不同温度下环氧树脂代木搪塑模具的固化过程

引用本文: 张欢欢, 许东华, 管东波, 姚卫国, 石彤非. 不同温度下环氧树脂代木搪塑模具的固化过程[J]. 应用化学, 2016, 33(3): 299-306. doi: 10.11944/j.issn.1000-0518.2016.03.150230 shu

Citation: ZHANG Huanhuan, XU Donghua, GUAN Dongbo, YAO Weiguo, SHI Tongfei. The Curing Process of Epoxy Resin Tooling Board for Slush Mold at Different Temperature[J]. Chinese Journal of Applied Chemistry, 2016, 33(3): 299-306. doi: 10.11944/j.issn.1000-0518.2016.03.150230 shu

不同温度下环氧树脂代木搪塑模具的固化过程

张欢欢 ^a,b,c, ,
许东华 ^b, ,
管东波 ^a, ,
姚卫国 ^{a,
,} ,
石彤非 ^{b,
,}

a.
a. 吉林大学材料科学与工程学院，教育部汽车材料重点实验室长春 130025;
b.
b. 中国科学院长春应用化学研究所，高分子物理与化学国家重点实验室长春 130022;
c.
c. 中国科学院大学北京 100049

通讯作者: 姚卫国,副教授;Tel:0431-84968881;Fax:0431-88999985;E-mail:wgyao@jlu.edu.cn;研究方向:高分子物理和化学;石彤非,研究员;Tel:0431-85262309;Fax:0431-85262969;E-mail:tfshi@ciac.ac.cn;研究方向:高分子物理; 姚卫国,副教授;Tel:0431-84968881;Fax:0431-88999985;E-mail:wgyao@jlu.edu.cn;研究方向:高分子物理和化学;石彤非,研究员;Tel:0431-85262309;Fax:0431-85262969;E-mail:tfshi@ciac.ac.cn;研究方向:高分子物理

基金项目:
国家自然科学基金资助项目（21274152，51473168，21234007，21174146）；国家重点基础研究发展规划（973计划）项目（2010CB631100）资助；吉林省科技厅科技发展计划项目（20120319）；汽车内饰产品搪塑工艺关键技术研究项目（2012362）

摘要: 采用流变学的方法研究了环氧树脂代木搪塑模具在不同温度下的固化过程。为了找到合适的测试条件，首先研究了应变和振荡频率对环氧树脂代木搪塑模具的测试结果的影响。环氧树脂代木搪塑模具固化过程中，体系交联程度逐渐变大；在不同的固化阶段，固化程度的变化快慢不同，先缓慢增加，然后迅速增加，最后缓慢增加至平台值；储能模量和损耗模量的变化速度在不同阶段的变化与固化程度的变化相似，根据储能模量和损耗模量的最快增长速率与温度的关系得到体系的活化能约为27.2 kJ/mol；随着固化温度升高，环氧树脂代木搪塑模具固化完全所需的时间减少，同时环氧树脂的施工容留时间也相应地减少。

关键词:

English

The Curing Process of Epoxy Resin Tooling Board for Slush Mold at Different Temperature

a.
a. Key Laboratory of Automobile Materials, Ministry of Education, College of Materials Science and Engineering, Jilin University, Changchun 130025, China;
b.
b. State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China;
c.
c. University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: 姚卫国,副教授;Tel:0431-84968881;Fax:0431-88999985;E-mail:wgyao@jlu.edu.cn;研究方向:高分子物理和化学;石彤非,研究员;Tel:0431-85262309;Fax:0431-85262969;E-mail:tfshi@ciac.ac.cn;研究方向:高分子物理; 姚卫国,副教授;Tel:0431-84968881;Fax:0431-88999985;E-mail:wgyao@jlu.edu.cn;研究方向:高分子物理和化学;石彤非,研究员;Tel:0431-85262309;Fax:0431-85262969;E-mail:tfshi@ciac.ac.cn;研究方向:高分子物理

