CN104974327A - Waterborne polyurethane emulsion and preparation method thereof - Google Patents
Waterborne polyurethane emulsion and preparation method thereof Download PDFInfo
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- CN104974327A CN104974327A CN201510483213.9A CN201510483213A CN104974327A CN 104974327 A CN104974327 A CN 104974327A CN 201510483213 A CN201510483213 A CN 201510483213A CN 104974327 A CN104974327 A CN 104974327A
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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
- C08G18/08—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
- C08G18/28—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
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with 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
- C08G18/28—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
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
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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
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a waterborne polyurethane emulsion and a preparation method thereof. The preparation method comprises the following steps: firstly carrying out vacuum dehydration on polymer polyol, a hydrophilic chain extender, isosorbide and N-methyl pyrrolidone at 90 DEG C for 1-2 hours, reducing the temperature to 80-90 DEG C, adding diisocyanate and reacting for 2.5-3 hours until NCO% reaches the theoretical value; then reducing the temperature, adding a neutralizer to an NCO-terminated polyurethane prepolymer and reacting at 60 DEG C for 0.5 hour until the neutralization degree is 95-100%; finally dispersing the polyurethane prepolymer containing isosorbide into deionized water under the high-speed shearing action of an agitator and dropwise adding a mixture of diamine and water after dispersing for a period of time, thus obtaining the waterborne polyurethane emulsion. Isosorbide is successfully introduced into the waterborne polyurethane emulsion, thus obviously improving the glossiness of waterborne polyurethane films.
Description
Technical field
The invention belongs to polyurethane finishing agent field, relate to a kind of aqueous polyurethane emulsion and preparation method thereof.
Background technology
Hide finishes is the important leather chemicals of one that outward appearance, use properties and economic worth to leather promote.Finishing agent forms the uniform film of one deck at leather surface, gives the use properties of leather excellence, as performances such as solvent resistant, Bearable dry and wet wipe, water-repellancy and glossiness.Along with the development of science and technology, the demand of people to leather quality is more and more higher, and the quality of two leathers depends on the quality of hide finishes to a great extent.Finishing agent gloss is a kind of optical signature of film coated surface, represents with the ability of its reflected light.Coating film gloss is the leading indicator weighing appearance of film quality, and high gloss film not only outward appearance is beautiful, plays good decoration function, and play a good protection to coated article to coated article surface.The practice of application application shows, the reduction of coating protective effect, often all from its surface luster declines.
Current hide finishes mainly contains nitrocellulose dope, polyhutadiene finishing agent, acrylic resin coating finiss, organosilicon finishing agent, polyurethane finishing agent etc., wherein waterborne polyurethane coating agent is the research emphasis of numerous investigator, is also the Main way of hide finishes development.As far back as 1972, polyurethane aqueous dispersion body formally used as hide finishes by German Bayer company.China to begin one's study waterborne polyurethane coating agent application in the leather from 20 century 70s.Aqueous Polyurethane Leather Finishing Agent in use nontoxic, pollution-free, film forming ability is strong, there is excellent winter hardiness, elasticity and comfortable feel, but because containing the hydrophilic radical such as a certain amount of-COOH ,-OH ,-O-in aqueous polyurethane molecular structure, formed the not resistance to wet rubbing of film, and formed film physical strength and glossiness not high.
Summary of the invention
In view of above problem, the object of this invention is to provide a kind of aqueous polyurethane film with high glossiness and preparation method thereof, concrete technical scheme is as follows:
A kind of aqueous polyurethane emulsion, comprises the component represented with parts by weight as follows:
The number-average molecular weight of described polymer polyatomic alcohol is 1000 ~ 2000, for the mixture of one or more in polyethylene glycol adipate dibasic alcohol, poly adipate succinic acid ester dibasic alcohol, polyneopentyl glycol adipate dibasic alcohol, polytetrahydrofuran dibasic alcohol, PCDL, polyoxyethylene ether dibasic alcohol, polyoxytrimethylene ether dibasic alcohol, poly-1,3-PD ether dibasic alcohol, polycaprolactone diols;
Described hydrophilic chain extender is one or more the mixture in N, N-dihydroxy ethyl list maleinamic acid, dimethylol propionic acid, dimethylolpropionic acid, the two amino propane sulfonic acid of 3-;
Described small molecule polyol is the mixture of one or more in Isosorbide and hexylene glycol, butyleneglycol, glycerol, TriMethylolPropane(TMP), glycol ether.
Described vulcabond is the mixture of one or more in hexamethylene diisocyanate, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate.
Described polyhydric amine compounds is the mixture of one or more in quadrol, hexanediamine, diethylenetriamine, triethylene tetramine, 3,3-bis-chloro-4,4-diamino-ditans.
