Sulfur-containing poly(alkenyl) ethers, prepolymers incorporating sulfur-containing poly(alkenyl) ethers, and uses thereof

Patent metadata

Field	Value
Publication number	US-11236201-B2
Application number	US-201716347410-A
Country	US
Kind code	B2
Filing date	Nov 3, 2017
Priority date	Nov 4, 2016
Publication date	Feb 1, 2022
Grant date	Feb 1, 2022

Abstract

Sulfur-containing poly(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 sulfur-containing poly(alkenyl) ether-containing polythioether prepolymers and/or sulfur-containing poly(alkenyl) ether curing agents exhibit improved physical properties suitable for use in aerospace sealant applications.

First claim

What is claimed is:

1. A polythioether prepolymer comprising a moiety of Formula (2):
—S—R 1 —[S-A-S—R 1 —] s —S—  (2)

wherein,
s is an integer from 1 to 60;
each R 1 is independently selected from C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, and —[(—CHR—) p —X—] q —(CHR) r —, wherein each R is independently selected from hydrogen and methyl, wherein,
each X is independently selected from —O— and —S—;
each p is independently an integer from 2 to 6;
q is an integer from 1 to 5; and
r is an integer from 2 to 10;

each A is independently selected from a sulfur-containing moiety of Formula (3a), a moiety of Formula (4a), and a moiety derived from an alkenyl-terminated polyfunctionalizing agent, wherein from 10 mol % to 90 mol % of the A moieties comprise a sulfur-containing moiety of Formula (3a):
—(CH 2 ) 2 —O—(CH 2 ) n —Y 1 —R 4 —Y 1 —(CH 2 ) n —O—(CH 2 ) 2 —  (3a)

—(CH 2 ) 2 —O—(R 2 —O) m —(CH 2 ) 2 —  (4a)

wherein,
each n is independently an integer from 1 to 4;
each Y 1 is independently selected from —O— and —S—;
m is an integer from 0 to 50; and
each R 2 is independently selected from C 2-6 n-alkanediyl, C 3-6 branched alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, and

—[(CH 2 ) p —X—] q —(CH 2 ) r —, wherein,
each p is independently an integer from 2 to 6;
q is an integer from 1 to 5; and
r is an integer from 2 to 10;

R 4 is selected from C 2-6 n-alkanediyl, C 3-6 branched alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, and —[(CH 2 ) p —X—] q —(CH 2 ) r —, wherein,
each X is independently selected from —O—, —S—, and —S—S—;
each p is an integer from 2 to 6;
q is an integer from 1 to 5; and
r is an integer from 2 to 10; and

at least one Y 1 is —S—, or R 4 is —[(CH 2 ) p —X—] q —(CH 2 ) r — and at least one X is selected from —S— and —S—S—,

wherein mol % is based on the total moles of A moieties in the prepolymer.

2. The polythioether prepolymer of claim 1 , wherein each A is further independently selected from a moiety derived from a polyalkenyl polyfunctionalizing agent, wherein the moiety has the structure of Formula (1a):
B{—V 1 —} 2 {—V 1 —S—[R 1 —S-A-S—] u —R 1 —SH} z-2   (1a)

wherein,
B is 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 terminal thiol groups; and
each —V 1 — is derived from the reaction of —V with a thiol group.

3. The polythioether prepolymer of claim 1 , wherein,
from 20 mol % to 60 mol % of the A moieties comprise a sulfur-containing moiety of Formula (3a); and
from 40 mol % to 80 mol % of the A moieties comprise a moiety of Formula (4a).

4. The polythioether prepolymer of claim 1 , wherein the polythioether prepolymer comprises a difunctional polythioether prepolymer of Formula (2a):
R 6 —S—R 1 —[S-A-S—R 1 —] s —S—R 6   (2a)

wherein each R 6 is selected from hydrogen and a moiety comprising a terminal functional group.

5. The polythioether prepolymer of claim 4 , wherein each R 6 is selected from hydrogen and a moiety comprising a terminal functional group, wherein the terminal functional group is selected from a thiol, hydroxyl, isocyanate, alkenyl, epoxy, polyalkoxysilyl, amino, and a Michael acceptor.