Received Date: 06 July 2015
Fund Project:
国家自然科学基金资助项目（21274152，51473168，21234007，21174146）；国家重点基础研究发展规划（973计划）项目（2010CB631100）资助；吉林省科技厅科技发展计划项目（20120319）；汽车内饰产品搪塑工艺关键技术研究项目（2012362）

Abstract: The curing process of epoxy resin tooling board for slush mold with different temperature was studied by the rheological method. To find the suitable test condition, the influence of strain and oscillatory frequency on the curing process of epoxy resin tooling board for slush mold was investigated firstly. During the process of curing, the degree of curing becomes larger with time. However, for different stages, the curing rate is different, from slow to fast and finally becomes slow again until plateau. This variation trend is also similar with the storage modulus and loss modulus. On the basis of the relation between the maximum increasing speed of modulus and the reaction temperature, the activation energy of epoxy resin tooling board for slush mold is calculated to be 27.2 kJ/mol. As the reaction temperature increases, the curing rate of the two-component epoxy resin for slush mold speeds up and less time is needed to finish the curing reaction of the epoxy resin. At the same time, the time which can be used to handle the epoxy resin for making mold becomes less with the increase of temperature.

Key words:

1. [1] XIE Haian. Research Status of Modification of Epoxy Resin[J]. Plast Sci Technol,2007,35(1):82-85(in Chinese).谢海安. 环氧树脂改性研究进展[J]. 塑料科技,2007,35(1):82-85.[1] XIE Haian. Research Status of Modification of Epoxy Resin[J]. Plast Sci Technol,2007,35(1):82-85(in Chinese).谢海安. 环氧树脂改性研究进展[J]. 塑料科技,2007,35(1):82-85.
2. [2] WANG Wei. The Research Development of Curing Technology and Curing Agents for Epoxy Resin[J]. Thermoset Resin,2001,16(3):29-33(in Chinese).王伟. 环氧树脂固化技术及其固化剂研究进展[J]. 热固性树脂,2001,16(3):29-33.[2] WANG Wei. The Research Development of Curing Technology and Curing Agents for Epoxy Resin[J]. Thermoset Resin,2001,16(3):29-33(in Chinese).王伟. 环氧树脂固化技术及其固化剂研究进展[J]. 热固性树脂,2001,16(3):29-33.
3. [3] LIU Ye,DU Ming. Research Progress in Modification Techniques New Methods and Mechanism of Toughening Epoxy Resins[J]. Chem Adhes,2007,29(3):197-200(in Chinese).刘野,杜明. 环氧树脂增韧改性技术研究进展和新方法及其机理[J]. 化学与粘合,2007,29(3):197-200.[3] LIU Ye,DU Ming. Research Progress in Modification Techniques New Methods and Mechanism of Toughening Epoxy Resins[J]. Chem Adhes,2007,29(3):197-200(in Chinese).刘野,杜明. 环氧树脂增韧改性技术研究进展和新方法及其机理[J]. 化学与粘合,2007,29(3):197-200.
