CN104693404A - Functional waterborne polyurethane leather finishing agent and preparation method thereof - Google Patents
Functional waterborne polyurethane leather finishing agent and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/30—Low-molecular-weight compounds
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- C08G18/348—Hydroxycarboxylic acids
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- 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
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- C08G18/44—Polycarbonates
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- 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
- C08G18/4833—Polyethers containing oxyethylene units
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- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- 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
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
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- 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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention provides a functional waterborne polyurethane leather finishing agent and a preparation method thereof. The method includes the steps that firstly, doping type surface-PEGlated nanometer titanium dioxide is prepared through a solvent-thermal method and then dissolved in polymer polyhydric alcohol, and modified nanometer titanium dioxide with visible-light responses is introduced to polyurethane through in-situ polymerization. The waterborne polyurethane leather finishing agent prepared through the method contains the nanometer titanium dioxide with the visible-light responses and is high in sterilization and mould-proof capacity due to the fact that visible light in sunlight can be completely utilized; PEG is grafted to the surface of the nanometer titanium dioxide, and in combination with photocatalytic activity of the nanometer titanium dioxide and the excellent protein adsorption resistance of the PEG, the self-cleaning function of a polyurethane coating is remarkably improved. Good dispersion of the nanometer titanium dioxide in polyurethane can be effectively promoted, the heat-resisting stability and mechanical strength of the coating are improved, and meanwhile the transparency of finishing materials is kept.
Description
Technical field
The present invention relates to self-cleaning material and aqueous polyurethane coating material for leather research field, be specifically related to a kind of functional Aqueous Polyurethane Leather Finishing Agent and preparation method thereof with photocatalytic degradation surface organic pollutant, fungus and mildew resistance performance.
Background technology
Self-cleaning material has environmental protection and saves the advantages such as cleaning charge, is more and more subject to the favor in market, is also subject to the extensive concern of academia.At present, based on different automatically cleaning principles, two class automatically cleaning finishing agents are developed.One class is super-hydrophobic automatic cleaning finishing agent, and it is rolled by water droplet and takes away dust, realizes the self-cleaning function being similar to lotus leaf.But there is complicated process of preparation, prepare the problems such as area is little, poor mechanical property, oil-proofness pollutent ability in this kind of material, lacks actual use value.Another kind of is automatically cleaning finishing agent based on inorganic photocatalytic semiconductor material, the most typically nano titanium oxide (TiO
2) coating and decorating material.
Urethane is one of outstanding synthetic resins of over-all properties, has defined the material family of a multi items, multi-series at present.Solvent type polyurethane coating kind is numerous, of many uses, occupies very important status in coating products, but solvent borne polyurethane can cause very large destruction to environment.The research of aqueous polyurethane starts from the 1950's, starts the aqueous polyurethane that suitability for industrialized production is used as hide finishes the seventies.After the nineties, along with the reinforcement of people's environmental consciousness and environmental regulation, the research and development of eco-friendly aqueous polyurethane come into one's own day by day, and its application constantly expands to the field such as coating, tamanori by hide finishes, progressively captures the market of solvent borne polyurethane.
First the present invention utilizes solvent-thermal method to prepare the nano-TiO of doping type, surface PEG
2, be then dissolved in polymer polyatomic alcohol, adopt situ aggregation method obtained containing above-mentioned modified Nano TiO
2polyurethane decorative paint for leather, solve nano-TiO
2dispersion problem.While not affecting coating and decorating material film forming properties, utilize nano-TiO
2photocatalytic activity and nano effect, make polyurethane decorative paint for leather have the performances such as photocatalytic self-cleaning, anti-ultraviolet ageing and fungus and mildew resistance.
Summary of the invention
The object of the invention is to provide a kind of functional Aqueous Polyurethane Leather Finishing Agent and preparation method thereof.Situ aggregation method is adopted to have visible light-responded nano-TiO
2be dispersed in aqueous polyurethane, the obtained Aqueous Polyurethane Leather Finishing Agent with automatically cleaning, fungus and mildew resistance and anti-ultraviolet ageing function.
