Mechanisms of molecular interactions in polybase-polyacid complex formed by copolymers of N,N-dimethylaminoethylmethacrylate with alkylmethacrylates and methacrylic acid with ethylacrylate

Mechanisms of molecular interaction in the blends of a polybase, a copolymer of N,N‐dimethylaminoethylmethacrylate with methylmethacrylate and butylmethacrylate (PDMAEMA–MMA/BMA), with a polyacid, a copolymer of methacrylic acid with ethylacrylate (PMAA‐co‐EA), and plasticizer, triethylcitrate (TEC)...

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Published in:	Journal of applied polymer science Vol. 112; no. 3; pp. 1142 - 1165
Main Authors:	Feldstein, Mikhail M., Kiseleva, Tatiana I., Bondarenko, Galina N., Kostina, Julia V., Singh, Parminder, Cleary, Gary W.
Format:	Journal Article
Language:	English
Published:	Hoboken Wiley Subscription Services, Inc., A Wiley Company 05-05-2009 Wiley
Subjects:	complex structure and energy hydrogen bonding ionic bonding polyelectrolyte complexes polymer blends
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Abstract	Mechanisms of molecular interaction in the blends of a polybase, a copolymer of N,N‐dimethylaminoethylmethacrylate with methylmethacrylate and butylmethacrylate (PDMAEMA–MMA/BMA), with a polyacid, a copolymer of methacrylic acid with ethylacrylate (PMAA‐co‐EA), and plasticizer, triethylcitrate (TEC), have been investigated with FTIR Spectroscopy and potentiometry. To evaluate the strengths of hydrogen and ionic bonds in the polyelectrolyte complexes, quantum‐chemical calculations were performed. According to this analysis, the energy of ionic and hydrogen bonding diminishes in the order: multi‐component complexes involving protonated aminogroup of DMAEMA (ammonium cation) in the presence of chlorine counterion with ionized or unchanged carboxyl groups and water molecules (690–520 kJ/mol) > ternary H‐bonded acid‐base complexes associated with molecule of water (520–420 kJ/mol) > binary ionic complex of carboxylate anion and ammonium cation (404 kJ/mol) > H‐bonded complex of carboxylate and ammonium ions (257 kJ/mol) > binary H‐bonded complex of uncharged carboxyl group with ammonium cation (114 kJ/mol) > ternary H‐bonded complex of uncharged carboxyl group, aminogroup and water molecule (43 kJ/mol) > binary H‐bonded complex between nonionized carboxyl and amino groups (26 kJ/mol). Proton‐donating capability of functional groups in the studied polyelectrolyte blends diminishes in the order: HN+(CH3)2 − > HOOC > HO. The proton‐donating capacity can be significantly improved in the presence of Cl− ions, the effect of which may be appreciably inhibited if Na+ cations are available in the blend or solution. Proton‐accepting capability weakens in the order: uncharged aminogroup > carboxylate anion > uncharged carboxyl group > hydroxyl group. The results of quantum chemical calculations facilitate interpretation of FTIR spectra. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009
AbstractList	Mechanisms of molecular interaction in the blends of a polybase, a copolymer of N,N‐dimethylaminoethylmethacrylate with methylmethacrylate and butylmethacrylate (PDMAEMA–MMA/BMA), with a polyacid, a copolymer of methacrylic acid with ethylacrylate (PMAA‐co‐EA), and plasticizer, triethylcitrate (TEC), have been investigated with FTIR Spectroscopy and potentiometry. To evaluate the strengths of hydrogen and ionic bonds in the polyelectrolyte complexes, quantum‐chemical calculations were performed. According to this analysis, the energy of ionic and hydrogen bonding diminishes in the order: multi‐component complexes involving protonated aminogroup of DMAEMA (ammonium cation) in the presence of chlorine counterion with ionized or unchanged carboxyl groups and water molecules (690–520 kJ/mol) > ternary H‐bonded acid‐base complexes associated with molecule of water (520–420 kJ/mol) > binary ionic complex of carboxylate anion and ammonium cation (404 kJ/mol) > H‐bonded complex of carboxylate and ammonium ions (257 kJ/mol) > binary H‐bonded complex of uncharged carboxyl group with ammonium cation (114 kJ/mol) > ternary H‐bonded complex of uncharged carboxyl group, aminogroup and water molecule (43 kJ/mol) > binary H‐bonded complex between nonionized carboxyl and amino groups (26 kJ/mol). Proton‐donating capability of functional groups in the studied polyelectrolyte blends diminishes in the order: HN+(CH3)2 − > HOOC > HO. The proton‐donating capacity can be significantly improved in the presence of Cl− ions, the effect of which may be appreciably inhibited if Na+ cations are available in the blend or solution. Proton‐accepting capability weakens in the order: uncharged aminogroup > carboxylate anion > uncharged carboxyl group > hydroxyl group. The results of quantum chemical calculations facilitate interpretation of FTIR spectra. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 Mechanisms of molecular interaction in the blends of a polybase, a copolymer of N,N-dimethylaminoethylmethacrylate with methylmethacrylate and butylmethacrylate (PDMAEMA-MMA/BMA), with a polyacid, a copolymer of methacrylic acid with ethylacrylate (PMAA-co-EA), and plasticizer, triethylcitrate (TEC), have been investigated with FTIR Spectroscopy and potentiometry. To evaluate the strengths of hydrogen and ionic bonds in the polyelectrolyte complexes, quantum-chemical calculations were performed. According to this analysis, the energy of ionic and hydrogen bonding diminishes in the order: multi-component complexes involving protonated aminogroup of DMAEMA (ammonium cation) in the presence of chlorine counterion with ionized or unchanged carboxyl groups and water molecules (690-520 kJ/mol) > ternary H-bonded acid-base complexes associated with molecule of water (520-420 kJ/mol) > binary ionic complex of carboxylate anion and ammonium cation (404 kJ/mol) > H-bonded complex of carboxylate and ammonium ions (257 kJ/mol) > binary H-bonded complex of uncharged carboxyl group with ammonium cation (114 kJ/mol) > ternary H-bonded complex of uncharged carboxyl group, aminogroup and water molecule (43 kJ/mol) > binary H-bonded complex between nonionized carboxyl and amino groups (26 kJ/mol). Proton-donating capability of functional groups in the studied polyelectrolyte blends diminishes in the order: HN+(CH3)2 - > HOOC > HO. The proton-donating capacity can be significantly improved in the presence of Cl- ions, the effect of which may be appreciably inhibited if Na+ cations are available in the blend or solution. Proton-accepting capability weakens in the order: uncharged aminogroup > carboxylate anion > uncharged carboxyl group > hydroxyl group. The results of quantum chemical calculations facilitate interpretation of FTIR spectra. Mechanisms of molecular interaction in the blends of a polybase, a copolymer of N,N‐dimethylaminoethylmethacrylate with methylmethacrylate and butylmethacrylate (PDMAEMA–MMA/BMA), with a polyacid, a copolymer of methacrylic acid with ethylacrylate (PMAA‐co‐EA), and plasticizer, triethylcitrate (TEC), have been investigated with FTIR Spectroscopy and potentiometry. To evaluate the strengths of hydrogen and ionic bonds in the polyelectrolyte complexes, quantum‐chemical calculations were performed. According to this analysis, the energy of ionic and hydrogen bonding diminishes in the order: multi‐component complexes involving protonated aminogroup of DMAEMA (ammonium cation) in the presence of chlorine counterion with ionized or unchanged carboxyl groups and water molecules (690–520 kJ/mol) > ternary H‐bonded acid‐base complexes associated with molecule of water (520–420 kJ/mol) > binary ionic complex of carboxylate anion and ammonium cation (404 kJ/mol) > H‐bonded complex of carboxylate and ammonium ions (257 kJ/mol) > binary H‐bonded complex of uncharged carboxyl group with ammonium cation (114 kJ/mol) > ternary H‐bonded complex of uncharged carboxyl group, aminogroup and water molecule (43 kJ/mol) > binary H‐bonded complex between nonionized carboxyl and amino groups (26 kJ/mol). Proton‐donating capability of functional groups in the studied polyelectrolyte blends diminishes in the order: HN + (CH 3 ) 2 − > HOOC > HO. The proton‐donating capacity can be significantly improved in the presence of Cl − ions, the effect of which may be appreciably inhibited if Na + cations are available in the blend or solution. Proton‐accepting capability weakens in the order: uncharged aminogroup > carboxylate anion > uncharged carboxyl group > hydroxyl group. The results of quantum chemical calculations facilitate interpretation of FTIR spectra. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009
Author	Kostina, Julia V. Bondarenko, Galina N. Cleary, Gary W. Kiseleva, Tatiana I. Feldstein, Mikhail M. Singh, Parminder
Author_xml	– sequence: 1 givenname: Mikhail M. surname: Feldstein fullname: Feldstein, Mikhail M. email: mfeld@ips.ac.ru organization: Research Group of Polymeric Adhesives, A.V. Topchiev Institute for Petrochemical Synthesis, Russian Academy of Sciences, 119991, Moscow, Russia – sequence: 2 givenname: Tatiana I. surname: Kiseleva fullname: Kiseleva, Tatiana I. organization: Research Group of Polymeric Adhesives, A.V. Topchiev Institute for Petrochemical Synthesis, Russian Academy of Sciences, 119991, Moscow, Russia – sequence: 3 givenname: Galina N. surname: Bondarenko fullname: Bondarenko, Galina N. organization: Research Group of Polymeric Adhesives, A.V. Topchiev Institute for Petrochemical Synthesis, Russian Academy of Sciences, 119991, Moscow, Russia – sequence: 4 givenname: Julia V. surname: Kostina fullname: Kostina, Julia V. organization: Research Group of Polymeric Adhesives, A.V. Topchiev Institute for Petrochemical Synthesis, Russian Academy of Sciences, 119991, Moscow, Russia – sequence: 5 givenname: Parminder surname: Singh fullname: Singh, Parminder organization: Corium International, 235 Constitution Drive, Menlo Park, California 94025 – sequence: 6 givenname: Gary W. surname: Cleary fullname: Cleary, Gary W. organization: Corium International, 235 Constitution Drive, Menlo Park, California 94025
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Snippet	Mechanisms of molecular interaction in the blends of a polybase, a copolymer of N,N‐dimethylaminoethylmethacrylate with methylmethacrylate and... Mechanisms of molecular interaction in the blends of a polybase, a copolymer of N,N-dimethylaminoethylmethacrylate with methylmethacrylate and...
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SubjectTerms	complex structure and energy hydrogen bonding ionic bonding polyelectrolyte complexes polymer blends
Title	Mechanisms of molecular interactions in polybase-polyacid complex formed by copolymers of N,N-dimethylaminoethylmethacrylate with alkylmethacrylates and methacrylic acid with ethylacrylate
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