光致变色聚乳酸/聚3-羟基丁酸酯共混纤维的纺制及其结构与性能

doi:10.13475/j.fzxb.20230905101

摘要/Abstract

摘要：

为开发一种具有良好力学性能和变色效果的生物基光致变色合成纤维,以聚乳酸(PLA)为纤维基体,聚3-羟基丁酸酯(PHB)为改性高分子材料,光致变色微胶囊(PCMs)为光敏指示剂,制备了光致变色PLA/PHB共混物,并系统研究了共混物的流变性能,确定了适纺的组分比;通过熔体纺丝制备了光致变色PLA/PHB共混纤维,重点分析牵伸工艺对纤维结构与性能的影响。结果表明:可连续稳定熔体纺丝的光致变色PLA/PHB共混物中,PHB的最高质量分数为20%;光致变色PLA/PHB共混纤维具有良好的力学性能,断裂强度为3.09~3.79 cN/dtex,断裂伸长率为21.78%~29.13%,初始模量为14.29~24.62 cN/dtex;随着牵伸温度的提高,纤维断裂强度保持不变,晶粒尺寸减小,初始模量下降,断裂伸长率呈现上升趋势;随着牵伸倍数的增大,纤维的结晶度和晶粒尺寸均增大,断裂强度和初始模量均提高,但断裂伸长率有所下降。该光致变色PLA/PHB共混纤维具有灵敏的光响应效果,良好的光致变色稳定性以及回复性。

关键词: 功能纤维, 聚3-羟基丁酸酯, 聚乳酸, 光致变色, 熔体纺丝, 共混纤维

Abstract:

Objective The requirements for environmental protection are getting higher and higher, and the use of bio-based polymers to replace petroleum-based polymers is an inevitable development trend. It is hence of interest to develop bio-based photochromic synthetic fibers with good mechanical properties and color-changing effects.

Method With polyactic acid (PLA) was as fiber matrix, polyhydroxybutyrate (PHB) as modified polymer material and phase-change materials (PCMs) as photosensitive indicator, a new bio-based photochromic synthetic fiber with good mechanical properties and chromic effect was prepared using melt spinning technology. The rheological properties of the photochromic PLA/PHB blend were analyzed. The effects of post-drafting process on the structure and properties of fibers were systematically studied.

Results The apparent viscosity of photochromic PLA/PHB blends decreased with the increase of temperature and shear rate, and the decrease was more obvious with the increase of PHB content. The blend is an incompatible system and the PHB is thermally degraded during processing. The cross section and surface of the fibers were smooth, with no obvious structural defects, and the diameter was about 20 μm.When the drafting multiple was 4.0 times, with the increase of the drafting temperature, the breaking strength of the fiber basically remained unchanged, the elongation at break increased, the initial modulus decreased somewhat, and the thermal shrinkage of the fiber decreased. XRD results showed that the addition of PHB and PCMs did not produce new crystal types, and the crystallinity of the fiber decreases and the grain size of the (200 & 110) crystal plane of PLA showed a downward trend. With the increase of the drafting ratio, the breaking strength of the fiber was increased, the elongation at break decreased, and the initial modulus increased. When the drafting ratio was 4.2, the fracture strength of F15-150-4.2 (the PHB mass fraction was 15%, the drafting temperature was 150 ℃, and the drafting multiple was 4.2 times) reached (3.79±0.40) cN/dtex, the elongation at break (25.51±1.72)%, and the initial modulus (20.19±2.51) cN/dtex, indicating the good mechanical properties. The thermal shrinkage rate of blended fiber showed an increasing trend. The crystallinity and grain size of the fibers was increasd, so the fracture strength and initial modulus increase with the increase of the drafting ratio. The fibers began to change color in the first second under the sunlight, from white to light green, and are responsive. After 50 times of ultraviolet illumination, the color difference value hardly changed, and the fiber returned to a color that was difficult to be distinguished by the naked eye in 10 min.

