CN105694699A - Extinction type aqueous polyurethane emulsion and preparation method of extinction type aqueous polyurethane emulsion - Google Patents
Extinction type aqueous polyurethane emulsion and preparation method of extinction type aqueous polyurethane emulsion Download PDFInfo
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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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- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
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- 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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- 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
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- 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
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- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- 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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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The invention provides extinction type aqueous polyurethane emulsion and a preparation method of the extinction type aqueous polyurethane emulsion. A polyurethane chain section is cladded on a hollow microsphere through a chemical bond by utilizing the large-grain-diameter hollow microsphere with an active functional group, so that a large-size latex particle is formed. The hollow microsphere has small density and has a hollow structure, so that the sedimentation problem of large-size polyurethane colloidal particles can be improved. Meanwhile, in a process of drying and forming a film, the particles can be gathered on the surface of the film to form certain roughness, so that the extinction aim is reached. The extinction degree can be regulated and controlled through adjusting the hollow structure and the grain size of the hollow microsphere, and aqueous polyurethane extinction emulsion, which meets different extinction requirements and is stable, can be prepared. According to the extinction type aqueous polyurethane emulsion provided by the invention, the extinction degree is adjustable; the solid content, the water resistance, the heat resistance and the mechanical properties are improved, and the extinction type aqueous polyurethane emulsion can be used as an extinction coating of leather, wood lacquer and the like.
Description
Technical field
The present invention relates to aqueous functional macromolecule emulsion technical field, in particular to a kind of extinction type aqueous polyurethane emulsion and preparation method thereof。
Background technology
Along with formulation and the enforcement of various countries' environmental protection law, water paint is owing to having incombustibility, nontoxic or low toxicity, and environmental injury is little, and has the advantage saving the energy and resource, replaces solvent based coating just gradually, becomes the important directions of world's paint development。And aqueous polyurethane coating can pass through MOLECULE DESIGN due to it, polyurethane chain introduces various functional group and carries out crosslinking and composite modified, be also increasingly becoming the development priority of water paint。
Aqueous polyurethane is according to the difference of glossiness after film forming, it is possible to be divided into Gao Guang, zero diopter, unglazed etc.。After its film forming of low-luster resin it is generally acknowledged, glossiness wants≤40。Along with the raising of people's living standard and aesthetic standards, the requirement of matting resin is also gradually stepped up。The resin of these low-lusters is widely used in the fields such as leather finish, woodcare paint, plastic coating, paper covering with paint。
