CN116285283B - Halogen-free flame retardant material and preparation method thereof - Google Patents

Halogen-free flame retardant material and preparation method thereof Download PDF

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CN116285283B
CN116285283B CN202211674673.6A CN202211674673A CN116285283B CN 116285283 B CN116285283 B CN 116285283B CN 202211674673 A CN202211674673 A CN 202211674673A CN 116285283 B CN116285283 B CN 116285283B
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parts
flame retardant
resin
pmma
surlyn
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CN116285283A (en
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梁伟成
康妉传
柏莲桂
文听雷
杨俊�
吕晓飞
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Sinochem Engineering Plastics Yangzhou Co ltd
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Sinochem Engineering Plastics Yangzhou Co ltd
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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
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a halogen-free flame retardant material, which comprises the following raw materials in parts by weight: 100 parts of PC; 5-10 parts of silicon PC; 10-20 parts of PA; 20-40 parts of transparent ABS; 40-50 parts of Surlyn; 20-40 parts of PMMA; 5-10 parts of ASA rubber powder; 1-5 parts of POSS resin; 5-15 parts of melamine polyphosphate; 3-8 parts of liquid phosphate flame retardant. According to the invention, through the synergistic effect of the components, the difference of viscosity and the steric hindrance repulsive effect are utilized, the PC resin is more easily melted and flows to the surface of the workpiece in injection molding, the PC resin is more left in the workpiece, the surface layers of PMMA and surlyn resin are formed on the outer layer, the PMMA and surlyn resin directly face the external environment, and the overall weather resistance of the material is improved by utilizing the excellent weather resistance of the PC resin; the possibility that various small molecules and light rays in the external environment permeate into the material is reduced, and the weather resistance is improved.

Description

Halogen-free flame retardant material and preparation method thereof
Technical Field
The invention relates to the technical field of materials, in particular to a halogen-free flame retardant material and a preparation method thereof.
Background
PC has better heat resistance, impact strength and tensile strength, ABS has good processability and dyeing property, PC/ABS alloy can be obtained by blending, the PC/ABS alloy can be complementary in performance, the alloy can have good properties of both PC and ABS, the PC/ABS alloy has good mechanical properties and good processability, the internal stress of the finished product is low, the sensitivity of the impact strength to the thickness of the product is reduced, the cracking probability of the product is greatly reduced, and the PC/ABS alloy is widely favored.
With the increasing application proportion of electronic and electric devices, the electronic and electric devices go deep into the aspects of life and work and new energy vehicles which are developed greatly in recent years, the popularization degree is higher and the risk of fire is also increased, so that the fireproof and flame-retardant requirements for material application go deep into the heart, especially the 21 st century, the environment-friendly pressure-maintaining capacity is unprecedented and the debate of halogen-based flame-retardant materials is becoming increasingly white, the proportion of halogen-free flame-retardant materials is increasing, PC/ABS materials belong to inflammable materials, the application amount and application range of the PC/ABS materials are increased, and the PC/ABS alloy is widely applied in the aspects of automobiles, household appliances, computers, communication, offices and the like in recent years, so that potential safety hazards caused by fire burial are prevented, and in order to reduce the occurrence of fire and improve the national fireproof safety, more and more application fields are popularizing halogen-free flame-retardant PC/ABS materials, and high-performance halogen-free flame-retardant PCABS is receiving wide attention.
The prior art discloses several patents on halogen-free flame retardant PCABS: chinese patent 112679932B discloses an antibacterial halogen-free flame-retardant PC/ABS composite material with high ball pressure temperature, which mainly comprises the following components in parts by weight: 59-88 parts of PC, 5-20 parts of ABS, 4-12 parts of organic phosphorus flame retardant, 2-5 parts of flexibilizer, 0.4-1 part of antibacterial agent, 0.2-0.5 part of anti-dripping agent, 0.2-1 part of dispersing agent and 0.2-1 part of antioxidant, and has good antibacterial performance, high ball pressure resistance temperature and good flame retardance, but the addition of more organic phosphorus flame retardant leads to insufficient heat resistance and poor weather resistance. Chinese patent 115011097A discloses a high-rigidity flame-retardant PC/ABS composite material, which comprises PC, ABS, glass fiber, flame retardant, toughening agent, stress cracking resistant agent, black master batch, antioxidant and dispersing agent, and the balance of silane modifier, styrene-acrylic emulsion, foaming agent and residual dose of defoaming agent after drying, and belongs to a high-rigidity high-toughness halogen-free flame-retardant V0-grade high-performance composite material.
Therefore, it is necessary to provide a low density, high heat resistant, weather resistant halogen free flame retardant PC/ABS material.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a halogen-free flame retardant material which has low density, high heat resistance and good weather resistance.
The invention provides a halogen-free flame retardant material which comprises the following raw materials in parts by weight:
Preferably, the material comprises the following raw materials in parts by weight:
Preferably, the PC is bisphenol A type PC, the melt index is 5g/10 min-10 g/10min, and the test condition is 300 ℃ 1.2kg;
The siloxane PC is polysiloxane-polycarbonate copolymer, the melt index is 30g/10min-40g/10min, and the test condition is 300 ℃ which is 1.2kg;
The melt index of the transparent ABS is 22g/10 min-35 g/10min, and the test condition is 220 ℃ 10kg;
The melt index of PMMA is 35g/10 min-45 g/10min, and the test condition is 230 ℃ which is 3.8kg.
Preferably, the PA resin is PA4T;
The POSS resin is dimethylsilyl cage-shaped polysilsesquioxane.
Preferably, the glue content of the ASA glue powder is more than or equal to 55 percent.
Preferably, the particle size of the melamine polyphosphate is less than or equal to 40 mu m.
Preferably, the liquid phosphate flame retardant is 2-ethylhexyl diphenyl phosphate.
Preferably, the Surlyn vicat softening point is greater than 75 ℃.
The invention provides a preparation method of a halogen-free flame retardant material, which comprises the following steps:
A) Mixing PC, silicon PC, transparent ABS, surlyn resin, PMMA and ASA rubber powder to obtain a first mixture;
B) Mixing PA, melamine polyphosphate and POSS resin to obtain a second mixture;
C) Adding the first mixture from a main feeding port of a double-screw extruder, adding the second mixture from a side feeding port of a fifth section of the extruder, adding the liquid phosphate flame retardant into the extruder from a sixth section of the extruder by a liquid scale through a liquid pump, extruding, and granulating to obtain the flame retardant.
Preferably, the temperature of the extruder at the 1-4 sections is set to 260 ℃, the temperature from the fifth section to the machine head is 325 ℃, the temperature in the liquid scale is 100 ℃, and the rotating speed is controlled to be 500-600 r/min.
Compared with the prior art, the invention provides a halogen-free flame retardant material, which comprises the following raw materials in parts by weight: 100 parts of PC; 5-10 parts of silicon PC; 10-20 parts of PA; 20-40 parts of transparent ABS; 40-50 parts of Surlyn; 20-40 parts of PMMA; 5-10 parts of ASA rubber powder; 1-5 parts of POSS resin; 5-15 parts of melamine polyphosphate; 3-8 parts of liquid phosphate flame retardant. According to the invention, through the synergistic effect of the components, the difference of viscosity and the steric hindrance repulsive effect are utilized, the PC resin is more easily melted and flowed to the surface of the workpiece in injection molding, the PC resin is more left in the workpiece, the surface layers of PMMA and surlyn resin are formed on the outer layer, the PMMA and surlyn resin directly face the external environment, and the overall weather resistance of the material is improved by utilizing the excellent weather resistance of the PC resin and the PMMA; secondly, on one hand, the possibility that various small molecules and light rays in the external environment penetrate into the material is reduced, so that the weather resistance is improved, and on the other hand, the heat resistance of the material is improved. Meanwhile, the material can be well organically combined, the dispersibility is better under the high-flow holding, and the flame retardant efficiency of the flame retardant is improved.
Detailed Description
The invention provides a halogen-free flame retardant material and a preparation method thereof, and the technical parameters can be properly improved by the technicians in the field with reference to the content of the invention. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and they are intended to be within the scope of the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the invention can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the invention.
The invention provides a halogen-free flame retardant material which comprises the following raw materials in parts by weight:
The invention provides a halogen-free flame retardant material, which comprises 100 parts by weight of PC. The PC is bisphenol A type PC, the melt index is 5g/10 min-10 g/10min, and the test condition is 300 ℃ which is 1.2kg;
The invention provides a halogen-free flame retardant material, which comprises 5-10 parts by weight of silicon PC; preferably comprising 5 to 9 parts by weight of silicon PC.
The silicon PC is siloxane PC, namely polysiloxane-polycarbonate copolymer, the melt index is 30g/10min-40g/10min, the test condition is 300 ℃ which is 1.2kg, such as SABIC PC EXL1890T, and the melt index is 35g/10min.
The invention provides a halogen-free flame retardant material, which comprises 10-20 parts by weight of PA; preferably comprising PA11 to 19 parts by weight. The PA resin is PA4T, such as Dissmann PA4T E11.
The invention provides a halogen-free flame retardant material, which comprises 20-40 parts by weight of transparent ABS; preferably comprises 21 to 38 parts by weight of transparent ABS; more preferably, the transparent ABS is included in an amount of 21 to 35 parts by weight; and most preferably comprises 21 to 32 parts by weight of transparent ABS.
The transparent ABS melt index is 22g/10 min-35 g/10min, and the test condition is 220 ℃ which is 10kg, such as LG MABS TR558A, and the melt index is 25g/10min.
The invention provides a halogen-free flame-retardant material, which comprises 40-50 parts by weight of Surlyn; more preferably, surlyn is included in an amount of 42 to 48 parts by weight; 43 to 47 parts by weight of Surlyn.
The Surlyn disclosed by the invention has a Vicat softening point of more than 75 ℃ (test standard ISO306, B50) such as Dupont Surlyn EMAA9950, and the Vicat softening point (B50) is 79 ℃.
The invention provides a halogen-free flame-retardant material, which comprises 20-40 parts by weight of PMMA; preferably, the PMMA is included in an amount of 21 to 38 parts by weight; more preferably, it comprises PMMA 21-36 parts by weight; more preferably, it comprises PMMA21 to 33 parts by weight.
The PMMA has a melt index of 35g/10 min-45 g/10min, and the test condition is 230 ℃ which is 3.8kg, such as PLASKOLITE company CA-42, and the melt index is 40g/10min.
The invention provides a halogen-free flame-retardant material, which comprises 5-10 parts by weight of ASA rubber powder; preferably comprises 6 to 9 weight parts of ASA rubber powder; more preferably 6 to 8 parts by weight.
The ASA rubber powder has a rubber content of 55% or more, such as UMGA600N ASA rubber powder with 60 percent of rubber content.
The invention provides a halogen-free flame retardant material, which comprises 1-5 parts by weight of POSS resin; more preferably, 2 to 5 parts of POSS resin is included. The POSS resin is preferably dimethylsilyl cage polysilsesquioxane.
The invention provides a halogen-free flame-retardant material, which comprises 5-15 parts by weight of melamine polyphosphate; more preferably, comprises 5 to 13 parts by weight of melamine polyphosphate; most preferably, it comprises 5 to 11 parts by weight of melamine polyphosphate. The particle size of the melamine polyphosphate is less than or equal to 40 mu m.
The invention provides a halogen-free flame retardant material, which comprises 3-8 parts by weight of liquid phosphate flame retardant; preferably, it comprises 4 to 8 parts by weight. The liquid phosphate flame retardant is 2-ethylhexyl diphenyl phosphate.
In a part of the preferred embodiment of the invention, the raw materials comprise the following parts by weight:
In order to realize excellent weather resistance of the flame-retardant PC/ABS, the invention adds high-flow PMMA and Surlyn resin, and adopts low-flow PC as matrix resin. Because PMMA material weather resistance is good, surlyn is an ethylene-methacrylic acid copolymer, surlyn resin and PMMA all contain methacrylic acid structure, have good compatibility, the ethylene chain segment in surlyn provides extremely good fluidity, further improve PMMA's mobility, but they all have certain steric hindrance with PC, surlyn resin can form the whole with high-flow PMMA in the process of moulding plastics, utilize the difference of viscosity, and steric hindrance repulsive effect, the higher priority melt flow of injection moulding is to the surface of finished piece, more PC resin is left in the finished piece, form PMMA and surlyn resin's top layer in the skin, directly face external environment, utilize their extremely good weather resistance to improve material overall weather resistance, in order to prevent surlyn to process the degradation at high temperature, therefore adopted the surlyn resin that heat-resisting is relatively high, and surlyn density is only 0.93-0.94g/cm 3, greatly reduced material's density.
In order to realize weather resistance and high heat resistance of the flame-retardant PC/ABS material, the PA4T is added, on one hand, the PA4T has excellent heat resistance, the PA4T is flame-retardant, the consumption of flame retardant is reduced, the heat resistance of the flame-retardant material is counteracted to be reduced due to the addition of the liquid flame retardant and the ABS, on the other hand, the PA4T has a plurality of hydrogen bonds, the crystallization speed is extremely high, the flame-retardant PC/ABS material is dispersed in the resin, the whole molecular chain distance of the material is pulled to be closer under the action of the hydrogen bonds, the structure is more compact, on the one hand, the possibility that various small molecules and light rays in the external environment penetrate into the material is reduced, so that the weather resistance is improved, and on the other hand, the heat resistance of the material is improved.
The flame-retardant PC/ABS material adopts high-flow transparent ABS, which is a copolymer of methyl methacrylate, acrylonitrile, butadiene and styrene (MABS), and ASA rubber powder is used for toughening, so that the ASA rubber powder has improved weather resistance, and meanwhile, because the MABS contains methyl methacrylate, PMMA and Surlyn, and both the ASA rubber powder and PC have good compatibility, the binding force between resins is increased, the heat resistance of the whole material is improved, and meanwhile, the weather resistance exerted by PMMA and Surlyn in the beneficial effect (1) is further improved, and the MABS adopts high-flow MABS, so that the MABS can be better dispersed in the material during blending, plays a bridge role, and connects the whole material body into a whole.
In order to realize high-efficiency flame retardance of the material, the high-flow type silicon PC is adopted, on one hand, the compatibility with the matrix resin PC is excellent, and on the other hand, the high-flow type silicon PC contains siloxane, so that the high-efficiency flame retardant has good compatibility with the dimethylsilyl cage-shaped polysilsesquioxane, and the dimethylsilyl cage-shaped polysilsesquioxane can be well combined with the 2-ethylhexyl diphenyl phosphate due to the existence of methyl, so that the material can be well organically combined, the dispersibility is better under the high-flow holding condition, and the flame retardant efficiency of the flame retardant is improved.
The invention provides a preparation method of a halogen-free flame retardant material, which comprises the following steps:
A) Mixing PC, silicon PC, transparent ABS, surlyn resin, PMMA and ASA rubber powder to obtain a first mixture;
B) Mixing PA, melamine polyphosphate and POSS resin to obtain a second mixture;
C) Adding the first mixture from a main feeding port of a double-screw extruder, adding the second mixture from a side feeding port of a fifth section of the extruder, adding the liquid phosphate flame retardant into the extruder from a sixth section of the extruder by a liquid scale through a liquid pump, extruding, and granulating to obtain the flame retardant.
The present invention has been described in detail with reference to the above components and proportions, and will not be described in detail herein.
The invention provides a preparation method of a halogen-free flame retardant material, which is characterized in that PC, silicon PC, transparent ABS, surlyn resin, PMMA and ASA rubber powder are mixed to obtain a first mixture. The mixing time is preferably 1h; more preferably in a high-speed mixer.
PA, melamine polyphosphate and POSS resin are mixed to give a second mixture. The mixing time is preferably 1h; more preferably in a high-speed mixer.
Adding the first mixture from a main feeding port of a double-screw extruder, adding the second mixture from a side feeding port of a fifth section of the extruder, adding the liquid phosphate flame retardant into the extruder from a sixth section of the extruder by a liquid scale through a liquid pump, extruding, and granulating to obtain the flame retardant.
Specifically, the temperature of the extruder at the 1-4 sections is set to 260 ℃, the temperature from the fifth section to the machine head is 325 ℃, the temperature in the liquid scale is 100 ℃, and the rotating speed is controlled to be 500-600 r/min.
The flame-retardant PC/ABS material has the advantages of light weight, good weather resistance and excellent flame retardant property, and can reach the V0 level of 0.8mm and simultaneously has excellent processing property.
In order to realize high-efficiency flame retardance of the material, melamine polyphosphate, dimethylsilyl cage-shaped polysilsesquioxane and PA4T are mixed and then added from a side feed, so that on one hand, the residence time of the flame retardant in a screw is reduced, the probability of decomposition of the flame retardant is reduced, the melamine polyphosphate and PA4T have better synergistic flame retardant effect, on the other hand, small-particle-size melamine polyphosphate and dimethylsilyl cage-shaped polysilsesquioxane are mixed, so that powder can permeate into a cage-shaped structure to form a wrapped network structure, on the one hand, the cage-shaped resin can form a carbon layer to isolate air, and meanwhile, resin is prevented from dripping, on the other hand, the dimethylsilyl cage-shaped polysilsesquioxane contains oxygen elements to better help the melamine polyphosphate to be decomposed into phosphoric acid by heating quickly, and then the phosphoric acid is synthesized to form a carbon layer, so that the air is isolated, and the flame retardant efficiency is greatly improved.
The invention adopts ethylhexyl diphenyl phosphate as a flame retardant with relatively low density (1.1+/-0.1 g/cm 3), can better realize low density, has good compatibility with surlyn resin (ethylene-methacrylic acid copolymer) due to the existence of ethyl, increases the binding force in the whole material, improves the flame retardant efficiency, and has benefits on weather resistance and heat resistance.
Particularly emphasized is that: the low density is based on heat resistance, PCABS material is used as the main body, and the flame retardant PCABS with Vicat B above 108 ℃ usually needs to be added with more than 75 percent of PC (density 1.2), the density is higher than 1.18g/cm 3, namely, the higher the PC content is, the better the heat resistance and flame retardance are, but the higher the density is, the PC density in PCABS is 1.2, the ABS is 1.04, namely, the PC/ABS material density is basically between 1.2 and 1.04, and the impossible lower PC/ABS material density is less than 1.04, so the drop gap is not too large. The ABS is more required to be low-density, the ABS affects heat resistance and flame retardance, flame retardance and no halogen cannot be 0.8V0, and Vicat is also poor, so that the invention can realize low-density and obvious progress, and is realized on the basis of ensuring heat resistance and flame retardance.
In order to further illustrate the present invention, the following describes in detail a halogen-free flame retardant material and a preparation method thereof according to examples.
In the method of the invention, the density of the material is measured according to ISO 1183-1 by adopting a drainage method. The heat resistance is characterized by Vicat softening point, the test method is measured according to ISO 306, B50, the weather resistance is expressed by reference standard SAE J1885, the color change delta E of the material is measured after 600KJ/m2 irradiation, and the flame retardance is judged according to UL94 vertical burning method and the flame retardance under a 0.8mm thickness sample.
Example 1
The low-density, high-heat-resistance and weather-proof halogen-free flame-retardant PC/ABS material comprises the following components in parts by weight:
the preparation method comprises the following steps:
a. and mixing PC, silicon PC, transparent ABS, surlyn resin, PMMA and ASA rubber powder in a high-speed mixer for 1 hour for later use.
B. PA, melamine polyphosphate and POSS resin were mixed in a high-speed mixer for 1 hour and then ready for use.
C. B, adding the raw material obtained in the step a from a main feeding port of a double-screw extruder, and adding the raw material obtained in the step b from a side feeding port of a fifth section of the extruder; the liquid phosphate flame retardant was fed from the liquid scale to the extruder through a liquid pump from the sixth stage of the extruder. Setting the temperature of the extruder at 260 ℃ in the 1-4 sections, setting the temperature of the extruder head at 325 ℃ from the fifth section, setting the temperature in a liquid scale at 100 ℃, controlling the rotating speed at 500-600r/min, and carrying out extrusion granulation.
Through testing, the performance parameters are as follows: the density is as follows: 1.13g/cm3 (ISO 1183-1), flame retardant properties of 0.8mm V0 (UL 94), vicat softening point 128 ℃ (ISO 306, B50), ΔE after energy irradiation of 1.2 (SAE J1885).
Example 2
The low-density, high-heat-resistance and weather-proof halogen-free flame-retardant PC/ABS material comprises the following components in parts by weight:
The specific preparation method is the same as in example 1
Through testing, the performance parameters are as follows: the density is as follows: 1.14g/cm3 (ISO 1183-1), flame retardant properties of 0.8mm V0 (UL 94), vicat softening point 125 ℃ (ISO 306, B50), ΔE after energy irradiation of 1.1 (SAE J1885).
Example 3
The low-density, high-heat-resistance and weather-proof halogen-free flame-retardant PC/ABS material comprises the following components in parts by weight:
The specific preparation method is the same as in example 1
Through testing, the performance parameters are as follows: the density is as follows: 1.12g/cm3 (ISO 1183-1), flame retardant properties of 0.8mm V0 (UL 94), vicat softening point 122 ℃ (ISO 306, B50), ΔE after energy irradiation of 1.2 (SAE J1885).
Example 4
The low-density, high-heat-resistance and weather-proof halogen-free flame-retardant PC/ABS material comprises the following components in parts by weight:
The specific preparation method is the same as in example 1
Through testing, the performance parameters are as follows: the density is as follows: 1.15g/cm3 (ISO 1183-1), flame retardant performance 0.8mm V0 (UL 94), vicat softening point 127 ℃ (ISO 306, B50), ΔE after energy irradiation 1.4 (SAE J1885).
Example 5
The low-density, high-heat-resistance and weather-proof halogen-free flame-retardant PC/ABS material comprises the following components in parts by weight:
The specific preparation method is the same as in example 1
Through testing, the performance parameters are as follows: the density is as follows: 1.14g/cm3 (ISO 1183-1), flame retardant performance 0.8mm V0 (UL 94), vicat softening point 129 ℃ (ISO 306, B50), ΔE after energy irradiation 1.1 (SAE J1885).
Comparative example 1
The low-density, high-heat-resistance and weather-proof halogen-free flame-retardant PC/ABS material comprises the following components in parts by weight:
Comparative example 1 was otherwise unchanged, lacking surlyn resin, and consistent with the specific preparation method, as compared to example 1.
Through testing, the performance parameters are as follows: the density is as follows: 1.19g/cm3 (ISO 1183-1), flame retardant properties of 0.8mm V1 (UL 94), vicat softening point 120 ℃ (ISO 306, B50), ΔE after energy irradiation of 2.0 (SAE J1885).
Comparative example 1, in comparison with example 1, lacks Surlyn resin, and on the other hand lacks synergy of Surlyn and PMMA, fails to provide excellent flowability by using the ethylene segment in Surlyn, and thus fails to further utilize the ultra-high flowability of the system consisting of PMMA and Surlyn, which is unfavorable for migration of PMMA resin to the surface, and thus the weatherability of the material is lowered, resulting in an increase in Δe.
Comparative example 2
The low-density, high-heat-resistance and weather-proof halogen-free flame-retardant PC/ABS material comprises the following components in parts by weight:
Comparative example 2 was otherwise identical to example 1 except that low melt PMMA was used, with the preparation being consistent with the preparation of the Xudi-formed PMMA 80N melt at 2g/10min (230 ℃ C. 3.8 kg).
Through testing, the performance parameters are as follows: the density is as follows: 1.18g/cm3 (ISO 1183-1), flame retardant properties of 0.8mm V1 (UL 94), vicat softening point of 120 ℃ (ISO 306, B50), ΔE after energy irradiation of 2.5 (SAE J1885).
Comparative example 2 compared with example 1, the PMMA with high flow is not adopted, the PMMA is not easy to migrate to the surface, PMMA with good weather resistance cannot be directly faced with natural environment, so the weather resistance of the material is poor, delta E after energy irradiation is increased to 2.5, the density of the whole system is reduced due to the synergistic effect of the components of the invention, the flame retardant property is good, the combination effect of the components of the material is poor due to the lower mobility of PMMA in comparative example 2, the density is increased, and the flame retardant property is reduced
Comparative example 3
The low-density, high-heat-resistance and weather-proof halogen-free flame-retardant PC/ABS material comprises the following components in parts by weight:
in comparison with example 2, the other components in comparative example 3 were unchanged, PA4T was absent, and the specific preparation method was consistent
Through testing, the performance parameters are as follows: the density is as follows: 1.16g/cm3 (ISO 1183-1), flame retardant properties of 0.8mm V1 (UL 94), vicat softening point 118 ℃ (ISO 306, B50), ΔE after energy irradiation of 2.1 (SAE J1885).
Due to the lack of the hydrogen bond action of the P4T, the binding force of the whole material is poor, the material is not compact, the weather resistance is poor, delta E is 2.1, and due to the lack of the flame retardant effect and high heat resistance of the PA4T, the melamine polyphosphate and the PA4T have better synergistic flame retardant effect, so that the heat resistance and flame retardant property of the whole material are also reduced.
Comparative example 4
The low-density, high-heat-resistance and weather-proof halogen-free flame-retardant PC/ABS material comprises the following components in parts by weight:
comparative example 4 was identical to the specific preparation without transparent ABS, other unchanged, as compared to the component of example 3.
Through testing, the performance parameters are as follows: the density is as follows: 1.16g/cm3 (ISO 1183-1), flame retardant properties of 0.8mm V1 (UL 94), vicat softening point 112 ℃ (ISO 306, B50), ΔE after energy irradiation of 2.2 (SAE J1885).
Because of the lack of transparent ABS (MABS), the MABS contains methyl methacrylate, and PMMA, surlyn, ASA rubber powder and PC have good compatibility, so that the binding force between resins is increased, the heat resistance of the whole material is improved, and meanwhile, the 'bridge' effect of the MABS is lacked, the whole material is not an organic whole, so that the Vicat of the material is reduced, the flame retardant level is reduced, and the delta E after energy irradiation is increased.
Comparative example 5
The low-density, high-heat-resistance and weather-proof halogen-free flame-retardant PC/ABS material comprises the following components in parts by weight:
Comparative example 5 was identical to example 4, except that no silicon PC was used, and the specific preparation method was identical.
Through testing, the performance parameters are as follows: the density is as follows: 1.19g/cm3 (ISO 1183-1), flame retardant properties of 0.8mm V1 (UL 94), vicat softening point 121 ℃ (ISO 306, B50), ΔE after energy irradiation of 2.3 (SAE J1885).
The lack of silicon PC in the material system reduces the binding force between PC and POSS resin and 2-ethylhexyl diphenyl phosphate, thereby reducing the flame resistance, heat resistance and weather resistance of the material.
Comparative example 6
The low-density, high-heat-resistance and weather-proof halogen-free flame-retardant PC/ABS material comprises the following components in parts by weight:
comparative example 6 As compared with example 4, 10g/10min (300 x 1.2 kg) of silicon PC was used, such as SABIC FXG1414T, the other components were unchanged, and the specific material preparation method was consistent
Through testing, the performance parameters are as follows: the density is as follows: 1.17g/cm3 (ISO 1183-1), flame retardant properties of 0.8mm V1 (UL 94), vicat softening point of 123 ℃ (ISO 306, B50), ΔE after energy irradiation of 2.2 (SAE J1885).
Because silicon PC with higher fluidity is not adopted, the dispersibility of the siloxane PC in the system is reduced, so that the materials cannot be well organically combined, the combination effect of the silicon PC on the flame retardant and the PC matrix cannot be well exerted, and the flame retardant efficiency of the flame retardant cannot be well improved.
Comparative example 7
The low-density, high-heat-resistance and weather-proof halogen-free flame-retardant PC/ABS material comprises the following components in parts by weight:
Comparative example 7 in comparison with example 5, the liquid phosphate flame retardant, which did not employ 2-ethylhexyl diphenyl phosphate, employed bisphenol a bis (diphenyl phosphate) (BDP), was identical in other components and in the specific preparation.
Through testing, the performance parameters are as follows: the density is as follows: 1.17g/cm3 (ISO 1183-1), flame retardant properties of 0.8mm V1 (UL 94), vicat softening point 118 ℃ (ISO 306, B50), ΔE after energy irradiation of 2.3 (SAE J1885).
Bisphenol A bis (diphenyl phosphate) (BDP) cannot exert the advantages of ethylhexyl diphenyl phosphate as a flame retardant, and cannot be well compatible with surlyn resin (ethylene-methacrylic acid copolymer), so that the materials form an organic combination whole, and therefore, the heat resistance, the flame retardance and the weather resistance are reduced.
Comparative example 8
The low-density, high-heat-resistance and weather-proof halogen-free flame-retardant PC/ABS material comprises the following components in parts by weight:
comparative example 8 the components were identical to example 5, with the specific preparation being different
Mixing PC, silicon PC, transparent ABS, surlyn resin, PMMA, ASA rubber powder, PA, melamine polyphosphate and POSS resin in a high-speed mixer for 1 hour.
B, feeding the raw material obtained in the step a from the main feed of the extruder, and adding the raw material into a feeding port; the liquid phosphate flame retardant was fed from the liquid scale to the extruder through a liquid pump from the sixth stage of the extruder. In order to be processed, the temperature of the extruder is set to 325 ℃ in each section, the temperature in the liquid scale is 100 ℃, the rotating speed is controlled to 500-600r/min, and extrusion granulation is carried out.
Through testing, the performance parameters are as follows: the density is as follows: 1.17g/cm3 (ISO 1183-1), flame retardant properties of 0.8mm V2 (UL 94), vicat softening point 103 ℃ (ISO 306, B50), ΔE after energy irradiation of 3.0 (SAE J1885).
The dimethyl silyl cage-shaped polysilsesquioxane and the PA4T are not added from side feeding after being mixed, so that on one hand, the retention time of the flame retardant in a screw is increased, the decomposition probability of the flame retardant is greatly improved, and on the other hand, the addition of the PA4T and other high-melting-point materials is required to set higher each section for processing, so that the molecular chain breakage degradation probability of the material is greatly increased, the overall result of the material is unstable, and the Vicat of the material is reduced, the weather resistance delta E is increased, the density is increased and the flame retardant performance is obviously reduced after the processing is finished.
Comparative example 9
The low-density, high-heat-resistance and weather-proof halogen-free flame-retardant PC/ABS material comprises the following components in parts by weight:
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Comparative example 9 compared to example 5, the POSS resin was absent: dimethylsilyl cage polysilsesquioxane. The specific preparation method is consistent.
Through testing, the performance parameters are as follows: the density is as follows: 1.16g/cm3 (ISO 1183-1), flame retardant properties of 0.8mm V2 (UL 94), vicat softening point 120 ℃ (ISO 306, B50), ΔE after energy irradiation of 1.6 (SAE J1885).
Due to the lack of POOS resin, the efficiency of carbon layer formation is reduced in the combustion process, the air isolation capability is achieved, and on the other hand, the lack of dimethyl silyl cage-shaped polysilsesquioxane contains oxygen elements, so that melamine polyphosphate is not easy to be heated and decomposed into phosphoric acid quickly, the efficiency of synthesizing the polyphosphoric acid again to form the carbon layer is not easy, the air isolation capability is achieved, and the flame retardant efficiency is greatly reduced.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (6)

1. The halogen-free flame retardant material comprises the following raw materials in parts by weight:
100 parts of PC;
5-10 parts of siloxane PC;
10-20 parts of PA;
20-40 parts of transparent ABS;
40-50 parts of Surlyn;
20-40 parts of PMMA;
5-10 parts of ASA rubber powder;
1-5 parts of POSS resin;
5-15 parts of melamine polyphosphate;
3-8 parts of liquid phosphate flame retardant;
the PC is bisphenol A type PC, the melt index is 5 g/10 min-10 g/10min, and the test condition is 300 ℃ and 1.2kg;
The siloxane PC is polysiloxane-polycarbonate copolymer, the melt index is 30 g/10 min-40 g/10min, and the test condition is 300 ℃ which is 1.2kg;
the melt index of the transparent ABS is 22g/10 min-35 g/10min, and the test condition is 220 ℃ 10kg;
The melt index of PMMA is 35g/10 min-45 g/10min, and the test condition is 230 ℃ 3.8kg;
The PA resin is PA4T;
the POSS resin is dimethylsilyl cage-shaped polysilsesquioxane;
the liquid phosphate flame retardant is 2-ethylhexyl diphenyl phosphate;
the Surlyn Vicat softening point is more than 75 ℃;
the preparation method of the halogen-free flame retardant material comprises the following steps:
A) Mixing PC, siloxane PC, transparent ABS, surlyn, PMMA and ASA rubber powder to obtain a first mixture;
B) Mixing PA, melamine polyphosphate and POSS resin to obtain a second mixture;
C) Adding the first mixture from a main feeding port of a double-screw extruder, adding the second mixture from a side feeding port of a fifth section of the extruder, adding the liquid phosphate flame retardant into the extruder from a sixth section of the extruder by a liquid scale through a liquid pump, extruding, and granulating to obtain the flame retardant.
2. The material according to claim 1, characterized by comprising the following raw materials in parts by weight:
100 parts of PC;
5-9 parts of siloxane PC;
11-19 parts of PA;
21-38 parts of transparent ABS;
42-48 parts of Surlyn;
21-38 parts of PMMA;
6-9 parts of ASA rubber powder;
2-5 parts of POSS resin;
5-13 parts of melamine polyphosphate;
4-8 parts of liquid phosphate flame retardant.
3. The material according to claim 1, wherein the ASA powder has a gum content of 55% or more.
4. The material of claim 1, wherein the melamine polyphosphate has a particle size of 40 μm or less.
5. A method for preparing the halogen-free flame retardant material according to any one of claims 1 to 4, comprising the steps of:
A) Mixing PC, siloxane PC, transparent ABS, surlyn, PMMA and ASA rubber powder to obtain a first mixture;
B) Mixing PA, melamine polyphosphate and POSS resin to obtain a second mixture;
C) Adding the first mixture from a main feeding port of a double-screw extruder, adding the second mixture from a side feeding port of a fifth section of the extruder, adding the liquid phosphate flame retardant into the extruder from a sixth section of the extruder by a liquid scale through a liquid pump, extruding, and granulating to obtain the flame retardant.
6. The preparation method according to claim 5, wherein the temperature of the extruder in the 1-4 sections is set to 260 ℃, the temperature from the fifth section to the machine head is 325 ℃, the temperature in the liquid scale is 100 ℃, and the rotating speed is controlled to 500-600 r/min.
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CN107474510A (en) * 2017-08-29 2017-12-15 华南理工大学 High fluidity high rigidity halogen-free flame retardant PC/ABS mixtures and preparation method thereof

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CN107619588A (en) * 2016-07-15 2018-01-23 江阴市志远汽车饰件有限公司 A kind of halogen-free flameproof automotive upholstery and preparation method thereof
CN114539758A (en) * 2022-03-15 2022-05-27 山东合创宏新材料科技有限公司 Halogen-free flame-retardant PC/ABS composite material and preparation method thereof
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CN107474510A (en) * 2017-08-29 2017-12-15 华南理工大学 High fluidity high rigidity halogen-free flame retardant PC/ABS mixtures and preparation method thereof

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