CN114316561B - High-gloss low-filling halogen-free hybrid flame-retardant PC material and preparation and application thereof - Google Patents
High-gloss low-filling halogen-free hybrid flame-retardant PC material and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a high-gloss low-filling halogen-free hybrid flame-retardant PC material, and preparation and application thereof. The material comprises the following components in parts by weight: 55-85 parts of polycarbonate; 5-14 parts of copolymerized polycarbonate; 1-10 parts of a flame retardant; 5-15 parts of a flame retardant; 1-10 parts of a flame retardant; 2-3 parts of methyl methacrylate-styrene grafted nano titanium dioxide; 1-2 parts of zinc borate. The material has high-grade flame retardance, low filling and high gloss, and simultaneously achieves smoke density and heat release of more than EN45545-2 R1 HL2.
Description
Technical Field
The invention belongs to the field of polycarbonate materials and preparation and application thereof, and particularly relates to a high-gloss low-filling halogen-free hybrid flame-retardant PC material and preparation and application thereof.
Background
The polycarbonate has good flame retardance, high heat resistance, impact resistance and small density, and is widely applied to the fields of electronic appliances, automobiles, rail transit, aerospace and the like. The materials currently used in wallboard require flame retardant ratings above EN45545-2 R1HL2, but the smoke density may increase as the heat release decreases. The general scheme is divided into three types, and the scheme is to add in PCThe raw materials are limited by factories such as Saibike, costa, diperson and the like, and the notch impact strength is made to be 10kJ/m 2 In the following, not only the high impact property of PC itself is lost, but also the mixed material may cause uneven appearance in the subsequent plastic uptake due to phase tolerance, and the product requirement can be met by post processing. The second scheme is that fillers for enhancing the carbon layer structure, such as wollastonite, talcum powder, glass fiber and the like, are added into the formula of EN45545-2, and the carbon layer structure is enhanced during carbonization. For interior parts applied to rail transit, weight reduction and spraying-free are the main requirements, the density of materials is increased along with the addition of fillers, and the appearance needs to be painted to achieve a corresponding surface effect.
Sabic in U.S. Pat. No. 9.266,541B2 blends polysilicone-PC and polyimide-structured PC to give a composition meeting the smoke density and heat release of R1HL 3, and the raw materials thereof are not sold to the outside.
Chinese patent CN112409770A discloses the use of organosilicon/phenoxycyclophosphazene copolymerization and composite inorganic filler as flame retardant smoke suppressant and heat insulator, but the addition of the powder is more than 5% to achieve the flame retardant level of R1HL2 or R1HL 3, in the examples, most of the powder is 15%, and the powder cannot be directly applied to appearance parts.
Chinese patent CN112852139A discloses the use of porous ceramics as smoke suppressant, which is effective in reducing smoke density at the time of testing for PC/ABS, but at 50kW/m 2 The required smoke density cannot be achieved in the heat source.
Therefore, it is necessary to study polycarbonate materials with a small amount of filler added and a smoke density and heat release of more than EN45545-2 R1 HL2.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-gloss low-filling halogen-free hybrid flame-retardant PC material, and preparation and application thereof, so as to overcome the defects that the polycarbonate material in the prior art has more filling amount, and smoke density and heat release can not meet the requirements.
The invention provides a high-gloss low-filling halogen-free hybrid flame-retardant PC material which comprises the following components in parts by weight:
the flame retardant 1 is a pentaerythritol diphosphate compound;
the flame retardant 2 is an organic silicon flame retardant;
the flame retardant 3 is an organic phosphorus flame retardant.
Preferably, the polycarbonate is a linear polycarbonate, and the linear polycarbonate is a bisphenol a polycarbonate.
Preferably, the polycarbonate has a weight average molecular weight Mw of 25,000-35,000 and a molecular weight distribution of 1-1.5.
Preferably, the polycarbonate has a melt index of (3-6) g/10min @300 ℃/1.2kg.
Preferably, the copolymerized polycarbonate is dimethoxysiloxane copolymerized polycarbonate, and the dimethoxysiloxane copolymerized polycarbonate is block polydimethylsiloxane copolymerized PC.
Preferably, the weight average molecular weight of the carbonate unit in the block polydimethylsiloxane co-PC is 29000-30000, the silicon weight fraction is 19wt% -20wt%, and the silicon mole fraction is 40% -80%.
Preferably, the block polydimethylsiloxane copolymer PC has a Tg point of 132 ℃ to 140 ℃.
Preferably, the pentaerythritol diphosphonate compound is isobutyl pentaerythritol diphosphonate.
Preferably, the TGA melting point of the pentaerythritol diphosphonate compound is 250-260 ℃, and the phosphorus content is 12-15 wt%.
Preferably, the organosilicon flame retardant is cross-linked polymethylphenylsiloxane, and the molar ratio of phenyl groups in the cross-linked polymethylphenylsiloxane is 60-80%, and the molar ratio of methyl groups in the cross-linked polymethylphenylsiloxane is 20-40%.
Preferably, the cross-linked polymethylphenylsiloxane has a weight-average molecular weight Mw of 16000-36000 and a methyl end group.
Preferably, the organophosphorus flame retardant is a phenoxy cyclic phosphazene flame retardant; the phenoxy cyclophosphazene flame retardant comprises one or more of phenoxy cyclotriphosphazene and derivatives thereof, phenoxy cyclotetraphosphazene and derivatives thereof, and phenoxy cyclopentapzene and derivatives thereof.
Preferably, the methyl methacrylate-styrene grafted nano titanium dioxide is obtained by sequentially adding methyl methacrylate, styrene, 3-ethoxy methacrylic propyl silane, an initiator and an anti-coagulating agent into a nano titanium dioxide dispersion liquid, and stirring for reaction.
Preferably, the preparation method of the methyl methacrylate-styrene grafted nano titanium dioxide comprises the following steps: stirring nano titanium dioxide in an absolute ethyl alcohol solution, and performing ultrasonic dispersion for 1-3 h after stirring; ultrasonically dispersed TiO 2 Methyl methacrylate, styrene, 3-ethoxy methacrylic propyl silane, an initiator and an anti-coagulating agent are sequentially added into the dispersion liquid, stirred and reacted for 3h to 6h at the temperature of 80 ℃ to 90 ℃, and after the reaction, the solvent is recovered through rotary evaporation, the concentration is increased, and then reduced pressure distillation is carried out to obtain the methyl methacrylate-styrene grafted nano titanium dioxide.
Preferably, the nano titanium dioxide crystal phase is rutile type, has a particle structure and has a particle size of 5-50 nm.
Preferably, the proportion of the nano titanium dioxide, the absolute ethyl alcohol solution, the methyl methacrylate, the styrene, the 3-ethoxy methyl acrylic propyl silane, the initiator and the anti-coagulating agent is 150-250g:5L-10L:450-550mL:150-250mL:45-55mL:0.3-0.8g:3-5g.
Preferably, the initiator is K 2 O 8 S 2 Potassium persulfate; the anti-agglomerating agent is calcium phosphate.
Preferably, the methyl methacrylate-styrene grafted nano titanium dioxide is extracted by tetrahydrofuran, and the grafting rate is 10wt% -30wt% in terms of weight after extraction and drying, wherein the PS ratio is below 20%.
Preferably, the zinc borate is 2 Zn.3B 2 O 3 ·3.5H 2 O, said 2 Zn.3B 2 O 3 ·3.5H 2 In O, B 2 O 3 45％-48％，2Zn·3B 2 O 3 ·3.5H 2 The temperature of the O-containing de-crystallization water is 280-320 ℃, and the particle size is 3-5 mu m.
The invention also provides a preparation method of the high-gloss low-filling halogen-free hybrid flame-retardant PC material, which comprises the following steps:
mixing the components except the methyl methacrylate-styrene grafted nano titanium dioxide and the zinc borate, feeding the mixture into a main feed of a double-screw extruder, feeding the methyl methacrylate-styrene grafted nano titanium dioxide and the zinc borate into the double-screw extruder from a side feed port, and performing melt extrusion to obtain the high-gloss low-filling halogen-free hybrid flame-retardant PC material, wherein the extrusion temperature is 265-280 ℃.
The invention also provides application of the high-gloss low-filling halogen-free hybrid flame-retardant PC material in rail transit wallboards.
The invention adopts a one-step method, a suspension polymerization method is adopted to coat the nano titanium dioxide, the nano titanium dioxide is firstly subjected to ultrasonic dispersion and then coated, a styrene monomer, methyl methacrylate and 3-ethoxy methyl acrylic propyl silane are added into a coating monomer as reaction units, and the two-step reaction of surface treatment of firstly treating the titanium dioxide is avoided.
At 50kW/m 2 Under the heat source, the surface temperature of the PC material is between 700 and 800 ℃, and the zinc borate is dehydrated and grafted TiO 2 The Lewis acid plays a role of Lewis acid at high temperature to promote isomerization reaction of the organosilicon flame retardant and PC, promotes crosslinking reaction of the PC at high temperature, and simultaneously generates carbon under the condition of the existence of P flame retardant to generate a carbon layer with a Si-C structure. The organosilicon fire retardant (such as cross-linked polymethylphenylsiloxane) reacts with PC to generate non-combustible micromolecule which can be rapidly foamed with water in the core containing the grafted nano titanium dioxide to generate a heat insulation carbon layer which can not only block external radiationThe heat transfer of the heat emitting source can also increase the path of PC micromolecules degraded by combustion which slowly diffuse to the sample testing surface, and slow down the combustion. The methyl methacrylate-styrene grafted nano titanium dioxide has good dispersibility relative to ungrafted titanium dioxide, can be uniformly distributed in a carbon layer during testing, and forms carbon together with an organic silicon flame retardant (such as cross-linked polymethylphenylsiloxane), thereby having good heat insulation effect. The organosilicon flame retardant (such as cross-linked polymethylphenylsiloxane) is partially diffused to the carbon layer, meanwhile, titanium dioxide containing a nano structure can adsorb part of the flame retardant, the strength of the formed carbon layer is higher, and degraded gas is not easy to escape.
Advantageous effects
(1) The invention overcomes the limitation of the raw material using the copolymerized PC, the carbon layer structure generated at the high temperature of 850 ℃ during the test can be enhanced by using the filling proportion of below 5 percent, the titanium dioxide (the specific gravity is 4.2-4.3) and the zinc borate (the specific gravity is 3.64) with higher specific gravity are selected as the fillers, the actual filling volume ratio is below 2 percent, and the appearance effect similar to the copolymerized PC is achieved;
(2) According to the invention, the methyl methacrylate-styrene grafted nano titanium dioxide and the zinc borate are compounded, so that the smoke density and heat release of the PC material are reduced, and meanwhile, the methyl methacrylate-styrene grafted nano titanium dioxide surface layer coating resin has the advantages of improved compatibility with PC, high surface gloss of the plate and no pockmarks. And the methyl methacrylate-styrene grafted nano titanium dioxide, zinc borate, the flame retardant 1, the flame retardant 2 and the flame retardant 3 act synergistically at the same time, so that PC foams and forms carbon, the porous carbon layer after the carbon formation effectively insulates heat, the smoke density and heat release during combustion are reduced, and the smoke density Ds (4 min) of the PC material is ensured<150/VOF(4min)<300, heat Release MARHE (maximum average Heat Release Rate)<60kW/m 2 Smoke density and heat release reach EN45545-2 R1 HL3 rating;
in conclusion, the PC material has high-grade flame retardance, low filling and high gloss, and simultaneously achieves smoke density and heat release of more than EN45545-2 R1HL2.
Drawings
FIG. 1 is a diagram of the smoke density Ds of a high-gloss low-filling halogen-free hybrid flame-retardant PC material in example 5 of the invention.
Fig. 2 is a heat release rate/time curve of the high gloss, low filling halogen-free hybrid flame retardant PC material in example 5 of the present invention, wherein sample 1, sample 2, and sample 3 are three tests of the PC material.
FIG. 3 is a solid diagram of the foamed carbon of the sample after the smoke density test of the high-gloss low-filling halogen-free hybrid flame-retardant PC material in example 5 of the invention.
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 can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
And (3) reagent sources:
polycarbonate (C): bisphenol A polycarbonate, melt index 3g/10min @300 ℃/1.2kg, WB1239 Covestro; copolymerized polycarbonate: block polydimethylsiloxane copolpc (silicon weight fraction 19.4% wt (SL 0301 gansu silver), PMDS flexblock Tg point-120 ℃;
flame retardant 1: isobutyl pentaerythritol diphosphate (15 wt% phosphorus content, 257 ℃ TGA melting point), FCX-210 Diricha;
flame retardant 2: crosslinked polymethylphenylsiloxane (60% molar ratio of phenyl groups and 40% molar ratio of methyl groups), KR 480;
flame retardant 3: phenoxy cyclotriphosphazene, SPB-100, tsukamur chemistry;
the preparation method of the methyl methacrylate-styrene grafted nano titanium dioxide comprises the following steps: stirring 200g of nano titanium dioxide (MZT-R15, a micro nano new material) in 5L of absolute ethanol solution, and ultrasonically dispersing for 2h after stirring; ultrasonically dispersed TiO 2 The dispersion was charged into a 10L reaction vessel, followed by sequentially adding 500ml of methyl methacrylate (commercially available 99.5% by GC), 200ml of styrene, 50ml (commercially available 99.5% by GC) of 3- [ diethoxy (methyl) silyl ] silyl]Propyl methacrylate, 0.5g K 2 O 8 S 2 Potassium persulfate initiator (commercially available) and 5g of calcium phosphate as an anti-coagulating agent (commercially available) were reacted at 85 ℃ for 6 hours with stirring. After the reaction, the solvent is recovered through rotary evaporation, the concentration is increased, and then reduced pressure distillation is carried out to obtain the methyl methacrylate-styrene grafted nano titanium dioxide. The grafting rate was 18wt% after extraction and drying by weight using a soxhlet extractor and tetrahydrofuran.
