ارگانوژل ابرتورمی جدید حاصل از رزین اپوکسی برای جذب و ژل‌سازی الکل‌ها و مایعات آلی قطبی

نوع مقاله: پژوهشی

نویسندگان

تهران، پژوهشگاه پلیمر و پتروشیمی ایران، پژوهشکده پتروشیمی، گروه رنگ چسب و رزین، صندوق پستی 115-14965

10.22063/jipst.2020.1750

چکیده

فرضیه: مواد جاذب حلال‌های آلی (ارگانوژل‌‌ها)، شبکه‌های درشت‌‌مولکولی آب‌گریز با قابلیت جذب و نگه‌داری حلال‌های آلی هستند. این مواد در کاربردهای مختلفی از جمله تولید ژل‌های ضدعفونی مصرفی در پزشکی و بهداشت عمومی، استفاده می‌شوند. مقاله حاضر، گزارشی مقدماتی درباره تبدیل رزین اپوکسی (DGEBA) به ارگانو‌ژل اَبَرجاذب جدید دارای گروه‌های فوران و تری‌آزول است.
روش‌ها: ارگانوژل، طی چهار مرحله اصلی از رزین اپوکسی و فوفوریل الکل تهیه شد. رزین اپوکسی، به‌ترتیب فورفوریل‌دار، ایزوسیانات‌دار و پروپارژیل‌دار شد. محصول نهایی، طی واکنش پلیمرشدن حلقه‌زایی 3،1-دوقطبی، ترکیب دی‌آزید تهیه‌شده از اپی‌کلروهیدرین با ترکیب پروپارژیل‌دار به‌دست آمد. ترکیب حدواسط و محصول نهایی با طیف‌نمایی FTIR شناسایی شدند.
محصول نهایی با میکروسکوپی الکترونی پویشی (SEM)، گرماسنجی پویشی تفاضلی (DSC) و گرماوزن‌سنجی (TGA) ارزیابی شد. رفتار رئولوژیکی در حلال N-متیل پیرولیدون (NMP) بررسی و ظرفیت تورم ارگانوژل نیز در حلال‌های مختلف اندازه‌گیری شد.
یافته‌ها: ارگانو‌ژل پلیمری جدید بدون استفاده از عامل شبکه‌ای‌کننده مجزا تهیه شد. ذرات خشک‌شده آن دارای ساختاری متخلخل با میانگین قطر 680nm بودند. تورم، با کاهش گرانروی و افزایش قطبیت حلال، افزایش می‌یابد. رفتار اَبَرتورمی به‌طور عمده، به تلفیقی از اتصالات عرضیِ محدود و نیز برهم‌کنش‌های ابرامولکولی میان گروه‌های عاملی پلیمر-پلیمر و پلیمر-حلال نسبت داده شد. ظرفیت جذب و ژل‌سازیِ حلال‌های قطبی با این ارگانوژل، بسیار زیاد است. ظرفیت تورم ارگانوژل در حلال‌ها به‌ترتیب اتیلن گلیکول ˃ کلروفرم ˃ اتانول ˃ استونیتریل ˃ دی‌متیل فرمامید ˃ دی‌متیل استامید ˃ دی‌متیل سولفوکسید ˃ NMP بود. به‌عنوان مثال، هر گرم از این ارگانو‌ژل می‌تواند در زمان حدود 1h، حدود 145g اتانول و 1853g از NMP را جذب کند و به‌حالت ژل درآید. پیش‌بینی می‌شود، گروه‌های 3،2،1-تری‌آزول، خاصیت ضدباکتری را به این ارگانو‌ژل القا می‌کنند.

