生物柴油在制备PVC助剂中的应用

简单介绍绿色能源生物柴油深加工在制备增塑剂、稳定剂及润滑剂等PVC助剂中的应用。其中以制备环氧脂肪酸甲酯和氯代甲氧基脂肪酸甲酯最为经济可行。指出利用环氧脂肪酸甲酯制备多功能PVC助剂是重要的发展方向。     

环氧脂肪酸甲酯的合成研究进展及应用

环氧脂肪酸甲酯无毒环保,符合欧盟RoHS环保指令,可用作聚氯乙烯(PVC)制品等的增塑剂。本文介绍了环氧脂肪酸甲酯合成的研究进展,概述了其应用现状;展望了环氧脂肪酸甲酯制备方法的发展趋势。     

PVC塑料用环氧脂肪酸甲酯增塑剂的研制

介绍了聚氯乙烯（PVC）增塑剂环氧脂肪酸甲酯的制备方法：采用生物型脂肪酸甲酯为原料,双氧水为给氧体,有机酸作载体,在不使用任何溶剂、稳定剂和酸性催化剂的条件下,采用封闭式冷却循环装置一步法制得环氧增塑剂产品;讨论丁环氧脂肪酸甲酯在PVC生产中的应用情况。     

地沟油改性制备PVC用环氧脂肪酸甲酯增塑剂

以地沟油为原料,采用分步甲酯化、酸催化-环氧化法制备环氧脂肪酸甲酯增塑剂,并对产品的化学结构进行表征。结果表明,产品在839.2cm-1处出现了环氧基特征峰;环氧化反应后原料中的不饱和脂肪酸甲酯含量显著降低,同时生成了环氧脂肪酸甲酯;产品的环氧化程度随环氧化时间的延长逐步提高,在环氧化时间为8h时环氧值达到最大3.9%,碘值相应地从87.7降至8.7;与邻苯二甲酸二辛酯（DOP）相比,环氧脂肪酸甲酯增塑剂闪点高于197℃,对聚氯乙烯（PVC）树脂有相似的增塑效率,50%的增塑剂可使PVC的玻璃化转变温度从87℃降低到-10℃,但耐迁移性尚不及DOP。     

环氧脂肪酸甲酯在PVC电线电缆料中的应用

研究以部分环氧脂肪酸甲酯替代对苯二甲酸二辛酯(DOTP)增塑聚氯乙烯(PVC)体系,考察了环氧脂肪酸甲酯用量对PVC电线电缆料性能的影响。研究结果表明,随着环氧脂肪酸甲酯用量的增加,材料的电阻率呈下降趋势、冲击脆化性能和热稳定性能改善,材料的拉伸性能变化不大。当环氧脂肪酸甲酯替代DOTP的量为30%时,材料综合性能与效益达到最优。     

环氧脂肪酸甲酯连续闪蒸脱水脱味精制工艺研究

环氧脂肪酸甲酯是以脂肪酸甲酯为原料制备的新型环保增塑剂。传统的生产工艺中,采用减压蒸馏制得的产品酸值、环氧值、色泽、气味、加热减量等指标不够理想。采用连续闪蒸脱水脱味精制工艺,制备的产品其加热减量≤0.30%,色泽≤100号(Pt-Co法),基本无味,达到了生产高品质浅色无味的环氧脂肪酸甲酯的目的。     

增塑剂：无毒增塑剂-环氧化脂肪酸甲酯的制备

标题环氧化脂肪酸甲酯用作无毒增塑剂或稳定剂,其结构式如图Ⅰ所示,其中R,R′为CnH2n＋1;n=0—15。该化合物以酸作催化剂,由脂肪酸甲酯与过氧化氢经环氧化反应制得。具有相容性好、低挥发性、耐热、光稳定、润滑效果好;分散性好等优点。PVC中添加量为5—30%。可替代对苯二甲酸二辛酯制备无毒PVC制品（如食品包     

环氧脂肪酸甲酯增塑剂的研制及应用

自制了S2O28-/介孔氧化锆固体酸催化剂,并通过氮气吸附脱附、XRD、TG-DSC对其结构进行表征。该催化剂参与制备环氧脂肪酸甲酯增塑剂,产物的环氧值达4.55%,表观理化性质分析、FI-IR及1H-NMR组分分析均表明,催化环氧化的效果较好。在相同条件下,分别考察环氧脂肪酸甲酯、DOP、DOTP增塑的环氧树脂固化体系的力学性能,结果表明,环氧脂肪酸甲酯能赋予固化体系较佳的综合力学性能。     

