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Chemical modification of polynorbornene: transformation of ester moiety containing polynorbornene to carboxylic acid structure

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Abstract

Polynorbornene (PNB) having methyl ester in side chain was partially hydrolyzed under alkaline condition in mixed organic solvents containing tetramethylammonium hydroxide as a base. Through hydrolysis of methyl ester group in PNB under basic condition, PNB having carboxylic acid can be obtained and degree of hydrolysis (DH) were evaluated by 1H NMR measurement from 0.1 to 0.8, depending upon reaction conditions such as reaction time, solvent, and amount of base. The resulting hydrolyzed PNB were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, and size exclusion chromatography. No remarkable decreasing of molecular weight was observed and chain scission does not occur during the hydrolysis of PNB in the reaction condition examined here. The glass transition temperature of hydrolyzed PNB increased with increase in DH which can be attributed to the existence of intermacromolecular association of carboxylic acid in hydrolyzed PNB. Esterification of PNB having carboxylic acid was also carried out by using alkyl halide and DBU.

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References

  1. Shin JY, Park JY, Liu C, He J, Kim SC (2005) Chemical structure and physical properties of cyclic olefine copolymers. Pure Appl Chem 77:801–814

    Article  CAS  Google Scholar 

  2. Inoue T, Okamoto H, Osaki K, Kohara T, Natsume T (1995) Dynamic birefringence of amorphous polyolefins II. Measurements on polymers containing five-membered ring in main chain. Polym J 27:943–950

    Article  Google Scholar 

  3. Kaita S, Matsushita K, Tobita M, Maruyama Y, Wakatsuki Y (2006) Cyclopentadienyl nickel and palladium complexes/activator system for the vinyl-type copolymerization of norbornene with norbornene carboxylic acid esters: control of polymer solubility and glass transition temperature. Macromol Rapid Commun 27:1752–1756

    Article  CAS  Google Scholar 

  4. Heinz BS, Alt FP, Heitz W (1998) Pd(II)-catalyzed vinylic polymerization of norbornene and copolymerization with norbornene carboxylic acid esters. Macromol Rapid Commun 19:251–256

    CAS  Google Scholar 

  5. Mathew JP, Reinmuth A, Melia J, Swords N, Risse W (1996) (η3-Allyl)palladium(II) and palladium(II) nitrile catalysts for the addition polymerization of norbornene derivatives with functional groups. Macromolecules 29:2755–2763

    Article  CAS  Google Scholar 

  6. Abd-El-Aziz AS, May LJ, Edel AL (2000) Synthesis of substituted norbornenes and their polymerization to polynorbornenes with flexible aliphatic side-chains. Macromol Rapid Commun 21:598–602

    Article  CAS  Google Scholar 

  7. Maughon BR, Weck M, Mohr B, Grubbs RH (1997) Influence of backbone rigidity on the thermotropic behavior of side-chain liquid crystalline polymers synthesized by ring-opening metathesis polymerization. Macromolecules 30:257–265

    Article  CAS  Google Scholar 

  8. Pugh C, Shao J, Ge JJ, Cheng SZD (1998) Correlation of model compounds and laterally attached side-chain liquid-crystalline polynorbornenes with an 11-carbon spacer. Macromolecules 31:1779–1790

    Article  CAS  Google Scholar 

  9. Sudo A, Morishita H, Endo T (2010) Synthesis of a norbornene monomer having cyclic carbonate moiety based on CO2 fixation and its transition metal-catalyzed polymerizations. J Polym Sci Part A 48:3896–3902

    Article  CAS  Google Scholar 

  10. Sudo A, Morishita H, Endo T (2011) Synthesis of reactive poly(norbornene): ring-opening metathesis polymerization of norbornene monomer bearing cyclic dithiocarbonate moiety. J Polym Sci Part A 49:1097–1103

    Article  CAS  Google Scholar 

  11. Tanaka S, Nishida H, Endo T (2009) Miscibility of polynorbornene/poly(styrene-co-hydroxystyrene) binary blend based on hydrogen-bonding interaction. Macromol Chem Phys 210:1235–1240

    Article  CAS  Google Scholar 

  12. De Loecker W, Smets G (1959) Hydrolysis of methacrylic acid-methyl methacrylate copolymers. J Polym Sci 40:203–216

    Article  Google Scholar 

  13. Smets G, De Loecker W (1959) Alkaline hydrolysis of methylacrylic acid-ester copolymers. J Polym Sci 41:375–380

    Article  CAS  Google Scholar 

  14. Glavis FJ (1959) Hydrolysis of crystallizable poly(methyl methacrylate). J Polym Sci 36:547–549

    Article  CAS  Google Scholar 

  15. Xiang M, Jiang M, Kong X, Yang Y, Lu W (1997) A novel synthesis of acrylic acid containing polymers. Macromol Rapid Commun 18:385–391

    Article  CAS  Google Scholar 

  16. Góźdź AS (1981) Phase transfer catalyzed reactions on polymers, 2. The alkaline hydrolysis of poly(methyl methacrylate). Makromol Chem Rapid Commun 2:443–448

    Article  Google Scholar 

  17. Smith P, Goulet L (1993) Effect of the addition of amine diluents on the physical properties of poly(methyl methacrylate-co-methacrylic acid) copolymers obtained by partial hydrolysis of PMMA. J Polym Sci Part B 31:327–338

    Article  CAS  Google Scholar 

  18. Matsuzaki K, Okamoto T, Ishida A (1964) Polymerization of butyl esters of methacrylic acid and hydrolysis of the polymers. J Polym Sci Part A 2:1105–1114

    Google Scholar 

  19. Bressy C, NGuyen MN, Tanguy B, Ngo VG, Margaillan A (2010) Poly(trialkylsilyl methacrylate)s: a family of hydrolysable polymers with tuneable erosion profiles. Polym Degrad Stab 95:1260–1268

    Article  CAS  Google Scholar 

  20. Otocka EP, Kwei TK (1968) Properties of ethylene-acrylic acid copolymers. Macromolecules 1:244–249

    Article  CAS  Google Scholar 

  21. Inomata K, Kawasaki S, Kameyama A, Nishikubo T (2001) Synthesis and photochemical properties of novel multifunctional photopolymers with both pendant epoxy groups and phenacyl ester groups. J Polym Sci Part A 39:530–538

    Article  CAS  Google Scholar 

  22. Maa YF, Chen SH (1989) Synthesis of thermotropic liquid crystalline side-chain polymers via chemical modification of polymeric carboxylic acids. Macromolecules 22:2036–2039

    Article  CAS  Google Scholar 

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  1. Molecular Engineering Institute, Kinki University, 11-6 Kayanomori, Iizuka, Fukuoka, 820-8555, Japan

    Shimon Tanaka & Takeshi Endo

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  1. Shimon Tanaka
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  2. Takeshi Endo
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Correspondence to Shimon Tanaka.

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Tanaka, S., Endo, T. Chemical modification of polynorbornene: transformation of ester moiety containing polynorbornene to carboxylic acid structure. Polym. Bull. 70, 643–651 (2013). https://doi.org/10.1007/s00289-012-0828-5

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  • DOI: https://doi.org/10.1007/s00289-012-0828-5

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