CN104117350A - Magnesium-aluminum solid catalyst for synthesizing ethoxyethyl acrylate through one step - Google Patents
Magnesium-aluminum solid catalyst for synthesizing ethoxyethyl acrylate through one step Download PDFInfo
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- CN104117350A CN104117350A CN201410358545.XA CN201410358545A CN104117350A CN 104117350 A CN104117350 A CN 104117350A CN 201410358545 A CN201410358545 A CN 201410358545A CN 104117350 A CN104117350 A CN 104117350A
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Abstract
The invention relates to a magnesium-aluminum solid catalyst for synthesizing ethoxyethyl acrylate through one step. The magnesium-aluminum solid catalyst is used for catalyzing one-step reaction of ethylene oxide/propylene oxide and double-bond-containing carboxylate ester so as to synthesize unsaturated alkoxyl alcohol ether ester. The magnesium-aluminum solid catalyst is characterized in that an aluminum salt and a magnesium salt are prepared into a mixed metal salt solution according to certain proportion, a coprecipitation method is adopted to obtain a precipitate, the precipitate is aged for a certain time at certain temperature, the precipitate is filtered out, soluble salt ions attached on the precipitate are washed by deionized water, then the precipitate is placed in a constant-temperature drying oven to be dried until constant weight is achieved, and then is placed in a muffle furnace to be roasted at high temperature to obtain the catalyst. The magnesium-aluminum solid catalyst has the advantages that the magnesium-aluminum composite solid catalyst has acid-base active sites, can catalyze the one-step oxyalkylation reaction of the double-bond-containing carboxylate ester and alkyleneoxide, and has the characteristics of easiness in separation, environmental friendliness and the like.
Description
Technical field
The present invention relates to a kind of magnalium solid catalyst for one-step synthesis acrylic acid ethoxy ethyl ester, specifically relate to a kind of magnalium solid catalyst with soda acid double activated position, and for catalysis epoxy second (third) alkane and the synthetic unsaturated alkoxyl alcohol ether-ether of double bond containing carboxylate single step reaction.Belong to catalyst preparation, technology of fine chemicals.
Background technology
In the molecular structure of acrylic acid alcohol ether Ester, contain all kinds of functional groups such as carbon-carbon double bond, ester bond, ehter bond, carbonyl, alkyl, and have the characteristics such as miscible, copolymerization, its copolymer product has the performances such as heat resistance, resistance to water.Its special construction and premium properties make acrylic acid alcohol ether-ether be widely used in the fields such as coating, resin, rubber.
The traditional handicraft of acrylic acid synthesizing alcohol ether-ether is that acrylic acid and correspondent alcohol synthesize by esterification process, and the main problem existing is product postprocessing difficulty, with aqua, environment is had to certain harm etc.Adopt esters of acrylic acid and epoxyalkane acrylic acid synthesizing alcohol ether Ester can avoid the problem in above-mentioned technique, but the main problem existing of this type of reaction is the selection of catalyst, is generally used for the homogeneous catalyst of alkoxylation and is not suitable for reacting of esters of acrylic acid and epoxyalkane.CN1315225A discloses a kind of preparation method of regular pore structure Al-Mg composite metal oxide catalyst, for the alkoxylation of alcohol ether, this kind of regular pore structure Al-Mg composite metal oxide catalyst only can be for the alkoxylation of saturated alcohol ether; CN100391597C discloses a kind of catalyst of being prepared by composite magnesium aluminate active component and activated clay, and catalyst is annular, and for the alkoxylation of fatty acid ester, and this kind of catalyst is also for the alkoxylation of saturated fatty acid ester.
Summary of the invention
The object of the present invention is to provide a kind of magnalium solid catalyst for one-step synthesis acrylic acid ethoxy ethyl ester.Magnalium solid catalyst has soda acid double activated position, for irregular pore structure, mesopore (aperture is at 2.5 ~ 25nm) structure is many, selectively strong, can the catalysis band two carboxylates of key and a step alkoxylation of epoxyalkane, have the features such as easily separated, environmental protection.
The object of the present invention is achieved like this: a kind of magnalium solid catalyst for one-step synthesis acrylic acid ethoxy ethyl ester, take mol ratio as n (Al
3+)/n (Mg
2+the aluminium salt of)=0.05 ~ 3, magnesium salts are mixed with mixed salt solution, by coprecipitation method, prepare, sediment is aging 0.5 ~ 36h under uniform temperature, filter out sediment, with deionized water washing, remove the Soluble salt ions adhering on sediment 3 ~ 4 times, be placed in the thermostatic drying chamber inner drying of 40 ~ 150 ℃ until constant weight, and be placed in Muffle furnace high-temperature roasting 2 ~ 10h at 200 ~ 900 ℃.
As a step more of the present invention is limited, catalyst adopts coprecipitation to prepare.Precipitating reagent is two kinds in potassium hydroxide, potash, ammoniacal liquor, ammonium carbonate, urea, oxalic acid;
As a step more of the present invention is limited, by add the slaines such as zirconates, cerium salt, zinc salt, calcium salt, pink salt, strontium salt in catalyst preparation process, to catalyst, carry out metal-modified; By the catalyst preparing is carried out to KOH, NaOH, HCl, HNO
3dipping Deng solution carries out soda acid modification to catalyst.
As a step more of the present invention is limited, the molar ratio that the magnalium catalyst preparation process that adopts coprecipitation to prepare is magnalium is n (Al
3+)/n (Mg
2+)=0.1 ~ 1, ageing time is 2 ~ 10h, and baking temperature is 100 ~ 130 ℃, and high-temperature roasting temperature is 300 ~ 600 ℃, and the high-temperature roasting time is 4 ~ 8h.
As a step more of the present invention is limited, take potassium hydroxide, potash mixed solution is precipitating reagent, and magnalium mol ratio is n (Al
3+)/n (Mg
2+)=0.8, ageing time is 6h, and baking temperature is 105 ℃, and high-temperature roasting temperature is 500 ℃, and the high-temperature roasting time is 5h.
A kind of method of using magnalium solid catalyst to prepare acrylic acid ethoxy ethyl ester, use magnalium solid catalyst, take ethyl acrylate, oxirane is raw material, and acetylacetone,2,4-pentanedione, phenthazine are composite polymerzation inhibitor, by autoclave reactor acrylic acid synthesizing ethoxy ethyl ester.
A purposes for magnalium solid catalyst, described catalyst is for catalysis epoxy second (third) alkane and the synthetic unsaturated alkoxyl alcohol ether-ether of double bond containing carboxylate single step reaction.
Advantage of the present invention is: Mg-Al composite oxide solid catalyst has soda acid double activated position, for irregular pore structure, mesopore (aperture is at 2.5 ~ 25nm) structure is many, selective strong, can the catalysis band two carboxylates of key and a step alkoxylation of epoxyalkane, have the features such as easily separated, environmental protection.
The specific embodiment
By following instance, invention is described further, but does not therefore limit the present invention.
In embodiment, each content of material in product carries out quantitative analysis by gas chromatography.Adopt GC9790 type gas chromatograph, split sampling, is furnished with temperature programming parts, flame ionization ditector.Capillary chromatograph is SE-54 (methyl polysiloxane) type 30m * 0.32mm * 0.45 μ m.
The prepared catalyst of following examples is all for a step ethoxylation acrylic acid synthesizing ethoxy ethyl ester of ethyl acrylate, oxirane.
embodiment 1
15.1g ANN aluminium nitrate nonahydrate, 10.2g Magnesium dichloride hexahydrate are dissolved in 50g deionized water, 4.1g potassium hydroxide, 10.1g potash are dissolved in 50g deionized water, two kinds of solution are mixed, aging, dry, high-temperature roasting.N (Al in described catalyst
3+)/n (Mg
2+)=0.8 catalyst sintering temperature is 500 ℃, and described catalyst is for the ethoxylation of ethyl acrylate, and oxirane conversion ratio is 68.08%
comparative example 2
15.0g ANN aluminium nitrate nonahydrate, 10.2g Magnesium dichloride hexahydrate, 14.1g citric acid are dissolved in 14.7g deionized water, by sol-gal process, prepare magnalium solid catalyst.Described catalyst is for the ethoxylation of ethyl acrylate, the basic non-activity of catalyst.
embodiment 3
18.2g Magnesium dichloride hexahydrate, 26.8g ANN aluminium nitrate nonahydrate, 2.3g eight hydration zirconium oxychlorides are dissolved in 77.8g deionized water, 11.8g potassium hydroxide, 14.6g potash are dissolved in 100g deionized water, two kinds of solution are mixed, aging, dry, high-temperature roasting.Described catalyst is for the ethoxylation of ethyl acrylate, and oxirane conversion ratio is 17.24%
embodiment 4
15.1g ANN aluminium nitrate nonahydrate, 10.2g Magnesium dichloride hexahydrate are dissolved in 50g deionized water, 4.1g potassium hydroxide, 10.1g potash are dissolved in 50g deionized water, two kinds of solution are mixed, aging, dry, high-temperature roasting, by KOH ethanolic solution dipping modification for the catalyst preparing, and dries to constant weight.Described catalyst is for the ethoxylation of ethyl acrylate, and oxirane conversion ratio is 61.30%.
embodiment 5
25.3g Aluminium chloride hexahydrate, 30.5g Magnesium dichloride hexahydrate are dissolved in 135g deionized water, 11.5g potassium hydroxide, 28.3g potash are dissolved in 135g deionized water, two kinds of solution are mixed, aging, dry, high-temperature roasting.N (Al in described catalyst
3+)/n (Mg
2+)=0.7, for the ethoxylation of ethyl acrylate, oxirane conversion ratio is 55.25%.
embodiment 6
32.6g Aluminium chloride hexahydrate, 30.5g Magnesium dichloride hexahydrate are dissolved in 155g deionized water, 13.2g potassium hydroxide, 32.5g potash are dissolved in 155g deionized water, two kinds of solution are mixed, aging, dry, high-temperature roasting.N (Al in described catalyst
3+)/n (Mg
2+)=0.9, for the ethoxylation of ethyl acrylate, oxirane conversion ratio is 50.46%.
embodiment 7
29.0g Aluminium chloride hexahydrate, 24.4g Magnesium dichloride hexahydrate are dissolved in 130g deionized water, 11.2g potassium hydroxide, 27.6g potash are dissolved in 130g deionized water, two kinds of solution are mixed, aging, dry, high-temperature roasting.N (Al in described catalyst
3+)/n (Mg
2+)=1.0, for the ethoxylation of ethyl acrylate, oxirane conversion ratio is 45.85%.
embodiment 8
29.0g Aluminium chloride hexahydrate, 30.5g Magnesium dichloride hexahydrate are dissolved in 150g deionized water, 12.6g potassium hydroxide, 31.1g potash are dissolved in 150g deionized water, two kinds of solution are mixed, aging, dry, high-temperature roasting.The high-temperature roasting temperature of described catalyst is 400 ℃, and for the ethoxylation of ethyl acrylate, oxirane conversion ratio is 60.01%.
embodiment 9
29.0g Aluminium chloride hexahydrate, 30.5g Magnesium dichloride hexahydrate are dissolved in 150g deionized water, 12.6g potassium hydroxide, 31.1g potash are dissolved in 150g deionized water, two kinds of solution are mixed, aging, dry, high-temperature roasting.The high-temperature roasting temperature of described catalyst is 600 ℃, and for the ethoxylation of ethyl acrylate, oxirane conversion ratio is 50.74%.
Claims (8)
1. for a magnalium solid catalyst for one-step synthesis acrylic acid ethoxy ethyl ester, it is characterized in that: take molar ratio as n (Al
3+)/n (Mg
2+the aluminium salt of)=0.05 ~ 3, magnesium salts are mixed with mixed salt solution, by coprecipitation method, prepare, sediment is aging 0.5 ~ 36h under uniform temperature, filter out sediment, with deionized water washing, remove the Soluble salt ions adhering on sediment, be placed in the thermostatic drying chamber inner drying of 40 ~ 150 ℃ until constant weight, and be placed in Muffle furnace high-temperature roasting 2 ~ 10h at 200 ~ 900 ℃.
2. according to a kind of magnalium solid catalyst for one-step synthesis acrylic acid ethoxy ethyl ester described in claims 1, it is characterized in that: when prepared by coprecipitation, the precipitating reagent of use is one or more in potassium hydroxide, potash, ammoniacal liquor, ammonium carbonate, urea, oxalic acid.
3. according to a kind of magnalium solid catalyst for one-step synthesis acrylic acid ethoxy ethyl ester described in claims 1 or 2, it is characterized in that: the molar ratio of magnalium is n (Al
3+)/n (Mg
2+)=0.1 ~ 1, ageing time is 2 ~ 10h, and baking temperature is 100 ~ 130 ℃, and high-temperature roasting temperature is 300 ~ 600 ℃, and the high-temperature roasting time is 4 ~ 8h.
4. according to a kind of magnalium solid catalyst for one-step synthesis acrylic acid ethoxy ethyl ester described in claims 1 or 2, it is characterized in that: in catalyst preparation process, add zirconates, cerium salt, zinc salt, calcium salt, pink salt or strontium salt pair catalyst and carry out modification.
5. according to a kind of magnalium solid catalyst for one-step synthesis acrylic acid ethoxy ethyl ester described in claims 1 or 2, it is characterized in that: by the catalyst preparing is carried out to KOH, NaOH, HCl or HNO
3the dipping of solution carries out modification to catalyst.
6. according to a kind of magnalium solid catalyst for one-step synthesis acrylic acid ethoxy ethyl ester described in claims 3, it is characterized in that: take potassium hydroxide, potash mixed solution is precipitating reagent, and magnalium mol ratio is n (Al
3+)/n (Mg
2+)=0.8, ageing time is 6h, and baking temperature is 105 ℃, and high-temperature roasting temperature is 500 ℃, and the high-temperature roasting time is 5h.
7. a method of using magnalium solid catalyst to prepare acrylic acid ethoxy ethyl ester, it is characterized in that: right to use requires the 1 magnalium solid catalyst making, take ethyl acrylate, oxirane is raw material, acetylacetone,2,4-pentanedione, phenthazine are composite polymerzation inhibitor, by autoclave reactor acrylic acid synthesizing ethoxy ethyl ester.
8. a purposes for magnalium solid catalyst, is characterized in that: the catalyst of claim 1 preparation is synthesized to unsaturated alkoxyl alcohol ether-ether for catalysis epoxy second (third) alkane and double bond containing carboxylate single step reaction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152931A (en) * | 2015-09-14 | 2015-12-16 | 常州大学 | One-step catalytic synthesis method for 2-methoxyethanol benzoate |
| CN106349072A (en) * | 2016-08-27 | 2017-01-25 | 安徽金邦医药化工有限公司 | Method for compounding ethoxy ethyl acrylate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706546A (en) * | 2005-04-12 | 2005-12-14 | 江南大学 | Al-Mg catalyst and catalytic synthesis process of alkoxyl carboxylate ether |
| CN102886227A (en) * | 2012-07-25 | 2013-01-23 | 中南大学 | Application of ethoxy ethyl acrylate polymer and preparation method thereof |
| CN103755564A (en) * | 2013-12-19 | 2014-04-30 | 抚顺安信化学有限公司 | Preparation method for ethoxyethyl methacrylate |
-
2014
- 2014-07-26 CN CN201410358545.XA patent/CN104117350A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706546A (en) * | 2005-04-12 | 2005-12-14 | 江南大学 | Al-Mg catalyst and catalytic synthesis process of alkoxyl carboxylate ether |
| CN102886227A (en) * | 2012-07-25 | 2013-01-23 | 中南大学 | Application of ethoxy ethyl acrylate polymer and preparation method thereof |
| CN103755564A (en) * | 2013-12-19 | 2014-04-30 | 抚顺安信化学有限公司 | Preparation method for ethoxyethyl methacrylate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152931A (en) * | 2015-09-14 | 2015-12-16 | 常州大学 | One-step catalytic synthesis method for 2-methoxyethanol benzoate |
| CN106349072A (en) * | 2016-08-27 | 2017-01-25 | 安徽金邦医药化工有限公司 | Method for compounding ethoxy ethyl acrylate |
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Application publication date: 20141029 |