CN110879018A - Fiber-reinforced composite plastic for motorcycle helmet and preparation method thereof - Google Patents
Fiber-reinforced composite plastic for motorcycle helmet and preparation method thereof Download PDFInfo
- Publication number
- CN110879018A CN110879018A CN201911222370.9A CN201911222370A CN110879018A CN 110879018 A CN110879018 A CN 110879018A CN 201911222370 A CN201911222370 A CN 201911222370A CN 110879018 A CN110879018 A CN 110879018A
- Authority
- CN
- China
- Prior art keywords
- fibrilia
- preparation
- fiber
- composite plastic
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H1/00—Personal protection gear
- F41H1/04—Protection helmets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
- D21B1/06—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by dry methods
- D21B1/061—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by dry methods using cutting devices
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
- D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
- D21B1/30—Defibrating by other means
- D21B1/36—Explosive disintegration by sudden pressure reduction
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
- C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Engineering & Computer Science (AREA)
- Helmets And Other Head Coverings (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to the field of helmet materials, in particular to a fiber-reinforced composite plastic for a motorcycle helmet and a preparation method thereof. According to the invention, the fibrilia is loosened through steam explosion treatment, the loosened fibrilia has good micropores, the foaming agent is placed in the micropores of the fibrilia, then thermosetting epoxy resin is coated, during secondary fluidized bed heat treatment, the built-in foaming agent generates gas to keep the micropores, meanwhile, the epoxy resin is heated and cured to form firm coating layers to coat the fibers, and the obtained fibers are loose fibrilia with micropores; after the fibrilia is coated by the thermosetting resin, the fibrilia is beneficial to the compatibility and dispersion in a fiber polycarbonate/ABS system, loose fibrilia is protected by the thermosetting resin, the micropores of the fibrilia cannot be filled up in the later granulation processing, and the obtained composite plastic can obtain better micropore retention in the shell of the finished helmet. Endows the strength of the helmet shell and has excellent light weight and buffering property.
Description
The technical field is as follows:
the invention relates to the field of helmet materials, in particular to a fiber-reinforced composite plastic for a motorcycle helmet and a preparation method thereof.
Background art:
the helmet is a head protection device mainly made of plastic and mainly comprises an outer shell, a buffer layer lining, a suspension device and the like. The shell is generally made of hard plastics such as ABS or PC with good abrasion resistance and compression resistance, and also made of carbon fiber composite materials or metal materials. The layer is required to be high in hardness, high in rigidity, wear-resistant and helpful for resisting penetration of sharp objects. At present, most helmet shell materials are reinforced, such as carbon fiber and glass fiber reinforced plastics. However, when used in helmet shell materials, it is important, in addition to the reinforcement, how to achieve the reinforcement while ensuring good cushioning and energy absorption properties of the plastic shell. Especially for a motorcycle moving at high speed, huge impact energy can be generated by instant collision, if the shell material cannot absorb energy and disperse the impact energy well, the buffering energy is far insufficient only by the buffer layer of the inner layer, and serious damage can be caused to the head.
The reinforcement can be realized, and simultaneously, good buffering and energy absorption effects can be generated, and technicians try to moderately foam the shell material, but the foaming has a relatively obvious influence on the strength.
Chinese patent CN105482480A discloses a bamboo fiber reinforced thermoplastic plastic, which is prepared by mixing the following raw materials in parts by weight: 30-60 parts of bamboo fiber, 30-80 parts of thermoplastic plastic, 0.25-0.6 part of coupling agent, 0.3-0.8 part of cross-linking agent and 0.5-1.5 parts of lubricating agent, and the bamboo fiber is pretreated to be used for reinforcing the plastic.
In view of the above, when the bamboo fiber and the hemp fiber are used for reinforcing the helmet shell plastic, the wood fiber is loose and light while the wood fiber is reinforced, and the shell material can be endowed with good buffering performance. However, when the wood fiber is processed in a thermoplastic system, the thermoplastic polymer, the lubricating assistant and the like can easily fill up the loose pores of the wood fiber, so that the loose performance of the wood fiber reinforced plastic is poor, and the buffering and energy absorption are not obvious.
