阅读说明：本技术 阻燃abs材料及其制备方法和应用 (Flame-retardant ABS material and preparation method and application thereof ) 是由 吕福成 李荣群 魏子芳 黄骎 于 2020-12-17 设计创作，主要内容包括：本发明公开了一种阻燃ABS材料及其制备方法和应用,该阻燃ABS材料由74～80份ABS树脂、18.2～20.2份阻燃剂、1～5份流体改善剂、0.5份润滑剂和0.3份抗氧剂按照重量份制备而成,其中,所述ABS树脂中,AS重均分子量分布为13万～20万之间。该阻燃ABS材料具有高流动性、高冲击性、优异的阻燃性并兼具耐油效果,可满足厨卫或餐厅等对耐油阻燃产品的需求。(The invention discloses a flame-retardant ABS material and a preparation method and application thereof, wherein the flame-retardant ABS material is prepared from 74-80 parts of ABS resin, 18.2-20.2 parts of flame retardant, 1-5 parts of fluid improver, 0.5 part of lubricant and 0.3 part of antioxidant according to parts by weight, wherein in the ABS resin, the weight average molecular weight distribution of AS is 13-20 ten thousand. The flame-retardant ABS material has high fluidity, high impact property, excellent flame retardance and oil resistance, and can meet the requirements of kitchens and bathrooms on oil-resistant flame-retardant products.)

1. The flame-retardant ABS material is characterized by being prepared from 74-80 parts of ABS resin, 18.2-20.2 parts of flame retardant, 1-5 parts of fluid improver, 0.5 part of lubricant and 0.3 part of antioxidant in parts by weight, wherein in the ABS resin, the AS weight average molecular weight is distributed between 13 ten thousand and 20 ten thousand.

2. The flame retardant ABS material of claim 1 wherein the flow improver is AS particles having a weight average molecular weight distribution of between 1 million and 2 million.

3. The flame retardant ABS material of claim 1 wherein the flame retardant is a combination of a brominated flame retardant and antimony trioxide and an anti-drip agent, wherein the brominated flame retardant and antimony trioxide are mixed in any ratio.

4. The flame retardant ABS material of claim 1 wherein the lubricant is selected from at least one of an internal lubricant and an external lubricant.

5. Flame-retardant ABS material according to claim 4, characterized in that the internal lubricant is selected from ethylene bis stearamides and the external lubricant is selected from calcium stearates.

6. The flame retardant ABS material of claim 1 wherein the antioxidant is selected from at least one of primary antioxidants and secondary antioxidants.

7. The method for preparing a flame retardant ABS material according to any of claims 1 to 6, characterized in that it comprises the following steps:

fully mixing the flame retardant, the lubricant, the antioxidant and the fluid improver according to the proportion to obtain a uniform first premix;

fully mixing the first premix and the dried ABS resin according to the proportion to obtain a uniform second premix;

and adding the second premix into a double-screw extruder, and carrying out melt blending, extrusion, cooling, granulation and drying to obtain the flame-retardant ABS material.

8. The method of claim 7, wherein the twin screw extruder has a processing temperature of: the first zone is 170 +/-10 ℃, the second zone is 180 +/-10 ℃, the third zone is 190 +/-10 ℃, the fourth zone is 190 +/-10 ℃, the fifth zone is 180 +/-10 ℃, the sixth zone is 190 +/-10 ℃, the head is 190 +/-10 ℃ and the screw rotation speed is 380 +/-20 r/min.

9. Use of a flame retardant ABS material according to any of claims 1 to 6 for the preparation of a display back cover for restaurants or kitchens.

Technical Field

The invention belongs to the technical field of modification of high polymer materials, and particularly relates to a flame-retardant ABS material and a preparation method thereof, and also relates to application of the flame-retardant ABS material.

Background

The acrylonitrile-butadiene-styrene copolymer resin (ABS for short) is a terpolymer consisting of styrene, butadiene and acrylonitrile, wherein the styrene provides excellent processing performance for the material, the double bond structure in the butadiene molecular chain ensures the material to have good toughness, the acrylonitrile provides the chemical corrosion resistance and better glossiness of the material, and the three components ensure that the ABS has excellent comprehensive performance and is widely applied to the fields of electronic appliances, living goods, automobile parts, military accessories and the like.

However, the oxygen index of the ABS material is only 18, and the ABS material belongs to flammable materials. With the improvement of the requirements on the use safety of materials, particularly materials in using areas such as restaurants, kitchens and the like, the conventional ABS materials are difficult to meet the use requirements, and the modification of ABS resin to achieve the purpose of flame retardance of the materials has become a main trend at present. With the continuous progress of intellectualization, display products with thin wall thickness and large size are increasingly produced in areas such as restaurants, kitchens and the like, and the display products require materials with high fluidity, good impact resistance, oil resistance, stain resistance, corrosion resistance and the like. However, the flame retardant ABS materials available in the market at present often only have some properties in consideration of flame retardancy, high toughness, high fluidity and resistance to oil corrosion, and thus the use requirements of such products are difficult to achieve.

