The hydroxy end groups of aromatic and aliphatic hyperbranched poly‐(urea urethane)s prepared with an AA* + B*B2 one‐pot method were modified with phenylisocyanate, butylisocyanate, and stearylisocyanate. The success of the modification reaction was verified with 1H NMR and IR spectroscopy. Linear model poly‐(urea urethane)s were prepared, too, for comparison. The bulk properties of OH functionalized hyperbranched poly(urea urethane)s, compared with those of linear analogues and modified hyperbranched poly(urea urethane)s, were studied with differential scanning calorimetry, thermogravimetric analysis, and temperature‐dependent Fourier transform infrared measurements. Transparent and smooth thin films could be prepared from all polymer samples and were examined with a light microscope, a microglider, and an atomic force microscope. The properties of the polymer surface were examined by measurements of the contact angle and zeta potential. For all samples, the properties were mainly governed by the strong interactions of the urea and urethane units within the backbone, whereas the influence of the nature of the end groups and of the branched structure was reduced in comparison with other hyperbranched polymer systems. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3376–3393, 2005

Elution fractionations of broadly molar mass-distributed, hyperbranched poly(urea-urethane)s with OH- and Ph- end groups were carried out to obtain a number of macromolecular samples possessing different molar masses at the same chemical structure. The characterization of the polymers was performed by SEC, MALLS, 1H-NMR, MALDI-TOF-MS and viscosity measurements. Modifications of the OH-end groups of the polymers were carried out. We observed a strong influence of the end groups on the solution behaviour of the hyperbranched samples. The molecular shape of the hyperbranched polymers in solution was compared to their linear analogue using the Kuhn-Mark-Houwink- Sakurada relationship. The calculated contraction factors between 0,15 and 0,7 depending on the molar masses correspond to a very compact structure of the modified branched polymers at high molar masses.

ABSTRACT:The present study demonstrates in situ realtime attenuated total reflection (ATR)-FTIR spectroscopy as a powerful tool for monitoring and analyzing different polymerization and polymer modification reactions. Thus, a metallocene catalyzed copolymerization of propene and 10-undecene-1-ol, a polycondensation reaction towards polysulfone, and a modification reaction of OH end groups of hyperbranched poly(urea-urethane) were investigated successfully. The interpretation of the development of FTIR spectra was carried out on the basis of typical vibration bands of chemical groups of the corresponding monomers and polymers in each case, e.g. of the CAC double bond of 10-undecene-1-ol during the copolymerization, the new COOOC group of polysulfone, and the new urethane end group of poly(urea-urethane). Kinetics prediction is also under consideration.

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Summary: Hyperbranched polyesteramides were prepared using phethalic anhydride (Ph An) or maleic anhydride (M An) as an A 2 monomer and diethanol amine (DEA) as B 0 B 2 monomer. Bulk condensation technique was used to synthesize polymers with both OH and modified polymers with long alkyl chain end groups. The prepared polymers were characterized using 1 H-NMR, FTIR and TGA. Solution viscosity for hyperbranched polyester amide with hydroxyl end groups was measured as well. Dielectric and electric properties of the modified samples were investigated over a range of frequency and temperatures. No relaxation peak is noticed in the dielectric spectrum e(n) at various temperatures. The illustration of the imaginary part of the electric modulus M 00 versus frequency shows a peak which is shifted towards higher frequency in increasing temperature.