Abs / pok composite material and preparation method and application thereof

Abstract

The application discloses an ABS / POK composite material and a preparation method and application thereof, and relates to the technical field of modified plastics. The application provides an ABS / POK composite material, which comprises the following components in parts by weight: ABS resin 40-65 parts, POK resin 15-30 parts, chlorinated polyethylene 15-30 parts and maleic anhydride-styrene random copolymer 2-5 parts; the chlorinated polyethylene has a Mooney viscosity of 65-80 under the test conditions of ML (1+4) and 125 DEG C according to the GB / T 1232.1-2000 standard. The application provides an ABS / POK composite material which is resistant to chemicals and has good hand feeling.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of modified plastics, in particular to an ABS / POK composite material and a preparation method and application thereof. BACKGROUND

[0002] ABS resin is a terpolymer composed of styrene, butadiene and acrylonitrile, which has excellent processing performance, low temperature resistance, electrical insulation, high gloss and excellent electroplating performance, and also has good creep resistance, high dimensional stability and small molding shrinkage, and is widely used in plastic products in the fields of household appliances, automobiles, electronics and electrical appliances. However, ABS material has poor resistance to oil and organic solvents, and is easy to swell and break in non-polar oil or chemical solvents. The unsaturated polybutadiene double bond in the structure is easy to age and discolor, which affects the appearance of the product. Such performance defects greatly limit the application and promotion of ABS material in some product fields. Moreover, ABS material has relatively high hardness, and for some handle parts, it is required to have a soft feel, and ABS material cannot meet the requirements. It is usually necessary to spray a hand feel paint or perform double-color injection molding for TPE encapsulation to achieve a good hand feel. POK resin is a fatty polyketone resin obtained by copolymerization of carbon monoxide and olefins (generally ethylene and propylene), which has good chemical resistance. These two characteristics can make up for the shortcomings of ABS material. However, ABS and POK are directly blended, and the obtained material has poor compatibility, poor product performance and appearance, and is difficult to be applied in practice.

[0003] Therefore, an ABS / POK composite material with good chemical resistance and good hand feel has broad application prospects. SUMMARY

[0004] Based on this, the purpose of the present application is to overcome the shortcomings of the prior art and provide an ABS / POK composite material with good chemical resistance and good hand feel and a preparation method and application thereof.

[0005] To achieve the above purpose, the technical solution adopted by the present application is as follows: an ABS / POK composite material, comprising the following components by weight: ABS resin 40-65 parts, POK resin 15-30 parts, chlorinated polyethylene (CPE) 15-30 parts, and maleic anhydride-styrene random copolymer 2-5 parts; the chlorinated polyethylene has a Mooney viscosity of 65-80 under the test conditions of ML (1+4) and 125 DEG C according to the GB / T 1232.1-2000 standard.

[0006] The present application introduces aliphatic polyketone (POK) resin into ABS resin, by adding maleic anhydride-styrene random copolymer, the anhydride reacts with the carbonyl group of POK, the crystallinity of POK is reduced, and the phase interface of amorphous ABS and semi-crystalline POK is weakened. At the same time, the addition of chlorinated polyethylene with a specific Mooney viscosity, the PE segment in chlorinated polyethylene is compatible with the olefin segment in POK, further improving the compatibility of ABS and POK. At the same time, the soft elasticity of chlorinated polyethylene makes the ABS alloy material show soft and good hand feeling. If the Mooney viscosity of chlorinated polyethylene is too low, the shear received during modification is small, and it is not easy to disperse uniformly, and the skin feeling is poor; if the Mooney viscosity of chlorinated polyethylene is too high, the material flowability is poor, it is difficult to injection molding, and the skin feeling is rough.

[0007] Preferably, the weight percentage of the ABS resin in the ABS / POK composite material is not less than 40%.

[0008] Preferably, the ABS / POK composite material comprises the following components by weight: ABS resin 50-60 parts, POK resin 20-25 parts, chlorinated polyethylene 20-25 parts, maleic anhydride-styrene random copolymer 3-4 parts.

