CN108137896A - 作为表面施胶剂的核/壳聚合物颗粒 - Google Patents
作为表面施胶剂的核/壳聚合物颗粒 Download PDFInfo
- Publication number
- CN108137896A CN108137896A CN201680056767.3A CN201680056767A CN108137896A CN 108137896 A CN108137896 A CN 108137896A CN 201680056767 A CN201680056767 A CN 201680056767A CN 108137896 A CN108137896 A CN 108137896A
- Authority
- CN
- China
- Prior art keywords
- core shell
- polymer beads
- monomer
- shell polymer
- acrylic acid
- 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.)
- Granted
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- 229920000642 polymer Polymers 0.000 title claims abstract description 100
- 239000011258 core-shell material Substances 0.000 title claims abstract description 73
- 239000011324 bead Substances 0.000 title claims abstract description 67
- 235000004258 Cordia alliodora Nutrition 0.000 title description 8
- 244000085692 Cordia alliodora Species 0.000 title description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000000178 monomer Substances 0.000 claims abstract description 70
- 238000004513 sizing Methods 0.000 claims abstract description 55
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 229920002678 cellulose Polymers 0.000 claims abstract description 19
- 239000001913 cellulose Substances 0.000 claims abstract description 19
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 50
- 239000008107 starch Substances 0.000 claims description 31
- 229920002472 Starch Polymers 0.000 claims description 30
- 235000019698 starch Nutrition 0.000 claims description 30
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 22
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000004026 adhesive bonding Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229920005615 natural polymer Polymers 0.000 claims description 6
- 229920001059 synthetic polymer Polymers 0.000 claims description 6
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 229920006320 anionic starch Polymers 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 24
