Polyimide composition

Patent metadata

Field	Value
Publication number	US-10214615-B2
Application number	US-201314422900-A
Country	US
Kind code	B2
Filing date	Aug 2, 2013
Priority date	Aug 24, 2012
Publication date	Feb 26, 2019
Grant date	Feb 26, 2019

Abstract

Polyimide formed from at least one dianhydride and at least one diamine, wherein at least 50 wt. % of the diamine is comprised of dimer fatty diamine, and a process of making the polyimide. The dianhydride is preferably a tetracarboxylic acid in which carbonyl groups are attached in pair to adjacent carbon atoms, and the dimer fatty diamine may be formed from a corresponding dimer fatty acid, especially the dimerisation products of C10 to C30 fatty acids such as oleic acid, linoleic acid, linolenic acid, palmitoleic acid, and elaidic acid. Also polyimide pre-polymer being polyamic acid formed by reaction of the dinhydride, and diamine comprised of dimer fatty diamine. The polyimide may be formed in to coatings, adhesives, or polymer films, said compositions in particular being self-healing.

First claim

The invention claimed is:

1. Polyimide formed from at least one dianhydride and at least one dimer fatty diamine and at least one aromatic diamine,
wherein at least 50 wt. % of the total amount of diamine is comprised of dimer fatty diamine, and
wherein at least one aromatic diamine is present in an amount of at least 5 wt. % of the total diamine,
wherein the dimer fatty diamine has a trimer fatty triamine content of less than 1 wt. %,
wherein the polyimide has a weight average molecular weight in the range 10,000 to 300,000, and
wherein the at least one aromatic diamine is selected from the group consisting of 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, o-tolidine, m-tolidine, 4,4′-diaminobenzanilide, p-phenylenediamine, and m-phenylenediamine.

2. The polyimide according to claim 1 , wherein the dianhydride is selected from 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride, 1,4-hydroquinone dibenzoate-3,3′,4,4′-tetracarboxylic dianhydride, 4,4′-oxydiphtalic dianhydride, and 1,2,3,4-butane-tetracarboxylic dianhydride.

3. The polyimide according to claim 1 , wherein the dimer fatty diamine is formed from a corresponding dimer fatty acid.

4. The polyimide according to claim 1 , wherein the dimer fatty diamine is derived from the dimerisation products of C 10 to C 30 fatty acids.

5. The polyimide according to claim 4 , wherein the dimer fatty diamine is derived from the dimerisation products of C 16 to C 20 fatty acids.

6. The polyimide according to claim 1 , wherein the molecular weight (weight average) of the dimer fatty diamine is in the range from 450 to 690.

7. The polyimide according to claim 1 , wherein the dimer fatty diamine is derived from linear or branched unsaturated fatty acids.

8. The polyimide according to claim 7 , wherein the dimer fatty diamine is derived from the dimerisation products of oleic acid, linoleic acid, linolenic acid, palmitoleic acid, or elaidic acid.

9. The polyimide according to claim 1 , wherein the total amount of diamine has a dimer fatty diamine content of greater than 60 wt. %.

10. The polyimide according to claim 1 , wherein the dimer fatty diamine has an amine value in the range from 140 mgKOH/g to 300 mgKOH/g.

11. The polyimide according to claim 9 , wherein the dimer fatty diamine has a bulk amine functionality greater than 1.8 and less than 2.3.

12. The polyimide according to claim 9 , wherein the dimer fatty diamine (at 25° C.) has a dynamic viscosity in the range from 200 to 300 mPa·s.

13. The polyimide according to claim 1 , wherein the polyimide can withstand the onset of thermal decomposition (500° C-520° C.), and can withstand a tension of 50 meganewtons per square meter (MN/m 2 ), or 500 kilograms-force per square centimeter (kgf/cm 2 ), at 300° C.

14. The polyimide according to claim 1 , wherein the polyimide has elastomeric properties which allow it to undergo a tensile deformation of at least 100% before break, and to recover its initial dimensions once the stress has been removed with a remnant deformation of less than 10% of its initial dimension.

