Continuous bulk polymerization and esterification process and compositions

Abstract

A continuous bulk polymerization and esterification process includes continuously charging into a reaction zone at least one ethylenically unsaturated acid-functional monomer and at least one linear or branched chain alkanol having greater than 11 carbon atoms. The process includes maintaining a flow rate through the reaction zone sufficient to provide an average residence time of less than 60 minutes and maintaining a temperature in the reaction zone sufficient to produce a polymeric product incorporating at least some of the alkanol as an ester of the polymerized ethylenically unsaturated acid-functional monomer. The polymeric product is used in various processes to produce water-based compositions including emulsions and dispersions such as oil emulsions, wax dispersions, pigment dispersions, surfactants and coatings which contain the polymeric product. A polymeric surfactant includes at least one ethylenically unsaturated acid-functional monomer which has been radically incorporated into the polymeric surfactant and at least one ester of the incorporated ethylenically unsaturated acid-functional monomer which has a linear or branched chain alkyl group with greater than 11 carbon atoms. The molar critical micelle concentration of the polymeric surfactant is less than 1.0×10 −2 moles/liter. Aqueous 2 percent solutions of certain polymeric surfactants have a surface tension of less than 45 mN/m at 30° C. and exhibit a decrease in surface tension of at least 5 mN/m as the temperature warms from 30° C. to 50° C.

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         13 . A water-based composition, comprising: 
 (a) water;    (b) from about 1 to about 100 percent by weight based on the total weight of the composition, disregarding the water, of the polymeric product according to  claim 1;  and 
 (c) up to about 99 percent by weight based on the total weight of the composition, disregarding the water, of an adjunct.  
   
     
     
         14 . The water-based composition according to  claim 13 , wherein the adjunct is selected from the group consisting of an emulsion polymer, a coalescing solvent, a plasticizer, a cross-linking agent, a defoamer, a pigment, a tackifier, a conventional surfactant, a starch, a wax, a slip aid, a wetting agent, a surface modifier, an inert filler, an inert extender, and mixtures thereof.  
     
     
         15 . The water-based composition according to  claim 13 , wherein the adjunct is present in an amount ranging from about 10 to about 99 percent by weight based on the total weight of the composition disregarding the water.  
     
     
         16 . The water-based composition according to  claim 14 , wherein the water-based composition is selected from the group consisting of an overprint varnish, an ink, a barrier coating material, a coil coating material, a paper coating material, a foil coating material, an adhesive, a floor polish, a paint, a primer, and a paper sizing agent.  
     
     
         17 . A water-based composition, comprising: 
 (a) water;    (b) from about 1 to about 100 percent by weight based on the total weight of the composition, disregarding the water, of a polymeric product produced by a continuous bulk polymerization and esterification process comprising: continuously charging at least one ethylenically unsaturated acid-functional monomer and at least one alkanol having the formula ROH, wherein R is a linear or branched chain alkyl moiety having greater than 11 carbon atoms, into a reaction zone to form a reaction mixture; maintaining a flow rate through the reaction zone sufficient to provide an average residence time of the reaction mixture in the reaction zone of less than 60 minutes; and maintaining an effective temperature in the reaction zone sufficient to produce the polymeric product incorporating at least some of the alkanol as an ester of the polymerized ethylenically unsaturated acid-functional monomer; and    (c) up to about 99 percent by weight based on the total weight of the composition, disregarding the water, of an adjunct.    
     
     
         18 . The water-based composition of  claim 17 , wherein the adjunct is selected from the group consisting of an emulsion polymer, a coalescing solvent, a plasticizer, a cross-linking agent, a defoamer, a pigment, a tackifier, a conventional surfactant, a starch, a wax, a slip aid, a wetting agent, a surface modifier, an inert filler, an inert extender, and mixtures thereof.  
     
     
         19 . The water-based composition according to  claim 17 , wherein the total adjunct is present in an amount ranging from about 10 to about 99 percent by weight based on the total weight of the composition disregarding the water.  
     
     
         20 . The water-based composition according to  claim 18 , wherein the water-based composition is selected from the group consisting of an overprint varnish, an ink, a barrier coating material, a coil coating material, a paper coating material, a foil coating material, an adhesive, a floor polish, a paint, a primer, and a paper sizing agent.  
     