In order to achieve the above object, this invention takes following technical scheme:
The functional Aqueous Polyurethane Leather Finishing Agent of one of the present invention, its preparation process comprises the nano-TiO of doping type, surface PEG
2preparation and containing above-mentioned nano-TiO
2preparation two steps of urethane.
The nano-TiO of doping type of the present invention, surface PEG
2preparation method as follows:
(1) precursor of titanium is joined in polyoxyethylene glycol, high-speed stirring, reaction for some time, obtain viscous solution;
(2) concentrated hydrochloric acid is added to above-mentioned viscous solution, pH is regulated to be 2 ~ 4, add the compound containing doped element, after continuing to stir for some time, proceed in autoclave, in 140 ~ 180 DEG C of reaction 4 ~ 8h, through absolute ethanol washing, centrifugal, dry, obtain the nano titanium oxide of doping type, surface PEG.
The molecular weight ranges of polyoxyethylene glycol recited above is 200 ~ 8000.
The precursor of titanium recited above is one or more mixtures of tetrabutyl titanate, titanium isopropylate, tetraethyl titanate.
Doped element recited above is one or more in Fe, Cu, Mn, Ag, N, S, I.
Nano-TiO containing doping type, surface PEG of the present invention
2functional Aqueous Polyurethane Leather Finishing Agent preparation method as follows:
(1) be dissolved in polymer polyatomic alcohol by the nano titanium oxide of doping type, surface PEG, vacuum hydro-extraction 2 ~ 5h at 110 ~ 120 DEG C, afterwards temperature of reaction is down to 70 ~ 80 DEG C, vacuum is converted to nitrogen, adds solvents tetrahydrofurane;
(2) in above-mentioned mixed solution, isocyanate-monomer is added fast, drip dibutyltin dilaurate catalyst, it is 80 ~ 90 DEG C that reaction 1 ~ 2h post-reactor heats up, and adds hydrophilic chain extender 2,2-dimethylol propionic acid, reaction 1 ~ 2h, add small molecule chain extender BDO afterwards, after reaction 3 ~ 5h, be cooled to 40 ~ 50 DEG C, then add triethylamine neutralization, continue reaction 30 ~ 40min;
(3) above-mentioned reaction product is added emulsifying water under high velocity agitation, the residual tetrahydrofuran (THF) of the removing of underpressure distillation afterwards, obtains functional Aqueous Polyurethane Leather Finishing Agent.
Polymer polyatomic alcohol recited above to be molecular weight be 200 ~ 8000 polyether glycol, polyoxypropyleneglycol, polytetrahydrofuran, polycarbonate diol, the mixture of one or more in polyoxyethylene glycol.
The nano titanium oxide of doping type recited above, surface PEG accounts for 1 ~ 8% of functional Aqueous Polyurethane Leather Finishing Agent dry weight.
Compared with the prior art the present invention, has following positively effect and advantage:
(1) nano-TiO of metal or nonmetal doping is contained in the Aqueous Polyurethane Leather Finishing Agent prepared by
2, have visible light-responded, can make full use of sunlight, antibacterial and mouldproof performance is strong; Nano titanium oxide surface grafting PEG, combine the photocatalytic activity of nano titanium oxide and the excellent anti-protein adsorption ability of polyoxyethylene glycol, coating self-cleaning function is good;
(2) nano titanium oxide surface grafting PEG, makes titanium dioxide surface contain more hydroxyl, increases the reaction site with isocyanate group, is polymerized in synthesis of polyurethane process in position, nano-TiO
2dispersion that can be good in polyurethane matrix, significantly improves heat-resistant stability and the mechanical strength of coating, keeps the transparency of coating and decorating material simultaneously.
