Weatherable glass fiber reinforced polyglycolic acid composites, methods of making and use thereof

Abstract

The application relates to the technical field of high polymer composite materials, and provides a weather-resistant glass fiber reinforced polyglycolic acid composite material as well as a preparation method and application thereof. The weather-resistant glass fiber reinforced polyglycolic acid composite material comprises a core material and at least one layer of outer material; the core material comprises a first polyglycolic acid resin, glass fibers and a first additive, the glass fibers continuously extend from one end of the core material to the opposite end; the outer material wraps the core material, the outer material comprises a second polyglycolic acid resin and a second additive, and the second additive comprises a weather-resistant master batch. The weather-resistant glass fiber reinforced polyglycolic acid composite material is designed based on a multi-module system, can uniformly disperse high content glass fibers in polyglycolic acid, greatly improves the performance of the composite material, improves the weather resistance of the composite material by adding the weather-resistant master batch, and provides a natural degradable polyglycolic acid composite material with good mechanical properties and weather resistance.

Description

TECHNICAL FIELD

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

[0002] Polyglycolic acid (PGA) is a biodegradable material with excellent mechanical properties, heat resistance and gas barrier properties. After using for a certain period of time, PGA gradually degrades into water and carbon dioxide, which is harmless to human beings, animals and plants, and the natural environment. PGA has good application prospects in the fields of oil exploitation, industrial production, biodegradable packaging materials, disposable utensils and medical health. However, PGA has low impact strength and poor weather resistance, and it is difficult to directly apply pure PGA in occasions with high requirements for weather resistance and impact strength. It is often necessary to blend and modify PGA to improve its weather resistance and impact strength. The weather resistance functionalization of PGA has not been disclosed in the prior art.

[0003] If applied in occasions with high requirements for weather resistance and impact strength, the existing PGA material is difficult to meet the use requirements. Therefore, it is of great significance to develop a new type of weather-resistant glass fiber reinforced polyglycolic acid composite material. SUMMARY

[0004] To solve the above technical problems, the present application provides a weather-resistant glass fiber reinforced polyglycolic acid composite material, a preparation method and application thereof.

[0005] The technical scheme adopted by the present application is as follows:

[0006] In a first aspect, the present application provides a weather-resistant glass fiber reinforced polyglycolic acid composite material, which comprises an inner core material and at least one outer layer material; the inner core material comprises a first polyglycolic acid resin, glass 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 second additive comprises a weather-resistant master batch.

[0007] As a preferred scheme of the composite material provided by the present application, in the composite material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the glass fibers is 10-200 parts by weight, preferably 10-150 parts by weight, and more preferably 20-150 parts by weight;

[0008] And / or, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the second polyglycolic acid resin is 1-100 parts by weight, preferably 10-100 parts by weight, and more preferably 50-100 parts by weight;

[0009] And / or, the second polyglycolic acid resin is used in an amount of 2-50 parts by weight, preferably 5-30 parts by weight, based on 100 parts by weight of the first polyglycolic acid resin.

[0010] As another preferred embodiment of the composite material provided by the present application, the weather-resistant master batch is a bio-based elastomer-loaded composite weather-resistant master batch, which comprises an antioxidant, an ultraviolet absorber, a light stabilizer, an anti-migration agent, a bio-based elastomer and a dispersing agent.

[0011] Preferably, the bio-based elastomer is used in an amount of 0.01-1 parts by weight, the antioxidant is used in an amount of 0.1-2 parts by weight, the ultraviolet absorber is used in an amount of 0.1-2 parts by weight, the light stabilizer is used in an amount of 0.1-2 parts by weight, the anti-migration agent is used in an amount of 0.01-10 parts by weight, and the dispersing agent is used in an amount of 0.1-10 parts by weight, based on 100 parts by weight of the weather-resistant master batch.

[0012] More preferably, the bio-based elastomer is used in an amount of 0.01-1 parts by weight, the antioxidant is used in an amount of 0.1-2 parts by weight, the ultraviolet absorber is used in an amount of 0.1-2 parts by weight, the light stabilizer is used in an amount of 0.1-2 parts by weight, the anti-migration agent is used in an amount of 0.01-10 parts by weight, and the dispersing agent is used in an amount of 0.5-5 parts by weight, based on 100 parts by weight of the weather-resistant master batch.

[0013] As another preferred embodiment of the composite material provided by the present application,

[0014] the antioxidant is selected from at least one of 2,6-di-tert-butyl-4-methylphenol (antioxidant BHT), tert-butylhydroquinone (antioxidant TBHQ), 1,1,3-tris(2-methyl-4-hydroxy-5-tert- butylphenyl)butane (antioxidant CA), pentaerythrityl tetra[β-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate] (antioxidant 1010), 2,2'-methylenebis(4-methyl-6-tert- butylphenol) (antioxidant 2246), 4,4'-thiobis-[3-methyl-6-tert-butylphenol] (antioxidant 300), 2,2'-thiobis-[4-methyl-6-tert-butylphenol] (antioxidant 2246-S), 1,3,5-di[β-(3,5-di-tert- butyl-4-hydroxyphenyl)propionyl]-hexahydroxy-triazine (antioxidant 3114), N,N'-di(β- naphthyl)para-phenylenediamine (antioxidant DNP), N,N'-diphenylpara-phenylenediamine (antioxidant PPD), N-phenyl-N'-cyclohexylpara-phenylenediamine (antioxidant 4010), dilaurylthiodipropionate (antioxidant DLTP), 2-mercaptobenzimidazole (antioxidant MB), 2- mercaptobenzothiazole (antioxidant MBT), triphenylphosphite, tris(nonylphenyl)phosphite, tris[2,4-di-tert-butylphenyl]phosphite (antioxidant 168), tri(ethylene glycol) bis[β-(3-tert- butyl-4-hydroxy-5-methylphenyl)propionate] (antioxidant 245), antioxidant Chinox 20N; preferably, the antioxidant is selected from at least one of 2,6-di-tert-butyl-4-methylphenol (antioxidant BHT), tert-butylhydroquinone (antioxidant TBHQ), tris[2.4-di-tert- butylphenyl]phosphite, pentaerythrityl tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tri(ethylene glycol) bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (antioxidant 245), antioxidant Chinox 20N;

[0015] and / or the antioxidant is a mixture of a hindered phenolic antioxidant and a phosphite antioxidant in a mass ratio of 1 :2 to 2:1, preferably 1 :1 ; preferably the hindered phenolic antioxidant is pentaerythrityl tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010) and / or tri(ethylene glycol) bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (antioxidant 245); and the phosphite antioxidant is tris[2.4-di-tert-butylphenyl]phosphite (antioxidant 168);

[0016] and / or the ultraviolet absorber is selected from at least one of 2-(2-hydroxy-3,5-di-tert- butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2'- hydroxy-3',5'-di-pentylphenyl)benzotriazole (UV-320), 2-(2'-hydroxy-3',5'-di-tert- amylphenyl)benzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone (UV-531), phenyl salicylate, m- resorcinol monobenzoate, o-nitrosoaniline, p-cresol, 2,4,6-tris(2-hydroxy-4-n- butyoxyphenyl)-1,3,5-triazine, 2-cyano-3,3-diphenyl acrylate, p-tert-butylphenyl salicylate, bisphenyl A bisalicylate, bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonate) monoethyl ester, 2,2'-thiobis(4-t-octylphenyloxy)nickel; preferably the ultraviolet absorber is selected from at least one of 2-(2'-hydroxy-3',5'-di-pentylphenyl)benzotriazole (UV-320), 2-hydroxy-4-n-octyloxybenzophenone (UV-531), 2,4,6-tris(2-hydroxy-4-n- butyoxyphenyl)-1,3,5-triazine;

[0017] and / or the light stabilizer is selected from at least one of poly(butylene succinate) (4-hydroxy-2,2,6,6-tetramethyl-1 -piperidinylethyl) ester (Chimassorb® 622), bis(1 - octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Chimassorb® HS-112), bis(1,2,2,6,6- pentamethylpiperidinol) sebacate, 1 -(methyl)-8-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]- 1,3,5-triazine-2,4-[(2,2,6,6,-tetramethyl-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl- 4-piperidinyl)imino]}; preferably the light stabilizer is selected from poly(butylene succinate) (4-hydroxy-2,2,6,6-tetramethyl-1 -piperidinylethyl) ester (Chimassorb® 622) and / or bis(1 - octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Chimassorb® HS-112);

[0018] and / or the anti-migrating agent is selected from at least one of blocked polyisocyanates; preferably phenol blocked polyisocyanates, caprolactam blocked polyisocyanates, butanone oxime blocked polyisocyanates;

[0019] and / or, the bio-based elastomer is selected from at least one of poly(sebacic acid-glycerol) ester elastomer, acrylated poly(sebacic acid-glycerol) ester elastomer, poly(limonene acid-1,8-octanediol) ester elastomer, copolymer of lactide-caprolactone, glycolide-lactide copolymer, glycolide-lactide-caprolactone terpolymer, poly(ester-carbonate) elastomer, poly(limonene acid-octanediol-sebacic acid) ester elastomer, poly(sebacic acid-glycerol-limonene acid) ester elastomer, poly(sebacic acid-1,2-propanediol-limonene acid) ester elastomer, poly(itaconate-isoprene-glycidyl methacrylate) elastomer, soybean oil-based elastomer, itaconate elastomer containing a trioxirane structure, myrcene bio-based elastomer;

[0020] and / or, the dispersant is selected from at least one of nano-sized inorganic powder, preferably nano-sized calcium carbonate, silicon dioxide, montmorillonite, zinc oxide, talc powder, titanium dioxide, carbon nanotube, graphene, carbon fiber, boron nitride, zirconium dioxide, wollastonite and zeolite; preferably nano-sized calcium carbonate and / or nano-sized fumed silica.

[0021] As another preferred scheme of the composite material provided by the present application, the preparation method of the bio-based elastomer loaded composite weather-resistant masterbatch comprises:

[0022] S1. dispersing the antioxidant, ultraviolet absorber, light stabilizer, anti-migration agent and dispersant by using an air flow crusher to obtain a powder;

[0023] S2. mixing the powder obtained in step S1 with the bio-based elastomer by using a banbury mixer;

[0024] S3. crushing the banbury product obtained in step S2 by using a freezer crusher and an air flow crusher to obtain a bio-based elastomer loaded composite weather-resistant masterbatch.

[0025] 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 are independently selected from homopolymer type polyglycolic acid and / or copolymer type polyglycolic acid; preferably, the content of glycolic acid monomer in the copolymer type polyglycolic acid is ≥ 90 mol%, preferably ≥ 95 mol%;

[0026] and / or, the melt flow rate of the first polyglycolic acid resin at 230°C under a load of 2.16 kg is 5-500 g / 10 min, preferably 10-200 g / 10 min, and more preferably 10-150 g / 10 min;

[0027] and / or, the melt flow rate of the second polyglycolic acid resin at 230℃, 2.16kg is 5-500g / 10min, preferably 10-200g / 10min, more preferably 10-150g / 10min.

[0028] As another preferred embodiment of the composite material provided by the present application, the first polyglycolic acid resin is used in an amount of 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 parts by weight of a first lubricant; preferably, the first polyglycolic acid resin is used in an amount of 100 parts by weight, and the first additive comprises at least one of 0.05-2 parts by weight of a first compatibilizer, 0.1-1 parts by weight of a first antioxidant, and 0.2-1 parts by weight of a first lubricant.

[0029] and / or, the second polyglycolic acid resin is used in an amount of 100 parts by weight, and the second additive further comprises at least one of 0.05-5 parts by weight of a second compatibilizer, 0.1-3 parts by weight of a second antioxidant, and 0.1-1 parts by weight of a second lubricant; preferably, the second polyglycolic acid resin is used in an amount of 100 parts by weight, and the second additive further comprises at least one of 0.05-2 parts by weight of a second compatibilizer, 0.1-1 parts by weight of a second antioxidant, and 0.2-1 parts by weight of a second lubricant.

[0030] As a preferred embodiment of the composite material provided by the present application, the first compatibilizer and the second compatibilizer are the same or different, and each is independently selected from at least one of coupling agents, preferably at least one of silane coupling agents, titanate coupling agents, and organic chromium complex coupling agents, more preferably at least one of silane coupling agents.

[0031] and / or, the first antioxidant and the second antioxidant are the same or different, each independently selected from at least one of 2,6-di-tert-butyl-4-methylphenol (antioxidant BHT), tert-butylhydroquinone (antioxidant TBHQ), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (antioxidant CA), pentaerythrityl tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (antioxidant 2246), 4,4'-thiobis-[3-methyl-6-tert-butylphenol] (antioxidant 300), 2,2'-thiobis-[4-methyl-6-tert-butylphenol] (antioxidant 2246-S), 1,3,5-di[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]-hexahydro-1,3,5-triazine (antioxidant 3114), N,N'-di(β-naphthyl)-p-phenylenediamine (antioxidant DNP), N,N'-diphenyl-p-phenylenediamine (antioxidant PPD), N-phenyl-N'-cyclohexyl-p-phenylenediamine (antioxidant 4010), dilauryl thiodipropionate (antioxidant DLTP), 2-mercaptobenzimidazole (antioxidant MB), 2-mercaptobenzothiazole (antioxidant MBT), triphenyl phosphite, tris(nonylphenyl)phosphite, tris[2,4-di-tert-butylphenyl]phosphite (antioxidant 168), tri(ethylene glycol) bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (antioxidant 245), antioxidant Chinox 20N; preferably at least one of 2,6-di-tert-butyl-4-methylphenol (antioxidant BHT), tert-butylhydroquinone (antioxidant TBHQ), tris[2.4-di-tert-butylphenyl]phosphite, pentaerythrityl tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tri(ethylene glycol) bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (antioxidant 245), antioxidant Chinox 20N;

[0032] and / or, the first lubricant and the second lubricant are the same or different, each independently selected from at least one of ethylene bis-stearamide, calcium stearate, monoglyceride fatty acid, polyethylene wax, erucamide, pentaerythritol stearate, preferably erucamide.

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

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

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

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

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

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

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

[0040] As another preferred embodiment of the preparation method provided by the present application, the mixing condition in step S3 is that the temperature is 40-60℃ and the time is 3-5min; and / or the melting temperature in step S3 is 230-260℃.

[0041] As another preferred embodiment of the preparation method provided by the present application, step S2 further comprises: performing a dispersion treatment and a preheating treatment on the continuous glass fiber before performing the first impregnation treatment on the continuous glass fiber; preferably, the preheating treatment is performed at a temperature of 80-250℃.

[0042] As another preferred embodiment of the preparation method provided by the present application, step S4 further comprises: after the second impregnation treatment, performing a pulling-out, a stretching, a cooling, a drying and a cutting treatment on the material obtained after the second impregnation treatment to obtain the weather-resistant glass fiber reinforced polyglycolic acid composite material.

[0043] 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, at least one first godet is arranged in the mold cavity of the first impregnation mold; the first godet can move between the fiber inlet and the fiber outlet; and / or the first godet can move in a direction perpendicular to the connecting line of the fiber inlet and the fiber outlet.

[0044] As another preferred scheme of the preparation method provided by the present application, the first impregnation treatment in step S2 is 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 in communication to form a combined flow channel for the fiber to pass through.

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

[0046] In a third aspect, the present application provides an application of the composite material or the composite material prepared by the preparation method in the field of building decoration and engineering plastics.

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

[0048] (1) The weather-resistant glass fiber reinforced polyglycolic acid composite material has an inner-outer layer composite structure. The continuous / constant-length glass fibers in the inner core material are treated by impregnation, which improves the flowability of the glass fibers in the matrix melt, makes the high-content glass fibers uniformly dispersed in the polyglycolic acid resin, and significantly improves the mechanical properties of the polyglycolic acid resin. The coating of the outer layer material can further enhance the comprehensive performance and surface quality of the inner core material, expand the application field of the polyglycolic acid composite material, and has excellent application value.

[0049] (2) The weather-resistant efficiency of the bio-based elastomer loaded composite weather-resistant master batch added in the outer layer material is high, and the toughness and impact resistance of the composite material are also improved. In addition, the bio-based elastomer loaded composite weather-resistant master batch effectively solves the problem of precipitation and failure of the weather-resistant agent in the composite material during use by compounding an anti-migration agent.

[0050] (3) The weather-resistant glass fiber reinforced polyglycolic acid composite material of the present application also has the advantages of low cost, simple preparation process, good dimensional stability and good surface quality. BRIEF DESCRIPTION OF DRAWINGS

[0051] Figure 1 A schematic diagram of a weather-resistant glass fiber reinforced polyglycolic acid composite material structure in an embodiment of the present application;

[0052] Figure 2 A schematic diagram of a weather-resistant glass fiber reinforced polyglycolic acid composite material manufacturing system structure in an embodiment of the present application;

[0053] Figure 3 A schematic diagram of a weather-resistant glass fiber reinforced polyglycolic acid composite material manufacturing system structure in another embodiment of the present application;

[0054] Figure 4 A cross-sectional view of a first impregnation die in an embodiment of the present application;

[0055] Figure 5 A cross-sectional view of a second impregnation die in an embodiment of the present application;

[0056] Figure 6 A cross-sectional view of a third impregnation die in an embodiment of the present application;

[0057] Figure 7 A schematic diagram of a second impregnation process in an embodiment of the present application;

[0058] Figure 8 A cross-sectional view of a forming die used in a second impregnation process in an embodiment of the present application.

[0059] Explanation of reference numerals:

[0060] 0-1, core material; 0-2, fiber bundle; 0-3, outer layer material;

[0061] 1, fiber stand and fiber guide device; 2, fiber pretreatment device; 3, first impregnation die; 4, molten plasticizing feeder; 5, forming die; 6, cooling water tank; 7, drying machine; 8, puller; 9, pelletizer; 10, collection box;

[0062] A300, first impregnation die die head; A1, fiber inlet; A2, second chute; A3, melt runner; A4, first chute; A5, upper die cover; A6, fiber outlet; A7, impregnation die body; A8, first godet;

[0063] B300, second impregnation die die head; B1, fiber inlet; B2, melt runner; B3, first module; B31, first module runner; B4, combined runner; B5, standardization joint; B6, intermediate module; B61, intermediate module runner; B7, second module; B71, second module runner; B8, fiber outlet;

[0064] C300, third impregnation die head; C1, melt split channel; C2, impregnation die outer body; C3, fiber inlet channel; C4, driving godet; C5, driven godet; C6, impregnation outlet;

[0065] 4-1, extruder I; 4-2, extruder II;

[0066] 5-1, core; 5-2, sheath; 5-3, sheath die plate; 5-4, strand; 5-5, second resin inlet. DETAILED DESCRIPTION

[0067] In order to make the technical problems, technical solutions and beneficial effects of the present application more clear, the present application will be further described in detail below in combination with specific embodiments. It should be understood that the specific embodiments described herein are only used to specifically illustrate the present patent and do not limit the protection scope of the present application in any way.

[0068] The weather-resistant 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, the second additive comprises a weather-resistant master batch.

[0069] In the present application, a first component comprising a first polyglycolic acid resin and a first additive is impregnated into continuous glass fibers to form an inner core material, and a second component comprising a second polyglycolic acid resin and a second additive is uniformly coated outside the inner core material, thereby forming a weather-resistant glass fiber reinforced polyglycolic acid composite material with the continuous glass fiber reinforced resin as the inner core material and the resin layer wrapped outside the inner core material as the outer layer material. Such a polyglycolic acid composite material has excellent mechanical properties. To further solve the problem of poor weather resistance of polyglycolic acid resin, a weather-resistant master batch is added to the second additive of the outer layer material.

[0070] In the present application, the terms "one end" and "opposite end" are generally relative to the longitudinal direction of the weather-resistant glass fiber reinforced polyglycolic acid composite material.

[0071] In the transverse cross-section of the weather-resistant 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 weather-resistant glass fiber reinforced polyglycolic acid composite material in the inner core material.

[0072] The glass fibers in the present application are glass fiber bundles, the length of the fiber bundles is substantially the same as the length (longitudinal dimension) of the weatherable glass fiber reinforced polyglycolic acid composite material, thus, the fiber bundles continuously extend from one end to the opposite end of the longitudinal direction of the inner core material. The inner core material does not contain short fibers, in particular, does not contain non-oriented short fibers.

[0073] In the weatherable glass fiber reinforced polyglycolic acid composite material of the present application, the outer layer material at least 80% covers the inner core material, for example, 80-99%, 85-95% covers the inner core material; the outer layer material can also continuously cover the inner core material.

[0074] The outer layer material is not limited in the number of layers, and can be one layer or multiple layers. In some embodiments, the multiple layers of the outer layer material can be formed of the same material or multiple materials.

[0075] The glass fibers are continuous and / or fixed-length glass fibers.

[0076] According to some embodiments of the present application, in the composite material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the glass fibers is 10-200 parts by weight, for example, can be 10, 20, 50, 60, 100, 150, 200 parts by weight, etc. Preferably, 10-150 parts by weight, more preferably, 20-150 parts by weight.

