双马来酰亚胺工艺改性及性能

周浩然; 荆佳奇; 王德志; 范旭鹏; 袁镇; 赵立伟

doi:10.13801/j.cnki.fhclxb.20191021.003

双马来酰亚胺工艺改性及性能

doi: 10.13801/j.cnki.fhclxb.20191021.003

周浩然¹,
荆佳奇¹,
王德志^{1, 2, ,},
范旭鹏¹,
袁镇¹,
赵立伟²

1.
哈尔滨理工大学　材料科学与工程学院，哈尔滨 150040
2.
黑龙江省科学院石油化学研究院，哈尔滨 150040

基金项目: 黑龙江省自然科学基金(JC2017015)；国家自然科学基金(51677045)

详细信息

通讯作者:
王德志，博士，研究员，硕士生导师，研究方向为高分子胶黏剂和基体树脂　E-mail：jim603@163.com

中图分类号: TQ323.7
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- 被引次数: 0
出版历程
- 收稿日期: 2019-07-05
- 录用日期: 2019-09-10
- 网络出版日期: 2019-10-30
- 刊出日期: 2020-06-15

Process modification and properties analysis of bismaleimide

1.
School of Materials Science and Engineering, Harbin University of Science and Technology, Harbin 150040, China
2.
Institute of Petrochemisty, Heilongjiang Academy of Sciences, Harbin 150040, China

摘要

摘要: 采用脂肪族双马来酰亚胺(HMDA-BMI)对4,4’-二苯甲烷型双马来酰亚胺(BDM)进行工艺改性，得到了一种低黏度、流动性好的基体树脂。当HMDA-BMI与BDM的摩尔比为1: 1时，黏度-温度曲线表明改性体系黏度可降低至0.50 Pa·s左右，低黏度平台的温度区间为85~175℃之间；黏度-时间曲线表明改性体系合适的充模温度为130~145℃，获得的改性基体树脂适合RTM成型工艺；通过DSC曲线确定了改性基体树脂固化工艺为160℃×2 h＋180℃×2 h＋200℃×2 h＋230℃×4 h；FTIR表明改性体系按照此工艺可以固化完全；DMA曲线和TG曲线分析结果表明改性体系的耐热性基本保持不变；共聚改性体系的拉伸强度和弯曲强度分别为80.1 MPa和116 MPa。
- 双马来酰亚胺 /
- 共聚 /
- 加工性 /
- 流变性能 /
- 改性
Abstract: Aliphatic bismaleimide(HMDA-BMI) was used to copolymerize with 4,4’-bismaleimide diphenylmethyene (BDM) for preparing a matrix resin with low viscosity and good processing. When the molar ratio of HMDA-BMI to BDM is 1: 1, the viscosity-temperature test result shows that the viscosity of the HMDA-BMI-BDM system can be reduced to about 0.5 Pa·s, and the temperature range of the low viscosity platform is between 85-175℃. The viscosity-time result shows that the suitable mold filling temperature of the modified system is 130-145℃, and the obtained modified matrix HMDA-BMI-BDM resin is suitable for RTM. The curing process determined by the DSC method is 160℃×2 h+180℃×2 h+200℃×2 h+230℃×4 h. FTIR result shows that the modified system can be completely cured according to this process.The results of DMA and TG analysis show that the heat resistance of the modified system remains basically unchanged. The tensile strength and flexural strength of the modified system reaches 80.1 MPa and 116 MPa, respectively.
- aliphatic bismaleimide /
- copolymerization /
- processability /
- rheological property /
- modification

HTML全文

图 1 4,4’-二苯甲烷型双马来酰亚胺(BDM)、脂肪族双马来酰亚胺(HMDA-BMI)和双烯丙基双酚A(DP)分子结构式

Figure 1. Molecular structures of 4,4’-bismaleimide diphenylmethyene (BDM), aliphatic bismaleimide(HMDA-BMI) and diallyl bisphenol A(DP)

下载: 全尺寸图片幻灯片

图 2 改性共聚体系的黏度-温度曲线和黏度-时间曲线

Figure 2. Viscosity-temperature curves and viscosity-time curves of the modified blend systems

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图 3 DP-BDM、HMDA-BMI-DP-BDM和DP-HMDA-BMI改性共聚体系的DSC曲线

Figure 3. DSC curves of DP-BDM, HMDA-BMI-DP-BDM and DP-HMDA-BMI blend systems

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图 4 HMDA-BMI-DP-BDM 改性共聚体系的T_i-β、T_p-β和T_f-β线性拟合

Figure 4. Linear fitting of T_i-β, T_p-β and T_f-β of HMDA-BMI-DP-BDM blend system

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图 5 HMDA-BMI-DP-BDM共聚体系固化前后的FTIR图谱

Figure 5. FTIR spectra before and after curing of HMDA-BMI-DP-BDM copolymerization system

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图 6 不同共聚体系的TG、DTG和DMA曲线

Figure 6. TG, DTG and DMA curves of different copolymerizaion system

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图 7 不同共聚体系的拉伸强度、拉伸模量及弯曲强度和弯曲模量

Figure 7. Tensile strength, tensile modulus and bending strength, bending modulus of different copolymerization systems

下载: 全尺寸图片幻灯片

表 1 不同共聚体系摩尔比

Table 1. Mole ratios of different copolymerization systems

Cololymerization system	BDM/mol	HMDA-BMI/mol	DP/mol
DP-BDM	1	0	0.87
HMDA-BMI-DP-BDM	0.5	0.5	0.87
DP-HMDA-BMI	0	1	0.87

下载: 导出CSV

表 2 HMDA-BMI-DP-BDM 体系不同升温速率下特征峰温度

Table 2. Characteristic peak temperatures at different heating rates of HMDA-BMI-DP-BDM system

β/(℃·min⁻¹)	T_i/℃	T_p/℃	T_f/℃
5	214	248	286
10	226	262	300
15	235	274	311
20	247	284	328
Notes: β—Temperature rate; T_i—Onset temperature; T_p—Peak temperature; T_f—End temperature.

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