CN117683186A - Cellulose modified polyester acrylate aqueous dispersion and preparation method and application thereof - Google Patents
Cellulose modified polyester acrylate aqueous dispersion and preparation method and application thereof Download PDFInfo
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- CN117683186A CN117683186A CN202311781081.9A CN202311781081A CN117683186A CN 117683186 A CN117683186 A CN 117683186A CN 202311781081 A CN202311781081 A CN 202311781081A CN 117683186 A CN117683186 A CN 117683186A
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- cellulose
- modified polyester
- polyester acrylate
- propylene glycol
- paint
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- 229920000728 polyester Polymers 0.000 title claims abstract description 67
- 239000006185 dispersion Substances 0.000 title claims abstract description 42
- 229920002678 cellulose Polymers 0.000 title claims abstract description 41
- 239000001913 cellulose Substances 0.000 title claims abstract description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 112
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 29
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 29
- 229920002554 vinyl polymer Polymers 0.000 claims description 29
- 229920002301 cellulose acetate Polymers 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 230000001502 supplementing effect Effects 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 150000007519 polyprotic acids Polymers 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 14
- 150000008064 anhydrides Chemical class 0.000 claims description 13
- 150000005846 sugar alcohols Polymers 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 11
- 238000004806 packaging method and process Methods 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical group CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- LNYYKKTXWBNIOO-UHFFFAOYSA-N 3-oxabicyclo[3.3.1]nona-1(9),5,7-triene-2,4-dione Chemical compound C1=CC(C(=O)OC2=O)=CC2=C1 LNYYKKTXWBNIOO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-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
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 229940100573 methylpropanediol Drugs 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 24
- 239000006184 cosolvent Substances 0.000 abstract description 12
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 abstract description 12
- 239000010410 layer Substances 0.000 abstract description 12
- 239000002344 surface layer Substances 0.000 abstract description 7
- 230000000740 bleeding effect Effects 0.000 abstract description 6
- 239000002612 dispersion medium Substances 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 3
- 230000001133 acceleration Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000035515 penetration Effects 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a cellulose modified polyester acrylate aqueous dispersion, a preparation method and application thereof, which promote the surface drying acceleration of water paint base paint and paint cover paint by using weather-resistant cellulose acetate butyrate, promote the quick volatilization of dispersion medium (water and hydrophilic cosolvent) in the paint, weaken the mutual permeation of the base paint and the surface paint in the color cover process, and control the occurrence of color bleeding phenomenon. Because cellulose not only has the effect of promoting volatilization, after the hydrophilic strong solvent (such as diacetone alcohol, propylene glycol methyl ether and the like) of the base paint is volatilized, the cosolvent (such as diacetone alcohol, propylene glycol methyl ether and the like) in the color paint volatilizes faster, but also the surface layer can promote the dispersion medium to be accelerated due to the presence of the acetin cellulose, the residual cosolvent in the surface layer after volatilization can not effectively dissolve the cellulose which is separated out by the volatilization of the cosolvent in the bottom layer when the surface layer contacts with the bottom layer, and the mutual penetration degree of the bottom layer and the surface layer is greatly reduced, so that the seepage of the deep color paint of the bottom layer is prevented.
Description
Technical Field
The invention relates to the technical field of dispersion preparation, in particular to a cellulose modified polyester acrylate aqueous dispersion, a preparation method and application thereof.
Background
At present, almost all of the water-based packaging barrel coatings at home and abroad adopt a polyester modified acrylic ester-amino crosslinking curing system, and in order to keep the performance required by the application environment of the packaging barrel, the coating adopts a water-soluble resin system which reduces some hydrophilic functional groups in resin and keeps part of cosolvent. The mechanical property, leveling property and medium resistance of the system can be suitable for complex and changeable application environments of the packaging barrel. However, in the existing packaging barrel coating line, in order to save energy consumption, a wet-wet coating process is adopted in the process of color matching of double-color paint, in fact, during color matching, the cosolvent in the first layer of coating cannot volatilize thoroughly, and generally about 5% of the total dispersion medium still remains, at this time, after the second layer of coating is coated, the cosolvent in the surface layer accelerates the dissolution of the bottom resin, at this time, serious interpenetration phenomenon can occur at the cross coverage part of the first layer and the second layer, deep color of the bottom layer seeps out, color seepage defect is generated, coating attractiveness of the packaging barrel is seriously affected, and additional cost is generated for later repair, which is a problem commonly encountered in the packaging barrel coating industry.
At present, the commercial aqueous cellulose acetate butyrate is water-emulsion, molecules exist in micelles, however, the state of molecular level miscibility cannot be achieved after the aqueous polyester-acrylic ester is mixed with the commercial cellulose acetate butyrate, the surface drying rate of an aqueous system cannot be obviously improved by introducing the water-emulsion cellulose, so that the intersectional partial miscibility phenomenon of the bottom surface coating cannot be forbidden, and the property and cost of the coating are greatly influenced by introducing a large amount of cellulose, so that no ideal scheme exists at present for solving the bleeding phenomenon in the coating process of the packaging barrel.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a cellulose modified polyester acrylate aqueous dispersion, a preparation method and application thereof, and solves the problem that bleeding is easy to occur in the color process of the existing water-based packaging barrel double-color paint.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing cellulose modified polyester acrylate water dispersion, comprising the following steps:
s1, preparation of a polyester oligomer: adding polyalcohol, polybasic acid and anhydride into a reflux solvent, then adding a catalyst, heating, stirring and dehydrating, and cooling to 50-60 ℃ for standby after the reaction system acid value is reduced to 50-60 mgKOH/g;
s2, preparing a cellulose acetate butyrate solution: adding cellulose acetate into propylene glycol methyl ether serving as an organic solvent, heating, stirring and dissolving to obtain cellulose acetate solution;
s3, preparing cellulose modified polyester acrylate aqueous dispersion: adding the cellulose acetate butyrate solution into the prepared polyester oligomer solution according to the stoichiometric ratio, supplementing propylene glycol methyl ether to the stoichiometric value, stirring, heating to 130-135 ℃, dropwise adding vinyl monomer and 80% of the stoichiometric initiator in the reaction, preserving heat for 1h after the dropwise adding is finished, then supplementing propylene glycol methyl ether and the rest 20% of the initiator, preserving heat for 3.5-4h after the dropwise adding is finished, distilling under reduced pressure to extract part of propylene glycol methyl ether, cooling to 50-70 ℃, adding a neutralizer, controlling the neutralization degree to 90-95%, adding deionized water, stirring uniformly, and filtering to obtain the cellulose modified polyester acrylate water dispersion.
Preferably, in step S1, the mass ratio of the polyol, the polybasic acid, the anhydride and the catalyst is 30-45:20-25:30-45:0.05-0.1.
Preferably, in step S1, the polyhydric alcohol is at least two selected from trimethylolpropane, methylpropanediol, propylene glycol, 1, 6-hexanediol, and neopentyl glycol; the polybasic acid is selected from succinic acid, adipic acid or sebacic acid; the anhydride is at least two selected from phthalic anhydride, maleic anhydride, isophthalic anhydride and tetrahydrophthalic anhydride; the catalyst is selected from monobutyl tin oxide and/or dibutyl tin oxide.
Preferably, in step S1, the temperature of the heating and stirring reaction is 220-230 ℃.
Preferably, in step S2, the mass fraction of the cellulose acetate butyrate solution is 25-30%.
Preferably, in the step S3, the mass ratio of the polyester oligomer, the cellulose acetate solution, the vinyl monomer and the initiator is 80-115:10-20:80-120:1.0-1.5.
Preferably, in step S3, the vinyl monomer is at least two selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, acrylic acid, butyl acrylate, butyl methacrylate, methyl methacrylate, and styrene.
Preferably, in step S3, the initiator is one or more selected from benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide and di-tert-amyl peroxide.
The invention provides the cellulose modified polyester acrylate water dispersion prepared by the preparation method.
The invention also provides application of the cellulose modified polyester acrylate aqueous dispersion in water-based packaging barrel anti-bleeding paint.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, based on the characteristics of the acebutyl cellulose, the solvent is introduced into the solvent for dispersion and dissolution in the traditional aqueous polyester-acrylic acid synthesis process, at the moment, the acebutyl cellulose, a polyester chain and a polyacrylic acid chain form molecular interpenetrating, each polymer chain segment can fully represent the molecular properties of the acebutyl cellulose, and the promotion of volatilization of dispersion medium (water and cosolvent) and the assistance of film leveling property can fully represent the acebutyl cellulose; the invention utilizes the emulsification function of acid groups on polyester chains and polyacrylate chains after neutralization (organic amine), realizes the technical approach of the water-based preparation of solvent-based cellulose acetate butyrate, reduces the introduction of hydrophilic functional groups in the water-emulsion cellulose acetate butyrate, fully realizes the compatibility of the cellulose acetate butyrate with acrylic acid chain segments and polyester chain segments, reduces the dosage of the water-emulsion cellulose acetate butyrate in a formula, and reduces the influence of the introduction of the water-emulsion cellulose acetate butyrate on the cost of the coating.
(2) According to the invention, weather-resistant cellulose acetate butyrate is utilized to promote the surface drying acceleration of water-based paint base paint and color paint, promote the quick volatilization of dispersion media (water and hydrophilic cosolvent) in the paint, weaken the mutual permeation of the base paint and the surface paint in the color process, and control the occurrence of color bleeding. Because the cellulose has the effect of promoting volatilization, after the hydrophilic strong solvent (such as diacetone alcohol) of the base paint volatilizes completely, the cosolvent (such as diacetone alcohol) in the color paint volatilizes quickly, the cosolvent volatilizes completely in a short time, and the residual cosolvent diacetone alcohol after the surface layer dries is less, so that the cellulose which is separated out from the bottom layer due to the volatilization of the diacetone alcohol cannot be effectively recycled, and the mutual penetration degree of the bottom layer and the surface layer is greatly reduced, thereby preventing the seepage of the deep color paint of the bottom layer; the cellulose modified polyester acrylic acid aqueous dispersion prepared by the method can effectively solve the bleeding phenomenon in the color register process of the double-color paint.
Detailed Description
The present invention will be described in further detail with reference to the following preferred examples, but the present invention is not limited to the following examples.
Unless otherwise specified, the chemical reagents involved in the present invention are all commercially available.
A method for preparing cellulose modified polyester acrylic acid aqueous dispersion, comprising the following steps:
s1, preparation of polyester oligomer
Adding polyalcohol, polybasic acid and anhydride into a solvent, then adding a catalyst, heating and stirring to react, and cooling to 50-60 ℃ for standby after the reaction system acid value is reduced to 50-60 mgKOH/g.
In this step, the mass ratio of the polyhydric alcohol, the polybasic acid, the acid anhydride and the catalyst is 30-45:20-25:30-45:0.05-0.1.
The polyalcohol is at least two selected from trimethylolpropane, methyl propylene glycol, 1, 6-hexanediol and neopentyl glycol;
the polybasic acid is selected from succinic acid, adipic acid or sebacic acid;
the anhydride is at least two selected from phthalic anhydride, maleic anhydride, isophthalic anhydride and tetrahydrophthalic anhydride;
the catalyst is selected from monobutyl tin oxide and/or dibutyl tin oxide;
in this step, the temperature of the heating and stirring reaction is 220-230℃and may be selected from 220℃222℃224℃225℃226℃228℃230 ℃.
S2, preparation of cellulose acetate butyrate solution
Adding cellulose acetate into propylene glycol methyl ether, heating, stirring and dissolving to obtain cellulose acetate solution.
In this step, the temperature of heating and stirring is 60-80deg.C, for example, 60deg.C, 65deg.C, 70deg.C, 75deg.C, 80deg.C can be selected;
the butyl cellulose acetate selected in the invention is butyl cellulose acetate with butyryl content not less than 37%, for example, CAB381 and CAB551 can be selected, and the small viscosity tends to be more and the large viscosity tends to be less;
the mass fraction of the cellulose acetate butyrate solution is 25-30%.
S3, preparation of cellulose modified polyester acrylate aqueous dispersion
Adding the cellulose acetate butyrate solution into the prepared polyester oligomer solution according to the stoichiometric ratio, supplementing propylene glycol methyl ether to the stoichiometric value, stirring, heating to 130-135 ℃, dropwise adding vinyl monomer and 80% of the stoichiometric initiator in the reaction, preserving heat for 1h after the dropwise adding is finished, then supplementing propylene glycol methyl ether and the rest 20% of the initiator, preserving heat for 3.5-4h after the dropwise adding is finished, distilling under reduced pressure to extract part of propylene glycol methyl ether, cooling to 50-70 ℃, adding a neutralizer, controlling the neutralization degree to 90-95%, adding deionized water, stirring uniformly, and filtering to obtain the cellulose modified polyester acrylate water dispersion.
In the step, the mass ratio of the polyester oligomer to the cellulose acetate solution to the vinyl monomer to the initiator is 80-115:10-20:80-120:1.0-1.5.
The vinyl monomer is at least two selected from hydroxyethyl acrylate, hydroxypropyl acrylate, acrylic acid, butyl acrylate, butyl methacrylate, methyl methacrylate and styrene.
The initiator is selected from one or more of benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide and di-tert-amyl peroxide.
In the step, the amount of the propylene glycol methyl ether supplemented for the first time is 60 weight percent of the total amount of vinyl monomers;
the second supplementation of propylene glycol methyl ether is 5wt% of the total vinyl monomer;
the neutralizing agent is selected from N, N-dimethylethanolamine or triethylamine and other organic amines.
The present invention will be further illustrated by the following specific examples, wherein the type of cellulose acetate butyrate selected in the present invention is CAB551, the compositions of the materials in examples 1 to 5 of the present invention and comparative example 1 are shown in Table 1 below, and comparative example 1 does not contain 25wt% cellulose acetate butyrate solution as compared with example 1;
TABLE 1 composition of the materials (unit: g) in examples 1-5 and comparative example 1
Example 1
The materials were added according to the formulation in example 1 of table 1, the specific preparation process being as follows:
s1, preparation of a polyester oligomer: adding polyalcohol, polybasic acid and anhydride into propylene glycol methyl ether solvent, then adding catalyst monobutyl tin oxide PC-4100, reacting at 230 ℃ for 10 hours, starting to measure acid value, ending the reaction when the acid value of the reaction system is reduced to 50mgKOH/g, and cooling to 60 ℃ for standby;
s2, preparing a cellulose acetate butyrate solution: adding cellulose acetate into propylene glycol methyl ether serving as an organic solvent, heating and stirring at 70 ℃ to dissolve the cellulose acetate to obtain 25wt% cellulose acetate solution;
s3, preparing cellulose modified polyester acrylate aqueous dispersion: adding the cellulose acetate butyrate solution into the prepared polyester oligomer solution according to the stoichiometric ratio, supplementing propylene glycol methyl ether to the stoichiometric value (the adding amount of the propylene glycol methyl ether is 60 percent by weight of the total amount of vinyl monomers), stirring, heating to 130 ℃, dropwise adding the vinyl monomers and 80 percent of initiator, preserving heat for 1h after the dropwise adding is finished, then supplementing propylene glycol methyl ether (5 percent by weight of the total amount of the vinyl monomers) and the rest 20 percent of initiator, preserving heat for 4h after the dropwise adding is finished, distilling under reduced pressure to extract the propylene glycol methyl ether accounting for 70 percent of the total amount of the propylene glycol methyl ether, cooling to 50 ℃, adding a neutralizer N, N-dimethylethanolamine, controlling the neutralization degree to 95 percent, adding deionized water, stirring uniformly, and filtering to obtain the cellulose modified polyester acrylate aqueous dispersion.
Example 2
The materials were added according to the formulation in example 2 of table 1, the specific preparation procedure being as follows:
s1, preparation of a polyester oligomer: adding polyalcohol, polybasic acid and anhydride into propylene glycol methyl ether solvent, then adding catalyst monobutyl tin oxide PC-4100, reacting at 230 ℃ for 10 hours, starting to measure acid value, ending the reaction when the acid value of the reaction system is reduced to 50mgKOH/g, and cooling to 60 ℃ for standby;
s2, preparing a cellulose acetate butyrate solution: adding cellulose acetate into propylene glycol methyl ether serving as an organic solvent, heating and stirring at 70 ℃ to dissolve the cellulose acetate to obtain 25wt% cellulose acetate solution;
s3, preparing cellulose modified polyester acrylate aqueous dispersion: adding the cellulose acetate butyrate solution into the prepared polyester oligomer solution according to the stoichiometric ratio, supplementing propylene glycol methyl ether to the stoichiometric value (the adding amount of the propylene glycol methyl ether is 60 percent by weight of the total amount of vinyl monomers), stirring, heating to 130 ℃, dropwise adding the vinyl monomers and 80 percent of initiator, preserving heat for 1h after the dropwise adding is finished, then supplementing propylene glycol methyl ether (5 percent by weight of the total amount of the vinyl monomers) and the rest 20 percent of initiator, preserving heat for 4h after the dropwise adding is finished, distilling under reduced pressure to extract the propylene glycol methyl ether accounting for 70 percent of the total amount of the propylene glycol methyl ether, cooling to 50 ℃, adding a neutralizer N, N-dimethylethanolamine, controlling the neutralization degree to 95 percent, adding deionized water, stirring uniformly, and filtering to obtain the cellulose modified polyester acrylate aqueous dispersion.
Example 3
The materials were added according to the formulation in example 3 of table 1, the specific preparation procedure being as follows:
s1, preparation of a polyester oligomer: adding polyalcohol, polybasic acid and anhydride into propylene glycol methyl ether solvent, then adding catalyst monobutyl tin oxide PC-4100, reacting at 230 ℃ for 10 hours, starting to measure acid value, ending the reaction when the acid value of the reaction system is reduced to 50mgKOH/g, and cooling to 60 ℃ for standby;
s2, preparing a cellulose acetate butyrate solution: adding cellulose acetate into propylene glycol methyl ether serving as an organic solvent, heating and stirring at 70 ℃ to dissolve the cellulose acetate to obtain 25wt% cellulose acetate solution;
s3, preparing cellulose modified polyester acrylate aqueous dispersion: adding the cellulose acetate butyrate solution into the prepared polyester oligomer solution according to the stoichiometric ratio, supplementing propylene glycol methyl ether to the stoichiometric value (the adding amount of the propylene glycol methyl ether is 60 percent by weight of the total amount of vinyl monomers), stirring, heating to 130 ℃, dropwise adding the vinyl monomers and 80 percent of initiator, preserving heat for 1h after the dropwise adding is finished, then supplementing propylene glycol methyl ether (5 percent by weight of the total amount of the vinyl monomers) and the rest 20 percent of initiator, preserving heat for 4h after the dropwise adding is finished, distilling under reduced pressure to extract the propylene glycol methyl ether accounting for 70 percent of the total amount of the propylene glycol methyl ether, cooling to 50 ℃, adding a neutralizer N, N-dimethylethanolamine, controlling the neutralization degree to 95 percent, adding deionized water, stirring uniformly, and filtering to obtain the cellulose modified polyester acrylate aqueous dispersion.
Example 4
The materials were added according to the formulation in example 4 of table 1, the specific preparation procedure being as follows:
s1, preparation of a polyester oligomer: adding polyalcohol, polybasic acid and anhydride into propylene glycol methyl ether solvent, then adding catalyst monobutyl tin oxide PC-4100, reacting at 230 ℃ for 10 hours, starting to measure acid value, ending the reaction when the acid value of the reaction system is reduced to 55mgKOH/g, and cooling to 60 ℃ for standby;
s2, preparing a cellulose acetate butyrate solution: adding cellulose acetate into propylene glycol methyl ether serving as an organic solvent, heating and stirring at 70 ℃ to dissolve the cellulose acetate to obtain 25wt% cellulose acetate solution;
s3, preparing cellulose modified polyester acrylate aqueous dispersion: adding the cellulose acetate butyrate solution into the prepared polyester oligomer solution according to the stoichiometric ratio, supplementing propylene glycol methyl ether to the stoichiometric value (the adding amount of the propylene glycol methyl ether is 60 percent by weight of the total amount of vinyl monomers), stirring, heating to 130 ℃, dropwise adding the vinyl monomers and 80 percent of initiator, preserving heat for 1h after the dropwise adding is finished, then supplementing propylene glycol methyl ether (5 percent by weight of the total amount of the vinyl monomers) and the rest 20 percent of initiator, preserving heat for 4h after the dropwise adding is finished, distilling under reduced pressure to extract the propylene glycol methyl ether accounting for 70 percent of the total amount of the propylene glycol methyl ether, cooling to 50 ℃, adding a neutralizer N, N-dimethylethanolamine, controlling the neutralization degree to 95 percent, adding deionized water, stirring uniformly, and filtering to obtain the cellulose modified polyester acrylate aqueous dispersion.
Example 5
The materials were added according to the formulation in example 5 of table 1, the specific preparation procedure being as follows:
s1, preparation of a polyester oligomer: adding polyalcohol, polybasic acid and anhydride into propylene glycol methyl ether solvent, then adding catalyst monobutyl tin oxide PC-4100, reacting at 230 ℃ for 10 hours, starting to measure acid value, ending the reaction when the acid value of the reaction system is reduced to 60mgKOH/g, cooling, and filtering to obtain polyester oligomer;
s2, preparing a cellulose acetate butyrate solution: adding cellulose acetate into propylene glycol methyl ether serving as an organic solvent, heating and stirring at 70 ℃ to dissolve the cellulose acetate to obtain a 20wt% cellulose acetate solution;
s3, preparing cellulose modified polyester acrylate aqueous dispersion: adding the cellulose acetate butyrate solution into the prepared polyester oligomer solution according to the stoichiometric ratio, supplementing propylene glycol methyl ether to the stoichiometric value (the adding amount of the propylene glycol methyl ether is 60 percent by weight of the total amount of vinyl monomers), stirring, heating to 130 ℃, dropwise adding the vinyl monomers and 80 percent of initiator, preserving heat for 1h after the dropwise adding is finished, then supplementing propylene glycol methyl ether (5 percent by weight of the total amount of the vinyl monomers) and the rest 20 percent of initiator, preserving heat for 4h after the dropwise adding is finished, distilling under reduced pressure to extract the propylene glycol methyl ether accounting for 70 percent of the total amount of the propylene glycol methyl ether, cooling to 50 ℃, adding a neutralizer N, N-dimethylethanolamine, controlling the neutralization degree to 95 percent, adding deionized water, stirring uniformly, and filtering to obtain the cellulose modified polyester acrylate aqueous dispersion.
Comparative example 1
The materials were added according to the formulation in comparative example 1 in table 1, and the specific preparation process was as follows:
s1, preparation of a polyester oligomer: adding polyalcohol, polybasic acid and anhydride into propylene glycol methyl ether solvent, then adding catalyst monobutyl tin oxide PC-4100, reacting at 230 ℃ for 10 hours, starting to measure acid value, ending the reaction when the acid value of the reaction system is reduced to 50mgKOH/g, cooling, and filtering to obtain polyester oligomer;
s2, preparing cellulose modified polyester acrylate aqueous dispersion: adding polyester oligomer into propylene glycol methyl ether solvent (the addition amount of propylene glycol methyl ether is 60wt% of the total amount of vinyl monomers), stirring, heating to 130 ℃, dropwise adding the vinyl monomers and 80% of initiator, preserving heat for 1h after dropwise adding, then adding propylene glycol methyl ether (5 wt% of the total amount of vinyl monomers) and the rest 20% of initiator, preserving heat for 4h after dropwise adding, distilling under reduced pressure to extract propylene glycol methyl ether accounting for 70% of the total amount of propylene glycol methyl ether, cooling to 50 ℃, adding a neutralizer N, N-dimethylethanolamine, controlling the neutralization degree to be 95%, adding deionized water, stirring uniformly, and filtering to obtain the cellulose modified polyester acrylate water dispersion.
Coatings were formulated using the aqueous cellulose-modified polyester acrylate dispersions prepared in examples 1 to 5 and comparative example 1, and the coating formulations and performance test results are shown in table 2:
TABLE 2
Wherein the model of the substrate wetting agent is Digao 4100; the model of the aqueous amino resin is 5717W, which is purchased from Jiangsu Sanmu chemical Co., ltd; the model of the aqueous defoamer is byk024; the model number of the aqueous dispersant 1 is byk104S; the model of the aqueous dispersant 2 is TEGO-760W; as can be seen from Table 2, the aqueous cellulose-modified polyester acrylate dispersion obtained by the present invention has good bleeding resistance during the color-setting process of packaging barrel paints.
Finally, it should be noted that: the above examples are not intended to limit the present invention in any way. Modifications and improvements will readily occur to those skilled in the art upon the basis of the present invention. Accordingly, any modification or improvement made without departing from the spirit of the invention is within the scope of the invention as claimed.
Claims (10)
1. A method for preparing an aqueous dispersion of cellulose modified polyester acrylate, comprising the steps of:
s1, preparation of a polyester oligomer: adding polyalcohol, polybasic acid and anhydride into a solvent, then adding a catalyst, heating and stirring for reaction, and cooling to 50-60 ℃ for standby after the reaction system acid value is reduced to 50-60 mgKOH/g;
s2, preparing a cellulose acetate butyrate solution: adding cellulose acetate into an organic solvent, heating, stirring and dissolving to obtain cellulose acetate solution;
s3, preparing cellulose modified polyester acrylate aqueous dispersion: adding the cellulose acetate butyrate solution into the prepared polyester oligomer solution according to the stoichiometric ratio, supplementing propylene glycol methyl ether to the stoichiometric value, stirring, heating to 130-135 ℃, dropwise adding vinyl monomer and 80% of the stoichiometric initiator in the reaction, preserving heat for 1h after the dropwise adding is finished, then supplementing propylene glycol methyl ether and the rest 20% of the initiator, preserving heat for 3.5-4h after the dropwise adding is finished, distilling under reduced pressure to extract propylene glycol methyl ether, cooling to 50-70 ℃, adding a neutralizer, controlling the neutralization degree to 90-95%, adding deionized water, stirring uniformly, and filtering to obtain the cellulose modified polyester acrylate aqueous dispersion.
2. The method for producing an aqueous cellulose-modified polyester acrylate dispersion according to claim 1, wherein in step S1, the mass ratio of the polyol, the polybasic acid, the acid anhydride and the catalyst is 30 to 45:20 to 25:30 to 45:0.05 to 0.1.
3. The method for producing an aqueous dispersion of cellulose-modified polyester acrylate according to claim 1 wherein in step S1, the polyhydric alcohol is at least two selected from the group consisting of trimethylolpropane, methylpropanediol, propylene glycol, 1, 6-hexanediol, and neopentyl glycol; the polybasic acid is selected from succinic acid, adipic acid or sebacic acid; the anhydride is at least two selected from phthalic anhydride, maleic anhydride, isophthalic anhydride and tetrahydrophthalic anhydride; the catalyst is selected from monobutyl tin oxide and/or dibutyl tin oxide.
4. The process for producing an aqueous cellulose-modified polyester acrylate dispersion according to claim 1 wherein in step S1, the temperature of the heating and stirring reaction is 220 to 230 ℃.
5. The method for producing an aqueous cellulose-modified polyester acrylate dispersion according to claim 1 wherein in step S2, the mass fraction of the cellulose acetate butyrate solution is 25 to 30%.
6. The method for producing an aqueous cellulose-modified polyester acrylate dispersion according to claim 1, wherein in step S3, the mass ratio of the polyester oligomer, the cellulose acetate solution, the vinyl monomer and the initiator is 80 to 115:10-20:80-120:1.0-1.5.
7. The method for producing an aqueous cellulose-modified polyester acrylate dispersion according to claim 1 wherein in step S3, the vinyl monomer is at least two selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, acrylic acid, butyl acrylate, butyl methacrylate, methyl methacrylate, and styrene.
8. The method for producing an aqueous dispersion of cellulose-modified polyester acrylate according to claim 1 wherein in step S3, the initiator is one or more selected from the group consisting of benzoyl peroxide, t-butyl peroxybenzoate, di-t-butyl peroxide and di-t-amyl peroxide.
9. An aqueous dispersion of cellulose-modified polyester acrylate prepared by the method of any one of claims 1 to 8.
10. Use of the aqueous cellulose modified polyester acrylate dispersion according to claim 9 in an aqueous packaging barrel anti-bleeding coating.
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