CN101851351A - Inorganic hydroxide composite flame retardant and high-performance halogen-free flame-retardant polyformaldehyde material using same for antiflaming - Google Patents
Inorganic hydroxide composite flame retardant and high-performance halogen-free flame-retardant polyformaldehyde material using same for antiflaming Download PDFInfo
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Abstract
The invention discloses an inorganic hydroxide composite flame retardant which comprises 20-38 parts of inorganic hydroxide, 3-20 pars of polyformaldehyde absorber, 3-20 parts of macromolecular carbon forming agent and 0.1-5 parts of flame-retardant synergist. The invention also discloses a high-performance halogen-free flame-retardant polyformaldehyde material using the composite flame retardant for antiflaming, which comprises 40-80 parts of polyformaldehyde, 20-53 parts of inorganic hydroxide composite flame retardant and 0.1-1 part of antioxidant. The materials are processed by melt extrusion and granulation to obtain the high-performance halogen-free flame-retardant polyformaldehyde material. The vertical burning UL 94 of the high-performance halogen-free flame-retardant polyformaldehyde material is V1- V0, the tensile strength is 45-52 MPa, and the notch impact strength is 4.7-5.2 kJ/m<2>. The inorganic hydroxide composite flame retardant has the functions of polyformaldehyde absorption, gas phase flame retardant, carbon formation and the like, and also has the functions of lubrication, compatibilization, plasticization and processing fluidity improvement. The high-performance halogen-free flame-retardant polyformaldehyde material has the advantages of favorable flame retardance, good mechanical properties and thermoplastic processability, high appearance quality, high safety, environmental protection, simple preparation and low cost.
Description
Technical field
The invention belongs to the inorganic hydroxide fire retardant and with its flame-proofed polymer material technical field, be specifically related to a kind of inorganic hydroxide composite flame-retardant agent and with its fire-retardant high-performance halogen-free flame retardant polyformaldehyde material.
Background technology
Though engineering plastics polyoxymethylene excellent property is the strategic engineering plastics product that China greatly develops at present, its limiting oxygen index(LOI) only 15% be one of the most incendive polymer materials, thereby its application is subjected to bigger restriction.
Generally speaking, adopting the additive flame retardant modified polyacetal should be a kind of comparatively easy method, but there is following difficult point in fire-retardant polyoxymethylene: 1) polyoxymethylene molecular chain thermo-oxidative stability is poor, be heated " zip mode " decomposition easily takes place, it is combustion-supporting to discharge inflammable gass such as a large amount of formaldehyde, formic acid simultaneously, and formic acid also can decompose by the catalysis polyoxymethylene; 2) responsive because of polyoxymethylene to acid, alkaline matter, and many fire retardants particularly phosphonium flame retardant when melt-processed, be heated easily to decompose and produce acidic substance, so can induce polyformaldehyde resin in the thermoplastic course of processing, to produce severely degrade, make it to be difficult to thermoplastic machine-shaping, therefore the chemical property to fire retardant systems requires very harsh; 3) since the polyoxymethylene molecular chain mainly by-(CH
2O)
n-unit constitutes, thereby compound with regular structure height, no side group, good, the easy crystallization of C-O key kindliness, it is a kind of low-pole line style high-crystallinity copolymer, poor with filler consistencies such as most fire retardants, fire retardant is difficult in matrix resin homodisperse, it is not good enough to combine with resin boundary surface, thereby can cause negative impact to the material over-all properties; 4) because polyoxymethylene is the most incendive polymer materials, and burning the time do not form the charcoal layer, thereby the fire retardant that needs to add higher amount just can reach the ideal flame retardant properties, but like this physical and mechanical properties of material declined to a great extent.Therefore, be applicable to that the additive flame retardant system of polyoxymethylene is less, make it to become the most difficult fire-retardant macromolecular material.
