CN1675431A - 含有乙烯基胺单元的聚合物作为烷基二烯酮上浆用促进剂的用途 - Google Patents
含有乙烯基胺单元的聚合物作为烷基二烯酮上浆用促进剂的用途 Download PDFInfo
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- CN1675431A CN1675431A CN03819313.2A CN03819313A CN1675431A CN 1675431 A CN1675431 A CN 1675431A CN 03819313 A CN03819313 A CN 03819313A CN 1675431 A CN1675431 A CN 1675431A
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- Prior art keywords
- vinyl
- polymer
- acid
- dispersion
- dienone
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- 229920000642 polymer Polymers 0.000 title claims abstract description 43
- 238000004026 adhesive bonding Methods 0.000 title abstract 2
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical group NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 title abstract 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000011780 sodium chloride Substances 0.000 claims abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 41
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 230000007062 hydrolysis Effects 0.000 claims description 23
- 238000006460 hydrolysis reaction Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 235000002639 sodium chloride Nutrition 0.000 claims description 19
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 14
- 238000009955 starching Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 7
- 229960002668 sodium chloride Drugs 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 description 56
- 239000000123 paper Substances 0.000 description 29
- 239000002002 slurry Substances 0.000 description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 27
- -1 alkyl ketene dimer Chemical compound 0.000 description 27
- 229920001577 copolymer Polymers 0.000 description 26
- 239000000203 mixture Substances 0.000 description 19
- 125000002091 cationic group Chemical group 0.000 description 17
- 239000000178 monomer Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 239000002585 base Substances 0.000 description 15
- 229920002472 Starch Polymers 0.000 description 14
- 125000000129 anionic group Chemical group 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- 239000000872 buffer Substances 0.000 description 12
- 239000007859 condensation product Substances 0.000 description 12
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 12
- 229920006317 cationic polymer Polymers 0.000 description 11
