CN1374978A - 对纸浆具有高亲和力的聚合物稳定剂 - Google Patents
对纸浆具有高亲和力的聚合物稳定剂 Download PDFInfo
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- CN1374978A CN1374978A CN00812987A CN00812987A CN1374978A CN 1374978 A CN1374978 A CN 1374978A CN 00812987 A CN00812987 A CN 00812987A CN 00812987 A CN00812987 A CN 00812987A CN 1374978 A CN1374978 A CN 1374978A
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- 239000003381 stabilizer Substances 0.000 title claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000004383 yellowing Methods 0.000 claims abstract description 16
- 239000002738 chelating agent Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 44
- 229910052760 oxygen Inorganic materials 0.000 claims description 42
- 239000001301 oxygen Substances 0.000 claims description 42
- 239000000126 substance Substances 0.000 claims description 42
- 229920001131 Pulp (paper) Polymers 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 238000010521 absorption reaction Methods 0.000 claims description 26
- -1 amino, hydroxyl Chemical group 0.000 claims description 23
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- 239000007795 chemical reaction product Substances 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 16
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
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- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
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- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical class C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 229920005604 random copolymer Polymers 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
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- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 claims description 4
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- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 3
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052736 halogen Inorganic materials 0.000 claims description 2
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- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims description 2
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract description 5
- 239000012965 benzophenone Substances 0.000 abstract description 5
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- 229920005610 lignin Polymers 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000006096 absorbing agent Substances 0.000 abstract description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006081 fluorescent whitening agent Substances 0.000 abstract 1
- 150000002443 hydroxylamines Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
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- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 8
- 238000004061 bleaching Methods 0.000 description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- BTNNPSLJPBRMLZ-UHFFFAOYSA-N benfotiamine Chemical compound C=1C=CC=CC=1C(=O)SC(CCOP(O)(O)=O)=C(C)N(C=O)CC1=CN=C(C)N=C1N BTNNPSLJPBRMLZ-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical group O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 6
