A method for refining and purifying 3,3',5,5'-tetramethylbiphenyl diphenol diglycidyl ether

Abstract

The application discloses the technical field of compound synthesis, purification and purification technology, and relates to a purification method of 3,3',5,5'-tetramethyl diphenyl bisphenol diglycidyl ether, which comprises the following steps: S1, 100g of 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenyl is weighed, 1600ml of epichlorohydrin is measured, and the mixture is mixed, a catalyst triethylbenzylammonium chloride is added, heating is performed until the temperature reaches 100 DEG C, reaction is started for 4 hours, the temperature is reduced to about 80 DEG C, 60g of sodium hydroxide is added, and heat preservation reaction is performed for 1 hour, 500ml of water is added, stirring and standing are performed, water is separated, 500ml of water is used for washing twice, and organic phase is reduced pressure distilled; S2, first, non-polar solvents with low dielectric constant are used to separate impurities with smaller polarity than the product; and S3, polar solvents with large dielectric constant are used to separate impurities with larger polarity than the product, the method can be directly implemented in a reaction post-treatment process stage or directly used for purification of a reaction crude product.

Description

Technical Field

[0001] This invention relates to the field of compound synthesis, purification and refining technology, and in particular to a method for purifying 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether. Background Technology

[0002] 3,3',5,5'-Tetramethylbiphenyl bisphenol diglycidyl ether (CAS: 27043-36-3) is an intermediate raw material for biphenyl-based specialty resin polymers. Due to its excellent heat resistance, it is used as a modifying monomer for many products such as polyesters, polyurethanes, polycarbonates, polysulfones, and epoxy resins, to manufacture excellent engineering plastics and composite materials. Because of its anti-aging effect caused by oxygen and heat and its non-polluting nature, it can also be used as an antioxidant for rubber and latex, an antioxidant for plastics, and a stabilizer for dye intermediates or petroleum products. Its polymers possess the advantages of liquid crystal order and network crosslinking, forming a highly molecularly ordered and deeply crosslinked polymer network. Compared with ordinary resins, its heat resistance, water resistance, and impact resistance are greatly improved, making it suitable for preparing high-performance composite materials. Furthermore, because biphenyl resins have a very small coefficient of linear expansion in the orientation direction, as well as high dielectric strength and low dielectric loss, they have a wide range of applications in some specialized fields.

[0003] In the process of producing 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl and epichlorohydrin from raw materials, the residual phenol in the raw material is easily oxidized in the air to form byproducts such as impurities quinone. In addition, there are other byproducts in the reaction process. These impurities are difficult to remove, resulting in a darker color and a lower content in the product, which directly affects the quality of the product. It is difficult to remove the color in the later processing by general decolorization and washing.

[0004] The reaction mechanism is as follows:

[0005]

[0006] The following side reactions also occur during the reaction process:

[0007] β-addition of oxychloropropane with 4,4'-biphenyl:

[0008]

[0009] Further processing of intermediate products:

[0010]

[0011] ③ Oxidation of raw material quinone:

[0012] Summary of the Invention

[0013] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of the invention, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0014] Therefore, the purpose of this invention is to provide a method for refining and purifying 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether, addressing the problems existing in the process of generating 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether from 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl and epichlorohydrin.

[0015] To solve the above-mentioned technical problems, the present invention provides a method for purifying 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether, which adopts the following technical solution: The specific steps are as follows:

[0016] S1: Weigh 100g of 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl and measure 1600mL of epichlorohydrin, mix them, add the catalyst triethylbenzylammonium chloride, heat to 100℃, react for 4 hours, then cool to about 80℃, add 60g of sodium hydroxide, keep the temperature and react for 1 hour, add 500ml of water, stir and let stand to separate the water, then wash twice with 500ml of water, distill the organic phase under reduced pressure, add methanol and cool to precipitate crude 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether;

[0017] S2: First, use a nonpolar solvent with a low dielectric constant to separate impurities that are less polar than the product;

[0018] S3: Then, using a polar solvent with a high dielectric constant, impurities with a higher polarity than the product are separated to obtain 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether with high purity.

[0019] Optionally, the nonpolar solvent in step S2 is petroleum ether, n-heptane, n-octane, isooctane, or cyclopentane.

[0020] Optionally, the polar solvent in step S3 is methanol, ethanol, propanol, or butanol.

[0021] Optionally, in step S2, before adding a nonpolar solvent with a low dielectric constant, the crude product of 3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether from step S13 is heated to above 106°C for melting.

[0022] Optionally, in step S2, after adding a non-polar solvent with a low dielectric constant, the solvent is stirred for 15 minutes and then allowed to stand to separate.

[0023] In summary, the present invention has at least one of the following beneficial effects:

[0024] 1. This method first uses extraction to separate the small polar impurities in 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether, and then uses polar solvent crystallization to remove the larger polar impurities. Through the above technical means, substances that affect the color and product content are removed.

[0025] 2. This method can be implemented directly in the post-reaction processing stage or the crude reaction product can be directly used for purification.

[0026] 3. This method has a simple operation, produces high-quality refined products, and the solvent used can be recovered and reused through distillation, making it suitable for industrial production processes. Detailed Implementation

[0027] The present invention will now be described in further detail.

