Exploration of the transition temperatures and crystal structure of highly crystalline poly(1,3-cyclohexadiene): An experimental and computational investigation

Bohdan Schatschneider, Robert Timothy Mathers, Richard H. Gee, Nichole M. Wonderling

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Experimental determination of transition temperatures for highly crystalline polymers such as poly-1,3-cyclohexadiene (PCHD) can be difficult due to reduced solubility and thermalization processes which occur during data acquisition. In order to facilitate further understanding of these processes for PCHD, density functional theory (DFT) and molecular dynamics (MD) were used in conjunction with differential scanning calorimetry (DSC) and powder X-ray diffraction (XRD) to explore the oligomer microstructures, the crystal structure, and the temperature dependence of the specific volume (1/ρ). DFT geometry minimizations on isolated oligomers were used to identify the lowest energy confirmer; revealing that alternating R,R and S,S chiral bonds between monomer units afford the lowest energy structure. MD simulations of crystalline PCHD were constructed so as to replicate the experimental XRD pattern of crystalline PCHD, with the best fit producing a monoclinic crystal structure. The temperature dependence of the specific volume derived from MD simulations provided insight into the glass/vitrification (Tg) and melting (Tm) transition temperatures. Comparison of the simulation transition temperatures with differential scanning calorimetry data of PCHD polymerized with Ni(acac)2/MAO shows good agreement and solidifies the fidelity of the newly defined PCHD crystalline structure.

Original languageEnglish (US)
Pages (from-to)6085-6090
Number of pages6
JournalPolymer
Volume55
Issue number23
DOIs
StatePublished - Nov 5 2014

Fingerprint

Superconducting transition temperature
Crystal structure
Crystalline materials
Molecular dynamics
Oligomers
Density (specific gravity)
Density functional theory
Differential scanning calorimetry
Vitrification
Computer simulation
X ray powder diffraction
Diffraction patterns
Melting point
Data acquisition
Solubility
Monomers
Monoamine Oxidase
X ray diffraction
Glass
Temperature

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics

Cite this

@article{3133a2cd9f3b49448d8d60dd42cd2131,
title = "Exploration of the transition temperatures and crystal structure of highly crystalline poly(1,3-cyclohexadiene): An experimental and computational investigation",
abstract = "Experimental determination of transition temperatures for highly crystalline polymers such as poly-1,3-cyclohexadiene (PCHD) can be difficult due to reduced solubility and thermalization processes which occur during data acquisition. In order to facilitate further understanding of these processes for PCHD, density functional theory (DFT) and molecular dynamics (MD) were used in conjunction with differential scanning calorimetry (DSC) and powder X-ray diffraction (XRD) to explore the oligomer microstructures, the crystal structure, and the temperature dependence of the specific volume (1/ρ). DFT geometry minimizations on isolated oligomers were used to identify the lowest energy confirmer; revealing that alternating R,R and S,S chiral bonds between monomer units afford the lowest energy structure. MD simulations of crystalline PCHD were constructed so as to replicate the experimental XRD pattern of crystalline PCHD, with the best fit producing a monoclinic crystal structure. The temperature dependence of the specific volume derived from MD simulations provided insight into the glass/vitrification (Tg) and melting (Tm) transition temperatures. Comparison of the simulation transition temperatures with differential scanning calorimetry data of PCHD polymerized with Ni(acac)2/MAO shows good agreement and solidifies the fidelity of the newly defined PCHD crystalline structure.",
author = "Bohdan Schatschneider and Mathers, {Robert Timothy} and Gee, {Richard H.} and Wonderling, {Nichole M.}",
year = "2014",
month = "11",
day = "5",
doi = "10.1016/j.polymer.2014.09.055",
language = "English (US)",
volume = "55",
pages = "6085--6090",
journal = "Polymer",
issn = "0032-3861",
publisher = "Elsevier BV",
number = "23",

}

TY - JOUR

T1 - Exploration of the transition temperatures and crystal structure of highly crystalline poly(1,3-cyclohexadiene)

T2 - An experimental and computational investigation

AU - Schatschneider, Bohdan

AU - Mathers, Robert Timothy

AU - Gee, Richard H.

AU - Wonderling, Nichole M.

PY - 2014/11/5

Y1 - 2014/11/5

N2 - Experimental determination of transition temperatures for highly crystalline polymers such as poly-1,3-cyclohexadiene (PCHD) can be difficult due to reduced solubility and thermalization processes which occur during data acquisition. In order to facilitate further understanding of these processes for PCHD, density functional theory (DFT) and molecular dynamics (MD) were used in conjunction with differential scanning calorimetry (DSC) and powder X-ray diffraction (XRD) to explore the oligomer microstructures, the crystal structure, and the temperature dependence of the specific volume (1/ρ). DFT geometry minimizations on isolated oligomers were used to identify the lowest energy confirmer; revealing that alternating R,R and S,S chiral bonds between monomer units afford the lowest energy structure. MD simulations of crystalline PCHD were constructed so as to replicate the experimental XRD pattern of crystalline PCHD, with the best fit producing a monoclinic crystal structure. The temperature dependence of the specific volume derived from MD simulations provided insight into the glass/vitrification (Tg) and melting (Tm) transition temperatures. Comparison of the simulation transition temperatures with differential scanning calorimetry data of PCHD polymerized with Ni(acac)2/MAO shows good agreement and solidifies the fidelity of the newly defined PCHD crystalline structure.

AB - Experimental determination of transition temperatures for highly crystalline polymers such as poly-1,3-cyclohexadiene (PCHD) can be difficult due to reduced solubility and thermalization processes which occur during data acquisition. In order to facilitate further understanding of these processes for PCHD, density functional theory (DFT) and molecular dynamics (MD) were used in conjunction with differential scanning calorimetry (DSC) and powder X-ray diffraction (XRD) to explore the oligomer microstructures, the crystal structure, and the temperature dependence of the specific volume (1/ρ). DFT geometry minimizations on isolated oligomers were used to identify the lowest energy confirmer; revealing that alternating R,R and S,S chiral bonds between monomer units afford the lowest energy structure. MD simulations of crystalline PCHD were constructed so as to replicate the experimental XRD pattern of crystalline PCHD, with the best fit producing a monoclinic crystal structure. The temperature dependence of the specific volume derived from MD simulations provided insight into the glass/vitrification (Tg) and melting (Tm) transition temperatures. Comparison of the simulation transition temperatures with differential scanning calorimetry data of PCHD polymerized with Ni(acac)2/MAO shows good agreement and solidifies the fidelity of the newly defined PCHD crystalline structure.

UR - http://www.scopus.com/inward/record.url?scp=84908461384&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84908461384&partnerID=8YFLogxK

U2 - 10.1016/j.polymer.2014.09.055

DO - 10.1016/j.polymer.2014.09.055

M3 - Article

AN - SCOPUS:84908461384

VL - 55

SP - 6085

EP - 6090

JO - Polymer

JF - Polymer

SN - 0032-3861

IS - 23

ER -