表面修饰纳米晶纤维素及其在双马来酰亚胺树脂中的应用

巩桂芬; 邢韵; 李泽; 辛浩; 曹景飞; 罗艳梅

doi:10.13801/j.cnki.fhclxb.20191104.001

表面修饰纳米晶纤维素及其在双马来酰亚胺树脂中的应用

doi: 10.13801/j.cnki.fhclxb.20191104.001

哈尔滨理工大学　材料科学与工程学院，哈尔滨 150040

基金项目: 国家自然科学基金(51372128)

详细信息

通讯作者:
巩桂芬，博士，教授，研究方向为纳米纤维素复合材料　E-mail：ggf-hust@163.com

中图分类号: TB332；O636
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- 被引次数: 0
出版历程
- 收稿日期: 2019-07-20
- 录用日期: 2019-09-30
- 网络出版日期: 2019-11-04
- 刊出日期: 2020-06-15

Surface modification of nano crystalline cellulose and application in bismaleimide resin

College of Material Science and Engineering, Harbin University of Science and Technology, Harbin 150040, China

摘要

摘要: 采用硫酸水解法制备了纳米晶纤维素(NCC)，以N,N-羰基二咪唑(CDI)为活化剂，甲代烯丙基醇(MPO)为改性剂，通过化学取代得到含有烯丙基碳酸酯的纳米晶纤维素(PCNCC)；以4,4′-二氨基二苯甲烷双马来酰亚胺(MBMI)、3,3′-二烯丙基双酚A(BBA)及双酚A双烯丙基醚(BBE)为原料制备了复合材料基体(MBAE)。采用FTIR、XRD、TEM和碘值法等对化学修饰的产物进行分析和表征。结果表明，当PCNCC中烯丙基碳酸酯的取代率为16.4%时，既能保持晶型不变，同时能在BBE中稳定悬浮；PCNCC中烯丙基碳酸酯的取代率过小或过大时均不适宜用作PCNCC/MBAE复合材料的增强相。利用原位聚合法将PCNCC掺杂在MBAE基体中制备PCNCC/MBAE复合材料，考察PCNCC质量分数对PCNCC/MBAE复合材料力学性能、介电性能及热性能的影响规律。结果显示，当PCNCC质量分数为0.2 wt%时，PCNCC/MBAE复合材料的弯曲强度和弯曲模量分别为148.1 MPa和6 GPa，较MBAE基体分别提高了50.5%和82.9%；冲击强度为13.9 kJ/m²，较MBAE基体提高54.8%；玻璃化转变温度T_g由纯MBAE的240.4℃提高到257.8℃。此时PCNCC/MBAE复合材料的介电常数明显提高，而介电损耗达到最低值。为扩展纳米晶纤维素及双马来酰亚胺树脂的应用提供了理论依据。
- 纳米晶纤维素 /
- 化学改性 /
- 4,4′-二氨基二苯甲烷双马来酰亚胺(MBMI) /
- 复合材料 /
- 性能
Abstract: The nano crystalline cellulose (NCC) was prepared through a sulfuric acid hydrolysis process, Then NCC was chemically modified with N, N-carbonyldiimidazole (CDI) and 2-Methyl-2-propen-1-ol (MPO) to obtain propenyl carbonate NCC (PCNCC). 4,4′-diamino diphenyl methane bismaleimide (MBMI), 3,3′-diallyl bisphenol A (BBA) and bisphenol-A diallyl ether (BBE) were used to synthesize MBMI-BBA-BBE (MBAE) matrix. The modification results were characterized by FTIR, XRD, TEM and iodine value method. When the replacement rate of PCNCC is 16.4%, the modified PCNCC preserve their type and high degree of crystallization, The PCNCC stably suspend in BBE; PCNCC with too low or too high replacement rate are not suitable for fillers in PCNCC/MBAE composites. The PCNCC/MBAE composites were prepared by doing PCNCC in an MBAE matrix by in-situ polymerization. The effects of modified PCNCC mass fraction on the mechanic properties, dielectric properties and thermal properties of PCNCC/MBAE composites were investigated. A strong interaction is observed between the PCNCC and MBAE, When the mass fraction of PCNCC is 0.2 wt%, the flexural strength and modulus of PCNCC/MBAE composite are 148.1 MPa and 6 GPa, increased by 50.5% and 82.9% than that of MBAE matrix. The impact strength of PCNCC/MBAE composite is 13.9 kJ/m², increased by 54.8% than that of MBAE matrix, respectively. The glass transition temperature T_g value from 240.4℃ of the pure MBAE to 257.8℃. The dielectric constant of PCNCC/MBAE composite increases and the dielectric loss reaches the lowest value. The improvement of mechanical properties and thermal stability of PCNCC/MBAE composites provides theoretical data for the expansion of nano cystalline cellulose and bismaleimide resin applications.
- nano crystalline cellulose /
- modification /
- 4,4′-diamino diphenyl methane bismaleimide(MBMI) /
- composites /
- properties

