CN101792390A - Preparation method of bisphenol monocarboxylic ester compound antioxidant - Google Patents
Preparation method of bisphenol monocarboxylic ester compound antioxidant Download PDFInfo
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- CN101792390A CN101792390A CN201010123967A CN201010123967A CN101792390A CN 101792390 A CN101792390 A CN 101792390A CN 201010123967 A CN201010123967 A CN 201010123967A CN 201010123967 A CN201010123967 A CN 201010123967A CN 101792390 A CN101792390 A CN 101792390A
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Abstract
The invention relates to a preparation method of a bisphenol monocarboxylic ester compound antioxidant product which mainly used for synthesizing high molecular materials of rubber, polyolefine plastics, engineering plastics and the like. The invention adopts bisphenol compound and fatty acyl chloride as raw materials, triethylamine as acid absorbent, and the aliphatic hydrocarbon as solvent to generate the bisphenol monocarboxylic ester compound antioxidant product by esterification reaction. Suitable process conditions for synthesizing the bisphenol monocarboxylic ester compound are as follows: the mol ratio of the bisphenol compound to the fatty acyl chloride is 1.1-1.3; the mol ratio of the bisphenol compound to the triethylamine is 1:1.3-1.5; the reaction temperature is 60-85 DEG C; and the reaction time is 120-240 minutes. The bisphenol monocarboxylic ester compound antioxidant product is obtained by filtering, separating, crystallizing and refining after the reaction. The invention has the characteristics of simple production process, high product yield, high quality and convenient industrialized production. The obtained white crystallized bisphenol monocarboxylic ester antioxidant product can be used for high molecular materials having high requirements for color.
Description
Technical field
The present invention relates to a kind of preparation method of bisphenol monocarboxylic ester compound oxidation inhibitor, bisphenol monocarboxylic ester compound antioxidant refers in particular to following formula (I):
R in the formula (I)
1=C
1～C
5Straight chain or have the alkyl of side chain;
R
2=H or CH
3
R
3=CH
3Or vinyl;
Bisphenol monocarboxylic ester oxidation inhibitor is a kind of good antioxidant product, is mainly used in the macromolecular materials such as synthetic rubber, polyolefin plastics, engineering plastics.
Background technology
Traditional bis-phenolic antioxidants in use can be converted into the quinones with tint permanence, causes the oxidation stain of macromolecular material, the use of restriction bis-phenolic antioxidants.Along with the order benefit raising of macromolecular material production, application level, the traditional double phenolic antioxidant can not satisfy macromolecular material to the mechanical property of itself, the anti-aging requirement of appearance luster.The investigator is arranged based on traditional bis-phenolic antioxidants, develop a series of bisphenol monocarboxylic ester kind antioxidants.Studies have shown that: compare with traditional oxidation inhibitor, improved anti-aging usefulness greatly.The bisphenol monocarboxylic ester can overcome traditional bisphenols oxidation inhibitor causes the macromolecular material variable color in the process of performance antioxygenation problem, can satisfy the stabilization demand of the macromolecular material that colour stability is had relatively high expectations, as be used for materials such as butadiene polymer such as cis-1,4-polybutadiene rubber (BR), styrene-butadiene rubber(SBR) (SBR), butylbenzene block polymerization thermoplastic elastomer (SBS), chloroprene rubber (CR), paracril (NR), ABS resin.
EP 0322166, introduced with 2,2 '-ethylene two (4, the 6-di-tert-pentyl phenol), vinylformic acid, phosphorus oxychloride, triethylamine are raw material, aliphatic hydrocarbon is a solvent, preparation bisphenolmonoacryatecompounds compounds product 2-[1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl)-ethyl]-4,6-di-tert-pentyl-phenyl acrylate.EP 0500323 introduced with 2,2 '-methylene bis (4, the 6-DI-tert-butylphenol compounds), vinylformic acid, phosphorus oxychloride, triethylamine etc. are raw material, preparation 2-(2-hydroxyl-3,5-di-t-butyl phenmethyl)-4,6-di-tert-butyl-phenyl acrylate processes method.More than the technology weak point of two kinds of patent introductions be, adopt phosphorus oxychloride as raw material, introduce phosphorous by product in the product, make the product appearance color yellow partially.By contrast, this product is used for the BR, the SBS that adopt solution polymerization process production to have the pure white outward appearance, can make product produce xanthochromia in storage process, influences the visual appearance of product.In addition, this technological process is after esterification finishes, solids component in the reaction solution is triethylamine hydrochloride and triethylamine phosphate mixture, be not easy to separate the one-component triethylamine hydrochloride of purifying out, can only adopt method for washing to remove, the result can produce a large amount of trade effluents, is unfavorable for large-scale industrial production.
US 4562281 has introduced with 2,2 '-methylene bis (the 6-tertiary butyl-4-methylphenol), acetate, Tosyl chloride, triethylamine etc. are raw material, synthesis technique prepares 2-(the 2-hydroxyl-3-tertiary butyl-5-methylbenzene the methyl)-6-tertiary butyl-4-aminomethyl phenyl acetic ester.The weak point of this method, after being that reaction finishes, solids component in the reaction solution is triethylamine hydrochloride and triethylamine tosic acid salt mixture, the same existence separated purification difficult, the triethylamine recovery value is little, adopt method for washing to remove and to produce a large amount of trade effluents, be unfavorable for large-scale industrial production.
Summary of the invention
A kind of processing method for preparing the bisphenol monocarboxylic ester compound antioxidant product of the present invention; with the bisphenol cpd is raw material, and without phosphorus fat acyl chloride is an acylating reagent, and triethylamine is as acid binding agent; in organic solvent, carry out esterification, preparation bisphenol monocarboxylic ester antioxidant product.
