CN104530365A - Waterborne polyurethane used for leather surface treatment and preparation method thereof - Google Patents
Waterborne polyurethane used for leather surface treatment and preparation method thereof Download PDFInfo
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- CN104530365A CN104530365A CN201410725072.2A CN201410725072A CN104530365A CN 104530365 A CN104530365 A CN 104530365A CN 201410725072 A CN201410725072 A CN 201410725072A CN 104530365 A CN104530365 A CN 104530365A
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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
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6212—Polymers of alkenylalcohols; Acetals thereof; Oxyalkylation products thereof
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses waterborne polyurethane used for leather surface treatment. The waterborne polyurethane is prepared by reacting dihydric-alcohol-terminated oxidized polyethlene wax, diisocyanate and dimethylolpropionic acid in acetone so as to obtain waterborne polyurethane prepolymer, neutralizing the waterborne polyurethane prepolymer with triethylamine, carrying out shearing and emulsifying after adding water, and carrying out decompressing to remove acetone so as to obtain the waterborne polyurethane. The waterborne polyurethane provided by the invention has the advantages of high gloss, water resistance, wear resistance and high tensile strength and can be widely used for the leather surface treatment.
Description
Technical field
The invention belongs to leather polyurethane material technical field, particularly a kind of leather surface treatment agent use urethane and preparation method thereof.
Technical background
In recent years, for meeting the demand of synthetic leather producer to leather surface process, auxiliary chemicals manufacturer competitively develops, be proposed the leather surface treatment agent of variable color, be full of cracks, foaming, sliding sense, the various performance such as highlighted, but these surface treatment agents are carrier mainly with common polyurethane resin or acrylic resin, be prepared from by auxiliary agents such as interpolation flatting silica, silicone oil, solvents.Coat leather surface in use, then make it form polyurethane coating at leather surface through heating.The organic solvents such as the DMF that these common urethane resins or acrylic resin adopt usually, in use can cause environmental pollution because of solvent evaporates, and after film forming glossiness and heat-resisting weathering resistance all not ideal enough.Therefore, people start to select washing urethane as leather surface treatment agent.
Aqueous polyurethane is dispersion medium with water, instead of traditional organic solvent, have do not pollute, transportation safety, advantages of environment protection, but there is the not good shortcoming such as water tolerance, solvent resistance, mechanical property, wear resistance.In the leather surface process had high requirements to film wear resistance, the wear resisting property of aqueous polyurethane is also difficult to the requirement reaching use.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists for above-mentioned prior art and provides a kind of leather surface treatment agent use urethane and preparation method thereof, and glossiness is high, water-fast, wear-resistant tensile intensity is good.
The technical scheme that the problem that the present invention is the above-mentioned proposition of solution adopts is:
A kind of leather surface process use urethane, it is by the oxidized polyethlene wax of dibasic alcohol end-blocking and vulcabond, dimethylol propionic acid water generation reaction base polyurethane prepolymer for use as in acetone, then described Waterborne Polyurethane Prepolymer through in triethylamine and after, and to obtain with water emulsification pretreatment.
A preparation method for leather surface process use urethane, comprises the steps:
(1) preparation of oxidized polyethlene wax dibasic alcohol: by oxidized polyethlene wax and dibasic alcohol by amount of substance 1:(1-3) be mixed in toluene, add sulfuric acid and make catalyzer, be heated to 100-110 DEG C of reaction 4-8h, removing toluene, obtains the oxidized polyethlene wax of dibasic alcohol end-blocking;
(2) preparation of base polyurethane prepolymer for use as: the oxidized polyethlene wax of dibasic alcohol end-blocking prepared by step (1) with vulcabond, dimethylol propionic acid by amount of substance than 1:2:(1-2) be dissolved in acetone, react 4-8 hour under 60-80 DEG C of condition, be cooled to room temperature and obtain Waterborne Polyurethane Prepolymer;
(3) preparation of aqueous polyurethane: add triethylamine and neutralize in Waterborne Polyurethane Prepolymer prepared by step (2), then add deionized water emulsification pretreatment 20-40min, be warming up to 40-60 DEG C and reduce pressure except namely acetone 10-20min obtains leather surface process use urethane.
