Allyl ester synthesis process

Abstract

The invention provides an allyl ester synthesis process which comprises the following steps: adding aromatic carboxylic acid into a reaction kettle, and adding a solvent to dissolve the aromatic carboxylic acid; adding a catalyst into the reaction kettle, and then adding an acid-binding agent while stirring; and adding an allyl substitute into the reaction kettle, sealing the reaction kettle, and carrying out a heat preservation reaction until the aromatic carboxylic acid is completely converted. The synthesis process has the advantages of simple process, short reaction time, low energy consumption, high yield and high purity, and is suitable for large-scale industrial production.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical synthesis, and specifically, to a synthesis process of allyl esters. Background Art

[0002] Triallyl trimellitate can be used as a monomer for synthesizing polymers, especially for the preparation of polyester and polyimide materials. It has good heat resistance, solvent resistance and mechanical strength, and is widely used in the fields of plastics, coatings, adhesives, etc. Triallyl 1,2,4-benzenetricarboxylate is mainly used as a photosensitive material and a polymer additive, and can be used to prepare a photo-curable polymer additive, and can be used to prepare photoresists, optical fiber preforms, etc. Diallyl terephthalate is an important monomer for synthesizing optical materials. The resin obtained by its self-polymerization or copolymerization with other monomers is widely used in the manufacture of optical lenses, optical discs, optical fibers, optoelectronic devices, etc. Diallyl isophthalate is a reactive diluent widely used in the fields of coatings, inks and adhesives. It has low volatility and high reactivity, and can improve the hardness, weather resistance and chemical resistance of the coating film. Allyl benzoate is mainly used as a food preservative, cosmetic raw material, etc. It can effectively inhibit the growth of bacteria and fungi, so it is often added to various foods and cosmetics.

[0003] Chinese Patent CN110627748A discloses a synthesis method of triallyl trimellitate. Ammonia is used as an acid-binding agent therein, and ammonia is continuously introduced according to the change of the system pressure during the reaction process. Since allyl chloride has a low boiling point, this reaction needs to be carried out under pressure conditions, and the excessive amount of allyl chloride will cause solvent waste. The introduction of ammonia cannot be used for large-scale industrial production, the operation difficulty is large, and the product purity is low.

[0004] Chinese Patent CN107418287A discloses a synthesis method of triallyl trimellitate. A strong alkaline catalyst is used in this method, resulting in difficult removal of the catalyst. And because allyl chloride has a relatively low boiling point (45°C), the reaction time is long under heating conditions in this process, and the solvent consumption is excessive.

[0005] Therefore, it is of great significance to develop a synthesis method of allyl esters with a simple reaction process, a short synthesis time and a high yield, which can be used for large-scale industrial production. Summary of the Invention

[0006] Aiming at the defects in the prior art, the purpose of the present invention is to provide a synthesis process of allyl esters.

[0007] The present invention provides a synthesis process of allyl esters, including:

[0008] Adding an aromatic carboxylic acid into a reaction kettle, and adding a solvent to dissolve it;

[0009] Add a catalyst in a preset ratio to the reaction kettle, and then add an acid-binding agent under stirring. The preset ratio is greater than or equal to zero;

[0010] Add an allyl substituent to the reaction kettle, seal the reaction kettle, and carry out a heat preservation reaction until all the aromatic carboxylic acid is completely converted, and the synthesis of allyl ester is achieved through the heat preservation process;

[0011] The reaction formula is as follows:

[0012]

[0013] Since the capacity of the reaction kettle is large, in order to avoid raw materials remaining on the inner wall of the kettle, solid raw materials need to be added first. During the subsequent addition of the solvent, the solvent is used to wash and dissolve the solid raw materials remaining on the inner wall of the reaction kettle, so as to achieve the full dissolution of the raw materials and better reaction.

[0014] Since the raw material used is aromatic carboxylic acid, adding an acid-binding agent can remove the H ions in the aromatic carboxylic acid. The generated anion attacks the allyl substituent as a nucleophile, and the chloride ions, bromide ions, etc. in the allyl substituent leave, forming hydrochloride with the acid-binding agent, making the reaction easier to occur. The substitution groups of the allyl substituent are Cl, Br, and OH, which are easy to obtain and relatively low in price. The substitution groups of these three allyl substituents are easier to leave and are more easily attacked by nucleophiles to obtain products.

[0015] Optionally, the molar ratio of the aromatic carboxylic acid, the catalyst, the allyl substituent, the acid-binding agent, and the solvent is 1:(0.05 - 0.1):(4 - 15):(1 - 3):(1 - 10).

[0016] The dosage of each component is mainly determined according to the number of carboxyl groups contained in the aromatic carboxylic acid. The dosage of the allyl substituent (such as allyl chloride) is 1.25 times the molar amount according to the number (i.e., the number of carboxyl groups) contained in the aromatic carboxylic acid. The acid-binding agent is added in an amount of 1 - 3 equivalents according to the number of carboxyl groups contained in the aromatic carboxylic acid. The catalyst and the solvent are respectively 0.05 - 0.1 times and 1 - 10 times the molar amount of the aromatic carboxylic acid.

[0017] Optionally, the dosage of the catalyst is 2.5 - 16.7 wt% of the feeding mass of the aromatic carboxylic acid.

[0018] Optionally, the dosage of the solvent is 1 - 10 wt% of the feeding mass of the aromatic carboxylic acid.

[0019] Optionally, the dosage of the acid-binding agent is 2 - 5 wt% of the feeding mass of the aromatic carboxylic acid.

[0020] Optionally, the catalyst is sodium bromide and / or sodium iodide to make the substitution groups of the allyl substituent easy to leave.

[0021] Optionally, the acid-binding agent is any one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium hydride, triethylamine, N,N-diisopropylethylamine, triethylenediamine, DBU, DMAP, tetramethylethylenediamine, DBN, N-methylmorpholine, and pyridine, so as to more easily abstract the proton of the aromatic carboxylic acid.

