CN114133692A - Flame-retardant ABS material and application thereof - Google Patents

Flame-retardant ABS material and application thereof Download PDF

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Publication number
CN114133692A
CN114133692A CN202111358645.9A CN202111358645A CN114133692A CN 114133692 A CN114133692 A CN 114133692A CN 202111358645 A CN202111358645 A CN 202111358645A CN 114133692 A CN114133692 A CN 114133692A
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flame retardant
flame
abs material
retardant abs
antimony
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Inventor
刘凯
陈平绪
叶南飚
杨霄云
付锦锋
秦旺平
王亮
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Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—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
    • 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
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic

Abstract

The invention discloses a flame-retardant ABS material and application thereof. The flame-retardant ABS material comprises the following components in parts by weight: 50-60 parts of ABS resin, 15-20 parts of permanent antistatic agent, 4-8 parts of talcum powder, 1-3 parts of compatilizer, 15-20 parts of flame retardant and 0.3-1 part of antioxidant, wherein the talcum powder is superfine talcum powder, and the mesh number is not less than 20000 meshes. According to the invention, the superfine talcum powder with the mesh number of more than or equal to 20000 meshes is added into the flame-retardant ABS material, so that the material can keep high rigidity and high toughness while excellent antistatic property is obtained.

Description

Flame-retardant ABS material and application thereof
Technical Field
The invention belongs to the field of plastics, and relates to a flame-retardant ABS material and application thereof.
Background
Acrylonitrile-butadiene-styrene terpolymer (ABS resin) is a material with balanced mechanical properties, high dimensional stability, excellent appearance and easy processing. The ABS resin is extremely easy to burn, and the flame-retardant ABS material prepared by flame-retardant modification of the ABS resin is widely applied to the fields of electronic appliances and the like. ABS is a high molecular material with excellent electrical insulation properties, usually with a surface resistance of > 1016Omega, electrostatic interaction is easily generated during the use process. Excessive charges accumulated by electrostatic action easily cause discharge phenomena, which may cause ignition of electric appliances and fire. Therefore, the preparation of flame retardant ABS material with antistatic function is necessary.
At present, the antistatic function of the flame-retardant ABS material is mainly endowed by adding auxiliary agents such as a surfactant, carbon black, carbon fiber, steel fiber, a permanent antistatic agent and the like. Wherein, the addition of the surfactant can cause the surface of the product to be atomized; the carbon black is added, only black products can be manufactured, color matching cannot be performed, and the resistance value is uneven; carbon fiber is added, only a dark product can be manufactured, color matching is not easy, and meanwhile, the toughness is low; the addition of steel fibers can result in excessive costs. The addition of permanent antistatic agents can avoid the above problems, but leads to a softer material and insufficient rigidity.
Therefore, it is very meaningful to research how to keep the flame retardant ABS material added with the permanent antistatic agent with good high rigidity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a flame-retardant ABS material and application thereof, and aims to ensure that the flame-retardant ABS material added with a permanent antistatic agent has good mechanical properties, such as high rigidity, high toughness and the like.
In order to achieve the above object, the first aspect of the present invention provides a flame retardant ABS material, which comprises the following components in parts by weight:
Figure BDA0003357598380000021
wherein the talcum powder is superfine talcum powder, and the mesh number is more than or equal to 20000 meshes.
The addition of permanent antistatic agents, usually in amounts of 10 to 25% by weight, to flame-retardant ABS materials leads to a drastic reduction in the rigidity (flexural strength) of the material. The talcum powder is a two-dimensional lamellar inorganic material, and due to large anisotropy, the rigidity (bending strength) of the material can be greatly improved by adding the talcum powder into the flame-retardant ABS material, but the toughness (cantilever notch impact strength) of the flame-retardant ABS material is obviously reduced by adding the conventional talcum powder. The inventor finds that the superfine talcum powder with the mesh number of more than or equal to 20000 meshes is added into the flame-retardant ABS material, so that the toughness of the material is slightly influenced while the rigidity increasing effect is achieved.
Preferably, the mesh number of the talcum powder is 20000-30000 meshes. When the mesh number of the talcum powder is 20000-30000 meshes, the high-rigidity reinforcing material not only can play a good rigidity reinforcing role, but also has small influence on the toughness of the material; when the mesh number of the talcum powder exceeds 30000 meshes, the rigidity and the toughness of the material are not further obviously influenced.
Preferably, the compatilizer is a long-chain amide compatilizer with carboxyl. The "long-chain amide-based compatibilizing agent having a carboxyl group" herein refers to a long-chain amide-based compatibilizing agent having a carboxyl group with a C atom number of 28 or more. The long-chain amide compatilizer with carboxyl has a long-chain alkyl skeleton, simultaneously carries an amide group and a long-chain carboxyl group, and has good amphipathy, wherein the long-chain alkane skeleton is compatible with ABS resin, and the amide and carboxyl groups are compatible with superfine talcum powder, so that the compatilizer can greatly improve the binding force between the ABS and the superfine talcum powder, thereby well improving the toughness of the flame-retardant ABS material. Meanwhile, the long-chain amide compatilizer with carboxyl can also improve the antistatic property of the flame-retardant ABS material, so that the antistatic property is more excellent and lasting.
Preferably, the compatibilizer has the formula RCONXCH2-CH2NXCOR, wherein X is C6～C26A monovalent linear carboxylic acid ofR is C6～C26Alkyl group of (1). The inventor finds that the specific compatilizer can well improve the toughness and the antistatic property of the flame-retardant ABS material, so that the rigidity of the obtained flame-retardant ABS material is more than 2100MPa, and the toughness is more than 16kJ/m2Surface resistivity of 1.3X 10 or less8Ω。
Preferably, the butadiene rubber content of the ABS resin is 20-40 wt%. The butadiene rubber content of the ABS resin is too low, so that the toughness of the flame-retardant ABS material is insufficient, and the material is brittle; the butadiene rubber content of the ABS resin is too high, so that the ABS resin is not easy to process (low in fluidity) and can cause insufficient rigidity of flame-retardant ABS, and the material is soft, so that the butadiene rubber content of the ABS resin is selected to be 20-40 wt% to obtain higher toughness and rigidity.
The present invention is not limited to the kind of permanent antistatic agent. As one example, the permanent antistatic agent is at least one of an amide-based permanent antistatic agent, an ester-based permanent antistatic agent, and the like. Amide permanent antistatic agents such as PELESTAT-6500 and ATMER 163, ester permanent antistatic agents such as SUNNICO ASA-2500, etc., and one or more of these permanent antistatic agents can be optionally added.
The present invention is not limited to the kind of flame retardant. As an example, the flame retardant comprises an antimony-based flame retardant and a bromine-based flame retardant, and the mass ratio of the antimony-based flame retardant to the bromine-based flame retardant is antimony-based flame retardant: a brominated flame retardant (3-5): (12-15). The antimony flame retardant and the bromine flame retardant are not limited in kind, and may be at least one selected from antimony trioxide, antimony pentoxide, etc., and bromine flame retardant is at least one selected from bromotriazine, tetrabromobisphenol A, brominated epoxy, etc.
The present invention is not limited in kind of the antioxidant. As an example, the antioxidant is at least one of a hindered phenol antioxidant, a phosphite antioxidant, and the like.
The preparation method of the flame-retardant ABS material is not limited, and the flame-retardant ABS material can be prepared by adopting the preparation method of the flame-retardant ABS material with any permanent antistatic agent in the prior art. As an example, the preparation method of the flame-retardant ABS material comprises the following steps: uniformly mixing ABS resin, permanent antistatic agent, talcum powder, compatilizer, flame retardant and antioxidant to obtain a premix; and mixing and extruding the premix to obtain the flame-retardant ABS material.
In a second aspect, the invention provides an application of the flame-retardant ABS material in electronic products.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the superfine talcum powder with the mesh number of more than or equal to 20000 meshes is added into the flame-retardant ABS material, so that the material can keep high rigidity and high toughness while obtaining excellent antistatic property; on the basis, the long-chain amide compatilizer with carboxyl is further added, so that the toughness and the antistatic property of the material can be improved.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.
The raw materials used in the examples and comparative examples were as follows:
ABS resin A: ABS GP-22, Brazier Korea, butadiene rubber content 30 wt%;
ABS resin B: ABS 750N SW, Korea brocade lake petrochemistry, butadiene rubber content 20 wt%;
ABS resin C: ABS DG-MG29, Tianjin Staphylol chemical Co., Ltd, butadiene rubber content 40 wt%;
permanent antistatic agent A: amide-based permanent antistatic agents;
permanent antistatic agent B: ester permanent antistatic agents;
talc powder A: HTPUltra5L, 30000 mesh, Italy Eimer;
talcum powder B: HTPUltra5, 25000 mesh, Eimeria Italy;
talc powder C: nanotalcum, 20000 mesh, Shanghai Yunjiang chemical Co., Ltd;
talc powder D: superfine talcum powder, 10000 meshes, brocade inorganic new material company;
talc powder E: TYT-777A, 3000 mesh, Xiamen Haichuan Industrial and trade Co., Ltd;
a compatilizer A: TAS 2A, Qingdao Sainuo chemical Co., Ltd, molecular formula RCONXCH2-CH2NXCOR, wherein X is C6-26R is C6-26Alkyl groups of (a);
a compatilizer B: styrene-maleic anhydride copolymer SMA 700;
a compatilizer C: maleic anhydride grafted ABS copolymer KT-2;
a compatilizer D: an amide lubricant EBS;
flame retardant A: the adhesive consists of brominated triazine and antimony trioxide, wherein the mass ratio of the brominated triazine to the antimony trioxide is as follows: antimony trioxide is 3: 15;
and (3) a flame retardant B: the adhesive consists of brominated triazine and antimony trioxide, wherein the mass ratio of the brominated triazine to the antimony trioxide is as follows: antimony trioxide 4: 14;
and (3) a flame retardant C: the adhesive consists of brominated triazine and antimony trioxide, wherein the mass ratio of the brominated triazine to the antimony trioxide is as follows: antimony trioxide 5: 12;
antioxidant: phosphite antioxidant tris (2, 4-di-tert-butylphenyl) phosphite.
The above-mentioned unspecified raw materials are commercially available, and some components (e.g., permanent antistatic agent A, flame retardant B, antioxidant, etc.) in each of examples and comparative examples are the same commercially available products.
Examples and comparative examples
Each of the examples and comparative examples provides a flame retardant ABS material, the composition of which is shown in tables 1-2 (in the table, "-" indicates a content of 0), and the preparation method comprises the following steps: adding ABS resin, permanent antistatic agent, talcum powder, compatilizer, flame retardant and antioxidant into a mixer, and uniformly mixing to obtain a premix; and (3) feeding the premix into an extruder, mixing and extruding, and processing to obtain the antistatic flame-retardant ABS material, wherein the extrusion temperature is 190-. Except for different formulas, the flame-retardant ABS materials of the examples and the comparative examples have the same preparation process steps and other process parameters.
TABLE 1 compositions/parts by weight of flame retardant ABS materials of examples 1-7 and comparative examples 1-4
Figure BDA0003357598380000051
Figure BDA0003357598380000061
TABLE 2 examples 4, 8-12 flame retardant ABS materials composition/parts by weight
Figure BDA0003357598380000062
Examples of effects
The performance test of the flame-retardant ABS materials of the examples and the comparative examples is carried out by the following specific method: flame retardant test standard: UL 94-2018, the thickness of a spline is 2.0 mm;
notched izod impact strength: ISO 180-;
flexural modulus: ISO 178-;
surface resistance: GB/T3048.5-2007.
The test results are shown in Table 3.
TABLE 3 Performance test results of flame retardant ABS materials obtained in each example and comparative example
Figure BDA0003357598380000063
Figure BDA0003357598380000071
Comparing examples 3-7 with comparative examples 1-4, it can be seen that, compared with talc powder with mesh number less than 20000, the addition of talc powder with mesh number greater than or equal to 20000 into ABS material can improve the rigidity (flexural modulus) effect, and at the same time, the impact on the toughness (impact strength) of the material is small, thus ensuring the material to have higher toughness; in the presence of the same amount of the long-chain amide compatilizer with carboxyl, the rigidity (flexural modulus) of the material is continuously improved and the toughness (impact strength) is slowly reduced along with the increase of the addition amount of the talcum powder with the mesh number of more than or equal to 20000 meshes, which shows that the talcum powder with the mesh number of more than or equal to 20000 meshes has a remarkable rigidity increasing effect and has small influence on the toughness in the presence of the long-chain amide compatilizer with carboxyl.
Compared with the comparative example 2, the examples 3, 4, 8-12 show that the addition of the long-chain amide compatilizer with carboxyl can reduce the surface resistivity of the material, namely, the antistatic performance of the material is improved to a certain extent; with the increase of the addition amount of the long-chain amide compatilizer with carboxyl, the toughness (impact strength) of the material is increased, the rigidity (flexural modulus) is almost unchanged, and the surface resistivity is slowly reduced; compared with other compatilizers, the long-chain amide compatilizer with carboxyl can better improve the toughness of the material and reduce the surface resistivity.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The flame-retardant ABS material is characterized by comprising the following components in parts by weight:
Figure FDA0003357598370000011
wherein the talcum powder is superfine talcum powder, and the mesh number is more than or equal to 20000 meshes.
2. The flame retardant ABS material as claimed in claim 1, wherein the talc has a mesh size of 20000-30000 mesh.
3. The flame retardant ABS material of claim 1 wherein the compatibilizer is a long chain amide compatibilizer having a carboxyl group.
4. The flame retardant ABS material of claim 3 wherein the compatibilizer has the formula RCONXCH2-CH2NXCOR, wherein X is C6～C26R is C6～C26Alkyl group of (1).
5. The flame retardant ABS material of claim 1 wherein the butadiene rubber content of the ABS resin is 20 to 40 wt%.
6. The flame retardant ABS material of claim 1 wherein the permanent antistatic agent is at least one of an amide type permanent antistatic agent and an ester type permanent antistatic agent.
7. The flame-retardant ABS material according to claim 1, wherein the flame retardant comprises an antimony flame retardant and a bromine flame retardant, and the mass ratio of the antimony flame retardant to the bromine flame retardant is that the antimony flame retardant: a brominated flame retardant (3-5): (12-15).
8. The flame retardant ABS material of claim 7 wherein the antimony based flame retardant is at least one of antimony trioxide, antimony pentoxide; the brominated flame retardant is at least one of brominated triazine, tetrabromobisphenol A and brominated epoxy.
9. The flame retardant ABS material of claim 1 wherein the antioxidant is at least one of a hindered phenolic antioxidant and a phosphite antioxidant.
10. Use of a flame retardant ABS material according to any of claims 1-9 in electronic products.
CN202111358645.9A 2021-11-16 2021-11-16 Flame-retardant ABS material and application thereof Pending CN114133692A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102020825A (en) * 2010-12-23 2011-04-20 余林华 Flame-retardant permanent antistatic ABS material and preparation method thereof
CN103819866A (en) * 2014-02-18 2014-05-28 金发科技股份有限公司 High-performance permanently-antistatic flame-retardant ABS (acrylonitrile butadiene styrene) material and preparation method and application
CN109593356A (en) * 2018-11-19 2019-04-09 江苏金发科技新材料有限公司 PA66 composite material and preparation method with excellent low temperature toughness, low water absorption and high rigidity
CN112552635A (en) * 2020-11-30 2021-03-26 金发科技股份有限公司 Halogen-free flame-retardant ABS material special for storage battery and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102020825A (en) * 2010-12-23 2011-04-20 余林华 Flame-retardant permanent antistatic ABS material and preparation method thereof
CN103819866A (en) * 2014-02-18 2014-05-28 金发科技股份有限公司 High-performance permanently-antistatic flame-retardant ABS (acrylonitrile butadiene styrene) material and preparation method and application
CN109593356A (en) * 2018-11-19 2019-04-09 江苏金发科技新材料有限公司 PA66 composite material and preparation method with excellent low temperature toughness, low water absorption and high rigidity
CN112552635A (en) * 2020-11-30 2021-03-26 金发科技股份有限公司 Halogen-free flame-retardant ABS material special for storage battery and preparation method and application thereof

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