催化环氧脂肪酸甲酯制备9(10)-羟基-10(9)-甲氧基脂肪酸甲酯

采用强酸性离子交换树脂(D002-H)催化环氧脂肪酸甲酯合成9(10)-羟基-10(9)-甲氧基脂肪酸甲酯。首先,以油酸甲酯在甲酸催化下制备中间体环氧脂肪酸甲酯,考察了反应时间、反应温度、甲酸和双氧水加入量对产物环氧值的影响。其次,以D002-H为催化剂,以环氧脂肪酸甲酯和甲醇为原料,通过开环醚化制备9(10)-羟基-10(9)-甲氧基脂肪酸甲酯,考察了反应时间、反应温度、醇油质量比和催化剂加入量对转化率的影响,并通过IR以及GC-MS对产物进行了表征。结果表明,反应时间12 h,反应温度65℃,催化剂加入量为环氧脂肪酸甲酯质量的6%,甲醇加入量为100%,在该条件下其转化率高达99%以上。     

催化环氧脂肪酸甲酯制备9(10)-羟基-10(9)-甲氧基脂肪酸甲酯

采用强酸性离子交换树脂(D002-H)催化环氧脂肪酸甲酯合成9(10)-羟基-10(9)-甲氧基脂肪酸甲酯。首先,以油酸甲酯在甲酸催化下制备中间体环氧脂肪酸甲酯,考察了反应时间、反应温度、甲酸和双氧水加入量对产物环氧值的影响。其次,以D002-H为催化剂,以环氧脂肪酸甲酯和甲醇为原料,通过开环醚化制备9(10)-羟基-10(9)-甲氧基脂肪酸甲酯,考察了反应时间、反应温度、醇油质量比和催化剂加入量对转化率的影响,并通过IR以及GC-MS对产物进行了表征。结果表明,反应时间12 h,反应温度65℃,催化剂加入量为环氧脂肪酸甲酯质量的6%,甲醇加入量为100%,在该条件下其转化率高达99%以上。     

甲氧基含量对氯代甲氧基脂肪酸甲酯应用性能的影响

本文以主要成分为十八碳脂肪酸甲酯的生物柴油为主要原料,以甲醇为甲氧基化试剂,在过氧化苯甲酰催化剂存在下,一步氯化法合成了氯代甲氧基脂肪酸甲酯,在反应时间为7～8h,温度为70～85℃的条件下合成的氯代甲氧基脂肪酸甲酯,探讨氯代甲氧基脂肪酸甲酯的甲氧基含量对其在PVC中增塑性能的影响。     

Synthesis and Evaluation of Soy Fatty Acid Ester Estolides as Bioplasticizers in Poly(Vinyl Chloride)

Plasticizers are nonvolatile organic liquids that impart flexibility to polymers. Due to environmental, health, and safety reasons, the industry is looking for bioplasticizers to replace petroleum-derived phthalates. To fulfill this need, soy fatty acid ester estolides were synthesized, characterized, and evaluated as phthalate replacements. Soybean oil was transesterified with methanol or glycerol to form lower molecular weight fatty acid esters that were epoxidized and ring opened with acetic acid and acetylated to give the final products. Ring opening and acetylation of the epoxidized oleic acid esters gave acyclic acetate fatty acid ester estolides, whereas the polyunsaturated fatty acid esters, linoleate, and linolenate gave cyclic tetrahydrofuran derivatives and cross-linked higher molecular weight materials. The cyclization mechanism to form the tetrahydrofuran derivatives was postulated. Soy fatty acid ester estolides were compounded with formulated poly(vinyl chloride), (PVC) and tested for their functional properties. The physical and functional properties of the new bioplasticizers were compared with commercial plasticizers. The elasticity of PVC compounded with experimental plasticizers and commercial phthalates was comparable. PVC compounded with fatty acid methyl ester estolide showed lower glass transition temperature and similar tensile properties compared to PVC compounded with the commercial phthalate. PVC compounded with the glyceryl fatty acid ester estolide showed a higher glass transition temperature, higher tensile properties compared to PVC compounded with the commercial phthalate.     

