Continuous adiabatic inverse emulsion polymerization process

Abstract

The present invention provides methods and systems for continuous polymerization of ethylenically unsaturated monomers in a water-in-oil inverse emulsion under adiabatic conditions without the need for external cooling during the polymerization. The method comprises neutralizing a monomer composition comprising at least one acidic vinyl monomer with a base in an aqueous medium comprising water and water ice to form an aqueous monomer solution therefrom; homogenizing and degassing to form an inverse monomer emulsion; initiating polymerization; passing the inverse emulsion through a tube reactor without cooling, and flash evaporating a portion of the water from inverse emulsion to cool and concentrate the resulting polymer-containing inverse emulsion. During neutralization, the aqueous medium comprises an amount of water ice sufficient to maintain a temperature of 30° C. or less, and the polymerization is initiated by adding a free-radical polymerization initiator to the emulsion prior to passing the emulsion through the tube reactor.

1 . A method for continuous polymerization of ethylenically unsaturated monomers in a water-in-oil inverse emulsion under adiabatic conditions, the method comprising the steps of:
 (a) neutralizing a monomer composition comprising at least one water-soluble, oil-insoluble, ethylenically unsaturated acidic monomer with a base in an aqueous medium comprising water and water ice to form an aqueous monomer solution characterized by a temperature of 30° C. or less;   (b) homogenizing the aqueous monomer solution with an oil phase, optionally in the presence of an emulsifier, to form a water-in-oil inverse emulsion;   (c) degassing the inverse emulsion;   (d) initiating polymerization of the neutralized monomer composition with a free-radical polymerization initiator;   (e) passing the inverse emulsion through a tube reactor comprising inline static mixing elements, at a flow rate sufficient to polymerize monomers; and   (f) flash evaporating a portion of the water from the inverse emulsion after it exits the tube reactor.   
     
     
         2 . The method of  claim 1 , wherein the polymerization initiator comprises a thermal initiator. 
     
     
         3 . The method of  claim 2 , wherein the thermal initiator comprises one or more material selected from the group consisting of an azo compound, an organic peroxide, and a dialkyl hyponitrite. 
     
     
         4 . The method of  claim 2 , wherein the thermal initiator comprises at least one azo compound selected from the group consisting of:
 2,2′-azobisisobutyronitrile,   1,1′-azobis(cyclohexanecarbonitrile), 2-t-butylazo-2-cyanopropane,   2,2′-azobis(2,4-dimethylvaleronitrile),   2,2′-azobis(2-amidinopropane)hydrochloride,   2-t-butylazo-2-cyanopropane,   2-t-butylazo-2-cyanobutane,   2-t-butylazo-1-cyanocyclohexane, and   2-t-butylazo-2-cyano-4-methoxy-4-methylpentane.   
     
     
         5 . The method of  claim 2 , wherein the thermal initiator comprises at least one organic peroxide compound selected from the group consisting of: dibenzoyl peroxide, di-t-butyl peroxide, bis-dodecanoyl peroxide, and t-butyl peroxyacetate. 
     
     
         6 . The method of  claim 2 , wherein the thermal initiator comprises at least one dialkyl hyponitrite selected from the group consisting of: di-t-butyl hyponitrite, and di-t-amyl hyponitrite. 
     
     
         7 . The method of  claim 1 , wherein the polymerization initiator comprises a redox pair initiator composed of an oxidizing agent and a reducing agent. 
     
     
         8 . The method of  claim 7 , wherein the oxidizing agent comprises a material selected from the group consisting of: hydrogen peroxide, an organic hydroperoxide, a bromate salt, and a chlorate salt. 
     
     
         9 . The method of  claim 7 , wherein the reducing agent comprises a material selected from the group consisting of: a metabisulfite salt, a formaldehyde sulfoxylate salt, complexed Fe 2+  ion, and ascorbic acid. 
     
     
         10 . The method of  claim 1 , wherein the polymerization initiator comprises a combination of a thermal initiator and a redox pair initiator composed of an oxidizing agent and a reducing agent. 
     
     
         11 . The method of  claim 10 , wherein the oxidizing agent comprises a bromate (BrO 3 —) salt and the reducing agent comprises a metabisulfite (S 2 O 5   2 ) salt. 
     
     
         12 . The method of  claim 10 , wherein the thermal initiator comprises 2,2′-azobis(2,4-dimethyl)valeronitrile. 
     
     
         13 . The method of  claim 10 , wherein the thermal initiator and the oxidizing agent of the redox initiator pair are added to the aqueous monomer solution and oil phase prior to the homogenizing and degassing, and the reducing agent is added to the inverse emulsion after homogenizing and degassing, and before the passing of the monomer solution through the tube reactor. 
     
     
         14 . The method of  claim 1 , wherein the emulsifier comprises at least one nonionic surfactant. 
     
     
         15 . The method of  claim 1 , wherein monomer composition further comprises at least one water-soluble nonionic monomer. 
     
     
         16 . The method of  claim 15 , wherein the acidic monomer comprises acrylic acid and the nonionic monomer comprises acrylamide. 
     
     
         17 . The method of  claim 1 , wherein monomer composition further comprises at least one water-soluble cationic monomer. 
     
     
         18 . The method of  claim 1 , wherein the inverse emulsion has an oil phase-to-water weight ratio is about 21:79 to about 23:77. 
     
     
         19 . The method of  claim 1 , wherein up to about 10 percent of the water of the inverse emulsion is removed during the flash evaporation. 
     
     
         20 . The method of  claim 1 , wherein the flow rate of the inverse emulsion through the tube reactor provides a residence time for the inverse emulsion in the tube reactor of about 6 to about 10 minutes. 
     
     
         21 . A system for continuous polymerization of ethylenically unsaturated monomers in a water-in-oil inverse emulsion under adiabatic conditions, the system comprising:
 a reactor vessel configured to neutralize a monomer composition comprising at least one water-soluble, oil-insoluble, ethylenically unsaturated acidic monomer with a base in an aqueous medium comprising water and water ice to form an aqueous monomer solution characterized by a temperature of 30° C. or less;   a mixing unit configured to homogenize the aqueous monomer solution with an oil phase, optionally in the presence of an emulsifier, to form a water-in-oil inverse emulsion, wherein the mixing unit is also configured to degas the inverse emulsion, and wherein the mixing unit is configured to receive a free-radical polymerization initiator that initiates polymerization of the neutralized monomer composition with the free-radical polymerization initiator;   a tube reactor configured to receive the inverse emulsion, the tube reactor comprising inline static mixing elements, at a flow rate sufficient to polymerize monomers; and   a flash evaporator unit configured to flash evaporate a portion of the water from the inverse emulsion after it exits the tube reactor.   
     
     
         22 . The system of  claim 21 , wherein the flow rate of the inverse emulsion through the tube reactor provides a residence time for the inverse emulsion in the tube reactor of about 6 to about 10 minutes. 
     
     
         23 . The system of  claim 21 , wherein up to about 10 percent of the water of the inverse emulsion is removed by the flash evaporation unit. 
     
     
         24 . The system of  claim 21 , wherein the polymerization initiator is a thermal initiator comprising one or more material selected from the group consisting of an azo compound, an organic peroxide, and a dialkyl hyponitrite.