CN116790089A - Modified phenolic resin, preparation method thereof, carbon fiber paper and fuel cell - Google Patents
Modified phenolic resin, preparation method thereof, carbon fiber paper and fuel cell Download PDFInfo
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- CN116790089A CN116790089A CN202310772525.6A CN202310772525A CN116790089A CN 116790089 A CN116790089 A CN 116790089A CN 202310772525 A CN202310772525 A CN 202310772525A CN 116790089 A CN116790089 A CN 116790089A
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- phenolic resin
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- high molecular
- weight thermoplastic
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 57
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 57
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000446 fuel Substances 0.000 title claims abstract description 8
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 132
- 239000005011 phenolic resin Substances 0.000 claims abstract description 132
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 72
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims description 65
- 239000007787 solid Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 22
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 150000002989 phenols Chemical class 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 229920000459 Nitrile rubber Polymers 0.000 claims description 17
- -1 aldehyde compounds Chemical class 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001723 curing Methods 0.000 claims description 11
- 239000007770 graphite material Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 36
- 229910052799 carbon Inorganic materials 0.000 description 33
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 150000001299 aldehydes Chemical class 0.000 description 11
- 238000003763 carbonization Methods 0.000 description 10
- 238000009835 boiling Methods 0.000 description 8
- 238000010000 carbonizing Methods 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 5
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 5
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 5
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 5
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 5
- 229920005549 butyl rubber Polymers 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 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 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 101100495270 Caenorhabditis elegans cdc-26 gene Proteins 0.000 description 1
- 101100491335 Caenorhabditis elegans mat-2 gene Proteins 0.000 description 1
- 101100495256 Caenorhabditis elegans mat-3 gene Proteins 0.000 description 1
- 102100040428 Chitobiosyldiphosphodolichol beta-mannosyltransferase Human genes 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/46—Non-siliceous fibres, e.g. from metal oxides
- D21H13/50—Carbon fibres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/48—Condensation polymers of aldehydes or ketones with phenols
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- 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
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Abstract
The invention relates to the technical field of novel materials, in particular to a modified phenolic resin and a preparation method thereof, carbon fiber paper and a fuel cell. The raw materials for forming the modified phenolic resin comprise: the resin comprises ultra-high molecular weight thermoplastic phenolic resin and thermosetting phenolic resin, wherein the number average molecular weight of the ultra-high molecular weight thermoplastic phenolic resin is 1200-1600, and the weight average molecular weight is 18500-23500. The phenolic resin is modified, so that the carbon fiber paper prepared by the phenolic resin has high carbon residue rate.
Description
Technical Field
The invention relates to the technical field of novel materials, in particular to a modified phenolic resin and a preparation method thereof, carbon fiber paper and a fuel cell.
Background
The carbon fiber paper is a carbon/carbon composite material with 3-6mm chopped carbon fibers as a framework and thermosetting resin as a binder. The domestic method for manufacturing the carbon fiber paper is generally a wet papermaking method, wherein 3-6mm chopped carbon fibers are used as raw materials, dispersing agents are used for uniformly dispersing the chopped carbon fibers in water, the carbon fibers are made into a thin felt state by wet papermaking equipment, and the carbon fiber raw paper is obtained through drying and forming by a dryer. And (3) dipping the manufactured carbon fiber base paper into a resin solution, and drying, curing and carbonizing to obtain the carbon fiber paper meeting the requirements.
The resin solution for impregnating the carbon fiber paper is generally phenolic resin, and has the following advantages: the adhesive has high adhesive strength, can be well compatible with various inorganic and organic fillers, has high wetting speed and particularly high wetting speed, and can provide certain mechanical strength and heat resistance for a die or a refractory material after crosslinking. However, the carbon fiber paper formed by the existing phenolic resin has low carbon residue rate, and the use of the carbon fiber paper is limited.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide modified phenolic resin, a preparation method thereof, carbon fiber paper and a fuel cell. According to the embodiment of the invention, the phenolic resin is modified, so that the carbon fiber paper prepared by the phenolic resin has high carbon residue rate.
The invention is realized in the following way:
in a first aspect, the present invention provides a modified phenolic resin with a high carbon residue ratio, the raw materials for forming the modified phenolic resin comprising: the resin comprises ultra-high molecular weight thermoplastic phenolic resin and thermosetting phenolic resin, wherein the number average molecular weight of the ultra-high molecular weight thermoplastic phenolic resin is 1200-1600, and the weight average molecular weight is 18500-23500.