At present in the more employing nitrogen-phosphorus of fire-retardant polyoxymethylene compound (expanded polystyrene veneer) flame-retardant system of reporting both at home and abroad, (H.Harashina such as Harashina, Y.Tajima, T.Itoh, Polym.Degrad.Stab., 2006,91:1996.H.Harashina, J.P.Pat.2004204167,2004.H.Harashina, U.S.Pat.6753363,2004) utilize red phosphorus, trimeric cyanamide, linear phenolic resin cooperative flame retardant polyoxymethylene, oxygen index reaches 37.5%, tests by UL 94 V-1 (0.8mm), and tensile strength also can reach 52MPa, should be the best report of present fire-retardant polyformaldehyde material over-all properties.But the red phosphorus water absorbability is strong, relatively poor with resin compatible, being heated easily produces poisonous PH
3Gas, frictional heat easily cause burning, thereby have potential safety hazard, make red phosphorus microcapsuleization so generally all will coat layer protecting film on the red phosphorus surface, with security, consistency and the color etc. of improving its use.Even so, when adopting micro encapsulation red phosphorus flame-retardant polyoxymethylene, still there is the processing safety problem, thereby still needs protection of inert gas such as nitrogen during fire-retardant blend melt-processed, otherwise easy severely degrade, difficult machine-shaping.In addition, the goods color that is obtained is dark (red-brown), practical application.
Inorganic hydroxide (mainly comprising magnesium hydroxide and aluminium hydroxide) is the present fire retardant kind of cleaning, environmental protection, advantage such as have the cigarette of pressing down, Heat stability is good, flame retardant effect is lasting, raw material is easy to get, production cost is low.(Liu Pengbo such as Liu Pengbo, the Xuwen, Li Yingjie, polymer material science and engineering, 2004,20:120) use the magnesium hydroxide flame retardant polyoxymethylene, when addition 60wt%, the material oxygen index can reach 40%, but can not test by vertical combustion, and tensile strength and notched Izod impact strength only are 32MPa and 1.6kJ/m
2Feng Dingsong etc. (what is flat for Feng Dingsong, Xie Hongquan, petrochemical technology and application, and 1999,17:79) use the aluminium hydroxide flame-retardant polyoxymethylene, when addition was 60wt%, batten can not be tested by vertical combustion, and tensile strength 20.1MPa only.This shows, adopt the fire-retardant polyoxymethylene of inorganic hydroxide separately, material does not possess the vertical combustion rank, and the serious deterioration of mechanical property, trace it to its cause and mainly contain 2 points: 1) because inorganic hydroxide is to produce water vapor by thermal endothermic decomposition to bring into play fire retardation, therefore flame retarding efficiency is not high, general material all needs higher addition (being about 60wt% usually) just can make material reach comparatively ideal flame retardant effect, and polyoxymethylene may need more high flame retardant agent addition because of being the most difficult fire-retardant polymer materials.2) because inorganic hydroxide contains many hydroxyls, make the fire retardant powder surface be " hydrophilic oleophobic " character, be the polarity filler, thereby it is not good enough with the polyoxymethylene consistency of low-pole, if add high-load polarity inorganic hydroxide powder, can imagine that it is difficult to homodisperse in the polyoxymethylene matrix, cause the processing and the physical and mechanical properties deterioration of material the most at last.
Summary of the invention
At the deficiencies in the prior art, primary and foremost purpose of the present invention provides a kind of inorganic hydroxide composite flame-retardant agent, thinks that flame retardant area provides a kind of novel multifunctional synergistic flame retardant.
Secondary objective of the present invention is the problem that exists at present prior art, provides the above-mentioned inorganic hydroxide composite flame-retardant agent of a kind of usefulness to come fire-retardant high-performance halogen-free flame retardant polyformaldehyde material.
Inorganic hydroxide composite flame-retardant agent provided by the invention, this fire retardant are powder or pellet, wherein contain inorganic hydroxide 20-38 part, inhale aldehyde agent 3-20 part, macromolecular carbon forming agent 3-20 part, retardant synergist 0.1-5 part, and the umber of each material is weight part.
The inorganic hydroxide that contains in the above-mentioned fire retardant is at least a in magnesium hydroxide and the aluminium hydroxide.
The suction aldehyde agent that contains in the above-mentioned fire retardant is at least a in close white amine, melem, urea, thiocarbamide, tricyanic acid, melamine cyanurate and the terpolycyantoamino-formaldehyde resin.This suction aldehyde agent not only has concurrently inhales the gentle mutually fire-retardant effect that waits of aldehyde, also can improve to add polyoxymethylene thermostability in man-hour, improves the Flame Retardancy energy.
