电纺十二酸十二酯@聚乙烯醇蓄热调温纤维的制备及性能

石峰; 张国庆; 刘国金; 周岚

doi:10.13801/j.cnki.fhclxb.20201022.002

电纺十二酸十二酯@聚乙烯醇蓄热调温纤维的制备及性能

doi: 10.13801/j.cnki.fhclxb.20201022.002

石峰^1,,
张国庆^{1, 2,},
刘国金^1,,
周岚^{1, 2, ,}

1.
浙江理工大学　纺织科学与工程学院(国际丝绸学院)，杭州 310018
2.
浙江理工大学　上虞工业技术研究院有限公司，绍兴 312300

基金项目: 国家自然科学基金 (22075252)；浙江省国际产业联合研发计划项目(2019C54003)

详细信息

通讯作者:
周岚，博士，副教授，硕士生导师，研究方向为功能性纺织品　 E-mail：lan_zhou330@163.com

中图分类号: TB34；TQ340.64
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- 被引次数: 0
出版历程
- 收稿日期: 2020-08-27
- 录用日期: 2020-10-16
- 网络出版日期: 2020-10-22
- 刊出日期: 2021-08-15

Preparation and properties of the electrospun dodecanol dodecanoate@polyvinyl alcohol thermo-regulated fibers

SHI Feng^1
,,
ZHANG Guoqing^{1, 2
,},
LIU Guojin^1
,,
ZHOU Lan^{1, 2
, ,}

1.
College of Textile Science and Engineering (International Institute of Silk), Zhejiang Sci-tech University, Hangzhou 310018, China
2.
Shangyu Industrial Technology Research Institute CO. LTD., Zhejiang Sci-Tech University, Shaoxing 312300, China

摘要

摘要: 以十二酸十二酯作为相变材料(PCM)，以聚乙烯醇(PVA)作为支撑材料，通过乳液静电纺丝技术制备十二酸十二酯@PVA蓄热调温纤维。应用SEM、TEM、DSC、TGA、迷你温度记录仪和红外热成像仪等研究了纺丝液组成及静电纺纤维的表面形貌、潜热值、热稳定性、调温性能、力学性能和水溶性。结果表明，当PVA浓度为10.0wt%、十二酸十二酯∶PVA质量比为50%时，纺丝液具有较好的稳定性和可纺性。十二酸十二酯@PVA静电纺纤维具有明显的芯-鞘结构，纤维中PCM的热分解温度比纯PCM提高了20℃，具有良好的热稳定性。十二酸十二酯@PVA静电纺纤维的潜热值在63 J/g左右，在降温冷却和热红外成像测试中，显示出良好的蓄热调温性能。经戊二醛交联后，静电纺纤维中支撑材料的热稳定性显著增强，而且，纤维的力学性能和水溶解性得到明显改善。
- 聚乙烯醇 /
- 相变材料 /
- 十二酸十二酯 /
- 静电纺丝 /
- 蓄热调温纤维
Abstract: With dodecanol dodecanoate as the phase change material (PCM) and polyvinyl alcohol (PVA) as the supporting material, the dodecanol dodecanoate@PVA thermo-regulated fibers were prepared by emulsion electrospinning technology. The SEM, TEM, DSC, TGA, mini temperature recorder and infrared thermal imager were applied to study the composition of the spinning solution and the surface morphology, latent heat value, thermal stability, temperature regulating properties, mechanical property and water solubility of the electrospun fibers. The results show that with 10.0wt% of PVA and dodecanol dodecanoate∶PVA mass ratio of 50%, the spinning solution has better stability and spinnability. The dodecanol dodecanoate@PVA electrospun fibers have apparent core-sheath structure, and the thermal decomposition temperature of PCM in the fibers is 20℃ higher than the pure PCM, displaying good thermal stability. The latent heat value of dodecanol dodecanoate@PVA electrospun fibers is about 63 J/g, showing good heat storage and temperature regulation performance in cooling process and thermal infrared imaging test. After the crosslinking with glutaraldehyde, the thermal stability of the support material in the electrospun fibers is significantly enhanced, and the mechanical properties and water solubility of the fibers have notable improvement.
- polyvinyl alcohol /
- phase change materials /
- dodecanol dodecanoate /
- electrospinning /
- thermo-regulated fiber

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图 1 不同PVA浓度下PCM@PVA纺丝液静置24 h后的照片

Figure 1. Photos of the PCM@PVA solutions with different PVA concentrations after 24 h ((a) 6.0wt%; (b) 8.0wt%; (c) 10.0wt%; (d) 14.0wt%)

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图 2 不同PVA浓度所得PCM@PVA纤维的SEM图像

Figure 2. SEM images of PCM@PVA fibers prepared at different PVA concentrations ((a) 6.0wt%; (b) 8.0wt%; (c) 10.0wt%; (d) 14.0wt%)

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图 3 10.0wt%和14.0wt%PVA浓度制备的静电纺纤维的SEM图像

Figure 3. SEM images of electrospun fibers with 10.0wt% and 14.0wt% PVA concentrations ((a) PVA fiber (10.0wt%); (b) PCM30@PVA fiber (10.0wt%); (c) PCM50@PVA fiber (10.0wt%); (d) PCM80@PVA fiber (10.0wt%); (e) PVA fiber (14.0wt%); (f) PCM30@PVA fiber (14.0wt%); (g) PCM50@PVA fiber (14.0wt%); (h) PCM80@PVA fiber (14.0wt%))

