Acrylic thermoplastic elastomers and comb‐shaped poly(methyl methacrylate) via the macromonomer technique

Radke, Wolfgang; Roos, Sebastian; Stein, Helga M.; Müller, Axel H. E.

doi:10.1002/masy.19961010105

Cited by 25 publications

(21 citation statements)

References 19 publications

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“…3,4 Obviously, a control of backbone chain length is not possible for this mechanism. Various strategies have been developed recently for a controlled radical polymerization.…”

Section: Introductionmentioning

confidence: 99%

Copolymerization of n-Butyl Acrylate with Methyl Methacrylate and PMMA Macromonomers: Comparison of Reactivity Ratios in Conventional and Atom Transfer Radical Copolymerization

1999

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The reactivity ratios of n-butyl acrylate (nBuA) with methyl methacrylate (MMA) and ω-methacryloyl-PMMA macromonomers (MM) in conventional and atom transfer radical copolymerization (ATRP) have been determined. For the copolymerization of nBuA with MMA, good agreement of the ratios is observed between conventional and controlled radical copolymerization, indicating that chemoselectivities in both processes are similar. The relative reactivity of the MM (1/r nBuA) in conventional copolymerization is significantly lower than that of MMA. It depends on the concentration of the comonomers but is not significantly influenced by the length of the MM. At high concentrations the relative reactivity decreases due to diffusion control of the MM addition. In ATRP the relative reactivity of the MM is much nearer to the value of MMA. This is explained by the different time scales of monomer addition in both processes: whereas the frequency for monomer addition is in the range of milliseconds for conventional polymerizations, it is in the range of seconds in ATRP; thus, diffusion control is less important here. This gives the opportunity to copolymerize at much higher concentrations than in conventional radical copolymerization. In addition, the graft copolymers obtained by ATRP have lower polydispersities.

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“…3,4 Obviously, a control of backbone chain length is not possible for this mechanism. Various strategies have been developed recently for a controlled radical polymerization.…”

Section: Introductionmentioning

confidence: 99%

Copolymerization of n-Butyl Acrylate with Methyl Methacrylate and PMMA Macromonomers: Comparison of Reactivity Ratios in Conventional and Atom Transfer Radical Copolymerization

1999

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“…2 ' 3 Obviously, a control of backbone chain length is not possible for this mechanism. Thus, we have used ATRP to synthesize the graft copolymers.…”

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confidence: 99%

Copolymerization of n-Butyl Acrylate with Methyl Methacrylate and PMMA Macromonomers by Conventional and Atom Transfer Radical Copolymerization

Roos

Müller

Matyjaszewski

2000

ACS Symposium Series

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The reactivity ratios of n-butyl acrylate (nBuA) with methyl methacrylate (MMA) and ω-methacryloyl-PMMA macromonomers (MM) in conventional and atom transfer radical copolymerization (ATRP) have been determined. For the copolymerization of nBuA with MMA, good agreement of the ratios is observed between conventional and controlled radical copolymerization, indicating that chemoselectivities in both processes are similar. The relative reactivity of the MM (1/r nBuA ) in conventional copolymerization is significantly lower than of MMA. It depends on the concentration of the comonomers but is not significantly influenced by the length of the MM. At high concentrations the relative reactivity decreases due to diffusion control of the MM addition. In ATRP the relative reactivity of the MM is much closer to the value of MMA. This is explained by the different time scales of monomer addition in both processes: whereas the frequency for monomer addition is in the range of milliseconds for conventional polymerizations, it is in the range of seconds or minutes in ATRP, thus diffusion control is less important here. This gives the opportunity to copolymerize at much higher concentrations than in conventional radical copolymerization. In addition, two-dimensional chromatography shows that the graft copolymers obtained by ATRP are much more homogeneous in terms of MWD and number of side-chains.Graft copolymers offer all properties of block copolymers but are usually easier to synthesize. Moreover, the branched structure leads to decreased melt Corresponding author.

