Halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material, preparation method and application thereof

Abstract

The present application relates to the technical field of high polymer composite material, and provides a halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material, a preparation method and application thereof.The halogen-free flame-retardant 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 fiber and a first additive, the glass fiber continuously extends from one end of the core material to the opposite end; the outer material wraps the core material, and the outer material comprises a second polyglycolic acid resin, a flame-retardant additive and a second additive.The composite material provided by the present application forms a core-shell structure based on a multi-module system design, the inner layer material is filled with high content of glass fiber to improve the mechanical properties of the composite material, and the flame-retardant additive is added to the outer layer material to improve the flame-retardant properties of the composite material, and the composite material has the characteristics of high glass fiber filling amount, uniform dispersion of glass fiber and flame-retardant additive, and the flame-retardant and mechanical properties of the composite material are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high polymer composites, more particularly to a halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material, a preparation method and application thereof. BACKGROUND

[0002] With the aggravation of environmental pollution, developing biobased degradable materials has become one of the current research hotspots. Polyglycolic acid (PGA) is a new type of degradable material. Compared with traditional degradable plastics such as PLA, PBST and PHA, PGA has a faster degradation rate, and the final degradation product is H2O and CO2, which can minimize environmental pollution. The mechanical strength of PGA is comparable to that of engineering plastic PEEK, and the oxygen permeability is better than that of EVOH material, and PGA has potential application value in the fields of agricultural production, catering packaging, oil field exploitation and tissue engineering. However, PGA material is a brittle material with low impact strength, and is easily flammable with a large amount of flaming molten droplets, which needs to be solved in the wide application of PGA.

[0003] Glass fiber has excellent insulation, heat resistance, corrosion resistance and mechanical strength, and is often used to reinforce polymer materials to improve the comprehensive performance and application field of the materials. Patent (CN110682520B) discloses a preparation method of glass fiber reinforced thermoplastic resin composite material, which improves the retention length and distribution uniformity of glass fiber in the resin by selecting a high aspect ratio screw and using special screw shearing elements to control, thereby improving the strength and modulus of the composite material. Patent (CN111019315B) discloses a glass fiber reinforced PC material and a preparation method and use thereof. The author promotes the dispersion of glass fiber in the PC matrix by modifying the glass fiber and adding a compatibilizer to prepare a PC composite material with high strength and high toughness, but when the modified glass fiber filling amount exceeds 50 phr, the elongation at break and notched impact strength of the composite material are obviously reduced. Blending and extruding glass fiber and polymer is a conventional method for preparing glass fiber reinforced composite materials, but this method has problems such as floating fiber, uneven dispersion, reduced melt flowability, and low glass fiber loading, which need to be solved. In addition, polymer materials are extremely flammable, especially for glass fiber reinforced polymer materials, which have a "candle core effect" during combustion, further exacerbating the fire hazard of the composite material. Therefore, glass fiber reinforced composite materials urgently need to be flame-retardant modified.

[0004] Phosphorus-nitrogen type flame retardants have the advantages of high efficiency, environmental protection, etc., and are widely used in flame-retardant polymer materials. Patent (CN106398137B) discloses a halogen-free flame-retardant long glass fiber reinforced PET composite material and a preparation method thereof. The author melt blends halogen-free flame retardant DIDOPO and triazine charring agent with PET, and then continuously impregnates the mixed melt with long glass fiber to prepare a flame-retardant glass fiber reinforced PET composite material. Patent (CN113150527A) reports a high-weather-resistant glass fiber reinforced flame-retardant PC material and a preparation method thereof. By adding 2-10 parts of nitrogen-containing flame retardant, phosphorus-containing flame retardant and organic sulfonate flame retardant, the flame-retardant property of the glass fiber reinforced PC composite material is ensured. However, the existing technology has not studied the modification of PGA by phosphorus-nitrogen type flame retardant.

[0005] It is of great significance to apply glass fiber and phosphorus-nitrogen type flame retardant to the modification of PGA, improve the dispersion uniformity of glass fiber and flame retardant, and develop a new type of high-efficiency flame-retardant PGA composite material with excellent impact resistance. SUMMARY

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

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

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

[0009] As a preferred scheme of the composite material provided by the present application, the flame-retardant auxiliary agent is a composite flame-retardant auxiliary agent, which comprises a flame retardant, a charring agent, an anti-dripping agent, an antioxidant, an epoxidized elastomer and a vulcanizing agent;

[0010] Preferably, the content of the charring agent is 10-40 parts by weight, and / or the content of the anti-dripping agent is 0.1-3 parts by weight, and / or the content of the antioxidant is 0.1-2 parts by weight, and / or the content of the epoxidized elastomer is 5-20 parts by weight, and / or the content of the vulcanizing agent is 0.1-1.0 parts by weight, based on 100 parts by weight of the flame retardant;

[0011] More preferably, the content of the char-forming agent is 20-30 parts by weight, and / or the content of the anti-dripping agent is 0.1-2 parts by weight, and / or the content of the antioxidant is 0.1-1 part by weight, and / or the content of the epoxy elastomer is 10-15 parts by weight, and / or the content of the vulcanizing agent is 0.1-0.5 parts by weight, based on 100 parts by weight of the content of the flame retardant.

[0012] As another preferred scheme of the composite material provided by the present application, the flame retardant is a halogen-free flame retardant; preferably a phosphorus-based flame retardant; more preferably at least one of ammonium polyphosphate, melamine polyphosphate, piperazine pyrophosphate, red phosphorus, [(6-oxo-(6H)-dibenz-(CE)(1,2)-oxaphosphorin-6-keto)methyl]-succinic acid, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, aluminum diethylphosphinate, aluminum hypophosphite, lanthanum hypophosphite, cerium hypophosphite; further preferably ammonium polyphosphate and piperazine pyrophosphate;

[0013] and / or, the char-forming agent is selected from pentaerythritol derivatives and / or triazine derivatives; preferably, the pentaerythritol derivative is at least one of pentaerythritol, dipentaerythritol, cage pentaerythritol phosphate (PEPA), phenylphosphoryl-(bis-cage pentaerythritol phosphate) (BCPPO), poly(4,4-diaminodiphenylmethane-O-dicyclopentaerythritol phosphate) (PDBPP); preferably cage pentaerythritol phosphate (PEPA) and / or phenylphosphoryl-(bis-cage pentaerythritol phosphate) (BCPPO); and / or, the triazine derivative is at least one of 1,3,5-tris(2-hydroxyethyl)isocyanurate (Saytex), terephthalic acid Saytex, N-ethyl triazine-piperazine copolymer, N-hydroxyethyl triazine-ethylenediamine copolymer (CFA), macromolecular triazine char-forming agent HF-T1020; preferably N-ethyl triazine-piperazine copolymer and / or macromolecular triazine char-forming agent HF-T1020;

[0014] and / or, the anti-dripping agent is at least one of TF-1645, MM-5935EF, FA500H; preferably TF-1645 and / or FA500H;

[0015] and / or, the antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 626, antioxidant 2246, antioxidant PEPQ, and antioxidant 12; preferably antioxidant 1010 and / or antioxidant 168;

[0016] And / or, the epoxidized elastomer comprises at least one of epoxidized ethylene-vinyl acetate elastomer, epoxidized guttapercha, epoxidized natural rubber, epoxidized polybutadiene rubber, epoxidized polystyrene-butadiene-styrene thermoplastic elastomer; preferably epoxidized natural rubber and / or epoxidized ethylene-vinyl acetate elastomer.

[0017] And / or, the vulcanizing agent comprises one of sulfur, dicumyl peroxide and benzoyl peroxide, preferably dicumyl peroxide.

[0018] As another preferred scheme of the composite material provided by the present application, the preparation method of the composite flame-retardant aid comprises:

[0019] (1) mixing flame retardant, charring agent, anti-dripping agent and antioxidant in a high-speed mixer;

[0020] (2) mixing and vulcanizing the mixed powder obtained in step (1) and epoxidized elastomer in an internal mixer;

[0021] (3) crushing the mixture obtained in step (2) to obtain granular composite flame-retardant aid.

[0022] As another preferred scheme of the composite material provided by the present application, in the inner core material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the glass fiber is 10-200 parts by weight, preferably 10-150 parts by weight, more preferably 20-150 parts by weight;

[0023] And / or, in the outer layer material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the second polyglycolic acid resin is 1-100 parts by weight, preferably 10-100 parts by weight, more preferably 50-100 parts by weight;

[0024] And / or, in the composite material, the amount of the second polyglycolic acid resin is 100 parts by weight, and the amount of the composite flame-retardant aid is 30-100 parts by weight, preferably 50-80 parts by weight.

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

[0026] And / or, the second polyglycolic acid resin is used in an amount of 100 parts by weight, the second auxiliary agent includes at least one of 0.05-5 parts by weight of a second compatibilizer, 0.1-3 parts by weight of a second antioxidant and 0.1-1 part by weight of a second lubricant; preferably, the second polyglycolic acid resin is used in an amount of 100 parts by weight, the second auxiliary agent includes at least one of 0.05-2 parts by weight of a second compatibilizer, 0.1-1 part by weight of a second antioxidant and 0.2-1 part by weight of a second lubricant.

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

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

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

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

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

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

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

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

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

[0036] S2. performing 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, the flame-retardant auxiliary agent 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 halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material.

[0039] As a preferred embodiment of the method for preparing the composite material, 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 method for preparing the composite material, 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 method for preparing the composite material, step S2 further comprises: dispersing and preheating the continuous glass fiber before performing the first impregnation treatment; preferably, the preheating temperature is 80-250℃.

[0042] As another preferred embodiment of the method for preparing the composite material, step S4 further comprises: after the second impregnation treatment, pulling out, stretching, cooling, drying and cutting the material obtained after the second impregnation treatment to obtain the halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material.

[0043] As another preferred embodiment of the method for preparing the composite material, 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 communicated to form a combined flow channel for the fiber to pass through.

[0045] As another preferred scheme of the preparation method provided by the present application, the first impregnation treatment in step S2 is performed in a third impregnation mold, the third impregnation mold is a strong turbulent flow 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 communicated with a mold cavity in 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 fields of automobile and household appliances, packaging materials, building decoration, agricultural production and oil field chemical industry.

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

[0048] (1) The halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material provided by the present application has an inner-outer layer composite structure, and the functions of the inner and outer layers are complementary by adding different auxiliary fillers. The inner core material is obtained by coating continuous / constant-length glass fibers with a first polyglycolic acid resin, and the special impregnation process of the present application ensures that the high filling amount of glass fibers can still be uniformly dispersed in the first polyglycolic acid resin, and the inner core material provides excellent impact resistance, bending resistance and deformation resistance for the composite material; the outer layer material including the second polyglycolic acid resin and the flame-retardant auxiliary agent is coated on the surface of the inner core material, and provides good flame-retardant function for the composite material.

[0049] (2) The green halogen-free flame-retardant component in the composite flame-retardant auxiliary agent matches the environmental friendliness of the polyglycolic acid; the epoxidized elastomer material can react with the terminal carboxyl and terminal hydroxyl groups of the polyglycolic acid to play the roles of chain extension, compatibilization and toughening, and improve the impact resistance of the polyglycolic acid.

[0050] (3) The halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material has the advantages of low cost, simple process, good impact resistance, stable flame-retardant effect, good surface quality and the like, expands the application field of polyglycolic acid, and can be produced in an integrated continuous mode, thereby simplifying the molding process and improving the application value of polyglycolic acid. BRIEF DESCRIPTION OF DRAWINGS

[0051] Figure 1 A structure diagram of the halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material in an embodiment of the present application;

[0052] Figure 2 A structure diagram of a manufacturing system of the halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material in an embodiment of the present application;

[0053] Figure 3 A structure diagram of a manufacturing system of the halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material in another embodiment of the present application;

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

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

[0056] Figure 6 A sectional view of a third impregnation mold 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 sectional view of a molding mold used in the second impregnation process in an embodiment of the present application.

[0059] REFERENCE SIGNS:

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

[0061] 1, fiber frame and fiber guide device; 2, fiber pretreatment device; 3, first impregnation mold; 4, molten plasticizing feeding device; 5, molding mold; 6, cooling water tank; 7, drying machine; 8, traction machine; 9, granulator; 10, collection box;

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

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

[0064] C300, third impregnation die head; C1, melt slot channel; C2, impregnation 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 to be solved by the present application, technical solutions and beneficial effects more clearly, 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] In a first aspect, the present application provides a halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material, which comprises a core material and at least one outer layer material; the core material comprises a first polyglycolic acid resin, glass fibers and a first additive, the glass fibers continuously extend from one end of the core material to the opposite end; the outer layer material wraps the core material, and the outer layer material comprises a second polyglycolic acid resin, a flame-retardant additive and a second additive.

[0069] In the present application, a first component comprising a first polyglycolic acid resin and a first additive is used to impregnate continuous glass fibers to form a core material, and a second component comprising a second polyglycolic acid resin, a composite flame-retardant additive and a second additive is uniformly coated outside the core material, thereby forming a halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material with continuous glass fiber reinforced resin as the core material and resin layer wrapped outside the core material as the outer layer material. Such a polyglycolic acid composite material has excellent mechanical properties; at the same time, by adding a flame-retardant additive in the outer layer material, the composite material has good flame-retardant effect.

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

[0071] In the cross section of the halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite, the inner core material and the outer layer material are arranged from inside to outside, and the glass fiber is oriented along the longitudinal direction of the halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite in the inner core material.

[0072] The glass fiber in the present application is a glass fiber bundle, and the length of the fiber bundle is substantially the same as the length (longitudinal dimension) of the halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite, so that the fiber bundle continuously extends 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, non-oriented short fibers.

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

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

[0076] According to some embodiments of the present application, the flame retardant aid is a composite flame retardant aid, preferably, the composite flame retardant aid comprises a flame retardant, a char-forming agent, an anti-dripping agent, an antioxidant, an epoxidized elastomer and a vulcanizing agent.

[0077] According to some embodiments of the present application, the content of the char-forming agent is 10-40 parts by weight, and / or the content of the anti-dripping agent is 0.1-3 parts by weight, and / or the content of the antioxidant is 0.1-2 parts by weight, and / or the content of the epoxidized elastomer is 5-20 parts by weight, and / or the content of the vulcanizing agent is 0.1-1.0 parts by weight, based on 100 parts by weight of the flame retardant.

[0078] For example, the content of the char-forming agent can be 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, etc., and / or the content of the anti-dripping agent can be 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 content of the antioxidant can be 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, 1.5 parts by weight, 2 parts by weight, etc., and / or the content of the epoxidized elastomer can be 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, etc., and / or the content of the vulcanizing agent can be 0.1 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1.0 parts by weight, based on 100 parts by weight of the flame retardant.

[0079] According to some embodiments of the present application, the content of the flame retardant is 20-30 parts by weight, the content of the anti-dripping agent is 0.1-2 parts by weight, the content of the antioxidant is 0.1-1 parts by weight, the content of the epoxy elastomer is 10-15 parts by weight, and the content of the vulcanizing agent is 0.1-0.5 parts by weight, based on 100 parts by weight of the flame retardant.

[0080] According to some embodiments of the present application, the flame retardant is a halogen-free flame retardant; preferably a phosphorus-based flame retardant; more preferably at least one of ammonium polyphosphate, melamine polyphosphate, piperazine pyrophosphate, red phosphorus, [(6-oxo-(6H)-dibenz-(CE)(1,2)-oxaphosphorin-6- one)methyl]-succinic acid, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10- phosphaphenanthrene-10-oxide, aluminum diethylphosphinate, aluminum hypophosphite, lanthanum hypophosphite, cerium hypophosphite; further preferably ammonium polyphosphate and / or piperazine pyrophosphate.

[0081] According to some embodiments of the present application, the char-forming agent is selected from at least one of pentaerythritol derivatives and / or triazine derivatives. Preferably, the pentaerythritol derivatives are at least one of pentaerythritol, dipentaerythritol, cage pentaerythritol phosphate (PEPA), phenylphosphoryl-(bis-cage pentaerythritol phosphate) (BCPPO), poly(4,4-diaminodiphenyl methane-O-dicyclopentaerythritol phosphate) (PDBPP); preferably cage pentaerythritol phosphate (PEPA) and / or phenylphosphoryl-(bis-cage pentaerythritol phosphate) (BCPPO).

