CN105694699B - A kind of extinction type aqueous polyurethane emulsion and preparation method thereof - Google Patents
A kind of extinction type aqueous polyurethane emulsion and preparation method thereof Download PDFInfo
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- CN105694699B CN105694699B CN201610055970.0A CN201610055970A CN105694699B CN 105694699 B CN105694699 B CN 105694699B CN 201610055970 A CN201610055970 A CN 201610055970A CN 105694699 B CN105694699 B CN 105694699B
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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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- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
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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
- C08G18/4205—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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G18/65—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
- 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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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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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
- C08G18/70—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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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The present invention provides a kind of extinction type aqueous polyurethane emulsions and preparation method thereof.The present invention is mainly to be coated on polyurethane segment on tiny balloon by chemical bond, using the big partial size tiny balloon for having active function groups to form a kind of large-sized emulsion particle.Since tiny balloon density is small and has hollow structure, the settlement issues of big partial size polyurethane micelle can be improved.Meanwhile during the drying and film forming process, it can assemble to form certain roughness in film surface, and then achieve the purpose that delustring.Light path degree can be offseted by the adjustment of tiny balloon hollow structure and particle size to be regulated and controled, and can be prepared and be met different delustring requirements and stable aqueous polyurethane delustring lotion.Extinction type aqueous polyurethane emulsion of the present invention, delustring degree has controllability, and solid content, water resistance, heat resistance, mechanical property are improved, and the delustred coating that can be used as leather, woodcare paint etc. uses.
Description
Technical field
The present invention relates to aqueous functional macromolecule emulsion technical fields, in particular to a kind of aqueous poly- ammonia of extinction type
Ester lotion and preparation method thereof.
Background technique
With the formulation and implementation of various countries' environmental protection law, water paint is right due to incombustibility, non-toxic or low-toxic
Environmental injury is small, and has the advantages that energy saving and resource, just gradually replaces solvent based coating, becomes world's paint development
Important directions.And aqueous polyurethane coating can introduce various functional groups by MOLECULE DESIGN due to it in polyurethane chain
Carry out crosslinking and it is composite modified, be also increasingly becoming the development priority of water paint.
Aqueous polyurethane can be divided into bloom, zero diopter, unglazed etc. according to the difference of glossiness after film forming.It is generally acknowledged that
Glossiness wants≤40 after its film forming of low-luster resin.With the raising of people's living standard and aesthetic standards, to matting resin
Requirement be also gradually increased.The resin of these low-lusters is widely used in leather finish, woodcare paint, plastic coating, paper
The fields such as covering with paint.
And current delustring technology depends on the method for additional flatting silica to reduce glossiness.Such as patent
CN201110404636.9 and CN201310123871.8 is after reducing emulsion film forming by the method for additional flatting silica
Glossiness.But this method has certain drawbacks, is exactly the poor compatibility of flatting silica and lotion, and it is heavy to be easy to happen layering
Drop；It is typically necessary and additionally incorporates other auxiliary agents to adjust, not only increase production cost and production stage is more cumbersome.
And the permeability and extinction of the lotion typically resulted in are also than the difference of solvent type lotion.And patent CN201310651725.2 is then
It is to use two kinds of various sizes of polyaminoester emulsions to carry out mixing compounding, one of emulsion components contain with cross-linked structure
And the biggish emulsion particle of partial size, and another lotion is then containing the lesser emulsion particle of partial size.Both lotions carry out mixing painting
After decorations, the biggish micella particle of partial size can make film surface have biggish roughness in the drying process, to reach delustring
Effect.And patent CN201410099458.7, CN201310292215.0 and CN201510386759.2 are then by synthesis side
The adjustment of method is directly prepared for using hydrophilic chain extender sulfonate and hydrazine chain extender containing large-sized aqueous polyurethane
Lotion.In emulsion film drying process, since the presence of big partial size micelle increases film surface roughness, disappear to reach
The effect of light.But these excessively large-sized lotions have apparent precipitated and separated and occur, although can be with redisperse, to cream
The stability that liquid is stored for a long time is still to have an impact.Further just there is patent CN201410467681.2 using a kind of absorbable light
Acrylic acid-grafted substance polyurethane molecular chain is blocked, prepare leather flatting lotion using the method for chemical quenching.
