Use of crosslinked polymers for lowering the cold filter plugging point of fuels

Abstract

The present invention concerns the use, for lowering the cold filter plugging point of a fuel composition, of one or more crosslinked polymers comprising at least one unit of the following formula (I): in which R 1 represents a hydrogen atom or a methyl group; E represents —O—CO—, or —CO—O— or —NH—CO— or —CO—NH—; and G represents a C 1 to C 34 alkyl group; said copolymer having a crosslinking rate of between 0.5 mol % and 30 mol %. The invention also concerns additive compositions containing such a polymer, and fuel compositions with such polymers as additives, in combination with a cold flow improver (CFI) chosen from the copolymers and terpolymers of ethylene and vinyl and/or acrylic ester(s).

1 . The use, for lowering the cold filter plugging point, measured according to standard NF EN 116, of a fuel composition, of one or more crosslinked polymers comprising at least one unit of the following formula (I): 
       
         
           
           
               
               
           
         
         wherein 
         R 1  represents a hydrogen atom or a methyl group, 
         E represents —O—CO—, or —CO—O— or —NH—CO— or —CO—NH—, 
         G represents a C 1  to C 34  alkyl group, 
         said copolymer having a degree of crosslinking, corresponding to the amount in moles of crosslinking agent relative to the total amount in moles of monomers in the polymer, excluding the crosslinking agent, in the range from 0.5% to 30%. 
       
     
     
         2 . (canceled) 
     
     
         3 . The use as claimed in  claim 1 , characterized in that the group E of the formula (I) is selected from: —CO—O— and —CO—NH—, on the understanding that the group E is linked to the vinyl carbon via the carbon atom, and preferably the group E of the formula (I) is the group —CO—O—. 
     
     
         4 . The use as recited in  claim 1 , characterized in that the group G of the formula (I) is a linear or branched acyclic C 1  to C 34 , preferably C 4  to C 34 , more preferentially C 4  to C 30 , more preferentially C 6  to C 24 , even more preferentially C 8  to C 22 , even better C 12  to C 14  or C 18  to C 22 , and even more preferentially C 12  to C 14  alkyl radical. 
     
     
         5 . The use as recited in  claim 4 , characterized in that the group E is a group —CO—O—, E being connected to the vinyl carbon via the carbon atom, and the group G is a linear or branched acyclic C 1  to C 34 , preferably C 4  to C 30 , more preferentially C 6  to C 24 , even more preferentially C 8  to C 22 , and even better C 12  to C 14  or C 18  to C 22 , and even more preferentially C 12  to C 14  alkyl radical. 
     
     
         6 . The use as recited in  claim 1 , characterized in that the crosslinked polymer is a homopolymer. 
     
     
         7 . The use as recited in  claim 1 , characterized in that the crosslinked polymer is a copolymer selected from block copolymers and statistical copolymers, preferably from statistical copolymers. 
     
     
         8 . (canceled) 
     
     
         9 . The use as recited in  claim 7 , characterized in that the polymer comprises additional units different from the units of the formula (I), preferably units derived from one or more vinyl monomers carrying a polar substituent. 
     
     
         10 . The use as recited in  claim 9 , characterized in that the polymer comprises units derived from one or more vinyl monomers selected from:
 2-phenoxyethylacrylate:   
       
         
           
           
               
               
           
         
         
           1-vinylimidazole: 
         
       
       
         
           
           
               
               
           
         
         
           N-vinylpyrrolidone: 
         
       
       
         
           
           
               
               
           
         
       
     
     
         11 . The use as recited in  claim 7 , characterized in that the copolymer contains at least 50 mol % of units of the formula (I), preferably at least 70 mol %. 
     
     
         12 . The use as recited in  claim 1 , characterized in that the polymer has a degree of crosslinking in the range from 1% to 20%, more preferentially from 2% to 10%, and even better from 3% to 6%. 
     
