CN101508644A - Novel synthesis method for hindered phenol anti-oxidants - Google Patents
Novel synthesis method for hindered phenol anti-oxidants Download PDFInfo
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Abstract
The invention provides a new method for the synthesis of hindered phenols antioxidants. Under the action of a composite catalyst, a compound II and a compound III are subjected to transesterification and byproducts-methanol is obtained via heating and decompression; the rate of conversion of the product is more than 98%, and the compound I of hindered phenols antioxidants is directly obtained without crystallizing and purifying reaction liquid by solvent. The composite catalyst is composed of a primary catalyst of carboxylates of organotin and a secondary catalyst of thioester compounds of phosphite ester. The primary catalyst can be recycled.
Description
Technical field
The invention provides a kind of hindered phenol anti-oxidants new synthetic method.Conversion rate of products height, reaction solution need not solvent crystallization and purify, and directly obtain the purpose product.
Background technology
Hindered phenol anti-oxidants is the protective agent of a kind of broad-spectrum plastics, rubber, macromolecular material, can effectively protect plastics, rubber, macromolecular material to avoid the aging damage of oxygen in the environment, thereby prolongs the work-ing life of material.The representative products of hindered phenol anti-oxidants has: four-[β-(3,5-di-t-butyl, 4-hydroxy phenyl) propionic acid] pentaerythritol ester (trade names: antioxidant 1010); 3,5-di-t-butyl, 4-hydroxy phenyl propionic acid stearyl alcohol ester (trade name: antioxidant 1076); 3,5-di-t-butyl, 4-hydroxy phenyl propionic acid hexylene glycol ester, (trade name: oxidation inhibitor 259); 2, two [β-(3,5-di-t-butyl, the 4-hydroxy phenyl) propionic acid] esters (oxidation inhibitor 1035) of 2/-sulfurous ethyl glycol; 3,5-di-t-butyl, 4-hydroxy phenyl propionic acid isooctyl alcohol ester (trade name: oxidation inhibitor 1135).The reaction of synthetic above-mentioned antioxidant is referred to as transesterification reaction.
The synthetic method of traditional hindered phenol anti-oxidants is: monobasic or polynary high fatty alcohol and 3, and the 5-di-t-butyl, the 4-hydroxyl, phenylpropionic acid methyl esters (being called for short 3,5 methyl esters) carries out transesterification reaction and generates the purpose product.For example typical hindered phenol anti-oxidants 1010 is tetramethylolmethane and 3,5 methyl esters carry out transesterification reaction under catalyst action, deviate from by-product carbinol, the synthetic reaction solution obtains the product antioxidant 1010 through solvent (as methyl alcohol, ethanol) hot melt, crystallisation by cooling, filtering separation, drying.Traditional catalyzer is alkali-metal alkylol cpd such as sodium methylate, potassium tert.-butoxide; Or alkali-metal ammoniate, as Lithamide, ammonification is received etc. and alkali-metal salt such as Lithium Acetate, sodium-acetate etc.The effective product yield of these basic catalysts is lower, and usually at 70-85%, and the compound that obtains is normally yellow or dark liquid, therefore must just can reach the specification of quality of product through the crystallization and purification of solvent.
The someone adopts the organic oxygen compound of metallic tin in recent years, as dibutyltin oxide, and the soap of metallic zinc carries out transesterification reaction as stannous octoate as catalyzer, though the reaction solution outward appearance makes moderate progress, but still need the solvent crystallization purification just can reach the specification of quality of product.
Aforesaid method is in French Patent 2212323, the clear 56-12342 of Japanese Patent, and European patent 0032459 all is described in detail in numerous patents that U.S. Pat 4716244 and Switzerland vapour Ba-Jia Ji company announces.
Summary of the invention
The invention provides a kind of new synthetic method of hindered phenol anti-oxidants, this method transformation efficiency height, product color are good, and reaction product need not solvent crystallization and purifies, directly cooling granulation or grind and obtain the purpose product.