- 239000002994 raw material Substances 0.000 description 24
- 239000000123 paper Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 12
- 229960002163 hydrogen peroxide Drugs 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
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- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920001592 potato starch Polymers 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 5
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000005213 imbibition Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000010525 oxidative degradation reaction Methods 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- -1 methyl Tert-butyl Chemical group 0.000 description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
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- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000011111 cardboard Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 241000274582 Pycnanthus angolensis Species 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 102400000830 Saposin-B Human genes 0.000 description 1
- 101800001697 Saposin-B Proteins 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229920001585 atactic polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011436 cob Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000009994 optical bleaching Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
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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
- D21H23/22—Addition to the formed paper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/08—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L1/02—Cellulose; Modified cellulose
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/18—Homopolymers or copolymers of nitriles
- C08L33/20—Homopolymers or copolymers of acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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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
- D21H17/20—Macromolecular organic compounds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/22—Polyalkenes, e.g. polystyrene
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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
- 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
- D21H21/16—Sizing or water-repelling agents
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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
- 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
- D21H21/50—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 form
- D21H21/52—Additives of definite length or shape
- D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads
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Abstract
本发明提供一种用于纤维素产品的表面施胶的核/壳聚合物颗粒,其中由基于所述核/壳聚合物颗粒中的单体的总重量含至少40%重量的选自(甲基)丙烯酸支链C3‑10烷基酯、苯乙烯、(甲基)丙烯酸直链C1‑10烷基酯和丙烯腈的单体的单体,聚合得到所述核/壳聚合物颗粒中的核聚合物和壳聚合物;条件是,所述核/壳聚合物颗粒中的聚合物包括至少40%重量的(甲基)丙烯酸支链C3‑6烷基酯和总计至少50%重量的(甲基)丙烯酸支链C3‑10烷基酯和苯乙烯、(甲基)丙烯酸直链C1‑10烷基酯和/或丙烯腈,基于所述核/壳聚合物颗粒中的单体的总重量。
Description
技术领域
本发明涉及纤维素产品(例如纸张)的表面施胶,和尤其涉及适合于表面施胶的核/壳聚合物颗粒。
背景技术
施胶是控制纸张和其他纤维素产品被诸如水、水性组合物和油墨之类的流体吸收和/或渗透而典型地使用的技术。纸张和其他纤维素产品可以施胶到各种程度和因各种目的。
可在纤维素产品完全形成之前通过直接添加内施胶剂到水性纸浆中以涂布纸浆纤维,或者在形成完工的纤维素产品之后通过施加施胶剂到产品的至少一个表面上从而填充产品的毛细管,来进行施胶。表面施胶通常不如内施胶昂贵,因为几乎全部施胶剂保留在处理过的产品的表面上。
商业上使用许多不同材料作为表面施胶剂,其中包括基于苯乙烯-马来酸酐(SMA)共聚物的合成产品,和天然存在的材料,例如蜡,和作为内施胶剂,例如链烯基琥珀酸酐、烷基烯酮二聚体或松香。尽管存在各种已知的表面施胶体系,但持续需要与已知的施胶体系相比提供改进的施胶性能(例如,通过Cobb方法测定的较低的吸水性)的施胶体系。
发明概述
因此,本发明的目的是提供用于表面施胶的聚合物,以便缓和已知的施胶体系的缺点。通过在独立权利要求中描述的核/壳聚合物颗粒,包含它的表面施胶剂及其使用方法,实现本发明的目的。在从属权利要求中公开了本发明的优选实施方案。
本发明基于下述认识:具有含特定配方的核/壳结构的聚合物颗粒的施胶效率好于在无规聚合物结构中含相同单体的聚合物颗粒。可采用不含乳化剂的聚合,制备本发明的核/壳聚合物颗粒的聚合物组合物。
附图简述
在下述中,参考附图,借助优选的实施方案更加详细地描述本发明,其中:
图1示出了用第一批次的不同施胶组合物施胶的纸张表面的吸水性;和
图2示出了用第二批次的不同施胶组合物施胶的纸张表面的吸水性。
发明详述
本发明提供用于纸张和纤维素产品的表面施胶的核/壳聚合物颗粒,其中由基于所述核/壳聚合物颗粒中的单体的总重量计包含至少40%、优选至少50%重量的选自(甲基)丙烯酸支链C3-10烷基酯(例如丙烯酸叔丁酯(t-BA))、苯乙烯、(甲基)丙烯酸直链C1-10烷基酯(例如丙烯酸正丁酯(n-BA))和丙烯腈(ACN)的单体的单体,聚合得到核/壳聚合物颗粒中的核聚合物和壳聚合物;条件是,核/壳聚合物颗粒中的聚合物包括至少40%、优选至少50%重量的(甲基)丙烯酸支链C3-6烷基酯,和总计至少50%、优选至少60%、甚至更优选至少70%重量的(甲基)丙烯酸支链C3-10烷基酯和苯乙烯、(甲基)丙烯酸直链C1-10烷基酯和/或丙烯腈,基于所述核/壳聚合物颗粒中的单体的总重量。
