CN112876363A - Preparation method of pentaerythritol tetraisooctanoate - Google Patents
Preparation method of pentaerythritol tetraisooctanoate Download PDFInfo
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Abstract
The invention discloses a preparation method of pentaerythritol tetraisooctanoate, which comprises the following steps: step one, synthesizing pentaerythritol tetraisooctoate: uniformly mixing pentaerythritol, isooctanoic acid and a catalyst according to mass fraction, adding the mixture into a reaction vessel, stirring at 200-; step two, centrifuging a pentaerythritol tetraisooctoate crude product: step three, post-treatment: washing the mixed solution of pentaerythritol tetraisooctoate with 5% aqueous alkali, separating with a separating funnel to obtain an oil phase, and washing to obtain pentaerythritol tetraisooctoate; step four, drying pentaerythritol tetraisooctoate: and adding the water removing agent into the pentaerythritol tetraiso-octoate, and separating the water removing agent through vacuum filtration after water removal to obtain the pentaerythritol tetraiso-octoate product. The pentaerythritol tetraisooctanoate prepared by the method has higher esterification rate and higher purity.
Description
Technical Field
The invention relates to fine chemical engineering, in particular to a preparation method of pentaerythritol tetraisooctanoate.
Background
Pentaerythritol tetraisooctanoate is a pale yellow oily liquid, and is widely used in the field of lubricant base oil due to good abrasion resistance, wear resistance and thermal stability.
However, in the process of preparing pentaerythritol tetraisooctanoate by esterification of pentaerythritol and isooctanoic acid, the conventional method is usually prepared by catalytic dehydration with strong acid such as concentrated sulfuric acid, and due to steric hindrance of pentaerythritol, the esterification rate is low, and the strong acid catalyst is more corrosive to equipment, which is not favorable for industrial production.
CN201310546287.3 discloses a process for synthesizing ethyl acetate and a refining method thereof, wherein ethanol, concentrated sulfuric acid and acetic acid are pumped into a reaction kettle according to a certain formula proportion, a small amount of zeolite catalyst is added, then water bath heating is carried out, generated ethyl acetate gas is introduced into a container through condensation, an equal amount of deionized water is added, the mixture is uniformly mixed, water bath evaporation is carried out, and the evaporated gas is dried by dried calcium chloride and condensed to obtain ethyl acetate. The invention takes ethanol and acetic acid as raw materials, synthesizes ethyl acetate under the action of the catalyst, has controllable process, rich raw materials, high product yield and good quality. CN201310195417.3 discloses a novel process for synthesizing ethyl acetate. The method specifically utilizes differential pressure thermal coupling to be combined with a reactive distillation dividing wall tower technology, simplifies the original flow by utilizing the dividing wall tower technology and saves equipment investment, and utilizes differential pressure operation of the top and the bottom of the dividing wall tower to finish heat exchange between the steam at the top of the tower and the distillate at the bottom of the tower by utilizing the differential pressure thermal coupling technology, thereby realizing large-scale energy coupling and saving energy consumption.
CN00123253.3 discloses a preparation method of ethyl acetate. The process is that ethanol and acetic acid in crude products of ethanol, acetic acid, acetaldehyde and other two-carbon oxygen-containing compounds synthesized from synthesis gas (H2+ CO) are directly esterified and distilled and separated to prepare ethyl acetate products. The advantages are that: the raw material source is rich, no grain and petroleum resource which is increasingly tense are consumed, the production cost is reduced, the boiling point of acetaldehyde in the synthesized crude product is much lower than that of other components, pure acetaldehyde products can be conveniently obtained by distillation and separation before or during esterification, and the acetaldehyde can be converted into ethyl acetate products by utilizing a mature disproportionation condensation technology.
The raw material pentaerythritol is prepared by reacting formaldehyde and acetaldehyde as raw materials in the presence of an alkaline catalyst. The alkaline catalyst is generally calcium hydroxide or sodium hydroxide, and metal ions are brought into the pentaerythritol tetraisooctanoate product along with the addition of pentaerythritol, thereby inevitably affecting the purity of the product.
In the prior art, concentrated sulfuric acid and other super-strong acid are generally adopted to catalyze esterification reaction, the esterification rate is low, the product performance is poor, and the performance stability of pentaerythritol tetraisooctanoate in the use process of lubricating oil is influenced.
Disclosure of Invention
The invention provides a preparation method of pentaerythritol tetraisooctanoate, and the pentaerythritol tetraisooctanoate obtained by the method has higher esterification rate and higher purity.
The preparation method of pentaerythritol tetraisooctoate is characterized by comprising the following steps:
step one, synthesizing pentaerythritol tetraisooctoate: uniformly mixing 136 parts of pentaerythritol, 690-750 parts of isooctanoic acid and 17.2-21.5 parts of a boron-containing catalyst according to mass fraction, adding into a reaction vessel, stirring at 300r/min under 200-;
step two, centrifuging a pentaerythritol tetraisooctoate crude product: centrifuging the crude pentaerythritol tetraiso-octoate product at the centrifuge rotation speed of 8000-30000r/min for 10-20min to obtain a boron-containing catalyst and a pentaerythritol mixed solution, drying the boron-containing catalyst and then recovering the boron-containing catalyst, wherein the pentaerythritol tetraiso-octoate mixed solution is reserved;
step three, post-treatment: washing the mixed solution of pentaerythritol tetraiso-octoate with 5% aqueous alkali, separating with a separating funnel to obtain an oil phase, repeatedly washing for 4-8 times, washing with water and saturated salt solution for 4-8 times according to the same method to obtain pentaerythritol tetraiso-octoate;
step four, drying pentaerythritol tetraisooctoate: and adding 90-120 parts of a water removing agent into the pentaerythritol tetraiso-octoate according to the mass parts, and separating the water removing agent through vacuum filtration after water removal to obtain the pentaerythritol tetraiso-octoate product.
Preferably, the preparation method of the boron-containing catalyst in the step one comprises the following steps:
step A, preparing emulsion: uniformly mixing 30-50 parts of sodium propylene sulfonate, 54-73 parts of styrene, 0.1-0.5 part of 4- (3-allylthiourea) benzoic acid, 0.1-0.5 part of 1-butenylboronic acid and 2-6 parts of an emulsifier according to the mass parts, adding into a three-neck flask, and dispersing at the normal temperature of 300-;
step B, preparation of polymer: adding 0.3-0.4 part of initiator and 0.01-0.05 part of retarder into the emulsion according to the mass parts, and heating to 80-100%oC, stirring at the rotation speed of 200-400r/min, reacting for 0.6-1.2h, then adding 0.6-0.8 part of initiator, reacting for 1.2-2.4h, stopping the reaction, and cooling to room temperature to obtain a polymer mixture;
step C, preparing a boron-containing catalyst by acidification: adding 35-50 parts by mass of concentrated hydrochloric acid with the concentration of 36% into the polymer mixture, acidifying for 1-2h, filtering, washing and drying to obtain the boron-containing catalyst.
Preferably, the emulsifier in the preparation process of the boron-containing catalyst is one or a combination of several of sodium dodecyl sulfate, sodium dodecyl diphenyl ether disulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and ammonium dodecyl sulfate.
Preferably, the initiator in the preparation process of the boron-containing catalyst is one or a combination of more of potassium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, dicumyl peroxide, benzoyl peroxide and dimethyl azodiisobutyrate.
Preferably, the retarder in the preparation process of the boron-containing catalyst is one or a combination of hydroquinone, DPPH, benzoquinone, aniline and MEHQ.
Preferably, the alkali in the third step is one or a combination of several of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate and sodium bicarbonate.
Preferably, the water removing agent in the fourth step is one or a combination of more of 4A molecular sieve, anhydrous sodium sulfate, phosphorus pentoxide, anhydrous calcium chloride, anhydrous calcium sulfate and anhydrous potassium carbonate.
In the preparation process of the boron-containing catalyst, the mechanism of partial polymerization reaction is shown as follows:
compared with the prior art, the invention has the beneficial effects that:
1. by adopting a self-made boron-containing catalyst, a polymer skeleton contains sulfonic acid groups, boric acid groups, carboxyl groups and sulfydryl groups, the catalytic activity is ideal, the selectivity is high, byproducts are greatly reduced, the esterification rate is greatly improved, the purity of the product is high, the esterification rate of the obtained pentaerythritol tetraisooctanoate is 99.5 percent, the purity is 99.9 percent, the water content is 0.01 percent, and four hydroxyl groups of pentaerythritol are esterified; and no boron-containing catalyst is added, the esterification rate of the pentaerythritol tetraiso-octoate is only 63%, the purity is 78%, and the water content is 0.3%, which shows that the technical scheme of the invention has remarkable progress.
2. By using the self-made boron-containing catalyst, the polymer skeleton contains sulfonic acid groups, boric acid groups and carboxyl groups, and the use of a strong acid catalyst is avoided, so that the corrosion to equipment is greatly reduced;
3. by using the water removing agent, the pentaerythritol tetraisooctanoate is prevented from being purified by distillation, the energy consumption is reduced, the pentaerythritol tetraisooctanoate is prevented from being hydrolyzed in the distillation process, and the purity is improved.
4. The existence of the boron-containing catalyst sulfydryl and boric acid groups can perform complex reaction with heavy metal ions, the metal ions brought by the raw material of pentaerythritol tetraiso-octoate can be adsorbed on the skeleton of the catalyst, and the product is separated by separation, so that the purity of the pentaerythritol tetraiso-octoate is improved.
Drawings
FIG. 1 is a Fourier infrared spectrum of the boron-containing catalyst obtained in example 1:
a stretching absorption peak of a benzene ring exists near 1612/1504/1454cm < -1 >, and a stretching absorption peak of hydrocarbon exists near 2942cm < -1 >, so that styrene participates in the reaction; a telescopic absorption peak of sulfonate ions exists near 1190/1116cm < -1 >, a telescopic absorption peak of a thiooxy double bond exists near 1039cm < -1 >, and a telescopic absorption peak of a thiooxy single bond exists near 760cm < -1 >, so that sodium propylene sulfonate participates in the reaction; the presence of a stretching absorption peak of a carbon-nitrogen single bond near 971cm-1, a stretching absorption peak of a sulfhydryl group near 2503cm-1 and a stretching absorption peak of a carbonyl group near 1807cm-1 indicates that 4- (3-allylthiourea) benzoic acid participates in the reaction; an absorption peak of a boron-oxygen bond exists near 1300cm < -1 >, which indicates that the 1-butenylboronic acid participates in the reaction.
Detailed Description
The raw materials used in the following examples are all commercially available products, and the examples are further illustrative of the present invention and do not limit the scope of the present invention;
the performance test methods are as follows:
1. the water content was measured by the Karl Fischer method.
2. And (3) the esterification rate is the actual water yield at the end of the reaction divided by the theoretical water yield at the key point of the reaction, and the water yield is tested by adopting a Karl Fischer method.
3. The purity of the product is tested by gas chromatography.
Example 1
Step one, synthesizing pentaerythritol tetraisooctoate: uniformly mixing 136g of pentaerythritol, 690g of isooctanoic acid and 17.2g of boron-containing catalyst, adding into a reaction vessel, stirring at 200r/min, heating to 100 ℃, reacting for 5 hours, and cooling to normal temperature to obtain a pentaerythritol tetraisooctanoate crude product;
step two, centrifuging a pentaerythritol tetraisooctoate crude product: centrifuging the pentaerythritol tetraisooctanoate crude product, wherein the rotating speed of a centrifuge is 8000r/min, the centrifuging time is 10min, separating to obtain a boron-containing catalyst and pentaerythritol mixed solution, drying the boron-containing catalyst and then recovering the boron-containing catalyst, and the pentaerythritol tetraisooctanoate mixed solution is reserved;
step three, post-treatment: washing the mixed solution of pentaerythritol tetraiso-octoate with 5% sodium hydroxide solution, separating with a separating funnel to obtain an oil phase, repeatedly washing for 4 times, washing with water and saturated salt solution for 4 times according to the same method to obtain pentaerythritol tetraiso-octoate;
step four, drying pentaerythritol tetraisooctoate: and adding 90g of anhydrous sodium sulfate into the pentaerythritol tetraiso-octoate, removing water, and separating the anhydrous sodium sulfate through reduced pressure suction filtration to obtain the pentaerythritol tetraiso-octoate product.
The preparation method of the boron-containing catalyst in the first step comprises the following steps:
step A, preparing emulsion: uniformly mixing 50g of sodium propylene sulfonate, 54g of styrene, 0.1g of 4- (3-allyl thiourea) benzoic acid, 0.1g of 1-butenylboronic acid and 2g of sodium dodecyl sulfate, adding the mixture into a three-neck flask, and dispersing for 30min at the normal temperature of 300r/min to obtain an emulsion;
step B, preparation of polymer: 0.3g of potassium persulfate and 0.01g of hydroquinone are added into the emulsion, and the temperature is raised to 80 DEGoC, stirring at the rotation speed of 200r/min, reacting for 0.6h, adding 0.6g of potassium persulfate, reacting for 1.2h, stopping the reaction, and cooling to room temperature to obtain a polymer mixture;
step C, preparing a boron-containing catalyst by acidification: and adding 35g of concentrated hydrochloric acid with the concentration of 36% into the polymer mixture, acidifying for 1h, filtering, washing and drying to obtain the boron-containing catalyst.
The esterification rate of the pentaerythritol tetraisooctoate was 98.5%, the purity was 99.5%, and the water content was 0.05%.
Example 2
Step one, synthesizing pentaerythritol tetraisooctoate: uniformly mixing 136g of pentaerythritol, 699.6g of isooctanoic acid and 18g of boron-containing catalyst, adding into a reaction vessel, stirring at 220r/min, heating to 110 ℃, reacting for 7.6h, and cooling to normal temperature to obtain a pentaerythritol tetraisooctanoate crude product;
step two, centrifuging a pentaerythritol tetraisooctoate crude product: centrifuging the pentaerythritol tetraisooctanoate crude product, wherein the rotating speed of a centrifuge is 15000r/min, the centrifuging time is 12.4min, separating to obtain a mixed solution of a boron-containing catalyst and pentaerythritol, drying the boron-containing catalyst and then recovering the boron-containing catalyst, and keeping the mixed solution of pentaerythritol tetraisooctanoate for later use;
step three, post-treatment: washing mixed solution of pentaerythritol tetraiso-octoate with 5% potassium hydroxide solution, separating with a separating funnel to obtain an oil phase, repeatedly washing for 5 times, washing with water and saturated salt solution for 5 times according to the same method to obtain pentaerythritol tetraiso-octoate;
step four, drying pentaerythritol tetraisooctoate: adding 96g of phosphorus pentoxide into the pentaerythritol tetraisooctanoate, removing water, and separating the phosphorus pentoxide by vacuum filtration to obtain the pentaerythritol tetraisooctanoate product.
The preparation method of the boron-containing catalyst in the first step comprises the following steps:
step A, preparing emulsion: uniformly mixing 50g of sodium propylene sulfonate, 58.1g of styrene, 0.2g of 4- (3-allyl thiourea) benzoic acid, 0.2g of 1-butenylboronic acid and 2.4g of sodium dodecyl diphenyl ether disulfonate, adding the mixture into a three-neck flask, and dispersing for 32.8min at the normal temperature of 320r/min to obtain emulsion;
step B, preparation of polymer: to the above emulsion was added 0.3g of azobisisobutyronitrile, 0.02g of DPPH, and the temperature was raised to 84.4oC, stirring at the rotation speed of 300r/min, reacting for 0.7h, adding 0.6g of azobisisobutyronitrile, reacting for 1.4h, stopping the reaction, and cooling to room temperature to obtain a polymer mixture;
step C, preparing a boron-containing catalyst by acidification: and adding 37.7g of concentrated hydrochloric acid with the concentration of 36% into the polymer mixture, acidifying for 1.2h, and filtering, washing and drying to obtain the boron-containing catalyst.
The esterification rate of the pentaerythritol tetraisooctoate was 98.6%, the purity was 99.5%, and the water content was 0.04%.
Example 3
Step one, synthesizing pentaerythritol tetraisooctoate: uniformly mixing 136g of pentaerythritol, 711.6g of isooctanoic acid and 18.6g of boron-containing catalyst, adding into a reaction vessel, stirring at 240r/min, heating to 136 ℃, reacting for 9.6h, and cooling to normal temperature to obtain a pentaerythritol tetraisooctanoate crude product;
step two, centrifuging a pentaerythritol tetraisooctoate crude product: centrifuging the pentaerythritol tetraisooctanoate crude product, wherein the rotating speed of a centrifuge is 20000r/min, the centrifuging time is 14.4min, separating to obtain a mixed solution of a boron-containing catalyst and pentaerythritol, drying the boron-containing catalyst and then recovering the boron-containing catalyst, and keeping the mixed solution of pentaerythritol tetraisooctanoate for later use;
step three, post-treatment: washing mixed solution of pentaerythritol tetraiso-octoate with 5% calcium hydroxide solution, separating with a separating funnel to obtain an oil phase, repeatedly washing for 6 times, washing with water and saturated salt solution for 6 times according to the same method to obtain pentaerythritol tetraiso-octoate;
step four, drying pentaerythritol tetraisooctoate: 102g of anhydrous calcium chloride is added into the pentaerythritol tetraiso-octoate, and the anhydrous calcium chloride is separated by vacuum filtration after water removal, so that the pentaerythritol tetraiso-octoate product is obtained.
The preparation method of the boron-containing catalyst in the first step comprises the following steps:
step A, preparing emulsion: uniformly mixing 50g of sodium propylene sulfonate, 60g of styrene, 0.3g of 4- (3-allyl thiourea) benzoic acid, 0.3g of 1-butenylboronic acid and 3.5g of sodium dodecyl benzene sulfonate, adding the mixture into a three-neck flask, and dispersing at the normal temperature of 340r/min for 36.8min to obtain emulsion;
step B, preparation of polymer: 0.3g of azobisisoheptonitrile and 0.03g of benzoquinone were added to the above emulsion, and the temperature was raised to 90%oC, stirring at the rotation speed of 380r/min, reacting for 0.8h, then adding 0.6g of azobisisoheptonitrile, reacting for 1.7h, stopping the reaction, and cooling to room temperature to obtain a polymer mixture;
step C, preparing a boron-containing catalyst by acidification: 41.9g of concentrated hydrochloric acid with the concentration of 36 percent is added into the polymer mixture to be acidified for 1.3h, and the boron-containing catalyst is obtained after suction filtration, washing and drying.
The esterification rate of the pentaerythritol tetraisooctoate was 98.8%, the purity was 99.6%, and the water content was 0.03%.
Example 4
Step one, synthesizing pentaerythritol tetraisooctoate: uniformly mixing 136g of pentaerythritol, 721.2g of isooctanoic acid and 19.4g of boron-containing catalyst, adding into a reaction vessel, stirring at 260r/min, heating to 158 ℃, reacting for 11.4h, and cooling to normal temperature to obtain a pentaerythritol tetraisooctanoate crude product;
step two, centrifuging a pentaerythritol tetraisooctoate crude product: centrifuging the pentaerythritol tetraisooctoate crude product, wherein the rotating speed of a centrifuge is 25000r/min, the centrifuging time is 15.4min, separating to obtain a mixed solution of a boron-containing catalyst and pentaerythritol, drying the boron-containing catalyst and then recovering the boron-containing catalyst, and keeping the mixed solution of pentaerythritol tetraisooctoate for later use;
step three, post-treatment: washing the mixed solution of pentaerythritol tetraiso-octoate with 5% sodium carbonate solution, separating with a separating funnel to obtain an oil phase, repeatedly washing for 7 times, washing with water and saturated salt solution for 7 times according to the same method to obtain pentaerythritol tetraiso-octoate;
step four, drying pentaerythritol tetraisooctoate: 105g of anhydrous calcium sulfate is added into the pentaerythritol tetraiso-octoate, and the anhydrous calcium sulfate is separated by vacuum filtration after water removal, so that the pentaerythritol tetraiso-octoate product is obtained.
The preparation method of the boron-containing catalyst in the first step comprises the following steps:
step A, preparing emulsion: uniformly mixing 50g of sodium propylene sulfonate, 64.1g of styrene, 0.4g of 4- (3-allylthiourea) benzoic acid, 0.3g of 1-butenylboronic acid and 3.9g of sodium dodecyl sulfate, adding the mixture into a three-neck flask, and dispersing for 42.4min at the normal temperature for 360r/min to obtain emulsion;
step B, preparation of polymer: 0.3g of dicumyl peroxide and 0.04g of aniline are added to the emulsion, and the temperature is raised to 94.4oC, stirring at the rotating speed of 360r/min, reacting for 0.8h, then adding 0.6g of dicumyl peroxide, reacting for 1.8h, stopping the reaction, and cooling to room temperature to obtain a polymer mixture;
step C, preparing a boron-containing catalyst by acidification: adding 45.8g of concentrated hydrochloric acid with the concentration of 36% into the polymer mixture, acidifying for 1.5h, filtering, washing and drying to obtain the boron-containing catalyst.
The esterification rate of the pentaerythritol tetraisooctoate was 99%, the purity was 99.6%, and the water content was 0.02%.
Example 5
Step one, synthesizing pentaerythritol tetraisooctoate: uniformly mixing 136g of pentaerythritol, 738g of isooctanoic acid and 20g of boron-containing catalyst, adding into a reaction vessel, stirring at 280r/min, heating to 174 ℃, reacting for 13.4h, and cooling to normal temperature to obtain a pentaerythritol tetraisooctanoate crude product;
step two, centrifuging a pentaerythritol tetraisooctoate crude product: centrifuging the pentaerythritol tetraisooctanoate crude product, wherein the rotating speed of a centrifuge is 28000r/min, the centrifuging time is 17.8min, separating to obtain a mixed solution of a boron-containing catalyst and pentaerythritol, drying the boron-containing catalyst and then recovering the boron-containing catalyst, and keeping the mixed solution of pentaerythritol tetraisooctanoate for later use;
step three, post-treatment: washing the mixed solution of pentaerythritol tetraisooctoate with 5% sodium bicarbonate solution, separating with a separating funnel to obtain an oil phase, repeatedly washing for 8 times, washing with water and saturated salt solution for 8 times according to the same method to obtain pentaerythritol tetraisooctoate;
step four, drying pentaerythritol tetraisooctoate: and adding 109.2g of anhydrous potassium carbonate into the pentaerythritol tetraiso-octoate, removing water, and separating the anhydrous potassium carbonate through reduced pressure suction filtration to obtain the pentaerythritol tetraiso-octoate product.
The preparation method of the boron-containing catalyst in the first step comprises the following steps:
step A, preparing emulsion: uniformly mixing 50g of sodium propylene sulfonate, 67.9g of styrene, 0.4g of 4- (3-allylthiourea) benzoic acid, 0.4g of 1-butenylboronic acid and 5g of ammonium dodecyl sulfate, adding the mixture into a three-neck flask, and dispersing at the normal temperature for 46.4min at 380r/min to obtain an emulsion;
step B, preparation of polymer: adding 0.3g of benzoyl peroxide and 0.05g of MEHQ into the emulsion, and heating to 100 DEGoC, stirring at the rotation speed of 320r/min, reacting for 0.9h, then adding 0.6g of benzoyl peroxide, reacting for 2.1h, stopping the reaction, and cooling to room temperature to obtain a polymer mixture;
step C, preparing a boron-containing catalyst by acidification: 49.7g of concentrated hydrochloric acid with the concentration of 36 percent is added into the polymer mixture to be acidified for 1.6h, and the boron-containing catalyst is obtained after suction filtration, washing and drying.
The esterification rate of the pentaerythritol tetraisooctoate was 99.1%, the purity was 99.6%, and the water content was 0.01%.
Example 6
Step one, synthesizing pentaerythritol tetraisooctoate: uniformly mixing 136g of pentaerythritol, 750g of isooctanoic acid and 21.5g of boron-containing catalyst, adding into a reaction vessel, stirring at 300r/min, heating to 200 ℃, reacting for 15h, and cooling to normal temperature to obtain a pentaerythritol tetraisooctanoate crude product;
step two, centrifuging a pentaerythritol tetraisooctoate crude product: centrifuging the pentaerythritol tetraisooctanoate crude product, wherein the rotating speed of a centrifuge is 30000r/min, the centrifuging time is 20min, separating to obtain a mixed solution of a boron-containing catalyst and pentaerythritol, drying the boron-containing catalyst and then recovering the boron-containing catalyst, and keeping the mixed solution of pentaerythritol tetraisooctanoate for later use;
step three, post-treatment: washing the mixed solution of pentaerythritol tetraiso-octoate with 5% potassium hydroxide solution, separating with a separating funnel to obtain an oil phase, repeatedly washing for 7 times, washing with water and saturated salt solution for 7 times according to the same method to obtain pentaerythritol tetraiso-octoate;
step four, drying pentaerythritol tetraisooctoate: adding 120g of 4A molecular sieve into the pentaerythritol tetraiso-octoate, removing water, and separating the 4A molecular sieve by vacuum filtration to obtain the pentaerythritol tetraiso-octoate product.
The preparation method of the boron-containing catalyst in the first step comprises the following steps:
step A, preparing emulsion: uniformly mixing 50g of sodium propylene sulfonate, 73g of styrene, 0.5g of 4- (3-allyl thiourea) benzoic acid, 0.5g of 1-butenylboronic acid and 6g of sodium dodecyl benzene sulfonate, adding the mixture into a three-neck flask, and dispersing for 50min at normal temperature at 400r/min to obtain an emulsion;
step B, preparation of polymer: to the above emulsion was added 0.4g of dimethyl azodiisobutyrate and 0.05g of DPPH, and the temperature was raised to 100oC, stirring at the rotation speed of 400r/min, reacting for 1.2h, then adding 0.8g of dimethyl azodiisobutyrate, and reacting for 2.4hStopping the reaction, and cooling to room temperature to obtain a polymer mixture;
step C, preparing a boron-containing catalyst by acidification: and adding 50g of concentrated hydrochloric acid with the concentration of 36% into the polymer mixture, acidifying for 2 hours, filtering, washing and drying to obtain the boron-containing catalyst.
The esterification rate of the pentaerythritol tetraisooctoate was 99.5%, the purity was 99.9%, and the water content was 0.01%.
Comparative example 1
Relative to example 1, no boron-containing catalyst was added, and the esterification rate of the pentaerythritol tetraisooctanoate obtained was 63%, the purity was 78%, and the water content was 0.3%.
Comparative example 2
Relative to example 1, phosphoric acid was added as a boron-containing catalyst for the esterification reaction, and otherwise, the esterification rate of the obtained pentaerythritol tetraisooctanoate was 75%, the purity was 85%, and the water content was 0.2%.
Comparative example 3
In contrast to the example 1, the process of the invention,
step A, preparing emulsion: uniformly mixing 50g of sodium propylene sulfonate, 58.1g of styrene, 0.2g of 1-butenylboronic acid and 2.4g of sodium dodecyl diphenyl ether disulfonate, adding the mixture into a three-neck flask, and dispersing for 32.8min at the normal temperature of 320r/min to obtain emulsion;
the esterification rate of the pentaerythritol tetraisooctanoate is 98.5 percent, the purity is 93.3 percent, and the water content is 0.1 percent.
Comparative example 4
In contrast to the example 1, the process of the invention,
step A, preparing emulsion: uniformly mixing 50g of sodium propylene sulfonate, 73g of styrene, 0.5g of 4- (3-allyl thiourea) benzoic acid and 6g of sodium dodecyl benzene sulfonate, adding into a three-neck flask, and dispersing for 50min at normal temperature at 400r/min to obtain emulsion;
the other components are unchanged, the esterification rate of the pentaerythritol tetraisooctanoate is 98.2 percent, the purity is 95.3 percent, and the water content is 0.1 percent.
Claims (7)
1. The preparation method of pentaerythritol tetraisooctoate is characterized by comprising the following steps:
step one, synthesizing pentaerythritol tetraisooctoate: uniformly mixing 136 parts of pentaerythritol, 690-750 parts of isooctanoic acid and 17.2-21.5 parts of catalyst according to mass fraction, adding into a reaction vessel, stirring at 300r/min for 200-;
step two, centrifuging a pentaerythritol tetraisooctoate crude product: centrifuging the crude pentaerythritol tetraisooctanoate, wherein the rotating speed of a centrifuge is 8000-;
step three, post-treatment: washing the mixed solution of pentaerythritol tetraiso-octoate with 5% aqueous alkali, separating with a separating funnel to obtain an oil phase, repeatedly washing for 4-8 times, washing with water and saturated salt solution for 4-8 times according to the same method to obtain pentaerythritol tetraiso-octoate;
step four, drying pentaerythritol tetraisooctoate: and adding 90-120 parts of a water removing agent into the pentaerythritol tetraiso-octoate according to the mass parts, and separating the water removing agent through vacuum filtration after water removal to obtain the pentaerythritol tetraiso-octoate product.
2. The method of claim 1, wherein the catalyst of step one is prepared by:
step A, preparing emulsion: uniformly mixing 30-50 parts of sodium propylene sulfonate, 54-73 parts of styrene, 0.1-0.5 part of 4- (3-allylthiourea) benzoic acid, 0.1-0.5 part of 1-butenylboronic acid and 2-6 parts of an emulsifier according to the mass parts, adding into a three-neck flask, and dispersing at the normal temperature of 300-;
step B, preparation of polymer: adding 0.3-0.4 part of initiator and 0.01-0.05 part of retarder into the emulsion according to the mass parts, and heating to 80-100%oC, stirring at the rotation speed of 200-400r/min, reacting for 0.6-1.2h, then adding 0.6-0.8 part of initiator, reacting for 1.2-2.4h, stopping the reaction, and cooling to room temperature to obtain a polymer mixture;
step C, preparing a catalyst by acidification: adding 35-50 parts by mass of concentrated hydrochloric acid with the concentration of 36% into the polymer mixture, acidifying for 1-2h, and carrying out suction filtration, washing and drying to obtain the catalyst.
3. The method of claim 2, wherein the emulsifier in step one is one or more of sodium dodecyl sulfate, sodium dodecyl diphenyl oxide disulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, and ammonium dodecyl sulfate.
4. The method of claim 2, wherein the initiator in step two is one or more selected from the group consisting of potassium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, dicumyl peroxide, benzoyl peroxide, and dimethyl azodiisobutyrate.
5. The method of claim 2, wherein the retarder in step two is one or more of hydroquinone, DPPH, benzoquinone, aniline, and MEHQ.
6. The method according to claim 1, wherein the alkali in the third step is one or a combination of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate and sodium bicarbonate.
7. The method according to claim 1, wherein the water removing agent in step four is one or a combination of 4A molecular sieve, anhydrous sodium sulfate, phosphorus pentoxide, anhydrous calcium chloride, anhydrous calcium sulfate and anhydrous potassium carbonate.
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