ABS composite material as well as preparation method and application thereof

Abstract

The invention discloses an ABS (Acrylonitrile Butadiene Styrene) composite material as well as a preparation method and application thereof. The ABS composite material comprises the following components in parts by weight: 80-92 parts of ABS resin; 5-20 parts of an organic phosphine oxide; 1-5 parts of a phosphate flame retardant; wherein the organic phosphine oxide has a structure as shown in a formula I which is described in the specification; r1 is selected from methyl, phenyl or ethyl, and R2 is selected from methylene, arylene or ethylidene; the melt flow rate of the ABS resin under the conditions of 220 DEG C and 10kg is greater than or equal to 18g / 10min; the phosphate flame retardant comprises one or more of bisphenol A-bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate) or hydroquinone bis (diphenyl phosphate). The ABS resin with a specific melt flow rate is adopted as matrix resin, and the organic phosphine oxide and the phosphate flame retardant are added for compounding, so that the prepared ABS composite material is good in flame retardance, relatively high in glossiness and relatively small in thermal retention color difference.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to an ABS composite material, its preparation method, and its application. Background Technology

[0002] Acrylonitrile-butadiene-styrene copolymer (ABS resin) is widely used in the automotive, electronics, general electrical appliances and office supplies industries due to its good impact resistance, low temperature resistance, chemical resistance and excellent electrical properties. However, ABS resin has poor flame retardant properties, and flame retardant modification is required when it is used in the housing of electrical equipment that requires electrical insulation and flame retardancy.

[0003] Most flame retardants commonly used in ABS resin are brominated flame retardants, which easily produce large amounts of dense smoke and release toxic and harmful gases when burning. Halogen-free flame-retardant ABS is the future development trend. However, adding halogen-free flame retardants causes ABS to lose its original luster, significantly affecting the appearance of the ABS material. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art in which halogen-free flame-retardant ABS composite materials cannot simultaneously possess flame-retardant properties and high gloss, and to provide an ABS composite material.

[0005] Another object of the present invention is to provide a method for preparing the ABS composite material.

[0006] Another object of the present invention is to provide applications of the ABS composite material.

[0007] To achieve the above objectives, the present invention employs the following technical solution:

[0008] An ABS composite material comprises the following components in parts by weight: 80-95 parts of ABS resin; 5-20 parts of organophosphorus oxides; 1-5 parts of phosphate ester flame retardant; The organophosphorus oxide has the structure shown in Formula I: Formula I; R1 is selected from methyl, phenyl or ethyl, and R2 is selected from methylene, aryl or ethylene; the melt flow rate of the ABS resin at 220°C and 10kg is ≥18g / 10min; the phosphate ester flame retardant includes one or more of bisphenol A-bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate) or hydroquinone bis(diphenyl phosphate).

[0009] This invention provides an ABS composite material that uses a combination of organophosphorus oxide and phosphate ester flame retardant as a halogen-free flame retardant. The phosphorus in the organophosphorus oxide is more easily decomposed to generate more PO and PO2 free radicals compared to the saturated valence state, which captures •H and •OH free radicals generated during combustion. At the same time, the phosphate ester flame retardant has a good plasticizing effect and good compatibility with the styrene-acrylonitrile part of ABS resin. The combination with organophosphorus oxide can ensure the flame retardant performance of the ABS composite material while also providing good gloss.

[0010] It should be noted that the organophosphorus oxides mentioned in this invention are 5 to 20 parts, for example, but not limited to 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, or 20 parts, etc., and the specific point values ​​between the above point values ​​are not exhaustively listed in this invention due to space limitations and for the sake of brevity.

[0011] It should be noted that the phosphate ester flame retardant described in this invention is 1 to 5 parts, for example, but not limited to 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts, 4.8 parts, or 5 parts, etc., and the specific point values ​​between the above point values ​​are not exhaustively listed in this invention due to space limitations and for the sake of brevity.

