Hydrogenated polymers with a radial structure having a core based on calixarenes and use thereof in lubricant compositions

Patent metadata

Field	Value
Publication number	US-10584299-B2
Application number	US-201515304757-A
Country	US
Kind code	B2
Filing date	Apr 16, 2015
Priority date	Apr 17, 2014
Publication date	Mar 10, 2020
Grant date	Mar 10, 2020

Abstract

Hydrogenated polymers with a radial structure having a core made up of calixarenes of the general formula (I), to the core of which is linked a number P of hydrogenated linear polymer segments selected from: —hydrogenated homopolymers or copolymers of conjugated dienes; or —hydrogenated copolymers of said conjugated dienes and monoalkenyl arenes, and —mixtures thereof said formula (I) in which: —R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen; a group containing carbon and hydrogen; a group also containing heteroatoms in addition to carbon and hydrogen; a group also containing silicon in addition to carbon, hydrogen and heteroatoms; —one of the two substituents R 5 and R 6 is hydrogen, while the other may be hydrogen or alkyl, with a number of carbon atoms between 1 and 6, preferably methyl and ethyl; —n is an integer in the range between 4 and 16.

First claim

The invention claimed is:

1. Hydrogenated polymers with a radial structure having a core made up of calixarenes of the general formula (I), to the core of which is linked a number P of hydrogenated linear polymer segments selected from:
hydrogenated homopolymers or copolymers of conjugated dienes; or
hydrogenated copolymers of said conjugated dienes and monoalkenyl arenes, and
mixtures thereof,
said formula (I) being

in which:
R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen; a group containing carbon and hydrogen; a group also containing heteroatoms in addition to carbon and hydrogen; a group also containing silicon in addition to carbon, hydrogen and heteroatoms;
one of the two substituents R 5 and R 6 is hydrogen, while the other may be hydrogen or alkyl, with a number of carbon atoms between 1 and 6;
n is an integer in the range between 4 and 16.

2. Hydrogenated radial polymers according to claim 1 , in which the linear polymer segments are hydrogenated homopolymers or hydrogenated copolymers of conjugated dienes selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 3-butyl-1,3-octadiene, 1-phenyl-1,3-butadiene and 1,3-hexadiene.

3. Hydrogenated radial polymers according to claim 2 , in which the linear polymer segments are selected from homopolymers or copolymers of butadiene and isoprene.

4. Hydrogenated radial polymers in which the linear polymer segments are hydrogenated copolymers of the conjugated dienes according to claim 2 and of monoalkenyl arenes selected from styrene, ortho-methylstyrene, para-methylstyrene, meta-methylstyrene, tert-butylstyrene and monovinylnaphthalene.

5. Hydrogenated radial polymers according to claim 4 , in which the linear polymer segments are hydrogenated copolymers of butadiene and styrene, or hydrogenated copolymers of isoprene and styrene.

6. Hydrogenated radial polymers according to claim 1 , in which R 1 and R 2 may be selected from:
an alkyl having a number of carbon atoms between 1 and 24; or
a group also containing heteroatoms in addition to carbon and hydrogen and having a number of carbon atoms between 1 and 16; or
a group also containing silicon in addition to carbon, hydrogen and heteroatoms in which the number of carbon atoms varies between 5 and 21; or
an unsaturated hydrocarbon group, with or without heteroatoms, having a number of carbon atoms between 2 and 16.

7. Hydrogenated radial polymers according to claim 1 in which R 3 , R 4 , R 5 and R 6 are simultaneously hydrogen.

8. Hydrogenated radial polymers according to claim 1 , in which P is between 4 and 72.

9. Hydrogenated radial polymers according to claim 1 , in which the weight-average molecular weight (M W ) of each of the hydrogenated linear polymer segments which make up the hydrogenated radial polymer is between 10000 and 200000.

10. Hydrogenated radial polymers according to claim 1 , in which the weight-average molecular weight (M W ) of the hydrogenated radial polymers is between 100000 and 2000000.

11. A synthesis method for the radial polymers according to claim 1 which comprises the following steps:
i. synthesising a calixarene of the general formula (I);
ii. preparing the linear polymer segments by anionic polymerisation in solution of one or more conjugated dienes, or by copolymerisation of one or more conjugated dienes and a monoalkenyl arene, in the presence of an ionic initiator to form a living anionic polymer;
iii. reacting the living anionic polymer obtained in (ii) with the calixarene synthesised in (i) to form a polymer with a radial structure; and
iv. reacting, by selective hydrogenation, the olefinic unsaturations present in the radial polymer obtained in (iii) to obtain a hydrogenated radial polymer.

12. A synthesis method for the radial polymers according to claim 11 , in which the living polymers are those arising from the copolymerisation of a conjugated diene with a monoalkenyl arene, and characterised by a monalkenyl arene content between 3% by weight and 30% by weight relative to the total weight of the copolymer, and a diene content between 97% by weight and 70% by weight relative to the total weight of the copolymer.

13. A method according to claim 12 , in which the living polymers are those arising from the copolymerisation of butadiene and styrene, and are characterised by a styrene content between 5% by weight and 25% by weight relative to the total weight of the copolymer and a butadiene content between 95% by weight and 75% by weight relative to the total weight of the copolymer.

14. A method according to claim 11 , in which the quantity of calixarene added in the coupling reaction of the living anionic polymer with the calixarene in step (iii) is between 0.8/P mol and 1.2/P mol per mol of living polymer.

15. A method according to claim 11 , in which the coupling reaction of the living anionic polymer with the calixarene in step (iii) is carried out in the presence of an inert solvent selected from aliphatic hydrocarbons, aromatic hydrocarbons and ethers.

16. A method according to claim 15 , in which the inert solvent is the same as that used in step (ii).

17. A method according to claim 11 , in which the temperature at which the coupling reaction of the living anionic polymer with the calixarene is carried out in step (iii) is between 0° C. and 150° C., and said reaction is carried out under an inert atmosphere at an absolute pressure in the range between 0.5 and 10 atm.

18. A method according to claim 11 , in which the radial polymer obtained in reaction stage (iii) is hydrogenated in reaction step (iv) in such a way that the degree of hydrogenation of the initially present olefinic unsaturations is greater than 85%.

19. The hydrogenated polymers with a radial structure according to claim 1 wherein one of the two substituents R5 and R6 is hydrogen, while the other is an alkyl, with a number of carbon atoms between 1 and 6.

Assignees

• Eni Spa
• Versalis Spa

Inventors

• Notari Marcello
• Cavallo Claudio
• Roselli Alberto
• Casnati Alessandro
• Sansone Francesco
• Burlini Alessandro

Classifications

• C10N2060/02

  Reduction, e.g. hydrogenation · CPC title

• C10N2020/073

  Star shaped polymers · CPC title

• C10N2070/00

  Specific manufacturing methods for lubricant compositions · CPC title

• C10N2030/02

  Pour-point; Viscosity index · CPC title

• C10N2030/68

  Shear stability · CPC title