CN104086417B - A kind of esterification process of tetramethylolmethane - Google Patents
A kind of esterification process of tetramethylolmethane Download PDFInfo
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- CN104086417B CN104086417B CN201410363737.XA CN201410363737A CN104086417B CN 104086417 B CN104086417 B CN 104086417B CN 201410363737 A CN201410363737 A CN 201410363737A CN 104086417 B CN104086417 B CN 104086417B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
The invention provides the esterification process of a kind of tetramethylolmethane, comprise the following steps, under the effect of tin catalyst, tetramethylolmethane and satisfied fatty acid are carried out esterification, obtains pentaerythritol ester；Described satisfied fatty acid is one or more in butanoic acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid and capric acid.The esterification process of the tetramethylolmethane that the present invention provides has higher product income and product quality, and post-esterification treatment is simple, pollutes little.Test result indicate that, the esterification that the present invention provides.Its conversion ratio is more than 99.5%, and the hydroxyl value in product is less than 1mg KOH/g.
Description
Technical field
The invention belongs to technical field of organic synthesis, particularly relate to the esterification process of a kind of tetramethylolmethane.
Background technology
Tetramethylolmethane is a kind of important industrial chemicals, is used primarily in coatings industry, may be used to manufacture alcohol
Acid resin coating, can make the hardness of paint film, gloss and durability be improved.It also serve as colored paint,
The abietinic raw material that varnish and printing-ink etc. are required, and can drying oil processed, smolderability coating and boat empty
Lubricating oil etc..The fatty acid ester of tetramethylolmethane, is called for short pentaerythritol ester, in industrial circle, Ji Wusi
Alcohol ester serves not only as plasticizer, the processing stabilizers of plastic material, releasing agent, dispersant, and
Or a kind of important neopentyl polyol ester.The ester group of pentaerythritol ester is many and do not has hydrogen former on the carbon of β position
Son, therefore has thermal oxidation stability good, and evaporation loss is low, greasy property, cryogenic property and viscosity-temperature characteristics
Feature can be waited well, due to pentaerythritol ester there is the greasy property of excellence, viscosity index (VI) is high, flame resistance is good,
Biological degradation rate reaches more than 90%, is therefore the synthesis preferable base oil of ester type fire resistant hydraulic oil, and can
Hydraulic oil, chain saw oil and water ride engine oil for formulation requirements environmental protection.Meanwhile, Ji Wusi
Alcohol ester is applied in cold-rolling of steel plate liquid, steel pipe drawing oil and other metal working fluid as oiliness improver, and
And pentaerythritol ester also has good surface filming.Can be used for soft, hard PVC sheet, sheet material is led
In section bar, tubing, clear vial material and heat shrink films.Also can be as the intermediate of leather auxiliary agent and spinning
Knit oil preparation.Therefore, in modern industry produces, pentaerythritol ester is widely used in aeroengine oil, automobile
Each field of industrial productions such as lubricant, air compressor oil and fire resistant hydraulic oil.
Just because of pentaerythritol ester is with a wide range of applications and application, the esterification of tetramethylolmethane is anti-
Should become current most study and have been realized in industrialized technique.But, due to by sterically hindered
Impact, polyhydric alcohol needs to be esterified step by step.Polyhydric alcohol is the least with the reaction equilibrium constant of carboxylic esterification, needs
Will in course of reaction vaccum dewatering, reaction could towards esterification direction carry out.Current industrial make more
With acidic catalyst, such as sulphuric acid, p-methyl benzenesulfonic acid and phosphoric acid etc., these catalyst relative low price,
Better catalytic activity, but the removal difficulty of catalyst is relatively big, and this is due to strong acid catalysts such as sulphuric acid,
When catalytic esterification, belong to homogeneous reaction, separate and have certain difficulty, because its higher oxidation
Property and stronger acidity, cause esterification reaction process being prone to produce by-product, properties of product are the most inadequate
Good, separating difficulty is relatively large, and operation is long, produces substantial amounts of industrial wastewater, and ambient pressure is bigger.On
The acid number stating the pentaerythritol ester that method produces is the highest, and when lubricating oil, bigger acid number can be directly
The corrosion of aggravation metal parts so that corrosion phenomenon is more serious.But the hydroxyl value of pentaerythritol ester is the most not
Can be relatively big, bigger hydroxyl value can cause the water absorption of lubricating oil relatively by force, also results in the increase of low temperature viscosity,
Add the corrosion of heavy metal parts simultaneously, be unsuitable for and cleannes harsh to water requirement higher under conditions of make
With.
