کاربرد حلال‌های بسیار اوتکتیک طبیعی به‌عنوان نرم‌کننده در تهیه فیلم‌های پلیمری طبیعی

نوع مقاله : تالیفی

نویسنده

پژوهشگاه استاندارد

چکیده

حلال ­های بسیار اوتکتیک (DES) جایگزین مایعات یونی (ILs) هستند. این حلال ­ها ترکیباتی زیست­ تخریب­ پذیر، غیرسمی یا با سمیت کم هستند که با روش آسان به ­دست می­ آیند. آن­ها معمولاً با کمپلکس ­شدن یک پذیرنده پیوند هیدروژنی (HBA) با یک دهنده پیوند هیدروژنی (HBD) تهیه می­ شوند که مخلوط بسیار اوتکتیک تشکیل می­ دهند. دمای ذوب این مخلوط از دمای ذوب هر یک از اجزای تشکیل­دهنده آن بسیار کمتر است. کشف حلال ­های بسیار اوتکتیک طبیعی (NADES) استفاده از آن­ها را به ­عنوان جایگزین حلال­ های آلی معمول، که ذاتاً سمی و بسیار فرارند، سرعت بخشیده است. پلی­ ساکاریدها فراوان­ترین پلیمرهای طبیعی هستند و به­ عنوان منابع اولیه احتمالی برای تولید مواد سبز و جایگزینی پلاستیک­ های زیست­­ تخریب ­نا­پذیر درنظرگرفته می­ شوند. با وجود این، معمولاً فیلم ­های تهیه ­شده از پلی­ ساکاریدهای خالص شکننده هستند و خواص مکانیکی ضعیفی دارند که کاربرد آن­ها را محدود می­ کند. این مسئله به توسعه مواد برپایه پلی­ ساکاریدهای اصلاح ­شده با روش شیمیایی یا افزودن پرکننده­ های تقویت­ کننده یا نرم­ کننده ­ها منجر شده است. تاکنون NADESها نه تنها در استخراج، جداسازی یا خالص ­سازی برخی پلیمرهای خاص استفاده شده ­اند، بلکه به ­عنوان اجزای تشکیل ­دهنده مواد برپایه پلی ­ساکاریدها، یعنی نرم ­کننده­ ها، سازگارکننده­ ها یا بهبود دهنده­ ها، نیز استفاده شده­ اند. به­ کارگیری NADES به ­عنوان نرم­ کننده بیشتر برای فیلم ­های نشاسته کاربرد دارد، با وجود این برای مشتقات سلولوز، کیتوسان، آگار و آگاروز نیز به ­کار می ­رود. در این مقاله، قابلیت کاربرد حلال­ های بسیار اوتکتیک طبیعی به­ عنوان نرم­کننده­ های سبز، ارزان و تجدیدپذیر در تهیه فیلم­ های پلیمری طبیعی مرور شده است.

کلیدواژه‌ها


عنوان مقاله [English]

Application of Natural Deep Eutectic Solvents as Plasticizer in Natural Polymeric Films Preparation

نویسنده [English]

  • Fezzeh Aryanasab
Standard Research Institute (SRI)
چکیده [English]

D eep eutectic solvents (DES) are an alternative for ionic liquids (ILs). These solvents are biodegradable, non- or low-toxic compounds that obtained via simple and convenient way. They are usually prepared by complexing of a hydrogen bond acceptor (HBA) and a hydrogen bond donor (HBD), forming a deep eutectic mixture, in such a way that the melting point of the  mixture is much lower than the melting points of each component. The recent discovery of natural deep eutectic solvents (NADES) has accelerated their use as an alternative to conventional organic solvents, which are inherently toxic and highly volatile. Polysaccharides are the most abundant natural polymers and are considered as prospective starting resources for the production of green materials and replacement of non-biodegradable plastics. However, films made from pure polysaccharides are usually brittle and demonstrate poor mechanical properties, that limit their use.This has led to to the development of polysaccharide-based materials modified either chemically or by the addition of reinforcing fillers and plasticizers. To date, NADES have been used not only in the extraction, separation or purification of some specific biopolymers, but also as components of polysaccharide-based materials, e.g. plasticizers, compatibilizers or modifiers. NADESs are used as plasticizer, mainly for starch films, however it is also used for cellulose derivatives, chitosan, agar and agarose. In this paper, the potential application of NADES as green, inexpensive and sustainable plasticizers in the production of natural polymer films is reviewed.

