ABS (Acrylonitrile Butadiene Styrene) resin composition as well as preparation method and application thereof

Abstract

The invention provides an ABS (Acrylonitrile Butadiene Styrene) resin composition as well as a preparation method and application thereof, and the ABS resin composition comprises the following components in parts by weight: 95-100 parts of ABS resin and 0.1-5 parts of a first auxiliary agent, the first auxiliary agent comprises a first compound; the molecular structure of the first compound contains a fluorenone structure and a triphenylamine structure. According to the ABS resin composition disclosed by the invention, the problem that an ABS material in the prior art is easy to turn blue at the initial stage of use under an illumination condition is solved.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to an ABS resin composition and a preparation method and application thereof. Background Art

[0002] ABS resin, acrylonitrile-butadiene-styrene copolymer, is a thermoplastic polymer material. Due to its excellent gloss, toughness, hardness and processing fluidity, it is widely used in household appliances, cleaning appliances, electronic appliances and other fields. However, ABS materials are prone to photodegradation under long-term sunlight exposure, resulting in color changes, which initially appear as blue, then gradually fade and eventually turn yellow, seriously affecting the appearance and service life of the product.

[0003] At present, most of the research focuses on the long-term light aging resistance of ABS materials, that is, solving the problem of yellowing and performance degradation of ABS materials under long-term oxygen and light conditions. There has been no in-depth research on how to reduce the blueing problem of ABS materials in the early stage of use.

[0004] Therefore, it is an urgent problem to be solved in the art to develop an ABS resin material that is resistant to blue discoloration, has a low change in the blue discoloration index in the initial use, and has good color stability. Summary of the invention

[0005] In view of the shortcomings of the prior art, the present invention aims to provide an ABS resin composition and a preparation method and application thereof. The ABS resin composition solves the problem that the ABS material in the prior art tends to turn blue under light conditions at the initial stage of use.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides an ABS resin composition, which comprises, by weight, 95 to 100 parts of ABS resin and 0.1 to 5 parts of a first auxiliary agent; the first auxiliary agent comprises a first compound; and the molecular structure of the first compound contains a fluorenone structure and a triphenylamine structure.

[0008] In the present invention, the fluorenone structure and the triphenylamine structure have good free radical scavenging effect. The molecular structure of the first compound contains the fluorenone structure and the triphenylamine structure, has excellent light stability, and can effectively protect the ABS resin, inhibit the short-term blue discoloration of the ABS resin during the light aging process, and enable the ABS resin to maintain excellent color stability. By adding a first auxiliary agent of a specific type and content, the ABS resin material is resistant to blue discoloration in a short period of time during the light aging process and has good color stability, which is beneficial to improving the overall performance of the ABS resin material and extending its service life.

[0009] In the present invention, 95 to 100 parts of ABS resin can be, for example, 95 parts, 95.2 parts, 95.4 parts, 95.6 parts, 95.8 parts, 96 parts, 96.2 parts, 96.4 parts, 96.6 parts, 96.8 parts, 97 parts, 97.2 parts, 97.4 parts, 97.6 parts, 97.8 parts, 98 parts, 98.2 parts, 98.4 parts, 98.6 parts, 98.8 parts, 99 parts, 99.2 parts, 99.4 parts, 99.6 parts, 99.8 parts, 100 parts, or a range consisting of any of the above values.

[0010] In the present invention, 0.1 to 5 parts of the first auxiliary agent can be, for example, 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.45 part, 0.5 part, 0.55 part, 0.6 part, 0.65 part, 0.7 part, 0.75 part, 0.8 part, 0.85 part, 0.9 part, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 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, 5 parts or the range composed of any of the above numerical values.

[0011] Preferably, the ABS resin composition comprises 97 to 99 parts of ABS resin and 0.3 to 1.1 parts of the first auxiliary agent, more preferably 0.42 to 1.05 parts of the first auxiliary agent, in parts by weight.

[0012] In the present invention, the mass percentage of ABS resin in the ABS resin composition is ≥90%, more preferably ≥95%.

[0013] In the present invention, the mass percentage of the first compound in the first auxiliary agent is ≥50%, more preferably ≥55%, and particularly preferably 60-80%.

