Locating the Reaction Site of 1,2,3,4-Butanetetracarboxylic Acid Carboxyl and Cellulose Hydroxyl in the Esterification Cross-Linking

Bolin Ji; Xiaowen Wang; Shoujia Gong; Weibing Zhong; Ruyi Xie

doi:10.1021/acsomega.1c04718

Locating the Reaction Site of 1,2,3,4-Butanetetracarboxylic Acid Carboxyl and Cellulose Hydroxyl in the Esterification Cross-Linking

ACS Omega. 2021 Oct 14;6(42):28394-28402. doi: 10.1021/acsomega.1c04718. eCollection 2021 Oct 26.

Authors

Bolin Ji^{1

2}, Xiaowen Wang¹, Shoujia Gong¹, Weibing Zhong³, Ruyi Xie^{4

2}

Affiliations

¹ National Engineering Research Center for Dyeing and Finishing of Textiles, College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620, PR China.
² National Innovation Center of Advanced Dyeing and Finishing Technology, Tai'an 271000, PR China.
³ State Key Laboratory of New Textile Materials and Advanced Processing Technologies, Wuhan Textile University, Wuhan 430200, PR China.
⁴ College of Textiles & Clothing, Qingdao University, Qingdao 266071, PR China.

Abstract

The modification of cellulose with polycarboxylic acid is an important technology to functionalize the substrate. 1,2,3,4-Butanetetracarboxylic acid (BTCA) can significantly improve the anti-wrinkle performance of treated cotton fabrics by cross-linking with cellulose. However, the reaction site of BTCA carboxyl and the cellulose hydroxyl has not yet been clarified, which hinders the in-depth understanding about the reaction mechanism and the development of new cross-linking reagents. This study combines Fourier transform infrared and two-dimensional correlation spectroscopy to try to make it clear. Results confirmed that BTCA anhydride is an active intermediate (corresponding to the generally accepted theory) to esterify with cellulose hydroxyl, especially the O(6)-H(6) and O(2)-H(2). Cellobiose was taken as a model of cellulose to react with BTCA at variable temperatures, proving the above conclusion. In addition, the C14- or C11-containing carboxyl of BTCA showed a higher reactivity. Based on calculating reaction kinetics and thermodynamics with Gaussian 09W software, the most likely reaction route between BTCA and cellulose was as follows: BTCA → BTCA C5C14 anhydride → C14O15 ester → C14O15 ester C31C34 anhydride → C14O15C33O ester.