CN103122097A - Thermoplastic low-smoke halogen-free flame-retardant environment-friendly sheath material for power cables and preparation method thereof - Google Patents
Thermoplastic low-smoke halogen-free flame-retardant environment-friendly sheath material for power cables and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a thermoplastic low-smoke halogen-free flame-retardant environment-friendly sheath material for power cables and a preparation method thereof. The thermoplastic low-smoke halogen-free flame-retardant environment-friendly sheath material for power cables comprises the following components in parts by weight: 60-80 parts of EVA (ethylene-vinyl acetate), 20-30 parts of HDPE (high-density polyethylene), 10-15 parts of EPDM (ethylene-propylene-diene monomer), 15-25 parts of compatiblizing agent, 100-150 parts of halogen-free flame retardant, 0.5-1 part of antioxidant 1035, 0.5-1 part of antioxidant DSTP, 1-2 parts of ethylene bis stearamide, 3-5 parts of DCP (dicumyl peroxide), 2-4 parts of zinc oxide, 1-2 parts of calcium stearate, 10-20 parts of dimethyl methyl phosphonate, 30-40 parts of nano kaolin, 2-3 parts of stearic acid and 0.5-1 part of isopropyl tri(dioctylpyrophosphate)titanate. The sheath material disclosed by the invention has the advantages of excellent physical and mechanical properties, excellent flame retardancy, favorable high/low temperature resistance, favorable oil resistance, favorable solvent resistance, favorable wear resistance, favorable ozone resistance, favorable aging resistance, high flexibility, crack resistance and the like, is very durable, environment-friendly and pollution-free, and can completely satisfy the requirements for modern power cables.
Description
Technical field
The present invention relates to a kind of power cable sheath material, be specifically related to a kind of power cable thermoplastic low-smoke halogen-free flame-resistant environment-friendly type sheath material and preparation method thereof.
Background technology
Along with the appearance of the ROHS of European Union and REACH environmental regulation and the needs of public safety, low-smoke halide-free fireproof composite polyolefine material substitutes PVC extensively and is widely used in the fields such as high-speed railway, urban track traffic and automobile, naval vessel, Nuclear power plants, Highrise buildings, optical communication, mobile communication base station field of cables at present.
Low-smoke non-halogen flame-retardant polyene cable jacket material is a kind of environmentally friendly machine, developing this class high-performance flame-retardant material is an important topic of flame-retarded technology, it is also a difficult point, because this flame-retardant system generally adopts hydrated inorganic filler as fire retardant, although this based flame retardant is nontoxic, low cigarette, its flame retarding efficiency is low, needs larger loading level just can reach high flame resistance, can cause like this reduction of mechanical property and the processing characteristics of material, especially comparatively serious on the latter's impact.The low-smoke halide-free fireproof composite polyolefine material of filling as height is easy to cracking, and this is the critical defect of cable product, has had a strong impact on cable work-ing life, has caused very large loss also for cable manufacturer.So be badly in need of a kind of cracking resistance low-smoke and halogen-free flame retardant polyolefin jacket material of exploitation.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, the power cable that a kind of cracking resistance with reliable use properties is provided is with thermoplastic low-smoke halogen-free flame-resistant environment-friendly type sheath material and preparation method thereof, reaches that oil resistant, heat-resisting, soft cracking resistance, screen resilience are good, the over-all propertieies such as anti-solvent, cold-resistant and low smoke high flame retardant.
The technical solution used in the present invention is as follows:
Power cable thermoplastic low-smoke halogen-free flame-resistant environment-friendly type sheath material, wherein each composition and weight part thereof are:
EVA 60-80
HDPE 20-30
EPDM 10-15
Compatilizer 15-25
Halogen-free flame retardants 100-150
Oxidation inhibitor 1035 0.5-1
Oxidation inhibitor DSTP 0.5-1
Ethylene bis stearamide 1-2
DCP 3-5
Zinc oxide 2-4
Calcium stearate 1-2
Dimethyl methyl phosphonate 10-20
Nano kaoline 30-40
Stearic acid 2-3
Sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester 0.5-1.
Preferably, power cable thermoplastic low-smoke halogen-free flame-resistant environment-friendly type sheath material, wherein each composition and weight part thereof are:
EVA 70
HDPE 20
EPDM 10
Compatilizer 20
Halogen-free flame retardants 130
Oxidation inhibitor 1,035 1
Oxidation inhibitor DSTP 0.5
Ethylene bis stearamide 1.5
DCP 4
Zinc oxide 3
Calcium stearate 1
Dimethyl methyl phosphonate 15
Nano kaoline 35
Stearic acid 2
Sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester 0.8.
In described EVA, VA content is 25-30%.
Described compatilizer is maleic anhydride graft EVA.
Described halogen-free flame retardants is take modified magnesium hydroxide as fire retardant, and microcapsule red phosphorus and melamine cyanurate are synergistic flame retardant, and wherein the weight ratio of modified magnesium hydroxide, microcapsule red phosphorus and melamine cyanurate is 40-50:1-2:1-2.
described modified magnesium hydroxide is made by following methods: magnesium hydroxide is dried by the fire 4-6h under 110-120 ℃, add distilled water to magnesium hydrate powder, make magnesium hydroxide pulp quality mark remain on 5-8%, being placed in thermostat water bath heats, the limit heating edge stirs by high shearing mixing emulsor, rotating speed is 4000-5000r/min, when temperature reaches 40-50 ℃, add the Silane coupling agent KH550 aqueous solution that is equivalent to magnesium hydrate powder weight 10-15%, Silane coupling agent KH550 and distilled water mass ratio are 1:10, continue to stir l-2h, suction filtration, dry at 105-115 ℃ of temperature, ground the 200-300 sieve, namely get modified magnesium hydroxide.
Being made by following methods of described microcapsule red phosphorus: (1) adds 10-15 part trimeric cyanamide, 180-200 part massfraction in the reactor is 37% formaldehyde solution, the rear 10-15% of the using sodium hydrogen carbonate solution that stirs is regulated pH value to 8.5-9.0, heating in water bath is to 70-80 ℃, speed constant temperature with 2500-3000rpm stirs 25-30min, and getting clear solution is the terpolycyantoamino-formaldehyde resin pre-polymer solution; (2) getting 2-4 part red phosphorus, 40-50 part distilled water, 6-8 part massfraction is 10% polyvinyl alcohol solution, stir 20-30min, then add 1-1.5 part emulsifier op-10 and 10-15 part terpolycyantoamino-formaldehyde resin pre-polymer solution, transfer PH to 5.5-6.0, stir 1-2h in 45-50 ℃ of water bath with thermostatic control, adding 3-5 part massfraction is 10% polyvinyl alcohol solution again, stirs 3-4min, transfers PH to 8.0-9.0, suction filtration, washing is dried 1-2h under 100-110 ℃, namely get microcapsule red phosphorus.
The power cable preparation method of thermoplastic low-smoke halogen-free flame-resistant environment-friendly type sheath material is characterized in that comprising the following steps:
(1) will add in high-speed mixer with stearic acid, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester after the nano kaoline drying, speed with 500-800rpm under 95-105 ℃ mixes 20-30min, then the nano kaoline with surface modification drops in the two forcing machines of screw rod, add again EVA, forcing machine melt zone temperature is controlled at 140-175 ℃, melt blending 10-20min under the rotating speed of 400-600r/min, then extruding pelletization, namely get the modified EVA particle;
(2) HDPE, EPDM, compatilizer and the above-mentioned modified EVA particle that makes are joined mixing 10-20min on mixing roll, temperature is 105-110 ℃, obtains rubber unvulcanizate;
(3) the above-mentioned rubber unvulcanizate that makes and calcium stearate, zinc oxide, halogen-free flame retardants are dropped in Banbury mixer, add dimethyl methyl phosphonate, ethylene bis stearamide to continue mixing 4-5min after mixing 2-3min, add at last the mixing 1-2min of remaining various auxiliary agent, Banbury mixer rotating speed 150-200r/min, temperature is controlled at 90-105 ℃;
(4) blended stock that obtains after banburying is conveyed into screw extrusion press through the bipyramid shearing and extrudes processing, body temperature when extruding is 140 ± 10 ℃, head temperature is 110 ± 10 ℃, vulcanize on vulcanizing press after extruding, at 160-180 ℃ of lower hot pressing 8-10min, the normal temperature 4-6min that colds pressing, sulfide stress 6-10MPa, going out linear velocity is 12-15m/min.
Beneficial effect of the present invention:
The present invention is by to magnesium hydroxide surface modifying, and and microcapsule red phosphorus, the fire-retardant synergistic Composite of two kinds of materials of melamine cyanurate, improved its flame retarding efficiency, and do not affected physical and mechanical properties, processing characteristics and the electric property of sheath material.The modified EVA particle that the present invention makes has improved the resistance to air loss of EVA, and delaying retrogradation hinders heat and enters rubber inner layer, thereby improves the heat aging property of sheath.The sheath material that the present invention produces not only has excellent physical and mechanical properties and flame retardant properties, and also have simultaneously advantages such as good resistant of high or low temperature, oil resistant, anti-solvent, wear resistance, anti-ozone, ageing-resistant, soft cracking resistance, durable in use, environment friendly and pollution-free, can satisfy the requirement of modern electric cable fully.
Embodiment
Power cable thermoplastic low-smoke halogen-free flame-resistant environment-friendly type sheath material, wherein each composition and weight part thereof are:
VA content is 70 parts of 28% EVA
20 parts of HDPE
10 parts of EPDM
20 parts of maleic anhydride graft EVA
120 parts of modified magnesium hydroxides
6 parts of microcapsule red phosphorus
4 parts of melamine cyanurates
1,035 1 parts, oxidation inhibitor
0.5 part of oxidation inhibitor DSTP
1.5 parts of ethylene bis stearamides
4 parts of DCP
3 parts, zinc oxide
1 part of calcium stearate
15 parts of dimethyl methyl phosphonates
35 parts of nano kaolines
2 parts of stearic acid
0.8 part of sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester.
wherein, described modified magnesium hydroxide is made by following methods: magnesium hydroxide is dried by the fire 5h under 115 ℃, add distilled water to magnesium hydrate powder, make magnesium hydroxide pulp quality mark remain on 6%, being placed in thermostat water bath heats, the limit heating edge stirs by high shearing mixing emulsor, rotating speed is 5000r/min, when temperature reaches 45 ℃, add the Silane coupling agent KH550 aqueous solution that is equivalent to magnesium hydrate powder weight 12%, Silane coupling agent KH550 and distilled water mass ratio are 1:10, continue to stir lh, suction filtration, dry at 110 ℃ of temperature, ground 300 sieves, namely get modified magnesium hydroxide.
Being made by following methods of described microcapsule red phosphorus: (1) adds 10 parts of trimeric cyanamides, 180 parts of massfractions in the reactor is 37% formaldehyde solution, rear use 10% sodium hydrogen carbonate solution that stirs is regulated pH value to 9.0, heating in water bath to 80 ℃, speed constant temperature with 3000rpm stirs 25min, and getting clear solution is the terpolycyantoamino-formaldehyde resin pre-polymer solution; (2) getting 3 parts of red phosphorus, 45 parts of distilled water, 6 parts of massfractions is 10% polyvinyl alcohol solution, stir 30min, then add 1.2 parts of emulsifier op-10s and 10 parts of terpolycyantoamino-formaldehyde resin pre-polymer solutions, transfer PH to 6.0, stir 1.5h in 50 ℃ of waters bath with thermostatic control, adding 3 parts of massfractions is 10% polyvinyl alcohol solution again, stirs 4min, transfers PH to 8.5, suction filtration, washing is dried 1h under 110 ℃, namely get microcapsule red phosphorus.
The power cable preparation method of thermoplastic low-smoke halogen-free flame-resistant environment-friendly type sheath material is characterized in that comprising the following steps:
(1) will add in high-speed mixer with stearic acid, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester after the nano kaoline drying, speed with 600rpm under 105 ℃ mixes 20min, then the nano kaoline with surface modification drops in the two forcing machines of screw rod, add again EVA, forcing machine melt zone temperature is controlled at 160 ℃, melt blending 15min under the rotating speed of 600r/min, then extruding pelletization, namely get the modified EVA particle;
(2) HDPE, EPDM, compatilizer and the above-mentioned modified EVA particle that makes are joined mixing 20min on mixing roll, temperature is 105 ℃, obtains rubber unvulcanizate;
(3) the above-mentioned rubber unvulcanizate that makes and calcium stearate, zinc oxide, halogen-free flame retardants are dropped in Banbury mixer, add dimethyl methyl phosphonate, ethylene bis stearamide to continue mixing 4min after mixing 3min, add at last the mixing 1min of remaining various auxiliary agent, Banbury mixer rotating speed 200r/min, temperature is controlled at 95 ℃;
(4) blended stock that obtains after banburying is conveyed into screw extrusion press through the bipyramid shearing and extrudes processing, body temperature when extruding is 145 ℃, head temperature is 110 ℃, vulcanize on vulcanizing press after extruding, at 170 ℃ of lower hot pressing 8min, the normal temperature 5min that colds pressing, sulfide stress 10MPa, going out linear velocity is 14m/min.
The main performance index of the sheath material that the present invention produces such as following table:
| Sequence number | Performance project | Unit | Technical indicator |
| 1 | Tensile strength | N/mm 2 | ≥10.0 |
| 2 | Elongation at break | % | ≥250 |
| 3 | The aging rear tensile strength velocity of variation of 120 ℃ * 168h | % | ±30 |
| 4 | The maximum velocity of variation of the aging rear elongation at break of 120 ℃ * 168h | % | ±30 |
| 5 | The maximum velocity of variation of 100 ℃ * 24h of immersion oil posttension intensity | % | -30 |
| 6 | The maximum velocity of variation of elongation at break after 100 ℃ * 24h of immersion oil | % | -30 |
| 7 | Heat is extended elongation under load | % | ≤175 |
| 8 | Heat is extended permanent elongation | % | ≤15 |
| 9 | Single vertical combustion (distance between starting point is partly gone up in upper bracket lower edge and charing) | mm | ＞50 |
| 10 | Single vertical combustion (burning extends downward apart from distance between the upper bracket lower edge) | mm | ≤540 |
| 11 | Burning smoke density (transmittance) | % | ≥80 |
| 12 | Evolved gas pH value during burning | - | ≥4.3 |
| 13 | The specific conductivity of evolved gas during burning | μS/mm | ≥10 |
| 14 | Burning halogen chlorination hydrogen release amount | % | ≤0.5 |
| 15 | Poison exponent during burning | - | ≤5 |
Claims (8)
1. power cable with thermoplastic low-smoke halogen-free flame-resistant environment-friendly type sheath material, is characterized in that, wherein each composition and weight part thereof are:
EVA 60-80
HDPE 20-30
EPDM 10-15
Compatilizer 15-25
Halogen-free flame retardants 100-150
Oxidation inhibitor 1035 0.5-1
Oxidation inhibitor DSTP 0.5-1
Ethylene bis stearamide 1-2
DCP 3-5
Zinc oxide 2-4
Calcium stearate 1-2
Dimethyl methyl phosphonate 10-20
Nano kaoline 30-40
Stearic acid 2-3
Sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester 0.5-1.
2. power cable with thermoplastic low-smoke halogen-free flame-resistant environment-friendly type sheath material, is characterized in that, wherein each composition and weight part thereof are:
EVA 70
HDPE 20
EPDM 10
Compatilizer 20
Halogen-free flame retardants 130
Oxidation inhibitor 1,035 1
Oxidation inhibitor DSTP 0.5
Ethylene bis stearamide 1.5
DCP 4
Zinc oxide 3
Calcium stearate 1
Dimethyl methyl phosphonate 15
Nano kaoline 35
Stearic acid 2
Sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester 0.8.
3. power cable according to claim 1 with thermoplastic low-smoke halogen-free flame-resistant environment-friendly type sheath material, is characterized in that, in described EVA, VA content is 25-30%.
4. power cable according to claim 1 with thermoplastic low-smoke halogen-free flame-resistant environment-friendly type sheath material, is characterized in that, described compatilizer is maleic anhydride graft EVA.
5. power cable according to claim 1 is with thermoplastic low-smoke halogen-free flame-resistant environment-friendly type sheath material, it is characterized in that, described halogen-free flame retardants is take modified magnesium hydroxide as fire retardant, microcapsule red phosphorus and melamine cyanurate are synergistic flame retardant, and wherein the weight ratio of modified magnesium hydroxide, microcapsule red phosphorus and melamine cyanurate is 40-50:1-2:1-2.
6. power cable according to claim 5 is with thermoplastic low-smoke halogen-free flame-resistant environment-friendly type sheath material, it is characterized in that, described modified magnesium hydroxide is made by following methods: magnesium hydroxide is dried by the fire 4-6h under 110-120 ℃, add distilled water to magnesium hydrate powder, make magnesium hydroxide pulp quality mark remain on 5-8%, being placed in thermostat water bath heats, the limit heating edge stirs by high shearing mixing emulsor, rotating speed is 4000-5000r/min, when temperature reaches 40-50 ℃, add the Silane coupling agent KH550 aqueous solution that is equivalent to magnesium hydrate powder weight 10-15%, Silane coupling agent KH550 and distilled water mass ratio are 1:10, continue to stir l-2h, suction filtration, dry at 105-115 ℃ of temperature, ground the 200-300 sieve, namely get modified magnesium hydroxide.
7. power cable according to claim 5 is with thermoplastic low-smoke halogen-free flame-resistant environment-friendly type sheath material, it is characterized in that, being made by following methods of described microcapsule red phosphorus: (1) adds 10-15 part trimeric cyanamide, 180-200 part massfraction in the reactor is 37% formaldehyde solution, the rear 10-15% of the using sodium hydrogen carbonate solution that stirs is regulated pH value to 8.5-9.0, heating in water bath is to 70-80 ℃, speed constant temperature with 2500-3000rpm stirs 25-30min, and getting clear solution is the terpolycyantoamino-formaldehyde resin pre-polymer solution; (2) getting 2-4 part red phosphorus, 40-50 part distilled water, 6-8 part massfraction is 10% polyvinyl alcohol solution, stir 20-30min, then add 1-1.5 part emulsifier op-10 and 10-15 part terpolycyantoamino-formaldehyde resin pre-polymer solution, transfer PH to 5.5-6.0, stir 1-2h in 45-50 ℃ of water bath with thermostatic control, adding 3-5 part massfraction is 10% polyvinyl alcohol solution again, stirs 3-4min, transfers PH to 8.0-9.0, suction filtration, washing is dried 1-2h under 100-110 ℃, namely get microcapsule red phosphorus.
8. power cable as claimed in claim 1 with the preparation method of thermoplastic low-smoke halogen-free flame-resistant environment-friendly type sheath material, is characterized in that comprising the following steps:
(1) will add in high-speed mixer with stearic acid, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester after the nano kaoline drying, speed with 500-800rpm under 95-105 ℃ mixes 20-30min, then the nano kaoline with surface modification drops in the two forcing machines of screw rod, add again EVA, forcing machine melt zone temperature is controlled at 140-175 ℃, melt blending 10-20min under the rotating speed of 400-600r/min, then extruding pelletization, namely get the modified EVA particle;
(2) HDPE, EPDM, compatilizer and the above-mentioned modified EVA particle that makes are joined mixing 10-20min on mixing roll, temperature is 105-110 ℃, obtains rubber unvulcanizate;
(3) the above-mentioned rubber unvulcanizate that makes and calcium stearate, zinc oxide, halogen-free flame retardants are dropped in Banbury mixer, add dimethyl methyl phosphonate, ethylene bis stearamide to continue mixing 4-5min after mixing 2-3min, add at last the mixing 1-2min of remaining various auxiliary agent, Banbury mixer rotating speed 150-200r/min, temperature is controlled at 90-105 ℃;
(4) blended stock that obtains after banburying is conveyed into screw extrusion press through the bipyramid shearing and extrudes processing, body temperature when extruding is 140 ± 10 ℃, head temperature is 110 ± 10 ℃, vulcanize on vulcanizing press after extruding, at 160-180 ℃ of lower hot pressing 8-10min, the normal temperature 4-6min that colds pressing, sulfide stress 6-10MPa, going out linear velocity is 12-15m/min.
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| CN201310022614.5A CN103122097B (en) | 2013-01-22 | 2013-01-22 | Power cable Thermoplastic low-smoke halogen-free flame-retardant environment-friendlysheath sheath material and preparation method thereof |
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| CN201310022614.5A CN103122097B (en) | 2013-01-22 | 2013-01-22 | Power cable Thermoplastic low-smoke halogen-free flame-retardant environment-friendlysheath sheath material and preparation method thereof |
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Denomination of invention: Thermoplastic low-smoke halogen-free flame-retardant environment-friendly sheath material for power cables and preparation method thereof Effective date of registration: 20191113 Granted publication date: 20160224 Pledgee: Anhui inaction rural commercial bank Limited by Share Ltd Pledgor: Anhui Huajin Cable Group Co., Ltd. Registration number: Y2019340000190 |
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