CN109651622A - A kind of synthesis mode of the organic-silicon-modified carbon nanotube suitable for pressure sensitive adhesive system - Google Patents
A kind of synthesis mode of the organic-silicon-modified carbon nanotube suitable for pressure sensitive adhesive system Download PDFInfo
- Publication number
- CN109651622A CN109651622A CN201910018217.8A CN201910018217A CN109651622A CN 109651622 A CN109651622 A CN 109651622A CN 201910018217 A CN201910018217 A CN 201910018217A CN 109651622 A CN109651622 A CN 109651622A
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- organic
- silicon
- sensitive adhesive
- pressure sensitive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Carbon And Carbon Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention provides a kind of synthesis modes of organic-silicon-modified carbon nanotube suitable for pressure sensitive adhesive system, first by functionalization, reuse chemical method and the organosiloxane molecule containing active group is grafted in carbon nanotube.It is mainly used in antistatic silicone pressure-sensitive adhesive protective film using the organic-silicon-modified carbon nanotube that this method obtains.The carbon nanotube has extraordinary dispersibility and storage characteristics, avoids common carbon nanometer tube material and the problems such as reuniting or settling easily occurs during difficulties in dispersion, storage in organic pressure-sensitive gel.And since carbon nanotube is handled using only polysiloxanes macromolecular chain, without elements such as P, N, S in system, subsequent applications will not be had an impact by being applied in pressure sensitive adhesive system.
Description
Technical field
The present invention relates to materials science field, especially a kind of organic-silicon-modified carbon nanotube suitable for pressure sensitive adhesive system
Synthesis mode.
Background technique
Carbon nanotube is as monodimension nanometer material, and light-weight, hexagonal structure connection is perfect, has many abnormal power
, electricity and chemical property.Goed deep into its wide application prospect also not with carbon nanotube and nano materials research in recent years
It shows disconnectedly.In materialogy field, carbon nanotube length is used as conductive materials and is added in material.Such as it applies and is having
In machine silicon pressure-sensitive adhesive protective film system, carbon nanotube can be used as conductive materials and glue-line be added, and imparting protective film glue-line is excellent to be resisted
Electrostatic even electric conductivity.But since layer of silica gel thickness only has 5-20 μm in most of pressure-sensitive adhesive protective films, common carbon nanotube
After addition, apparent black particle can be seen in glue surface, this is mainly that the generally existing dispersion of current carbon nanotube is uneven
The problem of, and the poor compatibility in silica gel system, it is easy to produce reunion, leads to macroscopic black particle, to make its hardly possible
To be applied in organic pressure-sensitive gel system.In addition to this, some carbon nanotubes by processing after modified, because in its system
Easily leading to the not cured substance of add-on type silica gel or its decentralized medium containing P, N, S etc. is that water causes silica gel not solidify or high boiling
Point organic solvent such as N-Methyl pyrrolidone is difficult to boil from pressure sensitive adhesive system out, it is caused to be difficult to apply to organic pressure-sensitive gel
In.In conclusion it is extremely urgent to develop a kind of novel carbon nanotube that can be applied to organic pressure-sensitive gel system.
Prior art discloses a kind of are grafted in carbon nanotube using long-chain macromolecule to improve the dispersion of carbon nanotube
Property, avoid the technical solution reunited, but its macromolecular used contains tetrabutylammonium bromide, can be suppressed to additional organosilicon glue
The solidification of class product, and it uses water solution system, hydrous matter can react under platinum catalyst effect with containing hydrogen silicone oil to be caused
Silica gel does not solidify.The patent also uses excessive sodium hydrate to handle final product, leads to product meta-alkalescence, is applied to silica gel system
In can lure that silica gel cracks at high temperature into, influence the use temperature of final products.
Prior art discloses a kind of processing mode for applying the carbon nanotube in organosilicon material system, in the patent
Carbon nanotube after handling acidification using only silane coupling agent small molecule, not can guarantee that treated, carbon nanotube will not be into one
Step occurs to reunite or settle, and the patent uses ball mill grinding mixture before obtaining final products composite heat-conducting silicone grease, should
Hybrid technique will be greatly reduced the length of carbon nanotube, and carbon pipe surface is subject to Physical Damage, so that carbon nanotube is excellent
Electrical and thermal conductivity performance also significantly weaken therewith.