embodiment:
Provide four embodiments of the present invention below, specifically described the preparation method of functional Aqueous Polyurethane Leather Finishing Agent by embodiment.What be necessary to herein means out is; embodiment is only for being further detailed the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
embodiment 1
The tetrabutyl titanate measuring 3mL joins in 6mLPEG400, high-speed stirring, reaction for some time, obtains viscous solution; Drip concentrated hydrochloric acid to gained viscous solution, regulate pH to be 2, adulterate a small amount of FeCl
3, continue to stir after for some time, proceed in autoclave, in 150 DEG C of reaction 6h, through absolute ethanol washing, centrifugal, dry, obtain the nano-TiO of Fe doping, surface PEG
2.Take the above-mentioned obtained nano-TiO of 0.6g
2be dissolved in 2g PEG400, pour in there-necked flask, vacuum hydro-extraction 2h at 110 DEG C; Temperature of reaction is down to 70 DEG C, vacuum is converted to nitrogen, adds 30mL tetrahydrofuran solvent, adds 4g isophorone diisocyanate fast, drip 3 dibutyltin dilaurate catalysts, reaction 1.5h; It is 80 DEG C that reaction unit heats up, and adds 1.07g hydrophilic chain extender 2,2-dimethylol propionic acid, reaction 1h; Take 0.72g small molecule chain extender BDO and pour there-necked flask into, reaction 3h, is cooled to 40 DEG C, adds 0.809g triethylamine, continues reaction 30min; Under high velocity agitation, add emulsifying water, the residual tetrahydrofuran (THF) of underpressure distillation removing, obtains functional Aqueous Polyurethane Leather Finishing Agent.
embodiment 2
The tetrabutyl titanate of 3mL is mixed with 6gPEG2000, high-speed stirring, reaction for some time, obtain viscous solution; Add concentrated hydrochloric acid to gained viscous solution, regulate pH to be 4, adulterate a small amount of KIO
3, stir for some time, proceed to autoclave, in 150 DEG C of reaction 7h, through absolute ethanol washing, centrifugal, dry, obtain the nano-TiO of I doping, surface PEG
2.Take the above-mentioned obtained nano-TiO of 0.7g
2be dissolved in 2gPEG2000, pour there-necked flask into, 110 DEG C of vacuum hydro-extraction 2.5h; Temperature of reaction is down to 80 DEG C, vacuum is converted to nitrogen, drips 30mL tetrahydrofuran solvent, adds 4g isophorone diisocyanate fast, drip 3 dibutyltin dilaurate catalysts, reaction 2h; It is 90 DEG C that reaction unit heats up, and adds 1.07g2,2-dimethylol propionic acid, reaction 1h; Take 0.72g BDO and pour there-necked flask into, reaction 3h, is cooled to 40 DEG C, adds 0.809g triethylamine, continues reaction 30min; Under high velocity agitation, after adding emulsifying water, the residual tetrahydrofuran (THF) of underpressure distillation removing, obtains functional Aqueous Polyurethane Leather Finishing Agent.
embodiment 3
The titanium isopropylate measuring 3.5mL joins in 6gPEG2000, high-speed stirring, reaction for some time, obtains viscous solution; Add concentrated hydrochloric acid to gained viscous solution, regulate pH to be 3, adulterate a small amount of KIO
3, continue to stir for some time, proceed to autoclave, in 160 DEG C of reaction 5h, through absolute ethanol washing, centrifugal, dry, obtain the nano-TiO of I doping, surface PEG
2.Take the above-mentioned obtained nano-TiO of 0.6g
2be dissolved in 2.5g polytetrahydrofuran, pour in there-necked flask, vacuum hydro-extraction 2.5h at 110 DEG C; Temperature of reaction is down to 70 DEG C, vacuum is converted to nitrogen, drips 40mL tetrahydrofuran solvent, adds 4g isophorone diisocyanate fast, drip 3 dibutyltin dilaurate catalysts, reaction 1.5h; It is 80 DEG C that reaction unit heats up, and adds 1.2g 2,2-dimethylol propionic acid, reaction 1.5h; Take 0.8g BDO and pour there-necked flask into, reaction 3.5h, is cooled to 45 DEG C, adds 0.9g triethylamine, continues reaction 30min; High-speed stirring, adds emulsifying water, and the residual tetrahydrofuran (THF) of underpressure distillation removing, obtains functional Aqueous Polyurethane Leather Finishing Agent.