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图 1 测试烯丙基碳酸酯纳米晶纤维素(PCNCC)取代率的反应原理

Figure 1. Reaction mechanism of testing propenyl carbonate nano crystalline cellulose(PCNCC) replacement rate

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图 2 PCNCC的合成

Figure 2. Synthesis of PCNCC

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图 3 PCNCC/MBAE复合材料反应原理

Figure 3. Reaction mechanism of PCNCC/MBAE composite

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图 4 NCC和PCNCC的FTIR图谱

Figure 4. FTIR spectra of NCC and PCNCC

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图 5 NCC和PCNCC的XRD图谱

Figure 5. XRD patterns of NCC and PCNCC

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图 6 NCC和PCNCC的TEM图像

Figure 6. TEM images of NCC and PCNCC

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图 7 NCC和PCNCC的分散性

Figure 7. Dispersibility of NCC and PCNCC

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图 8 MBAE和PCNCC/MBAE复合材料的FTIR图谱

Figure 8. FTIR spectra of MBAE and PCNCC/MBAE composites

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图 9 MBAE和PCNCC/MBAE复合材料的SEM图像

Figure 9. SEM images of MBAE and PCNCC/MBAE composites

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图 10 PCNCC/MBAE复合材料力学性能

Figure 10. Mechanic properties of PCNCC/MBAE composites

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图 11 PCNCC不同质量分数的PCNCC/MBAE复合材料介电性能

Figure 11. Dielectric properties of PCNCC/MBAE composites with diffierent PCNCC mass fractions

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图 12 PCNCC/MBAE复合材料DMA曲线

Figure 12. DMA curve of PCNCC/MBAE composites

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表 1 PCNCC/MBAE复合材料样品组分

Table 1. Component of PCNCC/MBAE composite samples

Component	Mass fraction of PCNCC/wt%
MBAE	0
PCNCC/MBAE	0.1−0.5
Note: MBAE—4,4′-diamino diphenyl methane bismaleimide (MBMI)-3,3′-diallyl bisphenol A (BBA)-bisphenol-A diallyl ether (BBE) matrix.

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表 2 PCNCC样品的取代率

Table 2. Replacement rates of PCNCC samples

Sample	PCNCC-A	PCNCC-B	PCNCC-C	PCNCC-D	PCNCC-E
NCC∶CDI∶MPO mole ratio	1∶1.5∶1.5	1∶1.5∶1.5	1∶3∶1.5	1∶3∶1.5	1∶3∶3
Temperature/℃	25	50	50	50	65
Time/h	6	6	6	12	12
Replacement rate/%	0.3	7.5	16.4	38.9	41.3
Notes：NCC—Nano crystalline cellulose；CDI—N,N-carbonyldiimidazole；MPO—2-Methyl-2-propen-1-ol.

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表 3 PCNCC/MBAE复合材料的DMA特征参数

Table 3. DMA characteristics of PCNCC/MBAE composites

Sample	T_g/℃	E′/MPa
Sample	T_g/℃	60℃	250℃
MBAE	240.4	2 190	224
0.1 wt%PCNCC/MBAE	245.5	2 330	254
0.2 wt%PCNCC/MBAE	257.8	2 611	425
0.3 wt%PCNCC/MBAE	252.7	2 486	346
0.4 wt%PCNCC/MBAE	248.4	2 424	288
0.5 wt%PCNCC/MBAE	246.2	2 260	243
Notes: T_g—Glass transition temperature; E'—Storage modulus.

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