CN114230603A - N- (4-hydroxybutyryl) -gamma-aminopropyl silane, preparation method and application in waterproof aspect of paper-based material - Google Patents
N- (4-hydroxybutyryl) -gamma-aminopropyl silane, preparation method and application in waterproof aspect of paper-based material Download PDFInfo
- Publication number
- CN114230603A CN114230603A CN202111641767.9A CN202111641767A CN114230603A CN 114230603 A CN114230603 A CN 114230603A CN 202111641767 A CN202111641767 A CN 202111641767A CN 114230603 A CN114230603 A CN 114230603A
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- China
- Prior art keywords
- silane
- water
- gamma
- paper
- aminopropyl
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- USTRESFWYYNLAD-UHFFFAOYSA-N OCCCC(NCCC[SiH3])=O Chemical compound OCCCC(NCCC[SiH3])=O USTRESFWYYNLAD-UHFFFAOYSA-N 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000000839 emulsion Substances 0.000 claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 51
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 229920003180 amino resin Polymers 0.000 claims abstract description 18
- 229910000077 silane Inorganic materials 0.000 claims abstract description 17
- 150000001343 alkyl silanes Chemical class 0.000 claims abstract description 14
- 239000012224 working solution Substances 0.000 claims abstract description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 7
- 238000007865 diluting Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000007493 shaping process Methods 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 4
- -1 aminoalkyl silane Chemical compound 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 21
- 125000002091 cationic group Chemical group 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000002736 nonionic surfactant Substances 0.000 claims description 14
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 13
- OBFQBDOLCADBTP-UHFFFAOYSA-N aminosilicon Chemical compound [Si]N OBFQBDOLCADBTP-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- 239000003093 cationic surfactant Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 229920013822 aminosilicone Polymers 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 4
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 4
- 229930188620 butyrolactone Natural products 0.000 claims description 4
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 3
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 3
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- MHNUEQUGTGMGFX-UHFFFAOYSA-N diethoxy-hexadecyl-methylsilane Chemical compound CCCCCCCCCCCCCCCC[Si](C)(OCC)OCC MHNUEQUGTGMGFX-UHFFFAOYSA-N 0.000 claims description 2
- DJVQMRRXRRBRIH-UHFFFAOYSA-N diethoxy-methyl-octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](C)(OCC)OCC DJVQMRRXRRBRIH-UHFFFAOYSA-N 0.000 claims description 2
- CTLDFURRFMJGON-UHFFFAOYSA-N dimethoxy-methyl-(3-piperazin-1-ylpropyl)silane Chemical compound CO[Si](C)(OC)CCCN1CCNCC1 CTLDFURRFMJGON-UHFFFAOYSA-N 0.000 claims description 2
- UBCPEZPOCJYHPM-UHFFFAOYSA-N dimethoxy-methyl-octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](C)(OC)OC UBCPEZPOCJYHPM-UHFFFAOYSA-N 0.000 claims description 2
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 claims description 2
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 2
- AILBOMWJRYLVFG-UHFFFAOYSA-N dodecyl-diethoxy-methylsilane Chemical compound CCCCCCCCCCCC[Si](C)(OCC)OCC AILBOMWJRYLVFG-UHFFFAOYSA-N 0.000 claims description 2
- PELGKMTVNFFDDL-UHFFFAOYSA-N dodecyl-dimethoxy-methylsilane Chemical compound CCCCCCCCCCCC[Si](C)(OC)OC PELGKMTVNFFDDL-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTUQSOKLGFJ-UHFFFAOYSA-N hexadecyl-dimethoxy-methylsilane Chemical compound CCCCCCCCCCCCCCCC[Si](C)(OC)OC MCTWTUQSOKLGFJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 2
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 claims description 2
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000007974 melamines Chemical class 0.000 claims 1
- 150000004756 silanes Chemical class 0.000 claims 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 76
- 239000001993 wax Substances 0.000 description 45
- 229910052710 silicon Inorganic materials 0.000 description 35
- 239000010703 silicon Substances 0.000 description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 34
- 235000013399 edible fruits Nutrition 0.000 description 24
- 230000035699 permeability Effects 0.000 description 14
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 11
- 238000004078 waterproofing Methods 0.000 description 8
- 238000005452 bending Methods 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 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 4
- 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 4
- 239000002585 base Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 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 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JXNGSNLOFNAVJI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]-n,n-dimethylpropan-1-amine Chemical compound CO[Si](C)(OC)CCCN(C)C JXNGSNLOFNAVJI-UHFFFAOYSA-N 0.000 description 2
- 229920003270 Cymel® Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 2
- VSTOSZXVTXTUBH-UHFFFAOYSA-N hexadecylsilicon Chemical compound CCCCCCCCCCCCCCCC[Si] VSTOSZXVTXTUBH-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical group [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- DKYUZAXMDWGNKE-UHFFFAOYSA-N 4-[3-(dimethylamino)propyl-methoxy-methylsilyl]oxybutan-1-amine Chemical compound CN(C)CCC[Si](OCCCCN)(OC)C DKYUZAXMDWGNKE-UHFFFAOYSA-N 0.000 description 1
