US20040149411A1 - Wet-strength finishing agents for paper - Google Patents
Wet-strength finishing agents for paper Download PDFInfo
- Publication number
- US20040149411A1 US20040149411A1 US10/479,515 US47951503A US2004149411A1 US 20040149411 A1 US20040149411 A1 US 20040149411A1 US 47951503 A US47951503 A US 47951503A US 2004149411 A1 US2004149411 A1 US 2004149411A1
- Authority
- US
- United States
- Prior art keywords
- paper
- weight
- wet strength
- acid
- epihalohydrin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920000962 poly(amidoamine) Polymers 0.000 claims abstract description 19
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims description 21
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical group NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 17
- 239000003623 enhancer Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000000123 paper Substances 0.000 description 24
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 16
- 230000007062 hydrolysis Effects 0.000 description 13
- 238000006460 hydrolysis reaction Methods 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 12
- 239000000178 monomer Substances 0.000 description 10
- 229920001131 Pulp (paper) Polymers 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
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- 125000002091 cationic group Chemical group 0.000 description 5
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- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- HXVJQEGYAYABRY-UHFFFAOYSA-N 1-ethenyl-4,5-dihydroimidazole Chemical class C=CN1CCN=C1 HXVJQEGYAYABRY-UHFFFAOYSA-N 0.000 description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 3
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
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- 239000000853 adhesive Substances 0.000 description 2
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- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
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- 229940073608 benzyl chloride Drugs 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- 229940008406 diethyl sulfate Drugs 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- FWQVHBXYJCMRDM-UHFFFAOYSA-N 1-ethenyl-2-ethyl-4,5-dihydroimidazole Chemical compound CCC1=NCCN1C=C FWQVHBXYJCMRDM-UHFFFAOYSA-N 0.000 description 1
- HFCLUHMYABQVOG-UHFFFAOYSA-N 1-ethenyl-2-ethylimidazole Chemical compound CCC1=NC=CN1C=C HFCLUHMYABQVOG-UHFFFAOYSA-N 0.000 description 1
- VDSAXHBDVIUOGV-UHFFFAOYSA-N 1-ethenyl-2-methyl-4,5-dihydroimidazole Chemical compound CC1=NCCN1C=C VDSAXHBDVIUOGV-UHFFFAOYSA-N 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 description 1
- MMFCEMSIUPCRLD-UHFFFAOYSA-N 1-ethenyl-4-methylimidazole Chemical compound CC1=CN(C=C)C=N1 MMFCEMSIUPCRLD-UHFFFAOYSA-N 0.000 description 1
- SHVBLBWXKTWTAK-UHFFFAOYSA-N 1-ethenyl-5-methylimidazole Chemical compound CC1=CN=CN1C=C SHVBLBWXKTWTAK-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- ZAXCZCOUDLENMH-UHFFFAOYSA-N 3,3,3-tetramine Chemical compound NCCCNCCCNCCCN ZAXCZCOUDLENMH-UHFFFAOYSA-N 0.000 description 1
- XUYDVDHTTIQNMB-UHFFFAOYSA-N 3-(diethylamino)propyl prop-2-enoate Chemical compound CCN(CC)CCCOC(=O)C=C XUYDVDHTTIQNMB-UHFFFAOYSA-N 0.000 description 1
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 1
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- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- DTSDBGVDESRKKD-UHFFFAOYSA-N n'-(2-aminoethyl)propane-1,3-diamine Chemical compound NCCCNCCN DTSDBGVDESRKKD-UHFFFAOYSA-N 0.000 description 1
- KMBPCQSCMCEPMU-UHFFFAOYSA-N n'-(3-aminopropyl)-n'-methylpropane-1,3-diamine Chemical compound NCCCN(C)CCCN KMBPCQSCMCEPMU-UHFFFAOYSA-N 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- GORGQKRVQGXVEB-UHFFFAOYSA-N n-ethenyl-n-ethylacetamide Chemical compound CCN(C=C)C(C)=O GORGQKRVQGXVEB-UHFFFAOYSA-N 0.000 description 1
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 description 1
- OFESGEKAXKKFQT-UHFFFAOYSA-N n-ethenyl-n-methylformamide Chemical compound C=CN(C)C=O OFESGEKAXKKFQT-UHFFFAOYSA-N 0.000 description 1
- DSENQNLOVPYEKP-UHFFFAOYSA-N n-ethenyl-n-methylpropanamide Chemical compound CCC(=O)N(C)C=C DSENQNLOVPYEKP-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- IUWVWLRMZQHYHL-UHFFFAOYSA-N n-ethenylpropanamide Chemical compound CCC(=O)NC=C IUWVWLRMZQHYHL-UHFFFAOYSA-N 0.000 description 1
- RCLLINSDAJVOHP-UHFFFAOYSA-N n-ethyl-n',n'-dimethylprop-2-enehydrazide Chemical compound CCN(N(C)C)C(=O)C=C RCLLINSDAJVOHP-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/56—Polyamines; Polyimines; Polyester-imides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
Definitions
- the present invention relates to wet strength enhancers for paper and to a process for producing wet-strengthened enhanced paper.