Bisphenol cpd among the present invention specifically refers to:
2,2 '-methylene bis (4-methyl-6-tert butyl phenol),
2,2 '-ethylene two (4, the 6-di-tert-pentyl phenol),
2,2 '-methylene bis (4, the 6-DI-tert-butylphenol compounds),
2,2 '-ethylene two (4, the 6-DI-tert-butylphenol compounds),
Bisphenol cpd is commercially available commercial size product;
Without phosphorus fat acyl chloride is without phosphorus acrylate chloride and without phosphorus Acetyl Chloride 98Min., is commercially available commercial size product; Triethylamine is commercially available commercial size product;
Organic solvent is normal hexane, sherwood oil, normal heptane, octane, octane-iso, toluene etc., is commercially available commercial size product.
Preparing product process of the present invention, the mol ratio of bisphenol cpd and fat acyl chloride are 1: 1.0～1.5, and suitable mol ratio is 1: 1.1～1.3.The mol ratio of bisphenol cpd and triethylamine is 1: 1.1～1.7, and suitable mol ratio is 1: 1.3～1.5.
Preparing product process of the present invention, fat acyl chloride, triethylamine raw material adopt the mode that drips charging simultaneously, and the temperature that drips fat acyl chloride, triethylamine raw material is 55～70 ℃.The suitable time that drips the fat acyl chloride raw material is 40～50 minutes.Drip the triethylamine raw material when dripping fat acyl chloride, the suitable time that drips the triethylamine raw material is 60～90 minutes, is preferably 70～80 minutes.
Preparing product process of the present invention after dripping fat acyl chloride, triethylamine raw material, is carried out insulation reaction.The insulation reaction temperature is 50～90 ℃; Optimal temperature is 60～85 ℃.The insulation reaction time is 90～300 minutes; The suitable insulation reaction time is 120～240 minutes.
Preparing product process of the present invention, in order to make bisphenol cpd fully dissolving in organic solvent, the mass ratio of bisphenol cpd and organic solvent is 1: 5.
Preparing product process of the present invention, after reaction finished, the reaction mixture that obtains was the anhydrous system that contains the triethylamine hydrochloride solidliquid mixture, triethylamine hydrochloride is as byproduct of the present invention.Product is dissolved in the organic solvent.Filter, filter cake washs with appropriate amount of organic, obtains the triethylamine hydrochloride product.Merging filtrate.From filtrate, isolate bisphenol monocarboxylic ester antioxidant product of the present invention.Conform to the bisphenol monocarboxylic ester compound structural formula that formula (I) is refered in particular to through IR, HMBC, the qualitative product of the present invention of NMR, MS.Product of the present invention refers to:
The 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenmethyl)-4-aminomethyl phenyl acrylate,
2-[1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl)-ethyl]-4,6-di-tert-pentyl-phenyl acrylate,
2,4-di-t-butyl-6-(3,5-di-t-butyl-2-hydroxyl-phenmethyl)-phenyl acrylate,
2,4-di-t-butyl-6-[1-(3,5-di-t-butyl-2-hydroxy phenyl)-ethyl]-phenyl acrylate,
2,4-di-t-butyl-6-(3,5 di-t-butyls-2-hydroxybenzene methyl)-phenylacetic acid ester,
The 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenmethyl)-4-aminomethyl phenyl acetic ester.
Advantage of the present invention is:
1, the present invention is a raw material with bisphenol cpd, without phosphorus fat acyl chloride, and triethylamine is that acid binding agent prepares bisphenol monocarboxylic ester oxidation inhibitor, has the advantages that production technique is simple, product yield is high, quality is good, be convenient to suitability for industrialized production.Obtain the use that white crystals bisphenol monocarboxylic ester antioxidant product can satisfy the macromolecular material that color is had relatively high expectations.
2, triethylamine adopts the charging of dropping mode, and the pH value that can control the reaction feed liquid suppresses the polymerization of acrylate chloride between 7.5～8.5, help the carrying out of main reaction, improves the yield of product.
3, after reaction finishes, remove triethylamine hydrochloride by product in the reaction solution, alleviate wastewater treatment pressure, simplify product purification technology with filter method; And triethylamine hydrochloride obtains the byproduct triethylamine hydrochloride through corresponding treatment process, and raw material availability is improved, and improves productivity effect.
Embodiment
Be embodiments of the invention below.
Embodiment 1
In five mouthfuls of flasks of the 5000mL that has agitator, thermometer, acrylate chloride feed hopper, triethylamine feed hopper, reflux cooler, adding 2,2 '-methylene bis (4-methyl-6-tert butyl phenol) 340.50g (1.00mol), normal heptane 1800mL.Air in the nitrogen replacement still, heating, stirring are warming up to 57～60 ℃.Under this temperature, keep constant, begin to drip acrylate chloride 99.56g (1.10mol), added in 40～50 minutes.When dripping acrylate chloride, drip 121.43g (1.20mol) triethylamine raw material, the time that drips the triethylamine raw material is 70～80 minutes.After adding the triethylamine raw material, reaction solution is warming up to 63～65 ℃.Under this temperature, insulation reaction 120～130 minutes.
After reaction finished, the reaction mixture that obtains was a solidliquid mixture.Filter, the filter cake triethylamine hydrochloride washs with the 200mL normal heptane, washed twice, washings and filtrate are merged, pack in the 5000mL thin-film evaporator, under 60～80 ℃, decompression steams normal heptane 1700mL, with remaining concentrated solution cooling in the thin-film evaporator, slowly be cooled to 5～7 ℃, make the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenmethyl)-4-aminomethyl phenyl acrylate product crystallization separate out, filter, 300mL normal heptane washed twice with 5～7 ℃ obtains product 334.18g of the present invention.Outward appearance is a white crystals, fusing point: 132.5～134.2.Liquid chromatography purity: 98.7%.Molar product yield 84.7%.Ultimate analysis: C, 79.20; H, 8.71; O, 12.09.(theoretical value: C, 79.15; H, 8.69; O, 12.17).
