CN104003841A - Method for preparing alkoxide of calcium - Google Patents
Method for preparing alkoxide of calcium Download PDFInfo
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- CN104003841A CN104003841A CN201310055834.8A CN201310055834A CN104003841A CN 104003841 A CN104003841 A CN 104003841A CN 201310055834 A CN201310055834 A CN 201310055834A CN 104003841 A CN104003841 A CN 104003841A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/68—Preparation of metal alcoholates
- C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
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Abstract
The invention relates to a method for preparing alkoxide of calcium. The method includes the step that an alcoholic compound is reacted with calcium carbide. The alcoholic compound is selected from monohydric alcohol and one or more of polyhydric alcohols which include larger than or equal to two hydroxide radicals.
Description
Technical field
The present invention relates to the synthetic field of organic compound, be specifically related to the preparation method of the alkoxide of calcium.
Background technology
The alkoxide of calcium, also referred to as alcoholate or the alcoholization calcium of calcium, belongs to metal alkoxide.In metal alkoxide, because Sauerstoffatom has stronger electronegativity, M-O key is polarized consumingly, and make metal alkoxide demonstrate certain polarity, its degree of polarization is also relevant with the electronegativity of metal.Therefore, metal alkoxide can be regarded the derivative of alcohol as, also can regard the derivative of metal hydroxides as.Thereby metal alkoxide is described as the metal-organic part of broad sense of having filled up blank between organic chemistry and inorganic chemistry by people.
The alkoxide of calcium has good surface properties, is widely used as catalyzer and for the preparation of materials such as rubber composite, nano material and potteries.At home, the alkoxide of calcium mainly relies on import, and this has hindered the industrial development of the alkoxide of calcium.The preparation method of the alkoxide of calcium is less at present, is mainly to utilize calcium metal and alcohol direct reaction to synthesize.For example, Chinese patent application 02134218.0 discloses under certain temperature and catalyzer exist, and calcium metal is put into and in alcohol reagent, stirred the alkoxide that makes calcium.The main drawback of above-mentioned synthesis method is that the activity of raw materials used calcium metal is higher, price is more expensive, is difficult for preparation and preserves; And react wayward, reaction is had relatively high expectations to catalyzer and conversion unit, and transformation efficiency is not high.Therefore, the invention provides a kind of method of the new alkoxide of preparing calcium.
Summary of the invention
On the one hand, the application relates to the preparation method of the alkoxide of calcium, and it comprises the step that alkylol cpd is reacted with calcium carbide, and described alkylol cpd is selected from monohydroxy-alcohol and comprises one or more in the polyvalent alcohol that is more than or equal to two hydroxyls.
In a preferred embodiment, under the temperature of reaction of 0 ° of C-600 ° of C, there is reacting of described alkylol cpd and calcium carbide.
In a preferred embodiment, under the absolute pressure of 0Mpa-20Mpa, there is reacting of described alkylol cpd and calcium carbide.
In a preferred embodiment, the mol ratio of described calcium carbide and described alkylol cpd is 1:0.01-1:100.
Brief description of drawings
Fig. 1 is the infared spectrum of the calcium ethylate compound of embodiment 3 preparations.
Detailed description of the present invention
As mentioned above, the application relates to the preparation method of the alkoxide of calcium, and it comprises the step that alkylol cpd is reacted with calcium carbide.Described alkylol cpd is selected from monohydroxy-alcohol, comprise and be more than or equal to the polyvalent alcohol of two hydroxyls and one or more in polymerized polyalcohol, is preferably C
1-C
50monohydroxy-alcohol, C
2-C
50one or more in polyvalent alcohol and polymerized polyalcohol.
The method of utilizing calcium carbide and reacting of alkylol cpd to synthesize the alkoxide of calcium that the application is related is based on following reaction principle: (polyvalent alcohol be take dibasic alcohol as example)
2ROH+CaC
2→Ca(RO)
2+C
2H
2
HOR
3r
4oH+CaC
2→ Ca (OR
3r
4o) and/or HOR
3r
4o-Ca-OR
3r
4oH and/or HOR
3r
4o-Ca-OR
4r
3oH/HOR
4r
3o-Ca-OR
3r
4oH and/or HOR
4r
3o-Ca-OR
4r
3oH+C
2h
2
In this application, term " alkyl " refers to the hydrocarbon chain group of straight or branched, and described hydrocarbon chain group is only formed, do not contained unsaturated by carbon and hydrogen atom, have 1 to 50 carbon atom, preferably 1 to 20 carbon atom or 1 to 10 carbon atom, and be connected with the rest part of molecule by singly-bound.
Term " thiazolinyl " refers to the hydrocarbon chain group of straight or branched, described hydrocarbon chain group only forms, contains one or more pairs of keys by carbon and hydrogen atom, there are 3 to 50 carbon atoms, preferably 3 to 20 carbon atoms or 3 to 10 carbon atoms, and be connected with the rest part of molecule by singly-bound.
Term " alkynyl " refers to the hydrocarbon chain group of straight or branched, described hydrocarbon chain group only forms, contains one or more triple bonds by carbon and hydrogen atom, there are 3 to 50 carbon atoms, preferably 3 to 20 carbon atoms or 3 to 10 carbon atoms, and be connected with the rest part of molecule by singly-bound.
Term " heteroaryl " refers to and comprises 3 to 50 carbon atoms and 1 to 15 heteroatomic aromatic ring group that is 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 condense or bridge joint; And the nitrogen in heteroaryl, carbon or sulphur atom are optionally oxidized; Nitrogen-atoms is optionally quaternized.Described heteroaryl preferably comprises 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms, preferably comprise 1-10, and more preferably 1-5 is individual, most preferably 1-3 heteroatoms that is selected from nitrogen, oxygen and sulphur.Described heteroaryl is preferably 5 yuan of above monocyclic, bicyclic or tricyclic systems.
Term " aryl " refers to the aromatic ring group that comprises 6 to 50 carbon atoms.Described aryl can be the loop systems at monocycle, dicyclo, three rings or Fourth Ring, and it can comprise loop systems 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 3 to 50 carbon atoms and 1 to 15 heteroatomic saturated nonaro-maticity cyclic group that is 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 condense or bridge joint; And the nitrogen in Heterocyclylalkyl, carbon or sulphur atom are optionally oxidized; Nitrogen-atoms is optionally quaternized.Described Heterocyclylalkyl preferably comprises 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms, preferably comprise 1-10, and more preferably 1-5 is individual, most preferably 1-3 heteroatoms that is selected from nitrogen, oxygen and sulphur.Described Heterocyclylalkyl is preferably 5 yuan of above monocyclic, bicyclic or tricyclic systems.
Term " heterocycloalkenyl " refers to and comprises heteroatomic, the nonaro-maticity cyclic group that contains one or more pairs of keys that 3 to 50 carbon atoms and 1 to 15 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 condense or bridge joint; And the nitrogen in heterocycloalkenyl, carbon or sulphur atom are optionally oxidized; Nitrogen-atoms is optionally quaternized.Described heterocycloalkenyl preferably comprises 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms, preferably comprise 1-10, and more preferably 1-5 is individual, most preferably 1-3 heteroatoms that is selected from nitrogen, oxygen and sulphur.Described heterocycloalkenyl preferably comprises 1-5, more preferably 1-3 unsaturated double-bond.Described heterocycloalkenyl is preferably 5 yuan of above monocyclic, bicyclic or tricyclic systems.
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 " Heterocyclylalkyl alkyl " 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 that contains a hydroxyl with 1-50 carbon atom, and it represents by general formula R OH, and wherein R represents that described group is selected from the C of straight chain, side chain or ring-type by the optional group replacing of one or more substituting groups
1-C
50the C of alkyl, straight chain, side chain or ring-type
3-C
50the C of thiazolinyl, straight or branched
3-C
50alkynyl, C
6-C
50aryl, C
3-C
50heteroaryl, C
3-C
50heterocyclylalkyl or heterocycloalkenyl, C
7-C
50aralkyl, C
4-C
50heteroaralkyl or C
4-C
50heterocyclylalkyl alkyl 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
5-C
10cycloalkyl, sulfydryl, halogen, cyano group, amino, aldehyde radical, carbonyl, C
1-C
10alkyl monosubstituted or disubstituted amino or C
1-C
10alkyl-O-CO-; Or described monohydroxy-alcohol is by general formula OH-[(CH
2)
no] m-R
1represent the integer that wherein n is 1-6, the integer that m is 1-5, R
1c for straight chain, side chain or ring-type
1-C
7alkyl, phenyl or benzyl, and n and m can not be 1 simultaneously.
In one embodiment, described monohydroxy-alcohol is preferably selected from 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, potato spirit, 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, cyclohexane methanol, octanol, sec-n-octyl alcohol, 2-Ethylhexyl Alcohol, 3,5,5-trimethyl hexanol, nonyl alcohol, 2,6-2,6-dimethyl-4-heptanol, decyl alcohol, undecyl alcohol, 5-ethyl-2-nonyl alcohol, lauryl alcohol, Exxal 12, tetradecyl alcohol, hexadecanol, heptadecyl alcohol, stearyl alcohol, cyclopentanol, hexalin, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 4 methyl cyclohexanol, phenylcarbinol, α-terpinol, rosin alcohol, phenylethyl alcohol, benzhydrol, naphthalene methyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, 1-methoxy-2-propanol, 1-oxyethyl group-2-propyl alcohol, 1-propoxy--2-propyl alcohol, 1-butoxy-2-propyl alcohol, Pyranton, ethylene chlorhydrin, ethylene bromohyrin, 1-chloro-2-propanol, trimethylene chlorohydrin, the chloro-n-butyl alcohol of 4-, the chloro-2-propyl alcohol of 1,3-bis-, 2,3-, bis-trimethylewne chlorohydrin 3-s, 3-methoxybutanol, vinyl alcohol, vinyl carbinol, alkene butanols, alkene amylalcohol, acetylene alcohol, propargyl alcohol, alkynes butanols, alkynes amylalcohol, 2,2,2 tfifluoroethyl alcohol, 3-hydroxypropionitrile, acetone cyanohydrin, 2-monoethanolamine, 2-(ethylamino) ethanol, 2-(dimethylamino) ethanol, 1-(fourth oxygen oxyethyl group)-2-propyl alcohol, 2-(diethylin) ethanol, 2-(dibutylamino) ethanol, 1-amino-2-propyl alcohol, pmethoxybenzyl alcohol, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, amyl lactate, 4-hydroxy-4-methyl-2-pentanone, 2-methyl-3-butyne-2-alcohol, methylpentynol or dimethylated hexynol.
In another embodiment, described monohydroxy-alcohol is preferably selected from ethylene glycol-monomethyl ether, ethylene glycol-mono-ether, 2-(methoxy methoxy base) 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, glycol ether-mono-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, triglycol-monomethyl ether, triglycol-mono-ether, Tetraglycol 99-monomethyl ether, Tetraglycol 99-mono-ether, dipropylene glycol-monomethyl ether, dipropylene glycol-mono-ether, dipropylene glycol-mono-propyl ether, dipropylene glycol-mono-isopropyl ether, dipropylene glycol-monobutyl ether, dipropylene glycol-mono-ethyl isobutyl ether, tripropylene glycol-monomethyl ether, tripropylene glycol-monomethyl ether.
In this application, term " polyol " refers to and contains the alkylol cpd that is more than or equal to two hydroxyls.The polyvalent alcohol using in method described in the application is preferably C
2-C
50polyvalent alcohol and polymerized polyalcohol.Described polyvalent alcohol can be by general formula R
2(OH)
nrepresent n=2-50 wherein, R
2expression is by the optional group replacing of one or more substituting groups, and described group is selected from the C of straight chain, side chain or ring-type
2-C
50the C of alkyl, straight chain, side chain or ring-type
4-C
50the C of thiazolinyl, straight or branched
4-C
50alkynyl, C
6-C
50aryl, C
3-C
50heteroaryl, C
3-C
50heterocyclylalkyl or heterocycloalkenyl, C
7-C
50aralkyl, C
4-C
50heteroaralkyl or C
4-C
50heterocyclylalkyl alkyl 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
5-C
10cycloalkyl, sulfydryl, halogen, cyano group, amino, aldehyde radical, carbonyl, C
1-C
10alkyl monosubstituted or disubstituted amino or C
1-C
10alkyl-O-CO-; Or by general formula OH-[(CH
2)
no] m-H represents, the integer that wherein n is 1-6, the integer that m is 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-propylene glycol, 1, ammediol, 1, 2-butyleneglycol, 1, 3-butyleneglycol, 1, 4-butyleneglycol, 2, 3-butyleneglycol, 1, 5-pentanediol, neopentyl glycol, 1, 2-hexylene glycol, 1, 2-cyclohexanediol, 1, 4-cyclohexanediol, 2-butylene-1, 4-glycol, 2-methyl-2, 4-pentanediol, 2-ethyl-1, 3-hexylene glycol, tetramethyl ethylene ketone, heptanediol, ethohexadiol, nonanediol, decanediol, triglycol, glycerol, 1, 2, 4-trihydroxybutane, 1, 2, 6-hexanetriol, 2-ethyl-2-(methylol)-1, ammediol, butantetraol, tetramethylolmethane, sorbyl alcohol, mannitol, Xylitol, glycol ether, triglycol, Tetraglycol 99, dipropylene glycol, tripropylene glycol, 3-chloro-1, 2-propylene glycol, diethanolamine, ethyldiethanolamine, butyl diethanolamine, trolamine, tri-isopropanolamine, thiodiglycol, 2-butyne-1, 4-glycol, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly-pentanediol, poly-hexylene glycol, polyglycerol etc.
In one embodiment, described alkylol cpd and calcium carbide are added in reactor, at the temperature of 0 ° of C-600 ° of C, preferably at the temperature of room temperature-450 ° C, more preferably under the temperature of reaction of 50 ° of C-350 ° of C, reacting of described alkylol cpd and calcium carbide occur.In addition, those skilled in the art can understand, can be according to the needs of practice, and the kind of selected alkylol cpd for example, selects to be suitable for the temperature of reaction.
In one embodiment, described alkylol cpd and calcium carbide are added in reactor, under the absolute pressure of 0Mpa-20Mpa, preferably under the absolute pressure of 0.1Mpa-15Mpa, more preferably under the absolute pressure of 0.1-12Mpa, there is reacting of described alkylol cpd and calcium carbide.Described absolute pressure is for example 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 be according to the needs of practice, and the kind of selected alkylol cpd for example, selects to be suitable for the absolute pressure of reaction.
Therefore, in the reacting of alkylol cpd and calcium carbide, the absolute pressure of temperature of reaction and reaction changes with the kind of alkylol cpd, preferably select applicable temperature of reaction and reaction absolute pressure so that alkylol cpd under liquid state, react with calcium carbide.
In a preferred embodiment, the reacting of described alkylol cpd and calcium carbide is to occur under the temperature of 0 ° of C-600 ° of C and the absolute pressure of 0Mpa-20Mpa, preferably under the temperature of room temperature-450 ° C and the absolute pressure of 0.1Mpa-15Mpa, occur, more preferably under the temperature of 50 ° of C-350 ° of C and the absolute pressure of 0.1Mpa-12Mpa, occur.
In one embodiment, the mol ratio of calcium carbide and described alkylol cpd is 1:0.01-1:100, preferably 1:0.05-1:50, more preferably 1:0.03-1:30, even more preferably 1:0.1-1:10, most preferably 1:0.1-1:3.
In a preferred embodiment, can before reaction and/or in reaction, in the reaction system of calcium carbide and alkylol cpd, be filled with shielding gas, to avoid the generation of side reaction.Described shielding gas be selected from rare gas element, nitrogen, carbonic acid gas and airborne one or more.Described rare gas element includes but not limited to helium, neon, argon gas and Krypton, preferably helium and argon gas.
Shown in reaction mechanism as described above, in the reacting of alkylol cpd and calcium carbide, when the mol ratio of the kind of selected alkylol cpd and alkylol cpd and calcium carbide is different, the kind of products therefrom is also thereupon different.
Therefore,, in the preparation method of the alkoxide of the calcium described in the application, products therefrom can be the monobasic alkoxide of calcium, the polynary alkoxide of calcium or its mixture.For example, when alkylol cpd is monohydroxy-alcohol, the product monobasic alkoxide that is calcium; When alkylol cpd is dibasic alcohol, according to the mol ratio of calcium carbide and alkylol cpd, products therefrom can be single dibasic alkoxide of calcium, two dibasic alkoxides of calcium or both mixtures, and in wherein said mixture, the ratio of single dibasic alkoxide of calcium and two dibasic alkoxides of calcium can be arbitrarily.When alkylol cpd is while containing the polyvalent alcohol that is greater than two hydroxyls, the polynary alkoxide that products therefrom is calcium or its mixture, in wherein said mixture, the ratio of various polynary alkoxide can be arbitrarily.
In this application, when monobasic alkoxide that product is calcium, it can be by general formula Ca (OR)
2represent, wherein R represents that described group is selected from the C of straight chain, side chain or ring-type by the optional group replacing of one or more substituting groups
1-C
50the C of alkyl, straight chain, side chain or ring-type
3-C
50the C of thiazolinyl, straight or branched
3-C
50alkynyl, C
6-C
50aryl, C
3-C
50heteroaryl, C
3-C
50heterocyclylalkyl or heterocycloalkenyl, C
7-C
50aralkyl, C
4-C
50heteroaralkyl or C
4-C
50heterocyclylalkyl alkyl 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
5-C
10cycloalkyl, sulfydryl, halogen, cyano group, amino, aldehyde radical, carbonyl, C
1-C
10alkyl monosubstituted or disubstituted amino or C
1-C
10alkyl-O-CO-; Or by general formula Ca{O-[(CH
2)
no] m-R
1}
2, the integer that wherein n is 1-6, the integer that m is 1-5, R
1c for 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 the monobasic alkoxide of described 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, secondary primary isoamyl alcohol calcium, potato spirit calcium, hexanol calcium, 4-methyl-2-amylalcohol calcium, 2-hexanol calcium, 2-ethyl butanol calcium, 2-methyl amyl alcohol calcium, 2-methyl-2-amylalcohol calcium, 2-methyl-3-amylalcohol calcium, 3-ethyl-3 amylalcohol calcium, enanthol calcium, 2-enanthol calcium, 3-enanthol calcium, cyclohexanemethanol calcium, octanol calcium, sec-n-octyl alcohol calcium, 2-Ethylhexyl Alcohol calcium, 3,5,5-trimethyl hexanol calcium, nonyl alcohol calcium, 2,6-2,6-dimethyl-4-heptanol calcium, decyl alcohol calcium, undecyl alcohol calcium, 5-ethyl-2-nonyl alcohol calcium, lauryl alcohol calcium, Exxal 12 calcium, tetradecyl alcohol calcium, hexadecanol calcium, heptadecyl alcohol calcium, stearyl alcohol calcium, cyclopentanol calcium, hexalin calcium, 2 methyl cyclohexanol calcium, 3 methyl cyclohexanol calcium, 4 methyl cyclohexanol calcium, phenylcarbinol calcium, α-terpinol calcium, rosin alcohol calcium, phenylethyl alcohol calcium, benzhydrol calcium, naphthalene calcium methylate, ethylene glycol-monomethyl ether calcium, ethylene glycol-mono-ether calcium, 2-(methoxy methoxy base) calcium ethylate, ethylene glycol-mono-propyl ether calcium, ethylene glycol-mono-isopropyl ether calcium, ethylene glycol-monobutyl ether calcium, ethylene glycol-mono-ethyl isobutyl ether calcium, ethylene glycol-monopentyl ether calcium, ethylene glycol-mono-isoamyl oxide calcium, ethylene glycol-monohexyl ether calcium, ethylene glycol-monophenyl ether calcium, ethylene glycol-mono-benzyl oxide calcium, furfuryl alcohol calcium, tetrahydrofurfuryl alcohol calcium, glycol ether-monomethyl ether calcium, glycol ether-mono-ether calcium, glycol ether-mono-propyl ether calcium, glycol ether-mono-isopropyl ether calcium, glycol ether-monobutyl ether calcium, glycol ether-mono-ethyl isobutyl ether calcium, glycol ether-monopentyl ether calcium, glycol ether-mono-isoamyl oxide calcium, triglycol-monomethyl ether calcium, triglycol-mono-ether calcium, Tetraglycol 99-monomethyl ether calcium, Tetraglycol 99-mono-ether calcium, 1-methoxy-2-propanol calcium, 1-oxyethyl group-2-calcium propylate, 1-propoxy--2-calcium propylate, 1-butoxy-2-calcium propylate, 1-(fourth oxygen oxyethyl group)-2-calcium propylate, dipropylene glycol-monomethyl ether calcium, dipropylene glycol-mono-ether calcium, dipropylene glycol-mono-propyl ether calcium, dipropylene glycol-mono-isopropyl ether calcium, dipropylene glycol-monobutyl ether calcium, dipropylene glycol-mono-ethyl isobutyl ether calcium, tripropylene glycol-monomethyl ether calcium, tripropylene glycol-monomethyl ether calcium, Pyranton calcium, ethylene chlorhydrin calcium, ethylene bromohyrin calcium, 1-chloro-2-propanol calcium, trimethylene chlorohydrin calcium, the chloro-n-butyl alcohol calcium of 4-, the chloro-2-calcium propylate of 1,3-bis-, the chloro-1-calcium propylate of 2,3-bis-, 3-methoxybutanol calcium, vinyl alcohol calcium, vinyl carbinol calcium, alkene calcium butoxide, alkene amylalcohol calcium, acetylene alcohol calcium, propargyl alcohol calcium, alkynes calcium butoxide, alkynes amylalcohol calcium, 2,2,2 tfifluoroethyl alcohol calcium, 3-hydroxypropionitrile calcium, acetone cyanohydrin calcium, 2-monoethanolamine calcium, 2-(ethylamino) calcium ethylate, 2-(dimethylamino) calcium ethylate, 2-(diethylin) calcium ethylate, 2-(dibutylamino) calcium ethylate, 1-amino-2-calcium propylate, pmethoxybenzyl alcohol calcium, methyl lactate calcium, ethyl lactate calcium, propyl lactate calcium, n-Butyl lactate calcium, amyl lactate calcium, 4-hydroxy-4-methyl-2-pentanone calcium, 2-methyl-3-butyne-2-alcohol calcium, methylpentynol calcium, dimethylated hexynol calcium etc.
In this application, when the polynary alkoxide of list that product is calcium, it can be by general formula (CaO
2)
yr
2(OH)
z(y>=1, z>=0, and 2y+z=2-50) expression, wherein R
2expression is by the optional group replacing of one or more substituting groups, and described group is selected from the C of straight chain, side chain or ring-type
2-C
50the C of alkyl, straight chain, side chain or ring-type
2-C
50the C of alkoxyl group, straight chain, side chain or ring-type
4-C
50the C of thiazolinyl, straight or branched
4-C
50alkynyl, C
6-C
50aryl, C
3-C
50heteroaryl, C
3-C
50heterocyclylalkyl or heterocycloalkenyl, C
7-C
50aralkyl, C
4-C
50heteroaralkyl or C
4-C
50heterocyclylalkyl alkyl 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
5-C
10cycloalkyl, sulfydryl, halogen, cyano group, amino, aldehyde radical, carbonyl, C
1-C
10alkyl monosubstituted or disubstituted amino or C
1-C
10alkyl-O-CO-; Or it can be by general formula Ca{O-[(CH
2)
no] m}, the integer that wherein n is 1-6, the integer that m is 1-5, and n and m can not be 1 simultaneously.
The example of the polynary alkoxide of list of described calcium includes but not limited to ethylene glycol calcium, 1,2-PD calcium, 1,3-PD calcium, 1,2-butyleneglycol calcium, 1,3 butylene glycol calcium, BDO calcium, 2,3-butanediol calcium, 1,5-PD calcium, neopentyl glycol calcium, 1,2-hexylene glycol calcium, 1,2-cyclohexanediol calcium, Isosorbide-5-Nitrae-cyclohexanediol calcium, 2-butylene-Isosorbide-5-Nitrae-glycol calcium, 2-methyl-2,4-pentanediol calcium, 2-ethyl-1,3-hexylene glycol calcium, tetramethyl ethylene ketone calcium, heptanediol calcium, ethohexadiol calcium, nonanediol calcium, decanediol calcium, 2-ethyl-2-(methylol)-1,3-PD calcium, butantetraol calcium, tetramethylolmethane calcium, sorbyl alcohol calcium, mannitol calcium, Xylitol calcium, glycol ether calcium, triglycol calcium, Tetraglycol 99 calcium, dipropylene glycol calcium, tripropylene glycol calcium, 3-chlorine-1,2-propylene glycol calcium, diethanolamine calcium, ethyldiethanolamine calcium, butyl diethanolamine calcium, trolamine calcium, tri-isopropanolamine calcium, thiodiglycol calcium, 2-butyne-Isosorbide-5-Nitrae-glycol calcium, 1,2-glycerol calcium, 1,3-glycerol calcium, 1,2-trihydroxybutane calcium, Isosorbide-5-Nitrae-trihydroxybutane calcium, 2,4-trihydroxybutane calcium, 1,2-hexanetriol calcium, 1,6-hexanetriol calcium, 2,6-hexanetriol calcium etc.
In this application, when two polynary alkoxide that product is calcium, it can be by general formula (OH)
ar
5(CaO
2)
yr
6(OH)
b(y>=1, a>=1, b>=1, and 2y+a+b=4-100) expression, wherein R
5, R
6represent that independently described group is selected from the C of straight chain, side chain or ring-type by the optional group replacing of one or more substituting groups
2-C
50the C of alkyl, straight chain, side chain or ring-type
2-C
50the C of alkoxyl group, straight chain, side chain or ring-type
4-C
50the C of thiazolinyl, straight or branched
4-C
50alkynyl, C
6-C
50aryl, C
3-C
50heteroaryl, C
3-C
50heterocyclylalkyl or heterocycloalkenyl, C
7-C
50aralkyl, C
4-C
50heteroaralkyl or C
4-C
50heterocyclylalkyl alkyl 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
5-C
10cycloalkyl, sulfydryl, halogen, cyano group, amino, aldehyde radical, carbonyl, C
1-C
10alkyl monosubstituted or disubstituted amino or C
1-C
10alkyl-O-CO-.
The example of two polynary alkoxide of described calcium includes but not limited to C
4h
10o
4ca (two-ethylene glycol-1-closes calcium), C
6h
14o
4ca (two-1,2-PD-1-O-closes calcium, two-1,2-PD-2-O-closes calcium, 1,2-PD-1-O-1, and 2-propylene glycol-2-O-closes calcium or its mixture, two-1,3-PD-1-O-closes calcium), C
8h
18o
4ca (two-1,2-butyleneglycol-1-O-closes calcium, two-1,2-butyleneglycol-2-O-closes calcium, 1,2-butyleneglycol-1-O-1, and 2-butyleneglycol-2-O-closes calcium or its mixture, two-1,3-butyleneglycol-1-O-closes calcium, two-1,3-butyleneglycol-3-O-closes calcium, 1,3 butylene glycol-1-O-1, and 3-butyleneglycol-3-O-closes calcium or its mixture, two-1,4-butyleneglycol-1-O-closes calcium, two-2,3-butanediol-2-O-closes calcium), C
10h
22o
4ca (two-1,5-PD-1-O-closes calcium, two-neopentyl glycol-1-O closes calcium), C
12h
26o
4ca (two-1,2-hexylene glycol-1-O-closes calcium, two-1,2-hexylene glycol-2-O-closes calcium, 1,2-hexylene glycol-1-O-1,2-hexylene glycol-2-O-closes calcium or its mixture, two-2-methyl-2, and 4-pentanediol-2-O-closes calcium, two-2-methyl-2, and 4-pentanediol-4-O-closes calcium, 2-methyl-2,4-pentanediol-2-O-2-methyl-2,4-pentanediol-4-O-closes calcium or its mixture), C
12h
22o
4ca (two-1,2-cyclohexanediol-1-O-closes calcium, two-1,2-cyclohexanediol-2-O-closes calcium, 1,2-cyclohexanediol-1-O-1,2-cyclohexanediol-2-O-closes that calcium or its mixture, two-Isosorbide-5-Nitrae-cyclohexanediol-1-O-close calcium, two-Isosorbide-5-Nitrae-cyclohexanediol-4-O-closes calcium, 1,4-cyclohexanediol-1-O-1,4-cyclohexanediol-4-O-closes calcium or its mixture), C
14h
30o
4ca (two-heptanediol calcium), C
16h
34o
4ca (two-ethohexadiol calcium), C
18h
38o
4ca (two-nonanediol calcium), C
20h
42o
4ca (two-decanediol calcium), C
12h
26o
8ca (two-triglycol calcium), C
6h
10o
6ca
3(two-1,2-glycerol calcium-3-O-closes calcium, two-1, and 3-glycerol calcium-2-O-closes calcium, 1,2-glycerol calcium-2-O-1,3-glycerol-3-O-closes calcium or its mixture), two glycerol-1,2,3-tricalcium, polyglycerol close calcium, C
8h
14o
6ca
3(two-1,2-trihydroxybutane calcium-4-O-closes calcium, two-Isosorbide-5-Nitrae-trihydroxybutane calcium-2-O-closes calcium, two-2, and 4-trihydroxybutane calcium-1-O-closes calcium, 1,2-trihydroxybutane calcium-4-O-1,4-trihydroxybutane-2-O-closes calcium, 1,2-trihydroxybutane calcium-4-O-2, and 4-trihydroxybutane-1-O-closes calcium, 1,4-trihydroxybutane calcium-2-O-2,4-trihydroxybutane-1-O-closes calcium or its mixture), poly-BT closes calcium, C
12h
22o
6ca
3(two-1,2-hexanetriol calcium-6-O-closes calcium, two-1, and 6-hexanetriol calcium-2-O-closes calcium, two-2, and 6-hexanetriol calcium-1-O-closes calcium, 1,2-hexanetriol calcium-6-O-1,6-hexanetriol-2-O-closes calcium, 1,2-hexanetriol calcium-6-O-2, and 6-hexanetriol-1-O-closes calcium, 1,6-hexanetriol calcium-2-O-2,6-hexanetriol-1-O-closes calcium or its mixture), poly-1,2,6-hexanetriol closes calcium or its mixture etc.;
In this application, when product is polymerized polyalcohol salt, the example of described polymerized polyalcohol salt includes but not limited to polyoxyethylene glycol calcium, polypropylene glycol calcium, polytetramethylene glycol calcium, poly-pentanediol calcium, poly-hexylene glycol calcium, polyglycerol calcium, poly-trihydroxybutane calcium, poly-penta triol calcium, poly-hexanetriol calcium etc.
Will be understood by those skilled in the art that to the description of reaction mechanism, to be in order to contribute to the understanding of the present invention above, rather than product is restricted to pure single compound.The alkoxide that it will be appreciated by those skilled in the art that the calcium of preparing by method mentioned above can be the mixture of multi-products, and such mixture is also contained within the scope of the invention.
Utilize calcium carbide and reacting of alkylol cpd described in the application, prepare in the method for alkoxide of calcium, the purity of calcium carbide and alkylol cpd can be 1-100% independently, the purity of described calcium carbide is preferably more than 60%, and the purity of described alcoholate is preferably more than 80%, more preferably more than 90%.In the product finally obtaining, the purity of the alkoxide cpd of calcium is 1-100%, preferably 50%-100%, more preferably 70%-100%, most preferably 90%-100%; Its transformation efficiency can reach more than 90% (in calcium, as follows).
Utilize calcium carbide and reacting of alkylol cpd described in the application are prepared in the method for alkoxide of calcium, have following one or more advantages: (1) raw material calcium carbide and alkylol cpd are cheap and be easy to be purchased, and running cost is low; (2) preparation technology is simple, easy handling; (3) reaction process is milder, is conducive to safety in production; (4) by product acetylene is collected by being used after separating-purifying; (5) products obtained therefrom non-environmental-pollution problem; (6) in the thick product of gained, impurity is easily separated with product, purifies comparatively simple.
Therefore the method for utilizing calcium carbide and reacting of alkylol cpd to prepare the alkoxide of calcium described in the application has important actual application value, can be applied to industrial production.
Below in connection with embodiment, the present invention will be described in detail, but those skilled in the art should be appreciated that those skilled in the art, according to the technical knowledge that discloses and itself have of the present invention, can carry out some change or modification to the present invention.Therefore, scope of the present invention is not limited to following embodiment, and should only by claims, be limited.
Embodiment
Embodiment 1:
Calcium carbide (53.6 grams, SILVER REAGENT) is placed in to reactor, then in reactor, adds ethanol (101.5 grams, analytical pure).Install reactor, be filled with subsequently nitrogen, to be heated to temperature of reaction be 60 ° of C and pressure is remained under 1.0MPa, reaction 5.0h.After having reacted, cooling reactor is also collected gas, the white solid that reaction product contains calcium ethylate (78.0g, yield approximately 80%).
Embodiment 2:
Except reacting by heating still to temperature of reaction be 130 ° of C, reaction pressure to 4.0MPa, adopt identical reactant, reaction conditions and reactions steps in embodiment 1, obtain the white solid product (90.0g, yield approximately 92%) containing calcium ethylate.
Embodiment 3
Except reacting by heating still to temperature of reaction is that 220 ° of C, reaction pressure are to 12.0MPa, adopt identical reactant, reaction conditions and reactions steps in embodiment 1, obtain the white solid product (93.0g, yield approximately 95%) containing calcium ethylate through infrared analysis.
Embodiment 4:
Calcium carbide (41.7 grams, SILVER REAGENT) is placed in to reactor, then in reactor, adds ethylene glycol (130.0 grams, analytical pure).Install reactor, to be heated to temperature of reaction be 80 ° of C and pressure is remained under 1.0MPa, reaction 6.0h.After having reacted, cooling reactor is also collected gas, and reaction product is the light yellow solid (45.0 grams, yield is about 75%) containing ethylene glycol calcium.
Embodiment 5
Except reacting by heating still to temperature of reaction be 220 ° of C, reaction pressure to 3.0MPa, adopt identical reactant, reaction conditions and reactions steps in embodiment 4, obtain the light yellow solid product that contains ethylene glycol calcium, (50.0g, yield approximately 83%).
Embodiment 6
Except reacting by heating still to temperature of reaction be 280 ° of C, reaction pressure to 10.0MPa, adopt identical reactant, reaction conditions and reactions steps in embodiment 4, obtain the light yellow solid product that contains ethylene glycol calcium, (52.0g, yield approximately 86%).
Claims (11)
1. the preparation method of the alkoxide of calcium, it comprises the step that alkylol cpd is reacted with calcium carbide, described alkylol cpd is selected from monohydroxy-alcohol and comprises one or more in the polyvalent alcohol that is more than or equal to two hydroxyls.
2. the method for claim 1, wherein 0 ° of C-600 ° of C, preferably room temperature-450 ° C, more preferably under the temperature of reaction of 50 ° of C-350 ° of C, there is reacting of described alkylol cpd and calcium carbide.
3. method as claimed in claim 1 or 2, wherein 0Mpa-20Mpa, preferably 0.1Mpa-15Mpa, more preferably under the absolute pressure of 0.1Mpa-12Mpa, there is reacting of described alkylol cpd and calcium carbide.
4. the method as described in arbitrary claim in claim 1-3, the mol ratio of wherein said calcium carbide and described alkylol cpd is 1:0.01-1:100, preferably 1:0.05-1:50, more preferably 1:0.03-1:30, even more preferably 1:0.1-1:10, most preferably 1:0.1-1:3.
5. the method as described in arbitrary claim in claim 1-4; it also comprises to the step that is filled with shielding gas in the reaction system of described calcium carbide and described alkylol cpd, described shielding gas include but not limited to rare gas element, nitrogen, carbonic acid gas and airborne one or more.
6. the method as described in arbitrary claim in claim 1-5, the purity of wherein said calcium carbide and described alkylol cpd is 1-100% independently, the purity of described calcium carbide is preferably more than 60%, and the purity of described alcoholate is preferably more than 80%, more preferably more than 90%.
7. the method as described in arbitrary claim in claim 1-6, wherein in product, the purity of the alkoxide of calcium is 1-100%, preferably 50%-100%, more preferably 70%-100%, most preferably 90%-100%.
8. the method as described in arbitrary claim in claim 1-7, wherein said monohydroxy-alcohol is C
1-C
50monohydroxy-alcohol, it represents by general formula R OH, wherein R represents that described group is selected from the C of straight chain, side chain or ring-type by the optional group replacing of one or more substituting groups
1-C
50the C of alkyl, straight chain, side chain or ring-type
3-C
50the C of thiazolinyl, straight or branched
3-C
50alkynyl, C
6-C
50aryl, C
3-C
50heteroaryl, C
3-C
50heterocyclylalkyl or heterocycloalkenyl, C
7-C
50aralkyl, C
4-C
50heteroaralkyl or C
4-C
50heterocyclylalkyl alkyl 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
5-C
10cycloalkyl, sulfydryl, halogen, cyano group, amino, aldehyde radical, carbonyl, C
1-C
10alkyl monosubstituted or disubstituted amino or C
1-C
10alkyl-O-CO-,
Wherein said monohydroxy-alcohol is preferably selected from 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, potato spirit, 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, cyclohexane methanol, octanol, sec-n-octyl alcohol, 2-Ethylhexyl Alcohol, 3,5,5-trimethyl hexanol, nonyl alcohol, 2,6-2,6-dimethyl-4-heptanol, decyl alcohol, undecyl alcohol, 5-ethyl-2-nonyl alcohol, lauryl alcohol, Exxal 12, tetradecyl alcohol, hexadecanol, heptadecyl alcohol, stearyl alcohol, cyclopentanol, hexalin, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 4 methyl cyclohexanol, phenylcarbinol, α-terpinol, rosin alcohol, phenylethyl alcohol, benzhydrol, naphthalene methyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, 1-methoxy-2-propanol, 1-oxyethyl group-2-propyl alcohol, 1-propoxy--2-propyl alcohol, 1-butoxy-2-propyl alcohol, Pyranton, ethylene chlorhydrin, ethylene bromohyrin, 1-chloro-2-propanol, trimethylene chlorohydrin, the chloro-n-butyl alcohol of 4-, the chloro-2-propyl alcohol of 1,3-bis-, 2,3-, bis-trimethylewne chlorohydrin 3-s, 3-methoxybutanol, vinyl alcohol, vinyl carbinol, alkene butanols, alkene amylalcohol, acetylene alcohol, propargyl alcohol, alkynes butanols, alkynes amylalcohol, 2,2,2 tfifluoroethyl alcohol, 3-hydroxypropionitrile, acetone cyanohydrin, 2-monoethanolamine, 2-(ethylamino) ethanol, 2-(dimethylamino) ethanol, 1-(fourth oxygen oxyethyl group)-2-propyl alcohol, 2-(diethylin) ethanol, 2-(dibutylamino) ethanol, 1-amino-2-propyl alcohol, pmethoxybenzyl alcohol, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, amyl lactate, 4-hydroxy-4-methyl-2-pentanone, 2-methyl-3-butyne-2-alcohol, methylpentynol or dimethylated hexynol,
Or
Described monohydroxy-alcohol is by general formula OH-[(CH
2)
no] m-R
1represent, the integer that wherein n is 1-6, the integer that m is 1-5, and n and m can not be 1, R simultaneously
1c for 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-(methoxy methoxy base) 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, glycol ether-mono-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, triglycol-monomethyl ether, triglycol-mono-ether, Tetraglycol 99-monomethyl ether, Tetraglycol 99-mono-ether, dipropylene glycol-monomethyl ether, dipropylene glycol-mono-ether, dipropylene glycol-mono-propyl ether, dipropylene glycol-mono-isopropyl ether, dipropylene glycol-monobutyl ether, dipropylene glycol-mono-ethyl isobutyl ether, tripropylene glycol-monomethyl ether, tripropylene glycol-monomethyl ether.
9. the method as described in arbitrary claim in claim 1-8, wherein said polyvalent alcohol is by the optional C replacing of one or more substituting groups
2-C
50polyvalent alcohol and polymerized polyalcohol, described substituting group is selected from C
1-C
10alkyl, halogen, amino, C1-C10 alkyl monosubstituted or disubstituted amino or sulfydryl, described polyvalent alcohol is preferably ethylene glycol, 1,2-PD, 1,3-PD, 1,2-butyleneglycol, 1,3 butylene glycol, BDO, 2,3-butanediol, 1,5-PD, neopentyl glycol, 1,2-hexylene glycol, 1,2-cyclohexanediol, Isosorbide-5-Nitrae-cyclohexanediol, 2-butylene-Isosorbide-5-Nitrae-glycol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexylene glycol, tetramethyl ethylene ketone, heptanediol, ethohexadiol, nonanediol, decanediol, triglycol, glycerol, BT, 1,2,6-hexanetriol, 2-ethyl-2-(methylol)-1,3-PD, butantetraol, tetramethylolmethane, sorbyl alcohol, mannitol, Xylitol, glycol ether, triglycol, Tetraglycol 99, dipropylene glycol, tripropylene glycol, 3-chlorine-1,2-propylene glycol, diethanolamine, ethyldiethanolamine, butyl diethanolamine, trolamine, tri-isopropanolamine, thiodiglycol, 2-butyne-Isosorbide-5-Nitrae-glycol, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly-pentanediol, poly-hexylene glycol, polyglycerol.
10. method as claimed in claim 8, the monobasic alkoxide that the alkoxide of wherein said calcium is calcium, 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, secondary primary isoamyl alcohol calcium, potato spirit calcium, hexanol calcium, 4-methyl-2-amylalcohol calcium, 2-hexanol calcium, 2-ethyl butanol calcium, 2-methyl amyl alcohol calcium, 2-methyl-2-amylalcohol calcium, 2-methyl-3-amylalcohol calcium, 3-ethyl-3 amylalcohol calcium, enanthol calcium, 2-enanthol calcium, 3-enanthol calcium, cyclohexanemethanol calcium, octanol calcium, sec-n-octyl alcohol calcium, 2-Ethylhexyl Alcohol calcium, 3,5,5-trimethyl hexanol calcium, nonyl alcohol calcium, 2,6-2,6-dimethyl-4-heptanol calcium, decyl alcohol calcium, undecyl alcohol calcium, 5-ethyl-2-nonyl alcohol calcium, lauryl alcohol calcium, Exxal 12 calcium, tetradecyl alcohol calcium, hexadecanol calcium, heptadecyl alcohol calcium, stearyl alcohol calcium, cyclopentanol calcium, hexalin calcium, 2 methyl cyclohexanol calcium, 3 methyl cyclohexanol calcium, 4 methyl cyclohexanol calcium, phenylcarbinol calcium, α-terpinol calcium, rosin alcohol calcium, phenylethyl alcohol calcium, benzhydrol calcium, naphthalene calcium methylate, ethylene glycol-monomethyl ether calcium, ethylene glycol-mono-ether calcium, 2-(methoxy methoxy base) calcium ethylate, ethylene glycol-mono-propyl ether calcium, ethylene glycol-mono-isopropyl ether calcium, ethylene glycol-monobutyl ether calcium, ethylene glycol-mono-ethyl isobutyl ether calcium, ethylene glycol-monopentyl ether calcium, ethylene glycol-mono-isoamyl oxide calcium, ethylene glycol-monohexyl ether calcium, ethylene glycol-monophenyl ether calcium, ethylene glycol-mono-benzyl oxide calcium, furfuryl alcohol calcium, tetrahydrofurfuryl alcohol calcium, glycol ether-monomethyl ether calcium, glycol ether-mono-ether calcium, glycol ether-mono-propyl ether calcium, glycol ether-mono-isopropyl ether calcium, glycol ether-monobutyl ether calcium, glycol ether-mono-ethyl isobutyl ether calcium, glycol ether-monopentyl ether calcium, glycol ether-mono-isoamyl oxide calcium, triglycol-monomethyl ether calcium, triglycol-mono-ether calcium, Tetraglycol 99-monomethyl ether calcium, Tetraglycol 99-mono-ether calcium, 1-methoxy-2-propanol calcium, 1-oxyethyl group-2-calcium propylate, 1-propoxy--2-calcium propylate, 1-butoxy-2-calcium propylate, 1-(fourth oxygen oxyethyl group)-2-calcium propylate, dipropylene glycol-monomethyl ether calcium, dipropylene glycol-mono-ether calcium, dipropylene glycol-mono-propyl ether calcium, dipropylene glycol-mono-isopropyl ether calcium, dipropylene glycol-monobutyl ether calcium, dipropylene glycol-mono-ethyl isobutyl ether calcium, tripropylene glycol-monomethyl ether calcium, tripropylene glycol-monomethyl ether calcium, Pyranton calcium, ethylene chlorhydrin calcium, ethylene bromohyrin calcium, 1-chloro-2-propanol calcium, trimethylene chlorohydrin calcium, the chloro-n-butyl alcohol calcium of 4-, the chloro-2-calcium propylate of 1,3-bis-, the chloro-1-calcium propylate of 2,3-bis-, 3-methoxybutanol calcium, vinyl alcohol calcium, vinyl carbinol calcium, alkene calcium butoxide, alkene amylalcohol calcium, acetylene alcohol calcium, propargyl alcohol calcium, alkynes calcium butoxide, alkynes amylalcohol calcium, 2,2,2 tfifluoroethyl alcohol calcium, 3-hydroxypropionitrile calcium, acetone cyanohydrin calcium, 2-monoethanolamine calcium, 2-(ethylamino) calcium ethylate, 2-(dimethylamino) calcium ethylate, 2-(diethylin) calcium ethylate, 2-(dibutylamino) calcium ethylate, 1-amino-2-calcium propylate, pmethoxybenzyl alcohol calcium, methyl lactate calcium, ethyl lactate calcium, propyl lactate calcium, n-Butyl lactate calcium, amyl lactate calcium, 4-hydroxy-4-methyl-2-pentanone calcium, 2-methyl-3-butyne-2-alcohol calcium, methylpentynol calcium, dimethylated hexynol calcium.
11. methods as claimed in claim 9, the alkoxide of wherein said calcium is the polynary alkoxide of calcium or the polymerized polyalcohol salt of calcium, the polynary alkoxide of described calcium is preferably ethylene glycol calcium, 1, 2-propylene glycol calcium, 1, ammediol calcium, 1, 2-butyleneglycol calcium, 1, 3-butyleneglycol calcium, 1, 4-butyleneglycol calcium, 2, 3-butyleneglycol calcium, 1, 5-pentanediol calcium, neopentyl glycol calcium, 1, 2-hexylene glycol calcium, 1, 2-cyclohexanediol calcium, 1, 4-cyclohexanediol calcium, 2-butylene-1, 4-glycol calcium, 2-methyl-2, 4-pentanediol calcium, 2-ethyl-1, 3-hexylene glycol calcium, tetramethyl ethylene ketone calcium, heptanediol calcium, ethohexadiol calcium, nonanediol calcium, decanediol calcium, C
4h
10o
4ca (two-ethylene glycol-1-closes calcium), C
6h
14o
4ca (two-1,2-PD-1-O-closes calcium, two-1,2-PD-2-O-closes calcium, 1,2-PD-1-O-1, and 2-propylene glycol-2-O-closes calcium or its mixture, two-1,3-PD-1-O-closes calcium), C
8h
18o
4ca (two-1,2-butyleneglycol-1-O-closes calcium, two-1,2-butyleneglycol-2-O-closes calcium, 1,2-butyleneglycol-1-O-1, and 2-butyleneglycol-2-O-closes calcium or its mixture, two-1,3-butyleneglycol-1-O-closes calcium, two-1,3-butyleneglycol-3-O-closes calcium, 1,3 butylene glycol-1-O-1, and 3-butyleneglycol-3-O-closes calcium or its mixture, two-1,4-butyleneglycol-1-O-closes calcium, two-2,3-butanediol-2-O-closes calcium), C
10h
22o
4ca (two-1,5-PD-1-O-closes calcium, two-neopentyl glycol-1-O closes calcium), C
12h
26o
4ca (two-1,2-hexylene glycol-1-O-closes calcium, two-1,2-hexylene glycol-2-O-closes calcium, 1,2-hexylene glycol-1-O-1,2-hexylene glycol-2-O-closes calcium or its mixture, two-2-methyl-2, and 4-pentanediol-2-O-closes calcium, two-2-methyl-2, and 4-pentanediol-4-O-closes calcium, 2-methyl-2,4-pentanediol-2-O-2-methyl-2,4-pentanediol-4-O-closes calcium or its mixture), C
12h
22o
4ca (two-1,2-cyclohexanediol-1-O-closes calcium, two-1,2-cyclohexanediol-2-O-closes calcium, 1,2-cyclohexanediol-1-O-1,2-cyclohexanediol-2-O-closes that calcium or its mixture, two-Isosorbide-5-Nitrae-cyclohexanediol-1-O-close calcium, two-Isosorbide-5-Nitrae-cyclohexanediol-4-O-closes calcium, 1,4-cyclohexanediol-1-O-1,4-cyclohexanediol-4-O-closes calcium or its mixture), C
14h
30o
4ca (two-heptanediol calcium), C
16h
34o
4ca (two-ethohexadiol calcium), C
18h
38o
4ca (two-nonanediol calcium), C
20h
42o
4ca (two-decanediol calcium), C
12h
26o
8ca (two-triglycol calcium), C
3h
6o
3ca (1,2-glycerol calcium, 1,3-glycerol calcium or its mixture), C
6h
10o
6ca
3(two-1,2-glycerol calcium-3-O-closes calcium, two-1, and 3-glycerol calcium-2-O-closes calcium, 1,2-glycerol calcium-2-O-1,3-glycerol-3-O-closes calcium or its mixture), two glycerol-1,2,3-tricalcium, polyglycerol close calcium, C
4h
8o
3ca (1,2-trihydroxybutane calcium, Isosorbide-5-Nitrae-trihydroxybutane calcium, 2,4-trihydroxybutane calcium or its mixture), C
8h
14o
6ca
3(two-1,2-trihydroxybutane calcium-4-O-closes calcium, two-Isosorbide-5-Nitrae-trihydroxybutane calcium-2-O-closes calcium, two-2, and 4-trihydroxybutane calcium-1-O-closes calcium, 1,2-trihydroxybutane calcium-4-O-1,4-trihydroxybutane-2-O-closes calcium, 1,2-trihydroxybutane calcium-4-O-2, and 4-trihydroxybutane-1-O-closes calcium, 1,4-trihydroxybutane calcium-2-O-2,4-trihydroxybutane-1-O-closes calcium or its mixture), poly-BT closes calcium, C
6h
12o
3ca (1,2-hexanetriol calcium, 1,6-hexanetriol calcium, 2,6-hexanetriol calcium or its mixture), C
12h
22o
6ca
3(two-1, 2-hexanetriol calcium-6-O-closes calcium, two-1, 6-hexanetriol calcium-2-O-closes calcium, two-2, 6-hexanetriol calcium-1-O-closes calcium, 1, 2-hexanetriol calcium-6-O-1, 6-hexanetriol-2-O-closes calcium, 1, 2-hexanetriol calcium-6-O-2, 6-hexanetriol-1-O-closes calcium, 1, 6-hexanetriol calcium-2-O-2, 6-hexanetriol-1-O-closes calcium or its mixture), poly-1, 2, 6-hexanetriol closes calcium, 2-ethyl-2-(methylol)-1, ammediol calcium, butantetraol calcium, tetramethylolmethane calcium, sorbyl alcohol calcium, mannitol calcium, Xylitol calcium, glycol ether calcium, triglycol calcium, Tetraglycol 99 calcium, dipropylene glycol calcium, tripropylene glycol calcium, 3-chloro-1, 2-propylene glycol calcium, diethanolamine calcium, ethyldiethanolamine calcium, butyl diethanolamine calcium, trolamine calcium, tri-isopropanolamine calcium, thiodiglycol calcium, 2-butyne-1, the mixture of 4-glycol calcium or two or more above-claimed cpd, described polymerized polyalcohol salt is preferably polyoxyethylene glycol calcium, polypropylene glycol calcium, polytetramethylene glycol calcium, poly-pentanediol calcium, poly-hexylene glycol calcium, polyglycerol calcium, poly-trihydroxybutane calcium, poly-penta triol calcium, poly-hexanetriol calcium.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140364580A1 (en) * | 2011-12-08 | 2014-12-11 | Changchun Institute Of Applied Chemistry Chinese Academy Of Sciences | Metal alkoxide complex, catalyst composition, and production method of polycaprolactone or polylactide |
| CN107673973A (en) * | 2017-09-29 | 2018-02-09 | 山东国邦药业股份有限公司 | A kind of preparation method of cyclopropylamine intermediate cyclopropanecarboxylic acid methyl esters |
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| US3341606A (en) * | 1965-10-22 | 1967-09-12 | Air Reduction | Process for producing vinyl ethers |
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| US3341606A (en) * | 1965-10-22 | 1967-09-12 | Air Reduction | Process for producing vinyl ethers |
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| Title |
|---|
| 刘青: "电石与甲醇、乙醇、异丙醇反应的研究", 《北京化工大学硕士研究生学位论文》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140364580A1 (en) * | 2011-12-08 | 2014-12-11 | Changchun Institute Of Applied Chemistry Chinese Academy Of Sciences | Metal alkoxide complex, catalyst composition, and production method of polycaprolactone or polylactide |
| US9676904B2 (en) * | 2011-12-08 | 2017-06-13 | Changchun Institute Of Applied Chemistry Chinese Academy Of Sciences | Metal alkoxide complex, catalyst composition, and production method of polycaprolactone or polylactide |
| CN107673973A (en) * | 2017-09-29 | 2018-02-09 | 山东国邦药业股份有限公司 | A kind of preparation method of cyclopropylamine intermediate cyclopropanecarboxylic acid methyl esters |
| CN107673973B (en) * | 2017-09-29 | 2020-08-18 | 山东国邦药业有限公司 | Preparation method of cyclopropylamine intermediate methyl cyclopropanecarboxylate |
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