CN110684229A - Foaming composite material for bicycle safety helmet and preparation method thereof - Google Patents

Foaming composite material for bicycle safety helmet and preparation method thereof Download PDF

Info

Publication number
CN110684229A
CN110684229A CN201911144839.1A CN201911144839A CN110684229A CN 110684229 A CN110684229 A CN 110684229A CN 201911144839 A CN201911144839 A CN 201911144839A CN 110684229 A CN110684229 A CN 110684229A
Authority
CN
China
Prior art keywords
composite material
safety helmet
polyether
bicycle safety
preparing
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
Application number
CN201911144839.1A
Other languages
Chinese (zh)
Other versions
CN110684229B (en
Inventor
张道增
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Yuanjing sporting goods Co.,Ltd.
Original Assignee
Zhejiang Distant View Sports Goods Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang Distant View Sports Goods Co Ltd filed Critical Zhejiang Distant View Sports Goods Co Ltd
Priority to CN201911144839.1A priority Critical patent/CN110684229B/en
Publication of CN110684229A publication Critical patent/CN110684229A/en
Application granted granted Critical
Publication of CN110684229B publication Critical patent/CN110684229B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • AHUMAN NECESSITIES
    • A42HEADWEAR
    • A42BHATS; HEAD COVERINGS
    • A42B3/00Helmets; Helmet covers ; Other protective head coverings
    • A42B3/04Parts, details or accessories of helmets
    • A42B3/10Linings
    • A42B3/12Cushioning devices
    • A42B3/121Cushioning devices with at least one layer or pad containing a fluid
    • AHUMAN NECESSITIES
    • A42HEADWEAR
    • A42BHATS; HEAD COVERINGS
    • A42B3/00Helmets; Helmet covers ; Other protective head coverings
    • A42B3/04Parts, details or accessories of helmets
    • A42B3/10Linings
    • A42B3/12Cushioning devices
    • A42B3/125Cushioning devices with a padded structure, e.g. foam
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066Use of inorganic compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0083Foam properties prepared using water as the sole blowing agent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02Polyalkylene oxides

Abstract

The invention belongs to the field of helmet functional materials, and particularly relates to a foaming composite material for a bicycle safety helmet and a preparation method thereof. The invention disperses the premix formed by silica wet gel, polyether and arabic gum powder in the pre-reacted polyurethane oligomer, the polyether and the oligomer are further foamed and reacted, at the same time, the wet gel and the arabic gum are uniformly dispersed in the polyurethane foam, and after the wet gel and the arabic gum are immersed in polyethylene glycol 600 for adsorption, the uniform non-Newtonian fluid formed by silica, arabic gum and polyethylene glycol 600 is formed in the polyurethane foam; the foaming material has good softness and cushioning property at ordinary times to endow good comfort feeling when in use, but when in severe collision, the non-Newtonian fluid formed by silica, gum arabic and polyethylene glycol 600 in the composite foaming material is rapidly gathered and hardened by softness due to rapid impact, so that the helmet is not easy to crack and pierce, and the head is protected from being injured.