Described neutralizing agent is triethylamine or sodium hydroxide or the mixture of the two.
The preparation method of above-mentioned arbitrary described aqueous polyurethane emulsion, comprises the steps:
By described polymer polyatomic alcohol, hydrophilic polyol, small molecule polyol, N-Methyl pyrrolidone at 80 ~ 95 DEG C of vacuum hydro-extraction 1.5 ~ 2h, be cooled to 80 ~ 90 DEG C, add vulcabond, reaction 2.5 ~ 3h, until NCO% reaches theoretical value, obtain the base polyurethane prepolymer for use as of NCO end-blocking;
Reduce system temperature, add neutralizing agent, at 60 ~ 80 DEG C of reaction 0.5 ~ 1h, obtain Waterborne Polyurethane Prepolymer, degree of neutralization is 95 ~ 100%;
Described Waterborne Polyurethane Prepolymer is dispersed under the high speed shear effect of stirrer, and drip the mixture of polyamine and water, hierarchy of control temperature is 30 ~ 40 DEG C, and emulsification 0.5 ~ 1h obtains described aqueous polyurethane emulsion.
Advantage of the present invention is as follows:
(1) on the basis of traditional waterborne polyurethane emulsion, introduce novel chainextender, change the molecular chain structure of urethane; By regulating the content of chainextender, the aqurous ployurethane emulsion of synthesis is made to have good mechanical property and glossiness; While small molecule polyol chain extension, introduce hydrophilic radical, keep emulsion to have certain wetting ability, finally obtain polyurethane prepolymer with appropriate diisocyanate monomer end-blocking, ensure to carry out chain extension with active polyamine after emulsification, the high performance aqueous polyurethane of final acquisition;
(2) control the content of hydrophilic radical in polyurethane molecular chain, make base polyurethane prepolymer for use as emulsification smoothly in deionized water, the emulsion obtained has excellent stability; By adding micromolecular chainextender, modification being carried out to urethane, improve mechanical property and the glossiness of polyaminoester emulsion film;
(3) aqurous ployurethane prepared, without the need to adding emulsifying agent in addition, improves emulsion intercalation method;
(4) also there is heat-resisting, the excellent properties such as solvent resistant, high-low temperature resistant.
Accompanying drawing explanation
Fig. 1 is heat-resisting test curve figure and the data of the product of embodiment 1 ~ 5;
Fig. 2 is the graphic representation of resistance to weightless test and the data of the product of embodiment 1 ~ 5;
Fig. 3 is high-low temperature resistant test curve figure and the data of the product of embodiment 1 ~ 5.
Embodiment
Below, specific embodiments of the present invention are further described in detail in conjunction with the accompanying drawings and embodiments, but should not limit the scope of the invention with this.
Embodiment 1
(1) be that the polyneopentyl glycol adipate glycol of 2000,4.5 parts of dimethylol propionic acids, 0 part of Isosorbide, 6 parts of N-Methyl pyrrolidone are at 90 DEG C of vacuum hydro-extraction 1.5 ~ 2h by 80 parts of molecular weight, be cooled to 80 ~ 90 DEG C, add 27.8 parts of isophorone diisocyanates, reaction 2.5 ~ 3h, until NCO% reaches theoretical value, obtain the base polyurethane prepolymer for use as of NCO end-blocking;
(2) reduce system temperature, add 3.3 parts of neutralizing agent triethylamines, at 60 DEG C of reaction 0.5h, obtain hydrophilic Waterborne Polyurethane Prepolymer, degree of neutralization is 95 ~ 100%;
(3) be dispersed under the high speed shear effect of stirrer in 250 parts of deionized waters by the hydrophilic Waterborne Polyurethane Prepolymer obtained, after for some time, drip the mixture of 3.1 parts of quadrols and 20 parts of water, hierarchy of control temperature is 30 ~ 40 DEG C.Emulsification times is 1h, and obtaining solid content is 30% aqueous polyurethane emulsion.
Embodiment 2
(1) be that the polyneopentyl glycol adipate glycol of 2000,4.8 parts of dimethylol propionic acids, 1.3 parts of Isosorbides, 6 parts of N-Methyl pyrrolidone are at 90 DEG C of vacuum hydro-extraction 1.5 ~ 2h by 80 parts of molecular weight, be cooled to 80 ~ 90 DEG C, add 31.8 parts of isophorone diisocyanates, reaction 2.5 ~ 3h, until NCO% reaches theoretical value, obtain the base polyurethane prepolymer for use as of NCO end-blocking;
(2) reduce system temperature, add 3.5 parts of neutralizing agent triethylamines, at 60 DEG C of reaction 0.5h, obtain hydrophilic Waterborne Polyurethane Prepolymer, degree of neutralization is 95 ~ 100%;
(3) be dispersed under the high speed shear effect of stirrer in 265 parts of deionized waters by the hydrophilic Waterborne Polyurethane Prepolymer obtained, after for some time, drip the mixture of 3.5 parts of quadrols and 20 parts of water, hierarchy of control temperature is 30 ~ 40 DEG C.Emulsification times is 1h, obtains the aqueous polyurethane emulsion that solid content is 29.7%.
Embodiment 3
(1) be that the polyneopentyl glycol adipate glycol of 2000,5.2 parts of dimethylol propionic acids, 4.0 parts of Isosorbides, 6 parts of N-Methyl pyrrolidone are at 90 DEG C of vacuum hydro-extraction 1.5 ~ 2h by 80 parts of molecular weight, be cooled to 80 ~ 90 DEG C, add 40.1 parts of isophorone diisocyanates, reaction 2.5 ~ 3h, until NCO% reaches theoretical value, obtain the base polyurethane prepolymer for use as of NCO end-blocking;
(2) reduce system temperature, add 3.8 parts of neutralizing agent triethylamines, at 60 DEG C of reaction 0.5h, obtain hydrophilic Waterborne Polyurethane Prepolymer, degree of neutralization is 95 ~ 100%;
(3) be dispersed under the high speed shear effect of stirrer in 295 parts of deionized waters by the hydrophilic Waterborne Polyurethane Prepolymer obtained, after for some time, drip the mixture of 4.5 parts of quadrols and 20 parts of water, hierarchy of control temperature is 30 ~ 40 DEG C.Emulsification times is 1h, obtains the aqueous polyurethane emulsion that solid content is 30%.
Embodiment 4
(1) be that the polyneopentyl glycol adipate glycol of 2000,5.8 parts of dimethylol propionic acids, 7.5 parts of Isosorbides, 6 parts of N-Methyl pyrrolidone are at 90 DEG C of vacuum hydro-extraction 1.5 ~ 2h by 80 parts of molecular weight, be cooled to 80 ~ 90 DEG C, add 50.7 parts of isophorone diisocyanates, reaction 2.5 ~ 3h, until NCO% reaches theoretical value, obtain the base polyurethane prepolymer for use as of NCO end-blocking;
(2) reduce system temperature, add 4.2 parts of neutralizing agent triethylamines, at 60 DEG C of reaction 0.5h, obtain hydrophilic Waterborne Polyurethane Prepolymer, degree of neutralization is 95 ~ 100%;
(3) be dispersed in the deionized water of 332 parts by the hydrophilic Waterborne Polyurethane Prepolymer obtained under the high speed shear effect of stirrer, after for some time, drip the mixture of 5.6 parts of quadrols and 20 parts of water, hierarchy of control temperature is 30 ~ 40 DEG C.Emulsification times is 1h, obtains the aqueous polyurethane emulsion that solid content is 34.2%.
Embodiment 5
(1) be that the polyneopentyl glycol adipate glycol of 2000,6.5 parts of dimethylol propionic acids, 11.9 parts of Isosorbides, 6 parts of N-Methyl pyrrolidone are at 90 DEG C of vacuum hydro-extraction 1.5 ~ 2h by 80 parts of molecular weight, be cooled to 80 ~ 90 DEG C, add 64.1 parts of isophorone diisocyanates, reaction 2.5 ~ 3h, until NCO% reaches theoretical value, obtain the base polyurethane prepolymer for use as of NCO end-blocking;
(2) reduce system temperature, add 4.8 parts of neutralizing agent triethylamines, at 60 DEG C of reaction 0.5h, obtain hydrophilic Waterborne Polyurethane Prepolymer, degree of neutralization is 95 ~ 100%;
(3) be dispersed in the deionized water of 380 parts by the hydrophilic Waterborne Polyurethane Prepolymer obtained under the high speed shear effect of stirrer, after for some time, drip the mixture of 7.1 parts of quadrols and 20 parts of water, hierarchy of control temperature is 30 ~ 40 DEG C.Emulsification times is 1h, obtains the aqueous polyurethane emulsion that solid content is 37.1%.
Embodiment 6 test result
Fig. 1, Fig. 2 and table 1 are respectively the heat-resisting test curve figure of product (being labeled as WPU0 ~ 4 respectively) and the data of embodiment 1 ~ 5; Table 2 is the water-fast test data of embodiment 1 ~ 5; Fig. 3 and table 3 is respectively high-low temperature resistant test curve figure and the data of the product of embodiment 1 ~ 5; Table 4 is the glossiness test data of the product of embodiment 1 ~ 5.