Prior art discloses a kind of organic silicon adhesive and preparation method thereof, adulterates to obtain height using various carbon materials and lead
Hot organic silicon adhesive.Acid is used only in the patent, and treated that the chloride of carbon nanotube elder generation carries out amino-functionalization processing again, reaction
Time is long, and not can guarantee that carbon nanotube is evenly dispersed in silica gel system, and grafted inorganic chopped carbon fiber does not improve carbon
The dispersibility of nanotube improves the risk that filler settles instead.Lead to carbon nanometer because being grafted with inorganic chopped carbon fiber
Graft reaction can not also occur with organosilicon systems again for pipe, and carbon nanotube is physical dispersion in adhesive in the product.Work as carbon
After nanotube is added to silica gel system, which improves the dispersibility of carbon nanotube by mill mixing, the hybrid technique
Also it will be greatly reduced the length of carbon nanotube, and carbon pipe surface is subject to Physical Damage, thus the conduction that carbon nanotube is excellent
Heating conduction also significantly weakens therewith.
The prior art additionally provides a kind of processing method of single-walled carbon nanotube, but dispersing agent described in this method: Luo Dan
Bright to contain N element, fluorescein isothiocynate element containing S, density gradient reagent is using the solution containing Iodixanol containing N element, use
Will lead to platinum catalyst activity to organic pressure-sensitive gel system reduces the problem of even inactivating.
In conclusion being directed to the industry requirement of antistatic silicone pressure sensitive adhesive, develops one kind and be uniformly dispersed and do not reunite, make
With low boiling point organic solvent, the novel organosilicon carbon modified of the active substance of platinum catalyst is inhibited to receive without using containing P, N, S etc.
The processing method of mitron is extremely urgent.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of processing methods of organic-silicon-modified carbon nanotube, it can have
Effect improves dispersibility of the carbon nanotube in silicone pressure sensitive glue, has no effect on the solidification of add-on type silica gel, storage stability
It is good, applied to the glue surface conductivity that can increase substantially pressure-sensitive adhesive protective film in pressure sensitive adhesive system, and to the light transmittance of protective film
And peeling force influence is smaller, to overcome the shortcomings of existing carbon nanotube dispersion technology, and has widened the application neck of carbon nanotube
Domain.
The specific technical solution of the present invention is as follows.
1. according to parts by weight, 1 part of carbon nanotube to be added to the mixed solution of 10 parts of sulfuric acid Yu nitric acid 1:3 volume ratio
In, first ultrasonic pretreatment 30min, then the 2h that flows back after being to slowly warm up to 120 DEG C, surface, which is obtained, after acid filtering contains hydroxyl and carboxyl
Functionalized carbon nano-tube (CNT-OH, CNT-COOH).
2. according to parts by weight, 1 part of surface to be contained to the functionalized carbon nano-tube and 2 parts of containing hydrogen silicone oils of hydroxyl and carboxyl
It is added in 97 parts of dewatered organic solvents, with platinum catalyst is added after ultrasonication, makes containing hydrogen silicone oil and functionalized carbon
Nanotube carries out dehydrogenation reaction, carries out heat treatment reflux to system after reaction, obtains after inactivating platinum catalyst organic
Si modification carbon nano-tube solution.
It is as follows to react formula.
。
Unlike the prior art, the technical program does not use silane coupling agent.
Carbon nanotube after handling acidification using only silane coupling agent small molecule, the carbon nanotube that not can guarantee that treated
It will not further occurrence reunion or sedimentation；Carbon nanotube, inorganic particulate phase are handled using inorganic particulates such as inorganic chopped carbon fibers
Mutual reunion increases the risk of carbon nanotube reunion sedimentation, and can not be uniformly dispersed in organic solvent.And working as has agglomeration
When generation, it will lead to product conductivity and light transmittance sharp fall, the dense of carbon nanotube solvent influenced whether when reuniting
Spend homogeneity.And this problem can be effectively avoided using polysiloxane macromonomer processing carbon nanotube, after being grafted organic macromolecular chain,
Carbon nanotube can not be adsorbed each other close to causing to reunite, and can improve the dispersibility in organosilicon systems and solvent.
As the preferred embodiment of the technical program, carbon nanotube is one kind of single-walled carbon nanotube and multi-walled carbon nanotube,
Diameter of single-wall carbon nano tube is 1-1.5nm, and length is 5-10 μm；Multi-wall carbon nano-tube pipe diameter is 4-8nm, and length is 5-10 μm.
Usual diameter of single-wall carbon nano tube and length distribution range are narrower than multi-walled carbon nanotube, select distribution of lengths between 5-10 μm
Carbon pipe is relatively specific for antistatic silicone pressure sensitive adhesive system, and length is poor less than the carbon pipe electric conductivity of 5um, it is difficult to be formed three-dimensional
Three-dimensional conductive network, and carbon pipe of the length greater than 10um is difficult to be uniformly dispersed, and part pressure sensitive adhesive thickness is lower than 10 μm.Diameter is big
It also greatly improves in the carbon nanotube dispersion difficulty of 8nm, and is affected to light transmittance, it is difficult to be suitable for pressure sensitive adhesive system.