The macromolecular carbon forming agent that contains in the above-mentioned fire retardant is at least a in polyether(poly)urethane, PAUR, polycarbonate, modified phenolic resins, polymeric amide or the polyvinyl alcohol.This macromolecular carbon forming agent not only has into effects such as charcoal, lubricated, increase-volume and aid dispersion concurrently, also can improve carbon residue amount behind the material combustion, improves the co-mixing system processing fluidity, improves consistency and the dispersiveness of filler in the polyoxymethylene matrix.
The retardant synergist that contains in the above-mentioned fire retardant is at least a in phospho-wolframic acid, silicotungstic acid, zinc borate, tetramethylolmethane, antimonous oxide, triphenylphosphate or the silicon-dioxide.This retardant synergist not only has plasticising and effect such as fire-retardant concurrently, also can consolidate charcoal layer structure, further improves flame retardant properties, improves processing fluidity.
Above inorganic hydroxide composite flame-retardant agent can prepare in following any mode: with inorganic hydroxide, inhale the aldehyde agent, macromolecular carbon forming agent and retardant synergist mix in high-speed mixer and got final product in 2-20 minute, or with inorganic hydroxide, inhale the aldehyde agent, it is that 120-250 ℃ mill or Banbury mixer fusion is compound that macromolecular carbon forming agent and retardant synergist are put into temperature, being ground into powder after the cooling again gets final product, or with inorganic hydroxide, inhale the aldehyde agent, macromolecular carbon forming agent and retardant synergist elder generation premix, the screw extrusion press fusion of putting into temperature then and be 120-250 ℃ is compound, and pelletizing becomes pellet to get final product again.
It then is with polyoxymethylene 40-80 part that the above-mentioned inorganic hydroxide composite flame-retardant agent of usefulness provided by the invention comes fire-retardant high-performance halogen-free flame retardant polyformaldehyde material; inorganic hydroxide composite flame-retardant agent 20-53 part and oxidation inhibitor 0.1-1 part are behind thorough mixing; putting into temperature and be 160-220 ℃ screw extrusion press melt extrudes granulation and obtains; wherein the umber of each material is weight part; and the vertical combustion UL 94 of gained material is the V1-V0 level; tensile strength is 45-52MPa, and notched Izod impact strength is 4.7-5.2kJ/m
2
Polyoxymethylene is preferably 40-70 part in the above-mentioned high-performance halogen-free flame retardant polyformaldehyde material, and the inorganic hydroxide composite flame-retardant agent is preferably 30-50 part.
Polyoxymethylene in the above-mentioned high-performance halogen-free flame retardant polyformaldehyde material is copolymerization or homopolymerization polyoxymethylene.
Oxidation inhibitor in the above-mentioned high-performance halogen-free flame retardant polyformaldehyde material is two [β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], four [β-(3 of Triethylene glycol, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] at least a in pentaerythritol ester, three (2, the 4-di-t-butyl) phenyl-phosphite.Oxidation inhibitor is to well known to a person skilled in the art technology, can be used, and the oxidation inhibitor that its precondition is to use has a negative impact to the realization and must not obtain of excellent results of the present invention of the object of the invention.
Compared with the prior art the present invention has following characteristics:
1, because inorganic hydroxide is to clean most, the additive flame retardant of environmental protection, and have wide material sources, price is low, advantages such as smoke suppressing effect is good, thereby serve as the main not only safety of polynary composite flame retardant system that multi-functional synergist constitutes that cooperates with it, environmental protection, cost is low, have suction aldehyde concurrently, gas phase is fire-retardant, become effects such as charcoal, and also have lubricated, increase-volume, plasticising, improve the processing fluidity effect, it is a kind of novel multifunctional inorganic hydroxide composite flame-retardant agent, having filled up the inorganic hydroxide flame retardant area does not have the blank of composite flame-retardant agent, has especially sought a kind of suitable Halogen additive flame retardant system for the most difficult fire-retardant polyoxymethylene.
2, because the present invention comes fire-retardant polyoxymethylene with prepared inorganic hydroxide composite flame-retardant agent, thereby make the most difficult fire-retardant polyoxymethylene not only have excellent flame retardancy concurrently can (especially it can pass through UL94 vertical combustion rank), mechanical property, thermoplastic processability and visual appearance, and safety, environmental protection, preparation are easy, with low cost.
