CN103093889B - Cable core - Google Patents
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- CN103093889B CN103093889B CN201310044286.9A CN201310044286A CN103093889B CN 103093889 B CN103093889 B CN 103093889B CN 201310044286 A CN201310044286 A CN 201310044286A CN 103093889 B CN103093889 B CN 103093889B
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Abstract
The invention relates to a cable core which comprises a bearing core (12) and a protective layer (13). The protective layer (13) covers the outer portion of the bearing core (12) through a winding process. The cable core is characterized in that the bearing core (12) is a composite of epoxy resin and carbon fibers, wherein the epoxy resin is heat resisting and high in mechanical property, and the protective layer (13) is the composite of epoxy resin and glass fibers, wherein the epoxy resin is high temperature resisting and weather resisting. Due to the fact that the bearing core and the protective layer are chosen to be different epoxy resin systems, the high mechanical property of the epoxy resin system of the bearing core cannot be influenced the epoxy resin system of the outer protective layer, the good weather resisting property of the outer protective layer protects the bearing core from being damaged by outer environment, and the combination property of the cable core is greatly improved.
Description
Technical field
The present invention relates to a kind of cable core.
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 ageing resistance etc., require very high to the combination property 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, compression strength, uvioresistant and ageing resistance, 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 by-product C 5 fraction and the carbonization of coal by-product light benzene fraction of cracking of ethylene, because chemism is high, it is the raw material of Petropols 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 cable core, 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, anti-flammability, compression strength, uvioresistant and ageing resistance.
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 compound that described load-bearing core (12) is heat-resisting strong mechanical performance epoxy resin and carbon fiber, the compound that described protective layer (13) is high temperature resistant weather resistance epoxy resin and glass fibre; The heat-resisting strong mechanical performance epoxy resin of described load-bearing core (12) is made up of following compositions: the blending epoxy of 100 mass parts; The curing agent of 20-75 mass parts; The diluent of 10-30 mass parts; The promoter 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, 5-10 mass parts diluent and 0.5-3.0 mass parts silane coupler; B component comprises following compositions: 15-35 mass parts amine curing agent, 0.1-3.0 mass parts promoter and 0.01-0.1 mass parts antioxidant, 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: 10-30:70-90; Wherein, 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, CH
3, C
2h
5, aryl or aralkyl:
; Described epoxy resin d is bisphenol A-type glycidyl ether type epoxy resin or bisphenol-f type glycidyl ether type epoxy resin; Wherein, the range of viscosities of bisphenol-f type glycidyl ether type epoxy resin or bisphenol A-type glycidyl ether type epoxy resin: 500-4000mPas(25 DEG C).
Described epoxy resin c is the 2-glycidyl amine type glycolylurea epoxide resin containing a glycolylurea ring, chemical structural formula
Under:
; Substituent R wherein
1and R
2selection mode is combined: 1) R below existing
1for H, R
2for the compound of H; 2) R
1for CH
3, R
2for the compound of H; 3) R
1for CH
3, R
2for CH
3compound; 4) R
1for C
2h
5, R
2for the compound of H; 5) R
1for C
2h
5, R
2for CH
3compound.
Further, the amine curing agent 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: 5-15:10-20; Described amine curing agent a is the polyether monoamine compound comprising two or more amido functional groups, 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 aliphat amine and modified aliphatic aminated compounds, is selected from one or more in diethylenetriamine, triethylene tetramine, TEPA, diamines, methylol ethylenediamine, methylol diethylenetriamine, beta-hydroxyethyl ethylenediamine.
Further, the promoter in described protective layer (13) is selected from: one or more in 2,4,6-tri-(dimethylamino methyl) phenol, boron trifluoride complex, triethanolamine.
Further; diluent in described protective layer (13) 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, resorcinolformaldehyde resin.
Further; coupling agent in described protective layer (13) is the silane coupling agent comprising epoxy functionality; be selected from gamma-aminopropyl-triethoxy-silane, the one in γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-(methacryloxy) propyl trimethoxy silicane.
Further, the antioxidant in described protective layer (13) is the combination of primary antioxidant and aid anti-oxidants, and the mass ratio of primary antioxidant and aid anti-oxidants is: 0.0095-0.08:0.0005-0.02; Described primary antioxidant is Hinered phenols antioxidant, be selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, 2,2-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) one in ethyl propionate or 4,6-bis-(pungent sulfidomethyl)-o-cresols; Described aid anti-oxidants monothioester kind antioxidant, is selected from the one in the two lauryl alcohol ester of thio-2 acid, the two tetradecyl alchohol ester of thio-2 acid or the two octadecyl of thio-2 acid.
Further, the curing agent in described load-bearing core (12) is selected from: one or more in phthalic anhydride, maleic anhydride, tetrahydrochysene phthalate anhydride, α-methacrylic acid.
Further, the diluent 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 promoter in described load-bearing core (12) is selected from: one or more in tertiary amine, benzyl dimethylamine, 2,4,6-tri-(dimethylamino methyl) phenol, boron trifluoride complex, 2-ethyl-4-methylimidazole.
Further, the inorganic filler in described load-bearing core (12) is selected from: one or more in calcium carbonate, kaolin, diatomite, bentonite, nano-titanium oxide, talcum powder.
A manufacture method for cable core, 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 precuring, obtained carbon fiber complex core, and diameter is 5 mm-12mm, regulates temperature to make curing degree 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 0.5 mm-2mm, and speed of wrap 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 hauling machine, and at closed reel, place collects.
This cable core, compared with traditional cable core, 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 wettability and adhesive strength to carbon fiber, cured product has good thermal endurance and mechanical strength, and the thermal endurance of the fibre reinforced cable adopting the present invention heat-resisting strong mechanical performance epoxy resin to make, moisture-proof, electric property, toughness and machinability 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 glass transition temperature, to meet heat resistant requirements, can use at a higher temperature after reprocessing, its finished product interior solid is good, air-gap-free, performance are homogeneous.
(4) diluent 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 performance of epoxy resin cured product.
(5) promoter in the heat-resisting strong mechanical performance epoxy resin of the present invention effectively can solve the problem of cold curing overlong time, while shortening curing time, ensure that the intensity of solidfied material 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 processability, flame resistance, the viscosity of resin and processing technology.
(7) the present invention adopts the blending type epoxy resin of glycolylurea epoxide resin and low viscosity epoxy resin (at least one in bisphenol A-type and bisphenol-f type glycidyl ether type epoxy resin) as resin matrix, glass fibre can not only be met to the low viscous requirement of resin, cable core can also be made to possess excellent resistance to elevated temperatures.
(8) be employed herein glycolylurea epoxide resin, it has, and viscosity is low, good manufacturability, has good wetting property to glass fibre, and owing to comprising five yuan of diazacyclos in its structure, also has the features such as Heat stability is good, thermal endurance is high, weather resisteant is good concurrently.
(9) the toughness functional groups such as multiple ehter bonds are comprised in the polyether monoamine curing agent structure used in the present invention, cable core can be made to have the shock resistance of high-strength and high ductility, by adopting the blending type curing system of polyether monoamine curing agent and aliphat amine curing agent, the problems such as solidfied material fragility, elongation at break are little effectively can be solved.
(10) the present invention adopts a certain amount of promoter to coordinate blending type amine curing agent to use together, effectively can solve the problem of cold curing overlong time, while shortening curing time, ensure that the intensity of solidfied material remains unchanged substantially.
(11) auxiliary agents such as silane coupler, antioxidant and diluent are employed herein.Wherein silane coupler can improve bonding strength between reinforcing glass fiber material and resin, improves interface state, is conducive to the mechanical performance and the electrical insulation capability that improve composite product; Antioxidant can suppress or slow down macromolecular material Auto-oxidation reaction speed; The effect of diluent can reduce the viscosity of whole composition.
(12) the present invention is chosen as different epoxy-resin systems due to load-bearing core and protective layer; therefore the epoxy-resin systems strong mechanical performance of load-bearing core can not be subject to the epoxy-resin systems impact of exterior cover sheets; and the excellent weather resistance of exterior cover sheets protects load-bearing core by the injury of external environment condition, the combination property of cable core is greatly improved.
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-hauling machine; 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 compound of heat-resisting strong mechanical performance epoxy resin and carbon fiber, and protective layer 13 is the compound 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 curing agent of 20-75 mass parts; The diluent of 10-30 mass parts; The promoter 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.
In 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, 5-10 mass parts diluent and 0.5-3.0 mass parts silane coupler; B component comprises following compositions: 15-35 mass parts amine curing agent, 0.1-3.0 mass parts promoter and 0.01-0.1 mass parts antioxidant, 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: 10-30:70-90; Wherein, 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, CH
3, C
2h
5, aryl or aralkyl:
; Described epoxy resin d is bisphenol A-type glycidyl ether type epoxy resin or bisphenol-f type glycidyl ether type epoxy resin; Wherein, the range of viscosities of bisphenol-f type glycidyl ether type epoxy resin or bisphenol A-type glycidyl ether type epoxy resin: 500-4000mPas(25 DEG C).
Amine curing agent 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: 5-15:10-20; Described amine curing agent a is the polyether monoamine compound comprising two or more amido functional groups, 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 aliphat amine and modified aliphatic aminated compounds, is selected from one or more in diethylenetriamine, triethylene tetramine, TEPA, diamines, methylol ethylenediamine, methylol diethylenetriamine, beta-hydroxyethyl ethylenediamine.
Promoter in protective layer 13 is selected from: one or more in 2,4,6-tri-(dimethylamino methyl) phenol, boron trifluoride complex, triethanolamine.
Diluent in protective layer 13 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, resorcinolformaldehyde resin.
Coupling agent in protective layer 13 is the silane coupling agent comprising epoxy functionality; be selected from gamma-aminopropyl-triethoxy-silane, the one in γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-(methacryloxy) propyl trimethoxy silicane.
Antioxidant in protective layer 13 is the combination of primary antioxidant and aid anti-oxidants, and the mass ratio of primary antioxidant and aid anti-oxidants is: 0.0095-0.08:0.0005-0.02; Described primary antioxidant is Hinered phenols antioxidant, be selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, 2,2-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) one in ethyl propionate or 4,6-bis-(pungent sulfidomethyl)-o-cresols; Described aid anti-oxidants monothioester kind antioxidant, is selected from the one in the two lauryl alcohol ester of thio-2 acid, the two tetradecyl alchohol ester of thio-2 acid or the two octadecyl of thio-2 acid.
Curing agent in load-bearing core 12 is selected from: one or more in phthalic anhydride, maleic anhydride, tetrahydrochysene phthalate anhydride, α-methacrylic acid.
Diluent in load-bearing core 12 is selected from: one or more in ethylene glycol diglycidylether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cylohexanediol diglycidyl ether.
Promoter in load-bearing core 12 is selected from: one or more in tertiary amine, benzyl dimethylamine, 2,4,6-tri-(dimethylamino methyl) phenol, boron trifluoride complex, 2-ethyl-4-methylimidazole.
Inorganic filler in load-bearing core 12 is selected from: one or more in calcium carbonate, kaolin, diatomite, bentonite, 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 precuring, obtained carbon fiber complex core, and diameter is 5-12mm, regulates temperature to make curing degree 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 0.5 mm-2mm, and speed of wrap 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 hauling machine 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 inorganic filler and diluent 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 curing 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 promoter 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, epoxide equivalent (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., epoxide number is 0.48-0.54), 5g glycidyl amine epoxy resin JEh-012(is purchased from Changhu Jiafa chemistry Co., Ltd., epoxide number 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, 10g 1, 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 phthalic anhydride is at room temperature stirred with the speed mechanical of 600 revs/min, then in stirring simultaneously, add 0.5g 2-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 differential scanning calorimetry (DSC method) test wrapper epoxy resin system, heating rate 5 DEG C/min and 15 DEG C/min, obtaining program curing by extrapolation is 28 DEG C of solidifications 5 hours, and 80 DEG C solidify 6 hours.According to standard GB/T/T 2586-1995, the hot strength of epoxy matrix resin of preparation, fracture elongation, tensile modulus of elasticity 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 hot strength recording this epoxy matrix resin is 68MPa, fracture elongation 5.7%, tensile modulus of elasticity 3.1GPa.Test the bending strength of epoxy matrix resin of preparation, the modulus of elasticity in static bending according to standard GB/T/T 2570-1995, 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 bending strength recording this epoxy matrix resin is 112MPa, modulus of elasticity in static bending 3.12GPa.Differential scanning calorimetry (DSC method) surveys vitrification point, heating rate 5 DEG C/min, and the vitrification point recording epoxy matrix resin is 82 DEG C, and adopt NDJ-8S type rotation viscometer testing tree oil/fat composition viscosity, viscosity when 25 DEG C is 520mPas.
High temperature resistant weathering performance composition epoxy resin manufacture 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 diluent 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 promoter, 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., epoxide number 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., epoxide number is 0.48-0.54) at 25 DEG C with the speed mechanical dispersed with stirring 5 minutes of 800 revs/min, add 5g 1 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 0.5g 2 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 differential scanning calorimetry (DSC method) test wrapper epoxy resin system, heating rate 5 DEG C/min and 15 DEG C/min, obtaining program curing by extrapolation 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/T 16421-1996, the hot strength of epoxy matrix resin of preparation, fracture elongation, tensile modulus of elasticity 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 hot strength recording this epoxy matrix resin is 58MPa, fracture elongation 4.0%, tensile modulus of elasticity 2.5GPa.Test the bending strength of epoxy matrix resin of preparation, the modulus of elasticity in static bending according to standard GB/T/T 16419-1996, 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 bending strength recording this epoxy matrix resin is 104MPa, modulus of elasticity in static bending 3.3GPa.Differential scanning calorimetry (DSC method) surveys vitrification point, heating rate 5 DEG C/min, and the vitrification point recording epoxy matrix resin is 155 DEG C, and adopt NDJ-8S type rotation viscometer 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 (10)
1. a 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 compound that described load-bearing core (12) is heat-resisting strong mechanical performance epoxy resin and carbon fiber, the compound that described protective layer (13) is high temperature resistant weather resistance epoxy resin and glass fibre; The heat-resisting strong mechanical performance epoxy resin of described load-bearing core (12) is made up of following compositions: the blending epoxy of 100 mass parts; The curing agent of 20-75 mass parts; The diluent of 10-30 mass parts; The promoter 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, 5-10 mass parts diluent and 0.5-3.0 mass parts silane coupler; B component comprises following compositions: 15-35 mass parts amine curing agent, 0.1-3.0 mass parts promoter and 0.01-0.1 mass parts antioxidant, 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: 10-30:70-90; Wherein, 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 b is bisphenol A-type glycidyl ether type epoxy resin or bisphenol-f type glycidyl ether type epoxy resin; Wherein, the range of viscosities 25 DEG C time of bisphenol-f type glycidyl ether type epoxy resin or bisphenol A-type glycidyl ether type epoxy resin: 500-4000mPas.
2. cable core according to claim 1, is characterized in that: the amine curing agent 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: 5-15:10-20; Described amine curing agent a is the polyether monoamine compound comprising two or more amido functional group, molecular weight ranges 200-2500, one or more in the polyether monoamine compound of the range of viscosities 25 DEG C time: 5-300mPas; Described amine curing agent b is one or more of aliphat amine and modified aliphatic aminated compounds, is selected from one or more in diethylenetriamine, triethylene tetramine, TEPA, diamines, methylol ethylenediamine, methylol diethylenetriamine, beta-hydroxyethyl ethylenediamine.
3. cable core according to claim 1, is characterized in that: the promoter in described protective layer (13) is selected from: one or more in 2,4,6-tri-(dimethylamino methyl) phenol, boron trifluoride complex, triethanolamine.
4. cable core according to claim 1; it is characterized in that: the diluent in described protective layer (13) 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, resorcinolformaldehyde resin.
5. cable core according to claim 1; it is characterized in that: the coupling agent in described protective layer (13) is the silane coupling agent comprising epoxy functionality; be selected from gamma-aminopropyl-triethoxy-silane, the one in γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-(methacryloxy) propyl trimethoxy silicane.
6. cable core according to claim 1, is characterized in that: the antioxidant in described protective layer (13) is the combination of primary antioxidant and aid anti-oxidants, and the mass ratio of primary antioxidant and aid anti-oxidants is: 0.0095-0.08:0.0005-0.02; Described primary antioxidant is Hinered phenols antioxidant, be selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester or 2,2-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) one in ethyl propionate; Described aid anti-oxidants monothioester kind antioxidant, is selected from the one in the two lauryl alcohol ester of thio-2 acid, the two tetradecyl alchohol ester of thio-2 acid or the two octadecyl of thio-2 acid.
7. cable core according to claim 1, is characterized in that: the curing agent in described load-bearing core (12) is selected from: one or more in phthalic anhydride, maleic anhydride, tetrahydrochysene phthalate anhydride, α-methacrylic acid.
8. cable core according to claim 1, is characterized in that: the diluent 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.
9. cable core according to claim 1, it is characterized in that: the promoter in described load-bearing core (12) is selected from: tertiary amine, benzyl dimethylamine, 2, one or more in 4,6-tri-(dimethylamino methyl) phenol, boron trifluoride complex, 2-ethyl-4-methylimidazole.
10. cable core according to claim 1, is characterized in that: the inorganic filler in described load-bearing core (12) is selected from: one or more in calcium carbonate, kaolin, diatomite, bentonite, nano-titanium oxide, talcum powder.
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| CN105593261A (en) * | 2013-09-30 | 2016-05-18 | 东丽株式会社 | Two-pack epoxy resin composition for fiber-reinforced composite material, and the fiber-reinforced composite material |
| CN104017333B (en) * | 2014-06-18 | 2016-01-20 | 国家电网公司 | Cold-resistant Pyrotenax material and preparation method thereof |
| CN105331044B (en) * | 2014-08-13 | 2018-03-06 | 中国蓝星（集团）股份有限公司 | Ageing-resistant composition epoxy resin of uvioresistant and preparation method thereof |
| CN106905659A (en) * | 2017-01-22 | 2017-06-30 | 江苏恒神股份有限公司 | A kind of winding resin of NOL rings tensile strength high |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4556455B2 (en) * | 2004-03-16 | 2010-10-06 | 株式会社明電舎 | Impregnating resin composition |
| CN101950622A (en) * | 2010-07-29 | 2011-01-19 | 蓝星(北京)化工机械有限公司 | High-performance carbon fiber composite cable core and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4556455B2 (en) * | 2004-03-16 | 2010-10-06 | 株式会社明電舎 | Impregnating resin composition |
| CN101950622A (en) * | 2010-07-29 | 2011-01-19 | 蓝星(北京)化工机械有限公司 | High-performance carbon fiber composite cable core and manufacturing method thereof |
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