Polymeric compositions composed of ethylene-vinyl ester copolymers alkyl (meth)acrylates, processes for production thereof and use thereof as pour point depressants for crude oils, mineral oils or mineral oil products

Patent metadata

Field	Value
Publication number	US-9574146-B2
Application number	US-201314108488-A
Country	US
Kind code	B2
Filing date	Dec 17, 2013
Priority date	Dec 18, 2012
Publication date	Feb 21, 2017
Grant date	Feb 21, 2017

Abstract

Polymeric compositions obtainable by free-radical polymerization of at least two different alkyl (meth)acrylates in the presence of at least one ethylene-vinyl ester copolymer, the alkyl (meth)acrylates used being a mixture comprising alkyl (meth)acrylates having linear C 12 - to C 60 -alkyl radicals and different alkyl (meth)acrylates having linear C 1 - to C 11 -alkyl radicals and/or branched C 4 - to C 60 -alkyl radicals and/or cyclic C 5 - to C 20 -alkyl radicals. The use of such polymeric compositions as pour point depressants for crude oils, mineral oils or mineral oil products.

First claim

The invention claimed is:

1. A polymeric composition prepared by a process of free-radical polymerization of monoethylenically unsaturated monomers (A) in the presence of at least one ethylene-vinyl ester copolymer (B),
the monomers (A) comprising at least 70% by weight of alkyl (meth)acrylates (A1) based on the amount of all monomers (A),
the ethylene-vinyl ester copolymers (B) comprising 55 to 85% by weight of ethylene and 15 to 45% by weight of vinyl esters of the general formula H 2 C═CH—O—(O)C—R 1 (III) where R 1 is H or a C 1 -C 4 hydrocarbyl radical, and
the amount of the monomers (A) being 70 to 90% by weight and that of the ethylene-vinyl ester copolymers (B) 10 to 30% by weight based on the sum of the monomers (A) and the ethylene-vinyl ester copolymers (B) together,
wherein the alkyl (meth)acrylates (A1) are a mixture of
(A1a) 50 to 99 mol % of at least one alkyl (meth)acrylate (A1a) of the general formula H 2 C═C(R 2 )—COOR 3 where R 2 is H or a methyl group and R 3 is a linear alkyl radical having 18 to 30 carbon atoms, and
(A1b) 1 to 49 mol % of at least one alkyl (meth)acrylate (A1b) of the general formula H 2 C═C(R 2 )—COOR 4 where R 4 is a hydrocarbyl radical selected from the group of R 4a , R 4b and R 4c radicals and the radicals are each defined as follows:
R 4a : linear alkyl radicals having 1 to 11 carbon atoms,
R 4b : branched alkyl radicals having 4 to 60 carbon atoms, and
R 4c : cyclic alkyl radicals having 5 to 20 carbon atoms,
with the proviso that the sum of the amounts of (A1a) and (A1b) adds up to 100 mol %.

2. The polymeric composition according to claim 1 , wherein R 4 is a hydrocarbyl radical of R 4b .

3. The polymeric composition according to claim 2 , wherein R 4b is a branched alkyl radical having 3 to 30 carbon atoms.

4. The polymeric composition according to claim 2 , wherein R 4b is a branched alkyl radical having 4 to 17 carbon atoms.

5. The polymeric composition according to claim 1 , wherein R 3 is a linear alkyl radical having 18 to 24 carbon atoms.

6. The polymeric composition according to claim 1 , wherein R 4a is a linear alkyl radical having 2 to 6 carbon atoms.

7. The polymeric composition according to claim 1 , wherein R 4c is a cyclic alkyl radical having 6 to 10 carbon atoms.

8. The polymeric composition according to claim 1 , wherein the mean molecular weight M w of the ethylene-vinyl ester copolymers used is at least 30 000 g/mol.

9. The polymeric composition according to claim 1 , wherein the ethylene-vinyl ester copolymers (B) comprise 55 to 75% by weight of ethylene and 25 to 40% by weight of vinyl esters.

10. The polymeric composition according to claim 1 , wherein the ethylene-vinyl ester copolymers (B) comprise 60 to 75% by weight of ethylene and 25 to 40% by weight of vinyl esters.

11. The polymeric composition according to claim 1 , wherein the monomers (A) is present from 75 to 85% by weight, and the ethylene-vinyl ester copolymers (B) present from 15 to 25% by weight, based on the sum of monomers (A) and ethylene-vinyl ester copolymers (B).

12. The polymeric composition according to claim 1 , which further comprises hydrocarbons as solvents.

13. The polymeric composition according to claim 12 , wherein the hydrocarbons have a flash point ≧60° C.

14. The polymeric composition according to claim 12 , wherein the concentration of the polymeric composition in the solvent is 20 to 80% by weight based on the sum of all components of the mixture.

15. A process for prevention of wax deposits on surfaces in contact with crude oil, mineral oil, and/or mineral oil products, said process comprising adding at least one polymeric composition according to claim 1 to the crude oil, mineral oil, and/or mineral oil products.

16. A polymeric composition prepared by a process of free-radical polymerization of monoethylenically unsaturated monomers (A) in the presence of at least one ethylene-vinyl ester copolymer (B),
the monomers (A) comprising at least 70% by weight of alkyl (meth)acrylates (A1) based on the amount of all monomers (A),
the ethylene-vinyl ester copolymers (B) comprising 55 to 75% by weight of ethylene and 25 to 40% by weight of vinyl esters of the general formula H 2 C═CH—O—(O)C—R 1 (III) where R 1 is H or a C 1 - to C 4 hydrocarbyl radical, and
the amount of the monomers (A) being 70 to 90% by weight and that of the ethylene-vinyl ester copolymers (B) 10 to 30% by weight based on the sum of the monomers (A) and the ethylene-vinyl ester copolymers (B) together,
wherein the alkyl (meth)acrylates (A1) are a mixture of
(A1a) 50 to 90 mol % of at least one alkyl (meth)acrylate (A1a) of the general formula H 2 C═C(R 2 )—COOR 3 where R 2 is H or a methyl group and R 3 is a linear alkyl radical having 18 to 24 carbon atoms, and
(A1b) 10 to 50 mol % of at least one alkyl (meth)acrylate (A1b) of the general formula H 2 C═C(R 2 )—COOR 4 where R 2 is as already defined and R 4 is a hydrocarbyl radical selected from the group of R 4a , R 4b and R 4c radicals and the radicals are each defined as follows:
R 4a : linear alkyl radicals having 2 to 6 carbon atoms,
R 4b : branched alkyl radicals having 4 to 17 carbon atoms, and
R 4c : cyclic alkyl radicals having 6 to 10 carbon atoms,
with the proviso that the sum of the amounts of (A1a) and (A1b) adds up to 100 mol %.

17. The polymeric composition according to claim 16 , further comprising hydrocarbons, the hydrocarbons having a flashpoint ≧60° C., and the concentration of polymer in the composition is 20 to 80% by weight based on the sum of hydrocarbons and polymer.

18. The polymeric composition according to claim 17 , wherein R 4 is a hydrocarbyl radical of R 4b .

19. The polymeric composition according to claim 17 , wherein the radical R 4b is selected from i-butyl, t-butyl, 2,2′-dimethylpropyl, 2-ethylhexyl, 2-propylheptyl, i-nonanol, i-decyl, i-tridecyl, or i-heptadecyl.

20. The polymeric composition according to claim 17 , wherein R 4 is a hydrocarbyl radical of R 4c .

21. The polymeric composition according to claim 17 , wherein the radical R 4c is selected from cyclopentyl, cyclohexyl, 4-methylcyclohexyl, cycloheptyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, or 2-(1,7,7-trimethylbicyclo[2.2.1]heptyl.

Assignees

• Basf Se

Inventors

• Garcia Castro Ivette
• Gumlich Kai
• Frenzel Stefan
• Heuken Maria
• Konrad Rouven
• Neubecker Karin

Classifications

• C10N2030/02

  Pour-point; Viscosity index · CPC title

• C10M2203/1006

  used as base material · CPC title

• C10M145/14

  Acrylate; Methacrylate · CPC title

• C10L10/16

  Pour-point depressants · CPC title

• C10G71/00 Primary

  Treatment by methods not otherwise provided for of hydrocarbon oils or fatty oils for lubricating purposes · CPC title