CN105566599B - A kind of aqueous polyurethane emulsion and preparation method thereof for apolar surfaces coating - Google Patents

A kind of aqueous polyurethane emulsion and preparation method thereof for apolar surfaces coating Download PDF

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CN105566599B
CN105566599B CN201511017803.9A CN201511017803A CN105566599B CN 105566599 B CN105566599 B CN 105566599B CN 201511017803 A CN201511017803 A CN 201511017803A CN 105566599 B CN105566599 B CN 105566599B
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aqueous polyurethane
polyurethane emulsion
glycol
polyol
polyalcohol
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CN105566599A (en
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张建森
罗楠
张冬海
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Cangzhou meiuite New Material Technology Co., Ltd
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Environmental Science & Technology (beijing) Co Ltd
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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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
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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
    • C08G18/30—Low-molecular-weight compounds
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    • C08G18/348—Hydroxycarboxylic acids
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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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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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
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
    • C08G18/6517—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
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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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
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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
    • C08G18/70—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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    • 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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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract

The invention belongs to aqueous functional macromolecule emulsion technical fields, and in particular to a kind of aqueous polyurethane emulsion and preparation method thereof for apolar surfaces coating.The aqueous polyurethane emulsion for apolar surfaces coating consists of the following compositions：Dendrimer, polyalcohol, isocyanates, hydrophilic chain extender, alcohols chain extender, amine chain extender, salt forming agent, catalyst, solvent and deionized water.Aqueous polyurethane emulsion of the present invention has good adhesive force to non-polar substrate, and emulsion solid content, water resistance, heat resistance, mechanical property are improved；Simultaneously because its surface energy can according to circumstances be adjusted, the transfer coated use of polar substrates can be further used as.

Description

A kind of aqueous polyurethane emulsion and preparation method thereof for apolar surfaces coating
Technical field
The invention belongs to aqueous functional macromolecule emulsion technical fields, and in particular to a kind of for apolar surfaces coating Aqueous polyurethane emulsion and preparation method thereof.
Background technology
In recent years, with a series of implementation of energy-saving and emission-reduction measures of country, traditional oil paint industry is organic due to its Solvent dosage is big, has damage to health and atmospheric environment, is just gradually replaced by water paint.Water paint is non-toxic and tasteless, The problems such as will not causing combustion explosion and environmental pollution, is widely used in building, adhesive, fabric coating and finishing agent, leather The fields such as finishing agent, paper surface finishing agent and fiber surface treatment agent.
But since water paint polarity is larger, surface energy is higher, when its as the coating of nonpolar coating in use, With the poor adhesive force of base material.To improve such case, researcher has carried out different trials.CN201410606232.1 passes through system The method of standby acrylic acid-polyurethane complex emulsions, chlorinated polypropylene is introduced into polyurethane chain, the attachment of itself and PP films is enhanced Power；Silane coupling agent is introduced into polyurethane synthesis by CN201410568769.3, and is closed to the monomer in synthesis The low polarity both sexes aqueous polyurethane coating with certain degree of cross linking is prepared in the selection of reason；201410788628.2 will carry The special polysiloxane of reactive group is added in polyurethane synthesis, and hydrophobic aqueous polyurethane coating is prepared； 201310410503.1 utilizations introduce acrylic monomers in polyaminoester emulsion building-up process, then are participated in product as polymeric monomer The synthesis of polyacrylate emulsion.By the selection of different acrylic monomers, the adjustable of polyester film surface tension may be implemented. The adjustment that also some inventions are formulated by aqueous polyurethane itself come obtain having suitable coating surface can product (CN201510143713.8, CN201410784122.4)；Or participate in water using some activated monomers for containing silicon or fluorine etc. Property polyurethane synthesis come adjust its final products surface energy (CN201410639443.5, CN201210581376.7, CN201410026461.6)。
The studies above all is attempting to find a suitable method, can both obtain the aqueous poly- ammonia that surface energy can be adjusted Ester lotion, and can further promote final lotion or resin property.But the adjustment of water-based polyaminoester emulsion formula, with And the allotment of PUA lotions all can only improve the surface energy of final products to a certain extent, and can not achieve complete manipulation.And The use of silanization monomer or fluoropolymer, polysiloxanes etc., though the surface tension of final product can be regulated and controled, they with The reactivity of aqueous polyurethane macromolecular is relatively low, and usage amount is also restrained, finally affects the using effect of product.
Invention content
In order to overcome the deficiencies of the prior art, the present invention provides a kind of aqueous polyurethane breasts for apolar surfaces coating Liquid and preparation method thereof, specific technical solution are as follows：
A kind of aqueous polyurethane emulsion for apolar surfaces coating, composition and mass fraction are as follows：
Further, the polyalcohol includes polyethylene terephthalate polyalcohol, polybutylene terephthalate Ester polyol, polyethylene glycol adipate polyalcohol, poly terephthalic acid hexylene glycol ester polyol, polyethylene oxide polyol, One kind in PolyTHF ethoxylated polyhydric alcohol, polyoxypropylene polyol, polycarbonate polyol, polycaprolactone polyol or one Kind or more；The molecular weight of the polyalcohol is 500-5000, preferably 500-4000, further preferably 800-3000.
The isocyanates includes isophorone diisocyanate, toluene di-isocyanate(TDI), diphenylmethane diisocyanate In ester, hexamethylene diisocyanate, 4,4'- dicyclohexyl methyl hydride diisocyanates, tetramethyl xylylene diisocyanate One or more；
The hydrophilic chain extender includes dihydromethyl propionic acid, dimethylolpropionic acid, ethylenediamine base ethanesulfonic acid sodium, 1,4- fourths One or more in glycol -2- sodium sulfonates, nonionic dihydroxylic alcohols；
The alcohols chain extender includes trimethylolpropane, pentaerythrite, glycerine, ethylene glycol, 1,4- butanediols, 1,6- Hexylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol；
The amine chain extender include diethanol amine, triethanolamine, ethylenediamine, ammonium hydroxide, isophorone diamine, hydrazine hydrate, One or more in diethylenetriamine, triethylene tetramine；
The salt forming agent includes the one or more in triethylamine, sodium hydroxide, potassium hydroxide；
The catalyst include dibutyl tin laurate, stannous octoate, one kind in di-n-butylacetic acid tin or it is a kind of with On；
The solvent include acetone, n,N-Dimethylformamide, n,N-dimethylacetamide, butanone, toluene, dimethylbenzene, One or more in ethyl acetate, N-Methyl pyrrolidone.
Further, the structure of the dendrimer is：
Wherein, A is polyfunctional compound, and B is isocyanates, and C is macromolecular polyol, and D is hydroxy-terminated polysiloxane Or Amino End Group polysiloxanes；A, the mass percent of B, C, D in dendrimer is followed successively by 1-20%, 10-50%, 10- 80%, 10-80%, preferably 1-18%, 10-40%, 20-80%, 10-70%, further preferably 1-15%, 15-40%, 20-70%, 20-70%.
The hydroxyl value of the dendrimer is 10-200mgKOH/g, preferably 20-150mgKOH/g, further preferably 40-120mgKOH/g, molecular weight are 2-25 ten thousand.
The polyfunctional compound includes one or both of polyol, multiamino compound；It is described more Hydroxy compounds be trimethylolpropane, pentaerythrite, glycerine, ethylene glycol, propylene glycol, 1,4- butanediols, 1,6-HD, One or more in neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol；The multiamino compound is three second Hydramine, diethanol amine, ammonium hydroxide, diethylenetriamine, triethylene tetramine, ethylenediamine, isophorone diamine, hydrazine hydrate, melamine In one or more；
The isocyanates includes isophorone diisocyanate, toluene di-isocyanate(TDI), diphenylmethane diisocyanate Ester, hexamethylene diisocyanate, 4,4'- dicyclohexyl methyl hydride diisocyanates, tetramethyl xylylene diisocyanate, four Xylylene diisocyanate dimer, one kind in durol dimethyl diisocyanate trimer or it is a kind of with On；
The macromolecular polyol include polyethylene terephthalate, polybutylene terephthalate (PBT), gather oneself two Sour glycol ester, polyethylene oxide, polytetrahydrofuran ether, polyoxypropylene polyol and its one kind in the fluorine substituent of part or More than one；The molecular weight of the macromolecular polyol is 100-2000, preferably 100-1500, further preferably 500- 1500。
The hydroxy-terminated polysiloxane includes that hydroxyl-terminated injecting two methyl siloxane, terminal hydroxy group ethoxylation or propoxylation are poly- The poly ethyldiol modified polysiloxanes of siloxanes, terminal hydroxy group, hydroxy-terminated polytetrahydrofuran modified polyorganosiloxane, terminal hydroxy group polycaprolactone One or more in modified polyorganosiloxane；The Amino End Group polysiloxanes includes Amino End Group dimethyl silicone polymer, end One kind or one in the poly- diethoxy siloxanes of amino polydiethylsiloxane, Amino End Group, the poly- dimethoxysiloxane of Amino End Group Kind or more；The molecular weight of the hydroxy-terminated polysiloxane or Amino End Group polysiloxanes be 100-2000, preferably 100-1500, into One step is preferably 100-1000.
The preparation method of aqueous polyurethane emulsion as described above, includes the following steps：
(1) isocyanates, polyalcohol and dendrimer are reacted 2-4 hours at 60-100 DEG C；
(2) hydrophilic chain extender, alcohols chain extender, catalyst and solvent is added, reacts 3-5 hours, obtains at 50-90 DEG C To performed polymer；
(3) it is cooled to 30-50 DEG C, salt forming agent and solvent is added, is stirred 30-60 minutes；
(4) it is cooled to 10-30 DEG C, appropriate amount of deionized water is added, while high-speed stirred is disperseed 30-60 minutes, is obtained aqueous Polyaminoester emulsion.
Further, after deionized water and high-speed stirred dispersion is added in step (4), amine chain extender can also be added, into One step chain extension, obtains aqueous polyurethane emulsion.
Further, in the aqueous polyurethane emulsion dendrimer molecular weight be 2-25 ten thousand, preferably 5-20 ten thousand, Further preferably 5-15 ten thousand；Emulsion solid content is 10-50%, preferably 10-45%, further preferably 15-40%.
Dendrimer monomer is introduced in the aqueous polyurethane emulsion of the present invention, and common of siliceous, fluorine constituent is gathered Reactive urethane monomer is wrapped up, and a tree-shaped reaction monomers are formed, and monomer end carries a large amount of reactive functional groups, ensure that Reaction efficiency in building-up process；And it, can be to the surface energy of final products by the content for adjusting middle layer silicon, fluorine constituent It is controlled, the more controllable aqueous polyurethane emulsion for apolar surfaces coating of processability.
Aqueous polyurethane emulsion of the present invention, to non-polar substrate have good adhesive force, emulsion solid content, Water resistance, heat resistance, mechanical property are improved；Simultaneously because its surface energy can according to circumstances be adjusted, it can be into one Walk the transfer coated use as polar substrates.
Beneficial effects of the present invention are：
(1) present invention participates in reaction using the dendrimer monomer with special construction, in the production that preparation is met the requirements While product, can also obtain high solids content, low viscosity lotion, substantially increase production and transportation efficiency.
(2) the dendrimer structure in the present invention can introduce functional silane, the crosslinking formed after silane and its hydrolysis Structure can further improve water resistance, solvent resistance, heat resistance, mechanical property of product etc..
(3) structure of the dendrimer monomer in the present invention has controllability, by middle layer non-polar monomer and The change of low polar monomer ratio can regulate and control the performance of final products, to realize to different nonpolarity or low pole Property base material all keeps good adhesive force.
Specific implementation mode
The present invention is described in further detail with reference to embodiments, but embodiments of the present invention and not only office It is limited to this.
Embodiment 1
Select dendrimer structure：A=pentaerythrites, B=isophorone diisocyanate, C=low molecular weights are gathered Tetrahydrofuran ethoxylated polyhydric alcohol, D=hydroxyl-terminated injecting two methyl siloxanes, the mass fraction for accounting for dendrimer composition are followed successively by 5.9%, 27.6%, 22.2%, 44.3%.
Polybutylene terephthalate (PBT) polyalcohol, 6 parts of dendrimers and the 16 parts of different Buddhists for being 3000 by 6 parts of molecular weight In your the dry reaction kettle of ketone diisocyanate input, at 90 DEG C, reacted 3-4 hours under 200-350rpm mixing speeds；
3 parts of dimethylolpropionic acids, 0.5 part of trimethylolpropane, 0.1 part of catalyst dibutyl tin dilaurate and molten is added Agent n,N-Dimethylformamide, the reaction was continued 2-3 hours, obtains performed polymer；
Temperature is reduced to 50 DEG C, 0.5 part of triethylamine is added, continuation is reacted 30-60 minutes under 300-400rpm rotating speeds；
30 DEG C are cooled to hereinafter, 70 parts of deionized waters are added under 1200-1500rpm rotating speeds, rapid dispersion 30-60 divides Clock；
2 parts of ethylenediamines are added, the reaction was continued under 300-400rpm rotating speeds 60-90 minute to get newborn to aqueous polyurethane Liquid.
Performance test：Gained aqueous polyurethane emulsion is diluted to 12% (wt%) with 80% ethyl alcohol, then with 4 μm of bar Directly by the lotion applicator after dilution on PP films；It is sticked on coating with adhesive tape after drying and measures coating stripping, coating is complete Nothing falls off；It is 32 to measure film surface dyne value with corona pen；Transparency does not change before and after PP films, hot pressing adhesion.
Embodiment 2
Select dendrimer structure：A=trimethylolpropanes, B=methyl diphenylene diisocyanates, C=polycyclic oxygen Ethane polyalcohol, D=Amino End Group dimethyl silicone polymers, the mass fraction for accounting for dendrimer composition are followed successively by 4.0%, 28%, 23%, 45%.
Polyethylene terephthalate polyalcohol, 5 parts of dendrimers and the 15 parts of different Buddhists for being 3000 by 5 parts of molecular weight In your the dry reaction kettle of ketone diisocyanate input, at 90 DEG C, reacted 3-4 hours under 200-350rpm mixing speeds；
3 parts of dihydromethyl propionic acids, 1 part of trimethylolpropane, 0.1 part of catalyst dibutyl tin dilaurate and solvent is added N-Methyl pyrrolidone, the reaction was continued 2-3 hours；
Temperature is reduced to 50 DEG C, 0.5 part of triethylamine continuation is added and is reacted 30-60 minutes under 300-400rpm rotating speeds；
30 DEG C are cooled to hereinafter, 80 parts of deionized waters are added under 1200-1500rpm rotating speeds, rapid dispersion 30-60 divides Clock is to get to aqueous polyurethane emulsion.
Performance test：Gained aqueous polyurethane emulsion is diluted to 12% (wt%) with 80% ethyl alcohol, then with 4 μm of bar Directly by the lotion applicator after dilution on PE films；It is sticked on coating with adhesive tape after drying and measures coating stripping, coating is complete Nothing falls off；It is 32 to measure film surface dyne value with corona pen；Transparency does not change before and after PE films, hot pressing adhesion.
Embodiment 3
Select dendrimer structure：A=pentaerythrites, B=toluene di-isocyanate(TDI)s, C=poly terephthalic acids second two Alcohol ester polyol, D=Amino End Group polydiethylsiloxanes, the mass fraction for accounting for dendrimer composition are followed successively by 3.2%, 27.9%, 44.9%, 24.0%.
Polybutylene terephthalate (PBT) polyalcohol, 16 parts of isophorone diisocyanate by 2 parts of molecular weight for 1500 With 10 parts of dendrimer inputs in dry reaction kettle, at 85 DEG C, reacted 3-4 hours under 200-350rpm mixing speeds；
Be added 4 parts of dihydromethyl propionic acids, 1.5 parts of trimethylolpropanes, 0.15 part of catalyst dibutyl tin dilaurate and Solvent butanone, the reaction was continued 2-3 hours；
Temperature is reduced to 50 DEG C, 1 part of triethylamine continuation is added and is reacted 30-60 minutes under 300-400rpm rotating speeds；
30 DEG C are cooled to hereinafter, 80 parts of deionized waters are added under 1200-1500rpm rotating speeds, rapid dispersion 30-60 divides Clock is to get to aqueous polyurethane emulsion.
Performance test：Gained aqueous polyurethane emulsion is diluted to 12% (wt%) with 80% ethyl alcohol, then with 4 μm of bar Directly by the lotion applicator after dilution in BOPP film；It is sticked on coating with adhesive tape after drying and measures coating stripping, coating is complete Whole nothing falls off；It is 32 to measure film surface dyne value with corona pen；Transparency does not change before and after BOPP film, hot pressing adhesion.
Embodiment 4
Select dendrimer structure：A=neopentyl glycols, the dimer of B=toluene di-isocyanate(TDI)s, C=are partially fluorinated Polyethylene glycol adipate polyalcohol, the poly- diethoxy siloxanes of D=Amino End Groups, account for dendrimer composition mass fraction according to Secondary is 4.2%, 32.9%, 25.0%, 37.9%.
5 parts of molecular weight are tree-shaped for 2000 PolyTHF ethoxylated polyhydric alcohol, 16 parts of isophorone diisocyanate and 7 parts In the dry reaction kettle of macromolecular input, at 90 DEG C, reacted 3-4 hours under 200-350rpm mixing speeds；
3 parts of dimethylolpropionic acids, 1 part of pentaerythrite, 0.2 part of catalyst dibutyl tin dilaurate and solvent acetic acid is added Ethyl ester, the reaction was continued 2-3 hours；
Temperature is reduced to 50 DEG C, 0.2 part of triethylamine continuation is added and is reacted 30-60 minutes under 300-400rpm rotating speeds；
30 DEG C are cooled to hereinafter, 80 parts of deionized waters are added under 1200-1500rpm rotating speeds, rapid dispersion 30-60 divides Clock；
2 parts of isophorone diamine are added, the reaction was continued under 300-400rpm rotating speeds 60-90 minutes gathers to get to aqueous Urethane lotion.
Performance test：Gained aqueous polyurethane emulsion is diluted to 12% (wt%) with 80% ethyl alcohol, then with 4 μm of bar Directly by the lotion applicator after dilution on LDPE films；It is sticked on coating with adhesive tape after drying and measures coating stripping, coating is complete Whole nothing falls off；It is 32 to measure film surface dyne value with corona pen；Transparency does not change before and after LDPE films, hot pressing adhesion.
Embodiment 5
Select dendrimer structure：A=triethanolamines, B=isophorone diisocyanate, the partially fluorinated polycyclics of C= Oxidative ethane polyalcohol, the poly ethyldiol modified polysiloxanes of D=terminal hydroxy groups, the mass fraction for accounting for dendrimer composition are followed successively by 3.5%, 28.2%, 43.8%, 24.5%.
7 parts of molecular weight are tree-shaped for 800 PolyTHF ethoxylated polyhydric alcohol, 16 parts of isophorone diisocyanate and 5 parts In the dry reaction kettle of macromolecular input, at 95 DEG C, reacted 3-4 hours under 200-350rpm mixing speeds；
4 parts of dihydromethyl propionic acids, 1 part of trimethylolpropane, 0.1 part of catalyst dibutyl tin dilaurate and solvent is added Butyl acetate, the reaction was continued 2-3 hours；
Temperature is reduced to 50 DEG C, 0.2 part of potassium hydroxide continuation is added and is reacted 30-60 minutes under 300-400rpm rotating speeds；
30 DEG C are cooled to hereinafter, 60 parts of deionized waters are added under 1200-1500rpm rotating speeds, rapid dispersion 30-60 divides Clock；
3 parts of hydrazine hydrates are added, the reaction was continued under 300-400rpm rotating speeds 60-90 minute to get newborn to aqueous polyurethane Liquid.
Performance test：Gained aqueous polyurethane emulsion is diluted to 12% (wt%) with 80% ethyl alcohol, then with 4 μm of bar Directly by the lotion applicator after dilution on HDPE film；It is sticked on coating with adhesive tape after drying and measures coating stripping, coating is complete Whole nothing falls off；It is 32 to measure film surface dyne value with corona pen；Transparency does not change before and after HDPE film, hot pressing adhesion.
Embodiment 6
Select dendrimer structure：A=glycerine, B=methyl diphenylene diisocyanates, C=polycarbonate polyols Alcohol, the poly- dimethoxysiloxane of D=Amino End Groups, the mass fraction for accounting for dendrimer composition are followed successively by 6.1%, 29.3%, 30.2%, 34.4%.
Polycarbonate polyol, 15 parts of toluene di-isocyanate(TDI)s and 5 parts of dendrimers that 6 parts of molecular weight are 800 are thrown Enter in dry reaction kettle, at 70 DEG C, is reacted 3-4 hours under 200-350rpm mixing speeds；
3 parts of dihydromethyl propionic acids, 1 part of pentaerythrite, 0.1 part of catalyst dibutyl tin dilaurate and solvent diformazan is added Benzene, the reaction was continued 2-3 hours；
Temperature is reduced to 50 DEG C, 0.2 part of sodium hydroxide continuation is added and is reacted 30-60 minutes under 300-400rpm rotating speeds；
30 DEG C are cooled to hereinafter, 70 parts of deionized waters are added under 1200-1500rpm rotating speeds, rapid dispersion 30-60 divides Clock；
5 parts of ammonium hydroxide are added, the reaction was continued under 300-400rpm rotating speeds 60-90 minutes to get to aqueous polyurethane emulsion.
Performance test：Gained aqueous polyurethane emulsion is diluted to 12% (wt%) with 80% ethyl alcohol, then with 4 μm of bar Directly by the lotion applicator after dilution on CPP films；It is sticked on coating with adhesive tape after drying and measures coating stripping, coating is complete Nothing falls off；It is 32 to measure film surface dyne value with corona pen；Transparency does not change before and after CPP films, hot pressing adhesion.
Embodiment 7
Select dendrimer structure：A=diethylenetriamines, B=hexamethylene diisocyanates, C=PolyTHFs Ethoxylated polyhydric alcohol, the poly ethyldiol modified siloxanes of D=terminal hydroxy groups, the mass fraction for accounting for dendrimer composition are followed successively by 4.2%, 26.9%, 18%, 40.9%.
Poly terephthalic acid hexylene glycol ester polyol, 16 parts of isophorone diisocyanate by 5 parts of molecular weight for 3000 With 4 parts of dendrimer inputs in dry reaction kettle, at 80 DEG C, reacted 3-4 hours under 200-350rpm mixing speeds；
3 parts of dimethylolpropionic acids, 2 parts of pentaerythrites, 0.1 part of catalyst dibutyl tin dilaurate and solvent diformazan is added Benzene, the reaction was continued 2-3 hours；
Temperature is reduced to 50 DEG C, 0.1 part of triethylamine continuation is added and is reacted 30-60 minutes under 300-400rpm rotating speeds；
30 DEG C are cooled to hereinafter, 85 parts of deionized waters are added under 1200-1500rpm rotating speeds, rapid dispersion 30-60 divides Clock；
Ethylenediamine is added, the reaction was continued under 300-400rpm rotating speeds 60-90 minutes obtains aqueous polyurethane emulsion.
Performance test：Gained aqueous polyurethane emulsion is diluted to 12% (wt%) with 80% ethyl alcohol, then with 4 μm of bar Directly on a pet film by the lotion applicator after dilution；After drying measurement coating stripping, the big portion of coating on coating are sticked to adhesive tape Divide tear-away；It is 32 to measure film surface dyne value with corona pen；Transparency does not change before and after PET film, hot pressing adhesion.
Embodiment 8
Select dendrimer structure：A=melamines, B=hexamethylene diisocyanates, C=are partially fluorinated poly- Ethylene glycol polyalcohol, D=terminal hydroxy group polyethoxy siloxanes, the mass fraction for accounting for dendrimer composition are followed successively by 4.0%, 32.1%, 43.2%, 20.7%.
By 3 parts of molecular weight be 2000 polycarbonate polyol, 15 parts of methyl diphenylene diisocyanates and 6 parts tree-shaped big In the dry reaction kettle of molecule input, at 80 DEG C, reacted 3-4 hours under 200-350rpm mixing speeds；
3 parts of dihydromethyl propionic acids, 2 parts of trimethylolpropanes, 0.1 part of catalyst dibutyl tin dilaurate and solvent is added Toluene, the reaction was continued 2-3 hours；
Temperature is reduced to 50 DEG C, 0.1 part of triethylamine continuation is added and is reacted 30-60 minutes under 300-400rpm rotating speeds；
30 DEG C are cooled to hereinafter, 80 parts of deionized waters are added under 1200-1500rpm rotating speeds, rapid dispersion 30-60 divides Clock；
2 parts of triethylamines are slowly added to, the reaction was continued under 300-400rpm rotating speeds 60-90 minutes obtains aqueous polyurethane Lotion.
Performance test：Gained aqueous polyurethane emulsion is diluted to 12% (wt%) with 80% ethyl alcohol, then with 4 μm of bar Directly by the lotion applicator after dilution on PA films；It is sticked on coating with adhesive tape after drying and measures coating stripping, coating is big absolutely Part is tear-away；It is 32 to measure film surface dyne value with corona pen；Transparency does not change before and after PA films, hot pressing adhesion.
Above example has carried out in detail the aqueous polyurethane emulsion and preparation method thereof for apolar surfaces coating It introduces.The explanation of above example is only applicable to the method for helping to understand the present invention and its core technology thought, should not be construed as Limitation of the present invention.Other are any not to violate any change made under technical spirits and principle of the present invention, modifies, replaces Generation, combination simplify, and should all be included in the protection scope of the present invention.

Claims (8)

1. a kind of aqueous polyurethane emulsion for apolar surfaces coating, which is characterized in that the aqueous polyurethane emulsion Composition and mass fraction are as follows：
The structure of the dendrimer is：
Wherein, A is polyfunctional compound, and B is isocyanates, and C is macromolecular polyol, and D is hydroxy-terminated polysiloxane or end Amino silicones；A, the mass percent of B, C, D in dendrimer be followed successively by 1-20%, 10-50%, 10-80%, 10-80%, the sum of mass percent of A, B, C, D are 100%.
2. aqueous polyurethane emulsion according to claim 1, which is characterized in that the hydroxyl value of the dendrimer is 10- 200mgKOH/g, molecular weight are 2-25 ten thousand.
3. aqueous polyurethane emulsion according to claim 1, which is characterized in that the polyfunctional compound includes polyhydroxy One or both of based compound, multiamino compound；
The isocyanates includes isophorone diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, six Methylene diisocyanate, 4,4'- dicyclohexyl methyl hydride diisocyanates, tetramethyl xylylene diisocyanate, tetramethyl One or more in xylylene diisocyanate dimer, durol dimethyl diisocyanate trimer；
The macromolecular polyol includes polyethylene terephthalate, polybutylene terephthalate (PBT), polyadipate second Diol ester, polyethylene oxide, polytetrahydrofuran ether, polyoxypropylene polyol and its one kind in the fluorine substituent of part or one kind More than；
The hydroxy-terminated polysiloxane includes hydroxyl-terminated injecting two methyl siloxane, terminal hydroxy group ethoxylation or the poly- silica of propoxylation The poly ethyldiol modified polysiloxanes of alkane, terminal hydroxy group, hydroxy-terminated polytetrahydrofuran modified polyorganosiloxane, terminal hydroxy group are Polycaprolactone modified One or more in polysiloxanes；The Amino End Group polysiloxanes includes Amino End Group dimethyl silicone polymer, Amino End Group The poly- diethoxy siloxanes of polydiethylsiloxane, Amino End Group, one kind in the poly- dimethoxysiloxane of Amino End Group or it is a kind of with On.
4. aqueous polyurethane emulsion according to claim 3, which is characterized in that the polyol is trihydroxy methyl Propane, pentaerythrite, glycerine, ethylene glycol, propylene glycol, 1,4- butanediols, 1,6-HD, neopentyl glycol, diethylene glycol, two One or more in propylene glycol, triethylene glycol；The multiamino compound is triethanolamine, diethanol amine, ammonium hydroxide, two One or more in ethylene triamine, triethylene tetramine, ethylenediamine, isophorone diamine, hydrazine hydrate, melamine.
5. aqueous polyurethane emulsion according to claim 1, which is characterized in that the molecular weight of the macromolecular polyol is The molecular weight of 100-2000, the hydroxy-terminated polysiloxane or Amino End Group polysiloxanes is 100-2000.
6. aqueous polyurethane emulsion according to claim 1, which is characterized in that the polyalcohol includes poly terephthalic acid Glycol ester polyalcohol, polybutylene terephthalate (PBT) polyalcohol, polyethylene glycol adipate polyalcohol, poly terephthalic acid Hexylene glycol ester polyol, polyethylene oxide polyol, PolyTHF ethoxylated polyhydric alcohol, polyoxypropylene polyol, makrolon One or more in polyalcohol, polycaprolactone polyol；The molecular weight of the polyalcohol is 500-5000；
The isocyanates includes isophorone diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, six One kind in methylene diisocyanate, 4,4'- dicyclohexyl methyl hydride diisocyanates, tetramethyl xylylene diisocyanate Or more than one；
The hydrophilic chain extender includes dihydromethyl propionic acid, dimethylolpropionic acid, ethylenediamine base ethanesulfonic acid sodium, 1,4- fourths two One or more in alcohol -2- sodium sulfonates；
The alcohols chain extender include trimethylolpropane, pentaerythrite, glycerine, ethylene glycol, 1,4- butanediols, 1,6- oneself two Alcohol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol；
The amine chain extender includes diethanol amine, triethanolamine, ethylenediamine, ammonium hydroxide, isophorone diamine, hydrazine hydrate, diethyl One or more in alkene triamine, triethylene tetramine；
The salt forming agent includes the one or more in triethylamine, sodium hydroxide, potassium hydroxide；
The catalyst includes the one or more in dibutyl tin laurate, stannous octoate, di-n-butylacetic acid tin；
The solvent includes acetone, n,N-Dimethylformamide, n,N-dimethylacetamide, butanone, toluene, dimethylbenzene, acetic acid One or more in ethyl ester, N-Methyl pyrrolidone.
7. the preparation method of claim 1-6 any one of them aqueous polyurethane emulsions, which is characterized in that including following step Suddenly：
(1) isocyanates, polyalcohol and dendrimer are reacted 2-4 hours at 60-100 DEG C；
(2) hydrophilic chain extender, alcohols chain extender, catalyst and solvent is added, reacts 3-5 hours, obtains pre- at 50-90 DEG C Aggressiveness；
(3) it is cooled to 30-50 DEG C, salt forming agent and solvent is added, is stirred 30-60 minutes；
(4) it is cooled to 10-30 DEG C, appropriate amount of deionized water is added, while high-speed stirred is disperseed 30-60 minutes, and aqueous poly- ammonia is obtained Ester lotion；
After deionized water and high-speed stirred dispersion is added in step (4), amine chain extender can also be added, further chain extension obtains Aqueous polyurethane emulsion.
8. preparation method according to claim 7, which is characterized in that dendrimer in the aqueous polyurethane emulsion Molecular weight is 2-25 ten thousand；Emulsion solid content is 10-50%.
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