面向熔体直纺的聚酰胺6降膜脱挥增黏反应过程模拟

doi:10.13475/j.fzxb.20241202201

纺织学报 ›› 2025, Vol. 46 ›› Issue (10): 1-10.doi: 10.13475/j.fzxb.20241202201

• 纤维材料 • 下一篇

面向熔体直纺的聚酰胺6降膜脱挥增黏反应过程模拟

陈世昌¹^,²(), 娄顺月¹^,², 陈文兴¹

1.浙江理工大学纺织纤维材料与加工技术国家地方联合实验室, 浙江杭州 310018
2.浙江省现代纺织技术创新中心, 浙江绍兴 312000

收稿日期:2024-12-10 修回日期:2025-04-19 出版日期:2025-10-15 发布日期:2025-10-15
作者简介:陈世昌(1988—),男,副教授,博士。研究方向为化纤绿色制造与应用技术。E-mail:scchen@zstu.edu.cn。
基金资助:
国家自然科学基金项目(52173047);国家自然科学基金项目(51803187);“纺织之光”中国纺织工业联合会应用基础研究项目(J202401)

Simulation of devolatilization and viscosity increase reaction of polyamide 6 falling film for direct melt spinning

CHEN Shichang¹^,²(), LOU Shunyue¹^,², CHEN Wenxing¹

1. National Engineering Laboratory for Textile Fiber Materials Processing Technology, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
2. Zhejiang Provincial Innovation Center of Advanced Textile Technology, Shaoxing, Zhejiang 312000, China

Received:2024-12-10 Revised:2025-04-19 Published:2025-10-15 Online:2025-10-15

摘要/Abstract

摘要： 针对聚酰胺6(PA6)生产中切片纺丝生产流程长、能耗高的现状,提出采用降膜脱挥反应方法直接制备可满足熔体直接纺丝加工的高品质聚酰胺6熔体的新工艺路线。利用流程模拟方法对降膜脱挥反应过程进行研究,在验证PA6二段水解聚合模拟结果基础上,结合降膜脱挥反应模型,考察了降膜脱挥反应器入口PA6相对黏度和工艺条件等对出口产物品质的影响规律。结果表明:在260 ℃、200 Pa的条件下,以相对黏度为2.35的PA6熔体进入降膜脱挥反应器时,出料熔体可增黏到3.1,单体和低聚物质量分数分别降低至0.23%和0.115%;增大进料熔体相对黏度、提高脱挥反应温度或降低真空压力值,可显著提升脱挥反应速率并降低端基浓度、小分子含量。模拟结果可为开发PA6熔体直纺新技术提供有益借鉴。

关键词: 聚酰胺6, 相对黏度, 降膜反应器, 脱挥, 过程模拟, 熔体直纺

Abstract:

Objective In view of the current situation of long chip spinning production process and high energy consumption in the production of polyamide 6(PA6), a process simulation analysis was conducted on the preparation of low-volatile polyamide 6 melt. By adding a falling film devolatilization reactor with vacuum facility after two-stage polymerization, multiple systems such as cooling granulation, hot water extraction, drying, solid phase adhesion and extrusion melting could be eliminated to realize the direct spinning of polyamide 6 fiber.

Method The outlet data of polyamide 6 two-stage VK tube established in Polymer Plus is taken as the inlet parameter of the falling film devolatilization reactor. The mathematical model established according to reaction kinetics, mass transfer and material balance is essentially a set of partial differential equations. MatLab is used to calculate the devolatilization and viscosity increase process of the falling film devolatilization reactor. When the reactor operation reaches a steady state, the concentration of each component in the reactor no longer changes with the change of time, and the concentration of the main component at the liquid phase outlet of the devolatilizing reactor and related technical indicators are obtained.

Results The model investigated the effects of different melt feed parameters, reaction temperature, pressure and other factors on the number average molecular weight (M_n), extractable content and end group concentration during the viscosity increasing process of falling film reactor. The results showed that high temperature and low pressure improved the performance of the product, but too low pressure caused costs increase for industrial production, making it more difficult to control. The by-products in high-temperature products tended to increase, which is not conducive to subsequent spinning. The results suggested that when the relative viscosity (η_r) of inlet melt was increased, the η_r of polymer increased slowly with the increase of reactor length, and the contents of monomer caprolactam (m_CPL) and oligomer (C_O) decreased gradually. When the reaction temperature of the falling film reactor was increased, the M_n of polyamide 6 melt gradually increased, while m_CPL and C_O gradually decreased. When the pressure of the reactor was reduced, the M_n gradually increased, and the m_CPL and C_O gradually decreased. Therefore, the process parameters of 260 ℃ and 200 Pa were selected to obtain a high viscosity polymer with a M_n of 21 709 g/mol, monomer content (m_CPL) of 0.230%, and oligomer content (C_O) of 0.115%.

