Composite material as well as preparation method and application thereof

Abstract

The invention relates to a composite material as well as a preparation method and application thereof, and belongs to the technical field of compositions of high-molecular compounds. The composite material provided by the invention comprises the following components in parts by weight: 10-70 parts of MS resin, 30-90 parts of SBC resin and 5-20 parts of AS resin, the mass content of methyl methacrylate in the MS resin is 20%-30%. The composite material has good bending resistance and can maintain relatively high transparency after being bent.

Description

Technical Field

[0001] The present invention relates to the technical field of compositions of polymer compounds, and particularly to a composite material, a preparation method thereof, and an application thereof. Background Art

[0002] A wire protection sleeve is a protective product used to protect wires and cables from physical damage, chemical corrosion, and environmental factors, and is widely used in various electrical installation and wiring projects to ensure the safety of wires and extend the service life of wires. According to different functions, common wire protection sleeves are mainly divided into sleeves with good chemical resistance and wear resistance, sleeves with good elasticity and flexibility, sleeves that can provide additional mechanical protection, and transparent protection sleeves, etc. Among them, the transparent protection sleeve can make the wire arrangement clearly visible, timely discover potential safety hazards, reduce safety hazard problems caused by opaque sleeves, and avoid safety accidents such as wire failures and electrical fires after long-term use of wires. The transparent protection sleeve is mainly made of transparent plastic resin. However, common transparent plastic resins such as PC, PMMA, GPPS, MABS, etc., although having good transparency (light transmittance close to 90%), have poor resistance to repeated bending, cannot be repeatedly bent and maintain good transparency after bending, and are difficult to apply to the actual working conditions of electrical cabinet wire arrangement protection sleeves. Summary of the Invention

[0003] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a composite material, a preparation method thereof, and an application thereof.

[0004] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0005] In a first aspect, the present invention provides a composite material, which comprises the following components by weight: 10 - 70 parts of MS resin, 30 - 90 parts of SBC resin, and 5 - 20 parts of AS resin; the mass content of methyl methacrylate in the MS resin is 20% - 30%.

[0006] The present invention combines a specific MS resin with SBC resin and AS resin. All three contain styrene copolymer units and have good compatibility with each other. After blending, not only can a high transparency be maintained, but it is also beneficial to increase the entanglement degree between molecular chains; moreover, the butadiene copolymer unit in the SBC resin is used to promote the improvement of the overall flexibility of the composite material, thereby improving the resistance to repeated bending; at the same time, AS resin is matched to make the composite material have appropriate rigidity. The three act synergistically to make the composite material still have high transparency and appropriate bending strength after repeated bending. Among them, the mass content of MS resin in the composite material ≥ 8%.

[0007] It should be noted that the above-mentioned MS resin refers to methyl methacrylate-styrene copolymer, the SBC resin refers to styrene-butadiene block copolymer, and the AS resin refers to styrene-acrylonitrile copolymer. The mass content of methyl methacrylate in the MS resin can be determined by first measuring the mass content of oxygen element by elemental analysis method and then calculating the mass content of methyl methacrylate.

[0008] Optionally, the weight parts of the MS resin in the above composite material can specifically be 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts; the weight parts of the SBC resin can specifically be 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts; the weight parts of the AS resin can specifically be 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts.

[0009] As a preferred embodiment of the composite material of the present invention, in the components of the composite material, the MS resin is 40-60 parts by weight, the SBC resin is 40-60 parts by weight, and the AS resin is 10-15 parts by weight.

[0010] As a preferred embodiment of the composite material of the present invention, the MS resin adopts the ISO 1133-2011 standard, and the melt mass flow rate at 220°C and 10 kg is 20-30 g / 10 min. Optionally, the melt mass flow rate of the MS resin can specifically be any one or the range value of any two of 20 g / 10 min, 22 g / 10 min, 24 g / 10 min, 26 g / 10 min, 28 g / 10 min, 30 g / 10 min.

[0011] As a preferred embodiment of the composite material of the present invention, the SBC resin adopts the ISO 1133-2011 standard, and the melt mass flow rate at 200°C and 5 kg is ≤10 g / 10 min, preferably 6-9 g / 10 min, and can specifically be any one or the range value of any two of 10 g / 10 min, 9 g / 10 min, 8 g / 10 min, 7 g / 10 min, 6 g / 10 min, 5 g / 10 min. It is found that using the SBC resin with this melt mass flow rate range as the toughening agent can not only achieve a good toughening effect on the MS resin, but also keep the composite material with high transparency.

[0012] As a preferred embodiment of the composite material of the present invention, the mass content of butadiene in the SBC resin is 25% to 30%. Optionally, the mass content of butadiene in the SBC resin can specifically be any one or the range value of any two of 25%, 26%, 27%, 28%, 29%, 30%. It has been found that the SBC resin with the above butadiene content can not only play a certain toughening role but also achieve a good transparency effect. The mass content of butadiene in the SBC resin can be measured by the dissolution precipitation method.

[0013] As a preferred embodiment of the composite material of the present invention, the mass content of acrylonitrile in the AS resin is 20% to 30%. Optionally, the mass content of acrylonitrile in the AS resin can specifically be any one or the range value of any two of 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%. The mass content of acrylonitrile in the AS resin can be measured by the infrared spectroscopy method.

[0014] As a preferred embodiment of the composite material of the present invention, the refractive index of the MS resin is 1.56 to 1.57; and / or, the refractive index of the SBC resin is 1.55 to 1.57. It has been found that the composite material formed by the MS resin or SBC resin with the above refractive index and the AS resin can maintain better transparency, and at the same time is also beneficial to the AS resin to better play the role of increasing rigidity, so that the composite material has appropriate stiffness to better meet the application scenarios that require support.

[0015] As a preferred embodiment of the composite material of the present invention, the components of the composite material further include 0.1 to 1 part by weight of a lubricant and 0.1 to 1 part by weight of an antioxidant. Optionally, the lubricant can specifically be at least one of ethylene bisstearamide, erucamide, and pentaerythritol stearate; the antioxidant can specifically be at least one of pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(2,4-di-tert-butyl)phenyl phosphite, distearyl thiodipropionate, and dioctadecyl thiodipropionate.

[0016] In the second aspect, the present invention provides a preparation method of the above composite material, including the following steps: mixing the components evenly and then performing melt extrusion to obtain the composite material.

[0017] Optionally, a twin-screw extruder can be used for melt extrusion in the above preparation method. The temperature of the melt extrusion is 190 to 210 °C, and the screw speed of the twin-screw extruder is 300 to 600 revolutions per minute.

[0018] In a third aspect, the present invention provides the application of the above composite material in the preparation of wire protective sleeves, flexible display protective layers, flexible packaging films, automotive transparent components, transparent components of wearable devices, charging or data cable sheaths, and battery encapsulation films.

[0019] In a fourth aspect, the present invention provides an electrical cabinet wire arrangement protective sleeve, which is mainly made of the above composite material.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] The present invention combines a specific MS resin with an SBC resin and an AS resin. All three contain styrene copolymer units and have good compatibility with each other. After blending, not only can a high transparency be maintained, but it is also beneficial to increase the entanglement degree between molecular chains. Moreover, the butadiene copolymer unit in the SBC resin is used to promote the improvement of the overall flexibility of the composite material, thereby enhancing the resistance to repeated bending. At the same time, the AS resin is used to make the composite material have appropriate rigidity. The three act synergistically to enable the composite material to still have high transparency and appropriate bending strength after repeated bending. Specific Embodiments

[0022] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0023] Other materials, reagents, etc. used in the examples and comparative examples can be obtained from commercial sources unless otherwise specified.

[0024] 1. Raw Materials and Reagents

[0025] MS resin 1, with a mass content of methyl methacrylate of 20%, a melt mass flow rate of 25 g / 10 min, manufactured by Nippon Steel&Sumikin Chemical Co., Ltd., and the grade is MS-200NT;

[0026] MS resin 2, with a mass content of methyl methacrylate of 30%, a melt mass flow rate of 27 g / 10 min, manufactured by Nippon Steel&Sumikin Chemical Co., Ltd., and the grade is MS-300NT;

[0027] MS resin 3, with a mass content of methyl methacrylate of 50%, a melt mass flow rate of 30 g / 10 min, manufactured by Nippon Steel&Sumikin Chemical Co., Ltd., and the grade is MS-500NT;

[0028] SBC resin 1, with a mass content of butadiene of 30%, a melt mass flow rate of 7 g / 10 min, manufactured by Denki Kagaku Kogyo Co., Ltd. of Japan, and the grade is DENKA NSBC220;

[0029] SBC resin 2, with a mass content of butadiene of 30%, a melt mass flow rate of 8 g / 10 min, manufactured by Guangdong Zhonggao New Technology Co., Ltd., and the grade is SBS 8036;

[0030] AS resin 1, with a mass content of acrylonitrile of 25%, a melt mass flow rate of 35 g / 10 min, manufactured by Liaoning Jinfa, and the grade is SAN KFA-130;

[0031] AS resin 2, with a mass content of acrylonitrile of 30%, a melt mass flow rate of 10 g / 10 min, manufactured by Liaoning Jinfa, and the grade is SAN KFA-180;

[0032] The antioxidant is compounded by RIANOX 1010 and RIANOX 168 in a mass ratio of 1:2, and the manufacturer is Tianjin Rianlon;

[0033] Lubricant, manufactured by Guangzhou Runfeng, and the grade is EBS B50.

[0034] 2. Preparation method of the composite material of the present invention

[0035] According to the formula, each component is mixed evenly and then added into a twin-screw extruder for melt extrusion to obtain the composite material; among them, the temperature of the melt extrusion is 190-210 °C, and the screw speed of the twin-screw extruder is 300-600 revolutions per minute.

[0036] Table 1 Weight parts of each component of the composite material in Examples 1-9

[0037]

[0038]

[0039] Table 2 Weight parts of each component of the composite material in Comparative Examples 1-5

[0040] Comparative example 1 2 3 4 5 MS resin 1 / 80 100 / 50 MS resin 3 50 / / / / SBC resin 1 50 20 / 100 50 AS resin 1 12 12 12 12 / Antioxidant 0.3 0.3 0.3 0.3 0.3 Lubricant 0.5 0.5 0.5 0.5 0.5

[0041] 3. Performance test

[0042] 1) Light transmittance: Tested according to the ISO 14782-2021 standard, and the thickness of the specimen is 2 mm.

[0043] 2) Flexural strength: Tested according to the ISO 178-2019 standard.

[0044] 3) Light transmittance retention rate: The composite materials in each example and comparative example were extruded and cut into sheets with a size of 50 mm × 50 mm × 0.5 mm, and the light transmittance m of the area to be bent was measured. Then the sheet was bent to an angle of 45° and held for 10 seconds, and then the external force was removed. This operation was repeated 200 times, and then the light transmittance n of the bent area was measured. The light transmittance retention rate (%) = n / m × 100%.

[0045] Table 3 Performance of the composite materials in each example and comparative example

[0046]

[0047]

[0048] According to the data in Table 3, it can be seen that the flexural strength of the composite materials in Examples 1-9 is ≥ 40 MPa, the light transmittance of the 2-mm-thick sheet reaches ≥ 87%, and the light transmittance retention rate of the 0.5-mm-thick sheet after 200 bending tests reaches more than 84%. This indicates that the composite materials of the present invention have good mechanical properties and bending resistance, and can maintain high transparency after bending. At the same time, it can be seen from Comparative Example 1 that when the mass content of methyl methacrylate in the MS resin is too high, the transparency of the composite material itself and the transparency after bending will be significantly reduced. In addition, it can be found from Comparative Examples 2-5 that when the content of MS resin in the composite material is too high, not only the transparency of the composite material will be reduced, but also the bending resistance of the composite material will be significantly reduced; when any two of the MS resin, SBC resin, and AS resin are combined, the obtained composite material is difficult to have both good mechanical properties and excellent bending resistance, indicating that only when the MS resin, SBC resin, and AS resin are combined can the mechanical properties and bending resistance of the composite material be effectively improved.

[0049] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention and do not limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A composite material, characterized in that, By weight parts, it comprises the following components: 10 - 70 parts of MS resin, 30 - 90 parts of SBC resin, 5 - 20 parts of AS resin; the mass content of methyl methacrylate in the MS resin is 20% - 30%.

2. The composite material according to claim 1, characterized in that, Among the components of the composite material, the MS resin is 40 - 60 weight parts, the SBC resin is 40 - 60 weight parts, and the AS resin is 10 - 15 weight parts.

3. The composite material according to claim 1, characterized in that, The MS resin adopts the ISO 1133 - 2011 standard, and the melt mass flow rate at 220°C and 10 kg is 20 - 30 g / 10 min.

4. The composite material according to claim 1, characterized in that, The SBC resin adopts the ISO 1133 - 2011 standard, and the melt mass flow rate at 200°C and 5 kg is ≤10 g / 10 min.

5. The composite material according to claim 1, wherein The mass content of butadiene in the SBC resin is 25% - 30%; and / or, the mass content of acrylonitrile in the AS resin is 20% - 30%.

6. The composite material according to claim 1, characterized in that, The refractive index of the MS resin is 1.56 - 1.57; and / or, the refractive index of the SBC resin is 1.55 - 1.

57.

7. The composite material according to claim 1, characterized in that, The components of the composite material further include 0.1 - 1 weight part of lubricant and 0.1 - 1 weight part of antioxidant.

8. The preparation method of the composite material according to any one of claims 1 to 7, characterized in that It includes the following steps: mixing the components evenly and then melt - extruding to obtain the composite material.

9. The application of the composite material according to any one of claims 1 - 7 in preparing wire protection sleeves, flexible display protective layers, flexible packaging films, automotive transparent components, transparent components of wearable devices, charging or data cable sheaths, and battery encapsulation films.

10. A cable arrangement protection sleeve for an electric cabinet, characterized in that, It is mainly made of the composite material according to any one of claims 1 - 7.

Images