And current delustring technology depends on the way of additional flatting silica to reduce glossiness。As patent CN201110404636.9 and CN201310123871.8 reduces the glossiness after emulsion film forming by the method for additional flatting silica。But this method has certain drawback, it is simply that the poor compatibility of flatting silica and emulsion, it is easy to delaminating deposition occurs；It is typically necessary and it is possible to additionally incorporate other auxiliary agent and adjust, not only add production cost, be also that production stage is more loaded down with trivial details。And the permeability of the emulsion typically resulted in and extinction are also than the difference of solvent-borne type emulsion。Patent CN201310651725.2 have employed two kinds of various sizes of polyaminoester emulsions to carry out mixing composite, and one of which emulsion components contains and has cross-linked structure and the bigger emulsion particle of particle diameter, and another kind of emulsion is then the emulsion particle less containing particle diameter。After both emulsions carry out mixing covering with paint, the micelle particle that particle diameter is bigger in dry run can make film surface have bigger roughness, thus reaching the effect of delustring。Patent CN201410099458.7, CN201310292215.0 and CN201510386759.2 are then the adjustment by synthetic method, utilize hydrophilic chain extender sulfonate and hydrazine chain extender to be directly prepared for the aqueous polyurethane emulsion containing big particle diameter。In emulsion film dry run, owing to the existence of big particle diameter micelle makes film surface roughness increase, thus having reached the effect of delustring。But, the emulsion of these excessive particle diameters has obvious precipitated and separated to be occurred, although can redispersion, but the stability of emulsion long-term storage has been still impact。Just there is patent CN201410467681.2 to adopt one polyurethane molecular chain to be terminated light-absorbing acrylic acid-grafted class material further, utilize the method for chemical quenching to prepare leather flatting emulsion。The leather covered with paint, lacquer, colour wash, etc. out has natural extinction effect, and water-fast, the solvent resistance of coating are improved。But this method is in end-blocking preparation process, it is necessary to repeatedly adding acetone and control viscosity, complicated operation, and emulsion with a large amount of inflammable and explosive solvents, still-process is wasted time and energy, it is also difficult to remove solvent completely。Patent CN201310616022.6 is with anionic occlusive polyurethane and nonionic polyurethane for seed emulsion, then acrylic acid mixture adds a kind of matting resin with phase separation structure wherein carrying out being polymerized and obtain。And the hydroxyl generation cross-linking reaction in anion occlusive polyurethane and acrylic resin, enhance mechanical strength and the anti-scratch performance of matting resin。But preparation process still cannot be avoided the use of a large amount of acetone diluent, and production stage is loaded down with trivial details, it is difficult to industrialized production。CN201410583478.1 adopts to add 2-hydroxy benzenes methyl sulfide to change refraction index to reach the purpose of delustring。But system is still and inevitably employs substantial amounts of poisonous auxiliary agent and alcohol ether solvent, it is difficult to meet the requirement of low VOC emission standard。
In view of this, the special proposition present invention。
Summary of the invention
The first object of the present invention is in that the extinction type aqueous polyurethane emulsion providing the preparation method of a kind of extinction type aqueous polyurethane emulsion to prepare, described extinction type aqueous polyurethane emulsion, its delustring degree has controllability, and solid content, resistance to water, thermostability, mechanical property are improved, it is possible to the delustred coating as leather, woodcare paint etc. uses。
The second object of the present invention is in that the preparation method providing a kind of above-mentioned extinction type aqueous polyurethane emulsion, the preparation method technique of described extinction type aqueous polyurethane emulsion is simple, can be adjusted according to required delustring degree, in addition can also improve the solid content of gained extinction type aqueous polyurethane emulsion, resistance to water, thermostability, mechanical property, be suitable to large-scale production and promote。
In order to realize the above-mentioned purpose of the present invention, spy by the following technical solutions:
A kind of extinction type aqueous polyurethane emulsion, including component A and B component, described component A is the water-based emulsion of the polyaminoester microball being coated on tiny balloon to be formed polyurethane, and described B component is aqueous polyurethane emulsion。