[0009] Optionally, the weight of the ABS resin is one of 40 parts, 45 parts, 50 parts, 55 parts, 58 parts, 60 parts, 61 parts, 63 parts, 65 parts, or a range value of any two thereof; the weight of the POK resin is one of 15 parts, 18 parts, 20 parts, 21 parts, 23 parts, 25 parts, 28 parts, 30 parts, or a range value of any two thereof; the weight of the chlorinated polyethylene is one of 15 parts, 18 parts, 20 parts, 21 parts, 23 parts, 25 parts, 28 parts, 30 parts, or a range value of any two thereof; the weight of the maleic anhydride-styrene random copolymer is one of 2 parts, 3 parts, 4 parts, 5 parts, or a range value of any two thereof.

[0010] Optionally, the Mooney viscosity of the chlorinated polyethylene is one of 65, 68, 70, 72, 75, 80, or a range value of any two thereof, according to the GB / T 1232.1-2000 standard under the test conditions of ML(1+4), 125℃.

[0011] Preferably, the rubber content of the ABS resin is ≥18wt%; further preferably, the rubber content of the ABS resin is 25-35wt%. The determination of the rubber content in the present application adopts high-speed centrifugal separation method, and the specific steps are as follows:

[0012] After drying the ABS, weigh 1.000g, and weigh the reagent bottle m1;

[0013] (1) Put ABS into the reagent bottle, add about 25ml of acetone, and ultrasonic oscillation for 3h;

[0014] (2) Put into high-speed centrifuge and centrifuge for 30min, centrifugal speed >15000r / min;

[0015] (3) Immediately remove the acetone after centrifugal separation with a syringe, and pay attention not to take out the solid;

[0016] (4) Add 25ml of acetone again, and ultrasonic oscillation for 3h;

[0017] (5) Centrifuge again, and remove the acetone solution after centrifugation;

[0018] (6) Put the reagent bottle into a vacuum oven at 80℃ and dry for 10h;

[0019] (7) Cool to room temperature, and weigh m2;

[0020] (8) Rubber content = (m2-m1) / 1*100wt%.

[0021] Preferably, the POK resin has a melt flow rate of ≥60g / 10min according to ISO 1133-1-2011 at 240℃, 2.16kg. Further preferably, the POK resin has a melt flow rate of 60-200g / 10min according to ISO 1133-1-2011 at 240℃, 2.16kg

[0022] Preferably, the mass percentage of maleic anhydride in the maleic anhydride-styrene random copolymer is 15-27%. Further preferably, the mass percentage of maleic anhydride in the maleic anhydride-styrene random copolymer is 15-23%.

[0023] Optionally, the rubber content of the ABS resin is one or a range value of any two of 18wt%, 20wt%, 23wt%, 25wt%, 27wt%, 33wt%, 33wt%, 35wt%.

[0024] Optionally, the melt flow rate of the POK resin is one or a range value of any two of 60g / 10min, 68g / 10min, 80g / 10min, 100g / 10min, 120g / 10min, 150g / 10min, 200g / 10min.

[0025] Optionally, the mass percentage of maleic anhydride in the maleic anhydride-styrene random copolymer is one or a range value of any two of 15%, 18%, 20%, 23%, 25%, 27%.

[0026] Preferably, the mass percentage of maleic anhydride in the present application can be determined by infrared spectroscopy: the infrared spectrum characteristic absorption peak of the sample with fixed thickness is obtained by Fourier infrared spectrometer, and the mass percentage of maleic anhydride can be calculated by comparing the ratio of the absorbance of carbonyl and methylene.

[0027] Preferably, the ABS / POK composite further comprises 0.5-2 parts of stabilizer, 0.5-2 parts of antioxidant and 0.5-2 parts of lubricant.

[0028] Optionally, the stabilizer is at least one of calcium-zinc stabilizer, barium-zinc stabilizer and organic tin stabilizer.

[0029] Optionally, the antioxidant is at least one of hindered phenolic antioxidant and phosphite antioxidant, such as antioxidant 168 (tris [2.4-di-tert-butylphenyl] phosphite), antioxidant 1010 (tetra [beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester) and the like.

[0030] Optionally, the lubricant is at least one of stearate, stearate ester and ethylene bis-stearamide, such as pentaerythritol stearate, zinc stearate and the like.

[0031] In addition, the present application provides a preparation method of the ABS / POK composite, comprising the following steps: mixing the components in proportion, melt extruding, granulating to obtain the ABS / POK composite.

[0032] Preferably, the preparation method of the ABS / POK composite, the extrusion temperature is 80-230℃, the screw rotation speed is 300-400 rpm, and the length-diameter ratio of the extruder is 48:1.

[0033] Further, the present application provides the application of the ABS / POK composite in the field of electronic appliances or household appliances.

[0034] Preferably, the present application provides the application of the ABS / POK composite in game handle, dust collector handle and refrigerator handle.

[0035] Compared with the prior art, the present application has the following beneficial effects: the present application introduces aliphatic polyketone (POK) resin into ABS resin, by adding maleic anhydride-styrene random copolymer, the anhydride reacts with the carbonyl group of POK, the crystallinity of POK is reduced, and the phase interface of amorphous ABS and semi-crystalline POK is weakened. At the same time, by adding chlorinated polyethylene with specific Mooney viscosity, the PE segment in chlorinated polyethylene is compatible with the olefin segment in POK, which further improves the compatibility of ABS and POK. At the same time, the softness and elasticity of chlorinated polyethylene make the ABS / POK composite have soft and good hand feeling and chemical resistance. DETAILED DESCRIPTION

[0036] For better illustrating the purpose, technical scheme and advantages of the present application, the present application will be further explained in combination with specific examples. The purpose is to understand the content of the present application in detail, but not to limit the present application. All other examples obtained by the ordinary skilled in the art without making creative efforts are within the protection scope of the present application. The experimental reagents and instruments designed in the examples and comparative examples are common reagents and instruments unless specially stated, and can be obtained from commercial channels. In the examples and comparative examples, the experimental methods used are conventional methods unless specially stated, and the raw materials used in parallel experiments are the same batch of raw materials unless specially stated.

[0037] Now the raw materials used in the examples and comparative examples will be explained as follows, but are not limited to these materials:

[0038] ABS resin-1: rubber content is 25wt%, brand ABS DG-417, manufacturer Tianjin Dagu Chemical Industry;

[0039] ABS resin-2: rubber content is 30wt%, brand ABS 780A, manufacturer South Korea Kumho;

[0040] ABS resin-3: rubber content is 35wt%, brand ABS D-120A, manufacturer China Taiwan Guojiao;

[0041] ABS resin-4: rubber content is 20wt%, brand ABS PA-757, manufacturer China Taiwan Qimei;

[0042] ABS resin-5: rubber content is 39wt%, brand ABS DG-MG29, manufacturer Tianjin Dagu Chemical Industry;

[0043] POK resin-1: melt flow rate is 60g / 10min (240℃ / 2.16kg), brand POKETONE M330F, manufacturer Hyosung Chemical Corporation;

[0044] POK resin-2: melt flow rate is 68g / 10min (240℃ / 2.16kg), brand POKETONE M33-R3A000, manufacturer Hyosung Chemical Corporation;

[0045] POK resin-3: melt flow rate is 200g / 10min (240℃ / 2.16kg), brand POKETONE M130F, manufacturer Hyosung Chemical Corporation;

[0046] Chlorinated polyethylene-1: Mooney viscosity 55 (ML (1+4) / 125℃), Weipren 6335, manufacturer Weifang Yaxing Chemical Co., Ltd.;

[0047] Chlorinated polyethylene-2: Mooney viscosity 65 (ML (1+4) / 125℃), Weipren 6135, manufacturer Weifang Yaxing Chemical Co., Ltd.;

[0048] Chlorinated polyethylene-3: Mooney viscosity 80 (ML (1+4) / 125℃), Weipren 6235, manufacturer Weifang Yaxing Chemical Co., Ltd.;

[0049] Chlorinated polyethylene-4: Mooney viscosity 100 (ML (1+4) / 125℃), Weipren 140B, manufacturer Weifang Yaxing Chemical Co., Ltd.;

[0050] Maleic anhydride-styrene random copolymer-1: mass percentage of maleic anhydride 18%, brand SMA700, manufacturer Jiaxing Huawen;

[0051] Maleic anhydride-styrene random copolymer-2: mass percentage of maleic anhydride 23%, brand SZ23110, manufacturer Polyscope Company, Netherlands;

[0052] Maleic anhydride-styrene random copolymer-3: mass percentage of maleic anhydride 25%, brand SMA-725, manufacturer Jiaxing Huawen;

[0053] Stabilizer: calcium-zinc stabilizer RUP-108, Aidi Fine Chemical Co., Ltd.;

[0054] Lubricant: zinc stearate, commercially available;

[0055] The antioxidant is a commercially available hindered phenolic antioxidant 1010 and a commercially available phosphite antioxidant 168 in a compound with a mass ratio of 1:1.

[0056] Examples and comparative examples

[0057] The components and weight parts of the ABS / POK composite material in the examples and comparative examples of the present application are shown in Tables 1-2, and the preparation method of the ABS / POK composite material comprises the following steps: mixing the components in proportion, melt extruding, granulating to obtain the ABS / POK composite material. The conditions of the melt extrusion are: zone 1 80℃, zone 2 160℃, zone 3 180℃, zone 4 230℃, zone 5 230℃, zone 6 230℃, zone 7 220℃, zone 8 220℃, zone 9 220℃, zone 10 220℃, zone 11 220℃, and the head 230℃, the screw rotation speed is 350 rpm, and the length-diameter ratio of the twin-screw extruder is 48:1.

[0058] Performance test

[0059] (1) Rockwell hardness: According to GB / T 230.1-2004 "Rockwell hardness test method", the test sample is a 6mm thick disc with a diameter of 6mm. The Rockwell hardness is controlled between 70-80.

[0060] (2) Dynamic friction coefficient: According to ASTM D1894-2014 "Standard test method for static and kinetic coefficient of friction of plastic film and sheet", the dynamic friction coefficient should be controlled between 0.15-0.25. If it is too high, it will produce obvious jerk. If it is too low, the smoothness is too good to cover the softness, so only the smoothness is shown.

[0061] (3) Skin feel evaluation: The skin feel of the sample is mainly affected by the dynamic friction coefficient and the Rockwell hardness. To achieve a suitable skin feel, the dynamic friction coefficient should be controlled between 0.15-0.25, and the Rockwell hardness should be between 70-80. In addition, a touch panel is used for skin feel evaluation. Specifically, 5 trained and screened people are used as the judges of the touch panel, to evaluate the feeling after touching the sample, mainly by sliding the sample surface with moderate force. Level 1 represents a skin-like smooth and soft touch, level 5 represents a hard and rough touch, levels 2-4 represent different levels of changes from smooth and soft to hard and rough, and levels 1-5 correspond to best, better, moderate, worse and very bad skin feel, respectively. The average value of the evaluation results of the 5 people is taken as the evaluation result. The skin feel of the present application should at least reach better or above, i.e. level 2 or below.

[0062] (4) Chemical resistance test: According to BS EN ISO 22088-3-2006 standard, standard tensile sample is loaded into a clamp with a strain of 1.5%, and the surface cracking of the tensile sample is observed after coating with glacial acetic acid. The chemical resistance evaluation levels are as follows: excellent, no change after 48 hours, marked as●; good, with small silver crack defects after 48 hours, marked as○; qualified, with cracks within 48 hours, marked as△; poor, with cracking damage within 48 hours, marked as X.

[0063] The test results are shown in Tables 1-2.

[0064] Table 1

[0065]

[0066]

[0067]

[0068] Table 2

[0069] Parts by weight Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 ABS Resin-1 50 50 50 50 POK Resin-1 20 20 20 20 Chlorinated polyethylene-2 0 0 20 0 Chlorinated polyethylene-1 20 0 0 0 Chlorinated polyethylene-4 0 20 0 0 Maleic anhydride-styrene random copolymer-1 3 3 0 3 SEBS 0 0 0 20 Maleic anhydride grafted SEBS 0 0 3 0 Calcium-zinc stabilizer 1 1 1 1 Lubricant 1 1 1 1 Antioxidant 1 1 1 1 Rockwell hardness 85 64 76 77 Dynamic friction coefficient 0.29 0.28 0.25 0.31 Skin feel evaluation 5 5 4 5 Chemical resistance ○ ● △ X

[0070] The ABS / POK composite material prepared by the embodiment has a Rockwell hardness of 70-80, a dynamic friction coefficient of 0.15-0.25, and a skin feeling evaluation grade of 2 or less, and has good or better skin feeling.

[0071] As can be seen from the comparison of Examples 1-5, the rubber content of the ABS resin greatly affects the Rockwell hardness and skin feeling of the ABS / POK composite material. When the rubber content of the ABS resin is 25-35 wt%, the hardness is more moderate, and the skin feeling evaluation is better.

[0072] As can be seen from the comparison of Example 1, Example 8, and Comparative Examples 1-2, the Mooney viscosity of the chlorinated polyethylene greatly affects the Rockwell hardness, dynamic friction coefficient, and skin feeling. When the Mooney viscosity of the chlorinated polyethylene is 65-80, the Rockwell hardness and dynamic friction coefficient of the ABS / POK composite material are suitable, the skin feeling evaluation grade is 2 or less, and the skin feeling is good or better. If the Mooney viscosity of the chlorinated polyethylene is too low, the chlorinated polyethylene is less sheared during modification and is not easily uniformly dispersed, and the skin feeling is poor. If the Mooney viscosity of the chlorinated polyethylene is too high, the material has poor flowability and is difficult to injection mold, and the skin feeling is rough.

[0073] As can be seen from the comparison of Example 1, Examples 11-13, and Comparative Examples 3-4, when the ABS / POK composite material contains 50-60 parts of ABS resin, 20-25 parts of POK resin, 20-25 parts of chlorinated polyethylene, and 3-4 parts of maleic anhydride-styrene random copolymer, the hardness and dynamic friction coefficient are suitable, the skin feeling evaluation grade is 2 or less, the skin feeling is good or better, and the chemical resistance is better.

[0074] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. An ABS / POK composite material, characterized in that, The product comprises the following components in parts by weight: 40-65 parts ABS resin, 15-30 parts POK resin, 15-30 parts chlorinated polyethylene, and 2-5 parts maleic anhydride-styrene random copolymer; wherein the chlorinated polyethylene has a Mooney viscosity of 65-80 under the test conditions of ML (1+4) and 125℃ according to GB / T 1232.1-2000 standard.

2. The ABS / POK composite material as described in claim 1, characterized in that, It includes the following components in parts by weight: 50-60 parts ABS resin, 20-25 parts POK resin, 20-25 parts chlorinated polyethylene, and 3-4 parts maleic anhydride-styrene random copolymer.

3. The ABS / POK composite material as described in claim 1, characterized in that, The rubber content of the ABS resin is ≥18wt%.

4. The ABS / POK composite material as described in claim 3, characterized in that, The rubber content of the ABS resin is 25-35 wt%.

5. The ABS / POK composite material as described in claim 1, characterized in that, The POK resin, according to ISO 1133-1-2011, has a melt flow rate ≥60 g / 10 min at 240°C and 2.16 kg.

6. The ABS / POK composite material as described in claim 1, characterized in that, The mass percentage of maleic anhydride in the maleic anhydride-styrene random copolymer is 15-27%.

7. The ABS / POK composite material as described in claim 1, characterized in that, The ABS / POK composite material also includes 0.5-2 parts stabilizer, 0.5-2 parts antioxidant and 0.5-2 parts lubricant.

8. A method for preparing the ABS / POK composite material as described in any one of claims 1-6, characterized in that, Includes the following steps: The components are mixed in proportion, melt extruded, and granulated to obtain the ABS / POK composite material.

9. The application of the ABS / POK composite material as described in any one of claims 1-6 in the field of electronic appliances or household appliances.

10. The application of an ABS / POK composite material as described in any one of claims 1-6 in game controllers, vacuum cleaner handles, and refrigerator handles.

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