Branched methacrylate copolymers from multifunctional monomers: chemical composition and physical architecture distributions

Costello, P.A; Martin, Ian K.; Slark, Andrew T.; Sherrington, David C.; Titterton, A

doi:10.1016/s0032-3861(01)00581-x

Cited by 152 publications

(179 citation statements)

References 16 publications

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“…The introduction of a chain transfer agent in this polymerization allowed the synthesis of various soluble highly branched polymers, thanks to the increase of primary chain concentration. This strategy, coined 'Strathclyde synthesis' 14 , was then enriched, thanks to living/ controlled radical polymerization mechanisms. The so-called controlled radical crosslinking copolymerization methodology has enabled the synthesis of various branched polymers with very well-defined primary chain lengths [15][16][17][18][19][20][21][22][23] .…”

mentioning

confidence: 99%

Controlled multi-vinyl monomer homopolymerization through vinyl oligomer combination as a universal approach to hyperbranched architectures

et al. 2013

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The three-dimensional structures of hyperbranched materials have made them attractive in many important applications. However, the preparation of hyperbranched materials remains challenging. The hyperbranched materials from addition polymerization have gained attention, but are still confined to only a low level of branching and often low yield. Moreover, the complication of synthesis only allows a few specialized monomers and inimers to be used. Here we report a 'Vinyl Oligomer Combination' strategy; a versatile approach that overcomes these difficulties and allows facile synthesis of highly branched polymeric materials from readily available multi-vinyl monomers, which have long been considered as formidable starting materials in addition polymerization. We report the alteration of the growth manner of polymerization by controlling the kinetic chain length, together with the manipulation of chain growth conditions, to achieve veritable hyperbranched materials, which possess nearly 70% branch ratios as well as numerous vinyl functional groups.

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confidence: 99%

Controlled multi-vinyl monomer homopolymerization through vinyl oligomer combination as a universal approach to hyperbranched architectures

et al. 2013

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“…The decrease in the polymer molecular weight can be enhanced by the presence of a retarder or a chain transfer reagent. 9,15,16 On the other hand, allyl monomers usually give oligomers only in a low yield by usual radical polymerzation because of degradative chain transfer reaction to the monomers. 17,18 However, allyl acetate (AAc) as an allyl monomer shows a considerably high reactivity in the radical copolymerization with vinyl acetate (VAc) as a non-conjugative monomer.…”

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confidence: 99%

Hyperbranched Polymer through Initiator-Fragment Incorporation Radical Copolymerization of Divinyl Adipate with Allyl Acetate: Synthesis, Characterization, Dye Solubilization, Metal-Nanoparticle Stabilization, and Porous Film Formation

Sato

Nomura

Hirano

et al. 2006

Polym J

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ABSTRACT:The copolymerization of divinyl adipate (DVA) as an effective cross-linker with allyl acetate (AAc) as a degradative chain transfer reagent was carried out at 70 and 80 C in benzene using dimethyl 2,2 0 -azobisisobutyrate (MAIB) of high concentrations as initiator. When the MAIB concentration as high as 0.60 mol/L was used, the copolymerization of DVA (0.20 mol/L) and AAc (0.50 mol/L) proceeded homogeneously without any gelation to give soluble copolymers in a yield of about 30% based on the total weight of DVA, AAc, and MAIB. The copolymer formed in the copolymerization at 80C for 6 h consisted of the DVA units with (3 mol %) and without (24 mol %) double bond, the AAc unit (35 mol %), and the methoxycarbonylpropyl group (38 mol %) from MAIB. Such a large fraction of the incorporated initiator-fragment as terminal group indicates that the copolymer has a hyperbranched structure. The copolymer showed an upper critical solution temperature (38 C on cooling) in a tetrahydrofuran (THF)-water [2:1 (v/v)] mixture, and also exhibited potentials in solubilization of Rhodamine 6G as a dye probe and stabilization of metal nanoparticles. A porous film was obtained simply by casting a copolymer solution in THF.

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“…Figure 7 shows the composition of the polymers formed at different times in the polymerization at 70 (runs 17-22 in Table 1) and 80 8C (runs 6,8,[12][13][14][15], in which the concentrations of 1 and 2 were 0.10 and 0.50 mol Á L À1 .…”

Section: Characterization Of the Resulting Polymermentioning

confidence: 99%

“…[8][9][10] We have successfully applied IFIRP to the synthesis of hyperbranched polymers based on divinyl monomers, such as divinylbenzene, ethylene glycol dimethacrylate (1, see below), and divinyl adipate. [11][12][13][14][15] Until now, the hyperbranched polymers have been obtained by IFIRPs of divinyl monomers in the presence of a monovinyl monomer or retarder or both.…”

Section: Introductionmentioning

confidence: 99%

Formation of Soluble Hyperbranched Polymer Nanoparticles by Initiator‐Fragment Incorporation Radical Polymerization of Ethylene Glycol Dimethacrylate

Hirano

Ihara

Miyagi

et al. 2005

Macro Chemistry & Physics

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Summary: Ethylene glycol dimethacrylate (1) was polymerized at 70 and 80 °C in benzene using high concentrations of the initiator, dimethyl 2,2′‐azobisisobutyrate (2). When the concentrations of 1 and 2 were 0.10 and 0.50 mol · L−1, respectively, the polymerization proceeded homogeneously without any gelation to yield a soluble polymer. The polymerization system involved ESR‐detectable polymer radicals in high concentration (3.1 × 10−6–7.5 × 10−6 mol · L−1 at 70 °C). The polymer formed at 80 °C after 4 h consisted of units of 1 with (4 mol‐%) and without (38 mol‐%) a double bond and a methoxycarbonylpropyl group (58 mol‐%) as the fragment of 2. Thus, the initiator‐fragment incorporation radical polymerization proceeds in the present polymerization to yield a hyperbranched polymer. The polymer showed an upper critical solution temperature (31 °C on cooling and 32 °C on heating) in an acetone/water mixture (4:1 v/v). The intrinsic viscosity of the polymer was very low (0.047 dL · g−1) at 30 °C in benzene despite its considerably high molecular weight ($\overline M _{\rm w}$ = 5.7 × l05 by MALLS). TEM confirmed that the individual polymer molecules were nanoparticles with diameters of 5–15 nm. The polymer was able to solubilize for the dye probe, Rhodamine 6G, by encapsulation in its hyperbranched structure.Hyperbranched structure of the resulting polymer.magnified imageHyperbranched structure of the resulting polymer.

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Branched methacrylate copolymers from multifunctional monomers: chemical composition and physical architecture distributions

Cited by 152 publications

References 16 publications

Controlled multi-vinyl monomer homopolymerization through vinyl oligomer combination as a universal approach to hyperbranched architectures

Controlled multi-vinyl monomer homopolymerization through vinyl oligomer combination as a universal approach to hyperbranched architectures

Hyperbranched Polymer through Initiator-Fragment Incorporation Radical Copolymerization of Divinyl Adipate with Allyl Acetate: Synthesis, Characterization, Dye Solubilization, Metal-Nanoparticle Stabilization, and Porous Film Formation

Formation of Soluble Hyperbranched Polymer Nanoparticles by Initiator‐Fragment Incorporation Radical Polymerization of Ethylene Glycol Dimethacrylate

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