     
         21 . A polymeric surfactant, comprising: 
 (a) at least one ethylenically unsaturated acid-functional monomer which has been radically incorporated into the polymeric surfactant; and    (b) at least one ester of the incorporated ethylenically unsaturated acid-functional monomer having an R alkyl group, wherein R is a linear or branched chain alkyl moiety having greater than 11 carbon atoms; wherein the molar critical micelle concentration of the polymeric surfactant is less than 1.0×10 −2  moles/liter.    
     
     
         22 . The polymeric surfactant according to  claim 21 , wherein the surface area per molecule of the polymeric surfactant is less than 36 Å 2 .  
     
     
         23 . The polymeric surfactant according to  claim 22 , wherein the surface area per molecule of the polymeric surfactant is less than 20 Å 2 .  
     
     
         24 . The polymeric surfactant according to  claim 21 , wherein R is a linear or branched chain alkyl radical having from 12 to 50 carbon atoms.  
     
     
         25 . The polymeric surfactant according to  claim 21 , wherein R is a linear or branched chain alkyl radical having from 12 to 22 carbon atoms.  
     
     
         26 . The polymeric surfactant according to  claim 21 , wherein R is a linear or branched chain alkyl radical having 14 carbon atoms.  
     
     
         27 . The polymeric surfactant according to  claim 21 , wherein R is a linear alkyl radical having 14 carbon atoms.  
     
     
         28 . The polymeric surfactant according to  claim 21 , wherein the molar critical micelle concentration is less than 8.2×10 −3  moles/liter.  
     
     
         29 . The polymeric surfactant according to  claim 21 , wherein the molar critical micelle concentration is less than 1.0×10 −3  moles/liter.  
     
     
         30 . The polymeric surfactant according to  claim 21 , further comprising at least one vinyl aromatic monomer incorporated into the polymeric surfactant.  
     
     
         31 . The polymeric surfactant according to  claim 21 , further comprising at least one non-aromatic monomer incorporated into the polymeric surfactant.  
     
     
         32 . The polymeric surfactant according to  claim 31 , wherein the ethylenically unsaturated acid-functional monomer is acrylic acid.  
     
     
         33 . The polymeric surfactant according to  claim 32 , wherein the polymeric surfactant comprises styrene and α-methylstyrene incorporated into the polymeric surfactant.  
     
     
         34 . A polymeric surfactant, comprising: 
 (a) at least one ethylenically unsaturated acid-functional monomer which has been radically incorporated into the polymeric surfactant; and    (b) at least one ester of the incorporated ethylenically unsaturated acid-functional monomer having an R alkyl group, wherein R is a linear or branched chain alkyl radical having greater than 11 carbon atoms; wherein a 2 percent by weight neutralized aqueous solution of the polymeric surfactant has a surface tension of less than 45 mN/m at 30° C. and undergoes a decrease in surface tension of at least 5 mN/m as the temperature warms from 30° C. to 50° C.    
     
     
         35 . The polymeric surfactant according to  claim 34 , wherein the molar critical micelle concentration of the polymeric surfactant is less than 1×10 −2  moles/liter.  
     
     
         36 . The polymeric surfactant according to  claim 34 , wherein the molar critical micelle concentration of the polymeric surfactant is less than 8.2×10 −3  moles/liter.  
     
     
         37 . The polymeric surfactant according to  claim 34 , wherein the molar critical micelle concentration of the polymeric surfactant is less than 1.0×10 −3  moles liter.  
     
     
         38 . The polymeric surfactant according to  claim 34 , wherein R is a linear or branched chain alkyl radical having from 12 to 50 carbon atoms.  
     
     
         39 . The polymeric surfactant according to  claim 34 , wherein R is a linear or branched chain alkyl radical having from 12 to 22 carbon atoms.  
     
     
         40 . The polymeric surfactant according to  claim 34 , further comprising at least one vinyl aromatic monomer incorporated into the polymeric surfactant.  
     
     
         41 . The polymeric surfactant according to  claim 34 , further comprising at least one vinyl non-aromatic monomer incorporated into the polymeric surfactant.  
     
     
         42 . The polymeric surfactant according to  claim 41 , wherein the ethylenically unsaturated acid-functional monomer is acrylic acid.  
     
