聚酰胺固化剂和缩水甘油醚稀释剂合成及改性性能研究
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摘要
环氧树脂胶黏剂间世已有60余年,并以其产品的多样化、卓越的性能、广泛的应用,使其应用在航空航天、军工汽车、石油化工、建筑建材、电子电器等日常生活和高新技术的领域。人们一直致力于改性环氧树脂的研究工作,并且在前人研究的基础上不断的进步,开发设计出更多新的环氧树脂胶黏剂。随着科技的进步,为了满足极端苛刻的使用要求,近几年的的改性方向主要是在添加剂上,如固化剂、稀释剂、增韧剂、增塑剂、促进剂等。对于探寻新的改性环氧树脂胶黏剂方法的步伐从未停止过。
     本文主要是在固化剂和稀释剂改性环氧树脂胶黏剂两个方面进行了一些探索。固化剂方面合成了低分子聚酰胺,并与环氧树脂E-44混合固化,对其固化体系的力学性能和热性能分析讨论;稀释剂方面改进了合成间苯二酚二缩水甘油醚的方法,使其生产成本降低,并研究了其与环氧树脂E-44共混体系的性能与组成的关系。
Comparing with other thermosetting resin, epoxy resin possesses its unique excellent performance, because it consists of such polar groups and active groups as epoxy base, hydroxyl, ether. Epoxy adhesive which can meet many practical applications, offering distinctive performances, whereas other kinds of thermosetting resin have not represented yet, can be prepared by blending epoxy resin with epoxy resin curing agent, promoting agents, modifier and additives. To satisfy the requirement of application for different fields, the focus of researchers worldwide on the modification of epoxy resin curing agent is strengthened recently, resulting in numerously valuable experiences. Moreover, investigation of the influence of different modification materials and conditions on the modified products and exploitation of new modification methods or the synthesis of new epoxy curing agent are still intriguing to scientists dedicated to epoxy adhesive. This thesis mainly investigates the mechanical properties and thermodynamic properties of epoxy adhesive using polyamide as curing agent or modified with epoxy thinners, which contribute considerably to designing formula and show great potential for industrial application.
     In the first part, polyamide class curing agents with relatively low molecular weight was synthesized by tuning the ratio of acid with respect to amine, followed by molecular structure characterization and essential tests about their physical properties. Then the well prepared polyamide was mixed with epoxy resin according to different weight ratio, and afterwards the effect of curing process on thermal properties mechanical properties was investigated. The results indicated that the curing rate under room temperature is relatively slow, costing about 7 days, while the curing process can be completed totally within 4h at 120℃. Moreover, the tensile strength of epoxy resin cured at 120℃could reach lOMPa, which is proved much higher than that cured at room temperature. Noticeably, the value of Tg of epoxy resin which had undergone curing process is higher than that without any treatment and polyamide itself, and increased with an increase in polyamide content relative to epoxy resin,
     In the second part, epoxy adhesive was modified with glycidyl ether class epoxy thinner in which synthetic process condition of RDGE was improved. Influence of reaction condition on product was investigated via the orthogonal experiment and single factor analysis method. Finally, E-44 was sequentially blended with RDGE described before. The relationship, between the viscosities of the hybrid system and composition or temperature, was investigated respectively. Most importantly, mechanical properties of all the blends were tested thoroughly here.
引文
[1]李广宇,李子东,吉利,刘戈等.环氧胶黏剂与应用技术[M].北京:化学工业出版社,2007.
    [2]贺曼罗.环氧树脂胶黏剂[M].北京:中国石化出版社,2004.
    [3]石学堂.改性胺类固化剂与特种建筑胶粘剂的制备研究[D].大连:大连理工大学化学工程专业,2008.
    [4]Ying Li, Suffern Mao. Study on the properties and application of epoxy resin/polyurethane semi-interpenetrating polymer networks. Journalof Applied Polymer Science,1996,61:2059-2063
    [5]N.Biolley, T. Pascal, B. Sillion. Polyimide-modified epoxy system: time-temperature-trans-formation diagrams, mechanical and thermal properties. Polymer,1994,35:558-564.
