# US 9,518,197 B2 · Cure-on-demand moisture-curable urethane-containing fuel resistant prepolymers and compositions thereof

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- Number: US 9,518,197 B2
- Document ID: US9518197B2
- Status: Granted
- Kind: B2
- Application number: 14/964,904
- Filed: 2015-12-10
- Published: 2016-03-31
- Granted: 2016-12-13
- Earliest claimed: 2014-03-07
- Assignees: PRC-DeSoto International, Inc.
- Applicants: PRC-DeSoto International, Inc.
- Inventors: Raquel Keledjian; Renhe Lin
- Web page: https://patentgrep.com/patent/US9518197B2

## CPC

- C09D 175/04: Polyurethanes
- C08G 18/10: Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G 18/12: using two or more compounds having active hydrogen in the first polymerisation step
- C08G 18/16: Catalysts (catalysts in general B01J)
- C08G 18/289: {containing silicon}
- C08G 18/307: {Atmospheric humidity}
- C08G 18/3868: {the sulfur atom belonging to a sulfide group}
- C08G 18/3893: {containing silicon}
- C08G 18/52: Polythioethers
- C08G 18/758: {containing two or more cycloaliphatic rings}
- C08G 75/045: from mercapto compounds and unsaturated compounds
- C08G 75/12: Polythioether-ethers (C08G75/0245 takes precedence)
- C08L 75/04: Polyurethanes
- C08L 75/08: from polyethers
- C08L 101/10: containing hydrolysable silane groups
- C09J 175/08: from polyethers
- C08G 2190/00: Compositions for sealing or packing joints
- C08K 9/10: Encapsulated ingredients
- 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)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

Cure-on-demand, moisture-curable, urethane-containing prepolymers having urethanes incorporated into a sulfur-containing prepolymer backbone and compositions thereof for use in sealant applications are disclosed. The cure-on-demand moisture-curable urethane-containing prepolymers are terminated with polyalkoxysilyl groups. The compositions contain a controlled-release moisture cure catalyst. Compositions containing the prepolymers provide cured sealants exhibiting improved tensile strength.

## Claims

### Claim 1

A composition comprising:
(a) a moisture-curable urethane-containing prepolymer comprising a reaction product of reactants comprising:
(i) an isocyanate-terminated urethane-containing adduct comprising the reaction product of reactants comprising:
a hydroxyl-terminated sulfur-containing adduct comprising the reaction product of reactants comprising a hydroxy vinyl ether and a thiol-terminated sulfur-containing prepolymer, wherein the thiol-terminated sulfur-containing prepolymer comprises a thiol-terminated polythioether, a thiol-terminated polysulfide, a thiol-terminated sulfur-containing polyformal, or a combination of any of the foregoing; and
a diisocyanate; and
(ii) a compound comprising:
a group reactive with an isocyanate group; and
at least one polyalkoxysilyl group; and
(b) a controlled release moisture cure catalyst.

### Claim 2 (depends on 1)

The composition of claim 1, wherein the hydroxyl-terminated sulfur-containing adduct comprises a hydroxyl-terminated polythioether adduct of Formula (10a), a hydroxyl-terminated polythioether adduct of Formula (10b), or a combination thereof:
R6—S—R1—[—S—(CH2)s—O—(R2—O)m—(CH2)2—S—R1—]n—S—R6 (10a)
{R6—S—R1—[—S—(CH2)s—O—(R2—O)m—(CH2)2—S—R1—]n—S—V′—}zB (10b)
wherein,
each R1 independently is selected from C2-10 alkanediyl, C6-8 cycloalkanediyl, C6-10 alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, and —[(—CHR3—)p—X—]q—(—CHR3—)r—, wherein,
p is an integer from 2 to 6;
q is an integer from 1 to 5;
r is an integer from 2 to 10;
each R3 is independently selected from hydrogen and methyl; and
each X is independently selected from —O—, —S—, and —NR—, wherein R is selected from hydrogen and methyl;
each R2 is independently selected from C1-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanecycloalkanediyl, and —[(—CHR3—)p—X—]q—(—CHR3—)r—, wherein p, q, r, R3, and X are as defined for R1;
m is an integer from 0 to 50;
n is an integer from 1 to 60; and
s is an integer from 2 to 6;
each R6 is independently selected from —CH2—CH2—O—R13—OH, wherein each R13 is C2-10 alkanediyl; and
B represents a core of a z-valent, polyfunctionalizing agent B(—V)z wherein,
z is an integer from 3 to 6; and
each V is a moiety comprising a terminal group reactive with a thiol group; and
each —V′— is derived from the reaction of —V with a thiol.