- 150000003053 piperidines Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 239000002655 kraft paper Substances 0.000 description 4
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 3
- HZKVDLABFATIAT-UHFFFAOYSA-N CCC(C(O)=O)O.CC(O)=O.S Chemical class CCC(C(O)=O)O.CC(O)=O.S HZKVDLABFATIAT-UHFFFAOYSA-N 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
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- 238000012545 processing Methods 0.000 description 3
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- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229920000875 Dissolving pulp Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 2
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- 238000005562 fading Methods 0.000 description 2
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- 238000009897 hydrogen peroxide bleaching Methods 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
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- GPOGLVDBOFRHDV-UHFFFAOYSA-N (2-nonylphenyl) dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(O)O GPOGLVDBOFRHDV-UHFFFAOYSA-N 0.000 description 1
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- 125000001421 myristyl 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])[H] 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- IYSYLWYGCWTJSG-XFXZXTDPSA-N n-tert-butyl-1-phenylmethanimine oxide Chemical compound CC(C)(C)[N+](\[O-])=C\C1=CC=CC=C1 IYSYLWYGCWTJSG-XFXZXTDPSA-N 0.000 description 1
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- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- 150000002978 peroxides Chemical class 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
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- 238000006303 photolysis reaction Methods 0.000 description 1
- 125000003386 piperidinyl group Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
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- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 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 1
- 238000003860 storage Methods 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
- C08G73/0213—Preparatory process
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
- C08G73/0213—Preparatory process
- C08G73/022—Preparatory process from polyamines and epihalohydrins
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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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
- 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
- D21H21/143—Agents preventing ageing of paper, e.g. radiation absorbing substances
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Abstract
具有硝基氧,羟胺或羟铵盐基团B侧基的经选择聚合物稳定剂是水溶性的或水可分散性的并对纸浆或纸具有高亲和力。这些稳定剂防止纸浆或纸亮度的损失和增强纸浆或纸的抗泛黄能力,尤其对于含有木质素的纸浆或纸。这些化合物在造纸过程的不同位置添加,尤其在液体处理部位,使得对纸浆或纸具有高亲和力的水溶性或水可分散性材料的需要成为不可缺少的。这些性能常常因为存在了选自UV吸收剂、阻聚剂、硝酮、荧光增白剂和金属螯合剂的一种或多种助添加剂而得到进一步增强。羟胺或它们的盐,苯并***或二苯甲酮UV吸收剂和金属螯合剂的结合物是特别有效的。
Description
本发明涉及含有硝基氧、羟胺或羟铵盐基团的新型聚合物稳定剂,这些基团用于仍然含有木质素的纸浆或纸防止亮度的损失和增强其抗泛黄的能力。这些性能常常因为存在选自UV吸收剂、阻聚剂、硝酮、萤光增白剂和金属螯合剂的一种或多种助添加剂而得到进一步增强。羟胺或它们的盐,苯并***或二苯甲酮UV吸收剂和金属螯合剂的结合物是特别有效的。
发明背景
高产率和超高产率木质纸浆经历快速光诱导的变色,尤其当它们暴露于户内荧光和日光中的近紫外线辐射(波长300-400毫微米)时。这一特性将它们的用途限于短寿命、低价值的纸类产品。高产率和超高产率木质纸浆能够漂白到高水平的白度。如果这些白度能够被稳定化防止变色,则这些漂白的高产率纸浆能够代替大量的更昂贵全漂白、低产率化学纸浆。
