CN106117551A - A kind of preparation method of easy dispersing Nano carbon tubes optical limiting materials - Google Patents
A kind of preparation method of easy dispersing Nano carbon tubes optical limiting materials Download PDFInfo
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- CN106117551A CN106117551A CN201610491714.6A CN201610491714A CN106117551A CN 106117551 A CN106117551 A CN 106117551A CN 201610491714 A CN201610491714 A CN 201610491714A CN 106117551 A CN106117551 A CN 106117551A
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- optical limiting
- limiting materials
- galla chinensis
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to the preparation method of a kind of easy dispersing Nano carbon tubes optical limiting materials, belong to optical Limiting preparing technical field.For when preparing optical limiting materials at present, CNT is susceptible to reunite, thus cause fluid matrix to be difficult to device, the problem being unfavorable for actual application, it is provided that a kind of by Galla Chinensis being pulverized extraction tannic acid, by tannic acid and CNT irradiation grafting, the little molecule of tannic acid is made to insert carbon nanotube molecule interchain, reducing the active force between carbon nanotube molecule so that it is do not reunite, the easy dispersing Nano carbon tubes optical limiting materials incident illumination of this preparation is at 5.0J/cm2Time, the easy dispersing Nano carbon tubes more common output intensity of optical limiting materials output intensity reduces by 40～50%, and dispersing Nano carbon tubes optical limiting materials device prepared by the present invention forms simplicity, and preparation process is simple, environmental protection, environmentally safe.
Description
Technical field
The present invention relates to the preparation method of a kind of easy dispersing Nano carbon tubes optical limiting materials, belong to optical Limiting technology of preparing neck
Territory.
Background technology
Along with the development of modern laser, various LASER Light Sources are not only widely used in scientific research, industry and army
In thing field, and it is increasingly used in daily life, so that there is the light of protective action to limit to laser
The research of web material and device becomes one of current hotspot.From first observed in 1967 to optical Limiting phenomenon to the nineties in 20th century
In the past, this field, mainly with semi-conducting material as study subject, was discovery and the theoretical developments stage of optical limiting materials.In recent years
Carrying out the research of optical limiting materials and had a swift and violent development, various novel organic and inorganic and macromolecule Optical limiting composites is day by day
Become the focus of scientist's research.Meanwhile, along with measure technology development, the mechanism of action of various optical limiting materials the most gradually by
People are recognized.
Research in recent years finds, carbon nano tube dispersion liquid has good optical limiting properties, i.e. at incident ray energy
Time relatively low, there is higher light transmittance；When incident intensity increases, light transmittance constantly declines, thus realizes laser weapon
Protection.But, CNT is susceptible to reunite, thus causes fluid matrix to be difficult to device, is unfavorable for actual application.
So, the optical limiting materials preparing a kind of effective solution CNT agglomeration traits is necessary.
Summary of the invention
The technical problem to be solved: for when preparing optical limiting materials at present, CNT is susceptible to group
Poly-, thus cause fluid matrix to be difficult to device, the problem being unfavorable for actual application, it is provided that a kind of by by Galla Chinensis
Pulverize and extract tannic acid, by tannic acid and CNT irradiation grafting, make the little molecule of tannic acid insert carbon nanotube molecule chain
Between, reduce the active force between carbon nanotube molecule so that it is do not reunite, efficiently solve CNT and be susceptible to group
Poly-, thus cause fluid matrix to be difficult to device, the problem being unfavorable for actual application.
For solving above-mentioned technical problem, the present invention uses the technical scheme as described below to be:
(1) collect ripe Galla Chinensis, cleaned and naturally dry, pulverizing in jet mill subsequently, be prepared into Galla Chinensis
Granule, then 1:5 in mass ratio, mix the stirring of Galla Chinensis granule and acetone and be placed in beaker, under 200～300W ultrasonic point
Dissipate and process 10～15min, Heat preservation 25～30min at 40～45 DEG C；
(2) after Heat preservation completes, sucking filtration also collects filtrate, rotates and be evaporated to the 1/5 of original volume at 50～55 DEG C, preparation
Obtain Galla Chinensis concentrated solution to be placed in culture dish, then 1:2 in mass ratio, CNT is added to Galla Chinensis concentrated solution, stirring
Culture dish is also placed in ultraviolet irradiation case by mixing, and regulation uviol lamp and culture dish lamp are away from for 10～15cm, to logical in irradiation box
Nitrogen gets rid of air, the most in a nitrogen atmosphere, to its irradiation grafting 25～30min；
(3), after inoculation to be irradiated completes, sucking filtration also collects filter cake, then count by weight, weigh respectively 25～30 parts of filter cakes, 5
～10 parts of kayexalates, 5～10 parts of 1mol/L hydrochloric acid solutions and 45～50 parts of deionized waters are placed in there-necked flask, stir
Mix mixing and be placed in ultrasonic disperse process 15～20min under 200～300W；
(4) after ultrasonic disperse completes, there-necked flask is placed in ice-water bath, there-necked flask is led to nitrogen and gets rid of air, subsequently
It is slowly added dropwise hydrochloric acid solution aniline identical in quality to there-necked flask, after being added dropwise to complete, heating in water bath 25 at 65～70 DEG C
～30min, the Ammonium persulfate. continuing thereafter with dropping aniline quality 1/5 is placed in there-necked flask, continues Heat preservation 10～12h；
(5) after Heat preservation completes, centrifugation 25～30min under 12000～15000r/min, collect lower sediment also
Wash respectively 3～5 times with dehydrated alcohol and deionized water, then at 65～80 DEG C, be dried 3～5h, a kind of easy point can be prepared into
Dissipate CNT optical limiting materials.
