CN109679196A - A kind of preparation method of ceramic fireproof polyolefin - Google Patents
A kind of preparation method of ceramic fireproof polyolefin Download PDFInfo
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- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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Abstract
The invention belongs to fireproof field of material technology, a kind of preparation method of ceramic fireproof polyolefin is disclosed, preparing raw material includes polyolefine material, Vitrified powder, support filler and functional additive, and support filler is one or more of hydrophily fume colloidal silica, hydrophily precipitated silica, hydrophily high-purity ground quartz.The present invention makes fire-resistant polyolefin avoid the formation of melting hole during high temperature forms ceramic body by improved filler formulation and preparation method, and cable breakdown occurs, and obtains the fire-resistant polyolefin material of insulation performance, mechanical property and excellent fire retarding performance.
Description
Technical field
The present invention relates to a kind of refractory material, especially a kind of preparation method of ceramic fireproof polyolefin.
Background technique
Fire-resisting cable has defined fireproof performance, can guarantee that route continues stable operation one under flame condition
The section time, work normally electric system and whistle control system under flame condition.Currently, domestic and international fireproof cable master
There is the fireproof cable of magnesium oxide mineral insulated fireproof cable and Mica tape inorganic insulation.Mineral insulated cable
Though having good fireproof performance, manufacturing process is complicated, production cost is high, difficulty of construction is very high.Mica tape
Although fireproof cable work simple process, become fragile after mica tape high-temp combustion, it is resistance to by powder of detached easy after strenuous vibration
Fire is ineffective.Fire resistant belt construction is simple, easy to operate is made with Ceramic silicon rubber, can mass production, but with ceramic SiClx
Composite band higher cost made from rubber, using being restricted.Fire-resisting ceramic silicone rubber CABLE MATERIALS is needed by dedicated rubber
Rubber extruding machine squeezes out, and it also requires vulcanizing treatment is carried out by heating vulcanization process, thus technique is relative complex, the scope of application
It is restricted.
Low smoke halogen-free flame-retardant polyolefin wire cable material is a kind of common insulating properties CABLE MATERIALS, but in actual conditions, resistance
The line security of fire-fighting equipment can not be effectively protected in combustion cable in a fire, can only be before fire flashes over, and the short time is hindered
The fast propagation of flame, and flash over occur after must just rely on the effect of fire-resisting cable.Which results in set using existing production
Standby production ceramic polyolefin fire-resistant wire and cable, becomes a kind of selection of cable manufacturer.Chinese patent application
Announce a kind of ceramic polyolefine material and preparation method thereof in CN104558805A, raw material includes polyolefin, Vitrified powder and anti-
Oxygen agent, Vitrified powder include borax, ammonium borate, zinc borate and glass powder with low melting point and raw material commonly used in the art, the substance
As the fluxing agent at porcelain filling, enable can ceramic polyolefin " easy fired ", can ceramic at a lower temperature, obtain
The ceramic body of intensity centainly is obtained, preferably performance fire-proof function.But the substance can melt in the case where continuous high temperature
It shrinks, so that ceramic body is formed melting hole or crack defect, breakdown is be easy to cause in fire resisting test, insulation performance is deteriorated.Meanwhile
Contain more metal ion (Ka in glass powder with low melting point+、Na+Deng), the insulating properties of cable is also resulted in during melted by heating
It can reduce.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of preparation method of ceramic fireproof polyolefin, the ceramics
Chemoprevention fire fire-resistant polyolefin makes fire-resistant polyolefin during high temperature forms ceramic body by improved filler formulation and technique
Melting hole is avoided the formation of, and cable breakdown occurs, obtains the ceramics of insulation performance, mechanical property and excellent fire retarding performance
Change polyolefine material.
The technical solution adopted by the present invention is that:
A kind of preparation method of ceramic fireproof polyolefin, the ceramic fireproof polyolefin prepare raw material
By including polyolefine material, Vitrified powder, support filler and functional additive, the support filler is hydrophily vapor phase method hard charcoal
One or more of black, hydrophily precipitated silica, hydrophily high-purity ground quartz, the functional additive are in 200-
650 DEG C of decomposition obtain the compound of metal oxide;
The preparation method comprises the following steps:
Support filler is mixed into dispersion with functional additive, then mix with polyolefine material heat up after mixing, then squeeze
It is granulated out, obtains ceramic polyolefin master batch;
Ceramic polyolefin master batch is mixed with Vitrified powder to mixing after heating, using being kneaded plasticizing, squeeze out, fervent wind
It is cold, obtain ceramic fireproof polyolefin.
