Composition of fuel oils

Abstract

The present invention relates to a fuel oil additive comprising A) a copolymer of ethylene and from 18 to 35 mol % of at least one acrylic ester or vinyl ester having a C1-C18-alkyl radical and a degree of branching of less than 5 CH3/100 CH2 groups, andB) a comb polymer comprising structural units formed fromB1) at least one olefin as monomer 1, which bears at least one C8-C18-alkyl radical on the olefinic double bond, andB2) at least one ethylenically unsaturated dicarboxylic acid as monomer 2, which bears at least one C8-C16-alkyl radical bonded via an ester group, in which the parameter Q

Description

EXAMPLES

TABLE 1
Characterization of the ethylene copolymers used
			CH3/100	Content of
Example	Comonomer(s)	V140	CH2	vinyl ester
A1 (C)	Ethylene/VAC/	110 mPas	4.2	13.3 mol%
	vinyl neodecanoate
A2	Ethylene/VAC	52 mPas	4.0	20.2 mol%
A3 (C)	Ethylene/VAC	154 mPas	3.0	16.7 mol%
A4 (C)	Ethylene/VAC	125 mPas	3.0	13.8 mol%
VAC = vinyl acetate

The vinyl ester content was measured by means of pyrolysis and subsequent titration.

The viscosity (V₁₄₀) was measured with a Haake Reostress 600 viscometer.

The degree of branching (CH₃/100CH₂) was measured on a ¹H NMR unit at 400 MHz in CDCl₃, and calculated by means of integration of the individual signals.

TABLE 2
Characterization of the comb polymers used
		Alcohol/		Acid number [mg
Example	Comonomers	Amine	Q	KOH/g]
B1	MSA-co-C14/16-α-	C12/C16	25.6	49.9
	olefin (1:0.5:0.5)	alcohol
		(85:15)
B2	MSA-co-C14/16-α-	C12 alcohol	25.0	48.2
	olefin (1:0.5:0.5)
B3	MSA-co-C14/16-α-	C12 alcohol	23.0	51.1
	olefin (1:0.5:0.5)

TABLE 3
Acrylates
C1 Poly(octadecyl acrylate), K value 32
C2 Poly(behenyl acrylate), K value 18

TABLE 4
Characterization of the test oils
	Oil No.:	CFPP [° C.]	Composition
	E1	−16	RME
	E2	−13	RME/AME 90:10
	E3	−11	RME/AME 80:20
	E4	−12	RME/SoyaME 92:8
	E5	−12	RME/SoyaME 80:20
	E6	−9	RME/SoyaME 60:40
	E7	−8	RME/PME 85:15
	SoyaME = soya methyl ester
	RME = rapeseed oil methyl ester
	PME = palm oil methyl ester
	AME = used oil methyl ester

TABLE 5
Methyl ester distribution of the test oils
	E1	E2	E3	E4	E5	E6	E7
C16:0	4.27	6.81	5.58	5.22	5.8	7.14	11.18
C18:0	0.92	2.35	2.35	1.01	1.94	2.25	2.25
C18:1	59.48	54.55	54.88	55.94	53.08	43.93	52.87
C18:2	29.56	20.79	21.84	23.48	25.27	32.04	19.43
C18:3	1.58	9.58	9.58	9.59	8.31	7.47	8.81
C20:1/2/3	1.48	1.49	1.61	1.43	1.33	1.09	1.23
C20:0	0.63	0.66	0.67	0.64	0.65	0.6	0.63
C22:0	0.23	0.39	0.44	0.39	0.39	0.39	0.34

In the tables which follow, the mixing ratio according to weight of the additives A, B and C is A:B=4:1, or, when C is present in the mixtures, A:B:C=4:1:0.2. The total amount of additive is evident from the top row of the table.

TABLE 6
CFPP testing in test oil E1
	Comb	Ethylene		1000	1200	1500
Ex.	polymer	copolymer	Polyacrylate	ppm	ppm	ppm
1	B1	A2	—	−23	−25	−27
2 (C)	B1	A1	—	−17	−19	−21

TABLE 7
CFPP testing in test oil E2
	Comb	Ethylene		1000
Ex.	polymer	copolymer	Polyacrylate	ppm	1200 ppm	1500 ppm
3 (C)	B1	A1	—	−12	−14	−17
4	B1	A2	C1	−13	−18	−22
5	B1	A2	—	−13	−17	−21
6 (C)	B2	A4	—	−14	−15	−15

