SiO<sub>2</sub>-苯并噁嗪/双马来酰亚胺树脂的固化反应动力学

贾园; 杨菊香; 曾莎; 刘振

doi:10.13801/j.cnki.fhclxb.20200630.001

SiO₂-苯并噁嗪/双马来酰亚胺树脂的固化反应动力学

doi: 10.13801/j.cnki.fhclxb.20200630.001

西安文理学院　化学工程学院陕西省表面工程与再制造重点实验室，西安 710065

基金项目: 西安市科技计划项目(2020KJWL18)；国家级大学生创新创业项目(201911080012)

详细信息

通讯作者:
贾园，博士，讲师，研究方向为功能高分子材料的制备及改性　E-mail：jiayu_an_happy@126.com

中图分类号: O631；TQ320.1
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出版历程
- 收稿日期: 2020-04-30
- 录用日期: 2020-06-28
- 网络出版日期: 2020-06-30
- 刊出日期: 2021-02-15

Curing reaction kinetics on SiO₂ contained benzoxazine/bismaleimide composites system

The Key Laboratory for Surface Engineering and Remanufacturing in Shanxi Province, College of Chemical Engineering, Xi’an University, Xi’an 710065, China

摘要

摘要: 为改善双马来酰亚胺树脂(BMI)脆性过大、耐热性不足的缺点，以末端含有氨基的纳米SiO₂(SiO₂-NH₂)为原料，通过溶剂法制备出结构中含有SiO₂的苯并噁嗪树脂单体(SiO₂-BOZ)，作为改性体系加入到BMI中进行共混，制备出一种耐热性能、韧性良好的新型SiO₂-BOZ/BMI树脂材料，并详细研究了SiO₂-NH₂的添加对BMI固化反应动力学的影响。结果表明，当SiO₂-BOZ添加量达到15.0wt%时，SiO₂-BOZ/BMI树脂复合材料的表观活化能较纯BMI树脂得到了一定程度的降低，SiO₂-BOZ/BMI的弯曲强度达到最大值166.12 MPa，较纯BMI 增加了32.3%，且具有比BMI更好的耐热性能。
- 双马来酰亚胺树脂 /
- 苯并噁嗪 /
- 固化反应动力学 /
- 力学性能 /
- 耐热性能
Abstract: To overcome the excessive brittleness and lower thermal resistant of bismaleimide resins, the silicon dioxide with amino terminal groups (SiO₂-NH₂) was chosen as raw materials to prepare benzoxazine monomer containing SiO₂ (SiO₂-BOZ). The SiO₂-BOZ was then used as the modified system to modify bismaleimide (BMI), aiming to obtain a kind of new SiO₂-BOZ/BMI composites with better processability and heat-resistant properties, while the influence of addition of SiO₂-BOZ on curing reaction kinetics of BMI was also studied. The results show that when the content of SiO₂-BOZ reaches 15.0wt%, the apparent activation energy of SiO₂-BOZ/BMI resin is reduced to a certain extent compared with that of pure BMI resin, and the bending strength of SiO₂-BOZ/BMI reaches a maximum of 166.12 MPa, which is 32.3% higher than that of pure BMI, the SiO₂-BOZ/BMI also possesses better heat resistance than that of BMI.
- bismaleimide /
- benzoxazine /
- curing reaction kinetics /
- mechanical properties /
- thermal resistant

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图 1 含SiO₂的苯并噁嗪单体(SiO₂-BOZ)的制备反应式

Figure 1. Reaction of benzoxazine monomer containing SiO₂ (SiO₂-BOZ)

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图 2 SiO₂-BOZ的FTIR图谱

Figure 2. FTIR spectra of SiO₂-BOZ

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图 3 SiO₂-BOZ/双马来酰亚胺树脂(BMI)的FTIR图谱

Figure 3. FTIR spectra of SiO₂-BOZ/bismaleimide resin (BMI)

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图 4 BMI与SiO₂-BOZ/BMI体系的凝胶时间-温度关系

Figure 4. Relationship between gelation time and temperature of BMI and SiO₂-BOZ/BMI resin

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图 5 BMI与SiO₂-BOZ/BMI体系的黏度-温度关系

Figure 5. Relationship between viscosity and temperature of BMI and SiO₂-BOZ/BMI resin

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图 6 BMI和15.0wt%SiO₂-BOZ/BMI体系在不同升温速率下的DSC曲线

Figure 6. DSC curves of BMI and 15.0wt%SiO₂-BOZ/BMI resin at different temperature increasing rates

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图 7 BMI和15.0wt%SiO₂-BOZ/BMI树脂峰值温度的线性回归直线

