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.

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Tensile properties and morphology of tetrafunctional multigraft copolymers are investigated dependent on PS volume fraction and number of branch points. It is found that tetrafunctional multigraft copolymers with 22 vol % PS and seven branch points show a surprising high strain at break of about 2100%, about double that of commercial thermoplastic elastomers (TPE's) such as Kraton. With increasing number of branch points, strain at break and tensile strength increases, and strain at break is about 2300% for a sample with 10 branch points. Investigation of morphology using transmission electron microscopy indicates that a sample with 22 vol % PS has a wormlike microphase-separated structure with much lower long range order than other TPE's s such as Kraton. The multigraft copolymers of this study have two PS arms at each branch point. This, together with a large number of branch points per molecule, allows the elastic PI backbone to couple into a large number of reinforcing PS domains, resulting in huge elasticity, combined with a high tensile strength. Two parameters for adjusting mechanical properties of multigraft copolymers are found in our investigations: (1) functionality of the graft copolymer, tri-or tetrafunctional, and (2) number of branch points per molecule.

The phase behavior of poly(styrene-b-butyl methacrylate), PS-b-PBMA, diblock copolymers was investigated by small-angle neutron scattering (SANS), neutron reflectometry (NR), and rheology. For a symmetrical P(dS-b-nBMA) diblock copolymer a lower critical order transition (LCOT) at 155°C was found by SANS and rheology. Furthermore, the temperature-dependent interaction parameter was determined in the temperature regime between 110 and 145°C from fits to the scattering curves in the disordered region. The interaction parameter increases with increasing temperature and shows a weak temperature dependence. The LCOT behavior thus is expected to be a large entropic contribution to . The interfacial width observed by NR is relatively large compared to other diblock copolymers. Different block copolymers were investigated with respect to the influence of miscibility on tensile properties. While poly(styrene-b-butyl methacrylate) diblock copolymers show significant synergistic effects on tensile properties, for poly(methyl methacrylate-b-butyl methacrylate) diblock copolymers no significant synergistic effects on tensile properties were observed due to the increased interaction parameter and the smaller interfacial width as compared to the case of PS-b-PBMA diblock copolymers.

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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.

Lamellae-forming styrene/butadiene star block copolymers are studied to investigate the influence of morphology on micromechanical deformation mechanisms and mechanical properties by using transmission electron microscopy and tensile testing. A large homogeneous plastic deformation of polystyrene (PS) lamellae is found in styrene/butadiene star block copolymers on the basis of the new mechanism called thin-layer yielding. This mechanism depends strongly on the thickness of the PS lamellae. At a critical thickness of PS lamellae of about 20 nm, a transition from thin-layer yielding mechanism to a crazelike deformation was observed. These new deformation zones are similar to crazes with respect to their propagation perpendicular to direction of external stress and similar to shear bands with respect to an internal shear deformation component of the lamellae in the deformation zones. As a result of our investigations, the mechanical properties of star block copolymers can be understood in correlation with morphology and micromechanical deformation mechanisms.

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