Mechanism Dictates Mechanics: A Molecular Substituent Effect in the Macroscopic Fracture of a Covalent Polymer Network

2021 ◽  
Author(s):  
Shu Wang ◽  
Haley K. Beech ◽  
Brandon H. Bowser ◽  
Tatiana B. Kouznetsova ◽  
Bradley D. Olsen ◽  
...  
Keyword(s):  
Substituent Effect ◽  
Polymer Network ◽  
Macroscopic Fracture

scholarly journals Mechanism Dictates Mechanics: A Molecular Substituent Effect in the Macroscopic Fracture of a Covalent Polymer Network

2021 ◽  
Author(s):  
Shu Wang ◽  
Haley Beech ◽  
Brandon Bowser ◽  
Tatiana Kouznetsova ◽  
Bradley Olsen ◽  
...  
Keyword(s):  
Single Molecule ◽  
Weak Link ◽  
Polymer Network ◽  
Single Molecule Force Spectroscopy ◽  
Molecule Reaction ◽  
Macroscopic Fracture ◽  
Resonance Stabilization ◽  
The Difference ◽  
Poly Ethylene ◽  
Kinetics Of

<div><p>Here, we report covalent polymer gels in which the macroscopic fracture “reaction” is controlled by mechanophores embedded within mechanically active network strands. We synthesized poly(ethylene glycol) (PEG) gels through the end-linking of azide-terminated tetra-arm PEG (M<sub>n </sub>= 5 kDa) with bis-alkyne linkers. Networks were formed under identical conditions, except that the bis-alkyne was varied to include either a <i>cis</i>-diaryl (<b>1</b>) or <i>cis</i>-dialkyl (<b>2</b>) linked cyclobutane mechanophore that acts as a mechanochemical “weak link” through a force-coupled cycloreversion. A control network featuring a bis-alkyne without cyclobutane (<b>3</b>) was also synthesized. The networks show the same linear elasticity (G' = 23~24 kPa, 0.1 – 100 Hz) and equilibrium mass swelling ratios (Q = 10~11 in tetrahydrofuran), but they exhibit tearing energies that span a factor of 8 (3.4 J∙m<sup>-2</sup>, 10.5 J∙m<sup>-2</sup>, and 27.1 J∙m<sup>-2</sup> for networks with <b>1</b>, <b>2</b>, and <b>3</b>, respectively). The difference in fracture energy is well aligned with the force-coupled scission kinetics of the mechanophores observed in single-molecule force spectroscopy experiments, implicating local resonance stabilization of a diradical transition state in the cycloreversion of <b>1 </b>as a key determinant of the relative ease with which its network is torn. The connection between macroscopic fracture and small molecule reaction mechanism suggests opportunities for molecular understanding and optimization of polymer network behavior. </p></div>

scholarly journals Mechanism Dictates Mechanics: A Molecular Substituent Effect in the Macroscopic Fracture of a Covalent Polymer Network

2021 ◽  
Author(s):  
Shu Wang ◽  
Haley Beech ◽  
Brandon Bowser ◽  
Tatiana Kouznetsova ◽  
Bradley Olsen ◽  
...  
Keyword(s):  
Single Molecule ◽  
Weak Link ◽  
Polymer Network ◽  
Single Molecule Force Spectroscopy ◽  
Molecule Reaction ◽  
Macroscopic Fracture ◽  
Resonance Stabilization ◽  
The Difference ◽  
Poly Ethylene ◽  
Kinetics Of

<div><p>Here, we report covalent polymer gels in which the macroscopic fracture “reaction” is controlled by mechanophores embedded within mechanically active network strands. We synthesized poly(ethylene glycol) (PEG) gels through the end-linking of azide-terminated tetra-arm PEG (M<sub>n </sub>= 5 kDa) with bis-alkyne linkers. Networks were formed under identical conditions, except that the bis-alkyne was varied to include either a <i>cis</i>-diaryl (<b>1</b>) or <i>cis</i>-dialkyl (<b>2</b>) linked cyclobutane mechanophore that acts as a mechanochemical “weak link” through a force-coupled cycloreversion. A control network featuring a bis-alkyne without cyclobutane (<b>3</b>) was also synthesized. The networks show the same linear elasticity (G' = 23~24 kPa, 0.1 – 100 Hz) and equilibrium mass swelling ratios (Q = 10~11 in tetrahydrofuran), but they exhibit tearing energies that span a factor of 8 (3.4 J∙m<sup>-2</sup>, 10.5 J∙m<sup>-2</sup>, and 27.1 J∙m<sup>-2</sup> for networks with <b>1</b>, <b>2</b>, and <b>3</b>, respectively). The difference in fracture energy is well aligned with the force-coupled scission kinetics of the mechanophores observed in single-molecule force spectroscopy experiments, implicating local resonance stabilization of a diradical transition state in the cycloreversion of <b>1 </b>as a key determinant of the relative ease with which its network is torn. The connection between macroscopic fracture and small molecule reaction mechanism suggests opportunities for molecular understanding and optimization of polymer network behavior. </p></div>