这一变色归因于高产率纸浆的总计约20-45%(质量)的高木质素含量。苯氧基基团是该反应机理中的关键中间体。已经提出几种光诱发的反应来说明这种基团在木质素中的形成,如从酚基团中抽取氢原子,苯甲酰甲基芳基醚基团的芳基醚键的***,或由饱和的芳基-甘油β-芳基醚结构形成的羰游离基的破坏。该苯氧基团被其它以氧为中心的基团(烷氧基,过氧,羟基和过羟基)所氧化而形成黄色生色团,如C.Heitner在“木质纤维素材料的光化学(Photochemistry ofLignocellulosic materials)”,C.Heitner,J.C.Sciano编;ACSSym.Ser.531,1-25(1993)中所教导的。
I.E.Arakin等人,Khymiya drevesiny(Chemistry of Wood),1982,No.2,114和A.D.Sergeev等人,同前,1984,No.5,20公开了亚胺氧基的使用,如TEMPO(1-氧基-2,2,6,6-四甲基哌啶)可用于使用一段氧-苏打(碱)过程的木材去木质素作用,但没有提及或建议由TEMPO提供的防止从该处理木材制得的纸张或纸浆的光诱导变色的任何活性。
EP 717,143和WO 97/36041描述了改变、减少或漂白木质素和含木质素材料的多组分体系,它包括氧化催化剂,和N-羟基介体化合物如N-羟基邻苯二甲酰亚胺或二烷基羟胺。这些参考文献致力于木材的去木质素作用。没有提及或建议由N-羟基化合物提供的防止由此类处理木材制得的纸张或纸浆的光诱导变色的任何活性。
V.I.Khodyrev等人,Vysokomol soyed,A29,No.3,616(1987)[Polymer Sci.U.S.S.R.,29,No.3,688(1987)]中揭示,氧的光诱发氧化作用会引起纤维素纺织材料如亚麻或棉花的老化,和纤维素的光稳定性能够通过光稳定剂如UV吸收剂,苯并苯酚类和1-氧基-2,2,6,6-四甲基-4-羟基哌啶来改进。该UV吸收剂没有提供保护作用,实际上是有害的。作者指出,稳定的硝酰基基团会与纤维素中的烷基相互作用,使其获得有益的稳定作用活性。该作者没有提出这一稳定作用活性能够在从其制得的木质纸浆和/或纸中成功地利用。
M-K.Syler等人,J.Assn.Paper Pulp Tech,29,135(1990)中揭示,经选择的金属盐如硫酸镁和低级链烷酸抑制了在漂白纸浆中的回色。
P.Fornier de Violet等人,Cellulose Chem.Tech.,24,225(1990)揭示了UV吸收剂和氢给体剂如硫醇类、抗坏血酸等的使用有助于防止过氧化氢漂白的木质纸浆的光诱发变色,但是,链断裂剂如位阻酚和位阻胺(具有>N-H或>N-CH2-结构部分)对于防止光诱发变色没有作用或甚至有不利影响。
R.Agnemo等人,6th International Symposium on Wood andPulping Chemistry,Appita,1991,证实了游离羟基加上木质素会导致在纸浆和纸中不希望有的光致泛黄。
S.Omori等人,J.Assn.Paper Pulp Tech,48,1388(1993)描述了抗氧化剂和UV吸收剂对光致回色的作用和总结出抗氧化剂和UV吸收剂的联合使用可以防止回色和在该活性中具有协同效应。
M.Paulsson等人,8th International Symposium Wood andPulping CHemistry,赫尔辛基,1995,说明了未漂白的纸或过氧化氢漂白的TMP纸浆的有效光稳定化可以通过乙酰化来获得。
已经建议了各种不同的途径来抑制机械纸浆的泛黄。这些包括:游离基清除剂和抗氧化剂;UV屏蔽剂;在生色团形成之后消除它们;通过烷基化或乙酰化对木质素的化学改性;阻聚剂;和组合使用的两种类型的助添加剂。Z-H.Wu等人,HolzforsChung,48,(1994),400讨论了游离基清除剂如苯基-N-叔丁基硝酮在减少机械制浆过程中生色团的形成方面的用途并得到更具光稳定性的纸浆。
C.Heitner,“Chemistry of Brightness Reversion and ItControl,CHapter 5”,在Pulp Bleaching-Principles and Practice中,C.W.Dence,D.W.Reeve编,TAPPI,Atlanta,1996,183-211页,概述了在含有木质素的纸浆,如热机械(TMP)和化学热机械(CTMP)纸浆的热和光诱发变黄方面的现状,显示了这些不希望有的效果的严重程度,一般性讨论了用于解决这一问题的当时已有技术的方法。这些包括漂白,使用亚磷酸酯,UV吸收剂,聚亚烷基二醇和自由基清除剂如抗坏血酸,硫醇类,硫醚,二烯烃和脂族醛和螯合剂如乙二胺四乙酸(EDTA)。该著作者作出结论,虽然取得了较大的进展,但是要发现含有木质素的纸浆和/或纸的亮度损失和不希望有的泛黄问题的成功的和实际的解决方法仍然需要付出努力。
同时待审的专利申请书序列号09/119,567;09/234,253;60/116,687和60/116,688描述了潜在的解决方案,其中将所选择的位阻胺硝基氧化物,位阻胺羟胺,N,N-二烷基羟胺或它们的盐与所选择的UV吸收剂和金属螯合剂联合使用,可以在机械或化学纸浆或纸(尤其是仍然含有大量木质素的机械纸浆或纸)中防止亮度的损失和增强抗泛黄的能力。
本发明提供了含有硝基氧、羟胺或羟铵盐基团的新型聚合物材料,它单独或与UV吸收剂、金属螯合剂和/或萤光增白剂相结合用于在仍然含有木质素的纸浆或纸中防止亮度的损失和增强抗泛黄的能力。
发明详述
本发明公开了具有硝基氧、羟胺或羟胺盐基团侧链的新型聚合物材料,它是水相容的,水溶性或水可分散性的并对所制得的纸浆和纸具有高的亲和力。这些稳定剂,当单独或与UV吸收剂、金属螯合剂、萤光增白剂、含硫抑制剂、含磷化合物、硝酮、苯并呋喃-2-酮和/或稳定聚合物相结合应用于仍然含有木质素的纸浆中时,获得了高效的光和热稳定性。
聚合物P选自以下聚合物或低聚物
1)分子量为500到2,000,000的聚亚乙基亚胺。
2)低聚亚乙基胺类
其中n是0到10,优选1到3。
其中n是0到8000,优选2到8000,尤其2到100;和m是1到8000,优选1到100。
其中n=10至5000和X是NH2,NHCH2N(CH3)2,OCH2CH2N(CH3)2,OCH2CH2N+(CH3)3
5)以下的无规低聚物或聚合物
其中I=0到8000,优选0到1000;m=1到8000,优选3到1000;和n=0到8000,优选0到1000。
其中n=5至1000
其中n=5至8000
其中n=1到10和m=1到500和R是氢或具有1-4个碳原子的烷基和端基优选是OH。
其中n=5到4000和m=5到4000
10)二甲胺和表氯醇的共聚物
其中n=1到100。
在这些聚合物上的用于连接侧链-B-A的活性部位是氨基(通常不是酰胺基)和OH基团,其中通常氢原子被侧链-B-A取代。叔氨基,例如在聚合物(5)中存在的那种,可以经过反应形成季铵基团,得到例如具有下式的单元的聚合物(5)
侧链的数目s优选是1到1000,更优选1到100,最优选2到100,尤其2到50。
其中在该哌啶环上的4位(虚线)连接于以上聚合物的结构上和
G是氢,氨基,羟基或氰基;
E是氧基,羟基,烷氧基,被羟基、氧代或羧基取代或被氧或羧基***的烷氧基,环烷氧基,链烯氧基,环烯基氧基,芳烷基,芳烷氧基,酰基,R(C=O)O-,RO(C=O)O-,RN(C=O)O-或氯,其中R是脂肪族或芳族结构部分。
