）。而此前，食品包装用聚氯乙烯薄膜中添加的增塑剂——邻苯二甲酸二辛酯（DOP）的毒性也引起了全球的广泛关注。     

BD耐污增塑剂的研究

<正> 一、前言增塑剂是聚氯乙烯等塑料必不可少的助剂。增塑剂主要作用是削弱聚合物分子间的范德华力,从而增加了聚合物分子链的移动性,降低了聚合物分子链的结晶性,亦即增加了聚合物的塑性。增塑剂分子里引进芳香环,能显著地提高耐污性能。如邻苯二甲酸丁苄酯(BBP)、邻苯二甲酸二苄酯(DB)、磷苯二甲酸呋喃甲酯苄酯、四氢呋喃甲酯苄酯、乙氧基乙酯苄酯、苯氧基乙酯苄酯、甲氧基乙酯苄酯等,都具有一定的耐污性能。BD增塑剂是含有60～65%的BBP和35～40%的DB的混和     

邻苯二甲酸丁苄酯合成的有效方法

邻苯二甲酸丁苄酯(BBP)用作聚氯乙烯主增塑剂。与DOP相比,可赋予制品以较低柔韧性;挥发性比DBP低,用于增塑发泡制品更有价值,BBP增塑制品具有抗污性,对抗污染性要求极高的壁纸、     

一种优异的软聚氯乙烯阻燃增塑剂——四溴邻苯二甲酸二(2—乙基己基)酯

将四溴邻苯二甲酸二(2-乙基己基)酯(TBPDO)作为PVC的阻燃增塑剂,代替软PVC中部分常规增塑剂DOP或TOTM,不仅可显著提高材料的阻燃性(氧指数可达45％),而且可保持甚至改善PVC的其他性能,如热稳定性、电绝缘性、颜色稳定性、柔顺性等。含TBPDO的PVC适于用作在高温下使用的电线及电缆绝缘层。本文叙述了TBPDO的制法、性能及在软PVC中的应用。     

邻苯二甲酸810酯的合成

邻苯二甲酸810酯又名邻苯二甲酸正辛基、正癸基酯，简称810。是一种综合性能十分优良的直链醇酯，属新型增塑剂，性能较DOP优良，具有挥发性低、低温柔性好、透明度高、迁移性小、水抽出率低、塑化效率高、耐老化性强等优点，是PVC的主增塑剂。     

Performance Evaluation and Biodegradation Study of Polyvinyl Chloride Films with Castor Oil-based Plasticizer

In the present study, a renewable resource-based plasticizer was synthesized by the lipase-catalyzed esterification reaction of furfuryl alcohol (FA) and castor oil fatty acid (COFA). The resultant ester (FA-COFA ester) was used as secondary plasticizers to the polyvinyl chloride (PVC) films. The PVC films were formulated using the combination of a conventional plasticizer di-butyl phthalate (DBP) and FA-COFA ester as a secondary plasticizer at different concentrations. Films were characterized by X-ray diffraction analysis, scanning electron microscopy, thermal analysis, mechanical performance, and migration stability. A biodegradability study of the PVC films showed increased degradability with increasing concentration of the FA-COFA ester in the PVC film. The study showed that ester of FA and COFA could be a substitute of DBP by as much as 80% of the total plasticizer with improved elongation and tensile properties, and such a kind of sustainable resource-based PVC blend films could be used as a good packaging material with biodegradable property.     

Migration of phthalate and non‐phthalate plasticizers out of plasticized PVC films into air

The aim of the present work is to provide information about the migration of phthalate and non‐phthalate plasticizers generally used in flexible polyvinyl chloride (PVC) applications. Plastisols (pastes) were prepared by mixing PVC, plasticizer, and thermal stabilizer. The plasticized PVC (p‐PVC) films are obtained by gelation at 160°C for 15 min. The p‐PVC films were heat treated at 50, 85, 100, 130, and 160°C up to 420 min to follow the mass loss to find out diffusivity of plasticizer out of films into air and to determine related activation energies. The films having di‐octyl terephthalate (DOTP) and di‐isononyl 1,2‐cyclohexanedicarboxylic acid (DINCH) exhibited the lowest mass loss in general, among the phthalate and non‐phthalate plasticizer having p‐PVC films, respectively, as confirmed by FTIR investigation. The same tendency was observed for diffusion coefficients and for the activation energies of migration. The diffusion coefficients were found to be around 3.5 × 10^?18–2.1 × 10^?17 m²/sec for the studied plasticizers in PVC at 50°C and around 4.0 × 10^?15–9.9 × 10^?14 m²/sec at 160°C. The activation energies for 85–160°C interval were determined to be between 70 and 153 kJ/mol (0.72–1.58 eV) for the plasticizers used herein those could be treated as a homologous series as deduced from the related compensation factors. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

非邻苯类环保增塑剂增塑二醋酸纤维素的研究

分别研究和对比了利用环保增塑剂聚乙二醇(PEG)、三醋酸甘油酯与乙酰柠檬酸烷基酯混合物(GA)与传统增塑剂邻苯二甲酸二乙酯(DEP)增塑二醋酸纤维素材料的性能。结果表明,当PEG、GA和DEP的含量分别为30份时,PEG30样品的力学强度低、吸水率高,且在相同温度下其流动性差, GA30样品的拉伸强度、膜撕裂强度、耐水性、增塑剂迁移率等与DP30样品基本相当,断裂伸长率较DP30样品增加了58.7 %。     