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- 230000014759 maintenance of location Effects 0.000 description 11
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 10
- 229920001131 Pulp (paper) Polymers 0.000 description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 150000003863 ammonium salts Chemical class 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 8
- 229920003043 Cellulose fiber Polymers 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229940044654 phenolsulfonic acid Drugs 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
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- 238000002360 preparation method Methods 0.000 description 7
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 150000001447 alkali salts Chemical class 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011436 cob Substances 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical group C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 3
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 239000013052 retention aid agent Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 2
- 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
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
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- 239000004698 Polyethylene Substances 0.000 description 2
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- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 2
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
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- 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
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- 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
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- 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
- D21H17/03—Non-macromolecular organic compounds
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- D—TEXTILES; PAPER
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- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
Landscapes
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明涉及含有乙烯基胺单元的K值为30~150(在5%浓度氯化钠水溶液中于25℃、pH值为7、聚合物浓度为0.5重量%条件下测定)的聚合物作为以烷基二烯酮对纸品进行机器上浆用的促进剂的用途。
Description
本发明涉及聚合物作为以烷基二烯酮对纸品进行机器上浆用的促进剂的用途。
用阳离子淀粉或阴离子乳化剂稳定的烷基二烯酮水分散体系是商业化的纸品用机器上浆剂。采用烷基二烯酮分散体系上浆的纸品的全部上浆效果直到上浆纸品经过储存后才能显现出来。因而这种纸品不能进一步加工,例如用涂布浆料处理,或者在制造纸品后立即在其上印刷。而且,它们必须储存至少24小时,直到已经显现出上浆效果。
US-A-4,317,756公开了一种浆料混合物,其含有能与纤维素反应的疏水浆料(例如烷基烯酮二聚体)和阳离子聚合物(例如表氯醇和二氨基丙基哌嗪的缩合物)。阳离子聚合物提高了上浆效果的形成速率,即它们起到促进剂的作用。
根据US-A-4,784,727借助含有苯乙烯、(甲基)丙烯酸N,N-二甲基氨基乙酯和丙烯腈作为聚合单元的三元共聚物可以更迅速地显现出烷基二烯酮水分散体的上浆效果。
WO-A-98/33979公开了一种纤维素用反应性浆料的水分散体,该分散体含有摩尔质量小于10000的阳离子有机化合物和阴离子稳定剂。
WO-A-00/23651公开了阴离子浆料水分散体,其可以通过在阴离子分散剂存在下将反应性浆料(例如烷基二烯酮或链烯基琥珀酸酐)分散在水中而得到。所用的分散剂例如为萘磺酸和甲醛的缩合物或者苯酚、苯酚磺酸和甲醛的缩合物或者疏水性单烯键式不饱和单体和具有阴离子基团的亲水性单体的两性共聚物。所述分散剂可以以游离酸或者以碱金属盐、碱土金属盐和/或铵盐的形式存在。将所述浆料分散体加入纸原料中,如果需要,可以同时使用造纸中常用的助滤剂、絮凝剂、助留剂和固定剂。即使使用阴离子烷基二烯酮分散体,纸品的完全上浆也不会立即发生,但是对于采用通过阳离子分散制备的烷基二烯酮分散体对纸品上浆的情况而言,只有在上浆纸品存储相当长时间后才会发生类似的情况。
EP-A-0 438 707涉及一种由含有干扰物质的纸原料制造纸张、纸板和卡纸板的方法,其中采用水解度至少为60%的N-乙烯基甲酰胺的水解的均聚物和共聚物作为干扰物质的固定剂。这些聚合物优选为与阳离子助留剂组合使用。
WO-A-97/05330公开了采用合成阳离子聚合物(例如聚乙烯基胺和聚乙烯基胺盐酸盐)作为促进剂用于以链烯基琥珀酸酐对纸品进行机器上浆。
本发明的一个目的是提供用于以烷基二烯酮对纸品进行机器上浆的另外的促进剂。
我们已经发现根据本发明该目的可以通过采用含有乙烯基胺单元的K值为30~150(在5%浓度的氯化钠水溶液中于25℃、pH值为7、聚合物浓度为0.5重量%的条件下测量)的聚合物作为用于以烷基二烯酮对纸品进行机器上浆的促进剂而实现。
适合的用于制造纸张、纸板和卡纸板的纤维素纤维是常用于该目的的所有类型的纤维素纤维,例如来自机械纸浆的纤维素纤维和所有由一年生植物得到的纤维。机械纸浆包括例如磨碎木料、热机械纸浆(TMP)、化学热机械纸浆(CTMP)、压力磨碎木料、半化学纸浆、高得率浆、精炼机制纸浆(RMP)和废纸。化学纸浆也是适合的,并可以以漂白或未漂白的形式使用。其实例是硫酸盐纸浆、亚硫酸盐纸浆和碱纸浆。优选采用未漂白纸浆,也被称为未漂白牛皮纸浆。所述纤维可以单独使用或以混合物的形式使用。
用于制备烷基二烯酮水分散体的适合浆料为例如由长链饱和的酰氯化物或通过用叔胺脱去氯化氢的烯键式不饱和的酰氯化物得到的脂肪烷基二烯酮。所述烷基二烯酮优选在烷基中含有12~22个碳原子。适合的烷基二烯酮例如为十四烷基二烯酮、棕榈基二烯酮、油基二烯酮、硬脂基二烯酮和山萮基二烯酮。具有不同烷基的烷基二烯酮也是适合的,例如硬脂基棕榈基二烯酮、山萮基硬脂基二烯酮、山萮基油基二烯酮或棕榈基山萮基二烯酮。优选采用硬脂基二烯酮、棕榈基二烯酮、山萮基二烯酮或者山萮基二烯酮和硬脂基二烯酮的混合物。
通过以下方式加工所述脂肪烷基二烯酮以得到水分散体:首先将其熔化,并在剪切力作用(例如借助于Ultraturrax设备)下在存在阳离子淀粉作为稳定剂的条件下将该熔体分散于水中。也可以采用阴离子化合物作为稳定剂。在例如WO-A-00/23651(参见第2~12页)中公开了制备烷基二烯酮的阴离子水分散体系的方法。对于浆料分散体的制备方法而言,通常将烷基二烯酮加热到高于其熔点,并在剪切力作用下以熔融形式将其在水中乳化。例如,可以采用均化器用于该目的。可以采用阳离子淀粉或选自以下组分的缩合物的至少一种阴离子分散剂将分散的浆料稳定于水相中:
a)萘磺酸和甲醛,
b)苯酚、苯酚磺酸和甲醛,
c)萘磺酸、甲醛和脲,和
d)苯酚、苯酚磺酸、甲醛和脲。
所述阴离子分散剂可以以游离酸、碱金属盐、碱土金属盐和/或铵盐的形式存在。所述铵盐可以源自氨或者伯胺、仲胺或叔胺,例如二甲基胺、三甲基胺、己胺、环己基胺、二环己基胺、乙醇胺、二乙醇胺和三乙醇胺的铵盐是合适的。上述缩合物是已知的并可以市售获得。它们通过使所述组分进行缩合反应而制备,也可以采用相应的碱金属盐、碱土金属盐或铵盐代替游离酸。缩合反应中合适的催化剂例如为酸,如硫酸、对甲苯磺酸和磷酸。萘磺酸或者其碱金属盐与甲醛优选为以1∶0.1~1∶2、一般为1∶0.5~1∶1的摩尔比进行缩合。用于制备苯酚、苯酚磺酸和甲醛的缩合物的摩尔比同样处于上述范围内,在与甲醛的缩合反应中采用任何所需的苯酚和苯酚磺酸的混合物代替萘磺酸。也可以采用苯酚磺酸的碱金属盐和铵盐代替苯酚磺酸。如果需要,上述起始原料的缩合反应还可以在存在脲的情况下进行。例如,以每摩尔萘磺酸或每摩尔苯酚与苯酚磺酸的混合物计使用0.1~5摩尔的脲。
所述缩合物例如具有800~100000的摩尔质量,优选1000~30000,特别优选4000~25000。优选采用的阴离子分散剂为例如通过用氢氧化锂、氢氧化钠、氢氧化钾或氨中和所述缩合物而得到的盐类。所述盐的pH值例如为7~10。
其它适合的阴离子分散剂为下列组分的两性共聚物:
i)疏水性单烯键式不饱和单体,和
