CN117903568A - Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material and preparation method and application thereof - Google Patents
Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN117903568A CN117903568A CN202211236101.XA CN202211236101A CN117903568A CN 117903568 A CN117903568 A CN 117903568A CN 202211236101 A CN202211236101 A CN 202211236101A CN 117903568 A CN117903568 A CN 117903568A
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- composite material
- tbe
- fiber cloth
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 239000002131 composite material Substances 0.000 title claims abstract description 94
- 229920001153 Polydicyclopentadiene Polymers 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 93
- 239000004917 carbon fiber Substances 0.000 claims abstract description 93
- 239000004744 fabric Substances 0.000 claims abstract description 71
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 15
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000011986 second-generation catalyst Substances 0.000 claims abstract description 11
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000005452 bending Methods 0.000 abstract description 9
- 239000011229 interlayer Substances 0.000 abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 239000012779 reinforcing material Substances 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 238000001721 transfer moulding Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 7
- 238000011417 postcuring Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002390 adhesive tape Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 4
- BZBMBZJUNPMEBD-UHFFFAOYSA-N tert-butyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC(C)(C)C)CC1C=C2 BZBMBZJUNPMEBD-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 3
- 238000010107 reaction injection moulding Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007676 flexural strength test Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011985 first-generation catalyst Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- 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
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention provides an Nb-TBE modified carbon fiber interlayer reinforced polydicyclopentadiene composite material, a preparation method and application thereof, which are prepared by carrying out vacuum auxiliary resin transfer molding copolymerization on 5-norbornene-2-tert-butyl formate (Nb-TBE) modified carbon fiber cloth and dicyclopentadiene, wherein the carbon fiber is T300-grade carbon fiber cloth. The Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material is prepared by selecting polymerizable Nb-TBE modified T300 carbon fiber cloth as a reinforcing material and copolymerizing dicyclopentadiene under the initiation of a Grubbs second-generation catalyst to prepare the high-strength composite material. The modified carbon fiber cloth improves the tensile strength and the bending strength of the polydicyclopentadiene composite material, and compared with the pure carbon fiber interlayer reinforced polydicyclopentadiene composite material, the tensile strength is improved by about 62.3 percent, and the bending strength is improved by about 152.8 percent.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a polymerizable 5-norbornene-2-tert-butyl formate (Nb-TBE) modified carbon fiber reinforced polydicyclopentadiene composite material, and a preparation method and application thereof.
Background
Polydicyclopentadiene (Polydicyclopentadiene, abbreviated as PDCPD) is an impact-resistant thermosetting engineering plastic, and is prepared from dicyclopentadiene (Dicyclopendiene, abbreviated as DCPD) monomer and catalyst through a reaction injection molding (Reaction Injection Molding, abbreviated as RIM) process and ring-opening metathesis polymerization (ring-Opening Metathesis Polymerization, abbreviated as ROMP). PDCPD has excellent mechanical and thermal properties and is widely applied to the fields of automobile accessories, sports equipment, furniture shells and the like. Since dicyclopentadiene has a low viscosity and a high polymerization rate, currently, a polydicyclopentadiene sheet is produced mainly by a reaction injection molding process.
The carbon fiber cloth is also called carbon fiber cloth, carbon fiber woven cloth, carbon fiber prepreg cloth, carbon fiber reinforced cloth, carbon fiber fabric, carbon fiber belt, carbon fiber sheet (prepreg cloth) and the like. The carbon fiber reinforced cloth is a unidirectional carbon fiber reinforced product and is woven by 12K carbon fiber filaments. The carbon fiber cloth is used for tensile, shearing and shock resistance reinforcement of structural members, and the material and the matched impregnating adhesive are used together to form a carbon fiber composite material, so that a complete carbon fiber cloth sheet reinforcing system can be formed, and the carbon fiber cloth sheet reinforcing system is suitable for reinforcement engineering for treating building use load increase, engineering use function change, material aging, concrete strength grade lower than a design value, structural crack treatment, repair and protection of service members in severe environments.
If the excellent physical and mechanical properties of the carbon fiber reinforced polydicyclopentadiene composite material are to be exhibited, it is critical that the carbon fibers have good affinity with the polydicyclopentadiene, the sizing agent on the surface of the carbon fibers is generally an epoxy sizing agent, the affinity with the polydicyclopentadiene is poor, the load cannot be well transferred between the resin and the fibers, and the mechanical properties of the prepared composite material are low.
