CN117801270A - Water-based polyaspartic acid ester resin and preparation method thereof - Google Patents
Water-based polyaspartic acid ester resin and preparation method thereof Download PDFInfo
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- acid ester
- polyaspartic acid
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- 229920005989 resin Polymers 0.000 title claims abstract description 182
- 239000011347 resin Substances 0.000 title claims abstract description 182
- 108010064470 polyaspartate Proteins 0.000 title claims abstract description 136
- 150000002148 esters Chemical class 0.000 title claims abstract description 129
- 229920000805 Polyaspartic acid Polymers 0.000 title claims abstract description 125
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 229920005862 polyol Polymers 0.000 claims abstract description 33
- 150000003077 polyols Chemical class 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 150000005846 sugar alcohols Polymers 0.000 claims abstract 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 claims description 23
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 23
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 229920001610 polycaprolactone Polymers 0.000 claims description 9
- 239000004632 polycaprolactone Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 2
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 30
- 238000000576 coating method Methods 0.000 abstract description 30
- 239000000126 substance Substances 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 25
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 238000003760 magnetic stirring Methods 0.000 description 17
- 239000000839 emulsion Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- -1 maleic acid ester Chemical class 0.000 description 9
- 229920002396 Polyurea Polymers 0.000 description 8
- 238000005809 transesterification reaction Methods 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- 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 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007888 film coating Substances 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 244000003416 Asparagus officinalis Species 0.000 description 1
- 235000005340 Asparagus officinalis Nutrition 0.000 description 1
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 229920000608 Polyaspartic Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- TUEYHEWXYWCDHA-UHFFFAOYSA-N ethyl 5-methylthiadiazole-4-carboxylate Chemical compound CCOC(=O)C=1N=NSC=1C TUEYHEWXYWCDHA-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Abstract
The application relates to the field of polyaspartic acid ester resins, and particularly discloses a water-based polyaspartic acid ester resin and a preparation method thereof. The aqueous polyaspartic acid ester resin comprises polyaspartic acid ester resin, polyalcohol, hydrophilic monomer and ester catalyst; the molar ratio of polyaspartic acid ester resin to polyol is 1:0.2 to 0.5 percent, wherein the hydrophilic monomer is polyethylene glycol Monoether (MPEG), and the mass fraction of the hydrophilic monomer is 5 to 30 percent of the polyaspartic acid ester resin; the preparation method comprises the following steps: uniformly mixing the polyaspartic acid ester resin, the polyol and the hydrophilic monomer to obtain a mixture A, adding a titanate catalyst into the mixture A, and preparing the water-based polyaspartic acid ester resin at 100-130 ℃ and a vacuum degree of less than 1000 pa. The average functionality of the aqueous polyaspartic acid ester resin is 2.5-4, and the crosslinking density is higher, so that the coating prepared from the aqueous polyaspartic acid ester resin serving as a raw material is better in water resistance and chemical resistance.
Description
Technical Field
The application relates to the field of polyaspartic acid ester resins, in particular to an aqueous polyaspartic acid ester resin and a preparation method thereof.
Background
The polyaspartic acid ester resin is solvent-free environment-friendly resin, is mainly used for preparing low-solvent paint and high-solid paint, and is applied to the industrial fields of waterproofing, terrace, corrosion resistance and the like. However, the coating prepared from the coating has different application fields and construction modes, and the coating can emit Volatile Organic Compounds (VOC) into the air during outdoor construction, and resin products with lower VOC emission and 0VOC are more suitable for the demands of consumers based on severe global warming. Thus, low VOC-based aqueous polyaspartic acid ester resins have evolved.
The aqueous technology of polyaspartic acid ester resin is rare, and only a small number of related technologies are adopted. Among other things, EP0849301 discloses an aqueous two-component polyaspartate coating which combines an HDI trimer with a hydrophilic monomer to form an aqueous HDI trimer, which is then mixed with an NH1520 resin, and the entire aqueous HDI trimer is dispersed in water as a relatively stable emulsion after mixing with the NH1520 resin due to its relatively strong water dispersibility. However, the introduction of hydrophilic monomers into aqueous HDI trimers reduces the trimer functionality, resulting in a decrease in the crosslinking density of the coating film, thereby affecting the drying, water resistance and solvent resistance of the coating film. US20160060380 discloses a method for synthesizing a hydrophilic polyaspartic acid ester resin by synthesizing a polyisocyanate containing a hydrophilic monomer and then reacting the polyisocyanate with an excess of polyaspartic acid ester resin, however, the process is too complicated in the use process. US7253252B2 discloses a synthesis method of a water-soluble polyaspartic acid ester resin, which is to perform transesterification between hydrophilic monomers (diethanol monoether, diethylene glycol monoether and triethylene glycol monoether) and maleic acid ester to obtain hydrophilic maleic acid ester, and then performing michael addition reaction on the maleic acid ester and primary ammonia to obtain the water-soluble polyaspartic acid ester resin, wherein an intermediate of transesterification between the hydrophilic monomers and the maleic acid ester is difficult to refine, the product has lower functionality, and has strong hydrophilicity and poor water resistance of a coating film. In the synthesis method of the aqueous polyaspartic acid ester disclosed in CN111303368B, the polyaspartic acid ester resin is prepared by performing transesterification on triethylene glycol monomethyl ether or tetraethylene glycol monomethyl ether and the asparaginic acid ester resin after the polyaspartic acid ester resin is generated by reacting primary ammonia with maleic acid ester, so that the water-soluble polyaspartic acid ester resin is obtained, however, the polyaspartic acid ester resin has only two functionalities and is too strong in hydrophilicity, and the water resistance of a coating film is poor.
In the related art, the aqueous polyaspartic acid ester resin is a linear resin with two functionalities, and the water resistance and the solvent resistance of the coating prepared by taking the resin as a raw material are poor due to the low crosslinking density.
Disclosure of Invention
In order to improve the functionality of the aqueous polyaspartic acid ester resin and prepare the aqueous asparaguse coating with water resistance and wear resistance, the application provides the aqueous polyaspartic acid ester resin and a preparation method thereof.
In a first aspect, the present application provides an aqueous polyaspartic acid ester resin, which adopts the following technical scheme:
an aqueous polyaspartic acid ester resin comprises polyaspartic acid ester resin, polyalcohol, hydrophilic monomer and ester catalyst; the molar ratio of the polyaspartic acid ester resin to the polyol is 1:0.2-0.5 percent, wherein the hydrophilic monomer is polyethylene glycol Monoether (MPEG), and the mass fraction of the hydrophilic monomer is 5-30 percent of the polyaspartic acid ester resin.
By adopting the technical scheme, the ester group in the polyaspartic acid ester resin can perform ester exchange reaction with the hydroxyl groups in the hydrophilic monomer and the polyol under the action of the catalyst, so that the hydrophilic monomer and the polyol can be connected into polyaspartic acid ester resin molecules.
The hydrophilic monomer is polyethylene glycol monoether, wherein the polyethylene glycol monoether is connected with the polyaspartic acid ester resin by a chemical bond, so that the polyethylene glycol monoether and the polyaspartic acid ester resin can carry out a chemical reaction, and the polyaspartic acid ester resin which cannot be emulsified in water can be emulsified in water; when the mass fraction of the hydrophilic monomer is less than 5% or more than 30% of the polyaspartic acid ester resin, the prepared aqueous polyaspartic acid ester resin is inferior in hardness, water resistance and solvent resistance, and therefore, only a coating emulsion excellent in water resistance and chemical resistance can be prepared by limiting the mass fraction of the hydrophilic monomer to 5% to 30% of the polyaspartic acid ester resin.
Meanwhile, polyol is adopted to replace monohydric alcohol, and finally, an internal emulsified water dispersion is formed, when the molar ratio of polyaspartic acid ester resin to polyol is 1: when the average functionality is 0.2-0.5, the aqueous polyaspartic acid ester resin with the average functionality of 2.5-4 is prepared, and the coating prepared by taking the aqueous polyaspartic acid ester resin as a main material has good emulsifying property, good film coating property and good water resistance and chemical resistance.
Preferably, the polyol is at least 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, polycaprolactone polyols.
By adopting the technical scheme, the polyol, the polyaspartic acid ester resin and the hydrophilic monomer are combined to form an internal emulsified dispersion system, and the prepared asparagus polyurea coating emulsion is free from demulsification, sedimentation and high in hardness; importantly, the polyol has low cost and is easy to obtain, and can be applied to large-scale industrial production.
Preferably, the molecular structure of the polyaspartic acid ester resin is as follows:
wherein R is 1 、R 2 The structure of the two can be the same or different, and the two can be one of methyl, ethyl, propyl, n-butyl and isobutyl; the structural formula of R is at least one of the following.
When R is (1), R1 is ethyl, the obtained polyaspartate resin is an asparate polyurea resin F420,
when R is (2), R1 is, R2 is ethyl, the obtained polyaspartate resin is an asparate polyurea resin F520,
when R is (3), n=2, R1 is, R2 is ethyl, the resulting polyaspartate resin is asparate polyurea resin F320,
when R is (3) n=3, R1 is, R2 is ethyl, the resulting polyaspartate resin is asparate polyurea resin F330,
when R is (4), R1 is, R2 is ethyl, the resulting polyaspartate resin is an asparate polyurea resin F530,
when R is (5), R1 is ethyl, the obtained polyaspartate resin is an asparate polyurea resin F540,
when R is (6), R1 is, and R2 is ethyl, the resulting polyaspartate resin is an asparate polyurea resin F620.
By adopting the technical scheme, the process flow of the polyaspartic acid ester resin with the structure is simpler in the use process, and the ethyl ester group in the polyaspartic acid ester resin is easier to carry out transesterification.
Preferably, the hydrophilic monomer is polyethylene glycol monoether, and the structural formula of the polyethylene glycol monoether is:
R 3 is one of methyl, ethyl, n-propyl, butyl, n-dodecyl and n-octadecyl, preferably methyl, namely polyethylene glycol monomethyl ether, and has a polymerization degree of n=4-40.
The polyethylene glycol monomethyl ether is one of MPEG400, MPEG450, MPEG500, MPEG550, MPEG600, MPEG650 and MPEG 700.
Through adopting above-mentioned technical scheme, when R3 is methyl, hydrophilic monomer's hydrophilicity is stronger, and it carries out the speed of transesterification more fast with polyaspartic acid ester resin, polyol between, simultaneously, the internal emulsification system that takes part in the formation by it is more stable even, and the water resistance and the film coating nature of the coating of preparation are better.
Preferably, the mass fraction of the hydrophilic monomer is 10% -20% of that of the aqueous polyaspartic acid ester resin.
In a second aspect, the present application provides a method for preparing an aqueous polyaspartic acid ester resin, which adopts the following technical scheme:
a preparation method of water-based polyaspartic acid ester resin comprises the following steps:
uniformly mixing the polyaspartic acid ester resin, the polyol and the hydrophilic monomer to obtain a mixture A, adding a titanate catalyst into the mixture A, and preparing the water-based polyaspartic acid ester resin at 100-130 ℃ and a vacuum degree of less than 1000 pa.
By adopting the technical scheme, after the polyaspartic acid ester resin, the polyol and the hydrophilic monomer are uniformly mixed, the temperature is directly raised to 100-130 ℃ under the action of the phthalate ester catalyst, no side reaction is generated in the reaction process, and the prepared water-based polyaspartic acid ester resin is better in color.
Preferably, the titanate catalyst is added into the mixture A, and the mass addition amount of the titanate catalyst is 0.01% -0.02% of the mass of the mixture A.
By adopting the technical scheme, the alkaline titanate catalyst is used as the transesterification catalyst, the dosage is controlled, and the color and the high viscosity of the product caused by excessive dosage are avoided.
Preferably, the titanate catalyst is one of tetraisopropyl titanate, tetra-n-butyl titanate and tetrabutyl zirconate, and more preferably is tetraisopropyl titanate.
By adopting the technical scheme, the tetraisopropyl titanate has better reaction activity, and can react with the mixture A with lower catalyst dosage.
Preferably, the temperature in the process of preparing the aqueous polyaspartic acid ester resin is 115-130 ℃, and the vacuum degree is less than 100pa.
By adopting the technical scheme, the vacuum degree is less than 100pa, which is favorable for reaction, can accelerate the reaction speed, shortens the reaction time, and ensures that the reaction can be quickly and completely carried out within the temperature range of 115-130 ℃.
In summary, the present application has the following beneficial effects:
1. the related technology adopts the application that the polyaspartic acid ester resin, the monohydric alcohol and the hydrophilic monomer are combined, and the prepared water-based polyaspartic acid ester resin has the problems of poor toughness, poor water resistance and the like of a coating film in the use process; the present application utilizes polyol to replace monohydric alcohol and controls the molar ratio of polyaspartic acid ester resin to polyol, when the molar ratio of polyaspartic acid ester resin to polyol is 1:0.2-0.5, according to the calculation of the Carother gel point equation, the added functionality of the aqueous polyaspartic acid ester resin is higher, and between 2.5 and 4, the aqueous polyaspartic acid ester resin prepared by the application has better hardness, water resistance and solvent resistance due to the improved functionality; in addition, the prepared aqueous polyaspartic acid ester resin is an internal emulsified dispersion system, the nature of the aqueous polyaspartic acid ester resin is a colloidal emulsion, the particle size of the colloidal emulsion is changed along with the different use amounts of the hydrophilic monomers, and when the content of the hydrophilic monomers is changed, the appearance of the dispersion of the resin product and water is gradually changed from milky milk to light blue liquid.
2. The mass fraction of the hydrophilic monomer in the application is 5% -30% of that of the aqueous polyaspartic acid ester resin, the hydrophilic monomer is polyethylene glycol monoether, the hydrophilic monomer can be quickly mixed with the polyaspartic acid ester resin with strong hydrophilicity, and the coating formed by combining the aqueous polyaspartic acid ester resin prepared by the hydrophilic monomer with the isocyanate curing agent has the advantages of high hardness, excellent solvent resistance and high hardness when in use.
3. According to the method, the whole process flow period is short, the catalyst dosage is small, the process temperature is low, meanwhile, the aqueous polyaspartic acid ester resin product prepared by the method is not demulsified, does not settle in 2 hours, and the appearance is a colorless and transparent film.
Detailed Description
The present application is described in further detail below in conjunction with tables and examples.
Examples
Example 1
290g (0.5 mol) of F520 resin, 277g (0.5 mol) of F420 resin, 39.33g (0.3333 mol) of 3-methyl-1, 5-pentanediol and 31.9g (about 5% by mass) of MPEG400 were put into a four-necked flask equipped with a magnetic stirrer, an automatic temperature controller, a nitrogen port and a vacuum pump, and 0.2g of tetraisopropyl titanate catalyst was added to react for 5H at a reaction temperature of 100℃under a vacuum of 100Pa to obtain an aqueous polyaspartate resin.
Example 2
580g (1 mol) of F520 resin, 39.33g (0.3333 mol) of 3-methyl-1, 5-pentanediol and 68.8g (mass fraction: 10%) of MPEG400 were put into a four-necked flask equipped with a magnetic stirrer, an automatic temperature controller, a nitrogen port and a vacuum pump, and 0.2g of tetraisopropyl titanate catalyst was added to react for 5H at a reaction temperature of 130℃under a vacuum of 100Pa, to obtain an aqueous polyaspartic acid ester resin.
Example 3
464g (0.8 mol) of F520 resin, 116g (0.2 mol) of F320 resin, 39.33g (0.3333 mol) of 3-methyl-1, 5-pentanediol and 154.8g (mass fraction: 20%) of MPEG400 were put into a four-necked flask equipped with a magnetic stirrer, an automatic temperature controller, a nitrogen port and a vacuum pump, and 0.2g of tetraisopropyl titanate catalyst was added to react for 5H at a reaction temperature of 115℃under a vacuum of 100Pa, to obtain an aqueous polyaspartic acid ester resin.
Example 4
580g (1 mol) of F520 resin, 39.33g (0.3333 mol) of 3-methyl-1, 5-pentanediol and 265.4g (mass fraction: 30%) of MPEG400 were put into a four-necked flask equipped with a magnetic stirrer, an automatic temperature controller, a nitrogen port and a vacuum pump, and 0.2g of tetraisopropyl titanate catalyst was added to react for 5H at a reaction temperature of 115℃under a vacuum of 100Pa, to obtain an aqueous polyaspartic acid ester resin.
Example 5
580g (1 mol) of F520 resin, 39.33g (0.3333 mol) of 3-methyl-1, 5-pentanediol and 67.1g (mass fraction: 10%) of MPEG700 were put into a four-necked flask equipped with a magnetic stirring, automatic temperature controller, nitrogen port and vacuum pump device, and 0.2g of tetraisopropyl titanate catalyst was added to react for 5H at a reaction temperature of 130℃under a vacuum of 100Pa, to obtain an aqueous polyaspartic acid ester resin.
Example 6
580g (1 mol) of F520 resin, 333.3g (0.3333 mol) of polycaprolactone polyol (PLACCEL 210N) and 101.5g (mass fraction: 10%) of MPEG400 were put into a four-necked flask equipped with a magnetic stirring, automatic temperature controller, nitrogen port and vacuum pump device, and 0.3g of tetraisopropyl titanate catalyst was added to react for 5H at a reaction temperature of 130℃under a vacuum of 100Pa, to obtain an aqueous polyaspartic acid ester resin.
Example 7
580g (1 mol) of F520 resin, 23.6g (0.2 mol) of 3-methyl-1, 5-pentanediol and 67.1g (mass fraction: 10%) of MPEG400 were put into a four-necked flask equipped with a magnetic stirring, automatic temperature controller, nitrogen port and vacuum pump device, and 0.2g of tetraisopropyl titanate catalyst was added to react for 5H at a reaction temperature of 130℃under a vacuum of 100Pa, to obtain an aqueous polyaspartic acid ester resin.
Example 8
580g (1 mol) of F520 resin, 59g (0.5 mol) of 3-methyl-1, 5 pentanediol and 71g (mass fraction: 10%) of MPEG400 were put into a four-necked flask equipped with a magnetic stirring, an automatic temperature controller, a nitrogen port and a vacuum pump device, 0.2g of tetraisopropyl titanate catalyst was added, and the mixture was reacted at a reaction temperature of 130℃under a vacuum of 100Pa for 5H to obtain an aqueous polyaspartic acid ester resin.
Example 9
580g (1 mol) of F520 resin, 333.3g (0.3333 mol) of polytetrahydrofuran, and 101.5g (mass fraction: 10%) of MPEG400 were put into a four-necked flask equipped with a magnetic stirring, automatic temperature controller, nitrogen port, and vacuum pump device, and 0.3g of tetraisopropyl titanate catalyst was added to react for 5H at a reaction temperature of 130℃under a vacuum of 100Pa, to obtain an aqueous polyaspartic acid ester resin.
Example 10 an aqueous polyaspartic acid ester resin was obtained by charging 580g (1 mol) of F520 resin, 39.33g (0.3333 mol) of 3-methyl-1, 5-pentanediol, and 154.8gg (20% by mass) of MPEG400 into a four-necked flask equipped with a magnetic stirrer, an automatic temperature controller, a nitrogen port, and a vacuum pump, adding 0.2g of tetraisopropyl titanate catalyst, and reacting at a reaction temperature of 130℃under a vacuum of 100Pa for 5H.
Example 11
580g (1 mol) of F520 resin, 39.33g (0.3333 mol) of 3-methyl-1, 5-pentanediol and 68.8g (mass fraction: 10%) of MPEG400 were put into a four-necked flask equipped with a magnetic stirrer, an automatic temperature controller, a nitrogen port and a vacuum pump, and 0.4g of tetraisopropyl titanate catalyst was added to react for 5H at a reaction temperature of 130℃under a vacuum of 100Pa, to obtain an aqueous polyaspartic acid ester resin.
Comparative example
Comparative example 1
290g (0.5 mol) of F520 resin, 277g (0.5 mol) of F420 resin, 39.33g (0.3333 mol) of 3-methyl-1, 5-pentanediol and 32.6g (mass fraction 5%) of MPEG400 were put into a four-necked flask equipped with magnetic stirring, and uniformly mixed to obtain an aqueous polyaspartic acid ester resin.
Comparative example 2
580g (1 mol) of F520 resin, 39.33g (0.3333 mol) of 3-methyl-1, 5-pentanediol and 68.8g (mass fraction 10%) of MPEG400 were put into a four-necked flask equipped with magnetic stirring, and uniformly mixed to obtain an aqueous polyaspartic acid ester resin.
Comparative example 3
464g (0.8 mol) of F520 resin, 116g (0.2 mol) of F320 resin, 39.33g (0.3333 mol) of 3-methyl-1, 5-pentanediol and 154.8g (mass fraction: 20%) of MPEG400 were put into a four-necked flask equipped with magnetic stirring, and uniformly mixed to obtain an aqueous polyaspartic acid ester resin.
Comparative example 4
580g (1 mol) of F520 resin, 39.33g (0.3333 mol) of 3-methyl-1, 5-pentanediol and 265.4g (mass fraction: 30%) of MPEG400 were put into a four-necked flask equipped with magnetic stirring, and uniformly mixed to obtain an aqueous polyaspartic acid ester resin.
Comparative example 5
580g (1 mol) of F520 resin and 64.4g (mass fraction: 10%) of MPEG400 were put into a four-necked flask equipped with a magnetic stirring, automatic temperature controller, nitrogen port and vacuum pump device, 0.2g of tetraisopropyl titanate catalyst was added, and the mixture was reacted at a reaction temperature of 130℃under a vacuum of 100Pa for 5H to obtain an aqueous polyaspartic acid ester resin.
Comparative example 6
580g (1 mol) of F520 resin, 34g (0.3333 mol) of n-hexanol and 71.6g (mass fraction: 10%) of MPEG400 were put into a four-necked flask equipped with a magnetic stirring, automatic temperature controller, nitrogen port and vacuum pump device, 0.3g of tetraisopropyl titanate catalyst was added, and the mixture was reacted at a reaction temperature of 130℃under a vacuum of 100Pa for 5H to obtain an aqueous polyaspartate resin.
Comparative example 7
580g (1 mol) of F520 resin and 333.3g (0.3333 mol) of polycaprolactone polyol (PLACCEL 210N) were put into a four-necked flask equipped with a magnetic stirring, automatic temperature controller, nitrogen port and vacuum pump device, and 0.3g of tetraisopropyl titanate catalyst was added to react for 5H at a reaction temperature of 130 ℃ under a vacuum of 100Pa to obtain an aqueous polyaspartic acid ester resin.
Comparative example 8
580g (1 mol) of F520 resin, 333.3g (0.3333 mol) of polycaprolactone polyol (PLACCEL 210N) and 101.5g (mass fraction 10%) of polypropylene glycol monomethyl ether with an average molecular weight of 400 are put into a four-necked flask equipped with a magnetic stirring, an automatic temperature controller, a nitrogen port and a vacuum pump device, 0.3g of tetraisopropyl titanate catalyst is added, and the mixture is reacted at a reaction temperature of 130 ℃ under a vacuum degree of 100Pa for 5H to obtain an aqueous polyaspartic acid ester resin.
Comparative example 9
580g (1 mol) of F520 resin, 333.3g (0.3333 mol) of polycaprolactone polyol (PLACCEL 210N) and 28.2g (mass fraction 3%) of MPEG400 were put into a four-necked flask equipped with a magnetic stirring, automatic temperature controller, nitrogen port and vacuum pump device, and 0.3g of tetraisopropyl titanate catalyst was added to react for 5H at a reaction temperature of 130℃under a vacuum of 100Pa to obtain an aqueous polyaspartic acid ester resin.
Comparative example 10
580g (1 mol) of F520 resin, 333.3g (0.3333 mol) of polycaprolactone polyol (PLACCEL 210N) and 491.8g (mass fraction: 35%) of MPEG400 were put into a four-necked flask equipped with a magnetic stirring, automatic temperature controller, nitrogen port and vacuum pump device, and 0.3g of tetraisopropyl titanate catalyst was added to react for 5H at a reaction temperature of 130℃under a vacuum of 100Pa, to obtain an aqueous polyaspartic acid ester resin.
Comparative example 11
580g (1 mol) of F520 resin, 150g (0.15 mol) of polycaprolactone polyol (PLACCEL 210N) and 81.1g (mass fraction: 10%) of MPEG400 were put into a four-necked flask equipped with a magnetic stirring, automatic temperature controller, nitrogen port and vacuum pump device, 0.3g of tetraisopropyl titanate catalyst was added, and the mixture was reacted at a reaction temperature of 130℃under a vacuum of 100Pa for 5H to obtain an aqueous polyaspartic acid ester resin.
Comparative example 12
580g (1 mol) of F520 resin, 600g (0.60 mol) of polycaprolactone polyol (PLACCEL 210N) and 131.1g (mass fraction: 10%) of MPEG400 were put into a four-necked flask equipped with a magnetic stirring, automatic temperature controller, nitrogen port and vacuum pump device, 0.3g of tetraisopropyl titanate catalyst was added, and the mixture was reacted at a reaction temperature of 130℃under a vacuum of 100Pa for 5H to obtain an aqueous polyaspartic acid ester resin.
Performance test
Test method
The viscosity of the aqueous polyaspartic acid ester resin was measured by the GB/T97511988 method and the results are shown in Table 1.
The functionality of the aqueous polyaspartic acid ester resin can be calculated according to the Carother gel point equation and the results are shown in Table 1.
The resulting aqueous polyaspartic acid ester resin was dispersed with water at a ratio of 1:1 at 700r/min for 10min, and then placed in a 30cm test tube to observe the appearance of the emulsion, the sedimentation condition after 2H of the emulsion, and whether the emulsion was broken or not, and the results are shown in table 2.
The aqueous polyaspartic acid ester resin obtained was mixed with polyisocyanate TPA-100 at a molar ratio of NH: NCO groups=1:1.4, dispersed at 700r/min for 10min, diluted with water to 50% solids content, observed whether the coating emulsion was demulsified, and a wet film of 100um thickness was coated on a glass plate using a film coater, and after drying, the appearance of the coating film was observed and the pencil hardness of the coating film was measured, and the results are shown in table 3.
Film coating water resistance test: the dried coating film was subjected to a test in hot water at 80℃to observe the change in appearance of the coating film, and the results are shown in Table 4.
Solvent resistance test of coating: the dried coating film was repeatedly rubbed with acetone 50 times, and the change in appearance of the coating film was observed, and the results are shown in table 4.
Performance data
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The data obtained in connection with examples 1-11 show that: when the molar ratio of polyaspartic acid ester resin to polyol is 1:0.2-0.5, when the mass fraction of the limited hydrophilic monomer is 5% -30% of the polyaspartic acid ester resin, the viscosity of the prepared aqueous polyaspartic acid ester resin is moderate and is not more than 25800cps, and the average functionality is not less than 2.5; importantly, the aqueous polyaspartic acid ester resin emulsion prepared by the method is uniformly mixed, does not delaminate, and does not generate sedimentation or demulsification after standing for 2 hours. After the aqueous polyaspartic acid ester resin is mixed with the polyisocyanate TPA-100, the formed coating also has no demulsification phenomenon, a colorless transparent film is formed, and the film is detected, so that the result is shown as follows: the hardness is moderate, and the water resistance and the solubility resistance are good.
Combining the data results of example 2, example 4 and example 10, it can be seen that: when the mass fraction of the hydrophilic monomer is different, the hardness of the formed coating film is different after the finally prepared aqueous polyaspartic acid ester resin is mixed with TPA-100, and when the mass fraction of the hydrophilic monomer is 20% of that of the polyaspartic acid ester resin, the hardness of the coating film is moderate, and the grade is H.
Combining the data results of example 2, example 6 and example 9, it can be seen that: the type of the polyol is different, and the hardness of the coating film formed after the finally prepared aqueous polyaspartic acid ester resin is mixed with TPA-100 is also different, wherein when the polyol is 3-methyl-1, 5 pentanediol, the hardness of the coating film formed is the highest and is 2H.
The data of example 1 and comparative example 1, example 2 and comparative example 2, example 3 and comparative example 3, example 41 and comparative example 4 are combined to show that: the stable aqueous polyaspartic acid ester resin cannot be obtained by only physically mixing the hydrophilic monomer with the resin without catalytic reaction.
From example 2, comparative example 5 and comparative example 6, in combination with tables two to four, it can be seen that the aqueous polyaspartic ester resin emulsion is inferior in stability, low in hardness, and inferior in water resistance and solvent resistance without adding a polyol or increasing the functionality of the aqueous resin by using a reaction of a monohydric alcohol instead of a polyol.
As can be seen from the comparison of example 6, comparative example 7 and comparative example 8, in combination with table two, the aqueous polyaspartic acid ester resin formed was not hydrophilic and could not be emulsified in water without the addition of the hydrophilic monomer MPEG.
From a comparison of example 6 with comparative example 9, in combination with Table II, it can be seen that at a hydrophilic monomer MPEG content of less than 5%, the aqueous polyaspartate resin formed is not emulsifiable in water.
As can be seen from a comparison of example 6 with comparative example 10, in combination with tables three and four, when the amount of MPEG of the hydrophilic monomer exceeds 30%, the aqueous polyaspartic acid ester resin formed is inferior in hardness, water resistance and solvent resistance.
As can be seen from a comparison of example 6 with comparative example 12, in combination with Table four, the stability, water resistance, and solvent resistance of the aqueous polyaspartic acid ester resin emulsion formed were significantly reduced when the ratio of resin to polyol was less than 1:0.2.
From a comparison of example 6 with comparative example 13, in combination with Table II, it can be seen that when the ratio of resin to polyol is greater than 1:0.5, the viscosity of the resin is large, and it is difficult to emulsify and disperse.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (9)
1. An aqueous polyaspartic acid ester resin is characterized by comprising polyaspartic acid ester resin, polyalcohol, hydrophilic monomer and ester catalyst; the molar ratio of the polyaspartic acid ester resin to the polyol is 1:0.2-0.5 percent, wherein the hydrophilic monomer is polyethylene glycol Monoether (MPEG), and the mass fraction of the hydrophilic monomer is 5-30 percent of the polyaspartic acid ester resin.
2. The aqueous polyaspartic acid ester resin according to claim 1, characterized in that: the polyalcohol is at least 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.
3. The aqueous polyaspartic acid ester resin according to claim 1, characterized in that: the molecular structure of the polyaspartic acid ester resin is as follows:
wherein the structure of R is at least one of the following.
4. The aqueous polyaspartic acid ester resin according to claim 1, characterized in that: the polyethylene glycol monomethyl ether is one of MPEG400, MPEG450, MPEG500, MPEG550, MPEG600, MPEG650 and MPEG 700.
5. The aqueous polyaspartic acid ester resin according to claim 1, characterized in that: the mass fraction of the hydrophilic monomer is 10% -20% of that of the water-based polyaspartic acid ester resin.
6. A method of preparing the aqueous polyaspartic acid ester resin according to any one of claims 1-5, comprising the steps of:
uniformly mixing the polyaspartic acid ester resin, the polyol and the hydrophilic monomer to obtain a mixture A, adding a titanate catalyst into the mixture A, and preparing the water-based polyaspartic acid ester resin at 100-130 ℃ and a vacuum degree of less than 1000 pa.
7. The aqueous polyaspartic acid ester resin according to claim 6, characterized in that: the mass addition amount of the titanate catalyst is 0.01% -0.02% of the mass of the polyaspartic acid ester resin.
8. The aqueous polyaspartic acid ester resin according to claim 7, wherein: the titanate catalyst is one of tetraisopropyl titanate, tetra-n-butyl titanate and tetrabutyl zirconate.
9. The aqueous polyaspartic acid ester resin according to claim 6, characterized in that: the temperature in the process of preparing the aqueous polyaspartic acid ester resin is 115-130 ℃, and the vacuum degree is less than 100pa.
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