纺织学报 ›› 2023, Vol. 44 ›› Issue (04): 8-15.doi: 10.13475/j.fzxb.20220306908

• 纤维材料 • 上一篇    下一篇

海岛纤维用增塑改性聚乙烯醇的制备及其性能

王双华1,2, 王冬1,2, 付少海1,2(), 仲鸿天3, 董朋3   

  1. 1.江苏省纺织品数字喷墨印花工程技术研究中心, 江苏 无锡 214122
    2.生态纺织教育部重点实验室(江南大学), 江苏 无锡 214122
    3.江苏聚杰微纤科技集团股份有限公司, 江苏 苏州 215200
  • 收稿日期:2022-03-18 修回日期:2022-12-09 出版日期:2023-04-15 发布日期:2023-05-12
  • 通讯作者: 付少海(1972—),男,教授,博士。主要研究方向为高分子材料改性。E-mail:shaohaifu@hotmail.com。
  • 作者简介:王双华(1996—),女,硕士生。主要研究方向为聚乙烯醇的改性及其在海岛纤维中的应用。
  • 基金资助:
    全国博士后管委会香江学者计划项目(XJ2021020)

Preparation and properties of plasticized polyvinyl alcohol for sea-island fiber production

WANG Shuanghua1,2, WANG Dong1,2, FU Shaohai1,2(), ZHONG Hongtian3, DONG Peng3   

  1. 1. Jiangsu Engineering Research Center for Digital Textile Inkjet Printing, Wuxi, Jiangsu 214122, China
    2. Key Laboratory of Eco-Textiles (Jiangnan University), Ministry of Education, Wuxi, Jiangsu 214122, China
    3. Jiangsu Jujie Microfiber Technology Group Co., Ltd., Suzhou, Jiangsu 215200, China
  • Received:2022-03-18 Revised:2022-12-09 Published:2023-04-15 Online:2023-05-12

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摘要：

为解决海岛纤维碱减量带来的环境污染问题,以双季戊四醇、硬脂酸钙和抗氧剂B225为复配增塑剂,对聚乙烯醇(PVA)进行增塑改性,通过熔融加工制备了高热分解温度的改性PVA。通过研究三者的添加量及熔融加工温度对PVA性能的影响,优化PVA的增塑改性工艺。对 PVA与复配增塑剂之间的氢键作用、 改性PVA的断面形貌、结晶结构进行了表征和分析。结果表明:当双季戊四醇、硬脂酸钙和抗氧剂B225的质量占比分别为15、3和1,熔融加工温度为200 ℃时,复配增塑剂与 PVA之间的氢键作用较强, PVA结晶度降低,熔点降低到178.2 ℃,热分解温度提高到301.3 ℃,提供了123.1 ℃的加工窗口;改性PVA水溶性良好,在25 ℃下也能完全溶解。研究结果为实现以PVA为海组分的绿色环保海岛纤维的制备提供参考和技术支持。

关键词: 聚乙烯醇, 熔融加工, 高热分解温度, 增塑改性, 水溶性, 海岛纤维

Abstract:

Objective Sea-island fibers, which are mostly prepared by melt composite spinning, are favored by the textile industry due to the excellent properties and high added value. Alkali-soluble polyester (COPET) is the common sea component of PVA to be removed by alkali decrement method that will cause environmental pollution. Polyvinyl alcohol (PVA) is expected to replace COPET as the sea component to solve environmental pollution, because it is green, non-toxic and water-soluble.
Method Due to amounts of strong intermolecular/intramolecular hydrogen bonds of PVA, the melting point is approximate to the thermal decomposition temperature, which leads to difficulty for melt processing. Modified PVA with high thermal decomposition temperature was prepared by melt blending with compound plasticizers, which consisted of dipentaerythritol, calcium stearate and irganox B225. The effects of compound plasticizers on thermal properties and fluidity of PVA were investigated by DSC, TG and melt flow rate. The suitable processing temperature of PVA was obtained by torque rheometer. The intermolecular hydrogen bonds, crystallinity and compatibility of modified PVA were analyzed by FT-IR, XRD and SEM.
Results The melt-forming property and thermostability of PVA were improved obviously via introducing compound plasticizers. When the contents of dipentathritol, calcium stearate and irganox B225 were 15%, 3%, and 1%, respectively, the thermal decomposition temperature of modified PVA was up to 301.3 ℃ and the melting point reduced to 178.2 ℃ (Fig. 1, Fig. 3 and Fig. 5), providing a thermal processing window of 123.1 ℃. The modified PVA showed a transparent appearance due to its good melt fluidity and outstanding oxidation resistance (Fig. 2, Fig. 4 and Fig. 6). The plasticization and melt fluidity of modified PVA were significantly enhanced with the increase of melting processing temperature (ranging from 195 to 210 ℃). Obviously, when the processing temperature reached up to 200 ℃, the modified PVA could be well plasticized (Tab. 2). The compound plasticizers could effectively destroy the intramolecular and/or intermolecular hydrogen bonds of PVA and reconstructed the fresh hydrogen bonds with PVA, reflected by the shift of absorption peak (Fig. 7). Interestingly, the compound plasticizers improved greatly the activity of PVA molecular chain, thereby reducing its crystallinity (Fig. 8). Addition, the cross section of the modified PVA was observed by scanning electron microscope (SEM). There were almost no obvious plasticizer particles precipitation, and some tiny particles were dispersed uniformly in PVA matrix without agglomeration, which indicated good compatibility between the composite plasticizers and PVA (Fig. 9). Furthermore, the resulting modified PVA could still be melt extruded smoothly at 250 ℃, which provided feasibility for melt composite spinning with PET. Particularly, it is unexpected that the modified PVA could be dissolved at 25 ℃ (Tab. 3), which demonstrates good water solubility, creating many opportunities for the subsequent alkali-free fiber opening process of sea-island fiber.
Conclusion The modified PVA was prepared by melting process and its compound plasticizer composed of dipentaerythritol, calcium stearate and irganox B225.The effects of compound plasticizers and processing temperature on the properties of PVA were investigated to optimize its plasticizing modification process. The compound plasticizers can effectively destroy the hydrogen bonds among PVA molecules and enhance the activity of PVA molecular chain to reduce its crystallinity and melting point. Meanwhile, the fresh hydrogen bonds between PVA and the compound plasticizer enhance the stability of PVA hydroxyl group, thereby improving the thermal stability of PVA. In conclusion, the modified PVA has excellent thermostability and melt fluidity as well as water solubility, providing reference and technical support for the preparation of sea-island fiber with PVA as the sea component.

Key words: polyvinyl alcohol, melt processing, high thermal decomposition temperature, plasticizing modification, water solubility, sea-island fiber

中图分类号: 

  • TQ325.9

表1

样品参数表"

样品编号 m(PVA ):m(双季戊四醇):
m(硬脂酸钙):m(抗氧剂B225 )
1# 100:7.5:3:1
2# 100:10:3:1
3# 100:12.5:3:1
4# 100:15:3:1
5# 100:17.5:3:1
6# 100:20:3:1
7# 100:15:0:1
8# 100:15:1:1
9# 100:15:2:1
10# 100:15:4:1
11# 100:15:5:1
12# 100:15:3:0
13# 100:15:3:0.5
14# 100:15:3:0.75
15# 100:15:3:1.25
16# 100:15:3:1.5

图1

PVA与不同双季戊四醇含量的改性PVA的DSC和TG曲线"

图2

双季戊四醇含量对改性PVA熔体流动速率的影响"

图3

PVA与不同硬脂酸钙含量的改性PVA的DSC和TG曲线"

图4

硬脂酸钙含量对改性PVA熔体流动速率的影响"

图5

PVA与不同抗氧剂含量的改性PVA的DSC和TG曲线"

图6

不同抗氧剂质量占比的改性PVA粒子的外观比较"

表2

加工温度对改性PVA加工性能的影响"

加工温
度/℃		 转速/
(r·min-1)		 塑化转矩/
(N·m)		 平衡转矩/
(N·m)		 开始熔融
时间/min		 塑化时
间/min
195 50 18.31 15.94 1.67 2.63
200 50 17.27 14.76 1.52 2.41
205 50 15.69 13.73 1.40 2.23
210 50 14.81 13.12 1.35 2.11

图7

PVA与改性PVA的红外谱图"

图8

PVA与改性PVA的 XRD 图"

图9

PVA与改性PVA的扫描电镜照片"

表3

改性PVA(4#)的水溶性"

样品质量/g 水量/mL 水温/℃ 溶解时间/min
1 100 25 97
1 100 40 70
1 100 50 58
1 100 60 41
1 100 70 32
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