Method of controlling scale in aqueous systems

Abstract

A method of inhibiting scale in an industrial water system includes the steps of dosing the industrial water system with a water treatment polymer comprising at least 10 mol % of carboxylic acid monomer and a quaternized naphthalimide fluorescent monomer as disclosed herein, and then monitoring the fluorescence of the water system. The polymers are also useful for flocculation and coagulation in wastewater treatment.

1 . A water treatment polymer formed from a polymerization mixture comprising:
 (i) at least one water-soluble carboxylic acid monomer, or salt or anhydride thereof, present in an amount of 10-99.999 mol % based on 100 mol % of the polymer;   (ii) at least one quarternized naphthalimide fluorescent monomer comprising either (a) Structure (I) comprising less than 8 mol %, based on 100 mol % of total Structure (I), of Structure (III) or (b) Structure (II) comprising less than 8 mol %, based on 100 mol % of Structure (II), of Structure (VI), wherein:   Structure (I) is:   
       
         
           
           
               
               
           
         
         wherein 
         R 4  and R 41  are independently selected from H, hydroxy, alkoxy, aryloxy, arylalkoxy, alkylaryloxy, (meth)allyloxy, vinylbenzyloxy, heteroaryl, —NO 2 , C 1 -C 4 alk-O—(CHR 5 CH 2 O—) n , —CO 2 H or a salt thereof, —SO 3 H or a salt thereof, —PO 3 H 2  or a salt thereof, -alkylene-CO 2 H or a salt thereof, -alkylene-SO 3 H or a salt thereof, and -alkylene-PO 3 H 2  or a salt thereof; 
         n=1-10; 
         R 1  and R 2  are independently C 1 -C 4 alkyl; 
         R 3  is selected from (meth)allyl, (meth)acryl, 2-hydroxy-3-(meth)allyloxypropyl, 1-hydroxy-3-(meth)allyloxypropyl, 2-(hydroxy)-3-(ethoxy)-propyl, 3-(allyloxy)-2-(3-(allyloxy)-2-hydroxypropoxy)-propyl, vinylbenzyl, 3-(meth)acrylamidopropyl, and 2-(meth)acryloyloxy ethyl, or alkyl; 
         R 5  is selected from H and C 1 -C 4 alkyl; 
         A is selected from the group consisting of alkyl, alkoxyalkyl, alkylamidoalkyl, arylalkyl or nonexistent; with the proviso that when A is nonexistent, B is nitrogen and B is bonded directly to the imide nitrogen; 
         B is sulfur or nitrogen with the proviso that when B is sulfur only one of R 1  or R 2  is present; and 
         X −  is an anionic counter ion; 
         Structure (II) is: 
       
       
         
           
           
               
               
           
         
         wherein
 m=1-10; 
 
         R 7  and R 8  and R 9  are each independently an alkyl and may be the same or different; 
         R 6  is selected from the group consisting of vinyl, alkenyl, and (meth)allyl; 
         D is oxygen or nonexistent, with the proviso that when D is nonexistent, (CH 2 ) m  is bonded directly to a carbon on the ring; and 
         X −  is an anionic counter ion; 
         Structure (III) is: 
       
       
         
           
           
               
               
           
         
         wherein A, B, R 1 , R 2 , R 4 , and R 41  are as defined above; and 
         Structure (VI) is: 
       
       
         
           
           
               
               
           
         
         wherein D, m, R 7 -R 9 , and X −  are as defined above and R 66  is H or alkyl; 
         said quaternized naphthalimide fluorescent monomer being present in said water treatment polymer in an amount of 0.001-10 mol % based on 100 mol % of the water treatment polymer; and 
         said quaternized napthalimide fluorescent monomer being incorporated into said water treatment polymer to an extent equal to or greater than 90%. 
       
     
     
         2 . The polymer of  claim 1 , wherein the polymerization mixture includes at least one monomer of Structure (I), wherein R 4  is alkoxy selected from methoxy, ethoxy, propyloxy, isopropyloxy, n-butoxy, isobutoxy, and tert-butoxy or hydroxy, and R 41  is H and R 3  is selected from (meth)allyl, (meth)acryl, 2-hydroxy-3-(meth)allyloxypropyl, 1-hydroxy-3-(meth)allyloxypropyl, 2-(hydroxy)-3-(ethoxy)-propyl, 3-(allyloxy)-2-(3-(allyloxy)-2-hydroxypropoxy)-propyl, vinylbenzyl, 3-(meth)acrylamidopropyl, and 2-(meth)acryloyloxy ethyl. 
     