ii)具有阴离子基团的亲水性单体,例如单烯键式不饱和羧酸、单烯键式不饱和磺酸、单烯键式不饱和膦酸或者它们的混合物。
合适的疏水性单烯键式不饱和单体
a)例如为具有2~150个碳原子的烯烃、苯乙烯、α-甲基苯乙烯、乙基苯乙烯、4-甲基苯乙烯、丙烯腈、甲基丙烯腈、单烯键式不饱和C3-C5羧酸和一元醇的酯、丙烯酸或甲基丙烯酸与C1-C24烷基胺的酰胺、具有2~24个碳原子的饱和一元羧酸的乙烯基酯、马来酸或富马酸与C1-C24一元醇的二酯、具有3~24个碳原子的醇的乙烯基醚,或者所述化合物的混合物。
所述两性共聚物含有作为亲水性单体(b)的例如单烯键式不饱和C3-C10羧酸或其酸酐、2-丙烯酰氨基-2-甲基丙磺酸、乙烯基磺酸、苯乙烯磺酸、乙烯基膦酸、所述单体的盐或者它们的混合物作为以聚合单元形式的具有阴离子基团的亲水性单体。特别优选的是含有以聚合单元形式的下述组分的两性共聚物作为阴离子分散剂的浆料水分散体,其摩尔质量Mw为1500~100000:
(a)具有4~12个碳原子的α-烯烃、苯乙烯或者它们的混合物作为疏水性单体,和
(b)马来酸、丙烯酸、甲基丙烯酸、马来酸与具有1~25个碳原子的醇的单酯或所述醇的烷氧基化产物、马来酸的单酰胺、所述单体的盐类或者这些化合物的混合物作为具有阴离子基团的亲水性单体。
优选的阴离子分散剂为马来酸酐与C4~C12烯烃、特别优选C8烯烃(例如1-辛烯和二异丁烯)的共聚物。非常特别优选的是二异丁烯。马来酸酐与烯烃的摩尔比例如为0.9∶1~3∶1,优选为0.95∶1~1.5∶1。这些共聚物优选为作为水溶液或水分散体以水解形式使用,同时酸酐基团以打开形式存在,并且部分或所有羧基优选地被中和。下列碱可以用于所述中和反应:碱金属碱,例如氢氧化钠、氢氧化钾、碳酸钠或碳酸钾;碱土金属盐,例如氢氧化钙、碳酸钙或氢氧化镁;氨、伯胺、仲胺或叔胺,例如三乙基胺、三乙醇胺、二乙醇胺、乙醇胺、吗啉等。
如果游离酸形式的两性共聚物不能充分溶于水,那么可以以水溶性盐的形式使用它们,例如使用相应的碱金属盐、碱土金属盐和铵盐。所述两性共聚物的摩尔质量Mw例如为800~250000,一般为1000~100000,优选为3000~20000,特别为1500~10000。所述两性共聚物的酸值例如为50~500mg KOH/g聚合物,优选为150~300mg KOH/g聚合物。
作为制备浆料分散体的阴离子分散剂的所述两性共聚物的用量以反应性浆料计例如为0.05~20重量%,优选为0.5~10重量%。所述两性共聚物的用量以待分散的浆料计优选为0.1~2重量%,特别为0.6~1重量%。当两性共聚物单独用作分散剂时,得到保存期长的不含甲醛的浆料水分散体。
为了制备阴离子浆料水分散体,例如,最初可以采用含有至少一种缩合物或至少一种两性共聚物的水溶液,并在例如20~100℃、优选40~90℃下将浆料分散于其中。所述浆料优选以熔体形式加入,并在剧烈搅拌或剪切下使其分散。分别冷却得到的分散体。例如,可以以这种方式制备含有6~65重量%分散的烷基二烯酮作为浆料的阴离子浆料水分散体。优选在0.1~5.0重量%的萘磺酸和甲醛的缩合物或分散形式的至少一种缩合物(b)、(c)和/或(d)存在下含有例如25~60重量%的烷基二烯酮作为浆料的高度浓缩的浆料分散体。
进一步优选的浆料分散体含有25~60重量%的烷基二烯酮作为浆料和0.1~5.0重量%的下列组分的两性共聚物:
(i)95~50重量%的异丁烯、二异丁烯、苯乙烯或其混合物,和
(ii)5~50重量%的丙烯酸、甲基丙烯酸、马来酸、马来酸单酯或其混合物
或者所述共聚物的水溶性盐。
所述高度浓缩的浆料分散体具有相对低的粘度,例如为20~100mPa·s(采用布氏粘度计在20℃下测量)。在水分散体的制备中,pH值例如为2~8,优选为3~4。得到浆料的平均粒度为0.1~3μm、优选0.5~1.5μm的阴离子浆料水分散体。
如果需要,阴离子烷基二烯酮分散体可以通过加入足量的阳离子淀粉而具有阳离子特性。
根据本发明,采用至少一种含有乙烯基胺单元的聚合物作为用于烷基二烯酮浆料的促进剂。所述阳离子聚合物的量以干纤维素纤维计例如为0.01~2.0重量%,优选0.01~0.1重量%。
含有乙烯基胺单元的聚合物是已知的,参见US-A-4,421,602、US-A-5,334,287、EP-A-0 216 387、US-A-5,981,689、WO-A-00/63295和US-A-6,121,409。通过使含有N-乙烯基羧酸酰胺单元的开链聚合物水解而制备所述聚合物。这些聚合物例如可以通过使N-乙烯基甲酰胺、N-乙烯基-N-甲基甲酰胺、N-乙烯基乙酰胺、N-乙烯基-N-甲基乙酰胺、N-乙烯基-N-乙基乙酰胺和N-乙烯基丙酰胺聚合而获得。所述单体可以单独聚合或者与其它单体一起聚合。
与N-乙烯基羧酸酰胺共聚的合适的单烯键式不饱和单体是可以与之共聚的所有化合物。其实例为具有1~6个碳原子的饱和羧酸的乙烯基酯,例如甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯和丁酸乙烯酯;乙烯基醚,例如C1-C6-烷基乙烯基醚,如甲基乙烯基醚或乙基乙烯基醚。其它合适的共聚单体为烯键式不饱和C3-C6-羧酸的酯、酰胺和腈,例如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酰胺和甲基丙烯酰胺、丙烯腈和甲基丙烯腈。
