CN107974026B - Extinction flame-retardant ABS material and preparation method thereof - Google Patents

Extinction flame-retardant ABS material and preparation method thereof Download PDF

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CN107974026B
CN107974026B CN201610921951.1A CN201610921951A CN107974026B CN 107974026 B CN107974026 B CN 107974026B CN 201610921951 A CN201610921951 A CN 201610921951A CN 107974026 B CN107974026 B CN 107974026B
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extinction
flame
retardant
flame retardant
abs material
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CN107974026A (en
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丁树岩
金滟
蔡涛
石胜鹏
康鹏
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

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

Abstract

The invention relates to a flame-retardant extinction ABS material and a preparation method thereof. The material comprises the following components in a blending mode: ABS resin, a delustering component, a flame retardant and an antioxidant. The extinction component comprises three components, namely SEBS, polyolefin resin and metal oxide. The flame retardant is divided into a main flame retardant and an auxiliary flame retardant. The extinction flame-retardant ABS material prepared by the invention has the characteristics of good extinction performance, high surface smoothness and good mechanical property, and can be widely applied to automobile interior trims, large-scale passenger car ceiling buckle plates, various electrical instrument shell types and the like.

Description

Extinction flame-retardant ABS material and preparation method thereof
Technical Field
The invention relates to the field of modified plastics, in particular to an extinction flame-retardant ABS material and a preparation method thereof.
Background
ABS and its alloy material have excellent comprehensive performance, and are widely used in automobile, household appliance, traffic and other fields. ABS has a high gloss, which enlarges its application range to a certain extent, and it also limits its application range owing to its high gloss. Thus, an interesting phenomenon has emerged in the study of ABS modification, on the one hand the efforts to increase gloss produce high gloss materials and on the other hand the efforts to decrease gloss produce matt materials. The invention mainly relates to research on ABS extinction.
The ABS extinction material is mainly used for the aspects of automobile internal parts, various electrical appliance instrument shells, cameras, traveling suitcases and the like. The traditional ABS extinction mainly comprises 4 methods, 1, laser or sand blasting treatment is carried out on the surface of a processing mould or a compression roller, so that the surface of a product can achieve the purpose of extinction; 2. adding delustering agents such as titanium dioxide, silicon dioxide and the like; 3. and spraying the surface of the ABS product. 4. SBS with high B section content is used to be blended and modified with AS and grafted rubber. The 4 methods described above all have relatively large disadvantages and thus limit the use of matt ABS. If the method 1 is used, the worn mold is frequently replaced, and the product is hardly subjected to the heat-type treatment. The use method 2 greatly reduces the toughness of the material and roughens the surface. The method 3 can increase VOC greatly and is harmful to health. Although the method 4 avoids the defects of other three methods, the core of the technology is to prepare ABS with ultrahigh B content and then perform extinction treatment on the ABS by using a graft. The performance of the material cannot be ensured, and the extinction effect is very common.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an extinction flame-retardant ABS material and a preparation method thereof. The method provides a new method and thought for preparing the extinction ABS material, and the extinction flame-retardant ABS material has excellent extinction performance, smooth and flat surface and excellent processing performance, overcomes the defect of poor toughness of common flame-retardant materials, and has good mechanical property. Can be applied to roof pinch plates of large buses, shell types of various electrical instruments and the like.
The invention aims to provide a delustering flame-retardant ABS material. The material comprises the following components in a blending mode: ABS resin, a delustering component, a flame retardant and an antioxidant.
The extinction flame-retardant ABS material comprises the following components in parts by weight based on 100 parts by weight: the extinction component is 5-20 parts by weight, preferably 5-15 parts by weight, the flame retardant is 10-20 parts by weight, preferably 10-18 parts by weight, and the antioxidant is 0.1-0.5 part by weight; the balance of ABS resin;
wherein the extinction component comprises SEBS, polyolefin resin and metal oxide; the weight using range of the SEBS, the polyolefin resin and the metal oxide is 5-15: 1-5: 0.1 to 0.8.
The ABS resin in the extinction flame-retardant ABS material can be randomly selected according to actual material performance requirements and processing conditions, and has no special requirements.
The extinction component in the extinction flame-retardant ABS material comprises three components, namely SEBS, polyolefin resin and metal oxide. SEBS is a linear triblock copolymer with polystyrene as the terminal and ethylene-butylene copolymer obtained by hydrogenation of butadiene as the middle elastic block. The SEBS does not contain unsaturated double bonds, has excellent elasticity and good stability and aging resistance. SEBS is classified into linear and star types. The SEBS selected by the invention is a linear SEBS with the molecular weight of 7-30 ten thousand. With regard to specific industrial products and specific uses of the present invention, we prefer a linear SEBS with a molecule of 22 tens of thousands. Polyolefin resin is required to have poor compatibility with ABS resin and certain compatibility with SEBS. We choose high density PE or grafted PE (maleic anhydride grafted, grafting ratio is 0.8-1%) with melt index of 0.5-20 g/10 min. Considering the processability and the application of the final product, the melt index is preferably 5 to 10g/10min of high-density PE or grafted PE (maleic anhydride grafting, grafting ratio is 0.8 to 1 percent). The metal oxide is TiO2、Sb2O3And one or more of metal oxides.
The flame retardant in the invention is divided into a main flame retardant and an auxiliary flame retardant. The main flame retardant is at least one of brominated ethylene oxide and brominated triazine in consideration of environmental requirements. Considering cost and flame retardant effect at the same time, we follow 3: 9, the two flame retardants are compounded. The addition amount can be adjusted according to different flame retardant grades. The auxiliary flame retardant is antimony trioxide. The flame retardant grade of the extinction flame-retardant ABS material is V0 grade. The weight ratio of the main flame retardant to the auxiliary flame retardant can be 2.5-3.5: 1.
The antioxidant added in the invention is a hindered phenol general antioxidant, and is used for ensuring the stability of the material performance in the blending and subsequent molding processing processes. The addition amount of the additive is changed between 0.1 and 0.5 weight part according to the specific actual requirement.
During the processing of the extinction flame-retardant ABS material, a certain amount of toughening agent, filler, color master batch and the like can be added according to specific requirements to adjust the material performance.
The second purpose of the invention is to provide a preparation method of the extinction flame-retardant ABS material. Namely, the components comprising ABS resin, extinction component, flame retardant and antioxidant are melted and blended according to the content to prepare the extinction flame-retardant ABS material. More specifically, the preparation method of the extinction flame-retardant ABS material comprises the steps of uniformly stirring the components including the ABS resin, the extinction component, the flame retardant and the antioxidant in a mixing device according to the proportion, carrying out melt blending extrusion through a blending device, keeping the vacuum degree of a vacuum system of the device higher than-0.08 MPa, and granulating to obtain the extinction flame-retardant ABS material.
In the processing process of the extinction flame-retardant ABS material, the melt blending temperature of the material is the blending temperature used in the common ABS processing, namely 200-220 ℃.
The mixing apparatus for mixing the materials in the above-mentioned production process of the present invention may employ various mixing apparatuses used in the prior art, such as a stirrer, a kneader, etc. The melt blending equipment used in the method is general blending equipment in the rubber and plastic processing industry, and can be a double-screw extruder, a BUSS mixing unit and the like.
The extinction flame-retardant ABS material has excellent extinction performance, smooth and flat surface and excellent processing performance, overcomes the defect of poor toughness of common flame-retardant materials, and has good mechanical property. Can be applied to roof pinch plates of large buses, shell types of various electrical instruments and the like.
Drawings
FIG. 1 is an electron microscope surface photograph (magnification of 150 times in each photograph) of the material prepared in comparative example 1;
FIG. 2 is an electron microscope surface photograph of the material prepared in comparative example 2;
FIG. 3 is an electron microscope surface photograph of the extinction flame retardant ABS material of the invention prepared in example 1;
FIG. 4 is an electron microscope surface photograph of the extinction flame retardant ABS material of the invention prepared in example 2.
Detailed Description
The present invention is further illustrated by the following specific examples. However, the present invention is not limited to the following examples.
Examples 1 to 4:
ABS resin (Shanghai Gaoqiao petrochemical, brand 8391), extinction component (including SEBS, Yueyang petrochemical production, brand YH-503; PE, Maoyang petrochemical production, brand HXB 4505M; TiO2Rutile titanium dioxide, grade 930; grafted PE, domestic, polychong bin, grafting rate 1%), flame retardant (brominated ethylene oxide, manufactured by Yabao corporation, trade name SAYTEX 8010; bromo-triazine, produced by Qingdao ocean institute, with a brand of FR245, antimony white (H1410-Y1009, China flash star) and an antioxidant (produced by Ciba Jiaji, a brand of B225) added into a high-speed mixer to be uniformly stirred, and then the mixed materials are granulated by a double-screw mixing unit, wherein the mixing temperature is 200-220 ℃, and the vacuum degree of a vacuum system of the equipment is kept to be higher than-0.08 MPa; thus obtaining the extinction flame-retardant ABS material. The specific formulation and the test results of the sample are shown in Table 1.
The prepared flame-retardant delustering ABS material is dried for 4 hours in a cyclone drying oven at the temperature of 90 ℃, and is extruded by a Themo Haake Polylab Os system produced by Hark company of Germany to prepare a plate for testing.
The test comprises the following steps:
measurement of gloss: the gloss of the material is tested according to the standard GB/T8807-1988;
surface photograph by electron microscope: and (5) photographing and detecting the form of the surface of the plate.
Comparative example 1:
the composition, preparation conditions and test procedures were the same as in example 1 except that no matting component was added. The specific formulation and the test results of the sample are shown in Table 1.
Comparative examples 2 to 3:
10 parts of SBS (Yanshan petrochemical Co., 4402) and 0.8 part of titanium dioxide powder are respectively added, and the rest components, preparation conditions and test process are the same as those in example 1.
The specific formulation and the test results of the sample are shown in Table 1.
TABLE 1 compounding ratio and test Performance data for examples 1-4 and comparative examples 1-3
Figure BDA0001135956300000051
Comparison of the matting Properties of the materials in addition to the measured values for gloss, the surface finish was compared. From the test results of the comparative examples and examples in table 1 and the accompanying drawings, it can be seen that:
1. the flame retardant had a certain good effect on the gloss properties, as in the formulation of comparative example 1, which was tested to a gloss value of above 90 if no flame retardant was added.
2. The addition of the flatting agent can reduce the glossiness of the ABS material, and simultaneously, the surface gel particles are uniformly distributed, so that the glossiness and the smoothness of a final product can meet the requirements.
3. The gloss test result of comparative example 3 was low, but the product surface was fish-scaly due to decomposition phenomenon in actual extrusion.
From the above, it can be known that the extinction flame-retardant ABS material has low glossiness, high smoothness, excellent flame-retardant performance, mechanical properties which are not reduced too much by adding a flame retardant, and convenient processing.

Claims (6)

1. The extinction flame-retardant ABS material is characterized by comprising the following blended components: ABS resin, extinction component, flame retardant and antioxidant;
the extinction flame-retardant ABS material is calculated by 100 parts by weight: 5-20 parts of extinction component, 10-18 parts of flame retardant and 0.1-0.5 part of antioxidant; the balance of ABS resin;
the extinction component comprises SEBS, polyolefin resin and metal oxide; the dosage ranges of the SEBS, the polyolefin resin and the metal oxide are 5-15: 1-5: 0.1 to 0.8; the SEBS is a linear SEBS with the molecular weight of 7-30 ten thousand; the polyolefin resin is high-density polyethylene or grafted polyethylene with the melt index of 0.5-20 g/10 min; the metal oxide is selected from TiO2、Sb2O3At least one of;
the flame retardant comprises a main flame retardant and an auxiliary flame retardant; the main flame retardant is selected from at least one of brominated ethylene oxide and brominated triazine; the auxiliary flame retardant is antimony trioxide; the proportion of the main flame retardant to the auxiliary flame retardant is 2.5-3.5: 1.
2. A delustering flame retardant ABS material according to claim 1 characterized in that:
the extinction flame-retardant ABS material is calculated by 100 parts by weight, and the extinction component accounts for 5-15 parts by weight.
3. A delustering flame retardant ABS material according to claim 1 characterized in that:
the extinction flame-retardant ABS material comprises the following components in parts by weight based on 100 parts by weight: 5-15 parts of extinction component, 10-18 parts of flame retardant and 0.1-0.5 part of antioxidant; the balance being ABS resin.
4. A delustering flame retardant ABS material according to any of claims 1 to 3 characterized in that: the flame retardant grade of the extinction flame-retardant ABS material is V0 grade.
5. The preparation method of the extinction flame-retardant ABS material according to any one of claims 1 to 4, characterized by comprising the following steps: and melting and blending components including ABS resin, a delustering component, a flame retardant and an antioxidant according to the using amount to prepare the delustering flame-retardant ABS material.
6. The preparation method of the extinction flame-retardant ABS material according to claim 5, characterized in that: the vacuum degree of the melt blending is more than-0.08 MPa.
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CN111087743B (en) * 2018-10-24 2022-09-20 中国石油化工股份有限公司 Extinction scratch-resistant ABS material and preparation method thereof
CN113388222B (en) * 2021-06-29 2022-08-05 上海朗杜新材料有限公司 Flame-retardant ABS composite material and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008141767A2 (en) * 2007-05-18 2008-11-27 Polimeri Europa S.P.A. Composite material based on vinyl aromatic polymers having enhanced thermal insulation properties and process for the preparation thereof
CN102010563A (en) * 2010-11-12 2011-04-13 浙江大学宁波理工学院 Nano clay compounded flame-retardant ABS resin
CN102675809A (en) * 2012-04-10 2012-09-19 江苏启蓝新材料有限公司 Extinction styrene copolymer composition and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008141767A2 (en) * 2007-05-18 2008-11-27 Polimeri Europa S.P.A. Composite material based on vinyl aromatic polymers having enhanced thermal insulation properties and process for the preparation thereof
CN102010563A (en) * 2010-11-12 2011-04-13 浙江大学宁波理工学院 Nano clay compounded flame-retardant ABS resin
CN102675809A (en) * 2012-04-10 2012-09-19 江苏启蓝新材料有限公司 Extinction styrene copolymer composition and preparation method thereof

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