环境友好型增塑剂增塑聚氯乙烯体系的性能表征

以传统增塑剂邻苯二甲酸二辛酯(DOP)为比较对象,研究了对苯二酸二辛酯(DOTP)、乙酰柠檬酸三丁酯(ATBC)、己二酸二辛酯(DOA)、癸二酸二辛酯(DOS)4种环境友好型增塑剂对聚氯乙烯(PVC)体系的力学性能和耐油、耐溶剂性能的影响,并采用傅里叶变换红外光谱法和差示扫描量热法对试样分子结构进行了表征。结果表明:①ATBC/PVC体系的Tg最高(-22.1℃);DOS/PVC体系的Tg最低(-65.4℃),耐寒性最佳;②ATBC、DOA、DOS增塑PVC的力学性能整体上优于DOP增塑的PVC;③在异辛烷、正己烷和ASTM 1#标准油3种萃取剂中,5种增塑剂在正己烷中的最终抽出率最大;在同一萃取剂中,ATBC的最终抽出率最小;④针对不同使用领域,DOPT、ATBC、DOA、DOS可替代DOP增塑PVC。     

树脂催化剂催化合成柠檬酸三丁酯系列增塑剂及其应用

采用负载双金属路易斯酸的树脂催化剂催化合成了柠檬酸三丁酯(TBC),再经乙酰化生成乙酰柠檬酸三丁酯(ATBC)、油酰柠檬酸三丁酯(OTBC)、十八碳酰柠檬酸三丁酯(ETBC)。经试验分析,催化剂KC124的催化效果最好,催化活性最强。使用TBC系列增塑剂,PVC样品的力学性能高于邻苯二甲酸二辛酯(DOP)和己二酸二辛酯(DOA),耐低温性能高于DOP和DOA,分子迁移率低,材料的耐久性能好。催化剂KC124使用寿命长,稳定性好。     

TBC复配增塑对聚氯乙烯防水卷材性能影响的研究

探讨了邻苯二甲酸二辛酯(DOP)和柠檬酸三丁酯(TBC)两种增塑剂对聚氯乙烯(PVC)防水卷材拉伸性能、撕裂性能、尺寸稳定性及增塑剂迁移率的影响。结果表明:在同等增塑剂用量的情况下,TBC增塑体系的力学性能优于DOP增塑体系,但尺寸稳定性和增塑剂迁移率较差。随着TBC/DOP复配体系中TBC含量的增加,PVC防水卷材的断裂伸长率、撕裂强度和尺寸稳定性均呈先增大后减小的趋势,而拉伸强度呈先增大后减小再增大的趋势,增塑剂迁移率呈增大趋势。当TBC/DOP以1:3复配时,PVC防水卷材的拉伸性能、撕裂性能、尺寸稳定性及增塑剂迁移率总体比较理想,均能满足GB/T 12592—2011的要求。     

无毒环保型增塑剂对聚氯乙烯性能的影响

选用了邻苯增塑剂(DOP)、柠檬酸酯类增塑剂（ATBC、ATOC）、对苯增塑剂（DOTP）、偏苯增塑剂（TOTM）及新型植物基增塑剂ID-37制备了增塑PVC材料,对所制备的PVC材料的拉伸强度、断裂伸长率、硬度、180℃热稳定性进行表征,测试结果表明,180℃静态热稳定性DOTP与TOTM最优,DOP与ID37次之,ATBC与ATOC相当。增塑剂对力学性能影响较小,对硬度差异影响较大,其中DOTP与TOTM所增塑PVC材料硬度比其余四种高约5度（邵氏A）。DSC测试结果表明,TOTM及ATBC增塑PVC的Tg相对较高,约为-22℃,其余四种较为接近,约为-25℃。     

