Abstract
Aqueous dispersions of fluorinated particles (PBF) based on copolymers of butyl acrylate with 2-(perfluorononenyloxy)ethyl methacrylate (FNEMA), 2,2,3,3-tetrafluoropropyl acrylate, and 2,2,3,3,4,4,5,5-octafluoropentyl acrylate, respectively, were synthesized by emulsion polymerization in the presence of unfluorinated and fluorinated anionic surfactant binary mixtures. These fluorinated dispersions showed good to excellent colloidal stability, as determined by freeze–thaw, centrifugation, and critical coagulation concentration measurements. Blending of small amounts (1–10 wt.%) of PBF latex particles with a waterborne hybrid poly(urethane-urea)-methacrylate (PUUA) resulted in a series of slightly fluorinated modified PUUA with good film-forming properties and low surface energy. The precursor PUUA had been synthesized separately by simultaneous chain extension of a poly(ester-urethane)-diisocyanate with ethylenediamine and soapless free radical polymerization of methyl methacrylate swelling the resulting branched or slightly cross-linked poly(urethane-urea) self-dispersible ionomer particles. The results of dynamic light scattering and zeta potential measurements suggest that the merging of PUUA and PBF particles and either engulfing or interdiffusion of the incompatible macromolecular phases occurred to some extent already in the colloidal state. Highly hydrophobic films with surface energy as low as 17 mJ/m2 were obtained upon the hybridization of PUUA with the FNEMA copolymer. Thermal annealing allowed minimizing the effects of fast surface dynamics, leading ultimately to water absorption, and promoting synergistic enhancement of the resulting hybrid film hardness, as required for coating applications.
Similar content being viewed by others
References
Dieterich D (1981) Aqueous emulsions, dispersions and solutions of polyurethanes; synthesis and properties. Prog Org Coat 9:281–340
Szycher M (1999) Szycher’s handbook of polyurethanes. CRC, Boca Raton
Lee JS, Kim BK (1995) Polyurethane cationomers from polypropylene glycol and isophorone diisocyanate: emulsion characteristics and tensile properties of cast films. Prog Org Coat 25:311–318
Madboulya SA, Otaigbe JU (2009) Recent advances in synthesis, characterization and rheological properties of polyurethanes and POSS/polyurethane nanocomposites dispersions and films. Progr Polym Sci 34:1283–1332
Jiang L, Xu Q, Hu CP (2006) Preparation and characterization of waterborne polyurethaneurea composed of dimer fatty acid polyester polyol. J Nanomater, pp 1–10
Barrère M, Landfester K (2003) High molecular weight polyurethane and polymer hybrid particles in aqueous miniemulsion. Macromolecules 36:5119–5125
Turri S, Levi M, Trombetta T (2004) Waterborne anionomeric polyurethane–ureas from functionalized fluoropolyethers. J Appl Polym Sci 93:136–144
Guyot A, Landfester K, Schork FJ, Wang C (2007) Hybrid polymer latexes. Prog Polym Sci 32:1439–1461
Hirose M, Zhou J, Nagai K (2000) The structure and properties of acrylic–polyurethane hybrid emulsions. Prog Org Coat 38:27–34
Hu YS, Tao Y, Hu CP (2001) Polyurethaneurea/vinyl polymer hybrid aqueous dispersions based on renewable material. Biomacromolecules 2:80–84
Chai SL, Jin MM (2009) Morphology and particle size of nanograde polyurethane/polyacrylate hybrid emulsions. J Appl Polym Sci 114:2030–2035
Peruzzo PJ, Anbinder PS, Pardini OR, Cost C, Leite CA, Galembeck F, Amalvy JI (2010) Polyurethane/acrylate hybrids: effects of the acrylic content and thermal treatment on the polymer properties. J Appl Polym Sci 116:2694–2705
Wang C, Chu F, Guyot A, Gauthier C, Boisson F (2006) Hybrid acrylic–polyurethane latexes: emulsion versus miniemulsion polymerization. J Appl Polym Sci 101:3927–3941
Udagama R, Degrandi-Contraires E, Creton C, Graillat C, McKenna TFL, Bourgeat-Lami E (2011) Synthesis of acrylic–polyurethane hybrid latexes by miniemulsion polymerization and their pressure-sensitive adhesive applications. Macromolecules 44:2632–2642
Li C-Y, Chiu W-Y, Lee C-F (2007) Morphological features of PU/PMMA hybrid latex prepared by miniemulsion polymerization. e-Polymers no. 015
Wang C, Chu F, Graillat C, Guyot A (2003) Hybrid acrylic–polyurethane latexes by miniemulsion polymerization. Polym React Eng 11:541–562
Zhu G (2007) Properties of polyurethane–poly(2,2,3,3-tetrafluoropropyl acrylate) triblock copolymer aqueous dispersion and its film cast from the dispersion. Fibers Polym 8:243–248
