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Thermal and mechanical properties of cationic starch-graft-poly(butyl acrylate-co-methyl methacrylate) latex film obtained by semi-continuous emulsion polymerization for adhesive application

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Abstract

In this work, thermal and mechanical properties of cationic cassava starch-g-poly(butyl acrylate-co-methyl methacrylate) films with different amounts of cationic cassava starch (CCS) were studied. The objective of this work was to substitute a portion the monomers (BA/MMA) by CCS in the copolymer and to investigate the consequent effects on the properties of the polymer latex films (e.g., graft percentage, surface tension, thermal and mechanical properties). The results show that the grafting percentage decreased as the concentration of CCS increased. Thermal and mechanical properties of polymer films showed a direct relationship with respect to the content of CCS used and the grafting percentage. Higher grafting percentage led to improvement of the thermal degradation, which indicated better thermal stability than neat poly(BA/MMA). DSC analysis showed that the Tg of the graft copolymers was a little lower as compared to Tg values of un-grafted copolymers. The addition of CCS increases the tensile, elastic modulus and hardness properties of the polymer film, but the elongation at break decreased dramatically. The optimal CCS contents that maximized not only thermal properties, but also mechanical properties, were 7 and 10 mass%, which are directly related to the grafting percentage and CCS content in the formulation. In addition, these results create a new approach for the application of CCS graft-polymer as an adhesive for wood, paper and shoes insole applications.

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References

  1. Srivastava S. Co-polymerization of acrylates. Des Monomers Polym. 2009;12:1–18. https://doi.org/10.1163/156855508X391103.

    Article  CAS  Google Scholar 

  2. Sun D, Zhang Y. Preparation of fast-drying waterborne nano-complex traffic-marking paint. J Coat Technol Res. 2012;9:151–6.

    Article  CAS  Google Scholar 

  3. Bao Y, Ma J, Zhang X, Shi C. Recent advances in the modification of polyacrylate latexes. J Mater Sci. 2015;50:6839–63.

    Article  CAS  Google Scholar 

  4. Cheng S, Xu J, Wu Y. Preparation and characterization of oxidized starch-graft-poly(styrene-butyl acrylate) latex via emulsion polymerization. J Polym Eng. 2014;34:611–6.

    Article  CAS  Google Scholar 

  5. Urban D, Takamura K. Polymer dispersions and their industrial applications. New York: Wiley-VCH Verlag GmbH & Co. KGaA; 2002.

    Book  Google Scholar 

  6. Messmer NR, Anjos EGR, Guerrini LM, Oliveira MP. Effect of geometry and hybrid adhesive on strength of finger joints of Pinus elliottii subject to humidity and temperature. J Adhes. 2018;94:614–957.

    Article  Google Scholar 

  7. Noordergraaf IW, Fourie TK, Raffa P. Free-radical graft polymerization onto starch as a tool to tune properties in relation to potential applications. A review. Processes. 2018;6:31. https://doi.org/10.3390/pr6040031.

    Article  CAS  Google Scholar 

  8. Meshram MW, Patil VV, Mhaske ST, Thorat BN. Graft copolymers of starch and its application in textiles. Carbohydr Polym. 2009;75:71–8.

    Article  CAS  Google Scholar 

  9. Alcázar-Alay SC, Meireles MAA. Physicochemical properties, modifications and applications of starches from different botanical sources. Food Sci Technol. 2015;35:215–36.

    Article  Google Scholar 

  10. Worzakowska M. Thermal studies on the starch-g-copolymers prepared from two terpene acrylate monomers under oxidative conditions. J Therm Anal Calorim. 2019;137:1559–65.

    Article  CAS  Google Scholar 

  11. Maurer HW, Kearney RL. Opportunities and challenges for starch in the paper industry. Starch-Stärke. 1998;50:396–402.

    Article  CAS  Google Scholar 

  12. Li H, Qi Y, Zhao Y, Chi J, Cheng S. Starch and its derivatives for paper coatings: a review. Progr Org Coat. 2019;135:213–27.

