CN102452903A - Preparation method of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene - Google Patents
Preparation method of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene Download PDFInfo
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Abstract
The invention provides a preparation method of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and the method comprises the following steps: in the presence of an acid catalyst, under a condensation reaction condition, allowing mesitylene and 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether to react in an organic solvent, removing the organic solvent in the mixture obtained in the reaction by distillation under a reduced-pressure condition. By using 3,5-di-tert-butyl-4-hydroxybenzyl methyl ether and mesitylene as raw materials, and by organic solvent removal through distillation under a reduced-pressure condition after the reaction, the conversion rate of the reaction is significantly improved; the yield and purity of the target product of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene are improved; and the organic solvent removal through distillation at a low temperature is realized.
Description
Technical field
The present invention relates to a kind of oxidation inhibitor 1,3,5-trimethylammonium-2,4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
Background technology
1; 3,5-trimethylammonium-2,4; 6-three (3; The 5-di-tert-butyl-4-hydroxyl benzyl) benzene is that a kind of oxidation inhibitor of high molecular weight hindered phenols structure (is claimed again: antioxidant 330), have good heat-resistant stability, low volatility and anti-extractibility, be widely used in the general and engineering plastic product that polyolefin modified and linear polyester and polymeric amide etc. require processing and application under hot conditions; And become the focus that world's polymer stabilising auxiliary agent and polymer processing industry are paid close attention to day by day, produce consumption and be the gesture that increases rapidly.
1,3,5-trimethylammonium-2,4, the following three kinds of methods of the general employing of the preparation of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene: the one, with 2,6-di-t-butyl-4-hydroxy-benzyl alcohol is that raw material prepares; The 2nd, with 2,6-di-tert-butyl-4-hydroxyl benzyl ether is that raw material prepares; The 3rd, be that raw material prepares [oxidation inhibitor 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene synthetic, Tian Jiangbo, meticulous and specialty chemicals, 2005 the 10th phases, 20-21] with the 2,6 di t butyl phenol.
In addition, to disclose a kind of be feedstock production oxidation inhibitor 1 with the 2,6 di t butyl phenol to patent US4754077; 3,5-trimethylammonium-2,4; The method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, this method are included in and add methyl alcohol, Paraformaldehyde 96,40% moisture n n dimetylaniline in the four-hole boiling flask; Reaction mixture is heated to the 2,6 di t butyl phenol solution that reflux temperature (about 68 ℃) begins to drip with tap funnel dissolve with methanol, keeps backflow, nitrogen protection to drip off in three hours.Dropwise, reacting rear material is moved in the two slurry formula voltage-resistant reactors of band, heating is stirred 4h at 80 ℃; Be cooled to 65 ℃ then; Material is moved in another reactor drum, and reaction mixture is heated with stirring to oily temperature 100-120 ℃ under nitrogen protection, with solvent evaporation remove 2; 6-di-t-butyl-4 hydroxybenzyl ether adds methylene dichloride, sym-trimethylbenzene, acetate in the reactor drum.Keep 3-7 ℃ of temperature of reaction, drip about 84% sulfuric acid as catalyzer with tap funnel, leave standstill then, separatory is got upper strata liquid and is added sodium carbonate solution, heats up to steam methylene dichloride to temperature >=85 ℃, gets title product with the heptane recrystallization.But, adopt above-mentioned patented process to prepare oxidation inhibitor 1,3,5-trimethylammonium-2; 4, during 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; Remove the higher product transmittance that influences of methylene dichloride temperature owing to steam, and steam, influence product crystal formation and purity except that being prone to caking in the process; And, be prone to cause the generation of by product (particularly two-(4-hydroxyl-3,5-di-tert-butyl-phenyl)-methane) because fluid sulphuric acid is also higher to the activity of side reaction.
Summary of the invention
The objective of the invention is to overcome oxidation inhibitor 1,3 in the prior art, 5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene prepares the problem that exists in the process, provides a kind of and can remove organic solvent at low temperatures; Improve 1,3 of product purity, 5-trimethylammonium-2; 4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
The invention provides 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; This method comprises: under the condensation reaction condition; Make sym-trimethylbenzene and 3, the 5-di-tert-butyl-4-hydroxyl benzyl methyl ether reacts in organic solvent, and under the condition of decompression, removes the organic solvent in the dereaction gained mixture through distillation.
According to preparation 1,3 of the present invention, 5-trimethylammonium-2,4,6-three (3; The 5-di-tert-butyl-4-hydroxyl benzyl) method of benzene, through with 3,5-di-tert-butyl-4-hydroxyl benzyl methyl ether and sym-trimethylbenzene are raw material, and after reaction finishes, remove organic solvent through under reduced pressure steaming; Can significantly improve the transformation efficiency of reaction, improve title product 1,3,5-trimethylammonium-2; 4, the productive rate and the purity of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, and can realize steaming except that organic solvent at low temperatures.
Embodiment
According to of the present invention 1,3,5-trimethylammonium-2; 4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; This method comprises: in the presence of acid catalyst, under the condensation reaction condition, make sym-trimethylbenzene and 3; The 5-di-tert-butyl-4-hydroxyl benzyl methyl ether reacts in organic solvent, and under the condition of decompression, removes the organic solvent in the dereaction gained mixture through distillation.
Preparation in accordance with the present invention, wherein, as 3 of raw material, the structure of 5-di-tert-butyl-4-hydroxyl benzyl methyl ether is suc as formula shown in (1),
In the present invention, employed 3, the 5-di-tert-butyl-4-hydroxyl benzyl methyl ether can obtain through existing various preparing methods, as being raw material with the 2,6 di t butyl phenol, prepares as catalyzer with oxyhydroxide or various amine; Also can be commercially available.
Preparation in accordance with the present invention, said reaction can be carried out in the presence of suppressor factor.
Preparation in accordance with the present invention; So-called suppressor factor is meant can be to being 3 except main reaction, and 5-di-tert-butyl-4-hydroxyl benzyl methyl ether and sym-trimethylbenzene reaction generate title product 1,3; 5-trimethylammonium-2; 4, inhibiting preparation is played in the side reaction outside 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.In the present invention, the consumption of said suppressor factor can suitably be selected, under preferred situation; With respect to 3 of 100 weight parts; The 5-di-tert-butyl-4-hydroxyl benzyl methyl ether, the consumption of said suppressor factor can be the 0.4-12 weight part, is preferably the 4-8 weight part.The consumption of said suppressor factor can effectively suppress the generation of side reaction in above-mentioned scope the time, improves the transformation efficiency of reaction.In the present invention, said suppressor factor can be at least a in the group formed of the ortho-formiate of 4-13 for being selected from by carbonatoms is the aldehyde of 1-7, organic carboxyl acid that carbonatoms is 1-7, the carbonic acid atomicity is 3-8 acetal or semi-acetal and carbonatoms.Be preferably and be selected from by formaldehyde, Paraformaldehyde 96, acetaldehyde, propionic aldehyde, butyraldehyde, phenyl aldehyde, oxalic acid, Hydrocerol A, formic acid, acetate, propionic acid, butyric acid, phenylformic acid, Methylal(dimethoxymethane), methylene diethyl ether, propylal, 1; 1-glycol dimethyl ether, 1; 1-diethoxyethane, 1, at least a in the group that 1-dipropoxy ethane, ethylene glycol acetal, Ucar 35 formal, trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate and tributyl orthoformate are formed.
Preparation in accordance with the present invention, wherein, said acid catalyst can be various materials with acid sites or acidic site; As long as can play catalysis 3,5-di-tert-butyl-4-hydroxyl benzyl methyl ether and sym-trimethylbenzene reaction generate 1,3; 5-trimethylammonium-2; 4, the effect of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene gets final product.Said acid catalyst and said 3, the mol ratio of 5-di-tert-butyl-4-hydroxyl benzyl methyl ether can be 0.5-1.5: 1, be preferably 0.8-1.2: 1.The consumption of said acid catalyst can effectively improve the speed of reaction in above-mentioned scope the time.In the present invention, said acid catalyst can be for being selected from least a in the group of being made up of inorganic liquid acid catalyst, inoganic solids acid catalyst and organic sulfonic acid catalyzer.Said inoganic solids acid catalyst can be various Lewis acids.Under preferred situation, said acid catalyst is to be selected from least a in the group that sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, trifluoracetic acid, aluminum chloride, aluminum bromide, zinc chloride, iron(ic)chloride, molecular sieve, methylsulphonic acid, ethylsulfonic acid, propyl sulfonic acid, trichloromethyl sulfonic acid, trifluoromethane sulfonic acid, Phenylsulfonic acid, toluene sulfonic acide, halogeno-benzene sulfonic acid and sulfonate resin form.When adopting above-mentioned acid, can under the prerequisite that guarantees speed of reaction, effectively suppress the generation of side reaction, improve the yield and the purity of reaction product as catalyzer.
Preparation in accordance with the present invention, wherein said 3, the mol ratio of 5-di-tert-butyl-4-hydroxyl benzyl methyl ether and said sym-trimethylbenzene can be 4-3: 1, be preferably 3.5-3.1: 1.3, the consumption of 5-di-tert-butyl-4-hydroxyl benzyl methyl ether and sym-trimethylbenzene can improve the speed of reaction in above-mentioned scope the time, improves utilization ratio of raw materials.
Preparation in accordance with the present invention, wherein, said condensation reaction condition can be 3; 5-di-tert-butyl-4-hydroxyl benzyl methyl ether and sym-trimethylbenzene generate 1,3,5-trimethylammonium-2; 4, the various normal conditions of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; Under preferred condition, said condensation reaction condition comprises: temperature of reaction can be-80～15 ℃, is preferably-50～5 ℃; Reaction times can be 0.5-6 hour, is preferably 1-3 hour.When under above-mentioned reaction conditions, reacting, can significantly improve the transformation efficiency of reaction, improve the yield of title product.
In the present invention, said organic solvent is not had special qualification, can for this area conventional various not with raw material 3; 5-di-tert-butyl-4-hydroxyl benzyl methyl ether, sym-trimethylbenzene and title product 1; 3,5-trimethylammonium-2,4; The organic solvent that 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene reacts.Can be lower halogenated alkane in the present invention, such as methylene dichloride etc.Carry out as long as the consumption of said organic solvent can guarantee successful reaction, just do not have special qualification, can be 1-8 times of raw material gross weight, be preferably 2-4 doubly.
In the present invention, also be included in and remove operations such as organic solvent, separation, washing and dry title product after reaction finishes, these operations are the conventional operation of art technology, can select according to actual needs.In the present invention, can be preferably under 30-60 ℃ and remove organic solvent at 0-90 ℃ through modes such as distillations; Can use lower alkanols alcohol as methyl alcohol etc. or cleaning solvents such as lower straight alkane such as heptane that the product that removes behind the organic solvent is washed, the consumption of said cleaning solvent can be products therefrom weight 4-12 doubly, be preferably 6-9 times; Said exsiccant mode can be the conventional drying mode in this area, and drying temperature can be 20-120 ℃, is preferably 40-60 ℃.
According to of the present invention 1,3,5-trimethylammonium-2,4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, said distillation can be carried out in the presence of tensio-active agent.
In this preparation method, after finishing, in the presence of tensio-active agent, to distill and remove beyond the organic solvent in reaction, other process is all identical with above-mentioned preparation method, therefore, repeats no more at this for same section.Below organic solvent is removed in distillation under tensio-active agent process be described in detail.
Preparation in accordance with the present invention, wherein, the method that organic solvent is removed in said distillation can adopt the conventional water distilling apparatus in this area that the organic solvent distillation is removed, and said distillatory temperature can be 0-90 ℃, is preferably 30-60 ℃.Said amount of surfactant does not have special requirement, under preferred situation, and with respect to 3 of 100 weight parts, the 5-di-tert-butyl-4-hydroxyl benzyl methyl ether, said amount of surfactant can be the 0.01-2.0 weight part, is preferably the 0.1-0.2 weight part.Said tensio-active agent can be AS and/or cats product.Under preferred situation, said AS can be carboxylate salt and/or sulphonate, and said cats product can be quaternary ammonium salt.
Under preferred situation, said carboxylate salt is the compound shown in the general formula (I),
(R’
1COO)
n1M
1 (I)
Wherein, R '
1For carbonatoms is the alkyl of 8-25, M
1At least a among Na, K, Ca and the Mg is according to M
1Valence state, n1 is 1 or 2;
Said sulphonate be general formula (II) or (III) shown in compound,
(R’
2SO
3)
n2M
2 (II)
Wherein, R '
2For carbonatoms is the alkyl of 8-25, M
2At least a among Na, K, Ca and the Mg is according to M
2Valence state, n2 is 1 or 2;
Wherein, R ' is the alkyl of 8-25 for carbonatoms, and M ' is Na or K;
Said quaternary ammonium salt is the compound shown in the general formula (IV),
Wherein, R
1, R
2, R
3And R
4Be the alkyl of 1-25 independently of one another for carbonatoms, and R
1, R
2, R
3And R
4In at least one be the alkyl of 8-25 for carbonatoms, X is a halogen.
Under further preferred situation, said carboxylate salt is the compound shown in the general formula (I),
(R’
1COO)M
1 (I)
Wherein, R '
1For carbonatoms is the alkyl of 8-16, M
1Be Na or K;
Said sulphonate be general formula (II) or (III) shown in compound,
(R’
2SO
3)M
2 (II)
Wherein, R '
2For carbonatoms is the alkyl of 8-16, M
2Be Na or K;
Wherein, R ' is the alkyl of 8-16 for carbonatoms, and M ' is Na or K;
Said quaternary ammonium salt is the compound shown in the general formula (IV),
Wherein, R
1, R
2, R
3And R
4Be the alkyl of 1-16 independently of one another for carbonatoms, and R
1, R
2, R
3And R
4In at least one be the alkyl of 8-16 for carbonatoms, X is a chlorine.
