CN105693974A - Solar polyurethane thermal insulation material - Google Patents

Solar polyurethane thermal insulation material Download PDF

Info

Publication number
CN105693974A
CN105693974A CN201610074105.0A CN201610074105A CN105693974A CN 105693974 A CN105693974 A CN 105693974A CN 201610074105 A CN201610074105 A CN 201610074105A CN 105693974 A CN105693974 A CN 105693974A
Authority
CN
China
Prior art keywords
parts
polyether polyol
insulation material
solar energy
heat insulation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201610074105.0A
Other languages
Chinese (zh)
Inventor
蒙胜杰
马庆
马珍
马佳乐
马祥
黄可煜
马付杰
吴定超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GUANGXI JISHUN ENERGY TECHNOLOGY Co Ltd
Original Assignee
GUANGXI JISHUN ENERGY TECHNOLOGY Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GUANGXI JISHUN ENERGY TECHNOLOGY Co Ltd filed Critical GUANGXI JISHUN ENERGY TECHNOLOGY Co Ltd
Priority to CN201610074105.0A priority Critical patent/CN105693974A/en
Publication of CN105693974A publication Critical patent/CN105693974A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • 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
    • 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
    • C08G18/64Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • 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
    • 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
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4081Mixtures of compounds of group C08G18/64 with other macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • 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
    • 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
    • C08G18/4891Polyethers modified with higher fatty oils or their acids or by resin acids
    • CCHEMISTRY; METALLURGY
    • 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
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • CCHEMISTRY; METALLURGY
    • 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
    • C08J9/143Halogen containing compounds
    • C08J9/144Halogen containing compounds containing carbon, halogen and hydrogen only
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
    • CCHEMISTRY; METALLURGY
    • 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
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to a thermal insulation material and discloses a solar polyurethane 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 diphenylmethane diisocyanate, 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 dichlorofluoroethane, 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 olive oil as an initiator and epoxy propane as a polymerization monomer. The thermal insulation material has better compressive strength, tensile strength and impact strength while the phenomena of water tank deformation, bulking, ridging and even cracking are avoided.

