CN105504203A - Polyurethane rigid foam - Google Patents
Polyurethane rigid foam Download PDFInfo
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- CN105504203A CN105504203A CN201610074137.0A CN201610074137A CN105504203A CN 105504203 A CN105504203 A CN 105504203A CN 201610074137 A CN201610074137 A CN 201610074137A CN 105504203 A CN105504203 A CN 105504203A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4891—Polyethers modified with higher fatty oils or their acids or by resin acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-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
- C08J9/14—Working-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
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08K2201/011—Nanostructured additives
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Abstract
The invention relates to a foam material, and discloses polyurethane rigid foam. A heat preservation material is prepared by mixing and foaming the following raw materials in parts by weight: 70 to 100 parts of isocyanate, 40 to 80 parts of polyether glycol I, 10 to 30 parts of polyether glycol II, 3 to 6 parts of expanded vermiculite, 5 to 8 parts of nanosilicon dioxide, 10 to 20 parts of a foaming agent, 1 to 5 parts of a catalyst, and 1 to 5 parts of 3-[poly(ethylene glycol-copolymerized-propylene glycol) mono methyl ether] chloropropyltrialkoxysilane, wherein the polyether glycol I is lignin polyether glycol; the polyether glycol II is polyether glycol polymerized by modified sunflower seed oil serving as a starting agent and epoxypropane serving as a polymeric monomer. The heat preservation material is higher in compressive strength, tensile strength and impact strength, and meanwhile, phenomena of deformation, bulging, ridging and even cracking of a water tank are avoided.
Description
Technical field
The present invention relates to foam materials, particularly relate to a kind of polyurethane hard foam.
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 energy source, wherein sun power is utilize and develop the renewable energy source the widest, development prospect is best, and be now widely used in all trades and professions, 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 first of solar water heater in the world uses state and producing country at present.
As everyone knows, concerning solar water heater, the selection of water tank heat preserving material is vital, and the lagging material that can be used as water tank at present mainly contains polyurethane foam, phenol formaldehyde foam, ultra-fine fibre etc.Polyurethane foam be by isocyanic ester to mix with polyether composition being poured in mould or water tank cavity foam obtained, wherein polyether composition contains polyether glycol, whipping agent, catalyzer, solidifying agent, fire retardant, stablizer etc., because polyurethane foam has the advantages such as moulding process is simple, thermal conductivity is low, it is the lagging material that water tank mainly adopts.
Containing alcoholic extract hydroxyl group in lignin structure, reaction can be carried out with isocyanic ester and prepares hard polyurethane foam by Substitute For Partial polyvalent alcohol, but due to hydroxy radical content lower, cause its activity lower, limit it and apply; In addition, in the process of preparation polyurethane foam, be woodenly usually dispersed in the middle of polyvalent alcohol with macromolecular particle form, cause the decline of reactivity worth and the uneven of abscess, so want to use xylogen in a large number in urethane, the problems of dissolution of xylogen just must be resolved.
The main molecules of vegetables oil consists of triacylglycerol ester, also has a small amount of free fatty acids and partial glycerol ester, the phosphatide of 0.1-0.5%, tocopherol and vitamin-E.In general, the oleic acid content in vegetables oil is higher, and linoleic acid plus linolenic acid content is lower, and its oxidative stability is better.Containing a large amount of carbon-carbon double bond in vegetable oil molecule, the oxidation mechanism main manifestations of vegetables oil is active allyl reaction, the major cause of this its oxidative stability difference just.Vegetables oil major part is obtained by stable raw material, is therefore a kind of worthwhile urethane raw, and shortcoming is that it lacks and the necessary reactive hydrogen of isocyanate reaction, therefore needs to carry out modification to vegetables oil.
Polyurethane hard foam in process of production, because of the reason of each side such as itself characteristic, production technique and direct labor's operating skill, the problem of ubiquity foam contraction, foam and housing parts is easily caused to come off or all come off, finally cause casing deformation, vacuum mouth of pipe foam ftractures, and What is more, polyurethane hard foam transverse direction between inner bag and shell or longitudinal cracking, greatly reduce the heat insulation effect of water tank.
