CN115028880B - Light-weight heat-preservation fireproof composite board and preparation process thereof - Google Patents
Light-weight heat-preservation fireproof composite board and preparation process thereof Download PDFInfo
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- CN115028880B CN115028880B CN202210639125.3A CN202210639125A CN115028880B CN 115028880 B CN115028880 B CN 115028880B CN 202210639125 A CN202210639125 A CN 202210639125A CN 115028880 B CN115028880 B CN 115028880B
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- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000004321 preservation Methods 0.000 title claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000010439 graphite Substances 0.000 claims abstract description 50
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000006260 foam Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- 229920005862 polyol Polymers 0.000 claims abstract description 8
- 150000003077 polyols Chemical class 0.000 claims abstract description 8
- 238000005187 foaming Methods 0.000 claims abstract description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- 239000004088 foaming agent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000007792 addition Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 10
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 7
- 229960004889 salicylic acid Drugs 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 abstract description 15
- 229920002635 polyurethane Polymers 0.000 abstract description 14
- 239000011159 matrix material Substances 0.000 abstract description 10
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 7
- 239000011147 inorganic material Substances 0.000 abstract description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003063 flame retardant Substances 0.000 abstract description 6
- 239000004566 building material Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000011368 organic material Substances 0.000 description 5
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical group FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical group N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011490 mineral wool Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
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- 238000003892 spreading Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
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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
- 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
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B80/00—Architectural or constructional elements improving the thermal performance of buildings
- Y02B80/10—Insulation, e.g. vacuum or aerogel insulation
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Building Environments (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a lightweight heat-insulating fireproof composite board and a preparation process thereof, belonging to the field of building materials, and comprising the following preparation steps: mixing toluene diisocyanate and diphenylmethane diisocyanate according to a weight ratio of 1:1 to obtain a black material; adding modified expanded graphite into polyether polyol, sequentially adding a foam stabilizer, a catalyst NaOH and a foaming agent, and uniformly stirring to obtain white materials; and adding the black material into the white material, rapidly stirring, standing to naturally foam, and cutting after foaming to obtain the composite board. According to the invention, through modifying the expanded graphite, the flame retardant property of the expanded graphite can be enhanced, and the organic molecular chain groups can be introduced into the surface of the expanded graphite, so that the compatibility of the expanded graphite and a polyurethane matrix is improved, the interfacial adhesion of the expanded graphite and the polyurethane matrix is improved, and the problem of mechanical property reduction caused by the introduction of inorganic materials is effectively avoided; the heat-insulating board with good mechanical property, good heat-insulating property and high fireproof grade is obtained.
Description
Technical Field
The invention belongs to the field of building materials, and particularly relates to a lightweight heat-insulating fireproof composite board and a preparation process thereof.
Background
The common heat insulating materials comprise inorganic materials and organic polymer materials, wherein the inorganic materials comprise rock wool, glass fibers, mineral wool and the like, the organic polymer materials comprise polystyrene, polypropylene, polyethylene and vinyl acetate copolymer, polyurethane (PU), phenolic resin, epoxy resin, urea-formaldehyde resin, unsaturated polyester, polyimide and the like, and the PU rigid foam plastic has excellent heat insulation and waterproof performance and is widely applied to industries such as household appliances, petrochemical industry, building industry and the like.
The PU rigid foam plastic not only has higher heat insulation and waterproof performance, but also has lower quality due to the foaming material, is easy to transport, and can meet the light-weight requirement of the building industry. However, in the preparation process of the PU hard foam insulation board, as the specific gravity of the organic material is small, the heat conductivity coefficient is low, the processing and the forming are easy, and various boards are convenient for construction, but the organic material has the defects of poor heat resistance, poor ageing resistance, easy combustion, release of a large amount of toxic smoke during combustion and acceleration of spreading of big fire; the inorganic material has high specific gravity and high heat conductivity coefficient, and the curing medium period is long in the construction or manufacturing process, so the inorganic material and the organic material are usually compounded, but substances such as carbon materials and the like in the adopted raw materials are difficult to be fully compatible with the polyurethane matrix in the compounding process of the inorganic material and the organic material, the interfacial bonding force between the organic material and the inorganic material is poor, and the breaking strength and the tensile strength of the prepared insulation board can only meet the corresponding line standard and national standard, and can not be well improved equally with the compressive strength. Therefore, developing an insulation board with good mechanical property, good insulation performance and high fireproof grade becomes an urgent problem to be solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a light-weight heat-insulation fireproof composite board and a preparation process thereof.
According to the invention, the flame retardant property of the expanded graphite can be enhanced by modifying the expanded graphite, and the organic molecular chain groups can be introduced into the surface of the expanded graphite, so that the compatibility of the expanded graphite and a polyurethane matrix is improved, and the interfacial adhesion of the expanded graphite and the polyurethane matrix is improved; thereby obtaining the heat-insulating board with good mechanical property, good heat-insulating property and high fireproof grade.
The aim of the invention can be achieved by the following technical scheme:
a preparation process of a light-weight heat-preservation fireproof composite board comprises the following steps:
firstly, mixing toluene diisocyanate and diphenylmethane diisocyanate according to a weight ratio of 1:1 to obtain a black material;
secondly, polyether polyol is taken, modified expanded graphite is added, then foam stabilizer, catalyst NaOH and foaming agent are sequentially added, and the mixture is uniformly stirred to obtain white materials;
thirdly, adding the black material into the white material according to a certain proportion, rapidly stirring, standing to naturally foam, and cutting after the foaming is finished to obtain the composite board.
Further, the mass ratio of the black material to the white material is 1:1, and the addition amount of the foam stabilizer, the catalyst NaOH and the foaming agent is sequentially 1%, 0.5% and 1.3% of the mass of the white material; the foam stabilizer is silicone oil L-600, and the foaming agent is trifluorochloromethane.
Further, the addition amount of the modified expanded graphite is 17-20% of the mass of the polyether polyol.
Further, the modified expanded graphite is prepared by the steps of:
s1, dissolving salicylic acid in ethanol in a round-bottom flask, dropwise adding ethylenediamine at room temperature, vigorously stirring, carrying out reflux reaction on the obtained mixture at 80 ℃ for 24 hours after the dropwise addition, cooling the reaction solution, distilling under reduced pressure to remove a solvent, dropwise adding an HCl solution with the concentration of 1mol/L into the product until the pH value of the reaction solution is 9-10, carrying out vacuum suction filtration, washing for 3-4 times with distilled water, and drying to obtain an intermediate; the dosage ratio of salicylic acid, ethanol and ethylenediamine is 1mol:400mL:1.2mol;
the salicylic acid and ethylenediamine undergo condensation acylation reaction to obtain an intermediate, and the molecule of the intermediate contains phenolic hydroxyl and-NH 2 Providing reaction sites for subsequent reactions, the reaction equation is as follows:
s2, sequentially adding hexachlorocyclotriphosphazene, triethylamine (catalyst) and tetrahydrofuran into a dry four-neck flask, introducing nitrogen, stirring for 28-35min at 350r/min under the nitrogen atmosphere, adding expanded graphite into a reaction system, heating to reflux temperature, carrying out reflux reaction for 12h, filtering, washing with water, and drying to obtain an expanded graphite derivative; the dosage ratio of hexachlorocyclotriphosphazene, triethylamine, tetrahydrofuran and expanded graphite is 5.8g to 10.1g to 50mL to 2.7g;
under the catalysis of triethylamine, the-OH functional group contained on the surface of the expanded graphite reacts with the P-Cl group on hexachlorocyclotriphosphazene, hexachlorocyclotriphosphazene is grafted on the surface of the expanded graphite, and the expanded graphite derivative is obtained, wherein the specific reaction equation is as follows:
the above-mentioned steps are carried out,
is a schematic diagram of expanded graphite;
s3, adding an expanded graphite derivative and toluene into a three-neck flask with a stirrer and a reflux condenser pipe, performing ultrasonic dispersion for 10min, adding an intermediate, starting mechanical stirring, introducing nitrogen for protection, slowly heating to 70 ℃ under constant stirring at 300r/min, slowly dropwise adding triethylamine, keeping the constant temperature of 70 ℃ for reaction for 6-7h after dropwise adding, performing suction filtration after the reaction liquid is cooled, washing for 3-4 times with distilled water, and drying to obtain modified expanded graphite; the dosage ratio of the expanded graphite derivative, toluene, the intermediate and triethylamine is 1.7g to 30mL to 3.4g to 20mL;
under the catalysis of triethylamine, the P-Cl group on hexachlorocyclotriphosphazene grafted on the surface of the expanded graphite derivative and the-NH on the intermediate molecule 2 The reaction is carried out to obtain the modified expanded graphite, and the reaction equation is as follows:
the expanded graphite is a material which can be expanded in volume under the high temperature condition to form a porous carbon layer so as to have the functions of heat insulation and oxygen insulation, and achieves a certain degree of flame retardant effect; in addition, the introduction of phosphorus element can also play a stronger role in inhibiting smoke; in addition, the surface of the expanded graphite is grafted with the cyclotriphosphazene group, and an intermediate structure is bonded through the cyclotriphosphazene group and the intermediate structure, so that agglomeration can be prevented, the hydrophilic characteristic of the expanded graphite can be obviously improved, the compatibility of the expanded graphite and a polyurethane matrix is improved, and uniform dispersion of the expanded graphite is promoted; and the intermediate structure contains phenolic hydroxyl groups, and the phenolic hydroxyl groups can participate in the polymerization process of polyurethane, so that the expanded graphite and the matrix form closer combination, and the flame retardant property is fully exerted.
The invention has the beneficial effects that:
according to the invention, the flame retardant property of the expanded graphite can be enhanced by modifying the expanded graphite, and the organic molecular chain groups can be introduced into the surface of the expanded graphite, so that the compatibility of the expanded graphite and a polyurethane matrix is improved, and the interfacial adhesion of the expanded graphite and the polyurethane matrix is improved; thereby obtaining the heat-insulating board with good mechanical property, good heat-insulating property and high fireproof grade.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing modified expanded graphite:
s1, dissolving 13.8g of salicylic acid in 40mL of ethanol in a round-bottom flask, dropwise adding 7.2g of ethylenediamine at room temperature, vigorously stirring, carrying out reflux reaction on the obtained mixture at 80 ℃ for 24 hours after the dropwise addition, cooling the reaction liquid, distilling under reduced pressure to remove the solvent, dropwise adding 1mol/L HCl solution into the product until the pH value of the reaction liquid is 9-10, carrying out reduced pressure suction filtration, washing for 3-4 times with distilled water, and drying to obtain an intermediate;
s2, sequentially adding 5.8g of hexachlorocyclotriphosphazene, 10.1g of triethylamine (catalyst) and 50mL of tetrahydrofuran into a dry four-neck flask, introducing nitrogen, stirring for 28min at 350r/min under the nitrogen atmosphere, adding 2.7g of expanded graphite into a reaction system, heating to reflux temperature, carrying out reflux reaction for 12h, filtering, washing with water, and drying to obtain an expanded graphite derivative;
s3, adding 1.7g of expanded graphite derivative and 30mL of toluene into a three-neck flask with a stirrer and a reflux condenser, performing ultrasonic dispersion for 10min, adding 3.4g of intermediate, starting mechanical stirring, introducing nitrogen for protection, slowly heating to 70 ℃ under 300r/min constant-speed stirring, slowly dropwise adding 20mL of triethylamine, keeping the constant temperature at 70 ℃ for reaction for 6h after the dropwise addition is finished, performing suction filtration after the reaction liquid is cooled, washing 3-4 times with distilled water, and drying to obtain the modified expanded graphite.
Example 2
Preparing modified expanded graphite:
s1, dissolving 13.8g of salicylic acid in 40mL of ethanol in a round-bottom flask, dropwise adding 7.2g of ethylenediamine at room temperature, vigorously stirring, carrying out reflux reaction on the obtained mixture at 80 ℃ for 24 hours after the dropwise addition, cooling the reaction liquid, distilling under reduced pressure to remove the solvent, dropwise adding 1mol/L HCl solution into the product until the pH value of the reaction liquid is 9-10, carrying out reduced pressure suction filtration, washing for 4 times with distilled water, and drying to obtain an intermediate;
s2, sequentially adding 5.8g of hexachlorocyclotriphosphazene, 10.1g of triethylamine (catalyst) and 50mL of tetrahydrofuran into a dry four-neck flask, introducing nitrogen, stirring for 35min at 350r/min under the nitrogen atmosphere, adding 2.7g of expanded graphite into a reaction system, heating to reflux temperature, carrying out reflux reaction for 12h, filtering, washing with water, and drying to obtain an expanded graphite derivative;
s3, adding 1.7g of expanded graphite derivative and 30mL of toluene into a three-neck flask with a stirrer and a reflux condenser, performing ultrasonic dispersion for 10min, adding 3.4g of intermediate, starting mechanical stirring, introducing nitrogen for protection, slowly heating to 70 ℃ under 300r/min constant-speed stirring, slowly dropwise adding 20mL of triethylamine, keeping the constant temperature at 70 ℃ for reaction for 7h after the dropwise addition is finished, performing suction filtration after the reaction liquid is cooled, washing 3-4 times with distilled water, and drying to obtain the modified expanded graphite.
Example 3
Preparing a light-weight heat-preservation fireproof composite board:
firstly, mixing toluene diisocyanate and diphenylmethane diisocyanate according to a weight ratio of 1:1 to obtain a black material;
step two, 50g of polyether polyol is taken, 8.5g of modified expanded graphite prepared in the embodiment 1 is added, and then 5g of silicone oil L-600, 2.5g of catalyst NaOH and 6.5g of trifluorochloromethane are sequentially added, and uniformly stirred to obtain white materials;
and thirdly, adding 50g of black materials into 50g of white materials, rapidly stirring, standing to naturally foam, and cutting after foaming to obtain the composite board.
Example 4
Preparing a light-weight heat-preservation fireproof composite board:
firstly, mixing toluene diisocyanate and diphenylmethane diisocyanate according to a weight ratio of 1:1 to obtain a black material;
step two, 50g of polyether polyol is taken, 9.2g of modified expanded graphite prepared in the embodiment 2 is added, and then 5g of silicone oil L-600, 2.5g of catalyst NaOH and 6.5g of trifluorochloromethane are sequentially added, and uniformly stirred to obtain white materials;
and thirdly, adding 50g of black materials into 50g of white materials, rapidly stirring, standing to naturally foam, and cutting after foaming to obtain the composite board.
Example 5
Preparing a light-weight heat-preservation fireproof composite board:
firstly, mixing toluene diisocyanate and diphenylmethane diisocyanate according to a weight ratio of 1:1 to obtain a black material;
step two, 50g of polyether polyol is taken, 10g of modified expanded graphite prepared in the embodiment 1 is added, and then 5g of silicone oil L-600, 2.5g of catalyst NaOH and 6.5g of trifluorochloromethane are sequentially added, and uniformly stirred to obtain white materials;
and thirdly, adding 50g of black materials into 50g of white materials, rapidly stirring, standing to naturally foam, and cutting after foaming to obtain the composite board.
Comparative example 1
The modified expanded graphite material in example 3 was replaced with expanded graphite without any treatment, and the remaining materials and the preparation process were unchanged.
Comparative example 2
The modified expanded graphite material of example 3 was removed and the remaining materials and preparation process were unchanged.
Performance test:
the composite panels prepared in examples 3-5 were cut to 50mm 10mm sizes and tested for oxygen index according to GB/T2406.1-2008; the mechanical properties (tensile strength and elongation at break) were measured by a universal tester, and the measurement results are shown in the following table:
as can be seen from the data in the table, the limiting oxygen index of the composite board prepared in the examples 3-5 reaches more than 27%, which indicates that the composite board prepared in the invention has excellent flame retardant property; compared with the polyurethane hard foam (comparative example 2), the composite plates prepared in examples 3-5 have almost the same polar tensile strength and elongation at break, but the mechanical properties of the polyurethane hard foam are greatly reduced without any modification, which means that in the invention, the expanded graphite can effectively improve the action and interface bonding property with the polymer matrix through modification treatment, and avoid the problem of mechanical property reduction caused by the addition of the expanded graphite.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (7)
1. The preparation process of the light-weight heat-preservation fireproof composite board is characterized by comprising the following steps of:
firstly, mixing toluene diisocyanate and diphenylmethane diisocyanate according to a weight ratio of 1:1 to obtain a black material;
secondly, polyether polyol is taken, modified expanded graphite is added, then foam stabilizer, catalyst NaOH and foaming agent are sequentially added, and the mixture is uniformly stirred to obtain white materials;
thirdly, adding black materials into white materials according to a certain proportion, rapidly stirring, standing to naturally foam the materials, and cutting after foaming to obtain the composite board;
the modified expanded graphite in the second step is prepared by the steps of:
s1, dissolving salicylic acid in ethanol in a round-bottom flask, dropwise adding ethylenediamine at room temperature, vigorously stirring, carrying out reflux reaction on the obtained mixture at 80 ℃ for 24 hours after the dropwise addition, cooling the reaction solution, distilling under reduced pressure to remove a solvent, dropwise adding an HCl solution with the concentration of 1mol/L into the product until the pH value of the reaction solution is 9-10, carrying out vacuum suction filtration, washing for 3-4 times with distilled water, and drying to obtain an intermediate;
s2, sequentially adding hexachlorocyclotriphosphazene, triethylamine and tetrahydrofuran into a dry four-neck flask, introducing nitrogen, stirring for 28-35min at 350r/min under the nitrogen atmosphere, adding expanded graphite into a reaction system, heating to reflux temperature, carrying out reflux reaction for 12h, filtering, washing with water, and drying to obtain an expanded graphite derivative;
s3, adding the expanded graphite derivative and toluene into a three-neck flask with a stirrer and a reflux condenser, performing ultrasonic dispersion for 10min, adding an intermediate, starting mechanical stirring, introducing nitrogen for protection, slowly heating to 70 ℃ under constant stirring at 300r/min, slowly dropwise adding triethylamine, keeping the constant temperature of 70 ℃ for reaction for 6-7h after dropwise adding, performing suction filtration after the reaction liquid is cooled, washing for 3-4 times with distilled water, and drying to obtain the modified expanded graphite.
2. The preparation process of the light-weight heat-insulating fireproof composite board according to claim 1, wherein the mass ratio of black material to white material is 1:1, and the addition amounts of the foam stabilizer, the catalyst NaOH and the foaming agent are sequentially 1%, 0.5% and 1.3% of the mass of the white material.
3. The preparation process of the light-weight heat-insulating fireproof composite board according to claim 1, wherein the addition amount of the modified expanded graphite is 17-20% of the mass of the polyether polyol.
4. The process for preparing the light-weight heat-insulating fireproof composite board according to claim 1, wherein the dosage ratio of salicylic acid, ethanol and ethylenediamine in the step S1 is 1mol:400mL:1.2mol.
5. The preparation process of the light-weight heat-insulating fireproof composite board according to claim 1, wherein the dosage ratio of hexachlorocyclotriphosphazene, triethylamine, tetrahydrofuran and expanded graphite in the step S2 is 5.8g:10.1g:50mL:2.7g.
6. The process for preparing the lightweight heat-insulating fireproof composite board according to claim 1, wherein the dosage ratio of the expanded graphite derivative, toluene, the intermediate and triethylamine in the step S3 is 1.7 g/30 mL/3.4 g/20 mL.
7. A lightweight thermal insulation fire protection composite board, characterized in that it is prepared according to any one of the preparation processes of claims 1-6.
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| CN113150392A (en) * | 2021-05-14 | 2021-07-23 | 北京化工大学 | Expandable graphite flame retardant coated with cyclophosphazene derivative on surface and preparation method thereof |
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| US5739173A (en) * | 1990-10-26 | 1998-04-14 | Basf Aktiengesellschaft | Preparation of flame-resistant soft polyurethane foams of reduced smoke density, and melamine/expandable graphite/polyether-polyol dispersions for this purpose |
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Application publication date: 20220909 Assignee: Anhui Ruijin Energy Saving Technology Co.,Ltd. Assignor: Anhui Ruilian Energy Saving Technology Co.,Ltd. Contract record no.: X2024980004583 Denomination of invention: A lightweight insulation and fireproof composite board and its preparation process Granted publication date: 20230512 License type: Exclusive License Record date: 20240424 |