     
         13 . The use as recited in  claim 1 , characterized in that the crosslinking agent of the polymer is selected from divinyl compounds, and preferably from diacrylates and dimethacrylates of the following formula (III): 
       
         
           
           
               
               
           
         
         with
 R representing a hydrocarbon chain comprising from 2 to 16 and preferably from 3 to 12 carbon atoms, which may be interrupted by one or more heteroatoms selected from N and O, and which may be substituted by one or more —OZ groups with Z representing a hydrogen atom or a C 1  to C 4  alkyl radical, and 
 R 2  and R 3  independently representing a hydrogen atom or a methyl group. 
 
       
     
     
         14 . The use as recited in  claim 13 , characterized in that the crosslinking agent is selected from
 1,6-hexanediol dimethacrylate;   di(ethylene glycol) dimethacrylate;   glycerol dimethacrylate;   1,6-hexanediol diacrylate;   di(ethylene glycol) diacrylate; and   1,6-hexanediol ethoxylate diacrylate.   
     
     
         15 . The use as recited in  claim 1 , characterized in that the fuel composition is selected from diesels, biodiesel, B x  type diesels and fuel oils such as domestic heating oils (DHO). 
     
     
         16 . The use as recited in  claim 1 , characterized in that said crosslinked polymer is used in combination with at least one cold flow improver selected from copolymers and terpolymers of ethylene and vinyl and/or acrylic ester(s), alone or as a mixture, preferably from ethylene/vinyl acetate (EVA), ethylene/vinyl propionate (EVP), ethylene/vinyl ethanoate (EVE) and ethylene/methyl methacrylate (EMMA) copolymers; and more preferentially among ethylene/vinyl acetate (EVA) and ethylene/vinyl propionate (EVP) copolymers; still more preferentially among ethylene/vinyl acetate (EVA) copolymers. 
     
     
         17 . The use as recited in  claim 1 , characterized in that said crosslinked polymer is used in a content ranging from 2 to 100 ppm by weight, even more preferentially from 3 to 50 ppm by weight, and even better from 3 to 10 ppm by weight, based on the total weight of the fuel composition. 
     
     
         18 . An additive composition comprising a crosslinked polymer as defined in  claim 1 , and one or more cold flow improver(s) selected from copolymers and terpolymers of ethylene and vinyl and/or acrylic ester(s); preferably among ethylene/vinyl acetate (EVA), ethylene/vinyl propionate (EVP), ethylene/vinyl ethanoate (EVE), ethylene/methyl methacrylate (EMMA) copolymers; and more preferentially among ethylene/vinyl acetate (EVA) and ethylene/vinyl propionate (EVP) copolymers; and more preferentially still among ethylene/vinyl acetate (EVA) copolymers. 
     
     
         19 . (canceled) 
     
     
         20 . (canceled) 
     
     
         21 . A fuel composition comprising:
 (1) at least one hydrocarbon cut from one or more sources selected from the group consisting of mineral, animal, vegetable and synthetic sources,   (2) at least one crosslinked polymer as defined in  claim 1 , and   (3) at least one cold flow improver selected from copolymers and terpolymers of ethylene and vinyl and/or acrylic ester(s).   
     
     
         22 . (canceled) 
     
     
         23 . The composition recited in  claim 21 , characterized in that it contains the crosslinked polymer(s) in a content of 2 to 100 ppm by weight, even more preferentially 3 to 50 ppm by weight, and even better 3 to 10 ppm by weight. 
     
     
         24 . The composition as recited in  claim 21 , characterized in that the cold flow improver(s) is (are) selected from ethylene/vinyl acetate (EVA), ethylene/vinyl propionate (EVP), ethylene/vinyl ethanoate (EVE), ethylene/methyl methacrylate (EMMA) copolymers; and more preferentially among ethylene/vinyl acetate (EVA) and ethylene/vinyl propionate (EVP) copolymers; even more preferentially among ethylene/vinyl acetate (EVA) copolymers. 
     
     
         25 . (canceled) 
     
     
         26 . A process for lowering the cold filter plugging point of a fuel composition comprising a step of treating said composition with at least one crosslinked polymer as defined in  claim 1 , and with one or more cold flow improver(s) selected from copolymers and terpolymers of ethylene and vinyl and/or acrylic ester(s).