Preparation method of polyol acrylate compound
By conducting esterification and aldol condensation reaction under acidic and alkaline conditions, the problem of poor purity and color in the synthesis of polyol acrylate compounds is solved, and the preparation and gentle reaction conditions of high-purity products are achieved.
Patent Information
- Application Number
- CN202311543975.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-11-17
- Publication Date
- 2025-05-20
AI Technical Summary
The existing synthesis methods of polyol acrylate compounds lead to poor purity and colority of the product, which affects its application in the field of photocuring.
Polyol-based acrylate compounds are prepared by conducting an esterification reaction in the presence of an acidic substance, contacting the polyol-based compounds with alkyl acidic compounds and/or alkyl ester compounds for esterification, and then undergoing aldol condensation reaction with formaldehyde and a polyprotein inhibitor in the presence of an alkaline substance to prepare polyol-based acrylate compounds.
This method can avoid side reactions such as polymerization during acrylic esterification, and obtain high-purity polyol-based acrylate compounds, while the reaction conditions are mild.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of organic synthesis, and particularly to a preparation method of polyol acrylate compounds. Background Art
[0002] Polyol acrylate compounds are crosslinking agents with excellent properties and are used in fields such as adhesives and rubbers. They can be used as co-vulcanization activators for special rubbers, crosslinking modifiers for various thermoplastic materials, modifiers for alkyl acrylates, etc. With the booming development of the photocuring industry, polyol acrylate compounds are widely used in the photocuring field as monomers or reactive diluents due to their advantages such as fast curing and low volatility.
[0003] Currently, the synthesis methods of polyol acrylate compounds are mainly obtained through direct esterification and transesterification. However, these compounds have high boiling points and are difficult to purify, and the product quality is mainly affected by the synthesis method and the purity of the raw material trimethylolpropane. The purity and chromaticity of the compounds prepared by the above routes are poor, seriously affecting their applications in the photocuring field. Therefore, it is of great significance to develop a synthesis method of polyol acrylate compounds with high purity and low chromaticity. Summary of the Invention
[0004] The purpose of the present invention is to overcome the problems of poor purity and chromaticity existing in the prior art, and provide a preparation method of polyol acrylate compounds. This preparation method can avoid side reactions such as polymerization during the acrylation process and obtain polyol acrylate compounds with high purity; meanwhile, the reaction conditions are mild.
[0005] To achieve the above purpose, the present invention provides a preparation method of polyol acrylate compounds, and the preparation method includes:
[0006] (1) Under esterification reaction conditions, contacting a polyol compound with an alkyl acid compound and / or an alkyl ester compound to carry out an esterification reaction to obtain an intermediate product; wherein, the esterification reaction is carried out in the presence of an acidic substance;
[0007] (2) Under aldol condensation reaction conditions, contacting the intermediate product obtained in step (1) with formaldehyde and an inhibitor to carry out an aldol condensation reaction to obtain a polyol acrylate compound; wherein, the aldol condensation reaction is carried out in the presence of a basic substance.
[0008] Through the above technical solutions, the beneficial technical effects obtained by the present invention are as follows:
[0009] The preparation method of the present invention uses polyol compounds and alkyl acid compounds and / or alkyl ester compounds as raw materials, conducts an esterification reaction in the presence of an acidic substance, and then conducts an aldol condensation reaction with formaldehyde in the presence of a basic substance to obtain the target product. This method can avoid side reactions such as polymerization during the acrylation process, obtain polyol acrylate compounds with high purity, and at the same time, the reaction conditions are mild. Detailed implementation manners
[0010] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.
[0011] The present invention provides a preparation method of polyol acrylate compounds, and the preparation method includes:
[0012] (1) Under esterification reaction conditions, contacting a polyol compound with an alkyl acid compound and / or an alkyl ester compound to conduct an esterification reaction to obtain an intermediate product; wherein, the esterification reaction is conducted in the presence of an acidic substance;
[0013] (2) Under aldol condensation reaction conditions, contacting the intermediate product obtained in step (1) with formaldehyde and a polymerization inhibitor to conduct an aldol condensation reaction to obtain polyol acrylate compounds; wherein, the aldol condensation reaction is conducted in the presence of a basic substance.
[0014] The preparation method of the present invention uses polyol compounds and alkyl acid compounds and / or alkyl ester compounds as raw materials, conducts an esterification reaction in the presence of an acidic substance, and then conducts an aldol condensation reaction with formaldehyde in the presence of a basic substance to obtain the target product. This method can avoid side reactions such as polymerization during the acrylation process, obtain polyol acrylate compounds with high purity, and at the same time, the reaction conditions are mild.
[0015] In the present invention, there is no double bond in the esterification reaction raw materials and products, and the stability is high, and ester compounds with high esterification degree can be obtained.
[0016] In the present invention, the aldol reaction conditions are mild, the polymerization of the product acrylate substances can be inhibited, and the reaction operation steps are simple.
[0017] In some embodiments of the present invention, the polyol compound is a primary alcohol or secondary alcohol compound containing at least two hydroxyl groups.
[0018] In some preferred embodiments of the present invention, the polyol compounds are selected from one or more of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2 - propanediol, 1,3 - propanediol, bis(1,3 - propanediol), 1,4 - butanediol, 1,5 - pentanediol, 1,6 - hexanediol, neopentyl glycol, glycerol, propoxylated neopentyl glycol, trimethylolpropane, bis(trimethylolpropane), ethoxylated trimethylolpropane, tris(2 - hydroxyethyl isocyanurate), pentaerythritol, ethoxylated pentaerythritol, and dipentaerythritol.
[0019] In some embodiments of the present invention, the alkyl acid compounds are selected from acetic acid and / or propionic acid;
[0020] In some embodiments of the present invention, the alkyl ester compounds are selected from one or more of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and propyl propionate.
[0021] In some embodiments of the present invention, the acidic substances are selected from one or more of concentrated sulfuric acid, polyphosphoric acid, hydrochloric acid, p - toluenesulfonic acid, trifluoromethanesulfonic acid, and methanesulfonic acid.
[0022] In some preferred embodiments of the present invention, the acidic substances are selected from concentrated sulfuric acid and / or p - toluenesulfonic acid.
[0023] In the present invention, the acidic substance acts as a catalyst for the esterification reaction, catalyzing the esterification reaction of the polyol compound with the alkyl acid compound and / or the alkyl ester compound.
[0024] In some embodiments of the present invention, the formaldehyde is from paraformaldehyde and / or aqueous formaldehyde solution.
[0025] In some embodiments of the present invention, the polymerization inhibitor is selected from p - methoxyphenol and / or 2,6 - di - tert - butyl - 4 - methylphenol.
[0026] In some embodiments of the present invention, the basic substances are selected from one or more of potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, potassium phosphate, sodium phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, piperidine, triethylamine, diethylamine, pyrrolidine, aniline, pyridine, and 4 - dimethylaminopyridine.
[0027] In some preferred embodiments of the present invention, the basic substances are selected from one or more of potassium carbonate, potassium bicarbonate, piperidine, triethylamine, and pyridine.
[0028] In the present invention, the basic substance acts as a catalyst for the aldol condensation reaction, catalyzing the aldol condensation reaction of the intermediate product with formaldehyde and the polymerization inhibitor.
[0029] In the present invention, there is no particular limitation on the amounts of the raw materials used in the preparation process of the compound.
[0030] In some embodiments of the present invention, the molar ratio of the alkyl acid compound and / or alkyl ester compound to the polyol compound is 3 - 10:1, preferably 3.5 - 8:1. That is, relative to 1 mol of the polyol compound, the amount of the alkyl acid compound and / or alkyl ester compound used is 3 - 10 mol, preferably 3.5 - 8 mol.
[0031] In some embodiments of the present invention, the molar ratio of the acidic substance to the polyol compound is 0.05 - 0.5:1, preferably 0.1 - 0.2:1. That is, relative to 1 mol of the polyol compound, the amount of the acidic substance used is 0.05 - 0.5 mol, preferably 0.1 - 0.2 mol.
[0032] In some embodiments of the present invention, the molar ratio of formaldehyde to the intermediate is 3 - 12:1, preferably 4 - 8:1. That is, relative to 1 mol of the intermediate, the amount of formaldehyde used is 3 - 12 mol, preferably 4 - 8 mol; wherein, when the formaldehyde is from paraformaldehyde, the mass of paraformaldehyde is calculated according to the product of the molar number and mass of formaldehyde.
[0033] In some embodiments of the present invention, the molar ratio of the basic substance to the intermediate is 0.2 - 0.6:1, preferably 0.3 - 0.4:1. That is, relative to 1 mol of the intermediate, the amount of the basic substance used is 0.2 - 0.6 mol, preferably 0.3 - 0.4 mol.
[0034] In some embodiments of the present invention, the molar ratio of the polymerization inhibitor to the intermediate is 200 - 1000 ppm:1, preferably 300 - 500 ppm:1. That is, relative to 1 mol of the intermediate, the amount of the basic substance used is 0.0002 - 0.001 mol, preferably 0.0003 - 0.0005 mol.
[0035] In the present invention, the esterification reaction can be the reaction conditions commonly used in esterification reactions.
[0036] In some embodiments of the present invention, the esterification reaction conditions include: the temperature is 100 - 160 °C, preferably 120 - 140 °C; the time is 5 - 12 h, preferably 6 - 8 h.
[0037] In the present invention, the aldol condensation reaction can be the reaction conditions commonly used in aldol condensation reactions.
[0038] In some embodiments of the present invention, the aldol condensation reaction conditions include: the temperature is 60 - 120 °C, preferably 70 - 100 °C; the time is 5 - 12 h, preferably 6 - 8 h.
[0039] In some embodiments of the present invention, the preparation method further includes: purifying the polyol acrylate compound.
[0040] In the present invention, the purification method is not particularly limited. For example, extraction and recrystallization methods can be independently used for purification. In some preferred embodiments of the present invention, after the reaction is completed, the extraction method is used for purification.
[0041] The preparation method adopted in the present invention can avoid side reactions such as polymerization during the acrylation process, and obtain polyol acrylate compounds with high purity; at the same time, the reaction conditions are mild, no polymerization inhibitor needs to be added during the reaction, and the purification steps are simplified.
[0042] The present invention will be described in detail below through preparation examples and examples, but the protection scope of the present invention is not limited to the following description.
[0043] For those not specified in the following preparation examples, examples and comparative examples, they are carried out according to conventional conditions or conditions recommended by the manufacturer. For reagents or instruments whose manufacturers are not specified, they are all conventional products that can be obtained through commercial channels.
[0044] Example 1
[0045] This example is to illustrate the polyol acrylate compound and its preparation method.
[0046] (1) Take trimethylolpropane (13.4 g, 100 mmol), add toluene (300 mL), propionic acid (25.9 g, 350 mmol); then add concentrated sulfuric acid (0.5 mL, 10 mmol) at room temperature, install a water separator and a reflux condenser on the reaction flask; heat up to 140 °C and react for 6 h. When the amount of water in the water separator no longer increases, cool back to room temperature; add 10% sodium carbonate solution (200 mL) to quench the reaction, separate the layers, and wash with water three times to obtain the organic phase. Remove the solvent by vacuum distillation to obtain trimethylolpropane tripropionate; after detection, the yield of the trimethylolpropane tripropionate product is 98.1%, and the purity is 96.3%;
[0047] (2) Take the trimethylolpropane tripropionate (29.6 g, 98 mmol) obtained in step (1), add 37% aqueous formaldehyde solution (44 mL, 588 mmol), piperidine (3 mL, 29.4 mmol) and p-methoxyphenol (3.64 mg, 0.029 mmol); after dropping, heat up to 70 °C and react for 8 h. After the reaction is completed, naturally cool to room temperature. Separate the aqueous phase to obtain the organic phase. The organic phase is washed with 10% sodium carbonate solution (200 mL), and then low-boiling impurities are removed by vacuum distillation to obtain the trimethylolpropane trimethacrylate product. After detection, the yield of the trimethylolpropane trimethacrylate product is 89.5%, and the purity is 97.7%.
[0048] The reaction process is as follows:
[0049]
[0050] Among them, R 1 is methyl, and R 2 is hydrogen.
[0051] Perform NMR characterization on the product obtained in Example 1: 1 H NMR (500 MHz, CDCl 3 ) δ 6.05 (s, 3H, CH 2 =), 5.61 (s, 3H, CH 2 =), 4.09 (s, 6H, CH 2 -O), 1.99 (s, 9H, CH 3 ), 1.54 (q, J = 7.4 Hz, 2H, CH 3 -CH 2 -C), 0.92 (t, J = 7.4 Hz, 3H, CH 3 -CH 2 -C).
[0052] Example 2
[0053] This example aims to illustrate polyol acrylate compounds and their preparation methods.
[0054] (1) Take trimethylolpropane (13.4 g, 100 mmol), add toluene (300 mL) and propionic acid (37.0 g, 500 mmol); then add p-toluenesulfonic acid (3.4 g, 20 mmol) at room temperature. Install a water separator and a reflux condenser on the reaction flask; heat up to 120 °C and react for 8 h. Wait until the amount of water in the water separator no longer increases, and then return to room temperature; add 10% sodium carbonate solution (200 mL) to quench the reaction. After liquid separation, wash with water three times to obtain the organic phase. Remove the solvent by vacuum distillation to obtain trimethylolpropane tripropionate; after detection, the yield of the trimethylolpropane tripropionate product is 99%, and the purity is 96.2%;
[0055] (2) Take the trimethylolpropane tripropionate (29.9 g, 99 mmol) prepared in step (1), add paraformaldehyde (11.9 g, 396 mmol), piperidine (3.96 mL, 39.6 mmol), n-hexane (300 mL) and p-methoxyphenol (5.52 mg, 0.05 mmol); after dropping, heat up to 100 °C and react for 6 h. After the reaction is completed, cool naturally to room temperature. Add 10% sodium carbonate solution (200 mL) to quench the reaction. Separate the liquid to obtain the organic phase, and remove the low-boiling impurities by vacuum distillation to obtain the trimethylolpropane trimethacrylate product. After detection, the yield of the trimethylolpropane trimethacrylate product is 90.5%, and the purity is 98.8%.
[0056] The reaction process is as shown in Example 1. Among them, R 1 is methyl, and R 2 is hydrogen.
[0057] Example 3
[0058] This example aims to illustrate polyol acrylate compounds and their preparation methods.
[0059] (1) Take trimethylolpropane (13.4 g, 100 mmol), add methyl propionate (70.4 g, 800 mmol); then add p-toluenesulfonic acid (0.8 g, 5 mmol) at room temperature, heat up to 100 °C and react for 5 h, while distilling out the methanol produced by the reaction, and then return to room temperature; add 10% sodium carbonate solution (200 mL) to quench the reaction. After liquid separation, wash with water three times to obtain the organic phase. Remove the solvent by vacuum distillation to obtain trimethylolpropane tripropionate;
[0060] (2) Take the trimethylolpropane tripropionate (23.0 g, 76 mmol) prepared in step (1), add 37% aqueous formaldehyde solution (57.0 mL, 760 mmol), triethylamine (6.4 mL, 46 mmol) and p-methoxyphenol (1.88 mg, 0.015 mmol); then heat to 60 °C and react for 12 h. After the reaction is completed, cool to room temperature naturally. Separate the aqueous phase to obtain the organic phase. The organic phase is washed with 10% sodium carbonate solution (200 mL), and then low-boiling impurities are removed by vacuum distillation to obtain the trimethylolpropane trimethacrylate product. After detection, the yield of the trimethylolpropane trimethacrylate product is 68.9%, and the purity is 75.3%.
[0061] The reaction process is as shown in Example 1. Among them, R 1 is methyl, and R 2 is methyl.
[0062] Example 4
[0063] This example aims to illustrate polyol acrylate compounds and their preparation methods.
[0064] (1) Take trimethylolpropane (13.4 g, 100 mmol), add acetic acid (18 g, 300 mmol), cyclohexane (300 mL); then add concentrated sulfuric acid (2.5 mL, 50 mmol) at room temperature, and install a water separator and a reflux condenser on the reaction flask; heat to 160 °C and react for 12 h. Wait until the amount of water in the water separator no longer increases, and return to room temperature; add 10% sodium carbonate solution (200 mL) to quench the reaction, wash three times with water after liquid separation to obtain the organic phase, and remove the solvent by vacuum distillation to obtain trimethylolpropane triacetate;
[0065] (2) Take the trimethylolpropane triacetate (18.2 g, 70 mmol) prepared in step (1), add paraformaldehyde (6.3 g, 210 mmol), pyridine (1.1 mL, 14 mmol), toluene (300 mL) and p-methoxyphenol (8.68 mg, 0.07 mmol); then heat to 120 °C and react for 5 h. After the reaction is completed, cool to room temperature naturally, add 10% sodium carbonate solution (200 mL) to quench the reaction, separate the liquid to obtain the organic phase, and remove low-boiling impurities by vacuum distillation to obtain the trimethylolpropane trimethacrylate product. After detection, the yield of the trimethylolpropane trimethacrylate product is 74.3%, and the purity is 69.4%.
[0066] The reaction process is as shown in Example 1. Among them, R 1 is hydrogen, and R 2 is hydrogen.
[0067] Example 5
[0068] This example is to illustrate polyol acrylate compounds and their preparation methods.
[0069] (1) Take pentaerythritol (13.6 g, 100 mmol), add propionic acid (29.6 g, 400 mmol) and toluene (300 mL); then add methanesulfonic acid (1.44 g, 15 mmol) at room temperature, install a water separator and a reflux condenser on the reaction flask; heat up to 140 °C and react for 6 h. Wait until the amount of water in the water separator no longer increases, and then return to room temperature; add 10% sodium carbonate solution (200 mL) to quench the reaction. After liquid separation, wash with water three times to obtain the organic phase, and remove the solvent by vacuum distillation to obtain pentaerythritol tetrapropionate;
[0070] (2) Take the pentaerythritol tetrapropionate (33.8 g, 94 mmol) prepared in step (1), add 37% aqueous formaldehyde solution (37.4 mL, 500 mmol), piperidine (3.25 mL, 33 mmol) and 2,6-di-tert-butyl-4-methylphenol (8.36 mg, 0.038 mmol); after dropping, heat up to 90 °C and react for 7 h. After the reaction is completed, naturally cool to room temperature. After liquid separation to remove the aqueous phase, obtain the organic phase. Wash the organic phase with 10% sodium carbonate solution (200 mL), and then remove the low-boiling impurities by vacuum distillation to obtain the pentaerythritol tetramethacrylate product. After detection, the yield of the pentaerythritol tetramethacrylate product is 82.9%, and the purity is 91.2%.
[0071] The reaction process is as follows:
[0072]
[0073] Among them, R 1 is methyl, and R 2 is hydrogen.
[0074] Example 6
[0075] (1) Take dipentaerythritol (25.4 g, 100 mmol), add toluene (300 mL) and acetic acid (48 g, 800 mmol); then add concentrated sulfuric acid (1 mL, 20 mmol) at room temperature, install a water separator and a reflux condenser on the reaction flask; heat up to 140 °C and react for 6 h. Wait until the amount of water in the water separator no longer increases, and then return to room temperature; add 10% sodium carbonate solution (200 mL) to quench the reaction. After liquid separation, wash with water three times to obtain the organic phase, and remove the solvent by vacuum distillation to obtain trimethylolpropane tripropionate; after detection, the yield of the dipentaerythritol hexaacetate product is 93.5%, and the purity is 97.2%;
[0076] (2) Take dipentaerythritol hexaacetate (47.3 g, 93.5 mmol) prepared in step (1), add 37% aqueous formaldehyde solution (56 mL, 748 mmol), piperidine (3.8 mL, 37.4 mmol) and p-methoxyphenol (5.9 mg, 0.047 mmol); after dropping, heat up to 100 °C and react for 8 h. After the reaction is completed, cool naturally to room temperature. Separate the aqueous phase to obtain an organic phase. Wash the organic phase with 10% sodium carbonate solution (200 mL), and then remove low-boiling impurities by vacuum distillation to obtain dipentaerythritol hexaacrylate product. After detection, the yield of the dipentaerythritol hexaacrylate product is 85.6%, and the purity is 95.8%.
[0077] The reaction process is as follows:
[0078]
[0079] Among them, R 1 is hydrogen, and R 2 is hydrogen.
[0080] Example 7
[0081] Prepare polyol acrylate compounds according to the method of Example 3. The difference is that in step (1), the addition amount of concentrated sulfuric acid is 17 g (100 mmol), and the other steps are the same as those in Example 3. After detection, the yield of the trimethylolpropane trimethacrylate product is 62.8%, and the purity is 75.6%.
[0082] The reaction process is as shown in Example 1. Among them, R 1 is hydrogen, and R 2 is methyl.
[0083] Example 8
[0084] Prepare polyol acrylate compounds according to the method of Example 3. The difference is that in step (2), the addition amount of triethylamine is 23.8 mL (100 mmol), and the other steps are the same as those in Example 3. After detection, the yield of the trimethylolpropane trimethacrylate product is 42.6%, and the purity is 49.3%.
[0085] The reaction process is as shown in Example 1. Among them, R 1 is hydrogen, and R 2 is methyl.
[0086] Comparative Example 1
[0087] This comparative example is used to illustrate the preparation method of the reference compound.
[0088] (1) Take trimethylolpropane (13.4 g, 100 mmol), add toluene (300 mL) and propionic acid (25.9 g, 350 mmol); install a water separator and a reflux condenser on the reaction flask; heat up to 140 °C and react for 6 h. Wait until the amount of water in the water separator no longer increases, and then cool back to room temperature; add 10% sodium carbonate solution (200 mL) to quench the reaction. After liquid separation, wash with water three times to obtain the organic phase. Distill off the solvent under reduced pressure to obtain trimethylolpropane tripropionate; after detection, the yield of the trimethylolpropane tripropionate product is 12%, and the purity is 9.1%.
[0089] (2) Take the trimethylolpropane tripropionate (3.78 g, 12 mmol) prepared in step (1), add 37% aqueous formaldehyde solution (5.39 mL, 72 mmol), piperidine (0.37 mL, 3.6 mmol) and p-methoxyphenol (0.45 mg, 0.0036 mmol); after dropping, heat up to 70 °C and react for 8 h. After the reaction is completed, cool naturally to room temperature. After liquid separation to remove the aqueous phase, obtain the organic phase. Wash the organic phase with 10% sodium carbonate solution (200 mL), and then distill off the low-boiling impurities under reduced pressure to obtain the trimethylolpropane trimethacrylate product. After detection, the yield of the trimethylolpropane trimethacrylate product is 69.5%, and the purity is 81.2%.
[0090] Comparative Example 2
[0091] This comparative example is used to illustrate the preparation method of the reference compound.
[0092] (1) Take trimethylolpropane (13.4 g, 100 mmol), add toluene (300 mL) and propionic acid (25.9 g, 350 mmol); then add concentrated sulfuric acid (05 mL, 10 mmol) at room temperature. Install a water separator and a reflux condenser on the reaction flask; heat up to 140 °C and react for 6 h. Wait until the amount of water in the water separator no longer increases, and then cool back to room temperature; add 10% sodium carbonate solution (200 mL) to quench the reaction. After liquid separation, wash with water three times to obtain the organic phase. Distill off the solvent under reduced pressure to obtain trimethylolpropane tripropionate;
[0093] (2) Take the trimethylolpropane tripropionate (29.6, 98 mmol) prepared in step (1), add 37% aqueous formaldehyde solution (44 mL, 588 mmol) and p-methoxyphenol (3.64 mg, 0.029 mmol); after dropping, heat up to 70 °C and react for 8 h. After the reaction is completed, cool naturally to room temperature. After liquid separation to remove the aqueous phase, obtain the organic phase. Wash the organic phase with 10% sodium carbonate solution (200 mL), and then distill off the low-boiling impurities under reduced pressure to obtain the trimethylolpropane trimethacrylate product. After detection, the yield of the trimethylolpropane trimethacrylate product is 9.8%, and the purity is 7.5%.
[0094] As can be seen from the above data, in the present invention, a polyol acrylate compound is prepared by esterifying a polyol compound with an alkyl acid compound and / or an alkyl ester compound and further carrying out aldol condensation, which can avoid side reactions such as polymerization during the acrylation process and obtain a polyol acrylate compound with high purity; meanwhile, the reaction conditions are mild.
[0095] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.
Claims
1. A method for preparing a polyol acrylate compound, characterized in that: The preparation method comprises: (1) contacting a polyol compound with an alkyl acid compound and / or an alkyl ester compound under esterification reaction conditions to carry out an esterification reaction to obtain an intermediate product; wherein the esterification reaction is carried out in the presence of an acidic substance; (2) under aldol condensation reaction conditions, contacting the intermediate product obtained in step (1) with formaldehyde and an inhibitor to carry out an aldol condensation reaction to obtain a polyol acrylate compound; wherein the aldol condensation reaction is carried out in the presence of an alkaline substance.
2. The preparation method according to claim 1, wherein The polyol compound is a primary alcohol or secondary alcohol compound containing at least two hydroxyl groups; Preferably, the polyol compound is selected from one or more of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, di(1,3-propylene glycol), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, glycerol, propoxylated neopentyl glycol, trimethylolpropane, di(trimethylolpropane), ethoxylated trimethylolpropane, tris(2-hydroxyethylthiocyanurate), pentaerythritol, ethoxypentaerythritol and dipentaerythritol.
3. The preparation method according to claim 1 or 2, wherein The alkyl acid compound is selected from acetic acid and / or propionic acid; The alkyl ester compound is selected from one or more of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate and propyl propionate.
4. The preparation method according to any one of claims 1 to 3, wherein The acidic substance is selected from one or more of concentrated sulfuric acid, polyphosphoric acid, hydrochloric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid and methanesulfonic acid; Preferably, the acidic substance is selected from concentrated sulfuric acid and / or p-toluenesulfonic acid.
5. The preparation method according to any one of claims 1 to 4, wherein: The formaldehyde comes from paraformaldehyde and / or formaldehyde solution; And / or, the polymerization inhibitor is selected from p-hydroxyanisole and / or 2,6-di-tert-butyl-4-methylphenol.
6. The preparation method according to any one of claims 1 to 4, wherein: The alkaline substance is selected from one or more of potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, potassium phosphate, sodium phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, piperidine, triethylamine, diethylamine, tetrahydropyrrole, aniline, pyridine and 4-dimethylaminopyridine; Preferably, the alkaline substance is selected from one or more of potassium carbonate, potassium bicarbonate, piperidine, triethylamine and pyridine.
7. The preparation method according to any one of claims 1 to 6, wherein: The molar ratio of the alkyl acid compound and / or alkyl ester compound to the polyol compound is 3-10:1, preferably 3.5-8:1; And / or, the molar ratio of the acidic substance to the polyol compound is 0.05-0.5:1, preferably 0.1-0.2:
1.
8. The preparation method according to any one of claims 1 to 7, wherein: The molar ratio of formaldehyde to the intermediate product is 3-12:1, preferably 4-8:1; and / or, the molar ratio of the alkaline substance to the intermediate product is 0.2-0.6:1, preferably 0.3-0.4:1; And / or, the molar ratio of the polymerization inhibitor to the intermediate product is 200-1000ppm:1, preferably 300-500ppm:
1.
9. The preparation method according to any one of claims 1 to 8, wherein: The esterification reaction conditions include: temperature of 100-160°C, preferably 120-140°C; time of 5-12h, preferably 6-8h; And / or, the aldol condensation reaction conditions include: temperature of 60-120° C., preferably 70-100° C.; time of 5-12 h, preferably 6-8 h.
10. The preparation method according to any one of claims 1 to 9, wherein: The preparation method further comprises: purifying the polyol acrylate compound; Preferably, the purification is performed by extraction.