CN103102551A - Natural light cross-linking low-smoke halogen-free flame retardant polyolefin material, and preparation method and usage method thereof - Google Patents
Natural light cross-linking low-smoke halogen-free flame retardant polyolefin material, and preparation method and usage method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Abstract
A natural light cross-linking low-smoke halogen-free flame retardant polyolefin material, and a preparation method and a usage method thereof. The invention relates to a low-smoke halogen-free flame retardant polyolefin material, and a preparation method and a usage method thereof, and aims to solve the problems of high production cost and large energy consumption of machinery and equipment in existing cross-linking method for producing cross-linking low-smoke halogen-free flame retardant polyolefin material. The natural light cross-linking low-smoke halogen-free flame retardant polyolefin material is prepared from a dry mixing polyolefin resin, a flame retardant agent, an initiator, a cross-linking assistant, an antioxidant, a coupling agent and a nucleating agent. The preparation method comprises steps of: 1, weighting the components; 2, preparing a mixed solution; 3, preparing a polyolefin resin after mixing; and 4, granulating by a twin-screw extruder. The usage method comprises: preparing the natural light cross-linking low-smoke halogen-free flame retardant polyolefin material into a sheet, and irradiating the sheet under sunlight to obtain the natural light cross-linking low-smoke halogen-free flame retardant polyolefin material. The invention can be used in preparation of natural light cross-linking low-smoke halogen-free flame retardant polyolefin materials.
Description
Technical field
The present invention relates to a kind of low-smoke halide-free fireproof composite polyolefine material and preparation method thereof and using method.
Background technology
The characteristics such as low-smoke non-halogen flame-retardant cross-linked polyolefin material has that tensile strength is high, elongation at break is large, heat-resisting, withstand voltage, corrosion resistance and good are widely used in the electric wire production.The cross-linking method of at present known low smoke halogen-free flame-retardant polyolefin has radiation crosslinking, peroxide crosslinking, crosslinked with silicane and ultraviolet light cross-linking.In four kinds of crosslinking methods, the polymer radiation crosslinking is with fastest developing speed in crosslinked field, the earliest, it is also the most crosslinked Cantonese, but the crosslinked facility investment that exists of high-energy radiation is large, maintenance of the equipment is complicated, price is high, it is discontinuous to extrude with crosslinking process, and the shortcoming such as production efficiency is low can not be generalized in middle-size and small-size electric wire enterprise.Peroxide crosslinking is to utilize the superoxide thermal degradation to produce free radical to cause the macromolecules cross-linking reaction, but needs high temperature when crosslinked, and temperature is controlled strict.Crosslinked with silicane is to utilize silane to pass through fusion-grafting, receives on macromolecular chain, and then side group is hydrolyzed, and dehydrating condensation under catalyzer exists forms Si-O-Si crosslinked, but need poach when crosslinked, expends man-hour long, and product stability is poor.Ultraviolet light cross-linking is a kind of crosslinking method that development in recent years is got up, by add light trigger in polyethylene, after UV-irradiation, the luminous energy that light trigger absorbs specific wavelength changes excited state into, produce free radical by the hydrogen of capturing on Polyethylene Chain, cause a series of rapid polymerization reactions, generate the crosslinked polyethylene with tridimensional network.Above several crosslinking method all needs a large amount of facility investments, causes that production cost is high, the machinery equipment power consumption is large.
Summary of the invention
The present invention will solve the cross-linking method of existing preparation cross-linking low smoke halogen-free fire retardant polyolefin material to have the high and machinery equipment of the production cost large problem that consumes energy, but and provides crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light and preparation method thereof and using method.
But the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light of the present invention is made by the mixing polyolefin resin of 100 parts of dryings, 80～150 parts of fire retardants, 0.2～0.8 part of initiator, 2～6 parts of additional crosslinkers, 0.01～0.6 part of oxidation inhibitor, 2～6 parts of coupling agents and 2～7 parts of transparent nucleaters by weight, the mass ratio of wherein said initiator and additional crosslinker is 1:(7～26), the mass ratio of described initiator and oxidation inhibitor is 1:(0.2～1.5).
But the preparation method of the low-smoke halide-free fireproof composite polyolefine material that above-mentioned natural light is crosslinked carries out according to the following steps:
One, take each component: take by weight the mixing polyolefin resin of 100 parts of dryings, 80～150 parts of fire retardants, 0.2～0.8 part of initiator, 2～6 parts of additional crosslinkers, 0.01～0.6 part of oxidation inhibitor, 2～6 parts of coupling agents and 2～7 parts of transparent nucleaters, the mass ratio of wherein said initiator and additional crosslinker is 1:(7～26), the mass ratio of described initiator and oxidation inhibitor is 1:(0.2～1.5);
Two, preparation mixing solutions: 0.2～0.8 part of initiator, 2～6 parts of additional crosslinkers and 0.01～0.6 part of oxidation inhibitor that step 1 is taken join in beaker simultaneously, the mass ratio of wherein said initiator and additional crosslinker is 1:(7～26), the mass ratio of described initiator and oxidation inhibitor is 1:(0.2～1.5), be to stir 20min～40min under the condition of 55 ℃～85 ℃ in temperature, make mixing solutions;
Three, the polyolefin resin of preparation after mixing: take the mixing solutions that 1～5 part of step 2 makes, 80～150 parts of fire retardants that itself and step 1 are taken, 2～6 parts of coupling agents and 2～7 parts of transparent nucleaters join mixing in polyolefin resin of 100 parts of dryings that step 1 takes simultaneously, be banburying 15min～20min under 145 ℃～160 ℃ conditions in temperature, namely obtain the polyolefin resin after mixing;
Four, twin screw extruder granulation: with the twin screw extruder Temperature Setting at 160 ℃～185 ℃, then step 3 is obtained mixing after polyolefin resin by the twin screw extruder granulation, but namely obtain the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light.
But the using method of the low-smoke halide-free fireproof composite polyolefine material that above-mentioned natural light is crosslinked is carried out according to the following steps:
But the low-smoke halide-free fireproof composite polyolefine material that natural light is crosslinked is made the sheet material that thickness is 0.4mm～1.0mm, is placed under daylight and shines, and light application time is 72h～120h, namely obtains natural light cross-linking low smoke halogen-free fire retardant polyolefin material.
But the present invention selects carry out sun exposure to the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light June～October, and the place is suburb, Jiamusi, and solar radiation mean value is 115.4 * 10
5Kw/m
2(solar radiation mean value is referring to Jiamusi University's journal (natural science edition) 2006,24 (1), 136-138).
Advantage of the present invention: but one, the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light of the present invention preparation need not special cross-linking apparatus, utilizes natural light to carry out effectively crosslinked, reduced crosslinked cost; Two, technique of the present invention is simple, easy to operate; Three, the present invention can reduce with the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light produce power consumption, environment friendly and pollution-free, cost is low, product is high temperature resistant, flame retardant properties is good; Four, the present invention is good with the crosslinked low-smoke halide-free fireproof composite polyolefine material performance of natural light, tensile strength 13MPa, fracture tension strain 190%, oxygen index 35 can pass through 158 ℃ * 168h thermal ageing test, and gel content reaches as high as 35.5%, heat extends 35%, has good application prospect; Five, the present invention with the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light can be used for thickness at 1.0mm with interior application scenario, as aspects such as electric wire and cable jacket or insulation, polyolefin panels section products.
Embodiment
Embodiment one: but the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light of present embodiment is made by the mixing polyolefin resin of 100 parts of dryings, 80～150 parts of fire retardants, 0.2～0.8 part of initiator, 2～6 parts of additional crosslinkers, 0.01～0.6 part of oxidation inhibitor, 2～6 parts of coupling agents and 2～7 parts of transparent nucleaters by weight, the mass ratio of wherein said initiator and additional crosslinker is 1:(7～26), the mass ratio of described initiator and oxidation inhibitor is 1:(0.2～1.5).
But the crosslinked low-smoke halide-free fireproof composite polyolefine material of the described natural light of present embodiment need not special cross-linking apparatus, utilizes natural light to carry out effectively crosslinked, has reduced crosslinked cost.
Embodiment two: what present embodiment was different from embodiment one is: described mixing polyolefin resin is comprised of 10～30 parts of polyethylene, 10～60 parts of ethylene-vinyl acetate copolymers, 15～30 parts of POE, 10～20 parts of polyethylene maleic anhydride grafts, 5～20 parts of ethene-vinyl acetate maleic anhydride grafts and 2～15 parts of ethylene octene maleic anhydride grafts by weight; Described fire retardant is magnesium hydroxide or aluminium hydroxide.Other is identical with embodiment one.
Embodiment three: what present embodiment was different from embodiment one or two is: described coupling agent is the mixture of the one or both in silane coupling agent and aluminate coupling agent; Described silane coupling agent is a kind of in vinyltriethoxysilane (A-151), vinyltrimethoxy silane (A-172), γ aminopropyltriethoxy silane (A-1100), benzene n-formyl sarcolysine ethyl triethoxy silicane alkane (south large-42), γ-second phenodiazine base propyl trimethoxy silicane (A-1120), β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane (A-186) and γ-propyl methacrylate base Trimethoxy silane (A-174) or several mixture wherein; Described aluminate coupling agent is a kind of in aluminate coupling agent DL411-B, aluminate coupling agent DL-811, aluminate coupling agent DL412-A, aluminate coupling agent DL412-B and aluminate coupling agent DL-467 or several mixture wherein; Described transparent nucleater is 2,2'-methylene radical-two (4,6-di-n-butyl phenol) (NA-11), 2,2'-methylene-bis (4, the 6-di-tert-butyl-phenyl) a kind of in phosphoric acid ester sodium (NP-508), dibenzal sorbitol (DBS), two (to the benzyl chloride fork) sorbyl alcohol (CDBS), MDBS (MDBS), two (to the ethyl benzal) sorbyl alcohol (EDBS), DMDBS (DMDBS), mica and silicon-dioxide or wherein several mixture.Other is identical with embodiment one or two.
When the described coupling agent of present embodiment is mixture, be mixed by any ratio between each component.
When the described silane coupling agent of present embodiment is mixture, be mixed by any ratio between each component.
When the described aluminate coupling agent of present embodiment is mixture, be mixed by any ratio between each component.
When the described transparent nucleater of present embodiment is mixture, be mixed by any ratio between each component.
Embodiment four: what present embodiment was different from one of embodiment one to three is: described initiator is 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone (BDMB, Irgacure369), Michler's keton (MK), 2,4-diethyl thioxanthone (DETX), isopropyl thioxanthone (ITX), benzoin dimethylether (initiator 651), 4-methyldiphenyl ketone (MBZ) and OXYBENZONE, a kind of in 4-chlorobenzophenone (initiator 1046) or several mixture wherein; Described additional crosslinker is a kind of in Viscoat 295 (TMPTA), the rare propyl ester of phthalic acid two (DAP), methyl methacrylate (MMA), methacrylate second diester (EDMA), trimethylammonium vulcabond and 4-dimethyl ethyl aminobenzoate (EDAB) or several mixture wherein; Described oxidation inhibitor is 2,6-di-tert-butyl-4-methy phenol (antioxidant 264, BHT), 3,5-di-tert-butyl-hydroxy phenyl propionic acid stearyl alcohol ester (antioxidant 1076), 4'4-thiobis (6-tert-butyl o cresols) (oxidation inhibitor 736), 2,2'-methylene-bis (4-methyl-6-tert-butylphenol) (antioxidant 2246), 4-[methylene radical-3-(3', 5'-di-t-butyl-4'-hydroxy phenyl) propionic acid] a kind of in pentaerythritol ester (antioxidant 1010), triphenylphosphate and triphenyl phosphite or several mixture wherein.Other is identical with one of embodiment one to three.
When the described initiator of present embodiment is mixture, be mixed by any ratio between each component.
When the described additional crosslinker of present embodiment is mixture, be mixed by any ratio between each component.
When the described oxidation inhibitor of present embodiment is mixture, be mixed by any ratio between each component.
Embodiment five: but the preparation method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light of present embodiment carries out according to the following steps:
One, take each component: take by weight the mixing polyolefin resin of 100 parts of dryings, 80～150 parts of fire retardants, 0.2～0.8 part of initiator, 2～6 parts of additional crosslinkers, 0.01～0.6 part of oxidation inhibitor, 2～6 parts of coupling agents and 2～7 parts of transparent nucleaters, the mass ratio of wherein said initiator and additional crosslinker is 1:(7～26), the mass ratio of described initiator and oxidation inhibitor is 1:(0.2～1.5);
Two, preparation mixing solutions: 0.2～0.8 part of initiator, 2～6 parts of additional crosslinkers and 0.01～0.6 part of oxidation inhibitor that step 1 is taken join in beaker simultaneously, the mass ratio of wherein said initiator and additional crosslinker is 1:(7～26), the mass ratio of described initiator and oxidation inhibitor is 1:(0.2～1.5), be to stir 20min～40min under the condition of 55 ℃～85 ℃ in temperature, make mixing solutions;
Three, the polyolefin resin of preparation after mixing: take the mixing solutions that 1～5 part of step 2 makes, 80～150 parts of fire retardants that itself and step 1 are taken, 2～6 parts of coupling agents and 2～7 parts of transparent nucleaters join mixing in polyolefin resin of 100 parts of dryings that step 1 takes simultaneously, be banburying 15min～20min under 145 ℃～160 ℃ conditions in temperature, namely obtain the polyolefin resin after mixing;
Four, twin screw extruder granulation: with the twin screw extruder Temperature Setting at 160 ℃～185 ℃, then step 3 is obtained mixing after polyolefin resin by the twin screw extruder granulation, but namely obtain the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light.
But the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light of present embodiment preparation need not special cross-linking apparatus, utilizes natural light to carry out effectively crosslinked, has reduced crosslinked cost.
Embodiment six: what present embodiment was different from embodiment five is: the mixing polyolefin resin described in step 1 is comprised of 10～30 parts of polyethylene, 10～60 parts of ethylene-vinyl acetate copolymers, 15～30 parts of POE, 10～20 parts of polyethylene maleic anhydride grafts, 5～20 parts of ethene-vinyl acetate maleic anhydride grafts and 2～15 parts of ethylene octene maleic anhydride grafts by weight; Fire retardant described in step 1 is magnesium hydroxide or aluminium hydroxide.Other is identical with embodiment five.
Embodiment seven: what present embodiment was different from embodiment five or six is: the coupling agent described in step 1 is the mixture of the one or both in silane coupling agent and aluminate coupling agent; Described silane coupling agent is a kind of in vinyltriethoxysilane (A-151), vinyltrimethoxy silane (A-172), γ aminopropyltriethoxy silane (A-1100), benzene n-formyl sarcolysine ethyl triethoxy silicane alkane (south large-42), γ-second phenodiazine base propyl trimethoxy silicane (A-1120), β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane (A-186) and γ-propyl methacrylate base Trimethoxy silane (A-174) or several mixture wherein; Described aluminate coupling agent is a kind of in aluminate coupling agent DL411-B, aluminate coupling agent DL-811, aluminate coupling agent DL412-A, aluminate coupling agent DL412-B and aluminate coupling agent DL-467 or several mixture wherein; Transparent nucleater described in step 1 is 2,2'-methylene radical-two (4,6-di-n-butyl phenol) (NA-11), 2,2'-methylene-bis (4, the 6-di-tert-butyl-phenyl) a kind of in phosphoric acid ester sodium (NP-508), dibenzal sorbitol (DBS), two (to the benzyl chloride fork) sorbyl alcohol (CDBS), MDBS (MDBS), two (to the ethyl benzal) sorbyl alcohol (EDBS), DMDBS (DMDBS), mica and silicon-dioxide or wherein several mixture.Other is identical with embodiment five or six.
When the described coupling agent of present embodiment is mixture, be mixed by any ratio between each component.
When the described silane coupling agent of present embodiment is mixture, be mixed by any ratio between each component.
When the described aluminate coupling agent of present embodiment is mixture, be mixed by any ratio between each component.
When the described transparent nucleater of present embodiment is mixture, be mixed by any ratio between each component.
Embodiment eight: what present embodiment was different from one of embodiment five to seven is: the initiator described in step 1 is 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone (BDMB, Irgacure369), Michler's keton (MK), 2,4-diethyl thioxanthone (DETX), isopropyl thioxanthone (ITX), benzoin dimethylether (initiator 651), 4-methyldiphenyl ketone (MBZ) and OXYBENZONE, a kind of in 4-chlorobenzophenone (initiator 1046) or several mixture wherein; Additional crosslinker described in step 1 is a kind of in Viscoat 295 (TMPTA), the rare propyl ester of phthalic acid two (DAP), methyl methacrylate (MMA), methacrylate second diester (EDMA), trimethylammonium vulcabond and 4-dimethyl ethyl aminobenzoate (EDAB) or several mixture wherein; Oxidation inhibitor described in step 1 is 2,6-di-tert-butyl-4-methy phenol (antioxidant 264, BHT), 3,5-di-tert-butyl-hydroxy phenyl propionic acid stearyl alcohol ester (antioxidant 1076), 4'4-thiobis (6-tert-butyl o cresols) (oxidation inhibitor 736), 2,2'-methylene-bis (4-methyl-6-tert-butylphenol) (antioxidant 2246), 4-[methylene radical-3-(3', 5'-di-t-butyl-4'-hydroxy phenyl) propionic acid] a kind of in pentaerythritol ester (antioxidant 1010), triphenylphosphate and triphenyl phosphite or several mixture wherein.Other is identical with one of embodiment five to seven.
When the described initiator of present embodiment is mixture, be mixed by any ratio between each component.
When the described additional crosslinker of present embodiment is mixture, be mixed by any ratio between each component.
When the described oxidation inhibitor of present embodiment is mixture, be mixed by any ratio between each component.
Embodiment nine: but the using method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light of present embodiment is carried out according to the following steps:
But the low-smoke halide-free fireproof composite polyolefine material that natural light is crosslinked is made the sheet material that thickness is 0.4mm～1.0mm, is placed under daylight and shines, and light application time is 72h～120h, namely obtains natural light cross-linking low smoke halogen-free fire retardant polyolefin material.
But present embodiment selects carry out airing to the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light June～October, and the place is suburb, Jiamusi, and solar radiation mean value is 115.4 * 10
5Kw/m
2(solar radiation mean value is referring to Jiamusi University's journal (natural science edition) 2006,24 (1), 136-138).
Present embodiment need not special cross-linking apparatus, utilizes natural light to carry out effectively crosslinked, has reduced crosslinked cost.
Present embodiment technique is simple, easy to operate.
Present embodiment can reduce with the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light produce power consumption, environment friendly and pollution-free, cost is low, product is high temperature resistant, flame retardant properties is good.
Present embodiment is good with the crosslinked low-smoke halide-free fireproof composite polyolefine material performance of natural light, tensile strength 13MPa, fracture tension strain 190%, oxygen index 35 can pass through 158 ℃ * 168h thermal ageing test, and gel content reaches as high as 35.5%, heat extends 35%, has good application prospect.
Present embodiment with the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light can be used for thickness at 1.0mm with interior application scenario, as aspects such as electric wire and cable jacket or insulation, polyolefin panels section products.
Adopt following verification experimental verification effect of the present invention:
Test one: but the preparation method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light carries out according to the following steps:
One, take each component: the mixing polyolefin resin, 90g flame retardant of magnesium hydroxide, 0.4g initiator benzoin dimethylether (initiator 651), 5.00g additional crosslinker Viscoat 295,0.4g antioxidant 1010,4g coupling agent vinyltriethoxysilane and the 4.0g transparent nucleater 2 that accurately take the 100g drying, 2'-methylene radical-two (4,6-di-n-butyl phenol);
Two, preparation mixing solutions: 0.4g initiator benzoin dimethylether (initiator 651), 5.00g additional crosslinker Viscoat 295 and 0.4g antioxidant 1010 that step 1 is taken join in beaker simultaneously, be to stir 0.5h under the condition of 70 ℃ in temperature, make mixing solutions;
Three, the polyolefin resin of preparation after mixing: take the mixing solutions that the 4g step 2 makes, 90g flame retardant of magnesium hydroxide, 4g coupling agent vinyltriethoxysilane and 4.0g transparent nucleater 2 that itself and step 1 are taken, 2'-methylene radical-two (4,6-di-n-butyl phenol) join simultaneously in the mixing polyolefin resin of the 100g drying that step 1 takes, be banburying 20min under 145 ℃ of conditions in temperature, namely obtain the polyolefin resin after mixing;
Four, twin screw extruder granulation: with the twin screw extruder Temperature Setting at 160 ℃～185 ℃, then step 3 is obtained mixing after polyolefin resin by the twin screw extruder granulation, but namely obtain the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light.
The mixing polyolefin resin of the described 100g drying of this testing sequence one is comprised of 10g polyethylene, 50g ethylene-vinyl acetate copolymer, 15g POE, 12g polyethylene maleic anhydride grafts, 5g ethene-vinyl acetate maleic anhydride grafts and 8g ethylene octene maleic anhydride grafts.
Test two: but the using method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light is carried out according to the following steps:
But the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light of test one preparation is made the sheet material that thickness is 1.0mm, be placed under daylight and shine, light application time is 72 hours, namely obtains natural light cross-linking low smoke halogen-free fire retardant polyolefin material.
The solar radiation mean value of this test is 115.4 * 10
5Kw/m
2
Detect according to JB/T10436-2004 " electric wire crosslinkable flame retardant polyolefine material " the natural light cross-linking low smoke halogen-free fire retardant polyolefin material that this test obtains, detected result is as follows: gel content is 17.5%, heat extends to 42.5%, tensile strength is 13.3MPa, elongation at break is 180%, oxygen index 32% can pass through 158 ℃ * 168h thermal ageing test.
Test three: but the preparation method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light carries out according to the following steps:
One, take each component: the mixing polyolefin resin, 100g flame retardant of magnesium hydroxide, the 0.5g initiator OXYBENZONE that accurately take the 100g drying, 4-chlorobenzophenone (initiator 1046), 6.00g additional crosslinker phthalic acid two rare propyl ester, 0.4g antioxidant 2246,4.5g coupling agent vinyltrimethoxy silane (A-172) and 3g transparent nucleater dibenzal sorbitol (DBS);
Two, preparation mixing solutions: the 0.5g initiator OXYBENZONE that step 1 is taken, 4-chlorobenzophenone (initiator 1046), 6.00g the rare propyl ester of additional crosslinker phthalic acid two and 0.4g antioxidant 2246 join in beaker simultaneously, be to stir 0.5h under the condition of 70 ℃ in temperature, make mixing solutions;
Three, the polyolefin resin of preparation after mixing: take the mixing solutions that the 3.5g step 2 makes, 100g flame retardant of magnesium hydroxide, 4.5g coupling agent vinyltrimethoxy silane (A-172) and the 3g transparent nucleater dibenzal sorbitol (DBS) that itself and step 1 are taken joins mixing in polyolefin resin of 100g drying that step 1 takes simultaneously, be banburying 20min under 145 ℃ of conditions in temperature, namely obtain the polyolefin resin after mixing;
Four, twin screw extruder granulation: with the twin screw extruder Temperature Setting at 160 ℃～185 ℃, then step 3 is obtained mixing after polyolefin resin by the twin screw extruder granulation, but namely obtain the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light.
The mixing polyolefin resin of the described 100g drying of this testing sequence one is comprised of 10g polyethylene, 50g ethylene-vinyl acetate copolymer, 15g POE, 12g polyethylene maleic anhydride grafts, 5g ethene-vinyl acetate maleic anhydride grafts and 8g ethylene octene maleic anhydride grafts.
Test four: but the using method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light is carried out according to the following steps:
But the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light of test three preparations is made the sheet material that thickness is 1.0mm, be placed under daylight and shine, light application time is 72 hours, namely obtains natural light cross-linking low smoke halogen-free fire retardant polyolefin material.
The solar radiation mean value of this test is 115.4 * 10
5Kw/m
2
Detect according to JB/T10436-2004 " electric wire crosslinkable flame retardant polyolefine material " the natural light cross-linking low smoke halogen-free fire retardant polyolefin material that this test obtains, detected result is as follows: gel content is 18.3%, heat extends to 40%, tensile strength is 13.8MPa, elongation at break is 186%, oxygen index 33.5% can pass through 158 ℃ * 168h thermal ageing test.
Test five: but the preparation method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light carries out according to the following steps:
One, take each component: the mixing polyolefin resin, 110g flame retardant of magnesium hydroxide, the 0.3g initiator OXYBENZONE that accurately take the 100g drying, 4-chlorobenzophenone (initiator 1046), 5.00g additional crosslinker 4-dimethyl ethyl aminobenzoate, 0.4g antioxidant 300,4.0g coupling agent γ-propyl methacrylate base Trimethoxy silane (A-174) and 3g transparent nucleater 2,2'-methylene-bis (4,6-di-tert-butyl-phenyl) phosphoric acid ester sodium (NP-508);
Two, preparation mixing solutions: the 0.3g initiator OXYBENZONE that step 1 is taken, 4-chlorobenzophenone (initiator 1046), 5.00g additional crosslinker 4-dimethyl ethyl aminobenzoate and 0.4g antioxidant 300 join in beaker simultaneously, be to stir 0.5h under the condition of 70 ℃ in temperature, make mixing solutions;
Three, the polyolefin resin of preparation after mixing: take the mixing solutions that the 2.5g step 2 makes, 110g flame retardant of magnesium hydroxide, 4.0g coupling agent γ-propyl methacrylate base Trimethoxy silane (A-174) and 3g transparent nucleater 2 that itself and step 1 are taken, 2'-methylene-bis (4, the 6-di-tert-butyl-phenyl) phosphoric acid ester sodium (NP-508) joins in the mixing polyolefin resin of the 100g drying that step 1 takes simultaneously, be banburying 20min under 145 ℃ of conditions in temperature, namely obtain the polyolefin resin after mixing;
Four, twin screw extruder granulation: with the twin screw extruder Temperature Setting at 160 ℃～185 ℃, then step 3 is obtained mixing after polyolefin resin by the twin screw extruder granulation, but namely obtain the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light.
The mixing polyolefin resin of the described 100g drying of this testing sequence one is comprised of 10g polyethylene, 50g ethylene-vinyl acetate copolymer, 15g POE, 12g polyethylene maleic anhydride grafts, 5g ethene-vinyl acetate maleic anhydride grafts and 8g ethylene octene maleic anhydride grafts.
Test six: but the using method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light is carried out according to the following steps:
But the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light of test five preparations is made the sheet material that thickness is 1.0mm, be placed under daylight and shine, light application time is 72 hours, namely obtains natural light cross-linking low smoke halogen-free fire retardant polyolefin material.
The solar radiation mean value of this test is 115.4 * 10
5Kw/m
2
Detect according to JB/T10436-2004 " electric wire crosslinkable flame retardant polyolefine material " the natural light cross-linking low smoke halogen-free fire retardant polyolefin material that this test obtains, detected result is as follows: gel content is 17.3%, heat extends to 40%, tensile strength is 13.9MPa, elongation at break is 172%, oxygen index 32.5% can pass through 158 ℃ * 168h thermal ageing test.
Test seven: but the preparation method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light carries out according to the following steps:
One, take each component: accurately take mixing polyolefin resin, 120g flame retardant of magnesium hydroxide, the 02g initiator OXYBENZONE of 100g drying, 4-chlorobenzophenone, 0.015g initiator phenylglyoxylic acid ester, 5.5g additional crosslinker Viscoat 295,0.2g oxidation inhibitor 736,3.5g aluminate coupling agent DL-811 and 3.5g transparent nucleater MDBS;
Two, preparation mixing solutions: the 0.2g initiator OXYBENZONE that step 1 is taken, 4-chlorobenzophenone, 0.015g initiator phenylglyoxylic acid ester, 5.5g additional crosslinker Viscoat 295 and 0.2g oxidation inhibitor 736 join in beaker simultaneously, be to stir 0.5h under the condition of 70 ℃ in temperature, make mixing solutions;
Three, the polyolefin resin of preparation after mixing: take the mixing solutions that the 4.0g step 2 makes, 120g flame retardant of magnesium hydroxide, 3.5g aluminate coupling agent DL-811 and the 3.5g transparent nucleater MDBS that itself and step 1 are taken joins mixing in polyolefin resin of 100g drying that step 1 takes simultaneously, be banburying 20min under 145 ℃ of conditions in temperature, namely obtain the polyolefin resin after mixing;
Four, twin screw extruder granulation: with the twin screw extruder Temperature Setting at 160 ℃～185 ℃, then step 3 is obtained mixing after polyolefin resin by the twin screw extruder granulation, but namely obtain the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light.
The mixing polyolefin resin of the described 100g drying of this testing sequence one is comprised of 10g polyethylene, 50g ethylene-vinyl acetate copolymer, 15g POE, 12g polyethylene maleic anhydride grafts, 5g ethene-vinyl acetate maleic anhydride grafts and 8g ethylene octene maleic anhydride grafts.
Test eight: but the using method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light is carried out according to the following steps:
But the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light of test seven preparations is made the sheet material that thickness is 1.0mm, be placed under daylight and shine, light application time is 72 hours, namely obtains natural light cross-linking low smoke halogen-free fire retardant polyolefin material.
The solar radiation mean value of this test is 115.4 * 10
5Kw/m
2
Detect according to JB/T10436-2004 " electric wire crosslinkable flame retardant polyolefine material " the natural light cross-linking low smoke halogen-free fire retardant polyolefin material that this test obtains, detected result is as follows: gel content is 17.9%, heat extends to 37.5%, tensile strength is 12.8MPa, elongation at break is 178%, oxygen index 33.5% can pass through 158 ℃ * 168h thermal ageing test.
Test nine: but the preparation method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light carries out according to the following steps:
One, take each component: the mixing polyolefin resin, 100g flame retardant of magnesium hydroxide, the 0.4g initiator 2-phenyl-2 that accurately take the 100g drying, 2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 4.5g help crosslinked methyl methacrylate, 0.15g antioxidant 264,3.8g aluminate coupling agent DL412-B and 3g transparent nucleater DMDBS (DMDBS);
Two, preparation mixing solutions: the 0.4g initiator 2-phenyl-2 that step 1 is taken, 2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 4.5g help crosslinked methyl methacrylate, 0.15g antioxidant 264 to join simultaneously in beaker, be to stir 0.5h under the condition of 70 ℃ in temperature, make mixing solutions;
Three, the polyolefin resin of preparation after mixing: take the mixing solutions that the 4.0g step 2 makes, 100g flame retardant of magnesium hydroxide, 3.8g aluminate coupling agent DL412-B and 3g transparent nucleater two (3 that itself and step 1 are taken, 4-dimethyl benzal) sorbyl alcohol (DMDBS) joins in the mixing polyolefin resin of the 100g drying that step 1 takes simultaneously, be banburying 20min under 145 ℃ of conditions in temperature, namely obtain the polyolefin resin after mixing;
Four, twin screw extruder granulation: with the twin screw extruder Temperature Setting at 160 ℃～185 ℃, then step 3 is obtained mixing after polyolefin resin by the twin screw extruder granulation, but namely obtain the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light.
The mixing polyolefin resin of the described 100g drying of this testing sequence one is comprised of 10g polyethylene, 50g ethylene-vinyl acetate copolymer, 15g POE, 12g polyethylene maleic anhydride grafts, 5g ethene-vinyl acetate maleic anhydride grafts and 8g ethylene octene maleic anhydride grafts.
Test ten: but the using method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light is carried out according to the following steps:
But the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light of test nine preparations is made the sheet material that thickness is 1.0mm, be placed under daylight and shine, light application time is 72 hours, namely obtains natural light cross-linking low smoke halogen-free fire retardant polyolefin material.
The solar radiation mean value of this test is 115.4 * 10
5Kw/m
2
Detect according to JB/T10436-2004 " electric wire crosslinkable flame retardant polyolefine material " the natural light cross-linking low smoke halogen-free fire retardant polyolefin material that this test obtains, detected result is as follows: gel content is 18.3%, heat extends to 37.5%, tensile strength is 13.7MPa, elongation at break is 182%, oxygen index 33% can pass through 158 ℃ * 168h thermal ageing test.
Test 11: but the preparation method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light carries out according to the following steps:
One, take each component: the mixing polyolefin resin, 100g flame retardant of magnesium hydroxide, the 0.6g initiator 2-phenyl-2 that accurately take the 100g drying, 2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 4.5g additional crosslinker Viscoat 295,0.25g oxidation inhibitor triphenyl phosphite, 4.6g aluminate coupling agent DL-467 and 3g transparent nucleater two (to the benzyl chloride fork) sorbyl alcohol;
Two, preparation mixing solutions: the 0.6g initiator 2-phenyl-2 that step 1 is taken, 2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 4.5g help crosslinked Viscoat 295 and 0.25g oxidation inhibitor triphenyl phosphite to join simultaneously in beaker, be to stir 0.5h under the condition of 70 ℃ in temperature, make mixing solutions;
Three, the polyolefin resin of preparation after mixing: take the mixing solutions that the 4.5g step 2 makes, 100g flame retardant of magnesium hydroxide, 4.6g aluminate coupling agent DL-467 and the 3g transparent nucleater two that itself and step 1 are taken (to the benzyl chloride fork) sorbyl alcohol joins mixing in polyolefin resin of 100g drying that step 1 takes simultaneously, be banburying 20min under 145 ℃ of conditions in temperature, namely obtain the polyolefin resin after mixing;
Four, twin screw extruder granulation: with the twin screw extruder Temperature Setting at 160 ℃～185 ℃, then step 3 is obtained mixing after polyolefin resin by the twin screw extruder granulation, but namely obtain the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light.
The mixing polyolefin resin of the described 100g drying of this testing sequence one is comprised of 10g polyethylene, 50g ethylene-vinyl acetate copolymer, 15g POE, 12g polyethylene maleic anhydride grafts, 5g ethene-vinyl acetate maleic anhydride grafts and 8g ethylene octene maleic anhydride grafts.
Test 12: but the using method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light is carried out according to the following steps:
But the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light of test 11 preparations is made the sheet material that thickness is 1.0mm, be placed under daylight and shine, light application time is 72 hours, namely obtains natural light cross-linking low smoke halogen-free fire retardant polyolefin material.
The solar radiation mean value of this test is 115.4 * 10
5Kw/m
2
Detect according to JB/T10436-2004 " electric wire crosslinkable flame retardant polyolefine material " the natural light cross-linking low smoke halogen-free fire retardant polyolefin material that this test obtains, detected result is as follows: gel content is 18.5%, heat extends to 40%, tensile strength is 13.6MPa, elongation at break is 186%, oxygen index 33% can pass through 158 ℃ * 168h thermal ageing test.
Test 13: but the preparation method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light carries out according to the following steps:
One, take each component: accurately take mixing polyolefin resin, 100g flame retardant of magnesium hydroxide, the 0.35g initiator 2 of 100g drying, 4-diethyl thioxanthone, 4.4g additional crosslinker 4-dimethyl ethyl aminobenzoate (EDAB), 0.45g antioxidant 1076,5.5g aluminate coupling agent DL411-B and 3.2g transparent nucleater two (to the ethyl benzal) sorbyl alcohol (EDBS);
Two, preparation mixing solutions: the 0.35g initiator 2 that step 1 is taken, 4-diethyl thioxanthone, 4.4g additional crosslinker 4-dimethyl ethyl aminobenzoate (EDAB) and 0.45g antioxidant 1076 join in beaker simultaneously, be to stir 0.5h under the condition of 70 ℃ in temperature, make mixing solutions;
Three, the polyolefin resin of preparation after mixing: take the mixing solutions that the 4.5g step 2 makes, 100g flame retardant of magnesium hydroxide, 5.5g aluminate coupling agent DL411-B and 3.2g transparent nucleater two (to the ethyl benzal) sorbyl alcohol (EDBS) that itself and step 1 are taken joins mixing in polyolefin resin of 100g drying that step 1 takes simultaneously, be banburying 20min under 145 ℃ of conditions in temperature, namely obtain the polyolefin resin after mixing;
Four, twin screw extruder granulation: with the twin screw extruder Temperature Setting at 160 ℃～185 ℃, then step 3 is obtained mixing after polyolefin resin by the twin screw extruder granulation, but namely obtain the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light.
The mixing polyolefin resin of the described 100g drying of this testing sequence one is comprised of 10g polyethylene, 50g ethylene-vinyl acetate copolymer, 15g POE, 12g polyethylene maleic anhydride grafts, 5g ethene-vinyl acetate maleic anhydride grafts and 8g ethylene octene maleic anhydride grafts.
Test 14: but the using method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light is carried out according to the following steps:
But the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light of test 13 preparations is made the sheet material that thickness is 1.0mm, be placed under daylight and shine, light application time is 72 hours, namely obtains natural light cross-linking low smoke halogen-free fire retardant polyolefin material.
The solar radiation mean value of this test is 115.4 * 10
5Kw/m
2
Detect according to JB/T10436-2004 " electric wire crosslinkable flame retardant polyolefine material " the natural light cross-linking low smoke halogen-free fire retardant polyolefin material that this test obtains, detected result is as follows: gel content is 17.8%, heat extends to 42%, tensile strength is 13.3MPa, elongation at break is 178%, oxygen index 33% can pass through 158 ℃ * 168h thermal ageing test.
Test 15: but the preparation method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light carries out according to the following steps:
One, take each component: the mixing polyolefin resin, 120g flame retardant of magnesium hydroxide, the 0.45g initiator isopropyl thioxanthone that accurately take the 100g drying, 3.6g additional crosslinker 4-dimethyl ethyl aminobenzoate, 0.45g oxidation inhibitor 736,6.0g coupling agent β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane (A-186) and 4.2g transparent nucleater silicon-dioxide;
Two, preparation mixing solutions: the 0.45g initiator isopropyl thioxanthone that step 1 is taken, 3.6g additional crosslinker 4-dimethyl ethyl aminobenzoate and 0.45g oxidation inhibitor 736 join in beaker simultaneously, be to stir 0.5h under the condition of 70 ℃ in temperature, make mixing solutions;
Three, the polyolefin resin of preparation after mixing: take the mixing solutions that the 4.5g step 2 makes, 120g flame retardant of magnesium hydroxide, 6.0g coupling agent β-(3 that itself and step 1 are taken, the 4-epoxycyclohexyl) ethyl trimethoxy silane (A-186) and 4.2g transparent nucleater silicon-dioxide join in the mixing polyolefin resin of the 100g drying that step 1 takes simultaneously, be banburying 20min under 145 ℃ of conditions in temperature, namely obtain the polyolefin resin after mixing;
Four, twin screw extruder granulation: with the twin screw extruder Temperature Setting at 160 ℃～185 ℃, then step 3 is obtained mixing after polyolefin resin by the twin screw extruder granulation, but namely obtain the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light.
The mixing polyolefin resin of the described 100g drying of this testing sequence one is comprised of 10g polyethylene, 50g ethylene-vinyl acetate copolymer, 15g POE, 12g polyethylene maleic anhydride grafts, 5g ethene-vinyl acetate maleic anhydride grafts and 8g ethylene octene maleic anhydride grafts.
Test 16: but the using method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light is carried out according to the following steps:
But the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light of test 15 preparations is made the sheet material that thickness is 1.0mm, be placed under daylight and shine, light application time is 72 hours, namely obtains natural light cross-linking low smoke halogen-free fire retardant polyolefin material.
The solar radiation mean value of this test is 115.4 * 10
5Kw/m
2
Detect according to JB/T10436-2004 " electric wire crosslinkable flame retardant polyolefine material " the natural light cross-linking low smoke halogen-free fire retardant polyolefin material that this test obtains, detected result is as follows: gel content is 17.9%, heat extends to 40%, tensile strength is 13.7MPa, elongation at break is 186%, oxygen index 32% can pass through 158 ℃ * 168h thermal ageing test.
Test 17: but the preparation method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light carries out according to the following steps:
One, take each component: the mixing polyolefin resin, 100g flame retardant of magnesium hydroxide, the 0.25g initiator OXYBENZONE that accurately take the 100g drying, 4-chlorobenzophenone, 0.02g additional crosslinker Viscoat 295,4.8g additional crosslinker methyl methacrylate, 0.05g antioxidant 1010,5.0g coupling agent γ aminopropyltriethoxy silane and 3.8g transparent nucleater 2,2'-methylene-bis (4,6-di-tert-butyl-phenyl) phosphoric acid ester sodium;
Two, preparation mixing solutions: the 0.25g initiator OXYBENZONE that step 1 is taken, 4-chlorobenzophenone, 0.02g additional crosslinker Viscoat 295,4.8g additional crosslinker methyl methacrylate and 0.05g antioxidant 1010 join in beaker simultaneously, be to stir 0.5h under the condition of 70 ℃ in temperature, make mixing solutions;
Three, the polyolefin resin of preparation after mixing: take the mixing solutions that the 4.5g step 2 makes, 100g flame retardant of magnesium hydroxide, 5.0g coupling agent γ aminopropyltriethoxy silane and 3.8g transparent nucleater 2 that itself and step 1 are taken, 2'-methylene-bis (4, the 6-di-tert-butyl-phenyl) phosphoric acid ester sodium joins in the mixing polyolefin resin of the 100g drying that step 1 takes simultaneously, be banburying 20min under 145 ℃ of conditions in temperature, namely obtain the polyolefin resin after mixing;
Four, twin screw extruder granulation: with the twin screw extruder Temperature Setting at 160 ℃～185 ℃, then step 3 is obtained mixing after polyolefin resin by the twin screw extruder granulation, but namely obtain the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light.
The mixing polyolefin resin of the described 100g drying of this testing sequence one is comprised of 10g polyethylene, 50g ethylene-vinyl acetate copolymer, 15g POE, 12g polyethylene maleic anhydride grafts, 5g ethene-vinyl acetate maleic anhydride grafts and 8g ethylene octene maleic anhydride grafts.
Test 18: but the using method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light is carried out according to the following steps:
But the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light of test 17 preparations is made the sheet material that thickness is respectively 0.48mm, 0.63mm, 0.75mm and 1.0mm, be placed under daylight and shine, light application time is 72 hours, namely obtains natural light cross-linking low smoke halogen-free fire retardant polyolefin material.
The solar radiation mean value of this test is 115.4 * 10
5Kw/m
2
Detect this test according to JB/T10436-2004 " electric wire crosslinkable flame retardant polyolefine material " and obtain natural light cross-linking low smoke halogen-free fire retardant polyolefin material, detected result is as shown in table 1:
Table 1
All can pass through 158 ℃ * 168h thermal ageing test.
After but the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light of test 17 preparations was made wire insulation, insulation thickness was 1.0mm, shines under daylight, and solar radiation mean value is 115.4 * 10
5Kw/m
2, after the different time sun exposure, performance index are as shown in table 2:
Table 2
| Time (h) | Tensile strength (MPa) | Elongation at break (%) | Heat is extended (%) | Gel content (%) |
| 12 | 12.3 | 186 | － | 4.95 |
| 24 | 12.8 | 176 | － | 5.74 |
| 36 | 12.7 | 186 | － | 6.52 |
| 48 | 12.9 | 186 | － | 8.73 |
| 60 | 12.5 | 174 | － | 13.26 |
| 72 | 13.9 | 176 | 60 | 18.41 |
| 84 | 12.6 | 182 | 45 | 20.08 |
| 96 | 13.8 | 186 | 40 | 21.83 |
| 108 | 13.4 | 190 | 40 | 25.46 |
| 120 | 12.6 | 184 | 37.5 | 29.08 |
Permanent set is 0.
As shown in Table 2, but after the low-smoke halide-free fireproof composite polyolefine material that natural light is crosslinked was applied in wire insulation, performance index met the JB/T10436-2004 electric wire with the requirement in crosslinkable fire retardant polyolefin material after illumination 12h.
Test 19: the performance comparison of natural light cross-linking low smoke halogen-free fire retardant polyolefin material and crosslinking electron beam irradiation low-smoke halide-free fireproof composite polyolefine material, ultraviolet light cross-linking low-smoke halide-free fireproof composite polyolefine material:
But the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light of test 17 preparations is made the sheet material that thickness is 1.0mm, and (solar radiation mean value is 115.4 * 10 to shine 72h under daylight
5Kw/m
2); Compare with the halogen-free low-smoke flame retardant material made from crosslinking electron beam irradiation and ultraviolet light cross-linking mode, result is as shown in table 3:
Table 3
| ? | Crosslinking electron beam irradiation | Ultraviolet light cross-linking | Natural light is crosslinked |
| Tensile strength/MPa | 14.2 | 13.5 | 13.9 |
| Elongation at break/% | 200 | 186 | 190 |
| Oxygen index/% | 33.5 | 35 | 34 |
| Heat extension/% | 40 | 40 | 35 |
| Gel/% | 30 | 17.3 | 35.5 |
| Thermal ageing (158 ℃ * 168h) | By | By | By |
As shown in Table 3, the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light is compared with the ultraviolet light cross-linking low-smoke halide-free fireproof composite polyolefine material with the crosslinking electron beam irradiation low-smoke halide-free fireproof composite polyolefine material, can reach identical performance., and do not need special cross-linking apparatus, crosslinked cost is low.
Claims (9)
1. but low-smoke halide-free fireproof composite polyolefine material that natural light is crosslinked, it is characterized in that but the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light made by the mixing polyolefin resin of 100 parts of dryings, 80～150 parts of fire retardants, 1～2 part of initiator, 2～6 parts of additional crosslinkers, 0.01～0.6 part of oxidation inhibitor, 2～6 parts of coupling agents and 2～7 parts of transparent nucleaters by weight, the mass ratio of wherein said initiator and additional crosslinker is 1:(7～26), the mass ratio of described initiator and oxidation inhibitor is 1:(0.2～1.5).
2. but the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light according to claim 1, is characterized in that described mixing polyolefin resin is comprised of 10～30 parts of polyethylene, 10～60 parts of ethylene-vinyl acetate copolymers, 15～30 parts of POE, 10～20 parts of polyethylene maleic anhydride grafts, 5～20 parts of ethene-vinyl acetate maleic anhydride grafts and 2～15 parts of ethylene octene maleic anhydride grafts by weight; Described fire retardant is magnesium hydroxide or aluminium hydroxide.
3. but the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light according to claim 1 is characterized in that described coupling agent is one or both the mixture in silane coupling agent and aluminate coupling agent; Described silane coupling agent is a kind of in vinyltriethoxysilane, vinyltrimethoxy silane, γ aminopropyltriethoxy silane, benzene n-formyl sarcolysine ethyl triethoxy silicane alkane, γ-second phenodiazine base propyl trimethoxy silicane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane and γ-propyl methacrylate base Trimethoxy silane or several mixture wherein; Described aluminate coupling agent is a kind of in aluminate coupling agent DL411-B, aluminate coupling agent DL-811, aluminate coupling agent DL412-A, aluminate coupling agent DL412-B and aluminate coupling agent DL-467 or several mixture wherein; Described transparent nucleater is 2,2'-methylene radical-two (4,6-di-n-butyl phenol), 2,2'-methylene-bis (4, the 6-di-tert-butyl-phenyl) a kind of in phosphoric acid ester sodium, dibenzal sorbitol, two (to the benzyl chloride fork) sorbyl alcohol, MDBS, two (to the ethyl benzal) sorbyl alcohol, DMDBS, mica and silicon-dioxide or wherein several mixture.
4. but the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light according to claim 1, it is characterized in that described initiator is 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, Michler's keton, 2,4-diethyl thioxanthone, isopropyl thioxanthone, benzoin dimethylether, 4-methyldiphenyl ketone and OXYBENZONE, a kind of in the 4-chlorobenzophenone or several mixture wherein; Described additional crosslinker is a kind of in Viscoat 295, the rare propyl ester of phthalic acid two, methyl methacrylate, methacrylate second diester, trimethylammonium vulcabond and 4-dimethyl ethyl aminobenzoate or several mixture wherein; Described oxidation inhibitor is 2,6-di-tert-butyl-4-methy phenol, 3,5-di-tert-butyl-hydroxy phenyl propionic acid stearyl alcohol ester, 4'4-thiobis (6-tert-butyl o cresols), 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 4-[methylene radical-3-(3', 5'-di-t-butyl-4'-hydroxy phenyl) propionic acid] a kind of in pentaerythritol ester, triphenylphosphate and triphenyl phosphite or several mixture wherein.
But 5. the preparation method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light as claimed in claim 1, but it is characterized in that the preparation method of the low-smoke halide-free fireproof composite polyolefine material that natural light is crosslinked carries out according to the following steps:
One, take each component: take by weight the mixing polyolefin resin of 100 parts of dryings, 80～150 parts of fire retardants, 0.2～0.8 part of initiator, 2～6 parts of additional crosslinkers, 0.01～0.6 part of oxidation inhibitor, 2～6 parts of coupling agents and 2～7 parts of transparent nucleaters, the mass ratio of wherein said initiator and additional crosslinker is 1:(7～26), the mass ratio of described initiator and oxidation inhibitor is 1:(0.2～1.5);
Two, preparation mixing solutions: 0.2～0.8 part of initiator, 2～6 parts of additional crosslinkers and 0.01～0.6 part of oxidation inhibitor that step 1 is taken join in beaker simultaneously, the mass ratio of wherein said initiator and additional crosslinker is 1:(7～26), the mass ratio of described initiator and oxidation inhibitor is 1:(0.2～1.5), be to stir 20min～40min under the condition of 55 ℃～85 ℃ in temperature, make mixing solutions;
Three, the polyolefin resin of preparation after mixing: take the mixing solutions that 1～5 part of step 2 makes, 80～150 parts of fire retardants that itself and step 1 are taken, 2～6 parts of coupling agents and 2～7 parts of transparent nucleaters join mixing in polyolefin resin of 100 parts of dryings that step 1 takes simultaneously, be banburying 15min～20min under 145 ℃～160 ℃ conditions in temperature, namely obtain the polyolefin resin after mixing;
Four, twin screw extruder granulation: with the twin screw extruder Temperature Setting at 160 ℃～185 ℃, then step 3 is obtained mixing after polyolefin resin by the twin screw extruder granulation, but namely obtain the crosslinked low-smoke halide-free fireproof composite polyolefine material of natural light.
6. but the preparation method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light according to claim 5, is characterized in that the mixing polyolefin resin described in step 1 is comprised of 10～30 parts of polyethylene, 10～60 parts of ethylene-vinyl acetate copolymers, 15～30 parts of POE, 10～20 parts of polyethylene maleic anhydride grafts, 5～20 parts of ethene-vinyl acetate maleic anhydride grafts and 2～15 parts of ethylene octene maleic anhydride grafts by weight; Fire retardant described in step 1 is magnesium hydroxide or aluminium hydroxide.
7. but the preparation method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light according to claim 5, it is characterized in that the coupling agent described in step 1 is the mixture of the one or both in silane coupling agent and aluminate coupling agent, described silane coupling agent is vinyltriethoxysilane, vinyltrimethoxy silane, γ aminopropyltriethoxy silane, benzene n-formyl sarcolysine ethyl triethoxy silicane alkane, γ-second phenodiazine base propyl trimethoxy silicane, β-(3, the 4-epoxycyclohexyl) a kind of ethyl trimethoxy silane and γ-propyl methacrylate base Trimethoxy silane) or several mixture wherein, described aluminate coupling agent is aluminate coupling agent DL411-B, aluminate coupling agent DL-811, aluminate coupling agent DL412-A, a kind of in aluminate coupling agent DL412-B and aluminate coupling agent DL-467 or several mixture wherein, transparent nucleater described in step 1 is 2,2'-methylene radical-two (4,6-di-n-butyl phenol), 2,2'-methylene-bis (4, the 6-di-tert-butyl-phenyl) a kind of in phosphoric acid ester sodium, dibenzal sorbitol, two (to the benzyl chloride fork) sorbyl alcohol, MDBS, two (to the ethyl benzal) sorbyl alcohol, DMDBS, mica and silicon-dioxide or wherein several mixture.
8. but the preparation method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light according to claim 5, it is characterized in that the initiator described in step 1 is 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, Michler's keton, 2,4-diethyl thioxanthone, isopropyl thioxanthone, benzoin dimethylether, 4-methyldiphenyl ketone and OXYBENZONE, a kind of in the 4-chlorobenzophenone or several mixture wherein; Additional crosslinker described in step 1 is a kind of in Viscoat 295, the rare propyl ester of phthalic acid two, methyl methacrylate, methacrylate second diester, trimethylammonium vulcabond and 4-dimethyl ethyl aminobenzoate or several mixture wherein; Oxidation inhibitor described in step 1 is 2,6-di-tert-butyl-4-methy phenol, 3,5-di-tert-butyl-hydroxy phenyl propionic acid stearyl alcohol ester, 4'4-thiobis (6-tert-butyl o cresols), 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 4-[methylene radical-3-(3', 5'-di-t-butyl-4'-hydroxy phenyl) propionic acid] a kind of in pentaerythritol ester, triphenylphosphate and triphenyl phosphite or several mixture wherein.
But 9. the using method of the crosslinked low-smoke halide-free fireproof composite polyolefine material of a kind of natural light as claimed in claim 1, but it is characterized in that the using method of the low-smoke halide-free fireproof composite polyolefine material that natural light is crosslinked carries out according to the following steps:
But the low-smoke halide-free fireproof composite polyolefine material that natural light is crosslinked is made the sheet material that thickness is 0.4mm～1.0mm, is placed under daylight and shines, and light application time is 72h～120h, namely obtains natural light cross-linking low smoke halogen-free fire retardant polyolefin material.
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| CN112063035B (en) * | 2020-08-25 | 2022-11-11 | 广东聚石化学股份有限公司 | Silane natural light crosslinked halogen-free flame-retardant cable material and preparation method thereof |
| CN112266527A (en) * | 2020-09-17 | 2021-01-26 | 杭州以田科技有限公司 | Silane and ultraviolet double-crosslinking low-smoke halogen-free cable material and preparation method thereof |
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Application publication date: 20130515 |