生物基增塑剂HM-828性能及其对PVC性能的影响

研究了新型环保生物基增塑剂二乙酰环氧植物油酸甘油酯(HM-828)的结构及主要性能;选用环氧大豆油(ESO)、邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二异壬酯(DINP)、已二酸二辛酯(DOA)、偏苯三酸三辛酯(TOTM)及HM-828为增塑剂分别制备了增塑聚氯乙烯(PVC),对添加40份增塑剂的PVC制品的动态热稳定性、热老化质量损失、拉伸性能、硬度等进行表征。结果表明:六种增塑PVC混合物料中,DOA扭矩最小,加工能耗最低;HM-828的增塑性能与DOP和DINP相近;DOP/DINP/DOA/TOTM四种物料的耐热性不及HM-828和ESO;六种增塑PVC制品的热老化质量损失为DOADOPDINPHM-828TOTMESO;其拉伸强度均大于20 MPa,断裂伸长率均大于270%;以DOP/DINP/DOA增塑PVC制品的邵氏硬度比另外三种高出7度左右。     

环境友好增塑剂在PVC中的应用

选用5种国际公认的非邻苯类环保增塑剂环己烷-1,2-二羧酸二异壬酯(DINCH)、环己烷-1,2-二羧酸二异辛酯(DEHCH)、乙酰柠檬酸三丁酯(ATBC)、偏苯三酸三辛酯(TOTM)和聚己二酸丙二醇酯(PPA)增塑PVC,与目前广泛使用的邻苯二甲酸二异辛酯(DEHP)增塑的PVC在力学性能、光学性能、热稳定性、耐溶剂抽出性等方面进行对比。结果表明:TOTM增塑PVC的力学性能最佳,拉伸强度可达24. 33 MPa,断裂伸长率可达340. 29%; TOTM和PPA增塑PVC的热稳定性优于其他增塑剂增塑样品,外延起始温度分别达到了281. 80和282. 88℃; PPA耐溶剂抽出性能最佳,50份PPA增塑PVC的样品分别在去离子水、乙醇和石油醚中浸泡96 h后质量损失基本为0。     

环境友好型增塑剂对软质PVC光稳定性能的影响

主要研究了六种增塑剂在软质聚氯乙烯(PVC)中的应用效果,及含增塑剂的软质PVC在紫外光老化前后的性能变化。含环己烷二酸酯类增塑剂(Hexamoll dinch)的增塑PVC在添加紫外线吸收剂UV326后表现出优异的耐紫外光能力,老化1000 h后色差值最小,仅为2.29。含聚酯类高分子增塑剂的PVC样品具有最高的拉伸强度(18.3 MPa)和撕裂强度(64.1 k N/m)。含癸二酸二辛酯(DOS)的增塑PVC样品的拉伸强度(12.7 MPa)和撕裂强度(46.3 k N/m)最低,但断裂伸长率最高(393%)。含邻苯二甲酸二(2-丙基庚)酯(DPHP)、邻苯二甲酸二辛酯(DOP)和邻苯二甲酸二异壬酯(DINP)的三种增塑PVC样品的力学性能差别不大。在添加UV326后,环保型增塑剂DPHP增塑的PVC样品的耐紫外光性能增强。     

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℃。     

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。     

DOP/TOTM并用对软质PVC性能的影响

研究了DOP和TOTM并用对软质PVC力学性能、玻璃化转变温度、热老化性能的影响。结果表明:随着TOTM用量的增加,软质PVC的断裂伸长率增加,拉伸强度减小,玻璃化转变温度降低,热老化后断裂强度变化率和断裂伸长率变化率减小,热失重质量减小,TOTM的增塑效果比DOP更好一些。     

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。     

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。     

壬二酸二辛酯对聚氯乙烯增塑体系性能的影响

利用壬二酸二辛酯(DOZ)为主增塑剂、邻苯二甲酸二辛脂(DOP)为辅增塑剂增塑聚氯乙烯,探究加入环保增塑剂壬二酸二辛酯后对产品性能的影响。通过对样品力学拉伸、维卡软化点和黏度等特性进行测试后发现,加入壬二酸二辛酯后,黏度和力学性能稍有下降,但断裂伸长率明显增大,而维卡温度并没有呈现巨大变化。随着壬二酸二辛酯加入量增加,样品断裂伸长率呈直线上升,柔性提高。不同增塑剂的不同结构决定了对增塑体系性能的影响。     

