聚乙二醇柠檬酸酯平滑剂合成及其复配油剂性能

doi:10.13475/j.fzxb.20231203101

摘要/Abstract

摘要： 针对涤纶工业丝油剂耐热性差、高温平滑性不佳等难题,采用聚乙二醇和柠檬酸为单体合成酯类平滑剂,优化了平滑剂合成工艺,复配聚醚类乳化剂、有机钾盐类抗静电剂及其它副组分,制备了耐热型纺丝油剂,并对油剂的平滑性能、界面性能、抗静电性能和热稳定性进行了表征。结果表明:在柠檬酸与聚乙二醇的量比为1∶2、催化剂质量分数为0.02%、170 ℃下反应1.5 h的条件下制得聚乙二醇柠檬酸酯,酯化率达到97%,酸值、羟值和皂化值分别为0.62、8、182 mgKOH/g,高温黏度和耐热性能均超过市售常用平滑剂;以聚乙二醇柠檬酸酯为平滑剂复配得到的油剂其表面张力为31.05 mN/m,接触角为11.2°,磨斑直径为0.538 mm,摩擦因数为0.043,电导率达到6.13 μS/cm;耐热性能最优的油剂在140 ℃和250 ℃下挥发2 h的损失率分别为1.4%和12%。该耐热型纺丝油剂在抗静电和热稳定性等方面均优于进口油剂。

关键词: 聚乙二醇柠檬酸酯, 纺丝油剂, 平滑剂, 耐热性, 涤纶工业丝, 化纤工业

Abstract:

Objective Chemical fibers need to undergo high-temperature thermal drawing and treating during post-processing, which can easily cause scattering and breakage. Oil agents can adjust friction characteristics and give fibers high-temperature smoothness during spinning processing to run smoothly and steadily for the fiber production. However, with domestically produced oil agents used at high temperatures, abnormal phenomenon such as serious coking of hot rollers and tangled (remnant) fibers would still occur. As a result, the spinning oil agents for PET industrial fibers in domestic large-scale production are independent of imports.

Method In view of the problems of poor heat resistance and poor high-temperature smoothness of domestic chemical fiber oils, compound design of oil components was carried out on the basis of successful synthesis of excellent smoothing agents, which was prepared from polyethylene glycol and citric acid as monomers. The smoothing agent synthesis conditions was optimized, then a heat-resistant spinning oil could be achieved with the presence of self-prepared smoothing agent, selected polyether emulsifiers and other components. The chemical structure, thermal properties and viscosity of the smoothing agent, and the smoothness, interface properties, antistatic properties and thermal stability of the oil agent were also characterized and compared with the current products.

Results The optimized conditions for the synthesis of polyethylene glycol citrate as smoothing agent are considered as: the acid-to-alcohol molar ratio of 1∶2, 0.02% of catalyst, the temperature of 170 ℃ with reaction time of 1.5 h in N₂ atmosphere, and the esterification rate reaches 97%. The acid value, hydroxyl value and saponification value of the synthetic smoothing agent are 0.62 mgKOH/g, 8 mgKOH/g and 182 mgKOH/g, respectively. The high temperature viscosity and heat resistance are higher than that of common smoothing agents. The vital performance parameters of the well-designed oil agent are excellent, as the surface tension is 31.05 mN/m, the wear scar diameter is 0.538 mm, the friction coefficient is 0.043, the specific resistance is 1.63 MΩ/cm, and the conductivity reaches 6.13 μS/cm, and the friction and antistatic properties exceed the imported oils. Even more importantly, the oil smokes well and has excellent thermal stability. The respective volatilization loss rate in 2 h at 140 ℃ and 250 ℃ are only 1.4% and 12%.

Conclusion The excellent physical and chemical properties of polyethylene glycol citrate were synthesized as a smoothing agent, whose viscosity and interfacial properties were equivalent to those of imported oils. With a careful selection of emulsifier, antistatic agent and other components, the formulation of the oil agent was configured to meet the high requirements of PET industrial fiber, the friction and antistatic properties exceed the imported oil. In terms of thermal properties, the three self-prepared oil agents could be completely comparable to the same type imported oil.

Key words: polyethylene glycol citrate ester, spinning oil agent, smoothing agent, heat resistance, polyester industrial filament, chemical fiber industry

中图分类号:

TQ340.47

陈世昌, 杨冬冬, 陈文兴. 聚乙二醇柠檬酸酯平滑剂合成及其复配油剂性能[J]. 纺织学报, 2024, 45(11): 128-135.

CHEN Shichang, YANG Dongdong, CHEN Wenxing. Synthesis of polyethylene glycol citrate ester smoothing agent and performance of compound formulation design for spinning oil agents[J]. Journal of Textile Research, 2024, 45(11): 128-135.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20231203101

http://www.fzxb.org.cn/CN/Y2024/V45/I11/128

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类别	酸值/ (mgKOH·g^-1)	羟值/ (mgKOH·g^-1)	皂化值/ (mgKOH·g^-1)
PETO	0.5	13	187
TMPTO	1	10	185
聚乙二醇柠檬酸酯	0.62	8	182

油剂类别	外观(25 ℃)	pH值	水分含量/%
进口油剂	黄色液体	8.18	1.38
1^#	黄色液体	8.05	1.00
2^#	黄色液体	7.67	1.64
3^#	黄色液体	7.89	1.57

油剂类别		润湿时间/s
进口油剂	34.36	4.5	12.9
1^#	31.05	5.1	11.2
2^#	33.37	4.3	13.4
3^#	33.25	4.3	14.5

油剂类别	高温冒烟	油剂热稳定性
进口油剂	少量蓝烟	无析出物
1^#	少量蓝烟	无析出物
2^#	少量蓝烟	无析出物
3^#	少量蓝烟	无析出物