CN100465152C - Organism-based polyol preparing by epoxy rapeseed oil - Google Patents
Organism-based polyol preparing by epoxy rapeseed oil Download PDFInfo
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- CN100465152C CN100465152C CNB2006100413809A CN200610041380A CN100465152C CN 100465152 C CN100465152 C CN 100465152C CN B2006100413809 A CNB2006100413809 A CN B2006100413809A CN 200610041380 A CN200610041380 A CN 200610041380A CN 100465152 C CN100465152 C CN 100465152C
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Abstract
The invention involves a bio-polyol prepared from epoxy rapeseed oil. The preparation method comprises: carrying out ring-opening reaction of epoxy rapeseed oil with an active hydrogen-bearing nucleophilic reagent at the presence of catalyst to obtain the mixed hydroxyl fatty acid triglyceride, and adding alcoholysis agent of alcohols or alkanolamine and heating for alcoholysis reaction to obtain mixed hydroxyl fatty acid monoester, i.e. biological-based polyol. The invention has the advantages of epoxy rapeseed oil being cheap and easy to get or self-design, reduction of dependence on petrochemical products, strong functions and high adjustability, and production of different functionality and pre-designed hydroxyl values of the bio-polyol according to requirements.
Description
Technical field
The present invention relates to a kind of method that adopts epoxy rapeseed oil to prepare biopolyol; it is by epoxy bond open loop in the epoxy rapeseed oil; acyl group and alcohol radical carry out transesterification reaction in the glyceryl ester; prepare and mix the hydroxy aliphatic acid monoester; abbreviate biopolyol as, belong to technical field of organic synthesis.
Background technology
Along with the fast development of global economy, all polyvalent alcohol demands of the whole world are in quick growth.Used in the past polyvalent alcohol mainly contains three classes, 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 P0P as), and normal and PPG is used; The third is the polyvalent alcohol by tetrahydrofuran ring opening polymerization.These products all are the derived product of oil, because the shortage 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.
Current, along with the mankind more and more pay close attention to environment, petroleum resources non-renewable reduces the dependency to petroleum chemicals, seeks new raw material, produces green, environmental protection, economy, gentle polyvalent alcohol, become an important directions of polyvalent alcohol development.At present, the epoxy rapeseed oil of reproducible rapeseed oil preparation is studied as softening agent, is applied to the urethane industry and prepare biopolyol with epoxy rapeseed oil, still finds no pass report in this respect.
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, adopts epoxy rapeseed oil to carry out the open loop alcoholysis and prepares biopolyol.
Epoxy is strong because triangle tension force in the epoxy rapeseed oil, unstable, ring-opening reaction easily takes place, obtain high functionality, high-molecular weight mixed hydroxyl fatty acid triglyceride, it is carried out alcoholysis reaction, obtain the oxy-compound of low-molecular-weight polyfunctionality, these oxy-compound are biopolyol, can directly be used for preparing polyurethane foam.
The present invention adopts following technical scheme:
Under the catalyzer existence condition, epoxy rapeseed oil and the hydrogen donor nucleophilic reagent that contains reactive hydrogen are reacted, generate mixed hydroxyl fatty acid triglyceride; After this add alcohol or hydramine and under comparatively high temps, carry out alcoholysis reaction, generate and mix hydroxy aliphatic acid monoester, i.e. biopolyol.
Above-mentioned biopolyol obtains the purified biopolyol after refining.
The present invention is this, and to be the polyvalent alcohol of raw material after by deep processing with the epoxy rapeseed oil compare with polyvalent alcohol in the past, it is strong to have the functionality controllability, narrow molecular weight distribution, the reactive behavior height is without olefin oxide, minimizing is to the characteristics such as dependence of petroleum chemicals, simultaneously raw material have cheap and easy to get, can homemade characteristics, in addition, the rapeseed oil that is used to prepare epoxy rapeseed oil is reproducible natural product, is to optimize ecological Green Product with the biopolyol of epoxy rapeseed oil preparation.Simultaneously to have a collectivity strong for technology of the present invention, and environmental pollution is little, and the product yield is advantage of higher also.
Chemical principle of the present invention is as follows:
1, ring-opening reaction:
Here R ' H refers to alcohol, hydramine.
2, alcoholysis reaction (carrying out alcoholysis with the adding glycerol is example):
Here, R " OH refers to glycerol.
In the above-mentioned ring-opening reaction, temperature is controlled between 65～200 ℃, 1～12 hour reaction times.
The catalyzer of ring-opening reaction and alcoholysis reaction is basic catalyst, be 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.; Or 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.
The weight of catalyzer is 0.05～0.9% of epoxy rapeseed oil and nucleophilic reagent weight summation in the ring-opening reaction.
In the ring-opening reaction with alcohol that reactive hydrogen atom can be provided, hydramine as nucleophilic reagent, adoptable nucleophilic reagent mainly contains alcohol, hydramine.The nucleophilic reagent consumption is calculating according to the oxirane value of epoxy rapeseed oil, its calculation formula is nucleophilic reagent consumption=coefficient * (mole/16 of the oxirane value * nucleophilic reagent of epoxy rapeseed oil) * (actual amount of epoxy rapeseed oil/100), and coefficient is 1.0～1.3 here.
Alcohol in the ring-opening reaction is selected from methyl alcohol, ethanol, propyl alcohol, butanols, butyleneglycol, 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.
Above-mentioned hydramine is selected from a Yi Bingchunan, diisopropanolamine (DIPA), tri-isopropanolamine, thanomin, diethanolamine, trolamine, alkyl alkanolamine, benzyl alkanolamine 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 70～240 ℃, and be reflected under the normal pressure early stage carries out, and the reaction times is 3～6 hours, and the later stage under reduced pressure reacts, and vacuum tightness is 100～750kPa, and the reaction times is 3～7 hours.
Alcohol as the alcoholysis agent in the alcoholysis reaction is selected from methyl alcohol, ethanol, propyl alcohol, butanols, 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 tri-isopropanolamine and trolamine, methyldiethanolamine, methyl diisopropanolamine (DIPA).
The alcoholysis agent add-on of alcoholysis reaction with the mol ratio of mixing the hydroxy aliphatic acid glyceride is: (2.0～3.8): 1.
The catalyzer of alcoholysis reaction can be selected identical catalyzer for use with ring-opening reaction, also available different catalyzer.
Alcoholysis reaction will be added catalyzer, the amount of adding catalyzer be in the whole system total mass 0.01%～2%.
The mixing hydroxy fatty acid monoester that mixed hydroxyl fatty acid triglyceride generates after alcoholysis reaction is directly made biopolyol and is used, and its process for purification is as follows:
Adopt acidic substance that basic catalyst is carried out neutralizing treatment, add sorbent material then and adsorb, after dehydration, filter and promptly obtain the purified biopolyol.
Adoptable acid is for providing H
+Acid, comprising: phosphoric acid, tetra-sodium, sulfuric acid, oxalic acid, hydrochloric acid etc., the mol ratio of its consumption and basic catalyst consumption is 1:(1.0～1.05).Preferably phosphoric acid and hydrochloric acid, more preferably phosphoric acid.
Adoptable sorbent material is the material with adsorption function, as diatomite, atlapulgite, pure aluminium silicate, Magnesium Silicate q-agent, activated carbon etc., and 0.08～3.00% of the refining thing of its used in amounts.
Temperature is 80～120 ℃ during dehydration, and vacuum tightness is 100～750KPa during dehydration, and dewatering time is 60～150min.
Filtration temperature is: 80～120 ℃, filter pressure is 1.5～3kg/cm
2
Adopt this technology to have the following advantages:
1. epoxy rapeseed oil is cheap and easy to get, can make by oneself simultaneously.
2. reduced dependence to petroleum chemicals.
3. product is functional strong, the controllability height.
4. can produce the biopolyol of different functionality and pre-design hydroxyl value as required.
Embodiment
Embodiment 1
Epoxy rapeseed oil 1000g joins in the glass still of 2L, adds glycol ether 420g again, and potassium hydroxide 4.9g stirs and heats up 65～200 ℃ of control reaction temperature, 1～12 hour reaction times.Add glycerol 211g, glycerine potassium alcoholate 4g, 70～240 ℃ of controlled temperature down for 65～100 ℃ in temperature then, carried out alcoholysis reaction 3～6 hours, the back kept 3～7 hours under vacuum tightness is the situation of 100～750kPa, back sampling analysis, and hydroxyl value is the crude product of 476mgKOH/g.After make with extra care, concrete grammar is as follows: add 50% phosphatase 11 8g carry out in and 15 minutes, add Magnesium Silicate q-agent 3g and adsorb, the back is under the temperature of 100～750KPa and 80～120 ℃ in vacuum tightness, dewatered 60 minutes, and after the filtration, got product 1540g purified biopolyol.
