Polyamide and bioresourced reinforcement compositions having improved mechanical properties

Patent metadata

Field	Value
Publication number	US-10358527-B2
Application number	US-200913130212-A
Country	US
Kind code	B2
Filing date	Nov 23, 2009
Priority date	Nov 21, 2008
Publication date	Jul 23, 2019
Grant date	Jul 23, 2019

Abstract

One subject of the present invention is a composition that combines at least one polyamide having at least one MXD entity, MXD denoting meta-xylylenediamine or a mixture of meta-xylylenediamine and of para-xylylenediamine, with a bioresourced reinforcement. The invention also relates to the conversion of these compositions, by injection molding or extrusion, into objects that have good mechanical properties, said objects corresponding to technical application specifications such as may be found, for example, in the automotive industry, construction, sport and in electrical or electronic fields.

First claim

The invention claimed is:

1. A composition comprising:
(1) a polyamide matrix consisting of:
(i) at least one polyamide of the formula MXDZ, or
(ii) at least one copolyamide of the formula A/MXDZ,
wherein MXD denotes meta-xylylenediamine or a mixture of meta-xylylenediamine and of para-xylylenediamine,
Z is an aliphatic dicarboxylic acid moiety comprising 10 carbon atoms and the A entity is a lactam, an α,ε-aminocarboxylic acid or the product of the reaction of an aliphatic, cycloaliphatic, arylaliphatic, or aromatic, C 4 -C 36 dicarboxylic acid with an aliphatic, cycloaliphatic, arylaliphatic or aromatic, C 4 -C 36 diamine;
(2) a natural reinforcement selected from the group consisting of predried flax, hemp, sisal, kenaf, abaca and jute fibers;
(3) optionally a non-natural second reinforcement; and
(4) optionally one additive, and optionally fillers, and
wherein the melting point of said at least one polyamide of the formula MXDZ and said at least one copolyamide of the formula A/MXDZ is less than or equal to 215° C.,
and
the tensile modulus of the composition, measured according to standard ISO 527 1BA on samples conditioned for 15 days at 23° C. and at 50% relative humidity, is greater than 3500 MPa.

2. The composition as claimed in claim 1 , wherein A is a lactam or an α,ω-aminocarboxylic acid comprising at least 6 carbon atoms.

3. The composition as claimed in claim 1 , wherein A is caprolactam, lactam 12, 11-aminoundecanoic acid or 12-aminododecanoic acid.

4. The composition as claimed in claim 1 , wherein A is the product of condensation of a diamine with a dicarboxylic acid, and said diamine is an aromatic diamine.

5. The composition as claimed in claim 1 , wherein the molar proportion of the MXDZ unit, in the copolyamide of formula A/MXDZ, represents more than 25%.

6. The composition as claimed in claim 1 , wherein the natural reinforcement is in the form of a ground material, a flour, a short fiber, a long fiber, woven continuous fibers, nonwoven continuous fibers, or a mat of woven or nonwoven fibers.

7. The composition as claimed in claim 1 , wherein at least one additive that is impact modifiers, processing aids, UV-stabilizers, heat-stabilizers, or fire-retardants is present.

8. The composition as claimed in claim 1 , wherein at least one filler is present.

9. The composition as claimed in claim 1 , wherein at least one non-natural second reinforcement is present.

10. The composition as claimed in claim 9 , wherein the natural reinforcement to non-natural second reinforcement mass ratio is greater than 0.3.

11. The composition as claimed in claim 9 , wherein the weight proportion of natural reinforcement and non-natural second reinforcement is between 5% and 80% of the total weight of the composition.

12. The composition as claimed in claim 9 , wherein the natural reinforcement and the non-natural second reinforcement have undergone a treatment aimed at improving their adhesion with respect to the polyamides, said treatment comprising:
a chemical treatment,
a precoating of the reinforcement with a polymeric coupling agent,
a plasma treatment,
a mechanical or thermomechanical treatment,
a laser treatment, or
a γ- or UV-irradiation.

13. The composition as claimed in claim 9 , wherein the second reinforcement is a carbon fiber, carbon nanotubes or glass fibers.

14. An object obtained from a composition according to claim 1 , by injection-molding, extrusion, forming, calendering, filament winding or pultrusion of said composition.

15. The object as claimed in claim 14 , that is a recyclable object.

16. The object as claimed in claim 14 wherein said object is an automotive object, a construction object, an electrical or electronic object, or a sporting goods object.

17. A method for producing the composite material of claim 1 , said method comprising:
A— compounding, in an extruder or a co-kneader, between 180 and 240° C., the natural reinforcement and the polyamide matrix
B— extruding of a rod,
C— granulating the rod.

18. A method for producing the composite material of claim 1 , said method comprising:
A— impregnating the natural reinforcement in the polyamide matrix in a molten state between 180 and 240° C. by means of a crosshead extruder,
B— extruding of a rod,
C— granulating of the rod.

19. A method for producing the composite material of claim 1 , said method comprising:
A— stacking of alternating natural reinforcement and films of the polyamide matrix, or rolling of natural reinforcement multilayers alternating with a film of the polyamide matrix,
B— hot-pressing of between 180 and 240° C.

20. A method for producing the composite material of claim 1 , said method comprising:
A— pre-impregnating of the natural reinforcement in a fluidized bed of the polyamide matrix by an electrostatic route and then heating in an oven brought to between 200° C. and 240° C., or heating in the polyamide matrix in a molten state,
B— winding a filament,
C— heating in an oven brought to between 180° C. and 240° C.

21. A method for producing the composite material of claim 1 , said method comprising:
A— pre-impregnating the natural reinforcement in a fluidized bed of the polyamide matrix or in a bath of the polyamide matrix in a molten state of between 180 and 240° C.,
B— producing sheets by hot-pressing of between 180 and 240° C.

22. A method for producing the composite material of claim 1 , said method comprising:
A— drawing of the natural reinforcement and continuous impregnation of the polyamide matrix in a molten state or in a fluidized bed of powder of the polyamide matrix,
B— passing through a heating fixture brought to between 180 and 240° C. giving the shape of the cross section of the profile.

Assignees

• Brule Benoit
• Bussi Philippe
• Hochstetter Gilles
• Le Guillaume
• Ramfel Barbara
• Arkema France

Inventors

• Brule Benoit
• Bussi Philippe
• Hochstetter Gilles
• Le Guillaume
• Ramfel Barbara

Classifications

• C08J5/06

  using pretreated fibrous materials · CPC title

• B29C48/154

  Coating solid articles, i.e. non-hollow articles · CPC title

• B29C48/34

  Cross-head annular extrusion nozzles, i.e. for simultaneously receiving moulding material and the preform to be coated · CPC title

• C08L77/06 Primary

  Polyamides derived from polyamines and polycarboxylic acids (C08L77/10 takes precedence) · CPC title

• C08J2377/06

  Polyamides derived from polyamines and polycarboxylic acids (C08J2377/10 takes precedence) · CPC title