超支化聚合物(HBPs)改性环氧树脂的研究进展
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摘要
超支化聚合物在不影响工艺性的前提下对环氧树脂有明显的增强、增韧作用。本文主要概述了超支化聚合物对环氧树脂力学性能、耐热性能的影响,主要包括:聚酯超支化聚合物改性环氧树脂、聚酰胺/聚酰亚胺/聚乙烯亚胺超支化聚合物改性环氧树脂、有机硅超支化聚合物改性环氧树脂以及其他超支化聚合物改性环氧树脂等。此外,还指出了目前超支化聚合物改性环氧树脂的缺点以及未来的发展方向。当前限制HBPs在环氧树脂改性领域内大规模应用的主要缺点在于大多数HBPs合成步骤繁琐复杂,合成成本较高。鉴于此,在未来随着更简单、绿色的合成方法的出现,HBPs在其他新兴领域以及改性树脂中的应用会越来越广泛。
Hyperbranched polymers(HBPs) are a new kind of polymers used as modifiers of epoxy resins to increase their strength and toughness without affecting the processability. The influence of some HBPs on the physical properties and thermal resistance of epoxy resin was summarized in this paper, including four parts: hyperbranched polyether as an epoxy modifier, hyperbranched polyamide/polyimide/polyethyleneimine as an epoxy modifier, hyperbranched polysiloxanes as an epoxy modifier and other hyperbranched polymers as an epoxy modifier. Then the drawback of hyperbranched polymers used as modifiers of epoxy resins was revealed. In addition, more and more fascinating materials and devices based on hyperbranched polymers will be successfully developed and fabricated in the future. The main limitation of the HBPs in the field of epoxy resin modification is that the synthesis steps of most HBPs are cumbersome. Thus, in the future, with the advent of simpler, greener synthetic methods, HBPs will be more widely used in other emerging fields and modified resins.
Hyperbranched polymers(HBPs) are a new kind of polymers used as modifiers of epoxy resins to increase their strength and toughness without affecting the processability. The influence of some HBPs on the physical properties and thermal resistance of epoxy resin was summarized in this paper, including four parts: hyperbranched polyether as an epoxy modifier, hyperbranched polyamide/polyimide/polyethyleneimine as an epoxy modifier, hyperbranched polysiloxanes as an epoxy modifier and other hyperbranched polymers as an epoxy modifier. Then the drawback of hyperbranched polymers used as modifiers of epoxy resins was revealed. In addition, more and more fascinating materials and devices based on hyperbranched polymers will be successfully developed and fabricated in the future. The main limitation of the HBPs in the field of epoxy resin modification is that the synthesis steps of most HBPs are cumbersome. Thus, in the future, with the advent of simpler, greener synthetic methods, HBPs will be more widely used in other emerging fields and modified resins.
引文
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[4] JAJAM K C,RAHMAN M M,HOSUR M V,et al.Fracture behavior of epoxy nanocomposites modified with polyol diluent and amino-functionalized multi-walled carbon nanotubes:a load-ing rate study[J].Composites Part A:Applied Science and Manufacturing,2014,59:57-69.
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[7] DINESH K K,KOTHANDARAMAN B.Modification of (DGEBA) epoxy resin with maleated depolymerised natural rub-ber[J].Express Polymer Letters,2008,2(4):302-311.
[8] RATNA D,BANTHIA A K.Rubber toughened epoxy[J].Macromolecular Reasearch,2004,12(1):11-21.
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[10] BARCIA F L,AMARAL T P,SOARES B G.Synthesis and properties of epoxy resin modified with epoxy-terminated liquid polybutadiene[J].Polymer,2003,44(19):5811-5819.
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[12] ZHANG D,LIU C,CHEN S,et al.Highly efficient prepa-ration of hyperbranched epoxy resins by UV-initiated thiol-ene click reaction[J].Progress in Organic Coatings,2016,101:178-185.
[13] BARUA S,CHATTOPADHYAY P,AIDEW L,et al.Infe-ction-resistant hyperbranched epoxy nanocomposite as a scaffold for skin tissue regeneration[J].Polymer International,2015,64(2):303-311.
[14] ZHANG Z Y,GU A J,LIANG G Z,et al.A novel hyperb-ranched polysiloxane containing epoxy and phosphaphenanthrene groups and its multi-functional modification of cyanate ester resin[J].Soft Materials,2013,11(3):346-352.
[15] ZHANG D,LIANG E,LI T,et al.The effect of molecular weight of hyperbranched epoxy resins with a silicone skeleton on performance[J].RSC Advances,2013(3):9522-9529.
[16] BOOGH L,PETTERSSON B,MANSON J E.Dendritic hyper-branched polymers as tougheners for epoxy resins[J].Polymer,1999,40(9):2249-2261.
[17] WU H,XU J,HEIDEN P.Investigation of readily processable thermoplastic-toughened thermosets Ⅴ epoxy resin toughened with hyperbranched polyester[J].Journal of Applied Polymer Science,1999,72(2):151-163.
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[19] ACHARY P,LATHA P,RAMASWAMY R.Room temper-ature curing of CTBN-toughened epoxy adhesive with elevated temperature service capability[J].Journal of Applied Polymer Science,1990,41:151-162.
[20] RATNA D.Modification of epoxy resins for improvement of adhesion:a critical review[J].Journal of Adhesion Science and Technology,2003,17(12):1655-1668.
[21] NIU S,YAN H,LI S,et al.Bright blue photoluminescence emitted from the novel hyperbranched polysiloxane-containing unconventional chromogens[J].Macromolecular Chemistry and Physics,2016,217(10):1185-1190.
[22] LU H,FENG L,LI S,et al.Unexpected strong blue photol-uminescence produced from the aggregation of unconventional chromophores in novel siloxane-poly(amidoamine) dendrimers[J].Macromolecules,2015,48(3):476-482.
[23] YANG W,PAN C.Synthesis and fluorescent properties of biodegradable hyperbranched poly(amido amine)s[J].Macrom-olecular Rapid Communications,2009,30(24):2096-2101.
[24] LIU Y,GOH S H.Blue photoluminescence from hyperbranched poly(amino ester)s[J].Macromolecules,2005,38:9906-9909.
[25] CARR P L,DAVIES G R,FEAST W J,et al.Dielectric and mechanical characterization of aryl ester dendrimer/PET blends[J].Polymer,1996,37(12):2395-2401.
[26] RATNA D,SIMON G P.Thermomechanical properties and morphology of blends of a hydroxy-functionalized hyperbranched polymer and epoxy resin[J].Polymer,2001,42(21):8833-8839.
[27] BLANCO I,CICALA G,FARO C L,et al.Thermomechanical and morphological properties of epoxy resins modified with functionalized hyperbranched polyester[J].Polymer Engineering & Science,2006,46(11):1502-1511.
[28] OH J H,JANG J,LEE S H.Curing behavior of tetrafunctional epoxy resin/hyperbranched polymer system[J].Polymer,2001,42(20):8339-8347.
[29] RATNA D,SIMON G P.Thermal and mechanical properties of a hydroxyl-functional dendritic hyperbranched polymer and trifunctional epoxy resin blends[J].Polymer Engineering & Science,2001,41(10):1815-1822.
[30] RATNA D,VARLEY R,RAMAN R K,et al.Studies on blends of epoxy-functionalized hyperbranched polymer and epoxy resin[J].Journal of Materials Science,2003,38(1):147-154.
[31] FERNANDEZ-FRANCOS X,FOIX D,SERRA A,et al.Novel thermosets based on DGEBA and hyperbranched polymers modified with vinyl and epoxy end groups[J].Reactive and Functional Polymers,2010,70(10):798-806.
[32] FERNANDEZ-FRANCOS X,SALLA J M,CADENATO A,et al.A new strategy for controlling shrinkage of DGEBA resins cured by cationic copolymerization with hydroxyl-terminated hyperbranched polymers and ytterbium triflate as an initiator[J].Journal of Applied Polymer Science,2008,111(6):2822-2829.
[33] MORANCHO J M,CADENATO A,RAMIS X,et al.Thermal curing and photocuring of an epoxy resin modified with a hyper-branched polymer[J].Thermochimica Acta,2010,510(1/2):1-8.
[34] MORELL M,ERBER M,RAMIS X,et al.New epoxy ther-mosets modified with hyperbranched poly(ester-amide) of differ-ent molecular weight[J].European Polymer Journal,2010,46(7):1498-1509.
[35] FLORES M,FERNANDEZ-FRANCOS X,FERRANDO F,et al.Efficient impact resistance improvement of epoxy/anhydride thermosets by adding hyperbranched polyesters partially modified with undecenoyl chains[J].Polymer,2012,53(23):5232-5241.
[36] FOIX D,YU Y,SERRA A,et al.Study on the chemical modi-fication of epoxy/anhydride thermosets using a hydroxyl termi-nated hyperbranched polymer[J].European Polymer Journal,2009,45(5):1454-1466.
[37] FLORES M,FERNANDEZ-FRANCOS X,RAMIS X,et al.Novel epoxy-anhydride thermosets modified with a hyperbr-anched polyester as toughness enhancer Ⅰ kinetics study[J].Thermochimica Acta,2012,544:17-26.
[38] DABRITZ F,VOIT B,NAGUIB M,et al.Hyperstar poly(ester-methacrylate)s as additives in thermally and photocured epoxy resins[J].Polymer,2011,52(25):5723-5731.
[39] SANGERMANO M,PRIOLA A,MALUCELLI G,et al.Phenolic hyperbranched polymers as additives in cationic photop-olymerization of epoxy systems[J].Macromolecular Materials and Engineering,2004,289(5):442-446.
[40] SANGERMANO M,MALUCELLI G,BONGIOVANNI R,et al.Investigation on the effect of the presence of hyperbranched polymers on thermal and mechanical properties of an epoxy UV-cured system[J].Polymer International,2005,54(6):917-921.
[41] MORANCHO J M,CADENATO A,RAMIS X,et al.Effect of a hyperbranched polymer over the thermal curing and the photocuring of an epoxy resin[J].Journal of Thermal Analysis and Calorimetry,2011,105(2):479-488.
[42] FOIX D,FERNANDEZ-FRANCOS X,SSALLA J M,et al.New thermosets obtained from bisphenol A diglycidyl ether and hydroxyl-ended hyperbranched polymers partially blocked with benzoyl and trimethylsilyl groups[J].Polymer International,2011,60(3):389-397.
[43] SANGERMANO M,SAYED H,VOIT B.Ethoxysilyl-modified hyperbranched polyesters as mulitfunctional coupling agents for epoxy-silica hybrid coatings[J].Polymer,2011,52(10):2103-2109.
[44] DENG S,YE L,FRIEDRICH K.Fracture behaviours of epoxy nanocomposites with nano-silica at low and elevated temper-atures [J].Journal of Materials Science,2007,42(8):2766-2774.
[45] YANG J,CHEN Z,YANG G,et al.Simultaneous improve-ments in the cryogenic tensile strength,ductility and impact str-ength of epoxy resins by a hyperbranched polymer[J].Polymer,2008,49(13/14):3168-3175.
[46] LIU T,NIE Y,CHEN R,et al.Hyperbranched polyether as an all-purpose epoxy modifier:controlled synthesis and toughening mechanisms[J].Journal of Materials Chemistry A,2015,3(3):1188-1198.
[47] JIN F L,PARK S J.Thermal properties and toughness perfo-rmance of hyperbranched-polyimide-modified epoxy resins[J].Journal of Polymer Science Part B:Polymer Physics,2006,44(23):3348-3356.
[48] SANTIAGO D,FERNANDEZ-FRANCOS X,RAMIS X,et al.Comparative curing kinetics and thermal-mechanical properties of DGEBA thermosets cured with a hyperbranched poly(ethylen-eimine) and an aliphatic triamine[J].Thermochimica Acta,2011,526(1/2):9-21.
[49] MORANCHO J M,FERNANDEZ-FRANCOS X,ACEBO C,et al.Thermal curing of an epoxy-anhydride system modified with hyperbranched poly(ethylene imine)s with different term-inal groups[J].Journal of Thermal Analysis and Calorimetry,2017,127(1):645-654.
[50] ZHU M,GU A,LIANG G,et al.High-performance transp-arent solvent-free silicone resins with stable storage and low viscosity based on new hyperbranched polysiloxanes[J].High Performance Polymers,2013,25(5):594-608.
[51] LIU P,GU A,LIANG G,et al.Preparation and properties of novel high performance UV-curable epoxy acrylate/hyperb-ranched polysiloxane coatings[J].Progress in Organic Coatings,2012,74(1):142-150.
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