4. [4] GUO Zhansheng,DU Shanyi,ZHANG Boming,et al. CURE Kinetics and Chemorheological Behavior of Epoxy Resin Used in Advanced Composites[J]. Acta Mater Compos Sin,2004,21(4):146-151(in Chinese).郭战胜,杜善义,张博明,等. 先进复合材料用环氧树脂的固化反应和化学流变[J]. 复合材料学报,2004,21(4):146-151.[4] GUO Zhansheng,DU Shanyi,ZHANG Boming,et al. CURE Kinetics and Chemorheological Behavior of Epoxy Resin Used in Advanced Composites[J]. Acta Mater Compos Sin,2004,21(4):146-151(in Chinese).郭战胜,杜善义,张博明,等. 先进复合材料用环氧树脂的固化反应和化学流变[J]. 复合材料学报,2004,21(4):146-151.
5. [5] ZENG Xiaoliang,LIU Jia,XIONG Yuanqin,et al. Progress in Research on High Heat Resistance of Epoxy Resins[J]. Chem Ind Eng Prog,2009,28(6):986-990(in Chinese).曾小亮,刘甲,熊远钦,等. 高耐热性环氧树脂的研究进展[J]. 化工进展,2009,28(6):986-990.[5] ZENG Xiaoliang,LIU Jia,XIONG Yuanqin,et al. Progress in Research on High Heat Resistance of Epoxy Resins[J]. Chem Ind Eng Prog,2009,28(6):986-990(in Chinese).曾小亮,刘甲,熊远钦,等. 高耐热性环氧树脂的研究进展[J]. 化工进展,2009,28(6):986-990.
6. [6] BAI Yunqi,XUE Limei,LIU Yunfu. Advance in Modification of Epoxy Resin[J]. Chem Adhes,2007,29(4):289-292(in Chinese).白云起,薛丽梅,刘云夫. 环氧树脂的改性研究[J]. 化学与粘合,2007,29(4):289-292.[6] BAI Yunqi,XUE Limei,LIU Yunfu. Advance in Modification of Epoxy Resin[J]. Chem Adhes,2007,29(4):289-292(in Chinese).白云起,薛丽梅,刘云夫. 环氧树脂的改性研究[J]. 化学与粘合,2007,29(4):289-292.
7. [7] HONG Bin,WANG Tianzhen. Market Analysis of Epoxy Applications[J]. Thermoset Resin,2011,26(3):54-58(in Chinese).洪彬,王天祯. 环氧树脂应用领域市场分析[J]. 热固性树脂,2011,26(3):54-58.[7] HONG Bin,WANG Tianzhen. Market Analysis of Epoxy Applications[J]. Thermoset Resin,2011,26(3):54-58(in Chinese).洪彬,王天祯. 环氧树脂应用领域市场分析[J]. 热固性树脂,2011,26(3):54-58.
8. [8] LI Bailin. Study on Key Technologies of Slush Mould Preparation and Slush Forming Process[D]. Changchun:Jilin University,2014(in Chinese).李佰林. 搪塑模具制备及搪塑工艺关键技术研究[D]. 长春：吉林大学,2014.[8] LI Bailin. Study on Key Technologies of Slush Mould Preparation and Slush Forming Process[D]. Changchun:Jilin University,2014(in Chinese).李佰林. 搪塑模具制备及搪塑工艺关键技术研究[D]. 长春：吉林大学,2014.
9. [9] WU Wei,LIU Mingchang,CHEN Yu,et al. Shifting of the Curing Kinetic of E-51 Epoxy Resin[J]. Acta Mater Compos Sin,2011,28(4):1-6(in Chinese).吴唯,刘明昌,陈玉,等. E-51环氧树脂固化反应中动力学转变[J]. 复合材料学报,2011,28(4):1-6.[9] WU Wei,LIU Mingchang,CHEN Yu,et al. Shifting of the Curing Kinetic of E-51 Epoxy Resin[J]. Acta Mater Compos Sin,2011,28(4):1-6(in Chinese).吴唯,刘明昌,陈玉,等. E-51环氧树脂固化反应中动力学转变[J]. 复合材料学报,2011,28(4):1-6.
10. [10] ZHANG Jing,HUANG Pei. Research Advances in Epoxy Resin Curing Kinetics[J]. Mater Rev,2009,23(7):58-61(in Chinese).张竞,黄培. 环氧树脂固化动力学研究进展[J]. 材料导报,2009,23(7):58-61.[10] ZHANG Jing,HUANG Pei. Research Advances in Epoxy Resin Curing Kinetics[J]. Mater Rev,2009,23(7):58-61(in Chinese).张竞,黄培. 环氧树脂固化动力学研究进展[J]. 材料导报,2009,23(7):58-61.