     
         3 . The polymer according to  claim 1 , wherein the polymerization mixture includes at least one monomer of Structure (I), wherein R 4  and R 41  are both other than H. 
     
     
         4 . The polymer of  claim 1 , wherein the polymerization mixture includes at least one monomer of Structure (I) wherein R 4  and R 41  are both alkoxy. 
     
     
         5 . The polymer of  claim 1 , wherein the polymerization mixture includes (a) N-(3-dimethylaminopropyl)-4-methoxy-1,8-naphthalimide, 1 or 2-hydroxy-3-(meth)allyloxypropyl quaternary salt comprising less than 5 mol % of (b)N-(3-dimethylaminopropyl)-4-methoxy-1,8-naphthalimide, based on 100 mol % of (a). 
     
     
         6 . The polymer of  claim 5 , wherein (a) is incorporated into the polymer to the extent of at least 98%. 
     
     
         7 . The polymer of  claim 1 , wherein the polymerization mixture includes at least one monomer of Structure (II). 
     
     
         8 . A method of controlling scale in a water system, the method comprising the steps of:
 (a) dosing the water system with a water treatment polymer according to  claim 1 ; and   (b) monitoring the fluorescent signal emitted from said industrial water system.   
     
     
         9 . A process of preparing the water treatment polymer according to  claim 1 , the process comprising the following steps:
 (a) polymerizing a polymerization mixture comprising:
 (i) at least one water-soluble carboxylic acid monomer, or salt or anhydride thereof, present in an amount of 10-99.999 mol % based on 100 mol % of the polymer; 
 (ii) at least one quarternized naphthalimide fluorescent monomer of either (a) Structure (I) comprising less than 8 mol %, based on 100 mol % of Structure (I), of Structure (III) or (b) Structure (II) comprising less than 8 mol %, based on 100 mol % of Structure (II), of Structure (VI); and 
   (b) ensuring the fluorescent monomer is incorporated into the water treatment polymer to an extent equal to or greater than 90%.   
     
     
         10 . A fluorescent monomer suitable for use in the process of  claim 9 , said monomer comprising either (a) Structure (I) comprising less than 8 mol %, based on 100 mol % of total naphthalimide fluorescent monomer, of Structure (III) or (b) Structure (II) comprising less than 8 mol %, based on 100 mol % of total naphthalimide fluorescent monomer, of Structure (VI), wherein:
 Structure (I) is:   
       
         
           
           
               
               
           
         
         wherein 
         R 4  and R 41  are independently selected from H, hydroxy, alkoxy, aryloxy, arylalkoxy, alkylaryloxy, (meth)allyloxy, vinylbenzyloxy, heteroaryl, —NO 2 , C 1 -C 4 alk-O—(CHR 5 CH 2 O—) n , —CO 2 H or a salt thereof, —SO 3 H or a salt thereof, —PO 3 H 2  or a salt thereof, -alkylene-CO 2 H or a salt thereof, -alkylene-SO 3 H or a salt thereof, and -alkylene-PO 3 H 2  or a salt thereof; 
         n=1-10; 
         R 1  and R 2  are independently C 1 -C 4 alkyl; 
         R 3  is selected from (meth)allyl, (meth)acryl, 2-hydroxy-3-(meth)allyloxypropyl, 1-hydroxy-3-(meth)allyloxypropyl, 2-(hydroxy)-3-(ethoxy)-propyl, 3-(allyloxy)-2-(3-(allyloxy)-2-hydroxypropoxy)-propyl, vinylbenzyl, 3-(meth)acrylamidopropyl, and 2-(meth)acryloyloxy ethyl, or alkyl; 
         R 5  is selected from H and C 1 -C 4 alkyl; 
         A is selected from the group consisting of alkyl, alkoxyalkyl, alkylamidoalkyl, arylalkyl or nonexistent; with the proviso that when A is nonexistent, B is nitrogen and B is bonded directly to the imide nitrogen; 
         B is sulfur or nitrogen with the proviso that when B is sulfur only one of R 1  or R 2  is present; and 
         X −  is an anionic counter ion; 
         Structure (II) is: 
       
       
         
           
           
               
               
           
         
         wherein 
         m=1-10; 
         R 7  and R 8  and R 9  are each independently an alkyl and may be the same or different; 
         R 6  is selected from the group consisting of vinyl, alkenyl, and (meth)allyl; 
         D is oxygen or nonexistent, with the proviso that when D is nonexistent, (CH 2 ) m  is bonded directly to a carbon on the ring; and 
         X −  is an anionic counter ion; 
         Structure (III) is: 
       
       
         
           
           
               
               
           
         
         wherein A, B, R 1 , R 2 , R 4 , and R 41  are as defined above; and 
         Structure (VI) is: 
       
       
         
           
           
               
               
           
         
         wherein D, m, R 7 -R 9 , and X −  are as defined above and R 66  is H or alkyl. 
       