Summary of the invention
Goal of the invention of the present invention is: for above-mentioned Problems existing, provides a kind of polyurethane hard foam.This polyurethane hard foam has the mechanical properties such as more excellent ultimate compression strength, tensile strength, overcomes the shortcoming that foaming post shrinkage is large simultaneously, avoids water tank to be out of shape, rises 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 polyurethane hard foam, described lagging material is obtained by the raw material mixed foaming of following weight fraction: isocyanic ester 70 ~ 100 parts, polyether glycol I 40 ~ 80 parts, polyether glycol II 10 ~ 30 parts, expanded vermiculite 3 ~ 6 parts, nano silicon 5 ~ 8 parts, whipping agent 10 ~ 20 parts, catalyzer 1 ~ 5 part, 3-[poly-(ethylene glycol-copolymerization-propylene glycol) monomethyl ether] propyl trialkoxy silane 1 ~ 5 part; Described polyether glycol I is lignin polyether polyvalent alcohol, described polyether glycol II be by modification plam oil be initiator, propylene oxide is the polyether glycol that polymerization single polymerization monomer is polymerized.
Further, described isocyanic ester is one or more in dimer acid diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate or '-diphenylmethane diisocyanate.
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 whipping agent is one or more in a fluorine dichloro hexane, Trichloromonofluoromethane, methyl chlorofluoride, chlorodifluoroethane and chloro fluoroethane.
Further, described catalyzer is di-alcohol monoisopropanolamine or hydroxyethylethylene diamine.
Further, the functionality of described polyether glycol I is 4.5 ~ 5.0, and its hydroxyl value is 370 ~ 410mgKOH/g, and its raw material according to following parts by weight and method are made:
(1) take 50 ~ 100 parts, xylogen, 30 ~ 50 parts, water, lignin peroxidase 1 ~ 5 part, catalase 1 ~ 3 part, 1 ~ 10 part, furans acetaldehyde and furfuryl alcohol 3 ~ 10 parts are in reactor, and temperature of reaction is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modified xylogen;
(2) 100 parts, enzymolysis modified xylogen, glycerol 250 ~ 350 parts, glycol ether 100 ~ 300 parts and Pd-Fe catalyzer 0.01 ~ 0.05 part are mixed in reactor, controlling temperature of reaction is 120 DEG C, lead to nitrogen bubble by reactor bottom to react, then vacuumize, add propylene oxide 2 ~ 10 parts, atmospheric closed reacts 2 hours, obtains described polyether glycol I.
Further, the functionality of described polyether glycol II is 5.0 ~ 6.0, and its hydroxyl value is 360 ~ 430mgKOH/g, and its raw material according to following parts by weight and method are made:
(1) take in ethylene glycol 20 ~ 50 parts and magnesium chloride 1 ~ 5 part to 100 ~ 300 parts plam oil, controlling temperature of reaction is 120 DEG C, reacts 3 hours, obtains modification plam oil;
(2) be mixed in reactor by modification plam oil 100 parts and Pd-Fe catalyzer 0.05 ~ 1.0 part, controlling temperature of reaction is 150 DEG C, leads to nitrogen bubble react by reactor bottom, then vacuumize, add propylene oxide 2 ~ 10 parts, atmospheric closed reacts 2 hours, obtains described polyether glycol II.
The present invention adopts lignin polyether polyvalent alcohol and isocyanic ester to carry out reaction to prepare hard polyurethane foam, increases the intensity of Polyurethane Thermal Insulation Building Materials.In system, the hydroxyl of xylogen can with isocyanate reaction, obtain lignin-base urethane.Xylogen has cancellated, containing firm groups such as phenyl ring macromolecular compound, can increase the intensity of foam in hard polyurethane foam.Therefore relative to hard bubbling (polyether glycol serves as soft section wherein) of being prepared by common polyether polyvalent alcohol, this lignin-base polyurethane foamed material shows better in tensile strength, ultimate compression strength etc.
Part employing modification plam oil of the present invention is initiator, propylene oxide is the polyether glycol that polymerization single polymerization monomer is polymerized, and plam oil structure is carried out modified, can introduce a large amount of hydroxyls on molecular chain, and the polyether polyols alcohol functionalities prepared is high, and hydroxyl value is high; It can reaction full and uniform with isocyanic ester in system, and promotes the Homogeneous phase mixing dispersion of other auxiliary agent in reactant, generates the fine and closely woven abscess that is evenly distributed, reduce foam-formed after shrinking percentage; Simultaneously because modification plam oil is renewable resources, thus indirectly decrease the use of petroleum derivative, decrease the dependence to petroleum resources, can as the raw material of novel foam.
Expanded vermiculite be a kind of laminate structure containing the secondary metamorphic mineral of water aluminosilicate of magnesium, raw ore is outer, and like mica, it is by fabric and raw-vermiculite sheet after high-temperature roasting, the vermiculite that its volume energy undergoes rapid expansion obtains after several times to tens times.Vermiculite after expanded is particulate state, have heat insulation, resistance toly to freeze, antibacterial, fire prevention, the excellent properties such as sound absorption, what the present invention adopted is particle diameter is 40 ~ 70 object expanded vermiculites, expanded vermiculite can be suitable the percentage of open area of increase polyurethane hard foam, and foamable gel and curing speed can be delayed, prevent foam from greatly and easily extruding inner bag and outer wall because of short period of time inner accumulated strength, reduce the generation of " bad foam ", reduce simultaneously foam-formed after shrinking percentage.
Nano silicon is a kind of ceramic of excellent performance, it is large that it has specific surface area, superficial attractive forces is strong, the performance that chemical purity is high, dispersing property good, thermal resistance etc. is special, with its superior stability, reinforcing, thickening property and thixotropy, show unique characteristics in numerous subject 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, foam materials, play the effect strengthening hole wall and foam stiffness, and can not foam structure be affected, mixed with nano-silicon dioxide also can improve the intensity of polyurethane hard foam simultaneously.
The suds-stabilizing agent that the present invention adopts is 3-[poly-(ethylene glycol-copolymerization-propylene glycol) monomethyl ether] propyl trialkoxy silane, it can reduce the surface tension of urethane raw mixture, be raised up between the maturation period at foam, the material preventing the thermodynamics unstable state of foam from occurring by surface tension.
After hard polyurethane foam formula material mixing jetting of the present invention, spherical or the oval spherical and fine and closely woven abscess that is evenly distributed of formation of foam can be made, foam material heat-insulating property is stablized, and increase the intensity of cell wall, because of the Material compression phenomenon of inside and outside differential pressure appearance when reducing foam-formed, increase the percentage of open area of foam simultaneously suitably, reduce foam-formed after shrinking percentage.
In sum, owing to have employed technique scheme, the invention has the beneficial effects as follows:
(1) the present invention adopts lignin polyether polyvalent alcohol in foaming formulation, and obtained lignin-base rigid foam material, compared with the foam materials prepared by traditional method, has more excellent ultimate compression strength, tensile strength and shock strength.
(2) polyurethane hard foam of the present invention compared with prior art, except possessing conventional polyurethanes foam materials high heat preservation performance, also reduce the foam contraction problem because each side reasons such as itself characteristic, production technique and direct labor's operating skill cause, avoid water tank to be out of shape, rise and heave the stupefied phenomenon even ftractureed.
Embodiment
All features disclosed in this specification sheets, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Arbitrary feature disclosed in this specification sheets (comprising any accessory claim, summary), unless specifically stated otherwise, all can be replaced by other equivalences or the alternative features with similar object.That is, unless specifically stated otherwise, each feature is an example in a series of equivalence or similar characteristics.
Embodiment 1
First prepare polyether glycol I, process is as follows:
(1) take xylogen 80g, water 40g, lignin peroxidase 5g, catalase 1g, furans acetaldehyde 1g and furfuryl alcohol 5g is in reactor, and temperature of reaction is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modified xylogen;
(2) enzymolysis modified xylogen 100g, glycerol 300g, glycol ether 200g and Pd-Fe catalyzer 0.03g are mixed in reactor, controlling temperature of reaction is 120 DEG C, lead to nitrogen bubble by reactor bottom to react, then vacuumize, add propylene oxide 8g, atmospheric closed reacts 2 hours, and obtaining functionality is 4.6, and hydroxyl value is the described polyether glycol I of 400mgKOH/g.
Prepare polyether glycol II again, process is as follows:
(1) take in ethylene glycol 40g and magnesium chloride 3g to 200g plam oil, controlling temperature of reaction is 120 DEG C, reacts 3 hours, obtains modification plam oil;
(2) modification plam oil 100g and Pd-Fe catalyzer 0.08g is mixed in reactor, controlling temperature of reaction is 150 DEG C, lead to nitrogen bubble by reactor bottom to react, then vacuumize, add propylene oxide 8g, atmospheric closed reacts 2 hours, and obtaining functionality is 5.6, and hydroxyl value is the described polyether glycol II of 370mgKOH/g.
A kind of polyurethane hard foam, described lagging material is obtained by the raw material mixed foaming of following weight fraction: take polyether glycol I 40g, polyether glycol II 10g, expanded vermiculite 3g, nanometer silica line 5g, one fluorine dichloro hexane 10g, di-alcohol monoisopropanolamine 2g and 3-[poly-(ethylene glycol-copolymerization-propylene glycol) monomethyl ether] propyl trialkoxy silane 2g mixes, then with dimer acid diisocyanate 80g mixed foaming, polyurethane hard foam of the present invention can be obtained after overcuring.
Embodiment 2
First prepare polyether glycol I, process is as follows:
(1) take xylogen 50g, water 30g, lignin peroxidase 3g, catalase 2g, furans acetaldehyde 3g and furfuryl alcohol 10g is in reactor, and temperature of reaction is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modified xylogen;
(2) enzymolysis modified xylogen 100g, glycerol 250g, glycol ether 100g and Pd-Fe catalyzer 0.01g are mixed in reactor, controlling temperature of reaction is 120 DEG C, lead to nitrogen bubble by reactor bottom to react, then vacuumize, add propylene oxide 4g, atmospheric closed reacts 2 hours, and obtaining functionality is 5.0, and hydroxyl value is the described polyether glycol I of 400mgKOH/g.
Prepare polyether glycol II again, process is as follows:
(1) take in ethylene glycol 20g and magnesium chloride 1g to 100g plam oil, controlling temperature of reaction is 120 DEG C, reacts 3 hours, obtains modification plam oil;
(2) modification plam oil 100g and Pd-Fe catalyzer 0.05g is mixed in reactor, controlling temperature of reaction is 150 DEG C, lead to nitrogen bubble by reactor bottom to react, then vacuumize, add propylene oxide 4g, atmospheric closed reacts 2 hours, and obtaining functionality is 5.5, and hydroxyl value is the described polyether glycol II of 390mgKOH/g.
A kind of polyurethane hard foam, described lagging material is obtained by the raw material mixed foaming of following weight fraction: take polyether glycol I 40g, polyether glycol II 10g, 40 order expanded vermiculite 3g, nanometer silica line 5g, Trichloromonofluoromethane 10g, hydroxyethylethylene diamine 2g and 3-[poly-(ethylene glycol-copolymerization-propylene glycol) monomethyl ether] propyl trialkoxy silane 2g mixes, then with 1, hexamethylene-diisocyanate 80g mixed foaming, can obtain polyurethane hard foam of the present invention after overcuring.
Embodiment 3
First prepare polyether glycol I, process is as follows:
(1) take xylogen 100g, water 50g, lignin peroxidase 2g, catalase-3 g, furans acetaldehyde 8g and furfuryl alcohol 6g is in reactor, and temperature of reaction is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modified xylogen;
(2) enzymolysis modified xylogen 100g, glycerol 350g, glycol ether 250g and Pd-Fe catalyzer 0.05g are mixed in reactor, controlling temperature of reaction is 120 DEG C, lead to nitrogen bubble by reactor bottom to react, then vacuumize, add propylene oxide 10g, atmospheric closed reacts 2 hours, and obtaining functionality is 4.7, and hydroxyl value is the described polyether glycol I of 410mgKOH/g.
Prepare polyether glycol II again, process is as follows:
(1) take in ethylene glycol 50g and magnesium chloride 5g to 300g plam oil, controlling temperature of reaction is 120 DEG C, reacts 3 hours, obtains modification plam oil;
(2) modification plam oil 100g and Pd-Fe catalyzer 1.0g is mixed in reactor, controlling temperature of reaction is 150 DEG C, lead to nitrogen bubble by reactor bottom to react, then vacuumize, add propylene oxide 8g, atmospheric closed reacts 2 hours, and obtaining functionality is 6.0, and hydroxyl value is the described polyether glycol II of 350mgKOH/g.
A kind of polyurethane hard foam, described lagging material is obtained by the raw material mixed foaming of following weight fraction: take polyether glycol I 80g, polyether glycol II 20g, 60 order expanded vermiculite 6g, nanometer silica line 8g, methyl chlorofluoride 20g, hydroxyethylethylene diamine 5g and 3-[poly-(ethylene glycol-copolymerization-propylene glycol) monomethyl ether] propyl trialkoxy silane 4g mixes, then with tolylene diisocyanate 100g mixed foaming, polyurethane hard foam of the present invention can be obtained after overcuring.
Embodiment 4
First prepare polyether glycol I, process is as follows:
(1) take xylogen 80g, water 40g, lignin peroxidase 1g, catalase-3 g, furans acetaldehyde 10g and furfuryl alcohol 5g is in reactor, and temperature of reaction is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modified xylogen;
(3) enzymolysis modified xylogen 100g, glycerol 300g, glycol ether 200g and Pd-Fe catalyzer 0.03g are mixed in reactor, controlling temperature of reaction is 120 DEG C, lead to nitrogen bubble by reactor bottom to react, then vacuumize, add propylene oxide 8g, atmospheric closed reacts 2 hours, and obtaining functionality is 5.0, and hydroxyl value is the described polyether glycol I of 370mgKOH/g.
Prepare polyether glycol II again, process is as follows:
(1) take in ethylene glycol 40g and magnesium chloride 3g to 200g plam oil, controlling temperature of reaction is 120 DEG C, reacts 3 hours, obtains modification plam oil;
(3) modification plam oil 100g and Pd-Fe catalyzer 0.08g is mixed in reactor, controlling temperature of reaction is 150 DEG C, lead to nitrogen bubble by reactor bottom to react, then vacuumize, add propylene oxide 8g, atmospheric closed reacts 2 hours, and obtaining functionality is 5.5, and hydroxyl value is the described polyether glycol II of 360mgKOH/g.
A kind of polyurethane hard foam, described lagging material is obtained by the raw material mixed foaming of following weight fraction: take polyether glycol I 70g, polyether glycol II 20g, 70 order expanded vermiculite 5g, hollow mesoporous silica nanospheres 7g, chloro fluoroethane 10g, di-alcohol monoisopropanolamine 5g and 3-[poly-(ethylene glycol-copolymerization-propylene glycol) monomethyl ether] propyl trialkoxy silane 2g mixes, then with dimer acid diisocyanate 80g mixed foaming, polyurethane hard foam of the present invention can be obtained after overcuring.
Detect the physical function parameter of the polyurethane hard foam that embodiment 1-4 prepares respectively, test result is as shown in table 1.
Table 1
From table, the thermal conductivity of polyurethane hard foam prepared by the above embodiment of the present invention, ultimate compression strength, tensile bond strength, the index such as dimensional stability and rate of closed hole all have than existing lagging material and improve significantly, the phenomenon such as ungauged regions, distortion, expansion, cracking under freezing or hot conditions is a kind of lagging material of excellent performance.
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature of disclosing in this manual or any combination newly, and the step of the arbitrary new method disclosed or process or any combination newly.
Claims (8)
1. a polyurethane hard foam, it is characterized in that, described lagging material is obtained by the raw material mixed foaming of following weight fraction: isocyanic ester 70 ~ 100 parts, polyether glycol I 40 ~ 80 parts, polyether glycol II 10 ~ 30 parts, expanded vermiculite 3 ~ 6 parts, nano silicon 5 ~ 8 parts, whipping agent 10 ~ 20 parts, catalyzer 1 ~ 5 part, 3-[poly-(ethylene glycol-copolymerization-propylene glycol) monomethyl ether] propyl trialkoxy silane 1 ~ 5 part; Described polyether glycol I is lignin polyether polyvalent alcohol, described polyether glycol II be by modification plam oil be initiator, propylene oxide is the polyether glycol that polymerization single polymerization monomer is polymerized.
2. polyurethane hard foam according to claim 1, is characterized in that: described isocyanic ester is one or more in dimer acid diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate or '-diphenylmethane diisocyanate.
3. polyurethane hard foam according to claim 1, is characterized in that: the particle diameter of described expanded vermiculite is 40 ~ 70 orders.
4. polyurethane hard foam according to claim 1, is characterized in that: described nano silicon is nanometer silica line or hollow mesoporous silica nanospheres.
5. polyurethane hard foam according to claim 1, is characterized in that: described whipping agent is one or more in a fluorine dichloro hexane, Trichloromonofluoromethane, methyl chlorofluoride, chlorodifluoroethane and chloro fluoroethane.
6. polyurethane hard foam according to claim 1, is characterized in that: described catalyzer is di-alcohol monoisopropanolamine or hydroxyethylethylene diamine.
7. the polyurethane hard foam according to any one of claim 1 to 6 claim, is characterized in that: the functionality of described polyether glycol I is 4.5 ~ 5.0, and its hydroxyl value is 370 ~ 410mgKOH/g, and its raw material according to following parts by weight and method are made:
(1) take 50 ~ 100 parts, xylogen, 30 ~ 50 parts, water, lignin peroxidase 1 ~ 5 part, catalase 1 ~ 3 part, 1 ~ 10 part, furans acetaldehyde and furfuryl alcohol 3 ~ 10 parts are in reactor, and temperature of reaction is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modified xylogen;
(2) 100 parts, enzymolysis modified xylogen, glycerol 250 ~ 350 parts, glycol ether 100 ~ 300 parts and Pd-Fe catalyzer 0.01 ~ 0.05 part are mixed in reactor, controlling temperature of reaction is 120 DEG C, lead to nitrogen bubble by reactor bottom to react, then vacuumize, add propylene oxide 2 ~ 10 parts, atmospheric closed reacts 2 hours, obtains described polyether glycol I.
8. the polyurethane hard foam according to any one of claim 1 to 6 claim, is characterized in that: the functionality of described polyether glycol II is 5.0 ~ 6.0, and its hydroxyl value is 360 ~ 430mgKOH/g, and its raw material according to following parts by weight and method are made:
(1) take in ethylene glycol 20 ~ 50 parts and magnesium chloride 1 ~ 5 part to 100 ~ 300 parts plam oil, controlling temperature of reaction is 120 DEG C, reacts 3 hours, obtains modification plam oil;
(2) be mixed in reactor by modification plam oil 100 parts and Pd-Fe catalyzer 0.05 ~ 1.0 part, controlling temperature of reaction is 150 DEG C, leads to nitrogen bubble react by reactor bottom, then vacuumize, add propylene oxide 2 ~ 10 parts, atmospheric closed reacts 2 hours, obtains described polyether glycol II.
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| CN201610074137.0A CN105504203A (en) | 2016-02-03 | 2016-02-03 | Polyurethane rigid foam |
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| CN201610074137.0A CN105504203A (en) | 2016-02-03 | 2016-02-03 | Polyurethane rigid foam |
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| CN105504203A true CN105504203A (en) | 2016-04-20 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106046295A (en) * | 2016-07-01 | 2016-10-26 | 南宁可煜能源科技有限公司 | Foaming method of polyurethane foam as insulation material of water tank of solar water heater |
| CN106146780A (en) * | 2016-07-01 | 2016-11-23 | 南宁可煜能源科技有限公司 | A kind of high-strength solar water heater water tank polyurethane foam heat insulation material |
| CN106907871A (en) * | 2017-01-17 | 2017-06-30 | 广西吉宽太阳能设备有限公司 | A kind of solar energy water tank shell |
| CN107513266A (en) * | 2017-08-31 | 2017-12-26 | 苏州市苏真床垫有限公司 | A kind of preparation method of mountain palm fibre foaming mattress |
| CN107603255A (en) * | 2017-08-31 | 2018-01-19 | 苏州市苏真床垫有限公司 | A kind of preparation method of monkey grass foam pad mattress |
| 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 |
| CN116535989A (en) * | 2023-04-17 | 2023-08-04 | 重庆永迪高分子材料有限公司 | Sponge adhesive tape and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106046295A (en) * | 2016-07-01 | 2016-10-26 | 南宁可煜能源科技有限公司 | Foaming method of polyurethane foam as insulation material of water tank of solar water heater |
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| CN106907871A (en) * | 2017-01-17 | 2017-06-30 | 广西吉宽太阳能设备有限公司 | A kind of solar energy water tank shell |
| CN107513266A (en) * | 2017-08-31 | 2017-12-26 | 苏州市苏真床垫有限公司 | A kind of preparation method of mountain palm fibre foaming mattress |
| CN107603255A (en) * | 2017-08-31 | 2018-01-19 | 苏州市苏真床垫有限公司 | A kind of preparation method of monkey grass foam pad mattress |
| 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 |
| CN116535989A (en) * | 2023-04-17 | 2023-08-04 | 重庆永迪高分子材料有限公司 | Sponge adhesive tape and preparation method thereof |
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