CN113637309B - Flame-retardant polycarbonate alloy composition with high thermal stability and preparation method and application thereof - Google Patents
Flame-retardant polycarbonate alloy composition with high thermal stability and preparation method and application thereof Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/329—Phosphorus containing acids
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- 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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention relates to a flame-retardant polycarbonate alloy composition with high thermal stability, a preparation method and application thereof. The flame-retardant polycarbonate alloy composition with high thermal stability comprises a polycarbonate flame retardant, a composite stabilizer, an anti-dripping agent and other auxiliaries. The flame-retardant polycarbonate alloy composition provided by the invention has good heat resistance (the thermal degradation activation energy is more than 200J/mol, the thermal stability is good), batch stability and stable flame-retardant performance, can reach a high flame-retardant grade of 3.0mm5VA, and the flame-retardant stability after water boiling is maintained at a 5VA grade.
Description
Technical Field
The invention belongs to the field of recycled plastics, and particularly relates to a flame-retardant polycarbonate alloy composition with high thermal stability, and a preparation method and application thereof.
Background
Polycarbonate (PC) is an engineering plastic with good comprehensive performance, has high oxygen index, certain self-extinguishing property and the advantages of high flame retardance and high toughness, and is the engineering plastic with the fastest growth speed and the largest capacity and scale in recent years. With the widespread use of polycarbonate, a large amount of polycarbonate waste is discarded, which causes a severe problem of plastic contamination.
At present, various types of solutions are proposed for waste polycarbonate, mainly the following solutions:
(1) the waste polycarbonate is treated by adopting incineration or landfill technology, but the method cannot utilize effective resources in the waste polycarbonate and causes secondary environmental pollution.
(2) The waste polycarbonate is simply recovered and subjected to grain extraction, and then directly degraded into common plastics for use, and the method can realize the recycling of the waste polycarbonate, but still cannot fully utilize the useful value of the polycarbonate.
(3) The waste polycarbonate is recovered and then modified to improve the performance of the waste polycarbonate. For example, commercially available SAG series or Joncry series, in which a polycarbonate is graft-modified with an epoxy graft and the heat resistance is improved by reacting an epoxy with a terminal group of the polycarbonate. Although epoxy has a good chain extension effect on low-molecular-weight polycarbonate, the introduction of epoxy groups into a PC system can reduce fluidity and impact strength, so that the requirement of excellent fluidity in the processing process of materials in the fields of electronics, electricity, communication and rail transit cannot be met, and the requirement of sufficient toughness to ensure the safety of products in the service process of the products can be met.
The patent CN104672834A provides a high-performance low-cost PC modified material, which takes recycled PC reclaimed materials as matrix resin, is modified by flame retardant, toughening agent, compatilizer, chain extender and the like, has excellent impact toughness, rigidity, heat resistance and flame retardance while keeping the original excellent physical and chemical properties of PC, and can reach the flame retardant grade of UL 94V-0; but the stability is not concerned, and whether the flame retardant meets the high requirements of 5V flame retardance and stable and consistent batch property cannot be known; and the chain extender is also used for carrying out reaction with the end group to reduce the part with small molecular weight, and the unfavorable problems of poor material fluidity, brittleness, reduced flame retardant grade and the like still exist.
Therefore, the development of a better technology for recycling the PC so as to effectively improve the stable flame retardant property, the toughness, the thermal stability and the batch stability of the PC has important research significance and value.
Disclosure of Invention
The invention aims to overcome the defects or shortcomings of poor flame retardant property and heat resistance, poor toughness and poor batch stability of PC materials obtained by a PC recycling technology in the prior art, and provides a flame-retardant polycarbonate alloy composition with high thermal stability. The flame-retardant polycarbonate alloy composition provided by the invention has the advantages of higher toughness, better heat resistance, batch stability and stable flame retardance, and can be widely applied to the fields of electronics, electrics, communication, rail transit, new energy and the like.
Another object of the present invention is to provide a method for preparing the above flame retardant polycarbonate alloy composition with high thermal stability.
The invention also aims to provide application of the high-thermal-stability flame-retardant polycarbonate alloy composition in preparing electronic products, communication products and new energy products.
In order to achieve the purpose, the invention adopts the following technical scheme:
a flame-retardant polycarbonate alloy composition with high thermal stability comprises the following components in parts by weight:
the composite stabilizer is a mixture of a phosphite heat stabilizer and a phosphoric acid aqueous solution, and the weight fraction of the phosphite stabilizer in the composite stabilizer is 60-85%.
