CN109651622B - synthetic method of organic silicon modified carbon nano-tube suitable for pressure-sensitive adhesive system - Google Patents
synthetic method of organic silicon modified carbon nano-tube suitable for pressure-sensitive adhesive system Download PDFInfo
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- CN109651622B CN109651622B CN201910018217.8A CN201910018217A CN109651622B CN 109651622 B CN109651622 B CN 109651622B CN 201910018217 A CN201910018217 A CN 201910018217A CN 109651622 B CN109651622 B CN 109651622B
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 35
- 239000010703 silicon Substances 0.000 title claims abstract description 35
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 34
- -1 silicon modified carbon nano-tube Chemical class 0.000 title claims abstract description 19
- 238000010189 synthetic method Methods 0.000 title claims description 3
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 68
- 239000002109 single walled nanotube Substances 0.000 claims description 49
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 45
- 239000001257 hydrogen Substances 0.000 claims description 45
- 229910052697 platinum Inorganic materials 0.000 claims description 34
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 32
- 229920002545 silicone oil Polymers 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- 238000010992 reflux Methods 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000002048 multi walled nanotube Substances 0.000 claims description 13
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- 238000006243 chemical reaction Methods 0.000 claims description 9
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 7
- 150000001875 compounds Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 11
- 230000001681 protective effect Effects 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 description 10
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- 239000000853 adhesive Substances 0.000 description 6
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- 238000002834 transmittance Methods 0.000 description 6
- 239000003292 glue Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 230000007423 decrease Effects 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- MHMNJMPURVTYEJ-UHFFFAOYSA-N fluorescein-5-isothiocyanate Chemical compound O1C(=O)C2=CC(N=C=S)=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 MHMNJMPURVTYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NBQNWMBBSKPBAY-UHFFFAOYSA-N iodixanol Chemical compound IC=1C(C(=O)NCC(O)CO)=C(I)C(C(=O)NCC(O)CO)=C(I)C=1N(C(=O)C)CC(O)CN(C(C)=O)C1=C(I)C(C(=O)NCC(O)CO)=C(I)C(C(=O)NCC(O)CO)=C1I NBQNWMBBSKPBAY-UHFFFAOYSA-N 0.000 description 1
- 229960004359 iodixanol Drugs 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a synthesis mode of organic silicon modified carbon nano-tubes suitable for a pressure-sensitive adhesive system, which comprises functionalizing a carbon nano-tube, grafting an organic siloxane molecule containing an active group onto the carbon nano-tube by using a chemical method, wherein the organic silicon modified carbon nano-tube obtained by using the method is mainly applied to an antistatic organic silicon pressure-sensitive adhesive protective film.
Description
Technical Field
The invention relates to the field of material science, in particular to a synthesis mode of organic silicon modified carbon nanotubes applicable to a pressure-sensitive adhesive system.
Background
The carbon nano tube is used as a dimensional nano material, is light in weight, is perfectly connected in a hexagonal structure, and has a plurality of abnormal mechanical, electrical and chemical properties, the application prospect of is wide with the research of the carbon nano tube and the nano material in recent years, in the field of materials, the carbon nano tube is long used as a conductive substance to be added into materials, for example, the carbon nano tube can be used as the conductive substance to be added into a glue layer in a silicon pressure-sensitive adhesive protective film system, so that the protective film has excellent antistatic and even conductive performance, but the carbon nano tube can be used as the conductive substance to be added into the glue layer in most pressure-sensitive adhesive protective films, the carbon nano tube can be used as the conductive substance to be added into the glue layer, but the carbon nano tube can be used as the conductive substance to be added into the glue layer, so that the protective film has 5-20 mu m thickness, after the common carbon nano tube is added, obvious black particles can be seen on the glue layer, which is mainly the problem that the existing carbon nano tube is not uniformly dispersed in the current, and the silicon system is easy to generate agglomeration, so that black particles which can be seen by naked eyes, besides, the carbon nano tube is difficult to be applied to the organic silicon pressure-sensitive adhesive system, the development of the new-sensitive adhesive is difficult to be applied to the organic silicon pressure-sensitive adhesive system, such as 36.
The prior art discloses technical schemes for improving the dispersibility of carbon nanotubes and avoiding agglomeration by grafting long-chain macromolecules onto the carbon nanotubes, but the macromolecules used by the method contain tetrabutylammonium bromide, which can inhibit the solidification of addition type organic silica gel products, and an aqueous solution system is used, and water-containing substances can react with hydrogen-containing silicone oil under the action of a platinum catalyst to cause the silica gel not to be solidified.
The prior art discloses carbon nanotube treatment modes applied to an organosilicon material system, in the patent, only silane coupling agent micromolecules are used for treating acidified carbon nanotubes, the treated carbon nanotubes cannot be guaranteed not to agglomerate or settle in steps, in addition, a ball mill is used for grinding a mixture before a final product, namely the composite heat-conducting silicone grease, the mixing process can greatly reduce the length of the carbon nanotubes, and the surface of the carbon nanotubes is easy to be physically damaged, so that the excellent electric and heat conducting performance of the carbon nanotubes is also greatly weakened.
The prior art discloses organosilicon adhesives and a preparation method thereof, wherein a plurality of carbon materials are doped to obtain the high-thermal-conductivity organosilicon adhesive, the patent only uses carbon nanotubes subjected to acid treatment to be firstly subjected to acyl chlorination and then subjected to amine functionalization treatment, the reaction time is long, the uniform dispersion of the carbon nanotubes in a silica gel system cannot be ensured, inorganic chopped carbon fibers are grafted, the dispersion of the carbon nanotubes is not improved, but the risk of filler sedimentation is improved.
The prior art also provides a treatment method of single-walled carbon nanotubes, but in the method, the dispersing agent, namely rhodamine, fluorescein isothiocyanate and density gradient reagent, contains N elements by using iodixanol-containing solution, and the problem that the activity of a platinum catalyst is reduced and even inactivated by using an organic silicon pressure sensitive adhesive system is solved.
In view of the above, in response to the industrial demand of antistatic silicone pressure-sensitive adhesives, a novel method for treating silicone-modified carbon nanotubes, which is uniformly dispersed and non-agglomerated at , uses a low-boiling-point organic solvent, and does not use a substance containing P, N, S or the like to inhibit the activity of a platinum catalyst, is urgently developed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a treatment method of organic silicon modified carbon nanotubes, which can effectively improve the dispersibility of the carbon nanotubes in organic silicon pressure-sensitive adhesive water, does not influence the curing of addition type silica gel, has good storage stability, can greatly improve the adhesive surface conductivity of a pressure-sensitive adhesive protective film when being applied to a pressure-sensitive adhesive system, has small influence on the light transmittance and stripping force of the protective film, overcomes the defects of the existing carbon nanotube dispersion technology, and widens the application field of the carbon nanotubes.
The specific technical scheme of the invention is as follows.
1. Adding 1 part of carbon nano tube into 10 parts of mixed solution of sulfuric acid and nitric acid in a volume ratio of 1:3, performing ultrasonic pretreatment for 30min, slowly heating to 120 ℃, refluxing for 2h, and filtering acid to obtain the functionalized carbon nano tube (CNT-OH and CNT-COOH) with the surface containing hydroxyl and carboxyl.
2. Adding 1 part of functionalized carbon nanotube with hydroxyl and carboxyl on the surface and 2 parts of hydrogen-containing silicone oil into 97 parts of dehydrated organic solvent, treating with ultrasonic waves, adding a platinum catalyst, carrying out dehydrogenation reaction on the hydrogen-containing silicone oil and the functionalized carbon nanotube, and carrying out heat treatment reflux on the system after the reaction is finished, so as to obtain the organic silicon modified carbon nanotube solution after the platinum catalyst is inactivated.
The reaction formula is shown below.
Different from the prior art, the technical scheme does not use a silane coupling agent.
The acidified carbon nanotubes are treated by only using silane coupling agent micromolecules, so that the treated carbon nanotubes cannot be guaranteed to be agglomerated or settled in the step , inorganic particles such as inorganic chopped carbon fibers are used for treating the carbon nanotubes, the agglomeration of the inorganic particles increases the risk of agglomeration and settlement of the carbon nanotubes, and the carbon nanotubes cannot be uniformly dispersed in an organic solvent, when the agglomeration phenomenon occurs, the electric conductivity and the light transmittance of a product are greatly reduced, the concentration uniformity of the carbon nanotube solvent is affected by when the agglomeration occurs, the problem can be effectively avoided by using siloxane macromolecules to treat the carbon nanotubes, after the organic macromolecular chains are grafted, the carbon nanotubes cannot be adsorbed to each other to cause agglomeration, and the dispersibility in an organic silicon system and the solvent can be improved.
As a preferred scheme of the technical scheme, the carbon nanotubes are types of single-walled carbon nanotubes and multi-walled carbon nanotubes, the diameter of the single-walled carbon nanotube is 1-1.5nm, the length of the single-walled carbon nanotube is 5-10 mu m, the diameter of the multi-walled carbon nanotube is 4-8nm, the length of the multi-walled carbon nanotube is 5-10 mu m, the diameter and the length distribution range of the single-walled carbon nanotube are generally narrower than those of the multi-walled carbon nanotube, carbon tubes with the length distribution between 5 and 10 mu m are selected to be suitable for an antistatic organic silicon pressure sensitive adhesive system, carbon tubes with the length of less than 5 mu m are poor in conductivity and difficult to form a three-dimensional conductive network, carbon tubes with the length of more than 10 mu m are difficult to disperse uniformly, the dispersion difficulty of partial pressure sensitive adhesive is greatly improved, the influence on light transmittance is large.
As the preferable scheme of the technical scheme, the organic solvent is or more of toluene, ethanol, isopropanol, ethyl acetate and 120# solvent oil, the boiling points of the solvents are all less than 150 ℃, and the solvents can boil out in the system in the curing process of the pressure-sensitive adhesive and cannot influence later application.
As a preferable scheme of the technical scheme, the viscosity of the hydrogen-containing silicone oil in the step 2) is 100-5000 mPa & s, and the hydrogen content is 0.1% -1.6%. The hydrogen-containing silicone oil has low viscosity, so that the dispersibility of the carbon nano tubes in the product is reduced and the carbon nano tubes are easy to agglomerate, the viscosity is too high, so that the grafting reaction with the carbon nano tubes is difficult, and the reaction time needs to be greatly prolonged to ensure the high grafting rate of the carbon nano tubes. The hydrogen content of the hydrogen-containing silicone oil is too low, the number of active hydrogen groups is low, excessive hydrosilyl groups cannot be combined with vinyl in an organic silicon pressure-sensitive adhesive system after the reaction is finished, the grafting ratio of the hydrogen-containing silicone oil and the carbon nano tube is reduced, the hydrogen content is too high, the reaction is too fast, even a single macromolecular chain reacts with a multi-carbon tube, and the dispersibility of the carbon nano tube is influenced.
As a preferable scheme of the technical scheme, the ultrasonic treatment time in the step 2) is 20-50 min. Too short a treatment time may result in an unsatisfactory dispersion degree, and too long a treatment time may result in a decrease in the length of the carbon nanotubes and a breakage of the tube wall, thereby affecting the conductivity of the product.
As a preferable scheme of the technical scheme, the dehydrogenation reaction temperature in the step 2) is 80-100 ℃, and the reaction time is 1.5-2.5 h. The activity of the platinum catalyst is high in the reaction temperature, the reaction speed is high, and the catalyst is inactivated due to overhigh temperature.
As a preferable scheme of the technical scheme, the heat treatment temperature in the step 2) is 150-160 ℃, and the treatment time is 1-1.5 h. The reaction temperature can lead to catalyst deactivation, and prevents residual platinum catalyst from generating adverse effect on subsequent application.
As a preferable mode of the present invention, the platinum catalyst is any kinds of chloroplatinic acid or platinum/alkenylsiloxane complex, and the addition amount is 40ppm in terms of mass fraction of platinum.
Compared with the prior art, the invention mainly has the following advantages.
1. The carbon nano tube with the surface containing hydroxyl and carboxyl is obtained by chemical treatment, and the organic silicon macromolecules containing active groups are grafted to the carbon nano tube by using a chemical method, so that the dispersibility of the carbon nano tube in a solvent can be greatly improved, the carbon nano tube is prevented from being adsorbed, and the carbon nano tube is prevented from being agglomerated in the storage process.
2. The modified carbon nanotube is grafted with an organic silicon macromolecular chain, has very good dispersibility and compatibility when applied to an organic silicon pressure-sensitive adhesive system, can realize the dispersion of a carbon nanotube solution in the organic silicon system by simple stirring, has simple mixing process, and can realize the antistatic and even conductive effects of the pressure-sensitive adhesive protective film with lower addition amount (less than 0.1%).
3. The modified carbon nanotube system does not contain P, N, S and other elements, does not influence the curing process of the addition type organic silicon pressure-sensitive adhesive system, and does not cause the situations that the activity of the catalyst is inhibited or even inactivated and the like.
Drawings
FIG. 1 is a photograph of a metallographic microscope showing a gel surface with 10% of carbon nanotubes added, obtained in example 1.
FIG. 2 is a photograph of a metallurgical microscope showing a 10% addition of a commercially available carbon nanotube dispersion on a surface of a glass.
Detailed Description
The present application will be described in further detail with reference to the following drawings and specific examples , but the present application is not limited by the drawings and examples.
Example 1.
The method for processing the organic silicon modified carbon nano tube comprises the following steps.
1) Adding 1 part of single-walled carbon nanotube SWCNT into 10 parts of mixed solution of 100ml sulfuric acid and 300ml nitric acid according to parts by weight, firstly carrying out ultrasonic pretreatment for 30min, then slowly heating to 120 ℃, and refluxing for 2h to obtain the single-walled carbon nanotube (SWCNT-OH and SWCNT-COOH) with hydroxyl and carboxyl on the surface.
2) Adding 1g of functionalized single-walled carbon nanotube with hydroxyl and carboxyl on the surface and 2g of hydrogen-containing silicone oil (with the viscosity of 50cps and the hydrogen content of 1.0%) into 97g of mixed solution of dehydrated toluene and 120# solvent oil (with the volume ratio of 1: 1), treating with ultrasonic waves for 30min, adding 0.8g of platinum catalyst (5000 ppm), carrying out dehydrogenation reaction on the hydrogen-containing silicone oil and the functionalized carbon nanotube at 80 ℃ for 1.5h, and then carrying out heat treatment and reflux at 150 ℃ for 1h to inactivate the platinum catalyst, thus obtaining the organosilicon modified single-walled carbon nanotube solution.
Example 2.
The method for processing the organic silicon modified carbon nano tube comprises the following steps.
1) Adding 1 part of multi-walled carbon nanotube (MWCNT) into 10 parts of mixed solution of 100ml sulfuric acid and 300ml nitric acid according to parts by weight, firstly carrying out ultrasonic pretreatment for 30min, then slowly heating to 120 ℃, and then refluxing for 2h to obtain the multi-walled carbon nanotube (MWCNT-OH and MWCNT-COOH) with the surface containing hydroxyl and carboxyl.
2) Adding 1g of functionalized multi-walled carbon nanotube with hydroxyl and carboxyl on the surface and 2g of hydrogen-containing silicone oil (with the viscosity of 50cps and the hydrogen content of 1.0%) into 97g of dehydrated toluene solution, treating the solution for 30min by ultrasonic waves, adding 0.8g of platinum catalyst (5000 ppm), carrying out dehydrogenation reaction on the hydrogen-containing silicone oil and the functionalized carbon nanotube at 80 ℃ for 2h, and then carrying out heat treatment and reflux at 150 ℃ for 1h to inactivate the platinum catalyst to obtain the organic silicon modified multi-walled carbon nanotube solution.
Example 3.
The method for processing the organic silicon modified carbon nano tube comprises the following steps.
1) Adding 1 part of single-walled carbon nanotube SWCNT into 10 parts of mixed solution of 100ml sulfuric acid and 300ml nitric acid according to parts by weight, firstly carrying out ultrasonic pretreatment for 30min, then slowly heating to 120 ℃, and refluxing for 2h to obtain the single-walled carbon nanotube (SWCNT-OH and SWCNT-COOH) with hydroxyl and carboxyl on the surface.
2) Adding 1g of functionalized single-walled carbon nanotube with hydroxyl and carboxyl on the surface and 2g of hydrogen-containing silicone oil (with the viscosity of 50cps and the hydrogen content of 1.0%) into 97g of dehydrated ethanol and isopropanol (volume ratio of 1: 1), treating with ultrasonic waves for 30min, adding 0.8g of platinum catalyst (5000 ppm), carrying out dehydrogenation reaction on the hydrogen-containing silicone oil and the functionalized carbon nanotube at 80 ℃ for 1.5h, and then carrying out heat treatment and reflux at 150 ℃ for 1h to inactivate the platinum catalyst, thus obtaining the organosilicon modified single-walled carbon nanotube solution.
Example 4.
The method for processing the organic silicon modified carbon nano tube comprises the following steps.
