DOI QR코드

DOI QR Code

Synthesis of Biodegradable Carboxymethylcellulose-Alginate Hydrogel Using Dual Cross-Linking Method

이중 가교법을 이용한 생분해성 carboxymethylcellulose-alginate 하이드로겔 제조

  • So Yeon An (School of Energy, Materials & Chemical Engineering, Korea University of Technology and Education) ;
  • Da Yeon Ryu (School of Energy, Materials & Chemical Engineering, Korea University of Technology and Education) ;
  • Young Mi Chung (School of Energy, Materials & Chemical Engineering, Korea University of Technology and Education)
  • 안소연 (한국기술교육대학교 에너지신소재화학공학부) ;
  • 류다연 (한국기술교육대학교 에너지신소재화학공학부) ;
  • 정영미 (한국기술교육대학교 에너지신소재화학공학부)
  • Received : 2025.02.06
  • Accepted : 2025.03.11
  • Published : 2025.04.10

Abstract

This study investigates the development and application potential of eco-friendly and biodegradable hydrogel in response to growing interest in environmental issues and sustainable materials. Carboxymethyl cellulose (CMC) and sodium alginate (NAG) are both biodegradable polymers derived from natural sources, characterized by non-toxicity, cost-effectiveness, abundant availability, and strong water absorption capabilities through hydrogen bonding. In this study, a dual-crosslinking technique was employed to maximize the physical strength and swelling properties of hydrogel by pre-treating CMC/NAG-based hydrogels with citric acid, followed by crosslinking with calcium chloride (CaCl2). The manufactured hydrogel exhibited the highest hygroscopicity under crosslinking conditions using CaCl2 after pretreatment with citric acid at high concentrations of CMC/NAG. It also demonstrated the property of maintaining or even enhancing hygroscopicity under pressurized conditions. This study presents an efficient manufacturing process and optimal conditions for the development of biodegradable hydrogels. By producing CMC/NAG in bead form, this work optimizes the porous structure and absorption rate, showcasing its potential for applications in various fields such as agriculture, pharmaceuticals, and consumer goods.

본 연구에서는 환경 문제와 지속 가능한 소재에 대한 관심이 증가함에 따라, 친환경적이고 생분해 가능한 초흡수성 하이드로겔의 개발 및 응용 가능성을 연구하였다. CMC (carboxymethyl cellulose)와 NAG (sodium alginate)는 모두 자연 유래의 생분해성 고분자로, 비독성, 경제성, 풍부한 공급 가능성을 특징으로 하며, 물과의 강한 수소결합을 통해 우수한 흡수 능력을 발휘한다. 본 연구에서는 CMC/NAG를 기반으로 하여 구연산(citric acid, CA)으로 하이드로겔을 전처리한 뒤 염화칼슘(CaCl2)을 가교제로 사용하는 이중 가교 기술을 통해 CMC의 물리적 강도와 팽윤 특성을 극대화하였다. 제조된 하이드로겔은 고농도의 CMC/NAG, CA 전처리 후 염화칼슘을 이용한 가교조건에서 흡습도가 가장 높은 것으로 밝혀졌으며, 가압상태에서도 흡습도가 유지되거나 향상되는 성질을 보였다. 본 연구는 생분해성 하이드로겔 개발을 위한 효율적인 제조 공정과 최적 조건을 제시하며, CMC/NAG를 비드 복합체 형태로 제작함으로써 다공성 구조와 흡수 속도를 최적화하여 농업, 의약품, 생활용품 등 다양한 분야에서의 적용 가능성을 보여준다.

Keywords

Acknowledgement

이 논문은 2023년 지역특화산업육성 R&D사업 (S3368057) 및 2023년도 한국기술교육대학교 교수 교육연구진흥과제의 지원에 의해 수행된 연구결과입니다.

