K Sugiyama; S Akita; Y Tomoi; K Hanaki; K Shiraishi; K Ueda
NIPPON KAGAKU KAISHI CHEMICAL SOC JAPAN (2) 139 - 146 0369-4577 1997/02
Polyetherurethaneureas (PEUUs) including methyl- or fluoro substituted biphenyldiyls(BP, nMBP, nFBP) in main chain were obtained from a typical two step addition polymerization of polytetrahydrofuran #1000(PTHF) to 4,4'-methylene bis(phenyl isocyanate) (MPI) in the presence of the substituted biphenyldiols, using ethylenediamine (EDA) as a chain extension reagent. Biphenyldiols used were 4,4'-biphenyldiol (BP), 3,3'-dimethyl-4,4'-biphenyldiol (2MBP), 3,3', 5,5'-tetramethyl-4,4'-biphenyldiol(4MBP), 3,3'-difluoro-4,4'-biphenyldiol (2MBP), 3,3', 5,5'-tetrafluoro-4,4'-biphenyldiol (4FBP), and 2,2', 3,3', 5,5', 6,6'-octafluoro-4,4'-biphenyldiol (8FBP). Polyaddtion with a molar ratio of 0.5 : 0.5 : 2 : 1 for the biphenyidiol : PTHF : MPI : EDA in the mixed solvent of DMSO and IBMK(1 : 1) gave the PEUUs such as PEUU-BP, PEUU-nMBP, PEUU-nFBP. Parent polyetherurethaneurea (PEUU) was also prepared with a molar ratio of 1 : 2 : 1 for PTHF : MPI : EDA. XPS spectra of the PEUUs indicated that the hydrophobic segments containing the substituted biphenyldiyl moieties are located on the surface of the PEUUs film in air. The measurements of contact angle to water confirmed that the introduction of methyl groups or fluorine atoms into biphenyl ring results in higher hydrophobicity of PEUUs film surface. The tensile modulus(E) showed the values of E=109.1 MPa and E=129.3 MPa for PEUU-4MBP and PEUU-4FBP, respectively. It was also found that PEUU-nMBP and PEUU-nFBP, adsorb both bovine serum albumin and human serum gamma-globulin with a single layer. In cell culture test, the PEUUs films showed the adhesiveness of mouse fibroblast(L-929). Because of their mechanical and biocompatible properties, PEUU-nMBP and PEUU-nFBP are expected to be useful materials as an artificial blood vessel.