CN101108803A - Bio-surfactant polylol manufactured with jatropha curcas oil - Google Patents
Bio-surfactant polylol manufactured with jatropha curcas oil Download PDFInfo
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Abstract
The invention relates to the bio-polyol prepared by the Jatropha Curcasl oil by the following methods: the Jatropha Curcasl oil is added with the epoxidizing agent to conduct epoxidation reaction to produce epoxy Jatropha Curcasl oil under the condition that the catalyst exists; the produced epoxy Jatropha Curcasl oil conducts the epoxy bond addition reaction with the ring opening agent containing active hydrogen to produce the mixed hydroxyl fatty acid glyceride; after that, the alcohol or the alcohol amine are added and heated to carry out the alcoholysisreaction to produce the mixed hydroxyl fatty acid ester, namely the bio-polyol. The invention has the advantages that the inventions is high in reaction degree, wide in operation process range, convenient in control, higher in production functionality, convenient in raw material purchase and lower in cost, and does not fight for food with the people and is not affected by the petroleum resource, which is a green product optimizing the ecology. In addition, the invention also has the advantages of strong technology collectiveness and high product conversion.
Description
Technical field
The present invention relates to a kind of biopolyol that adopts the Jatropha curcas oil preparation, it belongs to the organic synthesis field.
Background technology
Along with the fast development of global economy, all polyvalent alcohol demands of the whole world are in quick growth.Usually the polyvalent alcohol that adopts is a polyether glycol, and its technology of preparing is that everybody knows.Along with shortage, price owing to petroleum resources raise up, the mankind more and more pay close attention to environment simultaneously, and wish to reduce the dependency to oil, and the polyvalent alcohol exploitation of green, environmental protection, economy has become the important directions that polyvalent alcohol is developed.
At present, more existing adopt the technology report of the polyvalent alcohols of vegetables oil preparation, carry out alcoholysis reaction as adopting polyols such as glycerine with vegetables oil, back and epoxide carry out addition reaction, prepare the urethane vegetable oil polyol; Or vegetables oil is prepared the urethane vegetable oil polyol by hydrolysis, saponification, hydrogenation, epoxidation and amination reaction.
In addition, what former patent documentation was reported all is to adopt soybean oil, Canadian rapeseed oil, linseed oil, Oleum Gossypii semen, palm wet goods as raw material, prepares the urethane vegetable oil polyol.
Adopt the shortcoming of the vegetable oil polyol of above raw material and prepared to be: technology is complicated, and raw materials cost is higher, and strives food with the people.
Adopt Jatropha curcas oil to prepare biopolyol, do not see reported in literature so far as yet as raw material.
Summary of the invention
The technical problem to be solved in the present invention be exactly existing employing vegetables oil prepare technology that the biopolyol method deposited complexity, poor-performing, raw materials cost than problems such as height, provide a kind of employing Jatropha curcas oil as raw material, adopt the method for epoxidation, hydroxylation prepared biopolyol.
The little seeds of a tung oil tree are being commonly called as of Cortex jatrophae, have another name called lotus tree, tar paulownia, are Euphorbiaceae Cortex jatrophae platymiscium, small idesia oleaginousness higher, surpass the oleaginousness of the common oil crops of Semen Brassicae campestris and soybean.Jatropha curcas oil anorexia usefulness, wherein the content of unsaturated fatty acids is 74.0～83.0%, the content of saturated fatty acid is 17.0～26.0%.And the unsaturated fatty acids in the soybean oil, vegetable seed wet goods vegetables oil is than its height.The lipid acid major ingredient of Jatropha curcas oil is oleic acid, linolic acid, palmitinic acid, stearic acid, Zoomeric acid, linolenic acid, erucic acid etc., two key activity in the molecular structure are higher, can pass through epoxidation reaction, hydroxylating under certain conditions, can utilize the ester bond in the molecular structure to carry out alcoholysis reaction again, finally can obtain the oxy-compound of higher functionality.
These oxy-compound can be used as finished product and use, and directly are used for preparing polyurethane foam, also can be used as the oxy-compound that intermediate and olefin oxide continue reaction generation higher molecular weight, are used for preparing polyurethane foam.