生物基增塑剂异山梨醇二庚酯在PVC中的应用

以异山梨醇和正庚酸为原料合成了一种生物基增塑剂异山梨醇二庚酯(SDH),并与石油基增塑剂邻苯二甲酸二辛酯(DOP)和对苯二甲酸二辛酯(DOTP)对比考察了对聚氯乙烯(PVC)的增塑性能。通过红外分析表征增塑剂与PVC分子间相互作用;通过拉伸试验与动态力学测试表征PVC试样的力学性能;通过热重分析与迁移性实验表征增塑剂的稳定性。结果表明,SDH与PVC分子间的相互作用更强;PVC/40SDH试样较同比例的DOP和DOTP增塑PVC表现出更高柔韧性,其中PVC/40SDH的断裂伸长率较PVC/40DOP和PVC/40DOTP分别提高26.29%和33.89%,玻璃化转变温度则分别降低1.67℃和4.15℃;SDH的热稳定性、挥发性和耐抽提性介于DOP和DOTP之间。SDH的综合增塑性能较优,可以替代DOP和DOTP用于PVC的增塑。     

对苯二甲酸(TPA)合成对苯二甲酸二异辛酯(DOTP)的新型催化剂

正一、项目简介DOTP因具有低挥发、耐高低温、高绝缘、抗迁移、抗抽出和对聚氯乙烯(PVC)的相容性佳等优点,已在塑料、橡胶、涂料、润滑油、造纸等领域获得广泛的应用。作为PVC的增塑剂,DOTP的综合性能已优于邻苯二甲酸二异辛酯(DOP)。目前世界上年产苯二甲酸二酯类的增塑剂已接近1千万吨。至今生产DOP和DOTP的催化剂存在的主要问题是单元     

生物基增塑剂异山梨醇酯的研究

以异山梨醇为原料合成了一种生物基增塑剂异山梨醇酯,通过与传统增塑剂邻苯二甲酸二辛酯(DOP)和对苯二甲酸二辛酯(DOTP)对比,考察了其聚氯乙烯(PVC)制片的应用性能。结果表明,合成的异山梨醇酯在PVC制片中具有更优良的力学性能、耐抽出性、耐挥发性及相容性,异山梨醇酯作为生物基增塑剂可替代传统增塑剂的DOP和DOTP用于PVC制品中。     

食品包装材料中柠檬酸酯增塑剂的迁移研究

制备了几种食品包装材料在不同测试条件下的正己烷和橄榄油浸泡液,采用气相色谱-质谱法(GC-MS)检测了样品浸泡液中柠檬酸三乙酯(TEC)、柠檬酸三丁酯(TBC)、乙酰柠檬酸三丁酯(ATBC)、柠檬酸三辛酯(TOC)增塑剂的迁移量,研究了样品中几种柠檬酸酯增塑剂的迁移行为。结果表明:特定温度下,柠檬酸酯增塑剂的迁移量随着浸泡时间的延长而增大;随着浸泡温度的升高,柠檬酸酯的迁移量呈增大趋势;与橄榄油相比,正己烷是一种较苛刻的迁移模拟物,同等条件下迁入正己烷中的增塑剂比迁入橄榄油中的多;另外,迁移过程中的振荡处理也会大大提高迁移效率。     

环保PVC增塑剂乳酸基酯的合成及性能

以L-乳酸、环己醇、乙酸酐为原料,合成了乙酰化环己烷乳酸酯(ACHL),并用作PVC树脂增塑剂。使用傅里叶变换红外光谱(FTIR)、氢核磁共振波谱(~1H-NMR)对目标产物ACHL的结构进行了表征。对使用不同增塑剂PVC试样的扫描电镜、耐迁移性、拉伸性能测试发现:ACHL与PVC树脂具有较好的相容性,24 h内在环己烷和无水乙醇中的质量损失率分别为14.27%和25.16%,优于乙酰化柠檬酸三丁酯(ATBC)和对苯二甲酸二辛酯(DOTP),杨氏模量与ATBC相当。证明ACHL具有较好的增塑性能与材料力学特性,有望成为替代邻苯类主增塑剂的一种新型环保PVC助剂。     

聚氯乙烯新型增塑剂DOTP

对苯二甲酸二(2-乙基己)酯(简称对苯二甲酸二辛酯(DOTP)(Dioctyl te-rephthalate)是聚氯乙烯的新型增塑剂。与邻苯二甲酸二辛酯(DOP)相比,它的电绝缘性和低挥发性比DOP好得多,是一种较佳的PVC增塑剂。又由于DOTP与金属和二氧化硅填料的湿润性佳,已广泛用于聚氯乙烯电缆料的生产。     

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.     

