CN102992963B - Preparation method of hindered phenol antioxidant 330 - Google Patents
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Abstract
The invention relates to a preparation method of a hindered phenol antioxidant 330, which comprises the following steps of: mixing 1,3,5-trichloromethyl-2,4,6-trimethylbenzene and 2,6-ditertbutylphenol at a molar ratio of 1:(3-4); adding a silicon dioxide-loaded phosphotungstic acid catalyst, wherein the dosage of the silicon dioxide-loaded phosphotungstic acid catalyst is 0.5-10% of that of the 1,3,5-trichloromethyl-2,4,6-trimethylbenzene by mass; adding an organic solvent and performing heating reflux reaction for 5-48 hours; filtering to obtain a solid; and re-crystallizing to obtain a target product 1,3,5-trimethyl-2,4,6-tri(3,5-ditertbutyl-4-hydroxybenzyl)benzene. Compared with the existing synthesis method, the method disclosed by the invention has the advantages that the raw material is cheap and easily available, the operation is simple, the reaction conditions are mild, the product is easy to separate and purify, the one-way catalysis life of the catalyst is long, repeated use and regeneration can be realized and the like.
Description
Technical field
The invention belongs to the preparation method of macromolecular material functional agent, be specifically related to a kind of preparation method of Hinered phenols antioxidant 330.
Background technology
In the terminal use procedure of manufacture, storage and the course of processing and plastics, all can there is oxidizing reaction because of the effect of light, heat, oxygen etc. in macromolecular material, cause the variation of high polymer material chemical structure, thereby cause its mechanical property deteriorated, for example tensile strength reduces, check surface, goods yellowing variable color etc.Suppress or slow down the most frequently used of macromolecular material performance degradation and effective means are the suitable macromolecular material functional agents of interpolation.
Oxidation inhibitor is of paramount importance macromolecular material functional agent, and it suppresses the thermooxidative degradation of macromolecular material by the effective group in self structure.Hinered phenols antioxidant 330, chemistry by name 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene is the macromolecular material functional agent that performance is very excellent, its Application Areas comprises the elastomer materials such as the thermoplastic polyesters such as polyolefine, PET and PBT, polymeric amide, styrene resin and urethane, natural rubber, is specially adapted to the manufacture field of the goods such as polyolefin pipe, injection-molded item, electric wire of high temperature process.In addition, due to nontoxic, do not pollute, can keep the good colour of plastics, therefore can be used for the wrapping material with Food Contact.
Current antioxidant 330 mainly production company has: the U.S. refined treasured (Albemarle) company and Taiwan chemistry on National Day, in recent years, Hinered phenols antioxidant 330 product productions are the rapid growth impetus year by year in the international market, have very strong vitality, and development prospect is wide.Therefore, developing new efficient process for cleanly preparing receives much concern.
In existing preparation method, document (fine chemistry industry, 2008,25(8), 806-809) reported that catalysis of functional ionic liquid sym-trimethylbenzene and 2,6-di-t-butyl-4-hydroxyl benzyl methyl ether prepare the method for antioxidant 330, but raw material 2,6-di-t-butyl-4-hydroxyl benzyl methyl ether is difficult for preparing purifying.United States Patent (USP) (US3026264, US4340767) has been invented the method for preparing antioxidant 330 with sulphuric acid catalysis sym-trimethylbenzene and 2,6-di-t-butyl-4-hydroxy-benzyl alcohol, and purifying products is difficult, yield is low, spent acid amount is large, and 2,6-di-t-butyl-4-hydroxy-benzyl alcohol does not have market supply.In United States Patent (USP) (US4754007, US5292669), with sulfuric acid or methanesulfonic acid catalyzed sym-trimethylbenzene and 2,6-di-t-butyl-4-hydroxyl benzyl oxide, prepare antioxidant 330 respectively, also exist yield low, the problem such as the large or catalyzer of spent acid amount is expensive.In Japanese Patent (JP56-092235), introduced and take the method that sym-trimethylbenzene and 2,6 di t butyl phenol be main raw material one-step synthesis antioxidant 330, yield only has 42%, and unstable product quality can not meet the requirement of suitability for industrialized production.Document (Bohai University's journal (natural science edition), 2010,31(2), 117-120) reported presence of acidic ionic liquid catalyst 1,3,5-trisbromomethyl-2,4,6-Three methyl Benzene and 2,6 di t butyl phenol are prepared the method for antioxidant 330, but the raw material 1 of this method, 3,5-trisbromomethyl-2, the preparation cost of 4,6-Three methyl Benzene and catalyzer is high.Recently, Chinese patent (CN101717326) discloses a kind of solid superacid as catalyst 1,3,5-trihalogenmethyl-2, and 4,6-Three methyl Benzene and 2,6 di t butyl phenol are prepared the method for antioxidant 330.This method solid acid has overcome the shortcoming of liquid acid, have easily separated with liquid-phase reaction system, not etching apparatus, aftertreatment simply, seldom contaminate environment, selectivity high.But this method use 1,3,5-trihalogenmethyl-2,4,6-Three methyl Benzene there is no the source of suitable scale operation.The solid super acid catalyst that this method is used belongs to single component solid super-strong acid, its main active component SO
4 2-more easily loss in reaction, particularly easy inactivation under higher temperature conditions, although there is good initial catalytic activity, one way catalytic life is shorter, thereby has improved production cost.
And silicon dioxide carried heteropolyacid catalyst can provide larger specific surface area, increases acid site density and intensity, increase anticatalyst poisoning capability, improve the effects such as physical strength.Numerous bibliographical informations are introduced solid acid that heteropolyacid modification forms, and to have higher stability, catalytic activity, one way catalytic life permanent, and the main active component after Reusability is difficult for running off.But also do not report that at present silicon dioxide carried heteropoly acid catalysis prepares the method for antioxidant 330.
Summary of the invention
The object of this invention is to provide a kind of Hinered phenols antioxidant 1,3,5-trimethylammonium-2, the preparation method of 4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, concrete technical scheme is as follows:
The preparation method of hindered phenol antioxygen 330 of the present invention, by 1, 3, 5-trichloromethyl-2, 4, 6-Three methyl Benzene and 2, 6-DI-tert-butylphenol compounds is that mix 1:3～4 in molar ratio, add silicon dioxide carried phosphotungstic acid catalyst, by percentage to the quality, silicon dioxide carried phosphotungstic acid catalyst consumption is 1, 3, 5-trichloromethyl-2, 4, 0.5～10% of 6-Three methyl Benzene, add again organic solvent temperature rising reflux reaction 5～48 hours, after filtration, obtain solid, through recrystallization, obtain target product 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
Described organic solvent is methylene dichloride, chloroform or tetracol phenixin, and add-on is 1,3,5-trichloromethyl-2,4～15 times of 4,6-Three methyl Benzene weight.
After adding the reaction of organic solvent temperature rising reflux to filter, the liquid of filtration can reclaim silicon dioxide carried phosphotungstic acid catalyst.
Of the present invention 1,3,5-trichloromethyl-2, the product that 4,6-Three methyl Benzene can adopt commercially available product or additive method to prepare; Also can adopt preparation with the following method:
By sym-trimethylbenzene: concentration 30～37% hydrochloric acid: paraformaldehyde be take mol ratio and mixed as 1:6～12:4～8, add silicon dioxide carried phospho-wolframic acid as solid acid catalyst, the consumption of silicon dioxide carried phosphotungstic acid catalyst is 0.5～10% of sym-trimethylbenzene quality again; Then be heated to reflux, back flow reaction 12～36 hours, reaction solution cooling, after the solid drying of separating out, adds sherwood oil to reflux 1 hour, and solid is separated out in filtrate cooling, dries and obtains 1,3,5-trichloromethyl-2,4,6-Three methyl Benzene.
Silicon dioxide carried phosphotungstic acid catalyst preparation method of the present invention is: in water, 1200～6000 order superfine silicon dioxides and phospho-wolframic acid, be that 0.5～5:1 mixes in mass ratio, under room temperature, flood 12～36 hours, then filter, filter cake is dried 2～4 hours at 100 ℃, calcination activation 2～5 hours at 200 ℃, obtains silicon dioxide carried phosphotungstic acid catalyst again.
The present invention compares with existing synthetic method, has raw material cheap and easy to get, simple to operate, reaction conditions is gentle, product is easy to separating-purifying, and catalyzer one way long catalytic life also can be repeatedly used and the advantage such as regeneration.
Embodiment
Following examples will contribute to understand the present invention, but be not limited to content of the present invention:
Embodiment 1
Silicon dioxide carried phosphotungstic acid catalyst preparation process is as follows: in 200L water, add successively 60kg superfine silicon dioxide (2500 order), 40kg phospho-wolframic acid (No. CAS: 12501-23-4), under room temperature, flood 24 hours, then filter, filter cake is dried 3 hours at 100 ℃, more calcination activation obtains silicon dioxide carried phosphotungstic acid catalyst for 3 hours at 200 ℃.
Embodiment 2
Silicon dioxide carried phosphotungstic acid catalyst preparation process is as follows: in 200L water, add successively 20kg superfine silicon dioxide (6000 order), 40kg phospho-wolframic acid (No. CAS: 12501-23-4), under room temperature, flood 12 hours, then filter, filter cake is dried 2 hours at 100 ℃, more calcination activation obtains silicon dioxide carried phosphotungstic acid catalyst for 2 hours at 200 ℃.
Embodiment 3
Silicon dioxide carried phosphotungstic acid catalyst preparation process is as follows: in 200L water, add successively 100kg superfine silicon dioxide (1200 order), 20kg phospho-wolframic acid (No. CAS: 12501-23-4), under room temperature, flood 36 hours, then filter, filter cake is dried 4 hours at 100 ℃, more calcination activation obtains silicon dioxide carried phosphotungstic acid catalyst for 5 hours at 200 ℃.
Embodiment 4
The concentrated hydrochloric acid that is 36% by 10mol sym-trimethylbenzene, 75mol mass percent concentration and 60mol paraformaldehyde mix, add 60g according to the silicon dioxide carried phosphotungstic acid catalyst of embodiment 1 preparation, then heated and stirred back flow reaction is 12 hours, reaction solution cooling, material is separated out, after the solid drying that separation obtains, add sherwood oil to reflux 1 hour, suction filtration reclaims silicon dioxide carried phosphotungstic acid catalyst, the cooling solid of separating out of filtrate, oven dry obtains 1,3,5-trichloromethyl-2,4,6-Three methyl Benzene [169～172 ℃ of fusing points
1h NMR(400MHz, CDCl
3): 4.70(s, 6H), 2.51(s, 9H)].
By resulting 9.3mol1, 3, 5-trichloromethyl-2, 4, 6-Three methyl Benzene and 32mol2, 6-DI-tert-butylphenol compounds is mixed, add 60g according to the silicon dioxide carried phosphotungstic acid catalyst of embodiment 1 preparation, then add 20kg methylene chloride reflux reaction 36 hours, cool to room temperature, the phosphotungstic acid catalyst that filtered and recycled is silicon dioxide carried, filtrate concentration and recovery solvent obtains solid, with sherwood oil recrystallization, obtain 6.40kg white crystal, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, total recovery 83%, 242～244 ℃ of fusing points,
1h NMR(400MHz, CDCl
3): 6.93(s, 6H), 5.04(s, 3H) and 4.03(s, 6H), 2.29(s, 9H) and, 1.35(s, 54H).
Embodiment 5
10mol sym-trimethylbenzene, 72mol37% concentrated hydrochloric acid and 68mol paraformaldehyde are mixed, add 20g according to the silicon dioxide carried phosphotungstic acid catalyst of embodiment 1 preparation, then heated and stirred back flow reaction is 36 hours, reaction solution cooling, material is separated out, after the solid drying that separation obtains, add sherwood oil to reflux 1 hour, filtering recovering catalyst, the cooling solid of separating out of filtrate, oven dry obtains 1,3,5-trichloromethyl-2,4,6-Three methyl Benzene, 170～172 ℃ of fusing points.
By resulting 9.2mol1,3,5-trichloromethyl-2,4,6-Three methyl Benzene and 34mol2,6-DI-tert-butylphenol compounds is mixed, and adds 50g according to the silicon dioxide carried phosphotungstic acid catalyst of embodiment 1 preparation, then adds 36kg tetracol phenixin back flow reaction 36 hours, cool to room temperature, filtering recovering catalyst, filtrate concentration and recovery solvent obtains solid, with sherwood oil recrystallization, obtains 6.5kg white crystal, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, total recovery 85%, 243～244 ℃ of fusing points.
