Barrier structure based on MPMDT/XT copolyamide with a high Tg

Patent metadata

Field	Value
Publication number	US-11345131-B2
Application number	US-201616062231-A
Country	US
Kind code	B2
Filing date	Dec 15, 2016
Priority date	Dec 18, 2015
Publication date	May 31, 2022
Grant date	May 31, 2022

Abstract

A barrier structure for the storage and/or transport of fluids, including at least one barrier layer (1) including an MPMDT/XT copolyamide in which: MPMDT is a unit with an amide motif having a molar ratio of between 5 and 50%, particularly between 5 and 45%, preferably between 15 and 45%, more preferably between 20 and 45%, where MPMD is 2-methyl pentamethylene diamine (MPMD) and T is terephthalic acid, XT being a unit with a majority amide motif having a molar ratio of between 50 and 95%, particularly between 55 and 95%, preferably between 55 and 85%, more preferably between 55 and 80%, where X is a C9 to C18, preferably C9, C10, C11 and C12, linear aliphatic diamine, and where T is terephthalic acid, the copolyamide having a melting point of 250° C.<T f ≤300° C. as determined according to the ISO norm 1 1357-3 (2013).

First claim

The invention claimed is:

1. A barrier structure chosen from bottles, tanks, containers, pipes, receptacles and films, comprising at least one barrier layer (1) comprising an MPMDT/XT copolyamide wherein:
MPMDT is a unit comprising an amide moiety present in a molar content ranging from 5 to 50%, where MPMD represents 2-methylpentamethylenediamine (MPMD) and T represents terephthalic acid,
XT is a unit comprising a major amide moiety present in a molar content ranging from 50 to 95%, where X is a C 9 to C 18 , linear aliphatic diamine and where T is terephthalic acid,
said copolyamide having a melting point: 250° C.<T m ≤300° C. as determined according to the standard ISO 11357-3 (2013), wherein said copolyamide has a glass transition temperature Tg of greater than 125° C., determined according to the standard ISO 11357-2: 2013,
in the MPMDT and/or XT units, independently of one another, up to
30 mol %, relative to the total amount of dicarboxylic acids, of the terephthalic acid can be replaced with other aromatic, aliphatic or cycloaliphatic dicarboxylic acids comprising 6 to 36 carbon atoms, and
in the MPMDT and/or XT units, independently of one another, up to 30 mol % of the MPMD and/or where appropriate of X, relative to the total amount of diamines, can be replaced with other diamines comprising from 4 to 36 carbon atoms, in particular 6 to 12 carbon atoms, and
in the copolyamide, no more than 30 mol %, relative to the total amount of monomers, can be formed by lactams or aminocarboxylic acids, and
on the condition that the sum of the monomers which replace the terephthalic acid, the MPMD and X does not exceed a concentration of 30 mol %, relative to the total amount of monomers used in the copolyamide, and
on the condition that the MPMD is not totally substituted,

said at least one barrier layer (1) being devoid of reinforcing fibers, wherein, regardless of the substitution that is carried out for the diacids and/or diamines, the proportion of MPMDT/XT remains within the range 5 to 45 mol % and of XT remains within the range of 55 to 95 mol %,
wherein said barrier structure further comprises a second layer (2), the layers (1) and (2) being capable of adhering to one another, wherein said layer (2) is formed from one or more aliphatic polyamides,
wherein the aliphatic polyamides are formed from the polycondensation of at least one lactam and of at least one aminocarboxylic acid, of at least one aliphatic or cycloaliphatic diamine and at least one aliphatic or cycloaliphatic dicarboxylic acid, or of a mixture thereof,
and wherein layer (1) is the layer in contact with a fuel.

2. The barrier structure as claimed in claim 1 , wherein said copolyamide has a glass transition temperature Tg≥131° C. determined according to the standard ISO 11357-2: 2013.

3. The barrier structure as claimed in claim 1 , wherein X is 1,10-decanediamine.

4. The barrier structure as claimed in claim 1 , wherein none of the monomers of said copolyamide is substituted with another diamine, another dicarboxylic acid or a lactam.

5. The barrier structure as claimed in claim 1 , wherein said layer (1) comprises an impact modifier and/or a modifier of core-shell type.