As the preferred embodiment of the technical program, organic solvent is toluene, ethyl alcohol, isopropanol, ethyl acetate, 120# solvent
One of oil is a variety of.A few class solvent boiling points are respectively less than 150 DEG C, can boil in system out not in pressure sensitive adhesive curing process
Later period application can be had an impact.
As the preferred embodiment of the technical program, containing hydrogen silicone oil viscosity is 100 ~ 5000 mPas, hydrogen content in step 2
It is 0.1% ~ 1.6%.The too low carbon nanotube dispersibility that will lead in product of containing hydrogen silicone oil viscosity reduces and easy to reunite, and viscosity is too high to be led
It causes and carbon nanotube graft reaction is difficult, need significantly to extend the reaction time to guarantee the high grafting rate of carbon nanotube.It is hydrogeneous
Silicone oil hydrogen content is too low, and reactive hydrogen group number is lower, and not can guarantee has extra silicon hydrogen-based and silicone pressure sensitive after the reaction was completed
Vinyl in colloid system combines, and reduces with the grafting rate of carbon nanotube, and hydrogen content is too high to be caused to react too fast or even can go out
Existing single macromolecular chain influences the dispersibility of carbon nanotube with mostly with carbon tube reaction.
As the preferred embodiment of the technical program, ultrasonic treatment time is 20-50min in step 2.Handle time mistake
The short degree of scatter that will lead to is not ideal enough, and the processing time is too long to will lead to length of carbon nanotube decaying, tube wall breakage to influencing
To product electric conductivity.
As the preferred embodiment of the technical program, dehydrogenation reaction temperature is 80-100 DEG C in step 2, and the reaction time is
1.5-2.5h.Platinum catalyst activity is higher in the reaction temperature, and reaction speed is fast, and temperature is excessively high to will lead to catalyst inactivation.
As the preferred embodiment of the technical program, heat treatment temperature is 150-160 DEG C in step 2, and the processing time is 1-
1.5h.It will lead to catalyst inactivation in the reaction temperature, prevent remaining platinum catalyst from generating adverse effect to subsequent applications.
As the preferred embodiment of the technical program, platinum catalyst is in chloroplatinic acid or platinum/olefinic siloxane complex
Any one, additional amount is calculated as 40ppm by the mass fraction of platinum.
Compared with prior art, the present invention is primarily present the following aspects advantage.
1. handling the carbon nanotube for obtaining surface and containing hydroxyl and carboxyl by chemical method, chemistry side is further used
Silicone macromolecule containing active group is grafted in carbon nanotube by method, and such mode can increase substantially carbon nanotube
Dispersibility in a solvent prevents to adsorb between carbon nanotube, it is avoided to reunite during storage.
2. the modified carbon nano-tube is used in organic pressure-sensitive gel system and has due to being grafted with silicone macromolecule chain
There are extraordinary dispersibility and compatibility, simple agitation that dispersion of the carbon nano-tube solution in organosilicon systems can be realized, mixes
Simple process is closed, compared with the antistatic or even conductive effect that pressure-sensitive adhesive protective film can be realized in few additive (< 0.1%).
3. consolidating without containing elements such as P, N, S to additional organosilicon pressure sensitive adhesive system in the modified carbon nano-tube system
Change process does not have an impact, and not will lead to it and situations such as catalyst activity is suppressed even inactivation occurs.
Detailed description of the invention
Fig. 1 is the metallographic microscope glue surface shooting picture that 1 gained carbon nanotube additional amount of embodiment is 10%.
Fig. 2 is the metallographic microscope glue surface shooting picture that certain commercially available carbon nano tube dispersion liquid additional amount is 10%.
Specific embodiment
Further the application is specifically described below with reference to drawings and the specific embodiments, but the application is not by attached
Any restriction of figure and embodiment.
Embodiment 1.
The processing method of organic-silicon-modified carbon nanotube, includes the following steps.
1) 1 part of single-walled carbon nanotube SWCNT by weight, is added to the mixed of 10 parts of 100ml sulfuric acid and 300ml nitric acid
It closes in solution, first ultrasonic pretreatment 30min, then the 2h that flows back after being to slowly warm up to 120 DEG C, obtains surface and contain hydroxyl and carboxyl
Single-walled carbon nanotube (SWCNT-OH, SWCNT-COOH).
