CN1884289A - Di-2,4-dicumylphenyl pntaerythritol dphosphite preparation method - Google Patents

Abstract

The invention relates to a preparation method of di-2,4-dicumylphenyl pentaerythritol bisphosphite, which mainly solves the problems of low product yield, poor quality and complicated operation in the prior art. In the present invention, organic amine is used as catalyst, toluene, n-hexane or a mixed solution of the two are used as solvent, and 2,4-dicumylphenol is first reacted with phosphorus trichloride, and the resulting compound is further esterified with pentaerythritol. The technical scheme for producing di-2,4-dicumylphenyl pentaerythritol bisphosphite better solves this problem and can be used in the industrial production of polyethylene, polypropylene, ABS and other polymers.

Description

Two-2, the preparation method of 4-dicumylphenyl pentaerythritol bis-phosphite

Technical field

The present invention relates to two-2, the preparation method of 4-dicumylphenyl pentaerythritol bis-phosphite antioxidant.

Technical background

As everyone knows, polymkeric substance and goods thereof are the variation of recurring structure inevitably in preparation, processing and application process, makes intensity and appearance damage, and until losing use value, this phenomenon is called the aging of macromolecular material.The aging of macromolecular material is a kind of non-reversible process, mainly is to be caused by factors such as the light in the external world, oxygen, heat.Wherein, react by the autoxidation that oxygen causes, owing to can under lower temperature, carry out, and more be prone to than pure pyrolysis, so oxidative degradation is more even more important than pure thermolysis.In order effectively to prevent macromolecule material aging, normally add the material to suppress or to delay polymkeric substance oxidative degradation in manufacturing, processing and use, Here it is oxidation inhibitor.Usually according to mechanism of action classification, traditional antioxidant systems generally comprises four types of primary antioxidant, auxiliary antioxidant, heavy metal ion passivator and antiozonidates etc. to oxidation inhibitor.Primary antioxidant is a major function to catch the polymkeric substance peroxy radical, claims again " peroxy radical trapping agent " to comprise arylamine class and Hinered phenols two big series compounds.Auxiliary antioxidant has the decomposing copolymer peralcohol, prevents that its homolysis from bringing out the polymkeric substance thermal-oxidative degradation, claim again " peroxide decomposer " to comprise sulfo-dicarboxylic ester class and phosphite ester compound, usually and primary antioxidant be used.

Phosphite ester kind antioxidant is mainly used in the macromolecular materials such as polyethylene (PE), polypropylene (PP), ABS, prevents its oxidation and improves color and luster.Phosphorous acid ester and phenolic antioxidant are used has good interoperability, can significantly improve the processing stability of polyolefin resin.In polyolefin resin, add phosphite antioxidant and then can suppress the color and luster variation that polyolefin resin adds man-hour to greatest extent, improve the color stability of goods.

U.S. Pat 5917076 has been reported under tributylamine catalysis, phosphorus trichloride is splashed into 2, in the n-heptane solution of 4-DI-tert-butylphenol compounds, tetramethylolmethane, the dropping time is 2 hours, and temperature rising reflux shows that when acid number＜1 reaction finishes, aftertreatment gets two-2,4-di-tert-butyl-phenyl pentaerythritol bis-phosphite compound, purity 99.8%, yield 93.0%.

US 46925539 has reported at N, dinethylformamide (DMF) exists down, the phosphorus trichloride of 2.6 times of molar weights is splashed in the toluene solution of tetramethylolmethane, in 25～60 ℃ of reactions 5.5 hours, phosphorus trichloride that pressure reducing and steaming is excessive and part toluene obtain the toluene solution of dichloro pentaerythritol bis-phosphite.

J.Am.Chem.Soc., 72,5491 (1950) preparation methods that reported the dichloro pentaerythritol bis-phosphite.1.5 mole of pentaerythritol are added in 1 mole the dichloromethane solution of phosphorus trichloride, reflux continues to reflux 1 hour to the tetramethylolmethane completely dissolve, and the pressure reducing and steaming solvent obtains the dichloro pentaerythritol bis-phosphite, again with the chloroform recrystallization purifying.This method is not reported the yield of product, and phosphorus trichloride is excessive 0.5 mole, and is all influential to the recovery and the environment of solvent.

