CN101139252B - Biological radical polyatomic alcohol prepared by Jatropha curcas oil - Google Patents
Biological radical polyatomic alcohol prepared by Jatropha curcas oil Download PDFInfo
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- CN101139252B CN101139252B CN2007101308503A CN200710130850A CN101139252B CN 101139252 B CN101139252 B CN 101139252B CN 2007101308503 A CN2007101308503 A CN 2007101308503A CN 200710130850 A CN200710130850 A CN 200710130850A CN 101139252 B CN101139252 B CN 101139252B
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Abstract
The present invention relates to a preparation method for a biological polybasic alcohol by using of an aleurites fordii. The preparation method is as follows: an alcohol-decomposing agent is added into the aleurites fordii to make the alcohol-decomposing reaction in the catalyzing environment to create a mixing ester of fatty acid; and then an epoxidizing agent is added into the mixing ester of fatty acid to make the epoxidizing reaction in the catalyzing environment to create a mixing epoxidizing ester of fatty acid; the mixing epoxidizing ester of fatty acid takes the opening reaction of epoxidizing key with an opening agent to create a mixing hydroxylic ester of fatty acid, i.e. a biological polybasic alcohol. The biological polybasic alcohol takes the addition reaction with an oxidation alkene in the catalyzing environment to create a biological polybasic alcohol with much higher molar weight. The preparation technics and operation of the present invention are more convenient; the adjustability for the product function is much better with much better performance. The aleurites fordii materials used in the present invention is a reproducible materials; so the cost is much lower and the material is abundant, which can replace the petrifaction polyether glycol to prepare the polyurethane foam plastic so that the dependence to the polyurethane product decreases.
Description
Technical field
The present invention relates to utilize Jatropha curcas oil to carry out the biopolyol that prepared in reaction such as alcoholysis, epoxidation, open loop go out, belong 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 biopolyol of prepared such as alcoholysis, epoxidation, open loop.
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 alcoholysis reaction with the alcoholysis agent in the presence of catalyzer, generate mixed aliphatic ester, epoxidation reaction is carried out in it and epoxidizing agent, generate the hybrid epoxidized fatty acid ester, after hybrid epoxidized fatty acid ester and the ring opening agent that generates carried out ring-opening reaction, generate and mix hydroxy fatty acid fat, 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, alcoholysis reaction (carrying out alcoholysis with the adding glycerol is example)
Here, R " OH refers to glycerol.
2, epoxidation reaction:
Above-mentioned is example with the mono-glycerides.
2, ring-opening reaction
Above-mentioned ring opening agent is example with the diethanolamine.
In the above-mentioned alcoholysis reaction, temperature of reaction is controlled between 65～240 ℃, 1～16 hour reaction times.
The available catalyzer of alcoholysis reaction is mineral alkali and/or organotin, 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 sodium methylate, sodium ethylate, potassium methylate, alcohol dewater with oxyhydroxide, pure identical in aforementioned alcohol and the following alcoholysis agent.
The weight of catalyzer is 0.005～1.3% of Jatropha curcas oil and alcoholysis agent weight summation in the alcoholysis reaction.
Alcoholysis agent in the alcoholysis reaction is alcohol or hydramine.Alcohol 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 is selected from a Yi Bingchunan, diisopropanolamine (DIPA), tri-isopropanolamine, thanomin, diethanolamine, trolamine, methyldiethanolamine, methyl diisopropanolamine (DIPA), alkyl alkanolamine, benzyl alkanolamine etc., preferred diisopropanolamine (DIPA), diethanolamine, tri-isopropanolamine, trolamine.
The mol ratio of alcoholysis agent add-on and Jatropha curcas oil is: (2.0～5.7): 1.
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 mixed aliphatic ester reacts, and generates the epoxy mixed aliphatic ester;
Second method is earlier by hydrogen peroxide and organic acid reaction, prepares the peroxide organic acid, carries out alcoholysis reaction with mixed aliphatic ester again, generates the epoxy mixed aliphatic ester.
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 mixed aliphatic ester unsaturated double-bond value;
When adopting second method, the organic acid that is adopted comprises formic acid, acetate, phenylformic acid, alkyl para Toluic Acid, the molar weight of hydrogen peroxide is 1.0～1.5 times of mixed aliphatic ester unsaturated double-bond values, and the organic acid mole number is 0.5～3 times of mixed aliphatic ester unsaturated double-bond value.
In the above-mentioned epoxidation reaction, catalyst sulfuric acid or phosphoric acid weight account for 0.1～5% of mixed aliphatic ester weight.