[0077] According to some embodiments of the present application, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the second polyglycolic acid resin is 1-100 parts by weight, for example, can be 1, 10, 20, 50, 60, 80, 100 parts by weight, etc., preferably 10-100 parts by weight, more preferably 50-100 parts by weight.

[0078] 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 weatherable masterbatch is 2-50 parts by weight, for example, can be 2, 5, 10, 15, 20, 25, 30, 50 parts by weight, etc., preferably 5-30 parts by weight.

[0079] According to some embodiments of the present application, the weatherable masterbatch is a bio-based elastomer-loaded composite weatherable masterbatch, which comprises an antioxidant, an ultraviolet absorber, a light stabilizer, an anti-migration agent, a bio-based elastomer, and a dispersing agent.

[0080] Preferably, the amount of the bio-based elastomer is 100 parts by weight, the content of the antioxidant is 0.01-1 parts by weight, the content of the ultraviolet absorber is 0.1-2 parts by weight, the content of the light stabilizer is 0.1-2 parts by weight, the content of the anti-migration agent is 0.01-10 parts by weight, and the content of the dispersing agent is 0.1-10 parts by weight.

[0081] For example, the content of the antioxidant can be 0.01 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, etc., based on 100 parts by weight of the bio-based elastomer; and / or the content of the ultraviolet absorber can be 0.1 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, 1.3 parts by weight, 1.5 parts by weight, 2 parts by weight, etc.; and / or the content of the light stabilizer can be 0.1 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, 1.3 parts by weight, 1.5 parts by weight, 2 parts by weight, etc.; and / or the content of the anti-migrating agent can be 0.01 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, 3 parts by weight, 5 parts by weight, 10 parts by weight, etc.; and / or the content of the dispersing agent can be 0.1 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, 3 parts by weight, 5 parts by weight, 10 parts by weight, etc.

[0082] More preferably, the content of the antioxidant is 0.01-1 parts by weight, the content of the ultraviolet absorber is 0.1-2 parts by weight, the content of the light stabilizer is 0.1-2 parts by weight, the content of the anti-migrating agent is 0.01-10 parts by weight, and the content of the dispersing agent is 0.5-5 parts by weight, based on 100 parts by weight of the bio-based elastomer.

[0083] In the present application, the bio-based elastomer-loaded composite weather-resistant master batch is a supported blend of weather-resistant components such as antioxidants, ultraviolet absorbers, and light stabilizers with bio-based elastomer particles. Controlling the content of the bio-based elastomer in the bio-based elastomer-loaded composite weather-resistant master batch can help reduce the moisture absorption of the weather-resistant master batch during storage, while improving the impact resistance of the composite material and increasing its operability and service life during actual application.

[0084] According to some embodiments of the application, the antioxidant is selected from at least one of 2,6-di-tert-butyl-4-methylphenol (antioxidant BHT), tert-butylhydroquinone (antioxidant TBHQ), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (antioxidant CA), pentaerythrityl tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (antioxidant 2246), 4,4'-thiobis-[3-methyl-6-tert-butylphenol] (antioxidant 300), 2,2'-thiobis-[4-methyl-6-tert-butylphenol] (antioxidant 2246-S), 1,3,5-di[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]- hexahydrotriazine (antioxidant 3114), N,N'-di(β-naphthyl)-p-phenylenediamine (antioxidant DNP), N,N'-diphenyl-p-phenylenediamine (antioxidant PPD), N-phenyl-N'- cyclohexyl-p-phenylenediamine (antioxidant 4010), dilauryl thiodipropionate (antioxidant DLTP), 2-mercaptobenzimidazole (antioxidant MB), 2- mercaptobenzothiazole (antioxidant MBT), triphenyl phosphite, tris(nonylphenyl) phosphite, tris[2,4-di-tert-butylphenyl] phosphite (antioxidant 168), tri(ethylene glycol) bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (antioxidant 245), antioxidant Chinox 20N.

[0085] Preferably, the antioxidant is selected from at least one of 2,6-di-tert-butyl-4-methylphenol (antioxidant BHT), tert-butylhydroquinone (antioxidant TBHQ), tris[2.4-di-tert-butylphenyl] phosphite, pentaerythrityl tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tri(ethylene glycol) bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (antioxidant 245), antioxidant Chinox 20N.

[0086] According to some preferred embodiments of the application, the antioxidant is a mixture of a hindered phenolic antioxidant and a phosphite antioxidant in a mass ratio of 1 :2 to 2:1, preferably 1 :1.

[0087] Preferably, the hindered phenolic antioxidant is pentaerythrityl tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010) and / or tri(ethylene glycol) bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (antioxidant 245); and / or, the phosphite antioxidant is tris[2.4-di-tert-butylphenyl] phosphite (antioxidant 168).

[0088] According to some embodiments of the present application, the ultraviolet absorber is selected from at least one of 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-pentylphenyl)benzotriazole (UV-320), 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone (UV-531), phenyl salicylate, m- resorcinol monobenzoate, o-nitroaniline, p-cresol, 2,4,6-tris(2-hydroxy-4-n-butyloxyphenyl)- 1,3,5-triazine, 2-cyano-3,3-diphenylacrylic acid 2-ethylhexyl ester, p-tert-butylphenyl salicylate, bisphenol A bis-salicylate, bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonate monoethyl ester), 2,2'-thiobis(4-t-octylphenyloxy)nickel.

[0089] Preferably, the ultraviolet absorber is selected from at least one of 2-(2'-hydroxy-3',5'-di-pentylphenyl)benzotriazole (UV-320), 2-hydroxy-4-n-octyloxybenzophenone (UV-531), 2,4,6-tris(2-hydroxy-4-n-butyloxyphenyl)-1,3,5-triazine.

[0090] According to some embodiments of the present application, the light stabilizer is selected from at least one of poly(succinato-4-hydroxy-2,2,6,6-tetramethyl-1-piperidinemethanol) (Chimassorb® 622), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Chimassorb® HS-112), bis(1,2,2,6,6-pentamethylpiperidinol) sebacate, 1-(methyl)-8-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2,4-[(2,2,6,6,-tetramethyl-piperidyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidyl)imino]}.

[0091] Preferably, the light stabilizer is selected from poly(succinato-4-hydroxy-2,2,6,6-tetramethyl-1-piperidinemethanol) (Chimassorb® 622) and / or bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Chimassorb® HS-112).

[0092] According to some embodiments of the present application, the anti-migration agent is selected from at least one of blocked polyisocyanates; preferably phenol blocked polyisocyanates, caprolactam blocked polyisocyanates, butanone oxime blocked polyisocyanates.

[0093] According to some embodiments of the present application, the bio-based elastomer is selected from at least one of poly(glycol sebacate) (PGS) elastomer, acrylated PGS elastomer, poly(1,8-octanediol citrate) (POC) elastomer, copolymer of lactide-caprolactone, glycolide-lactide copolymer, glycolide-lactide-caprolactone terpolymer, poly(ester-carbonate) elastomer, poly(l,8-octanediol sebacate) (POSC) elastomer, poly(glycol sebacate citrate) (PGSC) elastomer, poly(1,2-propanediol sebacate citrate) (PPSC) elastomer, poly(itaconate-isoprene-glycidyl methacrylate) elastomer, soy oil-based elastomer (ring-opening polymerization of epoxidized soybean oil with a primary diamine), itaconate elastomer containing a tri-epoxy structure, myrcene bio-based elastomer.

[0094] According to some embodiments of the present application, the dispersant is selected from at least one of nano-sized inorganic powder, preferably nano-sized calcium carbonate, silica, montmorillonite, zinc oxide, talc, titanium dioxide, carbon nanotube, graphene, carbon fiber, boron nitride, zirconium dioxide, wollastonite and zeolite; preferably nano-sized calcium carbonate and / or nano-sized fumed silica.

[0095] According to some embodiments of the present application, the preparation method of the bio-based elastomer loaded composite weatherable masterbatch comprises:

[0096] S1. dispersing the antioxidant, ultraviolet absorber, light stabilizer, anti-migration agent and dispersant by using an airflow crusher to obtain a powder;

[0097] S2. mixing the powder obtained in step S1 with the bio-based elastomer by using a banbury mixer;

[0098] S3. crushing the banbury product obtained in step S2 by using a freezer crusher and an airflow crusher to obtain the bio-based elastomer loaded composite weatherable masterbatch.

[0099] 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 are independently selected from homopolymer type polyglycolic acid and / or copolymer type polyglycolic acid.

[0100] Preferably, the content of glycolic acid monomer in the copolymer type polyglycolic acid is ≥ 90 mol%, preferably ≥ 95 mol%.

[0101] The comonomer of the copolymerized polyglycolic acid can include: cyclic monomers such as 1,4-dioxane-2,3-dione, lactide, lactone (for example, pivalolactone, butyrolactone, pivalolactone, butyrolactone, 8-valerolactone, ethyl 8-valerolactone, E-caprolactone), carbonate (for example, trimethylene carbonate), ether (for example, 1,3-dioxane), ether ester (for example, dioxanone), amide (for example, E-caprolactam), lactic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, and 6-hydroxyhexanoic acid, and alkyl esters of hydroxycarboxylic acids; substantially equimolar mixtures of aliphatic diols (for example, ethylene glycol and 1,4-butanediol) and aliphatic dicarboxylic acids (for example, succinic acid and adipic acid) or alkyl esters thereof; and combinations of two or more of the above.

[0102] The synthesis method of the polyglycolic acid can be selected from glycolic acid liquid phase polycondensation, glycolic acid solid phase polycondensation, glycolic acid melt polycondensation, or glycolide ring-opening polymerization; preferably, glycolide ring-opening polymerization. The raw material of the glycolide can be obtained by a coal chemical method.

[0103] In different embodiments of the present application, the melt flow rate of the first polyglycolic acid resin and the second polyglycolic acid resin is not particularly limited, and the melt flow rate of the first polyglycolic acid resin and the second polyglycolic acid resin can be selected according to the desired performance.

[0104] In particular, the present inventors have found that the polyglycolic acid composite material with high surface quality performance and comprehensive performance can be prepared according to the parameters (for example, melt flow rate) of the present application. For example, the melt flow rate of the first polyglycolic acid resin is higher than that of the second polyglycolic acid resin, so that the polyglycolic acid composite material has improved mechanical properties; on the contrary, the melt flow rate of the second polyglycolic acid resin is higher than that of the first polyglycolic acid resin, so that the polyglycolic acid composite material has improved gloss.

[0105] According to some embodiments of the present application, the melt flow rate of the first polyglycolic acid resin at 230°C under the condition of 2.16 kg is 5-500 g / 10 min, for example, it can be 5, 10, 11, 30, 40, 80, 96, 100, 150, 200, 300, 330, 400, 500 g / 10 min, etc., preferably 10-200 g / 10 min, more preferably 10-150 g / 10 min.

[0106] 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, 5, 10, 11, 30, 40, 80, 96, 100, 150, 200, 300, 330, 400, 500 g / 10 min, etc., preferably 10-200 g / 10 min, more preferably 10-150 g / 10 min.

[0107] According to some embodiments of the present application, the first polyglycolic acid resin is used in an amount of 100 parts by weight, and the first auxiliary agent includes at least one of 0.05-5 parts by weight of a first compatibilizer, 0.1-3 parts by weight of a first antioxidant, and 0.1-1 part by weight of a first lubricant.

[0108] For example, the first compatibilizer can be used in an amount of 0.05 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 1 parts by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, etc.; and / or the first antioxidant can be used in an amount of 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 1 parts by weight, 2 parts by weight, 3 parts by weight, etc.; and / or the first lubricant can be used in an amount of 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, etc.

[0109] Preferably, the first polyglycolic acid resin is used in an amount of 100 parts by weight, and the first auxiliary agent includes at least one of 0.05-2 parts by weight of a first compatibilizer, 0.1-1 parts by weight of a first antioxidant, and 0.2-1 part by weight of a first lubricant.

[0110] According to some embodiments of the present application, the second polyglycolic acid resin is used in an amount of 100 parts by weight, and the second auxiliary agent further includes at least one of 0.05-5 parts by weight of a second compatibilizer, 0.1-3 parts by weight of a second antioxidant, and 0.1-1 part by weight of a second lubricant.

[0111] 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.

[0112] Preferably, the second polyglycolic acid resin is used in an amount of 0.05 to 2 parts by weight, based on 100 parts by weight of the second compatibilizer, the second antioxidant, and the second lubricant, wherein the second compatibilizer includes at least one of 0.05 to 2 parts by weight of a second compatibilizer, 0.1 to 1 parts by weight of a second antioxidant, and 0.2 to 1 parts by weight of a second lubricant.

[0113] According to some embodiments of the present application, the first compatibilizer and the second compatibilizer are the same or different, and each is independently selected from at least one of a coupling agent, preferably at least one of a silane coupling agent, a titanate coupling agent, an organic chromium complex coupling agent, and more preferably a silane coupling agent. Examples of the silane coupling agent suitable for use in the present application include, but are not limited to, KH-550, KH-560.

[0114] According to some embodiments of the present application, the first antioxidant and the second antioxidant are the same or different, and each is independently selected from at least one of 2,6-di-tert-butyl-4-methylphenol (antioxidant BHT), tert-butylhydroquinone (antioxidant TBHQ), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (antioxidant CA), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (antioxidant 2246), 4,4'-thiobis-[3-methyl-6-tert-butylphenol] (antioxidant 300), 2,2'-thiobis-[4-methyl-6-tert-butylphenol] (antioxidant 2246-S), 1,3,5-di[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]-hexahydroisotriazine (antioxidant 3114), N,N'-di(β-naphthyl)-p-phenylenediamine (antioxidant DNP), N,N'-diphenyl-p-phenylenediamine (antioxidant PPD), N-phenyl-N'-cyclohexyl-p-phenylenediamine (antioxidant 4010), dilauryl thiodipropionate (antioxidant DLTP), 2-mercaptobenzimidazole (antioxidant MB), 2-mercaptobenzothiazole (antioxidant MBT), triphenyl phosphite, tris(nonylphenyl)phosphite, tris[2,4-di-tert-butylphenyl]phosphite (antioxidant 168), tri(ethylene glycol) bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (antioxidant 245), and antioxidant Chinox 20N; preferably at least one of 2,6-di-tert-butyl-4-methylphenol (antioxidant BHT), tert-butylhydroquinone (antioxidant TBHQ), tris[2.4-di-tert-butylphenyl]phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tri(ethylene glycol) bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (antioxidant 245), and antioxidant Chinox 20N.

[0115] According to some embodiments of the present application, the first lubricant and the second lubricant are the same or different, and each is independently selected from at least one of ethylene bis-stearamide, calcium stearate, monoglyceride fatty acid, polyethylene wax, erucamide, and pentaerythritol stearate, preferably erucamide.

[0116] In different embodiments of the present application, the first and second additives are not limited to specific types and amounts of the additives, and each can have a wide range of selection. For example, the first and second additives each can further include a slip agent and / or a plasticizer, and are not limited to specific types and amounts of the additives, and each can have a wide range of selection.

[0117] According to some embodiments of the present application, the composite material is in a strip, rod or particle shape.

[0118] In the present application, the strip, rod or particle shape of the weather-resistant glass fiber reinforced polyglycolic acid composite material can be cut from a continuous filament shape of the weather-resistant glass fiber reinforced polyglycolic acid composite material.

[0119] Preferably, the length of the strip or rod shape of the composite material is 6-25 mm, such as 6 mm, 8 mm, 10 mm, 12 mm, 15 mm, 20 mm, 22 mm, 25 mm, etc., preferably 8-20 mm, and more preferably 10-15 mm.

[0120] The particle size of the particle shape of the composite material is 3-5 mm, such as 3 mm, 4 mm, 5 mm, etc. Preferably, the particle size is 3-4 mm.

[0121] The present application does not have special requirements for the cross-sectional shape of the weather-resistant glass fiber reinforced polyglycolic acid composite material. In some embodiments, the cross-section of the particle or rod shape of the weather-resistant glass fiber reinforced polyglycolic acid composite material is circular or circular-like. In other embodiments, the cross-section of the particle or strip shape of the weather-resistant glass fiber reinforced polyglycolic acid composite material is rectangular or square.

[0122] The present application provides a preparation method of the weather-resistant glass fiber reinforced polyglycolic acid composite material, comprising:

[0123] S1. mixing and melting the first polyglycolic acid resin and the first additive to obtain a first component melt;

[0124] S2. performing a first impregnation treatment on the continuous glass fiber and the first component melt in step S1 to form a filamentous inner core material;

[0125] S3. mixing and melting the second polyglycolic acid resin and the second additive to obtain a second component melt;

[0126] S4. subjecting the inner core material obtained in step S2 to at least one second impregnation treatment with the second component melt obtained in step S3 to obtain the weather-resistant glass fiber reinforced polyglycolic acid composite material.

[0127] The preparation method of the present application can be performed continuously in line to obtain a continuous filamentous product, which can be directly stored and used, or cut into a strip, rod or granular product with a certain length or particle size.

[0128] According to some embodiments of the present application, the mixing conditions in step S1 are: temperature 40-60℃, time 3-5 min; and / or, the melting temperature in step S1 is 230-260℃.

[0129] According to some embodiments of the present application, the mixing conditions in step S3 are: temperature 40-60℃, time 3-5 min; and / or, the melting temperature in step S3 is 230-260℃.

[0130] In the present application, the temperature range for steps S1, S3 and melting time can be selected to be relatively wide, so as to enable the first polyglycolic acid resin and the first auxiliary agent, and the second polyglycolic acid resin and the second auxiliary agent to be fully melted to obtain a melt.

[0131] According to some embodiments of the present application, the step S2 further comprises: before the first impregnation treatment of the continuous glass fiber, performing a dispersion treatment and a preheating treatment on the continuous glass fiber. Preferably, the temperature of the preheating treatment is 80-250℃. The dispersion treatment process in the present application adopts a conventional fiber dispersion treatment process in the art.

[0132] According to some embodiments of the present application, the step S4 further comprises: after the second impregnation treatment, performing a pulling-out, stretching, cooling, drying and granulation treatment on the material obtained after the second impregnation treatment to obtain the weather-resistant glass fiber reinforced polyglycolic acid composite material. The process conditions for the pulling-out, stretching, cooling, drying and granulation treatment are not particularly limited, and a person skilled in the art can adjust them according to the specific performance requirements of the weather-resistant glass fiber reinforced polyglycolic acid composite material to be prepared.

[0133] According to some embodiments of the present application, the first impregnation treatment in step S2 can be performed in a first impregnation mold, the first impregnation mold being an adjustable impregnation mold, the first impregnation mold comprising a fiber inlet, a fiber outlet and a melt flow channel, at least one first godet being arranged in the mold cavity of the first impregnation mold; the first godet being movable between the fiber inlet and the fiber outlet; and / or, the first godet being movable in a direction perpendicular to the connecting line of the fiber inlet and the fiber outlet.

[0134] According to some embodiments of the present application, the first impregnation treatment in step S2 can be performed in a second impregnation die, which is a combined impregnation die, the second impregnation die comprising a first module, an intermediate module and a second module connected in sequence, the first module being provided with a fiber inlet and a first module flow channel, the second module being provided with a fiber outlet and a second module flow channel, and the intermediate module being provided with an intermediate module flow channel; after the first module, the intermediate module and the second module are connected in sequence, the first module flow channel, the intermediate module flow channel and the second module flow channel are connected in communication to form a combined flow channel for the fibers to pass through.

[0135] According to some embodiments of the present application, the first impregnation treatment in step S2 can also be performed in a third impregnation die, which is a strong turbulence impregnation die, the third impregnation die comprising a fiber inlet channel, an impregnation outlet and a melt slit flow channel, all of which are in communication with a die cavity inside the third impregnation die; wherein the die cavity of the third impregnation die is provided with a second godet, the second godet comprising at least one driving godet, the driving godet being driven to rotate by a driving device.

[0136] 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.

[0137] 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 weather-resistant glass fiber reinforced polyglycolic acid composite materials.

[0138] 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 die. The forming die is composed of a core, a sleeve and a sleeve mouth die plate. The core is located inside the sleeve to form a forming cavity with the sleeve, and the resin melt can enter the cavity from the bottom or top or both sides of the sleeve. The core can move forward and backward in the sleeve, and the pressure of the melt in the cavity can be 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 sleeve. The working principle of the forming die is as follows: the strip formed by the inner layer impregnated material after passing through the impregnation die is guided to pass through the hole in the middle of the core, and then the forming of the inner and outer layer material composite structure is realized in the cavity filled with mixed melt formed by the core and the sleeve, and finally it is guided out through the sleeve mouth die plate.

[0139] The present application will be further described below with reference to the accompanying drawings.

[0140] Figure 1 The structure of the weather-resistant glass fiber reinforced polyglycolic acid composite material of the present application is shown. As shown in Figure 1 the cross section of the weather-resistant glass fiber reinforced polyglycolic acid composite material of the present application is circular, sequentially comprising inner core material 0-1 and outer layer material 0-3 from inside to outside, the inner core material 0-1 has fiber bundles 0-2 oriented in the longitudinal direction distributed therein, and the fiber bundles 0-2 are uniformly dispersed in the inner core material 0-1.

[0141] As shown in Figure 2 and Figure 3 the manufacturing system of the present application comprises, in sequence, fiber rack and fiber guiding device 1, fiber pretreatment device 2, first impregnation die 3, melt plasticizing feeding device 4, forming die 5, cooling water tank 6, drying machine 7, traction machine 8, granulator 9, collection box 10 and electric control system (not shown in the figure).

[0142] In the manufacturing system, the forming die 5 is used for the forming of the weather-resistant glass fiber reinforced polyglycolic acid composite material, and the structure thereof is shown in Figure 8 .

[0143] In the manufacturing system, the first impregnation die 3 is used for the impregnation of the fiber with the first polyglycolic acid resin melt.

[0144] As shown in Figure 4 in one embodiment, the first impregnation die is an impregnation device with adjustable position of the guide roller, comprising a first impregnation die die head A300, which comprises an impregnation die body A7, a fiber inlet A1, a fiber outlet A6 and a melt flow channel A3. At least one first guide roller A8 is arranged in the die cavity, wherein the first guide roller A8 can move between the fiber inlet A1 and the fiber outlet A6, or the first guide roller A8 can move in a direction perpendicular to the connecting line of the fiber inlet A1 and the fiber outlet A6, or the first guide roller A8 can move both between the fiber inlet A1 and the fiber outlet A6 and in a direction perpendicular to the connecting line of the fiber inlet A1 and the fiber outlet A6.

[0145] Taking a rectangular first impregnation die die head A300 as an example, a plurality of first guide rollers A8 are arranged in the first impregnation die die head A300, and the axial direction of each first guide roller A8 is the width direction of the first impregnation die die head A300, so that each first guide roller A8 can move in the length direction of the first impregnation die die head A300 and also in the height direction, thereby changing the position of the first guide roller A8 in the first impregnation die die head A300.

[0146] It can be understood that the axial direction of the first guide roller A8 can also be the length direction of the first impregnation die head A300, at this time each first guide roller A8 can move along the width direction of the first impregnation die head A300, and can also move along the height direction of the first impregnation die head A300, so as to change the position of the first guide roller A8 in the first impregnation die head A300.

[0147] Since the fiber needs to pass the first guide roller A8 in the mold cavity in the first impregnation die head A300 in turn when it travels in the mold cavity, by changing the position (horizontal position, vertical position, etc.) of the first guide roller A8 in the first impregnation die head A300, the travel path of the fiber in the mold cavity can be changed, so that when the required impregnation condition of the fiber changes, a new die does not need to be replaced, but only the position of the first guide roller 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.

[0148] Specifically, the application concept is to achieve the purpose of adjusting the position of the first guide roller A8 by slotting the inner wall of the mold cavity of the first impregnation die head A300.

[0149] The first inner wall of the first impregnation die head A300 is provided with a first sliding groove A4, the first sliding groove A4 extends between the fiber inlet A1 and the fiber outlet A6 (i.e. Figure 4 The X-axis direction shown), the first guide roller A8 moves along the first sliding groove A4 to change its horizontal position in the first impregnation die head A300.

[0150] Further, the first inner wall of the first impregnation die head A300 is also provided with a second sliding groove A2, the second sliding groove extends in a direction perpendicular to the first sliding groove A4 (i.e. Figure 4 The Y-axis direction shown), the first guide roller A8 moves along the second sliding groove A2 to change its vertical position in the die head.

[0151] It should be noted that the first sliding groove A4 and the second sliding groove A2 can be connected. Therefore, the first guide roller A8 can be arbitrarily moved in the longitudinal direction or the transverse direction, so that its position is changed.

[0152] Among them, the cross section of the first sliding groove A4 and the second sliding groove A2 can be trapezoidal, circular, arc-shaped or rectangular, etc., and the application does not limit this.

[0153] Both ends of the first godet roll A8 are provided with an adjusting device (not shown in the figure), which is used to adjust the axial length of the first godet roll A8, wherein the minimum axial length of the first godet roll A8 is smaller than the distance between the first inner wall and the second inner wall, and the maximum axial length of the first godet roll A8 is greater than the distance between the first inner wall and the second inner wall.

[0154] As shown in Figure 5 In another embodiment of the present application, the second impregnation die is a combined impregnation die, which comprises a second impregnation die head B300, and the second impregnation die head B300 comprises a first module B3, an intermediate module B6 and a second module B7 connected in sequence. Wherein the first module B3 is provided with a fiber inlet B1 and a first module flow channel B31, the second module B7 is provided with a fiber outlet B8 and a second module flow channel B71, and the intermediate module B6 is provided with an intermediate module flow channel B61.

[0155] 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, the second module B7 is the last 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.

[0156] That is, the number of intermediate modules B6 can be increased or decreased as needed, so that when the impregnation requirements change, different intermediate modules B6 are selected to form a combined second impregnation die head B300, thereby improving the continuity and production efficiency of the production and saving the cost of additional die opening.

[0157] Furthermore, by selecting different intermediate modules B6, the shape parameters (such as curvature, etc.) of the combined flow channel B4 formed can be changed, so that the flow path of the fiber and the melt can be changed, and then the fiber impregnation angle and fiber tension in different stations of the die can be changed, ultimately achieving the purpose of adjusting and optimizing the whole fiber impregnation process, and improving the adaptability of the second impregnation die head B300 to polyglycolic acid resin and fiber.

[0158] The above-mentioned first module B3, intermediate module B6 and second module B7 are placed in the die holder, and the constraint action of the die holder makes them closely contact with each other, thereby ensuring the sealing property of the combined flow channel B4 formed.

[0159] As shown in Figure 5 An embodiment with 2 intermediate modules B6 is shown. In Figure 5In 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.

[0160] Understandably, different combinations of flow channels B4 can be obtained by selecting different intermediate modules B6.

[0161] 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.

[0162] 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.

[0163] The impregnation mold body C2 has a second guide roller inside its cavity. This second guide roller includes at least one active guide roller C4, which is driven to rotate by a drive device (not shown in the figure). Since the rotation of the active guide roller C4 is driven by the drive device, rather than by the fiber's traction, the actively rotating active guide roller C4 helps reduce the fiber's traction tension and the friction between the fiber and the active guide roller C4 as the fiber passes through it. This reduces fiber breakage, ensures fiber integrity, and prevents fiber breakage, thereby improving the material's mechanical properties.

[0164] Preferably, the second guide roller further includes at least one driven guide roller C5, which is driven by the fiber passing through the active guide roller C4; or the driven guide roller C5 and the active guide roller C4 are connected by a belt mechanism, a gear mechanism or a chain mechanism.

[0165] like Figure 6The diagram illustrates an example with one active guide roller C4 and two driven guide rollers C5, wherein the two driven guide rollers C5 are arranged one above the other to extend the impregnation path of the fibers passing through them. The active guide roller C4 and the driven guide rollers C5 may be at the same or different heights within the die cavity.

[0166] Furthermore, the driving device can be a motor, hydraulic mechanism, or gearbox, or any device capable of driving the active guide roller C4 to rotate.

[0167] Based on the fiber's traveling speed v1 in the mold cavity of the impregnation mold body C2, the corresponding tangential speed v2 of the active guide roller C4 can be selected. For example, the tangential speed v2 of the active guide roller C4 can be made the same as the fiber's traveling speed v1, i.e., v1 = v2. This reduces fiber breakage and wear, thus ensuring fiber integrity, promoting the degree of fiber impregnation, shortening impregnation time, and improving production efficiency.

[0168] like Figure 2 As shown, the melt plasticizing feeding device 4 consists of a twin-screw extruder used for melting and plasticizing materials. The twin-screw extruder is a co-rotating twin-screw extruder with a screw diameter of 25mm-95mm and a length-to-diameter ratio of 36:1-65:1. When the melt plasticizing feeding device 4 consists of a single extruder 4, the melt plasticizing material in the extruder is divided by a melt distributor and fed into the impregnation die and the forming die respectively, and the flow rate of each die is controlled by a melt flow control valve.

[0169] like Figure 3 As shown, when the melt plasticizing feeding device 4 consists of two extruders 4-1 and 4-2, the molten plasticized melts from extruder I 4-1 and extruder II 4-2 are respectively fed into the impregnation mold and the forming mold. In this embodiment, the melt plasticizing feeding device consists of two extruders I 4-1 and extruder II 4-2, and the molten plasticized melts from extruder I 4-1 and extruder II 4-2 are respectively fed into the first impregnation mold 3 and the forming mold 5. Extruder I 4-1 and extruder II 4-2 can be fed with the same or different materials, thus enabling the preparation of composite materials with the same or different materials for the inner and outer layers.

[0170] The fiber pretreatment device 2 consists of a tension roller and a hot drying tunnel. This combination allows for some release of tension on the fibers as they enter the hot drying tunnel, thus accommodating fibers of different strengths and preventing fibers with lower strength from breaking before entering the impregnation die. The surface of the tension roller in the fiber pretreatment device 2 needs to be ceramic-coated to increase surface roughness and reduce friction on the fibers.

[0171] In the manufacturing system, the fiber stand and fiber guiding device 1 is used for guiding and untwisting the fiber, and the device is equipped with an automatic control untwisting device, which is connected with the traction machine 8 and is electrically connected with an electric control system (such as a PLC control device).

[0172] 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, and will not be described here.

[0173] Figure 7 A schematic diagram of the second impregnation treatment using a forming die is shown, Figure 8 A cross-sectional view of the forming die used in the second impregnation treatment is shown.

[0174] As Figure 8 shown, in one 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, forming a cavity with the outer sleeve 5-2, and the resin melt can enter the cavity from the bottom or top or both sides of the outer sleeve 5-2. The core 5-1 can move forward and backward in the outer sleeve 5-2, and the pressure of the melt in the cavity can be adjusted by adjusting the size of the cavity formed. The pressure of the melt in the cavity can also be adjusted by the angle between the core 5-1 and the outer sleeve 5-2. The working principle of the forming die 5 is as follows: the strand formed after the impregnation die 3 forms the inner layer of the impregnated material, is guided through the hole in the middle of the core 5-1, and then realizes the forming of the inner and outer layer material composite structure in the cavity filled with mixed melt formed by the core 5-1 and the outer sleeve 5-2, and finally is guided out through the outer sleeve die plate 5-3.

[0175] As Figure 7 shown, the strand 5-4 enters the cavity formed by the core (not shown) and the outer sleeve 5-2 filled with the second component melt, wherein the second component melt is fed into the cavity from the second resin inlet 5-5.

