CN110157072A

CN110157072A - A kind of fireproof aluminum-plastic board containing nano-meter flame retardants and its dedicated core material

Info

Publication number: CN110157072A
Application number: CN201910431326.2A
Authority: CN
Inventors: 杜作政; 邢锦; 罗奕桢
Original assignee: Dongguan Walltes Decorative Material Co Ltd
Current assignee: Dongguan Walltes Decorative Material Co Ltd
Priority date: 2019-05-22
Filing date: 2019-05-22
Publication date: 2019-08-23

Abstract

The present invention relates to aluminium-plastic panel technical fields, and in particular to a kind of fireproof aluminum-plastic board containing nano-meter flame retardants and its dedicated core material.The core material includes the raw material of following parts by weight: 45-55 parts of polyethylene, 25-30 parts of polycarbonate, modified nylon 15-18 parts of enhancing, 2-3 parts of nano-meter flame retardants, 1.5-2.5 parts of modified nano cerium oxide, 2-6 parts of synergist, 3-8 parts of compatilizer and 1-2 parts of lubricant.Core material of the invention has excellent fire retardant performance, and mobility is strong, is readily extruded molding and injection molding prepares sandwich layer, and its sandwich layer intensity obtained of utilization is high, hardness is good, bend-resistance, is unlikely to deform, weatherability is good；Wherein, by using nano-meter flame retardants, with synergist collective effect, it can make core material that there is preferable fire retardant performance, and synergist, while it plays flame retardant effect, powder state can promote the dispersibility between material, improve the rheological characteristic of core material in the subsequent process.

Description

A kind of fireproof aluminum-plastic board containing nano-meter flame retardants and its dedicated core material

Technical field

The present invention relates to aluminium-plastic panel technical fields, and in particular to a kind of fireproof aluminum-plastic board containing nano-meter flame retardants and its specially Use core material.

Background technique

Aluminium-plastic panel is made by two kinds of materials of metal and plastics, the key property of former composition material has both been remained, such as plastics Lightweight, aluminium shape surface tight structure bring corrosion resistance characteristic etc., and mutually overcome the deficiency of former composition material, such as color Dicoration, weatherability, corrosion resistance, sound insulation, heat-insulated, easy processing mouldability etc. are widely applied as a kind of new decorative material In building exposed wall, curtain wallboard, old building transforming renovation, indoor wall and ceiling finishing, advertising signboard, exhibition bench frame etc..

Although and the aluminum profile energy high temperature resistant on its surface of aluminium-plastic panel, plastic core layer therein are easy by surfaces of aluminum at present The high temperature of profile influences, and causes to be heated excessively, phenomena such as smoldering, spontaneous combustion occurs, flame retardant property is undesirable, and at present for sandwich layer Material it is fire-retardant it is basic use inorganic fire retardants, flame retardant property is single, is not able to satisfy and wants at present to the flame retardant property of core material It asks.

Summary of the invention

In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide one kind to hinder containing nanometer Fire agent the dedicated core material of fireproof aluminum-plastic board, the core material have excellent fire retardant performance, mobility is strong, be readily extruded molding and Injection molding prepares sandwich layer, and its sandwich layer intensity obtained of utilization is high, hardness is good, bend-resistance, is unlikely to deform, weatherability is good.

The purpose of the present invention is to provide a kind of fireproof aluminum-plastic board containing nano-meter flame retardants, the fireproof aluminum-plastic board intensity It is high, hardness is good, bend-resistance, is unlikely to deform, weatherability is good, and its preparation process is simple, convenient operation and control, and quality is stablized, raw Produce high-efficient, production cost is low, can large-scale industrial production.

The purpose of the invention is achieved by the following technical solution: a kind of dedicated core of the fireproof aluminum-plastic board containing nano-meter flame retardants Material, the core material include the raw material of following parts by weight:

The present invention prepares core material by using above-mentioned raw materials, and compatibility is preferable between material, good dispersion, the group of being less prone to Phenomena such as poly-, makes core material obtained have preferable fire protection flame retarding, weatherability and intensity and the mechanical performances such as resistant to bending； Wherein, by using modified enhancing nylon material, the mechanical performances such as tensile strength, the bending strength of core material can be improved；It is logical It crosses using nano-meter flame retardants, with synergist collective effect, can make core material that there is preferable fire retardant performance, and synergist is at it While playing flame retardant effect, powder state can promote the dispersibility between material, improve the stream of core material in the subsequent process Denaturation；The heat resistance and thermal stability of core material can be effectively improved by using nano modification cerium oxide, and its nano-powder can have Effect improves the mobility of core material material, is easy to subsequent extrusion molding process and injection molding；And by using compatilizer, it can mention Crosslinked polymeric between high density polyethylene, polycarbonate and modified enhancing nylon, and improve the dispersibility and compatibility of storeroom； By using lubricant, the dispersibility between material can be improved, and improves release property of the core material in subsequent injection molding, is easy to Demoulding, makes not easily damaged deformation in its knockout course.

Preferably, every part of nano-meter flame retardants include 8-10 parts of hexaphenoxycyclotriphosphazenes, 3-5 parts of nanometer titanium dioxides Silicon, 2-4 part ammonium polyphosphate, 2-4 parts of Magnesium Hydroxide Nano-particles and 5-6 parts of Nano glass powders.

Nano-meter flame retardants of the invention use inorganic nanometer powder, organic phosphoric acid fire retardant and polyfunctional group based flame retardant Mutually compounding synergistic effect, can significantly improve weatherability, the fire-retardant fireproof of core material, and nano silica therein, nanometer hydrogen There is pole between the nano-powder structure of magnesium oxide powder and Nano glass powder, with polyethylene, polycarbonate and modified enhancing nylon Big contact surface area can have excellent nano-dispersion effect in polyethylene core material system, can effectively facilitate material part Dispersibility and mobility, be easy to subsequent extrusion molding process and injection molding processes；Wherein, six phenoxy group rings three of use P, N hybrid structure of phosphonitrile can be formed with polyethylene, polycarbonate matrix into charcoal system, and three's collective effect at high temperature Carbon residue yield is improved, polyethylene, polycarbonate matrix decomposition generation gas phase combustible is reduced, reduces the Heat liberation unit of burning, and Since carbon residue is to warm, the barrier action of oxygen and imflammable gas, the combustion intensity of core material system, another party further reduced Face, in the case of a high temperature, phenyloxy groups in hexaphenoxycyclotriphosphazene due to phosphorus oxygen key fracture and from six phenoxy group rings It dissociates and on three phosphonitrile molecules, disproportionated reaction then occurs and generates the structures such as Pyrogentisinic Acid and phenyl ring, and further decomposes, and phosphorus Cracking occurs at high temperature and generates PO and PO for nitrile ring₂Small molecules fragments, and phenoxy group that above-mentioned all Pintsch process generate and its Gasification product and phosphoric-oxygenic compound Jun Ju You temper go out the gaseous phase free radical effect of burning, promote layer of charcoal at charcoal effect, two aspects It acts on simultaneously, effectively improves the performances such as thermal stability, anti-flammability, high limit oxygen index (OI) and the release of low cigarette of core material, and non-stimulated Property smell release.

The nano silica molecule of use is tridimensional network, and surface has unsaturated residual bond and different bond styles Hydroxyl, and the bond energy of Si-O key is higher by much relative to the bond energy of the bond energy of C-O, the bond energy of C-C and Si-C, so Si-O key There is excellent thermal stability and antioxygenic property at high temperature, and have between its Nano grade and polymer and greatly contact Surface area, polyethylene, polycarbonate and modified enhancing nylon form around Nano grade silica dioxide granule and closely divide Subchain effectively improves the thermal stability and anti-flammability of core material system；On the other hand, in silica and hexaphenoxycyclotriphosphazene P elements, there is between nitrogen excellent flame retardant synergistic effect, in core material combustion process, P elements, nitrogen promote The formation of carbon-coating, and element silicon then increases the thermal stability of layer of charcoal, stablizes Char Residues Structure closely, improve core material oxygen index (OI) and Heat-insulating flame-retardant performance.

And the ammonium polyphosphate used decomposes release ammonia and water at high temperature, and generates phosphoric acid, sour component catalysis carbon-forming, shape At layer of charcoal surfacing, heat-insulated oxygen barrier fire-retardant effect is played, and process does not generate the corrosive gas such as hydrogen halides, thermal stability Height, raw smoke is extremely low when burning, and flame retarding efficiency is high；The oxonium ion of the magnesium hydroxide used is tightly packed for six sides, Al³⁺Symmetrically It is distributed in the octahedral coordination center that oxonium ion surrounds, lattice energy is big, and fusing point is high, boiling point is high, can significantly improve the fire-retardant of core material Effect, and smoke can be inhibited, droppings is not generated, do not generate toxic gas；The Nano glass powder of use is after melted by heating, tool There is higher stickiness, core layer surface is made to form ceramic, forms heat resistant fire-proof system, improve the heat resistance and anti-flammability of sandwich layer.

Preferably, the hexaphenoxycyclotriphosphazene is made by following steps:

Step (1): ammonium chloride powder being added into chlorobenzene, is stirred evenly, and mixture A is made；

Step (2): mixture A made from step (1) is warming up to 75-95 DEG C, ZnO is added, is then added while stirring Phosphorus pentachloride, while it being passed through chlorine, heating stirring reflux 12-16h cools down after completion of the reaction, takes out press filtration, and washing is made six Three phosphonitrile of chlorine ring；

Step (3): phenol being dissolved in tetrahydrofuran, is stirred evenly, and mixture B is made；

Step (4): mixture B made from step (3) is instilled into sodium hydroxide solution, is warming up to 70-75 DEG C, stirring Flow back 18-24h, and phenol sodium solution is made；

Step (5): hexachlorocyclotriph,sphazene made from step (2) is dissolved in dioxane, and mixture C is made；

Step (6): mixture C made from step (5) is instilled into phenol sodium solution made from step (4), side stirring Side instills, and is warming up to 70-75 DEG C, is stirred at reflux 25-30h, and mixture D is made；

Step (7): mixture D made from step (6) is cooling, concentration is subsequently poured into the deionized water of 1L, stand, Filtering, carries out concentration purification for filtered filtrate, and hexaphenoxycyclotriphosphazene is made.

Preferably, in the step (1), the mixed liquor ratio of ammonium chloride powder and chlorobenzene is 2-3:4；The step (2) In, the mixed proportion of phosphorus pentachloride and mixture A are 3-5:6, and chlorine intake is 180-250m³Phosphorus pentachloride is added in/min When speed of agitator be 800-1000rpm；In the step (3), the mixed liquor ratio of phenol and tetrahydrofuran is 2-3:6；Institute It states in step (4), the mixed proportion of mixture B and sodium hydroxide solution is 1-2:1；In the step (5), hexachlorocyclotriph,sphazene Mixed liquor ratio with dioxane is 1-3:5；In the step (6), speed of agitator when instilling mixture C is 600- 900rpm。

The present invention prepares hexaphenoxycyclotriphosphazene by using above-mentioned steps, easy to operate, and each step of strict control Mixed proportion, yield can be effectively improved, side reaction product is few, and low energy consumption, high production efficiency, and stability is high；Wherein, by adopting It uses ammonium chloride, phosphorus pentachloride, chlorine as raw material, under the effect of the catalyst, hexachlorocyclotriph,sphazene yield obtained can be made to reach 95%, with conventionally employed ammonium chloride, phosphorus pentachloride mixing high temperature preparation method compared with, substantially reduce reaction duration, lower Energy consumption, and yield improves 50%.

Thereafter hexachlorocyclotriph,sphazene obtained is dissolved in dioxane, its solubility can be improved, and be easy to and phenol Sodium solution mixing phase reaction, and be added dropwise in phenol sodium solution while stirring, it can guarantee that storeroom has biggish contact area, Reaction sufficiently, reduces the generation of side reaction, improves the yield and purity of hexaphenoxycyclotriphosphazene.

Preferably, the modified enhancing nylon includes the raw material of following parts by weight:

The present invention prepares modified enhancing nylon by using above-mentioned raw materials, make it have preferable associativity, rheological characteristic and Stability is easy to continuous flow rate and extrusion to subsequent extrusion molding in the process；Wherein, PA resin is carried out by using toughener It is modified, the mechanical performances such as its toughness, intensity, dimensional stability can be improved, itself and polyethylene, polycarbonate phase separation are made, are improved The performances such as hardness, intensity, tensile strength, the bend-resistance intensity of core material；And the short glass fiber used has excellent flowing Property, the dispersing uniformity of each material in modified enhancing nylon material can be promoted, and while improving PA mechanical strength of resin, improve it Rheological characteristic, and the material rheological characteristic of core material is effectively improved, it is extruded into modified enhancing nylon and unclassified stores obtained subsequent It is easy to continuous flow rate and extrusion during type；And the modification ethylene bis-fatty acid amides used have good inside and outside lubricity, Demoulding type and finish can accelerate melting in the process such as feeding, extrusion and injection molding, reduce melt viscosity, save Power consumption of polymer processing increases the toughness of modified enhancing nylon, prolongs its service life.

Preferably, the modified ethylene bis-fatty acid amides are work of the ethylene bis-fatty acid amides in cumyl peroxide Under, the BAB type copolymer to be formed is reacted with the reactive monomer divinylbenzene containing polar group or maleic anhydride；It is described The mixture that toughener is made of polyvinyl butyral and dioctyl phthalate with weight ratio for 2-4:1.

The present invention carries out oxygen to ethylene bis-fatty acid amides by using reactive monomer divinylbenzene or maleic anhydride Change and be modified, the weatherability and thermal stability of ethylene bis-fatty acid amides can be improved, so that it is further increased the heat resistance of core material, mention The heat-resisting quantity and fire retardant performance of high sandwich layer.

Toughener of the present invention by using mentioned kind, and the mixed proportion of both strict controls can effectively improve and change Property enhancing nylon the mechanical performances such as intensity, toughness, bend-resistance, tensile strength, further have sandwich layer obtained preferable The mechanical performances such as intensity, dimensional stability, stability is high；Wherein, the polyvinyl butyral of use has excellent softness Property and flexibility, the compatibility of modified enhancing nylon and polyethylene, polycarbonate can be improved, stability is high.

Preferably, the modified enhancing nylon is made by following steps:

Step (1): in parts by weight, nylon, toughener and short glass fiber is dried respectively, then mixed Stirring, obtains mixture；

Step (2): being added to extrusion equipment for mixture obtained in step (1) and squeeze out, and will modified ethylene pair Fatty acid amide is added from the side feeding inlet of extrusion equipment, and latter same extrusion is mixed with mixture, and then cooling, granulation is made Modified enhancing nylon.

Preferably, in the step (1), stirring rate 800-1200rpm；In the step (2), the ginseng of extrusion equipment Number are as follows: area's temperature is 270-280 DEG C, and two area's temperature are 260-270 DEG C, and three area's temperature are 260-270 DEG C, and four area's temperature are 250-260 DEG C, five area's temperature are 240-250 DEG C.

The present invention prepares modified enhancing nylon, and the speed of agitator and extrusion of strict control mixing through the above steps Temperature can make modified enhancing nylon obtained have excellent heat resistance, wear resistance, self-lubrication and intensity resistant to bending etc. Comprehensive performance, coefficient of friction is low, and water absorption rate is small, and dimensional stability is strong；Wherein, by the way that toughener and staple glass fibre will first be added Dimension carries out the modification of toughness, compatibility, flexibility and flexibility to PA resin, while improving the dispersibility of material, and thereafter from The ethylene bis-fatty acid amides Jing Guo modification are added in the side material mouth of extrusion equipment, while improving lubricity in material, Its heat resistance is improved, the heat-resisting quantity and fire retardant performance of sandwich layer are further increased.

Preferably, the modified nano cerium oxide is made by following steps:

Step is 1.: ethyl alcohol, isopropanol and deionized water being mixed evenly with volume ratio for 15-18:5-10:1, are made Then solvent A titanate coupling agent is added into solvent A, 40-50min is mixed, and modified solution is made；

Step is 2.: ethyl alcohol and isopropanol being mixed evenly with volume ratio for 3-8:1, solvent B is made, then by nanometer Cerium oxide is added into solvent B, and nano oxygen is made in ultrasonic disperse 30-40min under conditions of frequency is 15000-20000Hz Change cerium solution；

Step is 3.: by step 2. nano-cerium oxide solution obtained in temperature be stirring in water bath at 65-75 DEG C, while stirring By step, 1. modified solution obtained is added dropwise in nano-cerium oxide solution, continues to stir 5-10min after being added dropwise, and then will Mixture filtering, filter residue are washed 2-4 times with cleaning solution, are then to dry 6-8h at 70-80 DEG C in temperature by the filter residue after washing, Modified nano cerium oxide is made in grinding.

The present invention prepares nano modification cerium oxide by using above-mentioned steps, makes it have higher activity and reinforcement is made With the high temperature resistance and fire-retardant fireproof of core material can be significantly improved；Wherein, step (1) by using ethyl alcohol, isopropanol and is gone Ionized water mixing is used as solvent A, can fully be dispersed therein titanate coupling agent, promote its subsequent molten with nano-cerium oxide The reaction process of liquid mixing；And step (2) by using ethyl alcohol and isopropanol as solvent A, can be by nano-cerium oxide fully It is dispersed therein, and by the way of ultrasonic disperse, and strict control supersonic frequency and time, point of nano-cerium oxide can be promoted The uniformity is dissipated, promotes its subsequent and modified solution hybrid reaction process；And step (3) is received by the way that modified solution to be slowly dropped into In rice cerium oxide solution, the completeness of modified-reaction can be promoted, keep titanate coupling agent sufficiently modified to nano-cerium oxide and molten Contain ethyl alcohol and isopropanol in agent A, solvent B, the ingredient of the two solvent is similar, and the two can be made to be sufficiently mixed dispersion, be not easy out Phenomena such as being now layered, and the later period dries readily volatilized removal, and is washed using ethanol water, and nano modification oxidation is improved The purity and quality of cerium.

Preferably, the step 1. in, the solid-liquid ratio of titanate coupling agent and solvent A is 1:30-35, and the titanate esters are even Connection agent is Di(dioctylpyrophosphato) ethylene titanate；The step 2. in, the partial size of nano-cerium oxide is 20- 200nm, for nano-cerium oxide in advance through 55-70 DEG C of drying 4-6h, the solid-liquid ratio of nano-cerium oxide and solvent B are 1:15-18；It is described Step 3. in, the revolving speed of stirring in water bath is 800-1200rpm, and the cleaning solution is to be with volume ratio by ethyl alcohol and deionized water The mixture of 15-18:1 composition.

The present invention is used as modified coupling agent by using Di(dioctylpyrophosphato) ethylene titanate, and controls it With the solid-liquid ratio of solvent A, modification efficiency is high, can carry out sufficient surface to nano-cerium oxide and be modified, with nano-cerium oxide surface Hydroxyl condensation reaction occurs, form chemical bonds, make nano modification cerium oxide obtained that can promote point of core material material Property is dissipated, the agglomeration for reducing material occurs, and nano modification cerium oxide can be made to absorb the freedom that core material is generated due to high temperature Base, improves the thermal stability of core material, and then improves its heat-resisting quantity and flame retardant property.On the other hand, using bis- (two octyloxies cokes It is phosphate-based) powder in the ester modified nano-cerium oxide of ethylene metatitanic acid, with the nano-powder and synergist in nano-meter flame retardants Body structure phase separation is effectively improved dispersibility of each powder structure in polyethylene-polycarbonate system, anti-settling, and improves The loading of powder structure in the polymer improves waterproof, the fire-retardant fireproof, antiseptic property of core material.

And pass through the partial size of strict control nano-cerium oxide, and by preparatory drying and processing, it can be made to be well-dispersed in molten In agent A, keep its subsequent progress high effective and modified；And pass through the revolving speed of strict control stirring in water bath, titanate coupling agent can be made and received Rice cerium oxide come into full contact with, to nano-cerium oxide surface carry out it is high effective and modified, if revolving speed is slower, reduce modified reaction into Journey reduces the contact frequency and contact area of titanate coupling agent and nano-cerium oxide if revolving speed is very fast, reduces modified effect Fruit.

Preferably, every part of synergist includes 8-12 parts of zinc oxide, 4-7 parts of silicon carbide and 3-5 parts of mica powders；The phase Holding agent is by styrene-grafted maleic anhydride and ethylene-acrylic acid-butyl ester graft glycidyl methacrylate with weight ratio For the mixture of 2-4:1 composition；The lubricant is by pentaerythritol stearate and hydrogenation ethylenebisstearamide with weight Amount is than the mixture for 2.4-3.2:1 composition.

The present invention can significantly improve the heat resistance, anti-flammability, machinery of core material by force by using the synergist of mentioned kind The performances such as degree, dimensional stability, while its powder state can promote the dispersing uniformity of each material in core material, anti-settling, and mention The loading of high powder structure in the polymer；Wherein, the zinc oxide used can absorb core material at high temperature for amphoteric oxide The Determining Micro Acid or alkaline matter that degradation generates, slow down the decomposition of core material at high temperature, and heat resistance and the acid and alkali-resistance for improving sandwich layer are rotten Corrosion；The silicon carbide of use plays the role of inert material, inhibits the contraction of firing product in core material burning cracking process, mentions The dimensional stability of high sandwich layer makes it have preferable high temperature resistant, fire retardant performance；The mica powder of use has excellent exhausted Edge is used in compounding with silicon carbide, zinc oxide, and sandwich layer obtained can be made to be converted into mechanical strength and insulating properties when encountering high temperature Preferable ceramic substance, so that sandwich layer still has original insulating properties after baked wheaten cake, high temperature resistance is good, avoids the occurrence of because of height Temperature and spontaneous combustion, phenomena such as smoldering.

And by using the compatilizer of mentioned kind, polarity is higher, can promote polyethylene, polycarbonate and modified enhancing Buddhist nun Intermolecular linkage resultant force between dragon, promotes the two to combine blending, improves the dispersibility and compatible blended of storeroom；Wherein, The styrene-grafted maleic anhydride of use has the characteristics that high fluidity of molten and fast shaping, can make core material it is subsequent extrusion and Rheological characteristic is good in injection molding process, and molding is very fast, improves the preparation efficiency and yield of sandwich layer.

Another object of the present invention is achieved through the following technical solutions: a kind of fireproof aluminum-plastic board containing nano-meter flame retardants, The fireproof aluminum-plastic board includes from top to bottom sequentially connected upper aluminium sheet, the first adhesive-layer, sandwich layer, the second adhesive-layer and lower aluminium Plate, the core material of the sandwich layer from the above mentioned are made, and the sandwich layer is made by following steps:

According to parts by weight, the item for being 70-85 DEG C in temperature by polyethylene, polycarbonate, modified enhancing nylon and compatilizer 20-30min is mixed under part, then cools to room temperature, remaining material is added while stirring, be uniformly mixed, add to It being squeezed out in extrusion equipment, the material after extrusion is directly added to carry out injection molding processing in injection molding apparatus, and it is cooling, it is made Sandwich layer.

Preferably, the extrusion parameter of the extrusion equipment are as follows: area's temperature is 315-325 DEG C, and two area's temperature are 305-315 DEG C, three area's temperature are 295-305 DEG C, and four area's temperature are 290-300 DEG C, and five area's temperature are 280-290 DEG C, and six area's temperature are 270- 280℃；The temperature of the injection molding is 295-310 DEG C.

The present invention, which passes through, first mixes polyethylene, polycarbonate, modified enhancing nylon three with compatilizer, and at high temperature Stirring promotes polyethylene, polycarbonate, the modified compatibility and cross-linked polymeric enhanced between nylon under the action of compatilizer Property, and the mixing dispersibility of mixture and subsequent material is improved, it then is cooled to room temperature down and is mixed with unclassified stores, promote material Between dispersibility, squeeze out material system uniformly in extrusion process, and directly carry out injection molding after squeezing out, save intermediate cold But, each area's temperature and be molded into that the processes such as granulation, master batch melting, energy saving, raising production efficiency, and strict control squeeze out The temperature of type can make sandwich layer obtained have excellent hardness, tensile strength, bend-resistance, weatherability, dimensional stability etc. comprehensive Performance is closed, is unlikely to deform, fire retardant performance is good.

The beneficial effects of the present invention are: the dedicated core material of fireproof aluminum-plastic board that the present invention contains nano-meter flame retardants has excellent Fire retardant performance, mobility is strong, is readily extruded molding and injection molding prepares sandwich layer, and utilize its sandwich layer intensity obtained It is high, hardness is good, bend-resistance, be unlikely to deform, weatherability is good.Fireproof aluminum-plastic board intensity of the invention is high, hardness is good, bend-resistance, no Easily-deformable, weatherability is good, and its preparation process is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low, It can large-scale industrial production.

Detailed description of the invention

Fig. 1 is the cross-sectional view of fireproof aluminum-plastic board of the present invention；

Appended drawing reference are as follows: 1-upper aluminium sheet, the 2-the first adhesive-layer, 3-sandwich layers, the 4-the second adhesive-layer, 5-lower aluminum sheets.

Specific embodiment

For the ease of the understanding of those skilled in the art, make below with reference to 1 couple of present invention of examples and drawings further Illustrate, the content that embodiment refers to not is limitation of the invention.

Embodiment 1

A kind of dedicated core material of the fireproof aluminum-plastic board containing nano-meter flame retardants, the core material includes the raw material of following parts by weight:

Every part of nano-meter flame retardants include 8 parts of hexaphenoxycyclotriphosphazenes, 3 parts of nano silicas, 2 parts of polyphosphoric acids Ammonium, 2 parts of Magnesium Hydroxide Nano-particles and 5 parts of Nano glass powders.

The hexaphenoxycyclotriphosphazene is made by following steps:

Step (2): mixture A made from step (1) is warming up to 75 DEG C, ZnO is added, pentachloro- is then added while stirring Change phosphorus, while being passed through chlorine, heating stirring reflux 12h cools down after completion of the reaction, takes out press filtration, and three phosphorus of chlordene ring is made in washing Nitrile；

Step (4): mixture B made from step (3) is instilled into sodium hydroxide solution, 70 DEG C is warming up to, stirs back For 24 hours, phenol sodium solution is made in stream；

Step (6): mixture C made from step (5) is instilled into phenol sodium solution made from step (4), side stirring Side instills, and is warming up to 70 DEG C, is stirred at reflux 30h, and mixture D is made；

In the step (1), the mixed liquor ratio of ammonium chloride powder and chlorobenzene is 2:4；It is phosphoric in the step (2) The mixed proportion of phosphorus and mixture A are 3:6, and chlorine intake is 180m³/ min, speed of agitator when phosphorus pentachloride is added are 800rpm；In the step (3), the mixed liquor ratio of phenol and tetrahydrofuran is 3:6；In the step (4), mixture B with The mixed proportion of sodium hydroxide solution is 1:1；In the step (5), the mixed liquor ratio of hexachlorocyclotriph,sphazene and dioxane For 1:5；In the step (6), speed of agitator when instilling mixture C is 600rpm.

The modified enhancing nylon includes the raw material of following parts by weight:

The modified ethylene bis-fatty acid amides are ethylene bis-fatty acid amides under the action of cumyl peroxide, with Reactive monomer divinylbenzene or maleic anhydride containing polar group react the BAB type copolymer to be formed；The toughener The mixture being made of polyvinyl butyral and dioctyl phthalate with weight ratio for 2:1.

The modified enhancing nylon is made by following steps:

Step (2): being added to extrusion equipment for mixture obtained in step (1) and squeeze out, and will modified ethylene pair Fatty acid amide is added from the side feeding inlet of extrusion equipment, and latter same extrusion is mixed with mixture, and then cooling, granulation is made Modified enhancing nylon；

In the step (1), stirring rate 800rpm；In the step (2), the parameter of extrusion equipment an are as follows: Qu Wen Degree is 270 DEG C, and two area's temperature are 260 DEG C, and three area's temperature are 260 DEG C, and four area's temperature are 250 DEG C, and five area's temperature are 240 DEG C.

The modified nano cerium oxide is made by following steps:

Step is 1.: ethyl alcohol, isopropanol and deionized water is mixed evenly with volume ratio for 15:5:1, solvent A is made, Then titanate coupling agent is added into solvent A, 40min is mixed, modified solution is made；

Step is 2.: ethyl alcohol and isopropanol being mixed evenly with volume ratio for 3:1, solvent B is made, then by nano oxygen Change cerium to be added into solvent B, nano-cerium oxide solution is made in ultrasonic disperse 40min under conditions of frequency is 15000Hz；

Step is 3.: by step, 2. nano-cerium oxide solution obtained in temperature is stirring in water bath at 65 DEG C, while stirring will 1. modified solution obtained is added dropwise in nano-cerium oxide solution step, continues to stir 5min after being added dropwise, then will mixing Object filtering, filter residue are washed 2 times with cleaning solution, are then to dry 8h at 70 DEG C in temperature by the filter residue after washing, grind, be made and change Property nano-cerium oxide.

The step 1. in, the solid-liquid ratio of titanate coupling agent and solvent A is 1:30, and the titanate coupling agent is double (two octyloxy pyrophosphoric acid ester groups) ethylene titanate esters；The step 2. in, the partial size of nano-cerium oxide is 20nm, nano-cerium oxide In advance through 55 DEG C of drying 6h, the solid-liquid ratio of nano-cerium oxide and solvent B are 1:15；The step 3. in, the revolving speed of stirring in water bath The mixture being made of for 800rpm, the cleaning solution ethyl alcohol and deionized water with volume ratio for 18:1.

Every part of synergist includes 8 parts of zinc oxide, 4 parts of silicon carbide and 3 parts of mica powders；The compatilizer is by styrene The mixing that grafted maleic anhydride and ethylene-acrylic acid-butyl ester graft glycidyl methacrylate are formed with weight ratio for 2:1 Object；The lubricant is what 2.4:1 was formed with weight ratio by pentaerythritol stearate and hydrogenation ethylenebisstearamide Mixture.

A kind of fireproof aluminum-plastic board containing nano-meter flame retardants, the fireproof aluminum-plastic board include on from top to bottom sequentially connected Aluminium sheet 1, the first adhesive-layer 2, sandwich layer 3, the second adhesive-layer 4 and lower aluminum sheet 5, the core material of the sandwich layer 3 from the above mentioned is made, described Sandwich layer 3 is made by following steps:

According to parts by weight, by polyethylene, polycarbonate, modified enhancing nylon and compatilizer under conditions of temperature is 70 DEG C 30min is mixed, then cools to room temperature, remaining material is added while stirring, is uniformly mixed, adds to extrusion equipment Middle extrusion, the material after extrusion is directly added to carry out injection molding processing in injection molding apparatus, cooling, and sandwich layer 3 is made.

Embodiment 2

Every part of nano-meter flame retardants gather including 8.5 parts of hexaphenoxycyclotriphosphazenes, 3.5 parts of nano silicas, 2.5 parts Ammonium phosphate, 2.5 parts of Magnesium Hydroxide Nano-particles and 5.2 parts of Nano glass powders.

The hexaphenoxycyclotriphosphazene is made by following steps:

Step (2): mixture A made from step (1) is warming up to 80 DEG C, ZnO is added, pentachloro- is then added while stirring Change phosphorus, while being passed through chlorine, heating stirring reflux 13h cools down after completion of the reaction, takes out press filtration, and three phosphorus of chlordene ring is made in washing Nitrile；

Step (4): mixture B made from step (3) is instilled into sodium hydroxide solution, 71 DEG C is warming up to, stirs back 22h is flowed, phenol sodium solution is made；

Step (6): mixture C made from step (5) is instilled into phenol sodium solution made from step (4), side stirring Side instills, and is warming up to 71 DEG C, is stirred at reflux 29h, and mixture D is made；

In the step (1), the mixed liquor ratio of ammonium chloride powder and chlorobenzene is 2.2:4；In the step (2), pentachloro- The mixed proportion for changing phosphorus and mixture A is 3.5:6, and chlorine intake is 190m³Speed of agitator when phosphorus pentachloride is added in/min For 8500rpm；In the step (3), the mixed liquor ratio of phenol and tetrahydrofuran is 2.8:6；In the step (4), mixing The mixed proportion of object B and sodium hydroxide solution is 1.2:1；In the step (5), the mixing of hexachlorocyclotriph,sphazene and dioxane Solid-liquid ratio is 1.5:5；In the step (6), speed of agitator when instilling mixture C is 700rpm.

The modified ethylene bis-fatty acid amides are ethylene bis-fatty acid amides under the action of cumyl peroxide, with Reactive monomer divinylbenzene or maleic anhydride containing polar group react the BAB type copolymer to be formed；The toughener The mixture being made of polyvinyl butyral and dioctyl phthalate with weight ratio for 2.5:1.

The modified enhancing nylon is made by following steps:

In the step (1), stirring rate 900rpm；In the step (2), the parameter of extrusion equipment an are as follows: Qu Wen Degree is 272 DEG C, and two area's temperature are 262 DEG C, and three area's temperature are 262 DEG C, and four area's temperature are 252 DEG C, and five area's temperature are 242 DEG C.

The modified nano cerium oxide is made by following steps:

Step is 1.: ethyl alcohol, isopropanol and deionized water is mixed evenly with volume ratio for 16:6:1, solvent A is made, Then titanate coupling agent is added into solvent A, 42min is mixed, modified solution is made；

Step is 2.: ethyl alcohol and isopropanol being mixed evenly with volume ratio for 4:1, solvent B is made, then by nano oxygen Change cerium to be added into solvent B, nano-cerium oxide solution is made in ultrasonic disperse 38min under conditions of frequency is 16000Hz；

Step is 3.: by step, 2. nano-cerium oxide solution obtained in temperature is stirring in water bath at 68 DEG C, while stirring will 1. modified solution obtained is added dropwise in nano-cerium oxide solution step, continues to stir 6min after being added dropwise, then will mixing Object filtering, filter residue are washed 2 times with cleaning solution, are then to dry 7.5h at 72 DEG C in temperature by the filter residue after washing, grind, be made Modified nano cerium oxide.

The step 1. in, the solid-liquid ratio of titanate coupling agent and solvent A is 1:31, and the titanate coupling agent is double (two octyloxy pyrophosphoric acid ester groups) ethylene titanate esters；The step 2. in, the partial size of nano-cerium oxide is 50nm, nano-cerium oxide In advance through 58 DEG C of drying 5.5h, the solid-liquid ratio of nano-cerium oxide and solvent B are 1:16；The step 3. in, stirring in water bath turn Speed is 900rpm, the mixture that the cleaning solution is made of ethyl alcohol and deionized water with volume ratio for 17:1.

Every part of synergist includes 9 parts of zinc oxide, 5 parts of silicon carbide and 3.5 parts of mica powders；The compatilizer is by benzene second What alkene grafted maleic anhydride and ethylene-acrylic acid-butyl ester graft glycidyl methacrylate were formed with weight ratio for 2.5:1 Mixture；The lubricant is with weight ratio by pentaerythritol stearate and hydrogenation ethylenebisstearamide for 2.6:1 group At mixture.

According to parts by weight, by polyethylene, polycarbonate, modified enhancing nylon and compatilizer under conditions of temperature is 74 DEG C 28min is mixed, then cools to room temperature, remaining material is added while stirring, is uniformly mixed, adds to extrusion equipment Middle extrusion, the material after extrusion is directly added to carry out injection molding processing in injection molding apparatus, cooling, and sandwich layer 3 is made.

Embodiment 3

Every part of nano-meter flame retardants include 9 parts of hexaphenoxycyclotriphosphazenes, 4 parts of nano silicas, 3 parts of polyphosphoric acids Ammonium, 3 parts of Magnesium Hydroxide Nano-particles and 5.5 parts of Nano glass powders.

The hexaphenoxycyclotriphosphazene is made by following steps:

Step (2): mixture A made from step (1) is warming up to 85 DEG C, ZnO is added, pentachloro- is then added while stirring Change phosphorus, while being passed through chlorine, heating stirring reflux 14h cools down after completion of the reaction, takes out press filtration, and three phosphorus of chlordene ring is made in washing Nitrile；

Step (4): mixture B made from step (3) is instilled into sodium hydroxide solution, 73 DEG C is warming up to, stirs back 21h is flowed, phenol sodium solution is made；

Step (6): mixture C made from step (5) is instilled into phenol sodium solution made from step (4), side stirring Side instills, and is warming up to 73 DEG C, is stirred at reflux 28h, and mixture D is made；

In the step (1), the mixed liquor ratio of ammonium chloride powder and chlorobenzene is 2.5:4；In the step (2), pentachloro- The mixed proportion for changing phosphorus and mixture A is 4:6, and chlorine intake is 210m³/ min, speed of agitator when phosphorus pentachloride is added are 900rpm；In the step (3), the mixed liquor ratio of phenol and tetrahydrofuran is 2.5:6；In the step (4), mixture B Mixed proportion with sodium hydroxide solution is 1.5:1；In the step (5), the mixture of hexachlorocyclotriph,sphazene and dioxane Liquor ratio is 2:5；In the step (6), speed of agitator when instilling mixture C is 750rpm.

The modified ethylene bis-fatty acid amides are ethylene bis-fatty acid amides under the action of cumyl peroxide, with Reactive monomer divinylbenzene or maleic anhydride containing polar group react the BAB type copolymer to be formed；The toughener The mixture being made of polyvinyl butyral and dioctyl phthalate with weight ratio for 3:1.

The modified enhancing nylon is made by following steps:

In the step (1), stirring rate 1000rpm；In the step (2), the parameter of extrusion equipment an are as follows: Qu Wen Degree is 275 DEG C, and two area's temperature are 265 DEG C, and three area's temperature are 265 DEG C, and four area's temperature are 255 DEG C, and five area's temperature are 245 DEG C.

The modified nano cerium oxide is made by following steps:

Step is 1.: ethyl alcohol, isopropanol and deionized water being mixed evenly with volume ratio for 16.5:8:1, solvent is made Then A titanate coupling agent is added into solvent A, 45min is mixed, and modified solution is made；

Step is 2.: ethyl alcohol and isopropanol being mixed evenly with volume ratio for 5:1, solvent B is made, then by nano oxygen Change cerium to be added into solvent B, nano-cerium oxide solution is made in ultrasonic disperse 35min under conditions of frequency is 18000Hz；

Step is 3.: by step, 2. nano-cerium oxide solution obtained in temperature is stirring in water bath at 70 DEG C, while stirring will 1. modified solution obtained is added dropwise in nano-cerium oxide solution step, continues to stir 8min after being added dropwise, then will mixing Object filtering, filter residue are washed 3 times with cleaning solution, are then to dry 7h at 75 DEG C in temperature by the filter residue after washing, grind, be made and change Property nano-cerium oxide.

The step 1. in, the solid-liquid ratio of titanate coupling agent and solvent A is 1:32, and the titanate coupling agent is double (two octyloxy pyrophosphoric acid ester groups) ethylene titanate esters；The step 2. in, the partial size of nano-cerium oxide is 100nm, nano oxidized For cerium in advance through 63 DEG C of drying 5h, the solid-liquid ratio of nano-cerium oxide and solvent B are 1:16.5；The step 3. in, stirring in water bath Revolving speed is 1000rpm, the mixture that the cleaning solution is made of ethyl alcohol and deionized water with volume ratio for 16.5:1.

Every part of synergist includes 01 part of zinc oxide, 5.5 parts of silicon carbide and 4 parts of mica powders；The compatilizer is by benzene What Vinyl Graft maleic anhydride and ethylene-acrylic acid-butyl ester graft glycidyl methacrylate were formed with weight ratio for 3:1 Mixture；The lubricant is with weight ratio by pentaerythritol stearate and hydrogenation ethylenebisstearamide for 2.8:1 group At mixture.

According to parts by weight, by polyethylene, polycarbonate, modified enhancing nylon and compatilizer under conditions of temperature is 78 DEG C 25min is mixed, then cools to room temperature, remaining material is added while stirring, is uniformly mixed, adds to extrusion equipment Middle extrusion, the material after extrusion is directly added to carry out injection molding processing in injection molding apparatus, cooling, and sandwich layer 3 is made.

Embodiment 4

Every part of nano-meter flame retardants gather including 9.5 parts of hexaphenoxycyclotriphosphazenes, 4.5 parts of nano silicas, 3.5 parts Ammonium phosphate, 3.5 parts of Magnesium Hydroxide Nano-particles and 5.8 parts of Nano glass powders.

The hexaphenoxycyclotriphosphazene is made by following steps:

Step (2): mixture A made from step (1) is warming up to 90 DEG C, ZnO is added, pentachloro- is then added while stirring Change phosphorus, while being passed through chlorine, heating stirring reflux 15h cools down after completion of the reaction, takes out press filtration, and three phosphorus of chlordene ring is made in washing Nitrile；

Step (4): mixture B made from step (3) is instilled into sodium hydroxide solution, 74 DEG C is warming up to, stirs back 19h is flowed, phenol sodium solution is made；

Step (6): mixture C made from step (5) is instilled into phenol sodium solution made from step (4), side stirring Side instills, and is warming up to 74 DEG C, is stirred at reflux 26h, and mixture D is made；

In the step (1), the mixed liquor ratio of ammonium chloride powder and chlorobenzene is 2.8:4；In the step (2), pentachloro- The mixed proportion for changing phosphorus and mixture A is 4.5:6, and chlorine intake is 230m³Speed of agitator when phosphorus pentachloride is added in/min For 950rpm；In the step (3), the mixed liquor ratio of phenol and tetrahydrofuran is 2.2:6；In the step (4), mixture The mixed proportion of B and sodium hydroxide solution is 1.8:1；In the step (5), the mixture of hexachlorocyclotriph,sphazene and dioxane Liquor ratio is 2.5:5；In the step (6), speed of agitator when instilling mixture C is 800rpm.

The modified ethylene bis-fatty acid amides are ethylene bis-fatty acid amides under the action of cumyl peroxide, with Reactive monomer divinylbenzene or maleic anhydride containing polar group react the BAB type copolymer to be formed；The toughener The mixture being made of polyvinyl butyral and dioctyl phthalate with weight ratio for 3.5:1.

The modified enhancing nylon is made by following steps:

In the step (1), stirring rate 1100rpm；In the step (2), the parameter of extrusion equipment an are as follows: Qu Wen Degree is 278 DEG C, and two area's temperature are 268 DEG C, and three area's temperature are 268 DEG C, and four area's temperature are 258 DEG C, and five area's temperature are 248 DEG C.

The modified nano cerium oxide is made by following steps:

Step is 1.: ethyl alcohol, isopropanol and deionized water is mixed evenly with volume ratio for 17:9:1, solvent A is made, Then titanate coupling agent is added into solvent A, 48min is mixed, modified solution is made；

Step is 2.: ethyl alcohol and isopropanol being mixed evenly with volume ratio for 6:1, solvent B is made, then by nano oxygen Change cerium to be added into solvent B, nano-cerium oxide solution is made in ultrasonic disperse 32min under conditions of frequency is 19000Hz；

Step is 3.: by step, 2. nano-cerium oxide solution obtained in temperature is stirring in water bath at 73 DEG C, while stirring will 1. modified solution obtained is added dropwise in nano-cerium oxide solution step, continues to stir 9min after being added dropwise, then will mixing Object filtering, filter residue are washed 3 times with cleaning solution, are then to dry 6.5h at 78 DEG C in temperature by the filter residue after washing, grind, be made Modified nano cerium oxide.

The step 1. in, the solid-liquid ratio of titanate coupling agent and solvent A is 1:33, and the titanate coupling agent is double (two octyloxy pyrophosphoric acid ester groups) ethylene titanate esters；The step 2. in, the partial size of nano-cerium oxide is 150nm, nano oxidized For cerium in advance through 66 DEG C of drying 4.5h, the solid-liquid ratio of nano-cerium oxide and solvent B are 1:17；The step 3. in, stirring in water bath Revolving speed is 1100rpm, the mixture that the cleaning solution is made of ethyl alcohol and deionized water with volume ratio for 16:1.

Every part of synergist includes 11 parts of zinc oxide, 6 parts of silicon carbide and 4.5 parts of mica powders；The compatilizer is by benzene Vinyl Graft maleic anhydride and ethylene-acrylic acid-butyl ester graft glycidyl methacrylate are formed with weight ratio for 3.5:1 Mixture；The lubricant is with weight ratio by pentaerythritol stearate and hydrogenation ethylenebisstearamide for 3.0:1 The mixture of composition.

According to parts by weight, by polyethylene, polycarbonate, modified enhancing nylon and compatilizer under conditions of temperature is 82 DEG C 22min is mixed, then cools to room temperature, remaining material is added while stirring, is uniformly mixed, adds to extrusion equipment Middle extrusion, the material after extrusion is directly added to carry out injection molding processing in injection molding apparatus, cooling, and sandwich layer 3 is made.

Embodiment 5

Every part of nano-meter flame retardants include 10 parts of hexaphenoxycyclotriphosphazenes, 5 parts of nano silicas, 4 parts of polyphosphoric acids Ammonium, 4 parts of Magnesium Hydroxide Nano-particles and 6 parts of Nano glass powders.

The hexaphenoxycyclotriphosphazene is made by following steps:

Step (2): mixture A made from step (1) is warming up to 95 DEG C, ZnO is added, pentachloro- is then added while stirring Change phosphorus, while being passed through chlorine, heating stirring reflux 16h cools down after completion of the reaction, takes out press filtration, and three phosphorus of chlordene ring is made in washing Nitrile；

Step (4): mixture B made from step (3) is instilled into sodium hydroxide solution, 75 DEG C is warming up to, stirs back 18h is flowed, phenol sodium solution is made；

Step (6): mixture C made from step (5) is instilled into phenol sodium solution made from step (4), side stirring Side instills, and is warming up to 75 DEG C, is stirred at reflux 25h, and mixture D is made；

In the step (1), the mixed liquor ratio of ammonium chloride powder and chlorobenzene is 3:4；It is phosphoric in the step (2) The mixed proportion of phosphorus and mixture A are 5:6, and chlorine intake is 250m³/ min, speed of agitator when phosphorus pentachloride is added are 1000rpm；In the step (3), the mixed liquor ratio of phenol and tetrahydrofuran is 2:6；In the step (4), mixture B with The mixed proportion of sodium hydroxide solution is 2:1；In the step (5), the mixed liquor ratio of hexachlorocyclotriph,sphazene and dioxane For 3:5；In the step (6), speed of agitator when instilling mixture C is 900rpm.

The modified ethylene bis-fatty acid amides are ethylene bis-fatty acid amides under the action of cumyl peroxide, with Reactive monomer divinylbenzene or maleic anhydride containing polar group react the BAB type copolymer to be formed；The toughener The mixture being made of polyvinyl butyral and dioctyl phthalate with weight ratio for 4:1.

The modified enhancing nylon is made by following steps:

In the step (1), stirring rate 1200rpm；In the step (2), the parameter of extrusion equipment an are as follows: Qu Wen Degree is 280 DEG C, and two area's temperature are 270 DEG C, and three area's temperature are 270 DEG C, and four area's temperature are 260 DEG C, and five area's temperature are 250 DEG C.

The modified nano cerium oxide is made by following steps:

Step is 1.: ethyl alcohol, isopropanol and deionized water being mixed evenly with volume ratio for 18:10:1, solvent is made Then A titanate coupling agent is added into solvent A, 50min is mixed, and modified solution is made；

Step is 2.: ethyl alcohol and isopropanol being mixed evenly with volume ratio for 8:1, solvent B is made, then by nano oxygen Change cerium to be added into solvent B, nano-cerium oxide solution is made in ultrasonic disperse 30min under conditions of frequency is 20000Hz；

Step is 3.: by step, 2. nano-cerium oxide solution obtained in temperature is stirring in water bath at 75 DEG C, while stirring will 1. modified solution obtained is added dropwise in nano-cerium oxide solution step, continues to stir 10min after being added dropwise, then will mixing Object filtering, filter residue are washed 4 times with cleaning solution, are then to dry 6h at 80 DEG C in temperature by the filter residue after washing, grind, be made and change Property nano-cerium oxide.

The step 1. in, the solid-liquid ratio of titanate coupling agent and solvent A is 1:35, and the titanate coupling agent is double (two octyloxy pyrophosphoric acid ester groups) ethylene titanate esters；The step 2. in, the partial size of nano-cerium oxide is 200nm, nano oxidized For cerium in advance through 70 DEG C of drying 4h, the solid-liquid ratio of nano-cerium oxide and solvent B are 1:18；The step 3. in, stirring in water bath turn Speed is 1200rpm, the mixture that the cleaning solution is made of ethyl alcohol and deionized water with volume ratio for 15:1.

Every part of synergist includes 12 parts of zinc oxide, 7 parts of silicon carbide and 5 parts of mica powders；The compatilizer is by benzene second Alkene grafted maleic anhydride and ethylene-acrylic acid-butyl ester graft glycidyl methacrylate are formed with weight ratio for 4:1 mixed Close object；The lubricant is made of pentaerythritol stearate and hydrogenation ethylenebisstearamide with weight ratio for 3.2:1 Mixture.

According to parts by weight, by polyethylene, polycarbonate, modified enhancing nylon and compatilizer under conditions of temperature is 85 DEG C 20min is mixed, then cools to room temperature, remaining material is added while stirring, is uniformly mixed, adds to extrusion equipment Middle extrusion, the material after extrusion is directly added to carry out injection molding processing in injection molding apparatus, cooling, and sandwich layer 3 is made.

Comparative example 1

This comparative example and the difference of above-described embodiment 3 are:

The core material includes the raw material of following parts by weight:

Comparative example 2

The nano-cerium oxide is modified using commercially available silane coupling agent, specially KH-570 type silane coupling agent.

Comparative example 3

Every part of nano-meter flame retardants include 4 parts of nano silicas, 3 parts of ammonium polyphosphate, 3 parts of Magnesium Hydroxide Nano-particles With 5.5 parts of Nano glass powders.

Comparative example 4

Hexaphenoxycyclotriphosphazene in the nano-meter flame retardants uses traditional preparation method, specially ammonium chloride, five Phosphorus chloride reaction in atent solvent prepares hexachlorocyclotriph,sphazene, then is being more than by the inertia solution dissolved with hexachlorocyclotriph,sphazene It is added dropwise in the environment of 100 DEG C in the mixture of atent solvent, phenol, alkali metal hydroxide and water, high temperature prepares six benzene oxygen Three phosphonitrile of basic ring.

And the atent solvent wherein used is one of chlorobenzene, o-dichlorohenzene, toluene, dimethylbenzene, tetrachloroethanes or several Kind.

Comparative example 5

Every part of nano-meter flame retardants include 9 parts of hexaphenoxycyclotriphosphazenes, 4 parts of nano montmorillonites, 3 parts of ammonium polyphosphate, 3 Part Magnesium Hydroxide Nano-particles and 5.5 parts of Nano glass powders.

Aluminium-plastic panel made from embodiment 1-5 and comparative example 1-5 is subjected to bending strength, impact resistance, sandwich layer oxygen index (OI), core The performance tests such as layer combustion heat value, sandwich layer heat distortion temperature, it is shown that test result is as follows:

The bending strength and impact resistance of the plastic-aluminum slab products are according to " GB/T17748-2008 building curtain wall plastic-aluminum Composite plate " standard tested, the flame retardant rating of the aluminium-plastic panel is according to " GB 8624-2012 construction material and product burns Grading performance " standard tested, the combustion heat value of the sandwich layer is according to " GB/T 14402-2007 construction material and product Combustibility combustion heat value " standard tested.

By above-mentioned comparison it is found that aluminium-plastic panel produced by the present invention has excellent fire retardant performance, and intensity is high, hardness By force, bend-resistance, be unlikely to deform, weatherability is good, and thermal stability is high, reduces high temperature influence caused by sandwich layer of lower aluminum sheet.

Compared with Example 3, there is no by modification, plastic-aluminum slab products obtained for the nylon resin in 1 core material of comparative example Bending strength be only 110KPa, impact resistance is only 56 (kgcm), the product bending strength far below embodiment 1-5 and anti- Impact illustrates that the present invention by using the nylon resin modified by the present invention, can significantly improve the bending strength of sandwich layer, resist The mechanical strengths such as impact improve the comprehensive performances such as bending strength and the impact resistance of plastic-aluminum slab products, resistant to bending, stability It is high.

Compared with Example 3, the modified nano cerium oxide in 2 core material of comparative example is modified using silane coupling agent, system Oxygen index (OI), combustion heat value and the heat distortion temperature of the sandwich layer obtained are declined, and wherein oxygen index (OI) decline is significant, illustrate the present invention By using nano modification cerium oxide, and utilize titanate coupling agent [specially bis- (two octyloxy pyrophosphates of the invention Base) ethylene titanate esters] nano-cerium oxide is modified, strict control modification procedure, heat resistance, the heat of sandwich layer can be effectively improved Stability, heat-resisting quantity and anti-flammability, reduce aluminum profile excessive temperature influences caused by sandwich layer, improves the fire-retardant of aluminium-plastic panel Property.

Compared with Example 3, hexaphenoxycyclotriphosphazene is not used in the nano-meter flame retardants in 3 core material of comparative example, compared Hexaphenoxycyclotriphosphazene is prepared using traditional preparation method in nano-meter flame retardants in 4 core material of example, obtained sandwich layer oxygen Index, combustion heat value and heat distortion temperature are decreased obviously, and wherein each performance decline of comparative example 3 becomes apparent, and illustrate this hair The bright hexaphenoxycyclotriphosphazene prepared by using the method for the present invention, forms into charcoal system with polymer matrix, reduces burning Heat liberation unit, so reduce core material system combustion intensity, and its Pintsch process generate phenoxy group and its gasification product and Phosphoric-oxygenic compound Jun Ju You temper goes out the gaseous phase free radical effect of burning, promote layer of charcoal at charcoal effect, two aspects act on simultaneously, energy The oxygen index (OI), combustion heat value and heat distortion temperature of sandwich layer are significantly improved, fire retardant performance is excellent, and thermal stability is high.

Compared with Example 3, nano silica is replaced using montmorillonite in the nano-meter flame retardants in 5 core material of comparative example, Obtained sandwich layer oxygen index (OI), combustion heat value and heat distortion temperature is decreased obviously, and illustrates the present invention by using Nano grade There is great contact surface area between silica, with polymer, form close strand, effectively improve core material system Thermal stability and anti-flammability；And under the high temperature conditions, the P elements in hexaphenoxycyclotriphosphazene, nitrogen promote the shape of carbon-coating At, and element silicon then increases the thermal stability of layer of charcoal, stablizes Char Residues Structure closely, improves the oxygen index (OI) and heat-insulating flame-retardant of core material Performance.

Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way, Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.

Claims

1. a kind of dedicated core material of the fireproof aluminum-plastic board containing nano-meter flame retardants, it is characterised in that: the core material includes following weight The raw material of part:

2. a kind of dedicated core material of the fireproof aluminum-plastic board containing nano-meter flame retardants according to claim 1, it is characterised in that: every Part nano-meter flame retardants include 8-10 parts of hexaphenoxycyclotriphosphazenes, 3-5 parts of nano silicas, 2-4 parts of ammonium polyphosphate, 2- 4 parts of Magnesium Hydroxide Nano-particles and 5-6 parts of Nano glass powders.

3. a kind of dedicated core material of the fireproof aluminum-plastic board containing nano-meter flame retardants according to claim 2, it is characterised in that: institute Hexaphenoxycyclotriphosphazene is stated to be made by following steps:

Step (2): mixture A made from step (1) is warming up to 75-95 DEG C, ZnO is added, pentachloro- is then added while stirring Change phosphorus, while being passed through chlorine, heating stirring reflux 12-16h cools down after completion of the reaction, takes out press filtration, and chlordene ring is made in washing Three phosphonitriles；

Step (4): mixture B made from step (3) is instilled into sodium hydroxide solution, 70-75 DEG C is warming up to, is stirred at reflux Phenol sodium solution is made in 18-24h；

Step (6): mixture C made from step (5) is instilled into phenol sodium solution made from step (4), is dripped while stirring Enter, be warming up to 70-75 DEG C, be stirred at reflux 25-30h, mixture D is made；

Step (7): mixture D made from step (6) is cooling, concentration is subsequently poured into the deionized water of 1L, is stood, filtering, Filtered filtrate is subjected to concentration purification, hexaphenoxycyclotriphosphazene is made.

4. a kind of dedicated core material of the fireproof aluminum-plastic board containing nano-meter flame retardants according to claim 3, it is characterised in that: institute It states in step (1), the mixed liquor ratio of ammonium chloride powder and chlorobenzene is 2-3:4；In the step (2), phosphorus pentachloride with mix The mixed proportion of object A is 3-5:6, and chlorine intake is 180-250m³/ min, speed of agitator when phosphorus pentachloride is added are 800- 1000rpm；In the step (3), the mixed liquor ratio of phenol and tetrahydrofuran is 2-3:6；In the step (4), mixture B Mixed proportion with sodium hydroxide solution is 1-2:1；In the step (5), the mixture of hexachlorocyclotriph,sphazene and dioxane Liquor ratio is 1-3:5；In the step (6), speed of agitator when instilling mixture C is 600-900rpm.

5. a kind of dedicated core material of the fireproof aluminum-plastic board containing nano-meter flame retardants according to claim 1, it is characterised in that: institute State the raw material that modified enhancing nylon includes following parts by weight:

The modified ethylene bis-fatty acid amides are ethylene bis-fatty acid amides under the action of cumyl peroxide, and are contained The reactive monomer divinylbenzene or maleic anhydride of polar group react the BAB type copolymer to be formed；The toughener be by The mixture that polyvinyl butyral and dioctyl phthalate are formed with weight ratio for 2-4:1.

6. a kind of dedicated core material of the fireproof aluminum-plastic board containing nano-meter flame retardants according to claim 5, it is characterised in that: institute Modified enhancing nylon is stated to be made by following steps:

Step (1): in parts by weight, nylon, toughener and short glass fiber being dried respectively, and then mixing is stirred It mixes, obtains mixture；

Step (2): being added to extrusion equipment for mixture obtained in step (1) and squeeze out, and will the modified double fat of ethylene Sour amide is added from the side feeding inlet of extrusion equipment, and latter same extrusion is mixed with mixture, and modification is made in then cooling, granulation Enhance nylon；

In the step (1), stirring rate 800-1200rpm；In the step (2), the parameter of extrusion equipment an are as follows: Qu Wen Degree be 270-280 DEG C, two area's temperature be 260-270 DEG C, three area's temperature be 260-270 DEG C, four area's temperature be 250-260 DEG C, five Area's temperature is 240-250 DEG C.

7. a kind of dedicated core material of the fireproof aluminum-plastic board containing nano-meter flame retardants according to claim 1, it is characterised in that: institute Modified nano cerium oxide is stated to be made by following steps:

Step is 1.: ethyl alcohol, isopropanol and deionized water being mixed evenly with volume ratio for 15-18:5-10:1, solvent is made Then A titanate coupling agent is added into solvent A, 40-50min is mixed, and modified solution is made；

Step is 2.: ethyl alcohol and isopropanol is mixed evenly with volume ratio for 3-8:1, solvent B is made, it then will be nano oxidized Cerium is added into solvent B, and nano-cerium oxide is made in ultrasonic disperse 30-40min under conditions of frequency is 15000-20000Hz Solution；

Step is 3.: by step 2. nano-cerium oxide solution obtained in temperature be stirring in water bath at 65-75 DEG C, while stirring will step Suddenly 1. modified solution obtained is added dropwise in nano-cerium oxide solution, continues to stir 5-10min after being added dropwise, then will mixing Object filtering, filter residue are washed 2-4 times with cleaning solution, are then to dry 6-8h at 70-80 DEG C in temperature by the filter residue after washing, are ground Modified nano cerium oxide is made in mill.

8. a kind of dedicated core material of the fireproof aluminum-plastic board containing nano-meter flame retardants according to claim 7, it is characterised in that: institute State step 1. in, the solid-liquid ratio of titanate coupling agent and solvent A is 1:30-35, and the titanate coupling agent is bis- (two octyloxies Pyrophosphoric acid ester group) ethylene titanate esters；The step 2. in, the partial size of nano-cerium oxide is 20-200nm, and nano-cerium oxide is preparatory Through 55-70 DEG C of drying 4-6h, the solid-liquid ratio of nano-cerium oxide and solvent B are 1:15-18；The step 3. in, stirring in water bath Revolving speed is 800-1200rpm, the mixture that the cleaning solution is made of ethyl alcohol and deionized water with volume ratio for 15-18:1.

9. a kind of dedicated core material of the fireproof aluminum-plastic board containing nano-meter flame retardants according to claim 1, it is characterised in that: every Part synergist includes 8-12 parts of zinc oxide, 4-7 parts of silicon carbide and 3-5 parts of mica powders；The compatilizer is connect by styrene The mixing that branch maleic anhydride and ethylene-acrylic acid-butyl ester graft glycidyl methacrylate are formed with weight ratio for 2-4:1 Object；The lubricant is with weight ratio by pentaerythritol stearate and hydrogenation ethylenebisstearamide for 2.4-3.2:1 group At mixture.

10. a kind of fireproof aluminum-plastic board containing nano-meter flame retardants, it is characterised in that: the fireproof aluminum-plastic board include from top to bottom according to Upper aluminium sheet, the first adhesive-layer, sandwich layer, the second adhesive-layer and the lower aluminum sheet of secondary connection, the sandwich layer is by any one of claim 1-9 The core material is made, and the sandwich layer is made by following steps:

According to parts by weight, by polyethylene, polycarbonate, modified enhancing nylon and compatilizer under conditions of temperature is 70-85 DEG C 20-30min is mixed, then cools to room temperature, remaining material is added while stirring, is uniformly mixed, adds to extrusion It being squeezed out in equipment, the material after extrusion is directly added to carry out injection molding processing in injection molding apparatus, and it is cooling, core is made Layer.