The present invention is achieved through the following technical solutions: under the effect of composite catalyst, a kind of ester compound II and a kind of aliphatic alcohols compound III are carried out transesterification reaction, by heating, decompression, deviate from by-product carbinol, reaction steams excessive reaction raw materials and Primary Catalysts after finishing, and obtains purpose product compound I hindered phenol anti-oxidants; The general structure of described hindered phenol anti-oxidants Compound I is:
Wherein: R1, R2 are the straight or branched alkane of C1-C8, R1, and the carbochain number of R2 can be identical, also can be inequality, R3 is the alkyl of C4-C20 or contains oxyalkyl, m is 1,2, or 3; N is 1,2,3 or 4;
Described reaction raw materials ester compound II general structure is:
Wherein: R1, R2 are the straight or branched alkane of C1-C8, R1, and the carbochain number of R2 can be identical, also can be inequality, R3 is the alkyl of C1-C3, m is 1,2, or 3;
The general structure of described reaction raw materials aliphatic alcohols compound III is:
R-(OH)n
Wherein R is the straight or branched alkane of C1-C20, and n quantity is 1,2,3 or 4, and the position is primary, the second month in a season, uncle, the alcohols hydroxyl in season.
Specifically: monohydroxy-alcohol or multi-alcohol and 3; 5 methyl esters carry out transesterification reaction; under the composite catalyst effect; by heating; by-product carbinol is extracted in decompression out, and reaction steams excessive reaction raw materials 3 after finishing; 5 methyl esters and Primary Catalysts, directly cooling granulation or grind and obtain hindered phenol anti-oxidants.
Described composite catalyst is a kind of binary composite catalyst, Primary Catalysts is: the carboxylate of organotin, for example: 1. dibutyl tin laurate, 2. Bis(lauroyloxy)dioctyltin, 3. two cis-butenedioic acid mono ethyl maleate dioctyltins, 4. the different monooctyl ester di-n-butyltin dilaurate of two maleic acid lists, 5. two Kunshun butene two acid mono-character ester di-n-butyl tins, 6. the different monooctyl ester dioctyltin of two maleic acid lists, 7. the different monooctyl ester di-n-butyl tin of two maleic acid lists, 8. lauric acid toxilic acid dibutyl tin, 9. toxilic acid dioctyltin.Above-mentioned nine kinds of Primary Catalystss are chosen any one kind of them and promotor collocation use all has good catalyzed reaction effect.After reaction finished, Primary Catalysts together steamed together with excess raw material, continues to recycle.
Promotor is: phosphorous acid ester, the monothioester compound, for example: a. three-(2, the 4-DI-tert-butylphenol compounds) phosphorous acid ester, b. diphosphorous acid tetramethylolmethane distearyl alcohol ester, c. two (2,4 DI-tert-butylphenol compounds) pentaerythritol phosphite, d. Tyox B, e. thio-2 acid two (14) alcohol ester, f. thio-2 acid two (18) alcohol ester.Above-mentioned six kinds of promotors are chosen any one kind of them and Primary Catalysts collocation use all has good catalyzed reaction effect.They be promotor also be plastics industry auxiliary antioxidant commonly used, usually as antioxidant 1010,1076 auxilliary antioxidant mixes composite use.
The promotor add-on is few in addition, accounts for about 0.1% of weight of material usually, remains in the antioxidant finished product, does not influence quality product.
The effect of the existing catalyzed reaction efficiently of composite catalyst of the present invention has good product color protection effect again; after transesterification reaction finishes; reaction solution is a colourless transparent liquid; conversion rate of products is greater than 98%; need not to adopt traditional solvent crystallization to purify; separate drying process, the direct cooling granulation of reaction solution or grind and obtain the purpose product.Save energy reduces waste discharge.
The composite weight ratio of described Primary Catalysts and promotor is 1～10:1, and the recommendation proportioning is 6:1.Nine kinds of Primary Catalystss and six kinds of promotors that the present invention is listed, the combination collocation of can choosing any one kind of them separately.Two class promotors: monothioester class and phosphorous acid ester, only need add when composite wherein a kind ofly with Primary Catalysts, though can select two kinds to add simultaneously, can't therefore produce better reaction effect.Still add wherein a kind of being advisable from angle easy and simple to handle.
