纺织学报 ›› 2026, Vol. 47 ›› Issue (1): 168-175.doi: 10.13475/j.fzxb.20250601501

• 染整工程 • 上一篇    下一篇

二氧化碳基聚氨酯丙烯酸酯乳液制备及其胶膜性能

刘旭颖1,2, 银倩琳3, 王先成3, 樊高晴4, 戚栋明1, 陈智杰2()   

  1. 1.浙江理工大学 纺织科学与工程学院(国际丝绸学院), 浙江 杭州 310018
    2.温州职业技术学院 智能制造学院, 浙江 温州 325035
    3.杭州宏华数码科技股份有限公司, 浙江 杭州 310051
    4.现代纺织技术创新中心(鉴湖实验室), 浙江 绍兴 312030
  • 收稿日期:2025-06-09 修回日期:2025-11-06 出版日期:2026-01-15 发布日期:2026-01-15
  • 通讯作者: 陈智杰(1989—),男,助理研究员,博士。主要研究方向为功能性复合乳胶制备及成膜。E-mail:chenzhijie5262@163.com。
  • 作者简介:刘旭颖(2001—),女,硕士生。主要研究方向为功能高分子聚合物的合成及应用。
  • 基金资助:
    浙江省“尖兵”“领雁”攻关计划项目(2024C01198);温州市基础性科研项目(G20240060)

Preparation of CO2-based polyurethane acrylate emulsion and its film properties

LIU Xuying1,2, YIN Qianlin3, WANG Xiancheng3, FAN Gaoqing4, QI Dongming1, CHEN Zhijie2()   

  1. 1. College of Textile Science and Engineering (International Institute of Silk), Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
    2. Intelligent Manufacturing College, Wenzhou Vocational and Technical College, Wenzhou, Zhejiang 325035, China
    3. Hangzhou Honghua Digital Technology Co., Ltd., Hangzhou, Zhejiang 310051, China
    4. Modern Textile Technology Innovation Center (Jianhu Laboratory), Shaoxing, Zhejiang 312030, China
  • Received:2025-06-09 Revised:2025-11-06 Published:2026-01-15 Online:2026-01-15

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摘要：

针对现有数码喷墨墨水黏合剂多以石化原料为主、可再生性差、难以兼顾牢度和柔性的问题,以二氧化碳基聚碳酸亚丙酯二醇(PPCD)为软段,异佛尔酮二异氰酸酯为硬段,丙烯酸羟丙酯为封端剂,丙烯酸丁酯和甲基丙烯酸甲酯为共聚单体,通过乳液聚合制备了具有高牢度、高柔韧性的改性聚氨酯丙烯酸酯(PUA)乳液,并将其用于数码喷墨涂料墨水的制备。通过傅里叶变换红外光谱、核磁共振氢谱技术表征二氧化碳基聚氨酯丙烯酸酯乳液的分子结构,对比分析PPCD与聚乙二醇(PEG)、聚四氢呋喃(PTMEG)为软段的PUA乳液反应转化率、反应前后粒径、胶膜力学性能、胶膜表面微相结构及相应涤纶平纹数码印花织物的服用性能等。结果显示:相较于PEG和PTMEG,因PPCD分子结构中同时含有醚键和酯键,故由其所制PUA胶膜展现出较高的断裂强度和延展性,其断裂强度达10.8 MPa,断裂伸长率达825%;相应的涤纶平纹印花织物具备4~5级的耐干湿摩擦牢度、较低的硬挺度和较好的透气性。

关键词: 聚碳酸亚丙酯二醇, 聚氨酯丙烯酸酯, 涂料墨水, 喷墨印花, 黏合剂, 工艺优化

Abstract:

Objective In view of the fact that the current digital inkjet ink adhesives are mainly composed of petrochemical raw materials, with poor renewability and difficulty in achieving both durability and flexibility, the aim of this research is to use CO2-based polycarbonate propylene carbonate diol (PPCD) as the soft segment, isophorone diisocyanate (IPDI) as the hard segment, hydroxypropyl acrylat (HPA) as the end-capping agent, and butyl acrylat (BA) and methyl methacrylate (MMA) as the copolymer monomers to prepare a water-based polyurethane acrylate (PUA) emulsion with environmentally friendly properties and high durability and flexibility, which is then applied in the preparation of digital inkjet ink.

Method CO2-based waterborne polyurethane prepolymer (VWPU) was prepared by copolymerization of CO2-based PPCD, IPDI, HPA and 2,2-dimethylolbutyric acid (DMBA). The VWPU was characterized by Fourier transform infrared spectroscopy (FT-IR) and H nudear magnetic resonance spectroscopy (1HNMR). Consequently, BA and MMA were introduced into VWPU for emulsion polymerization to obtain CO2-based PUA.

Results The particle size distributions of emulsions prepared by different polyols are unimodal, and the average particle size of PPCD-PUA was the smallest (50.79 nm), lower than PTMEG-PUA (68.69 nm) and significantly lower than PEG-PUA (146.10 nm). The conversion test results of PUA emulsion showed that the reaction rate of PPCD-PUA was the fastest, which was attributed to the increase of free radical capture efficiency and chain growth driving force of small particle size droplets. The mechanical tests of PUA film showed that the elastic modulus of PPCD-PUA film (42.0 MPa), fracture strength (10.8 MPa) and elongation at break (825%) were between that of PEG-PUA and that of PTMEG-PUA, indicating a soft and tough film. AFM analysis of PUA film revealed that PPCD-PUA had the lowest surface roughness. According to the PUA printing fabric wearing performance test results and SEM images, dry and wet rubbing fastness of PPCD-PUA ink increased to level 4-5. The relative stiffness of PPCD-PUA printed fabrics was found relatively low, enabling a comfortable feel, and the comprehensive performance was confirmed to meet the needs of high-end pigment printing.

Conclusion The VWPU prepolymer with good reactivity was prepared by using PPCD as soft segment, and PUA emulsion with particle size of about 60 nm was prepared by emulsion polymerization. Compared with PEG and PTMEG, PPCD has both ether bonds and ester bonds, resulting in a higher cohesion energy and lower crystallinity. This enables the PUA film produced there from to have a higher elongation at break (825%) and a higher fracture strength (10.8 MPa), meeting the performance requirements of high-end printing adhesives. The printed fabric made of PPCD-PUA has higher dry and wet rubbing fastness, higher softness and better air permeability, which has greater comprehensive advantages than the printed fabric made of PEG-PUA and PTMEG-PUA.

Key words: polypropylene carbonate diol, polyurethane acrylate, coating ink, inkjet printing, adhesive, process optimization

中图分类号: 

  • TQ325

图1

PPCD-VWPU封端前后的红外谱图"

图2

PPCD-VWPU的核磁共振氢谱图"

图3

不同多元醇制备PUA聚合乳化前后的粒径图"

图4

不同多元醇制备的PUA乳液转化率"

表1

PUA胶膜的断裂强度、断裂伸长率及弹性模量"

多元醇种类 断裂强度/MPa 断裂伸长率/% 弹性模量/MPa
PTMEG 22.4 216 149.7
PPCD 10.8 825 42.0
PEG 4.2 1 072 20.2

图5

不同多元醇制备的PUA胶膜AFM图像"

表2

PUA印花织物的耐干湿摩擦色牢度、相对硬挺度及透气率"

多元醇
种类		 耐摩擦色牢度/级 相对
硬挺度/%		 透气率/
(mm·s-1)
干 湿
PEG 3 2~3 142 482.56
PTMEG 4~5 3~4 206 494.61
PPCD 4~5 4 152 568.24

图6

不同多元醇制备的PUA印花织物湿摩擦前后的SEM照片"

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