Synthesis and Characterization of Hyperbranched Epoxy with Terminal Ally Group and Its Application of Toughen Bismaleimide

Abstract

A hyperbranched epoxy (AHEP) resin with terminal allyl groups was synthesized. The number average molecular weight of the synthesized AHEP is 1 260, the multi-dispersion coefficient is 1.88, and the branching degree is 0.9. The hyperbranched epoxy resin and bismaleimide(BMI) monomer were heated to extend the chain and then blended and cured with methyl nadic anhydride. Studies have found that when the molar ratio of AHEP: BDM is 1:2, the mechanical properties and heat resistance of the resin casting body reach the best. Among them, the impact toughness was 15.05 kg/m², the bending strength was 101 MPa, and the heat resistance temperature index was 229.23 °C. We used AHEP to toughen bismaleimide resin in three ways simultaneously: hyperbranched structure, allyl copolymerized brackets chain and flexible side chain (epoxy group) addition. Experiments have proved that AHEP can improve the flexibility of the BMI chain and maintain its heat resistance, thereby forming a matrix with excellent mechanical properties and processing properties.

Keywords

hyperbranched / toughen / resins

References

[1] Yuan Q, Huang F, Jiao Y. Characterization of Modified Bismaleimide Resin[J]. Journal of Applied Polymer Science, 2015, 62(3): 459-464.

[2] Peter Dr R, Eisenbarth Dr P, Schlemmer L. Bismaleimide Resin[J]. EP, 1991, 32(6): 256-263.

[3] Ge M, Miao J T, Yuan L. Building and Origin of Bio-based Bismaleimide Resins with Good Processability, High Thermal, and Mechanical Properties[J]. Journal of Applied Polymer Science, 2017, 3(22): 45 947-45 948.

[4] Bao L R. Effect of Temperature on Moisture Absorption in a Bismaleimide Resin and Its Carbon Fiber Composites[J]. Polymer -London, 2002, 43(14): 3987-3997.

[5] Li S, Yan H, Feng S. Phosphorus-containing Flame-retardant Bismaleimide Resin with High Mechanical Properties[J]. Polymer Bulletin, 2016, 73(12): 3547-3557.

[6] Ding F C, Chen Q S, Lai S L. Bismaleimide (BMI) Resin Modified by PEEK Bearing Pendant Reactive Propenyl Groups[J]. Advanced Materials Research, 2011, 197–198: 1299-1305.

[7] Agag T, Takeichi T. Synthesis and Characterization of Novel Benzoxazine Monomers Containing Allyl Groups and Their High Performance Thermosets[J]. Macromolecules, 2003, 36(16): 6010-6017.

[8] Jiang H, Li Z, Gan J. Improved Thermal and Mechanical Properties of Bismaleimide Nanocomposites Via Incorporation of a New Allylated Siloxane Graphene Oxide[J]. Rsc Advances, 2020, 10(5): 374-382.

[9] Qin H, Mather P T, Baek J. Modification of Bisphenol-A Based Bismaleimide Resin (BPA-BMI) with an Allyl-terminated Hyperbranched Polyimide (AT-PAEKI)[J]. Polymer, 2006, 47(8): 2813-2821.

[10] Wang Y, Yuan L, Liang G. Achieving Ultrahigh Glass Transition Temperature, Halogen-free and Phosphorus-free Intrinsic Flame Retardancy for Bismaleimide Resin through Building Network with Diallyloxy-diphenyldisulfide[J]. Polymer, 2020, 47(11): 515-526.

[11] Baek J-B, Ferguson J B, Tan L-S. Room-Temperature Free-Radical-Induced Polymerization of 1,1’-(Methylenedi-1,4-phenylene)Bismaleimide Via a Novel Diphenylquinoxaline-Containing Hyperbranched Aromatic Polyamide[J]. Macromolecules, 2014, 36(12): 4385-4396.

[12] Wang X, Jiang Q, Xu W. Effect of Carbon Nanotube Length on Thermal, Electrical and Mechanical Properties of CNT/Bismaleimide Composites[J]. Carbon, 2013, 53: 145-152. Complete)

[13] Jin W, Yuan L, Liang G. Multifunctional Cyclotriphosphazene/hexagonal Boron Nitride Hybrids and Their Flame Retarding Bismaleimide Resins with High Thermal Conductivity and Thermal Stability.[J]. Acs Applied Materials & Interfaces, 2014, 6(17): 14

[14] Mandhakini Mohandas Chandramohan. Nanoindentation Studies of Nano Alumina-Reinforced Ether-Linked Bismaleimide Toughened Epoxy-Based Nanocomposites[J]. Polymer-Plastics Technology and Engineering, 2014, 53(10): 975-989.

[15] Cheng Q, Bao J, Park J G. High Mechanical Performance Composite Conductor: Multi-Walled Carbon Nanotube Sheet/Bismaleimide Nanocomposites[J]. Advanced Functional Materials, 2009, 19(20): 34-40.

[16] Musto P, Martuscelli E, Ragosta G. An Interpenetrated System Based on a Tetrafunctional Epoxy Resin and a Thermosetting Bismaleimide: Structure-properties Correlation[J]. Journal of Applied Polymer Science, 2015, 69(5): 1029-1042.

[17] Jiang H, Ji Y, Gan J. Enhancement of Thermal and Mechanical PropertieEs of Bismaleimide Using a Graphene Oxide Modified by Epoxy Silane[J]. Materials, 2020, 13(17): 3836-3844.

[18] Kumar R S, Alagar M. Studies on the Synthesis and Characterization of Diglycidylether-terminated Polydimethyl Siloxane-modified Epoxy-Bismaleimide Matrices[J]. High Performance Polymers, 2007, 19(1): 3-20.

[19] Premkumar S, Chozhan C K, Alagar M. Studies on Thermal, Mechanical and Morphological Behaviour of Caprolactam Blocked Methylenediphenyl Diisocyanate Toughened Bismaleimide Modified Epoxy Matrices[J]. European Polymer Journal, 2008, 44(8): 2599-2607.

[20] Costa M L, Almeida S F M D, Rezende M C. The Influence of Porosity on the Interlaminar Shear Strength of Carbon/Epoxy and Carbon/Bismaleimide Fabric Laminates[J]. Composites Science & Technology, 2001, 61(14): 2101-2108.

[21] Ji L, Gu A, Liang G. Novel Modification of Bismaleimide—Triazine Resin by Reactive Hyperbranched Polysiloxane[J]. Journal of Materials Science, 2010, 45(7): 1859-1865.

[22] Niu S, Yan H, Li S. A Multifunctional Silicon-containing Hyperbranched Epoxy: Controlled Synthesis, Foughening Bismaleimide and Fluorescent Properties[J]. Journal of Materials Chemistry C, 2016, 4(28): 6881-6893.

[23] Selvaganapathi A, Alagar M, Gnanasundaram P. Studies on Synthesis and Characterization of Hydroxyl-Terminated Polydimethylsiloxane-Modified Epoxy Bismaleimide Matrices[J]. High Performance Polymers, 2013, 25(6): 622-633.

[24] Zhang L, Chen P, Gao M. Synthesis, Characterization, and Curing Kinetics of Novel Bismaleimide Monomers Containing Fluorene Cardo Group and Aryl ether Linkage[J]. Designed Monomers & Polymers, 2014, 6(18): 181-193.

[25] Vijayakumar C T, Surender R, Rajakumar K. Synthesis and Thermal Studies of Bisphenol-A Based Bismaleimide[J]. Journal of Thermal Analysis & Calorimetry, 2011, 103(2): 693-699.

[26] Stenzenberger H D. Comonomers for Bismaleimides: o,o’-Diallylbisphenols[J]. High Performance Polymers, 2016, 9(13): 68-75.

[27] Dao B, Hawthorne D G, Hodgkin J H. Preparation and Characterization of Some Novel Bismaleimide Monomers and Polymers Based on Diaminobisimides[J]. High Performance Polymers, 2016, 24(8): 1081-1093.

[28] Liu X, Li L, Chen Z. Curing Behavior, Thermal, and Mechanical Properties of N,N′-(4,4′-diphenylmethane)Bismaleimide/2,2′-diallylbisphenol A/3-allyl-5,5-Dimethylhydantoin Resin System[J]. High Performance Polymers, 2020, 32(6): 631-644.

[29] Voit B. New Developments in Hyperbranched Polymers[J]. Journal of Polymer Science Part A Polymer Chemistry, 2015, 38(14): 2505-2525.

[30] Sunder A, Heinemann J, Frey H. Controlling the Growth of Polymer Trees: Concepts and Perspectives for Hyperbranched Polymers[J]. Chemistry, 2015, 6(14): 2499-2506.

[31] Gao C. Hyperbranched Polymers: from Synthesis to Applications[J]. Progress in Polymer Science, 2004, 12(11): 313-321.

[32] Chang H T, Fréchet J M J. Proton-Transfer Polymerization: A New Approach to Hyperbranched Polymers[J]. Journal of the American Chemical Society, 2016, 121(10): 2313-2314.

[33] Chen M R, Jin Y Z. Hyperbranched Polymer[J]. Thermosetting Resin, 2003, 21(19): 433-435.

[34] Stefan Hecht Jean. Dendritic Encapsulation of Function: Applying Nature’s Site Isolation Principle from Biomimetics to Materials Science[J]. Angewandte Chemie International Edition, 2001, 59(2): 150-162.

[35] Kolhe P, Misra E, Kannan R M. Drug Complexation, in Vitro Release and Cellular Entry of Dendrimers and Hyperbranched Polymers[J]. Int. J. Pharm., 2003, 259(1–2): 143-160.

[36] Daniel Wilms S-E S, Frey H. Hyperbranched Polyglycerols: From the Controlled Synthesis of Biocompatible Polyether Polyols to Multipurpose Applications[J]. Accounts of Chemical Research, 2010, 43(1): 129-141.

[37] Dominik Konkolewicz Angus. Hyperbranched Polymers by ThiolYne Chemistry: From Small Molecules to Functional Polymers[J]. Journal of the American Chemical Society, 2009, 131(50): 18075-18077.

[38] Stiriba S E, Kautz H, Frey H. Hyperbranched Molecular Nanocapsules: Comparison of the Hyperbranched Architecture with the Perfect Linear Analogue[J]. Journal of the American Chemical Society, 2002, 124(33): 9698-9699.

[39] De B, Karak N. RSC Advances[J]. Royal Society of Chemistry, 2015: 35080–35088

[40] Zhang A. Effect of Epoxy Resin on Mechanical Properties of Metakaolin Based Geopolymer and Microscopic Analysis[J]. Journal of Wuhan University of Technology-Mater. Sci. Ed., 2020, 35(2): 431-434.