POLYMER MODIFIED ALONG THE CHAIN AND PROCESS FOR THE SYNTHESIS THEREOF

• US 20170174794A1
• Filed: 07/09/2015
• Published: 06/22/2017
• Est. Priority Date: 07/21/2014
• Status: Active Grant

• Current Assignee: Compagnie générale des établissements Michelin
• Original Assignee: Compagnie générale des établissements Michelin, Michelin Recherche et Technique SA (Compagnie Generale DES Etablissements Michelin SCA)
• Inventors: FLEURY, Etienne, THUILLIEZ, Julien, FAVROT, Jean-Michel
• Granted Patent: US 10,435,485 B2
• Time in Patent Office: Days
• CPC Class Codes: B60C 1/00 Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• CPC Class Codes: C08C 19/22 Incorporating nitrogen atoms into the molecule
• CPC Class Codes: C08F 8/30 Introducing nitrogen atoms or nitrogen-containing groups
• CPC Class Codes: C08K 3/04 Carbon
• CPC Class Codes: C08K 3/36 Silica

Abstract

A polymer comprises randomly distributed units UA, UB, UC and UD and at least one unit bearing a subunit F according to the respective molar percentages m, n, o, p and f

• • F pendant along the chain of the polymer and bearing an associative group comprising at least one nitrogen atom,
  • R₁ and R₂, which are identical or different, denoting a hydrogen atom, a methyl radical or a phenyl radical which is unsubstituted or substituted in the ortho, meta or para position by a methyl radical,
  • m≧50, n≧0, o≧0, f>0, 0<o+p≦25, m, n, o, p and f ranging from 0 to 100, the respective molar percentages of m, n, o, p and f calculated based on the sum of m+n+p+f, which is equal to 100.

Claims

1. A polymer which comprises the following units UA, UB, UC and UD and at least one unit bearing a subunit F,

2. A polymer according to claim 1, which contains the following units UE distributed randomly within the polymer,

3. A polymer according to claim 2, which contains the following units UF distributed randomly within the polymer,

4. A polymer according to claim 1, in which at least one of the two percentages n and o is different from 0.

5. A polymer according to claim 1, in which n and o are different from 0.

6. A polymer according to claim 1, in which at least one of the two molar percentages p and q is not equal to 0.

7. A polymer according to claim 2, which contains, as monomer units, only the units UA, UB, UC, UD and UE and the units bearing the subunit F according to their respective molar percentages m, n, o, p, q and f.

8. A polymer according to claim 1, which contains, as monomer units, only the units UA, UB, UC and UD and the units bearing the subunit F according to their respective molar percentages m, n, o, p and f.

9. A polymer according to claim 1, in which R₁ and R₂ are identical and denote a hydrogen atom.

10. A polymer according to claim 1, in which f varies from 0.01 to 50%.

11. A polymer according to claim 1, in which the associative group is selected from the group consisting of the imidazolidinyl, triazolyl, triazinyl, bis-ureyl and ureido-pyrimidyl groups.

12. A polymer according to claim 1, in which the associative group corresponds to one of the following formulae (I) to (V):

13. A polymer according to claim 1, in which the associative group corresponds to the formula (VI):

14. A polymer according to claim 1, which is an elastomer.

36. A rubber composition which comprises a reinforcing filler and an elastomer defined according to claim 14.

37. A tire which comprises a rubber composition according to claim 36.

15. A process for preparing a polymer modified by grafting, which process comprises the reaction of a starting diene polymer with a modifying agent, which starting diene polymer comprises the following units UA, UB, UC and UD, which modifying agent comprises, on the one hand, an associative group comprising at least one nitrogen atom and, on the other hand, a subunit G containing a group which is reactive with regard to the chain of the starting diene polymer, the units UA, UB, UC and UD being present in the starting diene polymer according to the respective molar percentages m′

, n′

, o′ and

p′ and

being distributed randomly within the starting diene polymer,

16. A process according to claim 15, in which G denotes a subunit containing a group which is reactive with regard to at least one diene unit of the starting diene polymer.

17. A process according to claim 15, in which the reactive group present in G is selected from the group consisting of the SH functional group, the azodicarbonyl group and a dipole containing at one nitrogen atom.

18. A process according to claim 15, in which the modifying agent contains an SH functional group and is of formula (VII):

 

 

(VII)

where;

X denotes an oxygen or sulphur atom or an —

NH group,

Ch denotes a carbon chain which can optionally contain heteroatoms,

G denotes a subunit containing, as reactive group, the SH functional group.

19. A process according to claim 15, in which the modifying agent contains an azodicarbonyl group and is of formula (VIII):

W—

CO—

N═

N—

CO-Sp-A 

 

(VIII)

where;

A represents the associative group comprising at least one nitrogen atom,

Sp is a divalent spacer group connecting the azodicarbonyl group to the associative group A,

W represents;

a group of formula;

R′

—

Z—

in which;

Z represents an oxygen or sulphur atom or an —

NH or —

NR′

group,

R′

represents a C₁-C₂₀ alkyl group,

or

a group of formula;

-Sp′

-A′

in which;

Sp′

, which is identical to or different from Sp, is a divalent spacer group connecting the azodicarbonyl group to another associative group A′

,

A′

, which is identical to or different from A, is an associative group comprising at least one nitrogen atom.

20. A process according to claim 19, in which the associative group comprising at least one nitrogen atom, in the case in point A and optionally A′

, is selected from an imidazolidinyl, ureyl, bis-ureyl, ureido-pyrimidyl or triazolyl group.

21. A process according to claim 19, in which the associative group comprising at least one nitrogen atom, in the case in point A and optionally A′

, corresponds to one of the formulae (IX) to (XIII);

22. A process according to claim 15, in which the modifying agent contains a group Q and a group A connected together by a group B, in which:

Q comprises a dipole containing at least one nitrogen atom,

A represents the associative group comprising at least one nitrogen atom,

B is an atom or a group of atoms forming a bond between Q and A.

23. A process according to claim 22, in which the group A corresponds to one of the following formulae (XXII) to (XXVI):

24. A process according to claim 23, in which the group A corresponds to the formula (XXVII):

 

 

(XXVII)

where ** represents a direct attachment to B.

25. A process according to claim 22, in which the modifying agent is a nitrile oxide, a nitrone or a nitrilimine.

26. A process according to claim 25, in which Q represents the subunit corresponding to the formula (XXVIII) in which four of the five symbols R₄ to R₈, which are identical or different, are each an atom or a group of atoms and the fifth symbol denotes a direct attachment to B.

 

 

(XXVIII),

27. A process according to claim 26, in which R₄, R₆ and R₈ are identical.

28. A process according claim 26, in which R₄, R₆ and R₈ are each an alkyl group of 1 to 6 carbon atoms.

29. A process according to claim 28, in which R₄, R₆ and R₈ are each a methyl or ethyl.

30. A process according to claim 26, in which the modifying agent is one of the 1,3-dipolar compounds of formula (XXIX) to (XXXIV):

31. A process according to claim 25, in which Q contains the dipole —

C═

N(fi O)—

.

32. A process according to claim 31, in which Q comprises the subunit corresponding to the formula (XXXV) or (XXXVI):

33. A process according to claim 32, in which the modifying agent is one of the 1,3-dipolar compounds of formula (XXXVII) to (XLI):

35. A process according to claim 15, in which R₁ and R₂ are each a hydrogen atom.

34. A process according to claim 51, in which the content of modifying agent varies from 0.01 to 50 molar equivalents of associative group A per 100 mol of monomer units constituting the starting diene polymer.