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
In sealing end preparation process, need to be added acetone repeatedly to control viscosity, it is complicated for operation, and lotion is with a large amount of inflammable and explosive molten
Agent, distillation process are time-consuming and laborious, it is also difficult to completely remove solvent.Patent CN201310616022.6 is poly- with anionic closing
Urethane and nonionic polyurethane are seed emulsion, then acrylic acid mixture is added thereto polymerize obtained from a kind of tool
There is the matting resin of phase separation structure.And anion occlusive polyurethane is crosslinked with the hydroxyl in acrylic resin and is reacted, and is increased
The strong mechanical strength and anti-scratch performance of matting resin.But preparation process is not avoided that the use of a large amount of acetone diluents still,
And production stage is cumbersome, it is difficult to industrialized production.CN201410583478.1 be then using addition 2- hydroxyl thioanisole come
Change refraction index to achieve the purpose that delustring.But it is still inevitable in system and has used a large amount of toxic auxiliary agent and alcohol
Ether solvent, it is difficult to meet the requirement of low VOC emission standard.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is what the preparation method for providing a kind of extinction type aqueous polyurethane emulsion was prepared
Extinction type aqueous polyurethane emulsion, the extinction type aqueous polyurethane emulsion, delustring degree has controllability, and contains admittedly
Amount, water resistance, heat resistance, mechanical property are improved, and the delustred coating that can be used as leather, woodcare paint etc. uses.
The second object of the present invention is to provide a kind of preparation method of above-mentioned extinction type aqueous polyurethane emulsion, described
Extinction type aqueous polyurethane emulsion preparation method simple process, can be adjusted according to required delustring degree, additionally
Solid content, the water resistance, heat resistance, mechanical property that gained extinction type aqueous polyurethane emulsion can be improved, are suitable for large-scale production
It promotes.
In order to realize above-mentioned purpose of the invention, spy uses following technical scheme：
A kind of extinction type aqueous polyurethane emulsion, including component A and B component, the component A are that polyurethane is coated to sky
The water-based emulsion of the polyaminoester microball formed on heart microballoon, the B component are aqueous polyurethane emulsion.
Extinction type aqueous polyurethane emulsion of the present invention, is prepared using specified raw material, and delustring degree has adjustable
Property, and solid content, water resistance, heat resistance, mechanical property are improved, the delustred coating that can be used as leather, woodcare paint etc. makes
With.
Preferably, the partial size of the tiny balloon be 700-2000nm, preferably 700-1800nm, further preferably
800-1500nm。
Preferably, the wall thickness of the tiny balloon is 50-800nm, preferably 50-700nm, further preferably 50-
600nm；
Preferably, the tiny balloon surface has the functional group that can be reacted with isocyanates, preferably hydroxyl and amino
One or both of；The tiny balloon is preferably functionalized SiO 2 hollow microsphere, in polystyrene hollow microballoon
It is one or more.
The hollow structure of tiny balloon is adjustable, i.e., its wall thickness can choose.According to the difference of its wall thickness, light is influenced
Scattering situation therebetween.It, can be to the delustring degree after final emulsion film forming along with the selection of different tiny balloon partial sizes
It is adjusted.It can be selected by simple raw material to prepare the waterborne polyurethane coating agent with different delustring degree.
Preferably, the partial size of the polyaminoester microball be 900-3000nm, preferably 900-2500nm, further preferably
1000-2000nm。
Preferably, in the B component, the partial size of particle is 20-500nm, preferably 20- in aqueous polyurethane emulsion
400nm, further preferably 50-400nm.
Polyurethane molecular chain is coated on tiny balloon by the present invention by the method being chemically bonded, and obtains a kind of big partial size
Polyurethane micelle.Due to the density and hollow structure of tiny balloon, the sedimentation situation of big partial size polyurethane micelle is improved, is made
It can be stably dispersed in lotion.And by the adjustment to component A and B component partial size, to reach required delustring degree.This
Outside, the addition of tiny balloon is a kind of rigid filled equal to joined, to the mechanical property, water resistance, solvent resistant of final finishing agent
Property is all improved.
The polyurethane is mainly by polyalcohol, isocyanates, chain extender, salt forming agent, and initiator is prepared.