在这些定义的范围内的任何烷基优选是C1-C18烷基,其中包括甲基,乙基,丙基如正-或异丙基,丁基如正-,异-,仲-和叔丁基,戊基,己基,庚基,辛基,壬基,癸基,十一烷基,十二烷基,十三烷基,十四烷基,十五烷基,十六烷基,十七烷基或十八烷基。烷氧基是O-烷基,优选C1-C8烷氧基。环烷基通常是C5-C12环烷基,优选环己基。链烯氧基通常是C3-C12链烯氧基,尤其烯丙氧基。芳烷基和芳烷氧基通常具有7到15个碳原子和优选是C7-C15苯基烷基或C7-C15苯基烷氧基。酰基优选是C1-C12烷基-CO,尤其乙酰基,C2-C3链烯基-CO,苯甲酰基。作为脂族或芳族结构部分的R优选是C1-C18烷基,苯基,C7-C15苯基烷基,环己基,C2-C3链烯基。
本发明的稳定剂是根据所属技术领域中已知的方法或类似于该方法或按照在本发明实施例中所述,通过通式(1)到(10)的聚合物与本技术领域中已知的合适离析物(educts)反应来获得。例如,通过1-氧基-2,2,6,6-四甲基哌啶-4-酮与含有伯胺基或仲胺基的聚合物的还原胺化来形成直接的键(桥基1)(MarCH,J AdvancedOrganic Chemistry,第四版,Wiley-Interscience:New York,1992900-902页)。通过在1-氧基-2,2,6,6-四甲基-4-缩水甘油氧基哌啶中的环氧基(Cunkle,US专利6,080,864)与选择聚合物中的羟基或胺基反应,获得了具有桥接基团3的稳定剂(March,J AdvancedOrganic chemistry,第四版,Wiley-Interscience:New York,1992391页和416页)。通过在该聚合物和1-氧基-2,2,6,6-四甲基-4-羧基哌啶或1-氧基-2,2,6,6-四甲基-4-(羧基甲氧基)哌啶(Cunkle,美国专利6,080,864)之间形成酯或酰胺,获得了分别具有桥接基团2和4的稳定剂。用4-(ω-溴烷氧基)-2,2,6,6-四甲基哌啶衍生物(Bossmann,S.H.等人,Synthesis 1996,1313)将所选择聚合物中的胺基烷基化的方法可用于产生含有桥接基团9的稳定剂。在所选择聚合物中的伯和仲胺基以Michael加成反应加成到1-氧基-4-(丙烯酰氧基)-2,2,6,6-四甲基哌啶上(Karrer,F.E.Makromol.Chem.(1980),181(3),595-634),能够形成具有桥接基团11的稳定剂。
可使用多官能化合物如琥珀酸和马来酸,1,6-二异氰酸根己烷和氰尿酰氯与羟基或氨基反应将化合物如1-氧基-2,2,6,6-四甲基-4-羟基哌啶和1-氧基-2,2,6,6-四甲基-4-胺基哌啶与该选择聚合物桥接,产生具有桥接基团5-8,10,12,14和15的稳定剂。
在4-位上携带氧代、羟基、氨基或羧基的哌啶离析物(educts)是已知的化合物。例如,1-氧基-2,2,6,6-四甲基哌啶-4-酮,1-氧基-2,2,6,6-四甲基-4-羟基哌啶,1-氧基-2,2,6,6-四甲基-4-胺基哌啶和1-氧基-2,2,6,6-四甲基-4-羧基哌啶是已知化合物和能够通过商业途径获得(Aldrich Chemical Company)。
优选地,对于通式I和IA的基团A,G是氢或羟基,尤其是氢,和对于通式I,E是氧基或羟基。
当聚合物P是1)时,优选的桥接基团B是:1,2,3,4,5,7,9或11。
当聚合物P是1)时,更优选的桥接基团B是:1,3,9或11。
当聚合物P是1)时,最优选的桥接基团B是:1或3。
当聚合物P是2)时,优选的桥接基团B是:1,2,3,4,5,7,9或11。
当聚合物P是2)时,更优选的桥接基团B是:1,3,9或11。
当聚合物P是2)时,更优选的桥接基团B是:1或3。
当聚合物P是3)时,优选的桥接基团B是:2,3,4,5,7,9或11。
当聚合物P是3)时,更优选的桥接基团B是:3,9或11。
当聚合物P是3)时,最优选的桥接基团B是3。
当聚合物P是4)时,优选的桥接基团B是:3或9。
当聚合物P是4)时,最优选的桥接基团B是3。
当聚合物P是5)时,优选的桥接基团B是:3或9。
当聚合物P是6)时,优选的桥接基团B是:2,3,4,或9。
当聚合物P是6)时,最优选的桥接基团B是2。
当聚合物P是7)时,优选的桥接基团B是:2,3,4,或9。
当聚合物P是7)时,最优选的桥接基团B是2。
当聚合物P是8)时,优选的桥接基团B是:3或9。
当聚合物P是8)时,最优选的桥接基团B是3。
当聚合物P是9)时,优选的桥接基团B是:1,2,3,4,5,9或11。
当聚合物P是9)时,最优选的桥接基团B是3。
当聚合物P是10)时,优选的桥接基团B是:3或9。
当聚合物P是10)时,最优选的桥接基团B是3。
一般而言,优选的桥接基团B是直接键(1),羰基(2),或具有通式3,4,5,7,9或11;最优选的桥接基团是1,2,3或9。
其中在通式IX和IXA中的Hal表示卤素,尤其表示Cl或Br,和在通式III-IXA中的E是与以上通式I中所述的相同。
更优选地,本发明的稳定剂是分子量500到2,000,000的聚亚乙基亚胺1),或低聚亚乙基胺2);或聚合物8)与具有通式III到IXA的一种或多种化合物的反应产物;
或无规共聚物3)与具有通式III到IXA的化合物中的一种或多种的反应产物;
或聚丙烯酰胺4)与具有通式IV、IVA、IX、IXA的化合物中的一种或多种的反应产物;
或无规低聚物或聚合物5)与具有通式IV、IVA、IX和IXA的化合物中的一种或多种的反应产物;
或二醇6)与具有通式IV、IVA、VII、VIIA、VIII、VIIIA、IX和IXA的化合物中的一种或多种的反应产物;
或通式的聚合物7)与通式IV,IVA,VII,VIIA,VIII,VIIIA,IX和IXA的化合物中一种或多种的反应产物;
或聚合物10)与具有通式IV和IVA的化合物中一种或多种的反应产物。
最优选的是本发明的聚合物稳定剂,它是聚亚乙基亚胺1),或低聚亚乙基胺2),或的无规共聚物3),或聚合物8),或聚合物10),与其中Hal是Cl或Br和E是氧基或OH的通式III,IV,或IX的一种或多种化合物的反应产物。
本发明还涉及防止纸浆或纸、尤其是仍然含有木质素的化学机械或热机械纸浆或纸的亮度损失及增强其抗泛黄能力的方法,该方法包括:
用有效稳定量的以上所述的任何一种化合物处理该纸浆或纸。
所述化合物的有效稳定量是0.001-5wt%,基于纸浆或纸。优选地,有效稳定量是0.005-2wt%;优选0.01-1wt%。
当助添加剂稳定剂也存在时,助添加剂的有效稳定量也是0.001-5wt%,基于纸浆或纸;优选0.005-2wt%;最优选0.01-2wt%;尤其0.01-1wt%,基于纸浆或纸。
本发明的化合物可以另外包括有效稳定量的至少一种稳定剂,它选自UV吸收剂,阻聚剂,含硫抑制剂,含磷化合物,硝酮,苯并呋喃-2-酮,萤光增白剂,位阻胺羟胺和它们的盐,位阻胺硝基氧和它们的盐,位阻胺和它们的盐,苯并呋喃-2-酮和金属螯合剂。
还包括UV吸收剂的组合物是尤其优选的。该UV吸收剂选自苯并***,s-三嗪,二苯甲酮,α-氰基丙烯酸酯,草酰二苯胺,氧氮杂萘酮,苯甲酸酯和α-烷基肉桂酸酯。
优选,该UV吸收剂是苯并***,s-三嗪或二苯甲酮,最尤其是苯并***UV吸收剂或二苯甲酮UV吸收剂。
典型的和有用的UV吸收剂是,例如,
5-氯-2-(2-羟基-3,5-二-叔丁基苯基)-2H-苯并***;