The invention content is as follows:
aiming at the defects of low strength and insufficient shock resistance of the ABS/polycarbonate system adopted by the existing shell material of the motorcycle helmet, the invention provides a fiber reinforced composite plastic for the motorcycle helmet, which is remarkably different from the existing fiber reinforced plastic in that: the invention endows the fibrilia with micropores, firmly coats the thermosetting resin on the fibrilia, the fiber is easy to disperse in an ABS/polycarbonate system, and the fiber keeps loose micropores, thereby being used for a plastic shell to improve the shock resistance and effectively increase the elasticity of the shell to increase the buffer performance. Further provides a preparation method of the fiber reinforced composite plastic for the motorcycle helmet.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the fiber reinforced composite plastic for the motorcycle helmet is characterized in that: the preparation method comprises the following steps:
(1) carrying out steam explosion and loosening treatment on the fibrilia, dispersing azodicarbonamide and alkali liquor in a mass ratio of 1:5 to obtain foaming liquid, and spraying the foaming liquid on the exploded fibrilia to enable the foaming liquid to permeate the fibrilia; then drying at 80-100 ℃ to obtain the pretreated fibrilia;
(2) preparing liquid epoxy resin, pentaerythritol, toluene diisocyanate and a curing agent into colloidal liquid; adding the pretreated fibrilia into a high-speed stirrer for high-speed stirring, and spraying colloidal liquid on the pretreated fibrilia which is stirred and suspended at high speed to coat the colloidal liquid and permeate the fibrilia;
(3) transferring the fibrilia obtained in the step (2) into a second-stage heating fluidized bed, wherein the temperature of hot air flow of the first-stage fluidized bed is 120 ℃, and the temperature of hot air flow of the second-stage fluidized bed is 190 ℃; the colloidal liquid is pre-cured on the surfaces of the fibrilia through primary hot air flow suspension treatment and has certain flexibility, the secondary hot air flow suspension treatment is carried out at a higher temperature, so that azodicarbonamide permeated by the fibrilia generates gas to enable the fibrilia to form micropores, and the colloidal liquid is further cured to form a firm coating layer, thereby finally obtaining the loose fibrilia coated by the thermosetting epoxy resin;
(4) and (3) adding the loose fibrilia obtained in the step (3), polycarbonate, ABS, an antioxidant, a lubricant and a flame retardant into a high-speed mixer, uniformly mixing, extruding by a screw extruder, water-cooling, bracing, granulating, screening and dehydrating to obtain the fiber-reinforced motorcycle helmet composite plastic.
Preferably, the steam explosion in the step (1) is a conventional treatment method for treating the fibrilia. The fibrilia is immersed in hot water to be fully softened, then the water is drained, the fibrilia is placed in a reaction vessel of a steam explosion device, the fibrilia is heated until the pressure in the reaction vessel rises to 1.0-1.5MPa, the pressure is maintained for 5min, and then the pressure is quickly released, so that the fibrilia is loosened to form micropores. The fibrilia has the characteristics of good toughening, strengthening and light weight, and is favorable for further loosening the fibrilia through steam explosion treatment, and the loosened fibrilia has good micropores and is very obvious in improving the buffering property of the material.
Preferably, the spraying amount of the foaming liquid in the step (1) is controlled to be 3-5% of the mass of the fibrilia. The loosened fibrilia micropores are easy to be filled and blocked by thermoplastic plastics, auxiliary agents and the like during the thermoplastic processing of plastics. For this reason, the present invention resides the blowing agent in the cells so that the hemp fibers still maintain good cells upon post-heat treatment.
Preferably, the colloidal liquid in the step (2) is liquid epoxy resin, pentaerythritol, toluene diisocyanate and a curing agent in a mass ratio of 40-50: 2-5: 1-3: 3-5, preparation; the liquid epoxy resin is bisphenol A type epoxy resin of Sanmu SM609-50, and the epoxy resin solution has low viscosity, good fluidity and easy spraying; the curing agent is dicyandiamide.
Preferably, the spraying amount of the colloidal liquid in the step (2) is based on uniformly coating the pretreated fibrilia; the preferred selection is that the spraying amount of the colloidal liquid is 5-10% of the mass of the pretreated fibrilia.
As a preferable technical scheme of the invention, the raw materials in the step (4) are as follows by weight: 10-15 parts of loose fibrilia, 40-60 parts of polycarbonate, 30-50 parts of ABS, 0.05-0.1 part of antioxidant, 0.5-1 part of lubricant and 0.5-2 parts of flame retardant.
Preferably, the polycarbonate in the step (4) is a Korean high-fluidity polycarbonate with LG model PC-201-22, which is advantageous for dispersing with hemp fiber; the antioxidant is prepared by mixing an antioxidant 1010 and an antioxidant 168 according to a weight ratio of 1: 2. The lubricant is at least one of stearic acid amide, paraffin, polyethylene wax and silicone powder.
As a preferred technical scheme of the invention, the temperature of the high-speed mixer in the step (4) is controlled to be 80-110 ℃, which is beneficial to melting and dispersing the lubricant; the screw extruder is a single screw extruder, and a double screw extruder is not recommended to be selected; the shearing force of the single-screw extruder is relatively weak, so that the light powder is prevented from being damaged by excessive shearing; the extrusion granulation temperature is controlled at 220-260 ℃.
