Journal of Textile Research ›› 2026, Vol. 47 ›› Issue (06): 122-130.doi: 10.13475/j.fzxb.20260100701

• Dyeing and Finishing Engineering • Previous Articles     Next Articles

Preparation of CO2-based polyurethane hot melt adhesive and its application in digital heat transfer printing

DENG Fukun1, CHEN Zhijie2(), YIN Qianlin3, CHEN Yu4, WEN Lei4, QI Dongming1,5   

  1. 1 School 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 Zhejiang Aoyu New Materials Technology Co.， Ltd.， Quzhou， Zhejiang 324100， China
    5 Modern Textile Technology Innovation Center （Jianhu Laboratory）， Shaoxing， Zhejiang 312030， China
  • Received:2026-01-04 Revised:2026-04-20 Online:2026-06-15 Published:2026-08-19
  • Contact: CHEN Zhijie E-mail:chenzhijie5262@163.com

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Abstract:

Objective To improve the recyclability of the traditional petroleum-based polyurethane hot melt adhesives （TPU）， this study aims to prepare an environmentally friendly CO2-based TPU with high durability， high mechanical properties and high flexibility. The hard segment is dicyclohexylmethane diisocyanate （HMDI）， the soft segment is carbon dioxide-based polypropylene carbonate （PPCD）， and 1， 4-butanediol （BDO） is used as the chain extender. This CO2-based TPU is used for white ink heat transfer printing on polyester-cotton fabrics.

Method Polypropylene diol polycarbonate （PPCD） was copolymerized with different isocyanates to synthesize polyurethane prepolymers. Following that， chain extender BDO was added for chain extension to prepare carbon dioxide-based thermoplastic polyurethane hot melt adhesive， which was characterized by Fourier transform infrared spectroscopy （FT-IR） and nuclear magnetic resonance hydrogen spectroscopy （1H-NMR）. Polyurethane hot melt adhesive was selected， suitable for white ink heat transfer printing on polyester-cotton fabrics through screening.

Results It was learnt from the differential scanning calorimetry （DSC） curve graph that the glass transition temperature （-5.6 ℃） of HMDI type TPU was lower than that of MDI type TPU and IPDI type TPU， which makes the adhesive film moderately soft at room temperature. Thermogravimetric analysis （TGA） showed that all three types of CO2-based TPU had good heat resistance， with their decomposition temperatures higher than the general heat transfer processing temperatures， leading to good thermal stability. The mechanical property test results of CO2-based TPU demonstrated that the tensile strength （15.557 MPa） and elongation at break （596.137%） of HMDI type polyurethane were between those of diphenylmethane diisocyanate type （MDI） polyurethane and isophorone diisocyanate type （IPDI） polyurethane， and HMDI type polyurethane have both strength and flexibility. Microstructure analysis indicated that HMDI type TPU had a moderate degree of microphase separation. It not only formed sufficient hard segment micro-regions to provide cohesive strength but also maintained the mobility of molecular chain segments， thus better wetting the substrate during bonding. The dry/wet rubbing fastness of HMDI printed fabrics reached grade 4-5. The printed fabrics showed relatively low stiffness， enabling satisfactory fabric softness and wearing comfort.

Conclusion Three types of CO2-based TPU were successfully prepared using PPCD as the soft segment， IPDI， MDI and HMDI as the hard segments respectively， and BDO as the capping agent. HMDI type TPU proved to be the best comprehensive balance in all key performance aspects. Its glass transition temperature （-5.6 ℃） is moderate， which helps to achieve optimal softness and durability of HMDI type. In terms of mechanical properties， its breaking strength （15.557 MPa） and elongation at break （596.137%） are reasonably matched with Shore A hardness （61）， featuring both excellent bonding strength and the ability to adapt to fabric deformation. The intrinsic mechanism for the balanced performance of HMDI type TPU lies in its moderate microphase separation structure， with the degree of phase separation between MDI type and IPDI type. This structure enables it to better penetrate the substrate during bonding， ensuring bonding reliability. Printed fabrics made of HMDI type CO2-based TPU performed the best. It has a relatively high dry and wet rubbing fastness and a relatively low stiffness， achieving a unity of wearing comfort and pattern durability.

Key words: polypropylene carbonate diol, digital heat transfer printing, thermoplastic polyurethane hot melt adhesive, dicyclohexylmethane-4, 4'-diisocyanate, isophorone diisocyanate, CO2-based polyurethane

CLC Number: 

  • TS195.1

Fig.1

Synthesis route and molecular structure of HMDI type TPU"

Fig.2

FT-IR images of different hard segment CO2-based TPU"

Fig.3

Structures of different hard segment CO2-based TPU and 1H-NMR spectra"

Fig.4

DSC curves of CO2-based TPU with different hard segments"

Fig.5

TGA curves of CO2-based TPU with different hard segments"

Tab.1

TGA characteristic temperatures of CO2-based TPU with different hard segments"

异氰酸酯种类 T5/℃ T50/℃ Tmax/℃
IPDI 278.5 317.0 322.9
HMDI 282.1 324.0 329.5
MDI 291.8 326.6 332.6

Tab.2

Breaking strength， elongation at break， elasticity modulus and shore hardness of CO2-based TPU films"

异氰酸酯
种类		 断裂强
度/MPa		 断裂伸长
率/%		 弹性模
量/MPa		 邵氏A
硬度
MDI 20.119 548.206 9.736 88
HMDI 15.557 596.137 8.732 61
IPDI 14.840 774.309 4.066 54

Tab.3

Bonding/peel strength of CO2-based TPU with different hard segments to different substrates"

异氰酸酯种类 黏结强度/MPa 剥离强度/（N·mm-1）
IPDI 1.50 ± 0.15 1.14
HMDI 2.64 ± 0.34 3.08
MDI 2.67 ± 0.21 1.08

Fig.6

Photos of failure surfaces of CO2-based TPU stainless steel sheets with different hard segments after bonding strength tests"

Fig.7

AFM images of CO2-based TPU films with different hard segments. （a） IPDI type TPU； （b） HMDI type TPU； （c） MDI type TPU"

Tab.4

Dry and wet rubbing fastness， relative stiffness and washing fastness of heat transfer printed fabrics made from different hard segments of CO2-based TPU and petroleum-based TPU"

TPU
种类		 耐干摩擦色
牢度/级		 耐湿摩擦色
牢度/级		 相对硬挺
度/%		 耐水洗色
牢度/级
MDI型 2~3 2~3 308 2~3
IPDI型 2~3 2~3 115 2
HMDI型 4~5 4~5 126 4~5
石油基TPU粉 4 4 202 4

Fig.8

Pattern retention status of heat transfer printed fabrics made from different hard segments of IPDI type（a）， MDI type（b）， HDMT type TPU（c） and petroleum-based TPU after repeated washing 50 times"

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