At present, most of researches on polydicyclopentadiene/carbon fiber composite materials are focused on improving interface bonding quality, but quite a lot of surface treatment modes have low efficiency and high cost, and cannot meet the production requirements of industry. In addition, the polydicyclopentadiene/carbon fiber composite material is generally formed by injection molding, and a new molding mode is required to be developed for meeting different requirements of the product and cost control, so that the modification of the carbon fiber is carried out, the bonding strength of the carbon fiber and cyclopentadiene is improved, and the preparation of the composite material by using a new low-cost molding mode has important significance.
The 5-norbornene-2-tert-Butyl formate, which is named as tert-Butyl5-Norbornene-2-carboxylate for short Nb-TBE, contains norbornenyl groups and dicyclopentadiene also contains norbornenyl groups, so that the 5-norbornene-2-tert-Butyl formate can be subjected to copolymerization reaction with dicyclopentadiene under the action of a catalyst, and on the other hand, the polar groups of the 5-norbornene-2-tert-Butyl formate are fully compatible with the surface of the carbon fiber cloth and are subjected to condensation reaction with the polar groups on the surface of the carbon fiber, so that the interfacial interaction between polydicyclopentadiene and the surface of the carbon fiber can be obviously improved, and the mechanical property is improved.
According to the Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material, 5-norbornene-2-tert-butyl formate modified T300-grade carbon fiber cloth is selected as a reinforcing material to be mixed and polymerized with dicyclopentadiene to form the composite material, the tensile strength and bending strength of the polydicyclopentadiene composite material are obviously improved by the modified carbon fiber cloth, and compared with the tensile strength of a pure carbon fiber interlayer reinforced polydicyclopentadiene composite material, the tensile strength of the composite material in comparative example 1 is improved from 395MPa to 641MPa of the composite material in example 5, the tensile strength of the composite material in comparative example 1 is improved by about 62.3%, the bending strength of 178MPa to 450MPa, and the tensile strength of the composite material in comparative example is improved by 152.8%.
In addition, the preparation method of the Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material is simple to operate, easy to implement and high in preparation efficiency.
Disclosure of Invention
Stage heating
The temperature of the reaction mould is raised to 80 ℃ and is pumped and discharged to vacuum, the mixed solution containing the catalyst and DCPD is rapidly injected into the mould, the mould is sealed after being filled with nitrogen, the temperature of the mould is raised to 120 ℃ after the reaction is carried out for 1 hour, the post-curing treatment is carried out for 1 hour, and the modified carbon fiber reinforced polydicyclopentadiene composite material is taken out after the mould is cooled and is demoulded. Or curing at 40-80 deg.c for 1-5 hr to form, and post-treatment at 120-150 deg.c for 1-5 hr.
The invention aims to provide a Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material, a preparation method and application thereof.
The technical scheme of the invention is that the Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material has the tensile strength of 475-641MPa.
The invention also provides an Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material with 232-450MPa bending strength.
The invention also discloses a preparation method of the Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material, which comprises the following steps:
(1) Uniformly mixing 5-norbornene-2-tert-butyl formate and isopropanol in a volume ratio of 1-5:100 to form a transparent solution;
(2) Fully soaking the carbon fiber cloth in the transparent solution in the step (1), taking out, and putting into a preheated oven for drying;
(3) Fixing the carbon fiber cloth dried in the step (2) on two sides of a die;
(4) Weighing the materials with the mass ratio of 500-100000: 1, dissolving the catalyst in an organic solvent, adding the catalyst into dicyclopentadiene, stirring uniformly, and then carrying out vacuum pumping until no bubble is generated;
(5) And (3) injecting the mixed solution obtained in the step (4) into the die obtained in the step (3), sealing after filling inert gas, and cooling and demolding after stage heating and solidification.
In some preferred embodiments, the carbon fiber cloth in step (3) is selected from one of SM unidirectional carbon fiber cloth, T300 grade carbon fiber cloth, or T700 grade carbon fiber cloth.
In some preferred embodiments, the organic solvent in step (4) is at least one or more of dichloromethane, toluene, ethyl acetate or tetrahydrofuran.
