Conductive PC alloy and preparation method and application thereof

Abstract

The invention discloses a conductive PC alloy and a preparation method and application thereof, and belongs to the technical field of high polymer materials. Under the condition that a carbon nanotube conductive agent is introduced into the product, ABS resin and PBT resin of specific types are selected to be matched with matrix PC resin, meanwhile, acrylic organic silicon rubber is selected as a flexibilizer, and the conductive PC alloy is prepared. The product not only can realize high conductivity and meet the requirements of the application field of electronic appliances, but also has good low-temperature impact resistance and high glossiness, and is wide in application range.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a conductive PC alloy and a preparation method and application thereof. Background Art

[0002] Conductive PC alloy materials refer to materials commonly used in the field of electronic appliances, which are made by adding components such as conductive masterbatch and conductive agent to PC alloys to improve the overall conductivity without losing basic performance, and prevent static electricity accumulation or static electricity adsorption. At present, based on production costs and comprehensive performance considerations, the conductive components in conductive PC alloy materials are mostly carbon-based materials, such as carbon nanotubes, carbon black, etc. However, with the upgrading of usage requirements, electronic and electrical products often need to achieve sufficient impact resistance in some extreme environments such as sub-zero temperatures, but the current conductive PC alloy products cannot achieve similar effects. At the same time, due to the problem of alloy system dispersion, these products generally have low gloss and are difficult to use in some products that require gloss on the appearance. Summary of the invention

[0003] Based on the defects of the prior art, the purpose of the present invention is to provide a conductive PC alloy. This product, while introducing a carbon nanotube conductive agent, selects specific types of ABS (acrylonitrile-butadiene-styrene terpolymer) resin and PBT (polybutylene terephthalate resin) resin to match with a base PC resin, and selects acrylic silicone rubber as a toughening agent. The product can not only achieve high conductivity and meet the requirements of electronic and electrical application fields, but also has good low-temperature impact resistance and high gloss, and the product has a wide range of applications.

[0004] In order to achieve the above object, the technical solution adopted by the present invention is:

[0005] A conductive PC alloy comprises the following components in parts by weight:

[0006] 60-85 parts of PC resin, 5-20 parts of ABS resin, 2-10 parts of PBT resin, 5-20 parts of toughening agent, and 0.5-3 parts of carbon nanotubes;

[0007] The intrinsic viscosity of the PBT resin at 25° C. is ≤1.05 dL / g;

[0008] The mass fraction of butadiene in the ABS resin is 16-25%;

[0009] The toughening agent is an acrylic silicone toughening agent.

[0010] Conductive PC alloy products mostly use carbon-based materials, especially carbon nanotubes, which are cheap and have high intrinsic conductivity, as conductive agents. In order to ensure the dispersibility of such inorganic powders and enable them to exert normal conductive effects, the matrix resin in the product needs to ensure a certain fluidity when combining with inorganic powders. However, such products cannot take into account high impact resistance in use, especially in low temperature environments, these products cannot meet the normal toughness working index requirements; on the other hand, due to the use of inorganic conductive agents, the gloss of existing conductive PC alloy products is generally low, and the appearance is not up to standard when prepared as electronic and electrical packaging materials, and the scope of application is limited. For this reason, in the technical solution of the present invention, the product introduces ABS resin and PBT resin into the PC resin-carbon nanotube alloy product system, and is matched with a specific acrylic silicone toughening agent. The alloy product formed not only has good low-temperature impact resistance and gloss, but also has high dispersibility of carbon nanotubes in the product system. The product can still maintain high conductivity and excellent comprehensive performance.

