Synthesis of polyethylene and polypropylene containing fluorene units in the side chain

Abstract

Copolymerizations of ethylene or propylene and allyl monomers containing 9‐fluorenyl group, diallyl‐di‐9‐fluorenylsilane (DAFS), 9,9‐diallylfluorene (DAF), and 9‐allylfluorene (AF), were investigated with various zirconocene catalysts using methylaluminoxane as a cocatalyst. The bridged zirconocene catalysts, especially a syndioselective catalyst, showed a higher reactivity for all the comonomers than the nonbridged catalysts. DAFS was mainly incorporated into the polymer chain via cyclization insertion, whereas DAF was copolymerized via both 1,2‐ and cyclization insertions. Cyclization selectivity, ratio of cyclized insertion unit, of DAF in the copolymerization with propylene was higher than that in the copolymerization with ethylene. Copolymerization with AF yielded low‐molecular weight copolymer because of frequent chain transfer reaction. Optical properties of the propylene based‐copolymers were investigated by UV‐vis and photoluminescence spectroscopy, and absorption‐ and emission‐derived from fluorenyl groups were detected in the copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3542–3552, 2010

Synthesis and photophysical properties of polyethylene containing pyrenyl units in the side chain

“…Catalyst 2 showed higher incorporation of APyS than Catalyst 1 . The same results of catalyst nature were observed in the copolymerization of ethylene and α,ω‐nonconjugated dienes or DAFS 6, 10. The wide accommodation of Catalyst 2 should allow high reactivity of the APyS insertion.…”

“…The cyclization selectivity decreased with increasing of the APyS content in the copolymer. We previously reported similar tendency in the copolymerization with DAFS,6 that is, Catalyst 2 showed lower [C] than Catalyst 1 due to the steric hindrance of fluorenyl ligand of Catalyst 2 in the cyclization insertion of DAFS unit. The low cyclization selectivity of APyS units in the copolymers obtained with Catalyst 2 should be derived from the same reason.…”

“…The polymers showed efficient fluorescence derived from the fluorenyl units 2, 3, 5. We reported synthesis of olefin‐based copolymers having fluorescent group by means of the copolymerization of ethylene or propylene with allyl monomers containing 9‐fluorenyl group, diallyl‐di‐9‐fluorenylsilane (DAFS), 9,9‐diallylfluorene (DAF), and 9‐allylfluorene (AF) with zirconocene catalysts 6. The copolymerization yielded the corresponding copolymer.…”

Perfectly Regioregular Electroactive Polyolefins: Impact of Inter-Chromophore Distance on PLED EQE

“…To determine the effects of chromophore separation on device parameters, we have prepared a set of perfectly regioregular electroactive polyolefins with carefully controlled average chromophore–chromophore distances. As shown in Figure A, regioregular electroactive polyolefins comprise a class of materials in which the active pendant group occurs at exactly defined backbone run length intervals (spacer lengths). , These regioregular materials are analogous to previously reported vinyl type or regiorandom polymers containing pendant electroactive moieties (Figure B). − Similar to main chain π-functional materials (Figure C), − pendant π-functional polymers offer the opportunity for inclusion of various electroactive units, which may serve their purposes cooperatively (e.g., various chromophores for white emission, emissive units and charge transporters, etc. ) ,, and thus afford an interesting and relatively new avenue for exploration into optoelectronic materials, as compared to conjugated polymers (Figure D).…”

Fluorene-functionalized aliphatic polycarbonates: design, synthesis and aqueous self-assembly of amphiphilic block copolymers

“…Biocompatibility, degradability, solubility and stability in aqueous conditions are some of the key requirements to consider when designing materials for biomedical applications. Though to a large extent numerous block copolymers and homopolymers containing electro-active side chains [12][13][14][15][16][17][18][19][20][21] and main-chains 2,6,[22][23][24][25][26][27] have been reported for biomedical applications, there are only limited synthetic reports describing the installation of these electro-active moieties into a degradable platform. 6,[22][23][24][25] To date and to the best of our knowledge, there are no reports describing the synthesis of degradable materials containing electro-active groups via a controlled polymerization strategy whilst exerting precise compositional control.…”