Antistatic glass fiber reinforced polyglycolic acid composite material, preparation method and application thereof

Abstract

The application relates to the technical field of high polymer composite materials, and provides an antistatic glass fiber reinforced polyglycolic acid composite material and a preparation method and application thereof. The antistatic glass fiber reinforced polyglycolic acid composite material comprises a core material and at least one layer of outer material; the core material comprises a first polyglycolic acid resin, glass fibers and a first additive, the first additive comprises a first antistatic agent, and the glass fibers continuously extend from one end of the core material to the opposite end; the outer material wraps the core material, the outer material comprises a second polyglycolic acid resin and a second additive, and the second additive comprises a second antistatic agent. The polyglycolic acid reinforced material is designed based on a multi-module system, can make high-content glass fibers uniformly disperse in polyglycolic acid, and greatly improves the performance of the composite material. The antistatic polyglycolic acid reinforced composition has good mechanical properties and antistatic performance and can be naturally degraded.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high polymer composite materials, and more particularly to an antistatic glass fiber reinforced polyglycolic acid composite material, a preparation method and application thereof. BACKGROUND

[0002] Polyglycolic acid (PGA) is a biodegradable material, which has excellent mechanical properties, heat resistance, gas barrier property, biocompatibility and biodegradability, and gradually degrades into water and carbon dioxide after a certain period of use, and is harmless to the human body, animals and plants, and the natural environment, and has good application prospects in the fields of oil exploitation, industrial production, biodegradable packaging materials, disposable tools and medical health. However, the impact strength of polyglycolic acid is low, and the antistatic property is poor, and when the application scene has high requirements on antistatic and impact strength, it is necessary to blend and modify the polyglycolic acid in order to improve the comprehensive performance.

[0003] Glass fiber is an inorganic non-metallic material with excellent performance, which has the characteristics of good heat resistance and high mechanical strength, and is often used to reinforce composite materials. Patent (CN109553937B) discloses a glass fiber reinforced PET material, which solves the problem of strength rigidity and light weight while meeting the use requirements; Li Weiming (Tianjin University of Science and Technology. 2013) studied the glass fiber modified PHB / PLA composite material, and when the addition amount is 30%-40%, the tensile strength and impact strength of the system are improved by more than 50%, and the shrinkage rate of the material is effectively reduced. Glass fiber has been applied in traditional plastics for reinforcing resins, and should also have broad application prospects in the field of biodegradable materials, especially PGA materials. The current research difficulty is how to realize the uniform dispersion of high content of glass fiber in PGA, while ensuring the improvement of the mechanical properties of the product, and making PGA have the characteristics of low cost, high stability and easy processing. It should be noted that the surface resistivity of glass fiber reinforced composite material is high, and the glass fiber reinforced composite material is prone to static spark and other problems during use. Therefore, when using glass fiber reinforced PGA in application scenes with high requirements on fire resistance and flame retardation, fire, explosion and other disasters are easily caused due to static accumulation.

[0004] Graphene is a single-atom layer thick two-dimensional nanocarbon material composed of sp2 hybridized carbon atoms. Since Geim et al. of Manchester University first obtained single-layer and thin-layer graphene by micro-mechanical exfoliation in 2004, subsequent studies have shown that graphene has special electronic properties, such as high electron mobility (20,000 cm 2 V -1 S -1), room temperature quantum Hall effect, and high modulus, high strength and other mechanical properties. In addition, the surface of graphene exists conjugated pi bond, sp2 structure ensures the electron's ballistic transport, compared with the traditional carbon black, acetylene black, metal fiber and other permanent antistatic materials containing a large number of sp3 carbon structure makes the conductivity is relatively low, these characteristics make graphene has good electrical conductivity. At present, the main method for preparing graphene is oxidation-reduction method, liquid phase exfoliation method and gas phase deposition method. Among them, the oxidation-reduction method is to use concentrated sulfuric acid, potassium permanganate and other strong oxidants to oxidize the graphite to obtain graphene oxide, and then reduce the graphene oxide into graphene by high temperature or chemical method. This method is the most common method at present, and the industrial production is the most. However, the graphene prepared by the strong oxidant has many defects, even after reduction, the physical and chemical properties are still lost. Moreover, a large amount of strong oxidants, acids and other chemical reagents are used in the preparation process, which causes serious environmental pollution. The liquid phase exfoliation method mainly uses ultrasonic exfoliation, that is, ultrasonic exfoliation in organic solvent for a long time. The graphene prepared by this method has few defects, but the use of organic solvent is harmful to human body, and there are problems such as low yield and small size of prepared graphene. The gas phase deposition (CVD) method uses methane and other carbon-containing compounds as raw materials to grow graphene on the surface of metal substrate by high temperature decomposition. CVD method is the main method for preparing graphene film at present. However, the process of CVD method is not mature, and the cost is high, which limits its large-scale application. Therefore, the preparation of graphene is still an important research field in the field of graphene.

[0005] It is of great significance to apply graphene to PGA resin modification and develop a new type of antistatic glass fiber reinforced polyglycolic acid composite material. SUMMARY

[0006] The purpose of the present application is to provide an antistatic glass fiber reinforced polyglycolic acid composite material and its preparation method and application, so as to solve the technical problems of low impact strength of polyglycolic acid forming body, high addition amount of antistatic agent and poor antistatic performance in the prior art.

[0007] The technical scheme adopted by the present application is:

[0008] In a first aspect, the present application provides an antistatic glass fiber reinforced polyglycolic acid composite material, which comprises an inner core material and at least one outer layer material. The inner core material comprises a first polyglycolic acid resin, glass fiber and a first additive, the first additive comprises a first antistatic agent, and the glass fiber continuously extends from one end of the inner core material to the opposite end. The outer layer material wraps the inner core material, and the outer layer material comprises a second polyglycolic acid resin and a second additive, and the second additive comprises a second antistatic agent.

[0009] As a preferred scheme of the composite material provided by the present application, the second antistatic agent is edge-modified graphene.

[0010] Preferably, the average flake diameter of the edge-modified graphene is 2-30 μm, preferably 5-20 μm;

[0011] and / or the average aspect ratio of the edge-modified graphene is 600-10000:1, preferably 800-4500:1, more preferably 1000-3000:1;

[0012] and / or the electrical conductivity of the edge-modified graphene is 200-1000 S / m, preferably 500-1000 S / m;

[0013] and / or the oxygen content in the edge-modified graphene is 0.5wt%-20wt%, preferably 3wt%-10wt%; and / or the hydrogen content is 0.01wt%-1wt%, preferably 0.05wt%-0.5wt%;

[0014] and / or the edge-modified graphene is prepared by grinding graphite under supercritical carbon dioxide.

[0015] As another preferred scheme of the composite material provided by the present application, the first antistatic agent is carbon nanotube.

[0016] Preferably, the purity of the carbon nanotube is greater than 95%;

[0017] and / or the diameter of the carbon nanotube is 10-20 nm;

[0018] and / or the length of the carbon nanotube is 30-100 μm;

[0019] and / or the specific surface area of the carbon nanotube is greater than 165 m 2 / g, preferably 165-500 m 2 / g, more preferably 260-340 m 2 / g;

[0020] and / or the thermal conductivity of the carbon nanotube is not less than 2000 W / mK, preferably 2000-3000 W / mK;

[0021] and / or the electrical conductivity of the carbon nanotube is greater than 1250 s / cm, preferably 1250-3000 s / cm.

[0022] As another preferred embodiment of the composite material provided by the present application, in the inner core material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the glass fiber is 10-200 parts by weight, preferably 10-150 parts by weight, and more preferably 20-150 parts by weight; and / or, the amount of the first polyglycolic acid resin is 100 parts by weight, and the first additive includes 0.1-2 parts by weight of the first antistatic agent;

[0023] and / or, in the outer layer material, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second additive includes 0.01-10 parts by weight of the second antistatic agent; preferably, the second additive includes 0.05-5 parts by weight of the second antistatic agent; and more preferably, the second additive includes 0.1-1 parts by weight of the second antistatic agent;

[0024] and / or, in the composite material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the second polyglycolic acid resin is 1-100 parts by weight, preferably 10-100 parts by weight, and more preferably 50-100 parts by weight.

[0025] As another preferred embodiment of the composite material provided by the present application, the amount of the first polyglycolic acid resin is 100 parts by weight, and the first additive further includes at least one of 0.05-5 parts by weight of the first compatibilizer, 0.1-3 parts by weight of the first antioxidant, and 0.1-1 parts by weight of the first lubricant; preferably, the amount of the first polyglycolic acid resin is 100 parts by weight, and the first additive further includes at least one of 0.05-2 parts by weight of the first compatibilizer, 0.1-1 parts by weight of the first antioxidant, and 0.2-1 parts by weight of the first lubricant;

[0026] and / or, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second additive further includes at least one of 0.05-5 parts by weight of the second compatibilizer, 0.1-3 parts by weight of the second antioxidant, and 0.1-1 parts by weight of the second lubricant; preferably, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second additive further includes at least one of 0.05-2 parts by weight of the second compatibilizer, 0.1-1 parts by weight of the second antioxidant, and 0.2-1 parts by weight of the second lubricant.

[0027] As another preferred embodiment of the composite material provided by the present application, the first compatibilizer and the second compatibilizer are the same or different, and each is independently selected from at least one of a coupling agent, preferably at least one of a silane coupling agent, a titanate coupling agent, and an organic chromium complex coupling agent, and more preferably a silane coupling agent;

[0028] and / or, the first antioxidant and the second antioxidant are the same or different, each independently selected from at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 2246, antioxidant CA and antioxidant 626, preferably at least one of antioxidant 1010, antioxidant 168;

[0029] and / or, the first lubricant and the second lubricant are the same or different, each independently selected from at least one of ethylene bis-stearamide, calcium stearate, monoglyceride fatty acid, polyethylene wax, erucamide, pentaerythritol stearate.

[0030] As another preferred embodiment of the composite material provided by the present application, the first polyglycolic acid resin and the second polyglycolic acid resin are the same or different, each independently selected from homopolymer polyglycolic acid and / or copolymer polyglycolic acid; preferably, the content of glycolic acid monomer in the copolymer polyglycolic acid is ≥ 90 mol%, preferably ≥ 95 mol%;

[0031] and / or, the melt flow rate of the first polyglycolic acid resin at 230°C, 2.16 kg is 5-500 g / 10 min, preferably 10-200 g / 10 min, more preferably 10-150 g / 10 min;

[0032] and / or, the melt flow rate of the second polyglycolic acid resin at 230°C, 2.16 kg is 5-500 g / 10 min, preferably 10-200 g / 10 min, more preferably 10-150 g / 10 min.

[0033] As another preferred embodiment of the composite material provided by the present application, the inner core material does not contain non-oriented short fibers, preferably the inner core material is composed of the first polyglycolic acid resin, glass fibers and the first auxiliary agent.

[0034] In a second aspect, the present application provides a preparation method of the above-mentioned composite material, comprising:

[0035] S1. mixing and melting the first polyglycolic acid resin and the first auxiliary agent to obtain a first component melt;

[0036] S2. performing first impregnation treatment on the continuous glass fibers with the first component melt in step S1 to form a filamentous inner core material;

[0037] S3. mixing and melting the second polyglycolic acid resin and the second auxiliary agent to obtain a second component melt;

[0038] S4. performing at least one second impregnation treatment on the inner core material obtained in step S2 with at least one second component melt obtained in step S3 to obtain the antistatic glass fiber reinforced polyglycolic acid composite material.

[0039] As a preferred scheme of the preparation method provided by the present application, the mixing condition of step S1 is that the temperature is 40-60 DEG C and the time is 3-5 min; and / or the melting temperature of step S1 is 230-260 DEG C.

[0040] And / or, the mixing condition of step S3 is that the temperature is 40-60 DEG C and the time is 3-5 min; and / or the melting temperature of step S3 is 230-260 DEG C.

[0041] And / or, step S2 further comprises: dispersing and preheating the continuous glass fiber before the first impregnation treatment; preferably, the preheating temperature is 80-250 DEG C.

[0042] And / or, step S4 further comprises: after the second impregnation treatment, pulling out, stretching, cooling, drying and cutting the anti-material obtained by the second impregnation treatment.

[0043] As another preferred scheme of the preparation method provided by the present application, the first impregnation treatment in step S2 is carried out in a first impregnation mold, the first impregnation mold is an adjustable impregnation mold, the first impregnation mold comprises a fiber inlet, a fiber outlet and a melt flow channel, at least one first godet is arranged in the mold cavity of the first impregnation mold; the first godet can move between the fiber inlet and the fiber outlet; and / or the first godet can move in a direction perpendicular to the connecting line of the fiber inlet and the fiber outlet.

[0044] As another preferred scheme of the preparation method provided by the present application, the first impregnation treatment in step S2 is carried out in a second impregnation mold, the second impregnation mold is a combined impregnation mold, the second impregnation mold comprises a first module, an intermediate module and a second module connected in sequence, the first module is provided with a fiber inlet and a first module flow channel, the second module is provided with a fiber outlet and a second module flow channel, and the intermediate module is provided with an intermediate module flow channel; after the first module, the intermediate module and the second module are connected in sequence, the first module flow channel, the intermediate module flow channel and the second module flow channel are communicated to form a combined flow channel for the fiber to pass through.

[0045] As another preferred scheme of the preparation method provided by the application, the first impregnation treatment in step S2 is performed in a third impregnation die, the third impregnation die is a strong turbulent flow impregnation die, the third impregnation die comprises a fiber inlet channel, an impregnation outlet and a melt slit runner, and the fiber inlet channel, the impregnation outlet and the melt slit runner are all connected with a die cavity inside the third impregnation die; wherein a second godet is arranged in the die cavity of the third impregnation die, and the second godet comprises at least one driving godet, and the driving godet is driven to rotate by a driving device.

[0046] In a third aspect, the application provides an application of the composite material or the composite material prepared by the preparation method in the fields of catering, building decoration, oil field chemical industry and engineering plastic.

[0047] The application has at least the following beneficial effects:

[0048] (1) The antistatic glass fiber reinforced polyglycolic acid composite material has an inner-outer layer composite structure. The inner core material of the inner layer comprises continuous / constant-length glass fibers, and the flowability of the glass fibers in the matrix melt is improved through impregnation treatment, so that the high-content glass fibers are uniformly dispersed in the polyglycolic acid, and the bending, heat resistance and impact performance of the polyglycolic acid are greatly enhanced. Then the outer layer material is used to coat the inner core material, so that the comprehensive performance and surface quality of the composite material can be further strengthened.

[0049] (2) The sheet layer integrity of the edge-modified graphene added in the outer layer material of the antistatic glass fiber reinforced polyglycolic acid composite material is good, and a good conductive network is easily formed. As an antistatic agent of the polyglycolic acid composite material, the edge-modified graphene can achieve better antistatic effect with a lower addition amount than conventional antistatic agents.

[0050] (3) The carbon nanotubes added in the inner core material of the antistatic glass fiber reinforced polyglycolic acid composite material and the edge-modified graphene added in the outer layer material form an interpenetrating network structure, which effectively conducts the charge of the composite material and significantly reduces the surface resistivity and volume resistivity of the composite material. Compared with traditional organic exudation antistatic agents, the antistatic agent system is a long-acting antistatic agent, and the antistatic performance decreases by not more than 5% after 6 months of use.

[0051] (4) The antistatic glass fiber reinforced polyglycolic acid composite material also has the advantages of low cost, simple preparation process, dimensional stability, good surface quality and biodegradability. BRIEF DESCRIPTION OF DRAWINGS

[0052] Figure 1 FIG. 1 is a structural schematic diagram of the antistatic glass fiber reinforced polyglycolic acid composite material in an embodiment of the application;

[0053] Figure 2 A schematic diagram of a system for manufacturing an antistatic glass fiber reinforced polyglycolic acid composite material according to an embodiment of the present application;

[0054] Figure 3 A schematic diagram of a system for manufacturing an antistatic glass fiber reinforced polyglycolic acid composite material according to another embodiment of the present application;

[0055] Figure 4 A sectional view of a first impregnation die according to an embodiment of the present application;

[0056] Figure 5 A sectional view of a second impregnation die according to an embodiment of the present application;

[0057] Figure 6 A sectional view of a third impregnation die according to an embodiment of the present application;

[0058] Figure 7 A schematic diagram of a second impregnation process according to an embodiment of the present application;

[0059] Figure 8 A sectional view of a molding die used in a second impregnation process according to an embodiment of the present application.

[0060] Explanation of Reference Numerals:

[0061] 0-1, core material; 0-2, fiber bundle; 0-3, outer layer material;

[0062] 1, fiber stand and fiber guide device; 2, fiber pretreatment device; 3, first impregnation die; 4, molten plasticizing supply device; 5, molding die; 6, cooling water tank; 7, drying machine; 8, puller; 9, pelletizer; 10, collection box;

[0063] A300, first impregnation die die head; A1, fiber inlet; A2, second chute; A3, melt runner; A4, first chute; A5, upper die cover; A6, fiber outlet; A7, impregnation die body; A8, first godet;

[0064] B300, second impregnation die die head; B1, fiber inlet; B2, melt runner; B3, first module; B31, first module runner; B4, combined runner; B5, standardization joint; B6, intermediate module; B61, intermediate module runner; B7, second module; B71, second module runner; B8, fiber outlet;

[0065] C300, third impregnation die die head; C1, melt split runner; C2, impregnation die outer body; C3, fiber inlet passage; C4, driving godet; C5, driven godet; C6, impregnation outlet;

[0066] 4-1, extruder I; 4-2, extruder II;

[0067] 5-1, core; 5-2, sheath; 5-3, sheath die plate; 5-4, strand; 5-5, second resin inlet. DETAILED DESCRIPTION

[0068] In order to make the technical problems to be solved by the present application, technical solutions and beneficial effects more clearly understood, the present application will be further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to specifically illustrate the present patent and do not limit the protection scope of the present application in any way.

[0069] The anti-static glass fiber reinforced polyglycolic acid composite material provided by the present application comprises an inner core material and at least one outer layer material; the inner core material comprises a first polyglycolic acid resin, glass fibers and a first additive, the first additive comprises a first anti-static agent, the glass fibers continuously extend from one end of the inner core material to the opposite end; the outer layer material wraps the inner core material, and the outer layer material comprises a second polyglycolic acid resin and a second additive, the second additive comprises a second anti-static agent.

[0070] The present inventors have found that by impregnating continuous glass fibers with a first component comprising a first polyglycolic acid resin and a first additive to form an inner core material, and uniformly coating a second component comprising a second polyglycolic acid resin and a second additive on the outer side of the inner core material, an anti-static glass fiber reinforced polyglycolic acid composite material is formed, which has an inner core material of continuous glass fiber reinforced resin and an outer layer material of resin layer wrapped on the outer side of the inner core material. Such a polyglycolic acid composite material has excellent mechanical properties; at the same time, by adding an anti-static agent in the inner core material and the outer layer material, the polyglycolic acid composite material has excellent anti-static properties, and a degradable composite material applicable in application scenarios with high requirements for anti-static and impact strength is prepared.

[0071] In the present application, the terms "one end" and "opposite end" are generally relative to the longitudinal direction of the anti-static glass fiber reinforced polyglycolic acid composite material.

[0072] In the transverse cross-section of the anti-static glass fiber reinforced polyglycolic acid composite material, the inner core material and the outer layer material are sequentially arranged from inside to outside, and the glass fibers are oriented along the longitudinal direction of the anti-static glass fiber reinforced polyglycolic acid composite material in the inner core material.

[0073] The glass fibers in the present application are glass fiber bundles, and the length of the fiber bundle is substantially the same as the length (longitudinal dimension) of the anti-static glass fiber reinforced polyglycolic acid composite material, so that the fiber bundle continuously extends from one end to the opposite end in the longitudinal direction of the inner core material. The inner core material does not contain short fibers, especially non-oriented short fibers.

[0074] In the anti-static glass fiber reinforced polyglycolic acid composite of the present application, the outer layer material at least 80% covers the inner core material, for example, 80-99%, 85-95% covers the inner core material; the outer layer material can also continuously cover the inner core material.

[0075] The outer layer material is not limited in number of layers, and can be one layer or multiple layers. In some embodiments, the multiple layers of outer layer material can be formed of the same material or multiple materials.

[0076] The glass fiber is continuous and / or fixed-length glass fiber.

[0077] According to some embodiments of the present application, the second anti-static agent is edge-modified graphene.

[0078] According to some embodiments of the present application, the average flake size of the edge-modified graphene is 2-30 μm, preferably 5-20 μm.

[0079] According to some embodiments of the present application, the average aspect ratio of the edge-modified graphene is 600-10000:1, preferably 800-4500:1, and more preferably 1000-3000:1.

[0080] In the present application, the "aspect ratio" refers to the ratio of the long side (flake size) of graphene and the thickness.

[0081] According to some embodiments of the present application, the electrical conductivity of the edge-modified graphene is 200-1000 S / m, preferably 500-1000 S / m.

[0082] According to some embodiments of the present application, the edge-modified graphene is edge-carboxyl-modified graphene.

[0083] According to some embodiments of the present application, in the edge-modified graphene, the oxygen element content is 0.5wt%-20wt%, preferably 3wt%-10wt%; and / or the hydrogen element content is 0.01wt%-1wt%, preferably 0.05wt%-0.5wt%.

[0084] The flake size of the edge-modified graphene in the present application is in the micron level, has adjustable aspect ratio and carbon and oxygen element content, has higher electrical conductivity, and can be significantly distinguished from the existing nanoscale graphene, and can overcome the problem of easy aggregation of nanoscale graphene.

[0085] According to some embodiments of the present application, the edge-modified graphene is prepared by grinding graphite with a grinding disc under supercritical carbon dioxide.

[0086] Under supercritical carbon dioxide condition, the properties of carbon dioxide change greatly, the density is close to liquid, the viscosity is close to gas, and the diffusion coefficient is 100 times of liquid. Under this condition, carbon dioxide inserts into graphite layers, reduces the π-π interaction between graphite layers, and when it is sheared by the grinding disc, graphite is exfoliated into graphene; meanwhile, the grinding disc shearing also breaks graphite or graphene, and the newly generated high-activity edge reacts with carbon dioxide, resulting in modification of carboxyl groups on the edge of graphene. Compared with the ordinary ball milling method, this method can prepare edge-carboxylated graphene without grinding graphite to a particularly fine size, while the ordinary ball milling method must grind graphite to a nanoscale, otherwise graphene cannot be prepared.

[0087] According to a specific embodiment of the present application, the preparation method of the edge-modified graphene comprises:

[0088] S1. adding purified or un-purified graphite powder into a high-pressure grinding disc kettle;

[0089] S2. passing carbon dioxide into the high-pressure grinding disc kettle and making it in a supercritical state to form a material containing graphite powder and supercritical carbon dioxide;

[0090] S3. grinding the material containing graphite powder and supercritical carbon dioxide.

[0091] According to some embodiments of the present application, the graphite powder is selected from flake graphite powder and expanded graphite powder.

[0092] According to some embodiments of the present application, the particle size of the graphite powder is 10-80 mesh, preferably 20-60 mesh.

[0093] According to some embodiments of the present application, the graphite powder is preferably pre-treated before grinding, for example, by ultrasonic cleaning and / or chemical treatment, to remove impurities such as impurity elements and impurity substances.

[0094] According to some embodiments of the present application, in step S2, carbon dioxide is made into a supercritical state by making the temperature in the kettle exceed 32.26℃ and the pressure exceed 72.9atm.

[0095] According to some embodiments of the present application, the weight ratio of graphite powder to carbon dioxide is 1:5-1:40, preferably 1:5-1:25.

[0096] According to some embodiments of the present application, in step S3, after grinding is completed, the pressure in the high-pressure grinding disc kettle is rapidly reduced; preferably, the pressure in the high-pressure grinding disc kettle is reduced to below 1atm within 5-20 seconds.

[0097] According to some embodiments of the present application, the temperature in the high-pressure attrition disc reactor is 35-200℃, preferably 35-100℃, and more preferably 35-70℃.

[0098] According to some embodiments of the present application, the pressure in the high-pressure attrition disc reactor is 50-165atm, preferably 75-150atm, and more preferably 75-125atm.

[0099] According to some embodiments of the present application, the rotation speed of the attrition disc in the high-pressure attrition disc reactor is 500-10000r / min, preferably 500-5000r / min.

[0100] According to some embodiments of the present application, the grinding time is 6-48 hours.

[0101] In the present application, the high-pressure attrition disc reactor is used to mix graphite and supercritical carbon dioxide sufficiently, and to grind and exfoliate the graphite.

[0102] The edge-modified graphene prepared by the above method has good sheet integrity, and can easily form a good conductive network. When used as an antistatic agent, the edge-modified graphene can achieve a better antistatic effect with a lower addition amount than conventional antistatic agents. Furthermore, the polyglycolic acid composite material with the edge-modified graphene as an antistatic agent in the outer layer is a non-crosslinked structure, and can be naturally degraded like pure polyglycolic acid resin.

[0103] According to some embodiments of the present application, the first antistatic agent is carbon nanotubes.

[0104] According to some embodiments of the present application, the purity of the carbon nanotubes is greater than 95%.

[0105] According to some embodiments of the present application, the diameter of the carbon nanotubes is 10-20nm.

[0106] According to some embodiments of the present application, the length of the carbon nanotubes is 30-100μm.

[0107] According to some embodiments of the present application, the specific surface area of the carbon nanotubes is greater than 165m 2 / g, preferably 165-500m 2 / g, and more preferably 260-340m 2 / g.

[0108] According to some embodiments of the present application, the thermal conductivity of the carbon nanotubes is not less than 2000W / mK, and preferably 2000-3000W / mK.

[0109] According to some embodiments of the present application, the carbon nanotubes have an electrical conductivity greater than 1250 s / cm, preferably between 1250 s / cm and 3000 s / cm.

[0110] In the present application, the carbon nanotubes can be prepared by a vapor deposition method, an arc discharge method, or a fluidized bed method, and are preferably oriented multi-walled carbon nanotubes prepared by a vapor deposition method.

[0111] According to some embodiments of the present application, in the inner core material, the amount of glass fiber is 10-200 parts by weight based on 100 parts by weight of the first polyglycolic acid resin, for example, 10 parts by weight, 20 parts by weight, 30 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, etc. Preferably, the amount of glass fiber is 10-150 parts by weight, and more preferably, the amount of glass fiber is 20-150 parts by weight.

[0112] According to some embodiments of the present application, in the inner core material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the first auxiliary agent includes 0.1-2 parts by weight of the first antistatic agent, for example, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 1 parts by weight, 1.5 parts by weight, 2 parts by weight, etc.

[0113] According to some embodiments of the present application, in the outer layer material, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second auxiliary agent includes 0.01-10 parts by weight of the second antistatic agent, for example, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 1 parts by weight, 1.5 parts by weight, 2 parts by weight, 5 parts by weight, 10 parts by weight, etc. Preferably, the second auxiliary agent includes 0.05-5 parts by weight of the second antistatic agent, and more preferably, the second auxiliary agent includes 0.1-1 parts by weight of the second antistatic agent.

[0114] According to some embodiments of the present application, in the composite material, the amount of the second polyglycolic acid resin is 1-100 parts by weight based on 100 parts by weight of the first polyglycolic acid resin, for example, 1 parts by weight, 10 parts by weight, 30 parts by weight, 50 parts by weight, 60 parts by weight, 80 parts by weight, 100 parts by weight, etc. Preferably, the amount of the second polyglycolic acid resin is 10-100 parts by weight, and more preferably, the amount of the second polyglycolic acid resin is 50-100 parts by weight.

[0115] According to some embodiments of the present application, the first polyglycolic acid resin is used in an amount of 100 parts by weight, and the first auxiliary agent further comprises at least one of 0.05-5 parts by weight of a first compatibilizer, 0.1-3 parts by weight of a first antioxidant, and 0.1-1 part by weight of a first lubricant. For example, the first compatibilizer can be used in an amount of 0.05 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 1 parts by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, etc.; and / or the first antioxidant can be used in an amount of 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 1 parts by weight, 2 parts by weight, 3 parts by weight, etc.; and / or the first lubricant can be used in an amount of 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, etc.

[0116] Preferably, the first polyglycolic acid resin is used in an amount of 100 parts by weight, and the first auxiliary agent further comprises at least one of 0.05-2 parts by weight of a first compatibilizer, 0.1-1 parts by weight of a first antioxidant, and 0.2-1 part by weight of a first lubricant.

[0117] According to some embodiments of the present application, the second polyglycolic acid resin is used in an amount of 100 parts by weight, and the second auxiliary agent further comprises at least one of 0.05-5 parts by weight of a second compatibilizer, 0.1-3 parts by weight of a second antioxidant, and 0.1-1 part by weight of a second lubricant. For example, the second compatibilizer can be used in an amount of 0.05 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 1 parts by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, etc.; and / or the second antioxidant can be used in an amount of 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 1 parts by weight, 2 parts by weight, 3 parts by weight, etc.; and / or the second lubricant can be used in an amount of 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, etc.

[0118] Preferably, the second polyglycolic acid resin is used in an amount of 100 parts by weight, and the second auxiliary agent further comprises at least one of 0.05-2 parts by weight of a second compatibilizer, 0.1-1 parts by weight of a second antioxidant, and 0.2-1 part by weight of a second lubricant.

[0119] According to some embodiments of the present application, the first compatibilizer and the second compatibilizer are the same or different, and each is independently selected from at least one of a coupling agent, preferably at least one of a silane coupling agent, a titanate coupling agent, an organic chromium complex coupling agent, more preferably a silane coupling agent. Examples of silane coupling agents suitable for use in the present application include, but are not limited to: KH-550, KH-560.

[0120] According to some embodiments of the present application, the first antioxidant and the second antioxidant are the same or different, and each is independently selected from at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 2246, antioxidant CA, and antioxidant 626, preferably at least one of antioxidant 1010 and antioxidant 168.

[0121] According to some embodiments of the present application, the first lubricant and the second lubricant are the same or different, and each is independently selected from at least one of ethylene bis-stearamide, calcium stearate, monoglyceride fatty acid, polyethylene wax, erucamide, pentaerythritol stearate.

[0122] In different embodiments of the present application, the first additive and the second additive are not particularly limited in the specific type and amount of the several additives, and each can have a wide range of selection. For example, the first additive and the second additive each can further include at least one of a chain extender, a slip agent, and a plasticizer.

[0123] According to some embodiments of the present application, the first polyglycolic acid resin and the second polyglycolic acid resin are the same or different, and each is independently selected from a homopolymer polyglycolic acid and / or a copolymer polyglycolic acid; preferably, the content of glycolic acid monomer in the copolymer polyglycolic acid is ≥ 90 mol%, preferably ≥ 95 mol%.

[0124] In the present application, the comonomer of the copolymer polyglycolic acid can include: cyclic monomers such as 1,4-dioxane-2,3-dione, lactide, lactone (e.g., pivalolactone, butyro lactone, pivalolactone, butyrolactone, 8-valerolactone, ethyl 8-valerolactone, E-caprolactone), carbonate (e.g., trimethylene carbonate), ether (e.g., 1,3-dioxane), ether ester (e.g., dioxanone), amide (e.g., E-caprolactam), lactic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, and 6-hydroxyhexanoic acid, and alkyl esters of hydroxycarboxylic acids; substantially equimolar mixtures of aliphatic diols (e.g., ethylene glycol and 1,4-butanediol) and aliphatic dicarboxylic acids (e.g., succinic acid and adipic acid) or alkyl esters thereof; and combinations of two or more of the above.

[0125] The synthesis method of polyglycolic acid can be selected from glycolic acid liquid phase polycondensation, glycolic acid solid phase polycondensation, glycolic acid melt polycondensation, or glycolide ring-opening polymerization; preferably, glycolide ring-opening polymerization. The raw material of glycolide can be obtained by a coal chemical method.

[0126] In different embodiments of the present application, the melt flow rate of the first polyglycolic acid resin and the second polyglycolic acid resin is not particularly limited, and the melt flow rate of the first polyglycolic acid resin and the second polyglycolic acid resin can be selected according to the desired performance.

[0127] In particular, the present inventors have found that the parameters according to the present application (e.g. melt flow rate) can be used to prepare polyglycolic acid composite materials having both high surface quality and comprehensive performance. For example, the melt flow rate of the first polyglycolic acid resin is higher than that of the second polyglycolic acid resin, so that the polyglycolic acid composite material has improved mechanical properties; conversely, the melt flow rate of the second polyglycolic acid resin is higher than that of the first polyglycolic acid resin, so that the polyglycolic acid composite material has improved gloss.

[0128] According to some embodiments of the present application, the melt flow rate of the first polyglycolic acid resin at 230°C, 2.16 kg is 5-500 g / 10 min, for example, it can be 5 g / 10 min, 10 g / 10 min, 20 g / 10 min, 40 g / 10 min, 50 g / 10 min, 80 g / 10 min, 100 g / 10 min, 150 g / 10 min, 200 g / 10 min, 300 g / 10 min, 400 g / 10 min, 500 g / 10 min, etc. Preferably, it is 10-200 g / 10 min, more preferably, it is 10-150 g / 10 min.

[0129] According to some embodiments of the present application, the melt flow rate of the second polyglycolic acid resin at 230°C, 2.16 kg is 5-500 g / 10 min, for example, it can be 5 g / 10 min, 10 g / 10 min, 20 g / 10 min, 40 g / 10 min, 50 g / 10 min, 80 g / 10 min, 100 g / 10 min, 150 g / 10 min, 200 g / 10 min, 300 g / 10 min, 400 g / 10 min, 500 g / 10 min, etc. Preferably, it is 10-200 g / 10 min, more preferably, it is 10-150 g / 10 min.

[0130] According to some embodiments of the present application, the composite material is in the form of a strip, a rod or a particle.

[0131] In the present application, the strip-shaped, rod-shaped or particle-shaped antistatic glass fiber reinforced polyglycolic acid composite material can be cut from a continuous filament-shaped antistatic glass fiber reinforced polyglycolic acid composite material.

[0132] Further preferably, the length of the strip-shaped or rod-shaped composite material is 6-25 mm, for example, it can be 6 mm, 8 mm, 10 mm, 12 mm, 15 mm, 20 mm, 22 mm, 25 mm, etc. Preferably, it is 8-20 mm, more preferably, it is 10-15 mm; the particle size of the particle-shaped composite material is 3-5 mm, for example, it can be 3 mm, 4 mm, 5 mm, etc. Preferably, it is 3-4 mm.

[0133] The present application does not have special requirements for the cross-sectional shape of the antistatic glass fiber reinforced polyglycolic acid composite material. In some embodiments, the cross-section of the granular or rod-shaped antistatic glass fiber reinforced polyglycolic acid composite material is circular or circular-like. In other embodiments, the cross-section of the granular or rod-shaped antistatic glass fiber reinforced polyglycolic acid composite material is rectangular or square.

[0134] In a second aspect, the present application provides a method for preparing an antistatic glass fiber reinforced polyglycolic acid composite material, comprising:

[0135] S1. mixing and melting the first polyglycolic acid resin and the first auxiliary agent to obtain a first component melt;

[0136] S2. performing a first impregnation treatment on the continuous glass fiber with the first component melt in step S1 to form a filamentous inner core material;

[0137] S3. mixing and melting the second polyglycolic acid resin and the second auxiliary agent to obtain a second component melt;

[0138] S4. performing at least one second impregnation treatment on the inner core material obtained in step S2 with at least one second component melt obtained in step S3 to obtain the antistatic glass fiber reinforced polyglycolic acid composite material.

[0139] The preparation method of the present application can be carried out continuously in line to obtain a continuous filamentous product. Such a continuous filamentous product can be directly stored and used, or can be cut into a strip-shaped, rod-shaped or granular product with a certain length or particle size.

[0140] According to some embodiments of the present application, the mixing conditions of step S1 are: temperature 40-60℃, time 3-5min; and / or the melting temperature of step S1 is 230-260℃.

[0141] According to some embodiments of the present application, the mixing conditions of step S3 are: temperature 40-60℃, time 3-5min; and / or the melting temperature of step S3 is 230-260℃.

[0142] In the present application, the melting time of steps S1 and S3 can have a relatively wide selection range, in order to enable the first polyglycolic acid resin and the first auxiliary agent, and the second polyglycolic acid resin and the second auxiliary agent to be fully melted to obtain a melt.

[0143] According to some embodiments of the present application, the step S2 further comprises: before the first impregnation treatment of the continuous glass fiber, dispersing and preheating the continuous glass fiber; preferably, the preheating temperature is 80-250℃. The dispersing process in the present application adopts the conventional glass fiber dispersing process in the art.

[0144] According to some embodiments of the present application, the step S4 further comprises: after the second impregnation treatment, drawing out, stretching, cooling, drying and granulating the material obtained after the second impregnation treatment to obtain the antistatic glass fiber reinforced polyglycolic acid composite material. The process conditions of the drawing out, stretching, cooling, drying and granulating are not particularly limited, and can be adjusted by those skilled in the art according to the specific performance requirements of the antistatic glass fiber reinforced polyglycolic acid composite material to be prepared.

[0145] According to some embodiments of the present application, the first impregnation treatment in step S2 can be carried out in a first impregnation mold, the first impregnation mold being an adjustable impregnation mold, the first impregnation mold comprising a fiber inlet, a fiber outlet and a melt flow channel, at least one first godet being arranged in the mold cavity of the first impregnation mold; the first godet can move between the fiber inlet and the fiber outlet; and / or the first godet can move in a direction perpendicular to the connecting line of the fiber inlet and the fiber outlet.

[0146] According to some embodiments of the present application, the first impregnation treatment in step S2 can be carried out in a second impregnation mold, the second impregnation mold being a combined impregnation mold, the second impregnation mold comprising a first module, an intermediate module and a second module connected in sequence, the first module being provided with a fiber inlet and a first module flow channel, the second module being provided with a fiber outlet and a second module flow channel, the intermediate module being provided with an intermediate module flow channel; after the first module, the intermediate module and the second module are connected in sequence, the first module flow channel, the intermediate module flow channel and the second module flow channel are connected to form a combined flow channel for the fiber to pass through.

[0147] According to some embodiments of the present application, the first impregnation treatment in step S2 can also be carried out in a third impregnation mold, the third impregnation mold being a strong turbulence impregnation mold, the third impregnation mold comprising a fiber inlet channel, an impregnation outlet and a melt slit flow channel, all of which are connected to the mold cavity inside the third impregnation mold; wherein the second godet is arranged in the mold cavity of the third impregnation mold, the second godet comprising at least one driven godet, the driven godet being driven to rotate by a driving device.

[0148] The first impregnation mold, the second impregnation mold and the third impregnation mold used in the present application are described in Chinese patent applications CN202011193483.3, 202011191450.5 and 202011199839.4, which are incorporated herein by reference in their entirety.

[0149] It should be noted that the first impregnation mold, the second impregnation mold and the third impregnation mold described above can be applied to any existing manufacturing system and preparation technology of antistatic glass fiber reinforced polyglycolic acid composite material.

[0150] According to some embodiments of the preparation method of the present application, the second impregnation treatment in step S4 can be carried out in a forming mold. The forming mold is composed of a core, a sleeve and a sleeve die plate. The core is located inside the sleeve to form a forming cavity with the sleeve, and the resin melt can enter the cavity from the bottom or top or both sides of the sleeve. The core can move forward and backward in the sleeve, and the pressure of the melt in the cavity can be determined by adjusting the size of the cavity space formed. The pressure of the melt in the cavity can also be adjusted by the angle between the core and the sleeve. The working principle of the forming mold is as follows: the strip formed after the impregnation mold is guided to pass through the hole in the middle of the core, and then the inner and outer layer material composite structure is formed in the cavity filled with mixed melt formed by the core and the sleeve, and finally it is discharged through the sleeve die plate.

[0151] The present application will be further described below with reference to the accompanying drawings.

[0152] Figure 1 The structure of the antistatic glass fiber reinforced polyglycolic acid composite material of the present application is shown. As shown in Figure 1 The cross section of the antistatic glass fiber reinforced polyglycolic acid composite material of the present application is circular, and sequentially includes an inner core material 0-1 and an outer layer material 0-3 from inside to outside, the inner core material 0-1 has fiber bundles 0-2 oriented in the longitudinal direction distributed therein, and the fiber bundles 0-2 are uniformly dispersed in the inner core material 0-1.

[0153] As shown in Figure 2 and Figure 3 The manufacturing system of the present application includes a fiber rack and fiber guiding device 1, a fiber pretreatment device 2, a first impregnation mold 3, a molten plasticizing feeding device 4, a forming mold 5, a cooling water tank 6, a drying machine 7, a traction machine 8, a granulator 9, a collection box 10 and an electric control system (not shown in the figure) connected in sequence.

[0154] In the manufacturing system, the forming mold 5 is used for the forming of the antistatic glass fiber reinforced polyglycolic acid composite material, and its structure is shown in Figure 8 .

[0155] In the manufacturing system, the first impregnation die 3 is used for impregnation of the fiber with the first polyglycolic acid resin melt.

[0156] As shown in Figure 4 one embodiment, the first impregnation die is an impregnation device capable of adjusting the position of the godet, which includes a first impregnation die head A300, the first impregnation die head A300 including an impregnation die body A7, a fiber inlet A1, a fiber outlet A6, and a melt flow channel A3. At least one first godet A8 is provided in the die cavity, wherein the first godet A8 is movable between the fiber inlet A1 and the fiber outlet A6, or the first godet A8 is movable in a direction perpendicular to the line connecting the fiber inlet A1 and the fiber outlet A6, or the first godet A8 is movable both between the fiber inlet A1 and the fiber outlet A6 and in a direction perpendicular to the line connecting the fiber inlet A1 and the fiber outlet A6.

[0157] Taking a rectangular first impregnation die head A300 as an example, a plurality of first godets A8 are provided in the first impregnation die head A300, and the axial direction of each first godet A8 is the width direction of the first impregnation die head A300. Therefore, each first godet A8 is movable in the length direction of the first impregnation die head A300 and is also movable in the height direction, so as to change the position of the first godet A8 in the first impregnation die head A300.

[0158] It can be understood that the axial direction of the first godet A8 can also be the length direction of the first impregnation die head A300. At this time, each first godet A8 is movable in the width direction of the first impregnation die head A300 and is also movable in the height direction of the first impregnation die head A300, so as to change the position of the first godet A8 in the first impregnation die head A300.

[0159] Since the fiber needs to pass around the first godet A8 in the die cavity when it travels in the die cavity of the first impregnation die head A300, by changing the position (horizontal position, longitudinal position, etc.) of the first godet A8 in the first impregnation die head A300, the travel path of the fiber in the die cavity can be changed. Therefore, when the required impregnation conditions of the fiber change, it is not necessary to replace a new die, but only to adjust the position of the first godet A8 in the first impregnation die head A300, thereby improving the production efficiency and the continuity of production. At the same time, the number of first impregnation die heads A300 can be reduced, and the production cost can be saved.

[0160] Specifically, the present application is to achieve the purpose of adjusting the position of the first godet A8 by slotting the inner wall of the die cavity of the first impregnation die head A300.

[0161] A first sliding groove A4 is arranged on the first inner wall of the first impregnation die head A300, and the first sliding groove A4 extends between the fiber inlet A1 and the fiber outlet A6 (i.e. in the X-axis direction as shown in the figure), and the first godet A8 moves along the first sliding groove A4 to change its horizontal position in the first impregnation die head A300. Figure 4 Further, a second sliding groove A2 is arranged on the first inner wall of the first impregnation die head A300, and the second sliding groove A2 extends in a direction perpendicular to the first sliding groove A4 (i.e. in the Y-axis direction as shown in the figure), and the first godet A8 moves along the second sliding groove A2 to change its vertical position in the die head.

[0162] Further, a second sliding groove A2 is arranged on the first inner wall of the first impregnation die head A300, and the second sliding groove A2 extends in a direction perpendicular to the first sliding groove A4 (i.e. in the Y-axis direction as shown in the figure), and the first godet A8 moves along the second sliding groove A2 to change its vertical position in the die head. Figure 4 Further, a second sliding groove A2 is arranged on the first inner wall of the first impregnation die head A300, and the second sliding groove A2 extends in a direction perpendicular to the first sliding groove A4 (i.e. in the Y-axis direction as shown in the figure), and the first godet A8 moves along the second sliding groove A2 to change its vertical position in the die head.

[0163] It should be noted that the first sliding groove A4 and the second sliding groove A2 can be connected. Thus, the first godet A8 can be arbitrarily moved in the longitudinal direction or the transverse direction, so that its position is changed.

[0164] The cross section of the first sliding groove A4 and the second sliding groove A2 can be trapezoidal, circular, arc-shaped or rectangular, and the present application does not limit the shape.

[0165] Both ends of the first godet A8 are provided with adjusting devices (not shown in the figure), and the adjusting devices are used to adjust the axial length of the first godet A8. The minimum axial length of the first godet A8 is smaller than the distance between the first inner wall and the second inner wall, and the maximum axial length of the first godet A8 is greater than the distance between the first inner wall and the second inner wall.

[0166] As shown in the figure, in another embodiment of the present application, the second impregnation die is a combined impregnation die, which comprises a second impregnation die head B300, and the second impregnation die head B300 comprises a first module B3, an intermediate module B6 and a second module B7 connected in sequence. The first module B3 is provided with a fiber inlet B1 and a first module flow channel B31, the second module B7 is provided with a fiber outlet B8 and a second module flow channel B71, and the intermediate module B6 is provided with an intermediate module flow channel B61. Figure 5 After the first module B3, the intermediate module B6 and the second module B7 are connected in sequence, the first module flow channel B31, the intermediate module flow channel B61 and the second module flow channel B71 are connected to form a combined flow channel B4 for the fiber to pass through, and the number of the intermediate module B6 is at least one. That is, the first module B3 is the first module, the second module B7 is the last module, and there is one or more intermediate modules B6 between the two. It should be noted that these intermediate modules B6 are also connected in sequence.

[0167]

[0168] ​That is, the number of intermediate modules B6 can be increased or decreased as required, so that different intermediate modules B6 are combined to form the combined second impregnation die B300 when the impregnation requirements change, thereby improving the continuity and efficiency of production and saving the cost of additional die opening.

[0169] Furthermore, by selecting different intermediate modules B6, the shape parameters (such as curvature, etc.) of the combined flow channel B4 formed can be changed, so that the flow path of the fiber and the melt can be changed, the fiber impregnation angle and fiber tension in different stations of the die can be changed, the entire fiber impregnation process can be adjusted and optimized, and the adaptability of the second impregnation die B300 to polyglycolic acid resin and fiber is improved.

[0170] The above-mentioned first module B3, intermediate module B6 and second module B7 are placed in the die holder, and the die holder constrains them to be in close contact with each other, thereby ensuring the sealing of the combined flow channel B4 formed.

[0171] As shown in Figure 5 , an embodiment with 2 intermediate modules B6 is shown. In the embodiment shown in Figure 5 , the downstream end of the first module flow channel B31 is connected to the upstream end of one of the intermediate module flow channels B61, the two intermediate module flow channels B61 are connected to each other, and the downstream end of the other intermediate module flow channel B61 is connected to the upstream end of the second intermediate module flow channel B71, thereby forming a combined flow channel B4 extending from the fiber inlet B1 to the fiber outlet B8.

[0172] It can be understood that by selecting different intermediate modules B6, different combined flow channels B4 can be obtained.

[0173] As shown in Figure 5 , the downstream end of the first module flow channel B31, the upstream end of the second module flow channel B71 and the two ends of the intermediate module flow channel B61 are located in the same plane and are provided with standardized joints B5. In other words, the connection between the first module flow channel B31, the intermediate module flow channel B61 and the second module B71 is connected by the standardized joints B5. Since the standardized joints B5 are located in the same plane and have the same shape and size, the combination and connection between different modules are facilitated.

[0174] As shown in Figure 6As shown, in still another embodiment of the present application, the third impregnation die is a strong turbulent impregnation die, which comprises a third impregnation die head C300, the third impregnation die head C300 comprises an impregnation die outer body C2, the impregnation die outer body C2 is provided with a fiber inlet channel C3, an impregnation outlet C6 and a melt slit runner C1, the fiber inlet channel C3, the impregnation outlet C6 and the melt slit runner C1 are all connected with the die cavity inside the impregnation die outer body C2.

[0175] The second godet roller comprises at least one driving godet roller C4, the driving godet roller C4 is driven to rotate by a driving device (not shown in the figure). Since the rotation of the driving godet roller C4 is driven by the driving device rather than being driven by the traction of the fiber, when the fiber passes through the driving godet roller C4, the driving rotation of the driving godet roller C4 helps to reduce the traction tension of the fiber and the friction between the fiber and the driving godet roller C4, thereby reducing the breaking amount of the fiber, ensuring the integrity of the fiber, avoiding the situation that the fiber is pulled off, and thus improving the mechanical properties of the material.

[0176] Preferably, the second godet roller further comprises at least one driven godet roller C5, the driven godet roller C5 is driven by the fiber passing through the driving godet roller C4; or the driven godet roller C5 is connected with the driving godet roller C4 through a belt mechanism, a gear mechanism or a chain mechanism.

[0177] As shown in the figure, Figure 6 The driving godet roller C4 and the driven godet roller C5 can have the same height in the die cavity or different heights.

[0178] Further, the driving device can be a motor, a hydraulic mechanism or a reduction box and the like which can drive the driving godet roller C4 to rotate.

[0179] According to the running speed v1 of the fiber entering the die cavity of the impregnation die outer body C2, the corresponding tangential speed v2 of the driving godet roller C4 can be selected, for example, the tangential speed v2 of the driving godet roller C4 is the same as the running speed v1 of the fiber, i.e. v1=v2, so as to achieve the purpose of reducing the breaking and wear of the fiber, thus ensuring the integrity of the fiber and promoting the impregnation degree of the fiber, shortening the impregnation time and improving the production efficiency.

[0180] As shown in the figure, Figure 2As shown, the melt plasticizing feeding device 4 consists of a twin-screw extruder used for melting and plasticizing materials. The twin-screw extruder is a co-rotating twin-screw extruder with a screw diameter of 25mm-95mm and a length-to-diameter ratio of 36:1-65:1. When the melt plasticizing feeding device 4 consists of a single extruder 4, the melt plasticizing material in the extruder is divided by a melt distributor and fed into the impregnation die and the forming die respectively, and the flow rate of each die is controlled by a melt flow control valve.

[0181] like Figure 3 As shown, when the melt plasticizing feeding device 4 consists of two extruders 4-1 and 4-2, the molten plasticized melts from extruder I 4-1 and extruder II 4-2 are respectively fed into the impregnation mold and the forming mold. In this embodiment, the melt plasticizing feeding device consists of two extruders I 4-1 and extruder II 4-2, and the molten plasticized melts from extruder I 4-1 and extruder II 4-2 are respectively fed into the first impregnation mold 3 and the forming mold 5. Extruder I 4-1 and extruder II 4-2 can be fed with the same or different materials, thus enabling the preparation of composite materials with the same or different materials for the inner and outer layers.

[0182] The fiber pretreatment device 2 consists of a tension roller and a hot drying tunnel. This combination allows for some release of tension on the fibers as they enter the hot drying tunnel, thus accommodating fibers of different strengths and preventing fibers with lower strength from breaking before entering the impregnation die. The surface of the tension roller in the fiber pretreatment device 2 needs to be ceramic-coated to increase surface roughness and reduce friction on the fibers.

[0183] In the manufacturing system, the fiber frame and fiber guiding device 1 are used for fiber output and untwisting. The device is equipped with an automatic control untwisting device, which is linked with the traction machine 8 and electrically connected to the electrical control system (such as a PLC control device).

[0184] In the manufacturing system, the cooling water tank 6, dryer 7, traction machine 8, pelletizer 9, and collection box 10 are conventional equipment or devices known to those skilled in the art, and will not be described in detail here.

[0185] Figure 7 A schematic diagram showing the second impregnation process using a molding die is shown. Figure 8 A cross-sectional view of the molding die used in the second impregnation process is shown.

[0186] like Figure 8As shown, in one embodiment, the forming mold 5 is composed of a core 5-1, an outer sleeve 5-2, and an outer sleeve die plate 5-3. The core 5-1 is located inside the outer sleeve 5-2, and forms a cavity with the outer sleeve 5-2, and the resin melt can enter the cavity from the bottom or top or both sides of the outer sleeve 5-2. The core 5-1 can move forward and backward in the outer sleeve 5-2, and the pressure of the melt in the cavity can be adjusted by adjusting the size of the cavity formed. The pressure of the melt in the cavity can also be adjusted by the angle between the core 5-1 and the outer sleeve 5-2. The working principle of the forming mold 5 is as follows: the strip formed after impregnation in the impregnation mold 3 is guided to pass through the hole in the middle of the core 5-1, and then the inner and outer layer material composite structure is formed in the cavity formed by the core 5-1 and the outer sleeve 5-2, which is filled with mixed melt, and finally it is guided out through the outer sleeve die plate 5-3.

[0187] As shown in Figure 7 , the strip 5-4 enters the cavity formed by the core (not shown) and the outer sleeve 5-2, which is filled with the second component melt, for processing, wherein the second component melt is fed into the cavity from the second resin inlet 5-5.

[0188] In the following examples and comparative examples, the manufacturing system shown in Figure 3 is used to prepare the antistatic glass fiber reinforced polyglycolic acid composite material, wherein the first impregnation treatment uses the first impregnation mold shown in Figure 4 , and the second impregnation treatment uses the forming mold shown in Figure 8 .

[0189] The antistatic glass fiber reinforced polyglycolic acid composite material and the preparation method thereof provided by the present application will be described in detail below in conjunction with specific examples.

[0190] Unless otherwise defined, the technical terms used in the following examples have the same meanings as generally understood by those skilled in the art to which the present application belongs. The reagents used in the following examples, unless otherwise specified, are conventional biochemical reagents; the raw materials, instruments and equipment used in the following examples can be purchased on the market or can be obtained by existing methods; the amount of the reagents, unless otherwise specified, is the amount of the reagents in conventional experimental operations; the experimental methods, unless otherwise specified, are conventional methods.

[0191] In each embodiment and comparative example of the present application, the test method of each performance data is as follows:

[0192] (1) Tensile strength: GB / T 1040-2018;

[0193] (2) Flexural modulus: GB / T 9341-2008;

[0194] (3) Impact strength: GB / T 1843-2008;

[0195] (4) Heat distortion temperature: GB / T 1634-2004, A method, bending stress 1.8 MPa;

[0196] (5) Volume resistivity: GB / T31838.2-2019;

[0197] (6) Surface resistivity: GB / T31838.3-2019.

[0198] In the embodiments and comparative examples of the present application, the materials used are as follows:

[0199] (1) Polyglycolic acid: homopolymer polyglycolic acid, melt index 10, 40, 100, 150 g / 10 min (2.16 kg, 230°C), the first two were purchased from Shanghai Pu Jing Chemical Co., Ltd., and the last two were purchased from Japan Wu Yu and Liaoning Jinmei.

[0200] (2) Glass fiber: alkali-free glass fiber, diameter 17 μm, linear density 2400 tex, Chongqing International Composite Material Co., Ltd.

[0201] (3) Antioxidant 1010: BASF, Germany.

[0202] (4) Antioxidant 168: BASF, Germany.

[0203] (5) Silane coupling agent: KH-550, Nanjing Youpu Chemical Co., Ltd.

[0204] (6) Calcium stearate: carbon content 6.5%, Ino Kai Co., Ltd.

[0205] (7) Carbon nanotube: oriented multi-walled carbon nanotube, Nanjing Jicang Nanotechnology Co., Ltd.

[0206] Purity ≥ 99.5%, diameter 10-20 nm, length less than 50 μm, specific surface area 260-340 m 2 / g, thermal conductivity 2000 W / (m·K), electrical conductivity 1400 S / m.

[0207] (8) Edge-modified graphene: self-made by Beijing Research Institute of Chemical Industry;

[0208] Sheet diameter 10-20 μm, thickness 10 nm, aspect ratio 1000-2000, oxygen content 5.3 wt%, hydrogen content 0.30 wt%, electrical conductivity 870 S / m;

[0209] The preparation method is as follows: the gap between the upper mill disc and the lower mill disc is adjusted to 1 mm, then 100 g of 32 mesh flake graphite powder is placed in the kettle body; 2.5 kg of carbon dioxide is injected into the kettle through the gas inlet, and the pressure in the kettle is 60 atm; the temperature in the kettle is heated to 55℃ through the jacket; then the rotating speed of the mill disc is set to 1000 rpm, and the magnetic rotating part is turned on; the pressure in the kettle is increased to 120 atm; after 24 h, the experiment is stopped; the gas inlet is opened, and the pressure in the kettle is reduced to 1 atm within 10 s, and the material is discharged from the discharge port at the bottom of the kettle body, and the edge modified graphene is obtained.

[0210] (9) Carbon black: Cabot.

[0211] (10) Nanoscale chemical exfoliation graphene: flake diameter 100-200 nm, thickness 10 nm, length-height ratio 10-20, oxygen content 32 wt%, hydrogen content 0, electrical conductivity 75 S / m, purchased from Nanjing Jicang Nanotechnology Co., Ltd.

[0212] (11) Natural graphite: Nanjing Jicang Nanotechnology Co., Ltd.

[0213] Carbon content ≥ 99.9%, bulk density 0.019-0.15 g / cm, BET > 3 m 2 / g, particle size 13.5-15.5 μm, electrical conductivity: 334.6 S / cm,

[0214] Example 1

[0215] (1) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) is mixed with 0.5 parts by weight of carbon nanotubes, 1 part by weight of KH550, 0.2 parts by weight of antioxidant 168, 0.3 parts by weight of antioxidant 1010, and 0.2 parts by weight of calcium stearate in a high-speed mixer at 50℃ for 3 minutes, and then the melt is sent into the impregnation mold.

[0216] (2) The continuous glass fiber is introduced into the impregnation mold under the action of the traction machine, and impregnated and dispersed with the above-mentioned melt to form a sample, which is used as the inner layer material, and the glass fiber content is 60 parts by weight.

[0217] (3) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) is mixed with 0.5 parts by weight of edge modified graphene, 2 parts by weight of KH550, 0.1 parts by weight of antioxidant 1010, and 0.5 parts by weight of calcium stearate in a high-speed mixer at 50℃ for 3 minutes, which is used as the outer layer material, and is sent into the double-screw extruder connected with the forming mold.

[0218] (4) The inner layer material enters the forming mold under the action of the traction machine, is guided to pass through the hole in the middle of the core, and is formed in the cavity filled with the mixed melt of the outer layer material between the core and the outer sleeve. Finally, it is guided out through the outer sleeve die plate.

[0219] (5) The amount of the outer layer material is adjusted by selecting the size (4 mm) of the outer sleeve die plate of the forming mold, and the cutter rotation speed of the granulator is adjusted to control the length of the obtained polyglycolic acid composite particles to be 15 mm. The content of the first polyglycolic acid in the obtained composite is 100 parts by weight, the content of the glass fiber is 60 parts by weight, and the content of the second polyglycolic acid is 100 parts by weight.

[0220] (6) The polyglycolic acid composite prepared by the above method is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0221] Comparative Example 1

[0222] (1) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) was mixed with 0.5 parts by weight of carbon nanotubes, 1 part by weight of KH550, 0.2 parts by weight of antioxidant 168, 0.3 parts by weight of antioxidant 1010, 0.2 parts by weight of calcium stearate, and 60 parts by weight of glass fiber (4-6 mm) in a high-speed mixer at 50°C for 3 minutes.

[0223] (2) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) was mixed with 0.5 parts by weight of edge-modified graphene, 2 parts by weight of KH550, 0.1 parts by weight of antioxidant 1010, and 0.5 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes.

[0224] (3) The above two mixtures were added together into a twin-screw extruder for melt granulation, and the obtained polyglycolic acid composite particles had a length of 15 mm. The content of the first polyglycolic acid in the obtained composite was 100 parts by weight, the content of the glass fiber was 60 parts by weight, and the content of the second polyglycolic acid was 100 parts by weight.

[0225] (4) The polyglycolic acid composite prepared above was injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0226] Comparative Example 2

[0227] (1) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) was mixed with 0.5 parts by weight of carbon nanotubes, 1 part by weight of KH550, 0.2 parts by weight of antioxidant 168, 0.3 parts by weight of antioxidant 1010, 0.2 parts by weight of calcium stearate, and 60 parts by weight of glass fiber (4-6 mm) in a high-speed mixer at 50°C for 3 minutes, and then melt granulation was performed to obtain polyglycolic acid composite 1.

[0228] (2) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) was mixed with 0.5 parts by weight of edge-modified graphene, 2 parts by weight of KH550, 0.1 parts by weight of antioxidant 1010, and 0.5 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, and then melt granulation was performed to obtain polyglycolic acid composite 2.

[0229] (3) Polyglycolic acid composite 1 and polyglycolic acid composite 2 were added together into a twin-screw extruder for melt granulation, and the obtained polyglycolic acid composite particles had a length of 15 mm. In the obtained composite, the content of the first polyglycolic acid was 100 parts by weight, the content of the glass fiber was 60 parts by weight, and the content of the second polyglycolic acid was 100 parts by weight.

[0230] (4) The polyglycolic acid composite prepared above was injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0231] Example 2

[0232] (1) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) was mixed with 0.5 parts by weight of carbon nanotubes, 0.05 parts by weight of KH550, 0.05 parts by weight of antioxidant 168, 0.05 parts by weight of antioxidant 1010, and 0.5 parts by weight of erucamide in a high-speed mixer at 50°C for 3 minutes, and then melt granulation was performed to obtain polyglycolic acid composite 2.

[0233] (2) Continuous glass fibers were introduced into the impregnation mold under the action of a traction machine, impregnated and dispersed with the above melt to form a sample bar, which was used as an inner layer material, and the content of the glass fiber was 20 parts by weight.

[0234] (3) 100 parts by weight of polyglycolic acid (melt index 150 g / 10 min) was mixed with 0.2 parts by weight of edge-modified graphene, 0.1 parts by weight of KH550, 0.2 parts by weight of antioxidant 1010, and 0.2 parts by weight of erucamide in a high-speed mixer at 50°C for 3 minutes, which was used as an outer layer material and was fed into a twin-screw extruder connected to a forming mold.

[0235] (4) The inner layer material was introduced into the forming mold under the action of the traction machine, guided through the hole in the middle of the core, and realized the molding of the composite structure of the inner and outer layer materials in the cavity filled with the mixed melt of the outer layer material formed by the core and the outer sleeve. Finally, it was guided out through the outer sleeve die plate.

[0236] (5) The amount of the outer layer material is adjusted by selecting the size of the outer sleeve die plate (4 mm) of the forming die, and the cutter rotation speed of the cutter granulator is adjusted to control the length of the obtained polyglycolic acid composite granules to be 10 mm. In the obtained composite, the content of the first polyglycolic acid is 100 parts by weight, the content of the glass fiber is 20 parts by weight, and the content of the second polyglycolic acid is 50 parts by weight.

[0237] (6) The polyglycolic acid composite prepared by the above method is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0238] Example 3

[0239] (1) 100 parts by weight of polyglycolic acid (melt index 150 g / 10 min) is mixed with 1 part by weight of carbon nanotubes, 2 parts by weight of KH550, 0.5 parts by weight of antioxidant 168, 0.5 parts by weight of antioxidant 1010, and 1 part by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, and then the mixture is sent into an impregnation mold after melting.

[0240] (2) The continuous glass fiber is introduced into the impregnation mold under the action of a traction machine to impregnate and disperse with the above-mentioned melt to form a sample bar, which is used as the inner layer material, and the content of the glass fiber is 150 parts by weight.

[0241] (3) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) is mixed with 0.5 parts by weight of edge-modified graphene, 0.05 parts by weight of KH550, 1 part by weight of antioxidant 1010, and 1 part by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, which is used as the outer layer material and is sent into a double-screw extruder connected to the forming die.

[0242] (4) The inner layer material is introduced into the forming die under the action of the traction machine, guided through the hole in the middle of the core, and realizes the forming of the composite structure of the inner and outer layer materials in the cavity filled with the mixed melt of the outer layer material formed by the core and the outer sleeve, and finally guided out through the outer sleeve die plate.

[0243] (5) The amount of the outer layer material is adjusted by selecting the size of the outer sleeve die plate (4 mm) of the forming die, and the cutter rotation speed of the cutter granulator is adjusted to control the length of the obtained polyglycolic acid composite granules to be 3 mm. In the obtained composite, the content of the first polyglycolic acid is 100 parts by weight, the content of the glass fiber is 150 parts by weight, and the content of the second polyglycolic acid is 60 parts by weight.

[0244] (6) The polyglycolic acid composite prepared by the above method is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0245] Example 4

[0246] (1) 100 parts by weight of polyglycolic acid (melt index 100 g / 10 min) was mixed with 0.5 parts by weight of carbon nanotubes, 0.5 parts by weight of KH550, 0.1 parts by weight of antioxidant 168, 0.2 parts by weight of antioxidant 1010, and 0.2 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, and then the mixture was sent into an impregnation mold after melting.

[0247] (2) Continuous glass fibers were introduced into the impregnation mold under the action of a traction machine, impregnated and dispersed with the above-mentioned melt to form a sample, which was used as an inner layer material, wherein the glass fiber content was 100 parts by weight.

[0248] (3) 100 parts by weight of polyglycolic acid (melt index 100 g / 10 min) was mixed with 1 part by weight of edge-modified graphene, 1 part by weight of KH550, 0.5 parts by weight of antioxidant 1010, and 0.2 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, and then the mixture was sent into a double-screw extruder connected to a forming mold as an outer layer material.

[0249] (4) The inner layer material was introduced into the forming mold under the action of the traction machine, guided through the hole in the middle of the core, and then the inner and outer layer materials were combined in the cavity filled with the mixed melt of the outer layer material to form the forming of the composite structure of the inner and outer layer materials, and finally guided out through the outer sleeve die plate.

[0250] (5) The amount of outer layer material was adjusted by selecting the size (4 mm) of the outer sleeve die plate of the forming mold, and the length of the obtained polyglycolic acid composite material was controlled to be 4 mm by adjusting the cutter speed of the cutter. The first polyglycolic acid content in the obtained composite material was 100 parts by weight, the glass fiber content was 100 parts by weight, and the second polyglycolic acid content was 80 parts by weight.

[0251] (6) The polyglycolic acid composite material prepared by the above method was injection molded into a standard sample, and performance tests were conducted. The test results are shown in Table 1.

[0252] Comparative Example 3

[0253] The preparation process was the same as in Example 1, except that 0.5 parts by weight of edge-modified graphene was not added in step (3). The polyglycolic acid composite material was injection molded into a standard sample, and performance tests were conducted. The test results are shown in Table 1.

[0254] Comparative Example 4

[0255] The preparation process was the same as in Example 1, except that 0.5 parts by weight of carbon nanotubes was not added in step (1). The polyglycolic acid composite material was injection molded into a standard sample, and performance tests were conducted. The test results are shown in Table 1.

[0256] Example 5

[0257] The preparation process is the same as that of Example 1, except that 0.5 parts by weight of edge-modified graphene added in step (3) is replaced by 0.5 parts by weight of carbon nanotubes. The polyglycolic acid composite is injection molded into standard bars for performance testing. The test results are shown in Table 1.

[0258] Example 6

[0259] The preparation process is the same as that of Example 1, except that 0.5 parts by weight of carbon nanotubes added in step (1) is replaced by 0.5 parts by weight of edge-modified graphene. The polyglycolic acid composite is injection molded into standard bars for performance testing. The test results are shown in Table 1.

[0260] Example 7

[0261] The preparation process is the same as that of Example 1, except that 0.5 parts by weight of edge-modified graphene added in step (3) is replaced by 0.5 parts by weight of nanoscale chemical exfoliated graphene. The polyglycolic acid composite is injection molded into standard bars for performance testing. The test results are shown in Table 1.

[0262] Example 8

[0263] The preparation process is the same as that of Example 1, except that 0.5 parts by weight of carbon nanotubes added in step (1) is replaced by 0.5 parts by weight of carbon black; and 0.5 parts by weight of edge-modified graphene added in step (3) is replaced by 0.5 parts by weight of natural graphite. The polyglycolic acid composite is injection molded into standard bars for performance testing. The test results are shown in Table 1.

[0264] Comparative Example 5

[0265] The preparation process is the same as that of Example 1, except that 0.5 parts by weight of carbon nanotubes is not added in step (1); and 0.5 parts by weight of edge-modified graphene is not added in step (3). The polyglycolic acid composite is injection molded into standard bars for performance testing. The test results are shown in Table 1.

[0266] Table 1: Material performance test of examples and comparative examples

[0267]

[0268] From Examples 1 and Comparative Examples 1 and 2, it can be seen that the glass fiber reinforced polyglycolic acid described herein can uniformly disperse glass fibers and long-acting antistatic agents in the matrix resin, greatly improving the mechanical strength and antistatic performance of the composite material, and effectively expanding the application range of polyglycolic acid in fields with high requirements for antistatic performance.

[0269] In addition, the polyglycolic acid composite of Example 2 has improved gloss.

[0270] It should be noted that the foregoing examples have been provided merely for the purposes of illustration and are not intended to limit the application in any way. Descriptions and examples of materials and processes of the application are intended to be illustrative not limiting. Any modifications of the application and other applications of the application will occur to those skilled in the art to which the application pertains and many options for modification of the application will suggest themselves. The application lies in the broadest aspects of the technological concepts involved. Descriptions and examples of specific chemical materials and processes are intended to be illustrative of the application and it is intended that requests for patent protection be limited to one of the specific embodiments described above, described in the following claims, and any equivalents thereof.

Claims

1. An antistatic glass fiber reinforced polyglycolic acid composite material, characterized in that, The device includes an inner core material and at least one outer layer material; the inner core material includes a first polyglycolic acid resin, glass fiber, and a first additive, the first additive including a first antistatic agent, the glass fiber extending continuously from one end of the inner core material to its opposite end; the outer layer material encloses the inner core material, the outer layer material including a second polyglycolic acid resin and a second additive, the second additive including a second antistatic agent; The first antistatic agent is carbon nanotubes; The second antistatic agent is edge-modified graphene; In the core material, the amount of the first polyglycolic acid resin is 100 parts by weight, the amount of glass fiber is 10 to 200 parts by weight, and the first additive includes 0.1 to 2 parts by weight of the first antistatic agent. In the outer layer material, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second additive includes 0.1 to 1 part by weight of the second antistatic agent. In the composite material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the second polyglycolic acid resin is 50-100 parts by weight.

2. The composite material according to claim 1, characterized in that, The average sheet diameter of the edge-modified graphene is 2~30μm; And / or the average aspect ratio of the edge-modified graphene is 600~10000:1; And / or the electrical conductivity of the edge-modified graphene is 200-1000 S / m; And / or the oxygen content in the edge-modified graphene is 0.5wt%-20wt%; and / or the hydrogen content is 0.01wt%-1wt%; And / or the edge-modified graphene is prepared by grinding graphite with a grinding wheel under supercritical carbon dioxide.

3. The composite material according to claim 2, characterized in that, The average sheet diameter of the edge-modified graphene is 5~20μm; And / or the average aspect ratio of the edge-modified graphene is 800~4500:1; And / or the electrical conductivity of the edge-modified graphene is 500-1000 S / m; And / or the oxygen content in the edge-modified graphene is 3wt%-10wt%; and / or the hydrogen content is 0.05wt%-0.5wt%.

4. The composite material according to claim 3, characterized in that, The average aspect ratio of the edge-modified graphene is 1000~3000:

1.

5. The composite material according to any one of claims 1-4, characterized in that, The purity of the carbon nanotubes is greater than 95%; And / or the diameter of the carbon nanotubes is 10~20 nm; And / or the length of the carbon nanotubes is 30~100μm; And / or the specific surface area of ​​the carbon nanotubes is greater than 165 m². 2 / g; And / or the thermal conductivity of the carbon nanotubes is not less than 2000 W / mK; And / or the electrical conductivity of the carbon nanotubes is greater than 1250 S / cm.

6. The composite material according to claim 5, characterized in that, The specific surface area of ​​the carbon nanotubes is 165~500m². 2 / g; And / or the thermal conductivity of the carbon nanotubes is 2000-3000 W / mK; And / or the electrical conductivity of the carbon nanotubes is 1250-3000 S / cm.

7. The composite material according to claim 6, characterized in that, The specific surface area of ​​the carbon nanotubes is 260-340 m². 2 / g.

8. The composite material according to any one of claims 1-4, characterized in that, In the core material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of glass fiber is 10 to 150 parts by weight.

9. The composite material according to claim 8, characterized in that, In the core material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of glass fiber is 20 to 150 parts by weight.

10. The composite material according to any one of claims 1-4, characterized in that, The first polyglycolic acid resin is used in 100 parts by weight, and the first additive further includes at least one of 0.05-5 parts by weight of a first compatibilizer, 0.1-3 parts by weight of a first antioxidant, and 0.1-1 parts by weight of a first lubricant; And / or, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second additive further includes at least one of 0.05-5 parts by weight of a second compatibilizer, 0.1-3 parts by weight of a second antioxidant, and 0.1-1 parts by weight of a second lubricant.

11. The composite material according to claim 10, characterized in that, The amount of the first polyglycolic acid resin is 100 parts by weight, and the first additive further includes at least one of the following: 0.05-2 parts by weight of a first compatibilizer, 0.1-1 parts by weight of a first antioxidant, and 0.2-1 parts by weight of a first lubricant; And / or, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second additive further includes at least one of 0.05-2 parts by weight of a second compatibilizer, 0.1-1 parts by weight of a second antioxidant, and 0.2-1 parts by weight of a second lubricant.

12. The composite material according to claim 10, characterized in that, The first compatibilizer and the second compatibilizer may be the same or different, and each is independently selected from at least one coupling agent; And / or, the first antioxidant and the second antioxidant may be the same or different, and each is independently selected from at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 2246, antioxidant CA and antioxidant 626; And / or, the first lubricant and the second lubricant may be the same or different, each independently selected from at least one of ethylene bis-stearamide, calcium stearate, mono-fatty acid glyceride, polyethylene wax, erucamide, and pentaerythritol stearate.

13. The composite material according to claim 12, characterized in that, The first compatibilizer and the second compatibilizer may be the same or different, and each is independently selected from at least one of silane coupling agents, titanate coupling agents, and organochromium complex coupling agents; And / or, the first antioxidant and the second antioxidant may be the same or different, and each is independently selected from at least one of antioxidant 1010 and antioxidant 168.

14. The composite material according to claim 13, characterized in that, The first compatibilizer and the second compatibilizer may be the same or different, and each is independently selected from silane coupling agents.

15. The composite material according to any one of claims 1-4, characterized in that, The first polyglycolic acid resin and the second polyglycolic acid resin may be the same or different, and each is independently selected from homopolymer polyglycolic acid and / or copolymer polyglycolic acid; And / or, the melt flow rate of the first polyglycolic acid resin at 230°C and 2.16 kg is 5-500 g / 10 min; And / or, the melt flow rate of the second polyglycolic acid resin at 230°C and 2.16 kg is 5-500 g / 10 min.

16. The composite material according to claim 15, characterized in that, The content of glycolic acid monomer in the copolymerized polyglycolic acid is ≥90 mol%; And / or, the melt flow rate of the first polyglycolic acid resin at 230°C and 2.16 kg is 10-200 g / 10 min; And / or, the melt flow rate of the second polyglycolic acid resin at 230°C and 2.16 kg is 10-200 g / 10 min.

17. The composite material according to claim 16, characterized in that, The content of glycolic acid monomer in the copolymerized polyglycolic acid is ≥95 mol%; And / or, the melt flow rate of the first polyglycolic acid resin at 230°C and 2.16 kg is 10-150 g / 10 min; And / or, the melt flow rate of the second polyglycolic acid resin at 230°C and 2.16 kg is 10-150 g / 10 min.

18. The composite material according to any one of claims 1-4, characterized in that, The core material does not contain non-oriented short fibers.

19. The composite material according to claim 18, characterized in that, The core material is composed of a first polyglycolic acid resin, glass fiber, and a first additive.

20. A method for preparing the composite material according to any one of claims 1-19, characterized in that, include: S1. The first polyglycolic acid resin and the first additive are mixed and melted to obtain the first component melt; S2. The continuous glass fiber is subjected to a first impregnation treatment with the first component melt in step S1 to form a filamentous core material; S3. The second polyglycolic acid resin and the second additive are mixed and melted to obtain the second component melt; S4. The core material obtained in step S2 is subjected to at least one second impregnation treatment with at least one second component melt obtained in step S3 to obtain the antistatic glass fiber reinforced polyglycolic acid composite material.

21. The preparation method according to claim 20, characterized in that, The mixing conditions for step S1 are: temperature of 40-60℃ and time of 3-5 min; and / or the melting temperature of step S1 is 230-260℃. And / or, the mixing conditions in step S3 are: temperature of 40-60℃, time of 3-5 min; and / or the melting temperature in step S3 is 230-260℃; And / or, step S2 further includes: dispersing and preheating the continuous glass fibers before subjecting them to the first impregnation treatment; And / or, step S4 further includes: after the second impregnation treatment, the material obtained by the second impregnation treatment is subjected to pull-out, strip-drawing, cooling, drying and pelletizing treatment to obtain an antistatic glass fiber reinforced polyglycolic acid composite material.

22. The preparation method according to claim 21, characterized in that, The preheating temperature is 80-250℃.

23. The preparation method according to any one of claims 20-22, characterized in that, In step S2, the first impregnation process is performed in a first impregnation mold. The first impregnation mold is an adjustable impregnation mold, which includes a fiber inlet, a fiber outlet, and a melt flow channel. At least one first guide roller is provided in the mold cavity of the first impregnation mold. The first guide roller is movable between the fiber inlet and the fiber outlet. And / or, the first guide roller is movable along a direction perpendicular to the line connecting the fiber inlet and the fiber outlet.

24. The preparation method according to any one of claims 20-22, characterized in that, In step S2, the first impregnation process is carried out in the second impregnation mold. The second impregnation mold is a combined impregnation mold, which includes a first module, an intermediate module, and a second module connected in sequence. The first module is provided with a fiber inlet and a first module flow channel. The second module is provided with a fiber outlet and a second module flow channel. The intermediate module is provided with an intermediate module flow channel. After the first module, the intermediate module, and the second module are connected in sequence, the first module flow channel, the intermediate module flow channel, and the second module flow channel are connected to form a combined flow channel for the fiber to pass through.

25. The preparation method according to any one of claims 20-22, characterized in that, In step S2, the first impregnation process is carried out in a third impregnation mold. The third impregnation mold is a strong turbulent impregnation mold. The third impregnation mold includes a fiber inlet channel, an impregnation outlet, and a melt gap channel. The fiber inlet channel, the impregnation outlet, and the melt gap channel are all connected to the mold cavity inside the third impregnation mold. A second guide roller is provided inside the mold cavity of the third impregnation mold. The second guide roller includes at least one active guide roller, which is driven to rotate by a driving device.

26. The application of the composite material according to any one of claims 1-19 or the composite material prepared by the preparation method according to any one of claims 20-25 in the fields of catering, building decoration, oilfield chemical industry, and engineering plastics.

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