Cross-linked organic polymers for use as elastomers in high temperature applications
Methods are disclosed to prepare elastomeric materials by providing aromatic polymer(s) which is/are non-elastomeric at room temperature; cross-linking the aromatic polymer using a cross-linking compound to form a cross-linked aromatic polymer which is substantially cured; and heating the cross-linked aromatic polymer to a temperature at or above a glass transition temperature of the cross-linked aromatic polymer. Materials formed thereby and end products are also described which may be formed using the aromatic polymer cross-linking techniques to develop strong elastomeric materials for high temperature and/or harsh condition end applications.
1. A method of preparing an elastomeric material, comprising
(a) providing an aromatic polymer which is non-elastomeric at room temperature;
(b) cross-linking the aromatic polymer using a cross-linking compound to form a cross-linked aromatic polymer that is substantially cured, wherein the cross-linking compound has a structure according to formula (II):
wherein A is an arene moiety having a molecular weight of less than 10,000 g/mol, R 1 is selected from a group consisting of hydroxide (—OH), amine (—NH 2 ), halide, ether, ester, or amide, and x is about 2.0 to about 6.0; and
(c) heating the cross-linked aromatic polymer to a temperature at or above a glass transition temperature of the cross-linked aromatic polymer.
2. The method of preparing an elastomeric material according to claim 1 , wherein, in step (b), the aromatic polymer is at least about 80% cured.
3. The method of preparing an elastomeric material according to claim 2 , wherein the aromatic polymer is at least about 90% cured.
4. The method of preparing an elastomeric material according to claim 3 , wherein the aromatic polymer is fully cured.
5. The method of preparing an elastomeric material according to claim 1 , wherein the aromatic polymer is selected from the group consisting of poly(arylene ether)s, polysulfones, polyethersulfones, polyarylene sulfides, polyimides, polyamides, polyureas, polyurethanes, polyphthalamides, polyamide-imides, poly(benzimidazole)s, polyarylates, liquid crstalline polymers (LCPs) and polyaramids.
6. The method of preparing an elastomeric material according to claim 1 , wherein the aromatic polymer is a poly(arylene ether) including polymer repeating units having the following structure:
—(—O—Ar 1 —O—Ar 2 —) m (—O—Ar 3 —O—Ar 4 —) n —
wherein Ar 1 ,Ar 2 , Ar 3 and Ar 4 are identical or different aryl radicals, m=0 to 1.0, and n=1 m.
7. The method of preparing an elastomeric material according to claim 1 , wherein the cross-linking compound has a structure selected from a group consisting of
8. The method of preparing an elastomeric material according to claim 1 , wherein the arene moiety has a molecular weight of about 1,000 g/mol to about 9,000 g/mol.
9. The method of preparing an elastomeric material according to claim 1 , wherein the arene moiety has a molecular weight of about 2,000 g/mol to about 7,000 g/mol.
10. The method of preparing an elastomeric material according to claim 1 , wherein step (b) further comprises cross-linking the organic polymer with the cross-linking compound and a cross-linking reaction additive selected from an organic acid and/or an acetate compound, wherein the cross-linking reaction additive is capable of reacting with the cross-linking compound to form a reactive intermediate in the form of an oligomer, which reactive intermediate oligomer is capable of cross-linking the organic polymer.
11. The method of preparing an elastomeric material according to claim 10 , wherein the cross-linking reaction additive is an organic acid selected from glacial acetic acid, formic acid, and/or benzoic acid.
12. The method of preparing an elastomeric material according to claim 10 , wherein the cross-linking reaction additive is an acetate compound having a structure according to formula (XI):
wherein M is a Group I or a Group II metal; and R 2 is a alkyl, aryl or aralkyl group, wherein the alkyl group comprises a hydrocarbon group of 1 to about 15 carbon atoms which has from 0 to about 5 ester or ether groups along or in a chain of the hydrocarbon group, and wherein R 2 comprises 0 to about 5 functional groups selected from sulfate, phosphate, hydroxyl, carbonyl, ester, halide, mercapto or potassium.
13. The method of preparing an elastomeric material according to claim 12 , wherein the acetate compound is selected from lithium acetate hydrate sodium acetate, and/or potassium acetate, and salts and derivatives thereof.
14. The method of preparing an elastomeric material according to claim 10 , wherein the weight percentage ratio of the cross-linking compound to the cross-linking reaction additive is about 10:1 to about 10,000:1.