[0022] Optionally, the solvent is any one or more of toluene, benzene, acetonitrile, xylene, dimethyl carbonate, DMF, NMP, 1,4-dioxane, 1,2-dimethylimidazole, 1,3-dimethylimidazole, and 1,3-dimethyl-3,4,5,6-tetrahydro-2-pyrimidinone (DMPU), so as to better dissolve the aromatic carboxylic acid and make the system form a homogeneous system.

[0023] Optionally, the temperature of the heat preservation reaction is 50 - 100 °C.

[0024] Optionally, the temperature of the heat preservation reaction is 60 - 80 °C.

[0025] In the reaction of the present invention, increasing the temperature will accelerate the reaction rate and improve the activity of the reactants. However, too high a temperature may also cause side reactions to occur. The possible side reactions include the self-polymerization of allyl substituents and even dehydration reactions. At the same time, the temperature setting also needs to consider maintaining the activity of the catalyst. Within the above temperature range, a relatively high reaction rate can be maintained. At the same time, due to the relatively low temperature, the equilibrium is more likely to shift towards the product direction, thereby increasing the yield of allyl ester.

[0026] Optionally, the time of the heat preservation reaction is 4 - 24 h to ensure a high conversion rate of the raw materials. Under the conditions of the selected temperature and catalyst, the completion time required for the reaction is closely related to the reaction rate. Prolonging the reaction time can increase the conversion rate of the reactants, but too long a time may lead to an increase in side reactions.

[0027] Optionally, the process further includes:

[0028] After cooling the reaction system to room temperature, it is concentrated to recover the excessive allyl substituent and the solvent; the completely concentrated system contains all the products and the solid hydrochloride salt of the base. Here, the base refers to the acid-binding agent added to abstract the proton of the carboxyl group, and the hydrochloride salt of the base is generated during the reaction;

[0029] 10% aqueous sodium hydroxide solution is added and stirred and separated at room temperature, then extracted with ethyl acetate, the organic phase is concentrated to recover the acid-binding agent, and then recrystallized to obtain pure allyl ester with a purity > 99%.

[0030] The allyl ester obtained through the heat preservation process is the crude product of the product. Since it contains the hydrochloride salt of the base, the product is impure. The allyl ester after being processed through the above procedures removes the impurities in the reaction system and improves the purity of the product.

[0031] In the present invention, first, an aromatic carboxylic acid and a catalyst are dissolved in a solvent, and then through an acid-binding agent and an allyl substituent, heating and stirring (heating and heat preservation process), solvent desolvation (process of recovering the solvent after the reaction is completed), and recrystallization (process of purifying the product), different allyl esters are prepared.

[0032] Compared with the prior art, the present invention has at least one of the following beneficial effects:

[0033] The synthesis process of the allyl ester provided by the present invention mainly uses an aromatic carboxylic acid, an allyl substituent, a solvent, an acid-binding agent, and a catalyst to obtain the allyl ester through heat preservation and mixing. This synthesis process is simple, has a short reaction time, low energy consumption, and both the yield and purity are relatively high, and can be used for large-scale industrial production. In addition, the solvent and the allyl substituent therein can be recycled, which can reduce the solvent usage and thus reduce the process cost. Description of the Drawings

[0034] By reading the detailed description of the non-limiting embodiments with reference to the following drawings, other features, purposes, and advantages of the present invention will become more obvious:

[0035] Figure 1 It is a schematic flow chart of the synthesis process of the allyl ester in an embodiment of the present invention;

[0036] Figure 2 It is the HPLC chart of triallyl trimesate after heat preservation in Example 57 of the present invention;

[0037] Figure 3 It is the HPLC chart of triallyl trimesate after purification in Example 57 of the present invention;

[0038] Figure 4 It is the NMR chart of triallyl trimesate in Example 57 of the present invention. Detailed Embodiments

[0039] The present invention will be described in detail below with reference to specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made. These all belong to the protection scope of the present invention.

[0040] Figure 1 The schematic flow chart of the synthesis process of the allyl ester in the following embodiments is shown.

[0041] Example 1

[0042] This example provides a preparation method of triallyl trimellitate, which includes the following steps:

[0043] Add 315 g of trimellitic acid into a 2 L autoclave, add 300 mL of DMF to dissolve trimellitic acid, then add 3 g of sodium bromide as a catalyst, add DIPEA with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure the system is heated and stirred under a sealed environment, keep the temperature at 70 °C for 6 h, and then open the autoclave to take samples.

[0044] After testing, the HPLC purity of triallyl trimellitate is greater than 99%, and the yield is greater than 95%.

[0045] Example 2

[0046] This example provides a preparation method of triallyl trimesate, which includes the following steps:

[0047] Add 315 g of trimesic acid into a 2 L autoclave, add 300 mL of DMF to dissolve trimesic acid, then add 15 g of sodium bromide in catalytic amount, add DIPEA with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure the system is heated and stirred under a sealed environment, keep the temperature at 70 °C for 24 h, and then open the autoclave to take samples.

[0048] After testing, the HPLC purity of triallyl trimesate is greater than 95%, and the yield is greater than 85%.

[0049] Example 3

[0050] This example provides a preparation method of diallyl terephthalate, which includes the following steps:

[0051] Add 330 g of terephthalic acid into a 2 L autoclave, add 300 mL of DMF to dissolve terephthalic acid, then add 10 g of sodium bromide in catalytic amount, add DIPEA with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure the system is heated and stirred under a sealed environment, keep the temperature at 70 °C for 8 h, and then open the autoclave to take samples.

[0052] After testing, the HPLC purity of diallyl terephthalate is greater than 95%, and the yield is greater than 90%.

[0053] Example 4

[0054] This example provides a preparation method of diallyl isophthalate, which includes the following steps:

[0055] Add 330 g of isophthalic acid to a 2-L autoclave. Add 300 mL of DMF to dissolve the isophthalic acid. Then add 10 g of sodium bromide as a catalytic amount. Add DIPEA with a stir bar under manual stirring, and then add allyl chloride. Close the autoclave and tighten it to ensure that the system is heated and stirred under a closed environment. Keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0056] After testing, the HPLC purity of diallyl isophthalate is greater than 92%, and the yield is greater than 90%.

