PDI catalyst for preparing cresol trozole trisiloxane, preparation method of PDI catalyst and preparation method of cresol trozole trisiloxane

Abstract

The invention relates to the technical field of fine chemical synthesis, and discloses a PDI catalyst for preparing cresol trozole trisiloxane, a preparation method of the PDI catalyst and a preparation method of cresol trozole trisiloxane, (MePDI) FeBr2, sodium and naphthalene are dissolved in an ultra-dry solvent and stirred to react in a nitrogen atmosphere, a reaction product is post-treated, and the PDI catalyst is prepared; the preparation method comprises the following steps: dissolving 2-(2 '-hydroxy-3'-methallyl-5 '-methylphenyl) benzotriazole and a PDI catalyst in an organic solvent, heating to 50-60 DEG C, dropwise adding bis (trimethylsiloxy) methylsilane, carrying out heat preservation reaction for 6-10 hours, carrying out vacuum concentration to remove the organic solvent, and crystallizing to obtain cresol trozole trisiloxane. The iron complex catalyst is adopted to replace a traditional platinum catalyst, so that the risk of heavy metal residues can be avoided while the material cost is reduced; and higher catalytic activity and selectivity can be realized by using a small amount of iron complex catalyst.

Description

Technical Field

[0001] The invention relates to the technical field of fine chemical synthesis, and in particular to a PDI catalyst for preparing drometrizole trisiloxane, a preparation method and a preparation method of drometrizole trisiloxane. Background Art

[0002] Drometrizole trisiloxane is prepared by hydrosilylation of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole.

[0003]

[0004] The hydrosilylation reaction is usually catalyzed by a platinum-containing reagent, such as Karstedt catalyst, chloroplatinic acid, N-heterocyclic carbene platinum complex, polymer platinum complex catalyst, various platinum-supported catalysts, etc. Although these catalysts can make the reaction run, the high price of platinum greatly limits the material cost optimization space of drometrizole trisiloxane. At the same time, platinum is a heavy metal, and the residual platinum also poses a great challenge to the quality of the product.

[0005]

[0006] Therefore, it is necessary to develop a catalyst that can replace the traditional platinum catalyst to catalyze the hydrosilylation, which can greatly reduce the material cost and avoid the risk of heavy metal residues. This obviously has positive practical significance. Summary of the invention

[0007] In view of the above problems existing in the prior art, the present application provides a PDI catalyst for preparing drometrizole trisiloxane, a preparation method and a preparation method of drometrizole trisiloxane, which can reduce the material cost and avoid the risk of heavy metal residues.

[0008] To solve the above problems, the present invention provides the following technical solutions:

[0009] In the first aspect, the present application provides a PDI catalyst for preparing drometrizole trisiloxane, the structural formula of which is shown in Formula I:

[0010]

[0011] Wherein, R is methyl or ethyl.

[0012] In a second aspect, the present application provides a method for preparing a PDI catalyst, comprising the following steps:

[0013] Will( MePDI)FeBr2, sodium and naphthalene are dissolved in an ultra-dry solvent and reacted with stirring under a nitrogen atmosphere, and the reaction product is post-treated to obtain a PDI catalyst.

[0014] In one embodiment of the present application, ( Me The molar ratio of FeBr2, sodium and naphthalene is 40:20:1.

[0015] In one embodiment of the present application, the ultra-dry solvent is selected from ultra-dry tetrahydrofuran, ultra-dry methanol, ultra-dry toluene, ultra-dry acetonitrile, ultra-dry acetone, and ultra-dry methyl tert-butyl ether.

[0016] In one embodiment of the present application, the ultra-dry solvent is selected from ultra-dry tetrahydrofuran.

[0017] In one embodiment of the present application, the stirring reaction temperature is 20-30° C., and the stirring reaction time is 4-6 h.

[0018] In one embodiment of the present application, the post-treatment is to concentrate the ultra-dry solvent under reduced pressure, add methyl tert-butyl ether to the residue, dissolve it, filter it to remove salt, and concentrate it under reduced pressure until no distillation occurs.