[0012] Furthermore, the content of organophosphorus oxide in the ABS composite material is 5~20wt%.

[0013] Furthermore, in the organophosphorus oxide, R1 is phenyl and R2 is arylene; or in the organophosphorus oxide, R1 is phenyl and R2 is ethylene.

[0014] Furthermore, in the organophosphorus oxide, R1 is phenyl and R2 is arylene.

[0015] Furthermore, the phosphate ester flame retardant includes bisphenol A-bis(diphenyl phosphate) and / or hydroquinone bis(diphenyl phosphate).

[0016] Furthermore, the mass ratio of the organophosphorus oxide to the phosphate ester flame retardant is (2~17):1, for example, but not limited to, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1 or 17:1, etc., and the specific values ​​between the above points are not exhaustively listed in this invention due to space limitations and for the sake of brevity.

[0017] Furthermore, the mass ratio of the organophosphorus oxide to the phosphate ester flame retardant is (2.5~16.5):1.

[0018] Furthermore, the mass ratio of the organophosphorus oxide to the phosphate ester flame retardant is (10~15):1.

[0019] It should be noted that the ABS resin described in this invention has a melt flow rate ≥18g / 10min at 220℃ and 10kg, for example, but not limited to, ≥18g / 0min, 20g / 10min, 22g / 10min, 25g / 10min, 28g / 10min, 30g / 10min, 32g / 10min, 35g / 10min, 38g / 10min, 40g / 10min, 42g / 10min. The specific point values ​​included in the ranges are 45g / 10min, 48g / 10min, 50g / 10min, 52g / 10min, 55g / 10min, 58g / 10min, 60g / 10min, 62g / 10min, 65g / 10min, 68g / 10min, or 70g / 10min, as well as the specific point values ​​between the above-mentioned point values. Due to space limitations and for the sake of brevity, the specific point values ​​included in the ranges will not be exhaustively listed in this invention.

[0020] Furthermore, the melt flow rate of the ABS resin at 220°C and 10kg is 20~70g / 10min.

[0021] Furthermore, the test standard for the melt flow rate of the ABS resin is GB / T 3682.1-2018.

[0022] Furthermore, in the ABS composite material, the ABS resin content is preferably not less than 75 wt%.

[0023] Furthermore, without affecting the appearance, flame retardant properties, and heat retention color difference of the ABS composite material described in this invention, it also includes 0.1 to 10 parts of processing aids.

[0024] Furthermore, the processing aids include, but are not limited to, one or more of antioxidants, lubricants, weathering agents, antistatic agents, or colorants.

[0025] Specifically, the antioxidant may be a commonly used antioxidant, such as, but not limited to, hindered phenolic antioxidants and / or phosphate antioxidants.

[0026] Specifically, the hindered phenolic antioxidant is one or more of N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide) (Irganox 1098), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 259), octadecyl β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate (Irganox 1076), or 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acrylic acid]-1,1-dimethyl}-2,4,8,10-tetraoxaspirocycloundecane (ADK AO-80).

[0027] The phosphate ester antioxidant is one or more of tris(2,4-di-tert-butylphenyl) phosphite (Irganox 168), bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate (PEP-36), or 627A.

[0028] Commonly used lubricants can be selected in this invention. For example, but not limited to, one or more of erucamide, oleamide, vinyl bis-stearamide, polysiloxane, calcium stearate, magnesium stearate, zinc stearate, or PE wax.

[0029] The present invention can use commonly used weathering agents. For example, but not limited to, one or more of hydroxybenzophenone light stabilizers, hydroxybenzotriazole light stabilizers, and hindered amine light stabilizers.

[0030] The present invention can use commonly used antistatic agents, such as, but not limited to, one or more of ethoxylated alkylamines, ethoxylated alkyl acid amines, or glyceryl stearate.

[0031] The present invention can use commonly used colorants, such as, but not limited to, pigments and / or pigment masterbatches.