11. [11] XIE Hongfeng,LIU Binghua,SUN Qing,et al. The Influence of Vapor-Grown Carbon Fibers on the Cure Reaction of Epoxy and the Curing Kinetics of the Composites[J]. Acta Polym Sin,2005,6:891-895(in Chinese).谢鸿峰,刘炳华,孙清,等. 气相生长碳纤维对环氧树脂固化反应的影响及其复合物固化动力学研究[J]. 高分子学报,2005,6:891-895.[11] XIE Hongfeng,LIU Binghua,SUN Qing,et al. The Influence of Vapor-Grown Carbon Fibers on the Cure Reaction of Epoxy and the Curing Kinetics of the Composites[J]. Acta Polym Sin,2005,6:891-895(in Chinese).谢鸿峰,刘炳华,孙清,等. 气相生长碳纤维对环氧树脂固化反应的影响及其复合物固化动力学研究[J]. 高分子学报,2005,6:891-895.
12. [12] GAN Li,SUN Zhijie,GU Zhizhuo,et al. Epoxy Resin Curing Reaction Studied by Dynamic and Isothermal Model Free Kinetics[J]. Acta Polym Sin,2010,8:1016-1021(in Chinese).甘丽,孙志杰,顾轶卓,等. 升温与等温法非模型动力学研究环氧树脂固化反应[J]. 高分子学报,2010,8:1016-1021.[12] GAN Li,SUN Zhijie,GU Zhizhuo,et al. Epoxy Resin Curing Reaction Studied by Dynamic and Isothermal Model Free Kinetics[J]. Acta Polym Sin,2010,8:1016-1021(in Chinese).甘丽,孙志杰,顾轶卓,等. 升温与等温法非模型动力学研究环氧树脂固化反应[J]. 高分子学报,2010,8:1016-1021.
13. [13] MAO Youan,TONG Yiqing. A Study of the Curing Kinetic of Epoxy Resin by DSC[J]. Polym Mater Sci Eng,1991,3:18-22(in Chinese).毛友安,童乙青. 用DSC 研究环氧树脂固化动力学[J]. 高分子材料科学与工程,1991,3:18-22.[13] MAO Youan,TONG Yiqing. A Study of the Curing Kinetic of Epoxy Resin by DSC[J]. Polym Mater Sci Eng,1991,3:18-22(in Chinese).毛友安,童乙青. 用DSC 研究环氧树脂固化动力学[J]. 高分子材料科学与工程,1991,3:18-22.
14. [14] Skordos A A,Partridge I K. Cure Kinetics Modeling of Epoxy Resins Using a Nonparametric Numerical Procedure[J]. Polym Eng Sci,2001,41(5):793-805.[14] Skordos A A,Partridge I K. Cure Kinetics Modeling of Epoxy Resins Using a Nonparametric Numerical Procedure[J]. Polym Eng Sci,2001,41(5):793-805.
15. [15] Cañmero-Martínez P,Fernández-García M,Dela Fuente J L. Rheological Cure Characterization of a Polyfunctional Epoxy Acrylic Resin[J]. React Funct Polym,2010,70(10):761-766.[15] Cañmero-Martínez P,Fernández-García M,Dela Fuente J L. Rheological Cure Characterization of a Polyfunctional Epoxy Acrylic Resin[J]. React Funct Polym,2010,70(10):761-766.
16. [16] CHEN Xianhua,SHEN Guiping,ZHANG Xu,et al. Rheological Characteristics of Epoxy Asphalt Binders and Their Allowable Reserved[J]. J Highw Transp Res Dev,2010,27(6):29-33(in Chinese).陈先华,沈桂平,张旭,等. 环氧沥青结合料的流变特性与施工容留时间预测[J]. 公路交通科技,2010,27(6):29-33.[16] CHEN Xianhua,SHEN Guiping,ZHANG Xu,et al. Rheological Characteristics of Epoxy Asphalt Binders and Their Allowable Reserved[J]. J Highw Transp Res Dev,2010,27(6):29-33(in Chinese).陈先华,沈桂平,张旭,等. 环氧沥青结合料的流变特性与施工容留时间预测[J]. 公路交通科技,2010,27(6):29-33.
