CN1844183A - Rigid polyurethane foam prepared by using rape seed oil - Google Patents
Rigid polyurethane foam prepared by using rape seed oil Download PDFInfo
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- CN1844183A CN1844183A CN 200610039943 CN200610039943A CN1844183A CN 1844183 A CN1844183 A CN 1844183A CN 200610039943 CN200610039943 CN 200610039943 CN 200610039943 A CN200610039943 A CN 200610039943A CN 1844183 A CN1844183 A CN 1844183A
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Abstract
This invention is preparation method of rigid polyurethane foam plastics with rape oil. The procedure is as followings: 1) epoxidise the rape oil and epoxidation agent to produce epoxidised rape oil. 2) React with nucleophilic reagent toget mixed hydroxy fatty acid glycerin; 3) add alcohol or alcohol amine, heat to get mixed hydroxy fatty acid monoesters-biological polyatomic alcohol. 4) Mix with auxiliary catalysis, foam stabilizer and water to form polyether polyol. 5) Mix with foaming agent and isocyanate to obtain rigid polyurethane foam plastics. This invention has a high compatibility with alkane foaming and low cost. It's a good heat insulating material.
Description
Technical field
The present invention relates to be adopt the rapeseed oil preparation rigid urethane foam, belong to the polyurethane synthetic material field.
Background technology
Rigid urethane foam is widely used in industries such as home freezer, refrigerator-freezer, building heat preservation and pipeline owing to have excellent heat-insulating property, good plasticity-and processing characteristics.It is the foam article that is formed by chemical reaction under catalyst action by combined polyether (ester) polyvalent alcohol, whipping agent and isocyanic ester.Wherein polyethers (ester) polyvalent alcohol is the main raw material of preparation polyurethane foam.
Along with the fast development of global economy, the whole world is to comprising that all polyvalent alcohol demands of above-mentioned polyethers (ester) polyvalent alcohol are in quick growth.But existing polyvalent alcohol all is 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, but the applicant still finds no the successful report of research.
Summary of the invention
The present invention will solve be exactly that existing rigid urethane foam depends on the oil is the problem of raw material, come the synthesising biological polylol then adopt vegetables oil to carry out the technology deep processing, utilize biopolyol to prepare the rigid urethane foam of better performances again.
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, can pass through epoxidation reaction under certain conditions, ring-opening reaction, alcoholysis reaction 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.
Rigid urethane foam of the present invention is made by following steps:
1) rapeseed oil and epoxidizing agent are carried out epoxidation reaction in the presence of catalyzer, generate epoxy rapeseed oil;
2), generate and mix the hydroxy aliphatic acid glyceride again with epoxy rapeseed oil that generates and the nucleophilic reagent generation epoxy bond ring-opening reaction that contains reactive hydrogen;
3) add the intensification of alcoholysis agent alcohol or hydramine and carry out alcoholysis reaction, generate and mix hydroxy aliphatic acid monoester, i.e. biopolyol;
4) be basic material with biopolyol and polyethers or polyester polyol, be aided with catalyzer, suds-stabilizing agent, water and be mixed with combined polyether glycol;
5) with combined polyether glycol, mix with whipping agent, foam with isocyanate reaction again, can prepare rigid urethane foam.
Aforementioned biopolyol and olefin oxide carry out addition reaction, can generate the biopolyol of higher molecular weight.
Above-mentioned two kinds of biopolyols all can be used as the intermediate product that is used to prepare rigid urethane foam among the present invention.
In abovementioned steps 1)-3) prepare in the process of intermediates biopolyol, because the difference of the catalyzer that is adopted, epoxidizing agent, nucleophilic reagent, alcoholysis agent etc., the concrete moiety of the biopolyol that is generated and containing of each composition also can be different.
Involved in the present invention as follows with chemical principle:
1, epoxidation reaction
Here R ' comprise-H ,-CH
3,-C
6H
5,-CH
3(CH
2)
nC
6H
5
2, ring-opening reaction:
Here R ' H refers to alcohol, hydramine, acid
3, alcoholysis reaction (carrying out alcoholysis with the adding glycerol is example):
Here, R " OH refers to glycerol.
In the above-mentioned epoxidation reaction, temperature is controlled between 30～70 ℃, 2.5～12 hours reaction times.
In the above-mentioned epoxidation reaction, adopt the peroxide organic acid as epoxidizing agent, the carrying out of epoxidation reaction can be adopted following two kinds of methods:
First method is directly to adopt peroxide organic acid and rapeseed oil to react, and generates epoxy rapeseed oil;
Second method is to adopt hydrogen peroxide as oxygenant, and organic acid is as the precursor of transition oxygenant, and adopting sulfuric acid, phosphoric acid is catalyzer, and H is provided
+Effect, accelerate the peroxide organic acid and generate, after make peroxide organic acid and rapeseed oil carry out epoxidation reaction, the generation epoxy rapeseed oil.
