CN107446108A - A kind of aqueous polyurethane acrylate emulsion and preparation method thereof - Google Patents
A kind of aqueous polyurethane acrylate emulsion and preparation method thereof Download PDFInfo
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- CN107446108A CN107446108A CN201710625916.XA CN201710625916A CN107446108A CN 107446108 A CN107446108 A CN 107446108A CN 201710625916 A CN201710625916 A CN 201710625916A CN 107446108 A CN107446108 A CN 107446108A
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- acrylate emulsion
- aqueous polyurethane
- nonionic
- polyurethane acrylate
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 41
- 239000000839 emulsion Substances 0.000 title claims abstract description 39
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000004945 emulsification Methods 0.000 title abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012948 isocyanate Substances 0.000 claims abstract description 18
- 229920000728 polyester Polymers 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 14
- 239000003112 inhibitor Substances 0.000 claims abstract description 14
- 150000002009 diols Chemical class 0.000 claims abstract description 12
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- -1 alicyclic isocyanate Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- 230000033228 biological regulation Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 claims description 2
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- QBUKAFSEUHGMMX-MTJSOVHGSA-N (5z)-5-[[3-(1-hydroxyethyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical group C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1C(C)O QBUKAFSEUHGMMX-MTJSOVHGSA-N 0.000 claims 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims 1
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 7
- 239000003973 paint Substances 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 5
- 229920007019 PC/ABS Polymers 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 230000037452 priming Effects 0.000 abstract description 2
- 239000002966 varnish Substances 0.000 abstract description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GKGXKPRVOZNVPQ-UHFFFAOYSA-N diisocyanatomethylcyclohexane Chemical compound O=C=NC(N=C=O)C1CCCCC1 GKGXKPRVOZNVPQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
-
- 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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of aqueous polyurethane acrylate emulsion and preparation method thereof, it is made up of the component of following parts by weight：25~45 parts of polyester diol, 20~40 parts of the hydrophilic dihydric alcohol of nonionic, 40~60 parts of isocyanates, 1~5 part of chain extender, 1~5 part of crosslinking agent, 100~150 parts of trifunctional acrylic monomers, 0.01~0.5 part of polymerization inhibitor, 0.02~1 part of catalyst.Gained emulsion of the invention has good stability, gloss of film degree, levelling are preferable, hardness is higher, there is good adhesive force on the plastics such as PC/ABS, available for the configuration of the priming paint on plastics, finish paint and finishing varnish, can be very good to improve levelling, attachment and the various chemical resistances of paint film.
Description
Technical field
The invention belongs to polymeric material field, and in particular to a kind of aqueous polyurethane acrylate emulsion and its preparation side
Method.
Background technology
Aqueous polyurethane and water polyacrylic acid are the environment-friendly materials using water as medium, in coating, adhesive, oil
Ink, Textileather coating agent etc. are widely used.Polyurethane has an excellent mechanical property, excellent cold resistance, resistance to
Mill property and elasticity, but its heat-resisting quantity, weatherability, anti-hydrolytic performance are poor, and polyacrylate has preferable gloss, water resistance
With the characteristic of resistance to outdoor aging, but hardness is big, tack, pliability are poor.Utilize polyurethane（PU）And polyacrylate（PA）
Complementation in performance, polyurethane resin is modified by acrylate, the excellent polyurethane-acrylate of availability
Composite.Aqueous polyurethane-acrylate is mainly gathered with blending method, interpenetrating polymer networks method (IPN), emulsion and microemulsion
Legal preparation, polyurethane is first generally prepared using progressively polymerization（PU）Emulsion, then trigger acrylate (PA) radical polymerization,
But by technologies such as existing PU and PA blending methods, interpenetrating networks, otherwise the compatibility, mutually of two class materials is simply mixed in PU and PA
Traversal degree is poor, it is impossible to the advantages of giving full play to PU and PA resins, or double bond on PU strands have it is most of because of probability
And activity factor is not engaged in radical polymerization, PU and PA performance of copolymer is caused also to be difficult to reach design object.
Other aqueous polyurethane is the most commonly used to introduce the self-emulsifying anionic of hydroxy-acid group, but anion-type water-thinned polyurethane
May only be in the lower use in pH >=7, and need to be neutralized with amine nertralizer, it is larger so as to there is emulsion smell, to the person
Body produces harm, and which limits use range.
The content of the invention
The purpose of the present invention is on the basis of existing technology, there is provided a kind of aqueous polyurethane acrylate emulsion.
It is a further object of the present invention to provide a kind of preparation method of above-mentioned aqueous polyurethane acrylate emulsion.
The purpose of the present invention can be reached by following measures：
A kind of aqueous polyurethane acrylate emulsion, it is made up of the component of following parts by weight：25~45 parts of polyester diol, it is non-
20~40 parts of ionic hydrophilic dihydric alcohol, 40~60 parts of isocyanates, 1~5 part of chain extender, 1~5 part of crosslinking agent, trifunctional third
100~150 parts of acrylic monomer, 0.01~0.5 part of polymerization inhibitor, 0.02~1 part of catalyst.
In a kind of preferred scheme, this aqueous polyurethane acrylate emulsion is made up of the component of following parts by weight：Polyester
30~40 parts of dihydric alcohol, 25~35 parts of the hydrophilic dihydric alcohol of nonionic, 45~55 parts of isocyanates, 1~5 part of chain extender, crosslinking agent 1
~4 parts, 110~140 parts of trifunctional acrylic monomers, 0.01~0.5 part of polymerization inhibitor, 0.02~1 part of catalyst.
The number-average molecular weight of signified polyester diol is 1900~2200 in the present invention, and preferably number-average molecular weight is
2000。
The number-average molecular weight of the hydrophilic dihydric alcohol of signified nonionic is 800~1200 in the present invention, preferably counts equal molecule
Measure as 1000.The hydrophilic dihydric alcohol of nonionic can specifically use Sweden Bai Situo Ymer N120.Experiment is found, is used in this programme
Nonionic polyurethane pass through the repulsion that hydrophilic radical and " association " of hydrone and steric effect form balance so that it is poly-
Adduct molecule is stably dispersed in aqueous phase, in outer acid adding, alkali, salt plasma compound, film is had splendid stabilization
Property, and without the bad smell of amine substance.
The one kind or several of signified isocyanates in alicyclic isocyanate or aromatic isocyanate in the present invention
Kind, the alicyclic isocyanate is IPDI or the cyclohexyl methane diisocyanate of 4,4- bis-.Can basis
Actual conditions are adjusted, such as in the case where xanthochromia requirement is not strict, can select the higher virtue of cheaper hardness
Fragrant race's isocyanates.
Signified chain extender is trimethyolol propane monoallyl ether in the present invention.
Signified crosslinking agent is trimethylolpropane in the present invention.
Signified trifunctional acrylic monomers is pentaerythritol triacrylate, further, Ke Yitong in the present invention
Cross and change the species of acrylic monomers and change the degree of functionality of final polyurethane acrylic resin.
Signified polymerization inhibitor is MEHQ in the present invention.
Signified catalyst is dibutyl tin laurate in the present invention.
The preparation method of the aqueous polyurethane acrylate emulsion of the present invention comprises the following steps：
（1）Polyester diol and the hydrophilic dihydric alcohol of nonionic are dehydrated under 100~115 DEG C, vacuum；
（2）Dehydration terminates rear material cooling, adds isocyanates, is reacted at 70~85 DEG C, when measure nco value reaches reason
By value, carry out in next step.
（3）Chain extender is added in 70~85 DEG C of reactions；
（4）Crosslinking agent is added in 70~85 DEG C of reactions；
（5）Temperature is reduced to 65~75 DEG C；The mixture of trifunctional acrylic monomers, polymerization inhibitor and catalyst is added into control
Temperature is reacted below 75 DEG C, is reacted to NCO and is down to less than 0.1% stopping reaction, cooling, obtained resin is poured into
Deionized water regulation solid content is added in dispersion machine, it is scattered at a high speed, obtain polyurethane-acrylate emulsion.
In step（1）In, it is preferred that polyester diol and the hydrophilic dihydric alcohol of nonionic are under 110 DEG C, vacuum 0.9MPa
Carry out 0.8~1.2h of dehydration.
In step（2）In, it is preferred that reaction temperature is 80 DEG C, and the reaction time is 1.5 ~ 2h.
In step（3）Or（4）In, it is preferred that reaction temperature is 80 DEG C, reaction time 0.5h.
In step（5）In, it is preferred that 50 DEG C are cooled to after stopping reaction, obtained resin is poured into dispersion machine and added
Enter deionized water and adjust solid content to 30~60%, 8~12min is disperseed under 1800~2200r/min, obtains polyurethane propylene
Acid esters emulsion.
The present invention prepares nonionic polyurethane emulsion using pre-polymer process, is connect hydrophilic monomer by chemical method
Branch solves the problem of poor chemical stability into prepolymer.Water-based UV polyaminoester emulsions of the present invention are nonionic
Type, gained emulsion have good stability, and gloss of film degree, levelling are preferable, and hardness is higher, have on the plastics such as PC/ABS
There is good adhesive force, available for the configuration of the priming paint on plastics, finish paint and finishing varnish, can be very good to improve the stream of paint film
Flat, attachment and various chemical resistances.
Embodiment
Present disclosure is described further with reference to embodiments, but protection scope of the present invention is not limited to
Following embodiment.
