潜伏型环氧固化剂甲基异丁基酮二亚胺的合成及工艺优化

doi:10.11949/0438-1157.20210208

化工学报 ›› 2021, Vol. 72 ›› Issue (7): 3832-3838.doi: 10.11949/0438-1157.20210208

• 材料化学工程与纳米技术 • 上一篇下一篇

潜伏型环氧固化剂甲基异丁基酮二亚胺的合成及工艺优化

韩维辰¹(),王佳铭¹,贺曼罗²,贺高红¹,焉晓明¹,阮雪华¹()

^1.大连理工大学化工学院盘锦分院，辽宁盘锦 124221
^2.中国科学院大连化学物理研究所，辽宁大连 116023

收稿日期:2021-02-03 修回日期:2021-04-19 出版日期:2021-07-05 发布日期:2021-07-05
通讯作者: 阮雪华 E-mail:379081783@qq.com;xuehuaruan@dlut.edu.cn
作者简介:韩维辰(1995—)，男，硕士研究生，379081783@qq.com
基金资助:
国家自然科学基金项目(21978033);中国博士后科学基金项目(2019M650055);兴辽英才计划项目(XLYC1907063)

Process optimization for synthesizing latent epoxy curing agent based on methyl isobutyl ketone and m-xylylenediamine

HAN Weichen¹(),WANG Jiaming¹,HE Manluo²,HE Gaohong¹,YAN Xiaoming¹,RUAN Xuehua¹()

^1.School of Chemical Engineering at Panjin Campus, Dalian University of Technology, Panjin 124221, Liaoning, China
^2.Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2021-02-03 Revised:2021-04-19 Published:2021-07-05 Online:2021-07-05
Contact: RUAN Xuehua E-mail:379081783@qq.com;xuehuaruan@dlut.edu.cn

摘要/Abstract

摘要：

间苯二甲胺（MXDA）与甲基异丁基酮（MIBK）合成的甲基异丁基酮二亚胺（MIBKDI），是单组分环氧胶常用的潜伏型固化剂。反应残余的MXDA，可直接与环氧树脂发生交联，显著降低储存稳定性。工业生产通过超高酮胺比使MXDA充分转化，但MIBK损失大、回收能耗高。本研究首先采用正交实验对反应温度、时间和酮胺比进行权重分析和因素效应分析，然后通过单因素实验系统研究反应时间、酮胺比对MXDA转化率的影响。结果表明，酮胺摩尔比超过5∶1（反应温度170℃、时间4 h）制备的固化剂，储存稳定性满足市场需求。在典型条件下，环氧树脂完全固化后剪切强度12.9 MPa，拉伸强度19.2 MPa，达到国家标准GB/T 2567—2008要求。与工业方案相比，酮胺比优化为5∶1以后，能耗大大降低，同时MIBK消耗有效节约，总成本得到客观降低。

关键词: 甲基异丁基酮, 间苯二甲胺, 潜伏型固化剂, 环氧树脂, 储存稳定性, 优化

Abstract:

The di-imine matter synthesized from methyl isobutyl ketone(MIBK) and m-xylylenediamine (MXDA), abbreviated as MIBKDI, is a frequently-utilized latent curing agent for one-component epoxy adhesive. The remained MXDA in the curing agent, due to its direct cross-linking with epoxy resin, would significantly impair epoxy_{adhesive's stability in storage. In industrial synthesis processes, ultrahigh molar proportion between MIBK and MXDA (>10∶1) is applied to enhance MXDA conversion as much as possible; nevertheless, MIBK loss and energy consumption for its recovery would result in extensive cost. In this research, the orthogonal experiments were used at first to make weight analysis and factorial effect analysis for reaction temperature, time and reagent ratio; and the single-factor experiments were carried through systematically to investigate the effects of reaction time and reagent ratio on MXDA conversion ratio. It is resulted that the epoxy adhesives could be stable enough for sale with the curing agent synthesized with the MIBK/MXDA molar ratio higher than 5∶1, while the reaction was sustained for 4 h under 170℃. Under the typical condition for adhesion, the cured epoxy resin behaved excellent with shear strength up to 12.9 MPa and tensile strength equal to 19.2 MPa, which can meet the demand defined in National Standard GB/T 2567—2008. When the MIBK/MXDA molar ratio was optimized to be 5∶1 for curing agent synthesis, energy consumption is greatly reduced, while MIBK consumption is effectively saved, and the total cost is reduced considerably.}

Key words: methyl isobutyl ketone, m-xylylenediamine, latent curing agent, epoxy adhesive, storage stability, optimization

中图分类号:

TQ 433.4

韩维辰, 王佳铭, 贺曼罗, 贺高红, 焉晓明, 阮雪华. 潜伏型环氧固化剂甲基异丁基酮二亚胺的合成及工艺优化[J]. 化工学报, 2021, 72(7): 3832-3838.

HAN Weichen, WANG Jiaming, HE Manluo, HE Gaohong, YAN Xiaoming, RUAN Xuehua. Process optimization for synthesizing latent epoxy curing agent based on methyl isobutyl ketone and m-xylylenediamine[J]. CIESC Journal, 2021, 72(7): 3832-3838.

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参考文献 31

1	贺曼罗, 王文军, 贺湘凌. 建筑结构胶黏剂与施工应用技术[M]. 2版. 北京: 化学工业出版社, 2016: 1-9.
	He M L, Wang W J, He X L. Construction Structural Epoxy Adhesive and Application Technology[M]. 2nd ed. Beijing: Chemical Industry Press, 2016: 1-9.
2	Jin F L, Li X, Park S J. Synthesis and application of epoxy resins: a review[J]. Journal of Industrial and Engineering Chemistry, 2015, 29: 1-11.
3	刘佳欣. 室温固化单组分建筑结构胶的制备与性能研究[D]. 大连: 大连理工大学, 2012.
	Liu J X. Preparation and characterization of room temperature curing one-component construction structural epoxy adhesive[D]. Dalian: Dalian University of Technology, 2012.
4	王权, 史铁钧, 张焱, 等. 聚双胍/环氧树脂体系潜伏性固化过程[J]. 化工学报, 2015, 66(1): 464-470.
	Wang Q, Shi T J, Zhang Y, et al. Latent curing of polybiguanide/epoxy resin[J]. CIESC Journal, 2015, 66(1): 464-470.
5	周红军, 尹国强, 林轩, 等. 环氧树脂/活化纳米氧化铝复合材料的固化动力学[J]. 化工学报, 2011, 62(6): 1749-1755.
	Zhou H J, Yin G Q, Lin X, et al. Curing kinetics of epoxy/activated nano-Al₂O₃ composites[J]. CIESC Journal, 2011, 62(6): 1749-1755.
6	Okuhira H, Kii T, Ochi M, et al. Novel moisture-curable epoxy resins and their characterization[J]. Journal of Applied Polymer Science, 2003, 89(1): 91-95.
7	Li B M, Wang X L, Bai M D, et al. Improvement of curing reaction activity of one-component room temperature-curable epoxy adhesive by the addition of functionalized graphene oxide[J]. International Journal of Adhesion and Adhesives, 2020, 98: 102537.
8	Zubkova Z A, Stetsyuk M F, Georgitsa T A. Modified amine curing agents of epoxy resins and materials on their basis[J]. Polymer Science, Series D, 2010, 3(3): 177-180.
9	George N, Bindu Sharmila T K, Kurian T. Preparation of a one-component epoxy adhesive using PET bottle waste derived terephthalic dihydrazide as latent curing agent[J]. International Journal of Adhesion and Adhesives, 2020, 98: 102524.
10	Wang Y R, Liu W S, Qiu Y P, et al. A one-component, fast-cure, and economical epoxy resin system suitable for liquid molding of automotive composite parts[J]. Materials, 2018, 11(5): E685.
11	Okuhira H, Iwamoto N, Ochi M, et al. Novel urethane/epoxy resin hybrid materials using a moisture-curing system[J]. Journal of Polymer Science Part B: Polymer Physics, 2004, 42(7): 1137-1144.
12	Okuhira H, Kii T, Ochi M, et al. Characterization of epoxy resin hardening with ketimine latent hardeners[J]. Journal of Adhesion Science and Technology, 2004, 18(2): 205-211.
13	虞静远, 虞鑫海, 刘万章, 等. 单组分环氧胶黏剂的研究现状[J]. 黏接, 2013, 34(9): 57-59, 63.
	Yu J Y, Yu X H, Liu W Z, et al. Current research status of one component epoxy resin adhesives[J]. Adhesion, 2013, 34(9): 57-59, 63.
14	Sathiyanarayanan S, Maruthan K, Muthukrishnan S, et al. High performance polyaniline containing coating system for wet surfaces[J]. Progress in Organic Coatings, 2009, 66(2): 113-117.
15	Yang C P, Lee L T. Synthesis and properties of polyamine resins from epoxy resins[J]. Journal of Polymer Science Part A: Polymer Chemistry, 1990, 28(7): 1861-1874.
16	Suzuki K, Matsu-Ura N, Horii H, et al. Reaction of glycidyl phenyl ether with imines: a model study of latent hardeners of epoxy resins in the presence of water[J]. Journal of Polymer Science Part A: Polymer Chemistry, 2002, 40(8): 971-975.
17	Elmore J D, Kincaid D S, Komar P C, et al. Waterborne epoxy protective coatings for metal[J]. Journal of Coatings Technology, 2002, 74(931): 63-72.
18	Constantinoiu C C, Molloy J B, Jorgensen W K, et al. Purification of immunoglobulins from chicken sera by thiophilic gel chromatography[J]. Poultry Science, 2007, 86(9): 1910-1914.
19	Pradhan S, Pandey P, Mohanty S, et al. Insight on the chemistry of epoxy and its curing for coating applications: a detailed investigation and future perspectives[J]. Polymer-Plastics Technology and Engineering, 2016, 55(8): 862-877.
20	Blass D, Kreling S, Dilger K. The impact of prepreg aging on its processability and the postcure mechanical properties of epoxy-based carbon-fiber reinforced plastics[J]. Proceedings of the Institution of Mechanical Engineers, Part L: Journal of Materials: Design and Applications, 2017, 231(1/2): 62-72.
21	Xin Y, Yuan J Y. Schiff's base as a stimuli-responsive linker in polymer chemistry[J]. Polymer Chemistry, 2012, 3(11): 3045.
22	Liu X L, Liu Y H, Shi Y C, et al. Application of Schiff's bases in organic synthesis[J]. Chinese Journal of Organic Chemistry, 2002, 22(7): 482-488.
23	武田敏充, 奥平浩之, 足立直也, 等. 室温固化单组分环氧胶粘剂[J]. 粘接, 2001, 22(3): 28-30.
	Toshimitsu T, Hiroyuki O, Naoya A, et al. Room temperature curing one-component epoxy adhesive [J]. Adhesion, 2001, 22(3): 28-30.
24	吴志胤. 室温快速固化单组分环氧胶的研究[D]. 福州: 福州大学, 2017.
	Wu Z Y. Study of fast curing one-component epoxy adhesive at room temperature[D]. Fuzhou: Fuzhou University, 2017.
25	贺曼罗, 刘佳欣, 任延煜. 单组分室温固化环氧建筑胶粘剂的研究动向[J]. 粘接, 2013, 34(10): 37-39.
	He M L, Liu J X, Ren Y Y. Research trend of one-component room temperature curable epoxy building adhesives[J]. Adhesion, 2013, 34(10): 37-39.
26	中华人民共和国国家质量监督检验检疫总局, 中国国家标准化管理委员会.树脂浇铸体性能试验方法: [S]. 北京: 中国标准出版社, 2008.
	General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China, Standardization Administration of the People's Republic of China. Test methods for properties of resin casting boby: [S]. Beijing: Standards Press of China, 2008.
27	胡玲玲, 吴雅红, 余坚, 等. 微波合成席夫碱[J]. 现代化工, 2012, 32(9): 59-61.
	Hu L L, Wu Y H, Yu J, et al. Synthesis of polyschiff base under microwave irradiation[J]. Modern Chemical Industry, 2012, 32(9): 59-61.
28	Kamura M, Kuzumoto Y, Aomori S, et al. Synthesis and investigation of π-conjugated azomethine self-assembled multilayers by layer-by-layer growth[J]. Thin Solid Films, 2010, 518(18): 5115-5120.
29	Cordes E H, Jencks W P. On the mechanism of Schiff base formation and hydrolysis[J]. Journal of the American Chemical Society, 1962, 84(5): 832-837.
30	Cozzi P G. Metal-salen Schiff base complexes in catalysis: practical aspects[J]. Chemical Society Reviews, 2004, 33(7): 410-421.
31	Borisova N E, Reshetova M D, Ustynyuk Y A. Metal-free methods in the synthesis of macrocyclic Schiff bases[J]. Chemical Reviews, 2007, 107(1): 46-79.

