CN101463160A - Halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate and preparation thereof - Google Patents
Halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate and preparation thereof Download PDFInfo
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- CN101463160A CN101463160A CNA2009100451575A CN200910045157A CN101463160A CN 101463160 A CN101463160 A CN 101463160A CN A2009100451575 A CNA2009100451575 A CN A2009100451575A CN 200910045157 A CN200910045157 A CN 200910045157A CN 101463160 A CN101463160 A CN 101463160A
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Abstract
The invention discloses a halogen-free flame retarding macromolecule sandwich layer material used in a fireproofing aluminium-plastic panel, which is characterized in that the material comprises the components according to the parts by weight: 5-20 of polyethylene, 5-30 of modified polyethylene, 60-80 of halogen-free flame retardant, 2-10 of retardant synergist, 0.1-2 of resin acceptor, 0.5-3 of chemical inhibitor, and 0.1-5 o f other addition agents. The fireproofing aluminium-plastic panel uses the halogen-free flame retarding macromolecule sandwich layer material and is characterized by low cost, halogen-free, low smoke, flame retarding, high heat pressing bonding strength, a flexible coiling plank stuff and the like. And when the material of the invention is used for composite producing the fireproofing aluminium-plastic panels, the composite molding technique has good performance, can meet the requirements of the aluminium-plastic panel and the technique requirements of continuous industrial production line. the combustion performance of the halogen-free flame retarding macromolecule sandwich layer material can be completely in line with the requirements of B-s1, d0, t1 level stated in GB20286-2006; the material has smaller thermal value when in flaming and are very close to A2 level (GB8624-2006) flame retarding sandwich layer materials.
Description
Technical field
The present invention relates to a kind of halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate and preparation method thereof.
Background technology
The composited aluminum and plastic decking core material that present patent application discloses a few days ago, uses and sells has three kinds of fire-retardant core material of pure resistant sandwich materials with polyethylene and Halogen and halogen-free flameproof core materials.First kind be pure resistant sandwich materials with polyethylene at present on market mass selling be applied to the conventional aluminium plastic clad plate and make core material, account for more than 90%, but because its oxygen index only is 17.5, not fire-retardant, belong to inflammable material, the burning back is the fusion drippage easily, initiation fire spreads, so used by public security fire-fighting department and the restriction of building design and construction department at present, especially in important public place, as drome, station, occasions such as top grade entertainment place and high-grade Highrise buildings indoor and outdoor decoration require to use difficult to burn or do not fire a grade fire proof construction finishing material.Second kind is the Halogen inflaming retarding core material, though have certain flame retardant resistance, but because of body material Halogen or adding halogen/antimony fire retardant, when taking place, fire can produce a large amount of deleterious carbon monoxide and severe corrosive hydrogen halide smog because of burning, cause secondary pollution, thus with its aluminium-plastic panel of doing core material production because of do not meet environmental protection industry policy and require and in the world the developing direction of fire retardant chemistry building materials just progressively be eliminated.The third is the halogen-free flameproof core material, and application at present is more extensive, as drome, station, and occasions such as top grade entertainment place and high-grade Highrise buildings indoor and outdoor decoration.But the organic content of this halogen-free flameproof core material is than higher, so the calorific value of this halogen-free flameproof core material when burning is bigger.Can only belong to the fire-retardant core material of B level (GB8624--2006).Chinese patent application 200510093592.7, disclose a kind of halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate and preparation method thereof, each component of this core material umber by weight is: new LDPE (film grade) 15-30 part, LLDPE 15-20 part, ethene and hot rare multipolymer 3-15 part, aluminium hydroxide 30-45 part, magnesium hydroxide 10-15 part, retardant synergist 2-25 part, coupling agent 0.5-5 part.Because the hydrocarbon compound of this invention is more than 40% (weight part), therefore, this patent does not relate to halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate maximum heat after the goods perfect combustion when burning and releases total amount.Therefore, this invention is generally the B grade fireproof aluminum and moulds the plate halogen-free flame-retardant polymer sandwich layer material.
Summary of the invention
The objective of the invention is in order to overcome deficiency of the prior art, provide a kind of and have fire-retardant, resistance and drip and halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate nontoxic, that the hot pressing bonding strength is high.
For realizing above purpose, the present invention is achieved through the following technical solutions:
A kind of halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate, it is characterized in that, in parts by weight, its component comprises polyethylene: 5～20, modified poly ethylene: 5～30, halogen-free flame retardants 60～80, retardant synergist: 2～10, coupling agent: 0.1～2, oxidation inhibitor: 0.5～3, other auxiliary agents: 0.1～5.
The existence of polyethylene and modified poly ethylene in the halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate of the present invention has constituted the matrix resin of whole fire-retardant polyethylene material.These resins have significantly improved the deterioration of caused material mechanical performance of fire retardant filling and processing characteristics, have guaranteed aluminium-plastic panel of the present invention flame-proof polyethylene core excellent comprehensive performances.
Wherein, described polyethylene is one or more in new LDPE (film grade), high density polyethylene(HDPE), the linear low density polyethylene, and its melt flow rate (MFR) is 0.3～5.0g/10min.
Wherein, described modified poly ethylene is ethene-Sipacril 2739OF (EAA), ethene-vinyl acetate copolymer (EVA), terpolymer EP rubber (EPDM), ethylene-propylene rubber(EPR).Perhaps modified poly ethylene is one or more in the polarity graft copolymer of polyolefine and unsaturated monoprotic acid or unsaturated dibasic acid or MALEIC ANHYDRIDE (MAH), and its melt index is 0.40～100g/10min.
Wherein, described modified poly ethylene, its component by weight:
Sipacril 2739OF (EAA) 30～50
Ethene-vinyl acetate polymers (EVA) 10～30
Terpolymer EP rubber 15～40
Linear low density polyethylene 20～50
Polarity grafted monomer: 0.1～5.0
Peroxide initiator: 0.01～1.0
Grafting auxiliary agent: 0.05～0.5
Wherein, the component of the polarity graft copolymer of polyethylene and MALEIC ANHYDRIDE (MAH) is
Linear low density polyethylene 20～50
Polarity grafted monomer: 0.1～5.0
Peroxide initiator: 0.01～1.0
Grafting auxiliary agent: 0.05～0.5.
Wherein, described halogen-free flame retardants is not halogen-containing inorganic mineral based flame retardant.Comprise aluminium hydroxide, magnesium hydroxide, calcium sulfate, mineral its compound or that contain these compounds, its powder size are that 0.1～50um and/or diameter are 0.1～0.5um, the length whisker less than 80um.These fire retardants reduce thermal value and flame temperature in beginning thermal endothermic decomposition dehydration more than 195 ℃, dilute fire-retardant air; Decompose the carburization zone of the metal oxide of generation, play an adiabatic protection and a resistance incarbonization, thereby the inhibition burning reduces the amount of being fuming in material surface formation one deck firm compact.
Wherein, described retardant synergist is selected from one or more in non-halogen phosphoric acid ester, hydroxy silicon oil, zinc borate, zinc oxide, antimonous oxide, molybdenum dioxide, silicon powder and the ammonium polyphosphate.The existence of these materials can be brought into play the synergistic effect between different flame retardant better, makes flame retardant effect more outstanding, and the fire retardant total amount reduces.
Wherein coupling agent is for effectively improving the material of fire retardant and polyethylene base material boundary face consistency, and described coupling agent is selected from one or more in phthalate ester coupling agent, aluminate coupling agent and the silane coupling agent.Specifically comprise titanate coupling agent such as sec.-propyl three (stearyl-) titanic acid ester, sec.-propyl three (different capryloyl) titanic acid ester, sec.-propyl three (certain herbaceous plants with big flowers acyl group) titanic acid ester, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester (KR-95); KR-TTS, KR-38S etc., aluminate coupling agent such as DL-411-D, DL411F, aluminate coupling agent 1628.Silane coupling agent such as A-150, A-151, A-171, A-172, A-1100, A-187, A-174, A-1891, A-189, A-1120.
Wherein, described other auxiliary agents are selected from one or more in dispersion agent, rheological agent, oxidation inhibitor, anti-dripping agent, linking agent and the tinting material.Dispersion agent such as magnesium stearate, with rheological agent etc. be dispersed and extrude processing fluidity for improving each component, thereby reduce the chemical substance of mixture viscosity, specifically comprise lipid acid and acid amides thereof or salt, low-molecular-weight polyolefin, organic silicone and/or fluorinated rheological agent etc.; Oxidation inhibitor (as 1010), linking agent (as DCP), tinting material are (as TiO
2Or carbon black) etc. be for effectively improving the material of performances such as material thermo oxidative aging, photoaging, degree of crosslinking and color.
Also can add UV light absorber among the present invention, as UV-531, UV-T.
Another object of the present invention provides a kind of method for preparing halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate, it is characterized in that, earlier selected halogen-free flame retardants and coupling agent are carried out pre-treatment in high-speed mixer, mixing time is 2～10 minutes, mixing temperature is 90～120 ℃, put into the Banbury mixer banburying after being mixed together evenly with other components then, the banburying time is 5～15 minutes in the Banbury mixer continuously, the banburying temperature is 140～170 ℃, adopt parallel double-screw to extrude fervent granulation then, the extruding pelletization temperature is 120～185 ℃.
In the component of the present invention, polyethylene and modified poly ethylene content are relatively low, for increasing the consistency of itself and other component, adopt Banbury mixer banburying step among the preparation method, have improved the consistency of polyethylene and modified poly ethylene and other component.
Halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate of the present invention is compared with traditional flame-proof polyethylene core, not halogen-containing, fusion is not dripped, and dependence generates non-harmful carbon dioxide and plays the moisture of cooling diluting effect and the metal oxide that energy covering material surface takes blocking effect through the thermal endothermic decomposition reaction of inorganic mineral based flame retardant under high temperature (burning) environment of coupling activation treatment.Owing to adopted as above-mentioned particular design on the prescription, therefore halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate of the present invention has characteristics such as low cost, halide-free smokeless, fire-retardant, hot pressing bonding strength height and the flexible rolling of sheet material, and when adopting the compound production fireproof aluminum-plastic board of material of the present invention, composite molding technique is functional, can satisfy the processing requirement of aluminium-plastic panel standard and continuous industry production line.The combustionproperty of this halogen-free flameproof core material meets the B-s1 of GB20286-2006 regulation, d0, the requirement of t1 level fully.Calorific value during burning is smaller.Very near the fire-retardant core material of A2 level (GB8624-2006).
Embodiment
Below in conjunction with embodiment the present invention is described in detail:
Example formulations sees attached list 1 and table 2, and its concrete operations step is basic identical, and promptly the first step is carried out surface preparation by the composite back of all or part of halogen-free flame retardants of prescription with composite coupler, carries out in homogenizer.Second step by the prescription weighing, was mixed together the even Banbury mixer banburying of using with all the other components, and the banburying process temperature and time is basic identical.In the 3rd step, the uniform mixture of above-mentioned internal mixing and plasticizing is extruded the die face hot cut pellet through the double-screw extruding pelletizing unit; In the 4th step, hot cut pellet is promptly made the flame-proof polyethylene pellet through the cooling of secondary cyclone separator, vibratory screening apparatus go-on-go packing.Prepared fire-retardant PE pellet adopts screw slenderness ratio greater than 32 the single screw rod plate squeezing of vacuum exhaust formula unit, becomes halogen-free flameproof PE roll bending material through three-roll press-polishing.
Preparation method of the present invention, the first step uses homogenizer to mix, and mixing time is 2～10 minutes in the high-speed mixer, and mixing temperature is 90～120 ℃; Embodiment 1-2 temperature is 90 ℃; Embodiment 3,4 temperature are 100 ℃, and embodiment 5 temperature are 95 ℃, and embodiment 6,7 temperature are 110 ℃, and embodiment 8,9 temperature are 120 ℃; Second step, the banburying time is 5～15 minutes in continuous Banbury mixer, and the banburying temperature is 140～170 ℃, and embodiment 1-2 temperature is 140 ℃; Embodiment 3,4 temperature are 145 ℃, and embodiment 5 temperature are 140 ℃, and embodiment 6,7 temperature are 150 ℃, and embodiment 8,9 temperature are 165 ℃; The extruding pelletization temperature is 120～185 ℃, is preferably 130～185 ℃, and embodiment 1-2 temperature is 120 ℃; Embodiment 3,4 temperature are 160 ℃, and embodiment 5 temperature are 130 ℃, and embodiment 6,7 temperature are 175 ℃, and embodiment 8,9 temperature are 150 ℃;
The extrusion board technological temperature is 130～190 ℃, is preferably 140～185 ℃, and 50～95 ℃ of tri-roll press machine temperature are preferably 60～95 ℃, and vacuum tightness is-and more than the 0.02Mpa, screw slenderness ratio is more than 32, and is preferred more than 35.
Table 1: prescription is formed
Table 2:
Halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate technical performance index of the present invention is: tensile strength is 6.5～10.5Mpa, notched Izod impact strength: 6.0～13.50KJ/m
2, vicat softening temperature is 82～90 ℃, stripping strength 8.5～11.5N/mm, and oxygen index is up to 34%-42.
Use the fireproof aluminum-plastic board of the compound production of halogen-free flame-retardant polymer sandwich layer material of the present invention, combustionproperty meets the B-s1 of GB20286-2006 regulation, d0, the requirement of t1 level fully.Calorific value during burning is smaller.Very near the fire-retardant core material of A2 level (GB8624--2006).Detect through national fire-proof construction material quality supervision and test center, burning rate of rise index (W/S) (GB/T 20284-2006) is 0; Total heat burst size (WJ) (GB/T 20284-2006) is 0.9 in the 600s; Flame laterally spreads length (m) (GB/T 20284-2006) and meets the requirements; Burning length (m) (GB/T 8626-2007) is 0; Flue gas generating rate index (m
2/ s
2) (GB/T20284-2006) be 2, total smoke-producing amount (m in the 600s
2) (GB/T 20284-2006) be 38; Burning dropping/particulate (GB/T 20284-2006) technical indicator is not have burning dropping/particulate in the 600s, and test result meets the requirements; Filter paper (GB/T 8626-2007) technical indicator of whether being ignited is that filter paper is not ignited, and test result meets the requirements; Produce smoke toxicity (level) (GB/T 20285-2006), technical indicator is for reaching ZA
3, test result is ZA
3
Embodiment among the present invention only is used for that the present invention will be described, does not constitute the restriction to the claim scope, and other substituting of being equal in fact that those skilled in that art can expect are all in protection domain of the present invention.
Claims (9)
1. halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate, it is characterized in that, in parts by weight, its component comprises polyethylene: 5～20, modified poly ethylene: 5～30, halogen-free flame retardants 60～80, retardant synergist: 2～10, coupling agent: 0.1～2, oxidation inhibitor: 0.5～3, other auxiliary agents: 0.1～5.
2. halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate according to claim 1, it is characterized in that, described polyethylene is one or more in new LDPE (film grade), high density polyethylene(HDPE), the linear low density polyethylene, and its melt flow rate (MFR) is 0.3～5.0g/10min.
3. halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate according to claim 1, it is characterized in that, described modified poly ethylene is one or more in the polarity graft copolymer of ethene-Sipacril 2739OF, ethene-vinyl acetate copolymer, terpolymer EP rubber, ethylene-propylene rubber(EPR), polyolefine and unsaturated monoprotic acid or unsaturated dibasic acid or MALEIC ANHYDRIDE, and its melt index is 0.40～100g/10min.
4. halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate according to claim 1 is characterized in that, its component of described modified poly ethylene by weight:
Sipacril 2739OF 30～50
Ethene-vinyl acetate polymers 10～30
Terpolymer EP rubber 15～40
Linear low density polyethylene 20～50
Polarity grafted monomer: 0.1～5.0
Peroxide initiator: 0.01～1.0
Grafting auxiliary agent: 0.05～0.5.
5. halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate according to claim 1 is characterized in that, described halogen-free flame retardants is not halogen-containing inorganic mineral based flame retardant.
6. halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate according to claim 1, it is characterized in that described retardant synergist is selected from one or more in non-halogen phosphoric acid ester, hydroxy silicon oil, zinc borate, zinc oxide, antimonous oxide, molybdenum dioxide, silicon powder and the ammonium polyphosphate.
7. halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate according to claim 1 is characterized in that described coupling agent is selected from one or more in phthalate ester coupling agent, aluminate coupling agent and the silane coupling agent.
8. halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate according to claim 1, it is characterized in that described other auxiliary agents are selected from one or more in dispersion agent, UV light absorber, rheological agent, oxidation inhibitor, anti-dripping agent, linking agent and the tinting material.
9. the preparation method of the described halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate of the arbitrary claim of claim 1-8, it is characterized in that, earlier selected halogen-free flame retardants and coupling agent are carried out pre-treatment in high-speed mixer, mixing time is 2～10 minutes, mixing temperature is 90～120 ℃, put into the Banbury mixer banburying after being mixed together evenly with other components then, the banburying time is 5～15 minutes in the Banbury mixer continuously, the banburying temperature is 140～170 ℃, adopt parallel double-screw to extrude fervent granulation then, the extruding pelletization temperature is 120～185 ℃.
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| CN103360667A (en) * | 2012-03-27 | 2013-10-23 | 上海科悦高分子材料有限公司 | Halogen-free flame retarding macromolecule sandwich layer material for high strength light fireproofing aluminum-plastic panel and preparation method thereof |
| CN105017613A (en) * | 2015-07-13 | 2015-11-04 | 上海金泛斯标识有限公司 | Core material for flame resistant aluminum-plastic panel and preparation method of core material |
| CN105400057A (en) * | 2015-12-03 | 2016-03-16 | 苏州沃尔兴电子科技有限公司 | Halogen-free flame-retardant temperature-resistant polyolefin pyrocondensation material and preparation method thereof |
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| CN103360667A (en) * | 2012-03-27 | 2013-10-23 | 上海科悦高分子材料有限公司 | Halogen-free flame retarding macromolecule sandwich layer material for high strength light fireproofing aluminum-plastic panel and preparation method thereof |
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| CN103342845B (en) * | 2013-06-25 | 2016-07-06 | 江苏科悦新材料有限公司 | Fire proofing material and preparation method thereof, light fire-proof aluminium-plastic panel |
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| CN106046491B (en) * | 2016-07-02 | 2018-07-06 | 苏州横远微控技术有限公司 | PE based composites and its preparation method and application |
| CN108724849A (en) * | 2018-05-02 | 2018-11-02 | 安徽九牛塑业科技有限公司 | A kind of plastic-aluminum plank and preparation method thereof that bend-resistance is anti-aging |
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| CN113614167A (en) * | 2019-04-03 | 2021-11-05 | 陶氏环球技术有限责任公司 | Extrudable halogen-free flame retardant compositions |
| CN109988437A (en) * | 2019-04-17 | 2019-07-09 | 上海吉祥塑铝制品有限公司 | A kind of halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate and preparation method thereof |
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