CN102351657A - Method for preparing 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene - Google Patents

Method for preparing 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene Download PDF

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CN102351657A
CN102351657A CN2011102390484A CN201110239048A CN102351657A CN 102351657 A CN102351657 A CN 102351657A CN 2011102390484 A CN2011102390484 A CN 2011102390484A CN 201110239048 A CN201110239048 A CN 201110239048A CN 102351657 A CN102351657 A CN 102351657A
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butyl
tert
benzene
trimethylammonium
methyl phenol
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CN102351657B (en
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赵文军
吴成
王�华
赵丽君
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention relates to a method for preparing 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene. The method comprises the following steps of: catalyzing the reaction of mesitylene and 2,6-di-tert-butyl-4-methoxyl methylphenol in a halogenated hydrocarbon solution by using a catalyst prepared from an amino organic sulfonic acid ylid and sulfuric acid; evaporating methanol serving as a reactant by using an azeotropic evaporation technology; promoting high-yield synthesis of the 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene (antioxidant 330); adding petroleum ether after synthesizing; and recovering the catalyst through phase separation for direct use in a next reaction. Due to the adoption of the method, the recovery of an ion liquid catalyst is realized, the cost is reduced, and the yield is approximate to that of the conventional low-temperature sulfuric acid catalysis method for industrial application.

Description

1,3,5-trimethylammonium-2,4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene
Technical field
The present invention relates to a kind of 1,3,5-trimethylammonium-2,4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (antioxidant 330).
Background technology
Polysubstituted hindered phenol antioxygen is the hindered phenol antioxygen of the high molecular weight of a kind of tasteless, low volatility, low stripping, low migration.Tool representative be antioxidant 330 [1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene] and 1,3,5-trimethylammonium-2-(3-methyl-5-tertiary butyl-4-hydroxy benzyl)-4,6-two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.It has superior dielectric properties; Be applicable to elastomer materials such as thermoplastic polyesters such as polyolefine films for electrical purposes, PET and PBT, polymeric amide, styrene resin and urethane, tree elastomer; Have and characteristics such as good, the anti-extraction of consistency of resin, low volatilization, antioxygen efficient height and electrical insulating property are good; Being specially adapted to the processing products field such as polyolefine (like PP, PE etc.) tubing, injection-molded item, electric wire of high temperature process, is antioxidant 1010,1076 ideal substitute.Auxiliary antioxidants such as itself and phosphorous acid ester, monothioester, benzofuranone and carbon radicals trapping agent have good synergy.
The method of the synthetic antioxidant 330 of report has (1) at present: with 2,6-di-t-butyl-4-methylolphenol is the raw material single stage method; (2): with the 2,6 di t butyl phenol is the raw material single stage method; (3) with 3,5-di-t-butyl-4-hydroxyl benzyl ethyl ester raw material single stage method; (4): with 2,6-di-t-butyl-4-methoxyl methyl phenol single stage method.
US:4340767, US:3925488, US:3026264 are with 2, and 6-di-t-butyl-4-methylolphenol is the synthetic polysubstituted benzene oxidation inhibitor of raw material, and this method exists productive rate low, and product needs shortcomings such as secondary recrystallization.
JP: clear 56-92235 is the synthetic polysubstituted benzene oxidation inhibitor of raw material with the 2,6 di t butyl phenol.Though this method can be saved the step of synthetic benzylalcohol, it exists restive, and yield is low, shortcomings such as quality instability.
SU:2036893 is with 3, and 5-di-t-butyl-4-hydroxyl benzyl ethyl ester raw material synthesizes polysubstituted benzene oxidation inhibitor.This fragrant method exists in the aftertreatment and contains more acid, phenol and acetic acid owing in the extraction liquid, has increased aftertreatment and the difficulty that reclaims glacial acetic acid, causes cost high.
US:4259534, US:4754077, JP: clear 56-92237, US:4870214, US:4898994 are with 2, and 6-di-t-butyl-4-methoxyl methyl phenol is the synthetic polysubstituted benzene oxidation inhibitor of raw material.Though this method productive rate is high, product does not need secondary crystal, exist in the reaction must maintain the temperature at about 0 ℃, and sour dropping or acid and 2 of needing, 6-di-t-butyl-4-methoxyl methyl phenol drips shortcomings such as long reaction time simultaneously.