其它合适的羧酸酯源自二元醇或聚亚烷基二醇,在每种情况中只有一个OH基团被酯化,例如丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟丙酯、甲基丙烯酸羟丁酯以及摩尔质量为500~10000的聚亚烷基二醇的丙烯酸单酯。其它合适的共聚单体为烯键式不饱和羧酸与氨基醇的酯,例如丙烯酸二甲基氨基乙酯、甲基丙烯酸二甲基氨基乙酯、丙烯酸二乙基氨基乙酯、甲基丙烯酸二乙基氨基乙酯、丙烯酸二甲基氨基丙酯、甲基丙烯酸二甲基氨基丙酯、丙烯酸二乙基氨基丙酯、丙烯酸二甲基氨基丁酯和丙烯酸二乙基氨基丁酯。所述碱性丙烯酸酯可以以游离碱、与无机酸(例如盐酸、硫酸或硝酸)的盐、与有机酸(如甲酸、乙酸或丙酸、磺酸)的盐、或季铵化的形式使用。合适的季铵化试剂例如为硫酸二甲酯、硫酸二乙酯、氯代甲烷、氯代乙烷和苄基氯。
其它合适的共聚单体为烯键式不饱和羧酸的酰胺,例如丙烯酰胺、甲基丙烯酰胺;和具有1~6个碳原子烷基的单烯键式不饱和羧酸的N-烷基单酰胺和二酰胺,例如N-甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N-甲基异丁烯酰胺、N-乙基丙烯酰胺、N-丙基丙烯酰胺和叔丁基丙烯酰胺;以及碱性丙烯酰胺和异丁烯酰胺,例如二甲基氨基乙基丙烯酰胺、二甲基氨基乙基异丁烯酰胺、二乙基氨基乙基丙烯酰胺、二乙基氨基乙基异丁烯酰胺、二甲基氨基丙基丙烯酰胺、二乙基氨基丙基丙烯酰胺、二甲基氨基丙基异丁烯酰胺和二乙基氨基丙基异丁烯酰胺。
其它合适的共聚单体为N-乙烯基吡咯烷酮、N-乙烯基己内酰胺、丙烯腈、甲基丙烯腈、N-乙烯基咪唑以及取代的N-乙烯基咪唑例如N-乙烯基-2-甲基咪唑、N-乙烯基-4-甲基咪唑、N-乙烯基-5-甲基咪唑、N-乙烯基-2-乙基咪唑;和N-乙烯基咪唑啉例如N-乙烯基咪唑啉、N-乙烯基-2-甲基咪唑啉和N-乙烯基-2-乙基咪唑啉。N-乙烯基咪唑和N-乙烯基咪唑啉不仅可以以游离碱的形式使用,也可以以用无机酸或有机酸中和的形式或季铵化形式使用,优选为采用硫酸二甲酯、硫酸二乙酯、氯代甲烷或苄基氯来进行季铵化。二烯丙基二烷基卤化铵例如二烯丙基二甲基氯化铵也是合适的。
所述共聚物含有例如以聚合单元形式存在的-95~5mol%,优选90~10mol%的至少一种N-乙烯基羧酸酰胺,和-5~95mol%,优选10~90mol%的其它可与之共聚的单烯键式不饱和单体。所述共聚单体优选不含酸基团。
含有乙烯基胺单元的聚合物优选从N-乙烯基甲酰胺的均聚物或者从可通过下列组分共聚得到的共聚物开始制备:
-N-乙烯基甲酰胺与
-甲酸乙烯基酯、乙酸乙烯基酯、丙酸乙烯基酯、丙烯腈、N-乙烯基己内酰胺、N-乙烯基脲、N-乙烯基吡咯烷酮或者C1-C6烷基乙烯基醚,并随后对所述均聚物或者共聚物进行水解,同时由聚合的N-乙烯基甲酰胺单元形成乙烯基胺单元,水解度例如为1~100mol%,优选为70~100mol%。水解程度特别地为80~100mol%。通过已知的方法在酸、碱或酶作用下进行上述聚合物的水解。当采用酸作为水解试剂时,聚合物的乙烯基胺单元以铵盐形式存在,当采用碱时,在水解过程中形成游离的氨基。含有乙烯基胺单元的聚合物可以以游离碱、铵盐或季铵化形式用作促进剂。
多数情况下,所用的均聚物和共聚物的水解度为90~95mol%。均聚物的水解度等于聚合物中乙烯基胺单元的含量。对于含有乙烯基酯作为聚合单元的共聚物而言,除了N-乙烯基甲酰胺单元的水解,还会出现酯基团的水解以及同时乙烯基醇单元的形成。尤其当在氢氧化钠溶液存在下进行共聚物的水解时是这种情况。在水解作用中以聚合单元形式存在的丙烯腈同样在化学上发生变化。例如,形成酰氨基或羧基。如果需要,含有乙烯基胺单元的均聚物和共聚物可以含有高达20mol%的脒单元,例如通过甲酸与两个相邻的氨基反应或通过氨基与相邻的酰氨基团(例如以聚合单元形式存在的N-乙烯基甲酰胺的酰氨基)的分子内反应形成所述脒单元。含有乙烯基胺单元的聚合物的摩尔质量Mw例如为500~10000000,优选为1000~5000000(通过光散射法测定)。该摩尔质量范围例如对应于K值为30~150,优选为60~90(根据H.Fikentscher在5%浓度氯化钠水溶液中于25℃、pH值为7、聚合物浓度为0.5重量%条件下测定)。特别优选采用K值为85~90的阳离子聚合物。
含有乙烯基胺单元的聚合物的平均摩尔质量Mw例如为8000~2000000,优选为70000~240000。
优选以不含盐的形式使用含有乙烯基胺单元的聚合物。含有乙烯基胺单元的聚合物的不含盐的水溶液例如可以通过由上述含盐的聚合物溶液在合适的截留值例如为1000~500000、优选10000~300000道尔顿的膜上借助超滤而制备。
含有乙烯基胺单元的聚合物的衍生物也可以用作阳离子聚合物。例如,可以由含有乙烯基胺单元的聚合物通过使所述聚合物的氨基酰胺化、烷基化、形成磺酰胺、形成脲、形成硫脲、形成氨基甲酸酯、酰化、羧甲基化、膦酰甲基化或迈克尔加成制备大量合适的衍生物。这里特别值得注意的是非交联的聚乙烯基胍,其可通过含有乙烯基胺单元的聚合物、优选聚乙烯基胺与氨腈(R1R2N-CN,其中R1和R2为H、C1-C4烷基、C3-C6环烷基、苯基、苄基、烷基取代的苯基或萘基)反应而得到,参见US-A-6,087,448第3栏第64行至第5栏第14行。
含有乙烯基胺单元的聚合物还包括例如N-乙烯基甲酰胺在聚亚烷基二醇、聚醋酸乙烯酯、聚乙烯醇、聚乙烯基甲酰胺、多糖(例如淀粉)、低聚糖或单糖上的水解的接枝聚合物。所述接枝聚合物可以通过如下方式得到:在含水介质中在至少一种所述接枝基体存在下将例如N-乙烯基甲酰胺(如果需要与其它可共聚的单体一起)进行自由基聚合和随后以已知的方式使接枝上的乙烯基甲酰胺单元水解而得到乙烯基胺单元。