[0032] Furthermore, the ABS composite material comprises the following components in parts by weight: 82-88 parts of ABS resin; 10-18 parts of organophosphorus oxides; 2-5 parts of phosphate ester flame retardant.

[0033] The present invention also provides a method for preparing the above-mentioned ABS composite material, comprising the following steps: The components are mixed evenly in proportion, and then melted, extruded and granulated to obtain ABS composite material.

[0034] Specifically, the extrusion granulation is performed using a twin-screw extruder.

[0035] Specifically, the screw speed of the twin-screw extruder is 300~500 rpm.

[0036] Specifically, the temperature of the twin-screw extruder is 80~100℃ in zone one, 180~190℃ in zone two, 190~200℃ in zones three to nine, and 200~210℃ at the die head.

[0037] The present invention also provides the application of the above-mentioned ABS composite material in the preparation of materials for home appliances, office supplies and electronic appliances, especially suitable for accessories that require high gloss, flame retardancy and low heat retention color difference, especially for larger parts or parts with complex structures.

[0038] A component made of the aforementioned ABS composite material, such as materials for large-size household appliance parts, printer parts, and especially display parts.

[0039] Compared with the prior art, the present invention has the following beneficial effects: This invention provides an ABS composite material, which uses ABS resin with a specific flow rate as the matrix resin and adds organophosphorus oxide and phosphate flame retardant as halogen-free flame retardant. This allows the ABS composite material to have good flame retardant properties, good appearance properties, and small heat retention color difference. Detailed Implementation

[0040] The present invention will be further described in detail below with reference to specific embodiments. These embodiments are only used to explain the present invention and are not intended to limit the scope of the present invention. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods; the materials and reagents used are commercially available unless otherwise specified.

[0041] 1. Raw materials used in each embodiment and comparative example: ABS resin: ABS resin 1: KF-740, with a melt flow rate of 38g / 10min at 220℃ and 10kg, manufactured by Liaoning Kingfa Science & Technology Co., Ltd. ABS resin 2: KF-730, with a melt flow rate of 22g / 10min at 220℃ and 10kg, is manufactured by Liaoning Kingfa Science & Technology Co., Ltd. ABS resin 3: ABS HF-681, with a melt flow rate of 45g / 10min at 220℃ and 10kg, manufactured by Jilin Petrochemical Company; ABS resin 4: ABS D670, with a melt flow rate of 70g / 10min at 220℃ and 10kg, manufactured by Guoqiao Petrochemical Co., Ltd. ABS resin 5: KF-718, with a melt flow rate of 11g / 10min at 220℃ and 10kg, is manufactured by Liaoning Kingfa Science & Technology Co., Ltd. Organophosphorus oxides: Organophosphorus oxide 1: p-Xylylbisdiphenylphosphine oxide, XDPO, with the structural formula shown in Formula I, where R1 is phenyl and R2 is phenylene, CAS number is 38661-56-2, and the manufacturer is Zibo Shengsen Fine Chemical Co., Ltd. Organophosphorus oxide 2: 1,2-bis(diphenylphosphoxy)ethane, EDPO, with the structural formula shown in Formula I, where R1 is phenyl and R2 is ethylene, CAS number 4141-50-8, and the manufacturer is Beijing Huawi Ruike Chemical Technology Co., Ltd. Organophosphorus oxide 3: Triphenylphosphine oxide, TPPO, CAS No. 791-28-6, manufactured by Shanghai Weifang Fine Chemical Co., Ltd. Organophosphorus oxide 4: Triphenyl phosphate, WSFR-TPP, CAS number 115-86-6, manufacturer is Zhejiang Wansheng; Organophosphorus oxide 5: 1,2-bis(diphenylphosphine)ethane, DPPE, CAS No. 1663-45-2, manufactured by Beijing Huawirui Chemical Technology Co., Ltd. Phosphate ester flame retardants: Phosphate ester flame retardant 1: Hydroquinone bis(diphenyl phosphate), WSFR-PX-220, manufactured by Zhejiang Wansheng Technology Co., Ltd. Phosphate ester flame retardant 2: Bisphenol A bis(diphenyl phosphate), WSFR-BDP-N2, manufactured by Zhejiang Wansheng Technology Co., Ltd. Phosphate ester flame retardant 3: Trimethyl phosphate, TCP, manufactured by Shandong Rongsheng New Materials Co., Ltd. Processing aids: Antioxidant: Hindered phenolic antioxidant, commercially available; Lubricant: Amide lubricant, commercially available; It should be noted that the same raw materials used in the parallel experiments of the embodiments and comparative examples in this invention are from the same source.

[0042] 2. The ABS composite materials described in each embodiment and comparative example were prepared according to the formulations in Tables 1-2 using the following preparation method: The components are added to a high-speed mixer in proportion and mixed evenly. The mixture is then fed into a twin-screw extruder, and the resulting material is melted, extruded, and granulated to obtain ABS composite material. The screw speed of the twin-screw extruder is 300~500 rpm. The temperature of the first zone of the twin-screw extruder is 80~100℃, the temperature of the second zone is 180~190℃, the temperature of the third to ninth zones is 190~200℃, and the die head temperature is 200~210℃.

[0043] 3. Performance Testing: (1) Flame retardant performance test: The ABS composite materials prepared in each example and comparative example were injection molded into standard burning test strips with a length of 125 mm, a width of 12.7 mm, and thicknesses of 1 mm and 2 mm, respectively. Vertical burning was tested according to the standard UL94-2018. (2) Surface gloss test: The ABS composite materials prepared in each example and comparative example are injection molded into standard color plates. The surface gloss is tested according to the standard GB 8807-1988 "Plastic Mirror Gloss Test Method" at a test angle of 60°. The gloss of pure ABS resin is about 92%, and usually ABS composite materials are required to reach more than 85% for high gloss. (3) Heat retention color difference test: The ABS composite materials prepared in each example and comparative example were injection molded into color plates at 220℃ and the color of the color plates was tested; the ABS composite materials were heat retained in the injection molding machine at 220℃ for 10 min and then injection molded into color plates and the color of the color plates was tested. The heat retention color difference was calculated and recorded as △E@220℃10min. The heat retention color difference should be less than 2 in order to meet the requirement that the parts have no obvious color change. L* represents lightness, ranging from 0 to 100, indicating colors from dark (black) to light (white).

[0044] a* represents red and green, and the value changes from positive to negative, indicating the color changes from red to green.

[0045] b* represents yellow to blue, and the value changes from positive to negative, indicating a color change from yellow to blue.

[0046] △L* represents the difference in brightness; a positive value indicates a lighter (whiter) lightness, while a negative value indicates a darker (blacker) lightness.

[0047] △a* represents the difference between red and green; a positive value indicates more red, and a negative value indicates more green.

[0048] △b* represents the difference between yellow and blue; a positive value indicates more yellow, and a negative value indicates more blue.

[0049] △E represents the total color difference. The calculation formula is as follows: △E@220℃10min=(△L*^2+△a*^2+△b*^2)^0.5.

[0050] Examples 1-10 and Comparative Examples 1-7 Table 1. Amounts (parts by weight) and properties of each component in the ABS composite material in each embodiment.

[0051] Table 2. Amounts (parts by weight) and properties of each component in the ABS composite materials of each comparative example.

[0052] As can be seen from Table 1, the ABS composite material prepared by the present invention has good flame retardant properties and can stably reach the V-2 flame retardant rating, while also having high gloss and low heat retention color change; specifically, both 1.0mm and 2.0mm can achieve V-2 flame retardancy, surface gloss is ≥85%, and heat retention color difference is ≤2.0.

[0053] As can be seen from Comparative Examples 1 and 2, if other structural organophosphorus oxides are used instead of the organophosphorus oxides of the present invention as flame retardants, the overall performance of the ABS composite material is significantly reduced.

[0054] As can be seen from Comparative Example 3, if a compound without phosphorus oxygen structure is used instead of the organophosphorus oxide of the present invention, the resulting ABS composite material has no obvious flame retardant effect and is difficult to pass the V-2 test.

[0055] As can be seen from Comparative Example 4, if the melt flow rate of the ABS resin used is too low, it will be difficult to drip quickly and extinguish the flame in time, thus failing to achieve the V-2 flame retardant rating.

[0056] As can be seen from Comparative Example 5, if only organophosphorus oxides are used, although the flame retardant performance is good, the dripping time is long and the heat cannot be carried away quickly, so the 2mm specimen is difficult to reach the V-2 level.

[0057] As can be seen from Comparative Example 6, if too little organophosphorus oxide is added and too much phosphate ester flame retardant is added, although it is easy to drip during combustion, the flame retardant performance is poor, and the flame cannot be extinguished after dripping, thus failing to reach the V-2 flame retardant rating.

[0058] As can be seen from Comparative Example 7, if other phosphate ester flame retardants are used instead of the phosphate ester flame retardants of this invention, the resulting ABS composite material has poor flame retardancy and reduced thermal retention stability.

[0059] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. An ABS composite material, characterized in that, Includes the following components, calculated in parts by weight: 80-92 parts of ABS resin; 5-20 parts of organophosphorus oxides; 1-5 parts of phosphate ester flame retardant; The organophosphorus oxide has the structure shown in Formula I: Formula I; R1 is selected from methyl, phenyl or ethyl, and R2 is selected from methylene, aryl or ethylene; the melt flow rate of the ABS resin at 220°C and 10kg is ≥18g / 10min; the phosphate ester flame retardant includes one or more of bisphenol A-bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate) or hydroquinone bis(diphenyl phosphate).

2. The ABS composite material according to claim 1, characterized in that, In the organophosphorus oxide, R1 is phenyl and R2 is arylene; or in the organophosphorus oxide, R1 is phenyl and R2 is ethylene. Preferably, in the organophosphorus oxide, R1 is phenyl and R2 is arylene.

3. The ABS composite material according to claim 1, characterized in that, The phosphate ester flame retardants include bisphenol A-bis(diphenyl phosphate) and / or hydroquinone bis(diphenyl phosphate).

4. The ABS composite material according to claim 1, characterized in that, The mass ratio of the organophosphorus oxide to the phosphate flame retardant is (2~17):1; preferably, the mass ratio of the organophosphorus oxide to the phosphate flame retardant is (2.5~16.5):1; more preferably, the mass ratio of the organophosphorus oxide to the phosphate flame retardant is (10~15):

1.

5. The ABS composite material according to claim 1, characterized in that, The melt flow rate of the ABS resin at 220°C and 10 kg is 20~70 g / 10 min.

6. The ABS composite material according to claim 1, characterized in that, It also includes 0.1 to 10 parts of processing aids; the processing aids include one or more of antioxidants, lubricants, weathering agents, antistatic agents or colorants.

7. The ABS composite material according to claim 1, characterized in that, Includes the following components, calculated in parts by weight: 82-88 parts of ABS resin; 10-18 parts of organophosphorus oxides; 2-5 parts of phosphate ester flame retardant.

8. A method for preparing the ABS composite material according to any one of claims 1 to 7, characterized in that, Includes the following steps: The components are mixed evenly, and then melted, extruded and granulated to obtain ABS composite material.

9. The application of the ABS composite material according to any one of claims 1 to 7 in the preparation of materials for household appliances, office supplies, and electronic appliances.

10. A housing component, characterized in that, It is prepared using the ABS composite material described in any one of claims 1 to 7.

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