Kinetic Studies on Oxirane Cleavage of Epoxidized Soybean Oil by Methanol and Characterization of Polyols

The kinetics of the oxirane cleavage of epoxidized soybean oil (ESO) by methanol (Me) without a catalyst was studied at 50, 60, 65, 70 °C. The rate of oxirane ring opening is given by k[Ep][Me]², where [Ep] and [Me] are the concentrations of oxiranes in ESO and methanol, respectively and k is a rate constant. From the temperature dependence of the kinetics thermodynamic parameters such as enthalpy (ΔH), entropy (ΔS), free energy of activation (ΔF) and activation energy (ΔE _a) were found to be 76.08 (±1.06) kJ mol⁻¹, −118.42 (±3.12) J mol⁻¹ k⁻¹, 111.39 (±2.86) kJ mol⁻¹, and 78.56 (±1.63) kJ mol⁻¹, respectively. The methoxylated polyols formed from the oxirane cleavage reaction , were liquid at room temperature and had three low temperature melting peaks. The results of chemical analysis via titration for residual oxiranes in the reaction system showed good agreement with IR spectroscopy especially the disappearance of epoxy groups at 825, 843 cm⁻¹ and the emergence of hydroxy groups at the OH characteristic absorption peak from 3,100 to 3,800 cm⁻¹.     

Oxirane Cleavage Kinetics of Epoxidized Soybean Oil by Water and UV‐Polymerized Resin Adhesion Properties

Di‐hydroxylated soybean oil (DSO), a biobased polyol synthesized from epoxidized soybean oil (ESO) could be used to formulate resins for adhesives; however, current DSO synthesis requires harsh reaction conditions that significantly increase both cost and waste generation. In this paper, we investigate the kinetics of oxirane cleavage in ESO to DSO by water and elucidate the role of different process parameters in the reaction rate and optimization of reaction conditions. Our kinetic study showed that ESO oxirane cleavage was a first‐order reaction and that the ESO oxirane cleavage rate was greatly influenced by tetrahydrofuran (THF)/ESO ratio, H₂O/ESO ratio, catalyst content, and temperature. Optimized reaction parameters were THF/ESO of 0.5, H₂O/ESO of 0.25, catalyst content of 1.5 %, and reaction time of 3 h at 25 °C. DSO with hydroxyl value of 242 mg KOH/g was obtained under these conditions. We also characterized the structure, thermal properties, adhesion performance, and viscoelasticity of UV‐polymerized resins based on this DSO. The resin tape exhibited peel adhesion strength of 3.6 N/in., which is comparable to some commercial tapes measured under similar conditions.     

环氧大豆油脱色工艺研究

研究在碱性介质下过氧化氢对环氧大豆油的脱色工艺,考察了过氧化氢和氢氧化钠用量、反应温度、反应时间等因素对脱色工艺的影响.得到最优脱色工艺条件为:物料配比(重量比)为ESO:NaOH(100%):H2O2(100%)=100:1.0～1.2:1 6～2 0,反应时间为50-60min,反应温度为75℃～80℃.在此条件下可将环氧大豆油的色泽由>250号降低至<150号,明显降低环氧大豆油的色泽,提高质量水平.     

Curing Characteristics and Mechanical Properties of Oil Palm Wood Flour Reinforced Epoxidized Natural Rubber Composites

Abstract

The paper reports on the curing characteristics and mechanical properties of oil palm wood flour (OPWF) reinforced epoxidized natural rubber (ENR) composites. Three sizes of OPWF at different filler loadings were compounded with a two roll mill. The cure (t ₉₀) and scorch times of all filler size decrease with increasing OPWF loading. Increasing OPWF loading in ENR compound resulted in reduction of tensile strength and elongation at break but increased tensile modulus, tear strength and hardness. The composites filled with smaller OPWF size showed higher tensile strength, tensile modulus and tear strength. Scanning electron microscope (SEM) micrographs showed that at lower filler loading the fracture of composites occurred mainly due to the breakage of fibre with minimum pull-out of fibres from the matrix. However as the filler loading is increased, the fibre pull-out became very prominent due to the lack of adhesion between fibre and rubber matrix.     

无溶剂法合成环氧蓖麻油的工艺研究

以可再生的蓖麻油为主要原料,H3P04作为催化剂,30% H2O2作为氧源,在无溶剂条件下合成环氧蓖麻油.通过正交实验的方法对蓖麻油环氧化反应进行了研究和探讨,得出最佳反应条件为:n(H202):n(蓖麻油双键)=1.4:1,n(甲酸):n(蓖麻油双键)=0.5:1,催化剂H3POa质量分数为蓖麻油的0.3%,反应时间...     

A Comparative Study on the Mechanical, Thermal and Morphological Characterization of Poly(lactic acid)/Epoxidized Palm Oil Blend

In this work, poly(lactic acid) (PLA) a fully biodegradable thermoplastic polymer matrix was melt blended with three different epoxidized palm oil (EPO). The aim of this research was to enhance the flexibility, mechanical and thermal properties of PLA. The blends were prepared at various EPO contents of 1, 2, 3, 4 and 5 wt% and characterized. The SEM analysis evidenced successful modification on the neat PLA brittle morphology. Tensile tests indicate that the addition of 1 wt% EPO is sufficient to improve the strength and flexibility compared to neat PLA. Additionally, the flexural and impact properties were also enhanced. Further, DSC analysis showed that the addition of EPO results in a decrease in T(g), which implies an increase in the PLA chain mobility. In the presence of 1 wt% EPO, TGA results revealed significant increase in the thermal stability by 27%. Among the three EPOs used, EPO(3) showed the best mechanical and thermal properties compared to the other EPO's, with an optimum loading of 1 wt%. Conclusively, EPO showed a promising outcome to overcome the brittleness and improve the overall properties of neat PLA, thus can be considered as a potential plasticizer.     

