蓖麻油基羧酸型聚氨酯亲水扩链剂的制备与应用
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摘要
通过蓖麻油与3-巯基丙酸间的巯基-烯点击反应合成了一种蓖麻油基多元羧酸(MCO),并将其作为亲水扩链剂与异佛尔酮二异氰酸酯(IPDI)和蓖麻油共聚制备了一系列羧基含量不同的蓖麻油基水性聚氨酯树脂(COPU)。用核磁氢谱(1H NMR)和核磁碳谱(13C NMR)确认了蓖麻油基亲水扩链剂的结构;采用红外光谱(FT-IR)对MCO及COPU的结构进行分析;并采用摆杆硬度测试、吸水率测试、示差扫描量热仪(DSC)和热重分析仪(TGA)对聚氨酯涂膜的机械性能和物理性能进行表征。结果表明:随着亲水基团含量的增加,涂膜的硬度逐渐降低、吸水率逐渐增大,对玻璃化转变温度(T g)及耐热性能影响不明显。水性聚氨酯涂膜浸泡192 h后不泛白,不开裂,吸水率仅为6.52%,有较好的耐水性。
A novel castor oil-based polybasic acid( MCO) was synthesized through thiol-ene coupling reaction between castor oil and 3-mercapto propionic acid,which was then used as a hydrophilic monomer reacting with isophorone diisocyanate( IPDI) and castor oil to prepare a series of bio-based waterborne polyurethane resin( COPU). The structure of castor oil-based chain extender was verified by1H NMR and13CNMR. FT-IR was used to characterize the structure of MCO and COPU. Furthermore,pendulum hardness test,water absorption test,differential scanning calorimetry( DSC) and thermal gravimetric analysis( TGA) were used to characterize the mechanical properties and thermal properties of COPU-based films. The result showed that with increase of the content of hydrophilic group,the hardness of COPU films was gradually decreased,but the water absorption was increased graduall and no obvious effect on the value of T g and thermal resistance. There was no blushing and crackingdefects on the COPU film after immersion in water for 192 h,and the water absorption was only 6. 52%,indicating good resistance to water.
A novel castor oil-based polybasic acid( MCO) was synthesized through thiol-ene coupling reaction between castor oil and 3-mercapto propionic acid,which was then used as a hydrophilic monomer reacting with isophorone diisocyanate( IPDI) and castor oil to prepare a series of bio-based waterborne polyurethane resin( COPU). The structure of castor oil-based chain extender was verified by1H NMR and13CNMR. FT-IR was used to characterize the structure of MCO and COPU. Furthermore,pendulum hardness test,water absorption test,differential scanning calorimetry( DSC) and thermal gravimetric analysis( TGA) were used to characterize the mechanical properties and thermal properties of COPU-based films. The result showed that with increase of the content of hydrophilic group,the hardness of COPU films was gradually decreased,but the water absorption was increased graduall and no obvious effect on the value of T g and thermal resistance. There was no blushing and crackingdefects on the COPU film after immersion in water for 192 h,and the water absorption was only 6. 52%,indicating good resistance to water.
引文
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[2]ESPINOSA L M D,MEIER M A R.Plant oils:the perfect renewable resource for polymer science[J].European Polymer Journal,2011,47(5):837-852.
[3]MEIER M A R,METZGER J O,SCHUBERT U S.Plant oil renewable resources as green alternatives in polymer science[J].Chemical Society Review,2007,36(11):1788-1802.
[4]GANOINI A.Polymers from renewable resources:a challenge for the future of macromolecular materials[J].Macromolecules,2008,41(24):9491-9504.
[5]MUTLU H,MEIER M A R.Castor oil as a renewable resource for the chemical industry[J].European Journal of Lipid Science and Technology,2010,112(1):10-30.
[6]CHANG C W,LU K T.Natural castor oil based 2-package waterborne polyurethane wood coatings[J].Progress in Organic Coatings,2012,75(4):435-443.
[7]KREYE O,TOTH T,MEIER M A R.Poly-α,β-unsaturated aldehydes derived from castor oil via ADMET polymerization[J].European Journal of Lipid Science and Technology,2011,113(1):31-38.
[8]付长清,程传杰,申亮,等.巯基点击反应研究进展[J].高分子通报,2012(1):29-36.FU C Q,CHEN C J,SHEN L,et al.Progress of thioibased click reaction[J].Polymer Bulletin,2012(1):29-36.
[9]HOJABRI L,KONG X H,NARINE S S.Fatty acid-derived diisocyanate and bio-based polyurethane produced from vegetable oil:synthesis,polymerization,and characterization[J].Biomacromolecules,2009,10(4):884-891.
[10]HOJABRI L,KONG X H,NARINE S S.Functional thermoplastics from linear diols and diisocyanates produced entirely from renewable lipid sources[J].Biomacromolecules,2010,11(4):911-918.
[11]STEMMELEN M,PESSEL F,LAPINTE V,et al.A fully biobased epoxy resin from vegetable oils:from the synthesis of the precursors by thiol-ene reaction to the study of the final material[J].Journal of Polymer Science Part A:Polymer Chemistry,2011,49(11):2434-2444.
[12]DESROCHES M,CAILLOL S,LAPINTE V,et al.Synthesis of biobased polyols by thiol-ene coupling from vegetable oils[J].Macromolecules,2011,44(8):2489-2500.
[13]许戈文.水性聚氨酯材料[M].1版.北京:化学工业出版社,2010.
[14]LEVCHIK S V,WEIL E D.Thermal decomposition,combustion and fire-retardancy of polyurethanes-a review of the recent literature[J].Polymer International,2004,53(11):1585-1610.