[0176] In the following examples and comparative examples, the manufacturing system shown in Figure 3 is used to prepare weather-resistant glass fiber reinforced polyglycolic acid composites, wherein the first impregnation treatment uses the first impregnation die shown in Figure 4 , and the second impregnation treatment uses the forming die shown in Figure 8 .

[0177] The weather-resistant glass fiber reinforced polyglycolic acid composites and the preparation method thereof provided by the present application will be described in detail below in conjunction with specific examples.

[0178] Unless otherwise defined, the technical terms used in the following examples have the same meanings as commonly understood by those skilled in the art to which this application belongs. The reagents used in the following examples are all conventional biochemical reagents unless otherwise specified. The raw materials, instruments and equipment used in the following examples can be purchased on the market or obtained by existing methods. The reagent usage is conventional unless otherwise specified. The experimental methods are conventional unless otherwise specified.

[0179] In the various embodiments and comparative examples of the present application, the test methods for each performance data are as follows:

[0180] (1) Tensile strength: GB / T 1040-2018;

[0181] (2) Flexural modulus: GB / T 9341-2008;

[0182] (3) Impact strength: GB / T 1843-2008;

[0183] (4) Heat distortion temperature: GB / T 1634-2004, A method, bending stress 1.8 MPa;

[0184] (5) Weather resistance test: GB / T 16422.2-2014, Plastic laboratory light source exposure test method; 100 hours and 500 hours of simulated sunlight aging test were respectively carried out, and the changes of main mechanical properties before and after the test were compared.

[0185] In the various embodiments and comparative examples of the present application, the materials used are as follows:

[0186] (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 Wu Yu and Liaoning Jinmei respectively;

[0187] (2) Glass fiber: alkali-free glass fiber, diameter 17 μm, linear density 2400 tex, Chongqing International Composite Materials Co., Ltd.;

[0188] (3) Tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester: antioxidant 1010, BASF, Germany;

[0189] (4) Tris[2,4-di-tert-butylphenyl] phosphite: antioxidant 168, BASF, Germany;

[0190] (5) Triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate]: antioxidant 245, BASF, Germany;

[0191] (6) Silane coupling agent: KH-550, Nanjing Youpu Chemical Co., Ltd.;

[0192] (7) Calcium stearate: calcium content 6.5 wt%, Inocor;

[0193] (8) Erucamide: purity greater than 98.5%, Aldon Reagent;

[0194] (9) Caprolactam blocked polyisocyanate: anti-migrating agent, Covestro;

[0195] (10) Butanone oxime blocked polyisocyanate: anti-migrating agent, Covestro;

[0196] (11) 2-(2'-hydroxy-3',5'-di-amyloxyphenyl) benzotriazole: UV absorber UV-320, BASF, Germany;

[0197] (12) 2-hydroxy-4-n-octyloxybenzophenone: UV absorber UV-531, BASF, Germany;

[0198] (13) 2,4,6-tris(2-hydroxy-4-n-butyloxyphenyl)-1,3,5-triazine: UV absorber, BASF, Germany;

[0199] (14) Bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate: light stabilizer HS-112, BASF, Germany;

[0200] (15) Poly(succinato-4-hydroxy-2,2,6,6-tetramethyl-1-piperidinoethanol) ester: light stabilizer 622, BASF, Germany;

[0201] (16) Poly(lactic acid-octanediol-sebacic acid) ester elastomer: Beijing Research Institute of Chemical Industry;

[0202] (17) Poly(sebacic acid-glycerol-lactic acid) ester (PGSC) elastomer: Beijing Research Institute of Chemical Industry;

[0203] (18) Poly(itaconate-isoprene-glycidyl methacrylate) elastomer: Beijing Research Institute of Chemical Industry;

[0204] (19) Talc: Guangxi Longsheng Huamei;

[0205] (20) Silicon dioxide: Dalian Fuji Mineral Products.

[0206] The following describes the preparation of a bio-based elastomer-loaded composite weather-resistant masterbatch in the form of a preparation example.

[0207] Preparation Example 1

[0208] Preparation of bio-based elastomer loaded composite weatherable masterbatch NH001:

[0209] a. 0.2 parts by weight of antioxidant 168, 0.2 parts by weight of antioxidant 245, 0.5 parts by weight of UV absorber UV-320, 0.2 parts by weight of light stabilizer HS-112, 0.5 parts by weight of caprolactam blocked polyisocyanate (anti-migrating agent), 0.5 parts by weight of talc were mixed using an air jet pulverizer for 15 minutes, motor power 300W;

[0210] b. The powder obtained in step a was mixed with 100 parts by weight of poly(lactic acid) using a Banbury mixer, Banbury mixer speed 10 rpm, Banbury mixer temperature 120 °C;

[0211] c. The Banbury product obtained in step b was sufficiently broken up using a freezer crusher and an air jet pulverizer to obtain bio-based elastomer loaded composite weatherable masterbatch NH001.

[0212] Preparation Example 2

[0213] Preparation of bio-based elastomer loaded composite weatherable masterbatch NH002:

[0214] a. 0.2 parts by weight of antioxidant 245, 0.2 parts by weight of antioxidant 168, 0.5 parts by weight of UV absorber UV-531, 0.2 parts by weight of light stabilizer HS-112, 0.5 parts by weight of caprolactam blocked polyisocyanate (anti-migrating agent), 0.5 parts by weight of talc were mixed using an air jet pulverizer for 15 minutes, motor power 300W;

[0215] b. The powder obtained in step a was mixed with 100 parts by weight of poly(glycol sebacic acid-lactic acid) ester (PGSC) elastomer using a Banbury mixer, Banbury mixer speed 10 rpm, Banbury mixer temperature 120 °C;

[0216] c. The Banbury product obtained in step b was sufficiently broken up using a freezer crusher and an air jet pulverizer to obtain bio-based elastomer loaded composite weatherable masterbatch NH002.

[0217] Preparation Example 3

[0218] Preparation of bio-based elastomer loaded composite weatherable masterbatch NH003:

[0219] a. 0.2 parts by weight of antioxidant 245, 0.2 parts by weight of antioxidant 168, 0.5 parts by weight of 2,4,6-tris(2-hydroxy-4-n-butyloxyphenyl)-1,3,5-triazine (UV absorber), 0.2 parts by weight of light stabilizer 622, 0.5 parts by weight of butanone oxime blocked polyisocyanate (anti-migrating agent), 0.5 parts by weight of silicon dioxide, 0.5 parts by weight of erucamide were mixed using an air jet pulverizer for 15 minutes, motor power 300W;

[0220] b. Mix the powder obtained in step a with 100 parts by weight of poly(itaconate-isoprene-glycidyl methacrylate) elastomer in an internal mixer at a speed of 10 rpm and a mixing temperature of 140°C.

[0221] c. The intensively mixed product obtained in step b is thoroughly crushed by a cryogenic crusher and an air jet mill to obtain bio-based elastomer-loaded composite weather-resistant masterbatch NH003.

[0222] Example 1

[0223] (1) 100 parts by weight of polyglycolic acid (melt index 40g / 10min) and 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 are mixed in a high-speed mixer at 50°C for 3 minutes. After melting, the mixture is sent to an impregnation mold.

[0224] (2) Continuous glass fibers are introduced into the impregnation mold under the action of the traction machine and impregnated and dispersed with the above melt to form a strip, which is used as the inner layer material, wherein the glass fiber content is 60 parts by weight.

[0225] (3) 100 parts by weight of polyglycolic acid (melt index 10g / 10min) and 10 parts by weight of bio-based elastomer composite weather-resistant masterbatch NH001, 1 part by weight of KH550, 0.1 parts by weight of antioxidant 1010 and 0.5 parts by weight of calcium stearate are stirred in a high-speed mixer at 50°C for 3 minutes. This mixture is used as the outer layer material and fed into a twin-screw extruder connected to the molding die.

[0226] (4) The inner layer material enters the molding die under the action of the traction machine, is guided through the hole in the middle of the core, and is formed in the cavity filled with the molten mixture of the outer layer material formed by the core and the outer jacket. Finally, it is exported through the outer jacket template.

[0227] (5) The amount of outer layer material is adjusted by selecting the size (4mm) of the outer mold outer template, and the cutting speed of the pelletizer is adjusted to control the pellet length of the obtained polyglycolic acid composite material to be 15mm. The content of the first polyglycolic acid in the obtained composite material is 100 parts by weight, the content of glass fiber is 60 parts by weight, and the content of the second polyglycolic acid is 100 parts by weight.

[0228] (6) The polyglycolic acid composite material prepared by the above method was injection molded into standard specimens and its performance was tested. The test results are shown in Table 1.

[0229] Comparative Example 1

[0230] (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, 0.2 parts by weight of calcium stearate, and 60 parts by weight of glass fiber (4-6 mm) in a high-speed mixer at 50°C for 3 minutes.

[0231] (2) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) was mixed with 10 parts by weight of bio-based elastomer composite weatherable masterbatch NH001, 1 part 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.

[0232] (3) The above two mixtures were added together into a twin-screw extruder for melt granulation, and the obtained polyglycolic acid composite particles had a length of 15 mm. In the obtained composite, the first polyglycolic acid content was 100 parts by weight, the glass fiber content was 60 parts by weight, and the second polyglycolic acid content was 100 parts by weight.

[0233] (4) The above prepared polyglycolic acid composite was injection molded into standard bars for performance testing. The test results are shown in Table 1.

[0234] Comparative Example 2

[0235] (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, 0.2 parts by weight of calcium stearate, and 60 parts by weight of glass fiber (4-6 mm) in a high-speed mixer at 50°C for 3 minutes, and then melt granulation was performed to obtain polyglycolic acid composite 1.

[0236] (2) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) was mixed with 10 parts by weight of bio-based elastomer composite weatherable masterbatch NH001, 1 part 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.

[0237] (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 first polyglycolic acid content was 100 parts by weight, the glass fiber content was 60 parts by weight, and the second polyglycolic acid content was 100 parts by weight.

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

[0239] Comparative Example 3

[0240] (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 part by weight of antioxidant 168, 0.3 part by weight of antioxidant 1010, and 0.2 part by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, and then fed into an impregnation mold after melting.

[0241] (2) Continuous glass fibers were introduced into the impregnation mold under the action of a pulling machine, impregnated and dispersed with the above-mentioned melt to form a sample, which was used as an inner layer material, wherein the glass fiber content was 60 parts by weight.

[0242] (3) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) was mixed with 0.02 part by weight of antioxidant 168, 0.02 part by weight of antioxidant 245, 0.05 part by weight of ultraviolet absorber UV-320, 0.02 part by weight of light stabilizer HS-112, 0.05 part by weight of caprolactam- blocked polyisocyanate, 0.05 part by weight of talc, 1 part by weight of KH550, 0.1 part by weight of antioxidant 1010, and 0.5 part by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, which was used as an outer layer material, and was fed into a double-screw extruder connected to a molding mold.

[0243] (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 formed in the cavity filled with the mixed melt of the outer layer material between the core and the outer sleeve to realize the molding of the inner and outer layer material composite structure, and finally guided out through the outer sleeve die plate.

[0244] (5) The amount of outer layer material was adjusted by selecting the size (4 mm) of the outer sleeve die plate of the molding mold, and the length of the obtained polyglycolic acid composite material was controlled to be 15 mm by adjusting the cutter speed of the granulator. The first polyglycolic acid content in the obtained composite material was 100 parts by weight, the glass fiber content was 60 parts by weight, and the second polyglycolic acid content was 100 parts by weight.

[0245] (6) The polyglycolic acid composite material prepared by the above method was injection molded into a standard sample, and performance tests were conducted. The test results are shown in Table 1.

[0246] Comparative Example 4

[0247] (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 part by weight of antioxidant 168, 0.3 part by weight of antioxidant 1010, and 0.2 part by weight of calcium stearate in a high-speed mixer at 50°C for 3 minutes, and then fed into an impregnation mold after melting.

[0248] (2) The continuous glass fiber is introduced into the impregnation mold under the action of the traction machine, impregnated and dispersed with the above-mentioned melt to form a sample, which is used as the inner layer material, wherein the glass fiber content is 60 parts by weight.

[0249] (3) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) is mixed with 0.02 parts by weight of antioxidant 168, 0.02 parts by weight of antioxidant 245, 0.05 parts by weight of ultraviolet absorber UV-320, 0.02 parts by weight of light stabilizer HS-112, 0.05 parts by weight of talc, 1 part 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, stirred at 50°C for 3 minutes, used as the outer layer material, and fed into the double-screw extruder connected with the forming mold.

[0250] (4) The inner layer material is introduced into the forming mold under the action of the traction machine, guided through the hole in the middle of the core, and realizes the forming of the inner and outer layer material composite structure in the cavity filled with the mixed melt of the outer layer material formed by the core and the outer sleeve. Finally, it is guided out through the outer sleeve die plate.

[0251] (5) The cladding amount of the outer layer material is adjusted by selecting the size (4 mm) of the outer sleeve die plate of the forming mold, and the cutter rotating speed of the granulator is adjusted to control the length of the obtained polyglycolic acid composite material to be 15 mm. The first polyglycolic acid content in the obtained composite material is 100 parts by weight, the glass fiber content is 60 parts by weight, and the second polyglycolic acid content is 100 parts by weight.

[0252] (6) The polyglycolic acid composite material prepared by the above method is injection molded into a standard sample for performance testing. The test results are shown in Table 1.

[0253] Example 2

[0254] (1) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) is 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 erucic acid amide in a high-speed mixer at 50°C for 3 minutes, and then fed into the impregnation mold after melting.

[0255] (2) The continuous glass fiber is introduced into the impregnation mold under the action of the traction machine, impregnated and dispersed with the above-mentioned melt to form a sample, which is used as the inner layer material, wherein the glass fiber content is 20 parts by weight.

[0256] (3) 100 parts by weight of polyglycolic acid (melt index 150 g / 10 min) was mixed with 10 parts by weight of bio-based elastomer composite weathering masterbatch NH002, 0.1 part by weight of KH550, 0.2 parts by weight of antioxidant 1010, and 0.2 parts by weight of erucic acid amide in a high-speed mixer at 50°C for 3 minutes, and was used as the outer layer material and was fed into a double-screw extruder connected to a forming die.

[0257] (4) The inner layer material was introduced into the forming die under the action of the traction machine, guided through the hole in the middle of the core, and formed a composite structure of the inner and outer layer materials in the cavity filled with the mixed melt of the outer layer material formed by the core and the outer sleeve. Finally, it was guided out through the outer sleeve die plate.

[0258] (5) The amount of outer layer material was adjusted by selecting the size (4 mm) of the outer sleeve die plate of the forming die, and the cutter speed of the granulator was adjusted to control the length of the obtained polyglycolic acid composite material to be 10 mm. The first polyglycolic acid content in the obtained composite material was 100 parts by weight, the glass fiber content was 20 parts by weight, and the second polyglycolic acid content was 50 parts by weight.

[0259] (6) The polyglycolic acid composite material prepared by the above method was injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0260] Example 3

[0261] (1) 100 parts by weight of polyglycolic acid (melt index 150 g / 10 min) was 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, and was fed into an impregnation die after melting.

[0262] (2) Continuous glass fibers were introduced into the impregnation die under the action of the traction machine, impregnated and dispersed with the above-mentioned melt to form a sample bar, which was used as the inner layer material, and the glass fiber content was 150 parts by weight.

[0263] (3) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) was mixed with 10 parts by weight of bio-based elastomer composite weathering masterbatch NH003, 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, and was used as the outer layer material and was fed into a double-screw extruder connected to a forming die.

[0264] (4) The inner layer material was introduced into the forming die under the action of the traction machine, guided through the hole in the middle of the core, and formed a composite structure of the inner and outer layer materials in the cavity filled with the mixed melt of the outer layer material formed by the core and the outer sleeve. Finally, it was guided out through the outer sleeve die plate.

[0265] (5) The amount of outer layer material is adjusted by selecting the size (4mm) of the outer mold outer template, and the cutting speed of the pelletizer is adjusted to control the pellet length of the obtained polyglycolic acid composite material to be 3mm. The content of the first polyglycolic acid in the obtained composite material is 100 parts by weight, the content of glass fiber is 150 parts by weight, and the content of the second polyglycolic acid is 60 parts by weight.

[0266] (6) The polyglycolic acid composite material prepared by the above method was injection molded into standard specimens and its performance was tested. The test results are shown in Table 1.

[0267] Example 4

[0268] (1) 100 parts by weight of polyglycolic acid (melt index 100g / 10min) and 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 are mixed in a high-speed mixer at 50°C for 3 minutes. After melting, the mixture is sent to an impregnation mold.

[0269] (2) Continuous glass fibers are introduced into the impregnation mold under the action of the traction machine and impregnated and dispersed with the above melt to form a strip, which is used as the inner layer material, wherein the glass fiber content is 100 parts by weight.

[0270] (3) 100 parts by weight of polyglycolic acid (melt index 100g / 10min) and 10 parts by weight of bio-based elastomer composite weather-resistant masterbatch NH003, 1 part by weight of KH550, 0.5 parts by weight of antioxidant 1010 and 0.2 parts by weight of calcium stearate are stirred in a high-speed mixer at 50°C for 3 minutes. This mixture is used as the outer layer material and fed into a twin-screw extruder connected to the molding die.

[0271] (4) The inner layer material enters the molding die under the action of the traction machine, is guided through the hole in the middle of the core, and is formed in the cavity filled with the molten mixture of the outer layer material formed by the core and the outer jacket. Finally, it is exported through the outer jacket template.

[0272] (5) The amount of outer layer material is adjusted by selecting the size (4mm) of the outer mold outer template, and the cutting speed of the pelletizer is adjusted to control the pellet length of the obtained polyglycolic acid composite material to be 4mm. The content of the first polyglycolic acid in the obtained composite material is 100 parts by weight, the content of glass fiber is 100 parts by weight, and the content of the second polyglycolic acid is 80 parts by weight.

[0273] (6) The polyglycolic acid composite material prepared by the above method was injection molded into standard specimens and its performance was tested. The test results are shown in Table 1.

[0274] Table 1. Material performance test results

[0275]

[0276]

[0277] Note: The results of 100 hours and 500 hours test give the retention rate of mechanical properties, i.e. the ratio of the mechanical properties measured at 100 hours or 500 hours to the mechanical properties measured at 0 hour.

[0278] From Example 1 and Comparative Examples 1-2, it can be seen that the weather-resistant glass fiber reinforced polyglycolic acid composite material described in the present application can uniformly disperse the weather-resistant master batch of glass fiber and bio-based elastomer load composite in the matrix resin, greatly improve the mechanical strength and weather resistance of the composite material, and effectively expand the application range of polyglycolic acid.

[0279] From Example 1 and Comparative Examples 3-4, it can be seen that the composite material added with the bio-based elastomer load composite weather-resistant master batch has stronger weather resistance, and the retention rate of mechanical strength after 100 hours and 500 hours is above 85% and 70% respectively. At the same time, the addition of the bio-based elastomer load composite weather-resistant master batch can improve the impact strength of the composite material and improve the toughness of the PGA glass fiber material.

[0280] In addition, the polyglycolic acid composite material of Example 2 has improved gloss.

[0281] It should be noted that the above-described examples are only used to explain the present application and do not constitute any limitation on the present application. The present application is described by referring to typical examples, but it should be understood that the words used therein are descriptive and explanatory words, rather than limiting words. The present application can be modified within the scope of the claims, and the present application can be revised without departing from the scope and spirit of the present application. Although the present application described therein relates to specific methods, materials and examples, it does not mean that the present application is limited to the specific examples disclosed therein, on the contrary, the present application can be extended to all other methods and applications with the same function.

Claims

1. A weatherable 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, the outer layer material comprises a second polyglycolic acid resin and a second additive, the second additive comprises a weather-resistant masterbatch; In the composite material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the glass fibers is 10-200 parts by weight; The amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the second polyglycolic acid resin is 50-100 parts by weight; The amount of the second polyglycolic acid resin is 100 parts by weight, and the amount of the weather-resistant masterbatch is 2-50 parts by weight; The weather-resistant masterbatch is a bio-based elastomer-loaded composite weather-resistant masterbatch, which comprises an antioxidant, a ultraviolet absorber, a light stabilizer, an anti-migration agent, a bio-based elastomer and a dispersing agent; The amount of the bio-based elastomer is 100 parts by weight, the content of the antioxidant is 0.01-1 part by weight, the content of the ultraviolet absorber is 0.1-2 parts by weight, the content of the light stabilizer is 0.1-2 parts by weight, the content of the anti-migration agent is 0.01-10 parts by weight, and the content of the dispersing agent is 0.1-10 parts by weight.

2. The composite material of claim 1, wherein, In the composite material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the glass fibers is 10-150 parts by weight; And / or, the amount of the second polyglycolic acid resin is 100 parts by weight, and the amount of the weather-resistant masterbatch is 5-30 parts by weight.

3. The composite material of claim 2, wherein, In the composite material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the glass fibers is 20-150 parts by weight.

4. The composite material of claim 1, wherein, The amount of the bio-based elastomer is 100 parts by weight, the content of the antioxidant is 0.01-1 part by weight, the content of the ultraviolet absorber is 0.1-2 parts by weight, the content of the light stabilizer is 0.1-2 parts by weight, the content of the anti-migration agent is 0.01-10 parts by weight, and the content of the dispersing agent is 0.5-5 parts by weight.

5. The composite material according to any one of claims 1 to 4, characterized in that, the antioxidant is at least one of 2,6-di-tert-butyl-4-methylphenol, tert-butyl hydroquinone, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-thiobis-[3-methyl-6-tert-butylphenol], 2,2'-thiobis-[4-methyl-6-tert-butylphenol], 1,3,5-di[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]-hexahydro-1,3,5-triazine, N,N'-bis(β-naphthyl)-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, dilaurylthiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, triphenyl phosphite, tris(nonylphenyl)phosphite, tris[2,4-di-tert-butylphenyl]phosphite, triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], antioxidant Chinox 20N; and / or, the antioxidant is a mass ratio of 1:2 to 2:1 of a hindered phenolic antioxidant and a phosphite antioxidant; and / or, the ultraviolet absorber is at least one of 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-pentylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, phenyl o-hydroxybenzoate, m-hydroxybenzoic acid resorcinol ester, o-nitroaniline, p-cresol, 2,4,6-tris(2-hydroxy-4-n-butyloxyphenyl)-1,3,5-triazine, 2-cyano-3,3-diphenylacrylic acid 2-ethylhexyl ester, p-tert-butylphenyl salicylate, bisphenol A bis-salicylate, bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester), 2,2'-thiobis(4-tert-octylphenyloxy)nickel; and / or, the light stabilizer is at least one of poly(succinato-4-hydroxy-2,2,6,6-tetramethyl-1-piperidinylethyl ester), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6-pentamethylpiperidinol)sebacate, 1-(methyl)-8-(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2,4-[(2,2,6,6,-tetramethyl-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]}; and / or, the anti-migrating agent is a blocked polyisocyanate; ​ and / or, the bio-based elastomer is selected from at least one of poly(sebacic acid-glycerol) ester elastomer, acrylated poly(sebacic acid-glycerol) ester elastomer, poly(limonene citrate-1,8-octanediol) elastomer, copolymer of lactide-caprolactone, glycolide-lactide copolymer, glycolide-lactide-caprolactone terpolymer, poly(ester-carbonate) elastomer, poly(limonene citrate-octanediol-sebacic acid) elastomer, poly(sebacic acid-glycerol-limonene citrate) elastomer, poly(sebacic acid-1,2-propanediol-limonene citrate) elastomer, poly(itaconate-isoprene-glycidyl methacrylate) elastomer, soy oil-based elastomer, itaconate elastomer containing a trioxirane structure, myrcene bio-based elastomer; and / or, the dispersant is selected from a nano-sized inorganic powder.

6. The composite material of claim 5, wherein, The antioxidant is selected from at least one of 2,6-di-tert-butyl-4-methylphenol, tert-butyl hydroquinone, tris[2.4-di-tert-butylphenyl] phosphite, tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], antioxidant Chinox 20N; and / or, the antioxidant is a mass ratio of 1:1 of a hindered phenolic antioxidant and a phosphite antioxidant; and / or, the hindered phenolic antioxidant is tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester and / or triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate]; and / or, the phosphite antioxidant is tris[2.4-di-tert-butylphenyl] phosphite; and / or, the ultraviolet absorber is selected from at least one of 2-(2'-hydroxy-3',5'-pentylphenyl) benzotriazole, 2-hydroxy-4-n-octyloxybenzophenone, 2,4,6-tris(2-hydroxy-4-n-butyloxyphenyl)-1,3,5-triazine; and / or, the light stabilizer is selected from poly(succinic acid (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol) ester and / or bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate; and / or, the anti-migration agent is selected from at least one of a phenol-blocked polyisocyanate, a caprolactam-blocked polyisocyanate, a butanone oxime-blocked polyisocyanate; and / or, the dispersant is selected from at least one of a nano-sized calcium carbonate, a nano-sized silicon dioxide, a nano-sized montmorillonite, a nano-sized zinc oxide, a nano-sized talc, a nano-sized titanium dioxide, a nano-sized carbon nanotube, a nano-sized graphene, a nano-sized carbon fiber, a nano-sized boron nitride, a nano-sized zirconium dioxide, a nano-sized wollastonite, and a nano-sized zeolite.

7. The composite material of claim 6, wherein, The dispersant is a nano-sized calcium carbonate and / or a nano-sized fumed silica.

8. The composite material according to any one of claims 1 to 4, wherein The preparation method of the bio-based elastomer-loaded composite weather-resistant master batch comprises: S1. dispersing the antioxidant, the ultraviolet absorber, the light stabilizer, the anti-migration agent, and the dispersant using an airflow crusher to obtain a powder; S2. performing internal mixing of the powder obtained in step S1 and the bio-based elastomer; S3. The banbury product obtained in step S2 is broken by a freezer crusher and an air flow crusher to obtain a bio-based elastomer-loaded composite weather-resistant master batch.

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

10. The composite material of claim 9, wherein, The content of glycolic acid monomer in the copolymer polyglycolic acid is ≥90 mol%; And / or, the melt flow rate of the first polyglycolic acid resin at 230°C, 2.16 kg is 10-200 g / 10 min; And / or, the melt flow rate of the second polyglycolic acid resin at 230°C, 2.16 kg is 10-200 g / 10 min.

11. The composite material of claim 10, wherein, The content of glycolic acid monomer in the copolymer polyglycolic acid is ≥95 mol%; And / or, the melt flow rate of the first polyglycolic acid resin at 230°C, 2.16 kg is 10-150 g / 10 min; And / or, the melt flow rate of the second polyglycolic acid resin at 230°C, 2.16 kg is 10-150 g / 10 min.

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 first auxiliary agent includes at least one of 0.05-5 parts by weight of a first compatibilizer, 0.1-3 parts by weight of a first antioxidant, and 0.1-1 part by weight of a first lubricant; And / or, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second auxiliary agent further includes at least one of 0.05-5 parts by weight of a second compatibilizer, 0.1-3 parts by weight of a second antioxidant, and 0.1-1 part by weight of a second lubricant.

13. The composite material of claim 12, wherein, The amount of the first polyglycolic acid resin is 100 parts by weight, and the first auxiliary agent 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 amount of the second polyglycolic acid resin is 100 parts by weight, and the second auxiliary agent further 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.

14. The composite material of claim 12, wherein, The first compatibilizer and the second compatibilizer are the same or different and are each independently selected from at least one of a coupling agent; and / or, the first antioxidant and the second antioxidant are the same or different, each independently selected from at least one of 2,6-di-tert-butyl-4-methylphenol, tert-butyl hydroquinone, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-thiobis-[3-methyl-6-tert-butylphenol], 2,2'-thiobis-[4-methyl-6-tert-butylphenol], 1,3,5-di[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]-hexahydrotriazine, N,N'-di(β-naphthyl)-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, dilaurylthiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, triphenyl phosphite, tris(nonylphenyl)phosphite, tris[2,4-di-tert-butylphenyl]phosphite, glyceryl tri[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], antioxidant Chinox 20N; and / or, the first lubricant and the second lubricant are the same or different, each independently selected from at least one of ethylene bis-stearamide, calcium stearate, monoglyceride fatty acid, polyethylene wax, erucamide, pentaerythritol stearate.

15. The composite material of claim 14, wherein, the first compatibilizer and the second compatibilizer are the same or different, each independently selected from at least one of silane coupling agent, titanate coupling agent, organic chromium complex coupling agent; and / or, the first antioxidant and the second antioxidant are the same or different, each independently selected from at least one of 2,6-di-tert-butyl-4-methylphenol, tert-butyl hydroquinone, tris[2.4-di-tert-butylphenyl]phosphite, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, glyceryl tri[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], antioxidant Chinox 20N; and / or, the first lubricant and the second lubricant are the same or different, each independently selected from erucamide.

16. The composite material of claim 15, wherein, the first compatibilizer and the second compatibilizer are the same or different, each independently selected from silane coupling agent.

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

18. The composite material of claim 17, wherein, The inner core material is composed of a first polyglycolic acid resin, glass fibers and a first aid.

19. A method of making a composite material as claimed in any one of claims 1 to 18, characterised by, comprising: S1. melt the first polyglycolic acid resin and the first aid after mixing to obtain a first component melt; S2. perform 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. melt the second polyglycolic acid resin and the second aid after mixing to obtain a second component melt; S4. perform at least one second impregnation treatment on the inner core material obtained in step S2 with at least one second component melt obtained in step S3 to obtain the weather-resistant glass fiber reinforced polyglycolic acid composite material.

20. The method of claim 19, wherein the composite material is prepared by a process comprising: The mixing condition of the step S1 is that the temperature is 40-60℃ and the time is 3-5min; and / or the melting temperature of the step S1 is 230-260℃. And / or, the mixing condition of the step S3 is that the temperature is 40-60℃ and the time is 3-5min; and / or the melting temperature of the step S3 is 230-260℃. And / or, the step S2 further comprises: dispersing treatment and preheating treatment of the continuous glass fiber before the first impregnation treatment. And / or, the step S4 further comprises: after the second impregnation treatment, the material obtained by the second impregnation treatment is subjected to pulling out, stretching, cooling, drying and granulating treatment to obtain the weather-resistant glass fiber reinforced polyglycolic acid composite material.

21. The method of claim 20, wherein the composite material is prepared by a process comprising: The temperature of the preheating treatment is 80-250℃.

22. The method of making according to any one of claims 19-21, wherein, The first impregnation treatment in the step S2 is carried out in a first impregnation mold, the first impregnation mold is an adjustable impregnation mold, the first impregnation mold comprises a fiber inlet, a fiber outlet and a melt flow channel, at least one first godet is arranged in the mold cavity of the first impregnation mold; the first godet can move between the fiber inlet and the fiber outlet; and / or the first godet can move in a direction perpendicular to the connecting line of the fiber inlet and the fiber outlet.

23. The method of making according to any one of claims 19-21, wherein, The first impregnation treatment in the 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.

24. The method of any one of claims 19-21, wherein, The first impregnation treatment in the 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 mold cavity of the third impregnation mold is provided with a second godet, the second godet comprises at least one driving godet, and the driving godet is driven to rotate by a driving device.

25. The use of the composite material of any one of claims 1-18 or the composite material prepared by the preparation method of any one of claims 19-24 in the field of building decoration and engineering plastics.

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