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Research on the preparation and performance of acrylic acid/methyl acrylate-modified starch catalyzed by an HRP binary initiation system

Abstract

Acrylic acid (AA)/methyl acrylate (MA)-modified starch was prepared via a catalytic process involving horseradish peroxidase (HRP)/acetylacetone (ACAC) as an initiation system. The structural analysis results demonstrated that the grafting of AA and MA onto starch was successful. Furthermore, the impact of the grafting reaction conditions on the grafting effect and the characteristics of the resulting grafted products were also examined. The results demonstrated that AA and MA were successfully grafted onto starch. The optimal conditions for starch grafting with AA/MA were identified as a reaction time of 4 h, an HRP enzyme concentration of 12 U/mL, a total monomer/starch ratio of 4:6, and a molar ratio of AA/MA feeding of 3:7. The viscosity and viscoelasticity of the modified starch slurry increased, and the film-forming property was enhanced. Compared with the original starch film, the modified film markedly increased the flexibility and tensile strength. Furthermore, an increased acrylic acid content maintained the original hydrophilicity of the modified starch film.

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References

  1. Lee H, Choi S, Kim J, Lee K. An experimental investigation on mechanical fatigue property of chemical starch-based ER fluids. J Intel Mat Syst Str. 2002;13:629 https://doi.org/10.1177/1045389X02013010004.

    Article  Google Scholar 

  2. Chen ND. Soochow University. TS103.846, SuZhou, 2012, https://doi.org/10.7666/d.y2122174.

  3. Cheng DS, Yu W, Wang S. Manufacture and property of Co60 Co-radiation grafted starch. Cotton Textile Technol. 2010; 4. https://doi.org/10.3969/j.issn.1001-7415.2010.02.001.

  4. Tan M, Xie J, Yang W, Xu D. Study of starch graft copolymerization initiation system. Ind Catal. 2005; 3. https://doi.org/10.3969/j.issn.1008-1143.2005.z1.088.

  5. Mostafa KM. Graft polymerization of acrylic acid onto starch using potassium permanganate acid (redox system). J Appl Polym Sci. 1995;56:263 https://doi.org/10.1002/app.1995.070560217.

    Article  CAS  Google Scholar 

  6. Wang S, Cheng D, Yu W. Analysis of the effect of Co-60 radiation modification on starch. China Textile Leader. 2008; 109. https://doi.org/10.3969/j.issn.1003-3025.2008.10.024.

  7. Yu F, Yao S. Ultraviolet photoinitiation of starch grafted with acrylonitrile (I). Polym Mater Sci Eng. 1998;02:32. https://doi.org/10.16865/j.cnki.1000-7555.1998.02.009.

    Article  Google Scholar 

  8. Shen S, Zhu Z, Liu F. Introduction of poly[(2-acryloyloxyethyl trimethyl ammonium chloride)-co-(acrylic acid)] branches onto starch for cotton warp sizing. Carbohydr Polym. 2016;138:280–9. https://doi.org/10.1016/j.carbpol.2015.11.058.

    Article  PubMed  CAS  Google Scholar 

  9. Xu L, Yang C, Duan B, Jiang C. Lipase-catalyzed synthesis of starch/polycaprolactone graft copolymers. Polym Mater Sci Eng. 2009;25:34. https://doi.org/10.3321/j.issn:1000-7555.2009.07.010.

    Article  CAS  Google Scholar 

  10. Chen FD. Jiangnan University. O636.12, 2009, https://doi.org/10.7666/d.y1584271.

  11. Lv S, Ma Y, Liu G, Hou M, Yan X, Gong R. pH control method for HRP-catalysed polymerization of sodium p-hydroxybenzenesulphonate and its applications. China Leather. 2011;40:5. https://doi.org/10.13536/j.cnki.issn1001-6813.2011.05.013.

    Article  Google Scholar 

  12. Lv S, Sun T, Zhou Q, Liu J, Ding H. Synthesis of starch-gp (DMDAAC) using HRP initiation and the correlation of its structure and sludge dewaterability. Carbohyd Polym. 2014;103:285. https://doi.org/10.1016/j.carbpol.2013.12.036.

    Article  CAS  Google Scholar 

  13. Wang S, Wang Q, Xu J, Fan X, Wang P. Preparation and its sizing properties of starch-poly(methyl acrylate) size catalyzed by horseradish peroxidase. J Text Res. 2017;38:6 https://doi.org/10.13475/j.fzxb.20160703006.

    Article  Google Scholar 

  14. Liu G, Lv S, Ma Y. Preparation and properties of HRP-catalysed starch-acrylamide graft copolymers. China Leather. 2010; 5. https://doi.org/10.13536/j.cnki.issn1001-6813.2010.05.002.

