# US 11,299,578 B2 · Self-restoring polyurethane-based polymer and preparation method therefor

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- Number: US 11,299,578 B2
- Document ID: US11299578B2
- Status: Granted
- Kind: B2
- Application number: 16/618,582
- Filed: 2018-07-11
- Published: 2020-05-21
- Granted: 2022-04-12
- Earliest claimed: 2017-07-12
- Assignees: Korea Research Institute of Chemical Technology
- Applicants: Korea Research Institute of Chemical Technology
- Inventors: Sung Yeon Hwang; Jeyoung Park; Dong Yeop Oh; Jong Geon Jegal; Seon Mi Kim; Hyeon Yeol Jeon
- Web page: https://patentgrep.com/patent/US11299578B2

## CPC

- C08G 18/3868: {the sulfur atom belonging to a sulfide group}
- C08G 18/10: Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G 18/246: {containing also tin-carbon bonds}
- C08G 18/4825: {Polyethers containing two hydroxy groups (C08G18/4833 - C08G18/5096 take precedence)}
- C08G 18/4854: {Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group}
- C08G 18/6666: {Compounds of group C08G18/48 or C08G18/52}
- C08G 18/722: {Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates}
- C08G 18/73: acyclic
- C08G 18/755: {and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate}
- C08J 5/18: Manufacture of films or sheets
- C09D 175/08: from polyethers
- C08J 2375/04: Polyurethanes
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## Abstract

A self-restoring polyurethane-based polymer obtained by polymerization of a composition containing an aromatic disulfide diol represented by Chemical Formula, HO—Ar1—S—S—Ar2—OH, an alicyclic polyisocyanate, and a polyol. Ar1 and Ar2 each are independently a substituted or unsubstituted C6-C30 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.

## Claims

### Claim 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—Ar1—S—S—Ar2—OH [Chemical Formula 1]
wherein Ar1 and Ar2 each are independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

### Claim 2 (depends on 1)

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.

### Claim 3 (depends on 1)

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.

### Claim 4 (depends on 1)

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≤T1/T0×100 [Equation 2]
wherein, T0 is a toughness (MJ/m3) of the self-restoring polyurethane-based polymer before cutting, and T1 is a toughness (MJ/m3) of the self-restoring polyurethane-based polymer obtained after cutting and re-conjugating at 25° C. for 2 hours.

### Claim 5 (depends on 1)

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.

### Claim 6 (depends on 5)

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.

### Claim 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—Ar1—S—S—Ar2—OH [Chemical Formula 1]
wherein Ar1 and Ar2 each are independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

### Claim 8 (depends on 1)

A self-restoring polyurethane-based coating film comprising the self-restoring polyurethane-based polymer of claim 1.

### Claim 9 (depends on 1)

The self-restoring polyurethane-based polymer of claim 1, wherein the composition further comprises dibutyltin dilaurate.

### Claim 10 (depends on 7)

The preparation method of claim 7, wherein the composition further comprises dibutyltin dilaurate.