In some preferred embodiments, the catalyst in step (4) is a ruthenium carbene structure catalyst, preferably a Grubbs second generation catalyst, and the concentration of the catalyst is from 35 to 50mg/ml, preferably from 40 to 50mg/ml.
In some preferred embodiments, the dicyclopentadiene to catalyst mass ratio in step (4) is 1000 to 10000:1.
In some preferred embodiments, the inert gas in step (5) is nitrogen, argon or helium.
In some preferred embodiments, the stage of the step (5) is heated and solidified to 40-80 ℃ for 1-5 hours, forming, and carrying out the post-treatment at 120-150 ℃ for 1-5 hours.
The invention also discloses the modified carbon fiber interlayer reinforced polydicyclopentadiene composite material prepared by the method, wherein the tensile strength of the composite material is 475-641MPa, and the bending strength of the composite material is 232-450MPa.
The invention also discloses application of the modified carbon fiber interlayer reinforced polydicyclopentadiene composite material in fan blades, automobile shells, high-speed rails, aerospace and the like.
In order to achieve the above purpose, the Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material adopts the following technical scheme: a polymerizable modifier modified carbon fiber interlayer reinforced polydicyclopentadiene composite material is formed by fixing Nb-TBE modified carbon fiber cloth on two sides of a die and copolymerizing dicyclopentadiene through a VARTM process, wherein the carbon fiber is T300-grade carbon fiber cloth. The tensile strength of the composite material is 475-641MPa. The bending strength of the composite material is 232-450MPa.
Compared with the prior art, the Grubbs second-generation catalyst selected by the technology disclosed by the invention is relatively water-resistant and oxygen-resistant, can keep certain activity in air and a small amount of water before reaction, is more convenient to operate compared with a bimetallic catalyst, and meanwhile, compared with a first-generation catalyst, the Grubbs second-generation catalyst has higher activity, and can increase the proportion of a monomer to the catalyst by several orders of magnitude, so that the raw material cost can be effectively saved. The polymerizable Nb-TBE selected by the invention contains norbornene groups, and dicyclopentadiene also contains norbornene groups, so that the Nb-TBE can be subjected to copolymerization reaction with the dicyclopentadiene under the action of a catalyst, and on the other hand, the polar groups of the Nb-TBE are fully compatible with the surface of the carbon fiber cloth and are subjected to condensation reaction with the polar groups on the surface of the carbon fiber, so that the interfacial interaction between the polydicyclopentadiene and the surface of the carbon fiber can be obviously improved, and the mechanical property can be improved.
According to the Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material, 5-norbornene-2-tert-butyl formate modified T300 grade carbon fiber plain cloth is selected as a reinforcing material to be mixed and polymerized with dicyclopentadiene to form the composite material, the modified carbon fiber cloth obviously improves the tensile strength and bending strength of the polydicyclopentadiene composite material, and compared with the pure carbon fiber interlayer reinforced polydicyclopentadiene composite material, the tensile strength is improved by 60%, and the bending strength is improved by 150%. In addition, the preparation method of the Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material is simple to operate, easy to implement and high in preparation efficiency, wherein the ruthenium-based carbene catalyst is stable and reliable, and has good water and oxygen resistance.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The starting materials used in the examples below are all commercially available.
Example 1 modified carbon fiber reinforced polydicyclopentadiene composite Material
Volume ratio 1:100 Nb-TBE and isopropanol are uniformly mixed, the reaction is carried out for 2 hours at 25 ℃ until the Nb-TBE is completely dissolved into a transparent solution, the T300 carbon fiber plain cloth is put into the prepared transparent solution, the surface of the carbon fiber is completely soaked, after soaking for 5 minutes, the surface of the carbon fiber is completely soaked under a microscope (Nikon Ci positive microscope, shanghai-Wen photoelectric company), and the Nb-TBE and the carbon fiber are fully reacted; and taking out the carbon fiber cloth, putting the carbon fiber cloth into a baking oven at the temperature of 100 ℃ to be baked until the weight of the carbon fiber cloth is not changed, namely, after being baked for 5 hours, removing isopropanol, and obtaining the Nb-TBE modified carbon fiber cloth.
Fixing the Nb-TBE modified carbon fiber cloth on two sides of a die by using high-temperature-resistant double-sided adhesive tapes; 58mg of Grubbs second generation catalyst powder was weighed with a sample bottle in a vacuum glove box, 1mL of a dichloromethane solution was injected thereto with a syringe and shaken well to form a uniform catalyst solution, then the catalyst solution was added to 100mL of DCPD solution to be sufficiently stirred to be uniform in color, and the dichloromethane solvent therein was evacuated with an oil pump until no bubbles were generated.
The reaction mould is preheated to 80 ℃ and pumped and discharged for three times to vacuum, the mixed solution is rapidly injected into the mould, the mould is sealed after being filled with nitrogen, after the reaction is carried out for 1 hour, the temperature of the mould is raised to 120 ℃ for carrying out post-curing treatment for 1 hour, and the modified carbon fiber reinforced polydicyclopentadiene composite material is taken out after the mould is cooled for standby.
Example 2 modified carbon fiber reinforced polydicyclopentadiene composite Material
Mixing the following components in volume ratio 2:100 Nb-TBE and isopropanol are uniformly mixed and reacted for 2 hours at 25 ℃ until the Nb-TBE is completely dissolved into transparent solution; placing the T300-grade carbon fiber plain weave cloth into a prepared transparent solution to completely infiltrate the surface of the carbon fiber, observing that the surface of the carbon fiber is fully infiltrated under a microscope after soaking for 30 minutes, and fully reacting Nb-TBE with the carbon fiber; and taking out the carbon fiber cloth, and putting the carbon fiber cloth into a 140 ℃ oven for drying until the weight of the carbon fiber cloth is not changed, namely, drying for 20 hours, thus obtaining the Nb-TBE modified carbon fiber cloth.
Fixing the Nb-TBE modified carbon fiber cloth on two sides of a die by using high-temperature-resistant double-sided adhesive tapes; 58mg of Grubbs' second generation catalyst powder was weighed with a sample bottle in a glove box, 1mL of a dichloromethane solution was injected thereto with a syringe and shaken well to form a uniform catalyst solution, then the catalyst solution was added to 100mL of DCPD solution with sufficient stirring, and the dichloromethane solvent inside was evacuated with an oil pump until no bubbles were generated.
The reaction mould is preheated to 80 ℃ and pumped and discharged for three times to vacuum, the mixed solution is rapidly injected into the mould, the mould is sealed after being filled with nitrogen, after the reaction is carried out for 1 hour, the temperature of the mould is raised to 120 ℃ for carrying out post-curing treatment for 1 hour, and the modified carbon fiber reinforced polydicyclopentadiene composite material is taken out after the mould is cooled for standby.
Example 3 modified carbon fiber reinforced polydicyclopentadiene composite Material
Volume ratio 3:100 Nb-TBE and isopropanol are uniformly mixed and reacted for 2 hours at 25 ℃ until the Nb-TBE is completely dissolved into transparent solution; placing the T300-grade carbon fiber plain weave cloth into a prepared transparent solution to completely infiltrate the surface of the carbon fiber, observing that the surface of the carbon fiber is fully infiltrated under a microscope after soaking for 10 minutes, and fully reacting Nb-TBE with the carbon fiber; and taking out the carbon fiber cloth, and putting the carbon fiber cloth into a 110 ℃ oven to be dried until the weight of the carbon fiber cloth is not changed any more, namely, after being dried for 7 hours, obtaining the Nb-TBE modified carbon fiber cloth.
Fixing the Nb-TBE modified carbon fiber cloth on two sides of a die by using high-temperature-resistant double-sided adhesive tapes; 58mg of Grubbs' second generation catalyst powder was weighed with a sample bottle in a glove box, 1mL of a dichloromethane solution was injected thereto with a syringe and shaken well to form a uniform catalyst solution, then the catalyst solution was added to 100mL of DCPD solution with sufficient stirring, and the dichloromethane solvent inside was evacuated with an oil pump until no bubbles were generated.
The reaction mould is preheated to 80 ℃ and pumped and discharged for three times to vacuum, the mixed solution is rapidly injected into the mould, the mould is sealed after being filled with nitrogen, after the reaction is carried out for 1 hour, the temperature of the mould is raised to 120 ℃ for carrying out post-curing treatment for 1 hour, and the modified carbon fiber reinforced polydicyclopentadiene composite material is taken out after the mould is cooled for standby.
Example 4 modified carbon fiber reinforced polydicyclopentadiene composite Material
Volume ratio 4:100 Nb-TBE and isopropanol are uniformly mixed and reacted for 2 hours at 25 ℃ until the Nb-TBE is completely dissolved into transparent solution; placing the T300-grade carbon fiber plain weave cloth into a prepared transparent solution to completely infiltrate the surface of the carbon fiber, observing that the surface of the carbon fiber is fully infiltrated under a microscope after 15 minutes of impregnation, and fully reacting Nb-TBE with the carbon fiber; and taking out the carbon fiber cloth, and putting the carbon fiber cloth into a baking oven at 120 ℃ to be baked until the weight of the carbon fiber cloth is not changed any more, namely, baking the carbon fiber cloth for 10 hours to obtain the Nb-TBE modified carbon fiber cloth.
Fixing the Nb-TBE modified carbon fiber cloth on two sides of a die by using high-temperature-resistant double-sided adhesive tapes; 58mg of Grubbs' second generation catalyst powder was weighed with a sample bottle in a glove box, 1mL of a dichloromethane solution was injected thereto with a syringe and shaken well to form a uniform catalyst solution, then the catalyst solution was added to 100mL of DCPD solution with sufficient stirring, and the dichloromethane solvent inside was evacuated with an oil pump until no bubbles were generated.
The reaction mould is preheated to 80 ℃ and pumped and discharged for three times to vacuum, the mixed solution is rapidly injected into the mould, the mould is sealed after being filled with nitrogen, after the reaction is carried out for 1 hour, the temperature of the mould is raised to 120 ℃ for carrying out post-curing treatment for 1 hour, and the modified carbon fiber reinforced polydicyclopentadiene composite material is taken out after the mould is cooled for standby.
Example 5 modified carbon fiber reinforced polydicyclopentadiene composite
Volume ratio 5:100 Nb-TBE and isopropanol are uniformly mixed and reacted for 2 hours at 25 ℃ until the Nb-TBE is completely dissolved into transparent solution; placing the T300-grade carbon fiber plain weave cloth into a prepared transparent solution to completely infiltrate the surface of the carbon fiber, observing that the surface of the carbon fiber is fully infiltrated under a microscope after 15 minutes of impregnation, and fully reacting Nb-TBE with the carbon fiber; and taking out the carbon fiber cloth, and putting the carbon fiber cloth into a 115 ℃ oven to be dried until the weight of the carbon fiber cloth is not changed any more, namely, drying for 15 hours, thus obtaining the Nb-TBE modified carbon fiber cloth.
Fixing the Nb-TBE modified carbon fiber cloth on two sides of a die by using high-temperature-resistant double-sided adhesive tapes; 58mg of Grubbs' second generation catalyst powder was weighed with a sample bottle in a glove box, 1mL of a dichloromethane solution was injected thereto with a syringe and shaken well to form a uniform catalyst solution, then the catalyst solution was added to 100mL of DCPD solution with sufficient stirring, and the dichloromethane solvent inside was evacuated with an oil pump until no bubbles were generated.
The reaction mould is preheated to 80 ℃ and pumped and discharged for three times to vacuum, the mixed solution is rapidly injected into the mould, the mould is sealed after being filled with nitrogen, after the reaction is carried out for 1 hour, the temperature of the mould is raised to 120 ℃ for carrying out post-curing treatment for 1 hour, and the modified carbon fiber reinforced polydicyclopentadiene composite material is taken out after the mould is cooled for standby.
Comparative example 1 carbon fiber reinforced polydicyclopentadiene composite
Wiping the surface of the T300-grade carbon fiber plain cloth with ethanol solution, putting the plain cloth into an oven at 100 ℃ for 10 hours to remove ethanol, and fixing the carbon fiber cloth on two sides of a die by using high-temperature-resistant double faced adhesive tape; 58mg of Grubbs' second generation catalyst powder was weighed with a sample bottle in a glove box, 1mL of a dichloromethane solution was injected thereto with a syringe and shaken well to form a uniform catalyst solution, then the catalyst solution was added to 100mlDCPD solution with sufficient stirring, and the dichloromethane solvent therein was pumped out with an oil pump until no bubbles were generated. The reaction mould is preheated to 80 ℃ and pumped and exhausted for three times until vacuum is achieved, the mixed solution is rapidly injected into the mould, the mould is sealed after being filled with nitrogen, after the reaction is carried out for 1 hour, the temperature of the mould is raised to 120 ℃ for carrying out post-curing treatment for 1 hour, and the polymerization product is taken out after the mould is cooled.
Test example 1 tensile Strength test
The composites prepared in examples 1-5 and comparative example 1 were tested for tensile properties according to ASTM D3039 at which the samples were tested for the desired 12 layers of carbon fiber plain cloth. After molding, the sheet was cut to 250mm by 25mm by 4mm dimensions, and reinforcing sheets (38 mm by 25 mm) were adhered to both ends, and tested according to the procedure detailed in ASTM D3039. The test was carried out on an Instron universal tester at a test speed of 5mm/min. At least 5 bars were tested per group and averaged.
Table 1 results of tensile strength test of composite materials
Comparative example 1 the tensile strength value of the composite material of carbon fiber not modified with t-butyl 5-norbornene-2-carboxylate (Nb-TBE) was much weaker than that of the composite material of carbon fiber modified with t-butyl 5-norbornene-2-carboxylate (Nb-TBE) in examples 1 to 5.
Specifically, the tensile strength of the composite of example 1 was 1.20 times that of the composite of comparative example 1, the tensile strength of the composite of example 2 was 1.31 times that of the composite of comparative example 1, the tensile strength of the composite of example 3 was 1.42 times that of the composite of comparative example 1, the tensile strength of the composite of example 4 was 1.52 times that of the composite of comparative example 1, and the tensile strength of the composite of example 5 was 1.62 times that of the composite of comparative example 1.
Test example 2 flexural Strength test
The composites prepared in examples 1-5 and comparative example 1 were tested for flexural properties of laminates using the three point loading method according to ASTM D7264. The composite laminate was cut to 80mm by 10mm by 4mm sizes and the number of layers of woven cloth required according to standard thickness was about 12. At least 5 bars per group were tested using an Instron universal tester at a test speed of 5mm/min and averaged.
Table 2 results of flexural Strength test of composite materials
The flexural strength value of the composite material of comparative example 1, which is carbon fiber not modified with t-butyl 5-norbornene-2-carboxylate (Nb-TBE), was much weaker than that of the composite material of examples 1 to 5, specifically, the flexural strength of the composite material of example 1 was 1.30 times that of the composite material of comparative example 1, the flexural strength of the composite material of example 2 was 1.79 times that of the composite material of comparative example 1, the flexural strength of the composite material of example 3 was 1.96 times that of the composite material of comparative example 1, the flexural strength of the composite material of example 4 was 2.64 times that of the composite material of comparative example 1, and the flexural strength of the composite material of example 5 was 2.50 times that of the composite material of comparative example 1.
While the preferred embodiments of the present application have been described in detail, the present application is not limited to the embodiments, and various equivalent modifications and substitutions can be made by those skilled in the art without departing from the spirit of the present application, and these equivalent modifications and substitutions are intended to be included in the scope of the present application as defined in the appended claims.
Claims (14)
1. The Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material is characterized in that the tensile strength of the composite material is 475-641MPa.
2. The composite of claim 1, wherein the composite has a flexural strength of 232-450MPa.
3. A preparation method of a Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material comprises the following steps:
(1) Uniformly mixing 5-norbornene-2-tert-butyl formate and isopropanol in a volume ratio of 1-5:100 to form a transparent solution;
(2) Fully soaking the carbon fiber cloth in the transparent solution in the step (1), taking out, and putting into a preheated oven for drying;
(3) Fixing the carbon fiber cloth dried in the step (2) on two sides of a die;
(4) Weighing the materials with the mass ratio of 500-100000: 1, dissolving the catalyst in an organic solvent, adding the catalyst into dicyclopentadiene, stirring uniformly, and then carrying out vacuum pumping until no bubble is generated;
(5) And (3) injecting the mixed solution obtained in the step (4) into the die obtained in the step (3), sealing after filling inert gas, and cooling and demolding after stage heating and solidification.
4. A method according to claim 3, characterized in that: the carbon fiber cloth in the step (3) is selected from one of SM unidirectional carbon fiber cloth, T300-grade carbon fiber cloth or T700-grade carbon fiber cloth.
5. A process according to claim 3, wherein the organic solvent in step (4) is at least one or more of dichloromethane, toluene, ethyl acetate or tetrahydrofuran.
6. A method according to claim 3, characterized in that: the catalyst in the step (4) is a ruthenium carbene structure catalyst, preferably a Grubbs second generation catalyst.
7. The method according to claim 6, wherein: the concentration of the catalyst is 35-50mg/ml, preferably 40-50mg/ml.
8. A method according to claim 3, characterized in that: the mass ratio of dicyclopentadiene to the catalyst in the step (4) is 1000-10000:1.
9. A method according to claim 3, characterized in that: the inert gas in the step (5) is nitrogen, argon or helium.
10. A method according to claim 3, wherein in step (5), the step of curing is carried out at 40 to 80 ℃ for 1 to 5 hours, and the post-treatment is carried out at 120 to 150 ℃ for 1 to 5 hours.
11. The modified carbon fiber interlaminar reinforced polydicyclopentadiene composite material prepared by the method according to any one of claims 3-10.
12. The composite of claim 11, wherein the composite has a tensile strength of 475-641MPa.
13. The composite of claim 12, wherein the composite has a flexural strength of 232 to 450MPa.
14. Use of the composite material according to any one of claims 1-2 and the composite material according to any one of claims 11-13 in fan blades, automotive housings, high-speed rail, aerospace and the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211236101.XA CN117903568A (en) | 2022-10-10 | 2022-10-10 | Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211236101.XA CN117903568A (en) | 2022-10-10 | 2022-10-10 | Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117903568A true CN117903568A (en) | 2024-04-19 |
Family
ID=90689872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211236101.XA Pending CN117903568A (en) | 2022-10-10 | 2022-10-10 | Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117903568A (en) |
-
2022
- 2022-10-10 CN CN202211236101.XA patent/CN117903568A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103201102B (en) | Epoxy resin composition for fiber reinforced composite material, prepreg, and fiber reinforced composite material | |
| US7642336B2 (en) | Phthalonitrile composites | |
| US5476908A (en) | Thermosetting resin composition, cured resin product, prepreg and fiber-reinforced plastic | |
| JPH1080933A (en) | Manufacture of fiber-reinforced composite material | |
| CN103917574B (en) | Fiber reinforced composite material two-liquid type composition epoxy resin and fiber reinforced composite material | |
| US9228083B1 (en) | Multifunctional additives in engineering thermoplastics | |
| JP2017513739A (en) | Process for composites impregnated with thermoplastic polymers obtained from prepolymers and chain extenders | |
| CN108485281A (en) | A kind of low dielectric high intensity wave-penetrating composite material and preparation method thereof | |
| US5104474A (en) | Method for making a fiber reinforced crosslinked polyimide matrix composite article | |
| CN101585966B (en) | Production method of three-dimensional orthogonal woven fabric reinforced PMR type polyimide composite material | |
| CN114349994A (en) | Modified bismaleimide carbon fiber prepreg, composite material and preparation method thereof | |
| CN1213084C (en) | Preparation method and application of modified double maleimide resin | |
| CN117903568A (en) | Nb-TBE modified carbon fiber reinforced polydicyclopentadiene composite material and preparation method and application thereof | |
| CN117903418A (en) | NA modified carbon fiber reinforced polydicyclopentadiene composite material and preparation and application thereof | |
| CN112341827B (en) | Hyperbranched polysiloxane modified cyanate ester resin composite material and preparation method thereof | |
| CN116063823A (en) | TOS modified carbon fiber reinforced polydicyclopentadiene composite material and preparation method thereof | |
| CN116003743A (en) | Preparation method of modified polydicyclopentadiene/carbon fiber composite material | |
| JP6961131B1 (en) | Reinforced fiber stitch base material, preform material, and fiber reinforced composite material, and methods for manufacturing them. | |
| CN114163671A (en) | Cyclic olefin resin-based fiber prepreg and preparation method and application thereof | |
| CN1155646C (en) | Modified dimaleimide resin capable of being used to transfer molding and its prepn | |
| Gu et al. | Polybenzoxazine/fiber composites | |
| CN115947931B (en) | Degradable benzoxazine copolymer and preparation method and application thereof | |
| CN113930052B (en) | Pultrusion method of high-viscosity epoxy resin composition for carbon fiber | |
| Moore et al. | Molecular composites based on thermosetting matrix polymers: Poly (p‐phenyleneterephthalamide)‐epoxy | |
| JPH048464B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication |