CN110669327B - Preparation method of light helmet composite plastic special for bicycle - Google Patents

Preparation method of light helmet composite plastic special for bicycle Download PDF

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CN110669327B
CN110669327B CN201911136095.9A CN201911136095A CN110669327B CN 110669327 B CN110669327 B CN 110669327B CN 201911136095 A CN201911136095 A CN 201911136095A CN 110669327 B CN110669327 B CN 110669327B
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light
inorganic powder
powder
fluidized bed
polyimide
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CN110669327A (en
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张道增
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Zhejiang Yuanjing sporting goods Co.,Ltd.
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Zhejiang Vista Sports Goods Co ltd
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • 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
    • C08J2423/08—Copolymers of ethene
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    • 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
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    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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  • Helmets And Other Head Coverings (AREA)

Abstract

The utility model relates to the field of helmet materials, in particular to a preparation method of light helmet composite plastic special for a bicycle. According to the utility model, the light inorganic powder is preloaded with azodicarbonamide capable of generating gas, then the azodicarbonamide is coated with a polyimide film, the azodicarbonamide is foamed to generate support through gradual temperature rise, so that the micropores of the powder are not blocked, the polyimide is solidified to form a stable coating film, and spherical light powder with complete closed pores is obtained and is used as a filler to be directly filled in plastic, and the polyimide is not melted at the processing temperature of the existing polycarbonate and ABS, so that the light characteristic of the light powder is better kept when the light powder is used for plastic compounding, and the light weight of the plastic is realized.

Description

Preparation method of light helmet composite plastic special for bicycle
Technical Field
The utility model relates to the field of helmet materials, in particular to a preparation method of light helmet composite plastic special for a bicycle.
Background
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 have high hardness, high rigidity and wear resistance, and is helpful for resisting the penetration of sharp objects; the buffer layer is closely attached to the inner side of the shell, and foam plastics such as EPS, EPO, EPP and the like are commonly used. The layer has the main function of resisting the impact force transmitted from the outer shell through large deformation of the foam body and absorbing the impact energy. However, in practice, the foam has a limited deformation distance for compression, and the cushioning effect is not ideal under the action of a large impact force. In addition, the foam is generally of a low rigidity, which is not beneficial to the dispersion and the transmission of impact force, so that the impact force is excessively concentrated, and the head of a wearer still has the risk of injury. This problem is often solved by increasing the thickness of the helmet shell, which at the same time increases the weight of the helmet, causing inconvenience to the user.
The shell of the existing bicycle helmet is made of a PC + ABS composite material, and the safety can be improved by a hard helmet shell with a proper thickness. However, with the added weight and comfort, thinner and stronger carbon fiber helmet shell materials have been developed. Obviously, the carbon fiber housing cost doubles. Meanwhile, the carbon fiber shell is more difficult to form, and compared with a PC + ABS composite material injection molding process, the carbon fiber forming process is more complicated.
In order to further reduce the density of PC + ABS composite materials for weight reduction, technicians have attempted to add lightweight microporous inorganic powders to plastics. However, when the lightweight inorganic powder is directly added to the plastic for compounding, the microporous pores of the lightweight inorganic powder adsorb hot-melt resin, lubricant, etc., and thus the effect of lightening the weight of the plastic after kneading is not significant. It is further desirable to use a closed-cell, lightweight inorganic powder, but on the one hand the closed-cell, lightweight material is limited in the materials that can be selected, and on the other hand, the inorganic closed-cell, lightweight material is largely particulate and brittle and is difficult to meet screw extrusion shear processing and dispersion processing.
Disclosure of Invention
The bicycle helmet material is developed to be light and thin, and the traditional ABS/polycarbonate system for the bicycle helmet material shell cannot meet the requirement. In order to further improve the lightweight performance of the bicycle helmet material, the utility model provides a preparation method of the lightweight helmet composite plastic special for the bicycle.