Fiber reinforced plastics are well known in the art, and carbon fibers, glass fibers, etc. are uniformly applied to reinforced plastics. However, when used in helmet shell materials, it is critical how to achieve reinforcement while ensuring good cushioning and impact resistance of the plastic shell. We have attempted to foam helmet shell materials in a way that, despite the increased cushioning properties, the strength is greatly reduced. Aiming at the problems, the invention utilizes the characteristics of good toughening, strengthening and light weight of the fibrilia, is beneficial to further loosening the fibrilia through steam explosion treatment, the loosened fibrilia has good micropores, the foaming agent is placed in the micropores of the fibrilia, then thermosetting epoxy resin is coated, when the secondary fluidized bed is subjected to heat treatment, the built-in foaming agent generates gas to keep the micropores, meanwhile, the epoxy resin is heated and cured to form firm coating layer coated fibers, and the obtained fibers are loose fibrilia with micropores, as shown in figure 1. Because the thermosetting epoxy resin is not softened and melted in the later polycarbonate/ABS hot processing granulation process after being cured, the loose fibrilia micropores can be reserved in the final granulation process, and the obtained composite plastic has the functions of light weight and buffering while being reinforced. The helmet shell prepared from the material has high strength, light weight and buffering and energy-absorbing effects.
The invention further protects the fiber reinforced composite plastic for the motorcycle helmet, which is prepared by the method. The base material is a polycarbonate/ABS system, loose fibrilia is dispersed in the polycarbonate/ABS system, and the loose fibrilia is formed by coating the fibrilia with thermosetting epoxy resin.
Compared with the prior art, the fiber reinforced composite plastic for the motorcycle helmet and the preparation method thereof have the following beneficial effects:
(1) the fibrilia is loosened through steam explosion treatment, the loosened fibrilia has good micropores, a foaming agent is placed in the micropores of the fibrilia, then thermosetting epoxy resin is coated, when secondary fluidized bed heat treatment is carried out, the built-in foaming agent generates gas to keep the micropores, meanwhile, the epoxy resin is heated and cured to form firm coating layers to coat the fibers, and the obtained fibers are loose fibrilia with the micropores.
(2) The loose fibrilia obtained by the invention is protected by thermosetting resin, and the micropores of the fibrilia cannot be filled during the later granulation and thermoforming processes, so that better micropores can be reserved in the shell of the finished helmet. Endows the strength of the helmet shell and has excellent light weight and buffering property.
(3) After the thermosetting resin coats the fibrilia, the compatibility and dispersion in a fiber polycarbonate/ABS system are facilitated.
(4) The preparation method is simple in preparation process, low in cost and suitable for large-scale production.
In conclusion, the invention has the advantages and practical value, and the related publicly published technologies are not found in the prior art products, so that the invention has obvious progress compared with the prior art, is more practical and has wide large-scale popularization and production values.
Description of the drawings:
in order to more clearly illustrate the technical solution of the present invention, the technical idea of the present invention will be shown in a schematic manner below.
FIG. 1 shows that the present invention results in loose fibrilia coated with a thermosetting epoxy resin.
Wherein: 1-a thermosetting epoxy resin coating; 2-foaming loose fibrilia.
FIG. 2 is a flow chart of the preparation of the present invention.
The specific implementation mode is as follows:
the invention will now be further described by way of specific examples, with reference to FIGS. 1-2:
in order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
(1) Cutting the fibrilia into 2-3mm fibers, immersing the fibrilia into hot water for fully softening, draining water, placing the fibrilia in a reaction container of a steam explosion device, heating the fibrilia until the pressure in the reaction container rises to 1.0MPa, maintaining the pressure for 5min, then quickly releasing the pressure to loosen the fibrilia to form micropores, dispersing azodicarbonamide and saturated sodium hydroxide alkaline liquor according to the mass ratio of 1:5 to obtain foaming liquid, spraying the foaming liquid on the exploded fibrilia, wherein the spraying amount of the foaming liquid is controlled to be 5% of the mass of the fibrilia, and the foaming liquid fully permeates the fibrilia for 1 h; then drying at 100 ℃ to obtain pretreated fibrilia;
(2) the preparation method comprises the following steps of mixing liquid epoxy resin of Sanmu SM609-50, pentaerythritol, toluene diisocyanate and a curing agent dicyandiamide in a mass ratio of 40: 5: 1: 3 preparing a colloidal solution; adding the pretreated fibrilia into a high-speed stirrer, stirring at a high speed of 1000rpm, and spraying colloidal liquid on the pretreated fibrilia which is stirred and suspended at the high speed to coat the colloidal liquid and permeate the fibrilia; the spraying amount of the colloidal liquid is 8 percent of the mass of the pretreated fibrilia;
(3) transferring the fibrilia obtained in the step (2) into a second-stage heating fluidized bed, wherein the temperature of hot air flow of the first-stage fluidized bed is 120 ℃, and the temperature of hot air flow of the second-stage fluidized bed is 190 ℃; the colloidal liquid is pre-cured on the surfaces of the fibrilia through primary hot air flow suspension treatment and has certain flexibility, the secondary hot air flow suspension treatment is carried out at a higher temperature, so that azodicarbonamide permeated by the fibrilia generates gas to enable the fibrilia to form micropores, and the colloidal liquid is further cured to form a firm coating layer, thereby finally obtaining the loose fibrilia coated by the thermosetting epoxy resin;
(4) and (3) adding 10 parts by weight of loose fibrilia obtained in the step (3), 45 parts by weight of PC-201-22 high-fluidity polycarbonate, 50 parts by weight of ABS, 0.1 part by weight of antioxidant, 0.5 part by weight of lubricant polyethylene wax and 1.5 parts by weight of flame retardant magnesium hydroxide into a high-speed mixer, stirring and dispersing for 15min at the rotating speed of 200rpm at 80 ℃, uniformly mixing, extruding at the temperature of 220 ℃ by a single-screw extruder with the length-diameter ratio of 25/1, water-cooling, drawing into strips, pelletizing, sieving and dehydrating to obtain the fiber-reinforced motorcycle helmet composite plastic. The antioxidant is prepared by mixing the antioxidant 1010 and the antioxidant 168 in a weight ratio of 1: 2.
Example 2
(1) Cutting the fibrilia into 2-3mm fibers, immersing the fibrilia into hot water for fully softening, draining water, placing the fibrilia in a reaction container of a steam explosion device, heating the fibrilia until the pressure in the reaction container rises to 1.0MPa, maintaining the pressure for 5min, then quickly releasing the pressure to loosen the fibrilia to form micropores, dispersing azodicarbonamide and saturated sodium hydroxide alkaline liquor according to the mass ratio of 1:5 to obtain foaming liquid, spraying the foaming liquid on the exploded fibrilia, wherein the spraying amount of the foaming liquid is controlled to be 3% of the mass of the fibrilia, and the foaming liquid fully permeates the fibrilia for 1 h; then drying at 80 ℃ to obtain pretreated fibrilia;
(2) the preparation method comprises the following steps of mixing liquid epoxy resin of Sanmu SM609-50, pentaerythritol, toluene diisocyanate and a curing agent dicyandiamide in a mass ratio of 40: 2: 1: 3 preparing a colloidal solution; adding the pretreated fibrilia into a high-speed stirrer, stirring at a high speed of 800rpm, and spraying colloidal liquid on the pretreated fibrilia which is stirred and suspended at the high speed to coat the colloidal liquid and permeate the fibrilia; the spraying amount of the colloidal liquid is 5 percent of the mass of the pretreated fibrilia;
(3) transferring the fibrilia obtained in the step (2) into a second-stage heating fluidized bed, wherein the temperature of hot air flow of the first-stage fluidized bed is 120 ℃, and the temperature of hot air flow of the second-stage fluidized bed is 190 ℃; the colloidal liquid is pre-cured on the surfaces of the fibrilia through primary hot air flow suspension treatment and has certain flexibility, the secondary hot air flow suspension treatment is carried out at a higher temperature, so that azodicarbonamide permeated by the fibrilia generates gas to enable the fibrilia to form micropores, and the colloidal liquid is further cured to form a firm coating layer, thereby finally obtaining the loose fibrilia coated by the thermosetting epoxy resin;
(4) and (3) adding 12 parts by weight of loose fibrilia obtained in the step (3), 45 parts by weight of PC-201-22 high-fluidity polycarbonate, 30 parts by weight of ABS, 0.05 part by weight of antioxidant, 0.5 part by weight of lubricant stearic acid amide and 0.5 part by weight of flame retardant magnesium hydroxide into a high-speed mixer, stirring and dispersing for 15min at the rotating speed of 200rpm at 110 ℃, uniformly mixing, extruding at the temperature of 240 ℃ by a single-screw extruder with the length-diameter ratio of 25/1, water-cooling, drawing into strips, granulating, sieving and dehydrating to obtain the fiber-reinforced motorcycle helmet composite plastic. The antioxidant is prepared by mixing the antioxidant 1010 and the antioxidant 168 in a weight ratio of 1: 2.
