【作者】 程喜娥；

【导师】 施文芳；

【作者基本信息】 中国科学技术大学 ， 高分子化学与物理， 2010， 博士

【摘要】 本论文合成了含硅丙烯酸酯、脂环族环氧低聚物及基于倍半硅氧烷的有机-无机杂化聚氨酯丙烯酸酯低聚物,并将其应用于紫外光固化体系中,分别得到自由基固化含硅丙烯酸酯／环氧丙烯酸酯、阳离子固化脂环族环氧低聚物／环氧树脂、有机-无机杂化聚氨酯丙烯酸酯低聚物／含磷丙烯酸酯体系。详细研究了阻燃涂层在紫外光辐照下的光固化动力学及固化膜的热性能、力学性能和阻燃机理；合成了半结晶超支化聚(酯-酰胺),探讨了其作为紫外光固化粉末涂层树脂的可能性。具体的研究内容如下：合成了三(丙烯酰氧基乙氧基)苯基硅烷(TAEPS)和二(丙烯酰氧基乙氧基)甲基苯基硅烷(DAEMPS)树脂,采用FTIR、1H NMR、13C NMR和29Si NMR对其进行了分子结构表征,并与商品化环氧丙烯酸酯EB600混合,在光引发剂存在下,以紫外光辐照快速固化成膜。体系最大光聚合速率随着TAEPS或DAEMPS含量的增加而增大,固化膜中最终双键转化率变化趋势却相反,采用Photo-DSC测试可达80%以上；添加TAEPS和DAEMPS可有效提高材料的阻燃性能,其极限氧指数(LOI)值从EB600固化膜的21提高到30以上；TAEPS和DAEMPS固化膜在氮气中800℃时的成炭量分别是EB600固化膜的3倍和2倍；固化膜的Tg随着TAEPS含量的增加而增大,而对于DAEMPS却相反,前者由于交联密度的增加,而后者由于Si-O和Si-C柔性结构起主导作用：由于交联结构中柔性链的引入,固化膜的拉伸强度随着TAEPS或DAEMPS含量的增加而减小；而相反,含量为85%TAEPS或DAEMPS固化膜的断裂伸长率却是40%含量固化膜的1.3倍以上。采用“醚交换-氧化法”合成了脂环族环氧树脂三(3,4-环氧基-环己基-1-甲氧基)苯基硅烷(TEMPS),利用FTIR、1H NMR、13C NMR和29Si NMR对其进行了分子结构表征,并将其与双酚A环氧树脂(EP828)以不同比例混合后进行阳离子光固化制备了一系列样品。DMTA结果表明,TEMPS和EP828具有良好的相容性,固化膜的Tg和Ts分别从纯EP828固化膜的138℃和93℃降到TEMPS含量为80%固化膜的122℃和79℃；固化膜的断裂伸长率随TEMPS含量的增加而提高,而拉伸强度变化趋势则相反；TEMPS的加入可有效提高材料的阻燃性能,其极限氧指数(LOI)值从EP828固化膜的22提高30以上；固化膜在空气中的最大降解速率对应的温度Tmax2随着TEMPS含量的增加而提高,空气中800℃时的成炭量从纯EP828固化膜0%提高到TEMPS含量为80%固化膜的14%；其阻燃过程为：固化膜燃烧受热时,低表面能的含硅物质由材料内部向表面迁移,并迅速聚集成炭,致密的含硅炭化层能阻碍热量和可燃气体的扩散,从而延缓燃烧和热释放速度,达到阻燃的目的。合成了基于纳米多元醇的有机／无机杂化聚氨酯丙烯酸酯(SHUA),将SHUA与含磷丙烯酸酯(TAEP)以不同的比例混合,制备了一系列紫外光可固化有机／无机杂化阻燃树脂。体系的最大光聚合速率和最终双键转化率随SHUA含量增加而减小；SHUA与TAEP有很好的相容性,固化膜的弹性模量和Tg均随SHUA含量增加先增大后减小,当SHUA含量为10%时,Tg达到最大值(150℃)；所有测试样品极限氧指数(LOI)值均在30以上,炭层的膨胀程度随SHUA含量增加呈先增大后减小趋势,当SHUA含量为20%时,膨胀程度最大；SHUA含量为40%固化膜在850℃时的成炭量是TAEP固化膜的6倍；固化膜的断裂伸长率随SHUA含量增加而提高,而拉伸强度则先增加后减小,当SHUA含量为5%时,体系获得最大拉伸强度(21.6 MPa)。以丁二酸酐为AA’单体,三羟甲基氨基甲烷为CB3单体,在无催化剂无溶剂条件下采用热缩聚法合成了超支化聚(酯-酰胺)(HP),采用1H NMR、GPC等对其分子结构进行了表征,并计算出其羟值为488mg KOH／g；将HP外围羟基进行烷基长链和丙烯酸酯改性后得到一系列半结晶超支化聚(酯-酰胺)(HP-LxDy)。HP处于无定形态,分子外围引入长链后,HP-LxDy具有内核无定形外围结晶的特殊结构,其Tg和Tm分别在40℃和120℃左右,满足低温光固化粉末涂层要求。HP-LxDy光聚合反应速率随光照时间迅速增加,最大光聚合速率随着树脂中双键含量的增加呈增大的趋势,最终双键转化率则呈减小的趋势。更多还原

