scholarly journals Conformational Entropy as a Means to Control the Behavior of Poly(diketonenamine) Vitrimers In and Out of Equilibrium

2019 ◽  
Author(s):  
Changfei He ◽  
Peter Christensen ◽  
Trevor Seguin ◽  
Brandon Wood ◽  
Kristin Persson ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Glass Transition ◽  
Characteristic Time ◽  
Degrees Of Freedom ◽  
Freezing Temperature ◽  
Thermomechanical Behavior ◽  
Polymer Chains ◽  
Network Density ◽  
Conformational Entropy ◽  
Conformational Degrees Of Freedom

Here we show how to control the thermomechanical behavior of vitrimers, both in and out of equilibrium, by incorporating into the dynamic covalent network linear polymer segments varying in both molecular weight (MW = 0–12 kg mol–1) and conformational degrees of freedom. While increasing MW of linear segments predictably yields a lower storage modulus (E’) at the rubbery plateau after softening above the glass transition (Tg), due to the lower network density, we further find that both Tg and the characteristic time (t*) of stress-relaxation when deformed are independently governed by the conformational entropy of the embodied linear segments. We also find that activation energies (Ea) for vitrimer bond exchange in the solid-state are lower, by as much as 19 kJ mol−1, for networks incorporating flexible chains, and that the network’s topology freezing temperature (Tv) decreases with increasing MW of flexible linear segments, but increases with increasing MW of stiff linear segments. Therefore, the dynamics of vitrimer reconfigurability are influenced not only by the energetics of associative bond exchange for a given network density, but also foundationally by the entropy of polymer chains within the network.

Conformational Entropy as a Means to Control the Behavior of Poly(diketonenamine) Vitrimers In and Out of Equilibrium

2019 ◽  
Author(s):  
Changfei He ◽  
Peter Christensen ◽  
Trevor Seguin ◽  
Brandon Wood ◽  
Kristin Persson ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Glass Transition ◽  
Characteristic Time ◽  
Degrees Of Freedom ◽  
Freezing Temperature ◽  
Thermomechanical Behavior ◽  
Polymer Chains ◽  
Network Density ◽  
Conformational Entropy ◽  
Conformational Degrees Of Freedom

Here we show how to control the thermomechanical behavior of vitrimers, both in and out of equilibrium, by incorporating into the dynamic covalent network linear polymer segments varying in both molecular weight (MW = 0–12 kg mol–1) and conformational degrees of freedom. While increasing MW of linear segments predictably yields a lower storage modulus (E’) at the rubbery plateau after softening above the glass transition (Tg), due to the lower network density, we further find that both Tg and the characteristic time (t*) of stress-relaxation when deformed are independently governed by the conformational entropy of the embodied linear segments. We also find that activation energies (Ea) for vitrimer bond exchange in the solid-state are lower, by as much as 19 kJ mol−1, for networks incorporating flexible chains, and that the network’s topology freezing temperature (Tv) decreases with increasing MW of flexible linear segments, but increases with increasing MW of stiff linear segments. Therefore, the dynamics of vitrimer reconfigurability are influenced not only by the energetics of associative bond exchange for a given network density, but also foundationally by the entropy of polymer chains within the network.

Understanding Conformational Entropy in Small Molecules

2020 ◽  
Author(s):  
Lucian Chan ◽  
Garrett Morris ◽  
Geoffrey Hutchison
Keyword(s):  
Small Molecules ◽  
Degrees Of Freedom ◽  
Absolute Error ◽  
Low Energy ◽  
Standard Entropy ◽  
Free Energies ◽  
Conformational Entropy ◽  
Wide Range ◽  
High Degree ◽  
Empirical Corrections

The calculation of the entropy of flexible molecules can be challenging, since the number of possible conformers grows exponentially with molecule size and many low-energy conformers may be thermally accessible. Different methods have been proposed to approximate the contribution of conformational entropy to the molecular standard entropy, including performing thermochemistry calculations with all possible stable conformations, and developing empirical corrections from experimental data. We have performed conformer sampling on over 120,000 small molecules generating some 12 million conformers, to develop models to predict conformational entropy across a wide range of molecules. Using insight into the nature of conformational disorder, our cross-validated physically-motivated statistical model can outperform common machine learning and deep learning methods, with a mean absolute error ≈4.8 J/mol•K, or under 0.4 kcal/mol at 300 K. Beyond predicting molecular entropies and free energies, the model implies a high degree of correlation between torsions in most molecules, often as- sumed to be independent. While individual dihedral rotations may have low energetic barriers, the shape and chemical functionality of most molecules necessarily correlate their torsional degrees of freedom, and hence restrict the number of low-energy conformations immensely. Our simple models capture these correlations, and advance our understanding of small molecule conformational entropy.