[0057] Example 5

[0058] This example provides a method for preparing allyl benzoate, which includes the following steps:

[0059] Add 366 g of benzoic acid to a 2-L autoclave. Add 300 mL of DMF to dissolve the benzoic acid. Then add 15 g of sodium bromide as a catalytic amount. Add DIPEA with a stir bar under manual stirring, and then add allyl chloride. Close the autoclave and tighten it to ensure that the system is heated and stirred under a closed environment. Keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0060] After testing, the HPLC purity of allyl benzoate is greater than 99%, and the yield is greater than 95%.

[0061] Example 6

[0062] This example provides a method for preparing triallyl benzene-1,3,5-tricarboxylate, which includes the following steps:

[0063] Add 315 g of benzene-1,3,5-tricarboxylic acid to a 2-L autoclave. Add 300 mL of DMF to dissolve the benzene-1,3,5-tricarboxylic acid. Then add DIPEA with a stir bar under stirring, and then add allyl chloride. Close the autoclave and tighten it to ensure that the system is heated and stirred under a closed environment. Keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0064] After testing, the HPLC purity of triallyl benzene-1,3,5-tricarboxylate is greater than 90%, and the yield is greater than 85%.

[0065] Example 7

[0066] This example provides a method for preparing triallyl trimellitate, which includes the following steps:

[0067] Add 315 g of trimellitic acid to a 2-L autoclave. Add 300 mL of DMF to dissolve the trimellitic acid. Then add DIPEA with a stir bar under stirring, and then add allyl chloride. Close the autoclave and tighten it to ensure that the system is heated and stirred under a closed environment. Keep it at 70 °C for 24 h, and then open the autoclave to take samples.

[0068] After testing, the HPLC purity of triallyl trimellitate is greater than 85%, and the yield is greater than 80%.

[0069] Example 8

[0070] This example provides a preparation method of diallyl terephthalate, including the following steps:

[0071] Add 330 g of terephthalic acid to a 2 L autoclave, add 300 mL of DMF to dissolve the terephthalic acid, add DIPEA with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure that the system is heated and stirred under a sealed environment, keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0072] After testing, the HPLC purity of diallyl terephthalate is greater than 90%, and the yield is greater than 85%.

[0073] Example 9

[0074] This example provides a preparation method of diallyl isophthalate, including the following steps:

[0075] Add 330 g of isophthalic acid to a 2 L autoclave, add 300 mL of DMF to dissolve the isophthalic acid, add DIPEA with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure that the system is heated and stirred under a sealed environment, keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0076] After testing, the HPLC purity of diallyl isophthalate is greater than 92%, and the yield is greater than 88%.

[0077] Example 10

[0078] This example provides a preparation method of allyl benzoate, including the following steps:

[0079] Add 366 g of benzoic acid to the autoclave, add 300 mL of DMF to dissolve the benzoic acid, add DIPEA with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure that the system is heated and stirred under a sealed environment, keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0080] After testing, the HPLC purity of allyl benzoate is greater than 95%, and the yield is greater than 90%.

[0081] Example 11

[0082] This example provides a preparation method of triallyl benzene-1,3,5-tricarboxylate, including the following steps:

[0083] Add 315 g of trimellitic acid to an autoclave, add 300 mL of DMF to dissolve trimellitic acid, add DIPEA with a stir bar under manual stirring, then add allyl bromide. Close the autoclave and tighten to ensure that the system is heated and stirred under a sealed environment. Keep it at 70 °C for 6 h, and then open the autoclave to take samples.

[0084] After testing, the HPLC purity of triallyl trimellitate is greater than 99%, and the yield is greater than 95%.

[0085] Example 12

[0086] This example provides a method for preparing triallyl trimellitate, which includes the following steps:

[0087] Add 315 g of trimellitic acid to a 2 L autoclave, add 300 mL of DMF to dissolve trimellitic acid, add DIPEA with a stir bar under manual stirring, then add allyl bromide. Close the autoclave and tighten to ensure that the system is heated and stirred under a sealed environment. Keep it at 70 °C for 24 h, and then open the autoclave to take samples.

[0088] After testing, the HPLC purity of triallyl trimellitate is greater than 90%, and the yield is greater than 85%.

[0089] Example 13

[0090] This example provides a method for preparing diallyl terephthalate, which includes the following steps:

[0091] Add 330 g of terephthalic acid to the autoclave, add 300 mL of DMF to dissolve terephthalic acid, add DIPEA with a stir bar under manual stirring, then add allyl bromide. Close the autoclave and tighten to ensure that the system is heated and stirred under a sealed environment. Keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0092] After testing, the HPLC purity of diallyl terephthalate is greater than 95%, and the yield is greater than 90%.

[0093] Example 14

[0094] This example provides a method for preparing diallyl isophthalate, which includes the following steps:

[0095] Add 330 g of isophthalic acid to a 2 L autoclave, add 300 mL of DMF to dissolve isophthalic acid, add DIPEA with a stir bar under manual stirring, then add allyl bromide. Close the autoclave and tighten to ensure that the system is heated and stirred under a sealed environment. Keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0096] After testing, the HPLC purity of diallyl isophthalate is greater than 94%, and the yield is greater than 90%.

[0097] Example 15

[0098] This example provides a preparation method of allyl benzoate, which comprises the following steps:

[0099] Add 366 g of benzoic acid into a 2 L autoclave, add 300 mL of DMF to dissolve benzoic acid, add DIPEA with a stir bar under manual stirring, then add allyl bromide, close the autoclave, tighten to ensure that the system is heated and stirred under a sealed environment, keep the temperature at 70 °C for 8 h, and then open the autoclave to take samples.

[0100] After testing, the HPLC purity of allyl benzoate is greater than 98%, and the yield is greater than 95%.

