CN105838228A - Stable waterborne polyurethane paint and preparing method thereof - Google Patents

Stable waterborne polyurethane paint and preparing method thereof Download PDF

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Publication number
CN105838228A
CN105838228A CN201610279925.3A CN201610279925A CN105838228A CN 105838228 A CN105838228 A CN 105838228A CN 201610279925 A CN201610279925 A CN 201610279925A CN 105838228 A CN105838228 A CN 105838228A
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李强
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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
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32—Radiation-absorbing paints
    • 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
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

The invention discloses stable waterborne polyurethane paint .The stable waterborne polyurethane paint is prepared from, by weight, 1-2 parts of lithium naphthenate, 0.1-0.13 part of p-chloro m-dimethylphenol, 10-14 parts of titanium tetrachloride, 0.3-0.7 part of ferric chloride hexahydrate, 30-40 parts of hydrogen peroxide solution of 28-30%, 600-700 parts of polyepsilon-caprolactone glycol, 470-500 parts of isophorone diisocyanate, 20-30 parts of acetone, 13-20 parts of dimethylolpropionic acid, 4-6 parts of diethylene glycol, 0.1-0.16 parts of stannous octoate, 5-7 parts of triethylamine, 1.8-2 parts of diacetone-acryloamide, 3-7 parts of vinyl carboxylate, 0.4-1 part of ammonium fatty alcohol polyoxyethylene ether sulfate, 0.9-1 part of diphenyl imidazoline and 3-4 parts of aluminum potassium sulfate .A paint film is high in ultraviolet light absorbing capacity, self-cleaning performance and tensile strength.

