A reinforced and toughened modified polyglycolic acid composite material, its preparation method and application

Abstract

This invention relates to the field of polymer composite materials technology, and provides a reinforced and toughened modified polyglycolic acid composite material, its preparation method, and its applications. The composite material includes an inner core material and at least one outer layer material; the inner core material includes a first polyglycolic acid resin, fibers, and a first additive, the fibers continuously extending from one end of the inner core material to its opposite end; the outer layer material encapsulates the inner core material, and the outer layer material includes a second polyglycolic acid resin, a toughening agent, a filler, and a second additive. The composite material of this invention is based on a multi-component material design, possessing high strength, high toughness, high heat resistance, good processability, and biodegradability. Simultaneously, the continuous fiber reinforcement allows for uniform dispersion of highly filler components such as fillers and toughening agents, fully leveraging the synergistic effect between components, resulting in a significant improvement in the overall performance of the polyglycolic acid composite material and expanding its application areas.

Description

Technical Field

[0001] This invention relates to the field of polymer composite materials, and more specifically, to a reinforced and toughened modified polyglycolic acid composite material, its preparation method, and its application. Background Technology

[0002] Polyglycolic acid (PGA), as a novel environmentally friendly biodegradable material, has received extensive research attention in recent years. PGA possesses a simple, regular linear molecular structure, high mechanical properties (tensile strength, flexural modulus, etc.), barrier properties, and heat resistance, making it a potential alternative to biodegradable materials with strengths exceeding those of engineering plastics. Currently, many companies are investing in the PGA industry, and with subsequent technological and production capacity optimization and upgrades, PGA will see even larger-scale applications.

[0003] Due to the high regularity of its molecular chains, PGA also suffers from defects such as similar melting and decomposition temperatures, a narrow processing window, and insufficient toughness, far lower than similar materials like PLA and PET. The brittleness and poor toughness of PGA limit its further applications. To improve the toughness of PGA materials, existing techniques mainly include physical modification and chemical modification. Physical modification primarily involves polymer composites. For example, Qiao Hu et al. studied the modification of polyglycolic acid with PBAT, improving the compatibilizer between the two phases by introducing epoxy chain extenders; however, the mechanical properties of the resulting modified product still had defects. Shen et al. systematically studied the effect of PGA content on the structure and properties of PGA / PBAT materials. PBAT / PGA composites generally exhibited a better balance between stiffness and ductility and higher processing stability, but the problem of poor PGA toughness was not completely resolved.

[0004] Long fibers can endow composite materials with excellent mechanical properties. Through structural design and toughening formulation control, composite materials with high modulus, high strength, and high toughness can be prepared, further improving the poor processability and toughness of PGA. In addition, long fibers themselves belong to a class of biodegradable materials and have broad application prospects in the modification of biodegradable materials; however, the dispersion of long fibers in biodegradable resin matrices is a research challenge, especially when blended with other fillers (such as toughening agents), where aggregation problems easily occur among multiple fillers.

[0005] To address the aforementioned issues, existing technologies cannot yet meet practical needs. Therefore, developing continuous fiber-reinforced polyglycolic acid composite materials with good processing performance, high toughness, uniform filler dispersion, and high filler content, along with their production processes and applications, has significant market value and research significance. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a reinforced and toughened modified polyglycolic acid composite material, its preparation method, and its application.

[0007] The technical solution adopted in this invention is:

[0008] In a first aspect, the present invention proposes a reinforced and toughened modified 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, fibers and a first additive, wherein the fibers extend continuously from one end of the inner core material to its opposite end; the outer layer material encapsulates the inner core material, and the outer layer material comprises a second polyglycolic acid resin, a toughening agent, a filler and a second additive.

[0009] As a preferred embodiment of the composite material provided by the present invention, in the core material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of glass fiber is 10-200 parts by weight, preferably 10-150 parts by weight, and more preferably 20-150 parts by weight.

[0010] And / or, in the outer layer material, the amount of the second polyglycolic acid resin is 100 parts by weight, the amount of the toughening agent is 1-59 parts by weight, preferably 2-40 parts by weight, more preferably 5-30 parts by weight; and / or the amount of the filler is 1-99 parts by weight, preferably 5-50 parts by weight, more preferably 10-50 parts by weight.

[0011] 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, more preferably 50-100 parts by weight.

[0012] As another preferred embodiment of the composite material provided by the present invention, the toughening agent is selected from at least one of biodegradable polyester, natural rubber, bio-based elastomers, polyolefin copolymers, and specialty rubbers; preferably polybutylene adipate terephthalate (PBAT), polybutylene terephthalate succinate (PBST), polybutylene succinate (PBS) and its copolymers, polyhydroxyalkanoates (PHA), polycaprolactone (PCL), natural rubber, ethylene-octene copolymer (POE) and its modifiers, hydrogenated nitrile butadiene rubber, etc. At least one of functionalized solution-polymerized styrene-butadiene; more preferably at least one of polybutylene terephthalate (PBAT), polybutylene terephthalate (PBST), ethylene-octene copolymer (POE) and its maleic anhydride-modified derivative, and hydrogenated nitrile butadiene rubber; even more preferably maleic anhydride-modified ethylene-octene copolymer (POE) and hydrogenated nitrile butadiene rubber; and even more preferably, the weight ratio of the maleic anhydride-modified ethylene-octene copolymer (POE) to the hydrogenated nitrile butadiene rubber is 0.2 to 5.

[0013] As another preferred embodiment of the composite material provided by the present invention, the filler is selected from at least one of organic fillers and inorganic fillers; preferably inorganic fillers; more preferably at least one of calcium carbonate, talc, glass microspheres, kaolin, silicon dioxide, carbon black, montmorillonite, barium sulfate, wollastonite, and whiskers; even more preferably at least one of calcium carbonate, talc, glass microspheres, kaolin, montmorillonite, and wollastonite.

[0014] And / or, the inorganic filler particle size is 0.05-100μm, preferably 0.06-50μm, more preferably 0.08-1μm.

[0015] As another preferred embodiment of the composite material provided by the present invention, the first polyglycolic acid resin and the second polyglycolic acid resin may be the same or different, and each is independently selected from homopolymer polyglycolic acid and / or copolymer polyglycolic acid; preferably, the content of glycolic acid monomer in the copolymer polyglycolic acid is ≥90mol%, preferably ≥95mol%.

[0016] And / or, the melt flow rate of the first polyglycolic acid resin at 230°C and 2.16 kg is 5-500 g / 10 min, preferably 10-200 g / 10 min, and more preferably 10-100 g / 10 min;

[0017] And / or, the melt flow rate of the second polyglycolic acid resin at 230°C and 2.16 kg is 5-500 g / 10 min, preferably 10-200 g / 10 min, and more preferably 10-100 g / 10 min.

[0018] As another preferred embodiment of the composite material provided by the present invention, the first polyglycolic acid resin is used in an amount of 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 parts by weight of a first lubricant; preferably, the first polyglycolic acid resin is used in an amount of 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 parts by weight of a first antioxidant, and 0.2-1 parts by weight of a first lubricant;

[0019] And / or, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second additive 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 amount of the second polyglycolic acid resin is 100 parts by weight, and the second additive 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.

[0020] As another preferred embodiment of the composite material provided by the present invention, the first compatibilizer and the second compatibilizer may be the same or different, and each is independently selected from at least one coupling agent, preferably at least one of silane coupling agents, titanate coupling agents, and organochromium complex coupling agents, and more preferably silane coupling agents.

[0021] And / or, the first antioxidant and the second antioxidant may be the same or different, and each is independently selected from at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 2246, antioxidant CA and antioxidant 626, preferably at least one of antioxidant 1010 and antioxidant 168;

[0022] And / or, the first lubricant and the second lubricant may be the same or different, and each is independently selected from at least one of ethylene bis-stearamide, calcium stearate, mono-fatty acid glyceride, polyethylene wax, erucamide, and pentaerythritol stearate.

[0023] As another preferred embodiment of the composite material provided by the present invention, the core material does not contain non-oriented short fibers. Preferably, the core material is composed of a first polyglycolic acid resin, glass fiber and a first additive.

[0024] Secondly, the present invention provides a method for preparing the above-mentioned reinforced and toughened modified polyglycolic acid composite material, comprising:

[0025] S1. The first polyglycolic acid resin and the first additive are mixed and melted to obtain the first component melt;

[0026] S2. The continuous glass fiber is subjected to a first impregnation treatment with the first component melt in step S1 to form a filamentous core material;

[0027] S3. The second polyglycolic acid, toughening agent, filler, and second additive are mixed and melted to obtain the second component melt;

[0028] S4. The core material obtained in step S2 is subjected to at least one second impregnation treatment with at least one second component melt from step S3 to obtain a reinforced and toughened modified polyglycolic acid composite material.

[0029] As a preferred embodiment of the preparation method provided by the present invention, the mixing conditions of step S1 are: temperature of 40-60℃, time of 3-5 min; and / or the melting temperature of step S1 is 230-260℃.