Table 1
Table 2
| Sample | Water ratio, (wt%) |
| WPU-0 | 16.39 |
| WPU-1 | 8.47 |
| WPU-2 | 5.84 |
| WPU-3 | 5.78 |
| WPU-4 | 3.53 |
Table 3
| Sample | T g，(℃) | T m，(℃) |
| WPU-0 | -32.5 | 139.2 |
| WPU-1 | -30.0 | 85.5 |
| WPU-2 | -31.5 | 80.7 |
| WPU-3 | -30.4 | 95.9 |
| WPU-4 | -33.3 | 117.2 |
Table 4
As can be seen from above-mentioned chart, compared with the WPU film not adding Isosorbide, after introducing Isosorbide, at 20 DEG C, the glossiness of WPU film is increased to 78.0% from 63.2%; At 60 DEG C, the glossiness of WPU film is increased to 87.9% from 80.9%; At 85 DEG C, the glossiness of WPU film is increased to 97.2% from 91.4%.
Claims (5)
1. an aqueous polyurethane emulsion, is characterized in that, comprises the component represented with parts by weight as follows:
The number-average molecular weight of described polymer polyatomic alcohol is 1000 ~ 2000, for the mixture of one or more in polyethylene glycol adipate dibasic alcohol, poly adipate succinic acid ester dibasic alcohol, polyneopentyl glycol adipate dibasic alcohol, polytetrahydrofuran dibasic alcohol, PCDL, polyoxyethylene ether dibasic alcohol, polyoxytrimethylene ether dibasic alcohol, poly-1,3-PD ether dibasic alcohol, polycaprolactone diols;
Described hydrophilic chain extender is one or more mixture of N, N-dihydroxy ethyl list maleinamic acid, dimethylol propionic acid, dimethylolpropionic acid, the two amino propane sulfonic acid of 3-;
Described small molecule polyol is the mixture of one or more in Isosorbide and hexylene glycol, butyleneglycol, glycerol, TriMethylolPropane(TMP), glycol ether.
2. aqueous polyurethane emulsion according to claim 1, it is characterized in that, described vulcabond is the mixture of one or more in hexamethylene diisocyanate, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate.
3. aqueous polyurethane emulsion according to claim 1, is characterized in that, described polyhydric amine compounds is the mixture of one or more in quadrol, hexanediamine, diethylenetriamine, triethylene tetramine, 3,3-bis-chloro-4,4-diamino-ditans.
4. aqueous polyurethane emulsion according to claim 1, is characterized in that, described neutralizing agent is triethylamine or sodium hydroxide or the mixture of the two.
5., according to the preparation method of the arbitrary described aqueous polyurethane emulsion of Claims 1-4, it is characterized in that, comprise the steps:
By described polymer polyatomic alcohol, hydrophilic chain extender, small molecule polyol, N-Methyl pyrrolidone at 80 ~ 95 DEG C of vacuum hydro-extraction 1.5 ~ 2h, be cooled to 80 ~ 90 DEG C, add vulcabond, reaction 2.5 ~ 3h, until NCO% reaches theoretical value, obtain the base polyurethane prepolymer for use as of NCO end-blocking;
Reduce system temperature, add neutralizing agent, at 60 ~ 80 DEG C of reaction 0.5 ~ 1h, obtain Waterborne Polyurethane Prepolymer, degree of neutralization is 95 ~ 100%;
Described Waterborne Polyurethane Prepolymer is dispersed under the high speed shear effect of stirrer, and drip the mixture of polyamine and water, hierarchy of control temperature is 30 ~ 40 DEG C, and emulsification 0.5 ~ 1h obtains described aqueous polyurethane emulsion.
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|---|---|---|---|---|
| CN105348468A (en) * | 2015-12-03 | 2016-02-24 | 上海蓝欧化工科技有限公司 | High-light-transmission and high-solid-content waterborne polyurethane and preparation method thereof |
| CN106010204A (en) * | 2016-06-23 | 2016-10-12 | 袁春华 | Preparation method of siloxy alkylated waterborne polyurethane flame-retardant coating |
| CN106380568A (en) * | 2016-08-31 | 2017-02-08 | 四川达威科技股份有限公司 | Waterborne polyurethane and preparation method thereof, and waterborne polyurethane leather filling agent |
| CN108425107A (en) * | 2018-03-23 | 2018-08-21 | 合肥工业大学 | A kind of method that aqueous polyurethane film induction mineralising prepares composite coating |
| CN108914619A (en) * | 2018-07-11 | 2018-11-30 | 刘志 | A method of improving aqueous polyurethane efficiency in synthetic leather production |
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