embodiment 4
The tetraethyl titanate measuring 4mL joins in 12gPEG4000, high-speed stirring, reaction for some time, obtains viscous solution; Drip concentrated hydrochloric acid to gained viscous solution, regulate pH to be 3, adulterate a small amount of CuCl
2, continue to stir for some time, proceed to autoclave, in 180 DEG C of reaction 6h, through absolute ethanol washing, centrifugal, dry, obtain the nano-TiO of Cu doping, surface PEG
2.Take the above-mentioned obtained nano-TiO of 0.5g
2be dissolved in 3g polytetrahydrofuran, pour there-necked flask into, vacuum hydro-extraction 3h at 110 DEG C; Temperature of reaction is down to 75 DEG C, vacuum is converted to nitrogen, drips 40mL tetrahydrofuran solvent, adds 8g isophorone diisocyanate fast, drip 3 dibutyltin dilaurate catalysts, reaction 1h; It is 85 DEG C that reaction unit heats up, and adds 2.2g2,2-dimethylol propionic acid, reaction 1.5h; Take 1.6g BDO and pour there-necked flask into, reaction 3.5h, is cooled to 40 DEG C, adds 1.5g triethylamine, continues reaction 35min; High-speed stirring, adds emulsifying water, and the residual tetrahydrofuran (THF) of underpressure distillation removing, obtains functional Aqueous Polyurethane Leather Finishing Agent.
Claims (2)
1. a functional Aqueous Polyurethane Leather Finishing Agent, it is characterized in that adopting the preparation of the method for in-situ polymerization and the nano titanium oxide simultaneously introducing doping type, surface PEG, obtain the functional Aqueous Polyurethane Leather Finishing Agent with fungus and mildew resistance, anti-ultraviolet ageing and self-cleaning function, its concrete preparation method is as follows:
(1) be dissolved in polymer polyatomic alcohol by the nano titanium oxide of doping type, surface PEG, vacuum hydro-extraction 2 ~ 5h at 110 ~ 120 DEG C, afterwards temperature of reaction is down to 70 ~ 80 DEG C, vacuum is converted to nitrogen, then adds solvents tetrahydrofurane;
(2) in above-mentioned mixed solution, isocyanate-monomer is added fast, drip dibutyltin dilaurate catalyst, be warmed up to 80 ~ 90 DEG C after reaction 1 ~ 2h, add hydrophilic chain extender 2,2-dimethylol propionic acid, reaction 1 ~ 2h, add small molecule chain extender BDO afterwards, after reaction 3 ~ 5h, be cooled to 40 ~ 50 DEG C, then add triethylamine neutralization, continue reaction 30 ~ 40min;
(3) above-mentioned reaction product is added emulsifying water under high velocity agitation, the residual tetrahydrofuran (THF) of the removing of underpressure distillation afterwards, obtains functional Aqueous Polyurethane Leather Finishing Agent;
Described polymer polyatomic alcohol to be molecular weight be 200 ~ 8000 polyether glycol, polyoxypropyleneglycol, polytetrahydrofuran, polycarbonate diol, the mixture of one or more in polyoxyethylene glycol;
Described doping type, the nano titanium oxide of surface PEG account for 1 ~ 8% of functional Aqueous Polyurethane Leather Finishing Agent dry weight.
2. functional Aqueous Polyurethane Leather Finishing Agent according to claim 1, is characterized in that the nano titanium oxide preparation method of described doping type, surface PEG is as follows:
(1) precursor of titanium is joined in polyoxyethylene glycol, high-speed stirring, reaction for some time, obtain viscous solution;
(2) concentrated hydrochloric acid is added to above-mentioned viscous solution, pH is regulated to be 2 ~ 4, add the compound containing doped element, after continuing to stir for some time, proceed in autoclave, in 140 ~ 180 DEG C of reaction 4 ~ 8h, through absolute ethanol washing, centrifugal, dry, obtain the nano titanium oxide of doping type, surface PEG;
The molecular weight ranges of described polyoxyethylene glycol is 200 ~ 8000;
The precursor of described titanium is one or more mixtures of tetrabutyl titanate, titanium isopropylate, tetraethyl titanate;
Described doped element is one or more in Fe, Cu, Mn, Ag, N, S, I.