The add-on of composite catalyst is the 0.05-3% of ester compound II weight in the ester-exchange reaction.The recommendation add-on is: 0.1-1%.Transesterification reaction temperature 120-240 ℃, 140-200 ℃ of recommendation response temperature.
Reaction of the present invention is under reduced pressure carried out, and tangible three phases is arranged.Fs is low insulation reaction, temperature 140-165 ℃, and pressure (absolute pressure, down together) 20000pa to 5000Pa; Subordinate phase is high insulation reaction, temperature 165-195 ℃, and pressure 5000-100Pa; Phase III steams 3,5 methyl esters, temperature 170-195, pressure 500-20Pa.
2-18 hour transesterification reaction time, 4-12 hour recommendation response time.
Generally, the transesterification reaction charge ratio is the excessive 5-80% of Compound I I molar percentage, recommends excessive 15-30%.Polyvalent alcohol is example with the tetramethylolmethane, tetramethylolmethane: 3,5 methyl esters=1:4-10, recommendation mol ratio are 1:5 (excessive 25%mol).Monohydroxy-alcohol is an example with positive stearyl alcohol, and positive stearyl alcohol: 3,5 methyl esters=1:1-3, recommendation mol ratio are 1:1.2 (excessive 20%mol).
Starting compound II is excessive to be not unalterable, when less with the compound III molecular weight of its reaction, when boiling point is low, then should be the compound III excessive 3-80%mol that feeds intake, hexanol for example, isooctyl alcohol etc.
After transesterification reaction finished, Primary Catalysts together steamed together with excessive reaction raw materials, continues to recycle.Reaction solution need not to adopt traditional solvent crystallization to purify, directly cooling granulation or grind and obtain the purpose product.The Primary Catalysts that reaction steams after finishing continues to recycle, and need not to add new Primary Catalysts again, only need add promotor in proportion and get final product.After repeatedly recycling, just need to replenish the Primary Catalysts of small loss.Technology in the past is to add acid after reaction finishes to destroy catalyzer, with the solvent crystallization washing, separates drying and obtains product, and will reclaim solvent then, and this process is very numerous and diverse, wastes energy, and increases raw material consumption.
Because Primary Catalysts together steams together with excessive raw material, so the content of tin can drop to below the 20ppm in the product.
The present invention has following advantage:
The transesterification reaction thing is a colourless transparent liquid, directly cooling granulation or grind the finished product that obtain meeting the antioxidant industry standard.
Need not to destroy Primary Catalysts, Primary Catalysts can recycle.
Compare traditional catalyzed reaction technology, omitted and add acid neutralization, solvent hot melt, crystallisation by cooling, filtering separation and drying, solvent recuperation process.Save energy reduces waste discharge.
Specific embodiments
Embodiment 1: with the typical products of antioxidant: four-[β-(3,5-di-t-butyl, 4-hydroxy phenyl) propionic acid] pentaerythritol esters (antioxidant 1010) are narrated enforcement of the present invention for example.
Agitator is being housed, condenser adds 136 gram (1 mole) tetramethylolmethanes, 3 of 1460 grams (5 moles) in the four-hole boiling flask of well heater, 5 methyl esters, (Primary Catalysts is the different monooctyl ester di-n-butyl tins of two maleic acid lists, and promotor is three-(2, the 4-DI-tert-butylphenol compounds) phosphorous acid esters to add the good composite catalyst of configured in advance 7 grams again, compound proportion is 6: 1), replace clean intrasystem air with pure nitrogen gas, give system decompression, heat up.Low insulation reaction of fs, temperature 140-165 ℃, pressure 5000-20000pa in 3 hours reaction times, extracts by-product carbinol out.165-190 ℃ of subordinate phase temperature of reaction, pressure 5000-100pa, 4 hours reaction times, continue to extract out by-product carbinol, phase III steams 3,5 methyl esters, temperature 170-190, pressure 500-20pa. changes condensator outlet, Primary Catalysts and excessive 3,5 methyl ester distilled in receiving flask, (steam 3,5 methyl esters and Primary Catalysts can be used for later reaction), when not having effluent, destroy vacuum with pure nitrogen gas, reaction solution is poured in clean a receiving plate, grind after the cooling and obtain product, the censorship result of laboratory test is as follows:
Weighing products 1170 grams reach 99.35% with the tetramethylolmethane calculated yield.
