CN103310908B - A kind of manufacture method of carbon fiber composite material cable wire - Google Patents
A kind of manufacture method of carbon fiber composite material cable wire Download PDFInfo
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- CN103310908B CN103310908B CN201310083899.3A CN201310083899A CN103310908B CN 103310908 B CN103310908 B CN 103310908B CN 201310083899 A CN201310083899 A CN 201310083899A CN 103310908 B CN103310908 B CN 103310908B
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- epoxy resin
- carbon fiber
- resin
- protective layer
- high temperature
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 37
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 108
- 239000003822 epoxy resin Substances 0.000 claims abstract description 105
- 239000011241 protective layer Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000003365 glass fiber Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004804 winding Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 34
- 235000006708 antioxidants Nutrition 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- -1 glycidyl ester Chemical class 0.000 claims description 29
- 150000001412 amines Chemical class 0.000 claims description 26
- 230000003078 antioxidant effect Effects 0.000 claims description 24
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 24
- 238000005470 impregnation Methods 0.000 claims description 24
- 239000004593 Epoxy Substances 0.000 claims description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 claims description 9
- 229930185605 Bisphenol Natural products 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000012546 transfer Methods 0.000 claims description 7
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- RYDVBNBVYVMEDT-UHFFFAOYSA-N n-carbamoyl-2-hydroxyacetamide Chemical group NC(=O)NC(=O)CO RYDVBNBVYVMEDT-UHFFFAOYSA-N 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 4
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 230000001360 synchronised effect Effects 0.000 claims description 3
- WVJGICATWRJGOQ-UHFFFAOYSA-N dioctyl benzene-1,2-dicarboxylate;ethane Chemical compound CC.CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC WVJGICATWRJGOQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 14
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 238000005452 bending Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 230000032683 aging Effects 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- HSDVRWZKEDRBAG-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COC(CCCCC)OCC1CO1 HSDVRWZKEDRBAG-UHFFFAOYSA-N 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- DIGDEPKXCWMYBK-UHFFFAOYSA-N (2-aminoethylamino)methanol Chemical compound NCCNCO DIGDEPKXCWMYBK-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 description 2
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- UJUPBNMOPOYXHW-UHFFFAOYSA-N [2-(2-aminoethylamino)ethylamino]methanol Chemical compound NCCNCCNCO UJUPBNMOPOYXHW-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 1
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 1
- SOCGXPPUVVILSX-UHFFFAOYSA-N C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1CCCCC1.[O] Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1CCCCC1.[O] SOCGXPPUVVILSX-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The present invention relates to the manufacture method of a kind of carbon fiber composite material cable wire; including 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; described load-bearing core (12) is the complex of high temperature resistant strong mechanical performance epoxy resin and carbon fiber, and described protective layer (13) is the complex of high temperature resistant weathering performance composition epoxy resin and glass fibre.The present invention uses the blending type epoxy resin of glycolylurea epoxide resin and low viscosity epoxy resin as resin matrix, can not only meet glass fibre requirement low viscous to resin, it is also possible to make cable core possess the resistance to elevated temperatures of excellence.
Description
Technical field
The present invention relates to a kind of cable core, especially relate to the manufacture method of a kind of carbon fiber composite material cable wire.
Background technology
The manufacture method of carbon fiber composite material cable wire is as the substitute products of tradition steel core, due to the highest
Temperature, at sunshine, works under the mal-condition such as climate change, it is desirable to while it has excellent mechanical property, also has high temperature resistant, anti-
Ultraviolet and ageing resistance etc., require the highest to the combination property of cable core.
The manufacture method structure of traditional carbon fiber composite material cable wire is internal carbon fibers and epoxy resin composite wood
The load-bearing core that material is made, the outside protective layer made with epoxy resin composite for glass fibre, both shared same resins
System.Under same resin system, high temperature resistant, tensile strength, bending strength, modulus, comprcssive strength, uvioresistant and anti-
Interact between the performances such as aging, increase performance in a certain respect often to sacrifice another aspect performance as generation by modification
Valency.
Owing to resin room temperature (18～25 DEG C) curing system often reacts too slow, inefficient, and it is not the completeest for reacting
Entirely so that room-temperature curing epoxy system tool has disadvantages that, as epoxy resin is the most crisp after hardening, there is toughness deficiency
Shortcoming, it is impossible to effectively play the performance of reinforcing fiber, when bearing load often due to the premature failure of epoxy resin causes multiple
The destruction of condensation material.
Additionally, System Curing At Room Temperature solidifies mostly under room temperature environment, the resistance to elevated temperatures of solidfied material is poor, it is impossible to
It is applicable to medium and high temperature environment or the occasion the highest to temperature requirement.In order to adapt to high performance composites to matrix resin
Demand, the modification of epoxy resin is always the study hotspot of association area, has toughness, temperature tolerance and excellent processing characteristics concurrently
Epoxy resin is always the developing direction of epoxy resin modification.
Summary of the invention
The present invention devises the manufacture method of a kind of carbon fiber composite material cable wire, and it solves the technical problem that it is tradition
In the manufacture method of carbon fiber composite material cable wire, owing to load-bearing core and protective layer are chosen as same resin system, cause
Cable core is between the performances such as high temperature resistant, tensile strength, bending strength, modulus, comprcssive strength, uvioresistant and ageing resistance
Interact or collide with each other.
In order to solve the technical problem of above-mentioned existence, present invention employs below scheme:
The manufacture method of a kind of carbon fiber composite material cable wire, including load-bearing core (12) and protective layer (13), described guarantor
Sheath (13) is coated on the outside of described load-bearing core (12) by winding process, and described load-bearing core (12) is high temperature resistant high mechanical property
Energy epoxy resin and the complex of carbon fiber, described protective layer (13) is high temperature resistant weathering performance epoxy resin and glass fibre
Complex, it is characterised in that: described high temperature resistant weathering performance epoxy resin is made up of following compositions: include component A and component B,
Wherein component A includes following compositions: 100 mass parts epoxy resin, 5-10 mass parts diluent and 0.5-3.0 mass parts silane are even
Connection agent；Component B includes following compositions: 15-35 mass parts amine curing agent, 0.1-3.0 mass parts accelerator and 0.01-0.1 matter
Amount part antioxidant, described epoxy resin is epoxy resin a and the combination of epoxy resin b, epoxy resin a and the matter of epoxy resin b
Amount ratio is: 10-30: 70-90；Wherein, described epoxy resin a is the contracting comprising one or more glycolylurea ring (five yuan of diazacyclos)
Water glycerol amine type, diglycidyl ether type or glycidyl ester type glycolylurea epoxide resin；Glycolylurea ring (five yuan of diazacyclos) structural formula
As follows, in glycolylurea ring (five yuan of diazacyclos) structural formula, substituent R 1 and R2 is 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, bisphenol-f type glycidyl ether type epoxy resin or the range of viscosities of bisphenol A-type glycidyl ether type epoxy resin:
500-4000mPa·s(25℃)。
Further, described epoxy resin a is the 2-glycidyl amine type glycolylurea epoxide resin containing a glycolylurea ring, chemistry
Structural formula is as follows:
Substituent R therein1And R2There is following combination selection mode: 1) R1For H, R2Compound for H；2)R1For CH3,
R2Compound for H；3)R1For CH3, R2For CH3Compound；4)R1For C2H5, R2Compound for H；5)R1For C2H5, R2For
CH3Compound.
Further, the high temperature resistant strong mechanical performance epoxy resin of described load-bearing core (12) is E51 epoxy resin, TDE86 ring
Epoxy resins (4,5-epoxide ring ethane-1,2 dioctyl phthalate 2-glycidyl ester), AG80 four-functional group epoxy resin, MY721 asphalt mixtures modified by epoxy resin
Fat, AFG90 trifunctional epoxy resin, Tao Shi produce DER331 liquid epoxies in one or more.
Further, described amine curing agent is amine curing agent a and the combination of amine curing agent b, amine curing agent a and amine
The mass ratio of class firming agent b is: 5-15: 10-20；Described amine curing agent a is for comprising two or more amido functional groups
Polyether amine compound, molecular weight ranges 200-2500, range of viscosities: the polyether amine chemical combination of 5-300mPa s (25 DEG C)
One or more in thing；Described amine curing agent b is aliphatic amine and the one of modified aliphatic aminated compounds or several
Kind, selected from diethylenetriamine, triethylene tetramine, TEPA, diamidogen, methylol ethylenediamine, methylol diethylenetriamine,
One or more in beta-hydroxyethyl ethylenediamine.
Further, described accelerator is selected from: 2,4,6-tri-(dimethylamino methyl) phenol, boron trifluoride complex, three second
One or more in hydramine.
Further, described diluent is the compound comprising two epoxy functionality and at least one ehter bond, selected from second
Hexanediol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cylohexanediol diglycidyl ether,
Cyclohexanedimethanodiglycidyl diglycidyl ether, neopentylglycol diglycidyl ether, polyethyleneglycol diglycidylether, resorcinol two
One or more in glycidyl ether.
Further, described coupling agent is the silane coupling agent comprising epoxy functionality, selected from γ-aminopropyl three ethoxy
In base silane, γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-(methacryloxy) propyl trimethoxy silicane
One.
Further, described antioxidant is the quality of the combination of primary antioxidant and aid anti-oxidants, primary antioxidant and aid anti-oxidants
Ratio is: 0.0095-0.08: 0.0005-0.02；Described primary antioxidant is Hinered phenols antioxidant, selected from four [β-(3,5-bis-uncles
Butyl-4-hydroxy phenyl) propanoic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid octadecanol ester, 2,
2-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate or 4, in 6-bis-(pungent sulfidomethyl)-o-cresol
Kind；Described aid anti-oxidants monothioester kind antioxidant, selected from the double lauryl alcohol ester of thio-2 acid, the double tetradecyl alchohol ester of thio-2 acid or
One in the double octadecyl of thio-2 acid.
Further, described protective layer (13) is also added with ultraviolet absorber, described ultraviolet absorber is UV-9, UV-531,
A kind of or the most several combination in UV-327, triazine-5.
Further, being also added with energy transfer agent in described protective layer (13), described energy transfer agent is three (1,2,2,6,6-
Pentamethvl base) one or both combinations in phosphite ester or AM101.
The manufacture method of the manufacture method of a kind of 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 high temperature resistant height
Mechanical property epoxy resin；
Second step, after impregnation completes, carbon fiber enters the first curing oven precuring, prepares carbon fiber complex core, a diameter of
5--12mm, regulation temperature makes curing degree reach more than 85%；
3rd, both sides glass fibre respectively enters the second impregnation district and the 3rd impregnation district impregnation, the ring of use after drawing
Epoxy resins is high temperature resistant weathe resistance epoxy resin；
4th step, after impregnation, glass fibre is by winding district voluble wrapping at carbon fiber core outer layer, and unilateral thickness is 0.5--
2mm, speed of wrap is by Serve Motor Control and pultrusion speed synchronised；
5th step, after carbon fiber complex core and glass fibre protective layer are compound together with by the second curing oven, regulate temperature
Both are made fully to solidify；
6th step, composite material cable core goods are by, after traction machine, collecting at closed reel.
The manufacture method of this carbon fiber composite material cable wire and the manufacture method of existing carbon fiber composite material cable wire
Compare, have the advantages that
(1) present invention uses glycolylurea epoxide resin and low viscosity epoxy resin (bisphenol A-type and bisphenol-f type glycidyl ether
At least one in based epoxy resin) blending type epoxy resin as resin matrix, glass fibre can not only be met to resin
Low viscous requirement, it is also possible to make cable core possess the resistance to elevated temperatures of excellence.
(2) glycolylurea epoxide resin being employed herein, it has, and viscosity is low, good manufacturability, has glass fibre very well
Wetting property, and owing to its structure comprising five yuan of diazacyclos, also have that Heat stability is good, thermostability be high, weather resisteant concurrently
The feature such as good.
(3) the polyether amine firming agent structure used in the present invention comprises the toughness functional groups such as multiple ehter bonds, it is possible to make
Cable core has the shock resistance of high-strength and high ductility, by using being blended of polyether amine firming agent and aliphatic amine curing agent
Type curing system, can effectively solve the problems such as solidfied material fragility, elongation at break be little.
(4) present invention uses a certain amount of accelerator to coordinate blending type amine curing agent to be used together, and can effectively solve
The problem of cold curing overlong time, ensure that the intensity of solidfied material is held essentially constant while shortening hardening time.
(5) auxiliary agents such as silane coupler, antioxidant and diluent is employed herein.Wherein silane coupler is permissible
Improve bonding strength between reinforcing glass fibrous material and resin, improve interface state, be conducive to improving composite product
Mechanical performance and electrical insulation capability；Antioxidant can suppress or slow down macromolecular material Auto-oxidation reaction speed；The work of diluent
By the viscosity that can reduce whole compositions.
(6) due to the fact that load-bearing core and protective layer are chosen as different epoxy-resin systems, the therefore epoxy of load-bearing core
Resin system strong mechanical performance will not be affected by the epoxy-resin systems of exterior cover sheets, and excellent weather-proof of exterior cover sheets
It is the most from the external environment that performance protects load-bearing core, makes the combination property of cable core be greatly improved.
(7) due to the fact that in protective layer, with the addition of ultraviolet absorber and energy transfer agent so that cable core has excellent
Good heat-resisting quantity, weatherability i.e. uvioresistant and ageing resistace.
Accompanying drawing explanation
Fig. 1 is the structural representation of carbon fiber composite material cable wire of the present invention；
Fig. 2 is the moulding process schematic diagram of carbon fiber composite material cable wire 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 3rd impregnation district；6-is wound around district；
7-the second curing oven；8-traction machine；9-closed reel；10-carbon fiber；11-glass fibre；12-load-bearing core；13-protective layer.
Detailed description of the invention
Below in conjunction with Fig. 1 and Fig. 2, the present invention will be further described:
As it is shown in figure 1, the manufacture method of a kind of carbon fiber composite material cable wire, including load-bearing core 12 and protective layer 13,
Protective layer 13 is coated on the outside of described load-bearing core 12 by winding process, and load-bearing core 12 is high temperature resistant strong mechanical performance asphalt mixtures modified by epoxy resin
Fat and the complex of carbon fiber, protective layer 13 is the complex of high temperature resistant weathering performance composition epoxy resin and glass fibre,
High temperature resistant weathering performance composition epoxy resin is made up of following compositions: including component A and component B, wherein component A includes following
Composition: 100 mass parts epoxy resin, 5-10 mass parts diluent and 0.5-3.0 mass parts silane coupler；Under component B includes
State composition: 15-35 mass parts amine curing agent, 0.1-3.0 mass parts accelerator and 0.01-0.1 mass parts antioxidant, asphalt mixtures modified by epoxy resin
Fat is epoxy resin a and the combination of epoxy resin b, and the mass ratio of epoxy resin a and epoxy resin b is: 10-30: 70-90；Its
In, epoxy resin a be comprise the glycidic amine type of one or more glycolylurea ring (five yuan of diazacyclos), diglycidyl ether type or
Glycidyl ester type glycolylurea epoxide resin；Glycolylurea ring (five yuan of diazacyclos) structural formula is as follows, glycolylurea ring (five yuan of diazas
Ring) substituent R 1 and R2 is H, CH3, C2H5, aryl or aralkyl in structural formula:
；Epoxy resin b is bisphenol A-type glycidyl ether type epoxy resin or bisphenol-f type glycidyl ether type epoxy resin；
Wherein, bisphenol-f type glycidyl ether type epoxy resin or the range of viscosities of bisphenol A-type glycidyl ether type epoxy resin: 500-
4000mPa·s(25℃)。
The high temperature resistant strong mechanical performance epoxy resin of load-bearing core 12 be E51 epoxy resin, TDE86 epoxy resin (4,5-ring
Oxygen cyclohexane-1,2 dioctyl phthalate 2-glycidyl ester), AG80 four-functional group epoxy resin, MY721 epoxy resin, AFG90 tri-official
Can roll into a ball epoxy resin, Tao Shi produce DER331 liquid epoxies in one or more.
Amine curing agent is amine curing agent a and the combination of amine curing agent b, amine curing agent a's and amine curing agent b
Mass ratio is: 5-15: 10-20；Described amine curing agent a is the polyether amine comprising two or more amido functional groups
Compound, molecular weight ranges 200-2500, range of viscosities: one in the polyether amine compound of 5-300mPa s (25 DEG C) or
Several；Described amine curing agent b is one or more of aliphatic amine and modified aliphatic aminated compounds, selected from divinyl
Triamine, triethylene tetramine, TEPA, diamidogen, methylol ethylenediamine, methylol diethylenetriamine, beta-hydroxyethyl second two
One or more in amine.
Accelerator is selected from: the one in 2,4,6-tri-(dimethylamino methyl) phenol, boron trifluoride complex, triethanolamine
Or it is multiple.
Diluent is the compound comprising two epoxy functionality and at least one ehter bond, shrinks sweet selected from ethylene glycol bisthioglycolate
Oil ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cylohexanediol diglycidyl ether, cyclohexanedimethanol
In diglycidyl ether, neopentylglycol diglycidyl ether, polyethyleneglycol diglycidylether, resorcinolformaldehyde resin
One or more.
Coupling agent is the silane coupling agent comprising epoxy functionality, selected from gamma-aminopropyl-triethoxy-silane, γ-
One in glycidyl ether oxygen propyl trimethoxy silicane or γ-(methacryloxy) propyl trimethoxy silicane.
Antioxidant is that the mass ratio of the combination of primary antioxidant and aid anti-oxidants, primary antioxidant and aid anti-oxidants is: 0.0095-
0.08∶0.0005-0.02；Primary antioxidant is Hinered phenols antioxidant, selected from four [β-(3,5-di-tert-butyl-hydroxy phenyls)
Propanoic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid octadecanol ester, 2,2-thiobis [3-(3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate or 4, the one in 6-bis-(pungent sulfidomethyl)-o-cresol；Described aid anti-oxidants sulfur
For esters antioxidant, selected from the double lauryl alcohol ester of thio-2 acid, the double tetradecyl alchohol ester of thio-2 acid or thio-2 acid double 18
One in alcohol ester.
Being also added with ultraviolet absorber in protective layer 13, described ultraviolet absorber is UV-9, UV-531, UV-327, triazine-5
In a kind of or the most several combination.
Being also added with energy transfer agent in protective layer 13, energy transfer agent is three (1,2,2,6,6-pentamethvl base) phosphorous
One or both combinations in acid esters or AM101.
As in figure 2 it is shown, be the moulding process schematic diagram of the manufacture method of carbon fiber composite material cable wire of the present invention, its work
Make forming principle 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 resistance to height
Temperature strong mechanical performance epoxy resin；
Second step, after impregnation completes, carbon fiber enters the first curing oven 3 precuring, prepares carbon fiber complex core, a diameter of
5-12mm, regulation temperature makes curing degree reach more than 85%；
3rd step, both sides glass fibre 11 respectively enters the second impregnation district 4 and the 3rd impregnation district 5 impregnation after drawing, and uses
Epoxy resin be high temperature resistant weathe resistance epoxy resin；
4th step, after impregnation, glass fibre is by winding district 6 voluble wrapping at carbon fiber core outer layer, and unilateral thickness is 0.5-
2mm, speed of wrap is by Serve Motor Control and pultrusion speed synchronised；
5th step, after carbon fiber complex core and glass fibre protective layer are compound together with by the second curing oven 7, regulate temperature
Both are made fully to solidify；
6th step, composite material cable core goods are by, after traction machine 8, collecting at closed reel 9.
High temperature resistant weathering performance composition epoxy resin manufacture method is as follows: comprise the following steps: step 1, by component A
Part epoxy resin a and b below 30 DEG C with speed mechanical dispersed with stirring 5-10 minute of 800-1000 rev/min；Step
2, diluent and coupling agent it are sequentially added into while stirring, with speed mechanical dispersed with stirring 5-10 minute of 800-1000 rev/min
Set aside for use under rear room temperature；Step 3, by composition amine curing agent a and b in component B at room temperature with 600-800 rev/min
Speed mechanical dispersed with stirring 5-10 minute；Step 4, add accelerator, primary antioxidant and aid anti-oxidants while stirring, in room
With speed mechanical dispersed with stirring 5-10 minute of 600-800 rev/min under temperature；Step 5, at room temperature component A and component B are mixed
Close, with speed mechanical dispersed with stirring 3-5 minute of 3000-3500 rev/min；High temperature resistant weathering is i.e. obtained after step 6, vacuum defoamation
Performance composition epoxy resin.
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 Lanxing Chemical New Material Co., Ltd. Wuxi
Resin processing plant, epoxide number is 0.48-0.54) at 25 DEG C with the speed mechanical dispersed with stirring 5 minutes of 800 revs/min, while stirring
Be sequentially added into 5g1,4-butanediol diglycidyl ether, 0.5g γ-glycidyl ether oxygen propyl trimethoxy silicane, with 800 turns/
Minute speed mechanical dispersed with stirring set aside for use under room temperature after 10 minutes, by 15.0g polyetheramine D230 and 20.0g triethylene four
Amine at room temperature with the speed mechanical dispersed with stirring 5 minutes of 600 revs/min, adds 0.5g2,4,6-tri-(diformazans while stirring
Amino methyl) phenol, 0.08g tetra-[β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester and 0.02g sulfur generation two
The double lauryl alcohol ester of propanoic acid, at room temperature with the speed mechanical dispersed with stirring 5 minutes of 600 revs/min.At room temperature by said components
Mixing, with the speed mechanical dispersed with stirring 3 minutes of 3000 revs/min, i.e. obtains described composition epoxy resin after vacuum defoamation,
It is subsequently poured into die casting solidification.The exothermic heat of reaction curve of differential scanning calorimetry (DSC method) test wrapper epoxy resin system, heats up
5 DEG C/min of speed 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,
180 DEG C solidify 2 hours.According to standard GB/T/T 16421-1996 to preparation the hot strength of epoxy matrix resin, fracture
Elongation percentage, tensile modulus of elasticity are tested, and specimen size is as follows: a length of 100mm ± 0.5mm, end portion width be 10mm ±
0.5mm, narrow parallel portion length 30mm ± 0.5mm, narrow parallel portion width 5mm ± 0.2mm, thickness be 2.2mm ±
0.2mm.Experiment repeats six times, and the hot strength recording this epoxy matrix resin is 58MPa, fracture elongation 4.0%, stretches bullet
Property modulus 2.5GPa.Bending strength, bending bullet according to the standard GB/T/T16419-1996 epoxy matrix resin to preparing
Property modulus is tested, and specimen size is as follows: a length of 40mm, and width is 3mm ± 0.2mm, and thickness is 2mm ± 0.2mm.Experiment
Repeating six times, the bending strength recording this epoxy matrix resin is 104MPa, modulus of elasticity in static bending 3.3GPa.Means of differential scanning calorimetry
Method (DSC method) surveys vitrification point, and 5 DEG C/min of heating rate, the vitrification point recording epoxy matrix resin is 155 DEG C, adopts
By NDJ-8S type rotating cylinder viscometer testing tree oil/fat composition viscosity, viscosity when 25 DEG C is 471mPa s.
Above in conjunction with accompanying drawing, the present invention is carried out exemplary description, it is clear that the realization of the present invention is not by aforesaid way
Restriction, as long as have employed method design and the various improvement that carry out of technical scheme of the present invention or the most improved by the present invention
Design and technical scheme directly apply to other occasion, the most within the scope of the present invention.
Claims (1)
1. a manufacture method for carbon fiber composite material cable wire, carbon fiber composite material cable includes load-bearing core (12) and protects
Sheath (13), described protective layer (13) is coated on the outside of described load-bearing core (12), described load-bearing core (12) by winding process
For the complex of high temperature resistant strong mechanical performance epoxy resin Yu carbon fiber, described protective layer (13) is high temperature resistant weathering performance epoxy
Resin combination and the complex of glass fibre, described high temperature resistant strong mechanical performance epoxy resin is E51 epoxy resin, TDE86
Epoxy resin (4,5-epoxide ring ethane-1,2 dioctyl phthalate 2-glycidyl ester), AG80 four-functional group epoxy resin, MY721 epoxy
Resin, AFG90 trifunctional epoxy resin, Tao Shi produce DER331 liquid epoxies in one or more；
Its manufacture method comprises the following steps:
Step 1, is drawn carbon fiber (10) by creel (1), enters the first impregnation district (2) impregnation, and the epoxy resin of use is resistance to
High temperature strong mechanical performance epoxy resin；
Step 2, after impregnation completes, carbon fiber enters the first curing oven (3) precuring, prepares carbon fiber complex core, a diameter of 5-
12mm, regulation temperature makes curing degree reach more than 85%；
Step 3, both sides glass fibre (11) respectively enters the second impregnation district (4) and the 3rd impregnation district (5) impregnation after drawing, and uses
Epoxy resin be high temperature resistant weathe resistance epoxy resin；Described high temperature resistant weathering performance composition epoxy resin is by following compositions system
Becoming: include component A and component B, wherein component A includes following compositions: 100 mass parts epoxy resin, 5-10 mass parts diluent
With 0.5-3.0 mass parts silane coupler；Component B includes following compositions: 15-35 mass parts amine curing agent, 0.1-3.0 mass
Part accelerator and 0.01-0.1 mass parts antioxidant, described epoxy resin is epoxy resin a and the combination of epoxy resin b, epoxy
The mass ratio of resin a and epoxy resin b is: 10-30: 70-90；Wherein, described epoxy resin a is for comprising one or more glycolylurea
Glycidic amine type, diglycidyl ether type or the glycidyl ester type glycolylurea epoxide resin of 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 is 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, bisphenol-f type glycidyl ether type epoxy resin or the range of viscosities of bisphenol A-type glycidyl ether type epoxy resin: 25 DEG C
Time 500-4000mPa s；Described antioxidant is the matter of the combination of primary antioxidant and aid anti-oxidants, primary antioxidant and aid anti-oxidants
Amount ratio is: 0.0095-0.08: 0.0005-0.02；Described primary antioxidant is Hinered phenols antioxidant, selected from four [β-(3,5-bis-
Tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid octadecanol ester,
2,2-thiobiss [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate or 4, in 6-bis-(pungent sulfidomethyl)-o-cresol
Kind；Described aid anti-oxidants is monothioester kind antioxidant, selected from the double lauryl alcohol ester of thio-2 acid, the double tetradecyl alchohol ester of thio-2 acid
Or the one in the double octadecyl of thio-2 acid；Described protective layer (13) is also added with ultraviolet absorber, described uv absorption
Agent is a kind of or the most several combination in UV-9, UV-531, UV-327, triazine-5；Described protective layer is also added with energy in (13)
Transfer agent, described energy transfer agent is the one or two in three (1,2,2,6,6-pentamethvl base) phosphite esters or AM101
Plant combination；
Step 4, after impregnation, glass fibre is by winding district (6) voluble wrapping at carbon fiber core outer layer, and unilateral thickness is 0.5-
2mm, speed of wrap is by Serve Motor Control and pultrusion speed synchronised；
Step 5, after carbon fiber complex core and glass fibre protective layer are compound together with made by the second curing oven (7), regulation temperature
Both fully solidifications；
Step 6, carbon fiber composite cable core goods are by, after traction machine (8), collecting at closed reel (9) place.
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| 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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