CN106916254A - Polymerization of acrylic modified polyurethane emulsion and preparation method thereof - Google Patents
Polymerization of acrylic modified polyurethane emulsion and preparation method thereof Download PDFInfo
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08G18/44—Polycarbonates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The present invention relates to a kind of polymerization of acrylic modified polyurethane emulsion and preparation method thereof, preparation method comprises the following steps：After first just macromolecular polyol, diisocyanate, 2,2 dihydromethyl propionic acids and silane coupler are uniformly mixed, catalyst reaction is added to obtain base polyurethane prepolymer for use as；Add crylic acid hydroxy ester react crylic acid hydroxy ester end-blocking base polyurethane prepolymer for use as；Add the 1h of acrylate monomer stirring reaction 0.5；It is subsequently adding nertralizer and chain extender obtains pre-emulsion, is eventually adding K2S2O3The 2.5h of reactant aqueous solution 2, obtains final product the polymerization of acrylic modified polyurethane emulsion.The polymerization of acrylic modified polyurethane emulsion that above-mentioned preparation method is obtained has good pliability, not drying property and after tack, and with good intermiscibility, water-based ink is can be widely applied to, in water paint.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly to a kind of polymerization of acrylic modified polyurethane emulsion and its
Preparation method.
Background technology
Polyurethane is the abbreviation of polyurethanes, is mainly lived with containing two officials or many officials by two officials or many official's isocyanates
Bold and vigorous hydrogen compound is progressively polymerized synthesis.Polyurethane has intensity big, and tensile property is excellent, various spies such as richness glossiness is high
Point, is widely used in coating, printing, the field such as adhesive.By changing isocyanates and kind containing active hydrogen compounds
Class and proportioning, can also synthesize the product with various structures and function.
Polyurethane will generally add substantial amounts of solvent to dilute reduction viscosity, so as to improve its easy construction.And solvent
With inflammable and explosive toxicity it is big the features such as, the volatilization of a large amount of solvents can also cause serious environmental pollution during construction, for construction
Personnel also have very big health hazard.Decentralized medium is substituted for water by aqueous polyurethane by solvent, solves low VOC emission, low
The Environmental Safety problem such as toxicity, greatly reduces the inflammability of polyurethane products, and the regulation of viscosity is more flexible, can use many
Plant various forms of construction work such as roller coat spraying.But water-base polyurethane material is in water resistance, solvent resistance, the property of the aspect such as mechanical strength
Can be also relatively poor, in order to improve the combination property of aqueous polyurethane, people have carried out the modified work of many to it.
Have to be introduced into bisphenol A epoxide resin (E-44) in the chain extending reaction of polyurethane and synthesized epoxide modified aqueous poly- ammonia
Ester, film mechanics and water resistance are improved, heat resistance enhancing.
What is had first IPDI, DMPA, polyester diol, trimethylolpropane, Isosorbide-5-Nitrae butanediol and hydroxy-ethyl acrylate are obtained
The aqueous polyurethane emulsion of HEA end-blockings, adding acrylate monomer carries out free radical polymerization and prepares acrylate changing
The aqueous polyurethane emulsion of property.The increase of allyl monomer amount improves the adhesion strength of adhesive for polyurethane, water-fast and resistance to
Hot property.
The aqueous polyurethane of the first synthesis HEA end-blockings having, adding solvent and acrylate monomer carries out free radical initiation
Polymerization is prepared into polymerization of acrylic modified polyurethane emulsion.
In above-mentioned technology, epoxide modified also have when epoxy introduces more that performed polymer thickening is obvious, and stability also declines, and
Acrylate Modified Aqueous Polyurethane is simply used than wide due to synthesis technique, but in synthesis also needing to solvent reduces body
It is that viscosity is runed counter to environmentally friendly original intention.
The content of the invention
Based on this, it is an object of the invention to provide a kind of method of uninanned platform polymerization of acrylic modified polyurethane emulsion,
Modified polyaminoester emulsion has a good pliability, drying property and not after tack, and with good intermiscibility, can be extensive
Water-based ink is applied to, in water paint.
Specific technical scheme is as follows：
A kind of preparation method of polymerization of acrylic modified polyurethane emulsion, comprises the following steps：
(1) by macromolecular polyol 10-20 mass parts, diisocyanate 8-16 mass parts, 2,2- dihydromethyl propionic acids 1-3
Mass parts and silane coupler 0.1-0.5 mass parts are uniformly mixed；
(2) mixture that step (1) is obtained is warming up to 45-55 DEG C, is dividedly in some parts catalyst 0.01-0.04 mass parts；
(3) 80-90 DEG C is warming up to again, and stirring reaction 5-6h obtains base polyurethane prepolymer for use as；
(4) 75-80 DEG C is cooled to, crylic acid hydroxy ester 0.1-0.3 mass parts are added, 1.5-2.5h is reacted, acrylic acid is obtained
The base polyurethane prepolymer for use as of hydroxy ester end-blocking；
(5) be cooled to 60-65 DEG C, add methyl methacrylate 1-2 mass parts, butyl acrylate 2-5 mass parts and
Methyl acrylate 1-2 mass parts, stirring reaction 0.5-1h；
(6) be cooled to 40-50 DEG C, add nertralizer 0.5-2 mass parts stirring reaction 0.5-1h, be then cooled to 30 DEG C with
Under, 5-8 DEG C of deionized water 50-70 mass parts being added, at a high speed emulsification 5-20min, emulsifying temperature is less than 20 DEG C；
(7) product for adding step (6) to obtain after chain extender 0.2-0.6 mass parts deionized water is diluted, stirring is anti-
1-1.5h is answered, pre-emulsion is obtained；
(8) pre-emulsion is warming up to 75-80 DEG C, the K of 0.1-0.2 mass parts is added dropwise2S2O3The aqueous solution, in 3-3.5h
Drip off, then be warming up to 83-85 DEG C of reaction 2-2.5h, obtain final product the polymerization of acrylic modified polyurethane emulsion.
Wherein in some embodiments, the diisocyanate is selected from isophorone diisocyanate, the isocyanide of diphenyl-methane two
One kind in acid esters, dicyclohexyl methyl hydride diisocyanate, toluene di-isocyanate(TDI) or 1,6- hexamethylene diisocyanates or
It is several.
Wherein in some embodiments, the macromolecular polyol is selected from polyether Glycols of the molecular weight more than 1000, gathers
Ester dihydroxylic alcohols or PCDL.
Wherein in some embodiments, the silane coupler is selected from γ-glycidyl ether oxygen propyl trimethoxy silicane,
γ-(methacryloxypropyl) propyl trimethoxy silicane or gamma-aminopropyl-triethoxy-silane.
Wherein in some embodiments, catalyst described in step (2) is dibutyl tin, stannous octoate or triethylamine.
Wherein in some embodiments, in step (3), the content of NCO is 4-5% in the base polyurethane prepolymer for use as.
Wherein in some embodiments, in step (4), the NCO of the base polyurethane prepolymer for use as of the crylic acid hydroxy ester end-blocking
Content be 3-4%.
Wherein in some embodiments, crylic acid hydroxy ester described in step (4) is hydroxyethyl methacrylate.
Wherein in some embodiments, the nertralizer is selected from triethylamine, dimethylethanolamine or triethanolamine；The expansion
Chain agent is selected from ethylenediamine, propane diamine, butanediamine or hexamethylene diamine.
It is a further object of the present invention to provide a kind of polymerization of acrylic modified polyurethane emulsion.
Above-mentioned preparation method prepares polymerization of acrylic modified polyurethane emulsion.
The polymerization of acrylic modified polyurethane emulsion that above-mentioned preparation method is obtained has the advantages that：
1st, acetone or other solvents need not be added to dilute in aforesaid propylene acid esters modified polyurethane emulsion building-up process.
The base polyurethane prepolymer for use as synthesizing HEMA end-blockings by early stage adds acrylate monomer and dilutes and add amine neutralizer pre-emulsification,
Adding peroxide carries out the acrylate modified polyaminoester emulsion of Raolical polymerizable generation.
2nd, water resistance is greatly improved.Silane coupler is introduced into resin chain by the synthesis of polyurethane performed polymer stage,
And the introducing of acrylic monomers improves the water-fast moisture-proof of resin.
3rd, rate of drying is improve, and does not return the viscous and excellent effect of resistance to alcoholic solvent.It is acrylate modified by hard monomer
Polyaminoester emulsion improves the drying type and not after tack of resin, and by the distinctive self-emulsifying of polyaminoester emulsion, carries
Its resistance to alcoholic solvent high has good stability of emulsion and intermiscibility.In can be widely applied to water-based ink coating.
4th, paint film performance is excellent.There is acrylate modified polyaminoester emulsion good glossiness to reach 80~85 °.Firmly
Degree is high, and adhesive force is excellent, also with good water-fast endurance.
Specific embodiment
For the ease of understanding the present invention, the present invention will be described more fully below.But, the present invention can be with perhaps
More different form is realized, however it is not limited to embodiment described herein.On the contrary, the purpose for providing these embodiments is to make
Understanding to the disclosure is more thorough comprehensive.
Unless otherwise defined, all of technologies and scientific terms used here by the article with belong to technical field of the invention
The implication that technical staff is generally understood that is identical.The term for being used in the description of the invention herein is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
The arbitrary and all of combination of the Listed Items of pass.
Embodiment 1
A kind of preparation method of polymerization of acrylic modified polyurethane emulsion of the present embodiment comprises the following steps：
1) by 7 parts of IPDIs, 1 part of DMPA (2,2- dihydromethyl propionic acid), 0.5 part of γ-(2,3- ring
The oxygen of oxygen third) propyl trimethoxy silicane (KH560), 15 part of 1000 molecular weight polyester dihydroxylic alcohols be placed in equipped with mechanical agitator, drop
In the four-hole boiling flask of liquid funnel and reflux condensing tube, stir 1 hour, DMPA is fully dispersed uniform；
2) 50 DEG C add 0.02 part of stannous octoate (adding in three times, per minor tick 0.5h) and keeping temperature is no more than 55
DEG C, it is warmed up to 80 DEG C, stirring reaction 6 hours, 400~600rpm of rotating speed；
3) cool to 75 DEG C, add HEMA (hydroxyethyl methacrylate), 75 DEG C of stirring reactions 2 hours；
4) 60 DEG C are cooled to, MMA (methyl methacrylate) is added, BA (butyl acrylate), MA (methyl acrylate) is stirred
Mixing 0.5 hour makes acrylate monomer be sufficiently mixed with polyurethane prepolymer；
5) 40~50 DEG C are cooled to again, adds 1 part of triethylamine to carry out neutralization salt-forming reaction, stir 0.5 hour；
6) neutralize end and cool to less than 30 DEG C, add 50 parts of deionized water (5~8 DEG C of water temperature), carried out in emulsion tank
, at 1800~2300 turns, emulsification times were at 5~10 minutes for emulsification rotating speed at a high speed；
7) it is added dropwise in 0.5 part of EDA instillation emulsion tanks, 30 DEG C are reacted 1 hour；
8) reaction is poured into retort pre-emulsion after terminating, and K is added dropwise2S2O8Number is 0.1, is progressively warmed up to 80 DEG C, 3
Hour drips off K2S2O8, then it is warmed up to 85 DEG C, and stirring reaction 2 hours, filtering and discharging is obtained final product.
Embodiment 2
A kind of preparation method of polymerization of acrylic modified polyurethane emulsion of the present embodiment, comprises the following steps：
1) by 7 parts of IPDIs, 1 part of DMPA, 0.5 part of γ-(2,3- the third oxygen of epoxy) propyl trimethoxy
Silane (KH560), 15 part of 1000 molecular weight polycarbonate dihydroxylic alcohols is placed in equipped with mechanical agitator, dropping funel and reflux condensation mode
In the four-hole boiling flask of pipe, stir 1 hour, DMPA is fully dispersed uniform；
2) 50 DEG C add 0.02 part of stannous octoate (adding in three times, per minor tick 0.5h) and keeping temperature is no more than 55
DEG C, it is warmed up to 80 DEG C, stirring reaction 6 hours, 400~600rpm of rotating speed；
3) cool to 75 DEG C, add HEMA, 75 DEG C of stirring reactions 2 hours；
4) 60 DEG C are cooled to, MMA, BA, MA is added, stirring makes acrylate monomer be filled with polyurethane prepolymer in 0.5 hour
Divide mixing；
5) 40~50 DEG C are cooled to again, adds 1.5 parts of dimethylethanolamine to carry out neutralization salt-forming reaction, stir 0.5 hour；
6) neutralize end and cool to less than 30 DEG C, add 70 parts of deionized water (5~8 DEG C of water temperature), carried out in emulsion tank
, at 1800~2300 turns, emulsification times were at 5~10 minutes for emulsification rotating speed at a high speed；
7) it is added dropwise in 0.5 part of EDA instillation emulsion tanks, 30 DEG C are reacted 1 hour；
8) reaction is poured into retort pre-emulsion after terminating, and K is added dropwise2S2O8Number is 0.1, is progressively warmed up to 80 DEG C, 3
Hour drips off K2S2O8, then it is warmed up to 85 DEG C, and stirring reaction 2 hours, filtering and discharging is obtained final product.