In order to achieve the purpose, the utility model adopts the following technical scheme:
the preparation method of the light helmet composite plastic special for the bicycle is characterized in that: the preparation method comprises the following steps:
(1) mixing porous light inorganic powder and azodicarbonamide according to a mass ratio of 100: 1-1.5, grinding in a ball mill after uniformly mixing, and entering micropores of the porous light inorganic powder along with the grinding and refining of azodicarbonamide to obtain composite porous light inorganic powder; the porous light inorganic powder is silicon dioxide aerogel powder;
(2) sending the composite porous light inorganic powder prepared in the step (1) into a high-speed stirrer, and starting a high-speed stirring device to suspend the composite porous light inorganic powder in high-speed stirring; then spraying the liquid polyimide to the composite porous light inorganic powder by a high-pressure atomization spray gun, and uniformly coating the liquid polyimide on the surface of the composite porous light inorganic powder under stirring and suspension due to the viscosity of the liquid polyimide;
(3) transferring the material obtained in the step (2) into a third-stage fluidized bed, wherein the temperature of hot air flow of the first-stage fluidized bed is 170 ℃, the temperature of hot air flow of the second-stage fluidized bed is 200 ℃, and the temperature of hot air flow of the third-stage fluidized bed is 280 ℃; after three-stage heating, polyimide is solidified on the surface of the composite porous light inorganic powder to form a uniform coating layer; discharging and cooling to obtain uniform and fine light powder;
(4) and (3) adding the light powder obtained in the step (3), polycarbonate, ABS, POE, nylon, glass fiber, antioxidant, lubricant and flame retardant into a high-speed mixer, uniformly mixing, and extruding and granulating by a screw extruder to obtain the light helmet composite plastic special for bicycles.
As a preferred technical scheme of the utility model, the porous light inorganic powder in the step (1) is silica aerogel powder with the porosity of more than 90 percent; such materials have good cell porosity, have a very low density, typically 50-200kg/m3, which makes composite plastics lighter when used in plastics.
As a preferred technical scheme of the utility model, the step (1) is ground and refined by azodicarbonamide, and the azodicarbonamide is easy to enter micropores of the porous light inorganic powder; the rotating speed of the ball mill is controlled at 20-35rpm, and the grinding time is controlled at 5-10 min; the grinding speed should not be too fast, the grinding time should not be too long, and too fast and too long grinding will result in the porous light inorganic powder being over-ground with micropores to disappear.
As a preferred technical scheme of the utility model, the high-speed stirring in the step (2) adopts a high rotating speed of 1000-1200rpm, so as to fully suspend the powder, and the material is fully suspended through the high-speed stirring so as to effectively disperse the powder.
As a preferable embodiment of the present invention, the liquid polyimide in the step (2) is selected from those having a viscosity of 2000-. More preferably, the liquid polyimide is a YE1001 type thermosetting liquid polyimide available from shanghai kojic corp, and the cured surface thereof is smooth and uniform.
As a preferred technical scheme of the utility model, the pressure of the high-pressure atomization spray gun adopted in the step (2) is controlled to be 1.2-1.5MPa, and the aperture of the nozzle mesh is 1.5 mm. Since the liquid polyimide has a certain viscosity, a spray gun having an excessively small pore diameter is not preferable. The liquid polyimide is sprayed to the composite porous light inorganic powder, so that the liquid polyimide is uniformly coated on the surface of the composite porous light inorganic powder.
As a preferable technical scheme of the utility model, the dosage of the liquid polyimide adopting the high-pressure atomization spray gun in the step (2) is preferably controlled to be 5-10% of the mass of the composite porous light inorganic powder.