Easy dispersing Nano carbon tubes optical limiting materials electrical conductivity prepared by the present invention is 34mScm-1, reach at incident intensity
5.0J/cm2, light transmittance is 20%.
The present invention is compared with additive method, and Advantageous Effects is:
(1) the easy dispersing Nano carbon tubes optical limiting materials incident illumination of this preparation is at 5.0J/cm2Time, easy dispersing Nano carbon tubes light
The more common output intensity of amplitude limit material output intensity reduces by 40～50%；
(2) the dispersing Nano carbon tubes optical limiting materials device that prepared by the present invention forms simplicity, and preparation process is simple, green ring
Protect, environmentally safe.
Detailed description of the invention
First collect ripe Galla Chinensis, cleaned and naturally dry, pulverize in jet mill subsequently, be prepared into five
Gall nut granule, then 1:5 in mass ratio, mix Galla Chinensis granule with acetone stirring and be placed in beaker, super under 200～300W
Sound dispersion processes 10～15min, Heat preservation 25～30min at 40～45 DEG C；After Heat preservation completes, sucking filtration is also collected
Filtrate, rotates at 50～55 DEG C and is evaporated to the 1/5 of original volume, be prepared into Galla Chinensis concentrated solution and be placed in culture dish, then by matter
Amount ratio 1:2, adds CNT to Galla Chinensis concentrated solution, and culture dish is also placed in ultraviolet irradiation case by stirring mixing, adjusts
Nitrogen logical in irradiation box, away from for 10～15cm, is got rid of air, the most in a nitrogen atmosphere, to it by joint uviol lamp and culture dish lamp
Irradiation grafting 25～30min；After inoculation to be irradiated completes, sucking filtration also collects filter cake, then count by weight, respectively weigh 25～
30 parts of filter cakes, 5～10 parts of kayexalates, 5～10 parts of 1mol/L hydrochloric acid solutions and 45～50 parts of deionized waters are placed in three
In mouth flask, stirring mixing is placed in ultrasonic disperse under 200～300W and processes 15～20min；After ultrasonic disperse completes, by three
Mouth flask is placed in ice-water bath, there-necked flask leads to nitrogen and gets rid of air, be slowly added dropwise the benzene that hydrochloric acid solution is identical in quality subsequently
Amine is to there-necked flask, after being added dropwise to complete, and heating in water bath 25～30min at 65～70 DEG C, continue thereafter with dropping aniline quality
The Ammonium persulfate. of 1/5 is placed in there-necked flask, continues Heat preservation 10～12h；After Heat preservation completes, 12000～
Centrifugation 25～30min under 15000r/min, collect lower sediment and wash 3～5 respectively with dehydrated alcohol and deionized water
Secondary, then at 65～80 DEG C, it is dried 3～5h, a kind of easily dispersing Nano carbon tubes optical limiting materials can be prepared into.
