CN104151828A - Method for improving heat resistance of organic silicone resin by nano-silica-coated multi-walled carbon nanotubes - Google Patents
Method for improving heat resistance of organic silicone resin by nano-silica-coated multi-walled carbon nanotubes Download PDFInfo
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- CN104151828A CN104151828A CN201410366113.3A CN201410366113A CN104151828A CN 104151828 A CN104151828 A CN 104151828A CN 201410366113 A CN201410366113 A CN 201410366113A CN 104151828 A CN104151828 A CN 104151828A
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Abstract
The invention discloses a method for improving heat resistance of organic silicone resin by nano-silica-coated multi-walled carbon nanotubes and relates to a method for improving heat resistance of organic silicone resin. The method comprises the following steps: 1) preparing carboxylated multi-walled carbon nanotubes; 2) preparing nano-MWCNTs/SiO2 composite particles; 3) preparing the silicone resin modified by the MWCNTs/SiO2 composite particles. The method disclosed by the invention utilizes a sol-gel method and the MWCNTs/SiO2 nano-composite particles are prepared by growing monodisperse silica on the surfaces of the carbon nanotubes. Thus, alcoholic hydroxyl groups of the silica on the surfaces of the carbon nanotubes easily react with terminal hydroxyl groups of the organic silicone resin, so that the terminal hydroxyl groups of the silicone resin are eliminated, the binding force with matrix resin is strengthened and the heat resistance of the silicone resin is further improved. According to the method, the excellent properties of the MWCNTs and the nano-SiO2 are introduced into the resin and the prepared modified organic silicone resin has relatively high heat resistance.
Description
Technical field
The present invention relates to a kind of method that improves heat resistance of organic silicon resin, be specifically related to a kind of method that adopts the coated multi-walled carbon nano-tubes of nano silicon to improve heat resistance of organic silicon resin.
Background technology
Silicone resin is highly cross-linked cancellated organopolysiloxane.It had both had the series of characteristics of inorganics quartz, had again the easily feature of processing of macromolecular material, was a kind of typical half inorganic polymer.This half inorganic polymer constructional feature, gives its excellent resistance toheat just, is widely applied to aerospace field.In order to adapt to the use properties of aerospacecraft of new generation under hot conditions and extreme particular surroundings, need further to improve the resistance toheat of silicone resin, be therefore necessary silicone resin to carry out study on the modification.The method that modified silicone resin improves resistance toheat with this has following several: (1) introduces thermotolerance group at main chain and the side chain of silicone resin, changes the structure of silicone resin; (2) add thermotolerance filler, improve the resistance toheat of silicone resin; (3) terminal hydroxy group of silicone resin can promote siloxane bond degraded, improves its resistance toheat by the method for elimination terminal hydroxy group.In these method of modifying, owing to adding the method for thermotolerance filler because raw material easily obtains, extensive modernization industry simple to operate and applicable is produced, and is a kind of method of the raising silicone resin resistance toheat effectively generally using.
Multi-walled carbon nano-tubes has the performances such as excellent mechanics, calorifics and optics, and there is good thermal stability, can be joined in resin matrix, resin is carried out to modification, be improved mechanical property, weathering resistance, thermal conductivity and the resistance toheat of resin with this.The properties (intensity, toughness, heat-resisting etc.) that carbon nanotube strengthens polymer matrix composites all has greatly improved, and has caused the extensive concern of industry.But carbon nanotube is easy to assemble agglomerating, be unfavorable for dispersion in resin matrix and lower with matrix resin interaction force, be unfavorable for the transmission of stress.In order to improve dispersiveness and the interaction force thereof of carbon nanotube in resin, improve greatly the thermotolerance of silicone resin, be necessary carbon nanotube to carry out finishing.
Monodisperse nano silicon dioxide is because the miniaturization of particle size, specific surface area sharply increases and hydrogen bonded that silanol base that surface is a large amount of and reactive silane key form, and there is high temperature resistant, insulativity, the special performance such as tough, mechanical property is excellent, be with a wide range of applications.
Summary of the invention
The coated multi-walled carbon nano-tubes of a kind of nano silicon the object of this invention is to provide improves the method for heat resistance of organic silicon resin.The method is by MWCNTs and nanometer SiO
2good characteristic be incorporated in resin, the modified organic silicone resin of making has higher resistance toheat.
