Self-restoring polyurethane-based polymer and preparation method therefor
A self-restoring polyurethane-based polymer obtained by polymerization of a composition containing an aromatic disulfide diol represented by Chemical Formula, HO—Ar 1 —S—S—Ar 2 —OH, an alicyclic polyisocyanate, and a polyol. Ar 1 and Ar 2 each are independently a substituted or unsubstituted C 6 -C 30 arylene group. The composition satisfies Equation, 0.1≤M [disulfide] /M [OH] . M [disulfide] is a total mole number of the aromatic disulfide diol in the composition, and M [OH] is a total mole number of the aromatic disulfide diol and the polyol in the composition.
1. A self-restoring polyurethane-based polymer obtained by polymerization of a composition containing an aromatic disulfide diol represented by Chemical Formula 1 below and comprising bis (4-hydroxyphenyl) disulfide, an alicyclic polyisocyanate comprising isophorone diisocyanate (IPDI), and a polyol, wherein the self-restoring polyurethane-based polymer has a self-restoring polyurethane rate of 50% or more at a temperature of 25° C.,
HO—Ar 1 —S—S—Ar 2 —OH [Chemical Formula 1]
wherein Ar 1 and Ar 2 each are independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.
2. The self-restoring polyurethane-based polymer of claim 1 , wherein the alicyclic polyisocyanate further comprises any one or two or more selected from the group consisting of 4,4′-dicyclohexylmethanediisocyanate, cyclohexylenediisocyanate, methylcyclohexylenediisocyanate, bis(2-isocyanatoethyl)-4-dicyclohexene-1,2-dicarboxylate and 2,5-norbornanediisocyanate and 2,6-norbornanediisocyanate.
3. The self-restoring polyurethane-based polymer of claim 1 , wherein the composition satisfies Equation 1 below,
0.1 ≤M [disulfide] /M [OH] [Equation 1]
wherein M [disulfide] is a total mole number of the aromatic disulfide diol in the composition, and M [OH] is a total mole number of the aromatic disulfide diol and the polyol in the composition.
4. The self-restoring polyurethane-based polymer of claim 1 , wherein the self-restoring polyurethane-based polymer satisfies a toughness restoring rate of Equation 2 below,
50≤ T 1 /T 0 ×100 [Equation 2]
wherein, T 0 is a toughness (MJ/m 3 ) of the self-restoring polyurethane-based polymer before cutting, and T 1 is a toughness (MJ/m 3 ) of the self-restoring polyurethane-based polymer obtained after cutting and re-conjugating at 25° C. for 2 hours.
5. The self-restoring polyurethane-based polymer of claim 1 , wherein the composition further comprises any one or two or more selected from aliphatic polyisocyanates and aromatic polyisocyanates.
6. The self-restoring polyurethane-based polymer of claim 5 , wherein the composition satisfies Equation 3 below,
0.15≤ M [cycloaliphatic] /M [NCO] ≤1 [Equation 3]
wherein M [cycloaliphatic] is a total mole number of the alicyclic polyisocyanate in the composition, and M [NCO] is a total mole number of the polyisocyanate-based compound in the composition.
7. A preparation method for a self-restoring polyurethane-based polymer, comprising polymerizing a composition containing an aromatic disulfide diol represented by Chemical Formula 1 below and comprising bis (4-hydroxyphenyl) disulfine, an alicyclic polyisocyanate comprising isophoronediisoyanate (IPDI), and a polyol,
wherein the self-restoring polyurethane-based polymer has a self-restoring polyurethane rate of 50% or more at a temperature of 25° C.,
HO—Ar 1 —S—S—Ar 2 —OH [Chemical Formula 1]
wherein Ar 1 and Ar 2 each are independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.
8. A self-restoring polyurethane-based coating film comprising the self-restoring polyurethane-based polymer of claim 1 .
9. The self-restoring polyurethane-based polymer of claim 1 , wherein the composition further comprises dibutyltin dilaurate.
10. The preparation method of claim 7 , wherein the composition further comprises dibutyltin dilaurate.