Multiple-function dispersant graft polymer
A grafted polymer, either polyolefin or polyester, containing monomers associated with sludge and varnish control as well as monomers associated with soot handling to provide a graft polymer exhibiting multiple performance attributes. Also described are methods for manufacturing these novel multiple-function graft polymers via solution and melt processes. Lubricating oil compositions containing these novel multiple-function polymers as an additive that display performance characteristics directed to good soot handling and sludge and varnish control as well as control of viscosity increase are described.
1. A multiple function dispersant graft polymer containing at least two different grafted monomers, each directly grafted to a polyolefin polymer backbone having a weight average molecular weight of from about 10,000 to about 1,000,000, the polyolefin polymer backbone having graftable sites, in which:
a first grafted monomer comprises an ethylenically unsaturated, aromatic monomer selected from the group consisting of 1-vinylimidazole, N-allylimidazole, 2-vinylpyridine, 4-vinylpyridine, 4-methyl-5-vinyl thiazole, N-allyl diisooctyl phenothiazine, 2-methyl-1-vinylimidazole, 3-methyl-1-vinylpyrazole, N-vinylpurine, and combinations thereof; and
a second grafted monomer comprises an acylating agent with which at least one amine has been reacted, wherein said amine is selected from the group consisting of N-phenylphenylenediamines, N-phenyl-1,4-phenylenediamine, N-phenyl-1,3-phenylenediamine, N-phenyl-1,2-phenylenediamine, N-naphthylphenylenediamine, N-phenylnaphthalenediamine, N′-aminopropyl-N-phenylphenylenediamine, N-arylphenylenediamines represented by the formula:
in which Ar is aromatic and R 1 is hydrogen, —NH-aryl, —NH-arylalkyl, —NH-alkylaryl, or a branched or straight chain radical having from 4 to 24 carbon atoms and the radical can be an alkyl, alkenyl, alkoxyl, arylalkyl, alkylaryl, hydroxyalkyl or aminoalkyl radical, R 2 is —NH 2 , —NH(CH 2 ) n —) m —NH 2 , —CH 2 —(CH 2 ) n —NH 2 , -aryl-NH 2 , in which n and m each has a value from 1 to 10, and R 3 is hydrogen or an alkyl, alkenyl, alkoxyl, arylalkyl, or alkylaryl radical, which may have from 4 to 24 carbon atoms; and
in which R 4 , R 5 , and R 6 are hydrogen or a linear or branched hydrocarbon radical containing from 1 to 10 carbon atoms and that radical may be an alkyl, alkenyl, alkoxyl, alkylaryl, arylalkyl, hydroxyalkyl, or aminoalkyl radical, and R 4 , R 5 and R 6 can be the same or different;
aminocarbazoles represented by the formula:
in which R 7 and R 8 represent hydrogen or an alkyl, alkenyl, or alkoxyl radical having from 1 to 14 carbon atoms, and R 7 and R 8 can be the same or different;
aminoindoles represented by the formula:
in which R 9 represents hydrogen or an alkyl radical having from 1 to 14 carbon atoms, amino-indazolinones represented by the formula:
in which R 10 is hydrogen or an alkyl radical having from 1 to 14 carbon atoms, aminomercaptotriazole represented by the formula:
aminoperimidines represented by the formula:
in which R 11 represents hydrogen or an alkyl or alkoxyl radical having from 1 to 14 carbon atoms and combinations thereof,
which has from about 1 mole to about 74 moles of first graft monomer per mole of backbone polymer and from about 1 mole to about 74 moles of second graft monomer per mole of backbone polymer, wherein the total moles of first graft monomer and second graft monomer per mole of backbone polymer is not greater than 75 moles;
wherein the multiple function dispersant graft polymer has a Rapid ADT response of at least 4.
2. The multiple function dispersant polymer of claim 1 , wherein said polymer backbone has a weight average molecular weight of from about 10,000 to about 500,000.
3. The multiple function dispersant polymer of claim 1 , wherein said polymer backbone has a polydispersity of from about 1 to about 15.
4. The multiple function dispersant polymer of claim 1 , wherein said polymer backbone comprises a polyolefin having a weight average molecular weight of from about 10,000 to about 500,000 and a polydispersity from about 1 to about 15.
5. The multiple function dispersant graft polymer of claim 1 , wherein said ethylenically unsaturated monomer is selected from the group consisting of 1-vinylimidazole N-allylimidazole, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-1-vinylimidazole, and combinations thereof.
6. The multiple function dispersant graft polymer of claim 5 , wherein said acylating agent is selected from the group consisting of maleic acid, fumaric acid, maleic anhydride, and combinations thereof.
7. The multiple function dispersant graft polymer of claim 5 , wherein said amine is selected from the group consisting of N-phenylphenylenediamines, N-phenyl-1,4-phenylenediamine, N-phenyl-1,3-phenylenediamine, N-phenyl-1,2-phenylenediamine, N-naphthylphenylenediamine, N-phenylnaphthalenediamine, N′-aminopropyl-N-phenylphenylenediamine,
and combinations thereof.
8. The multiple function dispersant graft polymer of claim 7 ,
wherein said polymer backbone comprises a polyolefin having a weight average molecular weight of from about 10,000 to about 500,000 and a polydispersity from about 1 to about 15; and
wherein said acylating agent is selected from the group consisting of maleic acid, fumaric acid, maleic anhydride, and combinations thereof,
the multiple function dispersant graft polymer has from about 5 moles to about 50 moles of first graft monomer per mole of backbone polymer and from about 5 moles to about 50 moles of second graft monomer per mole of backbone polymer.
9. The multiple function dispersant graft polymer of claim 1 , wherein said amine is N-phenyl-1,4-phenylenediamine.
10. The multiple function dispersant polymer of claim 1 , having a Rapid ADT response of from about 4 to about 32.
11. The multiple function dispersant polymer of claim 1 , having a Rapid ADT response of from about 4 to about 16.
12. The multiple function dispersant graft polymer of claim 1 , wherein said first graft monomer is 1-vinylimidazole; said second graft monomer is selected from the group consisting of maleic acid, fumaric acid, maleic anhydride, and combinations thereof; and said amine is N-phenyl-1,4-phenylenediamine.
13. The multiple function dispersant graft polymer of claim 12 ,
wherein said polymer backbone comprises a polyolefin having a weight average molecular weight of from about 10,000 to about 500,000 and a polydispersity from about 1 to about 15; and
the multiple function dispersant graft polymer has from about 5 moles to about 50 moles of first graft monomer per mole of backbone polymer and from about 5 moles to about 50 moles of second graft monomer per mole of backbone polymer.
14. The multiple function dispersant graft polymer of claim 12 , which has from about 5 moles to about 50 moles of first graft monomer per mole of backbone polymer and from about 5 moles to about 50 moles of second graft monomer per mole of backbone polymer.
15. The multiple function dispersant graft polymer of claim 12 , wherein the ratio of the first graft monomer to the second graft monomer is from about 0.3:1 to about 1:0.3.
16. A graft polymer according to claim 12 , wherein
the N-vinyl imidazole is present in an amount to sufficient to impart the graft polymer with dispersancy associated with sludge and varnish handling; and
the N-phenyl-1,4-diamine reacted to the acylating agent is present in an amount to sufficient to impart the graft polymer with soot handling performance.
17. The multiple function dispersant polymer of claim 1 having about 7 moles of first graft monomer per mole of backbone polymer and about 7 moles of second graft monomer per mole of backbone polymer.
18. The multiple function dispersant polymer of claim 1 , which has from about 3 moles to about 60 moles of first graft monomer per mole of backbone polymer and from about 3 moles to about 60 moles of second graft monomer per mole of backbone polymer.
19. The multiple function dispersant polymer of claim 18 , which has from about 5 moles to about 50 moles of first graft monomer per mole of backbone polymer and from about 5 moles to about 50 moles of second graft monomer per mole of backbone polymer.
20. The graft polymer of claim 1 , which has a Rapid ADT response of at least about 8.
21. The multiple function dispersant graft polymer of claim 1 , wherein the ratio of the first graft monomer to the second graft monomer is from about 0.3:1 to about 1:0.3.
22. The multiple function dispersant graft polymer of claim 1 , prepared by a process comprising:
grafting the acylating agent on the polymer backbone; and then
grafting the ethylenically unsaturated monomer on the polymer backbone; and then
reacting the amine with the acylating reagent.