臭氧氧化改性热稠化大豆油基聚氨酯合成及其性能研究
|
摘要
以大豆油为初始原料,通过配合运用热稠化和臭氧氧化/还原技术,成功制备出了生物基多元醇。系统研究了热稠化时间对多元醇性质的影响。大豆油所含亚麻酸和亚油酸具有双烯丙基结构,它们所含有的大量碳碳双键在高温下发生迁移生成共轭结构,继而发生分子内或分子间的Diels-Alder反应。随热稠化时间延长,碳碳双键的含量逐渐变少,臭氧氧化/还原后所得多元醇的羟值由220. 4 mg KOH/g降低为94. 3 mg KOH/g,从而影响所得聚氨酯薄膜的力学性能和热性能。聚氨酯薄膜样品由生物基多元醇与4,4'-二苯基甲烷二异氰酸酯(MDI)发生聚合反应制备得到。分别应用差示扫描量热仪(DSC)、热失重(TGA)、拉伸测试考察了聚氨酯薄膜的性能,并与大豆油直接臭氧氧化所得聚氨酯薄膜的性能进行了比较。研究发现,经过臭氧氧化,聚氨酯薄膜的韧性和断裂伸长率大幅度提高了。但是当热稠化时间达到3 h,所得多元醇的羟值大幅度降低,使得聚氨酯薄膜的力学性能劣化。为通过大豆油制备含有高反应活性伯羟基的生物基多元醇提供了一种简便、实用的方法,并有望应用于其他具有高含量亚麻酸或亚油酸的植物油。
Bio-based polyols could be successfully prepared from soybean oil through heat-bodying followed by ozonolysis. The effects of the heat-bodying time on the properties of the polyols had been systematically studied. The linolenic and linoleic fatty acids in soybean oil had diallyl structure,which could be transformed from carbon-carbon double bonds to conjugated structure at elevated temperature,facilitating intra or inter molecular Diels Alder Cyclization. As the increase of thickening time,the contents of carboncarbon double bonds could decrease and the hydroxyl value number of the polyols could decrease from 220. 4 mg KOH/g to 94. 3 mg KOH/g, which could affect the mechanical properties and thermal properties of polyurethane films. Polyurethane films were prepared by the polyreaction of 4, 4'-diphenylmethane diisocyanate( MDI) and bio-polyols, which could be investigated by differential scanning calorimetry( DSC),thermogravimetric analysis( TGA) and tensile test,and then compared with the polyurethane from ozonated unpolymerized soybean oil. The results reveal that mechanical properties,such as,elongation at break and toughness could be improved by ozone oxidition. However,when the heat-bodying time could achieve 3 hours,the hydroxyl value of polyols could decline dramatically and decrease the mechanical properties of polyurethane.This paper provides a simple and practical method to synthesize the polyols with high reactivity primary hydroxyl groups,which could apply to the usage of other vegetable oil contain linoleic or linolenic fatty acid.
Bio-based polyols could be successfully prepared from soybean oil through heat-bodying followed by ozonolysis. The effects of the heat-bodying time on the properties of the polyols had been systematically studied. The linolenic and linoleic fatty acids in soybean oil had diallyl structure,which could be transformed from carbon-carbon double bonds to conjugated structure at elevated temperature,facilitating intra or inter molecular Diels Alder Cyclization. As the increase of thickening time,the contents of carboncarbon double bonds could decrease and the hydroxyl value number of the polyols could decrease from 220. 4 mg KOH/g to 94. 3 mg KOH/g, which could affect the mechanical properties and thermal properties of polyurethane films. Polyurethane films were prepared by the polyreaction of 4, 4'-diphenylmethane diisocyanate( MDI) and bio-polyols, which could be investigated by differential scanning calorimetry( DSC),thermogravimetric analysis( TGA) and tensile test,and then compared with the polyurethane from ozonated unpolymerized soybean oil. The results reveal that mechanical properties,such as,elongation at break and toughness could be improved by ozone oxidition. However,when the heat-bodying time could achieve 3 hours,the hydroxyl value of polyols could decline dramatically and decrease the mechanical properties of polyurethane.This paper provides a simple and practical method to synthesize the polyols with high reactivity primary hydroxyl groups,which could apply to the usage of other vegetable oil contain linoleic or linolenic fatty acid.
