CN104803950A - Method adopting ionic liquid catalyst to catalyze and synthesize epoxy fatty acid glycol ester - Google Patents
Method adopting ionic liquid catalyst to catalyze and synthesize epoxy fatty acid glycol ester Download PDFInfo
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- CN104803950A CN104803950A CN201510154278.9A CN201510154278A CN104803950A CN 104803950 A CN104803950 A CN 104803950A CN 201510154278 A CN201510154278 A CN 201510154278A CN 104803950 A CN104803950 A CN 104803950A
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- fatty acid
- catalyst
- epoxidized fatty
- catalyze
- ionic liquid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method by adopting an ionic liquid catalyst to catalyze and synthesize epoxy fatty acid glycol ester. The method is characterized by adopting a chloroaluminate ionic liquid as a catalyst, wherein the catalyst is constituted by aluminium chloride and organic nitrogenous compounds ( alkyl quaternary ammonium salt, alkyl quaternary phosphine salt and alkyl replaced imidazole salt). The method comprises the following steps: mixing epoxy fatty acid methylester, dibasic alcohol and the ionic liquid catalyst in proportion; pumping in N2; stirring, and heating to 145 DEG C; reacting at the constant temperature till no liquid is distilled off; stopping heating, and removing the catalyst to obtain the epoxy fatty acid glycol ester. In the synthesis process, the ionic liquid is used as the catalyst for reaction. is good in catalytic activity, easy to be separated from the product after the reaction, capable of being repeatedly used and low in corrosivity, and has excellent industrial application prospects; the epoxy fatty acid glycol ester synthesized by using the method improves the extraction resistance and volatility resistance performance of an epoxy fatty acid plasticizer in PVC products, and has good market popularization prospects.
Description
Technical field
The present invention relates to a kind of field of plastics additives, be specifically related to a kind of method utilizing ionic-liquid catalyst to catalyze and synthesize dihydric alcohol epoxidized fatty acid.
Background technology
Phthalate is the softening agent that purposes is the widest, consumption is maximum, but adjacent benzoic acid ester plasticizer product is volatile in the course of processing, and with having exudative and transport property after PVC finished product, heavy dose enters human body has carinogenicity constantly.Find adjacent benzoic ether class substitute that is nontoxic, environmental protection and become extremely urgent task.Plant oil based softening agent utilizes crude vegetal, carries out structural transformation by functional group reactions to glyceryl ester, to improve the consistency of crude vegetal and PVC.The achievement in research mainly epoxidation grease of current this respect.Owing to there is epoxide group in epoxidized fatty acid methyl esters, resistance to extraction performance and the volatility resistance fatty acid methyl ester that compares is good, but its resistance to extraction performance and volatility resistance can differ too many compared with DOP, therefore the epoxidized fatty acid methyl esters softening agent released in the market can only substitute DOP on a small quantity, and more low-grade plasticized PVC goods can only be applied to, also cannot apply in enormous quantities.
Ionic liquid is as a kind of novel environmentally friendly solvent and liquid acid alkaline catalysts, there is the advantage that other organic and inorganic solvents and traditional catalyst do not possess, transesterification reaction is carried out as catalyzer with ionic liquid, catalytic activity is good, easy same product separation after reaction, reusable, corrodibility is low.
This technique proposes a kind of new synthetic route: take ionic liquid as catalyzer, epoxidized fatty acid methyl esters obtains dihydric alcohol epoxidized fatty acid with diol reaction, increase the molecular weight of epoxidized fatty acid softening agent, improve the resistance to extraction of epoxidized fatty acid softening agent in PVC product, volatility resistance energy.
Summary of the invention
The object of the present invention is to provide a kind of method utilizing ionic-liquid catalyst to catalyze and synthesize dihydric alcohol epoxidized fatty acid, the dihydric alcohol epoxidized fatty acid of this method synthesis improves the resistance to extraction of epoxidized fatty acid softening agent in PVC product, volatility resistance energy.
Preparation method of the present invention comprises the steps:
(1) epoxy aliphatic acid methyl ester, dibasic alcohol and ionic-liquid catalyst proportioning are as follows:
Epoxy aliphatic acid methyl ester 100
Dibasic alcohol 15 ~ 30
Ionic-liquid catalyst 1 ~ 10
(2) epoxidized fatty acid methyl esters, dibasic alcohol and ionic-liquid catalyst are mixed in proportion, pass into N
2, stir and be warming up to 145 DEG C, isothermal reaction steams to not having liquid, stops heating, and removing catalyzer, obtains dihydric alcohol epoxidized fatty acid.
In this technique epoxy aliphatic acid methyl ester can be synthesized by following grease: the natural animal-plant greases such as rapeseed oil, Oleum Gossypii semen, soybean oil, Oleum Cocois, Jatropha oil, sunflower seed oil, lard, fish oil and trench wet goods reclaim waste oil, or above-mentioned several mixture.
Dibasic alcohol in this technique is ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, glycol ether, Diethylene Glycol, polyoxyethylene glycol, polypropylene glycol.
Ionic-liquid catalyst used in this technique is chloro-aluminate, is made up of aluminum chloride and nitrogen-containing organic compound, and this nitrogen-containing organic compound is alkyl quaternary ammonium salts, alkyl quaternary phosphonium salt, alkyl substituted pyridines salt, alkyl substituted imidazole salt.
Advantage of the present invention is:
(1) carry out transesterification reaction with ionic liquid as catalyzer, catalytic activity is good, and easy same product separation after reaction, reusable, corrodibility is low, meets the requirement of green chemical industry, has good industrial applications prospect.
(2) this technique improves the resistance to extraction of epoxidized fatty acid softening agent in PVC product, volatility resistance energy.
Embodiment
The following examples can make professional and technical personnel more understand the present invention, but do not limit the present invention in any form.
Embodiment 1
100 g epoxy aliphatic acid methyl esters, 20 g ethylene glycol, catalyzer [bmim] Cl-AlCl is added in reactor
3(bmim is 1-butyl-3-Methylimidazole) 3g, stir and be warming up to 145 DEG C, isothermal reaction steams to not having liquid, stops heating, and removing catalyzer, obtains epoxyfatty acid second binary alcohol esters.
Embodiment 2
100 g epoxy aliphatic acid methyl esters, 20 g ethylene glycol, catalyzer [bmim] Br-AlCl is added in reactor
3(bmim is 1-butyl-3-Methylimidazole) 3g, stir and be warming up to 145 DEG C, isothermal reaction steams to not having liquid, stops heating, and removing catalyzer, obtains epoxyfatty acid second binary alcohol esters.
Embodiment 3
100 g epoxy aliphatic acid methyl esters, 25 g propylene glycol, catalyzer [emim] Cl-AlCl is added in reactor
3(emim is 1-ethyl-3-methylimidazole) 4g, stir and be warming up to 145 DEG C, isothermal reaction steams to not having liquid, stops heating, and removing catalyzer, obtains epoxyfatty acid third binary alcohol esters.
Embodiment 4
100 g epoxy aliphatic acid methyl esters, 25 g propylene glycol, catalyzer (CH is added in reactor
3)
3(NHCl)-AlCl
34g, stir and be warming up to 145 DEG C, isothermal reaction steams to not having liquid, stops heating, and removing catalyzer, obtains epoxyfatty acid third binary alcohol esters.
Claims (4)
1. the method utilizing ionic-liquid catalyst to catalyze and synthesize dihydric alcohol epoxidized fatty acid, it is characterized in that by chloroaluminate ionic liquid be catalyzer, this catalyzer is made up of aluminum chloride and nitrogen-containing organic compound (nitrogen-containing organic compound be alkyl quaternary ammonium salts, alkyl quaternary phosphonium salt, alkyl substituted pyridines salt, alkyl substituted imidazole salt); In mass ratio by epoxidized fatty acid methyl esters 100 parts, dibasic alcohol 15 ~ 30 parts and ionic-liquid catalyst 1 ~ 10 part mixing, pass into N
2, stir and be warming up to 145 DEG C, isothermal reaction steams to not having liquid, stops heating, and removing catalyzer, obtains dihydric alcohol epoxidized fatty acid.
2. a kind of method utilizing ionic-liquid catalyst to catalyze and synthesize dihydric alcohol epoxidized fatty acid according to claim 1, is characterized in that the dibasic alcohol in the transesterification reaction of epoxidized fatty acid methyl esters and dibasic alcohol is ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, glycol ether, Diethylene Glycol, polyoxyethylene glycol, polypropylene glycol.
3. a kind of method utilizing ionic-liquid catalyst to catalyze and synthesize dihydric alcohol epoxidized fatty acid according to claim 1, it is characterized in that catalyzer used is chloroaluminate ionic liquid, be made up of aluminum chloride and nitrogen-containing organic compound (alkyl quaternary ammonium salts, alkyl quaternary phosphonium salt, alkyl substituted pyridines salt, alkyl substituted imidazole salt).
4. a kind of method utilizing ionic-liquid catalyst to catalyze and synthesize dihydric alcohol epoxidized fatty acid according to claim 1, it is characterized in that described epoxy aliphatic acid methyl ester can be synthesized by following grease: the natural animal-plant greases such as rapeseed oil, Oleum Gossypii semen, soybean oil, Oleum Cocois, Jatropha oil, sunflower seed oil, lard, fish oil and trench wet goods reclaim waste oil, or above-mentioned several mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510154278.9A CN104803950A (en) | 2015-04-03 | 2015-04-03 | Method adopting ionic liquid catalyst to catalyze and synthesize epoxy fatty acid glycol ester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510154278.9A CN104803950A (en) | 2015-04-03 | 2015-04-03 | Method adopting ionic liquid catalyst to catalyze and synthesize epoxy fatty acid glycol ester |
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| CN104803950A true CN104803950A (en) | 2015-07-29 |
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| CN201510154278.9A Pending CN104803950A (en) | 2015-04-03 | 2015-04-03 | Method adopting ionic liquid catalyst to catalyze and synthesize epoxy fatty acid glycol ester |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114989489A (en) * | 2021-07-28 | 2022-09-02 | 深圳飞扬兴业科技有限公司 | Epoxy plasticizer and preparation method and application thereof |
-
2015
- 2015-04-03 CN CN201510154278.9A patent/CN104803950A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114989489A (en) * | 2021-07-28 | 2022-09-02 | 深圳飞扬兴业科技有限公司 | Epoxy plasticizer and preparation method and application thereof |
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Application publication date: 20150729 |
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| WD01 | Invention patent application deemed withdrawn after publication |