CN105601869A - Solar rigid polyurethane foam thermal insulation material - Google Patents

Solar rigid polyurethane foam thermal insulation material Download PDF

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Publication number
CN105601869A
CN105601869A CN201610074104.6A CN201610074104A CN105601869A CN 105601869 A CN105601869 A CN 105601869A CN 201610074104 A CN201610074104 A CN 201610074104A CN 105601869 A CN105601869 A CN 105601869A
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parts
thermal insulation
ppg
solar energy
building materials
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黄可煜
陆俊行
蒙献芳
马云
马广
孟沪生
李光明
周子茜
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GUANGXI JISHUN ENERGY TECHNOLOGY Co Ltd
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GUANGXI JISHUN ENERGY TECHNOLOGY Co Ltd
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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4804Two or more polyethers of different physical or chemical nature
    • C08G18/4816Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
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    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
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    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2615Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
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    • C08H8/00Macromolecular compounds derived from lignocellulosic materials
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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    • C08K3/34Silicon-containing compounds
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    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • C08J2375/08Polyurethanes from polyethers
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Abstract

The invention relates to a thermal insulation material and discloses a rigid polyurethane foam thermal insulation material. The thermal insulation material is prepared by mixing and foaming the following raw materials in parts by weight: 70-100 parts of toluene diisocynate, 40-80 parts of polyether polyol I, 10-30 parts of polyether polyol II, 3-6 parts of expanded vermiculite, 5-8 parts of nano silicon dioxide, 10-20 parts of trichlorofluoromethane, 1-5 parts of catalyst and 1-5 parts of foam stabilizer, wherein the polyether polyol I is lignin polyether polyol; and the polyether polyol II is polyether polyol polymerized by taking modified peanut oil as an initiator and epoxy propane as a polymerization monomer. The thermal insulation material has high compressive strength, tensile strength and impact strength and avoids the phenomena of deformation, bulging, barring and even cracking of a water tank.

Description

A kind of solar energy Polyurethane Thermal Insulation Building Materials
Technical field
The present invention relates to insulation material, relate in particular to a kind of solar energy Polyurethane Thermal Insulation Building Materials.
Background technology
The continuous increase of and environmental protection pressure day by day in short supply along with the energy, countries in the world all start to try hard to recommend exploitation renewable energySource, wherein solar energy is to utilize and exploitation is the widest, the best regenerative resource of development prospect, has now been widely used in each row eachIndustry, solar water heater industry is exactly one of them. China's solar energy resources that is richly stored with, solar energy utilizes prospect wideWealthy, be at present in the world solar water heater first use state and producing country.
As everyone knows, concerning solar water heater, the selection of water tank heat preserving material is vital, can be used as at presentThe insulation material of water tank mainly contains polyurethane foam, phenol formaldehyde foam, superfine fibre etc. Polyurethane foam is with poly-by isocyanatesEther composition mixing is poured into foaming in mould or water tank cavity and makes, and wherein polyether composition contains PPG, foamingAgent, catalyst, curing agent, fire retardant, stabilizing agent etc., because polyurethane foam has, moulding process is simple, thermal conductivity factor is low etc.Advantage is the insulation material that water tank mainly adopts.
In lignin structure, contain alcoholic extract hydroxyl group, can react and prepare polyurethane with isocyanates by Substitute For Partial polyalcoholHard bubble, but because hydroxy radical content is lower, cause its activity lower, limited its application; In addition, in the mistake of preparing polyurethane foamCheng Zhong, is woodenly usually dispersed in the middle of polyalcohol with macromolecular particle form, causes the decline of reactivity worth and abscess notEvenly, so want a large amount of lignin that use in polyurethane, just must resolve the problems of dissolution of lignin.
The main molecules of vegetable oil consists of triacylglycerol ester, also have a small amount of free fatty and partial glyceride,Phosphatide, tocopherol and the vitamin E of 0.1-0.5%. In general, the oleic acid content in vegetable oil is higher, linoleic acid plus linolenic acidContent is lower, and its oxidation stability is better. In vegetable oil molecule, contain a large amount of carbon-carbon double bonds, the oxidation mechanism of vegetable oil is mainShow as active allyl reaction, this is the poor main cause of its oxidation stability just. Vegetable oil major part is by stablizing raw materialObtaining, is therefore a kind of worthwhile urethane raw, and shortcoming is that it lacks and the necessary active hydrogen of isocyanate reaction, therefore needTo carry out modification to vegetable oil.
Polyurethane hard foam in process of production, because of itself characteristic, production technology and direct labor's operative skill etc.The reason of each side, the problem of ubiquity foam contraction, easily causes foam and housing parts to come off or all come off, finalCause casing deformation, vacuum mouth of pipe foam cracking, What is more, and the polyurethane hard foam between inner bag and shell is horizontal or longitudinalFtracture, reduced widely the heat insulation effect of water tank.
Summary of the invention
Goal of the invention of the present invention is: for the problem of above-mentioned existence, provide a kind of solar energy hard polyurethane foam insulationMaterial. This solar energy Polyurethane Thermal Insulation Building Materials has the better mechanical property such as compression strength, hot strength, the while gramTake the large shortcoming of foaming after-contraction, avoided water tank distortion, rise and heave the stupefied even phenomenon of cracking, and ensured hot waterThe heat-insulating property of device water tank.
The present invention is achieved by the following technical solutions:
A kind of solar energy Polyurethane Thermal Insulation Building Materials, described insulation material is by the raw material mixed foaming of following weight fraction: 70 ~ 100 parts of toluene di-isocyanate(TDI)s, 40 ~ 80 parts of PPG I, 10 ~ 30 parts of PPG II, expanded vermiculite 3 ~ 6Part, 5 ~ 8 parts of nano silicons, 10 ~ 20 parts of F-11s, 1 ~ 5 part of catalyst, 1 ~ 5 part of foam stabiliser; Described polyethersPolyalcohol I is lignin polyether polyalcohol, and described PPG II is to be that initiator, expoxy propane are for poly-by modification olive oilClose the PPG that monomer polymerization forms.
Further, the particle diameter of described expanded vermiculite is 40 ~ 70 orders.
Further, described nano silicon is nanometer silica line or hollow mesoporous silica nanospheres.
Further, described catalyst is diethanol monoisopropanolamine or AEEA.
Further, described foam stabiliser is silicone based foam stabiliser.
Further, the degree of functionality of described PPG I is 4.5 ~ 5.0, and its hydroxyl value is 370 ~ 410mgKOH/g, and it is pressedRaw material and method according to following parts by weight are made:
(1) take 50 ~ 100 parts, lignin, 30 ~ 50 parts, water, 1 ~ 5 part of lignin peroxidase, 1 ~ 3 part of catalase, furanMutter 3 ~ 10 parts of 1 ~ 10 part, acetaldehyde and furfuryl alcohols in reactor, and reaction temperature is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modifiedLignin;
(2) by 100 parts, enzymolysis modified lignin, 250 ~ 350 parts of glycerine, 100 ~ 300 parts of diethylene glycol (DEG)s and Pd-Fe catalyst 0.01~ 0.05 part is mixed in reactor, and controlling reaction temperature is 120 DEG C, is reacted by the logical nitrogen bubble of reactor bottom, then takes out trueSky, adds 2 ~ 10 parts of expoxy propane, and atmospheric closed reaction 2 hours, obtains described PPG I.
Further, the degree of functionality of described PPG II is 5.0 ~ 6.0, and its hydroxyl value is 360 ~ 430mgKOH/g, itsMake according to the raw material of following parts by weight and method:
(1) take in 1 ~ 5 part to 100 ~ 300 parts olive oil of 20 ~ 50 parts of ethylene glycol and magnesium chloride, controlling reaction temperature is 120 DEG C,React 3 hours, obtain modification olive oil;
(2) 0.05 ~ 1.0 part of 100 parts, modification olive oil and Pd-Fe catalyst is mixed in reactor, controls reaction temperature and be150 DEG C, reacted by the logical nitrogen bubble of reactor bottom, then vacuumize, add 2 ~ 10 parts of expoxy propane, atmospheric closed reaction 2Hour, obtain described PPG II.
Further, described silicone based foam stabiliser is 3-[MPEG-550] propyl trialkoxy siliconAlkane or 3-[gather (ethylene glycol-copolymerization-propane diols) monomethyl ether] propyl trialkoxy silane.
The present invention adopts lignin polyether polyalcohol to react and prepare hard polyurethane foam with toluene di-isocyanate(TDI), increasesThe intensity of Polyurethane Thermal Insulation Building Materials. In system, the hydroxyl of lignin can react with toluene di-isocyanate(TDI), obtains woodQuality based polyurethanes. Lignin is to have macromolecular compound cancellated, that contain the firm groups such as phenyl ring, at polyurethaneIn hard bubbling, can increase the intensity of foam. Therefore (PPG therein with respect to hard bubbling of being prepared by common PPGServe as soft section), this lignin-base polyurethane foamed material is better in the performance of the aspect such as hot strength, compression strength.
It is that initiator, expoxy propane are that the polyethers that is polymerized of polymerization single polymerization monomer is polynary that part of the present invention adopts modification olive oilAlcohol, olive oil structure is carried out after modification, can on strand, introduce a large amount of hydroxyls, the PPG degree of functionality preparingHeight, hydroxyl value is high; It can react with toluene di-isocyanate(TDI) is full and uniform in system, and promotes other auxiliary agent in reactantEvenly mix and disperse, generate the fine and closely woven abscess that is evenly distributed, reduce the shrinkage factor after foam-formed; Simultaneously because modification olive oil isRenewable resource, thus the use of petroleum derivative indirectly reduced, reducing the dependence to petroleum resources, can serve as newlyThe raw material of type foam.
Expanded vermiculite is a kind of secondary metamorphic mineral of water aluminosilicate containing magnesium of layer structure, and raw ore is outer like mica, itsFor by fabric and raw-vermiculite sheet after high-temperature roasting, its volume energy vermiculite obtaining after several times to tens times that expands rapidly. After expandedVermiculite is graininess, have heat insulation, resistance toly freeze, the excellent properties such as antibacterial, fire prevention, sound absorption, what the present invention adopted is that particle diameter is 40 ~ 70 ordersExpanded vermiculite, the percent opening of the increase polyurethane hard foam that expanded vermiculite can be suitable, and can delay foamable gel and solidify speedDegree, prevents that foam from greatly easily pushing inner bag and outer wall because of short time inner accumulated strength, reduces the generation of " bad foam ", simultaneouslyReduce the shrinkage factor after foam-formed.
Nano silicon is a kind of Inorganic Non-metallic Materials of excellent performance, and it is large that it has specific area, adsorptionPower is strong, the special performances such as chemical purity is high, dispersive property good, thermal resistance, with its superior stability, reinforcement, thickening property andThixotropy shows unique characteristics in numerous subjects and field, has the effect of not replacing. The nano silicon adopting is hereinNanometer silica line or hollow mesoporous silica nanospheres, after foaming raw material mixes, nano silicon can be distributed in bubbleIn the skeleton of hole wall, foamed material, play the effect that strengthens hole wall and foam stiffness, and can not affect foam structure, mix simultaneouslyAssorted nano silicon also can improve the intensity of solar energy Polyurethane Thermal Insulation Building Materials.
The present invention adopt machine silicon class A foam A stabilizing agent be 3-[MPEG-550] propyl trialkoxy silane or3-[gathers (ethylene glycol-copolymerization-propane diols) monomethyl ether] propyl trialkoxy silane, it can reduce urethane raw mixtureSurface tension, is raised up between the maturation period at foam, prevents by surface tension the material that the thermodynamics unstable state of foam occurs.
After hard polyurethane foam formula material mixing jetting of the present invention, can make formation of foam spherical or oval spherical and distributeEvenly fine and closely woven abscess, expanded material heat-insulating property is stable, and increases the intensity of cell wall, reduces when foam-formed because of interior external pressureThe poor material compression phenomena occurring suitably increases the percent opening of foam simultaneously, reduces the shrinkage factor after foam-formed.
In sum, owing to having adopted technique scheme, the invention has the beneficial effects as follows:
(1) the present invention adopts lignin polyether polyalcohol in foaming formulation, the lignin-base rigid foam material making and tradition sideThe prepared foamed material of method is compared, and has better compression strength, hot strength and impact strength.
(2) solar energy Polyurethane Thermal Insulation Building Materials of the present invention compared with prior art, steeps except possessing conventional polyurethanesOutside foam material high heat preservation performance, also reduce because of each side such as itself characteristic, production technology and direct labor's operative skillsThe foam contraction problem that reason causes, avoids water tank distortion, rises and heave the stupefied even phenomenon of cracking.
Detailed description of the invention
Disclosed all features in this description, or step in disclosed all methods or process, except mutually exclusiveFeature and/or step beyond, all can combine by any way.
Disclosed arbitrary feature in this description (comprising any accessory claim, summary), unless narration especially all canReplaced by other equivalences or the alternative features with similar object. ,, unless narration especially, each feature is a series ofAn example in equivalence or similar characteristics.
Embodiment 1
First prepare PPG I, process is as follows:
(1) take lignin 80g, water 40g, lignin peroxidase 5g, catalase 1g, furans acetaldehyde 1g and furfuryl alcohol 5gIn reactor, reaction temperature is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modified lignin;
(2) enzymolysis modified lignin 100g, glycerine 300g, diethylene glycol (DEG) 200g and Pd-Fe catalyst 0.03g are mixed in to reactionIn device, controlling reaction temperature is 120 DEG C, is reacted by the logical nitrogen bubble of reactor bottom, then vacuumizes, and adds expoxy propane8g, atmospheric closed reaction 2 hours, obtaining degree of functionality is 4.6, the described PPG I that hydroxyl value is 400mgKOH/g.
Prepare PPG II, process is as follows again:
(1) take ethylene glycol 40g and magnesium chloride 3g in 200g olive oil, controlling reaction temperature is 120 DEG C, react 3 hours,To modification olive oil;
(2) modification olive oil 100g and Pd-Fe catalyst 0.08g are mixed in reactor, controlling reaction temperature is 150 DEG C,Reacted by the logical nitrogen bubble of reactor bottom, then vacuumize, add expoxy propane 8g, atmospheric closed reaction 2 hours, obtains officialEnergy degree is 5.6, the described PPG II that hydroxyl value is 370mgKOH/g.
A kind of solar energy Polyurethane Thermal Insulation Building Materials, described insulation material is by the raw material mixed foaming of following weight fractionAnd obtain: take PPG I 40g, PPG II 10g, expanded vermiculite 3g, nanometer silica line 5g, trichloro-monofluoroMethane 10g, diethanol monoisopropanolamine 2g and 3-[MPEG-550] propyl trialkoxy silane 2g mixes, soWith toluene di-isocyanate(TDI) 80g mixed foaming, after overcuring, can obtain solar energy hard polyurethane foam of the present invention afterwardsInsulation material.
Embodiment 2
First prepare PPG I, process is as follows:
(1) take lignin 50g, water 30g, lignin peroxidase 3g, catalase 2g, furans acetaldehyde 3g and furfuryl alcohol10g is in reactor, and reaction temperature is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modified lignin;
(2) enzymolysis modified lignin 100g, glycerine 250g, diethylene glycol (DEG) 100g and Pd-Fe catalyst 0.01g are mixed in to reactionIn device, controlling reaction temperature is 120 DEG C, is reacted by the logical nitrogen bubble of reactor bottom, then vacuumizes, and adds expoxy propane4g, atmospheric closed reaction 2 hours, obtaining degree of functionality is 5.0, the described PPG I that hydroxyl value is 400mgKOH/g.
Prepare PPG II, process is as follows again:
(1) take ethylene glycol 20g and magnesium chloride 1g in 100g olive oil, controlling reaction temperature is 120 DEG C, react 3 hours,To modification olive oil;
(2) modification olive oil 100g and Pd-Fe catalyst 0.05g are mixed in reactor, controlling reaction temperature is 150 DEG C,Reacted by the logical nitrogen bubble of reactor bottom, then vacuumize, add expoxy propane 4g, atmospheric closed reaction 2 hours, obtains officialEnergy degree is 5.5, the described PPG II that hydroxyl value is 390mgKOH/g.
A kind of solar energy Polyurethane Thermal Insulation Building Materials, described insulation material is by the raw material mixed foaming of following weight fractionAnd obtain: take PPG I 40g, PPG II 10g, 40 order expanded vermiculite 3g, nanometer silica line 5g, trichlorineOne fluoromethane 10g, AEEA 2g and 3-[MPEG-550] propyl trialkoxy silane 2g mixes, soWith toluene di-isocyanate(TDI) 80g mixed foaming, after overcuring, can obtain solar energy hard polyurethane foam of the present invention afterwardsInsulation material.
Embodiment 3
First prepare PPG I, process is as follows:
(1) take lignin 100g, water 50g, lignin peroxidase 2g, catalase-3 g, furans acetaldehyde 8g and furfuryl alcohol6g is in reactor, and reaction temperature is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modified lignin;
(2) enzymolysis modified lignin 100g, glycerine 350g, diethylene glycol (DEG) 250g and Pd-Fe catalyst 0.05g are mixed in to reactionIn device, controlling reaction temperature is 120 DEG C, is reacted by the logical nitrogen bubble of reactor bottom, then vacuumizes, and adds expoxy propane10g, atmospheric closed reaction 2 hours, obtaining degree of functionality is 4.7, the described PPG I that hydroxyl value is 410mgKOH/g.
Prepare PPG II, process is as follows again:
(1) take ethylene glycol 50g and magnesium chloride 5g in 300g olive oil, controlling reaction temperature is 120 DEG C, react 3 hours,To modification olive oil;
(2) modification olive oil 100g and Pd-Fe catalyst 1.0g are mixed in reactor, controlling reaction temperature is 150 DEG C, byThe logical nitrogen bubble reaction of reactor bottom, then vacuumizes, and adds expoxy propane 8g, and atmospheric closed reaction 2 hours, obtains senseDegree is 6.0, the described PPG II that hydroxyl value is 350mgKOH/g.
A kind of solar energy Polyurethane Thermal Insulation Building Materials, described insulation material is by the raw material mixed foaming of following weight fractionAnd obtain: take PPG I 80g, PPG II 20g, 60 order expanded vermiculite 6g, nanometer silica line 8g, trichlorineOne fluoromethane 20g, AEEA 5g and 3-[gather (ethylene glycol-copolymerization-propane diols) monomethyl ether] propyl trialkoxy siliconAlkane 4g mixes, and then, with toluene di-isocyanate(TDI) 100g mixed foaming, can obtain of the present invention after overcuringSolar energy Polyurethane Thermal Insulation Building Materials.
Embodiment 4
First prepare PPG I, process is as follows:
(1) take lignin 80g, water 40g, lignin peroxidase 1g, catalase-3 g, furans acetaldehyde 10g and furfuryl alcohol5g is in reactor, and reaction temperature is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modified lignin;
(3) enzymolysis modified lignin 100g, glycerine 300g, diethylene glycol (DEG) 200g and Pd-Fe catalyst 0.03g are mixed in to reactionIn device, controlling reaction temperature is 120 DEG C, is reacted by the logical nitrogen bubble of reactor bottom, then vacuumizes, and adds expoxy propane8g, atmospheric closed reaction 2 hours, obtaining degree of functionality is 5.0, the described PPG I that hydroxyl value is 370mgKOH/g.
Prepare PPG II, process is as follows again:
(1) take ethylene glycol 40g and magnesium chloride 3g in 200g olive oil, controlling reaction temperature is 120 DEG C, react 3 hours,To modification olive oil;
(3) modification olive oil 100g and Pd-Fe catalyst 0.08g are mixed in reactor, controlling reaction temperature is 150 DEG C,Reacted by the logical nitrogen bubble of reactor bottom, then vacuumize, add expoxy propane 8g, atmospheric closed reaction 2 hours, obtains officialEnergy degree is 5.5, the described PPG II that hydroxyl value is 360mgKOH/g.
A kind of solar energy Polyurethane Thermal Insulation Building Materials, described insulation material is by the raw material mixed foaming of following weight fractionAnd obtain: take PPG I 70g, PPG II 20g, 70 order expanded vermiculite 5g, hollow mesoporous silica nanospheres7g, F-11 10g, diethanol monoisopropanolamine 5g and 3-[gather (ethylene glycol-copolymerization-propane diols) monomethyl ether] propyl groupTrialkoxy silane 2g mixes, and then, with toluene di-isocyanate(TDI) 80g mixed foaming, after overcuring, can obtain thisBright described solar energy Polyurethane Thermal Insulation Building Materials.
The physical function parameter of the solar energy Polyurethane Thermal Insulation Building Materials respectively embodiment 1-4 being prepared is examinedSurvey, test result is as shown in table 1.
Table 1
From table, thermal conductivity factor, the pressure resistance of solar energy Polyurethane Thermal Insulation Building Materials prepared by the above embodiment of the present inventionThe indexs such as degree, tensile bond strength, dimensional stability and rate of closed hole all have significantly and improve than existing insulation material, through coldFreeze or hot conditions under without phenomenons such as contraction, distortion, expansion, crackings, be a kind of insulation material of excellent performance.
The present invention is not limited to aforesaid detailed description of the invention. The present invention expands to any disclosure in this manualNew feature or any new combination, and the arbitrary new method disclosing or step or any new combination of process.

Claims (8)

1. a solar energy Polyurethane Thermal Insulation Building Materials, is characterized in that, described insulation material is former by following weight fractionExpect mixed foaming and obtain: 70 ~ 100 parts of toluene di-isocyanate(TDI)s, 40 ~ 80 parts of PPG I, 10 ~ 30 parts of PPG II,3 ~ 6 parts of expanded vermiculites, 5 ~ 8 parts of nano silicons, 10 ~ 20 parts of F-11s, 1 ~ 5 part of catalyst, foam stabiliser 1 ~ 5Part; Described PPG I is lignin polyether polyalcohol, described PPG II for by modification olive oil be initiator,Expoxy propane is the PPG that polymerization single polymerization monomer is polymerized.
2. solar energy Polyurethane Thermal Insulation Building Materials according to claim 1, is characterized in that: the grain of described expanded vermiculiteFootpath is 40 ~ 70 orders.
3. solar energy Polyurethane Thermal Insulation Building Materials according to claim 1, is characterized in that: described nano siliconFor nanometer silica line or hollow mesoporous silica nanospheres.
4. solar energy Polyurethane Thermal Insulation Building Materials according to claim 1, is characterized in that: described catalyst is diethylAlcohol monoisopropanolamine or AEEA.
5. solar energy Polyurethane Thermal Insulation Building Materials according to claim 1, is characterized in that: described foam stabiliser isSilicone based foam stabiliser.
6. according to the solar energy Polyurethane Thermal Insulation Building Materials described in claim 1 to 5 any one claim, its feature existsIn: the degree of functionality of described PPG I is 4.5 ~ 5.0, and its hydroxyl value is 370 ~ 410mgKOH/g, and it is according to following parts by weightRaw material and method make:
(1) take 50 ~ 100 parts, lignin, 30 ~ 50 parts, water, 1 ~ 5 part of lignin peroxidase, 1 ~ 3 part of catalase, furanMutter 3 ~ 10 parts of 1 ~ 10 part, acetaldehyde and furfuryl alcohols in reactor, and reaction temperature is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modifiedLignin;
(2) by 100 parts, enzymolysis modified lignin, 250 ~ 350 parts of glycerine, 100 ~ 300 parts of diethylene glycol (DEG)s and Pd-Fe catalyst 0.01~ 0.05 part is mixed in reactor, and controlling reaction temperature is 120 DEG C, is reacted by the logical nitrogen bubble of reactor bottom, then takes out trueSky, adds 2 ~ 10 parts of expoxy propane, and atmospheric closed reaction 2 hours, obtains described PPG I.
7. according to the solar energy Polyurethane Thermal Insulation Building Materials described in claim 1 to 5 any one claim, its feature existsIn: the degree of functionality of described PPG II is 5.0 ~ 6.0, and its hydroxyl value is 360 ~ 430mgKOH/g, and it is according to following weight portionRaw material and the method for number are made:
(1) take in 1 ~ 5 part to 100 ~ 300 parts olive oil of 20 ~ 50 parts of ethylene glycol and magnesium chloride, controlling reaction temperature is 120 DEG C,React 3 hours, obtain modification olive oil;
(2) 0.05 ~ 1.0 part of 100 parts, modification olive oil and Pd-Fe catalyst is mixed in reactor, controls reaction temperature and be150 DEG C, reacted by the logical nitrogen bubble of reactor bottom, then vacuumize, add 2 ~ 10 parts of expoxy propane, atmospheric closed reaction 2Hour, obtain described PPG II.
8. solar energy Polyurethane Thermal Insulation Building Materials according to claim 5, is characterized in that: described silicone based foamStabilizing agent is 3-[MPEG-550] propyl trialkoxy silane or poly-(ethylene glycol-copolymerization-propane diols) monomethyl of 3-[Ether] propyl trialkoxy silane.
CN201610074104.6A 2016-02-03 2016-02-03 Solar rigid polyurethane foam thermal insulation material Withdrawn CN105601869A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106279610A (en) * 2016-08-15 2017-01-04 黄宝兴 Polyurethane heat-insulating heat-preserving material
CN106279611A (en) * 2016-08-15 2017-01-04 黄宝兴 The preparation method of phenolic urethanes cellular insulant
CN109575218A (en) * 2018-11-14 2019-04-05 安徽明光中兴阳光新能源科技有限公司 A kind of solar water container polyurethane inorganic flame-retardant thermal insulation material and preparation method thereof
CN109593177A (en) * 2018-11-14 2019-04-09 安徽明光中兴阳光新能源科技有限公司 A kind of solar water heater flame-retardant thermal insulation material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102250340A (en) * 2010-05-21 2011-11-23 江苏绿源新材料有限公司 Method for synthesizing palm oil hard foamed polyether glycol
CN103319677A (en) * 2013-07-15 2013-09-25 广西吉顺能源科技有公司 Polyether polyol foam thermal-insulation material for water tank of solar water heater
CN103772693A (en) * 2014-01-23 2014-05-07 单成敏 Method for preparing lignin polyether polyols
WO2015083092A1 (en) * 2013-12-05 2015-06-11 Stora Enso Oyj A composition in the form of a lignin polyol, a method for the production thereof and use thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102250340A (en) * 2010-05-21 2011-11-23 江苏绿源新材料有限公司 Method for synthesizing palm oil hard foamed polyether glycol
CN103319677A (en) * 2013-07-15 2013-09-25 广西吉顺能源科技有公司 Polyether polyol foam thermal-insulation material for water tank of solar water heater
WO2015083092A1 (en) * 2013-12-05 2015-06-11 Stora Enso Oyj A composition in the form of a lignin polyol, a method for the production thereof and use thereof
CN103772693A (en) * 2014-01-23 2014-05-07 单成敏 Method for preparing lignin polyether polyols

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
伍久林等: "西施舌过氧化氢酶活性的研究", 《福州大学学报(自然科学版)》 *
郁志芳等: "鲜切芦蒿过氧化物酶特性的研究", 《食品科学》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106279610A (en) * 2016-08-15 2017-01-04 黄宝兴 Polyurethane heat-insulating heat-preserving material
CN106279611A (en) * 2016-08-15 2017-01-04 黄宝兴 The preparation method of phenolic urethanes cellular insulant
CN109575218A (en) * 2018-11-14 2019-04-05 安徽明光中兴阳光新能源科技有限公司 A kind of solar water container polyurethane inorganic flame-retardant thermal insulation material and preparation method thereof
CN109593177A (en) * 2018-11-14 2019-04-09 安徽明光中兴阳光新能源科技有限公司 A kind of solar water heater flame-retardant thermal insulation material and preparation method thereof

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