含笼型倍半硅氧烷的无机/有机纳米杂化物对环氧树脂的改性
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摘要
采用γ-胺丙基三乙氧基硅烷(KH-550)为原料合成胺基倍半硅氧烷(POSS-NH_2),并在此基础上与缩水甘油醚合成杂化物。POSS-NH_2/正丁基缩水甘油醚按化学摩尔比1:8、1:12、1:14、1:16进行反应合成DRT1类杂化物:DRT_(11)、DRT_(12)、DRT_(13)、DRT_(14);POSS-NH_2/正丁基缩水甘油醚/1,4-丁二醇二缩水甘油醚按化学摩尔比1:9:3、1:10:2、1:11:1合成DRT2类杂化物DRT_(21)、DRT_(22)、DRT_(23)。利用红外、核磁、质谱对POSS-NH_2及其杂化物进行了表征。
用所合成的杂化物添加到E-51环氧树脂中形成DRT/EP复合材料,杂化物的添加量分别为5wt%、10wt%、15wt%、20wt%。对改性后复合材料进行力学性能和热学性能测试,研究了POSS-NH_2顶点接枝链数量、接枝官能团及杂化物添加量对改性效果的影响。发现DRT_(12)具有较好的改性性能,在DRT_(12)含量为15wt%时,DRT_(12)/EP复合材料的冲击强度和断裂伸长率分别达到了7KJ/m2和6.6%。POSS-NH_2顶点上所接枝的官能团对复合材料性能也有显著影响,带有环氧基团的DRT2类杂化物比DRT1类杂化物具有更好的改性效果,在DRT_(22)含量为20wt%时,DRT_(22)/EP复合材料的冲击强度为8.1KJ/m2,其热学性能也有显著的提高。本文并通过SEM,XRD等对杂化物改性复合材料的作用机理进行了研究。
The compound of cageocta(aminopropyl silsesquioxane)(POSS-NH_2) was prepared in higher yield by the hydrolysis and polycondensation of trifunctional monomer H_2NCH_2CH_2CH_2Si(OC_2H_5)_3, then some inorganic/organic hybrid nano material was prepared through the reaction of cage octa(aminopropyl silsesquioxane)(POSS-NH_2) with n-Butyl glycidyl ether(XY-501)and 1,4-Butanedioldiglycidylether.
A series of polyhedral oligomeric silsesquioxane/epoxy nanocomposites (DRT/EP) containing 0 wt%, 5 wt%, 10 wt% and 15 wt% content of inorganic/organic hybrid nano material were prepared. Mechanical properties and thermal properties were used as the index to show the effect the amounts of chain and different functional group on inorganic/organic hybrid nano material.The result showed the DRT_(12)/EP has the good properties,its impact strength and elongation fracture measure up 7KJ/m~2 and 6.6% when DRT_(12) content is 15wt%,however DRT_(22)/EP showed the better properties, its impact strength reachs 8.1 KJ/m2 when DRT_(22) content is 20wt%.And the mechanism of the incorporation of oligomeric silsesquioxane/epoxy nano composites into epoxy networks enhancing the mechanical properties and thermal properties of epoxy was invested by scanning electron microscopy(SEM) and X-ray diffraction(XRD).
用所合成的杂化物添加到E-51环氧树脂中形成DRT/EP复合材料,杂化物的添加量分别为5wt%、10wt%、15wt%、20wt%。对改性后复合材料进行力学性能和热学性能测试,研究了POSS-NH_2顶点接枝链数量、接枝官能团及杂化物添加量对改性效果的影响。发现DRT_(12)具有较好的改性性能,在DRT_(12)含量为15wt%时,DRT_(12)/EP复合材料的冲击强度和断裂伸长率分别达到了7KJ/m2和6.6%。POSS-NH_2顶点上所接枝的官能团对复合材料性能也有显著影响,带有环氧基团的DRT2类杂化物比DRT1类杂化物具有更好的改性效果,在DRT_(22)含量为20wt%时,DRT_(22)/EP复合材料的冲击强度为8.1KJ/m2,其热学性能也有显著的提高。本文并通过SEM,XRD等对杂化物改性复合材料的作用机理进行了研究。
The compound of cageocta(aminopropyl silsesquioxane)(POSS-NH_2) was prepared in higher yield by the hydrolysis and polycondensation of trifunctional monomer H_2NCH_2CH_2CH_2Si(OC_2H_5)_3, then some inorganic/organic hybrid nano material was prepared through the reaction of cage octa(aminopropyl silsesquioxane)(POSS-NH_2) with n-Butyl glycidyl ether(XY-501)and 1,4-Butanedioldiglycidylether.