Example 3
(1) Cutting the fibrilia into 2-3mm fibers, immersing the fibrilia into hot water for fully softening, draining water, placing the fibrilia in a reaction container of a steam explosion device, heating the fibrilia until the pressure in the reaction container rises to 1.5MPa, maintaining the pressure for 5min, then quickly releasing the pressure to loosen the fibrilia to form micropores, dispersing azodicarbonamide and saturated sodium hydroxide alkali liquor according to the mass ratio of 1:5 to obtain foaming liquid, spraying the foaming liquid on the exploded fibrilia, wherein the spraying amount of the foaming liquid is controlled to be 3-5% of the mass of the fibrilia, and fully permeating the fibrilia for 1 h; then drying at 100 ℃ to obtain pretreated fibrilia;
(2) the preparation method comprises the following steps of mixing liquid epoxy resin of Sanmu SM609-50, pentaerythritol, toluene diisocyanate and a curing agent dicyandiamide in a mass ratio of 50: 5: 2: 3 preparing a colloidal solution; adding the pretreated fibrilia into a high-speed stirrer, stirring at a high speed of 1000rpm, and spraying colloidal liquid on the pretreated fibrilia which is stirred and suspended at the high speed to coat the colloidal liquid and permeate the fibrilia; the spraying amount of the colloidal liquid is 10 percent of the mass of the pretreated fibrilia;
(3) transferring the fibrilia obtained in the step (2) into a second-stage heating fluidized bed, wherein the temperature of hot air flow of the first-stage fluidized bed is 120 ℃, and the temperature of hot air flow of the second-stage fluidized bed is 190 ℃; the colloidal liquid is pre-cured on the surfaces of the fibrilia through primary hot air flow suspension treatment and has certain flexibility, the secondary hot air flow suspension treatment is carried out at a higher temperature, so that azodicarbonamide permeated by the fibrilia generates gas to enable the fibrilia to form micropores, and the colloidal liquid is further cured to form a firm coating layer, thereby finally obtaining the loose fibrilia coated by the thermosetting epoxy resin;
(4) adding 15 parts by weight of loose fibrilia obtained in the step (3), 60 parts by weight of PC-201-22 high-fluidity polycarbonate, 50 parts by weight of ABS, 0.1 part by weight of antioxidant, 0.5 part by weight of lubricant silicone powder and 1 part by weight of flame retardant magnesium hydroxide into a high-speed mixer, stirring and dispersing for 20min at the rotating speed of 400rpm at 110 ℃, uniformly mixing, extruding at the temperature of 235 ℃ through a single-screw extruder with the length-diameter ratio of 25/1, water-cooling, drawing into strips, granulating, sieving and dehydrating to obtain the fiber-reinforced motorcycle helmet composite plastic. The antioxidant is prepared by mixing the antioxidant 1010 and the antioxidant 168 in a weight ratio of 1: 2.
Comparative example 1
(1) Cutting the fibrilia into 2-3mm fibers, immersing the fibrilia into hot water for fully softening, draining water, placing the fibrilia in a reaction container of a steam explosion device, heating the fibrilia until the pressure in the reaction container rises to 1.0MPa, maintaining the pressure for 5min, then quickly releasing the pressure to loosen the fibrilia to form micropores, dispersing azodicarbonamide and saturated sodium hydroxide alkaline liquor according to the mass ratio of 1:5 to obtain foaming liquid, spraying the foaming liquid on the exploded fibrilia, wherein the spraying amount of the foaming liquid is controlled to be 5% of the mass of the fibrilia, and the foaming liquid fully permeates the fibrilia for 1 h; then drying at 100 ℃ to obtain pretreated fibrilia;
(2) transferring the fibrilia obtained in the step (1) into a second-stage heating fluidized bed, wherein the temperature of hot air flow of the first-stage fluidized bed is 120 ℃, and the temperature of hot air flow of the second-stage fluidized bed is 190 ℃; the second stage of hot air flow suspension treatment is carried out, the temperature is higher, so that the azodicarbonamide permeated by the fibrilia generates gas to enable the fibrilia to form micropores;
(3) and (3) adding 10 parts by weight of loose fibrilia obtained in the step (2), 45 parts by weight of PC-201-22 high-fluidity polycarbonate, 50 parts by weight of ABS, 0.1 part by weight of antioxidant, 0.5 part by weight of lubricant polyethylene wax and 1.5 parts by weight of flame retardant magnesium hydroxide into a high-speed mixer, stirring and dispersing for 15min at the rotating speed of 200rpm at 80 ℃, uniformly mixing, extruding at the temperature of 220 ℃ by a single-screw extruder with the length-diameter ratio of 25/1, water-cooling, drawing into strips, pelletizing, sieving and dehydrating to obtain the fiber-reinforced motorcycle helmet composite plastic. The antioxidant is prepared by mixing the antioxidant 1010 and the antioxidant 168 in a weight ratio of 1: 2.
Comparative example 1 no thermosetting epoxy resin was cured and coated on the surface of loose fibrilia, and the rest of the process and materials were the same as those of example 1. Because of lack of coating protection of epoxy resin, the loose fibrilia is dispersed in the polycarbonate/ABS system at the later stage, and the micropores of the loose fibrilia are filled with thermoplastic resin, lubricant and the like during thermoplastic processing, so that the obtained composite plastic has higher density and lower impact resistance and buffering performance.
Comparative example 2
Adding 45 parts by weight of PC-201-22 high-fluidity polycarbonate, 50 parts by weight of ABS, 0.1 part by weight of antioxidant, 0.5 part by weight of lubricant polyethylene wax and 1.5 parts by weight of flame retardant magnesium hydroxide into a high-speed mixer, stirring and dispersing for 15min at the rotating speed of 200rpm at 80 ℃, uniformly mixing, extruding by a single-screw extruder with the length-diameter ratio of 25/1 at the temperature of 220 ℃, water-cooling, drawing strips, granulating, sieving and dehydrating to obtain the fiber-reinforced motorcycle helmet composite plastic. The antioxidant is prepared by mixing the antioxidant 1010 and the antioxidant 168 in a weight ratio of 1: 2.
Comparative example 2 loose fibrilia was not added to the polycarbonate/ABS system, which on the one hand affected the strength of the composite plastic and on the other hand greatly reduced the impact resistance.
The composite plastics obtained in examples 1 to 3 and comparative examples 1 to 2 were compared in performance tests.
1. And (3) testing the density: referring to GB1033, the density of the composite plastic granules is tested by a specific gravity method, and the granules are not easy to sink in water and directly drain because the density of the granules is lower than that of water, therefore, porous metal is added into a measuring cylinder, the granules are forced into the water to be subjected to a drainage test, and the density is calculated.
2. Impact resistance: the composite plastic pellets obtained in examples 1 to 3 and comparative examples 1 to 2 were dried at 100 ℃ for 1 hour, and then injection-molded at 230 ℃. Referring to GB/T1843, the length L of the sample is 80mm, the width b is 10mm, the thickness h is 4mm, the residual width of the gap is 8.0mm, and the gap type is A type; the notched izod impact strength was measured by an izod impact test at a temperature of 23 ℃, as shown in table 1.
3. The buffer performance is as follows: the composite plastic granules obtained in the examples 1-3 and the comparative examples 1-2 are respectively subjected to injection molding at 230 ℃ to form a semi-spherical shape with the radius of 12cm, the shell of the simulated helmet is molded, the injection molding thickness is 4mm, the spherical surface of the shell of the semi-spherical helmet is downward, the shell freely falls at the height of 3m, and the ground is contacted with flat concrete; the test simulates the height to which the helmet shell is rebounded to gauge cushioning performance. As shown in table 1.
Table 1:
the above-mentioned embodiment is only one of the preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, so: all equivalent changes made according to the shape, structure and principle of the invention are covered by the protection scope of the invention.
Claims (8)
1. A preparation method of fiber-reinforced composite plastic for a motorcycle helmet is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) carrying out steam explosion and loosening treatment on the fibrilia, dispersing azodicarbonamide and alkali liquor in a mass ratio of 1:5 to obtain foaming liquid, and spraying the foaming liquid on the exploded fibrilia to enable the foaming liquid to permeate the fibrilia; then drying at 80-100 ℃ to obtain the pretreated fibrilia;
(2) preparing liquid epoxy resin, pentaerythritol, toluene diisocyanate and a curing agent into colloidal liquid; adding the pretreated fibrilia into a high-speed stirrer for high-speed stirring, and spraying colloidal liquid on the pretreated fibrilia which is stirred and suspended at high speed to coat the colloidal liquid and permeate the fibrilia;
(3) transferring the fibrilia obtained in the step (2) into a second-stage heating fluidized bed, wherein the temperature of hot air flow of the first-stage fluidized bed is 120 ℃, and the temperature of hot air flow of the second-stage fluidized bed is 190 ℃; the colloidal liquid is pre-cured on the surfaces of the fibrilia through primary hot air flow suspension treatment and has certain flexibility, the secondary hot air flow suspension treatment is carried out at a higher temperature, so that azodicarbonamide permeated by the fibrilia generates gas to enable the fibrilia to form micropores, and the colloidal liquid is further cured to form a firm coating layer, thereby finally obtaining the loose fibrilia coated by the thermosetting epoxy resin;
(4) and (3) adding the loose fibrilia obtained in the step (3), polycarbonate, ABS, an antioxidant, a lubricant and a flame retardant into a high-speed mixer, uniformly mixing, extruding by a screw extruder, water-cooling, bracing, granulating, screening and dehydrating to obtain the fiber-reinforced motorcycle helmet composite plastic.
2. The preparation method of the fiber-reinforced composite plastic for the motorcycle helmet as claimed in claim 1, wherein the preparation method comprises the following steps: and (2) the steam explosion in the step (1) is to immerse the fibrilia in hot water to be fully softened, drain the water, place the fibrilia in a reaction vessel of a steam explosion device, heat the fibrilia until the pressure in the reaction vessel rises to 1.0-1.5MPa, maintain the pressure for 5min, and quickly release the pressure to loosen the fibrilia to form micropores.
