CN105111813B - The preparation method of coating polyurethane-modified polyacrylate macromolecule dispersing agent - Google Patents
The preparation method of coating polyurethane-modified polyacrylate macromolecule dispersing agent Download PDFInfo
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- CN105111813B CN105111813B CN201510561006.0A CN201510561006A CN105111813B CN 105111813 B CN105111813 B CN 105111813B CN 201510561006 A CN201510561006 A CN 201510561006A CN 105111813 B CN105111813 B CN 105111813B
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- polyurethane
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- 239000002270 dispersing agent Substances 0.000 title claims abstract description 34
- 239000011248 coating agent Substances 0.000 title claims abstract description 22
- 238000000576 coating method Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920002276 poly(acrylate) macromolecule Polymers 0.000 title claims abstract description 16
- 229920002635 polyurethane Polymers 0.000 claims abstract description 21
- 239000004814 polyurethane Substances 0.000 claims abstract description 21
- -1 acrylic polyol Chemical class 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 12
- 229920002521 macromolecule Polymers 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 22
- 239000012948 isocyanate Substances 0.000 claims description 21
- 150000002513 isocyanates Chemical class 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 238000009835 boiling Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 229920000728 polyester Polymers 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 7
- 150000003512 tertiary amines Chemical class 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000000049 pigment Substances 0.000 abstract description 20
- 238000007667 floating Methods 0.000 abstract description 5
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000009736 wetting Methods 0.000 abstract description 2
- 229920000058 polyacrylate Polymers 0.000 abstract 3
- 230000000485 pigmenting effect Effects 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical class CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000011324 bead Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Abstract
Preparation method the present invention relates to coating with polyurethane-modified polyacrylate macromolecule dispersing agent, comprises the following steps：Prepared by acrylic polyol, the macromolecule polyurethane of synthesis monoisocyanates and polyurethane are to acrylate modified.The polyurethane-modified polyacrylate macromolecule dispersing agent preparation method of the present invention, preparation technology is simple, and product is easy to get, and no coupling product produces；Obtained polyurethane-modified polyacrylate has various opposed polarity segments, has extensive compatibility, suitable for various polar systems, does not influence Miscibility；Obtained polyurethane-modified polyacrylate has a variety of pigment wetting groups, and various pigment are respectively provided with good dispersive property, effectively improves pigmenting power；Obtained polyurethane-modified polyacrylate effectively reduces system viscosity, and the bin stability of dispersible pigment color paste is good, and anti-floating color, grow dim excellent performance.
Description
Technical field
The invention belongs to fine chemistry industry auxiliary agent field, it is related to the preparation of coating dispersant, more particularly to modified acroleic acid
The preparation of ester.
Background technology
In coating application process, in order to improve the surface decoration effect of coating, improve paint film property, generally require to add
Pigment.It is dispersed in order that the pigment of powdery is uniform and stable in the coating system of liquid, needs to add in coating production process
Dispersant is co-mulled and made into pigment, and in the presence of external force, pigment particles particle diameter gradually reduces, specific surface area increase, dispersant profit
It is wet and adsorb in surface of pigments, and by steric hindrance, charge effect stable pigments particle, so as to prepare tinting strength, tinting power it is prominent,
The dispersible pigment color paste having good stability.It can be seen that dispersant is the important component for preparing pigment printing paste.
The coating dispersant of prior art is divided into controlled flocculation type according to action principle and conciliates flocculation-type.Controlled flocculation type point
Powder typically has middle low molecule amount, passes through the repulsive interaction of its own charge, stable pigments particle, such dispersant system
Standby dispersible pigment color paste, possess the performances such as excellent storage stability, anti-floating color, ability of growing dim be good, but viscosity reduction effect is limited, is not suitable for system
Standby high concentration mill base.Solution flocculation-type dispersant typically has middle HMW, is acted on by steric hindrance, stable pigments particle,
Viscosity reduction effect protrudes, and is suitable for preparing dispersible pigment color paste.But most of solution flocculation-type dispersant is limited to molecular weight and molecule knot
Structure, different dispersants need to be selected for different pigment particles, opposed polarity system, versatility is not strong.Develop a kind of versatility
Wide high score subsolution flocculation-type dispersant is the important directions of dispersant.
The content of the invention
Based on this, for prior art, the technical problem to be solved in the present invention is to improve and solve the compatible of flocculation-type dispersant
Property, versatility and good stability.
It is an object of the invention to provide a kind of technique is simple, safety, no coupling product, easily prepared, not homopolarity can be applicable
Property system, bin stability and anti-floating color, grow dim coating polyurethane-modified polyacrylate macromolecule dispersing agent of good performance
Preparation method.
The technical solution used in the present invention is：
A kind of coating preparation method of polyurethane-modified polyacrylate macromolecule dispersing agent, comprises the following steps：
1) prepared by acrylic polyol
The propylene glycol methyl ether acetate for accounting for total mass fraction 50-150% is added to four equipped with stirring and condensing unit
In mouth flask, under the protection of 80 DEG C~160 DEG C temperature, 0.01MPa~1Mpa pressure and logical nitrogen, it is 1 that molar ratio, which is added dropwise:
The terminal hydroxy group acrylic monomers and dimethylaminoethyl methacrylate of (0.01~0.1), account for reactant gross mass 0.5~5%
Initiator mixture, 2~5h is added dropwise, and is incubated 1~5h, and cooling filtering is standby；
2) macromolecule polyurethane of monoisocyanates is synthesized
Weigh the isocyanates polymer of certain mass, be (2~6) with the isocyanates polymer molar ratio: 1
Monohydroxy polyethers and the isocyanates polymer molar ratio are (3~8): 1 monohydroxy polyester, account for total mass fraction
(0.05~0.2) % catalyst, and account for total mass fraction (30~150) % solvent be added to equipped with stirring and condensing unit
Four-hole boiling flask in, 50 DEG C~120 DEG C temperature, 0.01MPa~1Mpa pressure and logical nitrogen protection under, stir 2h~5h, drop
It is (1~3) to add with isocyanates polymer molar ratio: 1 monohydroxy tertiary amine, 0.5~1h are added dropwise, and is incubated 1h~5h,
Cooling filtering, it is standby；
3) polyurethane is to acrylate modified
It is (10~50) by molar ratio: the 1 monoisocyanates macromolecule polyurethane and the polyhydroxy acrylic acid
Ester, the catalyst for accounting for total mass fraction (0.05~0.2) %, the solvent that accounts for total mass fraction (50~300) % are added to and are equipped with
In the four-hole boiling flask of stirring and condensing unit, under the protection of 50 DEG C~120 DEG C temperature, 0.01MPa~1Mpa pressure and logical nitrogen,
Stir 1h~10h, cooling filtering.
Wherein, in step 1), the initiator in di-tert-butyl peroxide, two t-amyl peroxy compounds one
Kind；In step 2), the isocyanates polymer is selected fromOne kind in IL1351 and Polurene HR.B,.
In one of the embodiments, in step 1), 80~160 DEG C of reaction temperature, reaction pressure is 0.01~1Mpa, instead
3~10h between seasonable.
In one of the embodiments, in step 2), the macromolecule polyurethane of the synthesis monoisocyanates structure, structure
The II as shown in formula：
Wherein M1 represents the isocyanates polymer of 5-50 carbochain, M2 represent 5~100 carbochains monohydroxy polyethers,
Monohydroxy polyester, R2 represent the monohydroxy tertiary amine of 3~20 carbochains
In one of the embodiments, in step 2), the monohydroxy polyethers and the isocyanates polymer mol ratio
Example is (2~6): 1, the monohydroxy polyester and the isocyanates polymer molar ratio are (3~8): and 1, the monohydroxy
Tertiary amine and the isocyanates polymer molar ratio are (1-3): 1；The catalyst is organotin；Solvent is 3~20 carbon
The ethers and esters of chain, dosage are the 30~150% of gross mass.
In one of the embodiments, in step 3), the monoisocyanates macromolecule polyurethane and the polyhydroxy third
The molar ratio of olefin(e) acid ester is (10~50): 1, the catalyst is organotin, solvent be 2~20 carbon chain lengths benzene class,
Esters.
In one of the embodiments, in step 3), reaction temperature be 50 DEG C~120 DEG C, reaction pressure be 0.01Mpa~
1Mpa, reaction time are 1~10 hour.
Compared with the prior art, beneficial effects of the present invention are：
(1) preparation technology is simple, and product is easy to get, and no coupling product produces.
(2) there are various opposed polarity segments, there is extensive compatibility, suitable for various polar systems, do not influence body
It is compatibility.
(3) there are a variety of pigment wetting groups, various pigment are respectively provided with good dispersive property, pigment is effectively improved and
Color power.
(4) system viscosity is effectively reduced, the bin stability of dispersible pigment color paste is good, and anti-floating color, grow dim excellent performance.
Embodiment
First, the preparation method of the coating polyurethane-modified polyacrylate macromolecule dispersing agent of the present invention is illustrated.
The preparation method of the coating polyurethane-modified polyacrylate macromolecule dispersing agent of the application, including following step
Suddenly：
1) prepared by acrylic polyol
The solvent for accounting for total mass fraction 50-150% is added in the four-hole boiling flask equipped with stirring and condensing unit, 80
DEG C~160 DEG C of temperature, 0.01MPa~1Mpa pressure and logical nitrogen protection under, be added dropwise molar ratio be 1: the end of (0.01~0.1)
The acrylic monomers of acrylate monomers and polar functionalities, account for reactant gross mass 0.5~5% initiator mixing
Thing, 2~5h are added dropwise, and are incubated 1~5h, and cooling filtering is standby；
2) macromolecule polyurethane of monoisocyanates is synthesized
Weigh the isocyanates polymer of certain mass, be (2~6) with the isocyanates polymer molar ratio: 1
Monohydroxy polyethers and the isocyanates polymer molar ratio are (3~8): 1 monohydroxy polyester, account for total mass fraction
(0.05~0.2) % catalyst, and account for total mass fraction (30~150) % solvent be added to equipped with stirring and condensing unit
Four-hole boiling flask in, 50 DEG C~120 DEG C temperature, 0.01MPa~1Mpa pressure and logical nitrogen protection under, stir 2h~5h, drop
It is (1~3) to add with isocyanates polymer molar ratio: 1 monohydroxy tertiary amine, 0.5~1h are added dropwise, and is incubated 1h~5h,
Cooling filtering, it is standby；
3) polyurethane is to acrylate modified
It is (10~50) by molar ratio: the 1 monoisocyanates macromolecule polyurethane and the polyhydroxy acrylic acid
Ester, the catalyst for accounting for total mass fraction (0.05~0.2) %, the solvent that accounts for total mass fraction (50~300) % are added to and are equipped with
In the four-hole boiling flask of stirring and condensing unit, under the protection of 50 DEG C~120 DEG C temperature, 0.01MPa~1Mpa pressure and logical nitrogen,
Stir 1h~10h, cooling filtering.
Secondly, the preparation side of the coating polyurethane-modified polyacrylate macromolecule dispersing agent according to the application is illustrated
The embodiment of method.
Monohydroxy polyester embodiment：
Accurately weigh 1.863g (0.01mol) dodecyls alcohol, 9.196g (0.08mol) 6-caprolactone, 3.941g
(0.04mol) δ-valerolactone, 0.02g dibutyl tin dilaurates are added in the four-hole boiling flask equipped with backflow and agitating device, are led to
In the case of nitrogen protection, at 140-180 DEG C, after stirring 8-12h, faint yellow viscous liquid or lotion, product solid content are obtained
More than 95%, below acid number 5mgKOH/g.
Acrylic polyol A embodiments：
35.989g propylene glycol methyl ether acetate solvents are added in the four-hole boiling flask equipped with stirring and condensing unit,
At 135-145 DEG C of temperature and the protection of logical nitrogen, 34.417gSR495B NS, 1.572g dimethylaminoethyl methacrylates is added dropwise
And the mixture of 1.799g di-tert-butyl peroxides, 2-3h are added dropwise, 1-2h, cooling filtering, product solid part are incubated
50%.
Acrylic polyol B embodiment：
30.355g propylene glycol methyl ether acetate solvents are added in the four-hole boiling flask equipped with stirring and condensing unit,
At 140-150 DEG C of temperature and the protection of logical nitrogen, 20g propylene glycol methyl ether acetates, 48.783gPLACCEL FM3,1.572g is added dropwise
The mixture of dimethylaminoethyl methacrylate and the t-amyl peroxy compounds of 2.518g bis-, 2-3h are added dropwise, and are incubated 1-2h,
Cooling filtering, product solid part 50%.
Monoisocyanates polyurethane C embodiment：
Weigh 10g'sIL1351,13.714g monohydroxy polyester, 9.143gMPEG-1500,0.1643g
Dibutyl tin dilaurate and 13.027g butyl acetates are added in the four-hole boiling flask equipped with stirring and condensing unit, at 70-80 DEG C
Under temperature, logical nitrogen protection, 2-3h is stirred, 0.1698gN, N- dimethylethanolamines and 10g butyl acetates, 0.5h or so is added dropwise
It is added dropwise, is incubated 1-2h, cooling filtering, product solid part 50%, NCO%0.15-0.2%.
Monoisocyanates polyurethane D embodiments：
Weigh 10g Polurene HR.B, 13.714g monohydroxies polyester, 9.143gMPEG-1500,0.1643g February
The fourth tin of cinnamic acid two and 13.363g butyl acetates are added in the four-hole boiling flask equipped with stirring and condensing unit, in 70-80 DEG C of temperature
Under degree, logical nitrogen protection, 2-3h is stirred, 0.506gDMP-30 and 10g butyl acetates, 0.5h or so are added dropwise and are added dropwise, are incubated
1-2h, cooling filtering, product solid part 50%, NCO%0.15-0.2%.
Embodiment 1：
By 10g monoisocyanates polyurethane C and 0.3428g acrylic polyol A, 0.01g dibutyl tin dilaurate,
2.586g butyl acetates are added in the four-hole boiling flask equipped with stirring and condensing unit, are protected in 90-100 DEG C of temperature and logical nitrogen
Under, stir 3-5h, cooling filtering, product solid part 40%, NCO%≤0.05%.
Embodiment 2：
By 10g monoisocyanates polyurethane C and 0.4796g acrylic polyol B, 0.01g dibutyl tin dilaurate,
2.620g butyl acetates are added in the four-hole boiling flask equipped with stirring and condensing unit, are protected in 90-100 DEG C of temperature and logical nitrogen
Under, stir 3-5h, cooling filtering, product solid part 40%, NCO%≤0.05%.
Embodiment 3：
By 10g monoisocyanates polyurethane D and 0.2571g acrylic polyol A, 0.01g dibutyl tin dilaurate,
2.564g butyl acetates are added in the four-hole boiling flask equipped with stirring and condensing unit, are protected in 90-100 DEG C of temperature and logical nitrogen
Under, stir 3-5h, cooling filtering, product solid part 40%, NCO%≤0.05%.
Embodiment 4：
By 10g monoisocyanates polyurethane D and 0.3597g acrylic polyol B, 0.01g dibutyl tin dilaurate,
2.600g butyl acetates are added in the four-hole boiling flask equipped with stirring and condensing unit, are protected in 90-100 DEG C of temperature and logical nitrogen
Under, stir 3-5h, cooling filtering, product solid part 40%, NCO%≤0.05%.
Then, the method for testing and knot of the coating polyurethane-modified polyacrylate macromolecule dispersing agent of the application are illustrated
Fruit：
Embodiment 1, embodiment 2, embodiment 3 and embodiment 4 are separately added into transparent iron oxide red, organic red and carbonarius
In slurry formula, with reference to as follows：
1 transparent iron oxide red paste formula of table
| Raw material | Dosage |
| BASF A-81 | 21 |
| Dispersant | 3 |
| BASF L-2817 | 45 |
| Butyl acetate (BAC) | 16 |
| Propylene glycol methyl ether acetate (PMA) | 15 |
Add the bead (particle diameter 2-2.5mm) of 1.8 times of paste formula weight, speed lapping 3h on vibrating machine, filtering, obtain
It is as follows to mill base, test mill base performance：
The transparent iron oxide red mill base performance test of table 2
Embodiment 1, embodiment 2, embodiment 3 and embodiment 4 are to transparent iron oxide red it can be seen from the test result of table 2
It is respectively provided with good peptizaiton.
3 organic red slurry formula of table
Add the bead (particle diameter 2-2.5mm) of 1.8 times of paste formula weight, speed lapping 5h on vibrating machine, filtering, obtain
It is as follows to mill base, test mill base performance：
The organic red slurry performance test of table 4
Embodiment 2 and embodiment 4 are optimal to the dispersion effect of organic red pigment it can be seen from the test result of table 4.Selection
Example 2 and example 4 are carrying out the application experiment of carbon black color paste.
The black color paste formula of table 5
Add the bead (particle diameter 2-2.5mm) of 1.8 times of paste formula weight, speed lapping 5h on vibrating machine, filtering, obtain
It is as follows to mill base, test mill base performance：
The black color paste performance test of table 6
In summary test is as can be seen that from most easily scattered inorganic pigment, to more difficult scattered organic pigment, then to most
The scattered carbon black of hardly possible, the combination property of the dispersant of embodiment 4 show optimal all the time.
The carbon black black that carbon black black color paste prepared by embodiment 4 is prepared with the same type dispersant B 6 commonly used on the market
Mill base is respectively applied to thermoplastic acrylic, synthetic fatty acid, hydroxy acrylic acid, polyester system, tests its performance.
The various system black paint formulas of table 7
According to listed raw material in table 7, weigh, be well mixed successively.Then scratch respectively on a glass, according to each solid
Chemical industry skill, paint film is made, and it is as follows to test paint film property.
The paint film property of table 8 is tested
By test result in table 8, it can be seen that the performance of embodiment 4 and commercially available common dispersants B6 are relatively.Continue
Gray paint is made into, tests tinting strength, tinting power and anti-floating color, performance of growing dim.
The various system white colorant formulas of table 9
Add the bead (particle diameter 2-2.5mm) of 1.8 times of paste formula weight, speed lapping 2h on vibrating machine, filtering, obtain
To mill base.The white paint of different systems is prepared using different white colorants, formula is as follows：
The various system white paint formulas of table 10
According to listed raw material in table 10, weigh, be well mixed successively, then each system corresponding with table 7 respectively is black
Colored paint is made into gray paint, on a glass, according to respective curing process, paint film is made, and survey in blade coating according to 1: 10 mass ratio
It is as follows to try paint film property.
The paint film property of table 11 is tested
The dispersing agent performance of embodiment 4 approaches with commercially available B6 performance comparisions it can be seen from the paint film property surveyed by table 11, resists
Loose colour performance is outstanding compared with B6.In summary all tests, it can be seen that the dispersant of embodiment 4 has reached design requirement.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (6)
1. a kind of coating preparation method of polyurethane-modified polyacrylate macromolecule dispersing agent, it is characterised in that including following
Step：
A) prepared by acrylic polyol
The propylene glycol methyl ether acetate for accounting for total mass fraction 50-150% is added to four mouthfuls of burnings equipped with stirring and condensing unit
In bottle, under the protection of 80 DEG C~160 DEG C temperature, 0.01MPa~1MPa pressure and logical nitrogen, it is 1: (0.01 that molar ratio, which is added dropwise,
~0.1) terminal hydroxy group acrylic monomers and dimethylaminoethyl methacrylate, the initiation for accounting for reactant gross mass 0.5~5%
The mixture of agent, 2~5h are added dropwise, and are incubated 1~5h, and cooling filtering is standby；
B) macromolecule polyurethane of monoisocyanates is synthesized
Weigh the isocyanates polymer of certain mass, be (2~6): 1 single hydroxyl with the isocyanates polymer molar ratio
Base polyethers, with the isocyanates polymer molar ratio be (3~8): 1 monohydroxy polyester, account for total mass fraction (0.05~
0.2) % catalyst, and account for total mass fraction (30~150) % solvent and be added to equipped with stirring and four mouthfuls of condensing unit
In flask, 50 DEG C~120 DEG C temperature, 0.01MPa~1MPa pressure and logical nitrogen protection under, stir 2h~5h, be added dropwise with it is different
Cyanate polymer molar ratio is (1~3): 1 monohydroxy tertiary amine, 0.5~1h are added dropwise, and is incubated 1h~5h, cooled
Filter, it is standby；
C) polyurethane is to acrylate modified
It is (10~50) by molar ratio: the 1 monoisocyanates macromolecule polyurethane and the acrylic polyol, accounts for
Total mass fraction (0.05~0.2) % dibutyl tin dilaurate catalyst, the solvent for accounting for total mass fraction (50~300) % add
Enter into the four-hole boiling flask equipped with stirring and condensing unit, in 50 DEG C~120 DEG C temperature, 0.01MPa~1MPa pressure and logical nitrogen
Under gas shielded, 1h~10h, cooling filtering are stirred；
Wherein, in step a), the one kind of the initiator in di-tert-butyl peroxide, two t-amyl peroxy compounds；Step
It is rapid b) in, the isocyanates polymer is selected fromOne kind in IL1351 and Polurene HR.B.
2. the preparation method of coating polyurethane-modified polyacrylate macromolecule dispersing agent according to claim 1, its feature
It is, in step a), 80~160 DEG C of reaction temperature, reaction pressure is 0.01~1MPa, 3~10h of reaction time.
3. the preparation method of coating polyurethane-modified polyacrylate macromolecule dispersing agent according to claim 1, its feature
It is, in step b), the macromolecule polyurethane of the synthesis monoisocyanates structure, structure II as shown in formula：
Wherein M1 represents the isocyanates polymer of 5-50 carbochain, and M2 represents the monohydroxy polyethers of 5~100 carbochains, single hydroxyl
Base polyester, R2 represent the monohydroxy tertiary amine of 3~20 carbochains.
4. the preparation method of coating polyurethane-modified polyacrylate macromolecule dispersing agent according to claim 1, its feature
It is, in step b), the monohydroxy polyethers and the isocyanates polymer molar ratio are (2~6): 1, the monohydroxy
Polyester and the isocyanates polymer molar ratio be (3~8): 1, the monohydroxy tertiary amine and the isocyanates polymer
Molar ratio is (1-3): 1；The catalyst is organotin；Solvent is the ethers and esters of 3~20 carbochains, and dosage is total matter
The 30~150% of amount.
5. the preparation method of coating polyurethane-modified polyacrylate macromolecule dispersing agent according to claim 1, its feature
Be, in step c), the molar ratio of the monoisocyanates macromolecule polyurethane and the acrylic polyol for (10~
50): 1, the catalyst is organotin, and solvent is benzene class, the esters of 2~20 carbon chain lengths.
6. the preparation method of coating polyurethane-modified polyacrylate macromolecule dispersing agent according to claim 1, its feature
It is, in step c), reaction temperature is 50 DEG C~120 DEG C, and reaction pressure is 0.01MPa~1MPa, and the reaction time is 1~10
Hour.
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| CN113402688A (en) * | 2021-07-24 | 2021-09-17 | 珠海市金团化学品有限公司 | Polyurethane modified acrylic acid aqueous polymer dispersant and preparation method thereof |
| CN114349911A (en) * | 2021-12-17 | 2022-04-15 | 武汉科技大学 | Silicon micropowder dispersing agent based on carboxylic acid monomer |
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| CN102408537A (en) * | 2011-09-19 | 2012-04-11 | 福建宝利特新材料科技有限公司 | Preparation method of acrylate modified water-borne polyurethane emulsion for synthetic leather |
| CN103360561A (en) * | 2013-07-02 | 2013-10-23 | 广东海顺新材料科技有限公司 | Polyurethane modified acrylic emulsion, preparation method of acrylic emulsion and prepared artificial stone |
| CN104151890A (en) * | 2014-07-30 | 2014-11-19 | 中国海洋石油总公司 | Ultraviolet-curable cathode electrophoresis coating composition |
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| CN102408537A (en) * | 2011-09-19 | 2012-04-11 | 福建宝利特新材料科技有限公司 | Preparation method of acrylate modified water-borne polyurethane emulsion for synthetic leather |
| CN103360561A (en) * | 2013-07-02 | 2013-10-23 | 广东海顺新材料科技有限公司 | Polyurethane modified acrylic emulsion, preparation method of acrylic emulsion and prepared artificial stone |
| CN104151890A (en) * | 2014-07-30 | 2014-11-19 | 中国海洋石油总公司 | Ultraviolet-curable cathode electrophoresis coating composition |
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Denomination of invention: Preparation method of polyurethane modified acrylic polymer dispersant for coatings Effective date of registration: 20231213 Granted publication date: 20171226 Pledgee: China Postal Savings Bank Co.,Ltd. Zhuhai Doumen Branch Pledgor: KITO CHEMICAL Co.,Ltd. Registration number: Y2023980071382 |