CN1283711C - Semi-conductive mixture - Google Patents
Semi-conductive mixture Download PDFInfo
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- CN1283711C CN1283711C CN 200310104554 CN200310104554A CN1283711C CN 1283711 C CN1283711 C CN 1283711C CN 200310104554 CN200310104554 CN 200310104554 CN 200310104554 A CN200310104554 A CN 200310104554A CN 1283711 C CN1283711 C CN 1283711C
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Abstract
Basic polymer is generated by using 20 to 70 portions of low-density polythene by weight and 80 to 30 portions of other polyolefin polymer by weight, and 30 to 80 portions of conductive carbon black is added in 100 portions of the basic polymer by weight.
Description
Technical field
The present invention relates to be used in the semi-conductivity mixture of semi-conductive layers such as external semi-conductive layer such as cross-linked polyethylene insulated cable.
Background technology
Between the conductor and insulation layer that are applicable to cable such as high-tension cross-linked polyethylene insulated cable, in the semi-conductive layer of the inside semi-conductive layer of setting or external semi-conductive layer etc., use the semi-conductivity mixture.This material from the mitigation of current potential inclination or prevent that the shelf depreciation equal angles from considering, needs control to reduce volume opposing rate, in addition, and physical strength such as anti-extension in the longitudinal direction during for example laying cable that needs to keep high.
Such semi-conductivity mixture, be base polymer for example in the past, and wherein cooperated an amount of conductive carbon black to make with polyolefin polymers such as ethylene-vinyl acetate copolymer, ethene-acrylic acid ethyl ester multipolymer, ethene-alpha-olefin-diene terpolymer.
Therefore, when improving electroconductibility by the use level that increases conductive carbon black, the semi-conductivity mixture can harden, and causes breaking easily of semi-conductive layer.
Summary of the invention
The object of the present invention is to provide a kind of semi-conductivity mixture that keeps high physical strength, reduce volume opposing rate by the composition control of adjusting base polymer.
In order to solve above problem, semi-conductivity mixture of the present invention is characterized in that, in polyolefin polymers 100 weight parts of the new LDPE (film grade) that contains 20～70 weight parts, has cooperated the conductive carbon black of 30～80 weight parts.
Embodiment
Below semi-conductivity mixture that embodiments of the present invention are related to describe.
This semi-conductivity mixture is engaged in by the conductive carbon black with 30～80 weight parts in the electroconductibility base polymer of 100 weight parts and makes.
Above-mentioned base polymer is made by the new LDPE (film grade) (hereinafter referred to as [LDPE] or [the 1st composition]) of specified quantitative and the ratio of components mixed polymer of can adjusting of the polyolefin polymers (to call [the 2nd composition] in the following text) beyond the LDPE.
Above-mentioned the 1st composition (being LDPE) is 0.91～0.94g/cm by density
3Polyethylene or the density of alpha-olefin copolymer such as ethene and a spot of polypropylene, 1-hexene, 1-butylene be 0.89～0.91g/cm
3Ethylene copolymer form.
Poly density surpasses 0.94g/cm
3The time, crystallinity is too high and cause the really up to the mark of base polymer, and the flexibility variation of mixture.The density of ethylene copolymer is less than 0.89g/cm
3The time, crystallinity reduces, and the volume opposing rate of base polymer can not reduce.
Above-mentioned the 2nd composition can be a polyolefin polymers except the 1st composition (LDPE), as ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethene-alpha-olefin-diene terpolymer etc.
In the above-mentioned ethylene-vinyl acetate copolymer, vinyl acetate content is about 10～35 weight %, so melt flow rate (MFR) is that the processibility of 1～20 o'clock base polymer is good, and sooty disperses also to become easy.
In the above-mentioned ethylene-ethyl acrylate copolymer, its ethyl propenoate content is about 10～25 weight %, therefore can be in the base polymer additional flexibility.
Above-mentioned ethene-alpha-olefin-diene terpolymer, at ethylene propylene terpolymer (EPT) or ethene and 1-butylene, the 1-amylene, the 1-hexene, alpha-olefin low polymers and 1 such as 4-methyl-1-pentene, 4-hexadiene, dicyclopentadiene, in the material of non-conjugated diene hydrocarbon copolymerization such as 5-ethylidene-2-norbornene etc., select a kind of or the mixture more than 2 kinds wherein for use with any weight ratio.
This ethene-alpha-olefin-diene terpolymer, the main physical strength that improves in base polymer.The ratio of the ethene in ethene-alpha-olefin-diene terpolymer is according to required physical strength of mixture etc., in 50～95 moles of % scopes.
The proportion of composing of above-mentioned base polymer, the 1st composition (LDPE) is 20～70 weight parts, and the 2nd composition is 80～20 weight parts, and preferably the former is 30～60 weight parts, and the latter is 70～40 weight parts.
The 1st composition (LDPE) is during less than 20 weight parts, and the volume opposing rate of semi-conductive layer can not fully reduce, and during greater than 70 weight parts, is difficult to carry out the extrusion processing of mixture owing to hardening.
The carbon black that cooperates for additional guide in above-mentioned base polymer is electrical can be acetylene black, furnace black etc., and its blending ratio of base polymer 100 weight parts according to required electroconductibility, can be adjusted in 30～80 weight part scopes relatively.
In the above-mentioned semi-conductivity mixture, can add linking agent, crosslinking coagent, age resister etc. in case of necessity.
Linking agent, preferred dicumyl peroxide (DCP), 2,5-dimethyl-2, peroxyde crosslinked dose of 5-two (tert-butyl peroxide)-3-hexin etc., its use level, base polymer 100 weight parts are adjusted into about 0.2～3 weight part relatively.
Crosslinking coagent can be used cyamelide triallyl, triallyl cyanurate, tetraene propoxy-ethane, m-phenylene bismaleimides etc., and base polymer 100 weight parts are adjusted into 0.5～3 weight part relatively.
These linking agents and crosslinking coagent can and be used or used separately.Use under the situation of crosslinking coagent separately, the linking agent part in the isolator moves to semi-conductive layer, by forming crosslinked with this reaction of moving linking agent.
Age resister can use 4, and 4 '-thiobis (the 6-tertiary butyl-3-methylphenol) etc. can add Zinic stearas, zinc oxide, magnesium oxide etc. in case of necessity.
Semi-conductive layer, with said mixture on the conductor or the inboard of isolator with 120～140 ℃ extrusion temperature under extrusion molding and forming.
(effect)
Above-mentioned semi-conductivity mixture because the cooperation of selected base polymer can reduce volume opposing rate, and can improve physical strength such as extension.
Embodiment
The experimental example of above-mentioned embodiment below is described, clear and definite its action effect.
After mixture mixes with muller by use level shown in the last table 1 of this specification sheets, utilize thermocompressor under 200 ℃, to carry out hot pressing in 30 minutes and the test that is shaped with thin slice (thickness is 1mm), measured its volume opposing rate under 60 ℃, and the fail in tension elongation of having pressed the JIS-K-7113-1981 test method measuring.The result is as shown in table 1.
As can be seen from Table 1, the volume opposing rate of said mixture is all less than 700 Ω cm, and elongation is the high elongation rate more than 200%, demonstrates good physical strength.
Then, mixture shown in the table 1 (embodiment 1,5,8, comparative example 12～14) is used in the semi-conductive layer, having made the crosslinked polyetylene insulated ethene of 6.6KV level is cable (CV cable).Specifically, at 100mm
2Soft copper twist thread on, covered the inside semi-conductive layer formed by said mixture successively, cooperated insulation layer that the polyethylene (HFDJ-4201, Japanese ユ ニ カ one) of linking agent forms and by the external semi-conductive layer of forming with the mixture same material that forms above-mentioned inner semi-conductive layer.Measured the volume opposing rate (60 ℃) of inside and external semi-conductive layer after crosslinked.The result is as shown in table 2.
Table 2
| Embodiment | Comparative example | |||||
| 1 | 5 | 8 | 12 | 13 | 14 | |
| Inner semi-conductive layer | 800 | 700 | 700 | 4000 | 6000 | 15000 |
| External semi-conductive layer | 600 | 700 | 5000 | 2000 | 4000 | 8000 |
(unit: Ω cm)
From this table 2 as can be seen, the semi-conductive layer that said mixture is formed is compared with the semi-conductive layer that the mixture of comparative example is formed, and its volume opposing rate utmost point falls.
The invention effect
As mentioned above, semi-conductivity mixture of the present invention, as base polymer because therefore the mixed polymer that uses the VLDPE of specified quantitative and form except the polyolefin polymers of VLDPE has low volume opposing rate and high mechanical strength.
Cables such as cross-linked polyethylene insulated cable with semi-conductive layer of being made up of this mixture, the physical strength of its semi-conductive layer is good, for example can adapt to when laying cable the extension of cable on long all directions etc., thereby handle easily.
Table 1
| Embodiment. | Comparative example | ||||||||||||||||
| Cooperate | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 |
| LDPE *1 | 30 | 50 | 60 | 30 | 50 | 60 | 30 | 50 | 60 | 50 | 50 | ||||||
| EVA *2 | 70 | 50 | 40 | 50 | 50 | 100 | 50 | 50 | 50 | ||||||||
| EEA *3 | 70 | 50 | 40 | 100 | |||||||||||||
| EPT *4 | 70 | 50 | 40 | 100 | |||||||||||||
| PE *5 | 50 | 50 | 50 | ||||||||||||||
| Carbon black (1) *6 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | ||
| Carbon black (2) *7 | 40 | 40 | |||||||||||||||
| Zinic stearas | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Linking agent (1) *8 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | ||
| Linking agent (2) *9 | 1 | 1 | |||||||||||||||
| Age resister *10 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Volume opposing rate (60 ℃, Ω cm) | 600 | 400 | 300 | 700 | 500 | 400 | 600 | 400 | 400 | 300 | 200 | 1500 | 2000 | 2000 | 200 | 400 | 500 |
| Elongation (%) | 280 | 230 | 240 | 300 | 260 | 230 | 280 | 230 | 230 | 250 | 270 | 300 | 320 | 270 | 130 | 140 | 150 |
Unit of fit: weight part
*1 new LDPE (film grade) (シ ラ ソ Application 11, Mitsui petroleum chemistry)
*2 ethylene-vinyl acetate copolymer VA 28wt% (エ バ Off レ Star Network ス 250, Mitsui デ ユ ボ Application Port リ ケ ミ カ Le)
*3 ethylene-ethyl acrylate copolymers (Japanese レ Network ス ロ Application EEAA-4200, Japan petroleum chemistry)
*4 ethene-alpha-olefins-diene terpolymer (Mitsui rubber-X-75, Mitsui petroleum chemistry)
*5 new LDPE (film grade)s (シ ラ ソ Application 11, Mitsui petroleum chemistry)
*6 acetylene blacks (テ Application カ Block ラ Star Network, electrochemical industry)
*7 furnace blacks (バ Le カ Application XC-72, キ ユ ボ Star ト)
*8 dicumyl peroxides (Mitsui petroleum chemistry)
*92,5-dimethyl-2,5-two (tert-butyl peroxide)-3-hexin (バ one ヘ キ シ Application 258, Japanese grease)
*10 ノ Network ラ Star Network 300 (the emerging chemical industry of imperial palace)
Claims (1)
1. a semi-conductivity mixture is characterized in that, in polyolefin polymers 100 weight parts of the new LDPE (film grade) that contains 20～70 weight parts, cooperates the conductive carbon black of 30～80 weight parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310104554 CN1283711C (en) | 2003-10-31 | 2003-10-31 | Semi-conductive mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310104554 CN1283711C (en) | 2003-10-31 | 2003-10-31 | Semi-conductive mixture |
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| Publication Number | Publication Date |
|---|---|
| CN1611535A CN1611535A (en) | 2005-05-04 |
| CN1283711C true CN1283711C (en) | 2006-11-08 |
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| CN 200310104554 Expired - Fee Related CN1283711C (en) | 2003-10-31 | 2003-10-31 | Semi-conductive mixture |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6216347B2 (en) | 2015-03-20 | 2017-10-18 | 日清紡メカトロニクス株式会社 | Rubber composition for solar cell thermal / optical hybrid solar cell module |
| CN105985571B (en) * | 2015-07-05 | 2018-03-23 | 青岛科技大学 | A kind of semiconductive shieldin material for weakening positive temperature coefficient effect and preparation method thereof |
| CN104961966B (en) * | 2015-07-17 | 2018-06-08 | 广东环威电线电缆股份有限公司 | Heat the preparation method of cable, semi-conductive high polymer material and semi-conductive high polymer material |
| CN105820414A (en) * | 2016-04-21 | 2016-08-03 | 苏州市双虎科技有限公司 | Semiconductive polyethylene shielding material for cables |
| CN111635568A (en) * | 2019-03-01 | 2020-09-08 | 全球能源互联网研究院有限公司 | Semiconductive shielding material for high-voltage cable |
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