CN109305912A - The method for preparing 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate is condensed by isobutylaldehyde - Google Patents
The method for preparing 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate is condensed by isobutylaldehyde Download PDFInfo
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- CN109305912A CN109305912A CN201810599610.6A CN201810599610A CN109305912A CN 109305912 A CN109305912 A CN 109305912A CN 201810599610 A CN201810599610 A CN 201810599610A CN 109305912 A CN109305912 A CN 109305912A
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- reaction
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- isobutylaldehyde
- ionic liquid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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Abstract
The present invention relates to one kind by isobutylaldehyde condensation preparation 2,2,4- trimethyl -1, the method of 3- pentanediol mono isobutyrate, this method is using isobutylaldehyde as raw material, the raw material is mixed with catalyst and is heated jointly, makes raw material that two chemical reaction processes of aldol condensation and Cannizaro reaction occur in one section of reaction；Wherein the catalyst is ionic liquid.Using method of the invention, reaction condition is mild, and impurity level is few, high income；Ionic liquid recoverable, synthesis technology are environmental-friendly.Product can be purified using the method for the present invention, obtain the product that purity is more than or equal to 99.5%.
Description
Technical field
The present invention relates to chemical products synthesis technical fields, more particularly to a kind of be condensed by isobutylaldehyde to prepare 2,2,4- front threes
The method of base -1,3- pentanediol mono isobutyrate.
Background technique
Product 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate, referred to as Lauryl Alcohol ester or alcohol ester-12, are one
The ideal water-based system coalescing agent of kind has the effect of good filming between emulsion polymer, reduces minimum film formation temperature,
Suitable for various using (methyl) acrylate, styrene, vinyl acetate as the various lotions of Material synthesis, emulsion paint, adhesive
Equal water paints, can aid in the film forming of extensive stock lotion, its minimum film formation temperature are effectively reduced.The production of alcohol ester-12
The demand that not only can satisfy current social makes environmental type coating be more widely used, and can also reduce China's painting
The import of material and auxiliary agent increases the national product output value.The efficient production of alcohol ester-12 or the chemical company in China bring very
Big benefit, market prospects are boundless.
The method of synthesis alcohol ester-12 has isobutylaldehyde base catalysis method at present, i.e., using isobutylaldehyde as raw material, in basic catalyst
Under the action of carry out reaction generate this product.Catalyst is separated after the reaction was completed, remaining raw material, intermediate, impurity
Rectifying, which is carried out, with product obtains alcohol ester-12.The patent application of International Patent Publication No. WO9741088, discloses using 2-10%
NaOH and 0.1-6% two kinds of alkali hydroxide solns of LiOH collectively as catalyst.Chinese patent
CN01140554.6 is disclosed using industrial goods isobutylaldehyde as raw material, in 48-150 DEG C in the presence of alkaline earth metal hydroxide catalyst
Lower reaction 0.5-8h, one-step synthesis obtain reaction solution, are down to room temperature, and the reaction solution after isolating catalyst is again through full gear, decompression
Purpose product can be made in rectifying.The alkaline earth metal hydroxide catalyst is Ba (OH)2·H2O.Chinese patent CN02109500.0
Using Ba (OH)2·8H2O is catalyst, is prepared for alcohol ester-12.
The production of alcohol ester-12 at present mostly uses greatly two-stage process, and first segment carries out aldol reaction, second segment card
Ni Zhaluo reaction generates monoesters.If Chinese patent CN01142834.1 discloses a kind of preparation method of alcohol ester-12, risen using substep
Temperature, the synthetic method of two-stage reaction, i.e. isobutylaldehyde first carry out condensation reaction under cryogenic, and 10-60 DEG C of reaction temperature；Then
Heating, 60-150 DEG C of second segment reaction temperature are directly heated, the catalyst includes alkali or alkaline earth metal hydroxide, alkaline earth
Metal oxide, alkaline or alkaline-earth salts, organotin, stannous oxide etc..Chinese patent CN200610024373.8 first segment is adopted
With 5% sodium hydrate aqueous solution, second segment uses houghite class catalyst, after the reaction was completed using the method separation of filtering
Catalyst out.Chinese patent CN201010151778.4 first segment use 2% sodium hydrate aqueous solution, second segment use with
KF、K2CO3Or it is catalyst that KOAC, which is the modified metal oxide in activated centre,.Reaction mixture is sunk after the reaction was completed
Drop, is separated by filtration to obtain catalyst.Chinese patent CN201010213678.X first segment uses the sodium hydrate aqueous solution of 2-5%,
The stratiform magnalium Layered compound that second segment uses tert-butoxy anion pillared is catalyst.
Chinese patent CN201010283690.8 discloses a kind of preparation method of alcohol ester-12, and used catalyst is sodium alkoxide,
Inorganic base catalyst two-stage reaction complex process is avoided whereby, the disadvantages of energy consumption is high, also avoids Ba (OH)2Catalyst it is toxic and
The disadvantages of high to raw material isobutylaldehyde quality requirement.
Chinese patent CN201410324833.3 discloses a kind of continuous preparation method of alcohol ester-12, used catalyst
It is the bimetallic catalyst with spherical silica for carrier loaded caesium and potassium, method therefor is that two sections of series connection are calandria type fixed bed anti-
Answer device.
As seen from the above, the preparation part of alcohol ester-12 uses Ba (OH)2For catalyst, but there are catalyst itself to have
The disadvantages of malicious and high to raw material isobutylaldehyde quality requirement.The part prior art is prepared using two-stage method, and it is complicated that there are reaction process,
The disadvantages of energy consumption is high, and there are waste water handling problems for sodium hydrate aqueous solution.Wherein " section " of reaction process is to react item
Part is as distinguishing, and primary change of the every generation of reaction condition is known as one section or a stage, and constant reaction condition is then same reaction
Section.In addition, whether the technique of evaluation alcohol ester-12 is more excellent, mainly goes to investigate in terms of following three: (1) activity of catalyst: urging
Agent activity is bigger, and reaction condition requires milder.(2) selectivity of product: selectivity of product is high, is more conducive to purify.(3)
Reaction process: one-step method or two-step method, one-step method can save equipment investment, reduce production operation difficulty, energy-saving, drop
Low production cost.
Summary of the invention
The present invention is directed to overcome the shortcomings of inorganic base catalyst, the present invention provides a kind of by isobutylaldehyde condensation preparation 2,2,4-
The method of trimethyl -1,3- pentanediol mono isobutyrate, this method use ionic liquid as catalyst, in one section of reaction process
In be completed at the same time two reaction process of aldol condensation and Cannizaro reaction, the selectivity of feed stock conversion and alcohol ester-12 all compared with
It is high.
In order to solve the above problem of the prior art, the present invention provides a kind of be condensed by isobutylaldehyde and prepares 2,2,4- front threes
The method of base -1,3- pentanediol mono isobutyrate, this method mix the raw material and common using isobutylaldehyde as raw material with catalyst
Heating makes raw material that two chemical reaction processes of aldol condensation and Cannizaro reaction occur in one section of reaction；Wherein, described to urge
Agent is ionic liquid.
Ionic liquid, also known as ionic liquid are a kind of liquid being composed entirely of ions, such as the KCl under high temperature,
KOH is in liquid condition, and at this time they are exactly ionic liquid.What is be in a liquid state at a temperature of room temperature or near room temperature is made of ion
Substance, referred to as ionic liquid at room temperature, organic ion liquid etc..In ionic compound, the active force between zwitterion is
Coulomb force, size is related with the amount of charge of zwitterion and radius, and ionic radius is bigger, and the active force between them is got over
Small, the fusing point of this ionic compound is lower.The zwitterion of certain ionic compounds is sufficiently bulky, loosely organized, causes
Active force between them is lower, so that fusing point causes it to be in liquid condition at room temperature close to room temperature.In the present invention
In, ionic-liquid catalyst is primarily referred to as ionic liquid at room temperature.
Cannizaro reaction (Cannizzaro reaction) is that the aldehyde of no α active hydrogen issues raw intermolecular oxygen in highly basic effect
Change reduction reaction, generates organic disproportionated reaction of a carboxylic acids and a molecule alcohol.
A preferred embodiment according to the present invention, the ionic liquid include cation and anion, the cation choosing
Flowering structure formula one arrives one of structural formula six or a variety of freely:
Wherein, R1、R2、R3、R4=methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, hexyl, octyl or benzyl；
The anion is selected from F-, Cl-, Br-, I-, OH-, BF4 -, PF6 -, CH3COO-, CF3COO-, CF3SO3 -, NTf2 -One
Kind is several.
Wherein, NTf2 -Structural formula are as follows:
Preparation method of the invention, reaction process are as follows:
A preferred embodiment according to the present invention, the dosage of the catalyst are the 0.5- of isobutylaldehyde material quality
10wt%.
A preferred embodiment according to the present invention, reaction temperature are 50-200 DEG C, preferably 80-120 DEG C.
A preferred embodiment according to the present invention, reaction time 12-48h, preferably 20-24h.
A preferred embodiment according to the present invention after the reaction was completed cools reaction mass, connects by three
The distillation system of rectifying column composition carry out rectifying, first the top of the distillation column produces unreacted isobutylaldehyde, second rectifying
Column overhead produces intermediate, and third the top of the distillation column produces alcohol ester-12, and remaining ionic liquid is led in each tower bottom of rectifying tower
Out, for recycling.
The invention also includes: ionic liquid is condensed 2,2,4- trimethyls -1,3- of preparation as catalyst, in catalyzing iso-butane aldehyde
Application in pentanediol mono isobutyrate.
The beneficial effects of the present invention are:
Technique according to the invention, using isobutylaldehyde as raw material, using ionic liquid as catalyst, condensation preparation 2,2,4- tri-
Methyl-1,3- pentanediol mono isobutyrate, product yield is high, is greater than 50%, highest yield is 75.6%；By-product is few, always
Impurity is less than 2%.Rectifying is carried out using the distillation system of three concatenated rectifying column compositions, the alcohol ester-12 obtained after rectifying
Purity is greater than 99.5%.
The invention has the advantages that (1) ionic liquid is fluid substance, it can be fine with reaction raw materials in the reaction system
Ground is miscible, realizes homogeneous reaction, this also contributes to improving reaction rate and conversion ratio.(2) the Nomenclature Composition and Structure of Complexes of ionic liquid
It can regulate and control easily, by changing zwitterion composition and structure, regulate and control its catalytic performance.(3) showing the result is that: reaction
Mild condition, temperature are low, and the time is short, and by-product is few (impurity level is few), high income.(4) synthesis technology is environmental-friendly, and catalyst can
It is recycled.Therefore the present invention is a kind of method for preparing alcohol ester-12 for having prospects for commercial application.
Detailed description of the invention
The A figure of Fig. 1 is the mass spectrometric measurement figure of the product alcohol ester-12 after the preparation of the embodiment of the present invention 2 and rectifying, the B figure of Fig. 1
For the mass spectrogram of standard items.
Specific embodiment
In order to preferably explain the present invention, in order to understand, below by specific embodiment, present invention work is retouched in detail
It states.
Embodiment 1
The present embodiment uses the reaction kettle of 100mL, oil bath heating.50g isobutylaldehyde is added into reaction kettle, adds 0.5g
1- methyl -3- butyl-imidazolium tetrafluoroborate, reaction kettle is sealed, is heated to 100 DEG C, reacts 20h, it is cold after the reaction was completed
But cool down, the yield for measuring alcohol ester-12 is 71.8%, and total impurities content is 1.56%.
Embodiment 2
Using the reaction kettle of 1000L, heated using steam.500Kg isobutylaldehyde is added into reaction kettle, adds 10Kg tetra-
Butyl ammonium hydroxide seals reaction kettle, is heated to 80 DEG C, and reaction for 24 hours, after the reaction was completed cools reaction mass, surveys
Yield to alcohol ester-12 is 75.6%, and total impurities content is 1.28%.
Reaction mass is sent into three concatenated rectifying column rectifying, produces alcohol ester-12, mass spectrum in third the top of the distillation column
Test result schemes completely the same, purity 99.5% as shown in the A figure of Fig. 1, with the B of Fig. 1.Recycling remaining ion in tower reactor
Liquid catalyst.
Embodiment 3
The present embodiment uses the reaction kettle of 100mL, oil bath heating.50g isobutylaldehyde is added into reaction kettle, and is added
The ionic-liquid catalyst (tetrabutylammonium hydroxide) that 0.25g embodiment 2 recycles is heated to 200 DEG C, reacts 20h, and reaction is completed
The yield for measuring alcohol ester-12 afterwards is 73.6%, and total impurities content is 1.18%.
Embodiment 4
The present embodiment uses the reaction kettle of 100mL, oil bath heating.50g isobutylaldehyde is added into reaction kettle, and 5g reality is added
The ionic-liquid catalyst (tetrabutylammonium hydroxide) for applying the recycling of example 2 is heated to 50 DEG C, reacts 20h, measures alcohol after the reaction was completed
The yield of ester -12 is 72.4%, and total impurities content is 1.37%.
Embodiment 5
The present embodiment uses the reaction kettle of 100mL, oil bath heating.50g isobutylaldehyde is added into reaction kettle, adds 2.5g
1- ethyl-3-methylimidazole bis-trifluoromethylsulfoandimide salt, reaction kettle is sealed, is heated to 120 DEG C, reaction for 24 hours, has been reacted
It cools after, the yield for measuring alcohol ester-12 is 73.2%, and total impurities content is 1.38%.
Embodiment 6
The present embodiment uses the reaction kettle of 100mL, oil bath heating.50g isobutylaldehyde is added into reaction kettle, adds 4g's
Bis- (trimethyl fluoride sulfonyl) inferior amine salts of 1- methyl-1 propylpiperdine, reaction kettle is sealed, and is heated to 90 DEG C, reaction for 24 hours, is reacted
It cools after the completion, the yield for measuring alcohol ester-12 is 72.9%, and total impurities content is 1.45%.
Embodiment 7
The present embodiment uses the reaction kettle of 100mL, oil bath heating.50g isobutylaldehyde is added into reaction kettle, adds 2g's
P1111 (bis- (fluoroform sulphonyl) inferior amine salts of tetramethyl phosphorus, quaternary phosphonium type), reaction kettle is sealed, and is heated to 120 DEG C, reaction
For 24 hours, it cools after the reaction was completed, the yield for measuring alcohol ester-12 is 72.2%, and total impurities content is 1.42%.
Embodiment 8
The present embodiment uses the reaction kettle of 100mL, oil bath heating.50g isobutylaldehyde is added into reaction kettle, adds 1g's
N4441 (bis- (fluoroform sulphonyl) inferior amine salts of tributyl-methyl phosphonium ammonium, quaternary ammonium type), reaction kettle is sealed, is heated to 120 DEG C, instead
It should cool after the reaction was completed for 24 hours, the yield for measuring alcohol ester-12 is 72.5%, and total impurities content is 1.38%.
Claims (8)
1. a kind of method for being condensed 2,2,4- trimethyl -1,3- pentanediol mono isobutyrates of preparation by isobutylaldehyde, this method is with different
Butyraldehyde is raw material, which is mixed with catalyst and is heated jointly, makes raw material that aldol condensation and bank occur in one section of reaction
Ni Zhaluo reacts two chemical reaction processes；It is characterized by: the catalyst is ionic liquid.
2. the method according to claim 1, wherein the ionic liquid include cation and anion, it is described
Cation is selected from following structural formula one and arrives one of structural formula six or a variety of:
Wherein, R1、R2、R3、R4=methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, hexyl, octyl or benzyl；
Wherein, the anion is selected from F-, Cl-, Br-, I-, OH-, BF4 -, PF6 -, CH3COO-, CF3COO-, CF3SO3 -, NTf2 -'s
It is one or more of.
3. according to the method described in claim 2, it is characterized in that, the dosage of the catalyst is isobutylaldehyde material quality
0.5-10wt%.
4. according to the method in claim 2 or 3, which is characterized in that reaction temperature is 50-200 DEG C, preferably 80-120 DEG C.
5. according to the method in claim 2 or 3, which is characterized in that reaction time 12-48h, preferably 20-24h.
6. method according to claim 1-3, which is characterized in that after the reaction was completed, by the cooling drop of reaction mass
Temperature carries out rectifying into the distillation system being made of three concatenated rectifying columns, and first the top of the distillation column extraction is unreacted
Isobutylaldehyde, second the top of the distillation column produce intermediate, third the top of the distillation column extraction alcohol ester-12, residual in tower bottom of rectifying tower
The ionic liquid export stayed, for being recycled.
7. ionic liquid is condensed preparation 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate in catalyzing iso-butane aldehyde as catalyst
In application.
8. application according to claim 7, which is characterized in that the ionic liquid includes cation and anion；
Wherein, the cation is selected from following structural formula one and arrives one of structural formula six or a variety of:
Wherein, R1、R2、R3、R4=methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, hexyl, octyl or benzyl；
Wherein, the anion is selected from F-, Cl-, Br-, I-, OH-, BF4 -, PF6 -, CH3COO-, CF3COO-, CF3SO3 -, NTf2 -'s
It is one or more of.
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| CN201810599610.6A CN109305912B (en) | 2018-06-12 | 2018-06-12 | Method for preparing 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate by condensing isobutyraldehyde |
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| CN201810599610.6A CN109305912B (en) | 2018-06-12 | 2018-06-12 | Method for preparing 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate by condensing isobutyraldehyde |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875498A (en) * | 2020-08-27 | 2020-11-03 | 武汉昱鼎科技有限公司 | Preparation method of 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate |
| CN114262469A (en) * | 2021-12-24 | 2022-04-01 | 华昌智典新材料(江苏)有限公司 | Preparation process for preparing film forming additive by using alcohol ester hexadecane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098712A (en) * | 1994-05-27 | 1995-02-15 | 吉林化学工业公司江南设计研究院 | 2,2,4-trimethylammonium-1, the preparation method of 3-pentanediol mono isobutyrate |
| CN106631776A (en) * | 2016-11-15 | 2017-05-10 | 广州印田新材料有限公司 | Green preparation process for synthesizing 12-carbon alcohol ester by double catalytic system |
| CN107673975A (en) * | 2017-06-20 | 2018-02-09 | 兰州石化职业技术学院 | A kind of method for synthesizing the pentanediol mono isobutyrate of 2,2,4 trimethyl 1,3 |
-
2018
- 2018-06-12 CN CN201810599610.6A patent/CN109305912B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098712A (en) * | 1994-05-27 | 1995-02-15 | 吉林化学工业公司江南设计研究院 | 2,2,4-trimethylammonium-1, the preparation method of 3-pentanediol mono isobutyrate |
| CN106631776A (en) * | 2016-11-15 | 2017-05-10 | 广州印田新材料有限公司 | Green preparation process for synthesizing 12-carbon alcohol ester by double catalytic system |
| CN107673975A (en) * | 2017-06-20 | 2018-02-09 | 兰州石化职业技术学院 | A kind of method for synthesizing the pentanediol mono isobutyrate of 2,2,4 trimethyl 1,3 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875498A (en) * | 2020-08-27 | 2020-11-03 | 武汉昱鼎科技有限公司 | Preparation method of 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate |
| CN114262469A (en) * | 2021-12-24 | 2022-04-01 | 华昌智典新材料(江苏)有限公司 | Preparation process for preparing film forming additive by using alcohol ester hexadecane |
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