CN102408315A - Synthesis method of anacardol and butyl ether composition - Google Patents
Synthesis method of anacardol and butyl ether composition Download PDFInfo
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- CN102408315A CN102408315A CN2011102745782A CN201110274578A CN102408315A CN 102408315 A CN102408315 A CN 102408315A CN 2011102745782 A CN2011102745782 A CN 2011102745782A CN 201110274578 A CN201110274578 A CN 201110274578A CN 102408315 A CN102408315 A CN 102408315A
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- cardanol
- butyl ether
- anacardol
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Abstract
The invention discloses a synthesis method of an anacardol and butyl ether composition. The synthesis method comprises the following steps of: allowing anacardol to react with chloro-n-butane in the presence of a base catalyst and in the absence of oxygen; depressurizing and distilling after the reaction; and finally filtering out the generated salt to obtain the anacardol and butyl ether composition product, wherein, the base catalyst is alkali metal carbonate or alkali metal hydroxide. The method for synthesizing the anacardol with butyl ether is simple and has the advantage of higher yield; and meanwhile no water is added and no waste water is generated during the reaction process. As phenolic hydroxyl of the anacardol is replaced by alkoxy, the obtained product has the advantage of better color stability, and meanwhile corrosion of the anacardol on skin is greatly reduced. Therefore, the product can be used for preparing an epoxy hardener with good color stability and can be also utilized as a modifier in coating, an adhesive, rubber, plastics, an elastomer, a composite material and printing ink.
Description
Technical field
The present invention relates to a kind of compound method of ether, relate in particular to the compound method of one type of cardanol butyl ether.
Background technology
Cardanol is the natural biological phenol that there is the monohydroxy phenols structure of the long carbochain of one 15 carbon a kind of position, the cardanol nontoxicity, and non-corrosiveness is different from the high corrosion of oil phenol, high toxicity.Relatively more friendly to environment, human body.Its structure is following:
Wherein n is 0,1 or 2.
Cardanol is of many uses, can be used for resol, epoxy curing agent, tensio-active agent and emulsion splitter etc.But the phenolic hydroxyl group of cardanol is oxidised with air to quinone extremely easily, and color and luster is deepened.English Patent GB2262525 discloses and with oxyethane cardanol has been carried out ethoxylation and make the cardanol hydroxyethyl ether, is used to prepare tensio-active agent.
Chinese patent CN102030725 discloses the compound method of cardanol epoxy propyl ether, uses a kind of crown ether as phase-transfer catalyst, in the presence of sodium hydroxide solution, has synthesized cardanol epoxy propyl ether, overall yield 88%.Be used to prepare the cardanol polyol.
U.S. Cardolite Corp. discloses at U.S. Pat 6299054 and Chinese patent CN1332712 respectively and a kind ofly in the presence of the organic or inorganic catalyzer, with cyclic organic carbonates cardanol has been carried out the method for hydroxyalkylation and a kind of novel compsns of material obtained by this method.The unique molecular structure of cardanol makes can use multiple organic or inorganic basic catalyst in the hydroxyalkylation reaction, comprise triethylamine, imidazoles, and sodium hydroxide and yellow soda ash, and do not form a large amount of undesirable by products.According to this invention, can obtain high yield and highly purified final product, monohydroxy alkyl cashew nut phenolic group ether.This product has light colour and its colour stability is to be improved through the hydroxyl that substitutes phenol with more stable hydroxy alkoxy base.
Summary of the invention
For the phenolic hydroxyl group that solves cardanol is oxidized to the defective of quinone easily, the invention provides a kind of compound method of cardanol butyl ether compsn, the phenolic hydroxyl group alkoxy of cardanol substitutes, and colour stability is fine, has high boiling point.
Technical scheme of the present invention is: a kind of compound method of cardanol butyl ether compsn; Cardanol and n-propylcarbinyl chloride are in the presence of basic catalyst; The oxygen free condition reaction, reaction finishes underpressure distillation, and the salt that removes by filter generation obtains product cardanol butyl ether compsn; Described basic catalyst is alkaline carbonate or alkali metal hydroxide, and the general formula of molecular structure of described product cardanol butyl ether compsn is following:
wherein n is 0,1 or 2.
Reaction is under 80～120 ℃ of temperature, to carry out, and the reaction times is 2～6 hours.
Described alkaline carbonate, alkali metal hydroxide are arbitrary in salt of wormwood, yellow soda ash, lime carbonate, sodium hydroxide, the Pottasium Hydroxide.
Described cardanol, n-propylcarbinyl chloride and basic catalyst feed intake according to mol ratio 1:1～1.5:0.5～1.
Can use solvent in the described reaction or not use solvent, then add polar aprotic solvent as using solvent.
Described polar aprotic solvent is arbitrary in N, N,N-DIMETHYLACETAMIDE, acetone, the butanone.
Beneficial effect:
This product can be as the substitute of cardanol in coating, sizing agent, rubber, plastics, elastomerics, matrix material and printing ink.Compare with cardanol, this product has following advantage:
1. the very slight color of cardanol butyl ether.Cardanol can only be used for primer base because color and luster is very dark.If but use the cardanol butyl ether, just can be used for the field that topcoating etc. is had relatively high expectations to color as substitute.
2. the colour stability of cardanol butyl ether is fine.Cardanol not only color is dark, and colour stability is poor, and color and luster can be deepened along with the prolongation of shelf lives gradually.But the color of cardanol butyl ether can shoal along with the prolongation of shelf lives gradually.
3. the cardanol butyl ether can not cause allergic.As everyone knows, contain phenolic hydroxyl group in the cardanol molecule, can cause allergic constitution crowd's contact dermatitis.And the cardanol butyl ether has replaced phenolic hydroxyl group fully with butoxy, has stopped allergen.
Description of drawings
Fig. 1 is the gas chromatogram of cardanol butyl ether compsn.
Fig. 2 is that n is 0 cardanol butyl ether mass spectrum.
Fig. 3 is that n is 1 cardanol butyl ether mass spectrum.
Fig. 4 is that n is 2 cardanol butyl ether mass spectrum.
Embodiment
Technical scheme of the present invention is not limited to following specific embodiment, also comprises the combination of various specific embodiments.
The four-hole boiling flask that nitrogen feeds mouth, TM, whisking appliance and reflux condensate device of being furnished with that the salt of wormwood (dragon chemical reagent instrument plant of Chengdu section) of 1 mole of fresh cardanol (Tengzhou, Shandong Ya Lante biomaterial ltd), 1 mole of n-propylcarbinyl chloride (Yixing Changjili Chemicals Co., Ltd.) and 0.5 mole is added 1000 milliliters of specifications mixes stirring, and nitrogen outlet is with fluid-tight in the funnel back-off water.Feed the air that nitrogen was got rid of in the flask in 10 minutes.Temperature rises to 80 ℃ and kept 6 hours.At 96 ℃ of water that generate except that dereaction with rotatory evaporator and the underpressure distillation of recirculated water vacuum pump of heating in water bath, except that desalting, obtain faint yellow transparent cardanol butyl ether 340g, productive rate 95.5% with the B suction filtration.
Embodiment 2
The four-hole boiling flask that nitrogen feeds mouth, TM, whisking appliance and reflux condensate device of being furnished with that the salt of wormwood (dragon chemical reagent instrument plant of Chengdu section) of 1 mole of fresh cardanol (Tengzhou, Shandong Ya Lante biomaterial ltd), 1.5 moles of n-propylcarbinyl chlorides (Yixing Changjili Chemicals Co., Ltd.) and 1 mole is added 1000 milliliters mixes stirring, and nitrogen outlet is with fluid-tight in the funnel back-off water.Feed the air that nitrogen was got rid of in the flask in 10 minutes.Temperature rises to 120 ℃ and kept 2 hours.At 96 ℃ of water of removing excessive n-butyl chloride and react generation with rotatory evaporator and the underpressure distillation of recirculated water vacuum pump of heating in water bath, except that desalting, obtain faint yellow transparent cardanol butyl ether 350g, productive rate 98.3% with the B suction filtration.
Embodiment 3
The four-hole boiling flask that nitrogen feeds mouth, TM, whisking appliance and reflux condensate device of being furnished with that the yellow soda ash (Dihua factory is won in Tianjin) of 1 mole of fresh cardanol (Tengzhou, Shandong Ya Lante biomaterial ltd), 1.5 moles of n-propylcarbinyl chlorides (Yixing Changjili Chemicals Co., Ltd.), 200 milliliters of Ns and 1 mole is added 1000 milliliters mixes stirring, and nitrogen outlet is with fluid-tight in the funnel back-off water.Feed the air that nitrogen was got rid of in the flask in 10 minutes.Temperature rises to 120 ℃ and kept 2 hours.At 96 ℃ of water of removing excessive n-butyl chloride and react generation with rotatory evaporator and the underpressure distillation of recirculated water vacuum pump of heating in water bath, except that desalting, obtain faint yellow transparent cardanol butyl ether 347g, productive rate 97.5% with the B suction filtration.
Embodiment 4
Embodiment 2 resulting cardanol butyl ethers are made into 10% acetone soln, do the gas chromatography-mass spectrography test.Gas chromatography mass spectrometry analysis test method: chromatographic column: HP-5MS capillary column, carrier gas are helium, and flow velocity is 1ml/min; Column temperature heating schedule: be warming up to 200 ℃ from 80 ℃ with 10 ℃/branch; Kept 10 minutes, and be warming up to 280 ℃ from 200 ℃ with 10 ℃/branch again, kept 10 minutes.Finish gasification temperature: 280 ℃.Detector: flame ionization detector.Gas chromatogram is seen accompanying drawing 1.RT is that 29.773 minutes a peak is that n is 1 cardanol butyl ether in the accompanying drawing 1, and its mass spectrum is seen accompanying drawing 2.RT is that 29.825 minutes b peak is that n is 2 cardanol butyl ether in the accompanying drawing 1, and its mass spectrum is seen accompanying drawing 3.RT is that 29.934 minutes c peak is that n is 0 cardanol butyl ether in the accompanying drawing 1, and its mass spectrum is seen accompanying drawing 4.
Embodiment 5
With fresh cardanol with according to each 50 gram of embodiment 3 resultant cardanol butyl ethers, respectively in two identical shaped and big or small glass jar of not adding a cover of impouring.Take out at regular intervals under the room temperature, measure colourity with iron cobalt tintometer.The result sees attached list 1, finds that institute of the present invention synthetic cardanol butyl ether compsn compares with fresh cardanol, has better color stability.At room temperature placed 120 days, fresh cardanol color is deepened gradually, and cardanol butyl ether compsn color shoals gradually.
Claims (6)
1. the compound method of a cardanol butyl ether compsn; It is characterized in that cardanol and n-propylcarbinyl chloride are in the presence of basic catalyst, oxygen free condition reacts; Reaction finishes underpressure distillation; The salt that removes by filter generation obtains product cardanol butyl ether compsn, and described basic catalyst is alkaline carbonate or alkali metal hydroxide, and the general formula of molecular structure of described product cardanol butyl ether compsn is following:
2. the compound method of cardanol butyl ether compsn as claimed in claim 1 is characterized in that, reaction is under 80～120 ℃ of temperature, to carry out, and the reaction times is 2～6 hours.
3. the compound method of cardanol butyl ether compsn as claimed in claim 1 is characterized in that, described alkaline carbonate, alkali metal hydroxide are arbitrary in salt of wormwood, yellow soda ash, lime carbonate, sodium hydroxide, the Pottasium Hydroxide.
4. the compound method of cardanol butyl ether compsn as claimed in claim 1 is characterized in that described cardanol, n-propylcarbinyl chloride and basic catalyst feed intake according to mol ratio 1:1～1.5:0.5～1.
5. the compound method of cardanol butyl ether compsn as claimed in claim 1 is characterized in that, adds polar aprotic solvent in the described reaction.
6. the compound method of cardanol butyl ether compsn as claimed in claim 1 is characterized in that, described polar aprotic solvent is arbitrary in N, N,N-DIMETHYLACETAMIDE, acetone, the butanone.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011102745782A CN102408315A (en) | 2011-09-16 | 2011-09-16 | Synthesis method of anacardol and butyl ether composition |
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| CN2011102745782A CN102408315A (en) | 2011-09-16 | 2011-09-16 | Synthesis method of anacardol and butyl ether composition |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188617A (en) * | 2016-07-19 | 2016-12-07 | 中国林业科学研究院林产化学工业研究所 | A kind of Fructus anacardii phenolic group ether type plasticizer and synthetic method thereof and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2476696A (en) * | 1945-12-05 | 1949-07-19 | Harvel Corp | Mineral oil composition |
| US2586191A (en) * | 1948-08-21 | 1952-02-19 | Harvel Corp | Salts of sulfonated ethers of hydrogenated cardanol as inhibitors for mineral hydrocarbon oils |
| CN101690877A (en) * | 2009-08-10 | 2010-04-07 | 北京东方晴空科技有限公司 | Pentadecyl phenol polyethenoxy ether strong biodegradable surfactant |
-
2011
- 2011-09-16 CN CN2011102745782A patent/CN102408315A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2476696A (en) * | 1945-12-05 | 1949-07-19 | Harvel Corp | Mineral oil composition |
| US2586191A (en) * | 1948-08-21 | 1952-02-19 | Harvel Corp | Salts of sulfonated ethers of hydrogenated cardanol as inhibitors for mineral hydrocarbon oils |
| CN101690877A (en) * | 2009-08-10 | 2010-04-07 | 北京东方晴空科技有限公司 | Pentadecyl phenol polyethenoxy ether strong biodegradable surfactant |
Non-Patent Citations (1)
| Title |
|---|
| 王钰: "间十五烷基酚的合成及热力学研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188617A (en) * | 2016-07-19 | 2016-12-07 | 中国林业科学研究院林产化学工业研究所 | A kind of Fructus anacardii phenolic group ether type plasticizer and synthetic method thereof and application |
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Application publication date: 20120411 |