CN105199316A - Manufacturing method for carbon fiber composite material cable - Google Patents
Manufacturing method for carbon fiber composite material cable Download PDFInfo
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- CN105199316A CN105199316A CN201510552859.8A CN201510552859A CN105199316A CN 105199316 A CN105199316 A CN 105199316A CN 201510552859 A CN201510552859 A CN 201510552859A CN 105199316 A CN105199316 A CN 105199316A
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Abstract
The invention relates to a manufacturing method for a carbon fiber composite material cable. The method comprises the following steps that carbon fiber is led out from a creel and enters a first impregnation area for impregnation, and adopted epoxy resin has the heat-resisting high mechanical performance; the carbon fiber obtained after impregnation is performed enters a first curing furnace for procuring, a carbon fiber composite core is obtained, the diameter ranges from 5 mm to 12 mm, and the temperature is adjusted to enable the curing degree to reach more than 85%; glass fiber on the two sides is led out to enter a second impregnation area and a third impregnation area respectively for impregnation, and the adopted epoxy resin has the high temperature resistance and weather resistance; the impregnated glass fiber is wound through a winding area to coat the carbon fiber core, the thickness of the single side ranges from 0.2 mm to 2 mm, and the winding speed is controlled by a servo motor to be synchronous with the pultrusion speed; the carbon fiber composite core and a glass fiber protective layer are composited and pass through a second curing furnace, and the temperature is adjusted for sufficiently curing the carbon fiber composite core and the glass fiber protective layer; the composite material cable core is taken up at a winding disc after passing through a tractor.
Description
The divisional application that the application is the applying date is " on 02 05th, 2013 ", application number is " 2013100442638 ", name is called the application for a patent for invention of " a kind of making method of carbon fiber composite material cable wire ".
Technical field
The present invention relates to a kind of cable core, especially relate to a kind of making method of carbon fiber composite material cable wire.
Background technology
Cable core as the substitute products of traditional steel core, due to long-term high temperature in the wild, sunshine, work under the mal-conditions such as climate change, while requiring it to have excellent mechanical property, also there are high temperature resistant, uvioresistant and resistance to deterioration etc., require very high to the over-all properties of cable core.
Traditional cable core structure is the load-bearing core that internal carbon fibers and epoxy resin composite material are made, the outside protective layer being glass fibre and epoxy resin composite and making, both shared same resin systems.Under same resin system, interact between the performances such as high temperature resistant, tensile strength, bending strength, modulus, ultimate compression strength, uvioresistant and resistance to deterioration, by modification increase performance in a certain respect often with sacrifice on the other hand performance for cost.
Dicyclopentadiene (DCPD) is the dimer of cyclopentadiene, mainly come from cracking of ethylene by-product C 5 fraction and
Carbonization of coal by-product light benzene fraction, because chemically reactive is high, be the raw material of petroleum resin and multiple fine chemicals, be introduced into epoxy resin, Properties of Epoxy Resin can be made to improve, as its viscosity, mechanical property and good flame-retardance and toughness are all better than general purpose epoxy resin.
Summary of the invention
The present invention devises a kind of making method of carbon fiber composite material cable wire, and it is poor that its technical problem solved is that existing cable core exists the aspect of performances such as resistance to elevated temperatures, tensile strength, mechanical property, flame retardant resistance, ultimate compression strength, uvioresistant and resistance to deterioration.
In order to solve the technical problem of above-mentioned existence, present invention employs following scheme: a kind of cable core, comprise load-bearing core (12) and protective layer (13), described protective layer (13) is coated on the outside of described load-bearing core (12) by winding process, it is characterized in that: the mixture that described load-bearing core (12) is heat-resisting strong mechanical performance epoxy resin and carbon fiber, the mixture that described protective layer (13) is high temperature resistant weather resistance epoxy resin and glass fibre; Described load-bearing core
(12) heat-resisting strong mechanical performance epoxy resin is made up of following compositions: the blending epoxy of 100 mass parts; The solidifying agent of 20-75 mass parts; The thinner of 10-30 mass parts; The promotor of 0.5-5.0 mass parts; The filler of 0.5-5.0 mass parts; Described blending epoxy comprises epoxy resin a and epoxy resin b; Epoxy resin a is dicyclopentadiene (DCPD) type epoxy resin, and described epoxy resin b is the composition of glycidyl amine epoxy resin and bisphenol A-type glycidyl ether type epoxy resin; The mass ratio of epoxy resin a and epoxy resin b is: 50-80:20-50; The structural formula of described dicyclopentadiene type epoxy resin is as follows:
, in formula, n is the integer of 0 to 10; The mass ratio of the glycidyl amine epoxy resin in described epoxy resin b and bisphenol A-type glycidyl ether type epoxy resin is: 1:9-9:1.
In described protective layer (13), high temperature resistant weather resistance epoxy resin is made up of following compositions: comprise component A and B component, wherein component A comprises following compositions: 100 mass parts epoxy resin, 5-20 mass parts thinner, 0.5-5.0 mass parts silane coupling agent, the mineral filler of 0.5-5.0 mass parts; B component comprises following compositions: 25-45 mass parts amine curing agent, 0.5-5.0 mass parts promotor; Described epoxy resin is the combination of epoxy resin c and epoxy resin d, and the mass ratio of epoxy resin c and epoxy resin d is: 50-80:20-50; Described epoxy resin c is for comprising glycidic amine type, diglycidyl ether type or the glycidyl ester type glycolylurea epoxide resin of one or more glycolylurea ring (five yuan of diazacyclos), glycolylurea ring (five yuan of diazacyclos) structural formula is as follows, and in glycolylurea ring (five yuan of diazacyclos) structural formula, substituent R 1 and R2 are H, CH3, C2H5, aryl or aralkyl:
; Described epoxy resin d is at least one in following several epoxy resin: 4,5-oxirane ring ethane-1,2-dioctyl phthalate 2-glycidyl ester, bisphenol-f type glycidyl ether type epoxy resin or bisphenol A-type glycidyl ether type epoxy resin; Wherein, bisphenol-f type glycidyl ether type epoxy resin or bisphenol A-type glycidyl ether type epoxy resin preferred viscosity ranges: 500-4000mPas(25 DEG C).
Further, described protective layer (13) epoxy resin c is the 2-glycidyl amine type glycolylurea epoxide resin containing a glycolylurea ring, and chemical structural formula is as follows:
; There is following combination selection mode in substituent R 1 wherein and R2: the 1) compound of R1 to be H, R2 be H; 2) compound of R1 to be CH3, R2 be H; 3) compound of R1 to be CH3, R2 be CH3; 4) compound of R1 to be C2H5, R2 be H; 5) compound of R1 to be C2H5, R2 be CH3.
Further, amine curing agent described in described protective layer (13) is the combination of amine curing agent a and amine curing agent b, and the mass ratio of amine curing agent a and amine curing agent b is: 20-40:5-25; Described amine curing agent a is the polyether monoamine compound comprising two or more amido functional groups, preferably from molecular weight ranges 200-2500, range of viscosities: 5-300mPas(25 DEG C) polyether monoamine compound in one or more; Described amine curing agent b is one or more of aliphatics amine and modified aliphatic aminated compounds, preferably from one or more in diethylenetriamine, triethylene tetramine, tetraethylene pentamine, diamines, methylol quadrol, methylol diethylenetriamine, beta-hydroxyethyl quadrol.
Further, described in described protective layer (13), promotor is selected from: one or more in 2,4,6-tri-(dimethylamino methyl) phenol, boron trifluoride complex, trolamine.
Further; thinner described in described protective layer (13) is the compound comprising two epoxy functionality and at least one ehter bond, preferably from one or more in ethylene glycol diglycidylether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cylohexanediol diglycidyl ether, cyclohexanedimethanodiglycidyl diglycidyl ether, neopentylglycol diglycidyl ether, polyethyleneglycol diglycidylether, resorcinol diglycidyl ether.
Further, described in described protective layer (13), coupling agent is the silane coupling agent comprising epoxy functionality; Be preferably γ-aminopropyl triethoxysilane, the one in γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-(methacryloxy) propyl trimethoxy silicane.
Further, the solidifying agent in described load-bearing core (12) is selected from: one or more in Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, tetrahydrochysene phthalate anhydride, α-methacrylic acid.
Further, the thinner in described load-bearing core (12) is selected from: one or more in ethylene glycol diglycidylether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cylohexanediol diglycidyl ether.
Further, the promotor in described load-bearing core (12) is selected from: one or more in tertiary amine, benzyldimethylamine, 2,4,6-tri-(dimethylamino methyl) phenol, boron trifluoride complex, 2-ethyl-4-methylimidazole.
Further, the mineral filler in described load-bearing core (12) is selected from: one or more in calcium carbonate, kaolin, diatomite, wilkinite, nano-titanium oxide, talcum powder.
A making method for carbon fiber composite material cable wire, comprises the following steps:
The first step, is drawn carbon fiber by creel, enters the first impregnation district impregnation, and the epoxy resin of use is heat-resisting strong mechanical performance epoxy resin;
Second step, after impregnation completes, carbon fiber enters the first curing oven Procuring, obtained carbon fiber complex core, and diameter is 5mm-12mm, regulates temperature to make degree of cure reach more than 85%;
3rd, both sides glass fibre enters the second impregnation district and the 3rd impregnation district impregnation after drawing respectively, and the epoxy resin of use is high temperature resistant weather resistance epoxy resin;
4th step, after impregnation, glass fibre is outer at carbon fiber core by being wound around district's voluble wrapping, and one-sided thickness is 0.5mm-2mm, and wind-up speed is by Serve Motor Control and pultrusion speed synchronised;
5th step, carbon fiber complex core by the second curing oven, regulates temperature to make both fully solidifications together with after glass fibre protective layer compound;
6th step, composite material cable core goods are by after tractor, and at closed reel, place collects.
The making method of this carbon fiber composite material cable wire, compared with the making method of traditional carbon fiber composite material cable wire, has following beneficial effect:
(1) the heat-resisting strong mechanical performance epoxy resin of the load-bearing core in the present invention is selected from the composition of dicyclopentadiene type epoxy resin, glycidyl amine epoxy resin and glycidyl ether type epoxy resin, their constituent has strong mechanical performance and good flame-retardance performance, and resin long working life can meet the needs that cable uses.
(2) the present invention's heat-resisting strong mechanical performance epoxy resin has good wetting property and bonding strength to carbon fiber, cured product has good thermotolerance and physical strength, and the thermotolerance of the fibre reinforced cable adopting the present invention heat-resisting strong mechanical performance epoxy resin to make, wet fastness, electric property, toughness and workability are greatly enhanced.
(3) anhydrides compound or acids is adopted to import the curing agent mixture of molding epoxy resin as vacuum in the present invention, thus there is good toughness and higher second-order transition temperature, to meet heat resistant requirements, can use at a higher temperature after aftertreatment, its finished product interior solid is good, air-gap-free, performance are homogeneous.
(4) thinner in the heat-resisting strong mechanical performance epoxy resin of the present invention can reduce curing system viscosity, increases mobility, increases the service life, do not affect again the mechanical property of epoxy resin cured product.
(5) promotor in the heat-resisting strong mechanical performance epoxy resin of the present invention effectively can solve the problem of self-vulcanizing overlong time, while shortening set time, ensure that the intensity of cured article remains unchanged substantially.
(6) add filler in the heat-resisting strong mechanical performance epoxy resin of the present invention, except can reducing goods cost, also can improve epoxy resin processibility, flame resistivity, the viscosity of resin and processing technology.
(7) the present invention adopts glycolylurea epoxide resin and low viscosity epoxy resin (4,5-oxirane ring ethane-1,2-dioctyl phthalate 2-glycidyl ester, bisphenol-f type glycidyl ether type epoxy resin or bisphenol A-type glycidyl ether type epoxy resin) commixed type epoxy resin as resin matrix, can not only meet fibre reinforced composites vacuum imports shaping to the low viscous requirement of resin, and composite product can also be made to possess excellent resistance to elevated temperatures.
(8) glycolylurea epoxide resin used in the present invention has that viscosity is low, good manufacturability, good wetting property is had to glass fibre, carbon fiber and multiple filler, owing to comprising five yuan of diazacyclos in its structure, also have the features such as Heat stability is good, thermotolerance is high, weather resisteant is good concurrently.
(9) the toughness functional groups such as multiple ehter bonds are comprised in the polyether monoamine solidifying agent structure used in the present invention, composite product can be made to have the shock resistance of high-strength and high ductility, by adopting the commixed type curing system of polyether monoamine solidifying agent and aliphatics amine curing agent, the problems such as cured article fragility, elongation at break are little effectively can be solved.
(10) the present invention adopts a certain amount of promotor to coordinate commixed type amine curing agent to use together, effectively can solve the problem of self-vulcanizing overlong time, while shortening set time, ensure that the intensity of cured article remains unchanged substantially.
(11) the present invention adopts mineral filler can reduce the shrinking percentage of goods, improves the dimensional stability of goods, surface smoothness and smoothness etc., also can improve shock strength and the compressive strength of goods to a certain extent; In addition, filler add the consumption that can reduce epoxy resin, reduce costs.
(12) auxiliary agent that the present invention adopts also comprises silane coupling agent and thinner.Wherein silane coupling agent can improve bond strength between reinforcing fiber materials and resin, improves interfacial state, is conducive to the mechanical property and the electrical insulation capability that improve composite product; The effect of thinner can reduce the viscosity of whole composition.
Accompanying drawing explanation
Fig. 1 is the structural representation of cable core of the present invention;
Fig. 2 is the moulding process schematic diagram of cable core of the present invention.
Description of reference numerals: 1-creel; 2-the first impregnation district; 3-the first curing oven; 4-the second impregnation district; 5-the three impregnation district; 6-be wound around district; 7-the second curing oven; 8-tractor; 9-closed reel; 10-carbon fiber; 11-glass fibre; 12-load-bearing core; 13-protective layer.
Embodiment
Below in conjunction with Fig. 1 and Fig. 2, the present invention will be further described: as shown in Figure 1, a kind of cable core, comprise load-bearing core 12 and protective layer 13, protective layer 13 is coated on the outside of load-bearing core 12 by winding process, load-bearing core 12 is the mixture of heat-resisting strong mechanical performance epoxy resin and carbon fiber, and protective layer 13 is the mixture of high temperature resistant weather resistance epoxy resin and glass fibre; The heat-resisting strong mechanical performance epoxy resin of load-bearing core 12 is made up of following compositions: the blending epoxy of 100 mass parts; The solidifying agent of 20-75 mass parts; The thinner of 10-30 mass parts; The promotor of 0.5-5.0 mass parts; The filler of 0.5-5.0 mass parts; Described blending epoxy comprises epoxy resin a and epoxy resin b; Epoxy resin a is dicyclopentadiene (DCPD) type epoxy resin, and epoxy resin b is the composition of glycidyl amine epoxy resin and bisphenol A-type glycidyl ether type epoxy resin; The mass ratio of epoxy resin a and epoxy resin b is: 50-80:20-50; The structural formula of described dicyclopentadiene type epoxy resin is as follows:
In formula, n is the integer of 0 to 10; The mass ratio of the glycidyl amine epoxy resin in described epoxy resin b and bisphenol A-type glycidyl ether type epoxy resin is: 1:9-9:1.
Protective layer 13 epoxy resin c is the 2-glycidyl amine type glycolylurea epoxide resin containing a glycolylurea ring, and chemical structural formula is as follows:
; There is following combination selection mode in substituent R 1 wherein and R2: the 1) compound of R1 to be H, R2 be H; 2) compound of R1 to be CH3, R2 be H; 3) compound of R1 to be CH3, R2 be CH3; 4) compound of R1 to be C2H5, R2 be H; 5) compound of R1 to be C2H5, R2 be CH3.
Amine curing agent described in protective layer 13 is the combination of amine curing agent a and amine curing agent b, and the mass ratio of amine curing agent a and amine curing agent b is: 20-40:5-25; Described amine curing agent a is the polyether monoamine compound comprising two or more amido functional groups, preferably from molecular weight ranges 200-2500, range of viscosities: 5-300mPas(25 DEG C) polyether monoamine compound in one or more; Described amine curing agent b is one or more of aliphatics amine and modified aliphatic aminated compounds, preferably from one or more in diethylenetriamine, triethylene tetramine, tetraethylene pentamine, diamines, methylol quadrol, methylol diethylenetriamine, beta-hydroxyethyl quadrol.
Described in protective layer 13, promotor is selected from: one or more in 2,4,6-tri-(dimethylamino methyl) phenol, boron trifluoride complex, trolamine.
Thinner described in protective layer 13 is the compound comprising two epoxy functionality and at least one ehter bond, preferably from one or more in ethylene glycol diglycidylether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cylohexanediol diglycidyl ether, cyclohexanedimethanodiglycidyl diglycidyl ether, neopentylglycol diglycidyl ether, polyethyleneglycol diglycidylether, resorcinol diglycidyl ether.
Coupling agent described in protective layer 13 is the silane coupling agent comprising epoxy functionality; Be preferably γ-aminopropyl triethoxysilane, the one in γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-(methacryloxy) propyl trimethoxy silicane.
Also add uv-absorbing agent in protective layer 13, uv-absorbing agent is one in UV-9, UV-531, UV-327, triazine-5 or how several combination.
Also add energy transfer agent in protective layer 13, described energy transfer agent is one or both combinations in three (1,2,2,6,6-pentamethvl base) phosphorous acid esters or AM101.
Solidifying agent in load-bearing core 12 is selected from: one or more in Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, tetrahydrochysene phthalate anhydride, α-methacrylic acid.
Thinner in load-bearing core 12 is selected from: one or more in ethylene glycol diglycidylether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cylohexanediol diglycidyl ether.
Promotor in load-bearing core 12 is selected from: one or more in tertiary amine, benzyldimethylamine, 2,4,6-tri-(dimethylamino methyl) phenol, boron trifluoride complex, 2-ethyl-4-methylimidazole.
Mineral filler in load-bearing core 12 is selected from: one or more in calcium carbonate, kaolin, diatomite, wilkinite, nano-titanium oxide, talcum powder.
As shown in Figure 2, be the moulding process schematic diagram of cable core of the present invention, its operable profile principle is as follows:
The first step, is drawn carbon fiber 10 by creel 1, enters the first impregnation district 2 impregnation, and the epoxy resin of use is heat-resisting strong mechanical performance epoxy resin;
Second step, after impregnation completes, carbon fiber enters the first curing oven 3 Procuring, obtained carbon fiber complex core, and diameter is 5-12mm, regulates temperature to make degree of cure reach more than 85%;
3rd, both sides glass fibre 11 enters the second impregnation district 4 and the 3rd impregnation district 5 impregnation after drawing respectively, and the epoxy resin of use is high temperature resistant weather resistance epoxy resin;
4th step, after impregnation, glass fibre is outer at carbon fiber core by being wound around district 6 voluble wrapping, and one-sided thickness is 0.5mm-2mm, and wind-up speed is by Serve Motor Control and pultrusion speed synchronised;
5th step, carbon fiber complex core by the second curing oven 7, regulates temperature to make both fully solidifications together with after glass fibre protective layer compound;
6th step, composite material cable core goods are by after tractor 8, and at closed reel 9, place collects.
Wherein, the preparation method of heat-resisting strong mechanical performance epoxy resin, comprises the following steps: step 1, epoxy resin a and epoxy resin b mix and be incorporated in less than 40 DEG C with the speed mechanical dispersed with stirring 5-10 minute of 800-1000 rev/min; Step 2, add mineral filler and thinner successively while stirring, stand-by with left at room temperature after the speed mechanical dispersed with stirring 5-10 of 800-1000 rev/min minute; Step 3, by solidifying agent at 18 DEG C-25 DEG C with the speed mechanical dispersed with stirring 5-15 minute of 600-800 rev/min; Step 4, adding promotor while stirring, at room temperature with the speed mechanical dispersed with stirring 5-15 minute of 600-800 rev/min; Step 5, product obtained by step 2 to be mixed at 18 DEG C-25 DEG C with product obtained by step 4, with the speed mechanical dispersed with stirring 3-6 minute of 3000-3500 rev/min; Namely heat-resisting strong mechanical performance epoxy resin is obtained after step 6, vacuum defoamation.
Specifically, by 50g dicyclopentadiene (DCPD) type epoxy resin (purchased from Dai Nippon Printing HP-7200H, epoxy equivalent (weight) (EEW): 279), 45g bisphenol A-type glycidyl ether type epoxy resin E-51(is purchased from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54), 5g glycidyl amine epoxy resin JEh-012(is purchased from Changhu Jiafa chemistry Co., Ltd., oxirane value is 0.80-0.85) mixing, with the speed mechanical dispersed with stirring 5 minutes of 800 revs/min at 30 DEG C, add 0.5g kaolin successively while stirring, 10g1, 4-butanediol diglycidyl ether, with the speed mechanical dispersed with stirring of 800 revs/min after 10 minutes left at room temperature stand-by, 40g Tetra hydro Phthalic anhydride is at room temperature stirred with the speed mechanical of 600 revs/min, then in stirring simultaneously, add 0.5g2-ethyl-4-methylimidazole, at room temperature same with the speed mechanical dispersed with stirring 5-10 minute of 600 revs/min.At room temperature said components is mixed, with the speed mechanical dispersed with stirring 3 minutes of 3000 revs/min, after vacuum defoamation, namely obtain described composition epoxy resin, then pour die casting solidification into.The exothermic heat of reaction curve of dsc (DSC method) test wrapper epoxy resin system, temperature rise rate 5 DEG C/min and 15 DEG C/min, obtaining program curing by extrapotation is 28 DEG C of solidifications 5 hours, and 80 DEG C solidify 6 hours.According to standard GB/T/T2586-1995, the tensile strength of epoxy matrix resin of preparation, tension set, modulus in tension are tested, specimen size is as follows: length is 100mm ± 0.5mm, end portion width is 10mm ± 0.5mm, narrow parallel portion length 30mm ± 0.5mm, narrow parallel portion width 5mm ± 0.2mm, thickness is 2.2mm ± 0.2mm.Experiment repetition six times, the tensile strength recording this epoxy matrix resin is 68MPa, tension set 5.7%, modulus in tension 3.1GPa.Test the flexural strength of epoxy matrix resin of preparation, bending elastic modulus according to standard GB/T/T2570-1995, specimen size is as follows: length is 40mm, and width is 3mm ± 0.2mm, and thickness is 2mm ± 0.2mm.Experiment repetition six times, the flexural strength recording this epoxy matrix resin is 112MPa, bending elastic modulus 3.12GPa.Dsc (DSC method) surveys second-order transition temperature, temperature rise rate 5 DEG C/min, and the second-order transition temperature recording epoxy matrix resin is 82 DEG C, and adopt NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, viscosity when 25 DEG C is 520mPas.
Wherein, high temperature resistant weathering performance composition epoxy resin making method is as follows: comprise the following steps: step 1, by part epoxy resin c and d in component A below 30 DEG C with the speed mechanical dispersed with stirring 5-10 minute of 800-1000 rev/min; Step 2, add thinner and coupling agent successively while stirring, stand-by with left at room temperature after the speed mechanical dispersed with stirring 5-10 of 800-1000 rev/min minute; Step 3, by composition amine curing agent a and b in B component at room temperature with the speed mechanical dispersed with stirring 5-10 minute of 600-800 rev/min; Step 4, adding promotor, primary antioxidant and aid anti-oxidants while stirring, at room temperature with the speed mechanical dispersed with stirring 5-10 minute of 600-800 rev/min; Step 5, at room temperature by component A and B component mixing, with the speed mechanical dispersed with stirring 3-5 minute of 3000-3500 rev/min; Namely high temperature resistant weathering performance composition epoxy resin is obtained after step 6, vacuum defoamation.
By 10.0g glycolylurea epoxide resin MHR-070(purchased from Wuxi Meihua Chemical Co., Ltd., oxirane value is 0.70-0.74), 90.0g bisphenol A-type glycidyl ether type epoxy resin E-51(is purchased from Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd., oxirane value is 0.48-0.54) at 25 DEG C with the speed mechanical dispersed with stirring 5 minutes of 800 revs/min, add 5g1 successively while stirring, 4-butanediol diglycidyl ether, 0.5g γ-glycidyl ether oxygen propyl trimethoxy silicane, with the speed mechanical dispersed with stirring of 800 revs/min after 10 minutes left at room temperature stand-by, by 15.0g polyetheramine D230 and 20.0g triethylene tetramine at room temperature with the speed mechanical dispersed with stirring 5 minutes of 600 revs/min, adding 0.5g2 while stirring, 4, 6-tri-(dimethylamino methyl) phenol, 0.08g tetra-[β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] the two lauryl alcohol ester of pentaerythritol ester and 0.02g thio-2 acid, at room temperature with the speed mechanical dispersed with stirring 5 minutes of 600 revs/min.At room temperature said components is mixed, with the speed mechanical dispersed with stirring 3 minutes of 3000 revs/min, after vacuum defoamation, namely obtain described composition epoxy resin, then pour die casting solidification into.The exothermic heat of reaction curve of dsc (DSC method) test wrapper epoxy resin system, temperature rise rate 5 DEG C/min and 15 DEG C/min, obtaining program curing by extrapotation is 35 DEG C of solidifications 1 hour, and 110 DEG C solidify 2 hours, and 180 DEG C solidify 2 hours.According to standard GB/T/T16421-1996, the tensile strength of epoxy matrix resin of preparation, tension set, modulus in tension are tested, specimen size is as follows: length is 100mm ± 0.5mm, end portion width is 10mm ± 0.5mm, narrow parallel portion length 30mm ± 0.5mm, narrow parallel portion width 5mm ± 0.2mm, thickness is 2.2mm ± 0.2mm.Experiment repetition six times, the tensile strength recording this epoxy matrix resin is 58MPa, tension set 4.0%, modulus in tension 2.5GPa.Test the flexural strength of epoxy matrix resin of preparation, bending elastic modulus according to standard GB/T/T16419-1996, specimen size is as follows: length is 40mm, and width is 3mm ± 0.2mm, and thickness is 2mm ± 0.2mm.Experiment repetition six times, the flexural strength recording this epoxy matrix resin is 104MPa, bending elastic modulus 3.3GPa.Dsc (DSC method) surveys second-order transition temperature, temperature rise rate 5 DEG C/min, and the second-order transition temperature recording epoxy matrix resin is 155 DEG C, and adopt NDJ-8S type rotational viscosimeter testing tree oil/fat composition viscosity, viscosity when 25 DEG C is 471mPas.
Above by reference to the accompanying drawings to invention has been exemplary description; obvious realization of the present invention is not subject to the restrictions described above; as long as have employed the various improvement that method of the present invention is conceived and technical scheme is carried out; or design of the present invention and technical scheme directly applied to other occasion, all in protection scope of the present invention without to improve.
Claims (1)
1. the making method of a carbon fiber composite material cable wire, comprise the following steps: step 1, carbon fiber (10) is drawn by creel (1), enter the first impregnation district (2) impregnation, the epoxy resin used is heat-resisting strong mechanical performance epoxy resin, and described heat-resisting strong mechanical performance epoxy resin is made up of following compositions: the blending epoxy of 100 mass parts; The solidifying agent of 20-75 mass parts; The thinner of 10-30 mass parts; The promotor of 0.5-5.0 mass parts; The filler of 0.5-5.0 mass parts; Described blending epoxy comprises epoxy resin a and epoxy resin b; Epoxy resin a is dicyclopentadiene (DCPD) type epoxy resin, and described epoxy resin b is the composition of glycidyl amine epoxy resin and bisphenol A-type glycidyl ether type epoxy resin; The mass ratio of epoxy resin a and epoxy resin b is: 50-80:20-50; The structural formula of described dicyclopentadiene type epoxy resin is as follows:
, in formula, n is the integer of 0 to 10; The mass ratio of the glycidyl amine epoxy resin in described epoxy resin b and bisphenol A-type glycidyl ether type epoxy resin is: 1:9-9:1;
Step 2, after impregnation completes, carbon fiber enters the first curing oven (3) Procuring, obtained carbon fiber complex core, and diameter is 5-12mm, regulates temperature to make degree of cure reach more than 85%;
Step 3, both sides glass fibre (11) enters the second impregnation district (4) and the 3rd impregnation district (5) impregnation after drawing respectively, and the epoxy resin of use is high temperature resistant weather resistance epoxy resin; Described high temperature resistant weather resistance epoxy resin is made up of following compositions: comprise component A and B component, wherein component A comprises following compositions: 100 mass parts epoxy resin, 5-20 mass parts thinner, 0.5-5.0 mass parts silane coupling agent, the mineral filler of 0.5-5.0 mass parts; B component comprises following compositions: 25-45 mass parts amine curing agent, 0.5-5.0 mass parts promotor; Described epoxy resin is the combination of epoxy resin c and epoxy resin d, and the mass ratio of epoxy resin c and epoxy resin d is: 50-80:20-50; Described epoxy resin c is for comprising glycidic amine type, diglycidyl ether type or the glycidyl ester type glycolylurea epoxide resin of one or more glycolylurea ring (five yuan of diazacyclos), glycolylurea ring (five yuan of diazacyclos) structural formula is as follows, and in glycolylurea ring (five yuan of diazacyclos) structural formula, substituent R 1 and R2 are H, CH3, C2H5, aryl or aralkyl:
, described epoxy resin d is at least one in following several epoxy resin: 4,5-oxirane ring ethane-1,2-dioctyl phthalate 2-glycidyl ester, bisphenol-f type glycidyl ether type epoxy resin or bisphenol A-type glycidyl ether type epoxy resin;
Step 4, after impregnation, glass fibre is outer at carbon fiber core by being wound around district (6) voluble wrapping, and one-sided thickness is 0.5mm-2mm, and wind-up speed is by Serve Motor Control and pultrusion speed synchronised;
Step 5, carbon fiber complex core by the second curing oven (7), regulates temperature to make both fully solidifications together with after glass fibre protective layer compound;
Step 6, composite material cable core goods, by after tractor (8), are collected at closed reel (9) place;
Amine curing agent described in described protective layer (13) is the combination of amine curing agent a and amine curing agent b, and the mass ratio of amine curing agent a and amine curing agent b is: 20-40:5-25; Described amine curing agent a is the polyether monoamine compound comprising two or more amido functional groups, is selected from: molecular weight ranges 200-2500, one or more in the polyether monoamine compound of 25 DEG C of range of viscosities: 5-300mPas; Described amine curing agent b is one or more of aliphatics amine and modified aliphatic aminated compounds, is selected from: one or more in diethylenetriamine, triethylene tetramine, tetraethylene pentamine, diamines, methylol quadrol, methylol diethylenetriamine, beta-hydroxyethyl quadrol; Described in described protective layer (13), coupling agent is the silane coupling agent comprising epoxy functionality; Elect γ-aminopropyl triethoxysilane as, the one in γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-(methacryloxy) propyl trimethoxy silicane;
Thinner described in protective layer is the compound comprising two epoxy functionality and at least one ehter bond, is selected from one or more in ethylene glycol diglycidylether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cylohexanediol diglycidyl ether, cyclohexanedimethanodiglycidyl diglycidyl ether, neopentylglycol diglycidyl ether, polyethyleneglycol diglycidylether, resorcinol diglycidyl ether;
Mineral filler in described load-bearing core (12) is selected from: one or more in calcium carbonate, diatomite, wilkinite, talcum powder.
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| CN201510549159.3A Pending CN105118574A (en) | 2013-02-05 | 2013-02-05 | Manufacturing method for cable with excellent heatproof and mechanical properties |
| CN201510549107.6A Pending CN105374466A (en) | 2013-02-05 | 2013-02-05 | Cable making method |
| CN201310044263.8A Active CN103093896B (en) | 2013-02-05 | 2013-02-05 | A kind of manufacture method of carbon fiber composite material cable wire |
| CN201510549544.8A Pending CN105336429A (en) | 2013-02-05 | 2013-02-05 | Method for manufacturing composite-material cable |
| CN201510549295.2A Withdrawn CN105118575A (en) | 2013-02-05 | 2013-02-05 | Manufacturing method of carbon-fiber-contained composite material cable |
| CN201510552794.7A Withdrawn CN105244116A (en) | 2013-02-05 | 2013-02-05 | Cable wire manufacturing method |
| CN201510552859.8A Pending CN105199316A (en) | 2013-02-05 | 2013-02-05 | Manufacturing method for carbon fiber composite material cable |
| CN201510549516.6A Pending CN105118576A (en) | 2013-02-05 | 2013-02-05 | Manufacturing method of composite-material-based cable |
| CN201510548681.XA Pending CN105118573A (en) | 2013-02-05 | 2013-02-05 | Method of manufacturing cable with good anti-ultraviolet performance |
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| CN201510549107.6A Pending CN105374466A (en) | 2013-02-05 | 2013-02-05 | Cable making method |
| CN201310044263.8A Active CN103093896B (en) | 2013-02-05 | 2013-02-05 | A kind of manufacture method of carbon fiber composite material cable wire |
| CN201510549544.8A Pending CN105336429A (en) | 2013-02-05 | 2013-02-05 | Method for manufacturing composite-material cable |
| CN201510549295.2A Withdrawn CN105118575A (en) | 2013-02-05 | 2013-02-05 | Manufacturing method of carbon-fiber-contained composite material cable |
| CN201510552794.7A Withdrawn CN105244116A (en) | 2013-02-05 | 2013-02-05 | Cable wire manufacturing method |
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| CN113278179A (en) * | 2021-05-21 | 2021-08-20 | 四川东材科技集团股份有限公司 | High-temperature-resistance epoxy glass fiber insulating layer, molded part and preparation method thereof |
| CN113278180A (en) * | 2021-05-21 | 2021-08-20 | 四川东材科技集团股份有限公司 | High-temperature-resistance epoxy carbon fiber insulating layer, molded part and preparation method thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103093896B (en) | 2016-08-03 |
| CN105374466A (en) | 2016-03-02 |
| CN103093896A (en) | 2013-05-08 |
| CN105118576A (en) | 2015-12-02 |
| CN105118575A (en) | 2015-12-02 |
| CN105118573A (en) | 2015-12-02 |
| CN105244116A (en) | 2016-01-13 |
| CN105118574A (en) | 2015-12-02 |
| CN105336429A (en) | 2016-02-17 |
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