引文
[1]IONESCU M.Chemistry and technology of polyols for polyurethanes[M].Rapra Technol,2005:58.
[2]王莉莉,董侠,刘祥贵,等.热塑性聚氨酯及其复合材料的界面形态与流变特性[J].高分子学报,2013(3):367-376.
[3]张立强,张猛,周永红,等.聚氨酯用多元醇的制备方法研究进展[J].塑料工业,2014,42(1):5-8.
[4]李广龙,罗仡科,张凤桥,等.多元醇对NDI型聚氨酯微孔弹性体性能的影响[J].塑料工业,2014,42(11):68-71.
[5]吴素平,容敏智,章明秋,等.大豆油树脂基泡沫塑料的力学性能与生物降解性研究[J].高分子学报,2007(10):993-998.
[6]周威,贾普友,周永红,等.植物油基聚氨酯泡沫的研究进展[J].热固性树脂,2018,33(4):54-60.
[7]KANDANARACHCHI P,GUO A,PETROVIC Z.The hydroformylation of vegetable oils and model compounds by ligand modified rhodium catalysis[J].J Molecular Catal Chem,2002,184(1):65-71.
[8]代春兰.大豆油共轭化及其自由基共聚合合成热固性树脂的研究[D].上海:华南师范大学,2010.
[9]POWERS P O.Heat bodying of drying oils[J].J Am Oil Chem Soc,1950,27(11):468-472.
[10]PETROVIC'Z S,WEI ZHANG A,JAVNI I.Structure and properties of polyurethanes prepared from triglyceride polyols by ozonolysis[J].Biomacromolecules,2005,6(2):713-719.
[11]MIAO S,WANG P,SU Z,et al.Vegetable-oil-based polymers as future polymeric biomaterials[J].Acta Biomaterialia,2014,10(4):1692-1704.
[12]PETROVI C'Z S.Polyurethanes from Vegetable Oils[J].Polym Rev,2008,48(1):109-155.
[13]ERHAN S Z,BAGBY M O.Polymerization of vegetable oils and their uses in printing inks[J].J Am Oil Chem Soc,1994,71(11):1223-1226.
[14]KIATSIMKUL P P,SUPPES G J,SUTTERLIN W R.Production of new soy-based polyols by enzyme hydrolysis of bodied soybean oil[J].Ind Crops Prod,2007,25(2):202-209.
[15]YOON S C,RATNER B D.Surface and bulk structure of segmented poly(ether urethanes)with perfluoro chain extenders.2.FTIR,DSC,and x-ray photoelectron spectroscopic studies[J].Macromol,1988,21(8):2392-2400.
[16]BENGTSON B,FEGER C,MACKNIGHT W J,et al.Thermal and mechanical properties of solution polymerized segmented polyurethanes with butadiene soft segments[J].Polymer,1985,26(6):895-900.
[17]GUO A,DEMYDOV D,WEI Z,et al.Polyols and polyurethanes from hydroformylation of soybean oil[J].J Polym Environ,2002,10(1-2):49-52.
[18]WANG C S,YANG L T,NI B L,et al.Polyurethane networks from different soy-based polyols by the ring opening of epoxidized soybean oil with methanol,glycol,and 1,2-propanediol[J].J Appl Polym Sci,2010,114(1):125-131.
[19]PECHAR T W,WILKES G L,ZHOU B,et al.Characterization of soy-based polyurethane networks prepared with different diisocyanates and their blends with petroleum-based polyols[J].J Appl Polym Sci,2010,106(4):2350-2362.
