CN110256396A - Glycerine acetal (ketone) ether and its synthetic method - Google Patents
Glycerine acetal (ketone) ether and its synthetic method Download PDFInfo
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- CN110256396A CN110256396A CN201910371098.4A CN201910371098A CN110256396A CN 110256396 A CN110256396 A CN 110256396A CN 201910371098 A CN201910371098 A CN 201910371098A CN 110256396 A CN110256396 A CN 110256396A
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- C07—ORGANIC CHEMISTRY
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- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
- C07D317/22—Radicals substituted by singly bound oxygen or sulfur atoms etherified
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Abstract
The invention discloses a kind of glycerine acetal (ketone) ether and its synthetic methods, are related to technical field of chemical synthesis.Glycerine acetal (ketone) ether disclosed by the invention is that cyclic ketal (ketone) and Mi Liangzhong functional group are integrated into a molecule using glycerol as raw material, and the service efficiency of unit fuel oil additive can be improved in this glycerine acetal (ketone) ether.In disclosed synthetic method, there are two synthetic routes, can be first etherified and carry out acetal (ketone) change again, can also first carry out acetal (ketone) change and be etherified again.Wherein, etherification reaction is atomic economy reaction；The by-product that acetal (ketone) changes reaction only has a molecular water, and method is environmentally protective, high-efficient；The high income of glycerine acetal (ketone) ether in product, up to 99%；Using solid acid catalyst, cleaning efficiently, can be recycled, and significantly reduce cost, and industrial value is high.
Description
Technical field
The present invention relates to technical field of chemical synthesis more particularly to glycerine acetal (ketone) ether and its synthetic methods.
Background technique
With production of biodiesel flourishing in the whole world, glycerol is as biological diesel oil byproduct also a large amount of outputs.Estimate
The yield for counting the year two thousand twenty whole world glycerol will be up to 41,900,000 liters/year.In order to avoid the saturation of glycerol market, high added value is developed
Product consumes large excess of glycerol, will be a very urgent thing for Biodiesel.Although a variety of sweet
Oily deriving technology is all developed, such as synthesizing epoxy chloropropane, ethylene glycol or propylene glycol and dihydroxyacetone (DHA), but these are right
The effect of an utterly inadequate amount has been only served in the superfluous glycerol of consumption.Fuel oil industry is the very big and most suitable city of a potentiality
, if can develop comburant (-rent) oil derived from glycerol will bring following benefit: one side market prospects are very good, on the other hand quite
In the accessory substance of biodiesel is re-applied to fuel industry, this glycerol spin-off of the third aspect is biology base.
But glycerol is difficult to be directly used as fuel, because its calorific value is very low, polarity is very big.But, glycerol is easy to turn
It is melted into glycerol ketals or glycerol tertbutyl ether.Glycerol ketals or glycerol tertbutyl ether have proven to be very potential fuel oil
Oxygenated additive (Energy Fuels2010；24；2733–6；Journal of Catalysis 2007；245；428–35；
Biomass Bioenergy 2011；35；3636–42；Bioresource Technology 2010；101；6225–9).It is sweet
Oily ketal or glycerol tertbutyl ether may be used as the oxygenation agent or combustion-supporting agent of gasoline, have the octane number for improving gasoline, well
Low temperature flow, outstanding firing characteristic reduce the discharge of particulate matter, reduce formation (the Pet Chem 2011 of colloid；51:
61–9；Energy Fuels2008；22:4271–80；US Patent 6 2005；Excellent performance 890:364).In addition, sweet
Oil contracting acetone LC50 in the toxotest to fish can be up to 3162ppm, and existing frequently-used gasoline additive methyl
Tertbutyl ether (MTBE) is to water toxicity LC50 < < 1000ppm of fish, and therefore, glycerol ketals or glycerol tertbutyl ether are more green
Color, friendly fuel assistants.
To sum up, glycerol is made into glycerol acetonide acetone or is made into the ethers of glycerol for the additive of fuel oil to be that glycerol carries out high attached
The effective way of value added exploitation.However, the fuel oil additive of glycerols is with glycerol tertbutyl ether or glycerol acetonide acetone list at present
Solely exist, the performance as fuel oil additive is single, and Cetane number is general, also very general with the Combination of fuel oil.
Summary of the invention
The technical problem to be solved by the present invention is to integrate glycerine acetal (ketone) and glycerin ether, added with improving fuel oil
Add the performance of agent, improves Cetane number and its mixed performance with fuel oil.