The object of the invention is to be achieved through the following technical solutions:
One, the preparation of carboxylated multi-walled carbon nano-tubes: 1～4g multi-walled carbon nano-tubes is placed in to 250～1000mL single port flask, carefully add the mixing solutions (volume ratio of the vitriol oil and concentrated nitric acid is 3:1) of 120～480mL vitriol oil and concentrated nitric acid, 40～80 DEG C of lower magnetic forces stir oxidation 6～12h, in reacted solution, add 500～2000mL distilled water diluting, use porous membrane suction filtration, to leach a large amount of distilled water of thing and clean to washings and be neutral, vacuum-drying obtains carboxylic carbon nano-tube at 40～80 DEG C;
Two, nanometer MWCNTs/SiO
2the preparation of composite particles: a, be dispersed in 82～164mL dehydrated alcohol ultrasonic 0.3～0.6g carboxylic carbon nano-tube, form finely dispersed dispersion liquid; B, in dispersion liquid, add 3.36～6.75mL water, 5.6～11.2mL strong aqua successively, magnetic agitation 30min, mixes solution; C, add 8.9～17.8mL tetraethoxy (TEOS) fast, at room temperature react 12～18 hours; After d, experiment reaction finish, water, dehydrated alcohol centrifuge washing repeatedly successively, until solution becomes neutral, vacuum-drying obtains nanometer MWCNTs/SiO at 40～80 DEG C
2nano-complex particle;
Three, MWCNTs/SiO
2the preparation of composite particles modified silicone resin: add the MWCNTs/SiO that accounts for silicone resin quality 0.1～1% in silicone resin
2nano-complex particle, carries out polyreaction by magnetic stirring apparatus, and temperature of reaction is 60～100 DEG C, and the reaction times is 6～10h, and after completion of the reaction, underpressure distillation obtains the silicone resin of the coated multi-walled carbon nano-tubes modification of nano silicon.
The present invention has following beneficial effect:
1, make multi-wall carbon nano-tube tube-surface produce a large amount of carboxyl oxygen-containing functional groups by the method for acid oxidase:
2, utilize sol-gel method, at carbon nano tube surface growth mono-dispersed nano silicon-dioxide, preparation MWCNTs/SiO
2nano-complex particle.The alcoholic extract hydroxyl group of carbon nano tube surface silicon-dioxide easily reacts with the terminal hydroxy group of silicone resin like this, eliminates the terminal hydroxy group of silicone resin, has strengthened and the bonding force of matrix resin, and then has improved the resistance toheat of silicone resin.
3, starting material easily obtain, and free from environmental pollution as medium using alcohol, are beneficial to environmental protection, easily realize suitability for industrialized production, and are applicable to improve the resistance toheat of other thermosetting resins.
Brief description of the drawings
Fig. 1 is the SEM surface topography map of the MWCNTs for preparing of embodiment 1;
Fig. 2 is MWCNTs/SiO prepared by embodiment 1
2sEM surface topography map;
Fig. 3 is the silicone resin (a) prepared of embodiment 1 and contains 1%MWCNTs/SiO
2the TG curve of modified organic silicone resin (b) in nitrogen atmosphere.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited to this; every technical solution of the present invention is modified or is equal to replacement, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment 1:
One, the preparation of carboxylated multi-walled carbon nano-tubes: 1g multi-walled carbon nano-tubes is placed in to 250mL single port flask, carefully add the mixing solutions (v:v=3:1) of the 120mL vitriol oil and concentrated nitric acid, 40 DEG C of lower magnetic forces stir oxidation 10h, in reacted solution, add 500mL distilled water diluting, use porous membrane suction filtration, to leach a large amount of distilled water of thing and clean to washings and be neutral, vacuum-drying obtains carboxylic carbon nano-tube at 60 DEG C;
Two, nanometer MWCNTs/SiO
2the preparation of composite particles: a, be dispersed in 82mL dehydrated alcohol ultrasonic 0.3g carboxylic carbon nano-tube, form finely dispersed dispersion liquid; B, add 3.36mL water, 5.6mL strong aqua successively, magnetic agitation 30min, mixes solution; C, add 8.9mL tetraethoxy (TEOS) fast, at room temperature react 15 hours; After d, experiment reaction finish, water, dehydrated alcohol centrifuge washing repeatedly successively, until solution becomes neutral, vacuum-drying obtains nanometer MWCNTs/SiO at 60 DEG C
2nano-complex particle.
Three, MWCNTs/SiO
2the preparation of composite particles modified silicone resin: add the MWCNTs/SiO that accounts for silicone resin quality 1% in silicone resin
2nano-complex particle, carries out polyreaction by magnetic stirring apparatus, and temperature of reaction is 90 DEG C, and the reaction times is 7h, and after completion of the reaction, underpressure distillation obtains the silicone resin of the coated multi-walled carbon nano-tubes modification of nano silicon.
As can see from Figure 1, untreated original MWCNTs mat desultorily, agglomeration especially severe, presents network structure closely, and length is very long, reaches several microns; As can see from Figure 2, after acid oxidase, tetraethoxy sol-gel processing, multi-wall carbon nano-tube tube-surface has formed the fine and close and uniform monodisperse nano silicon dioxide of one deck, the alcoholic extract hydroxyl group terminal hydroxy group easy and silicone resin of carbon nano tube surface silicon-dioxide reacts, eliminate terminal hydroxy group, strengthen and the bonding force of matrix resin, and then improved the resistance toheat of silicon resin base composite material.
Table 1 MWCNTs and MWCNTs/SiO
2xPS constituent content
MWCNTs and MWCNTs/SiO thereof from table 1
2xPS constituent content analysis find, multi-walled carbon nano-tubes contains a large amount of C elements, O constituent content is low especially, only has 1.31%; And MWCNTs/SiO
2xPS spectrum figure on had Si element, and O constituent content improves greatly, illustrates at multi-wall carbon nano-tube tube-surface and formed mono-dispersed nano silicon-dioxide, its silicon content is 26.86%.
As can see from Figure 3, in the atmosphere of nitrogen, the initial decomposition temperature of silicone resin (onset temperature) is 120 DEG C of left and right, and rate of weight loss in the time of 900 DEG C is about 18.35%; And the initial decomposition temperature of silicone resin after modification is 168 DEG C of left and right, and rate of weight loss in the time of 900 DEG C is about 15.88%, and the thermotolerance of silicone resin obviously improves.
Embodiment 2:
One, the preparation of carboxylated multi-walled carbon nano-tubes: 4g multi-walled carbon nano-tubes is placed in to 1000mL single port flask, carefully add the mixing solutions (v:v=3:1) of the 480mL vitriol oil and concentrated nitric acid, 40 DEG C of lower magnetic forces stir oxidation 10h, in reacted solution, add 2000mL distilled water diluting, use porous membrane suction filtration, to leach a large amount of distilled water of thing and clean to washings and be neutral, vacuum-drying obtains carboxylic carbon nano-tube at 60 DEG C;
Two, nanometer MWCNTs/SiO
2the preparation of composite particles: a, be dispersed in 164mL dehydrated alcohol ultrasonic 0.6g carboxylic carbon nano-tube, form finely dispersed dispersion liquid; B, add 6.75mL water, 11.2mL strong aqua successively, magnetic agitation 30min, mixes solution; C, add 17.8mL tetraethoxy (TEOS) fast, at room temperature react 15 hours; After d, experiment reaction finish, water, dehydrated alcohol centrifuge washing repeatedly successively, until solution becomes neutral, vacuum-drying obtains nanometer MWCNTs/SiO at 60 DEG C
2nano-complex particle.
Three, MWCNTs/SiO
2the preparation of composite particles modified silicone resin: add the MWCNTs/SiO that accounts for silicone resin quality 0.5% in silicone resin
2nano-complex particle, carries out polyreaction by magnetic stirring apparatus, and temperature of reaction is 80 DEG C, and the reaction times is 8h, and after completion of the reaction, underpressure distillation obtains the silicone resin of the coated multi-walled carbon nano-tubes modification of nano silicon.
Claims (6)
1. the coated multi-walled carbon nano-tubes of nano silicon improves a method for heat resistance of organic silicon resin, it is characterized in that described method steps is as follows:
In silicone resin, add the MWCNTs/SiO that accounts for silicone resin quality 0.1～1%
2nano-complex particle, carries out polyreaction by magnetic stirring apparatus, and temperature of reaction is 60～100 DEG C, and the reaction times is 6～10h, and after completion of the reaction, underpressure distillation obtains the silicone resin of the coated multi-walled carbon nano-tubes modification of nano silicon.
2. the coated multi-walled carbon nano-tubes of nano silicon according to claim 1 improves the method for heat resistance of organic silicon resin, it is characterized in that described MWCNTs/SiO
2the preparation method of nano-complex particle is as follows:
A, be dispersed in 82～164mL dehydrated alcohol ultrasonic 0.3～0.6g carboxylic carbon nano-tube, form finely dispersed dispersion liquid; B, in dispersion liquid, add 3.36～6.75mL water, 5.6～11.2mL strong aqua successively, magnetic agitation 30min, mixes solution; C, add 8.9～17.8mL tetraethoxy fast, at room temperature react 12～18 hours; After d, experiment reaction finish, water, dehydrated alcohol centrifuge washing repeatedly successively, until solution becomes neutral, vacuum-drying obtains nanometer MWCNTs/SiO
2nano-complex particle.