TABLE 8
CFPP testing in test oil E3
	Comb	Ethylene			1000
Ex.	polymer	copolymer	Polyacrylate	800 ppm	ppm	1500 ppm
7 (C)	B1	A1	—	−11	−17	−20
8	B1	A2	—	−20	−22	−25
9 (C)	B1	A3	—	−11	−15	−15

TABLE 9
CFPP testing in test oil E4
	Comb	Ethylene			1500	2000
Ex.	polymer	copolymer	Polyacrylate	1200 ppm	ppm	ppm
10 (C)	B1	A1	—	−17	−19	−21
11	B1	A2	—	−21	−22	−23
12	B1	A2	C1	−20	−22	−23
13 (C)	B1	A3	—	−15	−17	−17
14 (C)	B2	A3	—	−14	−17	−17

TABLE 10
CFPP testing in test oil E5
	Comb	Ethylene
Ex.	polymer	copolymer	Polyacrylate	1500 ppm	2000 ppm
15 (C)	B1	A1	—	−18	−20
16	B1	A2	—	−20	−24
17 (C)	B1	A4	—	−16	−18

TABLE 11
CFPP testing in test oil E6
		Ethylene
Ex.	Comb polymer	copolymer	Polyacrylate	2000 ppm
18 (C)	B1	A1	—	−17
19	B1	A2	C2	−21
20	B1	A2	—	−20
21 (C)	B3	A4	—	−18

TABLE 12
CFPP testing in test oil E7
	Comb	Ethylene
Ex.	polymer	copolymer	Polyacrylate	4000	5000
22 (C)	B1	A1	—	−10	−14
23 (C)	B3	A3	—	−10	−14
24	B1	A2	—	−14	−16

Claims

1. A fuel oil additive comprising A) a copolymer of ethylene and from 18 to 35 mol % of at least one acrylic ester or vinyl ester having a C1-C18-alkyl radical and a degree of branching of less than 5 CH3/100 CH2 groups, andB) a comb polymer comprising structural units formed fromB1) at least one olefin as monomer 1, which bears at least one C8-C18-alkyl radical on the olefinic double bond, andB2) at least one ethylenically unsaturated dicarboxylic acid as monomer 2, which bears at least one C8-C16-alkyl radical bonded via an ester group, in which the parameter Q

2. The fuel oil additive as claimed in claim 1, wherein Q assumes values of from 24 to 26.

3. The fuel oil additive as claimed in claim 1, wherein constituent A) comprises from 18.5 to 27 mol % of at least one vinyl ester.

4. The fuel oil additive of claim 1, wherein constituent A) comprises from 0.5 to 10 mol % of olefins having from 3 to 10 carbon atoms.

5. The fuel oil additive of claim 1, wherein the degree of branching of constituent A) is less than 4 CH3/100 CH2 groups, determined by means of 1H NMR spectroscopy.

6. The fuel oil additive of claim 1, wherein the constituent B1) is an α-olefin.

7. The fuel oil additive of claim 1, wherein the monomer B1) and the comonomer B2) are present in copolymer B) in a molar ratio of between 1.5:1 and 1:1.5.

8. The fuel oil additive of claim 1, wherein copolymer B, as well as comonomers B1) and B2), also comprises up to 20 mol % of a further comonomer other than B1) and B2), selected from the group consisting of an olefin having less than 10 and more than 20 carbon atoms, an allyl polyglycol ether a C1-C30-alkyl (meth)acrylate, a vinylaromatic ether, a C1-C20-alkyl vinyl ether, and a polyisobutene having a molecular weight of up to 5000 g/mol.

9. The fuel oil additive of claim 1, wherein constituent A) has a melt viscosity V140 of from 5 to 100 mPas.

10. The fuel oil additive of claim 1, wherein constituent A) has a molecular weight Mw of from 1000 to 10 000 g/mol.

11. The fuel oil additive of claim 1, in which constituent B) has a molecular weight of from 1200 to 200 000 g/mol.

12. A fuel oil composition comprising a fuel oil of vegetable or animal origin or a mixture thereof and a fuel oil additive as claimed in claim 1.

13. The fuel oil composition as claimed in claim 12, wherein the fuel oil comprises a mixture of fatty acid esters of C1- to C4-alcohols.

14. The fuel oil composition as claimed in claim 13, wherein the fatty acid esters include stearic acid methyl ester and palmitic acid methyl ester in a proportion of at least 7% by weight.

15. A method for improving the cold behavior of a fuel oil of vegetable or animal origin or a mixture thereof, said method comprising adding the fuel oil additive of claim 1 to the fuel oil.