CN115820107A - UV (ultraviolet) photocuring powder coating resin and preparation method thereof - Google Patents
UV (ultraviolet) photocuring powder coating resin and preparation method thereof Download PDFInfo
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- CN115820107A CN115820107A CN202211634918.2A CN202211634918A CN115820107A CN 115820107 A CN115820107 A CN 115820107A CN 202211634918 A CN202211634918 A CN 202211634918A CN 115820107 A CN115820107 A CN 115820107A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 51
- 238000000576 coating method Methods 0.000 title claims abstract description 51
- 239000000843 powder Substances 0.000 title claims abstract description 51
- 229920005989 resin Polymers 0.000 title claims abstract description 38
- 239000011347 resin Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 13
- 239000012948 isocyanate Substances 0.000 claims abstract description 36
- -1 isocyanate ions Chemical class 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 150000002009 diols Chemical class 0.000 claims abstract description 16
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 4
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 15
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 5
- DDPRYTUJYNYJKV-UHFFFAOYSA-N 1,4-diethylpiperazine Chemical compound CCN1CCN(CC)CC1 DDPRYTUJYNYJKV-UHFFFAOYSA-N 0.000 claims description 5
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 5
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 5
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 5
- 238000005829 trimerization reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 4
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 3
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-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
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 5
- 238000003848 UV Light-Curing Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- GPASWZHHWPVSRG-UHFFFAOYSA-N 2,5-dimethylbenzene-1,4-diol Chemical compound CC1=CC(O)=C(C)C=C1O GPASWZHHWPVSRG-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a UV light-cured powder coating resin and a preparation method thereof, wherein the method comprises the following steps of: step 1: mixing 35-45 parts of first isocyanate, 10-15 parts of low molecular weight diol, 0.01-0.05 part of catalyst and 0.05-0.1 part of polymerization inhibitor together, stirring and reacting at 80-100 ℃ until the mass concentration of isocyanate ions reaches 12-16%, and cooling; and 2, step 2: when the temperature reaches below 70 ℃, adding 15-25 parts of hydroxyl acrylate until the mass concentration of isocyanate ions reaches 3-4%, and starting to heat; and 3, step 3: when the temperature reaches above 90 ℃, adding 10-15 parts of low molecular weight diol until the mass concentration of the isocyanate ions is less than 0.05%; and 4: and (3) adding 3-5 parts of photoinitiator into the system obtained in the step (3) to disperse for 30min until the mixture is uniform, and discharging, cooling and crushing to obtain the UV photocuring powder coating resin. Can prepare UV photo-curing powder coating resin with high hardness, low Tg and high gloss.
Description
Technical Field
The invention relates to the field of UV (ultraviolet) photocureable powder coating, in particular to UV photocureable powder coating resin and a preparation method thereof.
Background
The traditional powder coating adopts a thermosetting mode, namely melting, leveling and curing at a high temperature of 180-200 ℃, so as to realize surface coating of a coated device. Due to the high curing temperature, the energy consumption required for curing is high and can only be applied to non-heat-sensitive substrates.
With the development of social economy and the improvement of environmental awareness, the coating industry requires the realization of oil-to-powder, namely the conversion of oil paint into powder paint. But for heat sensitive substrates, conditions for high temperature curing are not applicable. The UV light curing can realize melting leveling at a lower temperature, such as 90-110 ℃, and then the curing is carried out under the UV light, so that the powder coating of heat-sensitive substrates, such as solid wood products, plastic products, metal alloys, paper products and the like is realized, and the application range of the powder coating is widened.
However, the existing UV light-cured powder coating resin has the problem of poor adhesion due to the mismatching of the UV light-cured powder coating and a substrate.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a UV photocuring powder coating resin and a preparation method thereof, which have the characteristics of high hardness, low Tg, high gloss and UV photocuring capability and further solve the technical problems in the prior art.
The purpose of the invention is realized by the following technical scheme:
a preparation method of UV light-cured powder coating resin comprises the following steps:
step 1: mixing 35-45 parts by mass of first isocyanate, 10-15 parts by mass of small molecular weight diol, 0.01-0.05 part by mass of catalyst and 0.05-0.1 part by mass of polymerization inhibitor together, stirring and reacting at 80-100 ℃, and cooling when the mass concentration of isocyanate ions reaches 12-16%;
step 2: adding 15-25 parts by mass of hydroxyl acrylate when the temperature reaches below 70 ℃, and starting to heat when the mass concentration of isocyanate ions reaches 3-4%;
and step 3: when the temperature reaches above 90 ℃, adding 10-15 parts by mass of small molecular weight diol until the mass concentration of the isocyanate ions is less than 0.05%;
and 4, step 4: and 3-5 parts by mass of a photoinitiator is added into the system in the step 3 and dispersed for 30min until the mixture is uniform, and finally, the UV photocuring powder coating resin is prepared after discharging, cooling and crushing.
Preferably, in the above method, the water contents of the first type of isocyanate, the small molecular weight diol, the catalyst, the polymerization inhibitor, the hydroxy acrylate and the photoinitiator are all less than 500ppm.
Preferably, in the above method, the first type of isocyanate is: at least one of isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and 4,4' -dicyclohexylmethane diisocyanate.
Preferably, in the above method, the small molecular weight diol is: at least one of neopentyl glycol, methyl propylene glycol and 1, 4-butanediol.
Preferably, in the above method, the hydroxy acrylate is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and pentaerythritol triacrylate.
Preferably, in the above method, the catalyst is: at least one of bis dimethylamino ethyl ether, pentamethyl diethylenetriamine, dimethyl cyclohexylamine, dibutyltin dilaurate, organic bismuth, triazine trimerization catalyst, solid amine, N-ethyl morpholine, N-methyl morpholine and N, N' -diethyl piperazine.
Preferably, in the above method, the catalyst is: at least one of bis-dimethylamino ethyl ether, pentamethyl diethylenetriamine, dimethyl cyclohexylamine, dibutyltin dilaurate, organic bismuth, triazine trimerization catalyst, solid amine, N-ethyl morpholine, N-methyl morpholine and N, N' -diethyl piperazine.
Preferably, in the above method, the photoinitiator is: at least one of 1-hydroxy-cyclohexylbenzophenone, benzophenone, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide.
The invention discloses UV (ultraviolet) light-cured powder coating resin which is prepared by the preparation method.
Compared with the prior art, the UV light curing powder coating resin and the preparation method thereof have the beneficial effects that:
the first-class isocyanate, the micromolecular diol, the catalyst, the polymerization inhibitor, the hydroxyl acrylate and the photoinitiator in a specific proportion are used as main raw materials, stirring and reaction are carried out according to the set reaction temperature and reaction time, and the content of each component can be better controlled by controlling each reaction step through the mass concentration of isocyanate ions, so that the UV photocuring powder coating resin with high hardness, low Tg, high gloss and UV photocuring performance is synthesized.
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described in combination with the specific content of the invention; it is to be understood that the described embodiments are merely exemplary of the invention, and are not intended to limit the invention to the particular forms disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The terms that may be used herein are first described as follows:
the term "and/or" means that either or both can be achieved, for example, X and/or Y means that both cases include "X" or "Y" as well as three cases including "X and Y".
The terms "comprising," "including," "containing," "having," or other similar terms of meaning should be construed as non-exclusive inclusions. For example: including a feature (e.g., material, component, ingredient, carrier, formulation, material, dimension, part, component, mechanism, device, process, procedure, method, reaction condition, processing condition, parameter, algorithm, signal, data, product, or article of manufacture), is to be construed as including not only the particular feature explicitly listed but also other features not explicitly listed as such which are known in the art.
The term "consisting of 823070 \8230composition" means to exclude any technical characteristic elements not explicitly listed. If used in a claim, the term shall render the claim closed except for the inclusion of the technical features that are expressly listed except for the conventional impurities associated therewith. If the term occurs in only one clause of the claims, it is defined only to the elements explicitly recited in that clause, and elements recited in other clauses are not excluded from the overall claims.
The term "parts by mass" is intended to indicate a mass ratio relationship between a plurality of components, for example: if X component is X parts by mass and Y component is Y parts by mass, the mass ratio of the X component to the Y component is X: Y;1 part by mass may represent any mass, for example: 1 part by mass may be 1kg or 3.1415926 kg. The sum of the parts by mass of all the components is not necessarily 100 parts, and may be more than 100 parts, less than 100 parts, or equal to 100 parts. Parts, ratios and percentages described herein are by mass unless otherwise indicated.
When concentrations, temperatures, pressures, dimensions, or other parameters are expressed as ranges of values, the ranges of values should be understood to specifically disclose all ranges formed by any pair of upper values, lower values, or preferred values within the range, regardless of whether the ranges are explicitly recited; for example, if a numerical range of "2 to 8" is recited, then that numerical range should be interpreted to include ranges such as "2 to 7," "2 to 6," "5 to 7," "3 to 4 and 6 to 7," "3 to 5 and 7," "2 and 5 to 7," and the like. Unless otherwise indicated, the numerical ranges recited herein include both the endpoints thereof and all integers and fractions within the numerical range.
The UV light-curable powder coating resin and the preparation method thereof provided by the present invention are described in detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to the person skilled in the art. Those not specifically mentioned in the examples of the present invention were carried out according to the conventional conditions in the art or conditions suggested by the manufacturer. The reagents or instruments used in the examples of the present invention are not specified by manufacturers, and are all conventional products available by commercial purchase.
The embodiment of the invention provides a preparation method of UV (ultraviolet) photocureable powder coating resin, which comprises the following steps:
step 1: mixing 35-45 parts by mass of first isocyanate, 10-15 parts by mass of low molecular weight diol, 0.01-0.05 part by mass of catalyst and 0.05-0.1 part by mass of polymerization inhibitor together, stirring at 80-100 ℃ for reaction until the mass concentration of isocyanate ions reaches 12-16%, and cooling;
step 2: when the temperature reaches below 70 ℃, adding 15-25 parts by mass of hydroxyl acrylate until the mass concentration of isocyanate ions reaches 3-4%, and starting to heat;
and step 3: when the temperature reaches above 90 ℃, adding 10-15 parts by mass of low molecular weight diol until the mass concentration of isocyanate ions is less than 0.05%;
and 4, step 4: and 3-5 parts by mass of photoinitiator is added and dispersed for 30min to be uniform, and finally, the UV photocuring powder coating resin is prepared through material discharging, cooling and crushing.
Specifically, the preparation method of the UV light curable powder coating resin includes the following embodiments:
(1) In the raw materials, the water contents of the hydroxyl acrylate, the first type isocyanate, the small molecular weight diol, the catalyst, the polymerization inhibitor and the photoinitiator are all lower than 500ppm, so that the influence of the alcohol raw material on the reaction between water and the isocyanate due to the fact that the alcohol raw material is easy to absorb water can be reduced.
(2) The first type isocyanate is at least one of isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.
(3) The low molecular weight diol is at least one of neopentyl glycol, methyl propylene glycol and 1, 4-butanediol.
(4) The hydroxyl acrylate is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, dipentaerythritol pentaacrylate and pentaerythritol triacrylate.
(5) The catalyst is at least one of bis dimethylamino ethyl ether, pentamethyl diethylenetriamine, dimethyl cyclohexylamine, dibutyltin dilaurate, organic bismuth, triazine trimerization catalyst, solid amine, N-ethyl morpholine, N-methyl morpholine and N, N' -diethyl piperazine.
(6) The polymerization inhibitor is at least one of p-hydroxyanisole, hydroquinone and 2, 5-dimethyl hydroquinone;
(7) The photoinitiator is at least one of 1-hydroxy-cyclohexyl benzophenone, benzophenone and diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide.
In summary, the preparation method of the embodiment of the invention takes the hydroxy acrylate, the first type of isocyanate, the small molecular diol, the catalyst, the polymerization inhibitor and the photoinitiator in a specific proportion as main raw materials, and the contents of the components can be better controlled by taking the specific reaction temperature, the specific reaction time and the specific mass concentration of the isocyanate ions as termination conditions of each step, so that the synthesized UV light-cured powder coating resin with high hardness, low Tg, high gloss and UV light curing performance is synthesized.
The embodiment of the invention also provides the UV photocuring powder coating resin prepared by the method.
In order to more clearly show the technical solutions and technical effects provided by the present invention, the following detailed description is provided for the UV light-curable powder coating resin and the preparation method thereof provided by the embodiments of the present invention with specific examples.
Example 1
The embodiment provides a UV light-cured powder coating resin, and a preparation method thereof comprises the following steps (by mass):
step 1: mixing 40 parts of isophorone diisocyanate, 15 parts of methyl propylene glycol, 0.03 part of dibutyltin dilaurate and 0.03 part of hydroquinone together, stirring at 90 ℃ for reaction until the mass concentration of isocyanate ions reaches 13%, and starting to cool;
step 2: adding 15 parts of hydroxyethyl acrylate when the temperature reaches 70 ℃ until the mass concentration of isocyanate ions reaches 3.4%, and starting to heat;
and step 3: when the temperature reaches 90 ℃, 15 parts of neopentyl glycol is added until the mass concentration of isocyanate ions is less than 0.05%;
and 4, step 4: 3.5 parts of 1-hydroxy-cyclohexyl benzophenone is added and dispersed for 30min to be uniform, and finally, the UV light-cured powder coating resin is prepared after discharging, cooling and crushing.
Example 2
This example provides a UV light curable powder coating resin, which is prepared by the following steps (parts by mass):
step 1: mixing 40 parts of isophorone diisocyanate, 15 parts of neopentyl glycol, 0.03 part of dibutyltin dilaurate and 0.03 part of hydroquinone together, stirring at 90 ℃ for reaction until the mass concentration of isocyanate ions reaches 14%, and cooling;
step 2: adding 15 parts of hydroxyethyl acrylate when the temperature reaches 70 ℃ until the mass concentration of isocyanate ions reaches 3.8%, and starting to heat;
and step 3: when the temperature reaches 90 ℃, 13 parts of methyl propylene glycol is added until the mass concentration of isocyanate ions is less than 0.05 percent;
and 4, step 4: 3.5 parts of 1-hydroxy-cyclohexyl benzophenone is added and dispersed for 30min to be uniform, and finally, the UV light-cured powder coating resin is prepared after discharging, cooling and crushing.
Example 3
This example provides a UV light curable powder coating resin, which is prepared by the following steps (parts by mass):
step 1: mixing 40 parts of isophorone diisocyanate, 15 parts of 1, 4-butanediol, 0.03 part of dibutyltin dilaurate and 0.03 part of hydroquinone together, stirring at 90 ℃ for reaction until the mass concentration of isocyanate ions reaches 14%, and starting to reduce the temperature;
step 2: adding 15 parts of hydroxyethyl acrylate when the temperature reaches 70 ℃ until the mass concentration of isocyanate ions reaches 3.2%, and starting to heat;
and step 3: when the temperature reaches 90 ℃, 15 parts of neopentyl glycol is added until the mass concentration of isocyanate ions is less than 0.05%;
and 4, step 4: 3.5 parts of 1-hydroxy-cyclohexyl benzophenone is added and dispersed for 30min to be uniform, and finally, the UV light-cured powder coating resin is prepared after discharging, cooling and crushing.
Performance detection
Comparative tests were carried out on the UV-light-curable powder coating resins obtained in examples 1 to 3 according to the invention and on conventional heat-curable powder coating resins as comparative examples:
the detection method comprises the following steps: the products prepared in the examples are crushed by a pulverizer, finally screened by a screening machine, and added with the same proportion of additives and pigments and fillers, so as to prepare the UV light-cured powder coating and the heat-cured powder coating. The UV light-cured powder coating and the thermosetting powder coating are electrostatically sprayed on the galvanized steel sheet, and the UV cured powder coating is baked for 10min at 100 ℃ for UV light curing; the final test results are shown in the following table 1 for the thermosetting powder coating after baking and curing at 180 ℃ for 15 min:
table 1 results of performance test of examples and comparative examples
As can be seen from table 1 above: the UV photocuring powder coating resin prepared in the embodiments 1 to 3 has extremely low melting and curing temperature and low viscosity, can be melted and leveled at a low temperature (namely 90-110 ℃), greatly saves curing time, has hardness, glossiness and adhesive force which are not inferior to those of a comparative case, and can better reduce energy consumption.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (9)
1. A preparation method of UV light-cured powder coating resin is characterized by comprising the following steps:
step 1: mixing 35-45 parts by mass of first isocyanate, 10-15 parts by mass of small molecular weight diol, 0.01-0.05 part by mass of catalyst and 0.05-0.1 part by mass of polymerization inhibitor together, stirring and reacting at 80-100 ℃, and cooling when the mass concentration of isocyanate ions reaches 12-16%;
step 2: adding 15-25 parts by mass of hydroxyl acrylate when the temperature reaches below 70 ℃, and starting to heat when the mass concentration of isocyanate ions reaches 3-4%;
and step 3: when the temperature reaches above 90 ℃, adding 10-15 parts by mass of small molecular weight diol until the mass concentration of the isocyanate ions is less than 0.05%;
and 4, step 4: and 3-5 parts by mass of a photoinitiator is added into the system in the step 3 and dispersed for 30min until the mixture is uniform, and finally, the UV photocuring powder coating resin is prepared after discharging, cooling and crushing.
2. The method of claim 1, wherein the water content of the first isocyanate, the low molecular weight diol, the catalyst, the polymerization inhibitor, the hydroxyacrylate, and the photoinitiator is less than 500ppm.
3. Process for the preparation of a UV light curable powder coating resin according to claim 1 or 2, characterized in that the first type of isocyanate is: at least one of isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and 4,4' -dicyclohexylmethane diisocyanate.
4. The method of preparing a UV light curable powder coating resin according to claim 1 or 2 wherein the small molecular weight diol is: at least one of neopentyl glycol, methyl propylene glycol and 1, 4-butanediol.
5. Method for the preparation of a UV light curable powder coating resin according to claim 1 or 2, characterized in that the hydroxy acrylate is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate.
6. The method of preparing a UV light curable powder coating resin according to claim 1 or 2, wherein the catalyst is: at least one of bis dimethylamino ethyl ether, pentamethyl diethylenetriamine, dimethyl cyclohexylamine, dibutyltin dilaurate, organic bismuth, triazine trimerization catalyst, solid amine, N-ethyl morpholine, N-methyl morpholine and N, N' -diethyl piperazine.
7. The method of preparing a UV light curable powder coating resin according to claim 1 or 2, wherein the catalyst is: at least one of bis dimethylamino ethyl ether, pentamethyl diethylenetriamine, dimethyl cyclohexylamine, dibutyltin dilaurate, organic bismuth, triazine trimerization catalyst, solid amine, N-ethyl morpholine, N-methyl morpholine and N, N' -diethyl piperazine.
8. The method for preparing a UV light curable powder coating resin according to claim 1 or 2, wherein the photoinitiator is: at least one of 1-hydroxy-cyclohexylbenzophenone, benzophenone, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide.
9. A UV light curable powder coating resin obtained by the production method according to any one of claims 1 to 8.
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