The effect of an epoxidized plasticizer on the thermo-oxidative ageing of poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomers

The effects of an epoxidized plasticizer on the mechanical properties and thermo-oxidative ageing behaviour of poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomers (TPEs) were investigated. Aged and unaged blends were characterized by FTIR, tensile properties, tear strength, hardness and dynamic mechanical analysis (DMA). The properties of the epoxidized soya oil (ESO) plasticized TPEs were compared with those of the di-2-ethylhexylphthalate (DOP) plasticized counterparts. The presence of epoxide groups in ESO has been shown to produce two conflicting effects. On the one hand, the presence of excessive epoxide groups has resulted in poor ageing behaviour. On the other hand, it has resulted in a good interaction and compatibility with PVC/ENR. It was found that the tensile strength of the ESO plasticized blends were comparable with the DOP plasticized ones, but the elongation at break (EB) of the ESO blends fell short of that of the DOP blends. Also the retention of both tensile properties for the ESO blends was poorer than for DOP blends. Hardening and embrittlement also occurred in the ESO blends. Despite these weaknesses, ESO could be an ideal plasticizer for the PVC/ENR system as indicated by plasticizer permanence and the greater efficiency of plasticization. © 1998 SCI.     

Preparation of epoxidized cardanol butyl ether as a novel renewable plasticizer and its application for poly(vinyl chloride)

A new type of plasticizer, epoxidized cardanol butyl ether (ECBE), was synthesized via etherification and epoxidation. Successful synthesis was confirmed from Fourier transform infrared, ¹H NMR and ¹³C NMR spectra. The obtained product was evaluated by adding it to poly(vinyl chloride) (PVC) incorporated with dioctyl phthalate (DOP). Mechanical and thermal properties of PVC blends were studied using tensile testing, thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). Processability, migration and volatility of plasticizing systems were also investigated. Tensile tests found a maximum increase of 17.8% in elongation at break. DMA results indicated that glass transition temperature shifted to lower temperature with a maximum decrease of 5.76 °C. TGA results revealed that PVC blends with higher content of ECBE had higher thermal stability; initial degradation temperature, 50% weight loss temperature and the first peak degradation temperature increased by 15.3, 14.8 and 4.1 °C, respectively. Processing time was extended from 11.56 to 59.94 min. The plasticizing performance of migration and volatility resistance were higher than those of neat DOP. © 2016 Society of Chemical Industry     

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。     

Effects of epoxidized sunflower oil on the mechanical and dynamical analysis of the plasticized poly(vinyl chloride)

Epoxidized soybean oil (ESBO), is one of the most commonly used epoxides because of its typical combined roles as a plasticizer and heat stabilizer. In this study, a novel plasticizer of poly(vinyl chloride) (PVC) resins, epoxidized sunflower oil (ESO), was synthesized, and its performance was evaluated. ESO was designed to act as a coplasticizer and a heat stabilizer like ESBO. ESO is used as organic coplasticizer for plasticized PVC containing Ca and Zn stearates as primary stabilizers and stearic acid as lubricant. Di‐(2‐ethylhexyl) phthalate (DEHP), a conventional plasticizer for PVC, was partially replaced by ESO. Mechanical properties (tensile and shore D hardness) were investigated. The performance of ESO to ESB0 (20 g) for comparison, indicated that ESO could be used as secondary plasticizer for PVC in combination with DEHP. All mechanical and dynamical properties of plasticized PVC sheets varied with the oxirane oxygen of the ESO. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

低相对分子质量PBA在PVC中的增塑作用研究

以己二酸和1,4丁二醇为原料,通过熔融缩聚法制备一系列不同特性黏度的低相对分子质量聚己二酸1,4丁二醇酯(PBA)。将低相对分子质量PBA作为增塑剂用于聚氯乙烯(PVC)中, 通过测定其玻璃化转变温度(Tg)、拉伸强度、断裂伸长率、极限氧指数和液相迁出,研究不同特性黏度的低相对分子质量PBA的增塑效率。结果表明,当添加量为30份时,PVC/PBA的Tg低于PVC/邻苯二甲酸二辛酯(DOP),并随着特性黏度的增加而增加;特性黏度为0.115 dL/g的PBA加入PVC时具有最佳断裂伸长率,可达271.9 %,优于加入同等量的DOP体系;此外PBA液相迁出率随特性黏度的增加而降低,最低几乎为零;且PVC/PBA比PVC/DOP具有更好的热稳定性和阻燃性。     

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.     