【Abstract】 The present thesis was aimed on the synthesis of silicon-containing acrylate, silicon-containing cycloaliphatic epoxy resin and silsesquioxane-based organic-inorganic hybrid urethane acrylate, and study on their photopolymerization kinetics, thermal degradation behavior, flame retardance as well as applications in UV curable coatings. A series of semi-crystalline hyperbranched poly (ester-amide)s were also synthesized and their application in UV-curable powder coating was studied. The detailed outline is elaborated as follows:The silicon-containing multifunctional acrylates, tri(acryloyloxyethyloxy) phenyl silane (TAEPS) and di(acryloyloxyethyloxy) methyl phenyl silane (DAEMPS) were synthesized and their molecular structures were confirmed by FTIR,1H NMR, 13C NMR and 29Si NMR spectroscopic analysis. The obtained TAEPS and DAEMPS were blended with a commercial epoxy acrylate (EB600) in different ratios to formulate a series of silicon-containing UV-curable resins. The maximum photopolymerization rate, which was monitored by Photo-DSC, increased along with the increase of TAEPS or DAEMPS content, while the final unsaturation conversion decreased. The limiting oxygen index (LOI) values of UV cured film increased from 21 for EB600 to 30 above for silicon-containing resins, which indicated that the addition of TAEPS or DAEMPS can efficiently enhance the flame retardancy of EB600. The char yields of cured TAEPS and DAEMPS films at 800℃measured under nitrogen atmospheres were two times and one times, respectively, higher than that of EB600. The glass transition temperatures of the UV-cured films increased with the increase of TAEPS content, and decreased with the increase of DAEMPS content. The tensile strength decreased with the increase of TAEPS or DAEMPS content, while the elongation-at-break increased.A novel silicon-containing trifunctional cycloaliphatic epoxide resin tri(3,4-epoxycyclohexylmethyloxy) phenyl silane (TEMPS) was synthesized via "transetherification and oxidation" method and characterized by FTIR,1H NMR, C NMR and 29Si NMR spectroscopic analysis. The obtained resin was then blended with bisphenol A epoxy resin (EP828) in different ratios to formulate a series of silicon-containing UV-curable resins. The data from the dynamic mechanical thermal analysis showed that TEMPS had good miscibility with EP828. The Tg and Ts both decreased from 138℃and 93℃for pure EP828 to 122℃and 79℃for sample with 80% TEMPS loading, respectively. The elongation-at-break increased with the increase of TEMPS content, while the tensile strength showed an opposite trend. The limiting oxygen index (LOI) values of cured film increased from 22 for EP828 to 30 for silicon-containing resins, which indicated that the addition of TEMPS can efficiently enhance the flame retardancy of EP828. The temperature at the maximum rate of weight loss Tmax2 increased with increasing TEMPS content. The char yields at 800℃measured under air atmospheres increased from 0% for pure EP828 to 14% for cured films with 80% TEMPS loading. Their flame retardant performance arise partly from the dilution function to more combustible organic gases, and partly from the barrier effect by the silicaceous residues formed in an advancing flame. While heating, the low surface energy of silicon migrates to the surface of coated film, following by the formation of a protective layer with high heat resistance. The high-performance char acts as an insulator and mass transport barrier, which can cut off the heat and oxygen transfer, and thus effectively improve the flame retradance of UV-cured resin.The silsesquioxane-based hybrid urethane acrylate (SHUA) was synthesized by modifying silsesquioxanebased hybrid polyol (SBOH) with the half adduct of isophorone diisocyanate and 2-hydroxyethyl acrylate, and characterized by FTIR and ’H NMR spectroscopy. The SHU A was mixed with a phosphorus-containing trifunctional acrylate (TAEP) with different ratios to prepare a series of UV-curable organic-inorganic hybrid resins. Both the maximum photopolymerization rate and final unsaturation conversion in the UV-cured films determined by photo-DSC decreased along with the increase of SHUA content. The data from the dynamic mechanical thermal analysis showed that SHUA had good miscibility with TAEP. Both the storage modulus in rubbery state and Tg first increased and then decreased along with the addition of SHUA content. The sample with 10% SHUA loading had the highest Tg of 150℃. The limiting oxygen index (LOI) values of all test samples were above 30. The char layer of sample with 20% SHUA loading had the maximum degree of expansion. The char yield of sample with 40% SHUA loading at 850℃was five times higher than that of TAEP. The elongation-at-break increased with the increase of SHUA content, while the tensile strength first increased and then decreased. The sample with 5% SHUA loading had the highest tensile strength of 21.6 MPa.Through thermal polycondensation from succinic anhydride as an AA’monomer and tris-(hydroxymethyl)aminomethane as a CB3 monomer in the absence of catalyst and solvent, hyperbranched poly (ester-amide) (HP) was synthesized and its structure was characterized by1H NMR and GPC. The calculated hydroxyl number of HP was 488 mg KOH/g. A series of semi-crystalline hyperbranched poly(ester-amide)s (HP-LχDy) was obtained by modifying hydroxyl end groups of HP with IPDI-C18 and IPDI-HEA in different ratios. HP is amorphous, while HP-LχDy is semi-crystalline due to the introduction of long alkyl chains. The degree of crystallinity increased with increasing the substitution degree of long alkyl chains emitting from the spherelike interior. The Tg and Tm of HP-LχDy were about 40℃and 120℃. The maximum photopolymerization rate, which was monitored by Photo-DSC, increased along with the increase IPDI-HEA content, while the final unsaturation conversion decreased.更多还原