- U.S. Pat. No. 2,926,154 discloses water-soluble reaction products of an epihalohydrin and polyamidoamines. The reaction products are used in papermaking by adding them to the paper stock as wet strength agents.
- WO-A-98/32798 discloses a polymer combination prepared by crosslinking a polymer mixture of a polyamidoamine and a vinylamine polymer with an epihalohydrin. These reaction products are added to the paper stock in a papermaking process to add dry and wet strength to the paper.
- U.S. Pat. No. 4,880,497 discloses copolymers which contain vinylamine units and which are formed by hydrolysis of copolymers of N-vinylformamide and other ethylenically unsaturated monomers.
- the copolymers containing vinylamine units are added to the paper stock in the papermaking process to enhance the dry and wet strength of paper.
- reaction products of the reaction of epihalohydrins with amino-containing compounds have the disadvantage of containing major amounts of chlorinous by-products.
- wet strength enhancers for paper comprising mixtures of
- wet strength enhancers comprising
- the invention also provides a process for producing paper by draining a paper stock in the presence of a wet strength enhancer, which comprises using wet strength enhancers comprising mixtures of
- the paper stock is admixed with (a) an epihalohydrin-crosslinked polyamidoamine and (b) at least one other cationic polymer concurrently or in any order, said components (a) and (b) being used in any event in a weight ratio of from 1 to 99.9:0.1 to 20.
- the invention further provides for the use of the above-described wet strength enhancers in the making of paper by addition to the paper stock before sheet formation in amounts of from 0.1 to 4% by weight, based on dry fiber.
- Component (a) of the paper wet strength enhancers according to the invention may be a water-soluble epihalohydrin-crosslinked polyamidoamine.
- Polyamidoamines may be prepared by condensation of dicarboxylic acids with polyalkylenepolyamines, cf. U.S. Pat. No. 2,926,154 and WO-A-98/32798. For example, from 0.8 to 1.4 mol of a polyalkylenepolyamine is used per mole of dicarboxylic acid.
- Polyamidoamines are preferably prepared using aliphatic dicarboxylic acids having 2 to 10 carbon atoms, for example oxalic acid, malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, azelaic acid and lauric acid.
- Preferred dicarboxylic acids are adipic acid and glutaric acid.
- polyalkylenepolyamines examples include diethylenetriamine, tripropylenetetramine, tetraethylenepentamine, methyl-bis-(3-aminopropyl)amine, diaminopropylethylenediamine, bisaminopropylethylenediamine and aminopropylethylenediamine.
- the condensation of dicarboxylic acids with polyalkylenepolyamines is effected at elevated temperature, for example at from 110 to 220° C.
- the water formed in the course of the condensation is distilled out of the reaction mixture.
- the condensation may also be effected in the presence of lactones or lactones of carboxylic acids having 4 to 8 carbon atoms.
- the reaction with epihalohydrins preferably epichlorohydrin, is effected in aqueous solution at for example from 20 to 100° C., preferably from 30 to 80° C.
- the reaction of polyamidoamines with epihalohydrins is carried on only to that point at which the resultant reaction products remain dissolved in water.
- the reaction is terminated by addition of an acid, for example acetic acid or formic acid.
- an acid for example acetic acid or formic acid.
- This provides aqueous solutions of an epichlorohydrin-crosslinked polyamidoamine having a viscosity of for example from 50 to 2000 mPas, preferably from 60 to 400 mPas (determined in a Brookfield viscometer at 20° C., spindle 2, 20 revolutions per minute, concentration of the aqueous polymer solution: 12.5% by weight).
- Useful cationic polymers may be derived for example from synthetic and natural cationic polymers.
- Useful natural polymers include for example cationic polysaccharides, cationic starch, cationic amylose and derivatives thereof, cationic amylopectin and derivatives thereof and also cationic guar derivatives.
- Synthetic cationic polymers include for example polyethyleneimines. They may be prepared by polymerizing ethyleneimine in aqueous solution in the presence of acid-detaching compounds, acids or Lewis acids. Polyethyleneimines are commercially available and their molar masses range for example from 200 to 2 000 000, preferably from 200 to 1 000 000. The process of the invention particularly preferably utilizes polyethylenimines having molar masses from 500 to 800 000.
- a further class of synthetic cationic compounds is that of the addition polymers containing vinylamine units. They may be prepared from open-chain N-vinylcarboxamides of the formula
- R 1 and R 2 are identical or different and are each selected from the group consisting of hydrogen and C 1 -C 6 -alkyl.
- Useful monomers include for example N-vinylformamide (R 1 ⁇ R 2 ⁇ H in formula I), N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-methylpropionamide and N-vinylpropionamide.
- the polymers may be prepared by polymerizing the monomers mentioned alone, mixed with each other or together with other monoethylenically unsaturated monomers.
- the addition polymers in question are preferably homo- or copolymers of N-vinylformamide.
- Useful monoethylenically unsaturated monomers for copolymerization with N-vinylcarboxamides include all compounds copolymerizable therewith. Examples thereof are vinyl esters of saturated carboxylic acids of 1 to 6 carbon atoms such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate.
- Useful comonomers further include ethylenically unsaturated C 3 -C 6 -carboxylic acids, for example acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid and vinyl ester acid and also their alkali metal and alkaline earth metal salts, esters, amides and nitriles of the carboxylic acids mentioned, for example methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate.
- C 3 -C 6 -carboxylic acids for example acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid and vinyl ester acid and also their alkali metal and alkaline earth metal salts, esters, amides and nitriles of the carboxylic acids mentioned, for example methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate.
- carboxylic esters are derived from glycols or polyalkylene glycols where in each case only one OH group is esterified, for example hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate and also monoacrylate esters of polyalkylene glycols having a molar mass of from 500 to 10 000.
- Useful comonomers further include esters of ethylenically unsaturated carboxylic acids with aminoalcohols, for example dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate and diethylaminobutyl acrylate.
- esters of ethylenically unsaturated carboxylic acids with aminoalcohols for example dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylamino
- Basic acrylates can be used in the form of the free bases, salts with mineral acids such as hydrochloric acid, sulfuric acid or nitric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid or of sulfonic acids or in quaternized form.
- Useful quaternizing agents include for example dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride.
- Useful comonomers for the monomers of the formula I further include amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and also N-alkylmonoamides and diamides of monoethylenically unsaturated carboxylic acids with alkyl radicals of from 1 to 6 carbon atoms, for example N-methylacrylamide, N,N-dimethylacrylamide, N-methylmethacrylamide, N-ethylacrylamide and N-propylacrylamide and tert-butylacrylamide and also basic (meth)acrylamides, for example dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, diethylaminoethylacrylamide, diethylaminoethylmethacrylamide, dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and diethylamin
- Useful comonomers for the monomers of the formula I further include N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, N-vinylimidazole and also substituted N-vinylimidazoles, for example N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole and N-vinylimidazolines such as N-vinylimidazoline, N-vinyl-2-methylimidazoline and N-vinyl-2-ethylimidazoline.
- N-Vinylimidazoles and N-vinylimidazolines are used not only in the form of the free bases but also after neutralization with mineral acids or organic acids or after quaternization, a quaternization being preferably effected with dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride. Also useful are diallyldialkylammonium halides, for example diallyldimethylammonium chlorides.
- Useful comonomers for N-vinylcarboxamides further include sulfo-containing monomers, for example vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, the alkali metal or ammonium salts of these acids or 3-sulfopropyl acrylate.
- sulfo-containing monomers for example vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, the alkali metal or ammonium salts of these acids or 3-sulfopropyl acrylate.
- the copolymers contain for example
- the degree of hydrolysis being for example in the range from 1 to 100 mol %.
- polyvinylamine is obtained by complete hydrolysis (degree of hydrolysis 100 mol %) of homopolymers of N-vinylformamide.
- R 1 is as defined for formula I.
- the homopolymers of the N-vinylcarboxamides of the formula I and their copolymers may be hydrolyzed to an extent in the range from 1 to 100 mol %, advantageously to an extent in the range from 5 to 100 mol %, preferably to an extent in the range from 10 to 100 mol %.
- the degree of hydrolysis of the homo- and copolymers is in the range from 20 to 95 mol %.
- the degree of hydrolysis of the homopolymers is synonymous with the vinylamine units content of the polymers.
- the hydrolysis of the N-vinylformamide units can be accompanied by a hydrolysis of the ester groups with the formation of vinyl alcohol units. This is the case especially when the hydrolysis of the copolymers is carried out in the presence of aqueous sodium hydroxide solution.
- Copolymerized acrylonitrile is likewise chemically modified in the hydrolysis, for example converted into amide groups or carboxyl groups.
- the homo- and copolymers containing vinylamine units may optionally contain up to 20 mol % of amidine units, formed for example by intramolecular reaction of an amino group with an adjacent amide group, for example of copolymerized N-vinylformamide.
- Polymers containing vinylamine units also include hydrolyzed graft polymers of N-vinylformamide on polysaccharides, polyalkylene glycols and polyvinyl acetate.
- the N-vinylformamide units grafted onto the polymers are converted into the corresponding addition polymers containing vinylamine units by hydrolysis to detach formyl groups.
- Graft polymers containing vinylamine units are described for example in U.S. Pat. No. 5,334,287, U.S. Pat. No. 6,048,945 and U.S. Pat. No. 6,060,566.
- the cationic polymers are used in the form of salt-free aqueous solutions or low-salt aqueous solutions containing not more than 5% by weight and preferably not more than 2% by weight of an inorganic salt.
- salt-free or low-salt solutions may be prepared by ultrafiltration or by precipitation of the neutral salts with organic solvents such as acetone, methyl ethyl ketone or alcohols.
- Preferred cationic polymers are
- the molar mass M w of the cationic polymers is not less than 15 000 and is preferably in the range from 50 000 to 10 million.
- the molar mass M w of the cationic polymers is determined by light scattering.
- the cationic polymers may have a charge density of at least 1.5 and preferably from 4 to 15 meq/g (measured at pH 7).
- Useful fibers for producing the pulps include all types customary for this purpose, for example mechanical pulp, bleached and unbleached chemical pulp and paper stocks from all annual plants.
- Mechanical pulp includes for example groundwood pulp, thermomechanical pulp (TMP), chemothermomechanical pulp (CTMP), pressure groundwood, semichemical pulp, high yield chemical pulp and refiner mechanical pulp (RMP).
- Useful chemical pulps include for example sulfate, sulfite and soda pulps. Preference is given to using unbleached chemical pulps, which is also known as unbleached kraft pulp.
- Useful annual plants for producing paper stocks include for example rice, wheat, sugarcane and kenaf. Pulps are also produced using waste paper alone or mixed with other fibers.
- Waste paper also includes coated waste, which, owing to its binder content for coating and printing ink compositions, gives rise to white pitch.
- Stickies are due to the adhesives from sticky labels and letter envelopes, due to adhesive materials from spine gluing and due to hotmelts.
- the fibers mentioned may be used alone or mixed with each other.
- the inventive wet strength enhancers comprised of components (a) and (b) contain for example from 0.1 to 20% and preferably from 0.2 to 5% by weight of a cationic natural and/or synthetic polymer.
- the wet strength enhancers are added to the paper stock in the papermaking process in amounts from 0.1 to 5% by weight, preferably from 0.5 to 4% by weight, each percentage being based on dry fiber.
- components (a) and (b) can also be added separately to the paper stock in the papermaking process, in the above-described ratio. It is possible, for instance, first to add component (a) to the paper stock and then to add component (b) just ahead of the headbox for example.
- the order of the components can also be reversed and similarly the two components can also be added concurrently through a two-material nozzle or through two separately disposed metering positions, to the paper stock.
- the wet strength enhancer of the invention provides a further increase in the wet strength of the paper.
- the percentages in the examples are by weight.
- the wet breaking length was determined according to DIN ISO 3781 following a 15 minute immersion in water.
- the stock model used was a 3.3 g/l consistency pulp of 100% bleached pine sulfate beaten to 32° SR and having a pH of 7.1. Samples of this pulp were each admixed with the wet strength agents reported in Table 1 and the mixture obtained in each case was drained on a Rapid-Köthen sheet former. The basis weight of the sheets of paper was 55 g/m 2 in each case. The sheets were stored at 110° C. for 5 minutes. The wet tensile strength of the sheets was then determined by the method indicated above. The materials used and the results obtained therewith are reported in the table.
- Wet strength agent 1 commercially available water-soluble epichlorohydrin-crosslinked polyamidoamine (Luresin® KNU), polymer concentration 13.5% by weight
- Wet strength agent 2 commercially available water-soluble epichlorohydrin-crosslinked polyamidoamine (Kymene® G 3), polymer concentration 16% by weight
- PVAm aqueous solution of polyvinylamine having a molar mass Mw of 400 000 g/mol, polymer concentration 11.8% by weight
Landscapes
- Paper (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/168,246 US8025767B2 (en) | 2001-06-11 | 2008-07-07 | Wet strength enhancers for paper |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10127829 | 2001-06-11 | ||
DE10127829.2 | 2001-06-11 | ||
PCT/EP2002/005900 WO2002101144A1 (fr) | 2001-06-11 | 2002-05-29 | Apprets pour papier conferant une resistance a l'humidite |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/168,246 Continuation US8025767B2 (en) | 2001-06-11 | 2008-07-07 | Wet strength enhancers for paper |
Publications (1)
Publication Number | Publication Date |
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US20040149411A1 true US20040149411A1 (en) | 2004-08-05 |
Family
ID=7687616
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/479,515 Abandoned US20040149411A1 (en) | 2001-06-11 | 2002-05-29 | Wet-strength finishing agents for paper |
US12/168,246 Expired - Fee Related US8025767B2 (en) | 2001-06-11 | 2008-07-07 | Wet strength enhancers for paper |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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US12/168,246 Expired - Fee Related US8025767B2 (en) | 2001-06-11 | 2008-07-07 | Wet strength enhancers for paper |
Country Status (6)
Country | Link |
---|---|
US (2) | US20040149411A1 (fr) |
EP (1) | EP1399623B1 (fr) |
JP (1) | JP2004529279A (fr) |
CN (1) | CN100436707C (fr) |
CA (1) | CA2447136A1 (fr) |
WO (1) | WO2002101144A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050178515A1 (en) * | 2002-06-19 | 2005-08-18 | Michael Ryan | Strong and dispersible paper products |
WO2006015698A1 (fr) * | 2004-08-05 | 2006-02-16 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Article en papier presentant une souplesse et une resistance a la dechirure a l'etat humide relative accrues, procede de fabrication et utilisation dudit article |
US20110079365A1 (en) * | 2008-06-24 | 2011-04-07 | Basf Se | Production of paper |
US8349134B2 (en) | 2004-11-23 | 2013-01-08 | Basf Se | Method for producing high dry strength paper, paperboard or cardboard |
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Publication number | Priority date | Publication date | Assignee | Title |
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US7125469B2 (en) | 2003-10-16 | 2006-10-24 | The Procter & Gamble Company | Temporary wet strength resins |
JP2005171410A (ja) * | 2003-12-10 | 2005-06-30 | Seiko Pmc Corp | 紙及び製造方法 |
EP1809712A1 (fr) * | 2004-11-08 | 2007-07-25 | Akzo Nobel N.V. | Composition pigmentaire sous forme de dispersion aqueuse |
US7259218B2 (en) | 2005-02-17 | 2007-08-21 | The Procter + Gamble Company | Processes for making temporary wet strength additives |
AR071441A1 (es) * | 2007-11-05 | 2010-06-23 | Ciba Holding Inc | N- vinilamida glioxilada |
DE102009044228B4 (de) * | 2009-10-09 | 2012-08-16 | Weiser Chemie + Technik UG (haftungsbeschränkt) | Verfahren zur Erzeugung nassverfestigter Papiere |
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US20050178515A1 (en) * | 2002-06-19 | 2005-08-18 | Michael Ryan | Strong and dispersible paper products |
US7767059B2 (en) | 2002-06-19 | 2010-08-03 | Kemira Oyj | Strong and dispersible paper products |
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US20080302497A1 (en) * | 2004-08-05 | 2008-12-11 | Joachim Storsberg | Paper Product with Increased Relative Wet Tensile Strength and Softness, Method for Production and Use Thereof |
US8349134B2 (en) | 2004-11-23 | 2013-01-08 | Basf Se | Method for producing high dry strength paper, paperboard or cardboard |
US20110079365A1 (en) * | 2008-06-24 | 2011-04-07 | Basf Se | Production of paper |
US8382948B2 (en) | 2008-06-24 | 2013-02-26 | Basf Se | Production of paper |
Also Published As
Publication number | Publication date |
---|---|
EP1399623A1 (fr) | 2004-03-24 |
CN1531613A (zh) | 2004-09-22 |
CN100436707C (zh) | 2008-11-26 |
CA2447136A1 (fr) | 2002-12-19 |
EP1399623B1 (fr) | 2015-01-07 |
US8025767B2 (en) | 2011-09-27 |
US20090008051A1 (en) | 2009-01-08 |
JP2004529279A (ja) | 2004-09-24 |
WO2002101144A1 (fr) | 2002-12-19 |
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