CN103626930B - A kind of preparation method of Aqueous acrylic urethane's matting resin with phase separation structure - Google Patents
A kind of preparation method of Aqueous acrylic urethane's matting resin with phase separation structure Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of Aqueous acrylic urethane's matting resin with phase separation structure, belong to aqueous antiglossing pigment field.Described has phase separation structure acroleic acid polyurethane matting resin, comprises the component of following weight portion meter: acrylate 30 68 parts；Ion-type occlusive polyurethane 10 34 parts；Nonionic polyurethane 5 17 parts；Initiator 0.18 0.41 parts；Chain-transferring agent 0.03 0.068 parts；Alkali compounds 4.2 11.7 parts；90 204 parts of water.Acroleic acid polyurethane matting resin prepared by the present invention, has curability at low temperatures, mold-mart shielding is excellent, flatting efficiency is high, resistance to water, and acidproof, alkali resistance highlights, the advantages such as anti-wear performance is good.And crosslink reaction by introducing anion occlusive polyurethane with the hydroxyl in acrylic resin, strengthen the crosslink density of interlaminar resin, improve mechanical strength and the surface erasibility of matting resin.
Description
Technical field
The invention belongs to aqueous antiglossing pigment field, particularly to a kind of poly-ammonia of water soluble acrylic acid with phase separation structure
The preparation method of ester matting resin.
Background technology
Widespread demand aqueous antiglossing pigment in recent years, but this antiglossing pigment great majority are all by adding delustering agent or disappearing
Light powder manufactures aqueous antiglossing pigment.As the aqueous antiglossing pigment of this preparation method, such as, silica dioxide delustring agent is divided
The method (CN101186773A) being dispersed in self-crosslinking acrylic resin；Delustering agent is added to acrylic acid modified polyurethane system
In aqueous mono-component matte varnish (CN102363702)；Delustering agent is added to and is formed inside polyacrylic polyols
Component A, then component A and component B anion-modified HDI polyisocyanates are mixed in proportion the aqueous double-component extinction type made
Clear finish (CN102363696A)；Flatting silica is added to shape in emulsion type anionic polyurethane resin and water-borne acrylic resin
Become the method (CN102533079A) of extinction type use for synthetic leather finishing agent.
But current technology there is also and needs in the dispersive process of some shortcoming, i.e. delustering agent to disperse by macromolecule
Agent, wetting agent, the various auxiliary agents such as anti-settling agent, the preparation process causing coating is loaded down with trivial details and complicated；Additionally, delustering agent is along with when placing
Between increase can produce precipitation, thus the application on aqueous antiglossing pigment produces impact.
And as the aqueous antiglossing pigment of resin type, have the two kinds of acrylic resins utilizing solubility parameter different and with
These resins do not have anion electrophoresis coating " the Unexamined Patent 10-46065 public affairs that the melmac of the compatibility is dispersed in water
Report "；Additionally, the resin that also will be provided with water dispersible mixes with melmac, the difference of the SP value of resin is utilized to obtain nothing
Light coating " JP 2001-131494 publication ".But the coating of above-mentioned two invention must toast, easily more than 170 DEG C
Make film produce be full of cracks, film performance is produced impact；Additionally its consumed energy increases, and can cause loss economically.
Additionally, there is use to contain carboxyl and the resin of hydroxyl, the water soluble electrocoating that blocked polyisocyanates compound manufactures,
Have obtain the excellent performance of 140 DEG C of baking-curings, film that gloss is low, but its mould scar shielding " Unexamined Patent 8-not
No. 41380 publications ".
The above-mentioned method medium vinyl resin manufacturing processes mentioned uses solution polymerization process mostly, manufacture process needs
Using organic solvent in a large number, coating is easily subject to the impact of solvent, and containing substantial amounts of VOC (Volatile
Organic compounds, VOC), pollute environment, human body is produced harm.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, the primary and foremost purpose of the present invention is to provide one to have the knot that is separated
Aqueous acrylic urethane's matting resin of structure, this acroleic acid polyurethane matting resin can solidify at low temperatures, stable storing
Property is good, and mold-mart shielding is excellent, flatting efficiency is high, and without organic solvent, 60 ° of lower gloss reach less than 20.
Another object of the present invention is to provide above-mentioned Aqueous acrylic urethane's matting resin with phase separation structure
Preparation method.
It is still another object of the present invention to provide above-mentioned Aqueous acrylic urethane's matting resin with phase separation structure
Application.
The purpose of the present invention is achieved through the following technical solutions: a kind of Aqueous acrylic urethane with phase separation structure
Matting resin, comprises the component of following weight portion meter:
Described acrylate is by carboxylic unsaturated acrylic ester monomer, hydroxyl unsaturation esters of acrylic acid list
Body and free-radical polymerised acrylic ester monomer mixing composition；
The acid number of described acrylate is 15-150mg KOH/g, preferably 40-100mg KOH/g；Hydroxyl value is 30-150mg
KOH/g, preferably 40-100mg KOH/g；Vitrification point is 20-60 DEG C, preferably 30-50 DEG C；Molecular weight is 10000-
100000, the scope of preferably 20000-60000；Molecular weight distribution is 1～5；
Described carboxylic unsaturated acrylic ester monomer be preferably the one in methacrylic acid or acrylic acid or
Two kinds；
The unsaturated acrylic ester monomer of described hydroxyl is preferably (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) third
Olefin(e) acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxy butyl ester, polypropylene glycol monomethacrylate or polypropylene glycol mono acrylic ester
In at least one；
Described free-radical polymerised acrylic ester monomer is preferably (methyl) acrylic acid methyl ester., (methyl) acrylic acid second
Ester, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) acrylic acid ten
Trialkyl ester, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, acrylonitrile, acrylamide, lauryl
Two or more monomers in ester, N methacrylamide etc. or styrene；
The compounding ratio of the described mix monomer in acrylate, is more preferably grouped by the one-tenth of following weight portion meter
Become:
Described anionic occlusive polyurethane be aromatic compound, aliphatic compound, alicyclic ring kind isocyanate and
PEPA is under catalyst action, through the polyurethane that small molecule alcohol and the chain extender addition polymerization Han carboxyl obtain；Described
Polyester polyol content (referring to account for the mass fraction of the polyurethane of synthesis) be 10-50%, preferably 25-45%；Polyester polyols used
Alcohol number-average molecular weight is 200-5000, preferably 400-1000；Synthesis of polyurethane molecular weight is 1000～7000, preferably 2000～
5000；Preferably alicyclic ring kind isocyanate and PEPA are under catalyst action, through small molecule alcohol and the chain extender Han carboxyl
The polyurethane that addition polymerization obtains；
Described anionic occlusive polyurethane molecular weight can be controlled by regulation polyester polyol molecule amount；
Described anionic occlusive polyurethane is prepared by following steps: 0.10mol isophorone diisocyanate
Mix with 0.025mol Polyethylene Glycol, add 1-2 and drip catalyst dibutyl tin laurate, 50ml acetone, stir, in 80 DEG C
Back flow reaction 1.5h in water bath with thermostatic control, adds 0.0125mol1,4-butanediol and continues reaction 1h, add under stirring
0.0525mol dihydromethyl propionic acid continues reaction 4h, continues back flow reaction 2h, survey by dibutyl amine method after adding 0.8mol end-capping reagent
Time in fixed output quota thing without the-NCO dissociated, cooling down to 60 DEG C, add 0.0525mol alkali compounds and continue reaction 0.5h,
Add distilled water, violent shear agitation 0.5h under high velocity agitation, cool, extract acetone, prepare anionic and close poly-
Urethane；
The molecular weight of described Polyethylene Glycol is preferably 400～1000；
In the preparation of anionic occlusive polyurethane, described end-capping reagent has phenolic compound, alcohol compound, oximes
Compound, active methylene group compounds, lactam analog compound, aminated compounds, glyoxaline compound, carbamide class chemical combination
Thing, carbamate compound etc.；Preferably oxime compound；More preferably methyl ethyl ketoxime；
In the preparation of anionic occlusive polyurethane, described alkali compounds is ethamine, propylamine, butylamine, benzylamine, list
Ethanolamine, neopentyl alcohol amine, 2-aminopropanol, 3-aminopropanol, diethylamine, triethylamine, 2-aminopropane., diisopropylamine, Tris(isopropylamine).,
Diethanolamine, diisopropanolamine (DIPA), triethanolamine, dimethylethanolamine, diethyl ethylene diamine, aqueous amine, sodium hydroxide or hydroxide
One in potassium, considers to be preferably triethylamine from combination property；
Described nonionic polyurethane is prepared by following steps: take 0.05mol hexamethylene diisocyanate three
Aggressiveness (HDI trimer) mixes with 0.15mol poly glycol monomethyl ether, add 1～2 catalyst dibutyl tin laurate,
50ml acetone, stirs, back flow reaction in 80 DEG C of waters bath with thermostatic control, measures in product without free-NCO by dibutyl amine method
Time, add distilled water, violent shear agitation 0.5h, cooling down under high velocity agitation, extract acetone, prepare the poly-ammonia of nonionic
Ester；
The molecular weight of described poly glycol monomethyl ether is 500～2000；
Described initiator is the one in potassium peroxydisulfate, sodium peroxydisulfate or Ammonium persulfate., preferably potassium peroxydisulfate；
Described chain-transferring agent is sulfur alcohol compound, preferably lauryl mercaptan；
Described alkali compounds is ethamine, propylamine, butylamine, benzylamine, monoethanolamine, neopentyl alcohol amine, 2-aminopropanol, 3-
Aminopropanol, diethylamine, triethylamine, 2-aminopropane., diisopropylamine, Tris(isopropylamine)., diethanolamine, diisopropanolamine (DIPA), triethanolamine,
One in dimethylethanolamine, diethyl ethylene diamine, aqueous amine, sodium hydroxide or potassium hydroxide；Consider from combination property, select second
Hydramine is best；The neutralization ratio reached by these alkaline matters is advisable with 30%～100%, especially more preferable with 60%～90%；
The preferred deionized water of described water.
The present invention has in phase separation structure acroleic acid polyurethane matting resin, can add as required pigment, dyestuff,
Cross-linking agent, defoamer, stabilizer etc. are adjusted, and optimize the performance of film further.
The preparation method of above-mentioned Aqueous acrylic urethane's matting resin with phase separation structure, comprises the following steps:
Under the protection of nitrogen, after anionic occlusive polyurethane and nonionic polyurethane are dissolved in water, add part
Acrylate, chain-transferring agent, the initiator of part, be sufficiently mixed, and reacts 0.5-1.5h at 75-85 DEG C, prepares seed emulsion；So
The remaining acrylate of rear dropping and remaining initiator, time for adding controls after 3-5h, dropping 75-85 DEG C of insulation
1-3h, reduction temperature is to 45 DEG C, and addition alkali compounds regulation pH value, to 8.0-9.5, obtains the aqueous with phase separation structure
Acroleic acid polyurethane matting resin.
Described part propylene acid esters is 1:3 with the mass ratio of remaining acrylate；
The initiator of described part is 1:3 with the mass ratio of remaining initiator.
Described one has phase separation structure acroleic acid polyurethane matting resin, and its application is for can having the knot that is separated
Structure acroleic acid polyurethane matting resin finished product coats drying and forming-film to woodenware or metal device, it is thus achieved that the painting of gloss less than 20
Film surface.
It is from the Extinction Characteristic of coating, coating that the present invention has the preparation of phase separation structure acroleic acid polyurethane matting resin
Stability, curability at low temperatures, the feature of environmental protection and physicochemical property each side consider, the contradiction between balance various factors, design
Go out coating performance and the most excellent product of workability, controlled the vitrification temperature of polymer by the ratio between soft or hard monomer
Degree, controls polymer molecular weight and distribution thereof by mercaptan；By hydroxy radical content reasonable in design, to provide suitable hydroxyl
Value；Introduce appropriate methacrylic acid and reach suitable acid number；Introduce styrene monomer, make coating possess resistance tocrocking and resistance to
Aqueous, reduces the compatibility between coating.By overall design, the emulsion of synthesis is made to possess good stability and physics and chemistry
Energy.
The reaction principle of the present invention is:
The present invention has the 1st elementary reaction prepared by phase separation structure acroleic acid polyurethane matting resin, by different Fo Er
Ketone diisocyanate and Polyethylene Glycol react under catalyst action, then pass through addition BDO, dihydromethyl propionic acid
Carry out chain extension, finally utilize end-capping reagent methyl ethyl ketoxime to block, be neutralized followed by triethylamine, prepare anionic and close poly-
Urethane；2nd stage by hexamethylene diisocyanate trimer (HDI trimer) and poly glycol monomethyl ether at catalysts conditions
Under carry out reaction and prepare nonionic polyurethane；3rd stage is by the unsaturated monomer containing hydroxyl, unsaturated single containing carboxyl
Body and other free-radical polymerised unsaturated acrylic ester monomer are at anionic occlusive polyurethane and nonionic polyurethane
After carrying out emulsion polymerization under conditions of existence, addition alkali compounds regulation pH value, to 8.0-9.5, obtains having phase separation structure
Acroleic acid polyurethane matting resin；In resin film forming procedure, anionic part occlusive polyurethane and the hydroxyl in acrylic resin
Crosslink reaction, strengthen the crosslink density of interlaminar resin, improve mechanical strength and the surface erasibility of matting resin；Meanwhile,
The anion occlusive polyurethane of excess and nonionic polyurethane are non-uniformly distributed in acrylic resin, promote phase separation structure
Occur, make coating produce ununiform shrinkage when film forming, form micro-rough surface, reduce the purpose of gloss.
The present invention compared with prior art has a characteristic that
1. the phase separation structure acroleic acid polyurethane matting resin that has prepared contains using water as disperse medium, VOC
Measuring low, abnormal smells from the patient is little, nontoxic pollution-free；
2. prepare has phase separation structure acroleic acid polyurethane matting resin, has curability at low temperatures, mold mark
Mark shielding is excellent, flatting efficiency is high, resistance to water, and acidproof, alkali resistance highlights, the advantages such as anti-wear performance is good.And by introducing the moon
Ion occlusive polyurethane crosslinks reaction with the hydroxyl in acrylic resin, strengthens the crosslink density of interlaminar resin, improves and disappear
The mechanical strength of photopolymer resin and surface erasibility.
3. nonionic occlusive polyurethane is insensitive to electrolyte, and the paint stability of preparation is preferable；Resin need not add
Add delustering agent, low cost；Raw material sources are extensive, and therefore application prospect is extensive.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of preparation method with phase separation structure acroleic acid polyurethane matting resin, comprises the following steps:
(1) anionic occlusive polyurethane is prepared: by 0.10mol isophorone diisocyanate and the poly-second of 0.025mol two
Alcohol (molecular weight 400) mixes, and adds 1-2 and drips catalyst dibutyl tin laurate, 50ml acetone, stirs, in 80 DEG C of constant temperature
Back flow reaction 1.5h in water-bath, adds 0.0125mol1,4-butanediol and continues reaction 1h, add 0.0525mol bis-under stirring
Hydroxymethyl propionic acid continues reaction 4h, adds 0.8mol methyl ethyl ketoxime and continues back flow reaction 2h, measures in product not by dibutyl amine method
During containing the-NCO dissociated, cooling down to 60 DEG C, add 0.0525mol triethylamine and continue reaction 0.5h, add under high velocity agitation
Enter distilled water, violent shear agitation 0.5h, cool, extract acetone, prepare anionic occlusive polyurethane；
(2) nonionic polyurethane is prepared: add 0.05molHDI trimer and 0.15mol Polyethylene Glycol in the reactor
Monomethyl ether (molecular weight 500), 1～2 catalyst dibutyl tin laurate, 50ml acetone, stir, in 80 DEG C of waters bath with thermostatic control
Middle back flow reaction 5h, with time in dibutyl amine method mensuration product without the-NCO dissociated, adds distilled water, acutely under high velocity agitation
Shear agitation 0.5h, cooling down, extract acetone, prepare nonionic polyurethane；
(3) by 5.4 parts of methyl methacrylates, 4.5 parts of hydroxyethyl methylacrylates, 2.4 parts of methacrylic acids, 6.0 parts
Butyl methacrylate, 7.2 parts of butyl acrylate, 4.4 parts of styrene mix homogeneously obtain acrylate mixture, standby；
(4) under the protection of nitrogen, by the anionic polyurethane of 10 parts of steps (1), the nonionic of 5 parts of steps (2)
Polyurethane is dissolved in 120 parts of deionized waters, is subsequently adding equipped with agitator, reflux condensing tube, thermometer and separatory funnel
In four mouthfuls of round-bottomed flasks, add 7.5 parts of acrylate mixture, 0.03 part of lauryl mercaptan, 5%(mass fraction) initiation
Agent potassium persulfate solution 0.9 part, is warming up to 75 DEG C in quick whipping process, after reaction 1.5h, prepare seed emulsion；Leak from dropping liquid
Bucket drips 22.5 parts of acrylate mixture and 5%(mass fraction) initiator sodium peroxydisulfate solution 2.7 parts, drip off in 5h,
Continuing to be incubated 3h at 75 DEG C, reduction temperature, to 45 DEG C, adds triethanolamine 4.2 parts regulation pH to about 8.5, i.e. can get milky white
Color, solid content 20.8% acroleic acid polyurethane matting resin A.
Described number is weight fraction.
Embodiment 2
A kind of preparation method with phase separation structure acroleic acid polyurethane matting resin, comprises the following steps:
(1) preparation method of anionic polyurethane is with embodiment 1 step (1)；
(2) nonionic polyurethane is prepared: add 0.05molHDI trimer and 0.15mol Polyethylene Glycol in the reactor
Monomethyl ether (molecular weight 1000), 1～2 catalyst dibutyl tin laurate, 50ml acetone, stir, in 80 DEG C of thermostatted waters
Back flow reaction 5h in bath, with time in dibutyl amine method mensuration product without the-NCO dissociated, adds distilled water under high velocity agitation, acute
Strong shear agitation 0.5h, cooling down, extract acetone, prepare nonionic polyurethane；
(3) by 12 parts of methyl methacrylates, 7.5 parts of hydroxyethyl methylacrylates, 5.0 parts of methacrylic acids, 7.7 parts of first
Base butyl acrylate, 10.2 parts of butyl acrylate, 7.6 parts of styrene mix homogeneously obtain acrylate mixture, standby；
(4) under the protection of nitrogen, by the anionic polyurethane of 25 parts of steps (1), the nonionic of 12.5 parts of steps (2)
Type polyurethane is dissolved in 150 parts of deionized waters, is subsequently adding equipped with agitator, reflux condensing tube, thermometer and separatory funnel
Four mouthfuls of round-bottomed flasks in, add 12.5 parts of acrylate mixture, 0.05 part of lauryl mercaptan, 5%(mass fraction) draw
Send out agent potassium persulfate solution 1.5 parts, quick whipping process is warming up to 80 DEG C, after reaction 1h, prepare seed emulsion；Leak from dropping liquid
Bucket drips 37.5 parts of acrylate mixture and 5%(mass fraction) initiator sodium peroxydisulfate solution 4.5 parts, drip off in 5h,
Continuing to be incubated 2h at 80 DEG C, reduction temperature, to 45 DEG C, adds triethanolamine 8.7 parts regulation pH to about 8.5, i.e. can get milky white
Color, solid content 20.5% acroleic acid polyurethane matting resin B.
Described number is weight fraction.
Embodiment 3
A kind of preparation method with phase separation structure acroleic acid polyurethane matting resin, comprises the following steps:
(1) anionic occlusive polyurethane is prepared: by 0.10mol isophorone diisocyanate and the poly-second of 0.025mol two
Alcohol (molecular weight 1000) mixes, and adds 1-2 and drips catalyst dibutyl tin laurate, 50ml acetone, stirs, in 80 DEG C of constant temperature
Back flow reaction 1.5h in water-bath, adds 0.0125mol1,4-butanediol and continues reaction 1h, add 0.0525mol bis-under stirring
Hydroxymethyl propionic acid continues reaction 4h, adds 0.8mol methyl ethyl ketoxime and continues back flow reaction 2h, measures in product not by dibutyl amine method
During containing the-NCO dissociated, cooling down to 60 DEG C, add 0.0525mol triethylamine and continue reaction 0.5h, add under high velocity agitation
Enter distilled water, violent shear agitation 0.5h, cool, extract acetone, prepare anionic occlusive polyurethane；
(2) preparation method of non-type polyurethane is with embodiment 1 step (2)
(3) by 17.2 parts of methyl methacrylates, 10.2 parts of hydroxyethyl methylacrylates, 6.8 parts of methacrylic acids, 10.7
Part butyl methacrylate, 13.1 parts of butyl acrylate, 10.0 parts of styrene mix homogeneously obtain acrylate mixture, standby
With；
(4) under the protection of nitrogen, by the anionic polyurethane of 34 parts of steps (1), the nonionic of 17 parts of steps (2)
Polyurethane is dissolved in 204 parts of deionized waters, is subsequently adding equipped with agitator, reflux condensing tube, thermometer and separatory funnel
In four mouthfuls of round-bottomed flasks, add 17 parts of acrylate mixture, 0.068 part of lauryl mercaptan, 5%(mass fraction) initiation
Agent potassium persulfate solution 2.04 parts, is warming up to 85 DEG C in quick whipping process, after reaction 0.5h, prepare seed emulsion；From dropping liquid
Funnel drips 51 parts of acrylate mixture and 5%(mass fraction) initiator sodium peroxydisulfate solution 6.12 parts, drip in 3h
Complete, continue to be incubated 1h at 85 DEG C, reduction temperature, to 45 DEG C, adds triethanolamine 11.7 parts regulation pH to about 9.0, the most available
Milky, solid content 20.2% acroleic acid polyurethane matting resin C.
Described number is weight fraction.
The acroleic acid polyurethane matting resin of embodiment 1～3 is added water and is made into 15%(mass fraction) coating (coating A,
B, C correspond respectively to embodiment 1,2,3), the compositions after dilution is placed in natural drying five days in glass drying oven, then at 50 DEG C
Baking oven is dried 24h.Film performance presses coating A～C such as table 1:
Table 1 acroleic acid polyurethane matting resin performance (after drying and forming-film)
Gloss is detected by the standard of GB/T9754；Pencil hardness is detected by the standard of GB/T6739；
Impact strength is detected by the standard of GB/T1732；
Abrasion resistance is detected by the standard of GB/T9266-2009；
Boiling water resistance: film (20 × 20 × 1mm) is placed on 30min in the boiling water of 100 DEG C, takes out and observes film coated surface
State；
Resistance to water: film (20 × 20 × 1mm) is placed in deionized water after impregnating 7 days, observes the state of film；
Acid resistance: film (20 × 20 × 1mm) is immersed in 5%H2SO4, after 24h, observe and be coated with membrane stage；
Alkali resistance: be immersed in the NaOH solution of 3% after 24h by film (20 × 20 × 1mm), observes and is coated with membrane stage；
Mould scar shielding: visual valuation: mould scar shielding is good；△ mould scar shielding is poor；× mould
Tool scar shielding is very poor；Mould scar shielding (L-value): use variable angle spectrophotometric meter GCMS-4 to survey under 90 degree
Fixed.The film that L-value is big is nebulousurine color, and mould scar shielding is good.
Storage stability: be placed in by the acroleic acid polyurethane matting resin of preparation in the water-bath of 50 DEG C 7 days, observes container bottom
Whether portion has precipitate.
As it can be seen from table 1 the present invention have Aqueous acrylic urethane's matting resin of phase separation structure preserving or
It is formed without gel or thickening in using, therefore possesses good storage stability, after drying and forming-film, mould scar can be obtained opacifying property
Get well, the smooth film of 60 ° of gloss less than 20.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. Aqueous acrylic urethane's matting resin with phase separation structure, it is characterised in that comprise following weight portion meter
Component:
Aqueous acrylic urethane's matting resin with phase separation structure the most according to claim 1, it is characterised in that:
Described acrylate is by carboxylic unsaturated acrylic monomer, hydroxyl unsaturation acrylic ester monomer and free radical
Polymerizable monomer A mixes composition；
The acid number of described acrylate is 15-150mg KOH/g；Hydroxyl value is 30-150mg KOH/g；Vitrification point is 20-60
℃；Molecular weight is the scope of 10000-100000；Molecular weight distribution is 1～5；
Described free radical polymerization monomer A is (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) acrylic acid fourth
Ester, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, (methyl) third
Olefin(e) acid stearate, (methyl) cyclohexyl acrylate, acrylonitrile, acrylamide, lauryl methacrylate, N-methacryl
Two or more monomers in amine or styrene.
Aqueous acrylic urethane's matting resin with phase separation structure the most according to claim 2, it is characterised in that:
Described carboxylic unsaturated acrylic monomer is one or both in methacrylic acid or acrylic acid；
The unsaturated acrylic ester monomer of described hydroxyl is (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxyl
In propyl ester, (methyl) acrylic acid 2-hydroxy butyl ester, polypropylene glycol monomethacrylate or polypropylene glycol mono acrylic ester at least
A kind of.
Aqueous acrylic urethane's matting resin with phase separation structure the most according to claim 3, it is characterised in that:
The compounding ratio of the described mix monomer in acrylate, for being grouped into by the one-tenth of following weight portion meter:
Aqueous acrylic urethane's matting resin with phase separation structure the most according to claim 1, it is characterised in that:
Described anionic occlusive polyurethane is aromatic compound, aliphatic compound, alicyclic ring kind isocyanate and polyester polyols
Alcohol is under catalyst action, through the polyurethane that small molecule alcohol and the chain extender addition polymerization Han carboxyl obtain；Described polyester is many
The mass fraction of the polyurethane that unit's alcohol content accounts for synthesis is 10-50%；PEPA number-average molecular weight used is 200-5000；
Synthesis of polyurethane molecular weight is 1000～7000.
Aqueous acrylic urethane's matting resin with phase separation structure the most according to claim 1, it is characterised in that:
Described anionic occlusive polyurethane is prepared by following steps: 0.10mol isophorone diisocyanate with
0.025mol Polyethylene Glycol mixes, and adds 1-2 and drips catalyst dibutyl tin laurate, 50ml acetone, stirs, in 80 DEG C of perseverances
Back flow reaction 1.5h in tepidarium, adds 0.0125mol1,4-butanediol and continues reaction 1h, add 0.0525mol under stirring
Dihydromethyl propionic acid continues reaction 4h, continues back flow reaction 2h, measure in product by dibutyl amine method after adding 0.8mol end-capping reagent
During without the-NCO dissociated, cooling down to 60 DEG C, add 0.0525mol alkali compounds and continue reaction 0.5h, in high-speed stirring
Mix lower addition distilled water, violent shear agitation 0.5h, cool, extract acetone, prepare anionic occlusive polyurethane；
The molecular weight of described Polyethylene Glycol is 400～1000；
Described end-capping reagent has phenolic compound, alcohol compound, oxime compound, active methylene group compounds, lactams
Compounds, aminated compounds, glyoxaline compound, urea compound, carbamate compound；
In the preparation of anionic occlusive polyurethane, described alkali compounds is ethamine, propylamine, butylamine, benzylamine, monoethanol
Amine, neopentyl alcohol amine, 2-aminopropanol, 3-aminopropanol, diethylamine, triethylamine, 2-aminopropane., diisopropylamine, Tris(isopropylamine)., diethyl
In hydramine, diisopropanolamine (DIPA), triethanolamine, dimethylethanolamine, diethyl ethylene diamine, aqueous amine, sodium hydroxide or potassium hydroxide
One.
