Polyurea that is particularly useful as an adhesion primer for adhering metal to rubber

Patent metadata

Field	Value
Publication number	US-9845376-B2
Application number	US-201314438382-A
Country	US
Kind code	B2
Filing date	Oct 16, 2013
Priority date	Oct 24, 2012
Publication date	Dec 19, 2017
Grant date	Dec 19, 2017

Abstract

A polyurea comprises at least urea base units of formula —NH—CO—NH— and additional units. The additional units comprise at least, on the one hand, a secondary alcohol functional group and, on the other hand, an ether, thioether or secondary amine functional group in the alpha position with respect to the secondary alcohol functional group. Such a polymer can be used as an adhesion primer for the adhesive bonding of a substrate, for example, glass or metal, to an unsaturated rubber or as corrosion-resistant protective coating for a metal substrate. Metal reinforcers, such as thread, cord, film or plate, coated can also be coated with such a polymer.

First claim

The invention claimed is:

1. A polyurea comprising at least urea base units of formula —NH—CO—NH— and additional units,
wherein the additional units are units of the sulfur-comprising polyaromatic polyamine type comprising at least one sub-unit corresponding to the formula:
—HN—Ar 1 —NH—CH 2 —CH(OH)—(CH 2 ) m —O—Z 1 —O—(CH 2 ) m —CH(OH)—CH 2 —[X] n —HN—Ar 2 —NH—  (I)

wherein X represents the string:
—HN—Ar 3 —NH—CH 2 —CH(OH)—(CH 2 ) m —O—Z 2 —O—(CH 2 ) m —CH(OH)—CH 2 —;

wherein n represents an integer equal to zero or different from zero;
wherein m, which are identical or different, represent an integer within a range from 1 to 10;
wherein Z 1 and Z 2 represent cyclohexane-1,4-dimethylene; and
wherein Ar 1 Ar 2 and Ar 3 , which are identical or different, each represent a phenylene group, at least one of these phenylene groups bearing 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 group which optionally comprises a heteroatom and which comprises from 1 to 10 carbon atoms.

2. The polyurea according to claim 1 , wherein n is equal to 1.

3. The polyurea according to claim 1 , wherein n is within a range from 2 to 20.

4. The polyurea according to claim 3 , wherein n is within a range from 2 to 10.

5. The polyurea according to claim 1 , wherein m, which are identical or different, represent an integer within a range from 1 to 5.

6. The polyurea according to claim 5 , wherein m, which are identical or different, represent an integer equal to 1 or 2.

7. The polyurea according to claim 6 , wherein m is preferably equal to 1.

8. The polyurea according to claim 1 , wherein each of the Ar 1 , Ar 2 and Ar 3 groups bears one, two, three or four groups of formula —S X —R.

9. The polyurea according to claim 8 , wherein each of the Ar 1 , Ar 2 and Ar 3 groups bears two groups of formula —S X —R.

10. The polyurea according to claim 9 , wherein the two groups of formula —S X —R are in the meta position with respect to one another on the phenylene nucleus.

11. The polyurea according to claim 1 , wherein x is within a range from 1 to 4.

12. The polyurea according to claim 11 , wherein x is equal to 1 or 2.

13. The polyurea according to claim 1 , wherein R is an alkyl.

14. The polyurea according to claim 13 , wherein R is an alkyl having from 1 to 5 carbon atoms.

15. The polyurea according to claim 14 , wherein R represents a methyl or an ethyl.

16. The polyurea according to claim 15 , wherein R is a methyl.

17. The polyurea according to claim 1 , wherein the phenylenediamino —HN—Ar 1 —NH—, —HN—Ar 2 —NH—and —HN—Ar 3 —NH— strings, which are identical or different, correspond to either of formulae (III-a) and (III-b):

18. The polyurea according to claim 1 , wherein the sulfur-comprising polyaromatic polyamine units having a sub-unit of formula (I) and the base structural units having urea —NH—CO—NH— units are connected to one another according to a sub-unit corresponding to the formula:
—HN—Ar 1 —NH—Y—[X] n —HN—Ar 2 —NH—CO—NH—Z 3 —NH—CO—  (IV)

wherein Ar 1 , Ar 2 , X, n, m and Z 1 are as defined above;
wherein Y represents the string:
—CH 2 —CH(OH)—(CH 2 ) m —O—Z 1 —O—(CH 2 ) m —CH(OH)—CH 2 —; and

wherein Z 3 represents an aliphatic, cycloaliphatic or aromatic divalent bonding group.

19. The polyurea according to claim 18 , wherein the aliphatic group comprises from 1 to 30 carbon atoms, the cycloaliphatic group comprises from 3 to 30 carbon atoms, and the aromatic group comprises from 6 to 30 carbon atoms.

20. An adhesion primer for the adhesive bonding of a substrate to an unsaturated rubber comprising the polyurea according to claim 1 .

21. The adhesion primer according to claim 20 , wherein the substrate is a substrate having at least a surface comprising glass or metal.

22. A corrosion-resistant protective coating for a substrate having at least the surface being at least partially metallic comprising the polyurea of claim 1 .

23. A substrate coated, at least in part, with a polyurea according to claim 1 .

24. The substrate according to claim 23 , wherein the substrate is made of glass or metal.

25. A metal reinforcer coated with a polyurea according to claim 1 .

26. A metal reinforcer in the form of a thread, cord, film or plate, at least a portion of the surface of which is made of brass-coated steel, wherein the brass-coated steel is coated with a polyurea according to claim 1 .

Assignees

• Michelin & Cie
• Michelin Rech Tech
• Michelin & Cie

Inventors

• Fedurco Milan
• Ribezzo Marco
• Delfino Antonio

Classifications

• Y10T428/31725

  Of polyamide · CPC title

• Y10T428/12569

  Synthetic resin · CPC title

• C09J175/02

  Polyureas · CPC title

• C09D175/02

  Polyureas · CPC title

• C08G2380/00

  Tyres · CPC title