2) the functionalization single-walled carbon nanotube of hydroxyl and carboxyl is contained on the surface 1g (viscosity 50cps contains with 2g containing hydrogen silicone oil
Hydrogen amount 1.0%) it is added in the dewatered toluene of 97g and 120# solvent naphtha (volume ratio 1:1) mixed solution, use ultrasonication
0.8g platinum catalyst (5000ppm) is added after 30min, makes containing hydrogen silicone oil and functionalized carbon nano-tube in 80 DEG C of dehydrogenation reactions
It is molten to obtain organic-silicon-modified single-walled carbon nanotube after inactivating platinum catalyst then in 150 DEG C of heat treatments reflux 1h by 1.5h
Liquid.
Embodiment 2.
The processing method of organic-silicon-modified carbon nanotube, includes the following steps.
1) 1 part of multi-walled carbon nanotube MWCNT by weight, is added to the mixed of 10 parts of 100ml sulfuric acid and 300ml nitric acid
It closes in solution, first ultrasonic pretreatment 30min, then the 2h that flows back after being to slowly warm up to 120 DEG C, obtains surface and contain hydroxyl and carboxyl
Multi-walled carbon nanotube (MWCNT-OH, MWCNT-COOH).
2) by 1g parts of surfaces contain hydroxyl and carboxyl function multi-walled carbon nano-tube and 2g containing hydrogen silicone oil (viscosity 50cps,
Hydrogen content 1.0%) it is added in the dewatered toluene solution of 97g, with addition 0.8g platinum catalyst after ultrasonication 30min
(5000ppm) makes containing hydrogen silicone oil and functionalized carbon nano-tube in 80 DEG C of dehydrogenation reaction 2h, then flows back 1h in 150 DEG C of heat treatments,
Platinum catalyst is set to inactivate to obtain organic-silicon-modified multi-walled carbon nanotube solution.
Embodiment 3.
The processing method of organic-silicon-modified carbon nanotube, includes the following steps.
1) 1 part of single-walled carbon nanotube SWCNT by weight, is added to the mixed of 10 parts of 100ml sulfuric acid and 300ml nitric acid
It closes in solution, first ultrasonic pretreatment 30min, then the 2h that flows back after being to slowly warm up to 120 DEG C, obtains surface and contain hydroxyl and carboxyl
Single-walled carbon nanotube (SWCNT-OH, SWCNT-COOH).
2) the functionalization single-walled carbon nanotube of hydroxyl and carboxyl is contained on the surface 1g (viscosity 50cps contains with 2g containing hydrogen silicone oil
Hydrogen amount 1.0%) it is added in the dewatered ethyl alcohol of 97g and isopropanol (volume ratio 1:1) mixed solution, with ultrasonication 30min
0.8g platinum catalyst (5000ppm) is added afterwards, makes containing hydrogen silicone oil and functionalized carbon nano-tube in 80 DEG C of dehydrogenation reaction 1.5h, so
Afterwards in 150 DEG C of heat treatments reflux 1h, organic-silicon-modified single-walled carbon nanotube solution is obtained after inactivating platinum catalyst.
Embodiment 4.
The processing method of organic-silicon-modified carbon nanotube, includes the following steps.
1) 1 part of single-walled carbon nanotube SWCNT by weight, is added to the mixed of 10 parts of 100ml sulfuric acid and 300ml nitric acid
It closes in solution, first ultrasonic pretreatment 30min, then the 2h that flows back after being to slowly warm up to 120 DEG C, obtains surface and contain hydroxyl and carboxyl
Single-walled carbon nanotube (SWCNT-OH, SWCNT-COOH).
2) the functionalization single-walled carbon nanotube of hydroxyl and carboxyl is contained on the surface 1g (viscosity 50cps contains with 2g containing hydrogen silicone oil
Hydrogen amount 1.0%) it is added in the dewatered ethyl alcohol of 97g and ethyl acetate (volume ratio 1:1) mixed solution, use ultrasonication
0.8g platinum catalyst (5000ppm) is added after 30min, makes containing hydrogen silicone oil and functionalized carbon nano-tube in 80 DEG C of dehydrogenation reactions
It is molten to obtain organic-silicon-modified single-walled carbon nanotube after inactivating platinum catalyst then in 150 DEG C of heat treatments reflux 1h by 1.5h
Liquid.
Embodiment 5.
The processing method of organic-silicon-modified carbon nanotube, includes the following steps.
1) 1 part of single-walled carbon nanotube SWCNT by weight, is added to the mixed of 10 parts of 100ml sulfuric acid and 300ml nitric acid
It closes in solution, first ultrasonic pretreatment 30min, then the 2h that flows back after being to slowly warm up to 120 DEG C, obtains surface and contain hydroxyl and carboxyl
Single-walled carbon nanotube (SWCNT-OH, SWCNT-COOH).
2) by the surface 1g contain hydroxyl and carboxyl functionalization single-walled carbon nanotube and 2g containing hydrogen silicone oil (viscosity 200cps,
Hydrogen content 1.0%) it is added in the dewatered toluene of 97g and 120# solvent naphtha (volume ratio 1:1) mixed solution, at ultrasonic wave
0.8g platinum catalyst (5000ppm) is added after managing 40min, makes containing hydrogen silicone oil and functionalized carbon nano-tube in 90 DEG C of dehydrogenation reactions
2h obtains organic-silicon-modified single-walled carbon nanotube solution after inactivating platinum catalyst then in 150 DEG C of heat treatments reflux 1h.
Embodiment 6.
The processing method of organic-silicon-modified carbon nanotube, includes the following steps.
1) 1 part of single-walled carbon nanotube SWCNT by weight, is added to the mixed of 10 parts of 100ml sulfuric acid and 300ml nitric acid
It closes in solution, first ultrasonic pretreatment 30min, then the 2h that flows back after being to slowly warm up to 120 DEG C, obtains surface and contain hydroxyl and carboxyl
Single-walled carbon nanotube (SWCNT-OH, SWCNT-COOH).
2) by the surface 1g contain hydroxyl and carboxyl functionalization single-walled carbon nanotube and 2g containing hydrogen silicone oil (viscosity 3000cps,
Hydrogen content 1.0%) it is added in the dewatered toluene of 97g and 120# solvent naphtha (volume ratio 1:1) mixed solution, at ultrasonic wave
0.8g platinum catalyst (5000ppm) is added after managing 45min, keeps containing hydrogen silicone oil and functionalized carbon nano-tube anti-in 100 DEG C of dehydrogenations
2.5h is answered, then in 150 DEG C of heat treatments reflux 1h, it is molten to obtain organic-silicon-modified single-walled carbon nanotube after inactivating platinum catalyst
Liquid.
Embodiment 7.
The processing method of organic-silicon-modified carbon nanotube, includes the following steps.
1) 1 part of single-walled carbon nanotube SWCNT by weight, is added to the mixed of 10 parts of 100ml sulfuric acid and 300ml nitric acid
It closes in solution, first ultrasonic pretreatment 30min, then the 2h that flows back after being to slowly warm up to 120 DEG C, obtains surface and contain hydroxyl and carboxyl
Single-walled carbon nanotube (SWCNT-OH, SWCNT-COOH).
2) by the surface 1g contain hydroxyl and carboxyl functionalization single-walled carbon nanotube and 2g containing hydrogen silicone oil (viscosity 200cps,
Hydrogen content 1.5%) it is added in the dewatered toluene of 97g and 120# solvent naphtha (volume ratio 1:1) mixed solution, at ultrasonic wave
0.8g platinum catalyst (5000ppm) is added after managing 40min, makes containing hydrogen silicone oil and functionalized carbon nano-tube in 90 DEG C of dehydrogenation reactions
2h obtains organic-silicon-modified single-walled carbon nanotube solution after inactivating platinum catalyst then in 150 DEG C of heat treatments reflux 1h.
Embodiment 8.
The processing method of organic-silicon-modified carbon nanotube, includes the following steps.
1) 1 part of single-walled carbon nanotube SWCNT by weight, is added to the mixed of 10 parts of 100ml sulfuric acid and 300ml nitric acid
It closes in solution, first ultrasonic pretreatment 30min, then the 2h that flows back after being to slowly warm up to 120 DEG C, obtains surface and contain hydroxyl and carboxyl
Single-walled carbon nanotube (SWCNT-OH, SWCNT-COOH).
2) by the surface 1g contain hydroxyl and carboxyl functionalization single-walled carbon nanotube and 2g containing hydrogen silicone oil (viscosity 200cps,
Hydrogen content 0.4%) it is added in the dewatered toluene of 97g and 120# solvent naphtha (volume ratio 1:1) mixed solution, at ultrasonic wave
0.8g platinum catalyst (5000ppm) is added after managing 40min, makes containing hydrogen silicone oil and functionalized carbon nano-tube in 90 DEG C of dehydrogenation reactions
2h obtains organic-silicon-modified single-walled carbon nanotube solution after inactivating platinum catalyst then in 150 DEG C of heat treatments reflux 1h.
Embodiment 9.
The processing method of organic-silicon-modified carbon nanotube, includes the following steps.
1) 1 part of single-walled carbon nanotube SWCNT by weight, is added to the mixed of 10 parts of 100ml sulfuric acid and 300ml nitric acid
It closes in solution, first ultrasonic pretreatment 30min, then the 2h that flows back after being to slowly warm up to 120 DEG C, obtains surface and contain hydroxyl and carboxyl
Single-walled carbon nanotube (SWCNT-OH, SWCNT-COOH).
2) the functionalization single-walled carbon nanotube of hydroxyl and carboxyl is contained on the surface 1g (viscosity 50cps contains with 2g containing hydrogen silicone oil
Hydrogen amount 1.0%) it is added in the dewatered toluene of 97g and 120# solvent naphtha (volume ratio 1:1) mixed solution, use ultrasonication
0.8g platinum catalyst (5000ppm) is added after 30min, makes containing hydrogen silicone oil and functionalized carbon nano-tube in 80 DEG C of dehydrogenation reactions
It is molten to obtain organic-silicon-modified single-walled carbon nanotube after inactivating platinum catalyst then in 160 DEG C of heat treatments reflux 1.5h by 1.5h
Liquid.
By the carbon nano tube dispersion liquid prepared in the embodiment of the present application 1 and certain commercially available carbon nano tube dispersion liquid in 10% ratio
It is added in organic pressure-sensitive gel system, glue application forms a film under remaining parameter unanimous circumstances.Gold is used to its surface
It is as illustrated in fig. 1 and 2 respectively that phase microscope amplifies 100 times of observations.1 carbon nano tube dispersion liquid of the embodiment of the present application is used as the result is shown
Without obvious agglomeration, favorable dispersibility (Fig. 1)；And then there is agglomeration (Fig. 2) using certain commercially available carbon nano tube dispersion liquid.
By the sample of above-described embodiment coating film forming further carry out following items test: peeling force (180 °) according to
ASTMD-3330 is tested；Pressure sensitive adhesive sheet resistance value is tested according to ASTMD-257；Light transmittance is according to ASTMD-1003
It is tested；Dispersibility observes every square decimeter of filter cloth residue particles number after being filtered carbon nano tube dispersion liquid with 400 mesh filter clothes
To verify；Dispersed result point 4 grades, " excellent " expressions granule number less than 2, " good " expression granule number between 2-5 it is a between,
" in " granule number is indicated between 6-9, " poor " expression granule number is greater than 10, and correlated results is shown in Table 1.
TableDifferent formulations correspond to the test data of print.
。
As can be seen from Table 1, with the raising of the additional amount of CNT, light transmittance is gradually decreased, and peeling force attenuation amplitude is also gradually
Rise, sheet resistance value is gradually reduced, and conductivity is promoted.Embodiment 2 for embodiment 1, light transmittance to product and
Peeling force influence is bigger, and needs higher additional amount to be just able to achieve lower glue surface resistance value, but its cost is very low, mainly due to more
Wall carbon nano tube market price is far below single-walled carbon nanotube.Therefore it should select to close according to actual needs during practice
Suitable formula.
2 different formulations of table correspond to the test data of print.
。
1,3,4 three group of experiment of comparative example can be seen that, using several solvents provided by this programme to the final shadow of product
It rings little.1,5,6 three group of experiment of comparative example can be seen that the containing hydrogen silicone oil viscosity used is bigger, and dispersibility is better, and apply
Into pressure sensitive adhesive, glue surface resistance value also has a declining tendency, but containing hydrogen silicone oil viscosity is bigger, and ultrasonic treatment time is longer, processing
Dehydrogenation reaction needs higher reaction temperature and longer reaction time afterwards.1,7,8 three group of experiment of comparative example can be seen that, make
Containing hydrogen silicone oil hydrogen content is lower, and the addition of carbon nanotube influences smaller, the dispersibility of carbon nanotube to pressure sensitive adhesive peeling force
Also it steps up.1,9 two group of experiment of comparative example can be seen that, improves heat treatment return time and temperature and disperses to carbon nanotube
Property influence less, mainly platinum inactivation it is more thorough, on pressure sensitive adhesive peeling force influence it is smaller.
Above in conjunction with specific embodiment, an exemplary description of the invention, it is clear that realization of the invention is not by upper
The limitation of mode is stated, as long as using the various improvement that the inventive concept and technical scheme of the present invention carry out, or not improved general
Conception and technical scheme of the invention directly apply to other occasions, are within the scope of the invention.