3. The preparation method of the fiber-reinforced composite plastic for the motorcycle helmet as claimed in claim 1, wherein the preparation method comprises the following steps: and (2) controlling the spraying amount of the foaming liquid in the step (1) to be 3-5% of the mass of the fibrilia.
4. The preparation method of the fiber-reinforced composite plastic for the motorcycle helmet as claimed in claim 1, wherein the preparation method comprises the following steps: the colloidal liquid in the step (2) is prepared from liquid epoxy resin, pentaerythritol, toluene diisocyanate and a curing agent in a mass ratio of 40-50: 2-5: 1-3: 3-5, preparation; the liquid epoxy resin is bisphenol A type epoxy resin of Sanmu SM 609-50; the curing agent is dicyandiamide.
5. The preparation method of the fiber-reinforced composite plastic for the motorcycle helmet as claimed in claim 1, wherein the preparation method comprises the following steps: the spraying amount of the colloidal liquid in the step (2) is 5-10% of the mass of the pretreated fibrilia.
6. The preparation method of the fiber-reinforced composite plastic for the motorcycle helmet as claimed in claim 1, wherein the preparation method comprises the following steps: the raw materials in the step (4) are as follows by weight: 10-15 parts of loose fibrilia, 40-60 parts of polycarbonate, 30-50 parts of ABS, 0.05-0.1 part of antioxidant, 0.5-1 part of lubricant and 0.5-2 parts of flame retardant.
7. The preparation method of the fiber-reinforced composite plastic for the motorcycle helmet as claimed in claim 1, wherein the preparation method comprises the following steps: controlling the temperature of the high-speed mixer in the step (4) to be 80-110 ℃; the extrusion granulation temperature is controlled at 220-260 ℃.
8. A fibre reinforced motorcycle helmet composite plastic, characterised in that it is prepared by the process of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911222370.9A CN110879018B (en) | 2019-12-03 | 2019-12-03 | Fiber-reinforced composite plastic for motorcycle helmet and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911222370.9A CN110879018B (en) | 2019-12-03 | 2019-12-03 | Fiber-reinforced composite plastic for motorcycle helmet and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110879018A true CN110879018A (en) | 2020-03-13 |
| CN110879018B CN110879018B (en) | 2020-09-01 |
Family
ID=69730096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911222370.9A Active CN110879018B (en) | 2019-12-03 | 2019-12-03 | Fiber-reinforced composite plastic for motorcycle helmet and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110879018B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029260A (en) * | 2020-09-21 | 2020-12-04 | 广东国立科技股份有限公司 | Fibrilia-reinforced PC/ABS composite material, and preparation method and application thereof |
| CN112321903A (en) * | 2020-12-03 | 2021-02-05 | 宿松晨辉塑料制品有限公司 | Biodegradable composite plastic production process |
| CN114103340A (en) * | 2021-12-23 | 2022-03-01 | 浙江远景体育用品有限公司 | Continuous fiber reinforced thermoplastic helmet shell material and preparation method thereof |
| CN115404701A (en) * | 2022-08-26 | 2022-11-29 | 东华大学 | Porous yarn with temperature adjusting function and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060099393A1 (en) * | 2004-11-08 | 2006-05-11 | Azdel, Inc. | Composite thermoplastic sheets including natural fibers |
| CN104073013A (en) * | 2014-06-30 | 2014-10-01 | 江苏旭华圣洛迪建材有限公司 | Continuous-fiber-reinforced wood plastic and preparation method thereof |
| CN105348720A (en) * | 2015-11-13 | 2016-02-24 | 安徽广源科技发展有限公司 | Recoverable composite plastic used for electric appliance elements |
| CN105924902A (en) * | 2016-05-16 | 2016-09-07 | 贵州省材料产业技术研究院 | Thermally-expandable solid epoxy resin microcellular foam material and preparation method thereof |
| CN110003677A (en) * | 2019-04-24 | 2019-07-12 | 安徽大学 | A kind of halogen-free polypropylene flame redardant wood plastic composite and preparation method thereof |
-
2019
- 2019-12-03 CN CN201911222370.9A patent/CN110879018B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060099393A1 (en) * | 2004-11-08 | 2006-05-11 | Azdel, Inc. | Composite thermoplastic sheets including natural fibers |
| CN104073013A (en) * | 2014-06-30 | 2014-10-01 | 江苏旭华圣洛迪建材有限公司 | Continuous-fiber-reinforced wood plastic and preparation method thereof |
| CN105348720A (en) * | 2015-11-13 | 2016-02-24 | 安徽广源科技发展有限公司 | Recoverable composite plastic used for electric appliance elements |
| CN105924902A (en) * | 2016-05-16 | 2016-09-07 | 贵州省材料产业技术研究院 | Thermally-expandable solid epoxy resin microcellular foam material and preparation method thereof |