17. [17] WANG Zhen,LI Qingxuan,GAO Lianxun,et al. Rheological Behavior of Themosetting Polyimide Resins[J]. Chinese J Appl Chem,2005,22(5):538-550(in Chinese).王震,李青璇,高连勋,等. 热固性聚酰亚胺基体树脂的流变行为[J]. 应用化学,2005,22(5):538-550.[17] WANG Zhen,LI Qingxuan,GAO Lianxun,et al. Rheological Behavior of Themosetting Polyimide Resins[J]. Chinese J Appl Chem,2005,22(5):538-550(in Chinese).王震,李青璇,高连勋,等. 热固性聚酰亚胺基体树脂的流变行为[J]. 应用化学,2005,22(5):538-550.
18. [18] Zhao C,Zhang G C,Zhao L. Effect of Curing Agent and Temperature on the Rheological Behavior of Epoxy Resin Systems[J]. Molecules,2012,17(7):8587-8594.[18] Zhao C,Zhang G C,Zhao L. Effect of Curing Agent and Temperature on the Rheological Behavior of Epoxy Resin Systems[J]. Molecules,2012,17(7):8587-8594.
19. [19] Palomo B,Habas-Ulloa A,Pignolet P,et al. Rheological and Thermal Study of the Curing Process of a Cycloaliphatic Epoxy Resin:Application to the Optimization of the Ultimate Thermomechanical and Electrical Properties[J]. J Phys D:Appl Phys,2013,46(6):065301-065310.[19] Palomo B,Habas-Ulloa A,Pignolet P,et al. Rheological and Thermal Study of the Curing Process of a Cycloaliphatic Epoxy Resin:Application to the Optimization of the Ultimate Thermomechanical and Electrical Properties[J]. J Phys D:Appl Phys,2013,46(6):065301-065310.
20. [20] Ramis X,Cadenato A,Morancho J M,et al. Curing of a Thermosetting Powder Coating by Means of DMTA, TMA and DSC[J]. Polymer,2003,44(7): 2067-2079.[20] Ramis X,Cadenato A,Morancho J M,et al. Curing of a Thermosetting Powder Coating by Means of DMTA, TMA and DSC[J]. Polymer,2003,44(7): 2067-2079.
21. [21] ZHANG Huanhuan,XU Donghua,GUAN Dongbo,et al. Rheological Properties of Two-Component Silicon Rubber During Cross-Linking by Addition Reaction[J]. Chem J Chinese Univ,2015,36(4):788-793(in Chinese).张欢欢,许东华,管东波,等. 双组分加成型硅橡胶交联固化过程的流变学研究[J]. 高等学校化学学报,2015,36(4):788-793.[21] ZHANG Huanhuan,XU Donghua,GUAN Dongbo,et al. Rheological Properties of Two-Component Silicon Rubber During Cross-Linking by Addition Reaction[J]. Chem J Chinese Univ,2015,36(4):788-793(in Chinese).张欢欢,许东华,管东波,等. 双组分加成型硅橡胶交联固化过程的流变学研究[J]. 高等学校化学学报,2015,36(4):788-793.
22. [22] SHI Minghui. Epoxy Resin Adhesive with High Thixotropy[J]. Adhes China,2008,29(11):19-22(in Chinese).石明辉. 高触变性环氧树脂胶粘剂的研究[J]. 粘结,2008,29(11):19-22.[22] SHI Minghui. Epoxy Resin Adhesive with High Thixotropy[J]. Adhes China,2008,29(11):19-22(in Chinese).石明辉. 高触变性环氧树脂胶粘剂的研究[J]. 粘结,2008,29(11):19-22.
23. [23] LI Jia,JI Tiezheng,CHEN Lixin. Study on Epoxy Resin Adhesive with High Temperature Curing[J]. China Adhes,2011,20(11):18-21(in Chinese).李佳,季铁正,陈立新. 高温固化环氧树脂胶粘剂的研究[J]. 中国胶粘剂,2011,20(11):18-21.[23] LI Jia,JI Tiezheng,CHEN Lixin. Study on Epoxy Resin Adhesive with High Temperature Curing[J]. China Adhes,2011,20(11):18-21(in Chinese).李佳,季铁正,陈立新. 高温固化环氧树脂胶粘剂的研究[J]. 中国胶粘剂,2011,20(11):18-21.