6. The polythioether prepolymer of claim 1 , wherein the polythioether prepolymer comprises a thiol-terminated polythioether prepolymer of Formula (2c), a thiol-terminated polythioether prepolymer of Formula (2d), or a combination thereof:
HS—R 1 —[S-A-S—R 1 ] s —SH  (2c)

{HS—R 1 —[S-A-S—R 1 —] s —S—V 1 —} z B  (2d)

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 terminal thiol groups; and
each —V 1 — is derived from the reaction of —V with a thiol group.

7. The polythioether prepolymer of claim 1 , wherein the polythioether prepolymer exhibits an onset of solidification at a temperature less than 60° F. (15.5° C.).

8. A polythioether prepolymer comprising reaction products of reactants comprising:
(a) a polythiol comprising a dithiol of Formula (7):
HS—R 1 —SH  (7)

wherein,
R 1 is selected from C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, and

—[—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— and —S—; and

(b) a sulfur-containing bis(alkenyl) ether of Formula (3):
CH 2 ═CH—O—(CH 2 ) n —Y 1 —R 4 —Y 1 —(CH 2 ) n —O—CH═CH 2   (3)

wherein,
each n is independently an integer from 1 to 4;
each Y 1 is independently selected from —O— and —S—; and
R 4 is selected from C 2-6 n-alkanediyl, C 3-6 branched alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, and —[(CH 2 ) p —X—] q —(CH 2 ) r —,

wherein,
each X is independently selected from —O—, —S—, and —S—S—;
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; and
at least one Y 1 is —S—, or R 4 is —[(CH 2 ) p —X—] q —(CH 2 ) r — and at least one X is selected from —S— and —S—S—; and

(c) a divinyl ether of Formula (4):
CH 2 ═CH—O—(—R 2 —O—) m —CH═CH 2   (4)

wherein,
m is an integer from 0 to 50; and
each R 2 is independently selected from C 2-6 n-alkanediyl, C 3-6 branched alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, and

—[(CH 2 ) p —X—] q —(CH 2 ) r —, wherein,
each p is independently an integer from 2 to 6;
q is an integer from 1 to 5; and
r is an integer from 2 to 10;

wherein the reactants comprise from 10 mol % to 90 mol % of the sulfur-containing bis(alkenyl) ether of Formula (3), wherein mol % is based on the total moles of the sulfur-containing bis(alkenyl) ether of Formula (3) and the divinyl ether of Formula (4).

9. The polythioether prepolymer of claim 8 , wherein the reactants further comprise: (d) a polyfunctionalizing agent of Formula (1):
B(—V) z   (1)

wherein,
B is 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, a terminal alkenyl group, or a combination thereof.

10. The polythioether prepolymer of claim 8 , wherein the reactants further comprise a sulfur-containing multifunctional(alkenyl) ether of Formula (10):
{CH 2 ═CH—O—(CH 2 ) n —Y 1 —R 4 —Y 1 —(CH 2 ) n —O—(CH 2 ) 2 —V 1 —} z B  (10)

wherein,
each n is independently an integer from 1 to 4;
each Y 1 is independently selected from —O— and —S—; and
each R 4 is independently selected from C 2-6 n-alkanediyl, C 3-6 branched alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, and [(CH 2 ) p —X—] q —(CH 2 ) r —, wherein,
each X is independently selected from —O—, —S—, and —S—S—;
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;

at least one Y 1 is —S—, or R 4 is —[(CH 2 ) p —X—] q —(CH 2 ) r — and at least one X is selected from —S— and —S—S—;
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 terminal alkenyl group; and

each —V 1 — is derived from the reaction of —V with an alkenyl group.

11. The polythioether prepolymer of claim 8 , wherein the polythioethe

Assignees

• Prc Desoto Int Inc

Inventors

• Cui Weibin
• Lin Renhe

Classifications

• C09K3/1012

  Sulfur-containing polymers, e.g. polysulfides · CPC title

• C08G75/0268

  using disulfides · CPC title

• C09D181/02

  Polythioethers; Polythioether-ethers · CPC title

• C08G75/12

  Polythioether-ethers (C08G75/0245 takes precedence) · CPC title

• C08G75/0209 Primary

  derived from monomers containing one aromatic ring · CPC title