Modified alkyl-phenol-aldehyde resins, use thereof as additives for improving the properties of liquid hydrocarbon fuels in cold conditions

Abstract

Modified alkylphenol-aldehyde resins include one or more alkylamines, having preferably at least one primary amine type group as well as their use for improving the flow properties of motor fuels and hydrocarbon fuels, such as in particular jet fuel, gas oil, fuel oil domestic, heavy fuel oil.

Claims

1. Modified alkylphenol-aldehyde resins obtained by a Mannich reaction of an alkylphenol-aldehyde condensation resin with: at least one aldehyde and/or one ketone having 1 to 8 carbon atoms; and at least one hydrocarbon compound having at least one alkylmonoamine or alkylpolyamine group (alkylamine) having at least one primary amine group and with an aliphatic chain having between 4 and 30 carbon atoms; the alkylphenol-aldehyde condensation resin being obtained by condensation: of at least one alkylphenol substituted by at least one linear or branched alkyl group having 1 to 30 carbon atoms; with at least one aldehyde and/or one ketone having 1 to 8 carbon atoms.

2. The resins according to claim 1, which are obtained from at least one alkylphenol substituted in para position.

3. The resins according to claim 1, which are obtained from at least one aldehyde and/or a ketone chosen from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethyl hexanal, benzaldehyde, or acetone.

4. The resins according to claim 1, wherein the alkylphenol is p-nonylphenol and wherein the aldehyde and/or ketone is formaldehyde.

5. The resins according to claim 1, which are obtained from at least one alkylamine with an aliphatic chain or a mixture of alkylamines with an aliphatic chain.

6. The resins according to claim 1, with a viscosity at 50 C. measured using a dynamic rheometer with a shear rate of 100 s-1 on a solution of the resin diluted with 30% by mass of an aromatic solvent comprised between 1,000 and 10,000 mPa.s.

7. The resins according to claim 1, wherein the aldehyde and/or ketone have 1 to 4 carbon atoms.

8. The resins according to claim 2, which are obtained from p nonylphenol.

9. The resins according to claim 3, which are obtained from at least formaldehyde.

10. The resins according to claim 1, wherein all the amine groups of the alkylamine compound are primary amines.

11. The resins according to claim 5, wherein the alkylamine(s) have a number of carbon atoms between 12 and 24.

12. The resins according to claim 6, wherein the viscosity is comprised between 1,500 and 6,000 mPa.s.

Description

DETAILED DESCRIPTION

EXAMPLE 1

Synthesis of Modified Alkylphenol-Aldehyde Resins by a Mannich Reaction

(1) In a first stage, several alkylphenol-aldehyde resins are prepared by condensation of para-nonylphenol and formaldehyde (for example according to the operating method described in EP 857 776) with viscosities at 50 C. (measured at 50 C. using a dynamic rheometer with a shear rate of 10 s.sup.1 on the resin diluted with 30% by mass of aromatic solvent (Solvesso 150) comprised between 1,800 and 4,800 mPa.Math.s. In a second stage, the alkylphenol-aldehyde resins originating from the first stage are modified by a Mannich reaction by the addition of formol and primary alkyl(poly)amine (for example an alkylpolyamine having a C12 alkyl chain (marketed under the name Noram C) for the resin (1 A)).

(2) The characteristics of the resins obtained are shown in the table 1 below: alkylamine used, amount of dry material, viscosity at 50 C. (measured on resin diluted with 30% by mass of Solvesso 150, shear rate 10 s.sup.1).

