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This work develops the Polyolefin Active‐Ester Exchange (PACE) process to afford well‐defined polyolefin–polyvinyl block copolymers. α‐Diimine Pd^II‐catalyzed olefin polymerizations were investigated through in‐depth kinetic studies in comparison to an analog to establish the critical design that facilitates catalyst activation. Simple transformations lead to a diversity of functional groups forming polyolefin macroinitiators or macro‐mediators for various subsequent controlled polymerization techniques. Preparation of block copolymers with different architectures, molecular weights, and compositions was demonstrated with ring‐opening polymerization (ROP), nitroxide‐mediated polymerization (NMP), and photoiniferter reversible addition–fragmentation chain transfer (PI‐RAFT). The significant difference in the properties of polyolefin–polyacrylamide block copolymers was harnessed to carry out polymerization‐induced self‐assembly (PISA) and study the nanostructure behaviors.

 

The manipulation of covalent polymer networks in the bulk or in the nanoscale seeks to broaden material property variations from an existing parent structure with the possibility to make fundamental changes in nanoparticle compositions which is otherwise difficult to accomplish through bottom up approaches. In this contribution, a parent nanoparticle network prepared by an intermolecular chain cross-linking process containing trithiocarbonate photoactive cross-linking groups has been investigated in its ability to form various novel nanonetworks through a photogrowth expansion process using 10-phenylphenothiazine (PTH) as a photoredox catayst under violet light irradiation, incorporating statistical copolymers and block copolymers into the existing nanonetwork. Hydrophilic and hydrophobic homo-and statistical copolymer incorporation leads to custom designed, tailored nanonetworks and stimuli-responsive behavior. For example, particles expanded by incorporation of PNIPAAM collapse after thermoresponsive behavior above 32 °C and shrink to approximately half of their original size. Furthermore, ABA triblocks and ABABA pentablocks of MA, TFEA, NIPAAM and t BA are integrated with a high degree of control into a parent particle. In this work, we have demonstrated the feasibility of parent nanonetwork structures to expand their network architecture reaching up to the microscale range to give soluble soft matter networks, containing controlled compositions of homopolymers, statistical copolymers, or pentablock structures. The taught concept gives opportunities to further design and alter the network topology in confined structures to tailor properties and function.