    Article  CAS  Google Scholar 

  13. Zeeman SC, Kossmann J, Smith AM. Starch: its metabolism, evolution, and biotechnological modification in plants. Annu Rev Plant Biol. 2010;61:209–34. https://doi.org/10.1146/annurev-arplant-042809-112301.

    Article  CAS  PubMed  Google Scholar 

  14. Niegelhell K, Chemelli A, Hobisch J, Griesser T, Reiter H, Hirn U, Spirk S. Interaction of industrially relevant cationic starches with cellulose. Carbohydr Polym. 2018;179:290–6.

    Article  CAS  Google Scholar 

  15. Kuo WY, Lai HM. Changes of property and morphology of cationic corn starches. Carbohydr Polym. 2007;69:544–53.

    Article  CAS  Google Scholar 

  16. Meimoun J, Wiatz V, Saint-Loup R, Parc J, Favrelle A, Bonnet F, Zinck P. Modification of starch by graft copolymerization. Starch/Stärke. 2017;70:1600351.

    Article  Google Scholar 

  17. Smeets NMB, Imbrogno S, Bloembergen S. Carbohydrate functionalized hybrid latex particles. Carbohydr Polym. 2017;73:233–52.

    Article  Google Scholar 

  18. Cummings S, Zhang Y, Smeets N, Cunningham M, Dubé MA. On the use of starch in emulsion polymerizations. Processes. 2019;7:140. https://doi.org/10.3390/pr7030140.

    Article  CAS  Google Scholar 

  19. Cazotti JC, Fritz AT, Garcia-Valdez O, Smeets NMB, Dube MA, Cunningham MF. Graft modification of starch nanoparticles using nitroxide-mediated polymerization and the grafting from approach. Carbohydr Polym. 2020. https://doi.org/10.1016/j.carbpol.2019.115384.

    Article  PubMed  Google Scholar 

  20. Jyothi AN, Carvalho AJF. In: Kalia S, Sabaa M, editors. Polysaccharide based graft copolymers. Berlin: Springer; 2013. p. 59–110.

    Chapter  Google Scholar 

  21. Cheng S, Zhao Y, Wu Y. Surfactant-free hybrid latexes from enzymatically hydrolyzed starch and poly(butyl acrylate-methyl methacrylate) for paper coating. Progr Org Coat. 2018;118:40–7.

    Article  CAS  Google Scholar 

  22. Xu J, Hu H. Preparation and characterization of styrene acrylate emulsion surface sizing agent modified with rosin. J Appl Polym Sci. 2012;123:611–6.

    Article  CAS  Google Scholar 

  23. Cho CG, Lee K. Preparation of starch-g-PMMA copolymer by emulsion polymerization. Carbohydr Polym. 2002;48:125–30.

    Article  CAS  Google Scholar 

  24. Pimpan V, Thothong P. Synthesis of cassava starch-g-poly(methyl methacrylate) copolymers with benzoyl peroxide as an initiator. J Appl Polym Sci. 2006;101:4083–9.

    Article  CAS  Google Scholar 

  25. Worzakowska M. Starch-g-poly(benzyl methacrylate) copolymers. J Therm Anal Calorim. 2016;124:1309–18.

    Article  CAS  Google Scholar 

  26. Zhang QL, Tian XH, Sun JY, Yuan YZ, Zhang KT. Preparation of starch-g-PMMA, starch-g-P(MMA/BMA) and starch-g-P(MMA/MA) nanoparticles and their reinforcing effect on natural rubber by latex blending: a comparative study. Polym Sci Ser A. 2017;59:708–17.

    Article  CAS  Google Scholar 

  27. Oliveira MP, Silva CR, Guerrini LM. Effect of itaconic acid on the wet scrub resistance of highly pigmented paints for architectural coatings. J Coat Technol Res. 2011;8:439–47.

    Article  Google Scholar 

  28. American Society for Testing and Materials (ASTM). Standard test method for water absorption of plastics. ASTM D570-98(2018). Annual Book of ASTM Standards. 2018. https://doi.org/10.1520/d0570-98r18.

  29. American Society for Testing and Materials (ASTM). Standard test methods for hardness of organic coatings by pendulum damping tests. ASTM D4366-16, Annual Book of ASTM Standards. (2016. https://doi.org/10.1520/d4366-16.

  30. American Society for Testing and Materials (ASTM). Standard test method for tensile properties of plastics. ASTM D638-14. Annual Book of ASTM Standards-Sec. 15.12. 2014. https://doi.org/10.1520/d0638-14.

  31. Cheng S, Zhao Y. Synthesis of eccentric core-shell particles by surfactant-free emulsion polymerization with enzymatically hydrolyzed starch as the stabilizer. Colloid Polym Sci. 2017;295:2233–41.

    Article  CAS  Google Scholar 

  32. Gaborieau M, De Bruyn H, Mange S, Castignolles P, Brockmeyer A, Gilbert RG. Synthesis and characterization of synthetic polymer colloids colloidally stabilized by cationized starch oligomers. J Polym Sci Part A Polym Chem. 2009;47:1836–52.

    Article  CAS  Google Scholar 

  33. Witono JR, Noordergraaf IW, Heeres HJ, Janssen LPBM. Graft copolymerization of acrylic acid to cassava starch-evaluation of the influences of process parameters by an experimental design method. Carbohydr Polym. 2012;90:1522–9.

    Article  CAS  Google Scholar 

  34. Fox TG, Flory PJ. Second-order transition temperatures and related properties of polystyrene. J Appl Phys. 1950;21:581–91.

    Article  CAS  Google Scholar 

  35. Emelie B, Pichot C, Guillot J. Batch emulsion copolymerization of butyl acrylate and methyl methacrylate in the presence of sodium dodecyl sulfate. Makromol Chem. 1991;192:1629–47.

    Article  CAS  Google Scholar 

  36. Cheng S, Zhao W, Wu Y. Optimization of synthesis and characterization of oxidized starch-graft poly(styrene-butyl acrylate) latex for paper coating. Starch/Stärke. 2015;67:493–501.

    Article  CAS  Google Scholar 

  37. Li MC, Lee JK, Cho UR. Synthesis, characterization, and enzymatic degradation of starch-grafted poly(methyl methacrylate) copolymer films. J Appl Polym Sci. 2012;125:405–14.

    Article  CAS  Google Scholar 

  38. Worzakowska M, Grochowicz M. Effect of some parameters on the synthesis and the physico-chemical properties of new amphiphilic starch-g-copolymers. Carbohydr Polym. 2015;130:344–52.

    Article  CAS  Google Scholar 

  39. Worzakowska M. The effect of starch-g-copolymers structure on the oxidative behavior studied by the TG/DSC/FTIR-coupled method. J Therm Anal Calorim. 2017;129:367–76.

    Article  CAS  Google Scholar 

  40. Kiatkamjornwong S, Thakeow P, Sonsuk M. Chemical modification of cassava starch for degradable polyethylene sheets. Polym Degrad Stab. 2001;73:363–75.

    Article  CAS  Google Scholar 

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Acknowledgements

The authors acknowledge the financial support received of the São Paulo Research Foundation (FAPESP, Grant 2013/25619-3 and 2018/12469-7), National Council for Scientific and Technological Development (CNPq, Grant 314898/2018-2). We also thank Dr. Marlon Santos of BASF SA (Brazil) for his aid in obtaining the reagents used in this work.

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  1. Laboratory of Polymer Synthesis and Process, Department of Science and Technology, Federal University of São Paulo, São José dos Campos, São Paulo, Brazil

    Lina Dayse Alcantara Rodrigues, Lilia Müller Guerrini & Maurício Pinheiro Oliveira

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  1. Lina Dayse Alcantara Rodrigues
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  2. Lilia Müller Guerrini
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  3. Maurício Pinheiro Oliveira
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Correspondence to Maurício Pinheiro Oliveira.

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Rodrigues, L.D.A., Guerrini, L.M. & Oliveira, M.P. Thermal and mechanical properties of cationic starch-graft-poly(butyl acrylate-co-methyl methacrylate) latex film obtained by semi-continuous emulsion polymerization for adhesive application. J Therm Anal Calorim 146, 143–152 (2021). https://doi.org/10.1007/s10973-020-09915-1

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