CN112574381A - Formaldehyde scavenging agent for tanning and preparation method thereof - Google Patents
Formaldehyde scavenging agent for tanning and preparation method thereof Download PDFInfo
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- CN112574381A CN112574381A CN202011420394.8A CN202011420394A CN112574381A CN 112574381 A CN112574381 A CN 112574381A CN 202011420394 A CN202011420394 A CN 202011420394A CN 112574381 A CN112574381 A CN 112574381A
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- formaldehyde scavenger
- titanium dioxide
- tanning
- nano titanium
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 239000002516 radical scavenger Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000010985 leather Substances 0.000 claims abstract description 31
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004970 Chain extender Substances 0.000 claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 7
- 150000003077 polyols Chemical class 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229920000768 polyamine Polymers 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 5
- 239000012948 isocyanate Substances 0.000 claims abstract description 5
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- -1 polybutylene adipate Polymers 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 150000003384 small molecules Chemical group 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 229920003180 amino resin Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- NTZRDKVFLPLTPU-UHFFFAOYSA-N CC[Na] Chemical compound CC[Na] NTZRDKVFLPLTPU-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical class C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001365 aminolytic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 102000035118 modified proteins Human genes 0.000 description 1
- 108091005573 modified proteins Proteins 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C15/00—Apparatus for chemical treatment or washing of hides, skins, or leather
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a formaldehyde scavenger for tanning and a preparation method thereof, wherein the formaldehyde scavenger comprises the following components in parts by weight: 1-10 parts of polyol, 0.1-2 parts of modified nano titanium dioxide, 0.2-5 parts of isocyanate, 0.05-1 part of micromolecular chain extender, 0.05-1 part of hydrophilic chain extender, 0.05-1 part of neutralizer, 0.01-1 part of graphene oxide, 0.05-1 part of polyamine compound and 2-80 parts of water; the formaldehyde scavenger is mainly used for a leather-making water field workshop section, and the nano titanium dioxide and polyurethane in the formaldehyde scavenger enter the leather together and are fixed in the leather in a cross-linking manner with the leather, so that free formaldehyde in the leather can be removed for a long time.
Description
Technical Field
The invention relates to the technical field of leather production, in particular to a formaldehyde scavenger for leather making and a preparation method thereof.
Background
In the process of processing and manufacturing leather, chemicals such as modified aldehyde, oxazolidine, amino resin, organic phosphine, modified protein and the like are synthesized by taking formaldehyde as a precursor, the chemicals contain a certain amount of formaldehyde, and the formaldehyde is brought into finished leather through tanning, retanning, filling, finishing and the like and is slowly released in the process of long-term use. In recent years, green consumption is gradually becoming a consumption trend at home and abroad, strict limits are provided on formaldehyde control, European Union is clearly specified in European Union chemical registration, evaluation, authorization and restriction regulations, and the formaldehyde content of leather and products thereof is not higher than 150 mg/kg. The national mandatory standards also specify: the formaldehyde content in the infant product is not higher than 20mg/kg, the formaldehyde content in the infant product is not higher than 75mg/kg when the infant product is directly contacted, and the formaldehyde content in the infant product is not higher than 300mg/kg when the infant product is not directly contacted. Therefore, the control and elimination of formaldehyde in leather products are of great significance to the sustainable development of the tanning industry and to the health of consumers.
At present, leather chemicals at home and abroad have three main components of formaldehyde catching agents and formaldehyde scavenging agents, namely proteins, amino and photocatalytic materials. But the adsorption capacity of the protein formaldehyde is limited, when the consumption is excessive, the finished leather board is hard and is easy to nourish bacteria to mildew; the formaldehyde adsorption capacity of the amino chemicals is strong, but the amino substances are limited by the synthesis process, the materials carry a certain amount of formaldehyde, and the formaldehyde is easily released slowly in the subsequent use, so that the health of a user is influenced; the photocatalytic material has the advantages of strong formaldehyde removal capability, long duration and the like, but the nano photocatalytic material has extremely poor dispersibility in aqueous solution, can only be added in a small amount in a coating workshop section, cannot be applied to a tanning water field workshop section to add the nano photocatalytic material into leather, and is difficult to rapidly remove formaldehyde in the leather.
