Cationic Polymers Containing 2-Hydrocyethyl-Methacrylic As Promoters For Asa Sizing

Abstract

The invention relates to polymers useful as a papermaking additives, The invention also relates to methods for making and using such additives.

1 . A cationic polymer useful as a papermaking additive, which is obtained by copolymerizing
 (1) a vinyl monomer selected from the group consisting of the formula (I), formula (Ia), and combinations thereof, wherein formula (I) and formula (Ia) are as follows:
   CH 2 ═CR 1 —COA(CH 2 )nN + R s R S R 3 X −   (I) 
   (CH 2 ═CHCH 2 ) 2 N + (R 2 ) 2 X −   (Ia) 
   wherein R 1  is a hydrogen atom or a methyl group, A is an oxygen atom or NH group, n is 2 or 3, R 2  and R 3  are each a methyl group or an ethyl group and X is a chlorine atom, a bromine atom, or X −  is a methyl sulfate ion; and   (2) a vinyl monomer of the formula:
   CH 2 ═CR 4 —CONH 2    (II) 
   wherein R 4  is a hydrogen atom or a methyl group; and   (3) a vinyl monomer selected from the group consisting of formula (III), (IIIa), and combinations thereof, wherein formula (III) and (IIIa) are as follows:
   CH 2 ═CR 5 COO(CH 2 ) n OH   (III) 
   CH 2 ═CR 6 COO(CH 2 ) m CHOHCH 2 OH   (III) 
   wherein R 5  and R 6  is a hydrogen atom or a methyl group, n is 1-4, inclusive and m is 1 or2.   
   
   
       2 . The polymer of  claim 1 , wherein the polymer has a cationic charge of at least 1 to 99 mole %. 
   
   
       3 . The polymer of  claim 1 , wherein the polymer comprises units derived from 2-hydroxyethyl methacrylate in an amount ranging from 1 to 30 mole percent. 
   
   
       4 . The polymer of  claim 1 , wherein the polymer has an average molecular weight ranging from 10,000 to 3,000,000 daltons. 
   
   
       5 . The polymer of  claim 1 , wherein the polymer is crosslinked or branched. 
   
   
       6 . An amphoteric polymer useful as a papermaking additive, which is obtained by copolymerizing
 (1) a vinyl monomer of the formula:
   CH 2 ═CR 1 —COA(CH 2 ) n N + R 2 R 2 R 3 X −   (I) 
   
     and/or
   (CH 2 ═CHCH 2 ) 2 N + (R 2 ) 2 X −   (Ia) 
 wherein R 1  is a hydrogen atom or a methyl group, A is an oxygen atom or NH group, n is 2 or 3, R 2  and R 3  are each a methyl group or an ethyl group and X is a chlorine atom, a bromine atom, or X −  is a methyl sulfate ion; and 
 (2) a vinyl monomer of the formula:
   CH 2 ═CR 4 —CONH 2    (II) 
 
 wherein R 4  is a hydrogen atom or a methyl group, and 
 (3) a vinyl monomer of the formula:
   CH 2 ═CR 5 COO(CH 2 ) n OH   (III) 
 
 
     and/or
   CH 2 ═CR 6 COO(CH 2 ) m CHOHCH 2 OH   (IIIa) 
 wherein R 5  and R 6  is a hydrogen atom or a methyl group and n is 1 or 4 and m is 1 or 2 ; and 
 (4) an anionic vinyl monomer of the formula:
   CH 2 ═CR 7 COOR 8    (IV) 
 
 wherein R 7  is a hydrogen atom or a methyl group, and R 8  is a hydrogen atom, an alkali metal, or am ammonium group. 
 
   
   
       7 . Polymer of Claim  6 , wherein the polymer has an anionic charge ranging from 0-40 mole percent. 
   
   
       8 . A method comprising
 (a) providing paper stock;   (b) adding to the paper stock a composition comprising:
 (i) synthetic sizing agent, and 
 (ii) a polymer including a cationic polymer useful as a paper additive, which is obtained by copolymerizing 
 (1) a vinyl monomer of the formula:
   CH 2 ═CR 1 —COA(CH 2 ) n N + R 2 R 2 R 3 X −   (I) 
 
   
     and/or
   (CH 2 ═CHCH 2 ) 2 N + (R 2 ) 2 X −   (Ia) 
 wherein R 1  is a hydrogen atom or a methyl group, A is an oxygen atom or NH group, n is 2 or 3, R 2  and R 3  are each a methyl group or an ethyl group and X is a chlorine atom, a bromine atom, or X −  is a methyl sulfate ion; and
 (2) a vinyl monomer of the formula:
   CH 2 ═CR 4 —CONH 2    (II) 
 
 
 wherein R 4  is a hydrogen atom or a methyl group, and
 (3) a vinyl monomer of the formula:
   CH 2 ═CR 5 COO(CH 2 ) n OH   (III) 
 
 
 
     and/or
   CH 2 ═CR 6 COO(CH 2 ) m CHOHCH 2 OH   (IIIa) 
 wherein R 5  and R 6  is a hydrogen atom or a methyl group and n is 1-4, inclusive and m is 1 or 2; and
 (iii) water or starch solution, and 
 
 (c) forming a web from said paper stock,
 wherein the web exhibits an improved sizing efficiency as compared to a web made without the cationic polymer. 
 
 
   
   
       9 . The method of Claim  8 , wherein the polymer a cationic charge of at least 1 to 99 mole %. 
   
   
       10 . The method of Claim  8 , wherein the polymer comprises 2-hydroxyethyl methacrylate in an amount ranging from 1 to 30 mole percent. 
   
   
       11 . The method of Claim  8 , wherein the weight ratio of synthetic sizing agent:polymer is added in an amount ranging from 1:0.05 to 1:1. 
   
   
       12 . The method of Claim  8 , wherein the synthetic sizing agent is emulsified. 
   
   
       13 . The method of Claim  8 , wherein the synthetic sizing agent is selected from the group consisting of alkenyl succinic anhydride, alkyl ketene dimer, alkeno ketene dimers, alkyl isocyanates, alkyl anhydrides, and combinations thereof. 
   
   
       14 . The method of Claim  8 , wherein the synthetic sizing agent is added in conjunction with the cationic polymer. 
   
   
       15 . The method of Claim  8 , wherein the temperature is ranges from 20 C to 40 C. 
   
   
       16 . The method of Claim  8 , wherein the synthetic sizing agent is added as an emulsion containing polymers or an emulsion containing polymers and starch. 
   
   
       17 . The method of Claim  8 , wherein the sizing efficiency: resistance of water to paper is increased, as determined by the ink penetration test or the Cobb test 
   
   
       18 . The method of Claim  8 , wherein the synthetic sizing agent added as a sizing emulsion containing surfactant and the emulsion is prepared under low shear conditions. 
   
   
       19 . The method of Claim  8 , wherein the synthetic sizing agent is added as a sizing emulsion containing surfactant and the emulsion is prepared under high shear conditions. 
   
   
       20 . The method of Claim  8 , wherein the sizing efficiency improvement ranges from 10 to 200 percent more, as compared to when the paper is prepared without the polymer. 
   
   
       21 . Paper made from the method of Claim  8 , wherein the paper has a ink penetration ranging from 50 to 1500 seconds. 
   
   
       22 . Paper made from the method of Claim  8 , wherein the paper has a cobb value ranging from 15 to 200 grams/m 2 . 
   
   
       23 . The method of Claim  8 , wherein the synthetic sizing agent is applied at a dosage ranging from 0.1 kg/metric ton to 10 kg/metric 
   
   
       24 . A method comprising:
 (a) providing paper stock;   (b) adding to the paper stock a composition comprising:
 (i) a synthethic sizing agent, and 
 (ii) an amphoteric polymer useful as a paper additive, which is obtained by copolymerizing 
 (1) a vinyl monomer of the formula:
   CH 2 ═CR 1 —COA(CH 2 ) n N + R 2 R 2 R 3 X −   (I) 
 
   
     and/or
   (CH 2 ═CHCH 2 ) 2 N + (R 2 ) 2 X −   (Ia) 
 wherein R 1  is a hydrogen atom or a methyl group, A is an oxygen atom or NH group, n is 2 or 3, R 2  and R 3  are each a methyl group or an ethyl group and X is a chlorine atom, a bromine atom, or X −  is a methyl sulfate ion; and
 (2) a vinyl monomer of the formula:
   CH 2 ═CR 4 —CONH 2    (II) 
 
 
 wherein R 4  is a hydrogen atom or a methyl group, and
 (3) a vinyl monomer of the formula:
   CH 2 ═CR 5 COO(CH 2 ) n OH   (III) 
 
 
 
     and/or
   CH 2 ═CR 6 COO(CH 2 ) m CHOHCH 2 OH   (IIIa) 
 wherein R 5  and R 6  is a hydrogen atom or a methyl group and n is 1 or 4 and m is 1 or 2; and
 (4) an anionic vinyl monomer of the formula:
   CH 2 ═CR 7 COOR 8    (IV) 
 
 
 wherein R 7  is a hydrogen atom or a methyl group, and R 8  is a hydrogen atom, an alkali metal, or an ammonium group; and 
 (iii) water or starch solution, and 
 (c) forming a web from said paper stock, 
 wherein the web exhibits an improved sizing efficiency as compared to a web made without the amphoteric polymer. 
 
   
   
       25 . A method for making a cationic polymer useful as a paper additive
 wherein the method comprises copolymerizing   (1) a vinyl monomer of the formula:
   CH 2 ═CR 1 —COA(CH 2 ) n N + R 2 R 2 R 3 X −   (I) 
   
     and/or
   (CH 2 ═CHCH 2 ) 2 N + (R 2 ) 2 Cl −   (Ia) 
 wherein R 1  is a hydrogen atom or a methyl group, A is an oxygen atom or NH group, n is 2 or 3, and R 2  and R 3  are each a methyl group or an ethyl group; and 
 (2) a vinyl monomer of the formula:
   CH 2 ═CR 4 —CONH 2    (II) 
 
 wherein R 4  is a hydrogen atom or a methyl group; and 
 (3) a vinyl monomer of the formula:
   CH 2 ═CR 5 COO(CH 2 ) n OH   (III) 
 
 
     and/or
   CH 2 ═CR 6 COO(CH 2 ) m CHOHCH 2 OH   (IIIa) 
 wherein R 5  and R 6  is a hydrogen atom or a methyl group, n is 1-4, inclusive, and m is 1 or 2. 
 
   
   
       26 . A method for malting an amphoteric polymer useful as a paper additive, wherein the method comprises copolymerizing
 (1) a vinyl monomer of the formula:
   CH 2 ═CR 1 —COA(CH 2 ) n N + R 2 R 2 R 3 X −   (I) 
   
     and/or
   (CH 2 ═CHCH 2 ) 2 N + (CH 3 ) 2 Cl − (Ia) 
 wherein R 1  is a hydrogen atom or a methyl group, A is an oxygen atom or NH group, n is 2 or 3, and R 2  and R 3  are each a methyl group or an ethyl group; and 
 (2) a vinyl monomer of the formula:
   CH 2 ═CR 4 —CONH 2    (II) 
 
 wherein R 4  is a hydrogen atom or a methyl group; and 
 (3) a vinyl monomer of the formula:
   CH 2 ═CR 5 COO(CH 2 ) n OH   (III) 
 
 
     and/or
   CH 2 ═CR 6 COO(CH 2 ) m CHOHCH 2 OH (IIIa) 
 wherein R 5  and R 6  is a hydrogen atom or a methyl group, n is 1 or 4 and m is 1 or 2. 
 
   
   
       27 . A method comprising
 (a) providing paper stock;   (b) forming a web from said paper stock,   (c) adding to the web a composition comprising:
 (i) alkenyl succinic anhydride, and 
 (ii) a cationic polymer useful as a paper additive which is obtained be copolymerizing 
 (1) a vinyl monomer of the formula:
   CH 2 ═CR 1 —COA(CH 2 ) n N + R 2 R 2 R 3 X − (I) 
 
   
     and/or
   (CH 2 ═CHCH 2 ) 2 N + (R 2 ) 2 X −   (Ia) 
   wherein R 1  is a hydrogen atom or a methyl group, A is an oxygen atom or NH group, n is 2 or 3, R 2  and R 3  are each a methyl group or an ethyl group and X is a chlorine atom, a bromine atom, or X −  is a methyl sulfate ion; and   (2) a vinyl monomer of the formula:
   CH 2 ═CR 4 —CONH 2    (II) 
   wherein R 4  is a hydrogen atom or a methyl group, and   (3) a vinyl monomer of the formula:
   CH 2 ═CR 5 COO(CH 2 ) n OH   (III) 
   
 
     and/or
   CH 2 ═CR 6 COO(CH 2 ) m OH   (IIIa) 
   wherein R 5  and R 6  is a hydrogen atom or a methyl group, n is 1-4, inclusive and m is 2 or 3; and   (iii) water or starch solution.   
 
   
   
       28 . A method comprising:
 (a) providing paper stock;   (b) forming a web from said paper stock,   (c) adding to the web a composition comprising:
 (i) alkenyl succinic anhydride, and 
 (ii) an amphoteric polymer useful as a paper additive, which is obtained by copolymerizing 
 (1) a vinyl monomer of the formula:
   CH 2 ═CR 1 —COA(CH 2 ) n N 30  R 2 R 2 R 3 X −   (I) 
 
   
     and/or
   (CH 2 ═CHCH 2 ) 2 N + (R 2 ) 2 X −   (Ia) 
 wherein R 1  is a hydrogen atom or a methyl group, A is an oxygen atom or NH group, n is 2 or 3, R 2  and R 3  are each a methyl group or an ethyl group and X is a chlorine atom, a bromine atom, or X −  is a methyl sulfate ion; and
 (2) a vinyl monomer of the formula:
   CH 2 ═CR 4 —CONH 2    (II) 
 
 
 wherein R 4  is a hydrogen atom or a methyl group, and
 (3) a vinyl monomer of the formula:
   CH 2 ═CR 5 COO(CH 2 ) n OH   (III) 
 
 
 
     and/or
   CH 2 ═CR 6 COO(CH 2 ) m CHOHCH 2 OH (IIIa) 
   wherein R 5  and R 6  is a hydrogen atom or a methyl group, n is 1 or 4 and m is or 2;   (4) an anionic vinyl monomer of the formula:
   CH 2 ═CR 7 COOR 8    (IV) 
   wherein R 7  is a hydrogen atom or a methyl group, and R 8  is a hydrogen atom, an alkali metal, ammonium group; and   (iii) water or starch solution.   
 
   
   
       29 . The process of Claim  28 , wherein the paper is further treated with polymers selected from the group consisting of anionic polymers, nonionic polymers, and combinations thereof.