优选地,由选自(甲基)丙烯酸支链C3-6烷基酯(例如丙烯酸叔丁酯和/或甲基丙烯酸叔丁酯)、苯乙烯、(甲基)丙烯酸直链C3-6烷基酯(例如丙烯酸正丁酯)和丙烯腈的单体,更优选选自丙烯酸叔丁酯、丙烯酸正丁酯和丙烯腈的单体,聚合得到核/壳聚合物颗粒中的核聚合物和壳聚合物。
当(甲基)丙烯酸支链C3-10烷基酯的单体比率下降到低于40%重量时,聚合物的疏水(hydrophobation)性能显著下降。
当与无规聚合物颗粒的颗粒组合物相比时,所提供的聚合物颗粒的核/壳结构提供改进的施胶性能。采用核/壳结构,也可用选自苯乙烯、(甲基)丙烯酸直链C1-10烷基酯(例如丙烯酸正丁酯)和丙烯腈的一种或多种单体替代一些昂贵的(甲基)丙烯酸支链C3-10烷基酯,且仍然维持施胶效率。另外,已发现,当(甲基)丙烯酸支链C3-10烷基酯(尤其是丙烯酸叔丁酯和/或甲基丙烯酸叔丁酯)位于聚合物颗粒的壳内时,获得最好的结果。
在本发明的一个实例中,核/壳聚合物颗粒包括(a)由包含至少25%重量的选自(甲基)丙烯酸支链C3-10烷基酯(例如丙烯酸叔丁酯和/或甲基丙烯酸叔丁酯)、苯乙烯、(甲基)丙烯酸直链C1-10烷基酯(例如丙烯酸正丁酯)和丙烯腈的单体聚合得到的核聚合物;和(b)由包含至少25%、更优选至少30%、甚至更优选至少50%重量的(甲基)丙烯酸支链C3-10烷基酯的单体聚合得到的壳聚合物,基于所述核/壳聚合物颗粒中的单体的总重量,和其中所述壳聚合物优选包封所述核聚合物。
优选地,核/壳聚合物颗粒包括至少50%重量的(甲基)丙烯酸支链C3-10烷基酯和总计至少75%重量的(甲基)丙烯酸支链C3-10烷基酯和丙烯腈,基于所述核/壳聚合物颗粒中的单体的总重量。特别地,核/壳聚合物包括至少60%、更优选至少75%重量的(甲基)丙烯酸支链C3-10烷基酯,优选(甲基)丙烯酸支链C3-6烷基酯,尤其是丙烯酸叔丁酯和/或甲基丙烯酸叔丁酯,基于所述核/壳聚合物颗粒中的单体的总重量。
当核/壳聚合物颗粒的壳(即,壳聚合物)包括基于壳聚合物单体的总重量至少50%、优选至少60%、更优选至少75%重量的(甲基)丙烯酸支链C3-10烷基酯,优选(甲基)丙烯酸支链C3-6烷基酯,尤其是丙烯酸叔丁酯和/或甲基丙烯酸叔丁酯时,获得最好的施胶性能。
核/壳聚合物颗粒的核(即,核聚合物)优选包括基于核聚合物单体的总重量50-100%、更优选80-100%重量的选自(甲基)丙烯酸支链C3-10烷基酯(例如丙烯酸叔丁酯和/或甲基丙烯酸叔丁酯)、苯乙烯、(甲基)丙烯酸直链C1-10烷基酯(例如丙烯酸正丁酯)、丙烯腈及其任何混合物的单体。存在丙烯腈允许(甲基)丙烯酸支链C3-10烷基酯的单体比率比存在的(甲基)丙烯酸C1-10烷基酯更低,但一部分(甲基)丙烯酸支链C3-10烷基酯可以被(甲基)丙烯酸直链C1-10烷基酯替代且没有显著改变施胶效率。
可在不同的组合中提供核/壳聚合物颗粒中的单体,条件是获得具有“核/壳”类型结构的聚合物颗粒。因此可以梯度或者按序,优选按序,改变单体组成。
核聚合物单体的重量与壳聚合物单体的重量之比优选为75:25至25:75。在不含苯乙烯的核/壳聚合物情况下,较厚的壳,尤其是较厚的丙烯酸叔丁酯壳,改进施胶性能。为了最佳的性能,壳聚合物的玻璃化转变温度为35-75℃,更优选40-65℃。进一步地,为了最佳的性能,核聚合物的玻璃化转变温度低于75℃,优选低于65℃。
在本发明的核/壳聚合物颗粒的尤其有利的实例中,(甲基)丙烯酸支链C3-10烷基酯单体是(甲基)丙烯酸支链C3-6烷基酯,例如丙烯酸叔丁酯和/或甲基丙烯酸叔丁酯,更优选(甲基)丙烯酸支链C3-6烷基酯,最优选丙烯酸叔丁酯。
典型地在降解淀粉或水溶性天然或合成聚合物存在下,由单体聚合得到所述核/壳聚合物颗粒中的核聚合物和壳聚合物。降解淀粉的分子量Mn典型地为500-10000。优选分散聚合(例如悬浮聚合或乳液聚合)单体,形成所需的核/壳聚合物颗粒。优选地,在降解淀粉和/或水溶性天然或合成聚合物(优选降解淀粉)存在下,通过自由基引发的分散聚合,获得核/壳聚合物颗粒。因此术语“核/壳聚合物颗粒中的单体的总重量”仅仅是指可聚合单体的量且不包括组合物中降解淀粉和水溶性天然或合成聚合物的量。典型地,降解淀粉和/或水溶性天然或合成聚合物的量为10-60%,优选15-40%,相对于所述核/壳聚合物颗粒中的全部固体内容物的重量,即单体和降解淀粉及水溶性天然或合成聚合物之和为100%。优选在不存在低分子量乳化剂,尤其是选自烷基磺酸钠、十二烷基硫酸钠、十二烷基苯磺酸钠、磺基琥珀酸酯、脂肪醇聚二元醇醚、烷芳基聚二元醇醚和类似物的那些低分子量乳化剂情况下,进行单体的聚合。