3, owing to contain the agent of suction aldehyde in the high-performance halogen-free flame retardant polyformaldehyde material provided by the invention; material be subjected to can reduce free formaldehyde gas in the thermal process; suppressing polyoxymethylene " zip mode " when melt-processed decomposes; improve fire-retardant polyformaldehyde material processing heat stability; thereby not only solved fire-retardant polyformaldehyde material melts machine-shaping than infusibility a difficult problem; and avoided the course of processing also need take protection of inert gas technical measures such as nitrogen, enabled to adopt conventional thermoplastic working method to prepare.
4, (synergistic is fire-retardant because the inorganic hydroxide composite flame-retardant agent that contains in the high-performance halogen-free flame retardant polyformaldehyde material provided by the invention has multiple synergistic effect, isolate, become charcoal, lubricated, increase-volume, aid dispersion), not only strengthened the multiple fire-retardant mechanism of gas phase and condensed phase, and improved the flowability of flame-retardant system, having strengthened inorganic hydroxide combines with interface between the polyoxymethylene matrix, improve the dispersiveness of inorganic hydroxide in the polyoxymethylene matrix, overcome the higher fire retardant material mechanical property that causes of inorganic hydroxide addition, the shortcoming of the serious deterioration of processing characteristics prepares the fire-retardant polyformaldehyde material of inorganic hydroxide of high comprehensive performance.
5,, thereby has application prospect widely because high-performance halogen-free flame retardant polyformaldehyde material provided by the invention is light goods.
Embodiment
Below by embodiment the present invention is further described.But given embodiment can not be interpreted as limiting the scope of the invention, thereby nonessential improvement and adjustment that the person skilled in the art in this field has done according to the content and the design philosophy of the invention described above also should belong to protection scope of the present invention.
What deserves to be explained is that the vertical combustion performance of the fire-retardant polyformaldehyde composite material of following examples preparation is according to the UL94-2006 standard testing, sample size is 127 * 12.7 * 1.6mm
3Limiting oxygen index(LOI) is according to the ASTMD2863-2009 standard testing, and sample size is 120 * 6.5 * 3mm
3The tensile strength of material is according to the ISO527/1-1993 standard testing, and batten is standard dumbbell shape (a 1A type), and middle narrower part width is 10mm, and thickness is 4mm, and Elongation test speed is 50mm/min; The notched Izod impact strength of material is according to the ISO179/1-2000 standard testing, and sample size is 80 * 10 * 4mm
3, notch depth is 2.0mm ± 0.2mm.
Embodiment 1
It is two roller mills of 170 ℃ after mixing compound 20 minutes that 20kg magnesium hydroxide, the close white amine of 10kg, 12kg polyether-type thermoplastic polyurethane and 0.1kg tetramethylolmethane are put into temperature, and being ground into median size is the composite flame-retardant agent powder of 0.2cm.Behind 40kg composite flame-retardant agent powder, 60kg kematal and 1kg oxidation inhibitor 245 solid phase premixs, put into screw extrusion press, be to melt extrude granulation under 170-180 ℃ promptly to get fire-retardant polyoxymethylene at plasticization temperature.
Record the vertical combustion UL94 V-1 level of this fire-retardant polyformaldehyde material, limiting oxygen index(LOI) 31%, tensile strength 45MPa, notched Izod impact strength 5.0kJ/m
2
Embodiment 2
It is 180 ℃ Banbury mixer after mixing compound 15 minutes that 30kg aluminium hydroxide, 3kg urea, 15kg polyester type thermoplastic polyurethane and 0.5kg silicotungstic acid are put into temperature, and being ground into median size is the composite flame-retardant agent powder of 0.5cm.Behind 30kg composite flame-retardant agent powder, 70kg kematal, 0.5kg antioxidant 1010 and 0.5kg oxidation inhibitor 168 solid phase premixs, put into screw extrusion press, be to melt extrude granulation under 180-190 ℃ promptly to get fire-retardant polyoxymethylene at plasticization temperature.
Record the vertical combustion UL94 V-1 level of this fire-retardant polyformaldehyde material, limiting oxygen index(LOI) 31%, tensile strength 46MPa, notched Izod impact strength 5.2kJ/m
2
Embodiment 3
It is 120 ℃ Banbury mixer after mixing compound 30 minutes that 25kg magnesium hydroxide, 15kg melamine cyanurate, 15kg modified phenolic resins and 0.5kg zinc borate are put into temperature, and being ground into median size is the composite flame-retardant agent powder of 0.8cm.Behind 50kg composite flame-retardant agent powder, 50kg homopolymerization polyoxymethylene and 1kg antioxidant 1010 solid phase premix, put into screw extrusion press, be to melt extrude granulation under 200-220 ℃ promptly to get fire-retardant polyoxymethylene at plasticization temperature.
Record the vertical combustion UL94 V-0 level of this fire-retardant polyformaldehyde material, limiting oxygen index(LOI) 35%, tensile strength 52MPa, notched Izod impact strength 4.8kJ/m
2
Embodiment 4
Behind 38kg magnesium hydroxide, 10kg terpolycyantoamino-formaldehyde resin, 12kg polymeric amide and 1kg triphenylphosphate premix, put into temperature and be that 220-250 ℃ screw extrusion press fusion is compoundly extruded, pelletizing becomes the composite flame-retardant agent pellet.Behind 53kg composite flame-retardant agent pellet, 40kg kematal and 0.1kg oxidation inhibitor 245 solid phase premixs, put into screw extrusion press, be to melt extrude granulation under 170-190 ℃ promptly to get fire-retardant polyoxymethylene at plasticization temperature.
Record the vertical combustion UL94 V-0 level of this fire-retardant polyformaldehyde material, limiting oxygen index(LOI) 38%, tensile strength 50MPa, notched Izod impact strength 4.8kJ/m
2
Embodiment 5
Behind 30kg aluminium hydroxide, 20kg thiocarbamide, 3kg polycarbonate and 5kg antimonous oxide premix, put into temperature and be that 200-250 ℃ screw extrusion press fusion is compoundly extruded, pelletizing becomes the composite flame-retardant agent pellet.Behind 45kg composite flame-retardant agent pellet, 30kg homopolymerization polyoxymethylene, 30kg kematal and 1kg oxidation inhibitor 245 solid phase premixs, put into screw extrusion press, be to melt extrude granulation under 175-195 ℃ promptly to get fire-retardant polyoxymethylene at plasticization temperature.
Record the vertical combustion UL94 V-0 level of this fire-retardant polyformaldehyde material, limiting oxygen index(LOI) 36%, tensile strength 46MPa, notched Izod impact strength 4.9kJ/m
2
Embodiment 6
15kg magnesium hydroxide, 20kg aluminium hydroxide, the close white amine of 5kg, 20kg modified phenolic resins, 1kg tetramethylolmethane and 1kg triphenylphosphate are put into high-speed mixer to be mixed 20 minutes.Behind 20kg mixing fire retardant material, 80kg kematal and 0.5kg oxidation inhibitor 245 solid phase premixs, put into screw extrusion press, be to melt extrude granulation under 170-180 ℃ promptly to get fire-retardant polyoxymethylene at plasticization temperature.
Record the vertical combustion UL94V-1 level of this fire-retardant polyformaldehyde material, limiting oxygen index(LOI) 30%, tensile strength 52MPa, notched Izod impact strength 4.9kJ/m
2
Embodiment 7
Behind 38kg aluminium hydroxide, 8kg tricyanic acid, 10kg polymeric amide, 2kg polycarbonate and 3kg phospho-wolframic acid premix, put into temperature and be that 210-240 ℃ screw extrusion press fusion is compoundly extruded, pelletizing becomes the composite flame-retardant agent pellet.Behind 38kg composite flame-retardant agent pellet, 62kg kematal and 0.8kg oxidation inhibitor 245 solid phase premixs, put into screw extrusion press, be to melt extrude granulation under 170-185 ℃ promptly to get fire-retardant polyoxymethylene at plasticization temperature.
Record the vertical combustion UL94 V-1 level of this fire-retardant polyformaldehyde material, limiting oxygen index(LOI) 34%, tensile strength 47MPa, notched Izod impact strength 4.8kJ/m
2
Embodiment 8
It is 140 ℃ Banbury mixer after mixing compound 15 minutes that 18kg magnesium hydroxide, 20kg aluminium hydroxide, 5kg thiocarbamide, the close white amine of 5kg, 10kg polyvinyl alcohol, 0.5kg phospho-wolframic acid and 0.5kg silicotungstic acid are put into temperature, and being ground into median size is the composite flame-retardant agent powder of 0.25cm.Behind 50kg composite flame-retardant agent powder, 50kg kematal and 1kg oxidation inhibitor 245 solid phase premixs, put into screw extrusion press, be to melt extrude granulation under 175-195 ℃ promptly to get fire-retardant polyoxymethylene at plasticization temperature.
Record the vertical combustion UL94 V-0 level of this fire-retardant polyformaldehyde material, limiting oxygen index(LOI) 37%, tensile strength 48MPa, notched Izod impact strength 4.7kJ/m
2
Embodiment 9
It is two roller mills of 160 ℃ after mixing compound 15 minutes that 25kg magnesium hydroxide, 10kg aluminium hydroxide, 8kg melem, 4kg polyether-type thermoplastic polyurethane, 3kg polyester type thermoplastic polyurethane and 3kg tetramethylolmethane are put into temperature, and being ground into median size is the composite flame-retardant agent powder of 0.3cm.Behind 52kg composite flame-retardant agent powder, 45kg kematal and 1kg antioxidant 1010 solid phase premix, put into screw extrusion press, be to melt extrude granulation under 160-180 ℃ promptly to get fire-retardant polyoxymethylene at plasticization temperature.
Record the vertical combustion UL94 V-0 level of this fire-retardant polyformaldehyde material, limiting oxygen index(LOI) 38%, tensile strength 46MPa, notched Izod impact strength 5.0kJ/m
2
Embodiment 10
It is two roller mills of 165 ℃ after mixing compound 18 minutes that 20kg magnesium hydroxide, 18kg aluminium hydroxide, 7kg Miller amine, 3kg tricyanic acid, 20kg polyester type thermoplastic polyurethane and 2kg silicon-dioxide are put into temperature, and being ground into median size is the composite flame-retardant agent powder of 0.5cm.Behind 42kg composite flame-retardant agent powder, 58kg kematal and 1kg oxidation inhibitor 168 solid phase premixs, put into screw extrusion press, be to melt extrude granulation under 180-195 ℃ promptly to get fire-retardant polyoxymethylene at plasticization temperature.
Record the vertical combustion UL94V-0 level of this fire-retardant polyformaldehyde material, limiting oxygen index(LOI) 35%, tensile strength 47MPa, notched Izod impact strength 5.1kJ/m
2
Comparative Examples 1
Behind 60kg magnesium hydroxide, 40kg kematal and 1kg oxidation inhibitor 245 solid phase premixs, put into screw extrusion press, be to melt extrude granulation under 170-185 ℃ promptly to get fire-retardant polyoxymethylene at plasticization temperature.
Record this fire-retardant polyformaldehyde material and can not pass through vertical combustion UL94, but limiting oxygen index(LOI) 38%, tensile strength 30MPa, notched Izod impact strength 1.5kJ/m
2
Comparative Examples 2
Behind 60kg aluminium hydroxide, 40kg kematal and 1kg oxidation inhibitor 245 solid phase premixs, put into screw extrusion press, be to melt extrude granulation under 170-185 ℃ promptly to get fire-retardant polyoxymethylene at plasticization temperature.
Record this fire-retardant polyformaldehyde material and can not pass through vertical combustion UL94, but limiting oxygen index(LOI) 34%, tensile strength 20MPa, notched Izod impact strength 1.3kJ/m
2
Claims (8)
1. inorganic hydroxide composite flame-retardant agent, this fire retardant is powder or pellet, wherein contains inorganic hydroxide 20-38 part, inhales aldehyde agent 3-20 part, macromolecular carbon forming agent 3-20 part, retardant synergist 0.1-5 part, and the umber of each material is weight part.
2. inorganic hydroxide composite flame-retardant agent according to claim 1, the inorganic hydroxide that contains in this fire retardant are at least a in magnesium hydroxide and the aluminium hydroxide.
3. inorganic hydroxide composite flame-retardant agent according to claim 1, the suction aldehyde agent that contains in this fire retardant are at least a in close white amine, melem, urea, thiocarbamide, tricyanic acid, melamine cyanurate and the terpolycyantoamino-formaldehyde resin.
4. inorganic hydroxide composite flame-retardant agent according to claim 1, the macromolecular carbon forming agent that contains in this fire retardant are at least a in polyether(poly)urethane, PAUR, polycarbonate, modified phenolic resins, polymeric amide or the polyvinyl alcohol.
5. inorganic hydroxide composite flame-retardant agent according to claim 1, the retardant synergist that contains in this fire retardant are at least a in phospho-wolframic acid, silicotungstic acid, zinc borate, tetramethylolmethane, antimonous oxide, triphenylphosphate or the silicon-dioxide.
6. high-performance halogen-free flame retardant polyformaldehyde material with each described inorganic hydroxide composite fire retardant among the claim 1-5; this material is with polyoxymethylene 40-80 part; inorganic hydroxide composite flame-retardant agent 20-53 part and oxidation inhibitor 0.1-1 part are behind thorough mixing; the screw extrusion press melting mixing extruding pelletization of putting into temperature and be 160-220 ℃ obtains; wherein the umber of each material is weight part; and the vertical combustion UL 94 of gained material is the V1-V0 level; tensile strength is 45-52MPa, and notched Izod impact strength is 4.7-5.2kJ/m
2
7. high-performance halogen-free flame retardant polyformaldehyde material according to claim 6, polyoxymethylene is 40-70 part in this material, the inorganic hydroxide composite flame-retardant agent is 30-50 part.
8. according to claim 6 or 7 described high-performance halogen-free flame retardant polyformaldehyde materials, the polyoxymethylene in this material is copolymerization or homopolymerization polyoxymethylene.
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| CN102061058A (en) * | 2010-12-20 | 2011-05-18 | 四川大学 | Halogen-free flame-resistant glass fiber reinforced polyformaldehyde composite material and preparation method thereof |
| CN102756404A (en) * | 2011-04-29 | 2012-10-31 | 中国林业科学研究院木材工业研究所 | Flame-retardant decorative plate, preparation method thereof and flame-retardant material comprising flame-retardant decorative plate |
| CN103435966A (en) * | 2012-12-19 | 2013-12-11 | 安徽科聚新材料有限公司 | Polyformaldehyde material and preparation method thereof |
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| CN108410119A (en) * | 2018-03-22 | 2018-08-17 | 广东纳路纳米科技有限公司 | polyformaldehyde composite material and preparation method thereof |
| CN114773776A (en) * | 2022-05-06 | 2022-07-22 | 安徽银隆塑业科技有限公司 | Halogen-free flame-retardant polyformaldehyde granules and production process thereof |
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| CN102061058B (en) * | 2010-12-20 | 2012-06-27 | 四川大学 | Halogen-free flame-resistant glass fiber reinforced polyformaldehyde composite material and preparation method thereof |
| CN102756404A (en) * | 2011-04-29 | 2012-10-31 | 中国林业科学研究院木材工业研究所 | Flame-retardant decorative plate, preparation method thereof and flame-retardant material comprising flame-retardant decorative plate |
| CN102756404B (en) * | 2011-04-29 | 2014-10-01 | 中国林业科学研究院木材工业研究所 | Flame-retardant decorative plate, preparation method thereof and flame-retardant material comprising flame-retardant decorative plate |
| CN103435966A (en) * | 2012-12-19 | 2013-12-11 | 安徽科聚新材料有限公司 | Polyformaldehyde material and preparation method thereof |
| CN104725826A (en) * | 2015-03-24 | 2015-06-24 | 湖州国信物资有限公司 | Novel flame-retardant polycarbonate composite material and preparation method thereof |
| CN105238004A (en) * | 2015-09-24 | 2016-01-13 | 安徽卓越电力设备有限公司 | Nonmetal corrosion-resistant prefabricated transformer substation box composite base plate |
| CN105820503A (en) * | 2016-05-16 | 2016-08-03 | 苏州新区华士达工程塑胶有限公司 | Modified polyformaldehyde inflaming retarding plastic |
| CN106751419A (en) * | 2016-11-22 | 2017-05-31 | 郑州仁宏医药科技有限公司 | A kind of POM flame retardant plastics and preparation method thereof |
| CN107759965A (en) * | 2017-11-09 | 2018-03-06 | 上海应用技术大学 | A kind of fire-retardant polyformaldehyde of intumescent compounding flame retardant and preparation method thereof |
| CN108410119A (en) * | 2018-03-22 | 2018-08-17 | 广东纳路纳米科技有限公司 | polyformaldehyde composite material and preparation method thereof |
| CN114773776A (en) * | 2022-05-06 | 2022-07-22 | 安徽银隆塑业科技有限公司 | Halogen-free flame-retardant polyformaldehyde granules and production process thereof |
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