- IDPRLSSOKIFTOF-UHFFFAOYSA-N 4-hydroxy-N-(3-trimethoxysilylpropyl)butanamide Chemical compound CO[Si](CCCNC(CCCO)=O)(OC)OC IDPRLSSOKIFTOF-UHFFFAOYSA-N 0.000 description 1
- QKDAMFXBOUOVMF-UHFFFAOYSA-N 4-hydroxy-n-(3-triethoxysilylpropyl)butanamide Chemical compound CCO[Si](OCC)(OCC)CCCNC(=O)CCCO QKDAMFXBOUOVMF-UHFFFAOYSA-N 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- KEBRDNWIYNXRKR-UHFFFAOYSA-N dodecyl(dimethoxy)silane Chemical compound CCCCCCCCCCCC[SiH](OC)OC KEBRDNWIYNXRKR-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- XOHGVHRQSJBUHK-UHFFFAOYSA-N dodecylsilicon Chemical compound CCCCCCCCCCCC[Si] XOHGVHRQSJBUHK-UHFFFAOYSA-N 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- FUESFIVIIFEDFI-UHFFFAOYSA-N octadecylsilicon Chemical group CCCCCCCCCCCCCCCCCC[Si] FUESFIVIIFEDFI-UHFFFAOYSA-N 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/485—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms containing less than 25 silicon atoms
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
- D21H17/51—Triazines, e.g. melamine
-
- 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
- D21H17/60—Waxes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paper (AREA)
Abstract
The invention discloses N- (4-hydroxybutyryl) -gamma-aminopropyl silane, a preparation method and application thereof in waterproof treatment of paper-based materials. Firstly, carrying out multi-component hydrolysis polycondensation reaction on self-made N- (4-hydroxybutyryl) -gamma-aminopropylsilane, amino-hydrocarbon silane and long-chain alkyl silane in a water phase, and firstly synthesizing a polysilsesquioxane emulsion HAW which contains C-hydroxyl, amino-hydrocarbon silicon chain links and long-chain alkane silicon chain links and has a dendritic structure; and then, taking the HAW emulsion as a material A and the water-soluble amino resin curing agent as a material B, diluting and uniformly stirring the two materials to prepare a two-component waterproof agent working solution, then soaking the paper-based material into the working solution for 5-10s, and drying and shaping to obtain a waterproof effect, wherein the treated paper-based material is waterproof, breathable and good in stiffness.
Description
Technical Field
The invention belongs to the field of papermaking additives, and particularly relates to a preparation method of N- (4-hydroxybutyryl) -gamma-aminopropyl silane and application thereof in preparation of a two-component water-based silicon wax waterproof agent and waterproof treatment of a paper-based material.
Background
In recent years, social development and technological progress have increased the demand for water-repellent agents for paper. As can be seen from the literature, the main adjuvants that impart water repellency to paper-based materials are: the organic silicon waterproof agent, saponified rosin or dispersed rosin, paraffin emulsion, alkyl ketene dimer AKD emulsion and the like are prepared based on hydroxyl silicone emulsion and hydrogen-containing silicone emulsion, wherein aliphatic waterproof agents such as the saponified rosin or dispersed rosin, the alkyl ketene dimer AKD emulsion and the like are used for internal sizing of papermaking pulp, and the organic silicon emulsion and the paraffin emulsion are used for surface sizing or surface waterproofing of paper. However, researchers find that although traditional organic silicon emulsions, wax emulsions and the like can endow paper or paper-based materials with certain water resistance and liquid infiltration resistance, the water resistance can not meet the new requirements of modern packing paper, fruit bag paper and the like on water resistance. In addition, the aliphatic wax emulsion has low price, and the treated paper base material has hard hand feeling but poor waterproofness; while the paper base material treated by the organic silicon emulsion has better waterproof and air permeability, the specific softening effect of the polydimethylsiloxane chain segment on the paper fiber can cause the stiffness of the treated paper to be reduced.
Disclosure of Invention
In order to solve the problem of poor stiffness of the paper base material treated by the traditional organic silicon, the invention discloses a preparation method of N- (4-hydroxybutyryl) -gamma-aminopropyl silane and application of the silane in preparation of a two-component water-based silicon wax waterproof agent based on two components, wherein the two-component water-based silicon wax waterproof agent is composed of a water-based C-hydroxyl modified cation amino silicon wax emulsion (material A) and an amino resin curing agent (material B).
The long-chain alkyl (also called wax group) is combined with the polyorganosiloxane (short for organic silicon), and simultaneously, the flexible polydimethylsiloxane chain segment is converted into the high-branched dendritic form, so that the advantages of the organic silicon and the wax substances can be integrated on the basis of keeping the original performance characteristics of the organic silicon, the waterproof effect can be further improved, the problems of poor stiffness and the like of a paper-based material treated by the traditional organic silicon can be solved, and the application range of the waterproof agent can be expanded.
Therefore, the invention adopts the following technical scheme:
a preparation method and application of a two-component water-based silicon wax waterproof agent for paper are disclosed, wherein the two-component water-based silicon wax waterproof agent consists of A, B materials; the material A is water-based C-hydroxyl modified cation amino silicon wax emulsion, namely polysilsesquioxane emulsion which contains C-hydroxyl/amino hydrocarbon silicon chain links and long-chain alkyl silicon wax chain links in a main component structure and has a dendritic structure, and is prepared by the multi-element hydrolytic polycondensation reaction of silane containing C-hydroxyl, namely N- (4-hydroxybutyryl) -gamma-aminopropyl alkoxy silane, commercially available amino hydrocarbon silane and long-chain alkyl silane in a water phase; the component B is a water-soluble amino resin curing agent.
The aqueous C-hydroxyl modified cationic amino silicon wax emulsion A can be prepared by a method comprising the following steps:
(1) synthesis of precursor C-hydroxysilane-N- (4-hydroxybutyryl) -gamma-aminopropylalkoxysilane
Taking gamma-aminopropyl silane (APS), weighing GBL according to the weight ratio of APS to butyrolactone (GBL) of about 1:1-1.1, uniformly stirring APS and GBL, heating to 70-80 ℃, stirring and reacting for about 4 hours to obtain colorless-light yellow transparent liquid, namely C-hydroxysilane-N- (4-hydroxybutyryl) -gamma-aminopropyl alkoxy silane (HSi) with the structure shown as formula (I), wherein R ═ CH3Or C2H5；R′＝CH3(ii) a x is 0 or 1.
(2) Preparation of aqueous C-hydroxyl modified cationic amino silicon wax emulsion
First, as long chain alkylsilanes (RSi): aminoalkylsilane (ASi): and (2) sequentially weighing RSi, ASi and HSi according to the mass ratio of 70-90% to 1-10% to 9-20% of C-Hydroxysilane (HSi), heating, stirring, dissolving and uniformly mixing to obtain a mixture D for later use.
Secondly, weighing the cationic/nonionic surfactant accounting for 5-10% of the mass of the D and deionized water accounting for 2.5-10 times of the mass of the D in sequence according to the mass part of the D, stirring, heating to 40-60 ℃ after the surfactant is dissolved into a transparent state, adjusting the pH of the system to be 9-10 by using alkali, and then dropwise adding the D to react for 10-12 hours at the temperature of 40-60 ℃; after the reaction is finished, cooling to room temperature, and adjusting the pH value to be about 5-6 by acid to obtain white emulsion with blue light, namely the water-based C-hydroxyl modified cationic amino silicon wax (HAW) emulsion.
The gamma-aminopropyl silane (APS) is one of gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma-aminopropyl methyl dimethoxy silane and gamma-aminopropyl methyl diethoxy silane.
The long-chain alkyl silane (RSi), also known as silicon wax silane, contains a C in the molecule12-18The long-chain alkyl silane containing 2-3 alkoxy functional groups is selected from one of dodecyl methyl dimethoxy silane, dodecyl trimethoxy silane, hexadecyl methyl dimethoxy silane, hexadecyl trimethoxy silane, octadecyl methyl dimethoxy silane, octadecyl trimethoxy silane, dodecyl methyl diethoxy silane, dodecyl triethoxy silane, hexadecyl methyl diethoxy silane, hexadecyl triethoxy silane, octadecyl methyl diethoxy silane and octadecyl triethoxy silane or a mixture of any two 2-3 functional alkoxy long-chain alkyl silanes.
The amino hydrocarbyl silane (ASi) is silane which contains 1 to 2 primary amino groups and secondary amino groups in the molecule and is connected with 2 to 3 alkoxy groups, one of γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane (KH-550), γ -aminopropylmethyldimethoxysilane, γ -aminopropylmethyldiethoxysilane, N- β -aminoethyl- γ -aminopropylmethyldimethoxysilane (KH-602), N- β -aminoethyl- γ -aminopropyltrimethoxysilane (KH-792), γ -piperazinylpropylmethyldimethoxysilane or N, N-dimethyl- γ -aminopropyl- γ -aminopropylmethyldimethoxysilane may be selected, together with or different from the APS.
The cation/nonionic surfactant is a mixture of a cation long-chain alkyl quaternary ammonium salt surfactant and an aliphatic nonionic surfactant, and the ratio of cation: the mass ratio of the nonionic surfactant is about 3:1-1: 4; the long-chain alkyl quaternary ammonium salt contains C in the structure12-18The organic quaternary ammonium salt of alkyl is one of octadecyl trimethyl ammonium chloride (1831), octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride (1631), hexadecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide and dodecyl benzyl dimethyl ammonium chloride (1227); the nonionic surfactant is one of water-soluble fatty alcohol polyoxyethylene ether, heterogeneous fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether and the like.
The water-soluble amino resin curing agent is etherified melamine such as methyl or butyl which can be used for a water-based system, has good water solubility or water dilutability and low formaldehyde release, the viscosity of the resin is about 500-6000mPa.s, the solid content is about 60-98%, and the water-soluble amino resin can be directly purchased from related manufacturers such as American Cymite company and the like, and the water-soluble amino resin selected by the invention is one of CYMEL385, CYMEL1158 and CYMEL1141 produced by the Cymite company or water-soluble amino resin (Hongke technology corporation, Fujian province) produced by domestic manufacturers and the like.
The application of the two-component water-based silicon wax waterproof agent in the aspect of waterproofing of paper-based materials comprises the following steps: taking a material A and a material B of the two-component water-based silicon wax waterproof agent, and mixing the materials according to the ratio of resin in the material A: and (3) weighing the resin in the B material curing agent according to the mass ratio of 4: 1-3: 1, respectively weighing the A material and the B material, diluting the A material and the B material with water, fully stirring and uniformly mixing the diluted materials to prepare the A + B waterproof working solution, then soaking the paper-based material into the working solution for 5-10s, and drying and shaping to obtain the waterproof effect.
The paper-based material comprises fruit bag paper, paper straws, paper cups, corrugated paper, packing paper, paperboard cartons and the like.
The application performance of the paper base material treated by the two-component water-based silicon wax waterproof agent is evaluated by the following method: taking fruit bag paper as an example. Dredging deviceWater-based: contact Angle (WCA) of water on the surface of fruit bag paperWater (W)) This shows that the water droplet size was 5. mu.L as measured by a static contact angle measuring instrument model JC-2000C 1. Stiffness (expressed as warp x weft bending stiffness): the measurement was carried out by a Derelix paper softness tester, and the slit width was 2cm and the pattern area (warp direction. times. weft direction) was 10X 10cm2The higher the bending rigidity, the higher the paper stiffness. Air permeability (μm/pa.s): by Swiss L&The air permeability of model 166 of W company is measured by a model 166 air permeability tester, and the test area is 50cm2The larger the air permeability value, the better the air permeability of the paper. Water resistance: and pouring 1mL of cold water on the surface of the paper, sealing and storing the paper by using a reversed beaker, standing the paper at room temperature for 12 hours, and observing whether the back of the paper has a leakage phenomenon. Hot water resistance: 2mL of hot water with the temperature of 80-100 ℃ is poured on the surface of the fruit bag paper, the phenomenon of air bubble overflow and leakage on the surface of the paper is observed, and if the air bubbles overflow rapidly, the air permeability of the paper can be intuitively explained.
The invention has the beneficial effects that: based on the characteristic that C-OH is easy to react with amino resin-etherified melamine, and in order to solve the defect that the paper material after the organic silicon emulsion is subjected to water-proof treatment has insufficient stiffness, the invention firstly utilizes the ring-opening reaction of gamma-aminopropyl silane and butyrolactone to synthesize C-hydroxysilane-N- (4-hydroxybutyryl) -gamma-aminopropyl alkoxy silane HSi, and then the HSi, aminoalkyl silane ASi and long-chain alkyl silane RSi are subjected to hydrolysis and copolycondensation, so that polysilsesquioxane resin emulsion, namely aqueous C-hydroxyl modified cationic amino silicon wax HAW emulsion, chemically bonded with aminoalkyl silicon, C-hydroxyl-N- (4-hydroxybutyryl) -gamma-aminopropyl silicon chain links and long-chain alkyl silicon wax chain links in the structure is synthesized; the HAW emulsion is used as a material A, and then the material A is mixed with a water-soluble amino resin, namely etherified melamine B, according to a metering ratio, so that the water-based two-component silicon wax waterproof agent is prepared. Taking paper-based material, fruit bag paper as an example, the application shows that the WCA is the fruit bag paper treated by the double-component waterproof agentWater (W)Reaches 112.3-133.6 degrees and is very stiffThe degree is represented by warp direction and weft direction bending rigidity and reaches 439mN/cm multiplied by 296mN/cm, the air permeability reaches 0.387-0.451 mu m/Pa.s, and the treated paper-based material is breathable, waterproof, good in stiffness and good in comprehensive application effect.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Synthesis of precursor C-hydroxysilane-N- (4-hydroxybutyryl) -gamma-aminopropyl alkoxy silane
Sequentially adding 0.1mol of gamma-aminopropyl silane (APS) and 0.1-0.11mol of butyrolactone (GBL) into a three-necked bottle provided with a thermometer, a stirrer and a reflux condenser, controlling the amount ratio of the APS to the GBL to be 1:1-1.1, stirring and uniformly mixing, heating to 70-80 ℃ and reacting for 4 hours to obtain colorless-light yellow transparent liquid, namely C-hydroxysilane-N- (4-hydroxybutyryl) -gamma-aminopropyl alkoxy silane (HSi) with the structure shown as formula (I), wherein R is CH3Or C2H5；R′＝CH3(ii) a x is 0 or 1. The HSi synthesized in each example and the amounts of the raw materials are listed in table 1.
TABLE 1 summary of raw materials for the synthesis of N- (4-hydroxybutyryl) -gamma-aminopropylalkoxysilane (HSi)
HSi-1: n- (4-hydroxybutyryl) - γ -aminopropyltriethoxysilane; HSi-2: n- (4-hydroxybutyryl) - γ -aminopropylmethyldimethoxysilane; HSi-3: n- (4-hydroxybutyryl) - γ -aminopropyltrimethoxysilane; HSi-4: n- (4-hydroxybutyryl) -gamma-aminopropylmethyldiethoxysilane.