Description

Foaming composite material for bicycle safety helmet and preparation method thereof
Technical Field
The invention belongs to the field of helmet functional materials, and particularly relates to a foaming composite material for a bicycle safety helmet and a preparation method thereof.
Background
The helmet is a head protection device mainly made of plastic and mainly comprises an outer shell, a lining, a suspension device and the like. Helmets are widely used in the construction industry, mining excavation, and sports fields. Particularly in the field of riding, such as cycling, helmets are required to be light and rigid. Both the shell and cushioning layer are required to protect the head and a light and comfortable feel is required. The existing helmet shell materials are generally divided into ABS engineering plastics, PC + ABS composite materials, glass fiber reinforced plastics, carbon fibers and the like, and the materials are required to have excellent heat resistance and weather resistance, excellent stability, wear resistance and impact resistance.
The buffer layer is attached to the inner part of the shell and mainly has the function of absorbing external impact force. The buffer layer mainly adopts white foaming styrene material and foaming polyurethane. However, the buffer layer is made of foam material, so that the strength and the extrusion resistance are poor. In practical use, the foam body has limited compressed deformation distance, and the formed buffering effect is not ideal under the action of larger 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. Upon a severe impact, the broken shell causes the cushioning layer to puncture, severely impacting head safety. In order to improve the safety performance of the helmet, the thickened outer shell is adopted for improvement at present. However, for a thickened helmet, the weight is increased, and the riding comfort is greatly reduced. There are also helmets with increased cushioning layer thickness, but too thick cushioning layers can make the helmet bulky and awkward.
Therefore, the development of new cushioning materials is particularly important to improve the comfort and safety of helmets. The prior art discloses attaching a layer of bubble pad between the outer shell and the lining foam cushion layer to assist in increasing the cushioning effect. However, the bubble pad is easily broken and loses the cushioning effect. non-Newtonian fluids are an intermediate material between solids and liquids and are of great value in the safety protection of helmets. The technical report is as follows: uk D3O developed a new gel material, a non-newtonian fluid with the dual properties of a liquid and a solid substance. It is a very soft, pliable gum when gently kneaded, but becomes very hard in the moment when hit strongly. The gel can be used on various helmets. Only provides a technical idea for further developing the safety and the comfort of the helmet.
However, there are few reports on how to make a non-newtonian fluid reasonable for use in helmets. Due to the special properties of the non-Newtonian fluid, the problems of precipitation, leakage and the like exist when the non-Newtonian fluid is used alone, and even if the non-Newtonian fluid is made into gel, the problem exists in how to be well combined with the buffer layer of the existing helmet.
Disclosure of Invention
In order to improve the safety and comfort of the bicycle helmet material, the invention provides a foaming composite material for a bicycle safety helmet and a preparation method thereof. The material is attached between the helmet shell and the buffer layer, rapidly gathers under the action of severe impact shearing, becomes hard from soft, absorbs impact energy, can prevent puncture, extrusion and the like during strong impact, and effectively protects the head.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a foaming composite material for a bicycle safety helmet is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) adding tetraethoxysilane into a reaction kettle, then adding water and ethanol, adding hydrofluoric acid while stirring, adjusting the pH value of the solution to 3-4, stirring until tetraethoxysilane is completely hydrolyzed, filtering to obtain wet gel, and then adding polyether and Arabic gum powder to obtain a premix;
(2) pre-reacting a polyether and an isocyanate to form an oligomer with an isocyanate at a terminal; then adding the premix obtained in the step (1), a catalyst and a surfactant, uniformly stirring, and quickly adding a plate-shaped mould with the thickness of 5-10mm for foaming and shaping;