[0101] Example 16

[0102] This example provides a preparation method of triallyl trimellitate, which comprises the following steps:

[0103] Add 315 g of trimellitic acid into a 2 L autoclave, add 300 mL of DMF to dissolve trimellitic acid, then add 1.5 g of sodium iodide as a catalytic amount, add DIPEA with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure that the system is heated and stirred under a sealed environment, keep the temperature at 70 °C for 6 h, and then open the autoclave to take samples.

[0104] After testing, the HPLC purity of triallyl trimellitate is greater than 99%, and the yield is greater than 98%.

[0105] Example 17

[0106] This example provides a preparation method of triallyl trimesate, which comprises the following steps:

[0107] Add 315 g of trimesic acid into the autoclave in this example, add 300 mL of DMF to dissolve trimesic acid, then add 11 g of sodium iodide as a catalytic amount, add DIPEA with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure that the system is heated and stirred under a sealed environment, keep the temperature at 70 °C for 24 h, and then open the autoclave to take samples.

[0108] After testing, the HPLC purity of triallyl trimesate is greater than 95%, and the yield is greater than 85%.

[0109] Example 18

[0110] This example provides a preparation method of diallyl terephthalate, which comprises the following steps:

[0111] Add 330 g of terephthalic acid to a 2-L autoclave, add 300 mL of DMF to dissolve terephthalic acid, then add 15 g of sodium iodide as a catalytic amount, add DIPEA with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure that the system is heated and stirred under a sealed environment, keep at 70 °C for 8 h, and then open the autoclave to take samples.

[0112] After testing, the HPLC purity of diallyl terephthalate is greater than 95%, and the yield is greater than 90%.

[0113] Example 19

[0114] This example provides a method for preparing diallyl isophthalate, which includes the following steps:

[0115] Add 330 g of isophthalic acid to a 2-L autoclave, add 300 mL of DMF to dissolve isophthalic acid, then add 15 g of sodium iodide as a catalytic amount, add DIPEA with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure that the system is heated and stirred under a sealed environment, keep at 70 °C for 8 h, and then open the autoclave to take samples.

[0116] After testing, the HPLC purity of diallyl isophthalate is greater than 95%, and the yield is greater than 90%.

[0117] Example 20

[0118] This example provides a method for preparing allyl benzoate, which includes the following steps:

[0119] Add 366 g of benzoic acid to a 2-L autoclave, add 300 mL of DMF to dissolve benzoic acid, then add 15 g of sodium iodide as a catalytic amount, add DIPEA with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure that the system is heated and stirred under a sealed environment, keep at 70 °C for 8 h, and then open the autoclave to take samples.

[0120] After testing, the HPLC purity of allyl benzoate is greater than 98%, and the yield is greater than 95%.

[0121] Example 21

[0122] This example provides a method for preparing triallyl benzene-1,3,5-tricarboxylate, which includes the following steps:

[0123] Add 315 g of benzene-1,3,5-tricarboxylic acid to a 2-L autoclave, add 300 mL of DMF to dissolve benzene-1,3,5-tricarboxylic acid, add DIPEA with a stir bar under manual stirring, then add allyl alcohol, close the autoclave, tighten to ensure that the system is heated and stirred under a sealed environment, keep at 70 °C for 6 h, and then open the autoclave to take samples.

[0124] After testing, the HPLC purity of triallyl trimellitate is greater than 95%, and the yield is greater than 90%.

[0125] Example 22

[0126] This example provides a preparation method of triallyl isophthalate, which includes the following steps:

[0127] Add 315 g of trimellitic acid to a 2 L autoclave, add 300 mL of DMF to dissolve the trimellitic acid, add DIPEA with a stir bar under manual stirring, then add allyl alcohol, close the autoclave, tighten to ensure that the system is heated and stirred under a sealed environment, keep it at 70 °C for 24 h, and then open the autoclave to take samples.

[0128] After testing, the HPLC purity of triallyl isophthalate is greater than 90%, and the yield is greater than 85%.

[0129] Example 23

[0130] This example provides a preparation method of diallyl terephthalate, which includes the following steps:

[0131] Add 330 g of terephthalic acid to a 2 L autoclave, add 300 mL of DMF to dissolve the terephthalic acid, add DIPEA with a stir bar under manual stirring, then add allyl alcohol, close the autoclave, tighten to ensure that the system is heated and stirred under a sealed environment, keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0132] After testing, the HPLC purity of diallyl terephthalate is greater than 95%, and the yield is greater than 92%.

[0133] Example 24

[0134] This example provides a preparation method of diallyl isophthalate, which includes the following steps:

[0135] Add 330 g of isophthalic acid to a 2 L autoclave, add 300 mL of DMF to dissolve the isophthalic acid, add DIPEA with a stir bar under manual stirring, then add allyl alcohol, close the autoclave, tighten to ensure that the system is heated and stirred under a sealed environment, keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0136] After testing, the HPLC purity of diallyl isophthalate is greater than 90%, and the yield is greater than 85%.

[0137] Example 25

[0138] This example provides a preparation method of allyl benzoate, which includes the following steps:

[0139] Add 366 g of benzoic acid to a 2-L autoclave. Add 300 mL of DMF to dissolve the benzoic acid. Add DIPEA with a stir bar under manual stirring, and then add allyl alcohol. Close the autoclave and tighten to ensure that the system is heated and stirred under a sealed environment. Keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0140] After testing, the HPLC purity of allyl benzoate is greater than 95%, and the yield is greater than 90%.

[0141] Example 26

[0142] This example provides a preparation method of triallyl trimellitate, which includes the following steps:

[0143] Add 315 g of trimellitic acid to a 2-L autoclave. Add 300 mL of DMF to dissolve the trimellitic acid. Then add 3 g of sodium bromide as a catalytic amount. Add DIPEA with a stir bar under manual stirring, and then add allyl chloride. Close the autoclave and tighten to ensure that the system is heated and stirred under a sealed environment. Keep it at 60 °C for 6 h, and then open the autoclave to take samples.

[0144] After testing, the HPLC purity of triallyl trimellitate is greater than 90%, and the yield is greater than 85%.

[0145] Example 27

[0146] This example provides a preparation method of triallyl trimesate, which includes the following steps:

[0147] Add 315 g of trimesic acid to a 2-L autoclave. Add 300 mL of DMF to dissolve the trimesic acid. Then add 15 g of sodium bromide as a catalytic amount. Add DIPEA with a stir bar under manual stirring, and then add allyl chloride. Close the autoclave and tighten to ensure that the system is heated and stirred under a sealed environment. Keep it at 60 °C for 24 h, and then open the autoclave to take samples.

[0148] After testing, the HPLC purity of triallyl trimesate is greater than 80%, and the yield is greater than 70%.

[0149] Example 28

[0150] This example provides a preparation method of diallyl terephthalate, which includes the following steps:

[0151] Add 330 g of terephthalic acid to a 2-L autoclave. Add 300 mL of DMF to dissolve the terephthalic acid. Then add 10 g of sodium bromide as a catalytic amount. Add DIPEA with a stir bar under manual stirring, and then add allyl chloride. Close the autoclave and tighten to ensure that the system is heated and stirred under a sealed environment. Keep it at 60 °C for 8 h, and then open the autoclave to take samples.

[0152] After testing, the HPLC purity of diallyl terephthalate is greater than 90%, and the yield is greater than 80%.

[0153] Example 29

[0154] This example provides a method for preparing diallyl isophthalate, which includes the following steps:

[0155] Add 330 g of isophthalic acid to a 2 L autoclave, add 300 mL of DMF to dissolve the isophthalic acid, then add 10 g of sodium bromide as a catalytic amount, add DIPEA with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure that the system is heated and stirred under a sealed environment, keep it at 60 °C for 8 h, and then take a sample after opening the autoclave.

[0156] After testing, the HPLC purity of diallyl isophthalate is greater than 85%, and the yield is greater than 80%.

[0157] Example 30

[0158] This example provides a method for preparing allyl benzoate, which includes the following steps:

[0159] Add 366 g of benzoic acid to a 2 L autoclave, add 300 mL of DMF to dissolve the benzoic acid, then add 15 g of sodium bromide as a catalytic amount, add DIPEA with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure that the system is heated and stirred under a sealed environment, keep it at 60 °C for 8 h, and then take a sample after opening the autoclave.

[0160] After testing, the HPLC purity of allyl benzoate is greater than 90%, and the yield is greater than 85%.

[0161] Example 31

[0162] This example provides a method for preparing triallyl trimesate, which includes the following steps:

[0163] Add 315 g of trimesic acid to a 2 L autoclave, add 300 mL of DMF to dissolve the trimesic acid, then add 3 g of sodium bromide as a catalytic amount, add triethylamine with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure that the system is heated and stirred under a sealed environment, keep it at 70 °C for 6 h, and then take a sample after opening the autoclave.

[0164] After testing, the HPLC purity of triallyl trimesate is greater than 95%, and the yield is greater than 90%.

[0165] Example 32

[0166] This example provides a method for preparing triallyl trimellitate, which includes the following steps:

[0167] Add 315 g of trimellitic acid to a 2-L autoclave. Add 300 mL of DMF to dissolve trimellitic acid. Then add 15 g of sodium bromide as a catalytic amount. Add triethylamine with a stir bar under manual stirring, and then add allyl chloride. Close the autoclave and tighten to ensure that the system is heated and stirred under a sealed environment. Keep it at 70 °C for 24 h, and then open the autoclave to take samples.

[0168] After testing, the HPLC purity of triallyl trimellitate is greater than 90%, and the yield is greater than 82%.

[0169] Example 33

[0170] This example provides a preparation method of diallyl terephthalate, which includes the following steps:

[0171] Add 330 g of terephthalic acid to a 2-L autoclave. Add 300 mL of DMF to dissolve terephthalic acid. Then add 10 g of sodium bromide as a catalytic amount. Add triethylamine with a stir bar under manual stirring, and then add allyl chloride. Close the autoclave and tighten to ensure that the system is heated and stirred under a sealed environment. Keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0172] After testing, the HPLC purity of diallyl terephthalate is greater than 95%, and the yield is greater than 90%.

[0173] Example 34

[0174] This example provides a preparation method of diallyl terephthalate, which includes the following steps:

[0175] Add 330 g of isophthalic acid to a 2-L autoclave. Add 300 mL of DMF to dissolve isophthalic acid. Then add 10 g of sodium bromide as a catalytic amount. Add triethylamine with a stir bar under manual stirring, and then add allyl chloride. Close the autoclave and tighten to ensure that the system is heated and stirred under a sealed environment. Keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0176] After testing, the HPLC purity of diallyl terephthalate is greater than 92%, and the yield is greater than 88%.

[0177] Example 35

[0178] This example provides a preparation method of allyl benzoate, which includes the following steps:

[0179] Add 366 g of benzoic acid to a 2-L autoclave. Add 300 mL of DMF to dissolve benzoic acid. Then add 15 g of sodium bromide as a catalytic amount. Add triethylamine with a stir bar under manual stirring, and then add allyl chloride. Close the autoclave and tighten to ensure that the system is heated and stirred under a sealed environment. Keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0180] After testing, the HPLC purity of allyl benzoate is greater than 95%, and the yield is greater than 90%.

[0181] Example 36

[0182] This example provides a preparation method of triallyl trimellitate, which includes the following steps:

[0183] Add 315 g of trimellitic acid to a 2 L autoclave, add 300 mL of DMF to dissolve trimellitic acid, add triethylamine with a stir bar under manual stirring, then add allyl bromide, close the autoclave, tighten to ensure that the system is heated and stirred under a closed environment, keep it at 70 °C for 6 h, and then open the autoclave to take samples.

[0184] After testing, the HPLC purity of triallyl trimellitate is greater than 95%, and the yield is greater than 90%.