Example II
Example 1
(1) Preparation of aqueous C-hydroxyl modified cationic amino silicon wax emulsion
As long chain alkylsilanes (RSi): aminoalkylsilane (ASi): the mass ratio of C-Hydroxysilane (HSi) is about 70%: 10%: 20%, 7.00g octadecyl trimethoxy silane, 1.0g gamma-aminopropyl triethoxy silane KH-550, 2.0g N- (4-hydroxybutyryl) -gamma-aminopropyl triethoxy silane (HSi-1) are weighed in turn, heated, stirred, dissolved and mixed evenly to obtain 10.0g of mixture in total, which is marked as D and placed in a heat-insulating dropping funnel for standby.
Sequentially weighing 10% by mass of a cationic/nonionic surfactant (1:1, wt/wt, the same below) consisting of octadecyl trimethyl ammonium chloride 1831 and fatty alcohol polyoxyethylene ether AEO-9 and 99.00g by mass of deionized water which is 10 times and 99.00g by mass of D in a four-necked flask provided with a thermometer, a stirrer, a reflux condenser tube and a heat-preservation dropping funnel, stirring and heating, heating to 40 ℃ after the surfactant is dissolved into a transparent state, adjusting the pH of the system to be 9-10 by using ammonia water, dropwise adding D while stirring, controlling the dropwise adding speed to ensure that D is completely dripped within 1-2h, continuously carrying out heat preservation reaction at 40 ℃ for 12h, adjusting the pH to be 5-6 by using acid to obtain a white-emulsion with blue light, namely the emulsion containing N- (4-hydroxybutyryl) -gamma-aminopropyl and gamma-aminopropyl silicon chain links and octadecyl silicon chain links in the structure The silsesquioxane emulsion, referred to as aqueous C-hydroxy modified cationic amino silicone wax emulsion for short, is designated HAW-1 and has a solids content of about 10.0%.
(2) Preparation of two-component water-based silicon wax waterproof agent working solution
30.00g of HAW-1 emulsion with solid content of about 10.0 percent, namely material A1 (containing 3.0g of resin), 1.25g of CYMEL385 aqueous amino resin curing agent with solid content of about 80 percent and viscosity of about 1000mPa.s, namely material B1 are taken, and the resin in the material A1 is controlled: the mass ratio of the resin in the B1 curing agent is about 3: 1; when in material mixing, firstly, taking part of water to dilute 80 percent of CYMEL385 until the solid content is about 10 percent, then, uniformly stirring and mixing A1 and B1, then, adding water to dilute until the content is about 1 to 5 percent, and obtaining the material liquid, namely the waterproof agent working liquid of the two-component water-based silicon wax A1 and B1 for standby.
Example 2
(1) Preparation of aqueous C-hydroxyl modified cationic amino silicon wax HAW-2 emulsion
As long chain alkylsilanes (RSi): aminoalkylsilane (ASi): the mass ratio of C-Hydroxysilane (HSi) is about 90%: 1%: 9%, according to the metering ratio, 9.00g dodecyl dimethoxy silane, 0.10g gamma-aminopropyl triethoxy silane KH-550, 0.9g N- (4-hydroxybutyryl) -gamma-aminopropyl methyl dimethoxy silane (HSi-2) are weighed in turn, heated, stirred, dissolved and mixed evenly to obtain 10.0g of mixture in total, which is marked as D and placed in a heat-preservation dropping funnel for standby.
In a four-necked bottle provided with a thermometer, a stirrer, a reflux condenser tube and a dropping funnel, 10 percent by mass of D, about 1.00g of cationic/nonionic surfactant consisting of 1631 cetyl trimethyl ammonium chloride and O-15 fatty alcohol-polyoxyethylene ether and 2.567 times by mass of D and about 25.67g of deionized water are sequentially weighed, stirred and heated, the surfactant is dissolved into a transparent state, then the temperature is raised to 60 ℃, the pH value of the system is adjusted to be about 9-10 by NaOH aqueous solution, then D is added dropwise while stirring, the dropwise adding speed is controlled to ensure that D is completely dripped within 1-2h, then the mixture is subjected to heat preservation reaction at 60 ℃ for 10h, the pH value is adjusted to be about 5-6 by acid, and white-blue-colored emulsion is obtained, namely the polysilsesquioxane emulsion containing N- (4-hydroxybutyryl) -gamma-aminopropyl and gamma-aminopropyl silicon chain joints and dodecyl silicon wax chain links in the structure, the water-based C-hydroxyl modified cationic amino silicon wax emulsion is called HAW-2 for short, and the solid content is about 30.0 percent.
(2) Preparation of two-component water-based silicon wax waterproof agent working solution
30.00g of HAW-2 with solid content of about 30.0 percent, namely material A2, 2.30g of domestic water-based amino resin (Fujian province, Macro science and technology Co., Ltd.) with solid content of about 98 percent and viscosity of about 6000mPa.s, namely curing agent B2 are taken, and the resin in the material A2 is controlled: the mass ratio of the resin in the B2 curing agent is about 4: 1; during material preparation, firstly, dissolving and diluting 98% of aqueous amino resin by using part of water until the solid content is about 30%, then, uniformly stirring and mixing A2 and B2, adding water to dilute until the content is about 1-5%, and obtaining the feed liquid, namely the working liquid of the two-component aqueous silicon wax waterproof agent A2+ B2 for later use.
