CN112250985B - Halogen-free flame-retardant ABS composition and preparation method and application thereof - Google Patents
Halogen-free flame-retardant ABS composition and preparation method and application thereof Download PDFInfo
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- CN112250985B CN112250985B CN202011121432.XA CN202011121432A CN112250985B CN 112250985 B CN112250985 B CN 112250985B CN 202011121432 A CN202011121432 A CN 202011121432A CN 112250985 B CN112250985 B CN 112250985B
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention discloses a halogen-free flame-retardant ABS composition, which comprises the following components in parts by weight: 43-79.8 parts of ABS resin, 12-25 parts of phosphazene compound, 10-30 parts of phosphoric acid compound and 0.2-2 parts of processing aid. In the formula of the halogen-free flame-retardant ABS composition, the phosphazene compound and the phosphoric acid compound are compounded and exert a synergistic effect, so that the obtained halogen-free flame-retardant ABS composition has the advantages of no halogen of V-0, high technical value of mass production application, excellent mechanical property and good material appearance, and can meet the material technical requirements of various fields of household appliances, electronic and electrical products, office supplies and the like. Meanwhile, the invention also discloses a preparation method and application of the halogen-free flame-retardant ABS composition.
Description
Technical Field
The invention belongs to the technical field of ABS composite materials, and particularly relates to a halogen-free flame-retardant ABS composition, and a preparation method and application thereof.
Background
ABS materials are commonly used as shells of household appliance products, and the products can cause fire due to ignition caused by overheating, electric leakage, aging and the like, thereby causing great threat to the lives of people. The flame-retardant ABS can realize V-0, V-1 and V-2 grades at present, only the V-2 grade can realize halogen-free flame retardance, and the V-0 grade can only realize brominated flame retardance at present, namely, the flame-retardant ABS material has halogen flame retardance and does not have a halogen-free V-0 flame-retardant system. The brominated flame-retardant ABS material can generate large smoke and toxic gas in the combustion process, so that the brominated flame-retardant ABS material can cause great harm to human health, and the halogen-free flame-retardant system has small harmfulness in the combustion process, so that the brominated flame-retardant ABS material is a development trend of future flame-retardant materials and also becomes a research hotspot all the time. With the continuous upgrade of environmental protection laws and regulations, halogen-free flame retardant materials will inevitably replace halogen-containing flame retardant materials in the future, and become a consensus in the material field.
ABS belongs to terpolymer, contains polybutadiene rubber component in the chemical structure, has inflammability, and is difficult to form carbon in the combustion process compared with engineering materials, so that the realization of high-grade flame retardant property has greater technical difficulty, only can realize halogen V-0 or 5VA flame retardant grade at present, does not have halogen-free V-0 flame retardant ABS material which has excellent mechanical property and can meet the application requirement. In the prior art, although the halogen-free V-0 grade can be realized in the flame retardant grade, the halogen-free V-0 flame retardant ABS has some performance defects, such as poor toughness, low glossiness, poor mechanical property and the like, and the research of the halogen-free V-0 flame retardant ABS only stays in the academic research stage and is far away from the industrial application.
Disclosure of Invention
Based on the above, the invention aims to overcome the defects of the prior art and provide a halogen-free flame retardant ABS composition.
In order to achieve the purpose, the invention adopts the technical scheme that: a halogen-free flame-retardant ABS composition comprises the following components in parts by weight: 43-79.8 parts of ABS resin, 12-25 parts of phosphazene compound, 10-30 parts of phosphoric acid compound and 0.2-2 parts of processing aid.
The composite flame retardant adopts the compounding synergism of the phosphazene compound and the phosphate compound, achieves the halogen-free V-0 flame retardant grade under the combined action of two flame retardants, has better appearance and mechanical property and good processing property, and is suitable for the application fields of household appliances, office supplies and the like.
Preferably, the weight ratio of the phosphoric acid compound to the phosphazene compound is: phosphoric acid compound: phosphazene compound (1-1.5): 1. the compounding of the above proportions can achieve better synergistic flame retardant effect.
Preferably, the ABS resin has a relative density of 1.03-1.08g/cm3(ii) a In the ABS resin, the polybutadiene accounts for 12-25% by weight.
Preferably, the phosphazene compound has the following structural formula:
wherein R is1、R2、R3、R4、R5、R6Are the same, and R1、R2、R3、R4、R5、R6Is selected from-SiH3、--SiCl3、SiHCl2、-SiHO3、-((CH3)5Si)2O、-SiOH2、-NHR、-NH2、-NR2、-NCH、-NO3、-NCO、-N(CH3)、-N2Cl、-C6H5One kind of (1).
More preferably, the phosphazene compound, R1、R2、R3、R4、R5、R6is-C6H5or-NH2. The chemical groups are easy to form active free radicals at high temperature to capture combustible free radicals and inhibit combustion chain reaction.
Preferably, the phosphate compound has the following structural formula:
wherein R is1、R2、R3Are the same, and R1、R2、R3Is selected from-SiH3、-SiCl3、SiHCl2、-SiHO3、-((CH3)5Si)2O、-NHR、-NH2、-NR2、-NCH、-NO3、-NCO、-N(CH3)、-N2Cl、-C2H5、-CH3One kind of (1).
More preferably, R in the phosphate compound1、R2、R3Are all-CH3。
Preferably, the processing aid comprises one or more of an antioxidant, a lubricant, an anti-drip agent;
the antioxidant is selected from one or more of alkyl monophenol antioxidant, alkyl polyphenol antioxidant and thiobisphenol antioxidant; the lubricant is selected from one or more of stearamide lubricants, EBS B50, EB-FF, EBS P400 and WK 1890; the anti-dripping agent is one or more selected from polytetrafluoroethylene compounds, SN80-SA7 and POLY TS 30A.
Meanwhile, the invention also discloses a preparation method of the halogen-free flame-retardant ABS composition, which comprises the following steps:
stirring and mixing all the components at a high speed to obtain a premix; and (3) feeding the premix into a double-screw extruder, extruding, cooling with water, and granulating to obtain the halogen-free flame-retardant ABS composition.
In addition, the invention also discloses application of the halogen-free flame-retardant ABS composition in household appliance products.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, in the formula of the halogen-free flame-retardant ABS composition, through the compounding of the phosphazene compound and the phosphoric acid compound, the phosphazene compound and the phosphoric acid compound play a synergistic effect, the obtained halogen-free flame-retardant ABS composition has no halogen V-0, has the technical value of mass production application, excellent mechanical property and good material appearance, and can meet the material technical requirements in various fields of household appliances, electronic and electrical products, office supplies and the like.
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.
The preparation method of the halogen-free flame-retardant ABS composite material in the embodiment and the comparative example of the invention comprises the following steps:
uniformly mixing all the components in a high-speed stirring mixer to obtain a premix; feeding the premix into a double-screw extruder, extruding, cooling with water, and granulating to obtain the halogen-free flame-retardant ABS composition; wherein the temperature of each section of screw of the double-screw extruder from a feed inlet to a machine head is respectively 80 ℃ in a first area, 160 ℃ in a second area, 180 ℃ in a third area, 190 ℃ in a fourth area, 190 ℃ in a fifth area, 190 ℃ in a sixth area, 180 ℃ in a seventh area, 180 ℃ in an eighth area, 180 ℃ in a ninth area, 200 ℃ in the machine head, the rotating speed of the screw is 350rpm, and the length-diameter ratio of the double-screw extruder is 40: 1.
in the embodiment of the application, the structural formula of the phosphazene compound is as follows:
the structural formula of the phosphate compound is as follows:
the test standards for each property in examples and comparative examples are shown in table 1:
TABLE 1 measurement standards for the respective Properties
The examples and comparative examples of the present invention employ, but are not limited to, the following raw materials:
ABS resin 1: styrene-acrylonitrile-butadiene copolymers; the relative density is 1.04g/cm3The polybutadiene accounts for 18-20 wt%, and the manufacturer is Jilin petrochemical and has a mark of ABS 0215A;
ABS resin 2: styrene-acrylonitrile-butadiene copolymerPolymer having a relative density of 1.03g/cm3The polybutadiene accounts for 55 to 70 percent by weight, and the manufacturer is Korea Jinhu and the brand is ABS HR 181;
phosphazene compound 1: in the structural formula R1、R2、R3、R4、R5、R6Are all-C6H5The manufacturer is Hubei Yuancheng Sai Chu science and technology company;
phosphazene compound 2: in the structural formula R1、R2、R3、R4、R5、R6Are all-NH2Commercially available;
phosphazene compound 3: in the structural formula R1、R2、R3、R4、R5、R6Are all-N (CH)3) Commercially available;
phosphoric acid compound 1: in the structure of R1、R2、R3Are all-CH3Group, Shanghai Michelin Biochemical technology, Inc.;
phosphoric acid compound 2: in the structure of R1、R2、R3Are all-C2H5Group, bailingwei technologies ltd, beijing;
processing aid: (the weight ratio of the antioxidant to the lubricant to the anti-dripping agent is 1:3:1)
Antioxidant: alkyl monophenol antioxidant Irganox 1076 from Pasteur company is selected;
lubricant: EBS B50, Changzhou Coisal, was selected;
anti-dripping agent: guangzhou entropy energy Inc., SN80-SA 7.
The invention sets the components and performance data in examples 1-10 and comparative examples 1-4, and the specific examples 1-10 and comparative examples 1-4 are shown in table 2:
TABLE 2 Components and Performance data for examples 1-10 and comparative examples 1-4
As can be seen from Table 2, compared with comparative examples 1 to 4, examples 1 to 9 of the present application all had better tensile strength, bending strength, notched Izod impact strength, gloss and vertical burning properties; comparative example 1 does not contain the phosphazene compound and the phosphoric acid compound of the application, comparative examples 2 and 3 only contain one of the phosphazene compound and the phosphoric acid compound, comparative example 4 contains the phosphazene compound and the phosphoric acid compound but the content of the phosphazene compound and the phosphoric acid compound is not in the range of the application, and comparative examples 1 to 4 have tensile strength, bending strength, izod notched impact strength, glossiness and vertical burning performance which are not as good as those of example 1;
comparing examples 1 to 4, it can be seen that in examples 1, 2 and 4, the weight ratio of the phosphoric acid compound to the phosphazene compound is (1 to 1.5): 1, in example 3, the weight ratio of the phosphoric acid compound to the phosphazene compound is not (1-1.5): 1, the tensile strength, flexural strength, Izod notched impact strength and gloss in example 3 were all different from those in examples 1, 2 and 4.
As is clear from comparison of example 5 with example 1, the ABS resin in example 5 does not satisfy the condition that the relative density is 1.03-1.08g/cm3Polybutadiene is 12-25% by weight, and the tensile strength, bending strength and glossiness of the polybutadiene are all different from those of the polybutadiene in example 1.
Comparing examples 6 and 7 with example 1, it can be seen that R in the phosphazene compound of example 7 is1、R2、R3、R4、R5、R6is-N (CH)3) The tensile strength, flexural strength, izod notched impact strength and gloss were all inferior to those of examples 6 and 1.
By comparing example 8 with example 1, it can be seen that R in the phosphoric acid compound in example 8 is1、R2、R3is-C2H5The tensile strength, flexural strength, Izod notched impact strength and gloss were all inferior to those of example 1.
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 (7)
1. The halogen-free flame-retardant ABS composition is characterized by comprising the following components in parts by weight: 43-79.8 parts of ABS resin, 12-25 parts of phosphazene compound, 10-30 parts of phosphoric acid compound and 0.2-2 parts of processing aid;
wherein the weight ratio of the phosphoric acid compound to the phosphazene compound is as follows: phosphoric acid compound: phosphazene compound (1-1.5): 1;
the structural formula of the phosphate compound is as follows:
wherein R is1、R2、R3Are the same, and R1、R2、R3is-CH3。
2. The halogen-free flame retardant ABS composition according to claim 1 wherein the ABS resin has a relative density of 1.03 to 1.08g/cm3(ii) a In the ABS resin, the polybutadiene accounts for 12-25% by weight.
3. The halogen-free flame retardant ABS composition according to claim 1 wherein the phosphazene compound has the following structural formula:
wherein R is1、R2、R3、R4、R5、R6Are the same, and R1、R2、R3、R4、R5、R6Is selected from-SiH3、-SiCl3、SiHCl2、-SiHO3、-((CH3)5Si)2O、-SiOH2、-NHR、-NH2、-NR2、-NCH、-NO3、-NCO、-N(CH3)、-N2Cl、-C6H5One kind of (1).
4. The halogen-free flame retardant ABS composition according to claim 3 wherein the phosphazene compound, R1、R2、R3、R4、R5、R6is-C6H5or-NH2。
5. The halogen-free flame retardant ABS composition according to claim 1 wherein the processing aid comprises one or more of an antioxidant, a lubricant, an anti-drip agent;
the antioxidant is selected from one or more of alkyl monophenol antioxidant, alkyl polyphenol antioxidant and thiobisphenol antioxidant; the lubricant is selected from one or more of stearamide lubricants, EBS B50, EB-FF, EBS P400 and WK 1890; the anti-dripping agent is one or more selected from polytetrafluoroethylene compounds, SN80-SA7 and POLY TS 30A.
6. The preparation method of the halogen-free flame retardant ABS composition as claimed in any of claims 1 to 5, characterized in that the method comprises the following steps:
stirring and mixing all the components at a high speed to obtain a premix; and (3) feeding the premix into a double-screw extruder, extruding, cooling with water, and granulating to obtain the halogen-free flame-retardant ABS composition.
7. Use of the halogen free flame retardant ABS composition according to any of claims 1 to 5 in household electrical appliances.
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| CN202011121432.XA CN112250985B (en) | 2020-10-19 | 2020-10-19 | Halogen-free flame-retardant ABS composition and preparation method and application thereof |
| PCT/CN2021/082257 WO2022083057A1 (en) | 2020-10-19 | 2021-03-23 | Halogen-free flame retardant abs composition, preparation method therefor and use thereof |
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| CN202011121432.XA CN112250985B (en) | 2020-10-19 | 2020-10-19 | Halogen-free flame-retardant ABS composition and preparation method and application thereof |
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| CN112250985B (en) * | 2020-10-19 | 2022-06-07 | 金发科技股份有限公司 | Halogen-free flame-retardant ABS composition and preparation method and application thereof |
| CN115044161B (en) * | 2022-06-16 | 2023-11-14 | 金发科技股份有限公司 | Flame-retardant ABS material and preparation method and application thereof |
| CN115181344B (en) * | 2022-07-28 | 2023-08-22 | 金发科技股份有限公司 | High heat-resistant flame-retardant HIPS material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6518336B1 (en) * | 1998-07-14 | 2003-02-11 | Otsuka Chemical Co., Ltd. | Flame-retardent resin compositions compring thermoplastic resin, thermotropic liquid crystal polymer, and hoalogen-free phosphazen compound |
| CN102936416A (en) * | 2012-11-22 | 2013-02-20 | 天津市飞荣达科技有限公司 | Halogen-free flame retardant, and application and polycarbonate composition thereof |
| JP2014221850A (en) * | 2013-05-13 | 2014-11-27 | 三菱エンジニアリングプラスチックス株式会社 | Resin composition for laser direct structuring, resin molding and method of producing resin molding provided with plating layer |
| CN109721768A (en) * | 2018-12-22 | 2019-05-07 | 广州市寅源新材料科技有限公司 | Bittern-free phosphorous-nitrogen composite flame-retardant agent and halogen-free combustion-proof thermoplastic polymer comprising it |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112250985B (en) * | 2020-10-19 | 2022-06-07 | 金发科技股份有限公司 | Halogen-free flame-retardant ABS composition and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6518336B1 (en) * | 1998-07-14 | 2003-02-11 | Otsuka Chemical Co., Ltd. | Flame-retardent resin compositions compring thermoplastic resin, thermotropic liquid crystal polymer, and hoalogen-free phosphazen compound |
| CN102936416A (en) * | 2012-11-22 | 2013-02-20 | 天津市飞荣达科技有限公司 | Halogen-free flame retardant, and application and polycarbonate composition thereof |
| JP2014221850A (en) * | 2013-05-13 | 2014-11-27 | 三菱エンジニアリングプラスチックス株式会社 | Resin composition for laser direct structuring, resin molding and method of producing resin molding provided with plating layer |
| CN109721768A (en) * | 2018-12-22 | 2019-05-07 | 广州市寅源新材料科技有限公司 | Bittern-free phosphorous-nitrogen composite flame-retardant agent and halogen-free combustion-proof thermoplastic polymer comprising it |
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