Sulfurized polybenzoxazine that can be used for coating metal and for the bonding of same to rubber

Patent metadata

Field	Value
Publication number	US-11624002-B2
Application number	US-201816621520-A
Country	US
Kind code	B2
Filing date	Jun 12, 2018
Priority date	Jun 14, 2017
Publication date	Apr 11, 2023
Grant date	Apr 11, 2023

Abstract

A polybenzoxazine sulfide has repeating units including at least one unit corresponding to formula (I) or (II):

in which the two oxazine rings are connected together via a central aromatic group, the benzene ring of which bears one, two, three or four groups of formula —S x —R in which “x” is an integer from 1 to 8 and R represents hydrogen or a hydrocarbon-based group including 1 to 10 carbon atoms and optionally a heteroatom chosen from O, S, N and P. Such a polybenzoxazine can be used as an adhesive layer on metal, in particular for the adhesive bonding of a metallic substrate, in particular made of carbon steel, to rubber.

First claim

The invention claimed is:

1. A polybenzoxazine sulfide or ring-opened polybenzoxazine sulfide, repeating units of which include at least one unit corresponding to formula (I) or (II):

in which the a is an integer from 1 to 4, x is an integer from 1 to 8, R represents hydrogen or a hydrocarbon-based group including 1 to 10 carbon atoms and optionally a heteroatom chosen from O, S, N and P, and *, which may be identical or different, represents any attachment to a carbon atom or to a heteroatom chosen from O, S, N and P.

2. The polybenzoxazine sulfide or ring-opened polybenzoxazine sulfide according claim 1 , wherein a is 2.

3. The polybenzoxazine sulfide or ring-opened polybenzoxazine sulfide according to claim 2 , wherein the two groups of formula —S x —R are in a meta-position relative to each other.

4. The polybenzoxazine sulfide or ring-opened polybenzoxazine sulfide according to claim 1 , wherein x is in a range from 1 to 4.

5. The polybenzoxazine sulfide or ring-opened polybenzoxazine sulfide according to claim 1 , wherein R is an alkyl containing from 1 to 5 carbon atoms.

6. The polybenzoxazine sulfide or ring-opened polybenzoxazine sulfide according to claim 5 , wherein R represents a methyl or an ethyl.

7. The polybenzoxazine sulfide or ring-opened polybenzoxazine sulfide according to claim 4 , wherein x is equal to 1 and R represents a methyl.

8. The polybenzoxazine sulfide or ring-opened polybenzoxazine sulfide according to claim 1 , the repeating units of which comprise at least one unit corresponding to formulae (I-bis) or (II-bis):

9. The polybenzoxazine sulfide or ring-opened polybenzoxazine sulfide according to claim 8 , the repeating units of which comprise at least one unit corresponding to formulae (I-a) or (II-a):

10. A polybenzoxazine sulfide or ring-opened polybenzoxazine sulfide, repeating units of which comprise at least one unit corresponding to formulae (I-a-1), (I-b-1), (II-a-1) or (II-b-1):

11. The polybenzoxazine sulfide or ring-opened polybenzoxazine sulfide according to claim 1 , the repeating units of which correspond to at least one of formulae (I-1) or (II-1) below:

in which:
X 1 and X 2 , which may be identical or different, represent O or S;
Ar 1 and Ar 2 , which may be identical or different, represent an aromatic group; and
Z represents O or (S) n , n representing an integer greater than or equal to 1.

12. The polybenzoxazine sulfide or ring-opened polybenzoxazine sulfide according to claim 11 , the repeating units of which correspond to at least one of formulae (I-1bis) or (II-1bis) below:

13. A method for polymeric coating of a substrate, wherein at least a surface of the substrate is at least partly metallic, comprising the step of:
coating the substrate with the polybenzoxazine sulfide or ring-opened polybenzoxazine sulfide according to claim 1 to form a coated substrate.

14. The method according to claim 13 , wherein the coated substrate is bonded to a rubber.

15. A substrate having at least a surface which is at least partly metallic, the at least partly metallic surface being coated with the polybenzoxazine sulfide or ring-opened polybenzoxazine sulfide according to claim 1 .

16. The substrate according to claim 15 , wherein the substrate is made of steel.

17. The substrate according to claim 16 , wherein the steel is a bright steel.

18. The substrate according to claim 16 , wherein the steel is at least partially coated with at least one layer of a second surface metal selected from the group consisting of aluminum, copper, zinc and alloys thereof.

19. The substrate according to claim 18 , wherein the second surface metal is brass.

Assignees

• Michelin & Cie

Inventors

• Fedurco Milan
• Ribezzo Marco

Classifications

• C08F136/14

  containing elements other than carbon and hydrogen · CPC title

• B60C2009/0014

  Surface treatments of steel cords · CPC title

• B60C9/0007

  Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal · CPC title

• C09J147/00

  Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Adhesives based on derivatives of such polymers (C09J145/00 takes precedence; based on conjugated diene rubbers C09J109/00 - C09J121/00) · CPC title

• B60C2009/0021

  Coating rubbers for steel cords · CPC title