Weather-resistant, reinforced, toughened, antistatic polyester masterbatch, preparation method, and application

Abstract

The present invention belongs to the technical field of antistatic polyester masterbatch, and specifically relates to a weather-resistant reinforced and toughened antistatic polyester masterbatch, a preparation method, and an application thereof. The antistatic polyester masterbatch comprises the following raw materials in parts by weight: 60-80 parts of a base resin, 15-20 parts of core-shell conductive particles, 10-20 parts of aminopolyethylene glycol polylactic acid represented by the structure of Formula I, 0.5-1 parts of a hydroxyl-terminated aromatic hyperbranched polyester, and 3-5 parts of a dispersant. The core-shell conductive particles use nano-conductive carbon black as the core and a styrene-glycidyl methacrylate copolymer as the shell, with the mass ratio of nano-conductive carbon black, styrene, and glycidyl methacrylate being 1:3-5:3-5. The organic shell layer of the core-shell conductive particles enhances the compatibility and interfacial bonding between the conductive particles and the base resin, prevents agglomeration of the conductive particles, and improves antistatic performance and weather resistance. The aminopolyethylene glycol polylactic acid and the core-shell conductive particles form a complete conductive network, improving antistatic performance.

Description

Technical Field

[0001] The invention belongs to the technical field of antistatic polyester masterbatch, and particularly relates to a weather-resistant reinforced and toughened antistatic polyester masterbatch, a preparation method and application thereof. Background Art

[0002] Polyethylene terephthalate (PET) boasts high strength, high rigidity, good heat resistance, excellent dimensional stability, and chemical insulation properties, making it widely used in electronic and electrical components, packaging, clothing, and automotive applications. However, due to its high resistivity, PET easily generates static electricity on its surface during friction and contact, causing significant challenges in its processing and application. In particular, in the electronics industry, static electricity leakage can cause semiconductor device malfunction and disrupt normal circuit operation.

[0003] Antistatic masterbatch is a granular material with antistatic properties, made from a carrier resin matrix and containing an antistatic agent and other additives. This material is then processed through mixing and granulation. The antistatic agent creates a conductive path on the surface of the material or reduces surface resistance, thereby quickly dissipating static electricity. Compared to directly incorporating an antistatic agent, antistatic masterbatch offers greater compatibility with the substrate, a more uniform and long-lasting antistatic effect, ease of use, and environmental friendliness.

[0004] Depending on the type of antistatic agent, antistatic masterbatch can be divided into organic and inorganic types. Since most organic antistatic agents have poor heat resistance and are not suitable for the processing and molding temperature of the matrix resin, inorganic antistatic agents have good temperature tolerance and have received widespread attention. For example, patent CN108084686B discloses a polyester-based conductive masterbatch based on a carbon nanotube and graphene compound system and its preparation method. First, the carbon nanotubes and graphene are uniformly dispersed in a volatile inert solvent and treated with an ultrasonic treatment device for 1 hour. The treated dispersion is then stirred with the raw materials in a high-speed blender according to a certain proportion. After mixing with a compatibilizer in a certain proportion at room temperature, it is melt-extruded through a twin-screw extruder to prepare a conductive masterbatch. Patent CN108440919B discloses an antistatic masterbatch and PET film and preparation method. The antistatic masterbatch includes a polyester resin, a conductive fiber, a flame retardant, and a dispersant. The conductive fiber is a polyacrylonitrile carbon fiber coated with conductive carbon black, and the flame retardant is a metal hydroxide. The present invention utilizes polyacrylonitrile carbon fiber to coat the conductive carbon black. The polyacrylonitrile carbon fiber has good three-dimensional network, conductivity and compatibility, and can enable the conductive carbon black to form a stable conductive network in the polyester resin, thereby having an antistatic effect.

[0005] The above is a technology for preparing antistatic masterbatch using inorganic conductive materials such as conductive carbon black, carbon fiber, carbon nanotubes, and graphene as antistatic agents. PET mixed with antistatic masterbatch has excellent antistatic properties, but inorganic conductive materials are usually easy to agglomerate and have poor compatibility with polyester resins, resulting in poor antistatic performance and weather resistance of antistatic PET products. Therefore, it is necessary to develop an antistatic polyester masterbatch with excellent antistatic and weather resistance. Summary of the Invention

[0006] To solve the above technical problems, the present invention provides a weather-resistant reinforced, toughened antistatic polyester masterbatch, a preparation method and an application. The core-shell conductive particles in the masterbatch have nano-conductive carbon black as the core and a copolymer of styrene and glycidyl methacrylate as the shell. The organic shell layer of the core-shell conductive particles helps to enhance the compatibility and interfacial bonding between the conductive particles and the substrate resin, prevent the conductive particles from agglomerating, and thus improve the antistatic performance and weather resistance of the material; the amino polyethylene glycol polylactic acid with antistatic action segments and the core-shell conductive particles form a complete conductive network inside the material, further improving the antistatic performance of the material.

[0007] In order to achieve the above objectives, the following technical solutions are adopted:

[0008] A weather-resistant, reinforced, toughened, and antistatic polyester masterbatch comprises the following raw materials in parts by weight: 60-80 parts of a base resin, 15-20 parts of core-shell conductive particles, 10-20 parts of aminopolyethylene glycol polylactic acid represented by formula I, 0.5-1 part of a hydroxyl-terminated aromatic hyperbranched polyester, and 3-5 parts of a dispersant. The core-shell conductive particles have nano-conductive carbon black as the core and a copolymer of styrene and glycidyl methacrylate as the shell. The mass ratio of the nano-conductive carbon black, styrene, and glycidyl methacrylate is 1:3-5:3-5.

[0009] Formula I: ,

[0010] Wherein m is an integer between 40 and 80, and n is an integer between 10 and 30.

[0011] The amino polyethylene glycol polylactic acid has a number average molecular weight of 3000-6000.

[0012] Amino polyethylene glycol polylactic acid is a block copolymer composed of amino, polyethylene glycol, and polylactic acid. Since the active amino group can easily react with epoxy groups, the polyethylene glycol part is a non-ionic antistatic agent, and the polylactic acid part can undergo ester exchange reaction with the base polyester, resulting in amino polyethylene glycol polylactic acid playing multiple roles in the masterbatch from multiple angles.

[0013] First, the ether bonds in the polyethylene glycol moiety exhibit excellent hydrophilicity. They form stable electrostatic conduction pathways through orderly arrangement within the material, synergizing with the core-shell conductive particles to achieve an antistatic effect. Second, the amino groups on the amino polyethylene glycol polylactic acid react with the epoxy groups on the core-shell conductive particles, enhancing the weatherability of the masterbatch. Finally, during the masterbatch preparation process, the lipophilic polylactic acid moiety undergoes an ester exchange reaction with the base polyester under the shearing action of the screw, grafting the antistatic polyethylene glycol moiety onto the base polyester molecules, further imparting the material with a long-lasting antistatic effect.

[0014] However, during the masterbatch preparation process, amino polyethylene glycol polylactic acid inevitably undergoes an ester exchange reaction with the base polyester, resulting in the grafting of flexible polyethylene glycol and polylactic acid moieties onto the base polyester, as well as the production of a small amount of low-molecular-weight polyethylene glycol and low-molecular-weight polylactic acid. These factors are detrimental to the regular arrangement of the polyester molecular chains, reducing the crystallinity of the polyester material and significantly adversely affecting the tensile strength of the material. Therefore, the use of a multifunctional hydroxyl-terminated aromatic hyperbranched polyester is necessary to improve its mechanical properties. Therefore, the relative amounts of core-shell conductive particles, amino polyethylene glycol polylactic acid, and hydroxyl-terminated aromatic hyperbranched polyester must be strictly controlled in order to obtain a material with excellent antistatic and weather resistance without compromising other material properties.

[0015] The average particle size of the nano-conductive carbon black is 20-50 nm.

[0016] The core-shell conductive particles are prepared by a method comprising the following steps:

[0017] In an inert atmosphere, styrene, glycidyl methacrylate, nano-conductive carbon black, surfactant, and water are mixed evenly, the temperature is increased, and the initiator solution is added dropwise. The reaction is carried out at a constant temperature after the addition is completed. After the reaction is completed, the temperature is lowered and post-processed to obtain core-shell conductive particles.

[0018] The amount of water used is 8-10 times the mass of the nano-conductive carbon black. The amount of the surfactant used is 1-3wt% of the nano-conductive carbon black. The surfactant is selected from one or a combination of two or more of sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and sodium dodecylsulfonate. The initiator is selected from one or a combination of two or more of potassium persulfate, sodium persulfate, and ammonium persulfate. The amount of the initiator used is 0.5-0.8wt% of the sum of the mass of styrene and glycidyl methacrylate. The solvent of the initiator solution is water, and the concentration is 8-10wt%. The temperature is raised to 60-80°C. The initiator solution is added dropwise in 30-60 minutes. The constant temperature reaction time is 3-5 hours. The post-treatment comprises centrifugation, washing, and drying. The washing step is 1-3 alternating washes with ethanol and water. The drying step is drying at 60-100°C to constant weight.

[0019] The terminal hydroxyl aromatic hyperbranched polyester has a functionality of 6-12 and a hydroxyl value of 180-240 mg KOH / g, and is selected from one or a combination of HyPer H401 and HyPer H402.

[0020] The dispersant is selected from one or a combination of two or more of calcium stearate, zinc stearate, sodium stearate, polyethylene wax, and hexenyl bisstearamide.

[0021] The base resin has an intrinsic viscosity of 0.5-0.7 dL / g and is selected from one or a combination of two or more of polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly(1,4-cyclohexanedimethanol terephthalate), and polyethylene 2,6-naphthalate.

[0022] The present invention also provides a method for preparing the weather-resistant, reinforced, toughened, antistatic polyester masterbatch, comprising the following steps:

[0023] At room temperature, the core-shell conductive particles and the amino polyethylene glycol polylactic acid shown in the structure of formula I are first mixed evenly, and then the base resin, the terminal hydroxyl aromatic hyperbranched polyester and the dispersant are added and mixed evenly, and extruded into granules in a twin-screw extruder to obtain a weather-resistant reinforced, toughened antistatic polyester masterbatch.

[0024] The twin-screw extruder has a screw length-diameter ratio of 25-40:1, a main engine speed of 200-500 r / min, and an extrusion temperature of 270-275° C. in zone 1, 275-280° C. in zone 2, 275-285° C. in zone 3, 285-290° C. in zone 4, and 285-290° C. in zone 5.

[0025] The weather-resistant reinforced and toughened antistatic polyester masterbatch of the present invention can be used to prepare antistatic thermoplastic polyester composite materials, and can endow the materials with excellent antistatic properties.

[0026] The content of the weather-resistant, reinforced, toughened and antistatic polyester masterbatch is 2-4 wt % of the thermoplastic polyester in the antistatic thermoplastic polyester composite material.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The core-shell conductive particles in the masterbatch of the present invention have nano-conductive carbon black as the core and a copolymer of styrene and glycidyl methacrylate as the shell. The organic shell layer of the core-shell conductive particles helps to enhance the compatibility and interfacial bonding between the conductive particles and the base resin, prevent the conductive particles from agglomerating, and thus improve the antistatic performance and weather resistance of the material. The amino polyethylene glycol polylactic acid with antistatic action segments and the core-shell conductive particles form a complete conductive network inside the material, further improving the antistatic performance of the material. DETAILED DESCRIPTION

[0029] The present invention will be further described below in conjunction with specific embodiment, but is not limited to the content on the specification sheets. Unless otherwise specified, "parts" described in the embodiments of the present invention are all parts by weight. All reagents used are commercially available reagents in this area.

[0030] Amino polyethylene glycol polylactic acid with a number average molecular weight of 5200 was purchased from Guangzhou Carbon Technology Co., Ltd., the number average molecular weight of the polyethylene glycol segment was 3400, and the number average molecular weight of the polylactic acid segment was 2000.

[0031] Amino polyethylene glycol polylactic acid with a number average molecular weight of 3100 was purchased from Guangzhou Carbon Technology Co., Ltd., the number average molecular weight of the polyethylene glycol segment was 2000, and the number average molecular weight of the polylactic acid segment was 1400.

[0032] Sinopec PET FC510A, intrinsic viscosity is 0.675dL / g.

[0033] Eastman Chemical PET PJ003, intrinsic viscosity 0.80 dL / g.

[0034] DENKA conductive carbon black LI400, with an average particle size of 48 nm, was purchased from Tianjin Yiborui Chemical Co., Ltd.

[0035] Example 1

[0036] 1) Under a nitrogen atmosphere, 300 g of styrene, 300 g of glycidyl methacrylate, 100 g of conductive carbon black LI400, 3 g of sodium dodecylbenzenesulfonate, and 800 g of water were mixed evenly, heated to 60°C, and 30 g of a 10 wt% potassium persulfate solution (solvent: water) was added dropwise for 30 min. The mixture was reacted at a constant temperature for 5 h. After the reaction, the mixture was cooled to room temperature, centrifuged, and the centrifugal precipitate was washed alternately with ethanol and water twice, and dried at 60°C to constant weight to obtain core-shell conductive particles.

[0037] 2) At room temperature, 20g of core-shell conductive particles and 20g of amino polyethylene glycol polylactic acid (Formula I) with a number-average molecular weight of 5200 were uniformly mixed. Then, 60g of PET FC510A, 1g of hydroxyl-terminated aromatic hyperbranched polyester HyPer H401, and 5g of calcium stearate were added and mixed uniformly. The mixture was extruded and pelletized in a twin-screw extruder to obtain an antistatic polyester masterbatch. The twin-screw extruder had a screw aspect ratio of 25:1, a main engine speed of 250 rpm, and extrusion temperatures of 270°C for zone 1, 275°C for zone 2, 280°C for zone 3, 285°C for zone 4, and 290°C for zone 5.

[0038] 3) 4 parts by mass of antistatic polyester masterbatch and 100 parts by mass of PET PJ003 were uniformly mixed, and then injection molded at 255° C. on an injection molding machine to prepare an antistatic PET composite material.

[0039] Example 2

[0040] The rest is the same as Example 1, except that in step 1), the amount of styrene used is 500 g.

[0041] Example 3

[0042] The rest is the same as Example 1, except that in step 1), the amount of glycidyl methacrylate used is 500 g.

[0043] Example 4

[0044] The rest is the same as Example 1, except that in step 2), an equal mass of amino polyethylene glycol polylactic acid with a number average molecular weight of 3100 is used to replace the amino polyethylene glycol polylactic acid with a number average molecular weight of 5200.

[0045] Example 5

[0046] The rest is the same as Example 1, except that in step 2), the amount of amino polyethylene glycol polylactic acid used is 10 g.

[0047] Example 6

[0048] The rest is the same as Example 1, except that in step 2), the amount of HyPer H401 used is 0.5 g.

[0049] Example 7

[0050] The rest is the same as Example 1, except that in step 2), the amount of core-shell conductive particles used is 10 g.

[0051] Example 8

[0052] 1) Under a nitrogen atmosphere, 500 g of styrene, 500 g of glycidyl methacrylate, 100 g of conductive carbon black LI400, 3 g of sodium dodecylbenzenesulfonate, and 800 g of water were mixed evenly, heated to 60°C, and 50 g of a 10 wt% potassium persulfate solution (solvent: water) was added dropwise. The mixture was added dropwise for 45 min and the temperature was kept constant for 5 h. After the reaction, the mixture was cooled to room temperature, centrifuged, and the centrifugal precipitate was washed alternately with ethanol and water twice, and dried at 60°C to constant weight to obtain core-shell conductive particles.

[0053] 2) At room temperature, 20g of core-shell conductive particles and 20g of amino polyethylene glycol polylactic acid (Formula I) with a number-average molecular weight of 5200 were uniformly mixed. Then, 80g of PET FC510A, 1g of hydroxyl-terminated aromatic hyperbranched polyester HyPer H402, and 5g of calcium stearate were added and mixed uniformly. The mixture was extruded and pelletized in a twin-screw extruder to obtain an antistatic polyester masterbatch. The twin-screw extruder had a screw aspect ratio of 25:1, a main engine speed of 250 rpm, and extrusion temperatures of 270°C for zone 1, 275°C for zone 2, 280°C for zone 3, 285°C for zone 4, and 290°C for zone 5.

[0054] 3) 2 parts by mass of antistatic polyester masterbatch and 100 parts by mass of PET PJ003 were mixed evenly, and then injection molded at 255° C. on an injection molding machine to prepare an antistatic PET composite material.

[0055] Comparative Example 1

[0056] The rest is the same as Example 1, except that in step 2), the amino polyethylene glycol polylactic acid with a number average molecular weight of 5200 is replaced by an equal mass of Haian Petrochemical PEG6000.

[0057] Comparative Example 2

[0058] 1) At room temperature, 20g of conductive carbon black LI400 and 20g of amino polyethylene glycol polylactic acid (Formula I) with a number-average molecular weight of 5200 were uniformly mixed. Then, 60g of PET FC510A, 1g of hydroxyl-terminated aromatic hyperbranched polyester HyPer H401, and 5g of calcium stearate were added and mixed uniformly. The mixture was extruded and pelletized in a twin-screw extruder to obtain an antistatic polyester masterbatch. The twin-screw extruder had a screw aspect ratio of 25:1, a main engine speed of 250 rpm, and extrusion temperatures of 270°C for zone 1, 275°C for zone 2, 280°C for zone 3, 285°C for zone 4, and 290°C for zone 5.

[0059] 2) 4 parts by mass of antistatic polyester masterbatch and 100 parts by mass of PET PJ003 were uniformly mixed, and then injection molded at 255° C. on an injection molding machine to prepare an antistatic PET composite material.

[0060] Comparative Example 3

[0061] The rest is the same as Example 1, except that in step 2), an equal mass of pentaerythritol is used to replace the hydroxyl-terminated aromatic hyperbranched polyester HyPer H401.

[0062] The materials prepared in the above examples and comparative examples were subjected to the following performance tests:

[0063] Tensile properties: tested according to GB / T1040-2006 standard, using Instron 1185 universal testing machine, testing temperature 23 ° C, clamping length 60 mm, tensile speed 5 mm / min.

[0064] Izod beam impact strength: tested according to GB / T1843-2008 standard.

[0065] Surface resistance: The anti-static PET composite material was pressed into a sheet at 230℃ for 45s to obtain a film with a thickness of 0.45mm. The film was tested according to GB / T1410-2006 Test method for volume resistivity and surface resistivity of solid insulating materials.

[0066] Weathering resistance: The surface resistivity sample was placed in a constant temperature and humidity aging chamber at 85°C and 85% humidity for one week. After being taken out, it was washed in 25°C deionized water with a rotor at a speed of 100 r / min for 3 minutes. After being fished out and air-dried at room temperature for 48 hours, the surface resistivity was remeasured and the resistivity increase rate was calculated.

[0067] Table 1 Performance test results

[0068] .

[0069] The performance test results in Table 1 show that the masterbatch prepared by the present invention has strengthening and toughening functions, and has a long-lasting antistatic effect and strong weather resistance. From Examples 1, 5, 7, Comparative Examples 1, and 2, it is clearly shown that amino polyethylene glycol polylactic acid synergizes with the core-shell conductive particles to improve toughness.

[0070] The above detailed description is a specific description of one feasible embodiment of the present invention. This embodiment is not intended to limit the patent scope of the present invention. Any equivalent implementation or modification that does not depart from the present invention should be included in the scope of the technical solution of the present invention.

Claims

1. A weather-resistant, reinforced, toughened antistatic polyester masterbatch, characterized in that: The invention comprises the following raw materials in parts by weight: 60-80 parts of a base resin, 15-20 parts of core-shell conductive particles, 10-20 parts of amino polyethylene glycol polylactic acid represented by the structure of formula I, 0.5-1 part of a hydroxyl-terminated aromatic hyperbranched polyester, and 3-5 parts of a dispersant. The core-shell conductive particles have nano-conductive carbon black as the core and a copolymer of styrene and glycidyl methacrylate as the shell. The mass ratio of the nano-conductive carbon black, styrene, and glycidyl methacrylate is 1:3-5:3-5. Formula I: , Wherein m is an integer between 40 and 80, and n is an integer between 10 and 30.

2. The weather-resistant, reinforced, toughened, antistatic polyester masterbatch according to claim 1, characterized in that: The amino polyethylene glycol polylactic acid has a number average molecular weight of 3000-6000.

3. The weather-resistant, reinforced, toughened, antistatic polyester masterbatch according to claim 1, characterized in that: The average particle size of the nano-conductive carbon black is 20-50 nm.

4. The weather-resistant, reinforced, toughened, antistatic polyester masterbatch according to claim 1, characterized in that: The core-shell conductive particles are prepared by a method comprising the following steps: In an inert atmosphere, styrene, glycidyl methacrylate, nano-conductive carbon black, surfactant, and water are mixed evenly, the temperature is increased, and the initiator solution is added dropwise. The reaction is carried out at a constant temperature after the addition is completed. After the reaction is completed, the temperature is lowered and post-processed to obtain core-shell conductive particles.

5. The weather-resistant, reinforced, toughened, antistatic polyester masterbatch according to claim 4, characterized in that: The amount of the surfactant is 1-3wt% of the nano conductive carbon black; the surfactant is selected from one or a combination of two or more of sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and sodium dodecylsulfonate; the initiator is selected from one or a combination of two or more of potassium persulfate, sodium persulfate, and ammonium persulfate; the amount of the initiator is 0.5-0.8wt% of the total mass of styrene and glycidyl methacrylate.

6. The weather-resistant, reinforced, toughened, antistatic polyester masterbatch according to claim 1, characterized in that: The terminal hydroxyl aromatic hyperbranched polyester has a functionality of 6-12 and a hydroxyl value of 180-240 mg KOH / g, and is selected from one or a combination of HyPer H401 and HyPer H402.

7. The weather-resistant, reinforced, toughened, antistatic polyester masterbatch according to claim 1, characterized in that: The base resin has an intrinsic viscosity of 0.5-0.7 dL / g and is selected from one or a combination of two or more of polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly(1,4-cyclohexanedimethanol terephthalate), and polyethylene 2,6-naphthalate.

8. A method for preparing the weather-resistant, reinforced, toughened, antistatic polyester masterbatch according to any one of claims 1 to 7, characterized in that: The steps include: At room temperature, the core-shell conductive particles and the amino polyethylene glycol polylactic acid shown in the structure of formula I are first mixed evenly, and then the base resin, the terminal hydroxyl aromatic hyperbranched polyester and the dispersant are added and mixed evenly, and extruded into granules in a twin-screw extruder to obtain a weather-resistant reinforced, toughened antistatic polyester masterbatch.

9. An application of the weather-resistant, reinforced, toughened, antistatic polyester masterbatch according to any one of claims 1 to 7, characterized in that: The weather-resistant reinforced and toughened antistatic polyester masterbatch is used for preparing antistatic thermoplastic polyester composite materials.

10. The use of the weather-resistant, reinforced, toughened, antistatic polyester masterbatch according to claim 9, characterized in that: The content of the weather-resistant, reinforced, toughened and antistatic polyester masterbatch is 2-4 wt % of the thermoplastic polyester in the antistatic thermoplastic polyester composite material.

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