Under further preferred situation, said tensio-active agent is at least a in Sodium octoate, potassium octanoate, X 2073 and the palmityl trimethyl ammonium chloride.
Preparing method of the present invention is through after finishing in reaction; In the presence of tensio-active agent, steam and remove organic solvent; Can obviously improve the form of title product, make title product become the Powdered of rule, obtain into the dope shape or blocky title product is compared with under surfactant-free, steaming in the prior art except that organic solvent; Have and help washing the advantage of removing impurities in the product, can obviously improve the purity of title product.
Preparation in accordance with the present invention, wherein, the method that organic solvent is removed in said distillation can adopt the conventional water distilling apparatus in this area that the organic solvent distillation is removed, and said distillatory temperature can be 0-90 ℃, is preferably 30-60 ℃.The condition of said decompression comprises that pressure can be-0.1MPa～0MPa, be preferably-0.08MPa～-0.04MPa.Remove organic solvent through distillation under the decompression in above-mentioned scope, can significantly improve the removal effect of organic solvent, further improve the purity of title product.
Below through enumerating embodiment to of the present invention 1,3,5-trimethylammonium-2,4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene explains in more detail, but preparation method of the present invention is not limited to following examples.
Among in the present invention all embodiment and Comparative Examples, 3, the 5-di-tert-butyl-4-hydroxyl benzyl methyl ether is through preparing according to the following method for preparing example 1; Other organic reagent is all available from Beijing northization fine chemicals ltd.
Preparation example 1
The 2,6 di t butyl phenol, the Paraformaldehyde 96 (n=18) of 12.1g, the methyl alcohol of 200mL, the piperazine of 0.5g and the N of 3.0mL that in the 500ml autoclave, add 49.6g, N; N '; N '-Tetramethyl Ethylene Diamine under nitrogen protection, is 110 ℃ in temperature and reacted 4 hours down.Be cooled to-5 ℃ of crystallizations then, separate obtaining 3,5-di-tert-butyl-4-hydroxyl benzyl methyl ether solid.Identify through liquid phase chromatography, gained 3, the purity of 5-di-tert-butyl-4-hydroxyl benzyl methyl ether is 99.3%.
Embodiment 1
It is provided by the invention 1,3 that present embodiment is used to explain, 5-trimethylammonium-2,4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
In four-hole boiling flask, add sym-trimethylbenzene 10mmol (1.20g) and 5mL methylene dichloride, place low-temp reaction to bathe reactor drum, temperature is controlled at-50 ℃; Under agitation with 34.1mmol sulfuric acid (concentration is 98 weight %) and 31mmol (7.75g) 3; 5-di-tert-butyl-4-hydroxyl benzyl methyl ether (being dissolved in the 75mL methylene dichloride) added in the reactor drum with constant speed with 35 minutes; Behind reinforced the end, react 2h down at-50 ℃ again.Reaction is poured reaction mixture in the separating funnel into after finishing, and standing demix is got upper solution with saturated sodium carbonate solution neutralization sulfuric acid wherein; Until the pH of solution value is 7～8, filters, and will filtrate to distill down-0.06MPa, 50 ℃ and remove methylene chloride, uses the 62ml methanol wash again three times; Obtain 6.59g white solid A1 50 ℃ of following dryings, identify that through liquid phase chromatography the gained white solid is 1 of a purity 99.8%; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (0.849mmol), but the productive rate of calculating principal reaction is 84.9%.
Comparative Examples 1
According to the method preparation 1,3 of embodiment 1,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, wherein, different is after preparing, and removes methylene chloride in normal pressure, 50 ℃ of following distillations.Obtain 6.23g white solid D1, identify that through liquid phase chromatography the gained white solid is 1,3 of a purity 88.1%, 5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (0.708mmol), calculating can know that productive rate is 70.8%.
Embodiment 2
It is provided by the invention 1,3 that present embodiment is used to explain, 5-trimethylammonium-2,4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
In four-hole boiling flask, add sym-trimethylbenzene 10mmol (1.20g) and 5mL methylene dichloride, Methylal(dimethoxymethane), place low-temp reaction to bathe reactor drum, temperature is controlled at-80 ℃; Under agitation with 40mmol tosic acid and 40mmol (10g) 3,5-di-tert-butyl-4-hydroxyl benzyl methyl ether (being dissolved in the 75mL methylene dichloride) added in the reactor drum with constant speed with 40 minutes, behind reinforced the end, reacted 2h down at-80 ℃ again.Reaction is poured reaction mixture in the separating funnel into after finishing, and standing demix is got upper solution with saturated sodium carbonate solution neutralization tosic acid wherein; Until the pH of solution value is 7～8, filters, and will filtrate to distill down-0.08MPa, 60 ℃ and remove methylene chloride, uses the 62ml methanol wash again three times; Obtain 6.01g white solid A2 60 ℃ of following dryings, identify that through liquid phase chromatography the gained white solid is 1 of a purity 98.7%; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (0.765mmol), but the productive rate of calculating principal reaction is 76.5%.
Embodiment 3
It is provided by the invention 1,3 that present embodiment is used to explain, 5-trimethylammonium-2,4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
In four-hole boiling flask, add sym-trimethylbenzene 10mmol (1.20g) and 5mL methylene dichloride, 0.9g trimethyl orthoformate, place low-temp reaction to bathe reactor drum, temperature is controlled at 15 ℃; Under agitation with 45mmol tosic acid and 30mmol (7.5g) 3,5-di-tert-butyl-4-hydroxyl benzyl methyl ether (being dissolved in the 75mL methylene dichloride) added in the reactor drum with constant speed with 30 minutes, behind reinforced the end, reacted 2h down at 15 ℃ again.Reaction is poured reaction mixture in the separating funnel into after finishing, and standing demix is got upper solution with saturated sodium carbonate solution neutralization tosic acid wherein; Until the pH of solution value is 7～8, filters, and will filtrate to distill down-0.04MPa, 50 ℃ and remove methylene chloride, uses the 62ml methanol wash again three times; Obtain 6.23g white solid A3 50 ℃ of following dryings, identify that through liquid phase chromatography the gained white solid is 1 of a purity 99.1%; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (0.796mmol), but the productive rate of calculating principal reaction is 79.6%.
Can know through comparing embodiment 1-3 and Comparative Examples 1, by of the present invention 1,3,5-trimethylammonium-2,4, the purity and the yield of the title product of preparing method's preparation of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene are higher.
Embodiment 4
It is provided by the invention 1,3 that present embodiment is used to explain, 5-trimethylammonium-2,4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
The methylal that in four-hole boiling flask, adds sym-trimethylbenzene 10mmol (1.20g) and 5mL methylene dichloride, 0.071g places low-temp reaction to bathe reactor drum, and temperature is controlled at 5 ℃; Under agitation with 3 of 34.1mmol sulfuric acid (concentration is 98 weight %) and 31mmol (7.75g); 5-di-tert-butyl-4-hydroxyl benzyl methyl ether (being dissolved in the 75mL methylene dichloride) added in the reactor drum with constant speed with 35 minutes; Behind reinforced the end, react 6h down at-50 ℃ again.Reaction is poured reaction mixture in the separating funnel into after finishing, and standing demix is got upper solution with saturated sodium carbonate solution neutralization sulfuric acid wherein; Until the pH of solution value is 7～8, filters, and adds the 0.13g sodium laurylsulfonate in the filtrating ,-0.06MPa, 50 ℃ down distillation remove methylene chloride; Use the 62ml heptane wash again three times, obtain 6.23g white powder A4 after the drying, identify that through liquid phase chromatography the gained white powder is 1 of a purity 98.5%; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (0.792mmol), but the productive rate of calculating principal reaction is 79.2%.
Embodiment 5
It is provided by the invention 1,3 that present embodiment is used to explain, 5-trimethylammonium-2,4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
The methylal that in four-hole boiling flask, adds sym-trimethylbenzene 10mmol (1.20g) and 5mL methylene dichloride, 0.96g places low-temp reaction to bathe reactor drum, and temperature is controlled at-50 ℃; Under agitation with 3 of 16mmol sulfuric acid (concentration is 98 weight %) and 32mmol (8g), 5-di-tert-butyl-4-hydroxyl benzyl methyl ether (being dissolved in the 75mL methylene dichloride) added in the reactor drum with constant speed with 38 minutes, behind reinforced the end, reacted 2h down at-50 ℃ again.Reaction is poured reaction mixture in the separating funnel into after finishing, and standing demix is got upper solution with saturated sodium carbonate solution neutralization sulfuric acid wherein; Until the pH of solution value is 7～8, filters, and adds the 0.016g palmityl trimethyl ammonium chloride in the filtrating ,-0.06MPa, 50 ℃ down distillation remove methylene chloride; Use the 62ml heptane wash again three times, obtain 6.30g white powder A5 after the drying, identify that through liquid phase chromatography the gained white powder is 1 of a purity 99.2%; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (0.806mmol), but the productive rate of calculating principal reaction is 80.6%.
Embodiment 6
It is provided by the invention 1,3 that present embodiment is used to explain, 5-trimethylammonium-2,4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
The methylal that in four-hole boiling flask, adds sym-trimethylbenzene 10mmol (1.20g) and 5mL methylene dichloride, 0.3875g places low-temp reaction to bathe reactor drum, and temperature is controlled at-50 ℃; Under agitation with 3 of 34.1mmol sulfuric acid (concentration is 98 weight %) and 31mmol (7.75g); 5-di-tert-butyl-4-hydroxyl benzyl methyl ether (being dissolved in the 75mL methylene dichloride) added in the reactor drum with constant speed with 40 minutes; Behind reinforced the end, react 2h down at-50 ℃ again.Reaction is poured reaction mixture in the separating funnel into after finishing, and standing demix is got upper solution with saturated sodium carbonate solution neutralization sulfuric acid wherein; Until the pH of solution value is 7～8, filters, and adds the 0.0078g X 2073 in the filtrating ,-0.06MPa, 50 ℃ down distillation remove methylene chloride; Use the 62ml heptane wash again three times, obtain 6.36g white powder A6 after the drying, identify that through liquid phase chromatography the gained white powder is 1 of a purity 99.3%; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (0.815mmol), but the productive rate of calculating principal reaction is 81.5%.
Comparative Examples 2
According to the method preparation 1,3 of embodiment 4,5-trimethylammonium-2; 4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; Wherein, different is after preparing, and removes methylene chloride in normal pressure, 50 ℃ of following distillations; No formal exists in the preparation process, and distillation is removed in the process of organic solvent and do not added sodium laurylsulfonate.Obtain 6.18g white blocks of solid D2, identify through liquid phase chromatography, gained white blocks of solid is 1,3 of a purity 88.1%, 5-trimethylammonium-2,4, and 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (0.702mmol), calculating can know that productive rate is 70.2%.
Can know through comparing embodiment 4-6 and Comparative Examples 2, by of the present invention 1,3; 5-trimethylammonium-2; 4, the purity and the yield of the title product of preparing method's preparation of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene are higher; And the form of the title product of preparation is Powdered for uniformly, and Comparative Examples 2 resulting products are blocks of solid.
Embodiment 7
It is provided by the invention 1,3 that present embodiment is used to explain, 5-trimethylammonium-2,4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
The methylal that in four-hole boiling flask, adds sym-trimethylbenzene 10mmol (1.20g) and 5mL methylene dichloride, 0.3875g places low-temp reaction to bathe reactor drum, and temperature is controlled at-50 ℃; Under agitation with 3 of 46.5mmol sulfuric acid (concentration is 98 weight %) and 31mmol (7.75g); 5-di-tert-butyl-4-hydroxyl benzyl methyl ether (being dissolved in the 93mL methylene dichloride) added in the reactor drum with constant speed with 40 minutes; Feed in raw material after the end, behind reinforced the end, react 2h down at-50 ℃ again.Reaction is poured reaction mixture in the separating funnel into after finishing, and standing demix is got upper solution with saturated sodium carbonate solution neutralization acid catalyst wherein; Until the pH of solution value is 7～8, filters, and adds the 0.13g X 2073 in the filtrating ,-0.06MPa, 50 ℃ down distillation remove methylene chloride; Through 93ml methanol wash three times, obtain 6.59g white powder A7 after the drying again, identify that through liquid phase chromatography the gained white powder is a purity 97.8%1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (0.831mmol), but the productive rate of calculating principal reaction is 83.1%.
Embodiment 8
It is provided by the invention 1,3 that present embodiment is used to explain, 5-trimethylammonium-2,4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
The methylal that in four-hole boiling flask, adds sym-trimethylbenzene 10mmol (1.20g) and 5mL methylene dichloride, 0.3875g places low-temp reaction to bathe reactor drum, and temperature is controlled at-50 ℃; Under agitation with 3 of 31mmo sulfuric acid (concentration is 98 weight %) and 31mmol (7.75g); 5-di-tert-butyl-4-hydroxyl benzyl methyl ether (being dissolved in the 31mL methylene dichloride) added in the reactor drum with constant speed with 40 minutes; Behind reinforced the end, react 2h down at-50 ℃ again.Reaction is poured reaction mixture in the separating funnel into after finishing, and standing demix is got upper solution with saturated sodium carbonate solution neutralization sulfuric acid wherein; Until the pH of solution value is 7～8, filters, and adds the 0.13g X 2073 in the filtrating, steams methylene chloride down-0.08MPa, 50 ℃; Through 31ml methanol wash three times, obtain 6.17g white powder A8 after the drying again, identify that through liquid phase chromatography the gained white powder is a purity 99.1%1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (0.789mmol), calculating can know that productive rate is 78.9%.
Embodiment 9
It is provided by the invention 1,3 that present embodiment is used to explain, 5-trimethylammonium-2,4, the preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
The methylal that in four-hole boiling flask, adds sym-trimethylbenzene 10mmol (1.20g) and 5mL methylene dichloride, 0.3875g places low-temp reaction to bathe reactor drum, and temperature is controlled at-50 ℃; Under agitation with 3 of 31mmol sulfuric acid (concentration is 98 weight %) and 31mmol (7.75g); 5-di-tert-butyl-4-hydroxyl benzyl methyl ether (being dissolved in the 31mL methylene dichloride) added in the reactor drum with constant speed with 40 minutes; Behind reinforced the end, react 2h down at-50 ℃ again.Reaction is poured reaction mixture in the separating funnel into after finishing, and standing demix is got upper solution with saturated sodium carbonate solution neutralization sulfuric acid wherein; Until the pH of solution value is 7～8, filters, and adds the 0.13g X 2073 in the filtrating, steams methylene chloride down-0.04MPa, 50 ℃; Through 50ml methanol wash three times, obtain 6.26g white powder A9 after the drying again, identify that through liquid phase chromatography the gained white powder is a purity 99.0%1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (0.789mmol), calculating can know that productive rate is 80.1%.
Therefore, preparation 1,3 of the present invention, 5-trimethylammonium-2,4; The method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, through with 3,5-di-tert-butyl-4-hydroxyl benzyl methyl ether and sym-trimethylbenzene are raw material, and after reaction finishes; Remove organic solvent through under reduced pressure steaming, can significantly improve the transformation efficiency of reaction, improve title product 1,3,5-trimethylammonium-2; 4, the productive rate and the purity of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, and can realize steaming except that organic solvent at low temperatures.Simultaneously, in the presence of suppressor factor, prepare and after reaction finishes, through under tensio-active agent, steaming except that organic solvent; Can effectively reduce the generation of side reaction; Reduce the generation of by product, effectively improve the transformation efficiency of reaction, and can further effectively improve product purity; Improve product form, make product become the Powdered of rule.
Claims (20)
1. one kind 3,5-trimethylammonium-2,4; The preparation method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, this method comprises: in the presence of acid catalyst; Under the condensation reaction condition; Make sym-trimethylbenzene and 3, the 5-di-tert-butyl-4-hydroxyl benzyl methyl ether reacts in organic solvent, and under the condition of decompression, removes the organic solvent in the dereaction gained mixture through distillation.
2. preparation method according to claim 1, wherein, the condition of said decompression comprises that pressure is-0.1MPa～0MPa.
3. preparation method according to claim 2, wherein, the condition of said decompression comprise pressure be-0.08MPa～-0.04MPa.
4. preparation method according to claim 1 wherein, carries out under the said existence that is reflected at suppressor factor.
5. preparation method according to claim 4, wherein, with respect to 3 of 100 weight parts, 5-di-tert-butyl-4-hydroxyl benzyl methyl ether, the consumption of said suppressor factor are the 0.4-12 weight part.
6. preparation method according to claim 5, wherein, with respect to 3 of 100 weight parts, 5-di-tert-butyl-4-hydroxyl benzyl methyl ether, the consumption of said suppressor factor are the 4-8 weight part.
7. according to any described preparation method among the claim 4-6; Wherein, said suppressor factor is that being selected from by carbonatoms is the aldehyde of 1-7, organic carboxyl acid that carbonatoms is 1-7, the carbonic acid atomicity is 3-8 acetal or semi-acetal and carbonatoms is at least a in the group formed of the ortho-formiate of 4-13.
8. preparation method according to claim 7; Wherein, Said suppressor factor is for being selected from by formaldehyde, Paraformaldehyde 96, acetaldehyde, propionic aldehyde, butyraldehyde, phenyl aldehyde, formic acid, acetate, propionic acid, butyric acid, phenylformic acid, oxalic acid, Hydrocerol A, Methylal(dimethoxymethane), methylene diethyl ether, propylal, 1; 1-glycol dimethyl ether, 1; 1-diethoxyethane, 1, at least a in the group that 1-dipropoxy ethane, ethylene glycol acetal, Ucar 35 formal, trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate and tributyl orthoformate are formed.
9. preparation method according to claim 1, wherein, said distillation is carried out in the presence of tensio-active agent.
10. preparation method according to claim 9, wherein, with respect to 3 of 100 weight parts, the 5-di-tert-butyl-4-hydroxyl benzyl methyl ether, said amount of surfactant is the 0.01-2 weight part.
11. preparation method according to claim 10, wherein, with respect to 3 of 100 weight parts, the 5-di-tert-butyl-4-hydroxyl benzyl methyl ether, said amount of surfactant is the 0.1-0.2 weight part.
12. according to any described preparation method among the claim 9-11, wherein, said tensio-active agent is AS and/or cats product.
13. preparation method according to claim 12, wherein, said AS is carboxylate salt and/or sulphonate, and said cats product is a quaternary ammonium salt.
14. preparation method according to claim 13, wherein, said carboxylate salt is the compound shown in the general formula (I),
(R’
1COO)
n1M
1 (I)
Wherein, R '
1For carbonatoms is the alkyl of 8-25, M
1At least a among Na, K, Ca and the Mg is according to M
1Valence state, n1 is 1 or 2;
Said sulphonate be general formula (II) or (III) shown in compound,
(R’
2SO
3)
n2M
2 (II)
Wherein, R '
2For carbonatoms is the alkyl of 8-25, M
2At least a among Na, K, Ca and the Mg is according to M
2Valence state, n2 is 1 or 2;
Wherein, R ' is the alkyl of 8-25 for carbonatoms, and M ' is Na or K;
Said quaternary ammonium salt is the compound shown in the general formula (IV),
Wherein, R
1, R
2, R
3And R
4Be the alkyl of 1-25 independently of one another for carbonatoms, and R
1, R
2, R
3And R
4In at least one be the alkyl of 8-25 for carbonatoms, X is a halogen.
15. according to claim 13 or 14 described preparing methods, wherein, said tensio-active agent is at least a in Sodium octoate, potassium octanoate, X 2073 and the palmityl trimethyl ammonium chloride.
16. preparation method according to claim 1, wherein, said acid catalyst and said 3, the mol ratio of 5-di-tert-butyl-4-hydroxyl benzyl methyl ether is 0.5-1.5: 1.
17. preparation method according to claim 16, wherein, said acid catalyst is to be selected from least a in the group of being made up of inorganic liquid acid catalyst, inoganic solids acids catalyzer and organic sulfonic acid class catalyzer.
18. preparation method according to claim 17; Wherein, said acid catalyst is to be selected from least a in the group that sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, trifluoracetic acid, aluminum chloride, aluminum bromide, zinc chloride, iron(ic)chloride, molecular sieve, methylsulphonic acid, ethylsulfonic acid, propyl sulfonic acid, trichloromethyl sulfonic acid, trifluoromethane sulfonic acid, Phenylsulfonic acid, toluene sulfonic acide, halogeno-benzene sulfonic acid and sulfonate resin form.
19. preparation method according to claim 1, wherein said 3, the mol ratio of 5-di-tert-butyl-4-hydroxyl benzyl methyl ether and said sym-trimethylbenzene is 4-3: 1.
20. preparation method according to claim 1, wherein, the condition of said reaction comprises: temperature of reaction is-80～15 ℃, and the reaction times is 0.5-6 hour.
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| CN102452905A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing 1,3,5,-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxy benzyl) benzene |
| CN108503512A (en) * | 2018-03-29 | 2018-09-07 | 江苏极易新材料有限公司 | A kind of method of new catalyst synthesis antioxidant 330 |
| CN109608310A (en) * | 2019-01-24 | 2019-04-12 | 淄博润源化工有限公司 | A kind of free of contamination antioxidant 330 preparation method |
| CN110734459A (en) * | 2018-07-20 | 2020-01-31 | 中国石油天然气股份有限公司 | bifunctional compounds, synthesis method thereof and application thereof as antioxidant |
| CN110734580A (en) * | 2018-07-20 | 2020-01-31 | 中国石油天然气股份有限公司 | compounds containing hindered phenol and pentaerythritol structure, synthesis method thereof and application thereof as antioxidant |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102452905A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing 1,3,5,-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxy benzyl) benzene |
| CN108503512A (en) * | 2018-03-29 | 2018-09-07 | 江苏极易新材料有限公司 | A kind of method of new catalyst synthesis antioxidant 330 |
| CN110734459A (en) * | 2018-07-20 | 2020-01-31 | 中国石油天然气股份有限公司 | bifunctional compounds, synthesis method thereof and application thereof as antioxidant |
| CN110734580A (en) * | 2018-07-20 | 2020-01-31 | 中国石油天然气股份有限公司 | compounds containing hindered phenol and pentaerythritol structure, synthesis method thereof and application thereof as antioxidant |
| CN110734459B (en) * | 2018-07-20 | 2022-03-29 | 中国石油天然气股份有限公司 | Bifunctional compound, synthesis method thereof and application of bifunctional compound as antioxidant |
| CN109608310A (en) * | 2019-01-24 | 2019-04-12 | 淄博润源化工有限公司 | A kind of free of contamination antioxidant 330 preparation method |
| CN112250550A (en) * | 2020-11-09 | 2021-01-22 | 兰州精细化工有限责任公司 | Preparation method of antioxidant 330 |
| 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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