Disclosure of Invention

In view of the above, the invention needs to provide a flame retardant ABS material and a preparation method thereof, which can realize the flame retardancy, oil resistance and high fluidity of the ABS material by selecting an ABS resin with a special distribution of AS molecular weight and matching with the formula of the invention, so AS to solve the above problems.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a flame-retardant ABS material which is prepared from 74-80 parts of ABS resin, 18.2-20.2 parts of flame retardant, 1-5 parts of fluid improver, 0.5 part of lubricant and 0.3 part of antioxidant in parts by weight, wherein in the ABS resin, the weight average molecular weight distribution of AS is 13-20 ten thousand.

According to the invention, ABS resin particles with special AS molecular weight distribution are added into ABS resin, and the formula combination of the flame retardant, the lubricant, the fluid improver and the antioxidant is matched, so that the obtained flame-retardant ABS material can meet the requirements of oil resistance, high flow property and high impact property while being conventional in flame retardance, and the use requirement of the ABS material under extreme conditions is met. The ABS resin is a terpolymer of three monomers of acrylonitrile (a), butadiene (B) and styrene (S), and the relative contents of the three monomers can be controlled by preparation and can be arbitrarily changed, without particular limitation.

Further, AS particles (styrene-acrylonitrile copolymers) may be a routine choice in the art, the fluid improver being AS particles having a weight average molecular weight distribution between 1 ten thousand and 2 ten thousand.

Furthermore, the flame retardant in the invention may be selected from conventional flame retardants in the art, which are not particularly limited, and may be a halogen flame retardant or a halogen-free flame retardant, and preferably, in some specific embodiments of the invention, the flame retardant is selected from a combination of a brominated flame retardant, antimony trioxide and an anti-dripping agent, and the brominated flame retardant and the antimony trioxide are mixed in any proportion and then used in combination with the anti-dripping agent, so that the flame retardant performance of the flame-retardant ABS material can reach a better state.

Further, the lubricant is selected from at least one of an internal lubricant and an external lubricant.

Further, the internal lubricant and the external lubricant may be selected from lubricants conventional in the art, specifically, the internal lubricant includes but is not limited to ethylene bis stearamide, and the external lubricant includes but is not limited to calcium stearate.

Further, the antioxidant is selected from at least one of a primary antioxidant and a secondary antioxidant. Wherein, the primary antioxidant includes but is not limited to 1076, and the secondary antioxidant includes but is not limited to 168.

The invention also provides a preparation method of the flame-retardant ABS material, which comprises the following steps:

fully mixing the flame retardant, the lubricant, the antioxidant and the fluid improver according to the proportion to obtain a uniform first premix;

fully mixing the first premix and the dried ABS resin according to the proportion to obtain a uniform second premix, wherein the mixing process of the first premix and the second premix is not particularly limited, such as the rotating speed, the mixing time and the like can be adjusted according to actual conditions, as long as the purpose of uniform mixing can be achieved;

and adding the second premix into a double-screw extruder, and carrying out melt blending, extrusion, cooling, granulation and drying to obtain the flame-retardant ABS material.

It is understood that the processing parameters of the twin-screw extruder are different according to the selection of the matrix resin and the auxiliary agent, can be adjusted according to the actual situation, and are not particularly limited, and preferably, in some specific embodiments of the invention, the processing temperature of the twin-screw extruder is: the first zone is 170 +/-10 ℃, the second zone is 180 +/-10 ℃, the third zone is 190 +/-10 ℃, the fourth zone is 190 +/-10 ℃, the fifth zone is 180 +/-10 ℃, the sixth zone is 190 +/-10 ℃, the head is 190 +/-10 ℃ and the screw rotation speed is 380 +/-20 r/min.

The invention also provides the application of the flame-retardant ABS material in the preparation of a displayer rear shell for a restaurant or kitchen, wherein the displayer rear shell for the restaurant or kitchen has the characteristics of thin wall thickness and large size and is required to have excellent flame retardance, high fluidity, impact resistance and oil resistance, and the flame-retardant ABS material completely meets the requirements.

Compared with the prior art, the flame-retardant ABS material has the following beneficial effects:

the AS particles with special molecular weight distribution are added into the ABS resin matrix, and a preferable formula system is matched, so that the obtained flame-retardant ABS material has high fluidity, high impact property, excellent flame retardance and oil resistance, an injection molding thin-wall part is convenient to form, good in oil resistance, high in toughness and stable in flame retardance, and the requirements of kitchens, bathrooms, restaurants and the like on oil-resistant flame-retardant products can be met.

Detailed Description

In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

The technical solution of the present invention will be further clarified by the following specific examples and comparative examples, wherein the flow improver used in the following examples is AS particles having a weight average molecular weight of 1 to 2 ten thousand, and is available commercially under the brand name of EMI 200, and other raw materials or auxiliaries, such AS those mentioned above, are not specifically mentioned.

Example 1

The preparation method of the flame-retardant ABS material in the embodiment specifically comprises the following steps:

weighing 30 parts of ABS resin AG10NP, 50 parts of ABS resin AG12A1, 1 part of fluid improver, 18.2 parts of flame retardant (wherein, 15 parts of bromotriazine, 3 parts of antimony trioxide and 0.2 part of polytetrafluoroethylene), 0.1 part of antioxidant 1076, 0.2 part of antioxidant 168, 0.3 part of lubricant stearic acid amide and 0.2 part of lubricant calcium stearate according to the weight part ratio;

uniformly premixing a flame retardant, a lubricant, a fluid improver and an antioxidant in a high-speed mixer to obtain a first premix;

then uniformly mixing the first premix and the dried ABS resin particles in a high-speed mixer to obtain a second premix;

adding the second premix into a double-screw extruder to perform melt blending, extrusion, cooling, granulation and drying to obtain the flame-retardant ABS material, wherein the processing temperature of the double-screw extruder is as follows: 170 ℃ in the first zone, 180 ℃ in the second zone, 190 ℃ in the third zone, 190 ℃ in the fourth zone, 180 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the head and 380 revolutions per minute of the screw. .

Example 2

The preparation method of the flame-retardant ABS material in the embodiment specifically comprises the following steps:

weighing 30 parts of ABS resin AG10NP, 44 parts of ABS resin AG12A1, 5 parts of fluid improver, 20.2 parts of flame retardant (wherein, 16 parts of bromotriazine, 4 parts of antimony trioxide and 0.2 part of polytetrafluoroethylene), 0.1 part of antioxidant 1076, 0.2 part of antioxidant 168, 0.3 part of lubricant stearic acid amide and 0.2 part of lubricant calcium stearate according to the weight part ratio;

the other steps are the same as in example 1.

Example 3

The preparation method of the flame-retardant ABS material in the embodiment specifically comprises the following steps:

weighing 35 parts of ABS resin AG10NP, 42 parts of ABS resin AG12A1, 20 parts of flame retardant (wherein, 15.8 parts of bromotriazine, 4 parts of antimony trioxide and 0.2 part of polytetrafluoroethylene), 3 parts of fluid improver, 0.5 part of lubricant calcium stearate and antioxidant 10760.1 and 1680.2 parts of antioxidant;

other procedures were as in example 1

Comparative example 1

This comparative example is different from example 1 in that "ABS resin AG10NP 30 parts, ABS resin AG12A 150 parts, fluid improving agent 1 part" was replaced with "ABS resin AG10NP 31 parts, ABS resin AG12A 150 parts", and the other parts were the same as example 1.

Comparative example 2

This comparative example is different from example 1 in that "ABS resin AG10NP 30 parts, ABS resin AG12A 150 parts, fluid improver 1 part" was replaced with "ABS resin AG10NP 23 parts, ABS resin AG12A 150 parts, fluid improver 8 parts", and the others were the same as example 1.

Comparative example 3

This comparative example is different from example 1 in that "30 parts of ABS resin AG10NP and 50 parts of ABS resin AG12A 1" were replaced with "80 parts of ABS resin having an AS weight average molecular weight distribution of 6 to 10 ten thousand", and the other points were the same AS example 1.

Test example

The flame-retardant ABS materials prepared in examples 1-2 and comparative examples 1-3 were dried in an oven at 80 ℃ for 4 hours, and a national standard notched impact specimen bar and a flame-retardant specimen bar of 2.0mm were injection-molded, and the specimen bar tested for oil resistance (olive oil) was a national standard tensile specimen bar.

Wherein, the oil resistance test: the method comprises the following steps of (1) fixedly bending two ends of a 3.2mm test sample strip on a die with a fixed radian, coating olive oil on the sample strip subjected to bending stress, judging the oil resistance effect of the material according to the cracking time of the sample strip, wherein the size of the sample strip is 128mm multiplied by 12.8mm multiplied by 3.2mm, and the longer the cracking time is, the better the oil resistance of the material is, and the worse the oil resistance is;

the melt index test conditions were: GB/T3682, 220 ℃/10 kg;

impact strength: GB/T1843, the sample size is 80mm multiplied by 10mm multiplied by 4 mm;

flame retardance: UL-94, spline size 128mm × 12.8mm × 2.0 mm.

The test results are shown in table 1:

TABLE 1 flame-retardant ABS materials Performance test results

	Example 1	Example 2	Comparative example 1	Comparative example 2	Comparative example 3
						Oil resistance	****	***	****	×	×××
Finger-shaped fusion	32	44	26	61	40
						Impact of	21	18	23	14	11
Flame-retardant	V0	V0	V0	V0	V0

Note: in table 1, x represents good olive oil resistance, and x represents poor olive oil resistance.

As shown in Table 1, the analysis of comparative examples 1 and 2 shows that the addition of the low molecular weight AS fluid improver can significantly improve the flowability of the material and the processability of the material in the process of forming a thin-wall large part. It can be seen from comparative example 2 that the addition of a high content of low molecular weight AS results in a large loss of toughness of the material and a reduction in oil resistance of the material. The comparison example 3 shows that the molecular weight of AS in the ABS matrix is small AS a whole, and the oil resistance of the material is poor.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.