{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,17]],"date-time":"2026-06-17T14:24:41Z","timestamp":1781706281646,"version":"3.54.5"},"reference-count":25,"publisher":"MDPI AG","issue":"3","license":[{"start":{"date-parts":[[2017,3,3]],"date-time":"2017-03-03T00:00:00Z","timestamp":1488499200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Polymers"],"abstract":"<jats:p>The impacts of hydrogen bonding on polymerization behavior has been of interest for a long time; however, universality and in-depth understanding are still lacking. For the first time, the effect of hydrogen bonding on the classical alternating-type copolymerization of styrene and maleimide was explored. N-phenylmaleimide (N-PMI)\/styrene was chosen as a model monomer pair in the presence of hydrogen bonding donor solvent 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), which interacted with N-PMI via hydrogen bonding. Reversible addition-fragmentation chain transfer polymerization (RAFT) technique was used to guarantee the \u201cliving\u201d polymerization and thus the homogeneity of chain compositions. In comparison with the polymerization in nonhydrogen bonding donor solvent (toluene), the copolymerization in HFIP exhibited a high rate and a slight deviation from alternating copolymerization tendency. The reactivity ratios of N-PMI and St were revealed to be 0.078 and 0.068, respectively, while the reactivity ratios in toluene were 0.026 and 0.050. These interesting results were reasonably explained by using computer simulations, wherein the steric repulsion and electron induction by the hydrogen bonding between HFIP and NPMI were revealed. This work first elucidated the hydrogen bonding interaction in the classical alternating-type copolymerization, which will enrich the research on hydrogen bonding-induced polymerizations.<\/jats:p>","DOI":"10.3390\/polym9030089","type":"journal-article","created":{"date-parts":[[2017,3,3]],"date-time":"2017-03-03T11:30:04Z","timestamp":1488540604000},"page":"89","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["RAFT Polymerization of Styrene and Maleimide in the Presence of Fluoroalcohol: Hydrogen Bonding Effects with Classical Alternating Copolymerization as Reference"],"prefix":"10.3390","volume":"9","author":[{"given":"Fangjun","family":"Yao","sequence":"first","affiliation":[{"name":"Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qingqing","family":"Liu","sequence":"additional","affiliation":[{"name":"Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhengbiao","family":"Zhang","sequence":"additional","affiliation":[{"name":"Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiulin","family":"Zhu","sequence":"additional","affiliation":[{"name":"Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2017,3,3]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"269","DOI":"10.1021\/ma071499l","article-title":"Stereoregulation in living radical polymerization","volume":"41","author":"Kamigaito","year":"2008","journal-title":"Macromolecules"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"1041","DOI":"10.1021\/ma047656n","article-title":"Atom transfer radical polymerization of methyl methacrylate in fluoroalcohol: Simultaneous control of molecular weight and tacticity","volume":"38","author":"Miura","year":"2005","journal-title":"Macromolecules"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"6147","DOI":"10.1002\/pola.21688","article-title":"Stereospecific living radical polymerization for simultaneous control of molecular weight and tacticity","volume":"44","author":"Kamigaito","year":"2006","journal-title":"J. Polym. Sci. Part A Polym. Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1436","DOI":"10.1002\/pola.21249","article-title":"Synthesis of well-defined syndiotactic poly(methyl methacrylate) with low-temperature atom transfer radical polymerization in fluoroalcohol","volume":"44","author":"Miura","year":"2006","journal-title":"J. Polym. Sci. Part A Polym. Chem."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"10003","DOI":"10.1021\/ja1042353","article-title":"AAB-sequence living radical chain copolymerization of naturally occurring limonene with maleimide: An end-to-end sequence-regulated copolymer","volume":"132","author":"Satoh","year":"2010","journal-title":"J. Am. Chem. Soc."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"104","DOI":"10.1021\/ma102223y","article-title":"Well-defined poly(sulfobetaine) brushes prepared by surface-initiated ATRP using a fluoroalcohol and ionic liquids as the solvents","volume":"44","author":"Terayama","year":"2011","journal-title":"Macromolecules"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"220","DOI":"10.1002\/(SICI)1099-0518(20000101)38:1<220::AID-POLA27>3.0.CO;2-P","article-title":"Free-radical copolymerization of vinyl esters using fluoroalcohols as solvents: The solvent effect on the monomer reactivity ratio","volume":"38","author":"Yamada","year":"2000","journal-title":"J. Polym. Sci. Part A Polym. Chem."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"2620","DOI":"10.1039\/C5PY00046G","article-title":"Hydrogen bonding promoting the controlled radical polymerization of 2-vinyl pyridine: Supramonomer for better control","volume":"6","author":"Wu","year":"2015","journal-title":"Polym. Chem."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"2731","DOI":"10.1039\/c2py20283b","article-title":"Favorable hydrogen bonding in room-temperature Cu(0)-mediated controlled radical polymerization of 4-vinylpyridine","volume":"3","author":"Wang","year":"2012","journal-title":"Polym. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"2015","DOI":"10.1039\/C5PY02047F","article-title":"RAFT polymerization of N-vinylpyrrolidone mediated by cyanoprop-2-yl-1-dithionaphthalate in the presence of a fluoroalcohol: The possibility of altering monomer properties by hydrogen bonding?","volume":"7","author":"Liu","year":"2016","journal-title":"Polym. Chem."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"6731","DOI":"10.1021\/acs.macromol.6b01563","article-title":"RAFT dispersion alternating copolymerization of styrene with N-phenylmaleimide: Morphology control and application as an aqueous foam stabilizer","volume":"49","author":"Yang","year":"2016","journal-title":"Macromolecules"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"2204","DOI":"10.1016\/j.tetlet.2008.02.001","article-title":"Triphenylphosphine oxide supported on non-cross-linked maleimide\u2013styrene copolymer: Application as a novel Hendrickson reagent","volume":"49","author":"Mahdavi","year":"2008","journal-title":"Tetrahedron Lett."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"5351","DOI":"10.1016\/j.polymer.2013.07.059","article-title":"Self-healing bio-based furan polymers cross-linked with various bis-maleimides","volume":"54","author":"Zeng","year":"2013","journal-title":"Polymer"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"132","DOI":"10.1016\/j.polymdegradstab.2011.11.011","article-title":"Copolymerization of maleimide-based benzoxazine with styrene and the curing kinetics of the resultant copolymer","volume":"97","author":"Ke","year":"2013","journal-title":"Polym. Degrad. Stab."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"9542","DOI":"10.1021\/ja0717616","article-title":"A facile procedure for controlling monomer sequence distribution in radical chain polymerizations","volume":"129","author":"Pfeifer","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"7360","DOI":"10.1021\/ma901064h","article-title":"Single-electron transfer living radical polymerization (SET-LRP) of methyl methacrylate (MMA) with a typical RAFT agent as an Initiator","volume":"42","author":"Zhang","year":"2009","journal-title":"Macromolecules"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"485","DOI":"10.1016\/j.saa.2013.08.044","article-title":"Spectroscopic, thermal analysis and DFT computational studies of salen-type Schiff base complexes","volume":"117","author":"Ebrahimi","year":"2014","journal-title":"Mol. Biomol. Spectrosc."},{"key":"ref_18","unstructured":"Dennington, R.D., Keith, T.A., and Millam, J.M. (2008). GaussView 5.0. 9, Gaussian Inc."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1080\/00222337508068644","article-title":"Analysis of the linear methods for determining copolymerization reactivity ratios. I. A new improved linear graphic method","volume":"9","author":"Kelen","year":"1975","journal-title":"J. Macromol. Sci. Chem."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"2277","DOI":"10.1002\/pol.1975.170131010","article-title":"Analysis of the linear methods for determining copolymerization reactivity ratios. II. A critical reexamination of cationic monomer reactivity ratios","volume":"13","author":"Kennedy","year":"1975","journal-title":"J. Polym. Sci. Polym. Chem. Ed."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.molstruc.2016.05.008","article-title":"Molecular structure, vibrational, UV, NMR, HOMO-LUMO, MEP, NLO, NBO analysis of 3,5 di tert butyl 4 hydroxy benzoic acid","volume":"1120","author":"Mathammal","year":"2016","journal-title":"J. Mol. Struct."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"189","DOI":"10.1016\/j.molstruc.2015.08.033","article-title":"Vibrational assignments, spectroscopic investigation (FT-IR and FT-Raman), NBO, MEP, HOMO.LUMO analysis and intermolecular hydrogen bonding interactions of 7-fluoroisatin, 7-bromoisatin and 1-methylisatin\u2014A comparative study","volume":"1101","author":"Polat","year":"2015","journal-title":"J. Mol. Struct."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"747","DOI":"10.1126\/science.218.4574.747","article-title":"Role of frontier orbitals in chemical reactions","volume":"218","author":"Fukui","year":"1982","journal-title":"Science"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"2981","DOI":"10.1016\/j.corsci.2008.08.043","article-title":"The use of quantum chemical methods in corrosion inhibitor studies","volume":"50","author":"Gece","year":"2008","journal-title":"Corros. Sci."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"5120","DOI":"10.1021\/cr900115u","article-title":"Stereospecific living radical polymerization: Dual control of chain length and tacticity for precision polymer synthesis","volume":"109","author":"Satoh","year":"2009","journal-title":"Chem. Rev."}],"container-title":["Polymers"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4360\/9\/3\/89\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T18:29:42Z","timestamp":1760207382000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4360\/9\/3\/89"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2017,3,3]]},"references-count":25,"journal-issue":{"issue":"3","published-online":{"date-parts":[[2017,3]]}},"alternative-id":["polym9030089"],"URL":"https:\/\/doi.org\/10.3390\/polym9030089","relation":{},"ISSN":["2073-4360"],"issn-type":[{"value":"2073-4360","type":"electronic"}],"subject":[],"published":{"date-parts":[[2017,3,3]]}}}