[0030] And / or, the mixing conditions in step S3 are: temperature of 40-60℃, time of 3-5 min; and / or the melting temperature in step S3 is 230-260℃;

[0031] And / or, step S2 further includes: dispersing and preheating the continuous glass fibers before the first impregnation treatment; preferably, the temperature of the preheating treatment is 80-250°C;

[0032] And / or, step S4 further includes: after the second impregnation treatment, the material obtained by the second impregnation treatment is subjected to pull-out, strip-drawing, cooling, drying and pelletizing treatment to obtain a reinforced and toughened modified polyglycolic acid composite material.

[0033] As another preferred embodiment of the preparation method provided by the present invention, in step S2, the first impregnation treatment is performed in a first impregnation mold. The first impregnation mold is an adjustable impregnation mold, which includes a fiber inlet, a fiber outlet, and a melt flow channel. At least one first guide roller is provided in the mold cavity of the first impregnation mold. The first guide roller is movable between the fiber inlet and the fiber outlet. And / or, the first guide roller is movable along a direction perpendicular to the line connecting the fiber inlet and the fiber outlet.

[0034] As another preferred embodiment of the preparation method provided by the present invention, in step S2, the first impregnation treatment is carried out in the second impregnation mold. The second impregnation mold is a combined impregnation mold, which includes a first module, an intermediate module and a second module connected in sequence. The first module is provided with a fiber inlet and a first module flow channel. The second module is provided with a fiber outlet and a second module flow channel. The intermediate module is provided with an intermediate module flow channel. After the first module, the intermediate module and the second module are connected in sequence, the first module flow channel, the intermediate module flow channel and the second module flow channel are connected to form a combined flow channel for the fiber to pass through.

[0035] As another preferred embodiment of the preparation method provided by the present invention, in step S2, the first impregnation treatment is carried out in a third impregnation mold. The third impregnation mold is a strong turbulent impregnation mold. The third impregnation mold includes a fiber inlet channel, an impregnation outlet, and a melt gap flow channel. The fiber inlet channel, the impregnation outlet, and the melt gap flow channel are all connected to the mold cavity inside the third impregnation mold. A second guide roller is provided inside the mold cavity of the third impregnation mold. The second guide roller includes at least one active guide roller, which is driven to rotate by a driving device.

[0036] Thirdly, the present invention provides applications of the above-mentioned reinforced and toughened modified polyglycolic acid composite material or the reinforced and toughened modified polyglycolic acid composite material prepared by the above-mentioned preparation method in the fields of catering, construction, oilfield chemical industry, and engineering plastics.

[0037] The beneficial effects of this invention are at least as follows:

[0038] (1) The reinforced and toughened modified polyglycolic acid composite material of the present invention is a double-layer structure design with an outer toughening layer and an inner reinforcement layer. The inner layer material contains continuous / fixed-length fibers. Through the impregnation process of the present invention, not only can a high content of long fibers be uniformly dispersed in polyglycolic acid, but fiber leakage can also be prevented, giving full play to the role of long fibers in increasing rigidity and improving heat resistance. The outer layer material is toughened and reinforced by the synergistic use of toughening agents and fillers. In addition, the combined use of fillers and toughening agents can effectively improve the processing fluidity of polyglycolic acid, while significantly reducing the cost of the composite material.

[0039] (2) The reinforced and toughened modified polyglycolic acid composite material of the present invention is based on a multi-component material design, which has high strength, high toughness, high heat resistance, good processing performance and biodegradability. At the same time, while continuous fiber reinforcement, the filler, toughening agent and other high filler components can be evenly dispersed, giving full play to the synergistic effect between the components, which significantly improves the comprehensive performance of the polyglycolic acid composite material and expands the application field. Attached Figure Description

[0040] Figure 1 This is a schematic diagram of the reinforced and toughened modified polyglycolic acid composite material structure in one embodiment of the present invention;

[0041] Figure 2 This is a schematic diagram of a manufacturing system for reinforced and toughened modified polyglycolic acid composite materials according to one embodiment of the present invention;

[0042] Figure 3 This is a schematic diagram of the structure of a reinforced and toughened modified polyglycolic acid composite material manufacturing system according to another embodiment of the present invention;

[0043] Figure 4 This is a cross-sectional view of the first impregnation mold in one embodiment of the present invention;

[0044] Figure 5 This is a cross-sectional view of the second impregnation mold in one embodiment of the present invention;

[0045] Figure 6 This is a cross-sectional view of the third impregnation mold in one embodiment of the present invention;

[0046] Figure 7 This is a schematic diagram of the second impregnation treatment in one embodiment of the present invention;

[0047] Figure 8 This is a cross-sectional view of the molding die used in the second impregnation process according to one embodiment of the present invention.

[0048] Explanation of reference numerals in the attached figures:

[0049] 0-1, Inner core material; 0-2, Fiber bundle; 0-3, Outer layer material;

[0050] 1. Fiber rack and fiber guiding device; 2. Fiber pretreatment device; 3. First impregnation mold; 4. Melting and plasticizing feeding device; 5. Molding mold; 6. Cooling water tank; 7. Dryer; 8. Traction machine; 9. Pelletizer; 10. Collection box;

[0051] A300, First impregnation die head; A1, Fiber inlet; A2, Second chute; A3, Melt flow channel; A4, First chute; A5, Upper die cover; A6, Fiber outlet; A7, Impregnation die body; A8, First guide roller;

[0052] B300, Second impregnation die head; B1, Fiber inlet; B2, Melt channel; B3, First module; B31, First module channel; B4, Combined channel; B5, Standardized connector; B6, Intermediate module; B61, Intermediate module channel; B7, Second module; B71, Second module channel; B8, Fiber outlet;

[0053] C300, Third impregnation die head; C1, Melt flow channel; C2, Impregnation die body; C3, Fiber inlet channel; C4, Active guide roller; C5, Driven guide roller; C6, Impregnation outlet;

[0054] 4-1. Extruder I; 4-2. Extruder II;

[0055] 5-1 Core; 5-2 Outer shell; 5-3 Outer shell opening template; 5-4 Material strip; 5-5 Second resin inlet. Detailed Implementation

[0056] To make the technical problem to be solved, the technical solution, and the beneficial effects of this invention clearer, the invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely for illustrating this patent and do not limit the scope of protection of this invention in any way.

[0057] In a first aspect, the reinforced and toughened modified polyglycolic acid composite material proposed in this invention includes an inner core material and at least one outer layer material; the inner core material includes a first polyglycolic acid resin, fibers, and a first additive, wherein the fibers extend continuously from one end of the inner core material to its opposite end; the outer layer material encapsulates the inner core material, and the outer layer material includes a second polyglycolic acid resin, a toughening agent, a filler, and a second additive.

[0058] The reinforced and toughened modified polyglycolic acid composite material of the present invention uses a first component comprising a first polyglycolic acid resin and a first additive to impregnate continuous fibers to form an inner core material, and a second component comprising a second polyglycolic acid resin, a toughening agent, a filler, and a second additive to uniformly coat the outer side of the inner core material. This forms a reinforced and toughened modified polyglycolic acid composite material with continuous fiber-reinforced resin as the inner core material and a resin layer surrounding the inner core material as the outer layer material. Such a polyglycolic acid composite material exhibits excellent mechanical properties. By adding a toughening agent and filler to the outer layer material, the composite material can be reinforced and toughened.

[0059] In this invention, the terms "one end" and "opposite end" are generally used relative to the longitudinal direction of the reinforced and toughened modified polyglycolic acid composite material.

[0060] In the transverse cross section of the reinforced and toughened modified polyglycolic acid composite material, from the inside out are the inner core material and the outer layer material, and the fibers are oriented along the longitudinal direction of the reinforced and toughened modified polyglycolic acid composite material in the inner core material.

[0061] The fibers in this invention are fiber bundles, and the length of the fiber bundles is substantially the same as the length (longitudinal dimension) of the reinforced and toughened modified polyglycolic acid composite material. Thus, the fiber bundles extend continuously from one end of the inner core material in the longitudinal direction to the opposite end in the longitudinal direction. The inner core material does not contain short fibers, particularly non-oriented short fibers.

[0062] In the reinforced and toughened modified polyglycolic acid composite material of the present invention, the outer layer material covers at least 80% of the inner core material, for example, 80-99% or 85-95% of the inner core material; the outer layer material may also continuously cover the inner core material.

[0063] The number of outer layers is not limited; it can be one or more layers. In some embodiments, the multiple outer layers can be formed from the same material or from multiple materials.

[0064] The glass fiber is a continuous glass fiber and / or a fixed-length glass fiber.

[0065] According to some embodiments of the present invention, the composite material is in the form of strips, rods, or granules.

[0066] In this invention, the strip-shaped, rod-shaped, or granular reinforced and toughened modified polyglycolic acid composite material can be cut from a continuous filament-shaped reinforced and toughened modified polyglycolic acid composite material.

[0067] According to some embodiments of the present invention, the length of the strip-shaped or rod-shaped composite material is 6-25 mm, for example, it can be 6 mm, 8 mm, 10 mm, 12 mm, 15 mm, 20 mm, 22 mm, 25 mm, etc., preferably 8-20 mm, more preferably 10-15 mm; and / or the particle size of the granular composite material is 3-5 mm, for example, it can be 3 mm, 4 mm, 5 mm, etc., preferably 3-4 mm.

[0068] This invention does not impose special requirements on the cross-sectional shape of the reinforced and toughened modified polyglycolic acid composite material. In some embodiments, the cross-section of the granular or rod-shaped reinforced and toughened modified polyglycolic acid composite material is circular or near-circular. In other embodiments, the cross-section of the granular or strip-shaped reinforced and toughened modified polyglycolic acid composite material is rectangular or square.

[0069] According to some embodiments of the present invention, in the core material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of glass fiber is 10-200 parts by weight, for example, 10 parts by weight, 20 parts by weight, 30 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, etc., preferably 10-150 parts by weight, more preferably 20-150 parts by weight.

[0070] According to some embodiments of the present invention, in the outer layer material, the amount of the second polyglycolic acid resin is 100 parts by weight, the amount of the toughening agent is 1-59 parts by weight, for example, it can be 1 part by weight, 2 parts by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight, 50 parts by weight, 59 parts by weight, etc., preferably 2-40 parts by weight, more preferably 5-30 parts by weight; and / or the amount of the filler is 1-99 parts by weight, for example, it can be 1 part by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 70 parts by weight, 99 parts by weight, etc., preferably 5-50 parts by weight, more preferably 10-50 parts by weight.

[0071] According to some embodiments of the present invention, in the composite material, the first polyglycolic acid resin is used in an amount of 100 parts by weight, and the second polyglycolic acid resin is used in an amount of 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, it is 10-100 parts by weight, more preferably 50-100 parts by weight.

[0072] According to some embodiments of the present invention, the toughening agent is selected from at least one of biodegradable polyester, natural rubber, bio-based elastomers, polyolefin copolymers, and specialty rubbers; preferably at least one of polybutylene adipate, polybutylene terephthalate, polybutylene succinate and its copolymers, polyhydroxy fatty acids, polycaprolactone, natural rubber, ethylene-octene copolymers and their modified forms, hydrogenated nitrile butadiene rubber, and functionalized solution-polymerized styrene-butadiene rubber; more preferably at least one of polybutylene adipate, polybutylene terephthalate, ethylene-octene copolymers and their maleic anhydride modified forms, and hydrogenated nitrile butadiene rubber; even more preferably, the maleic anhydride modified form of ethylene-octene copolymer and hydrogenated nitrile butadiene rubber; and even more preferably, the weight ratio of the maleic anhydride modified form of ethylene-octene copolymer to the hydrogenated nitrile butadiene rubber is 0.2 to 5, for example, 0.2, 0.25, 0.5, 1, 2, 3, 4, 5, etc.

[0073] According to some embodiments of the present invention, toughening agents comprising natural rubber and / or hydrogenated nitrile rubber require vulcanization treatment. The vulcanization treatment can employ commonly used rubber vulcanization processes.

[0074] In this invention, adding a toughening agent to the reinforced and toughened modified polyglycolic acid composite material can improve the impact resistance of the composite material. The toughening agent can be prepared by crushing rubber through internal mixing-vulcanization, or it can be directly prepared into powder by spray drying.

[0075] According to some embodiments of the present invention, a method for preparing a maleic anhydride-modified ethylene-octene copolymer and a toughening agent for hydrogenated nitrile butadiene rubber includes:

[0076] The modified hydrogenated nitrile butadiene rubber masterbatch is prepared by mixing maleic anhydride modified ethylene-octene copolymer, hydrogenated nitrile butadiene rubber, and antioxidant.

[0077] Modified hydrogenated nitrile butadiene rubber masterbatch, zinc oxide, stearic acid, carbon black, antioxidant, vulcanizing agent and vulcanizing agent are mixed and then subjected to intensive mixing and vulcanization to obtain vulcanized rubber.

[0078] The toughening agent is obtained by physically crushing vulcanized rubber.

[0079] According to some embodiments of the present invention, the filler is selected from at least one of organic fillers and inorganic fillers; preferably inorganic fillers; more preferably at least one of calcium carbonate, talc, glass microspheres, kaolin, silicon dioxide, carbon black, montmorillonite, barium sulfate, wollastonite, and whiskers; and even more preferably at least one of calcium carbonate, talc, glass microspheres, kaolin, montmorillonite, and wollastonite.

[0080] According to some embodiments of the present invention, the inorganic filler particle size is 0.05 to 100 μm, for example, it can be 0.05 μm, 0.1 μm, 5 μm, 10 μm, 20 μm, 50 μm, 60 μm, 100 μm, etc., preferably 0.06 to 50 μm, more preferably 0.08 to 1 μm.

[0081] According to some embodiments of the present invention, the first polyglycolic acid resin and the second polyglycolic acid resin may be the same or different, and each is independently selected from homopolymer polyglycolic acid and / or copolymer polyglycolic acid; preferably, the content of glycolic acid monomer in the copolymer polyglycolic acid is ≥90 mol%, preferably ≥95 mol%.

[0082] In different embodiments of the present invention, the melt flow rates of the first polyglycolic acid resin and the second polyglycolic acid resin are not particularly limited, and the melt flow rates of the first polyglycolic acid resin and the second polyglycolic acid resin can be selected according to the desired performance.

[0083] In particular, the inventors of this application have discovered that polyglycolic acid composite materials with high surface quality and overall performance can be prepared using the parameters (e.g., melt flow rate) according to the present invention. For example, if the melt flow rate of the first polyglycolic acid resin is higher than that of the second polyglycolic acid resin, the polyglycolic acid composite material can have improved mechanical properties; conversely, if the melt flow rate of the second polyglycolic acid resin is higher than that of the first polyglycolic acid resin, the polyglycolic acid composite material can have improved gloss.

[0084] According to some embodiments of the present invention, the melt flow rate of the first polyglycolic acid resin at 230°C and 2.16 kg is 5-500 g / 10 min, for example, it can be 5 g / 10 min, 10 g / 10 min, 20 g / 10 min, 40 g / 10 min, 50 g / 10 min, 80 g / 10 min, 100 g / 10 min, 150 g / 10 min, 200 g / 10 min, 300 g / 10 min, 400 g / 10 min, 500 g / 10 min, etc., preferably 10-200 g / 10 min, and more preferably 10-100 g / 10 min.

[0085] According to some embodiments of the present invention, the melt flow rate of the second polyglycolic acid resin at 230°C and 2.16 kg is 5-500 g / 10 min, for example, it can be 5 g / 10 min, 10 g / 10 min, 20 g / 10 min, 40 g / 10 min, 50 g / 10 min, 80 g / 10 min, 100 g / 10 min, 150 g / 10 min, 200 g / 10 min, 300 g / 10 min, 400 g / 10 min, 500 g / 10 min, etc., preferably 10-200 g / 10 min, more preferably 10-100 g / 10 min.

[0086] According to some embodiments of the present invention, the ratio of the melt flow rate of the first polyglycolic acid resin at 230°C and 2.16 kg to the melt flow rate of the second polyglycolic acid resin at 230°C and 2.16 kg is 1-4:1, for example, 1:1, 2:1, 3:1, 3.5:1, 4:1.

[0087] This invention does not limit the specific types and amounts of various additives in the first and second additives, with the aim of achieving the relevant properties of the composite material and realizing the function of the relevant additives.

[0088] According to some embodiments of the present invention, the first polyglycolic acid resin is used in an amount of 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 parts by weight of a first lubricant. For example, the amount of the first compatibilizer may be 0.05 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, etc.; and / or the amount of the first antioxidant may be 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, etc.; and / or the amount of the first lubricant may be 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 part by weight, etc. 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 parts by weight of a first antioxidant, and 0.2-1 parts by weight of a first lubricant.

[0089] According to some embodiments of the present invention, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second additive 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. For example, the amount of the second compatibilizer may be 0.05 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, etc.; and / or, the amount of the second antioxidant may be 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, etc.; and / or, the amount of the second lubricant may be 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 part by weight, etc. Preferably, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second additive 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.

[0090] According to some embodiments of the present invention, the first compatibilizer and the second compatibilizer may be the same or different, and each is independently selected from at least one coupling agent, preferably at least one of silane coupling agents, titanate coupling agents, and organochromium complex coupling agents, more preferably silane coupling agents. Examples of silane coupling agents suitable for use in the present invention include, but are not limited to: KH-550 and KH-560.

[0091] According to some embodiments of the present invention, the first antioxidant and the second antioxidant may be the same or different, and each is independently selected from at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 2246, antioxidant CA and antioxidant 626, preferably at least one of antioxidant 1010 and antioxidant 168.

[0092] According to some embodiments of the present invention, the first lubricant and the second lubricant may be the same or different, and each is independently selected from at least one of ethylene bis-stearamide, calcium stearate, mono-fatty acid glyceride, polyethylene wax, erucamide, and pentaerythritol stearate.

[0093] In different embodiments of the present invention, the first and second additives are not limited to specific types and amounts of these additives, and can have a wide range of selection. For example, the first and second additives may each independently include at least one of chain extenders, slip agents, antistatic agents, and plasticizers.

[0094] Secondly, the present invention provides a method for preparing the above-mentioned reinforced and toughened modified polyglycolic acid composite material, comprising:

[0095] S1. The first polyglycolic acid resin and the first additive are mixed and melted to obtain the first component melt;

[0096] S2. The continuous glass fiber is subjected to a first impregnation treatment with the first component melt in step S1 to form a filamentous core material;

[0097] S3. The second polyglycolic acid, toughening agent, filler, and second additive are mixed and melted to obtain the second component melt;

[0098] S4. The core material obtained in step S2 is subjected to at least one second impregnation treatment with at least one second component melt from step S3 to obtain a reinforced and toughened modified polyglycolic acid composite material.

[0099] The preparation method of the present invention can be carried out online continuously to obtain continuous filamentous products. Such continuous filamentous products can be directly stored and used, or they can be cut into strips, rods or granules with a certain length or particle size.

[0100] According to some embodiments of the present invention, the mixing conditions of step S1 are: temperature of 40-60°C and time of 3-5 min; and / or the melting temperature of step S1 is 230-260°C.

[0101] According to some embodiments of the present invention, the mixing conditions of step S3 are: temperature of 40-60°C, time of 3-5 min; and / or the melting temperature of step S3 is 230-260°C.

[0102] In this invention, steps S1 and S3 and the melting time can have a wide range of selection, with the aim of enabling the first polyglycolic acid resin and the first additive, as well as the second polyglycolic acid resin, toughening agent and the second additive, to be fully melted to obtain a melt.

[0103] According to some embodiments of the present invention, step S2 further includes: dispersing and preheating the continuous glass fibers before performing the first impregnation treatment; preferably, the preheating temperature is 80-250°C. The dispersion process in the present invention employs conventional fiber dispersion processes in the art.

[0104] According to some embodiments of the present invention, step S4 further includes: after the second impregnation treatment, subjecting the material obtained by the second impregnation treatment to pull-out, stretching, cooling, drying, and pelletizing treatments to obtain a reinforced and toughened modified polyglycolic acid composite material. The present invention does not particularly limit the process conditions for pull-out, stretching, cooling, drying, and pelletizing treatments, and those skilled in the art can adjust them according to the specific performance requirements of the prepared reinforced and toughened modified polyglycolic acid composite material.

[0105] According to some embodiments of the present invention, the first impregnation process in step S2 can be performed in a first impregnation mold, the first impregnation mold being an adjustable impregnation mold, the first impregnation mold including a fiber inlet, a fiber outlet and a melt flow channel, and at least one first guide roller being disposed in the mold cavity of the first impregnation mold; the first guide roller is movable between the fiber inlet and the fiber outlet; and / or, the first guide roller is movable along a direction perpendicular to the line connecting the fiber inlet and the fiber outlet.

[0106] According to some embodiments of the present invention, the first impregnation process in step S2 can be performed in a second impregnation mold. The second impregnation mold is a combined impregnation mold, which includes a first module, an intermediate module, and a second module connected in sequence. The first module is provided with a fiber inlet and a first module flow channel, and the second module is provided with a fiber outlet and a second module flow channel. The intermediate module is provided with an intermediate module flow channel. After the first module, the intermediate module, and the second module are connected in sequence, the first module flow channel, the intermediate module flow channel, and the second module flow channel are connected to form a combined flow channel for the fiber to pass through.

[0107] According to some embodiments of the present invention, the first impregnation process in step S2 can also be performed in a third impregnation mold, the third impregnation mold being a strong turbulent impregnation mold, the third impregnation mold including a fiber inlet channel, an impregnation outlet and a melt gap flow channel, the fiber inlet channel, the impregnation outlet and the melt gap flow channel being connected to the mold cavity inside the third impregnation mold; wherein, a second guide roller is provided inside the mold cavity of the third impregnation mold, the second guide roller including at least one active guide roller, the active guide roller being driven to rotate by a driving device.

[0108] The first impregnation mold, the second impregnation mold, and the third impregnation mold used in this invention are described in Chinese patent applications CN202011193483.3, 202011191450.5, and 202011199839.4, the entire contents of which are incorporated herein by reference.

[0109] It should be noted that the first impregnation mold, the second impregnation mold, and the third impregnation mold described above in this invention can be applied to any existing manufacturing system and preparation technology for reinforced and toughened modified polyglycolic acid composite materials.

[0110] According to some embodiments of the preparation method described in this invention, the second impregnation treatment in step S4 can be performed in a molding die. The molding die consists of a core, an outer jacket, and an outer jacket opening template. The core is located inside the outer jacket, forming a cavity with it. The resin melt can enter the cavity from the bottom, top, or both sides of the outer jacket. The core can move back and forth within the outer jacket, and the pressure of the melt in the cavity is determined by adjusting the size of the formed cavity space. The pressure of the melt in the cavity can also be adjusted by the angle between the core and the outer jacket. The working principle of this molding die is as follows: after passing through the impregnation die, a strip of inner impregnated material is formed, guided through the hole in the middle of the core, and then, in the cavity filled with the mixed melt formed by the core and the outer jacket, the composite structure of the inner and outer layers is formed, and finally, it is discharged through the outer jacket opening template.

[0111] The invention will now be further described with reference to the accompanying drawings.

[0112] Figure 1 The structure of the reinforced and toughened modified polyglycolic acid composite material of the present invention is shown. For example... Figure 1 As shown, the cross-section of the reinforced and toughened modified polyglycolic acid composite material of the present invention is circular, and from the inside out, it includes an inner core material 0-1 and an outer layer material 0-3. The inner core material 0-1 contains fiber bundles 0-2 that are oriented longitudinally, and the fiber bundles 0-2 are uniformly dispersed in the inner core material 0-1.

[0113] like Figure 2 and Figure 3 As shown, the manufacturing system of the present invention includes a fiber rack and fiber guiding device 1, a fiber pretreatment device 2, a first impregnation mold 3, a melt plasticizing feeding device 4, a molding mold 5, a cooling water tank 6, a dryer 7, a traction machine 8, a pelletizer 9, a collection box 10, and an electrical control system (not shown in the figure), which are connected in sequence.

[0114] In the manufacturing system, molding die 5 is used for molding the reinforced and toughened modified polyglycolic acid composite material, and its structure is as follows: Figure 8 As shown.

[0115] In the manufacturing system, the first impregnation mold 3 is used to impregnate the fiber with the first polyglycolic acid resin melt.

[0116] like Figure 4As shown, in one embodiment, the first impregnation mold is an impregnation device with an adjustable guide roller position, including a first impregnation mold head A300. The first impregnation mold head A300 includes an impregnation mold body A7, a fiber inlet A1, a fiber outlet A6, and a melt flow channel A3. At least one first guide roller A8 is provided in the mold cavity, wherein the first guide roller A8 is movable between the fiber inlet A1 and the fiber outlet A6, or the first guide roller A8 is movable along a direction perpendicular to the line connecting the fiber inlet A1 and the fiber outlet A6; or, the first guide roller A8 is movable both between the fiber inlet A1 and the fiber outlet A6 and along a direction perpendicular to the line connecting the fiber inlet A1 and the fiber outlet A6.

[0117] Taking a rectangular first impregnation mold head A300 as an example, the first impregnation mold head A300 is provided with a plurality of first guide rollers A8. The axial direction of each first guide roller A8 is the width direction of the first impregnation mold head A300. Therefore, each first guide roller A8 can move along the length direction of the first impregnation mold head A300 or along the height direction, thereby changing the position of the first guide roller A8 within the first impregnation mold head A300.

[0118] Understandably, the axial direction of the first guide roller A8 can also be the length direction of the first impregnation mold head A300. In this case, each first guide roller A8 can move along the width direction of the first impregnation mold head A300 or along the height direction of the first impregnation mold head A300, thereby changing the position of the first guide roller A8 within the first impregnation mold head A300.

[0119] Since the fiber needs to pass around the first guide roller A8 in sequence within the mold cavity of the first impregnation mold head A300, the fiber's path within the mold cavity can be altered by changing the position of the first guide roller A8 within the first impregnation mold head A300 (horizontal position, longitudinal position, etc.). Therefore, when the required impregnation conditions change, it is not necessary to replace the mold; only the position of the first guide roller A8 within the first impregnation mold head A300 needs to be adjusted. This improves production efficiency and continuity. It also reduces the number of first impregnation mold heads A300, saving production costs.

[0120] Specifically, the inventive concept is to achieve the purpose of adjusting the position of the first guide roller A8 by slotting the inner wall of the mold cavity of the first impregnation mold head A300.

[0121] A first groove A4 is provided on the first inner wall of the first impregnation mold head A300, and the first groove A4 extends between the fiber inlet A1 and the fiber outlet A6 (i.e., Figure 4(As shown in the X-axis direction), the first guide roller A8 moves along the first groove A4 to change its horizontal position within the first impregnation mold head A300.

[0122] Furthermore, a second groove A2 is also provided on the first inner wall of the first impregnation mold head A300, and the second groove extends in a direction perpendicular to the first groove A4 (i.e. Figure 4 (As shown in the Y-axis direction), the first guide roller A8 moves along the second slide groove A2 to change its vertical position in the die head.

[0123] It should be noted that the first groove A4 and the second groove A2 can be connected. Therefore, the first guide roller A8 can move arbitrarily in the longitudinal or transverse direction, thereby changing its position.

[0124] The cross-sections of the first groove A4 and the second groove A2 can be trapezoidal, circular, arc-shaped, or rectangular, etc., and the present invention does not limit them.

[0125] Both ends of the first guide roller A8 are provided with adjustment devices (not shown in the figure). The adjustment devices 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.

[0126] like Figure 5 As shown, in another embodiment of the present invention, the second impregnation mold is a combined impregnation mold, including a second impregnation mold head B300. The second impregnation mold head B300 includes a first module B3, an intermediate module B6, and a second module B7 connected in sequence. The first module B3 is provided with a fiber inlet B1 and a first module flow channel B31, the second module B7 is provided with a fiber outlet B8 and a second module flow channel B71, and the intermediate module B6 is provided with an intermediate module flow channel B61.

[0127] After sequentially connecting the first module B3, intermediate module B6, and second module B7, the first module flow channel B31, intermediate module flow channel B61, and second module flow channel B71 are connected to form a combined flow channel B4 for the fiber to pass through. The number of intermediate modules B6 is at least one. That is, the first module B3 is the head module, the second module B7 is the tail module, and there are one or more intermediate modules B6 between them. It should be noted that these intermediate modules B6 are also sequentially connected.

[0128] In other words, the number of intermediate modules B6 can be increased or decreased as needed, so that when the impregnation requirements change, different intermediate modules B6 can be combined to form a combined second impregnation mold head B300, thereby improving production continuity and efficiency and saving the cost of additional mold opening.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] Understandably, different combinations of flow channels B4 can be obtained by selecting different intermediate modules B6.

[0133] 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.

[0134] 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.

[0135] The impregnation mold body C2 has a second guide roller inside its cavity. This second guide roller includes at least one active guide roller C4, which is driven to rotate by a drive device (not shown in the figure). Since the rotation of the active guide roller C4 is driven by the drive device, rather than by the fiber's traction, the actively rotating active guide roller C4 helps reduce the fiber's traction tension and the friction between the fiber and the active guide roller C4 as the fiber passes through it. This reduces fiber breakage, ensures fiber integrity, and prevents fiber breakage, thereby improving the material's mechanical properties.

[0136] Preferably, the second guide roller further includes at least one driven guide roller C5, which is driven by the fiber passing through the active guide roller C4; or the driven guide roller C5 and the active guide roller C4 are connected by a belt mechanism, a gear mechanism or a chain mechanism.

[0137] like Figure 6 The diagram illustrates an example with one active guide roller C4 and two driven guide rollers C5, wherein the two driven guide rollers C5 are arranged one above the other to extend the impregnation path of the fibers passing through them. The active guide roller C4 and the driven guide rollers C5 may be at the same or different heights within the die cavity.

[0138] Furthermore, the driving device can be a motor, hydraulic mechanism, or gearbox, or any device capable of driving the active guide roller C4 to rotate.

[0139] Based on the fiber's traveling speed v1 in the mold cavity of the impregnation mold body C2, the corresponding tangential speed v2 of the active guide roller C4 can be selected. For example, the tangential speed v2 of the active guide roller C4 can be made the same as the fiber's traveling speed v1, i.e., v1 = v2. This reduces fiber breakage and wear, thus ensuring fiber integrity, promoting the degree of fiber impregnation, shortening impregnation time, and improving production efficiency.

[0140] like Figure 2 As shown, the melt plasticizing feeding device 4 consists of a twin-screw extruder used for melting and plasticizing materials. The twin-screw extruder is a co-rotating twin-screw extruder with a screw diameter of 25mm-95mm and a length-to-diameter ratio of 36:1-65:1. When the melt plasticizing feeding device 4 consists of a single extruder 4, the melt plasticizing material in the extruder is divided by a melt distributor and fed into the impregnation die and the forming die respectively, and the flow rate of each die is controlled by a melt flow control valve.

[0141] like Figure 3As shown, when the melt plasticizing feeding device 4 consists of two extruders 4-1 and 4-2, the molten plasticized melts from extruder I 4-1 and extruder II 4-2 are respectively fed into the impregnation mold and the forming mold. In this embodiment, the melt plasticizing feeding device consists of two extruders I 4-1 and extruder II 4-2, and the molten plasticized melts from extruder I 4-1 and extruder II 4-2 are respectively fed into the first impregnation mold 3 and the forming mold 5. Extruder I 4-1 and extruder II 4-2 can be fed with the same or different materials, thus enabling the preparation of composite materials with the same or different materials for the inner and outer layers.

[0142] The fiber pretreatment device 2 consists of a tension roller and a hot drying tunnel. This combination allows for some release of tension on the fibers as they enter the hot drying tunnel, thus accommodating fibers of different strengths and preventing fibers with lower strength from breaking before entering the impregnation die. The surface of the tension roller in the fiber pretreatment device 2 needs to be ceramic-coated to increase surface roughness and reduce friction on the fibers.

[0143] In the manufacturing system, the fiber frame and fiber guiding device 1 are used for fiber output and untwisting. The device is equipped with an automatic control untwisting device, which is linked with the traction machine 8 and electrically connected to the electrical control system (such as a PLC control device).

[0144] In the manufacturing system, the cooling water tank 6, dryer 7, traction machine 8, pelletizer 9, and collection box 10 are conventional equipment or devices known to those skilled in the art, and will not be described in detail here.

[0145] Figure 7 A schematic diagram showing the second impregnation process using a molding die is shown. Figure 8 A cross-sectional view of the molding die used in the second impregnation process is shown.

[0146] like Figure 8 As shown, in one embodiment, the molding die 5 consists of a core 5-1, an outer sleeve 5-2, and an outer sleeve opening template 5-3. The core 5-1 is located inside the outer sleeve 5-2, forming a cavity with the outer sleeve 5-2. The resin melt can enter the cavity from the bottom, top, or both sides of the outer sleeve 5-2. The core 5-1 can move back and forth within the outer sleeve 5-2, and the pressure of the melt in the cavity is determined by adjusting the size of the formed cavity space. The pressure of the melt in the cavity can also be adjusted by the angle between the core 5-1 and the outer sleeve 5-2. The working principle of the molding die 5 is as follows: the strip of inner impregnated material formed after passing through the impregnation mold 3 is guided through the hole in the middle of the core 5-1, and then the composite structure of the inner and outer layer materials is formed in the cavity filled with mixed melt formed by the core 5-1 and the outer sleeve 5-2. Finally, it is discharged through the outer sleeve opening template 5-3.

[0147] like Figure 7 As shown, the material strip 5-4 enters the cavity filled with the second component melt formed by the core (not shown) and the outer sleeve 5-2 for processing, wherein the second component melt is fed into the cavity from the second resin inlet 5-5.

[0148] In the following embodiments and comparative examples, the following methods are employed: Figure 3 The manufacturing system shown prepares reinforced and toughened modified polyglycolic acid composites, wherein the first impregnation treatment is selected from... Figure 4 The first immersion mold shown, the second immersion treatment uses Figure 8 The molding die shown.

[0149] The following detailed description, with reference to specific embodiments, illustrates the reinforced and toughened modified polyglycolic acid composite material and its preparation method provided by the present invention.

[0150] Unless otherwise defined, the technical terms used in the following embodiments have the same meaning as commonly understood by those skilled in the art. Unless otherwise specified, the reagents used in the following embodiments are conventional biochemical reagents; the raw materials, instruments, and equipment used in the following embodiments can all be obtained commercially or by existing methods; unless otherwise specified, the reagent dosages are those used in routine experimental operations; unless otherwise specified, the experimental methods are conventional methods.

[0151] In the various embodiments and comparative examples of the present invention, the testing methods for each performance data are as follows:

[0152] (1) Tensile strength: GB / T 1040-2018;

[0153] (2) Flexural modulus: GB / T 9341-2008;

[0154] (3) Impact strength: GB / T 1843-2008;

[0155] (4) Heat distortion temperature: GB / T 1634-2004, Method A, bending stress 1.8MPa.

[0156] The materials used in the various embodiments and comparative examples of the present invention are as follows:

[0157] (1) Polyglycolic acid: homopolymer polyglycolic acid with melt indexes of 10, 40, 100, and 150 g / 10 min (2.16 kg, 230 °C). The first two were purchased from Shanghai Pujing Chemical, and the latter two were purchased from Kureha, Japan and Jinmei, Liaoning, respectively.

[0158] (2) Glass fiber: Alkali-free glass fiber, diameter 17μm, linear density 2400tex, Chongqing International Composite Materials Co., Ltd.

[0159] (3) Talc: Particle size 50μm, Inokai Company.

[0160] (4) Calcium carbonate: 0.1 μm, Inokai Company.

[0161] (5) Montmorillonite: 10μm, Inokai Company.

[0162] (6) Antioxidant 1010: Irganox 1010, Ciba, Germany.

[0163] (7) Antioxidant 168: Irgafos168, BASF, Germany.

[0164] (8) Silane coupling agent: KH-550, Nanjing Youpu Chemical Co., Ltd.

[0165] (9) Calcium stearate: 6.5 wt% Ca, Inokai Company.

[0166] (10) Hydrogenated nitrile butadiene rubber (HNBR): saturation of 99%, acrylonitrile content of 36%, Mooney viscosity of 65, Zeon Corporation, Japan.

[0167] (11) Maleic anhydride grafted ethylene-octene copolymer (POE-g-MAH): CMG5805-L, Jia Yirong Company.

[0168] (12) Polybutylene adipate / terephthalate (PBAT): TH801T, Lanshan Tunhe;

[0169] (13) Polycaprolactone (PCL): 6800, Solvay, USA.

[0170] (14) Mixed toughening agent 1#: hydrogenated nitrile rubber: POE-g-MAH = 80:20 (by weight).

[0171] The preparation method is as follows:

[0172] a. Add 20 parts by weight of POE-g-MAH to a mixer and melt it at 180°C. Then add 80 parts by weight of hydrogenated nitrile butadiene rubber and 0.1 parts by weight of antioxidant RD (Ningkang Chemical). Stir at 50 r / min and mix for 5 minutes to obtain modified hydrogenated nitrile butadiene masterbatch.

[0173] b. Modified hydrogenated nitrile butadiene masterbatch was prepared into vulcanized rubber using ordinary rubber processing technology: 100 parts by weight of modified hydrogenated nitrile butadiene masterbatch, 5 parts by weight of zinc oxide (Beijing Inokai), 1 part by weight of stearic acid (Beijing Inokai), 40 parts by weight of N-220 carbon black (Tianjin Baochi Chemical), 1 part by weight of antioxidant RD (Ningkang Chemical), 8 parts by weight of peroxide vulcanizing agent F-40 (Beijing Inokai), and 2 parts by weight of triallyl isocyanate (co-vulcanizing agent, Beijing Inokai) were mixed in an internal mixer and then vulcanized in an ordinary flat vulcanizing machine at 180℃ for 10 minutes.

[0174] c. Vulcanized rubber is physically crushed to obtain mixed toughening agent 1#.

[0175] (15) Mixed toughening agent 2#: hydrogenated nitrile rubber: POE-g-MAH = 50:50 (weight ratio).

[0176] The preparation method is as follows:

[0177] a. Add 50 parts by weight of POE-g-MAH to a mixer and melt it at 180°C. Then add 50 parts by weight of hydrogenated nitrile butadiene rubber and 0.1 parts by weight of antioxidant RD (Ningkang Chemical). Stir at 50 r / min and mix for 5 minutes to obtain modified hydrogenated nitrile butadiene masterbatch.

[0178] b. Modified hydrogenated nitrile butadiene masterbatch was prepared into vulcanized rubber using ordinary rubber processing technology: 100 parts by weight of modified hydrogenated nitrile butadiene masterbatch, 2.5 parts by weight of zinc oxide (Beijing Inokai), 1 part by weight of stearic acid (Beijing Inokai), 25 parts by weight of N-220 carbon black (Tianjin Baochi Chemical), 1 part by weight of antioxidant RD (Ningkang Chemical), 5 parts by weight of peroxide vulcanizing agent F-40 (Beijing Inokai), and 1.25 parts by weight of triallyl isocyanate (co-vulcanizing agent, Beijing Inokai) were mixed in an internal mixer and then vulcanized in an ordinary flat vulcanizing machine at 180℃ for 10 minutes.

[0179] c. Vulcanized rubber is physically crushed to obtain mixed toughening agent 2#.

[0180] (16) Mixed toughening agent 3#: hydrogenated nitrile rubber: POE-g-MAH = 20:80 (weight ratio).

[0181] The preparation method is as follows:

[0182] a. Add 80 parts by weight of POE-g-MAH to a mixer and melt it at 180°C. Then add 20 parts by weight of hydrogenated nitrile butadiene rubber and 0.1 parts by weight of antioxidant RD (Ningkang Chemical). Stir at 50 r / min and mix for 5 minutes to obtain modified hydrogenated nitrile butadiene masterbatch.

[0183] b. Modified hydrogenated nitrile butadiene masterbatch was prepared into vulcanized rubber using ordinary rubber processing technology: 100 parts by weight of modified hydrogenated nitrile butadiene masterbatch, 1 part by weight of zinc oxide (Beijing Inokai), 0.5 parts by weight of stearic acid (Beijing Inokai), 10 parts by weight of N-220 carbon black (Tianjin Baochi Chemical), 0.5 parts by weight of antioxidant RD (Ningkang Chemical), 2 parts by weight of peroxide vulcanizing agent F-40 (Beijing Inokai), and 0.5 parts by weight of triallyl isocyanate (co-vulcanizing agent, Beijing Inokai) were mixed in an internal mixer and then vulcanized in an ordinary flat vulcanizing machine at 180℃ for 10 minutes.

[0184] c. Vulcanized rubber is physically crushed to obtain mixed toughening agent 3#.

[0185] (17) Hydrogenated butadiene-acrylonitrile rubber:

[0186] The preparation method is as follows:

[0187] Hydrogenated nitrile butadiene rubber (NBR) was prepared using a conventional rubber processing method: 100 parts by weight of hydrogenated NBR masterbatch (99% saturation, 36% acrylonitrile content, Mooney viscosity 65, from Zeon Corporation, Japan), 5 parts by weight of zinc oxide (Beijing Inokai), 1 part by weight of stearic acid (Beijing Inokai), 50 parts by weight of N-220 carbon black (Tianjin Baochi Chemical), 2 parts by weight of antioxidant RD (Ningkang Chemical), 8 parts by weight of peroxide vulcanizing agent F-40 (Beijing Inokai), and 2 parts by weight of triallyl isocyanate (co-vulcanizing agent, Beijing Inokai) were mixed in a Banbury mixer, then vulcanized in a conventional flat vulcanizing machine at 180℃ for 10 minutes, and finally physically crushed to obtain hydrogenated NBR.

[0188] Example 1

[0189] (1) 100 parts by weight of polyglycolic acid (melt index 40g / 10min) and 1 part by weight of silane coupling agent (KH550), 0.2 parts by weight of antioxidant 168, 0.3 parts by weight of antioxidant 1010 and 0.2 parts by weight of calcium stearate are stirred in a high-speed mixer at 50°C for 3 minutes. After melting, the mixture is sent to an impregnation mold.

[0190] (2) Continuous glass fibers are introduced into the impregnation mold under the action of the traction machine and impregnated and dispersed with the above melt to form a strip, which is used as the inner layer material, wherein the glass fiber content is 60 parts by weight.

[0191] (3) 100 parts by weight of polyglycolic acid (melt index 10g / 10min) are mixed with 10 parts by weight of talc powder, 15 parts by weight of mixed toughening agent 1#, 2 parts by weight of silane coupling agent (KH550), 0.1 parts by weight of antioxidant 1010 and 0.5 parts by weight of calcium stearate in a high-speed mixer and stirred at 50°C for 3 minutes. This mixture is used as the outer layer material and fed into a twin-screw extruder connected to the molding die.

[0192] (4) The inner layer material enters the molding die under the action of the traction machine, is guided through the hole in the middle of the core, and is formed in the cavity filled with the molten mixture of the outer layer material formed by the core and the outer jacket. Finally, it is exported through the outer jacket template.

[0193] (5) Adjust the amount of outer material coverage by selecting the size (4mm) of the outer mold outer template, adjust the cutting speed of the pelletizer, and control the pellet length of the obtained polyglycolic acid composite material to be 15mm.

[0194] (6) The polyglycolic acid composite material prepared by the above method was injection molded into standard specimens and its performance was tested. The test formula is shown in Table 1 and the test results are shown in Table 2.

[0195] Comparative Example 1

[0196] (1) 100 parts by weight of polyglycolic acid (melt index 40g / 10min), 1 part by weight of silane coupling agent (KH550), 0.2 parts by weight of antioxidant 168, 0.3 parts by weight of antioxidant 1010, 0.2 parts by weight of calcium stearate, and 60 parts by weight of glass fiber (25mm) are stirred in a high-speed mixer at 50°C for 3 minutes.

[0197] (2) Mix 100 parts by weight of polyglycolic acid (melt index 10g / 10min) with 10 parts by weight of talc powder, 15 parts by weight of mixed toughening agent 1#, 2 parts by weight of silane coupling agent (KH550), 0.1 parts by weight of antioxidant 1010 and 0.5 parts by weight of calcium stearate in a high-speed mixer and stir at 50°C for 3 minutes.

[0198] (3) Add the two mixtures together into a twin-screw extruder for melt granulation, and the resulting polyglycolic acid composite material particles are 15 mm in length.

[0199] (4) The polyglycolic acid composite material prepared above was injection molded into standard specimens and its performance was tested. The test formula is shown in Table 1 and the test results are shown in Table 2.

[0200] Comparative Example 2

[0201] (1) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min), 1 part by weight of silane coupling agent (KH550), 0.2 parts by weight of antioxidant 168, 0.3 parts by weight of antioxidant 1010, 0.2 parts by weight of calcium stearate, and 60 parts by weight of glass fiber (25 mm) were stirred in a high-speed mixer at 50°C for 3 minutes, and then melt-granulated to obtain polyglycolic acid composite material 1.

[0202] (2) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min), 10 parts by weight of talc, 15 parts by weight of mixed toughening agent 1#, 2 parts by weight of silane coupling agent (KH550), 0.1 parts by weight of antioxidant 1010 and 0.5 parts by weight of calcium stearate were stirred at 50°C for 3 minutes in a high-speed mixer, and then melt granulated to obtain polyglycolic acid composite material 2.

[0203] (3) Add polyglycolic acid composite material 1 and 2 together into a twin-screw extruder for melt granulation. The resulting polyglycolic acid composite material particles are 15 mm long.

[0204] (4) The polyglycolic acid composite material prepared above was injection molded into standard specimens and its performance was tested. The test formula is shown in Table 1 and the test results are shown in Table 2.

[0205] Example 2

[0206] (1) 100 parts by weight of polyglycolic acid (melt index 150g / 10min) are mixed with 2 parts by weight of silane coupling agent (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 and stirred at 50°C for 3 minutes. After melting, the mixture is sent to an impregnation mold.

[0207] (2) Continuous glass fibers are introduced into the impregnation mold under the action of the traction machine and impregnated and dispersed with the above melt to form a strip, which is used as the inner layer material, wherein the glass fiber content is 150 parts by weight.

[0208] (3) 100 parts by weight of polyglycolic acid (melt index 40g / 10min) and 50 parts by weight of montmorillonite, 15 parts by weight of mixed toughening agent 1#, 0.05 parts by weight of silane coupling agent (KH550), 1 part by weight of antioxidant 1010 and 1 part by weight of calcium stearate are mixed in a high-speed mixer and stirred at 50°C for 3 minutes. This mixture is used as the outer layer material and fed into a twin-screw extruder connected to the molding die.

[0209] (4) The inner layer material enters the molding die under the action of the traction machine, is guided through the hole in the middle of the core, and is formed in the cavity filled with the molten mixture of the outer layer material formed by the core and the outer jacket. Finally, it is exported through the outer jacket template.

[0210] (5) Adjust the amount of outer material coverage by selecting the size of the outer mold outer template (4mm), adjust the cutting speed of the pelletizer, and control the pellet length of the obtained polyglycolic acid composite material to be 3mm.

[0211] (6) The polyglycolic acid composite material prepared by the above method was injection molded into standard specimens and its performance was tested. The test results are shown in Table 1.

[0212] Example 3

[0213] (1) 100 parts by weight of polyglycolic acid (melt index 100g / 10min) and 0.5 parts by weight of silane coupling agent (KH550), 0.1 parts by weight of antioxidant 168, 0.2 parts by weight of antioxidant 1010 and 0.2 parts by weight of calcium stearate are stirred in a high-speed mixer at 50°C for 3 minutes. After melting, the mixture is sent to an impregnation mold.

[0214] (2) Continuous glass fibers are introduced into the impregnation mold under the action of the traction machine and impregnated and dispersed with the above melt to form a strip, which is used as the inner layer material, wherein the glass fiber content is 100 parts by weight.

[0215] (3) 100 parts by weight of polyglycolic acid (melt index 100g / 10min) and 30 parts by weight of calcium carbonate, 10 parts by weight of mixed toughening agent 1#, 1 part by weight of silane coupling agent (KH550), 0.5 parts by weight of antioxidant 1010 and 0.2 parts by weight of calcium stearate are mixed in a high-speed mixer and stirred at 50°C for 3 minutes. This mixture is used as the outer layer material and fed into a twin-screw extruder connected to the molding die.

[0216] (4) The inner layer material enters the molding die under the action of the traction machine, is guided through the hole in the middle of the core, and is formed in the cavity filled with the molten mixture of the outer layer material formed by the core and the outer jacket. Finally, it is exported through the outer jacket template.

[0217] (5) Adjust the amount of outer material coverage by selecting the size (4mm) of the outer mold outer template, adjust the cutting speed of the pelletizer, and control the pellet length of the obtained polyglycolic acid composite material to be 4mm.

[0218] (6) The polyglycolic acid composite material prepared by the above method was injection molded into standard specimens and its performance was tested. The test results are shown in Table 1.

[0219] Example 4

[0220] The preparation process was the same as in Example 1, except that 15 parts by weight of mixed toughening agent 1# in step (3) were replaced with 15 parts by weight of POE-g-MAH. The polyglycolic acid composite material was then injection molded into standard specimens for performance testing. The test results are shown in Table 2.

[0221] Example 5

[0222] The preparation process was the same as in Example 1, except that 10 parts by weight of talc were not added in step (3). The polyglycolic acid composite material was then injection molded into standard specimens for performance testing. The test results are shown in Table 2.

[0223] Example 6

[0224] The preparation process was the same as in Example 1, except that 15 parts by weight of the mixed toughening agent 1# were not added in step (3). The polyglycolic acid composite material was then injection molded into standard specimens for performance testing. The test results are shown in Table 2.

[0225] Example 7

[0226] The preparation process was the same as in Example 1, except that 15 parts by weight of mixed toughening agent 1# in step (3) were replaced with 15 parts by weight of hydrogenated butadiene nitrile rubber. The polyglycolic acid composite material was then injection molded into standard specimens for performance testing. The test results are shown in Table 2.

[0227] Example 8

[0228] The preparation process was the same as in Example 1, except that 15 parts by weight of mixed toughening agent 1# in step (3) was replaced with 15 parts by weight of PBAT. The polyglycolic acid composite material was then injection molded into standard specimens for performance testing. The test results are shown in Table 2.

[0229] Example 9

[0230] The preparation process was the same as in Example 1, except that 15 parts by weight of mixed toughening agent 1# in step (3) were replaced with 15 parts by weight of PCL. The polyglycolic acid composite material was then injection molded into standard specimens for performance testing. The test results are shown in Table 2.

[0231] Comparative Example 3

[0232] The preparation process was the same as in Example 1, except that 10 parts by weight of talc, 15 parts by weight of mixed toughening agent 1#, and 2 parts by weight of silane coupling agent (KH550) were added in step (1), while no further additions were made in step (3). The polyglycolic acid composite material was then injection molded into standard specimens for performance testing. The test results are shown in Table 2.

[0233] Comparative Example 4

[0234] The preparation process was the same as in Example 1, except that: in step (1), 5 parts by weight of talc, 7.5 parts by weight of mixed toughening agent 1#, and 1 part by weight of silane coupling agent (KH550) were added; and in step (3), 5 parts by weight of talc, 7.5 parts by weight of mixed toughening agent 1#, and 1 part by weight of silane coupling agent (KH550) were added. The polyglycolic acid composite material was then injection molded into standard specimens for performance testing. The test results are shown in Table 2.

[0235] Example 10

[0236] The preparation process was the same as in Example 1, except that 15 parts by weight of mixed toughening agent 1# in step (3) was replaced with 15 parts by weight of mixed toughening agent 2#. The polyglycolic acid composite material was then injection molded into standard specimens for performance testing. The test results are shown in Table 2.

[0237] Example 11

[0238] The preparation process was the same as in Example 1, except that: in step (3), 15 parts by weight of mixed toughening agent 1# was replaced with 15 parts by weight of mixed toughening agent 3#. The polyglycolic acid composite material was then injection molded into standard specimens for performance testing. The test results are shown in Table 2.

[0239] Table 1. Proportioning of major components in the composite materials of the examples and comparative examples.

[0240]

[0241]

[0242] Table 2 Material Performance Tests for Examples and Comparative Examples

[0243]

[0244] As can be seen from the results of Example 1 and Comparative Examples 1 and 2, the performance of the modified product obtained by directly melting and blending the inner and outer layer materials is significantly lower than that of the polyglycolic acid composite material obtained by the preparation method described in this invention. This shows that the present invention can uniformly disperse high content fillers and maintain the length of the filler fibers, ultimately obtaining a polyglycolic acid composite material with excellent performance.

[0245] A comparison of Examples 1 and 5-6 shows that, under the same technical methods, the combined use of a toughening agent and filler, including maleic anhydride-grafted ethylene-octene copolymer and hydrogenated nitrile rubber, has a synergistic toughening and strengthening effect, resulting in better overall performance of the composite material.

[0246] The comparison between Examples 1 and Examples 4 and 7-9 shows that, under the same technical methods, adding a mixed toughening agent, including maleic anhydride-grafted ethylene-octene copolymer and hydrogenated nitrile rubber, to the composite material can result in better overall performance than adding other toughening agents.

[0247] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A reinforced and toughened modified polyglycolic acid composite material, characterized in that, It includes an inner core material and at least one outer layer material; the inner core material includes a first polyglycolic acid resin, glass fiber, and a first additive, the glass fiber extending continuously from one end of the inner core material to its opposite end; the outer layer material encapsulates the inner core material, and the outer layer material includes a second polyglycolic acid resin, a toughening agent, a filler, and a second additive. In the core material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of glass fiber is 10-200 parts by weight. In the outer layer material, the amount of the second polyglycolic acid resin is 100 parts by weight, the amount of the toughening agent is 5-30 parts by weight, and the amount of the filler is 5-50 parts by weight. 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. The toughening agent is selected from at least one of biodegradable polyester, natural rubber, bio-based elastomer, polyolefin copolymer and specialty rubber; The filler is selected from at least one of organic fillers and inorganic fillers.

2. The composite material according to claim 1, characterized in that, In the core material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of glass fiber is 10-150 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 filler is 10-50 parts by weight.

3. The composite material according to claim 2, characterized in that, In the core material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of glass fiber is 20-150 parts by weight.

4. The composite material according to any one of claims 1-3, characterized in that, The toughening agent is selected from at least one of polybutylene adipate, polybutylene terephthalate, polybutylene succinate and its copolymers, polyhydroxy fatty acids, polycaprolactone, natural rubber, ethylene-octene copolymers and their modifications, hydrogenated nitrile butadiene rubber, and functionalized solution-polymerized styrene-butadiene.

5. The composite material according to claim 4, characterized in that, The toughening agent is selected from at least one of polybutylene adipate terephthalate, polybutylene terephthalate succinate, ethylene-octene copolymer and its maleic anhydride modified form, and hydrogenated nitrile rubber.

6. The composite material according to claim 5, characterized in that, The toughening agent is selected from maleic anhydride modified from ethylene-octene copolymer and hydrogenated nitrile butadiene rubber.

7. The composite material according to claim 6, characterized in that, The weight ratio of the maleic anhydride modified ethylene-octene copolymer to the hydrogenated nitrile rubber is 0.2 to 5.

8. The composite material according to any one of claims 1-3, characterized in that, The packing material is selected from inorganic packing materials.

9. The composite material according to claim 8, characterized in that, The filler is selected from at least one of calcium carbonate, talc, glass microspheres, kaolin, silicon dioxide, carbon black, montmorillonite, barium sulfate, wollastonite, and whiskers; And / or, the inorganic filler has a particle size of 0.05~100μm.

10. The composite material according to claim 9, characterized in that, The filler is selected from at least one of calcium carbonate, talc, glass microspheres, kaolin, montmorillonite, and wollastonite; And / or, the inorganic filler has a particle size of 0.06~50μm.

11. The composite material according to claim 10, characterized in that, The inorganic filler has a particle size of 0.08~1μm.

12. The composite material according to any one of claims 1-3, characterized in that, The first polyglycolic acid resin and the second polyglycolic acid resin may be the same or different, and each is independently selected from homopolymer polyglycolic acid and / or copolymer polyglycolic acid; And / or, the melt flow rate of the first polyglycolic acid resin at 230°C and 2.16 kg is 5-500 g / 10 min; And / or, the melt flow rate of the second polyglycolic acid resin at 230°C and 2.16 kg is 5-500 g / 10 min.

13. The composite material according to claim 12, characterized in that, The content of glycolic acid monomer in the copolymerized polyglycolic acid is ≥90 mol%; And / or, the melt flow rate of the first polyglycolic acid resin at 230°C and 2.16 kg is 10-200 g / 10 min; And / or, the melt flow rate of the second polyglycolic acid resin at 230°C and 2.16 kg is 10-200 g / 10 min.

14. The composite material according to claim 13, characterized in that, The content of glycolic acid monomer in the copolymerized polyglycolic acid is ≥95 mol%; And / or, the melt flow rate of the first polyglycolic acid resin at 230°C and 2.16 kg is 10-100 g / 10 min; And / or, the melt flow rate of the second polyglycolic acid resin at 230°C and 2.16 kg is 10-100 g / 10 min.

15. The composite material according to any one of claims 1-3, characterized in that, The amount of the first polyglycolic acid resin is based on 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 parts by weight of a first lubricant; And / or, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second additive 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.

16. The composite material according to claim 15, characterized in that, 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 parts by weight of a first antioxidant, and 0.2-1 parts by weight of a first lubricant; And / or, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second additive 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.

17. The composite material according to claim 15, characterized in that, The first compatibilizer and the second compatibilizer may be the same or different, and each is independently selected from at least one coupling agent; And / or, the first antioxidant and the second antioxidant may be the same or different, and each is independently selected from at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 2246, antioxidant CA and antioxidant 626; And / or, the first lubricant and the second lubricant may be the same or different, and each is independently selected from at least one of ethylene bis-stearamide, calcium stearate, mono-fatty acid glyceride, polyethylene wax, erucamide, and pentaerythritol stearate.

18. The composite material according to claim 17, characterized in that, The first compatibilizer and the second compatibilizer may be the same or different, and each is independently selected from at least one of silane coupling agents, titanate coupling agents, and organochromium complex coupling agents; And / or, the first antioxidant and the second antioxidant may be the same or different, and each is independently selected from at least one of antioxidant 1010 and antioxidant 168.

19. The composite material according to claim 18, characterized in that, The first compatibilizer and the second compatibilizer may be the same or different, and each is independently selected from silane coupling agents.

20. The composite material according to any one of claims 1-3, characterized in that, The core material does not contain non-oriented short fibers.

21. The composite material according to claim 20, characterized in that, The core material is composed of a first polyglycolic acid resin, glass fiber, and a first additive.

22. A method for preparing a reinforced and toughened modified polyglycolic acid composite material as described in any one of claims 1-21, characterized in that, include: S1. The first polyglycolic acid resin and the first additive are mixed and melted to obtain the first component melt; S2. The continuous glass fiber is subjected to a first impregnation treatment with the first component melt in step S1 to form a filamentous core material; S3. The second polyglycolic acid, toughening agent, filler, and second additive are mixed and melted to obtain the second component melt; S4. The core material obtained in step S2 is subjected to at least one second impregnation treatment with at least one second component melt from step S3 to obtain a reinforced and toughened modified polyglycolic acid composite material.

23. The preparation method according to claim 22, characterized in that, The mixing conditions for step S1 are: temperature of 40-60℃ and time of 3-5 min; and / or the melting temperature of step S1 is 230-260℃. And / or, the mixing conditions in step S3 are: temperature of 40-60℃, time of 3-5 min; and / or the melting temperature in step S3 is 230-260℃; And / or, step S2 further includes: dispersing and preheating the continuous glass fibers before subjecting them to the first impregnation treatment; And / or, step S4 further includes: after the second impregnation treatment, the material obtained by the second impregnation treatment is subjected to pull-out, strip-drawing, cooling, drying and pelletizing treatment to obtain a reinforced and toughened modified polyglycolic acid composite material.

24. The preparation method according to claim 23, characterized in that, The preheating temperature is 80-250℃.

25. The preparation method according to any one of claims 22-24, characterized in that, In step S2, the first impregnation process is performed in a first impregnation mold. The first impregnation mold is an adjustable impregnation mold, which includes a fiber inlet, a fiber outlet, and a melt flow channel. At least one first guide roller is provided in the mold cavity of the first impregnation mold. The first guide roller is movable between the fiber inlet and the fiber outlet. And / or, the first guide roller is movable along a direction perpendicular to the line connecting the fiber inlet and the fiber outlet.

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

27. The preparation method according to any one of claims 22-24, characterized in that, In step S2, the first impregnation process is carried out in a third impregnation mold. The third impregnation mold is a strong turbulent impregnation mold. The third impregnation mold includes a fiber inlet channel, an impregnation outlet, and a melt gap channel. The fiber inlet channel, the impregnation outlet, and the melt gap channel are all connected to the mold cavity inside the third impregnation mold. A second guide roller is provided inside the mold cavity of the third impregnation mold. The second guide roller includes at least one active guide roller, which is driven to rotate by a driving device.

28. The application of the reinforced and toughened modified polyglycolic acid composite material according to any one of claims 1-21 or the reinforced and toughened modified polyglycolic acid composite material prepared by the preparation method according to any one of claims 22-27 in the fields of catering, construction, oilfield chemical industry and engineering plastics.

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