Preferably, in the preparation step of the ceramic polyolefin master batch heat up after mixing be warming up to 140~150 DEG C it is close
Refine 15-25min.
Preferably, it is described ceramic polyolefin master batch is mixed with Vitrified powder heating after mixing be to be warming up to 145~155 DEG C
Mixing 20-25min.
Preferably, the mixing plasticizing, extrusion, earnestly air-cooled pair formed in double screw extruder, single screw extrusion machine
It is carried out on rank extruding pelletization unit, the temperature setting of the double screw extruder are as follows: 120 DEG C of an area~130 DEG C, 130 DEG C of 2nd area
~135 DEG C, 135 DEG C~140 DEG C of 3rd area, 140 DEG C~150 DEG C of 4th area, 150~155 DEG C of 5th area, 150 DEG C of 6th area~155 DEG C, seven
150 DEG C~155 DEG C of area, 145 DEG C~150 DEG C of 8th area, single screw extrusion machine temperature setting are as follows: 120 DEG C of an area~130 DEG C, 2nd area
130 DEG C~135 DEG C, 130 DEG C~135 DEG C of 3rd area, 140~145 DEG C of the head temperature of single screw extrusion machine.
Preferably, the raw material further includes antioxidant, when the raw material includes antioxidant, the ceramic polyolefin master batch
Preparation be that filler will be supported to mix dispersion with functional additive, then mixed with polyolefine material, antioxidant, then be warming up to
140~150 DEG C of mixing 15-20min, obtain ceramic polyolefin master batch.
The polyolefine material is not specifically limited, preferably be selected from polyethylene (PE), polypropylene (PP), EP rubbers (EPR),
One or more of ethylene propylene diene rubber (EPDM), ethylene-vinyl acetate copolymer (EVA), ethene-alpha-olefin copolymer.
It is highly preferred that the polyolefine material is ethylene-vinyl acetate copolymer (EVA), melt flow rate (MFR) 1-
5g/10min (test condition is 190 DEG C, 2.16Kg, testing standard ASTMD1238), VA content 9-28%;Or it is described poly-
Olefin material is ethene-alpha-olefin copolymer, melt flow rate (MFR) be 1-5g/10min (test condition is 190 DEG C, 2.16Kg,
Testing standard is ASTMD1238), microcaloire softening point is more than or equal to 80 DEG C (testing standard ASTMD1525).
Preferably, the support filler is hydrophily fume colloidal silica or hydrophily deposition white carbon black.
Preferably, the specific surface area of the support filler, which is greater than, is equal to 150m2/g。
Preferably, the surface hydroxyl number of the support filler is 2-10/(nm2), the test method ginseng of surface hydroxyl number
It examines: vinyltriethoxysilane surface-modified nano SiO2, Ou Yangzhaohui, Wu Lin, Li Kongbiao, Yi Delian, Qin Xiaorong, chemical industry
New material, the 2nd phase 28-30 of volume 2006.2 the 34th.
Preferably, in terms of the polyolefine material of 100 parts by weight, the dosage of the support filler is 10-60 parts by weight.
Metal oxide of the present invention is the metal oxide with catalytic action, and specific substance is not particularly limited,
Including metal oxide, oxide mixture etc., it is preferred that the metal oxide include zinc oxide, aluminium oxide, magnesia,
One or more of zirconium oxide, titanium oxide, alumina-ferric oxide.
Preferably, the functional additive is zinc carbonate, basic zinc carbonate (ZnCO3·2Zn(OH)2·H2O), boric acid
Zinc (2ZnO3B2O3·3.5H2O), basic magnesium carbonate (4MgCO3·Mg(OH)2·5H2O), magnesium carbonate, in boehmite
It is one or more of.
Preferably, the average grain diameter of the functional additive is 5nm-50 microns.
Preferably, in terms of the polyolefine material of 100 parts by weight, the dosage of the functional additive is 5-25 parts by weight.
It is furthermore preferred that the amount ratio of the functional additive and support filler is (0.35-1.5): 1.
It joined support filler and functional additive in fire-resistant polyolefin of the invention, functional additive is heated to be divided
The metal oxide obtained after solution can be used as catalyst, promote the hydroxyl condensation on support filler particles surface, make to support filler hair
Raw interaction forms stable support frame, and then forms the hard ceramic body with inner support skeleton, which is holding
Contraction will not be obviously melted in the case where continuous high temperature.The mode that low-melting glass powder material is added in compared with the existing technology can be with
Dimensional stability and insulation performance of the ceramic body under the conditions of continuous high temperature are significantly improved, guarantees the fire resistance of cable.
Preferably, the Vitrified powder is one or more of mica powder, kaolin, talcum powder, montmorillonite, bentonite.
Preferably, in terms of the polyolefine material of 100 parts by weight, the dosage of the Vitrified powder is 50-200 parts by weight.It is more excellent
Selection of land, in terms of the polyolefine material of 100 parts by weight, the dosage of the Vitrified powder is 100-200 parts by weight.
Preferably, the Vitrified powder is surface treated Vitrified powder, described to be surface-treated the surface treating agent used
For one or more of silane coupling agent, titante coupling agent, aluminate coupling agent.It is furthermore preferred that at the surface
Reason agent is silane coupling agent A171, silane coupling agent KH570, propyl trimethoxy silicane, propyl-triethoxysilicane, fourth
Base trimethoxy silane, butyl triethoxysilane, octyl trimethoxy silane, octyltri-ethoxysilane, dodecyl three
Methoxy silane, dodecyl triethoxysilane, hexadecyl trimethoxy silane, hexadecyl, titanium
Esters of gallic acid coupling agent 201 or aluminate coupling agent 101.Preferably, the method for the surface treatment is: at ceramic powder and surface
110-120 DEG C of constant temperature stirring 5-18min is warming up to after reason agent mixing.Preferably, the quality of the surface treating agent is porcelain
Change the 0.2%-2% of silty amount.
The compatibility of polyolefin and Vitrified powder can be improved by surface treatment in the present invention, improves ceramic fire resisting polyene
The performances such as tensile strength, melt flow rate (MFR), the weatherability of hydrocarbon.
Preferably, the raw material further includes antioxidant, is selected from anti-oxidant Irganox 1010, irgasfos 168, antioxidant 264
One or more of.When the raw material includes antioxidant, the preparation of the ceramic polyolefin master batch be will support filler with
Functional additive mixing dispersion, then mixes with polyolefine material, antioxidant, then be warming up to 140~150 DEG C of mixing 15-
20min obtains ceramic polyolefin master batch.
Preferably, the quality of the antioxidant is the 0.2%-2% of polyolefine material.
The invention has the following advantages:
The formula that ceramic fireproof polyolefin of the invention is combined using support filler with functional additive, makes resistance to
Fiery composition avoided during continuous high temperature occur melting shrink, and occur cable breakdown, finally obtain insulation performance,
The cable material of mechanical property and excellent fire retarding performance is effectively improved using the ceramic fire-resistant polyolefin as fire resisting layer material
The reliability of fire-resisting cable in practical applications.
Specific embodiment
Specific embodiments of the present invention are given below, the test method reference of surface hydroxyl number in following embodiment: ethylene
Ethyl triethoxy silicane alkane surface-modified nano SiO2, Ou Yangzhaohui, Wu Lin, Li Kongbiao, Yi Delian, Qin Xiaorong, chemical industry novel-section
Material, the 2nd phase 28-30 of volume 2006.2 the 34th;The test condition of melt flow rate (MFR) is 190 DEG C, 2.16Kg, and testing standard is
ASTMD1238, microcaloire softening temperature testing standard ASTMD1525;The manufacturer of mixer is Rui'an City rubber manufacturing machinery, equipment
Model X (S) N 55*30, the manufacturer of single screw extrusion machine are that Zhangjagang City mutual hundred million obtains Machinery Co., Ltd., device model
SJ-65, the manufacturer for double rank extruding pelletization units that double screw extruder, single screw extrusion machine form are that Kunshan section believes rubber and plastic
Machinery Co., Ltd., device model KSJ-52/100.
Embodiment 1
Ceramic fireproof polyolefin the preparation method is as follows:
By hydrophily fume colloidal silica (Degussa A300, specific surface area 300m2/ g, surface hydroxyl number be 3.3/
(nm2)) 25kg is mixed with basic zinc carbonate 10kg (7 microns of average grain diameter) and is uniformly dispersed, then is total to 100kg ethene-alpha-olefin
Polymers (Tao Shi POE8450, melt flow rate (MFR) 3.0g/10min, 84 DEG C of microcaloire softening temperature), 0.5kg antioxidant 1010 are together
Mixing, which is put into mixer, is warming up to 145 DEG C of mixings 18 minutes, and discharging enters single screw extrusion machine and carries out extruding pelletization, obtains
Ceramic polyolefin master batch;
110 DEG C of constant temperature are warming up to after mica powder 170kg is mixed with hexadecyl trimethoxy silane 1.7kg to be stirred
10min obtains pretreated mica powder;Ceramic polyolefin master batch is added in mixer, then is put into pretreated
Mica powder then heats to 150 DEG C of mixings 22 minutes, using the double ranks being made of double screw extruder, single screw extrusion machine
Extruding pelletization unit carries out mixing plasticizing, extrusion, earnestly air-cooled, ceramic fireproof polyolefin is obtained, wherein setting double spiral shells
The temperature in bar extruder one area to 8th area is respectively 130 DEG C of an area, 130 DEG C of 2nd area, 140 DEG C of 3rd area, 150 DEG C of 4th area, five areas 150
DEG C, 155 DEG C of 6th area, 150 DEG C of 7th area, 145 DEG C of 8th area, single screw extrusion machine temperature setting be 120 DEG C of an area, 130 DEG C of 2nd area, three
130 DEG C of area, the head temperature of single screw extrusion machine is set as 145 DEG C.
Embodiment 2
Ceramic fireproof polyolefin the preparation method is as follows:
By hydrophily fume colloidal silica (Cabot M5, specific surface area 200m2/ g, surface hydroxyl number are 2.8/(nm2))
45kg is mixed with basic zinc carbonate 12kg (7 microns of average grain diameter) and is uniformly dispersed, then with one acetate ethylene copolymer (Beijing of ethylene
Organic, EVA14-2) (melt flow rate (MFR) 2.0g/10min, VA content 14%) 100kg, antioxidant 1010 0.5kg throw together
Enter into mixer, discharging enters single screw extrusion machine progress extruding pelletization after being warming up to 145 DEG C of mixings 18 minutes, obtains ceramics
Change polyolefin master batch;
110 DEG C of constant temperature are warming up to after kaolin 100kg is mixed with hexadecyl trimethoxy silane 0.5kg to be stirred
15min obtains pretreated kaolin;Ceramic polyolefin master batch is added in mixer, then is put into pretreated
Kaolin is warming up to 150 DEG C of mixings 22 minutes, squeezes out using the double ranks being made of double screw extruder, single screw extrusion machine
It is granulated unit and carries out mixing plasticizing, extrusions, earnestly air-cooled, ceramic fireproof polyolefin is obtained, wherein setting twin-screw is crowded
The temperature in Chu Ji mono- area to 8th area be respectively 130 DEG C of an area, 130 DEG C of 2nd area, 140 DEG C of 3rd area, 150 DEG C of 4th area, 150 DEG C of 5th area,
Six 155 DEG C of areas, 150 DEG C of 7th area, 145 DEG C of 8th area, single screw extrusion machine temperature setting are 120 DEG C of an area, 130 DEG C of 2nd area, 3rd area
130 DEG C, the head temperature of single screw extrusion machine is set as 145 DEG C.
Embodiment 3
Ceramic fireproof polyolefin the preparation method is as follows:
By 18kg hydrophily fume colloidal silica (Cabot EH-5, specific surface area 380m2/ g, surface hydroxyl number are 5.0
A/(nm2)) mix and be uniformly dispersed with 23kg basic zinc carbonate (7 microns of average grain diameter), then with ethylene-vinyl acetate copolymer
(Yangtze BASF, EVAV5110J) (melt flow rate (MFR) 2.8g/10min, VA content 18%) 100kg, antioxidant 1010
0.5kg is put into together in mixer be warming up to 145 DEG C of mixings 18 minutes after discharging enter single screw extrusion machine carry out squeeze out make
Grain, obtains ceramic polyolefin master batch;
It is mixed that 110 DEG C of constant temperature stirrings are warming up to after kaolin 175kg is mixed with hexadecyl trimethoxy silane 1.75kg
10min is closed, pretreated kaolin is obtained;Ceramic polyolefin master batch is added in mixer, then after putting into pretreatment
Kaolin, be warming up to 150 DEG C of mixings 22 minutes, squeezed using the double ranks being made of double screw extruder, single screw extrusion machine
It is granulated unit out and carries out mixing plasticizing, extrusions, fervent air-cooled, ceramic fireproof polyolefin is obtained, wherein setting twin-screw
The temperature in extruder one area to 8th area is respectively 130 DEG C of an area, 130 DEG C of 2nd area, 140 DEG C of 3rd area, 150 DEG C of 4th area, five areas 150
DEG C, 155 DEG C of 6th area, 150 DEG C of 7th area, 145 DEG C of 8th area, single screw extrusion machine temperature setting be 120 DEG C of an area, 130 DEG C of 2nd area, three
130 DEG C of area, the head temperature of single screw extrusion machine is set as 145 DEG C.
Embodiment 4
Ceramic fireproof polyolefin the preparation method is as follows:
By hydrophily fume colloidal silica, (Degussa A380, surface hydroxyl number are 5/(nm2)) 35kg and magnesium carbonate
20kg (1250 mesh) mixing is uniformly dispersed, with ethylene-vinyl acetate copolymer (Beijing is organic, EVA14-2) (melt flow rate (MFR)
2.0g/10min, VA content 14%) 100kg, antioxidant 1010 0.5kg put into mixer together and be warming up to 145 DEG C of mixings
18 minutes, discharging entered single screw extrusion machine and carries out extruding pelletization, obtained ceramic polyolefin master batch;
It is mixed that 110 DEG C of constant temperature stirrings are warming up to after talcum powder 165kg is mixed with hexadecyl trimethoxy silane 1.75kg
15min is closed, pretreated talcum powder is obtained;Ceramic polyolefin master batch is added in mixer, then after putting into pretreatment
Talcum powder, be warming up to 150 DEG C of mixings 22 minutes, squeezed using the double ranks being made of double screw extruder, single screw extrusion machine
It is granulated unit out and carries out mixing plasticizing, extrusions, fervent air-cooled, ceramic fireproof polyolefin is obtained, wherein setting twin-screw
The temperature in extruder one area to 8th area is respectively 130 DEG C of an area, 130 DEG C of 2nd area, 140 DEG C of 3rd area, 150 DEG C of 4th area, five areas 150
DEG C, 155 DEG C of 6th area, 150 DEG C of 7th area, 145 DEG C of 8th area, single screw extrusion machine temperature setting be 120 DEG C of an area, 130 DEG C of 2nd area, three
130 DEG C of area, the head temperature of single screw extrusion machine is set as 145 DEG C.
Embodiment 5
Ceramic fireproof polyolefin the preparation method is as follows:
By hydrophily precipitation method White Carbon black, (FINE-SIL518, Wanzai County Hui Ming Chemical Co., Ltd., surface hydroxyl number are
6.0/(nm2)) 58kg, boehmite 20kg (Shandong Berry Chemical Industry Science Co., Ltd, specific surface area >=260m2/ g) it is mixed
Conjunction is uniformly dispersed, with one acetate ethylene copolymer of ethylene (Beijing is organic, EVA14-2) (melt flow rate (MFR) 2.0g/10min, VA
Content 14%) 100kg, antioxidant 1010 0.5kg put into mixer together and be warming up to 145 DEG C of mixings 18 minutes, discharge into
Enter single screw extrusion machine and carry out extruding pelletization, obtains ceramic polyolefin master batch;
110 DEG C of constant temperature are warming up to after kaolin 75kg is mixed with hexadecyl trimethoxy silane 1.4kg to be stirred
10min obtains pretreated kaolin;Ceramic polyolefin master batch is added in mixer, then is put into pretreated
Kaolin is warming up to 150 DEG C of mixings 22 minutes, squeezes out using the double ranks being made of double screw extruder, single screw extrusion machine
It is granulated unit and carries out mixing plasticizing, extrusions, earnestly air-cooled, ceramic fireproof polyolefin is obtained, wherein setting twin-screw is crowded
The temperature in Chu Ji mono- area to 8th area be respectively 130 DEG C of an area, 130 DEG C of 2nd area, 140 DEG C of 3rd area, 150 DEG C of 4th area, 150 DEG C of 5th area,
Six 155 DEG C of areas, 150 DEG C of 7th area, 145 DEG C of 8th area, single screw extrusion machine temperature setting are 120 DEG C of an area, 130 DEG C of 2nd area, 3rd area
