二聚酸二丁氧基乙酯的合成与增塑性能
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摘要
以二聚酸和乙二醇丁醚为原料,在催化剂钛酸四丁酯催化作用下,采用直接酯化法工艺合成了二聚酸二丁氧基乙酯。考察了原料配比、催化剂用量、带水剂用量、反应时间等因素对酯化反应的影响。结果表明:当乙二醇丁醚和二聚酸摩尔比为2.5∶1,钛酸四丁酯用量为二聚酸质量的1.0%,带水剂环己烷用量为二聚酸质量的17.5%,反应时间5h时,酯化率可达99.6%。建立了酯化反应表观动力学模型,反应速率方程为:r=9.2×105e–49.1/RTcA。通过FTIR和1H NMR对产物结构进行表征,并将二聚酸二丁氧基乙酯和DOP分别加入到PVC树脂中,通过溶剂铸膜法制成PVC塑料试片,对比其性能,二聚酸二丁氧基乙酯有良好的耐油、耐水抽出及热稳定性,可作为DOP的升级产品使用。
A synthesis process of dimer acid di(2-butoxyethyl) ester from dimer acid and ethylene glycol butyl ether was studied.The process was carried out with the catalyst of tetrabutyl titanate and employed the direct esterification method.The effect of the ratio of reactants,dosage of catalyst,dehydrating agent and reaction time was investigated.The result showed that the esterification yield was 99.6%.when the molar ratio of ethylene glycol butyl ether to dimer acid was 2.5∶1,the dosage of catalyst was 1.0% on the basis of the mass of dimer acid,the amount of dehydrating agent was 17.5% on the basis of the mass of dimer acid,and the reaction time was 5h.The apparent kinetics model of esterification was developed,and the equation for reaction rate is:r=9.2×105e–49.1/RTcA.The product was characterized by FTIR and 1H NMR.PVC test pieces was prepared by adding the dimer acid di(2-butoxyethyl) ester and DOP into the PVC resin separately.Dimer acid di(2-butoxyethyl) ester has good oil and water resistance and thermal stability which can be used as DOP upgrade products.
A synthesis process of dimer acid di(2-butoxyethyl) ester from dimer acid and ethylene glycol butyl ether was studied.The process was carried out with the catalyst of tetrabutyl titanate and employed the direct esterification method.The effect of the ratio of reactants,dosage of catalyst,dehydrating agent and reaction time was investigated.The result showed that the esterification yield was 99.6%.when the molar ratio of ethylene glycol butyl ether to dimer acid was 2.5∶1,the dosage of catalyst was 1.0% on the basis of the mass of dimer acid,the amount of dehydrating agent was 17.5% on the basis of the mass of dimer acid,and the reaction time was 5h.The apparent kinetics model of esterification was developed,and the equation for reaction rate is:r=9.2×105e–49.1/RTcA.The product was characterized by FTIR and 1H NMR.PVC test pieces was prepared by adding the dimer acid di(2-butoxyethyl) ester and DOP into the PVC resin separately.Dimer acid di(2-butoxyethyl) ester has good oil and water resistance and thermal stability which can be used as DOP upgrade products.
引文
[1]蒋平平,张书源,冷炎,等.催化合成环保增塑剂的研究及其应用进展[J].化工进展,2012,31(5):953-964.
[2]谈继淮,陈慕华,董琳,等.对苯二甲酸二(环己二醇甲醚)酯合成工艺研究[J].能源化工,2014,35(6):44-47.
[3]MARCILL A,GARIA S,GARCIA-QUESDAD J C.Study of the migration of PVC plasticizers[J].Journal of Analytical and Applied Pyrolysis,2004,71(2):457-463.
[4]LATINI G,FELICE C D,VERROTTI A.Plasticizers,Infant nutrition and reproductivehealth[J].Reproductive Toxicology,2004,19(1):27-33.
[5]LTINI G.The potentialhazards of exposure to di-(2-ethylhexyl)phthalate in babies[J].Biology of Neonate,2000,78(4):269-276.
[6]石万聪,石志博,蒋平平.增塑剂及其应用[M].北京:化学工业出版社,2002:745.
[7]陈慕华,方亮,刘准,等.催化合成脂肪族二元酸烷氧基酯的反应动力学研究[J].化学工艺与工程技术,2012,33(6):1-3.
[8]赵志正.新型增塑剂己二酸二丁氧基乙酯在耐寒橡胶密封件生产中的应用前景[J].世界橡胶工业,2012,39(4):13-16.
[9]王筠翔,陈慕华,刘准,等.HZSM-5分子筛催化合成癸二酸二丁氧基乙酯[J].化工进展,2012,31(12):2720-2723.
[10]张树林,赵地顺,杨建忠.棉油皂脚脂肪酸合成二聚酸的研究[J].河北化工,1992(3):27-28.
[11]杨兴明.自生压合成妥尔油二聚脂肪酸的工艺研究[J].广东化工,1995(1):20-23.