In the epoxidation reaction, the peroxide organic acid comprises: peroxyformic acid, Peracetic Acid, benzoyl hydroperoxide, mistake oxyalkyl para Toluic Acid; Peroxide organic acid mole dosage is 1.0～1.2 times of rapeseed oil unsaturated double-bond value.If adopt second method, the organic acid that is adopted comprises formic acid, acetate, phenylformic acid, alkyl para Toluic Acid, adopts excessive hydrogen peroxide as oxygenant, and the molar weight of hydrogen peroxide is 1.0～1.2 times of rapeseed oil unsaturated double-bond values.Sulfuric acid or phosphoric acid weight account for 0.5～5% of rapeseed oil weight.
In the above-mentioned ring-opening reaction, temperature is controlled between 65～170 ℃, 1～12 hour reaction times.
The catalyzer of ring-opening reaction is a basic catalyst, is selected from the alkoxide of metal hydroxides or metal, is preferably alkali metal hydroxide or alkali-metal alkoxide, 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, 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.
Alcohol, hydramine, sour as nucleophilic reagent so that reactive hydrogen atom can be provided in the ring-opening reaction, adoptable nucleophilic reagent mainly contains alcohol, hydramine, acid.The nucleophilic reagent mole dosage is 1.0～1.3 times of oxirane value of epoxy rapeseed oil.
Alcohol in the ring-opening reaction is selected from methyl alcohol, butanols, 1,4-butyleneglycol, glycol ether, triglycol, ethylene glycol, glycerol, propylene glycol, tetramethylolmethane, Xylitol, sorbyl alcohol 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.
In the above-mentioned ring-opening reaction excessive alcohol or hydramine can be directly as the alcoholysis agent of alcoholysis reaction.
Alcoholysis reaction directly adopts the catalyzer in the ring-opening reaction to carry out.Temperature of reaction is 120～240 ℃, and leading portion is reflected under the normal pressure and carries out, and later stage vacuum tightness is 100～750kPa, and the reaction times is 3～15 hours.
Alcohol as the alcoholysis agent in the alcoholysis reaction is selected from methyl alcohol, ethanol, propyl alcohol, butanols etc. with 1,4-butyleneglycol, glycol ether, triglycol, ethylene glycol, glycerol, propylene glycol, tetramethylolmethane, Xylitol, sorbyl alcohol etc., dibasic alcohol or trivalent alcohols such as glycerol, TriMethylolPropane(TMP) such as preferred propylene glycol, butyleneglycol, glycol ether, triglycol, ethylene glycol.
Hydramine as the alcoholysis agent in the alcoholysis reaction is selected from a Yi Bingchunan, diisopropanolamine (DIPA), tri-isopropanolamine, thanomin, diethanolamine, trolamine, alkyl alkanolamine, benzyl alkanolamine etc., preferred tri-isopropanolamine and trolamine, methyldiethanolamine, methyl diisopropanolamine (DIPA).
The alcoholysis agent consumption of alcoholysis reaction with the mol ratio of mixing the hydroxy aliphatic acid glyceride is: 2.0～3.8: 1.
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 Shen 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 mixing hydroxy aliphatic acid glyceride generates after alcoholysis reaction can directly be made biopolyol and use, 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.
Mixing hydroxy fatty acid monoester that generates after the alcoholysis reaction and olefin oxide generation addition reaction can be prepared the biopolyol of higher molecular weight, then it are made with extra care, and process for purification is with the method for above-mentioned biopolyol without addition reaction.
Olefin oxide in the above-mentioned addition reaction is the mixture of ethylene oxide, propylene oxide, oxybutylene or their optional ratios; 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 adopt in the ring-opening reaction be alkali metal hydroxide or alkali metal alkoxide as catalyzer, can directly adopt the catalyzer of ring-opening reaction need not carry out refining in advance during addition reaction.When the contained catalyst concn of unpurified biopolyol is low, add catalyzer as required, make the weight of addition reaction catalyst account for 0.2～1.5% of the pure and mild olefin oxide gross weight of addition bio-based polyhydric not.
The aforesaid combination polyethers is formulated by weight by following component:
Biopolyol 5～30%, polyether glycol 48～94.4%, catalyzer 0.1～10%, suds-stabilizing agent 0.5～5%, water 0.01～7%.
Polyether glycol in the combined polyether can be selected from poly(propylene oxide) or the oxyethane polyethers that hydroxyl value is 150～800mgKOH/g;
Catalyzer in the combined polyether is a composite catalyst, and this composite catalyst can be amines catalyst or amines catalyst and tin class mixture of catalysts.Wherein, amines catalyst is selected from: N, N,-dimethylcyclohexylamine, triethylenediamine, dimethyl benzylamine, N, N '; N "-three (dimethylaminopropyl)-Hexahydrotriazines, trolamine, Yi Bingchunan, pentamethyl--diethylenetriamine, quaternary amine or their compound or similar catalyzer can be one of above-mentioned substances, also can two or more mixtures with arbitrary proportion.Tin class catalyzer is selected from: di-n-butyltin dilaurate and similar catalyzer.When catalyzer is during by amines catalyst and tin class mixture of catalysts, wherein amines catalyst should account for more than 30% of composite catalyst gross weight.
Suds-stabilizing agent in the combined polyether is silicon-oxygen or silico-carbo type tensio-active agent, can be selected from: German Sa company: B8460, B8461, B8462, B8465, B8471, B8474, B8476, B8481 etc.; The silicide of GE company has L6900, L6988, L6912 and the suds-stabilizing agent DC5604 of Dow Corning Corporation, DC5357, and dolantin generation wound company produces suds-stabilizing agent AK8805, AK8815, AK8812, AK8809 etc.Suds-stabilizing agent can be one of above-mentioned also can be that two or more arbitrary proportion mixes and uses.
Weight ratio 100 when combined polyether mixed with whipping agent: (0～38).
Above-mentioned whipping agent can be selected from: HCFC-141b, pentamethylene, iso-pentane, HFC-245fa, HFC-365mfc.Choose any one kind of them or multiple mixture with arbitrary proportion.
Above-mentioned isocyanic ester can be selected from tolylene diisocyanate, diphenyl diisocyanate, polymethine polyphenyl polyisocyanate (being commonly called as PAPI) or their mixture, preferred polymethine polyphenyl polyisocyanate.Preferred polymethine polyphenyl polyisocyanate, the present manufacturer and the trade mark can be the DesmodurN of Bayer company, 44V20L, 44V10L etc. usually; Huntsman Corporation's Super ace5005,2085 etc.; The PAPI27 of DOW company; The MR200 in the Mitsui East Asia of BASF AG, the C1130 of Japanese NPU company, PM2010 of domestic Yantai Wan Hua company etc.
Isocyanic ester and combined polyether are 1.0～3.0 by the equivalence ratio of NCO/OH during foaming, and preferred range is 1.05～1.2.
At least a biopolyol in the above-mentioned combined polyether prescription that contains biopolyol, one or more polyether glycol, and auxiliary agents such as corresponding suds-stabilizing agent, composite catalyst, water.
The present invention is that the biopolyol that obtains after by deep processing of raw material is as intermediates with the rapeseed oil, this biopolyol is compared with polyvalent alcohol in the past, and it is strong to have the functionality controllability, narrow molecular weight distribution, the reactive behavior height can prepare the characteristics such as product of high functionality.The while raw material has cheap and easy to get, buys convenient, reproducible characteristics, is to optimize ecological Green Product.The technology of synthesising biological polylol has that collectivity is strong, and environmental pollution is little, and the product yield is advantage of higher also.Preparing rigid urethane foam with biopolyol as intermediates compares with traditional preparation method, have with alkane foaming consistency good, characteristics such as cost is lower, prepared rigid urethane foam is well behaved thermal insulation material, is applied to fields such as refrigerator thermal insulation, refrigerator thermal insulation, building heat preservation, piping insulation.
Embodiment
Describe the present invention in more detail below by embodiment and reference example, but the present invention is not limited in these examples.
At first by embodiment 1～16th, preparation intermediates biopolyol of the present invention is further described below.
Embodiment 1～16th in the table 1, prepares the further instruction of rigid urethane foam to adopting intermediates biopolyol of the present invention.Wherein: the polyether glycol parameter index in the table 1 is:
Polyether glycol M hydroxyl value is poly(propylene oxide) or the oxyethane polyethers of 320～450mgKOH/g;
Polyether glycol N hydroxyl value is poly(propylene oxide) or the oxyethane polyethers of 440～560mgKOH/g;
Polyether glycol P hydroxyl value is poly(propylene oxide) or the oxyethane polyethers of 400～460mgKOH/g;
Polyether glycol Q hydroxyl value is poly(propylene oxide) or the oxyethane polyethers of 170～280mgKOH/g.
Embodiment 1
To in the glass still of 2L, add the sulfuric acid of smart rapeseed oil meter 1000g, 250g formic acid (80%), 45g50%, stir, drip 37% the hydrogen peroxide of 375g, under 30～70 ℃ condition, reacted 5～10 hours, standing demix is isolated sour water, adds 6% sodium carbonate solution neutralization, is 70～80 ℃ water washing 3 times again with temperature, decompression, vacuum tightness is that 100～700kPa removes residual moisture content.Get the product epoxy rapeseed oil, the oxirane value of testing product is 5.21%.
Embodiment 2
To in the glass still of 2L, add the phosphoric acid of smart rapeseed oil meter 980g, 536g phenylformic acid, 60g50%, stir, drip 38% the hydrogen peroxide of 410g, under 30～70 ℃ condition, reacted 5～10 hours, standing demix is isolated sour water, adds 5% sodium carbonate solution neutralization, is 70～80 ℃ water washing 3 times again with temperature, decompression, vacuum tightness is that 100～700kPa removes residual moisture content.Get the product epoxy rapeseed oil, the oxirane value of testing product is 5.71%.
Embodiment 3
Product epoxy rapeseed oil 1050g among the embodiment 1 is joined in the glass still of 2L, add glycol ether 420g again, potassium hydroxide 4.9g stirs and heats up 65～170 ℃ of control reaction temperature, 5～10 hours reaction times.Add glycerol 211g, 120～240 ℃ of controlled temperature carried out alcoholysis reaction 4 hours, and the back is to keep 4 hours under the situation of 100～750kPa in vacuum tightness, 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 6g 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 1540g purified biopolyol A.
Embodiment 4
Product epoxy rapeseed oil 1049g among the embodiment 2 is joined in the glass still of 2L, add propylene glycol 332g again, potassium hydroxide 5g stirs and heats up 65～170 ℃ of control reaction temperature, 5～10 hours reaction times.Add TriMethylolPropane(TMP) 308g, 120～240 ℃ of controlled temperature carried out alcoholysis reaction 4 hours, and the back is to keep 3～7 hours under the situation of 100～750kPa in vacuum tightness, back sampling analysis, and hydroxyl value is the crude product of 502mgKOH/g.After make with extra care, concrete grammar is as follows: add 50% phosphatase 11 6.4g 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 1550g refined biological polylol B.
Embodiment 5
To in the glass still of 5L, add smart rapeseed oil meter 967g, stir, and drip 1670g peroxyformic acid (18%), under 30～70 ℃ condition, reacted 7～12 hours.Standing demix is isolated sour water, adds 5% sodium carbonate solution neutralization, is 70～80 ℃ water washing 4 times again with temperature, reduces pressure and removes residual moisture content.Get the product epoxy rapeseed oil, the oxirane value of testing product is 5.8%.
Embodiment 6
Product epoxy rapeseed oil 1050g among the embodiment 5 is added in the glass still of 2L, and add ethanol 170g, 10% ethanol potassium alcoholate 38g stirs and heats up 65～170 ℃ of control reaction temperature, 5～9 hours reaction times.The back adds tri-isopropanolamine 440g, 120～225 ℃ of controlled temperature, carried out alcoholysis reaction 3～6 hours, the back kept 5～7 hours under vacuum tightness is the situation of 100～750kPa, cooling to 70～80 ℃ makes with extra care, concrete grammar is as follows: add 50% phosphatase 11 2.4g carry out in and 20 minutes, adding atlapulgite 15g adsorbs, the back is under the temperature of 100～750KPa and 80～120 ℃ in vacuum tightness, dewatered 60 minutes, after the filtration, get 1570g purified biopolyol C, hydroxyl value is 465mgKOH/g.
Embodiment 7
To in the glass still of 5L, add smart rapeseed oil meter 978g, stir, Dropwise 35 20g benzoyl hydroperoxide (19%), under 30～70 ℃ condition, react 6～10 hours.Standing demix is isolated sour water, adds 5% sodium carbonate solution neutralization, is 70～80 ℃ water washing 4 times again with temperature, reduces pressure and removes residual moisture content.Get the product epoxy rapeseed oil, the oxirane value of testing product is 5.59%.
Embodiment 8
Product epoxy rapeseed oil 1046g among the embodiment 7 is added in the glass still of 2L, and add trolamine 665g, potassium hydroxide 2.3g stirs and heats up 65～170 ℃ of control reaction temperature, 4～10 hours reaction times.Add propylene glycol 175g and be warming up to 120～240 ℃ gradually, carried out alcoholysis reaction 3～6 hours, the back kept 4～6 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% phosphoric acid 7.5g 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 ℃ in vacuum tightness, dewatered 60 minutes, after the filtration, get 1755g purified biopolyol D, hydroxyl value is 396mgKOH/g.
Embodiment 9
Product epoxy rapeseed oil 1050g among the embodiment 7 is added in the glass still of 2L, and add diisopropanolamine (DIPA) 594g, sodium hydroxide 1.65g stirs and heats up 65～170 ℃ of control reaction temperature, 4～10 hours reaction times.Add ethylene glycol 103g and be warming up to 120～240 ℃ gradually, carried out alcoholysis reaction 3～6 hours, the back kept 4～6 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% phosphoric acid 8.2g 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 ℃ in vacuum tightness, dewatered 60 minutes, after the filtration, get 1630g purified biopolyol E, hydroxyl value is 443mgKOH/g.
Embodiment 10
To in the glass still of 2L, add the sulfuric acid of smart rapeseed oil meter 1000g, 270g acetate, 50g50%, and be stirred under 30～70 ℃ the condition and reacted 3～10 hours.Standing demix is isolated sour water, adds 8% sodium carbonate solution neutralization, is 70～80 ℃ water washing 3 times again with temperature, reduces pressure and removes residual moisture content.Get the product epoxy rapeseed oil, the oxirane value of testing product is 5.62%.
Embodiment 11
Product epoxy rapeseed oil 1050g among the embodiment 10 is added in the glass still of 2L, and add tetramethylolmethane 136g, butanols 225g, 10% butanols potassium alcoholate 30g stirs and heats up 65～170 ℃ of control reaction temperature, 4～10 hours reaction times.Add with glycerol 210g and be warming up to 120～240 ℃ 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 .8g 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 ℃ in vacuum tightness, dewatered 60 minutes, after the filtration, get 1550g purified biopolyol F, hydroxyl value is 471mgKOH/g.
Embodiment 12
With the crude product meter 1300g of embodiment 3,80～120 ℃ of control reaction temperature join in the glass still of 2L, add the 506g propylene oxide, 4～6 hours reaction times.Sampling analysis, getting hydroxyl value is the coarse biometric polylol of 340mgKOH/g.After make with extra care, concrete grammar is as follows: add 50% phosphatase 11 6g carry out in and 15 minutes, add Magnesium Silicate q-agent 4.2g and adsorb, the back is under the temperature of 100～750KPa and 100～110 ℃ in vacuum tightness, dewatered 60 minutes, and after the filtration, got product 1728g purified biopolyol G.
Embodiment 13
With the crude product meter 1300g among the embodiment 4,80～120 ℃ of control reaction temperature join in the glass still of 2L, add the 400g propylene oxide, 4～7 hours reaction times.Analyze to such an extent that hydroxyl value is the coarse biometric polylol of 358mgKOH/g.After make with extra care, concrete grammar is as follows: add 50% phosphatase 11 6.2g 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 100～110 ℃ in vacuum tightness, dewatered 60 minutes, and after the filtration, got product 1430g purified biopolyol H.
Embodiment 14
Crude product meter 1000g with among the embodiment 9 adds potassium hydroxide 4g, joins in the glass still of 2L, and 80～120 ℃ of control reaction temperature add 400g propylene oxide and 300g ethylene oxide, 4 hours reaction times.Analyze to such an extent that hydroxyl value is the coarse biometric polylol of 344mgKOH/g.After make with extra care, concrete grammar is as follows: add 50% phosphatase 11 9.2g carry out in and 20 minutes, add Magnesium Silicate q-agent 3.6g, adsorb, the back is under the temperature of 100～750KPa and 100～120 ℃, to dewater 60 minutes in vacuum tightness, after the filtration, get 1635g purified biopolyol I.
Embodiment 15
Product epoxy rapeseed oil 1050g among the embodiment 2 is joined in the glass still of 5L, add hexanodioic acid 638g again, potassium hydroxide 5.5g stirs and heats up 65～170 ℃ of control reaction temperature, 5～10 hours reaction times.Add sorbyl alcohol 190g, butyleneglycol 108g, 120～240 ℃ of controlled temperature carried out alcoholysis reaction 4 hours, and the back is to keep 3～7 hours under the situation of 100～700kPa in vacuum tightness, back sampling analysis, hydroxyl value is the crude product of 475mgKOH/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 4g 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 1851g purified biopolyol J.
Embodiment 16
Crude product meter 570g with among the embodiment 9 adds 30% Trimethylamine 99 10g, joins in the glass still of 2L 80～120 ℃ of control reaction temperature, the mixture (70/30) of adding 300g propylene oxide and ethylene oxide, 4～6 hours reaction times.Analyze to such an extent that hydroxyl value is the coarse biometric polylol of 365mgKOH/g.After make with extra care, concrete grammar is as follows: add 10% hydrochloric acid 5.2g carry out in and 20 minutes, add diatomite 9g, adsorb, the back is under the temperature of 100～750KPa and 100～120 ℃, to dewater 60 minutes in vacuum tightness, after the filtration, get 830g purified biopolyol K.
Get the foregoing description preparation at least a biopolyol, one or more polyether glycol, and auxiliary agent levels such as suds-stabilizing agent, composite catalyst, water become combined polyether accordingly, get the combined polyether glycol after the preparation then, technology mixes itself and whipping agent routinely, foam with isocyanate reaction again, can prepare hard polyurethane foams.
Table 1 shows by the combined polyether of biopolyol and the hard polyurethane foams that whipping agent, isocyanic ester are mixed with of containing of the present invention, the foam that does not contain the combined polyether preparation of biopolyol compares, discovery contains the foaming properties of biopolyol near the foaming properties that does not contain biopolyol, anti-active higher, the compressive strength better performances.
Table 1:
| Embodiment | Reference example | |||||||
| Numbering | 1 | ?2 | ?3 | ?4 | ?5 | ?6 | ?7 | ?8 |
| Biopolyol A | 25 | ?20 | ?5 | |||||
| Biopolyol B | 0 | ?5 | ||||||
| Biopolyol C | ?5 | ?10 | ||||||
| Biopolyol D | ?10 | |||||||
| Biopolyol E | ?10 | ?20 | ||||||
| Polyether glycol M | 40 | ?35 | ?45 | ?43.8 | ?34.1 | ?48.5 | ||
| Polyether glycol N | ?38.9 | ?20 | ?25 | ?50 | ||||
| Polyether glycol P | 28.9 | ?34.5 | ?10 | ?38 | ?30 | ?30 | ?38.5 | |
| Polyether glycol Q | ?20 | ?10 | ?15 | ?5 | ||||
| Suds-stabilizing agent | 2.0 | ?2.0 | ?2.0 | ?2.0 | ?2.0 | ?2.0 | ?2.0 | ?2.0 |
| Catalyzer | 2.1 | ?1.5 | ?2.1 | ?2.2 | ?1.5 | ?1.6 | ?2.5 | ?2.5 |
| Water | 2.0 | ?2.0 | ?2.0 | ?2.0 | ?3.5 | ?2.3 | ?2.0 | ?2.0 |
| HFC-245fa | 25 | ?25 | ?25 | |||||
| Pentamethylene | ?13 | ?11 | ?12 | |||||
| HCFC-141b | ?22 | ?16 | ||||||
| The NCO/OH equivalence ratio | 1.08 | ?1.08 | ?1.08 | ?1.07 | ?1.1 | ?1.06 | ?1.08 | ?1.08 |
| Molding density, kg/m 3 | 33.0 | ?34 | ?33.7 | ?32.6 | ?33.1 | ?33.9 | ?34.5 | ?32.8 |
| Thermal conductivity, W/mK | 0.0191 | ?0.0197 | ?0.0185 | ?0.0189 | ?0.0192 | ?0.0198 | ?0.0198 | ?0.0190 |
| Dimensional stability (30 ℃, 24h), % | 0.15 ? | ?0.2 ? | ?0.12 ? | ?0.1 ? | ?0.08 ? | ?0.11 ? ? | ?0.08 ? | ?0.12 ? |
| Compressive strength, KPa | 175 | ?188 | ?169 | ?166 | ?190 | ?187 | ?173 | ?165 |
Table 1 (continuing)
| Embodiment | Reference example | |||||||
| Numbering | 9 | ?10 | ?11 | ?12 | ?13 | ?14 | ?15 | ?16 |
| Biopolyol F | 5 | ?20 | ||||||
| Biopolyol G | ?5 | |||||||
| Biopolyol H | 10 | ?5 | ||||||
| Biopolyol I | ?5 | ?10 | ||||||
| Biopolyol J | ?5 | ?10 | ||||||
| Biopolyol K | ?20 | |||||||
| Polyether glycol M | ?35 | ?45 | ?42.5 | |||||
| Polyether glycol N | 45 | ?39.5 | ?26 | ?38.7 | ?5 | ?50 | ||
| Polyether glycol P | 34.7 | ?34 | ?10 | ?42.5 | ?35 | ?42 | ?38.5 | |
| Polyether glycol Q | ?40 | ?45 | ?5 | |||||
| Suds-stabilizing agent | 2.5 | ?2.5 | ?2.5 | ?2.5 | ?2.5 | ?2.5 | ?2.5 | ?2.0 |
| Catalyzer | 0.8 | ?1.5 | ?1.0 | ?2.0 | ?1.5 | ?1.5 | ?2.0 | ?2.5 |
| Water | 2.0 | ?2.0 | ?2.0 | ?2.0 | ?3.5 | ?2.3 | ?3.5 | ?2.0 |
| HFC-365mfc | 28 | ?26 | ?26 | |||||
| Pentamethylene | ?13 | ?10 | ||||||
| HCFC-141b | ?22 | |||||||
| The NCO/OH equivalence ratio | 1.09 | ?1.09 | ?1.09 | ?1.09 | ?1.09 | ?1.09 | ?1.09 | ?1.09 |
| Molding density, kg/m 3 | 33.0 | ?36 | ?37.6 | ?32.6 | ?62.7 | ?34.1 | ?640 | ?33.5 |
| Thermal conductivity, W/mK | 0.0190 | ?0.0200 | ?0.0188 | ?0.0184 | ?0.0242 | ?0.0202 | ?0.0239 | ?0.0190 |
| Dimensional stability (30 ℃, 24h), % | 0.11 ? | ?0.22 ? | ?0.16 ? | ?0.13 ? | ?0.06 ? | ?0.08 ? | ?0.09 ? | ?0.07 ? |
| Compressive strength, KPa | 176 | ?201 | ?192 | ?161 | ?345 | ?187 | ?338 | ?167 |
Claims (31)
1, a kind of rigid urethane foam that adopts the rapeseed oil preparation is characterized in that adopting the following step to be prepared from:
1) rapeseed oil and epoxidizing agent are carried out epoxidation reaction in the presence of catalyzer, generate epoxy rapeseed oil;
2), generate and mix the hydroxy aliphatic acid glyceride again with epoxy rapeseed oil that generates and the nucleophilic reagent generation epoxy bond ring-opening reaction that contains reactive hydrogen;
3) add the intensification of alcohol or hydramine and carry out alcoholysis reaction, generate and mix hydroxy aliphatic acid monoester, i.e. biopolyol;
4) be basic material with biopolyol and polyethers or polyester polyol, be aided with catalyzer, suds-stabilizing agent, water and be mixed with combined polyether glycol;
5) with combined polyether glycol, mix with whipping agent, foam with isocyanate reaction again, can prepare rigid urethane foam.
2, according to the rigid urethane foam of the described employing rapeseed oil preparation of claim 1, it is characterized in that biopolyol and olefin oxide that step 3) is generated carry out addition reaction, can generate the biopolyol of higher molecular weight.
3, according to the rigid urethane foam of claim 1 or 2 described employing rapeseed oil preparations, it is characterized in that the step 1) epoxidation reaction temperature is controlled between 30～70 ℃, 2.5～10 hours reaction times.
4,, it is characterized in that the step 1) epoxidation reaction adopts the peroxide organic acid as epoxidizing agent, can adopt one of following method when specifically reacting according to the rigid urethane foam of claim 1 or 2 described employing rapeseed oil preparations:
First method is directly to adopt peroxide organic acid and rapeseed oil to react, and generates epoxy rapeseed oil;
Second method is to adopt hydrogen peroxide as oxygenant, and organic acid adopts sulfuric acid, phosphoric acid as catalyzer as the precursor of transition oxygenant, and H is provided
+Effect, accelerate the peroxide organic acid and generate, after make peroxide organic acid and rapeseed oil carry out epoxidation reaction, the generation epoxy rapeseed oil.
5, according to the rigid urethane foam of the described employing rapeseed oil preparation of claim 4, it is characterized in that the peroxide organic acid comprises: peroxyformic acid, Peracetic Acid, benzoyl hydroperoxide, mistake oxyalkyl para Toluic Acid; Peroxide organic acid mole dosage is 1.0～1.2 times of rapeseed oil unsaturated double-bond value; If adopt second method, the organic acid that is adopted comprises formic acid, acetate, phenylformic acid, alkyl para Toluic Acid, adopts excessive hydrogen peroxide as oxygenant, and the mole dosage of hydrogen peroxide is 1.0～1.2 times of rapeseed oil unsaturated double-bond values; The organic acid mole dosage is 0.8～1.1 times of a rapeseed oil unsaturated double-bond value; Sulfuric acid or phosphoric acid catalyst weight account for 0.5～5% of rapeseed oil weight.
6, according to the rigid urethane foam of claim 1 or the preparation of 2 described employing rapeseed oils, it is characterized in that step 2) the ring-opening reaction temperature is controlled between 65～170 ℃ 1～12 hour reaction times.
7, the rigid urethane foam for preparing according to claim 1 or 2 described employing rapeseed oils, it is characterized in that step 2) catalyzer of ring-opening 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.Catalyst consumption is 0.05～0.9% of epoxy rapeseed oil and a nucleophilic reagent consumption summation in the ring-opening reaction.
8, according to the rigid urethane foam of claim 1 or the preparation of 2 described employing rapeseed oils, it is characterized in that step 2) nucleophilic reagent that adopted in the ring-opening reaction mainly contains alcohol, hydramine, also usable acid; The nucleophilic reagent mole dosage is 1.0～1.3 times of oxirane value of epoxy rapeseed oil.
9, the rigid urethane foam for preparing according to the described employing rapeseed oil of claim 8, it is characterized in that step 2) alcohol in the ring-opening 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 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);
Acid select oneself diacid, phthalic acid.
10, according to the rigid urethane foam of claim 1 or 2 described employing rapeseed oil preparations, it is characterized in that the step 3) alcoholysis reaction directly adopts the catalyzer in the ring-opening reaction to carry out; Temperature of reaction is 120～240 ℃, and leading portion is reflected under the normal pressure and carries out, and later stage vacuum tightness is 100～750kPa, and the reaction times is 3～15 hours.
11, the rigid urethane foam for preparing according to claim 1 or 2 described employing rapeseed oils, the alcoholysis agent that it is characterized in that the step 3) alcoholysis reaction is selected from methyl alcohol, ethanol, propyl alcohol, butanols, 1 when being pure, 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, alkyl alkanolamine, benzyl alkanolamine etc., preferred tri-isopropanolamine and trolamine, methyldiethanolamine, methyl diisopropanolamine (DIPA).
12, according to the rigid urethane foam of claim 1 or 2 described employing 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.
13,, it is characterized in that epoxy rapeseed oil has a deacidification dehydration procedure before carrying out ring-opening reaction according to the rigid urethane foam of claim 1 or 2 described employing rapeseed oil preparations.
14,, 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 the rigid urethane foam of claim 1 or the preparation of 2 described employing rapeseed oils.
15,, it is characterized in that the deacidification dehydration of epoxy rapeseed oil before ring-opening reaction can adopt one of following two kinds of methods according to the rigid urethane foam of the described employing rapeseed oil of claim 13 preparation:
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.
16, the rigid urethane foam for preparing according to the described employing rapeseed oil of claim 15, the temperature that it is characterized in that alkali cleaning and washing is 60 ℃～90 ℃, the salt washing is 40～80 ℃, and the vacuum tightness during underpressure distillation is 80kPa～750kPa, and temperature is 80 ℃～120 ℃.
17, according to the rigid urethane foam of the described employing rapeseed oil preparation of claim 14, it is characterized in that described 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.
18,, it is characterized in that described acidic substance are selected to carry H according to the rigid urethane foam of the described employing rapeseed oil of claim 17 preparation
+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
19,, it is characterized in that the olefin oxide in the addition reaction is the mixture of ethylene oxide, propylene oxide, oxybutylene or their optional ratios according to the rigid urethane foam of the described employing 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, and coefficient gets 1.0～1.22 in the formula.
20, according to the rigid urethane foam of the described employing 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.
21, the rigid urethane foam for preparing according to the described employing rapeseed oil of claim 2, the catalyzer that it is characterized in that addition reaction is selected alkali metal alkoxide, alkali metal hydroxide for use, organic amine, the wherein preferred potassium hydroxide of alkali metal hydroxide, sodium hydroxide, product after preferred dibasic alcohol of alkali metal alkoxide or trivalent alcohol and the potassium hydroxide dehydration, the preferred Trimethylamine 99 of organic amine, triethylamine, dimethylamine.
22, the rigid urethane foam for preparing according to the described employing rapeseed oil of claim 2, the catalyzer that it is characterized in that addition reaction is selected from alkali metal hydroxide or alkali metal alkoxide or organic amine, 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 adopt in the ring-opening reaction be alkali metal hydroxide or alkali metal alkoxide as catalyzer, can directly adopt the catalyzer of ring-opening reaction need not carry out refining in advance during addition reaction; When the contained catalyst concn of unpurified biopolyol is low, add catalyzer as required, make the weight of addition reaction catalyst account for 0.2～1.5% of the pure and mild olefin oxide gross weight of addition bio-based polyhydric not.
23,, it is characterized in that the described combined polyether of step 4) is formulated by weight by following component according to the rigid urethane foam of claim 1 or 2 described employing rapeseed oil preparations:
Biopolyol 5～30%, polyether glycol 48～94.4%, catalyzer 0.1～10%, suds-stabilizing agent 0.5～5%, water 0.01～7%.
24, according to the rigid urethane foam of the described employing rapeseed oil preparation of claim 23, it is characterized in that containing in the combined polyether one or more biopolyols and one or more polyether glycol.
25,, it is characterized in that the ratio of whipping agent and the weight of combined polyether is 0～38: 100 in the step 5) according to the rigid urethane foam of claim 1 or the preparation of 2 described employing rapeseed oils.
26, the rigid urethane foam for preparing according to claim 1 or 2 described employing rapeseed oils, it is characterized in that the isocyanic ester in the step 5) is selected from tolylene diisocyanate, diphenyl diisocyanate, polymethine polyphenyl polyisocyanate or their mixture, preferred polymethine polyphenyl polyisocyanate; The equivalence ratio of the NCO/OH of isocyanic ester and combined polyether is 1.0～3.0, and preferred scope is 1.05～1.2.
27, according to the rigid urethane foam of the described employing rapeseed oil preparation of claim 23, it is characterized in that the catalyzer in the combined polyether comprises amines catalyst or amine and tin class mixture of catalysts; Amines catalyst comprises: N, N,-dimethylcyclohexylamine, triethylenediamine, dimethyl benzylamine, N, N '; N " three (dimethylaminopropyl)-Hexahydrotriazines, trolamine, Yi Bingchunan, pentamethyl--diethylenetriamine, quaternary amine or their compound or similar catalyzer, can be one of above-mentioned substance, also can two or more mixtures with arbitrary proportion; Tin class catalyzer comprises: di-n-butyltin dilaurate and similar catalyzer; At least contain the catalyzer of accelerating the foam curing performance in the complex class catalyzer, as N, N ', N "-three (dimethylaminopropyl) Hexahydrotriazines or quaternary amine or their compound or similar catalyzer; When catalyzer is during by amines catalyst and tin class mixture of catalysts, wherein amines catalyst should account for more than 30% of composite catalyst gross weight.
28, according to the rigid urethane foam of the described employing rapeseed oil preparation of claim 23, it is characterized in that the suds-stabilizing agent in the combined polyether is silicon-oxygen or silico-carbo type tensio-active agent.
29, according to the rigid urethane foam of claim 1 or 2 described employing rapeseed oil preparations, it is characterized in that the whipping agent in the step 5) can be selected from: the mixture of any one or more arbitrary proportion among HCFC-141b, pentamethylene, iso-pentane, HFC-245fa, the HFC-365mfc.
30, according to the rigid urethane foam of claim 1 or 2 described employing rapeseed oil preparations, it is characterized in that the water yield of step 4) use is relevant with whipping agent weight, when whipping agent was 0, it was 1～7% that water weight accounts for the combined polyether gross weight; When whipping agent when or not 0, it is 0.01～7% that water weight accounts for the combined polyether gross weight.
31, according to the application of the rigid urethane foam of any described employing rapeseed oil preparation of claim 1 to 31 as thermal insulation material.
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