脂肪酸甲酯乙氧基化物及其磺酸盐的生产与应用探讨

探索和研究新型的表面活性剂一直是人们感兴趣的课题,本文探讨了一种高效的表面活性剂——脂肪酸甲酯乙氧基化物(FMEE)及其磺酸盐衍生物(FMES)的生产工艺与相关应用性能,包括渗透性、耐碱性、低温流动性等性质,也探索了其在造纸、煤炭浮选、硬表面清洗、纺织印染等领域的相关应用。     

Increasing of PVC resin bulk density and free flow by treatment with organic compounds

The ability of different organic additives to increase the bulk density (BD) and the free flow (FF) of PVC was investigated. PVC was treated by quarternary ammonium salts, low-molecular glycols, polyethylene glycols, polyethylene wax, stearic acid, butyl stearate, oxyethylated fatty acids and alcohol, non-oxyethylated and oxyethylated partial fatty acid esters of polyhydric alcohols. Increasing one of the mentioned values is not always accompanied by increasing the other. There exist additives which increase the BD only, the FF only, and both values simulataneously. The BD of treated PVC is often instable; it may increase and decrease on standing. The additives used do not affect the structure of PVC particles, but may change the volume of external voids between them. The efficiency of each additive depends on its polarity and structure of the chains. The mechanism of the action of additives altering the BD and FF was considered. It was expected that the additives leading to denser packing of the PVC powder reduce the interparticle interaction at the expense of particle-additive interaction.     

Biodiesel production from tall oil with synthesized Mn and Ni based additives: Effects of the additives on fuel consumption and emissions

In this study, biodiesel fuel and fuel additives were produced from crude tall oil that is a by-product in the pulp manufacturing by craft or sulphate pulping process. Fatty acids and resinic acids were obtained from crude tall oil by distillation method. Tall oil methyl ester (biodiesel) was produced from fatty acids. Resinic acids were reacted with NiO and MnO₂ stoichiometrically for production of metallic fuel additives. Each metallic fuel additive was added at the rate of 8 μmol/l and 12 μmol/l to make mixtures of 60% tall oil methyl ester/40% diesel fuel (TE60) for preparing test fuels. Metallic fuel additives improved properties of biodiesel fuels, such as pour point and viscosity values. Biodiesel fuels were tested in an unmodified direct injection diesel engine at full load condition. Specific fuel consumption of biodiesel fuels increased by 6.00%, however, in comparison with TE60, it showed trend of decreasing with adding of additives. Exhaust emission profile of biodiesel fuels improved. CO emissions and smoke opacity decreased up to 64.28% and 30.91% respectively. Low NO_x emission was also observed in general for the biodiesel fuels.     

Diels-Alder adducts from safflower oil fatty acids

Methyl esters of alkali-isomerized safflower oil fatty acids after elaidinization with sulfur were treated with styrene in the presence of hydroquinone, with or without solvents. A combination of column chromatography and gas liquid chromatography techniques was employed for the estimation of the methyl esters of unreacted fatty acids, Diels-Alder adduct and polymers in the reaction products. Maximum yield of the Diels-Alder adduct (26.6%) was obtained when the elaidinized methyl esters of the fatty acids were treated with 1.5 moles of styrene per mole of linoleic acid in safflower oil fatty acids at 200–210 C for 6 hr. The methyl ester of the adduct was isolated in about 90% purity from the reaction product by vacuum distillation followed by solvent fractionation. The butyl ester of the adduct and the epoxy derivative of the methyl ester adduct were prepared and characterized.     

An efficient plasticizer based on waste cooking oil: Structure and application

Recently, phthalates have been continuously banned in numerous fields by many countries. Therefore, the development of sustainable and efficient plasticizers has become particularly urgent. The waste cooking oil was used as the main raw materials in this study to synthesize an efficient plasticizer (acetylated-fatty acid methyl ester-trimellitic acid ester, AC-FAME-TAE). The structure of AC-FAME-TAE was characterized by FT-IR and ¹H NMR. The performance of the poly(vinyl chloride) (PVC) plasticized by AC-FAME-TAE was tested and compared with those of the PVC plasticized with di-2-ethylhexyl phthalate (DOP) and EFAME (epoxy fatty acid methyl ester), respectively. DSC results indicated that AC-FAME-TAE had excellent plasticizing efficiency for PVC. The mechanical properties of PVC plasticized by AC-FAME-TAE were as comparable as PVC plasticized by DOP from the results of tensile test. In addition, the PVC plasticized by AC-FAME-TAE had excellent thermal stability and solvent resistance by the results of leaching test and TGA.     

生物柴油制备脂肪酸镧及其应用研究

用生物柴油即脂肪酸甲酯与氧化镧熔融反应制备脂肪酸镧,考察脂肪酸镧与硬脂酸锌、辅助稳定剂的配比和用量对聚氯乙烯热稳定性和机械性能的影响,结果表明：由生物柴油制备脂肪酸镧是可行的,亚磷酸二苯-季戊四醇酯与镧锌皂之间有协同作用,合成的镧锌复合稳定剂具有良好的热稳定性,优于某些其他工业产品。