References

  1. H. M. Dardeer, A. N. Gad, and M. Y. Mahgoub, Promising superabsorbent hydrogel based on carboxymethyl cellulose and polyacrylic acid: Synthesis, characterization, and applications in fertilizer engineering, BMC Chem., 15, 1-13 (2024).
  2. B. Singh, S. Sharma, and A. Dhiman, Design of antibiotic containing hydrogel wound dressings: Biomedical properties and histological study of wound healing, Int. J. Pharm., 457, 82-91 (2013). https://doi.org/10.1016/j.ijpharm.2013.09.028
  3. E. Fu, S. Zhang, Y. Luan, Y. Zhang, S. Saghir, and Z. Xiao, Novel superabsorbent polymer composites based on α-cellulose and modified zeolite: Synthesis, characterization, water absorbency and water retention capacity, Cellulose, 28, 1727-1737 (2021).
  4. A. Sorokin, P. Sukhanov, V. Popov, S. Kannykin, and M. Lavlinskaya, A new approach to increasing the equilibrium swelling ratio of the composite superabsorbents based on carboxymethyl cellulose sodium salt, Cellulose, 28, 159-173 (2021).
  5. G. O. Akalin, Alginate/carboxymethylcellulose-based hydrogels as pH-sensitive drug delivery systems: Facile production with enhanced degradation, thermal and mechanical properties, Iran. Polym. J., 32, 1013-1032 (2023). https://doi.org/10.1007/s13726-023-01182-9
  6. C. W. Shin and S. K. Choi, Depolymerization of sodium alginates by e-beam irradiation, Appl. Chem. Eng., 25, 227-232 (2014). https://doi.org/10.14478/ace.2014.1023
  7. J. E. Jung, K. Song, and S. M. Kang, Recent advances in the development of hydrogel-based functional adsorbents, Appl. Chem. Eng., 34, 461-471 (2023).
  8. T. Fekete, J. Borsa, E. Takács, and L. Wojnárovits, Synthesis of carboxymethylcellulose/starch superabsorbent hydrogels by gamma-irradiation, Chem. Cent. J., 11, 1-10 (2017). https://doi.org/10.1186/s13065-016-0232-6
  9. H. X. Li, X Tian, L. Zhang, L. Wang, L. Jin, and Q. Cao, Synthesis and properties of cellulose-based superabsorbent hydrogel by a new crosslinker, Fibers Polym., 21, 1395-1402 (2020). https://doi.org/10.1007/s12221-020-9978-5
  10. Y. Sheng, J. Gao, Z. Z. Yin, J. Kang, and Y. Kong, Dual-drug delivery system based on the hydrogels of alginate and sodium carboxymethyl cellulose for colorectal cancer treatment, Carbohydr. Polym., 269, 118325 (2021). https://doi.org/10.1016/j.carbpol.2021.118325
  11. W. Lan, L. He, and Y. Liu, Preparation and properties of sodium carboxymethyl cellulose/sodium alginate/chitosan composite film, Coatings, 8, 291, 1-17 (2018).
  12. K. Zhang, Y. Wang, Q. Wei, X. Li, Y. Guo, and S. Zhang, Design and fabrication of sodium alginate/carboxymethyl cellulose sodium blend hydrogel for artificial skin, Gels, 7, 115 (2021). https://doi.org/10.3390/gels7030115
  13. N. F. Che Nan, N. Zainuddin, and M. Ahmad, Preparation and swelling study of CMC hydrogel as potential superabsorbent, Pertanika J. Sci. Technol., 27, 489-498 (2019)
  14. B. Kim, T. H. Kim, and B, Lee, Optimal synthesis of carboxymethylcellulose-based composite superabsorbents, Korean J. Chem. Eng., 37, 215-225 (2020).
  15. C. D. Bucak, Porous alginate hydrogel beads cross-linked with citric acid containing tannic acid: Structural analysis, antimicrobial properties and release behavior, Cellulose, 30, 1-12 (2023). https://doi.org/10.1007/s10570-022-04947-2
  16. M. G. Raucci, M. A. Alvarez-Perez, C. Demitri, D. Giugliano, V. De Benedictis, A. Sannino, and L. Ambrosio, Effect of citric acid crosslinking cellulose-based hydrogels on osteogenic differentiation, J. Biomed. Mater. Res. A, 103, 2045-2056 (2015). https://doi.org/10.1002/jbm.a.35343
  17. T. QI, Preparation and Characterization of Citric Acid Cross-Linked Carboxymethylcellulose Hydrogel, BSc Thesis, Universiti Sains Malaysia, Malaysia (2021).
  18. N. Grishkewich, N. Mohammed, and K. C. Tam, Impact of crosslinking agents on the adsorptive performance of cellulose nanocrystal–alginate hydrogel beads, Cellulose, 30, 6933-6943 (2023). https://doi.org/10.1007/s10570-023-05300-x
  19. V. S. D. Mesias, D. P. Penaloza Jr, Synthesis, characterization, and controlled release property evaluation of carboxymethyl cellulose/alginate (CMC/Alg) encapsulated NPK Fertilizers, Philipp J. Sci., 150, 183-191 (2021).
  20. W. M. Hosny, A. H. Basta, and H. El-Saied, Metal chelates with some cellulose derivatives: V. synthesis and characterization of some iron (III) complexes with cellulose ethers, Polym. Int., 42, 157-162 (1997). https://doi.org/10.1002/(SICI)1097-0126(199702)42:2<157::AID-PI632>3.0.CO;2-7
  21. D. Hawkins, Addition of Chelated Trivalent Cations to Solutions of the Polymer Sodium Carboxymethylcellulose (CMC), MSc Thesis, Rochester Institute of Technology, USA (1999).