Copolymer and use thereof for reducing crystallization of paraffin crystals in fuels

Patent metadata

Field	Value
Publication number	US-11060044-B2
Application number	US-201716099870-A
Country	US
Kind code	B2
Filing date	May 16, 2017
Priority date	May 24, 2016
Publication date	Jul 13, 2021
Grant date	Jul 13, 2021

Abstract

The present invention relates to a copolymer obtainable by copolymerization of
(A) at least one unsaturated dicarboxylic acid or derivatives thereof,
(B) at least one α-olefin having from at least 6 up to and including 20 carbon atoms,
(C) optionally at least one C 3 - to C 20 -alkyl ester of acrylic acid or methacrylic acid or a mixture of such alkyl esters and
(D) optionally one or more further copolymerizable monomers other than monomers (A), (B) and (C),
with a molar incorporation ratio of (A):(B):(C):(D) of 1:0.5 to 2.0:0 to less than 0.5:0 to 0.1
followed by the reaction with at least one dialkylamine (E), where the two alkyl radicals in the at least one dialkylamine (E) are independently alkyl radicals having at least 17 up to 30 carbon atoms.

First claim

The invention claimed is:

1. A fuel composition, comprising:
a fuel,
a copolymer having a wax anti-settling effect, and
at least one further component comprising a cold flow improver,
wherein the copolymer is obtained by copolymerization of monomers comprising:
(A) at least one unsaturated dicarboxylic acid or derivative thereof;
(B) at least one α-olefin comprising from 6 to 20 carbon atoms;
(C) optionally at least one C 3 - to C 20 -alkyl ester of acrylic acid or methacrylic acid or a mixture of such alkyl esters; and
(D) optionally at least one further copolymerizable monomer other than monomers (A), (B) and (C),
wherein a molar incorporation ratio of (A):(B):(C):(D) is from 1:0.5 to 2.0:0 to less than 0.5:0 to 0.1,
followed by reaction with at least one dialkylamine (E), where the two alkyl radicals in the at least one dialkylamine (E) are independently alkyl radicals comprising from 17 to 30 carbon atoms,
wherein the molar ratio of dialkylamine (E) based on units of the dicarboxylic acid (A) incorporated in the copolymer is at least 1.1:1.

2. The fuel composition according to claim 1 , wherein monomer (A) is at least one selected from the group consisting of maleic acid, fumaric acid, 2-methylmaleic acid, 2,3-dimethylmaleic acid, 2-methylfumaric acid, 2,3-dimethylfumaric acid, methylenemalonic acid and tetrahydrophthalic acid and derivatives thereof.

3. The fuel composition according to claim 1 , wherein monomer (B) is at least one selected from the group consisting of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and -eicosene.

4. The fuel composition according to claim 1 , wherein monomer (C) is at least one selected from the group consisting of esters of acrylic acid and methacrylic acid with n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, n-pentanol, tert-pentanol, n-hexanol, n-heptanol, n-octanol, 2-ethylhexanol, n-nonanol, isononanol, n-decanol, 2-propylheptanol, n-undecanol, isoundecanol, n-dodecanol, n-tridecanol, isotridecanol, 3,3,5,5,7-pentamethyloctanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, isoheptadecanol, 3,3,5 5,7,7,9-heptamethyldecanol, n-octadecanol and n-eicosanol.

5. The fuel composition according to claim 1 , wherein the optional monomer (D) is at least one selected from the group consisting of cycloaliphatic (meth)acrylates (D1), (meth)acrylates of polyalkylene glycol monoalkyl ethers (D2), vinyl alkanoates (D3), allyl compounds (D4), vinyl ethers (D5), N-vinyllactams (D6), N-vinylimidazoles (D7), ethylenically unsaturated aromatics (D8), sulfur dioxide (D9), ethylenically unsaturated nitriles (D10) and esters of acrylic acid or methacrylic acid that bear at least one aromatic ring system (D11).

6. The fuel composition according to claim 1 , wherein the monomers in copolymerized form have a molar incorporation ratio of (A):(B):(C):(D) of 1:0.6 to 1.5:more than 0 to less than 0.5:0 to 0.05.

7. The fuel composition according to claim 1 , wherein the dialkylamine (E) is di-n-octadecylamine, di-n-nonadecylamine or di-n-eicosylamine.

8. The fuel composition according to claim 1 , wherein the molar ratio of dialkylamine (E) based on incorporated units of the dicarboxylic acid (A) in the copolymer is at least 1.2:1 and up to 2.0:1.

9. The fuel composition according to claim 1 , wherein the monomers in copolymerized form have a molar incorporation ratio of (A):(B):(C):(D) of 1:0.6 to 1.5:0:0 to 0.05, with the proviso that the sum total of the statistical average number of carbon atoms in the monomer (B) and the statistical average number of carbon atoms of the alkyl radicals in the dialkylamine (E) is at least 30.

10. The fuel composition according to claim 9 , wherein the molar ratio of dialkylamine (E) based on incorporated units of the dicarboxylic acid (A) in the copolymer is from 1.1:1 to 1.9:1.

11. The fuel composition according to claim 1 , wherein the copolymer has a weight-average molecular weight (M w ) of 2000 to 20,000 as determined by gel permeation chromatography.

12. The fuel composition according to claim 1 , wherein the copolymer is obtained by solvent polymerization, emulsion polymerization, precipitation polymerization or bulk polymerization at a polymerization temperature of 50 to 250° C. in at least one apparatus operated continuously or batchwise.

13. A process, comprising reducing crystallization of paraffin crystals in a fuel, the process comprising:
combining the fuel and a cold flow improver with a copolymer having a wax anti-settling effect, thereby reducing crystallization of paraffin crystals in the fuel and obtaining the fuel composition according to claim 1 .

14. A process for improving a cold flow property of a fuel oil and/or improving filterability of a fuel oil, the process comprising:
combining the fuel, a cold flow improver, and a copolymer having a wax anti-settling effect, thereby obtaining the fuel composition according to claim 1 .

15. The fuel composition according to claim 1 , wherein the fuel composition has a content of 10 to 5000 ppm by weight of one or more of the copolymer; and
wherein the fuel composition optionally further comprises at least one further additive selected from the group consisting of paraffin dispersants, conductivity improvers, anticorrosion additives, lubricity additives, antioxidants, metal deactivators, antifoams, demulsifiers, detergents, cetane number improvers, solvents or diluents, dyes and fragrances.

Assignees

• Basf Se

Inventors

• Troetsch-Schaller Irene
• Garcia Castro Ivette
• Schroers Michael
• Rebholz Uwe
• Faul Dieter
• Oswald Anke

Classifications

• C10L2270/026

  for diesel engines, e.g. automobiles, stationary, marine · CPC title

• C10L2230/14

  for improving storage or transport of the fuel · CPC title

• C10L10/16

  Pour-point depressants · CPC title

• C10L1/238

  obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds {(C10L1/221 takes precedence)} · CPC title

• C10L1/1966

  poly-carboxylic · CPC title