丙烯酸化环氧大豆油泡沫塑料的研究

以环氧大豆油为原料，通过丙烯酸化改性，制备出可自由基聚合的树脂。然后在引发剂作用下，与稀释剂苯乙烯和甲基丙烯酸甲酯共聚并发泡形成泡沫塑料。详细研究了丙烯酸化条件对环氧大豆油酯化程度的影响，发现N，N-二甲基苄胺是适宜的催化剂，所得产物结构与预期一致。还研究了引发体系和稀释单体对泡沫塑料性能的影响，结果表明，以过氧化苯甲酰为引发剂所得泡沫塑料的压缩性能较好，残余单体的含量较低。     

提高环氧大豆油环氧值的研究

探索了提高环氧大豆油环氧值的几种途径.     

绿色增塑剂环氧大豆油的合成与表征

用自制的催化剂合成了一种环氧大豆油。通过L16(45)正交试验考察了双氧水用量、催化剂用量、反应时间和反应温度对环氧大豆油环氧值的影响。结果表明:在双氧水用量100份、催化剂用量0.5份(大豆油用量定为100份)、反应温度50℃、反应时间12.5 h的最佳工艺条件下,产品的环氧值为6.58%,碘值为0.83 gI/100g。产品通过红外和核磁共振表征,确定大豆油被环氧化生成环氧大豆油。     

Rigid Polyurethane Foam Production from Palm Oil-Based Epoxidized Diethanolamides

A new type of rigid polyurethane foam was produced by incorporating oxazolidone heterocyclic rings on to polyurethane backbones. Epoxidized diethanolamides were synthesized by reacting palm oil blends of epoxidized palm olein and refined bleached deodorized palm kernel olein with diethanolamine to produce rigid polyurethane foams. Epoxides, retained in the diethanolamides, reacted with isocyanate during foam production in the presence of AlCl₃–THF complex catalyst to form oxazolidone linkages in the polyurethane network. The carbonyl stretch of oxazolidone was identified at 1,750 cm⁻¹ through Fourier Transform Infra Red analysis. Chemical modifications of the polyurethane network also improved the thermal and mechanical properties of the foams. In addition, isocyanate index 1.4 was determined to be the most suitable in the production of foams from this newly synthesized epoxidized diethanolamides.     

高品质环氧大豆油的实验研究

环氧大豆油是强前增塑效果比较好的无毒、环保、可再生资源捌备的增塑翔,主要是用大豆油采用过氧化物氧化而制得的一种化工产品。近年来,我国已成为甄洲地区增塑剂生产量和消费最多的国家,随着人们环境保护意识的增强,医药以及食品包装、日用品、玩具等塑料制品对增塑剂提出了更高的卫生要求。文章通过实验研究了制备环氧大豆油的最佳原料配比,工艺条件和影响产晶质量的因素,并通过正交试验确定了最佳制备工艺条件。     

环氧大豆油对软PVC性能影响的研究

研究了环氧大豆油对软聚氯乙烯(PVC)性能的影响。实验表明,铅盐和有机锡的热稳定性较好,单独使用硬脂酸钙、硬脂酸锌、环氧大豆油或不足量的有机锡热稳定剂时,PVC样品很快变色。环氧大豆油与硬脂酸钙、硬脂酸锌、有机锡热稳定剂并用时,环氧大豆油具有很好的协同效应;但环氧大豆油和硬脂酸钙、硬脂酸锌不能简单替代有机锡稳定剂。热重分析证明了不同热稳定剂的效果。作为辅助增塑剂,环氧大豆油用量应低于5份。     

无味环氧豆油的合成技术研究

本文阐述无味环氧豆油的合成技术，将精制大豆油，乙酸与其它辅料按配方比例投入反应釜，再慢慢滴加双氧水，使之环氧化反应，待反应完全后，经水洗，中和，脱水等一系列工艺，制成无味环氧豆油成品。这种合成方法，工艺简单，产品质量稳定优良。     

国产镍基催化剂加氢性能研究

国产镍基催化剂用于棕榈油加氢制硬化油的实验结果与进口催化剂进行比较表明,其催化性能基本达到替代进口催化剂的水平;在此基础上,通过正交试验得出国产催化剂YM9002用于棕榈油加氢过程中的最佳工艺操作条件为反应压力2.5 MPa,反应时间60 min,催化剂用量为0.3%。     

Ring-Opening Polymerization of Epoxidized Soybean Oil

Ring-opening polymerization of epoxidized soybean oil (ESO) catalyzed by boron trifluoride diethyl etherate (BF₃·OEt₂) in methylene chloride was conducted in an effort to develop useful biodegradable polymers. The resulting polymerized ESO (PESO) were characterized using infrared (IR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), ¹H NMR, ¹³C NMR, solid state ¹³C NMR and gel permeation chromatography (GPC). The results indicated that PESO materials were highly crosslinked polymers. They had glass transition temperatures ranging from −16 to −48 °C. TGA results showed the PESO polymers were thermally stable at temperatures up to 220 °C. Decomposition of the polymers was found to occur at temperature greater than 340 °C. GPC results indicated the extracted soluble substances from PESO polymers were ESO dimers, trimers and polymers with low molecular weights. The resulting crosslinked polymers can be converted into hydrogels by chemical modification, such as hydrolysis. These soy based hydrogels will find applications in personal care and health care areas.