(3) and (3) drying the foamed material obtained in the step (2), immersing the dried foamed material into molten polyethylene glycol 600, adsorbing the polyethylene glycol 600, and cooling to obtain the foamed composite material for the bicycle safety helmet.
Further, the mass ratio of the ethyl orthosilicate, the water and the ethanol in the step (1) is 1: 3-5:3-5.
Further, stirring in the step (1) until the tetraethoxysilane is completely hydrolyzed for 1-2 hours.
Further, the wet gel, the polyether and the gum arabic powder in the step (1) are mixed according to the mass ratio of 10-15:20-25:5-10 to obtain a premix. Wherein the wet gel is a semi-dry wet gel that naturally filters out most of the water.
Further, in the step (2), the mass ratio of the polyether to the isocyanate, the premix, the catalyst and the surfactant is as follows: 50:30-35: 50-60:0.1-0.2:0.5-1.
Further, in the steps (1) and (2), polyether 330 is selected as the polyether.
Further, in the step (2), the isocyanate is selected from one of isophorone diisocyanate, toluene diisocyanate and 4, 4' -dicyclohexylmethane diisocyanate.
Further, in the step (2), the catalyst is one of dibutyltin dilaurate and stannous octoate.
Further, the surfactant in the step (2) is silicone oil.
The second object of the present invention is to provide a foamed composite material for a bicycle safety helmet, prepared by the above method. The foam material is directly cut and bonded in the shell layer of the bicycle helmet during use, and has an excellent buffering function. More remarkable functions are represented as follows: firstly, preparing wet gel of silicon dioxide, dispersing a premix formed by the wet gel, polyether and Arabic gum powder in a pre-reacted oligomer, further foaming and reacting the polyether and the oligomer, uniformly dispersing the wet gel and the Arabic gum in polyurethane foam, and forming non-Newtonian fluid formed by uniformly dispersing the silicon dioxide, the Arabic gum and the polyethylene glycol 600 in the polyurethane foam after the non-Newtonian fluid is absorbed by immersing the polyethylene glycol 600; the foaming material has good flexibility and buffering performance, and is directly cut and adhered to the inside of a helmet shell when being used as a bicycle helmet material. The foaming material has good softness and cushioning property at ordinary times to endow good comfort when in use, but when in severe collision, the non-Newtonian fluid formed by silica, gum arabic and polyethylene glycol 600 in the composite foaming material is rapidly gathered and becomes soft and hard due to high impact speed, so that the helmet is not easy to crack and pierce, and the head is protected from being injured.
It is known that the inner layer of the helmet shell is provided with a buffer layer, which can better protect the head when being slightly impacted, but when being strongly impacted, the buffer layer has an unobvious protection effect, and even the head is threatened by piercing and the like along with the fracture of the shell. The non-Newtonian fluid formed by the silicon dioxide, the gum arabic and the polyethylene glycol 600 is creatively and uniformly loaded in the foaming polyurethane to form the composite foaming material, and the material has good softness and buffering property under the common use condition; when the composite foam material is impacted by strong force, the non-Newtonian fluid in the composite foam material is rapidly gathered under the impact shearing action due to the high impact speed, becomes hard from soft, absorbs impact energy, can prevent puncture, extrusion and the like during strong impact, effectively protects the head, and is a safety helmet material with high practicability.
Compared with the prior art, the foaming composite material for the bicycle safety helmet and the preparation method have the following beneficial effects:
(1) by preparing wet gel of silicon dioxide, the wet gel, polyether and Arabic gum powder form a premix, so that when the premix is used as a reactant and is subjected to foaming reaction with pre-reacted oligomer, the polyether and the oligomer in the premix are subjected to foaming reaction under the action of a catalyst and moisture of the wet gel, and the wet gel and the Arabic gum are uniformly dispersed in polyurethane foam, so that uniform load dispersion is realized;
