CN115286892B - PC/ABS composite material and preparation method and application thereof - Google Patents

PC/ABS composite material and preparation method and application thereof Download PDF

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CN115286892B
CN115286892B CN202210965254.1A CN202210965254A CN115286892B CN 115286892 B CN115286892 B CN 115286892B CN 202210965254 A CN202210965254 A CN 202210965254A CN 115286892 B CN115286892 B CN 115286892B
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attapulgite
modified attapulgite
composite material
abs composite
abs
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CN115286892A (en
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梁靖
李华东
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Xi'an Magnifcent Composite Materials Co ltd
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Xi'an Magnifcent Composite Materials 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
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • 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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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to the technical field of flame-retardant composite materials, in particular to a PC/ABS composite material, a preparation method and application thereof. The invention provides a PC/ABS composite material, which comprises the following components in parts by mass: 65-74 parts of ABS, 6-7 parts of attapulgite flame retardant synergist, 14-16 parts of tetrabromobisphenol A, 2-3 parts of antimonous oxide, 3-6 parts of mullite whisker, 0.5-1 part of antioxidant, 0.5-1 part of lubricant and 0.5-1 part of anti-dripping agent; the attapulgite flame retardant synergist is a mixture of PC and organic modified attapulgite and/or PC coated organic modified attapulgite; the PC coated organic modified attapulgite is prepared by a solution blending method. The PC/ABS composite material has excellent flame retardant property and good mechanical property.

Description

PC/ABS composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of flame-retardant composite materials, in particular to a PC/ABS composite material, a preparation method and application thereof.
Background
For a long time, the flame retardant of ABS mainly adopts halogenide, wherein brominated flame retardants such as decabromodiphenyl ether, tetrabromobisphenol A, octabromoether and the like have the best flame retardant effect, and when the brominated flame retardant is combined with antimony trioxide, ABS can achieve excellent flame retardant property. However, the amount of the flame retardant is higher to achieve higher flame retardancy, and the impact is greatly reduced, so that the heat resistance is obviously reduced.
Along with the increasing global safety awareness, the requirements of people on fire safety and comprehensive performance of products are higher and higher, and the development of materials with higher flame retardant grades and better comprehensive performance becomes one of important research subjects in the field of flame retardance in recent years, so that the material has important social and economic significance.
ABS resin is a flammable polymer material, the horizontal burning speed is very fast, about 2.5-5.1 cm/min, a large amount of black smoke is generated during burning, the flame still continues to burn after leaving fire, the flame is yellow black smoke, and plastics soften and burn after burning, but no molten drops exist. This disadvantage limits its application range, and therefore, how to improve the flame retardancy of ABS resins has become a very important and urgent issue in the current society.
The repeating unit of the Polycarbonate (PC) backbone is (-O-R-O-CO-), which is a linear high molecular polymer. PC is largely classified into several types of polycarbonates, including aliphatic, alicyclic and aromatic, according to the types of repeating units in the main chain. The bisphenol A polycarbonate has good heat resistance and high mechanical strength, is a main variety of industrial production in PC, and has self-extinguishing property due to certain flame retardant property. The material has high dimensional stability and can replace metal and other materials. PC has the disadvantage of high processing temperature and poor flowability, and the formed product is prone to internal stress, resulting in stress cracking of the product.
Attapulgite (also called palygorskite) is a silicate clay mineral containing water and rich in magnesium and aluminum, has a 2:1 chain layered structure, and belongs to the sepiolite family. The attapulgite crystal is in a rod shape, the diameter of a single crystal is 20-70 nm, and the length is 0.5-5 mu m. The attapulgite is different from the silicon oxide nano-rod, has the shape of a rod crystal, and has regular pore channels, wherein zeolite water, coordination water and structural water are arranged in the pore channels; also unlike porous silicon materials, it not only has regular pores, but also spacing rod-like crystal morphology and surface active silicon or aluminum hydroxyl groups. Therefore, not only can attapulgite rod crystals and surface hydroxyl be utilized, but also new materials can be constructed by using the nano-pore canal, and the method has congenital advantages in the aspect of constructing functional materials.
Mullite (3 Al) 2 O 3 ，2SiO 2 ) Is Al 2 O 3 ，SiO 2 The only compound capable of being stably existing in the binary system is a compound formed by [ A1O 4 ]And [ SiO ] 4 ]The tetrahedron structural elements are formed in a spatial arrangement according to a certain rule, and have quite high structural stability. The stable structural properties determine that mullite has high temperature resistance, creep resistance, stable thermal and chemical properties, a low expansion coefficient, and excellent dielectric properties. Mullite whisker is a small crystal with a certain length-diameter ratio, extremely small size, almost perfect crystal form, no or extremely few internal defects and almost approximate strength to a theoretical value, is an enhanced toughness reinforcing material with excellent performance, and has few reports on preparing a composite material with ABS.
