Additive mixture as component of mineral oil compositions

Abstract

An additive mixture as component of compositions of mineral oil as the main component and trace portions of an additive mixture contains the additive components a) ethylene-vinylester copolymers with molecular mass weight averages from 3000 to 50000 and an ethylene proportion of 50 to 90 mass %, and b) mixed esters of glycerine in which 50 to 80 mol % of the hydroxy groups are esterified with unsaturated C 12 -C 40 monocarboxylic acids and 20 to 50 mol % of the hydroxy groups are esterified with partially imidated and/or partially esterified maleic anhydride copolymers, and/or c) partially and/or completely imidated copolymers consisting of maleic anhydride and α-methylstyrene with molecular mass number averages from 1500 to 15000 and at least one terminal group based on dimeric α-methyl styrene, and/or d) wax compositions based on natural starting materials of type d1) wax-like oligomeric esters based on glyceryl monostearate and dimeric acid and/or d2) wax esters with vaseline-like consistency, based on at least two different straight-chain and/or branched C 14 -C 36 -alcohols and dimeric acid whereby the content of the additive mixture in the mineral oil is 0.005 to 1 mass % and the mass proportion of the additive components a/b or a/c or a/d is in the range from 10:90 to 90:10, respectively. The mineral oil compositions are suitable as flowable media to be transported at low temperatures and as mineral oil fuels with high lubricity and flowability.

1 . Compositions of mineral oil as the main component and trace portions of an additive mixture wherein the additive mixture comprises the additive components 
 a) ethylene-vinylester copolymers with molecular mass weight averages from 3000 to 50000 and an ethylene proportion of 50 to 90 mass %,    and    b) mixed esters of glycerine in which 50 to 80 mol % of the hydroxy groups are esterified with unsaturated C 12 -C 40  monocarboxylic acids and 20 to 50 mol % of the hydroxy groups are esterified with partially imidated and/or partially esterified maleic anhydride copolymers,    and/or    c) partially and/or completely imidated copolymers of maleic anhydride and α-methylstyrene with molecular mass number averages from 1500 to 15000 and at least one terminal group based on dimeric α-methylstyrene,    and/or    d) wax compositions based on natural starting materials of type    d1) wax-like oligomeric esters based on glyceryl monostearate and dimeric acid in which the conversion product corresponds to the                           structure by at least 90 mass %, 
 where n=1 to 20, the total of a+b+c+d=30, z=12 to 20 
                     
 and/or  
   d2) wax esters with vaseline-like consistency based on at least two different straight-chain and/or branched C 14 -C 36  alcohols and dimeric acids in which the conversion product corresponds to the                           structure by at least 80 mass %, 
 where i=13 to 35; s=13 to 35,  
 the total of k+m+n+p is 30 to 34, and (CH 2 ) i  or (CH 2 ) s  are straight-chain or straight-chain and branched,  
 whereby the content of the additive mixture in the mineral oil is 0.005 to 1 mass % and the mass proportion of the additive components a/b or a/c or a/d is in the range from 10:90 to 90:10, respectively.  
   
   
   
       2 . The compositions according to  claim 1  wherein the ethylene-vinylester copolymers of the additive mixture are ethylene-vinylacetate copolymers with a vinylacetate content of 12 to 50 mass %.  
   
   
       3 . The compositions according to  claim 1  wherein the ethylene-vinylester copolymers of the additive mixture are mixtures of 10 to 90 mass % of unmodified ethylene-vinylester copolymers and 90 to 10 mass % of ethylene-vinylester copolymers modified by polar groups.  
   
   
       4 . The compositions according to  claim 3  wherein the modified ethylene-vinylester copolymers of the additive mixture are oxidized ethylene-vinylester copolymers, partially saponified ethylene-vinylester copolymers, hemiacetals of partially saponified ethylene-vinylester copolymers and/or ethylene-vinylester copolymers grated with polar unsaturated monomers of the vinyl ester, (meth)acryl ester, and/or vinyl ether type.  
   
   
       5 . The compositions according to one or several of  claim 1  wherein the C 12 -C 40 -monocarboxylic acids contained as esterifying components in the mixed esters of glycerine of the additive mixture consist of 45 to 52 mass % C 22 -monocarboxylic acids in relation to the overall weight of the C 12 -C 24 -monocarboxylic acids, and wherein the partially imidated maleic anhydride copolymers contained as esterifying components are maleic anhydride-α-methylstyrene copolymers partially imidated with C 6 -C 40 -monoalkylamines in which the mole ratio of anhydride groups in the copolymer/C 6 -C 24 -monoalkylamine bound in the copolymer is in the range of from 8:1 to 1.3:01.  
   