In an alternative embodiment, the ultra-high molecular weight thermoplastic phenolic resin is used in an amount of 50-70% of the solids content of the thermosetting phenolic resin.
Preferably, the solid content of the thermosetting phenolic resin is 70-72%;
preferably, the viscosity of the ultra-high molecular weight thermoplastic phenolic resin is 10000-12000.Cps/105 ℃.
In an alternative embodiment, the raw materials forming the modified phenolic resin further comprise: graphite material, borate and carboxyl terminated nitrile rubber.
In an alternative embodiment, the carboxyl terminated nitrile rubber is used in an amount of 10-15% of the solids content of the thermosetting phenolic resin; the dosage of the graphite material is 0.5-1% of the solid content of the thermosetting phenolic resin; the mass ratio of the borate to the ultra-high molecular weight thermoplastic phenolic resin is (2-3) (30-50).
In a second aspect, the present invention provides a method for preparing a modified phenolic resin with high carbon residue according to the foregoing embodiment, wherein the modified phenolic resin is formed by co-curing an ultra-high molecular weight thermoplastic phenolic resin and a thermosetting phenolic resin.
In an alternative embodiment, the method of preparing the ultra-high molecular weight thermoplastic phenolic resin comprises: mixing, heating and refluxing a catalyst, a part of phenolic compounds and a part of aldehyde compounds, then adding the rest of phenolic compounds and the rest of aldehyde compounds, heating and refluxing, adding hydroxide when the viscosity of a reaction system reaches 10000-12000.CPs/105 ℃, and adjusting the pH value to 5-6; heating for dehydration, and filtering small particles; wherein the molar ratio of all phenolic compounds to all aldehydes is 0.8-1:1, and the dosage of the catalyst is 0.5-2% of the total mass of the phenolic compounds and the aldehydes;
preferably, the catalyst is concentrated sulfuric acid;
preferably, the preparation method of the ultra-high molecular weight thermoplastic phenolic resin comprises the following steps: mixing concentrated sulfuric acid, a part of phenolic compounds and a part of aldehyde compounds, heating and refluxing for 3-5 hours, wherein the part of phenolic compounds and the part of aldehyde compounds account for 70-85% of the total mass of the reaction raw materials;
then adding the residual phenolic compound and the residual aldehyde compound, and heating and refluxing for 1-3 hours;
when the viscosity of the reaction system reaches 10000-12000.CPs/105 ℃, adding sodium hydroxide, and adjusting the pH value to 5-6; heating for dewatering and filtering small particles.
In an alternative embodiment, the method comprises: mixing and dissolving the ultra-high molecular weight thermoplastic phenolic resin and an alcohol solvent, wherein the mass ratio of the ultra-high molecular weight thermoplastic phenolic resin to the alcohol solvent is 1 (0.8-1).
In an alternative embodiment, the method further comprises: mixing and heating thermosetting phenolic resin, graphite material and carboxyl-terminated nitrile rubber to 60-80 ℃ and stirring for 1-3 hours to form a mixture, and then mixing with the ultra-high molecular weight thermoplastic phenolic resin and borate; wherein the mass ratio of the mixture to the ultra-high molecular weight thermoplastic phenolic resin to the borate is (40-80): 30-50): 2-3.
In a third aspect, the present invention provides a carbon fiber paper prepared from the modified phenolic resin with high carbon residue as described in any one of the foregoing embodiments.
In a fourth aspect, the present invention provides a fuel cell prepared from the modified phenolic resin with high carbon residue as described in any one of the preceding embodiments or the carbon fiber paper as described in the preceding embodiments.
The invention has the following beneficial effects: according to the embodiment of the invention, the carbon residue rate of the resin system can be greatly improved by adopting the specific thermoplastic phenolic resin and thermosetting phenolic resin for co-curing, namely, the carbon residue rate of the carbon fiber paper prepared by the resin system is improved, and the use of the carbon fiber paper is further enlarged.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The embodiment of the invention provides a modified phenolic resin, which comprises an ultra-high molecular weight thermoplastic phenolic resin and a thermosetting phenolic resin as raw materials, wherein the ultra-high molecular weight thermoplastic phenolic resin has a number average molecular weight of 1200-1600, a weight average molecular weight of 18500-23500 and a softening point of 132-137 ℃. According to the embodiment of the invention, the ultra-high molecular weight thermoplastic phenolic resin with specific molecular weight and the thermosetting phenolic resin are adopted to be cured together, so that the formed modified phenolic resin has higher carbon residue rate.
Further, the viscosity of the ultra-high molecular weight thermoplastic phenolic resin is 10000-12000.CPs/105 ℃, i.e. the viscosity of the ultra-high molecular weight thermoplastic phenolic resin is 10000-12000.CPs at 105 ℃.
The ultra-high molecular weight thermoplastic phenolic resin may satisfy the above requirements, and the thermosetting phenolic resin may be a thermosetting phenolic resin which has been commercially available.
The solid content of the thermosetting phenolic resin is 70-72%; such as any number between 70-72%, such as 70%, 71%, 72%, etc.
The dosage of the ultra-high molecular weight thermoplastic phenolic resin is 50-70% of the solid content of the thermosetting phenolic resin; the carbon residue rate of the modified phenolic resin can be further improved by controlling the dosage of the modified phenolic resin and the modified phenolic resin.
Further, carbon residue after phenolic resin carbonization belongs to hard graphitized carbon, and then the electric conductivity and the thermal conductivity of carbon fiber paper formed by the carbon residue need to be improved, and the toughness of carbon fiber paper formed by the existing phenolic resin also needs to be improved.
In order to improve the problems, the embodiment of the invention adopts carboxyl-terminated nitrile rubber, graphite materials (for example, graphene with the particle size of 30-100 nanometers) and borate to cooperate, so that the electric conductivity, the thermal conductivity and the toughness of the modified phenolic resin can be improved.
Wherein the dosage of the carboxyl-terminated nitrile rubber is 10-15% of the solid content of the thermosetting phenolic resin; for example, 10%, 11%, 12%, 13%, 14%, 15%, etc., of any number between 10 and 15%; the dosage of the graphite material is 0.5-1% of the solid content of the thermosetting phenolic resin; for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, etc. 0.5-1.0%; the mass ratio of borate to the ultra-high molecular weight thermoplastic phenolic resin is (2-3): (30-50), for example 2:35, 3:30, 2:50, 2: 30. 3:50, 2: 45. 3:40, 3: 45. 3:48, 3:33, 2:37, etc. (2-3): any number between (30-50).
In a second aspect, an embodiment of the present invention provides a method for preparing the modified phenolic resin, including:
s1, preparing an ultra-high molecular weight thermoplastic phenolic resin:
weighing phenolic compounds, aldehyde compounds and catalysts according to the amount, wherein the molar ratio of the phenolic compounds to the aldehyde compounds is 0.8-1:1, and the amount of the catalysts is 0.5-2% of the total mass of the phenolic compounds and the aldehyde compounds; the catalyst may be concentrated sulfuric acid.
Specifically, mixing concentrated sulfuric acid, a part of phenolic compounds and a part of aldehyde compounds, heating and refluxing for 3-5 hours, wherein the part of phenolic compounds and the part of aldehyde compounds account for 70-85% of the total mass of the reaction raw materials; then adding the residual phenolic compound and the residual aldehyde compound, and heating and refluxing for 1-3 hours; when the viscosity of the reaction system reaches 10000-12000.CPs/105 ℃, adding sodium hydroxide, and adjusting the pH value to 5-6; heating for dewatering and filtering small particles.
Wherein the phenolic compound can be one or more of phenol, cardanol, resorcinol, bisphenol A and tricresyl, and the aldehyde compound is one or more of formaldehyde and butyraldehyde.
S2, forming a thermoplastic phenolic resin solution;
mixing and dissolving the ultra-high molecular weight thermoplastic phenolic resin and an alcohol solvent, wherein the mass ratio of the ultra-high molecular weight thermoplastic phenolic resin to the alcohol solvent is 1:0.8-1. The alcohol solvent may be selected from conventional monohydric alcohol solvents such as ethanol, methanol, and isopropanol.
S3, forming modified phenolic resin;
mixing and heating thermosetting phenolic resin, graphite material and carboxyl-terminated nitrile rubber to 60-80 ℃ and stirring for 1-3 hours to form a mixture, and then mixing with the ultra-high molecular weight thermoplastic phenolic resin solution and borate solution; wherein the mass ratio of the mixture to the ultra-high molecular weight thermoplastic phenolic resin to the borate is (40-80): 30-50): 2-3.
In the step of forming the modified phenolic resin in S3, the thermosetting phenolic resin, the graphite material and the carboxyl terminated nitrile rubber may be mixed and cured with the ultra-high molecular weight thermoplastic phenolic resin and the borate, or the thermosetting phenolic resin, the graphite material, the carboxyl terminated nitrile rubber, the high molecular weight thermoplastic phenolic resin and the borate may be directly mixed and cured.
In a third aspect, the present invention provides a carbon fiber paper prepared from the modified phenolic resin with high carbon residue as described in any one of the foregoing embodiments.
In a fourth aspect, the present invention provides a fuel cell prepared from the modified phenolic resin with high carbon residue as described in any one of the preceding embodiments or the carbon fiber paper as described in the preceding embodiments.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a preparation method of a modified phenolic resin with high carbon residue rate, which comprises the following steps:
step 1: a. phenol and formaldehyde were weighed in a molar ratio of 0.8:1, and concentrated sulfuric acid was weighed as a catalyst in an amount of 1% by weight based on the total weight of phenol and added aldehyde. b. Mixing phenol, aldehyde and concentrated sulfuric acid, heating to boiling, and refluxing for 1 hour; wherein phenol and formaldehyde account for 75% of the total mass of the reaction system. c. The remaining phenol and aldehyde were added, heated to boiling and refluxed for 2 hours. d. Testing the viscosity of the resin system, and adding sodium hydroxide when the viscosity reaches 600.CPs/105 ℃, and regulating the pH value to 6-7; heating for dehydration, and filtering small particles to obtain the thermoplastic phenolic resin with ultrahigh molecular weight. The softening point of the resin was 135 ℃, the number average molecular weight was 1300, and the weight average molecular weight was 19000.
Step 2: dissolving the ultra-high molecular weight thermoplastic phenolic resin with alcohol, wherein the mass ratio of the resin to the alcohol is 1:1, obtaining an ultra-high molecular weight thermoplastic phenolic resin solution.
Step 3: the preparation method comprises the steps of selecting B30 phenolic resin of China academy of sciences as thermosetting resin, adding carboxyl-terminated nitrile rubber with the solid content of 70% and the solid content of 15% of B30 phenolic resin, adding conductive graphite with the solid content of 1wt% of B30 phenolic resin and the particle size of 50 nanometers, heating to 60 ℃ and stirring for 1 hour to form a uniform mixture.
Step 4: mixing an ultrahigh molecular weight thermoplastic phenolic resin solution, a mixture and a sodium borate solution to form a final modified phenolic resin; the mass ratio was 30% (mixture): 68% (thermoplastic ultra-high molecular weight phenolic resin): 2% (borate); the ultra-high molecular weight thermoplastic phenolic resin was used in an amount of 67% of the solids content of the B30 phenolic resin.
Example 2
The embodiment provides a preparation method of a modified phenolic resin with high carbon residue rate, which comprises the following steps:
step 1: a. phenol and formaldehyde were weighed in a molar ratio of 0.8:1, and concentrated sulfuric acid was weighed as a catalyst in an amount of 1.2% based on the total weight of phenol and formaldehyde. b. Mixing phenol, aldehyde and concentrated sulfuric acid, heating to boiling, and refluxing for 2 hours; wherein phenol and formaldehyde account for 80% of the total mass of the reaction system. c. The remaining phenol and aldehyde were added, heated to boiling and refluxed for 3 hours. d. Testing the viscosity of the resin system, and adding sodium hydroxide when the viscosity reaches 800.CPs/105 ℃, and regulating the pH value to 6-7; heating for dehydration, and filtering small particles to obtain the thermoplastic phenolic resin with ultrahigh molecular weight. The softening point of the resin was 135 ℃, the number average molecular weight was 1500, and the weight average molecular weight was 23000.
Step 2: dissolving the ultra-high molecular weight thermoplastic phenolic resin with alcohol, wherein the mass ratio of the resin to the alcohol is 1:1, obtaining an ultra-high molecular weight thermoplastic phenolic resin solution.
Step 3: the preparation method comprises the steps of selecting B30 phenolic resin of China academy of sciences as thermosetting resin, adding carboxyl-terminated nitrile rubber with the solid content of 70% and the solid content of 10% of B30 phenolic resin, adding conductive graphite with the solid content of 1wt% of B30 phenolic resin and the particle size of 50 nanometers, heating to 60 ℃ and stirring for 1 hour to form a uniform mixture.
Step 4: mixing the ultra-high molecular weight thermoplastic phenolic resin solution, the mixture and the borate solution to form a final modified phenolic resin; the mass ratio was 30% (mixture): 68% (thermoplastic ultra-high molecular weight phenolic resin): 2% (borate); the amount of the ultra-high molecular weight thermoplastic phenolic resin is 60% of the solid content of the B30 phenolic resin.
Example 3
The embodiment provides a preparation method of a modified phenolic resin with high carbon residue rate, which comprises the following steps:
step 1: a. cardanol and formaldehyde are weighed according to a molar ratio of 0.8:1, and concentrated sulfuric acid is weighed according to 1% of the total weight of the cardanol and the formaldehyde to serve as a catalyst. b. Mixing phenol, aldehyde and concentrated sulfuric acid, heating to boiling, and refluxing for 2 hours; wherein cardanol and formaldehyde account for 75% of the total mass of the reaction system. c. The remaining phenol and aldehyde were added, heated to boiling and refluxed for 3 hours. d. Testing the viscosity of the resin system, and adding sodium hydroxide when the viscosity reaches 1200.CPs/105 ℃, and regulating the pH value to 6-7; heating for dehydration, and filtering small particles to obtain the thermoplastic phenolic resin with ultrahigh molecular weight. The Tg of the resin is 135 ℃, the number average molecular weight is 1300, and the weight average molecular weight is 20000.
Step 2: dissolving the ultra-high molecular weight thermoplastic phenolic resin with alcohol, wherein the mass ratio of the resin to the alcohol is 1:1, obtaining an ultra-high molecular weight thermoplastic phenolic resin solution.
Step 3: the preparation method comprises the steps of selecting B30 phenolic resin of China academy of sciences as thermosetting resin, adding carboxyl-terminated nitrile rubber with the solid content of 70% and the solid content of 5% of B30 phenolic resin, adding conductive graphite with the solid content of 1% by weight and the particle size of 50 nanometers, heating to 60 ℃ and stirring for 1 hour to form a uniform mixture.
Step 4: mixing the ultra-high molecular weight thermoplastic phenolic resin solution, the mixture and the borate solution to form a final modified phenolic resin; the mass ratio was 30% (mixture): 68% (thermoplastic ultra-high molecular weight phenolic resin): 2% (borate); the amount of the ultra-high molecular weight thermoplastic phenolic resin is 60% of the solid content of the B30 phenolic resin.
Example 4
The embodiment provides a preparation method of a modified phenolic resin with high carbon residue rate, which comprises the following steps:
step 1: a. alkylphenol and formaldehyde were weighed according to a molar ratio of 0.8:1, and concentrated sulfuric acid was weighed as a catalyst according to 1% of the total weight of alkylphenol and formaldehyde. b. Mixing phenol, aldehyde and concentrated sulfuric acid, heating to boiling, and refluxing for 2 hours; wherein alkylphenol and formaldehyde account for 75% of the total mass of the reaction system. c. The remaining phenol and aldehyde were added, heated to boiling and refluxed for 3 hours. d. Testing the viscosity of the resin system, and adding sodium hydroxide when the viscosity reaches 800.CPs/105 ℃, and regulating the pH value to 6-7; heating for dehydration, and filtering small particles to obtain the thermoplastic phenolic resin with ultrahigh molecular weight. The softening point of the resin was 135 ℃, the number average molecular weight was 1200, and the weight average molecular weight was 18000.
Step 2: dissolving the ultra-high molecular weight thermoplastic phenolic resin with alcohol, wherein the mass ratio of the resin to the alcohol is 1:1, obtaining an ultra-high molecular weight thermoplastic phenolic resin solution.
Step 3: the preparation method comprises the steps of selecting B30 phenolic resin of China academy of sciences as thermosetting resin, adding carboxyl-terminated nitrile rubber with the solid content of 70% and the solid content of 5% of B30 phenolic resin, adding conductive graphite with the solid content of 1.5% and the solid content of B30 phenolic resin and the particle size of 50 nanometers, heating to 60 ℃ and stirring for 1 hour to form a uniform mixture.
Step 4: mixing the ultra-high molecular weight thermoplastic phenolic resin solution, the mixture and the borate solution to form a final modified phenolic resin; the mass ratio was 30% (mixture): 68% (thermoplastic ultra-high molecular weight phenolic resin): 2% (borate); the ultra-high molecular weight thermoplastic phenolic resin was used in an amount of 67% of the solids content of the B30 phenolic resin.
Examples 5 to 8
Examples 5-8 all provide a method for preparing carbon fiber paper, comprising:
60g of the mat (Hengsheng) was pre-impregnated with the phenolic resins prepared in examples 1 to 4 above, respectively, using a pre-impregnation machine, and oven-dried to prepare prepreg mats, respectively prepreg mat 1, prepreg mat 2, prepreg mat 3 and prepreg mat 4, wherein the resin contents were 65%.
And heating and pressurizing the prepreg felt 1, the prepreg felt 2, the prepreg felt 3 and the prepreg felt 4 by using a hot press to cure to obtain the carbon fiber felt 1, the carbon fiber felt 2, the carbon fiber felt 3 and the carbon fiber felt 4, wherein the curing system is 150 ℃ at 30min plus the pressure of 1MPa.
And heating and carbonizing the carbon fiber felt 1, the carbon fiber felt 2, the carbon fiber felt 3 and the carbon fiber felt 4 to obtain the finished carbon paper. Carbon paper 1, carbon paper 2, carbon paper 3 and carbon paper 4, respectively. The heating rate of the carbonization process is 0-800 ℃ and 1.5 ℃/min, the heating rate of 800-1500 ℃ is 1 ℃/min, and the heating rate of 1500-1800 ℃ is 0.5 ℃/min.
Comparative example 1: comparative example 1 provides a method for preparing carbon fiber paper, comprising:
60g of felt (Hengsheng) was presoaked with thermosetting phenolic resin 2124 by a presoaked machine and dried to prepare a presoaked felt 5 in which the resin contents were 65% each.
And heating and pressurizing the prepreg felt 5 by using a hot press to cure, so as to obtain the carbon fiber felt 5 with a curing system of 150 ℃ at 30min plus pressure of 1MPa.
And heating and carbonizing the carbon fiber felt 5 to obtain the finished carbon paper. Is carbon paper 5. The heating rate of the carbonization process is 0-800 ℃ and 1.5 ℃/min, the heating rate of 800-1500 ℃ is 1 ℃/min, and the heating rate of 1500-1800 ℃ is 0.5 ℃/min.
Comparative example 2: comparative example 2 provides a method for preparing carbon fiber paper, comprising:
60g of felt (Hengsheng) was presoaked with thermosetting phenolic resin 2127 by a presoaked machine and dried to prepare a presoaked felt 6 in which the resin contents were 65% each.
And heating and pressurizing the prepreg felt 6 by a hot press to cure the prepreg felt 6 to obtain the carbon fiber felt 6 with a curing system of 150 ℃ at 30min plus pressure of 1MPa.
And heating and carbonizing the carbon fiber felt 6 to obtain the finished carbon paper. Is carbon paper 6. The heating rate of the carbonization process is 0-800 ℃ and 1.5 ℃/min, the heating rate of 800-1500 ℃ is 1 ℃/min, and the heating rate of 1500-1800 ℃ is 0.5 ℃/min.
Comparative example 3: comparative example 3 provides a method for preparing carbon fiber paper, comprising:
the carboxylated nitrile rubber in example 1-step 3 was replaced with butyl rubber, the remainder being unchanged, to give a butyl rubber modified phenolic resin.
60g of felt (Hengsheng) was presoaked with butyl rubber modified phenolic resin by a presoaked machine and dried to prepare a presoaked felt 7 in which the resin content was 65% in each case.
And heating and pressurizing the prepreg felt 7 by using a hot press to cure, so as to obtain the carbon fiber felt 7 with a curing system of 150 ℃ at 30min plus pressure of 1MPa.
And heating and carbonizing the carbon fiber felt 7 to obtain the finished carbon paper. Is carbon paper 7. The heating rate of the carbonization process is 0-800 ℃ and 1.5 ℃/min, the heating rate of 800-1500 ℃ is 1 ℃/min, and the heating rate of 1500-1800 ℃ is 0.5 ℃/min.
Comparative example 4: comparative example 4 provides a method of preparing carbon fiber paper, comprising:
the ultra-high molecular weight thermoplastic phenolic resin in example 1-step 1 was changed to a normal thermoplastic phenolic resin having a molecular weight average molecular weight of 2000, and the remainder was unchanged, modified 1 phenolic resin.
60g of felt (Hengsheng) is presoaked with modified 1 phenolic resin by a presoaked machine, and is dried to prepare presoaked felt 8, wherein the resin content is 65 percent.
And heating and pressurizing the prepreg felt 8 by using a hot press to cure, so as to obtain the carbon fiber felt 8 with a curing system of 150 ℃ at 30min plus pressure of 1MPa.
And heating and carbonizing the carbon fiber felt 8 to obtain the finished carbon paper. Is carbon paper 8. The heating rate of the carbonization process is 0-800 ℃ and 1.5 ℃/min, the heating rate of 800-1500 ℃ is 1 ℃/min, and the heating rate of 1500-1800 ℃ is 0.5 ℃/min.
Comparative example 5: comparative example 5 provides a method of preparing carbon fiber paper, comprising:
the ultra-high molecular weight thermoplastic phenolic resin in example 1-step 1 was changed to a normal thermoplastic phenolic resin having a molecular weight average molecular weight of 4000, the remainder being unchanged, a modified 2 phenolic resin.
60g of felt (Hengsheng) is presoaked with modified 2 phenolic resin by a presoaked machine, and is dried to prepare presoaked felt 9, wherein the resin content is 65 percent.
And heating and pressurizing the prepreg felt 9 by a hot press to cure the prepreg felt 9, so as to obtain the carbon fiber felt 9 with a curing system of 150 ℃ at 30min and a pressure of 1MPa.
And heating and carbonizing the carbon fiber felt 9 to obtain the finished carbon paper. Is carbon paper 9. The heating rate of the carbonization process is 0-800 ℃ and 1.5 ℃/min, the heating rate of 800-1500 ℃ is 1 ℃/min, and the heating rate of 1500-1800 ℃ is 0.5 ℃/min.
Comparative example 6: comparative example 6 provides a method of preparing carbon fiber paper, comprising:
the borates in examples 1-4 were replaced with an equal mass of conductive graphite, the remainder unchanged, modified 3 phenolic resin.
60g of felt (Hengsheng) is presoaked with modified 3 phenolic resin by a presoaked machine, and is dried to prepare the presoaked felt 10, wherein the resin content is 65 percent.
And heating and pressurizing the prepreg felt 10 by a hot press to cure the prepreg felt 10, so as to obtain the carbon fiber felt 10 with a curing system of 150 ℃ at 30min and a pressure of 1MPa.
And heating and carbonizing the carbon fiber felt 10 to obtain the finished carbon paper. Is carbon paper 10. The heating rate of the carbonization process is 0-800 ℃ and 1.5 ℃/min, the heating rate of 800-1500 ℃ is 1 ℃/min, and the heating rate of 1500-1800 ℃ is 0.5 ℃/min.
Comparative example 7: the existing japanese eastern 60 carbon paper was purchased and noted as carbon paper 11.
Detection of
The carbon fiber papers prepared in examples 5 to 8 and comparative examples 1 to 7 were examined, and specific results are shown in tables 1 and 2.
TABLE 1 carbon paper Performance test results
TABLE 2 carbon paper Performance test results
As can be seen from tables 1 and 2, (1) the high molecular weight thermoplastic resin was carbonized to have higher conductivity and carbon residue than the low molecular weight phenolic resin as can be seen from carbon papers 1, 8 and 9. (2) It is understood from the carbon papers 1 to 6 that the higher the residual carbon content of the resin itself, the higher the conductivity after carbonization. (3) As can be seen from carbon papers 1-3 and 67, carboxylated nitrile rubber has a better toughening effect than butyl rubber. (4) As can be seen from the carbon papers 1 and 10, the borate salt used together with the conductive graphite is better in conductivity than the conductive graphite alone. (5) According to the carbon paper 1-4, the weight average molecular weight is 18000-23000, and the conductivity of the carbonized carbon paper is equivalent. (6) From the carbon papers 1 and 4, cardanol was found to have a low flexural modulus and a good toughness after carbonization.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The modified phenolic resin with high carbon residue rate is characterized in that the raw materials for forming the modified phenolic resin comprise: the resin comprises ultra-high molecular weight thermoplastic phenolic resin and thermosetting phenolic resin, wherein the number average molecular weight of the ultra-high molecular weight thermoplastic phenolic resin is 1200-1600, and the weight average molecular weight is 18500-23500.
2. The modified phenolic resin with high carbon residue ratio according to claim 1, wherein,
the solid content of the thermosetting phenolic resin is 70-72%;
preferably, the viscosity of the ultra-high molecular weight thermoplastic phenolic resin is 10000-12000.CPs/105 ℃;
preferably, the ultra-high molecular weight thermoplastic phenolic resin is used in an amount of 50-70% of the solids content of the thermosetting phenolic resin.
3. The high char yield modified phenolic resin of claim 1 or 2, wherein the raw materials forming the modified phenolic resin further comprise: graphite material, borate and carboxyl terminated nitrile rubber.
4. The modified phenolic resin of claim 3, wherein the carboxyl terminated nitrile rubber is present in an amount of 10 to 15% of the solids content of the thermosetting phenolic resin; the dosage of the graphite material is 0.5-1% of the solid content of the thermosetting phenolic resin; the mass ratio of the borate to the ultra-high molecular weight thermoplastic phenolic resin is (2-3) (30-50).
5. A method of preparing the modified phenolic resin of claim 1, wherein the modified phenolic resin is formed by co-curing an ultra-high molecular weight thermoplastic phenolic resin and a thermosetting phenolic resin.
6. The method of preparing the ultra-high molecular weight thermoplastic phenolic resin according to claim 5, wherein the method of preparing the ultra-high molecular weight thermoplastic phenolic resin comprises: mixing, heating and refluxing a catalyst, a part of phenolic compounds and a part of aldehyde compounds, then adding the rest of phenolic compounds and the rest of aldehyde compounds, heating and refluxing, adding hydroxide when the viscosity of a reaction system reaches 10000-12000.CPs/105 ℃, and adjusting the pH value to 5-6; heating for dehydration, and filtering small particles; wherein the molar ratio of all phenolic compounds to all aldehydes is (0.8-1): 1, the catalyst is used in an amount of 0.5-2% of the total mass of the phenolic compounds and the aldehydes;
preferably, the catalyst is concentrated sulfuric acid;
preferably, the preparation method of the ultra-high molecular weight thermoplastic phenolic resin comprises the following steps: mixing concentrated sulfuric acid, a part of phenolic compounds and a part of aldehyde compounds, heating and refluxing for 3-5 hours, wherein the part of phenolic compounds and the part of aldehyde compounds account for 70-85% of the total mass of the reaction raw materials;
then adding the residual phenolic compound and the residual aldehyde compound, and heating and refluxing for 1-3 hours;
when the viscosity of the reaction system reaches 10000-12000.CPs/105 ℃, adding sodium hydroxide, and adjusting the pH value to 5-6; heating for dewatering and filtering small particles.
7. The method according to claim 5, comprising: mixing and dissolving the ultra-high molecular weight thermoplastic phenolic resin and an alcohol solvent, wherein the mass ratio of the ultra-high molecular weight thermoplastic phenolic resin to the alcohol solvent is 1 (0.8-1).
8. The method of manufacturing according to claim 5, further comprising: mixing and heating thermosetting phenolic resin, graphite material and carboxyl-terminated nitrile rubber to 60-80 ℃ and stirring for 1-3 hours to form a mixture, and then mixing with the ultra-high molecular weight thermoplastic phenolic resin and borate; wherein the mass ratio of the mixture to the ultra-high molecular weight thermoplastic phenolic resin to the borate is (40-80): 30-50): 2-3.
9. A carbon fiber paper prepared from the modified phenolic resin of high char yield according to any one of claims 1 to 4.
10. A fuel cell prepared from the modified phenolic resin with high carbon residue ratio according to any one of claims 1 to 4 or the carbon fiber paper according to claim 9.
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