# US 10,370,561 B2 · Urethane/urea-containing bis(alkenyl) ethers, prepolymers prepared using urethane/urea-containing bis(alkenyl) ethers, and uses thereof

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- Number: US 10,370,561 B2
- Document ID: US10370561B2
- Status: Granted
- Kind: B2
- Application number: 15/194,607
- Filed: 2016-06-28
- Published: 2017-12-28
- Granted: 2019-08-06
- Earliest claimed: 2016-06-28
- Assignees: PRC-DeSoto International, Inc.
- Applicants: PRC-DeSoto International, Inc.
- Inventors: Weibin Cui; Renhe Lin
- Web page: https://patentgrep.com/patent/US10370561B2

## CPC

- C09D 181/02: Polythioethers; Polythioether-ethers
- C08G 18/6715: {Unsaturated monofunctional alcohols or amines}
- 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}
- C08G 59/00: Polycondensates containing more than one epoxy group per molecule (low-molecular-weight polyepoxy compounds C07); Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G 75/045: from mercapto compounds and unsaturated compounds
- C08K 3/26: Carbonates; Bicarbonates
- C08L 81/02: Polythioethers; Polythioether-ethers
- C09K 3/1012: {Sulfur-containing polymers, e.g. polysulfides}
- C09K 3/1021: {Polyurethanes or derivatives thereof}
- C08G 2190/00: Compositions for sealing or packing joints
- 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
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

Urethane/urea-containing bis(alkenyl) ethers can be incorporated into the backbone of polythioether prepolymers and can be used as curing agents in thiol-terminated polythioether prepolymer compositions. Cured sealants prepared using compositions containing urethane/urea-containing bis(alkenyl) ether-containing polythioether prepolymers and/or urethane/urea-containing bis(alkenyl) ether curing agents exhibit improved physical properties suitable for use in aerospace sealant applications.

## Claims

### Claim 1

A urethane/urea-containing bis(alkenyl) ether of Formula (2), a urethane/urea-containing bis(alkenyl) ether of Formula (2c), or a combination thereof:
CH2═CH—O—R5—Y′—C(═O)—NH—R4—NH—C(═O)—Y′—R5—O—CH═CH2 (2)
{CH2═CH—O—R5—Y′—C(═O)—NH—R4—NH—C(═O)—Y′—R5—O—(CH2)2—V′—}zB (2c)
wherein,
each Y′ independently comprises —NH— or —O—;
R4 comprises a core of a diisocyanate;
each R5 independently comprises C1-10 alkanediyl, C5-10 cycloalkanediyl, or C6-20 cycloalkane-alkanediyl;
B comprises a core of a z-valent polyfunctionalizing agent B(—V)z, wherein,
z is an integer from 3 to 6; and
each —V is independently a moiety comprising a terminal group reactive with an alkenyl group; and
each —V′— comprises a moiety derived from the reaction of —V with an alkenyl group.

### Claim 2 (depends on 1)

The urethane/urea-containing bis(alkenyl) ether of claim 1, wherein,
R4 comprises a core of an aliphatic diisocyanate; and
each R5 independently comprises C1-5 alkanediyl.

### Claim 3 (depends on 1)

A composition comprising the urethane/urea-containing bis(alkenyl) ether of claim 1.

### Claim 4 (depends on 3)

The composition of claim 3, further comprising a thiol-terminated sulfur-containing prepolymer.

### Claim 5 (depends on 3)

A part sealed with the composition of claim 3.

### Claim 6 (depends on 3)

A method of sealing a part, comprising:
applying the composition of claim 3 to a part; and
curing the applied composition to seal the part.

### Claim 7

A polythioether prepolymer comprising a moiety of Formula (1):
—S—R1—[—S-A-S—R1—]s—S— (1)
wherein,
s is an integer from 1 to 60;
each R1 comprises C2-10 alkanediyl, C6-8 cycloalkanediyl, C6-10 alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, or —[(—CHR—)p—X—]q—(—CHR—)r—, wherein:
each p is independently an integer from 2 to 6;
q is an integer from 1 to 5;
r is an integer from 2 to 10;
each R is independently selected from hydrogen and methyl; and
each X is independently selected from —O—, —S—, and —NR5—, wherein R5 is selected from hydrogen and methyl;
each A independently comprises a moiety of Formula (2a) or a moiety of Formula (3a):
—(CH2)2—O—R5—Y′—C(═O)—NH—R4—NH—C(═O)—Y′—R5—O—(CH2)2— (2a)
—(CH2)2—O—(R2—O)m—(CH2)2— (3a)
wherein,
m is an integer from 1 to 50;
each Y′ is independently selected from —O— and —NH—;
each R2 comprises C2-6 n-alkanediyl, C3-6 branched alkanediyl, C6-8 cycloalkanediyl, C6-10 alkanecycloalkanediyl, or —[(—CH2—)p—O—]q—(—CH2—)r—, wherein,
each p is independently an integer ranging from 2 to 6;
q is an integer from 1 to 5; and
r is an integer from 2 to 10;
R4 comprises a core of a diisocyanate;
each R5 independently comprises C1-10 alkanediyl, C5-10 cycloalkanediyl, or C6-20 cycloalkane-alkanediyl; and
at least one A comprises a moiety of Formula (2a).