Figure 7. Linear regression curves of peak temperature on DSC curves of BMI and 15.0wt%SiO₂-BOZ/BMI

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图 8 BMI和15.0wt%SiO₂-BOZ/BMI树脂体系中 −ln(β/T_m²)与1/T_m的线性关系

Figure 8. Linear regression curves of −ln(β/T_m²) and 1/T_m of BMI and 15.0wt%SiO₂-BOZ/BMI

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图 9 BMI和15.0wt%SiO₂-BOZ/BMI树脂中lnβ与1/T_m的线性关系

Figure 9. Linear regression curves of lnβ and 1/T_mof BMI and 15.0wt%SiO₂-BOZ/BMI

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图 10 SiO₂-BOZ含量对SiO₂-BOZ/BMI树脂弯曲强度的影响

Figure 10. Flexural strength of SiO₂-BOZ/BMI rein with different contents of SiO₂-BOZ

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图 11 BMI和SiO₂-BOZ含量为15wt%的SiO₂-BOZ/BMI树脂的TGA曲线

Figure 11. TGA curves of the BMI and SiO₂-BOZ/BMI composites with 15.0wt%SiO₂-BOZ

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表 1 不同升温速率下BMI的DSC固化曲线上放热峰的峰值温度

Table 1. Peak temperature on DSC curves of BMI at different temperature increasing rates

Heating rate/(℃·min⁻¹)	5	10	15
T_i/℃	175.74	203.76	212.85
T_m/℃	250.67	270.33	280.07
T_f/℃	294.82	310.89	345.27
Notes: T_i—Temperature of onset; T_m—Temperature of peak; T_f—Temperature of ending.

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表 2 不同升温速率下SiO₂-BOZ/BMI的DSC固化曲线上放热峰的峰值温度

Table 2. Peak temperature on DSC curves of SiO₂-BOZ/BMI at different temperature increasing rates

Heating rate/(℃·min⁻¹)	5	10	15
T_i/℃	197.96	207.47	210.93
T_m/℃	238.65	258.59	271.99
T_f/℃	291.89	306.28	311.38

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参考文献(22)

