CN115819673A - Silicon-containing polymer, treating agent, and preparation method and application thereof - Google Patents
Silicon-containing polymer, treating agent, and preparation method and application thereof Download PDFInfo
- Publication number
- CN115819673A CN115819673A CN202211300863.1A CN202211300863A CN115819673A CN 115819673 A CN115819673 A CN 115819673A CN 202211300863 A CN202211300863 A CN 202211300863A CN 115819673 A CN115819673 A CN 115819673A
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- CN
- China
- Prior art keywords
- ltoreq
- alkyl
- silicon
- group
- aralkyl
- Prior art date
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 38
- 229920005573 silicon-containing polymer Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 104
- 229920000642 polymer Polymers 0.000 claims abstract description 60
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 59
- 239000010703 silicon Substances 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000004575 stone Substances 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 61
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 56
- 125000003118 aryl group Chemical group 0.000 claims description 54
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 51
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 48
- -1 morpholino, piperidino Chemical group 0.000 claims description 38
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 26
- 238000011282 treatment Methods 0.000 claims description 21
- 125000002947 alkylene group Chemical group 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 16
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000004033 plastic Substances 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
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- 239000004567 concrete Substances 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 239000004745 nonwoven fabric Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052895 riebeckite Inorganic materials 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 239000002649 leather substitute Substances 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
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- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
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- 238000012360 testing method Methods 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
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- 235000019698 starch Nutrition 0.000 description 15
- 238000000576 coating method Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
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- 229920001131 Pulp (paper) Polymers 0.000 description 7
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- 239000011436 cob Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 102100026735 Coagulation factor VIII Human genes 0.000 description 4
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 3
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- 125000006832 (C1-C10) alkylene group Chemical group 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 240000000111 Saccharum officinarum Species 0.000 description 2
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- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- CDDDRVNOHLVEED-UHFFFAOYSA-N 1-cyclohexyl-3-[1-[[1-(cyclohexylcarbamoylamino)cyclohexyl]diazenyl]cyclohexyl]urea Chemical compound C1CCCCC1(N=NC1(CCCCC1)NC(=O)NC1CCCCC1)NC(=O)NC1CCCCC1 CDDDRVNOHLVEED-UHFFFAOYSA-N 0.000 description 1
- CCTFAOUOYLVUFG-UHFFFAOYSA-N 2-(1-amino-1-imino-2-methylpropan-2-yl)azo-2-methylpropanimidamide Chemical compound NC(=N)C(C)(C)N=NC(C)(C)C(N)=N CCTFAOUOYLVUFG-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
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- 101150065749 Churc1 gene Proteins 0.000 description 1
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- 240000003183 Manihot esculenta Species 0.000 description 1
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
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- CZSHOUBXIGQRDI-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;sulfuric acid;hydrate Chemical compound O.OS(O)(=O)=O.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 CZSHOUBXIGQRDI-UHFFFAOYSA-N 0.000 description 1
- LSGUXGJUXCTZPW-UHFFFAOYSA-N bis[2-(5-methyl-4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;hydrochloride Chemical compound Cl.N1C(C)CN=C1C(C)(C)N=NC(C)(C)C1=NCC(C)N1 LSGUXGJUXCTZPW-UHFFFAOYSA-N 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Classifications
-
- 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
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
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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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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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
- C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- 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
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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
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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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a silicon-containing polymer, a treating agent, and a preparation method and application thereof. The silicon-containing polymer comprises a repeating unit generated by a silicon-containing monomer I and a repeating unit generated by a monomer II, wherein the silicon-containing monomer I comprises a silicon-containing monomer I-1a and/or a silicon-containing monomer I-1b. The definition of each monomer is as the specification. The polymer or the treating agent containing the polymer can be used for treating various articles such as paper products, textiles, stones and the like, and endows the articles with the functions of oil repellency and water repellency.
Description
Technical Field
The invention relates to a silicon-containing polymer, a treating agent containing the polymer, a preparation method and application thereof, which can be used for surface and internal additive treatment of various articles, such as paper products, natural stone, concrete, fiber fabrics, synthetic leather, non-woven fabrics, asbestos, fur or plastics, and endows the surfaces of the articles with oil and water repellent functions.
Technical Field
Polymers have been widely used for surface and interior additive treatments of paper, textiles, leather, stone, etc., which can impart multiple functions to the surface of an article, thereby improving the durability of the article, e.g., after paper treatment, can tolerate foods rich in grease; after the textile treatment, the ability of resisting various stains can be improved; after the stone is treated, the self appearance of the stone can be kept for a long time.
CN103975107B proposed a solution using barrier coatings, which mainly uses emulsion polymerization to produce a polymer emulsion by adding starch and emulsifier, and then coating the polymer emulsion on paper. Although the mode can also block grease, two problems are brought, namely the grease-proof effect can be achieved only by large coating amount, and the oil-proof effect can not be directly achieved on a common paper machine only by being suitable for the paper machine with coating equipment, so that the process applicability is not strong, and the cost is high. CN100360612C proposes that polysiloxane and polyvinyl alcohol are crosslinked under the action of a catalyst, and are dispersed by a surfactant, and the obtained treating agent can be used for paper coating treatment, but the process applicability is not strong. CN112513370a proposes a method of treating paper with long chain acrylate copolymers to achieve oil and water repellency, but this method has been found to be poor in thermal oil barrier effect at temperatures above 80 ℃.
CN107849187A proposes a method for finishing textiles by using a polymer formed by copolymerizing acrylate and monomers such as chloroethylene, and the polymer has a good water repellent effect. CN110114435A provides a copolymer which adopts acrylic ester, and then is compounded with wax emulsion and the like to finish the textile, and has good water repellent effect. CN105377935B adopts a polyurethane aqueous dispersion to finish textiles, and has good water repellent effect. However, these polymers have poor oil repellency and limited barrier properties.
CN105764980B proposes that long-chain acrylate is adopted to form emulsion under the action of cationic emulsifier, and can physically treat porous articles such as fiber, stone, leather and the like, thereby having the effects of water repellency and oil diffusion. But at the same time, the expansion prevention effect is found to be limited, and the blocking effect on grease is particularly poor.
Disclosure of Invention
It is an object of the present invention to provide a silicon-containing polymer and a treating agent comprising the same, which can treat various articles to impart oil-and water-repellent properties to the surfaces of the articles. The application also provides a preparation method of the treating agent.
In a first aspect, the invention provides a silicon-containing polymer comprising repeating units derived from silicon-containing monomer I and repeating units derived from monomer II, silicon-containing monomer I comprising silicon-containing monomer I-1a or/and silicon-containing monomer I-1b,
the structural general formula of the silicon-containing monomer I-1a is shown as the formula I-1 a:
CH 2 ＝C(R 1 )-W-B-Z I-1a
in the formula I-1a, R 1 Selected from hydrogen atoms or C 1 -C 20 An alkyl group;
w is selected from the group consisting of W-1, W-2, W-3 and W-4,
-O-C(O)-N(R 2 )- W-2
-O-C(O)-O- W-3
-O-C(O)-O-D-N(R 2 )- W-4
R 2 selected from hydrogen atoms or C 1 -C 20 Alkyl, D is C 1 -C 20 An alkylene group of (a); when W is selected from W-1, B is absent or is C 1 -C 20 When W is selected from W-2,W-3,W-4, B is C 1 -C 20 An alkylene group of (a);
the structural general formula of the silicon-containing monomer I-1b is shown as a formula I-1 b:
in the formula I-1b, R 1 Selected from hydrogen atoms or C 1 -C 20 An alkyl group; b is C 1 -C 20 OfAn alkyl group;
in formulas I-1a and I-1b, each Z is independently selected from the structures shown in the following formulas:
in the formula, R 4 Each independently is C 1 -C 20 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Or R is 5 -O-R 6 A group R 5 Is C 1 -C 10 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of, R 6 Is C 1 -C 10 1. Ltoreq. A.ltoreq.200;
Y 1 and Y 2 Are the same or different and are each independently selected from C 1 -C 20 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 And an alkylaryl group of formula (I):
R 7 each independently is C 1 -C 20 Alkyl or C 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 An alkylaryl group of (a); r 8 Each independently is C 1 -C 20 Alkyl of (C) 6 -C 20 Aryl of, C 7 -C 12 Aralkyl or C 7 -C 12 Or R is alkylaryl or 9 -O-R 10 A group in which R 9 Is C 1 -C 10 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of, R 10 Is C 1 -C 10 0. Ltoreq. B.ltoreq.200;
the structural general formula of the monomer II is shown as the formula (II):
CH 2 ＝C(R 1 )-P-B-N(R 3 R 4 ) (II)
in the formula (II), P is selected from the group consisting of P-1 and P-2,
-C(O)-O-
P-1
-C(O)-N(R 2 )-
P-2
b is C 1 -C 20 An alkylene group of (a); r is 1 And R 2 Each independently of the other being a hydrogen atom or C 1 -C 20 An alkyl group; r is 3 And R 4 Each independently is a hydrogen atom, C 1 -C 18 Alkyl, hydroxyethyl or benzyl, or R 3 And R 4 Combined and taken together with the nitrogen atom to form a morpholino, piperidino or pyrrolidino group.
According to some embodiments of the polymer of the present invention,
can be
According to some embodiments of the polymers of the present invention, in formula I-1a, B may be absent when W is selected from W-1, i.e. formula I-1a is CH 2 ＝C(R 1 )-W-Z。
According to some embodiments of the polymer of the present invention, silicon-containing monomer I further comprises silicon-containing monomer I-2,
the structural general formula of the silicon-containing monomer I-2 is shown as a formula I-2:
CH 2 ＝C(R 1 )-X-B-Z I-2
in the formula I-2, R 1 Selected from hydrogen atoms or C 1 -C 20 Alkyl groups of (a); b is C 1 -C 20 An alkylene group of (a);
x is selected from the group consisting of X-1 and X-2,
-C(O)-O-
X-1
-C(O)-N(R 2 )-
X-2
R 2 selected from hydrogen atoms or C 1 -C 20 Alkyl groups of (a);
z is selected from the structures shown in the following:
in the formula R 4 Each independently is C 1 -C 20 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Or R is 5 -O-R 6 A group R 5 Is C 1 -C 10 Alkyl of (C) 6 -C 20 Aryl of, C 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of, R 6 Is C 1 -C 10 1. Ltoreq. A. Ltoreq.200;
Y 1 and Y 2 Are the same or different and are each independently selected from C 1 -C 20 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 And an alkylaryl group of formula (I):
R 7 each independently is C 1 -C 20 Alkyl or C 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 An alkylaryl group of (a); r 8 Each independently is C 1 -C 20 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Or R is alkylaryl or 9 -O-R 10 -a group of (a) and (b),wherein R is 9 Is C 1 -C 10 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of (2), R 10 Is C 1 -C 10 0. Ltoreq. B.ltoreq.200.
According to some embodiments of the polymer of the present invention, in Z of formula I-1a and/or formula I-1b and/or formula I-2,
when a is 1, Y 1 And/or Y 2 Is a structure of formula (I), when a is greater than 1 and less than or equal to 200, at least one Y 1 Is a structure of formula (I) and/or at least one Y 2 Is a structure of formula (I):
R 7 each independently is C 1 -C 20 Alkyl or C 6 -C 20 Aryl of, C 7 -C 12 Aralkyl or C 7 -C 12 An alkylaryl group of (a); r 8 Each independently is C 1 -C 20 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Or R is alkylaryl or R 9 -O-R 10 A group in which R 9 Is C 1 -C 10 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of (2), R 10 Is C 1 -C 10 0. Ltoreq. B.ltoreq.200.
Preferably, R 7 Each independently is C 1 -C 10 Alkyl or C 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 An alkylaryl group of (a); r 8 Each independently is C 1 -C 10 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Or R is alkylaryl or 9 -O-R 10 A group in which R 9 Is C 1 -C 10 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of, R 10 Is C 1 -C 10 An alkylene group of (a).
Preferably, 0. Ltoreq. B.ltoreq.100.
Preferably, R 7 Each independently is C 1 -C 6 Alkyl or C 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 An alkylaryl group of (a); r 8 Each independently is C 1 -C 6 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Or R is alkylaryl or 9 -O-R 10 A group in which R 9 Is C 1 -C 6 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of, R 10 Is C 1 -C 6 An alkylene group of (a).
According to some embodiments of the polymer of the present invention, the polymer further comprises repeat units derived from monomer III, as shown in formula III:
CH 2 ＝C(R 1 )-G-(R 2 O) q -R 3 III
in the formula III, R 1 Represents a hydrogen atom or a methyl group, R 2 Each independently is C 1 -C 6 Alkylene of (3), preferably C 2 -C 4 Q is an integer of 1 to 50, preferably an integer of 1 to 20; r is 3 Represents a hydrogen atom or C 1 -C 20 Alkyl of (2), preferably a hydrogen atom or C 1 -C 10 More preferably a hydrogen atom or C 1 -C 3 Alkyl groups of (a);
wherein G is selected from the group consisting of G-1 and G-2,
-C(O)-O-(CH 2 ) n -
G-1
-C(O)-N(R 4 )-(CH 2 ) n -
G-2
R 4 represents a hydrogen atom or a methyl group, and n is an integer of 0 to 10, preferably 0 to 5.
According to some embodiments of the polymer of the present invention, the ratio of the repeating units derived from the silicon-containing monomer I-1a and/or the silicon-containing monomer I-1b to the repeating units derived from the silicon-containing monomer I is 1% to 100%,5% to 100%,10% to 100%, or 50% to 100%, for example, 1%, 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% such as 1%, 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or a range of any two of them. The total amount of repeating units derived from silicon-containing monomers I-1a and I-1b and repeating units derived from silicon-containing monomer I-2 is the total amount of repeating units derived from silicon-containing monomer I.
According to some embodiments of the polymer of the present invention, the content of repeating units derived from the silicon-containing monomer I in the polymer is in the range of 30 to 90% by mass, preferably 40 to 85% by mass, more preferably 50 to 80% by mass, for example 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% by mass or any combination of both of them.
According to some embodiments of the polymer of the present invention, the content of the repeating units derived from monomer II in the polymer is in the range of 5 to 65% by mass, preferably 10 to 50% by mass, more preferably 15 to 45% by mass, such as 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65% by mass or any combination thereof.
According to some embodiments of the polymer of the present invention, the mass content of the repeat units derived from monomer III in the polymer is in the range of 1 to 40%, preferably 5 to 30%, more preferably 10 to 25%, such as 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or any two thereof.
As is readily understood by those skilled in the art, the silicon-containing polymer of the present invention is prepared by polymerizing monomers, wherein the monomers used for polymerization comprise the silicon-containing monomer I and the monomer II, the silicon-containing monomer I comprises the silicon-containing monomer I-1a or/and the silicon-containing monomer I-1b, and optionally the monomer III.
According to some embodiments of the polymer of the present invention, the silicon-containing monomer I-1a and/or the silicon-containing monomer I-1b accounts for 1% to 100%,5% to 100%,10% to 100%, or 50% to 100%, for example, 1%, 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, for example, 1%, 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or a range consisting of any two thereof, in terms of mass percentage of the silicon-containing monomer I-1a and/or the silicon-containing monomer I-1b.
According to some embodiments of the polymer of the present invention, the proportion of the silicon-containing monomer I in the total amount of monomers is 30 to 90% by mass, preferably 40 to 85% by mass, more preferably 50 to 80% by mass, for example 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% by mass or a range consisting of any two of them.
According to some embodiments of the polymer of the present invention, the proportion of monomer II in the total amount of monomers is in the range of 5 to 65% by mass, preferably 10 to 50% by mass, more preferably 15 to 45% by mass, such as 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65% by mass or any two of them.
According to some embodiments of the polymer of the present invention, the proportion of monomer III in the total amount of monomers is 1 to 40% by mass, preferably 5 to 30% by mass, more preferably 10 to 25% by mass, for example 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40% by mass or a range consisting of any two of them.
According to some embodiments of the present invention, R in the silicon-containing monomers I-1a, I-1b and I-2 is 1 Selected from a hydrogen atom or a methyl group.
According to some embodiments of the invention, silicon-containing monomers I-1a, I-1In B and I-2, B is selected from C 1 -C 10 Alkylene of (3), preferably C 1 -C 6 An alkylene group of (a).
According to some embodiments of the invention, D in the silicon-containing monomers I-1a is selected from C 1 -C 10 Alkylene of (3), preferably C 1 -C 6 An alkylene group of (a).
According to some embodiments of the present invention, R in the silicon-containing monomers I-1a, I-1b and I-2 2 Selected from a hydrogen atom or a methyl group.
According to some embodiments of the invention, R in Z 4 Each independently is C 1 -C 10 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Or R is 5 -O-R 6 A group R 5 Is C 1 -C 10 Alkyl of (C) 6 -C 10 Aryl of, C 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of, R 6 Is C 1 -C 10 And/or 1. Ltoreq. A.ltoreq.80; r 7 Each independently is C 1 -C 10 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 An alkylaryl group of (a); r 8 Each independently is C 1 -C 10 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Or R is alkylaryl, or 9 -O-R 10 A group in which R 9 Is C 1 -C 10 Alkyl of (C) 6 -C 10 Aryl of, C 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of (2), R 10 Is C 1 -C 10 And/or 0. Ltoreq. B.ltoreq.80.
According to some embodiments of the invention, R in Z 4 Each independently is C 1 -C 6 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 10 Aralkyl or C 7 -C 10 Or R is alkylaryl or R 5 -O-R 6 A group R 5 Is C 1 -C 6 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 10 Aralkyl or C 7 -C 10 Alkylaryl of, R 6 Is C 1 -C 6 1. Ltoreq. A.ltoreq.30; r 7 Each independently is C 1 -C 6 Alkyl of (C) 6 -C 10 Aryl of, C 7 -C 10 Aralkyl or C 7 -C 10 An alkylaryl group of (a); r 8 Each independently is C 1 -C 6 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 10 Aralkyl or C 7 -C 10 Or R is alkylaryl, or 9 -O-R 10 A group in which R 9 Is C 1 -C 6 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 10 Aralkyl or C 7 -C 10 Alkylaryl of, R 10 Is C 1 -C 6 0. Ltoreq. B.ltoreq.30.
In some embodiments, a is an integer from 1 to 80, an integer from 1 to 30, an integer from 1 to 20, or an integer from 1 to 10.
In some embodiments, b is 0. In some embodiments, b is an integer from 1 to 30, an integer from 1 to 20, an integer from 1 to 10, or an integer from 1 to 5.
In some embodiments, each Z is independently selected from one or more of the following structures i-1 to i-6:
each R is independently selected from C 1 -C 10 Alkyl radical, C 6 -C 10 Aryl radical, C 7 -C 12 Aralkyl or C 7 -C 12 An alkylaryl group of (a);
m +1 is 1. Ltoreq. M + 1. Ltoreq.60, preferably 1. Ltoreq. M + 1. Ltoreq.30; p is 0. Ltoreq. P.ltoreq.60, preferably 0. Ltoreq. P.ltoreq.30; q is 0. Ltoreq. Q.ltoreq.60, preferably 0. Ltoreq. Q.ltoreq.30; 1. Ltoreq. X.ltoreq.9, preferably 1. Ltoreq. X.ltoreq.7.
In some embodiments, R is C 1 -C 3 Alkyl groups such as methyl.
In some preferred embodiments, Z is selected from the following structures:
one or more of (a);
me represents methyl, ph represents phenyl; 1. Ltoreq. M + 1. Ltoreq.60, preferably 1. Ltoreq. M + 1. Ltoreq.30; p is 0. Ltoreq. P.ltoreq.60, preferably 0. Ltoreq. P.ltoreq.30; q is 0. Ltoreq. Q.ltoreq.60, preferably 0. Ltoreq. Q.ltoreq.30; 1. Ltoreq. X.ltoreq.9, preferably 1. Ltoreq. X.ltoreq.7.
In some embodiments, m is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.
In some embodiments, x is 1, 2, 3, 4, 5, 6, or 7.
According to some embodiments of the polymer of the present invention, in the structure of monomer II, R 1 And R 2 Selected from a hydrogen atom or a methyl group; b is C 1 -C 6 An alkylene group of (a); r 3 And R 4 Are each independently C 1 -C 3 Alkyl, hydroxyethyl or benzyl, or R 3 And R 4 Bonded to and taken together with the nitrogen atom to form a morpholino, piperidino or pyrrolidino group.
According to some embodiments of the polymer of the present invention, silicon-containing monomer I-1a is selected from
CH 2 ＝CH-ph-Si(OSi(CH 3 ) 3 ) 3 (ph represents
CH 2 ＝CH-ph-(CH 2 ) 2 Si(OSi(CH 3 ) 3 ) 3 (ph represents
CH 2 ＝CH-ph-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Denotes butyl, ph denotes
CH 2 ＝CH-O-C(O)-NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ，
CH 2 ＝CH-O-C(O)-NH-(CH 2 ) 3 -[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Represents butyl) (1. Ltoreq. N. Ltoreq.25), CH 2 ＝CH-O-C(O)-O-(CH 2 ) 3 -Si(OSi(CH 3 ) 3 ) 3 ，
CH 2 ＝CH-O-C(O)-O-(CH 2 ) 3 -[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Represents butyl) (1. Ltoreq. N. Ltoreq.25) CH 2 ＝CH-O-C(O)-O-(CH 2 ) 2 -NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 And are and
CH 2 ＝CH-O-C(O)-O-(CH 2 ) 2 -NH-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 represents a butyl group) (1. Ltoreq. N. Ltoreq.25).
According to some embodiments of the polymer of the present invention, silicon-containing monomer I-1b is selected from
CH 2 ＝CH-C(O)-N[-(CH 2 ) 3 -Si(OSi(CH 3 ) 3 ) 3 ] 2 ，
CH 2 ＝CH-C(O)-N[-(CH 2 ) 3 -Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ] 2 ，
CH 2 ＝CH-C(O)-N[-(CH 2 ) 3 -(Si(CH 3 ) 2 O) n -Si(CH 3 ) 2 C 4 H 9 ] 2 (C 4 H 9 Represents a butyl group) (1. Ltoreq. N. Ltoreq.25) And
CH 2 ＝C(CH 3 )-C(O)-N[-(CH 2 ) 3 -(Si(CH 3 ) 2 O) n -Si(CH 3 ) 2 C 4 H 9 ] 2 (C 4 H 9 represents a butyl group) (1. Ltoreq. N. Ltoreq.25).
According to some embodiments of the polymer of the present invention, silicon-containing monomer I-2 is selected from
CH 2 ＝C(CH 3 )-C(O)-O-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ，
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Represents butyl) (1. Ltoreq. N. Ltoreq.25), CH 2 ＝C(CH 3 )C(O)-NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 And are and
CH 2 ＝C(CH 3 )C(O)-NH-(CH 2 ) 3 -[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 represents a butyl group) (1. Ltoreq. N. Ltoreq.25).
According to some embodiments of the polymer of the present invention, monomer II is selected from one or more of dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, N-tert-butylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dipropylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide.
According to some embodiments of the polymer of the present invention, monomer III is selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, preferably hydroxyethyl methacrylate, 4-hydroxybutyl acrylate.
According to some embodiments of the polymer of the present invention, the weight average molecular weight of the polymer is in the range of from 800 to 200 ten thousand, preferably from 2000 to 150 ten thousand. According to some embodiments of the polymer of the present invention, the polymer is in the form of an ammonium salt or an nitroxide.
The present invention further provides a treating agent comprising the above-described silicon-containing polymer of the present invention and a solvent comprising water and/or an organic solvent. Preferably, the organic solvent is one or more of acetone, methyl ethyl ketone, 4-methyl-2-pentanone, ethyl acetate, butyl acetate, N-methyl-2-pyrrolidone, N-dimethylformamide, ethanol, isopropanol, N-propanol, butyl carbitol and dipropylene glycol methyl ether.
The present invention also relates to a method for producing the above treating agent, which comprises the steps of:
(1) Monomers (including silicon-containing monomer I, monomer II, and optionally monomer III) are polymerized in an organic solvent to obtain a polymer solution.
According to some embodiments of the present invention, the silicon-containing monomer I-1a and/or I-1b accounts for 1% to 100%,5% to 100%,10% to 100%,50% to 98%, for example, 1%, 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, for example, 1%, 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or a range consisting of any two thereof, by mass of the silicon-containing monomer I-1a and/or I-1b.
According to some embodiments of the present invention, the silicon-containing monomer I is used in a proportion of 30 to 90% by mass, preferably 40 to 85% by mass, more preferably 50 to 80% by mass, for example, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% by mass or a range composed of any two of them, based on the total amount of the monomers.
According to some embodiments of the present invention, the amount of the monomer II is 5 to 65% by mass, preferably 10 to 50% by mass, more preferably 15 to 45% by mass, for example, 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65% by mass or a range consisting of any two of them, based on the total amount of the monomers.
According to some embodiments of the present invention, the amount of the monomer III is 0 to 40%, preferably 1 to 40%, more preferably 5 to 30%, and even more preferably 10 to 25%, for example 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or any two of them.
The manufacturing method may further include any one or more of the following steps (2), (3), (4), as necessary:
(2) Adding water for dispersion, and simultaneously removing the organic solvent from the polymer solution, or removing the solvent first and then adding the water for dispersion;
(3) Adding organic acid to convert the amino group in the polymer into ammonium salt;
(4) An oxidizing agent (e.g., hydrogen peroxide) is added to convert the amino groups of the polymer to nitroxides.
In addition, the invention also provides the application of the silicon-containing polymer or the treating agent in fiber fabrics, leather, non-woven fabrics, asbestos, fur, concrete, natural stones, paper products or plastics. In addition, the invention also provides a product treated by the silicon-containing polymer or the treating agent, wherein the product can be fiber fabric, leather, non-woven fabric, asbestos, fur, concrete, natural stone, paper products or plastics.
Examples of paper products in this application include, but are not limited to, paper carriers such as paper cups, paper bowls, paper trays, and the like.
ADVANTAGEOUS EFFECTS OF INVENTION
The silicon-containing polymer and the treatment agent produced by the silicon-containing polymer can be conveniently dispersed in a solvent or water, and can be applied to treatment of various articles, such as paper products, natural stones, concrete, fiber fabrics, synthetic leather, non-woven fabrics, asbestos, fur or plastics, and the treatment mode comprises coating, soaking or internal addition and other modes for treatment, and the silicon-containing polymer and the treatment agent can endow the surface of the articles with oil repellency and water repellency after treatment.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. These examples are only for explaining the present invention and do not constitute any limitation to the present invention. The actual scope of the invention is set forth in the following claims.
In the present application, unless otherwise specified, terms used have the ordinary meanings known to those skilled in the art.
In the present application, the term "alkyl" refers to straight or branched chain alkyl groups, non-limiting examples of which include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl and the like.
In the present application, the term "alkylene" refers to a straight or branched chain alkylene, non-limiting examples of which include: methylene, ethylene, n-propylene, n-butylene, n-pentylene, -CHCH 3 CH 2 -、-CHCH 3 CH 2 CH 2 -、CH 2 CH 3 CHCH 2 -and the like.
In the present application, "%" means mass percent unless otherwise specified.
1. Polymerization process
The polymerization mode of the copolymer is not particularly limited, and any of conventional radical polymerization modes such as bulk polymerization, solution polymerization in an organic solvent, and emulsion polymerization in water can be used.
In the present invention, it is preferable that after polymerization (e.g., solution polymerization or emulsion polymerization), water and an acid are added and then the solvent is removed to obtain an aqueous dispersion; or after removing the solvent, adding water and acid to obtain the aqueous dispersion.
As the initiator of the polymer, peroxide, azo-based compound or persulfate-based compound can be used, and the polymerization initiator may be selected from oil-soluble or water-soluble initiators depending on the polymerization system.
Examples of oil-soluble polymerization initiators are preferably 2,2 '-azobis (2-methylpropanenitrile), 2,2' -azobis (2-methylbutyronitrile), 2,2 '-azobis (2,4-dimethylvaleronitrile), 2,2' -azobis (2,4-dimethyl-4-methoxyvaleronitrile), 1,1 '-azobis (ethylene-1-carbonitrile), dimethyl-2,2' -azobis (2-methylpropionate), benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like.
Examples of the water-soluble polymerization initiator are preferably 2,2' -azobisisobutylamidine dihydrochloride, 2,2' azobis (2-methylpropionamidine) hydrochloride, 2,2' -azobis [2- (2-imidazolin-2-yl) propane ] hydrochloride, 2,2' -azobis [2- (2-imidazolin-2-yl) propane ] sulfate hydrate, 2,2' -azobis [2- (5-methyl-imidazolin-2-yl) propane ] hydrochloride, potassium persulfate, barium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydrogen peroxide and the like.
The polymerization initiator is preferably a peroxide or a coupling compound having a half-life of 10 hours and a decomposition temperature of 40 ℃ or higher, such as t-butyl peroxypivalate, 2,2' -azobis (2-methylpropanenitrile), or the like.
A typical solution polymerization process of the present invention is as follows,
adding a solvent, adding a corresponding monomer for dissolving, introducing nitrogen to replace oxygen, adding an initiator, heating to the reaction temperature of 40-120 ℃, and reacting for 4-20 hours.
The process for producing the treating agent of the present invention comprises the following steps:
(1) Putting a silicon-containing monomer I, a monomer II and an optional monomer III into an organic solvent in proportion, and adding an initiator for polymerization;
(2) According to the requirement, after the polymerization is finished, adding water for dispersion, and removing the organic solvent;
(3) A process of converting amino groups in the polymer into ammonium salts by adding an acid as required;
(4) Adding an oxidant into the dispersion to treat the dispersion according to the requirement;
2. test method
Paper processing and testing method
The paper which can be treated includes thin paper, thick paper, cardboard, or molded pulp, etc., from unit area (meter) 2 ) A carton of up to 300 grams, again per unit area (meter) 2 ) Kraft paper up to 80 grams per unit area (meters) 2 ) Up to 100 grams of tissue paper to unit area (meters) 2 ) Paper-plastic products up to 200 g can be processed.
The paper material may be chemically bleached or unbleached pulp, wood pulp, chemimechanical pulp, mechanical pulp, etc., and it is also possible to add resin components such as polyamide, polyolefin, polyvinyl alcohol, etc. to these pulp sheets. The method of paper treatment is as follows:
(1) Wet end treatment: the weight of the paper and the plastic is 350 g/m 2
The method comprises the steps of directly pulping a sugarcane pulp board, wherein the degree of deduction is 600ml of Canadian freedom, the concentration of paper pulp is 0.3%, sequentially adding a sizing agent of Alkyl Ketene Dimer (AKD) into the sugarcane pulp board, wherein the addition amount of the sizing agent is 2% of the weight of dry paper, and then adding a synthesized treating agent, and the addition amount of the synthesized treating agent is 1-15% of the weight of the dry paper.
The pulp was poured into a 10 "disc mold screen by the specified weight and then the water was removed by vacuum filtration. The oil and water repellency of the disc tableware was evaluated by baking at 150 ℃ for 120 seconds in a mold.
(2) Surface sizing treatment example:
preparation of test paper: paper weight 50 g/m 2
Chemical pulp board LBKP (broad leaf bleached kraft pulp) and NBKP (needle bleached kraft pulp) are adopted, the proportion is 5:5, and the pulp board is buckled, and the degree of the buckling is 200ml of Canadian freedom. Adding cationic starch MC-2 type starch produced by Guangxi Ming Yang Yang Biochemical company into paper during papermaking, wherein the addition amount is 1% of the weight of a pulp board, and papermaking with a fourdrinier machine to obtain the paper with the weight of 50 g/m 2 Tissue paper of (4).
The starch solution used for sizing was a non-ionically modified hydroxyethyl starch, a Penford Gum 290 starch from Penford, inc., at a concentration of 5%. Heating the starch solution to above 90 ℃ for gelatinization, and adding the synthesized treating agent after the gelatinization, wherein the concentration of the treating agent in the starch solution is 1-15% by weight. Controlling the temperature of the starch solution to be not lower than 70 ℃, firstly performing surface sizing treatment on the paper, and then performing drying treatment to obtain the treated paper, wherein the liquid absorption amount is more than 70%.
(3) Example of surface coating:
preparation of test paper: the weight of the paper is 230 g/m 2
The paper is compounded with five layers, including bottom layer and top layer of chemical pulp board LBKP and NBKP in the ratio of 7:3, and middle three layers of chemical and mechanical pulp board compounded in paper machine to weight 230 g/m 2 The paperboard of (1).
The coating starch is cassava coating starch MS-1 produced by Guangxi Ming Yang Yang Biochemical company. The starch concentration is 20%, the starch is added with water and heated to more than 90 ℃ for gelatinization, the synthesized paper treating agent is added after the gelatinization is finished, and the concentration of the treating agent in the starch solution is 1-15% (mass concentration). Controlling the starch temperature to be not lower than 50 ℃, and coating the starch on the top layer of the paperboard by using a paper coating machine, wherein the coating weight is 3-8 g/m 2 。
Evaluation of oil repellency and Water repellency
The present invention will be described specifically with reference to the following examples and comparative examples, but the description is not intended to limit the present invention. In the following experiments, the% addition amounts are in parts by weight unless otherwise specified.
The test methods used below are as follows.
Evaluation of oil repellency test
(1) Hot oil resistance test
Hot oil (salad oil, peanut oil, rapeseed oil) at 85 ℃ was poured onto the paper product, and the paper product was rated by observing for 20 minutes to see if there was any penetration.
5, the surface does not change color;
4, slightly discoloring the surface;
the surface has color change and slight permeation is divided into 3 points;
2, severe infiltration;
evaluation of Water repellency
(1) Cobb test
The test was carried out according to GB/T1540-2002 or ISO 535 1991,
the principle is that the height of water supporting 10mm is measured to be 100cm 2 The weight (g) of water absorbed on the paper in 1 minute, and the value is converted into the weight per 1 square meter (g/m) 2 )。
The Cobb absorbency tester typically employs a roll-over cylinder tester. The metal cylinder is a cylinder with an internal cross-sectional area of typically (100 + -0.2) cm 2 The corresponding inner diameter is (112.8. + -. 0.2) mm. If a small area cylinder is used, it is recommended that the area should be not less than 50cm 2 At this time, the volume of water should be correspondingly reduced to ensure the water height of 10 mm. The cylinder has a height of 50mm, and the portion of the cylinder ring surface in contact with the sample should be smooth and have sufficient roundness to prevent the edge of the cylinder from damaging the sample. In order to prevent water leakage, a layer of elastic but non-absorbent rubber pad or gasket should be added on the turnover cylinder cover and the flat-pressing base, the roller width of the metal pressing roller should be (200 plus or minus 0.5) mm, the mass should be (10 plus or minus 0.5) kg, and the surface should be smooth.
The treated paper sample was cut into 10 (5 on each front and back) samples each having a (125. + -.5) mm square or phi (125. + -.5) mm circular shape. For an instrument with a small test area, the size of a sample is slightly larger than the outer diameter of the cylinder, so that water leakage caused by the fact that the sample is too small is avoided, and the influence on operation caused by the fact that the sample is too large is also avoided.
Before placing the sample, the surface of the cylinder ring and the rubber pad which are contacted with the sample are dry, and hands are not contacted with the testing area. 100mL of water was measured with a graduated cylinder and poured into the cylinder, and then the weighed mass of the sample was placed on the annular face of the cylinder with the test face down. The gland was capped and clamped onto the sample to secure it to the cylinder.
The cylinder is turned over 180 degrees, and simultaneously a stopwatch is started to time, and water is absorbed for 60 seconds. And (5) turning the cylinder right before the water absorption is finished for 10-15 s, loosening the gland clamping device and taking down the sample. Note that after 5 tests, the test water should be changed to avoid affecting the test results. At the moment when the predetermined water absorption time is reached, the sample taken out of the cylinder is placed on a previously laid absorbent paper with the water absorption surface facing downward. And placing a piece of absorbent paper on the sample, and then immediately rolling the sample in a metal press roll in a reciprocating way within 4s without applying other pressure to suck the residual water on the surface of the sample. The sample is taken out quickly, the water absorption surface is folded inwards, and then the sample is folded once again and weighed to be accurate to 0.001g. For thick cardboard, the sample may not be easily folded, in which case the second weighing should be done as soon as possible.
The Cobb value is expressed by the following equation: c = (g 2-g 1)/F
In the formula: c cobb value;
g 2-sample weight after water absorption;
g1- -sample weight before water absorption;
F—100cm 2 testing the area;
(2) Hot water resistance test
The method is used for directly testing the hot water resistance of paper, is relatively simple, generally makes the treated paper into a container capable of holding liquid, pours boiled water at 100 ℃ into the container, observes for 30 minutes to see whether leakage exists or not, and does not pass through the leakage, and is suitable for pulp molding products.
The stone processing and testing method comprises the following steps:
the natural stone that can be treated includes: marble, granite, sandstone, slate, and the like.
