Molecular Modeling of Cross-Linked Polymers with Complex Cure Pathways: A Case Study of Bismaleimide Resins

Radue, Matthew S.; Varshney, Vikas; Baur, Jeffery W.; Roy, Ajit K.; Odegard, Gregory M.

doi:10.1021/acs.macromol.7b01979

Cited by 75 publications

(67 citation statements)

References 58 publications

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“…(1) Cross-linking and Monte-Carlo or molecular dynamics simulations using a coarse-grained model and then conversion back to the original atomistic description [8][9][10][11] (2) Starting with a stoichiometric mixture of the epoxy monomer and the hardener and then "polymerizing" the mixture in conjunction with atomistic molecular dynamics (MD) simulations. This method has also proven effective for complex cross-linking reactions [12] The most extensive research effort is found in the polyepoxy systems EPON 862 resin cross-linked with diethyltoluenediamine (DETDA) [13][14][15][16] and triethylenetetramine (TETA) [17][18][19][20] because of their wide use in the fields of modern aeronautics and composite materials and their use in the development of micro-and nanodevices with desired properties. The cross-linking of the diglycidyl ether of bisphenol-A (DGEBA) resin was also widely studied with different hardeners, i.e., isophorone diamine (IPD) [21,22], trimethylene glycol di-p-aminobenzoate (TMAB) [23], DETDA [24], diaminodiphenyl sulfone (DDS) [9], methylenedianiline [25], poly(oxopropylene) diamines (POP) [26,27], 4,4 ′ -methylenebis(cyclohexylamine) (MCA) [26], diethylenetriamine (DETA) [28], and JEFFAMINE® D-230 [29].…”

Section: Introductionmentioning

confidence: 99%

Model of the DGEBA-EDA Epoxy Polymer: Experiments and Simulation Using Classical Molecular Dynamics

Gavrielides

Duguet

Aufray

et al. 2019

International Journal of Polymer Science

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Polyepoxy samples are synthesized from diglycidylether of bisphenol A (DGEBA) and ethylene diamine (EDA) monomers at a stoichiometric ratio of 2 DGEBA : 1 EDA in model conditions in order to promote a high degree of polymerization and a low density of defects and to try to approach the ideal models obtained by simulation. A slow polymerization (>24 h at ambient temperature) and a postcuring achieved in an inert atmosphere lead to a conversion degree of 92±2% and a midpoint glass transition temperature of 391±1 K. In parallel, a model is created with a multistep cross-linking procedure. In this work, all-atom molecular dynamics (MD) simulations are performed with LAMMPS and the GAFF 1.8 force field. In the initial liquid mixture of reactants (600 molecules), proper mixing is demonstrated by the calculation of the partial radial distribution functions (RDF), which show a minimum intermolecular distance of 2.8 Å and similar distributions for EDA-EDA, DGEBA-DGEBA, and DGEBA-EDA molecules in the simulation boxes. Then, in alternation with MD equilibrations, cross-linking is performed on frozen configurations by creating covalent bonds between reactive pairs within a reaction radius of 3 Å. The resulting boxes show conversion rates of 90-93% and densities close to the experimental value. Finally, a cooling ramp from 700 K to 25 K is applied in order to monitor the specific volume and the coefficient of volumetric thermal expansion (CVTE) of the polymer and to derive the glass transition temperature. Experimental thermomechanical analyses (TMA) compares well with simulations for both the specific volume and the CVTE evolutions with temperature. Whereas the uncertainty remains high with the fitting procedure used, we calculate a glass transition temperature of 390±8 K which compares very well with the experimental values (391±1 K from DSC and 380 K from TMA).

