可熔融丙烯腈-N-乙烯基咪唑共聚物及纤维的制备与性能

doi:10.7503/cjcu20150309

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (10): 2073.doi: 10.7503/cjcu20150309

• 高分子化学 • 上一篇

可熔融丙烯腈-N-乙烯基咪唑共聚物及纤维的制备与性能

韩娜, 李慧慧, 李传宝, 张兴祥(), 李伟, 王栋

天津工业大学材料科学与工程学院, 改性与功能纤维天津市重点实验室, 天津 300387

收稿日期:2015-04-07 出版日期:2015-10-10 发布日期:2015-10-10
作者简介:联系人简介: 张兴祥, 男, 教授, 博士生导师, 主要从事功能材料及智能材料的合成与应用研究. E-mail:zhangxingxiang@tjpu.edu.cn
基金资助:
国家自然科学基金(批准号: 21206123)、教育部博士学科点专项科研基金(批准号: 20111201120001)、博士后面上基金(批准号: 2014M551026)、天津市应用基础与前沿计划重点项目(批准号: 13JCZDJC32100)、天津市应用基础与前沿技术研究计划青年基金(批准号: 13JCQNJC02300)和山东省博士后创新专项资金(批准号: 201402011) 资助

Synthesis and Properties of Melt Processable Acrylonitrile-N-vinylimidazole Copolymers and Fiber^†

HAN Na, LI Huihui, LI Chuanbao, ZHANG Xingxiang^*(), LI Wei, WANG Dong

Tianjin Municipal Key Lab of Fiber Modification and Functional Fiber, Institute of Functional Fibers,School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300387, China

Received:2015-04-07 Online:2015-10-10 Published:2015-10-10
Contact: ZHANG Xingxiang E-mail:zhangxingxiang@tjpu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.21206123), the Research Fund for the Doctoral Program of Higher Education of China(No.20111201120001), the China Postdoctoral Science Foundation(No.2014M551026), the Key Project of Applied Basic Research and Frontier Technology Research Programs Funded by Tianjin Municipal Science and Technology Commission, China(No.13JCZDJC32100), the Applied Basic Research and Frontier Technology Research Programs of Young Foundation Funded by Tianjin Municipal Science and Technology Commission, China(No.13JCQNJC02300) and the Postdoctoral Foundation of Shandong Province, China(No.201402011)

摘要/Abstract

摘要：

采用自由基溶液聚合法制备了不同投料摩尔比的丙烯腈(AN)-N-乙烯基咪唑(VIM)共聚物[P(AN-co-VIM)]. 将n(AN)∶n(VIM)为82∶18和80∶20的P(AN-co-VIM)共聚物于210~220 ℃熔融纺丝制备了P(AN-co-VIM)初生纤维. 通过傅里叶变换红外光谱、核磁共振(¹H NMR)谱、差示扫描量热分析、 X射线衍射分析和热台显微镜对P(AN-co-VIM)共聚物的组成、热力学和结晶行为进行了表征. 结果表明, 自由基溶液聚合法可成功制备P(AN-co-VIM)共聚物, 当VIM的摩尔分数大于10%时, 共聚物具有可熔融加工性. 随着VIM摩尔分数的增加, 共聚物的熔点降低, 当VIM含量为20%时, 共聚物的熔点从317 ℃降低至180 ℃, 其分解温度最高为313.7 ℃. 扫描电子显微镜(SEM)和电子单纤维强力测试. 结果表明, 纤维的表面光滑, 断面结构致密, 初生纤维的断裂强度为1.58 cN/dtex, 断裂伸长率为11.2%, 有望广泛应用于碳纤维领域.

关键词: 丙烯腈, N-乙烯基咪唑, 溶液聚合, 熔融纺丝, 纤维

Abstract:

Polyacrylonitrile(PAN) and acrylonitrile(AN)-N-vinylimidazole(VIM) copolymers[abbreviated as P(AN-co-VIM)] with various n(AN)∶n(VIM)(93∶7—80∶20) were synthesized by free-radical solution copolymerization in dimethyl formamide(DMF). The P(AN-co-VIM) copolymers(82∶18 and 80∶20) possessed good melt processability, which were melt spun at the temperature of 210—220 ℃. The crystallinity, thermodynamics behavior and the composition of P(AN-co-VIM) copolymers were studied and characterized by ubbelodhe viscosimeter, Fourier transform infrared spectroscopy(FTIR), nuclear magnetic resonance(¹H NMR), differential scanning calorimetry(DSC), X-ray diffraction(XRD) analyses and hot stage microscope. The results revealed that P(AN-co-VIM) could be synthesized successfully by free-radical solution copolymerization. P(AN-co-VIM) could be melt processable as VIM molar fraction is higher than 10%. The melting temperature of P(AN-co-VIM) shifts continuously to the lower temperature with the comonomer contents increasing. When the molar fraction of VIM is increased to 20%, the melting point of P(AN-co-VIM) copolymer reduced from 317 ℃ to 180 ℃. The highest decomposition temperature is 313.7 ℃. The apparent morphology and mechanical properties of the P(AN-co-VIM) fibers were characterized by scanning electron microscope(SEM) and single fiber electronic tensile strength test. The results show that the fibers have smooth surface and compact cross section. As-spun P(AN-co-VIM) fiber gets the fracture strength of 1.58 cN/dtex and the elongation at break attained 11.2%. After post-treatment, the fiber is expected to be widely used in the field of carbon fiber.

Key words: Acrylonitrile, N-vinylimidazole, Solution copolymerization, Melt spinning, Fiber

中图分类号:

TrendMD:

韩娜, 李慧慧, 李传宝, 张兴祥, 李伟, 王栋. 可熔融丙烯腈-N-乙烯基咪唑共聚物及纤维的制备与性能. 高等学校化学学报, 2015, 36(10): 2073.

