CN118006220A - A water-based bio-based light-heat dual-curing material based on citric acid and epoxidized soybean oil and a preparation method thereof - Google Patents
A water-based bio-based light-heat dual-curing material based on citric acid and epoxidized soybean oil and a preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-based bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil and a preparation method thereof. The invention has the advantages of high content of biological base, reproducibility, environmental protection and low cost; amine neutralization is not needed, so that the residue of unreacted amine in the material is reduced; photo-curing groups with high functionality and photo-thermal dual curing system designs; and the material performance can be regulated and controlled by adjusting the proportion of raw materials, and the cured material has the characteristics of high hardness, high mechanical property, high water resistance, high impact resistance and the like by comprehensive cooperation.
Description
Technical Field
The invention relates to the technical field of water-based bio-based photo-thermal dual-curing materials, in particular to a water-based bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil and a preparation method thereof.
Background
The water-based bio-based photo-curing coating is a green environment-friendly coating, and has the characteristics of low Volatile Organic Compound (VOC) emission, no toxicity, no harm, reproducibility, rapid curing and the like, so that the water-based bio-based photo-curing coating is widely applied to the fields of printing, packaging, wood furniture, floors and the like.
The ultraviolet light curing coating prepared by taking soybean oil as a bio-based raw material is a common bio-based light curing material, and has been studied more, and the main method is that firstly, the soybean oil is subjected to oil oxidation and then reacts with acrylic acid to prepare the soybean oil-based epoxy acrylate resin. In recent years, researchers have been developing and utilizing new bio-based raw materials to prepare aqueous bio-based photo-thermal dual-cured materials. The citric acid has wide sources, low cost and no toxicity, has three carboxyl groups and one hydroxyl group in the molecular structure, and is a new bio-based raw material for preparing the epoxy acrylate by the reaction of the acrylic acid and the epoxidized soybean oil after modification. CN 116217845A discloses a water-based bio-based photo-curing material and a preparation method thereof, the method successfully prepares the water-based bio-based epoxy acrylate resin based on citric acid and epoxy soybean oil, and the product resin has the characteristics of good hydrophilicity, good storage stability, good mutual compatibility and easy compounding, mixing and modification, so that the coating after photo-curing has the characteristics of high adhesive force, high flexibility, high impact resistance and high glossiness. However, this method has the following disadvantages: (1) The performance of the water-based bio-based epoxy acrylate resin based on the citric acid and the epoxy soybean oil is poor, the material performance is improved by a physical blending method of the water-based bio-based epoxy acrylate resin based on the citric acid and the petroleum-based epoxy resin, the modification method of the physical blending of the emulsion cannot fully and uniformly blend polymers in emulsion particles, and the modification effect is limited. Meanwhile, the water-based bio-based epoxy acrylate resin based on the citric acid and the epoxidized soybean oil is high in bio-based content, but the bio-based content is obviously reduced after the water-based bio-based epoxy acrylate resin based on the citric acid and the petroleum-based epoxy resin is blended and modified. (2) The prepared waterborne bio-based epoxy acrylate resin is an anionic polymer, the waterborne epoxy acrylate resin is neutralized by triethylamine, the triethylamine has a high boiling point and is easy to remain in a photocuring coating film to cause the performance degradation, and meanwhile, the use of a neutralizing agent of triethylamine increases the VOCs emission of a material system.
(3) The prepared water-based bio-based photo-curing material has low hardness and poor mechanical property.
Disclosure of Invention
In view of the defects existing at present, the invention provides the aqueous bio-based photo-thermal dual-curing material based on the citric acid and the epoxidized soybean oil and the preparation method thereof, and the aqueous bio-based photo-thermal dual-curing material based on the citric acid and the epoxidized soybean oil has the advantages of high bio-based content, reproducibility, environmental protection and low cost, does not need amine neutralization, reduces the residues of unreacted amine, has the design of a photo-curing group with high functionality and a photo-thermal dual-curing system, can regulate and control the material performance by adjusting the proportion of raw materials, comprehensively coordinates the characteristics of high hardness, high mechanical property, high water resistance and high impact resistance of a photo-cured coating, and has great application prospects in the fields of printing and packaging, wood furniture, antibacterial and antiviral coatings, medical sanitation, children toys and the like.
In order to achieve the above purpose, the invention provides a preparation method of an aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil, which comprises the following steps:
Step 1: in an inert gas atmosphere, mixing citric acid, a solvent, a catalyst and a polymerization inhibitor, slowly heating to 60-90 ℃, slowly dropwise adding an epoxy compound with double bonds after the citric acid is completely dissolved, preserving heat for 1h after dropwise adding, and heating to 90-110 ℃ for reacting for 1-4 h;
preferably, the inert atmosphere is nitrogen.
Preferably, the above reaction is carried out in an apparatus equipped with a stirrer, a constant pressure hopper, a condenser tube and a thermometer.
Step 2: then adding polyethylene glycol diglycidyl ether and liquid epoxy resin, and reacting at 90-110 ℃ until the acid value is unchanged;
step 3: then adding citric acid and epoxy compound with double bonds, and reacting at 90-110 ℃ until the acid value is unchanged;
Step 4: adding liquid epoxy resin and epoxidized soybean oil, and reacting at 90-110 ℃ until the acid value is unchanged;
Step 5: removing the solvent, cooling to 50-70 ℃, adding the active diluent under stirring, and then adding deionized water under vigorous stirring for 0.2-1 h;
preferably, the above solvent removal is specifically: vacuumizing to less than or equal to-0.09 MPa, and maintaining for 1h to remove the solvent.
Step 6: adding a photoinitiator, a flatting agent and a defoaming agent under the stirring state, uniformly mixing, and then adding a water-based isocyanate curing agent to obtain the water-based bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil.
The vigorous stirring is 1000-2000r/min; stirring at 400-600r/min.
According to one aspect of the invention, in steps 1-5, the mass percentages of the components are as follows:
According to one aspect of the invention, in step 1, the solvent is one or more of 1, 4-dioxane, N-dimethylformamide and dimethyl sulfoxide;
The catalyst is one of triphenylphosphine, N-dimethylaniline, N-dimethylbenzylamine and tetrabutylammonium bromide;
the polymerization inhibitor is one of hydroquinone, p-benzoquinone and p-methoxyphenol;
The epoxy compound with double bonds is one of glycidyl methacrylate and allyl glycidyl ether;
the liquid epoxy resin is one or more of liquid bisphenol A epoxy resin, hydrogenated liquid bisphenol A epoxy resin, 1, 4-cyclohexanediol diglycidyl ether, resorcinol diglycidyl ether and 1, 2-cyclohexanediol diglycidyl ether;
The polyethylene glycol diglycidyl ether is polyethylene glycol diglycidyl ether with an epoxy value of 1.0-3.5 mmol/g.
According to one aspect of the invention, in step 1, the molar ratio of the citric acid to the epoxy compound having a double bond is 1:1.9 to 2.1.
According to one aspect of the invention, in step 2, the molar ratio of the polyethylene glycol diglycidyl ether to the epoxy groups of the liquid epoxy resin is 1:0.1-1.
According to one aspect of the invention, in step 3, the molar ratio of the citric acid to the epoxy compound having a double bond is 1:0.9 to 1.1.
In accordance with one aspect of the present invention, in step 4, the epoxy group molar ratio of the liquid epoxy resin to the epoxidized soybean oil is 1:1 to 10.
According to one aspect of the invention, the reactive diluent is one or more of diethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene phthalate diacrylate and pentaerythritol triacrylate.
According to one aspect of the invention, in step 6, the photoinitiator accounts for 2 to 6% by mass based on the mass of the product prepared in step 5; the mass ratio of the leveling agent is 0.05-0.5%; the mass ratio of the defoaming agent is 0.1-1%; the mass ratio of the aqueous isocyanate curing agent is 2-20%;
The photoinitiator is one or more of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenylpropion, 2-hydroxy-3- (2' -thioxanthone oxy) -N, N, N-trimethyl-1-propylamine chloride, 1-hydroxy-cyclohexyl benzophenone and 2-hydroxy-2 methyl-1-phenylpropion;
The leveling agent is an organosilicon surface auxiliary agent; preferably, the leveling agent is one of organosilicon surface additives BYK-333 and Tego 822.
The defoaming agent is an organosilicon defoaming agent; the defoaming agent is one of organosilicon defoaming agents BYK-024 and Tego 4100.
Preferably, the aqueous isocyanate curing agent is one or a mixture of more than one of Desmodur N3900 and Bayhydur 401-70MPA/X of the Kochia company.
Based on the same inventive concept, the invention also provides the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil, which is prepared by the preparation method.
The invention has the beneficial effects that:
The aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil has the advantages of high bio-based content, reproducibility, environmental protection and low cost due to the adoption of citric acid, epoxidized soybean oil and bio-based polyethylene glycol diglycidyl ether (ethylene glycol bio-based source).
According to the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil, the main resin is subjected to waterborne treatment through the hydrophilic polyethylene glycol chain segments, and amine neutralization is not needed, so that the influence of residues of non-reacted organic amine on the material performance is avoided, and the emission of VOCs (volatile organic compounds) of a material system is reduced due to the absence of organic amine emission.
According to the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil, raw materials are added step by step through molecular structure design and gradual polymerization process control, so that the occurrence of gel in the reaction process is effectively avoided, the existing photo-curing groups with high functionality in the main resin are realized, and the photo-curing performance in the later stage of a system is ensured; the polyurethane resin has a large number of hydroxyl groups, and can be added with water-based isocyanate curing agent to react partial hydroxyl groups, so that the polyurethane chain segments are introduced into the main resin, the crosslinking density of the material is further improved, and various properties of the material such as hardness, tensile strength and the like are improved. The dual-curing system design combines the advantages of photo-curing and thermal-curing, so that the prepared material can realize quick primary curing and fixing through photo-curing, and the material performance such as adhesive force, crosslinking density, hardness, mechanical property and the like can be improved through thermal curing.
According to the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil, the material feeding proportion of raw materials is adjusted in various modes, so that the material performance can be adjusted and controlled. The content of hydrophilic polyethylene glycol chain segments can be reduced by adjusting the proportion of the liquid epoxy resin to the polyethylene glycol diglycidyl ether, and the rigid groups in the liquid epoxy resin are introduced into the main resin, so that the balance regulation of the hydrophilicity and the lipophilicity of the main resin and the performance regulation of the cured material are realized; more rigid groups in the liquid epoxy resin can be introduced into the main resin by adjusting the ratio of the liquid epoxy resin to the epoxidized soybean oil, so that the performance regulation and control of the cured material can be further realized; the content of the polyurethane chain segment can be regulated by regulating the addition amount of the aqueous isocyanate curing agent, so that the performance regulation and control of the cured material can be further realized. Therefore, the comprehensive synergy enables the photo-cured coating to have excellent performances such as high hardness, high mechanical property, high water resistance, high impact resistance and the like, and has great application prospects in the fields of printing packaging, wood furniture, antibacterial and antiviral coatings, medical sanitation, children toys and the like.
According to the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil, raw materials with different structures are introduced in the synthesis process to improve the material performance, so that the problem that the emulsion particles cannot be fully and uniformly mixed in the later emulsion due to physical blending and the modification effect is limited is avoided.
Drawings
FIG. 1 is a synthetic route diagram of an aqueous bio-based photo-thermal dual cure material based on citric acid and epoxidized soybean oil according to example 2 of the present invention;
Fig. 2 is an infrared spectrum of a main raw material and a preparation stage product of an aqueous bio-based photo-thermal dual curing material based on citric acid and epoxidized soybean oil according to example 2 of the present invention.
Detailed Description
In order that the invention may be more readily understood, the invention will be further described with reference to the following examples. It should be understood that these examples are intended to illustrate the invention and not to limit the scope of the invention, and that the described embodiments are merely some, but not all, of the embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Unless defined otherwise, the terms of art used hereinafter are consistent with the meanings understood by those skilled in the art; unless otherwise indicated, all the materials and reagents referred to herein are commercially available or may be prepared by well-known methods.
The main raw material glycidyl methacrylate of the water-based bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil is marked as GMA, and polyethylene glycol diglycidyl ether is marked as EPEGE; the liquid bisphenol a epoxy resin is noted BPAEP; epoxidized soybean oil is designated ESO.
In the preparation method of the aqueous bio-based photo-thermal dual curing material based on citric acid and epoxidized soybean oil according to each embodiment of the present application, the reaction product of (1) is denoted as C2G, (2) is denoted as ECG, (3) is denoted as AECG, and (4) is denoted as EPCG.
Further details are provided below in connection with specific examples.
Example 1
The preparation method of the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil comprises the following steps: (1) In a device provided with a stirrer, a constant pressure funnel, a condenser tube and a thermometer, 6.72 grams of citric acid, 20.0 grams of dioxane solvent, 0.50 grams of triphenylphosphine catalyst and 0.50 grams of p-methoxyphenol polymerization inhibitor are added, nitrogen is introduced, the temperature is slowly increased to 80 ℃, 9.95 grams of epoxy compound with double bonds of glycidyl methacrylate is slowly added dropwise after the citric acid is completely dissolved, the temperature is kept for 1 hour after the dropwise addition, and the temperature is increased to 100 ℃ for reaction for 2 hours. (2) Then, 38.18g of polyethylene glycol diglycidyl ether having an epoxy value of 1.65mmol/g and 1.59g of liquid bisphenol A epoxy resin were added and reacted at 100℃until the acid value was unchanged. (3) Then, 6.72g of citric acid and 4.98g of an epoxy compound having a double bond of glycidyl methacrylate were added thereto, and the mixture was reacted at 100℃until the acid value was unchanged. (4) 3.98g of liquid bisphenol A epoxy resin and 4.69g of epoxidized soybean oil were further added and reacted at 100℃until the acid value was unchanged. (5) Vacuumizing to less than or equal to-0.09 MPa, maintaining for 1h to remove the solvent, cooling to 60 ℃, adding 2.50g of dipropylene glycol diacrylate active diluent under stirring (500 r/min), and adding 120g of deionized water under vigorous stirring (1500 r/min) for 0.5h. (6) Adding 4.00g of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether-phenyl acetone photoinitiator, 0.50g of BYK-333 flatting agent and 0.50g of BYK-024 defoamer under the stirring state (500 r/min), uniformly mixing, and then adding 6.60g Bayhydur 401-70MPA/X aqueous isocyanate curing agent to obtain the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil.
Example 2
The preparation method of the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil comprises the following steps of: (1) In a device provided with a stirrer, a constant pressure funnel, a condenser tube and a thermometer, adding 6.72G of citric acid, 20.0G of dioxane solvent, 0.50G of triphenylphosphine catalyst and 0.50G of p-methoxyphenol polymerization inhibitor, introducing nitrogen, slowly heating to 80 ℃, slowly dropwise adding 9.95G of Glycidyl Methacrylate (GMA) epoxy compound with double bonds until the citric acid is completely dissolved, keeping the temperature for 1h after dropwise adding, and heating to 100 ℃ for 2h to obtain a reaction product C2G. (2) Then 33.94g of polyethylene glycol diglycidyl ether (EPEGE for short) with an epoxy value of 1.65mmol/g and 3.18g of liquid bisphenol A epoxy resin (BPAEP for short) are added, and the reaction product ECG is obtained after the reaction at 100 ℃ until the acid value is unchanged. (3) Then, 6.72g of citric acid and 4.98g of glycidyl methacrylate (GMA for short) of an epoxy compound having a double bond were added, and the mixture was reacted at 100℃until the acid value was unchanged, to obtain a reaction product AECG. (4) 3.98g of liquid bisphenol A epoxy resin (BPAEP for short) and 4.69g of epoxidized soybean oil (ESO for short) are added, and the mixture is reacted at 100 ℃ until the acid value is unchanged, thus obtaining a reaction product EPCG. (5) Vacuumizing to less than or equal to-0.09 MPa, maintaining for 1h to remove the solvent, cooling to 60 ℃, adding 2.50g of dipropylene glycol diacrylate active diluent under stirring (500 r/min), and adding 115g of deionized water under vigorous stirring (1500 r/min) for 0.5h. (6) Adding 4.00g of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether-phenyl acetone photoinitiator, 0.50g of BYK-333 flatting agent and 0.50g of BYK-024 defoamer under the stirring state (500 r/min), uniformly mixing, and then adding 6.60g Bayhydur 401-70MPA/X aqueous isocyanate curing agent to obtain the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil. The infrared spectrogram of the main raw materials and the products in the preparation process is shown in figure 2.
Example 3
The preparation method of the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil comprises the following steps: (1) In a device provided with a stirrer, a constant pressure funnel, a condenser tube and a thermometer, 6.72 grams of citric acid, 20.0 grams of dioxane solvent, 0.50 grams of triphenylphosphine catalyst and 0.50 grams of p-methoxyphenol polymerization inhibitor are added, nitrogen is introduced, the temperature is slowly increased to 80 ℃, 9.95 grams of epoxy compound with double bonds of glycidyl methacrylate is slowly added dropwise after the citric acid is completely dissolved, the temperature is kept for 1 hour after the dropwise addition, and the temperature is increased to 100 ℃ for reaction for 2 hours. (2) 29.70g of polyethylene glycol diglycidyl ether having an epoxide number of 1.65mmol/g and 4.78g of liquid bisphenol A epoxy resin were then added and reacted at 100℃until the acid number was unchanged. (3) Then, 6.72g of citric acid and 4.98g of an epoxy compound having a double bond of glycidyl methacrylate were added thereto, and the mixture was reacted at 100℃until the acid value was unchanged. (4) 3.98g of liquid bisphenol A epoxy resin and 4.69g of epoxidized soybean oil were further added and reacted at 100℃until the acid value was unchanged. (5) Vacuumizing to less than or equal to-0.09 MPa, maintaining for 1h to remove the solvent, cooling to 60 ℃, adding 2.50g of dipropylene glycol diacrylate active diluent under stirring (500 r/min), and adding 110g of deionized water under vigorous stirring (1500 r/min) for 0.5h. (6) Adding 4.00g of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether-phenyl acetone photoinitiator, 0.50g of BYK-333 flatting agent and 0.50g of BYK-024 defoamer under the stirring state (500 r/min), uniformly mixing, and then adding 6.60g Bayhydur 401-70MPA/X aqueous isocyanate curing agent to obtain the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil.
Example 4
The preparation method of the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil comprises the following steps: (1) In a device provided with a stirrer, a constant pressure funnel, a condenser tube and a thermometer, 6.72 grams of citric acid, 20.0 grams of dioxane solvent, 0.50 grams of triphenylphosphine catalyst and 0.50 grams of p-methoxyphenol polymerization inhibitor are added, nitrogen is introduced, the temperature is slowly increased to 80 ℃, 9.95 grams of epoxy compound with double bonds of glycidyl methacrylate is slowly added dropwise after the citric acid is completely dissolved, the temperature is kept for 1 hour after the dropwise addition, and the temperature is increased to 100 ℃ for reaction for 2 hours. (2) Then 33.94g of polyethylene glycol diglycidyl ether having an epoxy value of 1.65mmol/g and 3.18g of liquid bisphenol A epoxy resin were added and reacted at 100℃until the acid value was unchanged. (3) Then, 6.72g of citric acid and 4.98g of an epoxy compound having a double bond of glycidyl methacrylate were added thereto, and the mixture was reacted at 100℃until the acid value was unchanged. (4) 3.98g of liquid bisphenol A epoxy resin and 4.69g of epoxidized soybean oil were further added and reacted at 100℃until the acid value was unchanged. (5) Vacuumizing to less than or equal to-0.09 MPa, maintaining for 1h to remove the solvent, cooling to 60 ℃, adding 2.50g of dipropylene glycol diacrylate active diluent under stirring (500 r/min), and adding 115g of deionized water under vigorous stirring (1500 r/min) for 0.5h. (6) Adding 4.00g of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether-phenyl acetone photoinitiator, 0.50g of BYK-333 flatting agent and 0.50g of BYK-024 defoamer under the stirring state (500 r/min), uniformly mixing, and then adding 9.90g Bayhydur 401-70MPA/X aqueous isocyanate curing agent to obtain the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil.
Example 5
The preparation method of the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil comprises the following steps: (1) In a device provided with a stirrer, a constant pressure funnel, a condenser tube and a thermometer, 6.72 grams of citric acid, 20.0 grams of dioxane solvent, 0.50 grams of triphenylphosphine catalyst and 0.50 grams of p-methoxyphenol polymerization inhibitor are added, nitrogen is introduced, the temperature is slowly increased to 80 ℃, 9.95 grams of epoxy compound with double bonds of glycidyl methacrylate is slowly added dropwise after the citric acid is completely dissolved, the temperature is kept for 1 hour after the dropwise addition, and the temperature is increased to 100 ℃ for reaction for 2 hours. (2) Then 33.94g of polyethylene glycol diglycidyl ether having an epoxy value of 1.65mmol/g and 3.18g of liquid bisphenol A epoxy resin were added and reacted at 100℃until the acid value was unchanged. (3) Then, 6.72g of citric acid and 4.98g of an epoxy compound having a double bond of glycidyl methacrylate were added thereto, and the mixture was reacted at 100℃until the acid value was unchanged. (4) 1.59g of liquid bisphenol A epoxy resin and 7.51g of epoxidized soybean oil were further added and reacted at 100℃until the acid value was unchanged. (5) Vacuumizing to less than or equal to-0.09 MPa, maintaining for 1h to remove the solvent, cooling to 60 ℃, adding 2.50g of dipropylene glycol diacrylate active diluent under stirring (500 r/min), and adding 115g of deionized water under vigorous stirring (1500 r/min) for 0.5h. (6) Adding 4.00g of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether-phenyl acetone photoinitiator, 0.50g of BYK-333 flatting agent and 0.50g of BYK-024 defoamer under the stirring state (500 r/min), uniformly mixing, and then adding 6.60g Bayhydur 401-70MPA/X aqueous isocyanate curing agent to obtain the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil.
Comparative example 1
The preparation method of the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil comprises the following steps: (1) In a device provided with a stirrer, a constant pressure funnel, a condenser tube and a thermometer, 6.72 grams of citric acid, 20.0 grams of dioxane solvent, 0.50 grams of triphenylphosphine catalyst and 0.50 grams of p-methoxyphenol polymerization inhibitor are added, nitrogen is introduced, the temperature is slowly increased to 80 ℃, 9.95 grams of epoxy compound with double bonds of glycidyl methacrylate is slowly added dropwise after the citric acid is completely dissolved, the temperature is kept for 1 hour after the dropwise addition, and the temperature is increased to 100 ℃ for reaction for 2 hours. (2) 42.42g of polyethylene glycol diglycidyl ether having an epoxide number of 1.65mmol/g were added and reacted at 100℃until the acid number was unchanged. (3) Then, 6.72g of citric acid and 4.98g of an epoxy compound having a double bond of glycidyl methacrylate were added thereto, and the mixture was reacted at 100℃until the acid value was unchanged. (4) 9.39g of epoxidized soybean oil was further added thereto and reacted at 100℃until the acid value was unchanged. (5) Vacuumizing to less than or equal to-0.09 MPa, maintaining for 1h to remove the solvent, cooling to 60 ℃, adding 2.50g of dipropylene glycol diacrylate active diluent under stirring (500 r/min), and adding 120g of deionized water under vigorous stirring (1500 r/min) for 0.5h. (6) Adding 4.00g of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether-phenyl acetone photoinitiator, 0.50g of BYK-333 flatting agent and 0.50g of BYK-024 defoamer under the stirring state (500 r/min), uniformly mixing, and then adding 6.60g Bayhydur 401-70MPA/X aqueous isocyanate curing agent to obtain the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil.
Comparative example 2
The preparation method of the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil comprises the following steps: (1) In a device provided with a stirrer, a constant pressure funnel, a condenser tube and a thermometer, 6.72 grams of citric acid, 20.0 grams of dioxane solvent, 0.50 grams of triphenylphosphine catalyst and 0.50 grams of p-methoxyphenol polymerization inhibitor are added, nitrogen is introduced, the temperature is slowly increased to 80 ℃, 9.95 grams of epoxy compound with double bonds of glycidyl methacrylate is slowly added dropwise after the citric acid is completely dissolved, the temperature is kept for 1 hour after the dropwise addition, and the temperature is increased to 100 ℃ for reaction for 2 hours. (2) 42.42g of polyethylene glycol diglycidyl ether having an epoxide number of 1.65mmol/g were added and reacted at 100℃until the acid number was unchanged. (3) Then, 6.72g of citric acid and 4.98g of an epoxy compound having a double bond of glycidyl methacrylate were added thereto, and the mixture was reacted at 100℃until the acid value was unchanged. (4) 3.98g of liquid bisphenol A epoxy resin and 4.69g of epoxidized soybean oil were further added and reacted at 100℃until the acid value was unchanged. (5) Vacuumizing to less than or equal to-0.09 MPa, maintaining for 1h to remove the solvent, cooling to 60 ℃, adding 2.50g of dipropylene glycol diacrylate active diluent under stirring (500 r/min), and adding 120g of deionized water under vigorous stirring (1500 r/min) for 0.5h. (6) Adding 4.00g of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether-phenyl acetone photoinitiator, 0.50g of BYK-333 flatting agent and 0.50g of BYK-024 defoamer under the stirring state (500 r/min), uniformly mixing, and then adding 6.60g Bayhydur 401-70MPA/X aqueous isocyanate curing agent to obtain the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil.
Comparative example 3
The preparation method of the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil comprises the following steps: (1) In a device provided with a stirrer, a constant pressure funnel, a condenser tube and a thermometer, 6.72 grams of citric acid, 20.0 grams of dioxane solvent, 0.50 grams of triphenylphosphine catalyst and 0.50 grams of p-methoxyphenol polymerization inhibitor are added, nitrogen is introduced, the temperature is slowly increased to 80 ℃, 9.95 grams of epoxy compound with double bonds of glycidyl methacrylate is slowly added dropwise after the citric acid is completely dissolved, the temperature is kept for 1 hour after the dropwise addition, and the temperature is increased to 100 ℃ for reaction for 2 hours. (2) Then 33.94g of polyethylene glycol diglycidyl ether having an epoxy value of 1.65mmol/g and 3.18g of liquid bisphenol A epoxy resin were added and reacted at 100℃until the acid value was unchanged. (3) Then, 6.72g of citric acid and 4.98g of an epoxy compound having a double bond of glycidyl methacrylate were added thereto, and the mixture was reacted at 100℃until the acid value was unchanged. (4) 9.39g of epoxidized soybean oil was further added thereto and reacted at 100℃until the acid value was unchanged. (5) Vacuumizing to less than or equal to-0.09 MPa, maintaining for 1h to remove the solvent, cooling to 60 ℃, adding 2.50g of dipropylene glycol diacrylate active diluent under stirring (500 r/min), and adding 120g of deionized water under vigorous stirring (1500 r/min) for 0.5h. (6) Adding 4.00g of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether-phenyl acetone photoinitiator, 0.50g of BYK-333 flatting agent and 0.50g of BYK-024 defoamer under the stirring state (500 r/min), uniformly mixing, and then adding 6.60g Bayhydur 401-70MPA/X aqueous isocyanate curing agent to obtain the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil.
Comparative example 4
The preparation method of the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil comprises the following steps: (1) In a device provided with a stirrer, a constant pressure funnel, a condenser tube and a thermometer, 6.72 grams of citric acid, 20.0 grams of dioxane solvent, 0.50 grams of triphenylphosphine catalyst and 0.50 grams of p-methoxyphenol polymerization inhibitor are added, nitrogen is introduced, the temperature is slowly increased to 80 ℃, 9.95 grams of epoxy compound with double bonds of glycidyl methacrylate is slowly added dropwise after the citric acid is completely dissolved, the temperature is kept for 1 hour after the dropwise addition, and the temperature is increased to 100 ℃ for reaction for 2 hours. (2) Then 33.94g of polyethylene glycol diglycidyl ether having an epoxy value of 1.65mmol/g and 3.18g of liquid bisphenol A epoxy resin were added and reacted at 100℃until the acid value was unchanged. (3) Then, 6.72g of citric acid and 4.98g of an epoxy compound having a double bond of glycidyl methacrylate were added thereto, and the mixture was reacted at 100℃until the acid value was unchanged. (4) 3.98g of liquid bisphenol A epoxy resin and 4.69g of epoxidized soybean oil were further added and reacted at 100℃until the acid value was unchanged. (5) Vacuumizing to less than or equal to-0.09 MPa, maintaining for 1h to remove the solvent, cooling to 60 ℃, adding 2.50g of dipropylene glycol diacrylate active diluent under stirring (500 r/min), and adding 115g of deionized water under vigorous stirring (1500 r/min) for 0.5h. (6) Adding 4.00g of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether-phenyl acetone photoinitiator, 0.50g of BYK-333 flatting agent and 0.50g of BYK-024 defoamer under the stirring state (500 r/min), and uniformly mixing to obtain the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil.
Comparative example 5
The preparation method of the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil comprises the following steps: (1) In a device provided with a stirrer, a constant pressure funnel, a condenser tube and a thermometer, 6.72 grams of citric acid, 20.0 grams of dioxane solvent, 0.50 grams of triphenylphosphine catalyst and 0.50 grams of p-methoxyphenol polymerization inhibitor are added, nitrogen is introduced, the temperature is slowly increased to 80 ℃, 9.95 grams of epoxy compound with double bonds of glycidyl methacrylate is slowly added dropwise after the citric acid is completely dissolved, the temperature is kept for 1 hour after the dropwise addition, and the temperature is increased to 100 ℃ for reaction for 2 hours. (2) 14.93g of polyethylene glycol diglycidyl ether having an epoxide number of 3.75mmol/g and 3.18g of liquid bisphenol A epoxy resin were then added and reacted at 100℃until the acid number was unchanged. (3) Then, 6.72g of citric acid and 4.98g of an epoxy compound having a double bond of glycidyl methacrylate were added thereto, and the mixture was reacted at 100℃until the acid value was unchanged. (4) 3.98g of liquid bisphenol A epoxy resin and 4.69g of epoxidized soybean oil were further added and reacted at 100℃until the acid value was unchanged. (5) Vacuumizing to less than or equal to-0.09 MPa, maintaining for 1h to remove the solvent, cooling to 60 ℃, adding 2.50g of dipropylene glycol diacrylate active diluent under stirring (500 r/min), and adding 120g of deionized water under vigorous stirring (1500 r/min) for 0.5h. (6) Adding 4.00g of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether-phenyl acetone photoinitiator, 0.50g of BYK-333 flatting agent and 0.50g of BYK-024 defoamer under the stirring state (500 r/min), uniformly mixing, and then adding 6.60g Bayhydur 401-70MPA/X aqueous isocyanate curing agent to obtain the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil.
Performance detection and result analysis:
The aqueous bio-based photo-thermal dual curing materials based on citric acid and epoxidized soybean oil prepared in the above examples 1 to 5 and comparative examples 1 to 5 were coated and molded with 150 micro-wire rods, dried at room temperature for 2 hours, dried in a 40 ℃ drying oven for 2 hours, and finally irradiated with a 4kW high-pressure mercury lamp for 10cm for 20s, and heated in an 80 ℃ oven for 3 hours to obtain the cured coating.
Visual inspection is adopted for appearance; storage stability visual appearance change on centrifuge at 3000r centrifuge for 15 min; the adhesive force is obtained by referring to GB/T4893.4-2013 furniture surface paint film physicochemical property test part 4: the adhesive force cross cutting measurement method adopts an adhesive force tester to test by a cross-cut method; the pencil hardness is tested by adopting a pencil hardness method according to GB/T6739-2006 paint film hardness measured by a colored paint and varnish pencil method; flexibility is tested with reference to GB/T1731-1993 paint film flexibility assay; impact resistance is tested by referring to GB/T1732-1993 paint film impact resistance assay; the water resistance is that a coating film is firstly dried in an oven at 60 ℃ for 24 hours and then weighed by W0, then soaked in deionized water at 20 ℃ for 24 hours and then weighed by W1, and finally the water resistance S= (W1-W0) is calculated to be 100%/W0; tensile strength and elongation at break were measured with a universal tester at a tensile rate of 10 mm/min; biobased content is calculated from the United states department of agriculture by defining the biobased content of a product as "the percentage of biochar content in a material or product to the weight (mass) of total organic carbon in the product". The results of each performance test are shown in Table 1.
TABLE 1 results of Performance test of different aqueous bio-based photo-thermal Dual curing materials based on citric acid and epoxidized Soybean oil
As can be seen from examples 1 to 5 of Table 1, the aqueous bio-based photo-thermal dual-curing materials prepared by the preparation method of the invention have the advantages of good storage stability, good flexibility, good impact resistance, good mechanical property, good water resistance, high bio-based content, good adhesive force and high hardness, and have great application prospects in the fields of aqueous bio-based photo-curing materials, especially in the fields of printing packaging, wood furniture, antibacterial and antiviral coatings, medical and health, children toys and the like. As can be seen from the comparative analysis of examples 1 to 5 and comparative example 1 of Table 1, the aqueous bio-based photo-thermal dual-cured materials based on citric acid and epoxidized soybean oil prepared without introducing liquid bisphenol A epoxy resin in the preparation method step (2) and step (4) were inferior in both water resistance and mechanical properties. As is clear from the comparative analysis of examples 1 to 5, comparative example 1 and comparative example 2 of Table 1, the aqueous bio-based photo-thermal dual curing material based on citric acid and epoxidized soybean oil prepared without introducing liquid bisphenol A epoxy resin in the step (2) of the preparation method had poor water resistance and mechanical properties, but was better than that of comparative example 1. As is evident from comparative analysis of examples 1-5, comparative examples 1-2 and comparative example 3 of Table 1, the aqueous bio-based photo-thermal dual curing material based on citric acid and epoxidized soybean oil prepared without introducing liquid bisphenol A epoxy resin in the step (4) of the preparation method has poor mechanical properties but better water resistance than those of comparative examples 1 and comparative example 2. Therefore, the introduction of the liquid bisphenol A epoxy resin in the step (2) of the preparation method is proved to be a necessary condition for improving the water resistance of the material, and the introduction of the liquid bisphenol A epoxy resin in the step (4) of the preparation method can improve the water resistance and mechanical property of the material as a whole. As can be seen from the comparative analysis of examples 3,4 and 4 in table 1, the aqueous bio-based photo-thermal dual curing material based on citric acid and epoxidized soybean oil prepared without introducing the aqueous isocyanate curing agent in the step (6) of the preparation method has low hardness, poor water resistance and poor mechanical properties, so that the introduction of the aqueous isocyanate curing agent is proved to be very important for improving the material properties and is also a necessary raw material for designing the photo-thermal dual curing material system. As is evident from the comparative analysis of example 2 and comparative example 5 of Table 1, the aqueous bio-based photo-thermal dual curing material based on citric acid and epoxidized soybean oil prepared by using polyethylene glycol diglycidyl ether having an epoxy value of 3.75mmol/g in step (2) of the preparation method has poor storage stability, poor impact resistance, low elongation at break and low bio-based content, thus proving that the preference of polyethylene glycol diglycidyl ether having different epoxy values is critical to the material properties.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil is characterized by comprising the following steps of:
Step 1: in an inert gas atmosphere, mixing citric acid, a solvent, a catalyst and a polymerization inhibitor, slowly heating to 60-90 ℃, slowly dropwise adding an epoxy compound with double bonds after the citric acid is completely dissolved, preserving heat for 1h after dropwise adding, and heating to 90-110 ℃ for reacting for 1-4 h;
step 2: then adding polyethylene glycol diglycidyl ether and liquid epoxy resin, and reacting at 90-110 ℃ until the acid value is unchanged;
step 3: then adding citric acid and epoxy compound with double bonds, and reacting at 90-110 ℃ until the acid value is unchanged;
Step 4: adding liquid epoxy resin and epoxidized soybean oil, and reacting at 90-110 ℃ until the acid value is unchanged;
step 5: removing the solvent, cooling to 50-70 ℃, adding the active diluent under stirring, and then adding deionized water under vigorous stirring for 0.2-1 h;
Step 6: adding a photoinitiator, a flatting agent and a defoaming agent under the stirring state, uniformly mixing, and then adding a water-based isocyanate curing agent to obtain the water-based bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil.
2. The method for preparing the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil according to claim 1, wherein in the step 1-5, the mass percentages of the components are as follows:
3. The method for preparing an aqueous bio-based photo-thermal dual curing material based on citric acid and epoxidized soybean oil according to claim 1, wherein in step 1, the solvent is one or more of 1, 4-dioxane, N-dimethylformamide and dimethyl sulfoxide; the catalyst is one of triphenylphosphine, N-dimethylaniline, N-dimethylbenzylamine and tetrabutylammonium bromide;
The polymerization inhibitor is one of hydroquinone, p-benzoquinone and p-methoxyphenol; the epoxy compound with double bonds is one of glycidyl methacrylate and allyl glycidyl ether;
the liquid epoxy resin is one or more of liquid bisphenol A epoxy resin, hydrogenated liquid bisphenol A epoxy resin, 1, 4-cyclohexanediol diglycidyl ether, resorcinol diglycidyl ether and 1, 2-cyclohexanediol diglycidyl ether;
The polyethylene glycol diglycidyl ether is polyethylene glycol diglycidyl ether with an epoxy value of 1.0-3.5 mmol/g.
4. The method for preparing an aqueous bio-based photo-thermal dual curing material based on citric acid and epoxidized soybean oil according to claim 1, wherein in step 1, the molar ratio of the citric acid to the epoxy compound having a double bond is 1:1.9-2.1.
5. The method for preparing an aqueous bio-based photo-thermal dual curing material based on citric acid and epoxidized soybean oil according to claim 1, wherein in step 2, the molar ratio of the polyethylene glycol diglycidyl ether to the epoxy groups of the liquid epoxy resin is 1:0.1-1.
6. The method for preparing an aqueous bio-based photo-thermal dual curing material based on citric acid and epoxidized soybean oil according to claim 1, wherein in step 3, the molar ratio of the citric acid to the epoxy compound having a double bond is 1:0.9-1.1.
7. The method for preparing an aqueous bio-based photo-thermal dual curing material based on citric acid and epoxidized soybean oil according to claim 1, wherein in step 4, the epoxy group molar ratio of the liquid epoxy resin and the epoxidized soybean oil is 1:1 to 10.
8. The method for preparing the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil according to claim 1, wherein the reactive diluent is one or more of diethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol phthalate diacrylate and pentaerythritol triacrylate.
9. The method for preparing the aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil according to claim 1, wherein in step 6, the mass ratio of the photoinitiator is 2-6% based on the mass of the product prepared in step 5; the mass ratio of the leveling agent is 0.05-0.5%; the mass ratio of the defoaming agent is 0.1-1%; the mass ratio of the aqueous isocyanate curing agent is 2-20%;
The photoinitiator is one or more of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenylpropion, 2-hydroxy-3- (2' -thioxanthone oxy) -N, N, N-trimethyl-1-propylamine chloride, 1-hydroxy-cyclohexyl benzophenone and 2-hydroxy-2 methyl-1-phenylpropion; the leveling agent is an organosilicon surface auxiliary agent;
the defoaming agent is an organosilicon defoaming agent.
10. The aqueous bio-based photo-thermal dual-curing material based on citric acid and epoxidized soybean oil prepared by the preparation method according to any one of claims 1 to 9.
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