Formulation and properties' evaluation of PVC/(dioctyl phthalate)/(epoxidized rubber seed oil) plastigels

Epoxidized rubber seed oil (4.5% oxirane content, ERSO) was prepared by treating the oil with peracetic acid generated in situ by reacting glacial acetic acid with hydrogen peroxide. The thermal behavior of the ERSO was determined by differential scanning calorimetry. The effect of the epoxidized oil on the thermal stability of poly (vinyl chloride) (PVC) plastigels, formulated to contain dioctyl phthalate (DOP) plasticizer and various amounts of the epoxidized oil, was evaluated by using discoloration indices of the polymer samples degraded at 160°C for 30 min and thermogravimetry at a constant heating rate of 10°C/min up to 600°C. The thermal behavior of the ERSO was characterized by endothermic peaks at about 150°C, which were attributed to the formation of network structures via epoxide groups, and at temperatures above 300°C, which were due to the decomposition of the material. Up to 50% of the DOP plasticizer in the PVC plastisol formulation could be substituted by ERSO without a marked deleterious effect on the consistency of the plastigel formed. In the presence of the epoxidized oil, PVC plastigel samples showed a marked reduction in discoloration and the number of conjugated double bonds, as well as high temperatures for the attainment of specific extents of degradation. These results showed that the ERSO retarded/inhibited thermal dehydrochlorination and the formation of long (n > 6) polyene sequences in PVC plastigels. The plasticizer efficiency/permanence of ERSO in PVC/DOP plastigels was evaluated from mechanical properties' measurements, leaching/migration tests, and water vapor permeability studies. The results showed that a large proportion of DOP could be substituted by ERSO in a PVC plastisol formulation without deleterious effects on the properties of the plastigels. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers.     

环保增塑剂及热稳定剂在PVC中的协同作用

以农林剩余物资源腰果酚为原料合成腰果酚基乙酸酯增塑剂(CA),并用不饱和天然油脂为原料制备多效的油脂源钙锌复合热稳定剂(OMFCTS),将其与聚氯乙烯(PVC)进行共混,通过动态力学性能,热重分析,拉伸性能测试以及静态热稳定性分析,研究其增塑效果及协同作用,并与增塑剂邻苯二甲酸二辛酯(DOP)及热稳定剂硬脂酸钙锌盐进行对比。结果表明,含有20份CA增塑剂及OMFCTS热稳定剂的PVC增塑体系的玻璃化转变温度及储能模量低于PVC/DOP增塑体系;热失重10%及50%的温度明显升高,第一最大失重速率温度和第二最大失重速率温度基本保持不变;断裂伸长率提高到了248.66%,拉伸强度降至5.84 MPa;静态热稳定时间可延长到50 min以上。综上可知,CA增塑剂及OMFCTS热稳定剂联用,可有效改善PVC共混体系的相容性、力学性能及热稳定性,提高制品的综合应用性能及环保性。     

PE-C增韧PVC防水卷材的性能研究

为改善聚氯乙烯(PVC)防水卷材的性能,用不同组分的氯化聚乙烯(PE-C)与PVC共混,并用邻苯二甲酸二辛酯(DOP)作为增塑剂进行改性.结果表明,随着PE-C、DOP含量的增加,PVC防水卷材的拉伸强度、硬度单调减小,其中拉伸强度最低减小47.6%,硬度最低减小9.8%;断裂伸长率和熔体流动速率单调增加,最大增加值分别为62%、644%.比较不同组分试样的拉伸曲线发现,DOP含量为20 g,PVC、PE-C配比为70/30时,其拉伸曲线有屈服现象产生;但PE-C含量对拉伸曲线的形态无影响,无屈服现象.扫描电子显微镜照片从微观形态上验证了实验结果的合理性.     

