Graphene nanosheets (GNs) often results in incompatibility with the hydrophobic polymer matrix, and the tendency to form aggregates during processing. Herein, hyperbranched polycaprolactone modified GNs (PGNs) was obtained using 3,4,9,10-perylenetetracarboxylic acid anhydride (PTCDA)reacted with GNs and caprolactone. Firstly, π-π stacking interactions between GNs and perylenebisimide derivatives (PBI), and then in-situ polymerization of ε-caprolactone. The structure and characteristic of PGNs were investigated by infrared spectroscopy, wide angle X-ray diffractometry, thermogravimetric analysis and ultraviolet spectrum. PGNs was added into epoxy matrix at different contents to improve the mechanical and thermal properties of epoxy. At 1.0 wt.% PGNs content, the impact strength and tensile strength of PGNs/epoxy composites were 43.41 kJ/m2 and 91.60 MPa. Compared with those of pure epoxy, these value increased by148% and 87%, respectively, as well as the Tg increased by about 20 °C.
This is a preview of subscription content, log in to check access.
Buy single article
Instant unlimited access to the full article PDF.
Price includes VAT for USA
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
This is the net price. Taxes to be calculated in checkout.
Zhang X, Alloul O, He Q, Zhu J, Verde MJ, Li Y, Wei S, Guo Z (2013) Strengthened magnetic epoxy nanocomposites with protruding nanoparticles on the graphene nanosheets. Polymer 54:3594–3604
Zhu J, Wei S, Ryu J, Budhathoki M, Liang G, Guo ZJ (2010) Conductive polypyrrole/tungsten oxide metacomposites with negative permittivity. Mater Chem 20:4937–4948
Azeez AA, Rhee KY, Park SJ, Hui D (2013) Epoxy clay nanocomposites – processing, properties and applications: a review. Compos Part B Eng 45:308–320
Cui LJ, Geng HZ, Wang WY, Chen LT, Gao J (2013) Functionalization of multi-wall carbon nanotubes to reduce the coefficient of the friction and improve the wear resistance of multi-wall carbon nanotube/epoxy composites. Carbon 48:277–282
Zaman I, Phan TT, Kuan HC, Meng Q, La LTB, Luong L, Youssf O, Ma J (2011) Epoxy/graphene platelets nanocomposites with two levels of interface strength. Polymer 52:1603–1611
Rafiee MA, Rafiee J, Wang Z, Song H, Yu ZZ, Koratkar N (2009) Enhanced mechanical properties of nanocomposites at low graphene content. ACS Nano 3:3884–3890
Lee C, Wei X, Kysar JW, Hone J (2008) Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321:385–388
Westervelt RM (2008) Graphene Nanoelectronics. Science 320:324–325
Liang J, Wang Y, Huang Y, Ma Y, Liu Z, Cai J, Zhang C, Gao H, Chen Y (2009) Electromagnetic interference shielding of graphene/epoxy composites. Carbon 47:922–925
Pang H, Chen C, Zhang YC, Ren PG, Yan DX, Li ZM (2011) The effect of electric field, annealing temperature and filler loading on the percolation threshold of polystyrene containing carbon nanotubes and graphene nanosheets. Carbon 49:1980–1988
Song P, Cao Z, Cai Y, Zhao L, Fang Z, Fu S (2011) Fabrication of exfoliated graphene-based polypropylene nanocomposites with enhanced mechanical and thermal properties. Polymer 52:4001–4010
Yan J, Wei T, Shao B, Fan Z, Qian W, Zhang M, Wei F (2010) Preparation of a graphene nanosheet/polyaniline composite with high specific capacitance. Carbon 48:487–493
Qi B, Yuan Z, Lu S, Liu K, Li S, Yang L, Yu J (2014) Mechanical and thermal properties of epoxy composites containing graphene oxide and liquid crystalline epoxy. Fiber Polym 15:326–333
Backes C, Hauke F, Hirsch A (2011) The potential of perylene bisimide derivatives for the solubilization of carbon nanotubes and graphene. Adv Mater 23:2588–2601
Hsiao ST, Ma CCM, Tien HW, Liao WH, Wang YS, Li SM, Huang YC (2013) Using a non-covalent modification to prepare a high electromagnetic interference shielding performance graphene nanosheet/water-borne polyurethane composite. Carbon 60:57–66
Wang Y, Chen X, Zhong Y, Zhu F, Loh KP (2009) Large area, continuous, few-layered graphene as anodes in organic photovoltaic devices. Appl Phys Lett 95:063302–063302-3
Georgakilas V, Otyepka M, Bourlinos AB, Chandra V, Kim N, Kemp KC, Hobza P, Zboril R, Kim KS (2012) Functionalization of graphene: covalent and non-covalent approaches, derivatives and applications. Chem Rev 112:6156–6214
Teng CC, Ma CCM, Lu CH, Yang SY, Lee SH, Hsiao MC, Yen MY, Chiou KC, Lee TM (2011) Thermal conductivity and structure of non-covalent functionalized graphene/epoxy composites. Carbon 49:5107–5116
Wang T, Li M, Gao H, Wu Y (2011) Nanoparticle carriers based on copolymers of poly(ε-caprolactone) and hyperbranched polymers for drug delivery. J Colloid Interf Sci 353:107–115
Lönnberg H, Zhou Q, Rd BH, Teeri TT, Malmström E, Hult A (2006) Grafting of cellulose fibers with poly(epsilon-caprolactone) and poly(L-lactic acid) via ring-opening polymerization. Biomacromolecules 7:2178–2185
Roy D, Semsarilar M, Guthrie JT, Perrier S (2009) Cellulose modification by polymer grafting: a review. Cheminform 40:2046–2064
Labet M, Thielemans W (2009) Synthesis of polycaprolactone: a review. Chem Soc Rev 38:3484–3504
Zhang J, Lin T, Cheung SCP, Wang CH (2012) The effect of carbon nanofibres on self-healing epoxy/poly(ε-caprolactone) blends. Compos Sci Technol 72:1952–1959
Haas U, Thalacker C, Adams J, Fuhrmann J, Riethmüller S, Beginn U, Ziener U, Möller M, Dobrawa R, Würthner F (2003) Fabrication and fluorescence properties of perylene bisimide dye aggregates bound to gold surfaces and nanopatterns. J Mater Chem 13:767–772
Huskić M, Pulko I (2015) The synthesis and characterization of multiarm star-shaped graft copolymers of polycaprolactone and hyperbranched polyester. Eur Polym J 70:384–391
Liu Y, Nguyen J, Steele T, Merkel O, Kissel T (2009) A new synthesis method and degradation of hyper-branched polyethylenimine grafted polycaprolactone block mono-methoxyl poly (ethylene glycol) copolymers (hy-PEI-g-PCL-b-mPEG) as potential DNA delivery vectors. Polymer 50:3895–3904
Johansson M, Malmström E, Jansson A, Hult A (2000) Novel concept for low temperature curing powder coatings based on hyperbranched polyesters. J Coating Technol 72:49–54
Trollsås M, Hawker CJ, Remenar JF, Hedrick JL, Johansson M, Ihre H, Hult A (2015) Highly branched radial block copolymers via dendritic initiation of aliphatic polyesters. J Polym Sci Pol Chem 36:2793–2798
Fang M, Wang K, Lu H, Yang Y, Nutt S (2009) Covalent polymer functionalization of graphene nanosheets and mechanical properties of composites. J Mater Chem 19:7098–7105
Wan YJ, Tang LC, Gong LX, Yan D, Li YB, Wu LB, Jiang JX, Lai GQ (2014) Grafting of epoxy chains onto graphene oxide for epoxy composites with improved mechanical and thermal properties. Carbon 69:467–480
Feng QP, Shen XJ, Yang JP, Fu SY, Mai YW, Friedrich K (2011) Synthesis of epoxy composites with high carbon nanotube loading and effects of tubular and wavy morphology on composite strength and modulus. Polymer 52:6037–6045
Zhang X, He Q, Gu H, Wei S, Guo Z (2013) Polyaniline stabilized barium titanate nanoparticles reinforced epoxy nanocomposites with high dielectric permittivity and reduced flammability. J Mater Chem C 1:2886–2899
Ramanathan T, Abdala AA, Stankovich S, Dikin DA, Herreraalonso M, Piner RD, Adamson DH, Schniepp HC, Chen X, Ruoff RS (2008) Functionalized graphene sheets for polymer nanocomposites. Nat Nanotechnol 3:327–331
Stankovich S, Dikin DA, Dommett GH, Kohlhaas KM, Zimney EJ, Stach EA, Piner RD, Nguyen ST, Ruoff RS (2006) Graphene-based composite materials. Nature 442:282–286
Park YT, Qian Y, Chan C, Suh T, Nejhad MG, Macosko CW, Stein A (2015) Epoxy toughening with low graphene loading. Adv Funct Mater 25:575–585
Zhang Y, Wang Y, Yu J, Chen L, Zhu J, Hu Z (2014) Tuning the interface of graphene platelets/epoxy composites by the covalent grafting of polybenzimidazole. Polymer 55:4990–5000
The authors gratefully acknowledge the financial support of the National Natural Science Foundation of China (51605109, 51763009 and 51463007), the Natural Science Foundation of Guangxi Province, China (2015GXNSFBA139231 2018GXNSFAA281296 and 2018GXNSFBA281052), Guangxi Ministry-Province Jointly-Constructed Cultivation Base for State Key Laboratory of Processing for Non-ferrous Metal and Featured Materials (19-KF-2 and 19-KF-9).
Conflict of interest
The authors declare no conflict of interest.
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Hou, L., Gao, J., Ruan, H. et al. Mechanical and thermal properties of hyperbranched poly(ε-caprolactone) modified graphene/epoxy composites. J Polym Res 27, 32 (2020) doi:10.1007/s10965-020-2008-x
- Hyperbranched poly(ε-caprolactone)
- Epoxy resin
- Mechanical properties