[0185] Example 37

[0186] This example provides a preparation method of triallyl trimesate, which includes the following steps:

[0187] Add 315 g of trimesic acid to a 2 L autoclave, add 300 mL of DMF to dissolve trimesic acid, add triethylamine with a stir bar under manual stirring, then add allyl bromide, close the autoclave, tighten to ensure that the system is heated and stirred under a closed environment, keep it at 70 °C for 24 h, and then open the autoclave to take samples.

[0188] After testing, the HPLC purity of triallyl trimesate is greater than 85%, and the yield is greater than 82%.

[0189] Example 38

[0190] This example provides a preparation method of diallyl terephthalate, which includes the following steps:

[0191] Add 330 g of terephthalic acid to a 2 L autoclave, add 300 mL of DMF to dissolve terephthalic acid, add triethylamine with a stir bar under manual stirring, then add allyl bromide, close the autoclave, tighten to ensure that the system is heated and stirred under a closed environment, keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0192] After testing, the HPLC purity of diallyl terephthalate is greater than 95%, and the yield is greater than 90%.

[0193] Example 39

[0194] This example provides a preparation method of diallyl isophthalate, which includes the following steps:

[0195] Add 330 g of isophthalic acid to a 2 L autoclave. Add 300 mL of DMF to dissolve the isophthalic acid. Add triethylamine with a stir bar under manual stirring, then add allyl bromide. Close the autoclave and tighten to ensure the system is heated and stirred under a sealed environment. Keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0196] After testing, the HPLC purity of diallyl isophthalate is greater than 93%, and the yield is greater than 87%.

[0197] Example 40

[0198] This example provides a method for preparing allyl benzoate, which includes the following steps:

[0199] Add 366 g of benzoic acid to a 2 L autoclave. Add 300 mL of DMF to dissolve the benzoic acid. Add triethylamine with a stir bar under manual stirring, then add allyl bromide. Close the autoclave and tighten to ensure the system is heated and stirred under a sealed environment. Keep it at 70 °C for 8 h, and then open the autoclave to take samples.

[0200] After testing, the HPLC purity of allyl benzoate is greater than 95%, and the yield is greater than 90%.

[0201] Example 41

[0202] This example provides a method for preparing triallyl benzene-1,3,5-tricarboxylate, which includes the following steps:

[0203] Add 315 g of benzene-1,3,5-tricarboxylic acid to a 2 L autoclave. Add 300 mL of 1,2-dichloroethane to dissolve the benzene-1,3,5-tricarboxylic acid. Then add 3 g of sodium bromide as a catalytic amount. Add DIPEA with a stir bar under manual stirring, then add allyl chloride. Close the autoclave and tighten to ensure the system is heated and stirred under a sealed environment. Keep it at 70 °C for 16 h, and then open the autoclave to take samples.

[0204] After testing, the HPLC purity of triallyl benzene-1,3,5-tricarboxylate is greater than 90%, and the yield is greater than 85%.

[0205] Example 42

[0206] This example provides a method for preparing triallyl trimellitate, which includes the following steps:

[0207] Add 315 g of trimellitic acid to a 2 L autoclave. Add 300 mL of 1,2-dichloroethane to dissolve the trimellitic acid. Then add 3 g of sodium bromide as a catalytic amount. Add DIPEA with a stir bar under manual stirring, then add allyl chloride. Close the autoclave and tighten to ensure the system is heated and stirred under a sealed environment. Keep it at 70 °C for 32 h, and then open the autoclave to take samples.

[0208] After testing, the HPLC purity of triallyl trimellitate is greater than 85%, and the yield is greater than 80%.

[0209] Example 43

[0210] This example provides a preparation method of diallyl terephthalate, including the following steps:

[0211] Add 330 g of terephthalic acid to a 2 L autoclave, add 300 mL of 1,2-dichloroethane to dissolve terephthalic acid, then add 10 g of sodium bromide in catalytic amount, add DIPEA with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure that the system is heated and stirred under a closed environment, keep warm at 70 °C for 16 h, and then open the autoclave to take samples.

[0212] After testing, the HPLC purity of diallyl terephthalate is greater than 95%, and the yield is greater than 92%.

[0213] Example 44

[0214] This example provides a preparation method of diallyl isophthalate, including the following steps:

[0215] Add 330 g of isophthalic acid to a 2 L autoclave, add 300 mL of 1,2-dichloroethane to dissolve isophthalic acid, then add 10 g of sodium bromide in catalytic amount, add DIPEA with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure that the system is heated and stirred under a closed environment, keep warm at 70 °C for 816 h, and then open the autoclave to take samples.

[0216] After testing, the HPLC purity of diallyl isophthalate is greater than 85%, and the yield is greater than 80%.

[0217] Example 45

[0218] This example provides a preparation method of allyl benzoate, including the following steps:

[0219] Add 366 g of benzoic acid to a 2 L autoclave, add 300 mL of 1,2-dichloroethane to dissolve benzoic acid, then add 15 g of sodium bromide in catalytic amount, add DIPEA with a stir bar under manual stirring, then add allyl chloride, close the autoclave, tighten to ensure that the system is heated and stirred under a closed environment, keep warm at 70 °C for 8 h, and then open the autoclave to take samples.

[0220] After testing, the HPLC purity of allyl benzoate is greater than 93%, and the yield is greater than 90%.

[0221] Example 46

[0222] This example provides a preparation method of triallyl benzene-1,3,5-tricarboxylate, including the following steps:

[0223] Add 315 g of trimellitic acid to a 2 L autoclave, add 10% sodium hydroxide aqueous solution to dissolve trimellitic acid, then add 500 mL of 1,2-dichloroethane, then add allyl bromide, close the autoclave, tighten to ensure that the system is heated and stirred under a closed environment, keep warm at 70 °C for 16 h, and then open the autoclave to take samples.

[0224] After testing, the HPLC purity of triallyl trimellitate is greater than 92%, and the yield is greater than 88%.

[0225] Example 47

[0226] This example provides a preparation method of triallyl trimellitate, including the following steps:

[0227] Add 315 g of trimellitic anhydride to a 2 L autoclave, add 10% sodium hydroxide aqueous solution to dissolve trimellitic anhydride, then add 500 mL of 1,2-dichloroethane, then add allyl bromide, close the autoclave, tighten to ensure that the system is heated and stirred under a closed environment, keep warm at 70 °C for 32 h, and then open the autoclave to take samples.

