K. Sugiyama et al., PREPARATION AND CHARACTERIZATION OF POLYE THERURETHANEUREAS CONTAINING METHYL-SUBSTITUTED OR FLUORO SUBSTITUTED BIPHENYLDIYL IN HARD SEGMENTS, Nippon kagaku kaishi, (2), 1997, pp. 139-146
Polyetherurethaneureas (PEUUs) including methyl- or fluoro substituted
biphenyldiyls(BP, nMBP, nFBP) in main chain were obtained from a typi
cal two step addition polymerization of polytetrahydrofuran #1000(PTHF
) to 4,4'-methylene bis(phenyl isocyanate) (MPI) in the presence of th
e substituted biphenyldiols, using ethylenediamine (EDA) as a chain ex
tension reagent. Biphenyldiols used were 4,4'-biphenyldiol (BP), 3,3'-
dimethyl-4,4'-biphenyldiol (2MBP), 3,3', 5,5'-tetramethyl-4,4'-bipheny
ldiol(4MBP), 3,3'-difluoro-4,4'-biphenyldiol (2MBP), 3,3', 5,5'-tetraf
luoro-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 o
f DMSO and IBMK(1 : 1) gave the PEUUs such as PEUU-BP, PEUU-nMBP, PEUU
-nFBP. Parent polyetherurethaneurea (PEUU) was also prepared with a mo
lar ratio of 1 : 2 : 1 for PTHF : MPI : EDA. XPS spectra of the PEUUs
indicated that the hydrophobic segments containing the substituted bip
henyldiyl moieties are located on the surface of the PEUUs film in air
. The measurements of contact angle to water confirmed that the introd
uction of methyl groups or fluorine atoms into biphenyl ring results i
n 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 PEU
U-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 adhesi
veness of mouse fibroblast(L-929). Because of their mechanical and bio
compatible properties, PEUU-nMBP and PEUU-nFBP are expected to be usef
ul materials as an artificial blood vessel.