Fuel oil compositions with improved cold flow properties

Abstract

The use is described of polymers which contain, in copolymerized form, an α-olefin, a vinyl ester and an ester of an α,β-unsaturated carboxylic acid as an additive for fuel oils and lubricants and in particular as a cold flow improver in fuel oils. In addition, the fuel oils and lubricants additized with these polymers; and also additive packages comprising such polymers are described.

1 . A polymer which contains, in copolymerized form,
 an α-olefin,   a vinyl ester, and   a C 1 -C 20 -hydrocarbyl ester of an α,β-unsaturated carboxylic acid.   
   
   
       2 . The polymer according to  claim 1 , which contains the vinyl ester and the ester of an α,β-unsaturated carboxylic acid copolymerized in random distribution. 
   
   
       3 . The polymer according to  claim 1 , which is composed of monomers including M1, M2 and M3 and wherein M1, M2 and M3 have the following general formulae: 
     
       
         
         
             
             
         
       
     
     where
 R 1  is H or C 1 -C 40 -hydrocarbyl; 
 R 2 , R 3  and R 4  are each independently H or C 1 -C 4 -alkyl; 
 R 5  is C 1 -C 20 -hydrocarbyl; 
 R 6 , R 7  and R 8  are each independently H or C 1 -C 4 -alkyl; and 
 R 9  is C 1 -C 20 -hydrocarbyl. 
 
   
   
       4 . The polymer according to  claim 3 , wherein the monomers M1, M2 and M3 are present in the following molar proportions:
 M1: from 0.60 to 0.98   M2: from 0.01 to 0.20   M3: from 0.01 to 0.20.   
   
   
       5 . The polymer according to  claim 3 , wherein monomer M1 is ethylene. 
   
   
       6 . The polymer according to  claim 3 , wherein R 2 , R 3  and R 4  are each H or two of the R 2 , R 3  and R 4  radicals are each H and the other radical is methyl. 
   
   
       7 . The polymer of  claim 3 , wherein M1 is ethylene, propene, or 1-butene. 
   
   
       8 . The polymer of  claim 3 , wherein M2 is n-butyl acrylate, 2-ethylhexyl acrylate, or lauryl acrylate. 
   
   
       9 . The polymer of  claim 3 , wherein M3 is vinyl acetate. 
   
   
       10 . The polymer of  claim 3 , wherein M1 is ethylene, M2 is 2-ethylhexyl acrylate, and M3 is vinyl acetate. 
   
   
       11 . The polymer of  claim 3 , wherein monomers M1, M2 and M3 are present in the following molar proportions Mx/(M1+M2+M3) in the polymer:
 M1: from 0.60 to 0.98,   M2: from 0.01 to 0.20,   M3: from 0.01 to 0.20; and   has a number average molecular weight ranging from 1,000 to 20,000, and/or a weight-average molecular weight ranging from 1,000 to 30,000, and/or a M w /M n  ratio ranging from 1.5 to 5.0.   
   
   
       12 . The polymer of  claim 3 , wherein monomers M1, M2 and M3 are present in the following molar proportions Mx/(M1+M2+M3) in the polymer:
 Ml: from 0.80 to 0.90,   M2: from 0.02 to 0.16,   M3: from 0.03 to 0.09; and   has a number average molecular weight ranging from 1,500 to 5,000, and/or a weight-average molecular weight ranging from 2,000 to 30,000, and/or a M w /M n  ratio ranging from 1.9 to 3.5.   
   
   
       13 . The polymer of  claim 3 , which is made by free-radical polymerization. 
   
   
       14 . A fuel oil composition comprising the polymer of  claim 1 . 
   
   
       15 . The fuel oil composition of  claim 14  which contains a fuel oil selected from the group consisting of gasoline, middle distillates, diesel fuel, low sulfur diesel, ultra-low sulfur diesel, biodiesel, kerosene, heating oil, and low sulfur heating oil. 
   
   
       16 . The fuel oil composition of  claim 14 , further comprising a coadditive. 
   
   
       17 . A lubricant composition comprising a conventional lubricant and the polymer of  claim 1 . 
   
   
       18 . An additive concentrate comprising the polymer of  claim 1  in an amount ranging from 0.1 to 80% by weight based on the total weight of the concentrate, a diluent, and at least one coadditive. 
   
   
       19 . A method for making a fuel oil composition or a lubricant composition comprising admixing the polymer of  claim 1  with a fuel oil or a lubricant. 
   
   
       20 . A method for improving the cold flow properties of a fuel oil or a lubricant comprising adding the polymer of  claim 1  to a fuel oil or a lubricant.