Embodiment 6
The concentrated hydrochloric acid of 10mol sym-trimethylbenzene, 80mol36% and 80mol paraformaldehyde are mixed, then add 12g according to the silicon dioxide carried phosphotungstic acid catalyst of embodiment 1 preparation, then heated and stirred back flow reaction is 30 hours, reaction solution cooling, material is separated out, after the solid drying that separation obtains, add sherwood oil to reflux 1 hour, filtering recovering catalyst, the cooling solid of separating out of filtrate, oven dry obtains 1,3,5-trichloromethyl-2,4,6-Three methyl Benzene, 171～172 ℃ of fusing points.
By resulting 9.3mol1,3,5-trichloromethyl-2,4,6-Three methyl Benzene and 35mol2,6-DI-tert-butylphenol compounds is mixed, and adds 20g according to the silicon dioxide carried phosphotungstic acid catalyst of embodiment 1 preparation, then adds 9.8kg chloroform back flow reaction 20 hours, cool to room temperature, suction filtration reclaims catalyzer, and filtrate concentration and recovery solvent obtains solid, with sherwood oil recrystallization, obtains 6.59kg white crystal, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, total recovery 86%, 242～244 ℃ of fusing points.
Embodiment 7
The concentrated hydrochloric acid of 10mol sym-trimethylbenzene, 120mol30% and 40mol paraformaldehyde are mixed, then add 6g according to the silicon dioxide carried phosphotungstic acid catalyst of embodiment 2 preparations, then heated and stirred back flow reaction is 36 hours, reaction solution cooling, material is separated out, after the solid drying that separation obtains, add sherwood oil to reflux 1 hour, filtering recovering catalyst, the cooling solid of separating out of filtrate, oven dry obtains 1,3,5-trichloromethyl-2,4,6-Three methyl Benzene, 171～172 ℃ of fusing points.
By resulting 9.3mol1,3,5-trichloromethyl-2,4,6-Three methyl Benzene and 27.9mol2,6-DI-tert-butylphenol compounds is mixed, and adds 6g according to the silicon dioxide carried phosphotungstic acid catalyst of embodiment 1 preparation, then adds 15kg chloroform back flow reaction 36 hours, cool to room temperature, suction filtration reclaims catalyzer, and filtrate concentration and recovery solvent obtains solid, with sherwood oil recrystallization, obtains 6.36kg white crystal, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, total recovery 82%, 242～244 ℃ of fusing points.
Embodiment 8
The concentrated hydrochloric acid of 10mol sym-trimethylbenzene, 60mol36% and 60mol paraformaldehyde are mixed, then add 120g according to the silicon dioxide carried phosphotungstic acid catalyst of embodiment 1 preparation, then heated and stirred back flow reaction is 12 hours, reaction solution cooling, material is separated out, after the solid drying that separation obtains, add sherwood oil to reflux 1 hour, filtering recovering catalyst, the cooling solid of separating out of filtrate, oven dry obtains 1,3,5-trichloromethyl-2,4,6-Three methyl Benzene, 171～172 ℃ of fusing points.
By resulting 9.4mol1,3,5-trichloromethyl-2,4,6-Three methyl Benzene and 35mol2,6-DI-tert-butylphenol compounds is mixed, and adds 123g according to the silicon dioxide carried phosphotungstic acid catalyst of embodiment 1 preparation, then adds 20kg chloroform back flow reaction 5 hours, cool to room temperature, suction filtration reclaims catalyzer, and filtrate concentration and recovery solvent obtains solid, with sherwood oil recrystallization, obtains 6.74kg white crystal, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, total recovery 87%, 242～244 ℃ of fusing points.
Embodiment 9
The concentrated hydrochloric acid of 10mol sym-trimethylbenzene, 80mol36% and 80mol paraformaldehyde are mixed, then add 120g according to the silicon dioxide carried phosphotungstic acid catalyst of embodiment 3 preparations, then heated and stirred back flow reaction is 36 hours, reaction solution cooling, material is separated out, after the solid drying that separation obtains, add sherwood oil to reflux 1 hour, filtering recovering catalyst, the cooling solid of separating out of filtrate, oven dry obtains 1,3,5-trichloromethyl-2,4,6-Three methyl Benzene, 171～172 ℃ of fusing points.
