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Optical microscopy, neutron reflectivity, and small angle neutron scattering studies were used to investigate the structure of thin films of symmetric diblock copolymers of P(dS-b-MMA) as the interactions between the copolymer and the substrate were changed in a systematic manner. In cases where there was a strong preferential segregation of one of the components to the substrate, the lamellar microdomains were oriented parallel to the film surface. However, on a nearly neutral substrate, a mixed morphology was found where the lamellae adjacent to the free surface are oriented parallel to the plane of the film, while the lamellae adjacent to the substrate are oriented normal to the plane of the film.

The efficiency of the macromonomer (MM) synthetic strategy for the creation of nonlinear complex macromolecular architectures (miktoarm stars, α,ω‐branched polymers, random/exact comb and graft copolymers, dendritic polymers, molecular brushes) is reviewed. In addition, the solution/bulk properties and the potential applications of polymacromonomers (PMM), as well as new synthetic ideas are presented. The synthesis of macromonomers and living polymacromonomers in situ leads to many novel linear and nonlinear structures, as for example PMM‐b‐PS‐b‐PMM, (PS)2PMM. The use of multichlorosilylstyrenes as monomer/linking agents opens new ways for structures with multichain macromonomeric building blocks.The use of multichlorosilylstyrenes as monomer/linking agents opens new ways for structures having multichain macromonomeric building blocks.magnified imageThe use of multichlorosilylstyrenes as monomer/linking agents opens new ways for structures having multichain macromonomeric building blocks.

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