Conclusion When the η_r of inlet material increases, the η_r of melt decreases with the increase of falling film flow distance, and the m_CPL and C_O decrease gradually. After the melt with a η_r of 2.35 passes through the falling film devolatilization reactor, its η_r can be increased to 3.1. The effects of reaction temperature, pressure and other conditions on polymer number, M_n, η_r, m_CPL, C_O and end group concentration in falling film devolatilization reactor were studied. With the increase of reaction temperature, the M_n of polymers in a certain range increased linearly, the m_CPL decreased from 7.062% to 0.230%, the C_O decreased from 0.710% to 0.115%, and the end group concentration([NH₂] and [COOH]) also decreased gradually. By controlling the pressure of the falling film devolatilization reactor, it is shown that the relative viscosity of the polymer is improved at low pressure. Reduce the m_CPL and C_O in melt. By adjusting and controlling the inlet melt parameters of the falling film devolatilization reactor, high quality PA6 melt can be obtained under suitable devolatilization reaction temperature and vacuum degree. The research results are conducive to the development of direct spinning technology of PA6 melt.

Key words: polyamide 6, relative viscosity, falling film reactor, devolatilization, process simulation, direct melt spinning

中图分类号:

TQ342.1

陈世昌, 娄顺月, 陈文兴. 面向熔体直纺的聚酰胺6降膜脱挥增黏反应过程模拟[J]. 纺织学报, 2025, 46(10): 1-10.

CHEN Shichang, LOU Shunyue, CHEN Wenxing. Simulation of devolatilization and viscosity increase reaction of polyamide 6 falling film for direct melt spinning[J]. Journal of Textile Research, 2025, 46(10): 1-10.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20241202201

http://www.fzxb.org.cn/CN/Y2025/V46/I10/1

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参数	目标值	模拟值
数均分子量M_n	12 000~15 000 g/mol	14 538 g/mol
相对黏度η_r	2.100~2.400	2.350
端胺基初始浓度[NH₂]	—	45.634 mmol/kg
端羧基初始浓度[COOH]	—	62.228 mmol/kg
水初始浓度[H₂O]	—	60.088 mmol/kg
己内酰胺质量分数m_CPL	7.000%~9.000%	7.060%
低聚物O质量分数C_O	0.080%~2.000%	0.710%

反应编号	反应方程式
S1	$\mathrm{P}_{1}+\mathrm{P}_{1} \underset{k_{1} / K_{1}}{\stackrel{k_{1}}{\rightleftharpoons}} \mathrm{COOH}-\mathrm{NH}_{2}+\mathrm{H}_{2} \mathrm{O}$
S2	$\mathrm{NH}_{2}+\mathrm{COOH} \underset{k_{1} / K_{1}}{\stackrel{k_{1}}{\rightleftharpoons}} \mathrm{~B} \_\mathrm{ACA}-\mathrm{B} \_\mathrm{ACA}+\mathrm{H}_{2} \mathrm{O}$
S3	$\mathrm{P}_{1}+\mathrm{COOH} \underset{k_{1} / K_{1}}{\stackrel{k_{1}}{\rightleftharpoons}} \mathrm{COOH}-\mathrm{B} \_\mathrm{ACA}+\mathrm{H}_{2} \mathrm{O}$
S4	$\mathrm{P}_{1}+\mathrm{NH}_{2} \underset{\overline{k_{1} / K_{1}}}{\stackrel{k_{1}}{\rightleftharpoons}} \mathrm{NH}_{2}-\mathrm{B} \_\mathrm{ACA}+\mathrm{H}_{2} \mathrm{O}$
S5	$\mathrm{CPL}+\mathrm{H}_{2} \mathrm{O} \underset{k_{2} / K_{2}}{\stackrel{k_{2}}{\rightleftharpoons}} \mathrm{P}_{1}$
S6	$\mathrm{P}_{1}+\mathrm{CPL} \underset{k_{3} / K_{3}}{\stackrel{k_{3}}{\rightleftharpoons}} \mathrm{NH}_{2}-\mathrm{COOH}$
S7	$\mathrm{NH}_{2}+\mathrm{CPL} \underset{k_{3} / K_{3}}{\stackrel{k_{3}}{\rightleftharpoons}} \mathrm{NH}_{2}-\mathrm{B} \_\mathrm{ACA}$
S8	$\mathrm{O}+\mathrm{H}_{2} \mathrm{O} \underset{\overline{k_{4} / K_{4}}}{\stackrel{k_{4}}{\rightleftharpoons}} \mathrm{COOH}-\mathrm{NH}_{2}$
S9	$\mathrm{O}+\mathrm{P}_{1} \underset{k_{5} / K_{5}}{\stackrel{k_{5}}{\rightleftharpoons}} \mathrm{COOH}-\mathrm{B} \_\mathrm{ACA}-\mathrm{NH}_{2}$
S10	$\mathrm{O}+\mathrm{NH}_{2} \underset{k_{5} / K_{5}}{\stackrel{k_{5}}{\rightleftharpoons}} \mathrm{~B} \_\mathrm{ACA}-\mathrm{B} \_\mathrm{ACA}-\mathrm{NH}_{2}$

面向熔体直纺的聚酰胺6降膜脱挥增黏反应过程模拟

Simulation of devolatilization and viscosity increase reaction of polyamide 6 falling film for direct melt spinning

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