Self-restoring polyurethane-based polymer and preparation method therefor

Patent metadata

Field	Value
Publication number	US-11299578-B2
Application number	US-201816618582-A
Country	US
Kind code	B2
Filing date	Jul 11, 2018
Priority date	Jul 12, 2017
Publication date	Apr 12, 2022
Grant date	Apr 12, 2022

Abstract

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.

First claim

The invention claimed is:

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.

Assignees

• Korea Res Inst Chemical Tech

Inventors

• Hwang Sung Yeon
• Park Jeyoung
• Oh Dong Yeop
• Jegal Jong Geon
• Kim Seon Mi
• Jeon Hyeon Yeol

Classifications

• C08G18/246

  containing also tin-carbon bonds · CPC title

• C08J2375/04

  Polyurethanes · CPC title

• C08G18/3868 Primary

  the sulfur atom belonging to a sulfide group · CPC title

• C08G18/73

  acyclic · CPC title

• C08J5/18 Primary

  Manufacture of films or sheets · CPC title