[20]LU Y,LAROCK R C.Soybean-oil-based waterborne polyurethane dispersions:Effects of polyol functionality and hard segment content on properties[J].Biomacromolecules,2008,9(11):3332-3340.
[2]王莉莉,董侠,刘祥贵,等.热塑性聚氨酯及其复合材料的界面形态与流变特性[J].高分子学报,2013(3):367-376.
[3]张立强,张猛,周永红,等.聚氨酯用多元醇的制备方法研究进展[J].塑料工业,2014,42(1):5-8.
[4]李广龙,罗仡科,张凤桥,等.多元醇对NDI型聚氨酯微孔弹性体性能的影响[J].塑料工业,2014,42(11):68-71.
[5]吴素平,容敏智,章明秋,等.大豆油树脂基泡沫塑料的力学性能与生物降解性研究[J].高分子学报,2007(10):993-998.
[6]周威,贾普友,周永红,等.植物油基聚氨酯泡沫的研究进展[J].热固性树脂,2018,33(4):54-60.
[7]KANDANARACHCHI P,GUO A,PETROVIC Z.The hydroformylation of vegetable oils and model compounds by ligand modified rhodium catalysis[J].J Molecular Catal Chem,2002,184(1):65-71.
[8]代春兰.大豆油共轭化及其自由基共聚合合成热固性树脂的研究[D].上海:华南师范大学,2010.
[9]POWERS P O.Heat bodying of drying oils[J].J Am Oil Chem Soc,1950,27(11):468-472.
[10]PETROVIC'Z S,WEI ZHANG A,JAVNI I.Structure and properties of polyurethanes prepared from triglyceride polyols by ozonolysis[J].Biomacromolecules,2005,6(2):713-719.
[11]MIAO S,WANG P,SU Z,et al.Vegetable-oil-based polymers as future polymeric biomaterials[J].Acta Biomaterialia,2014,10(4):1692-1704.
[12]PETROVI C'Z S.Polyurethanes from Vegetable Oils[J].Polym Rev,2008,48(1):109-155.
[13]ERHAN S Z,BAGBY M O.Polymerization of vegetable oils and their uses in printing inks[J].J Am Oil Chem Soc,1994,71(11):1223-1226.
[14]KIATSIMKUL P P,SUPPES G J,SUTTERLIN W R.Production of new soy-based polyols by enzyme hydrolysis of bodied soybean oil[J].Ind Crops Prod,2007,25(2):202-209.
[15]YOON S C,RATNER B D.Surface and bulk structure of segmented poly(ether urethanes)with perfluoro chain extenders.2.FTIR,DSC,and x-ray photoelectron spectroscopic studies[J].Macromol,1988,21(8):2392-2400.
[16]BENGTSON B,FEGER C,MACKNIGHT W J,et al.Thermal and mechanical properties of solution polymerized segmented polyurethanes with butadiene soft segments[J].Polymer,1985,26(6):895-900.
[17]GUO A,DEMYDOV D,WEI Z,et al.Polyols and polyurethanes from hydroformylation of soybean oil[J].J Polym Environ,2002,10(1-2):49-52.
[18]WANG C S,YANG L T,NI B L,et al.Polyurethane networks from different soy-based polyols by the ring opening of epoxidized soybean oil with methanol,glycol,and 1,2-propanediol[J].J Appl Polym Sci,2010,114(1):125-131.
[19]PECHAR T W,WILKES G L,ZHOU B,et al.Characterization of soy-based polyurethane networks prepared with different diisocyanates and their blends with petroleum-based polyols[J].J Appl Polym Sci,2010,106(4):2350-2362.
[20]LU Y,LAROCK R C.Soybean-oil-based waterborne polyurethane dispersions:Effects of polyol functionality and hard segment content on properties[J].Biomacromolecules,2008,9(11):3332-3340.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |