紫外光/湿气双固化聚硅氧烷树脂的制备及其固化机理的研究
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摘要
聚硅氧烷树脂可以通过硅羟基缩合及硅氢加成反应进行交联固化,同时固化产物具有优良的耐高低温性能和弹性的可调节性,广泛用于粘接、密封领域,在航天、电子等领域是不可或缺的材料。研究和开发有机硅材料的新固化方式是有机硅开发的重要方向之一。本论文通过结构设计,合成具有双固化特点的新型官能化聚硅氧烷树脂(ATPS),综合了紫外光固化技术快速固化和湿气固化方便的特点,同时解决了紫外光固化存在的阴影及湿固化定位速度慢的难题,扩展了有机硅材料的应用。因此,研究新型官能化聚硅氧烷树脂(ATPS)不仅具有重要的现实应用意义,而且对新型紫外光固化预聚物的研发具有指导意义。
本论文研究了各种反应条件及原料配比对合成反应的影响,同时采用IR、1H-NMR、13C-NMR、29Si-NMR等方法研表征了树脂的结构,通过平板-小刀法、实时红外(RTIR)等方法对双固化机理进行了考察,用DSC、TG方法研究了树脂双固化物的热性能。
主要工作如下：
1.设计反应路线,由端羟基聚二甲基硅氧烷与甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)通过脱醇缩合反应得到端甲基丙烯酰氧基烷氧基的线形有机硅长链分子(ATPS),并且建立了实现这种反应路线所需的工艺体系。
2.通过IR、NMR等手段表征了ATPS树脂,从结构上确定了其具备双固化特性,且证明了该树脂结构为线形长链聚合物。
3.研究了ATPS的双固化行为,结果表明,在紫外光固化过程中,光引发剂添加量、光照强度、光引发剂种类均受与双固化预聚物相容性影响；在湿气过程中,通过测定湿气固化过程的凝胶时间,经Arrhenius公式推导计算,在28%相对湿度的环境测试下,双固化预聚物的湿气固化反应表观活化能为23.2kJ/mol,频率指数lnA=-5.466。
4.考察了通过添加胺类促进剂和加入活性含硅稀释剂两种提高ATPS树脂光固化速率的方法,结果表明,胺类促进剂在该体系中自身的阻聚作用强于对氧阻聚的抑制作用,而使光固化速率降低；活性含硅稀释剂的加入能在一定程度上加快光固化速率。
5.研究了双固化树脂固化后的热力学性能,通过DSC测试双固化物的玻璃化转变温度Tg为-81.4℃,TGA测试该固化物的热失重10%的温度为427.8℃,经过公式推算,可以得出其热分解活化能为129.3kJ/mol。
6.设计反应路线,将光引发剂1173与侧基为氢基的线形有机硅长链分子(PMHS)进行脱氢取代反应,合成了侧基含有光引发剂基团的长链聚硅氧烷树脂。相容性实验表明,其与ATPS树脂的相容性较好。
Polysiloxane resin can be cured by condensation of Si-OH or hydrosilylation, and their cured product has excellent resistance, high and low temperature performace and adjustable flexibility. They are widely used in the area of bonding and sealing, which become essential materials in the aerospace, electronics and other fields. Research and development of the new curing method is an important direction in the area of silicone materials. The functionalized polysiloxane resin (Acrylate and alkoxy-terminated polysiloxane, ATPS) was designed and synthesized, which combined fast curing of UV curing technology and convenient moisture curing. The problems of the existence of the shadow in the UV curing and slow positioning in the moisture curing were solved by the synthesis of ATPS, which extending the application of silicone materials. Therefore, the study of the new functionalized polysiloxane resin (ATPS) has not only very important practical applications, but also has instructive development of UV curable prepolymer.
In this thesis, the reaction conditions and raw materials ratio on the synthesis were investigated, the structure of the resin was characterized by IR,1H-NMR,13C-NMR and 29Si-NMR. The dual cure mechanisms were studied by real-time infrared (RTIR) and plane-knife method, and also thermal properties were considerred by DSC and TG.
1. ATPS with acrylate and alkoxy-terminated groups was synthesized by transesterification reaction ofγ-(methacryloyloxy)propyltrimeth oxysilane with hydroxyl-terminated polydimethylsiloxane, and the reaction route system was also established.
2. ATPS was characterized by IR and NMR, its characteristics of dual curing and long linear structure were proved and determined.
3. Dual curing behavior of ATPS was studied, the addition of photoinitiator, light intensity and different photoinitiator types were influenced by the compatibility of dual-curing prepolymer in the UV curing process. In Moisture curing process, the gel time was measured, according to the formula of Arrhenius, the moisture curing apparent activation energy was 23.2kJ/mol, frequency index lnA=-5.466, which was tested at 28% relative humidity.
4. Adding the amine accelerator and activity diluent to increased ATPS' UV curing rate were investigated. The results showed that the amine accelerator in this system was its own inhibitor stronger than the inhibition of oxygen inhibition, leaving the curing rate decrease; By adding the Si-contained diluents, the curing rate can be accelerated at a certain extent.
5. Thermal properties of dual curing product were studied by DSC and TG. The results show that the Tg was -81.4℃, the temperature of thermal decomposition of cured product 10% was 427.8℃. After the formula projections, the thermal decomposition activation energy was 129.3kJ/mol, which can be drawn from the projected formula.
6. polysiloxane modified Photoinitiator was synthesized from polymethylhydrosiloxane(PMHS) by dehydrocoupling reaction. The experiments showed that the Si-contained photoinitiator had good compatibility with ATPS.
本论文研究了各种反应条件及原料配比对合成反应的影响,同时采用IR、1H-NMR、13C-NMR、29Si-NMR等方法研表征了树脂的结构,通过平板-小刀法、实时红外(RTIR)等方法对双固化机理进行了考察,用DSC、TG方法研究了树脂双固化物的热性能。
主要工作如下：
1.设计反应路线,由端羟基聚二甲基硅氧烷与甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)通过脱醇缩合反应得到端甲基丙烯酰氧基烷氧基的线形有机硅长链分子(ATPS),并且建立了实现这种反应路线所需的工艺体系。
2.通过IR、NMR等手段表征了ATPS树脂,从结构上确定了其具备双固化特性,且证明了该树脂结构为线形长链聚合物。
3.研究了ATPS的双固化行为,结果表明,在紫外光固化过程中,光引发剂添加量、光照强度、光引发剂种类均受与双固化预聚物相容性影响；在湿气过程中,通过测定湿气固化过程的凝胶时间,经Arrhenius公式推导计算,在28%相对湿度的环境测试下,双固化预聚物的湿气固化反应表观活化能为23.2kJ/mol,频率指数lnA=-5.466。
4.考察了通过添加胺类促进剂和加入活性含硅稀释剂两种提高ATPS树脂光固化速率的方法,结果表明,胺类促进剂在该体系中自身的阻聚作用强于对氧阻聚的抑制作用,而使光固化速率降低；活性含硅稀释剂的加入能在一定程度上加快光固化速率。
5.研究了双固化树脂固化后的热力学性能,通过DSC测试双固化物的玻璃化转变温度Tg为-81.4℃,TGA测试该固化物的热失重10%的温度为427.8℃,经过公式推算,可以得出其热分解活化能为129.3kJ/mol。
6.设计反应路线,将光引发剂1173与侧基为氢基的线形有机硅长链分子(PMHS)进行脱氢取代反应,合成了侧基含有光引发剂基团的长链聚硅氧烷树脂。相容性实验表明,其与ATPS树脂的相容性较好。
Polysiloxane resin can be cured by condensation of Si-OH or hydrosilylation, and their cured product has excellent resistance, high and low temperature performace and adjustable flexibility. They are widely used in the area of bonding and sealing, which become essential materials in the aerospace, electronics and other fields. Research and development of the new curing method is an important direction in the area of silicone materials. The functionalized polysiloxane resin (Acrylate and alkoxy-terminated polysiloxane, ATPS) was designed and synthesized, which combined fast curing of UV curing technology and convenient moisture curing. The problems of the existence of the shadow in the UV curing and slow positioning in the moisture curing were solved by the synthesis of ATPS, which extending the application of silicone materials. Therefore, the study of the new functionalized polysiloxane resin (ATPS) has not only very important practical applications, but also has instructive development of UV curable prepolymer.