  15. Wang S, Xu J, Wang Q, Fan X, Yu Y, Wang P, et al. Preparation and rheological properties of starch-g-poly (butyl acrylate) catalyzed by horseradish peroxidase. Process Biochem. 2017;59:104 https://doi.org/10.1016/j.procbio.2017.01.014.

    Article  CAS  Google Scholar 

  16. Shogren RL, Willett JL, Biswas A. HRP-mediated synthesis of starch–polyacrylamide graft copolymers. Carbohyd Polym. 2009;75:189 https://doi.org/10.1016/j.carbpol.2008.07.004.

    Article  CAS  Google Scholar 

  17. Xu S, Fan X, Wang Q, Xu J. Preparation and properties of binary grafted starch modified by horseradish peroxidase. N Chem Mater. 2019;47:5. https://doi.org/CNKI:SUN:HGXC.0.2019-08-049.

    Google Scholar 

  18. Liu Z, Jiang H. Synthesis of water-soluble sodium and methyl acrylate copolymers and study of their dispersion properties. Appl Chem Ind. 2009;38:4. https://doi.org/10.16581/j.cnki.issn1671-3206.2009.03.010.

    Article  CAS  Google Scholar 

  19. Biller P, Ross A. Pyrolysis GC–MS as a novel analysis technique to determine the biochemical composition of microalgae. Algal Res. 2014;6:91. https://doi.org/10.1016/j.algal.2014.09.009.

    Article  Google Scholar 

  20. Zhang Y, Gu Z, Hong Y, Li Z, Cheng L. Pasting and rheologic properties of potato starch and maize starch mixtures. Starch-Starke. 2011;63:11 https://doi.org/10.1002/star.200900255.

    Article  CAS  Google Scholar 

  21. Angles MN, Dufresne A. Plasticized starch/tunicin whiskers nanocomposites. 1. Structural analysis. Macromolecules. 2000;33:8344. https://doi.org/10.1021/MA0008701.

    Article  CAS  Google Scholar 

  22. Liu M, Wu J, Xie Y. Study on the pattern of graft copolymerization reaction between butyl acrylate and potato starch. Polym Mater Sci Eng. 1993;9:5. https://doi.org/10.1007/BF02943552.

    Article  Google Scholar 

  23. Hu C, Lv T, Zhang Y. Synthesis of polymeric chelating agents by starch-grafted methyl acrylate and ethylenediamine. Chin J Chem. 2007;24:716. https://doi.org/10.3969/j.issn.1000-0518.2007.06.025.

    Article  CAS  Google Scholar 

  24. Fan H, Chen Z. Synthesis and characterization of starch/DMDAAC-AM graft copolymers. Polym Mater Sci Eng. 2002;18:62. https://doi.org/10.16865/j.cnki.1000-7555.2002.05.014.

    Article  CAS  Google Scholar 

  25. Braun D, Czerwinski W, Disselhoff G, Tüdős F, Kelen T, Turcsányi B. Analysis of the linear methods for determining copolymerization reactivity ratios, VII. A critical reexamination of radical copolymerizations of styrene. Angew Makromol Chem. 1984;125:161. https://doi.org/10.1002/apmc.1984.051250112.

    Article  CAS  Google Scholar 

  26. Gao Y, Wang L. Cracking chromatography/mass spectrometry study of acrylic emulsion polymers. Paint Coat Ind. 1993; 4. CNKI:SUN:TLGY.0.1993-06-013.

  27. Tang D, Wang W. Cracking gas chromatography-mass spectrometry study of acrylic resins. China Coat. 2013; 5. https://doi.org/10.13531/j.cnki.china.coatings.2013.04.007.

  28. Wu J, Zhang G, Xue S, Jiang L. Pyrolysis mechanism of acrylate polymers by cracking-gas chromatography-mass spectrometry technique. Polym Mater Sci Eng. 1987; 80. https://doi.org/10.16865/j.cnki.1000-7555.1987.05.014.

  29. Li H, Li M, Wang X. Synthesis and application of starch/BA-VAc graft copolymer. Polym Mater Sci Eng. 1997;13:4. https://doi.org/10.16865/j.cnki.1000-7555.1997.01.031.

    Article  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Key Research and Development Program of China (2021YFC2104000). We are grateful for the support from the International Joint Research Laboratory for Eco-Textile Technology at Jiangnan University.

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Wenda Wang: Conceptualization, methodology, software, formal analysis, investigation, and writing—original draft. Qiang Wang: Conceptualization, methodology, validation, resources, supervision, and writing—review & editing. Ping Wang: Supervision.

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Correspondence to Qiang Wang.

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Wang, W., Wang, Q. & Wang, P. Research on the preparation and performance of acrylic acid/methyl acrylate-modified starch catalyzed by an HRP binary initiation system. Polym J 57, 189–201 (2025). https://doi.org/10.1038/s41428-024-00982-x

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