CN1654451A - Process for synthesis of diol monoether carboxylate - Google Patents
Process for synthesis of diol monoether carboxylate Download PDFInfo
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- CN1654451A CN1654451A CN 200410021796 CN200410021796A CN1654451A CN 1654451 A CN1654451 A CN 1654451A CN 200410021796 CN200410021796 CN 200410021796 CN 200410021796 A CN200410021796 A CN 200410021796A CN 1654451 A CN1654451 A CN 1654451A
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Abstract
The present invention relates to the method of synthesizing dihydric alcohol monoether carboxylate, and is especially synthesis of glycol monoether carboxylate or propylene glycol monoether carboxylate. Specifically, cyclic carbonate and carboxylate react under the presence of catalyst, and the product is rectified and separated to produce dihydric alcohol monoether carboxylate. The said process is simple and efficient.
Description
The present invention relates to the synthetic method of dialcohol monomethyl ether carboxylicesters.
Existing ehter bond has carbonyl again in the dialcohol monomethyl ether carboxylicesters molecule, also has different alkyl, promptly in a part, have nonpolar part and polarity part simultaneously, therefore its both solubilized organic molecule, synthetic and natural macromolecular compound, can dissolve each other with water or water-soluble cpds to some extent again, has purposes very widely, in particular for top grade paint aspect.
Synthetic method about the dialcohol monomethyl ether carboxylicesters has: dialcohol monomethyl ether and carboxylic acid direct esterification method, be the ester-interchange method etc. of ester-interchange method, dialcohol monomethyl ether and carboxylicesters of two-step approach, oxirane and the carboxylicesters of raw material with oxirane, pure and mild acid.
About dialcohol monomethyl ether and carboxylic acid direct esterification method, GB 2303132, CN 1243040, CN 1100970, CN 1097654, CN 1097651, CN 1180589, CN 1243036 etc. report with tosic acid, layer molecule sieve, zirconates, cerium salt and Zirconium oxide, ion exchange resin, Ti
2+/ SiO
2, Ti
2+/ HZSM-5 etc. are catalyst for esterification reaction catalysis ethylene glycol mono-ether and acetate synthesizing glycol monoether acetic ester.The advantage of this synthesis method is the technology comparative maturity, and the quality of product is good.But because this reaction is reversible balanced reaction, move to improve the yield of purpose product dialcohol monomethyl ether carboxylicesters to the product direction, need to adopt a kind of raw material greatly excessive or in reaction, one of product is shifted out reactive system for promoting balance.The general method that adopts is to add entrainer or entrainment agent shifts out reaction system with the water that generates in reaction system.Band water entrainer commonly used has toluene, ethylbenzene, hexanaphthene, octane etc.Wherein the toxicity of toluene is higher, and it is restricted in industrial use; Though the toxicity of octane is low, but not to be well suited for body series, because it has also taken a large amount of reactant ethylene glycol mono-ether and acetate out of in azeotropic band water, and in its carry-over, the weight percent of ethylene glycol mono-ether up to 20%, the weight percent of acetate is up to 30%, causes by the flash point of the water of Organic pollutants very lowly like this, operates dangerous, increased the expense of operation, the loss of a large amount of raw materials causes the increase of product cost equally; Also there are same problem in ethylbenzene, hexanaphthene etc.Replace above-mentioned entrainer can solve the shortcoming that reactant is taken out of though patent GB2303132, GB2312673, US5659073 report adopt butylacetate, dibutyl ether or propyl carbinol to wait, the recovery of entrainer is still relatively more difficult.In addition, the purpose product had both dissolved each other with water and had separated, and dissolved each other with unreacted raw material again, had formed a series of azeotrope, and product separation is difficulty very, refining expense height.
About oxirane, pure and mild acid is the two-step approach of raw material, and it is that raw material goes on foot synthesizing glycol monoether carboxylicesters through etherificate and esterification two under the effect of catalyzer that reports such as US 3681204, DE 333710, the clear 56-20544 of TOHKEMY, GB2063261 adopt oxyethane, pure and mild acid.This method not only has comprehensive shortcoming of above-mentioned direct esterification method, but also the shortcomings such as potentially dangerous that have seriously corroded, environmental pollution is serious and blast is arranged.
Ester-interchange method about dialcohol monomethyl ether and carboxylicesters, reports such as US 3700726, the clear 43-16966 of TOHKEMY are catalytic material synthesizing glycol ether acetic ester with ethylene glycol ethyl ether and ethyl acetate, though this method has successfully been avoided in the above-mentioned direct esterification method because the azeotropic that generation brought of water, and owing to adding the azeotropic problem that entrainer brings, but produced an other azeotropic problem, it is the azeotropic of by product ethanol and reactant ethyl acetate, and reaction is balanced reaction, be to guarantee that the yield of product must use a large amount of excessive ethyl acetate.
Ester-interchange method about oxirane and carboxylicesters, US 4022808, DE 3008174, the clear 56-36431 of TOHKEMY etc. is reported in Al, Ti, Fe, Zn or Sn basic catalyst, dosing nitrogenous organic base helps under the catalysis of catalytic zirconium-containing compound, oxyethane and carboxylicesters obtain the purpose product through the direct transesterify of pressurizeing, the advantage of this method is that reaction mixture is simple, reaction process neither generates water, do not generate alcohol yet, post catalyst reaction is removed easily, product separation and refining also than being easier to control, but owing to use oxyethane to be raw material in the reaction, the active strong polymerization easily of oxyethane, cause having in the product by products such as glycol ether and triglycol to generate, also have the danger of poisoning and exploding simultaneously.
Just as described above, exist reactant in the method for synthesis of dibasic alcohol monoether carboxylicesters in the past and have toxicity, corrodibility or azeotrope and be difficult to isolating problem.Therefore the object of the present invention is to provide and do not use highly corrosive, have toxic material and be raw material, but and with simple tripping device and the program novel method with regard to synthesis of dibasic alcohol monoether carboxylicesters.
Technical conceive of the present invention is such:
The present invention is a raw material with cyclic carbonate and carboxylicesters, carries out transesterify and prepare the dialcohol monomethyl ether carboxylicesters in the presence of catalyzer.Because cyclic carbonate and the carboxylicesters selected for use are low toxicity or nontoxic compound, in the time of if can using non-corrosive catalyzer simultaneously, just can realize that the green of dialcohol monomethyl ether carboxylicesters is synthesized.Reaction by rectification process liquid, obtains required dialcohol monomethyl ether carboxylicesters after finishing, and unreacted raw material and catalyst recirculation are used.
Realize the technical scheme of the object of the invention:
The present invention is a raw material with cyclic carbonate and carboxylicesters, carries out transesterify and prepare the dialcohol monomethyl ether carboxylicesters in the presence of catalyzer, and temperature of reaction generally can be selected in 50～350 ℃ wide region, but preferably selects in 100～250 ℃ of scopes; Reaction times is then different because of the difference of other condition, is generally several minutes to tens hour, preferably 30 minutes to 15 hours scope; Cyclic carbonate can be determined arbitrarily with the mol ratio of carboxylicesters, but be good with 1: 5～5: 1 usually; Though reaction can be carried out under normal pressure or pressurized conditions, under surpassing the temperature of raw material boiling point during reaction to be pressurised into, the pressure of reaction generally can be selected in the scope of 0.1～15MPa, but with in 0.1～10MPa scope for well; Catalyst consumption adopts general catalyst consumption to get final product, and without particular limitation, but as if the angle from economy, catalyst consumption can be selected in the scope of 0.01～10% (weight percent is in the weight of raw mix).
After reaction finishes, adopt lock out operation commonly used just can from the reaction solution that the utilization aforesaid method obtains, separate to purify and obtain desired dialcohol monomethyl ether carboxylicesters.
About method of the present invention, be illustrated with following example, but the present invention never is subjected to the restriction of these examples.
[example 1] is with NSC 11801 1.63g (0.01852mol), phenylacetate 5ml (0.03706mol) and triphenylphosphine 0.1g (0.3817mmol, 1.506wt%) join in the 50ml four-hole boiling flask that thermometer, reflux condensing tube, agitator and nitrogen ingress pipe are housed, in the presence of nitrogen, in 190 ℃ of reactions 10 hours.Reacted reaction solution is analyzed with gas chromatograph, the yield 89.35% of ethylene glycol phenyl ether acetic ester.
[example 2] is with NSC 11801 1.63g (0.01852mol), phenylacetate 5ml (0.03706mol) and La
2O
30.1g (0.3069mmol 1.506wt%) joins in the 50ml four-hole boiling flask that thermometer, reflux condensing tube, agitator and nitrogen ingress pipe are housed, in the presence of nitrogen, in 190 ℃ of reactions 10 hours.Reacted reaction solution is analyzed with gas chromatograph, the yield 60.13% of ethylene glycol phenyl ether acetic ester.
[example 3] is with NSC 11801 3.26g (0.03706mol), phenylacetate 10ml (0.07412mol) and (C
12H
25) N (CH
3)
3(0.7579mmol 0.1506wt%) joins in the 50ml four-hole boiling flask that thermometer, reflux condensing tube, agitator and nitrogen ingress pipe are housed Cl 0.2g, in the presence of nitrogen, in 190 ℃ of reactions 10 hours.Reacted reaction solution is analyzed with gas chromatograph, the yield 89.34% of ethylene glycol phenyl ether acetic ester.
Claims (8)
1. in the presence of catalyzer, the cyclic carbonate shown in the general formula 1 is with the method for the dialcohol monomethyl ether carboxylicesters shown in the synthetic general formula 6 of the reaction of the carboxylicesters shown in the general formula 2,3,4,5.
[chemical structural formula]
General formula 1:
General formula 2:
R
2-COO-R
3
General formula 3:
Ar
1-COO-R
4
General formula 4:
R
5-COO-Ar
2
General formula 5:
Ar
3-COO-Ar
4
General formula 6:
R
6-OR
1OOC-R
7
In the formula: R
1Represent C
2～C
18Alkyl or the C that replaces by alkoxyl group, aryloxy, halogen etc.
1～C
18Alkyl; R
2, R
4Represent C
1～C
18Alkyl or the C that replaces by alkoxyl group, aryloxy, halogen etc.
1～C
18Alkyl; R
3, R
5Represent hydrogen atom, C
1～C
18Alkyl or the C that replaces by alkoxyl group, aryloxy, halogen etc.
1～C
18Alkyl; Ar
1～Ar
4Represent unsubstituted or the C that replaces through 1～5 alkyl, alkoxyl group, aryl, aryloxy, halogen, nitro, sulfonic group
6～C
10Aryl, C
6～C
10Heterocycle; R
6Represent C
1～C
18Alkyl, the C that replaces by alkoxyl group, aryloxy, halogen etc.
1～C
18C alkyl, unsubstituted or that replace through 1～5 alkyl, alkoxyl group, aryl, aryloxy, halogen, nitro, sulfonic group
6～C
10Aryl, C
6～C
10Heterocycle; R
7Represent hydrogen atom, C
1～C
18Alkyl, the C that replaces by alkoxyl group, aryloxy, halogen etc.
1～C
18C alkyl, unsubstituted or that replace through 1～5 alkyl, alkoxyl group, aryl, aryloxy, halogen, nitro, sulfonic group
6～C
10Aryl, C
6～C
10Heterocycle.
2. the method for claim 1, it is characterized in that general formula 1 expression cyclic carbonate, NSC 11801, propylene carbonate, 4-ethyl-1 specifically, 3-dioxane penta-2-ketone, 4,5-dimethyl-1,3-dioxane penta-2-ketone, 4,5-diethyl-1,3-dioxane penta-2-ketone etc., but in these compounds, be specially adapted to NSC 11801, propylene carbonate.
3. the method for claim 1, it is characterized in that general formula 2 expression aliphatic carboxylic acid alkyl esters, comprise methyl-formiate, ethyl formate, propyl formate, isopropyl formate, n-buty formate, tetryl formate, sec.-butyl formate, t-butyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, sec-butyl acetate, tert.-butyl acetate, acetate 2-ethoxy ethyl ester, acetate 2-butoxy ethyl ester, methyl propionate, ethyl propionate, propyl propionate, butyl propionate etc.As consider the source of raw material and the practicality of product, be good with methyl acetate, ethyl acetate, butylacetate, acetate 2-ethoxy ethyl ester, acetate 2-butoxy ethyl ester.
4. the method for claim 1, it is characterized in that the aromatic carboxylic acid alkyl ester shown in the general formula 3, comprise methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, the positive butyl ester of phenylformic acid, isobutyl benzoate, the secondary butyl ester of phenylformic acid, t-butyl perbenzoate, o, m or p-tolyl acid ethyl ester, 2,4-mesitylenic acid ethyl ester, 3,5-mesitylenic acid ethyl ester, 4-phenoxy benzoic acid ethyl ester, Phenylacetic acid ethylester etc.
5. the method for claim 1, it is characterized in that the aliphatic carboxylic acid aryl ester shown in the general formula 4, comprise phenyl formate, phenylacetate, phenylpropionate, jasmal, propionic acid 4-methyl phenyl ester, butyric acid 4-chlorobenzene ester, caproic acid phenyl ester, benzyl hexanoate, acetate 4-methyl phenyl ester etc.
6. the method for claim 1, it is characterized in that the aromatic carboxylic acid aryl ester shown in the general formula 5, comprise phenol benzoate, peruscabin, phenylformic acid 4-methyl phenyl ester, phenylformic acid 4-chlorobenzene ester, phenylformic acid 4-methoxyl group phenyl ester, phenylformic acid 4-phenoxy group phenyl ester, phenylformic acid 2,4-dimethyl phenyl ester, phenylformic acid 3,5-dimethyl phenyl ester, o, m or p-tolyl acid phenyl ester, 2,4-mesitylenic acid phenyl ester, 3,5-mesitylenic acid phenyl ester, 4-phenoxy benzoic acid phenyl ester, toluylic acid phenyl ester etc.
7. the method for claim 1 is characterized in that above-mentioned raw material is imported reactor, makes it reaction in the presence of catalyzer.
8. method as claimed in claim 7 is characterized in that used catalyzer can be the compound of metallic compound or nitrogenous or phosphorus.Metallic compound can be oxide compound, alkoxide, oxyhydroxide, hydrochloride, acetate, carbonate and organometallic compound etc., specifically can list La
2O
3, CeO
2, ZnO, MgO, CaO, PbO, Pb
3O
4, TiO
2, Nb
2O
5, MnO
2, Fe
2O
3, ZrO
2, CoO, NiO
2, CuO, SnO, Al
2O
3, FeO, NaOH, KOH, Ca (OH)
2, Na
2CO
3, K
2CO
3, Zn (OAc)
2, Pb (OAc)
2, Co (OAc)
2, Ni (OAc)
2, AlX
3, BX
3, FeX
3, SnX
4, SnOX
2, TiX
4, ZnX
2(X represents halogen, alkyl, aryl, alkoxyl group, aryloxy) etc.Wherein optimal catalyzer is La
2O
3, CeO
2And SnX
4, SnOX
2, TiX
4, ZnX
2, AlX
3Shown compound.Compound nitrogenous or phosphorus has following general formula, wherein R
8～R
25Represent C
1～C
16Alkyl, C
6～C
10Aryl, C
7～C
22Aralkyl, C
6～C
10Aryloxy and C
6～C
10Heterocycle, Y
1～Y
4Represent halogen atom, hydroxyl.Object lesson can list Et
3N, Et
2NH, EtNH
2, Et
4N
+Cl
-, Et
4N
+Br
-, Et
4N
+I
-, Et
4N
+OH
-, (C
12H
25) N (CH
3)
3Cl, Me
4N
+Cl
-, Me
4N
+Br
-, Me
4N
+I
-, Me
4N
+OH
-, Me
3N, Me
2NH, MeNH
2, (HOCH
2CH
2)
3N, PPh
3, PMe
3, PEt
3, PPhMe
2, PEtPh (n-Pr), PBu
3, (p-ClPh)
3P, PPh
2Me, Ph
3PO, (p-ClPh)
3PO, PhMe
2PO, Bu
3PO, Ph
2MePO, EtPh (n-Pr) PO, Ph
3PCl
2, Ph
3PBr
2, Ph
3PI
2, Ph
4P
+Cl
-, Ph
4P
+Br
-, Ph
4P
+I
-, Et
4P
+Br, Et
4P
+I
-, Me
4P
+Br
-, Me
4P
+I
-, Ph
4P
+AcO
-, Ph
4P
+PhCOO
-, Ph
4P
+BF
4 -, (p-ClPh)
4P
+BF
4 -
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410021796 CN1654451A (en) | 2004-02-12 | 2004-02-12 | Process for synthesis of diol monoether carboxylate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410021796 CN1654451A (en) | 2004-02-12 | 2004-02-12 | Process for synthesis of diol monoether carboxylate |
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|---|---|
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Family
ID=34892249
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008247873A (en) * | 2007-03-30 | 2008-10-16 | Univ Nagoya | Complex, catalyst for synthesizing ester, and method for producing the ester |
-
2004
- 2004-02-12 CN CN 200410021796 patent/CN1654451A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008247873A (en) * | 2007-03-30 | 2008-10-16 | Univ Nagoya | Complex, catalyst for synthesizing ester, and method for producing the ester |
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