In the above-mentioned epoxidation reaction, 30～70 ℃ of temperature of reaction controls, reaction times: 1～10 hour.
In the above-mentioned ring-opening reaction, temperature of reaction is controlled between 65～180 ℃, 1～10 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.; Pure identical in the product after alkali-metal alkoxide can be selected from sodium methylate, sodium ethylate, potassium methylate or alcohol and dewaters with oxyhydroxide, aforementioned alcohol and ring opening agent.
Organic bases is an organic amine compound, as dimethylamine, Trimethylamine 99, triethylamine, N, and N-dimethyl cyclohexyl amine, pentamethyl-diethylenetriamine etc.
The weight of catalyzer is 0～1.5% of epoxy mixed aliphatic ester and ring opening agent weight summation in the ring-opening reaction.
Ring opening agent in the ring-opening reaction is alcohol or hydramine.Alcohol 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.Preferred propylene glycol, butyleneglycol, glycol ether, triglycol, ethylene glycol or glycerol, TriMethylolPropane(TMP).
Hydramine is selected from a Yi Bingchunan, diisopropanolamine (DIPA), tri-isopropanolamine, thanomin, diethanolamine, trolamine, alkyl alkanolamine, benzyl alkanolamine etc.Preferred tri-isopropanolamine, diisopropanolamine (DIPA), trolamine, diethanolamine.
Ring opening agent is (0.8～1.6) with the ratio of hybrid epoxidized mixed aliphatic ester epoxy bond mole number: 1.
Catalyzer in the above-mentioned addition reaction is identical with the method for synthetic petroleum polyethers, and wherein olefin oxide is ethylene oxide, propylene oxide, oxybutylene or their optional mixtures; 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.
The temperature of reaction of addition reaction is 80～150 ℃, reaction pressure≤1.0MPa, 2～6 hours reaction times.
The catalyzer of 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.Wherein the preferred potassium hydroxide of alkali metal hydroxide adopts organic amine can be selected from dimethylamine, Trimethylamine 99 or triethylamine.
Embodiment
Embodiment 1
Add Jatropha curcas oil 1000g, glycerol 215g in the glass still of 2L, potassium hydroxide 1.0g stirs, and is warming up to 160～240 ℃, carries out alcoholysis reaction 5h, and the back is to keep 3h under the situation of 100～750kPa in vacuum tightness.Refining then, get mixed aliphatic ester 1185g.
Embodiment 2
The phosphoric acid of getting mixed aliphatic ester 1000g among the embodiment 1 and 74g formic acid (85%), 20g adds in the glass still of 2L, stirs Dropwise 5 07g hydrogen peroxide (27.5%), under 30～70 ℃ condition, react 8h, after refining, get the hybrid epoxidized fatty acid ester, oxirane value is 3.41%.
Embodiment 3
With the product hybrid epoxidized fatty acid ester 1000g among the embodiment 2, add trolamine 380g again, potassium hydroxide 1.2g, join in the glass still of 2L, stir and heat up 120～160 ℃ of control reaction temperature, reaction times 6h, get biopolyol A product 1280g after refining, hydroxyl value is 490mgKOH/g, moisture :≤0.10%.
Embodiment 4
With the unpurified biopolyol 933g among the embodiment 3, join in the glass still of 2L, stir and heat up, feed oxyethane 20g and propylene oxide 60g, 80～120 ℃ of control reaction temperature are behind the reaction times 4h.Through refining biopolyol product E 960g, hydroxyl value is 454mgKOH/g, moisture :≤0.10%.
Embodiment 5
Add Jatropha curcas oil 870g, glycol ether 216g in the glass still of 2L, potassium hydroxide 1.1g stirs, and is warming up to 140～240 ℃, carries out alcoholysis reaction 5.5h, and the back is to keep 3h under the situation of 100～720kPa in vacuum tightness.Make with extra care then, get mixed aliphatic ester 1013g.
Embodiment 6
Mixed aliphatic ester 1000g and 72g formic acid (85%), the 20g sulfuric acid (50%) got among the embodiment 5 add in the glass still of 2L, stir, and drip 494g hydrogen peroxide (27.5%), react 6～10h under 30～70 ℃ condition.After refining, get the hybrid epoxidized fatty acid ester, the oxirane value that detects it is 3.32%.
Embodiment 7
With the product hybrid epoxidized fatty acid ester 1000g among the embodiment 6, add diisopropanolamine (DIPA) 330g again, (10%) glycerol potassium 28g, join in the glass still of 5L, stir and heat up 120～180 ℃ of control reaction temperature, reaction times 7～10h, through refining product biopolyol B1250g, hydroxyl value is 411mgKOH/g, moisture :≤0.10%.
Embodiment 8
With the unpurified biopolyol B929g among the embodiment 7, join in the glass still of 2L, stir and heat up, feed oxyethane 200g and propylene oxide 416g, 80～120 ℃ of control reaction temperature are behind reaction times 2～6h.Through refining biopolyol product F 1480g, hydroxyl value is 250mgKOH/g, moisture :≤0.10%.
Embodiment 9
Add Jatropha curcas oil 1000g, propylene glycol 183g in the glass still of 2L, 10% glycerol potassium 35g stirs, and is warming up to 160～200 ℃, carries out alcoholysis reaction 4h, and the back is to keep 3～5h under the situation of 100～750kPa in vacuum tightness.Get mixed aliphatic ester 1100g after refining.
Embodiment 10
Mixed aliphatic ester 1000g and 76g formic acid (85%), the 20g sulfuric acid (50%) got among the embodiment 9 add in the glass still of 2L, stir, and Dropwise 5 21 gram hydrogen peroxide (27.5%) react 5～10h under 30～70 ℃ condition.After refining, get the hybrid epoxidized fatty acid ester, the oxirane value that detects it is 3.50%.
Embodiment 11
Product hybrid epoxidized fatty acid ester 1000g with among the embodiment 10 adds diethanolamine 275g again, and sodium hydroxide 1.23g joins in the glass still of 2L, stirs to heat up 100～180 ℃ of control reaction temperature, reaction times 5～8h.Refining biopolyol ℃ product 1210g, hydroxyl value 449mgKOH/g, moisture :≤0.11%.
Embodiment 12
Not refined biological polylol C 853g with among the embodiment 11 joins in the glass still of 2L, stirs to heat up, and feeds oxyethane 60g and propylene oxide 100g, and 80～150 ℃ of control reaction temperature are behind reaction times 2～6h.Through refining biopolyol product G 960g, hydroxyl value is 380mgKOH/g, moisture :≤0.11%.
Embodiment 13
Add Jatropha curcas oil 1100g, ethylene glycol 150g in the glass still of 2L, potassium hydroxide 0.9g stirs, and is warming up to 130～240 ℃, carries out alcoholysis reaction 5h, and the back is to keep 3～6h under the situation of 100～750kPa in vacuum tightness.Get mixed aliphatic ester 1175g after refining.
Embodiment 14
Mixed aliphatic ester 1000g and 79g formic acid (85%), the 20g phosphoric acid got among the embodiment 13 add in the glass still of 2L, stir, Dropwise 5 42g hydrogen peroxide (27.5%), under 30～70 ℃ condition, react 5～10h, after refining, get the hybrid epoxidized fatty acid ester, the oxirane value that detects it is 3.64%.
Embodiment 15
With the product hybrid epoxidized fatty acid ester 1000g among the embodiment 14, add diisopropanolamine (DIPA) 363g again, potassium hydroxide 1.2g, join in the glass still of 2L, stir and heat up 120～180 ℃ of control reaction temperature, reaction times 7～10h, get biopolyol D product 1280g after refining, hydroxyl value is 445mgKOH/g, moisture :≤0.11%.
Embodiment 16
Not refined biological polylol D 851g with among the embodiment 15 joins in the glass still of 2L, stirs to heat up, logical oxyethane 100g and propylene oxide 243g, and 80～120 ℃ of control reaction temperature are behind reaction times 3～6h.Through refining biopolyol product K 1110g, hydroxyl value is 320mgKOH/g, moisture :≤0.10%.
Claims (7)
1. utilize the biopolyol of Jatropha curcas oil preparation, it is characterized in that employing is prepared as follows method and forms: Jatropha curcas oil is added the alcoholysis agent carry out alcoholysis reaction, generate mixed aliphatic ester in the presence of catalyzer; Again mixed aliphatic ester is added epoxidizing agent in the presence of catalyzer and carry out epoxidation reaction, generate the hybrid epoxidized fatty acid ester; With hybrid epoxidized fatty acid ester and ring opening agent generation epoxy bond ring-opening reaction, generate and mix hydroxy fatty acid fat, i.e. biopolyol then;
The temperature of above-mentioned alcoholysis reaction is controlled between 65～240 ℃, 1～16 hour reaction times; The alcoholysis agent is hydramine or alcohol, and its add-on is (2.0～5.7) with the ratio of the mole number of Jatropha curcas oil: 1; Catalyzer is alkali metal hydroxide, alkali-metal alkoxide or organotin, and its weight is 0.005～1.3% of Jatropha curcas oil and alcoholysis agent weight summation;
In the above-mentioned epoxidation reaction, adopt the peroxide organic acid as epoxidizing agent, adopting sulfuric acid or phosphoric acid is catalyzer, and the temperature of epoxidation reaction is controlled at 30～70 ℃, 1～10 hour reaction times;
Above-mentioned ring-opening reaction is the reaction that hybrid epoxidized fatty acid ester and ring opening agent are carried out in the presence of catalyzer, and the temperature of ring-opening reaction is controlled between 65～180 ℃, the reaction times: 1～10 hour; Described ring opening agent is alcohol or hydramine, and its ratio with hybrid epoxidized mixed aliphatic ester epoxy bond mole number is (0.8～1.6): 1; Described catalyzer is alkali metal hydroxide, alkali-metal alkoxide or organic bases, and its weight is 0～1.5% of epoxy mixed aliphatic ester and ring opening agent weight summation.
2. utilize the biopolyol of Jatropha curcas oil preparation according to claim 1, it is characterized in that alcoholysis reaction alcoholysis agent is selected from a Yi Bingchunan, diisopropanolamine (DIPA), tri-isopropanolamine, thanomin, diethanolamine or trolamine when adopting hydramine; The alcoholysis agent is selected from methyl alcohol, ethanol, propyl alcohol, butanols, butyleneglycol, TriMethylolPropane(TMP), glycol ether, triglycol, ethylene glycol, glycerol, propylene glycol, tetramethylolmethane, Xylitol or sorbyl alcohol when adopting alcohol.
3. as utilizing the biopolyol of Jatropha curcas oil preparation as described in the claim 2, it is characterized in that hydramine is selected from tri-isopropanolamine, diisopropanolamine (DIPA), trolamine, diethanolamine, alcohol is selected from propylene glycol, butyleneglycol, glycol ether, triglycol, ethylene glycol or glycerol, TriMethylolPropane(TMP).
4. utilize the biopolyol of Jatropha curcas oil preparation according to claim 1, the catalyzer that it is characterized in that alcoholysis reaction is selected from sodium hydroxide, potassium hydroxide or lithium hydroxide during for alkali metal hydroxide; Catalyzer is selected from sodium methylate, sodium ethylate, potassium methylate when being alkali-metal alkoxide; Catalyzer is selected from stannous octoate, dibutyl tin laurate during for organotin.
5. utilize the biopolyol of Jatropha curcas oil preparation according to claim 1, be selected from a Yi Bingchunan, diisopropanolamine (DIPA), tri-isopropanolamine, thanomin, diethanolamine, trolamine when it is characterized in that ring opening agent for hydramine, ring opening agent is selected from methyl alcohol, ethanol, propyl alcohol, butanols, butyleneglycol, TriMethylolPropane(TMP), glycol ether, triglycol, ethylene glycol, glycerol, propylene glycol, tetramethylolmethane, Xylitol, sorbyl alcohol when being alcohol.
6. as utilizing the biopolyol of Jatropha curcas oil preparation as described in the claim 5, it is characterized in that hydramine is selected from tri-isopropanolamine, diisopropanolamine (DIPA), trolamine, diethanolamine, alcohol is selected from propylene glycol, butyleneglycol, glycol ether, triglycol, ethylene glycol or glycerol, TriMethylolPropane(TMP).
7. utilize the biopolyol of Jatropha curcas oil preparation according to claim 1, it is characterized in that being selected from sodium hydroxide, potassium hydroxide or lithium hydroxide as the alkali metal hydroxide of ring-opening reaction catalyzer; Alkali-metal alkoxide as the ring-opening reaction catalyzer is selected from sodium methylate, sodium ethylate, potassium methylate; Organic bases as the ring-opening reaction catalyzer is selected from dimethylamine, Trimethylamine 99, triethylamine, N, N-dimethylcyclohexylamine or pentamethyl-diethylenetriamine.
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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 |
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| US20090246430A1 (en) | 2008-03-28 | 2009-10-01 | The Coca-Cola Company | Bio-based polyethylene terephthalate polymer and method of making same |
| WO2010101698A2 (en) | 2009-03-03 | 2010-09-10 | The Coca-Cola Company | Bio-based polyethylene terephthalate packaging and method of making thereof |
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| CN106467462A (en) * | 2016-09-20 | 2017-03-01 | 江南大学 | A kind of synthesis technique of branched chain fatty acid methyl ester |
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| CN1837180A (en) * | 2006-04-16 | 2006-09-27 | 南京红宝丽股份有限公司 | Bio-based polyhydric alcohol prepared by using rape seed oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CF01 | Termination of patent right due to non-payment of annual fee |