CN110143872A - The preparation method of neopentyl polyol ester - Google Patents
The preparation method of neopentyl polyol ester Download PDFInfo
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- CN110143872A CN110143872A CN201910525496.7A CN201910525496A CN110143872A CN 110143872 A CN110143872 A CN 110143872A CN 201910525496 A CN201910525496 A CN 201910525496A CN 110143872 A CN110143872 A CN 110143872A
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Abstract
The invention belongs to technical field of chemical synthesis, and in particular to a kind of preparation method of neopentyl polyol ester.It uses methyl oleate and alcohol for raw material, using sodium methoxide as catalyst, reacts and neopentyl polyol ester is made；Wherein, alcohol is 2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- glycol or 2- methylol -2- butoxymethyl-propyl alcohol -1,3- glycol.Being used as lubricating oil using the synthetic ester that the method for the present invention obtains has very excellent comprehensive performance, it has preferable high-temperature stability, higher viscosity-temperature characteristics and preferable cryogenic property simultaneously, compared to other lubricating oil, the synthetic ester is the synthesizing ester oil for meeting oil product requirement, new product selection is provided for application of the synthesizing ester oil in lubricating oil, and there is better application value.
Description
Technical field
The invention belongs to technical field of chemical synthesis, and in particular to a kind of preparation method of neopentyl polyol ester.
Background technique
Synthesizing ester oil be a kind of comprehensive performance preferably, development and application a kind of synthetic lubricant fluid earlier；It has very
The performances such as good temperature characterisitic, lubricity, thermo oxidative stability and biodegradable, are mainly used for aero-engine and pressure
Contracting machine lubricating oil, jet engine lubricating oil almost all in the world is Esters oil at present.Therefore, this is a kind of very heavy
The synthetic lubricant fluid wanted.
The molecular characterization of synthesizing ester oil is all to contain ester functional groups in molecule.According to the quantity of ester group in molecule
With the difference of position, synthesizing ester oil is divided into dibasic acid esters, polyol ester and multiple ester again.There are two ester groups for dibasic acid esters, are with dicarboxylic acids
With monohydric alcohol, or the ester reacted with dihydric alcohol with monocarboxylic acid.Polyol ester has more than two ester groups, common more
First alcohol ester has the trihydroxymethylpropanyl ester and pentaerythritol ester of C5-C9 fatty acid.Multiple ester is grown up by binary acid, polyhydric alcohol
Chain molecule, end group use monohydric alcohol or monoacid to be esterified and obtain again, and its structure is complicated, and average molecular weight is generally 800-1500,
Its viscosity is high compared with dibasic acid esters and polyol ester, but its thermal stability is good not as good as polyol ester.In addition to this, there are also one kind bio oils
The lubricating oil in esters of preparation is a kind of environmental-friendly with preferable biological degradability, frictional property and reusable property
Lubricating oil, but since its thermal stability is poor, application field is not extensive.
In these synthesizing esters oil, there is a kind of more special synthetic ester-neopentyl polyol ester, its main feature is that point
It is not hydrogeneous on β carbon atom in son, thus its thermal stability is got well than other esters.Neopentyl polyol ester is because of its special knot
Structure feature and have many advantages, such as excellent high temperature performance, viscosity-temperature characteristics energy, thermo oxidative stability, lubricity, low volatility, simultaneously
With advantages such as excellent biological degradability, low toxicity and raw material reproducibilities, current industrial development pair can be better met
In the requirement of novel lubricating material.Simultaneously because the multi-hydroxy structure on neopentyl polyol ester space structure, from different knots
The linear chain or branched chain fatty acid composition of structure type, makes the ester have wide adjusting performance range, and synthesized neopentyl is polynary
Alcohol ester has the unrivaled superiority of other esters, becomes the optimal selection of current high-end synthesis ester oil grease.Neopentyl is more
First alkoxide oil can be used for grease base plinth oil, mainly protect machine part under harsh use condition, especially suitable
In low temperature and Hmp grease.
Alcohol used in synthesis neopentyl polyol ester generally has pentaerythrite, neopentyl glycol etc., and the β carbon of these polyalcohols is former
Not hydrogen atoms on son.In the selection of acid, some researches show that the esters using oleic acid as Material synthesis may be used as lubricating oil.With
Oleic acid is the synthetic ester that raw material obtains, and can keep good mobility under cryogenic, therefore can be in lower temperature
And used under some extreme weather conditions, but poor high temperature stability.Its viscosity of currently used synthesis ester oil grease refers to
Number is 140-200, and flash-point is 190-330 DEG C, and pour point is-1-- 40 DEG C.For lubricating oil, high-temperature stability, viscous temperature
Performance and cryogenic property are very important index, and the lubricating oil haveing excellent performance needs while keeping indices preferable, mesh
Preceding lubricating oil is more difficult while reaching preferable high-temperature stability, preferable viscosity-temperature characteristics and preferable low-temperature characteristics, usually
Another performance is lost in order to meet certain performance；Such as pentaerythritol ester, Viscosity Index 198, but its pour point compared with
It is low, only -6 DEG C.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of neopentyl polyol ester, have using methyl oleate and with glycerol
There is the alcohols of similar structures as raw material, the polyol ester of synthesizing new structure, with preferable high-temperature stability, preferable
Viscosity-temperature characteristics and preferable low-temperature characteristics.
The preparation method of neopentyl polyol ester of the present invention is to use methyl oleate and alcohol for raw material, with sodium methoxide
As catalyst, reacts and neopentyl polyol ester is made；Wherein, alcohol is 2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- bis-
Alcohol or 2- methylol -2- butoxymethyl-propyl alcohol -1,3- glycol.
2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- glycol preparation method is by (the hydroxyl first of 3,3- bis-
Base)-propylene oxide, ethyl alcohol and sulfuric acid mixing, pH is added anhydrous magnesium sulfate after being adjusted to neutrality, obtains sticky opaque liquid,
By the opaque liquid extracted by ether, 2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- glycol is obtained.
Specific step is as follows for 2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- glycol preparation method:
With 3,3- bis- (methylol)-propylene oxide for raw material, it is added into ethyl alcohol, while sulfuric acid is added, at room temperature
Stirring is added sodium bicarbonate powder, anhydrous magnesium sulfate is added after being adjusted to neutrality, is put into ice bath, is removed by filtration precipitating
Sticky opaque liquid is obtained after salt, which is cleaned by petroleum ether, and put it into Soxhlet extractor
Middle to use extracted by ether, removing the thick liquid obtained after diethyl ether is 2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- bis-
Alcohol.
Wherein, the mass ratio of 3,3- bis- (methylol)-propylene oxide, ethyl alcohol, sulfuric acid and anhydrous magnesium sulfate is 1:7-10:
0.02-0.05:0.4-0.6, preferably 1:8:0.03:0.5, mixing time 72-74h are 12h with the extracted by ether time.
2- methylol -2- butoxymethyl-propyl alcohol -1,3- glycol preparation method is by (the hydroxyl first of 3,3- bis-
Base)-propylene oxide, butanol and sulfuric acid mixing, pH is added anhydrous magnesium sulfate after being adjusted to neutrality, obtains sticky opaque liquid,
By the opaque liquid extracted by ether, 2- methylol -2- butoxymethyl-propyl alcohol -1,3- glycol is obtained.
Specific step is as follows for 2- methylol -2- butoxymethyl-propyl alcohol -1,3- glycol preparation method:
With 3,3- bis- (methylol)-propylene oxide for raw material, it is added into butanol, while sulfuric acid is added, at room temperature
Stirring is added sodium bicarbonate powder, anhydrous magnesium sulfate is added after being adjusted to neutrality, is put into ice bath, is removed by filtration precipitating
Then salt obtains sticky opaque liquid, which is cleaned by petroleum ether, and put it into Soxhlet and mention
It takes with extracted by ether in device, removing the thick liquid obtained after butyl oxide is 2- methylol -2- butoxymethyl-propyl alcohol -1,
3- glycol.
Wherein, the mass ratio of 3,3- bis- (methylol)-propylene oxide, butanol, sulfuric acid and anhydrous magnesium sulfate is 1:1-3:
0.02-0.04:0.4-0.6, preferably 1:2:0.03:0.5, mixing time 96h are 12h with the extracted by ether time.
3,3- bis- (methylol)-propylene oxide preparation method is by pentaerythrite, diethyl carbonate and hydrogen-oxygen
Change potassium mixed dissolution and carry out decarboxylic reaction in dehydrated alcohol, obtains 3,3 two (methylol)-propylene oxide of product.
Specific step is as follows for 3,3- bis- (methylol)-propylene oxide preparation method:
Pentaerythrite, diethyl carbonate and potassium hydroxide are added in round-bottomed flask, is mixed and is dissolved in dehydrated alcohol
In, it is heated to 110-120 DEG C in oil bath, potassium hydroxide is added to again in which after reflux and is then heated to 140-150 DEG C,
Stirring is again heated to 150-200 DEG C after removing the ethyl alcohol of addition, removes diethyl carbonate by Vigreux splitter, will be whole
A system access vacuum pump makes carbonate carry out decarboxylic reaction, and distillation is carried out at 135-165 DEG C can be obtained 3,3 two (hydroxyl of product
Methyl)-propylene oxide.
Wherein, pentaerythrite, diethyl carbonate, potassium hydroxide (gross mass of potassium hydroxide is added twice) and dehydrated alcohol
Mass ratio be 1:3-6:0.1-0.2:0.05-0.06, preferably 1:4:0.1:0.05, potassium hydroxide for the first time be added and second
The mass ratio of secondary addition is 1:1, return time 4-6h, mixing time 4-5h.
The preparation method of the neopentyl polyol ester, includes the following steps:
(1) methyl oleate and alcohol Hybrid Heating are reacted；
(2) sodium methoxide is then added as catalyst, heating obtains mixture；
(3) mixture vacuum back-flow purifies product, obtains neopentyl polyol ester.
The molar ratio of methyl oleate described in step (1) and alcohol is 3-4:1.
Reaction temperature described in step (1) is 65-85 DEG C, reaction time 10-15min.
The additional amount of sodium methoxide described in step (2) is that 0.1-0.6mmol sodium methoxide is added in every 1mol methyl oleate.
Heating time described in step (2) is 1-2h, is heated to 160-190 DEG C.
Reflux temperature described in step (3) is 160-180 DEG C, return time 1.5-4h.
The preparation method of neopentyl polyol ester of the present invention, comprises the following specific steps that:
(1) methyl oleate and alcohol Hybrid Heating are reacted；
(2) sodium methoxide is then added as catalyst, heating；In this process, methanol is removed, mixture is obtained；
(3) mixture flows back under conditions of vacuum, then cools to room temperature, and ether dilution cleaning is added to neutrality, has
Machine layer is dried and passes through suction filtration and removes, and removes remaining methyl oleate, while purifying to product, it is more to obtain neopentyl
First alcohol ester.
The method of removal methanol is vacuum filtration in step (2).
Organic layer is dried using anhydrous magnesium sulfate in step (3), and remaining methyl oleate is removed by vacuum distillation.
The present invention uses 2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- glycol or 2- methylol -2- butoxymethyl -
Propyl alcohol -1,3- glycol synthesizes corresponding neopentyl polyol ester 2- methylol -2- ethoxyl methyl-propyl alcohol-as raw material, preparation
1,3- diol ester or 2- methylol -2- butoxymethyl-propyl alcohol -1,3- diol ester, the neopentyl polyol ester of the synthesis are used as
Lubricating oil has preferable characteristic.
Reaction equation of the invention is as follows:
Wherein, R1For CH2OCH2CH3Or CH2OCH2CH2CH2CH3, R2For oleic acid alkyl chain.
The structural formula of 3,3 2 (methylol)-propylene oxide is as follows:
2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- diol ester structural formula is as follows:
Wherein, R2For oleic acid alkyl chain.
2- methylol -2- butoxymethyl-propyl alcohol -1,3- diol ester structural formula is as follows:
Wherein, R2For oleic acid alkyl chain.
The present invention is mainly to improve the performance of synthetic ester, ethoxyl methyl or butoxy first therein by adjusting group
The introducing of base can improve to a certain extent the Viscosity Index of synthetic ester, while can reduce pour point.
