Conductive polyglycolic acid composite material, and preparation method and application thereof

Abstract

The application relates to the technical field of high polymer composite materials, and provides a conductive polyglycolic acid composite material and a preparation method and application thereof.The conductive 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 glass fibers continuously extend from one end of the core material to the opposite end; the outer material wraps the core material, and the outer material comprises a second polyglycolic acid resin, conductive fillers and a second additive.The conductive polyglycolic acid composite material is designed based on multi-component materials, can greatly increase the proportion of the conductive fillers in the composite material, can also make the conductive fillers uniformly disperse in the polyglycolic acid resin, can fully play the synergistic effect between the continuous / constant-length glass fibers and the conductive fillers, can obviously improve the mechanical and conductive properties of the polyglycolic acid composite material, and can expand the application field.

Description

TECHNICAL FIELD

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

[0002] As a polyester with a simple and regular linear molecular structure, polyglycolic acid is an environmentally friendly biodegradable material that has received widespread attention in recent years. Compared with polylactic acid, polyglycolic acid has better tensile strength, bending modulus and heat resistance; in addition, polyglycolic acid also has excellent gas barrier properties and can be widely used in packaging, medical, oil and gas and other fields. Therefore, polyglycolic acid has great market application potential.

[0003] Polyglycolic acid is an insulating material, and its electrical conductivity and electron transport capacity need to be greatly increased when it is applied in the fields of electromagnetic shielding and sensors. Generally, polyglycolic acid is mixed with conductive fillers to prepare composite polymer conductive materials to improve its electrical conductivity. Composite polymer conductive materials have the advantages of good environmental performance, simple manufacturing, low cost, wide application, adjustable electrical conductivity, etc. The conductive fillers used to prepare composite polymer conductive materials mainly include carbon materials, metals and metal oxides. Among them, carbon materials include carbon black, carbon fiber, single-walled carbon nanotube, multi-walled carbon nanotube, graphene, fullerene, mesocarbon microbead, graphite, expanded graphite and acetylene black, etc. Carbon materials have the characteristics of variety, corrosion resistance, low density, high electrical conductivity and relatively low cost, and can improve the electrical conductivity of the material while improving the mechanical properties of the material, which is a good choice for conductive fillers. However, in order to make the composite polymer conductive material reach the conductive level, a large amount of conductive fillers need to be added, and the use of mixing and other means to prepare master batches for addition will result in multiple processing of polyglycolic acid, which will reduce the relative molecular mass and affect the mechanical properties of the final product.

[0004] Therefore, it is of great market value and research significance to develop a new type of polyglycolic acid composite material with high mechanical strength, high conductive filler filling amount and uniform dispersion. SUMMARY

[0005] To solve the above technical problems, the present application provides a conductive polyglycolic acid composite material, a preparation method and application thereof.

[0006] The technical scheme adopted by the present application is:

[0007] In a first aspect, the present application provides a conductive polyglycolic acid composite material, comprising a core material and at least one outer layer material; the core material comprises a first polyglycolic acid resin, glass fibers and a first additive, the glass fibers continuously extend from one end of the core material to the opposite end; the outer layer material wraps the core material, and the outer layer material comprises a second polyglycolic acid resin, a conductive filler and a second additive.

[0008] As a preferred scheme of the composite material provided by the present application, the conductive filler is at least one of carbon material, metal, and metal oxide;

[0009] Preferably, the carbon material comprises at least one of carbon black, carbon fiber, single-walled carbon nanotube, multi-walled carbon nanotube, graphene, fullerene, mesocarbon microbead, graphite, expanded graphite, and acetylene black; and / or the metal comprises at least one of copper powder, silver powder, aluminum powder, aluminum-steel composite fiber, iron powder, and gold powder; and / or the metal oxide comprises at least one of Al2O3, MgO, TiO2, and Fe2O3.

[0010] More preferably, the conductive filler comprises at least acetylene black.

[0011] As another preferred scheme of the composite material provided by the present application, the conductive filler comprises acetylene black and edge-modified graphene.

[0012] Preferably, the weight ratio of the acetylene black to the edge-modified graphene is (20-100):1.

[0013] And / or the average flake diameter of the edge-modified graphene is 2-30 μm, preferably 5-20 μm.

[0014] And / or the average aspect ratio of the edge-modified graphene is 600-10000:1, preferably 800-4500:1, and more preferably 1000-3000:1.

[0015] And / or the electrical conductivity of the edge-modified graphene is 200-1000 S / m, preferably 500-1000 S / m.

[0016] And / or in the edge-modified graphene, the oxygen content is 0.5wt%-20wt%, preferably 3wt%-10wt%, and the hydrogen content is 0.01wt%-1wt%, preferably 0.05wt%-0.5wt%.

[0017] And / or the edge-modified graphene is prepared by grinding graphite under supercritical carbon dioxide.

[0018] 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;

[0019] and / or, in the outer layer material, the amount of the second polyglycolic acid resin is 100 parts by weight, and the amount of the conductive filler is 1-99 parts by weight, preferably 5-50 parts by weight, and more preferably 10-50 parts by weight;

[0020] 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.

[0021] 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, and each is independently selected from the group consisting of 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%;

[0022] and / or, the melt flow rate of the first polyglycolic acid resin at 230°C under a load of 2.16 kg is 5-500 g / 10 min, preferably 10-200 g / 10 min, and more preferably 10-100 g / 10 min;

[0023] and / or, the melt flow rate of the second polyglycolic acid resin at 230°C under a load of 2.16 kg is 5-500 g / 10 min, preferably 10-200 g / 10 min, and more preferably 10-100 g / 10 min.

[0024] 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 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 part by weight of a first lubricant; preferably, the amount of the first polyglycolic acid resin is 100 parts by weight, and the first additive includes at least one of 0.05-2 parts by weight of a first compatibilizer, 0.1-1 part by weight of a first antioxidant, and 0.2-1 part by weight of a first lubricant;

[0025] And / or, the second polyglycolic acid resin is used in an amount of 100 parts by weight, the second auxiliary agent 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; preferably, the second polyglycolic acid resin is used in an amount of 100 parts by weight, the second auxiliary agent 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.

[0026] 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, an organic chromium complex coupling agent, more preferably a silane coupling agent;

[0027] And / or, 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 245 (triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], CAS: 36443-68-2), antioxidant CA and antioxidant 626, preferably at least one of antioxidant 1010, antioxidant 168 and antioxidant 245;

[0028] And / or, 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.

[0029] As another preferred embodiment of the composite material provided by the present application, the inner core material does not contain non-oriented short fibers, and preferably the inner core material is composed of the first polyglycolic acid resin, glass fibers and the first auxiliary agent.

[0030] In a second aspect, the present application provides a preparation method of the above-mentioned conductive polyglycolic acid composite material, comprising:

[0031] S1. Mixing and melting the first polyglycolic acid resin and the first auxiliary agent to obtain a first component melt;

[0032] S2. performing a first impregnation treatment on the continuous glass fibers with the first component melt in step S1 to form a filamentous inner core material;

[0033] S3. mixing and melting the second polyglycolic acid, the conductive filler and the second auxiliary agent to obtain a second component melt;

[0034] S4. performing at least one second impregnation treatment on the inner core material obtained in step S2 and the melt of the second component in step S3 to obtain the conductive polyglycolic acid composite material.

[0035] As a preferred embodiment of the preparation method provided by the present application, the mixing condition in step S1 is that the temperature is 40-60°C and the time is 3-5 min; and / or the melting temperature in step S1 is 230-260°C.

[0036] As a preferred embodiment of the preparation method provided by the present application, the mixing condition in step S1 is that the temperature is 40-60°C and the time is 3-5 min; and / or the melting temperature in step S1 is 230-260°C.

[0037] As a preferred embodiment of the preparation method provided by the present application, the step S2 further comprises: dispersing and preheating the continuous glass fibers before the first impregnation treatment; preferably, the preheating temperature is 80-250°C.

[0038] As a preferred embodiment of the preparation method provided by the present application, the step S4 further comprises: after the second impregnation treatment, pulling out, stretching, cooling, drying and cutting the material obtained after the second impregnation treatment to obtain the conductive polyglycolic acid composite material.

[0039] As another preferred embodiment of the preparation method provided by the present application, the first impregnation treatment in step S2 is performed 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, and 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.

[0040] As another preferred embodiment of the preparation method provided by the present application, the first impregnation treatment in step S2 is performed 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 connected to form a combined flow channel for the fibers to pass through.

[0041] As another preferred scheme of the preparation method provided by the present application, the first impregnation treatment in step S2 is performed in a third impregnation die, the third impregnation die being a strong turbulent flow impregnation die, the third impregnation die comprising a fiber inlet channel, an impregnation outlet and a melt slit runner, all of which are in communication with a die cavity inside the third impregnation die; wherein a second godet is arranged in the die cavity of the third impregnation die, the second godet comprising at least one driving godet, the driving godet being driven to rotate by a driving device.

[0042] In a third aspect, the present application provides an application of the conductive polyglycolic acid composite material or the conductive polyglycolic acid composite material prepared by the preparation method in the field of electromagnetic shielding and sensors.

[0043] The present application has at least the following beneficial effects:

[0044] (1) The conductive polyglycolic acid composite material of the present application has an inner-outer layer composite structure. The continuous / constant-length glass fibers contained in the inner layer material are treated by impregnation, which not only realizes the uniform dispersion of high-content long fibers in polyglycolic acid, but also prevents the leakage of fibers, fully exerting the effects of increasing rigidity and improving heat resistance of long fibers. The conductive fillers contained in the outer layer material can effectively improve the flowability of polyglycolic acid, and also effectively enhance the mechanical strength and electrical conductivity of polyglycolic acid.

[0045] (2) The conductive polyglycolic acid composite material of the present application, through the inner-outer layer composite structure, makes the continuous / constant-length glass fibers and the conductive fillers with high filling amount synergistically modify the polyglycolic acid, and prepares a polyglycolic acid composite material with good dispersibility of conductive fillers, high electrical conductivity, high rigidity, high heat resistance and biodegradability, which can expand the application range of the polyglycolic acid composite material and improve its market value. BRIEF DESCRIPTION OF DRAWINGS

[0046] Figure 1 FIG. 1 is a structure schematic diagram of a conductive polyglycolic acid composite material according to an embodiment of the present application;

[0047] Figure 2 FIG. 2 is a structure schematic diagram of a conductive polyglycolic acid composite material manufacturing system according to an embodiment of the present application;

[0048] Figure 3 FIG. 3 is a structure schematic diagram of a conductive polyglycolic acid composite material manufacturing system according to another embodiment of the present application;

[0049] Figure 4 FIG. 4 is a sectional view of a first impregnation die according to an embodiment of the present application;

[0050] Figure 5 FIG. 5 is a sectional view of a second impregnation die according to an embodiment of the present application;

[0051] Figure 6 A cross-sectional view of a third impregnation die in one embodiment of the present application;

[0052] Figure 7 A schematic view of a second impregnation process in one embodiment of the present application;

[0053] Figure 8 A cross-sectional view of a forming die used in the second impregnation process in one embodiment of the present application.

[0054] Explanation of Reference Numerals:

[0055] 0-1, core material; 0-2, fiber bundle; 0-3, outer layer material;

[0056] 1, fiber stand and fiber guide device; 2, fiber pretreatment device; 3, first impregnation die; 4, melt plasticizing feeder; 5, forming die; 6, cooling water tank; 7, drying machine; 8, puller; 9, pelletizer; 10, collection box;

[0057] A300, first impregnation die die head; A1, fiber inlet; A2, second runner; A3, melt flow channel; A4, first runner; A5, upper die cover; A6, fiber outlet; A7, impregnation die body; A8, first godet;

[0058] B300, second impregnation die die head; B1, fiber inlet; B2, melt flow channel; B3, first module; B31, first module flow channel; B4, combined flow channel; B5, standardization joint; B6, intermediate module; B61, intermediate module flow channel; B7, second module; B71, second module flow channel; B8, fiber outlet;

[0059] C300, third impregnation die die head; C1, melt split flow channel; C2, impregnation die outer body; C3, fiber inlet passage; C4, driving godet; C5, driven godet; C6, impregnation outlet;

[0060] 4-1, extruder I; 4-2, extruder II;

[0061] 5-1, core; 5-2, outer sleeve; 5-3, outer sleeve die plate; 5-4, strand; 5-5, second resin inlet. DETAILED DESCRIPTION

[0062] 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.

[0063] In a first aspect, the present application provides a conductive polyglycolic acid composite material, comprising 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 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 comprises a second polyglycolic acid resin, a conductive filler and a second additive.

[0064] 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 the outer side of the inner core material with a second component comprising a second polyglycolic acid resin, a conductive filler and a second additive, a conductive 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 outside the inner core material. Such a polyglycolic acid composite material has excellent mechanical properties; at the same time, by adding a conductive filler to the second polyglycolic acid resin, the electrical conductivity of the conductive polyglycolic acid composite material can be adjusted.

[0065] In the present application, the terms "one end" and "opposite end" are generally relative to the longitudinal direction of the conductive polyglycolic acid composite material.

[0066] In the transverse cross-section of the conductive 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 conductive polyglycolic acid composite material in the inner core material.

[0067] 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 conductive 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, in particular, non-oriented short fibers.

[0068] In the conductive polyglycolic acid composite material of the present application, the outer layer material at least 80% wraps the inner core material, for example, 80-99%, 85-95% wraps the inner core material; the outer layer material can also continuously wrap the inner core material.

[0069] The outer layer material is not limited in the number of layers, and can be one layer or multiple layers. In some embodiments, the multiple layers of the outer layer material can be formed of the same material or multiple materials.

[0070] The glass fibers are continuous and / or fixed-length glass fibers.

[0071] According to some embodiments of the present application, the composite material is in the form of a strip, a rod or a particle.

[0072] In the present application, the strip-shaped, rod-shaped or granular conductive polyglycolic acid composite material can be cut from the continuous filament-shaped conductive polyglycolic acid composite material.

[0073] Further preferably, the length of the strip-shaped or rod-shaped composite material is 5-30 mm, for example, 5 mm, 6 mm, 8 mm, 10 mm, 12 mm, 15 mm, 20 mm, 22 mm, 25 mm, 30 mm, etc., preferably 5-25 mm, more preferably 6-15 mm. And / or the particle size of the granular composite material is 2-5 mm, for example, 2 mm, 3 mm, 4 mm, 5 mm, etc., preferably 3-4 mm.

[0074] The present application does not have special requirements for the cross-sectional shape of the conductive polyglycolic acid composite material. In some embodiments, the cross-section of the granular or rod-shaped conductive polyglycolic acid composite material is circular or circular-like. In other embodiments, the cross-section of the granular or strip-shaped conductive polyglycolic acid composite material is rectangular or square.

[0075] According to some embodiments of the present application, the conductive filler is at least one of carbon material, metal, metal oxide.

[0076] According to some embodiments of the present application, the carbon material includes at least one of carbon black, carbon fiber, single-walled carbon nanotube, multi-walled carbon nanotube, graphene, fullerene, mesocarbon microbead, graphite, expanded graphite, acetylene black; and / or, the metal includes at least one of copper powder, silver powder, aluminum powder, aluminum steel composite fiber, iron powder, gold powder; and / or, the metal oxide includes at least one of AI2O3, MgO, TiO2, Fe2O3.

[0077] According to some embodiments of the present application, the conductive filler at least includes acetylene black.

[0078] Acetylene black has the characteristics of small specific gravity, large specific surface area and high conductivity. The molten polyglycolic acid can enter the interior of the acetylene black to form an interpenetrating network structure, which is more conducive to improving the conductivity of the composite material than other conductive fillers.

[0079] According to some embodiments of the present application, the particle size of the acetylene black is 1-10 μm, the oil absorption value is 1-10 mL / g, the specific surface area is 40-200 m 2 / g, and the pH value is 5-9; preferably, the particle size of the acetylene black is 2-5 μm, the oil absorption value is 2-6 mL / g, the specific surface area is 50-100 m 2 / g, and / or the pH value is 6-7.5.

[0080] According to some embodiments of the present application, the conductive filler includes acetylene black and edge-modified graphene.

[0081] According to some embodiments of the present application, the weight ratio of the acetylene black and the edge-modified graphene is (20-100):1, for example, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, etc.

[0082] 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.

[0083] 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.

[0084] In the present application, the "aspect ratio" refers to the ratio of the length (flake size) of the graphene to the thickness.

[0085] According to some embodiments of the present application, the conductivity of the edge-modified graphene is 200-1000 S / m, preferably 500-1000 S / m.

[0086] According to some embodiments of the present application, the edge-modified graphene is graphene modified with carboxyl groups at the edges.

[0087] According to some embodiments of the present application, in the edge-modified graphene, the oxygen content is 0.5wt%-20wt%, preferably 3wt%-10wt%; and the hydrogen content is 0.01wt%-1wt%, preferably 0.05wt%-0.5wt%.

[0088] According to some embodiments of the present application, the edge-modified graphene is prepared by grinding graphite under supercritical carbon dioxide.

[0089] The flake size of the edge-modified graphene in the present application is in the micron level, and has adjustable aspect ratio and carbon and oxygen content, and has higher conductivity, which can be significantly distinguished from the existing nanoscale graphene, and can overcome the problem of easy aggregation of nanoscale graphene. The edge-modified graphene has good flake integrity, and can easily form a good conductive network, and when used in combination with acetylene black, the conductive performance of the composite material can be obviously improved with a small amount of addition.

[0090] According to some embodiments of the present application, the edge-modified graphene is prepared by grinding graphite under supercritical carbon dioxide.

[0091] 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. In this state, 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.

[0092] According to a specific embodiment of the present application, the preparation method of the edge-modified graphene comprises:

[0093] S101. Adding purified or un-purified graphite powder into a high-pressure grinding disc kettle;

[0094] S102. 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;

[0095] S103. Grinding the material containing graphite powder and supercritical carbon dioxide.

[0096] According to some embodiments of the present application, the graphite powder is selected from flake graphite powder and expanded graphite powder.

[0097] According to some embodiments of the present application, the particle size of the graphite powder is 10-80 mesh, preferably 20-60 mesh.

[0098] 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.

[0099] According to some embodiments of the present application, in step S102, carbon dioxide is made into a supercritical state by making the temperature in the kettle exceed 32.26℃ and the pressure exceed 72.9atm.

[0100] 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.

[0101] According to some embodiments of the present application, in step S103, 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.

[0102] According to some embodiments of the present application, the temperature in the high-pressure grinding disc reactor is 35-200℃, preferably 35-100℃, and more preferably 35-70℃.

[0103] According to some embodiments of the present application, the pressure in the high-pressure grinding disc reactor is 50-165 atm, preferably 75-150 atm, and more preferably 75-125 atm.

[0104] According to some embodiments of the present application, the rotation speed of the grinding disc in the high-pressure grinding disc reactor is 500-10000 r / min, preferably 500-5000 r / min.

[0105] According to some embodiments of the present application, the grinding time is 6-48 hours.

[0106] In the present application, the graphite can be mixed with supercritical carbon dioxide and ground and exfoliated by using a high-pressure grinding disc reactor.

[0107] 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 amount of the glass fiber is 10-200 parts by weight, for example, 10 parts by weight, 20 parts by weight, 30 parts by weight, 50 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 10-150 parts by weight, and more preferably 20-150 parts by weight.

[0108] 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 amount of the conductive filler is 1-99 parts by weight, for example, 1 part by weight, 2 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 20 parts by weight, 20.5 parts by weight, 21 parts by weight, 22 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 60 parts by weight, 80 parts by weight, 99 parts by weight, etc., preferably 5-50 parts by weight, and more preferably 10-50 parts by weight.

[0109] According to some embodiments of the present application, 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, for example, 1 part 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 10-100 parts by weight, and more preferably 50-100 parts by weight.

[0110] According to some embodiments of 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%.

[0111] The comonomer of the copolymer polyglycolic acid can include: cyclic monomers such as 1,4-dioxane-2,3-dione, lactide, lactone (e.g. pivalolactone, butyrolactone, 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, etc. Hydroxycarboxylic acid and its alkyl ester; essentially equimolar mixture of aliphatic diols (e.g. ethylene glycol and 1,4-butanediol) and aliphatic dicarboxylic acids (e.g. succinic acid and adipic acid) or their alkyl esters; and combinations of two or more of the above.

[0112] 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 coal chemical method.

[0113] 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.

[0114] In particular, the present inventors found that polyglycolic acid composites with high surface quality performance and comprehensive performance can be prepared according to the parameters (e.g. melt flow rate) of the present application. 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 has improved mechanical properties; on the contrary, 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 has improved gloss.

[0115] According to some embodiments of the present application, the first polyglycolic acid resin has a melt flow rate of 5-500 g / 10 min under the condition of 230°C, 2.16 kg, for example, 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 10-200 g / 10 min, and more preferably 10-100 g / 10 min.

[0116] According to some embodiments of the present application, the second polyglycolic acid resin has a melt flow rate of 5-500 g / 10 min under the condition of 230°C, 2.16 kg, for example, 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 10-200 g / 10 min, and more preferably 10-100 g / 10 min.

[0117] The specific types and amounts of the various additives in the first additive and the second additive are not limited in the present application, which aims to achieve the relevant properties of the composite material and the effects of the relevant additives.

[0118] According to some embodiments of the present application, the first additive 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 part by weight of a first lubricant, based on 100 parts by weight of the first polyglycolic acid resin. 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. Preferably, the first additive includes 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, based on 100 parts by weight of the first polyglycolic acid resin.

[0119] 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 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 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. Preferably, the second polyglycolic acid resin is used in an amount of 100 parts by weight, and the second auxiliary agent 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 part by weight of a second lubricant.

[0120] 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.

[0121] 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 245 (tri(ethylene glycol) bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], CAS: 36443-68-2), antioxidant CA, and antioxidant 626, preferably at least one of antioxidant 1010, antioxidant 168, and antioxidant 245.

[0122] 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, a monoglyceride, a polyethylene wax, erucamide, pentaerythritol stearate.

[0123] In different embodiments of the present application, the first auxiliary agent and the second auxiliary agent are not limited to specific types and amounts of the several auxiliary agents, and each can have a wide range of selection. For example, the first auxiliary agent and the second auxiliary agent each independently can further include at least one of a slip agent, an antistatic agent, and a plasticizer.

[0124] In a second aspect, the present application provides a preparation method of the conductive polyglycolic acid composite material, comprising:

[0125] S1. mixing and melting the first polyglycolic acid resin and the first auxiliary agent to obtain a first component melt;

[0126] 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;

[0127] S3. mixing and melting the second polyglycolic acid, the conductive filler and the second auxiliary agent to obtain a second component melt;

[0128] S4. performing at least one second impregnation treatment on the inner core material obtained in step S2 with at least one second component melt in step S3 to obtain the conductive polyglycolic acid composite material.

[0129] The preparation method of the present application can be performed continuously in line to obtain a continuous filamentous product, which can be directly stored and used, or cut into a strip-shaped, rod-shaped or particulate product with a certain length or particle size.

[0130] According to some embodiments of the present application, the mixing conditions in step S1 are that the temperature is 40-60℃ and the time is 3-5 min; and / or the melting temperature in step S1 is 230-260℃.

[0131] According to some embodiments of the present application, the mixing conditions in step S3 are that the temperature is 40-60℃ and the time is 3-5 min; and / or the melting temperature in step S3 is 230-260℃.

[0132] In the present application, the melting time in steps S1 and S3 can have a wide selection range, so as 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.

[0133] According to some embodiments of the present application, the step S2 further comprises: performing a dispersion treatment and a preheating treatment on the continuous glass fiber before performing the first impregnation treatment; preferably, the preheating treatment is performed at a temperature of 80-250℃. The dispersion treatment process in the present application adopts a conventional fiber dispersion treatment process in the art.

[0134] According to some embodiments of the present application, the step S4 further comprises: after the second impregnation treatment, the material subjected to the second impregnation treatment is subjected to pulling-out, stretching, cooling, drying, and granulation treatment to obtain the conductive polyglycolic acid composite material. In the present application, the process conditions of the pulling-out, stretching, cooling, drying, and granulation treatment are not particularly limited, and those skilled in the art can adjust them according to the specific performance requirements of the prepared conductive polyglycolic acid composite material.

[0135] According to some embodiments of the present application, the first impregnation treatment in step S2 can be performed in a first impregnation mold, which is an adjustable impregnation mold, comprising a fiber inlet, a fiber outlet, and a melt flow channel, and 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.

[0136] According to some embodiments of the present application, the first impregnation treatment in step S2 can be performed in a second impregnation mold, which is a combined impregnation mold, comprising 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 connected to form a combined flow channel for the fiber to pass through.

[0137] According to some embodiments of the present application, the first impregnation treatment in step S2 can also be performed in a third impregnation mold, which is a strong turbulence 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 a second godet is arranged in the mold cavity of the third impregnation mold, and the second godet comprises at least one driven godet, which is driven to rotate by a driving device.

[0138] 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.

[0139] It should be noted that the first, second and third impregnation molds described above can be applied to any existing manufacturing system and preparation technology of the conductive polyglycolic acid composite material.

[0140] According to some embodiments of the preparation method of the application, the second impregnation treatment in step S4 can be performed 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 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 to adjust the size of the cavity formed to determine the pressure of the melt in the cavity. 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 forms the inner layer of the impregnated material, is guided to pass through the hole in the middle of the core, and then realizes the forming of the composite structure of the inner and outer layers of the material in the cavity filled with the mixed melt formed by the core and the sleeve, and finally is guided out through the sleeve die plate.

[0141] The application will be further described below with reference to the accompanying drawings.

[0142] Figure 1 The structure of the conductive polyglycolic acid composite material of the application is shown. As shown in Figure 1 , the cross section of the conductive polyglycolic acid composite material of the 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.

[0143] As shown in Figure 2 and Figure 3 , the manufacturing system of the 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.

[0144] In the manufacturing system, the forming mold 5 is used for the forming of the conductive polyglycolic acid composite material, and the structure thereof is shown in Figure 8 .

[0145] In the manufacturing system, the first impregnation mold 3 is used for the impregnation of the fiber and the first polyglycolic acid resin melt.

[0146] As shown in Figure 4As shown, in one embodiment, the first impregnation die is an adjustable godet position impregnation device, which includes a first impregnation die head A300, the first impregnation die head A300 includes an impregnation die body A7, a fiber inlet A1, a fiber outlet A6, and a melt channel A3. At least one first godet A8 is arranged 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.

[0147] Taking a rectangular first impregnation die head A300 as an example, a plurality of first godets A8 are arranged 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.

[0148] 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.

[0149] Since the fiber needs to pass around the first godet A8 in the die cavity when walking 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 walking path of the fiber in the die cavity can be changed. Therefore, when the required impregnation condition of the fiber changes, 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.

[0150] Specifically, the present application is to adjust the position of the first godet A8 by slotting the inner wall of the die cavity of the first impregnation die head A300.

[0151] The first inner wall of the first impregnation die head A300 is provided with a first sliding groove A4, and the first sliding groove A4 extends between the fiber inlet A1 and the fiber outlet A6 (i.e. Figure 4As shown in the Y-axis direction), the first guide roller A8 moves along the second sliding groove A2 to change its vertical position in the die.

[0152] Further, the first inner wall of the first impregnation die head A300 is also provided with a second sliding groove A2 extending in a direction perpendicular to the first sliding groove A4 (i.e. Figure 4 As shown in the Y-axis direction), the first guide roller A8 moves along the second sliding groove A2 to change its vertical position in the die.

[0153] It should be noted that the first sliding groove A4 and the second sliding groove A2 can be connected. Thus, the first guide roller A8 can be arbitrarily moved in the longitudinal direction or the transverse direction, so that its position is changed.

[0154] The cross section of the first sliding groove A4 and the second sliding groove A2 can be trapezoidal, circular, arc-shaped or rectangular, etc., which is not limited by the present application.

[0155] Both ends of the first guide roller A8 are provided with adjusting devices (not shown in the figure), which are used to adjust the axial length of the first guide roller A8. The minimum axial length of the first guide roller A8 is less than the distance between the first inner wall and the second inner wall, and the maximum axial length of the first guide roller A8 is greater than the distance between the first inner wall and the second inner wall.

[0156] As shown in the Y-axis direction), the first guide roller A8 moves along the second sliding groove A2 to change its vertical position in the die. Figure 5 As shown in the Y-axis direction), the first guide roller A8 moves along the second sliding groove A2 to change its vertical position in the die.

[0157] 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, wherein the number of intermediate modules B6 is at least one. That is, the first module B3 is the first module, and the second module B7 is the tail module, and there is one or more intermediate modules B6 between them. It should be noted that these intermediate modules B6 are also connected in sequence.

[0158] That is, the number of intermediate modules B6 can be increased or decreased as needed, so that when the impregnation requirement changes, different intermediate modules B6 are selected to be combined to form the combined second impregnation die head B300, thereby improving the continuity and production efficiency of production, and saving the cost of additional mold opening.

[0159] Furthermore, by selecting different intermediate modules B6, the shape parameters (such as curvature) of the formed combined flow channel B4 can be changed, thereby altering the flow path of the fiber and melt. This can change the impregnation angle and fiber tension of the fiber at different stations in the mold, ultimately achieving the purpose of adjusting and optimizing the entire impregnation process of the fiber and improving the adaptability of the second impregnation mold head B300 to polyglycolic acid resin and fiber.

[0160] The first module B3, the intermediate module B6, and the second module B7 are placed in the mold frame. The mold frame provides a constraint, ensuring that they are in close contact with each other and thus guaranteeing the sealing of the combined flow channel B4.

[0161] like Figure 5 As shown, an implementation with two intermediate modules B6 is illustrated. Figure 5 In the embodiment shown, 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 section 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.

[0162] Understandably, different combinations of flow channels B4 can be obtained by selecting different intermediate modules B6.

[0163] like Figure 5 As shown, the downstream end of the first module flow channel B31, the upstream end of the second module flow channel B71, and both ends of the intermediate module flow channel B61 are all located in the same plane and are constructed with standardized connectors B5. In other words, the connections between the first module flow channel B31, the intermediate module flow channel B61, and the second module B71 are made through standardized connectors B5. Since the standardized connectors B5 are all located in the same plane and have the same shape and size, it facilitates the combination and connection between different modules.

[0164] like Figure 6 As shown, in another embodiment of the present invention, the third impregnation mold is a strong turbulent impregnation mold, including a third impregnation mold head C300. The third impregnation mold head C300 includes an impregnation mold outer body C2. The impregnation mold outer body C2 is provided with a fiber inlet channel C3, an impregnation outlet C6, and a melt gap flow channel C1. The fiber inlet channel C3, the impregnation outlet C6, and the melt gap flow channel C1 are all connected to the mold cavity inside the impregnation mold outer body C2.

[0165] The second godet roller is arranged in the die cavity of the impregnation die outer body C2, and the second godet roller comprises at least one driving godet roller C4, and 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 godet roller C4 driven to rotate 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 of the fiber, ensuring the integrity of the fiber, avoiding the fiber being pulled off, and improving the mechanical properties of the material.

[0166] Preferably, the second godet roller further comprises at least one driven godet roller C5, and 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.

[0167] As shown in Figure 6 , an example having one driving godet roller C4 and two driven godet rollers C5 is shown, wherein the two driven godet rollers C5 are arranged one above the other to extend the impregnation path of the fiber passing therethrough. The heights of the driving godet roller C4 and the driven godet roller C5 in the die cavity can be the same or different.

[0168] Further, the driving device can be a motor, a hydraulic mechanism or a reduction box, etc. capable of driving the driving godet roller C4 to rotate.

[0169] According to the running speed v1 of the fiber entering the die cavity of the impregnation die outer body C2, the tangential speed v2 of the corresponding 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 reduce the breaking and wear of the fiber, thereby ensuring the integrity of the fiber and promoting the impregnation degree of the fiber, shortening the impregnation time and improving the production efficiency.

[0170] As shown in Figure 2 , the melt plasticizing feeding device 4 is composed of a double screw extruder for melt plasticizing the material. The double screw extruder is a co-rotating double screw extruder, the screw diameter is 25mm-95mm, and the length-diameter ratio is 36:1-65:1. When the melt plasticizing feeding device 4 is composed of one extruder 4, the melt plasticized melt in the extruder is divided by a melt distributor, respectively enters the impregnation die and the forming die, and the melt flow control valve is used to control the flow of each.

[0171] As shown in Figure 3As shown, when the melt plasticizing feed device 4 is composed of two extruders 4-1 and 4-2, the melt plasticized melt of each extruder I 4-1 and extruder II 4-2 is respectively fed into the impregnation die and the forming die. In this embodiment, the melt plasticizing feed device is composed of two extruders I 4-1 and extruder II 4-2, and the melt plasticized melt of each extruder I 4-1 and extruder II 4-2 is respectively fed into the first impregnation die 3 and the forming die 5. The extruder I 4-1 and the extruder II 4-2 can be fed with the same or different materials, so that the composite material with the same or different materials of the inner layer and the outer layer can be prepared.

[0172] The fiber pretreatment device 2 is composed of a combination of a tension roller and a hot oven, which combination releases the tension of the fiber when it enters the hot oven, so as to adapt to different strength of the fiber and avoid the fiber with small strength from being broken before entering the impregnation die. The surface of the tension roller in the fiber pretreatment device 2 needs to be treated with ceramic plating to increase the surface roughness and reduce the friction to the fiber.

[0173] In the manufacturing system, the fiber frame and fiber guide device 1 is used for guiding and untwisting the fiber, and is provided with an automatic control untwisting device and is connected with the traction machine 8 and the electric control system (such as the PLC control device).

[0174] In the manufacturing system, the cooling water tank 6, the drying machine 7, the traction machine 8, the pelletizer 9 and the collection box 10 are conventional devices or apparatuses known by those skilled in the art, which will not be described here.

[0175] Figure 7 A schematic diagram of the second impregnation treatment using the forming die is shown, Figure 8 A sectional view of the forming die used in the second impregnation treatment is shown.

[0176] As shown, Figure 8 In an embodiment, the forming die 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 to form a cavity with the outer sleeve 5-2, and the resin melt can enter the cavity from the bottom or top or two 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. The pressure of the melt in the cavity can also be adjusted by adjusting the angle between the core 5-1 and the outer sleeve 5-2. The working principle of the forming die 5 is as follows: the strip formed by the inner layer impregnated material after passing through the impregnation die 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 filled with mixed melt formed by the core 5-1 and the outer sleeve 5-2, and finally it is guided out through the outer sleeve die plate 5-3.

[0177] AsFigure 7 As shown, the strand 5-4 enters a cavity formed by the core (not shown) and the sheath 5-2, which is filled with the melt of the second component, where the melt of the second component is fed into the cavity from the second resin inlet 5-5.

[0178] In the following examples and comparative examples, the following materials were used Figure 3 The conductive polyglycolic acid composite was prepared by the manufacturing system shown in the figure, where the first impregnation treatment used Figure 4 The first impregnation mold shown in the figure, and the second impregnation treatment used Figure 8 The molding mold shown in the figure.

[0179] The conductive polyglycolic acid composite and the preparation method thereof provided by the present application will be described in detail below in conjunction with specific examples.

[0180] 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 all conventional biochemical reagents; the raw materials, instruments and equipment used in the following examples can be purchased on the market or obtained by existing methods; the reagent amount, unless otherwise specified, is the reagent amount in conventional experimental operation; the experimental method, unless otherwise specified, is a conventional method.

[0181] In each of the examples and comparative examples of the present application, the test method of each performance data is as follows:

[0182] (1) Tensile strength: GB / T 1040-2018;

[0183] (2) Flexural modulus: GB / T 9341-2008;

[0184] (3) Charpy notched impact strength: GB / T 1843-2008;

[0185] (4) Heat distortion temperature: GB / T 1634.2-2019, A method, bending stress 1.8 MPa;

[0186] (5) Volume resistivity: GB / T 31838.2-2019, Part 2: Resistive properties (DC method) of solid insulating materials - Dielectric and resistive properties.

[0187] In each of the examples and comparative examples of the present application, the materials used are as follows:

[0188] (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 Pujing Chemical Co., Ltd., and the last two were purchased from Japan Wuhe and Liaoning Jinmei, respectively;

[0189] (2) Glass fiber: Alkali-free glass fiber, diameter 17 μm, linear density 2400 tex, Chongqing International Composite Material Co., Ltd.;

[0190] (3) Antioxidant 1010: BASF, Germany;

[0191] (4) Antioxidant 168: BASF, Germany;

[0192] (5) Antioxidant 245: Li & Fung;

[0193] (6) Silane coupling agent: KH-550, Nanjing Youpu Chemical Co., Ltd.;

[0194] (7) Calcium stearate: Calcium content 6.5 wt%, InoKai Co., Ltd.;

[0195] (8) Acetylene black: Tianjin Huacai Chemical Co., Ltd.;

[0196] (9) Silver powder: Average particle size 3-5 μm, Shanghai Lianghan Nanometer Technology Development Co., Ltd.;

[0197] (10) Natural flake graphite: Nanjing Jicang Nanometer Technology Co., Ltd.;

[0198] (11) Conductive carbon black: Cabot;

[0199] (12) Edge-modified graphene: Self-made by Beijing Chemical Research Institute;

[0200] 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;

[0201] 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°C by the jacket; then the rotation 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, to obtain the edge-modified graphene.

[0202] Example 1

[0203] (1) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) is mixed with 1 part by weight of KH550, 0.2 parts by weight of antioxidant 168, 0.3 parts by weight of antioxidant 245, and 0.2 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes to obtain a first component melt, which is then fed into a first impregnation mold.

[0204] (2) The continuous glass fiber is introduced into the first impregnation die under the action of the pulling machine, impregnated and dispersed with the first component melt to form a sample, which is used as the inner layer material, wherein the glass fiber content is 60 parts by weight.

[0205] (3) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) is mixed with 20 parts by weight of acetylene black, 2 parts by weight of KH550, 0.1 part by weight of antioxidant 245, and 0.5 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, which is used as the outer layer material, wherein the acetylene black is forcedly fed through a side-feeding system and sent into a double-screw extruder connected to the forming die to obtain the second component melt.

[0206] (4) The inner layer material is introduced into the forming die under the action of the pulling 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 second component melt formed by the core and the outer sleeve, and finally guided out through the outer sleeve die plate.

[0207] (5) The amount of the outer layer material is adjusted by adjusting the amount of the extruder for the outer layer material and the diameter of the die plate outlet, so that it is coated according to the defined amount, and the cutter speed of the cutter is adjusted to control the length of the obtained polyglycolic acid composite material to be 15 mm. The content of the first polyglycolic acid in the obtained composite material is 100 parts by weight, the content of the glass fiber is 60 parts by weight, the content of the second polyglycolic acid is 100 parts by weight, and the content of the acetylene black is 20 parts by weight.

[0208] (6) The conductive polyglycolic acid composite material prepared by the above method is injection molded into a standard sample for performance testing. The test results are shown in Table 1.

[0209] Comparative Example 1

[0210] (1) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) is mixed with 1 part by weight of KH550, 0.2 parts by weight of antioxidant 168, 0.3 parts by weight of antioxidant 245, 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.

[0211] (2) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) is mixed with 20 parts by weight of acetylene black, 2 parts by weight of KH550, 0.1 part by weight of antioxidant 245, and 0.5 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes.

[0212] (3) The two mixtures above 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, the content of the second polyglycolic acid was 100 parts by weight, and the content of the acetylene black was 20 parts by weight.

[0213] (4) The conductive polyglycolic acid composite prepared above was injection molded into standard bars for performance testing. The test results are shown in Table 1.

[0214] Comparative Example 2

[0215] (1) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) was stirred with 1 part by weight of KH550, 0.2 parts by weight of antioxidant 168, 0.3 parts by weight of antioxidant 245, 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, followed by melt granulation, to obtain polyglycolic acid composite 1.

[0216] (2) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) was stirred with 20 parts by weight of acetylene black, 2 parts by weight of KH550, 0.1 parts by weight of antioxidant 245, and 0.5 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, followed by melt granulation, to obtain polyglycolic acid composite 2.

[0217] (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, the content of the second polyglycolic acid was 100 parts by weight, and the content of the acetylene black was 20 parts by weight.

[0218] (4) The conductive polyglycolic acid composite prepared above was injection molded into standard bars for performance testing. The test results are shown in Table 1.

[0219] Comparative Example 3

[0220] (1) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) was stirred with 1 part by weight of KH550, 0.2 parts by weight of antioxidant 168, 0.3 parts by weight of antioxidant 245, 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, followed by melt granulation, to obtain polyglycolic acid composite 1.

[0221] (2) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) was mixed with 20 parts by weight of acetylene black, 2 parts by weight of KH550, 0.1 part by weight of antioxidant 245, and 0.5 part by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, and then subjected to internal mixing, at a temperature of 220°C for 20 minutes, at a screw speed of 20 rpm, followed by extrusion and granulation, to obtain polyglycolic acid composite 2.

[0222] (3) Polyglycolic acid composite 1 and polyglycolic acid composite 2 were fed together into a twin-screw extruder for melt granulation, to obtain polyglycolic acid composite particles with a length of 15 mm. The content of the first polyglycolic acid in the obtained composite was 100 parts by weight, the content of glass fiber was 60 parts by weight, the content of the second polyglycolic acid was 100 parts by weight, and the content of acetylene black was 20 parts by weight.

[0223] (4) The conductive polyglycolic acid composite prepared above was injection molded into standard test bars for performance testing. The test results are shown in Table 1.

[0224] Example 2

[0225] (1) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) was mixed with 0.05 parts by weight of KH550, 0.05 parts by weight of antioxidant 168, 0.05 parts by weight of antioxidant 245, and 0.5 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, to obtain a first component melt, which was fed into a first impregnation mold.

[0226] (2) Continuous glass fibers were fed into the first impregnation mold under the action of a traction machine, impregnated and dispersed with the first component melt, to form a test bar, which was used as an inner layer material, and the content of glass fiber was 20 parts by weight.

[0227] (3) 100 parts by weight of polyglycolic acid (melt index 150 g / 10 min) was mixed with 20 parts by weight of acetylene black, 0.1 part by weight of KH550, 0.2 part by weight of antioxidant 1010, and 0.2 part by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, which was used as an outer layer material, and fed into a twin-screw extruder connected to a molding mold, to obtain a second component melt.

[0228] (4) The inner layer material was fed into the molding mold under the action of a traction machine, guided through a hole in the middle of the core, and formed into a composite structure of inner and outer layer materials in a cavity filled with the second component melt formed between the core and the outer sleeve, and finally guided out through the outer sleeve die plate.

[0229] (5) The amount of the outer layer material is adjusted by adjusting the amount of extrusion and the diameter of the die exit of the extruder for the outer layer material, so that the outer layer material is coated in a defined amount. The speed of the cutter of the cutter granulator is adjusted, and the length of the obtained polyglycolic acid composite is controlled to be 6 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, the content of the second polyglycolic acid is 100 parts by weight, and the content of the acetylene black is 20 parts by weight.

[0230] (6) The conductive polyglycolic acid composite prepared by the above method is injection molded into a standard sample bar, and performance testing is performed. The test results are shown in Table 1.

[0231] Example 3

[0232] (1) 100 parts by weight of polyglycolic acid (melt index 150 g / 10 min) is mixed with 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 to obtain a first component melt, which is then fed into a first impregnation mold.

[0233] (2) Continuous glass fibers are introduced into the first impregnation mold under the action of a traction machine, impregnated and dispersed with the second component melt described above to form a sample bar, which serves as an inner layer material, and the content of the glass fiber is 150 parts by weight.

[0234] (3) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) is mixed with 20 parts by weight of acetylene black, 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 an outer layer material, and is fed into a double-screw extruder connected to a molding mold to obtain a second component melt.

[0235] (4) The inner layer material is introduced into the molding mold under the action of the traction machine, guided through the hole in the middle of the core, and realizes the molding of the composite structure of the inner and outer layer materials in the cavity filled with the second component melt formed by the core and the outer sleeve, and finally guided out through the outer sleeve die plate.

[0236] (5) The amount of the outer layer material is adjusted by adjusting the amount of extrusion and the diameter of the die exit of the extruder for the outer layer material, so that the outer layer material is coated in a defined amount. The speed of the cutter of the cutter granulator is adjusted, and the length of the obtained polyglycolic acid composite is controlled to be 6 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, the content of the second polyglycolic acid is 100 parts by weight, and the content of the acetylene black is 20 parts by weight.

[0237] (6) The conductive 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 4

[0239] The preparation process is the same as that of Example 1, except that 5 parts by weight of acetylene black is added in step (3). The polyglycolic acid composite is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0240] Example 5

[0241] The preparation process is the same as that of Example 1, except that 40 parts by weight of acetylene black is added in step (3). The polyglycolic acid composite is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0242] Example 6

[0243] The preparation process is the same as that of Example 1, except that 20 parts by weight of acetylene black added in step (3) is replaced by 20 parts by weight of silver powder. The polyglycolic acid composite is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0244] Example 7

[0245] The preparation process is the same as that of Example 1, except that 20 parts by weight of acetylene black added in step (3) is replaced by 20 parts by weight of natural flake graphite. The polyglycolic acid composite is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0246] Example 8

[0247] The preparation process is the same as that of Example 1, except that 20 parts by weight of acetylene black added in step (3) is replaced by 20 parts by weight of conductive carbon black. The polyglycolic acid composite is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0248] Comparative Example 4

[0249] The preparation process is the same as that of Example 1, except that 20 parts by weight of acetylene black is not added in step (3). The polyglycolic acid composite is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0250] Example 9

[0251] The preparation process is the same as that of Example 5, except that 20 parts by weight of acetylene black is added in step (3), and 0.4 parts of edge-modified graphene is also added. The polyglycolic acid composite is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0252] Table 1 Material property test of examples and comparative examples

[0253]

[0254] From the test results of Example 1 and Comparative Examples 1-3, it can be seen that the performance of the composite material prepared by directly melt blending the inner and outer layer materials or by preparing the composite material after mixing in an internal mixer is much lower than that of the conductive polyglycolic acid composite material prepared according to the preparation method described in the present application, which shows that the conductive polyglycolic acid composite material provided by the present application can uniformly disperse a high content of conductive filler and maintain the length of the filled fiber, and finally obtain a conductive polyglycolic acid composite material with excellent performance.

[0255] From the test results of each example and Comparative Example 4, it can be seen that the addition of conductive filler in the outer layer material can significantly improve the conductive performance of the composite material.

[0256] From the test results of Example 1 and Examples 4-5, it can be seen that the addition amount of acetylene black affects the conductive performance and mechanical performance. The more the addition amount of acetylene black, the better the conductive performance, and the mechanical performance will decrease.

[0257] From the test results of Example 1 and Examples 6-8, it can be seen that the addition of acetylene black as a conductive filler compared to the addition of an equal amount of other conductive fillers can make the conductive performance of the composite material better.

[0258] From the test results of Example 9 and Example 5, it can be seen that the addition of a small amount of edge-modified graphene in combination with acetylene black can significantly reduce the amount of acetylene black while maintaining the same conductive performance of the composite material. The combination of edge-modified graphene and acetylene black can not only maintain the good conductive performance of the composite material, but also reduce the adverse effects of a large amount of acetylene black on the mechanical performance of the composite material.

[0259] In addition, the composite material of Example 2 has improved gloss performance.

[0260] It should be noted that the above-described examples are only used to explain the present application and do not constitute any limitation on the present application. The present application has been described by referring to typical examples, but it should be understood that the words used therein are descriptive and explanatory words, rather than limiting words. Modifications can be made to the present application within the scope of the claims of the present application, and the present application can be revised without departing from the scope and spirit of the present application. Although the present application described therein relates to specific methods, materials and examples, it does not mean that the present application is limited to the specific examples disclosed therein, on the contrary, the present application can be extended to all other methods and applications with the same function.

Claims

1. An electrically conductive polyglycolic acid composite, characterized in that, The composite material 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 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, a conductive filler, and a second additive; The conductive filler is at least one of a carbon material, a metal, and a metal oxide; In the inner core material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the glass fibers is 10-200 parts by weight; And / or, in the outer layer material, the amount of the second polyglycolic acid resin is 100 parts by weight, and the amount of the conductive filler is 10-50 parts by weight; 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 50-100 parts by weight.

2. The composite material of claim 1, wherein, The carbon material comprises at least one of carbon black, carbon fibers, single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, fullerenes, mesocarbon microbeads, graphite, expanded graphite, and acetylene black; and / or the metal comprises at least one of copper powder, silver powder, aluminum powder, aluminum-steel composite fibers, iron powder, and gold powder; and / or the metal oxide comprises at least one of Al2O3, MgO, TiO2, and Fe2O3.

3. The composite material of claim 2, wherein, The conductive filler at least comprises acetylene black.

4. The composite material of claim 1, wherein, The conductive filler comprises acetylene black and edge-modified graphene.

5. The composite material of claim 4, wherein, The weight ratio of the acetylene black to the edge-modified graphene is (20-100):1; And / or the average flake diameter of the edge-modified graphene is 2-30 μm; 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 in the edge-modified graphene, the oxygen content is 0.5wt%-20wt%, and the hydrogen content is 0.01wt%-1wt%; And / or the edge-modified graphene is prepared by grinding graphite under supercritical carbon dioxide.

6. The composite material of claim 5, wherein, The average flake diameter of the edge-modified graphene is 5-20 μm; 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 in the edge-modified graphene, the oxygen content is 3wt%-10wt%, and the hydrogen content is 0.05wt%-0.5wt%.

7. The composite material of claim 6, wherein, The average aspect ratio of the edge-modified graphene is 1000-3000:

1.

8. The composite material according to any one of claims 1 to 7, wherein In the inner core material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the glass fibers is 10-150 parts by weight.

9. The composite material of claim 8, wherein, In the inner core material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the glass fibers is 20-150 parts by weight.

10. The composite material according to any one of claims 1 to 7, wherein The first polyglycolic acid resin and the second polyglycolic acid resin are the same or different, and each is independently selected from homopolymerized polyglycolic acid and / or copolymerized polyglycolic acid. and / or, the melt flow rate of the first polyglycolic acid resin under the condition of 230℃, 2.16kg is 5-500g / 10min; and / or, the melt flow rate of the second polyglycolic acid resin under the condition of 230℃, 2.16kg is 5-500g / 10min.

11. The composite material of claim 10, wherein, The content of glycolic acid monomer in the copolymerized polyglycolic acid is ≥90mol%; and / or, the melt flow rate of the first polyglycolic acid resin under the condition of 230℃, 2.16kg is 10-200g / 10min; and / or, the melt flow rate of the second polyglycolic acid resin under the condition of 230℃, 2.16kg is 10-200g / 10min.

12. The composite material of claim 11, wherein, The content of glycolic acid monomer in the copolymerized polyglycolic acid is ≥95mol%; and / or, the melt flow rate of the first polyglycolic acid resin under the condition of 230℃, 2.16kg is 10-100g / 10min; and / or, the melt flow rate of the second polyglycolic acid resin under the condition of 230℃, 2.16kg is 10-100g / 10min.

13. The composite material of any one of claims 1-7, wherein, The amount of the first polyglycolic acid resin is 100 parts by weight, and the first auxiliary agent comprises 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 part by weight of the first lubricant; and / or, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second auxiliary agent comprises 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 part by weight of the second lubricant.

14. The composite material of claim 13, wherein, The amount of the first polyglycolic acid resin is 100 parts by weight, and the first auxiliary agent comprises at least one of 0.05-2 parts by weight of the first compatibilizer, 0.1-1 part by weight of the first antioxidant and 0.2-1 part by weight of the first lubricant; and / or, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second auxiliary agent comprises at least one of 0.05-2 parts by weight of the second compatibilizer, 0.1-1 part by weight of the second antioxidant and 0.2-1 part by weight of the second lubricant.

15. The composite material of claim 13, wherein, 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; and / or, 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 245, antioxidant CA and antioxidant 626; and / or, 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, polyethylene wax, erucamide, pentaerythritol stearate.

16. The composite material of claim 15, wherein, The first compatibilizer and the second compatibilizer are the same or different, and each is independently selected from at least one of a silane coupling agent, a titanate coupling agent, an organic chromium complex coupling agent; 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 245.

17. The composite material of claim 16, wherein, The first compatibilizer and the second compatibilizer are the same or different, each independently selected from a silane coupling agent.

18. The composite material of any one of claims 1-7, wherein, The inner core material does not contain non-oriented short fibers.

19. The composite material of claim 18, wherein, The inner core material is composed of a first polyglycolic acid resin, glass fibers and a first aid.

20. A method of making the conductive polyglycolic acid composite of any one of claims 1-19, wherein, Comprising: S1. After mixing the first polyglycolic acid resin and the first aid, melt to obtain a first component melt; S2. The continuous glass fiber is subjected to first impregnation treatment with the first component melt in step S1 to form a filamentous inner core material; S3. After mixing the second polyglycolic acid, the conductive filler and the second aid, melt to obtain a second component melt; S4. The inner core material obtained in step S2 is subjected to at least one second impregnation treatment with at least one second component melt in step S3 to obtain a conductive polyglycolic acid composite material.

21. The method of claim 20, wherein, The mixing conditions of step S1 are: temperature 40-60℃, time 3-5min; and / or the melting temperature of step S1 is 230-260℃; And / or, the mixing conditions of step S3 are: temperature 40-60℃, time 3-5min; and / or the melting temperature of step S3 is 230-260℃; And / or, the step S2 further comprises: before the first impregnation treatment of the continuous glass fiber, the continuous glass fiber is subjected to dispersion treatment and preheating treatment; And / or, the step S4 further comprises: after the second impregnation treatment, the material obtained after the second impregnation treatment is subjected to pulling out, stretching, cooling, drying, and cutting treatment to obtain a conductive polyglycolic acid composite material.

22. The method of claim 21, wherein, The temperature of the preheating treatment is 80-250℃.

23. The method of making according to any one of claims 20-22, wherein, 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.

24. The method of making according to any one of claims 20-22, wherein, 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.

25. The method of any one of claims 20-22, wherein, The first impregnation treatment in step S2 is performed in a third impregnation die, which is a strong turbulent impregnation die, and the third impregnation die comprises a fiber inlet channel, an impregnation outlet and a melt split runner, all of which are communicated 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.

26. Use of the composite material of any one of claims 1-19 or the composite material prepared by the preparation method of any one of claims 20-25 in the field of electromagnetic shielding, sensors.

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