### Claim 3 (depends on 1)

The composition of claim 1, wherein the thiol-terminated sulfur-containing prepolymer comprises a thiol-terminated polythioether prepolymer of Formula (6a), a thiol-terminated polythioether prepolymer of Formula (6b), or a combination thereof:
HS—R1—[—S—(CH2)s—O—(R2—O)m—(CH2)2—S—R1—]n—SH (6a)
{HS—R1—[—S—(CH2)s—O—(R2—O)m—(CH2)2—S—R1—]n—S—V′—}zB (6b)
wherein:
each R1 independently is selected from C2-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, and —[(—CHR3—)p—X—]q—(—CHR3—)r—, wherein:
p is an integer from 2 to 6;
q is an integer from 1 to 5;
r is an integer from 2 to 10;
each R3 is independently selected from hydrogen and methyl; and
each X is independently selected from —O—, —S—, and —NR—, wherein R is selected from hydrogen and methyl;
each R2 is independently selected from C1-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanecycloalkanediyl, and —[(—CHR3—)p—X—]q—(—CHR3—)r—, wherein p, q, r, R3, and X are as defined as for R1;
m is an integer from 0 to 50;
n is an integer from 1 to 60;
s is an integer from 2 to 6;
B represents a core of a z-valent, polyfunctionalizing agent B(—V)z wherein:
z is an integer from 3 to 6; and
each V is a group comprising a terminal group reactive with a thiol group; and
each —V′— is derived from the reaction of —V with a thiol.

### Claim 4 (depends on 1)

The composition of claim 1, wherein the isocyanate-terminated urethane-containing adduct comprises an isocyanate-terminated urethane-containing polythioether, an isocyanate-terminated urethane-containing polysulfide, an isocyanate-terminated urethane-containing sulfur-containing polyformal, or a combination of any of the foregoing.

### Claim 5 (depends on 1)

The composition of claim 1, wherein the compound (ii) comprises an aminosilane.

### Claim 6 (depends on 5)

The composition of claim 5, wherein the aminosilane comprises (3-aminopropyl)triethoxysilane.

### Claim 7 (depends on 1)

The composition of claim 1, comprising dimethoxy(methyl)(vinyl)silane.

### Claim 8 (depends on 1)

The composition of claim 1, formulated as a sealant.

### Claim 9 (depends on 8)

A cured sealant, prepared from the composition of claim 8.

### Claim 10 (depends on 8)

A part sealed with the composition of claim 8.

### Claim 11 (depends on 8)

A method of sealing a surface, comprising:
applying the composition of claim 8 to at least a portion of a surface;
activating the controlled release moisture cure catalyst; and
curing the applied composition to seal the surface.

### Claim 12

A composition comprising:
(a) a moisture-curable urethane-containing prepolymer comprising a moisture-curable urethane-containing prepolymer of Formula (2a), a moisture-curable urethane-containing prepolymer of Formula (2b), or a combination thereof:
R30—C(═O)—NH—R20—NH—C(═O)—[—R60—C(═O)—NH—R20—NH—C(═O)—]w—R60—C(═O)—NH—R20—NH—C(═O)—R30 (2a)
B{—V′—S—R50—S—(CH2)2—O—R13—O—[—C(═O)—NH—R20—NH—C(═O)—R60—]w—C(═O)—NH—R20—NH—C(═O)—R30}z (2b)
wherein,
w is an integer from 1 to 100;
each R13 independently comprises C2-10 alkanediyl;
each R20 independently comprises a core of a diisocyanate;
each R30 independently is a moiety comprising a terminal polyalkoxysilyl group;
each R50 independently comprises a core of a sulfur-containing prepolymer, wherein the sulfur-containing prepolymer comprises a polythioether, a polysulfide, a sulfur-containing polyformal, or a combination of any of the foregoing;
each R60 independently comprises a moiety having the structure of Formula (3):
—O—R13—O—(CH2)2—S—R50—S—(CH2)2—O—R13—O— (3)
B represents a core of a z-valent, polyfunctionalizing agent B(—V)z wherein,
z is an integer from 3 to 6; and
each V is a moiety comprising a terminal group reactive with a thiol group; and
each —V′— is derived from the reaction of —V with a thiol; and
(b) a controlled release moisture cure catalyst.

