CN111073469A - Anti-yellowing powder coating for architectural decoration - Google Patents

Anti-yellowing powder coating for architectural decoration Download PDF

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CN111073469A
CN111073469A CN201911396065.1A CN201911396065A CN111073469A CN 111073469 A CN111073469 A CN 111073469A CN 201911396065 A CN201911396065 A CN 201911396065A CN 111073469 A CN111073469 A CN 111073469A
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yellowing
parts
powder coating
architectural decoration
resistant
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王磊
江川
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention discloses a yellowing-resistant powder coating for architectural decoration, which comprises the following raw materials in parts by weight: 65-80 parts of epoxy acrylate resin, 10-15 parts of mica powder, 15-20 parts of pigment and filler, 3.5-5 parts of yellowing resistant agent, 1-2 parts of flatting agent, 3-6 parts of precipitated barium sulfate and 1-3 parts of benzoin; the epoxy acrylate resin is used as a substrate to prepare the yellowing-resistant agent with the structure of the formula m, and the yellowing-resistant agent contains a triazine ring and hindered amine double-light stable functional group in the same yellowing-resistant agent molecular structure, so that the effect of a light stabilizer can be improved, the utilization efficiency of molecules can be improved, and the epoxy acrylate resin can be coated on the surface of a building, can keep the coating layer from yellowing and powdering for a long time, and is suitable for decoration.

Description

Anti-yellowing powder coating for architectural decoration
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a yellowing-resistant powder coating for architectural decoration.
Background
The architectural decorative paint is mainly used for painting the inner wall and the outer wall of a building, and decorating ceilings and floors, including doors, windows, roofs and all wood members and metal members. In architectural coatings exposed to the external environment or sunlight, polymers in the coatings are easily oxidized and degraded along with the accumulated daily wind and sunshine, and the gloss of the coatings is reduced, the coatings fade, yellow, chalking, embrittling and the like, and finally the coatings are peeled off, so that the protection and decoration effects are lost.
In the prior art, an ultraviolet absorbent or an ultraviolet shielding agent is usually added into a coating to resist sunlight exposure, but a single ultraviolet shielding agent has limited absorption or shielding of ultraviolet light, so different types of ultraviolet shielding agents are compounded for use, but compounding is not simply and simply realized by adding various ultraviolet shielding agents together, otherwise, not only a synergistic effect but also an antagonistic effect may not be generated.
Disclosure of Invention
The invention aims to provide a yellowing-resistant powder coating for architectural decoration, which takes epoxy acrylate resin as a substrate to prepare a yellowing-resistant agent with a structure of a formula m, contains a triazine ring and a hindered amine double-light stable functional group in the same yellowing-resistant agent molecular structure, can improve the effect of a light stabilizer, improves the utilization efficiency of molecules, can permanently keep a coating from yellowing and powdering when being coated on the surface of a building, and is suitable for decoration.
The purpose of the invention can be realized by the following technical scheme:
an anti-yellowing powder coating for architectural decoration comprises the following raw materials in parts by weight: 65-80 parts of epoxy acrylate resin, 10-15 parts of mica powder, 15-20 parts of pigment and filler, 3.5-5 parts of anti-yellowing agent, 1-2 parts of flatting agent, 3-6 parts of precipitated barium sulfate and 1-3 parts of benzoin.
Furthermore, the Tg of the epoxy acrylate resin is 49-52 ℃, the number average molecular weight is 10000-14000, and the epoxy equivalent is 450-550.
Further, the preparation method of the yellowing-resistant agent specifically comprises the following steps:
firstly, adding 1mol of methyl 3-hydroxycinnamate, 1.05-1.1mol of 4-hydroxypiperidine, a catalyst and 3.5-5L of solvent xylene into a reaction kettle, introducing nitrogen to replace air in the reaction kettle, heating to 130-140 ℃ while stirring, preserving heat for ester exchange reaction for 6-8h, adding activated carbon for thermal decolorization for 3-5min after the reaction is finished, filtering while hot, and recrystallizing to obtain a raw material a;
secondly, adding 0.1mol of cyanuric chloride, 150-200ml of solvent trichloromethane and 0.25-0.35mol of anhydrous AlCl into a reaction kettle3After mixing and stirring uniformly, adding a cocatalyst and 0.21-0.22mol of the raw material a, stirring for 5h at room temperature, then heating to 55-60 ℃, keeping the temperature and stirring for 1h, continuously adding 0.10-0.11mol of the raw material a, heating to 70-75 ℃, carrying out reflux reaction for 5-7h, after the reaction is finished, carrying out rotary evaporation to remove the solvent, and carrying out column chromatography separation to obtain the yellowing-resistant agent with the structure of the formula m.
Further, in the first step, the catalyst is tin tetrachloride; the dosage of the catalyst is 10-15 mmol.
Further, in the first step, the recrystallization is carried out by using a 30% DMF diethyl ether solution.
Further, in the second step, the cocatalyst is BF3The amount of the cocatalyst added was 0.1 mol.
Further, in the second step, the chromatographic solution used for column chromatography is petroleum ether: dichloromethane: ethyl acetate 10:2: 3.
Further, the leveling agent is a powder leveling agent RB 505.
Further, the preparation method of the yellowing-resistant powder coating comprises the following steps: adding the raw materials of the components into a ball mill for grinding and mixing for 10-15min, putting the mixture into a double-screw extruder for extrusion and tabletting, wherein the extrusion temperature in the first zone is 105-.
The invention has the beneficial effects that:
the invention provides a yellowing-resistant powder coating for architectural decoration, which takes epoxy acrylate resin as a substrate to prepare a yellowing-resistant agent with a structure of a formula m, takes 3-hydroxy methyl cinnamate and 4-hydroxy piperidine as raw materials, and generates an ester exchange reaction under the action of a catalyst stannic chloride to prepare a raw material a, then one equivalent of cyanuric chloride firstly generates a friedel-crafts alkylation reaction with 2 equivalents to obtain a disubstituted triazine intermediate, 1 equivalent of the raw material a is continuously added, and the reaction is continued to obtain a trisubstituted yellowing-resistant agent m;
the nitrogen atom on the triazine ring in the yellowing resistant agent m can form an intramolecular hydrogen bond with the phenolic hydroxyl group to form an intramolecular six-membered ring containing the hydrogen bond:
Figure BDA0002346353480000031
the ultraviolet light-absorbing coating has a relatively stable conjugated structure, can effectively capture free radicals generated by degradation and oxidation under ultraviolet irradiation, can generate molecular thermal motion after absorbing ultraviolet light, breaks an internal hydrogen bond, releases ultraviolet energy in the form of heat energy or emits fluorescence, phosphorescence and the like with low energy, and thus inhibits the polymer in the coating from generating oxidation reaction; in addition, a hindered amine functional mechanism in the yellowing resistant agent m is firstly oxidized into a nitroxide radical in the light stabilization process, and the nitroxide radical can capture an active free radical generated in a polymer, so that the photooxidation reaction is broken, and the purpose of light stabilization is achieved;
the anti-yellowing agent contains triazine ring and hindered amine double-light stable functional groups in the same anti-yellowing agent molecular structure, not only can improve the effect of a light stabilizer, but also can improve the utilization efficiency of molecules, can be coated on the surface of a building, can keep the coating layer from yellowing and powdering for a long time, and is suitable for decoration and use.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a reaction scheme of a starting material a according to the present invention;
FIG. 2 shows a reaction formula of the yellowing resistant agent m of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Raw material methyl 3-hydroxycinnamate: cas 66417-46-7; purchased from shanghai shao reagents ltd;
raw material 4-hydroxypiperidine, cas 5382-16-1; purchased from shanghai shao reagents ltd;
referring to fig. 1-2, the method for preparing the anti-yellowing agent includes the following steps:
adding 1mol of methyl 3-hydroxycinnamate, 1.1mol of 4-hydroxypiperidine, 12mmol of catalyst stannic chloride and 4L of solvent xylene into a reaction kettle, introducing nitrogen to replace air in the reaction kettle, heating to 135 ℃ while stirring, preserving heat to perform ester exchange reaction for 6 hours, adding activated carbon to perform thermal decolorization for 5 minutes after the reaction is finished, filtering while hot, and recrystallizing by adopting 30% of DMF (dimethyl formamide) ether solution to obtain a raw material a;
secondly, adding 0.1mol of cyanuric chloride, 200ml of trichloromethane solvent and 0.3mol of anhydrous AlCl into a reaction kettle3After being mixed and stirred evenly, 0.1mol of cocatalyst BF is added3And 0.21mol of raw material a, stirring at room temperature for 5h, then heating to 55 ℃, keeping the temperature and stirring for 1h, continuously adding 0.11mol of raw material a, heating to 70 ℃, performing reflux reaction for 5, after the reaction is finished, performing rotary evaporation to remove the solvent, and performing column chromatography separation, wherein the chromatography liquid is petroleum ether: dichloromethane: ethyl acetate is 10:2:3, namely the yellowing-resistant agent with the structure of the formula m is obtained;
the detection result is that the following substances are obtained by GC-MS: yellowing resistant agent m (C)45H48N6O9) Has a molecular weight of 816.352.
Example 2
An anti-yellowing powder coating for architectural decoration comprises the following raw materials by weight: 75g of epoxy acrylate resin, 10g of mica powder, 20g of pigment filler (titanium dioxide), 3.5g of anti-yellowing agent, 1g of leveling agent, 6g of precipitated barium sulfate and 1g of benzoin.
The Tg of the epoxy acrylate resin is 49 ℃, the number average molecular weight is 12000, and the epoxy equivalent is 457;
the leveling agent is powder leveling agent RB 505;
the preparation method of the anti-yellowing powder coating comprises the following steps:
adding the raw materials of the components into a ball mill, grinding and mixing for 10min, putting the mixture into a double-screw extruder, extruding and tabletting at the extrusion temperature of 110 ℃ in the first zone and 130 ℃ in the second zone, crushing the tablets, finely crushing and sieving to obtain the yellowing-resistant powder coating with the particle size of 10-50 microns.
Example 3
An anti-yellowing powder coating for architectural decoration comprises the following raw materials by weight: 65g of epoxy acrylate resin, 12g of mica powder, 15g of pigment filler (titanium dioxide), 4g of anti-yellowing agent, 1g of leveling agent, 3g of precipitated barium sulfate and 2g of benzoin.
The Tg of the epoxy acrylate resin is 52 ℃, the number average molecular weight is 13000, and the epoxy equivalent is 512;
the leveling agent is powder leveling agent RB 505;
the preparation method of the anti-yellowing powder coating comprises the following steps:
adding the raw materials of the components into a ball mill, grinding and mixing for 15min, putting the mixture into a double-screw extruder, extruding and tabletting at the extrusion temperature of 105 ℃ in the first zone and 125 ℃ in the second zone, crushing the tablets, finely crushing and sieving to obtain the yellowing-resistant powder coating with the particle size of 10-50 microns.
Example 4
An anti-yellowing powder coating for architectural decoration comprises the following raw materials by weight: 80g of epoxy acrylate resin, 10g of mica powder, 20g of pigment filler (titanium dioxide), 5g of yellowing resistant agent, 2g of flatting agent, 5g of precipitated barium sulfate and 3g of benzoin.
The Tg of the epoxy acrylate resin is 52 ℃, the number average molecular weight is 12600, and the epoxy equivalent is 523;
the leveling agent is powder leveling agent RB 505;
the preparation method of the anti-yellowing powder coating comprises the following steps:
adding the raw materials of the components into a ball mill, grinding and mixing for 10-15min, putting the mixture into a double-screw extruder for extrusion and tabletting, wherein the extrusion temperature in a first zone is 105 ℃ and the extrusion temperature in a second zone is 130 ℃, crushing the tablets, finely crushing and sieving to obtain the yellowing-resistant powder coating with the particle size of 10-50 microns.
Comparative example 1
The procedure of example 4 was repeated except that no yellowing resistance agent was added.
Comparative example 2
The procedure of example 4 was repeated except that the yellowing-resistant agent was replaced with the raw material a.
Comparative example 3
Example 4 was repeated except that 5g of the yellowing resistant agent was replaced with 2.5g of the raw material a and 2.5g of an ultraviolet absorber UV-1164 (component: 2- (4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl) -5-octyloxyphenol).
Yellowing resistance test
The powder coatings prepared in examples 2 to 4 and comparative examples 1 to 3 were formulated into emulsions, which were applied to cement panels, respectively, using a deuterium lamp as a light source, and the coated panels were placed under test conditions satisfying a panel temperature of (55. + -. 3 ℃ C.) and an irradiance of 0.68W/m2And in a dry (condensation-free) fluorescent ultraviolet aging machine, the whole process is kept for 7 days under continuous illumination. Taking out after the illumination is finished, comparing with a test plate which is not illuminated, and measuring the color change by using a color difference meter; the smaller the measured value, the better the yellowing resistance; the results of the measurements are shown in the following table:
TABLE 1 yellowing resistance of coatings
Figure BDA0002346353480000071
As shown in Table 1, the powder coating prepared by the invention has good yellowing resistance and scrubbing resistance, effectively protects the polymer in the coating from oxidation reaction, can maintain the architectural coating from yellowing for a long time, and can maintain the decorative performance for a long time.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims (9)

1. A yellowing-resistant powder coating for architectural decoration is characterized in that: the feed comprises the following raw materials in parts by weight: 65-80 parts of epoxy acrylate resin, 10-15 parts of mica powder, 15-20 parts of pigment and filler, 3.5-5 parts of anti-yellowing agent, 1-2 parts of flatting agent, 3-6 parts of precipitated barium sulfate and 1-3 parts of benzoin.
2. The yellowing-resistant powder coating for architectural decoration according to claim 1, wherein: the Tg of the epoxy acrylate resin is 49-52 ℃, the number average molecular weight is 10000-14000, and the epoxy equivalent is 450-550.
3. The yellowing-resistant powder coating for architectural decoration according to claim 1, wherein: the preparation method of the yellowing resistant agent specifically comprises the following steps:
firstly, adding 1mol of methyl 3-hydroxycinnamate, 1.05-1.1mol of 4-hydroxypiperidine, a catalyst and 3.5-5L of solvent xylene into a reaction kettle, introducing nitrogen to replace air in the reaction kettle, heating to 130-140 ℃ while stirring, preserving heat for ester exchange reaction for 6-8h, adding activated carbon for thermal decolorization for 3-5min after the reaction is finished, filtering while hot, and recrystallizing to obtain a raw material a;
secondly, adding 0.1mol of cyanuric chloride, 150-200ml of solvent trichloromethane and 0.25-0.35mol of anhydrous AlCl into a reaction kettle3After mixing and stirring uniformly, adding a cocatalyst and 0.21-0.22mol of the raw material a, stirring for 5h at room temperature, then heating to 55-60 ℃, keeping the temperature and stirring for 1h, continuously adding 0.10-0.11mol of the raw material a, heating to 70-75 ℃, carrying out reflux reaction for 5-7h, after the reaction is finished, carrying out rotary evaporation to remove the solvent, and carrying out column chromatography separation to obtain the yellowing-resistant agent with the structure of the formula m.
4. The yellowing-resistant powder coating for architectural decoration according to claim 3, wherein: in the first step, the catalyst is tin tetrachloride; the amount of the catalyst is 10-15 mmol.
5. The yellowing-resistant powder coating for architectural decoration according to claim 3, wherein: in the first step, the recrystallization is carried out by using a 30% DMF diethyl ether solution.
6. The yellowing-resistant powder coating for architectural decoration according to claim 3, wherein: in the second step, the cocatalyst is BF3The amount of the cocatalyst added was 0.1 mol.
7. The yellowing-resistant powder coating for architectural decoration according to claim 3, wherein: in the second step, the chromatographic solution used for column chromatography is petroleum ether: dichloromethane: ethyl acetate 10:2: 3.
8. The yellowing-resistant powder coating for architectural decoration according to claim 1, wherein: the leveling agent is powder leveling agent RB 505.
9. The yellowing-resistant powder coating for architectural decoration according to claim 1, wherein: the preparation method of the anti-yellowing powder coating comprises the following steps: adding the raw materials of the components into a ball mill for grinding and mixing for 10-15min, putting the mixture into a double-screw extruder for extrusion and tabletting, wherein the extrusion temperature in the first zone is 105-.
CN201911396065.1A 2019-12-30 2019-12-30 Anti-yellowing powder coating for architectural decoration Withdrawn CN111073469A (en)

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Application publication date: 20200428