CN109306178A - A kind of carbon fiber-based composite material fishing rod and preparation method thereof - Google Patents
A kind of carbon fiber-based composite material fishing rod and preparation method thereof Download PDFInfo
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- CN109306178A CN109306178A CN201811017989.1A CN201811017989A CN109306178A CN 109306178 A CN109306178 A CN 109306178A CN 201811017989 A CN201811017989 A CN 201811017989A CN 109306178 A CN109306178 A CN 109306178A
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- 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
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
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Abstract
The invention discloses a kind of preparation methods of carbon fiber-based composite material fishing rod, include the following steps: the preparation of (one) oligomer solution, (2) preparation of matrix resin, (3) modified carbon nano-tube/nanometer boron fiber composite preparation, (4) preparation of prepreg, the preparation of (five) fishing rod.The invention also discloses the carbon fiber-based composite material fishing rods being prepared according to the preparation method.Disclosed by the invention preparation method is simple, and the carbon fiber-based composite material fishing rod being prepared is cheap, light-weight, rigidity is strong, good toughness, firmness are high, antistatic property and ageing-resistant performance are excellent.
Description
Technical field
The present invention relates to fishing gear technical fields more particularly to a kind of carbon fiber-based composite material fishing rod and preparation method thereof.
Background technique
Have become a kind of important amusement of people, stress-relieving activity with the continuous improvement of people's living standards, fishing, it is competing
Skill fishing is also frequently carried out in high gear.Essential one kind fishing gear is fishing rod in whiffing process, in whiffing process
In play very important effect.Ideal fishing rod not only needs preferable anti-rise intensity, yield strength and elongation etc.
Mechanical performance also requires its antistatic property, toughness and ageing-resistant performance excellent.
The material of existing fishing rod itself has glass fibre and two kinds of carbon fiber, and the material mainly used at present is carbon fiber
Dimension.And carbon fiber is different according to coefficient of elasticity modulus, is divided into low modulus and high-modulus etc..The carbon fiber good toughness of low modulus, jail
Soundness is high, but rigidity is poor, weight weight；And high modulus carbon fiber is light-weight, rigidity is strong, but firmness is not high, crisp, easy to be disconnected.
In addition, since carbon fibre material is conductive, it is expensive, so that the fishing rod price of carbon fiber manufacture is high, and do not have exhausted
Edge function.Using glass fibre as the fishing rod of reinforcing material since paving mode is single, the fishing rod intensity and modulus produced all compares
It is lower.
Ideal fishing rod is prepared, other than needing that reasonable fiber is selected to be enhanced, it is also necessary to which selection is suitable
Matrix resin and fishing rod preparation process, to promote the binding force between resin and fiber, to improve its mechanical mechanics property, so
And the binding force between matrix resin in the prior art and fiber is not strong, and in the curing process, it may appear that micropore and bubble,
It is used in long-term high-intensitive high-frequency situation, intensity and toughness meeting suppression ratio are very fast, easily cause the body of rod to deform, body of rod surface
Coating shedding, service life are shorter.
Therefore, develop it is a kind of it is cheap, light-weight, rigidity is strong, good toughness, firmness are high, antistatic property and resistance to old
It is imperative to change the fishing rod haveing excellent performance.
Summary of the invention
In order to overcome the defects of the prior art, the present invention is intended to provide a kind of light-high-strength carbon fiber-based composite material
Fishing rod, while preparation method being provided.The present invention is realized by the following scheme:
A kind of preparation method of carbon fiber-based composite material fishing rod, includes the following steps:
The preparation of I oligomer solution: by 2,4- diamino -6- vinyl-S- triazine, 1,4- bis- (2', 3'- glycidyl)
Perfluorinated butane, polymerization inhibitor and basic catalyst are added in high boiling solvent, 8-12 hours are stirred to react at 70-80 DEG C, mistake
Basic catalyst is filtered out, oligomer solution is obtained；
The preparation of II matrix resin: 4,4'- talan two will be added in the oligomer solution being prepared by step I
Carboxylic acid, 1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine form solution, then by solution
It is added in reaction kettle, with air in nitrogen or inert gas replacement kettle, 85-95 DEG C reaction 2.5-3.5 hours under normal pressure, then heat up
To 115-125 DEG C reaction 3-4 hours, after be warming up to 225-235 DEG C, primary polycondensate reacts 6-8 hours, then vacuumizes
(500Pa) is heated to 240-250 DEG C, then polycondensation reaction 8-10 hours, after be cooled to room temperature, be adjusted to normal pressure, settle out in water,
The polymer of precipitation is washed 3-5 times with ether, ether is evaporated off in back spin, obtains matrix resin；
The preparation of III modified carbon nano-tube/nanometer boron fiber composite: carbon nanotube, nanometer boron fibre are mixed equal
It is even, after be scattered in ethyl alcohol, add silane coupling agent KH560, be stirred to react at 60-80 DEG C 10-15 hours, rear take out is used
Methylene chloride is washed 3-5 times, then is placed in a vacuum drying oven at 70-80 DEG C and is dried 10-15 hours, and modified carbon nano-tube/nanometer is obtained
Boron fiber composite；
The preparation of IV prepreg: matrix resin, the epoxy resin, 2,4,6- trivinyl that will be prepared by step II
Boroxin, which is added in N-Methyl pyrrolidone, is made into glue, then the modification being prepared by step III is added into glue
Carbon nanotube/nano boron fiber composite, aramid fiber obtain prepreg after mixing evenly；
The preparation of V fishing rod: carbon cloth is immersed in the prepreg being prepared by step IV 3-5 hours, then
Carbon cloth is taken out, is put into radiation field under nitrogen atmosphere, is radiated at 100-120 DEG C using Co 60-γ radiation method,
Radiated time 30-40 minutes, after be placed at 130-140 DEG C of vacuum oven and dry 15-24 hours again, then by the carbon fiber after dipping
Cloth is according to obtaining fishing rod after design size cutting, pipe crimping, tape wrap fastening, demoulding, polishing, coating, drying, assembly.
Preferably ,-the 6- of 2,4- diamino described in step I vinyl-S- triazine, Isosorbide-5-Nitrae-two (2', 3'- glycidyl) are complete
Fluorine butane, polymerization inhibitor, basic catalyst, high boiling solvent mass ratio be 1:1.9:(0.2-0.4): 0.3:15.
Preferably, the polymerization inhibitor is selected from least one of tetrachloro naphthoquinones, 1,4-naphthoquinone.
Preferably, the basic catalyst is selected from one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or several
Kind；The high boiling solvent is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, N-Methyl pyrrolidone.
Preferably, oligomer solution described in step II, 4,4'- stilbenedicarboxylicacid acid, 1- ethyl-(3- dimethylamino
Base propyl) carbodiimide hydrochloride, 4-dimethylaminopyridine 21.2:1.63:(0.4-0.6): 0.3.
Preferably, the inert gas is selected from one or more of helium, neon, argon gas.
Preferably, carbon nanotube described in step III, nanometer boron fibre, ethyl alcohol, silane coupling agent KH560 mass ratio be
2:3:(15-20):0.5。
Preferably, matrix resin described in step IV, epoxy resin, 2,4,6- trivinyl boroxins, N- methyl pyrrole
Pyrrolidone, modified carbon nano-tube/nanometer boron fiber composite, aramid fiber mass ratio be 1:0.5:0.1:1.75:0.15:
0.1。
Preferably, carbon cloth described in step V, prepreg mass ratio be 1:(10-20).
Preferably, the fiber condition of the carbon cloth is middle long filament, and thickness 450D, unit millimeter hole count is 100F.
A kind of carbon fiber-based composite material fishing rod is prepared into using the preparation method of above-mentioned carbon fiber-based composite material fishing rod
It arrives.
The beneficial effects of adopting the technical scheme are that
1) preparation method of carbon fiber-based composite material fishing rod provided by the invention, simple process is easy to operate, to equipment according to
Bad property is not high, not harsh to reaction condition requirement, and raw material is easy to get, low in cost, is suitble to large-scale production.
2) it is more or less existing to overcome fishing rod in the prior art for carbon fiber-based composite material fishing rod provided by the invention
It is expensive, toughness is insufficient, firmness is poor, antistatic property and ageing-resistant performance need the technical issues of being further increased, tool
Have the advantages that cheap, light-weight, rigidity is strong, good toughness, firmness are high, antistatic property and ageing-resistant performance are excellent.
3) carbon fiber-based composite material fishing rod provided by the invention in the preparation process of prepreg, while adding carbon and receiving
Mitron, nanometer boron fibre and aramid fiber, while having the advantages that organic fiber and inorfil, the machine of fishing rod can be effectively improved
Tool mechanical property；Surface is carried out to inorfil to be modified, is on the one hand conducive to it and is uniformly dispersed, and improves fishing rod performance stable homogeneous
Property, also improves its compatibility with high molecular material, the epoxy group of surface modification easily be that hydroxyl is solidifying on matrix resin
Drying stage occurs chemical reaction and links together, and forms three-dimensional net structure, improves comprehensive performance.
4) carbon fiber-based composite material fishing rod provided by the invention, each ingredient and structure synergistic effect, so that fishing rod is comprehensive
Have excellent performance, matrix resin first passes through reaction and forms the oligomer that main chain contains fluorine and triazine structure, oligomer again with 4,4'- bis-
Styrene dicarboxylic acids polycondensation, so that contain fluorine, triazine, aromatic ring, amide on the matrix resin strand being prepared simultaneously
Structure improves its weatherability, ageing-resistant performance and mechanical property, extends the materials'use service life, while introducing hydroxyl side chains,
As crosslinking cure sites, be conducive to subsequent cure moulding process.
5) carbon fiber-based composite material fishing rod provided by the invention does not need additionally to add curing agent and initiator, finally
Being solidified by radiation-initiated polymerization, curing efficiency is high, and it is more environment-friendly and safer, 2,4,6- trivinyl boroxin segment is introduced,
It is also beneficial to improve fishing rod comprehensive performance.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, and make features described above of the invention,
Purpose and advantage are more clear understandable, and the present invention will be further explained with reference to the examples below.Embodiment is only used for
It is bright the present invention rather than limit the scope of the invention.
Raw material described in the following embodiments of the present invention is from upper Haiquan sunrise foreign trade Co., Ltd.
Embodiment 1
A kind of preparation method of carbon fiber-based composite material fishing rod, includes the following steps:
The preparation of I oligomer solution: by bis- (2', 3'- epoxy of 2,4- diamino -6- vinyl-S- triazine 100g, 1,4-
Propyl) perfluorinated butane 190g, tetrachloro naphthoquinones 20g and sodium carbonate 30g be added in dimethyl sulfoxide 1500g, it is stirred at 70 DEG C anti-
It answers 8 hours, is filtered to remove sodium carbonate, obtains oligomer solution；
The preparation of II matrix resin: 4,4'- hexichol second will be added in the oligomer solution 212g being prepared by step I
Docosene dicarboxylic acid 16.3g, 1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride 4g, 4-dimethylaminopyridine 3g are formed
Solution, then solution is added in reaction kettle, with air in nitrogen displacement kettle, lower 85 DEG C of normal pressure are reacted 2.5 hours, then are warming up to
115 DEG C are reacted 3 hours, after be warming up to 225 DEG C, primary polycondensate reacts 6 hours, then vacuumize (500Pa), be heated to 240 DEG C,
Polycondensation reaction 8 hours again, after be cooled to room temperature, be adjusted to normal pressure, settle out in water, the polymer of precipitation is washed 3 times with ether, after
Revolving removes ether, obtains matrix resin；
The preparation of III modified carbon nano-tube/nanometer boron fiber composite: carbon nanotube 20g, nanometer boron fibre 30g are mixed
Close uniformly, after be scattered in ethyl alcohol 150g, add silane coupling agent KH5605g, be stirred to react at 60 DEG C 10 hours, after take
It is washed 3 times with methylene chloride out, then is placed in a vacuum drying oven at 70 DEG C and dries 10 hours, it is fine to obtain modified carbon nano-tube/nanometer boron
Tie up composite material；
The preparation of IV prepreg: matrix resin 10g, epoxy resin 5g, the 2,4,6- tri- that will be prepared by step II
Ethylene boroxines 1g, which is added in N-Methyl pyrrolidone 17.5g, is made into glue, then is added into glue and passes through step III
The modified carbon nano-tube being prepared/nanometer boron fiber composite 1.5g, aramid fiber 1g is presoaked after mixing evenly
Material；
The preparation of V fishing rod: carbon cloth is immersed in the prepreg being prepared by step IV 3 hours, then will
Carbon cloth takes out, and is put into radiation field under nitrogen atmosphere, is radiated at 100 DEG C using Co 60-γ radiation method, when radiation
Between 30 minutes, after be placed at 130 DEG C of vacuum oven and dry 15 hours again, then the carbon cloth after dipping is cut out according to design size
It cuts, the fastening of pipe crimping, tape wrap, demoulding, polishing, coating, drying, obtain fishing rod after assembly；The quality of the carbon cloth, prepreg
Than for 1:10；The fiber condition of the carbon cloth is middle long filament, and thickness 450D, unit millimeter hole count is 100F.
A kind of carbon fiber-based composite material fishing rod is prepared into using the preparation method of above-mentioned carbon fiber-based composite material fishing rod
It arrives.
Embodiment 2
A kind of preparation method of carbon fiber-based composite material fishing rod, includes the following steps:
The preparation of I oligomer solution: by bis- (2', 3'- epoxy of 2,4- diamino -6- vinyl-S- triazine 100g, 1,4-
Propyl) perfluorinated butane 190g, 1,4-naphthoquinone 25g and potassium carbonate 30g be added in n,N-Dimethylformamide 1500g, at 73 DEG C
Under be stirred to react 9 hours, be filtered to remove potassium carbonate, obtain oligomer solution；
The preparation of II matrix resin: 4,4'- hexichol second will be added in the oligomer solution 212g being prepared by step I
Docosene dicarboxylic acid 16.3g, 1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride 4.5g, 4-dimethylaminopyridine 3g shape
It is added in reaction kettle at solution, then by solution, with air in helium replacement kettle, lower 88 DEG C of normal pressure are reacted 2.8 hours, then are warming up to
118 DEG C are reacted 3.2 hours, after be warming up to 228 DEG C, primary polycondensate reacts 6.5 hours, then vacuumizes (500Pa), is heated to
243 DEG C, then polycondensation reaction 8.5 hours, after be cooled to room temperature, be adjusted to normal pressure, settle out in water, by the polymer ether of precipitation
It washes 4 times, ether is evaporated off in back spin, obtains matrix resin；
The preparation of III modified carbon nano-tube/nanometer boron fiber composite: carbon nanotube 20g, nanometer boron fibre 30g are mixed
Close uniformly, after be scattered in ethyl alcohol 170g, add silane coupling agent KH5605g, be stirred to react at 65 DEG C 11.5 hours, after
Taking-up is washed 4 times with methylene chloride, then is placed in a vacuum drying oven at 73 DEG C and is dried 12 hours, and modified carbon nano-tube/nanometer boron is obtained
Fibrous composite；
The preparation of IV prepreg: matrix resin 10g, epoxy resin 5g, the 2,4,6- tri- that will be prepared by step II
Ethylene boroxines 1g, which is added in N-Methyl pyrrolidone 17.5g, is made into glue, then is added into glue and passes through step III
The modified carbon nano-tube being prepared/nanometer boron fiber composite 1.5g, aramid fiber 1g is presoaked after mixing evenly
Material；
The preparation of V fishing rod: carbon cloth is immersed in the prepreg being prepared by step IV 3.5 hours, then
Carbon cloth is taken out, is put into radiation field under nitrogen atmosphere, is radiated at 105 DEG C using Co 60-γ radiation method, radiation
Time 32 minutes, after be placed at 133 DEG C of vacuum oven and dry 18 hours again, then by the carbon cloth after dipping according to design size
Fishing rod is obtained after cutting, pipe crimping, tape wrap fastening, demoulding, polishing, coating, drying, assembly；The matter of the carbon cloth, prepreg
Amount is than being 1:13；The fiber condition of the carbon cloth is middle long filament, and thickness 450D, unit millimeter hole count is 100F.
A kind of carbon fiber-based composite material fishing rod is prepared into using the preparation method of above-mentioned carbon fiber-based composite material fishing rod
It arrives.
Embodiment 3
A kind of preparation method of carbon fiber-based composite material fishing rod, includes the following steps:
The preparation of I oligomer solution: by bis- (2', 3'- epoxy of 2,4- diamino -6- vinyl-S- triazine 100g, 1,4-
Propyl) perfluorinated butane 190g, tetrachloro naphthoquinones 30g and sodium hydroxide 30g be added in N-Methyl pyrrolidone 1500g, at 75 DEG C
Under be stirred to react 10 hours, be filtered to remove sodium hydroxide, obtain oligomer solution；
The preparation of II matrix resin: 4,4'- hexichol second will be added in the oligomer solution 212g being prepared by step I
Docosene dicarboxylic acid 16.3g, 1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride 5g, 4-dimethylaminopyridine 3g are formed
Solution, then solution is added in reaction kettle, with air in neon displacement kettle, lower 90 DEG C of normal pressure are reacted 3 hours, then are warming up to 120
DEG C reaction 3.5 hours, after be warming up to 230 DEG C, primary polycondensate reacts 7 hours, then vacuumize (500Pa), be heated to 245 DEG C,
Polycondensation reaction 9 hours again, after be cooled to room temperature, be adjusted to normal pressure, settle out in water, the polymer of precipitation is washed 4 times with ether, after
Revolving removes ether, obtains matrix resin；
The preparation of III modified carbon nano-tube/nanometer boron fiber composite: carbon nanotube 20g, nanometer boron fibre 30g are mixed
Close uniformly, after be scattered in ethyl alcohol 180g, add silane coupling agent KH5605g, be stirred to react at 70 DEG C 13 hours, after take
It is washed 5 times with methylene chloride out, then is placed in a vacuum drying oven at 76 DEG C and dries 13 hours, it is fine to obtain modified carbon nano-tube/nanometer boron
Tie up composite material；
The preparation of IV prepreg: matrix resin 10g, epoxy resin 5g, the 2,4,6- tri- that will be prepared by step II
Ethylene boroxines 1g, which is added in N-Methyl pyrrolidone 17.5g, is made into glue, then is added into glue and passes through step III
The modified carbon nano-tube being prepared/nanometer boron fiber composite 1.5g, aramid fiber 1g is presoaked after mixing evenly
Material；
The preparation of V fishing rod: carbon cloth is immersed in the prepreg being prepared by step IV 4 hours, then will
Carbon cloth takes out, and is put into radiation field under nitrogen atmosphere, is radiated at 110 DEG C using Co 60-γ radiation method, when radiation
Between 36 minutes, after be placed at 136 DEG C of vacuum oven and dry 19 hours again, then the carbon cloth after dipping is cut out according to design size
It cuts, the fastening of pipe crimping, tape wrap, demoulding, polishing, coating, drying, obtain fishing rod after assembly；The quality of the carbon cloth, prepreg
Than for 1:15；The fiber condition of the carbon cloth is middle long filament, and thickness 450D, unit millimeter hole count is 100F.
A kind of carbon fiber-based composite material fishing rod is prepared into using the preparation method of above-mentioned carbon fiber-based composite material fishing rod
It arrives.
Embodiment 4
A kind of preparation method of carbon fiber-based composite material fishing rod, includes the following steps:
The preparation of I oligomer solution: by bis- (2', 3'- epoxy of 2,4- diamino -6- vinyl-S- triazine 100g, 1,4-
Propyl) perfluorinated butane 190g, polymerization inhibitor 35g and basic catalyst 30g be added in high boiling solvent 1500g, stir at 78 DEG C
Reaction 11 hours is mixed, basic catalyst is filtered to remove, obtains oligomer solution；The polymerization inhibitor is tetrachloro naphthoquinones, 1,4- naphthoquinones
The mixture that 3:2 in mass ratio is mixed；The basic catalyst be sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide by
The mixture that mass ratio 1:2:1:1 is mixed；The high boiling solvent is dimethyl sulfoxide, N,N-dimethylformamide, N- first
The mixture that base pyrrolidones 2:3:1 in mass ratio is mixed；
The preparation of II matrix resin: 4,4'- hexichol second will be added in the oligomer solution 212g being prepared by step I
Docosene dicarboxylic acid 16.3g, 1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride 5.5g, 4-dimethylaminopyridine 3g shape
It is added in reaction kettle at solution, then by solution, with air in argon gas displacement kettle, lower 93 DEG C of normal pressure are reacted 3.3 hours, then are warming up to
123 DEG C are reacted 3.8 hours, after be warming up to 233 DEG C, primary polycondensate reacts 7.5 hours, then vacuumizes (500Pa), is heated to
248 DEG C, then polycondensation reaction 9.5 hours, after be cooled to room temperature, be adjusted to normal pressure, settle out in water, by the polymer ether of precipitation
It washes 5 times, ether is evaporated off in back spin, obtains matrix resin；
The preparation of III modified carbon nano-tube/nanometer boron fiber composite: carbon nanotube 20g, nanometer boron fibre 30g are mixed
Close uniformly, after be scattered in ethyl alcohol 190g, add silane coupling agent KH5605g, be stirred to react at 76 DEG C 14.5 hours, after
Taking-up is washed 5 times with methylene chloride, then is placed in a vacuum drying oven at 77 DEG C and is dried 14 hours, and modified carbon nano-tube/nanometer boron is obtained
Fibrous composite；
The preparation of IV prepreg: matrix resin 10g, epoxy resin 5g, the 2,4,6- tri- that will be prepared by step II
Ethylene boroxines 1g, which is added in N-Methyl pyrrolidone 17.5g, is made into glue, then is added into glue and passes through step III
The modified carbon nano-tube being prepared/nanometer boron fiber composite 1.5g, aramid fiber 1g is presoaked after mixing evenly
Material；
The preparation of V fishing rod: carbon cloth is immersed in the prepreg being prepared by step IV 4.5 hours, then
Carbon cloth is taken out, is put into radiation field under nitrogen atmosphere, is radiated at 115 DEG C using Co 60-γ radiation method, radiation
Time 38 minutes, after be placed at 137 DEG C of vacuum oven and dry 22 hours again, then by the carbon cloth after dipping according to design size
Fishing rod is obtained after cutting, pipe crimping, tape wrap fastening, demoulding, polishing, coating, drying, assembly；The matter of the carbon cloth, prepreg
Amount is than being 1:18；The fiber condition of the carbon cloth is middle long filament, and thickness 450D, unit millimeter hole count is 100F.
A kind of carbon fiber-based composite material fishing rod is prepared into using the preparation method of above-mentioned carbon fiber-based composite material fishing rod
It arrives.
Embodiment 5
A kind of preparation method of carbon fiber-based composite material fishing rod, includes the following steps:
The preparation of I oligomer solution: by bis- (2', 3'- epoxy of 2,4- diamino -6- vinyl-S- triazine 100g, 1,4-
Propyl) perfluorinated butane 190g, 1,4-naphthoquinone 40g and potassium hydroxide 30g be added in dimethyl sulfoxide 1500g, stir at 80 DEG C
Reaction 12 hours, is filtered to remove potassium hydroxide, obtains oligomer solution；
The preparation of II matrix resin: 4,4'- hexichol second will be added in the oligomer solution 212g being prepared by step I
Docosene dicarboxylic acid 16.3g, 1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride 6g, 4-dimethylaminopyridine 3g are formed
Solution, then solution is added in reaction kettle, with air in nitrogen displacement kettle, lower 95 DEG C of normal pressure are reacted 3.5 hours, then are warming up to
125 DEG C are reacted 4 hours, after be warming up to 235 DEG C, primary polycondensate reacts 8 hours, then vacuumize (500Pa), be heated to 250 DEG C,
Polycondensation reaction 10 hours again, after be cooled to room temperature, be adjusted to normal pressure, settle out in water, the polymer of precipitation is washed 5 times with ether,
Ether is evaporated off in back spin, obtains matrix resin；
The preparation of III modified carbon nano-tube/nanometer boron fiber composite: carbon nanotube 20g, nanometer boron fibre 30g are mixed
Close uniformly, after be scattered in ethyl alcohol 200g, add silane coupling agent KH5605g, be stirred to react at 80 DEG C 15 hours, after take
It is washed 5 times with methylene chloride out, then is placed in a vacuum drying oven at 80 DEG C and dries 15 hours, it is fine to obtain modified carbon nano-tube/nanometer boron
Tie up composite material；
The preparation of IV prepreg: matrix resin 10g, epoxy resin 5g, the 2,4,6- tri- that will be prepared by step II
Ethylene boroxines 1g, which is added in N-Methyl pyrrolidone 17.5g, is made into glue, then is added into glue and passes through step III
The modified carbon nano-tube being prepared/nanometer boron fiber composite 1.5g, aramid fiber 1g is presoaked after mixing evenly
Material；
The preparation of V fishing rod: carbon cloth is immersed in the prepreg being prepared by step IV 5 hours, then will
Carbon cloth takes out, and is put into radiation field under nitrogen atmosphere, is radiated at 120 DEG C using Co 60-γ radiation method, when radiation
Between 40 minutes, after be placed at 140 DEG C of vacuum oven and dry 24 hours again, then the carbon cloth after dipping is cut out according to design size
It cuts, the fastening of pipe crimping, tape wrap, demoulding, polishing, coating, drying, obtain fishing rod after assembly；The quality of the carbon cloth, prepreg
Than for 1:20；The fiber condition of the carbon cloth is middle long filament, and thickness 450D, unit millimeter hole count is 100F.
A kind of carbon fiber-based composite material fishing rod is prepared into using the preparation method of above-mentioned carbon fiber-based composite material fishing rod
It arrives.
Comparative example
A kind of carbon fiber fishing rod is prepared into using the preparation method of Chinese invention patent CN 107057325A embodiment 1
It arrives.
Correlated performance test, test result and test method are carried out to fishing rod obtained by above-described embodiment 1-5 and comparative example
As shown in table 1.
Table 1
As can be seen from the above table, compared with fishing rod in the prior art, carbon fiber-based disclosed by the embodiments of the present invention is compound
Material fishing rod has more excellent mechanical property.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (10)
1. a kind of preparation method of carbon fiber-based composite material fishing rod, which comprises the steps of:
The preparation of I oligomer solution: by 2,4- diamino -6- vinyl-S- triazine, 1,4- bis- (2', 3'- glycidyl) perfluor
Butane, polymerization inhibitor and basic catalyst are added in high boiling solvent, are stirred to react at 70-80 DEG C 8-12 hours, are crossed and are filtered out
Basic catalyst is removed, oligomer solution is obtained；
The preparation of II matrix resin: 4,4'- talan dicarboxyl will be added in the oligomer solution being prepared by step I
Acid, 1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine form solution, then solution are added
Enter in reaction kettle, with air in nitrogen or inert gas replacement kettle, 85-95 DEG C reaction 2.5-3.5 hours under normal pressure, then be warming up to
115-125 DEG C reaction 3-4 hours, after be warming up to 225-235 DEG C, primary polycondensate reacts 6-8 hours, then vacuumize (500Pa),
Be heated to 240-250 DEG C, then polycondensation reaction 8-10 hours, after be cooled to room temperature, be adjusted to normal pressure, settle out in water, by precipitation
Polymer is washed 3-5 times with ether, and ether is evaporated off in back spin, obtains matrix resin；
The preparation of III modified carbon nano-tube/nanometer boron fiber composite: carbon nanotube, nanometer boron fibre are uniformly mixed, after
It is scattered in ethyl alcohol, adds silane coupling agent KH560, be stirred to react at 60-80 DEG C 10-15 hours, rear take out uses dichloro
Methane is washed 3-5 times, then is placed in a vacuum drying oven at 70-80 DEG C and is dried 10-15 hours, and it is fine to obtain modified carbon nano-tube/nanometer boron
Tie up composite material；
The preparation of IV prepreg: matrix resin, epoxy resin, the 2,4,6- triethylene basic ring boron that will be prepared by step II
Oxygen alkane, which is added in N-Methyl pyrrolidone, is made into glue, then is added into glue and receives by the carbon modified that step III is prepared
Mitron/nanometer boron fiber composite, aramid fiber obtains prepreg after mixing evenly；
The preparation of V fishing rod: carbon cloth is immersed in the prepreg being prepared by step IV 3-5 hours, then by carbon
Fiber cloth is taken out, and is put into radiation field under nitrogen atmosphere, is radiated at 100-120 DEG C using Co 60-γ radiation method, radiation
Time 30-40 minute, after be placed at 130-140 DEG C of vacuum oven and dry 15-24 hours again, then the carbon cloth after dipping is pressed
According to obtaining fishing rod after design size cutting, pipe crimping, tape wrap fastening, demoulding, polishing, coating, drying, assembly.
2. the preparation method of carbon fiber-based composite material fishing rod according to claim 1, which is characterized in that institute in step I
State 2,4- diamino -6- vinyl-S- triazine, 1,4- bis- (2', 3'- glycidyl) perfluorinated butane, polymerization inhibitor, base catalysis
Agent, high boiling solvent mass ratio be 1:1.9:(0.2-0.4): 0.3:15.
3. the preparation method of carbon fiber-based composite material fishing rod according to claim 1, which is characterized in that the polymerization inhibitor
Selected from least one of tetrachloro naphthoquinones, 1,4- naphthoquinones.
4. the preparation method of carbon fiber-based composite material fishing rod according to claim 1, which is characterized in that the alkalinity is urged
Agent is selected from one or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide；The high boiling solvent is selected from diformazan
One or more of sulfoxide, N,N-dimethylformamide, N-Methyl pyrrolidone.
5. the preparation method of carbon fiber-based composite material fishing rod according to claim 1, which is characterized in that institute in step II
State oligomer solution, 4,4'- stilbenedicarboxylicacid acid, 1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride, 4- bis-
Methylamino pyridine 21.2:1.63:(0.4-0.6): 0.3.
6. the preparation method of carbon fiber-based composite material fishing rod according to claim 1, which is characterized in that the indifferent gas
Body is selected from one or more of helium, neon, argon gas.
7. the preparation method of carbon fiber-based composite material fishing rod according to claim 1, which is characterized in that institute in step III
State carbon nanotube, nanometer boron fibre, ethyl alcohol, silane coupling agent KH560 mass ratio be 2:3:(15-20): 0.5.
8. the preparation method of carbon fiber-based composite material fishing rod according to claim 1, which is characterized in that institute in step IV
State matrix resin, epoxy resin, 2,4,6- trivinyl boroxin, N-Methyl pyrrolidone, modified carbon nano-tube/nanometer boron
Fibrous composite, aramid fiber mass ratio be 1:0.5:0.1:1.75:0.15:0.1.
9. the preparation method of carbon fiber-based composite material fishing rod according to claim 1, which is characterized in that institute in step V
State carbon cloth, the mass ratio of prepreg is 1:(10-20)；The fiber condition of the carbon cloth is middle long filament, and thickness is
450D, unit millimeter hole count are 100F.
What 10. a kind of preparation method using any one of the claim 1-9 carbon fiber-based composite material fishing rod was prepared
Carbon fiber-based composite material fishing rod.
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| CN201811017989.1A CN109306178B (en) | 2018-09-03 | 2018-09-03 | Carbon fiber-based composite material fishing rod and preparation method thereof |
| CN202010950782.0A CN112048176A (en) | 2018-09-03 | 2018-09-03 | Light high strength carbon fiber based composite material fishing rod |
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| CN201811017989.1A CN109306178B (en) | 2018-09-03 | 2018-09-03 | Carbon fiber-based composite material fishing rod and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110078952A (en) * | 2019-03-20 | 2019-08-02 | 青岛中维新材料有限公司 | A kind of preparation method of aramid fiber carbon fiber composite reinforced material |
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| CN113994937B (en) * | 2021-01-25 | 2022-10-11 | 嘉兴太平洋钓具有限公司 | Light high strength carbon fiber fishing rod and apparatus for producing thereof |
| CN113402288A (en) * | 2021-06-16 | 2021-09-17 | 江苏集萃碳纤维及复合材料应用技术研究院有限公司 | Preparation method of carbon fiber reinforced high-strength and high-heat-conductivity composite film |
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| CN112048176A (en) | 2020-12-08 |
| CN109306178B (en) | 2021-05-28 |
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Effective date of registration: 20211026 Address after: 264200 no.88-1, Xier street, Beiguan village, Huancui District, Weihai City, Shandong Province Patentee after: WEIHAI KENY FISHING TOOLS Co.,Ltd. Address before: Room 350, 7th floor, Yannong complex building, Dongfanghong community, 459 Lusong Road, high tech Development Zone, Changsha City, Hunan Province, 410205 Patentee before: HUNAN QIWEI TECHNOLOGY Co.,Ltd. |
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Denomination of invention: A carbon fiber based composite material fishing rod and its preparation method Effective date of registration: 20230426 Granted publication date: 20210528 Pledgee: Weihai Commercial Bank Co.,Ltd. City Sub branch Pledgor: WEIHAI KENY FISHING TOOLS Co.,Ltd. Registration number: Y2023980039326 |