几种增塑剂对发泡PVC拉伸性能和微观结构的影响

研究了环氧大豆油(ESO)、邻苯二甲酸二辛酯(DOP)、对苯二甲酸二辛酯(DOTP)、乙酰环氧化植物油酸甘油酯(HM-828)、乙酰环氧植物油酸醇酯(HM-018)对PVC发泡材料的拉伸性能、泡孔结构、发泡倍率和析出性能的影响。HM-828与PVC相容性良好、碳酸钙与基体界面结合力比较理想,拉伸强度2.4 MPa、断裂伸长率达到26.2%;采用DOP和DOTP增塑的PVC泡孔大小不均匀、碳酸钙与基体界面结合力差。HM-828和HM-018增塑PVC的泡孔较均匀,与PVC的相容性较好,存放90 d无析出。ESO增塑PVC的泡孔均匀,但其与PVC的相容性较差,存放90 d出现严重析出。     

连续催化法合成柠檬酸三乙酯增塑剂

使用负载双金属路易斯酸的树脂催化剂,采用连续法工艺催化合成了柠檬酸三乙酯（TEC）。在原料摩尔比n（乙醇）/n（柠檬酸）=2/1、空速1m3/（m3.h）、反应压力1MPa,反应温度80℃,催化剂选用KC124树脂的条件下,酯化反应产率在90%以上。本实验制备的TEC增塑的聚氯乙烯（PVC）样品,力学、耐低温及耐久性能均优于用邻苯二甲酸辛酯（DOP）和己二酸二辛酯（DOA）增塑的PVC样品。KC124树脂催化剂的稳定性好,可长期使用。     

Emissivity values for poly(vinyl chloride) with varying plasticizer compositions

The emissivity of plasticized poly(vinly chloride) (PVC) containing varying compositions and amounts of plasticizer was investigated. The four plasticizers examined were dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisodecyl phthalate (DIDP) (Phthalic acid type), and dioctyl adipate (DOA) (adipic acid type). The emmissivity of plasticized PVC film increased almost equally with the difference in the compositions between DOP and DOA. It was also clear that the emissivity of the plasticized PVC film decreased gradually with the molecular sequence length of DBP, DOP, and DIDP.     

Effect of ketal group in castor oil acid-based plasticizer on the properties of poly(vinyl chloride)

Two castor oil acid esters containing a ketal or ketone group (KCL or CL), as alternative plasticizers for poly(vinyl chloride) (PVC), were prepared. The structures were confirmed by ¹H NMR and FTIR spectroscopies. The effects of the presence of a ketal or ketone group in these compounds on PVC plasticization were examined. The DMA and SEM results showed that both plasticizers were miscible with PVC and exhibited excellent plasticizing properties, compared to those of dioctyl phthalate (DOP). The PVC plasticized by KCL displayed a lower T_g value of 20.6 ° C, which was lower than that of PVC plasticized with DOP (22.3 ° C) and PVC plasticized with CL (40.5 ° C). Tensile tests indicated that PVC plasticized using KCL showed a 37% higher of elongation at break than PVC plasticized by CL and 30% higher than PVC plasticized by DOP. The plasticizing mechanism was also investigated. Moreover, exudation, volatility, and extraction tests, along with TGA indicated that the presence of ketal groups effectively improved the migration resistance of plasticizer and the thermal stability of PVC blends. Taken together, introducing ketal groups into plasticizer might be an effective strategy for improving its plasticizing efficiency.     

PVC增塑剂偏苯三酸基聚酯的研究

采用“二步法”将偏苯三酸酐（TMA）和甘油（Gl）经酯化、缩聚反应得到环保、可生物降解的偏苯三酸聚酯（P-Gl-TMAI）。将合成的P-GI-TMAI与邻苯二甲酸（2-乙基己基）酯（DOP）分别添加到聚氯乙烯（PVC）树脂中进行塑炼实验,研究2种增塑剂与PVC树脂的相容性能、塑炼试片的力学性能以及耐迁移性能。结果表明,与DOP相比,P-Gl-TMAI与PVC的相容性较好;且前者塑炼试片的拉伸强度达18.99 MPa,断裂伸长率为454.89 %;在挥发性和抽出性试验中,P-Gl-TMAI制备的试片分别仅有3.02 %和15.31 %的质量损失率,其韧性与耐迁移性均高于DOP。     

低分子量聚四氢呋喃二苯甲酸酯的增塑性能分析

以传统的邻苯二甲酸二辛酯（DOP）和聚醚型二甘醇二苯甲酸酯（DEDB）增塑剂作对比,对聚四氢呋喃二苯甲酸酯（PTMGDB₅₀₀）增塑剂增塑的聚氯乙烯（PVC）材料进行研究。本文对增塑剂增塑的PVC材料进行了FTIR和TG表征,并考察了其力学性能、耐乙醇抽出性及耐迁移性。结果表明,增塑剂PTMGDB₅₀₀增塑的PVC材料在力学性能上介于DOP和DEDB两者之间,而PTMGDB₅₀₀与PVC间的相互作用更强,在耐迁移、耐乙醇抽出、耐热及耐压等性能方面均优于DOP及DEDB,因此PTMGDB₅₀₀可作为部分替代DOP和DEDB的增塑剂。     

Application of Poly(butylenes 2-methylsuccinate) as Migration Resistant Plasticizer for Poly(vinyl chloride)

The bio-based and biodegradable polyester poly(butylenes 2-methylsuccinate) (PBM) was successfully used as a polymeric plasticizer to modify poly(vinyl chloride) (PVC) in this work. The tensile properties, plasticization efficiency estimated by the lowered glass transition temperature and the enhanced elongation at break of the PVC/PBM blends and the migration stability of the PBM were investigated. It was indicated that the migration-resistant property of PVC plasticized with PBM was greatly superior to that with dioctyl phthalate (DOP). Furthermore, the tensile properties were comparable to that of PVC/DOP, indicating that the environmentally friendly PBM can be used as an alternative plasticizer to remove the potential health risks from migrating phthalates during applications.     

Mechanical and barrier properties of polyvinyl chloride plasticized with dioctyl phthalate,epoxidized soybean oil,and epoxidized cardanol

Plasticized polyvinyl chloride (PVC) films were prepared by melt compounding and compression molding using epoxidized cardanol (EC), a biobased plasticizer and its plasticization effect was compared with epoxidized soybean oil (ESBO) and dioctyl phthalate (DOP). The mechanical, migration, thermal, and barrier properties of the plasticized films were compared. The effect of replacing DOP with EC on the properties of PVC films was also investigated. The tensile strength, elongation at break, tensile modulus and impact strength values of PVC/EC films were higher in comparison to PVC/DOP and PVC/ESBO films at a fixed plasticizer loading of 40 wt.%. Also, the films prepared with a mixture of DOP + EC showed higher tensile strength and elongation at break compared to that of films prepared with only DOP. The PVC/EC films showed good thermal stability and reduced oxygen transmission rate (OTR) compared to PVC/DOP films. The addition of graphene and nanoclay in the PVC/plasticizer system exhibited an increase in oxygen transmission. However, the oxygen barrier property of nano filler incorporated PVC/EC films was better than PVC/DOP films. All the films showed negligible water vapor transmission rate (WVTR).     

Poly(hexane succinate) plasticizer designed for poly(vinyl chloride) with a high efficiency,nontoxicity, and improved migration resistance

Poly(hexane succinate) (PHS) was designed as an alternative type of polyester plasticizer for the modification of poly(vinyl chloride) (PVC). The plasticizing effect of PHS was studied and compared with the traditional dioctyl phthalate (DOP) plasticizer. The results show that the PVC plasticized by PHS had the lowest tensile strength of 15.3 MPa and the highest elongation at break of 105.1% when 35 phr PHS was added. It also exhibited a lower glass‐transition temperature than PVC plasticized by DOP (PVC–DOP); this could be explained by the improvement of free volume for the amorphous part of PVC enhanced by high‐molecular‐weight PHS. The migration‐resistant properties of PVC–PHS was greatly superior to those of PVC–DOP. All of these results illustrate that PHS had a higher plasticizing efficiency than DOP for PVC. PHS could be used as an alternative plasticizer to remove the potential health risks of phthalates migrating out during applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46388.     

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。