[0014] Preferably, the first compound comprises

[0015] In the present invention, the first compound It can be prepared by itself. For example, the preparation method of the first compound includes: reacting 2,7-dibromofluorenone with 4-triphenylamine borate to obtain the first compound; the molar ratio of 2,7-dibromofluorenone to 4-triphenylamine borate is 1:(2-4); the reaction is carried out in the presence of a catalyst (including Pd(PPh3)4) and a solvent (including a mixed solvent of 3 mol / L potassium carbonate aqueous solution and toluene); the reaction temperature is 80-100°C, and the reaction time is 24-72h; after the reaction is completed, it also includes extraction and purification steps.

[0016] Preferably, the first auxiliary agent further comprises a second compound; the second compound comprises a benzotriazole compound.

[0017] Preferably, the second compound comprises 2-(2′-hydroxy-5′-methylphenyl)benzotriazole (UV-P, ) and / or 2-(2'-hydroxy-3',5'bis(a,a-dimethylbenzyl)phenyl)benzotriazole (UV-234,)

[0018]

[0019] Preferably, the mass ratio of the first compound to the second compound is 1:(0.1-1), wherein the specific value in (0.1-1) can be, for example, 0.1, 0.15, 0.2, 0.25, 0.3, 0.32, 0.34, 0.36, 0.38, 0.4, 0.42, 0.44, 0.46, 0.48, 0.5, 0.52, 0.54, 0.56, 0.58, 0.6, 0.62, 0.65, 0.68, 0.7, 0.72, 0.75, 0.78, 0.8, 0.85, 0.9, 0.95, 1 or a range consisting of any of the above values; a further preferred mass ratio is 1:(0.3-0.6).

[0020] In the present invention, by compounding the first compound and the second compound, the ABS material has both short-term blue discoloration resistance and long-term yellowing resistance. If the proportion of the second compound is too high, the short-term blue discoloration resistance effect is poor; if the proportion is too low, the long-term yellowing resistance is poor.

[0021] In the present invention, according to ASTM D1238-2010 standard, at 220°C and 10kg, the melt index of the ABS resin is 10 to 40 g / 10min, for example, 10 g / 10min, 12 g / 10min, 15 g / 10min, 18 g / 10min, 20 g / 10min, 21 g / 10min, 22 g / 10min, 23 g / 10min, 24 g / 10min, 25 g / 10min, 26 g / 10min, g / 10min, 27g / 10min, 28g / 10min, 29g / 10min, 30g / 10min, 31 g / 10min, 32g / 10min, 33g / 10min, 34g / 10min, 35g / 10min, 36g / 10min, 37g / 10min, 38g / 10min, 39g / 10min, 40g / 10min or ranges between any of the above values.

[0022] In the present invention, the ABS resin composition further comprises 0.5 to 3.5 parts of a second auxiliary agent, by weight, for example, 0.5 parts, 1 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts or any range between the above values.

[0023] Preferably, the second auxiliary agent includes an antioxidant and / or a lubricant.

[0024] Preferably, in parts by weight, the second auxiliary agent includes 0.5 to 2 parts of lubricant (for example, 0.5 parts, 1 parts, 1.5 parts, 2 parts or any range between the above values) and 0.2 to 1 parts of antioxidant (for example, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 parts or any range between the above values).

[0025] In the present invention, the antioxidant includes a primary antioxidant and a secondary antioxidant; the primary antioxidant includes but is not limited to tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester (antioxidant 1010), β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol ester (antioxidant 1076), triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] (antioxidant 245) and other hindered phenol antioxidants; the secondary antioxidant includes but is not limited to tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168), bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate (PEP36) and other phosphite antioxidants.

[0026] In the present invention, the lubricant includes but is not limited to vinyl bisstearamide, erucamide, stearate and the like.

[0027] In the present invention, the ABS resin composition may also be added with other second additives in addition to antioxidants and lubricants according to actual needs, illustratively including but not limited to colorants, antistatic agents (such as ethoxy lauric acid amine, dilauryl phosphate, glycerol monostearate, etc.), coupling agents (such as silane coupling agents, titanate coupling agents, etc.), compatibilizers (such as maleic anhydride grafted acrylonitrile-butadiene-styrene polymers, etc.), flame retardants (such as aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, melamine derivatives, etc.), etc.

[0028] In a second aspect, the present invention provides a method for preparing the ABS resin composition according to the first aspect, the preparation method comprising the following steps:

[0029] The ABS resin is mixed with the first auxiliary agent and extruded to obtain the ABS resin composition.

[0030] Preferably, the mixed material further comprises a second auxiliary agent.

[0031] In the present invention, the mixing can be carried out in a high-speed mixer; the mixing time is 3 to 5 minutes, and the rotation speed is 50 to 200 rpm.

[0032] Preferably, the extrusion temperature is 150-230°C.

[0033] In the present invention, the extrusion can be carried out in a twin-screw extruder; the temperature ranges of the twin-screw extruder are as follows: zone 1 150-180°C; zone 2 180-200°C; zone 3 180-200°C; zone 4 190-210°C; zone 5 200-220°C; zone 6 200-220°C; zone 7 200-220°C; zone 8 210-230°C; zone 9 210-230°C; zone 10 210-230°C; zone 11 210-230°C; the rotation speed of the twin-screw extruder is 300-600rpm, and the aspect ratio is 40-44:1.

[0034] In a third aspect, the present invention provides a blue discoloration resistant material, wherein the blue discoloration resistant material comprises the ABS resin composition described in the first aspect.

[0035] In the present invention, the blue discoloration resistant material can be used to prepare plastic housing parts required by household appliances, cleaning appliances, electronic appliances, etc.

[0036] The numerical range described in the present invention not only includes the point values ​​listed above, but also includes any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] The ABS resin composition provided by the present invention, by adding a first auxiliary agent of a specific type and content, makes the ABS resin material resistant to blue discoloration in a short period of time and has good color stability, which is beneficial to improving the overall performance of the ABS resin material and extending its service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a hydrogen nuclear magnetic resonance spectrum of the first compound provided by the present invention.

[0040] Figure 2 This is the UV-visible absorption spectrum of the first compound provided by the present invention. DETAILED DESCRIPTION

[0041] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0042] Unless otherwise specified, the materials used in the present invention can be purchased from the market or prepared by conventional methods; the materials used in the present invention are as follows:

[0043] ABS resin: DG 417, Tianjin Dagu, according to ASTM D1238-2010 standard, the melt index is 20g / 10min at 220℃ and 10kg.

[0044] First Compound

[0045] The preparation method comprises: adding 24 mL of chromatographically pure toluene and 16 mL of potassium carbonate aqueous solution (concentration of 3M) into a 100 mL round-bottom flask, then adding 2,7-dibromofluorenone and 4-boric acid triphenylamine in a molar ratio of 1:2.5, adding catalyst Pd(PPh3)4 (138 mg, 0.12 mmol) after degassing, and reflux at 90°C for 48 hours. After the reaction is completed, cool to room temperature, add a suitable volume of deionized water and stir, extract the reaction solution with dichloromethane, and extract repeatedly three times. Add an appropriate amount of silica gel to the extract and spin dry, and purify the spin-dried product by column chromatography, wherein the developing solvent during column chromatography purification is a mixed solution of petroleum ether and dichloromethane with a volume ratio of 3:1, to obtain the first compound; the yield is 90%.

[0046] Using H NMR spectroscopy ( 1 The structure of the first compound was characterized by H-NMR, and the specific method included: dissolving the first compound in deuterated dimethyl sulfoxide to prepare a solution with a mass concentration of 0.6 mg / mL; then testing it using a nuclear magnetic resonance hydrogen spectrometer (500 MHz); the results are as follows Figure 1 As shown; the relative atomic mass of the first compound was measured by mass spectrometry (MALDI-TOF MS) and was found to be 666.8.

[0047] The UV-visible absorption spectrum of the first compound was tested by UV-visible absorption spectrometer. Figure 2 shown by Figure 2 It can be seen that the first compound can absorb light of 250 to 550 nm.

[0048] Second compound

[0049] UV-234, commercially available; UV-P, commercially available.

[0050] Antioxidant: a compound antioxidant consisting of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1, commercially available.

[0051] Lubricant: Vinyl bisstearamide, commercially available.

[0052] Examples 1 to 10, Comparative Examples 1 to 2

[0053] Examples 1 to 10 and Comparative Examples 1 to 2 respectively provide an ABS resin composition, and the formula of the ABS resin composition is shown in Table 1, in parts by weight; wherein, “ / ” indicates that the component is not included in the formula; the preparation method of the ABS resin composition comprises: weighing raw materials by weight, and then putting them into a mixer with a rotation speed of about 100 rpm for dry mixing for 5 minutes, and then melt-extruding and granulating the mixed raw materials in a twin-screw extruder with a length-to-diameter ratio of 40:1, temperatures in different intervals of 160°C, 190°C, 190°C, 200°C, 210°C, 210°C, 220°C, 220°C, 220°C, and a rotation speed of 450 rpm to obtain the ABS resin composition.

[0054] Table 1

[0055]

[0056] Performance Testing

[0057] The ABS resin compositions provided in Examples 1 to 10 and Comparative Examples 1 to 2 were injection molded, and the obtained color plates were tested for the changes in the b value of the ABS resin compositions before and after aging according to ISO4892-2 standard; specifically: the lamp type is UVA-340, and the irradiation intensity is 0.5 W / m 2 ·nm, blackboard temperature at 60°C for 8 hours in the illumination stage; blackboard temperature at 50°C for 4 hours in the condensation stage. The aging test cycle is 168 hours, and the test is conducted once every 12 hours. The b value changes △b of the ABS resin compositions provided in Examples 1 to 10 and Comparative Examples 1 and 2 in different time periods are shown in Table 2.

[0058] Table 2

[0059]

[0060] As can be seen from Table 2, the ABS resin composition provided by the present invention, by adding a first auxiliary agent of a specific content and type, makes the ABS resin composition resistant to blue discoloration in a short period of time and has good color stability; under different aging times, Δb is between -3.18 and 5.23, and can even reach -0.1 to 1, which is close to 0.

[0061] In comparative example 1, ABS without any absorbent turned blue after illumination, with the maximum change of 12h b value being -3.22, and then gradually moved to the yellow phase; in comparative example 2, the second compound was added, and it turned blue immediately after illumination, with the maximum change of 12hb value being -5.01, and remained in the blue phase within 168 hours.

[0062] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. An ABS resin composition, characterized in that: In parts by weight, the ABS resin composition comprises 95 to 100 parts of ABS resin and 0.1 to 5 parts of a first auxiliary agent; The first auxiliary agent includes a first compound; the molecular structure of the first compound contains a fluorenone structure and a triphenylamine structure.

2. The ABS resin composition according to claim 1, characterized in that In parts by weight, the ABS resin composition comprises 97 to 99 parts of ABS resin and 0.3 to 1.1 parts of the first auxiliary agent.

3. The ABS resin composition according to claim 1 or 2, characterized in that: The first compound includes 4. The ABS resin composition according to any one of claims 1 to 3, characterized in that: The first auxiliary agent also includes a second compound; the second compound includes a benzotriazole compound; Preferably, the second compound comprises 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and / or 2-(2'-hydroxy-3',5'bis(a,a-dimethylbenzyl)phenyl)benzotriazole.

5. The ABS resin composition according to claim 4, characterized in that: The mass ratio of the first compound to the second compound is 1:(0.1-1), and more preferably the mass ratio is 1:(0.3-0.6).

6. The ABS resin composition according to any one of claims 1 to 5, characterized in that: The ABS resin composition further comprises 0.5 to 3.5 parts by weight of a second auxiliary agent.

7. The ABS resin composition according to claim 6, characterized in that: The second auxiliary agent includes an antioxidant and / or a lubricant.

8. A method for preparing the ABS resin composition according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: The ABS resin is mixed with the first auxiliary agent and extruded to obtain the ABS resin composition.

9. The preparation method according to claim 8, characterized in that: The mixed material also includes a second auxiliary agent; Preferably, the extrusion temperature is 150-230°C.

10. A blue discoloration resistant material, characterized in that: The blue discoloration resistant material comprises the ABS resin composition according to any one of claims 1 to 7.

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