Kyushu University · Materials Science
Professor Shingo Kobayashi's research lab specializes in the design, synthesis, and polymerization of functional monomers, with a strong focus on precision polymer synthesis using advanced catalytic methods such as ring-opening metathesis polymerization (ROMP) and anionic polymerization. The lab develops well-defined polymers with high regio- and stereoregularity, particularly for applications in advanced materials and biomedical engineering. Key research directions include the creation of model polyolefins (e.g., precision LLDPEs), non-thrombogenic coatings, and well-defined block copolymers with tailored thermal and mechanical properties.
Figures are computed from collected data and may differ slightly.
3-Substituted cis-cyclooctenes (3RCOEs, R = methyl, ethyl, hexyl, and phenyl) were synthesized and polymerized, and the polymers therefrom were hydrogenated to prepare model linear low density polyethylene (LLDPE) samples. The ring-opening metathesis polymerization (ROMP) of the 3RCOEs using Grubbs' catalyst proceeded in a regio- and stereoselective manner to afford polyoctenamers [poly(3RCOE)] exhibiting remarkably high head-to-tail regioregularity and high trans-stereoregularity. The overall s
The diene 3-methylenecyclopentene (2) was synthesized from the naturally occurring monoterpene myrcene (1) by ring-closing metathesis using Grubbs second generation catalyst. Radical, anionic, and cationic polymerizations of 2 were investigated. The anionic polymerization of 2 with sec-butyllithium (s-BuLi) in cyclohexane gave poly-2 in quantitative yield, with a narrow molecular weight distribution and predictable molecular weight based on the molar ratio of 2 and s-BuLi. Radical polymerization
A series of polyacrylates with different n-alkyl side chain lengths (1 to 6, and 12 carbons) and a ω-methoxy terminal group (poly(ω-methoxyalkyl acrylate): PMCxA) were prepared to study their nonthrombogenicity using human platelet adhesion, micro bicinchoninic acid (micro BCA) protein assay, and enzyme-linked immunosorbent assay (ELISA) tests. In all cases, human platelet adhesion was suppressed on the PMCxA-coated substrates, and the number of human platelets adhered to the PMC3A (poly(3-metho
Allyl-substituted cyclooctenes with ether side-chains [methoxy, methoxy-terminated oligo(ethylene glycol)s, and tetrahydrofurfuryloxy group] were prepared as monomers and polymerized by ring-opening metathesis polymerization (ROMP) using Grubbs second-generation catalyst. In all cases, the ROMP of allyl-substituted monomers proceeded in a regio- and stereoselective manner to afford polymers with remarkably high head-to-tail regioregularity with high trans-stereoregularity. The regio- and stereor
Anionic polymerizations of new styrene derivatives, 4-(1-adamantyl)styrene (1) and 3-(4-vinylphenyl)-1,1‘-biadamantane (2), were carried out with sec-butyllithium, cumylpotassium, and lithium- or potassium naphthalenide in THF at −78 °C for 3−4 h. The polymerizations of 1 and 2 quantitatively proceeded to afford the polymers possessing the predicted molecular weights based on the molar ratios between monomers and initiators and the narrow molecular weight distributions (Mw/Mn = 1.03−1.13). The s
The anionic polymerization of 4-(1-adamantyl)styrene (AdS) was carried out with s-BuLi in cyclohexane at 50 °C. The resulting poly(AdS) had predicted molecular weights, narrow molecular weight distributions, and high glass transition temperature (Tg) around 232 °C. A series of well-defined ABA type triblock copolymers, where B midblock stood for 1,4-polyisoprene and A end blocks for poly(AdS) (A), poly(AdS-ran-styrene) (AS), and polystyrene (S), were successfully synthesized by the sequential co
A series of variants of antithrombogenic poly(2-methoxyethyl acrylate) with controlled side-chain spacing were prepared via regio-selective ring-opening metathesis polymerization. In general, understanding the hydration state and its dynamics at the polymer/water interface is important for the development of biomaterials. To determine how the chemical design of polymeric materials can control the hydration state, we systematically investigated the effect of side-chain spacing not only on the hyd
Anionic polymerization of 2-(1-adamantyl)-1,3-butadiene (1) was carried out either with s-BuLi in cyclohexane at 40 °C or with potassium naphthalenide in THF at −78 °C. The polymerizations of 1 quantitatively proceeded to afford the polymers possessing the predicted molecular weights based on the molar ratios between monomers and initiators and the narrow molecular weight distributions. The microstructure of the resulting poly(1) was affected by the initiators and the solvents. The contents of 1
Functionalized linear low-density polyethylene (LLDPE) samples containing basic functional groups (cyano, primary amino-, or secondary amino-) were synthesized through the ring-opening metathesis terpolymerization of cyclooctene (COE), 5-n-hexyl-1-cyclooctene (HexCOE), and a functionalized cyclooctene (FCOE), followed by hydrogenation of the polymer backbone and deprotection of any requisite protecting group. Homopolymerization of the cyano- and tert-butoxycarbonyl (tBOC) protected amino-functio
Primary and secondary amino-functionalized polyethylenes were synthesized from commercially available maleic anhydride-modified polyethylene by reaction with mono-tert-butoxycarbonyl-protected diamines, N-(tert-butoxycarbonyl)-1,6-diaminohexane (tBocHMDA), and N-(tert-butoxycarbonyl)-N-ethyl-1,6-diaminohexane (tBocEtHMDA) followed by deprotection with trifluoroacetic acid. The structures of amino-functionalized polyethylenes were characterized by NMR and IR spectroscopies, and the data compared
Polymeric materials modified with tertiary amino groups exhibit attractive properties for use in aqueous environments. Ring-opening metathesis polymerization (ROMP) is one of the versatile tools to synthesize functionalized polymers; however, the ROMP of monocyclic cycloolefins with tertiary amino groups is challenging because of the polymerization inhibition by the nitrogen atom coordination to the catalyst center. In this study, the ROMP of tertiary amino-functionalized monocyclic cycloolefins
Model hexyl-branched linear low density polyethylene (C8-LLDPE) samples were synthesized by the ring-opening metathesis copolymerization (ROMP) of the 5-hexylcyclooct-1-ene (1) and cyclooctadiene (COD), followed by catalytic hydrogenation. The ROMP of 1 and copolymerization of 1 and COD using the Grubbs second generation catalyst (G2) afford polymers with the number of hexyl branches based on the feed composition. The resulting hexyl-branched polymers, poly(1) and poly(1-stat-COD), were complete
Abstract Anionic polymerization of a novel α‐methylstyrene derivative para ‐substituted with a bulky and rigid adamantyl group, 4‐(1‐adamantyl)‐α‐methylstyrene ( AdαMS ) is carried out with sec ‐butyllithium ( sec ‐BuLi) in tetrahydrofuran (THF) at −78 °C. The polymerizations of AdαMS quantitatively proceed to afford the polymers possessing controlled molecular weights and narrow molecular weight distributions ( M w / M n = 1.03–1.16). The propagating carbanion of poly( AdαMS ) is stable and und
Modifying the side chain of poly(meth)acrylate with moieties originating from biocompatible polymers can be an effective method for developing novel blood-compatible polymers. Inspired by biocompatible poly(2-methyl-2-oxazoline) (PMeOx) and poly(2-ethyl-2-oxazoline) (PEtOx), four water-soluble poly(tertiary amide acylate) analogues bearing a pendant tertiary amide were synthesized. The results of hemolysis and cell viability tests showed that all the poly(tertiary amide acylate) analogues were c
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