تهیه نانوهیبریدهای مقاوم گرمایی بر پایه رزین‌های نووالاک و اپوکسی و نانولوله‌های کربن اپوکسی‌دارشده

نوع مقاله: پژوهشی

نویسندگان

تبریز، دانشگاه صنعتی سهند تبریز، صندوق پستی: 1996-51335: 1- دانشکده مهندسی پلیمر، 2- پژوهشکده مواد پلیمری

چکیده

نانوکامپوزیت‌های دارای پایداری گرمایی زیاد از واردکردن نانولوله کربن اصلاح‌شده به داخل ماتریس رزین اپوکسی پخت‌شده با رزین نووالاک تهیه شدند. طی فرایند اصلاح، گروه‌های کربوکسیل در اثر اکسایش با نیتریک اسید و گروه‌های هیدروکسیل با استفاده از واکنش گروه‌های اسیدی ایجاد شده با بوتان دی‌ال روی نانولوله‌های کربن حاصل شدند. سپس، عاملیت اپوکسی روی سطح نانولوله با استفاده از عامل اتصال‌دهنده سیلانی (3- گلیسیدیلوکسی پروپیل)‌تری‌متوکسی‌سیلان ایجاد شد. نانولوله کربن اصلاح‌شده با عاملیت اپوکسی قابلیت واکنش‌پذیری با گروه‌های هیدروکسیل نووالاک را دارد. در اثر پخت نانولوله کربن اصلاح‌شده و رزین اپوکسی دارای گروه‌های اپوکسیدی با رزین نووالاک شبکه هیبریدی مقاوم گرمایی حاصل شد. با توجه به واکنش‌پذیری کم گروه‌های اپوکسی و هیدروکسیل در حالت کاتالیز نشده، از تری‌فنیل فسفین به‌عنوان کاتالیزگر برای تسریع واکنش پخت استفاده شد. در نهایت، نتایج حاصل از طیف‌سنجی زیرقرمز و فوتوالکترونی پرتو X نشان داد، اصلاح نانولوله کربن به‌طور مؤثری انجام شده است. آزمون پراش پرتو X، توزیع یکنواخت نانولوله کربن اصلاح‌شده را در ماتریس اپوکسی پخت‌شده، نشان داد. طبق نتایج تجزیه گرماوزن‌سنجی، واردکردن نانولوله کربن اصلاح‌شده به مقدار 2 و %4 وزنی در داخل شبکه هیبریدی اپوکسی پخت‌شده با نووالاک باعث افزایش شایان توجه مقدار خاکستر باقی‌مانده آن از %26.6 به مقادیر 32.8 و %38.2 شد. بر اساس نتایج به‌دست آمده از میکروسکوپی‌های الکترونی پویشی و عبوری، نانوله‌های کربن ساختارهای درهم تنیده و گره‌خورده با سطحی بسیار صاف و یکنواخت نشان دادند که حتی پس از اصلاح نیز ساختار خود را حفظ می‌کنند. این روش می‌تواند به‌عنوان روش مناسبی برای تهیه گرماسخت‌های با مقاومت گرمایی زیاد برای استفاده در کاربردهای محافظت گرمایی درنظر گرفته شود.

کلیدواژه‌ها


عنوان مقاله [English]

Preparation of Thermally-Resistant Nanohybrids Based on Novolac and Epoxy Resins and Epoxidized Carbon Nanotubes

نویسندگان [English]

  • Sina shahi
  • Hossein Roghani-Mamaqani
  • Mehdi Salami Kalajahi
  • Hamidreza Ebrahimi
Department of Polymer Engineering, 2. Institute of Polymeric Materials; Sahand University of Technology, P.O. Box: 51335-1996, Tabriz, Iran
چکیده [English]