高性能PVDC阻隔膜的制备及性能表征

通过单螺杆熔融挤出吹塑的方法制备了具有高阻隔性能的聚偏氯乙烯(PVDC)薄膜。研究了增塑剂环氧大豆油(ESBO)对PVDC薄膜结构与性能的影响。结果表明,当ESBO质量分数为3.5%时,其有效降低了PVDC薄膜的晶点尺寸和数量,并提高了薄膜的力学性能,同时使薄膜对水和氧的阻隔性能达到最佳。     

Effects of poly(butylene succinate) and ultrafine wollastonite on the physical properties of plasticized poly(vinyl chloride)

In this study, diisononyl phthalate (DINP), a conventional plasticizer of poly(vinyl chloride) (PVC), was partially replaced by a polymeric plasticizer, poly(butylene succinate) (PBS), in order to reduce the leaching out of low‐molecular‐weight plasticizer from the plasticized PVC. Samples were prepared by melt mixing on a two‐roll mill followed by compression molding into a 3‐mm thick sheet. The DINP/PBS‐plasticized PVC provides a dose‐dependent increase in the tensile properties (tensile strength, Young's modulus, and elongation at break), tear strength, and thermal stability, as compared with the DINP‐plasticized PVC. According to the overall properties, PVC plasticized with 10/30 phr (parts by weight per hundred parts of resin) DINP/PBS was selected for preparing composites with varied loadings of an ultrafine wollastonite (particle size of 1,200 mesh). Their tensile properties, tear strength, thermal stability, and morphology were evaluated and compared with the 40 phr of DINP‐plasticized PVC composites. The results showed an increase in the Young's modulus and thermal stability but a decrease in the tensile strength, elongation at break, and tear strength of either 40 phr of DINP‐ or 10/30 phr of DINP/PBS‐plasticized PVC composites. Therefore, the products may be useful where the dimensional and thermal stability of the plasticized PVC are needed. J. VINYL ADDIT. TECHNOL. 21:220–227, 2015. © 2014 Society of Plastics Engineers     

A new biobased plasticizer for poly(vinyl chloride) based on epoxidized cottonseed oil

The use of epoxidized cottonseed oil as plasticizer for poly(vinyl chloride) was studied. The plasticizer content was set to 70 phr and the optimum isothermal curing conditions were studied in the temperature range comprised between 160 and 220 °C with varying curing times in the 7.5–17.5 min range. The influence of the curing conditions on overall performance of cured plastisols was followed by the evolution of mechanical properties (tensile tests with measurements of tensile strength, elongation at break, and modulus), change in color, surface changes of fractured samples by scanning electron microscopy (SEM), thermal transitions by differential scanning calorimetry, and migration in n‐hexane. The optimum mechanical features of cured plastisols are obtained for curing temperatures in the 190–220 °C range. For these curing conditions, fractography analysis by SEM gives evidences of full curing process as no PVC particles and free plasticizer can be found. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43642.     

Insights into biobased epoxidized fatty acid isobutyl esters from biodiesel: Preparation and application as plasticizer

Biodiesel was used to prepare epoxidized fatty acid isobutyl esters (Ep-FABEs) as a biobased plasticizer in this work. Transesterification of biodiesel with isobutanol catalyzed by tetrabutyl titanate was carried out in a gas-liquid tower reactor. The conversion achieved nearly 100% within 5 h under the reaction temperature, the mass ratio of catalyst to fatty acid methyl esters (FAMEs), and isobutanol to FAMEs total molar ratio of 180 ℃, 0.4 %(mass), and 5.4:1, respectively. In addition, kinetic model of the transesterification reaction was developed at 150–190 ℃. The calculated activation energy was 48.93 kJ·mol^-1. Then, the epoxidation of obtained fatty acid isobutyl esters (FABEs) was conducted in the presence of formic acid and hydrogen peroxide. The Ep-FABEs was further analyzed for its plasticizing effectiveness to replace dioctyl phthalate (DOP) and compared with conventional epoxy plasticizer epoxidized fatty acid methyl esters (Ep-FAMEs). The results indicated that the thermal stability and mechanical properties of PVC films with Ep-FABEs plasticizer were significantly improved compared with those plasticized with DOP. In addition, the extraction resistance and migration stability of Ep-FABEs were better than those of Ep-FAMEs. Overall, the prepared Ep-FABEs via structural modification of biodiesel proved to be a promising biobased plasticizer.     

