Synthesis and wide-line NMR studies of α-deuterated polyacrylates and polyacrylonitrile

Mathias, Lon J.; Colletti, Ronald F.

doi:10.1021/ma00020a005

Cited by 11 publications

(8 citation statements)

References 2 publications

(2 reference statements)

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“…27 APMS-d was prepared from the reaction of CH3OD with a catalytic amount of DABCO. 28 This mixture was stirred at an ambient temperature for 2 days. Dried carbon black was added to eliminate the DABCO.…”

Section: Methodsmentioning

confidence: 99%

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Characterization of the Interface in Polymer−Silica Composites Containing an Acrylic Silane Coupling Agent

and

Blum

1999

Chem. Mater.

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Microscopic dynamics of the interfacial layer and macroscopic mechanical properties of [3-(acryloxy)propyl]trimethoxysilane (APMS) at a polymer-silica interface were studied using NMR and three-point bending tests. Wide-line deuterium NMR studies of deuterium-enriched [3-(acryloxy)propyl]trimethoxysilane-d (APMS-d), showed that when chemically bonded to silica, the acrylic group of APMS moved rapidly at the interface with air, more slowly when coated with a poly(methyl methacrylate) (PMMA) overlayer, and slowest when copolymerized with methyl methacrylate. A two-component line shape was found for the coated composite and these were assigned to relative immobile and mobile surface groups. From three-point bend tests, the PMMA/glass-fiber composite, made from glass laminates treated with APMS, had almost two times the flexural strength of a composite made from glass laminates not treated with APMS. Electron micrographs of the fracture surfaces revealed that the untreated fibers were smooth, while those from the APMS-treated glass were rougher, indicating the presence of polymer at the interface.

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Section: Methodsmentioning

confidence: 99%

“…[3-(Acryloxy)propyl]trimethoxysilane (APMS) was prepared from (3-chloropropyl)trimethoxysilane and acrylic acid in triethylamine via a condensation reaction . APMS- d was prepared from the reaction of CH 3 OD with a catalytic amount of DABCO . This mixture was stirred at an ambient temperature for 2 days.…”

Section: Methodsmentioning

confidence: 99%

Characterization of the Interface in Polymer−Silica Composites Containing an Acrylic Silane Coupling Agent

and

Blum

1999

Chem. Mater.

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“…Detailed molecular-level studies, however, have not been plentiful for polyacrylates in the bulk state. [18][19][20][21][22][23][24][25][26][27][28] Matsuzaki et al have already determined the stereochemical configurations by 1H NMR18 and 13C NMR19 spectra of several polyacrylates and model compounds in solvent. In contrast, the molecular motions have been studied by pulsed XH NMR20'21 and dielectric22 '23 and dynamic mechanical24-26 relaxation.…”

Section: Introductionmentioning

confidence: 99%

Molecular motions of poly(ethyl acrylate) and poly(n-butyl acrylate) studied by solid-state NMR and molecular dynamics computer experiments

Kikuchi¹,

Tokumitsu²,

Seki³

1993

Macromolecules

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“…A direct hydrogen-exchange reaction was chosen to prepare α-deuterated methyl acrylate. At room temperature methyl acrylate (8.32 g, 0.100 mol), deuterium oxide (33.99 g, 1.70 mol), and DABCO (1.61 g, 0.014 mol) were stirred in a 100 mL flask for 2 h. The deuterium oxide layer was removed with a separatory funnel.…”

Section: Methodsmentioning

confidence: 99%

“…A direct hydrogen-exchange reaction 19 Methyl acrylate-d (3.58 g, 0.041 mol) was polymerized in toluene (6.20 g, 0.067 mol) with 2,2′-azobis(isobutyronitrile) (0.06 g, 0.33 mmol) as the initiator. The solution was kept under nitrogen gas and bath-heated to 65 °C for 4 h. The yield of polymer was about 80%.…”

Section: Methodsmentioning

confidence: 99%

Segmental Motion of Surface-Bound Swollen Poly(methyl acrylate)-d

Liang

Blum

1996

Macromolecules

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Poly(methyl acrylate)-d (PMA-d), labeled in the backbone R position, was prepared and adsorbed from toluene on silica at a coverage of 0.38 mg of PMA-d/mg of silica. This coverage was roughly that of the maximum found in the adsorption isotherm. Comparisons of deuterium NMR spin-lattice relaxation time, T1, and spin-spin relaxation time, T2, for the adsorbed, swollen polymer at different temperatures were made to obtain information about the backbone motion of the surface-bound polymer. The results were consistent with a system where the fast local motions were similar to those in solution but the longer range segmental motions were more restricted than those in solution. The log-normal distribution yielded mean correlation times which were 4-10 times slower for the surface-bound species than that in solution. The Hall-Helfand (HH) model with two correlation times yielded slow correlation times more than an order of magnitude slower for the surface species. Compared to previous studies on terminally attached polymers which formed extended brushes, liquid-like segments of randomly attached homopolymers have significantly reduced longer range segmental motions.

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Synthesis and wide-line NMR studies of α-deuterated polyacrylates and polyacrylonitrile

Cited by 11 publications

References 2 publications

Characterization of the Interface in Polymer−Silica Composites Containing an Acrylic Silane Coupling Agent

Characterization of the Interface in Polymer−Silica Composites Containing an Acrylic Silane Coupling Agent

Molecular motions of poly(ethyl acrylate) and poly(n-butyl acrylate) studied by solid-state NMR and molecular dynamics computer experiments

Segmental Motion of Surface-Bound Swollen Poly(methyl acrylate)-d

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