Filter cake is at 105 ℃, and dry 2h gets white crystals triethylamine hydrochloride 150.20g, liquid chromatography purity: 95.2%, and molar product yield 99.2% (in acrylate chloride).
Embodiment 2
In five mouthfuls of flasks of the 5000mL that has agitator, thermometer, acrylate chloride feed hopper, triethylamine feed hopper, reflux cooler, adding 2,2 '-methylene bis (4-methyl-6-tert butyl phenol) 340.50g (1.00mol), sherwood oil 1800mL.Air in the nitrogen replacement still, heating, stirring are warming up to 63～65 ℃.Under this temperature, keep constant, begin to drip acrylate chloride 108.61g (1.20mol) raw material, added in 40～50 minutes.When dripping acrylate chloride, drip 131.55g (1.30mol) triethylamine raw material, the time that drips the triethylamine raw material is 70～80 minutes.After adding the triethylamine raw material, reaction solution is warming up to 67～70 ℃.Under this temperature, insulation reaction 150～160 minutes.
After reaction finished, the reaction mixture that obtains was a solidliquid mixture.Filter, filter cake triethylamine hydrochloride 200mL petroleum ether, washed twice, washings and filtrate are merged, pack in the 5000mL thin-film evaporator, under 60～80 ℃, decompression steams sherwood oil 1700mL, with remaining concentrated solution cooling in the thin-film evaporator, slowly be cooled to 5～7 ℃, make product crystallization of the present invention separate out, with 5～7 ℃ sherwood oil 300mL drip washing, wash twice, obtain the product 2-tertiary butyl-6-of the present invention (the 3-tertiary butyl-2-hydroxy-5-methyl base phenmethyl)-4-aminomethyl phenyl acrylate 337.73g.Outward appearance is a white crystals, fusing point: 132.3～134.4.Liquid chromatography purity: 98.8%.Molar product yield 85.6%.Ultimate analysis: C, 79.18; H, 8.72; O, 12.10.(theoretical value: C, 79.15; H, 8.69; O, 12.17).
Filter cake is at 105 ℃, and dry 2h gets white crystals triethylamine hydrochloride 164.19g, liquid chromatography purity: 96.0%, and molar product yield 99.4% (in acrylate chloride).
Embodiment 3
In five mouthfuls of flasks of the 5000mL that has agitator, thermometer, acrylate chloride feed hopper, triethylamine feed hopper, reflux cooler, adding 2,2 '-methylene bis (4-methyl-6-tert butyl phenol) 340.50g (1.00mol), sherwood oil 1800mL.Air in the nitrogen replacement still, heating, stirring are warming up to 64～66 ℃.Under this temperature, keep constant, begin to drip acrylate chloride 117.66g (1.30mol), added in 40～50 minutes.When dripping acrylate chloride, drip 141.67g (1.40mol) triethylamine, the time that drips the triethylamine raw material is 70～80 minutes.After adding the triethylamine raw material, reaction solution is warming up to 72～75 ℃.Under this temperature, insulation reaction 120～130 minutes.
After reaction finished, the reaction mixture that obtains was a solidliquid mixture.Filter, filter cake triethylamine hydrochloride 200mL petroleum ether, washed twice, washings and filtrate are merged, pack in the 5000mL thin-film evaporator, under 60～80 ℃, decompression steams sherwood oil 1700mL, with remaining concentrated solution cooling in the thin-film evaporator, slowly be cooled to 5～7 ℃, make product crystallization of the present invention separate out, with 5～7 ℃ sherwood oil 300mL drip washing, wash twice, obtain the product 2-tertiary butyl-6-of the present invention (the 3-tertiary butyl-2-hydroxy-5-methyl base phenmethyl)-4-aminomethyl phenyl acrylate 348.0g.Outward appearance is a white crystals, fusing point: 132.1～134.6.Liquid chromatography purity: 98.5%.Molar product yield 88.2%.Ultimate analysis: C, 79.20; H, 8.65; O, 12.15.(theoretical value: C, 79.15; H, 8.69; O, 12.17).
Filter cake is at 105 ℃, and dry 2h gets white crystals triethylamine hydrochloride 175.90g, liquid chromatography purity: 95.1%, and molar product yield 98.3% (in acrylate chloride).
Embodiment 4
In five mouthfuls of flasks of the 5000mL that has agitator, thermometer, acrylate chloride feed hopper, triethylamine feed hopper, reflux cooler, adding 2,2 '-methylene bis (4-methyl-6-tert butyl phenol) 340.50g (1.00mol), sherwood oil 1800mL.Air in the nitrogen replacement still, heating, stirring are warming up to 67～70 ℃.Under this temperature, keep constant, begin to drip acrylate chloride 126.71g (1.40mol) raw material, added in 40～50 minutes.When dripping acrylate chloride, drip 151.79g (1.50mol) triethylamine raw material, the time that drips the triethylamine raw material is 70～80 minutes.After adding the triethylamine raw material, reaction solution is warming up to 77～80 ℃.Under this temperature, insulation reaction 220～240 minutes.