United States Patent (USP) 5364895 has been reported the method for preparing pentaerythritol bis-phosphite.With 2,4-dicumyl phenol, phosphorus trichloride are cooled to 50 ℃ again 90 ℃ of reactions 1.25 hours, add tetramethylolmethane, react 8 hours, obtain two-2,4-dicumylphenyl pentaerythritol bis-phosphite earlier.When trolamine catalysis was arranged, yield was 66.0%; During no trolamine catalysis, yield is 75.4%.The acid number of product is 1～6.Shortcomings such as this process exists product acid number height, product yield is low, and product purity is poor, fusing point is low.

The Chinese patent CN1048019 of Dover Chemical Corp. has reported the synthetic method of content with US5364895, also reported a kind of preparation method in addition, promptly by triphenyl phosphite, tetramethylolmethane, phenol, under sodium Metal 99.5 catalysis, in 120～125 ℃ of reactions 5 hours, transesterify takes place form tetramethylolmethane diphosphite diphenyl ester, cooling steams by-product phenol, and adding a certain amount of sodium Metal 99.5 again is catalyzer, with 2,4-di-(1-phenylisopropyl) phenol generation transesterification reaction generates two-2, and 4-dicumylphenyl pentaerythritol bis-phosphite is at last with washed with isopropyl alcohol, dry, 230～232 ℃ of the product fusing points that obtains, acid number＜1, it is 98% that dsc is surveyed its purity.This method troublesome poeration, the pressure reducing and steaming by-product phenol needs higher temperature, and needs to use dangerous sodium Metal 99.5 to be catalyzer.

In the above-mentioned document, final synthetic compound two-2, the method for 4-dicumylphenyl pentaerythritol bis-phosphite is few, and product yield and purity are all not too high.

Summary of the invention

Technical problem to be solved by this invention is to overcome in the past to have preparation two-2 in the document, exist product yield low, of poor quality during 4-dicumylphenyl pentaerythritol bis-phosphite, the shortcoming of complicated operation, provide a kind of new two-2, the preparation method of 4-dicumylphenyl pentaerythritol bis-phosphite.This method has easy and simple to handle, product yield height, the characteristics that purity is high.

For solving the problems of the technologies described above, the technical scheme that the present invention takes is as follows: a kind of two-2, the preparation method of 4-dicumylphenyl pentaerythritol bis-phosphite I, with 2,4-dicumyl phenol II, phosphorus trichloride III and tetramethylolmethane IV are raw material, with at least a organic amine that is selected from triethylamine, tri-n-butylamine, three TERTIARY BUTYL AMINE or the trolamine is catalyzer, is solvent with toluene, normal hexane or the mixing solutions of the two, carries out according to the following steps:

A) 20～50 ℃ of temperature of reaction, under the organic amine catalyzer existence condition, to 2, the toluene of 4-dicumyl phenol II, in normal hexane or the mixing solutions of the two, drip phosphorus trichloride III, the dropping time is 0.5～2.5 hour, be warming up to and reflux and kept 0.5～4 hour, obtain containing the solution of compound V, unreacted phosphorus trichloride of pressure reducing and steaming and a small amount of solvent are added the fresh solvent of equivalent weight, wherein phosphorus trichloride III is to 2, the mol ratio of 4-dicumyl phenol II is 1.01～1.30, and the organic amine catalyst consumption is 2,0.3～2.0% of 4-dicumyl phenol II weight;

B) under 30～50 ℃ of conditions of temperature of reaction, in the above-mentioned solution that contains compound V, add tetramethylolmethane IV, be incubated 1～5 hour, be warming up to and reflux and kept 1～8 hour, obtain containing two-2, the solution of 4-dicumylphenyl pentaerythritol bis-phosphite I, wherein tetramethylolmethane IV is to 2, and the mol ratio of 4-dicumyl phenol II is (1.0～1.5): 2;

C) contain two-2 with above-mentioned, the solution decompression of 4-dicumylphenyl pentaerythritol bis-phosphite I boils off solvent, adds anhydrous methanol or dehydrated alcohol in the remaining solid, reflux 1～5 hour, cooling is filtered, obtain two-2,4-dicumylphenyl pentaerythritol bis-phosphite I product.

