阅读说明：本技术 一种低气味耐低温阻燃abs组合物及其制备方法 (Low-odor low-temperature-resistant flame-retardant ABS (acrylonitrile-butadiene-styrene) composition and preparation method thereof ) 是由 孙超正 范聪成 宋晓辉 肖华明 付锦锋 陶四平 王中林 杨霄云 于 2020-12-11 设计创作，主要内容包括：本发明提供了一种低气味耐低温阻燃ABS组合物及其制备方法,该组合物由包括如下重量份的原料制成：ABS 47-69份,磷系阻燃剂5-10份,成炭剂A 15-20份,成炭剂B 10-20份,物理吸附剂1-3份。本发明所述的低气味耐低温阻燃ABS组合物通过添加成炭剂A与成炭剂B,提高了材料在燃烧过程中的成炭率,并与磷酸酯阻燃剂协效,形成新型阻燃体系,材料具备良好的阻燃性能,实现了磷酸酯阻燃剂少量添加达到V-0阻燃等级。(The invention provides a low-odor low-temperature-resistant flame-retardant ABS composition and a preparation method thereof, wherein the composition is prepared from the following raw materials in parts by weight: 47-69 parts of ABS, 5-10 parts of phosphorus flame retardant, 15-20 parts of carbon forming agent A, 10-20 parts of carbon forming agent B and 1-3 parts of physical adsorbent. According to the low-odor low-temperature-resistant flame-retardant ABS composition, the charring agent A and the charring agent B are added, so that the charring rate of the material in the combustion process is improved, the charring agent A and the charring agent B are synergistic with a phosphate flame retardant to form a novel flame-retardant system, the material has good flame-retardant performance, and the purpose that the flame retardant of the phosphate is added in a small amount to reach the V-0 flame-retardant level is achieved.)

1. A low-odor low-temperature-resistant flame-retardant ABS composition is characterized in that: the composition is prepared from the following raw materials in parts by weight:

2. the low odor low temperature resistant flame retardant ABS composition of claim 1 wherein: the charring agent A is modified beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt; the carbon forming agent B is polycarbonate.

3. The low odor low temperature resistant flame retardant ABS composition of claim 1 wherein: the melt flow rate of the carbon forming agent B is 15-25g/10min under the conditions of 300 ℃ and 1.2 kg; the melt flow rate of the ABS at 200 ℃ and 10kg is 20-40g/10 min.

4. The low odor low temperature resistant flame retardant ABS composition of claim 1 wherein: the physical adsorbent is at least one of activated carbon, molecular sieve or silica gel.

5. The low odor low temperature resistant flame retardant ABS composition of claim 1 wherein: the phosphorus flame retardant is a phosphate flame retardant; preferably, the phosphorus flame retardant is at least one of bisphenol A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate) or triphenyl phosphate.

6. The low odor low temperature resistant flame retardant ABS composition of claim 1 wherein: the composition also comprises a processing aid accounting for 0.2-1% of the total mass of the raw materials; the processing aid is at least one of an antioxidant or a lubricant; the antioxidant is a hindered phenol antioxidant and a phosphate antioxidant, wherein the mass ratio of the hindered phenol antioxidant to the phosphate antioxidant is 1: 1; the hindered phenol antioxidant is at least one of THANOX 1010, antioxidant 1076 or antioxidant 1098; the phosphate antioxidant is at least one of THANOX 168, antioxidant Y-002 or antioxidant X-002; the lubricant is an amide lubricant; preferably, the lubricant is at least one of erucamide or EBS B50.

7. A preparation method of modified beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt is characterized by comprising the following steps: the method comprises the following steps:

(1) carrying out amidation reaction on 2-methyl-2, 5-dioxo-1, 2-oxyphospholane and p-nitroaniline to obtain a yellow precipitate, filtering, washing and dissolving the yellow precipitate in isopropanol, then carrying out heating reaction on the yellow precipitate and aluminum isopropoxide, and filtering, washing and drying after the reaction is finished to obtain beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt;

(2) and carrying out ultrasonic treatment, filtration and drying on the beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt to obtain the modified beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt.

8. The process according to claim 7 for the preparation of the modified aluminium salt of β - (p-nitrobenzamide) methylphosphinate, characterized in that: the temperature of the amidation reaction in the step (1) is 95-105 ℃, and the time is 4-6 h; the heating reaction in the step (1) is carried out at the temperature of 90-100 ℃ for 5-8 h.

9. The process according to claim 7 for the preparation of the modified aluminium salt of β - (p-nitrobenzamide) methylphosphinate, characterized in that: the dispersion liquid in the ultrasonic step in the step (2) is ethanol, the mass ratio of the dispersion liquid to the beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt is 8-10:1, and the time of the ultrasonic step is 1 h; the temperature of the drying step in the step (2) is 70-90 ℃, and the time is 10-18 h.

10. The method for preparing the low-odor low-temperature-resistant flame-retardant ABS composition as recited in any of claims 1 to 6, wherein: the method comprises the following steps: uniformly mixing all the raw materials, feeding the raw materials from a main feeding port of an extruder, and then melting, extruding and granulating to obtain the low-odor low-temperature-resistant flame-retardant ABS composition; the extruder is a double-screw extruder; the temperature of the melting step is 190-240 ℃.

Technical Field

The invention belongs to the field of modified plastics, and particularly relates to a low-odor low-temperature-resistant flame-retardant ABS composition and a preparation method thereof.

Background

The ABS material has the advantages of high gloss, high rigidity, impact resistance and the like, and is widely applied to the industries of household appliances, illumination, office, automobiles and the like. The ABS resin material has low char yield, and the flame retardant adopted by V-0 grade flame-retardant ABS in the market is generally a brominated flame retardant. In the reprocessing process and the injection molding process of the brominated flame-retardant ABS, small molecules such as bromide, ABS residual monomers, ABS synthetic solvent and the like are volatilized when the material is heated, so that a great smell is generated, the field smell of a processing workshop and an injection molding workshop is great, and the working environment experience is low. Furthermore, one type of application for ABS materials is in the case of battery compartments for electric vehicles. The conventional V-0 grade flame-retardant ABS adopts a brominated flame retardant which has large smell and is easy to generate smell when being heated in the charging process of an electric vehicle, so that unpleasant feeling is generated when the ABS is used by a terminal user. Therefore, the development of the low-odor V-0 flame-retardant ABS is beneficial to the improvement of the environment of a processing workshop and an injection molding workshop and can also provide good use experience for end consumers. In addition, electric bicycles are used even in low-temperature environments in winter, and materials having low-temperature resistance are required. None of the current commercial products can meet the above requirements.

Disclosure of Invention

In view of the above, the invention provides a low-odor low-temperature-resistant flame-retardant ABS composition and a preparation method thereof, aiming at overcoming the defects in the prior art.

In order to achieve the purpose, the technical scheme of the invention is realized as follows:

a low-odor low-temperature-resistant flame-retardant ABS composition is prepared from the following raw materials in parts by weight:

further, the carbon forming agent A is modified beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt; the carbon forming agent B is polycarbonate.

Further, the melt flow rate of the carbon forming agent B is 15-25g/10min at 300 ℃ under the condition of 1.2 kg; the melt flow rate of the ABS at 200 ℃ and 10kg is 20-40g/10 min.

Further, the physical adsorbent is at least one of activated carbon, molecular sieve or silica gel.

Further, the phosphorus flame retardant is a phosphate flame retardant; preferably, the phosphorus flame retardant is at least one of bisphenol A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate) or triphenyl phosphate.

Further, the composition also comprises a processing aid accounting for 0.2-1% of the total mass of the raw materials; the processing aid is at least one of an antioxidant or a lubricant; the antioxidant is a hindered phenol antioxidant and a phosphate antioxidant, wherein the mass ratio of the hindered phenol antioxidant to the phosphate antioxidant is 1: 1; the hindered phenol antioxidant is at least one of THANOX 1010, antioxidant 1076 or antioxidant 1098; the phosphate antioxidant is at least one of THANOX 168, antioxidant Y-002 or antioxidant X-002; the lubricant is an amide lubricant; preferably, the lubricant is at least one of erucamide or EBS B50.

A preparation method of modified beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt comprises the following steps:

(1) carrying out amidation reaction on 2-methyl-2, 5-dioxo-1, 2-oxyphospholane and p-nitroaniline to obtain a yellow precipitate, filtering, washing and dissolving the yellow precipitate in isopropanol, then carrying out heating reaction on the yellow precipitate and aluminum isopropoxide, and filtering, washing and drying after the reaction is finished to obtain beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt;

(2) and carrying out ultrasonic treatment, filtration and drying on the beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt to obtain the modified beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt.

Further, the temperature of the amidation reaction in the step (1) is 95-105 ℃, and the time is 4-6 h; the heating reaction in the step (1) is carried out at the temperature of 90-100 ℃ for 5-8 h.

Further, the dispersion liquid in the ultrasonic step in the step (2) is ethanol, the mass ratio of the dispersion liquid to the beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt is 8-10:1, and the time of the ultrasonic step is 1 h; the temperature of the drying step in the step (2) is 70-90 ℃, and the time is 10-18 h.

The preparation method of the low-odor low-temperature-resistant flame-retardant ABS composition comprises the following steps: uniformly mixing all the raw materials, feeding the raw materials from a main feeding port of an extruder, and then melting, extruding and granulating to obtain the low-odor low-temperature-resistant flame-retardant ABS composition; the extruder is a double-screw extruder; the temperature of the melting step is 190-240 ℃.

Compared with the prior art, the invention has the following advantages:

according to the low-odor low-temperature-resistant flame-retardant ABS composition, the charring agent A and the charring agent B are added, wherein the molecular chain main chains of the charring agent A and the charring agent B both contain benzene ring structures, aromatization carbon can be formed by combustion, the charring rate of an ABS material in the combustion process is improved, in addition, the specific surface area of the charring agent A is increased after modification treatment, the contact interface with ABS resin is increased, good charring and heat insulation effects can be achieved after combustion and heating, the charring agent is compounded, the condensed phase flame-retardant effect of a phosphate flame retardant is synergistic, a novel flame-retardant system is formed, the material has good flame-retardant performance, and the situation that the flame-retardant level of V-0 is achieved by adding a small amount of the phosphate.

According to the low-odor low-temperature-resistant flame-retardant ABS composition, the phosphorus flame retardant is adopted, and the physical adsorbent is adopted to adsorb small molecular components emitted in the processing process, so that compared with the traditional bromine flame-retardant system, the odor of the material is effectively reduced, and the low-odor effect is realized.

The low-odor low-temperature-resistant flame-retardant ABS composition disclosed by the invention is added with the antioxidant, so that the material is not easy to decompose in the processing process, and the low-odor low-temperature-resistant flame-retardant ABS composition is suitable for being used as a shell material of a battery compartment of an electric vehicle.

Detailed Description

Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.

In the embodiment of the invention, the ABS adopts PA-757K of Zhenjiang Qimei industry Co., Ltd;

in the embodiment of the invention, the phosphorus flame retardant adopts WSFR-BDP, which is very popular in Zhejiang river;

the 2-methyl-2, 5-dioxo-1, 2-oxyphospholane used in the synthetic process of the charring agent A in the embodiment of the invention is purchased from Germany Kelaien, raw materials such as p-nitroaniline, isopropanol, aluminum isopropoxide and the like are purchased from Chinese medicinal chemical reagent company;

in the embodiment of the invention, the charring agent B adopts PC 2405, Germany Bayer;

in the embodiment of the invention, the physical adsorbent adopts activated carbon, and the plastic company of Yueqiao reagent, Taishan city;

in the embodiment of the invention, the antioxidant adopts THANOX 1010 and THANOX 168, Tianjin Lianlong new material GmbH;

in the examples of the present invention, EBS B50, Indonesia PT. CMS was used as the lubricant.

The present invention will be described in detail with reference to examples.

Example 1

A low-odor low-temperature-resistant flame-retardant ABS composition is prepared from the following raw materials in parts by weight: 69 parts of ABS, 5 parts of phosphorus flame retardant, 15 parts of char forming agent A, 10 parts of char forming agent B, 1 part of physical adsorbent, 0.4 part of antioxidant and 0.2 part of lubricant.

A preparation method of modified beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt comprises the following steps:

(1) carrying out amidation reaction on 2-methyl-2, 5-dioxo-1, 2-oxyphospholane and p-nitroaniline for 5 hours at the temperature of 100 ℃ to obtain yellow precipitate, filtering, washing and dissolving the obtained yellow precipitate in isopropanol, then carrying out heating reaction on the yellow precipitate and aluminum isopropoxide for 6 hours at the temperature of 95 ℃, and filtering, washing and drying after the reaction is finished to obtain beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt, wherein the structural formula is as follows:

(2) performing ultrasonic treatment on the beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt for 1h, wherein a dispersion liquid is ethanol, the mass ratio of the ethanol to the beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt is 10:1, filtering, and drying at 80 ℃ for 16h to obtain the modified beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt.

The preparation method of the low-odor low-temperature-resistant flame-retardant ABS composition comprises the following steps: uniformly mixing all the raw materials, feeding the raw materials from a main feeding port of an extruder, and then melting, extruding and granulating to obtain the low-odor low-temperature-resistant flame-retardant ABS composition; the extruder is a double-screw extruder; the temperature of the melting step is 190-240 ℃.

Example 2

A low-odor low-temperature-resistant flame-retardant ABS composition is prepared from the following raw materials in parts by weight: 58 parts of ABS, 7 parts of phosphorus flame retardant, 18 parts of char forming agent A, 15 parts of char forming agent B, 2 parts of physical adsorbent, 0.4 part of antioxidant and 0.2 part of lubricant.

A modified beta- (p-nitrobenzamide) ethyl methylphosphinate aluminium salt was prepared as in example 1.

The preparation method of the low-odor low-temperature-resistant flame-retardant ABS composition is the same as that of example 1.

Example 3

A low-odor low-temperature-resistant flame-retardant ABS composition is prepared from the following raw materials in parts by weight: 57 parts of ABS, 8 parts of phosphorus flame retardant, 18 parts of char forming agent A, 15 parts of char forming agent B, 2 parts of physical adsorbent, 0.4 part of antioxidant and 0.2 part of lubricant.

A modified beta- (p-nitrobenzamide) ethyl methylphosphinate aluminium salt was prepared as in example 1.

The preparation method of the low-odor low-temperature-resistant flame-retardant ABS composition is the same as that of example 1.

Example 4

A low-odor low-temperature-resistant flame-retardant ABS composition is prepared from the following raw materials in parts by weight: 47 parts of ABS, 10 parts of phosphorus flame retardant, 20 parts of carbon forming agent A, 20 parts of carbon forming agent B, 3 parts of physical adsorbent, 0.4 part of antioxidant and 0.2 part of lubricant.

A modified beta- (p-nitrobenzamide) ethyl methylphosphinate aluminium salt was prepared as in example 1.

The preparation method of the low-odor low-temperature-resistant flame-retardant ABS composition is the same as that of example 1.

Comparative example 1

The flame-retardant ABS composition is prepared from the following raw materials in parts by weight: 90 parts of ABS, 10 parts of phosphorus flame retardant, 0.4 part of antioxidant and 0.2 part of lubricant.

The preparation method of the flame-retardant ABS composition comprises the following steps: uniformly mixing all the raw materials, feeding the raw materials from a main feeding port of an extruder, and then melting, extruding and granulating to obtain the low-odor low-temperature-resistant flame-retardant ABS composition; the extruder is a double-screw extruder; the temperature of the melting step is 190-240 ℃.

Comparative example 2

The flame-retardant ABS composition is prepared from the following raw materials in parts by weight: 77 parts of ABS, 18 parts of tetrabromobisphenol A, 5 parts of antimony white, 0.4 part of antioxidant and 0.2 part of lubricant.

The preparation method of the flame-retardant ABS composition is the same as that of comparative example 1.

Comparative example 3

The flame-retardant ABS composition is prepared from the following raw materials in parts by weight: 65 parts of ABS, 18 parts of beta- (p-nitrobenzamide) ethyl methylphosphinate aluminum salt, 15 parts of char forming agent B, 2 parts of physical adsorbent, 0.4 part of antioxidant and 0.2 part of lubricant.

The preparation method of the flame-retardant ABS composition is the same as that of comparative example 1.

Comparative example 4

The flame-retardant ABS composition is prepared from the following raw materials in parts by weight: 67 parts of ABS, 10 parts of phosphorus flame retardant, 20 parts of carbon forming agent B, 3 parts of physical adsorbent, 0.4 part of antioxidant and 0.2 part of lubricant.

The preparation method of the flame-retardant ABS composition is the same as that of comparative example 1.

The compositions obtained in examples 1 to 4 and comparative examples 1 to 4 were subjected to the test, and the results are shown in Table 1.

TABLE 1 test data

As shown in Table 1, in example 4, compared with comparative example 1, the addition of the char-forming agent and the physical adsorbent significantly improves the flame retardant performance of example 4, reaches V-0 level, and reduces the odor of the material. Example 3 compared to comparative example 2, the use of a flame retardant system provides significant advantages in both the odor and low temperature notched izod impact strength of example 3. Compared with the example 3, the impact strength of the material is obviously lower by adding the unmodified charring agent A in the comparative example 3, and the flame retardant effect of V-2 level can be realized only, so that the flame retardant is poorer.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.