A series of polyhedral oligomeric silsesquioxane/epoxy nanocomposites (DRT/EP) containing 0 wt%, 5 wt%, 10 wt% and 15 wt% content of inorganic/organic hybrid nano material were prepared. Mechanical properties and thermal properties were used as the index to show the effect the amounts of chain and different functional group on inorganic/organic hybrid nano material.The result showed the DRT_(12)/EP has the good properties,its impact strength and elongation fracture measure up 7KJ/m~2 and 6.6% when DRT_(12) content is 15wt%,however DRT_(22)/EP showed the better properties, its impact strength reachs 8.1 KJ/m2 when DRT_(22) content is 20wt%.And the mechanism of the incorporation of oligomeric silsesquioxane/epoxy nano composites into epoxy networks enhancing the mechanical properties and thermal properties of epoxy was invested by scanning electron microscopy(SEM) and X-ray diffraction(XRD).
引文
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[13]黄振宏,陈子达.医药用新型有机硅材料.中国医药工业杂志, 2003 , 34 (3) : 152～156.
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[16] RopartzLoic,Morris russell E,Schwarz Gary P. Dendrimer-bound tertiary phosphines for alkene hydroformylation[J]. inorganic chamistry communications, 2000.3:714～717
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[18] zhu wen wei, xiao steven, Ishiang Shih. Field-effect mobilities of polyhedral oligomeric silscsquioxanes anchored semiconducting polymers[J].Applied Surface Science, 2004, 221:358～363
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[24]李绍雄,刘益军.聚胺酯胶黏剂[M ].北京:化学工业出版社,1998.
[25]袁金颖,潘才元.一种新型螺环原碳酸酯共聚改性环氧树脂的研究[J].中国胶粘剂,1997,6 (5):1～3.
[26] Kevin GaW, M itsutoshi Jikei, Masaaki Kakinoto Jlkei, et al. Adhesion behavior of pol- ymeric acid cured epoxy [J]. Polymer, 1997, (38) : 4413～4415.
[27]耿同谋.聚胺酯改性环氧及其应用[J].化工新型材料,1998, (5) :28～30.
[28]金林生.综述环氧树脂的增韧途径[J ].高分子材料, 1996, (1) :30～31
[29]梁伟荣,王惠民,郑志才.聚醚砜增韧环氧树脂的结构与性能[J].热固性树脂,1997, (4):12～14.
[30] Harani, Fellahi, Bakar. Toughening of epoxy resing syn thesized polyurethane prepo- lymer based on hydroxyl teminateed polyesters[J]. Appl Polym Sci, 1998, 70 (13) :2603～2618
[31]饶秋华.改性聚醚增韧环氧树脂的研究[J ].高分子材料科学与工程, 1997, 13 (1) :96～98.
[32]王惠民,梁伟荣.聚醚砜环氧树脂复合体系的研究[J].高分子材料科学与工程, 1999,15 (6) :155～157.
[33]徐修成.环氧/聚醚砜体系及其增韧机理的研究[J].宇航材料工艺,1996, 2(1) :32～34.
[34]韦春.反应型液晶聚合物改性环氧树脂性能的研究[J].高分子材料科学与工程, 2003, 19 (1) :168～171.
[35] Lange F F. Model for the toughness of epoxy - rubber particulate composite[J]. PhilMag, 1970, (22) :983.
[36] Nnn Heml. Phase separation in rubber- modified thermoset resin: opticalmicroscopy and laser scattering[J]. J. of Appl. Polym Sci, 1986, (31) :15～25.
[37] Pinnavala T J, Tie Lan, Zhen Wang. Clay - reinforced epoxy nanocomposites: synthesis, properties and mechanism of forfation[J]. J Am Chem Soc,1996,( 17) :251～261.
[38] Usukia, Aizutanit F, Fujimoto I, et al. Composite Material Containing a Layered silicat- e :US,4889885[P]. 1989: 12～26.
[39]于浩,路太平.环氧树脂/聚胺酯互穿网络的研究[J]。热固性树脂,1996,11( 1) :13～16.
[40]管云林.聚胺酯/环氧树脂互穿网络聚合物相行为与粘接剪切性能的研究[J].高分子材料科学与工程,1996,12 (5) : 121～126.
[41]王超,张斌,李奇力.耐高温环氧树脂胶黏剂的研制[J].中国胶粘剂,1999, 3 :12～13.
[42]管云林.聚胺酯/呋喃树脂互穿聚合物网络性能的研究[J].化学工业与工程, 1997, 14 (1) :25～29.
[43] Yingli, Sufen Mao. Studyon the properties and application of epoxy resin/polyurethane Semi - interpenetrating Polymer net works[J]. J of Applpolym Sci, 1996, (61) :2059～2063.
[44]钱军民,李旭祥.环氧树脂改性研究进展[J ].绝缘材料, 2001, (5) :27～31
[45]蒋红梅.环氧-聚胺酯互穿聚合物网络导电涂料[J].涂料工业,1999, (3) :12～15.
[46]黄云辉,张志力.环氧聚胺酯涂料的研究[J ].南昌航空工业学院学报,1997, (4) :63～67.
[47]郑瑞琪,余云照。合成胶黏剂丛书[M ]。北京:化学工业出版社, 1985,6(2):19～23。
[48] Hoebbel, D.,Klaus, E., Thomas, R.,Irene, P. Inorganic-organic polymers derived from functional silicic acid derivatives by additive reaction[J]. J. Non-Cryst. Solids 1994, 176～179.
[49]汪佳凤,徐宏耀,鲍亮.POSS基高分子材料的合成与热性能[J]。高分子材料科学与工程,2005,21(5):10～13.
[50]刘磊,宋磊,张胜,胡源.POSS/PS复合材料的结构与燃烧性能[J].中国科学技术大学学报,2006,36(1):29～33.
[51]朱立新,黄凤来,祝亚菲,严慧明,顾均杨.高交联度不饱和聚酯增韧改性的固化特征及动力学分析[J].复合材料学报,2003,3(20):22～26.
[2] Lig, Wangl , Nih,etal.Polyhedral oligomeric silsesquioxane(POSS)polymers and copo- lymers:areview[J]. Inorg organometal Polym,2001,11(3): 123～154.
[3] Finaa,Abbenhuishcl,Tabuanid,etal.Metal functionalized POSS as fire retardants inpolyp- ropylene [J].Polymer Degradation and Stability, 2006 , 91: 2275～2281.
[4] Feherfj,Newmanda.Enhanced silylation reactivity of a model for silica surfaces[ J] . Am ChemSoc,1990,112(5): 1931～1936.
[5]汪佳凤,徐洪耀,鲍亮. POSS基高分子材料的合成及热性能[ J].高分子材料科学与工程,2005,21(5):10～13.
[6] Gilmanjw,Schlitzerds,Lichtenhanjd Low earth orbit resistant siloxane copolymers[J]. J Applied PolymSci,1996,66:591.
[7] Tsuchibaa,Bolnc,Sernetzfg,etal.Ethene and propene copolymers containing silsesquioxane side groups[ J].Macromolecules,1997,30 (10) : 2818～2822.