Hypothesis: Thermally stable nanocomposites were prepared by incorporation of carbon nanotubes (CNT) into the epoxy resin matrix cured by novolac resin. CNT modified with epoxy functional groups is capable of reaction with hydroxyl groups of novolac resin. Therefore, a new and robust method was planned for development of covalent bonding between the filler and matrix. On the other hand, due to slow reaction of epoxy and hydroxyl groups in the absence of catalyst, triphenylphosphine was used as the catalyst to accelerate the curing process.
Method: CNT was modified with nitric acid to obtain oxidized CNT (CNTCOOH). After grafting of butane diol at the surface of CNTCOOH, hydroxyl-containing CNT (CNTOH) was prepared. Afterward, epoxy functional groups were applied at the surface of CNTOH through its modification with (3-glycidyloxypropyl) triethoxysilane in order to prepare epoxy-containing CNT (CNTG). Finally, CNTG and epoxy resin were placed in the hybrid network through the curing process with novolac resin.
Finding: The results of FTIR-spectroscopy and X-ray photoelectron spectroscopy showed that modification of CNT was effectively carried out. X-ray diffraction analysis confirmed uniform distribution of CNTG in the matrix of cured epoxy resin. As thermogravimetric analysis exhibited, char yield of the cured epoxy resin (26.6%) was considerably increased to 32.8% and 38.2% through incorporation of 2 and 4 wt% of CNTG into the network, respectively. According to the scanning electron microscopy and transmission electron microscopy images, CNT showed tubular and entangled structure with smooth and uniform surface which even retained its structure after modification reaction. Finally, this approach can be successfully used for production of thermally-resistant thermoset hybrids for thermal protection applications.

کلیدواژه‌ها [English]

  • epoxy resin
  • novolac resin
  • carbon nanotube
  • Nanocomposite
  • thermal properties

