Polymeric-inorganic particles useful as lubricant additives
View Patent ↗The invention relates to polymeric-inorganic nanoparticles and preparation processes thereof. The invention also relates to a powder, concentrate and lubricating composition comprising these polymeric-inorganic nanoparticles, to a method of dispersing nanoparticles in lubricating oil, as well as the use of these polymeric-inorganic particles in an oil lubricant formulation to reduce pour point, friction and wear.
1. A polymeric-inorganic nanoparticle, comprising one inorganic nanoparticle covalently bonded to one or more polymers, each polymer comprising:
a) units derived from at least one compound of formula (I):
and
b) units derived from at least one alkyl (meth)acrylate, wherein the alkyl group of the alkyl (meth)acrylate comprises from 1 to 40 carbon atoms,
wherein:
at least two units a) of each polymer are covalently bonded to the inorganic nanoparticle;
R is H or CH 3 ;
Si(A) h (X) 3−h is a silane functional group, where 0≤h≤2;
A is a branched or unbranched C1 to C4 alkyl residue;
B is a branched or unbranched, aliphatic, aromatic or mixed aliphatic-aromatic C1 to C30 carbon-based group;
X is selected from H, Cl or a group OY, wherein Y is H or a C to C30 branched or unbranched alkyl-, alkenyl-, aryl-, or aralkyl- group, branched or unbranched C2 to C30 alkylether-group or branched or unbranched C2 to C30 alkylpolyether-group or a mixture thereof; and
the units b) derived from the at least one alkyl (meth)acrylate are selected from the group consisting of:
(b1) 0 to 30% by weight of units derived from at least one alkyl (meth)acrylate monomer of formula (II), based on the total weight of the monomer composition:
where R is hydrogen or methyl, and R 1 is a linear, branched or cyclic alkyl residue with 1 to 8 carbon atoms,
(b2) 0 to 99.9% by weight of units derived from at least one alkyl (meth)acrylate monomer of formula based on the total weight of the monomer composition:
where R is hydrogen or methyl, and R 2 is a linear, branched or cyclic alkyl residue with 9 to 15 carbon atoms, and
(b3) 0 to 99.9% by weight of units derived from at least one alkyl (meth)acrylate monomer of formula (IV), based on the total weight of the monomer composition:
where R is hydrogen or methyl, and R 3 is a linear, branched or cyclic alkyl residue with 16 to 40 carbon atoms,
wherein:
each polymer comprises at least 10% by weight of either monomer units b2) or b3) or a mixture of both, based on the total weight of the monomer composition; and
the amounts of monomers a), b1), b2) and b3) are selected to sum up to 100% by weight of the mixture of monomers a), b1), b2) and b3).
2. The polymeric-inorganic nanoparticle according to claim 1 , wherein the compound of formula (I) is selected from the group consisting of 3-(triethoxysilyl)propyl methacrylate, 3-(trimethoxysilyl)propyl methacrylate, and 3-(trichlorosilyl)propyl methacrylate.
3. The polymeric-inorganic nanoparticle according to claim 1 , wherein each polymer consists of the units a) and the units b).
4. The polymeric-inorganic nanoparticle according to claim 1 , wherein the at least one polymer further comprises comonomer units.
5. The polymeric-inorganic nanoparticle according to claim 1 , wherein the inorganic nanoparticle is selected from the group consisting of a metal oxide nanoparticle, an oxidized metal nitride nanoparticle, an oxidized metal carbide nanoparticle, a non-metal oxide nanoparticle, and mixtures thereof.
6. The polymeric-inorganic nanoparticle according to claim 1 , wherein the inorganic nanoparticle is selected from the group consisting of SiO 2 and TiO 2 .
7. The polymeric-inorganic nanoparticle according to claim 1 , wherein each polymer comprises 0.1% by weight to 50% by weight of the units a), based on the total weight of the monomer composition.
8. The polymeric-inorganic nanoparticle according to claim 1 , wherein each polymer comprises:
a) 0.1 to 50% by weight of the units a) derived from one or more compounds of formula (I), based on the total weight of the monomer composition;
b2) 0 to 99.9% by weight of units derived from at least one alkyl (meth)acrylate monomer of formula (III), based on the total weight of the monomer composition:
where R is hydrogen or methyl, and R 2 is a linear, branched or cyclic alkyl residue with 9 to 15 carbon atoms; and
b3) 0 to 99.9% by weight of units derived from at least one alkyl (meth)acrylate monomer of formula (IV), based on the total weight of the monomer composition:
where R is hydrogen or methyl, and R 3 is a linear, branched or cyclic alkyl residue with 16 to 40 carbon atoms,
wherein:
the at least one polymer comprises at least 10% by weight of either monomer units b2) or b3) or a mixture of both, based on the total weight of the monomer composition; and
the amounts of monomers a), b2) and b3) are selected to sum up to 100% by weight of the mixture of monomer units a), b2) and b3).
9. The polymeric-inorganic nanoparticle according to claim 1 , wherein each polymer comprises at least 50% by weight of either monomer units b2) or b3) or a mixture of both, based on the total weight of the monomer composition.
10. The polymeric-inorganic nanoparticle according to claim 9 , wherein the units derived from one or more alkyl (meth)acrylate monomers of Formula (II), (III) and (IV) comprise:
(b1) 0 to 5% by weight of units derived from at least one alkyl (meth)acrylate monomer of formula (II), based on the total weight of the monomer composition;
(b2) 40 to 75% by weight of units derived from at least one alkyl (meth)acrylate monomer of formula (III), based on the total weight of the monomer composition; and
(b3) 5 to 50% by weight of units derived from at least one alkyl (meth)acrylate monomer of formula (IV), based on the total weight of the monomer composition.
11. The polymeric-inorganic nanoparticle according to claim 1 , wherein each polymer comprises a terminal polymer chain end derived from silane-containing chain transfer agent.
12. The polymeric-inorganic nanoparticle according to claim 1 , wherein each polymer has a weight average molecular weight of 5 000 g/mol to 200 000 g/mol.
13. The polymeric-inorganic nanoparticle according to claim 1 , wherein a weight ratio between the nanoparticle and the one or more polymers covalently bonded to the inorganic nanoparticle is from 1:0.02 to 1:1.
14. A process for preparing the polymeric-inorganic nanoparticle of claim 1 , the process comprising:
(i) polymerizing a monomer composition comprising the at least one compound a) of formula (I) and the at least one alkyl (meth)acrylate b), to obtain the polymer; and
(ii) covalently bonding the polymer with the inorganic nanoparticles.
15. The process of claim 14 , wherein the covalently bonding step (ii) is conducted in a base oil or an organic solvent.
16. The process of claim 14 , wherein the covalently bonding step (ii) occurs with mixing at high speed greater than 4000 RPM, and optionally with an ultrasonic treatment.
17. The process of claim 14 , wherein the polymerizing step (i) occurs in the presence of a reactive silane containing chain transfer agent.
18. A concentrate, comprising the polymeric-inorganic nanoparticles of claim 1 , wherein 10 to 90% by weight of the polymeric-inorganic nanoparticles are dispersed in a base oil or an organic solvent, based on a total weight of the concentrate.
19. A powder, comprising the polymeric-inorganic nanoparticles of claim 1 .
20. A lubricating composition, comprising the polymeric-inorganic nanoparticles of claim 1 .
21. The lubricating composition as claimed in claim 20 , comprising 50 to 99.99% by weight of at least one base oil, based on a total weight of the lubricating composition.
22. A method for producing the polymeric-inorganic nanoparticle of claim 1 , the method comprising covalently bonding the inorganic nanoparticles dispersed in a lubricating oil with the one or more polymers.
23. An oil lubricant formulation for reducing friction and/or wear, wherein the oil lubricating formulation comprises the polymeric-inorganic nanoparticle of claim 1 .
24. A composition, comprising the polymeric-inorganic particle of claim 1 , wherein the composition is selected from the group consisting of a continuously variable transmission fluid, an engine oil, a gear oil, a hydraulic oil, and a grease.
25. A method for reducing the pour point of a lubricant composition, the method comprising adding the polymeric-inorganic nanoparticle of claim 1 to the lubricant composition.
26. A pour point depressant, comprising the polymeric-inorganic particles of claim 9 .