Example 3
(1) Preparation of aqueous C-hydroxyl modified cationic amino silicon wax HAW-3 emulsion
As long chain alkylsilanes (RSi): aminoalkylsilane (ASi): the mass ratio of C-Hydroxysilane (HSi) is about 80%: 5%: 15%, according to the metering ratio, weigh 8.00g hexadecyl trimethoxy silane, 0.50g N, N-dimethyl-gamma-aminopropyl methyl dimethoxy silane, 1.50g N- (4-hydroxybutyryl) -gamma-aminopropyl trimethoxy silane (HSi-3) in turn, heat and stir, dissolve and mix evenly, get 10.0g of mixture in total, note D, put in the dropping funnel of keeping warm, spare.
In a four-necked bottle provided with a thermometer, a stirrer, a reflux condenser tube and a dropping funnel, sequentially weighing 5% by mass of D, about 0.50g of cationic/nonionic surfactant consisting of dodecyl dimethyl benzyl ammonium chloride 1227 and fatty alcohol-polyoxyethylene ether O-20 and 5.95 times by mass of D and about 59.5g of deionized water by mass of D, stirring and heating, dissolving the surfactant into a transparent state, heating to 50 ℃, adjusting the pH of the system to be about 9-10 by using ammonia water, then dropwise adding D while stirring, controlling the dropwise adding speed to finish dropwise adding D within 1-2h, continuing to perform heat preservation reaction at 50 ℃ for 11h to obtain white-emulsion with blue light, namely the polysilsesquioxane emulsion containing N- (4-hydroxybutyryl) -gamma-aminopropyl, N-dimethyl-gamma-aminopropyl methyl silicon chain links and hexadecyl silicon wax chain links in the structure, the water-based C-hydroxyl modified cationic amino silicone wax emulsion is called HAW-3 for short, and the solid content is about 15.0 percent.
(2) Preparation of two-component water-based silicon wax waterproof agent working solution
30.00 parts of HAW-3 (material A3) with the solid content of about 15.0 percent, 1.53g of waterborne amino resin CYMEL 303 (curing agent B3) with the solid content of about 98 percent and the viscosity of about 4500mPa.s are taken, and the resin in the material A3 is controlled: the mass ratio of the resin in the B3 curing agent is about 3: 1; when in material mixing, firstly, taking part of water to dilute 98 percent of CYMEL 303 amino resin until the solid content is about 15.0 percent, then, uniformly stirring and mixing A3 and B3, then, adding water to dilute until the content is about 1 to 5 percent, and obtaining the material liquid, namely the waterproof agent working liquid of the two-component water-based silicon wax A3 and B3 for later use.
Example 4
(1) Preparation of aqueous C-hydroxyl modified cationic amino silicon wax HAW-4 emulsion
As long chain alkylsilanes (RSi): aminoalkylsilane (ASi): the mass ratio of C-Hydroxysilane (HSi) is about 75%: 5%: 20%, according to the stoichiometric ratio, weigh 7.50g hexadecyl trimethoxy silane, 0.50g N, N-dimethyl-gamma-aminopropyl methyl dimethoxy silane, 2.0g N- (4-hydroxybutyryl) -gamma-aminopropyl methyl diethoxy silane (HSi-4) sequentially, heat and stir, dissolve and mix, get 10.0g of mixture in total, note D, put in the dropping funnel that keeps warm, spare.
Sequentially weighing 8% by mass of an cationic/nonionic surfactant consisting of hexadecyltrimethylammonium chloride 1631 and fatty alcohol-polyoxyethylene ether O-20 and 4.92 times and 49.2g by mass of deionized water in a four-necked bottle provided with a thermometer, a stirrer, a reflux condenser and a dropping funnel, stirring and heating until the surfactant is dissolved into a transparent state, heating to 55 ℃, adjusting the pH of the system to be 9-10 by using ammonia water, then dropwise adding D while stirring, controlling the dropwise adding speed to finish dropwise adding D within 1-2h, and continuing to perform heat preservation reaction for 12h at 55 ℃ to obtain white-emulsion with blue light, namely the polysilsesquioxane emulsion containing N- (4-hydroxybutyryl) -gamma-aminopropyl methyl silicon, N-dimethyl-gamma-aminopropyl methyl silicon chain links and hexadecyl silicon wax chain links in the structure, the water-based C-hydroxyl modified cationic amino silicone wax emulsion is called HAW-4 for short, and the solid content is about 18.0 percent.
(2) Preparation of two-component water-based silicon wax waterproof agent working solution
30.00 parts of HAW-4 emulsion (A4 material) with the solid content of about 18.0 percent, 2.05g of CYMEL385 aqueous amino resin with the solid content of about 80 percent and the viscosity of about 1000mPa.s (namely B1 curing agent), and controlling the resin in the A4 material: the mass ratio of the resin in the B1 curing agent is about 3.3: 1; when in material mixing, 80 percent of CYMEL385 is firstly diluted by part of water until the solid content is about 18.0 percent, then A4 and B1 are uniformly stirred, water is added for dilution until the content is about 1 to 5 percent, and the obtained material liquid is the working liquid of the double-component water-based silicon wax A4 and B1 water-proofing agent for standby.