15. The method of preparing an elastomeric material according to claim 14 , wherein the weight percentage ratio of the cross-linking compound to the cross-linking reaction additive is about 20:1 to about 1000:1.
16. The method of preparing an elastomeric material according to claim 1 , wherein the method further comprises forming a composition comprising the cross-linked organic polymer and heating the composition to form a molded article and step (c) further comprises placing the molded article in use at a temperature at or above the glass transition temperature of the cross-linked organic polymer.
17. An article formed by the method of claim 1 .
18. The article according to claim 17 , selected from the group consisting of an O-ring, a V-ring, a U-cup, a gasket, at least one component of a seal stack, a packer element, a diaphragm, a thee seal, a bearing, a valve seat, an adapter, a wiper ring, a chevron seal back-up ring, an tubing.
19. A method of preparing an elastomeric material, comprising
(a) providing an aromatic polymer which is non-elastomeric at room temperature;
(b) cross-linking the aromatic polymer using a cross-linking compound to form a cross-linked aromatic polymer that is substantially cured; and
(c) heating the cross-linked aromatic polymer to a temperature at or above a glass transition temperature of the cross-linked aromatic polymer,
and wherein the aromatic polymer is a poly(arylene ether), and the polymer has repeating units having the structure of formula (I):
20. An elastomeric material formed by heating a cross-linked aromatic polymer that is substantially cured at or above a glass transition temperature of the cross-linked aromatic polymer, wherein the aromatic polymer is not elastomeric at room temperature prior to cross-linking, and wherein the aromatic polymer is cross-linked by reaction with a cross-linking compound having a structure according to formula (II):
wherein A is an arene moiety having molecular weight of less than 10,000 g/mol, R 1 is selected from a group consisting of hydroxide(—OH), amine (—NH 2 ), halide, ether, ester, or amide, and x is about 2.0 to about 6.0, or by thermally induced cross-linking of an aromatic polymer having a graft bonded to the aromatic polymer.
21. An elastomeric article formed by heat molding a composition comprising a cross-linked aromatic polymer to form a molded article, wherein the aromatic polymer is not elastomeric at room temperature prior to cross-linking, and wherein the cross-linked aromatic polymer is substantially cured, and heating the molded article at or above a glass transition temperature of the cross-linked aromatic polymer, wherein the aromatic polymer is cross-linked by reaction with a cross-linking compound having a structure according to formula (II):
wherein A is an arene moiety having a molecular weight of less than 10,000 g/mol, R 1 is selected from a group consisting of hydroxide (—OH),amine (—NH 2 ) halide, ether, ester, or, amide, and x is about 2.0 to about 6.0, or by thermally induced cross-linking of an aromatic polymer having a graft bonded to the aromatic polymer.
22. A composition for forming an elastomeric material, comprising
an aromatic polymer that is non-elastomeric at room temperature; and
a cross-linking compound, wherein the cross-linking compound and the aromatic polymer can react to form a cross-linked aromatic polymer that becomes elastomeric when heated at or above a glass transition temperature of the cross-linked aromatic polymer, and the cross-linking compound has a structure according to formula (II):
wherein A is an arene moiety having a molecular weight of less than 10,000 g/mol, R 1 is selected from a group consisting of hydroxide (—OH) amine (—NH 2 ), halide, ether, ester, or amide, and x is about 2.0 to about 6.0.
23. A method of using an organic polymer that is not elastomeric at room temperature in an elastomeric application, comprising
cross-linking the organic polymer using a cross-linking compound to form a cross-linked organic polymer to substantially cure the aromatic polymer, wherein the cross-linking compound has as structure according to formula(II):
wherein A is an arene moiety having a molecular weight of less than 10 000 g/mol, R 1 is selected from a group consisting of hydroxide (—OH), amine (—NH 2 ), halide, ether, ester, or amide, and x is about 2.0 to about 6.0; and
heating the cross-linked polymer in use at or above a glass transition temperature of the cross-linked polymer such that it becomes elastomeric.
24. The method of using an organic polymer in an elastomeric composition according to claim 23 , further comprising forming a composition comprising the cross-linked organic polymer, molding the composition into a molded article, placing the molded article in use and heating the molded article in use so as to heat the cross-linked polymer at or above the glass transition temperature of the cross-linked polymer.