Freeze-etch TEM of aqueous polymer gel network morphology

1986 ◽  
Vol 44 ◽  
pp. 796-797
Author(s):  
J. A. N. Zasadzinski ◽  
R. K. Prud'homme
Keyword(s):  
Metal Ion ◽  
Polymer Network ◽  
Polymer Gels ◽  
Polymer Gel ◽  
Deformation History ◽  
Crosslinked Polymer ◽  
Aqueous Polymer ◽  
History Of ◽  
Gel Network ◽  
Network Morphology

The rheological and mechanical properties of crosslinked polymer gels arise from the structure of the gel network. In turn, the structure of the gel network results from: thermodynamically determined interactions between the polymer chain segments, the interactions of the crosslinking metal ion with the polymer, and the deformation history of the network. Interpretations of mechanical and rheological measurements on polymer gels invariably begin with a conceptual model of,the microstructure of the gel network derived from polymer kinetic theory. In the present work, we use freeze-etch replication TEM to image the polymer network morphology of titanium crosslinked hydroxypropyl guars in an attempt to directly relate macroscopic phenomena with network structure.

Investigation of the Microscopic Viscoelastic Property for Cross-linked Polymer Network by Molecular Dynamics Simulation

2011 ◽  
Vol 39 (1) ◽  
pp. 44-58 ◽  
Author(s):  
Y. Masumoto ◽  
Y. Iida
Keyword(s):  
Molecular Dynamics ◽  
Molecular Dynamics Simulation ◽  
Analytical Method ◽  
Viscoelastic Properties ◽  
Polymer Network ◽  
Dynamics Simulation ◽  
Coarse Grained ◽  
The Cross ◽  
Microscopic Dynamic ◽  
Coarse Grained Molecular Dynamics

Abstract The purpose of this work is to develop a new analytical method for simulating the microscopic mechanical property of the cross-linked polymer system using the coarse-grained molecular dynamics simulation. This new analytical method will be utilized for the molecular designing of the tire rubber compound to improve the tire performances such as rolling resistance and wet traction. First, we evaluate the microscopic dynamic viscoelastic properties of the cross-linked polymer using coarse-grained molecular dynamics simulation. This simulation has been conducted by the coarse-grained molecular dynamics program in the OCTA) (http://octa.jp/). To simplify the problem, we employ the bead-spring model, in which a sequence of beads connected by springs denotes a polymer chain. The linear polymer chains that are cross-linked by the cross-linking agents express the three-dimensional cross-linked polymer network. In order to obtain the microscopic dynamic viscoelastic properties, oscillatory deformation is applied to the simulation cell. By applying the time-temperature reduction law to this simulation result, we can evaluate the dynamic viscoelastic properties in the wide deformational frequency range including the rubbery state. Then, the stress is separated into the nonbonding stress and the bonding stress. We confirm that the contribution of the nonbonding stress is larger at lower temperatures. On the other hand, the contribution of the bonding stress is larger at higher temperatures. Finally, analyzing a change of microscopic structure in dynamic oscillatory deformation, we determine that the temperature/frequency dependence of bond stress response to a dynamic oscillatory deformation depends on the temperature dependence of the average bond length in the equilibrium structure and the temperature/frequency dependence of bond orientation. We show that our simulation is a useful tool for studying the microscopic properties of a cross-linked polymer.

The diffusion coefficients 110mAg isotope in copper-contained chalcogenide films obtained by chemical deposition

2016 ◽  
Author(s):  
Д.Л. Байдаков
Keyword(s):  
Diffusion Coefficients ◽  
Chalcogenide Glasses ◽  
Film Formation ◽  
Polymer Network ◽  
Chemical Deposition ◽  
Film Deposition ◽  
Constant Current ◽  
Residual Pressure ◽  
Quartz Ampoule ◽  
Chalcogenide Films