     
     
         11 . The monomer of  claim 10 , which contains Structure (I) and less than 8 mol %, based on 100 mol % of total naphthalimide fluorescent monomer, of compounds of Structure (III). 
     
     
         12 . The monomer of  claim 11 , which is (a)N-(3-dimethylaminopropyl)-4-methoxy-1,8-naphthalimide, 1 or 2-hydroxy-3-(meth)allyloxypropyl quaternary salt comprising less than 5 mol % of (b)N-(3-dimethylaminopropyl)-4-methoxy-1,8-naphthalimide, based on 100 mol % of (a). 
     
     
         13 . A fluorescent monomer suitable for use in the process of  claim 9 , said monomer comprising Structure (I): 
       
         
           
           
               
               
           
         
         wherein 
         R 4  and R 41  are independently selected from H, hydroxy, and C 1 -C 4 alk-O—(CHR 5 CH 2 O) n  with the proviso R 4  and R 41  are not both H; or R 4  and R 41  are both alkoxy; 
         n=1-10; 
         R 1  and R 2  are independently C 1 -C 4 alkyl; 
         R 3  is selected from (meth)allyl, (meth)acryl, 2-hydroxy-3-(meth)allyloxypropyl, 1-hydroxy-3-(meth)allyloxypropyl, 2-(hydroxy)-3-(ethoxy)-propyl, 3-(allyloxy)-2-(3-(allyloxy)-2-hydroxypropoxy)-propyl, vinylbenzyl, 3-(meth)acrylamidopropyl, and 2-(meth)acryloyloxy ethyl; 
         R 5  is selected from H and C 1 -C 4 alkyl; 
         A is selected from the group consisting of alkyl, alkoxyalkyl, alkylamidoalkyl, arylalkyl or nonexistent; with the proviso that when A is nonexistent, B is nitrogen and B is bonded directly to the imide nitrogen; 
         B is sulfur or nitrogen with the proviso that when B is sulfur only one of R 1  or R 2  is present; and 
         X −  is an anionic counter ion. 
       
     
     
         14 . The monomer of  claim 13 , which is N-(3-dimethylaminopropyl)-4-hydroxy-1,8-naphthalimide, 1 or 2-hydroxy-3-(meth)allyloxypropyl quaternary salt. 
     
     
         15 . The monomer of  claim 13 , wherein R 4  and R 41  are both alkoxy. 
     
     
         16 . The monomer of  claim 13 , which is a mixture of two monomers of Structure (I), a first wherein R 4  is alkoxy and R 41  is H and a second wherein R 4  and R 41  are both alkoxy. 
     
     
         17 . A polymer prepared by polymerizing the monomer of  claim 10  with other monomers. 
     
     
         18 . The polymer according to  claim 17 , wherein the other monomers are selected from the group consisting of cationic, anionic, and/or nonionic monomers. 
     
     
         19 . The polymer according to  claim 17 , wherein the fluorescent monomer is incorporated into the polymer to an extent equal to or greater than 90%. 
     
     
         20 . A method for coagulation or flocculation in a water treatment system, the method comprising the steps of:
 (a) dosing the water system with the water treatment polymer according to  claim 1 ; and   (b) monitoring the fluorescent signal emitted from the water treatment system.   
     
     
         21 . A method for determining whether a given location has been cleaned comprising the steps of:
 (a) applying the water treatment polymer according to  claim 1  to the location;   (b) cleaning the location at least once; and   (c) attempting to detect the presence of the fluorescent naphthalimide derivative remaining at the location after said cleaning, which, presence, if detected, indicates that additional cleaning is needed.   
     
     
         22 . A method for coagulation or flocculation in a water treatment system, the method comprising the steps of:
 (a) dosing the water system with the water treatment polymer according to  claim 17 ; and   (b) monitoring the fluorescent signal emitted from the water treatment system.   
     
     
         23 . A method for determining whether a given location has been cleaned comprising the steps of:
 (a) applying the water treatment polymer according to  claim 17  to the location;   (b) cleaning the location at least once; and   (c) attempting to detect the presence of the fluorescent naphthalimide derivative remaining at the location after said cleaning, which, presence, if detected, indicates that additional cleaning is needed.