CN113604001A - Low-cost flame-retardant ABS material and preparation method thereof - Google Patents

Low-cost flame-retardant ABS material and preparation method thereof Download PDF

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Publication number
CN113604001A
CN113604001A CN202110668126.6A CN202110668126A CN113604001A CN 113604001 A CN113604001 A CN 113604001A CN 202110668126 A CN202110668126 A CN 202110668126A CN 113604001 A CN113604001 A CN 113604001A
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Prior art keywords
flame retardant
abs
retardant
flame
low
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CN202110668126.6A
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Chinese (zh)
Inventor
刘长来
夏诗忠
史锋
高国兴
刘世忠
徐建刚
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Camel Group Plastic Products Co ltd
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Camel Group Plastic Products Co ltd
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Priority to CN202110668126.6A priority Critical patent/CN113604001A/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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

The invention discloses a low-cost flame-retardant ABS material and a preparation method thereof. Belongs to the technical field of high polymer materials. The method mainly solves the problem that the recycled ABS storage battery shell is not flame-retardant and has influence on recycling due to trace acid residue. It is mainly characterized in that: the low-cost flame-retardant ABS material consists of 55-70% of recovered ABS resin, 15-20% of flame retardant, 1-5% of synergistic flame retardant, 1-5% of inorganic filler, 5-15% of toughening agent and 0.7-1.5% of other auxiliary agents; the preparation method comprises the steps of (1) weighing raw materials according to the mass proportion, and (2) putting the weighed components into a high-speed mixer, and stirring according to a mixing process to obtain a mixture; (3) and putting the mixture into a melt extruder for extrusion and granulation. The low-cost flame-retardant ABS material prepared by the invention has better mechanical property and flame retardant property. The invention is mainly used for recycling the ABS storage battery shell in the storage battery industry.

Description

Low-cost flame-retardant ABS material and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a low-cost flame-retardant ABS material and a preparation method thereof.
Background
The ABS resin is a graft copolymer of Acrylonitrile, Butadiene and Styrene, the relative contents of the three monomers are as follows, 15-35% of Acrylonitrile, 5-30% of Butadiene and 40-60% of Styrene, and the common ABS resin is ivory in appearance, non-toxic, tasteless, tough and rigid, and is a high-gloss thermoplastic high polymer material easy to process and form.
Because of its good mechanical properties and smooth appearance, as well as good insulating properties and chemical solvent resistance, ABS materials are often chosen as the battery case in the battery industry. After the service life of the battery is over, a large amount of recovered ABS material can be generated, and good economic benefit and social effect can be generated if the recovered ABS material is utilized.
ABS material is not good in flame retardant property, easy to burn, and generates a large amount of smoke and unpleasant odor in the burning process, most ABS materials used in the industry of storage batteries are not flame retardant, and recovered ABS materials are used as resin base materials for flame retardant modification, so that the material application can be expanded, the material value can be improved, but trace sulfuric acid is remained in the recovered materials, and the mechanical property and the flame retardant property of the materials can be influenced if the recovered materials are not treated.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a low-cost flame-retardant ABS material, and the invention further aims to provide a preparation method of the low-cost flame-retardant ABS material.
The above purpose of the invention is realized by the following technical scheme: the low-cost flame-retardant ABS material is characterized by comprising the following components in percentage by mass: 55-70% of recycled ABS resin, 15-20% of flame retardant, 1-5% of synergistic flame retardant, 1-5% of inorganic filler, 5-15% of toughening agent and 0.7-1.5% of other auxiliary agents.
Preferably, the recycled ABS resin accounts for 60-68%, the flame retardant accounts for 16-19%, the synergistic flame retardant accounts for 2-4%, the inorganic filler accounts for 2-4%, the toughening agent accounts for 8-12%, and other auxiliary agents account for 0.9-1.3%.
Preferably, the recovered ABS resin is a recovered ABS accumulator shell broken material.
Preferably, the flame retardant is a brominated flame retardant, including but not limited to one or more of decabromodiphenylethane, octabromoether, bromotriazine, brominated styrene, tetrabromobisphenol A and the like.
Preferably, the synergistic flame retardant is antimony trioxide.
Preferably, the inorganic filler is Mg (OH)2And Al (OH)3One or a mixture of the two.
Preferably, the toughening agent is one or a mixture of high rubber powder and MBS.
Preferably, the other auxiliary agents are an antioxidant, an anti-ultraviolet agent and a lubricant, wherein the antioxidant accounts for 0.2-0.5% of the total mass of the material; the lubricant accounts for 0.3-0.5% of the total mass of the material; the uvioresistant agent accounts for 0.2-0.5% of the total mass of the material.
Preferably, the antioxidant is compounded by a main antioxidant of tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester (1010) and an auxiliary antioxidant of tris (2, 4-di-tert-butylphenyl) phosphite ester, preferably 1: 2, compounding, wherein the compound accounts for 0.2-0.5% of the total mass of the material; the lubricant is N, N' -ethylene bis stearamide, and accounts for 0.3-0.5% of the total mass of the material; the uvioresistant agent is UV-770 or UV-531, and accounts for 0.2-0.5% of the total mass of the material.
The above further object of the present invention is achieved by the following technical solutions: a preparation method of a low-cost flame-retardant ABS material is characterized by comprising the following steps:
(1) preparing materials: weighing raw materials according to a mass ratio, wherein the raw materials comprise recovered ABS resin, a flame retardant, a synergistic flame retardant, an inorganic filler, a toughening agent and other auxiliaries;
(2) mixing: putting the weighed components into a high-speed mixer, and stirring according to a mixing process to obtain a mixture;
(3) melt extrusion: and putting the mixture into a melt extruder for extrusion and granulation.
Preferably, in the step (1), the recovered ABS resin is a recovered ABS storage battery shell, the flame retardant is one or a plurality of decabromodiphenylethane, octabromoether, bromotriazine, brominated styrene and tetrabromobisphenol A, the synergistic flame retardant is antimony trioxide, and the inorganic filler is Mg (OH)2And Al (OH)3One or both of the two components are compounded, the toughening agent is one or both of high rubber powder and MBS, and the other auxiliary agents are antioxidant accounting for 0.2-0.5 percent of the total mass of the material, anti-ultraviolet agent accounting for 0.2-0.5 percent of the total mass of the material and lubricant accounting for 0.3-0.5 percent of the total mass of the material.
Compared with the prior art, the invention has the following beneficial effects: the low-cost flame-retardant ABS material provided by the invention selects the recycled ABS material as the resin substrate, and has obvious cost advantage compared with the common flame-retardant ABS material. The inorganic filler magnesium hydroxide or/and aluminum hydroxide added into the material is alkalescent, can neutralize trace acid remained in the recovered material in the processing process, reduces the influence of the trace acid on the material, and makes up the influence of impurities in the flame retardant and the recovered material on the toughness of the material by the flexibilizer in the formula system. The low-cost flame-retardant ABS material prepared by the formula has better mechanical property and flame retardant property.
The invention is mainly used for recycling the ABS storage battery shell in the storage battery industry.
Detailed Description
The present invention is further explained with reference to the following examples, which are not intended to limit the present invention in any way.
The invention relates to a low-cost flame-retardant ABS material, which comprises the following components in percentage by mass: recovery of AB55-70% of S resin, 15-20% of flame retardant, 1-5% of synergistic flame retardant, 1-5% of inorganic filler, 5-15% of toughening agent and 0.7-1.5% of other auxiliary agents. Preferably, the paint comprises the following components in percentage by mass: 60-68% of recovered ABS resin, 16-19% of flame retardant, 2-4% of synergistic flame retardant, 2-4% of inorganic filler, 8-12% of toughening agent and 0.9-1.3% of other auxiliary agents. Wherein, the recovered ABS resin is the ABS accumulator shell recovered in the accumulator industry. The flame retardant is a brominated flame retardant, and comprises but is not limited to one or more of decabromodiphenylethane, octabromoether, bromotriazine, brominated styrene and tetrabromobisphenol A. The synergistic flame retardant is antimony trioxide. The inorganic filler is Mg (OH)2And Al (OH)3One or two of the components are compounded. The toughening agent is one or two of high rubber powder and MBS. The other auxiliary agents are an antioxidant, an anti-ultraviolet agent and a lubricant, wherein the antioxidant is a main antioxidant which is tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester (1010) and an auxiliary antioxidant which is tri (2, 4-di-tert-butylphenyl) phosphite which are compounded and account for 0.2-0.5% of the total mass of the material, the lubricant accounts for 0.3-0.5% of the total mass of the material, and the anti-ultraviolet agent is UV-770 or UV-531 and accounts for 0.2-0.5% of the total mass of the material.
The invention relates to a preparation method of a low-cost flame-retardant ABS material, which comprises the following steps:
(1) preparing materials: weighing raw materials according to a mass ratio, wherein the raw materials comprise recovered ABS resin, a flame retardant, a synergistic flame retardant, an inorganic filler, a toughening agent and other auxiliaries; wherein, the recovered ABS resin is the recovered ABS accumulator shell, the flame retardant is one or a plurality of decabromodiphenylethane, octabromoether, bromotriazine, brominated styrene and tetrabromobisphenol A, the synergistic flame retardant is antimony trioxide, the inorganic filler is Mg (OH)2And Al (OH)3One or both of the two is compounded, the toughening agent is one or both of high rubber powder and MBS, and the other auxiliary agents are antioxidant accounting for 0.2-0.5 percent of the total mass of the material, anti-ultraviolet agent accounting for 0.2-0.5 percent of the total mass of the material and lubricant accounting for 0.3-0.5 percent of the total mass of the material;
(2) mixing: putting the weighed components into a high-speed mixer, and stirring according to a mixing process to obtain a mixture;
(3) melt extrusion: and putting the mixture into a melt extruder for extrusion and granulation.
Example 1:
firstly, 69 mass percent of recovered ABS resin, 15 mass percent of decabromodiphenylethane, 4 mass percent of antimony trioxide, 8 mass percent of high-rubber powder (181 powder), 3 mass percent of aluminum hydroxide, 0.5 mass percent of antioxidant (a main antioxidant of tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester (1010) and an auxiliary antioxidant of tri (2, 4-di-tert-butylphenyl) phosphite are compounded in a ratio of 1: 2), 0.3 mass percent of lubricant (N, N' -ethylene bis stearamide) and 0.2 mass percent of uvioresistant agent UV-770 are put into a high-speed mixer to be mixed for two minutes, and then enter a double-screw extruder from a metering double-screw feeder to be plasticized and melted, and then extruded, cooled, magnetized and packaged to obtain the product.
Example 2:
firstly, 66 mass percent of recovered ABS resin, 16 mass percent of brominated triazine, 5 mass percent of antimony trioxide, 10 mass percent of high-rubber powder (181 powder), 2 mass percent of magnesium hydroxide, 0.5 mass percent of antioxidant (a main antioxidant of tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester (1010) and an auxiliary antioxidant of tri (2, 4-di-tert-butylphenyl) phosphite are compounded in a ratio of 1: 2), 0.3 mass percent of lubricant (N, N' -ethylene bis stearamide) and 0.2 mass percent of anti-ultraviolet agent UV-531 are put into a high-speed mixer to be mixed for two minutes, then enter a double-screw extruder from a metering feeder to be plasticized and melted, and then are extruded, cooled, magnetized and packaged to obtain the product.
The preparation method and process of examples 1 and 2 are as follows:
(1) treatment and mixing of raw materials:
putting the recovered ABS resin, the flame retardant, the synergistic flame retardant, the inorganic filler, the toughening agent and other auxiliaries into a high-speed mixer to mix for two minutes, so that all the components are fully stirred and uniformly dispersed;
(2) melt extrusion:
adding the mixed materials into a double-screw extruder, wherein the melt extrusion temperature is between 185 ℃ and 210 ℃, and the rotating speed of the screw is 360 revolutions per minute;
(3) granulation and post-treatment:
and cooling, air-drying, granulating, strong magnetic treatment and packaging the extruded material to obtain a finished product.
The properties of the low-cost flame-retardant ABS materials obtained in example 1 and example 2 are as follows:
Figure DEST_PATH_IMAGE001
the above is the preferred embodiment of the present invention.
The invention discloses a low-cost flame-retardant ABS material, which has good flame retardance and excellent mechanical property, wherein the recovered storage battery shell ABS material is used as a resin base material, the price of the resin base material is less than half of the price of a new material, magnesium hydroxide or aluminum hydroxide is used as filling in a formula, the residual trace acid in the recovered material can be neutralized, and a toughening agent is added in the formula system, so that the toughness of the material can be improved, and the material has good mechanical property under the condition of having a flame-retardant effect. The material prepared by the invention has extremely high cost performance.
All changes made according to the technical scheme of the invention, when the generated functional function does not exceed the scope of the technical scheme of the invention, belong to the protection scope of the invention.

Claims (9)

1. The low-cost flame-retardant ABS material is characterized by comprising the following components in percentage by mass: 55-70% of recycled ABS resin, 15-20% of flame retardant, 1-5% of synergistic flame retardant, 1-5% of inorganic filler, 5-15% of toughening agent and 0.7-1.5% of other auxiliary agents.
2. The low-cost flame-retardant ABS material according to claim 1, wherein: the recovered ABS resin is a recovered ABS accumulator shell crushing material.
3. A low cost flame retardant ABS material according to claim 1 or 2 characterized by: the flame retardant is a brominated flame retardant, and comprises but is not limited to one or more of decabromodiphenylethane, octabromoether, bromotriazine, brominated styrene and tetrabromobisphenol A.
4. A low cost flame retardant ABS material according to claim 1 or 2 characterized by: the synergistic flame retardant is antimony trioxide.
5. A low cost flame retardant ABS material according to claim 1 or 2 characterized by: the inorganic filler is Mg (OH)2And Al (OH)3One or a mixture of the two.
6. A low cost flame retardant ABS material according to claim 1 or 2 characterized by: the toughening agent is one or a mixture of high rubber powder and MBS.
7. A low cost flame retardant ABS material according to claim 1 or 2 characterized by: the other auxiliary agents comprise an antioxidant, an anti-ultraviolet agent and a lubricant, wherein the antioxidant accounts for 0.2-0.5% of the total mass of the material, the lubricant accounts for 0.3-0.5% of the total mass of the material, and the anti-ultraviolet agent accounts for 0.2-0.5% of the total mass of the material.
8. A method for preparing the low-cost flame-retardant ABS material of claim 1, which is characterized by comprising the following steps:
preparing materials: weighing raw materials according to a mass ratio, wherein the raw materials comprise recovered ABS resin, a flame retardant, a synergistic flame retardant, an inorganic filler, a toughening agent and other auxiliaries;
mixing: putting the weighed components into a high-speed mixer, and stirring according to a mixing process to obtain a mixture;
melt extrusion: and putting the mixture into a melt extruder for extrusion and granulation.
9. The method for preparing the low-cost flame-retardant ABS material according to claim 8, wherein: in the step (1), the recovered ABS resin is a recovered ABS storage battery shell, and the flame retardant is decabromodiphenylethane and octabromineOne or more of ether, bromotriazine, brominated styrene and tetrabromobisphenol A are compounded, the synergistic flame retardant is antimony trioxide, and the inorganic filler is Mg (OH)2And Al (OH)3One or both of the two components are compounded, the toughening agent is one or both of high rubber powder and MBS, and the other auxiliary agents are antioxidant accounting for 0.2-0.5 percent of the total mass of the material, anti-ultraviolet agent accounting for 0.2-0.5 percent of the total mass of the material and lubricant accounting for 0.3-0.5 percent of the total mass of the material.
CN202110668126.6A 2021-06-16 2021-06-16 Low-cost flame-retardant ABS material and preparation method thereof Pending CN113604001A (en)

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Application Number Priority Date Filing Date Title
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104262891A (en) * 2014-09-10 2015-01-07 四川塑金科技有限公司 Flame-retardant regenerated ABS particle and preparation method thereof
CN106832736A (en) * 2015-12-07 2017-06-13 宁波卡帝亚电器有限公司 A kind of high-temp resistant fire-retarding ABS material
CN110343378A (en) * 2019-07-10 2019-10-18 东莞市国亨塑胶科技有限公司 A kind of high flowing environment-friendlyflame-retardant flame-retardant material and preparation method thereof prepared by regenerated resources

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104262891A (en) * 2014-09-10 2015-01-07 四川塑金科技有限公司 Flame-retardant regenerated ABS particle and preparation method thereof
CN106832736A (en) * 2015-12-07 2017-06-13 宁波卡帝亚电器有限公司 A kind of high-temp resistant fire-retarding ABS material
CN110343378A (en) * 2019-07-10 2019-10-18 东莞市国亨塑胶科技有限公司 A kind of high flowing environment-friendlyflame-retardant flame-retardant material and preparation method thereof prepared by regenerated resources

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