After reaction finished, the reaction mixture that obtains was a solidliquid mixture.Filter, filter cake triethylamine hydrochloride 200mL petroleum ether, washed twice, washings and filtrate are merged, pack in the 5000mL thin-film evaporator, under 60～80 ℃, decompression steams sherwood oil 1700mL, with remaining concentrated solution cooling in the thin-film evaporator, slowly be cooled to 5～7 ℃, make product crystallization of the present invention separate out, with 5～7 ℃ sherwood oil 300mL drip washing, wash twice, obtain the product 2-tertiary butyl-6-of the present invention (the 3-tertiary butyl-2-hydroxy-5-methyl base phenmethyl)-4-aminomethyl phenyl acrylate 357.07g.Outward appearance is a white crystal, fusing point: 132.3～134.7.Liquid chromatography purity: 98.9%.Molar product yield 90.5%.Ultimate analysis: C, 79.13; H, 8.77; O, 12.10.(theoretical value: C, 79.15; H, 8.69; O, 12.17).
Filter cake is at 105 ℃, and dry 2h gets white crystals triethylamine hydrochloride 184.23g, liquid chromatography purity: 94.3%, and molar product yield 95.6% (in acrylate chloride).
Embodiment 5
In five mouthfuls of flasks of the 5000mL that has agitator, thermometer, acrylate chloride feed hopper, triethylamine feed hopper, reflux cooler, adding 2,2 '-two (4, the 6-di-tert-pentyl phenol) 494.79g (1.00mol), the octane 2500mL of ethylene.Air in the nitrogen replacement still.Heating, stirring are warming up to 60～65 ℃.Under this temperature, keep constant, begin to drip acrylate chloride 108.61g (1.20mol), added in 50～60 minutes.When dripping acrylate chloride, drip 126.49g (1.25mol) triethylamine raw material, the time that drips the triethylamine raw material is 80～90 minutes.After adding the triethylamine raw material, reaction solution is warming up to 75～80 ℃.Under this temperature, insulation reaction 150～160 minutes.
After reaction finished, the reaction mixture that obtains was a solidliquid mixture.Filter, the filter cake triethylamine hydrochloride washs with the 200mL octane, washed twice, washings and filtrate are merged, pack in the 5000mL thin-film evaporator, under 60～80 ℃, decompression steams octane 2300mL, with remaining concentrated solution cooling in the thin-film evaporator, slowly is cooled to 5～7 ℃, make product crystallization of the present invention separate out, with 5～7 ℃ octane 350mL drip washing, wash twice, obtain product 2-[1-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl)-and ethyl]-4,6-di-tert-pentyl-phenyl acrylate 464.87g.Outward appearance is a white crystal, fusing point: 117.3～118.1.Liquid chromatography purity: 98.6%.Molar product yield 84.7%.Ultimate analysis: C, 81.11; H, 10.26; O, 8.63.(theoretical value: C, 80.97; H, 10.28; O, 8.75).
Filter cake is at 105 ℃, and dry 2h gets white crystals triethylamine hydrochloride 160.55g, liquid chromatography purity: 94.3%, and molar product yield 97.2% (in acrylate chloride).
Embodiment 6
In five mouthfuls of flasks of the 5000mL that has agitator, thermometer, acrylate chloride feed hopper, triethylamine feed hopper, reflux cooler, adding 2,2 '-methylene bis (4, the 6-DI-tert-butylphenol compounds) 424.66g (1.00mol), octane-iso 2200mL.Air in the nitrogen replacement still.Heating, stirring are warming up to 57～60 ℃.Under this temperature, keep constant, begin to drip acrylate chloride 108.61g (1.20mol), added in 50～60 minutes.When dripping acrylate chloride, drip 131.55g (1.30mol) triethylamine raw material, the time that drips the triethylamine raw material is 80～90 minutes.After adding the triethylamine raw material, reaction solution is warming up to 65～70 ℃.Under this temperature, insulation reaction 150～160 minutes.
After reaction finished, the reaction mixture that obtains was a solidliquid mixture.Filter, the filter cake triethylamine hydrochloride washs with the 200mL octane-iso, washed twice, washings and filtrate are merged, pack in the 5000mL thin-film evaporator, under 60～80 ℃, decompression steams octane-iso 2000mL, with remaining concentrated solution cooling in the thin-film evaporator, slowly is cooled to 5～7 ℃, make product crystallization of the present invention separate out, with 5～7 ℃ octane-iso 350mL drip washing, wash twice, obtain product 2,4-di-t-butyl-6-(3,5-di-t-butyl-2-hydroxyl-phenmethyl)-phenyl acrylate 429.40g.Outward appearance is a white crystal, fusing point: 142.5～144.2.Liquid chromatography purity: 99.0%.Molar product yield 89.7%.Ultimate analysis: C, 80.25; H, 9.72; O, 10.03.(theoretical value: C, 80.29; H, 9.69; O, 10.03).
Filter cake is at 105 ℃, and dry 2h gets white crystals triethylamine hydrochloride 159.07g, liquid chromatography purity: 95.8%, and molar product yield 96.3% (in acrylate chloride).
Embodiment 7
In five mouthfuls of flasks of the 5000mL that has agitator, thermometer, acrylate chloride feed hopper, triethylamine feed hopper, reflux cooler, adding 2,2 '-methylene bis (4, the 6-DI-tert-butylphenol compounds) 424.66g (1.00mol), octane-iso 2200mL.Air in the nitrogen replacement still.Heating, stirring are warming up to 63～66 ℃.Under this temperature, keep constant, begin to drip acrylate chloride 117.66g (1.30mol), added in 50～60 minutes.When dripping acrylate chloride, drip 136.61g (1.35mol) triethylamine raw material, the time that drips the triethylamine raw material is 60～65 minutes.After adding the triethylamine raw material, reaction solution is warming up to 70～73 ℃.Under this temperature, insulation reaction 180～190 minutes.
After reaction finished, the reaction mixture that obtains was a solidliquid mixture.Filter, the filter cake triethylamine hydrochloride washs with the 200mL octane-iso, washed twice, washings and filtrate are merged, pack in the 5000mL thin-film evaporator, under 60～80 ℃, decompression steams octane-iso 2000mL, with remaining concentrated solution cooling in the thin-film evaporator, slowly is cooled to 5～7 ℃, make product crystallization of the present invention separate out, with 5～7 ℃ octane-iso 350mL drip washing, wash twice, obtain product 2,4-di-t-butyl-6-(3,5-di-t-butyl-2-hydroxyl-phenmethyl)-phenyl acrylate 432.75g.Outward appearance is a white crystal, fusing point: 142.1～144.7.Liquid chromatography purity: 99.0%.Molar product yield 90.4%.Ultimate analysis: C, 80.31; H, 9.64; O, 10.05.(theoretical value: C, 80.29; H, 9.69; O, 10.03).
Filter cake is at 105 ℃, and dry 2h gets white crystals triethylamine hydrochloride 169.28g, liquid chromatography purity: 95.9%, and molar product yield 94.6% (in acrylate chloride).
Embodiment 8
In five mouthfuls of flasks of the 5000mL that has agitator, thermometer, acrylate chloride feed hopper, triethylamine feed hopper, reflux cooler, adding 2,2 '-methylene bis (4, the 6-DI-tert-butylphenol compounds) 424.66g (1.00mol), octane-iso 2200mL.Air in the nitrogen replacement still.Heating, stirring are warming up to 67～70 ℃.Under this temperature, keep constant, begin to drip acrylate chloride 126.71g (1.40mol), added in 50～60 minutes.When dripping acrylate chloride, drip 146.73g (1.45mol) triethylamine raw material, the time that drips the triethylamine raw material is 75～80 minutes.After adding the triethylamine raw material, reaction solution is warming up to 77～80 ℃.Under this temperature, insulation reaction 220～230 minutes.
After reaction finished, the reaction mixture that obtains was a solidliquid mixture.Filter, the filter cake triethylamine hydrochloride washs with the 200mL octane-iso, washed twice, washings and filtrate are merged, pack in the 5000mL thin-film evaporator, under 60～80 ℃, decompression steams octane-iso 2000mL, with remaining concentrated solution cooling in the thin-film evaporator, slowly is cooled to 5～7 ℃, make product crystallization of the present invention separate out, with 5～7 ℃ octane-iso 350mL drip washing, wash twice, obtain product 2,4-di-t-butyl-6-(3,5-di-t-butyl-2-hydroxyl-phenmethyl)-phenyl acrylate 434.67g.Outward appearance is a white crystal, fusing point: 142.3～144.5.Liquid chromatography purity: 99.0%.Molar product yield 90.8%.Ultimate analysis: C, 80.27; H, 9.66; O, 10.07.(theoretical value: C, 80.29; H, 9.69; O, 10.03).
Filter cake is at 105 ℃, and dry 2h gets white crystals triethylamine hydrochloride 179.61g, liquid chromatography purity: 94.6%, and molar product yield 93.2% (in acrylate chloride).
Embodiment 9
In five mouthfuls of flasks of the 5000mL that has agitator, thermometer, acrylate chloride feed hopper, triethylamine feed hopper, reflux cooler, adding 2,2 '-two (4, the 6-DI-tert-butylphenol compounds) 438.69g (1.00mol), the octane-iso 2200mL of ethylene.Air in the nitrogen replacement still.Heating, stirring are warming up to 63～67 ℃.Under this temperature, keep constant, begin to drip acrylate chloride 108.61g (1.20mol), added in 50～60 minutes.When dripping acrylate chloride, drip 131.55g (1.30mol) triethylamine raw material, the time that drips the triethylamine raw material is 75～80 minutes.After adding the triethylamine raw material, reaction solution is warming up to 75～78 ℃.Under this temperature, insulation reaction 170～180 minutes.
After reaction finished, the reaction mixture that obtains was a solidliquid mixture.Filter, the filter cake triethylamine hydrochloride washs with the 200mL octane-iso, washed twice, washings and filtrate are merged, pack in the 5000mL thin-film evaporator, under 60～80 ℃, decompression steams octane-iso 2100mL, with remaining concentrated solution cooling in the thin-film evaporator, slowly is cooled to 5～7 ℃, make product crystallization of the present invention separate out, with 5～7 ℃ octane-iso 350mL drip washing, wash twice, the result gets product 2,4-di-t-butyl-6-[1-(3,5-di-t-butyl-2-hydroxy phenyl)-ethyl]-phenyl acrylate 429.66g.Outward appearance is a white crystal, fusing point: 188.2～189.7, and liquid chromatography purity: 98.6%.Molar product yield 87.2%.Ultimate analysis: C, 80.45; H, 9.86; O, 9.69.(theoretical value: C, 80.44; H, 9.82; O, 9.74).
Filter cake is at 105 ℃, and dry 2h gets white crystals triethylamine hydrochloride 157.42g, liquid chromatography purity: 96.6%, and molar product yield 95.3% (in acrylate chloride).
Embodiment 10
In five mouthfuls of flasks of the 5000mL that has agitator, thermometer, Acetyl Chloride 98Min. feed hopper, triethylamine feed hopper, reflux cooler, adding 2,2 '-methylene bis (4, the 6-DI-tert-butylphenol compounds) 424.66g (1.00mol), octane 2100mL.Air in the nitrogen replacement still.Heating, stirring are warming up to 55～58 ℃.Keep constant under this temperature, beginning dripping acetyl chloride 86.35g (1.10mol) added in 50～60 minutes.In dripping acetyl chloride, drip 121.43g (1.20mol) triethylamine raw material, the time that drips the triethylamine raw material is 80～90 minutes.After adding the triethylamine raw material, reaction solution is warming up to 65～68 ℃.Under this temperature, insulation reaction 150～160 minutes.
