Journal of Textile Research ›› 2024, Vol. 45 ›› Issue (03): 129-136.doi: 10.13475/j.fzxb.20230303001

• Dyeing and Finishing Engineering • Previous Articles     Next Articles

Synthesis and application of microfiber leather impregnated with waterborne polyurethane

LI Chen1,2, WANG Dong1,2, ZHONG Hongtian3, DONG Peng3, FU Shaohai1,2()   

  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:2023-03-13 Revised:2023-12-01 Online:2024-03-15 Published:2024-04-15
  • Contact: FU Shaohai E-mail:shaohaifu@hotmail.com

Abstract:

Objective As an artificial leather product, impregnated microfiber leather owns excellent thermodynamic properties, rebound resilience, softness, and fullness. However, the main material for its production is solvent polyurethane, which causes serious environmental pollution. Whereas waterborne polyurethane, an environmental-friendly material, brings problems of surface cracks and poor texture when applied to the impregnation of microfiber leather. In order to solve these problems, a particular waterborne polyurethane emulsion was designed and synthesized by referring to the solvent polyurethane with large molecular weight and small particle size, and then successfully applied to the production of impregnated microfiber leather.

Method The prepolymer method was adopted to synthesize the target waterborne polyurethane emulsion by using isophorone diisocyanate (IPDI) as the hard segment, polycarbonate diol (PCDL) as the soft segment, 2,2-bis(hydroxymethyl) propionic acid as the hydrophilic chain extender, and 1,4-butanediol as the flexible chain extender, trimethylolpropane (TMP) as internal cross-linking agent, and ethylenediamine as post chain extender. The relative molecular weight and emulsion particle size of waterborne polyurethane were controlled by adjusting the relative molecular weight of PCDL and the content of TMP, the waterborne polyurethane emulsion with the optimal formula was applied to the production of impregnated microfiber leather.

Results Firstly, emulsion tests were conducted to explore the influences of PCDL relative molecular weight and TMP content on the waterborne polyurethane emulsion in different aspects. According to the results, the relative molecular weight and emulsion particle size of the waterborne polyurethane emulsion was increased with the rising of the PCDL relative molecular weight, and the emulsion particle size decreases first and then increases sharply with the growth of TMP content. When the PCDL relative molecular weight reached 500, the emulsion would be cured smoothly to form a film, and when the PCDL relative molecular weight exceeds 3 000, the emulsion doesn't emulsify but disperses in a flocculating form due to the overlong molecular chain segment. When the TMP content surpasses 3%, the waterborne polyurethane emulsion obviously begins to precipitate due to excessive long-chain network structures and seriously intertwined segments. When the PCDL relative molecular weight amounts to 2 000 with a 3% TMP mass fraction, the synthesized waterborne polyurethane demonstrates a strong storage stability with a relative molecular weight of 5.93×104 and a particle size of merely 89.54 nm. After DSC, DMA, and mechanics property analysis tests on the cured films of the above waterborne polyurethane, it was concluded from PCDL molecular weight that the storage modulus and loss modulus of the films at high temperature can reach 2 837.57 MPa and 278.87 MPa, while the breaking strength was 3.725 MPa with an elongation at break of 763.99%. The target product was obtained by adopting the above waterborne polyurethane to produce the impregnated microfiber leather. Its cross-sectional SEM images showed that the internal bonding and curing of waterborne polyurethane were significantly improved with even and stable distribution. It was observed from the tensile diagrams of the microfiber leather that the surface cracks were also resolved.

Conclusion A waterborne polyurethane emulsion which had large molecular weight and small particle size was produced, with both its emulsion state and physical and chemical properties showing stability. While applied to the production of impregnated microfiber leather, it was observed that the obtained waterborne polyurethane demonstrated high performance as well as the possibility of large-scale production. The curing condition inside the microfiber leather has been improved by enhancing the wettability and bonding property of the substrate in the real application, thus effectively reducing surface cracks, and retaining a good texture and elasticity.