Disclosure of Invention
The embodiment of the application provides a formaldehyde scavenger for leather making and a preparation method thereof, solves the problems of poor adsorption force and poor dispersibility in water of the formaldehyde scavenger in the prior art, realizes the beneficial effect of adsorbing formaldehyde in leather, and is mainly used for a leather-making water field workshop section.
The embodiment of the application provides a formaldehyde scavenger for tanning, which comprises the following components in parts by weight:
further, the modified nano titanium dioxide comprises the following components in parts by weight:
1-10 parts of nano titanium dioxide
0.01-1 part of amino silane coupling agent
0.01-1 part of epoxy silane coupling agent.
Further, the nano titanium dioxide is anatase titanium dioxide, and the particle size of the nano titanium dioxide is 10-100 nm.
Further, the isocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate and toluene diisocyanate.
Further, the polyol is one or more of polypropylene glycol, polyethylene glycol, polytetrahydrofuran ether, polybutylene adipate diol and polycaprolactone diol.
Further, the small-molecule chain extender is one or more of ethylene glycol, propylene glycol, butanediol, diethylene glycol and triethylene glycol.
Further, the hydrophilic chain extender is one or more of dimethylolpropionic acid, dimethylolbutyric acid, tartaric acid, citric acid, 2, 4-diaminobenzene sulfonic acid, ethylene diamine ethyl sodium sulfonate, carboxyl-containing half-ester dihydric alcohol, N-methyldiethanolamine and triethylamine.
Further, the polyamine compound is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
A preparation method of a formaldehyde scavenger for tanning comprises the following steps:
(1) adding 1-10 parts of nano titanium dioxide into a reaction container, adding 0.01-1 part of aminosilane coupling agent, 0.01-1 part of epoxy silane coupling agent, 10-100 parts of water and 20-200 parts of ethanol, stirring and dispersing, adjusting the pH to 4-12, then performing ultrasonic dispersion for 3-30min, reacting at the temperature of 20-60 ℃ for 1-10h, filtering, washing and drying to obtain modified nano titanium dioxide;
(2) dehydrating 1-10 parts of polyol, adding the dehydrated polyol into a reactor, adding 0.2-5 parts of isocyanate, prepolymerizing at 70-100 ℃ for 0.5-4h, cooling to 60-70 ℃, adding 0-8 parts of acetone for dilution, and adding 0.05-1 part of micromolecular chain extender, and reacting for 2-6 h; adding 0.05-1 part of hydrophilic chain extender, reacting for 0.5-4h, cooling to 40-60 ℃, and adding 0.05-1 part of neutralizing agent for 10-100 min; controlling the temperature to be 25-45 ℃, adding 0.1-2 parts of modified nano titanium dioxide and 0.01-1 part of graphene oxide, and stirring at a high speed for reaction for 10-120 min; controlling the temperature to be 25-45 ℃, adding 2-80 parts of water while stirring at a high speed, and emulsifying and dispersing for 0.5-4 h; adding 0.01-1 part of polyamine compound, controlling the temperature at 25-45 ℃, stirring and reacting for 10-120min, and removing acetone in the emulsion to obtain the formaldehyde scavenger.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
1. the formaldehyde scavenger polyamine compound and the graphene oxide can serve as a cross-linking agent and a formaldehyde catching agent in a system, so that formaldehyde in leather is caught, and the formaldehyde scavenging effect in the formaldehyde scavenger is enhanced.
2. The formaldehyde scavenger is mainly used for a leather-making water field workshop section, and the nano titanium dioxide and polyurethane in the formaldehyde scavenger enter the leather together and are fixed in the leather in a cross-linking manner with the leather, so that free formaldehyde in the leather can be removed for a long time.
3. The silane coupling agent in the formaldehyde scavenger modifies the surface of the nano titanium dioxide, so that the compatibility and the dispersibility of the nano titanium dioxide in polyurethane can be improved, the silane coupling agent can also react with active groups on skin collagen fibers in leather to fix the nano titanium dioxide on the skin fibers, and the water washing resistance of the formaldehyde scavenger is improved.
4. The acetone in the formaldehyde scavenger can adjust the viscosity in a system, prevents the viscosity of the system from being too high, does not participate in the reaction of the system, and is removed after the reaction of the system is finished.
