环氧橡胶籽油增塑剂的研制

一、前言1947年Rohm and Hass公司首先把环氧增塑剂用于聚氯乙烯塑料,五十年代初期,发现它们与以钡、镉、锌的脂肪酸盐类为基础的稳定剂起协同作用,从此环氧增塑剂在塑料工业中的应用日益增加了。最常用的环氧增塑剂是环氧植物油。我国天然植物油脂的资源十分丰富,其中橡胶籽油就是资源较多的一种,橡胶籽含量大约是22～26%,是热带木本植物油料。橡胶籽     

Ti-SBA-15介孔分子筛催化制备环氧橡胶籽油的研究

以橡胶籽油(RSO)为原料,采用非均相介孔分子筛催化剂Ti-SBA-15催化制备环氧橡胶籽油(ERSO),探讨了催化剂用量、氧化剂叔丁基过氧化氢(TBHP)用量、反应时间、反应温度等因素对环氧化反应的影响。结果表明,Ti-SBA-15介孔分子筛催化剂催化制备ERSO的最佳工艺条件为:催化剂Ti-SBA-15用量0.062%(摩尔分数,以RSO物质的量计),TBHP与RSO物质的量比为1.3:1,反应时间6 h,反应温度70℃,此条件下制备的ERSO环氧值为68.9 mmol/g,产物转化率为82.22%,双键转化率为69.93%。通过FT-IR对比分析,进一步证实了环氧基团的生成。     

环氧橡胶籽油的开发与应用

综述了国内外PVC增塑剂环氧橡胶籽油的生产方法、工艺进展和主要应用领域,介绍了国内外工业化生产环氧橡胶籽油的主要方法、原理,并介绍了国内外环氧油的生产近况。     

橡胶籽油基多元醇的制备与表征

以环氧橡胶籽油（ERSO）为原料,甲醇和异丙醇为开环试剂,氟硼酸为催化剂,制备橡胶籽油基多元醇,以产物羟值为指标对制备工艺进行了优化,并对产物进行了表征。研究结果表明,橡胶籽油基多元醇的最佳制备条件为反应时间30min,反应温度70℃,醇与ERSO的质量比为4：1,氟硼酸用量为ERSO质量的1%,异丙醇与甲醇质量比为1：1。通过验证实验可知,在此条件下制备的橡胶籽油基多元醇酸值为2.68mg/g,羟值为219.32mg/g,平均相对分子质量为870.21,含水量为0.08%,黏度为4791mPa·s。同时,通过FT-IR、¹H NMR和¹³C NMR分析表征了橡胶籽油基多元醇的化学结构,结果表明,ERSO中的环氧基发生了开环反应,生成了多元醇。     

正交试验法优化橡胶籽油的提取工艺

采用溶剂法提取橡胶籽油,在单因素试验的基础上,用正交试验优化橡胶籽油的提取工艺。结果表明,橡胶籽油的最佳提取工艺为:提取溶剂为石油醚(60~90 ℃),原料粒度 0.90 mm 的橡胶籽 20 g,液料比7:1 (mL:g),提取温度 75 ℃,提取时间 8 h,此时橡胶籽油的得率为 35.17%。     

多价不饱和脂肪酸分离方法及在橡胶籽油中的应用

介绍了多价不饱和脂肪酸的分离纯化方法 ,以及在橡胶籽油中的应用前景。     

索氏法提取蓝莓籽油的工艺研究

目的：当前对于索氏法提取蓝莓籽油的研究未见报道,所以本文将着重对索氏法提取工艺进行研究,找到索氏法提取蓝莓籽油的最佳工艺条件,为蓝莓籽油的开发利用提供依据;方法：单因素及正交实验,在索氏法提取过程中,对提取溶剂、提取时间、提取温度、料液比进行单因素控制。并且检测相关数据进行对比分析,最终得到各个因素的最适合参数。最后在单因素试验基础上,选取对蓝莓籽油出油率影响较显著的的3个因素进行正交实验,对提取条件进行优化,得到索氏法提取蓝莓籽油的最佳工艺组合。结果：通过正交实验测得对蓝莓籽出油率影响程度依次为温度,料液比,最后是时间。得到的工艺条件为温度95℃,料液比为1∶15(g∶mL),时间为1h,最后按照正交实验的结果进行验证实验,证明了正交实验结果可靠。结论：通过正交实验优化索氏法提取蓝莓籽油的最佳工艺条件为：用石油醚作为提取溶剂,提取的温度为95℃,时间为1 h,料液比为1∶15(g∶m L),在此工艺条件下得到的蓝莓籽油的出油率为16.4375%。     

添加剂对橡胶籽油生物柴油氧化稳定性的改进

测定了橡胶籽油的物化性能及组成. 加入6种抗氧化剂,采用Rancimat法研究了其添加量及复配、温度、0#柴油添加量、金属铜、铁等对橡胶籽油生物柴油氧化稳定性能的影响. 结果表明,橡胶籽油所制生物柴油不饱和脂肪酸含量达82.1%,诱导期为0.81 h,达不到国家标准(6 h). 6种抗氧化剂在添加量为4000′10-6(w)时对橡胶籽油生物柴油的氧化稳定性能均有提升,其中TBHQ效果最好,使其氧化稳定性诱导期达13.09 h,6种抗氧化剂的抗氧化效果为TBHQ>BHT>D-TBHQ>OG>PG>BHA. PG与其他抗氧化剂复配后效果较好,而TBHQ与其他抗氧化剂复配后效果降低. 温度和0#轻柴油添加量对橡胶籽油生物柴油的氧化稳定性能影响很大,随温度升高,诱导期明显缩短,而随0#柴油添加量增大,诱导期增加,添加量较大时诱导期增幅很大. 铁、铜对其氧化稳定性能也有一定影响.     

橡胶籽油还原作用下铜渣的贫化

针对铜渣贫化过程碳排放问题,以橡胶籽油取代柴油作为铜渣贫化的还原剂,研究铜渣贫化过程中的热力学,分析橡胶籽油贫化铜渣机理。在不同温度和时间条件下进行喷吹橡胶籽油贫化实验,分析铜渣磁性铁含量和粘度的变化,用XRD和SEM对贫化后炉渣进行分析。结果表明,喷吹还原过程中主要还原剂是裂解产生的碳单质、H2和CO。贫化过程中磁性铁被橡胶籽油在高温下的裂解产物(H2, CO, C)还原成FeO,与渣中的SiO2结合生成铁橄榄石(Fe2SiO4);随贫化温度升高,相同喷吹时间内铜渣的磁性铁含量和粘度逐渐降低,使渣中的Cu相互碰撞聚集,最终沉降到坩埚底部。随贫化进行铜渣中的铁橄榄石相增多,磁性铁相减少。在坩埚底部聚集的铜颗粒粒度由1 cm增至3 cm,铜回收率达86%。     

乌桕籽油制备环氧脂肪酸异辛酯的工艺

选用具有丰富不饱和键的乌桕籽油为原料,采用了水解、酯化、环氧化等一系列反应合成了环保型增塑剂环氧脂肪酸异辛酯。并通过正交试验研究了脂肪酸异辛酯的环氧化工艺,确定了合成最佳工艺为:每百克脂肪酸异辛酯,甲酸30.37g,双氧水131.49g,反应温度65℃,反应4h后环氧值可达5.71。通过红外确定了产物的构成并考察了拉伸、热稳定性等性能,结果表明环氧脂肪酸异辛酯较邻苯二甲酸二辛酯(DOP)具有更好的热稳定性和挥发迁移性。     

Processability characteristics and physico‐mechanical properties of natural rubber modified with rubber seed oil and epoxidized rubber seed oil

The processability characteristics and physico‐mechanical properties of natural rubber (NR) modified with raw rubber seed oil and epoxidized rubber seed oil have been studied. The modified mixes showed higher scorch time and lower cure rate, crosslink density, and ultimate state of cure compared to an unmodified mix. The thermal stability of the vulcanizates was practically unaffected by the modification. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1413–1418, 2000     

Studies on epoxidized rubber seed oil as plasticizer for acrylonitrile butadiene rubber

The application of rubber seed oil (RSO) and epoxidized RSO (ERSO) as a plasticizer in acrylonitrile butadiene rubber (NBR) was studied using RSO and ERSO with different levels of epoxidation. The results indicated that ERSO could be used as a less leachable and low volatility plasticizer for NBR. The use of ERSO in NBR gave better abrasion resistance whereas the tensile strength and tear strength were comparable to those vulcanizates that contained dioctyl phthalate as a plasticizer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 668–673, 2003     

橡籽油的酸催化水解工艺研究

以橡籽油为原料进行常压一次酸催化水解反应。研究了反应温度、反应时间、催化剂用量、油水比和乳化剂用量对水解反应的影响,得出橡籽油水解的最优条件:反应温度为95℃,反应时间为9 h,催化剂浓硫酸用量为10%,油水比为1∶2,乳化剂十二烷基磺酸钠用量为1%,此时橡籽油的水解产物酸值为189.41mg KOH/g,水解率为94.71%。     

无硫酸环境环氧化大豆油合成条件优化

在无溶剂无硫酸条件下合成了环氧大豆油,对环氧化合成体系中的羧酸类型、用量及双氧水浓度等影响环氧值的若干因素进行了研究。甲酸的环氧化活性比乙酸和丙烯酸高。通过正交实验确定了最佳合成工艺条件为:m(大豆油)m(甲酸)m(双氧水)为1 0.15 1.0,反应温度60℃,反应时间5～6 h。产品环氧值≥6.20%,残留碘值<6.0%。产品经红外分析表明,在3008 cm-1处的原料C=C双键结构峰消失,在820 cm-1、787 cm-1处呈现出环氧键的伸缩振动的特征吸收峰。     

High value polyurethane resins from rubber seed oil

Rubber seed oil having high free fatty acid content and high unsaturation was used to obtain high quality polyurethane resins through epoxidation and ring opening with methanol and free fatty acids. Two polyols prepared with free fatty acids and without were cured with modified methylene diphenyl diisocyanate to obtain strong, high modulus glassy polyurethanes. The effect of structure on thermal and mechanical properties was analyzed. This showed that the polyol with free fatty acid utilized to obtain a branched structure gave superior crosslinking density and mechanical properties. © 2016 Society of Chemical Industry     

Nutritional and toxicological evaluation of rubber seed oil

Rubber (Hevea brasiliensis) seed oil (RSO) is available in India (Ca. 4500 tons per year) and is used mainly as a drying oil. The oil does not contain any unusual fatty acids, and it is a rich source of essential fatty acids C_18∶2 and C_18∶3 that make up 52% of its total fatty acid composition. Acute toxic potential in rats and the systemic effects and nutritional quality were assessed in a 13 week feeding study in weanling albino rats using a diet containing RSO or groundnut oil (GNO) (as the control) at a 10% level as the sole source of dietary fat. RSO did not manifest any acute toxic potential. Food consumption, growth rate and feed efficiency ratio of rats fed RSO were similar to those fed GNO. The digestibility of this oil was found to be 97%, as compared to 94% for GNO. There were no macroscopic or microscopic lesions in any of the organs which could be ascribed to the RSO incroporation in the diet. Thus the current data show that RSO could be used for edible purposes. However, it will be necessary to process the oil to achieve deodorization and to remove free fatty acids to make it organoleptically acceptable.     

Estimation of dilute solution viscosity parameters of rubber seed oil alkyds

Viscosity measurements were carried out in methyl ethyl ketone (MEK) and dimethyl formamide (DMF) for rubber seed oil alkyds having oil content of 20 (I), 30 (II), 35 (III), 40 (IV), 50 (V), and 60% (VI). Viscosity molecular weights, intrinsic viscosities, and viscosity parameters K and α, characteristic for both polymers and solvents, were determined. Generally, solubility properties were found to depend on molecular weight and polarity of the alkyds and solvent. Intrinsic viscosities of the alkyds were larger in DMF than in MEK, suggesting DMF to be a better solvent than MEK for rubber seed oil alkyds. Molecular weights determined for the alkyds range from 441 for sample III to 1323 for sample V. The viscosity molecular weights are in reasonable agreement with the values determined for samples II–V in MEK and samples I–IV in DMF. The values of Huggin's constant for these alkyds were also determined. Data reported also suggest that rubber seed oil alkyds tend to tolerate relatively basic solvent, such as DMF. Fractionation of the alkyds was considered to be in respect of molecular weight and polarity of the alkyds, and results show that low-molecular-weight species constitute greater proportion of the alkyds. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1987–1992, 1998     

亚临界水中橡胶籽油水解反应的试验研究

探讨油脂在亚临界水中水解反应的影响因素和反应动力学。以橡胶籽油为原料,在间歇式高温高压反应釜中进行水解反应,试验结果表明,在水与橡胶籽油体积比为3∶1(摩尔比为162∶1),反应温度280℃,压力15 MPa,反应时间40 m in时,橡胶籽油水解为脂肪酸的转化率可达96.2%;动力学计算表明,橡胶籽油在亚临界水中水解反应级数为1.4,反应活化能为43.5 kJ/mol。该研究为超临界二步法制备生物柴油的水解反应的动力学提供了理论基础。     

Optimization of rubber seed oil extraction using liquefied dimethyl ether

The objective of this study was to find the optimal condition for the extraction of rubber seed oil (RSO), using liquefied dimethyl ether (DME). Response surface methodology with a spherical central composite design model was employed to determine the optimal extraction condition, consisting of a seed moisture content (%wt), a solvent to solid ratio (g/g), and an extraction temperature (°C). A quadratic regression equation suggested the optimal extraction condition was a moisture content of 56.4%wt, a solvent to solid ratio of 6.7 (g/g), and a temperature of 33.3?°C. At this condition, the RSO yield predicted by the model gave a slight deviation of 0.68% from the experimentally validated results (41.48 versus 41.20%). RSO has a kinematic viscosity of 36.8 cSt, an acid value of 10.7 KOH/g oil, a fatty acid content of 5.1% and an unsaturated fatty acid content of 80%, resulting in the potential production of biodiesel, biolubricants, and biodegradable plastics.