CN100465151C - Method for preparing biology based polyalcohol by using monoester of hybrid epoxidized fatty acid produced from seed oil - Google Patents
Method for preparing biology based polyalcohol by using monoester of hybrid epoxidized fatty acid produced from seed oil Download PDFInfo
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- CN100465151C CN100465151C CNB2006100413813A CN200610041381A CN100465151C CN 100465151 C CN100465151 C CN 100465151C CN B2006100413813 A CNB2006100413813 A CN B2006100413813A CN 200610041381 A CN200610041381 A CN 200610041381A CN 100465151 C CN100465151 C CN 100465151C
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Abstract
This invention relates to a method for preparing biopolyols from mixed epoxy fatty acid monoesters generated from rapeseed oil. The method comprises: performing ring-opening reaction on mixed epoxy fatty acid monoesters generated from rapeseed oil and nucleophilic agent containing active hydrogen to obtain bopolyols. The biopolyols have adjustable performance and good functions. The method can be used for preparing biopolyols with different functionality degrees and preconcerted hydropolyol values by selecting different mixed epoxy fatty acid monoesters and hydrogen donors. The method does not use olefin oxide, and reduces the dependence on petrochemicals.
Description
Technical field
What the present invention relates to is a kind of method that is prepared biopolyol by the mixed epoxidized fatty acid monoester of rapeseed oil preparation of using.It is by with mixed epoxidized fatty acid monoester and hydrogen donor nucleophilic reagent generation addition reaction, mixes the hydroxy aliphatic acid monoester thereby make, and promptly biopolyol belongs to the organic synthesis field.
Background technology
Present polyvalent alcohol mainly contains three kinds, a kind of be with polyvalent alcohol or organic amine be initiator by with the polymkeric substance of propylene oxide or ethylene oxide, be called polyether glycol (abbreviating PPG as); Another kind of modify and graft polyether glycol is based on PPG, makes through bulk polymerization in polyvalent alcohol with vinyl monomer then, is called polymer polyatomic alcohol (abbreviating POP as), and normal and PPG is used; The third is the polyvalent alcohol by tetrahydrofuran ring opening polymerization.These three kinds of derived product that product all is an oil, because the non-renewable and shortage day by day of petroleum resources, the price of these products is higher.The throughput of domestic olefin oxide is limited in addition, needs import, buys inconvenience, directly has influence on the production of product.Seek a kind of new resource, more economical, the environmental protection of the product that makes reduces the dependence to petroleum chemicals simultaneously, is a direction of human research's polyvalent alcohol.
Because rapeseed oil can be regenerated, therefore rapeseed oil can constantly be produced through the mixed epoxidized fatty acid monoester of alcoholysis and epoxidation technique preparation, can obtain the mixing-in fat acid monoester of different functionality simultaneously in the alcoholysis process with different alcoholysis agent, the controllability of product improves.In addition; epoxy bond in the mixed epoxidized fatty acid monoester is because triangle tension force; very active; easy and nucleophilic reagent reacts, further derivatives such as prepared in reaction alcohol or dibasic alcohol, polyvalent alcohol, alkoxyl alcohol (ether alcohol), hydroxy ester (ester alcohol), N-hydroxyalkylamides, mercapto alcohol, amino alcohol, hydroxyl nitrile, chloropharin, hydroxyl sulfoacid sodium.Mixing hydroxy aliphatic acid monoester after the open loop is a biopolyol, can be applicable to prepare polyurethane foam.At present, do not see as yet and the mixed epoxidized fatty acid monoester by rapeseed oil preparation is carried out deep processing prepare that to mix the hydroxy aliphatic acid monoester be the report of biopolyol.
Summary of the invention
What the present invention will solve is exactly the synthetic existing technical problem of polyvalent alcohol of above-mentioned chemical industry, and a kind of method that is prepared biopolyol by the mixed epoxidized fatty acid monoester of rapeseed oil preparation of using is provided.
The present invention adopts following technical scheme:
To mixed epoxidized fatty acid monoester and the nucleophilic reagent generation ring-opening reaction that contains reactive hydrogen by the rapeseed oil preparation, generating mixing hydroxy aliphatic acid monoester is biopolyol in the presence of catalyzer.
Mixed epoxidized fatty acid monoester of the present invention is by the alcoholysis rapeseed oil, and the mixing unsaturated fatty acids acid monoester to alcoholysis carries out epoxidation and then obtains mixed epoxidized fatty acid monoester then.
