CN114196292A - Water-based LED photocureable coating and coating method - Google Patents
Water-based LED photocureable coating and coating method Download PDFInfo
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- CN114196292A CN114196292A CN202111591432.0A CN202111591432A CN114196292A CN 114196292 A CN114196292 A CN 114196292A CN 202111591432 A CN202111591432 A CN 202111591432A CN 114196292 A CN114196292 A CN 114196292A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6503—Five-membered rings
- C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
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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
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Epoxy Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a water-based LED photocureable coating and a coating method, belonging to the technical field of photocureable coating. The invention provides a coating method of a water-based LED photocureable coating, which comprises the following steps: coating a water-based LED photocuring primer coating on the surface of a substrate, and sequentially carrying out first UVLED photocuring and first drying to obtain a primer film layer; and coating a water-based LED photocuring finish paint on the surface of the primer film layer, and sequentially carrying out second UVLED photocuring and second drying to obtain the water-based LED photocuring coating. The ionic liquid is introduced into the water-based LED photocureable coating, so that the water solubility of the polymer for the photocureable coating and the photoinitiator for the water-based LED photocureable coating can be improved, the water-based LED photocureable coating obtained after coating has good hardness, adhesion resistance and solvent resistance, and the VOC release amount is 70-110 mg/mL.
Description
Technical Field
The invention relates to the technical field of photo-curing coating, in particular to a water-based LED photo-curing coating and a coating method.
Background
With the rapid development of national economy, China has become the first major coating producing country and consuming country in the world, but the coating consuming structure of China is unreasonable, and the highly-polluted solvent-based traditional coating occupies a considerable proportion, and the traditional coating takes an organic solvent as a diluent, so that a lot of volatile organic solvents (VOC) are released, and the natural environment on which people live is greatly destroyed. According to statistics, the VOC released by coating processing and production is second to the emission of automobile exhaust and is positioned at the second place of VOV pollution. With the increasing demand for environmental protection, the research on new environmental-friendly coatings such as water-based coatings without organic solvents has become a hot spot. At present, water-based paint is sold on the market, but the performance of the water-based paint is different from that of oil-soluble paint, but the trend that the water-based paint gradually replaces oil-based paint is out of gear, and the development of novel high-performance water-based paint research has practical application value.
The photocuring technology is a novel surface treatment technology of materials, and refers to a process in which monomers or oligomers can be polymerized and cross-linked under the irradiation of visible light/ultraviolet light to realize curing. The light curing technology has the characteristics of high efficiency, high quality, environmental protection, energy conservation and controllability. The resin used for the water-soluble light-cured coating needs to meet the requirement of water solubility, but the water solubility of the existing coating resin is often poor, so that the selectable range of the water-soluble light-cured resin is very limited.
Disclosure of Invention
In view of the above, the present invention aims to provide a water-based LED photocurable coating and a coating method. The ionic liquid is introduced into the water-based LED photocureable coating, so that the water solubility of the polymer for the photocureable coating and the photoinitiator for the water-based LED photocureable coating can be improved.
The invention provides application of ionic liquid in preparation of a water-based LED photocureable coating. According to the invention, an ionic liquid group is introduced into the structure of the polymer for the water-based LED photocureable coating and/or the photoinitiator for the water-based LED photocureable coating, so that an epoxy resin-based polymer with a structure shown in a formula A, a polyurethane-based polymer with a structure shown in a formula B and a photoinitiator with a structure shown in a formula C are obtained. According to the invention, ionic liquid groups are introduced into the epoxy resin-based polymer and the polyurethane-based polymer, so that the water solubility of the epoxy resin-based polymer and the polyurethane-based polymer can be improved, and the epoxy resin-based polymer and the polyurethane-based polymer are respectively used as the components of the primer and the finish of the waterborne LED photocureable coating, so that the hardness, the adhesion resistance and the solvent resistance of the coating can be effectively improved; according to the invention, ionic liquid groups are introduced into the structure of the photoinitiator, so that the water solubility of the photoinitiator can be improved; meanwhile, the initiator can be used as a polymerizable component to participate in curing in the LED photocuring process, the migration resistance is high, and the safety of the water-based LED photocuring coating can be effectively improved. The results of the examples show that the waterborne LED photocuring coating prepared by using the epoxy resin-based polymer, the polyurethane-based polymer and the water-soluble photoinitiator as raw materials has good hardness, adhesion resistance and solvent resistance, and the VOC release amount is 70-110 mg/mL.
The invention provides a coating method of a water-based LED photocureable coating, which comprises the following steps: coating a water-based LED photocuring primer coating on the surface of a substrate, and sequentially carrying out first UVLED photocuring and first drying to obtain a primer film layer; and coating a water-based LED photocuring finish paint on the surface of the primer film layer, and sequentially carrying out second UVLED photocuring and second drying to obtain the water-based LED photocuring coating. The water-based LED photocureable coating obtained after coating has good hardness, adhesion resistance and solvent resistance.
Drawings
FIG. 1 shows a coating process of a water-based LED photocureable coating.
Detailed Description
The invention provides an application of an ionic liquid in preparation of a water-based LED photocureable coating, which comprises preparation of a polymer for the water-based LED photocureable coating and/or a photoinitiator for the water-based LED photocureable coating.
The ionic liquid has a structure represented by formula W:
in the formula W, m is 1-10, preferably 2-8, and more preferably 4-6; x is hydroxyl or halogen, and the halogen is preferably Br, Cl or I. In formula W, the dotted line represents the attachment site.
The invention provides an epoxy resin-based polymer, which has a structure shown in a formula I:
in the formula A, R is independently CyH2y+1Y is 0 to 20, preferably 2 to 15, and more preferably 5 to 10;
ar is independently
m is 1 to 10, preferably 2 to 8, and more preferably 4 to 6.
n is 2 to 10, preferably 4 to 8, and more preferably 5 to 6.
As a specific embodiment of the present invention, the structural formula of the epoxy resin based polymer preferably has a structure represented by formula AI, formula AII, formula AIII or formula AIV:
the invention provides a preparation method of the epoxy resin-based polymer, which comprises the following steps:
carrying out substitution reaction on the epoxy resin with the structure shown in the formula A-1 and the ionic liquid with the structure shown in the formula b to obtain a compound with the structure shown in the formula c;
carrying out ring-opening addition reaction on a compound with a structure shown as a formula A-3 and a compound with a structure shown as a formula A-4 to obtain a compound with a structure shown as a formula A-5;
carrying out substitution reaction on a compound with a structure shown as a formula A-5 and a compound with a structure shown as a formula A-6 to obtain an epoxy resin-based polymer with a structure shown as a formula A;
in the invention, the epoxy resin with the structure shown in the formula A-1 and the ionic liquid with the structure shown in the formula A-2 are subjected to substitution reaction to obtain the compound with the structure shown in the formula A-3.
In the present invention, the substitution reaction is preferably carried out in an organic solvent, and the organic solvent is preferably dichloromethane, chloroform, toluene, xylene, chlorobenzene. In the present invention, the substitution reaction is preferably carried out in the presence of a catalyst, which is preferably potassium carbonate. In the invention, the temperature of the substitution reaction is preferably room temperature to 60 ℃, and the time is preferably 2 to 20 hours, and more preferably 5 to 15 hours.
After the substitution reaction, the present invention preferably sequentially washes, dries, and removes the organic solvent from the resulting substitution reaction product.
After the compound with the structure shown in the formula A-3 is obtained, the compound with the structure shown in the formula A-3 and the compound with the structure shown in the formula A-4 are subjected to ring-opening addition reaction to obtain the compound with the structure shown in the formula A-5. In the invention, the temperature of the ring-opening addition reaction is preferably room temperature to 100 ℃, and the time is preferably 10 to 36 hours, and more preferably 20 to 30 hours.
After the compound with the structure shown in the formula A-5 is obtained, the compound with the structure shown in the formula A-5 and the compound with the structure shown in the formula A-6 are subjected to substitution reaction to obtain the epoxy resin-based polymer with the structure shown in the formula A. In the present invention, the substitution reaction is preferably carried out in an organic solvent, and the organic solvent is preferably dichloromethane. In the invention, the temperature of the substitution reaction is preferably room temperature, and the time is preferably 0.5-5 h, and more preferably 2 h.
The invention provides an application of the epoxy resin-based polymer as a polymer for a water-based LED photocuring primer coating.
The invention provides a polyurethane-based polymer, which has a structure shown in a formula B:
in the formula B, R is independently CyH2y+1Y is 0 to 20, preferably 2 to 15, and more preferably 5 to 10.
A is aryl or- (CH)2)kK is 2 to 10, preferably 4 to 8, and more preferably 5 to 6.
In the present invention, the preferred aryl structure is as follows:
m is 1 to 10, preferably 2 to 8, and more preferably 4 to 6.
n is 2 to 10, preferably 4 to 8, and more preferably 5 to 6.
As a specific embodiment of the present invention, the polyurethane-based polymer has a structure represented by formula BI or formula BII:
the invention provides a preparation method of the polyurethane-based polymer, which comprises the following steps:
carrying out nucleophilic addition reaction on a compound with a structure shown as a formula B-1 and a compound with a structure shown as a formula B-2 to obtain a compound with a structure shown as a formula B-3;
carrying out nucleophilic addition reaction on a compound with a structure shown as a formula B-3 and a compound with a structure shown as a formula B-4 to obtain a compound with a structure shown as a formula B-5;
carrying out substitution reaction on a compound with a structure shown as a formula B-5 and ionic liquid with a structure shown as a formula B-6 to obtain a polyurethane-based polymer with a structure shown as a formula B;
in the present invention, a compound having a structure represented by formula B-1 and a compound having a structure represented by formula B-2 are subjected to a nucleophilic addition reaction to obtain a compound having a structure represented by formula B-3. In the present invention, the nucleophilic addition reaction is preferably carried out in an organic solvent, which is preferably acetonitrile. In the invention, the reaction temperature is preferably room temperature to 80 ℃, and the reaction time is preferably 0.5-10 h, and more preferably 2-5 h.
After the compound with the structure shown in the formula B-3 is obtained, the compound with the structure shown in the formula B-3 and the compound with the structure shown in the formula B-4 are subjected to nucleophilic addition reaction to obtain the compound with the structure shown in the formula B-5. In the present invention, the reaction is preferably carried out in an organic solvent, which is preferably acetonitrile. In the invention, the reaction temperature is preferably room temperature to 80 ℃, and the reaction time is preferably 0.5-10 hours, and more preferably 2-5 hours.
After the compound with the structure shown in the formula B-5 is obtained, the compound with the structure shown in the formula B-5 and the ionic liquid with the structure shown in the formula B-6 are subjected to substitution reaction to obtain the polyurethane-based polymer with the structure shown in the formula B. In the invention, the substitution reaction is preferably carried out in an organic solvent, and the organic solvent is preferably one or more of dichloromethane, chloroform, toluene, xylene and chlorobenzene; in the invention, the temperature of the substitution reaction is preferably room temperature to 100 ℃, and the time is preferably 10-36 h, and more preferably 24 h.
The invention provides an application of the polyurethane polymer as a polymer for a water-based LED photocuring finish paint.
The invention provides a water-soluble photoinitiator, which has a structure shown in a formula C:
in the formula C, R is independently CyH2y+1Y is 0 to 20, preferably 2 to 15, and more preferably 5 to 10.
m is 0 to 5, preferably 1 to 4, and more preferably 2 to 3.
As a specific embodiment of the present invention, the water-soluble photoinitiator has a structure represented by formula CI or formula CII:
the invention provides a preparation method of the water-soluble photoinitiator, which comprises the following steps:
carrying out substitution reaction on a compound with a structure shown as a formula C-1 and a compound with a structure shown as a formula C-2 to obtain a compound with a structure shown as a formula C-3;
carrying out substitution reaction on a compound with a structure shown as a formula C-3 and a compound with a structure shown as a formula C-4 to obtain a compound with a structure shown as a formula C-5;
carrying out substitution reaction on a compound with a structure shown as a formula C-5 and ionic liquid with a structure shown as a formula C-6 to obtain a photocatalyst with a structure shown as a formula C;
in the present invention, a compound having a structure represented by formula C-1 and a compound having a structure represented by formula C-2 are subjected to a substitution reaction to obtain a compound having a structure represented by formula C-3. In the present invention, the substitution reaction is preferably carried out in an organic solvent, preferably dichloromethane; in the present invention, the temperature of the substitution reaction is preferably room temperature, and the time is preferably 2 hours.
After the compound with the structure shown as C-3 is obtained, the compound with the structure shown as the formula C-3 and the compound with the structure shown as the formula C-4 are subjected to substitution reaction to obtain the compound with the structure shown as the formula C-5. In the present invention, the substitution reaction is preferably carried out in an organic solvent, and the organic solvent is preferably toluene. In the present invention, the temperature of the substitution reaction is preferably 100 ℃ and the time is preferably 6 hours.
After the compound with the structure shown in the formula C-5 is obtained, the compound with the structure shown in the formula C-5 and the ionic liquid with the structure shown in the formula C-6 are subjected to substitution reaction to obtain the photocatalyst with the structure shown in the formula C. In the present invention, the substitution reaction is preferably carried out in an organic solvent, and the organic solvent is preferably dichloromethane. In the present invention, the substitution reaction is preferably carried out in the presence of a catalyst, which is preferably potassium carbonate. In the invention, the temperature of the substitution reaction is preferably room temperature to 80 ℃, and the time is preferably 10-36 h, and more preferably 24 h.
The invention provides an application of the water-soluble photoinitiator as a photoinitiator for a water-based LED photocureable coating.
The invention provides a water-based LED photocuring primer coating which comprises the following components in percentage by mass:
the epoxy resin-based polymer is the epoxy resin-based polymer or the epoxy resin-based polymer prepared by the preparation method;
the water-soluble photoinitiator is the water-soluble photoinitiator or the water-soluble photoinitiator prepared by the preparation method.
The water-based LED photocuring primer coating provided by the invention comprises 30-90% of epoxy resin-based polymer by mass, preferably 40-80%, and more preferably 50-70%. In the present invention, the epoxy resin agent polymer has good water solubility.
The water-based LED photocuring primer coating provided by the invention comprises 0.1-10% of water-soluble photoinitiator by mass, preferably 0.5-8%, more preferably 1-6%, and further preferably 2-4%. In the invention, the water-soluble photoinitiator has good water solubility, can be used as a polymerizable component to participate in curing, has high migration resistance, and can effectively improve the safety of the water-based LED photocureable coating.
The water-based LED photocuring primer coating provided by the invention comprises 0.5-20% of inorganic filler by mass, preferably 1-15%, and more preferably 5-10%. In the invention, the inorganic filler is preferably one or more of calcium carbonate, barium sulfate, talcum powder, kaolin, porous quartz powder, white carbon black, mica powder, wollastonite, bentonite and attapulgite. In the present invention, the particle size of the inorganic filler is preferably 100 to 500nm, and more preferably 200 to 400 nm.
The water-based LED photocuring primer coating provided by the invention comprises 0.05-2% of defoaming agent by mass, preferably 0.1-1.5% and more preferably 0.5-1%. In the invention, the defoaming agent is preferably one or more of BYK-011, BYK-012 and TEGO-810.
The water-based LED photocuring primer coating provided by the invention comprises 0.5-10% of organic active solvent by mass percentage, preferably 1-8%, more preferably 2-6%, and more preferably 3-5%. In the invention, the organic active solvent is preferably one or more of dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether and ethanol. In the invention, the organic active solvent is used for improving the technological performance of the coating so as to facilitate the construction of the coating in the using process.
The water-based LED photocuring primer coating provided by the invention comprises 0.5-10% of thickening agent by mass, preferably 1-8%, more preferably 2-6%, and more preferably 3-5%. In the invention, the thickener is preferably one or more of hydroxyethyl cellulose, ethyl acrylate, bentonite and ViscoPlus 3000.
The water-based LED photocuring primer coating provided by the invention comprises the balance of water in percentage by mass.
The preparation method of the water-based LED photocuring primer coating has no special requirements, and the components are uniformly stirred.
The invention provides a water-based LED photocuring finish paint which comprises the following components in percentage by mass:
the polyurethane-based polymer is the polyurethane-based polymer or the polyurethane-based polymer prepared by the preparation method;
the water-soluble photoinitiator is the water-soluble photoinitiator or the water-soluble photoinitiator prepared by the preparation method.
The water-based LED photocuring finish paint provided by the invention comprises 40-80% of polyurethane-based polymer by mass percentage, and preferably 60%.
The water-based LED photocuring finish paint provided by the invention comprises 0.1-5% of water-soluble photoinitiator by mass percentage, and preferably 1.5%.
The water-based LED photocuring finish paint provided by the invention comprises 0.1-5% of defoaming agent by mass percentage, and preferably 0.5%. In the invention, the selectable types of the defoaming agent are the same as those of the defoaming agent in the water-based LED photocuring primer coating, and the details are not repeated.
The water-based LED photocuring finish paint provided by the invention comprises 1-10% of organic active solvent by mass percentage, and preferably 5%. In the present invention, the selectable types of the organic active solvent are the same as those of the organic active solvent in the water-based LED photocuring primer coating, and are not described herein again.
The water-based LED photocuring finish paint provided by the invention comprises 1-10% of thickening agent by mass percentage, and preferably 3%. In the present invention, the selectable types of the thickening agent are the same as those of the thickening agent in the water-based LED photocuring primer coating, and are not described in detail herein.
The water-based LED photocuring finish paint provided by the invention also comprises the balance of water in percentage by mass.
The invention provides a coating method of a water-based LED photocureable coating, which comprises the following steps:
coating a water-based LED photocuring primer coating on the surface of a substrate, and sequentially carrying out first UVLED photocuring and first drying to obtain a primer film layer;
and coating a water-based LED photocuring finish paint on the surface of the primer film layer, and sequentially carrying out second UVLED photocuring and second drying to obtain the water-based LED photocuring coating.
According to the invention, the surface of a substrate is coated with a water-based LED photocuring primer coating, and a first UVLED photocuring and first drying are sequentially carried out to obtain a primer film layer. In the present invention, the coating is preferably performed by spray coating. The present invention does not require any particular means for spraying, and can be applied by spraying means known to those skilled in the art. In the invention, the number of coating times is preferably 1-3, and the coating thickness of the water-based LED photocuring primer coating is preferably 40-150 μm, and more preferably 60-100 μm.
In the invention, the temperature of the first UVLED light curing is preferably room temperature, and the time is preferably 0.5-30 min, and more preferably 5-20 min. In the invention, the wavelength of the first UVLED light curing is preferably 320-390 nm.
In the present invention, the first drying preferably includes medium-wave infrared drying and long-wave infrared drying which are sequentially performed. In the invention, the wavelength of the medium-wave infrared drying is preferably 1.5-6 μm, and more preferably 2-4 μm; the temperature is preferably 80-150 ℃, and more preferably 100-120 ℃; the time is preferably 10s to 30min, and more preferably 5 to 20 min.
In the invention, the wavelength of the long-wave infrared drying is preferably 6-10 μm, more preferably 7-9 μm, the temperature is preferably 50-300 ℃, more preferably 100-200 ℃, and the time is preferably 1-60 min, more preferably 10-40 min.
After the primer film layer is obtained, coating a water-based LED photocuring finish paint on the surface of the primer film layer, and sequentially carrying out second UVLED photocuring and second drying to obtain the water-based LED photocuring coating. In the present invention, the coating is preferably performed by spray coating. The present invention does not require any particular means for spraying, and can be applied by spraying means known to those skilled in the art. In the invention, the number of coating times is preferably 1-3, and the coating thickness of the water-based LED photocuring finish paint is preferably 20-200 μm, and more preferably 50-150 μm.
In the invention, the temperature of the second UVLED light curing is preferably room temperature, and the time is preferably 0.5-30 min, and more preferably 5-20 min. In the invention, the wavelength of the second UVLED light curing is preferably 320-390 nm.
In the present invention, the second drying preferably includes medium-wave infrared drying and long-wave infrared drying which are sequentially performed. In the invention, the wavelength of the medium-wave infrared drying is preferably 1.5-6 μm, and more preferably 2-4 μm; the temperature is preferably 80-150 ℃, and more preferably 100-120 ℃; the time is preferably 10s to 30min, and more preferably 5 to 20 min.
In the invention, the wavelength of the long-wave infrared drying is preferably 6-10 μm, more preferably 7-9 μm, the temperature is preferably 50-300 ℃, more preferably 100-200 ℃, and the time is preferably 1-60 min, more preferably 10-40 min.
In the invention, the coating process of the water-based LED photocureable coating is preferably carried out in a dust-free production workshop, and flowing air is started in the coating process; in the invention, the outlet air of the coating process is preferably sent to a VOC tail gas treatment device for treatment.
The following will explain the water-based LED photocurable coating and the coating method of the present invention in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Synthesis of epoxy resin based polymer AI:
1.14kg of bisphenol F epoxy resin (I-1-1) was dissolved in 2L of methylene chloride, 276g of anhydrous potassium carbonate was added, after stirring at room temperature for 1 hour, 788g of an ionic liquid functional group compound (I-1-2) having an alkyl chain was added, after reflux reaction for 10 hours, the mixture was cooled to room temperature, washed three times with water, dried over anhydrous sodium sulfate, and concentrated to remove the solvent, thereby obtaining an epoxy resin intermediate compound I-1-3 containing an ionic liquid functional group.
1H NMR(500MHz,Chloroform)δ7.06(s,8H),6.82(s,8H),4.42(s,1H),4.26–3.84(m,12H),3.35(d,J＝16.1Hz,3H),3.08(d,J＝31.9Hz,3H),2.61–2.25(m,6H),2.17(s,1H),1.68–1.03(m,11H).13C NMR(125MHz,Common NMR Solvents)δ173.28,158.36,134.24,131.34,116.02,75.03,70.04,69.59,61.02,54.10,51.46,46.51,42.42,40.38,30.13,27.64,27.60,26.58.
1.103kg of intermediate compound (I-1-2) was dissolved in 2L of anhydrous toluene, 360g of glacial acetic acid was added to the reaction system, and the mixture was refluxed for 24 hours, cooled and concentrated to obtain epoxy resin I-1-4 containing an ionic liquid functional group and an acrylate structural unit.
1H NMR(500MHz,Chloroform)δ7.08(s,8H),6.84(s,8H),6.39(d,J＝5.6Hz,4H),6.11(s,2H),5.82(s,2H),4.44(d,J＝5.5Hz,3H),4.29–3.70(m,11H),3.40(d,J＝9.6Hz,3H),2.90(s,1H),2.43(s,2H),2.23(s,3H),1.70–1.03(m,8H).13C NMR(125MHz,Common NMR Solvents)δ173.29,165.14,158.36,134.24,131.34,129.94,128.27,116.02,89.84,75.03,72.30,70.04,69.61,61.01,54.09,42.43,40.38,30.12,27.60,24.40.
838g of epoxy resin I-1-4 containing an ionic liquid functional group and an acrylate structural unit is dissolved in dry dichloromethane, 180g of acryloyl chloride is dropwise added at room temperature, reaction is carried out for two hours at room temperature, and condensation is carried out to obtain the acryloyl-terminated epoxy resin-based polymer AI.
1H NMR(500MHz,Chloroform)δ7.09(d,J＝7.5Hz,8H),6.85(d,J＝7.5Hz,8H),6.77–6.66(m,2H),6.41(dd,J＝10.0,2.1Hz,4H),6.12(dd,J＝16.8,10.0Hz,4H),5.83(dd,J＝16.8,2.1Hz,4H),4.60–4.32(m,5H),4.18–3.86(m,9H),3.59(s,1H),3.37(t,J＝4.8Hz,2H),2.44(t,J＝5.0Hz,2H),2.08(s,1H),1.62–1.49(m,5H),1.41–1.19(m,4H).13C NMR(125MHz,Common NMR Solvents)δ173.29,164.38,158.36,134.24,131.34,129.94,128.27,116.02,87.19,75.03,70.93,70.04,69.61,61.01,54.09,42.43,40.38,30.12,27.60,24.40.
The synthetic route is shown as formula a:
example 2
Synthesis of epoxy resin-based Polymer AII:
1.25kg of bisphenol A epoxy resin (I-2-1) was dissolved in 2L of methylene chloride, 276g of anhydrous potassium carbonate was added, after stirring at room temperature for 1 hour, 788g of an ionic liquid functional group compound (I-2-2) having an alkyl chain was added, after reflux reaction for 10 hours, the mixture was cooled to room temperature, washed three times with water, dried over anhydrous sodium sulfate, and concentrated to remove the solvent, thereby obtaining an epoxy resin intermediate compound I-2-3 containing an ionic liquid functional group.
1H NMR(500MHz,Chloroform)δ7.35–7.17(m,8H),6.92–6.73(m,8H),4.41(tt,J＝12.6,9.7Hz,1H),4.22–4.03(m,6H),3.96(dd,J＝24.7,14.1Hz,2H),3.69(s,1H),3.50(d,J＝15.6Hz,2H),3.42–3.27(m,2H),3.22–2.93(m,2H),2.59–2.22(m,9H),1.72(s,12H),1.64–1.14(m,8H).13C NMR(125MHz,Common NMR Solvents)δ173.28,155.64,143.67,129.12,115.35,75.03,70.04,69.59,61.02,54.10,51.46,46.51,45.98,40.38,30.26,30.13,27.64,27.60,26.58.
1.36kg of intermediate compound I-2-3 is dissolved in 2L of anhydrous toluene, 288g of glacial acetic acid is added into the reaction system, reflux reaction is carried out for 24 hours, cooling and concentration are carried out, thus obtaining the epoxy resin I-2-4 containing ionic liquid functional groups and acrylate structural units.
1H NMR(500MHz,Chloroform)δ7.33–7.23(m,8H),6.90–6.80(m,8H),6.70–6.62(m,2H),6.41(dd,J＝19.8,4.6Hz,2H),6.12(dd,J＝33.5,19.8Hz,2H),5.86(d,J＝4.4Hz,1H),5.79(d,J＝4.4Hz,1H),4.55–4.37(m,3H),4.28–4.12(m,4H),4.07(dd,J＝9.4,0.8Hz,2H),3.41(dd,J＝18.7,10.2Hz,3H),3.07(s,2H),2.48–2.40(m,2H),1.77(s,3H),1.72(s,12H),1.60–1.31(m,8H),1.41–1.31(m,4H),1.39–1.26(m,4H).13C NMR(125MHz,Common NMR Solvents)δ173.28,165.14,155.64,143.67,129.94,129.12,128.27,115.35,89.84,75.03,72.30,70.04,69.61,61.02,54.10,45.98,40.38,30.26,30.13,27.60,24.40.
1.04kg of epoxy resin I-2-4 containing ionic liquid functional groups and acrylate structural units is dissolved in dry dichloromethane, 180g of acryloyl chloride is dropwise added at room temperature, the reaction is carried out for two hours at room temperature, and the acryloyl-terminated epoxy resin macromolecular material AII is obtained by concentration.
1H NMR(500MHz,Chloroform)δ7.28(d,J＝7.5Hz,8H),6.85(d,J＝7.5Hz,8H),6.82–6.77(m,2H),6.41(dd,J＝10.0,2.1Hz,4H),6.12(dd,J＝16.8,10.0Hz,4H),5.83(dd,J＝16.8,2.1Hz,4H),4.47(dd,J＝3.3,1.9Hz,4H),4.40(t,J＝4.5Hz,1H),4.08(dd,J＝9.7,4.4Hz,4H),3.88(d,J＝23.4Hz,2H),3.35(t,J＝7.3Hz,2H),2.55(s,1H),2.44(t,J＝5.1Hz,2H),2.20(s,3H),1.72(s,12H).13C NMR(125MHz,Common NMR Solvents)δ173.29,164.38,155.64,143.67,129.94,129.12,128.27,115.35,87.19,75.03,70.93,70.04,69.61,61.01,54.09,45.98,40.38,30.26,30.12,27.60,24.40.
The synthetic route is shown as formula b:
example 3
Synthesis of epoxy resin-based Polymer AIII:
bisphenol Z epoxy resin (I-3-1)1.41kg dissolved in 2L of dichloromethane, 276g of anhydrous potassium carbonate added, stirring at room temperature for 1 hour, adding 788g of ionic liquid functional group compound (I-3-2) with an alkyl chain, reflux reaction for 10 hours, cooling to room temperature, washing with water three times, drying with anhydrous sodium sulfate, and concentrating to remove the solvent, to obtain epoxy resin intermediate compound I-3-3 containing ionic liquid functional groups.
1H NMR(500MHz,Chloroform)δ7.37–7.18(m,8H),6.92–6.72(m,8H),4.61–4.40(m,1H),4.06(tdd,J＝73.6,24.8,14.1Hz,8H),3.52–2.85(m,7H),2.54–2.32(m,4H),2.28–1.76(m,11H),1.67–1.02(m,22H).13C NMR(125MHz,Common NMR Solvents)δ173.28,155.29,141.42,127.58,116.41,75.03,70.04,69.59,61.02,54.10,51.46,48.18,46.51,40.38,37.52,30.13,27.64,27.60,26.58,25.62,22.53.
1.53kg of intermediate compound I-3-3 is dissolved in 2L of anhydrous toluene, 288g of glacial acetic acid is added into the reaction system, reflux reaction is carried out for 24 hours, cooling and concentration are carried out, thus obtaining the epoxy resin I-3-4 containing ionic liquid functional groups and acrylate structural units.
1H NMR(500MHz,Chloroform)δ7.39–7.18(m,8H),7.02–6.73(m,8H),6.48–6.31(m,4H),6.12(dd,J＝33.5,19.8Hz,2H),5.83(dd,J＝33.5,4.4Hz,2H),4.60–4.35(m,3H),4.26–4.00(m,6H),3.42(dd,J＝39.2,26.2Hz,3H),2.79(d,J＝61.4Hz,2H),2.50–1.79(m,13H),1.70–0.97(m,20H).13C NMR(125MHz,Common NMR Solvents)δ173.29,165.14,155.29,141.41,129.94,128.27,127.57,116.41,89.84,75.03,72.30,70.04,69.61,61.01,54.09,48.17,40.38,37.52,30.12,27.60,25.61,24.40,22.52.
1.12kg of epoxy resin I-3-4-containing ionic liquid functional groups and acrylate structural units is dissolved in dry dichloromethane, 180g of acryloyl chloride is dripped at room temperature, the reaction is carried out for two hours at room temperature, and the acryloyl-terminated epoxy resin macromolecular material AIII is obtained by concentration.
1H NMR(500MHz,Chloroform)δ7.35–7.17(m,8H),7.15–7.03(m,2H),6.95–6.75(m,8H),6.41(dd,J＝19.9,4.5Hz,4H),6.12(dd,J＝33.5,19.8Hz,4H),5.83(dd,J＝33.5,4.4Hz,4H),4.56–4.26(m,5H),4.11(ddd,J＝10.6,8.5,5.1Hz,4H),3.67–3.08(m,4H),2.51–2.24(m,6H),2.01–0.93(m,26H).13C NMR(125MHz,Common NMR Solvents)δ173.28,164.38,155.29,141.42,129.94,128.27,127.58,116.41,87.19,75.03,70.93,70.04,69.61,61.01,54.09,48.17,40.38,37.52,30.12,27.60,25.61,24.40,22.52.
The synthetic route is shown as formula c:
example 4
Synthesis of epoxy resin-based Polymer AIV:
1.34kg of bisphenol S epoxy resin (I-4-1) was dissolved in 2L of methylene chloride, 276g of anhydrous potassium carbonate was added, after stirring at room temperature for 1 hour, 788g of an ionic liquid functional group compound (I-4-2) having an alkyl chain was added, after reflux reaction for 10 hours, the mixture was cooled to room temperature, washed three times with water, dried over anhydrous sodium sulfate, and concentrated to remove the solvent, thereby obtaining an epoxy resin intermediate compound I-4-3 containing an ionic liquid functional group.
1H NMR(500MHz,Chloroform)δ8.31–8.02(m,8H),7.11–6.69(m,8H),4.56–2.76(m,16H),2.68–2.12(m,9H),1.71–0.90(m,8H).13C NMR(125MHz,Common NMR Solvents)δ173.29,162.29,130.78,129.50,114.18,75.03,70.04,69.61,69.59,61.01,54.09,51.46,46.50,40.38,30.12,27.64,27.60,26.58.
1.96kg of intermediate compound (I-4-3) was dissolved in 2L of anhydrous toluene, 360g of glacial acetic acid was added to the reaction system, and the mixture was refluxed for 24 hours, cooled and concentrated to obtain epoxy resin I-4-4 containing an ionic liquid functional group and an acrylate structural unit.
1H NMR(500MHz,Chloroform)δ8.26–7.95(m,8H),7.06–6.65(m,8H),6.46–5.66(m,8H),4.70–3.91(m,9H),3.79–2.21(m,12H),1.73–1.04(m,6H).13C NMR(125MHz,Common NMR Solvents)δ173.28,165.14,162.29,130.78,129.94,129.51,128.27,114.18,89.84,75.03,72.30,70.04,69.61,61.02,54.10,40.38,30.13,27.60,24.40.
1.08g of epoxy resin I-4-4 containing ionic liquid functional groups and acrylate structural units is dissolved in dry dichloromethane, 180g of acryloyl chloride is dropwise added at room temperature, reaction is carried out for two hours at room temperature, and the acryloyl-terminated epoxy resin macromolecular material is obtained by concentration.
1H NMR(500MHz,Chloroform)δ8.18(d,J＝7.5Hz,1H),7.12–6.99(m,1H),6.94(d,J＝7.5Hz,1H),6.41(dd,J＝10.0,2.1Hz,1H),6.12(dd,J＝16.8,10.0Hz,1H),5.83(dd,J＝16.8,2.1Hz,1H),4.46(dd,J＝3.1,1.9Hz,1H),4.40–4.29(m,1H),4.15–2.33(m,2H),1.64–1.20(m,1H).13C NMR(125MHz,Common NMR Solvents)δ173.28,164.38,162.29,130.78,129.94,129.51,128.27,114.18,87.19,75.03,70.93,70.04,69.61,61.02,54.10,40.38,30.13,27.60,24.40.
The synthetic route is shown as formula d:
example 5
Synthesis of polyurethane-based Polymer BI:
2.51kg of 3, 5-diisocyanato-1-benzyl bromide (II-1-1) and 62g of ethylene glycol (II-1-2) were dissolved in 5L of anhydrous acetonitrile, and the mixture was refluxed for 5 hours, 251g of 3, 5-diisocyanato-1-benzyl bromide (II-1-1) was added thereto, and the reaction was continued for 1 hour, and the solvent was removed by concentration under reduced pressure to obtain a polyurethane macromolecular material II-1-3.
1H NMR(500MHz,Chloroform)δ7.84(s,2H),7.74(s,1H),7.68(s,2H),7.63(s,2H),7.17(s,2H),7.13(s,2H),6.84(s,2H),4.77(d,J＝25.5Hz,6H),4.31(s,8H).13C NMR(125MHz,Common NMR Solvents)δ154.83,145.09,140.47,134.83,134.25,134.10,128.73,120.60,114.71,112.74,110.98,105.34,60.78,31.04.
1.75kg of polyurethane macromolecular material I-1-3 is dissolved in anhydrous acetonitrile, 380g of alcohol compound (II-1-4) with acrylic ester is dripped at room temperature, and after the dripping is finished, the mixture is heated to reflux reaction for 5 hours to obtain the acrylic ester structure (II-1-5) with polymerizable terminal.
1H NMR(500MHz,Chloroform)δ7.74(t,J＝2.9Hz,3H),7.68(d,J＝3.1Hz,6H),7.23(s,6H),6.58–5.63(m,6H),4.93(s,6H),4.60–4.06(m,16H).13C NMR(125MHz,Common NMR Solvents)δ168.90,154.83,140.47,134.10,129.54,127.80,112.74,110.98,62.29,60.78,31.04.
1.11kg of an acrylate structure (II-1-5) with a polymerizable terminal and 319g of an ionic liquid compound (II-1-6) are dissolved in 2L of dichloromethane, 138g of potassium carbonate is added, reflux reaction is carried out for 24 hours, the temperature is reduced, and the solvent is removed by concentration under reduced pressure to obtain an ionic liquid functionalization reaction, so that the polyurethane-based polymer BI is obtained.
1H NMR(500MHz,Chloroform)δ7.74(t,J＝1.4Hz,3H),7.68(d,J＝1.4Hz,6H),7.29(s,4H),7.19(s,2H),6.41(dd,J＝10.0,2.1Hz,2H),6.12(dd,J＝16.8,10.0Hz,2H),5.83(dd,J＝16.8,2.1Hz,2H),4.80(s,6H),4.42–4.35(m,4H),4.35–4.26(m,12H),3.42(t,J＝7.6Hz,3H),3.38–3.30(m,12H),3.24(t,J＝5.3Hz,3H),2.97(t,J＝7.5Hz,3H),2.90(t,J＝5.3Hz,3H),2.70(t,J＝7.5Hz,3H),2.42(s,9H),1.60–1.45(m,12H),1.33(tt,J＝7.8,5.4Hz,6H).13C NMR(125MHz,Common NMR Solvents)δ168.90,154.83,149.81,139.58,134.73,129.54,127.80,120.77,119.58,74.30,71.61,62.29,60.78,55.39,50.40,49.59,41.00,29.72,27.49,24.40.
The synthetic route is shown as formula e:
example 6
Synthesis of polyurethane-based Polymer BII:
2.51kg of 3, 5-diisocyanato-1-benzyl bromide (II-2-1) and 62g of ethylene glycol (II-2-2) were dissolved in 5L of anhydrous acetonitrile, and the mixture was refluxed for 5 hours, 251g of 3, 5-diisocyanato-1-benzyl bromide (II-2-1) was added thereto, and the reaction was continued for 1 hour, and the solvent was removed by concentration under reduced pressure to obtain a polyurethane macromolecular material II-2-3.
1.75kg of polyurethane macromolecular material I-1-3 is dissolved in anhydrous acetonitrile, 380g of p-hydroxybenzyl acrylate compound (II-2-4) is dropwise added at room temperature, and after the dropwise addition is finished, the mixture is heated to reflux reaction for 5 hours to obtain an acrylate structure (II-2-5) with a polymerizable terminal.
1H NMR(500MHz,Chloroform)δ7.73(t,J＝3.0Hz,3H),7.67(d,J＝2.9Hz,6H),7.51(s,2H),7.36(s,2H),7.24(s,2H),7.17(s,8H),6.17(ddd,J＝52.9,26.6,12.5Hz,4H),5.73(dd,J＝33.2,4.8Hz,2H),5.02(s,4H),4.91(s,2H),4.31(s,8H).13C NMR(125MHz,Common NMR Solvents)δ165.45,154.83,154.46,148.91,147.20,140.47,134.11,129.19,127.17,122.89,122.67,112.74,110.98,60.77,31.04.
1.28kg of an acrylic ester structure (II-2-5) with a polymerizable terminal and 319g of an ionic liquid compound (II-2-6) were dissolved in 2L of dichloromethane, 138g of potassium carbonate was added, reflux reaction was carried out for 24 hours, the temperature was reduced, and the solvent was removed by concentration under reduced pressure to obtain an ionic liquid functionalization reaction and to obtain a polyurethane-based polymer BII.
1H NMR(500MHz,Chloroform)δ7.74(t,J＝1.4Hz,3H),7.68(d,J＝1.4Hz,6H),7.45(s,2H),7.24(s,4H),7.18(s,8H),6.24(dd,J＝10.1,2.2Hz,2H),6.10(dd,J＝16.8,10.0Hz,2H),5.74(dd,J＝16.8,2.1Hz,2H),4.80(s,6H),4.31(s,8H),3.54–2.26(m,37H),1.76–1.13(m,18H).
13C NMR(125MHz,Common NMR Solvents)δ165.45,154.83,154.46,149.81,148.91,147.20,139.58,134.73,129.19,127.17,122.89,122.67,120.77,119.58,74.30,71.61,60.78,55.39,50.40,49.59,41.00,29.72,27.49,24.40.
The synthetic route is shown as formula f:
example 7
Synthesis of water-soluble photoinitiator CI:
2.34kg of bis- (4-hydroxyphenyl) phosphine oxide (III-1-1) was dissolved in 5L of methylene chloride, 2.67kg of acryloyl chloride was added dropwise at room temperature, the reaction was continued for 2 hours after the completion of the dropwise addition, and the solvent was removed by concentration to obtain the key intermediate III-1-2 containing an acrylate end-cap.
1H NMR(500MHz,Chloroform)δ7.75–7.68(m,4H),7.46–7.40(m,4H),6.24(dd,J＝19.9,4.9Hz,2H),6.10(dd,J＝33.1,19.9Hz,2H),5.74(dd,J＝33.1,4.9Hz,2H).13C NMR(125MHz,Common NMR Solvents)δ165.45,149.40,149.37,132.04,131.94,129.19,127.17,124.97,123.95,123.91,123.88.
684g of key intermediate III-1-2 containing acrylate end-capping and 880g of anhydride I-1-3 were dissolved in 2L of toluene, refluxed for 6 hours, and concentrated under reduced pressure to remove the solvent, to obtain compound III-1-4 containing the TPO base nucleus.
1H NMR(500MHz,Chloroform)δ7.37–7.27(m,6H),7.27–7.09(m,4H),6.17(ddd,J＝52.9,26.5,12.4Hz,4H),5.74(dd,J＝33.1,4.9Hz,2H),2.22(s,6H).13C NMR(125MHz,Common NMR Solvents)δ193.40,165.45,146.02,139.92,137.66,135.44,134.14,129.19,127.17,125.04,124.97,118.69,20.75.
552g of compound III-1-4 containing TPO basic parent nucleus and 498g of ionic liquid compound (III-1-5) are dissolved in 2L of dichloromethane, 138g of potassium carbonate is added, reflux reaction is carried out for 24 hours, temperature reduction and reduced pressure concentration are carried out to remove the solvent, thus obtaining the target water-soluble polymerizable photoinitiator CI through ionic liquid functionalization reaction.
1H NMR(500MHz,Chloroform)δ7.36–7.27(m,4H),7.26–7.15(m,4H),6.86(s,2H),6.24(dd,J＝19.9,4.9Hz,2H),6.10(dd,J＝33.1,19.9Hz,2H),5.74(dd,J＝33.1,4.9Hz,2H),4.11(t,J＝10.2Hz,2H),3.73(s,1H),3.53(s,1H),3.11(s,1H),2.50–2.38(m,5H),2.22(s,6H),1.80(p,J＝10.4Hz,2H),1.54–1.19(m,6H).13C NMR(125MHz,Common NMR Solvents)δ193.40,173.29,165.45,160.22,146.02,138.49,135.44,129.19,128.60,127.17,124.97,118.69,116.01,69.66,61.01,54.09,40.38,28.80,27.64,27.60,26.58,20.75.
The synthetic route is shown as formula g:
example 8
Synthesis of water-soluble photoinitiator CII:
2.34kg of bis- (4-hydroxyphenyl) phosphine oxide (III-1-1) was dissolved in 5L of methylene chloride, 3.12kg of methacryloyl chloride was added dropwise at room temperature, the reaction was continued for 2 hours after the completion of the dropwise addition, and the solvent was removed by concentration to obtain a key intermediate III-2-2 containing a methacrylate end-cap.
1H NMR(500MHz,Chloroform)δ7.72(d,J＝15.0Hz,4H),7.43(d,J＝15.0Hz,4H),6.43(dq,J＝4.0,2.0Hz,2H),6.18(dq,J＝4.0,2.0Hz,2H),2.01(t,J＝2.0Hz,6H).13C NMR(125MHz,Common NMR Solvents)δ166.30,150.29,150.26,133.90,132.36,132.26,126.64,124.97,123.91,123.77,123.70,19.10.
740g of key intermediate III-1-2 containing methacrylate end capping and 880g of acid anhydride I-1-3 were dissolved in 2L of toluene, refluxed for 6 hours, and concentrated under reduced pressure to remove the solvent, to obtain compound III-2-4 containing the basic core of TPO.
1H NMR(500MHz,Chloroform)δ7.36–7.27(m,6H),7.25–7.16(m,4H),6.43(dq,J＝4.0,2.0Hz,2H),6.18(dq,J＝4.0,2.0Hz,2H),2.22(s,6H),2.01(t,J＝2.0Hz,6H).13C NMR(125MHz,Common NMR Solvents)δ166.30,156.14,142.83,138.74,133.90,132.31,130.63,129.23,126.64,126.12,117.89,20.75,19.10.
581g of compound III-1-4 containing TPO basic parent nucleus and 498g of ionic liquid compound (III-1-5) are dissolved in 2L of dichloromethane, 138g of potassium carbonate is added, reflux reaction is carried out for 24 hours, temperature reduction and reduced pressure concentration are carried out to remove the solvent, thus obtaining the target water-soluble polymerizable photoinitiator CII through ionic liquid functionalization reaction.
1H NMR(500MHz,Chloroform)δ7.34–7.31(m,1H),7.31–7.28(m,2H),7.24–7.21(m,3H),7.20–7.18(m,1H),6.86(s,2H),6.43(dq,J＝4.0,2.0Hz,2H),6.18(dq,J＝4.0,2.0Hz,2H),4.88(s,2H),4.44(s,2H),4.11(t,J＝10.1Hz,2H),3.26(t,J＝11.3Hz,1H),3.05–2.90(m,4H),2.22(s,6H),2.01(s,6H),1.80(ttd,J＝15.7,10.0,1.3Hz,2H),1.56–1.39(m,4H),1.37–1.20(m,2H).13C NMR(125MHz,Common NMR Solvents)δ204.77,166.30,161.59,153.82,139.97,136.97,133.90,128.91,127.10,126.65,125.16,124.36,118.12,114.70,81.84,73.24,69.66,51.17,37.81,28.80,27.64,27.49,26.58,20.75,19.10.
The synthetic route is shown as formula h.
Example 9
The formula of the water-based LED photocuring primer coating is shown in the table 1-8.
Table 1 formulation 1 of a water-based LED photocurable primer coating
Table 2 formulation 2 of water-based LED photocurable primer coating
Table 3 formulation 3 of water-based LED photocurable primer coating
Table 4 formulation 4 of waterborne LED photocurable primer coating
TABLE 5 formulation 5 of waterborne LED photocuring primer coating
TABLE 6 formulation 6 for waterborne LED photocuring primer coating
Table 7 formulation 7 of a water-based LED photocurable primer coating
TABLE 8 formulation 8 of waterborne LED photocuring primer coating
Example 9
The formula of the water-based LED photocuring finish paint is shown in tables 9-12.
TABLE 9 waterborne LED photocuring topcoat coating formulation 1
TABLE 10 waterborne LED photocuring topcoat coating formulation 2
TABLE 11 waterborne LED photocuring topcoat coating formulation 3
TABLE 12 waterborne LED photocuring topcoat coating formulation 4
Example 10
The primer and topcoat applications were the formulations referred to in the previous examples, with the combination scheme shown in Table 13.
TABLE 13 primer and topcoat combination formulations
The coating process is shown in fig. 1.
The specific coating process of the scheme 1 comprises the following steps:
and cleaning the surface of the base material by using zirconium salt and deionized water, removing oil and rust on the surface of the metal base material, and drying. And spraying the surface of the base material by taking the primer formula 1 as a primer, irradiating for 10 minutes by using a UV-LED to perform cross-linking curing, further drying by using medium-wave infrared and long-wave infrared respectively, spraying the surface paint by taking the finish formula 1 as a finish, irradiating for 10 minutes by using the UV-LED to perform cross-linking curing, further drying by using the medium-wave infrared and long-wave infrared respectively, and discharging. A small amount of VOC tail gas is treated, and no waste water and waste gas are discharged in the whole process.
The coating method of schemes 2 to 32 is the same as scheme 1.
The hardness, adhesion, solvent resistance (alcohol scrubbing times) and VOC emission of the coating obtained by the scheme 1-32 are tested. The hardness of the cured film is implemented according to GB/T6739-1996 pencil determination method for coating hardness, and the test range is 4B-6H; the adhesion test was performed according to the national standard GB/T9286-1998; the yellowing resistance test is carried out according to GB-T9761-2008 visual colorimetry of colored paint and varnish colored paint, and the solvent resistance test is carried out according to the A method (soaking method) in GB 9274-1988 determination of liquid medium resistance of colored paint and varnish; and VOC emission test is carried out by GB/T23986-2009 gas chromatography for determination of Volatile Organic Compound (VOC) content in colored paint and varnish.
The results are shown in Table 14.
TABLE 14 Performance test results for coatings obtained in schemes 1-32
The waterborne LED photocureable coating prepared by using the epoxy resin-based polymer, the polyurethane-based polymer and the water-soluble photoinitiator as raw materials has good hardness, adhesion resistance and solvent resistance, and the VOC release amount is 70-110 mg/mL.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (13)
1. The application of the ionic liquid structural unit in preparing the water-based LED photocureable coating comprises preparing a polymer for the water-based LED photocureable coating and/or a photoinitiator for the water-based LED photocureable coating;
the ionic liquid structural unit has a structure represented by formula W:
in the formula W, m is 1-10.
2. An epoxy-based polymer having the structure of formula I:
in the formula A, R is independently CyH2y+1Y is 0 to 20;
ar is independently
m is 1 to 10, and n is 2 to 10.
3. A process for the preparation of an epoxy resin based polymer as claimed in claim 2, comprising the steps of:
carrying out substitution reaction on the epoxy resin with the structure shown in the formula A-1 and the ionic liquid with the structure shown in the formula A-2 to obtain a compound with the structure shown in the formula A-3;
carrying out ring-opening addition reaction on a compound with a structure shown as a formula A-3 and a compound with a structure shown as a formula A-4 to obtain a compound with a structure shown as a formula A-5;
carrying out substitution reaction on a compound with a structure shown as a formula A-5 and a compound with a structure shown as a formula A-6 to obtain an epoxy resin-based polymer with a structure shown as a formula A;
4. use of the epoxy resin-based polymer according to claim 2 or the epoxy resin-based polymer prepared by the preparation method according to claim 3 as a polymer for a water-based LED photocuring primer coating.
5. A polyurethane-based polymer having the structure of formula B:
in the formula B, R is independently CyH2y+1Y is 0 to 20;
a is aryl or- (CH)2)k-, k is 2 to 10;
m is 1 to 10, and n is 2 to 10.
6. A method for preparing the polyurethane-based polymer according to claim 5, comprising the steps of:
carrying out nucleophilic addition reaction on a compound with a structure shown as a formula B-1 and a compound with a structure shown as a formula B-2 to obtain a compound with a structure shown as a formula B-3;
carrying out nucleophilic addition reaction on a compound with a structure shown as a formula B-3 and a compound with a structure shown as a formula B-4 to obtain a compound with a structure shown as a formula B-5;
carrying out substitution reaction on a compound with a structure shown as a formula B-5 and ionic liquid with a structure shown as a formula B-6 to obtain a polyurethane-based polymer with a structure shown as a formula B;
7. use of the polyurethane-based polymer according to claim 5 or the polyurethane polymer according to claim 6 as a polymer for an aqueous LED photocurable topcoat coating.
8. A water-soluble photoinitiator having a structure represented by formula C:
in the formula C, R is independently CyH2y+1Y is 0 to 20;
m is 0 to 5.
9. The method of preparing the water-soluble photoinitiator according to claim 8, comprising the steps of:
carrying out substitution reaction on a compound with a structure shown as a formula C-1 and a compound with a structure shown as a formula C-2 to obtain a compound with a structure shown as a formula C-3;
carrying out substitution reaction on a compound with a structure shown as a formula C-3 and a compound with a structure shown as a formula C-4 to obtain a compound with a structure shown as a formula C-5;
carrying out substitution reaction on a compound with a structure shown as a formula C-5 and ionic liquid with a structure shown as a formula C-6 to obtain a photocatalyst with a structure shown as a formula C;
10. use of the water-soluble photoinitiator according to claim 8 or the water-soluble photoinitiator prepared by the preparation method according to claim 9 as a photoinitiator for a water-based LED photocuring coating.
11. The water-based LED photocuring primer coating comprises the following components in percentage by mass:
the epoxy resin-based polymer is the epoxy resin-based polymer as claimed in claim 2 or the epoxy resin-based polymer prepared by the preparation method as claimed in claim 3;
the water-soluble photoinitiator is the water-soluble photoinitiator according to claim 8 or the water-soluble photoinitiator prepared by the preparation method according to claim 9.
12. A water-based LED photocuring finish paint comprises the following components in percentage by mass:
the polyurethane-based polymer is the polyurethane-based polymer according to claim 5 or the polyurethane-based polymer obtained by the production method according to claim 6;
the water-soluble photoinitiator is the water-soluble photoinitiator according to claim 8 or the water-soluble photoinitiator prepared by the preparation method according to claim 9.
13. A coating method of a water-based LED photocureable coating comprises the following steps:
coating the water-based LED photocuring primer coating of claim 11 on the surface of a substrate, and sequentially carrying out first UVLED photocuring and first drying to obtain a primer film layer;
coating the surface of the primer film layer with the water-based LED photocuring finish paint as defined in claim 12, and sequentially carrying out second UVLED photocuring and second drying to obtain the water-based LED photocuring coating.
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