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| CN201510138269.0A CN104693404B (en) | 2015-03-27 | 2015-03-27 | A kind of feature Aqueous Polyurethane Leather Finishing Agent and preparation method thereof |
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| CN201510138269.0A CN104693404B (en) | 2015-03-27 | 2015-03-27 | A kind of feature Aqueous Polyurethane Leather Finishing Agent and preparation method thereof |
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| CN104693404B CN104693404B (en) | 2017-06-16 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131656A (en) * | 2015-10-13 | 2015-12-09 | 中国石油化工股份有限公司 | Modification method for nanometer titania |
| CN105176367A (en) * | 2015-10-13 | 2015-12-23 | 中国石油化工股份有限公司 | Preparation method of environment-friendly self-cleaning coating |
| CN108755156A (en) * | 2018-05-31 | 2018-11-06 | 安徽银河皮革有限公司 | Corrosion-resistant, the functional green leather production method of resistance to deformation |
| EP3489370A1 (en) * | 2017-11-22 | 2019-05-29 | Institutul National de Cercetare-Dezvoltare Pentru Textile si Pielarie (INCDTP) Sucursala Institul de Cercetare Pielarie Incaltaminte (ICPI) | Leather with antimicrobial and self-cleaning properties and process for obtaining thereof |
| CN116640505A (en) * | 2023-06-12 | 2023-08-25 | 中轻检验认证有限公司 | Functional photo-curable leather finishing agent system and preparation method and application thereof |
| CN117701787A (en) * | 2024-02-02 | 2024-03-15 | 德州兴隆皮革制品有限公司 | Manufacturing method of antibacterial and bacteriostatic sofa leather |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921379A (en) * | 2010-04-16 | 2010-12-22 | 江苏大学 | Method for preparing aqueous polyurethane/nano titanium dioxide hybrid material |
| CN102643598A (en) * | 2012-04-09 | 2012-08-22 | 四川大学 | Antifouling seal-cleaning aqueous polyurethane leather finishing agent and preparation method thereof |
-
2015
- 2015-03-27 CN CN201510138269.0A patent/CN104693404B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921379A (en) * | 2010-04-16 | 2010-12-22 | 江苏大学 | Method for preparing aqueous polyurethane/nano titanium dioxide hybrid material |
| CN102643598A (en) * | 2012-04-09 | 2012-08-22 | 四川大学 | Antifouling seal-cleaning aqueous polyurethane leather finishing agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘新华等: "聚氨酯改性纳米二氧化钛整理剂的制备和应用", 《印染》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131656A (en) * | 2015-10-13 | 2015-12-09 | 中国石油化工股份有限公司 | Modification method for nanometer titania |
| CN105176367A (en) * | 2015-10-13 | 2015-12-23 | 中国石油化工股份有限公司 | Preparation method of environment-friendly self-cleaning coating |
| EP3489370A1 (en) * | 2017-11-22 | 2019-05-29 | Institutul National de Cercetare-Dezvoltare Pentru Textile si Pielarie (INCDTP) Sucursala Institul de Cercetare Pielarie Incaltaminte (ICPI) | Leather with antimicrobial and self-cleaning properties and process for obtaining thereof |
| CN108755156A (en) * | 2018-05-31 | 2018-11-06 | 安徽银河皮革有限公司 | Corrosion-resistant, the functional green leather production method of resistance to deformation |
| CN116640505A (en) * | 2023-06-12 | 2023-08-25 | 中轻检验认证有限公司 | Functional photo-curable leather finishing agent system and preparation method and application thereof |
| CN117701787A (en) * | 2024-02-02 | 2024-03-15 | 德州兴隆皮革制品有限公司 | Manufacturing method of antibacterial and bacteriostatic sofa leather |
| CN117701787B (en) * | 2024-02-02 | 2024-05-03 | 德州兴隆皮革制品有限公司 | Manufacturing method of antibacterial and bacteriostatic sofa leather |
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| CN104693404B (en) | 2017-06-16 |
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