CN114805075B - Synthesis method of bis [3, 3-di (3-tert-butyl-4-hydroxyphenyl) butyric acid ] ethylene diester - Google Patents

Synthesis method of bis [3, 3-di (3-tert-butyl-4-hydroxyphenyl) butyric acid ] ethylene diester Download PDF

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CN114805075B
CN114805075B CN202210665763.2A CN202210665763A CN114805075B CN 114805075 B CN114805075 B CN 114805075B CN 202210665763 A CN202210665763 A CN 202210665763A CN 114805075 B CN114805075 B CN 114805075B
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ethylene glycol
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CN114805075A (en
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叶克印
高天禹
徐春发
杨健
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Jiangsu Fuji New Material Research Institute Co ltd
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    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
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Abstract

The invention discloses a synthesis method of bis [3, 3-di (3-tert-butyl-4-hydroxyphenyl) butyric acid ] ethylene diester, which comprises the following steps: heating and decompressing methyl acetoacetate and glycol under the protection of a solid basic catalyst and nitrogen, filtering, washing, removing the solid basic catalyst, taking filtrate I, and distilling to remove methanol, methyl acetoacetate and glycol to obtain an intermediate ethylene glycol diacetyl acetate; and then adding 2-tert-butylphenol into the ethylene glycol diacetoacetate, heating and carrying out reduced pressure reaction under the protection of a solid acid catalyst and nitrogen atmosphere, then filtering and washing to remove the solid acid catalyst, taking filtrate II, and distilling to remove the 2-tert-butylphenol, methanol and water to obtain a target product antioxidant O3. The synthesis method of the invention improves the reaction conversion rate, the yield and the purity of the target product, the raw materials and the catalyst can be recycled, and the process is safe, green and environment-friendly.

Description

Synthesis method of bis [3, 3-di (3-tert-butyl-4-hydroxyphenyl) butyric acid ] ethylene diester
Technical Field
The invention relates to a method for synthesizing bis [3, 3-di (3-tert-butyl-4-hydroxyphenyl) butyric acid ] ethylene ester, belonging to the technical field of antioxidants.
Background
Ethylene bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate ], also known as 1;3- (1, 1-dimethylethyl) -B- [3- (1, 1-dimethylethyl) -4-hydroxyphenyl ] -4-hydroxy-B-methylbenzoic acid 1, 2-ethylene ester, commonly known as antioxidant O3, is a hindered phenol antioxidant which has both antioxidant function and ultraviolet screening effect and is used in polyolefins, polyesters and the like. The reports on synthesizing the antioxidant O3 of bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid ] ethylene glycol are few, 2-tert-butylphenol, methyl acetoacetate and ethylene glycol are mainly used as raw materials, mercaptan and hydrogen chloride gas are used for catalyzing phenyl to react with ketone groups, and dibutyltin oxide is used for catalyzing ester groups to react with alcohol groups to obtain bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid ] ethylene glycol, but the hydrogen chloride gas has strong acidity and strong corrosivity and has extremely high requirements on production equipment and pipelines, the dibutyltin oxide is also a highly toxic substance, and leakage can cause serious safety accidents, so the equipment cost is high and the potential risk is high; at present, zhang Hejing and the like disclose new synthesis process research of an antioxidant O3 containing a semi-hindered phenol structure, and report that methyl acetoacetate and 2-tert-butylphenol are firstly used to generate an intermediate 3, 3-bis [ 3-tert-butyl-4-hydroxyphenyl ] methyl butyrate under the catalysis of dodecyl mercaptan/organic acid such as methanesulfonic acid, and the intermediate is reacted with ethylene glycol to generate the antioxidant O3, although methanesulfonic acid is used to replace hydrogen chloride gas and lithium methoxide is used to replace dibutyltin oxide, the equipment investment can be greatly reduced, and the safety risk can also be reduced, but methanesulfonic acid has weak acidity relative to hydrogen chloride, still has a strong corrosion effect on metallic iron, copper, lead and the like, has high requirements on production equipment and pipelines, and is low in equipment cost, and the yield of products is reduced by using methanesulfonic acid lithium as a catalyst.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a synthesis method of bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid ] ethylene diester, which can improve the reaction conversion rate, improve the yield and purity of a target product, does not need to additionally add an organic solvent, can recycle raw materials and a catalyst, greatly improves the safety of the process, reduces the equipment requirement and the production cost, is green and environment-friendly, and is suitable for industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme: a synthetic method of bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate ] ethylene glycol is characterized by comprising the following steps:
(1) Preparing an intermediate: using methyl acetoacetate and ethylene glycol as raw materials, heating to 120-135 ℃ under the protection of a solid basic catalyst and nitrogen atmosphere, preserving heat and reducing pressure to 0.06-0.09 MPa, then reacting for 5-8 h, and keeping for 1-2 h after the reaction is completed, so that methanol generated by ester exchange is completely discharged and recovered, then washing the catalyst after filtration, filtering at 40-55 ℃ under normal pressure, washing with methanol, removing the solid basic catalyst to obtain a filtrate I, and distilling to remove the methanol, the methyl acetoacetate and the ethylene glycol to obtain an intermediate ethylene glycol bisacetoacetate;
(2) Preparing a target product: adding 2-tert-butylphenol into the ethylene glycol bisacetoacetate, heating to 40-60 ℃ under the protection of a solid acid catalyst and nitrogen atmosphere, preserving heat and reducing pressure to 0.06-0.09 MPa, carrying out post reaction for 2-4 h, filtering at normal pressure and 40-60 ℃, washing with methanol, removing the solid acid catalyst to obtain a filtrate II, and distilling to remove the 2-tert-butylphenol, the methanol and the water to obtain a target product, namely bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate ] ethyl diester;
the solid basic catalyst is a B/C supported solid catalyst, wherein B represents an alkali metal oxide, and C represents an aluminum metal-containing carrier;
the solid acid catalyst is an A/D supported solid catalyst, wherein A represents a metal chloride composition, and D represents a carrier containing sulfonic acid groups.