کلیدواژه‌ها [English]

  • Natural Deep Eutectic Solvents
  • natural polymeric film
  • plasticizer
  • biodegradable
  • Sustainable
1. Liu Y., Friesen J.B., McAlpine J.B., Lankin D.C., Chen S.N., and Pauli G.F., Natural Deep Eutectic Solvents: Properties,
Applications, and Perspectives, J. Nat. Prod., 81, 679-690, 2018.
2. Morais E.S., Lopes A.M.C., Freire M.G., Freire C.S.R., Coutinho J.A.P., and Silvestre A.J.D., Use of Ionic Liquids
and Deep Eutectic Solvents in Polysaccharides Dissolution and Extraction Processes towards Sustainable Biomass
Valorization, Molecules, 25, 3652-3703, 2020.
3. Choi Y.H., van Spronsen J., Dai Y., Verberne M., Hollmann F., Arends I.W.C.E., Witkamp G.J., and Verpoorte R., Are Natural Deep Eutectic Solvents the Missing Link in Understanding Cellular Metabolism and Physiology, Plant Physiol., 156,
1701-1705, 2011.
4. Abbott A.P., Capper G., Davies D.L., Rasheed R.K., and Tambyrajah V., Novel Solvent Properties of Choline Chloride/
Urea Mixtures, Chem. Commun., 70-71, 2003.
5. Abbott A.P., Ballantyne A.D., Conde J.P., Ryder K.S., and Wise W.R., Salt Modified Starch: Sustainable, Recyclable Plastics, Green Chem., 14, 1302-1307, 2012.
6. Zdanowicz M., Spychaj T., and Maka H., Imidazole-Based Deep Eutectic Solvents for Starch Dissolution and Plasticization,
Carbohyd. Polym., 140, 416-423, 2016.
7. Wang N., Zhang X., and Han N., A Facile Method for Preparation of Thermoplastic Starch/Urea Modified Montmorillonite
Nanocomposites, J. Comp. Mater., 44, 27-39, 2010.
8. Wilpiszewska K. and Spychaj T., Ionic Liquids: Media for Starch Dissolution, Plasticization and Modification, Carbohyd.
Polym., 86, 424-428, 2011.
9. Zdanowicz M. and Caisa J., Mechanical and Barrier Properties of Starch-Based Films Plasticized with Two- or Threecomponent Deep Eutectic Solvents, Carbohydr. Polym., 151, 103-112, 2016.
10. Zdanowicz M. and Johansson C., Impact of Additives on Mechanical and Barrier Properties of Starch-Based Films
Plasticized with Deep Eutectic Solvents, Starch, 69, 1700030, 2017.
11. Adamus J., Spychaj T., Zdanowicz M., and Jędrzejewski R., Thermoplastic Starch with Deep Eutectic Solvents and
Montmorillonite as a Base for Composite Materials, Ind. Crop. Prod., 123, 278-284, 2018.
12. Willett J.L., Mechanical Properties of LDPE/Granular Starch Composites, J. Appl. Polym. Sci., 54, 1685-1695, 1994.
13. Rodriguez-Gonzalez F.J., Ramsay B.A., and Favis B.D., High Performance LDPE/Thermoplastic Starch Blends: A
Sustainable Alternative to Pure Polyethylene, Polymer, 44, 1517-1526, 2003.
14. Abbott A.P. and Wright L.A., Thermoplastic Starch–Polyethylene Blends Homogenised Using Deep Eutectic Solvents, RSC Adv., 7, 7268-7273, 2017.
15. Zdanowicz M., Jedrzejewski R., and Pilawka R., Deep Eutectic Solvents as Simultaneous Plasticizing and Crosslinking Agentsfor Starch, Int. J. Biol. Macromol., 129, 1040-1046, 2019.
16. Grylewicz A., Spychaj T., and Zdanowicz M., Thermoplastic Starch/Wood Biocomposites Processed with Deep Eutectic
Solvents, Composite: Part A, 121, 517-524, 2019.
17. Zdanowicz M. and Spychaj T., Ionic Liquids as Starch Plasticizers or Solvents, Polymers, 56, 861-864, 2019.
18. Suyatma N.E., Tighzert L., Copinet A., and Coma V., Effects of Hydrophilic Plasticizers on Mechanical, Thermal, and
Surface Properties of Chitosan Films, J. Agr. Food Chem., 53, 3950-3957, 2005.
19. Galvis-Sánchez A.C., Sousa A.M.M., Hilliou L., Gonçalves M.P., and Souza H.K.S., Thermo-compression Molding
of Chitosan with a Deep Eutectic Mixture for Biofilms Development, Green Chem., 18, 1571-1580, 2016.
20. Almeida C.M.R., Magalhães J.M.C.S., Souza H.K.S., and Gonçalves M.P., The Role of Choline Chloride-Based Deep
Eutectic Solvent and Curcumin on Chitosan Films Properties, Food Hydrocoll., 81, 456-466, 2018.
21. Pereira P.F. and Andrade C.T., Optimized pH-Responsive Film Based on a Eutectic Mixture-Plasticized Chitosan, Carbohyd. Polym., 165, 238-246, 2017.
22. Sokolova M.P., Smirnov M.A., Samarov A.A., Bobrova N.V., Vorobiov V.K., Popova E.N. et al., Plasticizing of Chitosan
Films with Deep Eutectic Mixture of Malonic Acid and Choline Chloride, Carbohyd. Polym., 197, 548-557, 2018.
23. Wong W.Y., Wong C.Y., Rashmi W., and Khalid M., Choline Chloride-Urea-Based Deep Eutectic Solvent as Additive to
Proton Conducting Chitosan Films, J. Eng. Sci. Technol., 13, 2995-3006, 2018.
24. Almeida C.M.R., Magalhães J.M.C.S., Souza H.K.S., and Gonçalves M.P., The Role of Choline Chloride-Based Deep
Eutectic Solvent (DES) and Curcumin on Chitosan Films Properties, Food Hydrocoll., 81, 456-466, 2018.
25. Jakubowska E., Gierszewska M., Nowaczyk J., and Olewnik- Kruszkowska E., Physicochemical and Storage Properties of
Chitosan-Based Films Plasticized with Deep Eutectic Solvent, Food Hydrocoll., 108, 106007, 2020.
26. Alcalde R., Gutiérrez A., Atilhan M., and Aparicio S.,  An Experimental and Theoretical Investigation of the
Physicochemical Properties on Choline Chloride-Lactic Acid Based Natural Deep Eutectic Solvent (NADES), J. Mol. Liq.,
290, 110916, 2019.
27. Smirnov M.A., Nikolaeva A.L., Vorobiov V.K., Bobrova N.V., Abalov I.V., Smirnov A.V., and Sokolova M.P., Ionic
Conductivity and Structure of Chitosan Films Modified with Lactic Acid-Choline Chloride NADES, Polymers, 12, 350,
2020.
28. Wang S., Peng X., Zhong L., Jing S., Cao X., Lu F., and Sun R., Choline Chloride/Urea as an Effective Plasticizer for
Production of Cellulose Films, Carbohyd. Polym., 117, 133- 139, 2015.
29. Tenhunen T., Lewandowska A.E., Orelma H., Johansson L., Virtanen T., Harlin A., Österberg M. et al., Understanding the
Interactions of Cellulose Fibres and Deep Eutectic Solvent of Choline Chloride and Urea, Cellulose, 25, 137-150, 2018.
30. Sousa A.M.M., Souza H.K.S., Latona N., Liu C.K., Gonçalves M.P., and Liu L., Choline Chloride Based Ionic Liquid
Analogues as Tool for the Fabrication of Agar Films with Improved Mechanical Properties, Carbohyd. Polym., 111,
206-214, 2014.
31. Sousa A.M.M., Souza H.K.S., Liu L., and Gonçalves M.P., Alternative Plasticizers for the Production of Thermocompressed
Agar Films, Int. J. Biol. Macromol., 76, 138-145, 2015.
32. Shamsuri A.A. and Daik R., Plasticizing Effect of Choline Chloride/Urea Eutectic-Based Ionic Liquid on
Physicochemical Properties of Agarose Films, BioResources, 7, 4760-4775, 2012.
33. Shafie M.H., Samsudin D., Yusof R., and Gan C.Y., Characterization of Bio-Based Plastic Made From a Mixture
of Momordica Charantia Bioactive Polysaccharide and Choline Chloride/Glycerol Based Deep Eutectic Solvent, Int.
J. Biol. Macromol., 118, 1183-1192, 2018.