Taking sandstone as an example, soaking a sandstone sample into a treating agent solution diluted by a certain amount by water, taking out, naturally airing for 48 hours at the temperature of not lower than 25 ℃, then respectively dripping salad oil, mustard sauce, coffee, vinegar and the like on the surface of the sandstone, and observing the wetted state. If impermeable, the better the resistivity.
5, the surface does not change color;
4, slightly discoloring the surface;
the surface has color change and slight permeation is divided into 3 points;
2, severe infiltration;
2. examples and comparative examples
Chemical abbreviations see table 1:
TABLE 1
Example 1
A1000 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer was charged with 76 g of Si-ph-B3, 25 g of DN,15 g of HEMA and 120 g of Methyl Ethyl Ketone (MEK), nitrogen was introduced thereinto for 30 minutes, the temperature was slowly raised to 50 to 60 ℃ and 1.5 g of t-butyl peroxypivalate as a peroxide initiator was gradually added thereto, and the reaction was carried out at 60 ℃ for 20 hours while controlling the reaction temperature to obtain about 236 g of a polymer A solution having a solid content of about 50%.
340 g of water and 10 g of glacial acetic acid were added, and the mixture was stirred at 70 ℃ for 1 hour or more, and MEK in the polymer A solution was distilled off under reduced pressure to obtain an aqueous dispersion having a solid content of 25%.
Examples 2 to 7
<xnotran> 1 , I Si-ph-B3, Si-ph-B1 ( 2), si-N2-B2 ( 3), si-N2-B1 ( 4), si-OCN-B3 ( 5), si-OCO-B3 ( 6), si-ph0-B3 ( 7). </xnotran>
Comparative example 1
A1000 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet, a thermometer and a stirrer was charged with 76 g of Si-5 (average molecular weight 500), 25 g of DN,15 g of HEMA and 120 g of Methyl Ethyl Ketone (MEK), nitrogen was introduced thereinto for 30 minutes, the temperature was slowly raised to 50 to 60 ℃ and 1.5 g of t-butyl peroxypivalate as a peroxide initiator was gradually added thereto, and the reaction was carried out at 60 ℃ for 20 hours while controlling the reaction temperature to obtain about 236 g of a polymer A solution having a solid content of about 50%.
340 g of water and 10 g of glacial acetic acid were added, stirring was carried out at 70 ℃ for 1 hour or more, and MEK in the above-mentioned polymer A solution was distilled off under reduced pressure to obtain an aqueous dispersion having a solid content of 25%.
Performance test
Several articles were tested using the aqueous dispersions synthesized in the examples and comparative examples as treating agents:
1) Testing paper tableware: a1 wt% strength pulp solution was prepared, and a 10 inch disk weighing 20 grams was prepared by adding 2wt% AKD type sizing agent and 10wt%,6wt%,3wt%,2wt% treating agent, respectively, based on the weight of dry paper. Testing with 85 ℃ salad oil for 20 minutes, and grading according to the permeation condition; testing with 100 deg.C boiled water for 30 min, and recording passage or water leakage.
2) Testing of the paper: selecting 50 g/m 2 The paper of (1) was treated by surface sizing at concentrations of 5 wt.%, 4 wt.%, 3 wt.%, respectively, and tested for resistance to hot oil and Cobb water absorption.
3) Testing of the paper: selecting 230 g/m 2 The cardboard of (2) was treated by coating, and the concentrations of the treating agents were 5wt%,4wt%, and 3wt%, respectively, and tested for resistance to hot oil and Cobb water absorption.
4) Testing of sandstone: diluting the treating agent with water into 3wt%,2wt% and 1wt% liquids, taking the sandstone sample to soak the liquid, taking out the sandstone sample, naturally airing for 48 hours at a temperature of not less than 25 ℃, dripping salad oil and coffee on the surface of the sandstone respectively, observing the wetted state, and grading.
A summary of the test properties of examples 1-7 and comparative example 1 is shown in Table 2.
Table 2 comparison of test properties
As can be seen from the test performances of the above examples and comparative examples, various treatment agents all exhibited better oil and water repellent characteristics, wherein the treatment agents prepared using the branched silicon monomers Si-ph-B3, si-ph0-B3 exhibited better oil and water repellent effects at higher dosages, but the former two were significantly better than the latter two after the addition amount of the treatment agent was reduced, indicating that the former two had better oil and water repellent properties and higher efficiency.
Example 8
A1000 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet, a thermometer and a stirrer was charged with 48 g of Si-ph-B3, 28 g of Si-5 (average molecular weight 500), 25 g of DN,15 g of HEMA and 120 g of Methyl Ethyl Ketone (MEK), purged with nitrogen for 30 minutes, slowly warmed to 50 to 60 ℃, added 1.5 g of t-butylperoxypivalate as a peroxide initiator in portions, and reacted at 60 ℃ for 20 hours to give about 236 g of a polymer A solution having a solid content of about 50%.
340 g of water and 10 g of glacial acetic acid were added, and the mixture was stirred at 70 ℃ for 1 hour or more, and MEK in the polymer A solution was distilled off under reduced pressure to obtain an aqueous dispersion having a solid content of 25%.
Example 9
A1000 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet, a thermometer and a stirrer was charged with 76 g of Si-ph-B3, 25 g of DM,15 g of HEMA and 120 g of methyl ethyl ketone (hereinafter referred to as MEK), purged with nitrogen for 30 minutes, slowly heated to 50 to 60 ℃ and added 1.5 g of t-butylperoxypivalate as a peroxide initiator in portions, and the reaction temperature was controlled at 60 ℃ for 20 hours to obtain about 236 g of a polymer A solution having a solid content of about 50%.
340 g of water and 10 g of glacial acetic acid were added, stirring was carried out at 70 ℃ for 1 hour or more, and MEK in the above-mentioned polymer A solution was distilled off under reduced pressure to obtain an aqueous dispersion having a solid content of 25%.
Example 10
A1000 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer was charged with 76 g of Si-ph-B3, 25 g of DN,15 g of 4-HBA and 120 g of Methyl Ethyl Ketone (MEK), nitrogen was introduced for 30 minutes, the temperature was slowly raised to 50 to 60 ℃, 1.5 g of t-butylperoxypivalate as a peroxide initiator was added in portions, and the reaction was carried out at 60 ℃ for 20 hours while controlling the reaction temperature to obtain about 236 g of a polymer A solution having a solid content of about 50%.
340 g of water and 10 g of glacial acetic acid were added, stirring was carried out at 70 ℃ for 1 hour or more, and MEK in the above-mentioned polymer A solution was distilled off under reduced pressure to obtain an aqueous dispersion having a solid content of 25%.
A summary of the test properties of examples 8-10 is shown in Table 3.
TABLE 3 comparison table of test performances
The technical solution of the present invention is not limited to the limitations of the above specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention.