In the step (1), the specific distillation process of the filtrate I comprises the following steps: heating the filtrate I to 80 ℃, distilling to remove methanol, recovering the methanol, heating to 130-145 ℃, preserving heat and reducing pressure to 0.025-0.04 MPa, distilling to remove methyl acetoacetate, recovering methyl acetoacetate, continuously raising the temperature to 145-155 ℃, preserving heat and reducing pressure to 0.012-0.02 MPa, distilling to remove glycol, and recovering the glycol to obtain an intermediate, namely ethylene glycol bisacetoacetate.
In the step (2), the filtrate II is filtered, the filtrate II is heated to 80 ℃, the methanol is removed by distillation, the methanol is recovered, the filtrate II is heated to 110-125 ℃, the temperature is kept and the pressure is reduced to 0.07-0.08 MPa, the water is removed by distillation, the filtrate II is heated to 160-175 ℃, the temperature is kept and the pressure is reduced to 0.006-0.011 MPa, the 2-tert-butylphenol is distilled off and removed, and the 2-tert-butylphenol is recovered, so that the target product of the bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate ] ethyl ester is obtained.
The molar ratio of methyl acetoacetate to ethylene glycol is 2.3 to 3.1, and the molar ratio of 2-tert-butylphenol to ethylene glycol is 4.5 to 5.3.
The addition amount of the solid basic catalyst is 1.5-2.5% by weight of methyl acetoacetate.
The addition amount of the solid acid catalyst is 2.5-4% of the weight of 2-tert-butylphenol.
In the above B/C supported solid catalyst, the alkali metal oxide B is Li 2 O、Na 2 O、Rb 2 O、CeO 2 And the like.
In the B/C supported solid catalyst, the aluminum metal-containing carrier C is a silicon-aluminum molecular sieve, montmorillonite or gamma-Al 2 O 3 And the like.
More closely, the loading amount of the alkali metal oxide B in the solid basic catalyst is 15-30%.
In the A/D supported solid catalyst, the metal chloride composition A is SnCl 4 With AlCl 3 、FeCl 3 、ZnCl 2 And the like.
More closely, the single-component SnCl4 accounts for 20 to 35 percent of the metal chloride composition A.
In the A/D supported solid catalyst, the carrier D containing sulfonic acid groups is one of polystyrene sulfonic acid resin, phenol formaldehyde sulfonic acid resin and the like.
Furthermore, the loading amount of the metal chloride composition A in the solid alkaline catalyst is 5-15%.
The invention has the beneficial effects that:
1. according to the synthesis method, methyl acetoacetate and ethylene glycol are used as raw materials, a solid basic catalyst is used for catalyzing and reacting to prepare an intermediate ethylene glycol bisacetoacetate, then 2-tert-butylphenol is added, and a solid acidic catalyst is used for catalyzing and reacting to prepare a target product bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate ] ethylene glycol, namely an antioxidant O3, wherein the solid basic catalyst and the solid acidic catalyst are easy to separate from a reaction system and can be recycled, and corrosion to equipment, pipelines and the like is avoided; meanwhile, the residual raw materials generated by the reaction can be separated and reused in the preparation of the target product, and an additional organic solvent is not required to be added, so that the economy and the environmental protection are very remarkable.
2. The solid alkaline catalyst provided by the invention is loaded on an aluminum metal carrier by using an alkali metal oxide, can effectively catalyze the reaction, is high in ethylene glycol conversion rate and less in residue, has a high yield of intermediate ethylene glycol bisacetoacetate, and is beneficial to improving the yield of a target product bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate ] ethylene glycol.
3. The solid acid catalyst of the invention is SnCl 4 With AlCl 3 、FeCl 3 、ZnCl 2 Etc. and can effectively catalyze the reaction, the intermediate product is very little, and the target bis [3, 3-di (3-tert-butyl-4-hydroxyphenyl) butyric acid is]The yield and the purity of the ethylene glycol are high.
4. The synthesis method disclosed by the invention can greatly improve the safety of the process, reduce the equipment requirement and the production cost, is green and environment-friendly, and is suitable for industrial production.
Drawings
FIG. 1 is a flow chart of the synthesis process of the present invention.
Detailed Description
In order to more clearly and completely illustrate the invention, the following examples are given by way of illustration and not by way of limitation.
Preparative example 1 preparation of solid basic catalyst
The preparation method comprises the following steps:
(1) Mixing silicon-aluminum molecular sieve, montmorillonite or gamma-Al 2 O 3 Calcining the solid basic catalyst in a muffle furnace at 700 ℃ for 6 hours for activation, then soaking the activated solid basic catalyst in dilute sulfuric acid solution for 24 to 6 hours, then centrifugally separating out solid particles, sequentially and thoroughly cleaning the solid particles by using water and absolute ethyl alcohol, and drying the solid particles in vacuum for 4 to 5 hours to prepare a solid basic catalyst carrier containing aluminum metal;
(2) Adding absolute ethyl alcohol into the carrier containing the aluminum metal, then adding lithium hydroxide, sodium hydroxide, rubidium hydroxide or cerium hydroxide into the carrier, and stirring the mixture for 3 to 4 hours under reflux. Filtering, washing with anhydrous ethanol for 3 times, vacuum drying at 75 deg.C for 10 hr, and calcining in muffle furnace at 550 deg.C for 3 hr to obtain solid basic catalyst, i.e. B/C supported solid catalyst, wherein B represents alkali metal oxide and C represents aluminum metal-containing carrier; in the prepared solid basic catalyst, the loading capacity of the alkali metal oxide B in the solid basic catalyst is 15-30%;
(3) Grinding the obtained solid basic catalyst to obtain the solid basic catalyst with the grain diameter of 40-60 meshes for later use.
Preparative example 2 preparation of solid basic catalyst
The preparation method comprises the following steps:
(1) Washing one of polystyrene sulfonic acid resin or phenolic aldehyde sulfonic acid resin by pure water until the resin is not turbid, adding the resin into 95% ethanol for soaking for 4-5 h, removing impurities, washing by pure water to remove the ethanol, adding the resin into a dilute hydrochloric acid solution for soaking for 30-36 h for activation treatment, then washing by pure water, removing most of water at normal temperature, and performing vacuum drying at 80-85 ℃ for 24h to prepare a carrier containing sulfonic groups of the solid acidic catalyst;
the styrene sulfonic acid resin can be styrene sulfonic acid resin D001-CC, styrene sulfonic acid resin DO72 and the like, and the phenolsulfonic acid resin can be phenolsulfonic acid resin SMP-I, phenolsulfonic acid resin SMP-II and the like;
(2) Adding one of anhydrous aluminum trichloride, anhydrous ferric chloride or zinc dichloride into an anhydrous ethanol solution, stirring, adding anhydrous stannic chloride, adding a carrier containing sulfonic groups of the solid acid catalyst into the anhydrous ethanol solution, refluxing for 3-4 h, cooling to room temperature, filtering, washing with anhydrous ethanol and acetone for multiple times, standing for 1-2 h, and vacuum drying at 80-85 ℃ for 48-60 h to prepare the solid acid catalyst, namely an A/D supported solid catalyst, wherein A represents a metal chloride composition, and D represents a carrier containing sulfonic groups; in the prepared solid acid catalyst, the loading capacity of the metal chloride composition A in the solid base catalyst is 5-15%, and single-component SnCl 4 The proportion of the metal chloride composition A is 20 to 35 percent;
(3) Grinding the obtained solid acid catalyst to obtain the solid acid catalyst with the particle size of 40-60 meshes for later use.
Example 1
(1) Preparation of ethylene glycolBis (acetoacetic acid ester): 266.8g of methyl acetoacetate and 62g of ethylene glycol were put in a three-necked flask, and 4.01g of Li was added thereto with stirring 2 O/Si-Al molecular sieve supported solid catalyst, wherein, li 2 The load capacity of O in a solid alkaline catalyst is 15%, nitrogen is filled for replacement, the solid alkaline catalyst is heated to 120 ℃, the temperature is kept and the pressure is reduced to 0.06MPa, the subsequent reaction is carried out for 5 hours, the generated methanol is distilled and removed at the same time, the methanol is kept for 1 hour to be completely discharged, the methanol is recovered, the solid alkaline catalyst or the solid acidic catalyst which can be used for washing the subsequent filtration is filtered at normal pressure at 40 ℃, the methanol is used for washing, the solid alkaline catalyst is removed, a filtrate I is taken and added into a three-neck flask, then the three-neck flask is heated to 80 ℃, the methanol is distilled and removed, the temperature is heated to 130 ℃, the temperature is kept and the pressure is reduced to 0.04MPa, the methyl acetoacetate is removed by distillation, the temperature is heated to 145 ℃, the temperature is kept and the pressure is reduced to 0.012MPa, the ethylene glycol is removed by distillation, the residual intermediate is determined by nuclear magnetic resonance and is ethylene glycol bisacetoacetate, the purity of the methanol is greater than 99.9 percent, the purity of the methyl acetoacetate is greater than 99 percent by high performance liquid chromatography, the 46.98g is recovered, the purity of the ethylene glycol bisacetoacetate is greater than 99 percent, the purity of the 99.74 percent, the conversion of the ethylene glycol is greater than 8;
(2) Preparation of bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid]And (2) ethylene ester: 675g of 2-tert-butylphenol was added to the above ethylene glycol bisacetoacetate, and stirred, and 16.9g of SnCl was added 4 -AlCl 3 /polystyrene sulfonic acid resin supported solid acid catalyst, wherein SnCl 4 Occupied SnCl 4 -AlCl 3 20% of SnCl 4 -AlCl 3 Charging nitrogen gas for replacement when the loading amount of the solid acid catalyst is 5%, heating to 40 ℃, preserving heat and reducing pressure to 0.06MPa, reacting for 2h, filtering at 40 ℃ under normal pressure, flushing with methanol to remove the solid acid catalyst, taking filtrate II, adding into a three-neck flask, heating to 80 ℃, distilling to remove methanol and recovering, heating to 110 ℃, preserving heat and reducing pressure to 0.07MPa, distilling to remove water, heating to 160 ℃, preserving heat and reducing pressure to 0.006MPa, distilling to remove 2-tert-butylphenol, and determining the residual target product as bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) through nuclear magnetic resonance) Butyric acid]Determining the purity of the ethylene glycol by high performance liquid chromatography, wherein the purity of the methanol is more than 99.9 percent, the purity of the 2-tert-butylphenol is more than 99 percent, recovering 106.59g, and obtaining a target product, namely bis [3, 3-di (3-tert-butyl-4-hydroxyphenyl) butyric acid]The yield of the ethylene glycol is 94.72 percent, and the purity is 98.9 percent.
Example 2
(1) Preparation of ethylene glycol diacetoacetate: 290g of methyl acetoacetate and 62g of ethylene glycol were put into a three-necked flask, stirred, and 5.8g of Na was added 2 O/montmorillonite supported solid catalyst, wherein, na 2 The loading capacity of O in a solid alkaline catalyst is 20%, nitrogen is filled for replacement, the mixture is heated to 130 ℃, the mixture is subjected to heat preservation and pressure reduction to 0.07MPa, the subsequent reaction is carried out for 6 hours, the mixture is continuously maintained for 1.5 hours, the mixture is filtered at 50 ℃ under normal pressure and is washed by methanol, filtrate I is taken and added into a three-neck flask, the mixture is heated to 80 ℃, the methanol is removed, the mixture is heated to 135 ℃, the mixture is subjected to heat preservation and pressure reduction to 0.03MPa, methyl acetoacetate is removed, the mixture is heated to 150 ℃, the mixture is subjected to heat preservation and pressure reduction to 0.016MPa, ethylene glycol is removed, and an intermediate ethylene glycol bisacetoacetate is remained, the purity of the methanol is more than 99.9%, the purity of the methyl acetoacetate is more than 99%, 71.15g of recovered, the purity of the ethylene glycol is more than 99%, the conversion rate is 94.32%, and the purity of the ethylene glycol bisacetoacetate is 99.9% as measured by high performance liquid chromatography;
(2) Preparation of bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid]Ethylene glycol: 720g of 2-tert-butylphenol was added to the above ethylene glycol bisacetoacetate, and the mixture was stirred, and 21.6g of SnCl was added 4 -FeCl 3 Phenol formaldehyde sulfonic acid resin supported solid acid catalyst, wherein SnCl 4 Occupied SnCl 4 -FeCl 3 25% of SnCl 4 -FeCl 3 Filling nitrogen for replacement when the loading amount of the solid acid catalyst is 8%, heating to 50 ℃, preserving heat and reducing pressure to 0.075MPa, carrying out post reaction for 3h, filtering at 50 ℃ under normal pressure, washing with methanol to remove the solid acid catalyst, taking filtrate II, adding the filtrate II into a three-neck flask, heating to 80 ℃, removing methanol, heating to 120 ℃, preserving heat and reducing pressure to 0.075MPa, removing water, heating to 165 ℃, preserving heat and reducing pressure to 0.0075MPa, and removing 2-tert-butylphenol to obtain the target product bis [ 2 ], [ bis [ 2 ] ]3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid]The purity of the ethylene glycol is more than 99.9 percent and the purity of the 2-tert-butylphenol is more than 99 percent, the recovery amount is 154.29g, and the target product is bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid]The yield of the ethylene glycol is 94.30 percent, and the purity is 98.5 percent.
Example 3
(1) Preparation of ethylene glycol bisacetoacetate: 324.8g of methyl acetoacetate and 62g of ethylene glycol were put in a three-necked flask, and 8.1g of gRb was added thereto with stirring 2 O/γ-Al 2 O 3 Supported solid catalyst of which Rb 2 The loading capacity of O in a solid alkaline catalyst is 25%, nitrogen is filled for replacement, the mixture is heated to 130 ℃, the mixture is subjected to heat preservation and pressure reduction to 0.08MPa, the mixture is subjected to post-reaction for 7 hours, the mixture is kept for 2 hours, the mixture is filtered at 55 ℃ under normal pressure and is washed by methanol, filtrate I is taken and added into a three-neck flask, the mixture is heated to 80 ℃, methanol is removed, the mixture is heated to 140 ℃, the mixture is subjected to heat preservation and pressure reduction to 0.035MPa, methyl acetoacetate is removed, the mixture is heated to 155 ℃, the mixture is subjected to heat preservation and pressure reduction to 0.02MPa, glycol is removed, and the intermediate glycol diacetate is remained, the purity of the methanol is more than 99.9 percent, the purity of the methyl acetoacetate is more than 99 percent, 105.91g of recovered, the purity of the glycol is more than 99 percent, the conversion rate is 94.44 percent, and the purity of the glycol diacetate is 99.9 percent as determined by high performance liquid chromatography;
(2) Preparation of bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid]Ethylene glycol: 795g of 2-tert-butylphenol was added to the above ethylene glycol bisacetoacetate, and the mixture was stirred, followed by addition of 27.83g of SnCl 4 -ZnCl 2 /polystyrene sulfonic acid resin supported solid acid catalyst, wherein SnCl 4 Occupied SnCl 4 -ZnCl 2 30% of SnCl 4 -ZnCl 2 Charging nitrogen for replacement when the loading amount of the solid acid catalyst is 10%, heating to 60 ℃, preserving heat and reducing pressure to 0.09MPa, carrying out post-reaction for 4h, filtering at 60 ℃ under normal pressure, flushing with methanol, removing the solid acid catalyst, taking filtrate II, adding into a three-neck flask, heating to 80 ℃, removing methanol, heating to 125 ℃, preserving heat and reducing pressure to 0.08MPa, removing water, heating to 170 ℃, preserving heat and reducing pressure to 0.00 DEG CRemoving 2-tert-butylphenol under 95MPa to obtain a target product bis [3, 3-di (3-tert-butyl-4-hydroxyphenyl) butyric acid]The purity of the ethyl ester is more than 99.9 percent and the purity of the 2-tert-butylphenol is more than 99 percent through high performance liquid chromatography determination, 228.37g is recovered, and the target product is bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid]The yield of the ethylene glycol is 94.43 percent, and the purity is 98.6 percent.
Example 4
(1) Preparation of ethylene glycol diacetoacetate: 359.6g of methyl acetoacetate and 62g of ethylene glycol were put into a three-necked flask, and 6.45g of CeO was added thereto with stirring 2 /γ-Al 2 O 3 Supported solid catalyst of which CeO 2 Filling nitrogen for replacement when the loading capacity of a solid basic catalyst is 24%, heating to 135 ℃, preserving heat and reducing pressure to 0.09MPa, then reacting for 8 hours, continuing to keep for 2 hours, filtering at 55 ℃ under normal pressure, flushing with methanol, taking filtrate I, adding the filtrate I into a three-neck flask, then heating to 80 ℃, removing methanol, heating to 145 ℃, preserving heat and reducing pressure to 0.04MPa, removing methyl acetoacetate, heating to 155 ℃, preserving heat and reducing pressure to 0.02MPa, removing ethylene glycol, and leaving an intermediate ethylene glycol diacetate, wherein the purity of methanol is more than 99.9%, the purity of methyl acetoacetate is more than 99%, the recovery amount of 138.4g, the purity of ethylene glycol is more than 99%, the conversion rate of 95.34%, and the purity of ethylene glycol diacetate is 99.9% measured by high performance liquid chromatography;
(2) Preparation of bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid]Ethylene glycol: 795g of 2-tert-butylphenol was added to the above ethylene glycol bisacetoacetate, and after stirring, 27.83g of SnCl was added 4 -ZnCl 2 Phenol formaldehyde sulfonic acid resin supported solid acid catalyst, wherein SnCl 4 Occupied SnCl 4 -ZnCl 2 30% of SnCl 4 -ZnCl 2 Charging nitrogen for replacement when the loading amount of the solid acid catalyst is 10%, heating to 60 ℃, preserving heat and reducing pressure to 0.08MPa, carrying out post reaction for 3h, filtering at 60 ℃ under normal pressure, flushing with methanol, removing the solid acid catalyst, taking filtrate II, adding into a three-neck flask, heating to 80 ℃, removing methanol, heating to 125 ℃, preserving heat and reducing pressure to 0.08MPa, removing methanolRemoving water, heating to 175 ℃, keeping the temperature and reducing the pressure to 0.011MPa, removing the 2-tert-butylphenol, and obtaining the target product bis [3, 3-di (3-tert-butyl-4-hydroxyphenyl) butyric acid]The purity of the ethyl ester is more than 99.9 percent and the purity of the 2-tert-butylphenol is more than 99 percent through high performance liquid chromatography determination, 177.93g of the ethylene ester is recovered, and the target product is bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid]The yield of the ethylene glycol was 95.33% and the purity 98.4%.
Example 5
(1) Preparation of ethylene glycol diacetoacetate: 324.8g of methyl acetoacetate and 62g of ethylene glycol were put into a three-necked flask, and 6.5g of Li was added thereto with stirring 2 O/montmorillonite supported solid catalyst, wherein, li 2 The loading capacity of O in a solid alkaline catalyst is 30 percent, nitrogen is filled for replacement, the mixture is heated to 125 ℃, the mixture is subjected to heat preservation and pressure reduction to 0.08MPa, the mixture is subjected to reaction for 6 hours, the mixture is continuously kept for 2 hours, the mixture is filtered at 55 ℃ under normal pressure, the filtered solution is washed by methanol, filtrate I is taken and added into a three-neck flask, the heated mixture is heated to 80 ℃, the methanol is removed, the heated mixture is heated to 135 ℃, the heat preservation and pressure reduction is carried out to 0.03MPa, the methyl acetoacetate is removed, the heated mixture is heated to 145 ℃, the heat preservation and pressure reduction is carried out to 0.015MPa, the ethylene glycol is removed, and the intermediate ethylene glycol diacetate is left, the purity of the methanol is more than 99.9 percent, the purity of the methyl acetoacetate is more than 99 percent, 102.63g of the recovered, the purity of the ethylene glycol is more than 99 percent, the conversion rate is 95.74 percent, and the purity of the ethylene glycol diacetate is 99.7 percent;
(2) Preparation of bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid]And (2) ethylene ester: 690g of 2-tert-butylphenol was added to the above ethylene glycol bisacetoacetate, and the mixture was stirred, 17.25g of SnCl was added 4 -AlCl 3 /polystyrene sulfonic acid resin supported solid acid catalyst, wherein SnCl 4 Occupied SnCl 4 -AlCl 3 20% of SnCl 4 -AlCl 3 Charging nitrogen gas for replacement when the loading amount of the solid acid catalyst is 5%, heating to 55 deg.C, maintaining the temperature and reducing the pressure to 0.08MPa, reacting for 3h, filtering at 60 deg.C under normal pressure, washing with methanol to remove the solid acid catalyst, collecting filtrate II, adding into a three-necked flask, heating to 80 deg.C, removing methanol, heating to 120 deg.CMaintaining the temperature and reducing the pressure to 0.075MPa, removing water, heating to 170 ℃, maintaining the temperature and reducing the pressure to 0.008MPa, removing 2-tert-butylphenol, and obtaining a target product, namely bis [3, 3-di (3-tert-butyl-4-hydroxyphenyl) butyric acid]The purity of the ethylene glycol is more than 99.9 percent and the purity of the 2-tert-butylphenol is more than 99 percent, the recovery amount is 115.51g, and the target product is bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid]The yield of the ethylene glycol was 95.73% and the purity 98.7%.
Comparative example 1
(1) Preparation of ethylene glycol bisacetoacetate: 255.2g of methyl acetoacetate and 62g of ethylene glycol were put into a three-necked flask, and 6.68g of Li was added thereto with stirring 2 O/Si-Al molecular sieve supported solid basic catalyst, in which Li 2 The loading capacity of O in a solid alkaline catalyst is 14 percent, nitrogen is filled for replacement, the mixture is heated to 120 ℃, the temperature is kept and the pressure is reduced to 0.06MPa, the mixture reacts for 5 hours, the mixture is kept for 1 hour, the mixture is filtered under normal pressure at 40 ℃, methanol is used for washing, the solid alkaline catalyst is removed, filtrate I is taken and added into a three-neck flask, the mixture is heated to 80 ℃, the methanol is distilled and removed, the mixture is heated to 130 ℃, the temperature is kept and the pressure is reduced to 0.04MPa, methyl acetoacetate is distilled and removed, the mixture is heated to 145 ℃, the temperature is kept and the pressure is reduced to 0.012MPa, glycol is distilled and removed, the purity of methanol is more than 99.9 percent, the purity of methyl acetoacetate is more than 99 percent, 46.94g of recovered, the purity of glycol is more than 99 percent, the conversion rate is 89.74 percent, and the purity of glycol diacetate is 99.8 percent;
(2) Preparation of bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid]And (2) ethylene ester: 600g of 2-tert-butylphenol was added to the above ethylene glycol bisacetoacetate, and stirred, 15.84g of SnCl was added 4 -AlCl 3 /polystyrene sulfonic acid resin supported solid acid catalyst, wherein SnCl 4 Occupied SnCl 4 -AlCl 3 18% of SnCl 4 -AlCl 3 Charging nitrogen gas for replacement when the loading amount of the solid acid catalyst is 4%, heating to 40 deg.C, maintaining the temperature, reducing the pressure to 0.06MPa, reacting for 2h, filtering at 40 deg.C under normal pressure, washing with methanol to remove the solid acid catalyst, collecting filtrate II, adding into a three-neck flask, and filteringHeating to 80 ℃, distilling to remove methanol and recovering, heating to 110 ℃, preserving heat and reducing pressure to 0.07MPa, distilling to remove water, heating to 160 ℃, preserving heat and reducing pressure to 0.006MPa, distilling to remove 2-tert-butylphenol, determining by high performance liquid chromatography that the purity of methanol is more than 99.9 percent, the purity of 2-tert-butylphenol is 97.8 percent, recovering 125.3g, and obtaining the target product bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid]The yield of the ethylene glycol is 89.24 percent, and the purity is 97.8 percent.
In this comparative example 1, compared with example 1, in the case of the same ethanol addition, the addition amounts of methyl acetoacetate and 2-tert-butylphenol were reduced, the solid basic catalyst and the solid acidic catalyst were also reduced, and the loading amounts of the alkali metal oxide B in the solid basic catalyst, the metal chloride composition a in the solid basic catalyst and the single-component SnCl4 in the metal chloride composition a were also reduced, and it was found that the conversion of ethylene glycol was reduced to 89.74%, the yield of the target product, bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid ] ethylene diester, was reduced to less than 90%, and the purity of the target product was also reduced.
Comparative example 2
(1) Preparation of ethylene glycol bisacetoacetate: 371.2g of methyl acetoacetate and 62g of ethylene glycol were put into a three-necked flask, and 6.68g of CeO was added thereto with stirring 2 /γ-Al 2 O 3 Supported solid basic catalyst, wherein CeO 2 Filling nitrogen for replacement when the loading capacity of a solid basic catalyst is 32%, heating to 135 ℃, preserving heat and reducing pressure to 0.09MPa, then reacting for 8 hours, continuing to keep for 2 hours, filtering at 55 ℃ under normal pressure, flushing with methanol, taking filtrate I, adding the filtrate I into a three-neck flask, then heating to 80 ℃, removing methanol, heating to 145 ℃, preserving heat and reducing pressure to 0.04MPa, removing methyl acetoacetate, heating to 155 ℃, preserving heat and reducing pressure to 0.02MPa, removing ethylene glycol, and leaving an intermediate ethylene glycol diacetate, wherein the purity of methanol is more than 99.9%, the purity of methyl acetoacetate is more than 99%, the recovery amount of 150.45g, the purity of ethylene glycol is more than 99%, the conversion rate is 95.14%, and the purity of ethylene glycol diacetate is 99.8% measured by high performance liquid chromatography;
(2) Preparation of bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid]And (2) ethylene ester: 810g of 2-tert-butylphenol was added to the above ethylene glycol bisacetoacetate, and then stirred, 32.4g of SnCl was added 4 -ZnCl 2 /polystyrene sulfonic acid resin supported solid acid catalyst, wherein SnCl 4 Occupied SnCl 4 -ZnCl 2 Is 36 percent, snCl 4 -ZnCl 2 Filling nitrogen for replacement when the loading amount of the solid acid catalyst is 16 percent, heating to 60 ℃, preserving heat and reducing pressure to 0.08MPa, carrying out post reaction for 3 hours, filtering at 60 ℃ under normal pressure, flushing with methanol to remove the solid acid catalyst, taking filtrate II, adding the filtrate II into a three-neck flask, heating to 80 ℃, removing methanol, heating to 125 ℃, preserving heat and reducing pressure to 0.08MPa, removing water, heating to 175 ℃, preserving heat and reducing pressure to 0.011MPa, removing 2-tert-butylphenol, and obtaining a target product, namely bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid]The purity of the ethyl ester is more than 99.9 percent and the purity of the 2-tert-butylphenol is more than 99 percent, the recovery amount is 238.9g, and the target product is bis [3, 3-di (3-tert-butyl-4-hydroxyphenyl) butyric acid]The yield of the ethylene glycol is 95.08 percent, and the purity is 98.5 percent.
In this comparative example 2, compared with example 4, in the same case of ethanol addition, the addition amount of methyl acetoacetate and 2-tert-butylphenol was increased, the solid basic catalyst and the solid acidic catalyst were decreased, and the loading amount of the alkali metal oxide B in the solid basic catalyst, the loading amount of the metal chloride composition a in the solid basic catalyst and the proportion of single-component SnCl4 in the metal chloride composition a were decreased, and it was found that the conversion rate of ethylene glycol and the yield and purity of the target product bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid ] ethylene glycol were increased, but not significantly increased.
Comparative example 3
This comparative example 3 differs from example 1 in that the solid acid catalyst was selected as a solid catalyst for polystyrene sulfonic acid resin, and after recovery: 196.3g of 2-tert-butylphenol was recovered, and the recovery was more than 100%, which indicated that the product contained impurities, comprising unreacted intermediate ethylene glycol bisacetoacetate, and the desired product ethylene bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate ] was 83.75% in yield and 95.3% in purity.
Comparative example 4
This comparative example 4 differs from example 1 in that the solid acid catalyst was selected as AlCl 3/polystyrene sulfonic acid resin supported solid catalyst, and after recovery: 187.97g of 2-tert-butylphenol was recovered, and the recovery rate was more than 100%, which indicated that the product contained impurities, comprising unreacted intermediate ethylene glycol bisacetoacetate, and the target product ethylene bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate ] was 84.77% in yield and 96.4% in purity.
Comparative example 5
Comparative example 5 differs from example 1 in that the solid acid catalyst was chosen to be SnCl 4 Polystyrene sulfonic acid resin supported solid catalyst, after recovery: 152.4g of 2-tert-butylphenol was recovered, and the recovery rate was more than 100%, which indicated that the product contained impurities, i.e., unreacted intermediate ethylene glycol bisacetoacetate, and the target product, i.e., bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid]The yield of the ethylene glycol is 89.2 percent, and the purity is 97.2 percent.
Comparative examples 3 to 5 yield of the target product ethylene bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate ] was reduced to less than 90% and purity was also reduced to less than 98% as compared to example 1.
Comparative example 6
Comparative example 6 differs from example 1 in that the solid basic catalyst was selected to be Li 2 O/SiO 2 The purity of the ethylene glycol is more than 99 percent after the supported solid catalyst is recovered, the conversion rate is 83.46 percent, and the target product is bis [3, 3-di (3-tert-butyl-4-hydroxyphenyl) butyric acid]The yield of the ethylene glycol was 83.44% and the purity was 98.5%.
Comparative example 6 has a decreased conversion of ethylene glycol compared to example 1, resulting in a decreased yield of the target product ethylene bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butanoate ].
Finally, it should be noted that the above embodiments are only used for illustrating and not limiting the technical solutions of the present invention, and although the present invention is described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the present invention can be modified or replaced with equivalents without departing from the spirit and scope of the present invention, and all modifications or partial replacements should be covered in the claims of the present invention.

Claims (6)

1. A synthetic method of bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate ] ethylene glycol is characterized by comprising the following steps:
(1) Preparing an intermediate: heating methyl acetoacetate and ethylene glycol serving as raw materials to 120-135 ℃ under the protection of a solid basic catalyst and nitrogen atmosphere, preserving heat and reducing pressure to 0.06-0.09MPa, then reacting for 5-8 h, keeping for 1-2h after the reaction is completed, filtering at normal pressure and 40-55 ℃, washing with methanol to remove the solid basic catalyst, taking filtrate I, and distilling to remove the methanol, the methyl acetoacetate and the ethylene glycol to obtain an intermediate ethylene glycol diacetyl acetate;
(2) Preparing a target product: adding 2-tert-butylphenol into the ethylene glycol diacetyl ester, heating to 40 to 60 ℃ under the protection of a solid acidic catalyst and nitrogen, preserving heat and reducing pressure to 0.06 to 0.09MPa, reacting for 2 to 4 hours, filtering at the temperature of 40 to 60 ℃ under normal pressure, washing with methanol, removing the solid acidic catalyst, taking a filtrate II, and distilling to remove the 2-tert-butylphenol, the methanol and water to obtain a target product, namely bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid ] ethylene diester;
the solid basic catalyst is a B/C supported solid catalyst, wherein B represents an alkali metal oxide, and C represents an aluminum metal-containing carrier;
the solid acid catalyst is an A/D supported solid catalyst, wherein A represents a metal chloride composition, and D represents a carrier containing sulfonic acid groups;
the addition amount of the solid basic catalyst is 1.5 to 2.5 percent of the weight of methyl acetoacetate;
the addition amount of the solid acidic catalyst is 2.5 to 4 percent of the weight of 2-tert-butylphenol;
in the solid basic catalyst, the alkali metal oxide B is Li 2 O、Na 2 O、Rb 2 O、CeO 2 One kind of (1); the carrier C containing the aluminum metal is a silicon-aluminum molecular sieve, montmorillonite or gamma-Al 2 O 3 One of (a) or (b);
in the solid acid catalyst, the metal chloride composition A is SnCl 4 With AlCl 3 、FeCl 3 、ZnCl 2 A combination of (a); the carrier D containing sulfonic group is one of polystyrene sulfonic acid resin and phenol formaldehyde sulfonic acid resin.
2. The method for synthesizing ethylene bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate ] according to claim 1, wherein the molar ratio of methyl acetoacetate to ethylene glycol is 2.3 to 3.1, and the molar ratio of 2-tert-butylphenol to ethylene glycol is 4.5 to 5.3.
3. The method for synthesizing bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate ] ethylene glycol according to claim 1, wherein the loading amount of the alkali metal oxide B in the solid basic catalyst is 15 to 30%.
4. The method for synthesizing bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate ] ethylene glycol according to claim 1, wherein the loading amount of the metal chloride composition A in the solid basic catalyst is 5-15%.
5. The synthesis method of ethylene bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate ] according to claim 1, wherein the mass percentage of the single-component SnCl4 in the metal chloride composition A is 20 to 35%.
6. The method for synthesizing bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid ] ethylene ester according to claim 1, wherein the specific distillation process of the filtrate I in the step (1) is: heating the filtrate I to 80 ℃, distilling off methanol, recovering, heating to 130-145 ℃, preserving heat and reducing pressure to 0.025-0.04MPa, distilling off methyl acetoacetate, recovering, continuing to raise the temperature to 145-155 ℃, preserving heat and reducing pressure to 0.012-0.02MPa, distilling off glycol, and recovering to obtain an intermediate ethylene glycol bisacetoacetate;
in the step (2), heating the filtrate II to 80 ℃, distilling out methanol, recovering, heating to 110 to 125 ℃, keeping the temperature and reducing the pressure to 0.07 to 0.08MPa, distilling to remove water, heating to 160 to 175 ℃, keeping the temperature and reducing the pressure to 0.006 to 0.011MPa, distilling out 2-tert-butylphenol, and recovering to obtain the target product, namely the bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid ] diester.
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