CN108034040B - Tear-resistant buffer material and preparation method and application thereof - Google Patents
Tear-resistant buffer material and preparation method and application thereof Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention belongs to the field of functional materials, and discloses a tear-resistant buffer material, and a preparation method and application thereof. The buffer material comprises the following raw materials in parts by weight: 5-30 parts of carbon nanotube-based polyether polyol, 100 parts of polyether Voranol 3010, 3 parts of water, 1 part of silicone oil 2370, 0.3 part of 33% by mass of triethylene diamine solution, 0.12 part of stannous octoate and 41 parts of TDI 80/20. The tearing-resistant buffer material is prepared by mixing the substances and then foaming at 60 ℃. The invention synthesizes series of carbon nano tube-based polyether polyols by organically functionalizing the surface of the carbon nano tube, and the modified carbon nano tube can be filled into a system of the buffer material in a large quantity, thereby preparing the buffer material with excellent tear resistance.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a tear-resistant buffer material as well as a preparation method and application thereof.
Background
With the continuous improvement of living standard and the continuous pursuit of living comfort, the application range of the buffer material (also called slow rebound foam plastic or visco-elastic polyurethane foam plastic) is widened year by year, and the dosage is increased rapidly. Cushioning materials were originally developed by the united states general space agency (NASA) in the sixties of the last century, primarily to relieve the pressure experienced by astronauts, to protect their spines, and in particular to protect the astronauts' spines when space shuttles return to and leave the ground. The company Fager dala in sweden develops the product for the second time into a civil (medical) product, is firstly popularized and applied in a medical first aid and monitoring system, and is then rapidly popularized in developed countries such as japan where health is important. The application of the buffer material in China is in a blank state for a long time, and the buffer material is widely applied in the fields of furniture, automobile accessories, shoe materials, sports equipment, medical appliances and the like along with the rapid increase of the economy of China in recent years on the demand of high-quality materials.
The excellent performance of the cushioning material in various application fields is all derived from the special viscoelastic characteristics of the material, namely, when the material is impacted by pressure, the material is subjected to elastic deformation meeting Hooke's law and unrecoverable plastic deformation at the same time, namely, the deformation of the cushioning material is an organic combination of the two deformations. The plastic deformation consumes most of the impact energy, while the elastic deformation accumulates some of the energy to allow the cushioning material to slowly return to its pre-stressed shape after the external force is removed. Essentially, under the action of pressure, the molecular structure of the material can generate 'flow' displacement, deform to fit the contour of the pressure application surface, and spread the supporting points to the whole contact surface, so that the pressure can be dispersed on the whole contact surface. This feature is also referred to as the "pressure-uniform dispersion characteristic" of the cushioning material. According to the action principle, the principle of the performance of the cushioning material depends greatly on the cross-linked network structure, the cell size and the uniformity in the material.
The existing buffer material has the problem of insufficient tear resistance in long-term use, and the service life of the material is seriously influenced. It has been shown that the addition of nanoparticles or nanofibrous fillers, in particular carbon nanotubes, to the cushioning material improves the tear resistance of the material. But at the same time, the surface area of the nano filler is too large, so that the nano filler is easy to aggregate in a material system, and the using effect is difficult to achieve.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention mainly aims to provide a tear-resistant buffer material.
The invention also aims to provide a preparation method of the tear-resistant buffer material. The method is characterized in that the surface of the carbon nano tube is organically functionalized to synthesize series of carbon nano tube-based polyether polyols, and the modified carbon nano tube can be filled into a system of the buffer material in a large amount, so that the buffer material with excellent tear resistance is prepared.
Still another object of the present invention is to provide a use of the tear-resistant cushioning material.
The purpose of the invention is realized by the following technical scheme:
the tear-resistant buffer material is prepared from the following raw materials in parts by weight:
the TDI80/20 is a mixture of 80 mass percent of 2, 4-toluene diisocyanate and 20 mass percent of 2, 6-toluene diisocyanate.
The synthesis method of the carbon nanotube-based polyether polyol comprises the following steps:
(1) acyl chlorination reaction: 15g of carboxylated carbon nanotubes were weighed and 300mL of SOCl was added2Reacting with 5mLDMF at 70 deg.c via stirring for 24 hr; after cooling to room temperature, the reaction product is taken up in N2Washing and filtering with anhydrous THF under protection until the solution is clear; with N2Drying and then placing the product in a drying oven, drying and grinding to obtain black powdery acyl chloride carbon nano tubes;
(2) preparing carbon nanotube-based polyether polyol: taking 10g of the acyl chloride carbon nano tube obtained in the step (1), adding 300mL of oligomeric polyether polyamine solution, and stirring and reacting for 7h at the temperature of 110 ℃; and cooling to room temperature, washing the reaction product with anhydrous THF, and distilling under reduced pressure to obtain a dark brown viscous liquid, namely the carbon nanotube-based polyether polyol.
The average molecular weight of the oligomeric polyether polyamine in the step (2) is 2000-4000, and the concentration of the oligomeric polyether polyamine solution is 0.2 mol/L.
The preparation method of the tear-resistant buffer material comprises the following steps: mixing carbon nano tube-based polyether polyol, polyether Voranol 3010, water, silicone oil 2370, 33% by mass of triethylene diamine solution, stannous octoate and TDI 80/20; and foaming the obtained mixture at 60 ℃ to prepare the buffer material with hydrophobic surface.
The tear-resistant buffer material is applied to the field of tear-resistant buffer materials.
The reaction formula for synthesizing the carbon nanotube-based polyether polyol is shown in the following formula (1):
compared with the prior art, the invention has the following beneficial effects:
(1) the invention synthesizes series of carbon nano tube-based polyether polyols by organically functionalizing the surface of the carbon nano tube, and the modified carbon nano tube can be filled into a system of the buffer material in a large quantity, thereby preparing the buffer material with excellent tear resistance.
(2) The addition of the carbon nanotube-based polyether polyol remarkably improves the tear resistance of the buffer material.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
weighing 15g of a commercial carboxylated carbon nanotube, adding the commercial carboxylated carbon nanotube into 300ml of SOCl and 5ml of DMF, and stirring and reacting for 24 hours at the temperature of 70 ℃; after cooling to room temperature, the reaction product is taken up in N2Washing and filtering with anhydrous THF under protection until the solution is clear; with N2And after blow-drying, placing the product in a drying oven, drying and grinding to obtain a black powdery solid acyl chloride carbon nano tube. Then, 10g of acyl chloride carbon nano tube is taken, 300ml of oligomeric polyether polyamine solution with the concentration of 0.2mol/L (the average molecular weight of the oligomeric polyether polyamine is 2000) is added, and the mixture is stirred and reacts for 7 hours at the temperature of 90 ℃; cooling to room temperature, washing the reaction product with anhydrous THF, and distilling under reduced pressure to obtain dark brown viscous liquid, i.e. carbon nanotube-based polyether polyol (viscosity of 300 at 25 ℃)0mpas)。
Example 2:
weighing 15g of a commercial carboxylated carbon nanotube, adding the commercial carboxylated carbon nanotube into 300ml of SOCl and 5ml of DMF, and stirring and reacting for 24 hours at the temperature of 70 ℃; after cooling to room temperature, the reaction product is taken up in N2Washing and filtering with anhydrous THF under protection until the solution is clear; with N2Drying and then placing the product in a drying oven, drying and grinding to obtain a black powdery solid acyl chloride carbon nano tube; then, 10g of acyl chloride carbon nano tube is taken, 300ml of oligomeric polyether polyamine solution with the concentration of 0.2mol/L (the average molecular weight of the oligomeric polyether polyamine is 3000) is added, and the mixture is stirred and reacts for 8 hours at the temperature of 100 ℃; and cooling to room temperature, washing the reaction product with anhydrous THF, and distilling under reduced pressure to obtain a dark brown viscous liquid, namely the carbon nanotube-based polyether polyol (with the viscosity of 4000mpas at 25 ℃).
Example 3:
weighing 15g of a commercial carboxylated carbon nanotube, adding the commercial carboxylated carbon nanotube into 300ml of SOCl and 5ml of DMF, and stirring and reacting for 24 hours at the temperature of 70 ℃; after cooling to room temperature, the reaction product is taken up in N2Washing and filtering with anhydrous THF under protection until the solution is clear; with N2Drying and then placing the product in a drying oven, drying and grinding to obtain a black powdery solid acyl chloride carbon nano tube; then, 10g of acyl chloride carbon nano tube is taken, 300ml of oligomeric polyether polyamine solution with the concentration of 0.2mol/L (the average molecular weight of the oligomeric polyether polyamine is 4000) is added, and the mixture is stirred and reacts for 9 hours at the temperature of 100 ℃; and cooling to room temperature, washing the reaction product with anhydrous THF, and distilling under reduced pressure to obtain a dark brown viscous liquid, namely the carbon nanotube-based polyether polyol (with the viscosity of 5000mpas at 25 ℃).
Comparative example 1:
the components in the following formula are mixed according to the following proportion, stirred evenly, soaked at 60 ℃ to prepare the buffer material and tested.
Example 4:
the carbon nanotube-based polyether polyol obtained in example 1 was mixed with other raw materials in the following ratio, stirred uniformly, and soaked at 60 ℃ to prepare a tear-resistant buffer material, and the obtained buffer material was subjected to a performance test, see table 1.
Example 5:
the carbon nanotube-based polyether polyol obtained in example 2 was mixed with other raw materials in the following ratio, stirred uniformly, and soaked at 60 ℃ to prepare a tear-resistant buffer material, and the obtained buffer material was subjected to a performance test, see table 1.
Example 6:
the carbon nanotube-based polyether polyol obtained in example 3 was mixed with other raw materials in the following ratio, stirred uniformly, and soaked at 60 ℃ to prepare a tear-resistant buffer material, and the obtained buffer material was subjected to a performance test, see table 1.