[0082] The triazine derivatives are at least one of 1,3,5-tris(2-hydroxyethyl) isocyanurate (SEK), terephthalic acid SEK, N-ethyl triazine-piperazine copolymer, N-hydroxyethyl triazine- ethylenediamine copolymer (CFA), and macromolecular triazine char-forming agent HF-T1020; preferably N-ethyl triazine-piperazine copolymer and / or macromolecular triazine char-forming agent HF-T1020.

[0083] According to some embodiments of the present application, the anti-dripping agent is at least one of TF-1645, MM-5935EF, and FA500H; preferably TF-1645 and / or FA500H.

[0084] According to some embodiments of the present application, the antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 626, antioxidant 2246, antioxidant PEPQ, and antioxidant 12; preferably antioxidant 1010 and / or antioxidant 168.

[0085] According to some embodiments of the present application, the epoxidized elastomer comprises at least one of epoxidized ethylene-vinyl acetate elastomer, epoxidized guttapercha, epoxidized natural rubber, epoxidized polybutadiene rubber, epoxidized polystyrene-butadiene-styrene thermoplastic elastomer; preferably epoxidized natural rubber and / or epoxidized ethylene-vinyl acetate elastomer.

[0086] According to some embodiments of the present application, the vulcanizing agent comprises at least one of sulfur, dicumyl peroxide and benzoyl peroxide, preferably dicumyl peroxide.

[0087] According to some embodiments of the present application, the preparation method of the composite flame retardant aid comprises:

[0088] (1) mixing the flame retardant, the charring agent, the anti-dripping agent and the antioxidant in a high-speed mixer;

[0089] (2) mixing and vulcanizing the mixed powder obtained in step (1) and the epoxidized elastomer in an internal mixer;

[0090] (3) using an air jet mill to crush the mixture obtained in step (2) to obtain a granular composite flame retardant aid.

[0091] In the composite flame retardant aid of the present application, the flame retardant, the charring agent, the anti-dripping agent and the antioxidant are dispersed and coated by the epoxidized elastomer, which improves the dispersion effect of the flame retardant and other components in the polyglycolic acid resin and improves the flame retardant performance of the composite material. At the same time, the epoxidized elastomer can react with the terminal carboxyl and terminal hydroxyl groups of the polyglycolic acid, which plays a role of reactive compatibilization, chain extension and toughening in the polyglycolic acid matrix, improves the processing thermal stability and impact resistance of the composite material, and widens the application field of polyglycolic acid.

[0092] According to some embodiments of the present application, in the inner core material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the glass fiber is 10-200 parts by weight, for example, it can be 10 parts by weight, 20 parts by weight, 30 parts by weight, 50 parts by weight, 60 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, etc., preferably 10-150 parts by weight, more preferably 20-150 parts by weight.

[0093] According to some embodiments of the present application, in the composite material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the second polyglycolic acid resin is 1-100 parts by weight, for example, it can be 1 part by weight, 10 parts by weight, 30 parts by weight, 50 parts by weight, 60 parts by weight, 80 parts by weight, 100 parts by weight, etc., preferably 10-100 parts by weight, more preferably 50-100 parts by weight.

[0094] 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 composite flame retardant aid is 30-100 parts by weight, for example, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, etc., preferably 50-80 parts by weight.

[0095] The specific types and amounts of the various aids in the first aid and the second aid are not limited in the present application, and are intended to achieve the relevant performance of the composite material and the effects of the relevant aids.

[0096] According to some embodiments of the present application, the amount of the first polyglycolic acid resin is 100 parts by weight, and the first aid includes at least one of 0.05-5 parts by weight of a first compatibilizer, 0.1-3 parts by weight of a first antioxidant, and 0.1-1 parts by weight of a first lubricant. For example, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of the first compatibilizer can be 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 amount of the first antioxidant can be 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 amount of the first lubricant can be 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, etc. Preferably, the amount of the first polyglycolic acid resin is 100 parts by weight, and the first aid includes at least one of 0.05-2 parts by weight of a first compatibilizer, 0.1-1 parts by weight of a first antioxidant, and 0.2-1 parts by weight of a first lubricant.

[0097] According to some embodiments of the present application, the second polyglycolic acid resin is used in an amount of 100 parts by weight, and the second auxiliary agent includes at least one of 0.05-5 parts by weight of a second compatibilizer, 0.1-3 parts by weight of a second antioxidant, and 0.1-1 parts by weight of a second lubricant. For example, the second polyglycolic acid resin is used in an amount of 100 parts by weight, and the second compatibilizer can be used in an amount of 0.05 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 1 parts by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, etc.; and / or, the second antioxidant can be used in an amount of 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 1 parts by weight, 2 parts by weight, 3 parts by weight, etc.; and / or, the second lubricant can be used in an amount of 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, etc. Preferably, the second polyglycolic acid resin is used in an amount of 100 parts by weight, and the second auxiliary agent includes at least one of 0.05-2 parts by weight of a second compatibilizer, 0.1-1 parts by weight of a second antioxidant, and 0.2-1 parts by weight of a second lubricant.

[0098] According to some embodiments of the present application, the first compatibilizer and the second compatibilizer are the same or different, and each is independently selected from at least one of a coupling agent, preferably at least one of a silane coupling agent, a titanate coupling agent, an organic chromium complex coupling agent, more preferably a silane coupling agent. Examples of the silane coupling agent suitable for use in the present application include, but are not limited to, KH-550, KH-560.

[0099] According to some embodiments of the present application, the first antioxidant and the second antioxidant are the same or different, and each is independently selected from at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 2246, antioxidant CA, and antioxidant 626, preferably antioxidant 1010 and / or antioxidant 168.

[0100] According to some embodiments of the present application, the first lubricant and the second lubricant are the same or different, and each is independently selected from at least one of ethylene bis-stearamide, calcium stearate, monoglyceride fatty acid, polyethylene wax, erucamide, pentaerythritol stearate.

[0101] In different embodiments of the present application, the first auxiliary agent and the second auxiliary agent are not limited to the specific types and amounts of the auxiliary agents, and each can have a wide range of selection. For example, the first auxiliary agent and the second auxiliary agent each independently can further include at least one of a chain extender, a slip agent, an antistatic agent, and a plasticizer. The specific types and amounts of the auxiliary agents can each have a wide range of selection.

[0102] 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 polyglycolic acid and / or copolymer polyglycolic acid; preferably, the content of glycolic acid monomer in the copolymer polyglycolic acid is ≥ 90 mol%, preferably ≥ 95 mol%.

[0103] The comonomer of the copolymer polyglycolic acid can include: cyclic monomers such as 1,4-dioxane-2,3-dione, lactide, lactone (e.g., pivalolactone, butyrolactone, pivalolactone, butyrolactone, 8-valerolactone, ethyl 8-valerolactone, E-caprolactone), carbonate (e.g., trimethylene carbonate), ether (e.g., 1,3-dioxane), ether ester (e.g., dioxanone), amide (e.g., E-caprolactam), lactic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, and 6-hydroxyhexanoic acid, and alkyl esters thereof; essentially equimolar mixtures of aliphatic diols (e.g., ethylene glycol and 1,4-butanediol) and aliphatic dicarboxylic acids (e.g., succinic acid and adipic acid) or alkyl esters thereof; and combinations of two or more of the above.

[0104] 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 glycolide can be obtained by a coal chemical method.

[0105] 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.

[0106] In particular, the present inventors have found that the polyglycolic acid composite material prepared according to the parameters (e.g., melt flow rate) of the present application has high surface quality performance and comprehensive performance. For example, the melt flow rate of the first polyglycolic acid resin is higher than that of the second polyglycolic acid resin, so that the polyglycolic acid composite material has improved mechanical properties; 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.

[0107] According to some embodiments of the present application, the first polyglycolic acid resin has a melt flow rate of 5-500 g / 10 min at 230°C, 2.16 kg, for example, 5 g / 10 min, 10 g / 10 min, 20 g / 10 min, 40 g / 10 min, 50 g / 10 min, 80 g / 10 min, 100 g / 10 min, 150 g / 10 min, 200 g / 10 min, 300 g / 10 min, 400 g / 10 min, 500 g / 10 min, etc., preferably 10-200 g / 10 min, more preferably 10-150 g / 10 min.

[0108] 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 g / 10 min, 10 g / 10 min, 20 g / 10 min, 40 g / 10 min, 50 g / 10 min, 80 g / 10 min, 100 g / 10 min, 150 g / 10 min, 200 g / 10 min, 300 g / 10 min, 400 g / 10 min, 500 g / 10 min, etc., preferably 10-200 g / 10 min, more preferably 10-150 g / 10 min.

[0109] According to some embodiments of the present application, the composite material is in the form of a strip, a rod or a particle.

[0110] In the present application, the strip, rod or particle-shaped halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material can be cut from a continuous filament halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material.

[0111] Preferably, the length of the strip or rod-shaped composite material is 6-25 mm, for example, 6 mm, 8 mm, 10 mm, 12 mm, 15 mm, 20 mm, 22 mm, 25 mm, etc., preferably 8-20 mm, more preferably 10-15 mm; and / or the particle diameter of the particle-shaped composite material is 3-5 mm, for example, 3 mm, 4 mm, 5 mm, etc., preferably 3-4 mm.

[0112] The present application does not have special requirements for the cross-sectional shape of the halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material. In some embodiments, the cross-section of the particle or rod-shaped halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material is circular or circular-like. In other embodiments, the cross-section of the particle or strip-shaped halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material is rectangular or square.

[0113] In a second aspect, the present application provides a method for preparing a halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material, comprising:

[0114] S1. mixing and melting the first polyglycolic acid resin and the first additive to obtain a first component melt;

[0115] 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;

[0116] S3. mixing and melting the second polyglycolic acid resin, the flame-retardant additive and the second additive to obtain a second component melt;

[0117] 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 halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material.

[0118] 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.

[0119] According to some embodiments of the present application, the mixing conditions in step S1 are that the temperature is 40-60°C and the time is 3-5 min; and / or the melting temperature in step S1 is 230-260°C.

[0120] According to some embodiments of the present application, the mixing conditions in step S3 are that the temperature is 40-60°C and the time is 3-5 min; and / or the melting temperature in step S3 is 230-260°C.

[0121] In the present application, the time for melting in steps S1 and S3 can have a wide selection range, so as to enable the first polyglycolic acid resin and the first additive, and the second polyglycolic acid resin, the flame-retardant additive and the second additive to be fully melted to obtain a melt.

[0122] According to some embodiments of the present application, the step S2 further comprises: before performing the first impregnation treatment on the continuous glass fiber, performing a dispersion treatment and a preheating treatment on the continuous glass fiber; preferably, the temperature for the preheating treatment is 80-250°C. The dispersion treatment process in the present application adopts a conventional fiber dispersion treatment process in the art.

[0123] 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 granulating treatment on the composite material obtained after the second impregnation treatment to obtain the halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material. The process conditions for the pulling-out, stretching, cooling, drying and granulating treatment are not particularly limited, and a person skilled in the art can adjust them according to the specific performance requirements of the prepared halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material.

[0124] According to some embodiments of the present application, the first impregnation process in step S2 can be performed in a first impregnation die, which is an adjustable impregnation die, the first impregnation die comprising a fiber inlet, a fiber outlet and a melt runner, at least one first godet being arranged in a die cavity of the first impregnation die; 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 a line connecting the fiber inlet and the fiber outlet.

[0125] According to some embodiments of the present application, the first impregnation process in step S2 can be performed in a second impregnation die, which is a combined impregnation die, 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 runner, the second module being provided with a fiber outlet and a second module runner, the intermediate module being provided with an intermediate module runner; after the first module, the intermediate module and the second module are connected in sequence, the first module runner, the intermediate module runner and the second module runner are connected in communication to form a combined runner for the fibers to pass through.

[0126] According to some embodiments of the present application, the first impregnation process in step S2 can also be performed in a third impregnation die, which is a strong turbulent impregnation die, the third impregnation die comprising a fiber inlet channel, an impregnation outlet and a melt slit runner, the fiber inlet channel, the impregnation outlet and the melt slit runner all being connected 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 driven godet, the driven godet being driven to rotate by a driving device.

[0127] 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.

[0128] 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 halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite materials.

[0129] According to some embodiments of the preparation method of the present application, the second impregnation treatment in step S4 can be performed in a forming mold. The forming mold is composed of a core, an outer sleeve, and an outer sleeve die plate. The core is located inside the outer sleeve to form a cavity with the outer sleeve, and the resin melt can enter the cavity from the bottom or top or both sides of the outer sleeve. The core can move forward and backward in the outer sleeve to adjust the size of the cavity formed to determine the pressure of the melt in the cavity. The pressure of the melt in the cavity can also be adjusted by the angle between the core and the outer sleeve. The working principle of the forming mold is as follows: the strip formed after impregnation in the impregnation mold is guided to pass through the hole in the middle of the core, and then the inner and outer layer material composite structure is formed in the cavity formed by the core and the outer sleeve filled with mixed melt, and finally it is guided out through the outer sleeve die plate.

[0130] The present application will be further described below with reference to the accompanying drawings.

[0131] Figure 1 The structure of the halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material of the present application is shown. As shown in Figure 1 , the cross section of the halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material of the present application is circular, and sequentially includes an inner core material 0-1 and an outer layer material 0-3 from inside to outside, the inner core material 0-1 has fiber bundles 0-2 oriented in the longitudinal direction distributed therein, and the fiber bundles 0-2 are uniformly dispersed in the inner core material 0-1.

[0132] As shown in Figure 2 and Figure 3 , the manufacturing system of the present application includes a fiber rack and fiber guiding device 1, a fiber pretreatment device 2, a first impregnation mold 3, a melt plasticizing feeding device 4, a forming mold 5, a cooling water tank 6, a drying machine 7, a traction machine 8, a granulator 9, a collection box 10, and an electric control system (not shown in the figure) connected in sequence.

[0133] In the manufacturing system, the forming mold 5 is used for the forming of the halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material, and its structure is shown in Figure 8 .

[0134] In the manufacturing system, the first impregnation mold 3 is used for the impregnation of the fiber and the first polyglycolic acid resin melt.

[0135] As shown in Figure 4As shown, in one embodiment, the first impregnation die is an adjustable godet position impregnation device, which includes a first impregnation die head A300, the first impregnation die head A300 includes an impregnation die body A7, a fiber inlet A1, a fiber outlet A6, and a melt flow channel A3. At least one first godet A8 is arranged in the die cavity, wherein the first godet A8 is movable between the fiber inlet A1 and the fiber outlet A6, or the first godet A8 is movable in a direction perpendicular to the line connecting the fiber inlet A1 and the fiber outlet A6, or the first godet A8 is movable both between the fiber inlet A1 and the fiber outlet A6 and in a direction perpendicular to the line connecting the fiber inlet A1 and the fiber outlet A6.

[0136] Taking a rectangular first impregnation die head A300 as an example, a plurality of first godets A8 are arranged in the first impregnation die head A300, and the axial direction of each first godet A8 is the width direction of the first impregnation die head A300. Therefore, each first godet A8 is movable in the length direction of the first impregnation die head A300 and is also movable in the height direction, so as to change the position of the first godet A8 in the first impregnation die head A300.

[0137] It can be understood that the axial direction of the first godet A8 can also be the length direction of the first impregnation die head A300. At this time, each first godet A8 is movable in the width direction of the first impregnation die head A300 and is also movable in the height direction of the first impregnation die head A300, so as to change the position of the first godet A8 in the first impregnation die head A300.

[0138] Since the fiber needs to pass around the first godet A8 in the die cavity when walking in the die cavity of the first impregnation die head A300, by changing the position (horizontal position, longitudinal position, etc.) of the first godet A8 in the first impregnation die head A300, the walking path of the fiber in the die cavity can be changed. Therefore, when the required impregnation condition of the fiber changes, it is not necessary to replace a new die, but only to adjust the position of the first godet A8 in the first impregnation die head A300, thereby improving the production efficiency and the continuity of production. At the same time, the number of first impregnation die heads A300 can be reduced, and the production cost can be saved.