Synthesis and application of an environmental epoxy plasticizer with phthalate-like structure based on tung oil and cardanol for poly(vinyl chloride)

An epoxidized cardanol tungoleate (ECT) based on tung oil and cardanol was synthesized through esterification and epoxidation. The chemical structure of the compound was verified by Fourier transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (¹H-NMR). The plasticizing effects of ECT as the main plasticizer in poly(vinyl chloride) (PVC) was studied and compared with the commercial plasticizer dioctyl phthalate (DOP). The thermal migration stabilities, the thermal degradation process and the mechanical properties of PVC samples and the plasticization mechanism of ECT for PVC were investigated through the use of volatility, extraction, discoloration, and tensile tests as well as thermal gravity analysis (TGA), TGA–FTIR analysis, electronic universal testing machine and dynamic mechanical analysis (DMA). Compared with DOP, the ECT plasticized PVC can exhibits better thermal stability, more excellent tensile strength (17.28 MPa) and higher stretchability (629.41%), which is 1161% higher than DOP (1.37 MPa) plasticized PVC film. In addition, the migration resistance and volatility stability of ECT are much better than DOP. Therefore, this fully bio-based plasticizer based on tung oil and cardanol is a promising alternative plasticizer for PVC and may be an excellent phthalate substitute from the perspective of human health and sustainable development.     

Integration of biobased functionalized feedstock and plastisol in epoxy resin matrix toward developing structural jute biocomposites with enhanced impact strength and moisture resistance properties

Epoxy resin matrix based on diglycidyl ether of bisphenol A (DGEBA) was modified with addition of epoxidized soybean oil (ESBO). Structural jute composites prepared with ESBO modified DGEBA resin showed a decrease in tensile strengths, owing to reduced cross linking density. Percentage elongation of the samples increased with addition of ESBO. An optimized composition was identified, at which the composite showed increase in tensile strength, modulus and elongation. Interestingly, impact strengths increased initially with incorporation of ESBO, but with further increase in ESBO, impact strengths decreased. Structural Jute composites were also prepared by incorporating polyvinyl (chloride) (PVC) plastisol into the modified matrix which showed an increase in both tensile and impact strengths. Fourier transform infrared spectroscopy (FT‐IR) analysis indicated the curing state of the composites. The spectrum peaks became increasingly stronger in the O H band with increasing ESBO quantities. This could be attributed to the hydrophilic nature of ESBO, a result that was well supported by the moisture absorption test. Although, water uptake capacity of ESBO/DGEBA modified matrix composites recorded increasing trend with increased ESBO content, with inclusion of plastisol, the water uptake values dropped. Composite with DGEBA/ESBO/plastisol modified matrix actually recorded water uptake capacity comparable to composite with neat DGEBA, possibly owing to improved interfacial adhesion and hydrophobic nature of PVC plastisol. POLYM. COMPOS., 37:391–397, 2016. © 2014 Society of Plastics Engineers     

Synthesis and application of a novel thermostable epoxy plasticizer based on levulinic acid for poly(vinyl chloride)

Epoxy bisphenol acid isooctyl ester (EBAIE) was synthesized and characterized by FTIR and H-NMR. EBAIE was used as poly(vinyl chloride) (PVC) plasticizer for the first time, and its addition amount was 30 wt% of PVC. The mechanical properties, thermal stability, compatibility, and decomposition activation energy of PVC blends were systematically studied. Compared to the commercial plasticizer-dioctyl phthalate (DOP), the tensile strength had been significantly increased from 30.64 to 45.07 MPa, while the elongation at break had little difference. The thermal stability analysis showed that the static stability time at 180°C had been extended from 40 to 300 min. The decomposition activation energy indicated that the EBAIE plasticized PVC was with a higher thermal stability. The extraction and volatility resistance of the novel plasticizer were superior to those of DOP.     

硬脂酸异辛酯在聚氯乙烯加工中的应用及其流变性能的研究

研究了硬脂酸异辛酯(EHO)作为聚氯乙烯树脂增塑剂使用的可能性和适宜用量,以及对聚氯乙烯流变性能的影响。实验结果表明:EHO只能作为聚氯乙烯的辅助增塑剂使用,适宜用量为5～10份;当EHO与邻苯二甲酸二辛酯(DOP)以5:45混合使用时,可提高聚氯乙烯软制品的拉伸强度、断裂伸长率和耐寒性等性能。同时,通过流变性能实验,发现EHO在聚氯乙烯硬塑料中具有良好的润滑作用。     

干燥温度对纳米氧化石墨烯/PHBH复合膜结构及性能的影响

通过溶液浇铸法制备得到纳米氧化石墨烯（GO）/聚羟基丁酸-羟基己酸酯（PHBH）复合膜,利用SEM、XRD、DSC、拉伸测试、阻隔测试及透明度测试等检测手段,研究了不同干燥温度对复合膜结构及性能的影响,优化了制备工艺。结果表明：随着干燥温度的升高,GO在PHBH中的分散性以及复合膜的结晶度、断裂伸长率和阻隔性先增加后减小,而拉伸强度及透光率则随温度的增加而增加。当干燥温度为45℃→55℃梯度升温时,GO在PHBH中均匀分散,且复合膜的断面光滑,有良好的结晶度、热稳定性、力学及阻隔性能,其拉伸强度、断裂伸长率可分别达到20.11MPa、17.47%,且透氧系数及水蒸气透过系数分别为48cm³/(m²·d)、13.33g/(cm²·d),综合性能优于其他干燥温度下的复合膜。     

PVC/TPU/NBR三元共混物的制备及性能研究

对PVC／热塑性聚氨酯（TPU）／SR三元共混物的性能进行研究，重点讨论NBR品种、TPU／NBR并用比、PVC聚合度、增塑剂DOP和硫化剂DCP用量对PVC／TPU／NBR三元共混物性能的影响。结果表明。PVC／TPU／NBR-3604三元共混物的物理性能较优；PVC／TPU／NBR-3604三元共混物的拉断伸长率和拉断永久变形均随着PVC聚合度的增大基本呈上升趋势；随着增塑剂DOP用量的增大，共混物的邵尔A型硬度、拉伸强度、撕裂强度和拉断永久变形均基本呈下降趋势，拉断伸长率增大；随着硫化剂DCP用量的增大。共混物的拉伸强度和拉断伸长率变化不大，撕裂强度基本呈逐渐减小的趋势。不同PVC／TPU／SR三元共混物的扫描电子显微镜照片表明，NBR与PVC和TPU的相容性较好。     

一种新型蓖麻油酸季戊四醇酯的制备及应用

用季戊四醇和蓖麻油酸通过酯化反应反应制备了蓖麻油季戊四醇酯。采用红外光谱仪和核磁共振仪对制备的产品的化学结构进行表征。并将其作为增塑剂与聚氯乙烯（PVC）共混,研究了塑化PVC的平衡扭矩、热性能和力学性能,对该增塑剂在不同溶媒中的耐迁移性进行了研究,并与邻苯二甲酸二辛酯和环氧大豆油的塑化性能进行了对比。结果表明,蓖麻油季戊四醇酯塑化PVC的加工平衡扭矩为14.9 N·m,改善了PVC的加工稳定性;塑化PVC的拉伸强度为23.28 MPa,断裂伸长率为263.13 %,耐迁移性能较邻苯二甲酸酯和环氧豆油较好,可以作为PVC增塑剂使用。