And (3) application performance testing: take paper-based material-fruit bag paper as an example. Taking the A + B water repellent working solution prepared in the examples 1-4 and with the solid content of 3%, respectively soaking fruit bag paper into the water repellent working solution prepared in the examples 1-4 for 5-10s, taking out, squeezing out multipurpose water by a padder, then carrying out forced air drying at 80-100 ℃ for 10min, then carrying out setting at 160 ℃ for 30s, balancing the obtained paper at the room temperature of 25 +/-2 ℃ and RH being 48% for 24h, and carrying out performance measurement:
contact of water on the surface of the paper of the fruit bagAngle WCAWater (W)The water droplet size was 5. mu.L as measured by a JC-2000C1 type static contact angle measuring apparatus. Stiffness of the fruit bag paper: the bending stiffness was expressed in terms of warp direction x weft direction, and measured by a Derelix paper softness tester, and the slit width was 2cm and the pattern area (warp direction x weft direction) was 10 x 10cm2. Paper air permeability (μm/pa.s): by Swiss L&The air permeability of model 166 of W company is measured by a model 166 air permeability tester, and the test area is 50cm2. Water resistance: placing 1mL of cold water on the surface of the fruit bag paper, sealing and storing the fruit bag paper by using an inverted beaker, placing the fruit bag paper at room temperature for 12 hours, and observing whether the back of the paper has a leakage phenomenon. Hot water resistance: 2mL of hot water with the temperature of 80-100 ℃ is poured on the surface of the fruit bag paper, and the phenomenon of air bubble overflow and leakage on the surface of the paper is observed. Meanwhile, blank bag paper without treatment is used as reference 1, and the measurement is carried out by the same method. In addition, a commercially available organic silicon emulsion waterproof agent (main components of hydroxyl silicon emulsion and hydrogen-containing silicon emulsion) for papermaking with the solid content of about 30 percent is used as a reference 2, the waterproof agent is diluted by water to the solid content of about 3 percent to prepare a waterproof working solution, then fruit bag paper is soaked into the working solution for 5 to 10 seconds, and then the drying, shaping and performance measurement are carried out in the same way as in examples 1 to 4, and the organic silicon emulsion waterproof agent is also used as a reference of the invention. All test results are shown in table 2.
TABLE 2 comparison of the Performance of the two-component aqueous Silicone wax waterproofing agent treated fruit bag paper and the reference
Reference 1- -blank untreated fruit bag paper; reference 2-fruit bag paper treated with commercial silicone waterproofing agent. Excellent-air bubbles overflow from the surface of the paper, but no leakage phenomenon is found on the back surface of the paper after 30 min; o-air bubbles overflow from the surface of the paper, but a certain amount of steam leaks from the back of the paper after 30 min; x-air bubbles overflow from the paper surface, but a large amount of water vapor permeates from the back of the paper after 1-2 min.
From Table 2, it can be seen that the WCA, the fruit bag paper treated with the two-component aqueous silicone wax waterproofing agent of examples 1-4 of the present invention, is comparable to the reference 1, blank untreated fruit bag paperWater (W)Increase the bending rigidity of the warp and weft of the fruit bag paper, enhance the water resistance and increase the bending rigidity of the warp and weft of the fruit bag paperAlthough the air permeability is slightly reduced compared with the blank, the paper still has better air permeability; in contrast, WCA on the surface of the paper was found in the case of the paper of bags waterproofed with the two-component silicone wax of examples 1 to 4 of the present invention, as compared with the paper of reference 2, which is a commercially available silicone emulsionWater (W)The stiffness and the hot water resistance of the fruit bag paper are better than those of fruit bag paper treated by a commercial organosilicon waterproofing agent, the difference between the water resistance and the water resistance is not great, but the air permeability of the fruit bag paper treated by the commercial organosilicon waterproofing agent is slightly better. Obviously, the double-component silicon wax waterproof agent has the effect of improving the water resistance, water resistance and stiffness of paper.
Claims (10)
- N- (4-hydroxybutyryl) - γ -aminopropylsilane having the structural formula:
wherein R is CH3Or C2H5；R′＝CH3(ii) a x is 0 or 1. - 2. The process for preparing N- (4-hydroxybutyryl) - γ -aminopropylsilane according to claim 1, comprising the steps of:uniformly mixing gamma-aminopropyl silane and butyrolactone according to a molar ratio of 1 (1-1.1), and stirring for reaction at 70-80 ℃ to obtain N- (4-hydroxybutyryl) -gamma-aminopropyl silane;the gamma-aminopropyl silane is one of gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma-aminopropyl methyl dimethoxy silane and gamma-aminopropyl methyl diethoxy silane.