   
       6 . The compositions according to  claim 1  wherein the partially imidated copolymer of maleic anhydride and α-methylstyrene as additive component c) are maleic anhydride-α-methylstyrene copolymers partially imidated with C 6 -C 24  monoalkylamines in which the mole ratio of anhydride groups in the copolymer/bound C 6 -C 24  monoalkylamine in the copolymer is from 8:1 to 1.3:1.  
   
   
       7 . Compositions according to  claim 1  wherein the wax esters with vaseline-like consistency as additive component d2) are wax esters based on Guerbet alcohols of the 2-hexyldecane-1-ol, 2-octyldecane-1-ol or 2-octyldecane-1-ol type and dimeric acids obtained by splitting vegetable oils with a high oleic acid content and subsequent catalytic dimerization.  
   
   
       8 . Compositions of mineral oil according to  claim 1  wherein the mineral oils are crude oils or fuel oils from a middle distillate with a sulfur content under 0.05 mass %, preferably heating oils, gas oils, or diesel oils.  
   
   
       9 . Compositions of mineral oil according to  claim 1  wherein the mineral oil compositions contain a total of 0 up to 200 mass % in relation to the additive components a+b, a+c, a+d, a+b+c, a+b+c+d, or a+c+d of other additive components such as fatty acid mixtures, polar nitrogen compounds, preferably polyamines, etheramines, amino alcohols, amine salts, amides or imides of multivalent carboxylic acids; modified copolymers of ethylenically unsaturated C 4 -C 20 -dicarboxylic anhydrides, non-modified ethylene-vinylester copolymers, C 7 -C 30 -alcohols, polyalkylene glycols, esters or ethers of polyoxyalkylene compounds, C 2 -C 6 -oxyalkyl-bridged C 12 -C 40 -monocarboxylic acids, preferably C 3 -C 4 -oxyalkyl-bridged unsaturated C 16 -C 24 -monocarboxylic acids with a content of C 22 -monocarboxylic acids in relation to the overall weight of the C 16 -C 24 -monocarboxylic acids of 45 to 52 mass %, hydrocarbon polymers, alkylphenol-aldehyde copolymers, aromatic compounds with C 8 -C 100 -alkyl substituents, carboxylated polyamines, detergents, corrosion inhibitors, demulsifiers, metal deactivators, cetane number improvers, defoaming agents and/or cosolvents.  
   
   
       10 . A method for producing compositions of mineral oil as the main component and trace portions of an additive mixture wherein the additive mixture, which comprises the additive components 
 a) ethylene-vinylester copolymers with molecular mass weigh averages from 3000 to 50000 and an ethylene proportion of 50 to 90 mass 5, 
 and  
   b) mixed esters of glycerine in which 50 to 80 mol % of the hydroxy groups are sterified with unsaturated C 12 -C 40  monocarboxylic acids and 20 to 50 mol % of the hydroxy groups are esterified with partially imidated and/or partially esterified maleic anhydride copolymers, 
 and/or  
   c) partially and/or completely imidated copolymers of maleic anhydride and α-methylstyrene with molecular mass number averages from 1500 to 15000 and at least one terminal group based on dimeric α-methylstyrene,    and/or    d) wax compositions based on natural starting materials of type 
 d1) wax-like oligomeric esters based on glyceryl monostearate and dimeric acid in which the conversion product corresponds to the  
                     
  structure by at least 90 mass %, 
 where n=1 to 20, the total of a+b+c+d=30, z=12 to 20 
                     
 and/or  
 
 d2) wax esters with vaseline-like consistency based on at least two different straight-chain and/or branched C 14 -C 36  alcohols and dimeric acids in which the conversion product corresponds to the  
                     structure by at least 80 mass %,    where i=13 to 35; s=13 to 35,    the total of k+m+n+p is 30 to 34, and    (CH 2 ) i  or (CH 2 ) s  are straight-chain or straight-chain and branched,    whereby the content of the additive mixture in the mineral oil is 0.005 to 1 mass % and the mass proportion of the additive components a/b or a/c or a/d is in the range from 10:90 to 90:10, respectively, are produced in a prehomogenization process in which 
 solutions containing 1 to 60 mass % of additive components in mineral oil middle distillates are produced at 20 to 90° C. in a first process step, and  
 the solutions containing the additive components are homogenized with the mineral oil as the main component in a second process step,  
   while other additive components of a total of 0 to 200 mass % in relation to the additive components a+b, a+c, a+d, a+b+c, a+b+c+d, or a+c+d are added to the mineral oil in the first and/or second process step.    
   
   
   
       11 . Use of compositions according to  claim 1  as flowable media to be transported at low-temperatures and as mineral oil fuel with high lubricity and flowability.  
   
   
       12 . The compositions according to  claim 2  wherein the ethylene-vinylester copolymers of the additive mixture are mixtures of 10 to 90 mass % of unmodified ethylene-vinylester copolymers and 90 to 10 mass % of ethylene-vinylester copolymers modified by polar groups.  
   
   
       13 . The compositions according to  claim 12  wherein the modified ethylene-vinylester copolymers of the additive mixture are oxidized ethylene-vinylester copolymers, partially saponified ethylene-vinylester copolymers, hemiacetals of partially saponified ethylene-vinylester copolymers and/or ethylene-vinylester copolymers grated with polar unsaturated monomers of the vinyl ester, (meth)acryl ester, and/or vinyl ether type.  
   
   
       14 . The compositions according to  claim 2  wherein the C 12 -C 40 -monocarboxylic acids contained as esterifying components in the mixed esters of glycerine of the additive mixture consist of 45 to 52 mass % C 22 -monocarboxylic acids in relation to the overall weight of the C 12 -C 40 -monocarboxylic acids, and wherein the partially imidated maleic anhydride copolymers contained as esterifying components are maleic anhydride-α-methylstyrene copolymers partially imidated with C 6 -C 40 -monoalkylamines in which the mole ratio of anhydride groups in the copolymer/C 6 -C 24 -monoalkylamine bound in the copolymer is in the range of from 8:1 to 1.3:01.  
   
   
       15 . The compositions according to  claim 3  wherein the C 12 -C 40 -monocarboxylic acids contained as esterifying components in the mixed esters of glycerine of the additive mixture consist of 45 to 52 mass % C 22 -monocarboxylic acids in relation to the overall weight of the C 12 -C 40 -monocarboxylic acids, and wherein the partially imidated maleic anhydride copolymers contained as esterifying components are maleic anhydride-α-methylstyrene copolymers partially imidated with C 6 -C 40 -monoalkylamines in which the mole ratio of anhydride groups in the copolymer/C 6 -C 24 -monoalkylamine bound in the copolymer is in the range of from 8:1 to 1.3:01.  
   
   
       16 . The compositions according to  claim 4  wherein the C 12 -C 40 -monocarboxylic acids contained as esterifying components in the mixed esters of glycerine of the additive mixture consist of 45 to 52 mass % C 22 -monocarboxylic acids in relation to the overall weight of the C 12 -C 40 -monocarboxylic acids, and wherein the partially imidated maleic anhydride copolymers contained as esterifying components are maleic anhydride-α-methylstyrene copolymers partially imidated with C 6 -C 40 -monoalkylamines in which the mole ratio of anhydride groups in the copolymer/C 6 -C 24 -monoalkylamine bound in the copolymer is in the range of from 8:1 to 1.3:01.  
   
   
       17 . The compositions according to  claim 12  wherein the C 12 -C 40 -monocarboxylic acids contained as esterifying components in the mixed esters of glycerine of the additive mixture consist of 45 to 52 mass % C 22 -monocarboxylic acids in relation to the overall weight of the C 12 -C 40 -monocarboxylic acids, and wherein the partially imidated maleic anhydride copolymers contained as esterifying components are maleic anhydride-α-methylstyrene copolymers partially imidated with C 6 -C 40 -monoalkylamines in which the mole ratio of anhydride groups in the copolymer/C 6 -C 24 -monoalkylamine bound in the copolymer is in the range of from 8:1 to 1.3:01.  
   
   
       18 . The compositions according to  claim 13  wherein the C 12 -C 40 -monocarboxylic acids contained as esterifying components in the mixed esters of glycerine of the additive mixture consist of 45 to 52 mass % C 22 -monocarboxylic acids in relation to the overall weight of the C 12 -C 40 -monocarboxylic acids, and wherein the partially imidated maleic anhydride copolymers contained as esterifying components are maleic anhydride-α-methylstyrene copolymers partially imidated with C 6 -C 40 -monoalkylamines in which the mole ratio of anhydride groups in the copolymer/C 6 -C 24 -monoalkylamine bound in the copolymer is in the range of from 8:1 to 1.3:01.  
   
   
       19 . The compositions according to  claim 2  wherein the partially imidated copolymer of maleic anhydride and α-methyl-styrene as additive component c) are maleic anhydride-α-methylstyrene copolymers partially imidated with C 6 -C 24  monoalkylamines in which the mole ratio of anhydride groups in the copolymer/bound C 6 -C 24  monoalkylamine in the copolymer is from 8:1 to 1.3:1.  
   
   
       20 . The compositions according to  claim 3  wherein the partially imidated copolymer of maleic anhydride and α-methylstyrene as additive component c) are maleic anhydride-α-methyl-styrene copolymers partially imidated with C 6 -C 24  monoalkylamines in which the mole ratio of anhydride groups in the copolymer/bound C 6 -C 24  monoalkylamine in the copolymer is from 8:1 to 1.3:1.