     
         43 . The polymeric surfactant according to  claim 42 , wherein the polymeric surfactant comprises styrene and α-methylstyrene incorporated into the polymeric surfactant.  
     
     
         44 . A process for preparing an emulsion of a polyolefin resin, comprising: 
 (a) mixing together a polyolefin resin and a polymeric product, the polymeric product produced by a bulk polymerization and esterification process comprising: continuously charging at least one ethylenically unsaturated acid-functional monomer and at least one alkanol having the formula ROH, wherein R is a linear or branched chain alkyl moiety having greater than 11 carbon atoms, into a reaction zone to form a reaction mixture; maintaining a flow rate through the reaction zone sufficient to provide an average residence time of the reaction mixture in the reaction zone of less than 60 minutes; and maintaining an effective temperature in the reaction zone sufficient to produce the polymeric product incorporating at least some of the alkanol as an ester of the polymerized ethylenically unsaturated acid-functional monomer;    (b) mixing a base with the combination of (a); and    (c) mixing the combined base, resin and polymeric product with water.    
     
     
         45 . The process for preparing an emulsion of a polyolefin resin according to  claim 44 , further comprising adding a conventional surfactant to the combination of (a).  
     
     
         46 . The process for preparing an emulsion of a polyolefin resin according to  claim 45 , wherein the conventional surfactant is selected from the group consisting of an anionic surfactant and a non-ionic surfactant, and further wherein the conventional surfactant is present in an amount up to about 10 percent by weight based on the total weight of the solids.  
     
     
         47 . The process for preparing an emulsion of a polyolefin resin according to  claim 44 , wherein the polymeric product has an acid number from 20 to 740.  
     
     
         48 . The process for preparing an emulsion of a polyolefin resin according to  claim 44 , wherein the base is selected from the group consisting of ammonia, diethylaminoethanol, morpholine, sodium hydroxide, potassium hydroxide, and mixtures thereof.  
     
     
         49 . The process for preparing an emulsion of a polyolefin resin according to  claim 44 , wherein the polyolefin resin has a number average molecular weight ranging from about 500 to about 20,000.  
     
     
         50 . The process for preparing an emulsion of a polyolefin resin according to  claim 44 , wherein the polyolefin resin has an acid number of about 0 to about 150 and a melting point of about 40° C. to about 250° C.  
     
     
         51 . The process for preparing an emulsion of a polyolefin resin according to  claim 44 , wherein the polyolefin resin, the polymeric product, and the base are melted together to produce a molten mixture and the molten mixture is added to the water.  
     
     
         52 . The process for preparing an emulsion of a polyolefin resin according to  claim 44 , wherein the polyolefin resin and the polymeric product are heated to produce a molten mixture, the base is added to the molten mixture, and the water is subsequently added to the base and molten mixture.  
     
     
         53 . The process for preparing an emulsion of a polyolefin resin according to  claim 44 , wherein the polyolefin resin and the polymeric product are heated to produce a molten mixture, the base is added to the molten mixture, and the base and molten mixture are subsequently added to the water.  
     
     
         54 . The process for preparing an emulsion of a polyolefin resin according to  claim 44 , wherein the polyolefin resin and the polymeric product are heated to produce a molten mixture, the base is added to the molten mixture, and the water is subsequently added to the base and molten mixture.  
     
     
         55 . An emulsion prepared according to  claim 44 .  
     
     
         56 . An emulsion prepared according to  claim 46 .  
     
     
         57 . An emulsion prepared according to  claim 50 .  
     
     
         58 . An emulsion of a polyolefin resin, comprising: 
 (a) a polyolefin resin and a polymeric product consisting of 
 (i) about 3 to 97 percent by weight of at least one ethylenically unsaturated acid-functional monomer which has been polymerized into the polymeric product,  
 (ii) about 3 to 97 percent by weight at least one alkyl ester of the ethylenically unsaturated acid-functional monomers, wherein the alkyl group is a linear or branched chain alkyl radical having greater than 11 carbon atoms which has been polymerized into the polymeric product,  
 (iii) about 0 to about 85 percent by weight of at least one aromatic ethylenically unsaturated monomer which has been polymerized into the polymeric product; and  
 (iv) about 0 to about 85 percent by weight of at least one non-aromatic ethylenically unsaturated vinyl monomer which has been polymerized into the polymeric product, wherein an aqueous resin cut at a solids content of 30.5%, a pH of from 7.7 to 8.2, and a temperature of 25C., of the polymeric product has a solution viscosity which is less than about 50 percent of the solution viscosity of an aqueous resin cut at a solids content of 30.5%, a pH of 7.8, and a temperature of 25C., of a second polymeric product identical to the polymeric product except that it does not contain any of the alkyl ester of the ethylenically unsaturated acid-functional monomers of (ii), and wherein the weight percent of (i), (ii), (iii) and (iv) is base on the total weight of the polymeric product;  
   (b) a base; and    (c) water.    
     