[0139] Specifically, the present application is to adjust the position of the first godet A8 by slotting the inner wall of the die cavity of the first impregnation die head A300.

[0140] A first sliding groove A4 is arranged on the first inner wall of the first impregnation die head A300, and the first sliding groove A4 extends between the fiber inlet A1 and the fiber outlet A6 (i.e. Figure 4As shown in the Y-axis direction), the first godet roll A8 moves along the second runner A2 to change its vertical position in the die head.

[0141] Further, the first inner wall of the first impregnation die head A300 is also provided with a second runner A2 extending in a direction perpendicular to the first runner A4 (i.e. Figure 4 As shown in the Y-axis direction), the first godet roll A8 moves along the second runner A2 to change its vertical position in the die head.

[0142] It should be noted that the first runner A4 and the second runner A2 can be connected. Thus, the first godet roll A8 can be arbitrarily moved in the longitudinal direction or the transverse direction, so that its position is changed.

[0143] The cross section of the first runner A4 and the second runner A2 can be trapezoidal, circular, arc-shaped or rectangular, and the present application does not limit it.

[0144] The two ends of the first godet roll A8 are provided with adjusting devices (not shown in the figure), which are used to adjust the axial length of the first godet roll A8. The minimum axial length of the first godet roll A8 is less 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.

[0145] As Figure 5 As shown in another embodiment of the present application, the second impregnation die is a combined impregnation die, which includes a second impregnation die head B300. The second impregnation die head B300 includes a first module B3, an intermediate module B6 and a second module B7 connected in sequence. The first module B3 is provided with a fiber inlet B1 and a first module flow channel B31, the second module B7 is provided with a fiber outlet B8 and a second module flow channel B71, and the intermediate module B6 is provided with an intermediate module flow channel B61.

[0146] 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. 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.

[0147] That is, the number of intermediate modules B6 can be increased or decreased as required, so that different intermediate modules B6 are combined to form the combined second impregnation die B300 when the impregnation requirements change, thereby improving the continuity and efficiency of production and saving the cost of additional die opening.

[0148] Furthermore, by selecting different intermediate modules B6, the shape parameters (such as curvature, etc.) of the combined flow channel B4 formed can be changed, so that the flow path of the fiber and the melt can be changed, the fiber impregnation angle and fiber tension in different stations of the die can be changed, the entire fiber impregnation process can be adjusted and optimized, and the adaptability of the second impregnation die B300 to polyglycolic acid resin and fiber is improved.

[0149] The first module B3, the intermediate module B6 and the second module B7 are placed in the die holder, and the constraint action of the die holder makes them in close contact with each other, so as to ensure the sealing of the combined flow channel B4.

[0150] As shown in Figure 5 , an embodiment with 2 intermediate modules B6 is shown. In the embodiment shown in Figure 5 , the downstream end of the first module flow channel B31 is connected to the upstream end of one of the intermediate module flow channels B61, the two intermediate module flow channels B61 are connected to each other, and the downstream end of the other intermediate module flow channel B61 is connected to the upstream end of the second intermediate module flow channel B71, thereby forming a combined flow channel B4 extending from the fiber inlet B1 to the fiber outlet B8.

[0151] It can be understood that by selecting different intermediate modules B6, different combined flow channels B4 can be obtained.

[0152] As shown in Figure 5 , the downstream end of the first module flow channel B31, the upstream end of the second module flow channel B71 and the two ends of the intermediate module flow channel B61 are located in the same plane and are provided with standardized joints B5. In other words, the connection between the first module flow channel B31, the intermediate module flow channel B61 and the second module B71 is connected by the standardized joints B5. Since the standardized joints B5 are located in the same plane, and the shape and size of the standardized joints B5 are the same, the combination and connection between different modules are facilitated.

[0153] As shown in Figure 6As shown, in still another embodiment of the present application, the third impregnation die is a strong turbulent impregnation die, which comprises a third impregnation die head C300, the third impregnation die head C300 comprises an impregnation die outer body C2, the impregnation die outer body C2 is provided with a fiber inlet channel C3, an impregnation outlet C6 and a melt slit runner C1, the fiber inlet channel C3, the impregnation outlet C6 and the melt slit runner C1 are all connected with the die cavity inside the impregnation die outer body C2.

[0154] The die cavity of the impregnation die outer body C2 is provided with a second godet, the second godet comprises at least one driving godet C4, the driving godet C4 is driven to rotate by a driving device (not shown in the figure). Since the rotation of the driving godet C4 is driven by the driving device, rather than being driven by the traction of the fiber, when the fiber passes through the driving godet C4, the driving godet C4 driven to rotate helps to reduce the traction tension of the fiber and the friction between the fiber and the driving godet C4, thereby reducing the breaking amount of the fiber, ensuring the integrity of the fiber, avoiding the fiber being pulled off, and thus improving the mechanical properties of the material.

[0155] Preferably, the second godet further comprises at least one driven godet C5, the driven godet C5 is driven by the fiber passing through the driving godet C4; or the driven godet C5 is connected with the driving godet C4 through a belt mechanism, a gear mechanism or a chain mechanism.

[0156] As shown in the figure, Figure 6 An example with one driving godet C4 and two driven godets C5 is shown, wherein the two driven godets C5 are arranged one above the other to extend the impregnation path of the fiber passing therethrough. The heights of the driving godet C4 and the driven godets C5 in the die cavity can be the same or different.

[0157] Further, the driving device can be a motor, a hydraulic mechanism or a reduction box, etc. which can drive the driving godet C4 to rotate.

[0158] According to the running speed v1 of the fiber entering the die cavity of the impregnation die outer body C2, the corresponding tangential speed v2 of the driving godet C4 can be selected, for example, the tangential speed v2 of the driving godet C4 is the same as the running speed v1 of the fiber, i.e. v1=v2, so as to achieve the purpose of reducing the breaking and wear of the fiber, thus ensuring the integrity of the fiber and promoting the impregnation degree of the fiber, shortening the impregnation time and improving the production efficiency.

[0159] As shown in the figure, Figure 2As shown, the melt plasticizing feeding device 4 consists of a twin-screw extruder used for melting and plasticizing materials. The twin-screw extruder is a co-rotating twin-screw extruder with a screw diameter of 25mm-95mm and a length-to-diameter ratio of 36:1-65:1. When the melt plasticizing feeding device 4 consists of a single extruder 4, the melt plasticizing material in the extruder is divided by a melt distributor and fed into the impregnation die and the forming die respectively, and the flow rate of each die is controlled by a melt flow control valve.

[0160] 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.

[0161] 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.

[0162] In the manufacturing system, the fiber frame and fiber guiding device 1 are used for fiber output and untwisting. The device is equipped with an automatic control untwisting device, which is linked with the traction machine 8 and electrically connected to the electrical control system (such as a PLC control device).

[0163] In the manufacturing system, the cooling water tank 6, dryer 7, traction machine 8, pelletizer 9, and collection box 10 are conventional equipment or devices known to those skilled in the art, and will not be described in detail here.

[0164] Figure 7 A schematic diagram showing the second impregnation process using a molding die is shown. Figure 8 A cross-sectional view of the molding die used in the second impregnation process is shown.

[0165] like Figure 8As shown, in one embodiment, the forming mold 5 is composed of a core 5-1, an outer sleeve 5-2, and an outer sleeve die plate 5-3. The core 5-1 is located inside the outer sleeve 5-2, and forms a cavity with the outer sleeve 5-2, and the resin melt can enter the cavity from the bottom or top or both sides of the outer sleeve 5-2. The core 5-1 can move forward and backward in the outer sleeve 5-2, and the pressure of the melt in the cavity can be adjusted by adjusting the size of the cavity formed. The pressure of the melt in the cavity can also be adjusted by the angle between the core 5-1 and the outer sleeve 5-2. The working principle of the forming mold 5 is as follows: the rod formed after the impregnation mold 3 impregnates the inner layer impregnated material, is guided to pass 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 formed by the core 5-1 and the outer sleeve 5-2 filled with the mixed melt, and finally is guided out through the outer sleeve die plate 5-3.

[0166] As shown in Figure 7 , the rod 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.

[0167] In the following examples and comparative examples, the manufacturing system shown in Figure 3 is used to prepare halogen-free flame-retardant glass fiber reinforced polyglycolic acid composites, wherein the first impregnation treatment uses the first impregnation mold shown in Figure 4 , and the second impregnation treatment uses the forming mold shown in Figure 8 .

[0168] The halogen-free flame-retardant 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.

[0169] Unless otherwise defined, the technical terms used in the following examples have the same meanings as generally understood by those skilled in the art to which the present application belongs. The reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the raw materials, instruments and equipment used in the following examples can be purchased on the market or obtained by existing methods; the amount of the reagents, unless otherwise specified, is the amount of the reagents in conventional experimental operations; and the experimental methods, unless otherwise specified, are conventional methods.

[0170] In each of the embodiments and comparative examples of the present application, the test methods for each performance data are as follows:

[0171] (1) Tensile strength: GB / T 1040-2018;

[0172] (2) Flexural modulus: GB / T 9341-2008;

[0173] (3) Impact strength: GB / T 1843-2008;

[0174] (4) Heat distortion temperature: GB / T 1634-2004, A method, bending stress 1.8 MPa.

[0175] In the embodiments and comparative examples of the present application, the materials used are as follows:

[0176] (1) Polyglycolic acid: homopolymer polyglycolic acid, melt index 10, 40 g / 10 min (2.16 kg, 230°C), Shanghai Pujing Chemical Industry;

[0177] (2) Glass fiber: alkali-free glass fiber, diameter 17 μm, linear density 2400 tex, Chongqing International Composite Material Co., Ltd.;

[0178] (3) Flame retardant ammonium polyphosphate: AP422, Jinan Taixing Fine Chemical Co., Ltd.;

[0179] (4) Caged pentaerythritol phosphate: Guangzhou Xijia New Material Co., Ltd.;

[0180] (5) Macromolecular triazine charring agent: HF-T1020, Zhongshan Kangnuo New Material Co., Ltd.;

[0181] (6) Epoxidized natural rubber: ENR-50, Shandong Mingyao New Material Co., Ltd.;

[0182] (7) Natural rubber: SCR 5, Hainan Natural Rubber Industry Group Co., Ltd.

[0183] (8) Anti-dripping agent: TF-1645, 3M Company, USA;

[0184] (9) Antioxidant 1010: Irganox 1010, BASF, Germany;

[0185] (10) Antioxidant 168: Irgafos 168, BASF, Germany;

[0186] (12) Silane coupling agent: KH-550, Nanjing Youpu Chemical Co., Ltd.;

[0187] (13) Erucic acid amide: CHSLIP SEA, Hunan Changsha Hengchang Chemical Co., Ltd.;

[0188] (14) Calcium stearate: Nanjing Jinling Chemical Factory Co., Ltd.

[0189] (15) Dicumyl peroxide: analytical pure, National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0190] Preparation Example 1

[0191] (1) 100 parts by weight of ammonium polyphosphate, 30 parts by weight of caged pentaerythritol phosphate, 1.0 part by weight of anti-dripping agent TF-1645 and 0.2 part by weight of antioxidant 1010 were mixed in a high-speed mixer. The mixing time was 10 min and the rotation speed was 800 r / min.

[0192] (2) The uniformly mixed powder in (1) was mixed with 15 parts by weight of epoxidized natural rubber ENR-50 in a Haake torque rheometer for 15 min at a temperature of 100°C and a rotation speed of 70 r / min. After the blending was completed, the temperature was raised to 170°C, 0.3 parts by mass of dicumyl peroxide was added, and dynamic vulcanization was performed for 10 min.

[0193] (3) The mixture obtained in (2) was subjected to a crushing treatment to obtain a granular composite flame-retardant aid CFR-1.

[0194] Preparation Example 2

[0195] (1) 100 parts by weight of ammonium polyphosphate, 30 parts by weight of macromolecular triazine charring agent HF-T1020, 1.0 part by weight of anti-dripping agent TF-1645 and 0.2 part by weight of antioxidant 1010 were mixed in a high-speed mixer. The mixing time was 10 min and the rotation speed was 800 r / min.

[0196] (2) The uniformly mixed powder in (1) was mixed with 15 parts by weight of epoxidized natural rubber ENR-50 in a Haake torque rheometer for 15 min at a temperature of 100°C and a rotation speed of 70 r / min. After the blending was completed, the temperature was raised to 170°C, 0.3 parts by mass of dicumyl peroxide was added, and dynamic vulcanization was performed for 10 min.

[0197] (3) The mixture obtained in (2) was subjected to a crushing treatment to obtain a granular composite flame-retardant aid CFR-2.

[0198] Preparation Example 3

[0199] (1) 100 parts by weight of ammonium polyphosphate, 30 parts by weight of caged pentaerythritol phosphate, 1.0 part by weight of anti-dripping agent TF-1645 and 0.2 part by weight of antioxidant 1010 were mixed in a high-speed mixer. The mixing time was 10 min and the rotation speed was 800 r / min.

[0200] (2) The uniformly mixed powder in (1) was mixed with 15 parts by weight of natural rubber (not epoxidized) in a Haake torque rheometer for 15 min at a temperature of 100°C and a rotation speed of 70 r / min. After the blending was completed, the temperature was raised to 170°C, 0.3 parts by mass of dicumyl peroxide was added, and dynamic vulcanization was performed for 10 min.

[0201] (3) The mixture obtained in (2) was subjected to a crushing treatment to obtain a granular composite flame-retardant aid CFR-3.

[0202] Example 1

[0203] (1) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) was mixed with 1.0 part by weight of KH550, 0.25 part by weight of antioxidant 168, and 0.35 part by weight of erucic acid amide in a high-speed mixer, stirred at 50°C for 3 minutes to obtain a first component melt, and fed into a first impregnation mold.

[0204] (2) Continuous glass fibers were introduced into the first impregnation mold under the action of a pulling machine, impregnated and dispersed with the first component melt to form a sample, which was used as an inner layer material, and the glass fiber content was 100 parts by weight.

[0205] (3) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) was mixed with 80 parts by weight of composite flame retardant aid CFR-1, 1.0 part by weight of KH550, 0.25 part by weight of antioxidant 168, and 0.35 part by weight of erucic acid amide in a high-speed mixer, stirred at 50°C for 3 minutes, used as an outer layer material, and fed into a double-screw extruder connected to a molding mold to obtain a second component melt.

[0206] (4) The inner layer material was introduced into the molding mold under the action of the pulling machine, guided through the hole in the middle of the core, and the outer sleeve formed a cavity filled with the second component melt, realizing the molding of the inner and outer layer material composite structure, and finally guided out through the outer sleeve die plate.

[0207] (5) The amount of outer layer material was adjusted by adjusting the amount of extrusion of the extruder for the outer layer material and the diameter of the die outlet of the mold, so that it was coated according to the defined amount, and the cutter speed of the cutter was adjusted to control the length of the obtained polyglycolic acid composite material to be 15 mm. The content of polyglycolic acid in the obtained composite material was 100 parts by weight, the content of glass fiber was 50 parts by weight, and the content of composite flame retardant aid CFR-1 was 40 parts by mass.

[0208] (6) The halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material prepared by the above method was injection molded into a standard sample, and the limiting oxygen index (LOI), vertical burning (UL-94) and mechanical property tests were carried out. The test results are shown in Table 1.

[0209] Comparative Example 1

[0210] The preparation process was the same as that of Example 1, except that 80 parts by weight of composite flame retardant aid CFR-1 was not added in step (3). The polyglycolic acid composite material was injection molded into a standard sample, and the performance test was carried out. The test results are shown in Table 1.

[0211] Example 2

[0212] The preparation process is the same as that in Example 1, except that 80 parts by weight of the composite flame retardant aid CFR-1 in step (3) is replaced by the composite flame retardant aid CFR-3. The polyglycolic acid composite is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0213] Comparative Example 2

[0214] (1) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) is added to a high-speed mixer with 1.0 parts by weight of KH550, 0.25 parts by weight of antioxidant 168, and 0.35 parts by weight of erucic amide, stirred at 50°C for 3 minutes to obtain a first component melt, and fed into a first impregnation mold.

[0215] (2) Continuous glass fibers are introduced into the first impregnation mold under the action of a traction machine to impregnate and disperse with the above-mentioned first component melt, forming a sample bar, which is used as an inner layer material, wherein the glass fiber content is 100 parts by weight.

[0216] (3) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min), 54.6 parts by weight of ammonium polyphosphate, 16.4 parts by weight of caged pentaerythritol phosphate, 0.5 parts by weight of anti-dripping agent TF-1645, 0.1 parts by weight of antioxidant 1010, 8.2 parts by weight of epoxidized natural rubber ENR-50, and 0.2 parts by weight of vulcanizing agent dicumyl peroxide are mixed in a high-speed mixer for 10 minutes. It is used as an outer layer material and is fed into a double-screw extruder connected to a molding mold to obtain a second component melt.

[0217] (4) The inner layer material is introduced into the molding mold under the action of the traction machine, guided through the hole in the middle of the core, and realizes the molding of the inner and outer layer material composite structure in the cavity filled with the second component melt formed by the core and the outer sleeve. Finally, it is guided out through the outer sleeve die plate.

[0218] (5) The amount of outer layer material is adjusted by adjusting the amount of extrusion of the extruder for the outer layer material and the diameter of the die plate exit of the mold, so that it is coated according to the defined amount. The cutter speed of the granulator is adjusted to control the length of the obtained polyglycolic acid composite material to be 15 mm. The content of polyglycolic acid in the obtained composite material is 100 parts by weight, the content of glass fiber is 50 parts by weight, the content of ammonium polyphosphate is 27.3 parts by weight, the content of caged pentaerythritol phosphate is 8.2 parts by weight, and the content of epoxidized natural rubber ENR-50 is 4.1 parts by weight.

[0219] (6) The halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material prepared by the above method is injection molded into a standard sample bar for limiting oxygen index (LOI), vertical burning (UL-94) and mechanical property testing. The test results are shown in Table 1.

[0220] Comparative Example 3

[0221] (1) 100 parts by weight of polyglycolic acid (melt index 40 g / 10 min) was mixed with 1.0 parts by weight of KH550, 0.25 parts by weight of antioxidant 168, 0.35 parts by weight of erucamide, 100 parts by weight of glass fiber of 15 mm in length in a high-speed mixer, and stirred at 50°C for 3 minutes.

[0222] (2) 100 parts by weight of polyglycolic acid (melt index 10 g / 10 min) was mixed with 80 parts by weight of composite flame retardant aid CFR-1 in a high-speed mixer for 10 minutes.

[0223] (3) The two mixtures above were added together into a twin-screw extruder for melt granulation, and the obtained polyglycolic acid composite material particles were 15 mm in length. The obtained composite material contained 100 parts by weight of polyglycolic acid, 50 parts by weight of glass fiber, and 40 parts by weight of composite flame retardant aid CFR-1.

[0224] (4) The halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material prepared by the above method was injection molded into standard bars, and subjected to limiting oxygen index (LOI), vertical burning (UL-94), and mechanical property tests. The test results are shown in Table 1.

[0225] Comparative Example 4

[0226] The preparation process was the same as in Example 1, except that 80 parts by weight of composite flame retardant aid CFR-1 was not added in step (3), and 80 parts by weight of composite flame retardant aid CFR-1 was added in step (1). The polyglycolic acid composite material was injection molded into standard bars, and subjected to performance tests. The test results are shown in Table 1.

[0227] Comparative Example 5

[0228] The preparation process was the same as in Example 1, except that 40 parts by weight of composite flame retardant aid CFR-1 was added in step (1), and 40 parts by weight of composite flame retardant aid CFR-1 was added in step (3). The polyglycolic acid composite material was injection molded into standard bars, and subjected to performance tests. The test results are shown in Table 1.

[0229] Example 3

[0230] The preparation process is the same as that of Example 1, except that 1.0 parts by weight of KH550 in step (1) is replaced by 0.5 parts by weight of KH550, 80 parts by weight of the composite flame retardant aid CFR-1 in step (3) is replaced by the composite flame retardant aid CFR-2, 0.35 parts by weight of erucamide is replaced by 0.5 parts by weight of calcium stearate, and the pelletizing length of 15 mm in step (5) is replaced by a pelletizing length of 10 mm. The polyglycolic acid composite is injection molded into a standard sample bar, and performance testing is performed. The test results are shown in Table 1.

[0231] Example 4

[0232] The preparation process is the same as that of Example 1, except that the addition amount of the composite flame retardant aid CFR-1 in step (3) is replaced from 80 parts by weight to 50 parts by weight. The polyglycolic acid composite is injection molded into a standard sample bar, and performance testing is performed. The test results are shown in Table 1.

[0233] Example 5

[0234] The preparation process is the same as that of Example 1, except that the glass fiber content in step (2) is replaced from 100 parts by weight to 150 parts by weight. The polyglycolic acid composite is injection molded into a standard sample bar, and performance testing is performed. The test results are shown in Table 1.

[0235] Example 6

[0236] The preparation process is the same as that of Example 1, except that the glass fiber content in step (2) is replaced from 100 parts by weight to 20 parts by weight. The polyglycolic acid composite is injection molded into a standard sample bar, and performance testing is performed. The test results are shown in Table 1.

[0237] Table 1 Test results of material sample of examples and comparative examples

[0238]

[0239]

[0240] As can be seen from Example 1 and Comparative Example 1, the addition of the composite flame retardant aid endows the PGA composite material with better flame retardant performance, and the LOI is increased from 18.2% to 28.3%, and the vertical burning test reaches the V-0 level, but the mechanical properties of the composite material are reduced to some extent.

[0241] As can be seen from Example 1 and Example 2, the epoxidized elastomer is more beneficial to the mechanical properties of the composite material than the unepoxidized elastomer, because the epoxy group can react with the terminal hydroxyl and terminal carboxyl of the polyglycolic acid, has a certain chain extension effect, and weakens the deterioration of the mechanical properties of the composite material caused by heat processing.

[0242] From Example 1 and Comparative Example 2, it can be seen that adding the flame-retardant component in the form of a composite flame-retardant aid facilitates uniform dispersion of the flame-retardant aid and improves the flame-retardant properties of the composite material.

[0243] From Example 1 and Comparative Example 3, it can be seen that the processing method of impregnating continuous glass fibers can form a core-shell structure, the high content of glass fibers in the core layer is used to improve the mechanical properties of the PGA composite material, and the high content of flame retardant in the shell layer material is used to improve the flame-retardant properties of the PGA composite material, and the obtained PGA composite material has excellent mechanical properties and flame-retardant properties.

[0244] From Example 1 and Comparative Examples 4 and 5, it can be seen that the spatial distribution of the composite flame-retardant aid in the composite material has a significant effect on its flame-retardant properties. In the case of the same addition amount, adding the composite flame-retardant aid only in the inner layer or simultaneously adding it in the inner and outer layers is not conducive to the stable formation of the first melt-impregnated fibers, reduces the mechanical properties of the composite material, and simultaneously lacks or reduces the protection of the outer layer material by the flame-retardant layer, weakening the flame-retardant properties of the composite material.

[0245] From Comparative Examples 1-6, it can be seen that the composite flame-retardant aids CFR-1 and CFR-2 used in the present application both achieve good flame-retardant effects in the PGA matrix. The processing method of impregnating continuous glass fibers can achieve a high glass fiber addition amount, and a high glass fiber addition amount is conducive to improving the mechanical properties of the composite material, but the glass fiber reinforced composite material has a "wick effect" during combustion, which has a certain negative impact on the flame-retardant properties of the composite material.

[0246] It should be noted that the above-described examples are only used to explain the present application and do not constitute any limitation on the present application. The present application has been described by referring to typical examples, but it should be understood that the words used therein are descriptive and explanatory words, rather than limiting words. The present application can be modified as specified within the scope of the claims of the present application, and the present application can be revised without departing from the scope and spirit of the present application. Although the present application described therein relates to specific methods, materials and examples, it does not mean that the present application is limited to the specific examples disclosed therein, on the contrary, the present application can be extended to all other methods and applications with the same function.

