CN114015221B - Low-heat-release halogen-free hybrid flame-retardant PC material and preparation method thereof - Google Patents
Low-heat-release halogen-free hybrid flame-retardant PC material and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 46
- 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 40
- 239000000463 material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004417 polycarbonate Substances 0.000 claims abstract description 54
- 239000002994 raw material Substances 0.000 claims abstract description 5
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- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- UADBQCGSEHKIBH-UHFFFAOYSA-N 3-phenoxy-2,4-dihydro-1h-1,3,5,2,4,6-triazatriphosphinine Chemical compound P1N=PNPN1OC1=CC=CC=C1 UADBQCGSEHKIBH-UHFFFAOYSA-N 0.000 claims description 8
- -1 diaryl phosphate Chemical compound 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
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- 238000000576 coating method Methods 0.000 claims description 2
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- 238000009826 distribution Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims 1
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- 238000012360 testing method Methods 0.000 abstract description 15
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
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- 150000002367 halogens Chemical class 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 239000010456 wollastonite Substances 0.000 description 3
- 229910052882 wollastonite Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- BWRJIDMRILXEDW-UHFFFAOYSA-N 2,3,4-trichlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C(Cl)=C1Cl BWRJIDMRILXEDW-UHFFFAOYSA-N 0.000 description 1
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical group OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- NONJJLVGHLVQQM-JHXYUMNGSA-N phenethicillin Chemical compound N([C@@H]1C(N2[C@H](C(C)(C)S[C@@H]21)C(O)=O)=O)C(=O)C(C)OC1=CC=CC=C1 NONJJLVGHLVQQM-JHXYUMNGSA-N 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to a low-heat-release halogen-free hybrid flame-retardant PC material and a preparation method thereof. According to the invention, the polycarbonate resin is used as a base material, a synergistic flame-retardant system and a special filler are compounded, on the premise of not using a copolymerized PC raw material, the heat release of the material is reduced at different stages of PC thermal degradation, the heat release under the OSU test condition is divided into two sections, and the maximum heat release rate of 65kW/m in the 5-min test is reached 2 The method has good market application prospect.
Description
Technical Field
The invention belongs to the field of PC (polycarbonate) materials, and particularly relates to a low-heat-release halogen-free hybrid flame-retardant PC material and a preparation method thereof.
Background
The PC material has high impact and high heat resistance, can reach the flame retardant grade of V-0 when the thickness is more than or equal to 8mm, and is widely applied to the fields of electronic and electric appliances, rail transit, aerospace and the like with heat resistance and flame retardant requirements. Particularly in aeronautical materials, it is necessary to pass the OSU65/65 test, i.e. in the presence of a flame and 35kW/m 2 Under the condition of an irradiation source, the cumulative heat release rate of the first 2min needs to be less than 65kW/m 2 The maximum heat release rate in the first 5min is less than 65kW/m 2 . Although the principle of the heat release test of aviation is the same as that of rail transit, the method for calculating the heat release (MARHE) of rail transit is an integral average value, and a flameless condition is used in the test process, so long as the degradation rate of the material is low or prolonged, the material can pass through the test, and the difficulty is lower than that of the heat release of aviation.
At present, a halogen flame-retardant system is used for solving the problem of high heat release, for example, a KT plate is mainly prepared by copolymerizing chlorinated polyethylene and acrylic ester, the surface hardness is high, the scratch resistance is realized, the heat release is lower than the upper limit of the standard by 50%, but the halogen structure can cause high combustion smoke toxicity, so that the halogen flame-retardant system is only used on the surface layer when being used as an integral structural member and cannot be used in large area and thickness, the forming and the application of the halogen flame-retardant system are greatly limited, the size of an interior trim of an airplane and the density of materials are strictly limited, the maximum heat release is not more than 2.0mm, and the flame retardant is difficult to be supported under the thickness of 2.0 mm.
CN 112969575A uses the composite material structure to design the layering structure through low heat release PEI and PTFE, to achieve the low heat release purpose, the process structure is complex, and the composite material structure is suitable for structural members, but not suitable for the production of large-batch interior trim parts. WO2015/189831Al Sabic uses block silicon PC and other special resins such as co-polymer PC and PEI to meet the requirement of low heat release, which is low in heat release, and has problems of high difficulty in synthesizing block silicon PC resin, high cost of PEI, and difficult processing of PEI as a whole at a processing temperature of 300 ℃, and high cost, and no one is applied to mass production in companies other than Sabic. In the EP3237542B1 patent, PEI and trichlorobenzene sulfonate are used as flame retardants to achieve the purpose of flame retardance, and the flame retardant has good high-temperature performance, but has high smoke toxicity after combustion and is not suitable for closed airplane cabins. CN109777073B filled 1-30 parts with boehmite or talc reduced the heat release of the material, but only passed 50kW/m as in EN45545-2 2 The heat release in the absence of flame cannot meet the peak heat release requirements in aerospace.
Disclosure of Invention
The invention aims to solve the technical problem of providing a low-heat-release halogen-free hybrid flame-retardant PC material and a preparation method thereof, the material reduces the heat release of the material in different stages of PC thermal degradation by taking polycarbonate resin as a base material and compounding a synergistic flame-retardant system and a special filler on the premise of not using a copolymerized PC raw material, the heat release under the OSU test condition is divided into two sections, and the maximum heat release rate of the test for 5min is 65kW/m 2 The method has good market application prospect.
The invention provides a low-heat-release halogen-free hybrid flame-retardant PC material which comprises the following components in parts by weight:
the PC resin is bisphenol A polycarbonate, the weight average molecular weight is between 25,000 and 35,000, and the molecular weight distribution is between 1 and 1.5.
The mole fraction of diaryl phosphate in the poly (block-phosphonyl oxygen-carbonic ester) is between 10 and 20 percent, the mole fraction of phosphonyl oxygen is between 10 and 40 percent, and the mole fraction of other polycarbonate units is between 40 and 80 percent. The Tg point is between 132 ℃ and 140 ℃.
The phosphorus flame retardant is one or more of phenoxy cyclotriphosphazene and derivatives thereof, phenoxy cyclotetraphosphazene and derivatives thereof, and phenoxy cyclopentaphosphazene and derivatives thereof.
The organic silicon flame retardant is one or more of polyborosilazane and derivatives thereof, cross-linked polydimethylsiloxane and derivatives thereof, methyl phenyl siloxane and derivatives thereof, polyorganosilsesquioxane, polyhedral oligomeric silsesquioxane and derivatives thereof, and octaphenylcyclotetrasiloxane.
The reinforcing filler is one or more of round alkali-free glass fiber, flat alkali-free glass fiber, wollastonite, calcium carbonate, calcium sulfate whisker, mica powder, talcum powder and hydrotalcite. The mesh number is 8000-15000 meshes.
The surface of the nano silicate fiber is coated with dimethoxy organic siloxane and acrylic acid modified siloxane, the coating amount is between 3 and 5 weight percent, the weight average molecular weight is about 2000, the diameter is between 3 and 5nm, the length is between 1 and 5 mu m, and N 2 The adsorption capacity is 3-6 ml/g.
The invention also provides a preparation method of the low-heat-release halogen-free hybrid flame-retardant PC material, which comprises the following steps:
according to the proportion, raw materials except the nano silicate fiber are mixed, and then fed into a double-screw extruder, and then the nano silicate fiber is fed into the double-screw extruder from a side material port, and is melted and extruded at the temperature of 150-265 ℃, so that the low-heat-release halogen-free hybrid flame-retardant PC material is obtained.
The invention also provides application of the low-heat-release halogen-free hybrid flame-retardant PC material in rail transit or buildings.