[0011] However, in the product described in the present invention, the selection of ABS resin and PBT resin is not arbitrary. The inventors found that the butadiene content in the ABS resin is related to the low-temperature toughness of the product and the dispersibility of the carbon nanotubes. If the selection is inappropriate, not only can it not be guaranteed that the product has sufficient impact resistance in a low-temperature environment when combined with a toughening agent, but it may even fail to achieve the expected gloss due to the low dispersion and low compatibility of the carbon nanotubes. On the other hand, the PBT resin is a wetting agent for the carbon nanotubes in the resin system. When the carbon nanotubes are in contact, the viscosity of the PBT resin is related to the wetting effect of the carbon nanotubes and the dispersibility of the PBT resin in the overall resin system. If the viscosity is too high, the carbon nanotubes in the product cannot be well dispersed, the product has poor electrical conductivity, and the toughness effect at low temperatures cannot be achieved.

[0012] Preferably, in the conductive PC alloy, the total mass content of PC resin, ABS resin and PBT resin is ≥ 70wt%.

[0013] Preferably, the conductive PC alloy comprises the following components in parts by weight:

[0014] 70-80 parts of PC resin, 10-15 parts of ABS resin, 4-6 parts of PBT resin, 6-13 parts of toughening agent, and 1-2 parts of carbon nanotubes.

[0015] Preferably, the PC resin has a melt index of 8 to 30 g / 10 min at 300° C. and 1.2 kg according to ISO 1133-2011.

[0016] More preferably, the melt index of the PC resin at 300° C. and 1.2 kg is in the range of one or any two of 8 g / 10 min, 10 g / 10 min, 12 g / 10 min, 15 g / 10 min, 18 g / 10 min, 19 g / 10 min, 20 g / 10 min, 22 g / 10 min, 25 g / 10 min, 28 g / 10 min, and 30 g / 10 min.

[0017] More preferably, the PC resin has a melt index of 10 to 20 g / 10 min at 300° C. and 1.2 kg.

[0018] In the conductive PC alloy of the present invention, changes in the melt index of the PC resin will lead to changes in the compatibility of the overall resin, the overall strength and the dispersibility of the carbon nanotubes. Preferably, when the melt index of the PC resin is within the above range, the product can achieve higher surface gloss and low-temperature impact resistance while meeting lower resistance.

[0019] Preferably, the intrinsic viscosity of the PBT resin at 25° C. is 0.85 to 1.05 dL / g.

[0020] More preferably, the intrinsic viscosity of the PBT resin at 25° C. is in the range of one or any two of 0.85 dL / g, 0.88 dL / g, 0.90 dL / g, 0.92 dL / g, 0.95 dL / g, 1.0 dL / g, and 1.05 dL / g.

[0021] More preferably, the intrinsic viscosity of the PBT resin at 25° C. is 0.9 to 1.05 dL / g.

[0022] As mentioned above, the viscosity of the PBT resin will have some influence on the wettability and dispersibility of the carbon nanotubes in the product. When it is preferably within the above range, the PBT can fully react with the polar groups on the surface of the carbon nanotubes, so that the compatibility between the organic resin and the inorganic components in the product is better, thereby showing better overall performance.

[0023] Preferably, the average particle size of the ABS resin is 0.2-1.2 mm, and the mass fraction of acrylonitrile in the ABS resin is 15-50%.

[0024] Preferably, the mass fraction of butadiene in the ABS resin is in the range of one or any two of 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%.

[0025] Further preferably, the mass fraction of butadiene in the ABS resin is 18-22%.

[0026] When the ABS resin is selected to have a butadiene content within the above preferred range, the product can have better gloss and low-temperature impact resistance.

[0027] Preferably, the ABS resin has a melt index of ≥8 g / 10 min at 230° C. and 10 kg according to ISO 1133-2011.

[0028] More preferably, the melt index of the ABS resin at 230° C. and 10 kg is 10 to 20 g / 10 min.

[0029] More preferably, the melt index of the ABS resin at 230° C. and 10 kg is in the range of one or any two of 10 g / 10 min, 12 g / 10 min, 14 g / 10 min, 16 g / 10 min, 18 g / 10 min, and 20 g / 10 min.

[0030] Preferably, in the conductive PC alloy, the mass ratio of ABS resin to toughening agent is (2:1) to (5:4).

[0031] In the product of the present invention, both the ABS resin and the toughening agent will affect the toughness and component uniformity of the product. After optimization, the inventors found that when the mass ratio of the two is selected within the above range, the product can have better component uniformity and low-temperature mechanical properties.

[0032] It should be noted that the components of the product of the present invention also include 0.01 to 3 parts of processing aids. More preferably, the processing aids include lubricants, antioxidants, etc. Those skilled in the art can add them according to actual needs as long as they do not affect the expected technical effects of the product of the present invention.

[0033] Preferably, the conductive PC alloy further comprises 0.5 to 1 part of an antioxidant and 1 to 2 parts of a lubricant.

[0034] More preferably, the antioxidant includes at least one of hindered phenol antioxidants, phosphite antioxidants, and hindered amine antioxidants; and the lubricant includes at least one of stearic acid lubricants, amide lubricants, and alkanoic acid lubricants.

[0035] Preferably, the specific surface area of ​​the carbon nanotubes is 240 to 300 m 2 / g.

[0036] The specific surface area of ​​the carbon nanotubes is tested and confirmed by a nitrogen adsorption-desorption method, with reference to GBT-10722-2014.

[0037] Preferably, the acrylic silicone toughening agent has a core-shell structure, the core layer comprises a composite of silicone and polyacrylate, and the shell layer comprises polymethyl methacrylate.

[0038] Preferably, the acrylic silicone toughening agent has a melt flow rate of 8 to 15 g / 10 min at 300 ° C and 1.2 kg load according to ISO-1133-2011, and a density of 1 to 1.5 g / cm 3 .

[0039] Preferably, the mass ratio of the core layer to the shell layer in the acrylic silicone toughening agent is (0.5:9.5) to (1.5:8.5).

[0040] Another object of the present invention is to provide a method for preparing the conductive PC alloy, comprising the following steps:

[0041] After the components are uniformly mixed, they are melt-extruded and granulated in a screw extruder to obtain the conductive PC alloy.

[0042] The preparation method of the conductive PC alloy of the present invention has simple operation steps and can realize industrial-scale production.

[0043] Preferably, the temperature range of the screw extruder is set to: 200-320°C, the screw speed is 400-600r / min, and the screw aspect ratio is (45-50):1.

[0044] Another object of the present invention is to provide application of the conductive PC alloy in preparing electronic and electrical packaging materials.

[0045] Preferably, the electronic and electrical packaging materials include turnover boxes and electronic pallets.

[0046] Another object of the present invention is to provide an electronic and electrical packaging material, comprising the conductive PC alloy of the present invention.

[0047] The conductive PC alloy of the present invention has ideal comprehensive properties. It can not only maintain sufficient impact resistance in low temperature environment, but also can achieve at least 20KJ / m at -40°C. 2 It has high impact strength, high gloss and good conductivity, and meets the appearance and practicality requirements of electronic and electrical packaging materials.

[0048] The beneficial effect of the present invention is that the present invention provides a conductive PC alloy. When a carbon nanotube conductive agent is introduced into the product, a specific type of ABS resin and PBT resin are selected to be matched with a base PC resin, and acrylic silicone rubber is selected as a toughening agent. The product can not only achieve high conductivity and meet the requirements of the electronic and electrical application field, but also has good low-temperature impact resistance and high gloss, and the product has a wide range of applications. DETAILED DESCRIPTION

[0049] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments and comparative examples, the purpose of which is to understand the content of the present invention in detail, rather than to limit the present invention. All other embodiments obtained by those of ordinary skill in the art without making creative work premise belong to the protection scope of the present invention. The experimental reagents and instruments involved in the implementation of the present invention, unless otherwise specified, are all commonly used common reagents and instruments.

[0050] Examples 1 to 15

[0051] The conductive PC alloy and the preparation method and application embodiments of the present invention, the components of the conductive PC alloy are shown in Table 1.

[0052] The preparation method of the product comprises the following steps:

[0053] The components are mixed evenly, and then placed in a screw extruder for melt extrusion and granulation to obtain the conductive PC alloy.

[0054] The temperature zones of the screw extruder are set to: zone 1: 200°C, zone 2: 240°C, zone 3: 240°C, zone 4: 240°C, zone 5: 240°C, zone 6: 240°C, zone 7: 240°C, zone 8: 240°C, zone 9: 240°C, zone 10: 300°C, the screw speed is 500r / min, and the aspect ratio is 48:1.

[0055] Comparative Examples 1 to 6

[0056] The difference between the comparative examples and the embodiments is only in the types and proportions of components, as shown in Table 2.

[0057] Among the components described in each embodiment and comparative example,

[0058] PC resin 1 is PC2220 produced by Wanhua Chemical, with a melt index of 19 g / 10 min at 300 °C and 1.2 kg;

[0059] PC resin 2 is S-2000F produced by Mitsubishi of Japan, with a melt index of 10 g / 10 min at 300 °C and 1.2 kg;

[0060] PC resin 3 is L-1250 produced by Teijin of Japan, with a melt index of 8 g / 10 min at 300°C and 1.2 kg;

[0061] PC resin 4 is HPF1 produced by Sabic Corporation of the United States, with a melt index of 25 g / 10 min at 300 °C and 1.2 kg;

[0062] ABS resins 1 to 5 were directly prepared in the laboratory by a blending method, wherein the materials polybutadiene grafted SAN resin and SAN resin were uniformly mixed in a certain proportion, and extruded by a twin-screw extruder to prepare ABS resin particles;

[0063] The polybutadiene grafted SAN is EB-168 produced by Shandong Yigong Chemical Co., Ltd., with a butadiene mass fraction of 60%; the SAN resin is 310TR produced by Kumho, South Korea;

[0064] ABS resin 1: material ratio polybutadiene grafted SAN: SAN = 33:66, the butadiene mass fraction of the obtained product is 20%, and the melt index is 15g / 10min;

[0065] ABS resin 2: material ratio polybutadiene grafted SAN: SAN = 27:73, the butadiene mass fraction of the obtained product is 16%, and the melt index is 19g / 10min;

[0066] ABS resin 3: material ratio polybutadiene grafted SAN: SAN = 42:58, the butadiene mass fraction of the obtained product is 25%, and the melt index is 10g / 10min;

[0067] ABS resin 4: material ratio polybutadiene grafted SAN: SAN = 16.8:83.2, the butadiene mass fraction of the obtained product is 10%, and the melt index is 25g / 10min;

[0068] ABS resin 5: material ratio polybutadiene grafted SAN: SAN = 1:1, the butadiene mass fraction of the obtained product is 30%, and the melt index is 7g / 10min;

[0069] PBT resin 1 is PBT GX122J produced by Yizheng Petrochemical, with an intrinsic viscosity of 1.05 dL / g at 25°C;

[0070] PBT resin 2 is PBT GX121 produced by Yizheng Petrochemical, with an intrinsic viscosity of 0.95 dL / g at 25°C;

[0071] PBT resin 3 is GX112 produced by Yizheng Petrochemical, with an intrinsic viscosity of 0.85 dL / g at 25°C;

[0072] PBT resin 4 is PBT GL236 produced by Yizheng Petrochemical, with an intrinsic viscosity of 1.28 dL / g at 25°C;

[0073] The carbon nanotubes are GC-210 produced by Shandong Dazhan, with a specific surface area of ​​260g / m 2 ;

[0074] Toughener 1 is S-2001 produced by Mitsubishi of Japan, a core-shell structure acrylic silicone toughener, the core layer includes a composite of silicone and polyacrylate, and the shell layer is polymethyl methacrylate;

[0075] Toughener 2 is M-521 produced by Japan's Kaneka Chemical, a core-shell structured methyl methacrylate-butadiene-styrene toughener, the core layer includes a polymer of butadiene and styrene, and the shell layer is polymethyl methacrylate;

[0076] Toughener 3 is S-2100 produced by Mitsubishi of Japan, a core-shell structure acrylic silicone toughener, the core layer includes a composite of silicone and polyacrylate, and the shell layer is polymethyl methacrylate;

[0077] Toughener 4 is POE ENGAGE 8137 produced by Dow Chemical, USA, which is an ethylene-octene copolymer;

[0078] Unless otherwise specified, the components and raw materials used in the embodiments and comparative examples of the present invention are all commercially available raw materials, such as antioxidants, lubricants and other processing aids, and anti-dripping agents, and the components and raw materials used in each parallel experiment are all of the same kind.

[0079] Table 1

[0080]

[0081] Table 2

[0082] Component weight Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 PC resin 1 75 75 75 75 75 75 ABS resin 1 10 10 10 10 ABS resin 4 10 ABS resin 5 10 PBT resin 1 5 5 20 5 5 PBT resin 4 5 Carbon Nanotubes 1.5 1.5 1.5 1.5 1.5 1.5 Toughener 1 8 8 8 8 Toughener 2 8 Toughener 4 8

[0083] Effect Example 1

[0084] In order to verify the performance of the product of the present invention, the following performance tests were performed on the products of each embodiment and comparative example. The specific steps are as follows:

[0085] (1) Surface resistance test: Each product was injection molded (mold temperature 80°C, injection temperature 260°C) into a test square plate of 100×100×3 mm, and then directly tested using an RT1000 resistance meter. The average value of 5 samples was measured.

[0086] (2) Gloss test: Each product was injection molded (mold temperature 80°C, injection temperature 260°C) into a test square plate of 100×100×3 mm, and then tested using a YG60S gloss meter using the angle method at 60°.

[0087] (3) Low-temperature notched impact strength test: Each product was injection molded into a test impact specimen of (80±2)×(10.0±0.2)×(4.0±0.2) mm, with a notch residual width of (8.0±0.2) mm. The specimen was first placed in a -40°C freezer for 8 h, and then taken out for a notched impact strength test in accordance with GB / T1843-2008, with an A-type notch and an impact energy of 5.5 J. The test was completed within 20 s after being taken out.

[0088] The test results are shown in Tables 3 and 4.

[0089] Table 3

[0090]

[0091] Table 4

[0092] Component weight Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Surface resistance <![CDATA[2.71*10 6 ]]> <![CDATA[1.67*10 5 ]]> <![CDATA[9.78*10 8 ]]> <![CDATA[3.25*10 8 ]]> <![CDATA[4.89*10 9 ]]> <![CDATA[6.33*10 7 ]]> Glossiness(°) 88 60 29 52 69 67 <![CDATA[Low temperature Charpy impact strength (KJ / m 2 )]]> 5 33 22 8 5 4

[0093] As can be seen from Tables 3 and 4, in the product of the present invention, due to the selection of a specific PC / ABS / PBT resin system and a toughening agent, the PC alloy product containing conductive carbon nanotubes not only has good conductivity, but also has a surface resistance of E6 (i.e., less than 1*10 7 Ω) and below. In terms of use and appearance, the product has good low-temperature impact resistance, and the impact strength at -40°C reaches at least 20KJ / m 2 , and the glossiness is high, reaching 70° and above.

[0094] In the products of each embodiment, it can be seen from Embodiment 1 and Embodiments 4 to 6 that the melt index of the PC resin has a certain influence on the performance of the product. When it is preferably in the range of 10 to 20 g / 10 min, the gloss and low-temperature impact resistance of the obtained product can be maintained at a higher level without a significant increase in surface resistance, and the overall performance is better.

[0095] According to Example 1, Examples 7 to 8 and Comparative Examples 1 to 2, it can be seen that in the product, the butadiene content of the ABS resin has a great influence on the performance of the product. When the butadiene content is low, although the glossiness of the obtained product is high, the low-temperature impact resistance is extremely low and cannot be used normally in a low-temperature environment. As the butadiene content increases, the low-temperature impact resistance of the product can be improved while maintaining a high gloss level; however, if the butadiene content of the ABS resin is too high, as shown in Comparative Example 2, the glossiness of the product will be significantly reduced.

[0096] According to Example 1, Examples 9-10 and Comparative Example 3, it can be seen that the viscosity of the PBT resin in the product will directly affect the dispersibility of the carbon nanotubes and the compatibility and fluidity between the resins. When the intrinsic viscosity of the PBT resin at 25°C is maintained within 1.05dL / g, the product can achieve a good comprehensive level, especially when the intrinsic viscosity is maintained at 0.9dL / g and above, the product obviously has a lower surface resistance and a higher level of low-temperature impact resistance. However, if the specific performance of the PBT resin exceeds the range, the performance of the product will be greatly reduced. Not only will the surface resistance increase due to the decrease in the dispersibility of the carbon nanotubes, the glossiness will decrease, and the low-temperature impact resistance will also be significantly weakened. At the same time, the amount of PBT resin added cannot be too much. As shown in Comparative Example 4, if the addition ratio between the resins is inappropriate, the proportion of PBT resin is too high, and the various performances of the product cannot meet the standards.

[0097] On the other hand, in the conductive PC alloy of the present invention, the selection of the type of toughening agent is also crucial. In addition to affecting the low-temperature impact resistance of the product, this component also has a great influence on the dispersibility of carbon nanotubes in the resin. The products of Comparative Examples 5 and 6 use toughening agents not specified in the present invention. The surface resistance of the products is high and the glossiness is low. In addition, the low-temperature notched impact strength of the products is less than 10 KJ / m due to the poor compatibility of the two toughening agents in the product system. 2 .

[0098] In the product system, the inventors found through experiments that the addition ratio of toughening agent to ABS resin also affects the performance of the product to a certain extent. When the ratio of the two is preferably between (2:1) and (5:4), the surface resistance of the obtained product is lower, and the glossiness and low-temperature impact resistance are better overall.

[0099] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A conductive PC alloy, characterized in that: The composition comprises the following components in parts by weight: 60-85 parts of PC resin, 5-20 parts of ABS resin, 2-10 parts of PBT resin, 5-20 parts of toughening agent, and 0.5-3 parts of carbon nanotubes; The intrinsic viscosity of the PBT resin at 25° C. is ≤1.05 dL / g; The mass fraction of butadiene in the ABS resin is 16-25%; The toughening agent is an acrylic silicone toughening agent.

2. The conductive PC alloy according to claim 1, characterized in that: The PC resin has a melt index of 8 to 30 g / 10 min at 300° C. and 1.2 kg according to ISO1133-2011.

3. The conductive PC alloy according to claim 1, characterized in that: The intrinsic viscosity of the PBT resin at 25° C. is 0.85 to 1.05 dL / g.

4. The conductive PC alloy according to claim 1, characterized in that: The ABS resin has a melt index of ≥8 g / 10 min at 230° C. and 10 kg according to ISO 1133-2011.

5. The conductive PC alloy according to claim 1, characterized in that: In the conductive PC alloy, the mass ratio of ABS resin to toughening agent is (2:1) to (5:4).

6. The conductive PC alloy according to claim 1, characterized in that: The acrylic organosilicon toughening agent has a core-shell structure, wherein the core layer comprises a composite of organosilicon and polyacrylate, and the shell layer comprises polymethyl methacrylate.

7. The method for preparing the conductive PC alloy according to any one of claims 1 to 6, characterized in that: The following steps are involved: After the components are uniformly mixed, they are melt-extruded and granulated in a screw extruder to obtain the conductive PC alloy.

8. Use of the conductive PC alloy according to any one of claims 1 to 6 in the preparation of electronic and electrical packaging materials.

9. The use according to claim 8, characterized in that The electronic and electrical packaging materials include turnover boxes and pallets.

10. An electronic and electrical packaging material, characterized in that: The present invention comprises the conductive PC alloy as described in any one of claims 1 to 6.

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