کلیدواژه‌ها


عنوان مقاله [English]

A Novel Ultra-High Swelling Organogel: An Epoxy Resin Derived Gelator for Alcohols and Polar Organic Liquids

نویسندگان [English]

  • Zeinab Karami
  • Mohammad Jalal Zohuriaan-Mehr
Department of Adhesive and Resin, Faculty of Petrochemical, Iran Polymer and Petrochemical Institute, P.O. Box 14965-115, Tehran, Iran
چکیده [English]

Hypothesis: Organogels are hydrophobic macromolecular networks with ability to absorb and retain organic solvents. They have been used in various applications, e.g., production of disinfectant hygienic gels used in medicine and public health. The present paper is a preliminary report on the conversion of common epoxy resin (DGEBA) into a new superabsorbent organogel containing functional groups of furan, carbamate, and triazole.
Methods: The organogel was synthesized through a four-step strategy from epoxy resin and furfuryl alcohol. The furfurylated epoxy resin was converted to an isocyanate-terminated compound that then converted into a propargyl-terminated intermediate. The final product was produced by 1,3-dipolar cycloaddition polymerization reaction of a propargylated compound and a diazide compound prepared from epichlorohydrin. The intermediate compounds and the final product were characterized by Fourier transform infrared (FTIR) spectroscopy. The final product was characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Rheological behavior in solvent N-methyl-2-pyrrolidone (NMP) was preliminarily studied and swelling capacity of the organogel was determined in various solvents.
Findings: A novel polymeric organogel was synthesized without using a particular crosslinker. Its dried particles were found to have porosity with a pore diameter of ~680 nm. The organogel showed increased swelling capacity with dropping of solvent viscosity and increasing of solvent polarity. The high solvent uptake and storage capacity by this organogel has supported it as a superabsorbent organogelator. Its swelling capacity was determined in the solvents to be in order: ethylene glycol < chloroform < ethanol < acetonitrile < dimethylformamide < dimethylacetamide < dimethylsulfoxide < NMP. For instance, each gram of the organogel can absorb and gelate ~145 g ethanol, or ~1853 g NMP, within ~1 h. The super-swelling behavior of this solvent-retaining network was preliminarily attributed to a combination of limited crosslinkages as well as some polymer-polymer and polymer-solvent supramolecular interactions. The presence of 1,2,3-triazole groups is also expected to induce antibacterial properties in this organogel.

کلیدواژه‌ها [English]

