CN1837180A - Bio-based polyhydric alcohol prepared by using rape seed oil - Google Patents
Bio-based polyhydric alcohol prepared by using rape seed oil Download PDFInfo
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- CN1837180A CN1837180A CN 200610039780 CN200610039780A CN1837180A CN 1837180 A CN1837180 A CN 1837180A CN 200610039780 CN200610039780 CN 200610039780 CN 200610039780 A CN200610039780 A CN 200610039780A CN 1837180 A CN1837180 A CN 1837180A
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Abstract
The invention discloses a rape oil preparing biological radical polyatomic alcohol, which comprises the following steps: carrying on alcoholysis reaction with rape oil alcohol and accelerant; generating mixed unsaturated fatty acid monoesters; adding in epoxidation agent to proceed epoxidation reaction; getting mixed epoxy aliphatic acid monoesters-biological radical polyatomic alcohol. The invention has high reaction active, which is convenience to prepare high-functionality product.
Description
Technical field
The present invention relates to a kind of biopolyol that utilizes the rapeseed oil preparation, it is by alcoholysis reaction is taken place for rapeseed oil and alcohol, generate and mix the unsaturated fatty acids acid monoester, epoxidation is carried out to unsaturated double-bond in the back, again with the epoxy bond open loop, prepare and mix the hydroxy aliphatic acid monoester, abbreviate biopolyol as, 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.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 POP 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, the mankind more and more pay close attention to environment, wish to reduce the dependency to oil simultaneously, and green, environmental protection, economy, gentle polyvalent alcohol are developed, and have become the important directions that polyvalent alcohol is developed.Based on this, people carry out relevant Products Development research with the natural resources of chemical research directional steering reproducible utilization.
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, comes the synthesising biological polylol then adopt vegetables oil to carry out the technology deep processing.
Rapeseed oil is a kind of reproducible resource in the vegetables oil, it belongs to undersaturated mixed fatty acid, major ingredient is an oleic acid, linolic acid, linolenic acid, arachidonic acid, erucic acid, two key activity in the molecular structure are higher, under certain conditions can be by transesterify, epoxidation, open loop series deep processing operation, obtain the oxy-compound of polyfunctionality, these oxy-compound can be used as finished product and use, directly be used for preparing hard polyurethane foam or semihard bubble, the oxy-compound that also can be used as intermediate and olefin oxide continuation reaction generation higher molecular weight is 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:
Rapeseed oil in the presence of catalyzer, is added alcohol and carries out alcoholysis reaction, generate and mix the unsaturated fatty acids acid monoester; Add epoxidizing agent again and carry out epoxidation reaction, generate mixed epoxidized fatty acid monoester; With aforementioned mixed epoxidized fatty acid monoester and the nucleophilic reagent generation epoxy bond ring-opening reaction that contains reactive hydrogen, generate and mix hydroxy aliphatic acid monoester, i.e. biopolyol then.
Aforementioned biopolyol and olefin oxide carry out addition reaction, can generate the biopolyol of higher molecular weight.
More than two kinds of polyvalent alcohols all are target products of the present invention.
Aforementioned two kinds of polyvalent alcohols obtain the purified biopolyol after refining.
The present invention is this, and to be raw material with the rapeseed oil compare with the polyvalent alcohol of petrochemical material preparation by the polyvalent alcohol after adding deeply, and it is strong to have the functionality controllability, narrow molecular weight distribution, and the reactive behavior height can prepare the products characteristics of high functionality easily.The while raw material has cheap and easy to get, buys convenient, reproducible characteristics, is to optimize ecological Green Product.Simultaneously, production technique environmental pollution of the present invention is little, and the product yield is also higher.
The following chemical principle of the present invention's foundation:
1, alcoholysis reaction (alcohol is example with the glycerol):
Wherein: R ' OH represents glycerol
2, epoxidation reaction:
Here R ' comprise-H ,-CH
3,-C
6H
5,-CH
3(CH
2)
nC
6H
5
3, ring-opening reaction
Here, R '-H refers to nucleophilic reagent.Alcohol as claimed in claim, hydramine, acid.
The catalyzer of alcoholysis reaction of the present invention and ring-opening reaction is a basic catalyst, be selected from metal hydroxides or metal alkoxide conduct, preferred employing alkali metal hydroxide or alkali metal alkoxide are as the catalyzer of alcoholysis reaction and ring-opening reaction, and 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, glycerol potassium dewaters with oxyhydroxide.
In the above-mentioned alcoholysis reaction, temperature is controlled between 70～240 ℃, synthesis under normal pressure when react to early stage, and the vacuum tightness of late phase reaction is 100～750KPa, 3～15 hours reaction times.
The weight of catalyzer is 0.01～0.8% of rapeseed oil and pure weight summation in the alcoholysis reaction.
The middle alcohol of alcoholysis reaction can adopt one of following alcohol or their optional several mixtures:
Monohydroxy-alcohol: methyl alcohol, ethanol, propyl alcohol, butanols etc.
Dibasic alcohol: 1,4-butyleneglycol, glycol ether, triglycol, ethylene glycol, propylene glycol etc.;
Trivalent alcohol: glycerol, TriMethylolPropane(TMP);
Tetravalent alcohol: tetramethylolmethane, methylglucoside;
Hexavalent alcohol: sorbyl alcohol, N.F,USP MANNITOL;
Dibasic alcohol or glycerol or TriMethylolPropane(TMP)s such as preferred propylene glycol, butyleneglycol, glycol ether, triglycol, ethylene glycol.
In the alcoholysis reaction, the consumption of alcohol and the mole ratio of rapeseed oil are (2.0～3.6): 1.
In the above-mentioned epoxidation reaction, temperature is controlled between 30～70 ℃, 2.5～12 hours reaction times.
In the epoxidation reaction, adopt the peroxide organic acid as epoxidizing agent, the carrying out of epoxidation reaction can be adopted following two kinds of methods:
First kind is directly to adopt the peroxide organic acid and mix the unsaturated fatty acids acid monoester and react, and generates target product; Second method is to adopt hydrogen peroxide as oxygenant, and organic acid adopts sulfuric acid or acidic white earth or organic acid as catalyzer as the precursor of transition oxygenant, and H is provided
+Effect, accelerate the peroxide organic acid and generate, after make the peroxide organic acid and mix the unsaturated fatty acids acid monoester and carry out epoxidation reaction, the generation target product;
In the epoxidation reaction, the peroxide organic acid comprises: peroxyformic acid, Peracetic Acid, benzoyl hydroperoxide, cross the oxyalkyl para Toluic Acid, peroxide organic acid mole dosage is to mix 1.0～1.2 times of unsaturated double-bond value of unsaturated fatty acids acid monoester.Adopt in the second method, the organic acid that is adopted comprises formic acid, acetate, phenylformic acid, alkyl para Toluic Acid; Adopt excessive hydrogen peroxide as oxygenant, the mole dosage of hydrogen peroxide is to mix 1.0～1.2 times of unsaturated double-bond value of unsaturated fatty acids acid monoester, and the organic acid mole dosage is to mix 0.8～1.1 times of unsaturated double-bond value of unsaturated fatty acids acid monoester; When catalyzer was selected sulfuric acid for use, its weight accounts for mixed 0.5～5% of unsaturated fatty acids acid monoester weight; When catalyzer was acidic white earth, its weight accounts for mixed 1～7% of unsaturated fatty acids acid monoester weight; When catalyzer was organic acid, its weight accounts for mixed 1～30% of unsaturated fatty acids acid monoester weight.
In the above-mentioned ring-opening reaction, temperature is controlled between 65～170 ℃, 1～12 hour reaction times.
The weight of catalyzer is 0.05～0.9% of hybrid epoxidized fatty acid fat and nucleophilic reagent weight summation in the ring-opening reaction.
Alcohol, hydramine, sour as nucleophilic reagent so that reactive hydrogen atom can be provided in the ring-opening reaction, the nucleophilic reagent that is adopted mainly contains alcohol, hydramine, acid.The mole dosage of nucleophilic reagent is 1.0～1.3 times of hybrid epoxidized fatty acid monoester oxirane value.
Above-mentioned alcohol 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.
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);
Above-mentioned acid select oneself diacid, phthalic acid etc.;
The present invention can increase a neutralization washing separation circuit before the epoxidation reaction after alcoholysis reaction, these process using acidic substance carry out neutralizing treatment as the catalyst treatment agent to alkaline catalysts, and washing separates then.
Above-mentioned acidic substance are for can carry H
+Acid, comprise phosphoric acid, tetra-sodium, sulfuric acid, oxalic acid, hydrochloric acid etc., the mol ratio of its consumption and alkaline catalysts consumption is 1: 1.0～1.05.
Above-mentioned neutral temperature and washing temperature are controlled at 50～90 ℃, in and the time: 15～45 minutes.
Before ring-opening reaction, can adopt the dehydration that deacidifies of one of following two kinds of methods earlier:
A. alkali cleaning → washing process: with in 1～10% the sodium carbonate solution and excessive acid, with the saturated brine washing, wash with soft water the back again; Method with underpressure distillation dewaters at last;
B. salt water washing → washing process: after the saturated brine washing, with soft water washing 2～4 times, the method with underpressure distillation dewaters at last, and the salt brine solution consumption is 20～60% of a crude product, and soft water is 20～60% of crude product.
The temperature of alkali cleaning and washing is 60 ℃～90 ℃, and the temperature of salt washing is 40 ℃～80 ℃;
Dehydration: the vacuum tightness during underpressure distillation is 80kPa～750kPa, and temperature is 80 ℃～120 ℃.
The mixing hydroxy fatty acid monoester that the hybrid epoxidized fatty acid monoester generates after ring-opening reaction can directly be made biopolyol and use, and its process for purification is as follows:
Adopt acidic substance that alkaline catalysts 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 alkaline catalysts consumption is 1: 1.0～1.05.Preferably phosphoric acid and hydrochloric acid, more preferably phosphoric acid.
Above-mentioned neutral temperature: 50～90 ℃, in and the time: 15～45 minutes.
Adoptable sorbent material is the material with adsorption function, and as diatomite, atlapulgite, pure aluminium silicate, Magnesium Silicate q-agent, activated carbon etc., its weight is generally needs 0.08～3.00% of refining thing.
Mixing hydroxy fatty acid monoester that the hybrid epoxidized fatty acid monoester generates after ring-opening reaction and olefin oxide generation addition reaction, can prepare the biopolyol of higher molecular weight, then it is made with extra care, process for purification is with above-mentioned biopolyol without addition reaction.
Olefin oxide in the above-mentioned addition reaction 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.Coefficient gets 1.0～1.22 in the formula.
Temperature of reaction in the above-mentioned addition reaction is 80～120 ℃, reaction pressure≤1.0MPa.
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 remaining catalyzer in the ring-opening reaction during addition reaction, so the mixing hydroxy fatty acid monoester that generates after the ring-opening reaction need not before addition to carry out refining in advance.When contained catalyst concn is low in the unpurified mixing hydroxy fatty acid monoester, add catalyzer as required, the addition biopolyol promptly mixes 0.2～1.5% of hydroxy fatty acid monoester and olefin oxide gross weight to make the weight of addition reaction catalyst account for not.
Description of drawings
Fig. 1 is a process flow sheet of the present invention
Embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1
To add smart rapeseed oil meter 1000g, glycerol 211g in the glass still of 2L, potassium hydroxide 1.1g stirs, and is warming up to 120～240 ℃, carries out alcoholysis reaction 5 hours, and the back is to keep 3～6 hours under the situation of 100～750kPa in vacuum tightness.Be cooled to 75 ℃, add 50% phosphoric acid 3.6g, kept 30 minutes, add 250g water, stirred 15 minutes, leave standstill the back and separate, add water 250g again, stirred 15 minutes, leave standstill the back and separate, must mix unsaturated fatty acids acid monoester 1015g.
Embodiment 2
Mixing unsaturated fatty acids acid monoester 1185g and 250 gram formic acid (80%), 60 acidic white earths that restrain got in the foregoing description 1 add in the glass still of 2L, stir, drip 37% hydrogen peroxide of 376 grams, under 30～70 ℃ condition, reacted 6～10 hours, leave standstill the back and separate the upper strata; 70～80 ℃ of the temperature of control upper strata mixed epoxidized fatty acid monoester, yellow soda ash washing with 5% is washed each 2 times with saturated brine washing and soft water 2 times again, method with underpressure distillation dewaters at last, gets mixed epoxidized fatty acid monoester, and the oxirane value that detects it is 4.50%.
Embodiment 3
Product mixed epoxidized fatty acid monoester 1245g with among the embodiment 2 adds glycol ether 420g again, and potassium hydroxide 4.2g joins in the glass still of 2L, stirs to heat up 65～170 ℃ of control reaction temperature, 5～9 hours reaction times.After make with extra care, concrete grammar is as follows: add 50% phosphatase 11 3.7g carry out in and 15 minutes, adding Magnesium Silicate q-agent 2g adsorbs, the back is under the temperature of 100～750KPa and 80～120 ℃ in vacuum tightness, dewatered 60 minutes, after the filtration, get product 1400g purified biopolyol, hydroxyl value is 475mgKOH/g.
Embodiment 4
In the glass still of 2L, with the unpurified biopolyol meter 1000g of embodiment 3,80～120 ℃ of control reaction temperature add the 300g propylene oxide, 200g ethylene oxide, 2 hours reaction times.Sampling analysis, getting hydroxyl value is the biopolyol of 318mgKOH/g, the back add 50% phosphatase 11 4.7g carry out in and 15 minutes, adding Magnesium Silicate q-agent 3g adsorbed 30 minutes, the back is under the temperature of 100～750KPa and 100～110 ℃ in vacuum tightness, dewatered 60 minutes, and after the filtration, got 1438g purified biopolyol.
Embodiment 5
In the glass still of 2L, with the unpurified biopolyol meter 1020g of example 3,80～120 ℃ of control reaction temperature add the 250g propylene oxide, 2 hours reaction times.Sampling analysis, getting hydroxyl value is the biopolyol of 378mgKOH/g, the back add 50% phosphatase 11 5.0g carry out in and 15 minutes, adding Magnesium Silicate q-agent 3.8g adsorbed 30 minutes, the back is under the temperature of 100～750KPa and 100～110 ℃ in vacuum tightness, dewatered 60 minutes, and after the filtration, got 1205g purified biopolyol.
Embodiment 6
Add smart rapeseed oil meter 980g, glycol ether 244g in the glass still of 2L, potassium hydroxide 1.1g stirs, and is warming up to 120～240 ℃, carries out alcoholysis reaction 5.5 hours, and the back is to keep 3 hours under the situation of 100～720kPa in vacuum tightness.Be cooled to 75 ℃, add 50% phosphoric acid 3.6g, kept 30 minutes, add 150g water, stirred 15 minutes, leave standstill the back and separate, add water 150g again, stirred 15 minutes, leave standstill the back and separate, must mix unsaturated fatty acids acid monoester 1023g.
Embodiment 7
The sulfuric acid of getting mixing unsaturated fatty acids acid monoester 1200g among the embodiment 6 and 255g formic acid (80%), 45g50% adds in the glass still of 2L, stirs, and drips 38% hydrogen peroxide of 365 grams, reacts under 30～70 ℃ condition 6～10 hours.Leave standstill the back and separate the upper strata; 70～80 ℃ of the temperature of control upper strata mixed epoxidized fatty acid monoester, yellow soda ash washing with 5% 2 times, with saturated brine washing and soft water washing each 2 times, the method with underpressure distillation dewaters at last again, get mixed epoxidized fatty acid monoester, the oxirane value of testing product is 4.46%.
Embodiment 8
Product mixed epoxidized fatty acid monoester 1250g with among the embodiment 7 adds trolamine 622g again, and (10%) glycerol potassium 28g joins in the glass still of 5L, stirs to heat up 65～170 ℃ of control reaction temperature, 5～10 hours reaction times.After make with extra care, concrete grammar is as follows: add 50% phosphatase 79 .2g carry out in and 15 minutes, adding Magnesium Silicate q-agent 4g adsorbs, the back is under the temperature of 100～750KPa and 80～120 ℃ in vacuum tightness, dewatered 60 minutes, after the filtration, get product 1570g purified biopolyol, hydroxyl value is 512mgKOH/g.
Embodiment 9
In the glass still of 2L, add smart rapeseed oil meter 967g, glycerol 70g, tetramethylolmethane 140g, 10% glycerol potassium 45g stirs, and is warming up to 120～240 ℃, carried out alcoholysis reaction 5～7 hours, the back kept 3～5 hours under vacuum tightness is the situation of 100～750kPa.Be cooled to 75 ℃, add 50% phosphatase 11 4.7g, kept 30 minutes, add 200g water, stirred 15 minutes, leave standstill the back and separate, add water 200g again, stirred 15 minutes, leave standstill the back and separate, must mix unsaturated fatty acids acid monoester 1045g.
Embodiment 10
Get mixing unsaturated fatty acids acid monoester 1195g among the embodiment 9 and 270g acetate, 380g phenylformic acid, add in the glass still of 2L, stir, drip 38% hydrogen peroxide of 378 grams, under 30～70 ℃ condition, reacted 6～10 hours; Leave standstill the back and separate the upper strata, 70～80 ℃ of the temperature of control mixed epoxidized fatty acid monoester, with saturated brine washing and soft water washing each 2 times, the method with underpressure distillation dewaters at last, gets mixed epoxidized fatty acid monoester, and the oxirane value that detects it is 4.58%.
Embodiment 11
Product mixed epoxidized fatty acid monoester 1260g with among the embodiment 10 adds propyl alcohol 72g again, and sodium hydroxide 1.23g joins in the glass still of 2L, stirs to heat up 65～170 ℃ of control reaction temperature, 5～10 hours reaction times.After make with extra care, concrete grammar is as follows: add 50% phosphoric acid 6g carry out in and 20 minutes, add atlapulgite 18g, adsorb, the back is under the temperature of 100～700KPa and 80～120 ℃, to dewater 60 minutes, after the filtration in vacuum tightness, get product 1280g purified biopolyol, hydroxyl value 480mgKOH/g.
Embodiment 12
In the glass still of 2L, the unpurified biopolyol meter 1070g with example 8 adds 30% Trimethylamine 99 6g, and 80～120 ℃ of control reaction temperature add the 500g ethylene oxide, 2 hours reaction times.Sampling analysis, getting hydroxyl value is the biopolyol of 350mgKOH/g.The back add 50% phosphoric acid 5.2g carry out in and 20 minutes, add Magnesium Silicate q-agent 2g and pure aluminium silicate 2g, adsorbed 30 minutes, the back is under the temperature of 100～750KPa and 80～120 ℃, to dewater 60 minutes in vacuum tightness, after the filtration, gets 1500g purified biopolyol.
Embodiment 13
In the glass still of 2L, the unpurified biopolyol meter 1200g with example 11 adds 80～120 ℃ of potassium hydroxide 2.5g control reaction temperature, adds the 200g propylene oxide, 2 hours reaction times.Sampling analysis, getting hydroxyl value is the coarse biometric polylol of 413mgKOH/g; The back add 50% phosphatase 11 2.6g carry out in and 15 minutes, add Magnesium Silicate q-agent 2.5g and pure aluminium silicate 2g, adsorb, the back is under the temperature of 100～750KPa and 100～110 ℃, to dewater 60 minutes in vacuum tightness, after the filtration, gets 1340g purified biopolyol.
Embodiment 14
Add smart rapeseed oil meter 980g, propylene glycol 48g, TriMethylolPropane(TMP) 134g in the glass still of 2L, 10% propylene glycol potassium 45g stirs, and is warming up to 70～240 ℃, carries out alcoholysis reaction 5 hours, and the back is to keep 3 hours under the situation of 100～750kPa in vacuum tightness.Be cooled to 75 ℃, add 50% phosphatase 11 4.8g, kept 30 minutes, add 150g water, stirred 15 minutes, leave standstill the back and separate, add water 150g again, stirred 15 minutes, leave standstill the back and separate, must mix unsaturated fatty acids acid monoester 1025g.
Embodiment 15
The mixing unsaturated fatty acids acid monoester 1190g that gets among the embodiment 14 adds in the three-necked bottle of 3L, stirs, and dripping 1650g concentration is 18% peroxyformic acid, reacts under 30～70 ℃ condition 7～10 hours; Leave standstill separation upper strata, back, 70～80 ℃ of the temperature of control mixed epoxidized fatty acid monoester are washed each 2 times with saturated brine washing and soft water, and the method with underpressure distillation dewaters at last, gets mixed epoxidized fatty acid monoester, and the oxirane value that detects it is 4.63%.
Embodiment 16
Product mixed epoxidized fatty acid monoester 1250g with among the embodiment 16 adds diisopropanolamine (DIPA) 584g again, and sodium hydroxide 1.3g joins in the glass still of 2L, stirs to heat up 65～170 ℃ of control reaction temperature, 5～10 hours reaction times.After make with extra care, concrete grammar is as follows: add 50% phosphoric acid 6.5g carry out in and 15 minutes, add atlapulgite 18g, adsorbed 30 minutes, the back is under the temperature of 100～750KPa and 100～110 ℃, to dewater 60 minutes, after the filtration in vacuum tightness, get product 1720g purified biopolyol, hydroxyl value 508mgKOH/g.
Embodiment 17
In the stainless steel still of 5L, with the unpurified biopolyol meter 1300g of example 16,80～120 ℃ of control reaction temperature add the 240g propylene oxide, 2 hours reaction times.After add catalyzer potassium hydroxide 10g, add mixture (blending ratio the is 70/30) 850g of propylene oxide 1680g and propylene oxide and ethylene oxide.Sampling analysis, getting hydroxyl value is the biopolyol of 165mgKOH/g.With 15 minutes, add Magnesium Silicate q-agent 8g and pure aluminium silicate 8g during back adding 50% phosphoric acid 37.4g carries out, adsorbed 30 minutes, the back is under the temperature of 100～750KPa and 100～110 ℃ in vacuum tightness, dewatered 70 minutes, and after the filtration, got 3885g purified biopolyol.
Claims (23)
1, a kind of biopolyol that utilizes the rapeseed oil preparation is characterized in that being prepared from by following method: rapeseed oil in the presence of catalyzer, is added alcohol and carries out alcoholysis reaction, generate blended unsaturated fatty acids acid monoester; Add epoxidizing agent again and carry out epoxidation reaction, generate mixed epoxidized fatty acid monoester; With aforementioned epoxy fatty acid monoester and the nucleophilic reagent generation epoxy bond ring-opening reaction that contains reactive hydrogen, generate and mix hydroxy aliphatic acid monoester, i.e. biopolyol then.
2, according to the described biopolyol that utilizes the rapeseed oil preparation of claim 1, it is characterized in that the biopolyol that will be generated can carry out addition reaction with olefin oxide, generate the biopolyol of higher molecular weight.
3,, it is characterized in that before raw material, need carrying out refinement treatment without the biopolyol of addition reaction and biopolyol as preparation urethane through addition reaction to described according to claim 1 or the 2 described biopolyols that utilize rapeseed oil preparation.
4, according to claim 1 or the 2 described biopolyols that utilize the rapeseed oil preparation, it is characterized in that the alcohol of alcoholysis reaction can be selected from:
Monohydroxy-alcohol: methyl alcohol, ethanol, propyl alcohol, butanols etc.
Dibasic alcohol: 1,4-butyleneglycol, glycol ether, triglycol, ethylene glycol, propylene glycol;
Trivalent alcohol: glycerol, TriMethylolPropane(TMP);
Tetravalent alcohol: tetramethylolmethane, methylglucoside;
Hexavalent alcohol: sorbyl alcohol, N.F,USP MANNITOL;
Dibasic alcohol such as preferred propylene glycol, butyleneglycol, glycol ether, triglycol, ethylene glycol or glycerol, TriMethylolPropane(TMP);
The consumption of alcohol: alcohol is (2.0～3.6) with the mol ratio of rapeseed oil: 1.
5, according to claim 1 or the 2 described biopolyols that utilize the rapeseed oil preparation, it is characterized in that the used catalyzer of alcoholysis reaction can select metal hydroxides or metal alkoxide for use, preferred alkali metal hydroxide or alkali metal alkoxide, the aforementioned bases metal hydroxides is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide; Aforementioned alkali-metal alkoxide is selected from sodium methylate, sodium ethylate, potassium methylate, glycerol potassium etc., and the weight of catalyzer accounts for 0.01～0.8% of rapeseed oil weight.
6,, it is characterized in that before the epoxidation reaction neutralization washing separation circuit being arranged after the alcoholysis reaction according to claim 1 or the 2 described biopolyols that utilize rapeseed oil preparation.
7,, it is characterized in that with the peroxide organic acid can adopting one of following method when specifically reacting as epoxidizing agent according to claim 1 or the 2 described biopolyols that utilize rapeseed oil preparation:
First method is directly to adopt the peroxide organic acid and mix the unsaturated fatty acids acid monoester and react, and generates target product;
Second method is to adopt hydrogen peroxide as oxygenant, and organic acid adopts sulfuric acid or acidic white earth or organic acid as catalyzer as the precursor of transition oxygenant, and H is provided
+Effect, accelerate the peroxide organic acid and generate, back peroxide organic acid with mix the unsaturated fatty acids acid monoester and carry out epoxidation reaction, the generation target product;
8,, it is characterized in that epoxidizing agent is selected from peroxyformic acid, Peracetic Acid, benzoyl hydroperoxide, crosses the oxyalkyl para Toluic Acid, wherein a kind of or optional their mixture according to the described biopolyol that utilizes rapeseed oil preparation of claim 7.Peroxide organic acid mole dosage is 1.0～1.2 times of mixing unsaturated fatty acids acid monoester unsaturated double-bond value; If adopt second method, the organic acid that is adopted comprises formic acid, acetate, phenylformic acid, the alkyl para Toluic Acid, adopt hydrogen peroxide as oxygenant, the molar weight of hydrogen peroxide is 1.0～1.2 times of mixing unsaturated fatty acids acid monoester unsaturated double-bond value, the organic acid mole dosage is to mix 0.8～1.1 times of unsaturated double-bond value of unsaturated fatty acids acid monoester, wherein, when catalyzer is sulfuric acid, its weight accounts for mixes 0.5～5% of unsaturated fatty acids acid monoester weight, when catalyzer is acidic white earth, its weight accounts for mixes 1～7% of unsaturated fatty acids acid monoester weight, when catalyzer was organic acid, its weight accounts for mixed 1～30% of unsaturated fatty acids acid monoester consumption.
9,, it is characterized in that epoxy fatty acid monoester has a deacidification dehydration procedure before ring-opening reaction according to claim 1 or the 2 described biopolyols that utilize the rapeseed oil preparation.
10, according to claim 1 or the 2 described biopolyols that utilize the rapeseed oil preparation, it is characterized in that the preferred catalyzer of ring-opening reaction is alkali metal hydroxide or alkali metal alkoxide; The aforementioned bases metal hydroxides is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide; Described alkali-metal alkoxide is selected from the product after alcohol such as sodium methylate, sodium ethylate, potassium methylate, glycerol potassium dewater with alkali metal hydroxide; Preferred potassium hydroxide, glycerol potassium; The weight of catalyzer is 0.05～0.9% of hybrid epoxidized fatty acid monoester and nucleophilic reagent gross weight.
11, according to claim 1 or the 2 described biopolyols that utilize the rapeseed oil preparation, it is characterized in that alcohol, hydramine, sour as nucleophilic reagent so that reactive hydrogen atom can be provided, carry out ring-opening reaction; The add-on of nucleophilic reagent is: every mole mixed epoxidized fatty acid monoester needs 1.0～1.4 moles nucleophilic reagent.
12, according to claim 1 or the 2 described biopolyols that utilize rapeseed oil preparation, it is characterized in that the temperature of described alcoholysis reaction is controlled between 70～240 ℃, pressure is at-0.1～0.1MPa, 3～15 hours reaction times.
13, according to claim 1 or the 2 described biopolyols that utilize the rapeseed oil preparation, it is characterized in that the temperature of described epoxidation reaction is controlled between 30～70 ℃, 2.5～12 hours reaction times.
14, according to claim 1 or the 2 described biopolyols that utilize the rapeseed oil preparation, it is characterized in that the temperature of described ring-opening reaction is controlled between 65～170 ℃, 1～12 hour reaction times.
15, according to the described biopolyol that utilizes the rapeseed oil preparation of claim 11, it is characterized in that described alcohol 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 such as preferred propylene glycol, butyleneglycol, glycol ether, triglycol, ethylene glycol or glycerol, TriMethylolPropane(TMP); Described 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).Described acid is selected from phthalic acid, hexanodioic acid.
16, according to the described biopolyol that utilizes the rapeseed oil preparation of claim 9, it is characterized in that described is the deacidification dehydration of epoxidized fatty acid monoesters before ring-opening reaction, can adopt one of following two kinds of methods:
A. alkali cleaning → washing process: with in 1～10% the sodium carbonate solution and excessive acid, with the saturated brine washing, wash with soft water the back again; Method with underpressure distillation dewaters at last;
B, salt water washing → washing process: after the saturated brine washing, with soft water washing 2～4 times; Method with underpressure distillation dewaters at last; The salt brine solution consumption is 20～60% of a crude product.Soft water is 20～60% of crude product.
17, according to the described biopolyol that utilizes the rapeseed oil preparation of claim 16, the temperature that it is characterized in that alkali cleaning and washing is 60 ℃～90 ℃, and the temperature of salt washing is 40 ℃～80 ℃; Vacuum tightness during underpressure distillation is 80kPa～750kPa, and temperature is 60 ℃～120 ℃.
18, according to claim 1 and the 2 described biopolyols that utilize the rapeseed oil preparation, it is characterized in that described biopolyol process for purification is as follows:
Adopt 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.
19,, it is characterized in that above-mentioned described acidic substance are selected to carry H according to the described biopolyol that utilizes rapeseed oil preparation of claim 18
+Phosphoric acid, tetra-sodium, sulfuric acid, oxalic acid, hydrochloric acid, the mol ratio of its consumption and alkaline catalysts consumption is 1: 1.0～1.05; Above-mentioned sour preferably phosphoric acid and hydrochloric acid, more preferably phosphoric acid; Described sorbent material is selected from diatomite, atlapulgite, pure aluminium silicate, Magnesium Silicate q-agent, the activated carbon with adsorption function, and its weight is generally needs 0.08～3.00% of refining thing; Dehydration and filtration temperature: 80～120 ℃, dehydration vacuum tightness is 100～750KPa, and dewatering time 60～150min, filter pressure are 1.5～3kg/cm
2
20, according to the described biopolyol that utilizes rapeseed oil preparation of claim 6, it is characterized in that adding after the alcoholysis reaction acidic substance washing that neutralizes and separate, aforementioned acidic substance are selected from can carry H
+Phosphoric acid, tetra-sodium, sulfuric acid, oxalic acid, hydrochloric acid, the mol ratio of its consumption and alkaline catalysts consumption is 1: 1.0～1.05.The neutralization with washing temperature be 50～90 ℃, in and the time: 15～45 minutes.
21,, 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 described biopolyol that utilizes the rapeseed 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.Coefficient gets 1.0～1.22 in the formula.
22, according to the described biopolyol that utilizes the rapeseed oil preparation of claim 2, it is characterized in that the temperature of reaction in the addition reaction is 80～120 ℃, reaction pressure≤1.0MPa.
23, according to claim 2 and the 21 described biopolyols that utilize the rapeseed oil preparation, the catalyzer that it is characterized in that 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, and the weight of addition reaction catalyst accounts for 0.2～1.5% of the pure and mild olefin oxide gross weight of addition bio-based polyhydric not.
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