24. [24] Davidson E A,Janssens I A,Luo Y Q. On the Variability of Respiration in Terrestrial Ecosystems: Moving Beyond Q(10)[J]. Global Change Biol,2006,12(2):154-164.[24] Davidson E A,Janssens I A,Luo Y Q. On the Variability of Respiration in Terrestrial Ecosystems: Moving Beyond Q(10)[J]. Global Change Biol,2006,12(2):154-164.
25. [25] Nishinari K. Some Thoughts on the Definition of a Gel [J]. Prog Colloid Polym Sci,2009,136:87-94.[25] Nishinari K. Some Thoughts on the Definition of a Gel [J]. Prog Colloid Polym Sci,2009,136:87-94.
26. [26] Dela Caba K,Guerrero P,Eceiza A,et al. Kinetic and Rheological Studies of an Unsaturated Polyester Cured with Different Catalyst Amounts[J]. Polymer,1996,37(2):275-280.[26] Dela Caba K,Guerrero P,Eceiza A,et al. Kinetic and Rheological Studies of an Unsaturated Polyester Cured with Different Catalyst Amounts[J]. Polymer,1996,37(2):275-280.
27. [27] Boey F Y C,Song X L,Yue C Y,et al. Modeling the Curing Kinetics for a Modified Bismaleimide Resin[J]. J Polym Sci,Part A:Polym Chem,2000,38(5):907-913.[27] Boey F Y C,Song X L,Yue C Y,et al. Modeling the Curing Kinetics for a Modified Bismaleimide Resin[J]. J Polym Sci,Part A:Polym Chem,2000,38(5):907-913.
28. [28] Martin J S,Laza J M,Morr s M L,et al. Study of the Curing Process of a Vinyl Ester Resin by Means fo TSR and DMTA[J]. Polymer,2000,41(11):4203-4211.[28] Martin J S,Laza J M,Morr s M L,et al. Study of the Curing Process of a Vinyl Ester Resin by Means fo TSR and DMTA[J]. Polymer,2000,41(11):4203-4211.
29. [29] Djabourov M,Leblond J,Papon P. Gelation of Aqueous Gelatin Solutions.Ⅰ.Structural Investigation[J]. J Phys France,1988,49(2):319-332.[29] Djabourov M,Leblond J,Papon P. Gelation of Aqueous Gelatin Solutions.Ⅰ.Structural Investigation[J]. J Phys France,1988,49(2):319-332.
30. [30] Turi E A. Thermal Characterization of Polymeric Materials[M]. Vol. 2. New York:Academic Press,1998:1382-1451.[30] Turi E A. Thermal Characterization of Polymeric Materials[M]. Vol. 2. New York:Academic Press,1998:1382-1451.

扫一扫看文章

计量

PDF下载量: 0
文章访问数: 1119
HTML全文浏览量: 93

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

不同温度下环氧树脂代木搪塑模具的固化过程

English

The Curing Process of Epoxy Resin Tooling Board for Slush Mold at Different Temperature

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

不同温度下环氧树脂代木搪塑模具的固化过程

English

The Curing Process of Epoxy Resin Tooling Board for Slush Mold at Different Temperature

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs