CN103895297B - A kind of flame-retardant aluminum plastic composite sheet and preparation method thereof - Google Patents
A kind of flame-retardant aluminum plastic composite sheet and preparation method thereof Download PDFInfo
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- CN103895297B CN103895297B CN201410072774.5A CN201410072774A CN103895297B CN 103895297 B CN103895297 B CN 103895297B CN 201410072774 A CN201410072774 A CN 201410072774A CN 103895297 B CN103895297 B CN 103895297B
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- 239000002131 composite material Substances 0.000 title claims abstract description 86
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 81
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000003063 flame retardant Substances 0.000 title claims abstract description 56
- 239000004033 plastic Substances 0.000 title claims abstract description 51
- 229920003023 plastic Polymers 0.000 title claims abstract description 51
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004793 Polystyrene Substances 0.000 claims abstract description 49
- 229920002223 polystyrene Polymers 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 36
- 230000001070 adhesive effect Effects 0.000 claims abstract description 28
- 239000004411 aluminium Substances 0.000 claims abstract description 28
- 239000000853 adhesive Substances 0.000 claims abstract description 27
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 19
- 229920006380 polyphenylene oxide Polymers 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229920002678 cellulose Polymers 0.000 claims abstract description 13
- 235000010980 cellulose Nutrition 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 230000003111 delayed effect Effects 0.000 claims abstract description 5
- 238000001125 extrusion Methods 0.000 claims abstract description 3
- -1 polydimethylsiloxanes Polymers 0.000 claims description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 24
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 18
- 239000003292 glue Substances 0.000 claims description 16
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 14
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 13
- 238000004026 adhesive bonding Methods 0.000 claims description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 11
- 239000001913 cellulose Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000005453 pelletization Methods 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000004888 barrier function Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000002045 lasting effect Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 abstract 2
- 239000000463 material Substances 0.000 description 29
- 239000010410 layer Substances 0.000 description 10
- 239000003610 charcoal Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 7
- 238000003490 calendering Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000011162 core material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 241001502050 Acis Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004836 Glue Stick Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides a kind of flame-retardant aluminum plastic composite sheet, be made up of aluminium film, adhesive and polystyrene-based composite sheet, described aluminium film is through vacuum furnace coating adhesive, under 95 ~ 105 DEG C of conditions, the hot compound of roll-in, cold roll-in are delayed with polystyrene-based composite sheet again, obtained flame-retardant aluminum plastic composite sheet; Described polystyrene-based composite sheet is made by the raw materials melt blending extrusion of following weight portion: 40 ~ 60 parts of polystyrene, 17 ~ 26 parts of APPs, 5 ~ 10 parts of celluloses, 6 ~ 8 parts of modified montmorillonoids and 12 ~ 16 parts of polyphenylene oxide; Flame-retardant aluminum plastic composite sheet of the present invention has excellent lasting fire resistance, mechanical property, barrier property and weather resistance, and preparation method is simple, is suitable for suitability for industrialized production.
Description
(1) technical field
The present invention relates to field of compound material, be specifically related to a kind of flame-retardant aluminum plastic composite sheet and preparation method thereof.
(2) background technology
The multilayer materials that plastic-aluminum combined sheet material is take synthesized polymer material as sandwich layer, aluminium film is finish coat.Plastic-aluminum combined sheet material, with light weight environmental protection, fashion attractive in appearance, easy construction and high durable, high-barrier, the feature such as clean, is widely used in the fields such as building curtain wall, advertising board, indoor and outdoor decoration, car and boat decoration, Furniture manufacture.Plastic-aluminum combined sheet material is more economical relative to fine aluminium sheet material, more environmental protection, meets the requirement of developing a circular economy with low-carbon economy.But plastic-aluminum combined sheet material core material generally uses the materials such as inflammable polystyrene, polyethylene, this has buried hidden danger for breaking out of fire.For ensureing the safety in utilization of plastic-aluminum combined sheet material in the field such as building product, decorating and renovating material, promoting applying of this series products further, the fire resistance with improving product need be increased.
