Background and overview[1]
4,4′-biphenyldiphenol is widely used in the chemical industry to prepare engineering composites, polyester, Modified monomers of polyurethane, polyphenylsulfone, epoxy resin, etc., as well as rubber and latex, especially light-colored vulcanized rubber products, food packaging rubber and medical latex products; in addition, 4,4′-biphenyldiphenol can also be used Used as dye intermediate, can synthesize photosensitive materials, etc. Among them, high-purity 4,4′-biphenyldiphenol is mainly used in thermotropic liquid crystal polymer engineering plastics. At present, my country’s high-purity 4,4′-biphenyldiphenol mainly relies on imports. Literature reports that the synthesis methods of 4,4′-biphenyldiphenol mainly include: benzidine method; biphenyl sulfonation alkali fusion method; biphenyl halogenation high-pressure hydrolysis method; tetra-tert-butyl-4,4′-biphenyldiphenol Off tert-butyl method. In addition, 4,4′-biphenyldiphenol can also be produced using precious metal catalysts such as palladium.
Preparation[1]
The preparation of 4,4′-biphenyldiphenol is as follows: add 3g of newly prepared metal samarium powder and 0.26g of anhydrous copper chloride to a dry reaction vessel in sequence, and stir magnetically. Then add 3.4g of p-chlorophenol and 10 mL of chlorobutylmethylimidazole that has been dried beforehand. The reaction was carried out at room temperature. The color of the reaction mixture became darker within 3 hours, and the reaction was continued for 8 hours. The reaction solution was extracted with ethyl acetate, and the crude product of 4,4′-biphenyldiphenol was obtained after post-treatment. Then it was further separated by column chromatography and purified by recrystallization to obtain 4,4′-biphenyldiphenol with a yield of 87%. White solid, melting point 280-284°C. 1HNMR (500MHz, CDCl3) δppm 8.32 (s, 2H), 7.41 (d, J = 8.8Hz, 4H), 6.89 (d, J = 8.4Hz, 4H). In acetic acid Dichloromethane is added to the residual liquid after ethyl ester extraction, and the recovered ionic liquid is obtained by stirring, standing, transferring, merging, and evaporating to recover the solvent.
Apply[2-4]
4,4’-Biphenyldiphenol can be used as an intermediate in pharmaceutical synthesis. Examples of its applications are as follows:
1) Prepare a polyetheretherketone terpolymer. Use 4,4′-difluorobenzophenone, hydroquinone and 4,4′-biphenyldiphenol as raw materials, diphenyl sulfone as the solvent, and a mixture of sodium bicarbonate and potassium bicarbonate as the salt. agent, the polyetheretherketone terpolymer prepared has high thermal stability, good mechanical properties and good processing properties. Using hydroquinone and 4,4′-biphenyldiphenol as the phenolic monomer mixture increases the steric hindrance of the polyether ether ketone copolymer and improves the temperature resistance of the product. In addition, 4,4′ -Biphenyldiphenol is less susceptible to oxidation than hydroquinone. Adding 4,4′-biphenyldiphenol can improve the stability of phenolic monomers.
2) Prepare a 4,4′-diphenyldiphenol modified phenolic resin material, which is obtained by reacting the following raw materials: 100 parts of phenol, 20-30 parts of 4,4′-diphenyldiphenol, and solid polymer 40-50 parts of formaldehyde, 30-40 parts of hydrogenated castor oil, 1-2 parts of camphorsulfonic acid, 30-40 parts of hydroxyethyl cellulose, 15-25 parts of polysulfone, 100 parts of solvent and 1-3 parts of nano-silica share. In the present invention, 4,4′-biphenyl diphenol, phenol and linseed oil are mixed, and a polymerization reaction occurs with paraformaldehyde under acidic conditions. The addition of biphenyl diphenol greatly improves the heat resistance of phenolic resin materials. At the same time, the modification of the resin by linseed oil and polysulfone gives the phenolic resin excellent wear resistance and toughness. The material obtained by impregnating, treating and processing glass fiber in the phenolic resin has excellent heat resistance and wear resistance.
3) Prepare a 4,4’-biphenyl diglycidyl ether. The preparation method is a two-step synthesis using 4,4-biphenyldiphenol and epichlorohydrin as raw materials under the action of a phase catalyst. First, the ring-opening etherification reaction is carried out, and then the ring-closing reaction is carried out. During the alkali addition process, the water separation process is used to separate the water generated by the reaction, thereby shifting the reaction equilibrium to the right and controlling various hydrolysis side reactions in the system. The product obtained by this process has high epoxy equivalent, high yield, simple reaction steps and convenient post-processing. The experimental results show that its epoxy value is 0.65~0.67 and its melting range is 159.1~160.4℃.
Main reference materials
[1] (CN108715574) A method of synthesizing biphenyl diphenol
[2] CN201710704422.0 Preparation method of polyetheretherketone terpolymer
[3] CN201710385941.5 A 4,4’-biphenyldiphenol modified phenolic resin material
[4] CN201010551762.24, preparation method of 4’-biphenyl diglycidyl ether
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