15. A method of making polyimide comprising mixing:
at least one dianhydride; and
at least one dimer fatty diamine and at least one aromatic diamine,
wherein at least 50 wt. % of the total amount of diamine is comprised of dimer fatty diamine, and
wherein at least one aromatic diamine is present in an amount of at least 5 wt. % of the total diamine,
wherein the dimer fatty diamine has a trimer fatty triamine content of less than 1 wt. %,
wherein the polyimide has a weight average molecular weight in the range 10,000 to 300,000, and
wherein the at least one aromatic diamine is selected from the group consisting of 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, o-tolidine, m-tolidine, 4,4′-diaminobenzanilide, p-phenylenediamine, and m-phenylenediamine.

16. The method according to claim 15 , further comprising controlling the molecular weight of the formed polyimide with a chain stopper.

17. The method according to claim 15 , wherein the dianhydride is selected from the group consisting of 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride, 1,4-hydroquinone dibenzoate-3,3′,4,4′-tetracarboxylic dianhydride, 4,4′-oxydiphtalic dianhydride, and 1,2,3,4-butane-tetracarboxylic dianhydride.

18. A coating, adhesive, or polymer film composition comprising polyimide, said polyimide being formed from at least one dianhydride and at least one dimer fatty diamine and at least one aromatic diamine,
wherein at least 50 wt .% of the total amount of diamine is comprised of dimer fatty diamine, and
wherein at least one aromatic diamine is present in an amount of at least 5 wt. % of the total diamine,
wherein the dimer fatty diamine has a trimer fatty triamine content of less than 1 wt. %,
wherein the dimer fatty diamine comprises less than 4 mg/kg of halide ions,
wherein the polyimide has a weight average molecular weight in the range 10,000 to 300,000, and
wherein the at least one aromatic diamine is selected from the group consisting of 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, o-tolidine, m-tolidine, 4,4′-diaminobenzanilide, p-phenylenediamine, and m-phenylenediamine.

19. Polyimide pre-polymer, said pre-polymer being polyamic acid which is the reaction product of at least one dianhydride and at least one dimer fatty diamine and at least one aromatic diamine,
wherein at least 50 wt. % of the total amount of diamine is comprised of dimer fatty diamine, and
wherein at least one aromatic diamine is present in an amount of at least 5 wt. % of the total diamine,
wherein the dimer fatty diamine has a trimer fatty triamine content of less than 1 wt. %,
wherein the polyimide pre-polymer has a weight average molecular weight in the range 10,000 to 300,000, and
wherein the at least one aromatic diamine is selected from the group consisting of 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, o-tolidine, m-tolidine, 4,4′-diaminobenzanilide, p-phenylenediamine, and m-phenylenediamine.

20. The coating, adhesive, or polymer film composition according to claim 18 , wherein the dianhydride is selected from 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride, 1,4-hydroquinone dibenzoate-3,3′,4,4′-tetracarboxylic dianhydride, 4,4′-oxydiphtalic dianhydride, and 1,2,3,4-butane-tetracarboxylic dianhydride.

21. The polyimide pre-polymer according to claim 19 , wherein the dianhydride is selected from 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride, 1,4-hydroquinone dibenzoate-3,3′,4,4′-tetracarboxylic dianhydride, 4,4′-oxydiphtalic dianhydride, and 1,2,3,4-butane-tetracarboxylic dianhydride.

22. A film, adhesive, coating or moulded object comprising a polyimide as claimed in claim 1 .

23. The polyimide according to claim 1 , wherein the polyimide is capable of self-healing at 60° C. within 1 day after receiving damage.

24. The polyimide according to claim 1 , wherein the polyimide exhibits an amount of self-healing at room te

Assignees

• Croda Int Plc

Inventors

• Smits Angela Leonarda Maria
• Van Triet Remco Benjamin
• Dingemans Theodorus Jacobus
• Garcia-Espallargas Santiago Juan

Classifications

• C08G73/1082

  wholly aromatic in the tetracarboxylic moiety · CPC title

• C08L79/08

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title

• C08G73/1075

  Partially aromatic polyimides · CPC title

• C08G73/1014

  in the form of (mono)anhydrid · CPC title

• C09J179/08

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title