     
         59 . The emulsion of the polyolefin resin according to  claim 58 , further comprising a conventional surfactant.  
     
     
         60 . The emulsion of the polyolefin resin according to  claim 59 , wherein the conventional surfactant is selected from the group consisting of an anionic surfactant and a non-ionic surfactant, and further wherein the conventional surfactant is present in an amount up to about 10 percent by weight based on the total weight of the solids.  
     
     
         61 . The emulsion of the polyolefin resin according to  claim 58 , wherein the polymeric product has an acid number from 20 to 740.  
     
     
         62 . The emulsion of the polyolefin resin according to  claim 58 , wherein the base is selected from the group consisting of ammonia, diethylaminoethanol, morpholine, sodium hydroxide, potassium hydroxide, and mixtures thereof.  
     
     
         63 . The emulsion of the polyolefin resin according to  claim 58 , wherein the polyolefin resin has a number average molecular weight ranging from about 500 to about 20,000.  
     
     
         64 . The emulsion of the polyolefin resin according to  claim 63 , wherein the polyolefin resin has an acid number of about 0 to about 150 and a melting point of about 40° to about 250° C.  
     
     
         65 . A process for preparing a wax dispersion, comprising mixing a wax with an aqueous solution of a polymeric product, the polymeric product produced by a bulk polymerization and esterification process comprising: continuously charging at least one ethylenically unsaturated acid-functional monomer and at least one alkanol having the formula ROH, wherein R is a linear or branched chain alkyl moiety having greater than 11 carbon atoms, into a reaction zone to form a reaction mixture; maintaining a flow rate through the reaction zone sufficient to provide an average residence time of the reaction mixture in the reaction zone of less than 60 minutes; and maintaining an effective temperature in the reaction zone sufficient to produce the polymeric product incorporating at least some of the alkanol as an ester of the polymerized ethylenically unsaturated acid-functional monomer.  
     
     
         66 . The process for preparing a wax dispersion according to  claim 65 , further comprising adding a conventional surfactant.  
     
     
         67 . The process for preparing a wax dispersion according to  claim 66 , wherein the conventional surfactant is selected from the group consisting of an anionic surfactant and a non-ionic surfactant, and further wherein the conventional surfactant is present in an amount up to about 10 percent by weight based on the total weight of the solids.  
     
     
         68 . A wax dispersion prepared according to  claim 65 .  
     
     
         69 . A wax dispersion, comprising: 
 (a) a wax;    (b) the polymeric product consisting of 
 (i) about 3 to 97 percent by weight of at least one ethylenically unsaturated acid-functional monomer which has been polymerized into the polymeric product,  
 (ii) about 3 to 97 percent by weight at least one alkyl ester of the ethylenically unsaturated acid-functional monomers, wherein the alkyl group is a linear or branched chain alkyl radical having greater than 11 carbon atoms which has been polymerized into the polymeric product,  
 (iii) about 0 to about 85 percent by weight of at least one aromatic ethylenically unsaturated monomer which has been polymerized into the polymeric product; and  
 (iv) about 0 to about 85 percent by weight of at least one non-aromatic ethylenically unsaturated vinyl monomer which has been polymerized into the polymeric product, wherein an aqueous resin cut at a solids content of 30.5%, a pH of from 7.7 to 8.2, and a temperature of 25C., of the polymeric product has a solution viscosity which is less than about 50 percent of the solution viscosity of an aqueous resin cut at a solids content of 30.5%, a pH of 7.8, and a temperature of 25C., of a second polymeric product identical to the polymeric product except that it does not contain any of the alkyl ester of the ethylenically unsaturated acid-functional monomers of (ii), and wherein the weight percent of (i), (ii), (iii) and (iv) is base on the total weight of the polymeric product;  
   (c) an aqueous medium.    
     
