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

Abstract

The application relates to the technical field of high polymer composite materials, and provides a glass fiber reinforced polyglycolic acid composite material and a preparation method and application thereof. The glass fiber reinforced polyglycolic acid composite material comprises an inner core material and at least one layer of outer layer material; the inner core material comprises a first polyglycolic acid resin, glass fibers and a first additive, the glass fibers continuously extend from one end of the inner core material to the opposite end; the outer layer material wraps the inner core material, and the outer layer material comprises a second polyglycolic acid resin and a second additive. The glass fiber reinforced polyglycolic acid composite material has an inner-outer layer composite structure, the flowability of the glass fibers in the matrix melt is improved, the high-content glass fibers are uniformly dispersed in the polyglycolic acid, and the mechanical properties such as the bending, heat resistance and impact of the polyglycolic acid are greatly enhanced. The comprehensive performance and surface quality of the composite material coated by the outer layer material can be further strengthened, and meanwhile, the material forming process requirement can be reduced.

Description

TECHNICAL FIELD

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

[0002] Polyglycolic acid (PGA) is a high polymer material with simple chemical structure, excellent biodegradability and biocompatibility. Unlike traditional plastics and rubbers, PGA gradually degrades after a certain period of use, turning into carbon dioxide and water that are harmless to the human body and the environment, which is of great significance to solving the current white pollution.

[0003] PGA has good barrier properties, with a water vapor barrier that is 100 times higher than that of polylactic acid, and is not affected by environmental temperature. In addition, the tensile strength of PGA exceeds 100 MPa, showing great potential in replacing engineering plastics. However, the processing temperature range of PGA is 230-260℃, which has the problems of high melt processing temperature and narrow processing window. At the same time, due to the high stereoregularity, PGA has the problems of hard and brittle texture, low melt strength and insufficient toughness, which makes it difficult to apply. Chen Lanlan et al. (Plastics Industry. 2021, 49(1): 145-149) studied the modification of PGA with epoxy type chain extender and phosphite type antioxidant, and found that the melt viscosity, heat resistance and hydrolysis resistance of the modified PGA were improved to a certain extent. Shen et al. (DOI: 10.1002 / app.51285) introduced PBAT and epoxy chain extender into PGA, which effectively improved the toughness and interfacial compatibility of PGA. Chinese patent CN104684997B uses an extruder to melt mix PGA and inorganic fillers to effectively improve the hydrolysis resistance and toughness of PGA. Chinese patent CN111454552A discloses the use of rare earth polymer additives, chain extenders and nucleating agents to improve the hydrophobicity and toughness of PGA, and to extend the use time of PGA.

[0004] Glass fiber is an inorganic non-metallic material with excellent performance, and has the characteristics of good heat resistance and high mechanical strength, and is often used to reinforce composite materials. Chinese patent CN109553937B discloses a glass fiber reinforced PET material, which solves the problem of strength and rigidity and light weight while meeting the use requirements. Li Weiming (Tianjin University of Science and Technology. 2013) studied the modification of PHB / PLA composite material with glass fiber, and when the addition amount was 30%-40%, the tensile strength and impact strength of the system were improved by more than 50%, and the shrinkage rate of the material was effectively reduced. However, when glass fiber is used to modify resin materials, dispersion problems often occur, especially when it is blended with other fillers, the fillers tend to aggregate.

[0005] For the above problems, the prior art is difficult to meet the demand. Therefore, it is of great significance to develop a polyglycolic acid composite material with high content of glass fiber and wide processing window. SUMMARY

[0006] To solve the above technical problems, the present application provides a glass fiber reinforced polyglycolic acid composite material and a preparation method thereof.

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

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

[0009] As a preferred scheme of the composite material provided by the present application, the melt flow rate of the first polyglycolic acid resin under the condition of 230℃ and 2.16kg is 5-500g / 10min, preferably 10-200g / 10min, and more preferably 10-150g / 10min.

[0010] As another preferred scheme of the composite material provided by the present application, the melt flow rate of the second polyglycolic acid resin under the condition of 230℃ and 2.16kg is 5-500g / 10min, preferably 10-200g / 10min, and more preferably 10-150g / 10min.

[0011] As another preferred scheme of the composite material provided by the present application, the first polyglycolic acid resin and the second polyglycolic acid resin are the same or different, and each is independently selected from homopolymer polyglycolic acid and / or copolymer polyglycolic acid.

[0012] Further preferably, the content of glycolic acid monomer in the copolymer polyglycolic acid is ≥90mol%, preferably ≥95mol%.

[0013] As another preferred scheme of the composite material provided by the present application, the composite material is in the form of a strip, a rod or a particle.

[0014] Preferably, the length of the strip or rod-shaped composite material is 5-30mm, preferably 5-25mm, and more preferably 6-15mm; and / or the particle size of the particle-shaped composite material is 2-5mm, preferably 3-4mm.

[0015] As another preferred embodiment of the composite material provided by the present application, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the glass fiber is 10-200 parts by weight, preferably 10-150 parts by weight, and more preferably 20-150 parts by weight; the amount of the second polyglycolic acid resin is 1-100 parts by weight, preferably 10-100 parts by weight, and more preferably 50-100 parts by weight.

[0016] As another preferred embodiment of the composite material provided by the present application, the amount of the first polyglycolic acid resin is 100 parts by weight, and the first additive includes at least one of 0.05-5 parts by weight of the first compatibilizer, 0.1-3 parts by weight of the first antioxidant, and 0.1-1 part by weight of the first lubricant; preferably, the amount of the first polyglycolic acid resin is 100 parts by weight, and the first additive includes at least one of 0.05-2 parts by weight of the first compatibilizer, 0.1-1 part by weight of the first antioxidant, and 0.2-1 part by weight of the first lubricant.

[0017] 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 the second compatibilizer, 0.1-3 parts by weight of the second antioxidant, and 0.1-1 part by weight of the 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 the second compatibilizer, 0.1-1 part by weight of the second antioxidant, and 0.2-1 part by weight of the second lubricant.

[0018] As another preferred embodiment of the composite material provided by the present application, the compatibilizer is selected from at least one of a coupling agent, preferably at least one of a silane coupling agent, a titanate coupling agent, an organic chromium complex coupling agent, and more preferably a silane coupling agent.

[0019] As another preferred embodiment of the composite material provided by the present application, the antioxidant is selected from at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 2246, antioxidant CA, and antioxidant 626, preferably antioxidant 1010 and / or antioxidant 168.

[0020] As another preferred embodiment of the composite material provided by the present application, the lubricant is selected from at least one of ethylene bis-stearamide, calcium stearate, monoglyceride fatty acid, polyethylene wax, erucamide, and pentaerythritol stearate.

[0021] As another preferred embodiment of the composite material provided by the present application, the glass fiber is continuous and / or staple glass fiber.

[0022] As another preferred scheme of the composite material provided by the present application, the outer layer material further comprises a filler.

[0023] Further preferably, the amount of the second polyglycolic acid resin is 100 parts by weight, and the amount of the filler is 1-99 parts by weight, preferably 5-50 parts by weight, and more preferably 10-50 parts by weight.

[0024] Further preferably, the filler is an organic filler and / or an inorganic filler; preferably at least one of a particulate inorganic filler, a flaky inorganic filler, and a fibrous inorganic filler; and more preferably a fibrous inorganic filler, such as meerschaum fiber and / or glass fiber.

[0025] Further preferably, the particulate inorganic filler has a particle size of 0.05-100 μm, preferably 0.1-50 μm, and more preferably 0.1-10 μm.

[0026] Further preferably, the flaky inorganic filler has a particle size (flaky diameter) of 0.05-100 μm, preferably 0.1-50 μm, and more preferably 0.1-10 μm.

[0027] Further preferably, the fibrous inorganic filler has a diameter of 0.05-20 μm and an aspect ratio of 10-1000.

[0028] As another preferred scheme of the composite material provided by the present application, the inner core material does not contain non-oriented short fibers, and preferably, the inner core material is composed of the first polyglycolic acid resin, glass fiber, and the first auxiliary agent.

[0029] In a second aspect, the present application provides a preparation method of a glass fiber reinforced polyglycolic acid composite material, comprising:

[0030] S1. mixing and melting the first polyglycolic acid resin and the first auxiliary agent to obtain a first component melt;

[0031] S2. performing first impregnation treatment on the continuous glass fiber and the first component melt in step S1 to form a filamentous inner core material;

[0032] S3. mixing and melting the second polyglycolic acid resin and the second auxiliary agent to obtain a second component melt;

[0033] S4. performing at least one second impregnation treatment on the inner core material obtained in step S2 and at least one second component melt in step S3 to obtain a glass fiber reinforced polyglycolic acid composite material.

[0034] As a preferred scheme of the preparation method provided by the present application, the mixing condition of step S1 is a temperature of 40-60 °C and a time of 3-5 min; and / or the melting temperature of step S1 is 230-260 °C.

[0035] As another preferred embodiment of the preparation method provided by the present application, the mixing condition of step S3 is that the temperature is 40-60°C and the time is 3-5 min; and / or the melting temperature of step S3 is 230-260°C.