### Claim 8 (depends on 7)

The polythioether prepolymer of claim 7, wherein from 1 mol % to 20 mol % of the A moieties comprise moieties of Formula (2a).

### Claim 9 (depends on 7)

The polythioether prepolymer of claim 7, wherein the polythioether prepolymer comprises a terminal group selected from thiol, hydroxyl, isocyanate, alkenyl, epoxy, polyalkoxysilyl, and a Michael acceptor.

### Claim 10 (depends on 7)

The polythioether prepolymer of claim 7, wherein the polythioether prepolymer comprises a difunctional polythioether prepolymer of Formula (1a), a polyfunctional polythioether prepolymer of Formula (1b), or a combination thereof:
R6—S—R1—[—S-A-S—R1—]s—S—R6 (1a)
{R6—S—R1—[—S-A-S—R1—]s—S—V′—}zB (1b)
wherein,
each R6 is hydrogen or comprises a moiety comprising a terminal functional group;
B comprises 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 group.

### Claim 11 (depends on 7)

The polythioether prepolymer of claim 7, wherein the polythioether prepolymer comprises a thiol-terminated polythioether prepolymer of Formula (1c), a thiol-terminated polythioether prepolymer of Formula (1d), or a combination thereof:
HS—R1—[—S-A-S—R1—]s—SH (1c)
{HS—R1—[—S-A-S—R1—]s—S—V′—}zB (1d)
wherein,
B comprises 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 group.

### Claim 12 (depends on 7)

A composition comprising the polythioether prepolymer of claim 7.

### Claim 13 (depends on 12)

The composition of claim 12, wherein the polythioether prepolymer is thiol terminated.

### Claim 14 (depends on 12)

The composition of claim 12, further comprising a polyepoxide.

### Claim 15 (depends on 12)

A part sealed with the composition of claim 12.

### Claim 16 (depends on 12)

A method of sealing a part, comprising:
applying the composition of claim 12 to a part; and
curing the applied composition to seal the part.

### Claim 17

A urethane/urea-containing bis(alkenyl) ether comprising reaction products of reactants comprising:
a diisocyanate; and
a hydroxyl vinyl ether, an amino vinyl ether, or a combination thereof.

### Claim 18 (depends on 17)

The urethane/urea-containing bis(alkenyl) ether of claim 17, wherein,
the diisocyanate has the structure of Formula (10):
O═C═N—R4—N═C═O (10)
wherein R4 comprises a core of a diisocyanate; and
the hydroxyl vinyl ether and the amino vinyl ether has the structure of Formula (11):
CH2═CH—O—R5—Y (11)
wherein,
Y is —OH or —NH2; and
R5 comprises C1-10 alkanediyl, C5-10 cycloalkanediyl, or C6-20 cycloalkane-alkanediyl.

### Claim 19

A polythioether prepolymer comprising reaction products of reactants comprising:
(a) a polythiol comprising a dithiol of Formula (6):
HS—R1—SH (6)
wherein,
R1 comprises C2-10 alkanediyl, C6-8 cycloalkanediyl, C6-10 alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, or —[(—CHR—)p—X—]q—(—CHR—)r—, wherein:
each p is independently an integer from 2 to 6;
q is an integer from 1 to 5;
r is an integer from 2 to 10;
each R 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;
(b) a urethane/urea-containing bis(alkenyl) ether of Formula (2):
CH2═CH—O—R5—Y′—C(═O)—NH—R4—NH—C(═O)—Y′—R5—O—CH═CH2 (2)
wherein,
each Y′ independently comprises —NH— or —O—;
R4 comprises a core of a diisocyanate; and
each R5 independently comprises C1-10 alkanediyl, C5-10 cycloalkanediyl, or C6-20 cycloalkane-alkanediyl; and
(c) a divinyl ether of Formula (3):
CH2═CH—O—(—R2—O—)m—CH═CH2 (3)
wherein,
m is an integer from 0 to 50; and
each R2 independently comprises C2-6 n-alkanediyl, C3-6 branched alkanediyl, C6-8 cycloalkanediyl, C6-10 alkanecycloalkanediyl, or —[(—CH2—)p—O—]q—(—CH2—)r—, wherein,
each p is independently an integer ranging from 2 to 6;
q is an integer from 1 to 5; and
r is an integer from 2 to 10.

### Claim 20 (depends on 19)

The polythioether prepolymer of claim 19, wherein the reactants further comprise a polyfunctionalizing agent of Formula (9):
B(—V)z (9)
wherein,
B comprises a core of a z-valent polyfunctionalizing agent B(—V)z;
z is an integer from 3 to 6; and
each —V is independently a moiety comprising a terminal thiol group or a terminal alkenyl group.