Thermoassociative and exchangeable copolymers, and compositions comprising same

Patent metadata

Field	Value
Publication number	US-10377844-B2
Application number	US-201515114111-A
Country	US
Kind code	B2
Filing date	Jan 26, 2015
Priority date	Jan 27, 2014
Publication date	Aug 13, 2019
Grant date	Aug 13, 2019

Abstract

A composition results from the mixture of at least one copolymer A resulting from the copolymerization of at least one monomer functionalized by diol functions and at least one compound A2 comprising at last two boronic ester functions. They have rheological properties which are very varied according to the proportion of the A1 and A2 compounds used. The field is that of associative and exchangeable polymers.

First claim

The invention claimed is:

1. A composition resulting from a mixture comprising at least:
(a) a statistical copolymer A1 resulting from the copolymerization:
of at least one first monomer M1 of general formula (I):

in which:
R 1 is selected from a group formed by —H, —CH 3 , and —CH 2 —CH 3 ;
x is an integer ranging from 2 to 18;
y is an integer equal to 0 or 1;
X 1 and X 2 , identical or different, are selected from a group formed by hydrogen, tetrahydropyranyl, methyloxymethyl, ter-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl;

or
X 1 and X 2 form with the oxygen atoms a bridge of a following formula

in which:
the stars (*) symbolize the bonds to the oxygen atoms;
R′ 2 and R″ 2 , identical or different, are selected from a group formed by hydrogen and a C 1 -C 11 alkyl;

or
X 1 and X 2 form with the oxygen atoms a boronic ester of the following formula

in which:
the stars (*) symbolize the bonds to the oxygen atoms,
R′″ 2 is selected from a group formed by a C 6 -C 18 aryl, a C 7 -C 18 aralkyl and C 2 -C 18 alkyl;
with at least one second monomer M2 of general formula (II):

in which:
R 2 is selected from a group formed by —H, —CH 3 and —CH 2 —CH 3 ;
R 3 is selected from a group formed by a C 6 -C 18 aryl, a C 6 -C 18 aryl substituted by an R′ 3 , —C(O)—O—R′ 3 ; —O—R′ 3 , —S—R′ 3 and —C(O)—N(H)—R′ 3 group with R′ 3 a C 1 -C 30 alkyl group; and

(b) a compound A2 comprising at least two boronic ester functions.

2. The composition according to claim 1 , in which the statistical copolymer A1 results from the copolymerization of at least one monomer M1 with at least two monomers M2 having different R3 groups.

3. The composition according to claim 2 , in which one of the monomers M2 has the general formula (II-A):

in which:
R 2 is selected from a group formed by —H, —CH 3 and —CH 2 —CH 3 ;
R″ 3 is a C 1 -C 14 alkyl group;

and the other monomer M2 has a general formula (II-B):

in which:
R 2 is selected from a group formed by —H, —CH 3 and —CH 2 —CH 3 ; and
R′″ 3 is a C 15 -C 30 alkyl group.

4. The composition according to claim 1 , in which the side chains of the statistical copolymer A1 have an average length ranging from 8 to 20 carbon atoms.

5. The composition according to claim 1 , in which the statistical copolymer A1 has a molar percentage of monomer M1 of formula (I) in the copolymer ranging from 1 to 30.

6. The composition according to 1, in which the statistical copolymer A1 has a number-average degree of polymerization ranging from 100 to 2000.

7. The composition according to claim 1 , in which the statistical copolymer A1 has a polydispersity index (PDI) ranging from 1.05 to 3.75.

8. The composition according to claim 1 , in which the compound A2 is a compound of formula (III):

in which:
w 1 and w 2 , identical or different are integers selected between 0 and 1;
R 4 , R 5 , R 6 and R 7 , identical or different are selected from a group formed by hydrogen and a hydrocarbon-containing group having from 1 to 24 carbon atoms; and
L is a divalent bond group and selected from a group formed by a C 8 -C 18 aryl, a C 6 -C 18 aralkyl and a C 2 -C 24 hydrocarbon-containing chain.

9. The composition according to claim 1 , in which the compound A2 is a statistical copolymer resulting from the copolymerization
of at least one monomer M3 of formula (IV):

in which:
t is an integer equal to 0 or 1;
u is an integer equal to 0 or 1;
M and R 8 are divalent bond groups, identical or different, selected from a group formed by a C 6 -C 18 aryl, a C 7 -C 24 aralkyl and a C 2 -C 24 alkyl;
X is a function selected from a group formed by —O—C(O)—, —C(O)—O—, —C(O)—N(H)—, —N(H)—C(O)—, —S—, —N(H)—, —N(R′ 4 )— and —O— with R′ 4 a hydrocarbon-containing chain comprising from 1 to 15 carbon atoms;
R 9 is selected from a group formed by —H, —CH 3 and —CH 2 —CH 3 ;
R 10 and R 11 identical or different are selected from a group formed by hydrogen and a hydrocarbon-containing group having from 1 to 24 carbon atoms;
with at least one second monomer M4 of general formula (V):

in which:
R 12 is selected from a group formed by —H, —CH 3 and —CH 2 —CH 3 ; and
R 13 is selected from a group formed by a C 6 -C 18 aryl, a C 6 -C 18 aryl substituted by an R′ 13 , —C(O)—O—R′ 13 ; —O—R′ 13 , —S—R′ 13 and —C(O)—N(H)—R′ 13 group with R′ 13 a C 1 -C 25 alkyl group.

10. The composition according to claim 9 , in which the chain formed by the sequence of the R 10 , M, X and (R 8 ) u groups with u equal to 0 or 1 of the monomer of general formula (IV) has a total number of carbon atoms ranging from 8 to 38.

11. The composition according to claim 9 , in which the side chains of the copolymer A2 have an average length greater than or equal to 8 carbon atoms.

12. The composition according to claim 9 , in which the copolymer A2 has a molar percentage of monomer of formula (IV) in the copolymer ranging from 0.25 to 20%.

13. The composition according to claim 9 , in which the copolymer A2 has a number-average degree of polymerization ranging from 50 to 1500.

14. The composition according to claim 9 , in which the copolymer A2 has a polydispersity index (PDI) ranging from 1.04 to 3.54.

15. The composition according to claim 1 , in which the copolymer A1 content ranges from 0.1% to 50% by weight with respect to the total weight of the composition.

16. The composition according to claim 1 , in which the compound A2 content ranges from 0.1% to 50% by weight with respect to the total weight of the composition.

17. The composition according to claim 1 , in which the ratio by weight between the copolymer A1 and the compound A2 (ratio A1/A2) ranges from 0.005 to 200.

18. The composition according to claim 1 further comprising at least one additive selected from a group formed by the polymers, pigments, dyes, fillers, plasticizers, fibres, antioxidants, additives for lubricants, compatibilizing agents, anti-foaming agents, dispersant additives, adhesion promoters and stabilizing agents.

19. A composition comprising:
a base oil;
a copolymer composition resulting from a mixture comprising at least:
(a) a statistical copolymer A1 resulting from the copolymerization:
of at least one first monomer M1 of general formula (I):

in which:
R 1 is selected from a g

Assignees

• Total Marketing Services
• Ecole Superieure De Physique Et De Chimie Ind De La Ville De Paris Espci
• Centre Nat Rech Scient

Inventors

• Nguyen Thi Hang Nga
• Nicolay Renaud
• Deves Lise

Classifications

• C10N2030/02

  Pour-point; Viscosity index · CPC title

• C10M2209/084

  Acrylate; Methacrylate · CPC title

• C10M2209/04

  containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical · CPC title

• C10M2205/04

  containing aromatic monomers, e.g. styrene · CPC title

• C10M159/005

  Macromolecular compounds, e.g. macromolecular compounds composed of alternatively specified monomers not covered by the same main group · CPC title