25. A method of preparing an elastomeric material, comprising
(a) providing an aromatic polymer which is non-elastomeric at room temperature;
(b) cross-linking the aromatic polymer using a cross-linking compound to form a cross-linked aromatic polymer, wherein the cross-linking compound has a structure according to formula (II):
wherein A is an arene moiety having a molecular weight of less than 10,000 g/mol, R 1 is selected from a group consisting of hydroxide (—OH), amine (—NH 2 ), halide, ether, ester, or amide, and x is about 2.0 to about 6.0; and
(c) heating the cross-linked aromatic polymer to a temperature at or above a glass transition temperature of the cross-linked aromatic polymer.
26. The method of preparing an elastomeric material according to claim 25 , wherein, in step (b), the aromatic polymer is at least about 80% cured.
27. The method of preparing an elastomeric material according to claim 26 , wherein the aromatic polymer is at least about 90% cured.
28. The method of preparing an elastomeric material according to claim 27 , wherein the aromatic polymer is fully cured.
29. A method of preparing an elastomeric material according to claim 25 , wherein the aromatic polymer is selected from the group consisting of poly(arylene ether)s, polysulfones, polyethersulfones, polyarylene sulfides, polyimides, polyamides, polyureas, polyurethanes, polyphthalamides, polyamide-imides, poly(benzimidazole)s, polyarylates, liquid crstalline polymers (LCPs) and polyaramids.
30. The method of preparing an elastomeric material according to claim 29 , wherein the aromatic polymer is a poly(arylene ether) including polymer repeating units having the following structure:
—(—O—Ar 1 —O—Ar 2 —) m (—O—Ar 3 —O—Ar 4 —) n —
wherein Ar 1 , Ar 2 , Ar 3 and Ar 4 are identical or different aryl radicals, m=0 to 1.0, and n=1 m.
31. The method of preparing an elastomeric material according to claim 30 , wherein step (b) further comprises cross-linking the organic polymer with the cross-linking compound and a cross-linking reaction additive selected from an organic acid and/or an acetate compound, wherein the cross-inking reaction additive is capable of reacting with the cross-linking compound to form a reactive intermediate in the form of an oligomer, which reactive intermediate oligomer is capable of cross-linking the organic polymer.
32. The method of preparing an elastomeric material according to claim 31 , wherein the cross-linking reaction additive is an organic acid selected from glacial acetic acid, formic acid, and/or benzoic acid.
33. The method of preparing an elastomeric material according to claim 31 , wherein the cross-linking reaction additive is an acetate compound having a structure according to formula (XI):
wherein M is a Group I or a Group II metal; and R 2 is a alkyl, aryl or aralkyl group, wherein the alkyl group comprises a hydrocarbon group of 1 to about 15 carbon atoms which has from 0 to about 5 ester or ether groups along or in a chain of the hydrocarbon group, and wherein R 2 comprises 0 to about 5 functional groups selected from sulfate, phosphate, hydroxyl, carbonyl, ester, halide, mercapto or potassium.
34. The method of preparing an elastomeric material according to claim 33 , wherein the acetate compound is selected from lithium acetate hydrate sodium acetate, and/or potassium acetate, and salts and derivatives thereof.
35. The method of preparing an elastomeric material according to claim 31 , wherein the weight percentage ratio of the cross-linking compound to the cross-linking reaction additive is about 10:1 to about 10,000:1.
36. The method of preparing an elastomeric material according to claim 35 , wherein the weight percentage ratio of the cross-linking compound to the cross-linking reaction additive is about 20:1 to about 1000:1.
37. The method of preparing an elastomeric material according to claim 30 , wherein the organic polymer is a poly(arylene ether), m is 1 and n is 0 and the polymer has repeating units having the structure of formula (I):
38. The method of preparing an elastomeric material according to claim 25 , wherein the cross-linking compound has a structure selected from a group consisting of
39. The method of preparing an elastomeric material according to claim 25 , wherein the arene moiety has a molecular weight of about 1,000 g/mol to about 9,000 g/mol.
40. The method of preparing an elastomeric material according to claim 39 , wherein the arene moiety has a molecular weight of about 2,000 g/mol to about 7,000 g/mol.
41. The method of preparing an elastomeric material according to claim 25 , wherein the method further comprises forming a composition comprising the cross-linked organic polymer and heating the composition to form a molded article and step (c) further comprises placing the molded article in use at a temperature at or above the glass transition temperature of the cross-linked organic polymer.
42. An article formed by the method of claim 25 .
43. The article according to claim 42 , selected from the group consisting of an O-ring, a V-ring, a U-cup, a gasket, at least one component of a seal stack, a packer element, a diaphragm, a face seal, a bearing, a valve seat, an adapter, a wiper ring, a chevron seal back-up ring, an tubing.