CN1138282C - Kernel/shell particles modified anticorrosion stress-resistant core rod for high-voltage composite insulator - Google Patents
Kernel/shell particles modified anticorrosion stress-resistant core rod for high-voltage composite insulator Download PDFInfo
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- CN1138282C CN1138282C CNB001056360A CN00105636A CN1138282C CN 1138282 C CN1138282 C CN 1138282C CN B001056360 A CNB001056360 A CN B001056360A CN 00105636 A CN00105636 A CN 00105636A CN 1138282 C CN1138282 C CN 1138282C
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- soft
- epoxy resin
- monomer
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- nuclear
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- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 239000012212 insulator Substances 0.000 title claims abstract description 13
- 239000010420 shell particle Substances 0.000 title claims abstract description 6
- 239000003822 epoxy resin Substances 0.000 claims abstract description 17
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 17
- 239000003365 glass fiber Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000012779 reinforcing material Substances 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 239000004593 Epoxy Substances 0.000 claims description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
- 125000003609 aryl vinyl group Chemical group 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 150000002924 oxiranes Chemical class 0.000 claims description 2
- 239000003607 modifier Substances 0.000 abstract description 18
- 229920002430 Fibre-reinforced plastic Polymers 0.000 abstract description 8
- 239000011151 fibre-reinforced plastic Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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
- -1 Aryl ethylene Chemical compound 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FCZCIXQGZOUIDN-UHFFFAOYSA-N ethyl 2-diethoxyphosphinothioyloxyacetate Chemical compound CCOC(=O)COP(=S)(OCC)OCC FCZCIXQGZOUIDN-UHFFFAOYSA-N 0.000 description 1
- 238000009422 external insulation Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
The present invention belongs to the technical field of manufacturing fiber reinforced plastics. Epoxy resin is adopted as a basic material, E glass fiber of unidirectional untwisted straight yarn or double yarn is used as a reinforcing material, soft-kernel hard-shell particles are simultaneously added to the epoxy resin basic material as a modifier, and the composition of hard shell is 20 to 50% of the composition of particles. The present invention can maintain the excellent electrical and mechanical properties of an original E-glass fiber epoxy resin core rod and can also have stress corrosion resistance, and thus, a core rod with excellent comprehensive properties of electrical properties and stress corrosion resistance for a composite insulator is obtained.
Description
Technical field the invention belongs to fibre reinforced plastics manufacturing technology field, particularly High-Voltage Insulation made technology.
The background technology composite insulator dodges advantages such as performance is good, specific strength is high, no null value, operation maintenance convenience because of its resistant, obtained in China electric power system high voltage external insulation field in recent ten years using widely.Its basic structure is the composite construction of fiber reinforced plastics rod suit organic material umbrella cover, and two ends are the metal gold utensil.Wherein fiber reinforced plastics rod is as the carrier of interior insulating part and mechanical load, and its electric and mechanical performance are directly connected to the operational reliability of composite insulator.The fiber reinforced plastics rod that is used for high-voltage composite insulator generally by one-way glass fiber impregnation epoxy resin-base after continuously the manufacturing of pultrusion (or cite approvingly and pull out) technology form.
By consisting of of the expoxy glass steel core bar of pultrude process manufacturing: glass fibre weight accounts for 2/3～4/5, and all the other 1/5～1/3 are epoxy resin-base, and for the horizontal extruding equipment that generally uses, the shared scope of glass fibre weight is narrower, is 3/4～4/5.The epoxy resin-base prescription is the mixture by a kind of epoxy resin or several epoxy resin, adds necessary curing agent, promoter, inner pattern releasing agent applicable in proportion, also adds other auxiliary agent such as defoamer, diluent, interface inorganic agent, colouring agent etc. sometimes.
Through material and technologic updating for over ten years, this glass-reinforced plastic material has had electric property preferably.But in actual motion, that insulator is in is electric, under machinery and the chemical comprehensive function, after operation after a while, brittle fracture (abbreviation brittle failure) accident of core rod of insulator occurred on some circuits.Because core brittle fracture may cause the electric power system serious accident that goes offline such, therefore just the overall targets electric and mechanical two aspects of plug are had higher requirement.At present successfully carried out the simulation of core brittle fracture with stress corrosion (cracking) test in the laboratory, also there has been the corresponding standard draft in International Electrotechnical Commission (IEC) about the anticorrosion stress-resistant performance of core rod used in composite insulator.
At present the main body of composite electric insulator core bar material be based on the E glass fibre the epoxy glass laminate plug.E glass-epoxy plug electric property excellence, mechanical strength is also fine, but the anticorrosion stress-resistant poor-performing, and dispersed big, wayward.The plug that Germany Hirst Societe Des Ceramiques Techniques (Hoechst CeramTec) replaces the E glass fibre to make with a kind of ECR fiber, its anticorrosion stress-resistant function admirable, but its electric property is undesirable.
Summary of the invention the objective of the invention is for overcoming the weak point of prior art, the kernel/shell particles modified anticorrosion stress-resistant core rod for high-voltage composite insulator of a kind of usefulness is proposed, promptly in the manufacture process of E glass-epoxy plug, add modifier, make it keep excellent electric, the mechanical performance of original E glass-epoxy plug, and have the anticorrosion stress-resistant performance concurrently, to obtain the core rod used in composite insulator of a kind of electric property and anticorrosion stress-resistant performance synthesis function admirable.
The present invention proposes the kernel/shell particles modified anticorrosion stress-resistant core rod for high-voltage composite insulator of a kind of usefulness, adopt epoxy resin-base, and with unidirectional, the non-twist direct yarn or the E glass fibre of folded yarn are as reinforcing material, while has also added particles modified dose of " soft " nuclear " firmly " shell structure in epoxy resin-base, its " soft " nuclear is formed by the aryl vinyl monomer copolymerizable of the soft or hard degree of " soft " monomer that can form soft segment and adjusting " soft " nuclear, its " firmly " shell is the monomer by rigidity, contain and can form with the monomer and the crosslinking agent combined polymerization of the functional group of epoxy resin reaction, the composition of " firmly " shell accounts for the mass percent 20～50% of particulate composition;
The present invention said " soft " monomer adopts butadiene, butyl acrylate; Said aryl vinyl monomer adopts styrene; The mass percent that each constituent accounts for " soft " nuclear is: butadiene 0～80%; Butyl acrylate 0～90%; Styrene 10～50%;
Said rigidity monomer adopts styrene, methyl methacrylate; Said can be glycidyl methacrylate with the monomer of the functional group of epoxy resin reaction; And the crosslinking agent diene A of appropriateness, the mass percent that each constituent accounts for " firmly " shell is: styrene 5～90%; Methymethacrylate 0～90%; Glycidyl methacrylate 1～12%; Crosslinking agent diene A 0.25～10%, the structure of diene A is:
R=H, CH
3, n=1～10.
Particles modified dose of the present invention's said " soft " nuclear " firmly " shell structure, diameter of particle are less than 1 micron, and the epoxide number of particulate is 0.005～0.032 gram equivalent of per 100 gram material.Particles modified dose of said " soft " nuclear " firmly " shell structure, its consumption is 3～40% of an epoxy resin quality.
The present invention adds modifier in addition based on existing E glass fibre expoxy glass steel core bar in the epoxy resin-base prescription.The effect of modifier is solidification internal stress and the interface stress that improves decay resistance, reduces fiber reinforced plastics rod, to improve the anticorrosion stress-resistant performance of fiber reinforced plastics rod.Therefore the fiber reinforced plastics rod that adopts the present invention to make has kept excellent electric, the mechanical performance of existing E glass fibre expoxy glass steel core bar fully.And obviously given its anticorrosion stress-resistant performance, under the product of 50 millimeters all sizes of 10 millimeters～φ of diameter phi has all reached and has acted in 300 MPa mechanical stresses and 1 equivalent salpeter solution, the brittle failure time was brought up to more than 100 hours from original several hours to tens hours, and dispersiveness greatly reduces.
Embodiment
Embodiment
The present invention is an example with the plug of making 24 millimeters of diameter phi, presses the synthetic 6 kinds of modifier particulates of raw material ratio in the table 1.According to as shown in Figure 1 existing pultrude process, the proportioning of pressing reinforcing material, epoxy resin component and three kinds of stocks of modifier in the table 2 draws plug then.
The building-up process of modifier particulate is: 600 milliliters of deionized waters, odium stearate or enuatrol 2 grams and a small amount of sodium acid carbonate place reactor, logical nitrogen, stirring makes its dispersion, temperature is 50 ℃, " soft " nuclear monomer constituent and the 0.8 gram potassium peroxydisulfate pressed in the table 1 are introduced fully dispersion in the reactor, after the polymerization 8～10 hours, slowly be added dropwise to " firmly " shell monomer constituent, after 4 hours temperature is raised to 80 ℃, reacted again 2 hours, synthetic emulsion is filtered, breakdown of emulsion, oven dry gets final product after the methanol wash.
Respectively with 6 kinds of synthetic modifier of listed raw material ratio in the table 1, by the consumption drawing plug of table 2 requirement.
Table 1
| Modifier | " soft " nuclear | " firmly " shell | |||||
| Soft monomer | Aryl ethylene | The rigidity monomer | Contain can with the monomer of the functional group of epoxy resin reaction | Crosslinking agent | |||
| Butadiene (gram) | Butyl acrylate (gram) | Styrene (gram) | Styrene (gram) | Methyl methacrylate (gram) | Glycidyl methacrylate (gram) | Diene A (gram) | |
| 1 | 38.0 | 71.0 | 15.0 | 37.0 | 26.0 | 7.7 | 5.3 |
| 2 | 83.5 | 71.5 | 32.0 | 8.0 | 4.3 | 0.7 | |
| 3 | 82.0 | 29.0 | 7.0 | 76.0 | 2.4 | 3.6 | |
| 4 | 67.0 | 19.6 | 55.4 | 52.0 | 5.5 | 0.5 | |
| 5 | 94.0 | 36.0 | 62.0 | 6.5 | 0.5 | ||
| 6 | 92.0 | 16.0 | 82.0 | 9.0 | 1.0 | ||
Table 2
| Form | Composition | The trade mark | Proportioning |
| Reinforcing material | The E glass fibre | RS480-R50 (folded yarn) | 780 parts |
| The epoxy resin component | Epoxy resin | E51 | 100 parts |
| Curing agent | JHY906 | 80 parts | |
| Promoter | DMP-30 | 3.5 part | |
| Inner pattern releasing agent | PS125 | 2 parts | |
| The interface inorganic agent | 30%KH570 and 30%KH580 add 40%TTLPI-35B and mix | 3 | |
| Modifier | Modifier | ||
| 1 | Form and see Table 1 | 3 parts | |
| Modifier 2 | 28 parts | ||
| Modifier 3 | 20 parts | ||
| Modifier 4 | 12 parts | ||
| Modifier 5 | 37 parts | ||
| Modifier 6 | 40 parts |
The pulling process of plug is as follows: draw yarn bundle 2 from yarn cake 1, totally 160, through guide plate 3 and dividing sinker plate 4, pass diameter and be reduced to plastic squeeze ring 5,6,7,8 and the mould 9 of 24.2 millimeters of φ from 30 millimeters of φ, to draw-gear 10.Length is that three district's temperature of 1.2 meters mould 9 are set at 130 ℃, 185 ℃ and 180 ℃ respectively from arrival end.
Press table 2 proportioning with epoxy resin E51, it is standby that methyl tetrahydrochysene phthalate anhydride JHY906, inner pattern releasing agent applicable, interface inorganic agent and modifier mix the back.After treating that mold temperature reaches set point, adding DMP-30 stirs and is mixed with resin adhesive liquid 11, and the resin adhesive liquid of each preparation 11 service times should be above 6 hours.Pour the resin adhesive liquid 11 that preparation is finished into glue groove 12, yarn bundle 2 is pressed into glue groove 12 can starts draw-gear 10.
For making each component, particularly modifier fully mixes with the epoxy resin component, 13 pairs of resin adhesive liquid of swinging agitator 11 is housed on glue groove 12 carries out continuous stirring.After the resin adhesive liquid 11, pass through dividing sinker plate 4 through draw-gear 10 with the hauling speed of 10 centimetres of per minutes on yarn bundle 2 soaks in glue groove 12, plastic squeeze ring 5,6,7,8 squeezes and removes unnecessary glue.Behind the mould 9 of uncured resin fibre body 14 through heating, be solidified into plug 15, drew draw-gear 10 after, cut into needed length by cast-cutting saw 16.
Claims (3)
1. one kind with kernel/shell particles modified anticorrosion stress-resistant core rod for high-voltage composite insulator, adopt epoxy resin-base, and with unidirectional, the non-twist direct yarn or the E glass fibre of folded yarn are as reinforcing material, it is characterized in that, while has also added particles modified dose of " soft " nuclear " firmly " shell structure in epoxy resin-base, its " soft " nuclear is formed by the aryl vinyl monomer copolymerizable of the soft or hard degree of " soft " monomer that can form soft segment and adjusting " soft " nuclear, its " firmly " shell is the monomer by rigidity, contain and can form with the monomer and the crosslinking agent combined polymerization of the functional group of epoxy resin reaction, the composition of " firmly " shell accounts for the mass percent 20～50% of particulate composition;
Said " soft " monomer adopts butadiene, butyl acrylate; Said aryl vinyl monomer adopts styrene; The mass percent that each constituent accounts for " soft " nuclear is: butadiene 0～80%; Butyl acrylate 0～90%; Styrene 10～50%;
Said rigidity monomer adopts styrene, methyl methacrylate; Said can be glycidyl methacrylate with the monomer of the functional group of epoxy resin reaction; And the crosslinking agent diene A of appropriateness, the mass percent that each constituent accounts for " firmly " shell is: styrene 5～90%; Methymethacrylate 0～90%; Glycidyl methacrylate 1～12%; Crosslinking agent diene A 0.25～10%, the structure of diene A is:
R=H, CH
3, n=1～10.
2. anticorrosion stress-resistant core rod according to claim 1 is characterized in that, particles modified dose of said " soft " nuclear " firmly " shell structure, diameter of particle are less than 1 micron, and the epoxide number of particulate is 0.005～0.032 gram equivalent of per 100 gram material.
3. anticorrosion stress-resistant core rod according to claim 1 and 2 is characterized in that, particles modified dose of said " soft " nuclear " firmly " shell structure, and its consumption is 3～40% of an epoxy resin quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001056360A CN1138282C (en) | 2000-04-14 | 2000-04-14 | Kernel/shell particles modified anticorrosion stress-resistant core rod for high-voltage composite insulator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001056360A CN1138282C (en) | 2000-04-14 | 2000-04-14 | Kernel/shell particles modified anticorrosion stress-resistant core rod for high-voltage composite insulator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1267064A CN1267064A (en) | 2000-09-20 |
| CN1138282C true CN1138282C (en) | 2004-02-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001056360A Expired - Fee Related CN1138282C (en) | 2000-04-14 | 2000-04-14 | Kernel/shell particles modified anticorrosion stress-resistant core rod for high-voltage composite insulator |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1138282C (en) |
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2000
- 2000-04-14 CN CNB001056360A patent/CN1138282C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1267064A (en) | 2000-09-20 |
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