(3) TABLE-US-00001 TABLE 1 Average number Dry material Viscosity of phenolic alkylamine (1 g-30 min- at 50 C. nuclei per Resin No used 200 C.) (mPa .Math. s) resin molecule 1A Noram C 72.2% 3700 8.0 2A Trinoram S 70.30% 3675 4.1 2B Trinoram S 70.20% 1950 1.4 2C Trinoram S 70.10% 4855 14.1 2D Trinoram S 69.80% 4590 16.5 2E Trinoram S 69.00% 3180 10.1 2F Trinoram S 70.10% 4990 15.5 3A Noram SH 72.80% 2485 3.7

EXAMPLE 2

ARAL Sedimentation Tests

(4) Each of the modified alkylphenol resins of Example 1 are evaluated as anti-settling additive or WASA alone (i.e. not combined with another WASA dispersing constituent) in a gas oil (GOM 1) to which is added 300 ppm by mass of a CFPP additive which is an EVA in solution at 70% by mass in an aromatic solvent (Solvesso 150 type) marketed under the name CP7936C. Each modified alkylphenol resin is incorporated in the gas oil at a concentration of 70 ppm by mass (the resin being dissolved with 30% by mass of solvent, 100 ppm by mass of solution at 70% of active substance is used). By way of comparison, the gas oil GOM 1 to which is added 300 ppm of the CFPP additive described previously and the unmodified alkylphenol-aldehyde resin (comparative resin 1 with a viscosity measured at 50 C. using a dynamic rheometer diluted with 30% by mass Solvesso 150 equal to 2,000 mPa.Math.s) are also evaluated.

(5) The anti-settling properties of the additives are evaluated by the following ARAL settling test: 500 mL of middle distillate additives are cooled in a 500 mL test tube in a climatic chamber to 13 C. according to the following temperature cycle: passing from +10 C. to 13 C. in 4 h then isothermal at 13 C. for 16 h. At the end of the test, a visual score of the appearance of the sample and the volume of the settled phase is carried out, then the 20% constituting the volume at the bottom is taken out, for determination of cloud point CP (NF EN 23015) and CFPP (NF EN 116). Then the difference in the CP and CFPP is compared before and after settling (i.e. on the 20% volume at the bottom of the test tube), the lower difference, the better the performance of the CP, CFPP property measured.

(6) The results are shown in Table 2 below.

(7) TABLE-US-00002 TABLE 2 Volume of sediments CFPP measurement CP measurement (mL for ( C.) ( C.) Added 500 mL NF EN 116 NF EN 23015 resin N of sample) Visual score Before After Difference Before After Difference 16 Comparative 115 slightly cloudy 16 4 12 6 4 10 Resin 1 Resin 1A 90 cloudy 18 9 9 5 0 5 Resin 2A 35 cloudy 19 10 9 6 2 4 Resin 2B 50 cloudy 19 13 6 6 2 4 Resin 2C 0 homogeneous 18 19 1 6 6 0 Resin 3A 105 slightly cloudy 18 4 14 6 3 9

(8) It is noted that the unmodified standard alkylphenol resin (comparative resin 1) is not effective as regards anti-settling when it is used alone (i.e. without the addition of dispersant) whereas the modified alkylphenol resins according to the invention are, the most effective being the resin 2C, containing tallow dipropylenetriamine, particularly preferred. New ARAL sedimentation tests are carried out with the same gas oil of which the additivation rate of CFPP additive is unchanged (300 ppm) but for which the additivation rate of modified alklphenol-aldehyde resin (resin 2C) is different; once again, the modified alkylphenol-aldehyde resin is added in a solution concentrated to 70% by mass of active substance (resin) in 30% of solvent. By way of comparison, the gas oil GOM 1 to which is added 300 ppm of the CFPP additive described previously and an unmodified alkylphenol-aldehyde resin (comparative resin 1) combined with a nitrogenous polar dispersant of amidified dodecenylsuccinic anhydride type with a tallow dipropylenetriamine.

(9) The mixture of additives contains 20% by mass of resin 1 and 80% by mass of polar amidified dodecenylsuccinic anhydride dispersant with a tallow dipropylenetriamine. The results are shown in Table 3 below.

(10) TABLE-US-00003 TABLE 3 Resin added (ppm of Test tube solution at visual score CFPP measurement CP measurement WASA 70% m of (volume of ( C.) ( C.) additive(s) active sediments in mL on NF EN 116 NF EN 23015 used substance) 500 mL of sample) Before After Difference Before After Difference No WASA 0 16 Resin 2C 75 <5 homogeneous 20 17 3 6 6 0 comparative 75 <10 homogeneous 18 17 1 7 6 1 Resin 1 + dispersant Resin 2C 50 10 19 17 2 6 6 0 comparative 50 <10 homogeneous 20 19 1 7 6 1 Resin 1 + dispersant Resin 2C 25 10 homogeneous 18 18 0 6 6 0 comparative 25 125 Cloudy at 18 9 9 6 1 7 Resin 1 + the bottom dispersant Resin 2C 15 15 homogeneous 18 19 1 6 5 1 comparative 15 115 Cloudy at 16 7 9 6 1 7 Resin 1 + the bottom dispersant

(11) These results relating to the effectiveness of anti-settling as a function of concentration (of active substance) show that the modified alkylphenol resin 2C according to the invention is more effective than the combination of standard alkylphenol resin+dispersant (polar nitrogenous compound) below 50 ppm of active substance. New ARAL sedimentation tests are carried out with the resin 2C in 2 other engine gas oils (GOM 2 (gas oil of type B5, i.e. containing 5% by volume of MEVO) and GOM 3 (gas oil of type B0 without MEVO) the characteristics of which are shown in Table 6 below. By way of comparison, the anti-settling effectiveness of an unmodified alkylphenol-aldehyde resin (comparative resin 1) combined with a polar nitrogenous compound dispersant of dodecenylsuccinic anhydride type with a tallow dipropylenetriamine is evaluated; the results are shown in Tables 4 (tests in GOM 2) and 5 (tests in GOM 3)

(12) TABLE-US-00004 TABLE 4 evaluation in GOM 2 Resin added (ppm of solution at Test tube CFPP measurement CP measurement WASA 70% m of visual ( C.) ( C.) additive(s) active score NF EN 116 NF EN 23015 used substance) 500 mL Before After Difference Before After Difference comparative 112.5 100 27 10 17 4 1 5 Resin 1 + dispersant Resin 2C 112.5 <5 21* 16 5 4 4 0 *hard point at 16C.

(13) TABLE-US-00005 TABLE 5 evaluation in GOM 3 Resin added (ppm of solution to Test tube CFPP measurement CP measurement WASA 70% m of visual ( C.) ( C.) additive(s) active score NF EN 116 NF EN 23015 used substance) 500 mL Before After Difference Before After Difference comparative 100 0 19 19 0 7 7 0 Resin 1 + dispersant Resin 2C 100 <5 19 18 1 7 7 0

(14) TABLE-US-00006 TABLE 6 GOM GOM 1 GOM 2 GOM 3 Total waxes (% mass) 14.72 12.95 13.56 CFPP ( C.) NF EN 116 6 5 7 CPP ( C.) NF-T60-105 15 12 12 CP ( C.) NF EN 23015 7 5 5 MV15 (kg/m.sup.3) NF EN ISO12185 826.5 829.23 824.77 Sulphur content (mg/kg) 18.6 7.80 7.10 Monoaromatics (% mass) 19 15.7 15.7 NF EN 12916 Diaromatics (% mass) 4 2 1.8 NF EN 12916 Triaromatics (% mass) 0.3 0.5 0.5 NF EN 12916 Total aromatics (% mass) 23.3 18.2 18 NF EN 12916 Polyaromatics (% mass) 4.3 2.5 2.3 NF EN 12916 Distillation ASTM D86 ( C.) 0% 157.2 158.6 161.5 5% 178.7 183.7 183.9 10% 186.9 194 193.3 20% 207.9 215.4 211.9 30% 229.9 236.1 229.7 40% 250.1 255.60 248.1 50% 266.9 273.6 264 60% 282 289.1 277.9 70% 298.1 303.7 291.1 80% 315.5 319.5 306.7 90% 337.5 337.1 326.9 95% 353.5 350 343.6 100% 356.9 358.6 354.5 MEVO content (% vol) 0 5 0