Методом химического нанесения из растворов халькогенидных стекол в н-бутиламине получены многокомпонентные халькогенидные пленки CuI-As2Se3, CuI-PbI2-As2Se3, CuI-SbI3-As2Se3, CuI-SbI3-PbI2-As2Se3. Синтез многокомпонентных медьсодержащих халькогенидных стекол, использовавшихся для нанесения пленок, проводили методом вакуумной плавки в кварцевых ампулах при температуре 400…950 °С и остаточном давлении не более 0,13 Па. Закалку стекол производили от 600 °С в воду со льдом с разливом расплава в ампуле. Навеску стекла размельчали в порошок и кипятили в н-бутиламине до полного растворения. Для предотвращения процессов окисления, нанесение и отжиг пленок проводили в атмосфере химически инертного азота. Подложку помещали на устройство для вращения, наносили на нее раствор и вращали подложку со скоростью несколько тысяч оборотов в минуту. Отжиг пленок проводили при температуре 100 °С в течение 1 ч. Измерение электропроводности полученных пленок проводили на постоянном и переменном токе в зависимости от значений электропроводности в температурном интервале 20…100 °С. Измерение коэффициентов диффузии проводили абсорбционным методом. Из диффузионных экспериментов определены значения коэффициентов диффузии катионов изотопа 110mAg в медьсодержащих халькогенидных пленках. Установлено, что значения коэффициентов диффузии ионов Ag+ в химически нанесенных пленках и исходных стеклах практически не различаются. Аналогию значений коэффициентов диффузии изотопа 110mAg в халькогенидных стеклах и пленках на их основе можно объяснить сохранением полимерной сетки связей халькогенидных стекол при их растворении в органических основаниях (аминах). В процессе нанесения и формирования пленок полимерная (макромолекулярная) структура раствора халькогенидных стекол сохраняется. The method of chemical deposition from solutions of chalcogenide glasses in n-butyl amine obtained multicomponent chalcogenide films CuI-As2Se3, CuI-PbI2-As2Se3, CuI-SbI3-As2Se3, CuI-SbI3-PbI2-As2Se3. Synthesis of copper multicomponent chalcogenide glasses, used for film deposition was carried out by vacuum melting in quartz ampoule at a temperature of 400…950 °C and a residual pressure of not more than 0.13 Pa. The temperature of glass produced from the 600 °C to the ice water spill of the melt in the ampoule. Weigh glass comminuted to a powder and heated in n-butylamine until complete dissolution. To prevent oxidation, deposition and annealing of the films was carried out in an atmosphere of nitrogen chemically inert. The substrate is placed on a device for rotating, it was applied to the solution and the substrate was rotated at a speed of several thousand revolutions per minute. Annealing of the films was carried out at 100 °C for 1 hour. Measurement of the electrical conductivity of the obtained films was conducted at a constant current and variable depending on the conductivity values ​​in the temperature range from 20 to 100 °C. Measurement of diffusion coefficients was performed according to the absorption method. From diffusion experiments, the values ​​of the diffusion coefficients 110mAg isotope cations in copper chalcogenide films. It was found that the values ​​of the diffusion coefficients of the ions Ag+ in a chemically deposited films and the original glasses are indistinguishable. The analogy of the diffusion coefficient values ​​110mAg isotope in chalcogenide glasses and films based on them can be attributed to the preservation of the polymer network connections chalcogenide glasses when dissolved in organic bases (amines). During application and film formation the polymer (macromolecular) structure of chalcogenide glasses of the solution is maintained.

Substituent effect on wave numbers of C=O valence vibrations in ferrocene derivatives

1983 ◽  
Vol 48 (6) ◽  
pp. 1635-1646 ◽  
Author(s):  
Alexander Perjéssy ◽  
Štefan Toma
Keyword(s):  
Linear Correlation ◽  
Substituent Effect ◽  
Empirical Relation ◽  
Ferrocene Derivatives ◽  
Wave Numbers ◽  
Complex Structural ◽  
Transmission Factors

Wave numbers of C=O valence vibrations of 83 ferrocene derivatives have been measured in tetrachloromethane. For a series of 154 compounds containing ferrocene skeleton linear correlation has been found between wave numbers of C=O vibration and X+(R) constants of structural fragments in the sense of modified and extended Seth-Paul-Van Duyse equation. Validity has been verified of the recently derived empirical relation for calculation of the X+(R) constants of complex structural fragments from values of constants of substituents and transmission factors for simple structural groupings. The transmission factors γ and π' for 1,3- and 1,1'-ferrocene system have been found to be well applicable to calculation of constants of structural fragments containing ferrocene skeleton.

