金属氯化物对亚临界水中纤维素水解反应的影响

研究了纤维素在亚临界水中无催化水解及分别添加ZnCl2、FeCl3、CuCl2、AlCl3对水解反应的影响。实验结果显示,无催化剂时,葡萄糖的收率在280℃,60s及(7.0±0.2)MPa时达到最大为14.3%。添加ZnCl2、FeCl3、CuCl2及AlCl3均能促进纤维素的水解及葡萄糖的降解。纤维素的水解及葡萄糖的降解反应级数均为一级。利用一级反应模型对纤维素在260℃水解及葡萄糖的降解反应进行数据拟合,求得了纤维素的水解速率常数(k),葡萄糖的生成速率常数(k1)及葡萄糖的降解速率常数(k2)。添加AlCl3体系中纤维素的水解速率常数(k)大于葡萄糖的降解速率常数(k2),有利于葡萄糖的生成,在260℃,120s及(5.2±0.2)MPa时,葡萄糖收率达到最大为46.05%。添加ZnCl2、CuCl2及FeCl3体系中葡萄糖的降解速率常数(k2)大于纤维素的水解速率常数(k),不利于葡萄糖的生成。XRD分析显示,金属氯化物的加入并没有破坏纤维素的晶体类型,水解残渣仍然保持纤维素Ⅰ型晶体结构。     

花生壳在近临界水中催化水解反应及其动力学

以花生壳为原料,AlCl3为催化剂,在近临界水中,考察了反应温度,反应时间和AlCl3浓度对还原性糖收率的影响,并建立花生壳水解反应动力学方程。结果表明,当反应温度为493 K,AlCl3的质量分数为0.02%,反应180 s,还原性糖的收率达到最大值40.4%。花生壳在近临界水中水解为一级反应,花生壳水解与还原性糖降解的活化能分别为54.03和22.44 kJ/mol,指前因子分别为2.89×103和1.26 s-1。     

近临界水中薯蓣皂苷的水解反应

在近临界水中研究了薯蓣皂苷水解成薯蓣皂苷元的工艺和反应动力学,分别考察了反应温度、压力、时间等因素对薯蓣皂苷元收率的影响。实验结果表明,近临界水解法的较佳工艺条件为260℃,25 MPa,反应10 min。在此条件下,薯蓣皂苷元收率为1.46%。动力学研究结果表明,薯蓣皂苷在近临界水中水解是一级反应,活化能为76.7 kJ/mol,指前因子k0为5.99×104s-1。     

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     

近临界水中乙烯-醋酸乙烯酯共聚物水解反应动力学

为了开发聚醋酸乙烯酯绿色水解工艺,以聚乙烯醋酸乙烯酯为原料,研究了其在近临界水中的水解反应动力学。在考察了实验数据的重现性和物料配比对聚乙烯醋酸乙烯酯水解反应的影响之后,系统地测定了483.15～623.15K下聚醋酸乙烯酯的无催化和醋酸催化下水解反应动力学数据,并采用元素分析仪、傅立叶变换红外光谱仪、凝胶色谱仪、热重分析仪、示差扫描量热仪对水解产物进行了表征。结果表明,近临界水中聚醋酸乙烯酯水解改性是可行的,通过改变水解工艺条件可获得一系列不同醋酸乙烯酯、乙烯醇含量的水解产物;温度、物料配比以及原料不同酯基含量是影响水解速率的主要因素,同时在聚乙烯醋酸乙烯酯水解反应中醋酸的引入可大大提高反应速度。以自催化反应动力学模型对实验数据进行了拟合,得到了无催化和1mol·L-1醋酸催化下聚乙烯醋酸乙烯酯水解反应活化能分别为51.8kJ·mol-1和41.6kJ·mol-1。研究建立了一个近临界水中聚乙烯醋酸乙烯酯水解改性的新方法,方法具有绿色、可控等优点。     

近临界水中苯乙腈无催化水解反应动力学

为了开发苯乙酸的绿色制备工艺,系统地研究了近临界水中苯乙腈的无催化水解反应动力学.在研究了实验数据的重现性以及苯乙腈初始浓度对反应动力学影响之后,系统地测定了523.15～563.15 K下苯乙腈及其分解的中间产物苯乙酰胺的水解反应动力学数据,结果表明苯乙腈水解反应是典型的连串反应,以苯乙酰胺为中间产物.且能高选择性地得到最终产物苯乙酸.并以一级连串反应动力学模型对实验数据进行了拟合,得到了苯乙腈和苯乙酰胺水解反应活化能分别为64.4 kJ·mol-1和82.4 kJ·mol-1.论文工作为苯乙酸的绿色制各提供了重要的基础数据,同时能为其他腈类物质在近临界水中的水解提供参考.     

