COPOLYMER AND USE THEREOF FOR REDUCING CRYSTALLIZATION OF PARAFFIN CRYSTALS IN FUELS

Abstract

The present invention relates to a novel copolymer, to processes for preparation thereof and to the use thereof.

Claims

1. A copolymer, obtained by copolymerization of (A) at least one unsaturated dicarboxylic acid or a derivative thereof, (B) at least one α-olefin having from at least 6 up to and including 20 carbon atoms, (C) at least one C.sub.3- to C.sub.20-alkyl ester of acrylic acid or methacrylic acid or a mixture thereof and (D) optionally one or more further copolymerizable monomers other than monomers (A), (B) and (C), followed by reaction with at least one dialkylamine (E), where two alkyl radicals in the at least one dialkylamine (E) are independently alkyl radicals having at least 17 up to 30 carbon atoms.

2. The copolymer according to claim 1, wherein monomer (A) is 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 a derivative thereof.

3. The copolymer according to claim 1 , wherein monomer (B) is 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 1-eicosene.

4. The copolymer according to claim 1, wherein monomer (C) is an ester obtained by reacting acrylic acid or methacrylic acid with at least one alcohol selected from the group consisting of 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 copolymer according to claim 1, wherein the optional monomer (D) is selected from the group consisting of a cycloaliphatic (meth)acrylate (D1), a (meth)acrylate of a polyalkylene glycol monoalkyl ether (D2), a vinyl alkanoate (D3), an allyl compound (D4), a vinyl ether (D5), a N-vinyllactam (D6), a N-vinylimidazole (D7), an ethylenically unsaturated aromatic (D8), sulfur dioxide (D9), and an ethylenically unsaturated nitrile (D10).

6. The copolymer according to claim 1, wherein monomers (A) to (D) in copolymerized form have a molar incorporation ratio of (A):(B):(C):(D) of 1:0.5 to 2.0:0.5 to 2.0:0 to 0.1.

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

8. The copolymer according to claim 1, wherein a molar ratio of the 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 copolymer according to claim 1 having a weight-average molecular weight (M.sub.W) of 2000 to 20 000 determined by gel permeation chromatography.

10. A process for preparing the copolymer according to claim 1, the process comprising: carrying out the copolymerization at a temperature of 50 to 250° C. in an apparatus operated continuously or batchwise, and subsequently reacting with the at least one dialkylamine (E), wherein the copolymerization is solvent polymerization, emulsion polymerization, precipitation polymerization, or bulk polymerization.

11. A process for reducing a crystallization of paraffin crystal in fuel, the process comprising: introducing the copolymer according to claim 1 into the fuel.

12. A process for improving cold flow property of fuel oil or for improving filterability of fuel oil comprising cold flow improver additives, the process comprising: introducing the copolymer according to claim 1 into the fuel oil or the fuel oil comprising the cold flow improver additives.

13. A fuel oil, comprising 10 to 5000 ppm by weight of at least one copolymer according to claim 1 and optionally at least one further additive selected from the group consisting of a cold flow improver, a paraffin dispersant, a conductivity improver, an anticorrosion additive, a lubricity additive, an antioxidant, a metal deactivator, an antifoam, a demulsifier, a detergent, a cetane number improver, a solvent or diluents a diluent, a dye, and a fragrance.

Description

EXAMPLES

[0100] Preparation examples 1 to 16:

[0101] Step 1:

[0102] A 2 liter pilot stirrer system was initially charged with the amount of Solvesso® 150 and olefin specified in table A. The initial charge was sparged with N2 and heated up to 150° C. On attainment of the temperature, at the same time, the amount of maleic anhydride (MA) specified in table A, in molten form at 80° C., was added continuously to the reaction mixture through a heatable feed within 3 hours.

[0103] In parallel, the amount of tert-butyl peroxide specified in table A was metered into the reaction as initiator within 3 hours, as was, in a separate feed, the amount of the appropriate acrylate specified in table A. After the feeding of maleic anhydride and initiator had ended, the reaction mixture was left to stir further at 150° C. for one hour.

[0104] Step 2:

[0105] The amount of amine 1 specified in table A was added to the reaction mixture from step 1. The mixture was stirred at 160° C. for 4 hours. Subsequently, the amount of amine 2 specified in table A was again added all at once and the mixture was stirred for an additional 15 minutes. Subsequently, the reaction was cooled down and ended. If necessary, the copolymer was subsequently diluted to a content of 50% in Solvesso® 150.

[0106] Weight-average molecular weight (Mw) and polydispersity (PD) of the resultant copolymers were determined via GPC and reported in table B.

Use Examples

[0107] In the use examples, diesel fuels (DF) having the details of origin and indices reported in table C were used.

Efficacy as Paraffin Dispersants (WASAs)

[0108] In the examples which follow (tables 1-4), the copolymers prepared above were examined for their efficacy as paraffin dispersants (WASAs) in the presence of customary flow improvers (MDFIs).

[0109] The cloud point (CP) to ISO 3015 and the CFPP to EN 116 of the additized fuel samples were determined. Thereafter, the additized fuel samples in 500 ml glass cylinders, in order to determine the delta CP, were cooled to −16° C. in a cold bath and stored at this temperature for 16 hours. For each sample, the CP was again determined to ISO 3015 on the 20% by volume base phase separated off at −16° C. The smaller the deviation of the CP of the 20% by volume base phase from the original CP (delta CP) for the respective fuel sample, the better the dispersion of the paraffins.

[0110] The smaller the delta CP and the lower the CFPP, the better the cold flow characteristics of a diesel fuel.

[0111] The inventive copolymers improve the cold flow characteristics in terms of delta CP or CFPP or both parameters.

[0112] The procedure for the brief sediment test was analogous to Aral Method QSAA FKL 027, with the following modification:

[0113] Diesel fuels 1-4: cool to -16° C. and keep at this temperature for 16 h

[0114] WASA formulations comprise 36% by weight of the particular copolymer.

[0115] The MDFIs used are commercially available flow improver formulations: MDFI 1 is a mixture of an ethylene/vinyl acetate copolymer, an ethylene/vinyl acetate/propylheptyl acrylate terpolymer and a polyacrylate in Solvent Naphtha

[0116] MDFI 2 is an ethylene/vinyl acetate copolymer in Solvent Naphtha

[0117] MDFI 3 is an ethylene/vinyl acetate/propylheptyl acrylate terpolymer in Solvent Naphtha

[0118] MDFI 4 is an ethylene/vinyl acetate/ethylhexyl acrylate terpolymer in Solvent Naphtha

Efficacy as Cloud Point Depressants (CPD)

[0119] In table 5, the inventive copolymer from example 1 was tested in various diesel fuels for its efficacy as a cloud point depressant (CPD).

[0120] The greater the lowering of the CP compared to the unadditized fuel, the better the efficacy as a cloud point depressant.

[0121] The inventive copolymers significantly lower the CP.

[0122] CPD formulation comprises 36% by weight of the copolymer from example 1 in Solvent Naphtha.

Efficacy as a CFPP Improver (Booster)

[0123] In table 6, the inventive copolymer from example 1 was tested as a co-additive (booster) for further CFPP improvement in the presence of a customary MDFI.

[0124] By virtue of the inventive copolymers, it is possible to achieve the target CFPP with a lower total dosage, or a lower CFPP is achieved with the same total dosage.

[0125] The co-additive comprises 36% by weight of copolymer 1 in Solvent Naphtha.

TABLE-US-00001 TABLE A tert-Butyl Solvesso MA peroxide Example 150 (g) Olefin (g) (g) Acrylate (g) (g) Amine 1 (g) Amine 2 (0)  1 363 dodecene 175 102 lauryl acrylate 265 2.83 distearylamine 541 distearylamine 541  2 268.05 dodecene 129 75 lauryl acrylate 195 2.09 distearylamine 398 distearylamine 398  3 203.4 decene 87 70 lauryl acrylate 181 1.83 distearylamine 371 distearylamine 371  4 168.16 octene 72 74 lauryl acrylate 192 1.83 distearylamine 392 distearylamine 392  5 104.7 dodecene 116 68 heptadecyl acrylate 215.4 2.09 distearylamine 360 distearylamine 360  6 117.27 dodecene 129 75 tridecyl acrylate A 195 2.09 distearylamine 398 distearylamine 398  7 117.27 dodecene 129 75 tridecyl acrylate N 195 2.09 distearylamine 398 distearylamine 398  8 166.09 dodecene 180 106 nonyl acrylate 213 2.61 distearylamine 562 distearylamine 562  9 198.27 dodecene 213 124 n-butyl acrylate 162.5 2.61 distearylamine 657 distearylamine 657 10 315 dodecene 153 87 ethylhexyl acrylate 163.7 2.09 distearylamine 461 distearylamine 461 11 (comp.) 363 dodecene 175 102 lauryl acrylate 265 2.83 distearylamine 540 didodecylamine 368 12 (comp.) 150 — — 139 lauryl acrylate 361 2.61 distearylamine 737 distearylamine 737 13 (comp.) 495.8 dodecene 600 175 — — 4.85 distearylamine 928 distearylamine 928 14 (comp.) 313 C20-24 268 102 — — 4.2 distearylamine 541 distearylamine 541 15 (comp.) 96.8 dodecene 108.7 63.43 behenyl acrylate 227.9 2.09 distearylamine 336 distearylamine 336 16 (comp.) 363 dodecene 175 102 lauryl acrylate 265 2.83 didodecylamine 368 distearylamine 540

TABLE-US-00002 TABLE B Molecular weight Example (Mw) PD 1 4250 2 2 3750 2 3 3310 2 4 5150 2.2 5 5200 2.1 6 5670 2.1 7 4520 2.2 8 5390 2 9 5060 2.1 10 2860 2 11 (comp.) 4250 2 12 (comp.) 4450 2.1 13 (comp.) 4000 2 14 (comp.) 4200 2.1 15 (comp.) 7510 2.5 16 (comp.) 4250 2

TABLE-US-00003 TABLE C DF 1 DF 2 DF 3 DF 4 DF 7 DF 8 DF 9 DF 11 Central Central Eastern Central Southern Central Central DF 10 Eastern Origin Europe Europe Europe Europe Europe Europe Europe USA Europe Cloud point CP −5.6 −7.1 −8.3 −4.8 −5.3 −6.1 −4.9 −15.5 −7.8 [° C.] CFPP [° C.] −5 −8 −8 −5 −13 −8 −6 −18 −9 Density @15° C. 842.6 839.2 827.9 845.1 841.3 839.7 834.1 831.4 830 [kg/m3]  90% by vol.- 118 n.d. 115 113 127 124 114 116 113 20% by vol. [° C.] IBP [° C.] 168 n.d. 179 172 171 171 164 167 167 FBP [° C.] 359 n.d. 359 360 363 356 359 363 355 n-Paraffins [%] 18.2 19.1 21.9 17.1 15.2 19.3 17.2 15.6 16.9

TABLE-US-00004 TABLE 1 DF 1; CFPP: −5° C.; CP: −5.6° C. WASA with Dosage copolymer from Dosage CFPP Delta CP MDFI [ppm] example [ppm] [° C.] [K] MDFI 1 150 1 150 −29 2.4 MDFI 1 150 4 150 −30 3.2 MDFI 1 150 5 150 −27 1.7 MDFI 1 150 6 150 −28 2.7 MDFI 1 150 7 150 −27 2.8 MDFI 1 150 9 150 −28 2.8 MDFI 1 150 11 (comp.) 150 −25 5.5 MDFI 1 150 12 (comp.) 150 −16 3.2 MDFI 1 150 14 (comp.) 150 gelated n.a. MDFI 1 150 15 (comp.) 150 −9 6.1 MDFI 1 150 16 (comp.) 150 −19 4.1

TABLE-US-00005 TABLE 2 DF 2; CFPP: −8° C.; CP: −7.1° C. WASA with Dosage copolymer from Dosage CFPP Delta CP MDFI [ppm] example [ppm] [° C.] [K] MDFI 2 150 1 150 −29 1.3 MDFI 2 150 2 150 −27 0.9 MDFI 2 150 3 150 −27 1.4 MDFI 2 150 6 150 −29 1.5 MDFI 2 150 8 150 −27 1.4 MDFI 2 150 10 150 −27 1.4 MDFI 2 150 12 (comp.) 150 −27 2.4 MDFI 2 150 15 (comp.) 150 −10 5.1

TABLE-US-00006 TABLE 3 DF 3; CFPP: −8° C.; CP: −8.3° C. WASA with Dosage copolymer from Dosage CFPP Delta CP MDFI [ppm] example [ppm] [° C.] [K] MDFI 3 300 1 200 −28 1.9 MDFI 3 300 3 200 −28 1.1 MDFI 3 300 7 200 −29 2 MDFI 3 300 11 (comp.) 200 −27 9 MDFI 3 300 13 (comp.) 200 −24 4.1 MDFI 3 300 15 (comp.) 200 −20 6.3 MDFI 3 300 16 (comp.) 200 −20 2

TABLE-US-00007 TABLE 4 DF 4; CFPP: −5° C.; CP: −4.8° C. WASA with Dosage copolymer from Dosage CFPP Delta CP MDFI [ppm] example [ppm] [° C.] [K] MDFI 1 150 1 150 −29 3.3 MDFI 1 150 7 150 −26 3.4 MDFI 1 150 9 150 −26 3.1 MDFI 1 150 15 (comp.) 150 −7 6.4

TABLE-US-00008 TABLE 5 CP CP CP CP CP CPD Dosage [° C.] [° C.] [° C.] [° C.] [° C.] formulation [ppm] DF 7 DF 8 DF 9 DF 10 DF 11 — — −5.3 −6.1 −4.4 −15.5 −7.8 Copolymer from ex. 1 100 −6.2 — −5.8 −17.2 −9.1 Copolymer from ex. 1 300 −7.1 −8.5 −6.7 −17.9 −10 Copolymer from ex. 1 500 −7.7 −9 −7.1 −18.3 −10.6

TABLE-US-00009 TABLE 6 DF 11; CFPP: −9° C.; CP: −7.8° C. Dosage Copolymer Dosage CFPP MDFI [ppm] from example [ppm] [° C.] — — — — −9 MDFI 4 100 — — −13 MDFI 4 200 — — −20 MDFI 4 300 — — −23 MDFI 4 150 1 50 −23 MDFI 4 225 1 75 −28