Characterization of Functionalized Side-Chain Liquid Crystal Methacrylates Containing Nonmesogenic Units by Dielectric Spectroscopy

A. Martinez-Felipe, L. Santonja-Blasco, J. D. Badia, C.T. Imrie, A. Ribes-Greus*

*Corresponding author for this work

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

ABSTRACT: The dielectric response of a series of side-chain liquid crystal copolymers, SCLCPs, the poly[6-(4′-methoxyazobenzene-4′-oxy)hexyl methacrylate]-co-poly[methyl methacrylate]s, MeOAzB/MMA copolymers, is presented in the frequency range f = 10−2 to 107 Hz and over the temperature interval T = −150 to 120 °C. The relaxation spectra of these
polymers have been studied in terms of the complex dielectric permittivity (ε′ and ε″) and the dielectric loss tangent, tan(δ). The electric modulus, M*, has been also calculated. It is possible to distinguish two relaxations zones, one at low temperatures (including γ and β relaxations) and another at higher temperatures (including the α and β1 relaxations), all of them reported for liquid crystalline poly(methacrylate)s. The individual relaxations have been analyzed using Havriliak−Negami (HN) functions and the effect of conductivity at high temperatures is subtracted. The thermal activation of the relaxations at low temperatures is studied using the Arrhenius equations as a function of copolymer composition, while the α and β1 relaxations are analyzed using Vogel−Tammann−Fulcher equations. The activation entropy has been also evaluated for all the relaxations through the Eyring equation. The temperature ranges, activation energies, and entropies of the relaxations at low temperatures (γ and β) are similar in the homopolymer and copolymers. However, the introduction of MMA units promotes variations in all the parameters related to the relaxations associated with the motions of the ester groups adjoining the polymer backbone. Specifically, a decrease is observed in the activation entropy values of the β1 relaxation, which suggests that the activation of the local motions of the side groups involves smaller cooperative regions in the copolymers with respect to the homopolymer. This fact may account for the extinction of the smectic behavior, together with the dilution of the anisotropic interactions between the mesogenic units on increasing MMA content. The study of this β1 relaxation can be then applied to anticipate the formation and stability of smectic phases in functionalized SCLCPs, by controlling the local mobility resulting in different mesogenic behavior.
Original languageEnglish
Pages (from-to)8722-8731
Number of pages10
JournalIndustrial & Engineering Chemistry Research
Volume52
Issue number26
Early online date4 Jan 2013
DOIs
Publication statusPublished - Jul 2013

Keywords

  • order-disorder transition
  • polymer electrolytes
  • beta-relaxation
  • ion-transport
  • poly(ethyl methacrylate)
  • mechanical spectroscopy
  • cooperative relaxation
  • temperature-dependence
  • methyl-methacrylate
  • molecular mobility

Cite this

Characterization of Functionalized Side-Chain Liquid Crystal Methacrylates Containing Nonmesogenic Units by Dielectric Spectroscopy. / Martinez-Felipe, A.; Santonja-Blasco, L.; Badia, J. D.; Imrie, C.T.; Ribes-Greus, A.

In: Industrial & Engineering Chemistry Research, Vol. 52, No. 26, 07.2013, p. 8722-8731.