Ionic dimerisation of trifluoropropenenitrile and its addition reactions with methyl trifluoropropenoate

1980 ◽  
Vol 45 (2) ◽  
pp. 406-414 ◽  
Author(s):  
Jiří Svoboda ◽  
Oldřich Paleta ◽  
Václav Dědek
Keyword(s):  
Reaction Mechanism ◽  
Proton Transfer ◽  
Substituent Effect ◽  
Solvent Molecule ◽  
Addition Product ◽  
Potassium Fluoride ◽  
Relative Reactivity ◽  
Addition Reactions ◽  
Tertiary Amines ◽  
Optimum Conditions

Dimerisation of trifluoropropenenitrile (I) in the presence of potassium fluoride and tertiary amines afforded a mixture of stereoisomeric perfluoro-4-methyl-pentenedinitriles (II), higher-boiling compounds, and 2,3,3,3-tetrafluoropropanenitrile (III) which arises by proton transfer from the solvent molecule. Under optimum conditions, product II was obtained in about 50% yield. Reaction of the nitrile I with methyl trifluoropropenoate (IV) gave, besides the dimers II and V, the product of addition of the nitrile I to the propenoate, IV, i.e. methyl 4-cyanoperfluoro-2-pentenoate (VI), and the addition product of the propenoate IV to the nitrile I, i.e. methyl 4-cyanoperfluoro-2-methyl-3-butenoate (VII). The relative reactivity if I and IV is discussed. The ratio of stereoisomers in II, V, VI and VII indicates that the magnitude of the steric substituent effect, operating in the reaction mechanism, decreases in the order -CFCF3.(COOCH3) > -CFCF3(CN) > -COOCH3 > -CN.

Perturbation theory of substituent effect. Importance of the field effect in transmission of the substituent effect

1980 ◽  
Vol 45 (6) ◽  
pp. 1655-1661 ◽  
Author(s):  
Robert Ponec
Keyword(s):  
Perturbation Theory ◽  
Carboxylic Acids ◽  
Quantum Chemical ◽  
Substituent Effect ◽  
Field Effect ◽  
Adequate Description ◽  
Meta Position ◽  
Unsaturated Carboxylic Acids

Various quantum chemical approaches to the problem of transmission of the substituent effect were compared. It was shown that inclusion of the electronic repulsion (field effect) was necessary to give a true picture of differences in ρ constants for reactions of the cis and trans isomers of substituted unsaturated carboxylic acids; the same holds for an adequate description of transmission of the substituent effect from the meta position on a given skeleton.

Kinetic Study of Hydrolysis of Benzoates. Part XXVI. Variation of the Substituent Effect with Solvent in Alkaline Hydrolysis of Substituted Alkyl Benzoates

2006 ◽  
Vol 71 (11-12) ◽  
pp. 1557-1570 ◽  
Author(s):  
Vilve Nummert ◽  
Mare Piirsalu ◽  
Ilmar A. Koppel
Keyword(s):  
Kinetic Study ◽  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Substituent Effect ◽  
Substituent Effects ◽  
Alkyl Substituent ◽  
Solvent Parameters ◽  
Substituent Constants ◽  
Hydrolysis Of ◽  
Main Factor

The second-order rate constants k2 (dm3 mol-1 s-1) for the alkaline hydrolysis of substituted alkyl benzoates C6H5CO2R have been measured spectrophotometrically in aqueous 0.5 M Bu4NBr at 50 and 25 °C (R = CH3, CH2Cl, CH2CN, CH2C≡CH, CH2C6H5, CH2CH2Cl, CH2CH2OCH3, CH2CH3) and in aqueous 5.3 M NaClO4 at 25 °C (R = CH3, CH2Cl, CH2CN, CH2C≡CH). The dependence of the alkyl substituent effects on different solvent parameters was studied using the following equations:      ∆ log k = c0 + c1σI + c2EsB + c3∆E + c4∆Y + c5∆P + c6∆EσI + c7∆YσI + c8∆PσI     ∆ log k = c0 + c1σ* + c2EsB + c3∆E + c4∆Y + c5∆P + c6∆Eσ* + c7∆Yσ* + c8∆Pσ* .  ∆ log k = log kR - log kCH3. σI and σ* are the Taft inductive and polar substituent constants. E, Y and P are the solvent electrophilicity, polarity and polarizability parameters, respectively. In the data treatment ∆E = ES - EH2O , ∆Y = YS - YH2O , ∆P = PS - PH2O were used. The solvent electrophilicity, E, was found to be the main factor responsible for changes in alkyl substituent effects with medium. When σI constants were used, variation of the polar term of alkyl substituents with the solvent electrophilicity E was found to be similar to that observed earlier for meta and para substituents, but twice less when σ* constants were used. The steric term for alkyl substituents was approximately independent of the solvent parameters.

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