Description

A kind of stable type aqueous polyurethane coating and preparation method thereof
Technical field
The present invention relates to aqueous polyurethane coating technical field, particularly relate to a kind of stable type aqueous polyurethane coating and Preparation method.
Background technology
Aqueous polyurethane is using water as decentralized medium, compared with conventional solvent type polyurethane, have environmental protection, nonflammable, The advantage such as nontoxic, is widely used in the fields such as coating, adhesive, leather finishing agent, textile industry.But, aqueous polyurethane film Anti-ultraviolet ageing ability weak, and be easily contaminated, have impact on its using effect.Research shows, by inorganic nano particle modified Nano composite material not only there is the polymer such as character such as ductility, elasticity, and added inorganic material can be shown The character of material.Nano titanium oxide (TiO2) is a kind of important inorganic semiconductor material, has good photocatalytic, Gao Wen The excellent properties such as qualitative, nontoxic and intensive ultraviolet absorption.Therefore, modified by nano TiO 2, aqueous polyurethane can be given multiple Close film antibiotic property, self-cleaning and ultraviolet absorption ability etc., be a kind of effective way improving aqueous polyurethane film properties.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of stable type aqueous polyurethane coating and Preparation method.
The present invention is achieved by the following technical solutions:
A kind of stable type aqueous polyurethane coating, it is made up of the raw material of following weight parts:
Aphthenic acids lithium 1-2, PCMX 0.1-0.13, titanium tetrachloride 10-14, ferric chloride (FeCl36H2O) 0.3-0.7, The hydrogenperoxide steam generator 30-40 of 28-30%, poly-epsilon-caprolactone glycol 600-700, IPDI 470-500, third Ketone 20-30, dihydromethyl propionic acid 13-20, diethylene glycol (DEG) 4-6, stannous octoate 0.1-0.16, triethylamine 5-7, DAAM 1.8-2, vinyl carboxylate 3-7, AESA 0.4-1, diphenyl-imidazole quinoline 0.9-1, alum 3-4。
The preparation method of a kind of described stable type aqueous polyurethane coating, comprises the following steps:
(1) above-mentioned alum is joined in the deionized water of its weight 20-37 times, insulated and stirred 4-10 at 60-80 DEG C Minute, adding aphthenic acids lithium, stirring, to normal temperature, obtains sta-salt solution；
(2) above-mentioned titanium tetrachloride is joined in the deionized water of its weight 80-100 times, stirring mixing 20-30 at 3-5 DEG C Minute, adding ferric chloride (FeCl36H2O), dripping concentration under stirring condition is the ammonia spirit of 5-6%, and regulation pH is 8-8.6, stands 30-40 minute, add aforementioned stable salting liquid, stir, suction filtration, filter cake is washed 3-4 time, air drying, must adulterate heavy Form sediment；
(3) take above-mentioned diphenyl-imidazole quinoline, join in the absolute ethyl alcohol of its weight 10-13 times, stir, add diacetone Acrylamide, sends in the water-bath of 70-80 DEG C, and insulated and stirred 10-20 minute, discharging is cooled to normal temperature, obtains alcoholic solution；
(4) above-mentioned doping precipitation being joined in the deionized water of its weight 100-120 times, ultrasonic disperse 3-5 minute, in addition State the hydrogenperoxide steam generator of 28-30%, magnetic agitation 30-40 minute, be sent in boiling water bath, heated at constant temperature 3-5 hour, discharging, Mixing with above-mentioned alcoholic solution, add AESA, 300-500 rev/min is stirred 4-10 minute, is distilled off Ethanol, obtains doped titanium sol；
(5) by above-mentioned poly-epsilon-caprolactone glycol vacuum dehydration 10-15 minute at 100-110 DEG C, it is cooled to 30-40 DEG C, with upper Stating vinyl carboxylate mixing, stir, be passed through nitrogen, add above-mentioned IPDI, liter high-temperature is 80- 90 DEG C, constant temperature stirs 1.6-2 hour, adds the 20-30% of above-mentioned acetone weight, reduces temperature and is 30-40 DEG C, adds above-mentioned mixing Miscellaneous titanium colloidal sol, dihydromethyl propionic acid, rise high-temperature and be 76-80 DEG C, and insulation reaction 40-50 minute reduces temperature and is 40-50 DEG C, It is sequentially added into remaining acetone, diethylene glycol (DEG), stannous octoate, slowly rises high-temperature and be 70-75 DEG C, insulation reaction 5-6 hour, cooling To normal temperature, pour in Emulsion cask, add and remain each raw material, stir, add the deionized water of system weight 30-40%, 1200-1700 rev/min is stirred 16-20 minute, obtains stable type aqueous polyurethane coating.
Described a kind of stable type aqueous polyurethane coating and preparation method thereof, the using method of coating of the present invention is:
The base material needing coating is joined in the titanium doped washing polyurethane coating of the present invention, infiltrate 10-20 minute, after taking-up It is placed in ventilation 4-5 days under normal temperature, then is dried 6-10 hour at 46-50 DEG C,.
