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Novel hydrophobic macromonomers for potential amphiphilic block copolymers

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Abstract

Oligomers of 2-methyl nylon3 (2mN3) and 3-methyl nylon3 (3mN3) were synthesized by base-catalyzed hydrogen transfer polymerization (HTP) of methacrylamide and crotonamide, respectively. The detailed structural analyses of 2mN3 and 3mN3 were performed using MALDI-MS, 1H-NMR, elemental analysis and several end-group analyses to ascertain polymerization mechanism and exact chemical structures of final products. The structural analyses revealed that (1) base-catalyzed HTP of methacrylamide and crotonamide follows the sequence of: hydrogen abstraction from amide group of monomer by basic catalyst (NatBuO), addition of monomeric units to the anionic center, intramolecular hydrogen migration and finally, termination by hydrogen transfer from protonated catalyst (tBuOH) to anionic end-group, (2) both oligomeric products have olefinic chain-ends resulting from the initiation mechanism. The specific behavior of basic catalyst leads to the formation of olefinic chain-ends that are apt to possible end-group functionalization. Since the functional end-groups of a well-defined macromonomer are of importance in terms of chain extension, grafting, chemical modification, click chemistry, monolayer surface modification, etc., it was aimed to create more reactive functional end-groups by epoxylation and bromination. Disappearance of the signals belonging to the olefinic protons in 1H-NMR spectra of modified oligomers and existence of bromine and epoxy adducts in MALDI MS spectra of the modified oligomers were attributed to end-group modification as intended. Hence, four novel macromonomers of polyamidic backbone with functional chain-ends were synthesized successfully.

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References

  1. Masamoto J, Sasguri K, Ohizumi C, Yamaguchi K, Kobayashi H (1970) A new synthetic fiber made of nylon3. J Appl Polym Sci 14:667–680

    Article  CAS  Google Scholar 

  2. Masamoto J (2000) Nylon3. Rep Prog Polym Phys Jpn 43:867–876

    Google Scholar 

  3. Yamamoto F, Misumi T (1991) Preparation of poly-β-alanine from acrylamide. US Pat. 5,015,707 assigned to Asahi Chemical

  4. Graf R, Lohaus G, Borner K, Schmidt E, Bestian H (1962) β-Lactams, their polymerization and use as raw materials for fibers. Angew Chem Int Ed Engl 1:481–488

    Article  Google Scholar 

  5. Breslow DS, Hulse GE, Matlack AS (1957) Synthesis of poly-β-alanine from acrylamide. A novel synthesis of β-alanine. J Am Chem Soc 79:3760–3763

    Article  CAS  Google Scholar 

  6. Otsu T, Yamada B, İtahashi M, Mori T (1976) Hydrogen transfer polymerization of methyl substituted acrylamides. J Polym Sci Polym Chem Ed 14:1347–1361

    Article  CAS  Google Scholar 

  7. Yamaguchi K, Minoura Y (1972) Hydrogen-transfer polymerization of acrylamide and methacrylamide with optically active basic catalysts. J Polym Sci 10:1217–1231

    Article  CAS  Google Scholar 

  8. Guaita M, Thomas LF (1968) High resolution NMR investigation of poly(β-alanine) and poly(α-methyl-β-alanine). Makromolekul Chem 119:113–121

    Article  CAS  Google Scholar 

  9. Kobuke Y, Hanji K, Fukurawa J (1971) Hydrogen transfer polymerization of cis- and trans-crotonamides. J Polym Sci 9:431–440

    Article  CAS  Google Scholar 

  10. Eisenbach CD, Lenz RW, Duval M, Marchessault RH (1979) Polymerization of α, α-disubstituted β-propiolactones and lactams, 12. Properties and crystalline structure of poly(β-propiolactam)s. Makromolekul Chem 180:429–440

    Article  CAS  Google Scholar 

  11. Wexler H (1968) Migrational polymerization of methacrylamide. Makromolekul Chem 115:262–267

    Article  CAS  Google Scholar 

  12. Schmidt E (1970) Über optisch aktive poly-β-amide. Angew Macromol Chem 14:185–202

    Article  CAS  Google Scholar 

  13. Tan I, Zarafshani Z, Lutz JF, Titirici MM (2009) PEGylated chromatography: efficient bioseparation on silica monoliths grafted with smart biocompatible polymers. ACS Appl Mater Interfaces 1(9):1869–1872

    Article  CAS  Google Scholar 

  14. Goddard JM, Hotchkiss JH (2007) Polymer surface modification for the attachment of bioactive compounds. Prog Polym Sci 32:698–725

    Article  CAS  Google Scholar 

  15. Lemechko P, Renard E, Volet G, Colin CS, Guezennec J, Langlois V (2012) Functionalized oligoesters from poly(3-hydroxyalkanoate)s containing reactive end group for click chemistry: Application to novel copolymer synthesis with poly(2-methyl-2-oxazoline). React Funct Polym 72:160–167

    Article  CAS  Google Scholar 

  16. Fray ME, Skrobot J, Bolikal D, Kohn J (2012) Synthesis and characterization of telechelic macromers containing fatty acid derivatives. React Funct Polym 72:781–790

    Article  Google Scholar 

  17. Thompson MS, Vadala TP, Vadala ML, Lin Y, Riffle JS (2008) Synthesis and applications of heterobifunctional poly(ethylene oxide) oligomers. Polymer 49:345–373

    Article  CAS  Google Scholar 

  18. Masamoto J, Sasguri K, Ohizumi C, Kobayashi H (1970) Polymorphic forms of nylon3. J Polym Sci 8:1703–1711

    CAS  Google Scholar 

  19. Yasuda M (1931) Determination of iodine numbers of some lipids. J Biochem 94:401–409

    CAS  Google Scholar 

  20. Ogata N (1960) The transition polymerization of acrylamide. Part II. On the reaction mechanism. Makromol Chem 40:55–63

    Article  CAS  Google Scholar 

  21. Tani H, Oguni N, Araki T (1963) Initiation reaction in the strong base catalyzed polymerization of acrylamide. Makromol Chem 76:82–88

    Article  Google Scholar 

  22. Haldar U, Ramakrishnan L, Sivaprakasam K, De P (2014) Main-chain sulphur containing water soluble poly(N-isopropylacrylamide-co-N,N′-dimethylacrylamide sulphide) copolymers via interfacial polycondensation. Polymer 55:5656–5664

    Article  CAS  Google Scholar 

  23. Ballard N, Salsamendi M, Santos JI, Ruipérez F, Leiza JR, Asua JM (2014) Experimental evidence shedding light on the origin of the reduction of branching of acrylates in ATRP. Macromolecules 47:964–972

    Article  CAS  Google Scholar 

  24. Parent EE, Dence CS, Jenks C, Sharp TL, Welch MJ, Katzenellenbogen JA (2007) Synthesis and biological evaluation of [18F] bicalutamide, 4-[76Br] bromobicalutamide, and 4-[76Br] bromo-thiobicalutamide as non-steroidal androgens for prostate cancer imaging. J Med Chem 50:1028–1040

    Article  CAS  Google Scholar 

  25. Tong KH, Wong KY, Chan TH (2003) Manganese/bicarbonate-catalyzed epoxidation of lipophilic alkenes with hydrogen peroxide in ionic liquids. Org Lett 5:3423–3425

    Article  CAS  Google Scholar 

  26. de Gooijer JM, Scheltus M, Koning LE (2004) End group modification of polyamide-6 in supercritical and subcritical fluids: Part 2: Amine and carboxylic acid end group modification with 1,2-epoxybutane. J Supercrit Fluids 29:153–164

    Article  CAS  Google Scholar 

  27. Sugi R, Yokohama A, Yokozawa T (2003) Synthesis of well-defined telechelic aromatic polyamides by chain-growth polycondensation: application to the synthesis of block copolymers of polyamide and poly(tetrahydrofuran). Macromol Rapid Commun 24:1085–1090

    Article  CAS  Google Scholar 

  28. Hossainy SFA (2004) Rotary coating apparatus for coating implantable medical devices. US Patent 6.709.514 B1

  29. Facetti SD (2008) Biobeneficial polyamide/polyethylene glycol polymers for use with drug eluting stents. US Patent 7.435.788 B2

  30. Stuparu CM, Khan A (2016) Thiol-epoxy “click” chemistry: application in preparation and postpolymerization modification of polymers. J Poylm Sci Part A Polym Chem 54:3057–3070

    Article  CAS  Google Scholar 

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Acknowledgements

The authors wish to thank Dr. Mehmet Atakay for the MALDI mass measurements.

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Authors and Affiliations

  1. Department of Chemistry, Ordu University, 52200, Ordu, Turkey

    Efkan Çatıker

  2. Department of Chemistry, Hacettepe University, 06800, Ankara, Turkey

    Olgun Güven & Bekir Salih

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  1. Efkan Çatıker
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  2. Olgun Güven
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  3. Bekir Salih
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Correspondence to Efkan Çatıker.

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Çatıker, E., Güven, O. & Salih, B. Novel hydrophobic macromonomers for potential amphiphilic block copolymers. Polym. Bull. 75, 47–60 (2018). https://doi.org/10.1007/s00289-017-2014-2

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  • DOI: https://doi.org/10.1007/s00289-017-2014-2

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