环氧棉籽油增塑PVC性能研究

用过氧甲酸法制备环氧棉籽油,研究了环氧棉籽油全部或部分替代邻苯二甲酸二辛酯(DOP)类增塑剂对PVC性能的影响,并同环氧大豆油增塑PVC性能进行了对比研究。试验结果表明:在部分取代DOP时,环氧棉籽油与环氧大豆油增塑PVC的拉伸强度基本一致,但在完全取代DOP时,环氧棉籽油的断裂伸长率是环氧大豆油的300倍以上。     

环氧桐油合成研究

本文用硫酸和强酸性阳离子交换树脂作催化剂,桐油和过氧乙酸为原料,制备了环氧桐油,并将其与DOP、环氧大豆油作PVC增塑剂进行比较,探讨了制备过程中的影响因素。结果认为,催化剂以阳离子交换树脂为好。环氧桐油的增塑效果优于环氧大豆油,与DOP相近,其稳定性、耐寒性和润滑性优于DOP。     

环保增塑剂环氧腰果酚乙酸酯增塑PVC研究

首先,以腰果酚(cardanol)与乙酸酐为原料,对甲苯磺酸为催化剂,在无溶剂常温条件下合成了腰果酚乙酸酯(CA)。然后,以甲酸为催化剂双氧水为氧源合成环氧腰果酚乙酸酯(ECA)。考察了合成ECA的用量对聚氯乙烯(PVC)的热失重曲线、邵氏硬度、玻璃化转变温度、拉伸强度与断裂伸长率的影响。结果表明,随着增塑剂用量从20份增加到90份,PVC的热稳定性和断裂伸长率逐渐增加,拉伸强度、邵氏硬度以及玻璃化温度逐渐降低;与未加入增塑剂的PVC树脂及邻苯二甲酸二辛酯增塑的PVC树脂相比,所合成的ECA具有良好的增塑效果。     

环氧脂肪酸甲酯增塑剂替代DOP用于PVC的研究

将自制的橡胶籽油基环氧脂肪酸甲酯(ERSO)与邻苯二甲酸二辛酯(DOP)混合,得到不同配比的混合型增塑剂,考察其对聚氯乙烯(PVC)的增塑效果,评价ERSO对DOP的有效替代性。测试结果表明,混合型增塑剂可显著改善PVC的柔韧性、耐化学药品性、耐热性及加工流变性,但耐水性、挥发性及表面硬度略差。经综合比较,优选的混合型增塑剂配方是ED–20,与单独使用DOP相比,其PVC的断裂伸长率提高了29.83%,热老化整体变色时间提高了近3倍,玻璃化转变温度降至–1.06℃,动态热稳定时间延长了32.59%。ERSO对传统石油基邻苯类增塑剂的有效替代率可达50%,大大拓展了环保增塑剂的应用范围。     

环氧大豆油-癸二酸低分子量聚酯对PVC增塑性能的研究

将环氧大豆油(ESO)与癸二酸(SA)进行开环固化反应，通过控制反应时间得到3种不同分子量的环氧大豆油-癸二酸低分子聚酯(ESO-SA₅、ESO-SA₉和ESO-SA₁₃)，并对其化学结构进行了表征；再以ESO-SA_n为增塑剂，研究其分子量和添加量对聚氯乙烯(PVC)增塑效果、热性能及力学性能的影响；此外，对比了不同成型方式(溶剂流延膜和熔融压制膜)对PVC增塑膜性能的影响；最后，分析了热稳定剂的加入对熔融压制膜性能的影响。研究表明，不同成型方式制备的PVC增塑膜中，均为添加30份ES0-SA₉的增塑膜具有最好的性能，包括增塑效果、力学性能(断裂伸长率269.6%，拉伸强度28.7 MPa)及热性能(初始热分解温度284.3℃)等；熔融压制使PVC与增塑剂分子之间能到达更好的混合效果，可实现分子水平的混合；由于钙锌稳定剂与基体的相容性较差且同时破坏了ESO-SA_n在PVC中形成的增塑网络结构，热稳定剂的加入反而导致增塑膜的力学性能及热性能等出现一定程度的降...     