  • organogel
  • epoxy resin
  • cycloaddition
  • furfuryl alcohol
  • polymer gelator
  1. Vintiloiu A. and Leroux J.C., Organogels and Their Use in Drug Delivery-A Review, J. Contr. Rel., 125, 179-192, 2012.
  2. Suzuki M. and Hanabusa K., Polymer Organogelators that Make Supramolecular Organogels through Physical Cross-linking and Self-assembly, Chem. Soc. Rev., 39, 455-463, 2010.
  3. Tuncaboylu D.C. and Okay O., Preparation and Characterization of Single-hole Macroporous Organogel Particles of High Toughness and Superfast Responsivity, Eur. Polym. J., 45, 2033-2042, 2009.
  4. Sahoo S., Kumar N., Bhattacharya C., Sagiri S.S., Jain K., Pal K., Ray S.S., and Nayak B., Organogels-Properties and Applications in Drug, Des. Monomers. Polym., 14, 95-108, 2011.
  5. Esposito C.L., Kirilov P., and Roullin V.G., Organogels, Promising Drug Delivery Systems: An Update of State of the Art and Recent Applications, J. Contr. Rel., 271, 1-20, 2018.
  6. Zhao Q. and Liu C., Synthesis and Characterization Superabsorbent-Ethanol Polyacrylic Acid Gels, J. Appl. Polym. Sci., 105, 3458-3461, 2007.
  7. Kabiri K., Lashani S., Zohuriaan-Mehr M. J., and Kheirabadi M., Super Alcohol-absorbent Gels of Sulfonic Acid-contained Poly(acrylic acid) , J. Polym. Res., 18, 449-458, 2011.
  8. Kabiri K., Azizi A., Zohuriaan-Mehr M.J., Marandi G.B., and Bouhendi H., Poly(acrylic acid-sodium Styrene Sulfonate) Organogels: Preparation, Characterization, and Alcohol Superabsorbency, J. Appl. Polym. Sci., 119, 2760-2769, 2011.
  9. Kabiri K., Azizi A., Zohuriaan-Mehr M.J., Marandi G.B., and Bouhendi H., Alcohophilic Gels: Polymeric Organogels Composing Carboxylic and Sulfonic Acid Groups, J. Appl. Polym. Sci., 120, 3350-3356, 2011.
  10. Varid V., Mohammadi M., Buohendi H., and Kabiri K., The Absorption of Alcohol and Saline Solution by Carbopol Grafted with 2-Acrylamido-2-methylpropane Sulfonic Acid Prepared Through Ultrasonic Method, Iran. J. Polym. Sci. Technol. (Persian), 32, 255-266, 1398.
  11. Narimani F., Zohuriaan-Mehr M.J., Kabiri K., Bouhendi H., Omidian H., and Najafi V., Overentrant Swelling Behaviour of Poly(potassium, 3-sulfopropyl acrylate-acrylic acid) Gels, J. Polym. Res., 19, 2012. DOI: 10.1007/s10965-012-0007-2.
  12. Narimani F. and Lakouraj M.M., Swelling Behavior and Characterization of Alcohol-specific Superabsorbing Gels Based on Acrylic Acid and Allyl Tetrasodium Thiacalixarene Tetrasulfonate, J. Polym. Res., 22, 2015. DOI: 10.1007/s10965-015-0670-1.
  13. Doshi B., Sillanpaa M., and Kalliola S., A Review of Bio-based Materials for Oil Spill Treatment, Water Res., 135, 262-277, 2018.
  14. Prathap A. and Sureshan K.M., Sugar-Based Organogelators for Various Applications, Langmuir, 35, 6005-6014, 2019.
  15. Najafi V., Kabiri K., Ziaee F., Omidian H., Zohuriaan-Mehr M.J., Bouhendi H., and Farhadnejad H., Synthesis and Characterization of Alcogels Based on Ethylene Glycol Methyl Ether Methacrylate-vinyl Phosphonic Acid Copolymers, J. Polym. Res, 19, 2012. DOI: 10.1007/s10965-012-9866-9.
  16. Hajighasem A. and Kabiri K., Cationic Highly Alcohol-swellable Gels: Synthesis and Characterization, J. Polym. Res., 20, 2013. DOI: 10.1007/s10965-013-0218-1.
  17. Saadati K., Kabiri K., and Marandi G.B., Synthesis and Characterization of Phosphonic-Acrylic Organogels, Int. J. Polym. Mater. Polym. Biomater., 63, 430-437, 2014.
  18. Marandi G. B., Azizi A., Kabiri K., Zohuriaan-Mehr M.J., and Boohendi H., An Alcogel Based on Poly(2-acrylamido-2-methylpropane Sulphonic Acid) and the Effect of Neutralization Degree on its Swelling, Thermal and Mechanical Properties, Iran. J. Polym. Sci. Technol. (Persian), 23, 145-153, 2010.
  19. Zohuriaan-Mehr M. J., Kabiri K., and Kheirabadi M., Extraordinary Swelling Behavior of Poly(AMPS) Organogel in Solvent/DMSO Binary Mixed Media, J. Appl. Polym. Sci., 117, 1127–1136, 2010.
