Thermoassociative and exchangeable copolymers, composition comprising same

Patent metadata

Field	Value
Publication number	US-11859150-B2
Application number	US-201716463532-A
Country	US
Kind code	B2
Filing date	Nov 21, 2017
Priority date	Nov 23, 2016
Publication date	Jan 2, 2024
Grant date	Jan 2, 2024

Abstract

Compositions resulting from the mixing of at least one copolymer A1, resulting from the copolymerization of at least one monomer functionalized by diol functions with at least one styrenic monomer, and at least one compound A2 comprising at least two boronic ester functions. They have very varied rheological properties depending on the proportion of compounds A1 and A2 used. Composition resulting from the mixing of at least one lubricating oil with such a composition of associative and exchangeable polymers and use of this composition for lubricating a mechanical part.

First claim

The invention claimed is:

1. A composition resulting from the mixing of at least one polydiol random copolymer A1 resulting from the copolymerization:
of from 1 mol % to 30 mol % of at least one first monomer M1 of general formula (I):

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

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

in which:
the asterisks (*) symbolize the bonds to oxygen atoms,
R′ 2 and R″ 2 , which may be identical or different, are chosen from the 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 having the following formula:

in which:
the asterisks (*) symbolize the bonds to oxygen atoms,
R″ 2 is chosen from the group formed by a C 6 -C 30 aryl, a C 7 -C 30 aralkyl and a C 2 -C 30 alkyl;

with from 8 mol % to 92 mol % of at least one second monomer M2 of general formula (II-B):

in which:
R 2 is —CH 3 ; and
R′″ 3 is a linear C 9 -C 15 alkyl group, and with from 0.1 mol % to 62 mol % of at least one third monomer M2 of general formula (II B) in which:
R 2 is —CH 3 ; and
R′″ 3 is a linear C 16 C 24 alkyl group, and

with from 5 mol % to 22 mol % of styrene
wherein the polydiol random copolymer A1 is obtained by a process comprising at least:
one step of radical polymerization controlled by reversible addition fragmentation chain transfer in the presence of a transfer agent having a thiocarbonylthio group and

a step of removal of the thiocarbonylthio group from the polydiol random copolymer A1,
a compound A2 comprising at least two boronic ester functions,
wherein compound A2 is a compound of formula (III):

in which:
w 1 and w 2 , which may be identical or different, are integers chosen between 0 and 1;
R 4 , R 5 , R 6 and R 7 , which may be identical or different, represent a group chosen from a hydrogen atom, a hydrocarbon-based group comprising from 1 to 30 carbon atoms, optionally substituted with one or more groups chosen from: a hydroxyl, a group —OJ or —C(O)—O—J with J being a hydrocarbon-based group comprising from 1 to 24 carbon atoms;
L is a divalent bonding group chosen from the group formed by a C 6 -C 18 aryl, a C 6 -C 18 aralkyl and a C 2 -C 24 hydrocarbon-based chain, or compound A2 is a random copolymer resulting from the copolymerization

of at least one monomer M4 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 identical or different divalent bonding groups, chosen from the group formed by C 6 -C 18 aryl, a C 7 -C 24 aralkyl and a C 2 -C 24 alkyl,
X is a function chosen from the 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 being a hydrocarbon-based chain comprising from 1 to 15 carbon atoms;
R 9 is chosen from the group formed by —H, —CH 3 and —CH 2 —CH 3 ;
R 10 and R 11 , which may be identical or different, represent a group chosen from a hydrogen atom, a hydrocarbon-based group comprising from 1 to 30 carbon atoms, optionally substituted with one or more groups chosen from: a hydroxyl, a group —OJ or —C(O)—O—J with J being a hydrocarbon-based group comprising from 1 to 24 carbon atoms;

with at least one second monomer M5 of general formula (V):

in which:
R 12 is chosen from the group formed by —H, —CH 3 and —CH 2 —CH 3 ;
R 13 is chosen from the group formed by a C 6 -C 18 aryl, a C 6 -C 18 aryl substituted with a group R′ 13 , —C(O)—O—R′ 13 ; —S—R′ 13 , —C(O)—N(H)—R′ 13 with R′ 13 being a C 1 -C 30 alkyl group,

and wherein the mass ratio between copolymer A1 and compound A2 (ratio A1/A2) ranges from 0.05 to 20.

2. The composition as claimed in claim 1 , in which the side chains of the random copolymer A1 have a mean length ranging from 8 to 20 carbon atoms.

3. The composition as claimed in claim 1 , in which the random copolymer A1 has a molar percentage of monomer M1 of formula (I) in said copolymer ranging from 5% to 25%.

4. The composition as claimed in claim 1 , in which the random copolymer A1 has a number-average degree of polymerization ranging from 40 to 2000 and a polydispersity index (Ip) ranging from 1.05 to 4.0.

5. The composition as claimed in claim 1 , in which at least one of the following three conditions is met:
either, in formula (IV): u=1, R 9 is H and R 8 represents a C 6 -C 18 aryl or a C 7 -C 24 aralkyl and the double bond of the monomer M4 of formula (IV) is directly connected to the aryl group;
or, in formula (V): R 12 represents H and R 13 is chosen from the group formed by a C 6 -C 18 aryl and a C 6 -C 18 aryl substituted with a group R′ 13 with R′ 13 being a C 1 -C 25 alkyl group and the double bond of the monomer M5 of formula (V) is directly connected to the aryl group;
or, copolymer A2 comprises at least one third monomer M3 of formula (X)

in which:
Z 1 , Z 2 and Z 3 , which may be identical or different, represent groups chosen from a hydrogen atom, a C 1 -C 12 alkyl, and a group —OZ′ or —C(O)—O—Z′ with Z′ being a C 1 -C 12 alkyl.

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

7. The composition as claimed in claim 1 , in which the side chains of copolymer A2 have a mean length of greater than or equal to 8 carbon atoms.

8. The composition as claimed in claim 1 , in which copolymer A2 has a molar percentage of monomer of formula (IV) in said copolymer ranging from 0.25% to 30%.

9. The composition as claimed in claim 1 , in which copolymer A2 has a number-average degree of polymerization ranging from 50 to 1500 and a polydispersity index (Ip) ranging from 1.04 to 3.54.

10. The composition as claimed in claim 1 , in which the content of copolymer A1 ranges from 0.1% to 50% by weight relative to the total weight of the composition.

11. The composition as claimed in claim 1 , in which the content of compound A2 ranges from 0.1% to 50% by weight relative to total weight of the composition.

12. The composition as claimed in claim 1 , in which the mass ratio between copolymer A1 and compound A2 (ratio A1/A2) ranges from 1 to 10.

13. The compositi

Assignees

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

Inventors

• Derouineau Thibault
• Briand Fanny
• Descroix Gregory
• Nicolay Renaud

Classifications

• C10M145/14 Primary

  Acrylate; Methacrylate · CPC title

• C08F212/08

  Styrene · CPC title

• C08F220/1812

  C12-(meth)acrylate, e.g. lauryl (meth)acrylate · CPC title

• C08F220/20

  of polyhydric alcohols or phenols {, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate} · CPC title

• C08F230/06

  containing boron · CPC title