Primary Catalysts that embodiment 2:(reclaims for the first time and 3,5 methyl esters recycle experiment)
Agitator is being housed, and condenser adds 136 gram (1 mole) tetramethylolmethanes in the four-hole boiling flask of well heater, add 3 of recovery, 5 methyl esters (wherein containing Primary Catalysts), 292 grams add fresh 3 of 1168 grams (4 moles) again, 5 methyl esters, add 1 gram promotor three-(2, the 4-DI-tert-butylphenol compounds) phosphorous acid ester, replace clean intrasystem air with pure nitrogen gas, give system decompression, heat up.Low insulation reaction of fs, temperature 140-165 ℃, pressure 5000-20000pa in 3 hours reaction times, extracts by-product carbinol out.165-190 ℃ of subordinate phase temperature of reaction, pressure 5000-100pa, 4 hours reaction times, continue to extract out by-product carbinol, phase III: temperature 170-190, pressure 500-20pa. changes condensator outlet, Primary Catalysts and excessive 3,5 methyl ester distilled in receiving flask, (steam 3,5 methyl esters and Primary Catalysts can be used for later reaction), when not having effluent, destroy vacuum with pure nitrogen gas, reaction solution is poured in clean a receiving plate, grind after the cooling and obtain product, the censorship result of laboratory test is as follows:
Weighing products 1168 grams collect rate 99.1% with tetramethylolmethane
Embodiment 3. (Primary Catalysts after the circulation repeatedly and the experiment of 3,5 methyl esters)
Measure the Primary Catalysts quantity that contains in 3,5 methyl esters after circulating repeatedly well in advance, supply the main catalytic dosage of loss in the test.Agitator is being housed, condenser, add 68 gram (0.5 mole) tetramethylolmethanes in the four-hole boiling flask of well heater, the adding circulation repeatedly contains 3,5 methyl esters, 146 grams (0.5 mole) of Primary Catalysts, adds fresh 3 of 584 grams (2 moles), 5 methyl esters, add the main catalytic dosage of determining loss through chemically examining again, this experiment determines to add Primary Catalysts dibutyl tin laurate 1 gram, promotor thio-2 acid two (18) alcohol ester 0.5 gram.Replace clean intrasystem air with pure nitrogen gas, give system decompression, heat up.Three elementary reactions operation before continuing, steam clean 3,5 methyl esters and Primary Catalysts after, destroy vacuum with pure nitrogen gas, reaction solution is poured in clean a receiving plate, grind after the cooling and obtain product, the censorship result of laboratory test is as follows:
Weighing products 584 grams collect rate 99.18% with tetramethylolmethane.
Embodiment 4:
Another kind of representative products with antioxidant: β-(3,5-di-t-butyl, 4-hydroxy phenyl propionic acid) stearyl alcohol ester (trade name: be example antioxidant 1076), narrate enforcement of the present invention.
Agitator is being housed, condenser, add the positive stearyl alcohol of 270 grams (1 mole) in the four-hole boiling flask of well heater, 3,5 methyl esters of 350.4 grams (1.2 moles), (Primary Catalysts is a Bis(lauroyloxy)dioctyltin to add the good composite catalyst of configured in advance 1.8 grams again, promotor is a Tyox B, and compound proportion is 6:1), replace clean intrasystem air with pure nitrogen gas, give system decompression, heat up.Low insulation reaction of fs, temperature 130-155 ℃, pressure 5000-20000pa in 2 hours reaction times, extracts by-product carbinol out.155-175 ℃ of subordinate phase temperature of reaction, pressure 5000-100pa in 2 hours reaction times, continues to extract out by-product carbinol.Phase III steams 3,5 methyl esters, temperature 170-190, pressure 200-40pa, the transposing condensator outlet is excessive 3,5 is methyl ester distilled in receiving flask, (3,5 methyl esters and the Primary Catalysts that steam can be used for later reaction) be not when having effluent, destroy vacuum with pure nitrogen gas, reaction solution is poured in clean a receiving plate, ground after the cooling and obtain product, the censorship result of laboratory test is as follows:
Weighing products 522 grams reach 98.49% with positive stearyl alcohol calculated yield
The embodiment 5:(Fatty Alcohol(C12-C14 and C12-C18) excessive experimental example that feeds intake)
Another kind of representative products with antioxidant: 3,5-di-t-butyl, 4-hydroxy phenyl propionic acid isooctyl alcohol ester (trade name: be example oxidation inhibitor 1135), narrate wooden working of an invention.