Conclusion The photochromic PLA/PHB blend fibers were successfully prepared by melt spinning technology. The breaking strength of the fibers was (3.09-3.79) cN/dtex, the elongation at break was 21.78%-29.13%, and the initial modulus was (14.29-24.62) cN/dtex. The improvement of fiber properties is closely related to the post-drafting process. With the increase of drafting temperature, PHB forms a large amorphous region inside the fiber and entangles seriously with PLA macromolecular chains. The crystallinity and grain size of the fiber decrease, the thermal shrinkage rate decreases, the fracture strength remains unchanged, the initial modulus decreases, and the fiber flexibility improves. With the increase of the drafting ratio, the axial orientation of the macromolecular chain increases, the crystallinity and grain size increase, the fracture strength of the fiber increases, and the thermal shrinkage of the fiber increases. Photochromic PLA/PHB blend fiber can change color from white to light green in 1 s under the sunlight, and has a sensitive response. After 50 times of ultraviolet illumination, it can still maintain acceptable color difference, and has good light stability and good light recovery. It provides a scientific basis for developing functional bio-based synthetic fibers and expanding the application of PHB in textiles.

Key words: functional fiber, poly3-hydroxybutyrate, polylactic acid, photochromic, melt spinning, blended fibre

中图分类号:

TS102.52

欧宗权, 于金超, 潘志娟. 光致变色聚乳酸/聚3-羟基丁酸酯共混纤维的纺制及其结构与性能[J]. 纺织学报, 2024, 45(12): 9-17.

OU Zongquan, YU Jinchao, PAN Zhijuan. Spinning of photochromic polylactic acid/polyhydroxybutyrate blend fiber and its structure and properties[J]. Journal of Textile Research, 2024, 45(12): 9-17.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20230905101

http://www.fzxb.org.cn/CN/Y2024/V45/I12/9

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成分	质量分数/%	用途
三聚氰胺甲醛树脂	1~5	外壳材料
螺噁嗪类隐形染料	1~5	变色材料
1,2-二甲基-4-(1-苯乙基)苯	80~95	脂肪酸溶剂

样品编号	PHB质量分数/%	PLA质量分数/%
B0	0	96.3
B5	5	91.3
B10	10	86.3
B15	15	81.3
B20	20	76.3
B25	25	71.3
B30	30	66.3
B40	40	56.3
B100	96.3	0

纤维试样编号	断裂强度/ (cN·dtex^-1)	断裂伸长率/%	初始模量/ (cN·dtex^-1)
F15-130-4.0	3.58±0.29	23.57±1.43	18.32±2.48
F15-140-4.0	3.60±0.47	24.44±1.83	17.46±3.19
F15-150-4.0	3.60±0.57	25.21±1.88	15.76±2.61
F20-130-4.0	3.65±0.87	21.78±2.31	24.62±6.03
F20-140-4.0	3.71±0.63	22.34±2.59	18.18±4.12
F20-150-4.0	3.76±0.77	23.98±1.80	16.38±3.77
F15-150-3.5	3.09±0.19	29.13±1.44	14.97±1.50
F15-150-4.2	3.79±0.40	25.51±1.72	20.19±2.51
F20-150-3.5	3.13±0.76	27.60±2.40	14.29±4.63
F20-150-4.2	3.78±0.74	24.26±1.82	18.66±3.66

纤维试样编号	沸水热收缩率	干热收缩率
F15-130-4.0	30.20±0.91	21.00±0.16
F15-140-4.0	27.10±0.25	19.53±0.09
F15-150-4.0	27.10±0.74	16.73±0.25
F20-130-4.0	25.27±0.50	13.73±0.47
F20-140-4.0	25.40±0.66	14.80±0.16
F20-150-4.0	22.40±0.65	12.40±0.28
F15-150-3.5	25.60±0.33	15.07±0.25
F15-150-4.2	26.80±0.16	19.20±0.16
F20-150-3.5	21.40±0.33	10.50±0.19
F20-150-4.2	23.30±0.25	13.33±0.25

纤维试样编号	T_m/℃	ΔH_m/(J·g^-1)	X_c/%
F15-130-4.0	166.14	51.517	53.66
F15-140-4.0	165.88	50.685	52.80
F15-150-4.0	166.76	49.291	51.34
F20-130-4.0	165.33	51.065	52.73
F20-140-4.0	165.13	49.414	51.03
F20-150-4.0	165.48	49.051	51.16
F15-130-3.5	166.59	47.297	49.27
F15-150-4.2	166.26	49.811	51.44
F20-130-3.5	165.56	48.283	49.85
F20-150-4.2	165.54	50.311	51.95