The effect of chain architecture on the morphological and tensile properties of series of multigraft copolymers, with regularly spaced tri-, tetra-, and hexafunctional junction points, was investigated using transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and tensile testing. The materials were synthesized by coupling difunctional polyisoprene (PI) spacers and living polystyrene (PS) branches, made by anionic polymerization, with chlorosilanes of different functionalities. Since the coupling process is a step-growth polymerization, yielding polydisperse products, fractionation was utilized to separate each material into three fractions (high, middle, and low molecular weight), each of low polydispersity. All three fractions have the same chain architecture on a per junction point basis but differ in the number of junction point units per molecule. By applying the constituting block copolymer concept, the physical behavior of these molecules was compared with current theories. It was found that morphological behavior of these graft copolymers can be predicted using theoretical approaches and is independent on the number of junction points. The number of the junction points, however, greatly influences the long-range order of microphase separation. Additionally, two new parameters for adjusting mechanical properties of multigraft copolymers were found in this investigation: (1) functionality of the graft copolymerstri-, tetra-, or hexafunctionalsand (2) number of junction points per molecule. An increase in functionality causes a change in morphology, resulting in a high level of tensile strength for tetrafunctional (cylindrical) and hexafunctional (lamellae) multigraft copolymers, leading to about the twice the strength of the spherical trifunctional multigrafts of similar overall composition. Tetrafunctional multigraft copolymers show a surprisingly high strain at break, far exceeding that of commercial block copolymer thermoplastic elastomers (TPEs). Strain at break and tensile strength increase linearly with the number of junction points per molecule. Hysteresis experiments at about 300-900% deformation demonstrate that multifunctional multigraft copolymers have improved high elasticity as compared to commercial TPEs like Kraton or Styroflex.

Summary: PS-PI multigraft copolymers with tri-tetra-and hexafunctional polystyrene branch points have been studied to investigate the influence of molecular architecture on morphological and tensile properties and to find novel material concepts. It was found that the morphological behaviour of these grafted copolymers can be predicted using theoretical approaches. The number of branch points, however, greatly influences the long-range order of microphase separation. Additionally, two new parameters for adjusting mechanical properties of multigraft copolymers are found in our investigations: 1) functionality of the graft copolymer: tri-, tetra-or hexafunctional and 2) number of branch points per molecule. Tetrafunctional multigraft copolymers show surprising high strain at break values up to 1550 %. With increasing number of branch points strain at break and tensile strength increase, where a linear dependence of mechanical properties on the number of branch points is obvious. Excellent elasticity of tetra and hexafunctional multigraft copolymers at high deformation was proved in hysteresis experiments.

The phenomenon of contact angle hysteresis was studied on smooth films of polyimide, a polymer type used in the microelectronic industry, by dynamic cycling contact angle measurements based on axisymmetric drop shape analysis-profile in combination with variable angle spectroscopic ellipsometry (VASE). It was found that both advancing and receding contact angles became smaller with increasing the number of cycles and are, therefore, not a property of the dry solid alone. The changes of the wetting behavior during these dynamic cycling contact angle measurements are attributed mainly to swelling and/or liquid retention. To reveal the water-induced changes of the polymer film, the polyimide surface was studied before and after the contact with a water droplet by VASE. Both the experimental ellipsometric spectrum for Delta and that for Psi as well as the corresponding simulations show characteristic shifts due to the contact with water. The so-called effective medium approximation was applied to recover information about the thickness and effective optical constants of the polymer layer from the ellipsometrically measured values of Delta and Psi. On the basis of these results, the swelling and retention behavior of the polyimide films in contact with water droplets were discussed.