Agitator is being housed, condenser, add 292 gram (1 mole) 3,5 methyl esters in the four-hole boiling flask of well heater, the isooctyl alcohol of 195 grams (1.5 moles), (Primary Catalysts is a lauric acid toxilic acid dibutyl tin to add the good composite catalyst of configured in advance 1.7 grams again, promotor is thio-2 acid two (18) alcohol ester, and compound proportion is 6:1), replace clean intrasystem air with pure nitrogen gas, give system decompression, heat up.Low insulation reaction of fs, temperature 130-140 ℃, pressure 10000-20000pa in 2 hours reaction times, extracts by-product carbinol out.140-150 ℃ of subordinate phase temperature of reaction, pressure 10000-8000pa in 2 hours reaction times, continues to extract out by-product carbinol.Phase III steams excessive isooctyl alcohol, temperature 150-160 ℃, pressure 2000-8000pa, the transposing condensator outlet, excessive isooctyl alcohol is distilled in the receiving flask, and (isooctyl alcohol that steams and Primary Catalysts can be used for later reaction) be not when having effluent, destroy vacuum with pure nitrogen gas, the reactant that obtains is water white liquid.The censorship result of laboratory test is as follows:
| Project name | Oxidation inhibitor 1135 chemical industry standards | This batch sample detected result |
| Outward appearance | Colourless to weak yellow liquid | Colourless liquid |
| Flash-point (℃) | ≥150 | 158 |
| Fusing point (℃) | ≤10 | 4 |
| Viscosity (25 ℃) | 115-125mpa.s | 121 |
| Effective constituent (%) | ≥98 | 99.0 |
Weighing products 387 grams collect rate 99.2% with 35 methyl esters
Claims (8)
1. the new synthetic method of a hindered phenol anti-oxidants, it is characterized in that: under the effect of composite catalyst, a kind of ester compound II and a kind of aliphatic alcohols compound III are carried out transesterification reaction, by heating, decompression, deviate from by-product carbinol, reaction steams excessive reaction raw materials and Primary Catalysts after finishing, and obtains purpose product compound I hindered phenol anti-oxidants; The general structure of described hindered phenol anti-oxidants Compound I is:
Wherein: R1, R2 are the straight or branched alkane of C1-C8, R1, and the carbochain number of R2 can be identical, also can be inequality, R3 is the alkyl of C4-C20 or contains oxyalkyl, m is 1,2, or 3; N is 1,2,3 or 4;
Described reaction raw materials ester compound II general structure is:
Wherein: R1, R2 are the straight or branched alkane of C1-C8, R1, and the carbochain number of R2 can be identical, also can be inequality, R3 is the alkyl of C1-C3, m is 1,2, or 3;
The general structure of described reaction raw materials aliphatic alcohols compound III is:
R-(OH)n
Wherein R is the straight or branched alkane of C1-C20, and n quantity is 1,2,3 or 4, and the position is primary, the second month in a season, uncle, the alcohols hydroxyl in season.
Described composite catalyst is made up of Primary Catalysts and promotor, and Primary Catalysts is the carboxylate of organotin, and promotor is a phosphorous acid ester, the monothioester compound.