Claims (12)
1. A silicon-containing polymer comprising repeating units derived from a silicon-containing monomer I and repeating units derived from a monomer II, the silicon-containing monomer I comprising a silicon-containing monomer I-1a and/or a silicon-containing monomer I-1b,
the structural general formula of the silicon-containing monomer I-1a is shown as the formula I-1 a:
CH 2 ＝C(R 1 )-W-B-Z I-1a
in the formula I-1a, R 1 Selected from hydrogen atoms or C 1 -C 20 An alkyl group;
w is selected from the group consisting of W-1, W-2, W-3 and W-4,
-O-C(O)-N(R 2 )- W-2
-O-C(O)-O- W-3
-O-C(O)-O-D-N(R 2 )- W-4
R 2 selected from hydrogen atoms or C 1 -C 20 Alkyl, D is C 1 -C 20 An alkylene group of (a); when W is selected from W-1, B is absent or is C 1 -C 20 When W is selected from W-2,W-3,W-4, B is C 1 -C 20 An alkylene group of (a);
the structural general formula of the silicon-containing monomer I-1b is shown as a formula I-1 b:
in the formula I-1b, R 1 Selected from hydrogen atoms or C 1 -C 20 Alkyl, B is independently C 1 -C 20 An alkylene group of (a);
in formula I-1a and formula I-1b, each Z is independently selected from the structures shown in the following formulas:
in the formula, R 4 Each independently is C 1 -C 20 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Or R is 5 -O-R 6 A group R 5 Is C 1 -C 10 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of, R 6 Is C 1 -C 10 1. Ltoreq. A. Ltoreq.200;
Y 1 and Y 2 Are the same or different and are each independently selected from C 1 -C 20 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 And the structure of formula (I):
R 7 each independently is C 1 -C 20 Alkyl or C 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 An alkylaryl group of (a); r is 8 Each independently is C 1 -C 20 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Or R is alkylaryl or 9 -O-R 10 A group in which R 9 Is C 1 -C 10 Alkyl of (C) 6 -C 20 Aryl of, C 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of, R 10 Is C 1 -C 10 0. Ltoreq. B.ltoreq.200;
the structural general formula of the monomer II is shown as the formula (II):
CH 2 ＝C(R 1 )-P-B-N(R 3 R 4 ) (II)
in the formula (II), P is selected from the group consisting of P-1 and P-2,
-C(O)-O-
P-1
-C(O)-N(R 2 )-
P-2
b is C 1 -C 20 An alkylene group of (a); r 1 And R 2 Each independently of the other being a hydrogen atom or C 1 -C 20 An alkyl group; r 3 And R 4 Each independently of the other is a hydrogen atom, C 1 -C 18 Alkyl, hydroxyethyl or benzyl, or R 3 And R 4 Bonded to and taken together with the nitrogen atom to form a morpholino, piperidino or pyrrolidino group.
2. The silicon-containing polymer of claim 1, wherein the silicon-containing monomer I further comprises silicon-containing monomer I-2,
the structural general formula of the silicon-containing monomer I-2 is shown as a formula I-2:
CH 2 ＝C(R l )-X-B-Z I-2
in the formula I-2, R 1 Selected from hydrogen atoms or C 1 -C 20 Alkyl groups of (a); b is C 1 -C 20 An alkylene group of (a);
x is selected from the group consisting of X-1 and X-2,
-C(O)-O-
X-1
-C(O)-N(R 2 )-
X-2
R 2 selected from hydrogen atoms or C 1 -C 20 Alkyl groups of (a);
z is selected from the structures shown in the following:
in the formula R 4 Each independently is C 1 -C 20 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Or R is 5 -O-R 6 A group R 5 Is C 1 -C 10 Alkyl of (C) 6 -C 20 Aryl of, C 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of, R 6 Is C 1 -C 10 1. Ltoreq. A. Ltoreq.200;
Y 1 and Y 2 Same or different, each is independently selected from C 1 -C 20 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 And an alkylaryl group of formula (I):
R 7 each independently is C 1 -C 20 Alkyl or C 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 An alkylaryl group of (a); r is 8 Each independently is C 1 -C 20 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Or R is alkylaryl or 9 -O-R 10 A group in which R 9 Is C 1 -C 10 Alkyl of (C) 6 -C 20 Aryl of, C 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of, R 10 Is C 1 -C 10 0. Ltoreq. B.ltoreq.200.
3. The silicon-containing polymer according to claim 1 or 2, wherein in Z of formula I-1a and/or formula I-1b and/or formula I-2,
when a is 1, Y 1 And/or Y 2 Is a structure of formula (I), when a is greater than 1 and less than or equal to 200, at least one Y 1 Is a structure of formula (I) and/or at least one Y 2 Is a structure of formula (I):
R 7 each independently is C 1 -C 20 Alkyl or C 6 -C 20 Aryl of, C 7 -C 12 Aralkyl or C 7 -C 12 An alkylaryl group of (a); r 8 Each independently is C 1 -C 20 Alkyl of (C) 6 -C 20 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Or R is alkylaryl or 9 -O-R 10 A group in which R 9 Is C 1 -C 10 Alkyl of (C) 6 -C 20 Aryl of, C 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of, R 10 Is C 1 -C 10 0. Ltoreq. B.ltoreq.200;
preferably, R 7 Each independently is C 1 -C 10 Alkyl or C 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 An alkylaryl group of (a); r 8 Each independently is C 1 -C 10 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Or R is alkylaryl or 9 -O-R 10 A group in which R 9 Is C 1 -C 10 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of, R 10 Is C 1 -C 10 0. Ltoreq. B.ltoreq.100.
4. The silicon-containing polymer of any one of claims 1-3, wherein: also included are the repeating units derived from monomer III,
the structural general formula of the monomer III is shown as formula III:
CH 2 ＝C(R 1 )-G-(R 2 O) q -R 3 III
in the formula III, R 1 Represents a hydrogen atom or a methyl group, R 2 Each independently is C 1 -C 6 Alkylene of (3), preferably C 2 -C 4 Q is an integer of 1 to 50, preferably an integer of 1 to 20; r 3 Represents a hydrogen atom or C 1 -C 20 Alkyl of (2), preferably a hydrogen atom or C 1 -C 10 More preferably a hydrogen atom, C 1 -C 3 Alkyl groups of (a);
wherein G is selected from the group consisting of G-1 and G-2,
-C(O)-O-(CH 2 ) n -
G-1
-C(O)-N(R q )-(CH 2 ) n -
G-2
R 4 represents a hydrogen atom or a methyl group, and n is an integer of 0 to 10, preferably 0 to 5.
5. The silicon-containing polymer of any one of claims 1-4, wherein: the proportion of the silicon-containing monomer I-1a and/or I-1b in the total amount of the silicon-containing monomer I is 1 to 100 percent, 5 to 100 percent, 10 to 100 percent and 50 to 100 percent in percentage by mass; and/or
The content of the repeating units generated by the silicon-containing monomer I in the polymer is 30-90% by mass, preferably 40-85% by mass and more preferably 50-80% by mass; and/or the mass content of the repeating units derived from the monomer II in the polymer is 5 to 65%, preferably 10 to 50%, more preferably 15 to 45%; and/or the mass content of the recurring units derived from the monomer III in the polymer is from 1 to 40%, preferably from 5 to 30%, more preferably from 10 to 25%; and/or
The proportion of the silicon-containing monomer I in the total amount of the monomers is 30-90 percent, preferably 40-85 percent, and more preferably 50-80 percent in percentage by mass; and/or the proportion of the monomer II in the total amount of the monomers is 5-65%, preferably 10-50%, more preferably 15-45%; and/or the proportion of the monomer III in the total amount of the monomers is 1 to 40%, preferably 5 to 30%, more preferably 10 to 25%.