By resulting 9.2mol1,3,5-trichloromethyl-2,4,6-Three methyl Benzene and 35mol2,6-DI-tert-butylphenol compounds is mixed, and adds 235g according to the silicon dioxide carried phosphotungstic acid catalyst of embodiment 1 preparation, then adds 30kg methylene chloride reflux reaction 48 hours, cool to room temperature, suction filtration reclaims catalyzer, and filtrate concentration and recovery solvent obtains solid, with sherwood oil recrystallization, obtains 6.51kg white crystal, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, total recovery 85%, 242～244 ℃ of fusing points.
Embodiment 10
By 9.4mol1,3,5-trichloromethyl-2,4,6-Three methyl Benzene and 35mol2,6-DI-tert-butylphenol compounds is mixed, add 60g according to the silicon dioxide carried phosphotungstic acid catalyst of embodiment 1 preparation, then add 15kg chloroform back flow reaction 20 hours, cool to room temperature, suction filtration reclaims catalyzer, filtrate concentration and recovery solvent obtains solid, with sherwood oil recrystallization, obtains 6.75kg white crystal, and 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-t-butyl-4 hydroxybenzyl) benzene, 242～244 ℃ of fusing points.
Claims (4)
1. the preparation method of a Hinered phenols antioxidant 330, it is characterized in that 1, 3, 5-trichloromethyl-2, 4, 6-Three methyl Benzene and 2, 6-DI-tert-butylphenol compounds is that mix 1:3～4 in molar ratio, add silicon dioxide carried phosphotungstic acid catalyst, by percentage to the quality, silicon dioxide carried phosphotungstic acid catalyst consumption is 1, 3, 5-trichloromethyl-2, 4, 0.5～10% of 6-Three methyl Benzene, add again organic solvent temperature rising reflux reaction 5～48 hours, after filtration, obtain solid, through recrystallization, obtain target product 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, wherein, silicon dioxide carried phosphotungstic acid catalyst preparation method is 1200～6000 order superfine silicon dioxides and phospho-wolframic acid, to be that 0.5～5:1 mixes in mass ratio in water, under room temperature, flood 12～36 hours, then filter, filter cake is dried 2～4 hours at 100 ℃, calcination activation 2～5 hours at 200 ℃, obtains silicon dioxide carried phosphotungstic acid catalyst again.
2. the method for claim 1, is characterized in that described organic solvent is methylene dichloride, chloroform or tetracol phenixin, and add-on is 1,3,5-trichloromethyl-2,4～15 times of 4,6-Three methyl Benzene weight.
3. the method for claim 1, is characterized in that the silicon dioxide carried phosphotungstic acid catalyst of liquids recovery after filtering.
4. the method for claim 1, it is characterized in that 1,3,5-trichloromethyl-2,4, the preparation method of 6-Three methyl Benzene is: by sym-trimethylbenzene: concentration is 30～37% hydrochloric acid: paraformaldehyde be take mol ratio and mixed as 1:6～12:4～8, then adds silicon dioxide carried phospho-wolframic acid as solid acid catalyst, and the consumption of silicon dioxide carried phosphotungstic acid catalyst is 0.5～10% of sym-trimethylbenzene quality; Then be heated to reflux, back flow reaction 12～36 hours, reaction solution cooling, after the solid drying of separating out, adds sherwood oil to reflux 1 hour, and solid is separated out in filtrate cooling, dries and obtains 1,3,5-trichloromethyl-2,4,6-Three methyl Benzene.
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| CN105503513B (en) * | 2015-12-08 | 2018-04-24 | 天津利安隆新材料股份有限公司 | The method of silicon dioxide carried catalysis of phosphotungstic acid synthesis 4,4 '-dichloromethyl biphenyl |
| CN105401250B (en) * | 2015-12-30 | 2018-01-30 | 天津利安隆新材料股份有限公司 | There is antioxidant and the response type stabilizer of anti-yellowing agent double action for spandex |
| CN112250550B (en) * | 2020-11-09 | 2023-02-07 | 兰州精细化工有限责任公司 | Preparation method of antioxidant 330 |
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| CN101717326A (en) * | 2009-12-04 | 2010-06-02 | 渤海大学 | Method for synthesizing antioxidant 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene |
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| US5068481A (en) * | 1989-11-16 | 1991-11-26 | Kureha Kagaku Kogyo K.K. | Method for producing diarylmethanes |
| CN101717326A (en) * | 2009-12-04 | 2010-06-02 | 渤海大学 | Method for synthesizing antioxidant 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene |
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