    [6]姚康德,成国祥.环氧树脂增韧研究进展[J].热固性树脂,2001,16(2):22
    [7]杨保利.环氧树脂增韧剂及其应用试验研究[J].环氧树脂应用技术,2001,18(2):33
    [8]王庭慰,陈瑞珠,赵刚.端异氰酸酯聚醚增韧环氧树脂固化动力学研究[J].粘接,2001,22(6):4
    [9]阎恒海.环氧树脂增韧技术的发展[J].工程塑料应用,1989(2):45
    [10]欧召阳,马文石,潘慧铭.环氧树脂改性研究新进展[J].中国胶粘剂,2001,10(2):41
    [11]那兵.新型环氧树脂增韧剂的合成与研究[J].粘接,2002,23(4):21-22
    [12]樊庆春,孙波等.环氧树脂增韧剂CYH-277的应用性能[J].广州化工.2008,36(1):34-35
    [13]王琦洁.环氧树脂增韧进展[J].玻璃钢/复合材料,2004,(3):50-54.
    [14]亢雅君,殷立新.环氧树脂中温固化促进剂评述[J].热固性树脂1995(2):47-51.
    [15]何尚锦,石可瑜,沃华等.咪唑封端扩链脲改性环氧树脂E-51/酸酐MTHPQ体系性能研究[J].高分子材料科学与工程,2003,19(2):69-72.
    [16]袁剑民,邓剑如,蒋卫和.新型环氧稀释剂环己一醇-1,2二缩水甘油醚的合成[J].热固性树脂.2004,19(5):24-26.
    [17]黄坤,王石发,万厉.糠醇缩水甘油醚稀释的环氧体系的性能研究[J].热固性树脂.2009,24(5):1-5.
    [18]孙济菡,陆企华.活性阻燃环氧稀释剂的合成[J].热固性树脂,1988,(3):1-4.
    [19]ME Flory, A Abu Obairl, X H uang etal. Fiber/matrix interphase characterization using the dynamic interphase loading apparatus[J] Composites,2002,33A:1345-1348.
    [20]张宏军,周晓东,等.嵌段共聚偶联剂的合成及其对玻纤/环氧复合材料性能的影响[J].玻璃钢/复合材料.2005(3):30-33
    [21]马寒冰,陈章.偶联剂对制备环氧-低熔点金属复合材料的影响[J].化工技术与开发.2010,39(5):1-2.
    [22]吴志平,高永裕等.偶联剂对EP/APP体系燃烧和发烟性能的影响[J].化工新型材料.2010,38(3):79-81.
    [23]齐秋云,高克强.触变剂活性SiO2的阻燃性能研究.玻璃钢/复合材料[J].1993(1):26-28.
    [24]聚酰胺型触变剂和防沉剂[J].涂料工业,2000,(02)
    [25]N HEMI. Phase separation in rubber-modified thermoset resin:optical microscopy and laser scattering. [J]. J.of APP1. polym. Sci,1986, (31):15.
    [26]U. S. P:4126531,1978.
    [27]韩孝族,王莲芝等.端羧基丁腈橡胶增韧环氧树脂的研究[J].高分子学报,1989,(2):225.
    [28]J N Sultant, F J McCarry. Polym. Eng. Sci,1973,13:29.
    [29]韦亚兵,张玲等.互穿网络法增韧环氧树脂胶粘剂的研究[J].中国胶粘剂,2002,(1):6-8.
    [30]李己明,土晓敏等.以具有核壳结构的聚丙烯酸酯颗粒增韧环氧树脂胶粘剂[J].粘接,1993,(1):1.
    [31]魏伯荣,张海燕等.环氧一甲基丙烯酸酯树脂的固化特性研究[J].纤维复合 材料,2001,(3):18.
    [32]YING I. SUFEN MAO. Study on the Properties and Appli-cation of Epoxy Pesin/Polyurethane Semi-interpenetratingPolymer networks [J]. J. of Appl. Poly. Sci,1996, (61):2059.
    [33]P M stefani, S M Moschiar, M I Aranguren. Appl. polym. Sci,1998,26 (5):28.
    [34]郑亚萍,宁荣昌.纳米SiO2环氧树脂复合材料性能研究[J].玻璃钢/复合材料,2001,(2):34.
    [35]Ishizu K. Application of a series of novel curing agent and toughing modified for epoxy resin. Progress in Polymer Science,1998,23 (8): 1383-1408
    [36]顾媛娟,梁国正等.双马来酞亚胺改性TDE—85环氧树脂研究[J].高分子材料科学与工程,1996,(2):43.