2-(2-羟基-3,5-二-叔丁基苯基)-2H-苯并***;
2-(2-羟基-3,5-二-叔戊基苯基)-2H-苯并***;
2-(2-羟基-3,5-二-α-枯基苯基)-2H-苯并***;
2-(2-羟基-3-α-枯基-5-叔辛基苯基)-2H-苯并***;
2-(2-羟基-5-叔辛基苯基)-2H-苯并***;
2-(2-羟基-3-叔丁基-5-甲基苯基)-2H-苯并***-5-磺酸,钠盐;
3-叔丁基-4-羟基-5-(2H-苯并***-2-基)-氢化肉桂酸;
3-叔丁基-4-羟基-5-(2H-苯并***-2-基)-氢化肉桂酸12-羟基-3,6,9-三氧杂十二烷基酯;
3-叔丁基-4-羟基-5-(2H-苯并***-2-基)-氢化肉桂酸辛基酯;
4,6-双(2,4-二甲基苯基)-2-(4-(3-十二烷氧基*-2-羟基丙氧基)-2-羟苯基)-s-三嗪(*是C12-14氧基异构体的混合物);
4,6-双(2,4-二甲基苯基)-2-(4-辛氧基-2-羟苯基)-s-三嗪;
2,4-二羟基二苯甲酮;
2,2’,4,4’-四羟基-5,5’-二磺基二苯甲酮,二钠盐;
2-羟基-4-辛氧基二苯甲酮;
2-羟基-4-十二烷氧基二苯甲酮;
2,4二羟基二苯甲酮-5-磺酸和它的盐;
2-羟基-4-甲氧基二苯甲酮-5-磺酸和它的盐;
2,2’-二羟基-4,4’二甲氧基二苯甲酮-5,5’-磺酸二钠;和
3-(2H-苯并***-2-基)-4-羟基-5-仲丁基苯磺酸,钠盐(CIBAFASTW)。
其它优选的组合物是另外含有阻聚剂;优选聚(乙二醇),聚(丙二醇),聚(丁二醇)或聚(乙烯基吡咯烷酮)的那些。
仍然还有其它优选的组合物,其中另外的稳定剂是含硫抑制剂;优选聚乙二醇二硫羟乙酸酯,聚丙二醇二硫羟乙酸酯,聚亚丁基二醇二硫羟乙酸酯,1-硫甘油,2-巯基乙基醚,2,2’-硫代二乙醇,2,2’-二硫代二乙醇,2,2’-氧基二乙烷硫醇,乙二醇双硫代乙二醇酸酯,3-巯基-1,2-丙二醇,2-(2-甲氧基乙氧基)-乙硫醇,乙二醇二巯基乙酸酯,3,3’-二硫代丙酸,聚乙二醇二硫醇,聚丙二醇二硫醇,聚亚丁基二醇二硫醇或乙二醇双(巯基乙酸酯)。
其它优选的组合物是其中该另外稳定剂是以下这些含磷化合物的那些组合物:优选地,亚磷酸三(2,4-二-叔丁基苯基)酯,2,2’,2″-次氮基[三乙基三(3,3’,5,5’-四叔丁基-1,1’-联苯基-2,2’-二基)亚磷酸酯],亚磷酸双(2,4-二-叔丁基-6-甲基苯基)乙基酯,羟甲基次膦酸钠,4,4’-亚联苯基二亚膦酸四(2,4-二-丁基苯基)酯,亚磷酸三(壬基苯基)酯,双(2,4-二-叔丁基苯基)季戊四醇基二亚磷酸酯,氟亚磷酸2,2’-亚乙基双(2,4-二-叔丁基苯基)酯或2,4,6-三叔丁基苯基亚磷酸2-丁基-2-乙基丙烷-1,3-二基酯。
还有一些其它优选的组合物是其中该另外稳定剂是苯并呋喃-2-酮;优选5,7-二-叔丁基-3-(3,4-二甲基苯基)-2H-苯并呋喃-2-酮的那些组合物。
又一些其它优选的组合物是其中该另外稳定剂是以下金属鳌合剂的那些组合物:优选柠檬酸,酮酸,葡糖酸盐,七葡糖酸盐,磷酸盐,膦酸盐和氨基羧酸螯合剂,如乙二胺四乙酸(EDTA),二亚乙基三胺五乙酸(DTPA),羟乙基乙二胺三乙酸(HEDTA),次氮基三乙酸(NTA)和二亚乙基三胺五亚甲基膦酸(DTPMPA)。
一些优选的组合物含有另外稳定剂的混合物,如UV吸收剂和阻聚剂的混合物;或UV吸收剂和含硫化合物的混合物;或UV吸收剂和含磷化合物的混合物;或UV吸收剂和金属螯合剂的混合物;或阻聚剂和含硫化合物的混合物;或阻聚剂和含磷化合物的混合物;或含硫化合物和含磷化合物的混合物;或UV吸收剂,阻聚剂和含硫化合物的混合物;或UV吸收剂,阻聚剂和含磷化合物的混合物;或UV吸收剂,阻聚剂,含硫化合物和含磷化合物的混合物;或UV吸收剂,阻聚剂和金属螯合剂的混合物。
一些优选的组合物是这样一些组合物,其中该另外稳定剂是位阻胺羟胺与至少一种荧光增白剂如2,2’-[(1,1’-二苯基)-4,4’-二基-1,2-亚乙基二基]双-苯磺酸,二钠盐{或双[4,4’-(2-芪磺酸)],二钠盐}(它是TINOPALSK,Ciba)的混合物。
优选该组合物是这样一些组合物,其中通式I,II,III,IA,IIA或IIIA的化合物具有低分子量或含有亲水性结构部分或既具有低分子量,又含有亲水性结构部分。
本发明的抑制添加剂体系能够在制造或加工操作过程中的多个地点被加入到纸浆或纸中。这些包括
a.在潜伏池中的纸淤浆上;
b.在贮存、掺混或转移池中的漂白阶段中或之后的纸淤浆上;
c.在随后有滚筒干燥或急骤干燥操作的漂白、洗涤和脱水过程中或之后的纸浆上;
d.在清洗机之前或之后;
e.在将纸浆吹入造纸机压头箱的压气机之前或之后;
f.加入到造纸机白水中;
g.加入到料仓中或白水回收装置中;
h.在使用压胶器,涂敷器或喷管的压型段中;
i.在使用压胶器、涂敷器或喷管的干燥段中;
j.在使用压片箱的压延机上;
k.在机外涂布机或压胶器中的纸张上;和/或
i.在卷缩控制装置中。
显然,添加稳定剂添加剂的准确部位将取决于所使用的具体设备,所使用的具体工艺条件等。在一些情况下,可以在一个或多个部位添加添加剂以获得最佳的效果。
如果稳定剂或其它助添加剂它们本身不是“水溶性的”,则它们可以在应用之前利用标准方法加以分散或乳化。另外,稳定剂和/或助添加剂可以配制到纸张施胶或纸张涂敷配方中。
本发明的稳定剂也可用作有机材料,尤其有机聚合物的光稳定剂。因此,它们可以有利地用于本体聚合物如聚烯烃,膜,纤维或用于涂料中。基底材、助添加剂和满足此目的的具体应用方式包括现有技术领域中已知的那些,例如按照在US-5948836的3栏37行至9栏61行(基底材);1栏46行至3栏36行,和17栏65行至25栏30行(助添加剂);和17栏39-61行,26栏33-39行,和同样26栏52行到27栏18行,和28栏11-17行(应用方法)中所述。
下面的实施例仅仅是用于举例说明的目的,不应被认为以无论任何方式限制本发明。
手抄纸处理
全部的添加剂通过将合适wt%的添加剂结合物作为水溶液(当添加剂是水溶性的时)形式或作为在1∶1的乙醇/二噁烷中的溶液形式用注射器注射到漂白的热机械纸浆(BTMP)亮度方形料样(4厘米×4厘米)之上来应用。该夹定片材被风干1天。
在被控制的强度的条件下利用曝光来处理之前和之后,记录手抄纸的亮度。
通过在装有八只在5700埃下有最高光谱输出功率的荧光灯(总输出功率大约比正常办公室荧光灯高43倍)的风扇冷却的光箱中让处理过的片材进行加速光诱导泛黄,来进行加速试验。该灯与被照射的手抄纸相距大约10英寸。
将处理过的手抄纸以6英尺的标称距离放置在呈现正常冷白色荧光的办公室灯光下的桌面上,来进行环境试验。
在两种情况下,ISO亮度是作为光解时间的函数来跟踪并按常规方式换算为退色值(PC值)。
退色(PC)值被定义如下:
PC=[(k/s)之后-(k/s)之前]×100
k/s=(1-Rinf)2/2Rinf
其中k和S分别是吸收和散射系数,并且Rinf是ISO亮度的值。
在Rinf和发色团浓度之间的关系是非线性的,而PC值相对于样品中发色团的浓度粗略地成线性关系。
低PC值是所希望的,因为它们表示较低的泛黄性。
在使用环境试验条件下,将未处理的BTMP手抄纸与60天后的牛皮纸(Kraft)手抄纸进行对比,BTMP手抄纸的PC值是大约10,而牛皮纸的PC值是大约0.39。在暴露于环境光之后,该牛皮纸手抄纸明显比未处理的BTMP手抄纸有更浅的黄色。