The invention have the advantage that the film of the present invention has a good hot strength:
The particle of high mechanical stability becomes fixing site, limits the motion of substrate molecule chain, thus improves hot strength, receives Rice corpuscles is uniformly dispersed in the base, and material is by forming center of effort during force-extension, it is possible to cause more crazing, consume Substantial amounts of energy, serves the effect of reinforcement, therefore nano titanium oxide is joined organic polymer can improve organic The mechanical property of substrate, improves the hot strength of film；
The film of the present invention has good uv absorption capacity and a self-cleaning performance:
Fe3+ doped nano titanium dioxide colloidal sol has the strongest photocatalysis performance under visible light, it is possible to significantly improve film UV Aging Resistance；Its photocatalytic degradation capability can be utilized simultaneously to be removed by the contaminant degradation of surface attachment, the most also have There is good self-cleaning performance.
The film of the present invention adds aphthenic acids lithium, stannous octoate etc., and the stability effectively raising finished product film is strong Degree, improves peel strength.
Detailed description of the invention
A kind of stable type aqueous polyurethane coating, it is made up of the raw material of following weight parts:
Aphthenic acids lithium 1, PCMX 0.1, titanium tetrachloride 10, ferric chloride (FeCl36H2O) 0.3,28% hydrogen peroxide molten Esterdiol 600 in liquid 30, poly epsilon caprolactone, IPDI 470, acetone 20, dihydromethyl propionic acid 13, diethylene glycol (DEG) 4, pungent Acid stannous 0.1, triethylamine 5, DAAM 1.8, vinyl carboxylate 3, AESA 0.4, Diphenyl-imidazole quinoline 0.9, alum 3.
The preparation method of a kind of described stable type aqueous polyurethane coating, comprises the following steps:
(1) above-mentioned alum is joined in the deionized water of its weight 20 times, insulated and stirred 4 minutes at 60 DEG C, add Aphthenic acids lithium, stirring, to normal temperature, obtains sta-salt solution；
(2) being joined by above-mentioned titanium tetrachloride in the deionized water of its weight 80 times, at 3 DEG C, stirring mixing 20 minutes, add Ferric chloride (FeCl36H2O), under stirring condition drip concentration be the ammonia spirit of 5%, regulation pH be 8, stand 30 minutes, add above-mentioned surely Determine salting liquid, stir, suction filtration, filter cake is washed 3 times, air drying, precipitation of must adulterating；
(3) take above-mentioned diphenyl-imidazole quinoline, join in the absolute ethyl alcohol of its weight 10 times, stir, add diacetone third Acrylamide, sends in the water-bath of 70 DEG C, and insulated and stirred 10 minutes, discharging is cooled to normal temperature, obtains alcoholic solution；
(4) above-mentioned doping precipitation is joined in the deionized water of its weight 100 times, ultrasonic disperse 3 minutes, add above-mentioned 28% Hydrogenperoxide steam generator, magnetic agitation 30 minutes, be sent in boiling water bath, heated at constant temperature 3 hours, discharging, with above-mentioned alcoholic solution Mixing, adds AESA, and 300 revs/min are stirred 4 minutes, ethanol are distilled off, obtain doped titanium sol；
(5) by vacuum dehydration 10 minutes at 100 DEG C of esterdiol in above-mentioned poly epsilon caprolactone, it is cooled to 30 DEG C, with above-mentioned vinyl carboxylic acid Ester mixes, and stirs, is passed through nitrogen, adds above-mentioned IPDI, and rising high-temperature is 80 DEG C, and constant temperature stirs 1.6 hours, adding the 20% of above-mentioned acetone weight, reducing temperature is 30 DEG C, adds above-mentioned doped titanium sol, dihydromethyl propionic acid, Rising high-temperature is 76 DEG C, insulation reaction 40 minutes, and reducing temperature is 40 DEG C, is sequentially added into remaining acetone, diethylene glycol (DEG), octanoic acid Asia Tin, slowly rising high-temperature is 70 DEG C, and insulation reaction 5 hours is cooled to normal temperature, pours in Emulsion cask, adds and remain each raw material, stir Mixing uniformly, add the deionized water of system weight 30%, 1200 revs/min are stirred 16 minutes, obtain stable type aqueous polyurethane coating.
A kind of stable type aqueous polyurethane coating and preparation method thereof, the using method of coating of the present invention is:
The base material needing coating is joined in the titanium doped washing polyurethane coating of the present invention, infiltrate 10 minutes, take out rearmounted Ventilate 4 days under normal temperature, then be dried 6 hours at 46 DEG C,.
Performance test:
Water absorption rate 0.0141%, before water suction, cohesive force is 12.70 MPa, keeps after water suction immersion test soaks 3200 h 10.44MPa high cohesive force.

Claims (3)

1. a stable type aqueous polyurethane coating, it is characterised in that it is made up of the raw material of following weight parts:
Aphthenic acids lithium 1-2, PCMX 0.1-0.13, titanium tetrachloride 10-14, ferric chloride (FeCl36H2O) 0.3-0.7, The hydrogenperoxide steam generator 30-40 of 28-30%, poly-epsilon-caprolactone glycol 600-700, IPDI 470-500, third Ketone 20-30, dihydromethyl propionic acid 13-20, diethylene glycol (DEG) 4-6, stannous octoate 0.1-0.16, triethylamine 5-7, DAAM 1.8-2, vinyl carboxylate 3-7, AESA 0.4-1, diphenyl-imidazole quinoline 0.9-1, alum 3-4。
2. the preparation method of a stable type aqueous polyurethane coating as claimed in claim 1, it is characterised in that include following Step:
(1) above-mentioned alum is joined in the deionized water of its weight 20-37 times, insulated and stirred 4-10 at 60-80 DEG C Minute, adding aphthenic acids lithium, stirring, to normal temperature, obtains sta-salt solution；
(2) above-mentioned titanium tetrachloride is joined in the deionized water of its weight 80-100 times, stirring mixing 20-30 at 3-5 DEG C Minute, adding ferric chloride (FeCl36H2O), dripping concentration under stirring condition is the ammonia spirit of 5-6%, and regulation pH is 8-8.6, stands 30-40 minute, add aforementioned stable salting liquid, stir, suction filtration, filter cake is washed 3-4 time, air drying, must adulterate heavy Form sediment；
(3) take above-mentioned diphenyl-imidazole quinoline, join in the absolute ethyl alcohol of its weight 10-13 times, stir, add diacetone Acrylamide, sends in the water-bath of 70-80 DEG C, and insulated and stirred 10-20 minute, discharging is cooled to normal temperature, obtains alcoholic solution；
(4) above-mentioned doping precipitation being joined in the deionized water of its weight 100-120 times, ultrasonic disperse 3-5 minute, in addition State the hydrogenperoxide steam generator of 28-30%, magnetic agitation 30-40 minute, be sent in boiling water bath, heated at constant temperature 3-5 hour, discharging, Mixing with above-mentioned alcoholic solution, add AESA, 300-500 rev/min is stirred 4-10 minute, is distilled off Ethanol, obtains doped titanium sol；
(5) by above-mentioned poly-epsilon-caprolactone glycol vacuum dehydration 10-15 minute at 100-110 DEG C, it is cooled to 30-40 DEG C, with upper Stating vinyl carboxylate mixing, stir, be passed through nitrogen, add above-mentioned IPDI, liter high-temperature is 80- 90 DEG C, constant temperature stirs 1.6-2 hour, adds the 20-30% of above-mentioned acetone weight, reduces temperature and is 30-40 DEG C, adds above-mentioned mixing Miscellaneous titanium colloidal sol, dihydromethyl propionic acid, rise high-temperature and be 76-80 DEG C, and insulation reaction 40-50 minute reduces temperature and is 40-50 DEG C, It is sequentially added into remaining acetone, diethylene glycol (DEG), stannous octoate, slowly rises high-temperature and be 70-75 DEG C, insulation reaction 5-6 hour, cooling To normal temperature, pour in Emulsion cask, add and remain each raw material, stir, add the deionized water of system weight 30-40%, 1200-1700 rev/min is stirred 16-20 minute, obtains stable type aqueous polyurethane coating.
3. according to a kind of stable type aqueous polyurethane coating described in claim 1,2 and preparation method thereof, coating of the present invention Using method is:
The base material needing coating is joined in the titanium doped washing polyurethane coating of the present invention, infiltrate 10-20 minute, after taking-up It is placed in ventilation 4-5 days under normal temperature, then is dried 6-10 hour at 46-50 DEG C,.
CN201610279925.3A 2016-04-29 2016-04-29 Stable waterborne polyurethane paint and preparing method thereof Withdrawn CN105838228A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106566364A (en) * 2016-11-08 2017-04-19 芜湖市鸿坤汽车零部件有限公司 Flexible antimicrobial leather coating and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1786087A (en) * 2005-11-02 2006-06-14 刘应希 Nano-composite paint possessing light catalytic function and its preparation method
CN101921379A (en) * 2010-04-16 2010-12-22 江苏大学 Method for preparing aqueous polyurethane/nano titanium dioxide hybrid material
CN103073692A (en) * 2013-01-31 2013-05-01 烟台前进化工有限公司 Producing method of water-base polyurethane
CN103772644A (en) * 2014-01-21 2014-05-07 山东未来化工技术有限公司 Modified waterborne polyurethane resin and synthesis method
CN104263122A (en) * 2014-09-03 2015-01-07 天长市开林化工有限公司 Stable paint

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1786087A (en) * 2005-11-02 2006-06-14 刘应希 Nano-composite paint possessing light catalytic function and its preparation method
CN101921379A (en) * 2010-04-16 2010-12-22 江苏大学 Method for preparing aqueous polyurethane/nano titanium dioxide hybrid material
CN103073692A (en) * 2013-01-31 2013-05-01 烟台前进化工有限公司 Producing method of water-base polyurethane
CN103772644A (en) * 2014-01-21 2014-05-07 山东未来化工技术有限公司 Modified waterborne polyurethane resin and synthesis method
CN104263122A (en) * 2014-09-03 2015-01-07 天长市开林化工有限公司 Stable paint

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106566364A (en) * 2016-11-08 2017-04-19 芜湖市鸿坤汽车零部件有限公司 Flexible antimicrobial leather coating and preparation method thereof

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