    [37]候其德等.钻机刹车片用粘合剂的研究[J].精细化工,1997,14(4):40-42
    [38]自宗武,张秋红,汪晓东.耐高温改性环氧树脂粘接剂的制备及改性机理研究[J].功能高分子学报,1996,9(3):437-444.
    [39]S SPRENGER新奇的弹性体改性环氧预聚物[J].粘合剂技术(中文版),1999,(1):14-17.
    [40]赖士洪,邹贤武.环氧-聚砜结构胶粘剂耐环境性能的研究[J].中国胶粘剂,2002,11(6):19-21.
    [41]T-M Don, J P Bell. J. Appl. Polym. Sci,1998,69 (26):2395.
    [42]张影,唐小真,徐祥铭.高分子材料科学与工程,1998,14(5);136.
    [43]魏春鸣,顾毓仁,谢友干,高峰.双氰胺改性环氧树脂结构胶的研制[J].安徽化工,1983,(04):37-40
    [44]蒋伯成,孔德忠等.聚酰亚胺改性环氧树脂胶黏剂的研究[J].化学与粘合,2010,32(02):13-15
    [45]刘竞超,李小兵等.纳米二氧化硅增强增韧环氧树脂的研究[J].胶体与聚合物,2000,18(4):15-17.
    [46]欧育香.实用阻燃技术[M].北京:化学工业出版社,2002.
    [47]Grand A F, Wilkic C A. Fire Retardanc;y of Polymeric Matcrrials [M].New York:Marcel Dekker, Inc.2000.
    [48]胡晖,张有勇,中景强等.低烟无卤无磷阻燃热收缩材料的研制[J].化工新型材料,2006,34(6):78-82.
    [49]刘金刚,王德生,范琳等.环境友好型无卤无锑无磷阻燃环氧树脂的进展(iv)[J].热固性树脂,2004,19(4):23-28.
    [50]叶春生,陈连喜,自向鸽,等.阻燃型含硅环氧树脂的研究进展[J].山西化工,2009,29(3):33-37.
    [51]陈华堂,王建锋,伍小丽等.纳米SiO2改性环氧树脂工艺条件与性能研究[J].绝缘材料,2008,41(1):40-43.
    [52]田力普,李玲.新型含氮环氧树脂研究进展[J].中国胶黏剂.2009,18(2):58-61
    [53]黎艳,刘伟区,宣宜宁.有机硅改性双酚A型环氧树脂研究[J].高分子学报,2005(2):244-247.
    [54]袁才登,许勇深,王艳君,等.含氮酚醛树脂及其对环氧树脂的阻燃改性[J].热固性树脂,2004,15(2):12-14
    [55]郝建薇,吴娜,熊燕兵.固化体系对环氧树脂阻燃性能影响的研究[J].塑料助剂,2006(2):28-31
    [25]Wu Wan Lung, Hsn Kung Chung, Cheng Wu Hsun. A Simple Imide Compound as a Curing Agent for Epoxy Resin. iv. Synthesis and Properties [J]. Journal of Applied Polymer Science,2008,108(3):2052-2059.
    [57]陈艳雄.环氧树脂柔性固化剂的合成及其固化反应动力学研究[D].四川:四川大学材料学院,2007.
    [58]朱金风.以二聚酸制备酰胺树脂的研究[J].热固性树脂,1996,(4):59-60.
    [59]汪巩,周莉.从二聚酸制备聚酸胺[J].16-23.
    [60]孙涛,陆大年,朱建强.油墨连接料用聚酰胺树脂的研制[J].化学与黏合,2009,31(3):70-71.
    [61]牛古丹,杨秀春,张天娜.妥尔油、亚油酸二聚体混酸低分子聚酰胺固化剂的 合成[J].哈尔滨师范大学自然科学学报,2007,23(1):75-79.
    [62]杨兴明.650低分子聚酰胺的研制和应用[J].中国胶粘剂,5(2)42-43.
    [63]陈尔几,赵鸣玉,陈不松,唐少杰.低分子量聚酰胺的合成[J].浙江化工,1991,(4):28-31.
    [64]吴建良,郝聪俐,宋晓华.低分子量聚酰胺树脂的研究[J].2004,35,(03)19.
    [65]黄赤,叶龙,彭永利.低粘度聚酰胺的合成[J].武汉工程大学学报,2010,32(11):81-84.
    [66]刘云,辛红玲,闫云君,徐莉.基于生物柴油的二聚化及其聚酰胺树脂的合成[J].北京化工大学学报,2010,37(1):106-112.