By such scheme, in described step (1), oxidized polyethlene wax molecular formula is HOOCC
nh
2ncOOH, molecular weight is 300 ~ 3000.
By such scheme, the dibasic alcohol in described step (1) is one or both mixtures in any proportion in ethylene glycol or butyleneglycol.
By such scheme, the preferred 1:2 of amount of substance pressed by the oxidized polyethlene wax in described step (1) and dibasic alcohol.
By such scheme, the sulfuric acid in described step (1) is 98% vitriol oil, and its add-on is (0.4-0.6) % of oxidized polyethlene wax quality.
By such scheme, in described step (1), toluene is as solvent, and its add-on is 1-3 times of oxidized polyethlene wax quality.Preferably, step (1) toluene add-on is 2 times of oxidized polyethlene wax quality.
By such scheme, vulcabond is one or both mixtures in any proportion in isophorone diisocyanate or hexamethylene diisocyanate in described step (2).
By such scheme, in described step (2), the add-on of acetone is 1-3 times of the oxidized polyethlene wax quality of dibasic alcohol end-blocking.Preferably, the add-on of step (2) acetone is 2 times of the oxidized polyethlene wax quality of dibasic alcohol end-blocking.
By such scheme, in described step (3), triethylamine is equal with the amount of substance of dimethylol propionic acid.
By such scheme, in described step (3), the add-on of deionized water is 1-1.5 times of described Waterborne Polyurethane Prepolymer quality.Wherein, Waterborne Polyurethane Prepolymer quality is come in the summation of the oxidized polyethlene wax of dibasic alcohol end-blocking in step (2), vulcabond and dimethylol propionic acid three quality, and does not comprise acetone.
Compared with prior art, the invention has the beneficial effects as follows:
1) the present invention adopts that glossiness is high, hardness is large, good hand touch, and the oxidized polyethlene wax of excellent durability is raw material prepares leather surface process use urethane, leather surface has high glossiness, good hand touch after covering with paint, lacquer, colour wash, etc., because it contains hydrophobic alkyl backbones, coatings is made to have good hydrophobic weather resistance;
2) compared with traditional polyester, polyether(poly)urethane, the leather surface process use urethane prepared by the present invention take oxidized polyethlene wax as raw material, and main chain is high strength, chemically stable polyethylene, thus has better wear resistance and tensile strength;
3) compared with the emulsion finishing agent such as existing urethane, animal wax, raw materials cost of the present invention is cheaper, and products obtained therefrom is water miscible liquid, belongs to Green Product, free from environmental pollution.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but the present invention is not only confined to the following examples.
Embodiment 1
A preparation method for leather surface process use urethane, the step described in it is:
(1) preparation of oxidized polyethlene wax dibasic alcohol: add 30g oxidized polyethlene wax (Mw=300 in 250ml three-necked flask, i.e. 0.1mol) and 12.4g (i.e. 0.2mol) ethylene glycol, add 0.12g concentration 98% vitriol oil again as catalyzer and 60g toluene as solvent, 110 DEG C of reaction 4h are heated under mechanical agitation, revolve and steam removing toluene, obtain the oxidized polyethlene wax of second dibasic alcohol end-blocking;
(2) preparation of base polyurethane prepolymer for use as: be equipped with in the four-hole boiling flask of thermometer, reflux condensing tube, stirring, dropping funnel at 250ml, add the oxidized polyethlene wax (Mw=388 of ethylene glycol end-blocking prepared by 19.4g step (1), 0.05mol) different fluorine that ketone isocyanic ester, 6.7g (i.e. 0.05mol) bishydroxymethyl propionic acid, 38.8g acetone with 22.2g (i.e. 0.1mol), 60 DEG C of reaction 8h are heated under mechanical agitation, be cooled to room temperature, obtain Waterborne Polyurethane Prepolymer;
(3) preparation of aqueous polyurethane: 5.1g (i.e. 0.05mol) triethylamine neutralization in Waterborne Polyurethane Prepolymer prepared by step (2), then add 80.1g deionized water emulsification pretreatment 20min, be warming up to 40 DEG C and reduce pressure except acetone 20min obtains the leather surface process use urethane that solid content is 40%.