地沟油改性制备PVC用环氧脂肪酸甲酯增塑剂

以地沟油为原料,采用分步甲酯化、酸催化-环氧化法制备环氧脂肪酸甲酯增塑剂,并对产品的化学结构进行表征。结果表明,产品在839.2cm-1处出现了环氧基特征峰;环氧化反应后原料中的不饱和脂肪酸甲酯含量显著降低,同时生成了环氧脂肪酸甲酯;产品的环氧化程度随环氧化时间的延长逐步提高,在环氧化时间为8h时环氧值达到最大3.9%,碘值相应地从87.7降至8.7;与邻苯二甲酸二辛酯（DOP）相比,环氧脂肪酸甲酯增塑剂闪点高于197℃,对聚氯乙烯（PVC）树脂有相似的增塑效率,50%的增塑剂可使PVC的玻璃化转变温度从87℃降低到-10℃,但耐迁移性尚不及DOP。     

环氧油酸新戊二醇酯的制备及应用性能研究

以油酸和新戊二醇为原料,通过酯化反应和环氧化反应制备了新型环保增塑剂环氧油酸新戊二醇酯（ENDO）,采用红外光谱仪（FTIR）和核磁共振仪对ENDO的结构进行了表征,并通过转矩流变仪、超低温脆化试验仪、老化试验机和万能试验机测试对比了ENDO、邻苯二甲酸二辛酯（DOP）、已二酸二辛酯（DOA）或偏苯三酸三辛酯（TOTM）增塑的聚氯乙烯（PVC）样品的流变性能、低温脆化性能、耐溶剂抽出性能和耐老化性能。结果表明,本实验成功制备了预期增塑剂产品ENDO;增塑PVC混合物料扭矩由大到小对应的增塑剂为TOTM、ENDO、DOP、DOA,能耗由大到小对应的增塑剂为TOTM、ENDO、DOA、DOP;ENDO增塑PVC样品的低温脆化性能可通过-30 ℃测试;当溶剂为正己烷时,DOP、ENDO、DOA和TOTM增塑PVC样品的断裂伸长率残留率依次为88.24 %、87.99 %、1.69 %和0.71 %,当溶剂为无水乙醇时,为79.00 %、96.22 %、72.76 %和74.52 %;ENDO增塑PVC样品老化后的断裂伸长率残留率、拉伸强度变化率及热老化质量损失均小于TOTM增塑的PVC样品。     

软质PVC环保增塑体系的性能

将自制的橡胶籽油基环氧脂肪酸甲酯(ERSO)环保型增塑剂应用于软质PVC体系,评价高增塑剂浓度ERSO的增塑效果,并与传统石油基增塑剂进行对比.力学性能及热性能测试结果表明:与石油基增塑剂相比,ERSO可使体系的拉伸强度降低24.46％,有效改进PVC增塑体系的柔韧性;ERSO可使体系的热稳定时间达到45.15 min,平衡转矩降低,利于制品稳定性的改善及加工性能的提高.     

环氧葵花油的合成及其对PVC性能的影响

采用无溶剂工艺合成了环氧葵花油,并利用转矩流变仪、差示扫描量热仪等进一步研究了其对聚氯乙烯（PVC）热稳定性、增塑效果的影响。结果表明,反应温度为60 ℃、反应时间为5 h、过氧化氢和葵花油摩尔比为2:1、催化剂用量为原料总质量的3 %时,环氧葵花油的环氧值达到了6.78 %;环氧葵花油与钙锌稳定剂并用具有协同作用,可以增强PVC的长期热稳定性,效果比环氧大豆油更好;环氧葵花油还能使PVC的玻璃化转变温度、硬度、拉伸强度降低,断裂伸长率升高,可以作为PVC增塑剂使用。     