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“…The brushes are usually prepared by homopolymerization of the macromonomers. A number of brush polymers consisting of flexible polymer side chains have been prepared, including polystyrene (PSt), [5][6][7][8][9][10][11][12][13] poly(methyl methacrylate), 14 poly(ethylene oxide), [15][16][17] poly(N-isopropyl acrylamide), 18 poly(n-butyl acrylate), 19 core-shell brushes consisting of block copolymers of styrene with 2-vinylpyridine, 20 and "-caprolactone with n-butyl acrylate. 21 One interesting and important finding in conformational properties of the brushes with regular comb-branching structure is that the main chain remarkably stiffens in a solution, despite being composed of flexible chains and that the stiffness parameter ( À1 ) in the wormlike cylinder model increases with side chain length and solvent power.…”

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Characterization of Rodlike Poly(n-hexyl isocyanate) Macromonomers and Their Polymacromonomers by Light Scattering, SAXS, Intrinsic Viscosity, and Scanning Force Microscopy

Kikuchi

Mihara

Jinbo

et al. 2007

Polym J

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ABSTRACT:SEC-MALS, small-angle X-ray scattering (SAXS), and viscosity measurements were made on tetrahydrofuran (THF) and n-hexane of a series of 4-vinylbenzyl and methacrylate ended poly(n-hexyl isocyanate) (PHIC) macromonomers (VB-HIC-n and MA-HIC-n, where n is a degree of polymerization of HIC and in a range from 21 to 192), together with higher molecular weight PHIC chains than the macromonomers. The molecular weight dependence of z-average mean-square radius of gyration hRg 2 i z and intrinsic viscosity [] of the macromonomers and PHIC chains in THF at 25 C were quantitatively described by the wormlike chain model with the stiffness parameter ð À1 Þ ¼ 63 nm, the molecular weight per unit contour length ðM L Þ ¼ 725 nm À1 , and the hydrodynamic diameter ðd B Þ ¼ 1:6 nm. The SAXS scattering profile of VB-HIC-57 in n-hexane at 25 C was also perfectly described in terms of the straight cylinder model. The results imply that the macromonomers may be regarded as a rigid rod molecule in THF and n-hexane. Cylindrical brushes consisting of polystyrene as a main chain and PHIC chains as a side chain were prepared by homopolymerizations of VB-HIC-46 and their dimensional properties were investigated in THF at 25 C by SAXS and SEC-MALS measurements. The molecular weight dependence of hRg 2 i z of the brushes was quantitatively explained by the wormlike cylinder model with the parameters of À1 ¼ 48 nm, M L ¼ 2:40 Â 10 4 nm À1 , the cross-sectional radius of gyration of the cylinder hRc 2 i o 1=2 ¼ 4:66 nm, and the end effect ( ¼ 16:7 nm) arising from side chains near the mainchain ends. It was concluded, therefore, that the main chain stiffness of the brush remarkably increases by the presence of densely located rodlike side chains. Direct observation of single brush of the poly(VB-HIC-46) deposited on a mica was made by scanning force microscopy (SFM) to reveal the cylindrical brushes consisting of rodlike side chains with ca. 15 nm in a thickness.

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Acrylic thermoplastic elastomers and comb‐shaped poly(methyl methacrylate) via the macromonomer technique

Cited by 25 publications

References 19 publications

Copolymerization of n-Butyl Acrylate with Methyl Methacrylate and PMMA Macromonomers: Comparison of Reactivity Ratios in Conventional and Atom Transfer Radical Copolymerization

Copolymerization of n-Butyl Acrylate with Methyl Methacrylate and PMMA Macromonomers: Comparison of Reactivity Ratios in Conventional and Atom Transfer Radical Copolymerization

Copolymerization of n-Butyl Acrylate with Methyl Methacrylate and PMMA Macromonomers by Conventional and Atom Transfer Radical Copolymerization

Characterization of Rodlike Poly(n-hexyl isocyanate) Macromonomers and Their Polymacromonomers by Light Scattering, SAXS, Intrinsic Viscosity, and Scanning Force Microscopy

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