[12]张秀鲁,马永伟,吴玲之,等.利用米糠油脂肪酸试制二聚酸及其应用研究[J].油脂科技,1984(s2):581-591.
[13]孙立明,冯树波.粒状活性白土催化大豆油脂肪酸合成二聚酸的研究[J].中国油脂,2006,31(8):58-60.
[14]赵永和,万福成,徐启杰,等.Nd2O3催化聚合松香酯化反应的动力学研究[J].稀土,2008,29(2):90-94.
[15]李易安,周钰明.甲基磺酸催化高酸值地沟油酯化反应动力学研究[J].工业催化,2009,17(1):30-33.
[16]冯光炷,崔英德,渠海,等.C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐的制备及性能表征[J].精细化工,2006,23(4):341-345.
[17]王彬.两种新型环境友好润滑剂及其润滑性和应用型研究[D].上海:上海大学,2005.
[18]王彬,陶德华,蒋海珍.可生物降解二聚酸酯类的合成及其摩擦磨损性能研究[J].摩擦学学报,2005,25(5):403-407.
[19]孙翔月.二聚酸钠丙烯酸酯无皂乳液[D].长沙:湖南大学,2010.
[20]WASKITOAJI W,TRIWULANDARI E,h ARYONO A.Synthesis of plasticizers derived from plam oil and their application in polyvinyl chloride[J].Procedia Chemistry,2012(4):313-321.
[21]林新花,李幸,陈朝晖.环保醚酯型增塑剂TP-95在PVC中的应用[J].塑料科技,2010,38(5):84-88.
[22]杨万泰.聚合物材料表征与测试[M].北京:中国轻工业出版社,2008:243.
[2]谈继淮,陈慕华,董琳,等.对苯二甲酸二(环己二醇甲醚)酯合成工艺研究[J].能源化工,2014,35(6):44-47.
[3]MARCILL A,GARIA S,GARCIA-QUESDAD J C.Study of the migration of PVC plasticizers[J].Journal of Analytical and Applied Pyrolysis,2004,71(2):457-463.
[4]LATINI G,FELICE C D,VERROTTI A.Plasticizers,Infant nutrition and reproductivehealth[J].Reproductive Toxicology,2004,19(1):27-33.
[5]LTINI G.The potentialhazards of exposure to di-(2-ethylhexyl)phthalate in babies[J].Biology of Neonate,2000,78(4):269-276.
[6]石万聪,石志博,蒋平平.增塑剂及其应用[M].北京:化学工业出版社,2002:745.
[7]陈慕华,方亮,刘准,等.催化合成脂肪族二元酸烷氧基酯的反应动力学研究[J].化学工艺与工程技术,2012,33(6):1-3.
[8]赵志正.新型增塑剂己二酸二丁氧基乙酯在耐寒橡胶密封件生产中的应用前景[J].世界橡胶工业,2012,39(4):13-16.
[9]王筠翔,陈慕华,刘准,等.HZSM-5分子筛催化合成癸二酸二丁氧基乙酯[J].化工进展,2012,31(12):2720-2723.
[10]张树林,赵地顺,杨建忠.棉油皂脚脂肪酸合成二聚酸的研究[J].河北化工,1992(3):27-28.
[11]杨兴明.自生压合成妥尔油二聚脂肪酸的工艺研究[J].广东化工,1995(1):20-23.
[12]张秀鲁,马永伟,吴玲之,等.利用米糠油脂肪酸试制二聚酸及其应用研究[J].油脂科技,1984(s2):581-591.
[13]孙立明,冯树波.粒状活性白土催化大豆油脂肪酸合成二聚酸的研究[J].中国油脂,2006,31(8):58-60.
[14]赵永和,万福成,徐启杰,等.Nd2O3催化聚合松香酯化反应的动力学研究[J].稀土,2008,29(2):90-94.
[15]李易安,周钰明.甲基磺酸催化高酸值地沟油酯化反应动力学研究[J].工业催化,2009,17(1):30-33.
[16]冯光炷,崔英德,渠海,等.C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐的制备及性能表征[J].精细化工,2006,23(4):341-345.
[17]王彬.两种新型环境友好润滑剂及其润滑性和应用型研究[D].上海:上海大学,2005.
[18]王彬,陶德华,蒋海珍.可生物降解二聚酸酯类的合成及其摩擦磨损性能研究[J].摩擦学学报,2005,25(5):403-407.
[19]孙翔月.二聚酸钠丙烯酸酯无皂乳液[D].长沙:湖南大学,2010.
[20]WASKITOAJI W,TRIWULANDARI E,h ARYONO A.Synthesis of plasticizers derived from plam oil and their application in polyvinyl chloride[J].Procedia Chemistry,2012(4):313-321.
[21]林新花,李幸,陈朝晖.环保醚酯型增塑剂TP-95在PVC中的应用[J].塑料科技,2010,38(5):84-88.
[22]杨万泰.聚合物材料表征与测试[M].北京:中国轻工业出版社,2008:243.