The flame retardant is used for improving the flame retardant performance, and the composite stabilizer is used for improving the flame retardant stability. Through the synergistic effect of the flame retardant and the composite stabilizer, the obtained polycarbonate alloy composition has excellent flame retardant performance and flame retardant stability, high thermal degradation activation energy and good thermal stability, the performances of 3 batches are basically kept consistent, and the application range of polycarbonate (including recycled polycarbonate and new polycarbonate) can be widened.
Preferably, the high-heat-stability flame-retardant polycarbonate alloy composition comprises the following components in parts by weight:
preferably, the polycarbonate comprises recycled polycarbonate and virgin polycarbonate, and the weight fraction of the recycled polycarbonate in the polycarbonate is 60-100%.
It is to be understood that the recycled polycarbonate refers to a recycled material obtained by sorting and collecting waste polycarbonate according to a physical recycling treatment means which is conventional in the art. The new material polycarbonate is polycarbonate resin which is directly used after polymerization and is not injected or used.
According to the invention, the flame retardant is added into a resin system for recovering polycarbonate in a large proportion to improve the flame retardant property, but the system brings great batch property fluctuation due to high activity of the recovered resin, particularly great toughness notch fluctuation, hidden danger is brought to flame retardant stability, particularly high flame retardant grade 5V grade, high requirements on burning through and molten drop are high, and hidden danger such as high flame retardant failure caused by reduction of combustion melt strength is brought due to high content of the recovered polycarbonate.
On the basis of the above, the present invention is further improved by using a specific composite stabilizer. Specifically, due to the introduction of the phosphoric acid aqueous solution in the composite stabilizer, on one hand, the polycarbonate resin has higher and stable thermal degradation activation energy due to the existence of an acidic environment brought by phosphoric acid, is more stable under the conditions of heat and oxygen, is not easy to be hybridized to initiate degradation, realizes the passivation protection effect, and realizes the stable maintenance of flame retardance by keeping the stable isomerization of the resin in the flame retardant placing process; on the other hand, the introduction of a small amount of water not only promotes the uniform dispersion of the sulfonate in the PC resin but also can remove small molecular substances during the processing and deashing process; the phosphoric acid aqueous solution can endow the flame-retardant polycarbonate alloy composition with better flame-retardant stability and thermal stability; meanwhile, the phosphite ester stabilizer is compounded, so that the phosphite ester composite stabilizer can be fully exerted in a stable acid system, and the phosphite ester plays a role in capturing free radicals to promote combustion.
The flame-retardant polycarbonate alloy composition with high thermal stability provided by the invention has a stable flame-retardant 3.0mm5VA grade, the boiling flame-retardant stability is maintained at a 5VA grade, the thermal degradation activation energy is more than 200J/mol, the thermal stability is good, and the performances of 3 batches are basically kept consistent.
Preferably, the recycled polycarbonate has a melt index MI of not higher than 10g/10min under the condition of 300 ℃/1.2kg and a MI heat retention increase of not higher than 40% according to ISO1133-2011 standard, and has light transmittance of not lower than 75% at a wavelength of 500nm and a thickness of 2.0 mm.
More preferably, the recycled polycarbonate has a melt index MI of 6-10 g/10min and an MI heat retention increase of 20-40% under the condition of 300 ℃/1.2kg according to ISO1133-2011 standard; the recycled polycarbonate has a light transmittance of 75-89% at a wavelength of 500nm and a thickness of 2.0 mm.
The light transmittance is obtained by testing a sample plate with the thickness of 2mm by using a color difference meter under the wavelength of 500 nm.
The recovered polycarbonate under the condition has higher purity, and is beneficial to further improving the thermal degradation activation energy.
More preferably, the weight average molecular weight of the recycled polycarbonate is 48000 to 53000.
Preferably, the recycled polycarbonate is prepared by the following process: the waste polycarbonate is classified by physical machinery and then is polished, cleaned, dried, crushed, granulated, sieved and magnetized, and the polycarbonate is obtained.
Preferably, the weight-average molecular weight of the virgin polycarbonate is 32000-63000, the content of terminal hydroxyl groups is less than 100ppm, and the content of BPA is less than 20 ppm.
The content of the terminal hydroxyl groups is determined according to the GB12008.3-1989 standard.
The BPA content was determined by the following procedure: passing through a C18 chromatographic column and fixing the column temperature at 40 ℃, mobile phase acetonitrile: the methanol content is 9: 1 (volume ratio), the flow rate was fixed at 1m L/min, and the content was measured by the o-cresol internal standard method at a detection wavelength of 280 nm.
The new material polycarbonate under the condition has higher thermal stability, and can realize more stable flame retardance under proper thermal degradation activation energy.
More preferably, the terminal hydroxyl group content of the new polycarbonate is 0.5-30 ppm, and the BPA content is 0.01-18 ppm.
Preferably, the new polycarbonate is prepared by a phosgene method.
Preferably, the flame retardant is one or more of sulfonate flame retardants, fluorosulfonate flame retardants or carbonate flame retardants.
More preferably, the sulfonate flame retardant is one or two of sodium benzenesulfonate and potassium sulfonate.
More preferably, the fluorosulfonate-based flame retardant is potassium perfluorobutylsulfonate, potassium perfluorooctanesulfonate, or tetraethylammonium perfluoroethanesulfonate.
More preferably, the carbonate flame retardant is one or more of sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate or barium carbonate.
More preferably, the flame retardant is one or both of potassium sulfonate and potassium perfluorobutylsulfonate.
Preferably, the weight fraction of the phosphite stabilizer in the composite stabilizer is 72-83%.
Preferably, the phosphite based thermal stabilizer is one or more of tetrakis (2, 4-di-tert-butylphenol) 4,4' -biphenyldiphosphite, distearylpentaerythritol diphosphite or bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
More preferably, the phosphite based thermal stabilizer is one or more of PEPQ, 568 or 9228.
Preferably, the mass fraction of phosphoric acid in the phosphoric acid aqueous solution is 20-35%. More preferably 30%.
Preferably, the anti-drip agent is a fluoropolymer, which may comprise a fibrillated or non-fibrillated fluoropolymer, more preferably fibrillated or non-fibrillated Polytetrafluoroethylene (PTFE).
Preferably, the other auxiliary agent is one or more of hindered phenol antioxidant, pentaerythritol stearate (or toner).
More preferably, the weight fraction of the hindered phenol antioxidant in the flame-retardant polycarbonate alloy composition is 0.01-2%.
More preferably, the flame-retardant polycarbonate alloy composition contains 0.1-2% of pentaerythritol stearate by weight.
More preferably, the weight fraction of the toner in the flame-retardant polycarbonate alloy composition is 0.001-10%. The preparation method of the flame-retardant polycarbonate alloy composition with high thermal stability comprises the steps of mixing the polycarbonate flame retardant, the composite stabilizer, the anti-dripping agent and other auxiliaries, carrying out melt extrusion, and granulating to obtain the flame-retardant polycarbonate alloy composition with high thermal stability.
Preferably, the preparation method of the flame retardant polycarbonate alloy composition with high thermal stability comprises the following steps: and stirring and mixing the polycarbonate, the flame retardant, the composite stabilizer, the anti-dripping agent and other auxiliaries in a high-speed mixer, then carrying out melt extrusion in a double-screw extruder, and granulating to obtain the high-heat-stability flame-retardant polycarbonate alloy composition.
More preferably, the rotating speed of stirring and mixing is 20-50 revolutions/min; the length-diameter ratio of the double-screw extruder is 38-52: 1, the temperature of a screw cylinder is 220-260 ℃, and the rotating speed of a screw is 300-600 revolutions per mm.
The application of the high-heat-stability flame-retardant polycarbonate alloy composition in the preparation of electronic products, communication products and new energy products is also within the protection scope of the invention.
In particular, it can be applied to a housing material such as an adapter, a power supply, and the like.
Compared with the prior art, the invention has the following beneficial effects:
the flame-retardant polycarbonate alloy composition provided by the invention takes polycarbonate, even polycarbonate recovered in a large proportion as a resin system, and improves heat resistance, batch stability and stable flame retardance through the synergistic cooperation of a flame retardant and a composite stabilizer; the flame-retardant polycarbonate alloy composition with high thermal stability provided by the invention has the grade of stable flame retardance of 3.0mm and 5VA, the boiling flame-retardant stability is maintained to be 5VA, the thermal degradation activation energy is more than 200J/mol, the thermal stability is good, the performances of 3 batches are basically kept consistent, and the flame-retardant polycarbonate alloy composition can be widely applied to the fields of electronic products, communication products, new energy products and the like.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are those commercially available from conventional markets and the like unless otherwise specified. Any insubstantial changes from the invention, including those variations and alterations made by those skilled in the art, are intended to be covered by the claims.
Some of the reagents selected in the examples and comparative examples of the present invention are described below:
and the recovered polycarbonate 1# is recovered from a drinking water barrel after consumption and is treated as follows: carrying out physical recovery processes such as polishing, cleaning, drying, crushing, granulating, sieving, magnetizing and the like after physical mechanical classification to obtain recovered PC resin particles; a physically recycled resin grade having a melt index MI of 7.3g/10min at 300 ℃/1.2kg and a 25% increase in MI hot-retention according to ISO1133-2011 standard, a light transmittance of 81.7% at a wavelength of 500nm at a thickness of 2.0 mm; the weight average molecular weight is 53000;
and 2, recovering the polycarbonate 2# from the consumed plate, and performing the following treatment: carrying out physical recovery processes such as polishing, cleaning, drying, crushing, granulating, sieving, magnetizing and the like after physical mechanical classification to obtain recovered PC resin particles; a physically recycled resin grade having a melt index MI of 26.7g/10min at 300 ℃/1.2kg according to ISO1133-2011, a MI heat retention rise of 34%, a light transmittance at 2.0mm thickness and 500nm wavelength of 81.7%; the weight average molecular weight is 48000;
new material polycarbonate No. 1, S-2000F, Shanghai Mitsubishi, weight average molecular weight 58000, terminal hydroxyl group content 13ppm, BPA content 8ppm, phosgene method preparation get;
2# new material polycarbonate, BR-111, lihuayi, with a weight average molecular weight of 52000, a terminal hydroxyl group content of 108ppm and a BPA content of 23ppm, prepared by an ester exchange method;
flame retardant # 1, KSS (sulfonate salts), Arichem;
flame retardant # 2, TPP (phosphorus), adeka;
1# composite stabilizer, 30% phosphoric acid aqueous solution and 1# phosphite ester stabilizer, wherein the weight fraction of 1# phosphite ester stabilizer is 80%;
2# composite stabilizer, 30% phosphoric acid aqueous solution and 1# phosphite ester stabilizer, wherein the weight fraction of 1# phosphite ester stabilizer is 60%;
3# composite stabilizer, 30% phosphoric acid aqueous solution and 1# phosphite ester stabilizer, wherein the weight fraction of the 1# phosphite ester stabilizer is 85%;
compound stabilizer No. 4, a mixture of 20% phosphoric acid aqueous solution and phosphite ester stabilizer No. 1, wherein the weight fraction of phosphite ester stabilizer No. 2 is 80%;
5# composite stabilizer, 35% phosphoric acid aqueous solution and 1# phosphite ester stabilizer, wherein the weight fraction of the 1# phosphite ester stabilizer is 80%;
composite stabilizer No. 6, 30% phosphoric acid water solution and thiol stabilizer, the weight fraction of thiol stabilizer is 80%;
phosphite stabilizer # 1, PEPQ, clariant;
phosphite stabilizer # 2, S9228, clariant;
thiol stabilizers, 412S, linaloon;
a phosphoric acid aqueous solution which is obtained by diluting with concentrated phosphoric acid, and the weight fractions are 20%, 30% and 35%;
anti-drip agent, TS-30A, Korean Pacific;
other auxiliaries, antioxidant 1076, BASF.
The flame-retardant polycarbonate alloy compositions provided by the embodiments of the invention and the comparative examples are subjected to performance measurement according to the following test methods:
flame retardant rating: the flammability test was carried out according to the protocol "flammability test of plastic materials, UL 94". The flame rating is derived based on the burn rate, the extinguishing time, the ability to resist droops, and whether the droops are burning. Samples used for the test: 125mm length 13mm width, the thickness of the invention when tested is selected to be 1.0mm, and the flame retardant rating of the material can be classified as (UL94-HB) according to the UL94 protocol: judgment of V0, V1, V2, 5VA and/or 5VB as initial flame retardant grade;
water boiling flame retardant rating: the flame retardant rating of the adjusting treatment is that after the test sample strip is placed in a constant-temperature water bath box at 82 ℃ and boiled for 168 hours at constant temperature, the test sample strip is adjusted for 48 hours under the conditions of 25 ℃ and 50 percent of humidity, and the flame retardant rating of the material can be classified into (UL94-HB) according to the UL94 specification: judging the flame retardant grade after adjustment by using V0, V1, V2, 5VA and/or 5 VB;
thermal degradation activation energy: weighing 8 +/-1 mg of sample to be detected, setting the heating rates to be 5 ℃/min, 10 ℃/min, 15 ℃ min and 20 ℃/min respectively, fixing the temperature and the temperature to be detected in a nitrogen atmosphere, obtaining a TGA curve, and then obtaining the TGA curve according to an Arrhenius formula
(where A is a frequency factor, E is activation energy, and R is a gas constant), wherein a larger activation energy indicates a better thermal stability of the material.
3, batch stability: the stability between batches is characterized by measuring the thermal degradation activation energy of three batches of samples and representing the stability between batches by the variation coefficient CV value of the probability distribution discrete degree, which is defined as the ratio of standard deviation to average value, wherein the CV value of less than 5 percent is excellent in stability between batches, the CV value of 5 to 8 percent (including 5 percent but not 8 percent) is good in stability between batches, the CV value of 8 to 10 percent (including 8 percent but not 10 percent) is general in stability between batches, and the CV value of more than or equal to 10 percent is unstable between batches. In addition, the average value of the thermal degradation activation energy of three batches of samples was taken as the thermal degradation activation energy value of the sample.
The preparation process of the polycarbonate alloy compositions of the examples and comparative examples of the present invention is as follows: weighing the components according to the proportion, adding the components into a high-speed mixer, stirring and blending to obtain a premix, then extruding, and performing a melting granulation process to obtain the polycarbonate alloy composition. Wherein the stirring speed is 40 r/min, the length-diameter ratio of the double-screw extruder is 40:1, the temperature of the screw cylinder is 240 ℃, and the screw rotating speed is 350 r/min.
Examples 1 to 13
This example provides a series of highly thermally stable flame retardant polycarbonate alloy compositions having the formulation shown in Table 1.
TABLE 1 formulation of the high thermal stability flame retardant polycarbonate alloy compositions provided in examples 1 to 5 (parts)
TABLE 2 formulation of the stable flame retardant polycarbonate alloy compositions provided in examples 6-13 (parts)
Comparative examples 1 to 4
This comparative example provides a series of flame retardant polycarbonate alloy compositions having the formulation shown in Table 2.
TABLE 3 Components (parts) of flame retardant polycarbonate alloy compositions provided in comparative examples 1 to 4
The properties of the flame retardant polycarbonate alloy compositions of the respective examples and comparative examples were measured according to the above-mentioned test methods, and the test results are shown in Table 4.
TABLE 4 Performance test results of the flame retardant polycarbonate alloy compositions of the examples and comparative examples
As can be seen from table 4, the recycled polycarbonate in the flame retardant polycarbonate alloy composition provided in the embodiments of the present invention has a very high ratio (60% or more of the total polycarbonate used), and has excellent toughness, stable flame retardant performance, higher activation energy for thermal degradation and better stability: the flame retardant grade is 5VA grade (3.0mm), the water boiling is still kept as 5VA grade, the thermal degradation activation energy is more than 200J/mol, the thermal stability is good, the performances of 3 batches are basically kept consistent, and the comprehensive performance of the example 1 is the best; comparative example 1 does not perform stability modification treatment on a resin system, although initial flame retardance is not affected and can reach 5VA grade, the initial flame retardance is reduced to 5VB after water boiling, high flame retardance cannot be maintained, batch-to-batch volatility is large, pyrolysis activation energy is low, performance is far inferior to that of example 1, and certain use limitation is realized; the composite stabilizer added in the comparative example 2 is compounded by using a thiol stabilizer, and compared with the comparative example 1, although the pyrolysis activation energy is increased, the sufficient stability of a resin system cannot be provided due to insufficient free radical capture capacity, and meanwhile, the 5VA grade target cannot be realized due to negative influence on initial high flame retardance; comparative example 3 only phosphoric acid aqueous solution was added as a stabilizer, acidic hydrolysis of PC resin was caused due to synergy of the structure without phosphite, 5VA could not be achieved due to dripping and the pyrolysis temperature was sharply reduced, the batch stability was insufficient; comparative example 4 only phosphite stabilizer was added, initial flame retardant performance could reach 5VA, but pyrolysis activation energy was reduced, stability between batches was insufficient, and flame retardant rating could not be maintained after poaching.
It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art, having the benefit of this disclosure, may effect numerous modifications thereto and changes may be made without departing from the scope of the invention in its aspects.
Claims (7)
1. The flame-retardant polycarbonate alloy composition with high thermal stability is characterized by comprising the following components in parts by weight:
100 parts of polycarbonate (A), 100 parts of polycarbonate (B),
0.1 to 8.5 parts of a flame retardant,
0.1 to 3.5 parts of composite stabilizer,
0.001-10 parts of anti-dripping agent,
0-10 parts of other auxiliary agents;
the composite stabilizer is a mixture of a phosphite heat stabilizer and a phosphoric acid aqueous solution, and the weight fraction of the phosphite stabilizer in the composite stabilizer is 60-85%;
the polycarbonate comprises recovered polycarbonate and new polycarbonate, and the weight fraction of the recovered polycarbonate in the polycarbonate is 60-100%;
the flame retardant is a sulfonate flame retardant;
the phosphite ester heat stabilizer is one or more of tetra (2, 4-di-tert-butylphenol) 4,4' -biphenyl diphosphite, distearyl pentaerythritol diphosphite or bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
2. The high thermal stability flame retardant polycarbonate alloy composition of claim 1, comprising the following components in parts by weight:
100 parts of polycarbonate (A), 100 parts of polycarbonate (B),
0.2 to 8 parts of a flame retardant,
0.12 to 3 parts of a composite stabilizer,
0.1 to 5 parts of anti-dripping agent,
0.1-8 parts of other additives.
3. The highly thermally stable, flame retardant polycarbonate alloy composition of claim 1, wherein said recycled polycarbonate has a melt index MI of no greater than 10g/10min at 300 ℃/1.2kg, an MI hot-retention increase of no greater than 40% polycarbonate, and a light transmittance at 2.0mm of no less than 75%, according to ISO 1133-2011; the weight average molecular weight of the new polycarbonate is 32000-63000, the content of terminal hydroxyl is less than 100ppm, and the content of BPA is less than 20 ppm.
4. The highly thermally stable, flame retardant polycarbonate alloy composition of claim 1, wherein the weight fraction of the phosphite based stabilizer in the composite stabilizer is 72-83%.
5. The highly thermally stable, flame retardant polycarbonate alloy composition of claim 1, wherein the phosphoric acid in the aqueous phosphoric acid solution is present in an amount of 20 to 35% by weight.
6. The method for preparing a highly thermally stable flame retardant polycarbonate alloy composition as defined in any one of claims 1 to 5, comprising the steps of: and mixing the polycarbonate, the flame retardant, the composite stabilizer, the anti-dripping agent and other auxiliaries, melting, extruding and granulating to obtain the flame-retardant polycarbonate alloy composition with high thermal stability.
7. Use of the highly thermally stable flame retardant polycarbonate alloy composition of any of claims 1 to 5 in the preparation of electronic products, communication products, and new energy products.
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| CN115304900B (en) * | 2022-07-25 | 2023-11-10 | 宁波坚锋新材料有限公司 | Flame-retardant regenerated polycarbonate material and preparation method thereof |
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| DE69522852T2 (en) * | 1994-05-19 | 2002-05-02 | Gen Electric | stabilizer composition |
| US6066694A (en) * | 1998-03-04 | 2000-05-23 | General Electric Company | Polyester molding composition |
| JP4750960B2 (en) * | 2001-03-15 | 2011-08-17 | 帝人株式会社 | Thermoplastic resin composition |
| US20040127653A1 (en) * | 2002-08-30 | 2004-07-01 | General Electric Company | Polycarbonate/polyester copolymer blends and process for making thereof |
| CN106084718A (en) * | 2016-06-14 | 2016-11-09 | 江苏金发科技新材料有限公司 | High-temp resistant fire-retarding polycarbonate compositions and preparation method thereof |
| CN112513157A (en) * | 2018-07-31 | 2021-03-16 | 沙特基础工业全球技术有限公司 | Copolycarbonate compositions and articles |
| CN110746756B (en) * | 2019-09-18 | 2021-08-20 | 金发科技股份有限公司 | Flame-retardant polycarbonate composite material and preparation method thereof |
| CN112745651B (en) * | 2020-12-15 | 2022-05-20 | 金发科技股份有限公司 | Flame-retardant polycarbonate composition and preparation method and application thereof |
| CN112724629B (en) * | 2020-12-15 | 2022-05-20 | 金发科技股份有限公司 | Polycarbonate composition and preparation method and application thereof |
| CN113637309B (en) * | 2021-08-17 | 2022-08-19 | 金发科技股份有限公司 | Flame-retardant polycarbonate alloy composition with high thermal stability and preparation method and application thereof |
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