As a preferred technical scheme of the utility model, three-stage fluidized bed treatment is adopted in the step (3), hot air flow is utilized to enable the material to show the property similar to liquid, and the polyimide is further solidified under the heating condition. Particularly, the polyimide is incompletely cured at 170 ℃ through gradual temperature rise curing, the polyimide has certain plasticity, azodicarbonamide loaded in the composite porous light inorganic powder in the polyimide powder starts to generate gas, micropores of the composite porous light inorganic powder are not filled with a coating, and meanwhile, the polyimide coating layer forms spherical coating inorganic powder due to the foaming and supporting effects of the gas, so that the obtained coating composite powder is light and spherical; further passing through a second stage fluidized bed, taking azodicarbonamide release gas as a support at the temperature of 200 ℃, and curing the polyimide coating; and a third fluidized bed, wherein the polyimide is solidified and densified at the temperature of 280 ℃, and finally a hard coating layer is formed.
As a preferred technical scheme of the utility model, when the three-stage fluidized bed treatment is adopted in the step (3), in order to keep good curing reaction, the treatment time of the first-stage fluidized bed is 3 min; the second stage fluidized bed treatment time is 5 min; the processing time of the third fluidized bed is 8-10 min.
As a preferable technical scheme of the utility model, the raw materials in the step (4) are as follows by weight: 5-10 parts of light powder, 40-60 parts of polycarbonate, 30-50 parts of ABS, 1-3 parts of POE, 2-5 parts of nylon, 0.5-2 parts of glass fiber, 0.05-0.1 part of antioxidant, 0.5-1 part of lubricant and 0.5-2 parts of flame retardant.
As a preferred technical scheme of the utility model, 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 ℃.
The utility model further protects the light helmet composite plastic special for the bicycle, which is prepared by the method.
In order to achieve a lighter plastic material for helmets while maintaining good abrasion resistance and hardness, the addition of light microporous inorganic powders to plastics is a preferred technique. However, when the technicians try to compound the light inorganic powder directly into the plastic, the light inorganic powder has no obvious effect in the plastic because the micropores can adsorb hot-melt resin, lubricant and the like. In order to solve the technical problem, the utility model has the outstanding performance that the light inorganic powder is preloaded with azodicarbonamide which can generate gas, then a polyimide film is coated, the micro-pores of the powder are not blocked by the support generated by the foaming of the azodicarbonamide through the gradual temperature rise, and the polyimide is solidified to form a stable coating film, thereby obtaining the spherical light powder with complete closed pores. Polyimide is a high-temperature-resistant thermosetting engineering plastic, the temperature resistance of the polyimide can reach 300-400 ℃, so that closed-cell light powder formed by coating inorganic powder can be directly used as filler to be filled in the plastic, and the polyimide can not be melted at the processing temperature of the existing polycarbonate and ABS, so that the light property of the light powder is better kept when the light powder is used for compounding the plastic, and the light weight of the plastic is realized.
Furthermore, the polyimide has excellent hardness, thermal deformation resistance and excellent wear resistance, and the coated inorganic powder used as the filler for plastics has remarkable advantages in improving the wear resistance, hardness and the like of the plastics.
Compared with the prior art, the light helmet composite plastic special for the bicycle and the preparation method have the following beneficial effects:
(1) when the light inorganic powder is cured and coated by the polyimide, the azodicarbonamide preloaded by the light inorganic powder generates gas, thus effectively preventing micropores of the light inorganic powder from being filled and blocked by a coating material, supporting the polyimide curing coating layer to form a spherical coating layer, and preferably ensuring the light weight;
(2) the composite porous light inorganic powder is coated by the polyimide curing coating layer, the obtained light powder is used as a filler and directly used for the plastic of a polycarbonate and ABS system, and the temperature resistance of the polyimide can reach 300-400 ℃ and can not be melted at the processing temperature of the existing polycarbonate and ABS;
(3) according to the utility model, the polyimide curing layer is coated on the surface of the light inorganic powder, and the curing layer is compact, so that the light powder formed by coating the composite porous light inorganic powder with the polyimide can be directly added and used as a common filler, and the composite plastic has excellent wear resistance due to good toughness and wear resistance of the polyimide.
In conclusion, the utility model has the advantages and practical value, and the related publicly published technologies are not found in the prior art products, so that the utility model has obvious progress compared with the prior art, is more practical and has wide large-scale popularization and production values.
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 is a flow chart of the preparation of the present invention.
FIG. 2 is a schematic view of a light powder obtained in step (3) of example 1 of the present invention.
Wherein: 1-a polyimide coating layer; 2-composite porous light inorganic powder.
Detailed Description
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) Mixing QF type silicon dioxide aerogel powder of Nanaoko family Zhejiang with azodicarbonamide according to a mass ratio of 100: 1, grinding in a ball mill after uniformly mixing, controlling the rotating speed of the ball mill at 20rpm, grinding for 5min, and entering micropores of the porous light inorganic powder along with the grinding and refining of azodicarbonamide to obtain composite porous light inorganic powder;
(2) sending the composite porous light inorganic powder prepared in the step (1) into a high-speed stirrer, starting a high-speed stirring device, and adopting a high rotating speed of 1000rpm to fully suspend the powder, so that the powder is effectively dispersed by completely suspending the material through high-speed stirring; then, a high-pressure atomization spray gun is adopted to spray YE1001 type thermosetting liquid polyimide to the composite porous light inorganic powder under the action of 1.2MPa, and the liquid polyimide is uniformly coated on the surface of the composite porous light inorganic powder under the stirring suspension due to the viscosity of the liquid polyimide; the using amount of the liquid polyimide is controlled to be 5 percent of the mass of the composite porous light inorganic powder;
(3) transferring the material obtained in the step (2) into a three-stage fluidized bed, wherein the temperature of hot air flow of the first-stage fluidized bed is 170 ℃, and performing high-speed suspension treatment on the hot air flow for 3 min; the temperature of hot air flow of the second stage fluidized bed is 200 ℃, and the second stage fluidized bed is subjected to high-speed suspension treatment in the hot air flow for 5 min; the temperature of hot air flow of the third fluidized bed is 280 ℃, and the suspension treatment is carried out for 8min in the hot air flow at high speed; after three-stage heating, polyimide is solidified on the surface of the composite porous light inorganic powder to form a uniform coating layer; discharging and cooling to obtain uniform and fine light powder;
(4) adding 10 parts by weight of the light powder obtained in the step (3), 40 parts by weight of polycarbonate (Bayer PC1603), 50 parts by weight of ABS, 1 part by weight of POE (ENGAGE 8407 Dow), 662 parts by weight of nylon, 0.5 part by weight of glass fiber, 0.05 part by weight of antioxidant (1010), 1 part by weight of lubricant polyethylene wax and 0.5 part by weight of brominated triazine FR-245 plastic flame retardant into a high-speed mixer, controlling the temperature at 110 ℃, performing dispersion treatment at the rotating speed of 400rpm for 15min, then feeding into a single-screw extruder, controlling the extrusion granulation temperature at 230 ℃, and performing extrusion granulation to obtain the light helmet composite plastic special for bicycles.
Example 2
(1) Mixing QF type silicon dioxide aerogel powder of Nanaoko family Zhejiang with azodicarbonamide according to a mass ratio of 100: 1.5 grinding in a ball mill after uniformly mixing, controlling the rotating speed of the ball mill at 20rpm, grinding for 5min, and entering micropores of the porous light inorganic powder along with the grinding and refining of the azodicarbonamide to obtain composite porous light inorganic powder;
(2) sending the composite porous light inorganic powder prepared in the step (1) into a high-speed stirrer, starting a high-speed stirring device, and adopting a high rotating speed of 1000rpm to fully suspend the powder, so that the powder is effectively dispersed by completely suspending the material through high-speed stirring; then, a high-pressure atomization spray gun is adopted to spray YE1001 type thermosetting liquid polyimide to the composite porous light inorganic powder under the action of 1.2MPa, and the liquid polyimide is uniformly coated on the surface of the composite porous light inorganic powder under the stirring suspension due to the viscosity of the liquid polyimide; the using amount of the liquid polyimide is controlled to be 6 percent of the mass of the composite porous light inorganic powder;
(3) transferring the material obtained in the step (2) into a three-stage fluidized bed, wherein the temperature of hot air flow of the first-stage fluidized bed is 170 ℃, and performing high-speed suspension treatment on the hot air flow for 3 min; the temperature of hot air flow of the second stage fluidized bed is 200 ℃, and the second stage fluidized bed is subjected to high-speed suspension treatment in the hot air flow for 5 min; the temperature of hot air flow of the third fluidized bed is 280 ℃, and the suspension treatment is carried out for 8min in the hot air flow at high speed; after three-stage heating, polyimide is solidified on the surface of the composite porous light inorganic powder to form a uniform coating layer; discharging and cooling to obtain uniform and fine light powder;
(4) adding 10 parts by weight of the light powder obtained in the step (3), 45 parts by weight of polycarbonate (Bayer PC1603), 30 parts by weight of ABS, 2 parts by weight of POE (ENGAGE 8407 Dow), 663 parts by weight of nylon, 0.5 part by weight of glass fiber, 0.05 part by weight of antioxidant (1010), 1 part by weight of lubricant polyethylene wax and 0.5 part by weight of brominated triazine FR-245 plastic flame retardant into a high-speed mixer, controlling the temperature at 110 ℃, performing dispersion treatment at the rotating speed of 700rpm for 25min, then feeding into a single-screw extruder, controlling the extrusion granulation temperature at 235 ℃, and performing extrusion granulation to obtain the light helmet composite plastic special for bicycles.
Example 3
(1) Mixing QF type silicon dioxide aerogel powder of Nanaoko family Zhejiang with azodicarbonamide according to a mass ratio of 100: 1.5 grinding in a ball mill after uniformly mixing, controlling the rotating speed of the ball mill at 35rpm, grinding for 10min, and entering micropores of the porous light inorganic powder along with the grinding and refining of the azodicarbonamide to obtain composite porous light inorganic powder;
(2) sending the composite porous light inorganic powder prepared in the step (1) into a high-speed stirrer, starting a high-speed stirring device, and adopting a high rotating speed of 1000rpm to fully suspend the powder, so that the powder is effectively dispersed by completely suspending the material through high-speed stirring; then, a high-pressure atomization spray gun is adopted to spray YE1001 type thermosetting liquid polyimide to the composite porous light inorganic powder under the action of 1.2MPa, and the liquid polyimide is uniformly coated on the surface of the composite porous light inorganic powder under the stirring suspension due to the viscosity of the liquid polyimide; the using amount of the liquid polyimide is controlled to be 10 percent of the mass of the composite porous light inorganic powder;
(3) transferring the material obtained in the step (2) into a three-stage fluidized bed, wherein the temperature of hot air flow of the first-stage fluidized bed is 170 ℃, and performing high-speed suspension treatment on the hot air flow for 3 min; the temperature of hot air flow of the second stage fluidized bed is 200 ℃, and the second stage fluidized bed is subjected to high-speed suspension treatment in the hot air flow for 5 min; the temperature of hot air flow of the third fluidized bed is 280 ℃, and the suspension treatment is carried out in the hot air flow for 10min at high speed; after three-stage heating, polyimide is solidified on the surface of the composite porous light inorganic powder to form a uniform coating layer; discharging and cooling to obtain uniform and fine light powder;
(4) adding 10 parts by weight of the light powder obtained in the step (3), 60 parts by weight of polycarbonate (Bayer PC1603), 30 parts by weight of ABS, 3 parts by weight of POE (ENGAGE 8407 Dow), 662 parts by weight of nylon, 0.5 part by weight of glass fiber, 0.05 part by weight of antioxidant (1010), 1 part by weight of polyethylene wax serving as a lubricant and 1 part by weight of brominated triazine FR-245 plastic flame retardant into a high-speed mixer, controlling the temperature at 110 ℃, dispersing for 15min at the rotating speed of 400rpm, then feeding into a single-screw extruder, controlling the extrusion granulation temperature at 240 ℃, and extruding and granulating to obtain the light helmet composite plastic special for bicycles.
Comparative example 1
(1) Grinding QF type silicon dioxide aerogel powder of Nagaoko department of Zhejiang, wherein the rotating speed of the ball mill is controlled at 20rpm and the grinding is carried out for 5min to obtain porous light inorganic powder;
(2) sending the porous light inorganic powder prepared in the step (1) into a high-speed stirrer, starting a high-speed stirring device, and adopting a high rotating speed of 1000rpm to fully suspend the powder, so that the powder is effectively dispersed by completely suspending the material through high-speed stirring; then, a high-pressure atomization spray gun is adopted to spray YE1001 type thermosetting liquid polyimide to the porous light inorganic powder under the action of 1.2MPa, and the liquid polyimide is uniformly coated on the surface of the porous light inorganic powder under the stirring suspension due to the viscosity of the liquid polyimide; the using amount of the liquid polyimide is controlled to be 5 percent of the mass of the porous light inorganic powder;
(3) transferring the material obtained in the step (2) into a three-stage fluidized bed, wherein the temperature of hot air flow of the first-stage fluidized bed is 170 ℃, and performing high-speed suspension treatment on the hot air flow for 3 min; the temperature of hot air flow of the second stage fluidized bed is 200 ℃, and the second stage fluidized bed is subjected to high-speed suspension treatment in the hot air flow for 5 min; the temperature of hot air flow of the third fluidized bed is 280 ℃, and the suspension treatment is carried out for 8min in the hot air flow at high speed; after three-stage heating, polyimide is solidified on the surface of the porous light inorganic powder to form a uniform coating layer; discharging and cooling to obtain uniform and fine light powder;
(4) adding 10 parts by weight of the light powder obtained in the step (3), 40 parts by weight of polycarbonate (Bayer PC1603), 50 parts by weight of ABS, 1 part by weight of POE (ENGAGE 8407 Dow), 662 parts by weight of nylon, 0.5 part by weight of glass fiber, 0.05 part by weight of antioxidant (1010), 1 part by weight of lubricant polyethylene wax and 0.5 part by weight of brominated triazine FR-245 plastic flame retardant into a high-speed mixer, controlling the temperature at 110 ℃, performing dispersion treatment at the rotating speed of 400rpm for 15min, then feeding into a single-screw extruder, controlling the extrusion granulation temperature at 230 ℃, and performing extrusion granulation to obtain the light helmet composite plastic special for bicycles.
Comparative example 1 no silica aerogel was pre-loaded with azodicarbonamide, which was conducted in a manner consistent with example 1. Because azodicarbonamide is not preloaded, when the temperature is raised and the liquid polyimide is cured after being sprayed, the liquid polyimide can bury micropores of the silicon dioxide aerogel, and the density of the obtained cured powder is relatively high, and the effect of reducing the density of the plastic is not obvious.
