CN104086417A - Esterification method of pentaerythritol - Google Patents
Esterification method of pentaerythritol Download PDFInfo
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Abstract
The invention provides an esterification method of pentaerythritol, which comprises the following step: under the action of a tin catalyst, carrying out esterification reaction on pentaerythritol and saturated fatty acid to obtain pentaerythritol ester, wherein the saturated fatty acid is one or more of butyric acid, valeric acid, hexanoic acid, heptylic acid, octanoic acid, pelargonic acid and capric acid. The esterification method provided by the invention has the advantages of higher product yield, higher product quality, simple esterification after-treatment and low pollution. The experimental result indicates that the conversion rate of the esterification reaction is greater than 99.5%, and the hydroxyl value in the reaction product is lower than 1mg KOH/g.
Description
Technical field
The invention belongs to technical field of organic synthesis, relate in particular to a kind of esterification process of tetramethylolmethane.
Background technology
Tetramethylolmethane is a kind of important industrial chemicals, is mainly used in coatings industry, can be in order to manufacture phthalic resin coating, and can make hardness, gloss and the weather resistance of paint film be improved.It is also as the required abietinic raw material such as colored paint, varnish and printing-ink, and can siccative oil processed, smolderability coating and the empty lubricated wet goods of boat.The fatty acid ester of tetramethylolmethane, is called for short pentaerythritol ester, and in industrial circle, pentaerythritol ester not only can be used as softening agent, the processing stabilizers of plastic material, releasing agent, dispersion agent, but also be a kind of important neopentyl polyol ester.More than the ester group of pentaerythritol ester and on the carbon of β position, there is no hydrogen atom, therefore there is thermal oxidation stability good, vaporization losses is low, lubricity, low-temperature performance and viscosity-temperature characteristics can wait well feature, because pentaerythritol ester has excellent lubricity, viscosity index is high, non-flame properties good, biological degradation rate reaches more than 90%, is therefore the synthetic desirable base oil of ester type fire resistant hydraulic oil, and can be used for allocating the hydraulic efficiency oil, chain saw oil and the water ride engine oil that require environmental protection.Meanwhile, pentaerythritol ester is applied in cold-rolling of steel plate liquid processed, steel pipe drawing oil and other metal working fluid as oiliness improver, and pentaerythritol ester also has good surface filming.Can be used for soft, hard PVC sheet material, sheet material leads in section bar, tubing, clear vial material and heat-shrinkable film.Also can be used as intermediate and the textile finish oil of leather auxiliary agent.Therefore in modern industry is produced, pentaerythritol ester is widely used in each field of industrial productions such as aircraft oil, automotive lubricant, air compressor oil and fire resistant hydraulic oil.
Just because of pentaerythritol ester is with a wide range of applications and Application Areas, the esterification of tetramethylolmethane has become current most study and has realized industrialized technique.But owing to being subject to sterically hindered impact, polyvalent alcohol needs esterification step by step.The reaction equilibrium constant of polyvalent alcohol and carboxylic esterification is very little, need to be in reaction process vaccum dewatering, reaction could be carried out towards the direction of esterification.The at present industrial an acidic catalyst that uses more, such as sulfuric acid, tosic acid and phosphoric acid etc., these catalyzer relative low price, better catalytic activity, but the removal difficulty of catalyzer is larger, this is due to strong acid catalysts such as sulfuric acid, in the time of catalytic esterification, belongs to homogeneous reaction, separation has certain difficulty, because the oxidisability that it is higher and stronger acidity, cause being easy to produce by product in esterification reaction process, product performance are good relatively not, separating difficulty is relatively large, operation is long, produces a large amount of trade effluents, and environmental stress is larger.The acid number of the pentaerythritol ester that aforesaid method is produced is generally higher, and during for lubricating oil, larger acid number is the corrosion of aggravation metal parts directly, makes corrosion phenomenon more serious.But the hydroxyl value of pentaerythritol ester can not be larger, larger hydroxyl value can cause that the water-absorbent of lubricating oil is stronger, also can cause the increase of low temperature viscosity, increases the weight of the corrosion of metal parts simultaneously, is unsuitable for using under water requirement harshness and the higher condition of degree of cleaning.
Therefore, the problem occurring in order to solve an acidic catalyst esterification has higher product income, lower acid number and hydroxyl value simultaneously, is problem demanding prompt solution in industry always.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of esterification process of tetramethylolmethane, esterification process provided by the invention adopts the esterification of tin class catalyzer for tetramethylolmethane, there is higher product income and quality product, lower acid number and hydroxyl value, be applicable to the lubricating oil field under special conditions, and post-esterification treatment is simple, pollutes little.
The esterification process that the invention discloses a kind of tetramethylolmethane, comprises the following steps:
A) under the effect of tin class catalyzer, tetramethylolmethane and saturated fatty acid are carried out to esterification, obtain pentaerythritol ester;
Described saturated fatty acid is one or more in butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid and capric acid.
Preferably, described tin class catalyzer is one or several in tin protoxide, tin protochloride, stannic oxide, butyl stannic oxide, stannous octoate, stannous oxalate and QS-6.
Preferably, the mol ratio of described tetramethylolmethane and saturated fatty acid is 1:(1.0～6.0).
Preferably, the mol ratio of described tetramethylolmethane and saturated fatty acid is 1:(2.0～6.0).
Preferably, the quality of described tin class catalyzer and the mass ratio of tetramethylolmethane are (0.005～0.5): 100.
Preferably, the temperature of reaction of described esterification is 130～195 DEG C.
Preferably, the reaction times of described esterification is 4～8 hours, and the reaction pressure of described esterification is 3000～10000Pa.
Preferably, described steps A) be specially:
Under the effect of tin class catalyzer, tetramethylolmethane is reacted at the first temperature with saturated fatty acid, then continue heating and react, obtain pentaerythritol ester.
Preferably, described the first temperature is 130～160 DEG C, and the reaction times of reacting at described the first temperature is 2～4 hours; The temperature of described heating is 160～195 DEG C, and the time of described heating is 2～4 hours.
Preferably, the hydroxyl value of described pentaerythritol ester is less than or equal to 2mg KOH/g.
The esterification process that the invention discloses a kind of tetramethylolmethane, comprises the following steps: under the effect of tin class catalyzer, tetramethylolmethane and saturated fatty acid are carried out to esterification, obtain pentaerythritol ester; Described saturated fatty acid is one or more in butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid and capric acid.Compared with prior art, the present invention adopts tin class catalyzer to carry out esterification, utilize the free electronic orbit of tin class catalyzer, there is Lewis acidity, be combined with organic acid, form and be similar to organometallic compound, can activate carbonyl, positive charge on carbonylic carbon atom is increased, promote the carrying out of esterification.Further, the present invention is by controlling reaction process and reaction conditions, make tetramethylolmethane to be less than 10 saturated fatty acid with carbon atom quantity and carry out esterification, obtain pentaerythritol ester, and there is lower hydroxyl value, the application requiring of application requiring, the especially special lubricating oil in the lubricating oil field under can special conditions.The esterification process of tetramethylolmethane provided by the invention has higher product income and quality product, has lower acid number and hydroxyl value, and post-esterification treatment is simple, pollutes little.Experimental result shows, the transformation efficiency of esterification provided by the invention is greater than 99.5%, and the hydroxyl value in reaction product is less than or equal to 0.6 mgKOH/g, and acid number is 0.01mg KOH/g.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just in order to further illustrate the features and advantages of the present invention, instead of restriction to invention claim.
The esterification process that the invention provides a kind of tetramethylolmethane, comprises the following steps:
A) under the effect of tin class catalyzer, tetramethylolmethane and saturated fatty acid are carried out to esterification, obtain pentaerythritol ester;
Described saturated fatty acid is one or more in butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid and capric acid.
Esterifying reaction method provided by the invention, utilizes the free electronic orbit of tin class catalyzer, has Lewis acidity, be combined with organic acid, form and be similar to organometallic compound, can activate carbonyl, positive charge on carbonylic carbon atom is increased, promote the carrying out of esterification.Further, the present invention is by controlling reaction process and reaction conditions, makes tetramethylolmethane to be less than 10 saturated fatty acid with carbon atom quantity and carries out esterification, obtains pentaerythritol ester.The esterification process of tetramethylolmethane provided by the invention has higher product income and quality product, has lower acid number and hydroxyl value, be applicable to the lubricating oil field under special conditions, and post-esterification treatment is simple, pollutes little.
The all raw materials of the present invention, are not particularly limited its source, on market, buy.
The present invention is not particularly limited the purity of all raw materials, with material purity conventional in esterification well known to those skilled in the art, is preferably technical pure.
The present invention, under the effect of tin class catalyzer, carries out esterification by tetramethylolmethane and saturated fatty acid, obtains pentaerythritol ester.
Described saturated fatty acid is preferably one or more in butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid and capric acid, more preferably one or more in valeric acid, caproic acid, enanthic acid, sad and n-nonanoic acid; Described tin class catalyzer is preferably one or several in tin protoxide, tin protochloride, stannic oxide, butyl stannic oxide, stannous octoate, stannous oxalate and QS-6, more preferably tin protoxide, tin protochloride, stannic oxide, butyl stannic oxide, stannous octoate, stannous oxalate or QS-6, most preferably be tin protoxide, butyl stannic oxide or QS-6; The mol ratio of described tetramethylolmethane and saturated fatty acid is preferably 1:(1.0～6.0), more preferably 1:(2.0～5.0), most preferably be 1:(4.0～4.8); The quality of described tin class catalyzer and the mass ratio of tetramethylolmethane are preferably (0.005～0.5): 100, and more preferably (0.05～0.4): 100, most preferably be (0.05～0.1): 100; The temperature of reaction of described esterification is preferably 130～199 DEG C, more preferably 150～195 DEG C, most preferably is 170～190 DEG C; The reaction pressure of described esterification is preferably 3000～10000Pa, and more preferably 4000～8000Pa, most preferably is 5000～7000Pa; The reaction times of described esterification is preferably 4～8 hours, more preferably 5～7 hours, most preferably is 5.5～6.5 hours; The hydroxyl value of described pentaerythritol ester is preferably and is less than or equal to 5mg KOH/g, is more preferably less than or equal to 2mgKOH/g, most preferably is and is less than or equal to 1mg KOH/g; The acid number of described pentaerythritol ester is preferably and is less than or equal to 0.01mg KOH/g.
The present invention is for improving the quality of products, ensure that reacting balance carries out, and preferably adopts following reactions steps: first the present invention under the effect of tin class catalyzer, reacts with saturated fatty acid tetramethylolmethane at the first temperature, then continue heating and react, obtain pentaerythritol ester; Described the first temperature is preferably 130～160 DEG C, more preferably 140～155 DEG C, most preferably is 150～153 DEG C; The reaction times of reacting at described the first temperature is preferably 2～4 hours, more preferably 2.5～3.5 hours; The temperature of described heating is preferably 160～195 DEG C, and more preferably 170～193 DEG C, most preferably be 180～190 DEG C, the time of described heating is preferably 2～4 hours, more preferably 1～3 hour.
The present invention is not particularly limited the mode of described heating, and with the type of heating of esterification well known to those skilled in the art, the present invention carries out for ensureing reacting balance, is preferably constant-speed heating and heats up; The speed that the present invention heats up to described constant-speed heating is not particularly limited, those skilled in the art can according to temperature of reaction, reaction times and specifically other reaction conditionss adjust voluntarily.The present invention is not particularly limited other conditions of reaction, with the reaction conditions of esterification well known to those skilled in the art; The present invention does not have special requirement to conversion unit, with conversion unit well known to those skilled in the art.
The present invention, after above-mentioned esterification completes, is raising reaction product purity, the preferably product to esterification, and thick ester, carries out, after aftertreatment, finally obtaining pentaerythritol ester.The present invention is not particularly limited aftertreatment, with the post-processing step of preparing pentaerythritol ester well known to those skilled in the art, preferably adopt following methods to carry out, obtain thick ester through above-mentioned esterification, first cooling adds the acid in excessive alkali lye neutralization reaction system after filtering in reaction system, then alkali lye is removed in separation, then add gac to dewater, after finally filtering, obtain pentaerythritol ester.
The present invention is not particularly limited the temperature range of cooling, and with the filtration temperature of filtration esterification well known to those skilled in the art, the present invention is preferably 70～100 DEG C.The present invention is not particularly limited the mode of filtering, with filter type well known to those skilled in the art.The present invention is not particularly limited the concentration of alkali lye, and with the concentration of lye for neutralizing well known to those skilled in the art, it is 10% alkali lye that the present invention preferably adopts mass concentration.The present invention is not particularly limited the mode separating, and with separate mode well known to those skilled in the art, the present invention preferably adopts standing separation.The present invention is not particularly limited the method for dehydration, with aftertreatment dewatering well known to those skilled in the art, is preferably vacuum hydro-extraction, and the present invention is not particularly limited the vacuum tightness of described vacuum.
The present invention adopts tin class catalyzer to carry out esterification, utilizes the free electronic orbit of tin class catalyzer, has Lewis acidity, be combined with organic acid, form and be similar to organometallic compound, can activate carbonyl, positive charge on carbonylic carbon atom is increased, promote the carrying out of esterification.Further, the present invention, by controlling reaction process, makes tetramethylolmethane to be less than 10 saturated fatty acid with carbon atom quantity and carries out esterification, obtains pentaerythritol ester.The esterification process of tetramethylolmethane provided by the invention has higher product income and quality product, there is lower acid number and hydroxyl value, can be used in lubricating oil field under special conditions, lower hydroxyl value can weaken the water-absorbent of product and the avidity with metal, corrodibility to metal parts is little, is suitable for water requirement harshness and the higher working conditions of degree of cleaning; Lower acid number can not cause corrosion of metal, thereby better protects metal parts.It is simple that the esterification process of tetramethylolmethane provided by the invention also has aftertreatment, pollutes the features such as little.
The present invention has obtained pentaerythritol ester through above-mentioned reactions steps, and obtained pentaerythritol ester is detected, and experimental result shows, esterification provided by the invention.Its transformation efficiency is greater than 99.5%, and the hydroxyl value in reaction product is lower than 1mg KOH/g.
In order further to understand the present invention, below in conjunction with embodiment, the esterification process of tetramethylolmethane provided by the invention is elaborated, protection scope of the present invention is not limited by the following examples.
Comparative example 1
First 100g tetramethylolmethane, the positive valeric acid of 360g and 1.84g catalyst sulfuric acid hydrogen sodium are put into reactor, after mixing, be 180 DEG C at temperature condition, under the condition that pressure is 3000Pa, carry out esterification, after reaction 7h, being cooled to 80 DEG C of filtrations, be then in 10% alkali lye and excess acid to adding mass concentration in reaction system, then standing separation is removed alkali lye, the product finally aforesaid method being obtained is washed again, obtains pentaerythritol ester after distillation.
After above-mentioned pentaerythritol ester, the performance of pentaerythritol ester is tested obtaining, result shows, the transformation efficiency of esterification is 99.7%; Hydroxyl value is 0.3mgKOH/g, and acid number is 0.01mgKOH/g; Above-mentioned pentaerythritol ester is carried out to impurities analysis, and wherein S content, higher than detectability, is 97ppm, and Na content is less than 2.0ppm.
Embodiment 1
First by 100g tetramethylolmethane, the positive valeric acid of 360g and 0.46g stannous oxide catalyst are put into reactor, after mixing, first open heating system, being heated to temperature condition is 150 DEG C, pressure is under the condition of 3000Pa, carry out esterification, after reaction 4h, then proceed uniform speed slow heat temperature raising 3h, be warming up to after 198 DEG C, be cooled to 70 DEG C of filtrations, be in 10% alkali lye and excess acid to adding mass concentration in reaction system again, standing separation is removed alkali lye, finally to the product after separating, under the existence of the gac of the said products quality 0.5%, carry out vacuum hydro-extraction, after filtration, obtain pentaerythritol ester.
After above-mentioned pentaerythritol ester, the performance of pentaerythritol ester is tested obtaining, result shows, the transformation efficiency of esterification is 99.8%; Hydroxyl value is 0.6mgKOH/g, and acid number is 0.01mgKOH/g; Above-mentioned pentaerythritol ester is carried out to impurities analysis, and Sn content is less than 4.0ppm, lower than detectability; Na content is less than 2.0ppm, lower than detectability.
Embodiment 2
First by 100g tetramethylolmethane, the positive valeric acid of 360g and 0.23g catalyzer QS-6 put into reactor, after mixing, first open heating system, being heated to temperature condition is 155 DEG C, pressure is under the condition of 3000Pa, carry out esterification, after reaction 3h, then proceed uniform speed slow heat temperature raising 2h, be warming up to after 195 DEG C, be cooled to 80 DEG C of filtrations, be in 10% alkali lye and excess acid to adding mass concentration in reaction system again, standing separation is removed alkali lye, finally to the product after separating, under the existence of the gac of the said products quality 0.5%, carry out vacuum hydro-extraction, after filtration, obtain pentaerythritol ester.
After above-mentioned pentaerythritol ester, the performance of pentaerythritol ester is tested obtaining, result shows, the transformation efficiency of esterification is 99.9%; Hydroxyl value is 0.2mgKOH/g, acid number 0.01mgKOH/g; Above-mentioned pentaerythritol ester is carried out to impurities analysis, and Sn content is less than 4.0ppm, lower than detectability; Na content is less than 2.0ppm, lower than detectability.
Embodiment 3
First by 1mol tetramethylolmethane, the mixed fatty acid of 4.6mol (C5～C9) and 0.24g catalyzer butyl stannic oxide are put into reactor, after mixing, first open heating system, being heated to temperature condition is 160 DEG C, pressure is under the condition of 3000Pa, carry out esterification, after reaction 4h, then proceed uniform speed slow heat temperature raising 4h, be warming up to after 190 DEG C, be cooled to 100 DEG C of filtrations, be in 10% alkali lye and excess acid to adding mass concentration in reaction system again, standing separation is removed alkali lye, finally to the product after separating, under the existence of the gac of the said products quality 0.5%, carry out vacuum hydro-extraction, after filtration, obtain pentaerythritol ester.
After above-mentioned pentaerythritol ester, the performance of pentaerythritol ester is tested obtaining, result shows, the transformation efficiency of esterification is 99.6%; Hydroxyl value is 0.4mgKOH/g, acid number 0.01mgKOH/g; Above-mentioned pentaerythritol ester is carried out to impurities analysis, and Sn content is less than 4.0ppm, lower than detectability; Na content is less than 2.0ppm, lower than detectability.
To obtaining the Performance Detection of carrying out of pentaerythritol ester, its flash-point is 248 DEG C, 40 DEG C of kinematic viscosity are 19.18mm2/s,-40 DEG C of kinematic viscosity are 4765mm2/s, oxidation corrosion (SH/T0450) metal protection is 0.0,40 DEG C of kinematic viscosity are changed to 42.9%, and acid number changes 2.36mgKOH/g.
Above the esterification process of a kind of tetramethylolmethane provided by the present invention is described in detail.Applied a concrete example herein principle of the present invention and embodiment are set forth, the explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (10)
1. an esterification process for tetramethylolmethane, comprises the following steps:
A) under the effect of tin class catalyzer, tetramethylolmethane and saturated fatty acid are carried out to esterification, obtain pentaerythritol ester;
Described saturated fatty acid is one or more in butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid and capric acid.
2. esterification process according to claim 1, is characterized in that, described tin class catalyzer is one or several in tin protoxide, tin protochloride, stannic oxide, butyl stannic oxide, stannous octoate, stannous oxalate and QS-6.
3. esterification process according to claim 1, is characterized in that, the mol ratio of described tetramethylolmethane and saturated fatty acid is 1:(1.0～6.0).
4. esterification process according to claim 1, is characterized in that, the mol ratio of described tetramethylolmethane and saturated fatty acid is 1:(2.0～6.0).
5. esterification process according to claim 1, is characterized in that, the quality of described tin class catalyzer and the mass ratio of tetramethylolmethane are (0.005～0.5): 100.
6. esterification process according to claim 1, is characterized in that, the temperature of reaction of described esterification is 130～195 DEG C.
7. esterification process according to claim 1, is characterized in that, the reaction times of described esterification is 4～8 hours, and the reaction pressure of described esterification is 3000～10000Pa.
8. esterification process according to claim 1, is characterized in that, described steps A) be specially:
Under the effect of tin class catalyzer, tetramethylolmethane is reacted at the first temperature with saturated fatty acid, then continue heating and react, obtain pentaerythritol ester.
9. esterification process according to claim 8, is characterized in that, described the first temperature is 130～160 DEG C, and the reaction times of reacting at described the first temperature is 2～4 hours; The temperature of described heating is 160～195 DEG C, and the time of described heating is 2～4 hours.
10. esterification process according to claim 1, is characterized in that, the hydroxyl value of described pentaerythritol ester is less than or equal to 2mg KOH/g.
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| CN104803847A (en) * | 2015-03-05 | 2015-07-29 | 江苏雷蒙化工科技有限公司 | Technology for synthesizing ATBC (acetyl tributyl citrate) under catalysis of composite solid acid |
| CN104892414A (en) * | 2015-05-13 | 2015-09-09 | 常州大学 | Method used for catalyzed synthesis of monoprotic acid pentaerythritol ester with acid-base bifunctional solid catalyst CaO/HMCM-22 |
| CN105061203A (en) * | 2015-07-16 | 2015-11-18 | 中国石油化工股份有限公司 | Preparation method of pentaerythritol ester |
| CN106631782B (en) * | 2016-10-17 | 2019-11-26 | 中国石油化工股份有限公司 | A kind of preparation method of pentaerythrite quaternary acid esters |
| CN106631782A (en) * | 2016-10-17 | 2017-05-10 | 中国石油化工股份有限公司 | Preparation method of pentaerythritol tetrabasic acid ester |
| CN106975475A (en) * | 2017-04-26 | 2017-07-25 | 中国石油化工股份有限公司 | It is a kind of for catalyst of synthesizing trimethylol propane ester and preparation method thereof and application |
| CN106975475B (en) * | 2017-04-26 | 2019-12-20 | 中国石油化工股份有限公司 | Catalyst for synthesizing trimethylolpropane ester and preparation method and application thereof |
| CN109134247A (en) * | 2017-06-27 | 2019-01-04 | 中国石油天然气股份有限公司 | Preparation method and system of pentaerythritol ester |
| CN109134247B (en) * | 2017-06-27 | 2022-03-29 | 中国石油天然气股份有限公司 | Preparation method and system of pentaerythritol ester |
| CN107501092A (en) * | 2017-08-21 | 2017-12-22 | 大连理工大学 | A kind of method that continuous decompression catalytic distillation prepares pentaerythrite ester base oil |
| CN108191650A (en) * | 2017-12-25 | 2018-06-22 | 江苏雷蒙新材料有限公司 | A kind of preparation method of pentaerythrite tetra-acetate |
| CN111848403A (en) * | 2019-04-26 | 2020-10-30 | 南京纽邦生物科技有限公司 | Preparation method of pentaerythritol tetraisostearate |
| CN110527579A (en) * | 2019-08-31 | 2019-12-03 | 浙江工业大学 | A kind of synthetic method of lube base oil mixed esters of pentaerythritol |
| CN110655970A (en) * | 2019-10-21 | 2020-01-07 | 中国石油化工股份有限公司 | Biodegradable transformer oil and preparation method thereof |
| CN111423324A (en) * | 2020-02-26 | 2020-07-17 | 沈阳张明化工有限公司 | Process for synthesizing fatty acid ester by catalyzing tin oxide |
| CN112724016A (en) * | 2020-12-31 | 2021-04-30 | 潍坊加易加生物科技有限公司 | Method for recycling esterification catalyst stannous oxide |
| CN114426484A (en) * | 2022-01-21 | 2022-05-03 | 中国石油化工股份有限公司 | Synthetic method of pentaerythritol ester |
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