(2) after adsorbing the polyethylene glycol 600, the foaming polyurethane, silica (a dry product of wet gel) and gum arabic form a non-Newtonian fluid, the loading is firm, and the good softness and elasticity of the foaming material are kept during non-rapid impact; when the composite foam material is impacted by strong force, the non-Newtonian fluid in the composite foam material is rapidly gathered under the impact shearing action due to the high impact speed, becomes hard from soft, absorbs impact energy, can prevent puncture, extrusion and the like during strong impact, and effectively protects the head;
(3) the preparation treatment process is simple, has no special requirements on equipment, is easy to realize and is easy for large-scale production and popularization.
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.
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) Adding tetraethoxysilane into a reaction kettle, and then adding water and ethanol, wherein the mass ratio of tetraethoxysilane to water to ethanol is 1: 3:5, adding hydrofluoric acid while stirring, adjusting the pH value of the solution to 3, stirring for 1h until the tetraethoxysilane is completely hydrolyzed, filtering by using filter paper, naturally filtering for 30min, filtering most of water to obtain wet gel, and then adding polyether 330 and gum arabic powder to obtain a premix; mixing the wet gel, the polyether and the gum arabic powder in a mass ratio of 10:20: 10;
(2) polyether 330, toluene diisocyanate, a premix, a catalyst stannous octoate and a surfactant silicone oil are mixed according to the mass ratio: 50:30: weighing the materials at a ratio of 50:0.1: 0.5; pre-reacting polyether 330 and toluene diisocyanate for 30min to form oligomer with terminal isocyanate; then adding the premix, the catalyst and the surfactant, stirring uniformly, and quickly adding a plate-shaped mould with the thickness of 10mm for foaming and shaping;
(3) and (3) drying the foaming material obtained in the step (2), heating polyethylene glycol 600 to 70 ℃ to be completely melted, then soaking the foaming material into the adsorbed polyethylene glycol 600, and then cooling to obtain the foaming composite material for the bicycle safety helmet.
Example 2
(1) Adding tetraethoxysilane into a reaction kettle, and then adding water and ethanol, wherein the mass ratio of tetraethoxysilane to water to ethanol is 1: 4:3, adding hydrofluoric acid while stirring, adjusting the pH value of the solution to 3, stirring for 1h until the tetraethoxysilane is completely hydrolyzed, filtering by using filter paper, naturally filtering for 30min, filtering most of water to obtain wet gel, and then adding polyether 330 and gum arabic powder to obtain a premix; mixing the wet gel, the polyether and the gum arabic powder in a mass ratio of 10:20: 5;
(2) polyether 330, toluene diisocyanate, a premix, a catalyst dibutyltin dilaurate and a surfactant silicone oil are mixed according to the mass ratio: 50:35: weighing the materials at a ratio of 60:0.2: 1; pre-reacting polyether 330 and toluene diisocyanate for 45min to form oligomer with terminal isocyanate; then adding the premix, the catalyst and the surfactant, stirring uniformly, and quickly adding a plate-shaped mould with the thickness of 10mm for foaming and shaping;
(3) and (3) drying the foaming material obtained in the step (2), heating polyethylene glycol 600 to 70 ℃ to be completely melted, then soaking the foaming material into the adsorbed polyethylene glycol 600, and then cooling to obtain the foaming composite material for the bicycle safety helmet.
Example 3
(1) Adding tetraethoxysilane into a reaction kettle, and then adding water and ethanol, wherein the mass ratio of tetraethoxysilane to water to ethanol is 1: 5, adding hydrofluoric acid while stirring, adjusting the pH value of the solution to 3, stirring for 2 hours until the tetraethoxysilane is completely hydrolyzed, filtering by using filter paper, naturally filtering for 30 minutes, filtering most of water to obtain wet gel, and then adding polyether 330 and gum arabic powder to obtain a premix; mixing the wet gel, the polyether and the gum arabic powder in a mass ratio of 15:25: 10;
(2) polyether 330, isophorone diisocyanate, a premix, a catalyst stannous octoate and a surfactant silicone oil are mixed according to the mass ratio: 50:30: weighing materials at a ratio of 55:0.1: 0.5; pre-reacting polyether 330 and isophorone diisocyanate for 30min to form oligomer with isocyanate at the tail end; then adding the premix, the catalyst and the surfactant, stirring uniformly, and quickly adding a plate-shaped mould with the thickness of 10mm for foaming and shaping;
(3) and (3) drying the foaming material obtained in the step (2), heating polyethylene glycol 600 to 70 ℃ to be completely melted, then soaking the foaming material into the adsorbed polyethylene glycol 600, and then cooling to obtain the foaming composite material for the bicycle safety helmet.