Embodiment 2
A preparation method for leather surface process use urethane, the step described in it is:
(1) preparation of oxidized polyethlene wax dibasic alcohol: add 30g oxidized polyethlene wax (Mw=3000 in 250ml three-necked flask, i.e. 0.01mol) and 1.80g (i.e. 0.02mol) butyleneglycol, add 0.15g concentration 98% vitriol oil again as catalyzer and 60g toluene as solvent, 110 DEG C of reaction 8h are heated under mechanical agitation, revolve and steam removing toluene, obtain the oxidized polyethlene wax of fourth dibasic alcohol end-blocking;
(2) preparation of base polyurethane prepolymer for use as: be equipped with in the four-hole boiling flask of thermometer, reflux condensing tube, stirring, dropping funnel at 250ml, add the oxidized polyethlene wax (Mw=3144 of fourth dibasic alcohol end-blocking prepared by 31.44g step (1), 0.01mol) different fluorine that ketone isocyanic ester, 1.68 (0.01mol) hexa-methylene isocyanic ester, 2.68g (i.e. 0.02mol) bishydroxymethyl propionic acid, 62.88g acetone with 2.22g (i.e. 0.01mol), 80 DEG C of reaction 4h are heated under mechanical agitation, be cooled to room temperature, obtain Waterborne Polyurethane Prepolymer;
(3) preparation of aqueous polyurethane: 2.02g (i.e. 0.02mol) triethylamine neutralization in Waterborne Polyurethane Prepolymer prepared by step (2), then add 40.04g deionized water emulsification pretreatment 40min, be warming up to 60 DEG C and reduce pressure except acetone 10min obtains the leather surface process use urethane that solid content is 50%.
Embodiment 3
A preparation method for leather surface process use urethane, the step described in it is:
(1) preparation of oxidized polyethlene wax dibasic alcohol: add 30g oxidized polyethlene wax (Mw=1500 in 250ml three-necked flask, 0.02mol) with 1.80g (i.e. 0.02mol) butyleneglycol, 1.24g (i.e. 0.02mol) ethylene glycol, add 0.18g concentration 98% vitriol oil again as catalyzer and 60g toluene as solvent, 110 DEG C of reaction 6h are heated under mechanical agitation, revolve and steam removing toluene, obtain the oxidized polyethlene wax of butyleneglycol end-blocking;
(2) preparation of base polyurethane prepolymer for use as: be equipped with in the four-hole boiling flask of thermometer, reflux condensing tube, stirring, dropping funnel at 250ml, add the oxidized polyethlene wax (Mw=1616 of butyleneglycol end-blocking prepared by 16.16g step (1), 0.01mol) He 3.36 (0.02mol) hexa-methylene isocyanic ester, 2.01g (0.015mol) bishydroxymethyl propionic acid, 32.32g acetone, 70 DEG C of reaction 6h are heated under mechanical agitation, be cooled to room temperature, obtain Waterborne Polyurethane Prepolymer;
(3) preparation of aqueous polyurethane: 1.51g (0.015mol) triethylamine neutralization in Waterborne Polyurethane Prepolymer prepared by step (2), then add 28.16g deionized water emulsification pretreatment 30min, be warming up to 50 DEG C and reduce pressure except acetone 15min obtains the leather surface process use urethane that solid content is 45%.
Application testing
The leather surface process use urethane prepared by embodiment 1-3 carries out the test of the aspects such as glossiness, water-intake rate, wear rate and mechanical property respectively, and test result is as shown in table 1.