Example 1
First collect ripe Galla Chinensis, cleaned and naturally dry, pulverize in jet mill subsequently, be prepared into Galla Chinensis
Granule, then 1:5 in mass ratio, mix Galla Chinensis granule with acetone stirring and be placed in beaker, under 200W at ultrasonic disperse
Reason 10min, Heat preservation 25min at 40 DEG C；After Heat preservation completes, sucking filtration also collects filtrate, rotates and steam at 50 DEG C
Send to the 1/5 of original volume, be prepared into Galla Chinensis concentrated solution and be placed in culture dish, then 1:2 in mass ratio, CNT is added extremely
In Galla Chinensis concentrated solution, culture dish is also placed in ultraviolet irradiation case by stirring mixing, regulation uviol lamp and culture dish lamp away from for
10cm, gets rid of air, the most in a nitrogen atmosphere, to its irradiation grafting 25min to nitrogen logical in irradiation box；Inoculation to be irradiated is complete
Cheng Hou, sucking filtration also collects filter cake, then count by weight, weigh respectively 25 parts of filter cakes, 10 parts of kayexalates, 10 parts
1mol/L hydrochloric acid solution and 50 parts of deionized waters are placed in there-necked flask, and stirring mixing is placed in ultrasonic disperse under 200W and processes
15min；After ultrasonic disperse completes, there-necked flask is placed in ice-water bath, there-necked flask is led to nitrogen and gets rid of air, delay subsequently
The slow hydrochloric acid solution aniline identical in quality that drips is to there-necked flask, after being added dropwise to complete, and heating in water bath 25min at 65 DEG C, with
The rear Ammonium persulfate. continuing dropping aniline quality 1/5 is placed in there-necked flask, continues Heat preservation 10h；Treat that Heat preservation completes
After, centrifugation 25min under 12000r/min, collect lower sediment and wash respectively 3 times with dehydrated alcohol and deionized water,
At 65 DEG C, it is dried 3h again, a kind of easily dispersing Nano carbon tubes optical limiting materials can be prepared into.
Example 2
First collect ripe Galla Chinensis, cleaned and naturally dry, pulverize in jet mill subsequently, be prepared into Galla Chinensis
Granule, then 1:5 in mass ratio, mix Galla Chinensis granule with acetone stirring and be placed in beaker, under 250W at ultrasonic disperse
Reason 12min, Heat preservation 27min at 42 DEG C；After Heat preservation completes, sucking filtration also collects filtrate, rotates and steam at 52 DEG C
Send to the 1/5 of original volume, be prepared into Galla Chinensis concentrated solution and be placed in culture dish, then 1:2 in mass ratio, CNT is added extremely
In Galla Chinensis concentrated solution, culture dish is also placed in ultraviolet irradiation case by stirring mixing, regulation uviol lamp and culture dish lamp away from for
12cm, gets rid of air, the most in a nitrogen atmosphere, to its irradiation grafting 27min to nitrogen logical in irradiation box；Inoculation to be irradiated is complete
Cheng Hou, sucking filtration also collects filter cake, then count by weight, weigh respectively 27 parts of filter cakes, 6 parts of kayexalates, 7 parts
1mol/L hydrochloric acid solution and 47 parts of deionized waters are placed in there-necked flask, and stirring mixing is placed in ultrasonic disperse under 250W and processes
17min；After ultrasonic disperse completes, there-necked flask is placed in ice-water bath, there-necked flask is led to nitrogen and gets rid of air, delay subsequently
The slow hydrochloric acid solution aniline identical in quality that drips is to there-necked flask, after being added dropwise to complete, and heating in water bath 27min at 67 DEG C, with
The rear Ammonium persulfate. continuing dropping aniline quality 1/5 is placed in there-necked flask, continues Heat preservation 11h；Treat that Heat preservation completes
After, centrifugation 27min under 13500r/min, collect lower sediment and wash respectively 4 times with dehydrated alcohol and deionized water,
At 70 DEG C, it is dried 4h again, a kind of easily dispersing Nano carbon tubes optical limiting materials can be prepared into.
Example 3
First collect ripe Galla Chinensis, cleaned and naturally dry, pulverize in jet mill subsequently, be prepared into Galla Chinensis
Granule, then 1:5 in mass ratio, mix Galla Chinensis granule with acetone stirring and be placed in beaker, under 300W at ultrasonic disperse
Reason 15min, Heat preservation 30min at 45 DEG C；After Heat preservation completes, sucking filtration also collects filtrate, rotates and steam at 55 DEG C
Send to the 1/5 of original volume, be prepared into Galla Chinensis concentrated solution and be placed in culture dish, then 1:2 in mass ratio, CNT is added extremely
In Galla Chinensis concentrated solution, culture dish is also placed in ultraviolet irradiation case by stirring mixing, regulation uviol lamp and culture dish lamp away from for
15cm, gets rid of air, the most in a nitrogen atmosphere, to its irradiation grafting 30min to nitrogen logical in irradiation box；Inoculation to be irradiated is complete
Cheng Hou, sucking filtration also collects filter cake, then count by weight, weigh respectively 30 parts of filter cakes, 10 parts of kayexalates, 10 parts
1mol/L hydrochloric acid solution and 50 parts of deionized waters are placed in there-necked flask, and stirring mixing is placed in ultrasonic disperse under 300W and processes
20min；After ultrasonic disperse completes, there-necked flask is placed in ice-water bath, there-necked flask is led to nitrogen and gets rid of air, delay subsequently
The slow hydrochloric acid solution aniline identical in quality that drips is to there-necked flask, after being added dropwise to complete, and heating in water bath 30min at 70 DEG C, with
The rear Ammonium persulfate. continuing dropping aniline quality 1/5 is placed in there-necked flask, continues Heat preservation 12h；Treat that Heat preservation completes
After, centrifugation 30min under 15000r/min, collect lower sediment and wash respectively 5 times with dehydrated alcohol and deionized water,
At 80 DEG C, it is dried 5h again, a kind of easily dispersing Nano carbon tubes optical limiting materials can be prepared into.