Research output: Contribution to journalArticle

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title = "Characterization of Functionalized Side-Chain Liquid Crystal Methacrylates Containing Nonmesogenic Units by Dielectric Spectroscopy",
abstract = "ABSTRACT: The dielectric response of a series of side-chain liquid crystal copolymers, SCLCPs, the poly[6-(4′-methoxyazobenzene-4′-oxy)hexyl methacrylate]-co-poly[methyl methacrylate]s, MeOAzB/MMA copolymers, is presented in the frequency range f = 10−2 to 107 Hz and over the temperature interval T = −150 to 120 °C. The relaxation spectra of thesepolymers have been studied in terms of the complex dielectric permittivity (ε′ and ε″) and the dielectric loss tangent, tan(δ). The electric modulus, M*, has been also calculated. It is possible to distinguish two relaxations zones, one at low temperatures (including γ and β relaxations) and another at higher temperatures (including the α and β1 relaxations), all of them reported for liquid crystalline poly(methacrylate)s. The individual relaxations have been analyzed using Havriliak−Negami (HN) functions and the effect of conductivity at high temperatures is subtracted. The thermal activation of the relaxations at low temperatures is studied using the Arrhenius equations as a function of copolymer composition, while the α and β1 relaxations are analyzed using Vogel−Tammann−Fulcher equations. The activation entropy has been also evaluated for all the relaxations through the Eyring equation. The temperature ranges, activation energies, and entropies of the relaxations at low temperatures (γ and β) are similar in the homopolymer and copolymers. However, the introduction of MMA units promotes variations in all the parameters related to the relaxations associated with the motions of the ester groups adjoining the polymer backbone. Specifically, a decrease is observed in the activation entropy values of the β1 relaxation, which suggests that the activation of the local motions of the side groups involves smaller cooperative regions in the copolymers with respect to the homopolymer. This fact may account for the extinction of the smectic behavior, together with the dilution of the anisotropic interactions between the mesogenic units on increasing MMA content. The study of this β1 relaxation can be then applied to anticipate the formation and stability of smectic phases in functionalized SCLCPs, by controlling the local mobility resulting in different mesogenic behavior.",
keywords = "order-disorder transition, polymer electrolytes, beta-relaxation, ion-transport, poly(ethyl methacrylate), mechanical spectroscopy, cooperative relaxation, temperature-dependence, methyl-methacrylate, molecular mobility",
author = "A. Martinez-Felipe and L. Santonja-Blasco and Badia, {J. D.} and C.T. Imrie and A. Ribes-Greus",
note = "This paper is meant to be a tribute and recognition to the research activity of Professor Giulio Sarti. The authors would like to thank Dr. Victor Saenz de Juano for his advice during the discussion of the results and also the Spanish Ministry of Science and Innovation, through the Research Projects ENE2007-67584-C03, UPOVCE-3E-013, IT2009-0074, and ENE2011-28735-C02-01 and two FPI and FPU predoctoral grants, and the financial support of the Generalitat Valenciana, through the Grisolia and Forteza programs and the ACOMP/ 2011/189 program. UPV is also thanked for additional support through the PAID 05-09-4331 and PAID-06-11 programs.",
year = "2013",
month = "7",
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volume = "52",
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TY - JOUR

T1 - Characterization of Functionalized Side-Chain Liquid Crystal Methacrylates Containing Nonmesogenic Units by Dielectric Spectroscopy

AU - Martinez-Felipe, A.

AU - Santonja-Blasco, L.

AU - Badia, J. D.

AU - Imrie, C.T.

AU - Ribes-Greus, A.

N1 - This paper is meant to be a tribute and recognition to the research activity of Professor Giulio Sarti. The authors would like to thank Dr. Victor Saenz de Juano for his advice during the discussion of the results and also the Spanish Ministry of Science and Innovation, through the Research Projects ENE2007-67584-C03, UPOVCE-3E-013, IT2009-0074, and ENE2011-28735-C02-01 and two FPI and FPU predoctoral grants, and the financial support of the Generalitat Valenciana, through the Grisolia and Forteza programs and the ACOMP/ 2011/189 program. UPV is also thanked for additional support through the PAID 05-09-4331 and PAID-06-11 programs.