We are referred to as biopolyol with the oxy-compound that aforesaid method makes.
The present invention adopts following technical scheme:
Earlier Jatropha curcas oil is carried out epoxidation reaction with epoxidizing agent in the presence of catalyzer, generate the epoxy Jatropha curcas oil, again with epoxy Jatropha curcas oil that generates and the compound generation epoxy bond ring-opening reaction that contains reactive hydrogen, generate and mix the hydroxy aliphatic acid glyceride, after this add the intensification of alcohol or hydramine and carry out alcoholysis reaction, generate and mix hydroxy fatty acid, i.e. biopolyol.
Aforementioned biopolyol and olefin oxide carry out addition reaction, can generate the biopolyol of higher molecular weight.
Above-mentioned two kinds of biopolyols all are target products of the present invention.
The present invention is this with the Jatropha curcas oil be raw material by the polyvalent alcohol after adding deeply, have level of response height, operating procedure wide ranges, control functionality convenient, product is higher; Simultaneously raw material have buy convenient, cost is lower, do not strive food with the people, be not subjected to petroleum resources influence, belong to the characteristics of renewable resources, be the Green Product of optimizing ecology.Simultaneously of the present invention to have process set strong, the advantage that conversion rate of products is high.
Chemical principle of the present invention is as follows:
1, epoxidation reaction
Here R ' comprise-H ,-CH
3,-C
6H
5,-CH
3(CH
2)
nC
6H
5
2, ring-opening reaction:
Here R ' H refers to alcohol, hydramine
3, alcoholysis reaction (carrying out alcoholysis with the adding glycerol is example):
Here, R " OH refers to glycerol.
In the above-mentioned epoxidation reaction, temperature is controlled between 30～70 ℃, 2.5～12 hours reaction times.
In the above-mentioned epoxidation reaction, adopt the peroxide organic acid as epoxidizing agent, adopting sulfuric acid or phosphoric acid is catalyzer, and the carrying out of epoxidation reaction can be adopted following two kinds of methods:
First method is directly to add the peroxide organic acid and Jatropha curcas oil reacts, and generates the epoxy Jatropha curcas oil;
Second method is earlier by hydrogen peroxide and organic acid reaction, prepares the peroxide organic acid, carries out epoxidation reaction with Jatropha curcas oil again, generates the epoxy Jatropha curcas oil.
When adopting first method, the peroxide organic acid comprises: peroxyformic acid, Peracetic Acid, benzoyl hydroperoxide, mistake oxyalkyl para Toluic Acid, and peroxide organic acid mole dosage is 1.0～1.5 times of Jatropha curcas oil unsaturated double-bond value; When adopting second method, the organic acid that is adopted comprises formic acid, acetate, phenylformic acid, alkyl para Toluic Acid, and the molar weight of hydrogen peroxide is 1.0～1.5 times of Jatropha curcas oil unsaturated double-bond values, and the organic acid mole number is 1.0～4.1 times of Jatropha curcas oil mole number.
In the above-mentioned epoxidation reaction, catalyst sulfuric acid or phosphoric acid weight account for 0.5～5% of Jatropha curcas oil weight.
In the above-mentioned ring-opening reaction, temperature is controlled between 65～170 ℃, 1～12 hour reaction times.
The available catalyzer of ring-opening reaction is mineral alkali and/or organic bases, mineral alkali is selected from the alkoxide of metal hydroxides or metal, be preferably alkali metal hydroxide or alkali-metal alkoxide, wherein alkali metal hydroxide can be selected from sodium hydroxide, potassium hydroxide, lithium hydroxide etc.; Alkali-metal alkoxide can be selected from the product after this type of alcohol such as sodium methylate, sodium ethylate, potassium methylate, glycerine potassium alcoholate dewaters with oxyhydroxide.
Organic bases is an organic amine compound, as dimethylamine, Trimethylamine 99, triethylamine, N, and N-dimethylcyclohexylamine, pentamethyl-diethylenetriamine etc.
The weight of catalyzer is 0～1.5% of epoxy Jatropha curcas oil and ring opening agent weight summation in the ring-opening reaction.