环氧油酸多元醇酯的制备与塑化PVC性能研究

使用季戊四醇和油酸通过酯化反应和环氧化反应制备了环保增塑剂环氧油酸多元醇酯。采用傅立叶变换红外光谱仪和核磁共振仪对制备的产品进行了表征。结果显示得到了预期增塑剂产品。将其作为主增塑剂与聚氯乙烯热塑共混,研究了塑化聚氯乙烯的最低共混扭矩、热性能、力学性能,对该增塑剂在不同介质中的耐迁移性进行了研究,并与邻苯类增塑剂和环氧大豆油的塑化性能进行了对比。研究发现,作为主增塑剂,环氧油酸多元醇酯增塑的聚氯乙烯(PVC)共混体系的热降解温度达到了281.5℃,拉伸强度和断裂伸长率分别为22.12 MPa和332.12%,在蒸馏水、乙酸溶液、乙醇溶液、石油醚和橄榄油中的迁移量明显低于邻苯二甲酸酯和环氧大豆油增塑的PVC共混体系。     

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.     

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℃。     

环氧鱼油的性质及其应用研究

采用一步环氧化工艺制得环氧值为4．5％的环氧鱼油,研究环氧鱼油的性质及其在氯乙烯中的作用。研究结果表明：环氧鱼油耐热性高,用于聚氯乙烯中,与金属皂并用有良好的协同稳定作用,作用效果与环氧大豆油相当甚至更好些,可作为聚氯乙烯优良的增塑剂兼稳定剂。     

环氧菜籽油的合成及其在PVC中的应用

研究了环氧菜籽油的性质及其在聚氯乙烯中的应用。以活性炭固载磷钨酸为催化剂,采用无溶剂一步法环氧化工艺制得环氧菜籽油,此方法催化剂用量小且可回收,产品环氧值达4.8%以上。研究结果表明,环氧菜籽油起始分解温度高达310℃以上,使得PVC的热稳定时间由85 min提高到150 min。PVC的力学性能提高很多,撕裂强度提高达50%以上。环氧菜籽油的作用效果与环氧大豆油相当甚至更好些,可作为聚氯乙烯优良的增塑剂兼稳定剂。     

An efficient plasticizer based on waste cooking oil: Structure and application

Recently, phthalates have been continuously banned in numerous fields by many countries. Therefore, the development of sustainable and efficient plasticizers has become particularly urgent. The waste cooking oil was used as the main raw materials in this study to synthesize an efficient plasticizer (acetylated-fatty acid methyl ester-trimellitic acid ester, AC-FAME-TAE). The structure of AC-FAME-TAE was characterized by FT-IR and ¹H NMR. The performance of the poly(vinyl chloride) (PVC) plasticized by AC-FAME-TAE was tested and compared with those of the PVC plasticized with di-2-ethylhexyl phthalate (DOP) and EFAME (epoxy fatty acid methyl ester), respectively. DSC results indicated that AC-FAME-TAE had excellent plasticizing efficiency for PVC. The mechanical properties of PVC plasticized by AC-FAME-TAE were as comparable as PVC plasticized by DOP from the results of tensile test. In addition, the PVC plasticized by AC-FAME-TAE had excellent thermal stability and solvent resistance by the results of leaching test and TGA.     

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。     

环氧化菜籽油基PVC增塑剂的制备与性能研究

先将菜籽油用苯甲醇醇解,然后再将所得的苯甲醇酯环氧化,制得环氧菜籽油脂肪酸卞酯增塑剂。研究了该增塑剂对聚氯乙烯(PVC)玻璃化转变温度、热稳定性和力学性能的影响。结果表明:每100份PVC树脂加入80份环氧菜籽油脂肪酸卞酯后,PVC树脂的玻璃化转变温度从80℃下降到-28℃,5%热失重温度由240.1℃提升到272.8℃,10%热失重温度由259.9℃提高到288.4℃;分别用环氧菜籽油脂肪酸苄酯和DOP增塑的PVC树脂在常温下显示出相似的力学性能和耐迁移性能。     