3. the coated multi-walled carbon nano-tubes of nano silicon according to claim 2 improves the method for heat resistance of organic silicon resin, it is characterized in that described vacuum-drying temperature is 40～80 DEG C.
4. the coated multi-walled carbon nano-tubes of nano silicon according to claim 2 improves the method for heat resistance of organic silicon resin, the preparation method who it is characterized in that described carboxylated multi-walled carbon nano-tubes is as follows: 1～4g multi-walled carbon nano-tubes is placed in to 250～1000mL single port flask, carefully add the mixing solutions of 120～480mL vitriol oil and concentrated nitric acid, 40～80 DEG C of lower magnetic forces stir oxidation 6～12h, in reacted solution, add 500～2000mL distilled water diluting, use porous membrane suction filtration, to leach a large amount of distilled water of thing cleans to washings and is neutral, vacuum-drying obtains carboxylic carbon nano-tube.
5. the coated multi-walled carbon nano-tubes of nano silicon according to claim 4 improves the method for heat resistance of organic silicon resin, and the volume ratio that it is characterized in that the described vitriol oil and concentrated nitric acid is 3:1.
6. the coated multi-walled carbon nano-tubes of nano silicon according to claim 4 improves the method for heat resistance of organic silicon resin, it is characterized in that described vacuum-drying temperature is 40～80 DEG C.
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| CN104497577A (en) * | 2014-12-03 | 2015-04-08 | 哈尔滨工业大学 | Method for improving heat resistance of organic silicon resin by use of nano-silica-graphene oxide hybrid composite particles |
| CN105176090A (en) * | 2015-09-18 | 2015-12-23 | 安徽伊法拉电力科技有限公司 | Buffer rubber material for electric cable accessory and preparing method thereof |
| CN105505116A (en) * | 2015-12-25 | 2016-04-20 | 成都石大力盾科技有限公司 | Preparation method of SiO2-MWCNTs (multi-walled carbon nanotubes)-epoxy composite coating |
| CN106905562A (en) * | 2017-03-20 | 2017-06-30 | 江南大学 | A kind of bacteria cellulose in situ/functionalized multi-wall carbonnanotubes membrane material and preparation method thereof |
| CN109233722A (en) * | 2018-08-21 | 2019-01-18 | 新纳奇材料科技江苏有限公司 | A kind of high viscous solid translucent silane-modified joint trimming agent for building and preparation method thereof fastly |
| CN110105767A (en) * | 2019-05-31 | 2019-08-09 | 昆山兆科电子材料有限公司 | A kind of heat conductive flame-retarding insulating materials |
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| CN104497577A (en) * | 2014-12-03 | 2015-04-08 | 哈尔滨工业大学 | Method for improving heat resistance of organic silicon resin by use of nano-silica-graphene oxide hybrid composite particles |
| CN105176090A (en) * | 2015-09-18 | 2015-12-23 | 安徽伊法拉电力科技有限公司 | Buffer rubber material for electric cable accessory and preparing method thereof |
| CN105505116A (en) * | 2015-12-25 | 2016-04-20 | 成都石大力盾科技有限公司 | Preparation method of SiO2-MWCNTs (multi-walled carbon nanotubes)-epoxy composite coating |
| CN106905562A (en) * | 2017-03-20 | 2017-06-30 | 江南大学 | A kind of bacteria cellulose in situ/functionalized multi-wall carbonnanotubes membrane material and preparation method thereof |
| CN109233722A (en) * | 2018-08-21 | 2019-01-18 | 新纳奇材料科技江苏有限公司 | A kind of high viscous solid translucent silane-modified joint trimming agent for building and preparation method thereof fastly |
| CN110105767A (en) * | 2019-05-31 | 2019-08-09 | 昆山兆科电子材料有限公司 | A kind of heat conductive flame-retarding insulating materials |
| CN110133763A (en) * | 2019-06-03 | 2019-08-16 | 吉林大学 | A kind of Metal Substrate wide band antireflective self-cleaning bionic composite membrane and its preparation and application |
| CN114014328A (en) * | 2021-11-19 | 2022-02-08 | 常州大学 | Preparation method of mesoporous silica microspheres formed by multi-walled carbon nanotubes |
| CN114014328B (en) * | 2021-11-19 | 2023-12-01 | 常州大学 | Preparation method of mesoporous silica microspheres with holes formed by multi-wall carbon nanotubes |
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Application publication date: 20141119 |