Extinction type aqueous polyurethane emulsion of the present invention, adopts specified raw material to prepare, and its delustring degree has controllability, and solid content, resistance to water, thermostability, mechanical property are improved, it is possible to the delustred coating as leather, woodcare paint etc. uses。
Preferably, the particle diameter of described tiny balloon is 700-2000nm, it is preferred to 700-1800nm, more preferably 800-1500nm。
Preferably, the wall thickness of described tiny balloon is 50-800nm, it is preferred to 50-700nm, more preferably 50-600nm；
Preferably, described tiny balloon surface is with can with the functional group of isocyanate reaction, it is preferred to hydroxyl and one or both in amino；Described tiny balloon is preferably functionalized SiO 2 hollow microsphere, one or more in polystyrene hollow microsphere。
The hollow-core construction of tiny balloon can regulate, and namely its wall thickness can select。Difference according to its wall thickness, affects light scattering situation betwixt。Add the selection of different tiny balloon particle diameter, it is possible to the delustring degree after final emulsion film forming is adjusted。Just can prepare the waterborne polyurethane coating agent with different delustring degree by simple material choice。
Preferably, the particle diameter of described polyaminoester microball is 900-3000nm, it is preferred to 900-2500nm, more preferably 1000-2000nm。
Preferably, in described B component, in aqueous polyurethane emulsion, the particle diameter of granule is 20-500nm, it is preferred to 20-400nm, more preferably 50-400nm。
Polyurethane molecular chain is coated on tiny balloon by the method for chemical bonding by the present invention, obtains the polyurethane micelle of a kind of big particle diameter。Due to density and the hollow-core construction of tiny balloon, improve the sedimentation situation of big particle diameter polyurethane micelle so that it is can be stably dispersed in emulsion。And by the adjustment to component A and B component particle diameter, reach required delustring degree。Additionally, the addition of tiny balloon is a kind of rigid filled equal to adding, the mechanical property of final finishing agent, resistance to water, solvent resistance are all improved。
Described polyurethane is mainly by polyhydric alcohol, isocyanates, chain extender, salt forming agent, and initiator prepares。
Preferably, the molecular weight of described polyhydric alcohol is 500-5000, it is preferred to 500-4000, more preferably 500-3000；
Preferably, described polyhydric alcohol includes polyethylene terephthalate polyhydric alcohol, polybutylene terephthalate (PBT) polyhydric alcohol, 10PE27 polyhydric alcohol, poly terephthalic acid hexanediol ester polyol, polyethylene oxide polyol, PolyTHF ethoxylated polyhydric alcohol, one or more in polyoxypropylene polyol, polycarbonate polyol, polycaprolactone polyol；
Described isocyanates includes one or more in isophorone diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexyl methyl hydride diisocyanate, tetramethyl xylylene diisocyanate；
Described chain extender include dihydromethyl propionic acid, dimethylolpropionic acid, nonionic dihydroxylic alcohols, ethylenediamine base ethyl sulfonic acid sodium, 1,4-butanediol-2-sodium sulfonate, trimethylolpropane, tetramethylolmethane, glycerol, ethylene glycol, 1, one or more in 4 butanediols, 1,6 hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, ethylenediamine, ammonia, isophorone diamine, hydrazine hydrate, diethylenetriamine, triethylene tetramine；
Described salt forming agent includes one or more in triethylamine, sodium hydroxide, potassium hydroxide；
Described initiator includes one or more in dibutyl tin dilaurate, stannous octoate。
Adopting the different polyurethane that different raw materials will prepare, then be coated with tiny balloon, it is possible to obtain different extinction effects, actual extinction effect can by adopting the tiny balloon of specific polyurethane and specified particle diameter to carry out being coated with regulating。
Preferably, the polyurethane molecular amount in described extinction type aqueous polyurethane emulsion is 20000-250000, it is preferred to 50000-200000, more preferably 50000-150000。
Preferably, the solid content of described extinction type aqueous polyurethane emulsion is 10%-50%, it is preferred to 10%-45%, more preferably 15%-40%。
Adopt the solid content of specific polyurethane molecular amount and aqueous polyurethane emulsion, contribute to regulating to required delustring degree described extinction type aqueous polyurethane emulsion。
The preparation method of above-mentioned a kind of extinction type aqueous polyurethane emulsion, utilize the tiny balloon with active function groups, polyurethane segment is coated on tiny balloon by chemical bond, forms the water-based emulsion of polyaminoester microball, aqueous polyurethane emulsion is formed dispersed latex grain。
Polyurethane segment, mainly by the big particle diameter tiny balloon with active function groups, is coated on tiny balloon by the present invention by chemical bond, thus forming a kind of large-sized emulsion particle。Owing to tiny balloon density is little and has hollow-core construction, it is possible to improve the settlement issues of big particle diameter polyurethane micelle。Meanwhile, in drying and forming-film process, it is possible to form certain roughness at film surface aggregation, and then reach the purpose of delustring。Light degree can be offseted by the adjustment of tiny balloon hollow-core construction and size to regulate and control, it is possible to preparation meets different delustring and requires and stable aqueous polyurethane delustring emulsion。
The preparation method of above-mentioned a kind of extinction type aqueous polyurethane emulsion, comprises the steps:
(1) isocyanates, polyhydric alcohol, tiny balloon react；
(2) add chain extender, initiator and solvent, be obtained by reacting performed polymer；
(3) salt forming agent and solvent, stirring reaction are added after cooling；
(4) deionized water, dispersed with stirring are added after cooling；
(5) adding chain extender, chain extension obtains the water-based emulsion of polyaminoester microball。
Preferably, described solvent is N,N-dimethylacetamide。
The preparation method of above-mentioned a kind of extinction type aqueous polyurethane emulsion, comprises the steps:
(1) isocyanates, polyhydric alcohol react；
(2) add chain extender, initiator and solvent, be obtained by reacting performed polymer；
(3) salt forming agent and solvent, stirring reaction are added after cooling；
(4) deionized water, dispersed with stirring are added after cooling；
(5) adding chain extender, chain extension obtains aqueous polyurethane emulsion。
Preferably, described solvent is N,N-dimethylacetamide。
The water-based emulsion of polyaminoester microball obtains a kind of extinction type aqueous polyurethane emulsion with the dispersion of aqueous polyurethane emulsion Homogeneous phase mixing。
Preferably, water-based emulsion and the aqueous polyurethane emulsion of the polyaminoester microball in described extinction type aqueous polyurethane emulsion preferably employ identical polyurethane, dispersion of fully dissolving each other when contributing to follow-up mixing。
The water-based emulsion of the polyaminoester microball in described extinction type aqueous polyurethane emulsion can arbitrary volume mix than mutually with aqueous polyurethane emulsion, in order to regulates to required delustring degree；The water-based emulsion of polyaminoester microball and the volume ratio of aqueous polyurethane emulsion in described extinction type aqueous polyurethane emulsion are preferably 1-3:1-3, more preferably 1:1。
Compared with prior art, the invention have the benefit that
1. polyurethane molecular chain is coated on tiny balloon by the method for chemical bonding, obtains the polyurethane micelle of a kind of big particle diameter。Due to density and the hollow-core construction of tiny balloon, improve the sedimentation situation of big particle diameter polyurethane micelle so that it is can be stably dispersed in emulsion。
2. the hollow-core construction of tiny balloon can regulate, and namely its wall thickness can select。Difference according to its wall thickness, affects light scattering situation betwixt。Add the selection of different tiny balloon particle diameter, it is possible to the delustring degree after final emulsion film forming is adjusted。Just can prepare the waterborne polyurethane coating agent with different delustring degree by simple material choice。
3. the addition of tiny balloon is equal to adding a kind of rigid filled, to final finishing agent mechanical property, and resistance to water, solvent resistance is all improved。
Detailed description of the invention
Below in conjunction with embodiment, embodiment of the present invention are described in detail, it will be appreciated by those skilled in the art that the following example is merely to illustrate the present invention, and are not construed as restriction the scope of the present invention。Unreceipted actual conditions person in embodiment, conventionally the condition of condition or manufacturer's suggestion carries out。Agents useful for same or the unreceipted production firm person of instrument, be and can pass through the commercially available conventional products bought and obtain。
The preparation method that the invention provides a kind of extinction type aqueous polyurethane emulsion, described extinction type aqueous polyurethane emulsion is mainly prepared by component A and B component；
The preparation method of described component A, comprises the steps:
(1) by isocyanates, polyhydric alcohol, tiny balloon reacts 2-4 hour at 60-100 DEG C；
(2) add chain extender, initiator and solvent, react 3-5 hour at 50-90 DEG C, obtain performed polymer；
(3) cooling 30-50 DEG C adds salt forming agent and solvent, stirs 30 minutes to 1 hour；
(4) cooling 10-30 DEG C, adds appropriate amount of deionized water, and high-speed stirred is disperseed 30-60 minute simultaneously。
(5) add amine chain extender, further chain extension, obtain component A；
Described extinction type aqueous polyurethane emulsion is mainly prepared by component A and B component；
The preparation method of described B component, comprises the steps:
(1) by isocyanates, polyhydric alcohol reacts 2-4 hour at 60-100 DEG C；
(2) add chain extender, initiator and solvent, react 3-5 hour at 50-90 DEG C, obtain performed polymer；
(3) cooling 30-50 DEG C adds salt forming agent and solvent, stirs 30 minutes to 1 hour；
(4) cooling 10-30 DEG C, adds appropriate amount of deionized water, and high-speed stirred is disperseed 30-60 minute simultaneously。
(5) add amine chain extender, further chain extension, obtain B component。
Embodiment 1
The preparation method of a kind of extinction type aqueous polyurethane emulsion, comprises the steps:
(1) by polyethylene terephthalate polyhydric alcohol that 20g molecular weight is 1000 and 10g isophorone diisocyanate, 1g SiO 2 hollow microsphere (particle diameter 1000nm, wall thickness 100nm) adds in there-necked flask, reacts 3 hours at 90 DEG C；
(2) by 1.5g dihydromethyl propionic acid, 0.8g trimethylolpropane, 4gN, N-dimethyl acetylamide and a small amount of dibutyl tin laurate add reaction system, react 4 hours at 90 DEG C；
(3) it is cooled to 50 DEG C, adds 1g triethylamine and 4g acetone soln is neutralized, react 1 hour；
(4) it is cooled to less than 30 DEG C, adds 60g water and carry out emulsifying 30 minutes；
(5) add 0.7g ethylenediamine solution and again carry out chain extension 1 hour, filter discharging, obtain aqueous polyurethane emulsion component A。
(6) prepare the aqueous polyurethane emulsion without tiny balloon according to similarity condition and obtain component B。
After being mixed homogeneously by the proportioning of 1:1 by component A and component B, film on a glass, 120 DEG C of convection oven dry two hours, and film presents matte effect, test its 60 degree of angle glossiness 20 with vancometer。Be 1245nm, component B mean diameter by the mean diameter of particle size analyzer fractions tested A it is 342nm。Taking appropriate mixed emulsion centrifuge centrifugal 15 minutes at 3,000 rpm, emulsion, without obvious sediment。
Embodiment 2
The preparation method of a kind of extinction type aqueous polyurethane emulsion, comprises the steps:
(1) by PolyTHF ethoxylated polyhydric alcohol that 15g molecular weight is 1500 and 12g methyl diphenylene diisocyanate, 4g SiO 2 hollow microsphere (particle diameter 1500nm, wall thickness 80nm) adds in there-necked flask, reacts 4 hours at 80 DEG C；
(2) by 2.0g dimethylolpropionic acid, 0.5g trimethylolpropane, 4gN, N-dimethyl acetylamide and a small amount of dibutyl tin laurate add reaction system, react 4 hours at 80 DEG C；
(3) it is cooled to 50 DEG C, adds 1.2g triethylamine and 4g acetone soln is neutralized, react 1 hour；
(4) it is cooled to less than 30 DEG C, adds 55g water and carry out emulsifying 30 minutes；
(5) add 0.8g ethylenediamine solution and again carry out chain extension 1 hour, filter discharging, obtain aqueous polyurethane emulsion component A。
(6) prepare the aqueous polyurethane emulsion without tiny balloon according to similarity condition and obtain component B。
After being mixed homogeneously by the proportioning of 2:1 by component A and component B, film on a glass, 120 DEG C of convection oven dry two hours, and face is slightly white, light tight。Its 60 degree of angle glossiness are tested less than 10 with vancometer。Be 1785nm, component B mean diameter by the mean diameter of particle size analyzer fractions tested A it is 220nm。Taking appropriate mixed emulsion centrifuge centrifugal 15 minutes at 3,000 rpm, emulsion, without obvious sediment。
Embodiment 3
The preparation method of a kind of extinction type aqueous polyurethane emulsion, comprises the steps:
(1) by polycarbonate polyol that 22g molecular weight is 800 and 15g hexamethylene diisocyanate, 6g polystyrene hollow microsphere (particle diameter 1200nm, wall thickness 120nm) adds in there-necked flask, reacts 3 hours at 95 DEG C；
(2) by 1.0g dimethylolpropionic acid, 0.5g1,4-butanediol-2-sodium sulfonate, 0.6g trimethylolpropane, 4gN, N-dimethyl acetylamide and a small amount of dibutyl tin laurate add reaction system, react 3 hours at 82 DEG C；
(3) it is cooled to 50 DEG C, adds 0.8g triethylamine and 4g acetone soln is neutralized, react 1 hour；
(4) it is cooled to less than 30 DEG C, adds 70g water and carry out emulsifying 30 minutes；
(5) add 0.6g ethylenediamine solution and again carry out chain extension 1 hour, filter discharging, obtain aqueous polyurethane emulsion component A。
(6) prepare the aqueous polyurethane emulsion without tiny balloon according to similarity condition and obtain component B。
After being mixed homogeneously by the proportioning of 3:1 by component A and component B, film on a glass, 120 DEG C of convection oven dry two hours, and face is light tight, white。Its 60 degree of angle glossiness are tested less than 10 with vancometer。Be 1406nm, component B mean diameter by the mean diameter of particle size analyzer fractions tested A it is 258nm。Taking appropriate mixed emulsion centrifuge centrifugal 15 minutes at 3,000 rpm, emulsion, without obvious sediment。
Embodiment 4
The preparation method of a kind of extinction type aqueous polyurethane emulsion, comprises the steps:
(1) by poly terephthalic acid hexanediol ester polyol that 10g molecular weight is 2000 and 20g4,4'-dicyclohexyl methyl hydride diisocyanate, 6g SiO 2 hollow microsphere (particle diameter 2000nm, wall thickness 300nm) adds in there-necked flask, reacts 3 hours at 95 DEG C；
(2) by 2.0g dimethylolpropionic acid, 0.9g trimethylolpropane, 4gN, N-dimethyl acetylamide and a small amount of dibutyl tin laurate add reaction system, react 3 hours at 95 DEG C；
(3) it is cooled to 50 DEG C, adds 1.5g triethylamine and 4g acetone soln is neutralized, react 1 hour；
(4) it is cooled to less than 30 DEG C, adds 65g water and carry out emulsifying 30 minutes；
(5) add 1.2g ethylenediamine solution and again carry out chain extension 1 hour, filter discharging, obtain aqueous polyurethane emulsion component A。
(6) prepare the aqueous polyurethane emulsion without tiny balloon according to similarity condition and obtain component B。
After being mixed homogeneously by the proportioning of 1:3 by component A and component B, film on a glass, 120 DEG C of convection oven dry two hours, and face becomes matte effect, slightly turns white。Its 60 degree of angle glossiness 15 are tested with vancometer。Be 2275nm, component B mean diameter by the mean diameter of particle size analyzer fractions tested A it is 289nm。Taking appropriate mixed emulsion centrifuge centrifugal 15 minutes at 3,000 rpm, emulsion, without obvious sediment。
Embodiment 5
The preparation method of a kind of extinction type aqueous polyurethane emulsion, comprises the steps:
(1) by polyethylene oxide polyol that 15g molecular weight is 1500 and 22g isophorone diisocyanate, 5g SiO 2 hollow microsphere (particle diameter 1500nm, wall thickness 150nm) adds in there-necked flask, reacts 3 hours at 95 DEG C；
(2) by 1.0g dimethylolpropionic acid, 1.0g nonionic dihydroxylic alcohols, 0.5g trimethylolpropane, 4gN, N-dimethyl acetylamide and a small amount of dibutyl tin laurate add reaction system, react 3 hours at 95 DEG C；
(3) it is cooled to 50 DEG C, adds 0.7g triethylamine and 4g acetone soln is neutralized, react 1 hour；
(4) it is cooled to less than 30 DEG C, adds 50g water and carry out emulsifying 30 minutes；
(5) add 1.0g ethylenediamine solution and again carry out chain extension 1 hour, filter discharging, obtain aqueous polyurethane emulsion component A。
(6) prepare the aqueous polyurethane emulsion without tiny balloon according to similarity condition and obtain component B。
After being mixed homogeneously by the proportioning of 1:5 by component A and component B, film on a glass, 120 DEG C of convection oven dry two hours, and face becomes matte effect。Its 60 degree of angle glossiness 25 are tested with vancometer。Be 1807nm, component B mean diameter by the mean diameter of particle size analyzer fractions tested A it is 242nm。Taking appropriate mixed emulsion centrifuge centrifugal 15 minutes at 3,000 rpm, emulsion, without obvious sediment。
Embodiment 6
The preparation method of a kind of extinction type aqueous polyurethane emulsion, comprises the steps:
(1) by polycarbonate polyol that 20g molecular weight is 2000 and 25g methyl diphenylene diisocyanate, 7g SiO 2 hollow microsphere (particle diameter 1200nm, wall thickness 100nm) adds in there-necked flask, reacts 4 hours at 60 DEG C；
(2) by 1.5g dihydromethyl propionic acid, 1.0g nonionic dihydroxylic alcohols 0.6g trimethylolpropane, 4gN, N-dimethyl acetylamide and a small amount of dibutyl tin laurate add reaction system, react 4 hours at 60 DEG C；
(3) it is cooled to 50 DEG C, adds 0.8g triethylamine and 4g acetone soln is neutralized, react 1 hour；
(4) it is cooled to less than 30 DEG C, adds 50g water and carry out emulsifying 30 minutes；
(5) add 0.5g ethylenediamine solution and again carry out chain extension 1 hour, filter discharging, obtain aqueous polyurethane emulsion component A。
(6) prepare the aqueous polyurethane emulsion without tiny balloon according to similarity condition and obtain component B。
After being mixed homogeneously by the proportioning of 2:3 by component A and component B, film on a glass, 120 DEG C of convection oven dry two hours, and face becomes matte effect。Its 60 degree of angle glossiness 30 are tested with vancometer。Be 1407nm, component B mean diameter by the mean diameter of particle size analyzer fractions tested A it is 189nm。Taking appropriate mixed emulsion centrifuge centrifugal 15 minutes at 3,000 rpm, emulsion, without obvious sediment。
By above-described embodiment it can be seen that extinction type aqueous polyurethane emulsion of the present invention as required, can regulate delustring degree, and dispersion effect is high, it is simple to actual promote the use of。
Polyurethane molecular chain is coated on tiny balloon by the method for chemical bonding by the present invention, obtains the polyurethane micelle of a kind of big particle diameter。Due to density and the hollow-core construction of tiny balloon, improve the sedimentation situation of big particle diameter polyurethane micelle so that it is can be stably dispersed in emulsion。The hollow-core construction of tiny balloon can regulate, and namely its wall thickness can select。Difference according to its wall thickness, affects light scattering situation betwixt。Add the selection of different tiny balloon particle diameter, it is possible to the delustring degree after final emulsion film forming is adjusted。Just can prepare the waterborne polyurethane coating agent with different delustring degree by simple material choice。The addition of tiny balloon is equal to adding a kind of rigid filled, to final finishing agent mechanical property, and resistance to water, solvent resistance is all improved。
Although illustrate and describing the present invention with specific embodiment, however it will be appreciated that may be made that when without departing substantially from the spirit and scope of the present invention many other change and amendment。It is, therefore, intended that include all such changes and modifications belonging in the scope of the invention in the following claims。
Claims (10)
1. an extinction type aqueous polyurethane emulsion, it is characterised in that include component A and B component, described component A is the water-based emulsion of polyaminoester microball being coated on tiny balloon to be formed polyurethane, and described B component is aqueous polyurethane emulsion。
2. a kind of extinction type aqueous polyurethane emulsion according to claim 1, it is characterised in that the particle diameter of described tiny balloon is 700-2000nm, it is preferred to 700-1800nm, more preferably 800-1500nm。
3. a kind of extinction type aqueous polyurethane emulsion according to claim 2, it is characterised in that the wall thickness of described tiny balloon is 50-800nm, it is preferred to 50-700nm, more preferably 50-600nm；
Preferably, described tiny balloon surface is with can with the functional group of isocyanate reaction, it is preferred to hydroxyl and one or both in amino；Described tiny balloon is preferably functionalized SiO 2 hollow microsphere, one or more in polystyrene hollow microsphere。
4. a kind of extinction type aqueous polyurethane emulsion according to claim 1, it is characterised in that the particle diameter of described polyaminoester microball is 900-3000nm, it is preferred to 900-2500nm, more preferably 1000-2000nm。
5., according to a kind of extinction type aqueous polyurethane emulsion described in claim 1, it is characterised in that in described B component, in aqueous polyurethane emulsion, the particle diameter of granule is 20-500nm, it is preferred to 20-400nm, more preferably 50-400nm。
6. a kind of extinction type aqueous polyurethane emulsion according to claim 1, it is characterised in that described polyurethane is mainly by polyhydric alcohol, isocyanates, chain extender, salt forming agent, and initiator prepares；
Preferably, described polyhydric alcohol includes polyethylene terephthalate polyhydric alcohol, polybutylene terephthalate (PBT) polyhydric alcohol, 10PE27 polyhydric alcohol, poly terephthalic acid hexanediol ester polyol, polyethylene oxide polyol, PolyTHF ethoxylated polyhydric alcohol, one or more in polyoxypropylene polyol, polycarbonate polyol, polycaprolactone polyol；More having choosing, the molecular weight of described polyhydric alcohol is 500-5000；
Preferably, described isocyanates includes one or more in isophorone diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexyl methyl hydride diisocyanates, tetramethyl xylylene diisocyanate；
Preferably, described chain extender include dihydromethyl propionic acid, dimethylolpropionic acid, nonionic dihydroxylic alcohols, ethylenediamine base ethyl sulfonic acid sodium, 1,4-butanediol-2-sodium sulfonate, trimethylolpropane, tetramethylolmethane, glycerol, ethylene glycol, 1, one or more in 4 butanediols, 1,6 hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, ethylenediamine, ammonia, isophorone diamine, hydrazine hydrate, diethylenetriamine, triethylene tetramine；
Preferably, described salt forming agent includes one or more in triethylamine, sodium hydroxide, potassium hydroxide；
Preferably, described initiator includes one or more in dibutyl tin dilaurate, stannous octoate。
7. a kind of extinction type aqueous polyurethane emulsion according to claim 1, it is characterised in that the polyurethane molecular amount in described extinction type aqueous polyurethane emulsion is 20000-250000, it is preferred to 50000-200000, more preferably 50000-150000；
The solid content of described extinction type aqueous polyurethane emulsion is 10%-50%, it is preferred to 10%-45%, more preferably 15%-40%。
8. the preparation method of a kind of extinction type aqueous polyurethane emulsion as described in any one of claim 1-7, it is characterized in that, utilize the tiny balloon with active function groups, polyurethane segment is coated on tiny balloon by chemical bond, form the water-based emulsion of polyaminoester microball, aqueous polyurethane emulsion is formed dispersed latex grain。
9. the preparation method of a kind of extinction type aqueous polyurethane emulsion according to claim 8, it is characterised in that comprise the steps:
(1) isocyanates, polyhydric alcohol, tiny balloon react；
(2) add chain extender, initiator and solvent, be obtained by reacting performed polymer；
(3) salt forming agent and solvent, stirring reaction are added after cooling；
(4) deionized water, dispersed with stirring are added after cooling；
(5) adding chain extender, chain extension obtains the water-based emulsion of polyaminoester microball。
10. the preparation method of a kind of extinction type aqueous polyurethane emulsion according to claim 8, it is characterised in that comprise the steps:
(1) isocyanates, polyhydric alcohol react；
(2) add chain extender, initiator and solvent, be obtained by reacting performed polymer；
(3) salt forming agent and solvent, stirring reaction are added after cooling；
(4) deionized water, dispersed with stirring are added after cooling；
(5) adding chain extender, chain extension obtains aqueous polyurethane emulsion。
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