US:4992597, US:4994628, US:5292969 are with 2, and 6-di-t-butyl-4-methoxyl methyl phenol is the synthetic polysubstituted benzene oxidation inhibitor of raw material.This method is little with the acid amount, and productive rate is high, needs to keep low pressure in the reaction but exist in, and need a large amount of molecular sieves remove to absorb by-product carbinol, and still need drip 2,6-di-t-butyl-4-methoxyl methyl phenol, long reaction time, acid such as can't reclaim at shortcoming.
Summary of the invention
The object of the invention is; Provide a kind of 1; 3,5-trimethylammonium-2,4; 6-three (3; The 5-di-tert-butyl-4-hydroxyl benzyl) preparation method of benzene, this method utilize the catalyzer of amido organic sulfonic acid inner salt and sulfuric acid preparation, catalysis sym-trimethylbenzene and 2 in halohydrocarbon solution; 6-di-t-butyl-4-methoxyl methyl phenol reactant; Steam reactant methanol through the azeotropic vaporization technology, promote 1,3; 5-trimethylammonium-2; 4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (antioxidant 330) high yield synthetic; The synthetic back that finishes adds sherwood oil, reclaims catalyzer through being separated and also can directly be used for reacting next time.The present invention has not only realized the recovery of ionic-liquid catalyst, has reduced cost, and the low temperature sulfuric acid catalysis method of productive rate and present industrial application is close.
Of the present invention a kind of 1,3,5-trimethylammonium-2,4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, shown in chemical formula (1):
Concrete operations follow these steps to carry out:
A, in reactor, add catalyzer and sym-trimethylbenzene that mixture that solvent is halohydrocarbon or halogenated alkane and sherwood oil, amido organic sulfonic acid inner salt and sulfuric acid are prepared; Under agitation drip 2 earlier; The 40%-60% of 6-di-t-butyl-4-methoxyl methyl phenol and halohydrocarbon blended solution total amount, the dropping time is 0.1-0.3h;
B, add 2 of residual content on the solvent limit of the following evaporation reaction liquid of 0.02-0.1MPa pressure; 6-di-t-butyl-4-methoxyl methyl phenol and halohydrocarbon blended solution; The evaporation reaction temperature is 30-80 ℃, and the joining day is 0.2-2h, and the evaporation time of halohydrocarbon is 0.3-3h; Reaction generates 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Add sherwood oil after c, reaction finish, tell lower floor's catalyzer and be used for reacting next time, upper solution is through neutralization, and washing evaporates the residue halohydrocarbon, and crystallization separates, and can obtain 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
Amido organic sulfonic acid inner salt among the step a is by the compound of molecular formula shown in (2), cooperates with sulfuric acid to form ionic liquid:
Figure BSA00000559606500032
N=2,3 or 4 wherein; R 1, R 2, R 3The alkyl of=C1-C15, described alkyl are identical or different alkyl.
Amido organic sulfonic acid inner salt and sulfuric acid mol ratio are 1 in the said method: 1-4.
Catalyzer among the step a, sym-trimethylbenzene, 2; 6-di-t-butyl-4-methoxyl methyl phenol mol ratio is: amido organic sulfonic acid inner salt: 2; 6-di-t-butyl-4-methoxyl methyl phenol=1: 1-30, sym-trimethylbenzene: 2,6-di-t-butyl-4-methoxyl methyl phenol=1: 3-6;
Halohydrocarbon among the step a is methylene dichloride, trichloromethane, 1,1-ethylene dichloride, 1, and 2-ethylene dichloride or 1, sherwood oil are the alkane of C5-C9.
Step c sherwood oil is the alkane of C5-C9.