[0228] After testing, the HPLC purity of triallyl trimellitate is greater than 87%, and the yield is greater than 80%.

[0229] Example 48

[0230] This example provides a preparation method of diallyl terephthalate, including the following steps:

[0231] Add 330 g of terephthalic acid to a 2 L autoclave, add 10% sodium hydroxide aqueous solution to dissolve terephthalic acid, then add 500 mL of 1,2-dichloroethane, then add allyl bromide, close the autoclave, tighten to ensure that the system is heated and stirred under a closed environment, keep warm at 70 °C for 16 h, and then open the autoclave to take samples.

[0232] After testing, the HPLC purity of diallyl terephthalate is greater than 95%, and the yield is greater than 90%.

[0233] Example 49

[0234] This example provides a preparation method of diallyl isophthalate, including the following steps:

[0235] Add 330 g of isophthalic acid to a 2 L autoclave, add 10% sodium hydroxide aqueous solution to dissolve isophthalic acid, then add 500 mL of 1,2-dichloroethane, then add allyl bromide, close the autoclave, tighten to ensure that the system is heated and stirred under a closed environment, keep warm at 70 °C for 16 h, and then open the autoclave to take samples.

[0236] After testing, the HPLC purity of diallyl isophthalate is greater than 92%, and the yield is greater than 88%.

[0237] Example 50

[0238] This example provides a preparation method of allyl benzoate, which includes the following steps:

[0239] Add 366 g of benzoic acid to a 2 L autoclave, add 10% sodium hydroxide aqueous solution to dissolve benzoic acid, then add 500 mL of 1,2-dichloroethane, and then add allyl bromide. Close the autoclave and tighten it to ensure that the system is heated and stirred under a sealed environment. Keep the temperature at 70 °C for 8 h, and then open the autoclave to take samples.

[0240] After testing, the HPLC purity of allyl benzoate is greater than 96%, and the yield is greater than 93%.

[0241] Example 51

[0242] This example provides a preparation method of triallyl benzene-1,3,5-tricarboxylate, which includes the following steps:

[0243] Add 8 kg of benzene-1,3,5-tricarboxylic acid to a 50 L autoclave, add 8 kg of DMF to dissolve benzene-1,3,5-tricarboxylic acid, then add a catalytic amount of 80 g of sodium bromide, add DIPEA, seal the autoclave and start stirring. Add allyl chloride from the feeding funnel under mechanical stirring, close the feeding valve, and tighten each valve to ensure that the system is heated and stirred under a sealed environment. Keep the temperature at 80 °C for 3 h, and then open the autoclave to take samples.

[0244] After testing, the HPLC purity of triallyl benzene-1,3,5-tricarboxylate is greater than 95%, and the yield is greater than 90%.

[0245] Example 52

[0246] This example provides a preparation method of triallyl trimellitate, which includes the following steps:

[0247] Add 6 kg of trimellitic acid to a 50 L autoclave, add 10 kg of DMF to dissolve trimellitic acid, then add a catalytic amount of 294 g of sodium bromide, add DIPEA, seal the autoclave and start stirring. Add allyl chloride from the feeding funnel under mechanical stirring, close the feeding valve, and tighten each valve to ensure that the system is heated and stirred under a sealed environment. Keep the temperature at 80 °C for 7 h, and then open the autoclave to take samples.

[0248] After testing, the HPLC purity of triallyl trimellitate is greater than 93%, and the yield is greater than 87%.

[0249] Example 53

[0250] This example provides a preparation method of triallyl benzene-1,3,5-tricarboxylate, which includes the following steps:

[0251] Add 8 kg of trimellitic acid to a 50 L autoclave, add 10 kg of DMF to dissolve the trimellitic acid, then add 80 g of sodium bromide in catalytic amount, add DIPEA, seal the autoclave and start stirring. Add allyl chloride from the feeding funnel under mechanical stirring, close the feeding valve, tighten each valve to ensure that the system is heated and stirred under a closed environment. Keep it at 95 °C for 8 h, and then open the autoclave to take samples.

[0252] After testing, the HPLC purity of triallyl trimellitate is greater than 97%, and the yield is greater than 92%.

[0253] Example 54

[0254] This example provides a preparation method of triallyl trimellitate, which includes the following steps:

[0255] Add 6 kg of trimellitic anhydride to a 50 L autoclave, add 10 kg of DMF to dissolve the trimellitic anhydride, then add 294 g of sodium bromide in catalytic amount, add DIPEA, seal the autoclave and start stirring. Add allyl chloride from the feeding funnel under mechanical stirring, close the feeding valve, tighten each valve to ensure that the system is heated and stirred under a closed environment. Keep it at 100 °C for 7 h, and then open the autoclave to take samples.

[0256] After testing, the HPLC purity of triallyl trimellitate is greater than 96%, and the yield is greater than 90%.

[0257] Example 55

[0258] This example provides a preparation method of triallyl trimellitate, which includes the following steps:

[0259] Add 8 kg of trimellitic acid to a 50 L autoclave, add 10 kg of DMF to dissolve the trimellitic acid, then add 80 g of sodium bromide in catalytic amount, add DIPEA, seal the autoclave and start stirring. Add allyl chloride from the feeding funnel under mechanical stirring, close the feeding valve, tighten each valve to ensure that the system is heated and stirred under a closed environment. Keep it at 120 °C for 2 h, and then open the autoclave to take samples.

[0260] After testing, the HPLC purity of triallyl trimellitate is greater than 95%, and the yield is greater than 90%.

[0261] Example 56

[0262] This example provides a preparation method of triallyl trimellitate, which includes the following steps:

[0263] Add 6 kg of trimellitic acid to a 50 L autoclave, add 10 kg of DMF to dissolve trimellitic acid, then add a catalytic amount of 294 g of sodium bromide, add DIPEA, seal the autoclave, start stirring, add allyl chloride from the feeding funnel under mechanical stirring, close the feeding valve, displace air, fill with nitrogen until the pressure gauge reads 0.5 MPa, tighten each valve to ensure the system is heated and stirred under a closed environment at 100 °C for 4 h, and then open the autoclave to take samples.

[0264] After testing, the HPLC purity of triallyl trimellitate is greater than 96%, and the yield is greater than 92%.

[0265] Example 57

[0266] This example provides a preparation method of triallyl benzene-1,3,5-tricarboxylate, including the following steps:

[0267] Add 8 kg of benzene-1,3,5-tricarboxylic acid to a 50 L autoclave, add 10 kg of DMF to dissolve benzene-1,3,5-tricarboxylic acid, then add a catalytic amount of 80 g of sodium bromide, add DIPEA, seal the autoclave, start stirring, add allyl chloride from the feeding funnel under mechanical stirring, close the feeding valve, displace air, fill with nitrogen until the pressure gauge reads 0.5 MPa, tighten each valve to ensure the system is heated and stirred under a closed environment at 120 °C for 2 h, and then open the autoclave to take samples.

[0268] Figure 2 Show the HPLC chart of triallyl benzene-1,3,5-tricarboxylate after heat preservation in this example, Figure 3 Show the HPLC chart of triallyl benzene-1,3,5-tricarboxylate after purification in this example, Figure 4 Show the NMR chart of triallyl benzene-1,3,5-tricarboxylate in this example. After testing, the HPLC purity of triallyl benzene-1,3,5-tricarboxylate is greater than 99%, and the yield is greater than 95%.

[0269] Example 58

[0270] This example provides a preparation method of triallyl benzene-1,3,5-tricarboxylate, including the following steps:

[0271] Add 8 kg of benzene-1,3,5-tricarboxylic acid to a 50 L autoclave, add 10 kg of 2-MeTHF to dissolve benzene-1,3,5-tricarboxylic acid, then add a catalytic amount of 80 g of sodium bromide, add triethylamine, seal the autoclave, start stirring, add allyl chloride from the feeding funnel under mechanical stirring, close the feeding valve, displace air, fill with nitrogen until the pressure gauge reads 0.5 MPa, tighten each valve to ensure the system is heated and stirred under a closed environment at 120 °C for 2 h, and then open the autoclave to take samples.

[0272] After testing, the HPLC purity of triallyl benzene-1,3,5-tricarboxylate is greater than 89%, and the yield is greater than 85%.

[0273] Example 59

[0274] This example provides a preparation method of triallyl trimellitate, which includes the following steps:

[0275] Add 8 kg of trimellitic acid into a 50 L autoclave, add 10 kg of allyl chloride to dissolve part of the trimellitic acid, then add 80 g of sodium bromide in catalytic amount, add DIPEA, seal the autoclave and start stirring. Under mechanical stirring, add 10 kg of allyl chloride from the feeding funnel, close the feeding valve, flush in nitrogen until the pressure gauge reads 0.5 MPa, tighten each valve to ensure that the system is heated and stirred under a closed environment, keep the temperature at 120 °C for 2 h, and then open the autoclave to take samples.

[0276] After testing, the HPLC purity of triallyl trimellitate is greater than 78%, and the yield is greater than 75%.

[0277] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various deformations or modifications within the scope of the claims, which do not affect the essence of the present invention. The above preferred features can be used in any combination without conflict.

Claims

1. A synthesis process for allyl esters, characterized in that: include: Add aromatic carboxylic acid into a reaction kettle and add a solvent to dissolve it; Adding a catalyst in a preset ratio to the reactor, and then adding an acid binding agent under stirring, wherein the preset ratio is greater than or equal to zero; Adding the allyl substitution product to the reaction kettle, sealing the reaction kettle, and carrying out the heat-insulating reaction until the aromatic carboxylic acid is completely converted; The reaction formula is as follows:

2. The synthesis process of allyl ester according to claim 1, characterized in that The molar ratio of aromatic carboxylic acid, catalyst, allyl substitution product, acid binding agent and solvent is 1:(0.05-0.1):(4-15):(1-3):(1-10).

3. The synthesis process of allyl ester according to claim 1, characterized in that, Have at least one of the following characteristics: - The amount of catalyst used is 2.5-16.7wt% of the aromatic carboxylic acid feed mass; - The amount of solvent used is 1-10wt% of the aromatic carboxylic acid feed mass; - The amount of the acid binding agent is 2-5wt% of the aromatic carboxylic acid feed mass.

4. The synthesis process of allyl ester according to claim 1, characterized in that: The catalyst is sodium bromide and / or sodium iodide.

5. The synthesis process of allyl ester according to claim 1, characterized in that: The acid binding agent is any one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium hydride, triethylamine, N,N-diisopropylethylamine, triethylenediamine, DBU, DMAP, tetramethylethylenediamine, DBN, N-methylmorpholine and pyridine.

6. The synthesis process of allyl ester according to claim 1, characterized in that: The solvent is any one or more of toluene, benzene, acetonitrile, xylene, dimethyl carbonate, DMF, NMP, 1,4-dioxane, 1,2-dimethylimidazole, 1,3-dimethylimidazole and 1,3-dimethyl-3,4,5,6-tetrahydro-2-pyrimidinone.

7. The synthesis process of allyl ester according to claim 1, characterized in that: The temperature of the heat preservation reaction is 50-100°C.

8. The synthesis process of allyl ester according to claim 1, characterized in that: The temperature of the heat preservation reaction is 60-80°C.

9. The synthesis process of allyl ester according to claim 1, characterized in that: The reaction time is 4-24 hours.

10. The synthesis process of allyl ester according to claim 1, characterized in that: The process also includes: The reaction system is cooled to room temperature and then concentrated to recover excess allyl substituent and solvent; A sodium hydroxide aqueous solution was added and stirred at room temperature to separate the liquids, and then extracted with ethyl acetate. The organic phase was concentrated, the acid-binding agent was recovered, and then recrystallized to obtain pure allyl ester.

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