1, glossiness test: the method for the leather surface process use urethane roller coating of above-mentioned preparation is coated synthetic leather surface (original glossiness is 18 °), then in the baking oven of 100 DEG C, 30min is toasted, cool after complete drying, survey 60 degree of angle glossiness with vancometer;
2, water-intake rate test: by polyurethane coated on polyfluortetraethylene plate for the leather surface process use of above-mentioned preparation, toast 2h at 100 DEG C, the glued membrane obtained is immersed in 24h in distilled water, measures the rate of body weight gain before and after soaking;
3, wear rate test: by polyurethane coated on polyfluortetraethylene plate for the leather surface process use of above-mentioned preparation, toast 2h at 100 DEG C, the glued membrane obtained adopts GT-7012-T type abrasion performance tester, measures the abrasion loss of film by GB/T1768-2006;
4, Mechanics Performance Testing: by polyurethane coated on polyfluortetraethylene plate for the leather surface process use of above-mentioned preparation, 2h is toasted at 100 DEG C, be cut into dumbbell shape batten with cut-off knife, on universal testing machine GP-TS2000S/10KN, tested for tensile strength is with elongation at break.
Table 1. embodiment products obtained therefrom performance index
| Numbering | Glossiness/° | Water-intake rate/% | Wear rate/% | Tensile strength/MPa | Elongation at break/% |
| Embodiment 1 | 46 | 5.5 | 0.57 | 23.6 | 322 |
| Embodiment 2 | 67 | 2.8 | 0.21 | 32.4 | 305 |
| Embodiment 3 | 55 | 4.2 | 0.37 | 26.4 | 296 |
From upper table 1 detected result, original glossiness is the synthetic leather of 18 °, and after covering with paint, lacquer, colour wash, etc. the aqueous polyurethane of preparation of the present invention, glossiness all brings up to more than 45 °, reaches as high as 67 °; In addition, because the main chain of oxidized polyethlene wax is poly structure, have high strength, chemically stable characteristic, thus its water-intake rate is low, wear-resisting, mechanical property is all better.
It should be pointed out that for the person of ordinary skill of the art, without departing from the concept of the premise of the invention, can also make some improvement and conversion, these all belong to protection scope of the present invention.
Claims (10)
1. a leather surface process use urethane, it is by the oxidized polyethlene wax of dibasic alcohol end-blocking and vulcabond, dimethylol propionic acid water generation reaction base polyurethane prepolymer for use as in acetone, then described Waterborne Polyurethane Prepolymer neutralizes through triethylamine, and decompression obtains except acetone after the emulsification pretreatment that adds water.
2. the preparation method of leather surface process use urethane according to claim 1, is characterized in that comprising the steps:
(1) preparation of oxidized polyethlene wax dibasic alcohol: by oxidized polyethlene wax and dibasic alcohol by amount of substance 1:(1-3) be mixed in toluene, add sulfuric acid and make catalyzer, be heated to 100-110 DEG C of reaction 4-8h, removing toluene, obtains the oxidized polyethlene wax of dibasic alcohol end-blocking;
(2) preparation of base polyurethane prepolymer for use as: the oxidized polyethlene wax of dibasic alcohol end-blocking prepared by step (1) with vulcabond, dimethylol propionic acid by amount of substance than 1:2:(1-2) be dissolved in acetone, react 4-8 hour under 60-80 DEG C of condition, be cooled to room temperature and obtain Waterborne Polyurethane Prepolymer;
(3) preparation of aqueous polyurethane: add triethylamine and carry out neutralization reaction 0.5h in Waterborne Polyurethane Prepolymer prepared by step (2), then add deionized water emulsification pretreatment 20-40min, be warming up to 40-60 DEG C and reduce pressure except namely acetone 10-20min obtains leather surface process use urethane.
3. the preparation method of a kind of leather surface process use urethane according to claim 2, is characterized in that in described step (1), oxidized polyethlene wax molecular formula is HOOCC
nh
2ncOOH, molecular weight is 300 ~ 3000.
4. the preparation method of a kind of leather surface process use urethane according to claim 2, the dibasic alcohol that it is characterized in that in described step (1) is one or both mixtures in any proportion in ethylene glycol or butyleneglycol.