The relevant chemical principle that adopts rapeseed oil to prepare in the epoxy fatty acid monoester process is as follows:
1, alcoholysis principle:
R ' OH represents alcohol.
2, epoxidation principle:
RCOOH is an organic acid
Here R ' OOCHR
1=CHR
2Refer to mix the unsaturated fatty acids acid monoester.
The principle of ring-opening reaction involved in the present invention is as follows:
Here XH is meant nucleophilic reagent, is selected from alcohol, acid, amine or hydramine.
Catalyzer can adopt an acidic catalyst, metal hydroxides or metal alkoxide among the present invention.Preferred acidic catalyzer, alkali metal hydroxide or alkali metal alkoxide.
Above-mentioned an acidic catalyst is the sulfuric acid catalysis carclazyte;
Above-mentioned base metal catalysts is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide etc.; Alkali metal alkoxide is selected from the product after sodium methylate, sodium ethylate, potassium methylate, glycerine potassium alcoholate etc. or alcohol and oxyhydroxide reaction and the dehydration.
In the above-mentioned ring-opening reaction, temperature is controlled between 65 ℃～200 ℃, and the reaction times is 1～12h.
Catalyst consumption is 0.05～0.9% of mixed epoxidized fatty acid monoester and a nucleophilic reagent quality consumption summation in the ring-opening reaction.
Alcohol in the above-mentioned nucleophilic reagent is selected from methyl alcohol, ethanol, propyl alcohol, butanols, 1,4-butyleneglycol, glycol ether, triglycol, ethylene glycol, glycerol, propylene glycol, TriMethylolPropane(TMP), tetramethylolmethane, Xylitol, sorbyl alcohol, sucrose, glucose etc.Dibasic alcohol or trivalent alcohols such as glycerol, TriMethylolPropane(TMP) such as preferred propylene glycol, butyleneglycol, glycol ether, triglycol, ethylene glycol.
Hydramine in the above-mentioned nucleophilic reagent is selected from a Yi Bingchunan, diisopropanolamine (DIPA), tri-isopropanolamine, thanomin, diethanolamine, trolamine, alkyl alkanolamine, benzyl alkanolamine etc.Preferred tri-isopropanolamine, trolamine, methyldiethanolamine, methyl diisopropanolamine (DIPA);
Acid in the above-mentioned nucleophilic reagent is selected from adipic acid, phthalic acid etc.;
Amine in the above-mentioned nucleophilic reagent is selected from monobutyl amine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine etc.
After ring-opening reaction finishes, to make with extra care product, treating process is, when adopting acidic substance as catalyzer, with alkali acidic substance are carried out neutralizing treatment, when adopting alkaline matter, alkaline catalysts is carried out neutralizing treatment, add sorbent material then and adsorb, after dehydration, filtration promptly get purified mixing hydroxy aliphatic acid monoester with acid as catalyzer.
In the above-mentioned treating process, when acidic substance were handled, used alkali was sodium hydroxide solution or sodium carbonate solution, and its consumption is for making the system neutralization for neutral.
The above-mentioned acid of adopting is for providing H
+Acid, comprise phosphoric acid, tetra-sodium, sulfuric acid, oxalic acid, hydrochloric acid etc., the mol ratio of its consumption and alkaline catalysts consumption is 1:(1.0～1.05).Preferably phosphoric acid and hydrochloric acid, more preferably phosphoric acid.
Above-mentioned neutral temperature is controlled at 50 ℃～90 ℃, in and the time be 15～45min.
Sorbent material is the material with adsorption function in above-mentioned, and as diatomite, atlapulgite, pure aluminium silicate, activated carbon etc., its consumption is generally and mixes 0.08～3.0% of hydroxy fatty acid monoester.
Vacuum tightness is 100～750Kpa during filtration, and filtration temperature is 80 ℃～120 ℃.
By above-mentioned operation, obtain biopolyol.
The biological multielement alcohol that obtains with technology of the present invention has following advantage:
1, mixing the hydroxy aliphatic acid monoester is the performance controllability height of biopolyol, functional strong.
2, can select different mixed epoxidized fatty acid monoesters and hydrogen donor for use as required, thereby obtain the biopolyol of different functionality and pre-design hydroxyl value.
3, with the mixed epoxidized fatty acid monoester of reproducible rapeseed oil preparation as raw material, reduced dependence to petroleum chemicals.
4, this technology is without olefin oxide.
Embodiment
Below the present invention is further illustrated by example.
Embodiment 1
In the glass still of 2L, add mixed epoxidized fatty acid monoester 800g, propylene glycol 208g, add potassium hydroxide 1.2g, 65 ℃～200 ℃ the reaction 1～12 hour, after make with extra care, concrete grammar is as follows: add 50% phosphatase 24 .2g and carry out neutralization reaction 20min, adding Magnesium Silicate q-agent 4g adsorbs, the back is 150kPa in vacuum tightness, under 80 ℃～120 ℃ the temperature, dewaters about 1 hour, filter then, get 900g mixing hydroxy aliphatic acid monoester product.
Embodiment 2
In the glass still of 2L, add mixed epoxidized fatty acid monoester 800g, trolamine 408g, add sodium ethylate 1.2g, at 65 ℃～200 ℃ reaction 1～12h.Hour, after make with extra care, concrete grammar is as follows: add 50% phosphoric acid 2.5g and carry out neutralization reaction 20min, add Magnesium Silicate q-agent 4g and adsorb, the back is 150kPa in vacuum tightness, under 80 ℃～120 ℃ the temperature, dewatered about 1 hour, and filtered then, get 1110g mixing hydroxy aliphatic acid monoester product.
Embodiment 3
In the glass still of 2L, add mixed epoxidized fatty acid monoester 800g, diisopropanolamine (DIPA) 364g, add sodium ethylate 1.2g, 65 ℃～200 ℃ the reaction 1～12h hour, after make with extra care, concrete grammar is as follows: add 50% phosphoric acid 2.5g and carry out neutralization reaction 20min, adding Magnesium Silicate q-agent 4g adsorbs, the back is 150kPa in vacuum tightness, under 80 ℃～120 ℃ the temperature, dewaters about 1 hour, filter then, get 1008g mixing hydroxy aliphatic acid monoester product.
Embodiment 4
In the glass still of 2L, add mixed epoxidized fatty acid monoester 800g, adipic acid 384g, add sulfuric acid catalysis carclazyte 5g, 65 ℃～200 ℃ reactions 1～12 hour, after make with extra care, concrete grammar is as follows: it is neutral being neutralized to system with sodium carbonate solution, and the back is 150kPa in vacuum tightness, under 80 ℃～120 ℃ the temperature, dewatered about 1 hour, and filtered then, get 1100g mixing hydroxy aliphatic acid monoester product.
Embodiment 5
In the glass still of 2L, add mixed epoxidized fatty acid monoester 800g, monobutyl amine 166g, add potassium hydroxide 1.1g, 65 ℃～200 ℃ the reaction 1～12 hour, after make with extra care, concrete grammar is as follows: add 50% phosphoric acid 3.9g and carry out neutralization reaction 20min, adding Magnesium Silicate q-agent 4g adsorbs, the back is 150kPa in vacuum tightness, under 80 ℃～120 ℃ the temperature, dewaters about 1 hour, filter then, get 875g mixing hydroxy aliphatic acid monoester product.
Embodiment 6
In the glass still of 2L, add mixed epoxidized fatty acid monoester 800g, glycol ether 278g, add potassium hydroxide 1.1g, 65 ℃～200 ℃ the reaction 1～12 hour, after make with extra care, concrete grammar is as follows: add 50% phosphoric acid 3.9g and carry out neutralization reaction 20min, adding Magnesium Silicate q-agent 4g adsorbs, the back is 150kPa in vacuum tightness, under 80 ℃～120 ℃ the temperature, dewaters about 1 hour, filter then, get 935g mixing hydroxy aliphatic acid monoester product.
Claims (12)
1, a kind of method for preparing biopolyol by the mixed epoxidized fatty acid monoester of rapeseed oil preparation of using, it is characterized in that ring-opening reaction takes place for mixed epoxidized fatty acid monoester and the hydrogen donor nucleophilic reagent that contains reactive hydrogen in the presence of catalyzer, mix hydroxy aliphatic acid monoester, i.e. biopolyol thereby make.
2, according to the described method for preparing biopolyol by the mixed epoxidized fatty acid monoester of rapeseed oil preparation of using of claim 1, it is characterized in that the hydrogen donor nucleophilic reagent is selected from alcohol, amine, hydramine or acid.
3, according to the described method for preparing biopolyol by the mixed epoxidized fatty acid monoester of rapeseed oil preparation of using of claim 2, it is characterized in that alcohol in the nucleophilic reagent is selected from methyl alcohol or ethanol, propyl alcohol, butanols, 1,4-butyleneglycol, glycol ether, triglycol, ethylene glycol, glycerol, propylene glycol, TriMethylolPropane(TMP), tetramethylolmethane, Xylitol, sorbyl alcohol, sucrose, glucose.
4,, it is characterized in that amine in the nucleophilic reagent is selected from monobutyl amine or triethylene tetramine, tetraethylene pentamine according to the described method for preparing biopolyol by the mixed epoxidized fatty acid monoester of rapeseed oil preparation of using of claim 2.
5,, it is characterized in that in the nucleophilic reagent that hydramine is selected from a Yi Bingchunan or diisopropanolamine (DIPA), tri-isopropanolamine, thanomin, diethanolamine, trolamine, alkyl alkanolamine, benzyl alkanolamine according to the described method for preparing biopolyol by the mixed epoxidized fatty acid monoester of rapeseed oil preparation of using of claim 2.
6, according to the described method for preparing biopolyol by the mixed epoxidized fatty acid monoester of rapeseed oil preparation of using of claim 2, it is characterized in that the acid in the nucleophilic reagent is selected from adipic acid or phthalic acid.
7, according to the described method for preparing biopolyol by the mixed epoxidized fatty acid monoester of rapeseed oil preparation of using of claim 1, it is characterized in that catalyzer is acid, alkali metal hydroxide or alkali metal alkoxide.
8, according to the described method for preparing biopolyol by the mixed epoxidized fatty acid monoester of rapeseed oil preparation of using of claim 7, it is characterized in that acid catalyst is the sulfuric acid catalysis carclazyte.
9,, it is characterized in that alkali metal hydroxide is selected from sodium hydroxide or potassium hydroxide, lithium hydroxide according to the described method for preparing biopolyol by the mixed epoxidized fatty acid monoester of rapeseed oil preparation of using of claim 7; Alkali-metal alkoxide is selected from sodium methylate or sodium ethylate, potassium methylate, glycerol potassium.
10, according to the described method for preparing biopolyol by the mixed epoxidized fatty acid monoester of rapeseed oil preparation of using of claim 1, it is characterized in that the ring-opening reaction temperature is 65 ℃～200 ℃.
11, according to the described method that is prepared biopolyol by the mixed epoxidized fatty acid monoester of rapeseed oil preparation of using of claim 1, it is promptly refining to it is characterized in that after the ring-opening reaction carrying out neutralizing treatment to crude product; When making catalyzer with acidic substance, carry out neutralizing treatment with alkaline matter, when making catalyzer, carry out neutralizing treatment with acidic substance with alkaline matter; Add sorbent material then and adsorb, after vacuum hydro-extraction, filtering operation.
12, according to the described method that is prepared biopolyol by the mixed epoxidized fatty acid monoester of rapeseed oil preparation of using of claim 11, the acidic substance that it is characterized in that the neutralization bases catalyzer are selected from H can be provided
+Acid, be selected from phosphoric acid, tetra-sodium, sulfuric acid, oxalic acid or hydrochloric acid, the mol ratio of its consumption and alkaline catalysts consumption is 1:(1.0～1.05); The alkaline matter of neutralizing acid catalyzer is sodium hydroxide solution or sodium carbonate solution, and its consumption is neutral for making system; Selected sorbent material is the material with adsorption function, is selected from diatomite, atlapulgite, pure aluminium silicate or activated carbon, and its consumption is 0.08～3.0% of a mixed epoxidized fatty acid monoester; Dehydration and filtration temperature are: 80 ℃～120 ℃, vacuum tightness is 100KPa～750Kpa during dehydration, and dewatering time is 60～150min, and filter pressure is 1.5～3kg/cm
2
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| CN101020862B (en) * | 2007-03-22 | 2010-11-03 | 北京硕泰生物技术有限责任公司 | Two-step reaction process for preparing hydroxyl vegetable oil |
| US8022257B2 (en) | 2009-09-03 | 2011-09-20 | The Ohio State University Research Foundation | Methods for producing polyols using crude glycerin |
| CN107935967A (en) * | 2017-11-10 | 2018-04-20 | 广州市友聚米新材料有限公司 | A kind of bio-based is modified the preparation method of amido polyol |
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| Cargill公司开始生产生物基多元醇. 石油化工，第35卷第6期. 2006 |
| Cargill公司开始生产生物基多元醇. 石油化工，第35卷第6期. 2006 * |
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