Claims (1)
1. the preparation method of an easy dispersing Nano carbon tubes optical limiting materials, it is characterised in that concrete preparation process is:
(1) collect ripe Galla Chinensis, cleaned and naturally dry, pulverizing in jet mill subsequently, be prepared into Galla Chinensis
Granule, then 1:5 in mass ratio, mix the stirring of Galla Chinensis granule and acetone and be placed in beaker, under 200～300W ultrasonic point
Dissipate and process 10～15min, Heat preservation 25～30min at 40～45 DEG C；
(2) after Heat preservation completes, sucking filtration also collects filtrate, rotates and be evaporated to the 1/5 of original volume at 50～55 DEG C, preparation
Obtain Galla Chinensis concentrated solution to be placed in culture dish, then 1:2 in mass ratio, CNT is added to Galla Chinensis concentrated solution, stirring
Culture dish is also placed in ultraviolet irradiation case by mixing, and regulation uviol lamp and culture dish lamp are away from for 10～15cm, to logical in irradiation box
Nitrogen gets rid of air, the most in a nitrogen atmosphere, to its irradiation grafting 25～30min；
(3), after inoculation to be irradiated completes, sucking filtration also collects filter cake, then count by weight, weigh respectively 25～30 parts of filter cakes, 5
～10 parts of kayexalates, 5～10 parts of 1mol/L hydrochloric acid solutions and 45～50 parts of deionized waters are placed in there-necked flask, stir
Mix mixing and be placed in ultrasonic disperse process 15～20min under 200～300W；
(4) after ultrasonic disperse completes, there-necked flask is placed in ice-water bath, there-necked flask is led to nitrogen and gets rid of air, subsequently
It is slowly added dropwise hydrochloric acid solution aniline identical in quality to there-necked flask, after being added dropwise to complete, heating in water bath 25 at 65～70 DEG C
～30min, the Ammonium persulfate. continuing thereafter with dropping aniline quality 1/5 is placed in there-necked flask, continues Heat preservation 10～12h；
(5) after Heat preservation completes, centrifugation 25～30min under 12000～15000r/min, collect lower sediment also
Wash respectively 3～5 times with dehydrated alcohol and deionized water, then at 65～80 DEG C, be dried 3～5h, a kind of easy point can be prepared into
Dissipate CNT optical limiting materials.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250159A (en) * | 2011-04-28 | 2011-11-23 | 贵阳单宁科技有限公司 | Method for extracting and preparing high-purity tannic acid from plant raw material containing tannin |
| CN103091318A (en) * | 2013-02-07 | 2013-05-08 | 哈尔滨工业大学 | Preparation method of grapheme/polydiacetylene composite film and method for quantitatively detecting gas organic by applying composite film |
| CN103803523A (en) * | 2013-11-18 | 2014-05-21 | 广东电网公司电力科学研究院 | Surface modifying and dispersing method of carbon nano-tube |
-
2016
- 2016-06-29 CN CN201610491714.6A patent/CN106117551A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250159A (en) * | 2011-04-28 | 2011-11-23 | 贵阳单宁科技有限公司 | Method for extracting and preparing high-purity tannic acid from plant raw material containing tannin |
| CN103091318A (en) * | 2013-02-07 | 2013-05-08 | 哈尔滨工业大学 | Preparation method of grapheme/polydiacetylene composite film and method for quantitatively detecting gas organic by applying composite film |
| CN103803523A (en) * | 2013-11-18 | 2014-05-21 | 广东电网公司电力科学研究院 | Surface modifying and dispersing method of carbon nano-tube |
Non-Patent Citations (2)
| Title |
|---|
| 孙康宁 等: "《碳纳米管复合材料》", 31 January 2010, 机械工业出版社 * |
| 郭俊鹏 等: "水溶性聚苯胺/碳纳米管复合材料的制备及光限幅性能", 《清华大学学报 (自然科学版)》 * |
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Application publication date: 20161116 |