Method for producing high dry strength paper, paperboard or cardboard
The invention relates to a process for producing paper, board and cardboard of high dry strength by separately adding a polymer comprising vinylamine units and a polymeric anionic compound to a paper pulp, dewatering the pulp and drying the paper products, which comprises using as polymeric anionic compound at least one copolymer obtainable by copolymerizing (a) at least one N-vinylcarboxamide of the formula in which R 1 and R 2 are H or C 1 - to C 6 alkyl, (b) at least one monoethylenically unsaturated monomer comprising acid groups, and/or the alkali metal, alkaline earth metal or ammonium salts thereof, and if appropriate (c) other monoethylenically unsaturated monomers, and if appropriate (d) compounds having at least two ethylenically unsaturated double bonds in their molecule.
1. A process for producing paper, board and cardboard of high dry strength by separately adding a polymer comprising vinylamine units and a polymeric anionic compound to a paper pulp, dewatering the pulp and drying the paper products, wherein said polymeric anionic compound consists of the following monomers which are copolymerized:
(a) at least one N-vinylcarboxamide of the formula
in which R 1 and R 2 are H or C 1 to C 6 alkyl,
(b) at least one acidic monoethylenically unsaturated monomer and/or the alkali metal, alkaline earth metal or ammonium salts thereof, and, optionally,
(c) at least one other monoethylenically unsaturated monomer selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl ester, N-vinylpyrrolidone, N-vinylimidazole, acrylamide and methacrylamide.
2. The process according to claim 1 , wherein said polymeric anionic compound consists of the following monomers which are copolymerized:
(a) N-vinylformamide,
(b) acrylic acid, methacrylic acid, and/or the alkali metal or ammonium salts thereof, and, optionally,
(c) at least one other monoethylenically unsaturated monomer selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl ester, N-vinylpyrrolidone, N-vinylimidazole, acrylamide and methacrylamide.
3. The process according to claim 1 , wherein said polymeric anionic compound consists of the following monomers which are copolymerized:
(a) 10 to 95 mol % of units of the formula I,
(b) 5 to 90 mol % of units of a monoethylenically unsaturated carboxylic acid having 3 to 8 carbon atoms in its molecule, and/or the alkali metal, alkaline earth metal or ammonium salts thereof, and
(c) 0 to 30 mol % of units of at least one other monoethylenically unsaturated monomer selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl ester, N-vinylpyrrolidone, N-vinylimidazole, acrylamide and methacrylamide.
4. The process according to claim 1 , wherein said polymeric anionic compound consists of the following monomers which are copolymerized:
(a) 10 to 95 mol % of units of the formula I,
(b) 5 to 90 mol % of units of an acidic monoethylenically unsaturated monomer, and/or the alkali metal, alkaline earth metal or ammonium salts thereof, and
(c) 0 to 30 mol % of units of at least one other monoethylenically unsaturated monomer selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl ester, N-vinylpyrrolidone, N-vinylimidazole, acrylamide and methacrylamide.
5. A process for producing paper, board and cardboard of high dry strength by separately adding a polymer comprising vinylamine units and a polymeric anionic compound to a paper pulp, dewatering the pulp and drying the paper products, wherein said polymeric anionic compound consists of the following monomers which are copolymerized:
(a) at least one N-vinylcarboxamide of the formula
in which R 1 and R 2 are H or C 1 to C 6 alkyl,
(b) at least one monoethylenically unsaturated carboxylic acid having 3 to 8 carbon atoms in its molecule, and/or the alkali metal, alkaline earth metal or ammonium salts thereof, optionally,
(c) at least one other monoethylenically unsaturated monomer selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl ester, N-vinylpyrrolidone, N-vinylimidazole, acrylamide and methacrylamide, and
(d) a monomer containing vinylamine units,
wherein the vinylamine units (e) are obtained by partly eliminating groups —CO—R 1 from the monomers of the formula I copolymerized in the copolymer to form amino groups, wherein the amount of amino groups in the copolymer is at least 5 mol % below the amount of copolymerized acidic monomers (b).
6. The process according to claim 5 , wherein said polymeric anionic compound consists of the following monomers which are copolymerized:
(a) 10 to 95 mol % of units of the formula I,
(b) 5 to 90 mol % of units of an acidic monoethylenically unsaturated monomer, and/or the alkali metal, alkaline earth metal or ammonium salts thereof,
(c) 0 to 30 mol % of units of at least one other monoethylenically unsaturated monomer selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl ester, N-vinylpyrrolidone, N-vinylimidazole, acrylamide and methacrylamide,
(d) 0 to 42 mol % of vinylamine units, wherein the amount of amino groups in the copolymer is at least 5 mol % below the amount of copolymerized acidic monomers (b).
7. The process according to claim 1 , wherein said polymeric anionic compound consists of the following monomers which are copolymerized:
(a) 50 to 90 mol % of N-vinylformamide,
(b) 10 to 50 mol % of acrylic acid, methacrylic acid and/or the alkali metal or ammonium salts thereof, and, optionally,
(c) 0 to 30 mol % of at least one other monoethylenically unsaturated monomer selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl ester, N-vinylpyrrolidone, N-vinylimidazole, acrylamide and methacrylamide.
8. The process according to claim 1 , wherein said polymer comprising vinylamine units comprises at least one compound which is obtained by polymerizing at least one monomer of the formula I
in which R 1 and R 2 are H or C 1 to C 6 alkyl,
and then partly or completely eliminating the groups —CO—R 1 from the monomer I units copolymerized in the polymer to form amino groups.
9. The process according to claim 1 , wherein said polymer comprising vinylamine units comprises at least 10 mol % hydrolyzed homopolymer of N-vinylformamide.
10. The process according to claim 1 , wherein said polymer comprising vinylamine units comprises a copolymer which is obtained by copolymerizing
a) at least one N-vinylcarboxamide of the formula
in which R 1 and R 2 are H or C 1 to C 6 alkyl,
b) at least one acidic monoethylenically unsaturated monomer, and/or the alkali metal, alkaline earth metal or ammonium salts thereof, and, optionally,
c) at least one other monoethylenically unsaturated monomer selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl ester, N-vinylpyrrolidone, N-vinylimidazole, acrylamide and methacrylamide, and, optionally,
d) at least one compound selected from the group consisting of methylenebisacrylamide, glycol diacrylate, glycol dimethacrylate, glyceryl triacrylate, triallylamine, pentaerythritol triallyl ether, polyalkylene glycol at least twice esterified with acrylic acid and/or methacrylic acid, and a polyol,
e) a monomer containing vinylamine units,
wherein the vinylamine units (e) are obtained by partly or completely eliminating the groups —CO—R 1 from the monomer I units copolymerized in the polymer to form amino groups, wherein the fraction of amino groups in the copolymer is greater by at least 10 mol % than the fraction of units of monoethylenically unsaturated acidic monomers (b).
11. The process according to claim 1 , wherein said polymer comprising vinylamine units comprises polyvinylamine and/or at least 50 mol % hydrolyzed homopolymers of N-vinylformamide.
12. The process according to claim 1 , wherein the polymer comprising vinylamine units and said polymeric anionic compound are each used in an amount of 0.1 to 2.0% by weight, based on dry paper pulp.
13. The process according to claim 1 , wherein a ratio of the polymer comprising vinylamine units to the polymeric anionic compound is 5:1 to 1:5.
14. The process according to claim 1 , wherein a ratio of the polymer comprising vinylamine units to the polymeric anionic compound is 2:1 to 1:2.
15. The process according to claim 1 , wherein the vinyl ester is at least one vinyl acetate and vinyl propionate.
16. The process according to claim 1 , wherein said polymeric anionic compound consists of the monomers (a), (b), and (c) which are copolymerized.
17. The process according to claim 1 , wherein said polymeric anionic compound consists of the monomers (a) and (b) which are copolymerized.