CN115141157A - Isocyanuric acid triacrylate, and preparation method and application thereof - Google Patents
Isocyanuric acid triacrylate, and preparation method and application thereof Download PDFInfo
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- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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Abstract
The invention belongs to the technical field of acrylic resin preparation, and particularly relates to isocyanuric acid triacrylate as well as a preparation method and application thereof. The invention applies beta- (acryloyloxy) propionic acid to the preparation of the isocyanuric acid triacrylate, can reduce the problem that a large amount of high-COD esterified wastewater is generated when the prior art is used for preparing the isocyanuric acid triacrylate, can not cause the beta- (acryloyloxy) propionic acid to be azeotroped with water, has less amount of oligomers and gel generated in an esterification tower and a condenser, does not need frequent cleaning equipment, reduces the COD content of the wastewater, and has low COD content when the beta- (acryloyloxy) propionic acid is used for preparing the isocyanuric acid triacrylate, wherein the esterified wastewater is below 3mg KOH/g. The preparation of the isocyanuric acid triacrylate by taking the beta- (acryloyloxy) propionic acid as a raw material can be in a liquid state at low temperature, crystallization does not occur, the isocyanuric acid triacrylate does not need to be preheated before use, and the working procedures are reduced.
Description
Technical Field
The invention belongs to the technical field of acrylic resin preparation, and particularly relates to isocyanuric acid triacrylate as well as a preparation method and application thereof.
Background
The light curing technology is an energy-saving, clean and environment-friendly technology, the energy consumption of the light curing technology is only one tenth of that of the traditional mercury lamp, the light curing technology does not contain solvent, has the protection effect on the ecological environment, does not discharge toxic gas and carbon dioxide to the atmosphere, and is known as 'green technology'. The photo-curing technology is a photo-processing technology which makes liquid coating, ink or adhesive polymerize at high speed to form a solid state by ultraviolet irradiation with a certain wavelength. In recent years, with the emphasis on environmental issues, environmental friendly photo-curing technology has been rapidly developed.
The photocuring system has the advantages of fast curing, low energy consumption, outstanding glossiness and mechanical property and the like, and is widely applied to the fields of coatings, printing ink and the like. With the development of society, light-cured coatings or inks and the like have new requirements on high temperature resistance, such as resistance to cigarette end scalding and non-marking. The raw materials of the light-cured coating comprise resin, pigment, solvent, auxiliary agent and the like, wherein the resin is the main component of the coating and determines the basic characteristics of the coating. Conventional resin systems include epoxy acrylates, urethane acrylates, amino acrylates, polyester acrylates, and the like. Generally, the temperature resistance of the polyurethane acrylate does not exceed 150 ℃; the epoxy acrylate does not exceed 200 ℃; the amino acrylate has slightly good temperature resistance, but has the problem of formaldehyde residue, and is not suitable for popularization and application. Polyester acrylates having better temperature resistance are also less common.
Isocyanurates contain a stable triazine ring structure and have good thermal and chemical stability. If it is incorporated into the resin main chain, the strength and heat resistance of the coating can be improved. Chinese patent document CN102260221A discloses a preparation method of an isocyanuric acid triacrylate or an isocyanuric acid methacrylate monomer, which takes acrylic acid/methacrylic acid, tris (2-hydroxyethyl) isocyanurate, a water-carrying agent, a polymerization inhibitor and a catalyst as raw materials, and obtains the trifunctional isocyanuric acid triacrylate or the isocyanuric acid methacrylate monomer after esterification reaction, purification, separation and purification. In the esterification process of acrylic acid/methacrylic acid and tris (2-hydroxyethyl) isocyanurate, acrylic acid or methacrylic acid is azeotroped with water generated by esterification, a large amount of acrylic acid or methacrylic acid can form gel and oligomer in an esterification tower and a condenser, and frequent cleaning equipment is needed; in addition, the acid value of the waste water generated in the esterification process is between 30 and 150mgKOH/g, the waste water amount is large, and the COD is extremely high due to the large amount of acrylic acid or methacrylic acid contained in the waste water, generally between tens of thousands and hundreds of thousands.
Further, the isocyanuric acid triacrylate prepared by the prior art is very inconvenient in actual industrial production because the triacrylate is crystallized at low temperature, and the triacrylate is required to be heated to a liquid product in advance before use and then added into a formulation system.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that in the prior art, when the isocyanuric acid triacrylate is prepared, a large amount of acrylic acid or methacrylic acid can form gel and oligomer in an esterification tower and a condenser due to azeotropic boiling of the acrylic acid or the methacrylic acid and wastewater generated by esterification, frequent cleaning of equipment is required, and when the acrylic acid or the methacrylic acid is subjected to esterification reaction with tris (2-hydroxyethyl) isocyanurate, the amount of wastewater generated is large, the COD content is high and the like, so that the isocyanuric acid triacrylate, the preparation method and the application thereof are provided.
Therefore, the invention provides the following technical scheme.
The invention provides an application of beta- (acryloyloxy) propionic acid in preparation of isocyanuric acid triacrylate.
The invention also provides isocyanuric acid triacrylate, which has the following structural formula,
in addition, the invention provides a preparation method of the isocyanuric acid triacrylate, which comprises the following steps,
(1) Mixing tris (2-hydroxyethyl) isocyanurate, beta- (acryloyloxy) propionic acid and a catalyst uniformly to obtain a mixture; heating and reacting;
(2) And (3) determining the acid value of the reaction system after 5-8h of reaction, finishing the reaction when the acid value of the reaction system is lower than the theoretical acid value, cooling, washing with water, neutralizing, and removing the solvent to obtain the isocyanuric acid triacrylate.
The preparation method satisfies at least one of A-B,
A. the molar ratio of tris (2-hydroxyethyl) isocyanurate to beta- (acryloyloxy) propionic acid is 1 (3-4), preferably 1 (3-3.4);
B. the catalyst is at least one of methanesulfonic acid, p-toluenesulfonic acid and sulfuric acid.
The preparation method satisfies at least one of A-B,
A. in the step (1), the heating temperature is 100-120 ℃, preferably, the heating temperature is 100-105 ℃; in the preparation of the isocyanurate triacrylate, the temperature of the mixture inside the reaction vessel can be made to be between 75 and 95 ℃ by controlling the temperature outside the reaction vessel to be between 100 and 120 ℃ (that is, the temperature of the heating).
B. In the step (1), the pressure of the reaction is 10 to 100KPa, preferably 40 to 60KPa.
The preparation method satisfies at least one of A to E,
A. in the step (1), a step of adding a first polymerization inhibitor is further included before obtaining the mixture;
B. the step of adding a solvent before obtaining the mixture;
C. the step of adding an antioxidant is also included before the mixture is obtained;
D. in the step (2), a step of adding a solvent before the water washing is carried out is also included; the amount of solvent added is calculated as follows:
E. the method also comprises the step of adding a second polymerization inhibitor before removing the solvent.
When the isocyanuric acid triacrylate is prepared, the step (2) specifically comprises the steps of measuring the acid value of a reaction system after the reaction is carried out for 5-8 hours, cooling when the acid value of the reaction system is lower than the theoretical acid value, adding a solvent, and sequentially carrying out primary washing, neutralization, secondary washing, tertiary washing and solvent removal to obtain the isocyanuric acid triacrylate. Wherein the solution used for neutralization is at least one of 10wt% sodium hydroxide aqueous solution, 20wt% sodium hydroxide aqueous solution and 20wt% sodium carbonate aqueous solution.
The preparation method satisfies at least one of A to F,
A. the dosage of the catalyst is 1-4% of the total mass of the reaction materials, and preferably 1.5-2.5%; the catalyst is at least one of methanesulfonic acid, p-toluenesulfonic acid and sulfuric acid; wherein the methanesulfonic acid is added in the form of a 70wt% aqueous solution of methanesulfonic acid and the sulfuric acid is added in the form of a 98wt% aqueous solution of sulfuric acid;
B. the dosage of the first polymerization inhibitor is 0.01-1.0 percent of the total mass of the reaction materials, and preferably 0.02-0.1 percent;
C. the dosage of the solvent in the step (1) is 10-50% of the total mass of the reaction materials, and is preferably 25-35%;
D. the dosage of the antioxidant is 0.1 to 1 percent of the total mass of the reaction materials;
E. the second polymerization inhibitor is used in an amount of 0.01 to 1.0% by weight, preferably 0.04 to 0.06% by weight, based on the theoretical yield of isocyanurate triacrylate.
Wherein the total mass of the reaction materials refers to the total mass of tris (2-hydroxyethyl) isocyanurate (mosaic), beta- (acryloyloxy) propionic acid (beta-CEA), a catalyst, a first polymerization inhibitor, the solvent added in the step (1), a second polymerization inhibitor and an antioxidant.
The preparation method satisfies at least one of A-D,
A. the first polymerization inhibitor comprises at least one of copper chloride, copper sulfate and cuprous oxide;
preferably, the first polymerization inhibitor further comprises at least one of p-hydroxyanisole and 2, 6-di-tert-butyl-p-cresol;
B. the antioxidant is at least one of 50% hypophosphorous acid, 2, 6-di-tert-butyl-p-cresol and antioxidant 626; wherein the 50% hypophosphorous acid is a hypophosphorous acid aqueous solution with the mass concentration of 50%;
C. the solvent is at least one of toluene, benzene, cyclohexane and n-hexane;
D. the second polymerization inhibitor is at least one of p-hydroxyanisole and 2, 6-di-tert-butyl-p-cresol.
In the preparation method, sodium hydroxide or sodium bicarbonate is adopted for the neutralization step.
Further, the present invention provides the use of the above-mentioned isocyanuric acid triacrylate or the isocyanuric acid triacrylate prepared by the above-mentioned method in a coating, an ink or 3D printing.
The technical scheme of the invention has the following advantages:
1. the application of the beta- (acryloyloxy) propionic acid in the preparation of the isocyanuric acid triacrylate can solve the problems that a large amount of high-COD esterification wastewater is generated in the preparation of the isocyanuric acid triacrylate in the prior art, the beta- (acryloyloxy) propionic acid does not azeotrope with water, the amount of oligomers and gel generated in an esterification tower and a condenser is small, frequent cleaning equipment is not needed, the COD content of the wastewater is reduced, the esterification wastewater of the beta- (acryloyloxy) propionic acid in the preparation of the isocyanuric acid triacrylate is generally below 3mg KOH/g, and the COD of the generated wastewater is between hundreds and thousands. In addition, the preparation of the isocyanuric acid triacrylate by taking the beta- (acryloyloxy) propionic acid as a raw material can ensure that the isocyanuric acid triacrylate is in a liquid state under a low-temperature condition, does not generate crystallization, does not need to preheat the isocyanuric acid triacrylate before use, and reduces the working procedures.
Furthermore, the isocyanuric acid triacrylate prepared by taking the beta- (acryloyloxy) propionic acid as a raw material has heat resistance, the high-temperature weight loss of the isocyanuric acid triacrylate is less, and meanwhile, the isocyanuric acid triacrylate has better flexibility, can not be crystallized after being placed at the low temperature of minus 20 ℃ for a long time, and can not be cracked when being applied to coatings, printing ink or 3D printing.
2. The isocyanuric acid triacrylate provided by the invention can be liquid at low temperature (-20 ℃), cannot crystallize, and has better flexibility, low temperature resistance and the like.
3. The invention provides a preparation method of isocyanuric acid triacrylate, which comprises the steps of (1) uniformly mixing tris (2-hydroxyethyl) isocyanurate, beta- (acryloyloxy) propionic acid and a catalyst to obtain a mixture; heating and reacting; (2) And (3) measuring the acid value of the reaction system after the reaction is carried out for 5-8h, finishing the reaction when the acid value of the reaction system is lower than the theoretical acid value, cooling, washing with water, neutralizing, and removing the solvent to obtain the isocyanuric acid triacrylate. When the method is used for preparing the isocyanuric acid triacrylate, COD (chemical oxygen demand) in wastewater generated in the esterification process is extremely low, the treatment difficulty of the wastewater is reduced, the beta- (acryloyloxy) propionic acid cannot be azeotroped with water, oligomers and gels in an esterification tower and a condenser are reduced, the frequency of cleaning equipment is reduced, and the COD content in the wastewater is extremely low because the wastewater does not contain organic matters such as acrylic acid, the beta- (acryloyloxy) propionic acid and the like.
The isocyanuric acid triacrylate prepared by taking beta- (acryloyloxy) propionic acid as a raw material has excellent flexibility, does not have the problem of brittle fracture when being used in the fields of 3D printing, ink or coating, has better low-temperature resistance, can be stored in a liquid form at the temperature of-20 ℃, and does not crystallize.
Furthermore, the isocyanuric acid triacrylate prepared by the method is trifunctional, and compared with difunctional isocyanuric acid triacrylate, the trifunctional isocyanuric acid triacrylate has the advantages of higher curing speed and wider application range.
4. The preparation method of the isocyanuric acid triacrylate, provided by the invention, can reduce byproducts such as a self-polymerization product and a Michael addition product by controlling the reaction temperature and pressure, and improve the yield of the isocyanuric acid triacrylate, so that the yield of the product is over 90 percent. This is because the double bond activity of the acrylate is high, and when the temperature is too high, the activity is exponentially increased, and more byproducts are generated; the temperature and pressure of the mixture system are controlled, so that the mixture system can carry out forward reaction at a lower temperature, the yield is improved, and byproducts are reduced.
When the isocyanuric acid triacrylate is prepared, a solvent is added before the water washing step, so that the effect of dilution can be achieved, and the layering of a water phase and an oil phase is facilitated.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an infrared spectrum of an isocyanuric acid triacrylate obtained in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance image of isocyanuric acid triacrylate prepared in example 1 of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
This example provides a method for preparing isocyanurate triacrylate, comprising the following steps,
261kg of seek, 317.41kg of toluene, 454.01kg of beta- (acryloyloxy) propionic acid, 3.174kg of 50% hypophosphorous acid, 21.16kg of 70% of methanesulfonic acid, 0.212kg of p-hydroxyanisole and 1.058kg of copper chloride are placed into a reaction kettle, stirring is started, air is introduced from the bottom of the reaction kettle to uniformly mix reaction materials, the reaction kettle is heated to ensure that the external temperature of the reaction kettle is 100-105 ℃, the temperature of a mixture reaction system in the reaction kettle is 78-95 ℃, the pressure is 40-60KPa, and when the system begins to reflux and discharge water, the reaction is started and timing is carried out;
after 6 hours of reaction, measuring the acid value of the system, when the acid value is lower than the theoretical acid value of 18.48mg KOH/g, indicating that the reaction is finished, stopping the reaction, cooling to below 50 ℃, transferring the mixed solution in the reaction kettle to a water washing neutralization kettle, adding 641kg of toluene, adding 160kg of deionized water, stirring for 10min, carrying out primary water washing, standing for 2 hours, layering the water phase and the oil phase in the mixed solution, discharging the water phase, continuously standing until no wastewater drips, taking the oil phase to measure the acid value, wherein the acid value is 4.32mg KOH/g, adding 55kg of NaOH solution with the mass fraction of 10% according to the acid value, neutralizing, stirring for 10min, standing for 3 hours, layering the water phase and the oil phase, discharging the water phase, standing until no wastewater drips, adding 160kg of deionized water, stirring for 10min, carrying out secondary water washing, standing for 2 hours, layering the water phase and the oil phase, discharging the water phase, continuously standing for 2 hours, adding 160kg of deionized water, stirring for 10min, carrying out tertiary water washing, standing for layering, continuing to the water phase, transferring to a reaction kettle until no wastewater drips, adding 80 ppm of an isocyanuric acid ester, adding a solvent, standing for reaction kettle, and stopping the reaction, adding 500-75 ppm of the residual isocyanuric acid ester.
Example 2
This example provides a method for preparing isocyanuric acid triacrylate, comprising the following steps,
putting 261kg of mosaic, 318.35kg of toluene, 454.01kg of beta- (acryloyloxy) propionic acid, 3.183kg of 50% hypophosphorous acid, 23.35kg of 70% methanesulfonic acid, 0.212kg of p-hydroxyanisole and 1.061kg of copper chloride into a reaction kettle, starting stirring, introducing air from the bottom of the reaction kettle to uniformly mix reaction materials, heating the reaction kettle to ensure that the external temperature of the reaction kettle is 100-105 ℃, the temperature of a mixture reaction system in the reaction kettle is 78-95 ℃, the pressure is 40-60KPa, and indicating that the reaction starts to be carried out and timing when the system starts to reflux water;
after reacting for 6 hours, measuring the acid value of the system, when the acid value is lower than the theoretical acid value of 19.33mg KOH/g, indicating that the reaction is finished, stopping the reaction, cooling to below 50 ℃, transferring the mixed solution in the reaction kettle to a washing neutralization kettle, adding 615kg of methylbenzene, adding 160kg of deionized water, stirring for 10min, carrying out primary washing, then standing for 2 hours, layering the water phase and the oil phase in the mixed solution, discharging the water phase, continuously standing until no wastewater drips, taking the oil phase to measure the acid value, wherein the acid value is 4.43mg KOH/g, adding 56kg of NaOH solution with the mass fraction of 10% according to the acid value, stirring for 10min, standing for 3 hours, layering the water phase and the oil phase, discharging the water phase, continuously standing until no wastewater drips, adding 160kg of deionized water, stirring for 10min, carrying out secondary washing, standing for 2 hours, layering the water phase and the oil phase, discharging the water phase, continuously standing for 2 hours, adding 100kg of deionized water, stirring for 10min, carrying out tertiary washing, layering the water phase and the oil phase, continuously transferring to the reaction kettle until no wastewater drips, adding the solvent, keeping the reaction kettle at the temperature below 0.33 kg of the residual anisole, standing, adding the solvent, keeping the reaction kettle, and keeping the reaction kettle at the temperature, and keeping the reaction kettle at the temperature of 500ppm of the reaction kettle.
Example 3
This example provides a method for preparing isocyanuric acid triacrylate, comprising the following steps,
261kg of seek, 327kg of toluene, 475.63kg of beta- (acryloyloxy) propionic acid, 3.270kg of 50% hypophosphorous acid, 21.80kg of 70% of methanesulfonic acid, 0.218kg of p-hydroxyanisole and 1.090kg of copper chloride are placed into a reaction kettle, stirring is started, air is introduced from the bottom of the reaction kettle to uniformly mix reaction materials, the reaction kettle is heated to ensure that the external temperature of the reaction kettle is 100-105 ℃, the temperature of a mixture reaction system in the reaction kettle is 79-95 ℃, the pressure is 40-60KPa, and when the system begins to reflux and discharge water, the reaction is started and timing is carried out;
after reacting for 6 hours, measuring the acid value of the system, when the acid value is lower than the theoretical acid value of 26.39mg KOH/g, indicating that the reaction is finished, stopping the reaction, cooling to below 50 ℃, transferring the mixed solution in the reaction kettle to a washing neutralization kettle, adding 631.5kg of toluene, adding 160kg of deionized water, stirring for 10min, carrying out primary washing, then standing for 2 hours, layering the water phase and the oil phase in the mixed solution, discharging the water phase, continuously standing until no wastewater drips, taking the oil phase, measuring the acid value, wherein the acid value is 8.54mg KOH/g, adding 107kg of NaOH solution with the mass fraction of 10% according to the acid value, stirring for 10min, standing for 3 hours, layering the water phase and the oil phase, discharging the water phase, continuously standing until no wastewater drips, adding 160kg of deionized water, stirring for 10min, carrying out secondary washing, standing for 2 hours, layering the water phase and the oil phase, discharging the water phase, continuously standing for 2 hours, adding 160kg of deionized water, stirring for 10min, carrying out tertiary water washing for 2 hours, continuously standing until no wastewater drips, adding the oil phase and the oil phase, keeping the reaction kettle to a reaction kettle, adding the residual anisole, standing until the residual solvent is lower than 500-75 ppm of toluene, and stopping the reaction, and adding the reaction kettle, and keeping the residual anisole from the reaction kettle, and carrying out the reaction, and carrying out a reaction.
Example 4
This example provides a method for preparing isocyanuric acid triacrylate, comprising the following steps,
adding 261kg of cyc, 317.41kg of toluene, 454.01kg of beta- (acryloyloxy) propionic acid, 3.174kg of 50% hypophosphorous acid, 21.16kg of p-toluenesulfonic acid, 0.212kg of 2, 6-di-tert-butyl-p-cresol and 1.058kg of anhydrous copper sulfate into a reaction kettle, starting stirring, introducing air from the bottom of the reaction kettle to uniformly mix reaction materials, heating the reaction kettle to ensure that the external temperature of the reaction kettle is 100-105 ℃, the temperature of a mixture reaction system in the reaction kettle is 78-95 ℃, the pressure is 40-60KPa, and when the system begins to reflux and discharge water, indicating that the reaction starts to carry out and timing;
after 6 hours of reaction, measuring the acid value of the system, when the acid value is lower than the theoretical acid value 16.63mg KOH/g, indicating that the reaction is finished, stopping the reaction, cooling to below 50 ℃, transferring the mixed solution in the reaction kettle to a water washing neutralization kettle, adding 641kg of toluene, adding 160kg of deionized water, stirring for 10min, carrying out primary water washing, standing for 2 hours, layering the water phase and the oil phase in the mixed solution, discharging the water phase, continuously standing until no wastewater drips, taking the oil phase to measure the acid value, wherein the acid value is 5.27mg KOH/g, adding 60kg of NaOH solution with the mass fraction of 10% according to the acid value, neutralizing, stirring for 10min, standing for 3 hours, layering the water phase and the oil phase, discharging the water phase, standing for 10min, standing for 2 hours, layering the water phase and the oil phase, discharging the water phase, stirring for 10min, carrying out tertiary water washing, standing for 2 hours, standing for layering the water phase and the oil phase, adding 160kg of deionized water, stirring for 10min, continuing to the water phase, adding 80 ppm of the toluene after no wastewater drips, and removing the residual solvent from the reaction kettle, and adding 500ppm of the isocyanuric acid ester, and stopping the reaction.
Comparative example 1
The comparative example provides a method for preparing isocyanuric acid triacrylate, comprising the steps of,
putting 261kg of cyc, 230.93kg of toluene, 259.2kg of acrylic acid, 2.309kg50% hypophosphorous acid, 15.4kg70% of methanesulfonic acid, 0.154kg of p-hydroxyanisole and 0.770kg of copper chloride into a reaction kettle, starting stirring, introducing air from the bottom of the reaction kettle to uniformly mix reaction materials, heating the reaction kettle to ensure that the external temperature of the reaction kettle is 100-105 ℃, the temperature of a mixture reaction system in the reaction kettle is 78-95 ℃, and the pressure is 40-60KPa, and when the system begins to reflux and discharge water, indicating that the reaction starts to be carried out and timing;
after 6h of reaction, measuring the acid value of the system, when the acid value is lower than the theoretical acid value of 57.65mg KOH/g, indicating that the reaction is finished, stopping the reaction, cooling to below 50 ℃, transferring the mixed solution in the reaction kettle to a washing neutralization kettle, supplementing 405kg of toluene, adding 106kg of deionized water, stirring for 10min, carrying out primary washing, then standing for 2h, layering the aqueous phase and the oil phase in the mixed solution, discharging the aqueous phase, continuously standing until no wastewater drips, taking the oil phase, measuring the acid value, wherein the acid value is 28.32mg KOH/g, adding 235kg of 10 kg of NaOH according to the acid value, stirring for 10min, standing for 3h, layering the aqueous phase and the oil phase, discharging the aqueous phase, continuously standing until no wastewater drips, adding 106kg of deionized water, stirring for 10min, carrying out tertiary water, 2h, layering the aqueous phase and the oil phase, continuously standing for 2h, layering the aqueous phase and the oil phase, discharging the aqueous phase, adding 106kg of deionized water, stirring for 10min, continuously standing until no wastewater drips, discharging the aqueous phase and the oil phase, continuously standing until no wastewater drips, transferring the aqueous phase and the oil phase to the reaction kettle, adding 0.75 ppm of a solvent, standing, keeping the reaction kettle for dehydration solvent, and carrying out a reaction kettle, and carrying out a reaction, keeping the reaction kettle at the reaction kettle for 500-75 ppm of residual isocyanuric acid, and keeping the reaction kettle, and carrying out a reaction.
Test example 1
This experimental example provides a structural test of the isocyanuric acid triacrylate prepared in example 1.
Infrared spectroscopy was conducted on the product of example 1, and the results are shown in FIG. 1 at 1624cm -1 Is C = C double bond stretching vibration absorption peak, 3035cm -1 、1415cm -1 、987cm -1 、808cm -1 1730cm as a bending vibration absorption peak of unsaturated CH bond -1 Is the vibration absorption peak of the C = O double bond, several absorption peaks above illustrate the presence of ester bonds and C = C double bonds in the product; 1462cm -1 Is a characteristic absorption peak of triazine ring, 1693cm -1 Is the absorption peak of C = O on the triazine ring, 1462cm -1 And 1693cm -1 Two absorption peaks indicate the presence of triazine ring in the product; thus, the product prepared in inventive example 1 was isocyanuric acid triacrylate.
H-NMR measurement of the product obtained in example 1 revealed that, as shown in FIG. 2, peaks at shifts of 5.5 to 7.5 were H at the double bond in the acrylate bond, peaks between 3.5 and 5 were H at the ethoxy group originally present in trishydroxyethyl isocyanurate and H near the double bond in β - (acryloyloxy) propionic acid, and peaks between 2 and 3 were H at the carboxyl group originally linked to β - (acryloyloxy) propionic acid; thus, the product prepared in inventive example 1 was isocyanuric acid triacrylate.
Test example 2
The experimental example provides the appearance of the isocyanuric acid triacrylate prepared in each example and comparative example, and the refractive index, viscosity and yield thereof were measured as follows, and the results are shown in table 1.
The method for testing the refractive index comprises the following steps: testing the refractive index of the glass by using an Abbe refractometer, wherein the testing temperature is 25 ℃;
method for measuring viscosity: testing the viscosity by adopting a BROOKFIELD DV-II + Pro laminar viscometer;
the calculation method of the yield comprises the following steps: yield is the ratio of actual to theoretical yield.
TABLE 1 test results of isocyanuric acid triacrylates prepared in examples and comparative examples
The experimental results in table 1 show that the yield of the inventive isocyanuric acid triacrylate is high, the acid value of the generated esterification wastewater is low, the COD content of the wastewater is low, and further, the inventive isocyanuric acid triacrylate is in a liquid state, the problem of crystallization is avoided, preheating of the isocyanuric acid triacrylate before use is not required, and the number of processes is reduced.
Test example 3
It is suggested to provide a test method for flexibility and low temperature resistance of isocyanuric acid triacrylate prepared in each of examples and comparative examples and test results.
The isocyanuric acid triacrylate prepared in example 1 and comparative example 1 was prepared as a coating material, and the properties of the coating material were characterized by taking 50 parts by weight of a resin (manufactured by sandomar, model No. CN 9001), 30 parts by weight of isocyanuric acid triacrylate, 15 parts by weight of HDDA (hexanediol diacrylate), and 5 parts by weight of 184 (photoinitiator), and mixing them uniformly to obtain a coating material.
Flexibility test method: carrying out blade coating by using a square coater, obtaining a coating film with the thickness of 30 mu m after curing, and characterizing the flexibility of the coating film, wherein the characterization method of the flexibility comprises the following steps: and (3) folding the coating film in half at 180 degrees, and recording the folding times when the coating film is broken so as to represent the flexibility.
Test method of adhesion: coating the coating on a PC standard plate and an ABS standard plate respectively, obtaining a coating film with the thickness of 20 mu m after curing, and testing the adhesive force of the coating film by adopting a check method, wherein the results are shown in Table 2.
The hardness test method comprises the following steps: a film having a thickness of 20 μm was formed by using a four-side coater, and the hardness of the film was measured by using a pencil hardness tester, and the results are shown in Table 2.
TABLE 2 characterization of the Properties of the coatings made of isocyanuric acid triacrylate
| Examples of the invention | Number of folds at break | Hardness of | Adhesive force PC | Adhesion ABS | Tg/℃ | |
| Example 1 | 20 | | 5B | 5B | 12 | |
| Comparative example 1 | 5 | 2B | 5B | 4B | 26 |
The experimental results in Table 2 show that the coating prepared from the isocyanuric acid triacrylate has low glass transition temperature, good flexibility and low temperature; compared with the acrylic acid modified trihydroxyethyl isocyanurate in the comparative example 1, the trihydroxyethyl isocyanurate obtained by modifying beta- (acryloyloxy) propionic acid has better flexibility and excellent low-temperature performance on the basis of ensuring the hardness and the adhesive force.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. Application of beta- (acryloyloxy) propionic acid in preparing isocyanuric acid triacrylate.
2. An isocyanuric acid triacrylate, which is characterized by having the following structural formula,
3. a preparation method of isocyanuric acid triacrylate is characterized by comprising the following steps,
(1) Mixing tris (2-hydroxyethyl) isocyanurate, beta- (acryloyloxy) propionic acid and a catalyst uniformly to obtain a mixture; heating and reacting;
(2) And (3) measuring the acid value of the reaction system after the reaction is carried out for 5-8h, finishing the reaction when the acid value of the reaction system is lower than the theoretical acid value, cooling, washing with water, neutralizing, and removing the solvent to obtain the isocyanuric acid triacrylate.
4. The production method according to claim 3, wherein at least one of A to B is satisfied,
A. the molar ratio of the tris (2-hydroxyethyl) isocyanurate to the beta- (acryloyloxy) propionic acid is 1 (3-4), preferably 1 (3-3.4);
B. the catalyst is at least one of methanesulfonic acid, p-toluenesulfonic acid and sulfuric acid.
5. The production method according to claim 3 or 4, wherein at least one of A-B is satisfied,
A. in the step (1), the heating temperature is 100-120 ℃, preferably 100-105 ℃;
B. in the step (1), the pressure of the reaction is 10 to 100KPa, preferably 40 to 60KPa.
6. The production method according to any one of claims 3 to 5, wherein at least one of A to E is satisfied,
A. in the step (1), a step of adding a first polymerization inhibitor is further included before obtaining the mixture;
B. the step of adding a solvent before obtaining the mixture;
C. the step of adding an antioxidant is also included before the mixture is obtained;
D. in the step (2), before the water washing, a step of adding a solvent is further included;
E. the method also comprises the step of adding a second polymerization inhibitor before removing the solvent.
7. The production method according to claim 6, wherein at least one of A to F is satisfied,
A. the dosage of the catalyst is 1-4% of the total mass of the reaction materials, preferably 1.5-2.5%;
B. the dosage of the first polymerization inhibitor is 0.01-1.0 percent of the total mass of the reaction materials, and preferably 0.02-0.1 percent;
C. the dosage of the solvent in the step (1) is 10-50% of the total mass of the reaction materials, and is preferably 25-35%;
D. the using amount of the antioxidant is 0.1-1% of the total mass of the reaction materials;
E. the amount of the second polymerization inhibitor is 0.01 to 1.0% by weight, preferably 0.04 to 0.06% by weight, based on the theoretical yield of isocyanuric acid triacrylate.
8. The production method according to claim 6 or 7, wherein at least one of A to D is satisfied,
A. the first polymerization inhibitor comprises at least one of copper chloride, copper sulfate and cuprous oxide; preferably, the first polymerization inhibitor further comprises at least one of p-hydroxyanisole and 2, 6-di-tert-butyl-p-cresol;
B. the antioxidant is at least one of 50% hypophosphorous acid, 2, 6-di-tert-butyl-p-cresol and antioxidant 626;
C. the solvent is at least one of toluene, benzene, cyclohexane and n-hexane;
D. the second polymerization inhibitor is at least one of p-hydroxyanisole and 2, 6-di-tert-butyl-p-cresol.
9. The method of any one of claims 3 to 8, wherein the neutralizing step is performed using sodium hydroxide or sodium bicarbonate.
10. Use of the isocyanuric acid triacrylate as claimed in claim 2 or prepared by the process of any one of claims 3 to 9 in a coating, ink or 3D printing.
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