TY - JOUR
T1 - Partial specific volumes of methylsuccinates and poly(itaconate)s
AU - Hernández-Fuentes, I.
AU - Horta, A.
AU - Gargallo, L.
AU - Abradelo, C.
AU - Yazdani-Pedram, M.
AU - Radić, D.
PY - 1988
Y1 - 1988
N2 - 2-Methylsuccinates are structural analogues of the repeat unit in poly(itaconate)s. Partial specific volumes (ν20) of monomethyl and dibenzyl 2-methylsuccinates and the respective poly(itaconate)s have been determined in several solvents. ν̄20 of the monomethyl species depend on the solvent. Monomethyl 2-methylsuccinate has the same value in dioxane as in bulk. On going from dioxane, to MeOH, to H2O, ν20 decreases progressively. Dipolar interactions, hydrogen bonds (estimated as one per molecule), and dissociation of COOH (minimal effect) are discussed. Poly(monomethyl itaconate) (PMMeI) is much denser than the corresponding 2-methylsuccinate. Also, the macromolecule has a much lower ν̄2 in MeOH than in H2O. In H2O PMMeI has practically the same ν20 as poly(methacrylic acid) (PMA). But hydrophobicity of the α-group (-CH2-COO•CH3) seems low, making PMMeI more akin to poly(acrylic acid) than to PMA. Additivity of group contributions to the molar volume are used to calculate ν̄20. This calculation succeeds in predicting the correct order of ν̄20 in H2O and MeOH both for the 2-methylsuccinate and for the poly(itaconate) (using French and Criss method, adapted here for its application also to polymers). Dibenzyl 2-methylsuccinate in dioxane or toluene has practically the same ν̄20 as bulk dimethyl succinate (larger hydrocarbon groups in the molecule have no influence on ν̄20). Poly(dibenzy itaconate) in dioxane is denser (covalent linking along the chain). Its ν̄20 is predicted accurately by group contributions from rubbery polymers.
AB - 2-Methylsuccinates are structural analogues of the repeat unit in poly(itaconate)s. Partial specific volumes (ν20) of monomethyl and dibenzyl 2-methylsuccinates and the respective poly(itaconate)s have been determined in several solvents. ν̄20 of the monomethyl species depend on the solvent. Monomethyl 2-methylsuccinate has the same value in dioxane as in bulk. On going from dioxane, to MeOH, to H2O, ν20 decreases progressively. Dipolar interactions, hydrogen bonds (estimated as one per molecule), and dissociation of COOH (minimal effect) are discussed. Poly(monomethyl itaconate) (PMMeI) is much denser than the corresponding 2-methylsuccinate. Also, the macromolecule has a much lower ν̄2 in MeOH than in H2O. In H2O PMMeI has practically the same ν20 as poly(methacrylic acid) (PMA). But hydrophobicity of the α-group (-CH2-COO•CH3) seems low, making PMMeI more akin to poly(acrylic acid) than to PMA. Additivity of group contributions to the molar volume are used to calculate ν̄20. This calculation succeeds in predicting the correct order of ν̄20 in H2O and MeOH both for the 2-methylsuccinate and for the poly(itaconate) (using French and Criss method, adapted here for its application also to polymers). Dibenzyl 2-methylsuccinate in dioxane or toluene has practically the same ν̄20 as bulk dimethyl succinate (larger hydrocarbon groups in the molecule have no influence on ν̄20). Poly(dibenzy itaconate) in dioxane is denser (covalent linking along the chain). Its ν̄20 is predicted accurately by group contributions from rubbery polymers.
UR - https://www.scopus.com/pages/publications/28244457432
U2 - 10.1021/j100321a051
DO - 10.1021/j100321a051
M3 - Article
AN - SCOPUS:28244457432
SN - 0022-3654
VL - 92
SP - 2974
EP - 2978
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
IS - 10
ER -