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

Abstract

The invention provides an ABS composition and a preparation method and application thereof.The ABS composition is prepared from, by weight, 90-95 parts of ABS resin, 0.1-1 part of a compound mold scale inhibitor, 1-5 parts of a lubricant and 0.2-1 part of an antioxidant, the compound mold scale inhibitor comprises a mold scale inhibitor A and a mold scale inhibitor B, wherein the molecular structure of the mold scale inhibitor A comprises structural fragments as shown in a formula I and / or a formula II, and the mold scale inhibitor B is a high-molecular antistatic agent; the mold scale inhibitor A with the structure is introduced into the ABS composition and is matched with the mold scale inhibitor B, so that the injection mold scale problem existing in the ABS injection molding process can be greatly relieved and even solved.

Description

Technical Field

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

[0002] With the continuous development of society, the increasing popularity of personal computers, and the constant upgrading of home appliances, the demand for weather-resistant ABS (acrylonitrile-butadiene-styrene copolymer) special materials in fields such as personal computer casings, copier casings, printer casings, appliance casings, and air conditioner panels is increasing. However, because the butadiene component in ABS block copolymers contains unsaturated double bonds, it is prone to thermal oxidative degradation under the high temperature environment of injection molding (usually 200-240℃), generating degradation products such as low molecular weight polymer fragments and small molecule volatiles. At the same time, in order to avoid the degradation of the butadiene component and improve the weather resistance of ABS, a variety of additives are introduced. However, these additives can also migrate and precipitate during high-temperature processing. The degradation products and precipitated additives will be adsorbed and attached to the surface of the mold cavity. After multiple injection cycles and high-temperature curing, a hard and viscous injection mold fouling layer is gradually formed.

[0003] The formation of mold fouling increases melt flow resistance, prolongs injection molding cycle, and reduces production efficiency. It can also corrode and wear the mold cavity. In addition, mold fouling can cause appearance defects in the product, and the degradation products and additive precipitates remaining in the mold fouling may adhere to the product, further accelerating the aging of the product. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the purpose of this invention is to provide an ABS composition, its preparation method and application.

[0005] To achieve this objective, the present invention adopts the following technical solution: In a first aspect, the present invention provides an ABS composition, wherein, based on parts by weight, the ABS composition comprises: 90-95 parts ABS resin, 0.1-1 parts composite mold fouling inhibitor, 1-5 parts lubricant, and 0.2-1 parts antioxidant, wherein the composite mold fouling inhibitor comprises mold fouling inhibitor A and mold fouling inhibitor B, wherein: The molecular structure of the fouling inhibitor A includes structural segments shown in Formula I and / or Formula II, and the fouling inhibitor B is a polymeric antistatic agent. , ; Wherein, n, x, and y are each independently selected from integers from 1 to 5, such as 1, 2, 3, 4, 5, or any of the above values.

[0006] This invention, by introducing the above-described mold fouling inhibitor A into the ABS composition and cooperating with mold fouling inhibitor B, can greatly alleviate or even solve the problem of injection mold fouling in the ABS injection molding process.

[0007] In this invention, the 90-95 parts of ABS resin can be 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, or any of the above values; the 0.1-1 part of composite mold fouling inhibitor can be 0.1 parts, 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 part, or any of the above values; the 1-5 parts of lubricant can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, or any of the above values; and the 0.2-1 part of antioxidant can be 0.2 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 part, or any of the above values.

[0008] Preferably, the mass ratio of the scale inhibitor A to the scale inhibitor B is ≥0.5, for example, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 4, 5, 6 or any of the above values, preferably ≥1, for example, 1, 1.5, 2, 2.5, 3, 4, 5, 6 or any of the above values.

[0009] In this invention, when the mass ratio of the mold fouling inhibitor A to the mold fouling inhibitor B is within the above-mentioned range, the resulting ABS composition will have less residual mold fouling during injection molding. If the mass of the mold fouling inhibitor B is too large, it will not be conducive to reducing mold fouling.

[0010] Preferably, the molecular weight of the fouling inhibitor A is 1000-3000 g / mol, for example, 1000 g / mol, 1100 g / mol, 1200 g / mol, 1500 g / mol, 1800 g / mol, 2000 g / mol, 2200 g / mol, 2400 g / mol, 2500 g / mol, 2600 g / mol, 2800 g / mol, 3000 g / mol, or any of the above values.

[0011] Preferably, the polymeric antistatic agent includes a polyether ester type antistatic agent, and more preferably a polyether ester amide type antistatic agent and / or a polyether-modified polyester type antistatic agent.

[0012] The polyether ester type antistatic agent described in this invention refers to a copolymer antistatic agent whose main chain contains both polyether segments and polyester segments. When used in combination with mold fouling inhibitor A, it can reduce the generation of injection mold fouling and has an excellent effect in alleviating or even solving the problem of injection mold fouling in ABS injection molding.

[0013] Preferably, the method for preparing the fouling inhibitor A includes: subjecting 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate to a double bond polymerization reaction under the initiation of an initiator to obtain the fouling inhibitor A.

[0014] This invention utilizes a free radical initiator to initiate a double bond polymerization reaction to obtain the fouling inhibitor A. The preparation method will not be described in detail here; any parameters capable of achieving the double bond polymerization reaction described in this invention can be applied to this invention. Only exemplary examples are provided here: In this invention, the molar ratio of 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate is approximately 1:1. 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol or 2,2,6,6-tetramethyl-4-piperidinyl methacrylate can be in slight excess, or the reaction can be carried out at a molar ratio of 1:1. This invention does not impose further limitations.

[0015] In this invention, the initiator is a free radical initiator, preferably a peroxide initiator and / or an azo initiator. The peroxide initiator includes benzoyl peroxide (BPO), di-tert-butyl peroxide, dicumyl peroxide (DCP), or tert-butyl peroxide, etc., and the azo initiator includes azobisisobutyronitrile (AIBN) or azobisisoheptanenitrile (ABVN), etc., and will not be listed in detail in this invention.

[0016] Preferably, the reaction temperature is 50-60℃, such as 50℃, 52℃, 55℃, 58℃, 60℃ or any of the above values, and the reaction time is preferably 1-2 h, such as 1 h, 1.2 h, 1.5 h, 1.8 h, 2 h or any of the above values.

[0017] Preferably, based on the total mass of the ABS composition, the amount of the composite mold fouling inhibitor added is 0.1-1%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, or any of the above values.

[0018] Preferably, the lubricant comprises any one or a combination of at least two of vinyl bis-stearamide, erucamide, or stearate, with vinyl bis-stearamide being the most preferred.

[0019] Preferably, the melt index (ISO 1133, 220℃ / 10 kg) of the ABS resin is 6-40 g / 10min, for example, 6 g / 10min, 10 g / 10min, 15 g / 10min, 20 g / 10min, 22 g / 10min, 25 g / 10min, 28 g / 10min, 30 g / 10min, 32 g / 10min, 35 g / 10min, 38 g / 10min, 40 g / 10min or any of the above values, preferably 20-40 g / 10min.

[0020] When the melt index of the ABS resin described in this invention is within the above-mentioned range, it can meet the requirements of injection molding. If the melt index is too small, mold fouling is likely to occur.

[0021] Preferably, the antioxidant comprises hindered phenolic antioxidants, and / or a combination of hindered phenolic antioxidants and phosphite antioxidants.

[0022] The present invention does not particularly limit the preparation method of the ABS composition, but only provides exemplary examples: In a second aspect, the present invention provides a method for preparing the ABS composition as described in the first aspect, the method comprising: The components in the formula are mixed, melt-extruded, cooled and granulated to obtain the ABS composition.

[0023] Preferably, the melt extrusion is performed using a screw extruder. Preferably, the temperature of the screw extruder in zones one and two is 160-190°C, for example, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, or any value between these values; the temperature in zones three and five is 190-230°C, for example, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, or any value between these values; the temperature in zones six and ten is 200-220°C, for example, 200°C, 205°C, 210°C, 215°C, 220°C, or any value between these values; and the screw speed is 350-450 rpm, for example, 350 rpm, 360 rpm, 370 rpm, 380 rpm, 390 rpm, 400 rpm, 410 rpm. rpm, 420 rpm, 430 rpm, 440 rpm, 450 rpm or any of the above values.

[0024] Thirdly, the present invention provides the use of the ABS composition as described in the first aspect in the manufacture of electrical device housings.

[0025] Compared with the prior art, the present invention has the following beneficial effects: This invention, by introducing the above-described mold fouling inhibitor A into the ABS composition and cooperating with mold fouling inhibitor B, can greatly alleviate or even solve the problem of injection mold fouling in the ABS injection molding process. Attached Figure Description

[0026] Figure 1 Infrared spectrum of the fouling inhibitor A obtained in Example 1. Detailed Implementation

[0027] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0028] Preparation Example 1 This preparation example provides a method for preparing fouling inhibitor A, as follows: (1) In a three-necked round-neck flask, 26.53 g of 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol and 22.53 g of 2,2,6,6-tetramethyl-4-piperidinyl methacrylate were dissolved in tetrahydrofuran; (2) Nitrogen gas was introduced and stirred. 0.05 g of azobisisobutyronitrile was added dropwise while stirring. The reaction was carried out at 60℃ for 1 h. After the reaction was completed, the solid was collected by filtration, washed, and dried at 40℃ to obtain the scale inhibitor A with an average molecular weight of 2740 g / mol.

[0029] Figure 1 The infrared spectrum of the fouling inhibitor A obtained in this preparation example is shown in the figure. As can be seen from the figure, the molecular structure of the fouling inhibitor A provided by the present invention simultaneously contains the structural units of monomer 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol and monomer 2,2,6,6-tetramethyl-4-piperidinyl ester.

[0030] Preparation Example 2 This preparation example provides a method for preparing a fouling inhibitor A.

[0031] (1) In a three-necked flask, 26.53 g of 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol and 22.53 g of 2,2,6,6-tetramethyl-4-piperidinyl methacrylate were dissolved in... N,N -Dimethylformamide; (2) Nitrogen gas was introduced and stirred. 0.1 g of benzoyl peroxide was added dropwise while stirring. The reaction was carried out at 50°C for 2 h. After the reaction was completed, the solid was collected by filtration, washed, and dried at 40°C to obtain the scale inhibitor A with an average molecular weight of 2192 g / mol.

[0032] Unless otherwise specified, the raw materials involved in the following specific embodiments of the present invention are all conventional materials in the art, and can be purchased from commercially available products. Some raw material information is as follows: ABS resin 1: melt index (ISO 1133, 220℃ / 10 kg) 21 g / 10min, purchased from Liaoning Kingfa Science & Technology Co., Ltd., KF-730; ABS resin 2: melt index (ISO 1133, 220℃ / 10 kg) 35 g / 10min, purchased from Liaoning Kingfa Science & Technology Co., Ltd., KF-740; ABS resin 3: melt index (ISO 1133, 220℃ / 10 kg) 8 g / 10min, purchased from Liaoning Kingfa Science & Technology Co., Ltd., model GAR-322; Scuff inhibitor A-1: ​​Provided in Preparation Example 1; Fouling Inhibitor A-2: Preparation Example 2 provides: Scrub inhibitor A-3: 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol, purchased from Zhengzhou Alpha Chemical Co., Ltd. Scrub inhibitor A-4: 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, purchased from Zhengzhou Alpha Chemical Co., Ltd. Smudge inhibitor B-1: a high molecular weight antistatic agent, purchased from Sanyo Chemicals, model PELESTAT-6500; Smudge inhibitor B-2: a high molecular weight antistatic agent, purchased from Sanyo Chemicals, model PELESTAT-6200; Antioxidant 1: Antioxidant 1010, purchased from Rianon; Antioxidant 2: A combination of antioxidant 1076 (purchased from BASF) and antioxidant 168 (purchased from Rheinland) in a mass ratio of 1:1; Lubricant 1: Vinyl bis-stearamide, purchased from Nantong Zhonghe; Lubricant 2: Erucamide, purchased from GYC GROUP.

[0033] Examples 1-8 and Comparative Examples 1-5 This embodiment provides an ABS composition and its preparation method, the specific components and weight parts of which are shown in Table 1.

[0034] Table 1 Table 2 The preparation method is as follows: (1) Mix the components of the formula in a mixer for 4 min to obtain a mixture; (2) The mixture is melt-extruded and cooled and granulated using a screw extruder to obtain an ABS composition.

[0035] The temperature of the screw extruder is 180℃ in zones one and two, 220℃ in zones three and five, and 210℃ in zones six and ten. The screw speed is 400 rpm.

[0036] Performance testing The performance of the samples provided in the examples and comparative examples was tested using the following methods: (1) Injection mold fouling test: Inject ABS plastic particles into a mold fouling mold (refer to CN111283968A for mold fouling molds), continuously inject 200 molds using the same process, collect the generated mold fouling and weigh it.

[0037] The results are shown in Table 3: Table 3 As can be seen from the examples and performance tests, the ABS composition provided by the present invention produces extremely low amounts of injection mold fouling during injection molding.

[0038] As can be seen from the comparison of Examples 1-3, in the present invention, the mass ratio of mold fouling inhibitor A to mold fouling inhibitor B is ≥1, which can further reduce the amount of injection mold fouling.

[0039] As can be seen from the comparison between Examples 1 and Examples 5-6, when the melt index of the ABS resin of the present invention is in the range of 20-40 g / 10min, it can not only meet the injection molding requirements, but also further reduce the amount of mold fouling.

[0040] As can be seen from the comparison of Example 1 and Comparative Examples 1-4, only by introducing the mold fouling inhibitor A and mold fouling inhibitor B as defined in this invention in combination can the purpose of reducing the amount of injection mold fouling be achieved.

[0041] As can be seen from the comparison between Example 1 and Comparative Example 5, when the amount of the composite mold fouling inhibitor described in this invention is within the range defined by this invention, it can reduce the amount of injection mold fouling.

[0042] The applicant declares that the technical solution of this invention is illustrated through the above embodiments, but this invention is not limited to the above process steps, that is, it does not mean that this invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of the raw materials used in this invention, additions of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. An ABS composition, characterized in that, The ABS composition comprises, by weight, the following: 90-95 parts ABS resin, 0.1-1 parts composite mold fouling inhibitor, 1-5 parts lubricant, and 0.2-1 parts antioxidant, wherein the composite mold fouling inhibitor comprises mold fouling inhibitor A and mold fouling inhibitor B, wherein: The molecular structure of the fouling inhibitor A includes structural segments shown in Formula I and / or Formula II, and the fouling inhibitor B is a polymeric antistatic agent. 、 ； In this context, n, x, and y are each independently selected from integers from 1 to 5.

2. The ABS composition according to claim 1, characterized in that, The mass ratio of the scale inhibitor A to the scale inhibitor B is ≥0.5, preferably ≥1.

3. The ABS composition according to claim 1, characterized in that, The molecular weight of the fouling inhibitor A is 1000-3000 g / mol; And / or, the polymeric antistatic agent includes a polyether ester type antistatic agent.

4. The ABS composition according to claim 1, characterized in that, The preparation method of the fouling inhibitor A includes: carrying out a double bond polymerization reaction of 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate under the initiation of an initiator to obtain the fouling inhibitor A; Preferably, the reaction temperature is 50-60℃, and the reaction time is preferably 1-2 h.

5. The ABS composition according to claim 1, characterized in that, The amount of composite mold fouling inhibitor added is 0.1-1% based on the total mass of the ABS composition (100%).

6. The ABS composition according to claim 1, characterized in that, The lubricant includes any one or a combination of at least two of vinyl bis-stearamide, erucamide, or stearate, preferably vinyl bis-stearamide.

7. The ABS composition according to claim 1, characterized in that, The melt flow index of the ABS resin is 6-40 g / 10min, preferably 20-40 g / 10min.

8. The ABS composition according to claim 1, characterized in that, The antioxidants include hindered phenolic antioxidants, and / or combinations of hindered phenolic antioxidants and phosphite antioxidants.

9. A method for preparing an ABS composition according to any one of claims 1-8, characterized in that, The preparation method includes: The components in the formula are mixed, melt-extruded, cooled and granulated to obtain the ABS composition.

10. The use of an ABS composition as described in any one of claims 1-8 in the manufacture of electrical device housings.

Images