In the technique scheme, the organic amine preferred version is to be selected from least a in triethylamine, tri-n-butylamine or the trolamine.A) the temperature of reaction preferred version is 30～40 ℃ in the step, dropping time preferred version is 0.5～1.5 hour, the return time preferred version is 1～3 hour, phosphorus trichloride III is to 2, the mol ratio of 4-dicumyl phenol II is preferably 1.01～1.10, the organic amine catalyst consumption is preferably 2,0.5～1.2% of 4-dicumyl phenol II weight.B) the temperature of reaction preferred version is 35～45 ℃ in the step, and the soaking time preferred version is 1～3 hour, and the return time preferred version is 3～5 hours, and tetramethylolmethane IV is to 2, and the mol ratio of 4-dicumyl phenol II is (1.0～1.2): 2.

The present invention filters out more superior catalyzer of performance and solvent by existing reaction process is improved, and makes quality product and yield be significantly improved, and has obtained better technical effect.

The invention will be further elaborated below by specific embodiment.

Embodiment

[embodiment 1]

500 milliliters of four-hole boiling flasks dispose stirring, thermometer, dropping funnel respectively, reflux condensing tube and hydrogenchloride effusion absorption unit.Take by weighing 2,4-di-(1-phenylisopropyl) phenol 75 grams, triethylamine 0.6 gram with toluene 60 grams, normal hexane 60 gram dissolvings, are warming up to 35 ℃, and nitrogen protection drips phosphorus trichloride 31.3 grams down, and the dropping time is 1 hour, drips off to be warming up to backflow, and keeps 2 hours.Unreacted phosphorus trichloride of pressure reducing and steaming and a small amount of solvent be totally 30 grams, adds 30 gram fresh toluene/normal hexane mixing solutionss (toluene by weight/normal hexane weight=1).Be cooled to 45 ℃, add tetramethylolmethane 15.4 grams, vigorous stirring 2 hours is warming up to backflow, is incubated 4 hours.The pressure reducing and steaming solvent adds dehydrated alcohol 100 grams, reflux 3 hours in the remaining solid.Cooling is filtered, and with washing with alcohol twice, gets white powder flow solids 75.9 grams, and yield 78.8%, fusing point are 231.2 ℃, and it is 98.5% that DSC differential scanning method is surveyed its purity, and acid number mg KOH/g is 0.65, and P content is 7.14%.

[embodiment 2]

500 milliliters of four-hole boiling flask configurations are with embodiment 1, difference is to substitute 0.6 gram triethylamine with 0.6 gram tri-n-butylamine, substitute the mixing solutions that 60 gram toluene and 60 restrain normal hexanes with 120 gram normal hexanes, add the mixing solutions (toluene by weight/normal hexane weight=1) that the fresh normal hexane of 30 grams substitutes 30 gram toluene and just several alkane.Aftertreatment is identical, gets white powder flow solids 70.6 grams, and yield 73.2%, fusing point are 229.8 ℃, and it is 97.2% that DSC differential scanning method is surveyed its purity, and acid number mg KOH/g is 0.91, and P content is 7.46%.

[embodiment 3]

500 milliliters of four-hole boiling flask configurations are with embodiment 1, difference is to substitute with 120 gram toluene the mixing solutions of 60 gram toluene and 60 gram normal hexanes, adds the mixing solutions (toluene by weight/normal hexane weight=1) that 30 gram fresh toluenes substitute 30 gram toluene and just several alkane.In the aftertreatment, substitute dehydrated alcohol with anhydrous methanol and carry out purifying, get white powder flow solids 77.6 grams, yield 80.4%, fusing point are 230.8 ℃, and it is 98.3% that DSC differential scanning method is surveyed its purity, and acid number mg KOH/g is 0.87, and P content is 7.35%.