    [67]胡高平,李明轩,杨映霞,肖卫东.650#聚酰胺的差异对环氧树脂固化物性能的影响[J].湖北大学学报(自然科学版),1999,21(3):278-280.
    [68]胡高平,肖卫东.酚醛胺-低分子聚酰胺协同固化环氧树脂的研究[J].热固性树脂,2002,3(2):25-26.
    [69]夏建陵,聂小安,张燕,陈瑶,王定选.新型低分子低粘度聚酸胺与环氧树脂固化体系的性能研究[J].385-387
    [69]夏建陵,孙小梅,王定选.环氧树脂聚酰胺网络体系性能研究[J].热固性树脂,2005,20(6):14-17.
    [70]徐任信,周祖福,王钧.环氧树脂新型固化体系的动力学研究[J].玻璃钢学会第十三届全国玻璃钢/复合材料学术年会论文集,1999,A(3):18-22.
    [71]黄坤,夏建陵,李梅,丁海洋.桐油制备C21聚酰胺环氧固化剂的性能及固化反应动力学研究[J].精细化工,2009,26(2):109-114.
    [72]孙保帅,张琳琪.聚酰胺共混改性研究的进展[J].郑州工业高等专科学校学报,2004,20(3):26-27.
    [73]兰立丈,季铁正,周军辉,游鸿兰.环氧树脂低分子聚酸胺体系的固化反应特性及胶接强度[J].粘接,1986,7(1):1-3.
    [74]郭亚林,梁国正,丘哲明,刘爱华.聚酰胺固化有机硅改性环氧树脂研究[J].宇航材料工艺,2005,(6):30-33.
    [75]夏建陵,聂小安,张燕,陈瑶,王定选.新型聚酰胺/环氧固化体系性能的研究[J].热固性树脂,2004,19(5):27-28.
    [76]李春娥,王政,文闻,何平笙.环氧树脂-聚酰胺-玻璃微珠体系的固化[J].复合材料学报,2000,17(4):11-14.
    [77]张银生,尤瑜升,冀克俭,刘元俊.用红外光谱法研究环氧树脂基体的固化特性[J].工程塑料应用,1999,27(12):25-27.
    [78]刘静,赵敏,张荣珍,刘广田,巴信武..FTIR法研究环氧树脂固化反应动力学[J].功能高分子学报,2000,13(2):208-210.
    [79]张银生,冀克俭,刘元俊,哀克俭.用差示扫描量热法研究环氧树脂的固化特性[J].1997,25(6):22-24.
    [80]孙文兵,张超灿.等温DSC法研究聚酰胺与环氧树脂的固化动力学[J].武汉理工大学学报,2009,31(6):28-31.
    [81]孙文兵,张超灿,张藕生.不同聚酰胺用量下环氧树脂的非等温固化[J].武汉理工大学学报,2008,30(12):4-7.
    [82]黄水华,肖卫东,何培新,李建宗.环氧树脂聚酰胺固化物的热裂解反应研究[J].湖北大学学报(自然科学版),1995,17(4):363-367.
    [83]胡志鹏.我国环氧树脂市场发展综述[J].开发指南,2008,(1):16-18.
    [84]蔡永源,国外环氧树脂应用技术进展[J].合成树脂与塑料,1994,11(1):33-37.
    [85]白宗武,张秋红,荣俊峰.新型环氧树脂固化剂的合成与应用研究[J].热固性树脂,1995,(2):12-16.
    [85]洪重奎.间苯二酚二缩水甘油醚的合成及其应用.1999,(4):170-175
    [86]袁慧五,饶秋华.间苯二酚二缩水甘油醚的制备及其应用.2007,22(5):1-4
    [87]付东升,朱光明1,韩娟妮.环氧树脂的改性研究进展[J].中国胶粘剂,2002,12(3):51-54.
    [88]张凯,黄渝鸿,郝晓东,周德惠.环氧树脂改性技术研究进展[J].中国胶粘剂,2004,2(1):12-14.
    [89]欧召阳,马文石,潘慧铭.环氧树脂改性研究新进展[J].中国胶粘剂,2002,10(2):41-44.
    [90]张斌关,长参,王超.室温固化环氧胶粘剂的研究[J].中国胶粘剂,1994,4(6):29-32.
    [91]张在新.环氧树脂胶粘剂近展[J].中国胶粘剂,2003,12(6):56-60.