CN116987378B - Super-temperature-resistant benzoxazine-polyurethane foam material as well as preparation method and application thereof - Google Patents
Super-temperature-resistant benzoxazine-polyurethane foam material as well as preparation method and application thereof Download PDFInfo
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- CN116987378B CN116987378B CN202311256469.7A CN202311256469A CN116987378B CN 116987378 B CN116987378 B CN 116987378B CN 202311256469 A CN202311256469 A CN 202311256469A CN 116987378 B CN116987378 B CN 116987378B
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- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 35
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical group C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229920002635 polyurethane Polymers 0.000 claims abstract description 46
- 239000004814 polyurethane Substances 0.000 claims abstract description 46
- 238000005187 foaming Methods 0.000 claims abstract description 18
- 239000004088 foaming agent Substances 0.000 claims abstract description 16
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000009413 insulation Methods 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000446 fuel Substances 0.000 claims abstract description 5
- 238000001721 transfer moulding Methods 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 15
- 229930185605 Bisphenol Natural products 0.000 claims description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- QXHDYMUPPXAMPQ-UHFFFAOYSA-N 2-(4-aminophenyl)ethanol Chemical compound NC1=CC=C(CCO)C=C1 QXHDYMUPPXAMPQ-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 229920002866 paraformaldehyde Polymers 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000004156 Azodicarbonamide Substances 0.000 claims description 5
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 5
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- VMUXSMXIQBNMGZ-UHFFFAOYSA-N 3,4-dihydrocoumarin Chemical compound C1=CC=C2OC(=O)CCC2=C1 VMUXSMXIQBNMGZ-UHFFFAOYSA-N 0.000 claims description 3
- DZGWFCGJZKJUFP-UHFFFAOYSA-N Tyramine Natural products NCCC1=CC=C(O)C=C1 DZGWFCGJZKJUFP-UHFFFAOYSA-N 0.000 claims description 3
- DMSHWWDRAYHEBS-UHFFFAOYSA-N dihydrocoumarin Natural products C1CC(=O)OC2=C1C=C(OC)C(OC)=C2 DMSHWWDRAYHEBS-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 229960003732 tyramine Drugs 0.000 claims description 3
- DZGWFCGJZKJUFP-UHFFFAOYSA-O tyraminium Chemical compound [NH3+]CCC1=CC=C(O)C=C1 DZGWFCGJZKJUFP-UHFFFAOYSA-O 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 6
- 125000006850 spacer group Chemical group 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 4
- 238000007711 solidification Methods 0.000 abstract description 4
- 230000008023 solidification Effects 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 2
- 229920006015 heat resistant resin Polymers 0.000 abstract 1
- 239000006261 foam material Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000005130 benzoxazines Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- -1 masonry Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- C08J9/06—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 chemical blowing agent
- C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- 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
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- 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
- C08J2375/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention discloses a super temperature resistant benzoxazine-polyurethane foam material, a preparation method and application thereof, wherein the super temperature resistant benzoxazine-polyurethane foam material is prepared by foaming polyurethane containing benzoxazine groups, a catalyst and foaming agent master batch; the molecular structural formula of the benzoxazine group-containing polyurethane is as follows. The benzoxazine-polyurethane is used as a matrix, and the benzoxazine resin foaming material with super temperature resistance and low heat transfer coefficient is obtained through the heating solidification and foaming process, and has the following advantages: the product has excellent temperature resistance, which can reach more than 300 ℃; the temperature resistance and the heat insulation of the obtained foaming material are enhanced; the heat conductivity coefficient of the product is as low as 0.030W/(m.K); the heat-resistant resin has wide application in the fields of new energy automobiles, aerospace, electronics, fuel cells, resin transfer molding, transportation and the like, and can be applied to battery spacers of the new energy automobiles to have excellent heat resistance.
Description
Technical Field
The invention belongs to the technical field of heat-insulating foam materials, and particularly relates to a super-temperature-resistant benzoxazine-polyurethane foam material, and a preparation method and application thereof.
Background
The polyurethane foam is a porous polyurethane material composed of a large number of micropores and polyurethane resin pore wall channels and collaterals, and is mainly characterized by porous property, low density, and high specific strength, and the polyurethane foam has many characteristics in performance, besides low density, also has the characteristics of odorlessness, ventilation (open-pore type), high heat insulation (closed-pore type hard foam), uniform cells, aging resistance, organic solvent erosion resistance and the like, and has strong adhesion to dissimilar materials such as metal, wood, glass, masonry, fiber and the like, which are different from other foam materials, so that the polyurethane foam is popular in various industries. Polyurethane foams have taken a strong market place in the field of insulation applications. Polyurethane foam has better thermal stability than other foam materials, but only has the highest temperature resistance of 200 ℃.
However, in recent years scientists have made further research and improvement on polyurethane foam to increase its thermal stability. They found that the addition of some additives with high temperature stability to polyurethane resin can significantly improve the temperature resistance of polyurethane foam. The polyurethane foam is widely applied under the high-temperature working condition, however, the requirements of the application in the aspects of heat insulation in the aerospace field, heat insulation of engines in the automobile industry, heat insulation of batteries in new energy automobiles and the like on the high temperature resistance are higher. However, at present, the manufacturing technology and performance of the existing polyurethane foam have been significantly improved, but some defects still exist. First, the temperature resistance of polyurethane foam is still limited, the highest temperature resistance is 200 ℃, and the requirement may not be met under certain high temperature environments. Secondly, the manufacturing process of polyurethane foam involves the use of organic solvents and chemical reactions, with certain environmental pollution and health risks. For example, many conventional polyurethane foams have a heat resistance temperature limit of 120℃as in patent CN 111574743B, and most of the test results are not acceptable at 160 ℃.
Disclosure of Invention
The invention aims to: aiming at the problems existing in the prior art, the invention provides the benzoxazine-polyurethane foam material based on super-heat-resistant high-temperature insulation, and the foam material prepared by the invention has excellent thermal stability, can stably work for a long time at the environment temperature of 250 ℃, and effectively overcomes the defect that the highest temperature resistance of the traditional polyurethane foam is only below 200 ℃.
The invention also provides a preparation method and application of the benzoxazine-polyurethane foam material based on super-temperature resistance and high heat preservation.
The technical scheme is as follows: in order to achieve the aim, the super-heat-resistant high-temperature-resistant benzoxazine-polyurethane foam material is prepared by foaming benzoxazine-group-containing polyurethane, a catalyst and foaming agent master batch; the molecular structural formula of the benzoxazine group-containing polyurethane is as follows:
wherein-NH-R-NH-is one of the following structures:
。
preferably, the catalyst is maleic anhydride; the foaming agent master batch is azodicarbonamide foaming agent master batch.
The preparation method of the benzoxazine foam material based on the bio-based main chain comprises the following steps:
(1) Mixing bisphenol, 2- (4-aminophenyl) ethanol and paraformaldehyde, adding an organic solvent, heating for reaction, filtering reactants after stopping the reaction, washing filtrate with water, steaming in a rotary manner, and drying to obtain a solid product, namely a benzoxazine monomer;
(2) Adding a benzoxazine monomer and diisocyanate into a solvent, heating for reaction, and removing the solvent after the reaction is finished to obtain polyurethane containing benzoxazine groups;
(3) And (3) uniformly mixing the catalyst, the foaming agent master batch and the benzoxazine group-containing polyurethane in a melting way, pouring the mixture into a mould, and then performing foaming treatment to obtain the super-heat-resistant high-temperature-resistant benzoxazine-polyurethane foam material.
Mixing dihydrocoumarin and tyramine in the step (1), adding ethanol as a solvent, heating for reaction, performing rotary evaporation, and drying to obtain bisphenol raw materials;
。
wherein, bisphenol, 2- (4-aminophenyl) ethanol and paraformaldehyde are mixed in the step (1), and organic solvent is added for reaction for 4-10 hours at 80-130 ℃; the solvent is one or more of toluene, dimethylbenzene, N dimethylformamide and N, N dimethylacetamide, and the molar ratio of bisphenol to 2- (4-aminophenyl) ethanol to paraformaldehyde is 1:2:4-1:2:4.8.
Preferably, the molar ratio of bisphenol, 2- (4-aminophenyl) ethanol and paraformaldehyde is 1:2:4.4.
Wherein, the benzoxazine monomer structure is as follows:
。
and (2) adding the benzoxazine monomer and the diisocyanate into a solvent, heating to 60-90 ℃, reacting for 2-10 hours, and removing the solvent in a vacuum oven after the reaction is finished to obtain the polyurethane containing the benzoxazine group.
Wherein the structure of the diisocyanate is one of the following:
。
wherein, in the step (3), the catalyst, the foaming agent master batch and the polyurethane containing benzoxazine groups are melted and mixed uniformly at the temperature of 50-80 ℃, poured into a mould, foamed and molded at the normal pressure of 180-200 ℃, and then cleaned and polished.
The mass ratio of the catalyst to the foaming agent master batch to the synthesized polyurethane containing the benzoxazine group in the step (3) is 20:3:70-20:7:77.
The super-heat-resistant high-temperature-resistant benzoxazine-polyurethane foam material is applied to new energy automobiles, aerospace, electronic fields, fuel cells, resin transfer molding and transportation.
Preferably, the foam material prepared by the invention can be applied to a battery spacer of a new energy automobile and has excellent temperature resistance.
The super-heat-resistant high-temperature-resistant benzoxazine-polyurethane foam material prepared by the invention has the mass reduction of less than 10% at 300 ℃ for 1h, and the heat conductivity coefficient of 0.030-0.035W m -1 K -1 Apparent density of 0.03-0.10 g/cm 3 。
The invention synthesizes the benzoxazine group-containing polyurethane, and simultaneously uses the benzoxazine-polyurethane as a matrix, and the benzoxazine resin foaming material with super temperature resistance and low heat transfer coefficient is obtained through the processes of heating, solidifying and foaming. The foaming material has the following advantages: (1) The product has excellent temperature resistance, which can reach more than 300 ℃; (2) By utilizing the characteristic that benzoxazine can be subjected to ring-opening solidification, the temperature resistance and the heat insulation of the obtained foaming material are strongly enhanced; (3) the thermal conductivity of the product is as low as 0.030W/(m.K); (4) The obtained material has wide application in the fields of new energy automobiles, aerospace, electronics, fuel cells, resin transfer molding, transportation and the like, and can be applied to battery spacers of the new energy automobiles to have excellent temperature resistance.
The invention synthesizes a kind of polyurethane containing benzoxazine groups, and uses the polyurethane as a matrix of foam material, and the foam material based on the benzoxazine-containing polyurethane is obtained through foaming and curing treatment. The invention provides a preparation method of a polyurethane foam material based on benzoxazine, which utilizes the fact that benzoxazine groups capable of being subjected to ring opening solidification are introduced into a polyurethane structure, and then the foam material is prepared through ring opening solidification and foaming, so that the defect of poor thermal stability of the traditional foam material in the past is considered. The benzoxazine-containing polyurethane foam material prepared by the method has excellent thermal stability due to the highly crosslinked chemical structure of the benzoxazine, and can stably work for a long time at the environmental temperature of 250 ℃. The preparation process is simple and the cost is low, so that the preparation method has a plurality of potential applications in new energy automobiles, aerospace, electronic fields, fuel cells, resin transfer molding and transportation.
The invention synthesizes polyurethane containing benzoxazine groups with a brand new structure, and uses the polyurethane as a matrix of foam material, and the foam material based on the benzoxazine-containing polyurethane is obtained through foaming and curing treatment. Because of the highly cross-linked chemical structure of the benzoxazine, the prepared benzoxazine-containing polyurethane foam material has excellent thermal stability and can stably work for a long time at the environmental temperature of 250 ℃. The preparation process is simple and the cost is low, so that the preparation method has a plurality of potential applications in the fields of new energy automobiles, aerospace, electronics and the like. The benzoxazine group is introduced into polyurethane, and the foam material of the benzoxazine has extremely high heat resistance and low heat conductivity coefficient.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
(1) The invention aims to overcome the characteristic of poor temperature resistance of the traditional foam material, creatively selects the introduction of benzoxazine groups into a polyurethane main chain for the first time, takes the prepared polyurethane as a foam base material, and obtains the benzoxazine-containing polyurethane foam material through foaming and curing treatment.
(2) The foam material prepared by the invention can obtain excellent thermal stability after deep crosslinking by benzoxazine groups, the mass of the foam material is reduced by less than 10% at 300 ℃ for 1h, and the heat conductivity coefficient is 0.029-0.035W m - 1 K -1 Apparent density of 0.03-0.10 g/cm 3 。
(3) The invention utilizes the benzoxazine with high temperature resistance to be mixed with the traditional polyurethane from the aspect of molecular design, has simple preparation and high yield, and breaks through the temperature resistance limit of the traditional polyurethane foam. The battery spacer can stably work for a long time at the environment temperature of 250 ℃, and can be applied to the battery spacer of a new energy automobile and has excellent temperature resistance.
Drawings
FIG. 1 is an infrared spectrum of benzoxazine-containing polyurethane obtained in example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of benzoxazine-containing polyurethane obtained in example 1.
Detailed Description
The invention will be better understood from the following examples. However, it will be readily appreciated by those skilled in the art that the description of the embodiments is provided for illustration only and should not limit the invention as described in detail in the claims.
The experimental methods described in the examples, unless otherwise specified, are all conventional; the reagents and materials, unless otherwise specified, are commercially available.
Maleic anhydride is conventionally commercially available, shandong Zhengyu chemical technology Co., ltd., CAS108-31-6.
Azodicarbonamide foaming master batch, a conventional AC foaming agent, is purchased from Haitai environmental protection materials limited company in Quanzea.
Example 1
The first step: 1g (6.75 mmol) of dihydrocoumarin and 0.926g (6.75 mmol) of tyramine are mixed, 25mL of ethanol is added as a solvent, the mixture is reacted for 4 hours at 60 ℃, the solvent is removed by rotary evaporation, and the biomass bisphenol raw material is obtained by drying;
and a second step of: 1g (3.50 mmol) of biomass bisphenol, 0.96g (7.00 mmol) of 2- (4-aminophenyl) ethanol, 0.463g (15.40 mmol) of paraformaldehyde (Albumin C104190) are added into a flask, 50mL of toluene solution is added, stirring and reaction are carried out in an oil bath, the temperature is slowly raised to 120 ℃ from room temperature, the reaction is carried out for 6 hours, the reaction is filtered after stopping the reaction, the reaction solution is washed by ethanol, and then dried in a vacuum drying oven at 50 ℃ for 48 hours, so as to obtain benzoxazine monomer, and the yield is 81%. The reaction equation is as follows:
and a third step of: 2g of the benzoxazine monomer obtained in the second step, 0.573g of toluene-2, 4-diisocyanate was added into a flask, 30mL of DMF solution was added, stirring and reaction were performed in an oil bath, the temperature was slowly raised from room temperature to 80 ℃, reaction was performed for 10h, and drying was performed in a vacuum drying oven at 50 ℃ for 48h to remove the solvent, thus obtaining 2.434g of benzoxazine-containing polyurethane. The reaction equation is as follows:
fourth step: adding maleic anhydride and azodicarbonamide foaming agent master batch (the mass ratio of the benzoxazine-containing polyurethane to the maleic anhydride to the azodicarbonamide foaming agent master batch=75:20:5) into the benzoxazine-containing polyurethane obtained by the reaction, melting and mixing uniformly at 80 ℃, pouring the mixture into a mould, heating to 200 ℃, foaming and curing for 2 hours, and finally cleaning and polishing to obtain the foam material.
The foam material prepared by the invention has the mass reduction of 8.9% at 300 ℃ for 1h, and the heat conductivity coefficient of 0.031W m -1 K -1 Apparent density of 0.06g/cm 3 。
The sample prepared in the embodiment is placed in a high-temperature oven, the temperature of the oven is 250 ℃, the sample is taken out after being placed for 1 hour, the quality, the heat conductivity coefficient and the apparent density of the sample are tested, the sample is repeatedly placed for 50 times, the quality, the heat conductivity coefficient and the apparent density of the sample change within 1 percent, and the sample can stably work for a long time at the environment temperature of 250 ℃.
FIG. 1 is an infrared spectrum of benzoxazine-containing polyurethane prepared according to the present invention, wherein 937 and 937 cm -1 And 1229cm -1 Is the characteristic peak of oxazine ring.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of benzoxazine-containing polyurethane prepared by the method, wherein the double peaks with chemical shifts of about 4.2 ppm and 3.6 ppm are characteristic peaks of methylene on an oxazine ring.
From fig. 1 and 2, it can be seen that the present invention successfully synthesizes benzoxazine-containing polyurethane.
Example 2
The first and second steps are the same as example 1.
And a third step of: 2g of the benzoxazine monomer obtained in the second step, 0.284 g of 4,4' -methylenebis (phenyl isocyanate) are added into a flask, 30mL of DMF solution is added, the mixture is stirred and reacted in an oil bath, the temperature is slowly increased to 80 ℃ from room temperature, the reaction is carried out for 10 hours, and the mixture is dried in a vacuum drying box at 50 ℃ for 48 hours, so as to obtain 2.649g of benzoxazine-containing polyurethane. The reaction equation is as follows:
the fourth step is as in example 1. The mass of the prepared foam material is reduced by 9.2 percent at 300 ℃ for 1h, and the heat conductivity coefficient is 0.032 and 0.032W m -1 K -1 Apparent density of 0.07g/cm 3 。
Example 3
The first and second steps are the same as in example 1.
And a third step of: 2g of benzoxazine monomer obtained in the second step, 0.863g of dicyclohexylmethane 4,4' -diisocyanate are added into a flask, 30ml of LDMF solution is added, the mixture is stirred and reacted in an oil bath, the temperature is slowly increased to 80 ℃ from room temperature, the reaction is carried out for 10 hours, and the mixture is dried in a vacuum drying oven at 50 ℃ for 48 hours, so as to obtain 2.672g of benzoxazine-containing polyurethane. The reaction equation is as follows:
the fourth step is as in example 1. The mass of the prepared foam material is reduced by 9.6% at 300 ℃ for 1h, and the heat conductivity coefficient is 0.032 and 0.032W m -1 K -1 Apparent density of 0.09g/cm 3 。
Comparative example 1
Comparative example 1 the preparation of example 1 was used, except that in step four the benzoxazine-containing polyurethane was replaced with a polyurethane material (BCX 61). The foam material is 15% mass reduced at 300 ℃ for 1h, and the heat conductivity coefficient is 0.029W m -1 K -1 Apparent density of 0.07g/cm 3 . Taking out the sample after the sample is placed for 1 hour at the temperature of 250 ℃ in an oven, testing the quality, the heat conductivity coefficient and the apparent density of the sample, and repeatedly placing the sample for 50 timesThe thermal coefficient and apparent density change by more than 6%.
Comparative example 2
Comparative example 2 the preparation of example 1 was used, except that in step four the benzoxazine-containing polyurethane was replaced with a benzoxazine-containing polyurethane and polyurethane material (BCX 61) in a mass ratio of 1:1. The foam material is reduced by 12% in mass at 300 ℃ for 1h, and the heat conductivity coefficient is 0.030W m -1 K -1 Apparent density of 0.08g/cm 3 。
Claims (10)
1. The super heat-resistant high-temperature-resistant benzoxazine-polyurethane foam material is characterized in that the super heat-resistant high-temperature-resistant benzoxazine-polyurethane foam material is prepared by foaming benzoxazine-group-containing polyurethane, maleic anhydride and foaming agent master batch; the molecular structural formula of the benzoxazine group-containing polyurethane is shown as follows:；
wherein-NH-R-NH-is one of the following structures:
。
2. the super heat resistant and high thermal insulation benzoxazine-polyurethane foam material according to claim 1, wherein the foaming agent master batch is an azodicarbonamide foaming agent master batch.
3. The preparation method of the super heat-resistant high-temperature-resistant benzoxazine-polyurethane foam material according to claim 1 is characterized by comprising the following steps:
(1) Mixing bisphenol, 2- (4-aminophenyl) ethanol and paraformaldehyde, adding an organic solvent, heating for reaction, filtering reactants after stopping the reaction, washing filtrate with water, steaming in a rotary manner, and drying to obtain a solid product, namely a benzoxazine monomer;
(2) Adding a benzoxazine monomer and diisocyanate into a solvent, heating for reaction, and removing the solvent after the reaction is finished to obtain polyurethane containing benzoxazine groups;
(3) And (3) uniformly mixing maleic anhydride, foaming agent master batches and polyurethane containing benzoxazine groups in a melting way, pouring the mixture into a mould, and then performing foaming treatment to obtain the super-heat-resistant high-temperature-resistant benzoxazine-polyurethane foam material.
4. The preparation method according to claim 3, wherein in the step (1), dihydrocoumarin and tyramine are mixed, ethanol is added as a solvent, and after the heating reaction, the mixture is subjected to rotary evaporation and drying, so as to obtain bisphenol raw materials;
。
5. the process according to claim 3, wherein bisphenol, 2- (4-aminophenyl) ethanol and paraformaldehyde are mixed in step (1), and an organic solvent is added thereto to react at 80 to 130℃for 4 to 10 hours; the solvent is one or more of toluene, dimethylbenzene, N dimethylformamide and N, N dimethylacetamide, and the molar ratio of bisphenol to 2- (4-aminophenyl) ethanol to paraformaldehyde is 1:2:4-1:2:4.8.
6. The preparation method according to claim 3, wherein the benzoxazine monomer and the diisocyanate are added into a solvent in the step (2), the temperature is raised to 60-90 ℃, the reaction is carried out for 2-10 hours, and after the reaction is finished, the solvent is removed in a vacuum oven, so that the polyurethane containing the benzoxazine group can be obtained.
7. The method of claim 6, wherein the diisocyanate has one of the following structures:
。
8. the preparation method according to claim 3, wherein in the step (3), maleic anhydride, a foaming agent master batch and polyurethane containing benzoxazine groups are melted and mixed uniformly at the temperature of 50-80 ℃, and then poured into a mold to be foamed and molded at the normal pressure of 180-200 ℃.
9. The preparation method of claim 5, wherein the mass ratio of maleic anhydride, foaming agent master batch and synthetic benzoxazine group-containing polyurethane in the step (3) is 20:3:70-20:7:77.
10. An application of the super heat-resistant high-temperature-resistant benzoxazine-polyurethane foam material in the fields of new energy automobiles, aerospace and electronics, fuel cells, resin transfer molding and transportation.
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