In the ring-opening reaction with alcohol that reactive hydrogen atom can be provided, hydramine as ring opening agent, adoptable ring opening agent mainly contains alcohol, hydramine.The ring opening agent mole dosage is 0.9～1.3 times of oxirane value of epoxy Jatropha curcas oil.
Alcohol in the ring-opening reaction is selected from methyl alcohol, butanols, 1,4-butyleneglycol, glycol ether, triglycol, ethylene glycol, glycerol, propylene glycol, tetramethylolmethane, Xylitol, sorbyl alcohol, TriMethylolPropane(TMP) 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 ring-opening reaction is selected from a Yi Bingchunan, diisopropanolamine (DIPA), tri-isopropanolamine, thanomin, diethanolamine, trolamine, alkyl alkanolamine, benzyl alkanolamine, methyldiethanolamine, methyl diisopropanolamine (DIPA) etc., preferred tri-isopropanolamine and trolamine, methyldiethanolamine, methyl diisopropanolamine (DIPA).
In the above-mentioned ring-opening reaction excessive alcohol or hydramine can be directly as the alcoholysis agent of alcoholysis reaction.Alcoholysis reaction directly adopts the catalyzer in the ring-opening reaction to carry out.Temperature of reaction is 120～240 ℃, and react and carried out under normal pressure in 1～5 hour early stage, and 1～10 hour later stage carried out under vacuum, and vacuum tightness is 100～750kPa.
Alcohol as the alcoholysis agent in the alcoholysis reaction is selected from methyl alcohol, ethanol, propyl alcohol, butanols etc. with 1,4-butyleneglycol, glycol ether, triglycol, ethylene glycol, glycerol, propylene glycol, tetramethylolmethane, Xylitol, sorbyl alcohol etc., dibasic alcohol or trivalent alcohols such as glycerol, TriMethylolPropane(TMP) such as preferred propylene glycol, butyleneglycol, glycol ether, triglycol, ethylene glycol.
Hydramine as the alcoholysis agent in the alcoholysis reaction is selected from a Yi Bingchunan, diisopropanolamine (DIPA), tri-isopropanolamine, thanomin, diethanolamine, trolamine, alkyl alkanolamine, benzyl alkanolamine etc., preferred diisopropanolamine (DIPA), diethanolamine, tri-isopropanolamine, trolamine.
The alcoholysis agent add-on of alcoholysis reaction with the mol ratio of mixing the hydroxy aliphatic acid glyceride is: (2.0～4.2): 1.
Mix the mixing hydroxy fatty acid fat that the hydroxy aliphatic acid glyceride generates after alcoholysis reaction, can directly do the biopolyol use after refining, process for purification is identical with the process for purification of oil polyethers.
The mixing hydroxy fatty acid fat that generates after the alcoholysis reaction, can be in the presence of catalyzer and olefin oxide generation addition reaction, to prepare the polyvalent alcohol of higher molecular weight, then it is made with extra care, process for purification is identical with the process for purification of oil polyethers, prepares the higher biopolyol of molecular weight.
Olefin oxide in the above-mentioned addition reaction is the mixture of ethylene oxide, propylene oxide, oxybutylene or their optional two or more arbitrary proportions; Its consumption is to calculate according to the design hydroxyl value of biopolyol.Olefin oxide adds average functionality/biopolyol design hydroxyl value of weight=coefficient * (molecular-weight average before the molecular-weight average-addition after the addition)=coefficient * 56100 * biopolyol in every mole of biopolyol.Coefficient gets 1.0～1.22 in the formula.
Temperature of reaction in the above-mentioned addition reaction is 80～150 ℃, reaction pressure≤1.0MPa, 2～6 hours reaction times.
The catalyzer of above-mentioned addition reaction is selected from alkali metal hydroxide or alkali metal alkoxide or organic amine, the preferred potassium hydroxide of alkali metal hydroxide wherein, the preferred alkoxide potassium of alkali metal alkoxide; Organic amine is selected from dimethylamine, Trimethylamine 99, triethylamine.If what adopt in the ring-opening reaction is that alkali metal hydroxide or alkali metal alkoxide are as catalyzer, can directly adopt the catalyzer of ring-opening reaction during addition reaction, so the mixing hydroxy fatty acid fat that generates after the alcoholysis reaction need not before addition to carry out refining in advance.When contained catalyst concn is low in the unpurified mixing hydroxy fatty acid fat, add catalyzer as required, the addition biopolyol promptly mixes 0.1～1.5% of hydroxy fatty acid fat and olefin oxide gross weight to make the weight of addition reaction catalyst account for not.