[0019] In a third aspect, the present application provides a method for preparing drometrizole trisiloxane, comprising the following steps:

[0020] 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole and PDI catalyst are dissolved in an organic solvent, the temperature is raised to 50-60°C, bistrimethylsiloxymethylsilane is added dropwise, the temperature is kept for 6-10 hours, the organic solvent is removed by concentration under reduced pressure, and crystallization is performed to obtain drometrizole trisiloxane.

[0021] In one embodiment of the present application, the mass ratio of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole to the PDI catalyst is 1:0.001-0.010.

[0022] In one embodiment of the present application, the mass ratio of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole to the PDI catalyst is 1:0.001-0.006.

[0023] In one embodiment of the present application, the mass ratio of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole to bistrimethylsiloxymethylsilane is 1:1-1.05.

[0024] In one embodiment of the present application, the mass ratio of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole to bistrimethylsiloxymethylsilane is 1:1.04-1.05.

[0025] In one embodiment of the present application, the mass ratio of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole to bistrimethylsiloxymethylsilane is 1:1.04.

[0026] In one embodiment of the present application, the mass ratio of the organic solvent to 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole is 3:1.

[0027] In one embodiment of the present application, the organic solvent is selected from ethyl acetate.

[0028] Compared with the prior art, the present application adopts an iron complex catalyst to replace the traditional platinum catalyst. Iron-based metals are abundant, cheap and easy to obtain, which can reduce material costs while avoiding the risk of heavy metal residues. And using a small amount of iron complex catalyst can achieve higher catalytic activity and selectivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The drometrizole trisiloxane prepared in Example 2 1 HNMR spectrum;

[0030] Figure 2 The HPLC spectra of drometrizole trisiloxane prepared in Example 2 at detection wavelengths of 305 nm and 342 nm respectively. DETAILED DESCRIPTION

[0031] The following will provide a clear and complete description of the technical solutions in the embodiments of the present application in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments.

[0032] The "range" disclosed in this application is defined in the form of a lower limit and an upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of the particular range. The range defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range.

[0033] Unless otherwise specified, the percentages between liquids and liquids in the present invention are volume / volume percentages; the percentages between liquids and solids in the present invention are volume / weight percentages; the percentages between solids and liquids in the present invention are weight / volume percentages; and the rest are weight / weight percentages.

[0034] Example 1: Preparation of iron complex catalyst (PDI catalyst)

[0035]

[0036] Add 10g ( Me PDI)FeBr2 (CAS No.: 1214787-10-6), add 0.81g of sodium metal, add 0.11g of naphthalene, add 200mL of ultra-dry tetrahydrofuran, and stir at 20-30°C for 5h under nitrogen protection. Concentrate the tetrahydrofuran under reduced pressure, add methyl tert-butyl ether to the residue, dissolve it, filter and remove salt, and concentrate it under reduced pressure until no distillation occurs to obtain 6.2g of dark brown solid, which is directly used in the reaction of synthesizing drometrizole trisiloxane.

[0037] Example 2: Preparation of drometrizole trisiloxane

[0038] In a reaction flask, 450 g of ethyl acetate, 150 g of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole, and 0.15 g of the iron complex catalyst prepared according to the method described in Example 1 were added in sequence, the temperature was raised to 50-60° C., 144 g of bistrimethylsiloxymethylsilane was slowly added dropwise, and the mixture was kept at 50-60° C. for 8 hours. The ethyl acetate was removed by concentration under reduced pressure, and the mixture was crystallized with ethanol-water to obtain 226 g of the product drometrizole trisiloxane with a yield of 84% and a purity of 99.9%. 1 HNMR(400MHz,DMSO-d6)δ10.79(s,1H),8.08(dd,2H),7.89(s,1H),7.60(dd,2H),7.09(s,1H),2. 63(m,2H),2.35(s,3H),2.08(s,1H),0.96(d,3H),0.67(m,1H),0.44(m,1H),0.08-0.03(m,21H).

[0039] Example 3: Preparation of drometrizole trisiloxane

[0040] In a reaction flask, 450 g of ethyl acetate, 150 g of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole, and 0.09 g of the iron complex catalyst prepared according to the method described in Example 1 were added in sequence, the temperature was raised to 50-60° C., 144 g of bistrimethylsiloxymethylsilane was slowly added dropwise, and the mixture was kept at 50-60° C. for 12 hours. The ethyl acetate was removed by concentration under reduced pressure, and the mixture was crystallized with ethanol-water to obtain 221 g of the product drometrizole trisiloxane with a yield of 82% and a purity of 99.9%.