加速泛黄试验的入射光通量(实施例1-10)比正常办公室荧光灯高43倍,这可通过A.W.Speery SLM-110数字光功率计来测量。跟踪记录手抄纸的亮度并与按同样方式曝光的未处理片材对比。该处理片材表现出显著的抗泛黄能力,这可以从以下所述看出。
下面的实施例仅仅是用于举例说明的目的,不应认为以无论任何方式限制本发明。
实施例1
将0.20g(0.88mmol)1-氧基-2,2,6,6-四甲基-4-缩水甘油基氧基哌啶加入到6.06g聚亚乙基亚胺(LupasolTMPS,BASF;33%wt/wt在水中,Mw 750,000和Mn 60,000)和13.94g水的溶液中。该溶液在环境温度下搅拌2小时。由薄层色层分析法进行分析后表明全部的1-氧基-2,2,6,6-四甲基-4-缩水甘油基氧基哌啶被接枝到聚亚乙基亚胺上。
实施例2
1-氧基-2,2,6,6-四甲基-4-氧代哌啶与聚亚乙基亚胺LupasolPEI(Mw=25,000;Mn=10,000;无水)在氢气氛下使用Pt/C加氢催化剂进行反应。所形成的聚亚乙基亚胺聚合物具有侧挂的羟胺基团。
实施例3
1-氧基-2,2,6,6-四甲基-4-(3-溴丙氧基)-哌啶与聚亚乙基亚胺Lupasol PEI(Mw=25,000;Mn=10,000)反应。所形成的聚亚乙基亚胺聚合物具有侧挂的硝酰基基团。
实施例4
1-氧基-2,2,6,6-四甲基-4-(2-羟基-4,7,10-三氮杂癸氧基)哌啶
将2.21g(9.7mmol)的1-氧基-2,2,6,6-四甲基-4-缩水甘油基氧基哌啶滴加到1.0g(9.7mmol)二亚乙基三胺溶于50ml水中的剧烈搅拌溶液中。该混合物被搅拌18小时。在减压下除去水,得到红色油形式的3.2g产物。
实施例5
1,7-双-(1-羟基-2,2,6,6-四甲基哌啶-4-基)1,4,7-三氮杂庚烷
含有20.0g(0.117mol)1-氧基-2,2,6,6-四甲基哌啶-4-酮,6.0g(0.058mol)二亚乙基三胺,0.5g负载于碳上的8%Pt/2%Pd催化剂和120ml甲醇的Parr振荡瓶用氢气加压并振荡2小时。通过过滤分出该催化剂,该溶液被浓缩到40ml。通过添加200mL乙基醚,产物以白色固体形式沉淀下来:mp 118-124℃。
实施例6
25g的二烯丙基-二甲基氯化铵(DADMAC)和二烯丙基胺(DAA)的共聚物(87wt% DADMAC和13wt% DAA;Mw 250,000)的20%水溶液用25g水稀释。该pH值用50% NaOH水溶液调节到9.6。将0.77g(3.4mmol)1-氧基-2,2,6,6-四甲基-4-缩水甘油基氧基哌啶加入到溶液中,在室温下剧烈搅拌18小时进行反应。该溶液用2×50ml乙酸乙酯萃取,除去0.32g的未接枝1-氧基-2,2,6,6-四甲基-4-缩水甘油基氧基哌啶。所形成的DADMAC/DAA共聚物具有侧挂的硝酰基基团
实施例7
1-氧基-2,2,6,6-四甲基-4-(3-溴丙氧基)-哌啶与二烯丙基-二甲基氯化铵(DADMAC)和二烯丙基胺(DAA)(87wt% DADMAC和13wt% DAA;Mw 250,000)的共聚物的20%水溶液反应。所形成的DADMAC/DAA共聚物具有侧挂的硝酰基基团。
实施例8
1-氧基-2,2,6,6-四甲基-4-缩水甘油基氧基哌啶与2-丙烯酸2-(二甲基氨基)乙基酯的聚合物或含有2-丙烯酸2-(二甲基胺基)乙基酯的共聚物反应。所形成的聚合物具有侧挂的硝酰基基团。
实施例9
1-氧基-2,2,6,6-四甲基-4-缩水甘油基氧基哌啶与4-(二甲基氨基)-苯乙烯的聚合物或含有4-(二甲基氨基)-苯乙烯的共聚物反应。所形成的聚合物具有侧挂的硝酰基基团。
实施例10
1-羟基-2,2,6,6-四甲基-4-(3-溴丙氧基)-哌啶与4-(二甲基氨基)-苯乙烯的聚合物或含有4-(二甲基氨基)-苯乙烯的共聚物反应。所形成的聚合物具有侧挂的羟胺基团。
实施例11
通过在美国专利2,926,154中公开的操作程序,制备二亚乙基三胺(22.5g,0.218mol)和己二酸(29.0g,0.198mol)的共聚物。所形成的聚合物具有3500的Mn。制备10g的这一聚合物的50wt%水溶液。将1-氧基-2,2,6,6-四甲基-4-缩水甘油基氧基哌啶的四个0.54g(2.3mmol)等分试样以2小时的间隔加入到搅拌的聚合物溶液中。在最后一次添加之后,该混合物被搅拌另外18小时。薄层色层分析法表明全部的1-氧基-2,2,6,6-四甲基-4-缩水甘油基氧基哌啶已接枝到该聚合物上。
实施例12
在装有加料漏斗、冷却至10℃的冷凝器、机械搅拌器和充满水的鼓泡器的250mL三颈圆底烧瓶中加入50ml的二甲胺(DMA:17.96g;0.398mol)的40%水溶液(w/w)。该烧瓶被加热到75℃,经1小时的时间滴加25.5mL(30.15g,0.326mol)的表氯醇。在表氯醇添加之后,该反应被搅拌2小时。将来自鼓泡器的水加入到反应混合物中和将更多的水加入到鼓泡器中。该反应被搅拌另外2小时,然后冷却到室温。所形成的溶液具有56%的固体含量和该共聚物仅仅是二甲胺封端的。向10.0g的该聚合物溶液中添加0.44g(1.9mmol)的1-氧基-2,2,6,6-四甲基-4-缩水甘油基氧基哌啶,反应搅拌18小时。该反应溶液用25ml的乙酸乙酯洗涤两次。
实施例13
用高强度的灯的加速泛黄试验
BTMP片材用1.0wt%的实施例4的化合物处理。BTMP片材用实施例6,11和12的化合物处理,其用量可以达到与用第一种片材所达到的相同的硝基氧浓度。与未处理的对照片材相比,用这些新型稳定剂处理的片材显示出了对泛黄的显著抑制作用。在指定的照射时间之后测定的退色(PC)值示于下面的表中。低PC值是所希望的,因为它们表示较低的泛黄性。
PC值
时间(天) | 空白 | 实施例4 | 实施例6 | 实施例11 | 实施例12 |
0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
1 | 3.0 | 1.5 | 1.8 | -0.1 | 2.1 |
2 | 5.3 | 2.9 | 3.4 | 1.2 | 3.7 |
3 | 7.9 | 4.5 | 5.8 | 3.2 | 5.6 |
6 | 14.1 | 7.6 | 11.0 | 7.1 | 10.2 |
8 | 16.7 | 9.0 | 13.0 | 8.5 | 12.2 |
10 | 19.2 | 10.6 | 15.2 | 10.2 | 14.1 |
Claims (12)
1.一种包含具有侧基A的聚合物P的稳定剂,该侧基利用桥接基团B连接于聚合物P上
其中s是1到50,000,和
聚合物P选自聚合物或低聚物1)到10)
1)以下通式的聚亚乙基亚胺
其中m+n是10到50,000;
2)具有下式的低聚亚乙基胺
其中n是0到10;
4)具有下式的聚丙烯酰胺:
其中n是10-5000和X是NH2,NHCH2N(CH3)2,OCH2CH2N(CH3)2或OCH2CH2N+(CH3)3;
5)从以下聚合形成的无规共聚低聚物或共聚物
其中I是0到8000,m是1到8000和n是0到8000;
其中n是5到8000;
7)
其中n是5到8000;
其中n是1到10和m是1到500和R是氢或具有1-4个碳原子的烷基;
9)以下的无规共聚物
其中n是5到4000和m是5到4000;
其中n是1到100;
其中
G是氢,氨基,羟基或氰基;
E是氧基,羟基,烷氧基,被羟基、氧代或羧基取代或被氧或羧基***的烷氧基,环烷氧基,链烯氧基,环烯基氧基,芳烷基,芳烷氧基,酰基,R(C=O)O-,RO(C=O)O-,RN(C=O)O-或氯,其中R是脂肪族或芳族结构部分。
2.根据权利要求1的稳定剂,其中在通式I的基团A中的E选自氧基,羟基,C1-C18烷氧基;被羟基、氧代或羧基取代的或被氧或羧基***的C3-C18烷氧基;C5-C12环烷氧基;C3-C12链烯基氧基;环己烯基氧基;具有7-15个碳原子的芳烷基或芳烷氧基;C1-C12酰基;R(C=O)O-,RO(C=O)O-,RN(C=O)O-,其中R是C1-C18烷基,苯基,C7-C15苯基烷基,环己基,C2-C3链烯基。
3.根据权利要求1的稳定剂,其中桥接基团B是直接键,羰基,或具有通式3,4,5,7,9或11。
4.根据权利要求1的稳定剂,其中在通式1中,E是氧基或羟基和G是氢。
6.根据权利要求5的聚合物稳定剂,它是聚亚乙基亚胺1),或低聚亚乙基胺2),或聚合物8)与具有通式III到IXA的一种或多种化合物的反应产物;
或无规共聚物3)与具有通式III到XA的化合物中的一种或多种的反应产物;
或聚丙烯酰胺4)与具有通式IV、IVA、IX、IXA的化合物中的一种或多种的反应产物;
或无规低聚物或聚合物5)与具有通式IV、IVA、IX和IXA的化合物中的一种或多种的反应产物;
或二醇6)与具有通式IV、IVA、VII、VIIA、VIII、VIIIA、IX和IXA的化合物中的一种或多种的反应产物;
或聚合物10)与具有通式IV和IVA的化合物中一种或多种的反应产物。
7.根据权利要求6的聚合物稳定剂,它是聚亚乙基亚胺1),或低聚亚乙基胺2),或无规共聚物3),或聚合物8),或聚合物10),与其中Hal是Cl或Br和E是氧基或OH的通式III,IV,或IX的一种或多种化合物的反应产物。
8.一种防止纸浆或纸亮度的损失和增强纸浆或纸的抗泛黄能力的方法,它包括用有效稳定量的根据权利要求1的聚合物稳定剂来处理该纸浆或纸。
9.权利要求8的方法,其中该纸浆或纸是仍然含有木质素的化学机械或热机械纸浆或纸。
10.根据权利要求8的方法,其中聚合物稳定剂的有效稳定量是0.001-5wt%,基于纸浆或纸。
11.根据权利要求11的方法,其中稳定剂组合物另外包含有效稳定量的至少一种助添加剂,后者选自该UV吸收剂,阻聚剂,含硫抑制剂,含磷化合物,硝酮,苯并呋喃-2-酮,萤光增白剂,位阻胺羟胺和它们的盐,位阻胺硝基氧和它们的盐,位阻胺和它们的盐,苯并呋喃-2-酮和金属螯合剂。
12.根据权利要求11的方法,其中助添加剂的有效量是0.001-5wt%,基于纸浆或纸。
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Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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US6989449B1 (en) * | 1999-09-15 | 2006-01-24 | Ciba Specialty Chemicals Corporation | Chlorohydrin and cationic compounds having high affinity for pulp or paper |
US20030121630A1 (en) * | 2000-04-19 | 2003-07-03 | Zhirun Yuan | Inhibition of yellowing in papers |
CA2502911C (en) * | 2002-10-23 | 2008-12-16 | Pulp And Paper Research Institute Of Canada | Light-stable and process-stable lignocellulosic materials and their production |
WO2005005388A1 (en) * | 2003-07-14 | 2005-01-20 | Ciba Specialty Chemicals Holding Inc. | Hydrogen peroxide catalyzed process for the preparation of sterically hindered n-hydrocarbyloxyamines |
EP2215156B1 (de) * | 2007-11-28 | 2013-01-09 | Basf Se | Flüssige stabilisatormischung |
CA2728278C (en) | 2008-06-20 | 2016-06-28 | Zheng Tan | Composition and recording sheet with improved optical properties |
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US20180346834A1 (en) * | 2015-05-25 | 2018-12-06 | General Electric Company | Coal dust treatment methods and compositions |
CN112175198A (zh) * | 2020-10-14 | 2021-01-05 | 中国林业科学研究院林产化学工业研究所 | 一种新型反应型木质素基阻燃剂及其制备方法和应用 |
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Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4295931A (en) * | 1976-03-08 | 1981-10-20 | Hercules Incorporated | Sizing method and sizing composition for use therein |
US5181988A (en) * | 1988-07-08 | 1993-01-26 | Asahi Denka Kogyo Kabushiki Kaisha | Method for preventing the discoloration of paper and paper treated to prevent discoloring |
DE69008402T2 (de) * | 1989-03-21 | 1994-08-25 | Ciba Geigy Ag | Poly(1-hydrocarbyloxy-2,2,6,6-tetraalkylpiperidin)- Lichtstabilisatoren. |
CA2086487C (en) * | 1991-12-31 | 1999-02-16 | Ian A. Pudney | Cationic polyamines useful as drainage aids and stabilizers for rosin-based sizing agents |
EP0717143A1 (de) | 1994-12-16 | 1996-06-19 | Lignozym GmbH | Mehrkomponentensystem zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder ähnlichen Stoffen sowie Verfahren zu seiner Anwendung |
JPH09216917A (ja) * | 1996-02-09 | 1997-08-19 | Asahi Denka Kogyo Kk | 共重合体および記録紙塗工液添加剤 |
JPH09302026A (ja) * | 1996-03-12 | 1997-11-25 | Nitto Boseki Co Ltd | ポリアリルアミン系誘導体及びその製造方法 |
DE19612193A1 (de) | 1996-03-27 | 1997-10-02 | Consortium Elektrochem Ind | Mehrkomponentensystem zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder ähnlichen Stoffen sowie Verfahren zu seiner Anwendung |
EP0873991A1 (de) * | 1997-04-23 | 1998-10-28 | Ciba SC Holding AG | Polyalkylenglykolgruppen enthaltende gehinderte Amine als Stabilisatoren |
TW491872B (en) * | 1997-05-27 | 2002-06-21 | Ciba Sc Holding Ag | Block oligomers containing l-hydrocarbyloxy-2,2,6,6-tetramethyl-4- piperidyl groups as stabilizers for lower polyolefin |
US5932735A (en) * | 1997-06-13 | 1999-08-03 | Ciba Specialty Chemicals Corporation | Derivatives of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidine as polymerization inhibitors for (meth)acrylate monomers |
US5928558A (en) * | 1997-06-13 | 1999-07-27 | Ciba Specialty Chemicals Corporation | Derivatives of 1-oxyl-4-amino-2,2,6,6-tetramethylpiperidine as polymerization inhibitors for (meth)acrylate monomers |
CN100379724C (zh) * | 1997-07-23 | 2008-04-09 | 西巴特殊化学品控股有限公司 | 利用硝基氧和其它共添加剂抑制纸浆及纸张的返黄 |
CA2341372A1 (en) * | 1998-09-03 | 2000-03-16 | Ciba Specialty Chemicals Holding Inc. | Grafting of ethylenically unsaturated monomers onto polymers |
-
2000
- 2000-09-07 DE DE60006268T patent/DE60006268T2/de not_active Expired - Lifetime
- 2000-09-07 AT AT00962454T patent/ATE253094T1/de not_active IP Right Cessation
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- 2000-09-07 JP JP2001523672A patent/JP4820513B2/ja not_active Expired - Fee Related
- 2000-09-07 CA CA002383005A patent/CA2383005C/en not_active Expired - Fee Related
- 2000-09-07 KR KR1020027003379A patent/KR20020030822A/ko not_active Application Discontinuation
- 2000-09-07 CN CNB008129878A patent/CN1168759C/zh not_active Expired - Fee Related
- 2000-09-08 MY MYPI20004159A patent/MY122681A/en unknown
- 2000-09-11 US US09/658,923 patent/US6416627B1/en not_active Expired - Lifetime
- 2000-09-13 TW TW089118649A patent/TWI266777B/zh not_active IP Right Cessation
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101360764B (zh) * | 2005-11-14 | 2011-12-14 | 西巴控股公司 | 官能化的阳离子聚合物的制备以及它们的制品和在个人护理中的应用 |
Also Published As
Publication number | Publication date |
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EP1216269A1 (en) | 2002-06-26 |
AR032593A1 (es) | 2003-11-19 |
JP4820513B2 (ja) | 2011-11-24 |
CA2383005A1 (en) | 2001-03-22 |
MXPA02001951A (es) | 2002-08-20 |
US6416627B1 (en) | 2002-07-09 |
ATE253094T1 (de) | 2003-11-15 |
AU770858B2 (en) | 2004-03-04 |
WO2001019897A1 (en) | 2001-03-22 |
KR20020030822A (ko) | 2002-04-25 |
BR0014046B1 (pt) | 2010-11-03 |
ZA200202026B (en) | 2002-10-03 |
DE60006268D1 (de) | 2003-12-04 |
CA2383005C (en) | 2008-12-30 |
JP2003509555A (ja) | 2003-03-11 |
CN1168759C (zh) | 2004-09-29 |
TWI266777B (en) | 2006-11-21 |
MY122681A (en) | 2006-04-29 |
BR0014046A (pt) | 2002-05-21 |
AU7417900A (en) | 2001-04-17 |
DE60006268T2 (de) | 2004-08-05 |
EP1216269B1 (en) | 2003-10-29 |
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