Skip to main content
SpringerLink
Log in

Photo-cured organic–inorganic hybrid composites of methacrylate-terminated 4-arm star-shaped ε-caprolactone oligomer and methacrylate- or thiol-substituted polysilsesquioxane

  • Original Paper
  • Published:
Journal of Polymer Research Aims and scope Submit manuscript

Abstract

Methacrylate-terminated 4-arm star-shaped ε-caprolactone oligomer (ME4CLO) was synthesized by reaction of hydroxy-terminated 4-arm star-shaped ε-caprolactone oligomer (H4CLO) having a degree of polymerization per one oligocaprolactone chain, n = 5 and methacryloyl chloride in the presence of triethylamine. The ME4CLO was photo-cured with methacrylate-substituted polysilsesquioxane (ME-PSQ) or mercaptopropyl-substituted polysilsesquioxane (SH-PSQ) at the weight ratios of 16/0, 16/1, 16/2 and 16/4. Fourier transform infrared spectroscopy (FTIR) of the cured hybrid composites revealed addition polymerization of the methacryloyl groups and/or a thiol-ene reaction of methacryloyl and mercapto groups. Transmission electron microscope (TEM) observation revealed phase-separated spherical particles with a diameter of 5 μm for the cured ME4CLO/ME-PSQ 16/2, while the cured ME4CLO/SH-PSQ 16/2 had unstructured, finer-sized particles. DSC analysis revealed crystallization of the oligocaprolactone chain was largely disturbed by the crosslinking reaction and that the cured ME4CLO/ME-PSQ and ME4CLO/SH-PSQ 16/1 showed a higher glass transition temperature than cured ME4CLO. Tensile modulus of cured ME4CLO/ME-PSQ increased with increasing ME-PSQ content while cured ME4CLO/SH-PSQ showed a lower tensile modulus than cured ME4CLO.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. Inoue K (2000) Functional densrimers, hyperbranches and star polymers. Prog Polym Sci 25:453–571

    Article  CAS  Google Scholar 

  2. Cameron DJA, Shaver MP (2011) Aliphatic polyester polymer stars: synthesis, properties and applizcations in biomedicine and nanotechnology. Chem Soc Rev 40:1761–1776

    Article  CAS  Google Scholar 

  3. Acebo C, Picardi A, Fernández-Francos X, Flor SD, Ramis X, Serra À (2014) Effect of hydroxyl ended and end-capped multiarm star polymers on the curing process and mechanical characteristics of epoxy/anhydride thermosets. Prog Org Coatins 77:1288–1298

    Article  CAS  Google Scholar 

  4. Choi J, Kim IK, Kwak SY (2005) Synthesis and characterization of a series of star-branched poly (ε-caprolactone)s with the variation in arm numbers and lengths. Polymer 46:9725–9735

    Article  CAS  Google Scholar 

  5. Wang JL, Dong CM (2006) Physical properties, crystallization kinetics, and spherulitic growth of well-defined poly (ε-caprolactone)s with different arms. Polymer 47:3218–3228

    Article  CAS  Google Scholar 

  6. Sobczak M, Witkowska E, Olędzka E, Kolodziejski W (2008) Synthesis and structural analysis of polyester prodrugs of norfloxacin. Molecules 13:96–106

    Article  CAS  Google Scholar 

  7. Chung I, Xie D, Puckett AD, Mays JW (2003) Synthesis and evaluation of biodegradable multifunctional polymer networks. Eur Polym J 39:1817–1822

    Article  CAS  Google Scholar 

  8. Younes HM, Bravo-Grimaldo E, Amsden BG (2004) Synthesis, characterization and vitro degradation of a biodegradable elastomer. Biomaterials 25:5261–5269

    Article  CAS  Google Scholar 

  9. Amsden B, Wang S, Wyss U (2004) Synthesis and characterization of thermoset biodegradable elastomers based on star-poly (ε-caprolactone-co-D, L-lactide). Biomacromolecules 5:1399–1404

    Article  CAS  Google Scholar 

  10. Uto K, Yamamoto K, Hirase S, Aoyagi T (2006) Temperature-responsive cross-linked poly (ε-caprolactone) membrane that functions near body temperature. J Controlled Release 110:408–413

    Article  CAS  Google Scholar 

  11. Serra RSI, Ivirico JLE, Dueñas JMM, Balado AA, Ribelle JLG, Sánchez MS (2009) Segmental dynamics in poly (ε-caprolactone)/poly (L-lactide) copolymer networks. J Polym Sci Part B Polym Phys 47:183–193

    Article  CAS  Google Scholar 

  12. Cai L, Wang S (2010) Parabolic dependence of material properties and cell behavior on the composition of polymer networks via simultaneously controlling crosslinking density and crystallinity. Biomaterilas 31:7423–7434

    Article  CAS  Google Scholar 

  13. Hakala RA, Korhonen H, Meretoja VV, Seppälä JV (2011) Photo-cross-linked biodegradable polt (ester anhydride) networks prepared from alkenylsuccinic anhydride functionalized poly (ε-caprolactone) precursors. Biomacromolecules 12:2806–2814

    Article  CAS  Google Scholar 

  14. Liu Q, Jiang L, Shi R, Zhang L (2012) Synthesis, preparation, in vitro degradation, and application of novel degradable bioelastomers-A review. Prog Polym Sci 37:715–765

