碳纤维增强尼龙6复合材料的阴离子聚合反应注射成型工艺

周佳慧; 李金焕; 肖军; 王显峰; 任林林

doi:10.13801/j.cnki.fhclxb.20210302.002

碳纤维增强尼龙6复合材料的阴离子聚合反应注射成型工艺

doi: 10.13801/j.cnki.fhclxb.20210302.002

南京航空航天大学　材料科学与技术学院，南京 210001

基金项目: 装备发展部装备预研共用技术(41422010403)

详细信息

通讯作者:
李金焕，副教授，硕士生导师，研究方向为热塑性复合材料及高性能树脂开发等　 E-mail：jinhuan_nj@nuaa.edu.cn

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2020-12-16
- 录用日期: 2021-02-10
- 网络出版日期: 2021-03-02
- 刊出日期: 2021-12-01

Anionic polymerization reaction injection molding process of carbon fiber reinforced nylon 6 composite

School of Materials Science and Tecnology, Nanjing University of Aeronautics and Astronautics, Nanjing 210001, China

摘要

摘要: 以己内酰胺为原料，自制己内酰胺钠(C10)、双酰化内酰胺-1，6-己二胺(C20)分别为引发剂和活化剂，首先对适用于反应注射成型技术(RIM)的尼龙6(PA6)阴离子聚合工艺进行探究。实验结果表明，提高引发剂浓度可提升聚合反应速率，转化率受影响并不明显，但分子量有所降低；而提高活化剂浓度，会导致聚合反应不完全；随着聚合温度的升高，反应速率明显加快，同时分子量增大，结晶度呈下降趋势。最终选取1.5 mol%的C10、1 mol%的C20，浸胶温度100℃、聚合温度180℃的工艺参数，利用自行研制的反应注射设备成功制备了单向碳纤维增强尼龙6 (CF/PA6)复合材料单向板，其沿纤维方向的拉伸强度可达974.2 MPa，弯曲强度达786.9 MPa。
- 尼龙6 /
- 阴离子聚合 /
- 聚合工艺 /
- 反应注射成型 /
- 复合材料
Abstract: Caprolactam was used as raw material, sodium caprolactam (C10) and diacyllactam-1,6-hexanediamine (C20) as initiators and activators respectively. The anionic polymerization process of nylon 6 (PA6) suitable for reaction injection molding (RIM) technology was explored. The results show that polymerization rate can be improved by increasing the concentration of C10, but the limiting viscosity number is the opposite. However, increasing the concentration of C20 alone results in incomplete polymerization and low conversion. With the increase of polymerization temperature, the degree of polymerization can be increased. Finally, the unidirectional carbon fiber (CF)/PA6 composites with good properties were prepared by selecting the technological parameters of C10 1.5 mol%, C20 1 mol%, dipping temperature of 100℃ and polymerization temperature of 180℃. The tensile strength along the fiber direction can reach 974.2 MPa, and the bending strength can reach 786.9 MPa.
- nylon 6 /
- anionic polymerization /
- polymerization process /
- reaction injection molding /
- composite

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图 1 碳纤维增强尼龙6(CF/PA6)复合材料反应注射成型流程

Figure 1. Process of carbon/nylon 6 (CF/PA6) composite reaction injection molding

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图 2 不同己内酰胺钠(C10)浓度下聚合反应温度-时间关系

Figure 2. Temperature-time relationship of polymerization reaction under different sodium caprolactam (C10) concentrations

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图 3 不同C10浓度下聚合物PA6的转化率和特性黏数

Figure 3. Conversion rate and limiting viscosity number of polymers PA6 under different C10 concentrations

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图 4 双酰化内酰胺-1，6-己二胺(C20)结构式

Figure 4. Structure of activator diacyllactam-1,6-hexanediamine (C20)

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图 5 不同C20浓度下聚合反应温度-时间关系

Figure 5. Temperature-time relationship of polymerization reaction under different C20 concentrations

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图 6 不同C20浓度下聚合物PA6转化率

Figure 6. Conversion rate of polymers PA6 under different C20 concentrations

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图 7 不同聚合温度下聚合反应温度-时间关系

Figure 7. Temperature-time relationship of polymerization reaction at different polymerization temperatures

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图 8 不同聚合温度下聚合物PA6的转化率及特性黏数

Figure 8. Conversion rate and limiting viscosity number of polymers PA6 at different polymerization temperatures

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图 9 反应注射成型(RIM)法制得的CF/PA6复合材料平板

Figure 9. Carbon fiber reinforced PA6 composite plate by reaction injection molding (RIM)

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图 10 CF/PA6复合材料截面纤维分布SEM图像

Figure 10. SEM image of fiber distribution in CF/PA6 composite section

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图 11 CF/PA6复合材料拉伸断裂面SEM图像

Figure 11. SEM image of composite tensile fracture surface of CF/PA6 composite

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表 1 聚合实验配方

Table 1. Experimental formula of polymerization

Formulation	C10/mol%	C20/mol%
F1	1	1
F2	1.5	1
F3	2	1
F4	2.5	1
F5	1	1.5
F6	1	2
F7	1	2.5
Notes: C10—Sodium caprolactam; C20—Diacyllactam-1, 6-hexamediamine.

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表 2 不同聚合温度下聚合产物PA6结晶数据

Table 2. Crystallization data of polymerization products PA6 at different polymerization temperatures

Polymerization temperature/℃	Crystallization onset temperature/℃	Crystallization termination temperature/℃	Peak temperature/℃	Crystallization enthalpy/(J·g^-1)	Crystallinity/ %
160	179.4	164.7	171.6	61.69	26.82
170	173.6	160.2	167.9	45.59	19.82
180	180.9	165.2	172.8	48.92	21.27
190	180.9	163.8	172.5	48.69	21.17

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表 3 CF/PA6复合材料物理性质与力学性能

Table 3. Physical properties and mechanical properties of CF/PA6 composites

Characterization of CF/PA6	Value
Conversion rate/%	96.43
Liminting viscosity number/(mg·L^-1)	83.24
Crystallinity/%	24.82
0° tensile strength/MPa	974.2
90° tensile strength/MPa	20.46
0° flexural strength/MPa	786.9
90° flexural strength/MPa	38.55

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