Polyamide composites containing graphene

Patent metadata

Field	Value
Publication number	US-9469742-B2
Application number	US-201414178943-A
Country	US
Kind code	B2
Filing date	Feb 12, 2014
Priority date	Feb 13, 2013
Publication date	Oct 18, 2016
Grant date	Oct 18, 2016

Abstract

The present invention relates to polyamide composites containing graphene, a method for producing them and to their use as or for producing a material with gas barrier and/or electroconductive and/or thermally conductive properties and/or a mechanically reinforced material.

First claim

The invention claimed is:

1. A method for producing polyamide composites containing graphene, comprising the following steps:
(i) dispersing a graphitic or graphenic material in an aqueous medium to yield an exfoliated material, and optionally removing non-reacted starting material from the aqueous mixture;
(ii) mixing at least one lactam monomer with the aqueous mixture obtained in step (i);
(iii) adding at least one non-ionic surfactant to the aqueous mixture obtained in step (ii);
(iv) removing from the aqueous mixture obtained in step (iii) essentially all water contained therein;
(v) heating the mixture obtained in step (iv) to 100 to 200° C.;
(vi) if the water content of the mixture obtained in step (v) is higher than 300 ppm, subjecting the mixture obtained in step (v) to a further drying process to obtain a mixture with a water content of at most 300 ppm;
(vii) heating the mixture obtained in step (v) or (vi) to 100 to 200° C.;
(viii) adding an anionic polymerization activator;
(ix) adding an anionic polymerization catalyst; and
(x) after polymerization is completed, isolating the resulting polyamide composite;
where the graphitic or graphenic material used in step (i) and the at least one non-ionic surfactant added in step (iii) are used in a weight ratio of from 20:1 to 1:1.

2. The method as claimed in claim 1 , where the graphitic or graphenic material used in step (i) is graphite oxide.

3. The method as claimed in claim 1 , where dispersing in step (i) is carried out by a sonication treatment, high speed mixing or high pressure homogenization.

4. The method as claimed in claim 1 , where the at least one lactam monomer used in step (ii) is selected from the group consisting of ε-caprolactam, 2-piperidone, 2-pyrrolidone, caprylolactam, enantholactam, laurolactam and mixtures thereof.

5. The method as claimed in claim 4 , where the lactam monomer used in step (ii) is ε-caprolactam.

6. The method as claimed in claim 1 , where the graphitic or graphenic material and the at least one lactam monomer are used in a weight ratio of from 1:5 to 1:5000.

7. The method as claimed in claim 1 , where the graphitic or graphenic material and the at least one lactam monomer are use in a weight ratio of from 1:10 to 1:1000.

8. The method as claimed in claim 1 , where the at least one non-ionic surfactant used in step (iii) is selected from the group consisting of alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters alkoxylated with 1 to 100 equivalents of ethylene oxide and/or propylene oxide; and ethylene oxide/propylene oxide copolymers with a number average molecular weight M n of from 500 to 10000.

9. The method as claimed in claim 8 , where the at least one non-ionic surfactant used in step (iii) is selected from the group consisting of C 10 -C 20 -alcohol alkoxylated with 20 to 100 equivalents of ethylene oxide and ethylene oxide/propylene oxide copolymers with a number average molecular weight M n of from 1000 to 10000 and an ethylene oxide/propylene oxide ratio of from 1:10 to 10:1.

10. The method as claimed in claim 1 , where the graphitic or graphenic material used in step (i) and the at least one non-ionic surfactant added in step (iii) are used in a weight ratio of from 5:1 to 1:1.

11. The method as claimed in claim 10 , where the graphitic or graphenic material used in step (i) and the at least one non-ionic surfactant added in step (iii) are used in a weight ratio of from 3:1 to 1:1.

12. The method as claimed in claim 1 , where the graphitic or graphenic material used in step (i) and the at least one non-ionic surfactant added in step (iii) are used in a weight ratio of from 5:1 to 1:1.2.

13. The method as claimed in claim 1 , where the graphitic or graphenic material used in step (i) and the at least one non-ionic surfactant added in step (iii) are used in a weight ratio of from 3:1 to 1:1.

14. The method as claimed in claim 1 , where in step (v) the mixture is heated to 120 to 160° C.

15. The method as claimed in claim 1 , where in step (vi) the mixture obtained in step (v) is subjected to a further drying process to obtain a mixture with a water content of at most 100 ppm.

16. The method as claimed in claim 1 , where in step (vii) the mixture is heated to 120 to 160° C.

17. The method as claimed in claim 1 , where anionic polymerization activator added in step (viii) is selected from the group consisting of isocyanates, capped isocyanates, anhydrides, acyl halides, esters, ureas, allophanates and carbodiimides.

18. The method as claimed in claim 17 , where the anionic polymerization activator is selected from diisocyanates, capped diisocyanates, optionally capped with a lactam, and diacyl halides.

19. The method as claimed in claim 18 , where the anionic polymerization activator is selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, the capped derivatives of the two last-mentioned diisocyanates, optionally capped with a lactam, hexamethylenedioyl bromide, hexamethylenedioyl chloride and mixtures thereof.

20. The method as claimed in claim 19 , where the anionic polymerization activator is hexamethylene diisocyanate capped with the lactam used in step (ii), optionally with ε-caprolactam.

21. A gas barrier material or an electroconductive material or a thermally conductive material or a mechanically reinforced material comprising the polyamide composite as claimed in claim 20 .

22. The method as claimed in claim 18 , where the anionic polymerization catalyst is selected from sodium caprolactamate and potassium caprolactamate.

23. The method as claimed in claim 1 , where the anionic polymerization catalyst added in step (ix) is selected from the group consisting of sodium caprolactamate, potassium caprolactamate, magnesium bromide caprolactamate, magnesium chloride caprolactamate, magnesium biscaprolactamate, sodium hydride, sodium, sodium hydroxide, sodium methanolate, sodium ethanolate, sodium propanolate, sodium butanolate, potassium hydride, potassium, potassium hydroxide, potassium methanolate, potassium ethanolate, potassium propanolate, potassium butanolate and mixtures thereof.

24. Polyamide composite containing graphene, obtained by the method as claimed in claim 1 .

Assignees

• Basf Se

Inventors

• Park Hye Jin
• Xia Qi
• Schneider Cecile
• Desbois Philippe
• Bruchmann Bernd
• MüLHAUPT ROLF

Classifications

• C08K3/04 Primary

  Carbon · CPC title

• H01B1/24

  the conductive material comprising carbon-silicon compounds, carbon or silicon · CPC title

• C08K2201/011

  Nanostructured additives · CPC title

• C08K3/042

  Graphene or derivatives, e.g. graphene oxides · CPC title

• C09K5/14

  Solid materials, e.g. powdery or granular · CPC title