  20. Kabiri K., Azizi A., Zohuriaan-Mehr M.J., Marandi G.B., Bouhendi H., and Jamshidi A., Super-alcogels Based on 2-Acrylamido-2-methylpropane Sulphonic Acid and Poly(ethylene glycol) Macromer, Iran. Polym. J., 20, 3, 175-183, 2011.
  21. Karami Z., Zohuriaan-mehr M.J., and Rostami A., Biobased Diels-Alder Engineered Network from Furfuryl Alcohol and Epoxy Resin : Preparation and Mechano-Physical Characteristics, ChemistrySelect, 3, 12099-12105, 2018.
  22. Zolghadr M., Shakeri A., and Zohuriaan-mehr M.J., Self-healing Semi-IPN Materials from Epoxy Resin by Solvent-free Furan – maleimide Diels–Alder Polymerization, J. Appl. Polym. Sci., 136, 48015, 2019.
  23. Diaz D.D., Tellado J.J.M., Velazquez D.G., and Ravelo A.G., Polymer Thermoreversible Gels from Organogelators Enabled by ‘Click’ Chemistry, Tetrahedron Lett., 49, 1340-1343, 2008.
  24. Díaz D.D., Cid J.J., Vázquez P., and Torres T., Strength Enhancement of Nanostructured Organogels through Inclusion of Phthalocyanine-Containing Complementary Organogelator Structures and In Situ Cross-Linking by Click Chemistry, Chem. Eur. J., 14, 9261– 9273, 2008.
  25. Priyanka K.G., Mishra A.K., Kantheti S., and Narayan R., and  Raju K.V., Synthesis of Triazole Ring-Containing Pentol Chain Extender and Its Effect on the Properties of Hyperbranched Polyurethane-Urea Coatings, J. Appl. Polym. Sci., 126, 2024-2034, 2012.
  26. Hong J., Luo Q., and Shah B.K., Catalyst- and Solvent-Free ‘Click’ Chemistry: A Facile Approach to Obtain Cross-Linked Biopolymers from Soybean Oil, Biomacromolecules, 11, 2960-2965, 2010.
  27. James N.R. and Jayakrishnan A., Synthesis, Polymerization, and Copolymerization of Aliphatic Vinyl Azide, J. Appl. Polym. Sci., 87, 1852-1857, 2003.
  28. Moini N., Zohuriaan-Mehr M.J., Kabiri K., Khonakdar H.A., “Click” on SAP: Superabsorbent Polymer Surface Modification Via CuAAC Reaction Toward Antibacterial Activity and Improved Swollen Gel Strength, Appl. Surf. Sci., 487, 1131-1144, 2019.
  29. Nidhal Okhaya, Nathalie Mignarda, Corinne Jegata M.T., Diels–Alder Thermoresponsive Networks Based on High Maleimide-functionalized Urethane Prepolymers, Des. Monomers Polym., 16, 475-487, 2013.
  30. Karami Z., Nademi F., Zohuriaan-Mehr M.J., and Rostami A., An Efficient Fully Bio-based Reactive Diluent for Epoxy Thermosets: 2-[(Oxiran-2-ylmethoxy) Methyl] Furan Versus a Petroleum-based Counterpart, J. Appl. Polym. Sci., 134, 25, 44957, 2017.
  31. Retrieved, https://macro.lsu.edu/howto/solvents/Polarity%20index.htm, April 2020.
  32. Mondal J., Modak A., Dutta A., and Bhaumik A., Facile C–S Coupling Reaction of Aryl Iodide and Thiophenol Catalyzed by Cu-grafted Furfural Functionalized Mesoporous Organosilica, Dalton Trans., 40, 5228-5235, 2011.
  33. Gündüzalp A.B., Özsen İ., Alyar H., Alyar S., and Özbek N., Biologically Active Schiff Bases Containing Thiophene/Furan Ring and Their Copper(II) Complexes: Synthesis, Spectral, Nonlinear Optical and Density Functional Studies, J. Mol. Struct., 2016. DOI: 10.1016/j.molstruc.2016.05.002
  34. Dehno Khalaji A., Maghsodlou Rad G.S., and Grivani D., Nickel(II) and Copper(II) Complexes with an Asymmetric Bidentate Schiff-base Ligand Derived from Furfurylamine: Synthesis, Spectral, XRD, and Thermal Studies, J. Therm. Anal. Calorim., 103,747-751, 2011.
  35. Sumrra S.H., Ibrahim M., Ambreen S., Imran M., Danish M., and Rehmani F.S., Synthesis, Spectral Characterization, and Biological Evaluation of Transition Metal Complexes of Bidentate N, O Donor Schiff Bases, Bioinorg. Chem. Appl., 2014. DOI: 10.1155/2014/812924.
  36. Kohestanian M. and Bouhendi H., Novel Cross-linking Mechanism for Producing PAA Microgels Synthesized by Precipitation Polymerization Method, Colloid Polym. Sci., 293, 1983-1995, 2015.
  37. Kohestanian M., Bouhendi H., and Ghiass M., Synthesis and Characterization of PAA Microgels Using Multifunctional Epoxy Cross-linkers with a New Cross-linking Mechanism via a Precipitation Polymerization Method, J. Polym. Res.,24, 2017. DOI: 10.1007/s10965-017-1347-8