The effect of methyl and methoxy substituents on dianilines for a thermosetting polyimide system

2020 ◽  
Vol 32 (7) ◽  
pp. 801-822 ◽  
Author(s):  
John J La Scala ◽  
Greg Yandek ◽  
Jason Lamb ◽  
Craig M Paquette ◽  
William S Eck ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Molecular Weight ◽  
Glass Transition ◽  
Elevated Temperature ◽  
Methyl Substituent ◽  
Glass Transition Temperatures ◽  
High Performing ◽  
Methoxy Substituent ◽  
Acidic Conditions ◽  
Thermal Stability Of

4,4′-Methylenedianiline (MDA) is widely used in high-temperature polyimide resins, including polymerization of monomer reactants-15. The toxicity of MDA significantly limits the manufacturability using this resin. Modifying the substitution and electronics of MDA could allow for the reduction of toxicity while maintaining the high-performing properties of the materials derived from the modified MDA. The addition of a single methyl substituent, methoxy substituent, location of these substituents, and location of the amine relative to the phenolic bridge were modified as were other non-aniline diamines. Various anilines were condensed with paraformaldehyde under acidic conditions to yield dianilines. These dianilines and diamines were reacted with nadic anhydride and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride in methanol to form the polyamic acid oligomers and heated at elevated temperature to form polyimide oligomers. It was found that the molecular weight of the oligomers derived from MDA alternatives was generally lower than that of MDA oligomers resulting in lower glass transition temperatures ( T gs) and degradation temperatures. Additionally, methoxy substituents further reduce the T g of the polymers versus methyl substituents and reduce the thermal stability of the resin. Methyl-substituted alternatives produced polyimides with similar T gs and degradation temperatures. The toxicity of the MDA alternatives was examined. Although a few were identified with reduced toxicities, the alternatives with properties similar to that of MDA also had high toxicities.

Development of Reformative Surgery Method Using Partial Freezing for the Liver

2006 ◽  
Vol 128 (6) ◽  
pp. 862-866
Author(s):  
M. Takahashi ◽  
S. Nomura ◽  
M. Jindai ◽  
S. Shibata ◽  
X. Zhu ◽  
...  
Keyword(s):  
Cooling Rate ◽  
Degrees Of Freedom ◽  
Operation Time ◽  
Basic Research ◽  
Freezing Temperature ◽  
The Finite Element Method ◽  
Porcine Liver ◽  
Liver Sample ◽  
Peltier Module ◽  
Increment Rate

To minimize surgical stresses including blood loss and operation time to the patients during hepatic resection, we studied the feasibility of a combination of a partial liver freezing technique and shape-memory alloy, which also enables a free-designed resection curve. In this surgical procedure, the region surrounding a tumor in the liver is frozen to excise and prevent hemorrhage. The liver was frozen by a Peltier module. The effects of cooling rate and freezing temperature on the excision force that arise between a scalpel and the liver are carried out experimentally as a basic research for partial freezing surgical procedures. A porcine liver was used as a liver sample. The physical properties were estimated by using the finite element method based on the heat transfer characteristics of the liver. Isolation of the liver was conducted using a scalpel attached to the end-effector of a 3 degrees of freedom robot. In the experiments, the minimum excision force was obtained at a temperature between 272K and 275K; therefore, it is preferable that the liver be excised within this temperature range. Lowering of the cooling rate decreases the excision force even if the temperature of the liver remains unchanged. The lower the temperature of the liver is, the larger the increment rate of excision force is with regard to the cooling rate.

Stereo-chemical contributions to the glass transition and liquid–liquid phase separation in high molecular weight poly(N-vinyl carbazole)

RSC Advances ◽  
2016 ◽  
Vol 6 (35) ◽  
pp. 29326-29333 ◽  
Author(s):  
Abdul G. Al Lafi ◽  
James N. Hay
Keyword(s):  
Molecular Weight ◽  
Glass Transition ◽  
Phase Separation ◽  
Liquid Phase ◽  
High Molecular Weight ◽  
Structural Properties ◽  
Thermal History ◽  
Liquid Phase Separation ◽  
High Molecular Weight Poly ◽  
Liquid Liquid Phase Separation

Thermal history and purification effects on the structural properties of PVK were investigated. Liquid–liquid phase separation is suggested to occur by separation of isotactic rich segments from a matrix which is predominantly atactic.

Synthesis and Characterization of Poly(Aryl Ether Quinoxaline)s with Controlled Molecular Weight

2011 ◽  
Vol 391-392 ◽  
pp. 826-829
Author(s):  
Song Ya Zhang ◽  
Zhong Xiao Li ◽  
Jia Ling Pu
Keyword(s):  
Molecular Weight ◽  
Glass Transition ◽  
Strong Acid ◽  
Decomposition Temperature ◽  
Molar Ratio ◽  
Synthesis And Characterization ◽  
Aryl Ether ◽  
Good Solubility ◽  
Step Procedure

Novel poly(aryl ether quinoxaline)s (PEQs) were prepared via a two-step procedure. First, poly (ether benzil) (PEB) was synthesized by the polycondensation of 4,4’-difluorobenzil and 4,4’-isopropylidenediphenol.Then, PEB was reacted with 1,2-diaminobenzene and 4,4'-oxydibenzene-1,2-diamine to give the PEQs. The molecular weight of the PEQs could be adjusted easily by varying the molar ratio of 1,2-diaminobenzene to 4,4'-oxydibenzene-1,2-diamine. The PEQs exhibited good solubility in common organic solvents such as NMP, DMAc, DMF, cyclohexanone and chloroform. In addition, the PEQs also had high glass transition (Tg) temperatures and good thermal properties, with an initial thermal decomposition temperature above 475 oC and glass transition temperatures above 210 oC. They also exhibited excellent resistance to strong acid and alkali.