After reaction finished, the reaction mixture that obtains was a solidliquid mixture.Filter to isolate the solid filter cake triethylamine hydrochloride, wash with the 200mL octane, washed twice, washings and filtrate are merged, pack in the 5000mL thin-film evaporator, under 60～80 ℃, decompression steams octane 2000mL, with remaining concentrated solution cooling in the thin-film evaporator, slowly is cooled to 5～7 ℃, make product crystallization of the present invention separate out, with 5～7 ℃ octane 350mL drip washing, wash twice, obtain product 2 of the present invention, 4-di-t-butyl-6-(3,5 di-t-butyls-2-hydroxybenzene methyl)-phenylacetic acid ester 411.16g.Outward appearance is a white crystal, fusing point: 165.2～167.5, and liquid chromatography purity: 99.1%.Molar product yield 88.1%.Ultimate analysis: C, 79.77; H, 10.00; O, 10.23.(theoretical value: C, 79.78; H, 9.93; O, 10.28).
Filter cake is at 105 ℃, and dry 2h gets white crystals triethylamine hydrochloride 149.14g, liquid chromatography purity: 96.3%, and molar product yield 98.5% (in Acetyl Chloride 98Min.).
Embodiment 11
In five mouthfuls of flasks of the 5000mL that has agitator, thermometer, Acetyl Chloride 98Min. feed hopper, triethylamine feed hopper, reflux cooler, adding 2,2 '-methylene bis (4, the 6-DI-tert-butylphenol compounds) 424.66g (1.00mol), octane 2100mL.Air in the nitrogen replacement still.Heating, stirring are warming up to 63～66 ℃.Keep constant under this temperature, beginning dripping acetyl chloride 94.20g (1.20mol) added in 50～60 minutes.In dripping acetyl chloride, drip 126.49g (1.25mol) triethylamine raw material, the time that drips the triethylamine raw material is 80～90 minutes.After adding the triethylamine raw material, reaction solution is warming up to 72～75 ℃.Under this temperature, insulation reaction 180～190 minutes.
After reaction finished, the reaction mixture that obtains was a solidliquid mixture.Filter, the filter cake triethylamine hydrochloride washs with the 200mL octane, washed twice, washings and filtrate are merged, pack in the 5000mL thin-film evaporator, under 60～80 ℃, decompression steams octane 2000mL, with remaining concentrated solution cooling in the thin-film evaporator, slowly is cooled to 5～7 ℃, make product crystallization of the present invention separate out, with 5～7 ℃ octane 350mL drip washing, wash twice, obtain product 2 of the present invention, 4-di-t-butyl-6-(3,5 di-t-butyls-2-hydroxybenzene methyl)-phenylacetic acid ester 417.23g.Outward appearance is a white crystal, fusing point: 165.7～167.9, and liquid chromatography purity: 98.9%.Molar product yield 89.4%.Ultimate analysis: C, 79.90; H, 10.11; O, 9.99.(theoretical value: C, 79.78; H, 9.93; O, 10.28).Filter cake is at 105 ℃, and dry 2h gets white crystals triethylamine hydrochloride 157.42g, liquid chromatography purity: 94.7%, and molar product yield 95.3% (in Acetyl Chloride 98Min.).
Embodiment 12
In five mouthfuls of flasks of the 5000mL that has agitator, thermometer, Acetyl Chloride 98Min. feed hopper, triethylamine feed hopper, reflux cooler, adding 2,2 '-methylene bis (4, the 6-DI-tert-butylphenol compounds) 424.66g (1.00mol), octane 2100mL.Air in the nitrogen replacement still.Heating, stirring are warming up to 67～70 ℃.Keep constant under this temperature, beginning dripping acetyl chloride 102.05g (1.30mol) added in 50～60 minutes.In dripping acetyl chloride, drip 136.61g (1.35mol) triethylamine raw material, the time that drips the triethylamine raw material is 80～90 minutes.After adding the triethylamine raw material, reaction solution is warming up to 77～80 ℃.Under this temperature, insulation reaction 220～240 minutes.
After reaction finished, the reaction mixture that obtains was a solidliquid mixture.Filter, the filter cake triethylamine hydrochloride washs with the 200mL octane, washed twice, washings and filtrate are merged, pack in the 5000mL thin-film evaporator, under 60～80 ℃, decompression steams octane 2000mL, with remaining concentrated solution cooling in the thin-film evaporator, slowly is cooled to 5～7 ℃, make product crystallization of the present invention separate out, with 5～7 ℃ octane 350mL drip washing, wash twice, obtain product 2 of the present invention, 4-di-t-butyl-6-(3,5 di-t-butyls-2-hydroxybenzene methyl)-phenylacetic acid ester 420.50g.Outward appearance is a white crystal, fusing point: 165.7～167.1, and liquid chromatography purity: 98.9%.Molar product yield 90.1%.Ultimate analysis: C, 79.87; H, 10.05; O, 10.08.(theoretical value: C, 79.78; H, 9.93; O, 10.28).Filter cake is at 105 ℃, and dry 2h gets white crystals triethylamine hydrochloride 165.88g, liquid chromatography purity: 95.7%, and molar product yield 92.7% (in Acetyl Chloride 98Min.).
Embodiment 13
In five mouthfuls of flasks of the 5000mL that has agitator, thermometer, Acetyl Chloride 98Min. feed hopper, triethylamine feed hopper, reflux cooler, adding 2,2 '-methylene bis (4-methyl-6-tert butyl phenol) 340.50g (1.00mol), normal hexane 1800mL.Air in the nitrogen replacement still.Heating, stirring are warming up to 57～60 ℃.Keep constant under this temperature, beginning dripping acetyl chloride 86.35g (1.10mol) added in 50～60 minutes.In dripping acetyl chloride, drip 121.43g (1.20mol) triethylamine raw material, the time that drips the triethylamine raw material is 80～90 minutes.After adding the triethylamine raw material, reaction solution is warming up to 65～68 ℃.Under this temperature, insulation reaction 150～160 minutes.