Embodiment
Below by embodiment to further instruction of the present invention
Embodiment 1
The sulfuric acid that will in the glass still of 2L, add Jatropha curcas oil meter 1000g after coming unstuck, 120g formic acid (80%), 33.5g50%, stir, drip 37% the hydrogen peroxide of 452g, under 30～70 ℃ condition, reacted 4～10 hours, standing demix is isolated sour water, the aqueous sodium carbonate that oil phase is used is regulated pH value, and vaccum dewatering also filters.Get epoxy Jatropha curcas oil 1001g, oxirane value is 4.0%.
Embodiment 2
To in the glass still of 2L, add the phosphoric acid of smart Jatropha curcas oil meter 1000g, 230g acetate, 43.8g50%, stir, drip 35% the hydrogen peroxide of 471g, under 30～70 ℃ condition, reacted 4～10 hours, standing demix is isolated sour water, the aqueous sodium carbonate that oil phase is used is regulated pH value, and vaccum dewatering also filters.Get epoxy Jatropha curcas oil 996g, oxirane value is 3.92%.
Embodiment 3
Product epoxy Jatropha curcas oil 1000g among the embodiment 1 is joined in the glass still of 2L, add propylene glycol 233g again, potassium hydroxide 7.9g stirs and heats up 65～170 ℃ of control reaction temperature, 5～10 hours reaction times.Add glycerol 252g, 120～240 ℃ of controlled temperature carried out alcoholysis reaction 4 hours, after vacuum is analyzed to such an extent that hydroxyl value is the crude product of 497mgKOH/g except that behind the small molecules.Through making with extra care, get product 1389g purified biopolyol.
Embodiment 4
Product epoxy Jatropha curcas oil 995g among the embodiment 2 is joined in the glass still of 2L, add diethanolamine 285g again, stir and heat up 65～170 ℃ of control reaction temperature, 5～10 hours reaction times.Add TriMethylolPropane(TMP) 308g, 120～240 ℃ of controlled temperature carried out alcoholysis reaction 4 hours, after vacuum is analyzed to such an extent that hydroxyl value is the crude product of 511mgKOH/g except that behind the small molecules.Through making with extra care, get the 1490g biopolyol.
Embodiment 5
To in the glass still of 5L, add smart Jatropha curcas oil meter 982g, stir, drip 1670g peroxyformic acid (18%), phosphatase 11 5g, under 30～70 ℃ condition, react 7～12 hours.Standing demix is isolated sour water, and the aqueous sodium carbonate that oil phase is used is regulated pH value, and vaccum dewatering also filters.Get epoxy Jatropha curcas oil 996g, oxirane value is 3.78%.
Embodiment 6
Product epoxy Jatropha curcas oil 950g among the embodiment 5 is added in the glass still of 2L, and add methyl alcohol 85g and 10% potassium methylate 14g, stir and heat up 65～150 ℃ of control reaction temperature, 4～9 hours reaction times.The back adds tri-isopropanolamine 440g, and 120～230 ℃ of controlled temperature carried out alcoholysis reaction 3～8 hours, through vacuumize with refining after, filter product 1420g purified biopolyol, hydroxyl value is 499mgKOH/g.
Embodiment 7
To in the glass still of 5L, add smart Jatropha curcas oil meter 978g, stir, drip 3200g benzoyl hydroperoxide (19%), phosphatase 11 8g, under 30～70 ℃ condition, react 5～10 hours.Standing demix is isolated sour water, and the aqueous sodium carbonate that oil phase is used is regulated pH value, and vaccum dewatering also filters.Get epoxy Jatropha curcas oil 997g, oxirane value is 3.81%.
Embodiment 8
Product epoxy Jatropha curcas oil 975g among the embodiment 7 is added in the glass still of 2L, and add diisopropanolamine (DIPA) 455g, stir and heat up 70～170 ℃ of control reaction temperature, 4～10 hours reaction times.Add propylene glycol 175g, 120～230 ℃ of controlled temperature carried out alcoholysis reaction 3～8 hours, through vacuumize with refining after, filter product 1520g biopolyol, hydroxyl value is 467mgKOH/g.
Embodiment 9
Product epoxy Jatropha curcas oil 1050g among the embodiment 7 is added in the glass still of 2L, and add methyl diisopropanolamine (DIPA) 294g, diethanolamine 300g, sodium hydroxide 1.05g stirs and heats up 65～170 ℃ of control reaction temperature, 4～10 hours reaction times.Add ethylene glycol 105g and be warming up to 120～240 ℃ gradually, carried out alcoholysis reaction 3～6 hours, filter 1630g purified biopolyol, hydroxyl value is 495mgKOH/g.
Embodiment 10
To in the glass still of 2L, add the sulfuric acid of smart Jatropha curcas oil meter 1000g, 238g acetate, 35g50%, and be stirred under 30～70 ℃ the condition and reacted 3～10 hours.Standing demix is isolated sour water, and the aqueous sodium carbonate that oil phase is used is regulated pH value, and vaccum dewatering also filters.Get epoxy Jatropha curcas oil 1024g, oxirane value is 3.85%.
Embodiment 11
Product epoxy Jatropha curcas oil 1000g among the embodiment 10 is added in the glass still of 2L, and add tetramethylolmethane 131g, butanols 220g, 10% butanols potassium alcoholate 32g stirs and heats up 65～170 ℃ of control reaction temperature, 4～10 hours reaction times.Add with glycerol 189g and be warming up to 120～240 ℃ gradually, carried out alcoholysis reaction 3～6 hours, after vacuumize with refining the filtration after, 1502g purified biopolyol, hydroxyl value is 488mgKOH/g.
Embodiment 12
With the crude product meter 1300g of embodiment 3,80～120 ℃ of control reaction temperature join in the glass still of 2L, add the 506g propylene oxide, 4～6 hours reaction times.Sampling analysis, getting hydroxyl value is the coarse biometric polylol of 341mgKOH/g.After refining, get product 1728g purified biopolyol.
Embodiment 13
With the crude product meter 1315g among the embodiment 4,80～135 ℃ of control reaction temperature join in the glass still of 2L, add the 400g propylene oxide, 4～7 hours reaction times.Get 1680g after refining, hydroxyl value is the biopolyol of 385mgKOH/g.
Embodiment 14
Crude product meter 1000g with among the embodiment 9 adds potassium hydroxide 4g, joins in the glass still of 2L, and 80～125 ℃ of control reaction temperature add 450g propylene oxide and 310g ethylene oxide, 4 hours reaction times.Analyze to such an extent that hydroxyl value is the coarse biometric polylol of 335mgKOH/g, after after making with extra care 1675g purified biopolyol.
Embodiment 15
Crude product meter 575g with among the embodiment 9 adds 30% Trimethylamine 99 10g, joins in the glass still of 2L 80～120 ℃ of control reaction temperature, the mixture (70/30) of adding 304g propylene oxide and ethylene oxide, 4～6 hours reaction times.Analyze to such an extent that hydroxyl value is the coarse biometric polylol of 400mgKOH/g.After make with extra care the 841g biopolyol.
Claims (17)
1. a biopolyol that adopts the Jatropha curcas oil preparation is characterized in that being prepared from by following method: Jatropha curcas oil is added epoxidizing agent carry out epoxidation reaction in the presence of catalyzer, generate the epoxy Jatropha curcas oil; With epoxy Jatropha curcas oil that generates and the ring opening agent generation epoxy bond ring-opening reaction that contains reactive hydrogen, generate and mix the hydroxy aliphatic acid glyceride again; After this add the intensification of alcohol or hydramine and carry out alcoholysis reaction, generate and mix hydroxy fatty acid, i.e. biopolyol.
2. according to the biopolyol of the described employing Jatropha curcas oil preparation of claim 1, it is characterized in that the biopolyol that will be generated carries out addition reaction with olefin oxide in the presence of catalyzer, generate the biopolyol of higher molecular weight.
3. according to the biopolyol of claim 1 or 2 described employing Jatropha curcas oil preparations, it is characterized in that epoxidation reaction temperature is controlled between 30～70 ℃, 2.5～10 hours reaction times.
4. according to the biopolyol of claim 1 or 2 described employing Jatropha curcas oil preparations, it is characterized in that epoxidation reaction adopts the peroxide organic acid as epoxidizing agent, adopt sulfuric acid or phosphoric acid, can adopt one of following method when specifically reacting as catalyzer:
First method is directly to adopt peroxide organic acid and Jatropha curcas oil to react, and generates the epoxy Jatropha curcas oil;
Second method is to adopt hydrogen peroxide and organic acid reaction, prepares the peroxide organic acid, carries out epoxidation reaction with Jatropha curcas oil again, generates the epoxy Jatropha curcas oil.
5. according to the biopolyol of the described employing Jatropha curcas oil of claim 4 preparation, when it is characterized in that adopting first method, the peroxide organic acid is selected from: peroxyformic acid, Peracetic Acid, benzoyl hydroperoxide, cross the mixture of oxyalkyl para Toluic Acid or above-mentioned optional two or more; Wherein peroxide organic acid mole dosage is 1.0～1.5 times of Jatropha curcas oil unsaturated double-bond value; When adopting second method, organic acid is selected from formic acid, acetate, phenylformic acid or alkyl para Toluic Acid, and the mole dosage of hydrogen peroxide is 1.0～1.5 times of Jatropha curcas oil unsaturated double-bond values, and the organic acid mole number is 1.0～4.1 times of Jatropha curcas oil mole number; The weight of catalyzer accounts for 0.5～5% of Jatropha curcas oil weight.
6. according to the biopolyol of claim 1 or 2 described employing Jatropha curcas oil preparations, it is characterized in that the ring-opening reaction temperature is controlled between 65～170 ℃, 1～12 hour reaction times.
7. according to the biopolyol of claim 1 or the preparation of 2 described employing Jatropha curcas oils, the ring opening agent that it is characterized in that in the ring-opening reaction being adopted adopts alcohol or hydramine, and the ring opening agent mole dosage is 0.9～1.3 times of oxirane value of epoxy Jatropha curcas oil.
8. according to the biopolyol of the described employing Jatropha curcas oil preparation of claim 7, it is characterized in that the alcohol in the ring-opening reaction is selected from methyl alcohol, ethanol, propyl alcohol, butanols, butyleneglycol, glycol ether, triglycol, ethylene glycol, glycerol, propylene glycol, tetramethylolmethane, Xylitol, sorbyl alcohol or TriMethylolPropane(TMP);
Hydramine is selected from a Yi Bingchunan, diisopropanolamine (DIPA), tri-isopropanolamine, thanomin, diethanolamine, trolamine, methyldiethanolamine, methyl diisopropanolamine (DIPA), alkyl alkanolamine or benzyl alkanolamine.
9. according to the biopolyol of the described employing Jatropha curcas oil preparation of claim 8, it is characterized in that the preferred propylene glycol of alcohol, butyleneglycol, glycol ether, triglycol, ethylene glycol or glycerol, TriMethylolPropane(TMP) in the ring-opening reaction; The preferred tri-isopropanolamine of hydramine, trolamine, methyldiethanolamine or methyl diisopropanolamine (DIPA).
10. according to the biopolyol of claim 1 or the preparation of 2 described employing Jatropha curcas oils, it is characterized in that ring-opening reaction can adopt catalyzer to accelerate speed of reaction, catalyzer is mineral alkali and/or organic bases, and mineral alkali is selected from the alkoxide of metal hydroxides or metal; Organic bases is an organic amine compound; The weight of catalyzer is 0～1.5% of epoxy Jatropha curcas oil and ring opening agent weight summation in the ring-opening reaction.
11. biopolyol according to the described employing Jatropha curcas oil preparation of claim 10, preferred alkali metal hydroxide or alkali-metal alkoxide when it is characterized in that catalyzer in the ring-opening reaction is selected the alkoxide of metal hydroxides or metal for use, wherein alkali metal hydroxide is selected from sodium hydroxide, potassium hydroxide or lithium hydroxide; Alkali-metal alkoxide is selected from the product after sodium methylate, sodium ethylate, potassium methylate or glycerine potassium alcoholate and the oxyhydroxide dehydration; When selecting organic amine compound for use, catalyzer is selected from dimethylamine, Trimethylamine 99, triethylamine, N, N-dimethyl cyclohexyl amine or pentamethyl-diethylenetriamine.
12. the biopolyol according to claim 1 or 2 described employing Jatropha curcas oil preparations is characterized in that alcoholysis reaction directly adopts the catalyzer in the ring-opening reaction to carry out; Temperature of reaction is 120～240 ℃, and carry out 1～5 hour early stage under normal pressure, and 1～10 hour later stage carried out under vacuum, and vacuum tightness is 100～750kPa.
13. the biopolyol according to claim 1 or 2 described employing Jatropha curcas oil preparations is characterized in that the alcoholysis agent of alcoholysis reaction and the mol ratio of epoxy Jatropha curcas oil are: (2.0～4.2): 1.
14., it is characterized in that the olefin oxide in the addition reaction is ethylene oxide, propylene oxide, oxybutylene or their optional mixtures according to the biopolyol of the described employing Jatropha curcas oil preparation of claim 2; Its consumption is to calculate according to the design hydroxyl value of biopolyol, olefin oxide adds average functionality/biopolyol design hydroxyl value of weight=coefficient * (molecular-weight average before the molecular-weight average-addition after the addition)=coefficient * 56100 * biopolyol in every mole of biopolyol, and coefficient gets 1.0～1.22 in the formula.
15. the biopolyol according to the described employing Jatropha curcas oil preparation of claim 2 is characterized in that the temperature of reaction in the addition reaction is 80～150 ℃, reaction pressure≤1.0MPa.2～6 hours reaction times.
16. biopolyol according to the described employing Jatropha curcas oil preparation of claim 2, the catalyzer that it is characterized in that addition reaction is selected from alkali metal hydroxide or alkali metal alkoxide or organic amine, and the weight of addition reaction catalyst accounts for 0.1～1.5% of the pure and mild olefin oxide gross weight of addition bio-based polyhydric not.
17. the biopolyol according to the described employing Jatropha curcas oil preparation of claim 16 is characterized in that the preferred potassium hydroxide of alkali metal hydroxide, the preferred alkoxide potassium of alkali metal alkoxide; Organic amine is selected from dimethylamine, Trimethylamine 99 or triethylamine.
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| CN102911012A (en) * | 2012-10-22 | 2013-02-06 | 南京工业大学 | Bio-based polyalcohol and one-step synthetic method and application thereof |
| CN102911012B (en) * | 2012-10-22 | 2015-05-13 | 南京工业大学 | Bio-based polyalcohol and one-step synthetic method and application thereof |
| CN104231199A (en) * | 2014-10-11 | 2014-12-24 | 攀枝花学院 | Inflaming retarding bio-based polyhydric alcohol and preparation method thereof |
| CN105646225A (en) * | 2014-12-05 | 2016-06-08 | 中国石油化工股份有限公司 | Tung oil-based polyol and preparation method thereof |
| CN107151213B (en) * | 2016-03-03 | 2020-08-07 | 中国石油化工股份有限公司 | Halogen-free flame-retardant tung oil polyol and preparation method and application thereof |
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| CN106810514B (en) * | 2016-12-28 | 2019-05-10 | 华南农业大学 | Based on UV photocatalysis polyunsaturated vegetable oil polylol and preparation method and application |
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| CN110272447A (en) * | 2018-03-17 | 2019-09-24 | 南京工业大学 | A method of preparing organosilicon Biolubrication oil base oil |
| CN110272447B (en) * | 2018-03-17 | 2021-11-12 | 南京工业大学 | Method for preparing organic silicon biological lubricating oil base oil |
| CN108940117A (en) * | 2018-08-03 | 2018-12-07 | 郑州轻工业学院 | A kind of nonionic glycosyl type Gemini surface active agent of hydroxyl spacer group and preparation method thereof |
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