Example 7
The carbon nanotube-based polyether polyol obtained in example 1 was mixed with other raw materials in the following ratio, stirred uniformly, and soaked at 60 ℃ to prepare a tear-resistant buffer material, and the obtained buffer material was subjected to a performance test, see table 1.
TABLE 1 Performance testing of the cushioning materials of the present invention
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. A tear-resistant cushioning material characterized by: the buffer material is prepared from the following raw materials in parts by weight:
the synthesis method of the carbon nanotube-based polyether polyol comprises the following steps:
(1) acyl chlorination reaction: 15g of carboxylated carbon nanotubes were weighed and 300mL of SOCl was added2Reacting with 5mLDMF at 70 deg.c via stirring for 24 hr; after cooling to room temperature, the reaction product is taken up in N2Washing and filtering with anhydrous THF under protection until the solution is clear; with N2Drying and then placing the product in a drying oven, drying and grinding to obtain black powdery acyl chloride carbon nano tubes;
(2) preparing carbon nanotube-based polyether polyol: taking 10g of the acyl chloride carbon nano tube obtained in the step (1), adding 300mL of oligomeric polyether polyamine solution, and stirring and reacting for 7h at the temperature of 110 ℃; cooling to room temperature, washing the reaction product with anhydrous THF, and distilling under reduced pressure to obtain dark brown viscous liquid, namely the carbon nanotube-based polyether polyol;
the reaction formula for synthesizing the carbon nanotube-based polyether polyol is shown in the following formula (1):
2. the tear-resistant cushioning material of claim 1, wherein: the average molecular weight of the oligomeric polyether polyamine in the step (2) is 2000-4000, and the concentration of the oligomeric polyether polyamine solution is 0.2 mol/L.
3. The method of making a tear-resistant cushioning material of any of claims 1-2, characterized by the steps of: mixing carbon nano tube-based polyether polyol, polyether Voranol 3010, water, silicone oil 2370, a triethylene diamine solution with the mass fraction of 33%, stannous octoate and TDI 80/20; and foaming the obtained mixture at 60 ℃ to prepare the buffer material with hydrophobic surface.
4. Use of a tear-resistant cushioning material according to any of claims 1-2 in the field of tear-resistant cushioning materials.
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| CN109851757A (en) * | 2019-01-24 | 2019-06-07 | 天津市大邱庄泡沫塑料有限公司 | A kind of flexible polyurethane foam plastic product and its preparation process |
| CN110205079B (en) * | 2019-05-08 | 2021-03-30 | 苏州十一方生物科技有限公司 | Tear-resistant pressure-sensitive hot melt adhesive and preparation method thereof |
| CN110894363A (en) * | 2019-12-09 | 2020-03-20 | 株洲时代新材料科技股份有限公司 | Tear-resistant organic silicon foam material and preparation method thereof |
| CN113910725A (en) * | 2021-10-13 | 2022-01-11 | 泉州市勃力包装材料有限公司 | Novel PVDC coating film and manufacturing method thereof |
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| JP5368716B2 (en) * | 2007-03-01 | 2013-12-18 | 花王株式会社 | Method for producing polyurethane molded product |
| CN101333280A (en) * | 2007-06-26 | 2008-12-31 | 同济大学 | Method for preparing modified urethane elastomer |
| CN101250321A (en) * | 2008-03-18 | 2008-08-27 | 四川大学 | Preparation of light electric polyurethane foam plastic |
| EP2239290A1 (en) * | 2009-04-09 | 2010-10-13 | Bayer MaterialScience AG | Carbon nanotubes containing hydroxyl groups, method for creating same and polyurethane polymers containing these carbon nanotubes |
| WO2015035068A1 (en) * | 2013-09-04 | 2015-03-12 | Ghassan Dehni | Flexible polyurethane and polyurethane/polyorganosiloxane foam materials that absorb impact energy |
| CN103467974A (en) * | 2013-09-06 | 2013-12-25 | 重庆杰博科技有限公司 | Enhanced polyurethane microcellular elastomer composite material and preparation method thereof |
| CN105693968B (en) * | 2016-02-02 | 2018-09-25 | 宁波西博恩新材料科技有限公司 | High performance polyurethane buffering composite material based on Nano filling and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3743616A (en) * | 1971-05-17 | 1973-07-03 | D Kest | Elastomer-based pressure sensitive adhesive composition |
| CN1513757A (en) * | 2003-07-31 | 2004-07-21 | 上海交通大学 | Preparation method of block polymer grafted earbon nano-pipe |
| WO2009023337A2 (en) * | 2007-05-17 | 2009-02-19 | University Of Florida Research Foundation, Inc. | Supramolecular polymers associative to carbon nanotubes |
| CN104004487A (en) * | 2014-06-12 | 2014-08-27 | 哈尔滨理工大学 | Preparation method of alcohol-soluble polyurethane adhesive modified by multi-wall carbon nano-tubes |
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