5. The neutralizing agent can be used for adjusting the acidity of the system, and when the hydrophilic chain extender is acidic, such as dimethylolpropionic acid, organic alkali is needed for neutralization; when the hydrophilic chain extender is basic, it is necessary to neutralize it with an organic acid to maintain the pH of the system at neutral.
Detailed Description
In order to better understand the technical solutions, the technical solutions will be described in detail with reference to the description and the specific embodiments.
Example 1:
a preparation method of a formaldehyde scavenger for tanning comprises the following steps:
(1) adding 5 parts of anatase titanium dioxide into a reaction container, adding 0.4 part of aminosilane coupling agent, 0.1 part of epoxy silane coupling agent, 50 parts of water and 100 parts of ethanol, stirring and dispersing, adjusting the pH value to 10, and then ultrasonically dispersing for 5min (t is t)1) At 30 ℃ (T)1) At a temperature of 5h (t)2) Filtering, washing and drying to obtain the modified nano titanium dioxide.
(2) Taking 3 parts of polytetramethylene glycol, dehydrating, adding into a reactor, and adding0.8 part of isophorone diisocyanate, 80 ℃ (T)2) Prepolymerization for 2h (t)3). Cooling to 65 deg.C (T)3) Diluting with 0.4 part of acetone, adding 0.3 part of butanediol, and reacting for 4h (t)4). 0.1 part of dimethylolpropionic acid is added and the reaction is carried out for 2h (t)5). Cooling to 50 deg.C (T)4) Adding 0.1 part of triethylamine (neutralizing agent) to neutralize for 30min (t)6). Controlling the temperature to be 40 ℃ (T)5) Adding 0.2 part of modified nano titanium dioxide and 0.05 part of graphene oxide, and stirring at high speed for reaction for 60min (t)7). Controlling the temperature to be 40 ℃ (T)6) Adding 12 parts of water while stirring at high speed, emulsifying and dispersing for 1h (t)8). Adding 0.05 part of ethylenediamine, and controlling the temperature to be 30 ℃ (T)7) Stirring and reacting for 30min (t)9) And removing acetone in the emulsion to obtain the formaldehyde scavenger.
Example 2:
a preparation method of a formaldehyde scavenger for tanning is the same as that adopted in example 1, and the components and conditions are different, and are specifically shown in the following table 1:
TABLE 1
Example 3:
a preparation method of a formaldehyde scavenger for tanning, which is the same as the method adopted in the example 1, and has different components and conditions, and the preparation method is specifically shown in the following table 2:
TABLE 2
Example 4:
a method of making leather comprising the steps of:
taking conventional wet blue leather, wringing, shaving, weighing, softening, retanning, neutralizing according to a conventional process, and then filling, wherein the filling process is as follows:
50% of water was added to the drum, 10% of formaldehyde scavenger (from example 1) was added, the temperature was controlled at 30 ℃ and the drum was rotated for 40min, 3% of acrylic resin retanning agent TP340(ALPA leather chemical Co., Ltd.), 3% of acrylic resin retanning agent RE (BASF Co., Ltd.), and rotated for 30min, 3% of vegetable tanning agent ME (Jinfeng leather chemical Co., Ltd.), 1% of synthetic tanning agent T-M (BASF Co., Ltd.), 2% of synthetic tanning agent OS (Langsheng chemical Co., Ltd.), 3% of amino resin tanning agent HB (Toepler Co., Ltd.), 2% of amino resin tanning agent DCT (Staal leather chemical Co., Ltd.), 3% of vegetable tanning agent ME (Jinfeng leather chemical Co., Ltd.), 2% of dye and rotated for 120 min. Adding 150% water and 0.75% formic acid, controlling temperature at 50 deg.C, rotating for 20min, adding 0, 75% formic acid, rotating for 30min, and draining.
And (3) adding grease, color registering, drying and finishing according to a conventional process, and detecting the performance of the leather.
The formaldehyde scavengers obtained in example 1, example 2 and example 3 were tested to obtain the experimental data shown in table 3, and the leathers obtained in example 2 were tested to obtain the experimental data shown in table 4:
TABLE 3
TABLE 4
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (9)
1. The formaldehyde scavenger for tanning is characterized by comprising the following components in parts by weight:
2. the formaldehyde scavenger for tanning according to claim 1, wherein the modified nano titanium dioxide comprises the following components in parts by weight:
1-10 parts of nano titanium dioxide
0.01-1 part of amino silane coupling agent
0.01-1 part of epoxy silane coupling agent.