5. the preparation method of a kind of leather surface process use urethane according to claim 2, it is characterized in that the sulfuric acid in described step (1) is 98% vitriol oil, its add-on is (0.4-0.6) % of oxidized polyethlene wax quality.
6. the preparation method of a kind of leather surface process use urethane according to claim 2, is characterized in that in described step (1), toluene is as solvent, and its add-on is 1-3 times of oxidized polyethlene wax quality.
7. the preparation method of a kind of leather surface process use urethane according to claim 2, is characterized in that vulcabond in described step (2) is one or both mixtures in any proportion in isophorone diisocyanate or hexamethylene diisocyanate.
8. the preparation method of a kind of leather surface process use urethane according to claim 2, is characterized in that the add-on of acetone in described step (2) is 1-3 times of the oxidized polyethlene wax quality of dibasic alcohol end-blocking.
9. the preparation method of a kind of leather surface process use urethane according to claim 2, is characterized in that in described step (3), triethylamine is equal with the amount of substance of dimethylol propionic acid.
10. the preparation method of a kind of leather surface process use urethane according to claim 2, is characterized in that the add-on of deionized water in described step (3) is 1-1.5 times of described Waterborne Polyurethane Prepolymer quality.
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| CN201410725072.2A CN104530365B (en) | 2014-12-03 | 2014-12-03 | A kind of leather surface processing aqueous polyurethane and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105238017A (en) * | 2015-09-18 | 2016-01-13 | 扬中市天正合成材料研究中心 | Environmental-protection and high-flame retardation television shell composite material and preparation method thereof |
| CN105421076A (en) * | 2015-12-25 | 2016-03-23 | 江苏宝泽高分子材料股份有限公司 | Aqueous high-gloss gloss oil used for artificial leather and preparation method thereof |
| CN107524027A (en) * | 2017-08-14 | 2017-12-29 | 兴业皮革科技股份有限公司 | A kind of coating method for solving crust leather dyeing defect |
| CN108753145A (en) * | 2017-12-25 | 2018-11-06 | 叶昭君 | Polyurethane aqueous paint of one kind and preparation method thereof |
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| CN101235129A (en) * | 2008-03-05 | 2008-08-06 | 安徽大学 | Method for preparing polybutadiene-base water polyurethane and modified emulsion thereof |
| CN102863607A (en) * | 2012-08-28 | 2013-01-09 | 东莞市万钧化工新材料科技有限公司 | Emulsion of water-based primer for EVA materials |
| CN102977320A (en) * | 2012-11-12 | 2013-03-20 | 青岛文创科技有限公司 | Method for modifying water-based polyurethane by using hydroxyl terminated polybutadiene |
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| CN101235129A (en) * | 2008-03-05 | 2008-08-06 | 安徽大学 | Method for preparing polybutadiene-base water polyurethane and modified emulsion thereof |
| CN102863607A (en) * | 2012-08-28 | 2013-01-09 | 东莞市万钧化工新材料科技有限公司 | Emulsion of water-based primer for EVA materials |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105238017A (en) * | 2015-09-18 | 2016-01-13 | 扬中市天正合成材料研究中心 | Environmental-protection and high-flame retardation television shell composite material and preparation method thereof |
| CN105421076A (en) * | 2015-12-25 | 2016-03-23 | 江苏宝泽高分子材料股份有限公司 | Aqueous high-gloss gloss oil used for artificial leather and preparation method thereof |
| CN107524027A (en) * | 2017-08-14 | 2017-12-29 | 兴业皮革科技股份有限公司 | A kind of coating method for solving crust leather dyeing defect |
| CN107524027B (en) * | 2017-08-14 | 2020-01-10 | 兴业皮革科技股份有限公司 | Coating method for solving crust leather color pattern |
| CN108753145A (en) * | 2017-12-25 | 2018-11-06 | 叶昭君 | Polyurethane aqueous paint of one kind and preparation method thereof |
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| CN104530365B (en) | 2018-04-27 |
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