The carboxylate of described organotin is: dibutyl tin laurate, Bis(lauroyloxy)dioctyltin, two cis-butenedioic acid mono ethyl maleate dioctyltins, the different monooctyl ester di-n-butyltin dilaurate of two maleic acid lists, two Kunshun butene two acid mono-character ester di-n-butyl tins, the different monooctyl ester dioctyltin of two maleic acid lists, the different monooctyl ester di-n-butyl tin of two maleic acid lists, lauric acid toxilic acid dibutyl tin, the toxilic acid dioctyltin;
Described phosphite ester compound is: three-(2, the 4-DI-tert-butylphenol compounds) phosphorous acid ester, diphosphorous acid tetramethylolmethane distearyl alcohol ester, two (2,4 di-tert-butyl-phenyls) pentaerythritol phosphite, described monothioester compound is: Tyox B, thio-2 acid two (14) alcohol ester, thio-2 acid two (18) alcohol ester;
Any composite use of any and promotor of described Primary Catalysts.
2. method according to claim 1 is characterized in that, the composite weight ratio of Primary Catalysts and promotor is 10:1-5, and the add-on of composite catalyst is the 0.05-3% of ester compound II weight.
3. method according to claim 1 is characterized in that, described aliphatic alcohols compound is positive stearyl alcohol, 1,6 hexylene glycol, isooctyl alcohol, glycerol, tetramethylolmethane.
4. method according to claim 1 is characterized in that the representative products of described ester compound II is 3,5-di-t-butyl, 4-hydroxy phenyl methyl propionate.
5. method according to claim 1 is characterized in that, described transesterification reaction is through three phases: the fs is low insulation reaction, temperature 130-165 ℃, and pressure (absolute pressure, down with) 20000-5000Pa; Subordinate phase is high insulation reaction, temperature 165-195 ℃, and pressure 5000-100Pa; Phase III steams excessive raw material and Primary Catalysts, and temperature 180-195 ℃, pressure 500-20Pa.
6. method according to claim 1 is characterized in that, after transesterification reaction finishes, need not to adopt traditional solvent crystallization process, the direct cooling granulation of reaction solution or grind and obtain the purpose product.
7. method according to claim 1 is characterized in that, the Primary Catalysts that reaction steams after finishing continues to recycle.
8. method according to claim 1 is characterized in that promotor needn't separate from product, and can not influence the quality product of antioxidant.
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| CN102020555A (en) * | 2010-10-21 | 2011-04-20 | 利安隆（天津）化工有限公司 | Method for preparing hindered phenol antioxygens by ester exchange process |
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| CN102492524A (en) * | 2011-11-15 | 2012-06-13 | 中国科学院新疆理化技术研究所 | Synthesis method for liquid phenolic ester type antioxidants |
| CN104788292A (en) * | 2015-03-19 | 2015-07-22 | 东北石油大学 | Synthesis method for hindered phenolic compound antioxidant 330 |
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| CN109593026A (en) * | 2018-12-13 | 2019-04-09 | 东莞理工学院 | A kind of phenol color inhibition composition and its application |
| CN109534990A (en) * | 2018-12-17 | 2019-03-29 | 辽宁鼎际得石化股份有限公司 | A kind of method that composite catalyst prepares Hinered phenols antioxidant |
| CN110938239A (en) * | 2019-12-12 | 2020-03-31 | 梁山新翔新材料有限公司 | Hindered phenol antioxidant and synthesis method thereof |
| CN111334300A (en) * | 2020-04-01 | 2020-06-26 | 辽宁石化职业技术学院 | Preparation method of double-effect antioxidant |
| WO2022156543A1 (en) * | 2021-01-21 | 2022-07-28 | 天津利安隆新材料股份有限公司 | Composite liquid antioxidant and preparation method therefor |
| WO2022213904A1 (en) * | 2021-04-08 | 2022-10-13 | 天津利安隆新材料股份有限公司 | Intramolecular complex hindered phenol compound, preparation method therefor and use thereof |
| CN115197065A (en) * | 2021-04-08 | 2022-10-18 | 天津利安隆新材料股份有限公司 | Intramolecular compound hindered phenol compound, preparation method and application thereof |
| CN115197065B (en) * | 2021-04-08 | 2024-01-30 | 天津利安隆新材料股份有限公司 | Intramolecular compound hindered phenol compound, preparation method and application thereof |
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