Search results for "Butadiene"

Behaviour of modified and unmodified polybutadienes in the semidilute regime

1997

Abstract The association behaviour of polybutadiene modified with 4-phenyl-l,2,4-triazoline-3,5-dione was studied in semidilute solution through static (SLS) and dynamic light scattering (DLS). The results were compared with the unmodified polybutadiene, whose behavior in semidilute solution was also studied as function of the molecular weight. At higher concentrations a small-angle excess scattering in SLS and a slow mode motion in DLS were observed both for modified and unmodified polybutadienes suggesting the presence of large clusters. Increasing the polymer concentration, the mass fraction of the slow motion increases up to values near 1, indicating a proximity to the gel point. For po…

A model for polybutadiene coatings on porous silica

1993

Non-wetting viscous liquids such as oligobutadiene prefer “active” sites such as pores during the process of physisorption. Thus, polybutadiene (PBD) coatings on porous silica do not result in a homogeneous polymer film but in an inhomogeneous loading where the bulk polymer is mainly sited in the pores of the silica. An increasing polymer loading leads to increasingly filled pores instead of a thicker polymer film. We cannot exclude the possibility that most of the surface is covered at least with a thin polymer film since the chromatographic behaviour is relatively good for polypeptides, which are highly susceptible to the silanol groups of silica.

1993

4-(4-Carboxyphenyl)-3,5-dioxo-1,2,4-triazolidin-1-yl moieties resulting from 4-(3,5-dioxo-1,2,4-triazolin-4-yl)benzoic acid (U4A) randomly attached to 1,4-polybutadiene form supramolecular aggregates which act as effective junction zones in new thermoplastic elastomers. Deuteron nuclear magnetic resonance (2H NMR) spectroscopy was used to investigate the molecular dynamics of the polymer backbone and the junction zones in selectively labelled samples. The spectra show motional heterogeneity along the polymer chain as well as in the supramolecular domains. Polybutadiene segments which are adjacent to these polar clusters are restricted in their mobility, even at temperatures 100 K above the …

Direct Surface Relief Formation in Polymer Films

2013

Due to active development of nanoelectronics, the studies of methods of nanorelief surface formation in different materials, in particular polymers are very important. Organic polymer films in consequence of their dielectric and optical properties have been used as basis of these devices. In this paper, the possibility of UV optical record and electron beam lithography in different type of polymeric films was studied. Mechanisms of molecular structure changes: photoisomerization, destruction, cross-linking and oxidation have been discussed. The results of UV illumination of polyurethanes, polyacrylates, and some block-copolymers were described. The element analysis of polybutadiene block co…

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

1994

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…

Competitive Adsorption of Functionalized Polymers

1996

The adsorption and desorption of functionalized polystyrene-block-polybutadiene diblock copolymers from dilute solutions in toluene onto silicon wafers are investigated by means of null ellipsometry. The short polybutadiene block is functionalized by a reaction with 4-(3,5-dioxo-1,2,4-triazolidin-4-yl)benzoic acid. On the average there are six functional groups per chain. The polystyrene block does not adsorb on the surface. The adsorption depends on the length of the polystyrene block, and chains with short polystyrene blocks yield higher surface coverage than larger ones. When short and long chains are put together, the short chains displace the long ones in equilibrium conditions nearly …

1995

Supramolecular structures based on 4-(3,5-dioxo-1,2,4-triazolidin-4-yl) benzoic acid (U4A) units act as effective junction zones in functionalized polybutadienes, resulting in the formation of thermoplastic elastomers. The dynamics on a molecular scale of the phenyl rings have been probed by 2H-NMR. In the polymeric system, there are three spatially separated environments, which are reflected in the mobility of the polar units. Phenyl rings which are incorporated in the structures are either rigid or undergo 180° phenyl flips. The small fraction of free functional groups move isotropically and their mobility is coupled to the dynamics of the polybutadiene matrix. In two model compounds, whe…

1991

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

Dilute solution properties of polybutadiene modified by 4-phenyl-1,2,4-triazoline-3,5-dione

1996

The dilute solution properties of 4-phenyl-1,2,4-triazoline-3,5-dione-modified polybutadienes were studied in tetrahydrofuran by static and dynamic light scattering and compared with those from unmodified polybutadiene chains. For the unmodified polymer, the scaling laws were established and the coil interpenetration parameter k f0 was determined in the thermodynamically good solvent tetrahydrofuran ; the chains exhibited common flexible chain behavior. For the modified polybutadiene, the results indicate at infinite dilution a weak extent of intermolecular crosslinking via the urazole groups, coupled with a very high extent of intramolecular ring formation. In order to evaluate the fractio…

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

1991

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…