HAN Na, LI Huihui, LI Chuanbao, ZHANG Xingxiang, LI Wei, WANG Dong. Synthesis and Properties of Melt Processable Acrylonitrile-N-vinylimidazole Copolymers and Fiber^†. Chem. J. Chinese Universities, 2015, 36(10): 2073.

图/表 15

Table 1 P(AN-co-VIM) prepared with various n(AN)∶n(VIM)

P(AN-co-VIM)	n(AN)∶n(VIM)		Conversion(%)
P(AN-co-VIM)	Feed		Copolymer
A	100∶0	100.0∶0	88.5
B	93∶7	91.1∶8.9	66.2
C	90∶10	84.7∶15.3	68.9
D	88∶12	83.1∶16.9	78.0
E	85∶15	80.1∶19.9	83.5
F	82∶18	73.8∶26.2	72.9
G	80∶20	72.3∶27.7	84.9

Fig.1 FTIR spectra of PAN(a) and P(AN-co-VIM) copolymers(b—g)n(AN)∶n(VIM): a. 100∶0; b. 93∶7; c. 90∶10; d. 88∶12; e. 85∶15; f. 82∶18; g. 80∶20.

Fig.2 1H NMR spectrum of P(AN-co-VIM)(85∶15) copolymer

Fig.3 DSC heating curves(10 ℃/min) of PAN(a) and P(AN-co-VIM) copolymers(b—g)n(AN)∶n(VIM): a. 100∶0; b. 93∶7; c. 90∶10; d. 88∶12; e. 85∶15; f. 82∶18; g. 80∶20.

Table 2 Thermodynamic data of PAN and P(AN-co-VIM) copolymers

Sample	n(AN)/n(VIM)	T_g/℃	T_m/℃	T_do/℃	T_dp/℃
A	100∶0	135.0		261.6	265.2
B	93∶7	113.2	232.2	273.7	284.1
C	90∶10	112.7, 148.6	199.4	276.1	291.4
D	88∶12	114.0, 149.7	200.2	281.6	296.5
E	85∶15	117.1		286.9	302.1
F	82∶18	120.8		299.2	312.6
G	80∶20	118.9		294.7	313.7

Fig.4 DSC heating curves(60 ℃/min) of PAN(a) and P(AN-co-VIM) copolymers(b—g)n(AN)∶n(VIM): a. 100∶0; b. 93∶7; c. 90∶10; d. 88∶12; e. 85∶15; f. 82∶18; g. 80∶20.

Fig.5 DSC cooling curves(60 ℃/min) of PAN(a) and P(AN-co-VIM) copolymers(b—g)n(AN)∶n(VIM): a. 100∶0; b. 93∶7; c. 90∶10; d. 88∶12; e. 85∶15; f. 82∶18; g. 80∶20.

Fig.6 Hot stage microscope photos of P(AN-co-VIM)(85∶15) copolymer Temprature/℃: (A) 170; (B) 180; (C) 190; (D) 200.

Table 3 Melting temperature range of PAN and P(AN-co-VIM)

Sample	n(AN)∶n(VIM)	Melting temperature range/℃	Sample	n(AN)∶n(VIM)	Melting temperature range/℃
A	100∶0	Not melt	E	85∶15	170—200
B	93∶7	Not melt	F	82∶18	170—190
C	90∶10	190—200	G	80∶20	170—180
D	88∶12	190—205

Fig.7 X-ray diffraction patterns of PAN(a) and P(AN-co-VIM) copolymers(b—g)n(AN)∶n(VIM): a. 100∶0; b. 93∶7; c. 90∶10; d. 88∶12; e. 85∶15; f. 82∶18; g. 80∶20.

Table 4 Crystallinity and crystallite dimension of PAN and P(AN-co-VIM) copolymers

Sample	n(AN)∶n(VIM)	Crystallinity (%)	Crystallite dimension/nm	Sample	n(AN)∶n(VIM)	Crystallinity (%)	Crystallite dimension/nm
A	100∶0	48.4	4.0	E	85∶15	41.1	2.3
B	93∶7	38.3	3.3	F	88∶12	41.0	2.0
C	90∶10	41.0	2.6	G	80∶20	35.8	1.9
D	88∶12	39.0	2.4

Fig.8 SEM images of the surface of melt-spinning P(AN-co-VIM) fibers(A) P(AM-co-VIM)(82∶18); (B) P(AN-co-VIM)(80∶20).

Fig.9 SEM images of the cross-cutting section(A) and pull-broken section(B) of P(AN-co-VIM)(80∶20) fiber

Fig.10 Stress-strain curves of as-spun P(AN-co-VIM) fibers by melt spinning a. P(AN-co-VIM)(82∶18); b. P(AN-co-VIM)(80∶20).

Table 5 Physical mechanical properties of melt-spinning P(AN-co-VIM) fibers

Sample	n(AN)∶n(VIM)	Fineness/dtex	Tenacity/cN	Elongation(%)	Breaking strength/(cN·dtex^-1)
A	82∶18	104	145	7.1	1.4
B	80∶20	120	190	11.2	1.6

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可熔融丙烯腈-N-乙烯基咪唑共聚物及纤维的制备与性能

Synthesis and Properties of Melt Processable Acrylonitrile-N-vinylimidazole Copolymers and Fiber^†

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可熔融丙烯腈-N-乙烯基咪唑共聚物及纤维的制备与性能

Synthesis and Properties of Melt Processable Acrylonitrile-N-vinylimidazole Copolymers and Fiber†

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Synthesis and Properties of Melt Processable Acrylonitrile-N-vinylimidazole Copolymers and Fiber^†