PY - 2013/7

Y1 - 2013/7

N2 - ABSTRACT: The dielectric response of a series of side-chain liquid crystal copolymers, SCLCPs, the poly[6-(4′-methoxyazobenzene-4′-oxy)hexyl methacrylate]-co-poly[methyl methacrylate]s, MeOAzB/MMA copolymers, is presented in the frequency range f = 10−2 to 107 Hz and over the temperature interval T = −150 to 120 °C. The relaxation spectra of thesepolymers have been studied in terms of the complex dielectric permittivity (ε′ and ε″) and the dielectric loss tangent, tan(δ). The electric modulus, M*, has been also calculated. It is possible to distinguish two relaxations zones, one at low temperatures (including γ and β relaxations) and another at higher temperatures (including the α and β1 relaxations), all of them reported for liquid crystalline poly(methacrylate)s. The individual relaxations have been analyzed using Havriliak−Negami (HN) functions and the effect of conductivity at high temperatures is subtracted. The thermal activation of the relaxations at low temperatures is studied using the Arrhenius equations as a function of copolymer composition, while the α and β1 relaxations are analyzed using Vogel−Tammann−Fulcher equations. The activation entropy has been also evaluated for all the relaxations through the Eyring equation. The temperature ranges, activation energies, and entropies of the relaxations at low temperatures (γ and β) are similar in the homopolymer and copolymers. However, the introduction of MMA units promotes variations in all the parameters related to the relaxations associated with the motions of the ester groups adjoining the polymer backbone. Specifically, a decrease is observed in the activation entropy values of the β1 relaxation, which suggests that the activation of the local motions of the side groups involves smaller cooperative regions in the copolymers with respect to the homopolymer. This fact may account for the extinction of the smectic behavior, together with the dilution of the anisotropic interactions between the mesogenic units on increasing MMA content. The study of this β1 relaxation can be then applied to anticipate the formation and stability of smectic phases in functionalized SCLCPs, by controlling the local mobility resulting in different mesogenic behavior.

AB - ABSTRACT: The dielectric response of a series of side-chain liquid crystal copolymers, SCLCPs, the poly[6-(4′-methoxyazobenzene-4′-oxy)hexyl methacrylate]-co-poly[methyl methacrylate]s, MeOAzB/MMA copolymers, is presented in the frequency range f = 10−2 to 107 Hz and over the temperature interval T = −150 to 120 °C. The relaxation spectra of thesepolymers have been studied in terms of the complex dielectric permittivity (ε′ and ε″) and the dielectric loss tangent, tan(δ). The electric modulus, M*, has been also calculated. It is possible to distinguish two relaxations zones, one at low temperatures (including γ and β relaxations) and another at higher temperatures (including the α and β1 relaxations), all of them reported for liquid crystalline poly(methacrylate)s. The individual relaxations have been analyzed using Havriliak−Negami (HN) functions and the effect of conductivity at high temperatures is subtracted. The thermal activation of the relaxations at low temperatures is studied using the Arrhenius equations as a function of copolymer composition, while the α and β1 relaxations are analyzed using Vogel−Tammann−Fulcher equations. The activation entropy has been also evaluated for all the relaxations through the Eyring equation. The temperature ranges, activation energies, and entropies of the relaxations at low temperatures (γ and β) are similar in the homopolymer and copolymers. However, the introduction of MMA units promotes variations in all the parameters related to the relaxations associated with the motions of the ester groups adjoining the polymer backbone. Specifically, a decrease is observed in the activation entropy values of the β1 relaxation, which suggests that the activation of the local motions of the side groups involves smaller cooperative regions in the copolymers with respect to the homopolymer. This fact may account for the extinction of the smectic behavior, together with the dilution of the anisotropic interactions between the mesogenic units on increasing MMA content. The study of this β1 relaxation can be then applied to anticipate the formation and stability of smectic phases in functionalized SCLCPs, by controlling the local mobility resulting in different mesogenic behavior.

KW - order-disorder transition

KW - polymer electrolytes

KW - beta-relaxation

KW - ion-transport

KW - poly(ethyl methacrylate)

KW - mechanical spectroscopy

KW - cooperative relaxation

KW - temperature-dependence

KW - methyl-methacrylate

KW - molecular mobility

U2 - 10.1021/ie3031339

DO - 10.1021/ie3031339

M3 - Article

VL - 52

SP - 8722

EP - 8731

JO - Industrial & Engineering Chemistry Research

JF - Industrial & Engineering Chemistry Research

SN - 0888-5885

IS - 26

ER -