低迁移量环保食品罐密封圈的制备及其性能研究

以聚氯乙烯（PVC）糊树脂、Dinch增塑剂、聚酯增塑剂等其他助剂制备低迁移量环保密封圈。研究了PVC糊树脂的聚合度、发泡剂含量、加工温度和胶料存放时间对密封圈耐迁移性能的影响。结果表明,在聚合方法相同、颗粒形态相近的条件下,随着PVC糊树脂聚合度的提高,树脂吸收增塑剂的能力变强,密封圈的耐迁移性能随之提高;随着添加的发泡剂含量的增加,密封圈的泡孔变大且数量增加,与模拟液的接触面积变大而导致增塑剂迁移量变多;加工温度为195 ℃时制备得到的密封圈的增塑剂迁移量较少,加工温度过高或者过低会使密封圈部分结构受到破坏或者塑化程度过低,体系内游离的增塑剂含量较多;随着胶料存放时间的延长,密封胶的稳定性降低,密封圈的耐迁移性能随之降低。     

Effect of liquid plasticizers on crystallization of PCL in soft PVC/PCL/plasticizer blends

In this work, poly(ε-caprolactone) (PCL) and liquid plasticizer were combined used to plasticize poly(vinyl chloride) (PVC), and the possibility of using PVC/PCL/plasticizer blends to fabricate soft PVC with enhanced migration resistance was investigated. Through partial replacement of liquid plasticizers in soft PVC by equal quantity of PCL, flexibility was maintained while extraction loss of plasticizer by organic solvent was reduced significantly. Furthermore, crystallization of PCL in PVC/PCL/plasticizer blends with low PCL content was observed, and crystallization rate of PCL was found to be influenced by plasticizer contents and structures. For instance, crystallization rate of PCL in PVC/PCL/diisononyl phthalate (DINP) (100/40/100) was 3.7 times faster than in PVC/PCL/DINP (100/40/80), while crystallization rate of PCL in PVC/PCL/dioctyl adipate(DOA)(100/40/100) was 8.3 times faster than in PVC/PCL/diisononyl cyclohexane-1,2-dicarboxylate (DINCH) (100/40/100). Low-field ¹H NMR test manifested that different crystallization rate of PCL in PVC/PCL/plasticizer blends with different plasticizer structures was triggered by difference in plasticizers' compatibility with PVC, that is, the number of interaction point between PVC and plasticizers. It is concluded that PCL crystallization favored by liquid plasticizers in PVC/PCL/plasticizer blends was induced by interaction competition between PVC/plasticizer and PVC/PCL. As plasticizer content increases or its compatibility with PVC decreases, interaction competition becomes more intense and consequently faster crystallization of PCL occurs. Thus, to obtain soft PVC products with improve migration resistance while avoiding PCL crystallization, the total content of plasticizer (including both liquid plasticizer and PCL) should be lower than 66 phr (40 wt %). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48803.     

An innovative plasticizer for flexible PVC food contact applications

When flexible polyvinyl chloride (PVC) is used in food contact applications, there is potential for plasticizer migration. Concern over this migration has led to the development of a novel plasticizer. Eastman EPZ plasticizer is a distilled acetylated monoglyceride (DACM). EPZ is a fraction from the molecular distillation of the reaction mixture prepared by the interesterfication of fully hydrogenated coconut oil and glyceryl triacetate. It is lawful for both direct and indirect food contact according to U.S. Food & Drug Administration regulation 29 CFR 172.828. The performance of EPZ plasticizer compared with adipate and citrate plasticizers confirms its usefulness in flexible PVC. This performance, combined with its clearance as a direct and indirect food additive, offers vinyl formulators a new tool to expand the flexible vinyl market.     