[8] Waddonaj,Zhengl,Farrisrj,etal. Nanostructured polyethylene POSS copolymers: Contro- lofcrystallizationandaggregation[J].Nano Letters,2002,2( 10 ): 1149～1155.
[9]Huangjc,Hecb,Xlaoy,etal.Polyimide/POSSnanocomposites:interfacialinteraction,thermal properties and mechanical properties[J] . Polymer,2003,44:4491～4499.
[10] Constablegs,Lesseraj,Coughlineb.Morphological and mechanical evaluation of hybrid organic-inorganic thermoset copolymers of dicyclopentadiene and mono-ortris (norborne- nyl )-substituted polyhedral oligomeric silsesquioxanes[J]. Macromolecules,2004,37 (4 ): 1276～1282.
[11] Leea , Lichtenhan J D. Viscoelastic responses of polyhedral oligosilsesquioxane reinforc- ed epoxy systems[J].Macromolecules,1998,31(15) : 4970～4974.
[12] Cardoeng,Coughlineb.Hemrtelechelic polystyrene-POSS copolymers as model systems for the study of well-define dinorganic/organic hybrid materials [J]. Macromolecules, 2004,37 (13) : 5123～5126.
[13]黄振宏,陈子达.医药用新型有机硅材料.中国医药工业杂志, 2003 , 34 (3) : 152～156.
[14] Zhang C, Laine RM.Synthesis of silylated derivatives of the cubic octameric siliate species Si8O20 [J]. Am Chem Soc, 2000; 122(29):6979～6988.
[15] Day V W, KlempererWG, Mainz V V, Millar D M.Preparation and characterization ofoctasilsesquioxane cage monomers[J].Am Chem Soc,1985,107(26):8262～8264.
[16] RopartzLoic,Morris russell E,Schwarz Gary P. Dendrimer-bound tertiary phosphines for alkene hydroformylation[J]. inorganic chamistry communications, 2000.3:714～717
[17] xiao steven, My Nguyen,xiong gong, et al. stabilization of semiconducting polymers with silsesquioxane[J].Adv Funct Mater, 2003,13(1):25
[18] zhu wen wei, xiao steven, Ishiang Shih. Field-effect mobilities of polyhedral oligomeric silscsquioxanes anchored semiconducting polymers[J].Applied Surface Science, 2004, 221:358～363
[19] Lichtenhan. Polymers containing alternating silsesquioxane and bridging group segments and process for thei preparation[P]. USP 5412053.1995
[20] Joseph D. Lichtenhan, Ngo Q. Vu and Michanel J.Carr. Sisesquioxane-siloxane copolym- ers from polehedral oligosilsesquioxans[J]. Macromolecules, 1993,26:2141～2142
[21] Frank J. Feher, David A. Newan,and John F. Walzer. Sisesquioxanes as models for silica surfaces[J].Am Chem Soc,1989;[1]:1741～1748
[22]Lichtenhan, J. D., Haddad, T. S., Schwab, J. J., The next generation of silicon-based plastics: polyhedral oligomeric silsesquioxane (POSS) nanocomposites[J]. Polymer Preprints, 1998,39(l):489
[23] Lee Andre; Lichtenhan, J. D. Viscoelastic Responses of Polyhedral oligosilses quioxane Reinforced Epoxy Systems[J]. Macromolecules, 1998, 31(15), 4970
[24]李绍雄,刘益军.聚胺酯胶黏剂[M ].北京:化学工业出版社,1998.
[25]袁金颖,潘才元.一种新型螺环原碳酸酯共聚改性环氧树脂的研究[J].中国胶粘剂,1997,6 (5):1～3.
[26] Kevin GaW, M itsutoshi Jikei, Masaaki Kakinoto Jlkei, et al. Adhesion behavior of pol- ymeric acid cured epoxy [J]. Polymer, 1997, (38) : 4413～4415.
[27]耿同谋.聚胺酯改性环氧及其应用[J].化工新型材料,1998, (5) :28～30.