Embodiment 1
The parts by weight of component of aqueous polyurethane acrylate emulsion forms：
2000 molecular weight polyester dihydric alcohol 35g,
The hydrophilic dihydric alcohol 30g of 1000 molecular weight nonionics,
IPDI 50g,
Chain extender trimethyolol propane monoallyl ether 2.5g,
Crosslinking agent trimethylolpropane 1.5g,
Acrylic monomers pentaerythritol triacrylate 130g,
Polymerization inhibitor MEHQ 0.1g,
Catalyst dibutyltin dilaurylate 0.06g.
Preparation process is as follows：
（1）By dihydric alcohol（Including polyester diol and the hydrophilic dihydric alcohol of nonionic）Be added to equipped with mechanical agitation, thermometer and
In the four-hole boiling flask of vacuum plant, 1h is dehydrated under being 0.9MPa in 110 DEG C, vacuum.
（2）Dehydration terminates rear material and is cooled to 80 DEG C, isocyanates is added in four-hole boiling flask by several times, 80 DEG C of reactions, instead
It is 1.5 ~ 2h between seasonable, when measure nco value reaches theoretical value, progress is in next step.
（3）Add 80 DEG C of reaction 0.5h of chain extender.
（4）Add 80 DEG C of reaction 0.5h of crosslinking agent
（5）Temperature is reduced to 70 DEG C；The mixture of acrylic monomers, polymerization inhibitor and catalyst is added in four-hole boiling flask, this
React and be reacted to NCO below 75 DEG C for exothermic reaction, control temperature and be down to less than 0.1% stopping reaction, be cooled to 50 DEG C, will
Resin, which is poured into addition deionized water in dispersion machine, makes solid content be 50%, and 10min is disperseed under 2000r/min, is obtained milky white general
Blue polyurethane-acrylate emulsion.
Embodiment 2
The parts by weight of component of aqueous polyurethane acrylate emulsion forms：
2000 molecular weight polyester dihydric alcohol 39g,
The hydrophilic dihydric alcohol 29g of 1000 molecular weight nonionics,
4,4- bis- cyclohexyl methane diisocyanate 52g,
Chain extender trimethyolol propane monoallyl ether 2.9g,
Crosslinking agent trimethylolpropane 1.2g,
Acrylic monomers pentaerythritol triacrylate 134g,
Polymerization inhibitor MEHQ 0.1g,
Catalyst dibutyltin dilaurylate 0.06g.
Preparation process is the same as embodiment 1.
Embodiment 3
The parts by weight of component of aqueous polyurethane acrylate emulsion forms：
2000 molecular weight polyester dihydric alcohol 31g,
The hydrophilic dihydric alcohol 28g of 1000 molecular weight nonionics,
4,4- bis- cyclohexyl methane diisocyanate 48g,
Chain extender trimethyolol propane monoallyl ether 2.1g,
Crosslinking agent trimethylolpropane 1.2g,
Acrylic monomers pentaerythritol triacrylate 125g,
Polymerization inhibitor MEHQ 0.1g,
Catalyst dibutyltin dilaurylate 0.06g.
Preparation process is the same as embodiment 1.
Embodiment 4
Aqueous polyurethane acrylate emulsion to more than obtained by each example carries out performance test before and after use.
Individual layer film is prepared in substrate surface, coated on size is 6.8cm by aqueous polyurethane acrylate Emulsion Spraying
× 3.7cm2 PC/ABS plastic basis materials surface, the infrared baking 8min at 50 DEG C, it is then 1300mJ/ in energy
Ultraviolet light solidification is carried out under conditions of cm2, obtains the decoration coated with individual layer white film, to its toughness, hardness, stably
Property and chemical resistance are tested.It the results are shown in Table 1.
The aqueous polyurethane acrylate emulsion property testing result of the present invention of table 1
Comparative example 1
The hydrophilic dihydric alcohol of nonionic in embodiment 1 is removed, the dosage of polyester diol is changed to 75g, other same embodiments
1.In gained polyurethane-acrylate emulsion performance test, toughness, hardness, stability and chemical resistance are unqualified.
Claims (9)
1. a kind of aqueous polyurethane acrylate emulsion, it is characterised in that it is made up of the component of following parts by weight：Polyester binary
25~45 parts of alcohol, 20~40 parts of the hydrophilic dihydric alcohol of nonionic, 40~60 parts of isocyanates, 1~5 part of chain extender, crosslinking agent 1~5
Part, 100~150 parts of trifunctional acrylic monomers, 0.01~0.5 part of polymerization inhibitor, 0.02~1 part of catalyst.
2. aqueous polyurethane acrylate emulsion according to claim 1, it is characterised in that it by following parts by weight group
Divide and be made：30~40 parts of polyester diol, 25~35 parts of the hydrophilic dihydric alcohol of nonionic, 45~55 parts of isocyanates, chain extender 1~
5 parts, 1~4 part of crosslinking agent, 110~140 parts of trifunctional acrylic monomers, 0.01~0.5 part of polymerization inhibitor, catalyst 0.02~1
Part.
3. aqueous polyurethane acrylate emulsion according to claim 1 or 2, it is characterised in that the polyester diol
Number-average molecular weight is 1900~2200, and the number-average molecular weight of the hydrophilic dihydric alcohol of nonionic is 800~1200.
4. aqueous polyurethane acrylate emulsion according to claim 1 or 2, it is characterised in that the nonionic hydrophilic two
First alcohol is Sweden Bai Situo Ymer N120；The isocyanates is in alicyclic isocyanate or aromatic isocyanate
One or more, the alicyclic isocyanate are IPDI or the isocyanic acid of bis- cyclohexyl methane of 4,4- two
Ester.
5. aqueous polyurethane acrylate emulsion according to claim 1 or 2, it is characterised in that the chain extender is three hydroxyls
Monoallyl ether；The crosslinking agent is trimethylolpropane；The trifunctional acrylic monomers is pentaerythrite
Triacrylate；The polymerization inhibitor is MEHQ；The catalyst is dibutyl tin laurate.
6. aqueous polyurethane acrylate emulsion according to claim 1 or 2, it is characterised in that it is by comprising the following steps
Method be prepared：
（1）Polyester diol and the hydrophilic dihydric alcohol of nonionic are dehydrated under 100~115 DEG C, vacuum；
（2）Dehydration terminates rear material cooling, adds isocyanates, is reacted at 70~85 DEG C, when measure nco value reaches reason
By value, carry out in next step；
（3）Chain extender is added in 70~85 DEG C of reactions；
（4）Crosslinking agent is added in 70~85 DEG C of reactions；
（5）Temperature is reduced to 65~75 DEG C；The mixture of trifunctional acrylic monomers, polymerization inhibitor and catalyst is added into control
Temperature is reacted below 75 DEG C, is reacted to NCO and is down to less than 0.1% stopping reaction, cooling, obtained resin is poured into
Deionized water regulation solid content is added in dispersion machine, it is scattered at a high speed, obtain polyurethane-acrylate emulsion.
7. aqueous polyurethane acrylate emulsion according to claim 6, it is characterised in that in step（1）In, polyester two
First hydrophilic dihydric alcohol of alcohol and nonionic carries out 0.8~1.2h of dehydration under 110 DEG C, vacuum 0.9MPa；In step（2）In, instead
It is 80 DEG C to answer temperature, and the reaction time is 1.5 ~ 2h；In step（3）Or（4）In, reaction temperature is 80 DEG C, reaction time 0.5h；
In step（5）In, 50 DEG C are cooled to after stopping reaction, obtained resin is poured into dispersion machine and adds deionized water regulation admittedly
Content disperses 8~12min under 1800~2200r/min, obtains polyurethane-acrylate emulsion to 30~60%.
8. the preparation method of the aqueous polyurethane acrylate emulsion described in a kind of claim 1 or 2, it is characterised in that it is included
Following steps：
（1）Polyester diol and the hydrophilic dihydric alcohol of nonionic are dehydrated under 100~115 DEG C, vacuum；
（2）Dehydration terminates rear material cooling, adds isocyanates, is reacted at 70~85 DEG C, when measure nco value reaches reason
By value, carry out in next step；
（3）Chain extender is added in 70~85 DEG C of reactions；
（4）Crosslinking agent is added in 70~85 DEG C of reactions；
（5）Temperature is reduced to 65~75 DEG C；The mixture of trifunctional acrylic monomers, polymerization inhibitor and catalyst is added into control
Temperature is reacted below 75 DEG C, is reacted to NCO and is down to less than 0.1% stopping reaction, cooling, obtained resin is poured into
Deionized water regulation solid content is added in dispersion machine, it is scattered at a high speed, obtain polyurethane-acrylate emulsion.
9. the preparation method of the aqueous polyurethane acrylate emulsion according to claims requirement 8, it is characterised in that
In step（1）In, polyester diol and the hydrophilic dihydric alcohol of nonionic carried out under 110 DEG C, vacuum 0.9MPa dehydration 0.8~
1.2h；In step（2）In, reaction temperature is 80 DEG C, and the reaction time is 1.5 ~ 2h；In step（3）Or（4）In, reaction temperature is
80 DEG C, reaction time 0.5h；In step（5）In, 50 DEG C are cooled to after stopping reaction, obtained resin is poured into dispersion machine
Middle addition deionized water adjusts solid content to 30~60%, and 8~12min is disperseed under 1800~2200r/min, obtains polyurethane
Acrylic acid ester emulsion.
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