CN104974015A - Synthesis method of alcohol - Google Patents
Synthesis method of alcohol Download PDFInfo
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- CN104974015A CN104974015A CN201410145597.9A CN201410145597A CN104974015A CN 104974015 A CN104974015 A CN 104974015A CN 201410145597 A CN201410145597 A CN 201410145597A CN 104974015 A CN104974015 A CN 104974015A
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- ethylene glycol
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Abstract
The application relates to a synthesis method of alcohol, which particularly includes filling a reactor with an alcohol compound with calcium alcoholate, heating the reactor and carrying out a reaction to obtain the longer chain alcohol being increased in carbon number.
Description
Technical field
The present invention relates to organic compound synthesis field, be specifically related to the preparation method of alcohol.
Background technology
Alcohol compound is widely used all the time, and such as Virahol is a kind of conventional organic solvent and industrial chemicals, is widely used in chemical industry and pharmaceutical industries; Butanols is important Organic Chemicals, and at present, exploitation propyl carbinol causes especially as vehicle fuel to be paid close attention to widely, etc.And the equal step of synthetic method of alcohols is more loaded down with trivial details now, sepn process is more, the overwhelming majority needs catalyzer.
Alcohol calcium belongs to the one of metal alkoxide, and have M-O-C (M represents a metal center atom) unit in the molecular structure of metal alkoxide at least, because the electronegativity that Sauerstoffatom is stronger, metal alkoxide often demonstrates certain polarity.。Widely, such as titanium isopropylate is used as the catalyzer in organic synthesis to metal alkoxide purposes, and produces TiO
2precursor.Aluminum isopropylate is used as the reagent in organic synthesis.Tetraethyl silicate is as producing SiO
2precursor.Potassium tert.-butoxide is used as the alkali in eliminative reaction.Generally, alcohol calcium is used to catalyzer or prepares electron ceramic material.Liu Xuejun etc. are with alcohol calcium for solid base catalyst, and catalyzed transesterification prepares biofuel.CaSnO is synthesized by sol-gel technique
3, SrSnO
3and BaSnO
3.The people such as Azad A.M. study and find that calcium ethylate and the reaction of ethanol tin can prepare stannate (MSnO
3), stannate belongs to a kind of dielectric materials component, can be used for preparing the equipment of qualitative and quantitative detection carbonic acid gas and the capacity type probe of other gas sensitization equipment.
Above context analyzer shows, the utilization ways of existing alcohol calcium is all meticulousr Application Areas, and to prepare bulk product from calcium ethylate be a good utilization ways, present applicant proposes the novel method that one utilizes alkoxide and the more senior alcohol of " lower alcohol " preparation.
Summary of the invention
The application relates to a kind of synthetic method of alcohol, and it specifically comprises alkylol cpd and alcohol calcium are placed in reactor, reacting by heating, generates the method for the more long-chain alcohol that carbon number increases.Described alkylol cpd be selected from monohydroxy-alcohol and comprise be more than or equal to two hydroxyls polyvalent alcohol in one or more.
In a preferred embodiment, under the temperature of reaction of 0 DEG C-600 DEG C, there is the reaction of alcohol calcium and described alkylol cpd.
In a preferred embodiment, under the absolute pressure of 0Mpa-30Mpa, there is the reaction of alcohol calcium and described alkylol cpd.
In a preferred embodiment, the mol ratio of described alcohol calcium and described alkylol cpd is 1:0.1-100.
In a preferred embodiment, described alcohol calcium and described alkylol cpd react 0-50h at reacting by heating temperature.
Detailed description of the present invention
As mentioned above, the application relates to the synthetic method of alcohol, and it specifically comprises alkylol cpd and alcohol calcium are placed in reactor, after being heated to certain temperature reaction certain hour, generates the method for the more long-chain alcohol that carbon number increases.Described alkylol cpd be selected from monohydroxy-alcohol, polyvalent alcohol and polymerized polyalcohol one or more, be preferably C
1-C
20monohydroxy-alcohol, C
2-C
20one or more in polyvalent alcohol and polymerized polyalcohol.
The method of more long-chain alcohol that utilizes the reaction of calcium ethylate and alkylol cpd to synthesize involved by the application is based on following reaction principle:
Ca(OR
1)
2+2R
2OH→2R
1-R
2-OH+Ca(OH)
2
Or Ca (OR
1)
2+ 2R
2oH → 2R
2-R
1-OH+Ca (OH)
2
In this application, term " alkyl " refers to the hydrocarbon chain radical of straight or branched, and described hydrocarbon chain radical is only made up of carbon and hydrogen atom, not containing unsaturated, have 1 to 20 carbon atom, preferably 1 to 10 carbon atom or 1 to 5 carbon atom, and be connected with the rest part of molecule by singly-bound.
Term " thiazolinyl " refers to the hydrocarbon chain radical of straight or branched, described hydrocarbon chain radical is only made up of carbon and hydrogen atom, containing one or more double bond, there are 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms or 3 to 5 carbon atoms, and be connected with the rest part of molecule by singly-bound.
Term " alkynyl " refers to the hydrocarbon chain radical of straight or branched, described hydrocarbon chain radical is only made up of carbon and hydrogen atom, containing one or more triple bond, there are 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms or 3 to 5 carbon atoms, and be connected with the rest part of molecule by singly-bound.
Term " heteroaryl " refers to and comprises the heteroatomic non-aromatic ring radical that 3 to 20 carbon atoms and 1 to 8 are selected from nitrogen, oxygen and sulphur.Described heteroaryl can be the loop systems at monocycle, dicyclo, three rings or Fourth Ring, and it can comprise loop systems that is that condense or bridge joint; And nitrogen, carbon or sulphur atom in heteroaryl is optionally oxidized; Nitrogen-atoms is optionally quaternized.Described heteroaryl preferably comprises 3 to 20 carbon atoms, more preferably 3 to 8 carbon atoms, preferably comprises 1-8, more preferably 1-5, and most preferably 1-3 is selected from the heteroatoms of nitrogen, oxygen and sulphur.Described heteroaryl is preferably the monocyclic, bicyclic or tricyclic system of more than 5 yuan.
Term " aryl " refers to the non-aromatic ring radical comprising 6 to 20 carbon atoms.Described aryl can be the loop systems at monocycle, dicyclo, three rings or Fourth Ring, and it can comprise loop systems that is that condense or bridge joint.
Described aryl preferably comprises 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.Described aryl is preferably monocyclic, bicyclic or tricyclic system.Term " Heterocyclylalkyl " refers to and comprises the heteroatomic saturated nonaro-maticity cyclic group that 3 to 20 carbon atoms and 1 to 10 are selected from nitrogen, oxygen and sulphur.Described Heterocyclylalkyl can be the loop systems at monocycle, dicyclo, three rings or Fourth Ring, and it can comprise loop systems that is that condense or bridge joint; And nitrogen, carbon or sulphur atom in Heterocyclylalkyl is optionally oxidized; Nitrogen-atoms is optionally quaternized.Described Heterocyclylalkyl preferably comprises 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, preferably comprises 1-8, more preferably 1-5, and most preferably 1-3 is selected from the heteroatoms of nitrogen, oxygen and sulphur.Described Heterocyclylalkyl is preferably the monocyclic, bicyclic or tricyclic system of more than 5 yuan.
Term " heterocycloalkenyl " refers to and comprises heteroatomic, the nonaro-maticity cyclic group containing one or more double bond that 3 to 20 carbon atoms and 1 to 10 are selected from nitrogen, oxygen and sulphur.Described heterocycloalkenyl can be the loop systems at monocycle, dicyclo, three rings or Fourth Ring, and it can comprise loop systems that is that condense or bridge joint; And nitrogen, carbon or sulphur atom in heterocycloalkenyl is optionally oxidized; Nitrogen-atoms is optionally quaternized.Described heterocycloalkenyl preferably comprises 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, preferably comprises 1-8, more preferably 1-5, and most preferably 1-3 is selected from the heteroatoms of nitrogen, oxygen and sulphur.
Described heterocycloalkenyl preferably comprises 1-5, more preferably 1-3 unsaturated double-bond.Described heterocycloalkenyl is preferably the monocyclic, bicyclic or tricyclic system of more than 5 yuan.
Term " alkoxyl group " represents R
7o-structure, wherein R
7for alkyl as defined above.
Term " aralkyl " represents R
8-R
7-structure, wherein R
8for aryl as defined above, R
7for alkyl as defined above.
Term " heteroaralkyl " represents R
9-R
7-structure, wherein R
9for heteroaryl as defined above, R
7for alkyl as defined above.
Term " hetercycloalkylalkyl " represents R
10-R
7-structure, wherein R
10for Heterocyclylalkyl as defined above, R
7for alkyl as defined above.
Term " heterocycloalkenyl alkyl " represents R
11-R
7-structure, wherein R
11for heterocycloalkenyl as defined above, R
7for alkyl as defined above.
Term " monohydroxy-alcohol " is the alkylol cpd containing a hydroxyl with 1-20 carbon atom, and it is represented by general formula R OH, and wherein R represents the group optionally replaced by one or more substituting group, and described group is selected from the C of straight chain, side chain or ring-type
1-C
20the C of alkyl, direct-connected, side chain or ring-type
3-C
20the C of thiazolinyl, straight or branched
3-C
20alkynyl, C
6-C
20aryl, C
3-C
20heteroaryl, C
3-C
20heterocyclylalkyl or heterocycloalkenyl, C
7-C
20aralkyl, C
4-C
20heteroaralkyl or C
4-C
20hetercycloalkylalkyl or heterocycloalkenyl alkyl, described substituting group is selected from C
1-C
10alkyl, C
1-C
10alkoxyl group, C
1-C
10the C that alkoxyl group replaces
1-C
10alkoxyl group, C
1-C
10cycloalkyl, sulfydryl, halogen, cyano group, amino, aldehyde radical, carbonyl, C
1-C
10monosubstituted or the disubstituted amino of alkyl or C
1-C
10alkyl-O-CO-; Or described monohydroxy-alcohol is by general formula OH-[(CH
2)
no]
m-R
1represent, wherein n is the integer of 1-6, and m is the integer of 1-5, R
1for the C of straight chain, side chain or ring-type
1-C
7alkyl, phenyl or benzyl, and n and m can not be 1 simultaneously.
In an experimental program, described monohydroxy-alcohol is preferably methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, 2-methyl-1-butene alcohol, primary isoamyl alcohol, sec.-amyl alcohol, 3-amylalcohol, tertiary amyl alcohol, secondary primary isoamyl alcohol, hexanol, 4-methyl-2-amylalcohol, 2-hexanol, 2-ethyl butanol, 2-methyl amyl alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-ethyl-3-amylalcohol, enanthol, 2-enanthol, 3-enanthol, cyclohexanemethanol, octanol, sec-n-octyl alcohol, 2-Ethylhexyl Alcohol, 5-methyl-2-hexanol, 3,5,5-trimethyl hexanol, nonyl alcohol, 2,6-2,6-dimethyl-4-heptanol, 2-propyl group-1-heptanol, isodecyl alcohol, decyl alcohol, 2-hexyl decyl alcohol, undecyl alcohol, 5-ethyl-2-nonyl alcohol, lauryl alcohol, 2,6,8-trimethylammonium-4-nonyl alcohol, tetradecyl alcohol, hexadecanol, heptadecyl alcohol, stearyl alcohol, cyclopentanol, hexalin, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 4 methyl cyclohexanol, phenylcarbinol, phenylethyl alcohol, 1-methoxy-2-propanol, 1-oxyethyl group-2-propyl alcohol, 1-propoxy--2-propyl alcohol, 1-butoxy-2-propyl alcohol, ethylene chlorhydrin, ethylene bromohyrin, 1-chloro-2-propanol, trimethylene chlorohydrin, the chloro-n-butyl alcohol of 4-, vinyl alcohol, vinyl carbinol,
In another embodiment, described monohydroxy-alcohol is preferably ethylene glycol-monomethyl ether, ethylene glycol-mono-ether, 2-(methoxyl group) ethanol, ethylene glycol-mono-propyl ether, ethylene glycol-mono-isopropyl ether, ethylene glycol-monobutyl ether, ethylene glycol-mono-ethyl isobutyl ether, ethylene glycol-monopentyl ether, ethylene glycol-mono-isoamyl oxide, ethylene glycol-monohexyl ether, ethylene glycol-monophenyl ether, ethylene glycol-mono-benzyl oxide, glycol ether-monomethyl ether, diethylene glycol monoethyl ether, glycol ether-mono-propyl ether, glycol ether-mono-isopropyl ether, glycol ether-monobutyl ether, glycol ether-mono-ethyl isobutyl ether, glycol ether-monopentyl ether, glycol ether-mono-isoamyl oxide.
In this application, term " polyol " refers to the alkylol cpd containing being more than or equal to two hydroxyls.The polyvalent alcohol used in method described in the application is preferably C
2-C
20polyvalent alcohol and polymerized polyalcohol.Described polyvalent alcohol can by general formula R
2(OH)
nrepresent, wherein n=2-20, R
2represent the group that optionally replaced by one or more substituting group, described group is selected from the C of direct-connected, side chain or ring-type
1-C
20the C of alkyl, straight chain, side chain or ring-type
3-C
20the C of thiazolinyl, straight or branched
3-C
20alkynyl, C
6-C
20aryl, C
3-C
20heteroaryl, C
3-C
20heterocyclylalkyl or heterocycloalkenyl, C
7-C
18aralkyl, C
4-C
20heteroaralkyl or C
4-C
20hetercycloalkylalkyl or heterocycloalkenyl alkyl, described substituting group is selected from C
1-C
10alkyl, C
1-C
10alkoxyl group, C
1-C
10the C that alkoxyl group replaces
1-C
10alkoxyl group, C
1-C
10cycloalkyl, sulfydryl, halogen, cyano group, amino, aldehyde radical, carbonyl, C
1-C
10monosubstituted or the disubstituted amino of alkyl or C
1-C
10alkyl-O-CO-; Or described monohydroxy-alcohol is by general formula OH-[(CH
2)
no]
m-H represents, wherein n is the integer of 1-6, and m is the integer of 1-5, and n and m can not be 1 simultaneously.
The example of described polyvalent alcohol includes but not limited to ethylene glycol, 1,2-PD, 1,3-PD, 1,2-butyleneglycol, 1,3-butyleneglycol, BDO, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,2-hexylene glycol, heptanediol, ethohexadiol, glycerol, BT, 1,2,6-hexanetriol, glycol ether, triglycol, Tetraglycol 99, dipropylene glycol, tripropylene glycol.
In the preparation method of the alcohol described in the application, described alcohol calcium can be the unitary alkoxide of calcium, the polynary alkoxide of calcium or its mixture.When described alcohol calcium is monohydroxy-alcohol calcium, it can by general formula Ca (OR)
2represent, wherein R represents the group optionally replaced by one or more substituting group, and described group is selected from the C of straight chain, side chain or ring-type
1-C
20the C of alkyl, straight chain, side chain or ring-type
3-C
20the C of thiazolinyl, straight or branched
3-C
20alkynyl, C
6-C
20aryl, C
3-C
20heteroaryl, C
3-C
20heterocyclylalkyl or heterocycloalkenyl, C
7-C
20aralkyl, C
4-C
20heteroaralkyl or C
4-C
20hetercycloalkylalkyl or heterocycloalkenyl alkyl, described substituting group is selected from C
1-C
10alkyl, C
1-C
10alkoxyl group, C
1-C
10the C that alkoxyl group replaces
1-C
10alkoxyl group, C
1-C
10cycloalkyl, sulfydryl, halogen, cyano group, amino, aldehyde radical, carbonyl, C
1-C
10monosubstituted or the disubstituted amino of alkyl or C
1-C
10alkyl-O-CO-; Or by general formula Ca{O-[(CH
2)
no]
m-R
1}
2represent, wherein n is the integer of 1-6, and m is the integer of 1-5, R
1for the C of straight chain, side chain or ring-type
1-C
7alkyl, phenyl or benzyl, and n and m can not be 1 simultaneously.
The example of described monohydroxy-alcohol calcium includes but not limited to calcium methylate, calcium ethylate, calcium propylate, calcium isopropoxide, calcium butoxide, isopropylcarbinol calcium, sec-butyl alcohol calcium, calcium tert-butoxide, amylalcohol calcium, 2-methyl-1-butene alcohol calcium, primary isoamyl alcohol calcium, sec.-amyl alcohol calcium, 3-amylalcohol calcium, tertiary amyl alcohol calcium.
In this application, the example of the polynary alkoxide of described calcium includes but not limited to as ethylene glycol calcium, 1,2-propylene glycol calcium, 1, ammediol calcium, 1,2-butyleneglycol calcium, 1,3 butylene glycol calcium, BDO calcium, 2, the mixture of 3-butyleneglycol calcium, 1,5-PD calcium, neopentyl glycol calcium or two or more above-claimed cpds.
In one embodiment, described alkylol cpd and alcohol calcium are added in reactor, at the temperature of 0 DEG C-600 DEG C, at the temperature of preferred room temperature-500 DEG C, more preferably under the temperature of reaction of 350 DEG C-450 DEG C, the reaction of described alkylol cpd and alcohol calcium occur.In addition, those skilled in the art can understand, can according to the needs of practice, and the kind of such as selected alkylol cpd selects the temperature being suitable for reacting.
In a preferred embodiment, described alcohol calcium and described alkylol cpd are being heated to react 0-50h under temperature of reaction, preferred 0-10h, and the reaction times is that 0h refers to that temperature is lowered the temperature after rising to temperature of reaction immediately.
In one embodiment, described alkylol cpd and alcohol calcium are added in reactor, under the absolute pressure of 0Mpa-30Mpa, preferably under the absolute pressure of 0.1Mpa-10Mpa, more preferably, under the absolute pressure of 0.1-10Mpa, there is the reaction of described alkylol cpd and alcohol calcium.Described absolute pressure is such as 0,0.01,0.1,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 and 20Mpa.In addition, those skilled in the art can understand, can according to the needs of practice, and the kind of such as selected alkylol cpd selects the absolute pressure being suitable for reacting.
Therefore, in the reaction of alkylol cpd and alcohol calcium, the absolute pressure of temperature of reaction and reaction changes with the kind of alkylol cpd, preferably selects the absolute pressure of temperature of reaction and the reaction be applicable to better to react with alcohol calcium in the liquid state to make alkylol cpd.
In a preferred embodiment, the reaction of described alkylol cpd and alcohol calcium occurs under the absolute pressure of the temperature of 0 DEG C-600 DEG C and 0Mpa-30Mpa, preferably occur at the temperature of room temperature-500 DEG C and the absolute pressure of 0.1Mpa-15Mpa, more preferably occur under the absolute pressure of the temperature of 350 DEG C-450 DEG C and 0.1Mpa-10Mpa.
In one embodiment, the mol ratio of alcohol calcium and described alkylol cpd is 1:0.1-1:100, preferred 1:4-1:50, more preferably 1:5-1:30, most preferably 1:10-1:30.
In one embodiment, the reaction system of described alkylol cpd and alcohol calcium does not comprise the reaction of calcium ethylate and ethanol, can be filled with shielding gas, to avoid the generation of side reaction before the reaction and/or in reaction in the reaction system of alcohol calcium and alkylol cpd.Described shielding gas be selected from rare gas element, nitrogen, alcohol vapour one or more.Described rare gas element includes but not limited to helium, neon, argon gas and Krypton, preferred helium and argon gas.Shown in reaction mechanism as described above, in the reaction of alkylol cpd and alcohol calcium, when the kind of selected alkylol cpd, the kind of products therefrom is also thereupon different.
Will be understood by those skilled in the art that to be to contribute to the understanding of the present invention to the description of reaction mechanism above, instead of product is restricted to pure single compound.It will be appreciated by those skilled in the art that the alcohol prepared by method mentioned above can be the mixture of multi-products, such mixture is also contained within the scope of the invention.
Prepare in the method for the alcohol of more long-chain in the reaction of alcohol calcium and alkylol cpd that utilizes described in the application, the purity of alcohol calcium and alkylol cpd can be 1-100% independently, the purity of described alcohol calcium is preferably more than 90%, and the purity of described alcoholate is preferably more than 80%, and more preferably more than 90%; Its products collection efficiency can reach more than 40%.
The reaction of alcohol calcium and alkylol cpd that utilizes described in the application is prepared in the method for the alcohol of more long-chain, has following one or more advantages: (1) raw alcohol calcium and alkylol cpd easily obtain, and running cost is low; (2) preparation technology is simple, easy handling; (3) products obtained therefrom non-environmental-pollution problem.Therefore the method utilizing the reaction of alcohol calcium and alkylol cpd to prepare the alcohol of more long-chain described in the application has important actual application value, can be applied to industrial production
Hereafter will the present invention will be described in detail in conjunction with the embodiments, but those skilled in the art should be appreciated that those skilled in the art are according to the open and technical knowledge that itself has of the present invention, can carry out some to the present invention and change or revise.Therefore, scope of the present invention is not limited to following embodiment, and should only be limited by claims.
Embodiment
Embodiment 1:
Take calcium isopropoxide and Virahol that mol ratio is 1:10, be placed in high-temperature high-pressure reaction kettle and seal, to be filled with in argon purge still air subsequently three times, under 0.1MPa, to be heated to 380 DEG C, reaction 7h.After having reacted, cooling reactor is to room temperature, and collect liquid after being separated by solidliquid mixture suction filtration in still, wherein 4-methyl-2-amylalcohol productive rate reaches 32%.
Embodiment 2:
Take calcium isopropoxide and ethanol that mol ratio is 1:20, be placed in high-temperature high-pressure reaction kettle and seal, to be filled with in argon purge still air subsequently three times, under 0.3MPa, to be heated to 400 DEG C, reaction 20h.After having reacted, cooling reactor is to room temperature, and collect liquid after being separated by solidliquid mixture suction filtration in still, wherein 3-methyl-1-butanol productive rate reaches 43%.
Embodiment 3:
Take calcium ethylate and 1-octanol that mol ratio is 1:15, be placed in high-temperature high-pressure reaction kettle and seal, to be filled with in nitrogen purging still air subsequently three times, under 0.1MPa, to be heated to 420 DEG C, reaction 8h.After having reacted, cooling reactor is to room temperature, and collect liquid after being separated by solidliquid mixture suction filtration in still, wherein 1-decanol productive rate reaches 39.2%.
Embodiment 4:
Take calcium ethylate and DODECANOL, 1-that mol ratio is 1:9, be placed in high-temperature high-pressure reaction kettle and seal, be heated to 350 DEG C at 0.2 mpa, reaction 9h.After having reacted, cooling reactor is to room temperature, and collect liquid after being separated by solidliquid mixture suction filtration in still, wherein 1-tetradecanol productive rate reaches 35%.
Embodiment 5:
Take calcium ethylate and 1-cetyl alcohol that mol ratio is 1:23, be placed in high-temperature high-pressure reaction kettle and seal, under 0.1MPa, be heated to 390 DEG C, reaction 16h.After having reacted, cooling reactor is to room temperature, and collect liquid after being separated by solidliquid mixture suction filtration in still, wherein 1-Stearyl alcohol productive rate reaches 28%.
Embodiment 6:
Take n-propyl alcohol calcium and ethylene glycol that mol ratio is 1:10, be placed in high-temperature high-pressure reaction kettle and seal, to be filled with in nitrogen purging still air subsequently three times, under 0.25MPa, to be heated to 370 DEG C, reaction 11h.After having reacted, cooling reactor is to room temperature, and collect liquid after being separated by solidliquid mixture suction filtration in still, wherein 3,4-bis-octanol productive rates reach 18.6%.
Embodiment 7:
Take n-propyl alcohol calcium and ethanol that mol ratio is 1:18, be placed in high-temperature high-pressure reaction kettle and seal, to be filled with in nitrogen purging still air subsequently three times, under 0.1MPa, to be heated to 450 DEG C, reaction 10h.After having reacted, cooling reactor is to room temperature, and collect liquid after being separated by solidliquid mixture suction filtration in still, wherein 1-amylalcohol productive rate reaches 41%.
Embodiment 8:
Take propyl carbinol calcium and ethanol that mol ratio is 1:25, be placed in high-temperature high-pressure reaction kettle and seal, to be filled with in nitrogen purging still air subsequently three times, under 0.1MPa, to be heated to 360 DEG C, reaction 9h.After having reacted, cooling reactor is to room temperature, and collect liquid after being separated by solidliquid mixture suction filtration in still, wherein 1-hexanol productive rate reaches 29.2%.
Embodiment 9:
Take calcium ethylate and glycerol that mol ratio is 1:16, be placed in high-temperature high-pressure reaction kettle and seal, to be filled with in nitrogen purging still air subsequently three times, under 0.1MPa, to be heated to 360 DEG C, reaction 20h.After having reacted, cooling reactor is to room temperature, and collect liquid after being separated by solidliquid mixture suction filtration in still, wherein 4-ethyl-3,4,5-tri-enanthol productive rate reaches 21%.
Embodiment 10:
Take ethylene glycol calcium and ethanol that mol ratio is 1:13, be placed in high-temperature high-pressure reaction kettle and seal, to be filled with in nitrogen purging still air subsequently three times, under 0.1MPa, to be heated to 370 DEG C, reaction 19h.After having reacted, cooling reactor is to room temperature, and collect liquid after being separated by solidliquid mixture suction filtration in still, wherein 1,6-bis-hexanol productive rate reaches 19.7%.
Embodiment 11:
Take 1,2-butyleneglycol calcium and the ethanol that mol ratio is 1:19, be placed in high-temperature high-pressure reaction kettle and seal, to be filled with in nitrogen purging still air subsequently three times, under 0.1MPa, to be heated to 420 DEG C, reaction 9h.After having reacted, cooling reactor is to room temperature, and collect liquid after being separated by solidliquid mixture suction filtration in still, wherein 3-ethyl-1,6-bis-hexanol productive rate reaches 21.6%.
Claims (12)
1. a synthetic method for alcohol, it specifically comprises alkylol cpd and alcohol calcium is placed in reactor, reacting by heating, generates the method for the more long-chain alcohol that carbon number increases.
2. the method for claim 1, described alkylol cpd is selected from monohydroxy-alcohol and comprises one or more of the polyvalent alcohol that is more than or equal to two hydroxyls.
3., wherein at 0 DEG C-600 DEG C, under the temperature of reaction of preferred 350-450 DEG C, there is the reaction of alcohol calcium and described alkylol cpd in method as claimed in claim 1 or 2.
4., wherein under the absolute pressure of 0Mpa-30Mpa, preferably 0.1MPa-10MPa, there is the reaction of alcohol calcium and described alkylol cpd in the method as described in claim arbitrary in claim 1-3.
5. the method as described in claim arbitrary in claim 1-4, the mol ratio of described alcohol calcium and described alkylol cpd is 1:0.1-100, preferred 1:5-1:30.
6. the method as described in claim arbitrary in claim 1-5, comprise the step being filled with shielding gas in the reaction system of described alcohol calcium and described alkylol cpd, but the reaction of described alcohol calcium and described alkylol cpd does not comprise the reaction of calcium ethylate and ethanol; Described shielding gas include but not limited in rare gas element, nitrogen, alcohol vapour one or more.
7. the method as described in claim arbitrary in claim 1-6, the purity of wherein said alcohol calcium and alkylol cpd is independently 1-100%, and described alcohol calcium purity is preferably 90%-100%, and the purity of described alkylol cpd is preferably 90%-100%.
8. the method as described in claim arbitrary in claim 1-7, described alcohol calcium and described alkylol cpd reaction times are 0-50h, are preferably 0-10h.
9. the method as described in claim arbitrary in claim 1-8, wherein said monohydroxy-alcohol is C
1-C
20, it is represented by general formula R OH, and wherein R represents the group optionally replaced by one or more substituting group, and described group is selected from the C of straight chain, side chain or ring-type
1-C
20the C of alkyl, straight chain, side chain or ring-type
3-C
20the C of thiazolinyl, straight or branched
3-C
20alkynyl, C
6-C
20aryl, C
3-C
20heteroaryl, C
3-C
20heterocyclylalkyl or heterocycloalkenyl, C
7-C
20aralkyl, C
4-C
20heteroaralkyl or C
4-C
20hetercycloalkylalkyl or heterocycloalkenyl alkyl, described substituting group is selected from C
1-C
10alkyl, C
1-C
10alkoxyl group, C
1-C
10the C that alkoxyl group replaces
1-C
10alkoxyl group, C
1-C
10cycloalkyl, sulfydryl, halogen, cyano group, amino, aldehyde radical, carbonyl, C
1-C
10monosubstituted or the disubstituted amino of alkyl or C
1-C
10alkyl-O-CO-;
Wherein said monohydroxy-alcohol is preferably methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, 2-methyl-1-butene alcohol, primary isoamyl alcohol, sec.-amyl alcohol, 3-amylalcohol, tertiary amyl alcohol, secondary primary isoamyl alcohol, hexanol, 4-methyl-2-amylalcohol, 2-hexanol, 2-ethyl butanol, 2-methyl amyl alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-ethyl-3-amylalcohol, enanthol, 2-enanthol, 3-enanthol, cyclohexanemethanol, octanol, sec-n-octyl alcohol, 2-Ethylhexyl Alcohol, 5-methyl-2-hexanol, 3,5,5-trimethyl hexanol, nonyl alcohol, 2,6-2,6-dimethyl-4-heptanol, 2-propyl group-1-heptanol, isodecyl alcohol, decyl alcohol, 2-hexyl decyl alcohol, undecyl alcohol, 5-ethyl-2-nonyl alcohol, lauryl alcohol, 2,6,8-trimethylammonium-4-nonyl alcohol, tetradecyl alcohol, hexadecanol, heptadecyl alcohol, stearyl alcohol, cyclopentanol, hexalin, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 4 methyl cyclohexanol, phenylcarbinol, phenylethyl alcohol, 1-methoxy-2-propanol, 1-oxyethyl group-2-propyl alcohol, 1-propoxy--2-propyl alcohol, 1-butoxy-2-propyl alcohol, ethylene chlorhydrin, ethylene bromohyrin, 1-chloro-2-propanol, trimethylene chlorohydrin, the chloro-n-butyl alcohol of 4-, vinyl alcohol, vinyl carbinol,
Or
Described monohydroxy-alcohol is by general formula OH-[(CH
2)
no] m-R
1represent, wherein n is the integer of 1-6, and m is the integer of 1-5, and n and m can not be 1, R1 is simultaneously the C of straight chain, side chain or ring-type
1-C
7alkyl, phenyl or benzyl;
Wherein said monohydroxy-alcohol is preferably selected from ethylene glycol-monomethyl ether, ethylene glycol-mono-ether, 2-(methoxyl group) ethanol, ethylene glycol-mono-propyl ether, ethylene glycol-mono-isopropyl ether, ethylene glycol-monobutyl ether, ethylene glycol-mono-ethyl isobutyl ether, ethylene glycol-monopentyl ether, ethylene glycol-mono-isoamyl oxide, ethylene glycol-monohexyl ether, ethylene glycol-monophenyl ether, ethylene glycol-mono-benzyl oxide, glycol ether-monomethyl ether, diethylene glycol monoethyl ether, glycol ether-mono-propyl ether, glycol ether-mono-isopropyl ether, glycol ether-monobutyl ether, glycol ether-mono-ethyl isobutyl ether, glycol ether-monopentyl ether, glycol ether-mono-isoamyl oxide.
10. the method as described in claim arbitrary in claim 1-9, wherein said polyvalent alcohol is the C optionally replaced by one or more substituting group
2-C
20polyvalent alcohol and polymerized polyalcohol, described substituting group is selected from C
1-C
10alkyl, halogen, amino, C
1-C
10monosubstituted or the disubstituted amino of alkyl or sulfydryl, described polyvalent alcohol is preferably ethylene glycol, 1,2-PD, 1, ammediol, 1,2-butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol, 2,3-butyleneglycol, 1,5-PD, neopentyl glycol, 1,2-hexylene glycol, heptanediol, ethohexadiol, glycerol, 1,2,4-trihydroxybutane, 1,2,6-hexanetriol, glycol ether, triglycol, Tetraglycol 99, dipropylene glycol, tripropylene glycol.
11. methods as described in claim arbitrary in claim 1-10, the alkoxide of wherein said calcium is the unitary alkoxide of calcium, polynary alkoxide or polymeric polyols alkoxide, and wherein unitary alkoxide is preferably calcium methylate, calcium ethylate, calcium propylate, calcium isopropoxide, calcium butoxide, isopropylcarbinol calcium, sec-butyl alcohol calcium, calcium tert-butoxide, amylalcohol calcium, 2-methyl-1-butene alcohol calcium, primary isoamyl alcohol calcium, sec.-amyl alcohol calcium, 3-amylalcohol calcium, tertiary amyl alcohol calcium.
12. methods as described in claim arbitrary in claim 1-11, the polynary alkoxide of wherein said calcium is preferably ethylene glycol calcium, 1,2-propylene glycol calcium, 1, ammediol calcium, 1,2-butyleneglycol calcium, 1,3 butylene glycol calcium, BDO calcium, 2, the mixture of 3-butyleneglycol calcium, 1,5-PD calcium, neopentyl glycol calcium or two or more above-claimed cpds.
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3328470A (en) * | 1963-10-03 | 1967-06-27 | Continental Oil Co | Greater selectivity in the guerbet reaction |
CN1266418A (en) * | 1997-08-11 | 2000-09-13 | Rwe-Dea矿物油化学有限公司 | Method for producing metal-free guerbet alcohols |
-
2014
- 2014-04-11 CN CN201410145597.9A patent/CN104974015A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3328470A (en) * | 1963-10-03 | 1967-06-27 | Continental Oil Co | Greater selectivity in the guerbet reaction |
CN1266418A (en) * | 1997-08-11 | 2000-09-13 | Rwe-Dea矿物油化学有限公司 | Method for producing metal-free guerbet alcohols |
Non-Patent Citations (1)
Title |
---|
叶平平: "Guerbet醇缩合及醛酮参与的缩合反应研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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