CN1062879C - Semiconductive polyolefine as external shielding material of cable - Google Patents
Semiconductive polyolefine as external shielding material of cable Download PDFInfo
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- CN1062879C CN1062879C CN97115236A CN97115236A CN1062879C CN 1062879 C CN1062879 C CN 1062879C CN 97115236 A CN97115236 A CN 97115236A CN 97115236 A CN97115236 A CN 97115236A CN 1062879 C CN1062879 C CN 1062879C
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Abstract
The present invention relates to a semiconductive polyolefine material for an external shielding cable. Ethylene propylene terpolymer or EVA is adopted as basic resin of the material, chlorobutadiene rubber or chlorosulfonated polyethylene resin is adopted as modified resin, and in addition, acetylene carbon black, a vulcanization system, an antioxidant 1010, stearic acid, white oil, DPO, etc. are added. The preparation steps of the material comprise: firstly, the modified resin is refined in an open mode and drawn into sheets for use; secondly, the basic resin is measured, mixed and matched, the modified resin and other constituents are added, refined, molded, cut into granules and granulated to obtain the product. The physicochemical performance of the product meets standard requirements, and the peeling strength of the product can be regulated according to use requirements.
Description
The present invention relates to a kind of cross-linked polyolefin semiconduction external shield CABLE MATERIALS, belong to the polymer chemistry matrix material, functional materials or telecommunications engineering material.
Since 1979, domestic just the beginning developed the shielding material, and also has producer to go into operation successively, but the most dependence on import of starting material, and be limited to the production of inner shield material more, the production of external shield material is seldom, at present main dependence on import, and have following technical problem aborning to some extent.
(1) electrical property is unstable in the course of processing, has surpassed 10 as cable raw material specific resistance before processing
3Ω cm, when stranding was extruded once more, its value can reach 10
5Ω cm.
(2) processing characteristics is not good, as cross-linked shielding material, when extruding cable, top temperature is not higher than 130 ℃, and general production control is at 120 ℃, this high content of carbon black, the material of low resistance is extruding pelletization under low temperature like this, and mobile gesture is bad, because if controlled temperature is too high, cause crosslinkedly in early days, then can not satisfy later stage stranding requirement.
(3) because tramp material influences quality product, for this reason, general cable factory all relies on the imported raw material stranding, and ten thousand yuan/ton of import material 5-6 cause cost too high like this.Develop domestic raw material production cross-linking type external shield material for this reason the great social and economical benefit is arranged.
The objective of the invention is to utilize domestic raw materials, produce cross-linking type polyolefine external shield material, require raw material be based on domestic, cost is lower than import product of the same type, and can satisfy a kind of external shield CABLE MATERIALS of identical needs.Its key problem in technology is to solve the strippability problem of external shielding layer, and its stripping strength can be regulated between 8-40N/cm, to satisfy the needs of different purposes.
For achieving the above object, the technical solution used in the present invention is to select a kind of homemade polar polymer for use, dose in the formula system as material modified, when stranding, can form a kind of strippable external shielding layer with insulation layer (being non-polar polymer), it is good that this properties-correcting agent requires with the base-material consistency, and physics, mechanics, calorifics, electric property can reach corresponding standard.And require stable chemical performance, radiation hardness, heat-resisting can reach the cabling process requirement in the later stage cross-linking process.
At first be that starting material are selected, principle is to base on our country, and is cheap, and performance reaches service requirements.
1, terpolymer EP rubber or ethylene-vinyl acetate copolymer (EVA) are selected in the selection of base resin, the present invention for use, and its consumption is controlled at 10-30 part;
Ethylene-propylene rubber(EPR) terpolymer EP rubber (EPDM), 100 ℃ of mooney viscosities of its performance requriements are that 40 density are 0.865g/cm
3
Ethene, vinyl acetate copolymer (EVA) are selected high VA content, VA＞18%, the resin of melting index MI＜5 for use.
2, the selection of modified resin
Used modified resin requires the polarity height, good with the base resin consistency, good rippability is arranged again, the present invention selects for use chloroprene rubber or chlorosulfonated polyethylene rubber (CSPE) to determine that through test of many times its add-on is 70-90 part, promptly get base resin and modified resin and be 100 parts (weight), based on these two kinds of resins, add a certain amount of carbon black and promptly constitute the base-material of semiconduction external shield CABLE MATERIALS, be aided with vulcanization system again, oxidation inhibitor, lubricant, tenderizer can obtain satisfied product.
3, sooty is selected for use
Use Shawinigan black, consumption 15-25 part, what of consumption are decided according to the volume required resistance value of product and stripping performance.
4, vulcanization system selects for use
With polyvalent alcohol vulcanization system or metal oxide system:
Consisting of of polyvalent alcohol vulcanization system:
10 parts of tetramethylolmethanes (weight)
10 parts in magnesium oxide
0.3 part of dicumyl peroxide (DCP)
Metal oxide body is:
10 parts in magnesium oxide
10 parts in plumbous oxide
2 parts of bis-pentamethylenethiuram tetrasulfides (TRA)
0.5 part of curing hexichol isothiazole (DM)
5, oxidation inhibitor selects for use
Select 1010 for use, consumption is no more than 0.5 part.
6, lubricant selects for use
Generally use with hard ester acid and white oil, to improve the processing characteristics of compound, consumption is 4-6 part.
7, tenderizer selects for use
Generally select phthalate such as dioctyl phthalate (DOP) (DOP) for use, add-on is 10-15 part, can improve the flowability of compound, to satisfy processing requirement.
Prescription of the present invention is as follows:
Base resin: available terpolymer EP rubber (EPDR) or ethylene-vinyl acetate copolymer (EVA) consumption are the 10-30 weight part.
Modified resin: available chloroprene rubber or chlorosulfonated polyethylene rubber (CSPE) consumption is the 70-90 weight part.
More than two kinds of resins and be 100 weight parts.
Carbon black: use Shawinigan black, consumption is the 15-25 weight part.
Vulcanization system: with polyvalent alcohol vulcanization system or metal oxide system, consumption is the 18-23 weight part.
The proportioning of polyvalent alcohol vulcanization system is: tetramethylolmethane: magnesium oxide: dicumyl peroxide (DCP)=10: 10: 0.3
The proportioning of metal oxide system is: magnesium oxide: plumbous oxide: bis-pentamethylenethiuram tetrasulfide (TRA): curing hexichol isothiazole (DM)=10: 10: 2: 0.3
Oxidation inhibitor: four [3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester (1010) consumption is less than 0.5 weight part:
Lubricant: stearic acid+white oil consumption: 4-6 weight part
Tenderizer: dioctyl phthalate (DOP) (DOP) consumption 10-15 weight part, accompanying drawing 1 is a process flow sheet of the present invention, below in conjunction with accompanying drawing 1 technical process is described below:
1, earlier modified resin is opened refining with double roller plastic-making device, the control roller temperature is no more than 50 ℃, and the time is no more than 15 minutes, plasticizing evenly, after the thin-pass six times, it is standby to pull into thickness 1-1.5 millimeter sheet material.
2, the weighing of base resin and other additives is mixed and mediates; as when selecting terpolymer EP rubber for use; still need to mould with two roller mill refinings earlier, the control roller temperature is no more than 50 ℃, and the time is no more than 15 minutes; add mixing other components that add successively again of modified resin then; add while opening refining, controlled temperature is no more than 90 ℃, thin-pass five times; pull into the sheet material of thickness 1-1.5 mm thick, be cooled to 30 ℃ and deliver to dull and stereotyped dicing machine pelletizing.
If selecting ethylene-vinyl acetate copolymer for use is base resin, then other add component, mixing kneading in the high speed kneader, mixed 30 minutes, the material temperature is no more than 140 ℃, blowing, when being cooled to 90 ℃, mixing with modified resin again, evenly pelletizing on dull and stereotyped dicing machine again after the cooling, the particle that dull and stereotyped dicing machine cut out, again plastify granulation through the SJ-30/25 extruding granulator, and finally obtain finished product, and selected single screw extruder pelletizer L/D=25/1, the control of each section temperature is as follows;
Charging opening
1 section 2 sections 3 sections 4 sections head 60-80 ℃ 90-110 ℃ 110-130 130-140 ℃ 140-150 ℃
60-80 rev/min of forcing machine speed, the water cooling pelletizing packs.
The end properties test
Get a certain amount of pellet, at 175 ℃, be pressed into the sheet stock that thickness is the 1-2 millimeter in 15 minutes under pressure 18MPa, carry out following performance test, the index that conforms to standard code is qualified finished product, and table 1 is product test performance of the present invention and normal data contrast.
According to the product that the present invention produced, its technical performance index is down after 15 megarad dose irradiation are crosslinked:
Table 1
| Sequence number | Project | Unit | Country's chemical building material electricity heart measured value | Q is suitable/the used standard code of SJY/001-1996 | |
| 1 | Density | g/cm 3 | 1.0797 | 0.95-1.20 | GB1033-86 |
| 2 | 20 ℃ of volume resistivitys | Ω.cm | 65.3 | ≤100 | GB3084.3 |
| 3 | Crosslinked back draft intensity | MPa | 26.4 | ≥10 | GB1040-92 |
| 4 | Crosslinked back elongation at break | ％ | 454 | ≥300 | GB1040-92 |
| 5 | 135 ℃, 7 days aging back tensile strength velocity of variation extension at break velocity of variation | ％ ％ | 16.7 5.02 | ±30 ±30 | GB1040-92 |
| 6 | 200 ℃ of hot elongation tests 15 minutes, 0.2MPa is load elongation permanent set down down | ％ ％ | 32 3.8 | ≤80 ≤5 | GB2951.5-89 |
| 7 | 175 ℃ of stripping strengths, sample preparation, speed 50mm/ branch | N/1cm | 11.7 | 8-40 | Q is suitable/SJY-001-1996 |
This product has following advantage with the product contrast that prior art is produced:
This product has the semiconduction performance, volume specific resistance is less than 100 Ω cm, through processing repeatedly, volume specific resistance is constant, and constant at 20 ℃ of-90 ℃ of volume specific resistances that record, enough intensity is arranged, though use a large amount of carbon blacks, its expressing technique condition is still very excellent, and its elongation at break can be up to 300%, regulate formula constituent, peel strength value can change according to service requirements.
Description of drawings: Fig. 1 is a process flow sheet of the present invention.
It below is the embodiment of the invention.
Table 2 formula table: materials component: be material true weight (gram number) in the umber, parantheses
Table 2
| Sequence number | Component | Example 1 | Example 2 | Example 3 |
| 1 | Base resin EPDR EVA | 30(97.0) | 30(97.0) | 30(96.0) |
| 2 | Modified resin chloroprene rubber CSPE | 70(227.0) | 70(227.0) | 70(223.0) |
| 3 | The carbon black Shawinigan black | 17(55.0) | 17(55.0) | 17(54.0) |
| 4 | Vulcanization system (1) tetramethylolmethane Mgo DCP | 10(32.4) 10(32.4) 0.3(1.0) | 10(32.4) 10(32.4) 0.3(1.0) | |
| (2)Mgo Pbo TRA DM | 10(32.0) 10(32.0) 2(6.4) 0.5(2.0) | |||
| 5 | Antioxidant 1010 | 0.2(0.7) | 0.2(0.7) | 0.2(0.6) |
| 6 | The lubricant stearic acid white oil | 2(6.5) 3(10.0) | 2(6.5) 3(10.0) | 2(6.4) 3(9.6) |
| 7 | Tenderizer DOP | 12(38.0) | 12(38.0) | 12(38.0) |
The abbreviation meaning is seen the 8th page of synopsis of specification sheets in the table 2.
Embodiment 1:
With 227.0 gram CSPE, in two roller mills, to refine and mould, temperature is controlled at below 50 ℃, 10 minutes time, thin-pass six times, it is stand-by to pull into thick 1-1.5 millimeter sheet material afterwards.
In two roller mills, 97 gram EPDR are opened refining 10 minutes under＜50 ℃, through thin-pass six times; pull into the sheet material of 1-1.5 millimeter; it is mixing with it to open the good CSPE sheet material of refining afterwards, adds 1,010 0.7 grams afterwards successively, stearic acid 6.5 grams; white oil 10 grams; Dop38 gram, 90 ℃ to be mixed down evenly after marks criticize and add 55 gram acetylene blacks, be mixed even after; add tetramethylolmethane 32.4 grams; magnesium oxide 32.4 grams, DCP1.0 gram, mixing; thin-pass six times; notice that temperature can not surpass 90 ℃, pulls into the sheet material of 1-1.5 mm thick, slice; cooling is sent into dull and stereotyped dicing machine pelletizing about 30 ℃.
The above-mentioned particle that cuts, through the granulation of SJ-30/25 forcing machine, each section temperature is down in extruding:
1 section 2 sections 3 sections 4 sections head of charging opening
80℃ 100℃ 120℃ 140℃ 150℃
60 rev/mins of extruded velocities, cooling and dicing, qualified after testing, be packaged into bag, sealing is qualified product.
Testing conditions is taken a sample through 175 ℃, and 15 minutes, the 18.0Mpa compressing tablet, the thick 1-2 millimeter of sheet is tested it by related standards.
Embodiment 2:
With 227.0 gram chloroprene rubbers, on double roller plastic-making device, to refine and mould, temperature is controlled at below 50 ℃, 10 minutes time, thin-pass six times, the sheet material that pulls into thickness afterwards and be the 1-1.5 mm thick is stand-by.
In the high speed kneader, add the EVA97 gram successively, Shawinigan black 55.0 grams, tetramethylolmethane 32.4 grams, Mgo32.4 gram, the DCP1.0 gram, 10100.7 grams, stearic acid 6.5 grams, white oil 10 grams, the DOP38 gram, high-speed stirring 30 minutes notices that temperature can not surpass 140 ℃, discharging afterwards.
In under 90 ℃ in two roller mills, chloroprene rubber is wrapped on the roller equably, and slowly add in the above-mentioned high speed kneader mixed material; through 10 minutes, thin-pass six times was pulled out the sheet material of 1-1.5 millimeter after evenly; slice is cooled to below 30 ℃, with dull and stereotyped dicing machine pelletizing.
The above-mentioned particle that cuts, through the granulation of SJ-30/25 forcing machine, each section of forcing machine temperature distribution is as follows:
Reinforced 1 section 2 sections 3 sections 4 sections head
80℃ 100℃ 120℃ 140℃ 150℃
60 rev/mins of extruded velocities, cooling and dicing is gone into bag through the package encapsulation that is up to the standards, and gets qualified product.
Testing conditions, 175 ℃, 15 minutes, the 18.0Mpa lower sheeting, the thick 1-2 millimeter of sheet is tested it by related standards.
Embodiment 3:
Get 223.0 gram CSPE, refine in two roller mills and mould, temperature is controlled at below 50 ℃, 10 minutes time, and thin-pass six times, the sheet material that pulls into thickness afterwards and be the 1-1.5 mm thick is stand-by.
In the high speed kneader, add the EVA96.0 gram successively, Shawinigan black 54.0 grams, Mgo32.0 gram, Pbo32.0 gram, the TRA6.4 gram, DM2.0 gram, 10100.6 grams, stearic acid 6.4 grams, white oil 9.6 grams, the DOP38.0 gram, high-speed stirring 30 minutes notices that temperature can not surpass 140 ℃, discharging afterwards.
Under 90 ℃, in two roller mills, with above-mentioned high speed kneader mixed compound, join at leisure above the CSPE that has wrapped roller; through 10 minutes, thin-pass six times was pulled out the sheet material of 1-1.5 mm thick after evenly; slice is cooled to below 30 ℃, with dull and stereotyped dicing machine blank.
The above-mentioned particle that cuts, through the granulation of SJ-30/25 forcing machine, each section of forcing machine temperature distribution is as follows:
Reinforced 1 section 2 sections 3 sections 4 sections head
80℃ 100℃ 120℃ 140℃ 150℃
60 rev/mins of extruded velocities, cooling and dicing is gone into bag through the package encapsulation that is up to the standards, and gets qualified product.
Testing conditions, 175 ℃, 15 minutes, the 18.0Mpa lower sheeting, the thick 1-2 millimeter of sheet is tested it by related standards.
The used abbreviation table look-up of the present invention
EPDM: terpolymer EP rubber
EVA: ethylene-vinyl acetate copolymer
CSPE: chlorosulfonated polyethylene rubber
DCP: dicumyl peroxide
TRA: bis-pentamethylenethiuram tetrasulfide
DM: dibenzothiazyl disulfide
1010: four [3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester
DOP: dioctyl phthalate (DOP)
Mgo: magnesium oxide
Pbo: plumbous oxide
Claims (3)
1, a kind of semiconductive polyolefine as external shielding material of cable is characterized in that its formula range is as follows:
Base resin: terpolymer EP rubber
Or ethylene-vinyl acetate copolymer 10-30 part (weight)
The modified resin chloroprene rubber
Or chlorosulfonated polyethylene rubber 70-90 part (weight)
Shawinigan black 15-25 part (weight)
Vulcanization system 18-23 part (weight)
Oxidation inhibitor four [3-(3 ', 5 '-di-t-butyl
-4-hydroxy phenyl) propionic acid] pentaerythritol ester＜0.5 part (weight)
Stearic acid+white oil 4-6 part (weight)
Dioctyl phthalate (DOP) 10-15 part (weight)
Vulcanization system in the above-mentioned semiconductive polyolefine as external shielding material of cable prescription is polyvalent alcohol vulcanization system or metal oxide vulcanization system, and its prescription is as follows:
(1) polyvalent alcohol fluidisation system:
10 parts of tetramethylolmethanes (weight part)
10 parts in magnesium oxide
0.3 part of dicumyl peroxide
(2) metal oxide vulcanization system
10 parts in magnesium oxide (weight part)
20 parts in plumbous oxide
2 parts of bis-pentamethylenethiuram tetrasulfides
0.5 part of dibenzothiazyl disulfide
2, a kind of method for making of semiconductive polyolefine as external shielding material of cable is characterized in that its processing step is:
(1), earlier modified resin chloroprene rubber or sulfonated polyethylene rubber are opened refining with double roller plastic-making device, the control roller temperature is no more than 50 ℃, and the time is no more than 15 minutes, plasticizing evenly, after logical six times of the book, it is standby to pull into thickness 1-1.5 millimeter sheet material;
(2), the weighing of base resin and other additives is mixed and mediate,
A, when selecting terpolymer EP rubber for use, still need to mould with two roller mill refinings earlier, the control roller temperature is no more than 50 ℃, time is no more than 15 minutes, adds then that modified resin is mixing to add other components more successively, adds while open refining, controlled temperature is no more than 90 ℃, thin-pass five times pulls into the sheet material of thickness 1-1.5 mm thick, is cooled to 30 ℃ and delivers to dull and stereotyped dicing machine pelletizing;
B, to select ethylene-vinyl acetate copolymer resin for use be base resin; then add component with other; mixing kneading in the high speed kneader mixed 30 minutes, and the material temperature is no more than 140 ℃; blowing; when being cooled to 90 ℃, mixing with modified resin again, evenly pelletizing on dull and stereotyped dicing machine again after the cooling; the particle that dull and stereotyped dicing machine is cut out plastifies granulation again through extruding granulator.
3, the method for making of semiconductive polyolefine as external shielding material of cable according to claim 2 is characterized in that describedly plastifying granulation with tablets press, the single screw extruder pelletizer L/D=25/1 that selects for use, and the control of each section temperature is as follows;
Charging opening
1 section 2 sections 3 sections 4 sections head
60-80℃ 90-110℃ 110-130 130-140℃ 140-150℃
60-80 rev/min of forcing machine speed, the water cooling pelletizing packs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97115236A CN1062879C (en) | 1997-08-22 | 1997-08-22 | Semiconductive polyolefine as external shielding material of cable |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97115236A CN1062879C (en) | 1997-08-22 | 1997-08-22 | Semiconductive polyolefine as external shielding material of cable |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1178807A CN1178807A (en) | 1998-04-15 |
| CN1062879C true CN1062879C (en) | 2001-03-07 |
Family
ID=5173226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97115236A Expired - Fee Related CN1062879C (en) | 1997-08-22 | 1997-08-22 | Semiconductive polyolefine as external shielding material of cable |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351521A (en) * | 2013-06-19 | 2013-10-16 | 安徽电缆股份有限公司 | Polyphenylene ether and EVA composite cable material and preparation method thereof |
| CN103980601B (en) * | 2014-01-23 | 2016-05-11 | 安徽华源电缆集团有限公司 | A kind of flame-proof anti-aging cable jacket material |
| CN107000257B (en) | 2014-12-04 | 2019-10-11 | 巴塞尔聚烯烃股份有限公司 | The method for being used to prepare polyolefin composition |
| CN105885141A (en) * | 2016-05-20 | 2016-08-24 | 安徽德源电缆集团有限公司 | Ozone-resistant cable sheath material and production method thereof |
| CN108182992A (en) * | 2016-12-08 | 2018-06-19 | 王士勇 | A kind of fire-retardant frequency-conversion power cable of mesolow |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3846371A (en) * | 1973-04-09 | 1974-11-05 | Du Pont | Masterbatching elastomer blends |
| US5576401A (en) * | 1993-06-30 | 1996-11-19 | Bayer Aktiengesellschaft | Process for the production of gel-free ethylene/vinyl acetate copolymers with a high content of copolymerized vinyl acetate and a high mooney viscosity |
-
1997
- 1997-08-22 CN CN97115236A patent/CN1062879C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3846371A (en) * | 1973-04-09 | 1974-11-05 | Du Pont | Masterbatching elastomer blends |
| US5576401A (en) * | 1993-06-30 | 1996-11-19 | Bayer Aktiengesellschaft | Process for the production of gel-free ethylene/vinyl acetate copolymers with a high content of copolymerized vinyl acetate and a high mooney viscosity |
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| Publication number | Publication date |
|---|---|
| CN1178807A (en) | 1998-04-15 |
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