CN115073903A - PC/ABS alloy and preparation method and application thereof - Google Patents

PC/ABS alloy and preparation method and application thereof Download PDF

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Publication number
CN115073903A
CN115073903A CN202110262453.1A CN202110262453A CN115073903A CN 115073903 A CN115073903 A CN 115073903A CN 202110262453 A CN202110262453 A CN 202110262453A CN 115073903 A CN115073903 A CN 115073903A
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red phosphorus
temperature control
abs alloy
temperature
maleic anhydride
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袁好
陈少军
毕伟枫
张艳霞
胡致铨
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ZTE Corp
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ZTE Corp
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Priority to PCT/CN2022/070167 priority patent/WO2022188533A1/en
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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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08K3/02—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C08K3/02—Elements
    • C08K2003/026—Phosphorus
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The embodiment of the invention provides a PC/ABS alloy and a preparation method and application thereof, belonging to the field of high polymer materials. The PC/ABS alloy comprises the following components in parts by weight: 60-80 parts of polycarbonate; 20-40 parts of ABS plastic; 3-5 parts of a compatibilizer; 0-4 parts of a lubricant; 2-5 parts of red phosphorus master batch; 5-10 parts of a toughening agent; wherein, the red phosphorus master batch comprises the following components by taking the total mass percentage of the components in the red phosphorus master batch as 100 percent: 10 to 50 percent of red phosphorus; 50 to 90 percent of dispersant. The technical scheme of the embodiment of the invention can not only reduce the addition of red phosphorus, but also uniformly disperse the red phosphorus in the PC/ABS alloy, and simultaneously has good flame retardant effect, and can not cause the mechanical property of the PC/ABS alloy to be obviously deteriorated.

Description

PC/ABS alloy and preparation method and application thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a PC/ABS alloy and a preparation method and application thereof.
Background
Polycarbonate (PC) is a high molecular polymer containing carbonate groups in molecular chains, belongs to engineering plastics, and is easy to stress crack, sensitive to gaps and the like. Bisphenol a polycarbonate in PC has high mechanical strength due to a large number of rigid groups contained in the main chain, and also has characteristics such as heat resistance, non-toxicity and transparency, and is the most widely used polycarbonate because of the above properties.
ABS plastics are thermoplastic resins polymerized from three monomers of acrylonitrile (A), butadiene (B) and styrene (S), and have the characteristics of good wear resistance, easy processing and the like, but poor heat resistance and weather resistance.
The PC/ABS alloy combines good heat resistance and mechanical strength of PC and good processability and low-temperature impact strength of ABS, and has the excellent comprehensive properties of no toxicity, low water absorption, high chemical stability, high cost performance and the like. However, PC/ABS has poor flame retardant properties, and may present a safety hazard when used in electrical appliances, digital product housings, and automotive interior and exterior trim. Red phosphorus is a good inorganic material flame retardant material; however, the dispersion effect in the PC/ABS alloy is not ideal, so that more addition amount is needed to achieve the ideal flame retardant effect, and excessive addition amount of red phosphorus can negatively affect the mechanical properties of the PC/ABS alloy. Therefore, there is a need to provide a new solution to the problem of red phosphorus used as a flame retardant for PC/ABS alloys.
Disclosure of Invention
The embodiment of the invention mainly aims to provide a PC/ABS alloy, a preparation method and application thereof, and aims to solve the problem that the existing PC/ABS alloy has flame retardant effect only by needing more addition amount when red phosphorus is used as a flame retardant, but the mechanical property of the alloy is poor.
In a first aspect, embodiments of the present invention provide a PC/ABS alloy. The PC/ABS alloy comprises the following components in parts by weight:
Figure RE-RE-GDA0003150850020000011
wherein, the red phosphorus master batch comprises the following components by taking the total mass percentage of the components in the red phosphorus master batch as 100 percent:
10 to 50 percent of red phosphorus;
50 to 90 percent of dispersant.
According to the PC/ABS alloy provided by the first aspect of the embodiment of the invention, the red phosphorus and the dispersing agent are added into the PC/ABS alloy in a red phosphorus master batch mode, so that the addition amount of the red phosphorus can be reduced, the red phosphorus can be uniformly dispersed in the PC/ABS alloy, the PC/ABS alloy also has good flame retardant effect and environment-friendly effect, and the mechanical property of the PC/ABS alloy is not obviously deteriorated.
In a second aspect, an embodiment of the present invention further provides a method for preparing a PC/ABS alloy, where the method for preparing a PC/ABS alloy includes the following steps:
providing the polycarbonate, the ABS plastic, the compatibilizer, the lubricant, the red phosphorus master batch and the toughening agent;
mixing the polycarbonate, the ABS plastic, the compatibilizer, the lubricant, the red phosphorus master batch and the toughening agent to obtain a mixed material;
and carrying out melt extrusion treatment on the mixed material, and carrying out bracing and granulation treatment to obtain the PC/ABS alloy.
In a third aspect, an embodiment of the present invention further provides an application of the PC/ABS alloy described above in a communication base station device housing, a mobile terminal housing, and an automotive interior.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic flow chart of a preparation method of a PC/ABS alloy provided by an embodiment of the present invention;
FIG. 2 is a schematic flow chart of a method for preparing red phosphorus masterbatch according to an embodiment of the present invention;
FIG. 3 is a scanning electron microscope image of a cross section of the red phosphorus master batch provided in the embodiment 2;
FIG. 4 is an EDS energy spectrum of a cross section of a red phosphorus master batch provided in example 2 of the present invention;
FIG. 5 is a scanning electron microscope image of a cross section of the PC/ABS alloy provided in the embodiment 2;
FIG. 6 is an EDS energy spectrum of a cross section of a PC/ABS alloy provided in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The flow diagrams depicted in the figures are merely illustrative and do not necessarily include all of the elements and operations/steps, nor do they necessarily have to be performed in the order depicted. For example, some operations/steps may be decomposed, combined or partially combined, so that the actual execution sequence may be changed according to the actual situation.
It is to be understood that the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the specification of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The embodiment of the invention provides a PC/ABS alloy and a preparation method and application thereof. The PC/ABS alloy can be applied to communication base station equipment shells, mobile terminal shells and automotive trims, the mobile terminal can be used for electronic equipment such as mobile phones, tablet computers, notebook computers, desktop computers, personal digital assistants and wearable equipment, and the PC/ABS alloy has good flame retardant property, environmental protection effect and mechanical property as the communication base station equipment shells, the mobile terminal shells and the automotive trims which are made of the PC/ABS alloy. In addition, the material can also be used in household appliance shells, medical equipment shells, aerospace equipment shells and track traffic equipment shells.
Some embodiments of the invention are described in detail below with reference to the accompanying drawings. The embodiments described below and the features of the embodiments can be combined with each other without conflict.
The PC/ABS alloy provided by the embodiment of the invention contains polycarbonate, ABS plastic, a compatibilizer, a lubricant, red phosphorus master batch and a toughening agent, and the weight parts of the components in the PC/ABS alloy are 60-80 parts of polycarbonate; 20-40 parts of ABS plastic; 3-5 parts of a compatibilizer; 0-4 parts of a lubricant; 2-5 parts of red phosphorus master batch; 5-10 parts of a toughening agent; the phosphorus master batch comprises the following components in percentage by mass, wherein the total mass of the components in the phosphorus master batch is 100 percent: 10 to 50 percent of red phosphorus; 50 to 90 percent of dispersant. In some preferred embodiments, the mass percentage of the red phosphorus in the red phosphorus master batch is 25% -45%, and the mass percentage of the dispersing agent is 55% -75%.
In some alternative embodiments, the polycarbonate is selected from bisphenol A polycarbonate, such as bisphenol A polycarbonate which may be PC-110, and the like, wherein the bisphenol A polycarbonate of type PC-110 has a melt index of 10g/10min and a heat distortion temperature of 136 ℃.
The ABS plastic of the embodiment of the invention can be ABS plastic with the model number of PA-757 and the like. Wherein the melt index of the ABS plastic with the model of PA-757 is 1.8g/10min, and the heat distortion temperature is 190 ℃.
In some alternative embodiments, the compatibilizer is styrene-maleic anhydride copolymer (SMA), the styrene-maleic anhydride copolymer is a copolymer of styrene (S) and Maleic Anhydride (MA), the higher the content of MA in the styrene-maleic anhydride copolymer, the better the dispersion effect of each component in the PC/ABS alloy, but the higher the content of MA in the styrene-maleic anhydride copolymer, the higher the content of MA in the PC/ABS alloy, the higher the content of MA in the styrene-maleic anhydride copolymer, the better the thermal stability of the compatibilizer is affected, and therefore, the grafting ratio of maleic anhydride in the styrene-maleic anhydride copolymer is 10% -30%. In some preferred embodiments, the graft ratio of maleic anhydride in the styrene-maleic anhydride copolymer is 15% to 20%. The red phosphorus master batch has a dispersion effect on red phosphorus, and can be subjected to compatibilization compounding and secondary dispersion by combining a compatibilizer with the maleic anhydride grafting rate of 10-30%, so that the dispersion effect of the red phosphorus in the PC/ABS alloy is further improved. In some embodiments, the styrene-maleic anhydride copolymer may be SMA-701A, or the like.
In some alternative embodiments, the lubricant comprises an external lubricant and an internal lubricant; wherein the external lubricant is selected from zinc stearate (ZnSt) 2 ) At least one of pentaerythritol stearate (PETS), and the like; the internal lubricant is dioctyl phthalate (DOP) and the like.
In some alternative embodiments, the toughening agent is selected from at least one of methacrylic acid-butadiene-styrene copolymer (SMA), polyolefin thermoplastic elastomer (POE), thermoplastic polyurethane elastomer (TPU), Ethylene Butyl Acrylate (EBA), ethylene propylene diene monomer, ethylene vinyl acetate copolymer (EVA), and the like.
In some alternative embodiments, the dispersant is selected from at least one of ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH), maleic anhydride grafted polyethylene (PE-g-MAH), ethylene vinyl acetate copolymer grafted maleic anhydride (EVA-g-MAH).
On the basis of the PC/ABS alloy, the embodiment of the invention further provides a preparation method of the PC/ABS alloy.
Referring to fig. 1, fig. 1 is a schematic flow chart of a method for preparing a PC/ABS alloy according to an embodiment of the present invention.
As shown in FIG. 1, the preparation method of the PC/ABS alloy comprises steps S101 to S103.
Step S101, providing polycarbonate, ABS plastic, a compatibilizer, a lubricant, red phosphorus master batch and a toughening agent.
In the step S101, in the provided raw material components, by weight, 60-80 parts of polycarbonate, 20-40 parts of ABS plastic, 3-5 parts of compatibilizer, 0-4 parts of lubricant, 2-5 parts of red phosphorus master batch and 5-10 parts of toughening agent are included; in the red phosphorus master batch, the total mass percentage of all components in the red phosphorus master batch is 100 percent, and the red phosphorus accounts for 10 to 50 percent; the dispersant accounts for 50 to 90 percent. In some preferred embodiments, the mass percentage of the red phosphorus in the red phosphorus master batch is 25% -45%, and the mass percentage of the dispersing agent is 55% -75%. In some alternative embodiments, the water content of the polycarbonate is not higher than 0.02% and the water content of the ABS plastic is not higher than 0.02%. If the water content of the polycarbonate and the ABS plastic exceeds 0.02 percent, the polycarbonate and the ABS plastic can be respectively dried for 2 to 10 hours at the temperature of between 60 and 80 ℃ so as to ensure that the water content meets the requirement.
In some alternative embodiments, the polycarbonate is selected from the group consisting of bisphenol a polycarbonate; the compatibilizer is styrene-maleic anhydride copolymer (SMA) with 10% -30% of grafting rate of maleic anhydride. In some preferred embodiments, the graft ratio of maleic anhydride in the styrene-maleic anhydride copolymer is 15% to 20%.
In some alternative embodiments, the lubricant comprises an external lubricant and an internal lubricant; wherein the external lubricant is selected from zinc stearate (ZnSt) 2 ) At least one of pentaerythritol stearate (PETS), and the like; the internal lubricant is dioctyl phthalate (DOP) and the like.
In some alternative embodiments, the toughening agent is selected from at least one of methacrylic acid-butadiene-styrene copolymer (SMA), polyolefin thermoplastic elastomer (POE), thermoplastic polyurethane elastomer (TPU), Ethylene Butyl Acrylate (EBA), ethylene propylene diene monomer, ethylene vinyl acetate copolymer (EVA), and the like.
In some alternative embodiments, the dispersant is selected from at least one of ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH), maleic anhydride grafted polyethylene (PE-g-MAH), ethylene vinyl acetate copolymer grafted maleic anhydride (EVA-g-MAH).
And S102, mixing the polycarbonate, the ABS plastic, the compatibilizer, the lubricant, the red phosphorus master batch and the toughening agent to obtain a mixed material.
In step S012, the step of mixing the polycarbonate, the ABS plastic, the compatibilizer, the lubricant, the red phosphorus master batch, and the toughening agent may be performed in a mixing container for 5min to 20min, so that the polycarbonate, the ABS plastic, the compatibilizer, the lubricant, the toughening agent, and the red phosphorus master batch are mixed sufficiently to improve uniformity of the material.
And S103, carrying out melt extrusion treatment on the mixed material, and then carrying out bracing and granulation treatment to obtain the PC/ABS alloy.
In step S103, melt extrusion of the mixture is performed, the used equipment may be a twin-screw extruder, and during the melt extrusion, the melt extrusion temperature needs to be controlled so that the temperature of the whole melt extrusion is 190 ℃ to 225 ℃. In an alternative embodiment, the melt extrusion is divided into ten zones from a melt extrusion feed end to a melt extrusion discharge end, wherein the temperature of the first temperature control zone is 190-195 ℃, the temperature of the second temperature control zone is 190-195 ℃, the temperature of the third temperature control zone is 200-205 ℃, the temperature of the fourth temperature control zone is 200-205 ℃, the temperature of the fifth temperature control zone is 210-215 ℃, the temperature of the sixth temperature control zone is 210-215 ℃, the temperature of the seventh temperature control zone is 220-225 ℃, the temperature of the eighth temperature control zone is 220-225 ℃, the temperature of the ninth temperature control zone is 210-220 ℃ and the temperature of the tenth temperature control zone is 225 ℃. In the bracing process, the bracing is cooled to control the material forming, and the specific cooling mode can be water cooling and the like.
In one embodiment, specifically, referring to fig. 2, the red phosphorus masterbatch is prepared according to the following method:
step S201, red phosphorus and a dispersing agent are provided.
In step S201, red phosphorus is in a powder state, and the dispersant is at least one selected from the group consisting of ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH), maleic anhydride grafted polyethylene (PE-g-MAH), and ethylene vinyl acetate copolymer grafted maleic anhydride (EVA-g-MAH). In some embodiments, the red phosphorus has a particle size on the micro-nanometer scale, such as 2nm to 10 μm.
And step S202, mixing the red phosphorus and the dispersing agent to obtain a pre-dispersion body.
The red phosphorus and the dispersant can be mixed by an internal mixer for 10min-20 min. Through dense mixing, the red phosphorus has a good pre-dispersion effect, and a material foundation is laid for the subsequent uniform dispersion of the red phosphorus in PC/ABS.
And step S203, granulating the obtained pre-dispersion to obtain the red phosphorus master batch.
The granulation treatment of the pre-dispersion can be carried out in a single-screw granulator, red phosphorus and a dispersing agent are prepared into red phosphorus master batches, on one hand, the red phosphorus can be effectively dispersed, and thus the red phosphorus is dispersed in the PC/ABS alloy in a red phosphorus master batch mode; on the other hand, the dispersant of the embodiment of the invention has a coating effect on red phosphorus, so that the precipitation resistance of the red phosphorus in the PC/ABS alloy can be improved.
In order to better explain the technical scheme of the embodiment of the invention, the following further explains the technical scheme by a plurality of embodiments.
Example 1
A PC/ABS alloy and a preparation method thereof.
The PC/ABS alloy comprises the following components in parts by weight: 80 parts of polycarbonate, 20 parts of ABS plastic, 3 parts of compatibilizer, 2 parts of red phosphorus master batch and 5 parts of toughening agent.
The polycarbonate is PC-110, the ABS plastic is PA-757, the compatibilizer is a styrene-maleic anhydride copolymer with maleic anhydride grafting rate of 18%, and the toughening agent is a methacrylic acid-butadiene-styrene copolymer; the mass percentage of red phosphorus in the red phosphorus master batch is 25 percent, the mass percentage of the dispersing agent is 75 percent, and the dispersing agent is ethylene-octene copolymer grafted maleic anhydride.
The preparation method of the PC/ABS alloy provided by the embodiment is as follows:
(1) 8kg of PC-110, 2kg of PA-757, 0.3kg of styrene-maleic anhydride copolymer (SMA-701A), 0.2kg of red phosphorus master batch and 0.5kg of methacrylic acid-butadiene-styrene copolymer are provided, wherein the mass content of water in the PC-110 and the PA-757 is controlled to be not more than 0.02%;
(2) placing the provided PC-110, PA-757, styrene-maleic anhydride copolymer, methacrylic acid-butadiene-styrene copolymer and red phosphorus master batch in a mixing container for mixing treatment for 10min to obtain a mixed material;
(3) the method comprises the following steps of carrying out melt extrusion on a mixed material by adopting a double-screw extruder, and setting ten temperature control areas from a feeding end to a discharging end of the double-screw extruder, wherein the temperature of a first temperature control area is 190 ℃, the temperature of a second temperature control area is 195 ℃, the temperature of a third temperature control area is 200 ℃, the temperature of a fourth temperature control area is 205 ℃, the temperature of a fifth temperature control area is 210 ℃, the temperature of a sixth temperature control area is 215 ℃, the temperature of a seventh temperature control area is 220 ℃, the temperature of an eighth temperature control area is 225 ℃, the temperature of a ninth temperature control area is 215 ℃ and the temperature of a tenth temperature control area is 225 ℃. And extruding the mixed material, and then carrying out bracing (water cooling after bracing) and granulating by a granulator to obtain the PC/ABS alloy.
Example 2
A PC/ABS alloy and a preparation method thereof.
The PC/ABS alloy comprises the following components in parts by weight: 70 parts of polycarbonate, 30 parts of ABS plastic, 3 parts of compatibilizer, 1 part of external lubricant, 3 parts of internal lubricant, 3 parts of red phosphorus master batch and 5 parts of toughening agent.
Wherein the polycarbonate is PC-110 in type, the ABS plastic is PA-757 in type, and the compatibilizer is a styrene-maleic anhydride copolymer with maleic anhydride grafting rate of 18%; the external lubricant is zinc stearate, and the internal lubricant is dioctyl phthalate; the mass percentage of red phosphorus in the red phosphorus master batch is 25 percent, the mass percentage of a dispersing agent is 75 percent, and the dispersing agent is ethylene-octene copolymer grafted maleic anhydride; the toughening agent is methacrylic acid-butadiene-styrene copolymer.
The preparation method of the PC/ABS alloy provided by the embodiment is as follows:
(1) 7kg of PC-110, 3kg of PA-757, 0.3kg of styrene-maleic anhydride copolymer (SMA-701A), 0.1kg of zinc stearate, 0.3kg of dioctyl phthalate, 0.3kg of red phosphorus master batch and 0.5kg of methacrylic acid-butadiene-styrene copolymer, wherein the mass content of water in the PC-110 and the PA-757 is controlled to be not more than 0.02%;
(2) placing the provided PC-110, PA-757, styrene-maleic anhydride copolymer, methacrylic acid-butadiene-styrene copolymer, zinc stearate, dioctyl phthalate and red phosphorus master batch in a mixing container for mixing treatment for 10min to obtain a mixed material;
(3) the method comprises the following steps of carrying out melt extrusion on a mixed material by adopting a double-screw extruder, and setting ten temperature control areas from a feeding end to a discharging end of the double-screw extruder, wherein the temperature of a first temperature control area is 190 ℃, the temperature of a second temperature control area is 195 ℃, the temperature of a third temperature control area is 200 ℃, the temperature of a fourth temperature control area is 205 ℃, the temperature of a fifth temperature control area is 210 ℃, the temperature of a sixth temperature control area is 215 ℃, the temperature of a seventh temperature control area is 220 ℃, the temperature of an eighth temperature control area is 225 ℃, the temperature of a ninth temperature control area is 215 ℃ and the temperature of a tenth temperature control area is 225 ℃. And extruding the mixed material, and then carrying out bracing (water cooling after bracing) and granulating by a granulator to obtain the PC/ABS alloy.
Example 3
A PC/ABS alloy and a preparation method thereof.
The PC/ABS alloy comprises the following components in parts by weight: 60 parts of polycarbonate, 40 parts of ABS plastic, 3 parts of compatibilizer, 0.5 part of external lubricant, 1 part of internal lubricant, 4 parts of red phosphorus master batch and 10 parts of toughening agent.
Wherein the polycarbonate is PC-110 in model, the ABS plastic is PA-757 in model, and the compatibilizer is a styrene-maleic anhydride copolymer with maleic anhydride grafting rate of 18%; the external lubricant is zinc stearate; the internal lubricant is dioctyl phthalate; the mass percentage of red phosphorus in the red phosphorus master batch is 25 percent, the mass percentage of a dispersing agent is 75 percent, and the dispersing agent is ethylene-octene copolymer grafted maleic anhydride; the toughening agent is methacrylic acid-butadiene-styrene copolymer.
The preparation method of the PC/ABS alloy provided by the embodiment is as follows:
(1) 6kg of PC-110, 4kg of PA-757, 0.3kg of styrene-maleic anhydride copolymer (SMA-701A), 0.05kg of dioctyl phthalate, 0.1kg of zinc stearate, 0.4kg of red phosphorus master batch and 1kg of methacrylic acid-butadiene-styrene copolymer, wherein the mass content of water in the PC-110 and the PA-757 is controlled to be not more than 0.02%;
(2) placing the provided PC-110, PA-757, styrene-maleic anhydride copolymer, dioctyl phthalate, zinc stearate, red phosphorus master batch and methacrylic acid-butadiene-styrene copolymer in a mixing container for mixing treatment for 10min to obtain a mixed material;
(3) the method comprises the following steps of carrying out melt extrusion on a mixed material by adopting a double-screw extruder, and setting ten temperature control areas from a feeding end to a discharging end of the double-screw extruder, wherein the temperature of a first temperature control area is 190 ℃, the temperature of a second temperature control area is 195 ℃, the temperature of a third temperature control area is 200 ℃, the temperature of a fourth temperature control area is 205 ℃, the temperature of a fifth temperature control area is 210 ℃, the temperature of a sixth temperature control area is 215 ℃, the temperature of a seventh temperature control area is 220 ℃, the temperature of an eighth temperature control area is 225 ℃, the temperature of a ninth temperature control area is 215 ℃ and the temperature of a tenth temperature control area is 225 ℃. And extruding the mixed material, and then carrying out bracing (water cooling after bracing) and granulating by a granulator to obtain the PC/ABS alloy.
In order to verify the flame retardant property and mechanical property of the PC/ABS alloy provided in the embodiments 1-3 of the present invention, the following comparative examples are also provided.
Comparative example 1
A PC/ABS alloy and a preparation method thereof.
The PC/ABS alloy comprises the following components in parts by weight: 70 parts of polycarbonate, 30 parts of ABS plastic and 5 parts of toughening agent.
Wherein the polycarbonate is PC-110 in model, the ABS plastic is PA-757 in model, and the toughening agent is methacrylic acid-butadiene-styrene copolymer.
The preparation method of the PC/ABS alloy provided by the embodiment is as follows:
(1) providing 7kg of PC-110, 3kg of PA-757 and 0.5kg of methacrylic acid-butadiene-styrene copolymer, wherein the mass content of water in the PC-110 and the PA-757 is controlled to be not more than 0.02%;
(2) placing the provided PC-110, PA-757 and methacrylic acid-butadiene-styrene copolymer in a mixing container for mixing treatment for 10min to obtain a mixed material;
(3) the method comprises the following steps of carrying out melt extrusion on a mixed material by adopting a double-screw extruder, and setting ten temperature control areas from a feeding end to a discharging end of the double-screw extruder, wherein the temperature of a first temperature control area is 190 ℃, the temperature of a second temperature control area is 195 ℃, the temperature of a third temperature control area is 200 ℃, the temperature of a fourth temperature control area is 205 ℃, the temperature of a fifth temperature control area is 210 ℃, the temperature of a sixth temperature control area is 215 ℃, the temperature of a seventh temperature control area is 220 ℃, the temperature of an eighth temperature control area is 225 ℃, the temperature of a ninth temperature control area is 215 ℃ and the temperature of a tenth temperature control area is 225 ℃. And extruding the mixed material, and then carrying out bracing (water cooling after bracing) and granulating by a granulator to obtain the PC/ABS alloy.
Comparative example 2
A PC/ABS alloy and a preparation method thereof.
The PC/ABS alloy comprises the following components in parts by weight: 70 parts of polycarbonate, 30 parts of ABS plastic, 5 parts of a compatibilizer, 10 parts of resorcinol (diphenyl phosphate) (RDP) and 5 parts of a toughening agent.
The polycarbonate is PC-110, the ABS plastic is PA-757, the compatibilizer is a styrene-maleic anhydride copolymer with maleic anhydride grafting rate of 18%, and the toughening agent is a methacrylic acid-butadiene-styrene copolymer.
The preparation method of the PC/ABS alloy provided by the embodiment is as follows:
(1) providing 7kg of PC-110, 3kg of PA-757, 0.5kg of styrene-maleic anhydride copolymer (SMA-701A), 1kg of resorcinol (diphenyl phosphate) and 0.5kg of methacrylic acid-butadiene-styrene copolymer, wherein the mass content of water in the PC-110 and the PA-757 is controlled to be not more than 0.02%;
(2) placing the provided PC-110, PA-757, styrene-maleic anhydride copolymer, resorcinol (diphenyl phosphate) and methacrylic acid-butadiene-styrene copolymer in a mixing container for mixing treatment for 10min to obtain a mixed material;
(3) the method comprises the following steps of carrying out melt extrusion on a mixed material by adopting a double-screw extruder, and setting ten temperature control areas from a feeding end to a discharging end of the double-screw extruder, wherein the temperature of a first temperature control area is 190 ℃, the temperature of a second temperature control area is 195 ℃, the temperature of a third temperature control area is 200 ℃, the temperature of a fourth temperature control area is 205 ℃, the temperature of a fifth temperature control area is 210 ℃, the temperature of a sixth temperature control area is 215 ℃, the temperature of a seventh temperature control area is 220 ℃, the temperature of an eighth temperature control area is 225 ℃, the temperature of a ninth temperature control area is 215 ℃ and the temperature of a tenth temperature control area is 225 ℃. And extruding the mixed material, and then carrying out bracing (water cooling after bracing) and granulating by a granulator to obtain the PC/ABS alloy.
Comparative example 3
A PC/ABS alloy in the form of pellets of type HAC8265 FR.
Performance verification
The following examples 1 to 3 and comparative examples 1 to 3 were verified for flame retardancy and mechanical properties.
Wherein, the test standards and test conditions for flame retardant property and mechanical property are shown in table 1, and the flame retardant property and mechanical property of the PC/ABS alloys provided in examples 1 to 3 and comparative examples 1 to 3 are obtained according to the test standards and test conditions of table 1.
TABLE 1 test standards
Figure RE-RE-GDA0003150850020000071
Figure RE-RE-GDA0003150850020000081
TABLE 2PC/ABS alloy test standards
Figure RE-RE-GDA0003150850020000082
As can be seen from Table 2, the flame retardant grades of the examples 1 and 2 reach 1.6mm V-0 and the highest flame retardant grade, and in the example 3, the flame retardant grade is reduced by one grade due to the addition of excessive toughening agent, and the mechanical property is reduced to a certain extent; the comparative example 1 without using a flame retardant has no flame retardant effect, the comparative example 2 uses an RDP organic flame retardant, the flame retardant grade of which does not reach the standard, and the comparative example 3 is a PC/ABS alloy with a higher content of the currently used flame retardant, and can reach the flame retardant grade of 1.6mm V-0 because of the higher content of the flame retardant. Therefore, the PC/ABS alloy disclosed by the embodiment of the invention uses the red phosphorus master batch as the flame retardant, so that the use amount of red phosphorus is reduced, and meanwhile, the PC/ABS alloy can show stronger tensile strength, tensile strain at break, tensile elastic modulus and tensile yield stress; in addition, the red phosphorus has no pollution to the environment, so the PC/ABS alloy has good environmental protection performance.
The cross section of the red phosphorus master batch provided in example 2 was subjected to electron microscope Scanning (SEM) and EDS energy spectrum analysis, and the results are shown in fig. 3 and 4. It can be seen from fig. 3 and 4 that the phosphorus element has good dispersibility in the red phosphorus master batch.
The cross section of the PC/ABS alloy provided in example 2 was analyzed by electron microscope Scanning (SEM) and EDS spectroscopy, and the results are shown in FIGS. 5 and 6. It can be seen from fig. 5 and 6 that the red phosphorus master batch and the red phosphorus have good dispersibility in the PC/ABS alloy.
In conclusion, it can be seen from the results of examples 1 to 3, comparative examples 1 to 3, SEM and EDS that the PC/ABS alloy provided by the embodiments of the present invention has the characteristics of low red phosphorus content, uniform red phosphorus dispersion, flame retardant rating up to 1.6mm V-0 level, good environmental protection performance, good mechanical properties, etc., and solves the problem that the existing PC/ABS alloy has ideal flame retardant effect only by directly using red phosphorus as a flame retardant and requiring a large amount of red phosphorus, and also solves the problem that the mechanical properties of the PC/ABS alloy are deteriorated due to a large amount of red phosphorus.
It should be understood that the term "and/or" as used in this specification and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items. It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or system. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or system that comprises the element.
The above-mentioned serial numbers of the embodiments of the present invention are merely for description and do not represent the merits of the embodiments. While the invention has been described with reference to specific embodiments, the invention is not limited thereto, and various equivalent modifications and substitutions can be easily made by those skilled in the art without departing from the scope of the invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. The PC/ABS alloy is characterized by comprising the following components in parts by weight:
Figure FDA0002970578420000011
the red phosphorus master batch comprises the following components in percentage by mass, wherein the total content of the components in the red phosphorus master batch is 100 percent:
10 to 50 percent of red phosphorus;
50 to 90 percent of dispersant.
2. The PC/ABS alloy according to claim 1, wherein the PC/ABS alloy comprises the following components, based on 100% of the total mass of the components in the red phosphorus master batch:
25% -45% of red phosphorus;
55 to 75 percent of dispersant.
3. The PC/ABS alloy according to claim 1 or 2, wherein the dispersant is selected from at least one of ethylene-octene copolymer grafted maleic anhydride, maleic anhydride grafted polyethylene, ethylene vinyl acetate copolymer grafted maleic anhydride.
4. The PC/ABS alloy according to claim 1, wherein the compatibilizer is a styrene-maleic anhydride copolymer, and the graft ratio of maleic anhydride in the styrene-maleic anhydride copolymer is 10-30%.
5. The PC/ABS alloy according to claim 4, wherein the graft ratio of maleic anhydride in the styrene-maleic anhydride copolymer is 15% to 20%.
6. The PC/ABS alloy of claim 1, wherein the polycarbonate is a bisphenol A polycarbonate;
and/or the presence of a gas in the gas,
the lubricant comprises an external lubricant and an internal lubricant; the external lubricant is at least one of zinc stearate and pentaerythritol stearate; the internal lubricant is dioctyl phthalate;
and/or the presence of a gas in the gas,
the toughening agent is selected from at least one of methacrylic acid-butadiene-styrene copolymer, polyolefin thermoplastic elastomer, thermoplastic polyurethane elastomer, ethylene butyl acrylate, ethylene propylene diene monomer and ethylene-vinyl acetate copolymer.
7. The preparation method of the PC/ABS alloy is characterized by comprising the following steps:
providing a polycarbonate, an ABS plastic, a compatibilizer, a lubricant, a red phosphorus masterbatch, and a toughening agent according to any of claims 1 to 6;
mixing the polycarbonate, the ABS plastic, the compatibilizer, the lubricant, the red phosphorus master batch and the toughening agent to obtain a mixed material;
and carrying out melt extrusion treatment on the mixed material, and carrying out bracing and granulation treatment to obtain the PC/ABS alloy.
8. The method for preparing the PC/ABS alloy according to claim 7, wherein the melt extrusion comprises ten temperature control zones from the first temperature control zone to the tenth temperature control zone, wherein the temperatures of the first temperature control zone and the second temperature control zone are both 190-195 ℃; the temperature of the temperature control three area and the temperature control four area are both 200-205 ℃; the temperature of the temperature control five area and the temperature control six area are both 210-215 ℃; the temperature of the temperature control seven area and the temperature control eight area are both 220-225 ℃; the temperature of the nine temperature control areas is 210-220 ℃; the temperature in the ten temperature control zones was 225 ℃.
9. The preparation method of the PC/ABS alloy according to claim 7, wherein the red phosphorus master batch is prepared by the following method:
providing red phosphorus and a dispersant;
mixing red phosphorus and a dispersing agent to obtain a pre-dispersion body;
and granulating the pre-dispersion to obtain the red phosphorus master batch.
10. Use of the PC/ABS alloy according to any of claims 1-6 in housings of telecommunication base station equipment, mobile terminals, automotive interiors.
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