CN103978744B - Plastic-aluminum combined stiff sheet material of a kind of halogen-free flameproof and preparation method thereof - Google Patents
Plastic-aluminum combined stiff sheet material of a kind of halogen-free flameproof and preparation method thereof Download PDFInfo
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Abstract
The invention discloses plastic-aluminum combined stiff sheet material of a kind of halogen-free flameproof and preparation method thereof.This material is made up with the polyvinyl inflaming retarding core material compound scribbling polymerizable organosilicon nitride layer of the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate, and the gluing nitride layer of the ethene-vinyl acetate described in compound tense connects with polymerizable organosilicon nitride layer; Described polyvinyl inflaming retarding core material is made up of the raw material of following weight portion: 54 parts of-74 parts of high density polyethylene (HDPE)s, 16 portions of-28 portions of triphenyl phosphates and 10 parts of-18 parts of boron nitride fibers.This material has fire-retardant and smoke suppressing effect efficiently, and excellent tensile strength and barrier property, anti-ultraviolet ageing is good.Preparation method of the present invention first by melt blending polyethylene extrusion base inflaming retarding core material, then applies one deck organosilicon polymer on core, above finally the Aluminium film paste scribbling the gluing nitride layer of EVA being overlayed on, delays obtained through the hot compound of roll-in, cold roll-in.This preparation method is simple to operate, is suitable for suitability for industrialized production.
Description
Technical field
The present invention relates to field of compound material, be specifically related to plastic-aluminum combined stiff sheet material of a kind of halogen-free flameproof and preparation method thereof.
Background technology
Plastic-aluminum combined stiff sheet material on rigid plastics, pastes aluminium film and obtained composite.Plastic-aluminum combined stiff sheet material has the features such as quality is hard, fashionable appearance, anti-ultraviolet radiation, good barrier property, easy construction, has been widely used in the fields such as architectural engineering protection, advertising board, fitting-up, Furniture manufacture.More economical and the environmental protection relative to fine aluminium sheet material of plastic-aluminum combined stiff sheet material, meets the demand for development of social recycling economy and low-carbon economy.At present, the base material of plastic-aluminum combined stiff sheet material generally uses the macromolecular materials such as inflammable polystyrene, nylon, and this has buried hidden danger for breaking out of fire.For promoting the fire savety of plastic-aluminum combined stiff sheet material in the field such as architectural engineering, decorating and renovating material, promote that the scale of this series products is applied, the plastic-aluminum combined stiff sheet material of exploitation highly effective flame-retardant, low cigarette environmental protection is imperative.
The fire resistance strengthening plastic-aluminum combined stiff sheet material can by adding fire retardant to realize in base material and adhesion layer.Because the thickness of stiff sheet material is relatively thin, so also relatively high for the requirement of the fire retardant added.In general, the fire retardant being applicable to thin gauge sheet comprises: (1) halogenated flame retardant, such as decabromodiphenyl oxide, eight bromobiphenyl etc., this based flame retardant suppresses burning behavior by catching the free radical produced in macromolecular material thermal cracking processes, normal with antimony oxide conbined usage, be the efficient fire retardant of a kind of tradition.But, a large amount of toxic fumes can be discharged during halogenated flame retardant thermal cracking, and it is difficult to metabolism again after being entered in human body by nature food endless-chain and out, is therefore eliminated gradually.(2) P-N type fire retardant, such as organophosphorus ester, APP etc., in most cases phosphorus-nitrogen acts synergistically on by fire proofing, by forming the intumescent carbon-coating of one deck densification at inflammable polymer surface, comes the infiltration of blocking oxygen and spreading of flame.But the flame retarding efficiency of P-N type fire retardant is not high, during for thin gauge sheet, carbon source is not enriched, thus causes carbon-coating obstructing capacity not enough.(3) hydrated metal oxide, mainly refer to aluminium hydroxide and magnesium hydroxide, this based flame retardant is cheap, thermal stability good, do not produce etchant gas and the sour gas discharged in energy and in macromolecule thermal cracking processes, absorbed heat by dehydration and reduce environment temperature, there is nontoxic, environmental protection, press down the feature of cigarette.Such as, Chinese patent application CN01114843.8 discloses a kind of fire prevention shape aluminum composite plate manufacture method, comprise flame-retardant polyethylene plastic to add in single screw extrusion machine and be extruded into sheet material, become sheet material for sandwich layer with flame-retardant polyethylene plastic, outer subsides aluminium sheet composite skins, be combined into composited aluminum and plastic decking, wherein, the factory formula of flame-retardant polyethylene plastic is: fire retardant (one or both in aluminium hydroxide, magnesium hydroxide powder) 75 parts, titanate coupling agent (KH-201) 0.75 part, 0.2 part, ethyl acetate, polyethylene 27 parts, stearic acid 2 parts; The processing technology of flame-retardant polyethylene plastic is: activation process-batch mixing-granulation; This mould aluminum composite plate burn time low cigarette, without pernicious gas generation, there is fire-proof function.But, hydrated metal oxide will make to be reached excellent fire resistance by fire proofing, and often addition is very large, can destroy the intrinsic mechanical property of macromolecular material to a certain extent, adhesion between inorganic decentralized photo and macromolecule continuous phase is more weak, and composite becomes fragile.On the other hand, in polymer matrix composite system, inorganic component is excessive, such that material melt viscosity is excessive, plasticity is deteriorated, be difficult to be processed into slim composite sheet (thickness 0.5mm-2.0mm).
So, the aluminium plastic composite material of, thinner thickness hard for quality, by rational structural design, need introduce new flame retarding process, prepare a kind of Halogen, press down the plastic-aluminum combined stiff sheet material of functional form of cigarette, highly effective flame-retardant, to expand the range of application of plastic-aluminum combined stiff sheet material.
Summary of the invention
The invention provides the plastic-aluminum combined stiff sheet material of a kind of halogen-free flameproof, it has fire-retardant and smoke suppressing efficiently, and tensile strength is high, the feature such as to intercept and anti-ultraviolet ageing is good.
Present invention also offers the preparation method of the plastic-aluminum combined stiff sheet material of a kind of halogen-free flameproof, this preparation method is simple to operate, is suitable for suitability for industrialized production.
The present invention adopts following technical scheme:
The plastic-aluminum combined stiff sheet material of a kind of halogen-free flameproof, be made up with the polyvinyl inflaming retarding core material compound scribbling polymerizable organosilicon nitride layer of the aluminium film scribbling ethene-vinyl acetate (EVA) gluing nitride layer, the gluing nitride layer of the ethene-vinyl acetate described in compound tense connects with polymerizable organosilicon nitride layer.
Described polyvinyl inflaming retarding core material is mainly extruded through melt blending by the raw material of following weight portion and is made: 54 parts of-74 parts of high density polyethylene (HDPE)s (HDPE), 16 portions of-28 portions of triphenyl phosphates and 10 parts of-18 parts of boron nitride fibers.Triphenyl phosphate thermal decomposition at a certain temperature produces phosphoric acid, and phosphoric acid impels top layer polythene material to be dehydrated into charcoal, and layer of charcoal effectively can isolate spreading of oxygen and heat, and protection primer stops it to burn further; The boron nitride fiber of heat conduction and excellent fire retarding performance is uniformly distributed in inflaming retarding core material crisscrossly, after burning makes system reach uniform temperature, fiber sheath and layer of charcoal bond formation cross-linked network mutually, this structure effectively can strengthen the intensity of large area layer of charcoal, prevents Char Residues Structure from caving in and causes core to be exposed to resume combustion in air.Preferably, described boron nitride fiber length is 2mm-3mm, and diameter is 4.5 μm-9.5 μm, can reach effect of the present invention better.
Described organosilicon polymer selects Polyborosiloxane, and mean molecule quantity is 2000-3000.Polyborosiloxane can form continuous oxidation resistant silicate protective layer on layer of charcoal surface in combustion, promotes compactness and the barrier of layer of charcoal, suppresses diffusion and the heat radiation of oxygen further; Polyborosiloxane possesses gas phase flame retardant effect on the other hand, and in combustion process, the boron in Polyborosiloxane exists with the form of metaboric acid and metaboric acid ester, and it can eliminate the peroxy radical that polyethylene produces in thermal cracking, suppresses the oxicracking of polymer.
Described Polyborosiloxane can adopt following preparation method, comprising: boric acid, ethyl orthosilicate and absolute ethyl alcohol are mixed, be heated to 60 DEG C-70 DEG C, stirring and refluxing, then slowly add hydrochloride aqueous solution, after back flow reaction 3h-3.5h, decompression distillation obtains clear Polyborosiloxane; Wherein, the mol ratio of boric acid and ethyl orthosilicate is 2.1-2.2:1, and the mol ratio of hydrogen chloride and ethyl orthosilicate is 0.1-0.15:1 (being preferably 0.1-0.12:1).The excessive obtained Polyborosiloxane of molar ratio of boric acid and ethyl orthosilicate be Powdered, molecular weight is low and poor toughness; Ratio is too small is also unfavorable for that molecular weight increases for both, and Polyborosiloxane is deteriorated to the adhesive force of base material with to the adhesive property of EVA adhesive layer.
Described EVA sicker is mainly extruded through melt blending by the raw material of following weight portion and is made: 30 parts of-40 parts of EVA resin, 25 parts of-30 parts of rosin, 18 parts of-23 parts of paraffin, 5 parts of fillers, 7 parts of-17 parts of molybdenum compounds and appropriate antioxidant.The molybdenum compound added in the gluing nitride layer of EVA can promote that EVA sicker layer main body resin EVA pyrolysis is cross-linked coking; At high temperature there is the cracking reaction of polyenoid cation simultaneously, increase in gas phase and can reduce raw smoke which for the fuel of burning, and the aromatic series flue dust parent formed after core and organosilicon polymer thermal cracking is bonded in metal-aromatic series compound securely.
The inorganic filler that described filler can select this area conventional, the one in preferably clay, calcium carbonate, barium sulfate.
The one in molybdenum trioxide, ammonium heptamolybdate, ammonium octamolybdate selected by described molybdenum compound.
The antioxidant that described antioxidant can select this area conventional, preferably 2,6-toluene di-tert-butyl phenols, 4, the one in 4 ˊ-bis-(6-tert-butyl-m-cresol) thioether.The consumption of described antioxidant can add according to this area conventional amount used, and the weight of preferably described antioxidant is the 0.05%-0.2% of EVA resin, rosin, paraffin, filler and molybdenum compound gross weight.
The carry painting amount of described organosilicon polymer on polyvinyl inflaming retarding core material is preferably 50g/m
2-250g/m
2, the spread of EVA sicker on aluminium film is preferably 30g/m
2-75g/m
2, effect of the present invention can be reached better.
Described aluminium film gives the good obstruct of composite hard sheet material and anti-ultraviolet ageing, can select pure aluminum foil, generally selects thickness to be the pure aluminum foil of 0.01mm-0.02mm when making sheet material.
It is thinner that halogen-free flameproof of the present invention plastic-aluminum combined stiff sheet material can do, and thickness can be 0.50mm-2.50mm, still possesses fire-retardant and smoke suppressing efficiently, high-tensile, good obstruct and anti-ultraviolet ageing; The other forms of composites such as halogen-free flameproof aluminum-plastic composite board can also be prepared according to the formula of the plastic-aluminum combined stiff sheet material of halogen-free flameproof of the present invention, although cost can raise but still can keep fire-retardant and smoke suppressing efficiently when making sheet material, high-tensile, good obstruct and anti-ultraviolet ageing.
The thickness of described polyvinyl inflaming retarding core material not strict restriction, generally can adjust according to the thickness of required product, when required product is composite hard sheet material, the thickness of polyvinyl inflaming retarding core material can make into about 0.48mm-0.49mm in advance, then adjust the spacing of the adjacent pressure roller of formative stage, namely can obtain the composite of desired thickness (such as thickness is 0.62mm).
The preparation method of the plastic-aluminum combined stiff sheet material of halogen-free flameproof of the present invention, be made up of aluminium film, the gluing nitride layer of ethene-vinyl acetate, polymerizable organosilicon nitride layer and polyvinyl inflaming retarding core material compound, described aluminium film is after heating roller coat EVA sicker, delay with the polyvinyl the inflaming retarding core material hot compound of roll-in, the cold roll-in under 85 DEG C of-105 DEG C of conditions that scribble one deck organosilicon polymer again, obtained flame-retardant aluminum plastic composite hard sheet material.Specifically comprise the steps:
(1) by high density polyethylene (HDPE), triphenyl phosphate and boron nitride fiber at 60 DEG C of-70 DEG C of premixs, extrude through equidirectional parallel double-screw extruder melt blending after mixing, roll, draw and cooling forming, obtained polyvinyl inflaming retarding core material;
(2) by organosilicon polymer roller coat on described polyvinyl inflaming retarding core material, then at 60 DEG C-65 DEG C dry, obtain the polyvinyl inflaming retarding core material scribbling polymerizable organosilicon nitride layer;
(3) by ethylene-vinyl acetate resin, rosin, paraffin, filler, molybdenum compound and antioxidant in 130 DEG C of-150 DEG C of mixing 20min-30min, extruded by equidirectional parallel double-screw extruder melt blending again, through cooling, dry and pelletizing, obtain ethene-vinyl acetate sicker;
(4) by described ethene-vinyl acetate sicker after heating and melting roller coat on aluminium film, obtain the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate, the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate is delayed with polyvinyl the inflaming retarding core material hot compound of roll-in and the cold roll-in under 85 DEG C of-105 DEG C of conditions scribbling polymerizable organosilicon nitride layer, the obtained plastic-aluminum combined stiff sheet material of halogen-free flameproof, wherein, the gluing nitride layer of ethene-vinyl acetate described in the hot compound tense of roll-in connects with polymerizable organosilicon nitride layer.
In step (1), described premix can complete in high-speed mixer (rotating speed is generally more than 5000 revs/min).In described equidirectional parallel double-screw extruder, district's temperature is 150 DEG C ± 5 DEG C, and two district's temperature are 160 DEG C ± 5 DEG C, and 3rd district, four He Wu district of district temperature are 185 DEG C ± 5 DEG C, and six district's temperature are 195 DEG C ± 5 DEG C, and seven district's temperature are 190 DEG C ± 5 DEG C.
In step (2), described oven dry can adopt air blast to dry, and also can adopt other quick-drying mode.
In step (3), described mixingly can to complete in kneader.In described equidirectional parallel double-screw extruder, district's temperature is 90 DEG C ± 2 DEG C, and two district's temperature are 110 DEG C ± 2 DEG C, and 3rd district, four He Wu district of district temperature are 125 DEG C ± 2 DEG C, and six district's temperature are 130 DEG C ± 2 DEG C, and seven district's temperature are 125 DEG C ± 2 DEG C.
The present invention's raw material used all can adopt commercially available prod.
Tool of the present invention has the following advantages:
Halogen-free flameproof of the present invention plastic-aluminum combined stiff sheet material has fire-retardant and smoke suppressing effect efficiently, and excellent tensile strength and barrier property, anti-ultraviolet ageing is good.
Preparation method of the present invention first by melt blending polyethylene extrusion base inflaming retarding core material, then applies one deck organosilicon polymer on core, above finally the Aluminium film paste scribbling the gluing nitride layer of EVA being overlayed on, delays obtained through the hot compound of roll-in, cold roll-in.This preparation method is simple to operate, is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is halogen-free flameproof of the present invention plastic-aluminum combined stiff sheet material structure schematic diagram;
In figure: 1-aluminium foil, the gluing nitride layer of 2-EVA, 3-polymerizable organosilicon nitride layer, 4-polyvinyl inflaming retarding core material.
Detailed description of the invention
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail.
Embodiment 1
By 54kg high density polyethylene (HDPE) (5000S/ raises sub-petrochemical industry), 28kg triphenyl phosphate, 18kg boron nitride fiber, (length is 2mm, diameter is 4.5 μm) in high-speed mixer (rotating speed 5000r/min) in 70 DEG C of premixs, (150 DEG C, a district is extruded through equidirectional parallel double-screw extruder melt blending after mixing, two 160 DEG C, districts, 3rd district, four He Wu districts of district are 185 DEG C, six 195 DEG C, districts, seven 190 DEG C, districts), calendering, traction, cooling forming, obtained polyvinyl inflaming retarding core material.
129.8g boric acid, 208.3g ethyl orthosilicate, 1000ml absolute ethyl alcohol are placed in reactor, be heated to 60 DEG C, stirring and refluxing, then the 40g hydrochloride aqueous solution that mass percentage concentration is 10% is slowly added, after back flow reaction 3h, decompression distillation obtains clear Polyborosiloxane, and mean molecule quantity is 2000.
By 30kgEVA resin, 25kg rosin, 23kg paraffin, 5kg calcium carbonate, 17kg ammonium octamolybdate and 0.1kg2,6-toluene di-tert-butyl phenol joins in kneader in 150 DEG C of mixing 30min, (90 DEG C, a district is melt extruded again by equidirectional parallel double-screw extruder, two 110 DEG C, districts, three, four, five 125 DEG C, districts, six 130 DEG C, districts, seven 125 DEG C, districts), cooling, dry, pelletizing, obtain ethene-vinyl acetate sicker, for subsequent use.
By Polyborosiloxane roller coat on polyvinyl inflaming retarding core material, carrying painting amount is 250g/m
2(Polyborosiloxane that every square meter polyvinyl inflaming retarding core material scribbles is 250g), then air blast is dried at 60 DEG C, the polyvinyl inflaming retarding core material obtaining scribbling polymerizable organosilicon nitride layer is for subsequent use.
Be that on the pure aluminum foil of 0.01mm, spread is 55g/m at thickness by above-mentioned ethene-vinyl acetate sicker roller coat after heating and melting
2(the ethene-vinyl acetate sicker that every square meter pure aluminum foil scribbles is 55g), obtain the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate, the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate is delayed with polyvinyl the inflaming retarding core material hot compound of roll-in and the cold roll-in under 105 DEG C of conditions scribbling polymerizable organosilicon nitride layer, the obtained plastic-aluminum combined stiff sheet material of halogen-free flameproof, thickness is 0.62mm, wherein, the gluing nitride layer of roll-in hot compound tense ethene-vinyl acetate connects with polymerizable organosilicon nitride layer.
Embodiment 2
By 74kg high density polyethylene (HDPE) (5000S/ raises sub-petrochemical industry), 16kg triphenyl phosphate, 10kg boron nitride fiber, (length is 3mm, diameter is 9.5 μm) in high-speed mixer (rotating speed 5000r/min) in 70 DEG C of premixs, (150 DEG C, a district is extruded through equidirectional parallel double-screw extruder melt blending after mixing, two 160 DEG C, districts, 3rd district, four He Wu districts of district are 185 DEG C, six 195 DEG C, districts, seven 190 DEG C, districts), calendering, traction, cooling forming, obtained polyvinyl inflaming retarding core material.
129.8g boric acid, 208.3g ethyl orthosilicate, 1000ml absolute ethyl alcohol are placed in reactor, be heated to 70 DEG C, stirring and refluxing, then the 40g hydrochloride aqueous solution that mass percentage concentration is 10% is slowly added, after back flow reaction 3h, decompression distillation obtains clear Polyborosiloxane, and mean molecule quantity is 2000.
By 30kgEVA resin, 25kg rosin, 23kg paraffin, 5kg calcium carbonate, 17kg ammonium octamolybdate and 0.1kg2,6-toluene di-tert-butyl phenol joins in kneader in 150 DEG C of mixing 30min, (90 DEG C, a district is melt extruded again by equidirectional parallel double-screw extruder, two 110 DEG C, districts, three, four, five 125 DEG C, districts, six 130 DEG C, districts, seven 125 DEG C, districts), cooling, dry, pelletizing, obtain ethene-vinyl acetate sicker, for subsequent use.
By Polyborosiloxane roller coat on polyvinyl inflaming retarding core material, carrying painting amount is 250g/m
2, then air blast is dried at 65 DEG C, the polyvinyl inflaming retarding core material obtaining scribbling polymerizable organosilicon nitride layer is for subsequent use.
Be that on the pure aluminum foil of 0.02mm, spread is 55g/m at thickness by above-mentioned ethene-vinyl acetate sicker roller coat after heating and melting
2obtain the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate, the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate is delayed with polyvinyl the inflaming retarding core material hot compound of roll-in and the cold roll-in under 105 DEG C of conditions scribbling polymerizable organosilicon nitride layer, the obtained plastic-aluminum combined stiff sheet material of halogen-free flameproof, thickness is 0.62mm, wherein, the gluing nitride layer of roll-in hot compound tense ethene-vinyl acetate connects with polymerizable organosilicon nitride layer.
Embodiment 3
By 64kg high density polyethylene (HDPE) (5000S/ raises sub-petrochemical industry), 22kg triphenyl phosphate, 14kg boron nitride fiber, (length is 2.5mm, diameter is 7 μm) in high-speed mixer (rotating speed 5000r/min) in 70 DEG C of premixs, (150 DEG C, a district is extruded through equidirectional parallel double-screw extruder melt blending after mixing, two 160 DEG C, districts, 3rd district, four He Wu districts of district are 185 DEG C, six 195 DEG C, districts, seven 190 DEG C, districts), calendering, traction, cooling forming, obtained polyvinyl inflaming retarding core material.
129.8g boric acid, 208.3g ethyl orthosilicate, 1000ml absolute ethyl alcohol are placed in reactor, be heated to 65 DEG C, stirring and refluxing, then the 40g hydrochloride aqueous solution that mass percentage concentration is 10% is slowly added, after back flow reaction 3h, decompression distillation obtains clear Polyborosiloxane, and mean molecule quantity is 2000.
By 30kgEVA resin, 25kg rosin, 23kg paraffin, 5kg calcium carbonate, 17kg molybdenum trioxide and 0.1kg2,6-toluene di-tert-butyl phenol joins in kneader in 150 DEG C of mixing 30min, (90 DEG C, a district is melt extruded again by equidirectional parallel double-screw extruder, two 110 DEG C, districts, three, four, five 125 DEG C, districts, six 130 DEG C, districts, seven 125 DEG C, districts), cooling, dry, pelletizing, obtain ethene-vinyl acetate sicker, for subsequent use.
By Polyborosiloxane roller coat on polyvinyl inflaming retarding core material, carrying painting amount is 250g/m
2, then air blast is dried at 65 DEG C, the polyvinyl inflaming retarding core material obtaining scribbling polymerizable organosilicon nitride layer is for subsequent use.
Be that on the pure aluminum foil of 0.01mm, spread is 55g/m at thickness by above-mentioned ethene-vinyl acetate sicker roller coat after heating and melting
2obtain the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate, the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate is delayed with polyvinyl the inflaming retarding core material hot compound of roll-in and the cold roll-in under 105 DEG C of conditions scribbling polymerizable organosilicon nitride layer, the obtained plastic-aluminum combined stiff sheet material of halogen-free flameproof, thickness is 0.62mm, wherein, the gluing nitride layer of roll-in hot compound tense ethene-vinyl acetate connects with polymerizable organosilicon nitride layer.
Embodiment 4
By 64kg high density polyethylene (HDPE) (5000S/ raises sub-petrochemical industry), 22kg triphenyl phosphate, 14kg boron nitride fiber, (length is 2.5mm, diameter is 6 μm) in high-speed mixer (rotating speed 5000r/min) in 70 DEG C of premixs, (150 DEG C, a district is extruded through equidirectional parallel double-screw extruder melt blending after mixing, two 160 DEG C, districts, 3rd district, four He Wu districts of district are 185 DEG C, six 195 DEG C, districts, seven 190 DEG C, districts), calendering, traction, cooling forming, obtained polyvinyl inflaming retarding core material.
129.8g boric acid, 208.3g ethyl orthosilicate, 1000ml absolute ethyl alcohol are placed in reactor, be heated to 65 DEG C, stirring and refluxing, then the 40g hydrochloride aqueous solution that mass percentage concentration is 10% is slowly added, after back flow reaction 3.5h, decompression distillation obtains clear Polyborosiloxane, and mean molecule quantity is 3000.
By 40kgEVA resin, 25kg rosin, 23kg paraffin, 5kg calcium carbonate, 7kg molybdenum trioxide and 0.1kg2,6-toluene di-tert-butyl phenol joins in kneader in 150 DEG C of mixing 30min, (90 DEG C, a district is melt extruded again by equidirectional parallel double-screw extruder, two 110 DEG C, districts, three, four, five 125 DEG C, districts, six 130 DEG C, districts, seven 125 DEG C, districts), cooling, dry, pelletizing, obtain ethene-vinyl acetate sicker, for subsequent use.
By Polyborosiloxane roller coat on polyvinyl inflaming retarding core material, carrying painting amount is 50g/m
2, then air blast is dried at 65 DEG C, the polyvinyl inflaming retarding core material obtaining scribbling polymerizable organosilicon nitride layer is for subsequent use.
Be that on the pure aluminum foil of 0.01mm, spread is 30g/m at thickness by above-mentioned ethene-vinyl acetate sicker roller coat after heating and melting
2obtain the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate, the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate is delayed with polyvinyl the inflaming retarding core material hot compound of roll-in and the cold roll-in under 95 DEG C of conditions scribbling polymerizable organosilicon nitride layer, the obtained plastic-aluminum combined stiff sheet material of halogen-free flameproof, thickness is 0.62mm, wherein, the gluing nitride layer of roll-in hot compound tense ethene-vinyl acetate connects with polymerizable organosilicon nitride layer.
Embodiment 5
By 64kg high density polyethylene (HDPE) (5000S/ raises sub-petrochemical industry), 22kg triphenyl phosphate, 14kg boron nitride fiber, (length is 2.5mm, diameter is 6 μm) in high-speed mixer (rotating speed 5000r/min) in 70 DEG C of premixs, (150 DEG C, a district is extruded through equidirectional parallel double-screw extruder melt blending after mixing, two 160 DEG C, districts, 3rd district, four He Wu districts of district are 185 DEG C, six 195 DEG C, districts, seven 190 DEG C, districts), calendering, traction, cooling forming, obtained polyvinyl inflaming retarding core material.
129.8g boric acid, 208.3g ethyl orthosilicate, 1000ml absolute ethyl alcohol are placed in reactor, be heated to 65 DEG C, stirring and refluxing, then the 40g hydrochloride aqueous solution that mass percentage concentration is 10% is slowly added, after back flow reaction 3h, decompression distillation obtains clear Polyborosiloxane, and mean molecule quantity is 2000.
By 30kgEVA resin, 25kg rosin, 23kg paraffin, 5kg clay, 17kg molybdenum trioxide and 0.1kg2,6-toluene di-tert-butyl phenol joins in kneader in 150 DEG C of mixing 30min, (90 DEG C, a district is melt extruded again by equidirectional parallel double-screw extruder, two 110 DEG C, districts, three, four, five 125 DEG C, districts, six 130 DEG C, districts, seven 125 DEG C, districts), cooling, dry, pelletizing, obtain ethene-vinyl acetate sicker, for subsequent use.
By Polyborosiloxane roller coat on polyvinyl inflaming retarding core material, carrying painting amount is 150g/m
2, then air blast is dried at 65 DEG C, the polyvinyl inflaming retarding core material obtaining scribbling polymerizable organosilicon nitride layer is for subsequent use.
Be that on the pure aluminum foil of 0.01mm, spread is 75g/m at thickness by above-mentioned ethene-vinyl acetate sicker roller coat after heating and melting
2obtain the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate, the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate is delayed with polyvinyl the inflaming retarding core material hot compound of roll-in and the cold roll-in under 85 DEG C of conditions scribbling polymerizable organosilicon nitride layer, the obtained plastic-aluminum combined stiff sheet material of halogen-free flameproof, thickness is 0.62mm, wherein, the gluing nitride layer of roll-in hot compound tense ethene-vinyl acetate connects with polymerizable organosilicon nitride layer.
Embodiment 6
By 64kg high density polyethylene (HDPE) (5000S/ raises sub-petrochemical industry), 22kg triphenyl phosphate, 14kg boron nitride fiber, (length is 2.5mm, diameter is 6 μm) in high-speed mixer (rotating speed 5000r/min) in 70 DEG C of premixs, (150 DEG C, a district is extruded through equidirectional parallel double-screw extruder melt blending after mixing, two 160 DEG C, districts, 3rd district, four He Wu districts of district are 185 DEG C, six 195 DEG C, districts, seven 190 DEG C, districts), calendering, traction, cooling forming, obtained polyvinyl inflaming retarding core material.
136.0g boric acid, 208.3g ethyl orthosilicate, 1000ml absolute ethyl alcohol are placed in reactor, be heated to 65 DEG C, stirring and refluxing, then the 41.6g hydrochloride aqueous solution that mass percentage concentration is 10% is slowly added, after back flow reaction 3h, decompression distillation obtains clear Polyborosiloxane, and mean molecule quantity is 2500.
By 30kgEVA resin, 25kg rosin, 23kg paraffin, 5kg clay, 17kg molybdenum trioxide and 0.1kg4,4 '-bis-(6-tert-butyl-m-cresol) thioether joins in kneader in 150 DEG C of mixing 30min, (90 DEG C, a district is melt extruded again by equidirectional parallel double-screw extruder, two 110 DEG C, districts, three, four, five 125 DEG C, districts, six 130 DEG C, districts, seven 125 DEG C, districts), cooling, dry, pelletizing, obtain ethene-vinyl acetate sicker, for subsequent use.
By Polyborosiloxane roller coat on polyvinyl inflaming retarding core material, carrying painting amount is 150g/m
2, then air blast is dried at 65 DEG C, the polyvinyl inflaming retarding core material obtaining scribbling polymerizable organosilicon nitride layer is for subsequent use.
Be that on the pure aluminum foil of 0.01mm, spread is 75g/m at thickness by above-mentioned ethene-vinyl acetate sicker roller coat after heating and melting
2obtain the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate, the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate is delayed with polyvinyl the inflaming retarding core material hot compound of roll-in and the cold roll-in under 100 DEG C of conditions scribbling polymerizable organosilicon nitride layer, the obtained plastic-aluminum combined stiff sheet material of halogen-free flameproof, thickness is 0.62mm, wherein, the gluing nitride layer of roll-in hot compound tense ethene-vinyl acetate connects with polymerizable organosilicon nitride layer.
Comparative example 1:
By 64kg high density polyethylene (HDPE) (5000S/ raises sub-petrochemical industry), 36kg triphenyl phosphate in high-speed mixer in 70 DEG C of premixs, (150 DEG C, a district is extruded through equidirectional parallel double-screw extruder melt blending after mixing, two 160 DEG C, districts, 3rd district, four He Wu districts of district are 185 DEG C, six 195 DEG C, districts, seven 190 DEG C, districts), calendering, traction, cooling forming, obtained polyvinyl inflaming retarding core material (nonnitrogenousization boron fibre).
By 42kgEVA resin, 28kg rosin, 25kg paraffin, 5kg clay and 0.1kg2,6-toluene di-tert-butyl phenol joins in kneader in 150 DEG C of mixing 30min, (90 DEG C, a district is melt extruded again by equidirectional parallel double-screw extruder, two 110 DEG C, districts, three, four, five 125 DEG C, districts, six 130 DEG C, districts, seven 125 DEG C, districts), cooling, dry, pelletizing, obtain ethene-vinyl acetate sicker (not molybdate compound), for subsequent use.
Be that on the pure aluminum foil of 0.01mm, spread is 55g/m at thickness by the ethene-vinyl acetate sicker of above-mentioned not molybdate compound roller coat after heating and melting
2obtain scribbling the aluminium film of the gluing nitride layer of ethene-vinyl acetate of not molybdate compound, by the aluminium film of gluing for the ethene-vinyl acetate scribbling not molybdate compound nitride layer and the polyvinyl inflaming retarding core material of nonnitrogenousization boron fibre, the hot compound of roll-in and cold roll-in under 95 DEG C of conditions are delayed, obtained plastic-aluminum combined stiff sheet material, thickness is 0.62mm, wherein, the gluing nitride layer of ethene-vinyl acetate of the hot compound tense of roll-in not molybdate compound connects with the polyvinyl inflaming retarding core material of nonnitrogenousization boron fibre.
Plastic-aluminum combined stiff sheet material prepared by the halogen-free flameproof plastic-aluminum combined stiff sheet material prepare embodiment 1-6 and comparative example 1 carries out performance test, examination criteria: hot strength is tested according to GB/T1040-2006 " mensuration of plastic tensile performance "; Oxygen index (OI) is tested according to GB/T2406-2009 " plastics oxygen index method measures burning behavior "; Horizontal firing grade is according to GB/T2408-2008 " the mensuration Using Horizontal Bridgman Method of Plastics Combustion performance and normal beam technique " test, and test result is as follows:
| Hot strength (MPa) | Oxygen index (OI) (%) | Horizontal firing grade | |
| Comparative example 1 | 16.6 | 27.0 | HB75 |
| Embodiment 1 | 15.2 | 38.8 | HB |
| Embodiment 2 | 18.1 | 33.6 | HB |
| Embodiment 3 | 16.8 | 35.2 | HB |
| Embodiment 4 | 17.3 | 30.5 | HB |
| Embodiment 5 | 17.0 | 33.5 | HB |
| Embodiment 6 | 17.1 | 33.1 | HB |
Note: test samples thickness is 0.62mm.Oxygen index (OI) is higher shows that flame retardant effect is better, horizontal firing grade: HB flame retardant effect is better than HB75.
Only have the light cigarettes of trace to produce during the plastic-aluminum combined stiff sheet material combustion of halogen-free flameproof prepared by smoke suppressing: embodiment 1-6, but comparative example 1 prepare plastic-aluminum combined stiff sheet material combustion time the smoke which that produces obviously more on the high side and the color of cigarette is more obvious than embodiment 1-6 partially dark than embodiment 1-6.
As seen from the above table: (1) polyvinyl inflaming retarding core material is comparatively large to the contribution promoting plastic-aluminum combined stiff sheet material monolithic fire resistance, along with the increase of triphenyl phosphate in core and boron nitride fiber content, the fire resistance of composite hard sheet material improves.(2) the polymerizable organosilicon nitride layer on core has certain Fire resistances, and the increase (the carry painting amount of organosilicon polymer on polyvinyl inflaming retarding core material is high) of this layer thickness is conducive to the fire resistance promoting material.(3) because molybdenum compound in the gluing nitride layer of EVA can be bonded in the aromatic series flue dust parent formed after core and organosilicon polymer thermal cracking in metal-aromatic series compound securely, it is obvious that result shows its lifting smoke suppressing effect.The plastic-aluminum combined stiff sheet material of halogen-free flameproof prepared by embodiment 1-6 all shows excellent smoke-inhibiting flame retardant performance and mechanical property.Therefore, the present invention, by the synergy between layer material each in plastic-aluminum combined stiff sheet material and synergy between layers, can obtain having excellent smoke-inhibiting flame retardant performance and the plastic-aluminum combined stiff sheet material of mechanical property.
In composition of raw materials of the present invention, the change of parameter does not have a great impact the plastic-aluminum combined stiff sheet material property of halogen-free flameproof, all can obtain having excellent fire resistance and the plastic-aluminum combined stiff sheet material of mechanical property.In preparation method of the present invention, the change of parameter does not affect the preparation of the plastic-aluminum combined stiff sheet material of halogen-free flameproof, and therefore in preparation method of the present invention, the combination of arbitrary parameter all can realize the preparation of the plastic-aluminum combined stiff sheet material of halogen-free flameproof.Do not repeat them here.
Claims (9)
1. the plastic-aluminum combined stiff sheet material of halogen-free flameproof, it is characterized in that, be made up with the polyvinyl inflaming retarding core material compound scribbling polymerizable organosilicon nitride layer of the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate, the gluing nitride layer of the ethene-vinyl acetate described in compound tense connects with polymerizable organosilicon nitride layer;
Described polyvinyl inflaming retarding core material is made up of the raw material of following weight portion: 54 parts of-74 parts of high density polyethylene (HDPE)s, 16 portions of-28 portions of triphenyl phosphates and 10 parts of-18 parts of boron nitride fibers;
Described ethene-vinyl acetate sicker is made up of the raw material of following weight portion: 30 parts of-40 parts of ethylene-vinyl acetate resins, 25 parts of-30 parts of rosin, 18 parts of-23 parts of paraffin, 5 parts of fillers, 7 parts of-17 parts of molybdenum compounds and appropriate antioxidant.
2. the plastic-aluminum combined stiff sheet material of halogen-free flameproof according to claim 1, is characterized in that, described boron nitride fiber length is 2mm-3mm, and diameter is 4.5 μm-9.5 μm.
3. the plastic-aluminum combined stiff sheet material of halogen-free flameproof according to claim 1, is characterized in that, described organosilicon polymer is Polyborosiloxane, and mean molecule quantity is 2000-3000.
4. the plastic-aluminum combined stiff sheet material of halogen-free flameproof according to claim 3, it is characterized in that, the preparation method of described Polyborosiloxane comprises: boric acid, ethyl orthosilicate and absolute ethyl alcohol are mixed, be heated to 60 DEG C-70 DEG C, stirring and refluxing, then slowly add hydrochloride aqueous solution, after back flow reaction 3h-3.5h, decompression distillation obtains clear Polyborosiloxane; Wherein, the mol ratio of boric acid and ethyl orthosilicate is 2.1-2.2:1, and the mol ratio of hydrogen chloride and ethyl orthosilicate is 0.1-0.15:1.
5. the plastic-aluminum combined stiff sheet material of halogen-free flameproof according to claim 1, is characterized in that, described molybdenum compound is the one in molybdenum trioxide, ammonium heptamolybdate, ammonium octamolybdate.
6. the plastic-aluminum combined stiff sheet material of halogen-free flameproof according to claim 1, is characterized in that, described filler is the one in clay, calcium carbonate, barium sulfate.
7. the plastic-aluminum combined stiff sheet material of halogen-free flameproof according to claim 1, is characterized in that, described antioxidant is 2,6-toluene di-tert-butyl phenol, 4, the one in 4 ˊ-bis-(6-tert-butyl-m-cresol) thioether.
8. the plastic-aluminum combined stiff sheet material of halogen-free flameproof according to claim 1, is characterized in that, year painting amount of described organosilicon polymer on polyvinyl inflaming retarding core material is 50g/m
2-250g/m
2, the spread of described ethene-vinyl acetate sicker on aluminium film is 30g/m
2-75g/m
2.
9. the preparation method of the plastic-aluminum combined stiff sheet material of the halogen-free flameproof according to any one of claim 1-8, is characterized in that, comprise the steps:
(1) by high density polyethylene (HDPE), triphenyl phosphate and boron nitride fiber at 60 DEG C of-70 DEG C of premixs, extrude through equidirectional parallel double-screw extruder melt blending after mixing, roll, draw and cooling forming, obtained polyvinyl inflaming retarding core material;
(2) by organosilicon polymer roller coat on described polyvinyl inflaming retarding core material, then at 60 DEG C-65 DEG C dry, obtain the polyvinyl inflaming retarding core material scribbling polymerizable organosilicon nitride layer;
(3) by ethylene-vinyl acetate resin, rosin, paraffin, filler, molybdenum compound and antioxidant in 130 DEG C of-150 DEG C of mixing 20min-30min, extruded by equidirectional parallel double-screw extruder melt blending again, through cooling, dry and pelletizing, obtain ethene-vinyl acetate sicker;
(4) by described ethene-vinyl acetate sicker after heating and melting roller coat on aluminium film, obtain the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate, the aluminium film scribbling the gluing nitride layer of ethene-vinyl acetate is delayed with polyvinyl the inflaming retarding core material hot compound of roll-in and the cold roll-in under 85 DEG C of-105 DEG C of conditions scribbling polymerizable organosilicon nitride layer, the obtained plastic-aluminum combined stiff sheet material of halogen-free flameproof, wherein, the gluing nitride layer of ethene-vinyl acetate described in the hot compound tense of roll-in connects with polymerizable organosilicon nitride layer.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1445273A (en) * | 2002-03-19 | 2003-10-01 | 湖南省塑料研究所 | Fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board and its preparing method |
| CN201137269Y (en) * | 2007-12-12 | 2008-10-22 | 王兴正 | Fire-proof aluminum plastic composite board |
| CN103342845A (en) * | 2013-06-25 | 2013-10-09 | 上海科悦高分子材料有限公司 | Novel fire-proof material and preparing method thereof, light fire-proof aluminium-plastic panel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1445273A (en) * | 2002-03-19 | 2003-10-01 | 湖南省塑料研究所 | Fire-resistant polyethylene core material with no halogen applicable to fireproofing aluminum plastic board and its preparing method |
| CN201137269Y (en) * | 2007-12-12 | 2008-10-22 | 王兴正 | Fire-proof aluminum plastic composite board |
| CN103342845A (en) * | 2013-06-25 | 2013-10-09 | 上海科悦高分子材料有限公司 | Novel fire-proof material and preparing method thereof, light fire-proof aluminium-plastic panel |
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