Background and overview[1]
Triphenyl phosphite (TPP) is an important chemical raw material. It is a colorless to light yellow crystal when it is below room temperature, and it is a colorless or light yellow transparent liquid when it is above room temperature. The melting point is 22-24°C, normal pressure The lower boiling point is 360°C, the relative density is 1.184 (20°C), and the refractive index is 1.5900 (20°C). It is insoluble in water and soluble in organic solvents such as ethanol, benzene and acetone.
Triphenyl phosphite is mainly used as an antioxidant and stabilizer for polymers. It has good synergy with many phenolic antioxidants and is mainly suitable for polyolefins, polyesters, ABS resins, and epoxy resins. , synthetic rubber and other products, it can keep the products transparent and inhibit color changes; it can also be used as a plasticizer for fiber films, with excellent transparency and water resistance; used in engineering plastics, phenolic resins, and halogen Used together with flame retardants, it can exert flame retardant and antioxidant effects and has light stability; it is also an important intermediate for the preparation of trialkyl phosphite.
Preparation[1-2]
Report 1,
The preparation method of triphenyl phosphite includes the following steps:
(1) Add phenol to the reaction kettle, add catalyst 1, raise the temperature to 45°C, and start adding phosphorus trichloride dropwise. After the dropwise addition, keep the reaction for 2 hours, raise the temperature to 70°C, vent nitrogen, and keep warm. React for 2 hours, raise the temperature to 90°C, continue to vent nitrogen, keep the temperature for 1 hour, cool to 70°C, filter, heat the filtrate to 120°C, vacuum under reduced pressure, and obtain a triphenyl phosphite mixture;
(2) Add the triphenyl phosphite mixture obtained in step (1) into the distillation kettle, add catalyst 2, raise the temperature to 180°C, and keep the reaction for 2 hours. Add a trace amount of phenyl ester and a small amount of diphenyl phosphite. The ester is distilled out to obtain triphenyl phosphite;
Wherein, the catalyst 1 is triethylamine and N,N-dimethylcyclohexylamine, and the weight of the triethylamine and the N,N-dimethylcyclohexylamine in the catalyst 1 The ratio is 1:0.4; the catalyst 2 is a multi-stage pore zeolite molecular sieve and Silicalite-1 molecular sieve, and the weight ratio of the multi-stage pore zeolite molecular sieve to the Silicalite-1 molecular sieve is 1:0.26; the multi-stage pore zeolite molecular sieve It is ethyl orthosilicate, silane coupling agent KH550 and pentaerythritol modified zeolite molecular sieve; the molar ratio of the phenol and the phosphorus trichloride in the step (1) is 3.2:1; the step (1) The molar ratio of the phenol and the catalyst 1 described in the step (2) is 1:1.05; the weight ratio of the triphenyl phosphite mixture and the catalyst 2 in the step (2) is 1:0.18;
The preparation method of the multi-stage pore zeolite molecular sieve is as follows:
(1) Add ZSM-5 molecular sieve, NaOH solution, and pentaerythritol into the reactor, and stir for 1-2 hours at 80-90°C; the weight ratio of the ZSM-5 molecular sieve to the NaOH solution and pentaerythritol is 1:20:3;
(2) Add cetyltrimethylammonium bromide, deionized water, and ethyl orthosilicate to the reactor, and stir for 1-2 hours; the cetyltrimethylammonium bromide and The weight ratio of the deionized water and the ethyl orthosilicate is 1:25:2.4;
(3) Slowly add the mixed solution in step (2) dropwise into step (1). After the dropwise addition is completed, stir for 0.5h, add silane coupling agent KH550 dropwise, and then seal the reaction kettle and place it at 160°C Crystallize in the box for 20h, wash, dry and roast at 550℃ for 6h. The crude multi-stage pore zeolite molecular sieve is added with a mass fraction of 80% ethanol and soaked for 20h, filtered and dried under reduced pressure at 60℃ for 10h to obtain the above Multistage pore zeolite molecular sieve; the weight ratio of the ZSM-5 molecular sieve to the silane coupling agent KH550 is 1:0.05; the weight ratio of the ZSM-5 molecular sieve to the cetyltrimethylammonium bromide It is 1:0.12; the weight ratio of the crude hierarchical pore zeolite molecular sieve of water-washed kaolin and the mass fraction of 80% ethanol is 1:6.
Report 2,
A method for preparing green, environmentally friendly and energy-saving triphenyl phosphite. The preparation method includes the following steps:
(1) Add the molten phenol into the enamel kettle and maintain medium-speed stirring. The pressure is controlled at -0.01 vacuum degree. Keep the phenol in the molten state and add the phosphorus trichloride solution dropwise at a constant speed. During the dropping process, maintain the temperature at 25~45 ℃, control the dripping time to 4h, after the dripping is completed, raise the temperature to 130°C and slowly increase the vacuum to the ultimate vacuum of the water pearlescent pigment jet pump, and continue the reaction at this temperature for 5h, during this process the enamel kettle has been maintained Stir quickly, wherein the ratio of the amount of the phenol to the phosphorus trichloride is 3.5:1;
(2) The HCl produced during the reaction in step (1) is desorbed through the condenser and entered into the buffer tank, and then absorbed into hydrochloric acid through the falling film absorber;
(3) After the reaction is completed, break the vacuum and lower the temperature to room temperature, then transfer the materials in the enamel kettle to the distillation kettle for vacuum distillation separation;
(4) First, increase the vacuum in the distillation kettle to the ultimate vacuum of the Roots vacuum machine, and at the same time slowly increase the temperature, with the maximum temperature not exceeding 220°C. During the heating process, distillation and separation are carried out. The front fraction is phenol, which is distilled out first. After being condensed to room temperature by a condenser, it is collected into a phenol receiving tank. After phenol is no longer distilled out, the middle fraction is collected into crude triphenyl phosphite. After being condensed to room temperature by the condenser, the fore-distilled triphenyl phosphite is collected into the receiving tank. The latter distillate is purified triphenyl phosphite. It is collected 1 hour after the crude triphenyl phosphite is distilled and condensed to room temperature through the condenser. Then collect it into the after-distillation triphenyl phosphite receiving tank;
(5) Condensate the triphenyl purified phosphite collected by distillation in step (4) and collect it in barrels to obtain the finished productTriphenyl phosphite.