1. Liu Y. and Jing X., Pyrolysis and Structure of Hyperbranched Polyborate Modified Phenolic Resins, Carbon, 45, 1965-71, 2007.
2.Xu P. and Jing X., Pyrolysis of Hyperbranched Polyborate Modified Phenolic Resin, Polym. Eng. Sci., 50, 1382-1388, 2010.
3.Chiang C.L., Ma C.C.M., Wu D.L., and Kuan H.C., Preparation, Characterization, and Properties of Novolac-Type Phenolic/SiO2 Hybrid Organic–Inorganic Nanocomposite Materials by Sol-Gel Method, J. Polym. Sci., Part A: Polym Chem, 41, 905-913, 2003.
4.Lin J.M., Ma C.C., Wang F.Y., Wu H.D., and Kuang S.C., Thermal, Mechanical, and Morphological Properties of Phenolic Resin/Silica Hybrid Creamers, J. Polym. Sci., Part B: Polym. Phys., 38, 1699-1706, 2000.
5.Phenolic Resins, Encyclopedia of Polymer Science and Engineering, Mark H.F., Bikales N.M., Overberger C.G., Menges G., and Kroschwitz J.I. (Eds.), 11. New York, Wiley, 1988.
6.Zhang X., Looney M.G., Solomon D.H., and Whittaker A.K., The Chemistry of Novolac Resins: 3. 13C and 15N NMR Studies of Curing with Hexamethylenetetramine, Polymer, 38, 5835-5848, 1997.
7.Klett M.W., Dailey T.H., Jr, and Allison R., New Advancements in Phenolic Resin Pultrusion, Proceeding 25h International SAMPE Technical Conference., October 1993.
8.Branco C.M., Ferreira J.M., Fael P., and Richardson M.O.W., A Comparative Study of the Fatigue Behaviour of GRP Hand Lay-Up and Pultruded Phenolic Composites, Int. J. Fatigue, 18, 255-263, 1995.
9.Wu H.D., Wu Y.D., Su Y.F., and Ma C.C.M., Pultruded Fiber-Reinforced Polyurethane-Toughened Phenolic Resin. II. Mechanical Properties, Thermal Properties, and Flame Resistance, J. Appl. Polym. Sci., 62, 227-234, 1996.
10.Walton G., Manufacturers Tackle Phenolic Processing Challenges, High Perform. Compos., 6, 34-38, 1998.
11.Levchik S.V. and Weil E.D., Thermal Decomposition, Combustion and Flame-Retardancy of Epoxy Resins Review of the Recent Literature, Polym. Int., 53, 1901-1929, 2004.
12.Levchik S.V., Piotrowski A., Weil E.D., and Yao Q., New Developments in Flame Retardancy of Epoxy Resins, Polym. Degrad. Stabil., 88, 57-62, 2005.
13.Hale A., Macosko C.W., and Bair H.E., DSC and 13C-NMR Studies of the Imidazole-Accelerated Reaction Between Epoxides and Phenols, J. Appl. Polym. Sci., 38, 1253-1269, 1989.
14.Shechter L., Wynstra J., and Kurkjy R.P., Glycidyl Ether Reactions with Amines, Ind. Eng. Chem., 48, 94-97, 1956.
15.Mih W.C., Polymers in Electronics, Davidson T. (Ed.), ACS Symp Ser 242, American Chemical Society, Washington, 273, 1984.
16.Han S., Kim W.G., Yoon H.G., and Moon T.J., Curing Reaction of Biphenyl Epoxy Resin with Different Phenolic Functional Hardeners, J. Polym. Sci., Part A: Polym. Chem., 36, 773-783, 1998.
17.Han S., Yoon H.G., Suh K.S., Kim W.G., and Moon T.G., Cure Kinetics of Biphenyl Epoxy-Phenol Novolac Resin System using Triphenylphosphine as Catalyst, J. Polym. Sci., Part A: Polym. Chem., 37, 713-720, 1999.
18.Dogana M. and Unlu S.M., Flame Retardant Effect of Boron Compounds on Red Phosphorus Containing Epoxy Resins, Polym. Degrad. Stabil., 99, 12-17, 2014.
19.Ebrahimi H., Roghani‐Mamaqani H., Salami‐Kalajahi M., Shahi S., and Abdollahi A., Preparation of Furfuryl Alcohol‐Functionalized Carbon Nanotube and Epoxidized Novolac Resin Composites with High Char Yield, Polym. Compos., 39, E1231-E1236, 2018.
20.Mousavi A., Roghani-Mamaqani H., Salami-Kalajahi M., Shahi S., and Abdollahi A., Modification of Graphene with Silica Nanoparticles for Use in Hybrid Network Formation from Epoxy, Novolac, and Epoxidized Novolac Resins by Sol-Gel Method: Investigation of Thermal Properties, Express Polym. Lett., 12, 187-202, 2018.
21.Abdollahi A., Roghani-Mamaqani H., Salami-Kalajahi M., Mousavi A., Razavi B., and Shahi S., Preparation of Organic-Inorganic Hybrid Nanocomposites from Chemically Modified Epoxy and Novolac Resins and Silica-Attached Carbon Nanotubes by Sol-Gel Process: Investigation of Thermal Degradation and Stability, Prog. Organ. Coat., 117, 154-165, 2018.
22.Roghani-Mamaqani H., Haddadi-Asl V., Mortezaei M., and Khezri K., Furfuryl Alcohol Functionalized Graphene Nanosheets for Synthesis of High Carbon Yield Novolak Composites, J. Appl. Polym. Sci., 131, 40273, 2014.
23.Noparvar-Qarebagh A., Roghani-Mamaqani H., and Salami-Kalajahi M., Functionalization of Carbon Nanotubes by Furfuryl Alcohol Moieties for Preparation of Novolac Phenolic Resin Composites with High Carbon Yield Values. Colloid. Polym. Sci., 293, 3623-3631, 2015.