[1]	JIA Y, YAN H X, LI S, et al. Tribology property of benzoxazine-bismaleimide composites with hyperbranched polysilane-grafted multi-walled carbon Nanotubes[J]. Nano,2016,11(6):1650061. doi: 10.1142/S1793292016500612
[2]	陈宇飞, 武耘仲, 代国庆, 等. SiO₂包覆石墨烯/双马来酰亚胺复合材料的表征及性能[J]. 复合材料学报, 2020, 37(5):1015-1023. CHEN Y F, WU G Z, DAI G Q, et al. Characterization and properties of SiO₂-coated graphene/bismaleimide compo-sites[J]. Acta Materiae Compositae Sinica,2020,37(5):1015-1023(in Chinese).
[3]	YAN H X, LI S, JIA Y, et al. Hyperbranched polysiloxane grafted graphene for improved tribological performance of bismaleimide composites[J]. RSC Advances,2015,5(17):12578-12582. doi: 10.1039/C4RA13134G
[4]	HUANG Y, JIANG M, XU M, et al. Curing behavior and processability of BMI/3-APN system for advanced glass fiber composite laminates[J]. Journal of Applied Polymer Science,2016,133:43640.
[5]	陈宇飞, 郭红缘, 耿成宝, 等. 聚醚醚酮和烯丙基化合物改性双马来酰亚胺复合材料微观结构及力学性能[J]. 复合材料学报, 2018, 35(11):3081-3087. CHEN Y F, GUO H Y, GENG C B, et al. Microstructure and mechanical properties of bismaleimide composites modified with poly(ether ether ketone) and allyl compounds[J]. Acta Materiae Compositae Sinica,2018,35(11):3081-3087(in Chinese).
[6]	SANTHOSH K K S, REGHUNADHAN N C P, SADHANA R, et al. Benzoxazine-bismaleimide blends: Curing and thermal properties[J]. European Polymer Journal,2007,43(12):5084-5096. doi: 10.1016/j.eurpolymj.2007.09.012
[7]	CHENG Q F, FANG Z P, YI X S, et al. "Ex Situ" concept for toughening the RTMable BMI matrix composites, Part I: Improving the interlaminar fracture toughness[J]. Journal of Applied Polymer Science,2008,109(3):1625-1634. doi: 10.1002/app.27868
[8]	TAKEICHI T, SAITO Y, AGAG T, et al. High-performance polymer alloys of polybenzoxazine and bismaleimide[J]. Polymer,2008,49(5):1173-1179. doi: 10.1016/j.polymer.2008.01.041
[9]	SOKOLIK V N, GIZATULLIN S F, RAIGOROSKII I M, et al. Benzoxazine siloxanes as modifiers of epoxy resins for coatings[J]. Polymer Science,2017,10:123-127.
[10]	HARIHARAN A, SRINIVASAN K, MURTHY C, et al. Synthesis and characterization of a novel class of low temperature cure Benzoxazines[J]. Journal of Polymer Research,2018,25:20. doi: 10.1007/s10965-017-1423-0
[11]	ZHANG K, ZHUANG Q, LIU X, et al. A new benzoxazine containing benzoxazole-functionalized polyhedral oligomeric silsesquioxane and the corresponding polybenzoxazine nanocomposites[J]. Macromolecules,2014,46(7):2696-2704.
[12]	ZHANG J, HUANG J, DU W, et al. Thermal stability of the copolymers of silicon-containing arylacetylene resin and acetylene-functional benzoxazine[J]. Polymer Degradation and Stability,2011,96(12):2276-2283. doi: 10.1016/j.polymdegradstab.2011.04.022
[13]	WANG Z, ZHANG S J, LU Z J. Sulfonic acid-containing benzoxazine surfactant and its waterborne benzoxaizne resins[J]. European Polymer Journal, 2020, 141: 110086-110092.
[14]	AGAG T, JIN L, ISHIDA H. A new synthetic approach for difficult benzoxazine: Preparation and polymerization of 4, 4-diaminodiphenyl sulfone-based benzoxazine monomer[J]. Polymer,2009,50(25):5940-5944. doi: 10.1016/j.polymer.2009.06.038
[15]	WANG Y, KOU K, WU G, et al. The curing reaction of benzoxazine with bismaleimide/cyanate ester resin and the properties of the terpolymer[J]. Polymer,2015,77:354-360. doi: 10.1016/j.polymer.2015.09.059
[16]	GAO Y, HUANG F, ZHOU Y, et al. Synthesis and characterization of a novel acetylene- and maleimide-terminated benzoxazine and its high-performance thermosets[J]. Journal of Applied Polymer Science,2013,128(1):340-346. doi: 10.1002/app.38184
[17]	TAN Z W, WU X, ZHANG M, et al. Performances improvement of traditional polybenzoxazines by copolymerizing with cyclotriphosphazene-based benzoxazine monomers[J]. Polymer Bulletin,2015,72:1417-1431.
[18]	胡晓兰, 兰茜, 刘刚, 等. 苯并噁嗪树脂及其玻璃纤维增强复合材料的阻燃改性[J]. 复合材料学报, 2015, 32(6):1714-1720. HU X L, LAN Q, LIU G, et al. Flame retardant modification of benzoxazine resin and its glass fiber reinforced compo-sites[J]. Acta Materiae Compositae Sinica,2015,32(6):1714-1720(in Chinese).
[19]	任小明. 溶胶凝胶法制备纳米二氧化硅的研究[J]. 胶体与聚合物, 2017, 35(2):71-73. REN X M. Research of preparation of nano silica by sol-gel process[J]. Chinese Journal of Colloid & Polymer,2017,35(2):71-73(in Chinese).
[20]	杨成露, 晏石林, 李胜方, 等. 硅烷化氧化石墨烯/漆酚型苯并噁嗪-双马来酰亚胺共聚树脂复合材料的制备与性能[J]. 复合材料学报, 2018, 35(11):2942-2949. YANG C L, YAN S L, LI S F, et al. Preparation and properties of silaned graphene oxide/urushiol based benzoxazine-bismaleimide copolymer resin composites[J]. Acta Materiae Compositae Sinica,2018,35(11):2942-2949(in Chinese).
[21]	张明, 安学锋, 唐邦铭, 等. 高性能双组份环氧树脂固化动力学研究和TTT图绘制[J]. 复合材料学报, 2006, 23(1):17-25. doi: 10.3321/j.issn:1000-3851.2006.01.003 ZHANG M, AN X F, TANG B M, et al. Cure kinetics and TTT-diagram of a bicomponent high performance epoxy resin for advanced composites[J]. Acta Materiae Compositae Sinica,2006,23(1):17-25(in Chinese). doi: 10.3321/j.issn:1000-3851.2006.01.003
[22]	中国国家标准化管理委员会. 树脂浇铸体性能试验方法: GB/T 2567—2008[S]. 北京: 中国标准出版社, 2008. Standardization Administration of China. Test methods for properties of resin castings: GB/T 2567—2008[S]. Beijing: China Standard Press, 2008(in Chinese).