优选的含有乙烯基胺单元的聚合物为乙烯基胺均聚物、10~95%水解度的聚乙烯基甲酰胺,部分或者完全、优选90~95%水解的乙烯基甲酰胺与醋酸乙烯酯、乙烯醇、乙烯基吡咯烷酮或丙烯酰胺的共聚物,在每种情况下均具有30~150、特别地60~90的K值。
纸张、纸板和卡纸板一般通过对纤维素纤维的悬浮液进行排水而制备。特别优选使用牛皮纸浆。同样特别值得注意的是使用TMP和CTMP。纤维素纤维悬浮液的pH值例如为4~8,优选为6~8。纸原料可以在造纸机上间歇地或连续地排水。阳离子聚合物、机器上浆料和助留剂的添加次序可以自由选择。然而,优选的是向纤维素纤维水悬浮液中添加烷基二烯酮水分散体和至少一种含有乙烯基胺单元的化合物的混合物,或者先添加阳离子聚合物(优选为聚乙烯基胺)和然后添加至少一种烷基烯酮二聚体或者烷基烯酮二聚体的混合物的工序。其后,计量加入优选至少一种助留剂。根据本发明的另一个实施方案,首先计量加入至少一种烷基二烯酮,然后计量加入助留剂,最后计量加入含有乙烯基胺单元的聚合物。在对纸品进行机器上浆的过程中,烷基烯酮二聚体的用量分别以干燥的纸原料计例如为0.01~2重量%,优选为0.01~0.2重量%。如果烷基烯酮二聚体的水分散体已经包含至少一种含有乙烯基胺单元并用作促进剂的聚合物,那么以烷基烯酮二聚体计,该促进剂的用量例如为0.0001~2重量%,优选0.001~1重量%。
在纸原料已经排水并且纸制品已经干燥之后,可以得到机器上浆的基础重量例如为20~400g/m2、优选40~220g/m2的纸制品,例如纸张、纸板或卡纸板。
纸原料优选附加地在助留剂存在下排水。除了阴离子助留剂或非离子助留剂(例如聚丙烯酰胺)之外,优选采用阳离子助留剂作为助留剂和排水助剂。这样可以显著改善造纸机的运行能力。
可以使用的阳离子助留剂是可用于该目的的市售可得的所有制品。这些例如是阳离子聚丙烯酰胺、聚二烯丙基二甲基氯化铵、高分子量的聚乙烯基胺、K值大于150的高分子量聚乙烯基胺、聚乙烯亚胺、摩尔质量大于50000的聚胺、用吖丙啶接枝并且未交联或交联的改性聚胺、聚醚胺、聚乙烯基咪唑、聚乙烯基吡咯烷、聚乙烯基咪唑啉、聚乙烯基四氢pyrine、聚(二烷基氨基烷基乙烯基醚)、质子化或季铵化的聚((甲基)丙烯酸二烷基氨基烷基酯)、由二元羧酸(例如己二酸)得到的聚酰胺型胺类、根据DE-B-24 34 816与吖丙啶接枝和与聚乙二醇二表氯醇醚交联的聚亚烷基多胺(例如二亚乙基三胺)、或已经与表氯醇反应得到不溶于水的缩合物的聚酰胺型胺类、以及丙烯酰胺或甲基丙烯酰胺与丙烯酸二烷基氨基乙酯或甲基丙烯酸二烷基氨基乙酯的共聚物(例如丙烯酰胺与丙烯酸二甲基氨基乙酯的以盐酸成盐形式或与氯代甲烷季铵化形式的共聚物)。其它合适的助留剂为含有阳离子聚合物例如阳离子淀粉和细分二氧化硅的微粒体系或者含有阳离子聚合物例如阳离子聚丙烯酰胺和膨润土的微粒体系。
用作助留剂的阳离子聚合物例如具有大于150的Fikentscher K值(在5%浓度氯化钠水溶液于聚合物浓度为0.5重量%、温度为25℃、pH值为7的条件下进行测量)。它们的用量以干燥的纤维素纤维计优选为0.01~0.3重量%。
在下面的实施例中,除非文中明显指出,百分数以重量计。根据H.Fikentscher在“Cellulose-Chemie”(13)1932年,第58~64和71~74页中介绍的在5%浓度氯化钠水溶液中于25℃、pH值为7、聚合物浓度为0.5重量%的条件下测量K值。通过光散射来测量聚合物的摩尔质量Mw。
实施例
Cobb值
根据DIN 53 132将纸张存放在水中持续60秒来进行测量。吸水能力用g/m2表示。
借助Hercule Size Tester根据TAPPI测试方法T530pm-89测量HST值。
分散体1
固含量为12%硬脂基二烯酮和2%阳离子淀粉的水分散体。
分散体2
固含量为12%硬脂基二烯酮和2%阳离子淀粉以及附加的基于硬脂基二烯酮0.12%的K值为90的聚乙烯基胺的水分散体。
分散体3
固含量为12%硬脂基二烯酮和2%阳离子淀粉以及附加的基于硬脂基二烯酮0.12%的水解度为81%、K值为90的水解聚乙烯基甲酰胺的水分散体。
分散体4
固含量为12%硬脂基二烯酮和2%阳离子淀粉以及附加的基于硬脂基二烯酮0.12%的水解度为95%、K值为90的改性水解聚乙烯基甲酰胺的水分散体,其中按照WO-A-00/26468的实施例2通过将部分水解的聚乙烯基甲酰胺(67mol%的乙烯基甲酰胺单元和33mol%的乙烯基胺单元)反应而进行所述改性。
实施例1
向稠度为8g/l、含有打浆度为35°(Schopper-Riegler)的70%松木硫酸盐纸浆和30%桦木硫酸盐纸浆的完全漂白的混合物的纸原料中加入表1和表2中所述的分散体1~4的量、分别以干燥的纤维素纤维混合物计20%的碳酸钙、0.6%的阳离子玉米淀粉和0.04%的阳离子聚丙烯酰胺(PolyminKE2020)作为助留剂。使得该混合物的pH值达到7.0。随后在Rapid-Kthen纸页成型器上加工该混合物以得到基础重量为100g/m2的纸页。随后在蒸气加热的干燥筒上于90℃下干燥该纸页至含水量为7%。干燥后立即测量纸页的Cobb值和HST值。然后将纸页在25℃、相对湿度为50%的条件下存放24小时。重复测试上述测试过程。得到的结果如表1和2所示。
表1
测试号 | 分散体 | 基于干燥纸原料的硬脂基二烯酮[%] | Cobb 60[g/m2](立即) | Cobb 60[g/m2](24小时后) |