Advantageous effects
(1) The invention does not use resins with low heat release originally, such as PEI, PPC, si-PC and the like, takes common bisphenol A polycarbonate PC as a main material, is matched with a synergistic flame-retardant system, splits the combustion heat release of the PC into two peak values, reduces the highest heat release peak value, and leads the heat release to be in CCAR-25.853 35kW/m 2 Peak Heat Release 5min under test conditions with flame<65kW/m 2 ；
(2) The product of the invention has excellent performance, is suitable for injection molding and extrusion processing, has the melt mass flow rate of (5-15) g/10min, and is suitable for various molding modes such as extrusion, injection molding and the like;
(3) At 35kW/m 2 The irradiation source and the material under the flame condition can be ignited at the first time during testing, the methyl phenyl siloxane diffuses to the surface layer, and the phenoxy cyclotriphosphazene can preferentially generate phosphoric acid and pyrophosphoric acid functional groups at the first time while the combustion is slowed down, so that PC is carbonized. After the PC is carbonized by the flame retardant, the interface tension between the nano-fiber and the PC resin is large, the PC is still fixed by the nano-fiber after carbonization, the strength of the carbon layer is improved, the carbonized PC plays a heat insulation role in a matrix, and the heat transfer of the material under the degradation and irradiation of the material is delayed. Meanwhile, the viscosity of the bottom layer of PC resin is reduced by continuously testing high temperature and PC degradation, and at the moment, the phenoxy cyclotriphosphazene flame retardant is used for diluting PC degradation gas in nitrogen, carbon dioxide and water generated by oxidizing PC, so that the resin and the carbon layer are foamed, the release of PC combustible gas is slowed down, a heat insulation effect is achieved, and further the heat release is reduced. When the first carbon layer is broken and the resin and combustible gas diffuse out from the carbon layer, the main flame retardant poly (block-phosphonyl oxy-carbonic ester) with higher heat resistance per se and PC have undergone the second reaction, the carbon forming reaction gradually and slowly proceeds without increasing the heat release to 65kW/m 2 The peak heat release is reduced, and the maximum heat release rate of the material can be reduced to 65kW/m by using the flame-retardant system 2 The following.
Drawings
FIG. 1 is an SEM image of a material of nano silicate fiber used in the present invention;
FIG. 2 is a graph of the thermogravimetric profile of RDX or DMP-HDP phosphate flame retardant alone;
FIG. 3 is a graph of the thermogravimetric profile of the use of phenoxycyclotriphosphazene and poly (block-phosphonato-carbonate) flame retardants;
FIG. 4 is a thermal weight loss curve of nano silicate fiber at 5 parts by mass;
FIG. 5 is an OSU heat release test curve of example 5.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Examples and comparative examples source:
the preparation method comprises the following steps:
mixing the raw materials except the nano silicate fiber according to the proportion, feeding the mixture into a double-screw extruder, and then feeding the nano silicate fiber into the double-screw extruder from a side material port, wherein the length-diameter ratio of the screws is 40, and the mixture is melted and extruded at 150-265 ℃, so that the low-heat-release halogen-free hybrid flame-retardant PC material is obtained.
And (3) injection molding test: 150mm 1.5mm plate, OSU65/65 according to CCAR-25.853 test condition 35kW/m 2 There is a flame mode.
Conclusion 1:
the PC resin has a high rate of heat release and high amount of emissions without the addition of poly (block-phosphonato-carbonate) and nano-silicate fibers. In addition, wollastonite and glass fiber have the length-diameter ratio to reinforce the carbon layer, but the length-diameter ratio of the wollastonite and the glass fiber causes a wick effect during combustion, so that the heat release is larger in the first 2min, and the talc powder has the best effect in terms of the comprehensive maximum heat release rate and the total heat release amount.
Conclusion 2:
the RDX or DMP-HDP phosphate ester flame retardant is used, the heat resistance is 20-30 ℃ higher than that of common phosphate ester, but the heat release is still poor because the flame retardant reacts with PC and only has a peak value of heat release, so the maximum heat release rate is higher, and excessive flame retardant is added, so that the carbon forming reaction is too fast, and the peak value of heat release is larger, as shown in figure 2, the thermal weight loss differential curve in the first stage can show that the thermal decomposition peak value is caused by the flame retardant, and the reaction with PC can continuously occur, so the maximum heat release is increased.
In the embodiment, the more the fire retardant phenoxy cyclotriphosphazene and poly (block-phosphonyloxy-carbonate) are, the better the fire retardant phenoxy cyclotriphosphazene and poly (block-phosphonyloxy-carbonate) are, the first stage is the reaction of the fire retardant phenoxy cyclotriphosphazene and PC to form a loose porous carbon layer, and under the strong surface energy of the nanofiber, the carbon layer structure can block heat and slow down the reaction of PC and the fire retardant, such as the second peak value in TGA in figure 3; in the second stage, when the PC and the flame retardant react completely, the degradation of the PC can not be slowed down any more, and the peak values of the heat release in the two stages are less than 65kW/m 2 Upper limit of heat release.
Conclusion 3:
the individual nano material non-fiber structure, although the peak heat release will be reduced, the carbon layer strength is poor, and the resin and combustible gas flowing out still make the heat release reach 100kW/m 2 The above. As in example 6, the thermal weight loss of the nano silicate fiber is shown in FIG. 4 at 5% by mass, and the segmented carbon formation reaction divides the PC heat release reaction into three peak values, thereby effectively reducing the heat release. The OSU heat release test curve is shown in figure 5.
Claims (7)
1. A low-heat-release halogen-free hybrid flame-retardant PC material is characterized in that: the paint comprises the following components in parts by weight:
10-85 parts of PC resin;
5 to 10 portions of poly (block-phosphonyl oxy-carbonic ester);
5 to 10 parts of phosphorus flame retardant;
0.3 to 5 parts of an organic silicon flame retardant;
2-20 parts of reinforcing filler;
5363 parts of nano silicate fiber 1~5;
wherein the reinforcing filler is talcum powder; the phosphorus flame retardant is one or more of phenoxy cyclotriphosphazene, phenoxy cyclotetraphosphazene and phenoxy cyclopentaphosphazene.
2. The PC material of claim 1 wherein: the PC resin is bisphenol A polycarbonate, the weight average molecular weight is between 25,000 and 35,000, and the molecular weight distribution is between 1 and 1.5.
3. The PC material of claim 1 wherein: the mole fraction of diaryl phosphate in the poly (block-phosphonyl oxygen-carbonic ester) is between 10 and 20 percent, the mole fraction of phosphonyl oxygen is between 10 and 40 percent, and the mole fraction of polycarbonate units is between 40 and 80 percent.
4. The PC material of claim 1 wherein: the organic silicon flame retardant is one or more of polyborosilazane, cross-linked polydimethylsiloxane, methyl phenyl siloxane, polysilsesquioxane and octaphenylcyclotetrasiloxane.
5. The PC material of claim 1 wherein: the surface of the nano silicate fiber is coated with dimethoxy organic siloxane and acrylic acid modified siloxane, and the coating amount is between 3 and 5 weight percent.
6. A preparation method of the low heat release halogen-free hybrid flame retardant PC material as claimed in claim 1, comprising:
according to the proportion, the raw materials except the nano silicate fiber are mixed, then fed into a double-screw extruder, and then the nano silicate fiber is fed into the double-screw extruder from a side material port and melted and extruded at the temperature of 150-265 ℃ to obtain the low-heat-release halogen-free hybrid flame-retardant PC material.
7. Application of the low-heat-release halogen-free hybrid flame-retardant PC material as claimed in claim 1 in rail transit or construction.
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| CN103080192A (en) * | 2010-05-20 | 2013-05-01 | 道康宁公司 | Polymer compositions containing alkoxysilanes |
| KR101649186B1 (en) * | 2011-04-14 | 2016-08-18 | 에프알엑스 폴리머스, 인코포레이티드 | Polyphosphonate and copolyphosphonate additive mixtures |
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| WO2015069642A1 (en) * | 2013-11-05 | 2015-05-14 | Polyone Corporation | Phosphazene flame retardant polycarbonate compounds |
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