In this thesis, the reaction conditions and raw materials ratio on the synthesis were investigated, the structure of the resin was characterized by IR,1H-NMR,13C-NMR and 29Si-NMR. The dual cure mechanisms were studied by real-time infrared (RTIR) and plane-knife method, and also thermal properties were considerred by DSC and TG.
1. ATPS with acrylate and alkoxy-terminated groups was synthesized by transesterification reaction ofγ-(methacryloyloxy)propyltrimeth oxysilane with hydroxyl-terminated polydimethylsiloxane, and the reaction route system was also established.
2. ATPS was characterized by IR and NMR, its characteristics of dual curing and long linear structure were proved and determined.
3. Dual curing behavior of ATPS was studied, the addition of photoinitiator, light intensity and different photoinitiator types were influenced by the compatibility of dual-curing prepolymer in the UV curing process. In Moisture curing process, the gel time was measured, according to the formula of Arrhenius, the moisture curing apparent activation energy was 23.2kJ/mol, frequency index lnA=-5.466, which was tested at 28% relative humidity.
4. Adding the amine accelerator and activity diluent to increased ATPS' UV curing rate were investigated. The results showed that the amine accelerator in this system was its own inhibitor stronger than the inhibition of oxygen inhibition, leaving the curing rate decrease; By adding the Si-contained diluents, the curing rate can be accelerated at a certain extent.
5. Thermal properties of dual curing product were studied by DSC and TG. The results show that the Tg was -81.4℃, the temperature of thermal decomposition of cured product 10% was 427.8℃. After the formula projections, the thermal decomposition activation energy was 129.3kJ/mol, which can be drawn from the projected formula.
6. polysiloxane modified Photoinitiator was synthesized from polymethylhydrosiloxane(PMHS) by dehydrocoupling reaction. The experiments showed that the Si-contained photoinitiator had good compatibility with ATPS.
引文
[1]幸松民,王一璐.有机硅合成工艺及产品应用[M].北京：化学工业出版社,2000.
[2]来国桥,幸松民,等.有机硅产品合成及应用[M].北京：化学工业出版社,2009.
[3]范召东,张鹏,等.有机硅密封剂耐热性能研究[J].航空材料学报,2006,3(26)：203-206.
[4]黄毓礼,付国东,等.有机硅丙烯酸酯聚合物的紫外光固化反应[J].高分子材料科学与工程,2001,6(17)：61-63.
[5]胡生祥,张军营.紫外光固化有机硅丙烯酸酯的合成研究[J].化工新型材料,2008,3(36)：54-73.
[6]Tsai MF, Lee YD, Long YC. Synthesis of a polydimethylsiloxane-block-hydroxyl grafted acrylate prepolymer copolymer to improve the adhesion between silicone rubber and polyurethane by induced surface reconstruction. J Polym Res 2000; 7:73-9.
[7]Samuel K.Lai, Ashish Batra, Claude Cohen. Characterization of polydimethylsiloxane elastomer degradation via cross-linker hydrolysis. Polymer 2005;46:4204-4211.
[8]聂俊,肖鸣,等.光聚合技术与应用[M].北京：化学工业出版社,2008
[9]Yusong Qi, Jianwen Yang, Zhaohua Zeng, Zhengfu Liao, Yonglie Chen. Novel Reactive Diluents of UV/Moisture Dual-curable Coating. J Appl Polym Sci 2005;98:1500-1504.