Composition and molecular-weight dependence of the glass transition in polystyrene-poly(2,6-dimethylphenylene ether) blends

Polymer ◽  
1988 ◽  
Vol 29 (12) ◽  
pp. 2235-2243 ◽  
Author(s):  
Marco Aurelio de Araujo ◽  
Reimund Stadler ◽  
Hans-Joachim Cantow
Keyword(s):  
Molecular Weight ◽  
Glass Transition ◽  
Molecular Weight Dependence

Imide Oligomers Containing Pendent and Terminal Phenylethynyl Groups—II

1998 ◽  
Vol 10 (3) ◽  
pp. 273-283 ◽  
Author(s):  
J W Connell ◽  
J G Smith ◽  
P M Hergenrother
Keyword(s):  
Molecular Weight ◽  
Glass Transition ◽  
Transition Temperature ◽  
Glass Transition Temperature ◽  
Average Molecular Weight ◽  
Adhesive Tape ◽  
High Glass Transition Temperature ◽  
Compressive Properties ◽  
Compression Moulding ◽  
Imide Oligomers

As part of a programme to develop high-performance/high-temperature structural resins for aeronautical applications, imide oligomers containing pendent and terminal phenylethynyl groups were prepared, characterized and the cured resins evaluated as composite matrices. The oligomers were prepared at a calculated number-average molecular weight of 5000 g mol−1 and contained 15–20 mol% pendent phenylethynyl groups. In previous work, an oligomer containing pendent and terminal phenylethynyl groups exhibited a high glass transition temperature (∼313 °C), and laminates therefrom exhibited high compressive properties, but processability, fracture toughness, microcrack resistance and damage tolerance were less than desired. In an attempt to improve these deficiencies, modifications in the oligomeric backbone involving the incorporation of 1,3-bis(3-aminophenoxy)benzene were investigated as a means of improving processability and toughness without detracting from the high glass transition temperature and high compressive properties. The amide acid oligomeric solutions were prepared in N-methyl-2-pyrrolidinone and were subsequently processed into imide powder, thin films, adhesive tape and carbon fibre prepreg. Neat resin plaques were fabricated from imide powder by compression moulding. The maximum processing pressure was 1.4 MPa and the cure temperature ranged from 350 to 371 °C for 1 h for the mouldings, adhesives, films and composites. The properties of the 1,3-bis(3-aminophenoxy)benzene modified cured imide oligomers containing pendent and terminal phenylethynyl groups are compared with those of previously prepared oligomers containing pendent and terminal phenylethynyl groups of similar composition and molecular weight.

All-atomistic molecular dynamics study of the glass transition of amorphous polymers

2021 ◽  
Author(s):  
Zhiye Tang ◽  
Susumu Okazaki
Keyword(s):  
Molecular Dynamics ◽  
Glass Transition ◽  
Spatial Scale ◽  
Degrees Of Freedom ◽  
Main Chain ◽  
Polymer Materials ◽  
Coarse Grained ◽  
Mode Analysis ◽  
Radius Of Gyration ◽  
Chemical Structures

Glass transition is an important phenomenon of polymer materials and it has been intensively studied over the past a few decades. However, the influencing factors arising from the chemical structures of the polymers are often ignored due to a continuous or coarse-grained description of the polymer. Here, we approached this phenomenon using all-atomistic molecular dynamics (MD) simulations and two conventionally used polymer materials, polycarbonate (PC) and poly-(methyl methacrylate) (PMMA). We reproduced the glass transition temperatures (Tg) of the two materials reasonably well. Then we characterized and investigated the glass transition process by looking at the changes of potential energy, dihedral transition, and thermal fluctuation of the individual degrees of freedom in the systems, over the entire temperature range of glass transition. As previously reported, the dihedral angles stop their conformational changes gradually at the Tg, especially for the main chain dihedrals, and sidechain rotations immediately rooting from the main chain. The volumetric change during the temperature decrease is confirmed to be because of conformational adjustment, probably due to the tendency of chain stretching for the maintenance of the radius of gyration, and the loss of thermal energy. The strength of motions of single degrees of freedom and polymer chains, and overall slow motions obtained by normal mode analysis (NMA) shows that different motions at different spatial scale may gradually stop at distinct temperature in the MD simulation temporal and spatial scales. Presumably, the small spatial scale do not contribute to the glass transition at the experimental scale since the timescale is much longer than their relaxation time.

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