Comparative example 2
(1) Mixing QF type silicon dioxide aerogel powder of Nanaoko family Zhejiang with azodicarbonamide according to a mass ratio of 100: 1, grinding in a ball mill after uniformly mixing, controlling the rotating speed of the ball mill at 20rpm, grinding for 5min, and entering micropores of the porous light inorganic powder along with the grinding and refining of azodicarbonamide to obtain composite porous light inorganic powder;
(2) sending the composite porous light inorganic powder prepared in the step (1) into a high-speed stirrer, starting a high-speed stirring device, and adopting a high rotating speed of 1000rpm to fully suspend the powder, so that the powder is effectively dispersed by completely suspending the material through high-speed stirring; then, a high-pressure atomization spray gun is adopted to spray YE1001 type thermosetting liquid polyimide to the composite porous light inorganic powder under the action of 1.2MPa, and the liquid polyimide is uniformly coated on the surface of the composite porous light inorganic powder under the stirring suspension due to the viscosity of the liquid polyimide; the using amount of the liquid polyimide is controlled to be 5 percent of the mass of the composite porous light inorganic powder;
(3) transferring the material obtained in the step (2) into a fluidized bed, wherein the temperature of hot air flow of the fluidized bed is 200 ℃, and carrying out high-speed suspension treatment on the material in the hot air flow for 10 min; polyimide is solidified on the surface of the composite porous light inorganic powder to form a coating layer; discharging and cooling to obtain uniform and fine light powder;
(4) adding 10 parts by weight of the light powder obtained in the step (3), 40 parts by weight of polycarbonate (Bayer PC1603), 50 parts by weight of ABS, 1 part by weight of POE (ENGAGE 8407 Dow), 662 parts by weight of nylon, 0.5 part by weight of glass fiber, 0.05 part by weight of antioxidant (1010), 1 part by weight of lubricant polyethylene wax and 0.5 part by weight of brominated triazine FR-245 plastic flame retardant into a high-speed mixer, controlling the temperature at 110 ℃, performing dispersion treatment at the rotating speed of 400rpm for 15min, then feeding into a single-screw extruder, controlling the extrusion granulation temperature at 230 ℃, and performing extrusion granulation to obtain the light helmet composite plastic special for bicycles.
Comparative example 2 was not treated with a three stage fluidized bed but was cured directly at 200 c, at which time azodicarbonamide would rapidly release gas, while polyimide would also rapidly cure, easily causing the coating to loosen and become microporous, failing to form a dense coating, and failing to effectively form a closed-cell powder. Therefore, the powder is liable to adsorb a molten resin when used in the post-filling process, and the weight reduction is not significant.
Comparative example 3
According to parts by weight, 40 parts of polycarbonate (Bayer PC1603), 50 parts of ABS, 1 part of POE (ENGAGE 8407 Dow), 662 parts of nylon, 0.5 part of glass fiber, 0.05 part of antioxidant (1010), 1 part of lubricant polyethylene wax and 0.5 part of brominated triazine FR-245 plastic flame retardant are added into a high-speed mixer, the temperature is controlled at 110 ℃, the mixture is dispersed for 15min at the rotating speed of 400rpm, then the mixture is fed into a single-screw extruder, the extrusion granulation temperature is controlled at 230 ℃, and extrusion granulation is carried out to obtain the light helmet composite plastic special for bicycles.
Comparative example 3 no light powder was added.
The light weight helmet composite plastics obtained in the above examples 1 to 3 and comparative examples 1 to 3 were compared in performance tests.
1. And (3) testing the density: reference GB1033 adopts a specific gravity method to test the density of the composite plastic granules of the light helmet, and because the granules have lower density than water and are not easy to sink in water for direct drainage, porous metal is added into a measuring cylinder to force the granules into the water for drainage test, and the density is calculated.
2. And (3) testing the impact resistance: the light weight helmet composite plastic pellets obtained in examples 1 to 3 and comparative examples 1 to 3 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 ℃ and a humidity of 50%, as shown in Table 1.
Table 1:
Figure GDA0003152666000000121
through tests, after the lightweight treatment, the density of the composite plastic is greatly reduced, the good impact strength is ensured, and the strength requirement of the bicycle helmet shell material is met.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, so: all equivalent changes made according to the structure, shape and principle of the utility model are covered by the protection scope of the utility model.

