Method of recycling phenol resin-containing materials, especially phenol resin-based fiber composite materials

Patent metadata

Field	Value
Publication number	US-10633507-B2
Application number	US-201615774715-A
Country	US
Kind code	B2
Filing date	Nov 9, 2016
Priority date	Nov 13, 2015
Publication date	Apr 28, 2020
Grant date	Apr 28, 2020

Abstract

The present invention relates to a method for degradation of a phenolic resin-containing material, characterized in that the phenolic resin-containing material is subjected to an aminolysis with a reagent containing at least one amino group, as well as a method for synthesis and degradation of a phenolic resin-containing material, characterized in that the phenolic resin-containing material is created by curing the starting components at a temperature of less than 140° C. and is subjected to aminolysis with a reagent containing at least one amino group for the purpose of degradation.

First claim

What is claimed is:

1. A method for degradation of a phenolic resin-containing material, comprising the phenolic resin-containing material being subjected to aminolysis with a reagent containing at least one amino group, wherein the reagent containing at least one amino group is ammonia, an aliphatic or aromatic amine or hydrazine, which may contain additional functional groups, or a mixture of two or more of the aforementioned reagents.

2. The method according to claim 1 , wherein the reagent containing at least one amino group is selected from the group of compounds comprising aliphatic primary amines, aromatic amines, amino alcohols and diamines, wherein the reagent has one, two or more of these compounds.

3. The method according to claim 2 , wherein the aliphatic primary amines and diamines each have a linear or branched alkyl or alkylene radical.

4. The method according to claim 1 , wherein the reagent containing the at least one amino group is used under pressureless conditions or under pressure in a condensed state or after melting at an elevated temperature, as a solvent.

5. The method according to claim 1 , wherein the aminolysis is carried out in a solvent, selected from a cyclic ether, alcohol, chlorocarbon or a solvent containing nitrogen.

6. The method according to claim 5 , wherein the solvent is tetrahydrofuran, dimethyl sulfoxide, ethanol, water, dioxane, dichloromethane, chloroform, dimethylformamide or N-methyl-2-pyrrolidone.

7. The method according to claim 1 , wherein the phenolic resin-containing material contains an amount of dimethylene ether bridges corresponding to an oxygen content of the phenolic resin in the material of at least 17.0 wt %.

8. The method according to claim 1 , wherein the phenolic resin of the phenolic resin-containing material is a resol.

9. The method according to claim 1 , wherein the phenolic resin of the phenol resin-containing material is a novolak with dimethyleneamino bridges, wherein the amount of dimethyleneamino bridges corresponds to a nitrogen content of the phenolic resin in the material of at least 1.2 wt %.

10. The method according to claim 1 , wherein the phenolic resin is a novolak which has been produced by using at least one triglyceride or triglyceride mixture containing unsaturated fatty acids.

11. The method according to claim 1 , wherein the phenolic resin-containing material is a phenolic resin-based fiber composite plastic, and the fiber composite, optionally with phenolic resin residues remaining on it is separated from the reagent containing at least one amino group after aminolysis has been performed and then is optionally reused.

12. The method according to claim 11 , wherein the fibers of the plastic are selected from the group consisting of glass fibers, carbon fibers, aramid fibers, basalt fibers and natural fibers.

13. The method according to claim 11 , wherein the fibers of the plastic are polyamide fibers and the reagent containing the at least one amino group is a linear alkylamine having three to 12 carbons in the alkyl chain.

14. The method according to claim 1 , wherein the aminolysis is carried out with the input of microwave energy.

15. The method according to claim 1 , wherein the phenolic resin-containing material adheres in the form of an impurity to an object, and the object is separated from the reagent containing the at least one amino group after aminolysis has been performed.

16. A method for synthesis and degradation of a phenolic resin-containing material, wherein the phenolic resin-containing material is created by curing the starting components at a temperature of less than 140° C. and, for the purpose of degradation, is subjected to an aminolysis with a reagent containing at least one amino group according to claim 1 .

17. The method according to claim 16 , wherein the phenolic resin-containing material has an oxygen content of at least 17 wt %, based on the weight of the phenolic resin, and/or wherein the phenolic resin-containing material has a nitrogen content of at least 1.5 wt %, based on the weight of the phenolic resin.

18. A method for synthesis and degradation of a phenolic resin-containing material in the form of a novolak, wherein
(i) (a) the phenolic resin-containing material is created by curing the starting components at a temperature of less than 180° C., and/or
(b) the phenolic resin-containing material has been produced by using at least one triglyceride or triglyceride mixture, and/or
(c) the amount of amino compound provided for curing is >6 wt %, and

(ii) for the purposes of degradation, the resin is subjected to aminolysis with a reagent containing at least one amino group as defined in claim 1 .

19. A method for producing a novolak that is completely or partially degradable by aminolysis, comprising:
(a) reacting a phenolic component with an aldehyde in the presence of (i) an acid, (ii) an amine curing agent and (iii) a triglyceride or a triglyceride mixture, and
(b) curing the resin formed according to (a) at a temperature of ≤180° C., wherein the amine-curing agent is hexamethylenetetramine.

20. The method according to claim 19 , wherein
(a) the phenolic component is selected from the group consisting of phenol, xylene, cresol, condensed, optionally alkyl-substituted phenols and mixtures of two or more of these phenolic components, and/or
(b) the acid is an aromatic sulfonic acid and/or
(c) the aldehyde is selected from formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, glyoxal and furfural and a mixture of two or more of these aldehydes,
and/or
(d) the amine-curing agent is hexamethylenetetramine and/or
(e) wood oil is used as the triglyceride or triglyceride mixture.

21. A method for reusing a phenolic resin-containing material, comprising
degradation of the material as defined in claim 1 , wherein a liquid and components optionally in a solid condition are formed,
in the case of components remaining in the solid state, these components are separated from the liquid,
the liquid is treated to remove volatile products, under a reduced pressure and/or at an elevated temperature, forming a nonvolatile residue,
the nonvolatile residue is mixed with starting materials required for synthesis of a phenolic resin or with one or more compounds selected from monomers, oligomers or polymers having at least two functional groups which react with amino groups and/or hydroxyl groups, wherein the compounds are selected from isocyanates, activated (meth)acrylic acid compounds, cyanates and epoxy resins.

22. The method according to claim 10 , wherein wood oil is used as the triglyceride or triglyceride mixture.

Assignees

• Fraunhofer Ges Forschung

Inventors

• Sothje Dominik
• Dreyer Christian
• Bauer Monika
• Lang Jurgen

Classifications

• C08J2361/06

  of aldehydes with phenols · CPC title

• C08J11/28 Primary

  by treatment with organic compounds containing nitrogen, sulfur or phosphorus · CPC title

• C08G8/32

  by organic acids or derivatives thereof, e.g. fatty oils · CPC title

• C08G8/10

  with phenol · CPC title

• C08K5/17

  Amines; Quaternary ammonium compounds · CPC title