CN1218994C - Fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board and its preparing method - Google Patents

Fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board and its preparing method Download PDF

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CN1218994C
CN1218994C CN 02113998 CN02113998A CN1218994C CN 1218994 C CN1218994 C CN 1218994C CN 02113998 CN02113998 CN 02113998 CN 02113998 A CN02113998 A CN 02113998A CN 1218994 C CN1218994 C CN 1218994C
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halogen
polyethylene
fire
core material
applicable
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CN1445273A (en
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王小红
翦建政
何斌
肖顺秋
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Hunan Keoct Materials Co., Ltd.
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HUNAN PROVINCE PLASTICS INST
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Abstract

The present invention relates to a halogen-free flame-resistance polyethylene core layer material for a fireproof aluminium plastic composite board and a preparation method thereof. The core layer material contains 10 to 40 wt% of polyethylene, 5 to 20 wt% of modified polyethylene, 35 to 65 wt% of halogen-free flame-resistance agent, 0.5 to 10 wt% of flame-resistance synergistic agent, and 2.5 to 8.5 wt% of other auxiliary agents. The preparation method for the material comprises the steps: grain materials and board materials special for the flame-resistance polyethylene are prepared; parallel dual-screw extrusion hot cutting granulation technology and equipment are adopted; continuous kneading, extrusion, air cooling hot cutting technology and equipment are adopted to prepare the grain materials special for the flame-resistance polyethylene; and vacuum exhaust type single-screw extrusion board technology and equipment are adopted to prepare the board materials special for the flame-resistance polyethylene. The preparation method has the advantages of easy control of technology conditions, stable and reliable quality of the product, and continuous automatic production. The material is applied to compositely produce the fireproof aluminium plastic board, the grade of the combustion performance can reach the B1 grade of materials which is difficult to combust or the A grade of incombustible materials. Meanwhile, the rationalization performance and the processing forming performance of the material can satisfy the requirements of production technology.

Description

Non-halogen Fire Retardant Polyethylene Core Material Used For Aluminum Plates And Its Preparation Method
Technical field
The present invention relates to a kind of as new decorative material for building-fireproof aluminum-plastic board flame-proof polyethylene core material and preparation method thereof, particularly LSOH anti-flaming resistant sandwich materials with polyethylene and preparation method thereof.
Background technology
The composited aluminum and plastic decking core material that present patent application discloses a few days ago, uses and sells has two kinds of the fire-retardant core materials of pure resistant sandwich materials with polyethylene and Halogen.The former pure resistant sandwich materials with polyethylene at present on market mass selling be applied to the conventional aluminium plastic clad plate and make core material, account for more than 90%, but because its oxygen index only is 17.5, not fire-retardant, belong to inflammable material, the burning back is the fusion drippage easily, initiation fire spreads, so used by public security fire-fighting department and the restriction of building design and construction department at present, especially in important public place, as occasions such as drome, station, top grade entertainment place and high-grade Highrise buildings indoor and outdoor decorations, require to use difficult combustion or do not fire a grade fire proof construction finishing material.The latter is the Halogen inflaming retarding core material, though have certain flame retardant resistance, but because of body material Halogen or adding halogen/antimony fire retardant, when taking place, fire can produce a large amount of deleterious carbon monoxide and severe corrosive hydrogen halide smog because of burning, cause secondary pollution, thus with its aluminium-plastic panel of doing core material production because of do not meet environmental protection industry policy and require and in the world the developing direction of fire retardant chemistry building materials just progressively be eliminated.
Summary of the invention
Technical problem to be solved by this invention be to overcome the shortcoming of above-mentioned two kinds of core materials and provide a kind of Halogen, low cigarette, fire-retardant, resistance is dripped and Nonpoisonous, non-environmental-pollutionization, hot pressing bonding strength height and the flexible rolling of sheet material, be easy to the Non-halogen Fire Retardant Polyethylene Core Material Used For Aluminum Plates And Its Preparation Method of continuous large-scale production.
Solving the technology of the present invention problem is to realize by following technical proposals:
Fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board contains polyethylene, modified poly ethylene, halogen-free flame retardants, retardant synergist, other auxiliary agents etc., and its composition (weight percent) is: polyethylene 10~40%, modified poly ethylene 5~20%, halogen-free flame retardants 35~65%, retardant synergist 0.5~10%, other auxiliary agents 2.5~8.5%.
The preparation method of fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board of the present invention is: prepare the special-purpose pellet of flame-proof polyethylene earlier, and then make sheet material.The preparation method of the special-purpose pellet of flame-proof polyethylene, be to mix selected part or all of halogen-free flame retardants composite by a certain percentage earlier, in common high-speed mixer, carry out pre-treatment with part or all of composite coupler again, being mixed together even back with other remaining components adopts parallel double-screw to extrude fervent prepared by granulating process pellet, but preferably adopt in the continuous milling machine of closed and carry out kneading, after the plasticizing evenly, send into major diameter by conical double-screw feeder, in the single screw extrusion machine of little length-to-diameter ratio, through head die face hot cut pellet, secondary cyclone cooling back packing.The special-purpose pellet of the flame-proof polyethylene of preparation adopts the single screw rod plate squeezing of vacuum exhaust formula Processes and apparatus, extrudes the back three-roll press-polishing and makes Zero halogen flame resistance polyethylene roll bending material.
Use the fireproof aluminum-plastic board of the compound production of this material, the combustionproperty classification can reach nonflammable material B1 level or uninflammability A level, and its physicochemical property and machine-shaping property can satisfy the manufacturing technique requirent of composited aluminum and plastic decking simultaneously.Characteristics such as this material has that halide-free smokeless, fire-retardant resistance drip, hot pressing bonding strength height and the flexible rolling of sheet material.
Its preparation technology's uniqueness of material of the present invention can adopt the parallel double-screw extruding and pelletizing process, but preferably adopts the special-purpose pellet of continuous kneading+extrude+air-cooled hot cut pellet prepared flame-proof polyethylene; Adopt the single screw rod plate squeezing of vacuum exhaust formula Processes and apparatus, preparation fireproof aluminum-plastic board special-purpose anti-flaming polyethylene board.Described preparation method, processing condition are easy to control, and stable and reliable product quality can realize continuous automatic production.
Embodiment
Polyethylene can be a high-pressure polyethylene in the fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board of the present invention, one or more the composite compositions in high density polyethylene(HDPE) and/or the linear low density polyethylene etc., and its melt flow rate (MFR) is 0.15~5g/min.
Modified poly ethylene is one or more the composite compositions in the polarity graft copolymer of ethene-Sipacril 2739OF (EAA), ethene-vinyl acetate copolymer (EVA), terpolymer EP rubber (EPDM) and/or polyolefine and unsaturated monoprotic acid or unsaturated dibasic acid or MALEIC ANHYDRIDE (MAH) in the fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board of the present invention, and its melt index is 0.25~250g/10min.Described MALEIC ANHYDRIDE polarity graft copolymer, it specifically consists of (weight part):
TPO or thermoplastic elastomer: 100
Polarity grafted monomer: 0.5~5.0
Peroxide initiator: 0.1~1.0
Grafting auxiliary agent: 0.05~0.5
The existence of polyethylene and modified poly ethylene in the fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board of the present invention has constituted the matrix resin of whole fire-retardant polyethylene material.These resins have significantly improved the deterioration of caused material mechanical performance of fire retardant filling and processing characteristics, have guaranteed aluminium-plastic panel of the present invention flame-proof polyethylene core excellent comprehensive performances.
Fire retardant must be not halogenous in the fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board of the present invention, inorganic mineral based flame retardant preferably, these halogen-free flame retardantss comprise the mixing compound of hydrated aluminum oxide, magnesium hydroxide, magnesium basic carbonate, alkali magnesium sulfate crystal whisker and/or these compounds, and its powder size is that 0.1~50 μ m and/or diameter are 0.1~0.5 μ m, the length whisker less than 80 μ m.These fire retardants reduce thermal value and flame temperature, the dilution combustion air in beginning thermal endothermic decomposition dehydration more than 200 ℃; Decompose the carburization zone of the metal oxide of generation, play an adiabatic protection and a resistance incarbonization, thereby the inhibition burning reduces the amount of being fuming in material surface formation one deck firm compact.
Retardant synergist is the organic class or the inorganic matter of energy synergy fire retardant function in the fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board of the present invention, comprises the compound of red phosphorus microcapsule masterbatch or non-halogen phosphoric acid ester, hydroxy silicon oil, zinc borate or zinc oxide, silicon-dioxide or silicon powder, ammonium polyphosphate and/or these materials.The existence of these materials can be brought into play the synergistic effect between different flame retardant better, makes flame retardant effect more outstanding, and the fire retardant total amount reduces.
Other auxiliary agents comprise coupling agent, dispersion agent, rheological agent, oxidation inhibitor, UV light absorber, linking agent or tinting material etc. in the fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board of the present invention.Wherein coupling agent is for effectively improving the material of fire retardant and polyethylene base material boundary face consistency, as titanate coupling agent, aluminate coupling agent, silane coupling agent and/or several composite couplers wherein, specifically comprise KR-TTS, DL-411-D, A-174, A-172, A-151 etc.; Dispersion agent and rheological agent etc. are dispersed and extrude processing fluidity for improving each component, thereby reduce the chemical substance of mixture viscosity, specifically comprise lipid acid and acid amides thereof or salt, low-molecular-weight polyolefin, organic silicone and/or fluorinated rheological agent etc.; Oxidation inhibitor (as 1010), UV light absorber (as UV-531), linking agent (as DCP), tinting material are (as TiO 2Or carbon black) etc. be for effectively improving the material of performances such as material thermo oxidative aging, photoaging, degree of crosslinking and color.
Fireproof aluminum-plastic board of the present invention comprises the special-purpose pellet of preparation flame-proof polyethylene earlier, and then makes sheet material with Halogen combustion resistant sandwich materials with polyethylene preparation method.The preparation method of the special-purpose pellet of flame-proof polyethylene mixes selected part or all of halogen-free flame retardants composite earlier by a certain percentage, in common high-speed mixer, carry out pre-treatment with part or all of composite coupler again, being mixed together even back with other remaining components adopts parallel double-screw to extrude fervent prepared by granulating process pellet, but preferably adopt in the continuous milling machine of closed and carry out kneading, after the plasticizing evenly, send into major diameter by conical double-screw feeder, in the single screw extrusion machine of little length-to-diameter ratio, through head die face hot cut pellet, secondary cyclone cooling back packing.Pellet is extruded the back three-roll press-polishing with vacuum exhaust formula single screw extrusion machine become flame-proof polyethylene roll bending material.Traditional granulation process method for open the refining or banburying after board-like pelletizing; Or with cold drawn pelletizing of single, double screw mixing expressed water, these methods are if be used for preparing this material, and then not only labour intensity is big, processing condition are wayward, and fire retardant disperses uneven, and it is stable that quality product can't keep, or because of after the product suction pelletizing when dry again, complex operation, power consumption consuming time.Characteristics according to fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board of the present invention, the present invention adopts efficiently, clean and processing condition can accurately be controlled with the parallel double-screw of continuous automatic production and extrude fervent granulation process, but preferably adopt continuous kneading+extrude+air-cooled fervent granulation process and equipment.The special-purpose pellet of prepared Zero halogen flame resistance polyethylene can adopt the bigger twin screw plate squeezing technology of investment, and main is single screw rod plate squeezing Processes and apparatus that can adopt investment lower, carries out the continuous large-scale production of sheet material.
Fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board of the present invention is compared with traditional halogen containing polymers core or halogen/antimony flame-proof polyethylene core, not containing halide not only, fusion is not dripped, and dependence generates non-harmful carbon dioxide and plays the moisture of cooling diluting effect and the metal oxide that energy covering material surface takes blocking effect through the thermal endothermic decomposition reaction of inorganic mineral based flame retardant under high temperature (burning) environment of coupling activation treatment.Owing to adopted aforesaid particular design on the prescription, therefore fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board of the present invention has characteristics such as low cost, halide-free smokeless, fire-retardant, hot pressing bonding strength height and the flexible rolling of sheet material, and when adopting the compound production fireproof aluminum-plastic board of material of the present invention, composite molding technique is functional, can satisfy the processing requirement of aluminium-plastic panel standard and continuous industry production line.
Specific embodiments of the present invention is provided by embodiment.
Example formulations sees attached list 1, and its concrete operations step is basic identical, and promptly the first step is carried out surface preparation by the composite back of all or part of halogen-free flame retardants of prescription with composite coupler, carries out in homogenizer.Second step, press the prescription weighing, be mixed together evenly with all the other components and extrude hot cut pellet technology, but preferably join kneading plasticizing under given technological temperature and time in the continuous milling machine with parallel double-screw; In the 3rd step, above-mentioned kneading plastifies uniform mixture and sends into the extruding pelletization unit through conical double-screw feeder, extrudes the die face hot cut pellet; In the 4th step, hot cut pellet is promptly made the flame-proof polyethylene pellet through the cooling of secondary cyclone separator, vibratory screening apparatus go-on-go packing.Prepared fire-retardant PE pellet adopts screw slenderness ratio greater than 32 the single screw rod plate squeezing of vacuum exhaust formula unit, becomes halogen-free flameproof PE roll bending material through three-roll press-polishing.
The homogenizer mixing time of using among the preparation method of the present invention is 2-10 minute, and mixing temperature is 50-70 ℃; The kneading time is 5~15 minutes in the milling machine continuously, and the kneading temperature is 80-160 ℃, and two hello the grain machine temperature of awl are 110~150 ℃, and the extruding pelletization temperature is 120~190 ℃, is preferably 130~185 ℃.
The extrusion board technological temperature is 130~200 ℃, is preferably 140~190 ℃, and 50~100 ℃ of tri-roll press machine temperature are preferably 60~95 ℃, and vacuum tightness is-and more than the 0.02MPa, screw slenderness ratio is more than 32, preferably is not less than 35.
Fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board technical performance index of the present invention is: tensile strength is 7.5~10.5MPa, flexural strength 9.5-28.5MPa, notched Izod impact strength: 7.0-14.0KJ/m 2, vicat softening temperature is 80~86 ℃, and the longitudinal size velocity of variation is 18~25%, 180 ° of stripping strength 5.0~8.5N/mm, and oxygen index is up to 34%-42%.
Detailed performance perameter sees attached list 2
Use the fireproof aluminum-plastic board of the compound production of Zero halogen flame resistance polyethylene core material of the present invention, the combustionproperty classification can reach nonflammable material B1 level or uninflammability A level, wherein: burning residue length minimum value is 155-655mm, flue-gas temperature is 85~125 ℃, the flame cusp height is 5-20mm, and the smoke density grade is 5-65.Detailed combustionproperty index sees attached list 3.
Subordinate list 1 Example formulations is formed
Prescription is formed Embodiment
One Two Three Four Five Six
Polyethylene 25 28 32 30 20 10
Modified poly ethylene 15 10 8 4 12 15
Mg(OH) 2/AL(OH) 3 40 45 50 55 58 62
Zinc borate/ZnO 5
Silicon powder/magnesium salt whisker 5-10 0.5-5
Red phosphorus/ammonium polyphosphate 6 8 4
Phosphoric acid ester/hydroxy silicon oil 0-5 0.5-5 0.5-5 0.5-5 0-5 2-5
The peroxide initiator 0.1-0.5 0.1-0.5 0-0.5 0-0.5 0.1-0.5 0.1-0.5
Composite coupler 1.4 1.8 2.0 2.2 2.4 2.8
Rheological agent 0.1-0.5 0.1-0.5 0.1-0.5 0.1-0.5 0.1-0.5 0.1-0.5
Dispersion agent 1.5 1.8 2.0 2.2 2.4 2.8
Other 0-0.5 0-0.5 0-0.5 0-0.5 0-0.5 0-0.5
Subordinate list 2 Zero halogen flame resistance polyethylene core material performance index
Interventions Requested Unit Testing method Performance index
Tensile yield strength MPa GB1040 7.5-10.5
Flexural strength MPa GB1042 9.5-28.5
Notched Izod impact strength KJ/m 2 GB1043 7.0-14.0
Vicat softening temperature GB1633 80-86
180 ° of stripping strengths (aluminium-mould) N/mm GB/T2790 5.0-8.5
The longitudinal size velocity of variation GB/T2490 18-25
Oxygen index GB2406 34-42
Proportion g/cm 3 GB1033 1.28-1.48
HCL content mg/g 0
Subordinate list 3 fireproof aluminum-plastic board combustionproperty indexs
Interventions Requested The method of inspection The B1 level The A level Detect index
Burning residue length minimum value/mm GB/T8625 >0 ≥150 155-655
Burning residue length mean value/mm GB/T8625 ≥150 ≥350 180-685
Flue-gas temperature/℃ GB/T8625 ≤200 ≤125 85-125
Flame cusp height/mm GB/T8626 ≤150 ≤150 5-20
The smoke density grade GB/T8627 ≤75 ≤15 5-65

Claims (9)

1. fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board, contain polyethylene, modified poly ethylene, halogen-free flame retardants, retardant synergist, other processing aids, it is characterized in that its content composition (weight percent) is: polyethylene: 10-40%, modified poly ethylene: 5-20%, halogen-free flame retardants: 35-65%, retardant synergist: 0.5-10%, other auxiliary agents: 2.5-8.5%.
2. fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board according to claim 1, it is characterized in that described polyethylene is one or more the composite compositions in high-pressure polyethylene, high density polyethylene(HDPE) and/or the linear low density polyethylene, its melt flow rate (MFR) is 0.15~5g/min.
3. fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board according to claim 1, it is characterized in that described modified poly ethylene is one or more the composite compositions in the polarity graft copolymer of ethylene-methacrylic acid copolymer, ethylene-vinyl acetate copolymer, terpolymer EP rubber and/or polyolefine and unsaturated monoprotic acid or unsaturated dibasic acid or MALEIC ANHYDRIDE, its melt index is 0.25~250g/10min.
4. fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board according to claim 3 is characterized in that described MALEIC ANHYDRIDE polarity graft copolymer, and it specifically consists of (weight part):
TPO or thermoplastic elastomer: 100
Polarity grafted monomer: 0.5~5.0
Peroxide initiator: 0.1~1.0
Grafting auxiliary agent: 0.05~0.5.
5. fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board according to claim 1, it is characterized in that described halogen-free flame retardants is that 0.1~50 μ m and/or diameter are 0.1~0.5 μ m, the length whisker less than 80 μ m for not halogen-containing inorganic mineral based flame retardant comprises the compound of aluminium hydroxide, magnesium hydroxide, magnesium basic carbonate, alkali magnesium sulfate crystal whisker and/or these compounds, its powder size.
6. fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board according to claim 1 is characterized in that described retardant synergist comprises the compound of red phosphorus microcapsule masterbatch or non-halogen phosphoric acid ester, hydroxy silicon oil, zinc borate or zinc oxide, silicon-dioxide or silicon powder, ammonium polyphosphate and/or these materials.
7. the preparation method of a fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board, comprise the special-purpose pellet of preparation flame-proof polyethylene earlier, and then make sheet material, the preparation method who it is characterized in that the special-purpose pellet of flame-proof polyethylene mixes selected part or all of halogen-free flame retardants composite earlier by a certain percentage, in common high-speed mixer, carry out pre-treatment with part or all of composite coupler again, being mixed together even back with other remaining components adopts parallel double-screw to extrude fervent prepared by granulating process pellet, also can adopt in the continuous milling machine of closed and carry out kneading, after the plasticizing evenly, send into major diameter by conical double-screw feeder, in the single screw extrusion machine of little length-to-diameter ratio, through head die face hot cut pellet, secondary cyclone cooling back packing.
8. the preparation method of fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board according to claim 7, it is characterized in that mixing time is 2~10 minutes in the high-speed mixer, mixing temperature is 50~70 ℃, the kneading time is 5~15 minutes in the milling machine continuously, 80~160 ℃ of kneading temperature, the conical double-screw feeder temperature is 110~150 ℃, and the extruding pelletization temperature is 120~190 ℃.
9. the preparation method of fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board according to claim 7, it is characterized in that Zero halogen flame resistance polyethylene pellet to preparation, adopt the single screw rod plate squeezing of vacuum exhaust formula Processes and apparatus, extrude the back three-roll press-polishing and make Zero halogen flame resistance polyethylene roll bending material, the extrusion board technological temperature is 130~200 ℃, 50~100 ℃ of tri-roll press machine temperature, vacuum tightness be-more than the 0.02MPa, screw slenderness ratio is more than 32.
CN 02113998 2002-03-19 2002-03-19 Fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board and its preparing method Expired - Lifetime CN1218994C (en)

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