[Comparative Examples 1]

500 milliliters of four-hole boiling flasks dispose stirring, thermometer, dropping funnel respectively, reflux condensing tube and hydrogenchloride effusion absorption unit.Take by weighing 2,4-di-(1-phenylisopropyl) phenol 75 grams, triethylamine 0.6 gram, the mixing solutions dissolving with 60 gram toluene and 60 gram normal hexanes is warming up to 35 ℃, and nitrogen protection drips phosphorus trichloride 31.3 grams down, and the dropping time is 1 hour, drips off to be warming up to backflow, and keeps 2 hours.Unreacted phosphorus trichloride of pressure reducing and steaming and a small amount of solvent be totally 30 grams, adds 30 gram fresh toluene/normal hexane mixing solutionss (toluene by weight/normal hexane weight=1).Be cooled to 45 ℃, add tetramethylolmethane 15.4 grams, vigorous stirring 2 hours is warming up to backflow, is incubated 4 hours.Cooling is filtered, with dehydrated alcohol 100 grams, reflux 2 hours.Cooling is filtered, and with washing with alcohol twice, gets white powder flow solids 61.5 grams, and yield 63.7%, fusing point are 227.9 ℃, and it is 88.3% that DSC differential scanning method is surveyed its purity, and acid number mg KOH/g is 3.12, and P content is 7.74%.

Claims (4)

1. A preparation method of di-2,4-dicumylphenyl pentaerythritol bisphosphite I, using 2,4-dicumylphenol II, phosphorus trichloride III and pentaerythritol IV as raw materials, selected from At least one organic amine in triethylamine, tri-n-butylamine, tri-tert-butylamine or triethanolamine is a catalyst, with toluene, normal hexane or a mixed solution of the two as a solvent, and proceeds in the following steps: a) At a reaction temperature of 20-50°C and in the presence of an organic amine catalyst, add phosphorus trichloride III dropwise to 2,4-dicumylphenol II in toluene, n-hexane or a mixed solution of the two, and add dropwise The time is 0.5 to 2.5 hours, the temperature is raised to reflux and maintained for 0.5 to 4 hours to obtain a solution containing compound V, and the unreacted phosphorus trichloride and a small amount of solvent are evaporated under reduced pressure, and the same weight of fresh solvent is added. The molar ratio of phosphorus III to 2,4-dicumylphenol II is 1.01-1.30, and the amount of organic amine catalyst is 0.3-2.0% of the weight of 2,4-dicumylphenol II; b) At a reaction temperature of 30-50°C, add pentaerythritol IV to the above-mentioned solution containing compound V, keep it warm for 1-5 hours, raise the temperature to reflux and keep it for 1-8 hours to obtain di-2,4-dicumyl A solution of phenyl pentaerythritol bisphosphite I, wherein the mol ratio of pentaerythritol IV to 2,4-dicumylphenol II is (1.0～1.5): 2; c) Evaporate the above-mentioned solution containing di-2,4-dicumylphenylpentaerythritol bisphosphite I to remove the solvent under reduced pressure, add anhydrous methanol or ethanol to the remaining solid, heat and reflux for 1 to 5 hours, and cool , and filtered to obtain two-2,4-dicumylphenyl pentaerythritol bisphosphite I product. 2. The method for preparing di-2,4-dicumylphenylpentaerythritol bisphosphite I according to claim 1, wherein said organic amine is selected from triethylamine, tri-n-butylamine or triethanolamine at least one of . 3. The method for preparing di-2,4-dicumylphenylpentaerythritol bisphosphite I according to claim 1, characterized in that the reaction temperature in step a) is 30-40°C, and the dropping time is 0.5- 1.5 hours, the reflux time is 1-3 hours, the molar ratio of phosphorus trichloride III to 2,4-dicumylphenol II is 1.01-1.10, and the amount of organic amine catalyst is the weight of 2,4-dicumylphenol II 0.5-1.2% of the total. 4. The method for preparing di-2,4-dicumylphenylpentaerythritol bisphosphite I according to claim 1, characterized in that the reaction temperature in step b) is 35-45°C, and the holding time is 1-3 hours, the reflux time is 3-5 hours, and the molar ratio of pentaerythritol IV to 2,4-dicumylphenol II is (1.0-1.2):2.