Progress in the chemistry of polyreactive oligomers and some trends of its development. II. Specific features of network formation of oligomers and properties of network polymers

Berlin, A. A.; Matvejeva, N. G.

doi:10.1002/pol.1980.230150104

Cited by 14 publications

(3 citation statements)

References 38 publications

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“…The details of the preparation of these polymer samples will be described elsewhere. 13 Gel samples were prepared directly in 10-mm NMR tubes. The spectra of the gels were recorded 24 h after preparation to allow time for complete swelling.…”

Section: Methodsmentioning

confidence: 99%

Nature of residual unsaturation during cure of dimethacrylates examined by CPPEMAS carbon-13 NMR and simulation using a kinetic gelation model

Simon

Allen²,

Bennett³

et al. 1989

Macromolecules

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Section: Methodsmentioning

confidence: 99%

Nature of residual unsaturation during cure of dimethacrylates examined by CPPEMAS carbon-13 NMR and simulation using a kinetic gelation model

Simon

Allen²,

Bennett³

et al. 1989

Macromolecules

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“…Investigations of Structural Evolution. The development of heterogeneity during the evolution of highly cross-linked networks from homopolymerizations of multifunctional monomers impacts many applications and is an important area of research. − Current commercial applications of multifunctional monomers that would benefit from a better understanding of their cross-linked network structural evolution include abrasion-resistant coatings, dental materials, and flexographic printing plates, among others. A more complete understanding of nanoscale evolution of polymeric materials is critically important for their implementation in microelectronics and microdevice technologies as well as higher resolution applications such as molecular templating, , data storage, and quantum computing that necessitate nanoscale control and functionality.…”

Section: Introductionmentioning

confidence: 99%

Experimental Characterization of Structural Features during Radical Chain Homopolymerization of Multifunctional Monomers Prior to Macroscopic Gelation

2004

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An experimental methodology is presented to characterize the evolution of structural heterogeneities in cross-linked polymer networks formed by homopolymerizations of multifunctional monomers. In particular, intramolecularly cross-linked macromolecules (ICMs) were synthesized by individual initiation events and characterized. A set of complementary experimental tools, including atomic force microscopy (AFM), size exclusion chromatography, light scattering, and NMR, is used to provide information about size, intramolecular cross-link density, and kinetic chain length for poly(methacrylic anhydride) (PMA) ICMs. Images of PMA ICMs, which contain ca. 1000−2000 monomers, on average, are captured with AFM. Varying polymerization temperature from −13 to 70 °C led to an increase in the apparent size of the ICMs and an increase in the fraction of doubly reacted monomers. Furthermore, ICMs synthesized in the presence of tetraethylthiuram disulfide (TED), a photoiniferter precursor, were characterized. Iniferter-mediated polymerization of methacrylic anhydride created smaller ICMs with higher intramolecular cross-link density.

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“…Over the past several decades, many authors have contributed to the current, qualitative model of structural evolution from multifunctional monomer polymerizations that accounts for various aspects of polymerization kinetics, as well as indirect inferences and direct observations of film inhomogeneities. ,− Specifically, distinct regions of highly cyclized and cross-linked polymer form prior to macroscopic gelation. The regions of polymer become more highly cross-linked due to (1) enhancement of pendant double bond concentration in the vicinity of the propagating macroradical (relative to monomeric vinyl groups) and (2) minimization of bimolecular termination due to macroradical diffusion limitations, which results in higher bulk and local radical concentrations.…”

Section: Introductionmentioning

confidence: 99%

Off-Lattice Simulation of Multifunctional Monomer Polymerizations: Effects of Monomer Mobility, Structure, and Functionality on Structural Evolution at Low Conversion

Hutchison

Anseth

2004

J. Phys. Chem. B

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Fundamental insight into the polymerization behavior and structural evolution of highly cross-linked polymers synthesized from the chain polymerization of multifunctional monomers will benefit a number of current and emerging applications. This contribution reintroduces an off-lattice kinetic gelation model with refinements to the representations of monomer mobility, structure, and functionality, which more realistically capture low conversion propagation events during cross-linked network evolution. Intramolecularly cross-linked macromolecules (ICMs) are formed by simulation of a single propagating radical within a volume containing ca. 100 000 monomer units. Effects of monomer mobility, structure, and functionality on the relative size, kinetic chain length, and intramolecular cross-link density of ICMs are reported. Finally, aspects of percolation theory are applied to this off-lattice kinetic gelation simulation. The fractal dimension corresponds to the theoretical value for a lattice animal created by a three-dimensional percolation model and it is independent of conversion. Overall, this contribution demonstrates the utility of a unique approach for kinetic gelation simulation of multifunctional monomer polymerizations that affords more realistic representation of monomer structure and dynamics than traditional, lattice-based models.

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Progress in the chemistry of polyreactive oligomers and some trends of its development. II. Specific features of network formation of oligomers and properties of network polymers

Cited by 14 publications

References 38 publications

Nature of residual unsaturation during cure of dimethacrylates examined by CPPEMAS carbon-13 NMR and simulation using a kinetic gelation model

Nature of residual unsaturation during cure of dimethacrylates examined by CPPEMAS carbon-13 NMR and simulation using a kinetic gelation model

Experimental Characterization of Structural Features during Radical Chain Homopolymerization of Multifunctional Monomers Prior to Macroscopic Gelation

Off-Lattice Simulation of Multifunctional Monomer Polymerizations: Effects of Monomer Mobility, Structure, and Functionality on Structural Evolution at Low Conversion

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