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Experiment	A T/°C	B θ/ h	C MIBK∶MXDA	Conversion/%
P-1	140	1	2∶1	20
P-2	140	2	3∶1	32
P-3	140	3	4∶1	48
P-4	140	4	5∶1	64
P-5	140	5	6∶1	78
P-6	150	1	3∶1	30
P-7	150	2	4∶1	52
P-8	150	3	5∶1	72
P-9	150	4	6∶1	83
P-10	150	5	2∶1	40
P-11	160	1	4∶1	40
P-12	160	2	5∶1	62
P-13	160	3	6∶1	85
P-14	160	4	2∶1	42
P-15	160	5	3∶1	58
P-16	170	1	5∶1	56
P-17	170	2	6∶1	67
P-18	170	3	2∶1	48
P-19	170	4	3∶1	65
P-20	170	5	4∶1	83
P-21	180	1	6∶1	37
P-22	180	2	2∶1	32
P-23	180	3	3∶1	55
P-24	180	4	4∶1	67
P-25	180	5	5∶1	85

因素效应	A T/°C	B θ/ h	C MIBK∶MXDA
k₁/%	48.4	36.6	36.4
k₂/%	55.4	50.6	48.0
k₃/%	59.0	61.6	58.0
k₄/%	63.8	64.2	69.4
k₅/%	55.2	68.8	70.0
F	0.24	1.23	1.53
optimum group	A₄	B₅	C₅

Sample	MIBK∶MXDA	Reaction time/h	MXDA/ %(mass)	MIBK/ %(mass)	MIBKDI/ %(mass)	Amine value
S-1	4∶1	5	10.0	1.0	89.0	327
S-2	5∶1	4	4.1	0.8	95.1	283
S-3	5∶1	5	1.9	0.9	97.2	279
S-4	6∶1	4	2.2	0.8	97.0	275
S-5	6∶1	5	1.1	0.8	98.1	273
S-6	10∶1	5	0.4	0.6	99.0	271

Synthesis condition		Distillation/ h	Material consumption			Energy consumption		Total cost/ CNY
MIBK∶MXDA	Time/h	Distillation/ h	MXDA/g	MIBK/g	Cost/CNY	Power/kWh	Cost/CNY	Total cost/ CNY
5∶1	4	2.0	480	910	54.3	17.5	14.0	68.3
6∶1	4	2.5	470	960	54.4	21.0	16.8	71.2
10∶1	5	4.0	460	1210	58.0	34.5	27.6	85.6

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潜伏型环氧固化剂甲基异丁基酮二亚胺的合成及工艺优化

Process optimization for synthesizing latent epoxy curing agent based on methyl isobutyl ketone and m-xylylenediamine

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