    Article  CAS  Google Scholar 

  15. Lichtenhan JD, Vu NQ, Carter JA, Gilman JW, Feher FJ (1993) Silsesquioxane-siloxane copolymers from polyhedral silsesquioxanes. Macromolecules 26:2141–2142

    Article  CAS  Google Scholar 

  16. Lichtenhan JD, Otonari YA, Carr MJ (1995) Linear hybrid polymer building blocks: Methacrylate-functionalized polyhedral oligomeric silsesquioxane monomers and polymers. Macromolecules 28:8435–8437

    Article  CAS  Google Scholar 

  17. Haddad TS, Lichtenhan JD (1995) The incorporation of transition metals into polyhedral oligosilsesquioxane polymers. J Inorg Organomet Polym 5:237–246

    Article  CAS  Google Scholar 

  18. Yoon KH, Park JH, Min BG, Polk MB, Schiraldi DA (2005) Properties of poly (ethylene terephthalate) containing epoxy-functionalized polyhedral oligomeric silsesquioxane. Polym Int 254:47–53

    Article  Google Scholar 

  19. Hany R, Hartmann R, Böhlen C, Brandenberger S, Kawada J, Löwe C, Zinn M, Wilholt B, Marchessault RH (2005) Chemical synthesis and characterization of POSS-functionalized poly [3-hydroxyalkanoates]. Polymer 46:5025–5031

    Article  CAS  Google Scholar 

  20. Liu Y, Yang X, Zhang W, Zheng S (2006) Star-shaped poly (ε-caprolactone) with polyhedral oligomeric silsesquioxane core. Polymer 47:6814–6825

    Article  CAS  Google Scholar 

  21. Sakuma T, Kumagai A, Teramoto N, Shibata M (2008) Thermal and dynamic mechanical properties of organic–inorganic hybrid composites of itaconate-substituted poly (butylene succinate) and methacrylate-substituted polysilsesquioxane. J Appl Polym Sci 107:2159–2164

    Article  CAS  Google Scholar 

  22. Ando S, Someya Y, Takahashi T, Shibata M (2010) Thermal and mechanical properties of photo-cured organic–inorganic hybrid composites of terpene-based acrylate resin and methacrylate-substituted polysilsesquioxane. J Appl Polym Sci 115:3326–3331

    Article  CAS  Google Scholar 

  23. Shibata M, Obara S (2012) Photo-cured organic–inorganic hybrid composites of acrylated castor oil and methacrylate-substituted polysilsesquioxane. J Appl Polym Sci 126:E12–E20

    Article  CAS  Google Scholar 

  24. Fukuda T (2008) Technology of organic–inorganic hybrid material “Compoceran SQ series”. JETI 56:132–137

    CAS  Google Scholar 

  25. Schreck KM, Leung D, Bowman N (2011) Hybrid organic/inorganic thiol-ene-based photopolymerized networks. Macromolecules 44:7520–77529

    Article  CAS  Google Scholar 

  26. Lin H, Wan X, Jiang XS, Wang QK, Yin J (2011) A nanoimprint lithography hybrid photoresist based on the thiol-ene system. Adv Funct Polym 21:2960–2967

    Article  CAS  Google Scholar 

  27. Luo A, Jiang X, Lin H, Yin J (2011) “Thiol-ene” photo-cured hybrid materials based on POSS and renewable vegetable oil. J Mater Chem 21:12753–12760

    Article  CAS  Google Scholar 

  28. Li L, Liang R, Li Y, Liu H, Feng S (2013) Hybrid thiol-ene network nanocomposites based on multi (metha)acrylate POSS. J Colloid Interface Sci 406:3038

    Google Scholar 

  29. Wang X, Wang X, Song L, Xing W, Tang G, Hu W, Hu Y (2013) Preparation and thermal stability of UV-cured epoxy-based coatings modified with octamercaptopropyl POSS. Thermochimina Acta 568:130–139

    Article  CAS  Google Scholar 

  30. Wang L, Li J, Li L, Zheng S (2013) Organic-inorganic hybrid diblock copolymer composed of poly (ε-caprolactone) and poly (MA POSS): Synthesis and its nanocomposites with epoxy resin. J Polym Sci Part A Polym Chem 51:2079–2090

  31. Nakamura T, Chu X, Shimasaki T, Shibata M (2013) Organogelation behavior and thermal properties of supramolecular polymer network composed of carboxy- and pyridyl-terminated 4-arm star-shaped ε-caprolactone oligomers. J Colloid Interface Sci 404:8–15

    Article  CAS  Google Scholar 

  32. Hoyle CE, Lee TY, Roper T (2004) Thiol–enes: Chemistry of the past with promise for the Future. J Polym Sci Part A Polym Chem 49:1540–1573

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Life and Environmental Sciences Faculty of Engineering, Chiba Institute of Technology, 2-17-1 Tsudanuma, Narashino, Chiba, 275-0016, Japan

    Mamoru Ito, Toshiaki Shimasaki, Naozumi Teramoto & Mitsuhiro Shibata

Authors
  1. Mamoru Ito
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Toshiaki Shimasaki
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Naozumi Teramoto
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Mitsuhiro Shibata
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Mitsuhiro Shibata.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ito, M., Shimasaki, T., Teramoto, N. et al. Photo-cured organic–inorganic hybrid composites of methacrylate-terminated 4-arm star-shaped ε-caprolactone oligomer and methacrylate- or thiol-substituted polysilsesquioxane. J Polym Res 21, 507 (2014). https://doi.org/10.1007/s10965-014-0507-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10965-014-0507-3

Keywords

Search

Navigation