Xin H, Shen Y, Li X (2011) Novel cationic polyurethane–fluorinated acrylic hybrid latexes: synthesis, characterization and properties. Colloids Surf A: Physicochem Eng Aspects 384:205–211
Jiang M, Zheng Z, Ding X, Cheng X, Peng Y (2007) Convenient synthesis of novel fluorinated polyurethane hybrid latexes and core–shell structures via emulsion polymerization process with self-emulsification of polyurethane. Colloid Polym Sci 285:1049–1054
Yu Z, Zhang Z, Yuan Q, Ying S (2002) Surface analysis of coating based on novel water-diluted fluorinated polymer/silica hybrids. Adv Polym Technol 21:268–274
Li H, Zhang ZB, Hu CP, Wu SS, Ying SK (2004) Surface composition and property of film prepared with aqueous dispersion of polyurethaneurea–acrylate including fluorinated block copolymer. Eur Polym J 40:2195–2201
Makarov KN, Gervits LL, Cheburkov YuA, Knunyants IL, Sass VP (1977) Hexafluoropropene trimer. Synthesis and properties of functional derivatives. J Fluorine Chem 10:323–327
Hayakawa Y, Ono T (2006) Facile synthesis of polystyrene bearing highly branched perfluorinated groups. Eur Polym J 42:1357–1361
Chen L, Shi H, Wu H, Xiang J (2010) Preparation and characterization of a novel fluorinated acrylate resin. J Fluorine Chem 131:731–737
Zhang ZB, Ying SK, Zhang QL, Xu XD (2001) Well-controlled radical copolymerization of styrene with 2-[(perfluorononenyl)oxy]ethyl methacrylate and characterization of its copolymers. J Polym Sci Part A Polym Chem 39:2670–2676
Wang Z, Yang YJ, Dong Q, Liu T, Hu CP (2006) Polymerization of acrylonitrile in supercritical carbon dioxide. Polymer 47:7670–7679
Chen HQ, Huang ZX, Li H, Zhang YM, Liu YG (2009) Synthesis of pure (Co) polymers via supported cobalt(II)-catalyzed controlled/“living” radical polymerization. Polym Bull 62:151–166
Yang CC, Zhang ZB, Hu CP (2005) Water borne PUA modified with fluorinated polyacrylate microemulsion. China Synth Rubber Ind (Hecheng Xiangjiao Gongye) 28:69
Wilkinson MC, Kidwell RL (1971) A mathematical description of the harkins and brown correction curve for the determination of surface and interfacial tensions. J Colloid Interface Sci 35:114–119
Wu SH (1982) Polymer interfaces and adhesion. Marcel Dekker, New York
Cavagna F, Schumann C (1976) Non-bond F–F nuclear spin couplings II. Hexafluoropropene trimers. J Magn Resonance 22:333–344
Hayakawa Y, Nishida M, Ono T (2011) Novel polystyrene bearing highly branched hexafluoropropene trimer pendants. Polym Bull 67:805–814
Wang C, Yan P, Xing H, Jin C, Xiao J-X (2010) Thermodynamics of aggregation of ammonium/tetraalkylammonium perfluorooctanoates: effect of counterions. J Chem Eng Data 55:1994–1999
Simister EA, Lee EM, Lu JR, Thomas RK, Ottewill RH, Rennie AR, Penfold J (1992) Adsorption of ammonium perfluorooctanoate and ammonium decanoate at the air/solution interface. J Chem Soc Faraday Trans 88:3033–3041
Reid Dreher W, Jarrett WL, Urban MW (2005) Stable nonspherical fluorine-containing colloidal dispersions: synthesis and film formation. Macromolecules 38:2205–2212
Binks BP, Murakami R (2006) Phase inversion of particle-stabilized materials from foams to dry water. Nat Mater 5:865–869
Su T, Hu CP (2009) Preparation and properties of waterborne interpenetrating polymer networks composed of polyurethaneurea and graft vinyl ester resin. J Appl Polym Sci 114:1070–1079
Chai SL, Jin MM, Tan HM (2008) Comparative study between core–shell and interpenetrating network structure polyurethane/polyacrylate composite emulsions. Eur Polym J 44:3306–3313
Urban MW, Allison CL, Johnson GL, Di Stefano F (1986) Stratification of butyl acrylate/polyurethane (BA/PUR) latexes: ATR and step-scan photoacoustic studies. Appl Spectrosc 53:1520–1526
Acknowledgments
The GC-MS analyses were kindly performed by Dr. Alessia Andreotti at the Analytical Chemistry lab of the Department of Chemistry and Industrial Chemistry, the University of Pisa.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
ESM 1
(DOC 10718 kb)
Rights and permissions
About this article
Cite this article
Yang, C., Castelvetro, V., Zhang, Y. et al. Facile hydrophobic modification of hybrid poly(urethane-urea)methacrylate aqueous dispersions and films through blending with novel waterborne fluorinated acrylic copolymers. Colloid Polym Sci 290, 491–506 (2012). https://doi.org/10.1007/s00396-011-2565-y
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00396-011-2565-y