1) Adding 1 part of single-walled carbon nanotube SWCNT into 10 parts of mixed solution of 100ml sulfuric acid and 300ml nitric acid according to parts by weight, firstly carrying out ultrasonic pretreatment for 30min, then slowly heating to 120 ℃, and refluxing for 2h to obtain the single-walled carbon nanotube (SWCNT-OH and SWCNT-COOH) with hydroxyl and carboxyl on the surface.
2) Adding 1g of functionalized single-walled carbon nanotube with hydroxyl and carboxyl on the surface and 2g of hydrogen-containing silicone oil (with the viscosity of 50cps and the hydrogen content of 1.0%) into 97g of dehydrated ethanol and ethyl acetate (volume ratio of 1: 1), treating with ultrasonic waves for 30min, adding 0.8g of platinum catalyst (5000 ppm), carrying out dehydrogenation reaction on the hydrogen-containing silicone oil and the functionalized carbon nanotube at 80 ℃ for 1.5h, and then carrying out heat treatment and reflux at 150 ℃ for 1h to inactivate the platinum catalyst, thus obtaining the organosilicon modified single-walled carbon nanotube solution.
Example 5.
The method for processing the organic silicon modified carbon nano tube comprises the following steps.
1) Adding 1 part of single-walled carbon nanotube SWCNT into 10 parts of mixed solution of 100ml sulfuric acid and 300ml nitric acid according to parts by weight, firstly carrying out ultrasonic pretreatment for 30min, then slowly heating to 120 ℃, and refluxing for 2h to obtain the single-walled carbon nanotube (SWCNT-OH and SWCNT-COOH) with hydroxyl and carboxyl on the surface.
2) Adding 1g of functionalized single-walled carbon nanotube with hydroxyl and carboxyl on the surface and 2g of hydrogen-containing silicone oil (with the viscosity of 200cps and the hydrogen content of 1.0%) into 97g of mixed solution of dehydrated toluene and 120# solvent oil (with the volume ratio of 1: 1), treating with ultrasonic waves for 40min, adding 0.8g of platinum catalyst (5000 ppm), carrying out dehydrogenation reaction on the hydrogen-containing silicone oil and the functionalized carbon nanotube at 90 ℃ for 2h, and then carrying out heat treatment and reflux at 150 ℃ for 1h to inactivate the platinum catalyst, thus obtaining the organosilicon modified single-walled carbon nanotube solution.
Example 6.
The method for processing the organic silicon modified carbon nano tube comprises the following steps.
1) Adding 1 part of single-walled carbon nanotube SWCNT into 10 parts of mixed solution of 100ml sulfuric acid and 300ml nitric acid according to parts by weight, firstly carrying out ultrasonic pretreatment for 30min, then slowly heating to 120 ℃, and refluxing for 2h to obtain the single-walled carbon nanotube (SWCNT-OH and SWCNT-COOH) with hydroxyl and carboxyl on the surface.
2) Adding 1g of functionalized single-walled carbon nanotube with hydroxyl and carboxyl on the surface and 2g of hydrogen-containing silicone oil (the viscosity is 3000cps, the hydrogen content is 1.0%) into 97g of mixed solution of dehydrated toluene and 120# solvent oil (the volume ratio is 1: 1), treating with ultrasonic waves for 45min, adding 0.8g of platinum catalyst (5000 ppm), carrying out dehydrogenation reaction on the hydrogen-containing silicone oil and the functionalized carbon nanotube at 100 ℃ for 2.5h, and then carrying out heat treatment and reflux at 150 ℃ for 1h to inactivate the platinum catalyst, thus obtaining the organosilicon modified single-walled carbon nanotube solution.
Example 7.
The method for processing the organic silicon modified carbon nano tube comprises the following steps.
1) Adding 1 part of single-walled carbon nanotube SWCNT into 10 parts of mixed solution of 100ml sulfuric acid and 300ml nitric acid according to parts by weight, firstly carrying out ultrasonic pretreatment for 30min, then slowly heating to 120 ℃, and refluxing for 2h to obtain the single-walled carbon nanotube (SWCNT-OH and SWCNT-COOH) with hydroxyl and carboxyl on the surface.
2) Adding 1g of functionalized single-walled carbon nanotube with hydroxyl and carboxyl on the surface and 2g of hydrogen-containing silicone oil (with the viscosity of 200cps and the hydrogen content of 1.5%) into 97g of mixed solution of dehydrated toluene and 120# solvent oil (with the volume ratio of 1: 1), treating with ultrasonic waves for 40min, adding 0.8g of platinum catalyst (5000 ppm), carrying out dehydrogenation reaction on the hydrogen-containing silicone oil and the functionalized carbon nanotube at 90 ℃ for 2h, and then carrying out heat treatment and reflux at 150 ℃ for 1h to inactivate the platinum catalyst, thus obtaining the organosilicon modified single-walled carbon nanotube solution.
Example 8.
The method for processing the organic silicon modified carbon nano tube comprises the following steps.
1) Adding 1 part of single-walled carbon nanotube SWCNT into 10 parts of mixed solution of 100ml sulfuric acid and 300ml nitric acid according to parts by weight, firstly carrying out ultrasonic pretreatment for 30min, then slowly heating to 120 ℃, and refluxing for 2h to obtain the single-walled carbon nanotube (SWCNT-OH and SWCNT-COOH) with hydroxyl and carboxyl on the surface.
2) 1g of functionalized single-walled carbon nanotube with hydroxyl and carboxyl on the surface and 2g of hydrogen-containing silicone oil (viscosity 200cps, hydrogen content 0.4%) are added into 97g of dehydrated toluene and 120# solvent oil (volume ratio 1: 1) and (2) treating the mixed solution for 40min by using ultrasonic waves, adding 0.8g of platinum catalyst (5000 ppm), carrying out dehydrogenation reaction on the hydrogen-containing silicone oil and the functionalized carbon nanotube at 90 ℃ for 2h, and then carrying out heat treatment and reflux at 150 ℃ for 1h to inactivate the platinum catalyst to obtain the organosilicon modified single-walled carbon nanotube solution.
Example 9.
The method for processing the organic silicon modified carbon nano tube comprises the following steps.
1) Adding 1 part of single-walled carbon nanotube SWCNT into 10 parts of mixed solution of 100ml sulfuric acid and 300ml nitric acid according to parts by weight, firstly carrying out ultrasonic pretreatment for 30min, then slowly heating to 120 ℃, and refluxing for 2h to obtain the single-walled carbon nanotube (SWCNT-OH and SWCNT-COOH) with hydroxyl and carboxyl on the surface.
2) Adding 1g of functionalized single-walled carbon nanotube with hydroxyl and carboxyl on the surface and 2g of hydrogen-containing silicone oil (with the viscosity of 50cps and the hydrogen content of 1.0%) into 97g of mixed solution of dehydrated toluene and 120# solvent oil (with the volume ratio of 1: 1), treating with ultrasonic waves for 30min, adding 0.8g of platinum catalyst (5000 ppm), carrying out dehydrogenation reaction on the hydrogen-containing silicone oil and the functionalized carbon nanotube at 80 ℃ for 1.5h, and then carrying out heat treatment and reflux at 160 ℃ for 1.5h to inactivate the platinum catalyst, thus obtaining the organosilicon modified single-walled carbon nanotube solution.
The carbon nanotube dispersion liquid prepared in the embodiment 1 of the present application and a certain commercially available carbon nanotube dispersion liquid are added into an organic silicon pressure sensitive adhesive system according to a proportion of 10%, and the adhesive is coated to form a film under the condition that the rest parameters are .
The samples coated as films in the above examples were tested at for peel strength (180 °) according to astm d-3330, surface resistance of pressure sensitive adhesive according to astm d-257, light transmittance according to astm d-1003, dispersibility verified by observing the number of particles per square decimeter of filter cloth residue after filtering the carbon nanotube dispersion through a 400 mesh filter cloth, and dispersibility was rated at 4, wherein "excellent" means a particle number of less than 2, "good" means a particle number of between 2 and 5, "medium" means a particle number of between 6 and 9, "poor" means a particle number of more than 10, and the related results are shown in table 1.
Watch (A)
The different formulations correspond to the test data of the sample.
As can be seen from table 1, as the amount of CNT added increases, the transmittance gradually decreases, the peel force attenuation gradually increases, the surface resistance gradually decreases, and the conductivity increases. Compared with example 1, example 2 has a larger influence on the light transmittance and the peeling force of the product, and needs a higher addition amount to realize a lower veneer resistance value, but the cost is very low, mainly because the market price of the multi-wall carbon nanotube is far lower than that of the single-wall carbon nanotube. Therefore, in the actual application process, a proper formula is selected according to actual requirements.
Table 2 test data for different formulations corresponding to the coupons.