Of the present invention a kind of 1; 3; 5-trimethylammonium-2,4,6-three (3; The 5-di-tert-butyl-4-hydroxyl benzyl) preparation method of benzene; The purpose of this method evaporation halohydrocarbon is will react the methyl alcohol that generates through azeotropic vaporization to evaporate, and promotes reaction further to carry out the speed of halohydrocarbon velocity of evaporation >=adding halohydrocarbon solution; Vaporization temperature is that temperature of reaction is 30-80 ℃, pressure 0.02-0.1MPa; In method of the present invention; With 2,6-di-t-butyl-4-methoxyl methyl phenol is with 2-methyl-6-tert butyl-4-methoxymethyl phenol alternative energy synthetic 1,3; 5-trimethylammonium-2; 4,6-three (3-methyl-5-tertiary butyl-4-hydroxy benzyl) benzene, part alternative energy synthetic 1; 3; 5-trimethylammonium-2-(3-methyl-5-tertiary butyl-4-hydroxy benzyl)-4,6-two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
Embodiment
Embodiment 1
In the 500mL there-necked flask, add 5.0g[PyN (CH 2) 3SO 3H] [HSO 4The vitriol oil=1: 2), 85mL methylene dichloride and 3.6g sym-trimethylbenzene] ionic liquid (N-(3-sulfonic group) propyl group-pyridinium salt wherein:; Stir under the room temperature; Drip intermediate solution (10g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 30mL methylene dichloride) in 10 minutes;
Under normal pressure, reflux, 40 ℃ of reflux temperatures; Evaporation dichloromethane solvent limit, limit stream adds intermediate solution (the 10g intermediate 2 of residual content; 6-di-t-butyl-4-methoxyl methyl phenol and 30mL methylene dichloride), evaporation time is 0.3h, drips complete in 60 minutes; Reaction generates 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Reaction finishes, and adds the 60mL heptane, leaves standstill 20 minutes, tells lower floor's catalyzer and is used for reacting next time; Upper solution adds the 20mL weak ammonia, divides water-yielding stratum, uses 3 * 20mL washing again, is about 7 until pH; Organic layer is transferred in the single port bottle, steams methylene dichloride, crystallization is filtered; The filter cake methanol wash 50 ℃ of vacuum-dryings, can obtain 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene white crystal, productive rate is 84.5%.
Embodiment 2 to embodiment 6 is with embodiment 1 operation steps, and used ionic-liquid catalyst is that experiment is reclaimed among each embodiment, untreated direct application; Resultant 1,3,5-trimethylammonium-2; 4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene white crystal, productive rate is followed successively by: 86.1%; 83.2%; 82.4%, 81.9%, 80.7%.
Embodiment 7
In the 500mL there-necked flask, add 5.5g[MimN (CH 2) 3SO 3H] [HSO 4The vitriol oil=1: 1), 75mL chloroform and 3.6g sym-trimethylbenzene] ionic liquid (N-(3-sulfonic group) propyl group-imidazole salts wherein:, stir under the room temperature, drip intermediate solution (10g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 30mL chloroform) in 5 minutes;
Under 0.06MPa pressure; In 45 ℃ of following reflux of temperature, evaporating solvent chloroform limit, limit adds the intermediate solution (20g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 70mL chloroform) of residual content; Evaporation time is 0.5h; Dripped in 60 minutes and finish, reaction generates 1,3; 5-trimethylammonium-2; 4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Reaction finishes, and adds the 60mL heptane, leaves standstill 20 minutes, tells lower floor's catalyzer and is used for reacting next time; Upper solution adds the 20mL weak ammonia, divides water-yielding stratum, uses 3 * 20mL washing again, is 7 until pH; Organic layer is transferred in the single port bottle, steams chloroform, crystallization is filtered; The filter cake methanol wash in 50 ℃ of vacuum-dryings of temperature, can obtain 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene white crystal, productive rate is 89.8%.
Embodiment 8
In the 500mL there-necked flask, add 4.5g[(CH 3) 3N (CH 2) 3SO 3H] [HSO 4The vitriol oil=1: 3), 75mL 1] ionic liquid (N-(3-sulfonic group) propyl group-front three amine salt wherein:; 1-ethylene dichloride, 3.6g sym-trimethylbenzene stir under the room temperature, drip intermediate solution (10g intermediate 2 in 10 minutes; 6-di-t-butyl-4-methoxyl methyl phenol and 30mL 1, the 1-ethylene dichloride);
Under 0.07MPa pressure, in 6 ℃ of following reflux of temperature, limit evaporation 1; 1-ethylene dichloride limit stream adds the intermediate solution (15g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 50mL1,1-ethylene dichloride) of residual content; Evaporation time is 1h; Dripped in 60 minutes and finish, reaction generates 1,3; 5-trimethylammonium-2; 4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Reaction finishes, and adds the 60mL octane, leaves standstill 20 minutes, tells lower floor's catalyzer and is used for reacting next time; Upper solution adds the 20mL weak ammonia, divides water-yielding stratum, uses 3 * 20mL washing again, is 7 until pH; Organic layer is transferred in the single port bottle, steams 1,1-ethylene dichloride, crystallization; Filter, the filter cake methanol wash in 50 ℃ of vacuum-dryings of temperature, can obtain 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene white crystal, productive rate is 82.5%.