6. The barrier structure as claimed in claim 1 , wherein said layer (1) comprises a stabilizer chosen from an organic stabilizer, an inorganic stabilizer, and a mixture thereof.

7. The barrier structure as claimed in claim 1 , wherein said layer (1) comprises an antistatic filler chosen from carbon black, graphite, carbon fibers and carbon nanotubes.

8. The barrier structure as claimed in claim 1 , wherein said layer (1) comprises at least one additive chosen from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, a mineral filler, a flame retardant, a nucleating agent, a plasticizer and a dye.

9. The barrier structure as claimed in claim 1 , wherein said one or more aliphatic polyamides of the layer (2) is chosen from PA11, PA12, PA1010, PA1012, PA610 and PA612.

10. The barrier structure as claimed in claim 1 , wherein a plasticizer is present in the layer (2).

11. The barrier structure as claimed in claim 1 , wherein an impact modifier is present in the layer (2).

12. The barrier structure as claimed in claim 1 , wherein said layer (2) comprises a stabilizer chosen from an organic stabilizer, an inorganic stabilizer, and a mixture thereof.

13. The barrier structure as claimed in claim 1 , wherein the layer (1) comprises an organic stabilizer and the layer (2) comprises an inorganic stabilizer.

14. The barrier structure as claimed in claim 1 , wherein the layer (1) comprises an inorganic stabilizer, and the layer (2) comprises an organic stabilizer.

15. The barrier structure as claimed in claim 1 , wherein said layer (2) comprises an antistatic filler chosen from carbon black, graphite, carbon fibers and carbon nanotubes.

16. The barrier structure as claimed in claim 1 , wherein said layer (2) comprises at least one additive chosen from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, a mineral filler, a flame retardant, a nucleating agent, and a dye.

17. The barrier structure as claimed in claim 1 , wherein the layer (1) is a barrier layer, said fuel being a gasoline, or diesel, an oil, a brake fluid, urea solutions, a glycol-based cooling fluid, a gas, said barrier layer (1) being in contact with the fluid.

18. The barrier structure as claimed in claim 1 , additionally comprising a layer (3), the layer (3) being identical to or different than the layer (1).

19. The barrier structure as claimed in claim 18 , wherein the layer (3) is different than the layer (1) and is a tie layer and the structure comprises, from the outside to the inside, the following layers: (2)//(3)//(1), the layer (1) being in contact with said fuel.

20. The barrier structure as claimed in claim 19 , wherein at least one other layer (4) is present, the layer (1) being in contact with said fuel.

21. The barrier structure as claimed in claim 20 , wherein the layer (4) is a layer of EVOH.

22. The barrier structure as claimed in claim 20 , wherein the structure comprises, from the outside to the inside, the following layers: (2)//(4)//(3)//(1), the layer (1) being in contact with said fuel.

23. The barrier structure as claimed in claim 20 , wherein a tie layer (3′), identical to or different than the tie layer (3), is present.

24. The barrier structure as claimed in claim 23 , wherein the structure comprises, from the outside to the inside, the following layers: (2)//(3′)//(4)//(3)//(1), the layer (1) being in contact with said fuel.

25. Bottles, tanks, containers, pipes and receptacles manufactured with the structure as claimed in claim 1 .

26. Packagings consisting of the films manufactured with the structure as claimed in claim 1 .

27. The barrier structure as claimed in claim 1 , wherein the aliphatic diamine of the one or more aliphatic polyamides in the second layer is chosen from butanediamine, pentanediamine, heptanediamine, octanediamine, nonanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, hexadecanediamine, octadecanediamine, eicosanediamine, docosanediamine or diamines obtained from dimerized fatty acids.

28. The barrier structure as claimed in claim 1 , wherein the second layer (2) comprises reinforcing fibers.

Assignees

• Arkema France

Inventors

• Briffaud Thierry
• Capelot Mathieu
• Dufaure Nicolas

Classifications

• B32B27/34 Primary

  comprising polyamides · CPC title

• B32B2250/03

  3 layers · CPC title

• B32B2597/00

  Tubular articles, e.g. hoses, pipes · CPC title

• B32B27/365

  comprising polycarbonates · CPC title

• B32B2264/025

  Acrylic resin particles, e.g. polymethyl methacrylate or ethylene-acrylate copolymers · CPC title