3. The formaldehyde scavenger for tanning as claimed in claim 2, wherein the nano titanium dioxide is anatase titanium dioxide, and the particle size of the nano titanium dioxide is 10-100 nm.
4. The formaldehyde scavenger for tanning according to claim 1, wherein the isocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate, and toluene diisocyanate.
5. The formaldehyde scavenger for leather making according to claim 1, wherein the polyol is one or more of polypropylene glycol, polyethylene glycol, polytetrahydrofuran ether, polybutylene adipate diol, and polycaprolactone diol.
6. The formaldehyde scavenger for tanning according to claim 1, wherein the small molecule chain extender is one or more of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol and triethylene glycol.
7. The formaldehyde scavenger for tanning according to claim 1, wherein the hydrophilic chain extender is one or more of dimethylolpropionic acid, dimethylolbutyric acid, tartaric acid, citric acid, 2, 4-diaminobenzene sulfonic acid, sodium ethylene diamine ethanesulfonate, carboxyl-containing half ester diol, N-methyldiethanolamine, and triethylamine.
8. The formaldehyde scavenger for leather making according to claim 1, wherein the polyamine compound is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
9. A preparation method of a formaldehyde scavenger for tanning is characterized by comprising the following steps:
(1) adding 1-10 parts of nano titanium dioxide into a reaction container, adding 0.01-1 part of aminosilane coupling agent, 0.01-1 part of epoxy silane coupling agent, 10-100 parts of water and 20-200 parts of ethanol, stirring and dispersing, adjusting the pH to 4-12, then performing ultrasonic dispersion for 3-30min, reacting at the temperature of 20-60 ℃ for 1-10h, filtering, washing and drying to obtain modified nano titanium dioxide;
(2) dehydrating 1-10 parts of polyol, adding the dehydrated polyol into a reactor, adding 0.2-5 parts of isocyanate, prepolymerizing at 70-100 ℃ for 0.5-4h, cooling to 60-70 ℃, adding 0-8 parts of acetone for dilution, and adding 0.05-1 part of micromolecular chain extender, and reacting for 2-6 h; adding 0.05-1 part of hydrophilic chain extender, reacting for 0.5-4h, cooling to 40-60 ℃, and adding 0.05-1 part of neutralizing agent for 10-100 min; controlling the temperature to be 25-45 ℃, adding 0.1-2 parts of modified nano titanium dioxide and 0.01-1 part of graphene oxide, and stirring at a high speed for reaction for 10-120 min; controlling the temperature to be 25-45 ℃, adding 2-80 parts of water while stirring at a high speed, and emulsifying and dispersing for 0.5-4 h; adding 0.01-1 part of polyamine compound, controlling the temperature at 25-45 ℃, stirring and reacting for 10-120min, and removing acetone in the emulsion to obtain the formaldehyde scavenger.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4106897A (en) * | 1974-04-04 | 1978-08-15 | Bayer Aktiengesellschaft | Leather tanning with oligourethanes |
| CN110343460A (en) * | 2019-07-29 | 2019-10-18 | 湖南工程学院 | A kind of antibacterial is except methanal paint and preparation method thereof |
| CN111471385A (en) * | 2020-03-27 | 2020-07-31 | 江苏华彩化学科技有限公司 | Aqueous environment-friendly coating for removing formaldehyde and preparation method thereof |
| CN111620995A (en) * | 2020-05-20 | 2020-09-04 | 温州大学 | Preparation method of polyurethane for photocatalytic degradation of formaldehyde |
-
2020
- 2020-12-08 CN CN202011420394.8A patent/CN112574381A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4106897A (en) * | 1974-04-04 | 1978-08-15 | Bayer Aktiengesellschaft | Leather tanning with oligourethanes |
| CN110343460A (en) * | 2019-07-29 | 2019-10-18 | 湖南工程学院 | A kind of antibacterial is except methanal paint and preparation method thereof |
| CN111471385A (en) * | 2020-03-27 | 2020-07-31 | 江苏华彩化学科技有限公司 | Aqueous environment-friendly coating for removing formaldehyde and preparation method thereof |
| CN111620995A (en) * | 2020-05-20 | 2020-09-04 | 温州大学 | Preparation method of polyurethane for photocatalytic degradation of formaldehyde |
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