Hydrophobic, Oleophobic and Alcohol-Resistant Fluorochemical Additive

Abstract

A fluorochemical additive is the reaction product under polymerization conditions of monomers that include: (a) an aromatic polycarboxylic acid as an anhydride, ester, or ester chloride; (b) at least one fluorinated reactant; and (c) at least one aliphatic amine, mercaptan, or alcohol. Optionally, a crosslinking agent can be used. The components of the additive all can be viewed as contributing to the performance of the disclosed additive. The fluorine-containing component is generally insoluble in molten polymers and will tend to migrate to the cooled surface thereof where the fluorinated moieties provide repellency characteristics when used in adequate quantities, generally at least about 30 wt % depending on the fluorinated reactant used to make the additive. The aromatic component appears to facilitate solubility and speed up the orientation process of the additive within the molten polymer. The aliphatic component to the reaction mixture appears to assist in anchoring the reaction product additive in the bulk polymer structure. Together, the components form a fluorinated reaction product additive that can be added to a molten polymer for integration into the resulting product to impart improved resistance to oil, water, and alcohol.

1 . A polymeric product comprising a synthetic organic polymer and a fluorochemical additive, said fluorochemical additive comprising the reaction product under polymerization conditions of monomers that comprise: 
 (a) an aromatic polycarboxylic acid as an anhydride, ester, or ester chloride;    (b) at least one fluorinated reactant; and    (c) at least one reactive aliphatic amine, mercaptan, or alcohol.    
   
   
       2 . A polymeric product according to  claim 1 , wherein said fluorochemical additive comprising the reaction product under polymerization conditions of monomers that comprise: 
 (a) trimellitic anhydride,    (b) a fluorotelomer comprising a mixture of even-numbered C 6 -C 18  1,1,2,2-tetrahydroperfluoro-1-alcohols, and    (c) stearyl alcohol that has been polymerized at a temperature within the range from about 140°-180° C.    
   
   
       3 . A polymeric product according to  claim 1 , wherein said fluorochemical additive comprises the polymeric reaction under polymerization conditions of monomers that comprise: (a) an anhydride monomer that contains at least one anhydride functional group or is capable of forming an anhydride functional group under polymerization conditions, (b) a fluorine-containing amine, alcohol, or mercaptan, and (c) a reactive aliphatic alcohol or amine.  
   
   
       4 . A polymeric product according to  claim 3 , wherein said anhydride monomer is a carboxylic acid having 2-4 carboxylic acid groups or a carboxylic acid anhydride.  
   
   
       5 . A polymeric product according to  claim 4 , wherein said anhydride monomer comprises maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, 3-butene-1,2,3-tricarboxylic acid, acrylic anhydride allylsuccinic anhydride, citraconic anhydride, methacrylic anhydride, trimellitic anhydride, fumaric acid, fumaric anhydride, vinyl acetic acid, vinyl acetic anhydride, norbornene dicarboxylic acid, norbornene tricarboxylic acid, norbornene anhydride, cyclopentadiene dicarboxylic acid, cyclopentadiene tricarboxylic acid, cyclopentadiene anhydride, cyclohexyl dicarboxylic acid, cyclohexyl tricarboxylic acid, or cyclohexyl anhydride.  
   
   
       6 . A polymeric product according to  claim 5 , wherein said anhydride monomer comprises maleic anhydride, acrylic anhydride, allylsuccinic anhydride, citraconic anhydride, methacrylic anhydride, or trimellitic anhydride.  
   
   
       7 . A polymeric product according to  claim 3 , wherein said fluorine-containing reactant is a partially fluorinated or perfluorinated straight or branched chain alcohol comprising about 2 to about 40 carbon atoms in length.  
   
   
       8 . A polymeric product according to  claim 7 , wherein said fluorine-containing reactant is a partially fluorinated or perfluorinated straight or branched chain alcohol comprising about 6 to about 18 carbon atoms.  
   