| CN110003677A (en) * | 2019-04-24 | 2019-07-12 | 安徽大学 | A kind of halogen-free polypropylene flame redardant wood plastic composite and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029260A (en) * | 2020-09-21 | 2020-12-04 | 广东国立科技股份有限公司 | Fibrilia-reinforced PC/ABS composite material, and preparation method and application thereof |
| CN112321903A (en) * | 2020-12-03 | 2021-02-05 | 宿松晨辉塑料制品有限公司 | Biodegradable composite plastic production process |
| CN114103340A (en) * | 2021-12-23 | 2022-03-01 | 浙江远景体育用品有限公司 | Continuous fiber reinforced thermoplastic helmet shell material and preparation method thereof |
| CN114103340B (en) * | 2021-12-23 | 2022-11-04 | 浙江远景体育用品股份有限公司 | Continuous fiber reinforced thermoplastic helmet shell material and preparation method thereof |
| WO2023115768A1 (en) * | 2021-12-23 | 2023-06-29 | 浙江远景体育用品股份有限公司 | Continuous fiber-reinforced thermoplastic helmet shell material and preparation method therefor |
| CN115404701A (en) * | 2022-08-26 | 2022-11-29 | 东华大学 | Porous yarn with temperature adjusting function and preparation method thereof |
| CN115404701B (en) * | 2022-08-26 | 2023-08-29 | 东华大学 | Porous yarn with temperature regulating function and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110879018B (en) | 2020-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110879018B (en) | Fiber-reinforced composite plastic for motorcycle helmet and preparation method thereof | |
| Verma et al. | Physical and thermal characterization of chicken feather fiber and crumb rubber reformed epoxy resin hybrid composite | |
| CN107641242B (en) | Injection molding material | |
| CN101709130B (en) | Ultra-low density solid buoyant material and manufacture method | |
| CN106633385A (en) | Microcellular foaming wood-plastic composite material and preparation method thereof | |
| Ahmed et al. | Physico-mechanical properties of coir and jute fibre reinforced hybrid polyethylene composites | |
| RU2318666C2 (en) | Method of manufacture of the fibers reinforced articles on the basis of the epoxy resin | |
| CN106626202A (en) | Preparation method of expansive type thermoplastic polyurethane elastomer product | |
| CN106810857A (en) | A kind of composition of modified fiberglass reinforced PA 6 and preparation method thereof | |
| CN105694372A (en) | Carbon fiber reinforced epoxy resin composite and preparation method thereof | |
| CN109679312A (en) | A kind of polymer composites | |
| CN105694206B (en) | A kind of method for making foaming agent production long glass fiber-reinforced polypropylene foaming injection product with water | |
| CN100400258C (en) | Chopped strand and unsaturated polyester resin BMC moulding product made by it | |
| US6476087B1 (en) | Method of manufacturing syntactic foam | |
| Kumar et al. | Recent developments of lignocellulosic natural fiber reinforced hybrid thermosetting composites for high-end structural applications: A review | |
| CN107083019B (en) | sound insulation composite material and preparation method thereof | |
| John et al. | Thermosetting polymer based syntactic foams: an overview | |
| CN109735000A (en) | A kind of high-performance, low-density mineral filled polypropylene material and preparation method thereof | |
| CN106009666B (en) | A kind of carbon fiber reinforced bismalemide foamed material and preparation method thereof | |
| CN110549707A (en) | Foamed polypropylene composite sheet and preparation method thereof | |
| CN105542506A (en) | SMC (sheet molding compound) material for automobile accessories and preparation method thereof | |
| CN109251410A (en) | Low warp glass fiber reinforced polypropylene compound material and preparation method thereof | |
| CN115073877A (en) | Recyclable environment-friendly clothes hanger and preparation method thereof | |
| JPS63218325A (en) | Rim manufacture of thermosetting fiber-reinforced composite body | |
| WO2017056011A1 (en) | Compound material for hot-molding |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 317500 No. 399, Jinyuan Road, Songmen Town, Wenling City, Taizhou City, Zhejiang Province Patentee after: Zhejiang Yuanjing sporting goods Co.,Ltd. Address before: 317511 east side of Haitian Road, Southeast industrial gathering point, Songmen Town, Wenling City, Taizhou City, Zhejiang Province Patentee before: ZHEJIANG VISTA SPORTS GOODS CO.,LTD. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A fiber reinforced motorcycle helmet composite plastic and its preparation method Effective date of registration: 20220524 Granted publication date: 20200901 Pledgee: China Construction Bank Wenling sub branch Pledgor: Zhejiang Yuanjing sporting goods Co.,Ltd. Registration number: Y2022330000779 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220912 Granted publication date: 20200901 Pledgee: China Construction Bank Wenling sub branch Pledgor: Zhejiang Yuanjing sporting goods Co.,Ltd. Registration number: Y2022330000779 |