新型聚天冬氨酸酯聚脲的合成、结构与性能研究  

Study on Synthesis, Morphology and Properties of Novel Polyureas Based on Polyaspartic Esters

作　　者：吕平[1] 陈国华[2] 黄微波[2] 

机构地区：[1]青岛理工大学,山东青岛266033 [2]中国海洋大学,山东青岛266100

出　　处：《高校化学工程学报》2008年第1期106-112,共7页Journal of Chemical Engineering of Chinese Universities

基　　金：国家自然科学基金(50373009);建设部科技攻关项目(A04-2-033)

摘　　要：通过二步法:(1)4,4’-二氨基环己基甲烷(PACM)或3,3’-二甲基-4,4’-二氨基环己基甲烷(Laromin C260)与马来酸二乙酯的Michael加成反应,(2)反应(1)产物与E-51环氧树脂的加成反应,合成了新型聚天冬氨酸酯(PAEs)。与现有Michael加成法相比,二步法能明显缩短合成反应时间,更适合工业化生产。进一步通过PAEs与4,4’-二环已基甲烷二异氰酸酯(H12MDI)/聚四亚甲基二醇(PTMG)预聚物反应,常温合成了2种PAEs聚脲。采用FT-IR、1H-NMR和GPC等表征了PAEs,并采用FT-IR和DMA考察了PAEs聚脲的结构形态、反应活性和力学性质。研究结果表明,聚脲硬段氨基氢键化程度高,氢键键长为3.04-;脲羰基的氢键化程度分别为74.4%和73.2%,提高固化温度,有助于脲羰基氢键的形成。PAEs聚脲呈现微相分离的形态,是低活性、高强度的弹性体涂层材料。Two new polyaspartic esters （PAEs）, PAE-lb and PAE-2b, were prepared reaction： （1） Michael addition reaction between 4,4＇-methylenebis（cyclohexyl by two steps of addition amine） （PACM） or 4,4＇-methylenebis（2-methyl cyclohexyl amine） （Laromin C260） and dialkyl maleates; （2） The addition reaction of the two different products of step （1） with E-51 epoxy resin and forms PAE-lb and PAE-2b separately. The two-steps method proposed could reduce the reaction time in comparison with the current Michael addition reaction method, thus satisfying the industrialized production. New PAEs based polyureas were synthesized by reacting the different PAEs separately with aliphatic polyisocyanates 4,4＇-diisocyanato dicyclohexylmethane （HI2MDI） / polytetramethylene ether glycol （PTMG） prepolymer at room temperature. FT-IR, ^1H-NMR and GPC were employed to characterize the new PAEs prepared, and the morphology, reaction activity and mechanical properties of the prepared PAEs based polyureas were investigated by means of FT-IR and DMA. The results indicate that the hydrogen bonding degree of amidogen groups in hard segments of the polyureas prepared is high, the length of hydrogen bonding is 3.04A, the hydrogen bonding urea carbonyl increases with the increase of the curing temperature and at the curing temperature of 15 ℃, the hydrogen bonding degrees of urea carbonyl groups in PAE-lb based polyurea and PAE-2b based polyurea are 74.4% and 73.2%, respectively The new PAEs based polyureas prepared present microphase separated morphology, and they are kinds of elastomer coating materials with low activity and high strength.

关 键 词：聚脲 聚天冬氨酸酯 结构形态 Michael加成法 

分 类 号：TQ323.8[化学工程—合成树脂塑料工业]