CN102167808A - Method for preparing bio-based polyether glycol from jatropha curcas oil - Google Patents
Method for preparing bio-based polyether glycol from jatropha curcas oil Download PDFInfo
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- CN102167808A CN102167808A CN 201110054556 CN201110054556A CN102167808A CN 102167808 A CN102167808 A CN 102167808A CN 201110054556 CN201110054556 CN 201110054556 CN 201110054556 A CN201110054556 A CN 201110054556A CN 102167808 A CN102167808 A CN 102167808A
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- cortex jatrophae
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- polyether glycol
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Abstract
The invention discloses a method for preparing bio-based polyether glycol from jatropha curcas oil. The method comprises the following steps of: adding a small molecular alcohol or amine type compound and a catalyst A into the jatropha curcas oil and heating for reaction to prepare modified jatropha curcas oil; reacting the obtained modified jatropha curcas oil and propylene oxide serving as raw materials under the action of a catalyst B to prepare a bio-based polyether glycol crude product; neutralizing the obtained bio-based polyether glycol crude product with acid; and performing dehydration to obtain a bio-based polyether glycol product. In the method, the bio-based polyether glycol is prepared from the jatropha curcas oil serving as the raw material through modification; compared with the conventional polyether glycol, the bio-based polyether glycol has the characteristics of convenience for purchasing of the raw materials, reproducibility and reduced amount of propylene oxide and reduced cost, can meet environmental protection requirements well, and is mainly used for plastic runways, polyurethane glue and polyurethane elastomer.
Description
Technical field
The present invention relates to a kind of preparation method of biological poly ethoxylated polyhydric alcohol.
Background technology
At present elastomeric polyethers all be with glycerine, glycol ether, propylene glycol as initiator, propylene oxide and oxyethane is as chain propagation agent, the inside 98% above petroleum derivative, petroleum resources are Nonrenewable resources, along with expanding economy drains off.Utilize the alternative material of bio-based renewable resources as petroleum resources, minimizing is to the dependence of oil, some materials that past replaces: as: soybean oil, rapeseed oil, palm wet goods all belong to human edible resource, formed the situation of striving oil with the people, and Cortex jatrophae is oily because contain a spot of terpenoid, poisonous can't eating, and also Cortex jatrophae belongs to tropical plants, be fit to Guangxi, Yunnan, a large amount of plantations of Sichuan one band, for a contribution is made in western expanding economy.
The main molecules of vegetables oil consists of the triacylglycerol ester, also has phosphatide, tocopherol and the vitamin-E of small-amount free lipid acid and partial glycerol ester, 0.1-0.5%.In general, the shortcoming of vegetables oil is that it lacks and the necessary reactive hydrogen of isocyanate reaction.Therefore, must introduce in the above plant by the chemical means process reactive hydrogen that polyurethane industrial is required.According to the prior art level, the method that realizes this point is to adopt epoxidation and hydroxylation modification substantially.The method and technology that several preparation vegetable oil-based polyether polyols are arranged at present: (1) feeds propylene oxide after with hydrogen peroxide hydroxyl value vegetables oil, the synthetic vegetables oil rigid-foam polyether polyol that contains; (2) in synthetic plant oil polyether glycol, directly add the synthetic vegetables oil rigid-foam polyether of plam oil; (3) directly with vegetables oil and the synthetic vegetables oil rigid-foam polyether of small molecular alcohol; (4) with hydroxyl value vegetables oil and epoxidized vegetable oil reaction, the synthetic plant oil polyether glycol that contains.
Summary of the invention
The object of the present invention is to provide a kind of renewable, environmental protection, cost low prepare the method for biological poly ethoxylated polyhydric alcohol by Cortex jatrophae oil.
Technical solution of the present invention is:
A kind of by the oily method for preparing the biological poly ethoxylated polyhydric alcohol of Cortex jatrophae, it is characterized in that: comprise the following steps:
(1) small molecular alcohol or aminated compounds and catalyst A are joined reacting by heating in the Cortex jatrophae oil, make modification Cortex jatrophae oil; Catalyst A is basic metal (lithium, sodium, potassium, rubidium, caesium, francium) oxide compound, basic metal (lithium, sodium, potassium, rubidium, caesium, francium) oxyhydroxide, alkaline-earth metal (beryllium, magnesium, calcium, strontium, barium, radium) oxide compound, alkaline earth metal hydroxides, metal halide or aluminum oxide;
(2) be raw material with step (1) resulting modification Cortex jatrophae oil and propylene oxide, reaction makes biological poly ethoxylated polyhydric alcohol crude product under the catalyst B effect; Catalyst B is basic metal (lithium, sodium, potassium, rubidium, caesium, francium) oxide compound, basic metal (lithium, sodium, potassium, rubidium, caesium, francium) oxyhydroxide, alkaline-earth metal (beryllium, magnesium, calcium, strontium, barium, radium) oxide compound, alkaline earth metal hydroxides, metal halide or aluminum oxide;
(3) the biological poly ethoxylated polyhydric alcohol crude product that step (2) is obtained neutralizes with acid, carries out processed again, obtains biological poly ethoxylated polyhydric alcohol product.
Small molecular alcohol is ethylene glycol, propylene glycol, glycol ether, glycerine, tetramethylolmethane, a Virahol, diisopropanol or three Virahols; Aminated compounds is thanomin, diethanolamine, trolamine or alkyl ethanol amine.
The mol ratio of small molecular alcohol or aminated compounds and Cortex jatrophae oil is in the step (1): 1:1.0-4.0, temperature of reaction is 100-200 ℃.
The consumption of catalyst A is the 0.2-2.0% of reactant weight in the step (1); The consumption of catalyst B is the 0.1-1.0% of reactant weight in the step (2).
In carrying out with acid in the step (3) and the time, used acid is phosphoric acid or tetra-sodium, is neutralized to pH=5.5 ~ 7.5; The processed temperature is 90-120 ℃, and dewatering time is 60-150 minute.
The present invention adopts Cortex jatrophae oil to obtain the biological poly ethoxylated polyhydric alcohol for raw material by modification, this biological poly ethoxylated polyhydric alcohol and polyether glycol ratio in the past, having raw material buys conveniently, renewable, reduce the consumption of propylene oxide, the characteristics that reduce cost can satisfy environmental requirement better, and main application is plastic cement race track, polyurethane glue and polyurethane elastomer.
Embodiment
Embodiment 1:
In the glass still of 2L, add Cortex jatrophae 1000g, 180 glycol ethers, 4g sodium hydroxide stirs and is warming up to 170 degree, reacts 3 hours, detects hydroxyl value, and blowing records modification Cortex jatrophae oil A hydroxyl value: 112mgKOH/g.
A:520g adds in the autoclave with modification Cortex jatrophae oil, 2.5g catalyzer, vacuum is to the highest, and nitrogen replacement twice feeds the PO/EO(9.4/0.6 of 1000g) mixture (is the mixture of propylene oxide and oxyethane, the weight ratio of propylene oxide and oxyethane is 9.4:0.6), reaction times 2-4 hour, make with extra care (with acid neutralization and dehydration, during acid is carried out and the time, used acid is phosphoric acid or tetra-sodium, is neutralized to pH=7; The processed temperature is 100 ℃, and dewatering time is 100 minutes), obtaining hydroxyl value is the biological poly ethoxylated polyhydric alcohol of 36.4mgKOH/g.
Embodiment 2:
In the glass still of 2L, add Cortex jatrophae 1000g, 140 tetramethylolmethanes, 4g sodium hydroxide stirs and is warming up to 170 degree, reacts 3 hours, detects hydroxyl value, and blowing records modification Cortex jatrophae oil B hydroxyl value: 180mgKOH/g.
B:200g adds in the autoclave with modification Cortex jatrophae oil, 2.5g catalyzer, vacuum is to the highest, nitrogen replacement twice, the PO/EO(9.4/0.6 of feeding 1000g) mixture, reaction times 2-4 hour, make with extra care (with acid neutralization and dehydration, during acid is carried out and the time, used acid is phosphoric acid or tetra-sodium, is neutralized to pH=6; The processed temperature is 90 ℃, and dewatering time is 140 minutes), obtaining hydroxyl value is the biological poly ethoxylated polyhydric alcohol of 41.2mgKOH/g.
Embodiment 3:
In the glass still of 2L, add Cortex jatrophae 1000g, 160 trolamines, 4g sodium hydroxide stirs and is warming up to 170 degree, reacts 3 hours, detects hydroxyl value, and blowing records modification Cortex jatrophae oil C hydroxyl value: 201mgKOH/g.
C:210g adds in the autoclave with modification Cortex jatrophae oil, 2.5g catalyzer, vacuum is to the highest, nitrogen replacement twice, the PO mixture of feeding 800g, reaction times 2-4 hour, make with extra care (with acid neutralization and dehydration, during acid is carried out and the time, used acid is phosphoric acid or tetra-sodium, is neutralized to pH=5.5; The processed temperature is 120 ℃, and dewatering time is 60 minutes), obtaining hydroxyl value is 58.7mgKOH/g, viscosity 590mPas/25 ℃ biological poly ethoxylated polyhydric alcohol.
Embodiment 4:
A kind of by the oily method for preparing the biological poly ethoxylated polyhydric alcohol of Cortex jatrophae, it is characterized in that: comprise the following steps:
(1) small molecular alcohol or aminated compounds and catalyst A are joined reacting by heating in the Cortex jatrophae oil, make modified vegetable oil; Catalyst A is basic metal (lithium, sodium, potassium, rubidium, caesium, francium) oxide compound, basic metal (lithium, sodium, potassium, rubidium, caesium, francium) oxyhydroxide, alkaline-earth metal (beryllium, magnesium, calcium, strontium, barium, radium) oxide compound, alkaline earth metal hydroxides, metal halide or aluminum oxide;
(2) be raw material with step (1) resulting modification Cortex jatrophae oil and propylene oxide, reaction makes biological poly ethoxylated polyhydric alcohol crude product under the catalyst B effect; Catalyst B is alkalimetal oxide, alkali metal hydroxide, alkaline earth metal oxide, alkaline earth metal hydroxides, metal halide or aluminum oxide;
(3) the biological poly ethoxylated polyhydric alcohol crude product that step (2) is obtained neutralizes with acid, is carrying out processed, obtains biological poly ethoxylated polyhydric alcohol product;
Small molecular alcohol is ethylene glycol, propylene glycol, glycol ether, glycerine, tetramethylolmethane, a Virahol, diisopropanol or three Virahols; Aminated compounds is thanomin, diethanolamine, trolamine or alkyl ethanol amine.
The mol ratio of small molecular alcohol or aminated compounds and Cortex jatrophae oil is in the step (1): 1:1.0-4.0, temperature of reaction is 100-200 ℃.
The consumption of catalyst A is the 0.2-2.0% of reactant weight in the step (1); The consumption of catalyst B is the 0.1-1.0% of reactant weight in the step (2).All the other are with embodiment 1.
Claims (5)
1. one kind prepares the method for biological poly ethoxylated polyhydric alcohol by Cortex jatrophae oil, it is characterized in that: comprise the following steps:
(1) small molecular alcohol or aminated compounds and catalyst A are joined reacting by heating in the Cortex jatrophae oil, make modification Cortex jatrophae oil; Catalyst A is alkalimetal oxide, alkali metal hydroxide, alkaline earth metal oxide, alkaline earth metal hydroxides, metal halide or aluminum oxide;
(2) be raw material with step (1) resulting modification Cortex jatrophae oil and propylene oxide, reaction makes biological poly ethoxylated polyhydric alcohol crude product under the catalyst B effect; Catalyst B is alkalimetal oxide, alkali metal hydroxide, alkaline earth metal oxide, alkaline earth metal hydroxides, metal halide or aluminum oxide;
(3) the biological poly ethoxylated polyhydric alcohol crude product that step (2) is obtained neutralizes with acid, carries out processed again, obtains biological poly ethoxylated polyhydric alcohol product.
2. according to claim 1 by the oily method for preparing the biological poly ethoxylated polyhydric alcohol of Cortex jatrophae, it is characterized in that: small molecular alcohol is ethylene glycol, propylene glycol, glycol ether, glycerine, tetramethylolmethane, a Virahol, diisopropanol or three Virahols; Aminated compounds is thanomin, diethanolamine, trolamine or alkyl ethanol amine.
3. according to claim 1 and 2 by the oily method for preparing the biological poly ethoxylated polyhydric alcohol of Cortex jatrophae, it is characterized in that: the mol ratio of small molecular alcohol or aminated compounds and Cortex jatrophae oil is in the step (1): 1:1.0-4.0, temperature of reaction is 100-200 ℃.
4. according to claim 1 and 2 by the oily method for preparing the biological poly ethoxylated polyhydric alcohol of Cortex jatrophae, it is characterized in that: the consumption of catalyst A is the 0.2-2.0% of reactant weight in the step (1); The consumption of catalyst B is the 0.1-1.0% of reactant weight in the step (2).
5. according to claim 1 and 2ly prepare the method for biological poly ethoxylated polyhydric alcohol, it is characterized in that by Cortex jatrophae oil: in carrying out with acid in the step (3) and the time, used acid is phosphoric acid or tetra-sodium, is neutralized to pH=5.5 ~ 7.5; The processed temperature is 90-120 ℃, and dewatering time is 60-150 minute.
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| CN 201110054556 CN102167808A (en) | 2011-03-08 | 2011-03-08 | Method for preparing bio-based polyether glycol from jatropha curcas oil |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106366288A (en) * | 2016-08-27 | 2017-02-01 | 惠州市腾威新材料有限公司 | Novel environmental-friendly runway material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353422A (en) * | 2008-09-05 | 2009-01-28 | 绍兴市恒丰聚氨酯实业有限公司 | Synthetic method of polyether polyatomic alcohol |
| CN101805258A (en) * | 2010-03-18 | 2010-08-18 | 广东万华容威聚氨酯有限公司 | Preparation method of novel vegetable oil polyol for polyurethane rigid foam |
| CN102250304A (en) * | 2010-05-21 | 2011-11-23 | 江苏绿源新材料有限公司 | Method for preparing polyurethane foam from curcas oil base rigid foam polyether |
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- 2011-03-08 CN CN 201110054556 patent/CN102167808A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353422A (en) * | 2008-09-05 | 2009-01-28 | 绍兴市恒丰聚氨酯实业有限公司 | Synthetic method of polyether polyatomic alcohol |
| CN101805258A (en) * | 2010-03-18 | 2010-08-18 | 广东万华容威聚氨酯有限公司 | Preparation method of novel vegetable oil polyol for polyurethane rigid foam |
| CN102250304A (en) * | 2010-05-21 | 2011-11-23 | 江苏绿源新材料有限公司 | Method for preparing polyurethane foam from curcas oil base rigid foam polyether |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106366288A (en) * | 2016-08-27 | 2017-02-01 | 惠州市腾威新材料有限公司 | Novel environmental-friendly runway material and preparation method thereof |
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Application publication date: 20110831 |