### Claim 13 (depends on 12)

The composition of claim 12, wherein each R30 comprises a moiety of Formula (4a), a moiety of Formula (4b), or a combination thereof:
—NH(—R9—Si(—R7)x(—OR7)3-x) (4a)
—N(—R9—Si(—R7)x(—OR7)3-x)2 (4b)
wherein,
x is selected from 0, 1, and 2;
each R7 is independently selected from C1-4 alkyl; and
each R9 is independently C1-6 alkanediyl.

### Claim 14 (depends on 12)

The composition of claim 12, wherein each R50 comprises a moiety having the structure of Formula (5):
—R1—[—S—(CH2)s—O—(R2—O)m—(CH2)2—S—R1—]n— (5)
wherein,
each R1 independently is selected from C2-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, and —[(—CHR3—)p—X—]q—(—CHR3—)r—, wherein:
p is an integer from 2 to 6;
q is an integer from 1 to 5;
r is an integer from 2 to 10;
each R3 is independently selected from hydrogen and methyl; and
each X is independently selected from —O—, —S—, and —NR—, wherein R is selected from hydrogen and methyl;
each R2 is independently selected from C1-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanecycloalkanediyl, and —[(—CHR3—)p—X—]q—(—CHR3—)r—, wherein p, q, r, R3, and X are as defined as for R1;
m is an integer from 0 to 50;
n is an integer from 1 to 60; and
s is an integer from 2 to 6.

### Claim 15 (depends on 12)

The composition of claim 12, wherein each R30 is a moiety of Formula (4c):
—NH—(CH2)3—Si(—OCH3)3 (4c).

### Claim 16 (depends on 12)

The composition of claim 12, comprising dimethoxy(methyl)(vinyl)silane.

### Claim 17 (depends on 12)

The composition of claim 12, formulated as a sealant.

### Claim 18 (depends on 17)

A cured sealant prepared from the composition of claim 17.

### Claim 19 (depends on 17)

A part sealed with the composition of claim 17.

### Claim 20 (depends on 17)

A method of sealing a surface, comprising:
applying the composition of claim 17 to at least a portion of a surface;
activating the controlled release moisture cure catalyst; and
curing the applied composition to seal the surface.

### Claim 21 (depends on 2)

The composition of claim 2, wherein
each R1 is —(CH2)2—O—(CH2)2—O—(CH2)2—;
each R2 is —(CH2)2—; and
B(—V)z is triallyl cyanurate.

### Claim 22 (depends on 3)

The composition of claim 3, wherein
each R1 is —(CH2)2—O—(CH2)2—O—(CH2)2—;
each R2 is —(CH2)2—; and
B(—V)z is triallyl cyanurate.

### Claim 23 (depends on 14)

The composition of claim 14, wherein
each R1 is —(CH2)2—O—(CH2)2—O—(CH2)2—;
each R2 is —(CH2)2—; and
B(—V)z is triallyl cyanurate.

### Claim 24 (depends on 23)

The composition of claim 23, wherein the diisocyanate is selected from toluene diisocyanate, polycarbodiimide-modified diphenylmethene diisocyanate, 1,3-bis(6-isocyanatohexyl)-1,3-diazetidine-2,4-dione, isophorone diisocyanate, and 4,4-methylene dicyclohexyl diisocyanate.