Copolymers of bicyclic (meth)acrylates and alkyl (meth)acrylates and their use as rheology modifiers in fuels
The invention relates to a specific copolymer obtainable by co-polymerizing at least the following monomers: —at least one bicyclic (meth)acrylate ester —at least one C8-C24-alkyl (meth)acrylate —optionally, and preferably, at least one aromatic vinyl monomer; and —optionally other ethylenically unsaturated monomers, whereby the copolymer has a weight averaged molecular weight from 400,000 to 50,000,000 Dalton, as well as to the way to synthesize them and the use of such polymers to modify the rheology of a liquid in which they are soluble.
1. A copolymer that is soluble for at least 2 wt % in diesel at 25° C., the copolymer comprising the following monomers:
21 wt % or more, based on the weight of all monomers, of at least one bicyclic (meth)acrylate ester,
at least one C8-C24-alkyl (meth)acrylate, wherein the C8-C24-alkyl group is linear or branched, substituted or unsubstituted, saturated or unsaturated,
optionally at least one aromatic vinyl monomer, and
optionally other ethylenically unsaturated monomers,
wherein the copolymer has a weight averaged molecular weight from 400,000 to 50,000,000 Daltons.
2. The copolymer according to claim 1 , wherein the bicyclic (meth)acrylate ester is of formula (I)
wherein R is H or —CH 3 , A is CH 2 —, —CH(CH 3 )— or —C(CH 3 ) 2 —, and M is covalently bonded to a carbon atom of the six-membered ring and is selected from the group consisting of hydrogen, a methyl group and combinations thereof.
3. The copolymer according to claim 1 , wherein the copolymer is a random co-polymer.
4. The copolymer according to claim 1 , comprising:
21 to 95 wt % of bicyclic (meth)acrylate ester,
5 to 79 wt % of C8-C24-alkyl (meth)acrylate,
0 to 65 wt % of aromatic vinyl monomer, and
0 to 50 wt % of other ethylenically unsaturated monomers,
up to a total of 100 wt %, wherein the weight percentages of the monomer are based on the total weight of all the monomers.
5. The copolymer according to claim 4 , comprising
40 to 90 wt % of bicyclic (meth)acrylate ester,
10 to 35 wt % of C8-C24-alkyl (meth)acrylate,
5 to 50 wt % of aromatic vinyl monomer, and
0 to 40 wt % of other ethylenically unsaturated monomers,
up to a total of 100 wt %, wherein the weight percentages of the monomer are based on the total weight of all the monomers.
6. The copolymer according to claim 5 , comprising
60 to 85 wt % of bicyclic (meth)acrylate ester,
15 to 25 wt % of C8-C24-alkyl (meth)acrylate,
10 to 35 wt % of aromatic vinyl monomer,
0 to 40 wt % of other ethylenically unsaturated monomers,
up to a total of 100 wt %, wherein the weight percentages of the monomer are based on the total weight of all the monomers.
7. The copolymer according to claim 1 , comprising a total of bicyclic (meth)acrylate ester and C8-C24-alkyl (meth)acrylate in an amount of 35 wt % or more.
8. The copolymer according to claim 1 , comprising a total of bicyclic (meth)acrylate ester and aromatic vinyl monomer in an amount of 35 wt % or more.
9. The copolymer according to claim 1 , wherein the at least one bicyclic (meth)acrylate ester comprises isobornyl methacrylate.
10. The copolymer according to claim 1 , wherein the at least one C8-C24-alkyl methacrylate comprises lauryl (meth)acrylate, methacrylic ester 13.0, (iso)decyl (meth)acrylate and combinations thereof.
11. The copolymer according to claim 1 , wherein the at least one aromatic vinyl monomer comprises styrene.
12. The copolymer according to claim 1 , wherein the copolymer has a solubility of at least 2.0 weight percent in diesel B7 at 25° C.
13. The copolymer according to claim 1 , wherein the copolymer has a cloud point of 25° C. or lower in diesel B7 fuel.
14. The copolymer according to claim 1 , wherein the copolymer has a weight average molecular weight of at least 500,000 D.
15. The copolymer according to claim 1 , wherein the copolymer has a glass transition temperature from 50° C. to 190° C.
16. An additive package for fuels comprising the copolymer of claim 1 .
17. A method for the preparation of a copolymer of claim 1 comprising the step of radically polymerizing the monomers.
18. A method for the preparation of the additive package for fuels of claim 16 , the method comprising: (i) making a solution comprising a copolymer that is soluble for at least 2 wt % in diesel at 25° C., the copolymer comprising the following monomers:
at least one bicyclic (meth)acrylate ester,
at least one C8-C24-alkyl (meth)acrylate, wherein the C8-C24-alkyl group is linear or branched, substituted or unsubstituted, saturated or unsaturated,
optionally at least one aromatic vinyl monomer, and
optionally other ethylenically unsaturated monomers,
wherein the copolymer has a weight averaged molecular weight from 400,000 to 50,000,000 Daltons and (ii) adding one or more fuel additives to the solution.
19. A method for modifying the rheology of a fluid, the method comprising dissolving the copolymer of claim 1 into the fluid, wherein the fluid is not a fuel for combustion engines.
20. The copolymer according to claim 1 , comprising
5 to 40 wt % of C8-C24-alkyl (meth)acrylate.