环氧地沟油基PVC人造革增塑剂的制备与应用

以地沟油为原料,采用双氧水氧化法制备植物油基人造革增塑剂。通过红外光谱、碘值、环氧值对其化学结构进行分析,使用热重分析仪、万能试验机、萃取试验分析了增塑剂对人造革性能的影响。结果表明:FTIR光谱中双键特征峰信号减弱,在825.45cm~(-1)处出现环氧基特征峰,碘值由112g/100g降低至5.47g/100g,环氧值从零升至3.711%。将环氧地沟油应用于PVC人造革制备中,可以提升PVC人造革的热稳定性,加入环氧地沟油基增塑剂的PVC人造革的5%的失重温度为302.20℃,10%的失重温度为310.12℃,显示了比DOTP(对苯二甲酸二辛酯)基PVC人造革更优异的耐热性能,环氧地沟油基增塑剂和DOTP基增塑剂的人造革显示了相似的力学性能和耐久性。     

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。     

环氧油酸钙(锌)的合成及在PVC中的应用

以油酸、甲酸和双氧水为原料合成了环氧油酸,经复分解反应制得了环氧油酸钙(锌)盐,将其作为热稳定剂应用于PVC中,通过电导率、热老化以及热失重测试来考察环氧油酸钙(锌)的热稳定特性。研究结果表明:环氧油酸钙具有长期热稳定性,环氧油酸锌具有初期热稳定性,当环氧油酸锌/环氧油酸钙的比例为1∶3时,PVC的热稳定效果最好。     

环氧大豆油PVC人造革增塑剂的制备与应用研究

以大豆油为原料,在硫酸为催化剂条件下,经甲酸、双氧水环氧化制备环氧化大豆油增塑剂,通过红外光谱、碘值和环氧值对其结构进行表征,红外光谱显示双键特征峰减低,在822.48 cm-1出现环氧特征峰、碘值由136 g/100 g下降到2.31 g/100 g,环氧值由零升到6.754%,并将环氧化大豆油应用于PVC人造革的制备,结果显示:PVC人造革的5%失重温度为297.50℃,高于DOTP的249.17℃,对PVC人造革热稳定性提升,环氧化大豆油和DOTP增塑剂的人造革显示出相似的力学性能和耐迁移、耐抽出性能。     

环氧聚四氢苯酐二甘醇酯的合成及表征

以四氢苯酐、二甘醇、2-乙基己醇、双氧水为原料,钛酸四正丁酯、甲酸为催化剂,分别经酯化和环氧化两步合成功能化环氧聚酯增塑剂环氧聚四氢苯酐二甘醇酯。考察了酯化反应温度、时间、醇酸摩尔比、封端剂用量、催化剂用量以及环氧化反应温度、时间、双氧水用量、甲酸用量对环氧聚四氢苯酐二甘醇酯合成的影响。采用红外光谱仪(FT-IR)、核磁共振仪(1H-NMR)、热重分析仪(TGA)对产品的结构和热稳定性等进行了表征。结果显示,最佳酯化反应条件为:四氢苯酐、二甘醇、2-乙基己醇的摩尔比为1.0:1.25:0.50,催化剂用量为酸酐质量的0.80%,反应温度200℃,反应时间6 h。最佳环氧化条件为:聚四氢苯酐二甘醇酯、甲酸、H2O2的质量比为1.0:0.50:0.90,反应温度50℃,反应时间1 h。产品环氧值>1.40%,碘值<4.0 g(100g)1,具有较好的流动性和热稳定性,加入PVC树脂中后,有效地提高了PVC的热稳定性。     

植物油基环氧化聚甘油多酯增塑剂的合成及应用

以生物柴油的副产物粗甘油为原料,通过聚合反应得到聚合甘油;再与油酸通过酯化反应得到中间产物聚甘油不饱和脂肪酸多酯。然后在无溶剂条件下,以硫酸为催化剂进行环氧化反应得到增塑剂环氧化聚甘油多酯。考察了反应温度、反应时间、甲酸用量以及 H2O2用量对产物的环氧值的影响。同时采用了傅立叶变换红外光谱和热重分析对产物的结构和热稳定性进行表征。结果表明,最佳环氧化条件为：反应温度65℃,反应时间6 h,聚甘油不饱和脂肪酸多酯、甲酸、30％ H2O2质量比为1∶0.5∶1.2。产品的酸值为1.24 mg KOH／g,环氧值为6.4％,残留碘值为6.8 mg／100 g,具有较好的热稳定性,应用到 PVC 树脂中可有效地提高 PVC 的增塑性。     

由生物柴油合成环氧脂肪酸钙及在PVC中应用

报道了利用生物柴油制备环氧脂肪酸钙的方法,用刚果红试验、热烘试验、转矩流变仪混炼试验测试环氧脂肪酸钙作为聚氯乙烯(PVC)稳定剂的热稳定性能,同时分析其红外吸收光谱,测试其在应用于PVC时制品的力学性能,并与硬脂酸钙进行比较。结果表明:利用生物柴油制备环氧脂肪酸钙能改进工艺、降低成本;制备的环氧脂肪酸钙的热稳定性大于硬脂酸钙的,应用于PVC时制品的力学性能也好于使用硬脂酸钙的;可替代硬脂酸钙作为高效、无毒的PVC主稳定剂使用。     

用作PVC热稳定剂的环氧油酸盐的制备和应用

以油酸、双氧水和甲酸为原料合成了环氧油酸,通过复分解反应合成了环氧油酸钙、环氧油酸钡和环氧油酸锌。将3种环氧油酸盐复配用于PVC体系,采用刚果红法、热老化箱法及电导率法,考察了复合热稳定剂体系中不同金属配比对PVC体系热稳定性能的影响。结果表明:当环氧油酸钙/钡/锌的金属质量比为1/3/1时,体系的热稳定性最好。     

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。     

镧镁水滑石的制备及其对PVC热稳定性能的影响

采用共沉淀法,改变La~(3+)/Mg~(2+)投料摩尔比和陈化温度制备了一系列镧镁水滑石。采用镧镁水滑石作为PVC热稳定剂,通过刚果红实验和动态热稳定性实验,探讨了不同制备条件下镧镁水滑石对PVC静态、动态热稳定性能的影响。结果表明,La~(3+)/Mg~(2+)投料摩尔比和陈化温度是影响镧镁水滑石中镧含量的主要因素。镧镁水滑石可以显著提高PVC的静态、动态热稳定性能。镧镁水滑石制备过程中,陈化温度是影响PVC/镧镁水滑石热稳定性和加工性能的关键因素。当陈化温度分别为90、100和110℃时,PVC/镧镁水滑石静态、动态热稳定性能明显高于陈化温度为70℃时的性能;当陈化温度为100℃时,镧镁水滑石对PVC的静态、动态热稳定性的影响较优,同时,PVC/镧镁水滑石的塑化扭矩较低,相应的加工能耗较低。     

Evaluation effects of biobased plasticizer on the thermal,mechanical, dynamical mechanical properties,and permanence of plasticized PVC

Sunflower oil (SO) is a renewable resource that can be epoxidized, and the epoxidized SO has potential uses as an environmentally friendly in polymeric formulations, especially for poly (vinyl chloride) (PVC). Epoxidized sunflower oil (ESO) was prepared by treating the oil with peracetic acid generated in situ by reacting glacial acetic acid with hydrogen peroxide. Epoxidation was confirmed using spectroscopic and titration methods. ESO was used as a coplasticizer in PVC for the partial replacement of di‐(2‐ethyl hexyl) phthalate (DEHP). The effect of ESO on the thermal stability of plasticized PVC was evaluated by using synmero scale for the sheets. In presence of ESO plasticized PVC samples showed a reduction in discoloration and the number of conjugated double bonds. By using thermogravimetry, the incorporation of 15/45 of ESO/DEHP in PVC presents the lowest weight loss. The results of the shore hardness and mechanical properties showed that a proportion of DEHP could be substituted by ESO. By use of DMA, the formulation which contains 25 % wt of ESO in plasticizer system shifts the glass transition temperature (T_g) to ambient temperature. The migration phenomenon was studied on PVC based samples plasticized with DEHP and ESO in varying amounts. The migration was monitored by the weight loss percentage of the samples immersed into n‐hexane or heated in an oven. The amount of extracted or volatilized DEHP is proportional to the added ratio of ESO in plasticizer system. All of this favored the partial replacement of DEHP by ESO as biobased plasticizer for flexible PVC. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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.     