130 DEG C, the head temperature of single screw extrusion machine is set as 145 DEG C.
Comparative example:
The ceramic fireproof polyolefin of comparison the preparation method is as follows:
By ethene-alpha-olefin copolymer (Tao Shi POE8450, melt flow rate (MFR) 3.0g/10min, microcaloire softening temperature 84
DEG C) 100kg, mica powder 180kg, lead-free glass powder with low melting point (peace meter Wei Na D245, melt 450 DEG C) 20kg, antioxidant 1010
0.5kg, which is put into mixer, is warming up to 145 DEG C of mixings 25 minutes, using by double screw extruder, single screw extrusion machine group
At double rank extruding pelletization units carry out mixing plasticizing, extrusion, earnestly air-cooled, the ceramic fireproof polyene compared
Hydrocarbon, wherein the temperature in setting double screw extruder one area to 8th area is respectively 130 DEG C of an area, 130 DEG C of 2nd area, 140 DEG C of 3rd area, four
150 DEG C of area, 150 DEG C of 5th area, 155 DEG C of 6th area, 150 DEG C of 7th area, 145 DEG C of 8th area, single screw extrusion machine temperature setting are an area 120
DEG C, 130 DEG C of 2nd area, 130 DEG C of 3rd area, the head temperature of single screw extrusion machine is set as 145 DEG C.
Performance test embodiment
One, embodiment 1-5 and comparative example the ceramic fireproof polyolefin prepared are tested for the property, specifically
It is as follows:
1-4 test samples the preparation method comprises the following steps: can ceramic fire-resistant polyolefin material on 140 DEG C of two roller open mill
Mill is plasticized slice, is put into mold, on 150 DEG C of hydraulic presses after five minutes with 5MPa pressure pressure, then in 15MPa pressure pressure 15
Minute, it then is cooled to room temperature under 15MPa pressure, obtains test sample after cutting.
1, tensile strength is tested: being tested, is drawn on 503B universal tensile testing machine according to GB/T 1040.3-2006 standard
It stretches test to carry out at room temperature, tensile speed 250mm/min, test sample is the 5 type dumb bell samples with a thickness of 1mm.
2, volume resistivity: measuring on ZC36 type megger according to GB/T 1410-2006, and test temperature is 25 DEG C, surveys
Examination voltage is 1000V, and test sample is having a size of 80 ㎜ * of Φ, 1 ㎜ thickness disk.
3, it melt flow rate (MFR): is surveyed on GT-7100-MI shape glue melt index determination machine referring to GB/T 3682-2000
Fixed, test condition is 190 DEG C, 10Kg counterweight.
4, heat ageing: being put into RH-4015A ageing oven for test sample according to GB/T 2951.12-2008 standard, surveys
The change rate of the tensile strength before and after baking 168H at 100 DEG C is tried, test sample is the 5 type samples with a thickness of 1mm.
5, fire resistance is tested: being tested according to GB/T 19216.21-2003 standard;Test sample is respectively by reality
Apply fire-resisting cable made from a 1-5 and the ceramic fireproof polyolefin of comparative example.Fire-resisting cable the preparation method comprises the following steps:
It is 50mm in section2Copper conductor on squeeze out the polyethylene layer of 1.5mm thickness, placement is 8 small in 90 DEG C -95 DEG C of steam box
When complete crosslinking, the insulated wire cores after being crosslinked.Take that four insulated wire cores 0.2mm are thick, non-woven fabrics of 60mm wide is around being bundled into
Cable (overlap rate 30%), then the ceramic polyolefin inner restrictive coating of 5.0mm thickness is squeezed out, the material for finally squeezing out 2.0mm thickness again is
The low smoke and zero halogen external sheath layer of EVA and aluminium hydroxide, obtain fire-resisting cable.When test, flame temperature is set as 950 DEG C -1000
DEG C, voltage 450V is 90min for the fiery time, investigates for 90min during fire and there is fuse after ceasing fire during cooling 15min
Without disconnection, light bulb whether there is or not extinguishing, fuse is not turned off, and light bulb also passes through without extinguishing for experiment.
Test data is shown in Table 1.
Table 1
Two, the survey of ceramic performance is carried out to embodiment 1-5 and comparative example the ceramic fireproof polyolefin prepared
Examination, specific as follows:
Test sample the preparation method comprises the following steps:
By ceramic fireproof polyolefin, mill is plasticized to obtain 2.5 millimeters thick sheet materials on 140 DEG C of two roller open mill, is put into
In 1mm thickness mold, on 150 DEG C of hydraulic presses with 5MPa pressure pressure after five minutes, then 15MPa pressure press 15 minutes, then in
Room temperature is cooled under 15MPa pressure, cutting obtains 50mm long, the test sample of 20mm wide, 1mm thickness.
Test sample is put into 950 DEG C of Muffle furnace ablation 60 minutes, after taking out room temperature cooling, is tested after testing ablation
The cosmetic variation of the change in size of sample and formed ceramic body, test result are shown in Table 2.
Table 2
2 data of table are it is found that dimensional contraction significantly reduces after ceramic fireproof polyolefin high temperature ablation of the invention, ruler
Very little stability obviously increases, and effectively compensates for glass melting in current material and shrinks bring product defects, improves material
Fire resistance, and preparation method is simple.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (7)
1. a kind of preparation method of ceramic fireproof polyolefin, the ceramic fireproof polyolefin prepare raw material packet
Include polyolefine material, Vitrified powder, support filler and functional additive, the support filler be hydrophily fume colloidal silica,
One or more of hydrophily precipitated silica, hydrophily high-purity ground quartz, the functional additive are in 200-650
DEG C decomposition obtains the compound of metal oxide;The preparation method comprises the following steps:
Support filler mix into dispersion with functional additive, then mix with polyolefine material heat up after mixing, then extrusion is made
Grain, obtains ceramic polyolefin master batch;
Mixing is obtained using being kneaded plasticizing, squeezing out, earnestly air-cooled after ceramic polyolefin master batch is mixed heating with Vitrified powder
To ceramic fireproof polyolefin.
2. the preparation method of ceramic fireproof polyolefin as described in claim 1, which is characterized in that the support filler
Surface hydroxyl number be 2-10/(nm2)。
3. the preparation method of ceramic fireproof polyolefin as claimed in claim 1 or 2, which is characterized in that with 100 weight
The dosage of the polyolefine material meter of part, the support filler is 10-60 parts by weight.
4. the preparation method of ceramic fireproof polyolefin as described in claim 1, which is characterized in that the metal oxidation
Object includes one or more of zinc oxide, aluminium oxide, magnesia, zirconium oxide, titanium oxide, alumina-ferric oxide.
5. the preparation method of ceramic fireproof polyolefin as claimed in claim 1 or 3, which is characterized in that the function
Property additive be one of zinc carbonate, basic zinc carbonate, zinc borate, basic magnesium carbonate, magnesium carbonate, boehmite or several
Kind.
6. the preparation method of ceramic fireproof polyolefin as claimed in claim 2, which is characterized in that with 100 parts by weight
Polyolefine material meter, the dosage of the functional additive is 5-25 parts by weight.
7. the preparation method of ceramic fireproof polyolefin as claimed in claim 1 or 2, which is characterized in that the porcelain
Powder includes one or more of mica powder, kaolin, talcum powder, in terms of the polyolefine material of 100 parts by weight, the Vitrified powder
Dosage be 50-200 parts by weight.
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CN111273138A (en) * | 2020-02-24 | 2020-06-12 | 远东电缆有限公司 | Suspended cable fire resistance test device and method for super high-rise building |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1447344A (en) * | 2002-03-22 | 2003-10-08 | 尼克桑斯公司 | Insulation compsn. of safety cable |
CN1729272A (en) * | 2002-10-17 | 2006-02-01 | 陶瓷聚合体有限公司 | Fire resistant polymeric compositions |
CN101472983A (en) * | 2006-04-21 | 2009-07-01 | 欧莱克斯澳大利亚私人有限公司 | Fire resistant compositions |
CN103601954A (en) * | 2013-11-11 | 2014-02-26 | 深圳市沃尔核材股份有限公司 | Flame-retardant ceramic composite material and preparation method thereof |
CN104497404A (en) * | 2014-12-31 | 2015-04-08 | 深圳市沃尔核材股份有限公司 | Porcelainized polyolefin composite material and preparation method thereof |
CN104558805A (en) * | 2015-01-17 | 2015-04-29 | 中利科技集团股份有限公司 | Ceramic polyolefin material and preparation method thereof |
CN104744794A (en) * | 2014-12-24 | 2015-07-01 | 上海旭创高分子材料有限公司 | Ceramic fire-resistant polyolefin composition and preparation method thereof |
CN105694471A (en) * | 2016-04-17 | 2016-06-22 | 北京化工大学 | Preparation method of ceramizing fire-resistant silicon rubber |
CN105885197A (en) * | 2016-06-02 | 2016-08-24 | 沈阳化工大学 | Anti-flaming vitrified EVA and preparation method thereof |
CN106336563A (en) * | 2016-08-23 | 2017-01-18 | 江苏上上电缆集团有限公司 | Ceramic polyolefin cable material and preparation method thereof |
WO2017070893A1 (en) * | 2015-10-29 | 2017-05-04 | 国家纳米科学中心 | Ceramic silicone rubber, preparation method and use thereof |
CN106688052A (en) * | 2014-09-12 | 2017-05-17 | 普睿司曼股份公司 | Fire resistant cable with ceramifiable layer |
CN106905706A (en) * | 2017-05-09 | 2017-06-30 | 深圳市誉隆新材料有限公司 | A kind of fire resistant flame retardant constituent polyorganosiloxane composition |
CN108164805A (en) * | 2017-12-25 | 2018-06-15 | 天津科技大学 | One kind can porcelain EVA non-halogen flame-retardant cables and preparation method thereof |
-
2018
- 2018-12-24 CN CN201811585122.6A patent/CN109679196A/en active Pending
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1447344A (en) * | 2002-03-22 | 2003-10-08 | 尼克桑斯公司 | Insulation compsn. of safety cable |
CN1729272A (en) * | 2002-10-17 | 2006-02-01 | 陶瓷聚合体有限公司 | Fire resistant polymeric compositions |
CN101472983A (en) * | 2006-04-21 | 2009-07-01 | 欧莱克斯澳大利亚私人有限公司 | Fire resistant compositions |
CN103601954A (en) * | 2013-11-11 | 2014-02-26 | 深圳市沃尔核材股份有限公司 | Flame-retardant ceramic composite material and preparation method thereof |
CN106688052A (en) * | 2014-09-12 | 2017-05-17 | 普睿司曼股份公司 | Fire resistant cable with ceramifiable layer |
CN104744794A (en) * | 2014-12-24 | 2015-07-01 | 上海旭创高分子材料有限公司 | Ceramic fire-resistant polyolefin composition and preparation method thereof |
CN104497404A (en) * | 2014-12-31 | 2015-04-08 | 深圳市沃尔核材股份有限公司 | Porcelainized polyolefin composite material and preparation method thereof |
CN104558805A (en) * | 2015-01-17 | 2015-04-29 | 中利科技集团股份有限公司 | Ceramic polyolefin material and preparation method thereof |
WO2017070893A1 (en) * | 2015-10-29 | 2017-05-04 | 国家纳米科学中心 | Ceramic silicone rubber, preparation method and use thereof |
CN105694471A (en) * | 2016-04-17 | 2016-06-22 | 北京化工大学 | Preparation method of ceramizing fire-resistant silicon rubber |
CN105885197A (en) * | 2016-06-02 | 2016-08-24 | 沈阳化工大学 | Anti-flaming vitrified EVA and preparation method thereof |
CN106336563A (en) * | 2016-08-23 | 2017-01-18 | 江苏上上电缆集团有限公司 | Ceramic polyolefin cable material and preparation method thereof |
CN106905706A (en) * | 2017-05-09 | 2017-06-30 | 深圳市誉隆新材料有限公司 | A kind of fire resistant flame retardant constituent polyorganosiloxane composition |
CN108164805A (en) * | 2017-12-25 | 2018-06-15 | 天津科技大学 | One kind can porcelain EVA non-halogen flame-retardant cables and preparation method thereof |
Non-Patent Citations (3)
Title |
---|
《无机化学》编写组编: "《无机化学》", 28 February 1974, 上海人民出版社 * |
何培之: "《铸造材料化学》", 31 July 1981, 机械工业出版社 * |
李永河: "《橡胶硫化技术》", 31 May 2012, 黄河水利出版社 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111273138A (en) * | 2020-02-24 | 2020-06-12 | 远东电缆有限公司 | Suspended cable fire resistance test device and method for super high-rise building |
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