1 | 分散体1 | 0.07 | 56 | 32 |
2 | 分散体1 | 0.1 | 45 | 25 |
3 | 分散体2 | 0.07 | 44 | 29 |
4 | 分散体2 | 0.1 | 33 | 25 |
5 | 分散体3 | 0.07 | 40 | 28 |
6 | 分散体3 | 0.1 | 34 | 24 |
7 | 分散体4 | 0.1 | 31 | 24 |
测试1和2为对比实施例,测试3~7为根据本发明的实施例。
表2
测试号 | 分散体 | 分散体的量%纤维质量 | HST[秒](立即) | HST[秒](24小时后) |
8 | 分散体1 | 0.07 | 32 | 122 |
9 | 分散体1 | 0.1 | 128 | 256 |
10 | 分散体2 | 0.07 | 92 | 143 |
11 | 分散体2 | 0.1 | 187 | 299 |
12 | 分散体3 | 0.07 | 88 | 151 |
13 | 分散体3 | 0.1 | 167 | 278 |
14 | 分散体4 | 0.1 | 195 | 295 |
测试8和9为对比实施例,测试10~14为根据本发明的实施例。
Claims (6)
1.一种含有乙烯基胺单元的K值为30~150(在5%浓度氯化钠水溶液中于25℃、pH值为7、聚合物浓度为0.5重量%条件下测定)的聚合物作为以烷基二烯酮对纸品进行机器上浆用的促进剂的用途。
2.如权利要求1所述的用途,其中所述含有乙烯基胺单元的聚合物的K值为60~90。
3.如权利要求1或2所述的用途,其中使用水解度为1~100%的水解聚-N-乙烯基甲酰胺作为所述含有乙烯基胺单元的聚合物。
4.如权利要求1~3中任一项所述的用途,其中使用水解度为70~100%的水解聚-N-乙烯基甲酰胺作为所述含有乙烯基胺单元的聚合物。
5.如权利要求1~4中任一项所述的用途,其中使用聚乙烯基胺作为所述促进剂。
6.如权利要求1~5中任一项所述的用途,其中所述含有乙烯基胺单元的聚合物的用量以干燥的纸原料计为0.0001~2.0重量%。
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DE10237911A DE10237911A1 (de) | 2002-08-14 | 2002-08-14 | Verwendung von Vinylamineinheiten enthaltenden Polymeren als Promoter für die Alkyldiketenleimung |
DE10237911.4 | 2002-08-14 |
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US (1) | US20060162883A1 (zh) |
EP (1) | EP1530659A1 (zh) |
JP (1) | JP2005535798A (zh) |
CN (1) | CN1675431A (zh) |
AU (1) | AU2003254581A1 (zh) |
BR (1) | BR0313334A (zh) |
CA (1) | CA2495372A1 (zh) |
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JP2007514097A (ja) | 2003-12-10 | 2007-05-31 | フォイクト・ディーター | オイルポンプの回転数依存型圧力制御 |
DE102004010447A1 (de) * | 2004-03-01 | 2005-09-22 | Basf Ag | Wässrige Dispersion von Reaktivleimungsmitteln, Verfahren zu ihrer Herstellung und ihre Verwendung |
PT1819876E (pt) * | 2004-11-29 | 2011-03-07 | Basf Se | Agente de colagem interna de papel |
US20070261807A1 (en) * | 2006-05-12 | 2007-11-15 | Taggart Thomas E | Use of polyvinylamine to improve oil and water sizing in cellulosic products |
US20100016478A1 (en) * | 2006-12-20 | 2010-01-21 | Basf Se | Paper size mixtures |
DE102009036344A1 (de) * | 2009-08-06 | 2011-02-10 | Bk Giulini Gmbh | Leimungsmittel für Papier |
MX369909B (es) * | 2009-12-18 | 2019-11-26 | Hercules Inc | Composicion de encolado de papel. |
WO2012065951A1 (en) * | 2010-11-16 | 2012-05-24 | Basf Se | Manufacture of cellulosic pulp sheets |
EP2882899A2 (en) | 2011-11-14 | 2015-06-17 | Kemira Oyj | Akd composition and manufacture of paper and paperboard |