核/壳的聚合方法通常是本领域技术人员已知的。可例如通过在热水中分散降解的土豆淀粉,然后在两步中进料所需的单体:第一核单体,和然后壳单体,同时进料过氧化氢,进行核/壳聚合物颗粒的制备。在冷却并猝灭反应之后,过滤提供含所需核/壳聚合物颗粒的微细分散液。
可在引发聚合的接枝-连接水溶性氧化还原体系存在下,进行聚合。合适的体系包括含过氧化氢和重金属离子(例如铯、锰或铁(II)盐)的氧化还原体系。
核/壳聚合物颗粒的粒度分布D50优选低于110nm。
本文进一步提供含本文定义的核/壳聚合物颗粒的表面施胶组合物。典型地作为水溶液或分散液,在水性液体载体中提供表面施胶组合物,但也可存在少量的水溶性或水混溶的有机溶剂。表面施胶组合物溶液典型地包括与施胶化合物一起的淀粉,所述淀粉可以是阴离子、非离子、两性或阳离子淀粉,优选阴离子淀粉。淀粉浓度优选为1-30%,更优选5-25%,和施胶剂(即,核/壳聚合物颗粒)的浓度为0.1-20%重量,优选0.5-5.0%重量,基于干淀粉的重量。
用于施胶纸张和其他纤维素产品(例如纸板)的具体技术包括但不限于为施加施胶组合物到纤维素-基产品上在造纸中常用的那些技术。例如,可使用胶泥(puddle)或薄膜施胶机或施胶机,通过使用压延机或刮刀刀片,将水性施胶组合物施加到纸张的表面上。或者,可将施胶组合物喷洒在纸网上或者通过将纸张浸渍在水性表面施胶组合物内而施加。然后在高温下,干燥用表面施胶溶液处理过的纸张或其他纤维素产品,典型地纸张的温度为80-110℃。干燥纸网足以引起表面施胶剂和表面强度充分形成。
本文公开的施胶组合物也可与生产纸张和其他纤维素产品常规使用的其他添加剂联合或者先后使用。本领域通常已知的这种额外的添加剂包括但不限于着色剂,无机颜料和填料,抗卷曲剂,额外的常规组分,例如表面活性剂,增塑剂,润湿剂,消泡剂,UV吸收剂,耐光性提高剂,聚合的分散剂,媒染剂,光学增白剂和流平剂。
本发明进一步提供表面施胶纤维素产品(尤其是纸张)的方法,该方法包括施加含本文定义的核/壳聚合物颗粒的施胶组合物到纤维素产品的至少一个表面上。因此本文进一步提供用本文定义的核/壳聚合物颗粒或者本文定义的表面施胶组合物表面施胶的纸张。
表面施胶组合物施加到其上的纸张或其他纤维素产品可以宽泛地变化且与制造纸张所使用的纸浆种类无关。本文公开的表面施胶组合物适合于制备任何厚度和任何种类的施胶纸张,和因此可应用到由任何具体的纸浆及其混合物获得的纸张或纸板上。
纸张或其他纤维素产品也可含有诸如填料、染料、纸张增强剂、排水速率改进剂和内施胶剂之类的添加剂。
可使用Cobb 60方法,ISO 535:1991(E),在23℃和50%相对湿度下,测定用本发明的表面施胶组合物表面施胶的纸张的吸水性。
实施例
实施例1
在搅拌下,在具有冷却/加热夹套的1L玻璃反应器内,在氮气氛围下,在329g软化水中分散57.25g氧化降解的土豆淀粉(Perfectamyl A 4692)。通过加热混合物到85℃,并在85℃下蒸煮30分钟,使淀粉溶解。在淀粉溶解完全之后,将28.6g 0.66%浓度的七水合硫酸亚铁(II)水溶液加入到该反应器内。在10分钟之后,添加3.3g 30%浓度的过氧化氢。在10分钟之后,淀粉降解完全。然后将167.4g加热的软化水加入到该反应器中。在温度稳定在85℃之后,开始化学品进料。分两步进料单体:在60分钟期间首先进料83.7g丙烯酸正丁酯和丙烯腈的混合物(1:1重量)。然后在60分钟期间进料83.7g丙烯酸叔丁酯。在120分钟期间,同时进料48.8g 10%过氧化氢溶液与单体原料。在进料期间,反应器温度保持在85℃下,和在聚合后保持15分钟。然后冷却混合物到60℃,并逐滴添加5.2g 11.7%浓度的氢过氧化叔丁基溶液到该反应器内。保持温度在60℃下另外60分钟。之后,进行冷却到40℃,并添加5.9g 10%浓度的乙二胺四乙酸钠盐(EDTA-Na)溶液,接着用25%浓度的氢氧化钠溶液,调节pH到6,并冷却到室温。使用100微米滤布,进行过滤。获得固体含量为26.5%的微细分散体。
实施例2
采用在第一单体原料中83.7g丙烯酸正丁酯和苯乙烯(1:1重量)的混合物,和在第二单体原料中,83.7g丙烯酸叔丁酯,重复实施例1。在60分钟内进料第一原料,和在60分钟内进料第二原料。获得固体含量为26.7%的微细分散体。
实施例3
采用在第一单体原料中41.9g丙烯酸正丁酯和在第二单体原料中125.6g丙烯酸叔丁酯,重复实施例1。在30分钟内进料第一原料,和在90分钟内进料第二原料。获得固体含量为26.7%的微细分散体。
实施例4
采用在第一单体原料中41.9g丙烯酸正丁酯和在第二单体原料中125.6g丙烯酸叔丁酯,反复实施例1。在15分钟内进料第一原料的一半,和在45分钟内进料第二半。在第一原料之后15分钟开始进料第二原料。在45分钟内同时进料1/3第二原料和第一单体原料。之后,在60分钟内进料2/3第二单体原料。获得固体含量为26.8%的微细分散体。
实施例5
在搅拌下,在具有冷却/加热夹套的1L玻璃反应器内,在氮气氛围下,在348g软化水中分散60.6g氧化降解的土豆淀粉(Perfectamyl A 4692)。通过加热混合物到85℃,并在85℃下蒸煮30分钟,使淀粉溶解。在淀粉溶解完全之后,将30.2g 0.66%浓度的七水合硫酸亚铁(II)水溶液加入到该反应器内。在10分钟之后,添加3.3g 30%浓度的过氧化氢。在10分钟之后,淀粉降解完全。然后将177.1g加热的软化水加入到该反应器中。在温度稳定在85℃之后,开始化学品进料。分两步进料单体:在72分钟期间首先进料106.3g丙烯酸叔丁酯。70.8g在第一单体原料内丙烯酸正丁酯和苯乙烯(22:78重量)的混合物,和在第二单体原料内106.3g丙烯酸正丁酯。在48分钟内进料第一原料和在72分钟内进料第二原料。在120分钟期间,同时进料48.8g 10%过氧化氢溶液与单体原料。在进料期间,反应器温度保持在85℃下,和在聚合后保持15分钟。然后冷却混合物到60℃,并逐滴添加5.5g11.7%浓度的氢过氧化叔丁基溶液到该反应器内。保持温度在60℃下另外60分钟。之后,进行冷却到40℃,并添加6.2g 10%浓度的乙二胺四乙酸钠盐(EDTA-Na)溶液,接着用25%浓度的氢氧化钠溶液,调节pH到6,并冷却到室温。使用100微米滤布,进行过滤。获得固体含量为26.5%的微细分散体。
实施例6
在搅拌下,在具有冷却/加热夹套的1L玻璃反应器内,在氮气氛围下,在348g软化水中分散60.6g氧化降解的土豆淀粉(Perfectamyl A 4692)。通过加热混合物到85℃,并在85℃下蒸煮30分钟,使淀粉溶解。在淀粉溶解完全之后,将30.2g0.66%浓度的七水合硫酸亚铁(II)水溶液加入到该反应器内。在10分钟之后,添加3.5g 30%浓度的过氧化氢。在10分钟之后,淀粉降解完全。然后将177.1g加热的软化水加入到该反应器中。在温度稳定在85℃之后,开始化学品进料。分两步进料单体:在24分钟期间首先进料35.4g丙烯酸叔丁酯。然后,在96分钟期间,进料141.7g丙烯酸正丁酯和苯乙烯(1:3重量)的混合物。在120分钟期间,同时进料51.6g 10%过氧化氢溶液与单体原料。在进料期间,反应器温度保持在85℃下,和在聚合后保持15分钟。然后冷却混合物到60℃,并逐滴添加5.5g 11.7%浓度的氢过氧化叔丁基溶液到该反应器内。保持温度在60℃下另外60分钟。之后,进行冷却到40℃,并添加6.2g10%浓度的乙二胺四乙酸钠盐(EDTA-Na)溶液,接着用25%浓度的氢氧化钠溶液,调节pH到6,并冷却到室温。使用100微米滤布,进行过滤。获得固体含量为26.5%的微细分散体。
实施例7
在搅拌下,在具有冷却/加热夹套的1L玻璃反应器内,在氮气氛围下,在348g软化水中分散60.6g氧化降解的土豆淀粉(Perfectamyl A 4692)。通过加热混合物到85℃,并在85℃下蒸煮30分钟,使淀粉溶解。在淀粉溶解完全之后,将30.2g 0.66%浓度的七水合硫酸亚铁(II)水溶液加入到该反应器内。在10分钟之后,添加3.3g 30%浓度的过氧化氢。在10分钟之后,淀粉降解完全。然后将177.1g加热的软化水加入到该反应器中。在温度稳定在85℃之后,开始化学品进料。分两步进料单体:在72分钟期间首先进料106.3g丙烯酸叔丁酯。然后,在48分钟期间,进料70.8g丙烯酸正丁酯和苯乙烯(1:2重量)的混合物。在120分钟期间,同时进料48.8g 10%过氧化氢溶液与单体原料。在进料期间,反应器温度保持在85℃下,和在聚合后保持15分钟。然后冷却混合物到60℃,并逐滴添加5.5g 11.7%浓度的氢过氧化叔丁基溶液到该反应器内。保持温度在60℃下另外60分钟。之后,进行冷却到40℃,并添加6.2g 10%浓度的乙二胺四乙酸钠盐(EDTA-Na)溶液,接着用25%浓度的氢氧化钠溶液,调节pH到6,并冷却到室温。使用100微米滤布,进行过滤。获得固体含量为25.9%的微细分散体。
对比例1(CE1)
