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     

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。     

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。     

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。     

铜熔渣喷吹地沟油还原贫化

以地沟油为生物质还原剂,高温裂解后对铜火法冶炼铜渣进行还原贫化。结果表明,地沟油裂解产物主要是C, H2, CO和CH4等还原性小分子物质,1373, 1473和1573 K下裂解积碳的转化率分别为78.36%, 79.83%和80.07%,因此地沟油高温裂解时碳元素主要以积碳形式存在。热力学计算发现,高温下裂解产物均有良好的还原Fe3O4的活性,用地沟油替代传统化石类还原剂还原铜渣中磁性铁在热力学上是可行的。以N2为载气不仅有利于高温下地沟油顺利喷入铜熔渣中,且通过动量传递起到搅拌熔渣的作用,增大了微小铜滴碰撞聚集长大的机会。在熔炼温度1573 K、载气流量3 L/min、地沟油喷吹量2.055 mL/min、喷吹时间4 min、沉降时间50 min的最优还原贫化条件下,铜渣中Fe3O4含量从33.40wt%降至1.60wt%,含铜量从4.49wt%降至0.49wt%,渣中Fe3O4相转变为2FeO?SiO2相。根据Einstein?Roscoe方程分析,渣中Fe3O4含量减少有利于降低熔渣粘度,改善铜滴的沉降条件。继续增加地沟油喷吹时间沉降金属中杂质含量增加;沉降时间过长时,由于铜渣对铜的机械夹带和化学溶解作用,沉降效果不会更好。实验的铜回收率达89.09%。     

均匀设计优化环氧橡胶籽油的制备工艺

以橡胶籽油、甲酸和双氧水为原料,磷酸作催化剂,采用无溶剂法合成环氧橡胶籽油,采用均匀设计法研究了甲酸用量、反应时间及双氧水用量等对环氧值的影响。结果表明,最佳制备工艺条件为:橡胶籽油100 g,甲酸12.80 g,质量分数为30%的双氧水50.53 g,反应时间6 h,反应温度50～55℃,产品环氧值达11.68%。     

尿素包合法分离橡胶籽油中的多价不饱和脂肪酸

用尿素包合法从橡胶籽油混合脂肪酸中分离多价不饱和脂肪酸 ,用正交设计实验法对分离工艺进行研究 ,其最佳分离条件是 :原料配比为m(混合脂肪酸 )∶m(尿素 )∶m(乙醇 ) =1 0 0∶1 5∶1 8,回流时间 12 0min。经一次尿素包合法分离即可得到多价不饱和脂肪酸质量分数大于90 %的产品 ,实验收率大于 35 %     

橡胶籽油基复合型环保增塑剂用于PVC的研究

将自制的橡胶籽油基环氧脂肪酸甲酯（EFAME）与对苯二甲酸二辛酯（DOTP）混合后,与聚氯乙烯（PVC）共混成型,考查EFAME在软质PVC中的增塑性能及其对DOTP的替代效果。利用拉力试验机、差示扫描量热仪、动态热力学分析仪及热老化烘箱对塑化体系的力学性能、加工性能、耐热性及耐久性进行分析。结果表明,复合型增塑剂可有效改善PVC制品的柔韧性、耐磨性、热性能及加工流变性;EFAME用量为20份时,PVC制品的玻璃化转变温度由0.32 ℃降低至-4.63 ℃,质量损失10 % 和50 %时的温度得到提高,热老化整体变色时间提高了4倍。     

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。     

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.     

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     

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     

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     

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%。     

硼酸钙对铜渣中夹杂铜沉降效果的影响

考察了添加剂CaB2O3对转炉铜渣中夹杂铜沉降效果的影响,并结合铜渣的粘度测试及红外光谱表征,研究其影响机理,采用FactSage软件计算了添加剂对铜渣液相线温度的影响。结果表明,随添加剂含量增大,铜渣中夹杂铜的沉降效果逐渐增强,添加剂含量由0增至6wt%时,底部渣含铜量由4.10wt%增至6.85wt%,这是由于添加剂可有效降低铜渣粘度。随添加剂含量增大,渣粘度降低,但降低效果随温度增大而趋于平缓。随添加剂含量增大,铜渣的硅酸盐结构趋于简化,添加剂通过破坏铜渣复杂的硅酸盐结构降低铜渣粘度。铜渣的液相线温度随添加剂含量增大而减小,添加剂通过减少渣中固体颗粒的方式降低铜渣粘度。     

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.