Preferably, the molecular weight of the polyalcohol is 500-5000, preferably 500-4000, further preferably 500-
3000；
Preferably, the polyalcohol includes polyethylene terephthalate polyalcohol, polybutylene terephthalate (PBT)
Polyalcohol, poly terephthalic acid hexylene glycol ester polyol, polyethylene oxide polyol, gathers polyethylene glycol adipate polyalcohol
Tetrahydrofuran ethoxylated polyhydric alcohol, one of polyoxypropylene polyol, polycarbonate polyol, polycaprolactone polyol or more
Kind；
The isocyanates includes isophorone diisocyanate, toluene di-isocyanate(TDI), diphenylmethane diisocyanate
Ester, hexamethylene diisocyanate, 4,4'- dicyclohexyl methyl hydride diisocyanate, in tetramethyl xylylene diisocyanate
It is one or more；
The chain extender includes dihydromethyl propionic acid, dimethylolpropionic acid, nonionic dihydroxylic alcohols, ethylenediamine base ethanesulfonic acid
Sodium, 1,4-butanediol -2- sodium sulfonate, trimethylolpropane, pentaerythrite, glycerine, ethylene glycol, Isosorbide-5-Nitrae butanediol, 1,6 oneself two
Alcohol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, ethylenediamine, ammonium hydroxide, isophorone diamine, hydrazine hydrate, divinyl
One of triamine, triethylene tetramine are a variety of；
The salt forming agent includes one of triethylamine, sodium hydroxide, potassium hydroxide or a variety of；
The initiator includes one of dibutyl tin dilaurate, stannous octoate or a variety of.
The different polyurethane that will be prepared using different raw materials, then coated with tiny balloon, it can obtain
Different extinction effects, practical extinction effect can be coated by using the tiny balloon of specific polyurethane and specified particle diameter
To adjust.
Preferably, the polyurethane molecular amount in the extinction type aqueous polyurethane emulsion is 20000-250000, preferably
50000-200000, further preferably 50000-150000.
Preferably, the solid content of the extinction type aqueous polyurethane emulsion be 10%-50%, preferably 10%-45%, into
One step is preferably 15%-40%.
Using specific polyurethane molecular amount and the solid content of aqueous polyurethane emulsion, facilitate the extinction type water
Property polyaminoester emulsion is adjusted to required delustring degree.
The preparation method of above-mentioned a kind of extinction type aqueous polyurethane emulsion, using hollow micro- with active function groups
Polyurethane segment is coated on tiny balloon by chemical bond, forms the water-based emulsion of polyaminoester microball by ball, in aqueous poly- ammonia
Dispersed latex grain is formed in ester lotion.
The present invention is mainly that polyurethane segment is passed through chemical bond using the big partial size tiny balloon for having active function groups
It is coated on tiny balloon, to form a kind of large-sized emulsion particle.Since tiny balloon density is small and has hollow structure,
The settlement issues of big partial size polyurethane micelle can be improved.Meanwhile during the drying and film forming process, can assemble to be formed in film surface
Certain roughness, and then achieve the purpose that delustring.It can be to delustring by the adjustment of tiny balloon hollow structure and particle size
Degree is regulated and controled, and can be prepared and be met different delustring requirements and stable aqueous polyurethane delustring lotion.
A kind of preparation method of above-mentioned extinction type aqueous polyurethane emulsion, includes the following steps：
(1) isocyanates, polyalcohol, tiny balloon are reacted；
(2) chain extender, initiator and solvent is added, reaction obtains performed polymer；
(3) salt forming agent and solvent are added after cooling down, is stirred to react；
(4) deionized water is added after cooling down, is dispersed with stirring；
(5) chain extender is added, chain extension obtains the water-based emulsion of polyaminoester microball.
Preferably, the solvent is n,N-dimethylacetamide.
A kind of preparation method of above-mentioned extinction type aqueous polyurethane emulsion, includes the following steps：
(1) isocyanates, polyalcohol are reacted；
(2) chain extender, initiator and solvent is added, reaction obtains performed polymer；
(3) salt forming agent and solvent are added after cooling down, is stirred to react；
(4) deionized water is added after cooling down, is dispersed with stirring；
(5) chain extender is added, chain extension obtains aqueous polyurethane emulsion.
Preferably, the solvent is n,N-dimethylacetamide.
The water-based emulsion of polyaminoester microball uniformly mixes dispersion with aqueous polyurethane emulsion, and to obtain a kind of extinction type aqueous poly-
Urethane lotion.
Preferably, the water-based emulsion of the polyaminoester microball in the extinction type aqueous polyurethane emulsion and aqueous polyurethane cream
Liquid preferably uses identical polyurethane, dispersion of sufficiently dissolving each other when facilitating subsequent mixing.
