NZ227523A - Liquid hydrocarbon fuel containing the reaction product of linear alkyl succinic anhydride (or corresponding acid), an epoxide and a secondary amine having at least 14 carbon atoms - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £27523 o WO DRAWINGS 22 7 5 2 3 Priority Date(s): Complete Specification Filed: Cfaw: O.Q 2'fWW" Publication Date: P.O. Journal, No: ..J23&, NEW ZEALAND PATENTS ACT, 1953 c L.< No.: Date: COMPLETE SPECIFICATION LOW TEMPERATURE FLUIDITY IMPRi / n We. MOBIL OIL CORPORATION, a corporation organised under the laws Qf the i State of New York, United States of America, of 150 East 42nd Styre4t, New York, State of New York, United States of America, hereby declare the invention for which 2rI we pray that a patent may be granted to jjac/us, and the method by which it is to be performed, to be particularly described in and by the following statement: - (followed by page la) 22 7 5 2 3 F-4M* — j<a.— LOW TEMPERATURE FLUIDITY IMPROVER This invention relates to fuel compositions having improved low temperature characteristics. More particularly, this invention relates to compositions comprising distillate hydrocarbon fuels having minor amounts sufficient to improve cloud point, pour point and filterability of diesel and heating fuels of an additive prepared from the reaction products of long chain oligomeric alkylsuccinic anhydride or corresponding acid, a long chain mono-or polyfunctional epoxide and a long chain secondary amine.

As is well known to those skilled in the art, diesel fuels and the like present problems at low temperatures because of poor flow characteristics and clogging of fuel filters. Unmodified diesel fuels have especially poor flow characteristics at colder temperatures where wax crystal formation occurs. Consequently, there is a continuing need for more efficient means for solving these low temperature fluidity problems. The materials described herein, when added to such fuels, improve their low temperature filterability and flowability characteristics.

Although many lubricant and fuel additives have been described from various alkylsuccinic anhydrides and their esters, applicants have discovered that effective products for improving low temperature properties of diesel fuels and the like can be made from specific combinations of raw materials within a limited molecular weight range comprising an alkylsuccinic anhydride or long chain carboxylic acid or polyacid, a mono- or polyfunctional epoxide and a long chain secondary amine.

U.S. Patent 4,108,613 teaches the use of a mixture of (1) the reaction product of an epoxidized alpha-olefin with a nitrogen-containing compound selected from ammonia, an amine, a polyamine or a hydroxyamine and (2) an ethylene-olefin copolymer as an additive to depress the pour point of hydrocarbonaceous fuels and oils. e o Vw-- c C 227523 F-4508 -2- U.S. Patent 3,962,104 discloses lubricating oil compositions containing minor amounts of quaternary ammonium salts useful as oil improving additives wherein the quaternary ammonium salts utilize a cation derived from the reaction product of a tertiary amine with an olefin oxide and water. None of these prior art materials, however, use the specific combination of raw materials disclosed herein.

Applicants have now discovered novel fuel additive products useful in improving the low temperature characteristics of distillate fuel compositions, which compositions comprise a major proportion of a liquid hydrocarbon fuel and a minor proportion sufficient to impart improved filterability and flowability characteristics thereto, and to provide a lower pour point and lower cloud point to said composition comprising the reaction product of (1) a substantially linear alkylsuccinic anhydride or the corresponding acid prepared from a substantially linear oligomerized olefin of the following generalized structure: (RCH=CH2)n where n is 2-4, and where R is C2 to C^ hydrocarbyl; (2) a long chain, fatty or alphatic secondary amine having at least 14 carbon atoms. (3) and a long chain Cj2+ high molecular weight epoxide having at least 12 carbon atoms.

Applicants have found that to be effective the products for improving low temperature properties of diesel fuels or heating fuels in accordance with their discovery must be made from specific combinations of raw materials within a limited molecular weight range: (1) The alkylating olefin used to prepare the alkylsuccinic anhydride must be essentially linear. (2) The olefin must be carefully oligomerized so that for (RCH=CH2)n, n is 2-4. When n is 1, or 5 or more, the materials have proven ineffective. (Mixtures, however, may contain som©*^^ material where n is outside the limits). (3) The amine must be secondary; primary amines are ineffective.

F-450S —3— 22 75 23 (4) The epoxide should have a MW of at least 185.

Suitable liquid hydrocarbon fuels or distillates generally have an initial boiling point of 177°C (350°F) and an end point of 357°C (675°F). However, it is understood that the additives in accordance with this invention may be utilized in hydrocarbon fuels outside these specific boiling ranges. Generally speaking, these additive products may be utilized in any unmodified diesel fuel which has poor flow characteristics at winter temperatures and where wax crystal formation occurs.

Suitable alkyl succinic anhydrides are those wherein the alkyl group is an oligomer of long chain alkenes. As noted hereinabove, the chain must contain at least 14 carbon atoms. There is no critical upper limit. However, preferably, the chain should contain from 16 to 40 carbon atoms. With respect to the olefin described above as being (RCH=CF2)n, the nature of the R substituent is not critical but preferably will contain from 12 to 32 and preferably 16 to 24 carbon atoms.

The epoxides useful herein generally contain from 12 to 30 carbon atoms. The epoxides may be substituted with an aromatic or a saturated or unsaturated aliphatic group. Among the preferred epoxides that may be used in the present invention are decene epoxide, tetradecene epoxide and octadecene epoxide and the like. It is emphasized that the above list is non-limiting. Any other suitable epoxides, within the preferred group of epoxides having from 12 to 30 carbon atoms may be advantageously used. The MW of these epoxides will generally range from 185 to 500 or more.

Suitable secondary amines generally having the formula R-NH-R where R is to C-jq hydrocarbyl includes, but are not limited to the following: dicocoamine, or N-ethyl-oleylamine, N-methyl soya amine, di-tallow amine, and the like are also believed to be suitable.

Normal epoxide/amine reaction temperatures are room temperature or ambient to 225°C. Normal esterification conditions m V.„. c c 22 7 5 23 P-4508" --4-- are used (100-250°C, azeotropic removal of water, etc.). Any suitable method, however, is acceptable. Oligomerization may be by any convenient method as for example shown in Example 1, infra.

The additives in accordance with the invention may be used effectively in hydrocarbyl distillate diesel fuels in an amount ranging from 0.01 wt.l to 5 wt.% or more based on the total weight of the fuel composition. In certain cases depending, for example, on a particular fuel and/or on weather conditions, up to 10 wt.% may be used. Other known additives may also be used for their intended purposes without deleterious effect upon the additives of the invention.

EXAMPLE 1 Preparation of an Oligomer A commercial mixture of hexadecenes and octadecenes in which the double bond may be placed anywhere in the linear carbon chain (500g) was mixed with a 2.3g n-butanol and heated to 52-57°C in a dry inert atmosphere. Boron trifluoride (7.3g) was gradually added over a three hour period, maintaining the temperature in this range to accelerate the reaction without corrosion of the equipment. The reaction mixture was held at this temperature for a further three hours after the addition was complete. The catalyst was neutralized with 30 cc of concentrated ammonia in 200 cc water, and the product was washed.

EXAMPLE 2 Preparation of Alkylsuccinic Anhydride Ttie oligomer prepared in Example 1 (155.5g) was heated to 235°C and 41.5g maleic anhydride was added over a two hour period. Hie mixture was held at that temperature an additional three hours before stripping the excess maleic anhydride at 160°C under vacuum for three hours.

F 450(P 22 75 2 PRFPARATION OF ADDITIVES EXAMPLE 3 A commercial mixture of epoxidized C24-28 olefins (16.2 g, 0.04 moles), was heated with a commercial di(hydrogenated tallow) amine (21.3 g, 0.04 moles), with stirring at 125°C for three hours. A dimerized alkylsuccinic anhydride (12.8 g, 0.02 moles) prepared in the manner of Fxample 2 was added, the temperature raised to 175°C and the reaction mixture held at that temperature for three hours. The final acid value was 2.

EXAMPLE 4 A preparation similar to Example 3 was made substituting an equimolar amount of a commercial C]8-20 a*P^a olefin epoxide for the ^24-28 eP°x^e^ olefins.

COMPARATIVE EXAMPLES EXAMPLE 5 This Example uses a commercially available reaction product of tallow amine and a low molecular weight epoxide. A commercial reaction product of tallow amine and 2 moles of ethylene oxide, (57.6 g, 0.16 moles) was reacted with dimerized Cig_24+ alkylsuccinic anhydride at 160°C, using toluene to azeotropically remove the water. When no more water evolved, the reaction was finished at 150°C for 3 hours under vacuum. This product had no effect on the cloud point of the test Diesel Fuel.

EXAMPLE 6 This Example uses a long chain primary amine instead of the secondary amine of Example 3. Hydrogenated tallow amine (14.2 g, 0.05 moles) and 20.1 g C24_2g epoxidized olefins (0.05 moles) were heated at 125° for three hours. The same alkylsuccinic anhydride F-4568- — 6— 227523 used in Example 1 (15.9 g, 0.025 moles) was added and the reaction completed as in Example 3. This additive did not materially lower the cloud point.

The additive materials are blended (0.1* by weight) into a typical diesel fuel described below and tested for cloud point, pour-point, filterability by the LTFT procedure described below. Properties of the test diesel fuel are shown in Table 1.

TABLE 1 Typical Diesel Distillation °F °C Fuel Initial 366 186 50% 487 253 End 663 351 API Gravity 34.8 Sulfur 0.174 Aniline Point 54 °C (130 °F) LTFT, Low Temperature Flow Test for Diesel Fuels, is a filtration test under consideration oy CRC (Coordination Research Council). The LTFT Procedure is as follows: The test sample (200 ml) is gradually lowered to the desired testing temperature at a controlled cooling rate. After reaching that temperature the sample is removed from its cold box and filtered under vacuum through a 17 micrometer screen. If the entire sample can be filtered in less than 60 seconds its shall be considered as having passed the test. The cloud point and pour point data are obtained by standard ASTW Tests, respectively (D-250 and D-97).

A review of Table 2 highlights the criticality claimed for the individual reactants. Thus the data of Table 2 show the highly successful and improved results obtained when additives in accordance with the invention are incorporated into diesel fuels.

Claims (14)

22 7 5 2 3 TABLE 2 Example Cloud Point LTFT Pour Point F °C °F °C aF 1 ' flC Base Riel 22 -6 18 -8 0 -18 3 17 -8 14 -10 -20 -29 4 18 -8 14 -10 -40 -40 5 21 -6 - - - - 6 21 -6 - . - O e 22 7 5 2 3 jyHAT*riVE CLAIM IS:

1. A composition comprising a major proportion of a liquid hydrocarbon fuel and a minor proportion of an additive product comprising the reaction product of (a) a substantially linear alkylsuccinic anhydride or the corresponding acid prepared from a substantially linear oligomerized olefin of the following generalized structure: (RCH - CH2)n where n is from 2 to 4 and where R is from to C^2 hydrocarbyl (b) a mono- or polyfunctional epoxide having at least 12 carbon atoms, and Cc) a secondary amine having at least 14 carbon atoms.

2. The composition of claim 1 wherein said epoxide is monofunctional.

3. The composition of claim 1 wherein said epoxide is polyfunctional.

4. The composition of claim 1 which contains 0.01 wt % to 10 wt % of said additive product.

5. The composition of claim 1 wherein said alkylsuccinic anhydride is prepared from a mixture of hexadecene and octadecenes oligomerized olefins and maleic anhydride and where n is 2; the epoxide is a mixture of C24_28 eP°xidized olefins and the amine is a di(hydrogenated) tallow amine. 227523 —9--

6. The composition of claim 5 wherein said alkylsuccinic anhydride is prepared from a mixture of substantially linear ("16-18 olefins and the epoxide is a monofunctional epoxide.

7. The composition of claim 5 wherein the epoxide is a ^18~^20 olefin epoxide.

8. The composition of claim 5 wherein the epoxide is a polyfunctional epoxide.

9. The composition of claim 1 wherein said fuel is a diesel fuel.

10. An additive product suitable for use in liquid hydrocarbon fuels imparting thereto improved filterability characteristics and providing lower pour points and lower cloud points for said fuels, said additive product comprising the reaction product of (a) a substantially linear alkylsuccinic anhydride having been prepared from a substantially oligomerized olefin of the following generalized structure: (RCH = CH2)n where n is 2-4 and where R is from C12 to C^ hydrocarbyl, (b) a C24 to C2g mono or polyfunctional epoxide or mixtures thereof and, (c) a secondary amine having at least 14 carbon atoms.

11. A composition according to any one of claims 1 to 9 comprising a major proportion of a liquid hydrocarbon fuel and a minor proportion of an additive product substantially as herein described with reference to the Examples.

12. An additive product according to claim 10 suitable for use in liquid hydrocarbon fuels substantially as herein destysikgd fs. T E with reference to the Examples. A -10- 227523

13. A composition which comprises a major proportion of a liquid hydrocarbon fuel and a minor proportion of an additive comprising the reaction product of: a. an alkyl succinic anhydride, or the corresponding acid, prepared from an oligomer of a linear olefin, the oligomer having the formula: R is from to hydrocarbyl; and n is a number from 2 to 4; b. a mono- or polyfunctional epoxide having at least 12 carbon atoms, and c. a secondary amine having at least 14 carbon atoms.

14. The use of an additive defined in any of the preceding claims in a liquid hydrocarbon fuel to impart improved filterability, a lower pour point or a wherein: (RCH=CH2)n lower cloud point to the fuel. By fciu/thelr authorised Agents-, A. J. PARK & SON.