Comparative example 1
(1) Adding tetraethoxysilane into a reaction kettle, and then adding water and ethanol, wherein the mass ratio of tetraethoxysilane to water to ethanol is 1: 3:5, adding hydrofluoric acid while stirring, adjusting the pH value of the solution to 3, stirring for 1h until the tetraethoxysilane is completely hydrolyzed, filtering by using filter paper, naturally filtering for 30min, filtering most of water to obtain wet gel, and then adding polyether 330 and gum arabic powder to obtain a premix; mixing the wet gel and the polyether according to the mass ratio of 10: 20;
(2) polyether 330, toluene diisocyanate, a premix, a catalyst stannous octoate and a surfactant silicone oil are mixed according to the mass ratio: 50:30: weighing the materials at a ratio of 50:0.1: 0.5; pre-reacting polyether 330 and toluene diisocyanate for 30min to form oligomer with terminal isocyanate; then adding the premix, the catalyst and the surfactant, stirring uniformly, and quickly adding a plate-shaped mould with the thickness of 10mm for foaming and shaping;
(3) and (3) drying the foaming material obtained in the step (2), heating polyethylene glycol 600 to 70 ℃ to be completely melted, then soaking the foaming material into the adsorbed polyethylene glycol 600, and then cooling to obtain the foaming composite material for the bicycle safety helmet.
Comparative example 1 no gum arabic was added to the premix and the remaining formulation and process were consistent with example 1. Due to the absence of gum arabic, the effect of the formed non-newtonian fluid is reduced and the coagulation protection effect of the foamed material at high speed impact is lower.
Comparative example 2
The method comprises the following steps of mixing a first part of polyether 330, toluene diisocyanate, a second part of polyether 330, a catalyst stannous octoate, a surfactant silicone oil and water in a mass ratio: 50:30: 25:0.1:0.5: 1 weighing materials; pre-reacting a first portion of polyether 330 with toluene diisocyanate for 30min to form an oligomer with isocyanate at the end; then adding a second part of polyether 330, a catalyst, a surfactant and water, stirring uniformly, quickly adding a plate-shaped mould with the thickness of 10mm, foaming, shaping and drying to obtain the foamed polyurethane.
Comparative example 2 no non-newtonian fluid material was loaded in the foamed polyurethane and the foamed material had little protective effect at high speed impact.
The composite foams obtained in examples 1 to 3 and comparative examples 1 to 2 were subjected to a performance test and comparison.
1. The rebound resilience: cutting the composite foam materials obtained in the examples 1-3 and the comparative examples 1-2 into samples of 10cm × 10cm, respectively, pressing a 1kg pressing plate of 10cm × 10cm against the composite foam material, standing for 10min, and measuring the compression ratio (thickness before pressing/thickness after pressing) of the samples; then the pressure is removed, and the resilience (thickness of the removed pressure/original thickness) of the sample is measured; to measure its compressibility, flexibility, elasticity;
2. impact resistance the composite foams obtained in examples 1 to 3 and comparative examples 1 to 2 were each cut into 20cm × 20cm samples, laid flat on a hard plate, and an iron ball weighing 2kg was naturally dropped at 60cm above the plate to impact the composite foam, and the surface of the foam was observed to be impacted. As shown in table 1.
Table 1:
Figure BDA0002279327780000091
through tests, the composite foaming material has excellent resilience and soft and comfortable property in conventional use. When the material is impacted by strong rapid collision, the material is easy to aggregate and harden, and a protective layer can be well formed. The protective auxiliary material is used between a bicycle helmet and a buffer layer, can effectively prevent fragments and the like from being punctured due to violent impact, and is an excellent protective auxiliary material for the buffer layer of the conventional helmet. In contrast, comparative example 1, in which no gum arabic was added, the effect of forming a non-newtonian fluid was reduced, and the coagulation preventive effect of the foamed material was low at the time of high-speed impact. Comparative example 2 no non-newtonian fluid material was loaded in the foamed polyurethane and the foamed material had little protective effect at high speed impact.
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 invention are covered by the protection scope of the invention.