Claims (9)
1. a kind of synthesis mode of the organic-silicon-modified carbon nanotube suitable for pressure sensitive adhesive system, it is characterised in that including walking as follows
It is rapid:
1) according to parts by weight, 1 part of carbon nanotube is added in 10 parts of sulfuric acid and the mixed solution of nitric acid 1:3 volume ratio, first
Ultrasonic pretreatment 30min, then the 2h that flows back after being to slowly warm up to 120 DEG C, obtain the function that hydroxyl and carboxyl are contained in surface after acid filtering
It can carbon nano tube (CNT-OH, CNT-COOH)；
2) according to parts by weight, the functionalized carbon nano-tube that hydroxyl and carboxyl are contained in 1 part of surface is added to 2 parts of containing hydrogen silicone oils
In 97 parts of dewatered organic solvents, with platinum catalyst is added after ultrasonication, make containing hydrogen silicone oil and functionalized carbon nano-tube
Dehydrogenation reaction is carried out, heat treatment reflux is carried out to system after reaction, is obtained after inactivating platinum catalyst organic-silicon-modified
Carbon nano-tube solution.
2. the synthesis mode of the organic-silicon-modified carbon nanotube according to claim 1 suitable for pressure sensitive adhesive system, special
Sign is: not using silane coupling agent.
3. the synthesis mode of the organic-silicon-modified carbon nanotube according to claim 1 suitable for pressure sensitive adhesive system, special
Sign is: carbon nanotube described in step 1) is one kind of single-walled carbon nanotube and multi-walled carbon nanotube, and single-walled carbon nanotube is straight
Diameter is 1-1.5nm, and length is 5-10 μm；Multi-wall carbon nano-tube pipe diameter is 4-8nm, and length is 5-12 μm.
4. the synthesis mode of the organic-silicon-modified carbon nanotube according to claim 1 suitable for pressure sensitive adhesive system, special
Sign is: organic solvent described in step 2 is one of toluene, ethyl alcohol, isopropanol, ethyl acetate, 120# solvent naphtha or more
Kind.
5. the synthesis mode of the organic-silicon-modified carbon nanotube according to claim 1 suitable for pressure sensitive adhesive system, special
Sign is: containing hydrogen silicone oil viscosity described in step 2 is 10 ~ 5000 mPas, and hydrogen content is 0.1% ~ 1.6%.
6. the synthesis mode of the organic-silicon-modified carbon nanotube according to claim 1 suitable for pressure sensitive adhesive system, special
Sign is: ultrasonic treatment time described in step 2 is 20-50min.
7. the synthesis mode of the organic-silicon-modified carbon nanotube according to claim 1 suitable for pressure sensitive adhesive system, special
Sign is: dehydrogenation reaction temperature described in step 2 is 80-100 DEG C, reaction time 1.5-2.5h.
8. the synthesis mode of the organic-silicon-modified carbon nanotube according to claim 1 suitable for pressure sensitive adhesive system, special
Sign is: heat treatment temperature described in step 2 is 150-160 DEG C, and the processing time is 1-1.5h.
9. the synthesis mode of the organic-silicon-modified carbon nanotube according to claim 1 suitable for pressure sensitive adhesive system, special
Sign is: platinum catalyst described in step 2 is any one in chloroplatinic acid or platinum/olefinic siloxane complex, is added
Amount is calculated as 40ppm by the mass fraction of platinum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910018217.8A CN109651622B (en) | 2019-01-09 | 2019-01-09 | synthetic method of organic silicon modified carbon nano-tube suitable for pressure-sensitive adhesive system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910018217.8A CN109651622B (en) | 2019-01-09 | 2019-01-09 | synthetic method of organic silicon modified carbon nano-tube suitable for pressure-sensitive adhesive system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109651622A true CN109651622A (en) | 2019-04-19 |
| CN109651622B CN109651622B (en) | 2020-01-31 |
Family
ID=66119097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910018217.8A Active CN109651622B (en) | 2019-01-09 | 2019-01-09 | synthetic method of organic silicon modified carbon nano-tube suitable for pressure-sensitive adhesive system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109651622B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285769A (en) * | 2023-04-11 | 2023-06-23 | 斯迪克新型材料（江苏）有限公司 | Organosilicon pressure-sensitive adhesive tape and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100159219A1 (en) * | 2003-02-26 | 2010-06-24 | Jong Jin Park | Negative pattern of carbon nanotubes and carbon nanotube composite comprising surface-modified carbon nanotubes |
