CN103122097B - Power cable Thermoplastic low-smoke halogen-free flame-retardant environment-friendlysheath sheath material and preparation method thereof - Google Patents
Power cable Thermoplastic low-smoke halogen-free flame-retardant environment-friendlysheath sheath material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of power cable Thermoplastic low-smoke halogen-free flame-retardant environment-friendlysheath sheath material and preparation method thereof, wherein do are each composition and weight part thereof: 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, DCP3-5, 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.The sheath material that the present invention produces not only has excellent physical and mechanical properties and flame retardant properties, and also there is the advantages such as good resistant of high or low temperature, oil resistant, solvent resistant, wear resistance, resistance to ozone, ageing-resistant, soft cracking resistance simultaneously, durable in use, environment friendly and pollution-free, the requirement of modern electric cable can be met completely.
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-retardant environment-friendlysheath sheath material and preparation method thereof.
Background technology
At present along with European Union ROHS and the appearance of REACH environmental regulation and the needs of public safety, low-smoke halide-free fireproof composite polyolefine material substitutes PVC extensively and be 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 in field of cables.
Low-smoke non-halogen flame-retardant polyene cable jacket material is a kind of environmentally friendly machine, develop the important topic that this kind of high-performance flame-retardant material is flame-retarded technology, also be a difficult point, because this flame-retardant system generally adopts hydrated inorganic filler as fire retardant, although nontoxic, the low cigarette of this based flame retardant, its flame retarding efficiency is low, needs larger loading level just can reach high flame resistance, the mechanical property of material and the reduction of processing characteristics can be caused like this, especially comparatively serious on the impact of the latter.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, causes very large loss also to 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, a kind of power cable Thermoplastic low-smoke halogen-free flame-retardant environment-friendlysheath sheath material with the cracking resistance of reliable use properties and preparation method thereof is provided, reaches that oil resistant, heat-resisting, soft cracking resistance, screen resilience are good, the over-all properties such as solvent resistant, 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-retardant environment-friendlysheath sheath material, wherein each composition and weight part thereof are:
EVA60-80
HDPE20-30
EPDM10-15
Compatilizer 15-25
Halogen-free flame retardants 100-150
Oxidation inhibitor 10350.5-1
Oxidation inhibitor DSTP0.5-1
Ethylene bis stearamide 1-2
DCP3-5
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-retardant environment-friendlysheath sheath material, wherein each composition and weight part thereof are:
EVA70
HDPE20
EPDM10
Compatilizer 20
Halogen-free flame retardants 130
Oxidation inhibitor 10351
Oxidation inhibitor DSTP0.5
Ethylene bis stearamide 1.5
DCP4
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 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 obtained by following methods: magnesium hydroxide is dried 4-6h at 110-120 DEG C, distilled water is added to magnesium hydrate powder, magnesium hydroxide slurry massfraction is made to remain on 5-8%, be placed in thermostat water bath to heat, limit heating edge is stirred by high shearing mixing emulsor, rotating speed is 4000-5000r/min, when temperature reaches 40-50 DEG C, add the Silane coupling agent KH550 aqueous solution being 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 DEG C of temperature, ground 200-300 sieve, obtain modified magnesium hydroxide.
Being obtained by following methods of described microcapsule red phosphorus: (1) adds 10-15 part trimeric cyanamide in reactor, 180-200 part massfraction is the formaldehyde solution of 37%, use 10-15% sodium hydrogen carbonate solution adjust ph to 8.5-9.0 after stirring, heating in water bath is to 70-80 DEG C, stir 25-30min with the speed constant temperature of 2500-3000rpm, obtain clear solution and terpolycyantoamino-formaldehyde resin pre-polymer solution; (2) get 2-4 part red phosphorus, 40-50 part distilled water, 6-8 part massfraction be the polyvinyl alcohol solution of 10%, stir 20-30min, then add 1-1.5 part emulsifier op-10 and 10-15 part terpolycyantoamino-formaldehyde resin pre-polymer solution, adjust pH to 5.5-6.0,1-2h is stirred in 45-50 DEG C of water bath with thermostatic control, adding 3-5 part massfraction is again the polyvinyl alcohol solution of 10%, stirs 3-4min, adjusts pH to 8.0-9.0, suction filtration, washing, dries 1-2h, obtains microcapsule red phosphorus at 100-110 DEG C.
The preparation method of power cable Thermoplastic low-smoke halogen-free flame-retardant environment-friendlysheath sheath material, is characterized in that comprising the following steps:
(1) add in high-speed mixer by after nano kaoline drying with stearic acid, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, speed with 500-800rpm at 95-105 DEG C is uniformly mixed 20-30min, then the nano kaoline of surface modification is dropped in the two forcing machine of screw rod, add EVA again, forcing machine melt zone temperature controls at 140-175 DEG C, melt blending 10-20min, then extruding pelletization under the rotating speed of 400-600r/min, obtain modified EVA particle;
(2) HDPE, EPDM, compatilizer and above-mentioned obtained modified EVA particle are joined mixing 10-20min on mixing roll, temperature is 105-110 DEG C, obtains rubber unvulcanizate;
(3) above-mentioned obtained rubber unvulcanizate and calcium stearate, zinc oxide, halogen-free flame retardants are dropped in Banbury mixer, add dimethyl methyl phosphonate after mixing 2-3min, ethylene bis stearamide continues mixing 4-5min, finally add the mixing 1-2min of remaining various auxiliary agent, Banbury mixer rotating speed 150-200r/min, temperature controls at 90-105 DEG C;
(4) blended stock obtained after banburying is conveyed into screw extrusion press through bipyramid shearing and extrudes processing, body temperature when extruding is 140 ± 10 DEG C, head temperature is 110 ± 10 DEG C, on vulcanizing press, sulfuration is carried out after extruding, hot pressing 8-10min at 160-180 DEG C, normal temperature is colded pressing 4-6min, sulfide stress 6-10MPa, and going out linear velocity is 12-15m/min.
Beneficial effect of the present invention:
The present invention by magnesium hydroxide surface modifying, and and microcapsule red phosphorus, the fire-retardant synergistic Composite of melamine cyanurate two kinds of materials, improve its flame retarding efficiency, and do not affect the physical and mechanical properties of sheath material, processing characteristics and electric property.The modified EVA particle that the present invention obtains improves the resistance to air loss of EVA, delaying retrogradation, hinders heat to enter rubber inner layer, thus 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 there is the advantages such as good resistant of high or low temperature, oil resistant, solvent resistant, wear resistance, resistance to ozone, ageing-resistant, soft cracking resistance simultaneously, durable in use, environment friendly and pollution-free, the requirement of modern electric cable can be met completely.
Embodiment
Power cable Thermoplastic low-smoke halogen-free flame-retardant environment-friendlysheath sheath material, wherein each composition and weight part thereof are:
VA content is EVA70 part of 28%
HDPE20 part
EPDM10 part
Maleic anhydride graft EVA20 part
Modified magnesium hydroxide 120 parts
Microcapsule red phosphorus 6 parts
Melamine cyanurate 4 parts
10351 parts, oxidation inhibitor
Oxidation inhibitor DSTP0.5 part
Ethylene bis stearamide 1.5 parts
DCP4 part
3 parts, zinc oxide
Calcium stearate 1 part
Dimethyl methyl phosphonate 15 parts
Nano kaoline 35 parts
Stearic acid 2 parts
Sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester 0.8 part.
Wherein, described modified magnesium hydroxide is obtained by following methods: magnesium hydroxide is dried 5h at 115 DEG C, distilled water is added to magnesium hydrate powder, magnesium hydroxide slurry massfraction is made to remain on 6%, be placed in thermostat water bath to heat, limit heating edge is stirred by high shearing mixing emulsor, rotating speed is 5000r/min, when temperature reaches 45 DEG C, add the Silane coupling agent KH550 aqueous solution being 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 DEG C of temperature, ground 300 sieves, obtain modified magnesium hydroxide.
Being obtained by following methods of described microcapsule red phosphorus: (1) adds 10 parts of trimeric cyanamides in reactor, 180 parts of massfractions are the formaldehyde solution of 37%, by 10% sodium hydrogen carbonate solution adjust ph to 9.0 after stirring, heating in water bath to 80 DEG C, stir 25min with the speed constant temperature of 3000rpm, obtain clear solution and terpolycyantoamino-formaldehyde resin pre-polymer solution; (2) get 3 parts of red phosphorus, 45 parts of distilled water, 6 parts of massfractions are the polyvinyl alcohol solution of 10%, stir 30min, then add 1.2 parts of emulsifier op-10s and 10 parts of terpolycyantoamino-formaldehyde resin pre-polymer solutions, adjust pH to 6.0,1.5h is stirred in 50 DEG C of waters bath with thermostatic control, adding 3 parts of massfractions is again the polyvinyl alcohol solution of 10%, stirs 4min, adjusts pH to 8.5, suction filtration, washing, dries 1h, obtains microcapsule red phosphorus at 110 DEG C.
The preparation method of power cable Thermoplastic low-smoke halogen-free flame-retardant environment-friendlysheath sheath material, is characterized in that comprising the following steps:
(1) add in high-speed mixer by after nano kaoline drying with stearic acid, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, speed with 600rpm at 105 DEG C is uniformly mixed 20min, then the nano kaoline of surface modification is dropped in the two forcing machine of screw rod, add EVA again, forcing machine melt zone temperature controls at 160 DEG C, melt blending 15min, then extruding pelletization under the rotating speed of 600r/min, obtain modified EVA particle;
(2) HDPE, EPDM, compatilizer and above-mentioned obtained modified EVA particle are joined mixing 20min on mixing roll, temperature is 105 DEG C, obtains rubber unvulcanizate;
(3) above-mentioned obtained rubber unvulcanizate and calcium stearate, zinc oxide, halogen-free flame retardants are dropped in Banbury mixer, add dimethyl methyl phosphonate after mixing 3min, ethylene bis stearamide continues mixing 4min, finally add the mixing 1min of remaining various auxiliary agent, Banbury mixer rotating speed 200r/min, temperature controls at 95 DEG C;
(4) blended stock obtained after banburying is conveyed into screw extrusion press through bipyramid shearing and extrudes processing, body temperature when extruding is 145 DEG C, head temperature is 110 DEG C, on vulcanizing press, sulfuration is carried out after extruding, hot pressing 8min at 170 DEG C, normal temperature is colded pressing 5min, sulfide stress 10MPa, and going out linear velocity is 14m/min.
The main performance index of the sheath material that the present invention produces is 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 variation in tensile strength of 120 DEG C × 168h | % | ±30 |
| 4 | The maximum velocity of variation of the aging rear elongation at break of 120 DEG C × 168h | % | ±30 |
| 5 | The maximum velocity of variation of immersion oil 100 DEG C × 24h posttension intensity | % | -30 |
| 6 | The maximum velocity of variation of elongation at break after immersion oil 100 DEG C × 24h | % | -30 |
| 7 | Elongation under heat extension load | % | ≤175 |
| 8 | Heat extends permanent elongation | % | ≤15 |
| 9 | The single vertical burning spacing of starting point (on upper bracket lower edge and the charred portion) | mm | ＞50 |
| 10 | Single vertical burning (burning extends downward the spacing of distance 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 (4)
1. power cable Thermoplastic low-smoke halogen-free flame-retardant environment-friendlysheath sheath material, is characterized in that, wherein each composition and weight part thereof are:
EVA60-80
HDPE20-30
EPDM10-15
Compatilizer 15-25
Halogen-free flame retardants 100-150
Oxidation inhibitor 10350.5-1
Oxidation inhibitor DSTP0.5-1
Ethylene bis stearamide 1-2
DCP3-5
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;
Described halogen-free flame retardants 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 obtained by following methods: magnesium hydroxide is dried 4-6h at 110-120 DEG C, distilled water is added to magnesium hydrate powder, magnesium hydroxide slurry massfraction is made to remain on 5-8%, be placed in thermostat water bath to heat, limit heating edge is stirred by high shearing mixing emulsor, rotating speed is 4000-5000r/min, when temperature reaches 40-50 DEG C, add the Silane coupling agent KH550 aqueous solution being 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 DEG C of temperature, ground 200-300 sieve, obtain modified magnesium hydroxide,
Being obtained by following methods of described microcapsule red phosphorus:
(1) in reactor, add 10-15 part trimeric cyanamide, 180-200 part massfraction is the formaldehyde solution of 37%, use 10-15% sodium hydrogen carbonate solution adjust ph to 8.5-9.0 after stirring, heating in water bath is to 70-80 DEG C, stir 25-30min with the speed constant temperature of 2500-3000rpm, obtain clear solution and terpolycyantoamino-formaldehyde resin pre-polymer solution;
(2) get 2-4 part red phosphorus, 40-50 part distilled water, 6-8 part massfraction be the polyvinyl alcohol solution of 10%, stir 20-30min, then add 1-1.5 part emulsifier op-10 and 10-15 part terpolycyantoamino-formaldehyde resin pre-polymer solution, adjust pH to 5.5-6.0,1-2h is stirred in 45-50 DEG C of water bath with thermostatic control, adding 3-5 part massfraction is again the polyvinyl alcohol solution of 10%, stirs 3-4min, adjusts pH to 8.0-9.0, suction filtration, washing, dries 1-2h, obtains microcapsule red phosphorus at 100-110 DEG C.
2. power cable Thermoplastic low-smoke halogen-free flame-retardant environment-friendlysheath sheath material according to claim 1, is characterized in that, in described EVA, VA content is 25-30%.
3. power cable Thermoplastic low-smoke halogen-free flame-retardant environment-friendlysheath sheath material according to claim 1, is characterized in that, described compatilizer is maleic anhydride graft EVA.
4. the preparation method of power cable Thermoplastic low-smoke halogen-free flame-retardant environment-friendlysheath sheath material as claimed in claim 1, is characterized in that comprising the following steps:
(1) add in high-speed mixer by after nano kaoline drying with stearic acid, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, speed with 500-800rpm at 95-105 DEG C is uniformly mixed 20-30min, then the nano kaoline of surface modification is dropped in the two forcing machine of screw rod, add EVA again, forcing machine melt zone temperature controls at 140-175 DEG C, melt blending 10-20min, then extruding pelletization under the rotating speed of 400-600r/min, obtain modified EVA particle;
(2) HDPE, EPDM, compatilizer and above-mentioned obtained modified EVA particle are joined mixing 10-20min on mixing roll, temperature is 105-110 DEG C, obtains rubber unvulcanizate;
(3) above-mentioned obtained rubber unvulcanizate and calcium stearate, zinc oxide, halogen-free flame retardants are dropped in Banbury mixer, add dimethyl methyl phosphonate after mixing 2-3min, ethylene bis stearamide continues mixing 4-5min, finally add the mixing 1-2min of remaining various auxiliary agent, Banbury mixer rotating speed 150-200r/min, temperature controls at 90-105 DEG C;
(4) blended stock obtained after banburying is conveyed into screw extrusion press through bipyramid shearing and extrudes processing, body temperature when extruding is 140 ± 10 DEG C, head temperature is 110 ± 10 DEG C, on vulcanizing press, sulfuration is carried out after extruding, hot pressing 8-10min at 160-180 DEG C, normal temperature is colded pressing 4-6min, sulfide stress 6-10MPa, and going out linear velocity is 12-15m/min.
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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 |