Epoxidized Mesua ferrea L. seed oil‐plasticized thermostable PVC and PVC‐clay nanocomposites

The use of vegetable‐oil‐based polymeric plasticizers with nanotechnology can create new applications for plasticized poly(vinyl chloride) (PVC). Epoxidized Mesua ferrea L. (Ceylon Ironwood) seed oil was used as a plasticizer for PVC. Further, nanocomposites were prepared through an ex‐situ technique using epoxidized‐oil‐swelled organically modified montmorillonite (5 wt%) and PVC. Notable improvement in thermal and processing characteristics of the nanocomposites was observed over those of the virgin polymer (in both unplasticized and plasticized PVC), as studied by TGA. The prepared nanocomposites were characterized by FTIR, SEM, TEM, and XRD techniques. A dramatic decrease in viscosity (7‐fold) was observed in THF for a 10% solution of epoxidized‐oil‐modified PVC compared to unplasticized PVC in THF, as measured by Brookfield viscometer. Isothermal analysis at three different temperatures (100, 150, and 200°C) reveals sufficient stability of the epoxidized oil modified PVC nanocomposites, as confirmed by gravimetric and FTIR analysis. Augmentation of thermostability and good retention of mechanical properties of the (Mesua ferrea L.)‐plasticized‐PVC/clay nanocomposites with respect to rigid PVC vouch for the utility of the former as advanced industrial materials. J. VINYL ADDIT. TECHNOL., 18:168–177, 2012. © 2012 Society of Plastics Engineers     

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     

Soil burial degradation of new bio‐based additives. Part I. Rigid poly(vinyl chloride) films

Commercial sunflower oil was epoxidized, and the epoxidized sunflower oil (ESO) was used as a thermal stabilizer for poly(vinyl chloride) (PVC). Rigid formulations stabilized with ESO as a new stabilizer and epoxidized soybean oil (ESBO) as a commercial stabilizer for comparison were prepared. The aging of the PVC samples was investigated in landfill soil for 24 months. The structure modifications of the polymer were followed by Fourier transform infrared spectroscopy (FTIR). Furthermore, the variations of density and mechanical properties (tensile and Shore D hardness) were considered. The variations of the mass of the samples, the glass transition temperature (T_g), the molar mass distribution, and the weight loss were followed as a function of time of soil burial. The soil burial test showed the loss of additives by migration and biodegradation that led to the modification of density, mechanical properties, molar mass distribution, and weight loss of the PVC samples. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

Studies in the thermal degradation of poly(vinyl chloride)

Thermal degradation of poly(vinyl chloride) (PVC) was studied in nitrogen atmosphere in the presence of rubber seed oil and epoxidized rubber seed oil, barium and lead soaps of rubber seed oil, and epoxidized seed oil at various temperatures. The rate of dehydrochlorination at 1% degradation and the time required to attain 1% degradation were used to assess the effect of the thermal susceptibility of PVC to dehydrochlorination. It was found that epoxidized rubber seed oil, the metal soaps of rubber seed oil, and epoxidized rubber seed oil markedly enhance the thermal stability of PVC. The order of increasing stabilizing influence was metal soaps of epoxidized rubber seed oil > metal soaps of rubber seed oil > epoxidized rubber seed oil > rubber seed oil. © 1993 John Wiley & Sons, Inc.     

Study and optimization of a soaking treatment to reduce migration from plasticized polyvinyl chloride

Commercial sunflower oil was epoxidized, and epoxidized sunflower oil (ESO) was used as a thermal stabilizer for polyvinyl chloride (PVC). This work describes a process capable to reduce the additives migration between plasticized PVC stabilized with ESO and food simulants. For that purpose, samples were first soaked in n‐heptane and then dried. Soaking temperature and drying temperature with time were optimized by using the methodology of experiment plans. The optimal conditions found were applied to study the migration of additives in a fatty simulant (olive oil) at 40°C. The test conditions were 12 days. Twelve circular samples of plasticized PVC were immersed in 120 mL of olive oil. A circular sample and 10 mL of food simulant were taken off every day to be analyzed. The rate of mass variation was followed. The specific migrations of the present additives were investigated by using Fourier transform infrared spectroscopy, atomic absorption spectrometry and gas chromatography‐ mass spectrometry. The results showed that the studied process reduced considerably the additives migration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Research of the Thermal and Strength Properties for Materials Obtained with Sunflower Oil

The use of pulverized fly ash (PFA) obtained from thermal power plants and epoxidized sunflower oil (ESFO) as recycled material in the construction industry was investigated. Epoxidized sunflower oil, clay (C) and pulverized fly ash were mixed at various proportions and were fired at 160, 180 and 200°C. The thermal conductivity and strength (compressive strength, tensile strength and abrasion loss) of the samples were determinated. The lowest value of thermal conductivity, 0.25 W/mK, was measured for the sample with a 70% FA/30% C ratio and 50% ESFO processed at 200°C. This sample had the lowest compressivetensile strength (3.28 MPa–0.633 MPa) and the highest abrasion loss (4.39%). The highest compressivetensile strengths and the lowest value of abrasion loss observed, were 7.21 MPa–0.939 MPa and 1.15%, respectively.     

Synthese teilchlorierter epoxidierter Fettderivate und ihre Anwendung als Kunststoffadditive

Synthesis of Partially Chlorinated, Epoxidized Fat Derivatives and their Use as Plastics Additives Epoxidized oils and fatty acid esters can markedly increase the effectiveness of the primary stabilizer system in PVC. Epoxidized oils have no effect on the initial colouring, and expensive costabilizers have to be added in order to improve it. After being first partially chlorinated, unsaturated fats and fatty acid methyl esters were subsequently epoxidized. The samples were incorporated into PVC formulations and their stabilizing effect compared with that of commercially-available epoxidized fats. The long-term effect builds up as a function of the epoxy groups, and the initial colouring improves as a function of the Cl content (up to 7 wt. % Cl). The partially-chlorinated, epoxidized soybean oils with a Cl content of 4.5–6.5 wt. % impart a considerably better initial colour to the PVC samples than the commercially-available costabilizers on an epoxidized fat basis, while exhibiting a comparable long-time stability.     

Soil burial degradation of new bio‐based additives. Part II. plasticized poly(vinyl chloride) films

Commercial sunflower oil was epoxidized, and the epoxidized oil (ESO) was used as a new thermal stabilizer for poly(vinyl chloride) (PVC). Plasticized formulations stabilized with ESO and epoxidized soya bean oil as a commercial stabilizer were evaluated for comparison. Two plasticizers were used, dioctyl phthalate and diisononyl adipate. The aging of the PVC samples was investigated in landfill soil for 24 months. The modifications of the structure of the polymer were followed by Fourier, transform infrared spectroscopy. Furthermore, the variations of density and mechanical properties (tensile and Shore D hardness) were considered, and the variations of the mass of the samples, the glass transition temperature (T_g), the molar mass distribution, and the weight loss were followed as a function of duration of soil burial. The morphological changes were tracked by scanning electron microscopy. Results showed that the nature of the plasticizer and heat stabilizer affects the properties of PVC as well as the phenomena of migration and biodegradation. J. VINYL ADDIT. TECHNOL., 19:183‐191, 2013. © 2013 Society of Plastics Engineers