Key words: waterborne polyurethane, microfiber leather, impregnating process, emulsion particle size, trimethylolpropane, polycarbonate diol

CLC Number: 

  • TS193.5

Tab.1

Prescription of waterborne polyurethane"

样品编号 质量/g
PCDL IPDI DMPA BDO TMP EDA TEA H2O
WPU500-1 30 28.75 2.5 1.25 0 1.31 1.51 130.64
WPU1000-1 30 17.47 2.02 1.01 0 1.09 1.21 105.90
WPU2000-1 30 11.83 1.78 0.89 0 0.93 1.07 93.00
WPU3000-1 30 9.01 1.66 0.83 0 0.85 1.00 86.70
WPU2000-2 30 14.18 1.90 0.95 0.48(w=1%) 0.99 1.15 99.30
WPU2000-3 30 18.69 2.14 1.07 1.61(w=3%) 1.12 1.29 111.84
WPU2000-4 30 25.63 2.50 1.25 3.13(w=5%) 1.30 1.51 130.60
WPU2000-5 30 34.82 2.98 1.49 5.22(w=7%) 1.59 1.80 155.80

Tab.2

Influences of PCDL relative molecular weight on stability and film-forming state of WPU emulsions"

样品编号 乳液状态 离心稳定性 储存稳定性 成膜状态
WPU500-1 微透明带蓝光 稳定 >3个月 胶膜碎裂
WPU1000-1 微透明带蓝光 稳定 >3个月 透明稳定
WPU2000-1 微透明带蓝光 稳定 >3个月 透明稳定
WPU3000-1 凝絮状无法分散

Tab.3

Influences of TMP content on stability and film-forming state of WPU emulsions"

样品编号 乳液状态 离心稳定性 储存稳定性 成膜状态
WPU2000-1 微透明带蓝光 稳定 >3个月 透明稳定
WPU2000-2 微透明带淡蓝光 稳定 >3个月 透明稳定
WPU2000-3 微透明白色乳液 稳定 >3个月 透明稳定
WPU2000-4 白色乳液 微有沉淀 <1个月 表面粗糙
WPU2000-5 白色乳液 有沉淀 <1个月 有颗粒凸起

Fig.1

States of WPU emulsions with different TMP contents"

Fig.2

Influences of PCDL relative molecular weight (a) and TMP content (b) on particle size distribution of WPU emulsions"

Tab.4

Physical and chemical properties of WPU emulsions"

样品编号 固含量/% pH值 黏度/(mPa·s) 重均分子量 平均粒径/nm PDI值
WPU1000-1 32.1±1.1 7.84±0.09 55.34±1.75 3.42×104 89.54 0.179
WPU2000-1 31.8±0.6 7.71±0.04 40.58±0.57 5.27×104 122.00 0.175
WPU2000-3 32.3±0.8 7.73±0.05 49.87±1.62 5.93×104 94.55 0.217

Fig.3

Infrared spectrum of WPU film"

Fig.4

Influences of PCDL relative molecular weight (a) and TMP content (b) on glass transition temperature and crystallinity of WPU film"

Fig.5

Influences of PCDL relative molecular weight and TMP content on viscoelasticity of WPU film. (a)Influence of PCDL relative molecular weight on storage modulus; (b)Influence of PCDL relative molecular weight on loss modulus; (c) Influence of TMP content on storage modulus; (d) Influence of TMP content on loss modulus"

Fig.6

Influences of PCDL relative molecular weight (a) and TMP content (b) on mechanical properties of WPU film"

Fig.7

Cross-sectional SEM images of WPU-impregnated microfiber leather. (a) WPU2000-3 impregnated microfiber leather; (b) DIC WLI-630AR impregnated microfiber leather"

Tab.5

Performance results of different WPU-impregnated microfiber leather"

超纤革 急弹回复角/(°) 缓弹回复角/(°) 比压缩回弹率/% 柔软度/mm 开裂情况
空白样基布 85.3±0.36 93.5±1.59 1.72±0.02 8.97±0.05
DIC WLI-630AR含浸超纤革 94.2±0.62 120.4±1.84 4.22±0.03 7.63±0.08 裂纹多
WPU2000-3含浸超纤革 105.6±0.50 130.9±2.08 4.98±0.03 7.62±0.05 裂纹少
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