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图 4 10.0wt%和14.0wt%PVA浓度制备的静电纺纤维的平均直径

Figure 4. Average diameter profile of electrospun fibers with 10.0wt% and 14.0wt% PVA concentrations

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图 5 10.0wt% (a) 和14.0wt% (b) PVA浓度制备的静电纺纤维及PCM的DSC曲线

Figure 5. DSC curves of PCM and electrospun fibers with 10.0wt% (a) and 14.0wt% (b) PVA concentrations

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图 6 10.0wt%和14.0wt%PVA制备的PCM@PVA纤维热处理后在吸油纸上的照片

Figure 6. Photos of PCM@PVA fibers prepared by 10.0wt% and 14.0wt% PVA on oil-absorbing sheet after heat treatment ((a) PCM30@PVA fiber (10.0wt%); (b) PCM50@PVA fiber (10.0wt%); (c) PCM80@PVA fiber (10.0wt%); (d) PCM30@PVA fiber (14.0wt%); (e) PCM50@PVA fiber (14.0wt%); (f) PCM80@PVA fiber (14.0wt%))

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图 7 不同样品的TEM图像

Figure 7. TEM images of different samples((a) PVA fiber; ((b), (c)) PCM@PVA fiber; (d) CPVA-PCM fiber)

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图 8 不同样品的TGA曲线

Figure 8. TGA curves of different samples

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图 9 PVA纤维和PCM@PVA纤维的降温曲线

Figure 9. Cooling curves of PVA fibers and PCM@PVA fibers

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图 10 PVA纤维和PCM@PVA纤维的热红外成像图

Figure 10. Thermal infrared images of PVA fibers and PCM@PVA fibers((a) PVA fiber; (b) PCM30@PVA fiber; (c) PCM50@PVA fiber; (d) PCM80@PVA fiber)

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图 11 不同样品的拉伸曲线

Figure 11. Tensile curves of different samples

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图 12 PCM@PVA纤维 (a) 和CPVA-PCM纤维 (b) 在不同时间的水溶解情况

Figure 12. Water solubility of PCM@PVA fiber (a) and CPVA-PCM fiber (b) at different time

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表 1 材料名称与缩写对应

Table 1. Corresponding of material name and abbreviation

Sample		Abbreviation
Fibers with different dodecanol dodecanoate∶PVA mass ratios	30%	PCM30@PVA fiber
	50%	PCM50@PVA fiber
	80%	PCM80@PVA fiber
Dodecanol dodecanoate@polyvinyl alcohol thermal storage solution		PCM@PVA solution
Dodecanol dodecanoate-polyvinyl alcohol thermal storage fiber		PCM@PVA fiber
Crosslinked polyvinyl alcohol/dodecanol dodecanoate thermal storage fiber		CPVA-PCM fiber
Notes: PCM—Phase change material; PVA—Polyvinyl alcohol; CPVA—Crosslinking PVA.

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表 2 不同PCM@PVA纤维样品的热性能数据

Table 2. Thermal performance data of different PCM@PVA fiber samples

Sample	T_mo/℃	T_m/℃	ΔH_m/(J·g⁻¹)	T_co/℃	T_c1/℃	T_c2/℃	ΔH_c/(J·g⁻¹)
PCM	25.10	28.10	193.70	24.34	23.64	—	193.25
PVA fiber(10.0wt%)	—	—	—	—	—	—	—
PCM30@PVA fiber(10.0wt%)	25.96	28.72	26.91	24.81	23.99	8.51	26.99
PCM50@PVA fiber(10.0wt%)	26.30	29.71	63.18	25.11	24.88	14.63	62.52
PCM80@PVA fiber(10.0wt%)	26.69	29.07	72.48	25.07	25.01	14.29	72.32
PVA fiber(14.0wt%)	—	—	—	—	—	—	—
PCM30@PVA fiber(14.0wt%)	25.38	28.07	28.53	25.42	22.41	7.29	27.42
PCM50@PVA fiber(14.0wt%)	25.59	28.60	63.50	24.04	23.47	8.67	61.23
PCM80@PVA fiber(14.0wt%)	25.30	28.72	73.37	24.16	23.72	7.43	73.44
Notes: T_mo—Onset melting temperature; T_m—Melting temperature; ΔH_m—Melting enthalpy; T_co—Onest crystallizing temperature; T_c1—First crystallizing temperature; T_c2—Second crystallizing temperature; ΔH_c—Crystallization enthalpy.

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表 3 不同样品的热分解数据

Table 3. Thermal decomposition data of different samples

Sample	T₁/℃	W₁/wt%	T₂/℃	W₂/wt%	T₃/℃	W₃/wt%	T₄/℃	W₄/wt%	W/wt%
PCM	190	100	—	—	—	—	—	—	100
PVA fiber	20	7.5	270	64.5	445	22	—	—	94
PCM30@PVA fiber	20	7.5	210	13.5	270	57	434	15	93
PCM50@PVA fiber	20	7.5	210	21	270	44.5	420	21	94
PCM80@PVA fiber	20	7.5	210	29	270	42	434	14.5	93
CPVA-PCM fiber	20	7.5	210	42.5	355	25	450	19	94
Notes: T₁, T₂, T₃, T₄—Initial degradation temperatures of the 1st, 2nd, 3rd and 4th stages; W₁, W₂, W₃, W₄—Mass loss fractions of the 1st, 2nd, 3rd and 4th stages; W—Final mass loss fraction.

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