[0036] As another preferred embodiment of the preparation method provided by the present application, step S2 further comprises: dispersing and preheating the continuous glass fiber before the first impregnation treatment; preferably, the preheating temperature is 80-250°C.

[0037] As another preferred embodiment of the preparation method provided by the present application, step S4 further comprises: after the second impregnation treatment, pulling out, stretching, cooling, drying and cutting the material obtained by the second impregnation treatment to obtain the glass fiber reinforced polyglycolic acid composite material.

[0038] As another preferred embodiment of the preparation method provided by the present application, 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 10-150 g / 10 min.

[0039] As another preferred embodiment of the preparation method provided by the present application, 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 10-150 g / 10 min.

[0040] As another preferred embodiment of the preparation method provided by the present application, the first polyglycolic acid resin and the second polyglycolic acid resin are the same or different, and each is independently selected from homopolymer polyglycolic acid and / or copolymer polyglycolic acid. Preferably, the homopolymer polyglycolic acid.

[0041] Further preferably, the content of glycolic acid monomer in the copolymer polyglycolic acid is ≥90 mol%, and preferably ≥95 mol%.

[0042] As another preferred embodiment of the preparation method provided by the present application, the composite material is in the form of a strip, a rod or a particle.

[0043] Further preferably, the length of the strip or rod-shaped composite material is 5-30 mm, preferably 5-25 mm, and more preferably 6-15 mm; and the particle size of the particle-shaped composite material is 2-5 mm, and preferably 3-4 mm.

[0044] As another preferred embodiment of the preparation method provided by the present application, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the glass fiber is 10-200 parts by weight, preferably 10-150 parts by weight, and more preferably 20-150 parts by weight; the amount of the second polyglycolic acid resin is 1-100 parts by weight, preferably 10-100 parts by weight, and more preferably 50-100 parts by weight.

[0045] As another preferred embodiment of the preparation method provided by the present application, the amount of the first polyglycolic acid resin is 100 parts by weight, and the first additive includes at least one of 0.05-5 parts by weight of the first compatibilizer, 0.1-3 parts by weight of the first antioxidant, and 0.1-1 part by weight of the first lubricant; preferably, the amount of the first polyglycolic acid resin is 100 parts by weight, and the first additive includes at least one of 0.05-2 parts by weight of the first compatibilizer, 0.1-1 part by weight of the first antioxidant, and 0.2-1 part by weight of the first lubricant.

[0046] 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 the second compatibilizer, 0.1-3 parts by weight of the second antioxidant, and 0.1-1 part by weight of the 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 the second compatibilizer, 0.1-1 part by weight of the second antioxidant, and 0.2-1 part by weight of the second lubricant.

[0047] As another preferred embodiment of the preparation method provided by the present application, the compatibilizer is selected from at least one of a coupling agent, preferably at least one of a silane coupling agent, a titanate coupling agent, and an organic chromium complex coupling agent, and more preferably a silane coupling agent.

[0048] As another preferred embodiment of the preparation method provided by the present application, the antioxidant is selected from at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 2246, antioxidant CA, and antioxidant 626, and preferably antioxidant 1010 and / or antioxidant 168.

[0049] As another preferred embodiment of the preparation method provided by the present application, the lubricant is selected from at least one of ethylene bis-stearamide, calcium stearate, monoglyceride, polyethylene wax, erucamide, and pentaerythritol stearate.

[0050] As another preferred embodiment of the preparation method provided by the present application, the outer layer material further includes a filler.

[0051] Further preferably, the amount of the second polyglycolic acid resin is 100 parts by weight, and the amount of the filler is 1-99 parts by weight, preferably 5-50 parts by weight, and more preferably 10-50 parts by weight.

[0052] Further preferably, the filler is an organic filler and / or an inorganic filler; preferably at least one of a particulate inorganic filler, a flaky inorganic filler, and a fibrous inorganic filler; and more preferably a fibrous inorganic filler, such as meerschaum fiber and / or glass fiber.

[0053] Further preferably, the particulate inorganic filler has a particle size of 0.05-100 μm, preferably 0.1-50 μm, and more preferably 0.1-10 μm.

[0054] Further preferably, the flaky inorganic filler has a particle size (flaky size) of 0.05-100 μm, preferably 0.1-50 μm, and more preferably 0.1-10 μm.

[0055] Further preferably, the fibrous inorganic filler has a diameter of 0.05-20 μm and an aspect ratio of 10-1000.

[0056] As another preferred embodiment of the preparation method provided by the present application, the first impregnation treatment in step S2 is performed in a first impregnation mold, the first impregnation mold is an adjustable impregnation mold, the first impregnation mold comprises a fiber inlet, a fiber outlet, and a melt flow channel, and at least one first godet is arranged in the mold cavity of the first impregnation mold; the first godet is movable between the fiber inlet and the fiber outlet; and / or the first godet is movable in a direction perpendicular to the line connecting the fiber inlet and the fiber outlet.

[0057] As another preferred embodiment of the preparation method provided by the present application, the first impregnation treatment in step S2 is performed in a second impregnation mold, the second impregnation mold is a combined impregnation mold, the second impregnation mold comprises a first module, an intermediate module, and a second module connected in sequence, the first module is provided with a fiber inlet and a first module flow channel, the second module is provided with a fiber outlet and a second module flow channel, and the intermediate module is provided with an intermediate module flow channel; after the first module, the intermediate module, and the second module are connected in sequence, the first module flow channel, the intermediate module flow channel, and the second module flow channel are connected to form a combined flow channel for the fiber to pass through.

[0058] As another preferred scheme of the preparation method provided by the application, the first impregnation treatment in step S2 is performed in a third impregnation die, the third impregnation die is a strong turbulent flow impregnation die, the third impregnation die comprises a fiber inlet channel, an impregnation outlet and a melt slit runner, and the fiber inlet channel, the impregnation outlet and the melt slit runner are all connected with a die cavity inside the third impregnation die; wherein a second godet is arranged in the die cavity of the third impregnation die, and the second godet comprises at least one driving godet, and the driving godet is driven to rotate by a driving device.

[0059] In a third aspect, the application provides an application of the composite material or the composite material prepared by the preparation method in the fields of catering, building decoration, oil field chemical industry and engineering plastics.

[0060] The application has at least the following beneficial effects:

[0061] (1) The glass fiber reinforced polyglycolic acid composite material has an inner-outer layer composite structure. The inner layer material comprises continuous / constant-length glass fibers. Through the special impregnation process of the application, the flowability of the glass fibers in the matrix melt is improved, so that the high-content glass fibers are uniformly dispersed in the polyglycolic acid, greatly enhancing the mechanical properties such as bending, heat resistance and impact of the polyglycolic acid. Through the coating of the outer layer material, the comprehensive performance and surface quality of the obtained composite material can be further strengthened, and at the same time, the material forming process requirements can be reduced, the processing temperature window can be widened, the application field of the composite material can be expanded, and the application value is excellent.

[0062] (2) The glass fiber reinforced polyglycolic acid composite material of the application adds fillers in the outer layer material, which can reduce the cost of the composite material on the one hand, and further improve the mechanical strength and thermal stability of the composite material on the other hand.

[0063] (3) The glass fiber reinforced polyglycolic acid composite material of the application also has the advantages of simple preparation process, good performance stability, good dimensional stability, good surface quality and the like. BRIEF DESCRIPTION OF DRAWINGS

[0064] Figure 1 FIG. 1 is a structure schematic diagram of a glass fiber reinforced polyglycolic acid composite material in an embodiment of the application;

[0065] Figure 2 FIG. 2 is a structure schematic diagram of a glass fiber reinforced polyglycolic acid composite material manufacturing system in an embodiment of the application;

[0066] Figure 3 FIG. 3 is a structure schematic diagram of a glass fiber reinforced polyglycolic acid composite material manufacturing system in another embodiment of the application;

[0067] Figure 4This is a cross-sectional view of the first impregnation mold in one embodiment of the present invention;

[0068] Figure 5 This is a cross-sectional view of the second impregnation mold in one embodiment of the present invention;

[0069] Figure 6 This is a cross-sectional view of the third impregnation mold in one embodiment of the present invention;

[0070] Figure 7 This is a schematic diagram of the second impregnation treatment in one embodiment of the present invention;

[0071] 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.

[0072] Explanation of reference numerals in the attached figures:

[0073] 0-1, Inner core material; 0-2, Fiber bundle; 0-3, Outer layer material;

[0074] 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;

[0075] 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;

[0076] 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;

[0077] 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;

[0078] 4-1. Extruder I; 4-2. Extruder II;

[0079] 5-1 Core; 5-2 Outer shell; 5-3 Outer shell opening template; 5-4 Material strip; 5-5 Second resin inlet. Detailed Implementation

[0080] In order to make the technical problems, technical solutions and beneficial effects of the present application clearer, the present application will be further described in detail in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to illustrate the present patent and do not limit the protection scope of the present application in any way.

[0081] In the first aspect, the glass fiber reinforced polyglycolic acid composite material provided by the present application comprises an inner core material and at least one outer layer material; the inner core material comprises a first polyglycolic acid resin, glass fibers and a first additive, the glass fibers continuously extend from one end of the inner core material to the opposite end; the outer layer material wraps the inner core material, and the outer layer material comprises a second polyglycolic acid resin and a second additive.

[0082] In the present application, the terms "one end" and "opposite end" are generally relative to the longitudinal direction of the glass fiber reinforced polyglycolic acid composite material.

[0083] In the transverse cross section of the glass fiber reinforced polyglycolic acid composite material, the inner core material and the outer layer material are sequentially arranged from inside to outside, and the glass fibers are oriented along the longitudinal direction of the glass fiber reinforced polyglycolic acid composite material.

[0084] In the present application, the glass fibers are glass fiber bundles, and the length of the glass fiber bundles is substantially the same as the length (longitudinal dimension) of the glass fiber reinforced polyglycolic acid composite material, so that the glass fiber bundles continuously extend from one end to the opposite end in the longitudinal direction of the inner core material. The inner core material does not contain short fibers, especially non-oriented short fibers.

[0085] The present inventors have found that the use of a first component comprising a first polyglycolic acid resin and a first additive to impregnate continuous glass fibers to form an inner core material, and uniformly coating a second component comprising a second polyglycolic acid resin and a second additive on the outside of the inner core material, thereby forming a glass fiber reinforced polyglycolic acid composite material with continuous glass fiber reinforced resin as the inner core material and resin layer wrapped on the outside of the inner core material as the outer layer material, such polyglycolic acid composite material has excellent mechanical properties. In addition, by adjusting the properties and functions of the first polyglycolic acid resin in the inner core material and the second polyglycolic acid resin in the outer layer material, the performance of the glass fiber reinforced polyglycolic acid composite material can be adjusted.

[0086] In the glass fiber reinforced polyglycolic acid composite material of the present application, the outer layer material at least 80% coats the inner core material, for example, 80-99%, 85-95% coats the inner core material; the outer layer material can also continuously coat the inner core material.

[0087] The outer layer material is not limited in number of layers, and can be one layer or multiple layers. In some embodiments, the multiple layers of outer layer material can be formed of the same material or multiple materials.

[0088] According to some embodiments of the present application, the first polyglycolic acid resin has a melt flow rate of 5-500 g / 10 min at 230°C, 2.16 kg, for example, 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 10-150 g / 10 min.

[0089] According to some embodiments of the present application, the second polyglycolic acid resin has a melt flow rate of 5-500 g / 10 min at 230°C, 2.16 kg, for example, 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 10-150 g / 10 min.

[0090] In different embodiments of the present application, the melt flow rate of the first polyglycolic acid resin and the second polyglycolic acid resin is not particularly limited, and can be selected according to the desired performance.

[0091] In particular, the present inventors have found that the parameters (e.g., melt flow rate) according to the present application can be used to prepare polyglycolic acid composite materials with high surface quality performance and comprehensive performance. For example, the melt flow rate of the first polyglycolic acid resin is higher than that of the second polyglycolic acid resin, so that the polyglycolic acid composite material has improved mechanical properties; conversely, the melt flow rate of the second polyglycolic acid resin is higher than that of the first polyglycolic acid resin, so that the polyglycolic acid composite material has improved gloss.

[0092] According to some embodiments of the present application, the first polyglycolic acid resin and the second polyglycolic acid resin are the same or different, and each is independently selected from homopolymer polyglycolic acid and / or copolymer polyglycolic acid. Preferably, the homopolymer polyglycolic acid.

[0093] More preferably, the content of glycolic acid monomer in the copolymerized polyglycolic acid is ≥90 mol%, preferably ≥95 mol%.

[0094] The comonomers of copolymerized polyglycolic acid may include: cyclic monomers such as 1,4-dioxane-2,3-dione, lactide, lactones (e.g., p-propiolactone, p-butyrolactone, p-neopentrolactone, p-butyrolactone, 8-pentanolactone, p-ethyl-8-pentanolactone, E-caprolactone), carbonates (e.g., trimethylene carbonate), ethers (e.g., 1,3-dioxane), ether esters (e.g., dioxane), amides (e.g., E-caprolactam), lactic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid and 6-hydroxyhexanoic acid and their alkyl esters; substantially equimolar mixtures of aliphatic diols (e.g., ethylene glycol and 1,4-butanediol) and aliphatic dicarboxylic acids (e.g., succinic acid and adipic acid) or their alkyl esters; and combinations of two or more of the above.

[0095] The synthesis methods for polyglycolic acid can include liquid-phase polycondensation of glycolic acid, solid-phase polycondensation of glycolic acid, melt polycondensation of glycolic acid, or ring-opening polymerization of glycolide; ring-opening polymerization of glycolide is preferred, and the raw material for glycolide can be obtained by coal chemical processes.

[0096] According to some embodiments of the present invention, the composite material is in the form of strips, rods, or granules.

[0097] In this invention, the strip-shaped, rod-shaped, or granular glass fiber reinforced polyglycolic acid composite material can be cut from a continuous filament glass fiber reinforced polyglycolic acid composite material.

[0098] Further preferably, the length of the strip-shaped or rod-shaped composite material is 5-30 mm, for example, 5 mm, 6 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, etc. Preferably 5-25 mm, more preferably 6-15 mm; and / or the particle size of the granular composite material is 2-5 mm, for example, 2 mm, 3 mm, 4 mm, 5 mm, etc. Preferably 3-4 mm.

[0099] This invention does not impose special requirements on the cross-sectional shape of the glass fiber reinforced polyglycolic acid composite material. In some embodiments, the cross-section of the granular or rod-shaped glass fiber reinforced polyglycolic acid composite material is circular or near-circular. In other embodiments, the cross-section of the granular or strip-shaped glass fiber reinforced polyglycolic acid composite material is rectangular or square.

[0100] According to some embodiments of the present application, the first polyglycolic acid resin is used in an amount of 10-200 parts by weight, for example, 10 parts by weight, 20 parts by weight, 30 parts by weight, 50 parts by weight, 60 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, etc., preferably 10-150 parts by weight, more preferably 20-150 parts by weight, based on 100 parts by weight of the glass fiber; and / or 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 10-100 parts by weight, more preferably 50-100 parts by weight.

[0101] According to some embodiments of the present application, the first polyglycolic acid resin is used in an amount of 10-200 parts by weight, for example, 10 parts by weight, 20 parts by weight, 30 parts by weight, 50 parts by weight, 60 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, etc., preferably 10-150 parts by weight, more preferably 20-150 parts by weight, based on 100 parts by weight of the glass fiber; and / or 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 10-100 parts by weight, more preferably 50-100 parts by weight.

[0102] According to some embodiments of the present application, and / or, the second polyglycolic acid resin is used in an amount of 100 parts by weight, the second auxiliary agent includes at least one of 0.05-5 parts by weight of a second compatibilizer, 0.1-3 parts by weight of a second antioxidant, and 0.1-1 parts by weight of a second lubricant; for example, the second compatibilizer can be used in an amount of 0.05 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 1 parts by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, etc.; and / or, the second antioxidant can be used in an amount of 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 1 parts by weight, 2 parts by weight, 3 parts by weight, etc.; and / or, the second lubricant can be used in an amount of 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, etc. Preferably, the second polyglycolic acid resin is used in an amount of 100 parts by weight, the second auxiliary agent includes at least one of 0.05-2 parts by weight of a second compatibilizer, 0.1-1 parts by weight of a second antioxidant, and 0.2-1 parts by weight of a second lubricant.

[0103] According to some embodiments of the present application, the compatibilizer is selected from at least one of a coupling agent, preferably at least one of a silane coupling agent, a titanate coupling agent, an organic chromium complex coupling agent, more preferably a silane coupling agent. Examples of silane coupling agents suitable for use in the present application include, but are not limited to: KH-550, KH-560.

[0104] According to some embodiments of the present application, the antioxidant is selected from at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 2246, antioxidant CA, and antioxidant 626, preferably antioxidant 1010 and / or antioxidant 168.

[0105] According to some embodiments of the present application, the lubricant is selected from at least one of ethylene bis-stearamide, calcium stearate, monoglyceride fatty acid, polyethylene wax, erucamide, pentaerythritol stearate.

[0106] According to some embodiments of the present application, the glass fiber is continuous and / or chopped glass fiber.

[0107] In different embodiments of the present application, the first auxiliary agent and the second auxiliary agent are not limited to specific types and amounts of the several auxiliary agents, and each can have a wide range of selection. For example, the first auxiliary agent and the second auxiliary agent each independently can further include at least one of a chain extender, a slip agent, an antistatic agent, and a plasticizer.

[0108] According to some embodiments of the present application, the outer layer material further includes a filler.

[0109] According to some embodiments of the present application, the amount of the second polyglycolic acid resin is 100 parts by weight, and the amount of the filler is 1-99 parts by weight, for example, 1 part by weight, 5 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 70 parts by weight, 90 parts by weight, 99 parts by weight, etc. Preferably, the amount of the filler is 5-50 parts by weight, more preferably 10-50 parts by weight.

[0110] According to some embodiments of the present application, the filler is an organic filler and / or an inorganic filler.

[0111] Preferably, the filler is at least one of a particulate inorganic filler, a flaky inorganic filler, and a fibrous inorganic filler.

[0112] More preferably, the filler is a fibrous inorganic filler, for example, sepiolite fiber and / or glass fiber.

[0113] Specifically, the inorganic filler in the present application can be selected from calcium carbonate, talc, glass beads, kaolin, silica, carbon black, montmorillonite, barium sulfate, wollastonite, whisker, sepiolite fiber, glass fiber, etc.

[0114] According to some embodiments of the present application, the particle size of the particulate inorganic filler is 0.05-100 μm, for example, 0.05 μm, 0.1 μm, 1 μm, 3 μm, 5 μm, 10 μm, 20 μm, 30 μm, 50 μm, 60 μm, 80 μm, 100 μm, etc., preferably 0.1-50 μm, more preferably 0.1-10 μm.

[0115] According to some embodiments of the present application, the particle size (flaky size) of the flaky inorganic filler is 0.05-100 μm, for example, 0.05 μm, 0.1 μm, 1 μm, 3 μm, 5 μm, 10 μm, 20 μm, 30 μm, 50 μm, 60 μm, 80 μm, 100 μm, etc., preferably 0.1-50 μm, more preferably 0.1-10 μm.

[0116] According to some embodiments of the present application, the diameter of the fibrous inorganic filler is 0.05-20 μm, and the aspect ratio is 10-1000. For example, the diameter can be 0.05 μm, 0.1 μm, 1 μm, 3 μm, 5 μm, 10 μm, 15 μm, 20 μm, etc., and the aspect ratio can be 10, 20, 50, 80, 100, 200, 500, 800, 1000, etc.

[0117] The addition of the filler to the outer layer material can effectively improve the flowability of the polyglycolic acid resin, and also can enhance the mechanical strength of the composite material, while greatly reducing the cost of the composite material.

[0118] In a second aspect, the application provides a method for preparing the glass fiber reinforced polyglycolic acid composite material, comprising:

[0119] S1. mixing the first polyglycolic acid resin and the first auxiliary agent at 40-60℃ for 3-5min, and then melting at 230-260℃ to obtain a first component melt;

[0120] S2. performing first impregnation treatment on the continuous glass fiber with the first component melt in step S1 to form a filamentous inner core material;

[0121] S3. mixing the second polyglycolic acid and the second auxiliary agent at 40-60℃ for 3-5min, and then melting at 230-260℃ to obtain a second component melt;

[0122] S4. performing at least one second impregnation treatment on the inner core material obtained in step S2 with at least one second component melt in step S3 to obtain the glass fiber reinforced polyglycolic acid composite material.

[0123] The preparation method of the application can be performed continuously in line to obtain a continuous filamentous product, which can be directly stored and used, or cut into a strip-shaped, rod-shaped or particulate product with a certain length and particle size.

[0124] According to some embodiments of the application, the mixing conditions in step S1 are: temperature of 40-60℃ and time of 3-5min; and / or the melting temperature in step S1 is 230-260℃.

[0125] According to some embodiments of the application, the mixing conditions in step S3 are: temperature of 40-60℃ and time of 3-5min; and / or the melting temperature in step S3 is 230-260℃.

[0126] According to some embodiments of the application, step S2 further comprises: dispersing and preheating the continuous glass fiber before performing the first impregnation treatment; preferably, the preheating temperature is 80-250℃.

[0127] According to some embodiments of the application, step S4 further comprises: after the second impregnation treatment, pulling out, drawing, cooling, drying and cutting the material obtained after the second impregnation treatment to obtain the glass fiber reinforced polyglycolic acid composite material. In the application, the process conditions for pulling out, drawing, cooling, drying and cutting are not particularly limited, and those skilled in the art can adjust them according to the specific performance requirements of the prepared glass fiber reinforced polyglycolic acid composite material.

[0128] According to some embodiments of the present application, the first impregnation process in step S2 can be performed in a first impregnation die, which is an adjustable impregnation die, comprising a fiber inlet, a fiber outlet and a melt runner, and at least one first godet is arranged in the die cavity of the first impregnation die; the first godet is movable between the fiber inlet and the fiber outlet; and / or, the first godet is movable in a direction perpendicular to the line connecting the fiber inlet and the fiber outlet.

[0129] According to some embodiments of the present application, the first impregnation process in step S2 can be performed in a second impregnation die, which is a combined impregnation die, comprising a first module, an intermediate module and a second module connected in sequence, the first module is provided with a fiber inlet and a first module runner, the second module is provided with a fiber outlet and a second module runner, and the intermediate module is provided with an intermediate module runner; after the first module, the intermediate module and the second module are connected in sequence, the first module runner, the intermediate module runner and the second module runner are connected to form a combined runner for the fiber to pass through.

[0130] According to some embodiments of the present application, the first impregnation process in step S2 can also be performed in a third impregnation die, which is a strong turbulent impregnation die, comprising a fiber inlet channel, an impregnation outlet and a melt slit runner, all of which are connected to the die cavity inside the third impregnation die; wherein the die cavity of the third impregnation die is provided with a second godet, which comprises at least one driven godet, and the driven godet is driven to rotate by a driving device.

[0131] The first impregnation die, the second impregnation die and the third impregnation die used in the present application are described in Chinese patent applications CN202011193483.3, 202011191450.5 and 202011199839.4, which are incorporated herein by reference in their entirety.

[0132] It should be noted that the first impregnation die, the second impregnation die and the third impregnation die described above can be applied to any existing manufacturing system and preparation technology of glass fiber reinforced polyglycolic acid composite materials.

[0133] According to some embodiments of the preparation method of the present application, the second impregnation treatment in step S4 can be performed in a forming mold. The forming mold is composed of a core, an outer sleeve, and an outer sleeve die plate. The core is located inside the outer sleeve, forming a cavity with the outer sleeve, and the resin melt can enter the cavity from the bottom or top or both sides of the outer sleeve. The core can move forward and backward in the outer sleeve, and the pressure of the melt in the cavity can be adjusted by adjusting the size of the cavity space formed. The pressure of the melt in the cavity can also be adjusted by the angle between the core and the outer sleeve. The working principle of the forming mold is as follows: the strip formed after impregnation in the mold is guided to pass through the hole in the middle of the core, and then the inner and outer layer material composite structure is formed in the cavity formed by the core and the outer sleeve filled with mixed melt, and finally it is guided out through the outer sleeve die plate.

[0134] The present application will be further described below with reference to the accompanying drawings.

[0135] Figure 1 The structure of the glass fiber reinforced polyglycolic acid composite material of the present application is shown. As shown in Figure 1 , the cross section of the glass fiber reinforced polyglycolic acid composite material of the present application is circular, and sequentially includes an inner core material 0-1 and an outer layer material 0-3 from inside to outside, the inner core material 0-1 has glass fiber bundles 0-2 oriented in the longitudinal direction distributed therein, and the glass fiber bundles 0-2 are uniformly dispersed in the inner core material 0-1.

[0136] As shown in Figure 2 and Figure 3 , the manufacturing system of the present application includes a fiber rack and fiber guiding device 1, a fiber pretreatment device 2, an impregnation mold 3, a melt plasticizing feeding device 4, a forming mold 5, a cooling water tank 6, a drying machine 7, a traction machine 8, a granulator 9, a collection box 10, and an electric control system (not shown in the figure) connected in sequence.

[0137] In the manufacturing system, the forming mold 5 is used for the forming of the inner and outer layer composite structure of the polyglycolic acid composite material, and its structure is shown in Figure 8 .

[0138] In the manufacturing system, the first impregnation mold 3 is used for the impregnation of glass fiber and polyglycolic acid resin melt.

[0139] As shown in Figure 4As shown, in one embodiment, the first impregnation die is an impregnation device capable of adjusting the position of the godet, which includes a first impregnation die head A300, the first impregnation die head A300 including an impregnation die body A7, a fiber inlet A1, a fiber outlet A6, and a melt flow channel A3. At least one first godet A8 is arranged in the die cavity, wherein the godet A8 is movable between the fiber inlet A1 and the fiber outlet A6, or the first godet A8 is movable in a direction perpendicular to the line connecting the fiber inlet A1 and the fiber outlet A6, or the first godet A8 is movable both between the fiber inlet A1 and the fiber outlet A6 and in a direction perpendicular to the line connecting the fiber inlet A1 and the fiber outlet A6.

[0140] Taking a rectangular first impregnation die head A300 as an example, a plurality of first godets A8 are arranged in the first impregnation die head A300, and the axial direction of each first godet A8 is the width direction of the first impregnation die head A300, so that each first godet A8 is movable in the length direction of the first impregnation die head A300 and is also movable in the height direction, thereby changing the position of the first godet A8 in the first impregnation die head A300.

[0141] It can be understood that the axial direction of the first godet A8 can also be the length direction of the first impregnation die head A300, at this time each first godet A8 is movable in the width direction of the first impregnation die head A300 and is also movable in the height direction of the first impregnation die head A300, thereby changing the position of the first godet A8 in the first impregnation die head A300.

[0142] Since the fiber needs to pass around the first godet A8 in the die cavity when it travels in the die cavity of the first impregnation die head A300, by changing the position (horizontal position, longitudinal position, etc.) of the first godet A8 in the first impregnation die head A300, the travel path of the fiber in the die cavity can be changed, so that when the required impregnation conditions of the fiber change, a new die does not need to be replaced, but only the position of the first godet A8 in the first impregnation die head A300 needs to be adjusted, thereby improving the production efficiency and the continuity of production. At the same time, the number of first impregnation die heads A300 can be reduced, and the production cost can be saved.

[0143] Specifically, the inventive concept of the present application is to achieve the purpose of adjusting the position of the first godet A8 by slotting the inner wall of the die cavity of the first impregnation die head A300.

[0144] A first sliding groove A4 is arranged on the first inner wall of the first impregnation die head A300, and the first sliding groove A4 extends between the fiber inlet A1 and the fiber outlet A6 (i.e. Figure 4As shown in the Y-axis direction), the first guide roller A8 moves along the second sliding groove A2 to change its vertical position in the die.

[0145] Further, the first inner wall of the first impregnation die head A300 is also provided with a second sliding groove A2 extending in a direction perpendicular to the first sliding groove A4 (i.e. Figure 4 As shown in the Y-axis direction), the first guide roller A8 moves along the second sliding groove A2 to change its vertical position in the die.

[0146] It should be noted that the first sliding groove A4 and the second sliding groove A2 can be connected. Thus, the first guide roller A8 can be arbitrarily moved in the longitudinal direction or the transverse direction, so that its position is changed.

[0147] The cross section of the first sliding groove A4 and the second sliding groove A2 can be trapezoidal, circular, arc-shaped or rectangular, and the present application does not limit it.

[0148] Both ends of the first guide roller A8 are provided with an adjusting device (not shown in the figure), which is 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.

[0149] As shown in the Y-axis direction), the first guide roller A8 moves along the second sliding groove A2 to change its vertical position in the die. Figure 5 As shown in the Y-axis direction), the first guide roller A8 moves along the second sliding groove A2 to change its vertical position in the die.

[0150] After the first module B3, the intermediate module B6 and the second module B7 are connected in sequence, the first module flow channel B31, the intermediate module flow channel B61 and the second module flow channel B71 are connected to form a combined flow channel B4 for the fiber to pass through, wherein the number of intermediate modules B6 is at least one. That is, the first module B3 is the first module, and the second module B7 is the tail module, and there is one or more intermediate modules B6 between them. It should be noted that these intermediate modules B6 are also connected in sequence.

[0151] That is, the number of intermediate modules B6 can be increased or decreased as needed, so that when the impregnation requirement changes, different intermediate modules B6 are selected to be combined to form a combined second impregnation die head B300, thereby improving the continuity and production efficiency of production, and saving the cost of additional mold opening.

[0152] 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.

[0153] 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.

[0154] 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.

[0155] Understandably, different combinations of flow channels B4 can be obtained by selecting different intermediate modules B6.

[0156] 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.

[0157] 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.

[0158] The second godet roller is arranged in the die cavity of the impregnation die outer body C2, and the second godet roller comprises at least one driving godet roller C4, and the driving godet roller C4 is driven to rotate by a driving device (not shown in the figure). Since the rotation of the driving godet roller C4 is driven by the driving device rather than being driven by the traction of the fiber, when the fiber passes through the driving godet roller C4, the driving godet roller C4 driven to rotate helps to reduce the traction tension of the fiber and the friction between the fiber and the driving godet roller C4, thereby reducing the breaking of the fiber, ensuring the integrity of the fiber, avoiding the fiber being pulled off, and improving the mechanical properties of the material.

[0159] Preferably, the second godet roller further comprises at least one driven godet roller C5, and the driven godet roller C5 is driven by the fiber passing through the driving godet roller C4; or the driven godet roller C5 is connected with the driving godet roller C4 through a belt mechanism, a gear mechanism or a chain mechanism.

[0160] As shown in Figure 6 , an example with one driving godet roller C4 and two driven godet rollers C5 is shown, wherein the two driven godet rollers C5 are arranged one above the other to extend the impregnation path of the fiber passing therethrough. The heights of the driving godet roller C4 and the driven godet roller C5 in the die cavity can be the same or different.

[0161] Further, the driving device can be a motor, a hydraulic mechanism or a reduction box, etc. capable of driving the driving godet roller C4 to rotate.

[0162] According to the running speed v1 of the fiber entering the die cavity of the impregnation die outer body C2, the tangential speed v2 of the corresponding driving godet roller C4 can be selected, for example, the tangential speed v2 of the driving godet roller C4 is the same as the running speed v1 of the fiber, i.e. v1=v2, so as to reduce the breaking and wear of the fiber, thereby ensuring the integrity of the fiber and promoting the impregnation degree of the fiber, shortening the impregnation time and improving the production efficiency.

[0163] As shown in Figure 2 , the melt plasticizing feeding device 4 is composed of a double screw extruder for melt plasticizing the material. The double screw extruder is a co-rotating double screw extruder, the screw diameter is 25mm-95mm, and the length-diameter ratio is 36:1-65:1. When the melt plasticizing feeding device 4 is composed of one extruder 4, the melt plasticized melt in the extruder is divided by a melt distributor, respectively enters the impregnation die and the forming die, and the melt flow control valve is used to control the flow of each.

[0164] As shown in Figure 3As shown, when the melt plasticizing feed device 4 is composed of two extruders 4-1 and 4-2, the melt plasticized melt of each extruder I 4-1 and extruder II 4-2 is respectively fed into the impregnation die and the forming die. In this embodiment, the melt plasticizing feed device is composed of two extruders I 4-1 and extruder II 4-2, and the melt plasticized melt of each extruder I 4-1 and extruder II 4-2 is respectively fed into the first impregnation die 3 and the forming die 5. The extruder I 4-1 and the extruder II 4-2 can be fed with the same or different materials, so that the composite material with the same or different materials of the inner layer and the outer layer can be prepared.

[0165] The fiber pretreatment device 2 is composed of a combination of a tension roller and a hot oven, which combination releases the tension of the fiber when it enters the hot oven, so as to adapt to different strength of the fiber and avoid the fiber with small strength from being broken before entering the impregnation die. The surface of the tension roller in the fiber pretreatment device 2 needs to be treated with ceramic plating to increase the surface roughness and reduce the friction to the fiber.

[0166] In the manufacturing system, the fiber frame and fiber guide device 1 is used for guiding and untwisting the fiber, and is provided with an automatic control untwisting device and is connected with the traction machine 8 and the electric control system (such as the PLC control device).

[0167] In the manufacturing system, the cooling water tank 6, the drying machine 7, the traction machine 8, the pelletizer 9 and the collection box 10 are conventional devices or apparatuses known by those skilled in the art, which will not be described here.

[0168] Figure 7 A schematic diagram of the second impregnation treatment using the forming die is shown, Figure 8 A sectional view of the forming die used in the second impregnation treatment is shown.

[0169] As Figure 8 As shown, in an embodiment, the forming die 5 is composed of a core 5-1, an outer sleeve 5-2 and an outer sleeve die plate 5-3. The core 5-1 is located inside the outer sleeve 5-2 to form a cavity with the outer sleeve 5-2, and the resin melt can enter the cavity from the bottom or top or two sides of the outer sleeve 5-2. The core 5-1 can move forward and backward in the outer sleeve 5-2, and the pressure of the melt in the cavity can be adjusted by adjusting the size of the cavity. The pressure of the melt in the cavity can also be adjusted by adjusting the angle between the core 5-1 and the outer sleeve 5-2. The working principle of the forming die 5 is as follows: the strip formed by the inner layer impregnated material after passing through the impregnation die 3 is guided to pass through the hole in the middle of the core 5-1, and then the inner and outer layer material composite structure is formed in the cavity filled with mixed melt formed by the core 5-1 and the outer sleeve 5-2, and finally it is guided out through the outer sleeve die plate 5-3.

[0170] AsFigure 7 As shown, the strand 5-4 enters a core (not shown) formed by the outer sleeve 5-2 to form a cavity filled with the second component melt, wherein the second component melt is fed into the cavity from the second resin inlet 5-5.

[0171] In the following examples and comparative examples, the following materials are used Figure 3 The glass fiber reinforced polyglycolic acid composite material is prepared by the manufacturing system shown in the figure, wherein the first impregnation treatment selects Figure 4 The first impregnation mold shown in the figure is used for the first impregnation treatment, and the second impregnation treatment uses Figure 8 The molding mold shown in the figure.

[0172] The glass fiber reinforced polyglycolic acid composite material and the preparation method thereof provided by the present application will be described in detail below in combination with specific examples.

[0173] Unless otherwise defined, the technical terms used in the following examples have the same meanings as generally understood by those skilled in the art to which the present application belongs. The reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the raw materials, instruments and equipment used in the following examples can be purchased on the market or obtained by existing methods; the reagent amount, unless otherwise specified, is the reagent amount in conventional experimental operation; the experimental method, unless otherwise specified, is a conventional method.

[0174] In each of the embodiments and comparative examples of the present application, the test method of each performance data is as follows:

[0175] (1) Tensile strength: GB / T 1040-2018;

[0176] (2) Flexural modulus: GB / T 9341-2008;

[0177] (3) Impact strength: GB / T 1843-2008;

[0178] (4) Heat distortion temperature: GB / T 1634-2004, A method, bending stress 1.8 MPa.

[0179] In each of the embodiments and comparative examples of the present application, the materials used are as follows:

[0180] (1) Polyglycolic acid: homopolymer polyglycolic acid, melt index 10, 40, 100, 150 g / 10 min (2.16 kg, 230°C), the first two were purchased from Shanghai Pujing Chemical Co., Ltd., and the last two were purchased from Japan Wuhe and Liaoning Jinmei, respectively;

[0181] (2) Copolymer polyglycolic acid: melt index 100 g / 10 min (2.16 kg, 230°C), glycolic acid monomer content 95 mol%, lactic acid monomer content 5 mol%, self-made;

[0182] (2) Glass fiber: Alkali-free glass fiber, diameter 17 μm, linear density 2400 tex, Chongqing International Composite Material Co., Ltd.

[0183] (3) Antioxidant 1010: Irganox 1010, Germany Ciba;

[0184] (4) Antioxidant 168: Irgafos 168, Germany BASF;

[0185] (5) Silane coupling agent: KH-550, Nanjing Youpu Chemical Co., Ltd.

[0186] (6) Calcium stearate: 6.5 wt% Ca, Inokai Co., Ltd.

[0187] (7) Talc: particle size 50 μm, Inokai Co., Ltd.

[0188] (8) Calcium carbonate: particle size 0.1 μm, Inokai Co., Ltd.

[0189] (9) Montmorillonite: particle size 10 μm, Inokai Co., Ltd.

[0190] (10) Sepiolite fiber: diameter 0.1 μm, aspect ratio 100, Inokai Co., Ltd.

[0191] (11) Chopped glass fiber: diameter 15 μm, aspect ratio 50, China Jushi Group.

[0192] Example 1

[0193] (1) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) was mixed with 1 part by weight of KH550, 0.2 parts by weight of antioxidant 168, 0.3 parts by weight of antioxidant 1010, and 0.2 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes to obtain a first component melt, which was fed into a first impregnation mold.

[0194] (2) Continuous glass fiber was introduced into the first impregnation mold under the action of a pulling machine to impregnate and disperse with the above-mentioned first component melt to form a sample, which was used as an inner layer material, wherein the glass fiber content was 60 parts by weight.

[0195] (3) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) was mixed with 2 parts by weight of KH550, 0.1 parts by weight of antioxidant 1010, and 0.5 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, which was used as an outer layer material, and was fed into a double-screw extruder connected to a molding mold to obtain a second component melt.

[0196] (4) The inner layer material is introduced into the forming die under the action of the traction machine, guided through the hole in the middle of the core, and formed into a composite structure of the inner and outer layers in the cavity formed by the core and the outer sleeve filled with the melt of the second component. Finally, the material is guided out through the die plate of the outer sleeve.

[0197] (5) The amount of the outer layer material is adjusted by adjusting the amount of extrusion of the extruder for the outer layer material and the diameter of the die outlet of the die, so that the outer layer material is coated in a defined amount. The cutter speed of the cutter of the pelletizer is adjusted to control the length of the obtained polyglycolic acid composite material to be 15 mm. The content of the first polyglycolic acid in the obtained composite material is 100 parts by weight, the content of the glass fiber is 60 parts by weight, and the content of the second polyglycolic acid is 100 parts by weight.

[0198] (6) The glass fiber reinforced polyglycolic acid composite material prepared by the above method is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0199] Comparative Example 1

[0200] (1) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) is mixed with 1 part by weight of KH550, 0.2 parts by weight of antioxidant 168, 0.3 parts by weight of antioxidant 1010, 0.2 parts by weight of calcium stearate, and 60 parts by weight of glass fiber (25 mm) in a high-speed mixer at 50°C for 3 minutes.

[0201] (2) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) is mixed with 2 parts by weight of KH550, 0.1 parts by weight of antioxidant 1010, and 0.5 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes.

[0202] (3) The two mixtures are added together into a twin-screw extruder for melt granulation, and the obtained polyglycolic acid composite material has a length of 15 mm. The content of the first polyglycolic acid in the obtained composite material is 100 parts by weight, the content of the glass fiber is 60 parts by weight, and the content of the second polyglycolic acid is 100 parts by weight.

[0203] (4) The glass fiber reinforced polyglycolic acid composite material prepared by the above method is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0204] Comparative Example 2

[0205] (1) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) is mixed with 1 part by weight of KH550, 0.2 parts by weight of antioxidant 168, 0.3 parts by weight of antioxidant 1010, 0.2 parts by weight of calcium stearate, and 60 parts by weight of glass fiber (25 mm) in a high-speed mixer at 50°C for 3 minutes, and then melt granulated to obtain polyglycolic acid composite material 1.

[0206] (2) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) was mixed with 2 parts by weight of KH550, 0.1 part by weight of antioxidant 1010, and 0.5 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, and then melt granulation was performed to obtain polyglycolic acid composite 2.

[0207] (3) Polyglycolic acid composite 1 and polyglycolic acid composite 2 were added together into a twin-screw extruder for melt granulation, and the obtained polyglycolic acid composite particles had a length of 15 mm. In the obtained composite, the content of the first polyglycolic acid was 100 parts by weight, the content of the glass fiber was 60 parts by weight, and the content of the second polyglycolic acid was 100 parts by weight.

[0208] (4) The glass fiber reinforced polyglycolic acid composite prepared above was injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0209] Example 2

[0210] (1) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) was mixed with 0.05 parts by weight of KH550, 0.05 parts by weight of antioxidant 168, 0.05 parts by weight of antioxidant 1010, and 0.5 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes to obtain a first component melt, which was fed into a first impregnation mold.

[0211] (2) Continuous glass fiber was introduced into the first impregnation mold under the action of a traction machine to impregnate and disperse the above-mentioned first component melt, forming a sample bar, which was used as an inner layer material, and the content of the glass fiber was 20 parts by weight.

[0212] (3) 100 parts by weight of polyglycolic acid (melt index 150 g / 10 min) was mixed with 0.1 parts by weight of KH550, 0.2 parts by weight of antioxidant 1010, and 0.2 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, which was used as an outer layer material, and was fed into a twin-screw extruder connected to a forming mold to obtain a second component melt.

[0213] (4) The inner layer material was introduced into the forming mold under the action of the traction machine, guided through the hole in the middle of the core, and realized the molding of the composite structure of the inner and outer layer materials in the cavity filled with the second component melt formed by the core and the outer sleeve, and finally guided out through the outer sleeve die plate.

[0214] (5) The amount of the outer layer material is adjusted by adjusting the amount of extrusion and the diameter of the die exit of the extruder for the outer layer material, so that the outer layer material is coated in a defined amount. The speed of the cutter of the cutter granulator is adjusted, and the length of the obtained polyglycolic acid composite is controlled to be 6 mm. In the obtained composite, the content of the first polyglycolic acid is 100 parts by weight, the content of the glass fiber is 20 parts by weight, and the content of the second polyglycolic acid is 50 parts by weight.

[0215] (6) The glass fiber reinforced polyglycolic acid composite prepared by the above method is injection molded into a standard sample bar, and performance testing is performed. The test results are shown in Table 1.

[0216] Example 3

[0217] (1) 100 parts by weight of polyglycolic acid (melt index 150 g / 10 min) is mixed with 2 parts by weight of KH550, 0.5 parts by weight of antioxidant 168, 0.5 parts by weight of antioxidant 1010, and 1 part by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes to obtain a first component melt, which is then fed into a first impregnation mold.

[0218] (2) Continuous glass fibers are introduced into the first impregnation mold under the action of a traction machine to impregnate and disperse the above-mentioned first component melt, forming a sample bar, which is used as an inner layer material, wherein the content of the glass fiber is 150 parts by weight.

[0219] (3) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) is mixed with 0.05 parts by weight of KH550, 1 part by weight of antioxidant 1010, and 1 part by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, which is used as an outer layer material, and is fed into a double-screw extruder connected to a molding mold to obtain a second component melt.

[0220] (4) The inner layer material is introduced into the molding mold under the action of the traction machine, guided through the hole in the middle of the core, and realizes the molding of the composite structure of the inner and outer layer materials in the cavity filled with the second component melt formed by the core and the outer sleeve, and finally guided out through the outer sleeve die plate.

[0221] (5) The amount of the outer layer material is adjusted by adjusting the amount of extrusion and the diameter of the die exit of the extruder for the outer layer material, so that the outer layer material is coated in a defined amount. The speed of the cutter of the cutter granulator is adjusted, and the length of the obtained polyglycolic acid composite is controlled to be 3 mm. In the obtained composite, the content of the first polyglycolic acid is 100 parts by weight, the content of the glass fiber is 150 parts by weight, and the content of the second polyglycolic acid is 60 parts by weight.

[0222] (6) The glass fiber reinforced polyglycolic acid composite prepared by the above method is injection molded into a standard sample bar, and performance testing is performed. The test results are shown in Table 1.

[0223] Example 4

[0224] (1) 100 parts by weight of homopolymer polyglycolic acid (melt index 100 g / 10 min) was mixed with 0.5 parts by weight of KH550, 0.1 parts by weight of antioxidant 168, 0.2 parts by weight of antioxidant 1010, and 0.2 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes to obtain a first component melt, which was then fed into a first impregnation mold.

[0225] (2) Continuous glass fibers were introduced into the first impregnation mold under the action of a pulling machine to impregnate and disperse the first component melt to form a sample, which was used as an inner layer material, and the glass fiber content was 100 parts by weight.

[0226] (3) 100 parts by weight of homopolymer polyglycolic acid (melt index 100 g / 10 min) was mixed with 1 part by weight of KH550, 0.5 parts by weight of antioxidant 1010, and 0.2 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, which was used as an outer layer material, and was fed into a double-screw extruder connected to a molding mold to obtain a second component melt.

[0227] (4) The inner layer material was introduced into the molding mold under the action of the pulling machine, guided through the hole in the middle of the core, and the outer sleeve formed a cavity filled with the second component melt, realizing the molding of the inner and outer layer material composite structure, and finally guided out through the outer sleeve die plate.

[0228] (5) The amount of outer layer material was adjusted by adjusting the amount of extrusion of the extruder for the outer layer material and the diameter of the die outlet of the mold, so that the outer layer material was coated according to the defined amount, and the cutter speed of the cutter was adjusted to control the length of the obtained polyglycolic acid composite material to be 4 mm. The first polyglycolic acid content in the obtained composite material was 100 parts by weight, the glass fiber content was 100 parts by weight, and the second polyglycolic acid content was 80 parts by weight.

[0229] (6) The glass fiber reinforced polyglycolic acid composite material prepared by the above method was injection molded into a standard sample, and performance tests were conducted. The test results are shown in Table 1.

[0230] Example 5

[0231] The preparation process was the same as in Example 4, except that the homopolymer polyglycolic acid in step (1) was replaced by a copolymer polyglycolic acid with a melt index of 100 g / 10 min (glycolic acid monomer content of 95 mol%), and the homopolymer polyglycolic acid in step (3) was replaced by a copolymer polyglycolic acid with a melt index of 100 g / 10 min (glycolic acid monomer content of 95 mol%). The polyglycolic acid composite material was injection molded into a standard sample, and performance tests were conducted.

[0232] Example 6

[0233] The preparation process is the same as that of Example 1, except that 10 parts by weight of sepiolite fibers are added in step (3). The polyglycolic acid composite is injection molded into standard bars for performance testing.

[0234] Comparative Example 3

[0235] (1) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) is mixed with 1 part by weight of KH550, 0.2 parts by weight of antioxidant 168, 0.3 parts by weight of antioxidant 1010, 0.2 parts by weight of calcium stearate, and 60 parts by weight of glass fibers in a high-speed mixer at 50°C for 3 minutes.

[0236] (2) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) is mixed with 10 parts by weight of sepiolite fibers, 2 parts by weight of KH550, 0.1 parts by weight of antioxidant 1010, and 0.5 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes.

[0237] (3) The two mixtures above are added together into a twin-screw extruder for melt granulation, and the obtained polyglycolic acid composite particles have a length of 15 mm. In the obtained composite, the first polyglycolic acid content is 100 parts by weight, the glass fiber content is 60 parts by weight, the second polyglycolic acid content is 100 parts by weight, and the sepiolite fiber content is 10 parts by weight.

[0238] (4) The glass fiber reinforced polyglycolic acid composite prepared above is injection molded into standard bars for performance testing. The test results are shown in Table 1.

[0239] Comparative Example 4

[0240] (1) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) is mixed with 1 part by weight of KH550, 0.2 parts by weight of antioxidant 168, 0.3 parts by weight of antioxidant 1010, 0.2 parts by weight of calcium stearate, and 60 parts by weight of glass fibers in a high-speed mixer at 50°C for 3 minutes, and then melt granulation is performed to obtain polyglycolic acid composite 1.

[0241] (2) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) is mixed with 10 parts by weight of sepiolite fibers, 2 parts by weight of KH550, 0.1 parts by weight of antioxidant 1010, and 0.5 parts by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, and then melt granulation is performed to obtain polyglycolic acid composite 2.

[0242] (3) The polyglycolic acid composite 1 and the polyglycolic acid composite 2 were added together into a twin-screw extruder for melt granulation, and the obtained polyglycolic acid composite particles had a length of 15 mm. In the obtained composite, the content of the first polyglycolic acid was 100 parts by weight, the content of the glass fiber was 60 parts by weight, the content of the second polyglycolic acid was 100 parts by weight, and the content of the sepiolite fiber was 10 parts by weight.

[0243] (4) The glass fiber reinforced polyglycolic acid composite prepared above was injection molded into standard bars for performance testing. The test results are shown in Table 1.

[0244] Example 7

[0245] The preparation process was the same as that in Example 6, except that 10 parts by weight of sepiolite fiber in step (3) was replaced by 10 parts by weight of calcium carbonate. The polyglycolic acid composite was injection molded into standard bars for performance testing.

[0246] Example 8

[0247] The preparation process was the same as that in Example 6, except that 10 parts by weight of sepiolite fiber in step (3) was replaced by 10 parts by weight of talc. The polyglycolic acid composite was injection molded into standard bars for performance testing.

[0248] Example 9

[0249] The preparation process was the same as that in Example 6, except that 10 parts by weight of sepiolite fiber in step (3) was replaced by 10 parts by weight of montmorillonite. The polyglycolic acid composite was injection molded into standard bars for performance testing.

[0250] Example 10

[0251] The preparation process was the same as that in Example 6, except that 10 parts by weight of sepiolite fiber in step (3) was replaced by 10 parts by weight of short glass fiber. The polyglycolic acid composite was injection molded into standard bars for performance testing.

[0252] Example 11

[0253] The preparation process was the same as that in Example 3, except that 50 parts by weight of montmorillonite was added in step (3); in the obtained composite, the content of the first polyglycolic acid was 100 parts by weight, the content of the glass fiber was 150 parts by weight, the content of the second polyglycolic acid was 80 parts by weight, and the content of the montmorillonite was 40 parts by weight. The polyglycolic acid composite was injection molded into standard bars for performance testing.

[0254] Comparative Example 5

[0255] The preparation process is the same as that of Example 6, except that 10 parts by weight of sepiolite fibers are added in step (1) and no sepiolite fibers are added in step (3). The polyglycolic acid composite is injection molded into a standard sample bar for performance testing.

[0256] Comparative Example 6

[0257] The preparation process is the same as that of Example 6, except that 5 parts by weight of sepiolite fibers are added in step (1) and 5 parts by weight of sepiolite fibers are added in step (3). The polyglycolic acid composite is injection molded into a standard sample bar for performance testing.

[0258] Table 1 Mechanical property test results of glass fiber reinforced polyglycolic acid composite

[0259]

[0260]

[0261] It should be noted that the processing temperature of the first or second polyglycolic acid resin should be above 230°C, and when the glass fibers and other fillers are added, the processing temperature can be reduced to 210°C, that is, the glass fibers and other fillers can greatly expand the processing temperature window of polyglycolic acid, which may be due to the addition of glass fibers and fillers which can destroy the interaction between molecular chains.

[0262] In addition, after conventional melt processing, the surface layer of pure polyglycolic acid resin cools quickly, affecting heat conduction inside, which in turn causes certain porosity in the interior; while the glass fiber reinforced polyglycolic acid composite provided by the present application has uniform surface layer and core layer without porosity, which can solve the problem of unstable processing size of pure polyglycolic acid resin.

[0263] From the results of Example 1 and Comparative Examples 1 and 2, and Example 6 and Comparative Examples 3 and 4, it can be seen that the glass fiber reinforced polyglycolic acid composite provided by the present application can uniformly disperse glass fibers in the polyglycolic acid resin, greatly improving the mechanical strength of the composite material, and the performance of the composite material is more stable and reliable, which can effectively expand the application range of polyglycolic acid.

[0264] From Example 1 and Examples 6-10, it can be seen that the addition of inorganic fillers in the outer layer material can improve the strength of the composite material, but has an adverse effect on impact resistance. And the reinforcing effect of fibrous inorganic fillers is better than that of sheet-like and particulate inorganic fillers.

[0265] In addition, the polyglycolic acid composite of Example 2 has improved gloss.

[0266] It should be noted that the foregoing examples have been provided merely for the purposes of illustration and are not intended to limit the application in any way. Descriptions and examples of materials and processes of the application are intended to be illustrative not limiting. Any modifications of the application and other applications of the application will occur to those skilled in the art to which the application pertains and many options for modification of the application will suggest themselves. The application lies in the broadest aspects of the art, and there are many alternatives for the application of the application.

Claims

1. A glass fiber-reinforced polyglycolic acid composite, characterized in that, The composite material comprises an inner core material and at least one outer layer material; the inner core material comprises a first polyglycolic acid resin, glass fibers and a first additive, the glass fibers continuously extend from one end of the inner core material to the opposite end; the outer layer material wraps the inner core material, and the outer layer material comprises a second polyglycolic acid resin and a second additive; The amount of the first polyglycolic acid resin is 100 parts by weight, the amount of the glass fibers is 10-200 parts by weight, and the amount of the second polyglycolic acid resin is 50-100 parts by weight.

2. The composite material of claim 1, wherein, The melt flow rate of the first polyglycolic acid resin at 230°C and under a load of 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 under a load of 2.16 kg is 5-500 g / 10 min.

3. The composite material of claim 2, wherein, The melt flow rate of the first polyglycolic acid resin at 230°C and under a load of 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 under a load of 2.16 kg is 10-200 g / 10 min.

4. The composite material of claim 3, wherein, The melt flow rate of the first polyglycolic acid resin at 230°C and under a load of 2.16 kg is 10-150 g / 10 min. And / or, the melt flow rate of the second polyglycolic acid resin at 230°C and under a load of 2.16 kg is 10-150 g / 10 min.

5. The composite material according to any one of claims 1 to 4, characterized in that, The first polyglycolic acid resin and the second polyglycolic acid resin are the same or different, and each is independently selected from the group consisting of homopolymer polyglycolic acid and / or copolymer polyglycolic acid.

6. The composite material of claim 5, wherein, The content of glycolic acid monomer in the copolymer polyglycolic acid is ≥90 mol%.

7. The composite material of claim 6, wherein, The content of glycolic acid monomer in the copolymer polyglycolic acid is ≥95 mol%.

8. The composite material according to any one of claims 1 to 4, wherein The composite material is in the form of a strip, a rod or a particle.

9. The composite material of claim 8, wherein, The length of the strip or rod-shaped composite material is 5-30 mm; and / or the particle size of the particle-shaped composite material is 2-5 mm.

10. The composite material of claim 9, wherein, The length of the strip or rod-shaped composite material is 5-25 mm; and / or the particle size of the particle-shaped composite material is 3-4 mm.

11. The composite material of claim 10, wherein, The length of the strip or rod-shaped composite material is 6-15 mm.

12. The composite material of any one of claims 1-4, wherein, The amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the glass fibers is 10-150 parts by weight.

13. The composite material of claim 12, wherein, The amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the glass fibers is 20-150 parts by weight.

14. The composite material of any one of claims 1-4, wherein, The amount of the first polyglycolic acid resin is 100 parts by weight, and the first additive comprises at least one of 0.05-5 parts by weight of a first compatibilizer, 0.1-3 parts by weight of a first antioxidant and 0.1-1 part by weight of a first lubricant. And / or, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second additive comprises at least one of 0.05-5 parts by weight of a second compatibilizer, 0.1-3 parts by weight of a second antioxidant and 0.1-1 part by weight of a second lubricant.

15. The composite material of claim 14, wherein, The first polyglycolic acid resin is used in an amount of 100 parts by weight, and the first aid includes at least one of 0.05-2 parts by weight of a first compatibilizer, 0.1-1 part by weight of a first antioxidant, and 0.2-1 part by weight of a first lubricant; And / or, the second polyglycolic acid resin is used in an amount of 100 parts by weight, and the second aid includes at least one of 0.05-2 parts by weight of a second compatibilizer, 0.1-1 part by weight of a second antioxidant, and 0.2-1 part by weight of a second lubricant.

16. The composite material of claim 14, wherein, The compatibilizer is selected from at least one of a coupling agent; And / or, the antioxidant is selected from at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 2246, antioxidant CA, and antioxidant 626; And / or, the lubricant is selected from at least one of ethylene bis-stearamide, calcium stearate, monoglyceride fatty acid, polyethylene wax, erucamide, and pentaerythritol stearate.

17. The composite material of claim 16, wherein, The compatibilizer is selected from at least one of a silane coupling agent, a titanate coupling agent, and an organic chromium complex coupling agent; And / or, the antioxidant is selected from antioxidant 1010 and / or antioxidant 168.

18. The composite material of claim 17, wherein, The compatibilizer is selected from a silane coupling agent.

19. The composite material of any one of claims 1-4, wherein, The outer layer material further includes a filler.

20. The composite material of claim 19, wherein, The second polyglycolic acid resin is used in an amount of 100 parts by weight, and the filler is used in an amount of 1-99 parts by weight; And / or, the filler is an organic filler and / or an inorganic filler.

21. The composite material of claim 20, wherein, The second polyglycolic acid resin is used in an amount of 100 parts by weight, and the filler is used in an amount of 5-50 parts by weight; And / or, the filler is selected from at least one of a particulate inorganic filler, a flaky inorganic filler, and a fibrous inorganic filler.

22. The composite material of claim 21, wherein, The second polyglycolic acid resin is used in an amount of 100 parts by weight, and the filler is used in an amount of 10-50 parts by weight; And / or, the filler is selected from a fibrous inorganic filler; And / or, the particulate inorganic filler has a particle size of 0.05-100 μm; And / or, the flaky inorganic filler has a particle size of 0.05-100 μm; And / or, the fibrous inorganic filler has a diameter of 0.05-20 μm and an aspect ratio of 10-1000.

23. The composite material of claim 22, wherein, The filler is selected from sepiolite fibers and / or glass fibers; And / or, the particulate inorganic filler has a particle size of 0.1-50 μm; And / or, the flaky inorganic filler has a particle size of 0.1-50 μm.

24. The composite material of claim 23, wherein, The filler is selected from sepiolite fibers and / or glass fibers; And / or, the particulate inorganic filler has a particle size of 0.1-10 μm; And / or, the flaky inorganic filler has a particle size of 0.1-10 μm.

25. The composite material of any one of claims 1-4, wherein, The inner core material does not contain non-oriented short fibers.

26. The composite material of claim 25, wherein, The inner core material is composed of a first polyglycolic acid resin, glass fibers, and a first aid.

27. A method of making a glass fiber-reinforced polyglycolic acid composite according to any one of claims 1-26, wherein, Comprising: S1. Melting the first polyglycolic acid resin and the first aid after mixing to obtain a first component melt; S2. Performing a first impregnation treatment on the continuous glass fibers with the first component melt in step S1 to form a filamentous inner core material; S3. Melting the second polyglycolic acid and the second aid after mixing to obtain a second component melt; S4. The inner core material obtained in step S2 is subjected to at least one second impregnation treatment with the melt of at least one second component in step S3 to obtain the glass fiber reinforced polyglycolic acid composite material.

28. The method of claim 27, wherein, The mixing condition of step S1 is that the temperature is 40-60℃ and the time is 3-5 min; and / or the melting temperature of step S1 is 230-260℃; and / or, the mixing condition of step S3 is that the temperature is 40-60℃ and the time is 3-5 min; and / or the melting temperature of step S3 is 230-260℃; and / or, step S2 further comprises: dispersing and preheating the continuous glass fiber before the first impregnation treatment. and / or, step S4 further comprises: after the second impregnation treatment, pulling out, stretching, cooling, drying and granulating the material obtained after the second impregnation treatment to obtain the glass fiber reinforced polyglycolic acid composite material.

29. The method of claim 28, wherein, The preheating temperature is 80-250℃.

30. The method of any one of claims 27-29, wherein, The first impregnation treatment in step S2 is carried out in a first impregnation mold, the first impregnation mold is an adjustable impregnation mold, the first impregnation mold comprises a fiber inlet, a fiber outlet and a melt flow channel, at least one first godet is arranged in the mold cavity of the first impregnation mold; the first godet can move between the fiber inlet and the fiber outlet; and / or the first godet can move in a direction perpendicular to the line connecting the fiber inlet and the fiber outlet.

31. The method of any one of claims 27-29, wherein, The first impregnation treatment in step S2 is carried out in a second impregnation mold, the second impregnation mold is a combined impregnation mold, the second impregnation mold comprises a first module, an intermediate module and a second module connected in sequence, the first module is provided with a fiber inlet and a first module flow channel, the second module is provided with a fiber outlet and a second module flow channel, and the intermediate module is provided with an intermediate module flow channel; after the first module, the intermediate module and the second module are connected in sequence, the first module flow channel, the intermediate module flow channel and the second module flow channel are communicated to form a combined flow channel for the fiber to pass through.

32. The method of any one of claims 27-29, wherein, The first impregnation treatment in step S2 is carried out in a third impregnation mold, the third impregnation mold is a strong turbulence impregnation mold, the third impregnation mold comprises a fiber inlet channel, an impregnation outlet and a melt slit flow channel, all of which are communicated with the mold cavity inside the third impregnation mold; wherein the second godet is arranged in the mold cavity of the third impregnation mold, the second godet comprises at least one driving godet, and the driving godet is driven to rotate by a driving device.

33. The use of the composite material of any one of claims 1-26 or the composite material prepared by the method of any one of claims 27-32 in the fields of catering, building decoration, oil field chemical industry and engineering plastics.

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