[28]金林生.综述环氧树脂的增韧途径[J ].高分子材料, 1996, (1) :30～31
[29]梁伟荣,王惠民,郑志才.聚醚砜增韧环氧树脂的结构与性能[J].热固性树脂,1997, (4):12～14.
[30] Harani, Fellahi, Bakar. Toughening of epoxy resing syn thesized polyurethane prepo- lymer based on hydroxyl teminateed polyesters[J]. Appl Polym Sci, 1998, 70 (13) :2603～2618
[31]饶秋华.改性聚醚增韧环氧树脂的研究[J ].高分子材料科学与工程, 1997, 13 (1) :96～98.
[32]王惠民,梁伟荣.聚醚砜环氧树脂复合体系的研究[J].高分子材料科学与工程, 1999,15 (6) :155～157.
[33]徐修成.环氧/聚醚砜体系及其增韧机理的研究[J].宇航材料工艺,1996, 2(1) :32～34.
[34]韦春.反应型液晶聚合物改性环氧树脂性能的研究[J].高分子材料科学与工程, 2003, 19 (1) :168～171.
[35] Lange F F. Model for the toughness of epoxy - rubber particulate composite[J]. PhilMag, 1970, (22) :983.
[36] Nnn Heml. Phase separation in rubber- modified thermoset resin: opticalmicroscopy and laser scattering[J]. J. of Appl. Polym Sci, 1986, (31) :15～25.
[37] Pinnavala T J, Tie Lan, Zhen Wang. Clay - reinforced epoxy nanocomposites: synthesis, properties and mechanism of forfation[J]. J Am Chem Soc,1996,( 17) :251～261.
[38] Usukia, Aizutanit F, Fujimoto I, et al. Composite Material Containing a Layered silicat- e :US,4889885[P]. 1989: 12～26.
[39]于浩,路太平.环氧树脂/聚胺酯互穿网络的研究[J]。热固性树脂,1996,11( 1) :13～16.
[40]管云林.聚胺酯/环氧树脂互穿网络聚合物相行为与粘接剪切性能的研究[J].高分子材料科学与工程,1996,12 (5) : 121～126.
[41]王超,张斌,李奇力.耐高温环氧树脂胶黏剂的研制[J].中国胶粘剂,1999, 3 :12～13.
[42]管云林.聚胺酯/呋喃树脂互穿聚合物网络性能的研究[J].化学工业与工程, 1997, 14 (1) :25～29.
[43] Yingli, Sufen Mao. Studyon the properties and application of epoxy resin/polyurethane Semi - interpenetrating Polymer net works[J]. J of Applpolym Sci, 1996, (61) :2059～2063.
[44]钱军民,李旭祥.环氧树脂改性研究进展[J ].绝缘材料, 2001, (5) :27～31
[45]蒋红梅.环氧-聚胺酯互穿聚合物网络导电涂料[J].涂料工业,1999, (3) :12～15.
[46]黄云辉,张志力.环氧聚胺酯涂料的研究[J ].南昌航空工业学院学报,1997, (4) :63～67.
[47]郑瑞琪,余云照。合成胶黏剂丛书[M ]。北京:化学工业出版社, 1985,6(2):19～23。
[48] Hoebbel, D.,Klaus, E., Thomas, R.,Irene, P. Inorganic-organic polymers derived from functional silicic acid derivatives by additive reaction[J]. J. Non-Cryst. Solids 1994, 176～179.
[49]汪佳凤,徐宏耀,鲍亮.POSS基高分子材料的合成与热性能[J]。高分子材料科学与工程,2005,21(5):10～13.
[50]刘磊,宋磊,张胜,胡源.POSS/PS复合材料的结构与燃烧性能[J].中国科学技术大学学报,2006,36(1):29～33.
[51]朱立新,黄凤来,祝亚菲,严慧明,顾均杨.高交联度不饱和聚酯增韧改性的固化特征及动力学分析[J].复合材料学报,2003,3(20):22～26.