The invention discloses a method for improving ABS strength and flame retardant property after the Chinese patent application with publication number of CN110819057A, which prepares the modified attapulgite/magnesium hydroxide flame retardant material, but only 3mm of thickness of UL94 standard sample can be passed, the flame retardant grade is V-0 grade, and the impact strength is 13-15 KJ/m 2 The situation with higher requirements on comprehensive performance can not be satisfied.
Disclosure of Invention
The invention aims to provide a PC/ABS composite material, a preparation method and application thereof, wherein the PC/ABS composite material has excellent flame retardant property and good mechanical property.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a PC/ABS composite material, which comprises the following components in parts by mass:
the attapulgite flame retardant synergist is a mixture of PC and organic modified attapulgite and/or PC coated organic modified attapulgite;
the PC coated organic modified attapulgite is prepared by a solution blending method.
Preferably, the mass ratio of the attapulgite flame retardant synergist in the attapulgite flame retardant synergist is 5: (1-2).
Preferably, the preparation method of the organically modified attapulgite comprises the following steps:
mixing the attapulgite with a first acid solution, and performing first modification to obtain the acid modified attapulgite; the concentration of the first acid liquor is 1mol/L; the mass ratio of the attapulgite to the acid liquor is 1: (25-30);
mixing the acid modified attapulgite, the second acid liquid and the dispersing agent to obtain acid modified attapulgite dispersion liquid;
and mixing the acid modified attapulgite dispersion liquid with an acid coupling agent solution, and performing second modification to obtain the organic modified attapulgite.
Preferably, the preparation method of the PC coated organically modified attapulgite comprises the following steps:
and mixing the PC solution and the dichloromethane solution of the organic modified attapulgite, and coating to obtain the PC coated organic modified attapulgite.
Preferably, the content of butadiene in the ABS is 10-40 wt%;
the PC is bisphenol A type PC, and the molecular weight of the bisphenol A type PC is 25000-35000.
Preferably, the mullite whisker has a diameter of 0.2-3 μm and a length of 5-200 μm.
Preferably, the antioxidants include 1010 antioxidants and 168 antioxidants;
the mass ratio of the 1010 antioxidant to the 168 antioxidant is 1:2.
Preferably, the lubricant is one or more of polyethylene wax, ethylene bis-stearic acid amide, ethylene bis-12-hydroxystearamide, erucic acid amide and oleic acid amide;
the anti-dripping agent is polytetrafluoroethylene.
The invention also provides a preparation method of the PC/ABS composite material, which comprises the following steps:
and mixing the components of the PC/ABS composite material, and then extruding and granulating to obtain the PC/ABS composite material.
The invention also provides the PC/ABS composite material according to the technical scheme or the application of the PC/ABS composite material prepared by the preparation method according to the technical scheme in the flame-retardant field.
The invention provides a PC/ABS composite material, which comprises the following components in parts by mass: 65-74 parts of ABS, 6-7 parts of attapulgite flame retardant synergist, 14-16 parts of tetrabromobisphenol A, 2-3 parts of antimonous oxide, 3-6 parts of mullite whisker, 0.5-1 part of antioxidant, 0.5-1 part of lubricant and 0.5-1 part of anti-dripping agent; the attapulgite flame retardant synergist is a mixture of PC and organic modified attapulgite and/or PC coated organic modified attapulgite; the PC coated organic modified attapulgite is prepared by a solution blending method.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) The attapulgite used in the invention belongs to natural minerals, has low price and small specific gravity, and has good social value and economic value;
2) The oxygen index of PC resin is 25-27, the flame is self-extinguished, the oxygen index of ABS resin is 18-20, the PC resin is inflammable, and the addition of PC resin into the ABS resin is favorable for flame retardance; when PC is adopted to coat the organic modified attapulgite, the compatibility of the attapulgite and ABS can be further improved;
3) Because the strength of the mullite whisker is far higher than that of other chopped fibers, the mullite whisker has high reinforcing efficiency, low thermal expansion coefficient, good dimensional stability of products and small specific gravity, and can reduce the weight of products compared with other common fillers;
4) The PC/ABS composite material has the advantages that the impact strength, the flexural modulus and the flame retardant property are obviously improved, and the comprehensive performance of the PC/ABS composite material has obvious advantages compared with the existing materials (such as Qimei flame retardant ABS D-1200, LG flame retardant ABS 312C and bench ANC 180) on the market.
Detailed Description
The invention provides a PC/ABS composite material, which comprises the following components in parts by mass:
the attapulgite flame retardant synergist is a mixture of PC and organic modified attapulgite and/or PC coated organic modified attapulgite;
the PC coated organic modified attapulgite is prepared by a solution blending method.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
The PC/ABS composite material comprises 65-74 parts by mass of ABS, preferably 66-72 parts by mass, and more preferably 68-70 parts by mass. In the present invention, the butadiene content in the ABS is preferably 10 to 40%, more preferably 20 to 30%, and most preferably 23 to 26%. In an embodiment of the present invention, the model of the ABS is specifically D-180 available from Zhenjiang Qiyaku Kogyo Co. In the invention, the content of butadiene in the ABS is controlled within the range, so that the ABS can have good impact strength after antimony trioxide, mullite whiskers and attapulgite are added.
Based on the mass portion of the ABS, the PC/ABS composite material comprises 6-7 portions of attapulgite flame retardant synergist. In the invention, the mass ratio of the attapulgite flame retardant synergist in the attapulgite flame retardant synergist is preferably 5: (1-2). In the invention, the attapulgite flame retardant synergist is a mixture of PC and organic modified attapulgite and/or PC coated organic modified attapulgite; the mixture of the PC and the organic modified attapulgite is the organic modified attapulgite coated by the PC. In the present invention, the mixture of PC and organically modified attapulgite is understood to be obtained by adding PC and modified attapulgite separately during the preparation of the PC/ABS composite material.
In the present invention, the PC is preferably bisphenol a type PC; the bisphenol A type PC preferably has a molecular weight of 25000 to 35000, more preferably 28000 to 32000, and most preferably 29000 to 31000. In the present invention, the bisphenol a type PC is preferably a bisphenol a type PC prepared by a solution phosgene method. In the present invention, the solvent of the solution phosgene method is preferably methylene chloride and/or ethylene dichloride; the dichloromethane and/or dichloroethane are/is compatible with PC, and PC is electron donating, and the dichloromethane and/or dichloroethane is electrophilic, and the PC and solvent are solvated to accelerate the reaction rate. In an embodiment of the present invention, the bisphenol A type PC is a PC1100 available from Yu Mohua chemical group Co., ltd. In the present invention, controlling the molecular weight of the bisphenol A type PC within the above range can avoid the problems of poor mechanical and chemical resistance properties due to too low molecular weight and poor flowability due to too high molecular weight.
In the present invention, the preparation method of the organically modified attapulgite preferably comprises the following steps:
mixing the attapulgite with a first acid solution, and performing first modification to obtain the acid modified attapulgite; the concentration of the first acid liquor is 1mol/L; the mass ratio of the attapulgite to the acid liquor is 1: (25-30);
mixing the acid modified attapulgite, the second acid liquid and the dispersing agent to obtain acid modified attapulgite dispersion liquid;
and mixing the acid modified attapulgite dispersion liquid with an acid coupling agent solution, and performing second modification to obtain the organic modified attapulgite.
Mixing attapulgite and a first acid solution, and performing first modification to obtain the acid modified attapulgite; the concentration of the first acid liquor is 1mol/L; the mass ratio of the attapulgite to the acid liquor is 1: (25-30).
In the present invention, the attapulgite is preferably a rod-like crystal. In the present invention, the diameter of the single rod-like crystal is preferably 20 to 70nm, more preferably 30 to 60nm, most preferably 40 to 50nm; the length of the individual rod-like crystals is preferably 0.5 to 5. Mu.m, more preferably 1 to 4. Mu.m, most preferably 2 to 3. Mu.m.
In the present invention, the first acid solution is preferably hydrochloric acid or sulfuric acid, more preferably hydrochloric acid. In the invention, the mass ratio of the attapulgite to the acid liquor is preferably 1: (25 to 30), more preferably 1: (25 to 28), most preferably 1: (26-27).
The mixing process is not particularly limited, and may be performed by a process well known to those skilled in the art.
In the present invention, the first modification is preferably performed under ultrasonic conditions, and the temperature of the first modification is preferably 60 ℃, and the time is preferably 6 to 8 hours, more preferably 6.5 to 7.5 hours.
After the first modification is completed, the invention also preferably comprises standing; the time for the standing is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours, and most preferably 2.8 to 3.2 hours. In the invention, the purpose of the standing is to delaminate the solution, obtain a suspension and carbonate and quartz impurities of the bottom layer, and remove the carbonate and quartz impurities of the bottom layer.
After the standing is finished, the invention also preferably comprises the steps of washing, drying, grinding and sieving the suspension in sequence; the washing is preferably repeated with distilled water to neutrality the suspension. In the present invention, the drying is preferably drying. The drying and grinding processes are not particularly limited in the present invention, and may be performed by processes well known to those skilled in the art. In the present invention, the screening is preferably a 1000-1500 mesh screening, more preferably a 1000 mesh screening.
After the acid modified attapulgite is obtained, the acid modified attapulgite, the second acid liquid and the dispersing agent are mixed to obtain the acid modified attapulgite dispersion liquid.
In the present invention, the concentration of the second acid solution is preferably 1mol/L; the second acid solution is preferably hydrochloric acid or sulfuric acid, more preferably hydrochloric acid.
In the present invention, the dispersant is preferably one or more of sodium hexametaphosphate, sodium dodecylbenzenesulfonate and didecyl phosphoric acid diester sodium salt, more preferably sodium hexametaphosphate; when the dispersant is two or more of the above specific choices, the present invention does not have any particular limitation on the ratio of the above specific substances, and the above specific substances may be mixed in any ratio.
In the invention, the dosage ratio of the acid modified attapulgite, the dispersant and the second acid liquid is preferably 8g: (0.3-0.5) g: (400-500) mL, more preferably 8g: (0.35-0.45) g: (420-480) mL, most preferably 8g: (0.38-0.42) g: (430-450) mL.
In the present invention, the mixing preferably includes sequentially performing ultrasound and shaking; the ultrasonic process is not particularly limited, and may be performed by a process well known to those skilled in the art. In the present invention, the temperature of the shaking is preferably 50 ℃, and the time is preferably 1 to 2 hours, more preferably 1.3 to 1.6 hours. In the present invention, the frequency of the oscillation is preferably 40.+ -.2 kHz.
After the acid modified attapulgite dispersion liquid is obtained, the acid modified attapulgite dispersion liquid and the acid coupling agent solution are mixed for second modification, and the organic modified attapulgite is obtained.
In the present invention, the acidic coupling agent solution is preferably prepared by a process comprising the steps of: and (3) mixing absolute ethyl alcohol, water and a silane coupling agent, and then regulating the pH value to be acidic by hydrochloric acid to obtain the acidic coupling agent solution. In the invention, the model of the silane coupling agent is preferably one or more of KH-560, KH-792, KH-550 and KH-570; when the silane coupling agent is two or more of the above specific choices, the present invention does not have any particular limitation on the ratio of the above specific substances, and the above specific substances may be mixed in any ratio. In the invention, the mass ratio of the absolute ethyl alcohol, the water and the silane coupling agent is preferably (8-10): (10-12): (1 to 3), more preferably (8 to 9): (10-11): (1-2), most preferably 8:10:1. The mixing process is not particularly limited, and may be performed by a process well known to those skilled in the art. The concentration of the hydrochloric acid is not particularly limited, and may be any concentration known to those skilled in the art. The concentration of the hydrochloric acid is not particularly limited in the present invention, and the concentration well known to those skilled in the art may be used and the resulting coupling agent solution may be made acidic. In the present invention, the pH of the acidic coupling agent solution is preferably 5 to 6.
In the present invention, the second modification is preferably performed under reflux conditions, the temperature of the reflux is preferably 90 ℃, and the time is preferably 6 hours.
In the invention, in the second modification process, the silanol generated by hydrolysis of the silane coupling agent under the acidic condition and-OH on the surface of the attapulgite generate hydrogen bonds to react to generate Si-O groups, and meanwhile, the silanol obtained by hydrolysis can be dehydrated and condensed into siloxane (shown as formula 1) in pairs, so that aggregation and agglomeration among the attapulgite can be properly improved, the wettability and dispersibility of the powder are improved, and the bonding force of an interface is increased.
After the second modification is completed, the invention also preferably comprises suction filtration, washing, drying and grinding which are sequentially carried out. The process of suction filtration and grinding is not particularly limited in the present invention, and may be performed by a process well known to those skilled in the art. In the present invention, the washing is preferably performed by sequentially using absolute ethanol and distilled water. In the present invention, the temperature of the vacuum drying is preferably 60 ℃.
Or after the second modification is finished, the obtained attapulgite suspension is preferably added with dichloromethane and then the solution is layered, the upper layer is dichloromethane (comprising the prepared organic modified attapulgite), the lower layer is attapulgite reaction solution, and the upper layer is taken and the volume is fixed until the solid-liquid ratio is 1 (20-25) (the mass ratio of the organic modified attapulgite to the dichloromethane) to form a dichloromethane solution of the organic modified attapulgite. In the invention, the dichloromethane is adopted for layering, so that whether the organic modification is successful or not can be verified, and meanwhile, the dichloromethane provides a medium for the PC to coat the organic modified attapulgite.
In the invention, the preparation method of the PC coated organically modified attapulgite preferably comprises the following steps:
and mixing the PC solution and the dichloromethane solution of the organic modified attapulgite, and coating to obtain the PC coated organic modified attapulgite.
In the present invention, the preparation method of the PC solution preferably includes the steps of: PC and methylene chloride were mixed to obtain the PC solution. In the present invention, the ratio of PC to methylene chloride is preferably 200g: (200-300) mL, more preferably 200g: (220-260) mL, most preferably 200g: (230-250) mL. The mixing process is not particularly limited, and may be performed by a process well known to those skilled in the art, and in the embodiment of the present invention, the mixing manner is a standing process.
In the present invention, the dichloromethane solution of the organically modified attapulgite is preferably a dichloromethane solution of the organically modified attapulgite prepared after the second modification. Or the preparation method of the dichloromethane solution of the organic modified attapulgite is preferably that the organic modified attapulgite prepared by the technical proposal is mixed with dichloromethane to obtain the dichloromethane solution of the organic modified attapulgite. In the present invention, the solid-to-liquid ratio of the methylene chloride solution of the organically modified attapulgite is preferably 1 (20 to 25). In the present invention, the mixing is preferably performed under ultrasonic vibration; the time of ultrasonic oscillation is preferably 10min, and the temperature is preferably room temperature; the frequency of the ultrasonic oscillation is not particularly limited, and the ultrasonic oscillation is performed by using a frequency well known to those skilled in the art.
The mixing process of the PC solution and the dichloromethane solution of the organically modified attapulgite is not particularly limited, and can be performed by adopting a process well known to those skilled in the art.
In the present invention, the coating is preferably performed by placing the mixed solution obtained by mixing in a separating funnel, then dropping 300mL of distilled water, and heating and stirring the mixture. The dropping rate is not particularly limited in the present invention, and it is sufficient to adopt a dropping rate well known to those skilled in the art and ensure uniform dropping. In the present invention, the temperature of the heating and stirring is preferably 40 to 45 ℃.
After the heating and stirring are completed, the method also preferably comprises the steps of recycling dichloromethane and collecting the PC coated organically modified attapulgite. In the invention, the process of recovering the dichloromethane is preferably performed by a condensing reflux device; the process of collecting the PC coated organically modified attapulgite preferably comprises sequentially performing filtration and drying. In the invention, the drying mode is preferably drying; the filtering and drying process is not particularly limited, and may be performed by a process well known to those skilled in the art.
Based on the mass parts of the ABS, the PC/ABS composite material comprises 14-16 parts of tetrabromobisphenol A, preferably 14.5-15.5 parts, and more preferably 14.8-15.2 parts. In a specific embodiment of the present invention, the tetrabromobisphenol A is purchased from Shandong Tian-Chemie Co., ltd.
In the invention, the tetrabromobisphenol A is used as a flame retardant, so that the flowability of the material can be improved.
Based on the mass portion of the ABS, the PC/ABS composite material comprises 2-3 portions of antimonous oxide, preferably 2.2-2.8 portions, and more preferably 2.5-2.6 portions. In a specific embodiment of the present invention, the antimony trioxide is purchased from Shandong Hawang chemical Co., ltd.
In the invention, the antimony trioxide and the halogen flame retardant have good flame retardant effect on ABS.
Based on the mass portion of the ABS, the PC/ABS composite material comprises 3-6 portions of mullite whisker, and more preferably 4-5 portions. In the present invention, the mullite whisker preferably has a diameter of 0.2 to 3. Mu.m, and a length of 5 to 200. Mu.m. In a specific embodiment of the invention, the mullite whiskers are purchased from Zibo, inc. of new materials technologies.
Based on the mass portion of the ABS, the PC/ABS composite material comprises 0.5 to 1 portion of antioxidant, preferably 0.6 to 0.9 portion, and more preferably 0.7 to 0.8 portion. In the present invention, the antioxidant preferably includes 1010 antioxidant and 168 antioxidant; the mass ratio of the 1010 antioxidant to the 168 antioxidant is preferably 1:2. In a specific embodiment of the present invention, the antioxidant is specifically an antioxidant available from basf (china) limited.
Based on the mass parts of the ABS, the PC/ABS composite material comprises 0.5-1 part of lubricant, preferably 0.6-0.9 part, and more preferably 0.7-0.8 part. In the invention, the lubricant is preferably one or more of polyethylene wax, ethylene bis-stearic acid amide, ethylene bis-12-hydroxystearamide, erucamide and oleamide; the oleamide preferably comprises one or more of tea oil oleamide and animal oleamide; when the lubricant is two or more of the above specific choices, the present invention is not limited to any particular ratio of the above specific substances, and may be mixed in any ratio.
In the invention, the lubricant can reduce the friction force between ions before resin melting and also helps to prevent degradation caused by excessive heat generated by friction, wherein ethylene bis-stearamide has the characteristics of high-temperature lubricity and low-temperature anti-tackiness.
Based on the mass portion of the ABS, the PC/ABS composite material comprises 0.5-1 part of anti-dripping agent, preferably 0.6-0.9 part, and more preferably 0.7-0.8 part. In the present invention, the anti-dripping agent is preferably polytetrafluoroethylene.
In the present invention, the polytetrafluoroethylene is fibrillated to form a net structure to prevent dripping during the subsequent extrusion granulation process, and flame retardancy is improved.
The invention also provides a preparation method of the PC/ABS composite material, which comprises the following steps:
and mixing the components of the PC/ABS composite material, and then extruding and granulating to obtain the PC/ABS composite material.
In the invention, when the attapulgite flame retardant synergist is a mixture of PC and organically modified attapulgite, the mixing is to mix ABS, PC, tetrabromobisphenol A, antimony trioxide, attapulgite, mullite whisker, an antioxidant, a lubricant and an anti-dripping agent. When the attapulgite flame retardant synergist is PC coated organic modified attapulgite, the mixing is to mix ABS, tetrabromobisphenol A, antimony trioxide, PC coated organic modified attapulgite, mullite whisker, an antioxidant, a lubricant and an anti-dripping agent.
The mixing process is not particularly limited, and may be performed by a process well known to those skilled in the art. In a specific embodiment of the invention, the mixing is performed in a high speed mixer.
In the present invention, the temperature of the extrusion granulation is preferably 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 210 ℃, 220 ℃, 225 ℃, 230 ℃, 225 ℃ and 225 ℃.
In the present invention, the extrusion granulation is preferably performed in a twin-screw extruder, the main machine rotation speed of the twin-screw extruder is preferably 250r/min, and the screw aspect ratio of the twin-screw extruder is preferably (35 to 45): 1, more preferably 40:1.
After the extrusion granulation is completed, the present invention also preferably includes a process of molding and preparing samples, and the present invention is not limited to any particular process, and may be performed by a process known to those skilled in the art.
The invention also provides the PC/ABS composite material according to the technical scheme or the application of the PC/ABS composite material prepared by the preparation method according to the technical scheme in the flame-retardant field. The method of the present invention is not particularly limited, and may be carried out by methods known to those skilled in the art.
The PC/ABS composite material, the preparation method and the application thereof provided by the invention are described in detail below with reference to examples, but are not to be construed as limiting the scope of the invention.
Examples 1 to 3 and comparative examples 1 to 5
The preparation method comprises the following steps:
a: ABS resin (general-purpose ABS resin, available from Zhenjiang Qiyanjie Co., ltd., ABS D-180);
b: PC resin (bisphenol A type PC, having a molecular weight of 25000 to 35000, available from PC1100, va. Chemie Co., ltd.);
c: tetrabromobisphenol a;
d: antimony trioxide;
e: e1 acid-modified attapulgite;
e2, organically modifying the attapulgite;
e3 The PC is coated with organic modified attapulgite (the mass ratio of the PC to the attapulgite is 5:1);
f: mullite whiskers (purchased from Bozhong new materials science and technology Co., ltd., diameter of 0.03-0.5 μm, length of 15-20 μm);
g: antioxidants (antioxidant 1010 and antioxidant 168 in a mass ratio of 1:2, antioxidants available from basf (china) limited);
h: lubricants (ethylene bis-stearamide);
i: anti-drip agent (polytetrafluoroethylene)
The preparation method of the E1 acid modified attapulgite comprises the following steps:
mixing attapulgite with 1mol/L hydrochloric acid solution according to a mass ratio of 1:25, carrying out ultrasonic vibration at a constant temperature of 60 ℃ for 6 hours, standing for 2 hours, layering, removing carbonate and quartz impurities at the bottom layer, repeatedly washing the suspension with distilled water to obtain a neutral suspension, drying, grinding, and sieving with a 1000-mesh sieve for later use to obtain the acid modified attapulgite;
the preparation method of the E2 organically modified attapulgite comprises the following steps:
adding 8g of the acid modified attapulgite into a three-neck flask, adding 400mL of HCl solution with the concentration of 1mol/L, adding 0.5g of sodium hexametaphosphate, and carrying out ultrasonic oscillation for 1h at 50 ℃ with the oscillation frequency of 40+/-2 kHz;
mixing absolute ethyl alcohol, water and a silane coupling agent (KH-550) according to the mass ratio of 8:10:1, and then regulating the pH value to 5.5 by using hydrochloric acid to obtain an acidic coupling agent solution;
pouring the acidic coupling agent solution into a three-neck flask, heating to 90 ℃ for reflux reaction for 6 hours, performing suction filtration, repeatedly washing with absolute ethyl alcohol, washing with distilled water to be neutral, vacuum drying at 60 ℃, and grinding to obtain the organic modified attapulgite;
or adding dichloromethane into the obtained attapulgite suspension, wherein the upper layer of the solution layer is dichloromethane and the lower layer of the solution layer is attapulgite reaction liquid, the attapulgite with lipophilicity after being successfully modified is replaced into the dichloromethane, and the volume is fixed to a solid-liquid ratio of 1:20 (organic attapulgite: dichloromethane) to obtain a dichloromethane solution of the organically modified attapulgite;
e3 The preparation method of the PC coated organic modified attapulgite (the mass ratio of PC to attapulgite is 5:1) comprises the following steps:
200g of PC and 300mL of dichloromethane solution are mixed and kept stand to obtain PC solution;
and (3) carrying out ultrasonic vibration for 10min at normal temperature on 800mL of the dichloromethane solution of the organic modified attapulgite to obtain a modified attapulgite suspension.
Uniformly mixing the PC solution and the modified attapulgite suspension, placing the obtained mixed solution in a separating funnel, uniformly dripping the mixed solution into a three-neck flask with 300mL of distilled water, heating and stirring the mixed solution at 45 ℃, and recycling dichloromethane through a condensing and refluxing device;
forming particles with uniform size in the three-neck flask, filtering and drying to obtain the PC coated organic modified attapulgite;
the preparation method of the composite material comprises the following steps:
mixing ABS, PC, tetrabromobisphenol A, antimonous oxide, attapulgite, mullite whisker, an antioxidant, a lubricant and an anti-dripping agent, and performing extrusion granulation in a double-screw extruder, wherein the extrusion granulation temperature is 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 210 ℃, 220 ℃, 225 ℃, 230 ℃, 225 ℃ and 225 ℃;
the rotating speed of a host machine of the double-screw extruder is 250r/min, and the length-diameter ratio of a screw rod of the double-screw extruder is 40:1; then molding and preparing a sample to obtain a composite material;
the ratios of the raw materials of examples 1 to 3 and comparative examples 1 to 5 are shown in Table 1:
table 1 raw material ratio relationship of examples 1 to 3 and comparative examples 1 to 5
The products prepared in examples 1 to 3 and comparative examples 1 to 5 were subjected to mechanical properties and flame retardant property tests, and the test standards were:
notch impact test is performed with reference to national standard GB/T1843;
bending test is carried out by referring to national standard GB/T9341;
the flame retardant performance is carried out with reference to the thickness of a UL94 standard test specimen of 1.6 mm;
the test results are shown in table 2:
TABLE 2 mechanical Properties and flame retardant Properties of the products prepared in examples 1 to 3 and comparative examples 1 to 5
As is clear from tables 1 to 2, comparative examples 1 to 2 were poor in flame retardancy, failed to pass the flame retardant rating UL94 of 1.6mm V0, and comparative example 1 did not contain E1, E2, E3, and comparative example 2 did not contain antimony trioxide. Therefore, antimony trioxide and attapulgite have a synergistic effect, so that the flame retardance of the ABS composite material disclosed by the invention can be enhanced;
examples 1 and 2 are compared, and the impact strength of the composite material is 17.2KJ/m when 2 parts of E2 is used in example 2 2 In example 1, 1 part of E2 was used with an impact strength of 22KJ/m 2 ；
The impact properties of examples 1 to 3 are greatly different from those of comparative examples 1 to 3, and the use of E1 for comparative example 3 is inferior in compatibility with ABS to that of the attapulgite used in examples 1 to 3, and is shown to have an impact strength of only 16.1KJ/m 2 E2 was used in example 1, with an impact strength of 22KJ/m 2 E3 was used in example 3, with an impact strength of 25KJ/m 2 The performance is optimal, the flame retardant grade reaches ULM 941.6mm V0, and the PC coated organically modified attapulgite can be known to further improve the problem of compatibility with a resin matrix, and the performance is optimal when E3 is used;
example 3 in comparison with comparative examples 4 and 5, the mullite whisker used 3 parts of the mullite whisker of example 3 has the toughening and stiffening effects and has the impact strength of 25.0KJ/m 2 The cost of the product is reduced to a certain extent;
from this, it can be seen that example 3 of the present invention has a significant advantage over the comparative example. The manufactured high-strength high-impact-resistance high-efficiency flame-retardant PC/ABS composite material has the advantages of high strength, good impact, high flame-retardant grade and lower cost.
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 (8)

1. The PC/ABS composite material is characterized by comprising the following components in parts by weight:
the attapulgite flame retardant synergist is a mixture of PC and organic modified attapulgite and/or PC coated organic modified attapulgite;
the PC coated organic modified attapulgite is prepared by a solution blending method;
the preparation method of the organic modified attapulgite comprises the following steps:
mixing the attapulgite with a first acid solution, and performing first modification to obtain the acid modified attapulgite; the concentration of the first acid liquor is 1mol/L; the mass ratio of the attapulgite to the acid liquor is 1: (25-30);
mixing the acid modified attapulgite, the second acid liquid and the dispersing agent to obtain acid modified attapulgite dispersion liquid;
mixing the acid modified attapulgite dispersion liquid and an acid coupling agent solution, and performing second modification to obtain the organic modified attapulgite;
the preparation method of the PC coated organic modified attapulgite comprises the following steps:
and mixing the PC solution and the dichloromethane solution of the organic modified attapulgite, and coating to obtain the PC coated organic modified attapulgite.
2. The PC/ABS composite material according to claim 1, wherein the mass ratio of PC to organically modified attapulgite in the attapulgite flame retardant synergist is 5: (1-2).
3. The PC/ABS composite of claim 1 wherein the butadiene content of the ABS is 10 to 40wt%;
the PC is bisphenol A type PC, and the molecular weight of the bisphenol A type PC is 25000-35000.
4. The PC/ABS composite of claim 1 wherein the mullite whiskers have a diameter of 0.2 to 3 μm and a length of 5 to 200 μm.
5. The PC/ABS composite of claim 1 wherein the antioxidants comprise 1010 antioxidant and 168 antioxidant;
the mass ratio of the 1010 antioxidant to the 168 antioxidant is 1:2.
6. The PC/ABS composite of claim 1 wherein the lubricant is one or more of polyethylene wax, ethylene bis-stearamide, ethylene bis-12-hydroxystearamide, erucamide and oleamide;
the anti-dripping agent is polytetrafluoroethylene.
7. The method for preparing the PC/ABS composite material according to any one of claims 1 to 6, comprising the following steps:
and mixing the components of the PC/ABS composite material, and then extruding and granulating to obtain the PC/ABS composite material.
8. The PC/ABS composite material according to any one of claims 1 to 6 or the PC/ABS composite material prepared by the preparation method according to claim 7 is applied to the flame-retardant field.
CN202210965254.1A 2022-08-12 2022-08-12 PC/ABS composite material and preparation method and application thereof Active CN115286892B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107880250A (en) * 2017-11-27 2018-04-06 山东诺威新材料有限公司 Fuel transmission deep cooling pipeline hard polyaminoester composite and preparation method thereof
CN110819058A (en) * 2019-09-26 2020-02-21 江苏昇和新材料科技股份有限公司 Core-shell structure nano attapulgite/magnesium hydroxide doped ABS composite material
WO2020108204A1 (en) * 2018-11-27 2020-06-04 金发科技股份有限公司 Abs composite material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107880250A (en) * 2017-11-27 2018-04-06 山东诺威新材料有限公司 Fuel transmission deep cooling pipeline hard polyaminoester composite and preparation method thereof
WO2020108204A1 (en) * 2018-11-27 2020-06-04 金发科技股份有限公司 Abs composite material
CN110819058A (en) * 2019-09-26 2020-02-21 江苏昇和新材料科技股份有限公司 Core-shell structure nano attapulgite/magnesium hydroxide doped ABS composite material

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