After reaction finished, the reaction mixture that obtains was a solidliquid mixture.Filter, the filter cake triethylamine hydrochloride washs with the 200mL normal hexane, washed twice, washings and filtrate are merged, pack in the 5000mL thin-film evaporator, under 60～80 ℃, decompression steams normal hexane 1700mL, with remaining concentrated solution cooling in the thin-film evaporator, slowly be cooled to 5～7 ℃, make product crystallization of the present invention separate out, with 5～7 ℃ normal hexane 350mL drip washing, wash twice, obtain the product 2-tertiary butyl-6-of the present invention (the 3-tertiary butyl-2-hydroxy-5-methyl base phenmethyl)-4-aminomethyl phenyl acetic ester 333.96g.Outward appearance is a white crystal, fusing point: 99.5～103.2, and liquid chromatography purity: 99.0%.Molar product yield 87.3%.Ultimate analysis: C, 78.45; H, 9.01; O, 12.54.(theoretical value: C, 78.49; H, 8.96; O, 12.55).Filter cake is at 105 ℃, and dry 2h gets white crystals triethylamine hydrochloride 149.14g, liquid chromatography purity: 96.1%, and molar product yield 98.5% (Acetyl Chloride 98Min. meter).
Embodiment 14
In five mouthfuls of flasks of the 5000mL that has agitator, thermometer, Acetyl Chloride 98Min. feed hopper, triethylamine feed hopper, reflux cooler, adding 2,2 '-methylene bis (4-methyl-6-tert butyl phenol) 340.50g (1.00mol), toluene 1800mL.Air in the nitrogen replacement still.Heating, stirring are warming up to 63～66 ℃.Keep constant under this temperature, beginning dripping acetyl chloride 94.20g (1.20mol) added in 50～60 minutes.In dripping acetyl chloride, drip 126.49g (1.25mol) triethylamine raw material, the time that drips the triethylamine raw material is 80～90 minutes.After adding the triethylamine raw material, reaction solution is warming up to 72～75 ℃.Under this temperature, insulation reaction 180～190 minutes.
After reaction finished, the reaction mixture that obtains was a solidliquid mixture.Filter, filter cake triethylamine hydrochloride 200mL toluene wash, washed twice, washings and filtrate are merged, pack in the 5000mL thin-film evaporator, under 60～80 ℃, decompression steams toluene 1700mL, with remaining concentrated solution cooling in the thin-film evaporator, slowly be cooled to 5～7 ℃, make product crystallization of the present invention separate out, with 5～7 ℃ toluene 350mL drip washing, wash twice, obtain the product 2-tertiary butyl-6-of the present invention (the 3-tertiary butyl-2-hydroxy-5-methyl base phenmethyl)-4-aminomethyl phenyl acetic ester 337.02g.Outward appearance is a white crystal, fusing point: 98.7～103.1, and liquid chromatography purity: 98.6%.Molar product yield 88.1%.Ultimate analysis: C, 78.50; H, 9.05; O, 12.45.(theoretical value: C, 78.49; H, 8.96; O, 12.55).Filter cake is at 105 ℃, and dry 2h gets white crystals triethylamine hydrochloride 157.42g, liquid chromatography purity: 97.1%, and molar product yield 95.3% (Acetyl Chloride 98Min. meter).
Embodiment 15
In five mouthfuls of flasks of the 5000mL that has agitator, thermometer, Acetyl Chloride 98Min. feed hopper, triethylamine feed hopper, reflux cooler, adding 2,2 '-methylene bis (4-methyl-6-tert butyl phenol) 340.50g (1.00mol), toluene 1800mL.Air in the nitrogen replacement still.Heating, stirring are warming up to 67～70 ℃.Keep constant under this temperature, beginning dripping acetyl chloride 102.05g (1.30mol) added in 50～60 minutes.In dripping acetyl chloride, drip 136.61g (1.35mol) triethylamine raw material, the time that drips the triethylamine raw material is 80～90 minutes.After adding the triethylamine raw material, reaction solution is warming up to 77～80 ℃.Under this temperature, insulation reaction 230～240 minutes.
After reaction finished, the reaction mixture that obtains was a solidliquid mixture.Filter, filter cake triethylamine hydrochloride 200mL toluene wash, washed twice, washings and filtrate are merged, pack in the 5000mL thin-film evaporator, under 60～80 ℃, decompression steams toluene 1700mL, with remaining concentrated solution cooling in the thin-film evaporator, slowly be cooled to 5～7 ℃, make product crystallization of the present invention separate out, with 5～7 ℃ toluene 350mL drip washing, wash twice, obtain the product 2-tertiary butyl-6-of the present invention (the 3-tertiary butyl-2-hydroxy-5-methyl base phenmethyl)-4-aminomethyl phenyl acetic ester 340.46g.Outward appearance is a white crystal, fusing point: 99.2～103.6, and liquid chromatography purity: 98.3%.Molar product yield 89.0%.Ultimate analysis: C, 78.45; H, 9.01; O, 12.54.(theoretical value: C, 78.49; H, 8.96; O, 12.55).Filter cake is at 105 ℃, and dry 2h gets white crystals triethylamine hydrochloride 166.96g, liquid chromatography purity: 97.2%, and molar product yield 93.3% (Acetyl Chloride 98Min. meter).
