Compound containing cyclic group having disulfide structure and preparation method and application of compound

[0032] According to the present invention, the preparation method of the compound having a cyclic group containing a bisulfide structure includes: contacting the first reactant with the second reactant in the presence of a solvent and a polymerization inhibitor and under condensation reaction conditions; The first reactant is a compound represented by general formula (4), and the second reactant is a compound represented by general formula (5):

[0033]

[0034] In the general formula (4), R 2 And X is as defined in the foregoing content of the present invention, Y can be -OH or -NH 2;

[0035] In the general formula (5), R 1 As defined in the foregoing content of the present invention, Z can be -Cl or -OH;

[0036] And when Y is -OH, Z is -Cl, when Y is -NH 2 When, Z is -OH.

[0037] According to a specific embodiment of the present invention, Y in the first reactant is -OH, and Z in the second reactant is -Cl. When Y in the first reactant is -OH and Z in the second reactant is -Cl, the molar ratio of the first reactant to the second reactant and the condensation reaction conditions only need to ensure that the first It is sufficient that C in the reactant (4) and D in the second reactant (5) undergo a condensation reaction and are bonded via an -O- bond. Therefore, the above-mentioned molar ratio and conditions can be selected in a wide range.

[0038] According to the above specific embodiments of the present invention, preferably, the molar ratio of the first reactant to the second reactant may be 1:1-3, more preferably 1:1-2.

[0039] The conditions of the condensation reaction include the reaction temperature and the reaction time. The reaction temperature may be 40-70°C, preferably 50-60°C; the reaction time may be 4-8 hours, preferably 5-7 hours.

[0040] The type and amount of the polymerization inhibitor can be conventional types and amounts known to those skilled in the art, and its function is mainly to completely terminate the free radical polymerization reaction of vinyl monomers; preferably, the polymerization inhibitor is combined with The molar ratio of the first reactant is 0.005-0.02:1, more preferably 0.01-0.02:1.

[0041] The second reactant whose Z is -Cl has a wide range of options. In the present invention, the second reactant can be preferably selected from acrylic acid chloride, methacrylic acid chloride, ethacrylic acid chloride, and propylacrylic acid chloride. , At least one of butyl acryloyl chloride, pentyl acryloyl chloride and hexyl acryloyl chloride.

[0042] According to another specific embodiment of the present invention, Y in the first reactant is -NH 2 , Z in the second reactant is -OH. When Y in the first reactant is -NH 2 When the Z in the second reactant is -OH, the molar ratio of the first reactant to the second reactant and the conditions of the condensation reaction only need to ensure that the Y in the first reactant (4) and the second It is sufficient that Z in the reactant (5) undergo a condensation reaction and be bonded via a -NH- bond, so the above-mentioned molar ratio and conditions can be selected in a wide range.

[0043] According to the aforementioned specific embodiments of the present invention, preferably, the molar ratio of the first reactant to the second reactant is 1:1-3, preferably 1:1-2.

[0044] The conditions of the condensation reaction include heating the first reactant and the second reactant to reflux, and the heating and refluxing time is 1-5 hours. Preferably, in order to facilitate the reaction and improve the reaction efficiency, the heating and refluxing of the first reactant and the second reactant is performed under the catalysis of a catalyst. In this method, the amount of the catalyst is not particularly limited, as long as it can promote the reaction. Preferably, the molar ratio of the first reactant to the catalyst can be 0.1-0.5:1, and the catalyst can usually be concentrated sulfuric acid. Or sodium hydroxide.

[0045] The type and dosage of the polymerization inhibitor can be conventional types and dosages known to those skilled in the art; preferably, the molar ratio of the polymerization inhibitor to the first reactant can be 0.005-0.02:1, more preferably 0.01 -0.02:1.

[0046] The second reactant whose Z is -OH can be selected from a wide range. In the present invention, the second reactant can be preferably selected from acrylic acid, methacrylic acid, ethacrylic acid, propyl acrylic acid, and butyl acrylic acid. , At least one of pentyl acrylic acid and hexyl acrylic acid.

[0047] According to the above two specific embodiments of the present invention, in order to further promote the reaction to proceed in the positive direction, the contact of the first reactant and the second reactant further includes carrying out in the presence of an acid binding agent. The type and amount can be selected in a wide range, and can be various substances that can absorb or react with acids. For example, the acid binding agent can be selected from at least one of triethylamine, ethylenediamine and triethanolamine . In this method, the amount of acid-binding agent is not particularly limited, as long as it can promote the progress of the reaction. Preferably, the molar ratio of the first reactant to the acid-binding agent can be 1:1-1.5, more preferably 1. : 1.1-1.4. The polymerization inhibitor is preferably at least one selected from hydroquinone, p-methoxyphenol and benzoquinone. The solvent is preferably at least one selected from the group consisting of acetone, benzene, toluene and cyclohexane. The amount of the solvent is only required to ensure that the reactants are fully dissolved. Under normal circumstances, the molar ratio of the first reactant to the solvent can be 1:1 -15.

[0050] Example 1

[0051] This example is used to illustrate the compound having a bisulfide structure-containing cyclic group provided by the present invention and the preparation method thereof.

[0052] In a three-necked flask equipped with a thermometer, agitator, and reflux condenser, add 1 part lipoamine (scientific name: 6,8-dithiaoctamine), 10 parts solvent toluene and 0.01 part polymerization inhibitor based on the amount of substance Hydroquinone was heated to 60°C to dissolve it completely, and then 2 parts of methacrylic acid and 0.1 part of concentrated sulfuric acid (mass percentage concentration 98%) were added in sequence. Heat to reflux for about 3 hours first, then install a water separator for azeotropic dehydration. After 0.7 parts of water was separated, the temperature in the three-necked flask was maintained at 120°C. When it is observed that the released amount is equivalent to the theoretical value (1 part of water), the reaction is stopped, the temperature is lowered to room temperature, and the unreacted acrylic acid and solvent are distilled off under reduced pressure. After separating and removing the catalyst and the polymerization inhibitor through a silica gel column, a compound (acrylamide monomer) containing a cyclic group containing a bisulfide structure as in the structural formula (I) is obtained with a yield of 85.2%.

[0053]

[0054] The H1-NMR before and after the reaction showed that the hydrogen peak position (chemical shift 2.69 ppm) and the integrated area of ​​the C attached to S at positions 6 and 8 did not change, indicating that the electron cloud distribution of S has not changed or shifted. The bisulfide structure is not destroyed.

[0055] Example 2

[0056] This example is used to illustrate the compound having a bisulfide structure-containing cyclic group provided by the present invention and the preparation method thereof.

[0057] In a three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, add 0.01 part of the polymerization inhibitor hydroquinone based on the amount of material, and then add 1 part of thiooctanol (scientific name: 6,8-dithiol Octanol), 1.2 parts of triethylamine, 10 parts of toluene solvent, warm up to 50°C, then add 2 parts of methacrylic acid chloride (the molar ratio of the three is 1:1.2:2) in the dropping funnel, and add 1 dropwise After the dripping is completed, keep it at 50°C for 8 hours. After the reaction, the salt produced by the reaction was filtered off, distilled under reduced pressure to remove the solvent and excess acid chloride, then the product was poured into a beaker, and the hydroquinone and a small amount of acrylic acid were washed away with a 5% by mass NaOH aqueous solution, and then washed with water Several times, until it is neutral, it is dried in vacuum to obtain a compound (acrylate monomer) containing a cyclic group with a disulfide structure as in the structural formula (II) with a yield of 90.4%.

[0058]

[0059] The H1-NMR before and after the reaction showed that the hydrogen peak position (chemical shift 2.69 ppm) and the integrated area of ​​the C attached to S at positions 6 and 8 did not change, indicating that the electron cloud distribution of S has not changed or shifted. The bisulfide structure is not destroyed.