Beneficial effects of the present invention are as follows:
The invention proposes a kind of completely new methods using methyl oleate and alcohol as the high-quality polyol ester of Material synthesis.Using this
Inventive method has obtained the synthesis ester oil grease of structure novel, while the synthetic method is simple, is able to carry out prepare with scale, is
The lubricating oil that magnanimity is had excellent performance provides technical support.Being used as lubricating oil by the synthetic ester that this method obtains has very
Excellent comprehensive performance has preferable high-temperature stability, higher viscosity-temperature characteristics and preferable cryogenic property simultaneously, compares
In other lubricating oil, which is the synthesizing ester oil for meeting oil product requirement, for synthesizing ester oil in lubricating oil
Using new product selection is provided, there is better application value.
Specific embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
(1) 3,3- bis- (methylol)-propylene oxide preparation
Pentaerythrite, diethyl carbonate and potassium hydroxide are added in round-bottomed flask, is mixed and is dissolved in dehydrated alcohol
In.The mixture is heated to 110 DEG C in oil bath, and potassium hydroxide is added to again in which after the 4h that flows back.Then, mixture heats
To 140 DEG C, 4h is stirred, by Vigreux splitter, 180 DEG C is again heated to after removing the ethyl alcohol of addition, removes carbonic acid diethyl
Ester.Whole system is accessed into vacuum pump, carbonate is made to carry out decarboxylic reaction.Distillation is carried out at 145 DEG C can be obtained product -3,3
Two (methylol)-propylene oxide.
(2) 2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- glycol preparation
With 3,3- bis- (methylol)-propylene oxide of preparation for raw material, it is added into ethyl alcohol, while sulfuric acid is added.It is mixed
It closes object and 72h is stirred at room temperature.Sodium bicarbonate powder is added, anhydrous magnesium sulfate is added after mixture is adjusted to neutrality, is put into ice
In bath.Sticky opaque liquid is obtained after being removed by filtration the salt of precipitating.By the substance by petroleum ether clean, and by its
It is put into Soxhlet extractor with extracted by ether 12h.Removing the thick liquid obtained after diethyl ether is 2- methylol -2- second
Oxygroup methyl-propanol -1,3- glycol.
(3) preparation of synthetic ester
Methyl oleate is mixed with the 2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- glycol prepared in step (2) and is added
Then heat is added sodium methoxide as catalyst, 160 DEG C is slowly heated in 1h to 70 DEG C of reaction 12min.In this process,
Methanol is removed by vacuum filtration.Mixture 160 DEG C of holding 2h under conditions of reflux, vacuum.Then mixture is cooled to room
Ether dilution cleaning is added to neutrality in temperature.Organic layer is dried with anhydrous magnesium sulfate, and is removed by filtering.Remaining oil
Sour methyl esters is removed by vacuum distillation, while being purified to product, and 2- methylol -2- ethoxyl methyl-propyl alcohol-is finally obtained
1,3- diol ester.
The result shows that: the Viscosity Index of 2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- diol ester obtained: 195；It dodges
Point: 333 DEG C, condensation point: -35 DEG C.
Embodiment 2
(1) 3,3- bis- (methylol)-propylene oxide preparation
Pentaerythrite, diethyl carbonate and potassium hydroxide are added in round-bottomed flask, is mixed and is dissolved in dehydrated alcohol
In.The mixture is heated to 120 DEG C in oil bath, and potassium hydroxide is added to again in which after the 4h that flows back.Then, mixture heats
To 150 DEG C, 4h is stirred, by Vigreux splitter, 190 DEG C is again heated to after removing the ethyl alcohol of addition, removes carbonic acid diethyl
Ester.Whole system is accessed into vacuum pump, carbonate is made to carry out decarboxylic reaction.Distillation is carried out at 165 DEG C can be obtained product -3,3
Two (methylol)-propylene oxide.
(2) 2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- glycol
With 3,3- bis- (methylol)-propylene oxide of preparation for raw material, it is added into ethyl alcohol, while sulfuric acid is added.It is mixed
It closes object and 74h is stirred at room temperature.Sodium bicarbonate powder is added, anhydrous magnesium sulfate is added after mixture is adjusted to neutrality, is put into ice
In bath.Sticky opaque liquid is obtained after being removed by filtration the salt of precipitating.By the substance by petroleum ether clean, and by its
It is put into Soxhlet extractor with extracted by ether 12h.Removing the thick liquid obtained after diethyl ether is 2- methylol -2- second
Oxygroup methyl-propanol -1,3- glycol.
(3) preparation of synthetic ester
Methyl oleate is heated to the 2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- glycol prepared in step (2)
Then 70 DEG C of reaction 13min are added sodium methoxide as catalyst, 160 DEG C are slowly heated in 1h.In this process, pass through
Vacuum filtration removal methanol.Mixture 160 DEG C of holding 1.5h under conditions of reflux, vacuum.Then mixture is cooled to room temperature,
Ether dilution cleaning is added to neutrality.Organic layer is dried with anhydrous magnesium sulfate, and is removed by filtering.Remaining oleic acid first
Ester is removed by vacuum distillation, while being purified to product, and 2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- is finally obtained
Diol ester.
The result shows that: the Viscosity Index of 2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- diol ester obtained: 193；It dodges
Point: 330 DEG C, condensation point: -35 DEG C.
Embodiment 3
(1) 3,3- bis- (methylol)-propylene oxide preparation
Pentaerythrite, diethyl carbonate and potassium hydroxide are added in round-bottomed flask, is mixed and is dissolved in dehydrated alcohol
In.The mixture is heated to 110 DEG C in oil bath, and potassium hydroxide is added to again in which after the 4h that flows back.Then, mixture heats
To 140 DEG C, 4h is stirred, by Vigreux splitter, 170 DEG C is again heated to after removing the ethyl alcohol of addition, removes carbonic acid diethyl
Ester.Whole system is accessed into vacuum pump, carbonate is made to carry out decarboxylic reaction.Distillation is carried out at 140 DEG C can be obtained product -3,3
Two (methylol)-propylene oxide.
(2) 2- methylol -2- butoxymethyl-propyl alcohol -1,3- glycol preparation
With 3,3- bis- (methylol)-propylene oxide of preparation for raw material, it is added into butanol, while sulfuric acid is added.It is mixed
It closes object and 96h is stirred at room temperature.Sodium bicarbonate powder is added, anhydrous magnesium sulfate is added after mixture is adjusted to neutrality, is put into ice
In bath.It is removed by filtration the salt of precipitating, then obtains sticky opaque liquid.The substance is cleaned by petroleum ether, and
It puts it into Soxhlet extractor with extracted by ether 12h.Removing the thick liquid obtained after butyl oxide is 2- methylol-
2- butoxymethyl-propyl alcohol -1,3- glycol.
(3) preparation of synthetic ester
Methyl oleate is mixed with the 2- methylol -2- butoxymethyl-propyl alcohol -1,3- glycol prepared in step (2) and is added
Then heat is added sodium methoxide as catalyst, 180 DEG C is slowly heated in 1h to 70 DEG C of reaction 15min.In this process,
Methanol is removed by vacuum filtration.Mixture 160 DEG C of holding 2h under conditions of reflux, vacuum.Then mixture is cooled to room
Ether dilution cleaning is added to neutrality in temperature.Organic layer is dried with anhydrous magnesium sulfate, and is removed by filtering.Remaining oil
Sour methyl esters is removed by vacuum distillation, while being purified to product, and 2- methylol -2- butoxymethyl-propyl alcohol-is finally obtained
1,3- diol ester.
The result shows that: the Viscosity Index of 2- methylol -2- butoxymethyl-propyl alcohol -1,3- diol ester obtained: 194；It dodges
Point: 316 DEG C, condensation point: -33 DEG C.
Embodiment 4
(1) 3,3- bis- (methylol)-propylene oxide preparation
Pentaerythrite, diethyl carbonate and potassium hydroxide are added in round-bottomed flask, is mixed and is dissolved in dehydrated alcohol
In.The mixture is heated to 120 DEG C in oil bath, and potassium hydroxide is added to again in which after the 4h that flows back.Then, mixture heats
To 150 DEG C, 4h is stirred, by Vigreux splitter, 150 DEG C is again heated to after removing the ethyl alcohol of addition, removes carbonic acid diethyl
Ester.Whole system is accessed into vacuum pump, carbonate is made to carry out decarboxylic reaction.Distillation is carried out at 135 DEG C can be obtained product -3,3
Two (methylol)-propylene oxide.
(2) 2- methylol -2- butoxymethyl-propyl alcohol -1,3- glycol preparation
With 3,3- bis- (methylol)-propylene oxide of preparation for raw material, it is added into butanol, while sulfuric acid is added.It is mixed
It closes object and 96h is stirred at room temperature.Sodium bicarbonate powder is added, anhydrous magnesium sulfate is added after mixture is adjusted to neutrality, is put into ice
In bath.It is removed by filtration the salt of precipitating, then obtains sticky opaque liquid.The substance is cleaned by petroleum ether, and
It puts it into Soxhlet extractor with extracted by ether 12h.Removing the thick liquid obtained after butyl oxide is 2- methylol-
2- butoxymethyl-propyl alcohol -1,3- glycol.
(3) preparation of synthetic ester
Methyl oleate is heated to the 2- methylol -2- butoxymethyl-propyl alcohol -1,3- glycol prepared in step (2)
Then 70 DEG C of reaction 10min are added sodium methoxide as catalyst, 185 DEG C are slowly heated in 1h.In this process, pass through
Vacuum filtration removal methanol.Mixture 160 DEG C of holding 2h under conditions of reflux, vacuum.Then mixture is cooled to room temperature, and is added
Enter ether dilution cleaning to neutrality.Organic layer is dried with anhydrous magnesium sulfate, and is removed by filtering.Remaining methyl oleate
It is removed by vacuum distillation, while product is purified, finally obtain 2- methylol -2- butoxymethyl-propyl alcohol -1,3- bis-
Alcohol ester.
The result shows that: the Viscosity Index of 2- methylol -2- butoxymethyl-propyl alcohol -1,3- diol ester obtained: 201；It dodges
Point: 315 DEG C, condensation point: -35 DEG C.
Comparative example 1
(1) 3,3- bis- (methylol)-propylene oxide preparation
Pentaerythrite, diethyl carbonate and potassium hydroxide are added in round-bottomed flask, is mixed and is dissolved in dehydrated alcohol
In.The mixture is heated to 110 DEG C in oil bath, and potassium hydroxide is added to again in which after the 4h that flows back.Then, mixture heats
To 140 DEG C, 4h is stirred, by Vigreux splitter, 150 DEG C is again heated to after removing the ethyl alcohol of addition, removes carbonic acid diethyl
Ester.Whole system is accessed into vacuum pump, carbonate is made to carry out decarboxylic reaction.Distillation is carried out at 135 DEG C can be obtained product -3,3
Two (methylol)-propylene oxide.
(2) 2- methylol -2- methoxy-propyl alcohol -1,3- glycol preparation
With 3,3- bis- (methylol)-propylene oxide of preparation for raw material, it is added into methanol, while sulfuric acid is added.It is mixed
It closes object and 48h is stirred at room temperature.Sodium bicarbonate powder is added, anhydrous magnesium sulfate is added after mixture is adjusted to neutrality, is put into ice
In bath.It is removed by filtration the salt of precipitating, then obtains sticky opaque liquid.The substance is cleaned by petroleum ether, and
It puts it into Soxhlet extractor with extracted by ether 12h.Removing the thick liquid obtained after butyl oxide is 2- methylol-
2- methoxy-propyl alcohol -1,3- glycol.
(3) preparation of synthetic ester
Methyl oleate is heated to the 2- methylol -2- methoxy-propyl alcohol -1,3- glycol prepared in step (2)
Then 75 DEG C of reaction 10min are added sodium methoxide as catalyst, 185 DEG C are slowly heated in 1h.In this process, pass through
Vacuum filtration removal methanol.Mixture 160 DEG C of holding 2h under conditions of reflux, vacuum.Then mixture is cooled to room temperature, and is added
Enter ether dilution cleaning to neutrality.Organic layer is dried with anhydrous magnesium sulfate, and is removed by filtering.Remaining methyl oleate
It is removed by vacuum distillation, while product is purified, finally obtain 2- methylol -2- methoxy-propyl alcohol -1,3- bis-
Alcohol ester.
The result shows that: the Viscosity Index of 2- methylol -2- methoxy-propyl alcohol -1,3- diol ester obtained: 160；It dodges
Point: 306 DEG C, condensation point: -15 DEG C.
Comparative example 2
(1) 3,3- bis- (methylol)-propylene oxide preparation
Pentaerythrite, diethyl carbonate and potassium hydroxide are added in round-bottomed flask, is mixed and is dissolved in dehydrated alcohol
In.The mixture is heated to 120 DEG C in oil bath, and potassium hydroxide is added to again in which after the 4h that flows back.Then, mixture heats
To 150 DEG C, 4h is stirred, by Vigreux splitter, 150 DEG C is again heated to after removing the ethyl alcohol of addition, removes carbonic acid diethyl
Ester.Whole system is accessed into vacuum pump, carbonate is made to carry out decarboxylic reaction.Distillation is carried out at 135 DEG C can be obtained product -3,3
Two (methylol)-propylene oxide.
(2) 2- methylol -2- Phenoxymethyl-propyl alcohol -1,3- glycol preparation
Potassium hydroxide and phenol are dissolved in water in rustless steel container, add 3,3- bis- (methylol)-epoxy third
Alkane is heated to 170 DEG C of reaction 17h；It is cooling that water is added, while hydrochloric acid is added and is divided into two-phase；Then chloroform is added to be extracted, it will
It is 2- methylol -2- benzene oxygen that organic phase, which is put into the sticky brown liquid for drying, filtering in anhydrous magnesium sulfate and obtaining after centrifugation,
Methyl-propanol -1,3- glycol.
(3) preparation of synthetic ester
2- methylol -2- Phenoxymethyl-propyl alcohol -1,3- the glycol prepared in methyl oleate and step (2) is heated to 75
DEG C reaction 10min, then be added sodium methoxide as catalyst, 185 DEG C are slowly heated in 1h.In this process, by true
Empty pump, which filters off, removes methanol.Mixture 160 DEG C of holding 2h under conditions of reflux, vacuum.Then mixture is cooled to room temperature, and is added
Ether dilution is cleaned to neutrality.Organic layer is dried with anhydrous magnesium sulfate, and is removed by filtering.Remaining methyl oleate is logical
It crosses vacuum distillation to remove, while product is purified, finally obtain 2- methylol -2- Phenoxymethyl-propyl alcohol -1,3- glycol
Ester.
The result shows that: the Viscosity Index of 2- methylol -2- Phenoxymethyl-propyl alcohol -1,3- diol ester obtained: 164；It dodges
Point: 312 DEG C, condensation point: -16 DEG C.
The Specifeca tion speeification comparing result of 1 embodiment 1-4 of table, comparative example 1-2 and existing synthetic ester
Interpretation of result:
Comparative example 1 and comparative example 2 are in experimentation of the present invention using 2- methylol -2- methoxy-propyl alcohol -1,3-
Two pure and mild 2- methylol -2- Phenoxymethyls-propyl alcohol -1,3- glycol preparation, two kinds of synthetic esters, pentaerythritol ester and trihydroxy methyl
Propane oleate is existing synthetic ester.
By the data in table 1, it can be seen that the Viscosity Index (192-195) of synthetic ester obtained in the embodiment of the present invention
Higher than the Viscosity Index (160-164) of synthetic ester in comparative example, the flash-point (313-333 DEG C) of synthetic ester obtained in embodiment
Synthetic ester flash-point (306-312 DEG C) slightly above in comparative example, synthetic ester obtained in embodiment have excellent cryogenic property,
(- 35-- 32 DEG C) of the condensation point condensation points (- 16-- 15 DEG C) lower than synthetic ester in comparative example；It is above-mentioned to use this hair statistics indicate that only having
Bright selection two kinds of alcohol preparation two kinds of synthetic esters just simultaneously have preferable high-temperature stability, preferable viscosity-temperature characteristics and compared with
Good low-temperature characteristics, excellent combination property.
Synthetic ester obtained in the embodiment of the present invention is relative to existing synthetic ester pentaerythritol ester and trimethylolpropane
For oleate, flash-point is higher, condensation point is lower, and the comprehensive performance of synthetic ester prepared by the present invention will be significantly larger than existing synthesis
Ester.
Synthetic ester prepared by the present invention has excellent comprehensive performance, and the application range of synthetic ester will be widened significantly.
Claims (10)
1. a kind of preparation method of neopentyl polyol ester, it is characterised in that use methyl oleate and alcohol for raw material, with sodium methoxide
As catalyst, reacts and neopentyl polyol ester is made；Wherein, alcohol is 2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- bis-
Alcohol or 2- methylol -2- butoxymethyl-propyl alcohol -1,3- glycol.
2. the preparation method of neopentyl polyol ester according to claim 1, it is characterised in that the 2- methylol -2-
Ethoxyl methyl-propyl alcohol -1,3- glycol preparation method is to mix 3,3- bis- (methylol)-propylene oxide, ethyl alcohol and sulfuric acid,
Anhydrous magnesium sulfate is added after being adjusted to neutrality in pH, obtains sticky opaque liquid, which obtains
2- methylol -2- ethoxyl methyl-propyl alcohol -1,3- glycol.
3. the preparation method of neopentyl polyol ester according to claim 1, it is characterised in that the 2- methylol -2-
Butoxymethyl-propyl alcohol -1,3- glycol preparation method is to mix 3,3- bis- (methylol)-propylene oxide, butanol and sulfuric acid,
Anhydrous magnesium sulfate is added after being adjusted to neutrality in pH, obtains sticky opaque liquid, which obtains
2- methylol -2- butoxymethyl-propyl alcohol -1,3- glycol.
4. the preparation method of neopentyl polyol ester according to claim 2 or 3, it is characterised in that 3, the 3- bis-
The preparation method of (methylol)-propylene oxide is by pentaerythrite, diethyl carbonate and potassium hydroxide mixed dissolution in anhydrous second
Decarboxylic reaction is carried out in alcohol, obtains 3,3 two (methylol)-propylene oxide of product.
5. the preparation method of neopentyl polyol ester according to claim 1, it is characterised in that include the following steps:
(1) methyl oleate and alcohol Hybrid Heating are reacted；
(2) sodium methoxide is then added as catalyst, heating obtains mixture；
(3) mixture vacuum back-flow purifies product, obtains neopentyl polyol ester.
6. the preparation method of neopentyl polyol ester according to claim 5, it is characterised in that oil described in step (1)
The molar ratio of sour methyl esters and alcohol is 3-4:1.
7. the preparation method of neopentyl polyol ester according to claim 5, it is characterised in that anti-described in step (1)
Answering temperature is 65-85 DEG C, reaction time 10-15min.
8. the preparation method of neopentyl polyol ester according to claim 5, it is characterised in that first described in step (2)
The additional amount of sodium alkoxide is that 0.1-0.6mmol sodium methoxide is added in every 1mol methyl oleate.
9. the preparation method of neopentyl polyol ester according to claim 5, it is characterised in that add described in step (2)
The hot time is 1-2h, is heated to 160-190 DEG C.
10. the preparation method of neopentyl polyol ester according to claim 5, it is characterised in that described in step (3)
Reflux temperature is 160-180 DEG C, return time 1.5-4h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101853036B1 (en) * | 2017-09-12 | 2018-04-27 | 주식회사 광우 | A method for producing a functional synthetic oil using purified fatty acid and a functional synthetic oil using the same |
| CN108863785A (en) * | 2018-07-25 | 2018-11-23 | 湖南理工学院 | A kind of low pour point pentaerythritol oleate mixed ester and its synthetic method |
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2019
- 2019-06-18 CN CN201910525496.7A patent/CN110143872A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101853036B1 (en) * | 2017-09-12 | 2018-04-27 | 주식회사 광우 | A method for producing a functional synthetic oil using purified fatty acid and a functional synthetic oil using the same |
| CN108863785A (en) * | 2018-07-25 | 2018-11-23 | 湖南理工学院 | A kind of low pour point pentaerythritol oleate mixed ester and its synthetic method |
Non-Patent Citations (1)
| Title |
|---|
| IGOR MARQUES CAVALCANTE ，ET AL: "Synthesis and Characterization of New Esters of Oleic Acid and Glycerol Analogues as Potential Lubricants", 《NDUSTRIAL CROPS AND PRODUCTS》 * |
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