食品级增塑剂乙酰化单甘油脂肪酸酯(ACETEM)的应用研究

以纯天然植物油甘油和椰子油等原料合成具有不同碳链长度的植物油基环保型增塑剂乙酰化单甘油脂肪酸酯(ACETEM)。通过红外光谱(FT-IR)、气质联用(GC-MS)表征手段测定其结构,并利用热重分析仪(TGA)测定其本身及PVC试片的热稳定性能,对其PVC试片的迁移率和挥发损失率研究,探索了其与PVC的相容性能,结果表明,ACETEM具有较好的热稳定性能,并且与PVC具有较好的相容性,将其应用在食品包装材料上具有很好的前景。     

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.     

Energy and material cost savings with polyester/monomeric plasticized PVC compounds

Many plasticized PVC articles are exposed to harsh environments that cause loss of plasticizer through extraction, volatility, or migration. In order to survive in these applications, the PVC must contain plasticizers that have a reasonable degree of permanence. Two approaches are the use of low molecular weight polyester plasticizers, or higher molecular weight polyester/monomeric plasticizer blends. The blend approach can give better cost-performance and, due to faster fusion, reduced energy/manufacturing costs. The blends maintain their advantages even upon further dilution with monomeric plasticizers and in permanence tests of long duration. Although better than monomeric plasticizers, neither the low molecular weight polyester nor the blend system is recommended for applications requiring the ultimate in migration resistance.     

The effects of plasticizers on the properties of poly(vinyl chloride) foams

The effects of plasticizers on poly(vinyl chloride) (PVC) plastisol mixtures were investigated. The investigations were carried out by determining the density of the PVC foam obtained by gelling the plastisol, as well as its elasticity and degree of expansion. Two series of experiments using different types of PVC were performed, using eight plasticizers, individually or as mixtures. Two-component plasticizer mixtures showed better properties than single-component plasticizers, and mixtures of di-iso-heptyl phthalate (DiHP) and butyl benzyl phthalate (BBP) proved to be the most appropriate. The effect of plasticizer amount also was investigated, and of the three parameters studied, the foam density, which steadily increased with plasticizer amount, was the critical one. It was also shown that in order to obtain consistent results, the foam expansion had to be precisely timed and the temperature carefully chosen.     

环保醚酯型增塑剂TP-95在PVC中的应用

研究了环保醚酯型增塑剂TP-95和几种常用增塑剂对聚氯乙烯(PVC)的塑化效果、力学性能、耐寒性、耐热性及耐抽出性能的影响。结果表明:与添加的几种增塑剂相比,TP-95具有显著的增塑软化作用;随着增塑剂用量的增加,最低转矩明显下降,塑化时间缩短,塑化效果随之增强;与DOP和TOTM相比,TP-95表现出良好增塑效应及耐寒性;增塑剂用量均为50份时,TP-95的PVC开始热降解温度高于DOP和DOA;在水和环己烷介质中,随着随着增塑剂用量的增加,抽出损失随之增加;在环己烷介质中,TP-95的抽出损失为4.40%,低于TOTM和DOA,具有良好的耐抽出性。     

Solutions to reduce release behavior of plasticizers out of PVC-made equipments: binary blends of plasticizers and thermal treatment

In order to reduce migration of plasticizers out of polyvinyl chloride (PVC), several techniques were attempted. First, binary blends of plasticizers were added to PVC, migration was decreased 100 or 1,000 times as compared to PVC samples containing only one plasticizer: the diffusion coefficient was of the order of 10⁻⁸ cm² s⁻¹ for the blend di-2-ethylhexylphthalate (DEHP)/di-2-ethylhexylterephthalate (TDHP) or 10⁻⁹ cm² s⁻¹ for the blend DEHP/DBP. A thermal treatment of PVC samples containing only one plasticizer leads to diffusion coefficients of the order of 10⁻¹⁰ cm² s⁻¹. This second method was also applied to PVC samples plasticized with binary blends. It lowers even more migration of both plasticizers out of PVC. But no particular phenomena were observed with ternary blends of plasticizers introduced in PVC.