The water-based emulsion and aqueous polyurethane emulsion of polyaminoester microball in the extinction type aqueous polyurethane emulsion can be with
Arbitrary volume ratio mixes, to be adjusted to required delustring degree；Polyurethane in the extinction type aqueous polyurethane emulsion
The water-based emulsion of microballoon and the volume ratio of aqueous polyurethane emulsion are preferably 1-3:1-3, further preferably 1:1.
Compared with prior art, beneficial effects of the present invention are：
1. polyurethane molecular chain is coated on tiny balloon by the method being chemically bonded, obtain a kind of large-sized poly-
Urethane micelle.Due to the density and hollow structure of tiny balloon, the sedimentation situation of big partial size polyurethane micelle is improved, it can
It is stably dispersed in lotion.
2. the hollow structure of tiny balloon is adjustable, i.e., its wall thickness can choose.According to the difference of its wall thickness, light is influenced
The scattering situation of line therebetween.It, can be to the delustring journey after final emulsion film forming along with the selection of different tiny balloon partial sizes
Degree is adjusted.It can be selected by simple raw material to prepare the waterborne polyurethane coating agent with different delustring degree.
3. the addition of tiny balloon be equal to joined it is a kind of rigid filled, to the mechanical property of final finishing agent, water resistance,
Solvent resistance is all improved.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
The present invention provides a kind of preparation method of extinction type aqueous polyurethane emulsion, the extinction type aqueous polyurethane cream
Liquid is mainly prepared by component A and B component；
The preparation method of the component A, includes the following steps：
(1) by isocyanates, polyalcohol, tiny balloon reacts 2-4 hours at 60-100 DEG C；
(2) chain extender, initiator and solvent is added, is reacted 3-5 hours at 50-90 DEG C, obtains performed polymer；
(3) cool down 30-50 DEG C of addition salt forming agent and solvent, stirs 30 minutes to 1 hour；
(4) cool down 10-30 DEG C, appropriate amount of deionized water is added, while high-speed stirred is dispersed 30-60 minutes.
(5) amine chain extender is added, further chain extension obtains component A；
The extinction type aqueous polyurethane emulsion is mainly prepared by component A and B component；
The preparation method of the B component, includes the following steps：
(1) by isocyanates, polyalcohol reacts 2-4 hours at 60-100 DEG C；
(2) chain extender, initiator and solvent is added, is reacted 3-5 hours at 50-90 DEG C, obtains performed polymer；
(3) cool down 30-50 DEG C of addition salt forming agent and solvent, stirs 30 minutes to 1 hour；
(4) cool down 10-30 DEG C, appropriate amount of deionized water is added, while high-speed stirred is dispersed 30-60 minutes.
(5) amine chain extender is added, further chain extension obtains B component.
Embodiment 1
A kind of preparation method of extinction type aqueous polyurethane emulsion, includes the following steps：
(1) the polyethylene terephthalate polyalcohol and 10g isophorone diisocyanate for being 1000 by 20g molecular weight
Ester, 1g SiO 2 hollow microsphere (partial size 1000nm, wall thickness 100nm) are added in there-necked flask, react 3 hours at 90 DEG C；
(2) by 1.5g dihydromethyl propionic acid, 0.8g trimethylolpropane, 4g n,N-dimethylacetamide and a small amount of February
Reaction system is added in dilaurylate, reacts 4 hours at 90 DEG C；
(3) 50 DEG C are cooled to, 1g triethylamine is added and 4g acetone soln is neutralized, reacts 1 hour；
(4) 30 DEG C are cooled to and carries out emulsification 30 minutes hereinafter, 60g water is added；
(5) it adds 0.7g ethylenediamine solution to carry out again chain extension 1 hour, filtering and discharging, obtains aqueous polyurethane cream
Liquid component A.
(6) component B is obtained according to the aqueous polyurethane emulsion that tiny balloon is not added in similarity condition preparation.
Component A and component B is pressed 1：After mixing, film, 120 DEG C of convection ovens are dry on a glass for 1 proportion
Two hours, matte effect was presented in film, tested its 60 degree of angle glossiness 20 with vancometer.With being averaged for particle size analyzer fractions tested A
Partial size is 1245nm, and component B average grain diameter is 342nm.Appropriate mixed emulsion is taken to be centrifuged 15 points at 3,000 rpm with centrifuge
Clock, emulsion, no obvious sediment.