在搅拌下,在具有冷却/加热夹套的1L玻璃反应器内,在氮气氛围下,在329g软化水中分散57.25g氧化降解的土豆淀粉(Perfectamyl A 4692)。通过加热混合物到85℃,并在85℃下蒸煮30分钟,使淀粉溶解。在淀粉溶解完全之后,将28.6g 0.66%浓度的七水合硫酸亚铁(II)水溶液加入到该反应器内。在10分钟之后,添加3.3g 30%浓度的过氧化氢。在10分钟之后,淀粉降解完全。然后将167.4g加热的软化水加入到该反应器中。在温度稳定在85℃之后,开始化学品进料。在120分钟期间,进料167.5g丙烯酸正丁酯和丙烯酸叔丁酯(1:3重量)的混合物。在120分钟期间,同时进料48.8g 10%过氧化氢溶液与单体原料。在进料期间,反应器温度保持在85℃下,和在聚合后保持15分钟。然后冷却混合物到60℃,并逐滴添加5.2g 16.7%浓度的氢过氧化叔丁基溶液到该反应器内。保持温度在60℃下另外60分钟。之后,进行冷却到40℃,并添加5.9g 10%浓度的乙二胺四乙酸钠盐(EDTA-Na)溶液,接着用25%浓度的氢氧化钠溶液,调节pH到6,并冷却到室温。使用100微米滤布,进行过滤。获得固体含量为26.8%的微细分散体。
试验实施例
使用基重为约120和100g/m2的内部未施胶的循环的纤维箱板纸,针对表面施胶应用,测试一系列表面施胶剂和配制剂。在这些试验中使用Mathis施胶机。在15%参考浓度下,添加表面施胶剂到表面施胶淀粉(C*膜07311)溶液中至120g/m2的基重或添加到实施例编号1的试验系列中,和在18%固体含量参考浓度下至100g/m2的基重或添加到实施例编号2的试验系列中。在1.5、3.0和4.5%重量的浓度下添加疏水聚合物。在70℃的温度下进行施胶试验。采用Reatec NO1温度指示条,测定施胶机辊隙的温度,并调节施胶机压辊的水浴温度,以获得所需温度。使片材在2m/min(2Bar)下穿过水平池施胶机。使用接触干燥器或者转鼓干燥器,在95℃下干燥片材1min/面。使用Reatec NO82温度指示条,调节干燥器的温度。根据标准ISO 535:1991(E),在23℃和50%相对湿度下,通过测量Cobb60施胶程度,确定施胶效率。
使用Zetasizer Nano-装置,测量样品的粒度。使用差示扫描量热仪(DSC),由冷冻干燥的样品测量样品的玻璃化转变温度。使用Mettler Toledo Halogen湿度分析仪,测量新的表面施胶剂中的固体含量。
在表1和表2中示出了所测试的施胶剂的组成。图1和2示出了用不同的施胶组合物施胶的纸张表面的吸水性。在所测试的单体组合物中在壳聚合物内含丙烯酸叔丁酯的单体组合物得到最好的结果。
表1.采用底衬编号1,120g/m2的基重和核/壳聚合物CE1、1、2、3和4的施胶试验
*不包括淀粉
表2采用底衬编号2,100g/m2的基重和核/壳聚合物5、6和7的施胶试验
*不包括淀粉
对本领域技术人员来说显而易见的是,随着技术进步,可按照各种方式实施本发明的概念。本发明及其实施方案并不受限于以上描述的实施例,而是可在权利要求书的范围内变化。
Claims (20)
1.一种用于纤维素产品的表面施胶的核/壳聚合物颗粒,其中由包含至少40%重量的选自(甲基)丙烯酸支链C3-10烷基酯、苯乙烯、(甲基)丙烯酸直链C1-10烷基酯和丙烯腈的单体的单体,聚合得到所述核/壳聚合物颗粒的核聚合物和壳聚合物,其中所述%重量基于所述核/壳聚合物颗粒中的单体的总重量计;
条件是,所述核/壳聚合物颗粒中的聚合物包括至少40%重量的(甲基)丙烯酸支链C3-6烷基酯和总计至少50%重量的(甲基)丙烯酸支链C3-10烷基酯和苯乙烯、(甲基)丙烯酸直链C1-10烷基酯和/或丙烯腈,基于所述核/壳聚合物颗粒中的单体的总重量。
2.根据权利要求1的核/壳聚合物颗粒,其中所述核/壳聚合物包括:
(a)由包含至少25%重量的选自(甲基)丙烯酸支链C3-10烷基酯(例如丙烯酸叔丁酯和/或甲基丙烯酸叔丁酯)、苯乙烯、(甲基)丙烯酸直链C1-10烷基酯(例如丙烯酸正丁酯)和丙烯腈的单体的单体聚合得到的核聚合物;和
(b)由包含至少25%、更优选至少30%、甚至更优选至少50%重量的(甲基)丙烯酸支链C3-10烷基酯的单体的单体聚合得到的壳聚合物,和其中所述壳聚合物包封所述核聚合物。
3.根据权利要求1或2的核/壳聚合物颗粒,其中由选自丙烯酸支链C3-10烷基酯(例如丙烯酸叔丁酯)、苯乙烯、(甲基)丙烯酸直链C1-10烷基酯(例如丙烯酸正丁酯)和丙烯腈的单体聚合得到所述核/壳聚合物颗粒中的核聚合物和壳聚合物。
4.根据权利要求3的核/壳聚合物颗粒,其中所述单体选自丙烯酸叔丁酯、丙烯酸正丁酯和丙烯腈。
5.根据权利要求1-4任何一项的核/壳聚合物颗粒,其中所述核/壳聚合物包括至少50%重量的(甲基)丙烯酸支链C3-10烷基酯,和总计至少75%重量的丙烯酸支链C3-6烷基酯和丙烯腈,基于所述核/壳聚合物颗粒中的单体的总重量。
6.根据权利要求1-5任何一项的核/壳聚合物颗粒,其中所述核/壳聚合物包括至少60%重量的(甲基)丙烯酸支链C3-10烷基酯,基于所述核/壳聚合物颗粒中的单体的总重量。