24.Noparvar-Qarebagh A., Roghani-Mamaqani H., and Salami-Kalajahi M., Organic-Inorganic Nanohybrids of Novolac Phenolic Resin and Carbon Nanotube: High Carbon Yields by Using Carbon Nanotube Aerogel and Resin Incorporation into Aerogel Network, Microporous Mesoporous Mater., 224, 58-67, 2016.
25.Noparvar-Qarebagh A., Roghani-Mamaqani H., and Salami-Kalajahi M., Novolac Phenolic Resin and Graphene Aerogel Organic-Inorganic Nanohybrids: High Carbon Yields by Resin Modification and Its Incorporation into Aerogel Network, Polym. Degrad. Stabil., 124, 1-14, 2016.
26.Siouffi A.M., Silica Gel-Based Monoliths Prepared By the Sol-Gel Method: Facts and Figures, J. Chromatogr A, 1000, 801-818. 2003.
27.Noparvar-Qarebagh A., Roghani-Mamaqani H., Salami-Kalajahi M., and Kariminejad B., Nanohybrids of Novolac Phenolic Resin and Carbon Nanotube-Containing Silica Network, J. Therm. Anal. Calorim., 128, 1027-1037, 2017.
28.Najafi-Shoa S., Roghani-Mamaqani H., Salami-Kalajahi M.,Azimi R., and Gholipour-Mahmoudalilou M., Incorporation of Epoxy Resin and Carbon Nanotube into Silica/Siloxane Network for Improving Thermal Properties, J. Mater. Sci., 51, 9057-9073, 2016.
29.Najafi-Shoa S., Roghani-Mamaqani H., and Salami-Kalajahi M., Incorporation of Epoxy Resin and Graphene Nanolayers into Silica Xerogel Network: An Insight into Thermal Improvement of Resin, J. Sol-Gel Sci. Technol., 80, 362-377, 2016.
30.Ren S.P., Lan Y.X., Zhen Y.Q., Ling Y.D., and Lu M.G., Curing Reaction Characteristics and Phase Behaviors of Biphenol Type Epoxy Resins with Phenol Novolac Resins, Thermochim Acta, 440, 60-67, 2006.
31.Pourhosseini‐Pakdel Z., Roghani‐Mamaqani H., Azimi R., and Gholipour‐Mahmoudalilou M., Multifunctional Curing Component for Epoxidized Novolac Resin by Grafting Poly(amidoamine) on Carbon Nanotubes Using A Divergent Method, Polym. Adv. Technol., 29, 2216-2223, 2018.
32.Roghani-Mamaqani H. and Haddadi-Asl V., In-Plane Functionalizing Graphene Nanolayers with Polystyrene by Atom Transfer Radical Polymerization: Grafting from Hydroxyl Groups, Polym. Compos., 35, 386-395, 2014
33.Roghani-Mamaqani H., Haddadi-Asl V., Ghaderi-Ghahfarrokhi M., and Sobhkhiz Z., Reverse Atom Transfer Radical Polymerization of Methyl Methacrylate in the Presence of Azo-Functionalized Carbon Nanotubes: A Grafting from Approach, Colloid. Polym. Sci., 292, 2971-2981, 2014.
34.Roghani-Mamaqani H., Surface-Initiated ATRP of Styrene from Epoxy Groups of Graphene Nanolayers: Two fold Polystyrene Chains and Various Graft Densities, RSC Adv., 5, 53357-53368, 2015.
35.Gholipour-Mahmoudalilou M., Roghani-Mamaqani H., Azimi R., and Abdollahi A., Preparation of HyperbranchedPoly (Amidoamine)-Grafted Graphene Nanolayers as A Composite and Curing Agent for Epoxy Resin, Appl. Surf. Sci., 428, 1061-1069, 2018.
36.Azimi R., Roghani-Mamaqani H., and Gholipour-Mahmoudalilou M., Grafting Poly(amidoamine) Dendrimer-Modified Silica Nanoparticles to Graphene Oxide for Preparation of a Composite and Curing Agent for Epoxy Resin, Polymer, 126, 152-161, 2017.
37.Ma W.S., Li J., Deng B.J., and Zhao X.S., Preparation and Characterization of Long-Chain Alkyl Silane-Functionalized Graphene Film, J. Mater. Sci., 48,156-161, 2013.
38.Yang H.F., Li F.H., Shan C.S., Han D.X., Zhang Q.X., Niu L., and Ivaska A., Covalent Functionalization of Chemically Converted Graphene Sheets via Silane and Its Reinforcement, J. Mater. Chem., 19, 4632-4638, 2009.
39.Ma P.C., Kim J.K., and Tang B.Z., Functionalization of Carbon Nanotubes Using A Silane Coupling Agent, Carbon, 44 , 3232-3238, 2006.
40.Wang X., Xing W., Zhang P., Song L., Yang H., and Hu Y., Covalent Functionalization o Graphene with Organosilane and Its Use as A Reinforcement in Epoxy Composites, Compos. Sci. Technol., 72, 737-743, 2012.
41.Roghani-Mamaqani H., and Khezri K., A Grafting from Approach to Graft Polystyrene Chains to the Surface of Graphene Nanolayers by RAFT Polymerization: Various Graft Densities from Hydroxyl Groups, Appl. Surf. Sci., 360, 373-382, 2016.
42.Wan Y.J., Gong L.X., Tang L.C., Wu L.B., and Jiang J.X., Mechanical Properties of Epoxy Composites Filled with Silane-Functionalized Graphene Oxide, Composites Part A, 64, 79-89, 2014.
43.Wang Z., Wei P., Qian Y., and Liu J., The Synthesis of A Novel Graphene-Based Inorganic-Organic Hybrid Flame Retardant and Its Application in Epoxy Resin, Composites, B, 60, 341-9, 2014.
44.Lytle C.A., Bertsch W., and McKinley M., Determination of Novolac Resin Thermal Decomposition Products by Pyrolysis-Gas Chromatography-Mass Spectrometry, J. Anal. Appl. Pyrolysis, 45, 121-131, 1998.
45.Burns R. and Orrell E.W., A Thermal Analytical Study of Phenol Formaldehyde Resins, J. Mater. Sci., 2, 72-77, 1967.