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Section: Introductionmentioning

confidence: 99%

Model of the DGEBA-EDA Epoxy Polymer: Experiments and Simulation Using Classical Molecular Dynamics

Gavrielides

Duguet

Aufray

et al. 2019

International Journal of Polymer Science

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“…As shown in Scheme , during the curing process of EG‐BMI resins, the major reactions were ene reaction and styrene–maleimide copolymerization reaction. Meanwhile, self‐polymerization and Diels–Alder reaction also happened in the systems . It was worth noting that it was previously thought that the ene reaction was succeeded by a Diels–Alder reaction between the newly formed di‐ene (from benzene ring of eugenol) and electron‐poor dienophile in maleimides.…”

Section: Resultsmentioning

confidence: 94%

Eugenol‐Derived Bismaleimide High Performance Resins and Composites Using Diisocyanate as Property Modifier

Wang

et al. 2019

Macro Materials & Eng

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The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/mame.201800713. High Performance ResinsA new kind of high performance bismaleimide resin with good processability and improved toughness is synthesized by chemical modification of 4,4′bismaleimidodiphenylmethane (BMI) by eugenol (EG) and different contents of 4,4′-diphenylmethane diisocyanate (MDI). MDI-EG-BMI resins exhibit good thermal stability for its 5% weight loss temperatures around 300 °C and its residue of 41.61% at 900 °C, which are much higher than those of EG-BMI resin. Then, the carbon fiber-reinforced MDI-EG-BMI composites are fabricated. The mechanical properties of the composites matrixed by MDI-EG-BMI resins are better than those by EG-BMI resin. For carbon/MDI-EG-BMI composites, their glass transition temperatures are higher than 300 °C, and their flexural strength, moduli, and toughness are maintained at a range of 217.47-404.36 MPa, 35.12-48.49 GPa, and 1.16-2.63 MJ m −3 respectively; with the contents increasing of MDI in the resin formulation, the flexural properties first increase then decrease; comprehensively the composite with 30 wt% MDI has the best mechanical and thermal properties.

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“…DPBM reacted with the aromatic allyl compounds [44,45,51] like diallylbisphenol A DABPA, dipropargylether of bisphenol A DPBPA and Bis (propenyl phenoxybenzophenon) BPPB via Diels Alder reaction. A recent publication [15]…”

Section: Reaction Of Dpbm With Diallybisphenol a Via Diels Alders Reamentioning

confidence: 99%

Mono- and Bis- Maleimide Resins in Preimpregnated Fibres

Horacek¹,

Puchenau²

2020

J. Res. Updates Polym. Sci.

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Fibres are preimpregnated by solutions of mono-and bis-maleimides with comonomers. Imides alone polymerize to resins with too low energies of fracture. In the presence of Methylene dianiline or Aniline Diphenylmethylenebismaleimide reacts via Michael addition to equimolar addition products. When fibres are preimpregnated with these addition compounds alone or in combination with flame retardants, B-prepregs are obtained, which after curing show high glass temperatures and sufficient energies of fracture. 2.5 moles of Diphenylmethylene bismaleimide and 1mol Methylene dianiline or 1mole Aniline react to resins with glass temperatures of 350 and 380°C and energies of fracture of 75 and 100J/m 2. The resins contain no carcinogen or blood harming free amines. A one pot reaction starting from Methylene dianiline and Maleic anhydride is possible and more economic. As polymerized bismaleimides possess their imide bonds in the side chain, they are strictly spoken no polyimides with imide bonds in the main chain. Diphenylmethylenebismaleimide and styrene as copolymer react to an insoluble crosslinked polymer. Fibres are preimpregnated with equimolar mixtures of 2-Bromophenylmaleimide and styrene. After curing laminates with 285°C glass temperature and sufficient energies of fracture are obtained. The heat resistant resins are charring polymers and display higher Limiting Oxygen Indices, when the heats of combustion are increased. Differential Scanning Calorimetry determines the temperatures and the heats of glass transition, which indicate that the glass temperature is raised, when the enthalpy is increased and the entropy reduced, which is achievable by Diphenylbismaleimide and 2-Bromophenylmaleimide with their large side groups appropriate for intermolecular forces and steric hindrance.

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Molecular Modeling of Cross-Linked Polymers with Complex Cure Pathways: A Case Study of Bismaleimide Resins

Cited by 75 publications

References 58 publications

Model of the DGEBA-EDA Epoxy Polymer: Experiments and Simulation Using Classical Molecular Dynamics

Model of the DGEBA-EDA Epoxy Polymer: Experiments and Simulation Using Classical Molecular Dynamics

Eugenol‐Derived Bismaleimide High Performance Resins and Composites Using Diisocyanate as Property Modifier

Mono- and Bis- Maleimide Resins in Preimpregnated Fibres

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