EP2961886B1 (en) | 2013-03-01 | 2018-07-18 | Basf Se | Aqueous emulsion of a sizing agent |
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US2961366A (en) * | 1957-02-27 | 1960-11-22 | Hercules Powder Co Ltd | Sized paper and method of making same |
US4317756A (en) * | 1977-08-19 | 1982-03-02 | Hercules Incorporated | Sizing composition comprising a hydrophobic cellulose-reactive sizing agent and a cationic polymer |
DE3128478A1 (de) * | 1981-07-18 | 1983-02-03 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von linearen, basischen polymerisaten |
DE3203189A1 (de) * | 1982-01-30 | 1983-08-04 | Bayer Ag, 5090 Leverkusen | Leimungsmittel und seine verwendung |
DE3534273A1 (de) * | 1985-09-26 | 1987-04-02 | Basf Ag | Verfahren zur herstellung von vinylamin-einheiten enthaltenden wasserloeslichen copolymerisaten und deren verwendung als nass- und trockenverfestigungsmittel fuer papier |
DE4001045A1 (de) * | 1990-01-16 | 1991-07-18 | Basf Ag | Verfahren zur herstellung von papier, pappe und karton |
DE4133123A1 (de) * | 1991-10-05 | 1993-04-08 | Basf Ag | Verwendung von copolymerisaten aus langkettigen olefinen und maleinsaeureanhydrid in form der halbamide mit morpholin als leimungsmittel fuer papier |
DE4229142A1 (de) * | 1992-09-01 | 1994-03-03 | Basf Ag | Papierleimungsmittelmischungen |
JPH08146555A (ja) * | 1994-11-17 | 1996-06-07 | Mitsubishi Paper Mills Ltd | 写真印画紙用支持体 |
DE19607674A1 (de) * | 1996-02-29 | 1997-09-04 | Basf Ag | Verwendung von hydrolysierten Polymerisaten von N-Vinylcarbonsäureamiden als Mittel zur Erhöhung der Trockenfestigkeit von Papier, Pappe und Karton |
DE19654390A1 (de) * | 1996-12-27 | 1998-07-02 | Basf Ag | Verfahren zur Herstellung von Papier |
SE9704931D0 (sv) * | 1997-02-05 | 1997-12-30 | Akzo Nobel Nv | Sizing of paper |
US6368457B1 (en) * | 1997-08-05 | 2002-04-09 | Westvaco Corporation | Internal paper sizing agent |
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- 2003-07-24 CN CN03819313.2A patent/CN1675431A/zh active Pending
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- 2003-07-24 WO PCT/EP2003/008089 patent/WO2004022847A1/de not_active Application Discontinuation
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EP1530659A1 (de) | 2005-05-18 |
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