7.根据权利要求1-6任何一项的核/壳聚合物颗粒,其中所述壳聚合物包括至少50%重量的(甲基)丙烯酸支链C3-10烷基酯,基于所述壳聚合物单体的总重量。
8.根据权利要求1-7任何一项的核/壳聚合物颗粒,其中所述核聚合物包括50-100%重量的选自(甲基)丙烯酸支链C3-10烷基酯、苯乙烯、(甲基)丙烯酸直链C1-10烷基酯和丙烯腈及其混合物的单体,基于所述核聚合物单体的总重量。
9.根据权利要求1-6任何一项的核/壳聚合物颗粒,其中所述核聚合物单体的重量与所述壳聚合物单体的重量之比优选为75:25至25:75。
10.根据权利要求1-9任何一项的核/壳聚合物颗粒,其中所述壳聚合物的玻璃化转变温度为35-75℃,更优选40-65℃。
11.根据权利要求1-10任何一项的核/壳聚合物颗粒,其中所述核聚合物的玻璃化转变温度低于75℃,优选低于65℃。
12.根据权利要求1-11任何一项的核/壳聚合物颗粒,其中所述(甲基)丙烯酸支链C3-10烷基酯是丙烯酸叔丁酯。
13.根据权利要求1-12任何一项的核/壳聚合物颗粒,其中所述(甲基)丙烯酸直链C1-10烷基酯是丙烯酸正丁酯。
14.根据权利要求1-13任何一项的核/壳聚合物颗粒,其中所述核/壳聚合物颗粒的粒度分布D50为低于110nm。
15.根据权利要求1-14任何一项的核/壳聚合物颗粒,其中典型地在降解淀粉或水溶性天然或合成聚合物存在下,由单体聚合得到所述核/壳聚合物颗粒中的核聚合物和壳聚合物。
16.一种表面施胶组合物,其包含权利要求1-15任何一项的核/壳聚合物颗粒。
17.权利要求16的表面施胶组合物,其进一步包含淀粉,优选阴离子淀粉。
18.一种纤维素产品,其用权利要求1-15任何一项的核/壳聚合物颗粒或者权利要求16-17任何一项的表面施胶组合物表面施胶。
19.一种表面施胶纤维素产品(尤其是纸张)的方法,其包括施加权利要求16-17任何一项的施胶组合物到纤维素产品的至少一个表面上。
20.权利要求1-15任何一项的核/壳聚合物颗粒或者权利要求16-17任何一项的表面施胶组合物用于表面施胶纤维素产品(尤其是纸张)的用途。
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CN113166287A (zh) * | 2018-12-05 | 2021-07-23 | 赢创运营有限公司 | 用于制备聚合物颗粒的方法 |
CN111944359A (zh) * | 2020-08-21 | 2020-11-17 | 东北林业大学 | 一种核-壳型纤维素纳米颗粒自组装构筑微纳米层级超疏水涂层的制备方法 |
CN111944359B (zh) * | 2020-08-21 | 2021-05-18 | 东北林业大学 | 一种核-壳型纤维素纳米颗粒自组装构筑微纳米层级超疏水涂层的制备方法 |
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Publication number | Publication date |
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EP3344699A1 (en) | 2018-07-11 |
EP3344699B1 (en) | 2022-01-12 |
ES2909808T3 (es) | 2022-05-10 |
FI20155638L (fi) | 2017-03-05 |
FI128940B (en) | 2021-03-31 |
CA2997363A1 (en) | 2017-03-09 |
BR112018003329A2 (pt) | 2018-09-18 |
WO2017037347A1 (en) | 2017-03-09 |
RU2689743C1 (ru) | 2019-05-28 |
PL3344699T3 (pl) | 2022-05-02 |
EP3344699A4 (en) | 2019-06-05 |
PT3344699T (pt) | 2022-02-24 |
CN108137896B (zh) | 2021-04-16 |
US20180251945A1 (en) | 2018-09-06 |
BR112018003329B1 (pt) | 2022-05-17 |
US10640926B2 (en) | 2020-05-05 |
CA2997363C (en) | 2020-12-08 |
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