Embodiment 2
A kind of preparation method of extinction type aqueous polyurethane emulsion, includes the following steps：
(1) the polytetrahydrofuran ethoxylated polyhydric alcohol and 12g methyl diphenylene diisocyanate for being 1500 by 15g molecular weight, 4g
SiO 2 hollow microsphere (partial size 1500nm, wall thickness 80nm) is added in there-necked flask, reacts 4 hours at 80 DEG C；
(2) by 2.0g dimethylolpropionic acid, 0.5g trimethylolpropane, 4g n,N-dimethylacetamide and a small amount of February
Reaction system is added in dilaurylate, reacts 4 hours at 80 DEG C；
(3) 50 DEG C are cooled to, 1.2g triethylamine is added and 4g acetone soln is neutralized, reacts 1 hour；
(4) 30 DEG C are cooled to and carries out emulsification 30 minutes hereinafter, 55g water is added；
(5) it adds 0.8g ethylenediamine solution to carry out again chain extension 1 hour, filtering and discharging, obtains aqueous polyurethane cream
Liquid component A.
(6) component B is obtained according to the aqueous polyurethane emulsion that tiny balloon is not added in similarity condition preparation.
Component A and component B is pressed 2：After mixing, film, 120 DEG C of convection ovens are dry on a glass for 1 proportion
Two hours, film surface was slightly white, opaque.Its 60 degree of angle glossiness are tested less than 10 with vancometer.With particle size analyzer test group
The average grain diameter for dividing A is 1785nm, and component B average grain diameter is 220nm.Take appropriate mixed emulsion centrifuge at 3,000 rpm
Centrifugation 15 minutes, emulsion, no obvious sediment.
Embodiment 3
A kind of preparation method of extinction type aqueous polyurethane emulsion, includes the following steps：
(1) polycarbonate polyol and 15g hexamethylene diisocyanate for being 800 by 22g molecular weight, 6g polystyrene
Tiny balloon (partial size 1200nm, wall thickness 120nm) is added in there-necked flask, reacts 3 hours at 95 DEG C；
(2) by 1.0g dimethylolpropionic acid, 0.5g 1,4-butanediol -2- sodium sulfonate, 0.6g trimethylolpropane, 4g N,
Reaction system is added in N- dimethyl acetamide and a small amount of dibutyl tin dilaurate, reacts 3 hours at 82 DEG C；
(3) 50 DEG C are cooled to, 0.8g triethylamine is added and 4g acetone soln is neutralized, reacts 1 hour；
(4) 30 DEG C are cooled to and carries out emulsification 30 minutes hereinafter, 70g water is added；
(5) it adds 0.6g ethylenediamine solution to carry out again chain extension 1 hour, filtering and discharging, obtains aqueous polyurethane cream
Liquid component A.
(6) component B is obtained according to the aqueous polyurethane emulsion that tiny balloon is not added in similarity condition preparation.
Component A and component B is pressed 3：After mixing, film, 120 DEG C of convection ovens are dry on a glass for 1 proportion
Two hours, film surface was opaque, white.Its 60 degree of angle glossiness are tested less than 10 with vancometer.With particle size analyzer fractions tested A
Average grain diameter be 1406nm, component B average grain diameter be 258nm.Appropriate mixed emulsion is taken to be centrifuged at 3,000 rpm with centrifuge
15 minutes, emulsion, no obvious sediment.
Embodiment 4
A kind of preparation method of extinction type aqueous polyurethane emulsion, includes the following steps：
(1) the poly terephthalic acid hexylene glycol ester polyol and 20g 4,4'- dicyclohexyl first by 10g molecular weight for 2000
Alkane diisocyanate, 6g SiO 2 hollow microsphere (partial size 2000nm, wall thickness 300nm) are added in there-necked flask, react 3 at 95 DEG C
Hour；
(2) by 2.0g dimethylolpropionic acid, 0.9g trimethylolpropane, 4g n,N-dimethylacetamide and a small amount of February
Reaction system is added in dilaurylate, reacts 3 hours at 95 DEG C；
(3) 50 DEG C are cooled to, 1.5g triethylamine is added and 4g acetone soln is neutralized, reacts 1 hour；
(4) 30 DEG C are cooled to and carries out emulsification 30 minutes hereinafter, 65g water is added；
(5) it adds 1.2g ethylenediamine solution to carry out again chain extension 1 hour, filtering and discharging, obtains aqueous polyurethane cream
Liquid component A.
(6) component B is obtained according to the aqueous polyurethane emulsion that tiny balloon is not added in similarity condition preparation.
Component A and component B is pressed 1：After mixing, film, 120 DEG C of convection ovens are dry on a glass for 3 proportion
Two hours, film surface slightly whitened at matte effect.Its 60 degree of angle glossiness 15 are tested with vancometer.With particle size analyzer fractions tested A
Average grain diameter be 2275nm, component B average grain diameter be 289nm.Appropriate mixed emulsion is taken to be centrifuged at 3,000 rpm with centrifuge
15 minutes, emulsion, no obvious sediment.
Embodiment 5
A kind of preparation method of extinction type aqueous polyurethane emulsion, includes the following steps：
(1) polyethylene oxide polyol and 22g isophorone diisocyanate by 15g molecular weight for 1500,5g dioxy
SiClx tiny balloon (partial size 1500nm, wall thickness 150nm) is added 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, 4g N, N- dimethyl
Reaction system is added in acetamide and a small amount of dibutyl tin dilaurate, reacts 3 hours at 95 DEG C；
(3) 50 DEG C are cooled to, 0.7g triethylamine is added and 4g acetone soln is neutralized, reacts 1 hour；
(4) 30 DEG C are cooled to and carries out emulsification 30 minutes hereinafter, 50g water is added；
(5) it adds 1.0g ethylenediamine solution to carry out again chain extension 1 hour, filtering and discharging, obtains aqueous polyurethane cream
Liquid component A.
(6) component B is obtained according to the aqueous polyurethane emulsion that tiny balloon is not added in similarity condition preparation.
Component A and component B is pressed 1：After mixing, film, 120 DEG C of convection ovens are dry on a glass for 5 proportion
Two hours, film surface was at matte effect.Its 60 degree of angle glossiness 25 are tested with vancometer.With being averaged for particle size analyzer fractions tested A
Partial size is 1807nm, and component B average grain diameter is 242nm.Appropriate mixed emulsion is taken to be centrifuged 15 points at 3,000 rpm with centrifuge
Clock, emulsion, no obvious sediment.
Embodiment 6
A kind of preparation method of extinction type aqueous polyurethane emulsion, includes the following steps：
(1) polycarbonate polyol and 25g methyl diphenylene diisocyanate for being 2000 by 20g molecular weight, 7g dioxy
SiClx tiny balloon (partial size 1200nm, wall thickness 100nm) is added 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, 4g N, N- dimethyl
Reaction system is added in acetamide and a small amount of dibutyl tin dilaurate, reacts 4 hours at 60 DEG C；
(3) 50 DEG C are cooled to, 0.8g triethylamine is added and 4g acetone soln is neutralized, reacts 1 hour；
(4) 30 DEG C are cooled to and carries out emulsification 30 minutes hereinafter, 50g water is added；
(5) it adds 0.5g ethylenediamine solution to carry out again chain extension 1 hour, filtering and discharging, obtains aqueous polyurethane cream
Liquid component A.
(6) component B is obtained according to the aqueous polyurethane emulsion that tiny balloon is not added in similarity condition preparation.
Component A and component B is pressed 2：After mixing, film, 120 DEG C of convection ovens are dry on a glass for 3 proportion
Two hours, film surface was at matte effect.Its 60 degree of angle glossiness 30 are tested with vancometer.With being averaged for particle size analyzer fractions tested A
Partial size is 1407nm, and component B average grain diameter is 189nm.Appropriate mixed emulsion is taken to be centrifuged 15 points at 3,000 rpm with centrifuge
Clock, emulsion, no obvious sediment.
It can be seen from above-described embodiment that extinction type aqueous polyurethane emulsion of the present invention can be as needed, adjusting disappears
Light path degree, and dispersion effect is high, promotes the use of convenient for practical.
Polyurethane molecular chain is coated on tiny balloon by the present invention by the method being chemically bonded, and obtains a kind of big partial size
Polyurethane micelle.Due to the density and hollow structure of tiny balloon, the sedimentation situation of big partial size polyurethane micelle is improved, is made
It can be stably dispersed in lotion.The hollow structure of tiny balloon is adjustable, i.e., its wall thickness can choose.According to its wall thickness
Difference influences the scattering situation of light therebetween.It, can be to final emulsion film forming along with the selection of different tiny balloon partial sizes
Delustring degree afterwards is adjusted.It can be selected by simple raw material to prepare the aqueous poly- ammonia with different delustring degree
Ester finishing agent.The addition of tiny balloon be equal to joined it is a kind of rigid filled, to the mechanical property of final finishing agent, water resistance,
Solvent resistance is all improved.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (27)
1. a kind of extinction type aqueous polyurethane emulsion, which is characterized in that including component A and B component, the component A is by poly- ammonia
Ester is coated to the water-based emulsion of the polyaminoester microball formed on tiny balloon, and the B component is aqueous polyurethane emulsion；
The partial size of the tiny balloon is 700-2000nm；
The wall thickness of the tiny balloon is 50-800nm；
The partial size of the polyaminoester microball is 900-3000nm；
In the B component, the partial size of particle is 20-500nm in aqueous polyurethane emulsion；
Polyurethane molecular amount in the extinction type aqueous polyurethane emulsion is 20000-250000；
The solid content of the extinction type aqueous polyurethane emulsion is 10%-50%.
2. a kind of extinction type aqueous polyurethane emulsion according to claim 1, which is characterized in that the grain of the tiny balloon
Diameter is 700-1800nm.
3. a kind of extinction type aqueous polyurethane emulsion according to claim 2, which is characterized in that the grain of the tiny balloon
Diameter is 800-1500nm.
4. a kind of extinction type aqueous polyurethane emulsion according to claim 1, which is characterized in that the tiny balloon
Wall thickness is 50-700nm.
5. a kind of extinction type aqueous polyurethane emulsion according to claim 4, which is characterized in that the tiny balloon
Wall thickness is 50-600nm.
6. a kind of extinction type aqueous polyurethane emulsion according to claim 1, which is characterized in that the tiny balloon surface
With the functional group that can be reacted with isocyanates.
7. a kind of extinction type aqueous polyurethane emulsion according to claim 6, which is characterized in that the tiny balloon surface
With one or both of hydroxyl and amino.
8. a kind of extinction type aqueous polyurethane emulsion according to claim 1, which is characterized in that the tiny balloon is official
The SiO 2 hollow microsphere of energyization, one of polystyrene hollow microballoon or a variety of.
9. a kind of extinction type aqueous polyurethane emulsion according to claim 1, which is characterized in that the polyaminoester microball
Partial size is 900-2500nm.
10. a kind of extinction type aqueous polyurethane emulsion according to claim 9, which is characterized in that the polyaminoester microball
Partial size be 1000-2000nm.
11. according to a kind of extinction type aqueous polyurethane emulsion described in claim 1, which is characterized in that aqueous in the B component
The partial size of particle is 20-400nm in polyaminoester emulsion.
12. according to a kind of extinction type aqueous polyurethane emulsion described in claim 11, which is characterized in that aqueous in the B component
The partial size of particle is 50-400nm in polyaminoester emulsion.
13. a kind of extinction type aqueous polyurethane emulsion according to claim 1, which is characterized in that the component A and B group
Polyurethane in point is mainly by polyalcohol, isocyanates, chain extender, salt forming agent, and initiator is prepared.
14. a kind of extinction type aqueous polyurethane emulsion according to claim 13, which is characterized in that the polyalcohol includes
Polyethylene terephthalate polyalcohol, polybutylene terephthalate (PBT) polyalcohol, polyethylene glycol adipate polyalcohol,
Poly terephthalic acid hexylene glycol ester polyol, polyethylene oxide polyol, polytetrahydrofuran ethoxylated polyhydric alcohol, polypropylene oxide are polynary
One of alcohol, polycarbonate polyol, polycaprolactone polyol are a variety of.
15. a kind of extinction type aqueous polyurethane emulsion according to claim 13, which is characterized in that point of the polyalcohol
Son amount is 500-5000.
16. a kind of extinction type aqueous polyurethane emulsion according to claim 13, which is characterized in that the isocyanates packet
Include isophorone diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexamethylene diisocyanate,
One of 4,4'- dicyclohexyl methyl hydride diisocyanate, tetramethyl xylylene diisocyanate are a variety of.
17. a kind of extinction type aqueous polyurethane emulsion according to claim 13, which is characterized in that the chain extender includes
Dihydromethyl propionic acid, dimethylolpropionic acid, nonionic dihydroxylic alcohols, ethylenediamine base ethanesulfonic acid sodium, 1,4- butanediol -2- sodium sulfonate,
Trimethylolpropane, pentaerythrite, glycerine, ethylenediamine, ammonium hydroxide, isophorone diamine, hydrazine hydrate, diethylenetriamine, three second
One of alkene tetramine is a variety of.
18. a kind of extinction type aqueous polyurethane emulsion according to claim 17, which is characterized in that the nonionic binary
Alcohol includes one in ethylene glycol, 1,4-butanediol, 1,6- hexylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol and triethylene glycol
Kind is a variety of.
19. a kind of extinction type aqueous polyurethane emulsion according to claim 13, which is characterized in that the salt forming agent includes
One of triethylamine, sodium hydroxide, potassium hydroxide are a variety of.
20. a kind of extinction type aqueous polyurethane emulsion according to claim 13, which is characterized in that the initiator includes
One of dibutyl tin dilaurate, stannous octoate are a variety of.
21. a kind of extinction type aqueous polyurethane emulsion according to claim 1, which is characterized in that the extinction type is aqueous
Polyurethane molecular amount in polyaminoester emulsion is 50000-200000.
22. a kind of extinction type aqueous polyurethane emulsion according to claim 21, which is characterized in that the extinction type is aqueous
Polyurethane molecular amount in polyaminoester emulsion is 50000-150000.
23. a kind of extinction type aqueous polyurethane emulsion according to claim 1, which is characterized in that the extinction type is aqueous
The solid content of polyaminoester emulsion is 10%-45%.
24. a kind of extinction type aqueous polyurethane emulsion according to claim 23, which is characterized in that the extinction type is aqueous
The solid content of polyaminoester emulsion is 15%-40%.
25. such as a kind of described in any item preparation methods of extinction type aqueous polyurethane emulsion of claim 1-24, feature exists
In, using have active function groups tiny balloon, polyurethane segment is coated on tiny balloon by chemical bond, formed gather
The water-based emulsion of urethane microballoon forms dispersed latex grain in aqueous polyurethane emulsion.
26. a kind of preparation method of extinction type aqueous polyurethane emulsion according to claim 25, which is characterized in that including
Following steps：
(1) isocyanates, polyalcohol, tiny balloon are reacted；
(2) chain extender, initiator and solvent is added, reaction obtains performed polymer；
(3) salt forming agent and solvent are added after cooling down, is stirred to react；
(4) deionized water is added after cooling down, is dispersed with stirring；
(5) chain extender is added, chain extension obtains the water-based emulsion of polyaminoester microball.
27. a kind of preparation method of extinction type aqueous polyurethane emulsion according to claim 25, which is characterized in that including
Following steps：
(1) isocyanates, polyalcohol are reacted；
(2) chain extender, initiator and solvent is added, reaction obtains performed polymer；
(3) salt forming agent and solvent are added after cooling down, is stirred to react；
(4) deionized water is added after cooling down, is dispersed with stirring；
(5) chain extender is added, chain extension obtains aqueous polyurethane emulsion.
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| CN112876958A (en) * | 2019-11-29 | 2021-06-01 | 万华化学集团股份有限公司 | Water-based leather finishing agent and application thereof |
| CN112266714B (en) * | 2020-10-29 | 2021-12-28 | 浩力森化学科技（江苏）有限公司 | Preparation method of epoxy modified super-matte acrylic coating |
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| CN115559123B (en) * | 2022-10-25 | 2024-05-28 | 广东西顿新材料科技有限公司 | Water-based anti-fouling synthetic leather finishing agent for vehicle and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101506389A (en) * | 2006-08-22 | 2009-08-12 | 朗盛德国有限责任公司 | Dressed leather |
| CN103180395A (en) * | 2010-10-27 | 2013-06-26 | 株式会社钟化 | Curable composition |
| CN103740250A (en) * | 2013-12-06 | 2014-04-23 | 四川达威科技股份有限公司 | Preparation method of matting leather water-based polyurethane coating agent |
Family Cites Families (1)
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-
2016
- 2016-01-27 CN CN201610055970.0A patent/CN105694699B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101506389A (en) * | 2006-08-22 | 2009-08-12 | 朗盛德国有限责任公司 | Dressed leather |
| CN103180395A (en) * | 2010-10-27 | 2013-06-26 | 株式会社钟化 | Curable composition |
| CN103740250A (en) * | 2013-12-06 | 2014-04-23 | 四川达威科技股份有限公司 | Preparation method of matting leather water-based polyurethane coating agent |
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