[0041] Comparative Example 1

[0042] In a reaction flask, 450 g of ethyl acetate, 150 g of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole and 7.5 g of Custer's catalyst were added in sequence, the temperature was raised to 50-60°C, 144 g of bistrimethylsiloxymethylsilane was slowly added dropwise, and the mixture was kept at 50-60°C for 8 hours. The ethyl acetate was removed by concentration under reduced pressure, and the mixture was crystallized with ethanol-water to obtain 186 g of drometrizole trisiloxane with a yield of 69% and a purity of 97.2%.

[0043] Comparative Example 2

[0044] In a reaction flask, 450 g of ethyl acetate, 150 g of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole, and 7.5 g of a platinum-carbon catalyst (containing 5% platinum) were added in sequence. The temperature was raised to 50-60° C., and 144 g of bistrimethylsiloxymethylsilane was slowly added dropwise. After the addition was completed, the temperature was kept at 50-60° C. for 8 hours. The ethyl acetate was removed by concentration under reduced pressure, and the product was crystallized with ethanol-water to obtain 167 g of drometrizole trisiloxane with a yield of 62% and a purity of 96.4%.

[0045] It can be seen from Example 1 compared with Comparative Examples 1 and 2 that by using an iron complex catalyst instead of a traditional platinum catalyst and using a small amount of catalyst, higher catalytic activity and selectivity can be achieved.

[0046] The present application is described in detail above in conjunction with specific implementation methods and exemplary embodiments, but these descriptions cannot be understood as limiting the present application. Those skilled in the art understand that, without departing from the spirit and scope of the present application, the technical solution of the present application and its implementation methods may be subjected to a variety of equivalent substitutions, modifications or improvements, all of which fall within the scope of the present application.

Claims

1. A PDI catalyst for preparing drometrizole trisiloxane, the structural formula of which is shown in Formula I: in, R is methyl or ethyl.

2. A method for preparing a PDI catalyst as claimed in claim 1, characterized in that: The following steps are involved: Will( Me PDI)FeBr2, sodium and naphthalene are dissolved in an ultra-dry solvent and reacted with stirring under a nitrogen atmosphere, and the reaction product is post-treated to obtain a PDI catalyst.

3. The method for preparing the PDI catalyst according to claim 2, characterized in that: ( Me The molar ratio of FeBr2, sodium and naphthalene is 40:20:

1.

4. The method for preparing a PDI catalyst according to claim 2, characterized in that: The ultra-dry solvent is selected from one of ultra-dry tetrahydrofuran, ultra-dry methanol, ultra-dry toluene, ultra-dry acetonitrile, ultra-dry acetone, and ultra-dry methyl tert-butyl ether.

5. The method for preparing the PDI catalyst according to claim 2, characterized in that: The temperature of the stirring reaction is 20-30° C., and the time of the stirring reaction is 4-6 hours.

6. A method for preparing drometrizole trisiloxane, characterized in that: The preparation method is carried out under the catalysis of the PDI catalyst according to claim 1, and specifically comprises the following steps: 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole and PDI catalyst are dissolved in an organic solvent, the temperature is raised to 50-60°C, bistrimethylsiloxymethylsilane is added dropwise, the temperature is kept for 6-10 hours, the organic solvent is removed by concentration under reduced pressure, and crystallization is performed to obtain drometrizole trisiloxane.

7. The method for preparing drometrizole trisiloxane according to claim 6, characterized in that: The mass ratio of the 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole to the PDI catalyst is 1:0.001-0.

010.

8. The method for preparing drometrizole trisiloxane according to claim 7, characterized in that: The mass ratio of the 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole to the PDI catalyst is 1:0.001-0.

006.

9. The method for preparing drometrizole trisiloxane according to claim 6, characterized in that: The mass ratio of the 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole to bistrimethylsiloxymethylsilane is 1:1-1.

05.

10. The method for preparing drometrizole trisiloxane according to claim 6, characterized in that: The mass ratio of the organic solvent to 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole is 3:1; and the organic solvent is selected from ethyl acetate.

Images