Description

A kind of solar energy polyurethane heat insulation material
Technical field
The present invention relates to insulation material, particularly relate to a kind of solar energy polyurethane heat insulation material。
Background technology
Along with the energy is day by day in short supply and the continuous increase of environmental protection pressure, countries in the world all start to try hard to recommend exploitation regenerative resource, wherein solar energy is utilize and develop the regenerative resource the widest, development prospect is best, is now widely used to all trades and professions, and solar water heater industry is exactly one of them。China is richly stored with solar energy resources, and Solar use has a extensive future, and has been that the first of solar water heater in the world uses state and manufacturing country at present。
It is known that for solar water heater, the selection of water tank heat preserving material it is critical that, can serve as the insulation material of water tank at present mainly has polyurethane foam, phenol formaldehyde foam, superfine fibre etc.。Polyurethane foam is to be mixed with polyether composition by isocyanates to be poured in mould or water tank cavity foaming and prepare, wherein polyether composition contains polyether polyol, foaming agent, catalyst, firming agent, fire retardant, stabilizer etc., owing to polyurethane foam has the advantages such as moulding process is simple, heat conductivity is low, it it is the insulation material that mainly adopts of water tank。
Containing alcoholic extract hydroxyl group in lignin structure, it is possible to Substitute For Partial polyhydric alcohol and isocyanates react prepares hard polyurethane foam, but owing to hydroxy radical content is relatively low, causes that its activity is relatively low, limit its application;Additionally, in the process of preparation polyurethane foam, wooden usually it is dispersed in the middle of polyhydric alcohol with macromolecular particle form, causes the decline of reactivity worth and the uneven of abscess, then want to use in a large number lignin in polyurethane, be necessary for resolving the problems of dissolution of lignin。
The main molecules of vegetable oil consists of triacylglyceride, also has a small amount of free fatty and partial glyceride, the phospholipid of 0.1-0.5%, tocopherol and vitamin E。In general, the oleic acid content in vegetable oil is more high, and linoleic acid plus linolenic acid content is more low, and its oxidation stability is more good。Containing substantial amounts of carbon-carbon double bond in vegetable oil molecule, the oxidation mechanism main manifestations of vegetable oil is active allyl reaction, this main cause that its oxidation stability is poor just。Vegetable oil major part is obtained by stable raw material, is therefore a kind of worthwhile urethane raw, and shortcoming is that it lacks and active hydrogen necessary to isocyanate reaction, therefore needs vegetable oil is modified。
Polyurethane hard foam is in process of production, reason because of each side such as itself characteristic, production technology and direct labor's operant skills, the problem of ubiquity foam contraction, it is easily caused foam to come off with housing portion or all come off, ultimately resulting in casing deformation, vacuum mouth of pipe foam ftractures, and What is more, polyurethane hard foam between inner bag and shell laterally or longitudinally ftractures, and greatly reduces the heat insulation effect of water tank。
Summary of the invention
The goal of the invention of the present invention is in that: for above-mentioned Problems existing, it is provided that a kind of solar energy polyurethane heat insulation material。This solar energy polyurethane heat insulation material has the mechanical properties such as more excellent comprcssive strength, hot strength, overcome the shortcoming that foaming after-contraction is big simultaneously, avoid water tank deformation, rise and heave the stupefied phenomenon even ftractureed, and ensure that the heat-insulating property of water-heater water tank。
The present invention is achieved by the following technical solutions:
A kind of solar energy polyurethane heat insulation material, described insulation material is obtained by the raw material mixed foaming of following weight fraction: '-diphenylmethane diisocyanate 70 ~ 100 parts, polyether polyol I 40 ~ 80 parts, polyether polyol II 10 ~ 30 parts, expanded vermiculite 3 ~ 6 parts, nano silicon 5 ~ 8 parts, chloro fluoroethane 10 ~ 20 parts, catalyst 1 ~ 5 part, foam stabiliser 1 ~ 5 part;Described polyether polyol I is lignin polyether polyhydric alcohol, and described polyether polyol II is be initiator, expoxy propane by modified olive oil is the polyether polyol that polymerization single polymerization monomer is polymerized。
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 hydroxyethylethylene diamine。
Further, described foam stabiliser is silicone based foam stabiliser。
Further, the degree of functionality of described polyether polyol I is 4.5 ~ 5.0, and its hydroxyl value is 370 ~ 410mgKOH/g, and it is made according to raw material and the method for following parts by weight:
(1) weighing lignin 50 ~ 100 parts, 30 ~ 50 parts of water, lignin peroxidase 1 ~ 5 part, catalase 1 ~ 3 part, 1 ~ 10 part of furan acetaldehyde and furfuryl alcohol 3 ~ 10 parts in reactor, reaction temperature is 80 DEG C, stirring reaction 5 hours, obtains enzymolysis modified lignin;
(2) enzymolysis modified lignin 100 parts, glycerol 250 ~ 350 parts, diethylene glycol 100 ~ 300 parts and Pd-Fe catalyst 0.01 ~ 0.05 part are mixed in reactor, controlling reaction temperature is 120 DEG C, by the logical nitrogen bubble reaction of reactor bottom, then evacuation, add expoxy propane 2 ~ 10 parts, atmospheric closed reacts 2 hours, obtains described polyether polyol I。
Further, the degree of functionality of described polyether polyol II is 5.0 ~ 6.0, and its hydroxyl value is 360 ~ 430mgKOH/g, and it is made according to raw material and the method for following parts by weight:
(1) weighing in ethylene glycol 20 ~ 50 parts and 1 ~ 5 part to 100 ~ 300 parts olive oil of magnesium chloride, controlling reaction temperature is 120 DEG C, reacts 3 hours, obtains modified olive oil;
(2) being mixed in reactor by 100 parts of modified olive oil and Pd-Fe catalyst 0.05 ~ 1.0 part, controlling reaction temperature is 150 DEG C, by the logical nitrogen bubble reaction of reactor bottom, then evacuation, adding expoxy propane 2 ~ 10 parts, atmospheric closed reacts 2 hours, obtains described polyether polyol II。
Further, described silicone based foam stabiliser is 3-[MPEG-550] propyl trialkoxy silane or 3-[poly-(ethylene glycol-copolymerization-propylene glycol) monomethyl ether] propyl trialkoxy silane。
The present invention adopts lignin polyether polyhydric alcohol and '-diphenylmethane diisocyanate to react to prepare hard polyurethane foam, increase the intensity of Polyurethane Thermal Insulation Building Materials。In system, the hydroxyl of lignin can react with '-diphenylmethane diisocyanate, obtains lignin-base polyurethane。Lignin is to have macromolecular compound cancellated, containing firm groups such as phenyl ring, can increase the intensity of foam in hard polyurethane foam。Therefore, hard bubbling (polyether polyol serves as soft section wherein) relative to what prepared by common polyether polyhydric alcohol, this lignin-base polyurethane foamed material performs better than in hot strength, comprcssive strength etc.。
It is the polyether polyol that polymerization single polymerization monomer is polymerized that part of the present invention adopts modified olive oil to be initiator, expoxy propane, after olive oil structure is modified, can introduce substantial amounts of hydroxyl on strand, and the polyether polyols alcohol functionalities prepared is high, and hydroxyl value is high;Its in system can reaction full and uniform with '-diphenylmethane diisocyanate, and promote the Homogeneous phase mixing dispersion in reactant of other auxiliary agent, generate and be evenly distributed fine and closely woven abscess, reduce foam-formed after shrinkage factor;Simultaneously because modified olive oil is Renewable resource, thus indirectly decreasing the use of petroleum derivative, decrease the dependence to petroleum resources, it is possible to as the raw material of novel foam。
Expanded vermiculite is the secondary metamorphic mineral of water aluminosilicate containing magnesium of a kind of layer structure, and like Muscovitum outside raw ore, it is by fabric and raw-vermiculite sheet after high-temperature roasting, the Vermiculitum that its volume energy obtains after expanding rapidly several times to tens times。Vermiculitum after expanded is in granular form, have heat insulation, resistance to freeze, antibacterial, fire prevention, the excellent properties such as sound absorption, what the present invention adopted is particle diameter is the expanded vermiculite of 40 ~ 70 orders, expanded vermiculite can be suitable increase polyurethane hard foam percent opening, and foamable gel and curing rate can be delayed, prevent foam from greatly and easily extruding inner bag and outer wall because of short time inner accumulated strength, reduce the generation of " bad foam ", reduce simultaneously foam-formed after shrinkage factor。
Nano silicon is the Inorganic Non-metallic Materials of a kind of excellent performance, it is big that it has specific surface area, superficial attractive forces is strong, the special performances such as chemical purity height, good, the thermal resistance of dispersive property, with its superior stability, reinforcing, thickening property and thixotropy, show unique characteristics in numerous subjects and field, have the effect do not replaced。The nano silicon adopted herein is nanometer silica line or hollow mesoporous silica nanospheres, after foaming raw material mixing, nano silicon can be distributed in the skeleton of cell wall, foamed materials, play the effect strengthening hole wall and foam stiffness, and without influence on foam structure, mixed with nano-silicon dioxide also can improve the intensity of solar energy polyurethane heat insulation material simultaneously。
The machine silicon class A foam A stabilizer that the present invention adopts is 3-[MPEG-550] propyl trialkoxy silane or 3-[poly-(ethylene glycol-copolymerization-propylene glycol) monomethyl ether] propyl trialkoxy silane, it can reduce the surface tension of urethane raw mixture, during foam is raised up to ripening, prevent, 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, formation of foam can be made spherical or oval spherical and the fine and closely woven abscess that is evenly distributed, expanded material heat-insulating property is stable, and increase the intensity of cell wall, because of the material compression phenomena of inside and outside differential pressure appearance when reducing foam-formed, increase the percent opening of foam simultaneously suitably, reduce foam-formed after shrinkage factor。
In sum, owing to have employed technique scheme, the invention has the beneficial effects as follows:
(1) present invention adopts lignin polyether polyhydric alcohol in foaming formulation, and prepared lignin-base rigid foam material, compared with the foamed materials prepared by traditional method, has more excellent comprcssive strength, hot strength and impact strength。
(2) solar energy polyurethane heat insulation material of the present invention is compared with prior art, except possessing conventional polyurethanes foamed materials high heat preservation performance, also reduce the foam contraction problem because each side reasons such as itself characteristic, production technology and direct labor's operant skill cause, it is to avoid water tank deforms, rises and heave the stupefied phenomenon even ftractureed。
Detailed description of the invention
All features disclosed in this specification, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way。
This specification (include any accessory claim, summary) disclosed in any feature, unless specifically stated otherwise, all can by other equivalences or there is the alternative features of similar purpose replaced。That is, unless specifically stated otherwise, each feature is an example in a series of equivalence or similar characteristics。
Embodiment 1
First preparing polyether polyol I, process is as follows:
(1) weighing lignin 80g, water 40g, lignin peroxidase 5g, catalase 1g, furan acetaldehyde 1g and furfuryl alcohol 5g in reactor, reaction temperature is 80 DEG C, stirring reaction 5 hours, obtains enzymolysis modified lignin;
(2) enzymolysis modified lignin 100g, glycerol 300g, diethylene glycol 200g and Pd-Fe catalyst 0.03g are mixed in reactor, controlling reaction temperature is 120 DEG C, by the logical nitrogen bubble reaction of reactor bottom, then evacuation, add expoxy propane 8g, atmospheric closed reacts 2 hours, and obtaining degree of functionality is 4.6, and hydroxyl value is the described polyether polyol I of 400mgKOH/g。
Preparing polyether polyol II again, process is as follows:
(1) weighing in ethylene glycol 40g and magnesium chloride 3g to 200g olive oil, controlling reaction temperature is 120 DEG C, reacts 3 hours, obtains modified olive oil;
(2) modified olive oil 100g and Pd-Fe catalyst 0.08g is mixed in reactor, controlling reaction temperature is 150 DEG C, by the logical nitrogen bubble reaction of reactor bottom, then evacuation, add expoxy propane 8g, atmospheric closed reacts 2 hours, and obtaining degree of functionality is 5.6, and hydroxyl value is the described polyether polyol II of 370mgKOH/g。
A kind of solar energy polyurethane heat insulation material, described insulation material is obtained by the raw material mixed foaming of following weight fraction: weigh polyether polyol I 40g, polyether polyol II 10g, expanded vermiculite 3g, nanometer silica line 5g, chloro fluoroethane 10g, diethanol monoisopropanolamine 2g and 3-[MPEG-550] propyl trialkoxy silane 2g mix homogeneously, then with '-diphenylmethane diisocyanate 80g mixed foaming, solar energy polyurethane heat insulation material of the present invention can be obtained after overcuring。
Embodiment 2
First preparing polyether polyol I, process is as follows:
(1) weighing lignin 50g, water 30g, lignin peroxidase 3g, catalase 2g, furan acetaldehyde 3g and furfuryl alcohol 10g in reactor, reaction temperature is 80 DEG C, stirring reaction 5 hours, obtains enzymolysis modified lignin;
(2) enzymolysis modified lignin 100g, glycerol 250g, diethylene glycol 100g and Pd-Fe catalyst 0.01g are mixed in reactor, controlling reaction temperature is 120 DEG C, by the logical nitrogen bubble reaction of reactor bottom, then evacuation, add expoxy propane 4g, atmospheric closed reacts 2 hours, and obtaining degree of functionality is 5.0, and hydroxyl value is the described polyether polyol I of 400mgKOH/g。
Preparing polyether polyol II again, process is as follows:
(1) weighing in ethylene glycol 20g and magnesium chloride 1g to 100g olive oil, controlling reaction temperature is 120 DEG C, reacts 3 hours, obtains modified olive oil;
(2) modified olive oil 100g and Pd-Fe catalyst 0.05g is mixed in reactor, controlling reaction temperature is 150 DEG C, by the logical nitrogen bubble reaction of reactor bottom, then evacuation, add expoxy propane 4g, atmospheric closed reacts 2 hours, and obtaining degree of functionality is 5.5, and hydroxyl value is the described polyether polyol II of 390mgKOH/g。
A kind of solar energy polyurethane heat insulation material, described insulation material is obtained by the raw material mixed foaming of following weight fraction: weigh polyether polyol I 40g, polyether polyol II 10g, 40 order expanded vermiculite 3g, nanometer silica line 5g, chloro fluoroethane 10g, hydroxyethylethylene diamine 2g and 3-[MPEG-550] propyl trialkoxy silane 2g mix homogeneously, then with '-diphenylmethane diisocyanate 80g mixed foaming, solar energy polyurethane heat insulation material of the present invention can be obtained after overcuring。
Embodiment 3
First preparing polyether polyol I, process is as follows:
(1) weighing lignin 100g, water 50g, lignin peroxidase 2g, catalase-3 g, furan acetaldehyde 8g and furfuryl alcohol 6g in reactor, reaction temperature is 80 DEG C, stirring reaction 5 hours, obtains enzymolysis modified lignin;
(2) enzymolysis modified lignin 100g, glycerol 350g, diethylene glycol 250g and Pd-Fe catalyst 0.05g are mixed in reactor, controlling reaction temperature is 120 DEG C, by the logical nitrogen bubble reaction of reactor bottom, then evacuation, add expoxy propane 10g, atmospheric closed reacts 2 hours, and obtaining degree of functionality is 4.7, and hydroxyl value is the described polyether polyol I of 410mgKOH/g。
Preparing polyether polyol II again, process is as follows:
(1) weighing in ethylene glycol 50g and magnesium chloride 5g to 300g olive oil, controlling reaction temperature is 120 DEG C, reacts 3 hours, obtains modified olive oil;
(2) modified olive oil 100g and Pd-Fe catalyst 1.0g is mixed in reactor, controlling reaction temperature is 150 DEG C, by the logical nitrogen bubble reaction of reactor bottom, then evacuation, add expoxy propane 8g, atmospheric closed reacts 2 hours, and obtaining degree of functionality is 6.0, and hydroxyl value is the described polyether polyol II of 350mgKOH/g。
A kind of solar energy polyurethane heat insulation material, described insulation material is obtained by the raw material mixed foaming of following weight fraction: weigh polyether polyol I 80g, polyether polyol II 20g, 60 order expanded vermiculite 6g, nanometer silica line 8g, chloro fluoroethane 20g, hydroxyethylethylene diamine 5g and 3-[poly-(ethylene glycol-copolymerization-propylene glycol) monomethyl ether] propyl trialkoxy silane 4g mix homogeneously, then with '-diphenylmethane diisocyanate 100g mixed foaming, solar energy polyurethane heat insulation material of the present invention can be obtained after overcuring。
Embodiment 4
First preparing polyether polyol I, process is as follows:
(1) weighing lignin 80g, water 40g, lignin peroxidase 1g, catalase-3 g, furan acetaldehyde 10g and furfuryl alcohol 5g in reactor, reaction temperature is 80 DEG C, stirring reaction 5 hours, obtains enzymolysis modified lignin;
(3) enzymolysis modified lignin 100g, glycerol 300g, diethylene glycol 200g and Pd-Fe catalyst 0.03g are mixed in reactor, controlling reaction temperature is 120 DEG C, by the logical nitrogen bubble reaction of reactor bottom, then evacuation, add expoxy propane 8g, atmospheric closed reacts 2 hours, and obtaining degree of functionality is 5.0, and hydroxyl value is the described polyether polyol I of 370mgKOH/g。
Preparing polyether polyol II again, process is as follows:
(1) weighing in ethylene glycol 40g and magnesium chloride 3g to 200g olive oil, controlling reaction temperature is 120 DEG C, reacts 3 hours, obtains modified olive oil;
(3) modified olive oil 100g and Pd-Fe catalyst 0.08g is mixed in reactor, controlling reaction temperature is 150 DEG C, by the logical nitrogen bubble reaction of reactor bottom, then evacuation, add expoxy propane 8g, atmospheric closed reacts 2 hours, and obtaining degree of functionality is 5.5, and hydroxyl value is the described polyether polyol II of 360mgKOH/g。
A kind of solar energy polyurethane heat insulation material, described insulation material is obtained by the raw material mixed foaming of following weight fraction: weigh polyether polyol I 70g, polyether polyol II 20g, 70 order expanded vermiculite 5g, hollow mesoporous silica nanospheres 7g, chloro fluoroethane 10g, diethanol monoisopropanolamine 5g and 3-[poly-(ethylene glycol-copolymerization-propylene glycol) monomethyl ether] propyl trialkoxy silane 2g mix homogeneously, then with '-diphenylmethane diisocyanate 80g mixed foaming, solar energy polyurethane heat insulation material of the present invention can be obtained after overcuring。
The physical function parameter of the solar energy polyurethane heat insulation material respectively embodiment 1-4 prepared detects, and test result is as shown in table 1。
Table 1
From table, the indexs such as the heat conductivity of solar energy polyurethane heat insulation material, comprcssive strength, tensile bond strength, dimensional stability and rate of closed hole prepared by above example of the present invention all have than existing insulation material and improve significantly, the phenomenon such as ungauged regions, deformation, expansion, cracking under chilled or hot conditions, is the insulation material of a kind of excellent performance。
The invention is not limited in aforesaid detailed description of the invention。The present invention expands to any new feature disclosed in this manual or any new combination, and the step of the arbitrary new method disclosed or process or any new combination。

Claims (8)

1. a solar energy polyurethane heat insulation material, it is characterized in that, described insulation material is obtained by the raw material mixed foaming of following weight fraction: '-diphenylmethane diisocyanate 70 ~ 100 parts, polyether polyol I 40 ~ 80 parts, polyether polyol II 10 ~ 30 parts, expanded vermiculite 3 ~ 6 parts, nano silicon 5 ~ 8 parts, chloro fluoroethane 10 ~ 20 parts, catalyst 1 ~ 5 part, foam stabiliser 1 ~ 5 part;Described polyether polyol I is lignin polyether polyhydric alcohol, and described polyether polyol II is be initiator, expoxy propane by modified olive oil is the polyether polyol that polymerization single polymerization monomer is polymerized。
2. solar energy polyurethane heat insulation material according to claim 1, it is characterised in that: the particle diameter of described expanded vermiculite is 40 ~ 70 orders。
3. solar energy polyurethane heat insulation material according to claim 1, it is characterised in that: described nano silicon is nanometer silica line or hollow mesoporous silica nanospheres。
4. solar energy polyurethane heat insulation material according to claim 1, it is characterised in that: described catalyst is diethanol monoisopropanolamine or hydroxyethylethylene diamine。
5. solar energy polyurethane heat insulation material according to claim 1, it is characterised in that: described foam stabiliser is silicone based foam stabiliser。
6. the solar energy polyurethane heat insulation material according to claim 1 to 5 any one claim, it is characterized in that: the degree of functionality of described polyether polyol I is 4.5 ~ 5.0, its hydroxyl value is 370 ~ 410mgKOH/g, and it is made according to raw material and the method for following parts by weight:
(1) weighing lignin 50 ~ 100 parts, 30 ~ 50 parts of water, lignin peroxidase 1 ~ 5 part, catalase 1 ~ 3 part, 1 ~ 10 part of furan acetaldehyde and furfuryl alcohol 3 ~ 10 parts in reactor, reaction temperature is 80 DEG C, stirring reaction 5 hours, obtains enzymolysis modified lignin;
(2) enzymolysis modified lignin 100 parts, glycerol 250 ~ 350 parts, diethylene glycol 100 ~ 300 parts and Pd-Fe catalyst 0.01 ~ 0.05 part are mixed in reactor, controlling reaction temperature is 120 DEG C, by the logical nitrogen bubble reaction of reactor bottom, then evacuation, add expoxy propane 2 ~ 10 parts, atmospheric closed reacts 2 hours, obtains described polyether polyol I。
7. the solar energy polyurethane heat insulation material according to claim 1 to 5 any one claim, it is characterized in that: the degree of functionality of described polyether polyol II is 5.0 ~ 6.0, its hydroxyl value is 360 ~ 430mgKOH/g, and it is made according to raw material and the method for following parts by weight:
(1) weighing in ethylene glycol 20 ~ 50 parts and 1 ~ 5 part to 100 ~ 300 parts olive oil of magnesium chloride, controlling reaction temperature is 120 DEG C, reacts 3 hours, obtains modified olive oil;
(2) being mixed in reactor by 100 parts of modified olive oil and Pd-Fe catalyst 0.05 ~ 1.0 part, controlling reaction temperature is 150 DEG C, by the logical nitrogen bubble reaction of reactor bottom, then evacuation, adding expoxy propane 2 ~ 10 parts, atmospheric closed reacts 2 hours, obtains described polyether polyol II。
8. solar energy polyurethane heat insulation material according to claim 5, it is characterised in that: described silicone based foam stabiliser is 3-[MPEG-550] propyl trialkoxy silane or 3-[poly-(ethylene glycol-copolymerization-propylene glycol) monomethyl ether] propyl trialkoxy silane。
CN201610074105.0A 2016-02-03 2016-02-03 Solar polyurethane thermal insulation material Withdrawn CN105693974A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610074105.0A CN105693974A (en) 2016-02-03 2016-02-03 Solar polyurethane thermal insulation material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610074105.0A CN105693974A (en) 2016-02-03 2016-02-03 Solar polyurethane thermal insulation material

Publications (1)

Publication Number Publication Date
CN105693974A true CN105693974A (en) 2016-06-22

Family

ID=56230250

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610074105.0A Withdrawn CN105693974A (en) 2016-02-03 2016-02-03 Solar polyurethane thermal insulation material

Country Status (1)

Country Link
CN (1) CN105693974A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106221180A (en) * 2016-07-25 2016-12-14 广西南宁智翠科技咨询有限公司 A kind of novel solar water heater water tank environment-friendly insulating material
CN106279610A (en) * 2016-08-15 2017-01-04 黄宝兴 Polyurethane heat-insulating heat-preserving material
CN107814906A (en) * 2017-11-22 2018-03-20 南宁可煜能源科技有限公司 A kind of solar water heater polyurethane heat insulation material and preparation method thereof
CN110964309A (en) * 2019-12-11 2020-04-07 泉州玺堡家居科技有限公司 High-hardness sponge and processing technology thereof

Citations (3)

* 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
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 (3)

* 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
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
CN106221180A (en) * 2016-07-25 2016-12-14 广西南宁智翠科技咨询有限公司 A kind of novel solar water heater water tank environment-friendly insulating material
CN106279610A (en) * 2016-08-15 2017-01-04 黄宝兴 Polyurethane heat-insulating heat-preserving material
CN107814906A (en) * 2017-11-22 2018-03-20 南宁可煜能源科技有限公司 A kind of solar water heater polyurethane heat insulation material and preparation method thereof
CN110964309A (en) * 2019-12-11 2020-04-07 泉州玺堡家居科技有限公司 High-hardness sponge and processing technology thereof

Similar Documents

Publication Publication Date Title
CN105693976A (en) Polyurethane foam thermal insulation material
CN105504204A (en) Polyurethane heat preservation material
CN105504203A (en) Polyurethane rigid foam
CN105542104A (en) Polyurethane hard foam thermal-insulation material
CN105693974A (en) Solar polyurethane thermal insulation material
CN105693973A (en) Rigid foam thermal insulation material
CN105601868A (en) Rigid foam polyurethane thermal insulation material
CN102898778B (en) Preparation method for melamine formaldehyde resin closed-cell foam
CN105131237B (en) The preparation method of full water foamed plant oil base RPUF
CN102633974A (en) High-flame-retardance temperature preservation plate and preparation method thereof
CN106279610A (en) Polyurethane heat-insulating heat-preserving material
CN103319678B (en) Solar water heater water tank polyurethane hard foam lagging material
CN105601869A (en) Solar rigid polyurethane foam thermal insulation material
CN102173147A (en) Modified hard bubble polyurethane composite plate and manufacturing method thereof
CN106189192B (en) A kind of Kafra fiber-polyurethane composite foam material and preparation method thereof
CN103342792B (en) Polyurethane rigid foam organic fireproof heat preservation material for solar water tank
CN102229697A (en) Solar polyurethane thermal insulation material
CN102766247A (en) Rigid polyurethane/polyvinyl chloride composite foam plastic and preparation method thereof
CN107722221A (en) A kind of composite foamed thermal insulation building material of alumina fibre POSS modified polyurethanes and preparation method thereof
CN105504218A (en) Solar hard foam heat-preservation material
CN107903380A (en) Barrel of beer polyurethane foam heat insulation material and preparation method thereof
CN105693975A (en) Rigid polyurethane foam thermal insulation material
CN105669930A (en) Thermal insulation material
CN111647266A (en) Polyurethane foam material and preparation method thereof
CN114437544A (en) High-temperature-resistant bismaleimide-polyimide interpenetrating structure foam material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20160622

WW01 Invention patent application withdrawn after publication