Aqueous acrylic urethane's matting resin with phase separation structure the most according to claim 1, it is characterised in that:
Described nonionic polyurethane is prepared by following steps: take 0.05mol hexamethylene diisocyanate trimer with
0.15mol poly glycol monomethyl ether mixes, and adds 1～2 catalyst dibutyl tin laurate, 50ml acetone, stirs, in
Back flow reaction in 80 DEG C of waters bath with thermostatic control, with time in dibutyl amine method mensuration product without the-NCO dissociated, adds under high velocity agitation
Distilled water, violent shear agitation 0.5h, cooling down, extract acetone, prepare nonionic polyurethane；
The molecular weight of described poly glycol monomethyl ether is 500～2000；
Described initiator is the one in potassium peroxydisulfate, sodium peroxydisulfate or Ammonium persulfate.；
Described chain-transferring agent is sulfur alcohol compound；
Described alkali compounds is ethamine, propylamine, butylamine, benzylamine, monoethanolamine, neopentyl alcohol amine, 2-aminopropanol, 3-amino
Propanol, diethylamine, triethylamine, 2-aminopropane., diisopropylamine, Tris(isopropylamine)., diethanolamine, diisopropanolamine (DIPA), triethanolamine, diformazan
One in ethylethanolamine, diethyl ethylene diamine, aqueous amine, sodium hydroxide or potassium hydroxide；Reached by these alkaline matters
Neutralization ratio 30%～100%；
Described water is deionized water.
Aqueous acrylic urethane's matting resin with phase separation structure the most according to claim 1, it is characterised in that:
Described Aqueous acrylic urethane's matting resin with phase separation structure contains pigment, dyestuff, cross-linking agent, defoamer, steady
Determine agent.
9. the preparation of the Aqueous acrylic urethane's matting resin with phase separation structure described in any one of claim 1～8
Method, it is characterised in that comprise the following steps:
Under the protection of nitrogen, after anionic occlusive polyurethane and nonionic polyurethane are dissolved in water, add part propylene
Acid esters, chain-transferring agent, the initiator of part, be sufficiently mixed, and reacts 0.5-1.5h at 75-85 DEG C, prepares seed emulsion；Then drip
Adding remaining acrylate and remaining initiator, time for adding controls to be incubated 1-at 75-85 DEG C after 3-5h, dropping
3h, reduction temperature is to 45 DEG C, and addition alkali compounds regulation pH value, to 8.0-9.5, obtains the aqueous third with phase separation structure
Olefin(e) acid polyurethane matting resin；
Described part propylene acid esters is 1:3 with the mass ratio of remaining acrylate；
The initiator of described part is 1:3 with the mass ratio of remaining initiator.
10. the Aqueous acrylic urethane's matting resin with phase separation structure described in any one of claim 1～8 is applied to
Coat drying and forming-film to woodenware or metal device, it is thus achieved that the film coated surface of gloss less than 20.
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| CN106519133B (en) * | 2016-11-10 | 2019-01-29 | 万华化学集团股份有限公司 | A kind of sulfonic acid type water-based polyurethane-acrylate is from matting resin and its preparation method and application |
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| CN109535352B (en) * | 2018-11-30 | 2020-01-24 | 东莞大宝化工制品有限公司 | Hydroxy acrylic emulsion and preparation method thereof |
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| CN110951039A (en) * | 2019-11-24 | 2020-04-03 | 华南理工大学 | Environment-friendly self-extinction waterborne polyurethane and preparation method and application thereof |
| CN111234168B (en) * | 2020-03-05 | 2021-09-10 | 合肥安利聚氨酯新材料有限公司 | Nonionic neutralizer and preparation method thereof, waterborne polyurethane and preparation method and application thereof |
| CN114410174B (en) * | 2022-02-24 | 2023-09-29 | 郑州中科新兴产业技术研究院 | High-performance aqueous acrylic polyurethane coating and preparation method thereof |
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