Embodiment 9
In the 500mL there-necked flask, add 5.0g[PyN (CH 2) 3SO 3H] [HSO 4The vitriol oil=1: 4), 65mL1] ionic liquid (N-(3-sulfonic group) propyl group-pyridinium salt wherein:; 2-ethylene dichloride, 3.6g sym-trimethylbenzene stir under the room temperature, drip intermediate solution (10g intermediate 2 in 10 minutes; 6-di-t-butyl-4-methoxyl methyl phenol and 30mL1, the 2-ethylene dichloride);
Under 0.09MPa pressure, 80 ℃ of following reflux of temperature, limit evaporation 1; 2-ethylene dichloride limit stream adds the intermediate solution (20g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 70mL1,2-ethylene dichloride) of residual content; Evaporation time is 1.5h; Dripped in 60 minutes and finish, reaction generates 1,3; 5-trimethylammonium-2; 4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Reaction finishes, and adds the 60mL decane, leaves standstill 20 minutes, tells lower floor's catalyzer and is used for reacting next time; Upper solution adds the 20mL weak ammonia, divides water-yielding stratum, uses 3 * 20mL washing again, is 7 until pH; Organic layer is transferred in the single port bottle, steams 1,2-ethylene dichloride, crystallization; Filter, the filter cake methanol wash in 50 ℃ of vacuum-dryings of temperature, can obtain 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene white crystal, productive rate is 84.7%.
Embodiment 10
In the 500mL there-necked flask, add 4.5g[MimN (CH 2) 3SO 3H] [HSO 4] ionic liquid (N-(3-sulfonic group) propyl group-imidazole salts wherein: the vitriol oil)=1: 1), 75mL1; 1-ethylene dichloride, 3.6g sym-trimethylbenzene stir under the room temperature, drip intermediate solution (10g intermediate 2 in 10 minutes; 6-di-t-butyl-4-methoxyl methyl phenol and 30mL1, the 1-ethylene dichloride);
Under 0.1MPa pressure, in 58 ℃ of following reflux of temperature, limit evaporation 1; 1-ethylene dichloride limit stream adds the intermediate solution (20g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 70mL1,1-ethylene dichloride) of residual content; Evaporation time is 2h; Dripped in 45 minutes and finish, reaction generates 1,3; 5-trimethylammonium-2; 4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Reaction finishes, and adds the 60mL heptane, leaves standstill 20 minutes, tells lower floor's catalyzer and is used for reacting next time; Upper solution adds the 20mL weak ammonia, divides water-yielding stratum, uses 3 * 20mL washing again, is 7 until pH; Organic layer is transferred in the single port bottle, steams 1,1-ethylene dichloride, crystallization; Filter, the filter cake methanol wash in 50 ℃ of vacuum-dryings of temperature, can obtain 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene white crystal, productive rate is 80.8%.
Embodiment 11
In the 500mL there-necked flask, add 5.0g[PyN (CH 2) 3SO 3H] [HSO 4] ionic liquid (N-(3-sulfonic group) propyl group-pyridinium salt wherein: the vitriol oil)=1: 2,80mL1,1,1-trichloroethane, 3.6g sym-trimethylbenzene; Stir under the room temperature, drip intermediate solution (10g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 30mL1 in 10 minutes; 1, the 1-trichloroethane);
Under 0.02MPa pressure, in 30 ℃ of following reflux of temperature, limit evaporation 1; 1,1-trichloroethane limit stream adds intermediate solution (20g intermediate 2, the 6-di-t-butyl-4-methoxyl methyl phenol and the 80mL1 of residual content; 1, the 1-trichloroethane), evaporation time is 2.5h; Dripped in 55 minutes and finish, reaction generates 1,3; 5-trimethylammonium-2; 4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Reaction finishes, and adds the 60mL heptane, leaves standstill 20 minutes, tells lower floor's catalyzer and is used for reacting next time; Upper solution adds the 20mL weak ammonia, divides water-yielding stratum, uses 3 * 20mL washing again, is 7 until pH; Organic layer is transferred in the single port bottle, steams 1; Crystallization is filtered, and the filter cake methanol wash is in 50 ℃ of vacuum-dryings of temperature; Can obtain 1,3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene white crystal, productive rate is 82.1%.
Embodiment 12
In the 500mL there-necked flask, add 3.5g[PyN (CH 2) 3SO 3H] [HSO 4The vitriol oil=1: 1.5), 75mL methylene dichloride, 3.6g sym-trimethylbenzene] ionic liquid (N-(3-sulfonic group) propyl group-pyridinium salt wherein:; Stir under the room temperature; Drip intermediate solution (5g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 20mL methylene dichloride) in 5 minutes;
Under 0.07MPa pressure; In 30 ℃ of following reflux of temperature, evaporation methylene dichloride limit, limit stream adds the intermediate solution (25g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 80mL methylene dichloride) of residual content; Evaporation time is 3h; Dripped in 70 minutes and finish, reaction generates 1,3; 5-trimethylammonium-2; 4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Reaction finishes, and adds the 60mL heptane, leaves standstill 20 minutes, tells lower floor's catalyzer and is used for reacting next time; Upper solution adds the 20mL weak ammonia, divides water-yielding stratum, uses 3 * 20mL washing again, is 7 until pH; Organic layer is transferred in the single port bottle, steams methylene dichloride, crystallization is filtered; The filter cake methanol wash in 50 ℃ of vacuum-dryings of temperature, can obtain 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene white crystal, productive rate is 83.4%.
Embodiment 13
In the 500mL there-necked flask, add 5.0g[PyN (CH 2) 3SO 3H] [HSO 4The vitriol oil=1: 1), 70mL methylene dichloride, 3.6g sym-trimethylbenzene] ionic liquid (N-(3-sulfonic group) propyl group-pyridinium salt wherein:; Stir under the room temperature; Drip intermediate solution (10g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 30mL methylene dichloride) in 5 minutes;
Under 0.1MPa pressure; In 41 ℃ of following reflux of temperature, evaporation methylene dichloride limit, limit stream adds the intermediate solution (25g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 70mL methylene dichloride) of residual content; Evaporation time is 1.5h; Dripped in 65 minutes and finish, reaction generates 1,3; 5-trimethylammonium-2; 4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Reaction finishes, and adds the 60mL heptane, leaves standstill 20 minutes, tells lower floor's catalyzer and is used for reacting next time; Upper solution adds the 20mL weak ammonia, divides water-yielding stratum, uses 3 * 20mL washing again, is about 7 until pH; Organic layer is transferred in the single port bottle, steams methylene dichloride, crystallization is filtered; The filter cake methanol wash in 50 ℃ of vacuum-dryings of temperature, can obtain 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene white crystal, productive rate is 82.2%.
Embodiment 14
In the 500mL there-necked flask, add 5.0g[MimN (CH 2) 3SO 3H] [HSO 4The vitriol oil=1: 1), 75mL methylene dichloride, 3.6g sym-trimethylbenzene] ionic liquid (N-(3-sulfonic group) propyl group-imidazole salts wherein:; Stir under the room temperature; Drip intermediate solution (10g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 30mL methylene dichloride) in 10 minutes;
Under 0.09MPa pressure; In 38 ℃ of following reflux of temperature, evaporation methylene dichloride limit, limit stream adds the intermediate solution (20g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 70mL methylene dichloride) of residual content; Evaporation time is 0.3h; Dripped in 60 minutes and finish, reaction generates 1,3; 5-trimethylammonium-2; 4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Reaction finishes, and adds the 60mL heptane, leaves standstill 20 minutes, tells lower floor's catalyzer and is used for reacting next time; Upper solution adds the 20mL weak ammonia, divides water-yielding stratum, uses 3 * 20mL washing again, is 7 until pH; Organic layer is transferred in the single port bottle, steams methylene dichloride, crystallization is filtered; The filter cake methanol wash in 50 ℃ of vacuum-dryings of temperature, can obtain 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene white crystal, productive rate is 82.9%.
Embodiment 15
In the 500mL there-necked flask, add 4.0g[PyN (CH 2) 3SO 3H] [HSO 4The vitriol oil=1: 3), 75mL methylene dichloride, 3.6g sym-trimethylbenzene] ionic liquid (N-(3-sulfonic group) propyl group-pyridinium salt wherein:; Stir under the room temperature; Drip intermediate solution (7.5g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 30mL methylene dichloride) in 10 minutes;
Under 0.1MPa pressure; In 41 ℃ of following reflux of temperature, evaporation methylene dichloride limit, limit stream adds the intermediate solution (15g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 70mL methylene dichloride) of residual content; Evaporation time is 1h; Dripped in 60 minutes and finish, reaction generates 1,3; 5-trimethylammonium-2; 4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Reaction finishes, and adds the 60mL heptane, leaves standstill 20 minutes, tells lower floor's catalyzer and is used for reacting next time; Upper solution adds the 20mL weak ammonia, divides water-yielding stratum, uses 3 * 20mL washing again, is about 7 until pH; Organic layer is transferred in the single port bottle, steams methylene dichloride, crystallization is filtered; The filter cake methanol wash in 50 ℃ of vacuum-dryings of temperature, can obtain 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene white crystal, productive rate is 84.9%.
Embodiment 16
In the 500mL there-necked flask, add 5.0g[(CH 3) 3N (CH 2) 3SO 3H] [HSO 4The vitriol oil=1: 1), 75mL methylene dichloride, 3.6g sym-trimethylbenzene] ionic liquid (N-(3-sulfonic group) propyl group-front three amine salt wherein:; Stir under the room temperature; Drip intermediate solution (10g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 30mL methylene dichloride) in 10 minutes;
Under 0.09MPa pressure; In 39 ℃ of following reflux of temperature, evaporation methylene dichloride limit, limit stream adds the intermediate solution (15g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 70mL methylene dichloride) of residual content; Evaporation time is 0.5h; Dripped in 60 minutes and finish, reaction generates 1,3; 5-trimethylammonium-2; 4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Reaction finishes, and adds the 60mL hexane, leaves standstill 20 minutes, tells lower floor's catalyzer and is used for reacting next time; Upper solution adds the 20mL weak ammonia, divides water-yielding stratum, uses 3 * 20mL washing again, is about 7 until pH; Organic layer is transferred in the single port bottle, steams methylene dichloride, crystallization is filtered; The filter cake methanol wash in 50 ℃ of vacuum-dryings of temperature, can obtain 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene white crystal, productive rate is 81.3%.
Embodiment 17
In the 500mL there-necked flask, add 5.0g[MimN (CH 2) 3SO 3H] [HSO 4] ionic liquid (N-(3-sulfonic group) propyl group-imidazole salts wherein: the vitriol oil)=1: 1.5), 85mL methylene dichloride, 3.6g sym-trimethylbenzene; Stir under the room temperature; Drip intermediate solution (10g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 40mL methylene dichloride) in 10 minutes;
Under 0.07MPa pressure; In 30 ℃ of following reflux of temperature, evaporation methylene dichloride limit, limit stream adds the intermediate solution (27.5g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 100mL methylene dichloride) of residual content; Evaporation time is 0.8h; Dripped in 60 minutes and finish, reaction generates 1,3; 5-trimethylammonium-2; 4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Reaction finishes, and adds the 60mL octane, leaves standstill 20 minutes, tells lower floor's catalyzer and is used for reacting next time; Upper solution adds the 20mL weak ammonia, divides water-yielding stratum, uses 3 * 20mL washing again, is about 7 until pH; Organic layer is transferred in the single port bottle, steams methylene dichloride, crystallization is filtered; The filter cake methanol wash in 50 ℃ of vacuum-dryings of temperature, can obtain 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene white crystal, productive rate is 84.7%.
Embodiment 18
In the 500mL there-necked flask, add 5.0g[PyN (CH 2) 3SO 3H] [HSO 4] ionic liquid (N-(3-sulfonic group) propyl group-pyridinium salt wherein: the vitriol oil)=1: 2), 75mL methylene dichloride, 5mL heptane, 3.6g sym-trimethylbenzene; Stir under the room temperature, drip intermediate solution (10g intermediate 2-methyl-6-tert butyl-4-methoxymethyl phenol and 30mL methylene dichloride) in 10 minutes;
Under 0.09MPa pressure; In 38 ℃ of following reflux of temperature; Evaporation methylene dichloride limit, limit stream adds the intermediate solution (15g intermediate 2-methyl-6-tert butyl-4-methoxymethyl phenol and 70mL methylene dichloride) of residual content, and evaporation time is 3h, drips complete in 60 minutes; Reaction generates 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Reaction finishes, and adds the 60mL heptane, leaves standstill 20 minutes, tells lower floor's catalyzer and is used for reacting next time; Upper solution adds the 20mL weak ammonia, divides water-yielding stratum, uses 3 * 20mL washing again, is about 7 until pH; Organic layer is transferred in the single port bottle, steams methylene dichloride, crystallization is filtered; The filter cake methanol wash in 50 ℃ of vacuum-dryings of temperature, can obtain 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene white crystal, productive rate is 82.5%.
Embodiment 19
In the 500mL there-necked flask, add 5.0g[PyN (CH 2) 3SO 3H] [HSO 4The vitriol oil=1: 2), 75mL methylene dichloride, 3mL hexane, 3.6g sym-trimethylbenzene] ionic liquid (N-(3-sulfonic group) propyl group-pyridinium salt wherein:; Stir under the room temperature, drip intermediate solution (6.25g intermediate 2-methyl-6-tert butyl-4-methoxymethyl phenol and 30mL methylene dichloride) in 10 minutes;
Under 0.1MPa pressure; In 40 ℃ of following reflux of temperature, evaporation methylene dichloride limit, limit stream adds the intermediate solution (20g intermediate 2,6-di-t-butyl-4-methoxyl methyl phenol and 70mL methylene dichloride) of residual content; Evaporation time is 2h; Dripped in 60 minutes and finish, reaction generates 1,3; 5-trimethylammonium-2; 4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Reaction finishes, and adds the 60mL pentane, leaves standstill 20 minutes, tells lower floor's catalyzer and is used for reacting next time; Upper solution adds the 20mL weak ammonia, divides water-yielding stratum, uses 3 * 20mL washing again, is about 7 until pH; Organic layer is transferred in the single port bottle, steams methylene dichloride, crystallization is filtered; The filter cake methanol wash in 50 ℃ of vacuum-dryings of temperature, can obtain 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene white crystal, productive rate is 81.9%.

Claims (6)

1. one kind 3,5-trimethylammonium-2,4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene is characterized in that shown in chemical formula (1):
Figure FSA00000559606400011
Concrete operations follow these steps to carry out:
A, in reactor, add catalyzer and sym-trimethylbenzene that mixture that solvent is halohydrocarbon or halogenated alkane and sherwood oil, amido organic sulfonic acid inner salt and sulfuric acid are prepared; Under agitation drip 2 earlier; The 40%-60% of 6-di-t-butyl-4-methoxyl methyl phenol and halohydrocarbon blended solution total amount, the dropping time is 0.1-0.3h;
B, add 2 of residual content on the solvent limit of the following evaporation reaction liquid of 0.02-0.1MPa pressure; 6-di-t-butyl-4-methoxyl methyl phenol and halohydrocarbon blended solution; The evaporation reaction temperature is 30-80 ℃, and the joining day is 0.2-2h, and the evaporation time of halohydrocarbon is 0.3-3h; Reaction generates 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Add sherwood oil after c, reaction finish, tell lower floor's catalyzer and be used for reacting next time, upper solution is through neutralization, and washing evaporates the residue halohydrocarbon, and crystallization separates, and can obtain 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
2. according to right 1 said method, it is characterized in that the amido organic sulfonic acid inner salt among the step a is by the compound shown in the molecular formula (2), cooperate with sulfuric acid to form ionic liquid:
Figure FSA00000559606400021
N=2,3 or 4 wherein; R 1, R 2, R 3The alkyl of=C1-C15, described alkyl are identical or different alkyl.
3. according to right 2 described methods, it is characterized in that amido organic sulfonic acid inner salt and sulfuric acid mol ratio are 1: 1-4.
4. according to right 3 described methods; It is characterized in that catalyzer, sym-trimethylbenzene and 2 among the step a; 6-di-t-butyl-4-methoxyl methyl phenol mol ratio is: amido organic sulfonic acid inner salt: 2; 6-di-t-butyl-4-methoxyl methyl phenol=1: 1-30; Sym-trimethylbenzene: 2,6-di-t-butyl-4-methoxyl methyl phenol=1: 3-6.
5. according to right 4 described methods, it is characterized in that the solvent halohydrocarbon among the step a is methylene dichloride, trichloromethane, 1,1-ethylene dichloride, 1,2-ethylene dichloride or 1, sherwood oil are the alkane of C5-C9.
6. according to right 5 described methods, it is characterized in that step c sherwood oil is the alkane of C5-C9.
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