(1-Adamantyl)methyl glycidyl ether: a versatile building block for living polymerization.

(1-Adamantyl)methyl glycidyl ether (AdaGE) is introduced as a versatile monomer for oxyanionic polymerization, enabling controlled incorporation of adamantyl moieties in aliphatic polyethers. Via copolymerization with ethoxyethyl glycidyl ether (EEGE) and subsequent cleavage of the acetal protection groups of EEGE, hydrophilic linear polyglycerols with an adjustable amount of pendant adamantyl moieties are obtained. The adamantyl unit permits control over thermal properties and solubility profile of these polymers (LCST). Additionally, AdaGE is utilized as a termination agent in carbanionic polymerization, affording adamantyl-terminated polymers. Using these structures as macroinitiators for the polymerization of ethylene oxide affords amphiphilic, in-chain adamantyl-functionalized block copolymers.

Functional Group Distribution and Gradient Structure Resulting from the Living Anionic Copolymerization of Styrene and para-But-3-enyl Styrene.

The functional group distribution along the polymer backbone resulting from the living anionic copolymerization of styrene (S) and para-but-3-enyl styrene (pBuS) was investigated in cyclohexane at room temperature. A variety of copolymers with different comonomer contents x(S) = 0-0.84 have been synthesized with molecular weight dispersities Mw/Mn ≤1.12. All polymers have been characterized in detail by 1H NMR spectroscopy, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC). A detailed understanding of the monomer sequence distribution during the copolymerization was achieved by real-time 1H NMR spectroscopy. This technique permits us to determine the changing monomer concentration of each monomer in stock throughout the reaction. Consequently, monomer incorporation and thus the probability of incorporation can be determined at any time of the copolymerization, and a precise determination of the functional group density along the polymer chain is possible. To demonstrate accessibility of the olefin side chains of the copolymer for transformations, quantitative thiol-ene addition of a cysteine derivative has been studied.

Enlarging the Toolbox: Epoxide Termination of Polyferrocenylsilane (PFS) as a Key Step for the Synthesis of Amphiphilic PFS-Polyether Block Copolymers.

Epoxide termination and functionalization of living poly(ferrocenyldimethylsilane) (PFDMS) is introduced by precapping the living PFDMS with a 4/2 molar mixture of 1,1-diphenylethylene and 1,1-dimethylsilacyclobutane acting as a "carbanion pump" system. Subsequent addition of allyl glycidyl ether (AGE) leads to quantitatively functionalized PFDMS-AGE polymers with molecular weights between 1500 and 15 400 g mol-1 and polydispersity indices ≤1.10, carrying one hydroxyl group and an additional allylic double bond. PFDMS-AGE was then applied as a macroinitiator for the living anionic ring-opening polymerization of ethylene oxide (EO) to generate amphiphilic and water-soluble poly(ferrocenyldimethylsilane-b-ethylene oxide) block copolymers with a low polydispersity index. All polymers have been characterized by 1H NMR spectroscopy, DOSY 1H NMR spectroscopy, size exclusion chromatography (SEC), and MALDI-ToF mass spectrometry. In addition, for the characterization of the morphology of the PFDMS-b-PEO block copolymers transmission electron microscopy (TEM) was performed in methanol, confirming the formation of cylindrical micelles with an organometallic core and polyether corona.

Anionic Polymerization of para-(1-Ethoxy ethoxy)styrene: Rapid Access to Poly(p-hydroxystyrene) Copolymer Architectures.

Living anionic polymerization of para-(1-ethoxy ethoxy)styrene (pEES) resulting in molecular weights between 2700 and 69 000 g mol-1 and polydispersity indices ≤1.09 is introduced. PpEES can be used as a precursor for the synthesis of well-defined poly(p-hydroxystyrene) (PHS) architectures, enabling facile and rapid acidic deprotection at room temperature within a few minutes. In addition, a series of block copolymers containing pEES and 2-vinylpyridine (2VP) have been synthesized by anionic block copolymerization, with varied block ratios (X2VP) between 0.13 and 0.83. Characterization by 1H NMR spectroscopy, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC) was carried out, and all polymers have been deprotected, leading to the respective PHS-b-P2VP block copolymers. Furthermore, PHS-b-P2VP has been used as a macroinitiator for the anionic ring-opening polymerization of ethylene oxide (EO) to generate ((PHS-g-PEO51)13-b-P2VP40) graft-block copolymers.

Kinetic control of monomer sequence distribution in living anionic copolymerisation.

Sequence control in synthetic polymers is a subject that is sparsely reported with little research in the field of sequence control in chain growth polymerisation. We report herein preliminary investigations into anionic copolymerisation of diphenylethylene (DPE) and its derivatives with styrene. DPE is a monomer that will only copolymerise and can form alternating copolymers. However, by introducing electron donating or withdrawing substituents onto the phenyl rings of DPE it is possible to prepare new range of (alternating) copolymers and with careful choice of monomer combination and conditions, the kinetically controlled (simultaneous) copolymerisation of three or more monomers results in copolymers with a greater degree of monomer sequence control.