Solve the inflammable problem of plastic-aluminum combined sheet material mainly through adding fire retardant in the substrate to realize.Conventional fire retardant has: (a) halogen flame, this based flame retardant plays fire retardation with gas phase, but halogen flame can produce a large amount of poisonous mordant smog (comprising hydrogen halides, dioxin) when burning, easily cause secondary pollution, do not reach the requirement of environment-friendly building materials, therefore the fire retardant of aluminium plastic composite material base material with fire prevention, environment-friendly function should not be elected to be.B () phosphor nitrogen combustion inhibitor, this based flame retardant suppresses material combustion by the fire-retardant pattern of condensed phase.Its condensed phase is mainly porous foam layer of charcoal, effectively can isolate spreading of oxygen and heat, stop material to burn further, but be used alone the Char Residues Structure insufficient strength of phosphor nitrogen combustion inhibitor formation, easily cave in when large area sheet material is formed and again expose burning things which may cause a fire disaster.(c) metal hydroxide combustion inhibitor, this based flame retardant absorbs heat when high temperature dehydration, the heat that burning produces can be taken away, reduce burning velocity, prevent propagation of flame, reach the object suppressing burning, and do not produce thick smoke and toxic gas, secondary pollution can not be caused, now the existing core being used as the flame-retardant aluminum plastic composite (as 4mm heavy-gauge sheeting) of thicker size to environment.At present, there are German Alucobond, Mitsubishi Alpolic, U.S. Reynolds etc. in the overseas enterprise adopting this kind of scheme to manufacture flame-retardant aluminum plastic composite, there are the outstanding thing outstanding person in Hefei, the refined auspicious science and technology in Shanghai, Hunan plastic institute etc. in domestic enterprise, and Patents has CN102108145A, CN101475716B, CN1817813 etc.For reaching good flame retardant effect, the addition of the mineral-type such as metal hydroxides and Firebrake ZB synergist in aluminium plastic composite material core is large, and (common metal hydroxide weight portion is 60 ~ 80%, mineral-type synergist weight portion is 2 ~ 10%), cause material hardness large and fragility is large, plasticity be deteriorated and manufacture composite type based on thicker sheet material, slim flame-retardant aluminum plastic composite sheet (thickness 0.5 ~ 0.8mm) cannot be made.Therefore, it may be necessary and introduce new material, new technology, a kind of eco-friendly ultrathin flame-retardant aluminum plastic composite sheet of exploitation and preparation method thereof, to widen the application of aluminium plastic composite material.
(3) summary of the invention
The invention provides a kind of flame-retardant aluminum plastic composite sheet, it has excellent lasting fire resistance, mechanical property, barrier property and weather resistance.
Present invention also offers a kind of preparation method of flame-retardant aluminum plastic composite sheet, this preparation method is simple to operate, is suitable for suitability for industrialized production.
The present invention adopts following technical scheme:
A kind of flame-retardant aluminum plastic composite sheet, described flame-retardant aluminum plastic composite sheet is made up of aluminium film, organic silicon adhesive and polystyrene-based composite sheet, described aluminium film is coated with organic silicon adhesive through vacuum furnace, under 95 ~ 105 DEG C of conditions, the hot compound of roll-in, cold roll-in are delayed with polystyrene-based composite sheet again, obtained flame-retardant aluminum plastic composite sheet; Described polystyrene-based composite sheet is made by the raw materials melt blending extrusion of following weight portion: 40 ~ 60 parts of polystyrene, 17 ~ 26 parts of APPs, 5 ~ 10 parts of celluloses, 6 ~ 8 parts of modified montmorillonoids and 12 ~ 16 parts of polyphenylene oxide; Described modified montmorillonoid is alkyl trimethyl quaternary ammonium salt modified montmorillonoid, and the molecular structural formula of described alkyl trimethyl quaternary ammonium salt is CH
3(CH
2)
nn (CH
3)
3 +x
-, wherein, n=17 ~ 25, X is Cl or Br; Preferably described modified montmorillonoid is Cetyltrimethylammonium bromide modified montmorillonoid; The particle diameter of described modified montmorillonoid is 15 ~ 25um.
Organic silicon adhesive of the present invention, its main component is dimethyl silicone polymer, and described organic silicon adhesive stirs mixing making by raw material constant temperature at 25 ~ 40 DEG C of following weight portion: 70 ~ 80 parts of hydroxyl endblocked polydimethylsiloxanes, 6 ~ 10 parts of alkyl-blocked dimethyl silicone polymers, 1 ~ 2 part of dimethyl-penten diamines, 0.5 ~ 2 part of organotin catalysts and 6 ~ 22.5 parts of aerosils; Wherein, described organotin catalysts be selected from a kind of in dibutyltin diacetate, dibutyl tin laurate, stannous octoate or wherein any two kinds with the mixture of arbitrary proportion.
The source of modified montmorillonoid of the present invention is NANOCOR company of the U.S., and I.28E product type is.
The preferred pure aluminum foil of aluminium film of the present invention, thickness is 0.01 ~ 0.02mm; The thickness of described flame-retardant aluminum plastic composite sheet is 0.50 ~ 0.80mm.
Further, in the raw material of polystyrene-based composite sheet of the present invention, the degree of polymerization of described APP is 1000 ~ 1500, and phosphorus content is 31 ~ 32%, and particle diameter is 15 ~ 18um, if the degree of polymerization is too small, basic thermal stability declines; The degree of polymerization is excessive, and the initial heat decomposition temperature after fire met by material raises, and is unfavorable for promoting material dehydration carbonization in time; The cellulosic degree of polymerization described in recommendation is 2000 ~ 5000, and particle diameter is 15 ~ 25um, main one-tenth carbon synergist, and the degree of polymerization is too small, and its thermal stability declines; The degree of polymerization is excessive, and the Smelting Effect of itself and polystyrene resin declines; Described polyphenylene oxide is Powdered, and its glass transition temperature is 214 DEG C.
Further, described flame-retardant aluminum plastic composite sheet, the spread of described organic silicon adhesive is 30 ~ 75g/m
2aluminium film.
Further again, in flame-retardant aluminum plastic composite sheet, in the raw material of described organic silicon adhesive, the mean molecule quantity of described hydroxyl endblocked polydimethylsiloxane and described alkyl-blocked dimethyl silicone polymer is 1000 ~ 1500(1 ~ 15Pas, 25 DEG C); Molecular weight is too small, and the adhesive property of organic silicon adhesive to aluminium film and polystyrene-based composite sheet of formation declines; Molecular weight is excessive, and the viscosity of organic silicon adhesive is excessive, is strengthened, easily occur the problem that gluing is excessive or uneven by roll coating model to aluminium film gluing difficulty.
Concrete, the preparation method of flame-retardant aluminum plastic composite sheet of the present invention, comprises the steps:
(1) modified montmorillonoid and polyphenylene oxide melting mixing extruding pelletization are obtained imvite master batch, imvite master batch, polystyrene, APP, cellulose at 60 DEG C ~ 70 DEG C premixs, extrude through equidirectional parallel double-screw extruder melt blending after mixing, roll, draw, cooling forming, obtained polystyrene-based composite sheet;
(2) hydroxyl endblocked polydimethylsiloxane, alkyl-blocked dimethyl silicone polymer, dimethyl-penten diamines, organotin catalysts and aerosil are added glue cylinder, first glue cylinder is vacuumized, at 25 ~ 40 DEG C, constant temperature stirs mixing 20 ~ 30min again, obtained organic silicon adhesive.
(3) aluminium film presses spread 30 ~ 75g/m through vacuum furnace
2aluminium film is delayed with polystyrene-based the composite sheet hot compound of roll-in, cold roll-in under 95 ~ 105 DEG C of conditions after being coated with gluing, obtained flame-retardant aluminum plastic composite sheet.
During concrete operations, the conventional high-speed mixer (the general speed of mainshaft is 300r/min) in this area can be selected to carry out mixed material, the time of each mixing is generally 10 ~ 20min can make mixing of materials even.
Modified montmorillonoid and polyphenylene oxide melting mixing extruding pelletization prepare imvite master batch, can control at 250 ~ 260 DEG C by the temperature of melt zone; During obtained polystyrene-based composite sheet, the temperature of melt zone can be controlled at 230 ~ 240 DEG C.
Tool of the present invention has the following advantages:
Flame-retardant aluminum plastic composite sheet of the present invention has excellent lasting fire resistance, mechanical property, barrier property and weather resistance.
Preparation method of the present invention adopts polyphenylene oxide to carry out melting mixing to modified montmorillonoid and dials layer process, and the imvite master batch after process and polystyrene, APP, cellulose melting compound are prepared flame-retardant aluminum plastic composite sheet, simple to operate, is suitable for suitability for industrialized production.
(4) accompanying drawing explanation
Fig. 1 is flame-retardant system structural design schematic diagram;
In figure: 1-aluminium foil, 2-silicone adhesive layer, 3-inflaming retarding core material.
(5) detailed description of the invention
Below by specific embodiment, the present invention is further described, but protection scope of the present invention is not limited thereto.
Embodiment 1
By 1.6kg polyphenylene oxide (Asahi Chemical Industry of S201A/ Japan) and 0.8kg Cetyltrimethylammonium bromide modified montmorillonoid (NANOCOR company of the U.S., I.28E) elder generation (speed of mainshaft 300r/min) premix 10min in high-speed mixer, premix temperature is 70 DEG C, again through parallel equidirectional two-screw extruder melt blending extruding pelletization, obtained imvite master batch, melt zone temperature 250 ~ 260 DEG C.2.4kg imvite master batch and 4.0kg polystyrene (1300/ LG-DOW), 2.6kg APP, 1.0kg cellulose (speed of mainshaft 300r/min) premix 10min in high-speed mixer, premix temperature is 70 DEG C, extrude through parallel equidirectional two-screw extruder melt blending again, roll, draw, cooling forming, obtained polystyrene-based composite sheet, melt zone temperature controls at 230 ~ 240 DEG C, and calendering heat roller temperature controls at 125 ~ 180 DEG C.
8.0kg hydroxyl endblocked polydimethylsiloxane, the alkyl-blocked dimethyl silicone polymer of 1.0kg, 0.1kg dimethyl-penten diamines, 0.2kg dibutyltin diacetate, 0.7kg aerosil are added glue cylinder, first glue cylinder is vacuumized, constant temperature (32 ~ 40 DEG C) stirs mixing again, obtained organic silicon adhesive.
Aluminium film is coated with gluing (spread 35g/m through vacuum furnace
2), delay with the hot compound of polystyrene-based composite sheet roll-in (heat roller temperature 95 ~ 105 DEG C), cold roll-in, obtained flame-retardant aluminum plastic composite sheet.
Embodiment 2
By 1.2kg polyphenylene oxide (Asahi Chemical Industry of S201A/ Japan) and 0.6kg Cetyltrimethylammonium bromide modified montmorillonoid (NANOCOR company of the U.S., I.28E) elder generation (speed of mainshaft 300r/min) premix 10min in high-speed mixer, premix temperature is 70 DEG C, again through parallel equidirectional two-screw extruder melt blending extruding pelletization, obtained imvite master batch, melt zone temperature 250 ~ 260 DEG C.1.8kg imvite master batch and 6.0kg polystyrene (1300/ LG-DOW), 1.7kg APP, 0.5kg cellulose (speed of mainshaft 300r/min) premix 10min in high-speed mixer, premix temperature is 70 DEG C, extrude through parallel equidirectional two-screw extruder melt blending again, roll, draw, cooling forming, obtained polystyrene-based composite sheet, melt zone temperature controls at 230 ~ 240 DEG C, and calendering heat roller temperature controls at 125 ~ 180 DEG C.
8.0kg hydroxyl endblocked polydimethylsiloxane, the alkyl-blocked dimethyl silicone polymer of 1.0kg, 0.1kg dimethyl-penten diamines, 0.2kg dibutyltin diacetate, 0.7kg aerosil are added glue cylinder, first glue cylinder is vacuumized, constant temperature (32 ~ 40 DEG C) stirs mixing again, obtained organic silicon adhesive.
Aluminium film is coated with gluing (spread 35g/m through vacuum furnace
2), delay with the hot compound of polystyrene-based composite sheet roll-in (heat roller temperature 95 ~ 105 DEG C), cold roll-in, obtained flame-retardant aluminum plastic composite sheet.
Embodiment 3
By 1.5kg polyphenylene oxide (Asahi Chemical Industry of S201A/ Japan) and 0.7kg Cetyltrimethylammonium bromide modified montmorillonoid (NANOCOR company of the U.S., I.28E) elder generation (speed of mainshaft 300r/min) premix 10min in high-speed mixer, premix temperature is 70 DEG C, again through parallel equidirectional two-screw extruder melt blending extruding pelletization, obtained imvite master batch, melt zone temperature 250 ~ 260 DEG C.2.2kg imvite master batch and 5.0kg polystyrene (1300/ LG-DOW), 2.0kg APP, 0.8kg cellulose (speed of mainshaft 300r/min) premix 10min in high-speed mixer, premix temperature is 70 DEG C, extrude through parallel equidirectional two-screw extruder melt blending again, roll, draw, cooling forming, obtained polystyrene-based composite sheet, melt zone temperature controls at 230 ~ 240 DEG C, and calendering heat roller temperature controls at 125 ~ 180 DEG C.
8.0kg hydroxyl endblocked polydimethylsiloxane, the alkyl-blocked dimethyl silicone polymer of 1.0kg, 0.1kg dimethyl-penten diamines, 0.2kg dibutyltin diacetate, 0.7kg aerosil are added glue cylinder, first glue cylinder is vacuumized, constant temperature (32 ~ 40 DEG C) stirs mixing again, obtained organic silicon adhesive.
Aluminium film is coated with gluing (spread 35g/m through vacuum furnace
2), delay with the hot compound of polystyrene-based composite sheet roll-in (heat roller temperature 95 ~ 105 DEG C), cold roll-in, obtained flame-retardant aluminum plastic composite sheet.
Embodiment 4
By 1.5kg polyphenylene oxide (Asahi Chemical Industry of S201A/ Japan) and 0.7kg Cetyltrimethylammonium bromide modified montmorillonoid (NANOCOR company of the U.S., I.28E) elder generation (speed of mainshaft 300r/min) premix 10min in high-speed mixer, premix temperature is 70 DEG C, again through parallel equidirectional two-screw extruder melt blending extruding pelletization, obtained imvite master batch, melt zone temperature 250 ~ 260 DEG C.2.2kg imvite master batch and 5.0kg polystyrene (1300/ LG-DOW), 2.0kg APP, 0.8kg cellulose (speed of mainshaft 300r/min) premix 10min in high-speed mixer, premix temperature is 70 DEG C, extrude through parallel equidirectional two-screw extruder melt blending again, roll, draw, cooling forming, obtained polystyrene-based composite sheet, melt zone temperature controls at 230 ~ 240 DEG C, and calendering heat roller temperature controls at 125 ~ 180 DEG C.
8.0kg hydroxyl endblocked polydimethylsiloxane, the alkyl-blocked dimethyl silicone polymer of 1.0kg, 0.1kg dimethyl-penten diamines, 0.15kg dibutyl tin laurate, 0.05kg stannous octoate, 0.7kg aerosil are added glue cylinder, first glue cylinder is vacuumized, constant temperature (32 ~ 40 DEG C) stirs mixing again, obtained organic silicon adhesive.
Aluminium film is coated with gluing (spread 75g/m through vacuum furnace
2), delay with the hot compound of polystyrene-based composite sheet roll-in (heat roller temperature 95 ~ 105 DEG C), cold roll-in, obtained flame-retardant aluminum plastic composite sheet.
Embodiment 5
By 1.5kg polyphenylene oxide (Asahi Chemical Industry of S201A/ Japan) and 0.7kg Cetyltrimethylammonium bromide modified montmorillonoid (NANOCOR company of the U.S., I.28E) elder generation (speed of mainshaft 300r/min) premix 10min in high-speed mixer, premix temperature is 70 DEG C, again through parallel equidirectional two-screw extruder melt blending extruding pelletization, obtained imvite master batch, melt zone temperature 250 ~ 260 DEG C.2.2kg imvite master batch and 5.0kg polystyrene (1300/ LG-DOW), 2.0kg APP, 0.8kg cellulose (speed of mainshaft 300r/min) premix 10min in high-speed mixer, premix temperature is 70 DEG C, extrude through parallel equidirectional two-screw extruder melt blending again, roll, draw, cooling forming, obtained polystyrene-based composite sheet, melt zone temperature controls at 230 ~ 240 DEG C, and calendering heat roller temperature controls at 125 ~ 180 DEG C.
7.0kg hydroxyl endblocked polydimethylsiloxane, the alkyl-blocked dimethyl silicone polymer of 0.6kg, 0.1kg dimethyl-penten diamines, 0.05kg dibutyl tin laurate, 2.25kg aerosil are added glue cylinder, first glue cylinder is vacuumized, constant temperature (32 ~ 40 DEG C) stirs mixing again, obtained organic silicon adhesive.
Aluminium film is coated with gluing (spread 35g/m through vacuum furnace
2), delay with the hot compound of polystyrene-based composite sheet roll-in (heat roller temperature 95 ~ 105 DEG C), cold roll-in, obtained flame-retardant aluminum plastic composite sheet.
Embodiment 6
By 1.5kg polyphenylene oxide (Asahi Chemical Industry of S201A/ Japan) and 0.7kg Cetyltrimethylammonium bromide modified montmorillonoid (NANOCOR company of the U.S., I.28E) elder generation (speed of mainshaft 300r/min) premix 10min in high-speed mixer, premix temperature is 70 DEG C, again through parallel equidirectional two-screw extruder melt blending extruding pelletization, obtained imvite master batch, melt zone temperature 250 ~ 260 DEG C.2.2kg imvite master batch and 5.0kg polystyrene (1300/ LG-DOW), 2.0kg APP, 0.8kg cellulose (speed of mainshaft 300r/min) premix 10min in high-speed mixer, premix temperature is 70 DEG C, extrude through parallel equidirectional two-screw extruder melt blending again, roll, draw, cooling forming, obtained polystyrene-based composite sheet, melt zone temperature controls at 230 ~ 240 DEG C, and calendering heat roller temperature controls at 125 ~ 180 DEG C.
7.0kg hydroxyl endblocked polydimethylsiloxane, the alkyl-blocked dimethyl silicone polymer of 0.6kg, 0.1kg dimethyl-penten diamines, 0.05kg dibutyl tin laurate, 2.25kg aerosil are added glue cylinder, first glue cylinder is vacuumized, constant temperature (32 ~ 40 DEG C) stirs mixing again, obtained organic silicon adhesive.
Aluminium film is coated with gluing (spread 75g/m through vacuum furnace
2), delay with the hot compound of polystyrene-based composite sheet roll-in (heat roller temperature 95 ~ 105 DEG C), cold roll-in, obtained flame-retardant aluminum plastic composite sheet.
Comparative example 1:
1.5kg polyphenylene oxide (Asahi Chemical Industry of S201A/ Japan), 2.0kg DTAB modified montmorillonoid, 5.0kg polystyrene (1300/ LG-DOW), 1.5kg APP (speed of mainshaft 300r/min) premix 10min in high-speed mixer, premix temperature is 70 DEG C, extrude through parallel equidirectional two-screw extruder melt blending again, roll, draw, cooling forming, obtained polystyrene-based composite sheet, melt zone temperature controls at 245 ~ 255 DEG C, and calendering heat roller temperature controls at 125 ~ 180 DEG C.
Aluminium film is coated with gluing (polyvinyl acetate glue stick, spread 75g/m through vacuum furnace
2), delay with the hot compound of polystyrene-based composite sheet roll-in (heat roller temperature 95 ~ 105 DEG C), cold roll-in, obtained flame-retardant aluminum plastic composite sheet.
Performance test is carried out, examination criteria to flame-retardant aluminum plastic composite sheet prepared by embodiment 1 ~ 6 and comparative example 1: hot strength is tested according to GB/T1040-2006 " mensuration of plastic tensile performance "; Oxygen index (OI) is tested according to " plastics oxygen index method measures burning behavior "; Horizontal firing residual length 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 residual length (cm) | |
Comparative example 1 | 24.2 | 28 | 15 |
Embodiment 1 | 18.6 | 36 | 66 |
Embodiment 2 | 23.2 | 31 | 47 |
Embodiment 3 | 22.3 | 33 | 58 |
Embodiment 4 | 22.8 | 35 | 68 |
Embodiment 5 | 21.8 | 35 | 70 |
Embodiment 6 | 21.0 | 37 | 73 |
Note: test samples thickness is 0.6mm
Simple analysis is once carried out to result: from table, (1) increase of polyphenylene oxide and organo montmorillonite content in composite, be conducive to the fire resistance (oxygen index (OI) rising, horizontal firing residual length increase) promoting material, but be unfavorable for the mechanical property (hot strength decline) keeping material; (2) flame retardance element in organic silicon adhesive and base material is conducive to the collaborative fire resistance promoting composite, and generally speaking, resin added is larger, and oxygen index (OI) and horizontal firing residual length increase all to some extent; (3) in organic silicon adhesive, the minimizing of the relative amount of adhesion component hydroxyl endblocked polydimethylsiloxane, the alkyl-blocked dimethyl silicone polymer of crosslinking agent can weaken the mechanical property of composite, although its fire resistance has lifting (this mainly comes from the increase of aerosil relative amount in adhesive).Therefore, embodiment 4 has the optimum proportioning after optimization, can give the excellent fire resistance of composite and mechanical property.
For the sandwich construction feature of plastic-aluminum combined sheet material, through flame-retardant system structural design (as Fig. 1), intend working in coordination with by two aspects the fire resistance strengthening composite sheet.
A () be the fire-retardant use polyphenylene oxide of p-poly-phenyl ethene core, organophosphorus compounds (APP), charcoal source material (cellulose) and modified montmorillonoid first, organophosphorus ester thermal decomposition at a certain temperature produces phosphoric acid, phosphoric acid is worked in coordination with charcoal source material and is impelled top layer polystyrene material to be dehydrated into charcoal, layer of charcoal effectively can isolate spreading of oxygen and heat, and protection primer stops it to burn further; Modified montmorillonoid is uniformly distributed in inflaming retarding core material after surface modification treatment, after burning makes system reach uniform temperature, modified montmorillonoid to be bondd formation cross-linked network mutually by polyphenylene oxide pyrolysis product and layer of charcoal, this structure effectively can strengthen the intensity of large area layer of charcoal, prevents from Char Residues Structure from caving in causing primer to be exposed in air resume combustion occurs.
Secondly b (); at inflaming retarding core material surface coating one deck organosilicon polymer adhesive protective layer; continuous print, oxidation resistant silicate protective layer is formed on above-mentioned layer of charcoal surface on the one hand in polysiloxanes combustion process; promote compactness and the barrier of layer of charcoal, suppress diffusion and the heat radiation of oxygen further.Polysiloxanes also has the fire-retardant mechanism of gas phase on the other hand, in combustion process, polysiloxanes decomposes the intermediate form existence with silicic acid and esters of silicon acis, and they can eliminate the peroxy that polystyrene produces in oxicracking, play inhibitory action to the oxicracking of polymer.
Claims (9)
1. a flame-retardant aluminum plastic composite sheet, it is characterized in that described flame-retardant aluminum plastic composite sheet is made up of aluminium film, organic silicon adhesive and polystyrene-based composite sheet, described aluminium film is coated with organic silicon adhesive through vacuum furnace, under 95 ~ 105 DEG C of conditions, the hot compound of roll-in, cold roll-in are delayed with polystyrene-based composite sheet again, obtained flame-retardant aluminum plastic composite sheet; Described polystyrene-based composite sheet is made by the raw materials melt blending extrusion of following weight portion: 40 ~ 60 parts of polystyrene, 17 ~ 26 parts of APPs, 5 ~ 10 parts of celluloses, 6 ~ 8 parts of modified montmorillonoids and 12 ~ 16 parts of polyphenylene oxide; Described modified montmorillonoid is alkyl trimethyl quaternary ammonium salt modified montmorillonoid, and the molecular structural formula of described alkyl trimethyl quaternary ammonium salt is CH
3(CH
2)
nn (CH
3)
3 +x
-, wherein, n=17 ~ 25, X is Cl or Br; The particle diameter of described modified montmorillonoid is 15 ~ 25 μm;
Described organic silicon adhesive stirs mixing making by raw material constant temperature at 25 ~ 40 DEG C of following weight portion: 70 ~ 80 parts of hydroxyl endblocked polydimethylsiloxanes, 6 ~ 10 parts of alkyl-blocked dimethyl silicone polymers, 1 ~ 2 part of dimethyl-penten diamines, 0.5 ~ 2 part of organotin catalysts and 6 ~ 22.5 parts of aerosils; Wherein, described organotin catalysts be selected from a kind of in dibutyltin diacetate, dibutyl tin laurate, stannous octoate or wherein any two kinds with the mixture of arbitrary proportion.
2. flame-retardant aluminum plastic composite sheet as claimed in claim 1, it is characterized in that the source of described modified montmorillonoid is NANOCOR company of the U.S., I.28E product type is.
3. flame-retardant aluminum plastic composite sheet as claimed in claim 1, it is characterized in that described aluminium film is pure aluminum foil, thickness is 0.01 ~ 0.02mm; The thickness of described flame-retardant aluminum plastic composite sheet is 0.50 ~ 0.80mm.
4. flame-retardant aluminum plastic composite sheet as claimed in claim 1, it is characterized in that in the raw material of described polystyrene-based composite sheet, the degree of polymerization of described APP is 1000 ~ 1500, and phosphorus content is 31 ~ 32%, and particle diameter is 15 ~ 18 μm.
5. flame-retardant aluminum plastic composite sheet as claimed in claim 1, it is characterized in that, in the raw material of described polystyrene-based composite sheet, the described cellulosic degree of polymerization is 2000 ~ 5000, particle diameter is 15 ~ 25 μm.
6. flame-retardant aluminum plastic composite sheet as claimed in claim 1, it is characterized in that, in the raw material of described polystyrene-based composite sheet, described polyphenylene oxide is Powdered, its glass transition temperature is 214 DEG C.
7. flame-retardant aluminum plastic composite sheet as claimed in claim 1, it is characterized in that in described flame-retardant aluminum plastic composite sheet, the spread of described organic silicon adhesive is 30 ~ 75g/m
2aluminium film.
8. flame-retardant aluminum plastic composite sheet as claimed in claim 1, it is characterized in that in the raw material of described organic silicon adhesive, the mean molecule quantity of described hydroxyl endblocked polydimethylsiloxane is 1000 ~ 1500; The mean molecule quantity of described alkyl-blocked dimethyl silicone polymer is 1000 ~ 1500.
9. the preparation method of flame-retardant aluminum plastic composite sheet as claimed in claim 1, is characterized in that described preparation method comprises the steps:
(1) modified montmorillonoid and polyphenylene oxide melting mixing extruding pelletization are obtained imvite master batch, imvite master batch, polystyrene, APP, cellulose at 60 DEG C ~ 70 DEG C premixs, extrude through equidirectional parallel double-screw extruder melt blending after mixing, roll, draw, cooling forming, obtained polystyrene-based composite sheet;
(2) hydroxyl endblocked polydimethylsiloxane, alkyl-blocked dimethyl silicone polymer, dimethyl-penten diamines, organotin catalysts and aerosil are added glue cylinder, first glue cylinder is vacuumized, at 25 ~ 40 DEG C, constant temperature stirs mixing 20 ~ 30min again, obtained organic silicon adhesive;
(3) aluminium film presses spread 30 ~ 75g/m through vacuum furnace
2aluminium film is delayed with polystyrene-based the composite sheet hot compound of roll-in, cold roll-in under 95 ~ 105 DEG C of conditions after being coated with gluing, obtained flame-retardant aluminum plastic composite sheet.
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CN201249621Y (en) * | 2008-06-18 | 2009-06-03 | 盛奇龙 | Colorful aluminum-plastic composite embossed film |
CN102492231A (en) * | 2011-12-02 | 2012-06-13 | 太原理工大学 | Halogen-free flame-retarding polystyrene composite material and preparation method thereof |
CN103333423A (en) * | 2013-06-15 | 2013-10-02 | 太原理工大学 | Compound flame-retardant polystyrene composition and preparation method thereof |
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CN201249621Y (en) * | 2008-06-18 | 2009-06-03 | 盛奇龙 | Colorful aluminum-plastic composite embossed film |
CN102492231A (en) * | 2011-12-02 | 2012-06-13 | 太原理工大学 | Halogen-free flame-retarding polystyrene composite material and preparation method thereof |
CN103333423A (en) * | 2013-06-15 | 2013-10-02 | 太原理工大学 | Compound flame-retardant polystyrene composition and preparation method thereof |
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