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。     

亚临界萃取石榴籽油工艺的响应面优化

在单因素试验的基础上,运用响应面法优化石榴籽油的亚临界萃取工艺。结果表明萃取温度、萃取时间及液料比对石榴籽油得率有显著影响。优化得到的最佳工艺条件为:萃取温度38℃,萃取时间42min,液料比6。在此工艺条件下,石榴籽油得率达到21. 07%,与模型预测值21. 15%之间具有良好的拟合性。     

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%。     

近临界水中鱼肉水解制备氨基酸的反应动力学

利用鱼肉蛋白制备氨基酸不但具有经济效益,而且为生物质资源高效利用提供技术支持。采用HL-F(0.2 L+1.5 MG)/30 MPa-IIA超临界水反应装置,在无催化剂、反应温度分别为220,240,260℃,反应时间为30 min条件下,对鱼肉蛋白在近临界水中水解为氨基酸的反应动力学进行了实验研究。用AAA-Direct氨基酸分析仪测定不同反应时间中氨基酸总产率,以酸水解鱼肉蛋白得到的氨基酸量为完全水解标准。在水过量的情况下,得到了鱼肉蛋白水解率宏观反应动力学方程。结果表明鱼肉蛋白水解动力学的级数为1.614 7,220,240,260℃下的反应速率常数分别为0.001 7,0.004 5,0.009 7,活化能为145.125 kJ/mol,前置因子A为9.475 7×109,为工业化生产提供了基础数据。     

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     

木质纤维素在亚/超临界水中液化的初步研究

在保持盐浴温度为420℃、压力为25 MPa、反应时间为1 min的实验条件下,对亚/超临界水中木质纤维素的液化进行了实验研究。液化产物经高效液相色谱分析,结果表明,液相产物中含有酸、葡萄糖、果糖及其它一些水溶性有机物。通过扫描电镜(SEM)观察,水解残渣可以明显的发现木质纤维素从粒状高结晶束到粉化成絮状残渣的水解过程,同时发现在盐浴温度为420℃,压力在20 MPa时木质纤维素的液化率最高。     

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%。     

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     

Kaolin modified with sodium salt of rubber seed oil as a reinforcing filler for blends of natural rubber,polybutadiene rubber and acrylonitrile–butadiene rubber

Blends of natural rubber (NR) and synthetic rubbers are widely used in the rubber industry to meet specific performance requirements. Further, the emerging field of organomodified clay/rubber nanocomposites could provide a host of novel materials having a unique combination of properties to meet various stringent service conditions. Previous studies have shown that at very low dosages, china clay (kaolin) modified with sodium salt of rubber seed oil (SRSO) improved the cure characteristics and physico‐mechanical properties of NR. Results of the present study show improved cure characteristics and physico‐mechanical properties for blends of NR with butadiene rubber and nitrile rubber containing 4 phr of SRSO‐modified kaolin as indicated by reduction in optimum cure time along with higher tensile strength, tensile modulus and elongation at break for their vulcanizates as compared to those containing unmodified kaolin. The SRSO‐modified kaolin/rubber nanocomposites showed improved flex resistance, reduced heat build‐up, tan delta and loss modulus and higher chemical crosslink density index, indicating a reinforcing effect of the SRSO‐modified kaolin, enabling the nanocomposites to have potential industrial applications. © 2015 Society of Chemical Industry     

Epoxidation and hydroxlation of rubber seed oil: one‐pot multi‐step reactions

Epoxidized and hydroxylated rubber seed oils were prepared by peroxyformic acid generated in situ by reacting formic acid and hydrogen peroxide with RSO, a renewable resource. The structural and physico‐chemical properties of RSO have been determined. The fatty acid composition showed a high content of polyunsaturated fatty acids. The modified products were characterized with regard to their structure and properties. The findings of this study revealed that both hydroxylated and epoxidized RSO can be prepared by one‐pot multi‐step reactions.