Three experiments of comparative examples 1, 3 and 4 show that the final effect of the product is not much by using several solvents provided by the scheme. Three experiments of comparative examples 1, 5 and 6 show that the larger the viscosity of the hydrogen-containing silicone oil is, the better the dispersibility is, and the resistance value of the surface of the adhesive applied to the pressure-sensitive adhesive tends to be reduced, but the larger the viscosity of the hydrogen-containing silicone oil is, the longer the ultrasonic treatment time is, and the higher the reaction temperature and the longer the reaction time are required for dehydrogenation reaction after treatment. Compared with the three experiments of the examples 1, 7 and 8, the lower the hydrogen content of the hydrogen-containing silicone oil is, the smaller the influence of the addition of the carbon nano tube on the stripping force of the pressure-sensitive adhesive is, and the dispersibility of the carbon nano tube is gradually improved. Compared with two experiments of examples 1 and 9, the improvement of the heat treatment reflux time and temperature has little influence on the dispersibility of the carbon nano tube, mainly the platinum is inactivated more thoroughly, and the influence on the stripping force of the pressure-sensitive adhesive is smaller.
The present invention has been described in connection with the specific embodiments, and it is to be understood that the invention is not limited to the above-described embodiments, and various modifications may be made without departing from the spirit and scope of the invention.
Claims (8)
1, synthetic method of organic silicon modified carbon nano tube suitable for pressure sensitive adhesive system, which is characterized by comprising the following steps:
1) adding 1 part of carbon nano tube into 10 parts of mixed solution of sulfuric acid and nitric acid in a volume ratio of 1:3, performing ultrasonic pretreatment for 30min, slowly heating to 120 ℃, refluxing for 2h, and filtering acid to obtain a functionalized carbon nano tube with hydroxyl and carboxyl on the surface;
2) adding 1 part of functionalized carbon nanotube with hydroxyl and carboxyl on the surface and 2 parts of hydrogen-containing silicone oil into 97 parts of dehydrated organic solvent, treating with ultrasonic waves, adding a platinum catalyst, carrying out dehydrogenation reaction on the hydrogen-containing silicone oil and the functionalized carbon nanotube, and carrying out heat treatment reflux on a system after the reaction is finished so as to inactivate the platinum catalyst to obtain an organic silicon modified carbon nanotube solution;
the synthesis method does not use a silane coupling agent.
2. The method for synthesizing organosilicon modified carbon nanotubes applicable to pressure-sensitive adhesive system of claim 1, wherein the carbon nanotubes in step 1) are kinds of single-walled carbon nanotubes and multi-walled carbon nanotubes, the diameter of the single-walled carbon nanotubes is 1-1.5nm, the length of the single-walled carbon nanotubes is 5-10 μm, and the diameter of the multi-walled carbon nanotubes is 4-8nm, and the length of the multi-walled carbon nanotubes is 5-12 μm.
3. The method for synthesizing organosilicon modified carbon nanotubes applicable to pressure-sensitive adhesive system according to claim 1, wherein the organic solvent in step 2) is or more selected from toluene, ethanol, isopropanol, ethyl acetate and 120# solvent oil.
4. The method for synthesizing silicone modified carbon nanotubes suitable for use in a pressure sensitive adhesive system according to claim 1, wherein: the viscosity of the hydrogen-containing silicone oil in the step 2) is 10-5000 mPa & s, and the hydrogen content is 0.1% -1.6%.
5. The method for synthesizing silicone modified carbon nanotubes suitable for use in a pressure sensitive adhesive system according to claim 1, wherein: the ultrasonic treatment time in the step 2) is 20-50 min.
6. The method for synthesizing silicone modified carbon nanotubes suitable for use in a pressure sensitive adhesive system according to claim 1, wherein: in the step 2), the dehydrogenation reaction temperature is 80-100 ℃, and the reaction time is 1.5-2.5 h.
7. The method for synthesizing silicone modified carbon nanotubes suitable for use in a pressure sensitive adhesive system according to claim 1, wherein: the heat treatment temperature in the step 2) is 150-160 ℃, and the treatment time is 1-1.5 h.
8. The method for synthesizing organosilicon modified carbon nanotubes applicable to pressure-sensitive adhesive system of claim 1, wherein the platinum catalyst in step 2) is any kinds of chloroplatinic acid or platinum/olefin siloxane coordination compound, and the addition amount is 40ppm calculated by mass fraction of platinum.
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