     
         70 . The wax dispersion according to  claim 69 , further comprising a conventional surfactant.  
     
     
         71 . The wax dispersion according to  claim 70 , wherein the conventional surfactant is selected from the group consisting of an anionic surfactant and a non-ionic surfactant, and further wherein the conventional surfactant is present in an amount up to about 10 percent by weight based on the total weight of the solids.  
     
     
         72 . The process for preparing an oil emulsion, comprising: 
 (a) heating a mixture of an oil and a polymeric product, the polymeric product produced by a continuous bulk polymerization and esterification process comprising: continuously charging at least one ethylenically unsaturated acid-functional monomer and at least one alkanol having the formula ROH, wherein R is a linear or branched chain alkyl moiety having greater than 11 carbon atoms, into a reaction zone to form a reaction mixture; maintaining a flow rate through the reaction zone sufficient to provide an average residence time of the reaction mixture in the reaction zone of less than 60 minutes; and maintaining an effective temperature in the reaction zone sufficient to produce the polymeric product incorporating at least some of the alkanol as an ester of the polymerized ethylenically unsaturated acid-functional monomer;    (b) mixing a base with the heated mixture of the oil and the polymeric product; and    (c) mixing water with the components of (b).    
     
     
         73 . The process for preparing an oil emulsion according to  claim 72 , further comprising adding a conventional surfactant.  
     
     
         74 . The process for preparing an oil emulsion according to  claim 73 , wherein the conventional surfactant is selected from the group consisting of an anionic surfactant and a non-ionic surfactant, and further wherein the conventional surfactant is present in an amount up to about 10 percent by weight based on the total weight of the solids.  
     
     
         75 . The process for preparing an oil emulsion according to  claim 72 , wherein the base is selected from the group consisting of ammonia, diethylaminoethanol, morpholine, sodium hydroxide, potassium hydroxide, and mixtures thereof.  
     
     
         76 . The process of  claim 72 , wherein the water is added to the components of (b).  
     
     
         77 . The process of  claim 72 , wherein the components of (b) are added to the water.  
     
     
         78 . An oil emulsion prepared according to the process of  claim 72 .  
     
     
         79 . An oil emulsion, comprising: 
 (a) an oil    (b) a base    (c) the polymeric product consisting of 
 (i) about 3 to 97 percent by weight of at least one ethylenically unsaturated acid-functional monomer which has been polymerized into the polymeric product,  
 (ii) about 3 to 97 percent by weight at least one alkyl ester of the ethylenically unsaturated acid-functional monomers, wherein the alkyl group is a linear or branched chain alkyl radical having greater than 11 carbon atoms which has been polymerized into the polymeric product,  
 (iii) about 0 to about 85 percent by weight of at least one aromatic ethylenically unsaturated monomer which has been polymerized into the polymeric product; and  
 (iv) about 0 to about 85 percent by weight of at least one non-aromatic ethylenically unsaturated vinyl monomer which has been polymerized into the polymeric product, wherein an aqueous resin cut at a solids content of 30.5%, a pH of from 7.7 to 8.2, and a temperature of 25C., of the polymeric product has a solution viscosity which is less than about 50 percent of the solution viscosity of an aqueous resin cut at a solids content of 30.5%, a pH of 7.8, and a temperature of 25C., of a second polymeric product identical to the polymeric product except that it does not contain any of the alkyl ester of the ethylenically unsaturated acid-functional monomers of (ii), and wherein the weight percent of (i), (ii), (iii) and (iv) is base on the total weight of the polymeric product;  
   (d) water.    
     
     
         80 . The oil emulsion according to  claim 79 , further comprising a conventional surfactant.  
     
     
         81 . The oil emulsion according to  claim 80 , wherein the conventional surfactant is selected from the group consisting of an anionic surfactant and a non-ionic surfactant, and further wherein the conventional surfactant is present in an amount up to about 10 percent by weight based on the total weight of the solids.  
     
     
         82 . The oil emulsion according to  claim 79 , wherein the base is selected from the group consisting of ammonia, diethylaminoethanol, morpholine, sodium hydroxide, potassium hydroxide, and mixtures thereof.  
     
     
         83 . A process for improving the viscosity profile of an aqueous pigment dispersion, comprising adding a polymeric product to the aqueous pigment dispersion, the polymeric product produced by a continuous bulk polymerization and esterification process comprising: continuously charging at least one ethylenically unsaturated acid-functional monomer and at least one alkanol having the formula ROH, wherein R is a linear or branched chain alkyl moiety having greater than 11 carbon atoms, into a reaction zone to form a reaction mixture; maintaining a flow rate through the reaction zone sufficient to provide an average residence time of the reaction mixture in the reaction zone of less than 60 minutes; and maintaining an effective temperature in the reaction zone sufficient to produce the polymeric product incorporating at least some of the alkanol as an ester of the polymerized ethylenically unsaturated acid-functional monomer.  
     
     
         84 . An aqueous pigment dispersion with an improved viscosity profile comprising: 
 (a) an aqueous pigment dispersion; and    (b) the polymeric product consisting of 
 (i) about 3 to 97 percent by weight of at least one ethylenically unsaturated acid-functional monomer which has been polymerized into the polymeric product,  
 (ii) about 3 to 97 percent by weight at least one alkyl ester of the ethylenically unsaturated acid-functional monomers, wherein the alkyl group is a linear or branched chain alkyl radical having greater than 11 carbon atoms which has been polymerized into the polymeric product,  
 (iii) about 0 to about 85 percent by weight of at least one aromatic ethylenically unsaturated monomer which has been polymerized into the polymeric product; and  
 (iv) about 0 to about 85 percent by weight of at least one non-aromatic ethylenically unsaturated vinyl monomer which has been polymerized into the polymeric product, wherein an aqueous resin cut at a solids content of 30.5%, a pH of from 7.7 to 8.2, and a temperature of 25C., of the polymeric product has a solution viscosity which is less than about 50 percent of the solution viscosity of an aqueous resin cut at a solids content of 30.5%, a pH of 7.8, and a temperature of 25C., of a second polymeric product identical to the polymeric product except that it does not contain any of the alkyl ester of the ethylenically unsaturated acid-functional monomers of (ii), and wherein the weight percent of (i), (ii), (iii) and (iv) is base on the total weight of the polymeric product.  
   
     
     
         85 . A process for increasing the total solids concentration of an aqueous coating, comprising adding a polymeric product to the aqueous coating, the polymeric product produced by a continuous bulk polymerization and esterification process comprising: continuously charging at least one ethylenically unsaturated acid-functional monomer and at least one alkanol having the formula ROH, wherein R is a linear or branched chain alkyl moiety having greater than 11 carbon atoms, into a reaction zone to form a reaction mixture; maintaining a flow rate through the reaction zone sufficient to provide an average residence time of the reaction mixture in the reaction zone of less than 60 minutes; and maintaining an effective temperature in the reaction zone sufficient to produce the polymeric product incorporating at least some of the alkanol as an ester of the polymerized ethylenically unsaturated acid-functional monomer.  
     
     
         86 . An aqueous coating having an increase in total solids comprising: 
 (a) an aqueous coating; and    (b) the polymeric product consisting of 
 (i) about 3 to 97 percent by weight of at least one ethylenically unsaturated acid-functional monomer which has been polymerized into the polymeric product,  
 (ii) about 3 to 97 percent by weight at least one alkyl ester of the ethylenically unsaturated acid-functional monomers, wherein the alkyl group is a linear or branched chain alkyl radical having greater than 11 carbon atoms which has been polymerized into the polymeric product,  
 (iii) about 0 to about 85 percent by weight of at least one aromatic ethylenically unsaturated monomer which has been polymerized into the polymeric product; and  
 (iv) about 0 to about 85 percent by weight of at least one non-aromatic ethylenically unsaturated vinyl monomer which has been polymerized into the polymeric product, wherein an aqueous resin cut at a solids content of 30.5%, a pH of from 7.7 to 8.2, and a temperature of 25C., of the polymeric product has a solution viscosity which is less than about 50 percent of the solution viscosity of an aqueous resin cut at a solids content of 30.5%, a pH of 7.8, and a temperature of 25C., of a second polymeric product identical to the polymeric product except that it does not contain any of the alkyl ester of the ethylenically unsaturated acid-functional monomers of (ii), and wherein the weight percent of (i), (ii), (iii) and (iv) is base on the total weight of the polymeric product.  
   
     
     
         87 . A process for stabilizing a compound in an aqueous medium, comprising: 
 (a) providing a resin melt of a polymeric product in a reactor operating at or above atmospheric pressure, the polymeric product produced by a continuous bulk polymerization and esterification process comprising: continuously charging at least one ethylenically unsaturated acid-functional monomer and at least one alkanol having the formula ROH, wherein R is a linear or branched chain alkyl moiety having greater than 11 carbon atoms, into a reaction zone to form a reaction mixture; maintaining a flow rate through the reaction zone sufficient to provide an average residence time of the reaction mixture in the reaction zone of less than 60 minutes; and maintaining an effective temperature in the reaction zone sufficient to produce the polymeric product incorporating at least some of the alkanol as an ester of the polymerized ethylenically unsaturated acid-functional monomer;    (b) charging the reactor with a base and water;    (c) dispersing a compound selected from the group consisting of an oil and a wax into the resin melt; and    (d) charging additional water into the reactor.    
     
     
         88 . A stabilized compound prepared according to  claim 83 .  
     
     
         89 . A barrier coating, comprising: 
 (a) a polymeric product, the polymeric product produced by a continuous bulk polymerization and esterification process comprising: continuously charging at least one ethylenically unsaturated acid-functional monomer and at least one alkanol having the formula ROH, wherein R is a linear or branched chain alkyl moiety having greater than 11 carbon atoms, into a reaction zone to form a reaction mixture; maintaining a flow rate through the reaction zone sufficient to provide an average residence time of the reaction mixture in the reaction zone of less than 60 minutes; and maintaining an effective temperature in the reaction zone sufficient to produce the polymeric product incorporating at least some of the alkanol as an ester of the polymerized ethylenically unsaturated acid-functional monomer;    (b) an emulsion polymer; and    (c) a paraffin wax emulsion.    
     
     
         90 . The barrier coating according to  claim 89 , wherein the water vapor transmission rate of a film with a thickness of 0.9 mils is less than 6 grams per 100 square inches per 24 hours at 90 percent relative humidity and 37.8° C.  
     
     
         91 . The barrier coating according to  claim 90 , wherein the water vapor transmission rate of the film is less than 3 grams per 100 square inches per 24 hours at 90 percent relative humidity and 37.8° C.  
     
     
         92 . A barrier coating, comprising: 
 (a) the polymeric product consisting of 
 (i) about 3 to 97 percent by weight of at least one ethylenically unsaturated acid-functional monomer which has been polymerized into the polymeric product,  
 (ii) about 3 to 97 percent by weight at least one alkyl ester of the ethylenically unsaturated acid-functional monomers, wherein the alkyl group is a linear or branched chain alkyl radical having greater than 11 carbon atoms which has been polymerized into the polymeric product,  
 (iii) about 0 to about 85 percent by weight of at least one aromatic ethylenically unsaturated monomer which has been polymerized into the polymeric product: and  
 (iv) about 0 to about 85 percent by weight of at least one non-aromatic ethylenically unsaturated vinyl monomer which has been polymerized into the polymeric product, wherein an aqueous resin cut at a solids content of 30.5%, a pH of from 7.7 to 8.2, and a temperature of 25C., of the polymeric product has a solution viscosity which is less than about 50 percent of the solution viscosity of an aqueous resin cut at a solids content of 30.5%, a pH of 7.8, and a temperature of 25C., of a second polymeric product identical to the polymeric product except that it does not contain any of the alkyl ester of the ethylenically unsaturated acid-functional monomers of (ii), and wherein the weight percent of (i), (ii), (iii) and (iv) is base on the total weight of the polymeric product;  
   (b) an emulsion polymer; and    (c) a paraffin wax emulsion.    
     
     
         93 . The barrier coating according to  claim 92 , wherein the water vapor transmission rate of a film with a thickness of 0.9 mils is less than 6 grams per 100 square inches per 24 hours at 90 percent relative humidity and 37.8° C.  
     
     
         94 . The barrier coating according to  claim 93 , wherein the water vapor transmission rate of the film is less than 3 grams per 100 square inches per 24 hours at 90 percent relative humidity and 37.8° C.