Preparation and evaluation of acetylated mixture of citrate ester plasticizers for poly(vinyl chloride)

Tributyl citrate (TBC) and acetyl tributyl citrate (ATBC), as phthalate alternative plasticizers, show limited application due to low migration resistance, high volatilization rate and intense respiratory irritation. Meanwhile, the developed pure citrates, such as butyryl trihexyl citrate (BTHC) due to its high cost, and triisooctyl citrate (TOC) and acetyl triisooctyl citrate (ATOC) due to their low absorption property, are not attractive plasticizers to manufacture phthalate-free poly(vinyl chloride)s (PVCs). In this study, we developed an effective method to synthesize acetylated mixture of citrate esters (ATMC) composed of acetyl (dibutyl-monoisooctyl) citrate, acetyl (monobutyl-diisooctyl) citrate, and a small amount of ATBC and ATOC, as an alternative for phthalate plasticizers. ATMC combines the advantages of ATBC in being easily absorbed and ATOC in having good migration resistance. Characterization results showed that the dynamic viscosity, absorption property and plasticizing efficiency of ATMC11 (1:1 molar ratio of n-butyl alcohol to 2-ethylhexanol) were similar to those of di(2-ethylhexyl) phthalate (DEHP). The thermal volatilization and migration of ATMC11 were less than those of ATBC, and were comparable to those of DEHP, which could be attributed to the improved compatibility with PVC. The performance of ATMC11 was improved compared with that of the mixture of ATBC and ATOC. As an environmental bio-based plasticizer, ATMC11 was demonstrated as a biologically safe plasticizer by biological safety evaluation tests. Therefore, ATMC11 with excellent comprehensive performances and low cost can be candidate as an ideal phthalate alternative for soft PVC formulations.     

Epoxidized vegetable oil and bio‐based materials as PVC plasticizer

Phthalate esters received a considerable attention owing to its various applications and the harmful health effects resulting from phthalate exposure; thus, finding an alternative to phthalate derivatives became a necessity. Phthalate esters are commonly used as plasticizer in polymer formulation; in particular for poly(vinyl chloride) (PVC) formulation. According to the researches in the last 18 years, epoxidized vegetable oils are one of the alternatives that are strongly encouraged to substitute phthalate esters since they were proven to be valid in various applications, eco‐friendly and sustainable resource. However, most of the production practices for epoxidized vegetable oil are via conventional epoxidation that concentrates on a catalyst that is homogeneous and non‐reusable. This type of catalyst, however, causes several problems later in the process. Therefore, the selective epoxidation of vegetable oils process requires new catalytic systems that are more aligned with the green chemistry principles. This article reviews the harmful health effects associated with the exposure to phthalate esters products, explains the usage of oleochemicals resources as a substitute to phthalate esters and describes different approaches for the epoxidation of vegetable oils. Finally, it draws attention to the usage of epoxy and bio‐based compounds as plasticizers in PVC manufacturing. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46270.     

邻苯二甲酸酯类增塑剂合成与应用研究进展

综述了近年来邻苯二甲酸酯类聚氯乙烯(PVC)增塑剂合成与应用研究的进展,并对我国增塑剂向绿色、环保方向发展提出了建议。     

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.     

PVC玩具和儿童用品中6种限用邻苯二甲酸酯类增塑剂的同时测定

提出了气相色谱-质谱联用同时测定PVC玩具和儿童用品中6种限用增塑剂的方法,以乙酸乙酯为溶剂,采用微波萃取法提取PVC玩具和儿童用品中6种限用邻苯二甲酸酯类增塑剂,以DHP为内标进行定量。该方法平均回收率为91.15%~98.72%,RSD为1.98%~4.47%,检测限(S/N=5)分别为0.5 mg/L(DBP、BBP、DEHP、DNOP)和10 mg/L(DINP、DIDP)。     

软质PVC交联对增塑剂迁移行为的影响

研究了软质PVC交联前后,对苯二甲酸二辛酯(A)、乙酰柠檬酸三正丁酯(B)和邻苯二甲酸二辛酯(C)三类增塑剂在40℃橄榄油浸泡环境中的迁移行为.结果表明,不管PVC是否交联,A、B、C三类增塑剂的迁移率均随浸泡时间的延长,呈总体上升趋势;在浸泡的前24 h,迁移率迅速上升,当浸泡时间超过192 h后,迁移率上升逐渐趋于平缓.PVC交联对各类增塑剂的迁移均起到了明显的抑制作用,且随着凝胶含量的增加,其抑制作用越明显;当凝胶含量为最大值、增塑剂达到最终的迁移平衡时,均能降低约30%的增塑剂迁移率.几类增塑剂中,B 增塑剂迁移率>C增塑剂迁移率>A增塑剂迁移率;PVC交联对A、B、C三类增塑剂之间迁移抑制率的影响无明显规律.     

玩具和儿童用品中的邻苯二甲酸酯增塑剂方法比对结果分析与评价

采用EN14372:2004条款6.3.2、CPSC-CH-C1001-09.3和GB/T 22048-2008方法 B,测定玩具和儿童用品不同材料中邻苯二甲酸酯增塑剂的含量。对方法比对测试结果的分析表明,某些材料不同方法测试结果差异较大。玩具和儿童用品测试邻苯二甲酸酯增塑剂含量时,需按不同材料选择合适的测试方法。