Claims (10)
1. the preparation method of a bisphenol monocarboxylic ester compound antioxidant, it is characterized in that: be raw material with the bisphenol cpd, without phosphorus fat acyl chloride is an acylating reagent, and triethylamine is as acid binding agent, in organic solvent, carry out esterification, preparation bisphenol monocarboxylic ester antioxidant product; The mol ratio of bisphenol cpd and fat acyl chloride is 1: 1.0～1.5, and the mol ratio of bisphenol cpd and triethylamine is 1: 1.1～1.7.
2. the described preparation method of claim 1, it is characterized in that: described bisphenol cpd is 2,2 '-methylene bis (4-methyl-6-tert butyl phenol), 2,2 '-ethylene two (4, the 6-di-tert-pentyl phenol), 2,2 '-methylene bis (4, the 6-DI-tert-butylphenol compounds), or 2,2 '-ethylene two (4, the 6-DI-tert-butylphenol compounds).
3. the described preparation method of claim 1, it is characterized in that: described without phosphorus fat acyl chloride is without phosphorus acrylate chloride or without phosphorus Acetyl Chloride 98Min..
4. the described preparation method of claim 1, it is characterized in that: described organic solvent is normal hexane, sherwood oil, normal heptane, octane, octane-iso or toluene.
5. the described preparation method of claim 1, it is characterized in that: the structural formula of described bisphenol monocarboxylic ester compound is:
R in the formula
1=C
1～C
5Straight chain or have the alkyl of side chain;
R
2=H or CH
3
R
3=CH
3Or vinyl.
6. the described preparation method of claim 5, it is characterized in that: described bisphenol monocarboxylic ester compound is: the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenmethyl)-4-aminomethyl phenyl acrylate, 2-[1-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl)-and ethyl]-4,6-di-tert-pentyl-phenyl acrylate, 2,4-di-t-butyl-6-(3,5-di-t-butyl-2-hydroxyl-phenmethyl)-phenyl acrylate, 2,4-di-t-butyl-6-[1-(3,5-di-t-butyl-2-hydroxy phenyl)-ethyl]-phenyl acrylate, 2,4-di-t-butyl-6-(3,5 di-t-butyls-2-hydroxybenzene methyl)-phenylacetic acid ester or the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenmethyl)-4-aminomethyl phenyl acetic ester.
7. the described preparation method of claim 1 is specially: bisphenol cpd is joined the organic solution that forms bisphenol cpd in the organic flux, and the add-on of organic solvent should make bisphenol cpd fully dissolving in organic solvent; Adopt the mode that drips charging simultaneously to join in the organic solution of bisphenol cpd fat acyl chloride, triethylamine raw material, the temperature that drips fat acyl chloride, triethylamine raw material is 55～70 ℃, the time that drips the fat acyl chloride raw material is 40～50 minutes, and the time that drips the triethylamine raw material is 60～90 minutes; After dripping fat acyl chloride and triethylamine raw material, carry out insulation reaction, the insulation reaction temperature is 50～90 ℃, the insulation reaction time is 90～300 minutes; Remove by filter triethylamine hydrochloride, filtrate evaporated under reduced pressure, cooling concentration are promptly obtained bisphenol monocarboxylic ester oxidation inhibitor.
8. the described preparation method of claim 1, it is characterized in that: the mol ratio of bisphenol cpd and fat acyl chloride is 1: 1.1～1.3, the mol ratio of bisphenol cpd and triethylamine is 1: 1.3～1.5,, the mass ratio of bisphenol cpd and organic solvent is 1: 5.
9. the described preparation method of claim 7 is characterized in that: the time that drips the triethylamine raw material is 70～80 minutes, and the insulation reaction temperature is 60～85 ℃, and the insulation reaction time is 120～240 minutes.
10. the described preparation method of claim 7, it is characterized in that: described reaction mixture is the anhydrous system that contains the triethylamine hydrochloride solidliquid mixture, triethylamine hydrochloride is a byproduct.
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| CN102381968A (en) * | 2011-09-20 | 2012-03-21 | 广州合成材料研究院有限公司 | Method for preparing antioxidant of bisphenol monoacryate |
| CN102924238A (en) * | 2012-11-01 | 2013-02-13 | 常州大学 | Method for synthesizing 2, 2' -ethylene bis (4, 6-di-tert-amylphenol) product |
| CN103756061A (en) * | 2014-01-29 | 2014-04-30 | 中国科学院长春应用化学研究所 | Macromolecule antioxidant and preparation method and application thereof |
| CN108409556A (en) * | 2018-03-30 | 2018-08-17 | 吉林化工学院 | A kind of preparation method of one pot process bisphenol monoester kind antioxidant |
| CN108558942A (en) * | 2018-04-03 | 2018-09-21 | 吉林市银联科技有限公司 | A kind of bis-phenol list diphenylphosphite compound and preparation method |
| CN108911982A (en) * | 2018-07-19 | 2018-11-30 | 徐州博康信息化学品有限公司 | A kind of environment protection method for the styrene compound that synthesis acyloxy replaces |
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| CN102381968A (en) * | 2011-09-20 | 2012-03-21 | 广州合成材料研究院有限公司 | Method for preparing antioxidant of bisphenol monoacryate |
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| CN108409556A (en) * | 2018-03-30 | 2018-08-17 | 吉林化工学院 | A kind of preparation method of one pot process bisphenol monoester kind antioxidant |
| CN108558942A (en) * | 2018-04-03 | 2018-09-21 | 吉林市银联科技有限公司 | A kind of bis-phenol list diphenylphosphite compound and preparation method |
| CN108911982A (en) * | 2018-07-19 | 2018-11-30 | 徐州博康信息化学品有限公司 | A kind of environment protection method for the styrene compound that synthesis acyloxy replaces |
| CN111018676A (en) * | 2019-12-11 | 2020-04-17 | 乌海时联环保科技有限责任公司 | Method for preventing resorcinol from discoloring |
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