To solve the above-mentioned problems, the present invention proposes following technical scheme:
In a first aspect, the present invention proposes a kind of glycerine acetal (ketone) ether, which is characterized in that indicated by following structural formula:
Second aspect, the present invention propose the synthetic method of glycerine acetal (ketone) ether as described in relation to the first aspect, including following
Step:
A. etherification reaction, glycerol and alkene press the mass ratio of the material 1:1-10, under the action of the first solid acid catalyst,
20-250 DEG C of reaction 0.5-48h obtains glycerol monoethers；
B. acetal (ketone) changes reaction, glycerin ether and aldehyde (ketone) is pressed the mass ratio of the material 1:1-50, in the second solid acid catalysis
Under the action of agent, in 20-250 DEG C of reaction 0.5-48h, glycerine acetal (ketone) ether is obtained.
The third aspect, the present invention propose the synthetic method of glycerine acetal (ketone) ether as described in relation to the first aspect, including following
Step:
A) acetal (ketone) changes reaction, and glycerol and aldehyde (ketone) press the mass ratio of the material 1:1-50, in the second solid acid catalyst
Under effect, in 20-250 DEG C of reaction 0.5-48h, obtain glycerine acetal (ketone)；
Glycerine acetal (ketone) and alkene are pressed the mass ratio of the material 1:1-10, in the first solid acid catalyst by b) etherification reaction
Under the action of, in 20-250 DEG C of reaction 0.5-48h, obtain glycerine acetal (ketone) ether.
Further technical solution is for it, and the alkene is propylene, isobutene, iso-amylene, at least one in norbornene
Kind.
Further technical solution is for it, and the aldehyde (ketone) is formaldehyde, paraformaldehyde, acetaldehyde, at least one of acetone.
Further technical solution is for it, and the mass fraction of the glycerol is the mass fraction of 20-99.9%, the alkene
For 20-99.5%.
Further technical solution is for it, and first solid acid catalyst includes that alkyl-substituted benzene sulfonic acid, alkyl take
The naphthalene sulfonic acids in generation, non-alkyl-substituted benzene sulfonic acid, non-alkyl-substituted naphthalene sulfonic acids, poly- sulfonic resin, poly- perfluorosulfonic acid type tree
Rouge, heteropoly acid and heteropolyacid salt, molecular sieve, acidic ion liquid, single complex carrier SO4 2-/MXOYSolid super-strong acid,
S2O8 2-/MXOYAt least one of solid super-strong acid, wherein MXOYFor NiO, TiO2, ZrO2, SiO2, SnO2, Fe2O3, Al2O3,
WO3And MoO3At least one of.
Further technical solution is for it, and second solid acid catalyst includes that alkyl-substituted benzene sulfonic acid, alkyl take
The naphthalene sulfonic acids in generation, non-alkyl-substituted benzene sulfonic acid, non-alkyl-substituted naphthalene sulfonic acids, poly- sulfonic resin, poly- perfluorosulfonic acid type tree
Rouge, heteropoly acid and heteropolyacid salt, molecular sieve, acidic ion liquid, single complex carrier SO4 2-/MXOYSolid super-strong acid,
S2O8 2-/MXOYAt least one of solid super-strong acid, wherein MXOYFor NiO, TiO2, ZrO2, SiO2, SnO2, Fe2O3, Al2O3,
WO3And MoO3At least one of.
Further technical solution is for it, and the etherification reaction is in no solvent or carries out under the conditions of have existing for solvent anti-
It answers or is reacted in ionic liquid supercritical carbon dioxide；The acetal (ketone) changes reaction in no solvent or has solvent to deposit
It carries out reacting or being reacted in ionic liquid supercritical carbon dioxide under the conditions.
Further technical solution is for it, and the etherification reaction is in air atmosphere, nitrogen atmosphere, argon atmosphere, titanium dioxide
It is reacted under at least one of carbon atmosphere atmosphere；The acetal (ketone) changes reaction in air atmosphere, nitrogen atmosphere, argon gas
It is reacted under at least one of atmosphere, carbon dioxide atmosphere atmosphere.
Compared with prior art, the accessible technical effect of the present invention includes:
(1) cyclic ketal (ketone) and Mi Liangzhong functional group are integrated into a molecule and obtain glycerine acetal (ketone) ether, it is this
The using effect of unit fuel oil additive can be improved in acetal (ketone) ether；
(2) in the synthetic method of glycerine acetal (ketone) ether, there are two synthetic routes, can be first etherified and carry out acetal again
(ketone) is changed, and can also first carry out acetal (ketone) change and is etherified again.Wherein, etherification reaction is atomic economy reaction maximizing
Improve the conversion ratio of reactant；The by-product that acetal (ketone) changes reaction only has a molecular water；Synthetic method is environmentally protective, efficiency
Height, the high income of glycerine acetal (ketone) ether in product, up to 99%；Reaction is catalysis with solid super-strong acid or ionic liquid
Agent, cleaning, efficiently, catalyst can recycle；Cost is significantly reduced, industrial value is high.
Specific embodiment
The technical solution in embodiment will be clearly and completely described below.
It should be appreciated that ought use in this specification and in the appended claims, term " includes " and "comprising" instruction
Described feature, entirety, step, operation, the presence of element and/or component, but one or more of the other feature, whole is not precluded
Body, step, operation, the presence or addition of element, component and/or its set.
It is also understood that in this embodiment of the present invention term used in the description merely for the sake of description particular implementation
Example purpose and be not intended to limit the embodiment of the present invention.Such as the institute in specification and appended book of the embodiment of the present invention
As use, other situations unless the context is clearly specified, otherwise " one " of singular, "one" and "the" are intended to wrap
Include plural form.
The embodiment of the present invention proposes a kind of glycerine acetal (ketone) ether, is indicated by following structural formula:
Wherein, R is at least one of isopropyl, tert-butyl, tertiary pentyl, norborneol alkyl；R1 is H or methyl；R2 is H
Or methyl.
The embodiment of the present invention also provides the synthetic route of above-mentioned glycerine acetal (ketone) ether, as follows:
Wherein, Olefine indicates olefin compound；Aldehyde indicates aldehyde material；Acetone indicates letones；R
For at least one of isopropyl, tert-butyl, tertiary pentyl, norborneol alkyl；R1For H or methyl；R2For H or methyl.
Synthetic route one, comprising the following steps:
A. etherification reaction, glycerol and alkene press the mass ratio of the material 1:1-10, under the action of the first solid acid catalyst,
20-250 DEG C of reaction 0.5-48h obtains glycerin ether, wherein the mass ratio of the first solid acid catalyst and glycerol is 1:10-
1000；
B. acetal (ketone) changes reaction, glycerin ether and aldehyde (ketone) is pressed the mass ratio of the material 1:1-50, in the second solid acid catalysis
Under the action of agent, in 20-250 DEG C of reaction 0.5-48h, obtain glycerine acetal (ketone) ether, wherein the second solid acid catalyst with it is sweet
The mass ratio of oily ether is 1:10-1000.Such as:
In one embodiment, selection glycerol and alkene press the mass ratio of the material 1:1, in the effect of the first solid acid catalyst
Under, in 250 DEG C of reaction 0.5h, obtain glycerin ether, wherein the mass ratio of the first solid acid catalyst and glycerol is 1:10；It will be sweet
Oily ether and aldehyde (ketone) press the mass ratio of the material 1:1, under the action of the second solid acid catalyst, in 250 DEG C of reaction 0.5h, obtain sweet
Oily acetal (ketone) ether, wherein the mass ratio of the second solid acid catalyst and glycerin ether is 1:10.
In one embodiment, selection glycerol and alkene press the mass ratio of the material 1:3, in the effect of the first solid acid catalyst
Under, in 200 DEG C of reaction 4h, obtain glycerin ether, wherein the mass ratio of the first solid acid catalyst and glycerol is 1:50；By glycerol
Ether and aldehyde (ketone) press the mass ratio of the material 1:5, under the action of the second solid acid catalyst, in 200 DEG C of reaction 4h, obtain glycerol acetonide
Aldehyde (ketone) ether, wherein the mass ratio of the second solid acid catalyst and glycerin ether is 1:50.
In one embodiment, selection glycerol and alkene press the mass ratio of the material 1:5, in the effect of the first solid acid catalyst
Under, in 100 DEG C of reaction 12h, obtain glycerin ether, wherein the mass ratio of the first solid acid catalyst and glycerol is 1:200；It will be sweet
Oily ether and aldehyde (ketone) press the mass ratio of the material 1:10, under the action of the second solid acid catalyst, in 100 DEG C of reaction 12h, obtain sweet
Oily acetal (ketone) ether, wherein the mass ratio of the second solid acid catalyst and glycerin ether is 1:200.
In one embodiment, selection glycerol and alkene press the mass ratio of the material 1:8, in the effect of the first solid acid catalyst
Under, it is reacted at 50 DEG C for 24 hours, obtains glycerin ether, wherein the mass ratio of the first solid acid catalyst and glycerol is 1:500；By glycerol
Ether and aldehyde (ketone) press the mass ratio of the material 1:20, under the action of the second solid acid catalyst, are reacted for 24 hours at 50 DEG C, obtain glycerol
Acetal (ketone) ether, wherein the mass ratio of the second solid acid catalyst and glycerin ether is 1:500.
In one embodiment, selection glycerol and alkene press the mass ratio of the material 1:10, in the effect of the first solid acid catalyst
Under, in 25 DEG C of reaction 48h, obtain glycerin ether, wherein the mass ratio of the first solid acid catalyst and glycerol is 1:1000；It will be sweet
Oily ether and aldehyde (ketone) press the mass ratio of the material 1:50, under the action of the second solid acid catalyst, in 25 DEG C of reaction 48h, obtain sweet
Oily acetal (ketone) ether, wherein the mass ratio of the second solid acid catalyst and glycerin ether is 1:1000.
Synthetic route two, comprising the following steps:
A) acetal (ketone) changes reaction, and glycerol and aldehyde (ketone) press the mass ratio of the material 1:1-50, in the second solid acid catalyst
Under effect, in 20-250 DEG C of reaction 0.5-48h, obtain glycerine acetal (ketone), wherein the matter of the second solid acid catalyst and glycerol
Amount is than being 1:10-1000；
Glycerine acetal (ketone) and alkene are pressed the mass ratio of the material 1:1-10, in the first solid acid catalyst by b) etherification reaction
Under the action of, in 20-250 DEG C of reaction 0.5-48h, obtain glycerine acetal (ketone) ether, wherein the first solid acid catalyst and glycerol
The mass ratio of acetal (ketone) is 1:10-1000.Such as:
In one embodiment, glycerol and aldehyde (ketone) are pressed into the mass ratio of the material 1:2, in the effect of the second solid acid catalyst
Under, it in 220 DEG C of reaction 2h, obtains glycerine acetal (ketone), wherein the mass ratio of the second solid acid catalyst and glycerol is 1:20；
By glycerine acetal (ketone) and alkene by the mass ratio of the material 1:1 under the action of the first solid acid catalyst, in 220 DEG C of reaction 2h,
Obtain glycerine acetal (ketone) ether, wherein the mass ratio of the first solid acid catalyst and glycerine acetal (ketone) is 1:20.
In one embodiment, glycerol and aldehyde (ketone) are pressed into the mass ratio of the material 1:10, in the effect of the second solid acid catalyst
Under, it in 180 DEG C of reaction 8h, obtains glycerine acetal (ketone), wherein the mass ratio of the second solid acid catalyst and glycerol is 1:600；
By glycerine acetal (ketone) and alkene by the mass ratio of the material 1:4 under the action of the first solid acid catalyst, in 180 DEG C of reaction 8h,
Obtain glycerine acetal (ketone) ether, wherein the mass ratio of the first solid acid catalyst and glycerine acetal (ketone) is 1:600.
In one embodiment, glycerol and aldehyde (ketone) are pressed into the mass ratio of the material 1:40, in the effect of the second solid acid catalyst
Under, it in 120 DEG C of reaction 6h, obtains glycerine acetal (ketone), wherein the mass ratio of the second solid acid catalyst and glycerol is 1:30；
By glycerine acetal (ketone) and alkene by the mass ratio of the material 1:9 under the action of the first solid acid catalyst, in 120 DEG C of reaction 5h,
Obtain glycerine acetal (ketone) ether, wherein the mass ratio of the first solid acid catalyst and glycerine acetal (ketone) is 1:40.
It should be noted that the alkene in synthetic route one or synthetic route two is propylene, and isobutene, iso-amylene,
At least one of norbornene.
The aldehyde (ketone) in synthetic route one, synthetic route two is formaldehyde, paraformaldehyde, acetaldehyde, in acetone at least
It is a kind of.
The mass fraction of the glycerol in synthetic route one, synthetic route two is the quality of 20-99.9%, the alkene
Score is 20-99.5%.Such as:
In one embodiment, selecting mass fraction is 99% glycerol, and the alkene that mass fraction is 99.5% is reacted.
In one embodiment, selecting mass fraction is 75% glycerol, and the alkene that mass fraction is 80% is reacted.
In one embodiment, selecting mass fraction is 40% glycerol, and the alkene that mass fraction is 50% is reacted.
In one embodiment, selecting mass fraction is 20% glycerol, and the alkene that mass fraction is 20% is reacted.
First solid acid catalyst in synthetic route one, synthetic route two includes alkyl-substituted benzene sulfonic acid, alkane
Naphthalene sulfonic acids, the non-alkyl-substituted benzene sulfonic acid, non-alkyl-substituted naphthalene sulfonic acids, poly- sulfonic resin, poly- perfluorinated sulfonic acid of base substitution
Type resin, heteropoly acid and heteropolyacid salt, molecular sieve, acidic ion liquid, single complex carrier SO4 2-/MXOYSolid super-strong acid,
S2O8 2-/MXOYAt least one of solid super-strong acid, wherein MXOYFor NiO, TiO2, ZrO2, SiO2, SnO2, Fe2O3, Al2O3,
WO3And MoO3At least one of.
Second solid acid catalyst in synthetic route one, synthetic route two includes alkyl-substituted benzene sulfonic acid, alkane
Naphthalene sulfonic acids, the non-alkyl-substituted benzene sulfonic acid, non-alkyl-substituted naphthalene sulfonic acids, poly- sulfonic resin, poly- perfluorinated sulfonic acid of base substitution
Type resin, heteropoly acid and heteropolyacid salt, molecular sieve, acidic ion liquid, single complex carrier SO4 2-/MXOYSolid super-strong acid,
S2O8 2-/MXOYAt least one of solid super-strong acid, wherein MXOYFor NiO, TiO2, ZrO2, SiO2, SnO2, Fe2O3, Al2O3,
WO3And MoO3At least one of.
It should be noted that the first solid acid catalyst, the second solid acid catalyst can be Bronst acid and be also possible to
Lewis acid, can also be two kinds of sour mixtures, can with but be not limited to for example alkyl-substituted benzene sulfonic acid of solid acid, alkyl takes
The naphthalene sulfonic acids in generation, non-alkyl-substituted benzene sulfonic acid, non-alkyl-substituted naphthalene sulfonic acids, poly- sulfonic resin such as AmberlystTMSeries
(Rohm&Haas, USA, PA), poly- perfluorosulfonic acid type resin are such asIt is serial (Dupont, USA, lavare), single or multiple
Close the super acids SO of carrier4 2-/MXOYOr S2O8 2-/MXOYSolid super-strong acid, wherein MXOYFor NiO, TiO2, ZrO2, SiO2, SnO2,
Fe2O3, Al2O3, WO3And MoO3One of or more than one), heteropoly acid and heteropolyacid salt (its central atom can with but not office
Be limited to P, Si, Fe and Co, coordination atom can with but be not limited to be active carbon, metal oxide, molecular sieve, clay and have
Machine polymer, carbon nanotube, graphene) and natural or synthetic molecular sieve, it is also possible to ionic liquid (sulfuric acid, three chloroethenes
Acid, trifluoromethanesulfonic acid and alkyl sulfonic acid), including acidic ion liquid (can with but be not limited to SO3H- or COOH- functionalization from
Sub- liquid).
In one embodiment, the first solid acid catalyst, the second solid acid catalyst are identical.
In one embodiment, the first solid acid catalyst, the second solid acid catalyst be not identical.
In certain embodiments, synthetic route one, synthetic route two the etherification reaction in no solvent or have solvent
It carries out reacting or being reacted in ionic liquid supercritical carbon dioxide under the conditions of existing；The acetal (ketone) changes reaction and exists
There is no solvent or carries out reacting or being reacted in ionic liquid supercritical carbon dioxide under the conditions of having existing for solvent.Example
Such as,
In one embodiment, etherification reaction is reacted under the conditions of having existing for solvent；Acetal (ketone), which changes reaction, to be had
It is reacted under the conditions of solvent is existing.
In one embodiment, etherification reaction is reacted in ionic liquid supercritical carbon dioxide, and acetal (ketone) is changed anti-
It should be reacted in ionic liquid supercritical carbon dioxide.
In one embodiment, etherification reaction and acetal (ketone) are changed reaction and are reacted under the conditions of solvent-free existing.
In certain embodiments, the etherification reaction of synthetic route one, synthetic route two is in air atmosphere, nitrogen gas
It is reacted under at least one of atmosphere, argon atmosphere, carbon dioxide atmosphere atmosphere；The acetal (ketone) changes reaction in air
It is reacted under at least one of atmosphere, nitrogen atmosphere, argon atmosphere, carbon dioxide atmosphere atmosphere.For example,
In one embodiment, etherification reaction is reacted in air atmosphere；Acetal (ketone) changes reaction in air atmosphere
It is reacted.
In one embodiment, etherification reaction is reacted in a nitrogen atmosphere, and acetal (ketone) changes reaction in a nitrogen atmosphere
It is reacted.
In one embodiment, etherification reaction and acetal (ketone) are changed reaction and are reacted under an argon atmosphere.
It should be noted that the reaction condition that etherification reaction changes reaction with acetal (ketone) can be identical or not identical,
Specific reaction condition can voluntarily be selected according to the actual situation by technical staff, and the present invention repeats no more this.
Specific embodiment 1
The embodiment of the present invention provides a kind of glycerine acetal (ketone) ether A, and structural formula is as follows:
The embodiment of the present invention also provides the synthetic method such as glycerine acetal (ketone) ether A:
Acetal (ketone) changes reaction: taking 1000 grams of glycerol (analysis is pure), is added to the three-necked flask of 1000mL, is warming up to 100
DEG C, it is added portionwise 260-400 grams of paraformaldehyde.It is all dissolved to paraformaldehyde, A15 resin acid catalyst 20% is added (by sweet
The quality meter of oil).There-necked flask a bite is kept to open wide, being kept for 100 DEG C, the reaction was continued five hours.After being cooled to 40 DEG C, leaked with Bu Shi
Bucket vacuum filtration.It is 7 that sodium carbonate is added into flask and is neutralized to pH, removes solid impurity after standing.Filtrate Rotary Evaporators
Carry out product separation.It is removed water prior to 40-50 DEG C, then heats to 70-80 DEG C and steam the first fraction (by-product), then slowly risen
To 130-150 DEG C of 1118 grams of collection the second fraction, that is, glycerol formal (the colorless and transparent liquid for having certain viscosity), yield 95%
Above (based on glycerol).
Etherification reaction: above-mentioned glycerol formal is added to the reaction kettle of 5L, A15 resin acid catalyst (dosage is added in kettle
It is the 10% of glycerol formal quality), isobutene (3 equivalents, be equivalent to glycerol formal) are passed through, and be passed through a certain amount of nitrogen.
Stirring is started, is warming up to 70 DEG C, and is reacted 8 hours under this temperature.Stop reaction, room temperature to be down to recycles isobutene.It crosses and filters out
Catalyst is removed, pH to 7 is adjusted.Vacuum distillation obtains product A, yield 84%.
Specific embodiment 2
The embodiment of the present invention provides a kind of glycerine acetal (ketone) ether B, and structural formula is as follows:
The embodiment of the present invention also provides the synthetic method such as glycerine acetal (ketone) ether B:
Acetal (ketone) changes reaction: taking 1000 grams of glycerol (analysis is pure), is added to the three-necked flask of 1000mL, is warming up to 70
DEG C, SO is added4 2-/SiO2Catalyst (dosage is the 10% of qualities of glycerin), takes 3 equivalent of acetone, is slowly added dropwise into reaction system,
Being kept for 70 DEG C, the reaction was continued five hours.After being cooled to 40 DEG C, it is filtered by vacuum with Buchner funnel.Sodium carbonate is added into flask to neutralize
It is 7 to pH, removes solid impurity after standing.Filtrate carries out product separation with Rotary Evaporators, obtains glycerol acetonide acetone, and yield is
72%.
Etherification reaction: the reaction kettle of 5L is added in above-mentioned glycerol acetonide acetone, and SO is added in kettle4 2-/SiO2(dosage is catalyst
The 10% of glycerol acetonide acetone quality), it is passed through isobutene (1.5 equivalents are equivalent to glycerol acetonide acetone), and be passed through a certain amount of nitrogen.
Stirring is started, is warming up to 70 DEG C, and is reacted 8 hours under this temperature.Stop reaction, room temperature to be down to recycles isobutene.It crosses and filters out
Catalyst is removed, pH to 7 is adjusted.Vacuum distillation obtains B, yield 66%.
Specific embodiment 3
The embodiment of the present invention provides a kind of glycerine acetal (ketone) ether C, and structural formula is as follows:
The embodiment of the present invention also provides the synthetic method such as glycerine acetal (ketone) ether C:
Acetal (ketone) changes reaction: taking 1000 grams of glycerol (analysis is pure), is added to the three-necked flask of 1000mL, is warming up to 100
DEG C, SO is added3H-SBA-15 catalyst (dosage is the 20% of qualities of glycerin).Reaction system is added in 3 equivalent of acetaldehyde solution,
With thiacyclohexane band water, being kept for 100 DEG C, the reaction was continued five hours, until there is no moisture to go out.It is true with Buchner funnel after being cooled to 40 DEG C
Empty pump filter.It is 7 that sodium carbonate is added into flask and is neutralized to pH, removes solid impurity after standing.Filtrate is carried out with Rotary Evaporators
Product separation, obtains glycerol acetal, yield 92%.
Etherification reaction: the reaction kettle of 5L is added in above-mentioned glycerol acetal, and A35 resin acid catalyst is added in kettle, and (dosage is
The 10% of glycerol acetal quality), it is passed through propylene (1.5 equivalents are equivalent to glycerol acetal), and be passed through a certain amount of nitrogen.It opens
Dynamic stirring, is warming up to 70 DEG C, and react 8 hours under this temperature.Stop reaction, room temperature to be down to, Propylene recovery.It is filtered to remove and urges
Agent adjusts pH to 7.Vacuum distillation obtains C, yield 80%.
Specific embodiment 4
The embodiment of the present invention provides a kind of glycerine acetal (ketone) ether D, and structural formula is as follows:
The embodiment of the present invention also provides the synthetic method such as glycerine acetal (ketone) ether D:
Etherification reaction: 1000 grams of glycerol (analysis is pure) is added to the reaction kettle of 2L, SO3(dosage is H-MCM-41 catalyst
The 15% of qualities of glycerin).Reaction system is added in 1.2 equivalent of norbornene (being equivalent to glycerol), is warming up to 60 DEG C, and the reaction was continued 7
Hour.After being cooled to room temperature, it is filtered by vacuum with Buchner funnel.It is 7 that sodium carbonate is added into flask and is neutralized to pH, is removed after standing
Solid impurity.Filtrate carries out product separation with Rotary Evaporators.Obtain glycerol list norborneol ether, yield 82%.
Acetal (ketone) changes reaction: the three-necked flask of 2L is added in glycerol list norborneol ether, and SO is added in flask3H-MCM-41 is urged
Agent (dosage is the 10% of glycerol list norborneol ether quality), formalin is added, and (1.2 equivalents are equivalent to glycerol Dan Jiangbing
Piece ether), and 100 DEG C are warming up to, and react 5 hours or more under this temperature with water with thiacyclohexane, until there is no moisture to go out.Drop
To room temperature, Filtration of catalyst adjusts pH to 7.Vacuum distillation obtains compound D, yield 74%.
Specific embodiment 5
The embodiment of the present invention provides a kind of glycerine acetal (ketone) ether E, and structural formula is as follows:
The embodiment of the present invention also provides the synthetic method such as glycerine acetal (ketone) ether E:
Etherification reaction: 1000 grams of glycerol (analysis is pure) is added to the reaction kettle of 2L, SO3(dosage is H-MCM-41 catalyst
The 5% of qualities of glycerin).Reaction system is added in 1.2 equivalent of norbornene (being equivalent to glycerol), is warming up to 60 DEG C, and it is 7 small that the reaction was continued
When.After being cooled to room temperature, it is filtered by vacuum with Buchner funnel.It is 7 that sodium carbonate is added into flask and is neutralized to pH, is removed after standing solid
Body impurity.Filtrate carries out product separation with Rotary Evaporators.Obtain glycerol list norborneol ether, yield 82%.
Acetal (ketone) changes reaction: the three-necked flask of 2L is added in glycerol list norborneol ether, and SO3H-MCM-41 is added in flask and urges
Agent (dosage is the 5% of glycerol list norborneol ether quality), acetaldehyde solution is added, and (1.2 equivalents are equivalent to glycerol list norborneol
Ether), and 100 DEG C are warming up to, and react 5 hours or more under this temperature with water with thiacyclohexane, until there is no moisture to go out.It is down to
Room temperature, Filtration of catalyst adjust pH to 7.It is evaporated under reduced pressure isolated compound E, yield 68%.
Specific embodiment 6
The embodiment of the present invention provides a kind of glycerine acetal (ketone) ether F, and structural formula is as follows:
The embodiment of the present invention also provides the synthetic method such as glycerine acetal (ketone) ether F:
Etherification reaction: 1000 grams of glycerol (analysis is pure) is added to the reaction kettle of 2L, 1- alkyl -3- methyl-imidazoles hydrosulphuric acid
Salt catalyst (dosage is the 17% of qualities of glycerin).Reaction system is added in 1.1 equivalent of propylene (being equivalent to glycerol), is warming up to 60
DEG C, the reaction was continued 7 hours.After being cooled to room temperature, it is filtered by vacuum with Buchner funnel.Sodium carbonate is added into flask to be neutralized to pH and be
7, solid impurity is removed after standing.Filtrate carries out product separation with Rotary Evaporators.Glycerol list isopropyl ether is obtained, yield is
90%.
Acetal (ketone) changes reaction: the three-necked flask of 2L is added in glycerol list isopropyl ether, and SO3H-MCM-48 catalysis is added in flask
Agent (dosage is the 10% of glycerol list isopropyl ether quality), adds acetone (4 equivalents are equivalent to glycerol list isopropyl ether), is warming up to 70 DEG C,
It using acetone band water, and is reacted 7 hours or more under this temperature, is down to room temperature, Filtration of catalyst adjusts pH to 7, and decompression is steamed
It evaporates to obtain compound F, yield 64%.
In the above-described embodiments, it all emphasizes particularly on different fields to the description of each embodiment, is not described in some embodiment
Part, reference can be made to the related descriptions of other embodiments.
The above is a specific embodiment of the invention, but scope of protection of the present invention is not limited thereto, any ripe
It knows those skilled in the art in the technical scope disclosed by the present invention, various equivalent modifications can be readily occurred in or replaces
It changes, these modifications or substitutions should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with right
It is required that protection scope subject to.
Claims (10)
1. a kind of glycerine acetal (ketone) ether, which is characterized in that indicated by following structural formula:
2. a kind of synthetic method of glycerine acetal as described in claim 1 (ketone) ether, which comprises the following steps:
A. etherification reaction, glycerol and alkene press the mass ratio of the material 1:1-10, under the action of the first solid acid catalyst, in 20-
250 DEG C of reaction 0.5-48h obtain glycerol monoethers；
B. acetal (ketone) changes reaction, glycerin ether and aldehyde (ketone) is pressed the mass ratio of the material 1:1-50, in the second solid acid catalyst
Under effect, in 20-250 DEG C of reaction 0.5-48h, glycerine acetal (ketone) ether is obtained.
3. a kind of synthetic method of glycerine acetal as described in claim 1 (ketone) ether, which comprises the following steps:
A) acetal (ketone) changes reaction, and glycerol and aldehyde (ketone) press the mass ratio of the material 1:1-50, in the effect of the second solid acid catalyst
Under, in 20-250 DEG C of reaction 0.5-48h, obtain glycerine acetal (ketone)；
Glycerine acetal (ketone) and alkene are pressed the mass ratio of the material 1:1-10, in the work of the first solid acid catalyst by b) etherification reaction
Under, in 20-250 DEG C of reaction 0.5-48h, glycerine acetal (ketone) ether is obtained.
4. the synthetic method of glycerine acetal (ketone) ether as claimed in claim 2 or claim 3, which is characterized in that the alkene is propylene,
Isobutene, iso-amylene, at least one of norbornene.
5. the synthetic method of glycerine acetal (ketone) ether as claimed in claim 2 or claim 3, which is characterized in that the aldehyde (ketone) is first
Aldehyde, paraformaldehyde, acetaldehyde, at least one of acetone.
6. the synthetic method of glycerine acetal (ketone) ether as claimed in claim 2 or claim 3, which is characterized in that the quality of the glycerol
Score is 20-99.9%, the mass fraction of the alkene is 20-99.5%.
7. the synthetic method of glycerine acetal (ketone) ether as claimed in claim 2 or claim 3, which is characterized in that first solid acid
Catalyst includes alkyl-substituted benzene sulfonic acid, alkyl-substituted naphthalene sulfonic acids, non-alkyl-substituted benzene sulfonic acid, non-alkyl-substituted naphthalene
It is sulfonic acid, poly- sulfonic resin, poly- perfluorosulfonic acid type resin, heteropoly acid and heteropolyacid salt, molecular sieve, acidic ion liquid, single
The SO of complex carrier4 2-/MXOYSolid super-strong acid, S2O8 2-/MXOYAt least one of solid super-strong acid, wherein MXOYFor NiO,
TiO2, ZrO2, SiO2, SnO2, Fe2O3, Al2O3, WO3And MoO3At least one of.
8. the synthetic method of glycerine acetal (ketone) ether as claimed in claim 2 or claim 3, which is characterized in that second solid acid
Catalyst includes replacing including alkyl-substituted benzene sulfonic acid, alkyl-substituted naphthalene sulfonic acids, non-alkyl-substituted benzene sulfonic acid, non-alkyl
Naphthalene sulfonic acids, poly- sulfonic resin, poly- perfluorosulfonic acid type resin, heteropoly acid and heteropolyacid salt, molecular sieve, acidic ion liquid,
The SO of single complex carrier4 2-/MXOYSolid super-strong acid, S2O8 2-/MXOYAt least one of solid super-strong acid, wherein MXOYFor
NiO, TiO2, ZrO2, SiO2, SnO2, Fe2O3, Al2O3, WO3And MoO3At least one of.
9. the synthetic method of glycerine acetal (ketone) ether as claimed in claim 2 or claim 3, which is characterized in that the etherification reaction exists
There is no solvent or carries out reacting or being reacted in ionic liquid supercritical carbon dioxide under the conditions of having existing for solvent；It is described
Acetal (ketone) changes reaction and in no solvent or have existing for solvent under the conditions of carries out reaction or in the overcritical titanium dioxide of ionic liquid
It is reacted in carbon.
10. the synthetic method of glycerine acetal (ketone) ether as claimed in claim 2 or claim 3, which is characterized in that the etherification reaction exists
It is reacted under at least one of air atmosphere, nitrogen atmosphere, argon atmosphere, carbon dioxide atmosphere atmosphere；The acetal
(ketone) is changed reaction and is being carried out instead under at least one of air atmosphere, nitrogen atmosphere, argon atmosphere, carbon dioxide atmosphere atmosphere
It answers.
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| CN114904576A (en) * | 2022-05-09 | 2022-08-16 | 河南大学 | Catalyst for glycerol condensation reaction and preparation method and application thereof |
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