[0028] A method for refining and purifying 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether, S1: Weigh 100g of 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl and measure 1600mL of epichlorohydrin, mix them, add the catalyst triethylbenzylammonium chloride, heat to 100℃, react for 4 hours, then cool to about 80℃, add 60g of sodium hydroxide, keep the temperature and react for 1 hour, add 500ml of water, stir and let stand to separate the water, wash twice with 500ml, distill the organic phase under reduced pressure, add methanol and cool to precipitate crude 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether;

[0029] S2: First, use a non-polar solvent with a low dielectric constant to separate impurities with a lower polarity than the product. The non-polar solvents are petroleum ether, n-heptane, n-octane, isooctane, cyclopentane, etc. Before adding the non-polar solvent with a low dielectric constant, heat the crude product of 3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether in step S13 to above 106°C for melting. After adding the non-polar solvent with a low dielectric constant, stir for 15 minutes and then let it stand to separate the added solvent.

[0030] S3: Then, using a polar solvent with a high dielectric constant, impurities with a higher polarity than the product are separated to obtain 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether with high purity. The polar solvents include methanol, ethanol, propanol, butanol, etc.

[0031] Example 1: Weigh 100g of 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, measure 1600mL of epichlorohydrin, add the catalyst triethylbenzylammonium chloride (TEBAC), heat to 100℃, react for 4 hours, then cool to about 80℃, add 60g of sodium hydroxide, and keep the reaction at this temperature for 1 hour; add 500ml of water, stir and let stand to separate the water, then wash twice with 500ml of water, distill the organic phase under reduced pressure, add methanol and cool to precipitate crude 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether, product purity: 95%, product color 216.

[0032] Take 100g of the crude product obtained from the above reaction, melt it at 110℃, add 300ml of n-heptane, stir for 15 minutes, let it stand and separate, then add solvent; add 500ml of methanol to the product, cool and crystallize to obtain a white 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether product with a purity of 98.1% and a color of 42.

[0033] Example 2: 100g of crude 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether generated in Example 1 was melted at 110℃ and 300ml of n-octane was added. After stirring for 15 minutes, the mixture was allowed to stand and the solvent was added. Then, 500ml of ethanol was added to the product, and the mixture was cooled and crystallized to obtain a white 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether product with a purity of 98.3% and a color of 35.

[0034] Example 3: 100g of crude 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether generated in Example 1 was melted at 110℃ and 300ml of isooctane was added. After stirring for 15 minutes, the mixture was allowed to stand and the solvent was added. Then, 500ml of propanol was added to the product, and the mixture was cooled and crystallized to obtain a white 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether product with a purity of 98.2% and a color of 33.

[0035] Example 4: 100g of crude 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether generated in Example 1 was melted at 110°C and 300ml of isooctane was added. After stirring for 15 minutes, the mixture was allowed to stand and the solvent was added. Then, 500ml of propanol was added to the product, and the mixture was cooled and crystallized to obtain a white 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether product with a purity of 98.4% and a color of 26.

[0036] Example 5: 100g of crude 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether generated in Example 1 was melted at 110℃ and 300ml of cyclopentane was added. After stirring for 15 minutes, the mixture was allowed to stand and the solvent was added. Then, 500ml of butanol was added to the product, and the mixture was cooled and crystallized to obtain a white 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether product with a purity of 98.2% and a color of 21.

[0037] Example 6: In the reaction process of implementing the reaction in List 1, this method is directly applied to the post-processing process to achieve the purpose of purification.

[0038] Weigh 100g of 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, measure 1600mL of epichlorohydrin, add the catalyst triethylbenzylammonium chloride (TEBAC), heat to 100℃, and react for 4 hours. After cooling to about 80℃, add 60g of sodium hydroxide and keep the reaction at this temperature for 1 hour. Add 500ml of water, stir, let stand, and separate the water. Wash twice with 500ml of water, and recover the solvent by distillation of the organic phase. Add 360ml of n-heptane to the product after solvent removal, stir for 15 minutes, let stand, and separate the added solvent. Add 600ml of methanol to the product, cool, and crystallize to obtain a white 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether product with a purity of 98.2% and a color of 42.

[0039] Example 7: Based on Example 6, the washing process was adjusted as follows: 360 ml of n-octane was added to the product after solvent removal, stirred for 15 minutes, and then allowed to stand before adding solvent; 500 ml of ethanol was added to the product, and the mixture was cooled and crystallized to obtain a white 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether product with a purity of 98.3% and a color of 23.

[0040] The above are all preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Therefore, all equivalent changes made in accordance with the structure, shape and principle of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A method for purifying 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether, characterized in that: The specific steps are as follows: S1: Weigh 100g of 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl and measure 1600mL of epichlorohydrin, mix them, add the catalyst triethylbenzylammonium chloride, heat to 100℃, react for 4 hours, then cool to 80℃, add 60g of sodium hydroxide, keep the temperature for 1 hour, add 500ml of water, stir and let stand to separate the water, then wash twice with 500ml, distill the organic phase under reduced pressure, add methanol and cool to precipitate crude 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether; S2: First, use a non-polar solvent with a low dielectric constant to separate impurities with a lower polarity than the product. In step S2, before adding the non-polar solvent with a low dielectric constant, heat the crude product of 3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether from step S13 to above 106°C for melting. In step S2, after adding the non-polar solvent with a low dielectric constant, stir for 15 minutes and then let stand to separate the added solvent. S3: Using a polar solvent with a high dielectric constant, impurities with greater polarity than the product are separated to obtain 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether with high purity. The nonpolar solvent in step S2 is petroleum ether, n-heptane, n-octane, isooctane, or cyclopentane. The polar solvent in step S3 is methanol, ethanol, propanol, or butanol.

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