CN117801199A - Water-dispersible polyaspartic acid ester resin, preparation method and water-based paint - Google Patents
Water-dispersible polyaspartic acid ester resin, preparation method and water-based paint Download PDFInfo
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- CN117801199A CN117801199A CN202311857633.XA CN202311857633A CN117801199A CN 117801199 A CN117801199 A CN 117801199A CN 202311857633 A CN202311857633 A CN 202311857633A CN 117801199 A CN117801199 A CN 117801199A
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- water
- acid ester
- polyaspartic acid
- ester resin
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- 150000002148 esters Chemical class 0.000 title claims abstract description 108
- 229920000805 Polyaspartic acid Polymers 0.000 title claims abstract description 106
- 108010064470 polyaspartate Proteins 0.000 title claims abstract description 106
- 229920005989 resin Polymers 0.000 title claims abstract description 83
- 239000011347 resin Substances 0.000 title claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000003973 paint Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 15
- 239000006184 cosolvent Substances 0.000 claims abstract description 13
- -1 n-dodecyl Chemical group 0.000 claims abstract description 12
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003384 small molecules Chemical class 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 229940043375 1,5-pentanediol Drugs 0.000 claims abstract description 5
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims abstract description 5
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 5
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 5
- 125000004185 ester group Chemical group 0.000 claims abstract 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 claims description 8
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 4
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 4
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 4
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000003860 storage Methods 0.000 description 16
- 229920005862 polyol Polymers 0.000 description 14
- 150000003077 polyols Chemical class 0.000 description 14
- 238000001514 detection method Methods 0.000 description 13
- 230000032683 aging Effects 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- XXZCIYUJYUESMD-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(morpholin-4-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCOCC1 XXZCIYUJYUESMD-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- 229920000608 Polyaspartic Polymers 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- DMKSVUSAATWOCU-HROMYWEYSA-N loteprednol etabonate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)OCCl)(OC(=O)OCC)[C@@]1(C)C[C@@H]2O DMKSVUSAATWOCU-HROMYWEYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical compound NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Abstract
The application discloses a water-dispersible polyaspartic acid ester resin, a preparation method and a water-based paint, which are synthesized by polyaspartic acid ester, polyalcohol and hydrophilic monomer through an ester exchange method; the polyalcohol is one of 2-methyl-1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polycaprolactone polyalcohol and the like; the hydrophilic monomer has the structural formula of
Description
Technical Field
The application relates to a water-based paint, in particular to a water-dispersible polyaspartic acid ester resin, a preparation method and a water-based paint.
Background
The water paint is prepared through emulsifying resin, dispersing in water to form emulsion, adding stuffing, and the emulsion grain for preparing resin emulsion is polymer with certain molecular weight, high TG point and smelting point and high viscosity at room temperature. Under low temperature and long-term standing, the resin in the coating is easy to crack and settle, so that small molecular cosolvent such as: propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol monomethyl ether, and the like to lower the TG point of the latex particles.
However, the volatilization of VOC is less along with the water-based paint than with the oily paint, but a certain amount of VOC still exists.
Disclosure of Invention
In order to further reduce VOC volatilization of the water-based paint after use, and ensure safer and more environment-friendly, the preparation method of the 0VOC water-dispersible polyaspartic acid ester paint is provided.
The first object of the present invention is achieved by the following technical solutions:
a method for preparing water-dispersible polyaspartic acid ester resin,
the polyaspartic acid ester is synthesized from polyaspartic acid ester, polyalcohol and hydrophilic monomer by an ester exchange method;
the polyalcohol is one of 2-methyl-1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 12-dodecanediol, polyethylene glycol, polypropylene glycol, polytetrahydrofuran and polycaprolactone polyalcohol;
the hydrophilic monomer is polyethylene glycol monoether, and has a structural formula of
The polymerization degree n=an integer of 4-40, and the R3 is methyl, ethyl, n-propyl, butyl, n-dodecyl and n-octadecyl.
Through adopting above-mentioned technical scheme, replace hydrophilic monomer and R1, R2 base member through transesterification, show from this promotes the hydrophilicity of polyaspartic acid ester for polyaspartic acid ester dispersibility in water is better, and emulsified colloidal particles is difficult for subsidence and demulsification.
Optionally, R3 is methyl.
By adopting the technical scheme, when R3 is methyl, the transesterification reaction is easier to occur, and the production yield is higher.
Optionally, the hydrophilic monomer is one of MPEG400, MPEG450, MPEG500, MPEG550, MPEG600, MPEG650, MPEG 700.
By adopting the technical scheme, when the relative molecular weight of the polyethylene glycol monoether is 400-700, the polyethylene glycol monoether has low viscosity, is easy to disperse in a reaction liquid phase, has high reaction rate and has better product yield.
The second object of the present invention is achieved by the following technical solutions:
the water-dispersible polyaspartic acid ester resin is prepared by the preparation method.
Optionally, the mass content of the polyethylene glycol monoether hydrophilic monomer in the waterborne polyaspartic acid ester resin is 1-30%.
Optionally, the mass content of the polyethylene glycol monoether hydrophilic monomer in the aqueous polyaspartic acid ester resin is 5-20%.
Alternatively, the average functionality of the water-dispersible polyaspartate resin is 2.0-6.0.
By adopting the technical scheme, the water-based paint prepared from the water-dispersible polyaspartic acid ester resin has excellent gloss, hardness, water resistance, weather resistance and solvent resistance
The third object of the present invention is achieved by the following technical solutions: the 0VOC water dispersible polyaspartic acid ester water-based paint comprises the water dispersible polyaspartic acid ester resin, polyisocyanate, filler and water, and does not contain a small molecule cosolvent.
By adopting the technical scheme, the water-based paint can have excellent film forming property without adding small molecule cosolvent, can be normally dried and spread into a uniform film at room temperature, and has excellent gloss, hardness, water resistance, weather resistance and solvent resistance; when in use, the paint product can be adjusted to proper construction viscosity by adding water for dispersion and dilution, no cosolvent or film-forming auxiliary agent is needed, and the paint is more environment-friendly and safe; the small molecule cosolvent has no factors such as volatilization, room temperature reduction and the like in the storage process, and the storage time is longer and more stable than that of the common water-based paint.
In summary, the present application has at least the following beneficial effects:
1. hydrophilic monomers are replaced with the R1 and R2 matrixes through transesterification, so that the hydrophilicity of the polyaspartic acid ester is obviously improved, the dispersibility of the polyaspartic acid ester in water is better, and emulsified colloidal particles are not easy to settle and break.
2. The water-based paint has excellent film forming property without adding small molecule cosolvent, can be normally dried and spread into a uniform film at room temperature, and has excellent gloss, hardness, water resistance, weather resistance and solvent resistance; when in use, the paint product can be adjusted to proper construction viscosity by adding water for dispersion and dilution, no cosolvent or film-forming auxiliary agent is needed, and the paint is more environment-friendly and safe; the small molecule cosolvent has no factors such as volatilization, room temperature reduction and the like in the storage process, and the storage time is longer and more stable than that of the common water-based paint.
Detailed Description
The polyaspartic acid ester is derived from F420, F520, F320, F330, F530, F540 and F620 resins of Feiyang Junya company, and has the molecular structural formula:
r has the structural formula of
One or more of the following;
R 1 、R 2 independently has the structure of C n H 2n N=1 to 4 and is an integer.
Hydrophilic monomer:
polyethylene glycol monoethers of the formula
The polymerization degree n=an integer of 4-40, and the R3 is methyl, ethyl, n-propyl, butyl, n-dodecyl and n-octadecyl.
Example 1
A water-dispersed polyaspartic acid ester resin is prepared from polyaspartic acid ester, polyol and hydrophilic monomer through transesterification.
The preparation method comprises the following steps:
464g of F520 resin, 116g of F320 resin, 39.33g of 3-methyl-1, 5-pentanediol, 154.8g of MPEG400 are mixed under nitrogen;
adding 0.2g of catalyst tetraisopropyl titanate, reacting for 5 hours at the reaction temperature of 115 ℃ under the vacuum degree of 100Pa to obtain the water-dispersible polyaspartic acid ester resin, wherein the viscosity of the water-dispersible polyaspartic acid ester resin is 6630cps after detection, the amine value is 154.6mgKOH/g, and the average functionality is 3 after calculation through a Carother gel point equation.
Example 2
A water-dispersed polyaspartic acid ester resin is prepared from polyaspartic acid ester, polyol and hydrophilic monomer through transesterification.
The preparation method comprises the following steps:
290g of F520 resin, 39.33g of 3-methyl-1, 5-pentanediol, 68.8g of MPEG400 were mixed under nitrogen; adding 0.2g of catalyst tetraisopropyl titanate, and reacting for 5 hours at the reaction temperature of 130 ℃ under the vacuum degree of 100Pa to obtain the water-based polyaspartic acid ester resin.
The viscosity was measured to be 9500cps, the amine number was 172.7mgKOH/g, and the average functionality was 3 as calculated by the Carother gel point equation.
Example 3
A water-dispersed polyaspartic acid ester resin is prepared from polyaspartic acid ester, polyol and hydrophilic monomer through transesterification.
The preparation method comprises the following steps: 290g of F520 resin, 277g of F420 resin, 39.33g of 3-methyl-1, 5-pentanediol and 31.9g of MPEG400 are put into a reactor and mixed under the protection of nitrogen;
adding 0.2g of catalyst tetraisopropyl titanate, and reacting for 5 hours at the reaction temperature of 130 ℃ under the vacuum degree of 100Pa to obtain the water-based polyaspartic acid ester resin.
The viscosity was determined to be 12400cps, amine number was 181.7mgKOH/g, and the average functionality was 3 as calculated by the Carother gel point equation.
Example 4
A water-dispersed polyaspartic acid ester resin is prepared from polyaspartic acid ester, polyol and hydrophilic monomer through transesterification.
The preparation method comprises the following steps:
580g of F520 resin, 39.33g of 3-methyl-1, 5-pentanediol, 67.1g of MPEG700 were mixed under nitrogen; adding 0.2g of catalyst tetraisopropyl titanate, and reacting for 5 hours at the reaction temperature of 130 ℃ under the vacuum degree of 100Pa to obtain the water-dispersible polyaspartic acid ester resin.
The viscosity was measured to be 10100cps, the amine number was 172.2mgKOH/g, and the average functionality was 3 as calculated by the Carother gel point equation.
Example 5
A water-dispersed polyaspartic acid ester resin is prepared from polyaspartic acid ester, polyol and hydrophilic monomer through transesterification.
The preparation method comprises the following steps:
580g of F520 resin, 23.6g of 3-methyl-1, 5-pentanediol, 67.1g of MPEG400 were mixed under nitrogen; adding 0.2g of catalyst tetraisopropyl titanate, and reacting for 5 hours at the reaction temperature of 130 ℃ under the vacuum degree of 100Pa to obtain the water-dispersible polyaspartic acid ester resin.
The amine number was 181.7mgKOH/g, as measured by the Carother gel point equation, at a viscosity of 5760cps and an average functionality of 2.5.
Examples 6 to 10
A 0VOC water-dispersed polyaspartic acid ester waterborne coating comprising component A, B, C.
Wherein the component A is prepared by dispersing the following materials in a reaction kettle for 30min at 3000 r/min:
40g of polyaspartic acid ester resin,
0.3g of an antifoaming agent, and,
1.5g of a dispersing agent, which is used for dispersing the water,
27.0g of titanium dioxide powder,
30.0g of barium sulfate, and the like,
1.3g of leveling agent.
The defoamer was TEGO Airex 901W.
The dispersant TEGO Dispers 715W and the TEGO Dispers 740W are compounded, and the mass ratio is 1:2.
The leveling agent is prepared by compounding BYK 333, BYK 349, BYK 428 and BYK 425 according to the mass ratio of 3:2:4:4.
Component B is a polyisocyanate trimer, in this case HDI trimer, TPA-100 from Asahi chemical Co.
Component C is water.
The preparation method of the 0VOC water dispersible polyaspartic acid ester water-based paint comprises the following steps: A. the component B is uniformly mixed with isocyanate (NCO) in a molar ratio of 1:1.4 to obtain solvent-free paint, and after half of the water by mass of the component A is added, the paint is uniformly mixed with the water to obtain the creamy uniform raw paint.
When in subsequent use, a proper amount of water can be added according to different construction modes, and the final coating can be obtained. For the convenience of detection and sample below, the water amount is 220wt% of the A component, and the raw paint is added with water which is 1.7 times of the A component in mass for even mixing and then used as the final paint.
The sources of the polyaspartic ester resins used in component A of examples 6-10 are different and are shown in Table 1 below.
TABLE 1 Source list for the polyaspartic acid ester resins in component A of examples 6-10
| Sources for polyaspartic acid ester resins | |
| Example 6 | Example 1 |
| Example 7 | Example 2 |
| Example 8 | Example 3 |
| Example 9 | Example 4 |
| Example 10 | Example 5 |
Comparative example 1
The 0VOC water dispersible polyaspartic acid ester water paint is different from the example 2 in that the polyaspartic acid ester resin is prepared by compounding F520 resin and F420 resin according to the mass ratio of 290:277.
The paints of examples 6 to 10 and comparative example 1 were tested in the following manner: film forming property detection, storage aging detection and low-temperature storage aging detection.
The film forming property detection is to prepare a film with the film thickness of 50 mu m on a tinplate by using a film preparation device, test whether the film is formed or not, and record that the film is not formed if the film has defects of gaps, incapability of being uniformly coated, orange peel, needle eyes and the like, and the test times are 100 times; the non-film forming rate is more than 20 percent, and the film is marked as unqualified; the non-film forming rate was less than 2%, which was noted as good.
And the storage aging detection and the low-temperature storage aging take the time of any paint failure phenomenon of sedimentation, demulsification and chromatography observed by the paint as a record, and the longer the time is, the better the corresponding stability of the paint is.
The detection results are as follows:
TABLE 2 coating test results for examples 6-10 and comparative example 1
| Film forming property detection | Storage aging test | Aging at low temperature (0 ℃ C.) | |
| Example 6 | Good grade (good) | 763 | 610 |
| Example 7 | Good grade (good) | 741 | 593 |
| Example 8 | Good grade (good) | 733 | 587 |
| Example 9 | Good grade (good) | 742 | 591 |
| Example 10 | Good grade (good) | 751 | 602 |
| Comparative example | Failure to pass | 73 | 31 |
As can be seen from Table 2, the water-dispersible polyaspartic acid ester resin prepared in examples 6-10 of the application is used, and hydrophilic monomers and R1 and R2 matrixes are replaced by the resin through transesterification, so that the hydrophilicity of the polyaspartic acid ester is obviously improved, the dispersibility of the polyaspartic acid ester in water is better, emulsified colloidal particles are not easy to settle and demulsifie, the water-based paint of the application can have excellent film forming property without adding a small molecular cosolvent, and the paint can be normally dried and spread into a uniform film at room temperature; when in use, the paint product can be adjusted to proper construction viscosity by adding water for dispersion and dilution, no cosolvent or film-forming auxiliary agent is needed, and the paint is more environment-friendly and safe; the small molecule cosolvent has no factors such as volatilization, room temperature reduction and the like in the storage process, and the storage time is longer and more stable than that of the common water-based paint.
In addition, the polyol used in the synthesis of the water-dispersible polyaspartic acid ester resin of the present application has other options than 3-methyl-1, 5-pentanediol.
Examples 11 to 24
The water-dispersible polyaspartic acid ester resin differs from example 1 in the polyol used, wherein the polyol amounts of examples 11 to 24 are 0.33256mol, and the polyol amounts of examples 21 to 24 are 0.66512mol, calculated on the hydroxyl value. The specific types are as follows:
TABLE 3 polyol Table for examples 11-20
| Polyol used | |
| Example 11 | 2-methyl-1, 3-propanediol |
| Example 12 | 1, 4-butanediol |
| Example 13 | 1, 5-pentanediol |
| Example 14 | 1, 6-hexanediol |
| Example 15 | 1, 4-cyclohexanedimethanol |
| Example 16 | 1, 7-heptanediol |
| Example 17 | 1, 8-octanediol |
| Example 18 | 1, 9-nonanediol |
| Example 19 | 1, 10-decanediol |
| Example 20 | 1, 12-dodecanediol |
| Example 21 | Polyethylene glycol |
| Example 22 | Polypropylene glycol |
| Example 23 | Polytetrahydrofuran |
| Example 24 | Polycaprolactone polyols |
Examples 25 to 38
The 0VOC water-dispersed polyaspartic acid ester water-based paint differs from example 6 in that it uses a polyaspartic acid ester resin. The method comprises the following steps:
TABLE 4 polyol Table for examples 25-38
| Polyaspartic acid ester resin used | |
| Example 25 | Example 11 |
| Example 26 | Example 12 |
| Example 27 | Example 13 |
| Example 28 | Example 14 |
| Example 29 | Example 15 |
| Example 30 | Example 16 |
| Example 31 | Example 17 |
| Example 32 | Example 18 |
| Example 33 | Example 19 |
| Example 34 | Example 20 |
| Example 35 | Example 21 |
| Example 36 | Example 22 |
| Example 37 | Example 23 |
| Example 38 | Example 24 |
The 0VOC water-dispersed polyaspartic acid ester water-based paint of examples 25 to 38 was tested, and the test results were as follows:
TABLE 5 coating detection results Table for examples 25-38
As can be seen from the combination of Table 1 and Table 5, the polyhydric alcohol of the water-dispersible polyaspartic acid ester resin of the present application is one of 2-methyl-1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 12-dodecanediol, polyethylene glycol, polypropylene glycol, polytetrahydrofuran, and polycaprolactone polyol. Among them, 3-methyl-1, 5-pentanediol is preferable as a result of comparison between example 6 and examples 25 to 38.
Example 39
The water-dispersible polyaspartic acid ester resin differs from example 1 in that R3 in the hydrophilic monomer used is ethyl.
Example 40
The water-dispersible polyaspartic acid ester resin differs from example 1 in that R3 in the hydrophilic monomer used is n-propyl.
Example 41
The water-dispersible polyaspartic acid ester resin differs from example 1 in that R3 in the hydrophilic monomer used is butyl.
Example 42
The water-dispersible polyaspartic acid ester resin differs from example 1 in that R3 in the hydrophilic monomer used is n-dodecyl.
Example 43
The water-dispersible polyaspartic acid ester resin differs from example 1 in that R3 in the hydrophilic monomer used is n-octadecyl.
Examples 44 to 48
The 0VOC water-dispersed polyaspartic acid ester water-based paint is different from example 6 in that it uses a polyaspartic acid ester resin as follows.
TABLE 6 recording of the polyaspartic acid ester resins used in examples 44-48
| Polyaspartic acid ester resin used | |
| Example 44 | Example 39 |
| Example 45 | Example 40 |
| Example 46 | Example 41 |
| Example 47 | Example 42 |
| Example 48 | Example 43 |
The 0VOC water-dispersed polyaspartic acid ester water-based paint of examples 44 to 48 was tested, and the test results were as follows:
TABLE 7 coating test results Table for examples 44-48
| Film forming property detection | Storage aging test | Aging at low temperature (0 ℃ C.) | |
| Example 44 | Good grade (good) | 759 | 609 |
| Example 45 | Good grade (good) | 759 | 607 |
| Example 46 | Good grade (good) | 755 | 606 |
| Example 47 | Good grade (good) | 754 | 604 |
| Example 48 | Good grade (good) | 752 | 603 |
As can be seen from a combination of tables 1 and 7, R3 of the hydrophilic monomer in the water-dispersible polyaspartic acid ester resin of the present application may be R3 is ethyl, n-propyl, butyl, n-dodecyl or n-octadecyl, wherein example 6 is superior to examples 44 to 48, and thus R3 is methyl.
The influence of the polymerization degree on the dispersibility of the water-dispersible polyaspartic acid ester resin and the coating on the basis of R3, namely MPEG, as a hydrophilic monomer is also studied.
Examples 49 to 54
The water-dispersible polyaspartic acid ester resin differs from example 1 in the molecular weight of the MPEG used, as follows.
TABLE 8 recording of hydrophilic monomers used in examples 49-54
| Hydrophilic monomers used | |
| Example 49 | MPEG450 |
| Example 50 | MPEG500 |
| Example 51 | MPEG550 |
| Example 52 | MPEG600 |
| Example 53 | MPEG650 |
| Example 54 | MPEG700 |
Examples 55 to 60
The 0VOC water-dispersed polyaspartic acid ester water-based paint differs from example 6 in that the water-dispersed polyaspartic acid ester resin used is specifically as follows:
TABLE 9 recording of Water-dispersible polyaspartic acid ester resins used in examples 55 to 60
The 0VOC water-dispersed polyaspartic acid ester water-based paint of examples 55 to 60 was tested, and the test results were as follows:
table 10 coating test results Table of examples 55 to 60
| Film forming property detection | Storage aging test | Aging at low temperature (0 ℃ C.) | |
| Example 55 | Good grade (good) | 763 | 604 |
| Example 56 | Good grade (good) | 751 | 599 |
| Example 57 | Good grade (good) | 740 | 595 |
| Example 58 | Good grade (good) | 726 | 592 |
| Example 59 | Good grade (good) | 711 | 587 |
| Example 60 | Good grade (good) | 696 | 586 |
As can be seen from the combination of table 1 and table 10, as the polymerization degree of MPEG increases, the hydrophilic modification effect of the water-dispersible polyaspartic acid ester decreases, and the smaller the polymerization degree, the better the water-dispersible polyaspartic acid ester modification effect is under the condition that the introduction of a new VOC component is avoided.
The present application also refers to studies on the threshold of efficacy in modifying polyaspartic acid esters with hydrophilic monomers.
Example 61
The water-dispersible polyaspartic acid ester resin differs from example 1 in that it uses a different amount of MPEG400, which is 1wt% of the amount of the raw material.
Example 62
The water-dispersible polyaspartic acid ester resin differs from example 1 in that it uses a different amount of MPEG400, which is 5% by weight of the amount of the raw material.
Example 63
The water-dispersible polyaspartic acid ester resin differs from example 1 in that it uses a different amount of MPEG400, which is 10% by weight of the amount of the raw material.
Example 64
The water-dispersible polyaspartic acid ester resin differs from example 1 in that it uses a different amount of MPEG400, which accounts for 30wt% of the amount of the raw material.
Example 65
The 0VOC water-dispersed polyaspartic acid ester water-based paint is different from example 6 in that the water-dispersed polyaspartic acid ester resin used is example 61.
Example 66
The 0VOC water-dispersed polyaspartic acid ester water-based paint is different from example 6 in that the water-dispersed polyaspartic acid ester resin used is example 62.
Example 67
The 0VOC water-dispersed polyaspartic acid ester water-based paint is different from example 6 in that the water-dispersed polyaspartic acid ester resin used is example 63.
Example 68
The 0VOC water-dispersed polyaspartic acid ester water-based paint is different from example 6 in that the water-dispersed polyaspartic acid ester resin used is example 64.
The 0VOC water-dispersed polyaspartic acid ester water-based paint of examples 65 to 68 was tested, and the test results were as follows:
TABLE 11 coating test results Table for examples 65-68
| Film forming property detection | Storage aging test | Aging at low temperature (0 ℃ C.) | |
| Example 65 | Good grade (good) | 381 | 286 |
| Example 66 | Good grade (good) | 700 | 561 |
| Example 67 | Good grade (good) | 721 | 574 |
| Example 68 | Good grade (good) | 710 | 533 |
As can be seen from a combination of Table 1 and Table 11, examples 65-68 have significantly better film forming properties and storage failure than comparative example 1. The water-dispersible polyaspartic acid ester resin of example 61 used in example 65 has the MPEG400 content of only 1wt%, and can achieve remarkable synergy.
Further, as is evident from comparison of examples 6 and 68, the storage time of example 68 is slightly reduced due to the excessive amount of MPEG400 used, which results in transesterification of MPEG and the formation of amino ether by reaction of the exchanged MPEG with N-H on the poly (aspartic acid) ester resin, and the increase in TG.
Therefore, the polyethylene glycol monoether hydrophilic monomer in the application has a synergistic threshold value of content=1-30wt% in the waterborne polyaspartic acid ester resin, and the effect is better in the range of 5-20wt%.
The present embodiment is merely illustrative of the present invention and is not intended to be limiting, and modifications which would be obvious to those skilled in the art to which the present invention pertains without inventive contribution may be made as desired after having read the specification, but are intended to be protected by the patent law within the scope of the present invention.
Claims (9)
1. The preparation method of the water-dispersible polyaspartic acid ester resin is characterized by comprising the following steps of:
the polyaspartic acid ester is synthesized from polyaspartic acid ester, polyalcohol and hydrophilic monomer by an ester exchange method;
the polyalcohol is one of 2-methyl-1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 12-dodecanediol, polyethylene glycol, polypropylene glycol, polytetrahydrofuran and polycaprolactone polyalcohol;
the hydrophilic monomer is polyethylene glycol monoether, and has a structural formula of
The polymerization degree n=an integer of 4-40, and the R3 is methyl, ethyl, n-propyl, butyl, n-dodecyl and n-octadecyl.
2. The method for preparing a water dispersible polyaspartic acid ester resin according to claim 1, wherein R3 is methyl.
3. The method for preparing the water-dispersible polyaspartic acid ester resin according to claim 2, wherein the hydrophilic monomer is one of MPEG400, MPEG450, MPEG500, MPEG550, MPEG600, MPEG650, and MPEG 700.
4. The water-dispersible polyaspartic acid ester resin, which is characterized by being prepared by the preparation method of any one of claims 1 to 3.
5. The water-dispersible polyaspartic acid ester resin according to claim 4, wherein the mass content of the polyethylene glycol monoether hydrophilic monomer in the aqueous polyaspartic acid ester resin is 1-30%.
6. The water-dispersible polyaspartic acid ester resin according to claim 5, wherein the mass content of the polyethylene glycol monoether hydrophilic monomer in the aqueous polyaspartic acid ester resin is 5-20%.
7. The water dispersible polyaspartic acid ester resin of claim 4, wherein the water dispersible polyaspartic acid ester resin has an average functionality of from 2.0 to 6.0.
8.0VOC water dispersible polyaspartic acid ester water-based paint, characterized in that it comprises the water dispersible polyaspartic acid ester resin of claim 4, polyisocyanate, filler and water, and is free of small molecule co-solvents.
9.0VOC water dispersible polyaspartic acid ester water-based paint, characterized in that it comprises the water dispersible polyaspartic acid ester resin of any one of claims 5-7, polyisocyanate, filler and water, and does not contain small molecule cosolvent.
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