Polymers have become an indispensable material resource, representing billions of dollars worth of material consumption every year. The rising prices and exhaust of natural resources such as petroleum, combined with rising environmental concerns, have prompted the development of recyclable and degradable polymers. Polymers that can be reverted back to their monomers or to shorter repolymerizable oligomers, hence, reversible polymers are particularly enticing in this respect because they essentially prevent any material loss with multiple recycling. While reversible polymers have been known for a long time, there has been recent renewed interest in such polymers, since their reversibility can be exploited for repair at the molecular level.
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References
Gandini A. 2005 The application of the Diels-Alder reaction to polymer syntheses based on furan/maleimide reversible couplings. PolÃmeros: Ci ência e Tecnologia 15:95-101
Craven J.M. 1969 Cross-linked thermally reversible polymers produced from condensation polymers with pendant furan groups cross-linked with maleimides. US Patent 3,435,003
Stevens M., Jenkins A. 1979 Crosslinking of polystyrene via pendant maleimide groups. J Polym Sci 17:3675-3685
Chujo Y., Sada, K., Saegusa T. 1990 Reversible gelation of polyoxazoline by means of Diels-Alder reaction. Macromolecules 23:2636-2641
Imai Y., Itoh H., Naka K., Chujo Y. 2000 Thermally reversible IPN organic-inorganic polymer hybrids utilizing the Diels-Alder reaction. Macromolecules 33:4343-4346
Canary S.A., Stevens M.P. 1992 Thermally reversible crosslinking of polystyrene via the furan-maleimide Diels-Alder reaction. J Polym Sci: Polym Chem 30:1755-1760
Laita H., Boufi S., Gandini A. 1997 The application of the Diels-Alder reaction to polymers bearing furan moieties. 1. Reactions with maleimides. Eur Polym J 33:1203-1211
Gouss é C., Gandini A., Hodge P. 1998 Application of the Diels-Alder reaction to polymers bearing furan moieties. 2. Diels-Alder and retro-Diels-Alder reactions involving furan rings in some styrene copolymers. Macromolecules 31:314-321
Gheneim R., Perez-Berumen C., Gandini A. 2002 Diels-Alder reactions with novel polymeric dienes and dienophiles: synthesis of reversibly cross-linked elastomers. Macromolecules 35:7246-7253
Goiti E., Huglin M.B., Rego J.M. 2001 Some observations on the copolymerization of styrene with furfuryl methacrylate. Polymer 42:10187-10193
Goiti E., Huglin M.B., Rego J.M. 2003 Thermal breakdown by the retro Diels-Alder reaction of crosslinking in poly[styrene-co-(furfuryl methacrylate)]. Macromol Rapid Commun 24:692-696
Goiti E., Huglin M.B., Rego J.M. 2004 Some properties of networks produced by the Diels-Alder reaction between poly(styrene-co-furfuryl methacrylate) and bismaleimide. Eur Polym J 40:219-226
Goiti E., Huglin M.B., Rego J.M. 2004 Kinetic aspects of the Diels-Alder reaction between poly(styrene-co-furfuryl methacrylate) and bismaleimide. Eur Polym J 40:1451-1460
Gheneim R., Perez-Berumen C., Gandini A. 2002 Diels-Alder reactions with novel polymeric dienes and dienophiles: synthesis of reversibly cross-linked elastomers. Macromolecules 35:7246-7253
Kuramoto N., Hayashi K., Nagai K. 1994 Thermoreversible reaction of Diels-Alder polymer composed of difurfuryl adipate with bismaleimidodiphenylmethane. J Polym Sci: Polym Chem 32:2501-2504
Tesoro G.C., Sastri V.R. 1986 Synthesis of siloxane-containing bis(furans) and polymerization with bis(maleimides). Ind Eng Chem: Prod Res Dev 25:444-448
Diakoumakos C.D., Mikroyannidis J.A. 1992 Polyimides derived from Diels-Alder polymerization of furfuryl-substituted maleamic acids or from the reaction of bismaleamic with bisfurfurylpyromellitamic acids. J Polym Sci Polym Chem 30:2559-2567
Diakoumakos C.D., Mikroyannidis J.A. 1994 Heat-resistant resins derived from cyanosubstituted Diels-Alder polymers. Eur Polym J 30:465-472
Gouss é C., Gandini A. 1999 Diels-Alder polymerization of difurans with bismaleimides. Polym Intern 48:723-731
McElhanon J.R., Wheeler D.R. 2001 Thermally responsive dendrons and dendrimers based on reversible furan-maleimide Diels-Alder adducts. Org Lett 3:2681-2683
McElhanon J.R., Russick E.M., Wheeler D.R., Loy D.A., Aubert J.H. 2002 Removable foams based on an epoxy resin incorporating reversible Diels-Alder adducts. J Appl Polym Sci 85:1496-1502
Loy D.A., Wheeler D.R., McElhanon J.R., Durbin-Voss M.L. (2002) Method of making thermally removable Diels-Alder adduct-containing polyurethanes. US Patent 6403753
Loy D.A., Wheeler D.R., Russick E.M., McElhanon J.R., Sanders R.S. (2002) Method of making thermally removable epoxy resins. US Patent 6403753
Small J.H., Loy D.A., Wheeler D.R., McElhanon J.R., Saunders R.S. (2001) Method of making thermally removable polymeric encapsulants from maleimide resins. US Patent 6271335
Loy D.A., Wheeler D.R., Saunders R.S., McElhanon J.R., Small J.H. (2001) Method of making thermally removable polymeric encapsulants US Patent 6271335
Kamahori K., Tada S., Ito K., Itsuno S. 1999 Optically active polymer synthesis by DielsAlder polymerization with chirally modified lewis acid catalyst. Macromolecules 32:541-547
Gouss é C., Gandini A. 1998 Synthesis of 2-furfurylmaleimide and preliminary study of its Diels-Alder polycondensation. Polym Bull 40:389-394
Chen X., Dam M.A., Ono K., Mal A.K., Shen H., Nutt S.R., Sheran K., Wudl F. 2002 A thermally re-mendable cross-linked polymeric material. Science 295:1698-1702
Chen X., Wudl F., Mal A.K., Shen H., Nutt S.R. 2003 New thermally remendable highly cross-linked polymeric materials. Macromolecules 36:1802-1807
Wudl F., Chen X. (2004) Thermally re-mendable crosslinked polymers, monomers, their manufacture, and thermally mending. US Patent 2004014933
Liu Y.L., Hsieh C.Y. 2006 Crosslinked epoxy materials exhibiting thermal remendablility and removability from multifunctional maleimide and furan compounds. J Polym Sci: Polym Chem 44:905-913
Watanabe M., Yoshie N. 2006 Synthesis and properties of readily recyclable polymers from bisfuranic terminated poly(ethylene adipate) and multi-maleimide linkers. Polymer 47:4946-4952
Liu Y.L., Chen Y.W. 2007 Thermally reversible cross-linked polyamides with high toughness and self-repairing ability from maleimide- and furan-functionalized aromatic polyamides. Macromol Chem Phys 208:224-232
Gotsmann B., Duerig U., Frommer J., Hawker C.J. 2006 Exploiting chemical switching in a Diels-Alder polymer for nanoscale probe lithography and data storage. Adv Funct Mater 16:1499-1505
Stille J.K., Plummer L. 1961 Polymerization by the Diels-Alder reaction. J Org Chem 26: 4026-4029
Takeshita Y., Uoi M., Hirai Y., Uchiyama M. (1972) Polymers crosslinked through dicy-clopentadiene rings. German Patent 2164022
Kennedy J.P., Castner K.F. 1979 Thermally reversible polymer systems by cyclopentadienylation. I. A model for termination by cyclopentadienylation of olefin polymerization. J Polym Sci: Polym Chem Ed 17:2039-2054
Kennedy J.P., Castner K.F. 1979 Thermally reversible polymer systems by cyclopentadienylation. II. The synthesis of cyclopentadiene-containing polymers. J Polym Sci: Polym Chem Ed 17:2055-2070
Miura M., Akutsu F., Usui T., Ikebukuro Y., Nagakubo K. 1985 Soluble cyclopentadieny-lated polymers. Makromol Chem 186:473-481
Salamone J.C., Chung Y., Clough S.B., Watterson A.C. 1988 Thermally reversible, covalently crosslinked polyphosphazenes. J Polym Sci: Polym Chem Ed 26:2923-2939
Chen X.N., Ruckenstein E.J. 1999 Thermally reversible linking of halide-containing polymers by potassium dicyclopentadienedicarboxylate. J Polym Sci: Polym Chem 37:4390-4401
Ruckenstein E.J., Chen X.N. 2000 Crosslinking of chlorine-containing polymers by dicyclopentadiene dicarboxylic salts. J Polym Sci: Polym Chem 38:818-825
Chen X.N., Ruckenstein E.J. 2000 Thermally reversible covalently bonded linear polymers prepared from a dihalide monomer and a salt of dicyclopentadiene dicarboxylic acid. J Polym Sci: Polym Chem 38:1662-1672
Murphy E., Bolanos E., Wudl F. (2007) Manuscript in preparation.
Stevens M.P. 1984 Diels-Alder polymer of N-(2-anthryl)maleimide. J Polym Sci: Polym Lett Ed 22:467-471
Grigoras M., Colotin G. 2001 Copolymerization of a bisanthracene compound with bismaleimides by Diels-Alder cycloaddition. Polym Int 50:1375-1378
Jones J.R., Liotta C.L., Collard D.M., Schiraldi D.A. 1999 Cross-linking and modification of poly(ethylene terephthalate-co-2,6-anthracenedicarboxylate) by Diels-Alder reactions with maleimides. Macromolecules 32:5786-5792
Brand T., Klapper M. 1999 Control of viscosity through reversible addition of telechelics via repetitive Diels-Alder reaction in bulk. Des Monomers Polym 2:287-309
Muehlebach A., Hafner A., Van Der Schaaf P.A. (1996) Crosslinkable polymers and process for crosslinking them. Int Patent 9623829
Chen Y., Geh J.L. 1996 Copolymers derived from 7-acryloyloxy-4-methylcoumarin and acrylates: 2. Reversible photocrosslinking and photocleavage. Polymer 37:4481-4486
Matsui J., Ochi Y., Tamaki K. 2006 Photodimerization of anthryl moieties in a poly(methacrylic acid) derivative as reversible cross-linking step in molecular imprinting. Chem Lett 35:80-81
Zheng Y., Micic M., Mello S.V., Mabrouki M., Andreopoulos F.M., Konka V., Pham S.M., Leblanc R.M. 2002 PEG-based hydrogel synthesis via the photodimerization of anthracene groups. Macromolecules 35:5228-5234
Torii T., Ushiki H., Horie K. 1993 Fluorescence study on dynamics and structure of polymer chain. II. Dependence of intramacromolecular photocrosslinking reaction of polymers with anthryl and eosinyl moieties on number of crosslinkable side chains. Polym J 25:173-183
Chujo Y., Sada K., Nomura R., Naka A., Saegusa T. 1993 Photogelation and redox properties of anthracene-disulfide-modified polyoxazolines. Macromolecules 26:5611-5614
Chang J.M., Aklonis J.J. 1983 A photothermal reversibly crosslinkable polymer system. J Polym Sci: Polym Lett Ed 21:999-1004
Chung C.M., Roh Y.S., Cho S.Y., Kim J.G. 2004 Crack healing in polymeric materials via photochemical [2+2] cycloaddition. Chem Mater 16:3982-3984
Serpe M.J., Craig S.L. 2007 Physical organic chemistry of supramolecular polymers. Langmuir 23:1626-1634
Harada A., Hashidzume A., Takashima Y. 2006 Cyclodextrin-based supramolecular polymers. Adv Polym Sci 201:1-43
Lehn J.M. 2005 Dynamers: dynamic molecular and supramolecular polymers. Prog Polym Sci 30:814-831
Ciferri A. 2005 Supramolecular polymers, 2nd edn. Taylor & Francis, Boca Raton, FL
Armstrong G., Buggy M. 2005 Hydrogen-bonded supramolecular polymers: a literature review. J Mater Sci 40:547-559
Brunsveld L., Folmer B.J.B., Meijer E.W., Sijbesma R.P. 2001 Supramolecular polymers. Chem Rev 101:4071-4097
Moore J.S. 1999 Supramolecular polymers. Curr Opin Coll Int Sci 4:108-116
Sijbesma R.P., Beijer F.H., Brunsveld L., Folmer B.J.B., Ky Hirschberg J.H.K., Lange R.F.M., Lowe J.K.L., Meijer E.W. 1997 Reversible polymers formed from self-complementary monomers using quadruple hydrogen bonding. Science 278:1601-1604
Beijer F.H., Sijbesma R.P., Kooijman H., Spek A.L., Meijer E.W. 1998 Strong dimerization of ureidopyrimidones via quadruple hydrogen bonding. J Am Chem Soc 120:6761-6769
S öntjens S.H.M., Sijbesma R.P., van Genderen M.H.P., Meijer E.W. 2000 Stability and lifetime of quadruply hydrogen bonded 2-ureido-4[1H]-pyrimidinone dimers. J Am Chem Soc 122: 7487-7493
Ky Hirschberg J.H.K., Beijer F.H., van Aert H.A., Magusin P.C.M.M., Sijbesma R.P., Meijer E.W. 1999 Supramolecular polymers from linear telechelic siloxanes with quadruple-hydrogen-bonded units. Macromolecules 32:2696-2705
Lange R.F.M., Van Gurp M., Meijer E.W. 1999 Hydrogen-bonded supramolecular polymer networks. J Polym Sci: Polym Chem 37:3657-3670
Folmer B.J.B., Sijbesma R.P., Versteegen R.M., van der Rijt J.A.J., Meijer E.W. 2000 Supramolecular polymer materials: chain extension of telechelic polymers using a reactive hydrogen-bonding synthon. Adv Mater 12:874-878
El-ghayoury A., Peeters E., Schenning A.P.H.J., Meijer E.W. 2000 Quadruple hydrogen bonded oligo(p-phenylene vinylene) dimers. Chem Commun 19:1969-1970
Ky Hirschberg J.H.K., Brunsveld L., Ramzi A., Vekemans J.A.J.M., Sijbesma R.P., Meijer E.W. 2000 Helical self-assembled polymers from cooperative stacking of hydrogen-bonded pairs. Nature 407:167-170
Schenning A.P.H.J., Jonkheijm P., Peeters E., Meijer E.W. 2001 Hierarchical order in supramolecular assemblies of hydrogen-bonded oligo(p-phenylene vinylene)s. J Am Chem Soc 123: 409-416
El-Ghayoury A., Schenning A.P.H.J., Van Hal P.A., Van Duren J.K.J., Janssen R.A.J., Meijer E.W. 2001 Supramolecular hydrogen-bonded oligo(p-phenylene vinylene) polymers. Angew Chem Int Ed 40:3660-3663
Keizer H.M., Sijbesma R.P., Jansen J.F.G.A., Pasternack G., Meijer E.W. 2003 Polymerization-induced phase separation using hydrogen-bonded supramolecular polymers. Macromolecules 36:5602-5606
Keizer H.M., van Kessel R., Sijbesma R.P., Meijer E.W. 2003 Scale-up of the synthesis of ureidopyrimidinone functionalized telechelic poly(ethylenebutylene). Polymer 44: 5505-5511
Bosman A.W., Brunsveld L., Folmer B.J.B., Sijbesma R.P., Meijer E.W. 2003 Supramolecular polymers: From scientific curiosity to technological reality. Macromol Symp 201:143-154
Bosman A.W., Sijbesma R.P., Meijer E.W. 2004 Supramolecular polymers at work. Mater Today 7:34-39
Ligthart G.B.W.L., Ohkawa H., Sijbesma R.P., Meijer E.W. 2005 Complementary quadruple hydrogen bonding in supramolecular copolymers. J Am Chem Soc 127:810-811
Scherman O.A., Ligthart G.B.W.L., Sijbesma R.P., Meijer E.W. 2006 A selectivity-driven supramolecular polymerization of an AB monomer. Angew Chem Int Ed 45:2072-2076
Kautz H., van Beek D.J.M., Sijbesma R.P., Meijer E.W. 2006 Cooperative end-to-end and lateral hydrogen-bonding motifs in supramolecular thermoplastic elastomers. Macromolecules 39:4265-4267
Ohkawa H., Ligthart G.B.W.L., Sijbesma R.P., Meijer E.W. 2007 Supramolecular graft copolymers based on 2,7-diamido-1,8-naphthyridines. Macromolecules 40:1453-1459
Bleay S.M., Loader C.B., Hawyes V.J., Humberstone L., Curtis P.T. 2001 A smart repair system for polymer matrix composites. Composites A 32:1767-1776
Zako M., Takano N. 1999 Intelligent material systems using epoxy particles to repair microcracks and delamination damage in GFRP. J Int Mater Sys Struct 10:836-841
Dry C. 1991 Alteration of matrix permeability, pore and crack structure by the time release of internal chemicals. Ceramic Trans: Adv Cem Mater 16:729-768
Dry C. 1994 Matrix cracking repair and filling using active and passive modes for smart timed release of chemicals from fibres into cement matrices. Smart Mater Struct 3:118-123
Dry C., McMillan W. 1996 Three-part methylmethacrylate adhesive system as an internal delivery system for smart responsive concrete. Smart Mater Struct 5:297-300
Dry C. 2001 Three designs for the internal release of sealants, adhesives and waterproofing chemical into concrete to release. Cement Concrete Res 30:1969-1977
Li V.C., Lim Y.M., Chan Y.W. 1998 Feasibility of a passive smart self-healing cementitious composite. Composites B 29B:819-827
Dry C., Corsaw M., Bayer E. 2003 A comparison of internal self-repair with resin injection in repair of concrete. J Adh Sci Tech 17:79-89
Dry C., Corsaw M. 2003 A comparison of bending strength between adhesive and steel reinforced concrete with steel only reinforced concrete. Cem Conc Res 33:1723-1727
Dry C. (2007) Multiple function, self-repairing laminated composites with special adhesives. Int Patent 2007005657
Dry C. 1996 Procedure developed for self-repair of polymer matrix composite materials. Comp Struct 35:263-269
Dry C., Sottos N. (1996) Passive smart self-repair in polymer matrix composite materials. Proc SPIE: Smart Mater Struct 1916:438-444
Dry C., McMillan W. 1997 A novel method to detect crack location and volume in opaque and semi-opaque brittle materials. Smart Mater Struct 6:35-39
Motuku M., Vaidya U.K., Janowski G.M. 1999 Parametric studies on self-repairing approaches for resin infused composites subjected to low velocity impact. Smart Mater Struct 8:623-638
White S.R., Sottos N.R., Geubelle P.H., Moore J.S., Kessler M.R., Sriram S.R., Brown E.N., Viswanathan S. 2001 Autonomic healing of polymer composites. Nature 409:794-797
Kessler M.R., White S.R. 2001 Self-activated healing of delamination damage in woven composites. Composites A 32:683-699
Kessler M.R., Sottos N.R., White S.R. 2003 Self-healing structural composite materials. Composites A 34:743-753
Brown E.N., Sottos N.R., White S.R. 2002 Fracture testing of a self-healing polymer composite. Exp Mech 42:372-379
Brown E.N., Kessler M.R., Sottos N.R., White S.R. 2003 In situ poly (ureaformaldehyde) microencapsulation of dicyclopentadiene. J Microencapsul 20:719-730
Brown E.N., White S.R., Sottos N.R. 2004 Microcapsule induced toughening in a self-healing polymer composite. J Mater Sci 39:1703-1710
Jones A.S., Rule J.D., Moore J.S., White S.R., Sottos N.R. 2006 Catalyst morphology and dissolution kinetics of self-healing polymers. Chem Mater 18:1312-1317
Liu X., Lee J.K., Yoon S.H., Kessler M.R. 2006 Characterization of diene monomers as healing agents for autonomic damage repair. J Appl Polym Sci 101:1266-1272
Maiti S., Shankar C., Geubelle P.H., Kieffer J. 2006 Continuum and molecular-level modeling of fatigue crack retardation in self-healing polymers. J Eng Mat Tech 128:595-602
Cho S.H., Andersson H.M., White S.R., Sottos N.R., Braun P.V. 2006 Polydimethylsiloxane-based self-healing materials. Adv Mater 18:997-1000
Pang J.W.C., Bond I.P. 2004 Bleeding composites - damage detection and self-repair using a biomimetic approach. Composites A 36:183-188
Pang J.W.C., Jody W.C., Bond I.P. 2005 A hollow fibre reinforced polymer composite encompassing self-healing and enhanced damage visibility. Comp Sci Tech 65:1791-1799
Gollapudi U.K., Knutson C.L., Bang S.S., Islam M.R. 1995 A new method for controlling leaching through permeable channels. Chemosphere 30:695-705
Stocks-Fischer S., Galinat J.K., Bang S.S. 1999 Microbiological precipitation of CaCO3 . Soil Bio Biochem 31:1563-1571
Bang S.S., Galinat J.K., Ramakrishnan V. 2001 Calcite precipitation induced by polyurethane-immobilized Bacillus pasteurii. Enz Microb Tech 28:404-409
Bachmeier K., Williams A.E., Warmington J., Bang S.S. 2002 Urease activity in microbiologically-induced calcite precipitation. J Biotech 93:171-181
Holliday L. 1975 Ionic polymers. Wiley, New York
http://www2.dupont.com/Surlyn/en US/ and http://www2.dupont.com/Products/en RU/ Nucrel en.html
Eisenberg A., Kim J.S. 1998 Introduction to ionomers. Wiley, New York
Tant M.R., Mauritz K.A., Wilkes G.L. 1997 Ionomers: Synthesis, structure, properties, and applications. Chapman & Hall, New York
Wilson A.D., Prosser H.J. 1983 Developments in ionic polymers. Applied Science, New York
Kalista S.J. (2003) Self-healing of thermoplastic poly(ethylene-co-methacrylic acid) copolymers following projectile puncture. M.Sc. Thesis, Virginia Tech http://scholar.lib.vt.edu/theses/available/etd-12162003-103411/
Kalista S.J., Ward T.C., Oyetunji Z. 2003 Self-healing behavior of ethylene-based ionomers. Proc Ann Meet Adhes Soc 26:176-178
Kalista S.J., Ward T.C. 2004 A quantitative comparison of puncture-healing in a series of ethylene based ionomers. Proc Ann Meet Adhes Soc 27:212-214
Fall R. (2001) Puncture reversal of ethylene ionomers-mechanistic studies. M.Sc. Thesis, Virginia Tech http://scholar.lib.vt.edu/theses/available/etd-08312001-084412/
Huber A., Hinkley J.A. 2005 Impression testing of self-healing polymers. NASA Tech Man 2005-213532
Kalista S.J., Ward T.C. 2006 Self-healing in carbon nanotube filled thermoplastic poly(ethylene-co-methacrylic acid) ionomer composites. Proc Ann Meet Adhes Soc 29: 244-246
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Bergman, S.D., Wudl, F. (2007). Re-Mendable Polymers. In: van der Zwaag, S. (eds) Self Healing Materials. Springer Series in Materials Science, vol 100. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-6250-6_3
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