Claims (10)

1. A preparation method of a foaming composite material for a bicycle safety helmet is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) adding tetraethoxysilane into a reaction kettle, then adding water and ethanol, adding hydrofluoric acid while stirring, adjusting the pH value of the solution to 3-4, stirring until tetraethoxysilane is completely hydrolyzed, filtering to obtain wet gel, and then adding polyether and Arabic gum powder to obtain a premix;
(2) pre-reacting a polyether and an isocyanate to form an oligomer with an isocyanate at a terminal; then adding the premix obtained in the step (1), a catalyst and a surfactant, uniformly stirring, and quickly adding a plate-shaped mould with the thickness of 5-10mm for foaming and shaping;
(3) and (3) drying the foamed material obtained in the step (2), immersing the dried foamed material into molten polyethylene glycol 600, adsorbing the polyethylene glycol 600, and cooling to obtain the foamed composite material for the bicycle safety helmet.
2. The method for preparing a foamed composite material for a bicycle safety helmet according to claim 1, wherein: in the step (1), the mass ratio of the ethyl orthosilicate to the water to the ethanol is 1: 3-5:3-5.
3. The method for preparing a foamed composite material for a bicycle safety helmet according to claim 1, wherein: stirring in the step (1) until the tetraethoxysilane is completely hydrolyzed and is controlled to be 1-2 h.
4. The method for preparing a foamed composite material for a bicycle safety helmet according to claim 1, wherein: and (2) mixing the wet gel, the polyether and the Arabic gum powder in the step (1) according to the mass ratio of 10-15:20-25:5-10 to obtain a premix.
5. The method for preparing a foamed composite material for a bicycle safety helmet according to claim 1, wherein: in the step (2), the mass ratio of the polyether to the isocyanate to the premix to the catalyst to the surfactant is as follows: 50:30-35: 50-60:0.1-0.2:0.5-1.
6. The method for preparing a foamed composite material for a bicycle safety helmet according to claim 1, wherein: in the steps (1) and (2), polyether 330 is selected as the polyether.
7. The method for preparing a foamed composite material for a bicycle safety helmet according to claim 1, wherein: in the step (2), the isocyanate is selected from one of isophorone diisocyanate, toluene diisocyanate and 4, 4' -dicyclohexylmethane diisocyanate.
8. The method for preparing a foamed composite material for a bicycle safety helmet according to claim 1, wherein: in the step (2), the catalyst is one of dibutyltin dilaurate and stannous octoate.
9. The method for preparing a foamed composite material for a bicycle safety helmet according to claim 1, wherein: and (3) the surfactant in the step (2) is silicone oil.
10. A foamed composite material for a bicycle safety helmet, prepared by the preparation method of any one of claims 1 to 9.
CN201911144839.1A 2019-11-19 2019-11-19 Foaming composite material for bicycle safety helmet and preparation method thereof Active CN110684229B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911144839.1A CN110684229B (en) 2019-11-19 2019-11-19 Foaming composite material for bicycle safety helmet and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911144839.1A CN110684229B (en) 2019-11-19 2019-11-19 Foaming composite material for bicycle safety helmet and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110684229A true CN110684229A (en) 2020-01-14
CN110684229B CN110684229B (en) 2020-06-30

Family

ID=69117185

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911144839.1A Active CN110684229B (en) 2019-11-19 2019-11-19 Foaming composite material for bicycle safety helmet and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110684229B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115340704A (en) * 2022-09-23 2022-11-15 江苏正力新能电池技术有限公司 Manufacturing method of impact-resistant material, impact-resistant piece, battery box and battery pack

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030131400A1 (en) * 2001-12-31 2003-07-17 Clavell Rafael Calonge Inner cushions for helmets
CN101743263A (en) * 2007-05-15 2010-06-16 陶氏环球技术公司 High resilience foams
US9365692B2 (en) * 2012-08-08 2016-06-14 Provee Technologies, Llc Impact absorbing foam
CN105992780A (en) * 2013-09-04 2016-10-05 G·德恩 Flexible polyurethane and polyurethane/polyorganosiloxane foam materials that absorb impact energy
CN107149194A (en) * 2017-06-08 2017-09-12 中国科学院长春应用化学研究所 A kind of fire hat of inserted alloy framework load-bearing
CN109955570A (en) * 2017-12-26 2019-07-02 洛阳尖端技术研究院 A kind of composite material and preparation method and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030131400A1 (en) * 2001-12-31 2003-07-17 Clavell Rafael Calonge Inner cushions for helmets
CN101743263A (en) * 2007-05-15 2010-06-16 陶氏环球技术公司 High resilience foams
US9365692B2 (en) * 2012-08-08 2016-06-14 Provee Technologies, Llc Impact absorbing foam
CN105992780A (en) * 2013-09-04 2016-10-05 G·德恩 Flexible polyurethane and polyurethane/polyorganosiloxane foam materials that absorb impact energy
CN107149194A (en) * 2017-06-08 2017-09-12 中国科学院长春应用化学研究所 A kind of fire hat of inserted alloy framework load-bearing
CN109955570A (en) * 2017-12-26 2019-07-02 洛阳尖端技术研究院 A kind of composite material and preparation method and application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115340704A (en) * 2022-09-23 2022-11-15 江苏正力新能电池技术有限公司 Manufacturing method of impact-resistant material, impact-resistant piece, battery box and battery pack

Also Published As

Publication number Publication date
CN110684229B (en) 2020-06-30

Similar Documents

Publication Publication Date Title
CN104341770A (en) Preparation technology of novel environmentally friendly polyurethane foamed plastic
CN101948616B (en) Microporous polyurethane elastomer shock absorption element for high-speed railway and preparation method thereof
WO2018086635A1 (en) Vegetable oil-based cartilage bionic cushioning material, and preparation method therefor and application thereof
CN110684229B (en) Foaming composite material for bicycle safety helmet and preparation method thereof
CN104877103B (en) The preparation method of polyurethane elastomer high ferro vibration damper plate
US7078443B2 (en) Viscoelastic foam layer and composition
JP2016516920A (en) Protective headwear
JPH0423004B2 (en)
CN103030782A (en) Slow-rebound memory sponge insole material
CN111548475B (en) Slow-rebound memory cotton and preparation method thereof
CN105669935A (en) Hemp stalk core powder modified antibacterial type soft polyurethane composite foaming material
CN113248769A (en) Graphene polyurethane composite sponge material with good air permeability and application thereof
CN105418880A (en) Polyurethane foam with ultralow surface hardness and high press-to-sink ratio and preparation method thereof
Huo et al. Preparation and properties of shear thickening fluid (STF) capsule filled graded buffer composites
CN102634317A (en) Preparation method of polyurethane/molecular sieve composite adhesive
CN102250307A (en) Biobased micro-porous polyurethane material and preparation method thereof
CN114316344B (en) Filling type physical foaming plastic material and preparation method thereof
CN109836802A (en) A kind of composition, impact resistance polymer composite and preparation method thereof
CN102516491B (en) Low-resilience headrest foam and preparation method thereof
CN113651941A (en) Polyurethane damping material and preparation method thereof
CN109913078B (en) Bio-fiber road sealing material and preparation method thereof
RU2024564C1 (en) Composition for covering sport grounds
CN114516946B (en) Outer-layer buffering thermal insulation material for anti-drop impact light protective box
CN217117585U (en) Slow-rebound knee pad
CN109206584A (en) A kind of flame-proof environmental protection polyurethane elastomer

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 foaming composite material for bicycle safety helmet and its preparation method

Effective date of registration: 20220524

Granted publication date: 20200630

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: 20200630

Pledgee: China Construction Bank Wenling sub branch

Pledgor: Zhejiang Yuanjing sporting goods Co.,Ltd.

Registration number: Y2022330000779