Nano titanium dioxide: MZT-R15, a minimally invasive new material;
zinc borate: 2 Zn.3B 2 O 3 ·3.5H 2 O, the temperature of the crystallization water is 320 ℃, the particle size is 2-5 mu m, ZB23, borax in America;
the preparation method of the PC material comprises the following steps:
according to the mixture ratio of the following tables 1 and 2, mixing the components except the methyl methacrylate-styrene grafted nano titanium dioxide (or nano titanium dioxide) and the zinc borate, feeding the mixture into a double-screw extruder to form a main feed, feeding the methyl methacrylate-styrene grafted nano titanium dioxide (or nano titanium dioxide) and the zinc borate into the double-screw extruder from a side feed port, and performing melt extrusion to obtain the PC material, wherein the extrusion temperature is 260-280 ℃.
And (3) performance testing:
(1) Smoke density (Ds 4 min): according to ISO5659-2 standard, 50kW/m 2 Flameless, hazard grade: HL1 is less than or equal to 600, HL2 is less than or equal to 300, HL3 is less than or equal to 150;
(2) Smoke density (VOF (4 min)): according to ISO5659-2 standard, 50kW/m 2 Flameless, hazard grade: HL1 is less than or equal to 1200, HL2 is less than or equal to 600, HL3 is less than or equal to 300;
(3) Heat release (MARHE): according to ISO5660-1 standard, 50kW/m 2 And the danger level: HL2 is less than or equal to 90kW/m 2 ，HL3≤60kW/m 2 ；
(4) Gloss: according to ISO 2813-2014 standard, the test angle is 60 degrees and the thickness is 2mm.
TABLE 1 proportioning of examples (parts by weight)
TABLE 2 comparative example proportions (parts by weight)
As shown in tables 1 and 2, the content of the flame retardant 1 in example 2 is lower than that in example 1, the smoke density of example 2 is significantly reduced, and the heat release is improved, because the structure of the flame retardant 1 contains pentaerythritol units, which assists in carbon formation, effectively reduces heat release, and the use of the carbon-forming agent also causes the smoke density to increase.
In example 3, the content of the flame retardant 3 is higher than that in example 2, the heat release is reduced and the smoke density is improved in example 3, because the flame retardant 3 can be used as a part of gas source to expand a carbon layer after foaming, the effect of reducing the heat release is achieved, the heat release is reduced to be below 60, and the effect of reducing the heat release is achieved<60kW/m 2 Is released.
The content of the flame retardant 2 in the examples 6 and 5 is higher than that in the example 4, the heat release of the examples 5 and 6 is gradually reduced, and the smoke density is still slowly increased because the flame retardant 2 has the function of isomerizing PC, so the smoke density and the heat release are higher.
The comparative example 1, in which the content of the copolycarbonate is higher than the range of the present invention, has a smoke density (Ds 4) higher than that of example 5, because the PMDS structure in the copolyester is mainly carbon-forming at a low content, and the smoke generation amount of the PMDS structure is increased if the content is too large. Comparative example 2, which had no addition of copolycarbonate, had a smoke density and heat release greater than those of example 5, due to SiO generated by PMDS in copolymerization 2 Is a non-combustible substance and can be used for assisting to form a Si-C carbon layer, and can be used for assisting to form carbon in a PC phase together with a flame retardant.Comparative example 3, in which flame retardant 1 was not added, had a smoke density and a heat release higher than those of example 5, and in which carbon formation was poor when the main flame retardant was not added. Comparative example 4, without adding flame retardant 2, has smoke density and heat release greater than those of example 5, and if the degradation process between-2 and PC without flame retardant cannot be cut apart, the heat release of the material is increased more. Comparative example 5 has no flame retardant 3, and has smoke density and heat release higher than those of example 5, and the flame retardant 3 has a phosphazene structure, and can assist in foaming, play a role in heat insulation, and reduce smoke density and heat release. Comparative example 6 has no addition of grafted titanium dioxide, and has smoke density and heat release greater than those of example 5, because the flame retardant cannot be synergized to form a complex, the flame retardant itself is decomposed at high temperature, the flame retardant efficiency is low, and the target cannot be achieved by adjusting the addition amount. Comparative example 7 does not add zinc borate, and the smoke density and heat release are both greater than those of example 5, and the zinc borate is not added, so that the flame retardant cannot be synergized, and the effect of inhibiting smoke is achieved. Comparative example 8 added ungrafted titanium dioxide, which had a greater smoke density and heat release than example 5, due to the untreated TiO 2 The PC has poor dispersibility in PC, cannot become a core of carbon formation and foaming, effectively blocks a heat source, and further degrades the material. Therefore, the methyl methacrylate-styrene grafted nano titanium dioxide, zinc borate, the flame retardant 1, the flame retardant 2 and the flame retardant 3 are simultaneously synergistic, so that the smoke density and heat release during combustion can be reduced, and the EN45545-2 R1 HL3 grade is achieved.
Claims (9)
1. The high-gloss low-filling halogen-free hybrid flame-retardant PC material is characterized by comprising the following components in parts by weight:
the flame retardant 1 is a pentaerythritol diphosphate compound;
the flame retardant 2 is an organic silicon flame retardant; the organic silicon flame retardant is cross-linked polymethylphenyl siloxane, wherein the molar ratio of phenyl in the cross-linked polymethylphenyl siloxane is 60-80%, and the molar ratio of methyl is 20-40%;
the flame retardant 3 is an organic phosphorus flame retardant; the organophosphorus flame retardant is phenoxy cyclic phosphazene flame retardant;
the copolymerized polycarbonate is block polydimethylsiloxane copolymerized PC, the weight-average molecular weight of carbonate units in the block polydimethylsiloxane copolymerized PC is 29000-30000, and the silicon weight fraction is 19-20 wt%;
the methyl methacrylate-styrene grafted nano titanium dioxide is obtained by sequentially adding methyl methacrylate, styrene, 3-ethoxy methacrylic propyl silane, an initiator and an anti-coagulating agent into nano titanium dioxide dispersion liquid, and stirring for reaction.
2. The PC material of claim 1, wherein the polycarbonate is a linear polycarbonate, the linear polycarbonate being a bisphenol a polycarbonate; the polycarbonate has a weight average molecular weight Mw of 25,000-35,000; the melt index of the polycarbonate was (3-6) g/10min @300 ℃/1.2kg.
3. The PC material of claim 1 wherein the block polydimethylsiloxane co-PC has a Tg of 132 ℃ to 140 ℃.
4. The PC material of claim 1, wherein the pentaerythritol diphosphonate compound is isobutyl pentaerythritol diphosphonate; the TGA melting point of the pentaerythritol diphosphonate compound is 250-260 ℃, and the phosphorus content is 12-15 wt%.
5. The PC material of claim 1, wherein the cross-linked polymethylphenylsiloxane has a weight average molecular weight Mw of 16000-36000 and end groups of methyl groups.
6. The PC material of claim 1, wherein the phenoxy cyclophosphazene flame retardant comprises one or more of phenoxy cyclotriphosphazene and derivatives thereof, phenoxy cyclotetraphosphazene and derivatives thereof, and phenoxy cyclopentapzene and derivatives thereof.
7. The PC material of claim 1, wherein the zinc borate is 2 Zn.3B 2 O 3 ·3.5H 2 O。
8. A method of preparing a PC material as claimed in any one of claims 1 to 7, comprising the steps of:
mixing the components except the methyl methacrylate-styrene grafted nano titanium dioxide and the zinc borate, feeding the mixture into a main feed of a double-screw extruder, feeding the methyl methacrylate-styrene grafted nano titanium dioxide and the zinc borate into the double-screw extruder from a side feed port, and performing melt extrusion to obtain the high-gloss low-filling halogen-free hybrid flame-retardant PC material, wherein the extrusion temperature is 150-265 ℃.
9. Use of a PC material according to any one of claims 1-7 in rail transit wall panels.
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