Embodiment 2
Epoxy rapeseed oil 1000g joins in the glass still of 2L, adds propylene glycol 332g again, and potassium hydroxide 5g stirs and heats up 65～200 ℃ of control reaction temperature, 1～12 hour reaction times.65～100 ℃ of temperature, add TriMethylolPropane(TMP) 308g, potassium hydroxide 1.1g then, 70～240 ℃ of controlled temperature carried out alcoholysis reaction 3～6 hours, and the back kept 3～7 hours under vacuum tightness is the situation of 100～750kPa, back sampling analysis, hydroxyl value are the crude product of 470mgKOH/g.After make with extra care, concrete grammar is as follows: add 50% phosphoric acid 20g carry out in and 15 minutes, add Magnesium Silicate q-agent 3.2g and adsorb, the back is under the temperature of 100～750KPa and 80～120 ℃ in vacuum tightness, dewatered 60 minutes, and after the filtration, got product 1550g purified biopolyol.
Embodiment 3
Epoxy rapeseed oil 1000g adds in the glass still of 2L, and adds ethanol 180g, and 10% ethanol potassium alcoholate 38g stirs and heats up 65～200 ℃ of control reaction temperature, 1～12 hour reaction times.65～100 ℃ of temperature, add tri-isopropanolamine 440g then, 10% ethanol potassium alcoholate 14g, 70～240 ℃ of controlled temperature carried out alcoholysis reaction 3～6 hours,
The back is 100～750kPa in vacuum tightnessSituation under kept 3～7 hours, cooling to 70～80 ℃ makes with extra care, and body method is as follows: add 50% phosphatase 11 7g carry out in and 20 minutes, adding atlapulgite 15g adsorbs, the back is under the temperature of 100～750KPa and 80～120 ℃, to dewater 60 minutes, after the filtration in vacuum tightness, get product 1570g purified biopolyol, hydroxyl value is 330mgKOH/g.
Embodiment 4
Epoxy rapeseed oil 1000g adds in the glass still of 2L, and adds trolamine 665g, and potassium hydroxide 2.3g stirs and heats up 65～200 ℃ of control reaction temperature, 1～12 hour reaction times.Then 65～100 ℃ of temperature, add propylene glycol 175g, 16% propylene glycol potassium 5.5g, be warming up to 70～240 ℃ gradually, carried out alcoholysis reaction 3～6 hours, the back kept 3～7 hours under vacuum tightness is the situation of 100～750kPa, make with extra care after cooling to 70 ℃, concrete grammar is as follows: add 50% phosphatase 79 g carry out in and 20 minutes, add Magnesium Silicate q-agent 2g, pure aluminium silicate 2g adsorbs, the back is under the temperature of 100～750KPa and 80～120 ℃, to dewater 60 minutes, after the filtration in vacuum tightness, get 1755g purified biopolyol, hydroxyl value is 465mgKOH/g.
Embodiment 5
Epoxy rapeseed oil 1000g adds in the glass still of 2L, and adds diisopropanolamine (DIPA) 594g, and sodium hydroxide 1.65g stirs and heats up 65～200 ℃ of control reaction temperature, 1～12 hour reaction times.Then 65～100 ℃ of temperature, add ethylene glycol 120g, sodium hydroxide 0.5g, be warming up to 70～240 ℃ gradually, carried out alcoholysis reaction 3～6 hours, the back kept 3～7 hours under vacuum tightness is the situation of 100～750kPa, make with extra care after cooling to 70 ℃, concrete grammar is as follows: add 50% phosphatase 11 0.5g carry out in and 20 minutes, add Magnesium Silicate q-agent 2g, pure aluminium silicate 2g adsorbs, the back is under the temperature of 100～750KPa and 80～120 ℃, to dewater 60 minutes, after the filtration in vacuum tightness, get 1630g purified biopolyol, hydroxyl value is 495mgKOH/g.
Embodiment 6
Epoxy rapeseed oil 1000g adds in the glass still of 2L, and adds tetramethylolmethane 136g, butanols 225g, and 10% butanols potassium alcoholate 30g stirs and heats up 65～200 ℃ of control reaction temperature, 1～12 hour reaction times.Then 65～100 ℃ of temperature, add and glycerol 220g, 16% glycerine potassium alcoholate 6.8g, be warming up to 70～240 ℃ gradually, carried out alcoholysis reaction 3～6 hours, the back kept 3～7 hours under vacuum tightness is the situation of 100～750kPa, make with extra care after cooling to 70 ℃, concrete grammar is as follows: add 50% phosphatase 11 0.5g carry out in and 20 minutes, add diatomite 10g, pure aluminium silicate 2g adsorbs, the back is under the temperature of 100～750KPa and 80～120 ℃, to dewater 60 minutes, after the filtration in vacuum tightness, get 1550g purified biopolyol, hydroxyl value is 456mgKOH/g.
Claims (13)
1, a kind of biopolyol that adopts the epoxy rapeseed oil preparation, it is characterized in that being prepared from: under the catalyzer existence condition,, generate mixed hydroxyl fatty acid triglyceride with epoxy rapeseed oil and the nucleophilic reagent generation epoxy bond ring-opening reaction that contains reactive hydrogen by following method; After this add the intensification of alcoholysis agent alcohol or hydramine and carry out alcoholysis reaction, generate and mix hydroxy aliphatic acid monoester, i.e. biopolyol.
2, according to the biopolyol of the described employing epoxy rapeseed oil preparation of claim 1, it is characterized in that the ring-opening reaction temperature is controlled between 65～200 ℃, 1～12 hour reaction times.
3, according to the biopolyol of the described employing epoxy rapeseed oil preparation of claim 1, it is characterized in that the catalyzer of ring-opening reaction and alcoholysis reaction is basic catalyst, be selected from the alkoxide of metal hydroxides or metal; The weight of catalyzer is 0.05～0.9% of epoxy rapeseed oil and nucleophilic reagent weight summation in the ring-opening reaction; Catalyst consumption to be added 0.01%～2% of to the whole system total amount during alcoholysis reaction; Alcoholysis reaction and ring-opening reaction can be with identical catalyzer, also available different catalyzer.
4, the biopolyol for preparing according to the described employing epoxy rapeseed oil of claim 3, the catalyzer that it is characterized in that ring-opening reaction and alcoholysis reaction is alkali metal hydroxide or alkali-metal alkoxide, and the aforementioned bases metal hydroxides is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide; Alkali-metal alkoxide is selected from sodium methylate, sodium ethylate, potassium methylate, glycerine potassium alcoholate.
5, according to the biopolyol of the described employing epoxy rapeseed oil of claim 1 preparation, the nucleophilic reagent that it is characterized in that in the ring-opening reaction being adopted is selected from alcohol or hydramine; The nucleophilic reagent mole dosage is 1.0～1.3 times of oxirane value of epoxy rapeseed oil.
6, the biopolyol for preparing according to the described employing epoxy rapeseed oil of claim 4, it is characterized in that the alcohol as nucleophilic reagent is selected from methyl alcohol, ethanol, propyl alcohol, butanols, butyleneglycol, 1,4-butyleneglycol, glycol ether, triglycol, ethylene glycol, glycerol, propylene glycol, tetramethylolmethane, Xylitol, sorbyl alcohol, TriMethylolPropane(TMP) in the ring-opening reaction;
Hydramine as nucleophilic reagent is selected from a Yi Bingchunan, diisopropanolamine (DIPA), tri-isopropanolamine, thanomin, diethanolamine, trolamine, alkyl alkanolamine, benzyl alkanolamine.
7, according to the biopolyol of the described employing epoxy rapeseed oil preparation of claim 6, it is characterized in that the alcohol as nucleophilic reagent is selected from propylene glycol, butyleneglycol, glycol ether, triglycol, ethylene glycol or glycerol, TriMethylolPropane(TMP) in the ring-opening reaction; Be selected from tri-isopropanolamine or trolamine, methyldiethanolamine, methyl diisopropanolamine (DIPA) as the hydramine of nucleophilic reagent.
8, the biopolyol for preparing according to the described employing epoxy rapeseed oil of claim 1, the temperature that it is characterized in that alcoholysis reaction is 70～240 ℃, carry out the early stage that alcoholysis reaction begins under normal pressure, reaction times is 3～6 hours, the alcoholysis later stage carries out under vacuum tightness, vacuum tightness is 100～750kPa, and the reaction times is 3～7 hours.
9, the biopolyol for preparing according to the described employing epoxy rapeseed oil of claim 1, the alcoholysis agent that it is characterized in that alcoholysis reaction is selected from methyl alcohol, ethanol, propyl alcohol, butanols, 1,4-butyleneglycol, glycol ether, triglycol, ethylene glycol, glycerol, propylene glycol, tetramethylolmethane, Xylitol, sorbyl alcohol when being pure;
The alcoholysis agent is selected from a Yi Bingchunan, diisopropanolamine (DIPA), tri-isopropanolamine, thanomin, diethanolamine, trolamine, alkyl alkanolamine, benzyl alkanolamine during for hydramine.
10, according to the biopolyol of the described employing epoxy rapeseed oil preparation of claim 1, the alcoholysis agent that it is characterized in that alcoholysis reaction is selected from propylene glycol, butyleneglycol, glycol ether, triglycol, ethylene glycol or glycerol, TriMethylolPropane(TMP) when being pure; The alcoholysis agent is selected from tri-isopropanolamine or trolamine, methyldiethanolamine, methyl diisopropanolamine (DIPA) during for hydramine.
11, according to the biopolyol of claim 1 or 9 or 10 described employing epoxy rapeseed oil preparations, it is characterized in that the alcoholysis agent add-on of alcoholysis reaction with the mol ratio of mixing the hydroxy aliphatic acid glyceride is: 2.0～3.8:1.
12, the process for purification of the biopolyol of the described employing epoxy rapeseed oil preparation of claim 1 to 11, it is characterized in that adopting acidic substance that alkaline catalysts is carried out neutralizing treatment, add sorbent material then and adsorb, after can obtain the purified biopolyol after dewatering, filtering.
13, according to the described process for purification of claim 12, it is characterized in that described acidic substance are selected from can provide H
+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; Described sorbent material is selected from diatomite, atlapulgite, pure aluminium silicate, Magnesium Silicate q-agent, the activated carbon with adsorption function, and the consumption of sorbent material is not make with extra care 0.08～3.00% of thing; Dehydration and filtration temperature are: 80～120 ℃, dehydration vacuum tightness is 100～750KPa, and dewatering time 60～150min, filter pressure are 1.5～3kg/cm
2
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Cited By (2)
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| US10766841B2 (en) | 2018-11-13 | 2020-09-08 | Cpc Corporation | Method of preparing bio-polyols from epoxidized fatty acid esters |
| EP4053111A1 (en) | 2021-03-01 | 2022-09-07 | Komagra Spólka Z O.O. | The method of producing epoxidised rapeseed oil and method of producing biopolyol using epoxidised rapeseed oil |
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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 |
| CN102212043B (en) * | 2011-03-25 | 2013-04-24 | 湖北大学 | Preparation method of morpholine-based vegetable oil polyol |
| CN104326911B (en) * | 2014-09-16 | 2016-06-15 | 浙江恒丰新材料有限公司 | A kind of waste grease prepares method and the application of polyhydric alcohol |
| CN104311420B (en) * | 2014-09-16 | 2016-01-20 | 浙江恒丰新材料有限公司 | Bio oil one kettle way prepares method and the application of polyvalent alcohol |
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| CN113354863B (en) * | 2021-07-08 | 2023-05-26 | 山东东特环保科技有限公司 | Degradation method of waste polyurethane and polyurethane heat-insulating material |
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| CN1293678A (en) * | 1998-03-23 | 2001-05-02 | 宝洁公司 | Synthesis of higher polyol fatty acid polyesters by transesterification |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1293678A (en) * | 1998-03-23 | 2001-05-02 | 宝洁公司 | Synthesis of higher polyol fatty acid polyesters by transesterification |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10766841B2 (en) | 2018-11-13 | 2020-09-08 | Cpc Corporation | Method of preparing bio-polyols from epoxidized fatty acid esters |
| EP4053111A1 (en) | 2021-03-01 | 2022-09-07 | Komagra Spólka Z O.O. | The method of producing epoxidised rapeseed oil and method of producing biopolyol using epoxidised rapeseed oil |
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