Embodiment 3
A kind of preparation method of polymerization of acrylic modified polyurethane emulsion of the present embodiment, comprises the following steps：
1) by 7 parts of IPDIs, 1 part of DMPA, 0.5 part of γ-(2,3- the third oxygen of epoxy) propyl trimethoxy
Silane (KH560), 15 part of 1000 molecular weight polycaprolactone dihydroxylic alcohols is placed in equipped with mechanical agitator, dropping funel and reflux condensation mode
In the four-hole boiling flask of pipe, stir 1 hour, DMPA is fully dispersed uniform；
2) 50 DEG C add 0.02 part of stannous octoate (adding in three times, per minor tick 0.5h) and keeping temperature is no more than 55
DEG C, it is warmed up to 80 DEG C, stirring reaction 6 hours, 400~600rpm of rotating speed；
3) cool to 75 DEG C, add HEMA, 75 DEG C of stirring reactions 2 hours；
4) 60 DEG C are cooled to, MMA, BA, MA is added, stirring makes acrylate monomer be filled with polyurethane prepolymer in 0.5 hour
Divide mixing；
5) 40~50 DEG C are cooled to again, adds 1.5 parts of dimethylethanolamine to carry out neutralization salt-forming reaction, stir 0.5 hour；
6) neutralize end and cool to less than 30 DEG C, add 70 parts of deionized water (5~8 DEG C of water temperature), carried out in emulsion tank
, at 1800~2300 turns, emulsification times were at 5~10 minutes for emulsification rotating speed at a high speed；
7) it is added dropwise in 0.5 part of hexamethylene diamine instillation emulsion tank, 30 DEG C are reacted 1 hour；
8) reaction is poured into retort pre-emulsion after terminating, and K is added dropwise2S2O8Number is 0.1, is progressively warmed up to 80 DEG C, 3
Hour drips off K2S2O8, then it is warmed up to 85 DEG C, stirring reaction 2 hours, filtering and discharging.
Comparative example
A kind of preparation method of polymerization of acrylic modified polyurethane emulsion of the present embodiment, comprises the following steps：
1) by 7 parts of IPDIs, 1 part of DMPA, 0.5 part of γ-(2,3- the third oxygen of epoxy) propyl trimethoxy
Silane (KH560), 15 part of 2000 molecular weight polyester dihydroxylic alcohols proper amount of acetone is placed in equipped with mechanical agitator, dropping funel and backflow
In the four-hole boiling flask of condenser pipe, stir 1 hour, DMPA is fully dispersed uniform；
2) 50 DEG C add 0.02 part of stannous octoate (adding in three times, per minor tick 0.5h) and keeping temperature is no more than 55
DEG C, it is warmed up to 80 DEG C, stirring reaction 6 hours, 400~600rpm of rotating speed；Acetone is continuously added in reaction for reducing viscosity
3) cool to 75 DEG C, add HEMA, 75 DEG C of stirring reactions 2 hours；
4) 40~50 DEG C are cooled to, adds 3 parts of triethanolamine to carry out neutralization salt-forming reaction, add deionized water to carry out at a high speed
Stirring and emulsifying, emulsifies 2500 turns of rotating speed, and emulsification times 10 minutes are added dropwise in 0.5 part of hexamethylene diamine instillation emulsion tank, 30 DEG C of reactions
1 hour；
5) vacuum distillation, removes the acetone in pre-emulsion；
6) 60 DEG C are warmed up to, MMA, BA, MA is added, stirring makes acrylate monomer abundant with polyaminoester emulsion in 0.5 hour
Mixing；
7) pre-emulsion is poured into retort, K is added dropwise2S2O8Number is 0.1, is progressively warmed up to 80 DEG C, is dripped off within 3 hours
K2S2O8, then it is warmed up to 85 DEG C, stirring reaction 2 hours, filtering and discharging.
Test result
The polymerization of acrylic modified polyurethane emulsion that will synthesize in each embodiment, a certain amount of levelling agent of addition, defoamer,
Water, specific formulation for coating material such as table 1：
Table 1 can UV photocuring Compositions of Water-borne PU Coatings
The coating that will have been configured is coated on glass, then is placed on 60 DEG C of baking oven baking 5min, can obtain cured paint film, paint film
Can be as shown in table 2：
The test result of each embodiment of table 2
The polymerization of acrylic modified polyurethane emulsion synthesized using solventless method, water resistance strong advantage high with glossiness,
And technique is easy, it is not necessary to removed under reduced pressure acetone, it also avoid the problem of acetone residue in emulsion, more meets VOC emission mark
It is accurate.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of preparation method of polymerization of acrylic modified polyurethane emulsion, it is characterised in that comprise the following steps：
(1) by macromolecular polyol 10-20 mass parts, diisocyanate 8-16 mass parts, 2,2- dihydromethyl propionic acid 1-3 mass
Part and silane coupler 0.1-0.5 mass parts are uniformly mixed；
(2) mixture that step (1) is obtained is warming up to 45-55 DEG C, is dividedly in some parts catalyst 0.01-0.04 mass parts；
(3) 80-90 DEG C is warming up to again, and stirring reaction 5-6h obtains base polyurethane prepolymer for use as；
(4) 75-80 DEG C is cooled to, crylic acid hydroxy ester 0.1-0.3 mass parts are added, 1.5-2.5h is reacted, dihydroxypropyl is obtained
The base polyurethane prepolymer for use as of ester end-blocking；
(5) 60-65 DEG C is cooled to, methyl methacrylate 1-2 mass parts, butyl acrylate 2-5 mass parts and propylene is added
Sour methyl esters 1-2 mass parts, stirring reaction 0.5-1h；
(6) 40-50 DEG C is cooled to, nertralizer 0.5-2 mass parts stirring reaction 0.5-1h are added, less than 30 DEG C are then cooled to,
5-8 DEG C of deionized water 50-70 mass parts are added, at a high speed emulsification 5-20mi n, emulsifying temperature is less than 20 DEG C；
(7) product for adding step (6) to obtain after chain extender 0.2-0.6 mass parts deionized water is diluted, stirring reaction 1-
1.5h, obtains pre-emulsion；
(8) pre-emulsion is warming up to 75-80 DEG C, the K of 0.1-0.2 mass parts is added dropwise2S2O3The aqueous solution, drips off in 3-3.5h,
83-85 DEG C of reaction 2-2.5h is warming up to again, obtains final product the polymerization of acrylic modified polyurethane emulsion.
2. preparation method according to claim 1, it is characterised in that the diisocyanate is selected from the isocyanide of isophorone two
Acid, '-diphenylmethane diisocyanate, dicyclohexyl methyl hydride diisocyanate, toluene di-isocyanate(TDI) or 1,6- hexa-methylenes two are different
One or more in cyanate.
3. preparation method according to claim 1, it is characterised in that the macromolecular polyol is more than selected from molecular weight
1000 polyether Glycols, polyester diol or PCDL.
4. preparation method according to claim 1, it is characterised in that the silane coupler is selected from γ-glycidol ether
Oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane or gamma-aminopropyl-triethoxy-silane.
5. preparation method according to claim 1, it is characterised in that catalyst described in step (2) is dibutyl tin, pungent
Sour stannous or triethylamine.
6. preparation method according to claim 1, it is characterised in that in step (3), NCO in the base polyurethane prepolymer for use as
Content be 4-5%.
7. preparation method according to claim 1, it is characterised in that in step (4), the crylic acid hydroxy ester end-blocking
The content of the NCO of base polyurethane prepolymer for use as is 3-4%.
8. the preparation method according to claim any one of 1-7, it is characterised in that dihydroxypropyl described in step (4)
Ester is hydroxyethyl methacrylate.
9. the preparation method according to claim any one of 1-7, it is characterised in that the nertralizer is selected from triethylamine, two
Methylethanolamine or triethanolamine；The chain extender is selected from ethylenediamine, propane diamine, butanediamine or hexamethylene diamine.
10. the preparation method described in any one of claim 1-9 prepares polymerization of acrylic modified polyurethane emulsion.
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| CN115595036A (en) * | 2022-11-04 | 2023-01-13 | 广州立诺新材料科技有限公司（Cn） | Acrylic acid modified polyurethane dispersion for plastic-replacing gloss oil and preparation method thereof |
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