6. The silicon-containing polymer according to any one of claims 1 to 5,
in the silicon-containing monomer I, R 1 And R 2 Selected from hydrogen atoms or methyl groups, B and D being C 1 -C 10 Preferably B and D are C 1 -C 6 An alkylene group of (a); in Z, R 4 Each independently is C 1 -C 10 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Or R is 5 -O-R 6 A group R 5 Is C 1 -C 10 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of, R 6 Is C 1 -C 10 1. Ltoreq. A. Ltoreq.80; r 7 Each independently is C 1 -C 10 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 An alkylaryl group of (a); r 8 Each independently is C 1 -C 10 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Or R is 9 -O-R 10 A group in which R 9 Is C 1 -C 10 Alkyl of (C) 6 -C 10 Aryl of (C) 7 -C 12 Aralkyl or C 7 -C 12 Alkylaryl of, R 10 Is C 1 -C 10 0. Ltoreq. B.ltoreq.80;
in the monomer II, R 1 And R 2 Selected from a hydrogen atom or a methyl group; b is C 1 -C 10 Preferably B is C 1 -C 6 An alkylene group of (a); r 3 And R 4 Are each independently a hydrogen atom, C 1 -C 3 Alkyl, hydroxyethyl or benzyl, or R 3 And R 4 Bonded to and taken together with the nitrogen atom to form a morpholino, piperidino or pyrrolidino group.
7. The silicon-containing polymer of any one of claims 1 to 6,
each Z is independently selected from one or more of the following structures i-1 to i-6:
z is preferably selected from
One or more of;
each R is independently selected from C 1 -C 10 Alkyl radical, C 6 -C 10 Aryl radical, C 7 -C 12 Aralkyl or C 7 -C 12 An alkylaryl group of (a);
me represents methyl, ph represents phenyl; m +1 is 1. Ltoreq. M + 1. Ltoreq.60, preferably 1. Ltoreq. M + 1. Ltoreq.30; p is 0. Ltoreq. P.ltoreq.60, preferably 0. Ltoreq. P.ltoreq.30; q is 0. Ltoreq. Q.ltoreq.60, preferably 0. Ltoreq. Q.ltoreq.30; 1. Ltoreq. X.ltoreq.9, preferably 1. Ltoreq. X.ltoreq.7.
8. The silicon-containing polymer of any one of claims 1 to 7,
the silicon-containing monomer I-1a is selected from CH 2 ＝CH-ph-Si(OSi(CH 3 ) 3 ) 3 (ph represents
)，CH 2 ＝CH-ph-(CH 2 ) 2 Si(OSi(CH 3 ) 3 ) 3 (ph represents
)，CH 2 ＝CH-ph-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Denotes butyl, ph denotes
)(1≤n≤25)CH 2 ＝CH-O-C(O)-NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ，CH 2 ＝CH-O-C(O)-NH-(CH 2 ) 3 -[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Represents butyl) (1. Ltoreq. N. Ltoreq.25), CH 2 ＝CH-O-C(O)-O-(CH 2 ) 3 -Si(OSi(CH 3 ) 3 ) 3 ，CH 2 ＝CH-O-C(O)-O-(CH 2 ) 3 -[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Represents butyl) (1. Ltoreq. N. Ltoreq.25) CH 2 ＝CH-O-C(O)-O-(CH 2 ) 2 -NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ，CH 2 ＝CH-O-C(O)-O-(CH 2 ) 2 -NH-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Represents a butyl group) (1. Ltoreq. N. Ltoreq.25);
and/or
The silicon-containing monomer I-1b is selected from CH 2 ＝CH-C(O)-N[-(CH 2 ) 3 -Si(OSi(CH 3 ) 3 ) 3 ] 2 ，CH 2 ＝CH-C(O)-N[-(CH 2 ) 3 -Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ] 2 ，CH 2 ＝CH-C(O)-N[-(CH 2 ) 3 -(Si(CH 3 ) 2 O) n -Si(CH 3 ) 2 C 4 H 9 ] 2 (C 4 H 9 Represents butyl) (1. Ltoreq. N. Ltoreq.25) CH 2 ＝C(CH 3 )-C(O)-N[-(CH 2 ) 3 -(Si(CH 3 ) 2 O) n -Si(CH 3 ) 2 C 4 H 9 ] 2 (C 4 H 9 Representing a butyl radical) (1. Ltoreq. N. Ltoreq.25)
The silicon-containing monomer I-2 is selected from CH 2 ＝C(CH 3 )-C(O)-O-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ，CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Represents butyl) (1. Ltoreq. N. Ltoreq.25), CH 2 ＝C(CH 3 )C(O)-NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ，CH 2 ＝C(CH 3 )C(O)-NH-(CH 2 ) 3 -[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Represents a butyl group) (1. Ltoreq. N. Ltoreq.25);
monomer II is selected from one or more of dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, N-tert-butylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dipropylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide; and/or
The monomer III is selected from one or more of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and methoxy polyethylene glycol (meth) acrylate, preferably hydroxyethyl methacrylate and 4-hydroxybutyl acrylate.
9. A treating agent comprising the silicon-containing polymer of any one of claims 1 to 8 and a solvent comprising water and/or an organic solvent,
preferably, the organic solvent is one or more of acetone, methyl ethyl ketone, 4-methyl-2-pentanone, ethyl acetate, butyl acetate, N-methyl-2-pyrrolidone, N-dimethylformamide, ethanol, isopropanol, N-propanol, butyl carbitol and dipropylene glycol methyl ether.
10. A method for preparing the treating agent of claim 9, comprising the steps of:
(1) Polymerizing a monomer in an organic solvent to obtain a polymer solution;
optionally, (2) adding water to the polymer solution for dispersion, and then removing the organic solvent, or removing the solvent first and then adding the water dispersion;
optionally, (3) adding an acid to the polymer solution to convert amino groups in the polymer to ammonium salts;
optionally, (4) treating the polymer solution with an aqueous hydrogen peroxide solution to convert the amino groups to nitroxide compounds.
11. Use of the silicon-containing polymer according to any one of claims 1 to 8 or the treatment agent according to claim 9 or the treatment agent prepared by the process according to claim 10 in paper products, natural stone, concrete, fiber fabrics, synthetic leather, non-woven fabrics, asbestos, fur or plastics.
12. The product treated with the silicon-containing polymer according to any one of claims 1 to 8 or the treating agent according to claim 9 or the treating agent prepared by the method according to claim 10, which is paper product, natural stone, concrete, fiber fabric, synthetic leather, non-woven fabric, asbestos, fur or plastic.
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| CN102471419A (en) * | 2009-08-18 | 2012-05-23 | 大金工业株式会社 | Copolymer, treatment agent for paper, and treated paper |
| JP2016183251A (en) * | 2015-03-26 | 2016-10-20 | Jnc株式会社 | Photocurable composition and use thereof |
| CN114573768A (en) * | 2022-03-10 | 2022-06-03 | 北京马普新材料有限公司 | Water-dispersible polymer, composition containing same and application thereof |
| CN114573767A (en) * | 2022-03-10 | 2022-06-03 | 北京马普新材料有限公司 | Copolymer, treating agent for paper, and paper product |
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| CN102046673B (en) * | 2008-06-02 | 2016-02-24 | 旭硝子株式会社 | Multipolymer, its manufacture method, oil-repellent composition and process article thereof |
| EP3015480B1 (en) * | 2013-06-28 | 2019-11-06 | Daikin Industries, Ltd. | Surface treatment agent |
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| CN102471419A (en) * | 2009-08-18 | 2012-05-23 | 大金工业株式会社 | Copolymer, treatment agent for paper, and treated paper |
| JP2016183251A (en) * | 2015-03-26 | 2016-10-20 | Jnc株式会社 | Photocurable composition and use thereof |
| CN114573768A (en) * | 2022-03-10 | 2022-06-03 | 北京马普新材料有限公司 | Water-dispersible polymer, composition containing same and application thereof |
| CN114573767A (en) * | 2022-03-10 | 2022-06-03 | 北京马普新材料有限公司 | Copolymer, treating agent for paper, and paper product |
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