- 3. A preparation method of a water-based C-hydroxyl modified cationic amino silicone wax emulsion is characterized by comprising the following steps:according to the formula of long-chain alkyl silane: aminoalkyl silane: the mass ratio of N- (4-hydroxybutyryl) -gamma-aminopropylsilane (70-90) to (1-10) to (9-20) in claim 1, heating, stirring, dissolving and uniformly mixing to obtain a mixture D for later use;dissolving a cationic surfactant and a nonionic surfactant which are 5-10% of the mass of the mixture D in deionized water 2.5-10 times of the mass of the mixture D, heating to 40-60 ℃, adjusting the pH of the system to 9-10, then dropwise adding the mixture D, and carrying out heat preservation reaction at 40-60 ℃ for 10-12 h; after the reaction is finished, cooling to room temperature, and adjusting the pH value to 5-6 to obtain aqueous C-hydroxyl modified cationic amino silicone wax emulsion;the long-chain alkyl silane contains 1C in the molecule12-18Long chain alkyl and 2-3 alkoxy functional silanes;the amino hydrocarbyl silane is silane which contains 1-2 primary amino groups and/or secondary amino groups in the molecule and 2-3 alkoxy groups;the cationic surfactant contains C12-18Cationic long chain alkyl quaternary ammonium salt surfactants of alkyl groups; the nonionic surfactant is aliphatic nonionic surfactant.
- 4. The method of claim 3, wherein the long chain alkyl silane is one or more of dodecyl methyl dimethoxy silane, dodecyl trimethoxy silane, hexadecyl methyl dimethoxy silane, hexadecyl trimethoxy silane, octadecyl methyl dimethoxy silane, octadecyl trimethoxy silane, dodecyl methyl diethoxy silane, dodecyl triethoxy silane, hexadecyl methyl diethoxy silane, hexadecyl triethoxy silane, octadecyl methyl diethoxy silane, and octadecyl triethoxy silane.
- 5. The method as claimed in claim 3, wherein the aminoalkyl silane is one of γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, γ -aminopropylmethyldimethoxysilane, γ -aminopropylmethyldiethoxysilane, N- β -aminoethyl- γ -aminopropylmethyldimethoxysilane, N- β -aminoethyl- γ -aminopropyltrimethoxysilane, γ -piperazinylpropylmethyldimethoxysilane, N-dimethyl- γ -aminopropyl- γ -aminopropylmethyldimethoxysilane.
- 6. The method according to claim 3, wherein the mass ratio of the cationic surfactant to the nonionic surfactant is 3:1 to 1: 4.
- 7. The method according to claim 3, wherein the cationic surfactant is C12-18Long chain alkyl trimethyl ammonium chloride, C12-18One of long-chain alkyl trimethyl ammonium bromide and dodecyl dimethyl benzyl ammonium chloride; the nonionic surfactant is one of water-soluble fatty alcohol-polyoxyethylene ether, heterogeneous fatty alcohol-polyoxyethylene ether, nonylphenol polyoxyethylene ether and octylphenol polyoxyethylene ether.
- 8. An aqueous C-hydroxy modified cationic aminosilicone wax emulsion prepared by the process of any of claims 3 to 7.
- 9. A two-component water-based silicone wax waterproof agent composition for paper, which is characterized by comprising the water-based C-hydroxyl modified cationic amino silicone wax emulsion of claim 8 and a water-soluble amino resin curing agent;the water-soluble amino resin curing agent is methylated melamine or butylated melamine, the viscosity is 500-6000mPa.s, and the solid content is 60-98%;the mass ratio of the water-based C-hydroxyl modified cationic amino silicon wax emulsion to the water-soluble amino resin curing agent is (4-3) to 1.
- 10. A method of constructing the composition of claim 9, comprising the steps of:respectively weighing the water-based C-hydroxyl modified cationic amino silicon wax emulsion and the water-soluble amino resin curing agent, diluting with water respectively, stirring and mixing uniformly to prepare a double-component waterproof agent working solution, then soaking the paper-based material into the working solution for 5-10s, and drying and shaping to obtain the waterproof effect.
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| CN202111641767.9A Pending CN114230603A (en) | 2021-12-29 | 2021-12-29 | N- (4-hydroxybutyryl) -gamma-aminopropyl silane, preparation method and application in waterproof aspect of paper-based material |
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| US5997954A (en) * | 1998-07-15 | 1999-12-07 | Dow Corning Corporation | Method of rendering substrates water repellent using hyperbranched polymers containing silicon atoms |
| US6001945A (en) * | 1998-07-15 | 1999-12-14 | Dow Corning Corporation | Hyperbranched polymers containing silicon atoms |
| JP2015131412A (en) * | 2014-01-10 | 2015-07-23 | キヤノン株式会社 | Recording medium |
| CN110183965A (en) * | 2019-06-25 | 2019-08-30 | 江西省科学院应用化学研究所 | A kind of preparation method of novel aqueous organic silicon stone protective agent |
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| US5997954A (en) * | 1998-07-15 | 1999-12-07 | Dow Corning Corporation | Method of rendering substrates water repellent using hyperbranched polymers containing silicon atoms |
| US6001945A (en) * | 1998-07-15 | 1999-12-14 | Dow Corning Corporation | Hyperbranched polymers containing silicon atoms |
| JP2015131412A (en) * | 2014-01-10 | 2015-07-23 | キヤノン株式会社 | Recording medium |
| CN110183965A (en) * | 2019-06-25 | 2019-08-30 | 江西省科学院应用化学研究所 | A kind of preparation method of novel aqueous organic silicon stone protective agent |
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