[10]Cristina Iojoiu, Marc J.M. Abadie, Valeria Harabagiu, Mariana Pinteala, Bogdan C. Simionescu. Synthesis and photocrosslinking of benzyl acrylate substituted polydimethylsiloxanes. Eur Polym J 2000;36:2115-2123.
[11]周其凤,范星河,谢晓峰.耐高温聚合物及其复合材料合成、应用与进展.北京：化学工业出版社,2004
[12]Comyn J. Moisture cure of adhesives and sealants [J]. International Journal of Adhesion and Adhesives,1998,18:247-253
[13]潘涛,纪夕质等.有机硅材料及应用,1995,(6)：4.
[14]刘宏宇,张松.有机硅耐高温涂料的研制[J].有机硅材料,2008,22(6)：369-370.
[15]冯西桥.范召东,张鹏,成晓阳等.耐800℃密封材料(涂料)的研制[J].化工新型材料,2006,34(5)：61-63
[16]陈用烈,曾兆华,杨建文.辐射固化材料及其应用[M].北京：化学工业出版社,2003.
[17]王德海,江棂.紫外光固化材料理论与应用[M].北京：科学出版社,2001.6
[18]朱国巍.紫外光固化涂料的制备及其氧阻聚的研究[D].长春理工大学硕士论文,2006
[19]Sheng Shu Hou, Ping Lin Kuo. Function and performance of silicone copolymers,3a Synthesis and properties of a novel siliconized acrylic monomer containing three reactive sites. Macromol. Chem. Phys.1999;200:2501-2507.
[20]胡生祥,张军营.紫外光固化丙烯酸酯有机硅预聚物的合成与固化性能的研究[D].北京化工大学硕士论文,2008.
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[28]Sun F, Jiang S L. Synthesis and Characterization of Photosensitive Polysiloxane. Nuclear Inst. and Methods in Physics Research, B,2007,254:125-130.
[29]孙芳,黄毓礼,牛爱杰.有机硅聚氨酯丙烯酸酯预聚物的合成、表征及感光性[J1.高分子材料科学与工程,2002,18(5)：58-61.
[30]梁驻军,杨洪梅等.大分子光引发剂的研究进展.精细与专用化学品,2003,(20)：1-3.
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[32]安秋凤,路德待等.二苯甲酮类紫外吸收基聚硅氧烷的合成与表征[J].精细化工,2005,22(10)：707-727.
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[40]Yusong Qi, Jianwen Yang, Zhaohua Zeng, Zhengfu Liao, Yonglie Chen. Novel Reactive Diluents of UV/Moisture Dual-curable Coating. J Appl Polym Sci 2005;98:1500-1504.
[41]Sheng Shu Hou, Ping Lin Kuo. Function and performance of silicone copolymers,3a Synthesis and properties of a novel siliconized acrylic monomer containing three reactive sites. Macromol. Chem. Phys.1999;200:2501-2507.
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[2]来国桥,幸松民,等.有机硅产品合成及应用[M].北京：化学工业出版社,2009.
[3]范召东,张鹏,等.有机硅密封剂耐热性能研究[J].航空材料学报,2006,3(26)：203-206.
[4]黄毓礼,付国东,等.有机硅丙烯酸酯聚合物的紫外光固化反应[J].高分子材料科学与工程,2001,6(17)：61-63.
[5]胡生祥,张军营.紫外光固化有机硅丙烯酸酯的合成研究[J].化工新型材料,2008,3(36)：54-73.
[6]Tsai MF, Lee YD, Long YC. Synthesis of a polydimethylsiloxane-block-hydroxyl grafted acrylate prepolymer copolymer to improve the adhesion between silicone rubber and polyurethane by induced surface reconstruction. J Polym Res 2000; 7:73-9.
[7]Samuel K.Lai, Ashish Batra, Claude Cohen. Characterization of polydimethylsiloxane elastomer degradation via cross-linker hydrolysis. Polymer 2005;46:4204-4211.
[8]聂俊,肖鸣,等.光聚合技术与应用[M].北京：化学工业出版社,2008
[9]Yusong Qi, Jianwen Yang, Zhaohua Zeng, Zhengfu Liao, Yonglie Chen. Novel Reactive Diluents of UV/Moisture Dual-curable Coating. J Appl Polym Sci 2005;98:1500-1504.
[10]Cristina Iojoiu, Marc J.M. Abadie, Valeria Harabagiu, Mariana Pinteala, Bogdan C. Simionescu. Synthesis and photocrosslinking of benzyl acrylate substituted polydimethylsiloxanes. Eur Polym J 2000;36:2115-2123.
[11]周其凤,范星河,谢晓峰.耐高温聚合物及其复合材料合成、应用与进展.北京：化学工业出版社,2004
[12]Comyn J. Moisture cure of adhesives and sealants [J]. International Journal of Adhesion and Adhesives,1998,18:247-253
[13]潘涛,纪夕质等.有机硅材料及应用,1995,(6)：4.
[14]刘宏宇,张松.有机硅耐高温涂料的研制[J].有机硅材料,2008,22(6)：369-370.
[15]冯西桥.范召东,张鹏,成晓阳等.耐800℃密封材料(涂料)的研制[J].化工新型材料,2006,34(5)：61-63
[16]陈用烈,曾兆华,杨建文.辐射固化材料及其应用[M].北京：化学工业出版社,2003.
[17]王德海,江棂.紫外光固化材料理论与应用[M].北京：科学出版社,2001.6
[18]朱国巍.紫外光固化涂料的制备及其氧阻聚的研究[D].长春理工大学硕士论文,2006
[19]Sheng Shu Hou, Ping Lin Kuo. Function and performance of silicone copolymers,3a Synthesis and properties of a novel siliconized acrylic monomer containing three reactive sites. Macromol. Chem. Phys.1999;200:2501-2507.
[20]胡生祥,张军营.紫外光固化丙烯酸酯有机硅预聚物的合成与固化性能的研究[D].北京化工大学硕士论文,2008.
[21]Hockemeyer F, Preiner G US 4554339.1985.
[22]Christian Weitemeyer. US 4963438.1990.
[23]Michihiro O, Tetsuya M, Fujino T, Noshiro A (Dainippon printing and Shin-Etsu) Ger 2233514.1973.
[24]李光亮等.有机硅高分子化学[M].北京：科学出版社,1999：27.
[25]刘长利,吴文健等.光敏性有机硅丙烯酸酯的合成及表征[J].化工新型材料 2006,20(4)：44-48.
[26]Masatoshi A, Tsuneo K. Novel organsilane compounds. US 4845259.1989.
[27]Lee NG L, Lutz M A. EP 230342.1987.
[28]Sun F, Jiang S L. Synthesis and Characterization of Photosensitive Polysiloxane. Nuclear Inst. and Methods in Physics Research, B,2007,254:125-130.
[29]孙芳,黄毓礼,牛爱杰.有机硅聚氨酯丙烯酸酯预聚物的合成、表征及感光性[J1.高分子材料科学与工程,2002,18(5)：58-61.
[30]梁驻军,杨洪梅等.大分子光引发剂的研究进展.精细与专用化学品,2003,(20)：1-3.
[31]梁驻军,杨洪梅等.大分子光引发剂的研究进展.精细与专用化学品,2003,(19)：15-18.
[32]安秋凤,路德待等.二苯甲酮类紫外吸收基聚硅氧烷的合成与表征[J].精细化工,2005,22(10)：707-727.
[34]罗运军,桂红星.有机硅树脂及其应用[M].北京：化学工业出版社,2002
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