Application of new oligomeric plasticizers based on waste poly(ethylene terephthalate) for poly(vinyl chloride) compositions

In this study, chemical recycling products of waste poly(ethylene terephthalate) with oligoesters were used as new plasticizers for poly(vinyl chloride) (PVC). The preparation conditions of the dry blend mixtures of the suspension PVC containing synthesised plasticizers were similar to the conditions of the preparing mixtures with commercial plasticizers. The plasticization efficiency of PVC plasticizers was then examined by analysis of the mechanical, physical and chemical properties, as well as the thermal resistance and migration of plasticizer molecules from polymer matrix. Test results proved that compositions with synthesised oligomeric plasticizers possessed similar or better properties than those containing commercial oligomeric plasticizers and much better properties than those having monomeric plasticizers. Thermal stabilities of the proposed plasticizers were higher than those of the commercial plasticizers either monomeric (bis(2-ethylhexyl)phthalate) or oligomeric, despite the fact that the synthesised oligoesters did not contain any antioxidant. The best properties, especially low volatility, very good mechanical properties, low migration were resulted of the transesterification of the waste PET with oligoesters based on adipic acid, triethylene glycol and 2-ethylhexanol which were selected as plasticizers synthesised on the technical scale. The tested plasticized PVC compositions possessed very good tear resistance, tensile strength, decrease of weight loss after 168 h at 80 °C and low migration. Processing properties of PVC compositions containing these synthesised plasticizers confirmed their effectiveness in these compositions for extrusion process.     

Studies in Estolides,Part III : Plasticizer for Polyvinyl Chloride

Acetoxy butyl esters prepared from estolides (derived from castor oil fatty acids) were evaluated as plasticizers for poly (vinyl chloride) (PVC) resin. They showed limited compatibility. They were useful as secondary plasticizers for PVC along with dioctyl phthalate plasticizer. The properties of the plasticized stocks were generally comparable to the ones obtained by incorporating 12-acetoxy butyl oleate, the commercial secondary plasticizer. Among the estolides derivatives tried, the acetoxy butyl ester obtained from estolides of acid value 83 showed better performance. 1For parts I and II in the series ,see Refference 3 and 4     

Benzyl ester of dehydrated castor oil fatty acid as plasticizer for poly(vinyl chloride)

The poly(vinyl chloride) (PVC) industry plays an important role in today's total plastics industry. The major volume of PVC is used as soft and plasticized PVC. PVC applications consume approximately 80% of the total production of plasticizers. Most of the common plasticizers are aromatic esters of phthalic acid. In the majority of countries, phthalate plasticizers are banned due to their carcinogenic properties. The concern raised about toxicity led to a large demand for bio‐based non‐toxic plasticizers. Hence, there is an increasing interest in replacing the phthalate plasticizers with those produced from simple bio‐based materials. Dehydrated castor oil fatty acid (DCOFA) is a renewable resource which can be esterified and used as an environment friendly plasticizer for PVC. Benzyl ester (BE) was prepared by reacting DCOFA with benzyl alcohol in the presence of catalyst at 170–180 °C. Esterification was further confirmed by acid value, hydroxyl number, ¹H NMR and Fourier transform IR spectroscopy. The modified plasticizer was used in various proportions as a co‐plasticizer in PVC for partial replacement of dioctyl phthalate (DOP). With an increase in the proportion of BE in PVC samples, a good plasticizing performance was observed. The incorporation of BE also resulted in a reduction in viscosity and viscosity pick‐up and improved mechanical, exudation, thermal degradation and chemical resistance properties. The presence of BE showed a reduction in the whiteness index due to presence of conjugated double bonds in the structure. The results of DSC, XRD and Shore hardness studies showed no significant variation in properties compared with those of DOP‐plasticized sheets and thus we can conclude that BE can be used as a co‐plasticizer in PVC. © 2013 Society of Chemical Industry