Infrared spectroscopy on new multiphase thermoplastic elastomers based on hydrogen bond complexes - temperature dependence and orientation behaviour

The structure and deformation behaviour of a new class of thermoplastic elastomers is studied by temperature dependent infrared (IR) spectroscopy and by IR - dichroism spectroscopy. The thermoplastic elastomer is based on polybutadiene with statistically distributed side groups which form an anisotropic supramolecular structure via hydrogen bonds. Changes in the IR spectra at elevated temperatures are related to the melting of the ordered structure. The uniaxial deformation behaviour is studied by linear dichroism Fourier-transform (FT)-IR spectroscopy. A deformation model is developed which accounts for the major experimental results: while the polybutadiene segments behave as flexible cha…

Cooperative structure formation by combination of covalent and association chain polymers: 4. Designing functional groups for supramolecular structure formation

Abstract A small number of polar functional groups are attached to polybutadiene by a polymer analogous reaction. Depending on their molecular structure, different degrees of supramolecular ordering result from the aggregation of these polar groups. In the case of phenylurazole units, which carry a single site for hydrogen-bond complexation, binary contacts are formed; whereas linear association chain structures are formed in the case of polybutadiene carrying phenylurazole units additionally substituted with a carboxy group in meta or para positions of the phenyl ring. In the latter case, association chains aggregate cooperatively to an ordered supramolecular structure. The different struc…

Thermoanalytical studies on an order-disorder transition resulting from supramolecular organization of hydrogen bond motifs in an unpolar (polymer-) matrix are reported. Functional groups having two potential sites for hydrogen bonding (4-carboxyphenylarazole) are located statistically along the polybutadiene backbone. Multistep hydrogen bond formation leads to the formation of association chains whose lengths can be controlled by addition of monofunctional groups (phenylurazole) like in conventional stepgrowth polymers. The association chain length is estimated from the variation of transition enthalpy and «melting» temperature

Cooperative self-assembling in statistical copolymers: a new approach to high-temperature thermoplastic elastomers

Based on previous work, where it was shown that 4-urazoylbenzoic acid (U4A) groups, which are attached statistically to polybutadiene, form ordered supramolecular arrays in the unpolar polymer matrix, the present work describes the synthesis of a new molecular building block capable of self-assembling in the unpolar polymer matrix. 5-Urazoylisophthalic acid (U35A) groups attached to 1,4-polybutadiene chains cause the formation of a thermoplastic elastomer of improved properties. The clusters of functional groups show an endothermic transition. The melting temperature increases for low levels of modification from 130°C up to 190°C. The mechanical properties (stress–strain and dynamic mechani…