   
       9 . A polymeric product according to  claim 7 , wherein said fluorine-containing reactant is an alcohol that is completely fluorinated.  
   
   
       10 . A polymeric product according to  claim 7 , wherein said fluorine-containing reactant has between 2 and about 6 hydrogen substituents.  
   
   
       11 . A polymeric product according to  claim 7 , wherein said fluorine-containing reactant is a tetrahydro- substituted alcohol with remaining substituents being fluorine.  
   
   
       12 . A polymeric product according to  claim 7 , wherein said fluorine-containing reactant is an alcohol that contains a terminus of either (CH 3 —) or (CHF 2 —).  
   
   
       13 . A polymeric product according to  claim 7 , wherein said fluorine-containing reactant is a fluorotelomer.  
   
   
       14 . A polymeric product according to  claim 13 , wherein said fluorine-containing reactant is a mixture of even-numbered C 6 -C 18  1,1,2,2 - tetrahydroperfluoro-1-alcohols.  
   
   
       15 . A polymeric product according to  claim 3 , wherein said reactive alcohol or amine is a straight or branched alcohol with one or more hydroxyl moieties.  
   
   
       16 . A polymeric product according to  claim 15 , wherein the reactive alcohol has 12-30 carbon atoms.  
   
   
       17 . A polymeric product according to  claim 16 , wherein the reactive alcohol has 15-20 carbon atoms.  
   
   
       18 . A polymeric product according to  claim 1 , wherein said polymerization conditions comprise a temperature within the range from about  140 °-180° C.  
   
   
       19 . A polymeric product according to  claim 1 , that comprises the reaction product of: 
 (a) trimellitic anhydride, (b) a fluorotelomer comprising a mixture of even-numbered C 6 -C 18  1,1,2,2- tetrahydroperfluoro-1-alcohols, and (c) stearyl alcohol that has been polymerized a temperature within the range from about 140°-180° C.    
   
   
       20 . A polymeric product of  claim 1 , wherein said polymeric product is a mixture of said synthetic organic polymer and said fluorochemical additive.  
   
   
       21 . A polymeric product according to  claim 20  wherein said synthetic organic polymer is a thermoplastic polymer or a thermoset polymer.  
   
   
       22 . A polymeric product according to  claim 21 , wherein said thermoplastic polymer is a polyamide, a polyester, a polyolefin, a thermoplastic urethane, a polystyrene, or an acrylic.  
   
   
       23 . A polymeric product according to  claim 21 , wherein said thermoset polymer is an epoxy, or a thermoset polyurethane.  
   
   
       24 . A polymeric product according to  claim 1 , wherein said synthetic organic polymer is in the form of a fiber, a film, a nonwoven web, or a molded article.  
   
   
       25 . A polymeric product according to  claim 1 , wherein said synthetic organic polymer is in the form of a nonwoven web.  
   
   
       26 . A polymeric product according to  claim 1 , wherein said synthetic organic polymer is selected from the group consisting of nylon, polyethylene, polypropylene, and polyethylene terephthalate.  
   
   
       27 . A polymeric product according to  claim 24 , wherein said nonwoven web is a multilayer laminate comprising an inner layer, at least one middle layer, and an outer layer.  
   
   
       28 . A polymeric product according to  claim 27 , wherein said outer layer comprises a thermoplastic with said fluorochemical additive and said inner layer comprises a thermoplastic without said fluorochemical additive.  
   
   
       29 . A polymeric product according to  claim 28 , wherein said nonwoven web comprises two middle layers.  
   
   
       30 . A polymeric product according to  claim 28 , wherein said inner layer and said outer layer each have a spun bond structure.  
   
   
       31 . A polymeric product of  claim 1  wherein said synthetic organic polymer is an article in the form of a fiber, film, non-woven web or molded article and wherein said fluorochemical additive is applied as a surface treatment on said article.  
   
   
       32 . A polymeric product of  claim 1  wherein said synthetic organic polymer is an article in the form of a fiber, film, non-woven web or molded article and wherein said fluorochemical additive is formed as a mixture.