Claims

1. A halogen-free flame-retardant 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 fiber and a first additive, the glass fiber continuously extends from one end of the inner core material to the opposite end; the outer layer material wraps the inner core material, and the outer layer material comprises a second polyglycolic acid resin, a flame-retardant additive and a second additive; In the inner core material, the amount of first polyglycolic acid resin is 100 parts by weight, and the amount of glass fiber is 10-200 parts by weight; In the outer layer material, the amount of first polyglycolic acid resin is 100 parts by weight, and the amount of second polyglycolic acid resin is 50-100 parts by weight; In the composite material, the amount of second polyglycolic acid resin is 100 parts by weight, and the amount of composite flame-retardant additive is 30-100 parts by weight; The flame-retardant additive is a composite flame-retardant additive, which comprises a flame retardant, a char-forming agent, an anti-dripping agent, an antioxidant, an epoxidized elastomer and a vulcanizing agent; the flame retardant is a halogen-free flame retardant; The content of the flame retardant is 100 parts by weight, the content of the char-forming agent is 10-40 parts by weight, the content of the anti-dripping agent is 0.1-3 parts by weight, the content of the antioxidant is 0.1-2 parts by weight, the content of the epoxidized elastomer is 5-20 parts by weight, and the content of the vulcanizing agent is 0.1-1.0 parts by weight.

2. The composite material of claim 1, wherein, The content of the flame retardant is 100 parts by weight, the content of the char-forming agent is 20-30 parts by weight, and / or the content of the anti-dripping agent is 0.1-2 parts by weight, and / or the content of the antioxidant is 0.1-1 parts by weight, and / or the content of the epoxidized elastomer is 10-15 parts by weight, and / or the content of the vulcanizing agent is 0.1-0.5 parts by weight.

3. The composite material of claim 1, wherein, The flame retardant is a phosphorus-based flame retardant; And / or, the char-forming agent is selected from pentaerythritol derivatives and / or triazine derivatives; And / or, the anti-dripping agent is at least one of TF-1645, MM-5935EF, and FA500H; And / or, the antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 626, antioxidant 2246, antioxidant PEPQ, and antioxidant 12; And / or, the epoxidized elastomer comprises at least one of epoxidized ethylene-vinyl acetate elastomer, epoxidized guttapercha, epoxidized natural rubber, epoxidized polybutadiene rubber, and epoxidized polystyrene-butadiene-styrene thermoplastic elastomer; And / or, the vulcanizing agent comprises at least one of sulfur, dicumyl peroxide, and benzoyl peroxide.

4. The composite material of claim 3, wherein, The flame retardant is at least one of ammonium polyphosphate, melamine polyphosphate, piperazine pyrophosphate, red phosphorus, [(6-oxo-(6H)-dibenzo-(CE)(1,2)-oxaphosphorin-6-yl)methyl]-succinic acid, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, aluminum diethylphosphinate, aluminum hypophosphite, lanthanum hypophosphite, and cerium hypophosphite. And / or, the pentaerythritol derivative is at least one of pentaerythritol, dipentaerythritol, cage pentaerythritol phosphate, phenylphosphoryl-(bis-cage pentaerythritol phosphate), poly(4,4-diaminodiphenylmethane-O-dicyclopentaerythritol phosphate); And / or, the triazine derivative is at least one of 1,3,5-tris(2-hydroxyethyl) isocyanurate, terephthalic acid secco, N-ethyl triazine-piperazine copolymer, N-hydroxyethyl triazine-ethylenediamine copolymer, and macromolecular triazine charring agent HF-T1020; And / or, the anti-dripping agent is TF-1645 and / or FA500H; And / or, the antioxidant is antioxidant 1010 and / or antioxidant 168; And / or, the epoxidized elastomer includes epoxidized natural rubber and / or epoxidized ethylene-vinyl acetate elastomer; And / or, the vulcanizing agent is dicumyl peroxide.

5. The composite material of claim 4, wherein, The flame retardant is polyphosphoric acid ammonium, pyrazine pyrophosphate; And / or, the pentaerythritol derivative is cage pentaerythritol phosphate and / or phenylphosphoryl-(bis-cage pentaerythritol phosphate); And / or, the triazine derivative is N-ethyl triazine-piperazine copolymer and / or macromolecular triazine charring agent HF-T1020.

6. The composite material according to any one of claims 1 to 5, wherein The preparation method of the composite flame retardant aid includes: (1) mixing the flame retardant, charring agent, anti-dripping agent, and antioxidant in a high-speed mixer; (2) mixing and vulcanizing the mixed powder obtained in step (1) with the epoxidized elastomer in an internal mixer; (3) crushing the mixture obtained in step (2) to obtain a granular composite flame retardant aid.

7. The composite material according to any one of claims 1 to 5, wherein In the inner core material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of glass fiber is 10-150 parts by weight; And / or, in the composite material, the amount of the second polyglycolic acid resin is 100 parts by weight, and the amount of the composite flame retardant aid is 50-80 parts by weight.

8. The composite material of claim 7, wherein, In the inner core material, the amount of the first polyglycolic acid resin is 100 parts by weight, and the amount of glass fiber is 20-150 parts by weight.

9. The composite material according to any one of claims 1 to 5, wherein The amount of the first polyglycolic acid resin is 100 parts by weight, and the first aid 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 aid 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.

10. The composite material of claim 9, wherein, The amount of the first polyglycolic acid resin is 100 parts by weight, and the first aid includes at least one of 0.05-2 parts by weight of a first compatibilizer, 0.1-1 part by weight of a first antioxidant, and 0.2-1 part by weight of a first lubricant; And / or, the amount of the second polyglycolic acid resin is 100 parts by weight, and the second aid includes at least one of 0.05-2 parts by weight of a second compatibilizer, 0.1-1 part by weight of a second antioxidant, and 0.2-1 part by weight of a second lubricant.

11. The composite material according to any one of claims 1 to 5, wherein The first and second compatibilizers are the same or different, and each is independently selected from at least one of a silane coupling agent, a titanate coupling agent, and an organo-chromium complex coupling agent; The first and second antioxidants are the same or different, and each is independently selected from at least one of antioxidant 1010 and / or antioxidant 168. The first and second compatibilizers are the same or different, and each is independently selected from a silane coupling agent.

12. The composite material of any of claim 11, wherein, The first and second polyglycolic acid resins are the same or different, and each is independently selected from a homopolymer polyglycolic acid and / or a copolymer polyglycolic acid; The first polyglycolic acid resin has a melt flow rate of 5-500 g / 10 min at 230°C under a load of 2.16 kg.

13. The composite material of any of claim 12, wherein, The second polyglycolic acid resin has a melt flow rate of 5-500 g / 10 min at 230°C under a load of 2.16 kg.

14. The composite material of any one of claims 1-5, wherein, The content of glycolic acid monomers in the copolymer polyglycolic acid is ≥ 90 mol%. The first polyglycolic acid resin has a melt flow rate of 10-200 g / 10 min at 230°C under a load of 2.16 kg. The second polyglycolic acid resin has a melt flow rate of 10-200 g / 10 min at 230°C under a load of 2.16 kg.

15. The composite material of claim 14, wherein, The content of glycolic acid monomers in the copolymer polyglycolic acid is ≥ 95 mol%. The first polyglycolic acid resin has a melt flow rate of 10-150 g / 10 min at 230°C under a load of 2.16 kg. The second polyglycolic acid resin has a melt flow rate of 10-150 g / 10 min at 230°C under a load of 2.16 kg.

16. The composite material of claim 15, wherein, The inner core material does not contain non-oriented short fibers. The inner core material is composed of a first polyglycolic acid resin, glass fibers, and a first auxiliary agent. The method comprises the following steps:

17. The composite material of any one of claims 1-5, wherein, S1. Melting a mixture of a first polyglycolic acid resin and a first auxiliary agent to obtain a first component melt; 18. The composite material of claim 17, wherein, S2. Performing a first impregnation treatment on the continuous glass fibers with the first component melt in step S1 to form a filamentous inner core material; 19. A method of making a composite material as claimed in any one of claims 1 to 18, characterised by, S3. Melting a mixture of a second polyglycolic acid resin, a flame-retardant auxiliary agent, and a second auxiliary agent to obtain a second component melt; 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 a halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material. ​ ​ ​ 20. The method of claim 19, wherein, 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 a halogen-free flame-retardant glass fiber reinforced polyglycolic acid composite material.

21. The method of claim 20, wherein, 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 fields of automotive and home appliances, packaging materials, building decoration, agricultural production and oil field chemical industry.

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