Therefore, in order to solve acidic catalyst esterification produced problem, there is higher product simultaneously
Problem demanding prompt solution in income, relatively low acid number and hydroxyl value, always industry.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide the esterification process of a kind of tetramethylolmethane,
The esterification process that the present invention provides uses tin catalyst for the esterification of tetramethylolmethane, has higher
Product income and product quality, relatively low acid number and hydroxyl value, it is adaptable under specific condition lubricating oil neck
Territory, and post-esterification treatment is simple, pollutes little.
The invention discloses the esterification process of a kind of tetramethylolmethane, comprise the following steps:
A) under the effect of tin catalyst, tetramethylolmethane and satisfied fatty acid are carried out esterification,
To pentaerythritol ester；
Described satisfied fatty acid is in butanoic acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid and capric acid
Plant or several.
Preferably, described tin catalyst be Tin monoxide, stannous chloride, stannum oxide, butyl stannum oxide,
One or several in stannous octoate, stannous oxalate and QS-6.
Preferably, described tetramethylolmethane is 1:(1.0～6.0 with the mol ratio of satisfied fatty acid).
Preferably, described tetramethylolmethane is 1:(2.0～6.0 with the mol ratio of satisfied fatty acid).
Preferably, the quality of described tin catalyst is (0.005～0.5) with the mass ratio of tetramethylolmethane: 100.
Preferably, the reaction temperature of described esterification is 130～195 DEG C.
Preferably, the response time of described esterification is 4～8 hours, the reaction pressure of described esterification
Power is 3000～10000Pa.
Preferably, described step A) particularly as follows:
Under the effect of tin catalyst, tetramethylolmethane and satisfied fatty acid are carried out instead at the first temperature
Should, then proceed to heating and react, obtain pentaerythritol ester.
Preferably, described first temperature is 130～160 DEG C, when carrying out, at a temperature of described first, the reaction reacted
Between be 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 invention discloses the esterification process of a kind of tetramethylolmethane, comprise the following steps: in tin catalyst
Effect under, tetramethylolmethane and satisfied fatty acid are carried out esterification, obtain pentaerythritol ester；Described
Satisfied fatty acid is one or more in butanoic acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid and capric acid.
Compared with prior art, the present invention uses tin catalyst to carry out esterification, utilizes tin catalyst to have
Empty electron orbit, has Lewis acid, is combined with organic acid, is formed and is similar to Organometallic compounds
Thing, positive charge on carbonylic carbon atom can be made to increase with activated carbonyl, promotes the carrying out of esterification.
Further, the present invention is by controlling course of reaction and reaction condition so that tetramethylolmethane can be with carbon containing
The atomic number satisfied fatty acid less than 10 carries out esterification, obtains pentaerythritol ester, and has relatively low
Hydroxyl value, it is possible to the application requirement in the lubricating oil field under specific condition, especially special lubricating oil should
With requiring.The esterification process of the tetramethylolmethane that the present invention provides has higher product income and product quality,
There is relatively low acid number and hydroxyl value, and post-esterification treatment is simple, pollutes little.Test result indicate that, this
The conversion ratio of the esterification that invention provides is more than 99.5%, and the hydroxyl value in product is less than or equal to 0.6 mg
KOH/g, acid number is 0.01mg KOH/g.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is retouched
State, but it is to be understood that these descriptions are intended merely to further illustrate the features and advantages of the present invention, and
It it not the restriction to invention claim.
The invention provides the esterification process of a kind of tetramethylolmethane, comprise the following steps:
A) under the effect of tin catalyst, tetramethylolmethane and satisfied fatty acid are carried out esterification,
To pentaerythritol ester；
Described satisfied fatty acid is in butanoic acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid and capric acid
Plant or several.
The esterifying reaction method that the present invention provides, utilizes the electron orbit that tin catalyst is free, has
Lewis is acid, is combined with organic acid, and formation is similar to organo-metallic compound, can with activated carbonyl,
Make positive charge on carbonylic carbon atom increase, promote the carrying out of esterification.Further, the present invention passes through
Control course of reaction and reaction condition so that tetramethylolmethane can be with the carbon atom quantity saturated fat less than 10
Fat acid carries out esterification, obtains pentaerythritol ester.The esterification process tool of the tetramethylolmethane that the present invention provides
There are higher product income and product quality, there is relatively low acid number and hydroxyl value, it is adaptable under specific condition
Lubricating oil field, and post-esterification treatment is simple, pollutes little.
The all raw materials of the present invention, are not particularly limited its source, commercially buy.
The purity of all raw materials is not particularly limited by the present invention, with esterification well known to those skilled in the art
Material purity conventional in reaction, preferably technical pure.
Tetramethylolmethane and satisfied fatty acid, under the effect of tin catalyst, are carried out esterification by the present invention,
Obtain pentaerythritol ester.
Described satisfied fatty acid is preferably in butanoic acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid and capric acid
One or more, more preferably one or more in valeric acid, caproic acid, enanthic acid, octanoic acid and n-nonanoic acid；
Described tin catalyst is preferably Tin monoxide, stannous chloride, stannum oxide, butyl stannum oxide, octanoic acid Asia
One or several in stannum, stannous oxalate and QS-6, more preferably Tin monoxide, stannous chloride, oxygen
Change stannum, butyl stannum oxide, stannous octoate, stannous oxalate or QS-6, most preferably Tin monoxide, butyl
Stannum oxide or QS-6；Described tetramethylolmethane is preferably 1:(1.0～6.0 with the mol ratio of satisfied fatty acid),
More preferably 1:(2.0～5.0), most preferably 1:(4.0～4.8)；The quality of described tin catalyst and season
The mass ratio of penta tetrol is preferably (0.005～0.5): 100, more preferably (0.05～0.4): 100, optimum
Elect as (0.05～0.1): 100；The reaction temperature of described esterification is preferably 130～199 DEG C, more preferably
It is 150～195 DEG C, most preferably 170～190 DEG C；The reaction pressure of described esterification is preferably
3000～10000Pa, more preferably 4000～8000Pa, most preferably 5000～7000Pa；Described esterification is anti-
The response time answered is preferably 4～8 hours, more preferably 5～7 hours, most preferably 5.5～6.5 hours；
The hydroxyl value of described pentaerythritol ester is preferably less than equal to 5mg KOH/g, more preferably less than equal to 2mg
KOH/g, most preferably less than equal to 1mg KOH/g；The acid number of described pentaerythritol ester is preferably less than
Equal to 0.01mg KOH/g.
The present invention is for improving product quality, it is ensured that reacting balance is carried out, it is preferred to use following reactions steps:
The present invention is first under the effect of tin catalyst, by tetramethylolmethane with satisfied fatty acid at the first temperature
React, then proceed to heating and react, obtain pentaerythritol ester；Described first temperature is preferably
130～160 DEG C, more preferably 140～155 DEG C, most preferably 150～153 DEG C；Enter at a temperature of described first
The response time of row reaction is preferably 2～4 hours, more preferably 2.5～3.5 hours；The temperature of described heating
It is preferably 160～195 DEG C, more preferably 170～193 DEG C, most preferably 180～190 DEG C, described heating
Time is preferably 2～4 hours, more preferably 1～3 hour.
The mode of described heating is not particularly limited by the present invention, with esterification well known to those skilled in the art
The mode of heating of reaction, the present invention is for ensureing that reacting balance is carried out, and preferably constant-speed heating heats up；
The speed that described constant-speed heating is heated up by the present invention is not particularly limited, and those skilled in the art can basis
Reaction temperature, the response time and specifically other reaction conditions be adjusted voluntarily.The present invention is to reaction
Other conditions are not particularly limited, with the reaction condition of esterification well known to those skilled in the art；
Consersion unit is not specially required by the present invention, with consersion unit well known to those skilled in the art.
The present invention is after above-mentioned esterification completes, for improving product purity, preferably to esterification
Product, i.e. thick ester, after carrying out post processing, finally obtain pentaerythritol ester.Post processing is not had by the present invention
There is restriction especially, with the post-processing step preparing pentaerythritol ester well known to those skilled in the art,
Preferably employ following methods to carry out, obtain thick ester through above-mentioned esterification, after cooling is filtered, first to
Reaction system adds the acid in the alkali liquor of excess and in reaction system, then is separated off alkali liquor, then add
Enter activated carbon to be dehydrated, after finally filtering, obtain pentaerythritol ester.
The temperature range of cooling is not particularly limited, with filtration well known to those skilled in the art by the present invention
The filtration temperature of esterification, the present invention is preferably 70～100 DEG C.The mode filtered is not had by the present invention
There is restriction especially, with filter type well known to those skilled in the art.The present invention concentration to alkali liquor
It is not particularly limited, with the concentration of lye for neutralizing well known to those skilled in the art, the present invention
Preferably employ the alkali liquor that mass concentration is 10%.The mode separated is not particularly limited by the present invention, with this
Separate mode known to skilled person, present invention preferably employs standing separation.The present invention is to de-
The method of water is not particularly limited, with post processing dewatering well known to those skilled in the art, excellent
Electing vacuum dehydration as, the vacuum of described vacuum is not particularly limited by the present invention.
The present invention uses tin catalyst to carry out esterification, utilizes the electron orbit that tin catalyst is free,
There is Lewis acid, be combined with organic acid, formed and be similar to organo-metallic compound, can activate
Carbonyl, makes positive charge on carbonylic carbon atom increase, promotes the carrying out of esterification.Further, this
Bright by controlling course of reaction so that tetramethylolmethane can be with the carbon atom quantity satisfied fatty acid less than 10
Carry out esterification, obtain pentaerythritol ester.The esterification process of the tetramethylolmethane that the present invention provides has relatively
High product income and product quality, have relatively low acid number and hydroxyl value, it is possible to moistens under specific condition
Lubricating oil field, relatively low hydroxyl value can weaken product water absorption and with the affinity of metal, to metal portion
The corrosivity of part is little, is suitable to the use condition that water requirement is harsh and cleannes are higher；Relatively low acid number
Then will not cause corrosion of metal, thus preferably protect metal parts.The tetramethylolmethane that the present invention provides
Esterification process also to have post processing simple, pollute the features such as little.
The present invention has obtained pentaerythritol ester through above-mentioned reactions steps, enters obtained pentaerythritol ester
Row detection, test result indicate that, the esterification that the present invention provides.Its conversion ratio is more than 99.5%, reaction
Hydroxyl value in product is less than 1mg KOH/g.
In order to be further appreciated by the present invention, below in conjunction with the embodiment ester to the tetramethylolmethane that the present invention provides
Change method is described in detail, and 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
In, after mix homogeneously, it is 180 DEG C in temperature conditions, under conditions of pressure is 3000Pa, is esterified
Reaction, after reaction 7h, is cooled to 80 DEG C of filtrations, and then adding mass concentration in reaction system is 10%
Alkali liquor in and excess acid, then standing separation remove alkali liquor, the product finally obtained said method enters again
Row washing, obtains pentaerythritol ester after distillation.
After obtaining above-mentioned pentaerythritol ester, testing the performance of pentaerythritol ester, result shows,
The conversion ratio of esterification is 99.7%；Hydroxyl value is 0.3mgKOH/g, and acid number is 0.01mgKOH/g；
Above-mentioned pentaerythritol ester carries out impurities analysis, and wherein S content is higher than detection limit, for 97ppm,
Na content is less than 2.0ppm.
Embodiment 1
First 100g tetramethylolmethane, the positive valeric acid of 360g and 0.46g stannous oxide catalyst are put into reactor
In, after mix homogeneously, first turn on heating system, being heated to temperature conditions is 150 DEG C, and pressure is 3000Pa
Under conditions of, carry out esterification, after reaction 4h, then proceed by uniform speed slow heat temperature raising 3h,
After being warming up to 198 DEG C, it is cooled to 70 DEG C of filtrations, then addition mass concentration is 10% in reaction system
In alkali liquor and excess acid, standing separation removes alkali liquor, finally to the product after separating, in the said goods matter
Carry out vacuum dehydration in the presence of the activated carbon of amount 0.5%, after filtration, obtain pentaerythritol ester.
After obtaining above-mentioned pentaerythritol ester, testing the performance of pentaerythritol ester, result shows,
The conversion ratio of esterification is 99.8%；Hydroxyl value is 0.6mgKOH/g, and acid number is 0.01mgKOH/g；
Above-mentioned pentaerythritol ester carries out impurities analysis, and Sn content is less than 4.0ppm, less than detection limit；Na
Content is less than 2.0ppm, less than detection limit.
Embodiment 2
First 100g tetramethylolmethane, the positive valeric acid of 360g and 0.23g catalyst QS-6 are put in reactor,
After mix homogeneously, first turning on heating system, being heated to temperature conditions is 155 DEG C, and pressure is 3000Pa
Under conditions of, carry out esterification, after reaction 3h, then proceed by uniform speed slow heat temperature raising 2h,
After being warming up to 195 DEG C, it is cooled to 80 DEG C of filtrations, then addition mass concentration is 10% in reaction system
In alkali liquor and excess acid, standing separation removes alkali liquor, finally to the product after separating, in the said goods matter
Carry out vacuum dehydration in the presence of the activated carbon of amount 0.5%, after filtration, obtain pentaerythritol ester.
After obtaining above-mentioned pentaerythritol ester, testing the performance of pentaerythritol ester, result shows,
The conversion ratio of esterification is 99.9%；Hydroxyl value is 0.2mgKOH/g, acid number 0.01mgKOH/g；Right
Above-mentioned pentaerythritol ester carries out impurities analysis, and Sn content is less than 4.0ppm, less than detection limit；Na
Content is less than 2.0ppm, less than detection limit.
Embodiment 3
First by 1mol tetramethylolmethane, the fatty acid mixed of 4.6mol (C5～C9) and 0.24g catalyst
Butyl stannum oxide is put in reactor, after mix homogeneously, first turns on heating system, is heated to temperature strip
Part is 160 DEG C, under conditions of pressure is 3000Pa, carries out esterification, after reaction 4h, then proceedes to
Carry out uniform speed slow heat temperature raising 4h, after being warming up to 190 DEG C, be cooled to 100 DEG C of filtrations, then to reactant
Adding in the alkali liquor that mass concentration is 10% in system and excess acid, standing separation removes alkali liquor, finally to dividing
Product after from, carries out vacuum dehydration, after filtration in the presence of the activated carbon of the said goods quality 0.5%
Obtain pentaerythritol ester.
After obtaining above-mentioned pentaerythritol ester, testing the performance of pentaerythritol ester, result shows,
The conversion ratio of esterification is 99.6%；Hydroxyl value is 0.4mgKOH/g, acid number 0.01mgKOH/g；Right
Above-mentioned pentaerythritol ester carries out impurities analysis, and Sn content is less than 4.0ppm, less than detection limit；Na
Content is less than 2.0ppm, less than detection limit.
Carrying out performance detection to obtaining pentaerythritol ester, its flash-point is 248 DEG C, and 40 DEG C of kinematic viscositys are
19.18mm2/s ,-40 DEG C of kinematic viscositys are 4765mm2/s, and oxide etch (SH/T0450) metal is rotten
Erosion property is 0.0, and 40 DEG C of kinematic viscositys are changed to 42.9%, acid number change 2.36mgKOH/g.
Above the esterification process of a kind of tetramethylolmethane provided by the present invention is described in detail.Herein
In apply concrete individual example principle and the embodiment of the present invention be set forth, above example
Method and the core concept thereof being only intended to help to understand the present invention is described.It should be pointed out that, for this technology
For the those of ordinary skill in field, under the premise without departing from the principles of the invention, it is also possible to the present invention
Carrying out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (7)
1. an esterification process for tetramethylolmethane, comprises the following steps:
A) under the effect of tin catalyst, by tetramethylolmethane with satisfied fatty acid in the first temperature
Under react, then proceed to heating and react, obtain pentaerythritol ester；
Described satisfied fatty acid is in butanoic acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid and capric acid
One or more；
Described tin catalyst is Tin monoxide, QS-6 or butyl stannum oxide；
Described first temperature is 130～160 DEG C, carries out the response time reacted at a temperature of described first
It it is 2～4 hours；The temperature of described heating is 160～195 DEG C, and the time of described heating is 2～4 little
Time.
Esterification process the most according to claim 1, it is characterised in that described tetramethylolmethane with
The mol ratio of satisfied fatty acid is 1:(1.0～6.0).
Esterification process the most according to claim 1, it is characterised in that described tetramethylolmethane with
The mol ratio of satisfied fatty acid is 1:(2.0～6.0).
Esterification process the most according to claim 1, it is characterised in that described tin catalyst
The mass ratio of quality and tetramethylolmethane be (0.005～0.5): 100.
Esterification process the most according to claim 1, it is characterised in that described esterification
Reaction temperature is 130～195 DEG C.
Esterification process the most according to claim 1, it is characterised in that described esterification
Response time is 4～8 hours, and the reaction pressure of described esterification is 3000～10000Pa.
Esterification process the most according to claim 1, it is characterised in that described pentaerythritol ester
Hydroxyl value less than or equal to 2mg KOH/g.
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| 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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| CN103003227A (en) * | 2010-07-17 | 2013-03-27 | 奥克塞有限公司 | Method for aftertreating polyolesters |
| CN102958902A (en) * | 2010-08-24 | 2013-03-06 | Kh新化株式会社 | Tetraester of pentaerythritol |
| CN103429332A (en) * | 2011-02-21 | 2013-12-04 | 埃默里油脂化学有限公司 | Process and device for preparation of ester in granule form |
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