| CN102442660A (en) * | 2011-10-14 | 2012-05-09 | 苏州大学 | Surface modified carbon nanotube and preparation method thereof |
| CN104327512A (en) * | 2014-08-18 | 2015-02-04 | 杭州师范大学 | Preparation method of silicone rubber composite material containing carbon nanotubes |
| CN108623845A (en) * | 2017-03-24 | 2018-10-09 | 天津大学 | The method and its application of polysiloxane-modified carbon nanotube |
-
2019
- 2019-01-09 CN CN201910018217.8A patent/CN109651622B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100159219A1 (en) * | 2003-02-26 | 2010-06-24 | Jong Jin Park | Negative pattern of carbon nanotubes and carbon nanotube composite comprising surface-modified carbon nanotubes |
| CN102442660A (en) * | 2011-10-14 | 2012-05-09 | 苏州大学 | Surface modified carbon nanotube and preparation method thereof |
| CN104327512A (en) * | 2014-08-18 | 2015-02-04 | 杭州师范大学 | Preparation method of silicone rubber composite material containing carbon nanotubes |
| CN108623845A (en) * | 2017-03-24 | 2018-10-09 | 天津大学 | The method and its application of polysiloxane-modified carbon nanotube |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285769A (en) * | 2023-04-11 | 2023-06-23 | 斯迪克新型材料（江苏）有限公司 | Organosilicon pressure-sensitive adhesive tape and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109651622B (en) | 2020-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jin et al. | Poly (vinylidene fluoride)-assisted melt-blending of multi-walled carbon nanotube/poly (methyl methacrylate) composites | |
| CN106752119B (en) | A kind of preparation method of carbon black nano material | |
| Spinks et al. | Mechanical properties of chitosan/CNT microfibers obtained with improved dispersion | |
| Luo et al. | Effect of amino-functionalization on the interfacial adhesion of multi-walled carbon nanotubes/epoxy nanocomposites | |
| Gao et al. | Interfacial microstructure and enhanced mechanical properties of carbon fiber composites caused by growing generation 1–4 dendritic poly (amidoamine) on a fiber surface | |
| Kalinina et al. | Synthesis, dispersion, and viscosity of poly (ethylene glycol)-functionalized water-soluble single-walled carbon nanotubes | |
| Mougel et al. | Highly efficient and predictable noncovalent dispersion of single-walled and multi-walled carbon nanotubes by cellulose nanocrystals | |
| Schmid et al. | Efficient preparation of polystyrene/silica colloidal nanocomposite particles by emulsion polymerization using a glycerol-functionalized silica sol | |
| CN105754159B (en) | Latex composite, preparation and the application of a kind of high intensity, antistatic | |
| Meer et al. | Attributes of polymer and silica nanoparticle composites: A review | |
| Lu et al. | A flexible and transparent thin film heater based on a carbon fiber/heat-resistant cellulose composite | |
| Wang et al. | In-situ modification of cellulose nanofibrils by organosilanes during spray drying | |
| Ha et al. | Composites of Single‐Walled Carbon Nanotubes and Styrene‐Isoprene Copolymer Latices | |
| JP6201164B2 (en) | Active energy ray-curable nanocarbon dispersion, method for producing the same, and active energy ray-curable coating agent using the same | |
| Yang et al. | Incorporation of liquid-like multiwalled carbon nanotubes into an epoxy matrix by solvent-free processing | |
| Liu et al. | One-step preparation of oxygen/fluorine dual functional MWCNTs with good water dispersibility by the initiation of fluorine gas | |
| Ribeiro et al. | Silica nanoparticles surface charge modulation of the electroactive phase content and physical-chemical properties of poly (vinylidene fluoride) nanocomposites | |
| White et al. | Rheology of disentangled multiwalled carbon nanotubes dispersed in uncured epoxy fluid | |
| Chu et al. | Synergistic effect of nano‐SiO2 and small‐sized graphene oxide on carbon fiber/epoxy composite | |
| Inukai et al. | Preparation and properties of multiwall carbon nanotubes/polystyrene-block-polybutadiene-block-polystyrene composites | |
| CN107474550A (en) | A kind of fast-response high sensitive polymer matrix gas sensitive and preparation method and application | |
| CN109651622A (en) | A kind of synthesis mode of the organic-silicon-modified carbon nanotube suitable for pressure sensitive adhesive system | |
| Xu et al. | Rheology of end-linking polydimethylsiloxane networks filled with silica | |
| Liu et al. | Poly (tannin urethane)-stabilized multiwalled carbon nanotube aqueous dispersion for antistatic coating | |
| CN107057364A (en) | A kind of high-performance carbon nanotube composite and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |