Method for preparing allyl hydroxypropyl acrylate analogue and application

Abstract

The invention relates to a method for preparing an allyl hydroxypropyl acrylate analogue and application, and belongs to the technical field of fine chemical preparation. The specific method comprises the following steps: carrying out pretreatment dehydration on allyl glycidyl ether and an acrylic acid analogue, adding the obtained product into a reaction kettle, adding a polymerization inhibitor, introducing dry nitrogen to replace air in the kettle for multiple times, adding a catalyst after replacement is finished, uniformly stirring and mixing to obtain a mixture, heating to a preset reaction temperature, and cooling to room temperature; dropwise adding an acrylic acid analogue into the mixture at a constant speed, preserving heat after dropwise adding, sampling and analyzing to confirm whether the allyl glycidyl ether is completely converted or not, then cooling, adding solid alkali for neutralizing treatment, filtering out solid impurities after detecting and confirming that no acrylic acid residue exists, carrying out reduced pressure distillation on filtrate to recover the catalyst, and then carrying out reduced pressure distillation to collect a target product. The prepared allyl hydroxypropyl acrylate analogue has the advantages that the adhesive force is obviously improved, the curing shrinkage rate is reduced, and the odor is low.

Description

Technical Field

[0001] This invention belongs to the field of fine chemical preparation technology, and relates to a method for preparing allyl hydroxypropyl acrylate analogues and their applications. Background Technology

[0002] Allyl hydroxypropyl acrylate analogs are novel acrylate compounds with a dual functional group structure, containing both hydroxyl and acrylate groups. They are typically transparent, low-viscosity liquids, soluble in water and various organic solvents, exhibiting excellent resin dilution capabilities and good application adaptability. The propylene groups in the allyl hydroxypropyl acrylate analog molecule endow them with high reactivity, enabling them to effectively participate in free radical polymerization reactions, which is crucial for the preparation of polymers and copolymers with specific properties. The presence of hydroxyl groups facilitates further chemical modification, such as crosslinking or grafting, thereby improving the mechanical and thermal properties of the final material.

[0003] However, there are few reports on the synthesis and application of allyl hydroxypropyl acrylate analogs, and there is no corresponding industrial production, which makes them of great research value. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing allyl hydroxypropyl acrylate analogs and their applications. The allyl hydroxypropyl acrylate analogs prepared by this invention have significantly improved adhesion, reduced curing shrinkage, and low odor, and have good application prospects.

[0005] The objective of this invention can be achieved through the following technical solutions: A method for preparing allyl hydroxypropyl acrylate analogs, the method comprising the following steps: A1. Allyl glycidyl ether is pretreated with an acrylic acid analog to dehydrate, and the dehydrated allyl glycidyl ether is obtained. A2. Add the dehydrated allyl glycidyl ether to the reactor, add the polymerization inhibitor, and purge the air in the reactor with dry nitrogen gas several times to replace the air in the reactor. After the replacement is completed, add the catalyst and stir to mix evenly to obtain a mixture. A3. Heat to the preset reaction temperature, add acrylic acid analogue dropwise to the mixture at a uniform rate, keep warm after the addition is complete, obtain the material, and take a sample for analysis to confirm whether the allyl glycidyl ether in the material is completely converted. A4. Cool the material, add solid alkali for neutralization, and after confirming that there is no acrylic acid residue, filter out solid impurities, distill the filtrate under reduced pressure to recover the catalyst, and then distill under reduced pressure to collect the target product. Among them, acrylic acid analogues include acrylic acid or methacrylic acid.

[0006] Further, the molar ratio of allyl glycidyl ether to acrylic acid analog in step A1 is 1:1-1.3.

[0007] Further, the molar ratio of allyl glycidyl ether to acrylic acid analog in step A1 is 1:1.05-1.10.

[0008] Further, the pretreatment dehydration mentioned in step A1 refers to dehydrating the product using 4A molecular sieve at 20-30°C under dry nitrogen protection until the moisture content is <100ppm, and then filtering to remove the 4A molecular sieve; the amount of 4A molecular sieve used accounts for 20wt% of the total mass of allyl glycidyl ether and acrylic acid analog; the 4A molecular sieve is pre-activated by high-temperature calcination at 500-550°C for 2-4 hours and then cooled to room temperature.

[0009] Further, the polymerization inhibitor mentioned in step A2 is selected from one or more of 2,4-dinitrophenol, p-tert-butylcatechol, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-p-cresol, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, antioxidant 1010, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide, tetramethylpiperidine nitroxide free radical phosphite, and copper sulfate.

[0010] Further, the polymerization inhibitor in step A2 is 2,5-di-tert-butylhydroquinone or a mixture of p-tert-butylcatechol and phenothiazine.

[0011] Further, the amount of polymerization inhibitor used in step A2 is 0.05-0.2 wt% of the mass of the dehydrated allyl glycidyl ether.

[0012] Further, the catalyst in step A2 is selected from one or more of N,N-dimethylcyclohexylamine, tetramethylalkyldiamine, N,N-dimethylbenzylamine, triethanolamine, tri-n-butylamine, and triphenylphosphine.

[0013] Further, the catalyst in step A2 is selected from one of N,N-dimethylcyclohexylamine, tetramethylalkyldiamine, and N,N-dimethylbenzylamine.

[0014] Further, the amount of catalyst used in step A2 is 0.5-2.5 wt% of the mass of the dehydrated allyl glycidyl ether.

[0015] Furthermore, the preset reaction temperature in step A3 is 70-110℃; the dropping time is 3-6h; and the heat preservation time is 3-7h.

[0016] Furthermore, the cooling mentioned in step A4 refers to cooling to 30-40°C.

[0017] Furthermore, the allyl hydroxypropyl acrylate analogues can be applied to wood coatings, metal coatings, and automotive coatings.

[0018] The beneficial effects of this invention are: The allyl hydroxypropyl acrylate analog prepared in this invention is a photocurable monomer that combines the high reactivity of acrylates with the crosslinking ability of hydroxyl groups. It is mainly used in UV-curable coatings (such as high-abrasion-resistant wood coatings and metal coatings) and high-strength adhesives. The propyl ether segment structure in its molecule helps to impart excellent flexibility and low shrinkage stress to the cured material. Compared to VEEA (vinyl ethoxyethyl acrylate), the allyl hydroxypropyl acrylate analog has advantages in adhesion, chemical resistance (such as solvent resistance), and crosslinking density, making it more suitable for outdoor applications requiring high weather resistance (such as automotive coatings). Furthermore, the bifunctionality of the allyl hydroxypropyl acrylate analog allows for the construction of a denser crosslinked network structure, making it particularly suitable for metal or architectural coatings requiring high hardness, effectively balancing the needs for hardness and toughness.

[0019] Because of the high molecular weight of the polymer, the reaction system cannot be distilled out during the distillation process, resulting in a significant decrease in product yield and an increase in residue at the bottom of the vessel, which directly affects the formation of the final polymer. In this invention, a specific polymerization inhibitor is introduced during the preparation process. The allyl hydroxypropyl acrylate analog obtained contains both acrylate double bonds and allyl groups. Under heating or catalytic conditions, it has higher activity and is more likely to undergo self-polymerization and cross-polymerization, leading to polymer formation.

[0020] The allyl hydroxypropyl acrylate analog prepared by this invention has significantly improved adhesion, reduced curing shrinkage, and low odor, and has good application prospects. Attached Figure Description

[0021] To facilitate understanding by those skilled in the art, the present invention will be further described below with reference to the accompanying drawings.

[0022] Figure 1 This is a schematic diagram of the chemical structure of an allyl hydroxypropyl acrylate analog. Detailed Implementation

[0023] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with the accompanying drawings and preferred embodiments, is provided.

[0024] Example 1 A method for preparing allyl hydroxypropyl acrylate analogs, the method comprising the following steps: A1. Allyl glycidyl ether and acrylic acid are pretreated and dehydrated to obtain dehydrated allyl glycidyl ether; the pretreatment and dehydration refers to dehydration treatment using 4A molecular sieve at 25°C under dry nitrogen protection until the moisture content is <100ppm, and then filtering to remove the 4A molecular sieve; the amount of 4A molecular sieve used accounts for 20wt% of the total mass of allyl glycidyl ether and acrylic acid; the 4A molecular sieve is pre-activated by high-temperature calcination at 525°C for 3h and then cooled to room temperature. A2. Add 570.7g of dehydrated allyl glycidyl ether to the reactor, add 0.3g of phenothiazine and 0.3g of p-tert-butylcatechol, purge the air in the reactor with dry nitrogen gas several times, and after the replacement is completed, add 5.7g of N,N-dimethylbenzylamine, stir and mix evenly to obtain a mixture. A3. Heat to 90℃ and add 385.2g of acrylic acid dropwise to the mixture at a uniform rate. After 3.5h of dropwise addition, keep the temperature for 6.5h to obtain the material. Take a sample for analysis to confirm that the allyl glycidyl ether in the material has been completely converted. A4. Cool the material to 35°C, add 16g of calcium hydroxide, stir to neutralize the solid alkali, and after confirming that there is no acrylic acid residue, filter out solid impurities, distill the filtrate under reduced pressure to recover N,N-dimethylbenzylamine, and then distill under reduced pressure to collect the target product, obtaining 895.3g of product.

[0025] The product yield obtained in this embodiment is 96.20%, the product color number (APHA) is <10#, and the purity is 99.1%.

[0026] Example 2 A method for preparing allyl hydroxypropyl acrylate analogs, the method comprising the following steps: A1. Allyl glycidyl ether and acrylic acid are pretreated and dehydrated to obtain dehydrated allyl glycidyl ether; the pretreatment and dehydration refers to dehydration treatment using 4A molecular sieve at 25°C under dry nitrogen protection until the moisture content is <100ppm, and then filtering to remove the 4A molecular sieve; the amount of 4A molecular sieve used accounts for 20wt% of the total mass of allyl glycidyl ether and acrylic acid; the 4A molecular sieve is pre-activated by high-temperature calcination at 525°C for 3h and then cooled to room temperature. A2. Add 570.7g of dehydrated allyl glycidyl ether to the reactor, add 0.35g of phenothiazine and 0.3g of p-tert-butylcatechol, purge the air in the reactor with dry nitrogen gas several times, and after the replacement is completed, add 6.8g of N,N-dimethylcyclohexylamine, stir and mix evenly to obtain a mixture. A3. Heat to 90℃ and add 396g of acrylic acid dropwise to the mixture at a uniform rate. After 3.5h of dropwise addition, keep the temperature for 6.5h to obtain the material. Take a sample for analysis to confirm that the allyl glycidyl ether in the material has been completely converted. A4. Cool the material to 35°C, add 18g of calcium hydroxide, stir to neutralize the solid alkali, and after confirming that there is no acrylic acid residue, filter out solid impurities, and recover N,N-dimethylcyclohexylamine by vacuum distillation of the filtrate, and then collect the target product by vacuum distillation to obtain 887.9g of product.

[0027] The product yield obtained in this embodiment is 95.40%, the product color number (APHA) is <10#, and the purity is 98.8%.

[0028] Example 3 A method for preparing allyl hydroxypropyl acrylate analogs, the method comprising the following steps: A1. Allyl glycidyl ether and acrylic acid are pretreated and dehydrated to obtain dehydrated allyl glycidyl ether; the pretreatment and dehydration refers to dehydration treatment using 4A molecular sieve at 25°C under dry nitrogen protection until the moisture content is <100ppm, and then filtering to remove the 4A molecular sieve; the amount of 4A molecular sieve used accounts for 20wt% of the total mass of allyl glycidyl ether and acrylic acid; the 4A molecular sieve is pre-activated by high-temperature calcination at 525°C for 3h and then cooled to room temperature. A2. Add 570.7g of dehydrated allyl glycidyl ether to the reactor, add 0.35g of phenothiazine and 0.35g of p-tert-butylcatechol, purge the air in the reactor with dry nitrogen gas several times, and after the replacement is completed, add 11.4g of N,N-dimethylbenzylamine, stir and mix evenly to obtain a mixture. A3. Heat to 75℃, add 378g of acrylic acid dropwise to the mixture at a uniform rate, add for 5.5h, keep warm for 6.5h, obtain the material, and take a sample for analysis to confirm that the allyl glycidyl ether in the material has been completely converted. A4. Cool the material to 35°C, add 15g of calcium hydroxide, stir to neutralize the solid alkali, and after confirming that there is no acrylic acid residue, filter out solid impurities, and recover N,N-dimethylbenzylamine by vacuum distillation of the filtrate, and then collect the target product by vacuum distillation to obtain 880.4g of product.

[0029] The product yield obtained in this embodiment is 94.60%, the product color number (APHA) is <10#, and the purity is 98.3%.

[0030] Example 4 A method for preparing allyl hydroxypropyl acrylate analogs, the method comprising the following steps: A1. Allyl glycidyl ether and acrylic acid are pretreated and dehydrated to obtain dehydrated allyl glycidyl ether; the pretreatment and dehydration refers to dehydration treatment using 4A molecular sieve at 25°C under dry nitrogen protection until the moisture content is <100ppm, and then filtering to remove the 4A molecular sieve; the amount of 4A molecular sieve used accounts for 20wt% of the total mass of allyl glycidyl ether and acrylic acid; the 4A molecular sieve is pre-activated by high-temperature calcination at 525°C for 3h and then cooled to room temperature. A2. Add 570.7g of dehydrated allyl glycidyl ether to the reactor, add 0.3g of phenothiazine and 0.35g of 2,5-di-tert-butylhydroquinone, purge the air in the reactor with dry nitrogen gas several times, and after the replacement is completed, add 8.5g of N,N-dimethylbenzylamine, stir and mix evenly to obtain a mixture. A3. Heat to 105℃ and add 385.2g of acrylic acid dropwise to the mixture at a uniform rate. After 3.5h of dropwise addition, keep warm for 4.5h to obtain the material. Take a sample for analysis to confirm that the allyl glycidyl ether in the material has been completely converted. A4. Cool the material to 35°C, add 16g of calcium hydroxide, stir to neutralize the solid alkali, and after confirming that there is no acrylic acid residue, filter out the solid impurities. Distill the filtrate under reduced pressure to recover N,N-dimethylbenzylamine, and then distill it back under reduced pressure to collect the target product, obtaining 886g of product.

[0031] The product yield obtained in this embodiment is 95.20%, the product color number (APHA) is <25#, and the purity is 98.1%.

[0032] Example 5 A method for preparing allyl hydroxypropyl acrylate analogs, the method comprising the following steps: A1. Allyl glycidyl ether and acrylic acid are pretreated and dehydrated to obtain dehydrated allyl glycidyl ether; the pretreatment and dehydration refers to dehydration treatment using 4A molecular sieve at 25°C under dry nitrogen protection until the moisture content is <100ppm, and then filtering to remove the 4A molecular sieve; the amount of 4A molecular sieve used accounts for 20wt% of the total mass of allyl glycidyl ether and acrylic acid; the 4A molecular sieve is pre-activated by high-temperature calcination at 525°C for 3h and then cooled to room temperature. A2. Add 570.7g of dehydrated allyl glycidyl ether to the reaction vessel, add 0.6g of phenothiazine and 0.6g of 2,5-di-tert-butylhydroquinone, purge the air in the vessel with dry nitrogen gas several times to replace the air, and after the replacement is completed, add 5.7g of N,N-dimethylbenzylamine, stir and mix evenly to obtain a mixture. A3. Heat to 125℃ and add 378g of acrylic acid dropwise to the mixture at a uniform rate. After 3.5h of dropwise addition, keep warm for 3.5h to obtain the material. Take a sample for analysis to confirm that the allyl glycidyl ether in the material has been completely converted. A4. Cool the material to 35°C, add 15g of calcium hydroxide, stir to neutralize the solid alkali, and after confirming that there is no acrylic acid residue, filter out the solid impurities. Distill the filtrate under reduced pressure to recover N,N-dimethylbenzylamine, and then distill it under reduced pressure to collect the target product, obtaining 710.1g of product.

[0033] The product yield obtained in this embodiment was 76.30%, the product color number (APHA) was <30#, and the purity was 97.8%.

[0034] Example 6 A method for preparing allyl hydroxypropyl acrylate analogs, the method comprising the following steps: A1. Allyl glycidyl ether and acrylic acid are pretreated and dehydrated to obtain dehydrated allyl glycidyl ether; the pretreatment and dehydration refers to dehydration treatment using 4A molecular sieve at 25°C under dry nitrogen protection until the moisture content is <100ppm, and then filtering to remove the 4A molecular sieve; the amount of 4A molecular sieve used accounts for 20wt% of the total mass of allyl glycidyl ether and acrylic acid; the 4A molecular sieve is pre-activated by high-temperature calcination at 525°C for 3h and then cooled to room temperature. A2. Add 570.7g of dehydrated allyl glycidyl ether to the reactor, add 0.35g of phenothiazine and 0.3g of p-tert-butylcatechol, purge the air in the reactor with dry nitrogen gas several times, and after the replacement is completed, add 6.5g of sodium hydroxide, stir and mix evenly to obtain a mixture. A3. Heat to 85℃ and add 390.0g of acrylic acid dropwise to the mixture at a uniform rate. After 3.5h of dropwise addition, keep warm for 7.0h to obtain the material. Take a sample for analysis to confirm that the allyl glycidyl ether in the material has been completely converted. A4. Cool the material to 35°C, add 30g of calcium hydroxide, stir to neutralize the solid alkali, and after confirming that there is no acrylic acid residue, filter out solid impurities, distill the filtrate under reduced pressure to recover N,N-dimethylbenzylamine, and then distill under reduced pressure to collect the target product, obtaining 547.4g of product.

[0035] The product yield obtained in this embodiment was 58.82%, the product color number (APHA) was <40#, and the purity was 95.30%.

[0036] Example 7 A method for preparing allyl hydroxypropyl acrylate analogs, the method comprising the following steps: A1. Allyl glycidyl ether and acrylic acid are pretreated and dehydrated to obtain dehydrated allyl glycidyl ether; the pretreatment and dehydration refers to dehydration treatment using 4A molecular sieve at 25°C under dry nitrogen protection until the moisture content is <100ppm, and then filtering to remove the 4A molecular sieve; the amount of 4A molecular sieve used accounts for 20wt% of the total mass of allyl glycidyl ether and acrylic acid; the 4A molecular sieve is pre-activated by high-temperature calcination at 525°C for 3h and then cooled to room temperature. A2. Add 570.7g of dehydrated allyl glycidyl ether to the reaction vessel, add 0.35g of hydroquinone and 0.4g of p-hydroxyanisole, purge the air in the vessel with dry nitrogen gas several times to replace the air, and after the replacement is completed, add 5.7g of N,N-dimethylbenzylamine, stir and mix evenly to obtain a mixture. A3. Heat to 80℃ and add 385.2g of acrylic acid dropwise to the mixture at a uniform rate. After 4.0h of dropwise addition, keep warm for 7.0h to obtain the material. Take a sample for analysis to confirm that the allyl glycidyl ether in the material has been completely converted. A4. Cool the material to 35°C, add 16g of calcium hydroxide, stir to neutralize the solid alkali, and after confirming that there is no acrylic acid residue, filter out solid impurities, distill the filtrate under reduced pressure to recover N,N-dimethylbenzylamine, and then distill under reduced pressure to collect the target product, obtaining 578.0g of product.

[0037] The product yield obtained in this embodiment is 62.10%, the product color number (APHA) is <20#, and the purity is 97.2%.

[0038] Example 8 A method for preparing an allyl hydroxypropyl methacrylate analog, the method comprising the following steps: A1. Allyl glycidyl ether and methacrylic acid are pretreated and dehydrated to obtain dehydrated allyl glycidyl ether; the pretreatment and dehydration refers to dehydration treatment using 4A molecular sieve at 25°C under dry nitrogen protection until the moisture content is <100ppm, and then filtering to remove the 4A molecular sieve; the amount of 4A molecular sieve used accounts for 20wt% of the total mass of allyl glycidyl ether and methacrylic acid; the 4A molecular sieve is pre-activated by high-temperature calcination at 525°C for 3h and then cooled to room temperature. A2. Add 570.7g of dehydrated allyl glycidyl ether to the reactor, add 0.35g of phenothiazine and 0.35g of 2,5-di-tert-butylhydroquinone, purge dry nitrogen gas to replace the air in the reactor several times, and after the replacement is completed, add 8.6g of N,N-dimethylbenzylamine, stir and mix evenly to obtain a mixture. A3. Heat to 95℃ and add 437g of methacrylic acid dropwise to the mixture at a uniform rate. After 3.5h of dropwise addition, keep the temperature for 6.5h to obtain the material. Take a sample for analysis to confirm that the allyl glycidyl ether in the material has been completely converted. A4. Cool the material to 35°C, add 16g of calcium hydroxide, stir to neutralize the solid alkali, and after confirming that there is no methacrylic acid residue, filter out solid impurities, recover the catalyst by vacuum distillation of the filtrate, and then collect the target product by vacuum distillation to obtain 956.7g of product.

[0039] The product yield obtained in this embodiment is 95.60%, the product color number (APHA) is <10#, and the purity is 99.3%.

[0040] Comparative Example 1 Comparative Example 1 is based on Example 1, but with the polymerization inhibitors phenothiazine and p-tert-butylcatechol omitted, resulting in rapid polymerization.

[0041] The products of Example 1 (allyl hydroxypropyl acrylate) and Example 8 (allyl hydroxypropyl methacrylate) were subjected to performance tests with VEEA (vinyl ethoxyethyl acrylate, Nippon Shokubai). These tests included surface drying rate testing, adhesion testing, curing shrinkage rate testing, and odor testing. The specific test procedures are as follows: Test 1: Adhesion Test The sample to be treated was thoroughly mixed with 4% D1173 by mass until homogeneous. The resulting mixture was then uniformly coated onto the surface of different substrates. After the coating was irradiated and cured, it was tested. The adhesion was tested using the cross-cut adhesion test method, which was based on the standard GB / T 9286-1998 "Scratch Test for Paint and Varnish Film". The film was scratched with a blade, with 6 cuts in each direction. The spacing between the lines was 1.5 mm. After scratching, tape was applied to the scratched areas. The tape was pressed down with a finger to adhere it tightly, and then the tape was torn off with a momentary force. The sample was visually inspected for any peeling. The adhesion was expressed as an ASTM standard grade and recorded as shown in Table 1 below. Note: ASTM adhesion standard grades: 5B: The cut edge is completely smooth with no peeling; 4B: There is a small amount of coating peeling at the intersection of the cuts, and the actual damage within the grid does not exceed 5%; 3B: There is peeling at the cut or intersection, and the area is greater than 5% but not more than 15%; 2B: There is partial peeling or large-scale peeling along the cut edge, and the peeled area exceeds 15%-35%; 1B: Large-scale peeling at the cut edge or complete peeling of some grids, and the area is greater than 35% but not more than 65%; 0B: The degree of peeling exceeds the previous grade. Test 2: Surface drying rate test The sample to be treated was thoroughly mixed with 4% D1173 by mass until homogeneous; the resulting mixture was uniformly coated onto the surface of a PC substrate; the coating was subjected to irradiation curing treatment, and the applied irradiation energy was recorded simultaneously using an energy meter during the curing process; the surface drying performance of the cured coating was evaluated by the finger touch method, and the degree of surface drying was judged by observing the fingerprint imprint and stickiness on the surface after contact, and recorded as shown in Table 1 below; Test 3: Curing Shrinkage Rate Test The density of the liquid before curing was determined using a hydrometer, and the density of the solid after curing was determined using the buoyancy method. The shrinkage rate was calculated based on the density and recorded as shown in Table 1 below, where shrinkage rate = (ρafter - ρbefore) / ρafter × 100%, and ρafter and ρbefore are the densities before and after curing, respectively. Test 4: Odor Test The sample from the example was poured into a disposable cup (50 ml) and left for 2 minutes. Twelve judges were asked to rate and record the results of each sample. Based on odor intensity, six rating levels were assigned: 1 = no odor; 2 = slight odor; 3 = odorous but not irritating; 4 = irritating odor; 5 = strong irritating odor. The average rating from the judges was taken as the final test result, as shown in Table 1.

[0042] Table 1 As shown in Table 1, the surface drying rate of the allyl hydroxypropyl acrylate analog prepared by this invention is similar to that of vinyl ethoxyethyl acrylate, with significantly improved adhesion to different substrates, reduced curing shrinkage, and low odor, indicating good application prospects.

[0043] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any indirect modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A method for preparing allyl hydroxypropyl acrylate analogs, characterized in that: The method for preparing allyl hydroxypropyl acrylate analogues includes the following steps: A1. Allyl glycidyl ether is pretreated with an acrylic acid analog to dehydrate, and the dehydrated allyl glycidyl ether is obtained. A2. Add the dehydrated allyl glycidyl ether to the reactor, add the polymerization inhibitor, and purge the air in the reactor with dry nitrogen gas several times to replace the air in the reactor. After the replacement is completed, add the catalyst and stir to mix evenly to obtain a mixture. A3. Heat to the preset reaction temperature, add acrylic acid analogue dropwise to the mixture at a uniform rate, keep the temperature after the addition is complete, obtain the material, and take a sample for analysis to confirm whether the allyl glycidyl ether in the material is completely converted. A4. Cool the material, add solid alkali for neutralization, and after confirming that there is no acrylic acid residue, filter out solid impurities, distill the filtrate under reduced pressure to recover the catalyst, and then distill under reduced pressure to collect the target product. Among them, acrylic acid analogues include acrylic acid or methacrylic acid.

2. The method for preparing allyl hydroxypropyl acrylate analogs according to claim 1, characterized in that: The molar ratio of allyl glycidyl ether to acrylic acid analog in step A1 is 1:1-1.

3.

3. The method for preparing allyl hydroxypropyl acrylate analogs according to claim 1, characterized in that: The pretreatment dehydration mentioned in step A1 refers to the dehydration treatment using 4A molecular sieve at 20-30℃ under dry nitrogen protection until the moisture content is <100ppm, and then filtering to remove the 4A molecular sieve; the amount of 4A molecular sieve used accounts for 20wt% of the total mass of allyl glycidyl ether and acrylic acid analog; the 4A molecular sieve is pre-activated by high-temperature calcination at 500-550℃ for 2-4h and then cooled to room temperature.

4. The method for preparing allyl hydroxypropyl acrylate analogs according to claim 1, characterized in that: The polymerization inhibitor mentioned in step A2 is selected from one or more of the following: 2,4-dinitrophenol, p-tert-butylcatechol, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-p-cresol, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, antioxidant 1010, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide, tetramethylpiperidine nitroxide free radical phosphite, and copper sulfate.

5. The method for preparing allyl hydroxypropyl acrylate analogs according to claim 1, characterized in that: The amount of polymerization inhibitor used in step A2 is 0.05-0.2 wt% of the mass of the dehydrated allyl glycidyl ether.

6. The method for preparing allyl hydroxypropyl acrylate analogs according to claim 1, characterized in that: The catalyst in step A2 is selected from one or more of N,N-dimethylcyclohexylamine, tetramethylalkyldiamine, N,N-dimethylbenzylamine, triethanolamine, tri-n-butylamine, and triphenylphosphine.

7. The method for preparing allyl hydroxypropyl acrylate analogs according to claim 1, characterized in that: The amount of catalyst used in step A2 is 0.5-2.5 wt% of the mass of the dehydrated allyl glycidyl ether.

8. The method for preparing allyl hydroxypropyl acrylate analogs according to claim 1, characterized in that: The preset reaction temperature in step A3 is 70-110℃; the dropping time is 3-6h; and the heat preservation time is 3-7h.

9. The method for preparing allyl hydroxypropyl acrylate analogs according to claim 1, characterized in that: The cooling mentioned in step A4 refers to cooling to 30-40℃.

10. The application of an allyl hydroxypropyl acrylate analog prepared by the method according to any one of claims 1-9, characterized in that: The allyl hydroxypropyl acrylate analogues can be used in wood coatings, metal coatings, and automotive coatings.

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