Claims (8)

1. A preparation method of the light helmet composite plastic special for bicycles is characterized in that: the preparation method comprises the following steps:
(1) mixing porous light inorganic powder and azodicarbonamide according to a mass ratio of 100: 1-1.5, grinding in a ball mill after uniformly mixing, and entering micropores of the porous light inorganic powder along with the grinding and refining of azodicarbonamide to obtain composite porous light inorganic powder; the porous light inorganic powder is silicon dioxide aerogel powder with the porosity of more than 90 percent;
(2) sending the composite porous light inorganic powder prepared in the step (1) into a high-speed stirrer, and starting a high-speed stirring device to suspend the composite porous light inorganic powder in high-speed stirring; then spraying the liquid polyimide to the composite porous light inorganic powder by a high-pressure atomization spray gun, and uniformly coating the liquid polyimide on the surface of the composite porous light inorganic powder under stirring and suspension due to the viscosity of the liquid polyimide;
(3) transferring the material obtained in the step (2) into a third-stage fluidized bed, wherein the temperature of hot air flow of the first-stage fluidized bed is 170 ℃, the temperature of hot air flow of the second-stage fluidized bed is 200 ℃, and the temperature of hot air flow of the third-stage fluidized bed is 280 ℃; after three-stage heating, polyimide is solidified on the surface of the composite porous light inorganic powder to form a uniform coating layer; discharging and cooling to obtain uniform and fine light powder;
(4) adding the light powder obtained in the step (3), polycarbonate, ABS, POE, nylon, glass fiber, antioxidant, lubricant and flame retardant into a high-speed mixer, uniformly mixing, and extruding and granulating by a screw extruder to obtain the light helmet composite plastic special for bicycles; the raw materials are as follows by weight: 5-10 parts of light powder, 40-60 parts of polycarbonate, 30-50 parts of ABS, 1-3 parts of POE, 2-5 parts of nylon, 0.5-2 parts of glass fiber, 0.05-0.1 part of antioxidant, 0.5-1 part of lubricant and 0.5-2 parts of flame retardant.
2. The preparation method of the light weight helmet composite plastic special for bicycles, according to claim 1, is characterized in that: grinding and refining azodicarbonamide to facilitate the azodicarbonamide to enter micropores of porous light inorganic powder; the rotating speed of the ball mill is controlled at 20-35rpm, and the grinding time is controlled at 5-10 min.
3. The preparation method of the light weight helmet composite plastic special for bicycles, according to claim 1, is characterized in that: the high-speed stirring in the step (2) adopts a high rotating speed of 1000 and 1200 rpm.
4. The preparation method of the light weight helmet composite plastic special for bicycles, according to claim 1, is characterized in that: in the step (2), the liquid polyimide with the viscosity of 2000-2500mPa & s is selected.
5. The preparation method of the light weight helmet composite plastic special for bicycles, according to claim 1, is characterized in that: in the step (2), the pressure of a high-pressure atomizing spray gun is controlled to be 1.2-1.5MPa, and the aperture of a nozzle mesh is 1.5 mm; the dosage of the liquid polyimide adopting the high-pressure atomizing spray gun is controlled to be 5-10% of the mass of the composite porous light inorganic powder.
6. The preparation method of the light weight helmet composite plastic special for bicycles, according to claim 1, is characterized in that: in the step (3), three-stage fluidized bed treatment is adopted, and the treatment time in the first-stage fluidized bed is 3 min; the second stage fluidized bed treatment time is 5 min; the processing time of the third fluidized bed is 8-10 min.
7. The preparation method of the light weight helmet composite plastic special for bicycles, according to claim 1, is characterized in that: controlling the temperature of the high-speed mixer in the step (4) to be 80-110 ℃; the screw extruder is a single screw extruder; the extrusion granulation temperature is controlled at 220-260 ℃.
8. A lightweight helmet composite plastic for bicycles, characterized by being prepared by the method of any one of claims 1 to 7.
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US20070105967A1 (en) * 2005-11-08 2007-05-10 Govind Rauniyar Thermoplastic material
CN107296318A (en) * 2017-06-30 2017-10-27 福建泉州海滨防护装备有限公司 A kind of anti-riot helmet and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070105967A1 (en) * 2005-11-08 2007-05-10 Govind Rauniyar Thermoplastic material
CN107296318A (en) * 2017-06-30 2017-10-27 福建泉州海滨防护装备有限公司 A kind of anti-riot helmet and preparation method thereof

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