CN108192143A - A kind of method of modifying for the carbon nanotube for being used as gum filler - Google Patents
A kind of method of modifying for the carbon nanotube for being used as gum filler Download PDFInfo
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Abstract
Present invention aims at provide a kind of method of modifying for the carbon nanotube for being used as gum filler.The invention carries out hydroxylating processing using acid with strong oxidizing property and polyalcohol to carbon nano tube surface, is then graft-polymerized using unsaturated carboxylic acid polar monomer to styrene-butadiene latex, high dispersive type carbon nanotube is prepared finally by cladding processing.This solves the easy agglomeration traits of carbon nanotube, impart polymolecularity of the carbon nanotube in rubber matrix.
Description
Technical field
The present invention relates to a kind of rubber preparation methods of packing material surface modification of carbon nanotube.
Background technology
Carbon nanotube (Carbon Nanotube, abbreviation CNT) is a kind of novel carbon structure being just found for 1991, is
The tube body being rolled by the graphite flake layer that carbon atom is formed.Since carbon atom takes full SP in carbon nanotube2Hydridization links, compared to SP3
Hydridization SP2S orbital compositions are more in hydridization, and carbon-carbon bond bond energy is big, therefore carbon nanotube is made to have high-modulus, high intensity, and tension is strong
Degree reaches 50~200GPa, is 100 times of steel, and density but only has the 1/6 of steel；Its elasticity modulus is up to 100TPa, with diamond
Elasticity modulus is suitable.Thus the excellent mechanical property of carbon nanotube would be even more beneficial to assign high molecular material high intensity, low bulk,
The characteristics such as high abrasion are increasingly subject to the concern of people in the application prospect of field of rubber materials.But since carbon nanotube category is received
Rice material, grain size is small, specific surface is big, surface energy is high, easily reunites, and holds very much in the process participating in the mixed and modified of rubber material
Useless agglomerate is easily gathered into, causes to disperse non-uniform problem appearance, can not only influence filling-modified effect in this way, but also
The performance of rubber material can be damaged.
Carbon nanotube composite modification material studies oneself as one of hot spot of current Material Field research.So far, specially
There are many carbon nano-tube modification method of sharp document report.ZL 200310109074.0 carries out polarity to carbon nano tube surface first
It is handled with nonpolarity, is allowed to have amphiphilic performance, then carries out surface cladding processing with polyolefin, polyacrylic polymer,
So as to obtain carbon nanotube/high molecule nano composite material.ZL 200510009769.0 provides a kind of utilization ultrasonic wave and high speed
The effects that being dispersed with stirring the dispersion, crushing, activation of device, the aggregation and winding of destroying carbon nanometer tube in itself；Utilize surfactant
Organo-functional group and carbon nano tube surface carry out chemisorbed or chemical reaction, surfactant is made to be covered in carbon nanotube table
Face, so as to fulfill dispersion to surface modification of carbon nanotube and its in the epoxy.ZL 200410089036.8 is with poly- second
Alkene imidazoles is polymerized monomer, then by the use of silane, Wo Lan or titanate esters as coupling agent, through hydroxyl chemical etching method and micro-emulsion polymerization
The carbon nanotube/polyvinylimidazole nanocomposites materials that method prepares.ZL 200410017699.9 is by the strong oxygen of carbon nanotube
After the property changed acid processing, react with dichloro Asia alum, products therefrom and binary ammonia or diol reaction obtain surface carry amino or
The modified carbon nano-tube of hydroxyl；Modified carbon nano-tube and binary or multicomponent isocyanate of the surface with amino or hydroxyl is anti-
Should, obtain the functionalized carbon nano-tube that surface carries isocyanate groups.After ZL 200310109072.1 handles carbon nanotube
Its surface is made to carry specific initiation group；Then cause tert-butyl methacrylate monomer with atom transition free radical polymerization reaction
Polymerization, then tert-butyl methacrylate is hydrolyzed, it is allowed to slough tertiary butyl, generates carboxyl, obtain more carboxyls and gather
Close the water-soluble carbon nanometer tube of object grafting.
Invention content
Present invention aims at provide a kind of method of modifying for the carbon nanotube for being used as gum filler.The invention uses strong oxygen
The property changed acid and polyalcohol carry out hydroxylating processing to carbon nano tube surface, then using unsaturated carboxylic acid polar monomer to butadiene-styrene rubber
Breast is graft-polymerized, and high dispersive type carbon nanotube is prepared finally by cladding processing.This solves carbon nanotubes
Easy agglomeration traits, impart polymolecularity of the carbon nanotube in rubber matrix.
" part " of the present invention each means mass parts.
A kind of method of modifying of carbon nanotube as gum filler of the present invention, specific preparation process are：
(1) preparation of carbon nanotube hydroxyl：By 100 parts of carbon nanotubes and 150~200 parts of concentrated nitric acids, 50~100 parts it is dense
Sulfuric acid, 10~50 parts of potassium permanganate are put into togerther in reactor and mix, with 50~100kHz ultrasonications 1~2hr, Ran Houjia
For heat to 50~150 DEG C, stirring acid boils 1~10hr, and cooling, suction filtration, washing are in neutrality to filtrate, are eventually adding more than 200~500 parts
First alcohol is heated to 50~90 DEG C, is stirred to react 1~5hr, filters, washs, is dry, obtains the carbon nanometer that surface carries hydroxyl
Pipe.
(2) preparation of graft latex：100~300 parts of deionized waters are firstly added in polymeric kettle and then are sequentially added
100 parts of styrene-butadiene latexes, 1~10 part of emulsifier, 0.05~0.5 part of molecular weight regulator after being replaced with nitrogen, add in 1~10 part
Unsaturated carboxylic acid polar monomer, stirring, heating add in 0.05~0.3 part of initiation when kettle temperature degree to be polymerized reaches 30~50 DEG C
Agent, react 3~8hr after, add in 0.1~0.5 part of terminator, be made graft latex (0.1 ﹪ of grafting rate of styrene-butadiene latex~
1.5 ﹪).
(3) preparation of high dispersive type carbon nanotube：Take 100 parts of hydroxyl carbon nano tubes and 1~5 part of surfactant, 300
~500 parts of deionized waters, 1~6 part of buffer are added in polymeric kettle and are stirred 10~30min；Then 1~5 part of breast is added in
Agent, 1~10 part of graft latex, stirring are warming up to 50~70 DEG C, after being stirred to react 1~5hr, and washed, dehydration, is ground at drying
Grind the scattered type carbon nanotube that secures satisfactory grades.
Carbon nanotube of the present invention is nano level, and grain size is：0.3~30nm.
One kind in ethylene glycol, propylene glycol, glycerine, butanediol, pentaerythrite of polyalcohol of the present invention or
Several mixtures.
Styrene-butadiene latex of the present invention is to be gathered by conjugated diene hydrocarbon compound and aryl ethylene class compound by lotion
Amount to poly- form.Conjugated diene hydrocarbon compound is C4Class conjugated diene hydrocarbon compound.Aryl ethylene class compound be styrene, α-
Methyl styrene, 2- propenyl benzenes, ethyl styrene and their derivative.Wherein the solid content of styrene-butadiene latex is 20~45w%.
Unsaturated carboxylic acid polar monomer of the present invention is selected from acrylic acid (AA), methacrylic acid (MAA), 2- ethyls third
One kind in olefin(e) acid, preferably acrylic acid (AA).
Initiator of the present invention is water-soluble thermal initiator：Selected from ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, 2,
Bis- (the 2 one amidine oxazoline propane) hydrochlorides of 2-azo, 2,2-azo [2-(2-imidazoline-2-yl) propane] dihydrochloride
In one kind, initiator system of ammonium persulfate.In order to ensure the performance of styrene-butadiene latex, the addition of initiator needs stringent control.
Otherwise, in graft polymerization, excessive double bond will be attacked, can not thus ensure the styrene-butadiene latex of diene class in the later stage
Blending, vulcanization processing in have enough double bonds, the effect that carbon nanotube is modified rubber filling can be influenced.Institute in the present invention
The initiator addition stated is 0.05~0.3 part, preferably 0.07~0.2 part.
Surfactant of the present invention is selected from lauric acid glycol ester, lauric acid propylene glycol ester, lauric acid glycerine
The mixture of one or more of ester, lauric acid butanediol ester, lauric acid pentaerythritol ester.
The present invention may be used this field to used emulsifier, molecular weight regulator, buffer, terminator etc. and lead to
Conven-tional adjuvants, addition are also the conventional amount used that those skilled in the art can be calculated according to the dosage of latex,
The present invention does not do particular determination.Emulsifier as described in the present invention is known to those skilled in the art, is anion emulsifier
With it is one or more in nonionic emulsifier.Such as：Selected from fatty acid soaps, RA rosin acid, neopelex, dodecane
The mixture of one or more of base sodium sulphate, Tween-80, preferably neopelex.
Molecular weight regulator of the present invention is selected from ten carbon mercaptan of uncle, tert-dodecyl mercaptan, 14 carbon mercaptan of uncle, uncle ten
One kind in six carbon mercaptan, preferably tert-dodecyl mercaptan.
The one kind of buffer of the present invention in sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonium hydroxide, ammonium hydrogen carbonate,
It is preferred that sodium hydroxide.
Terminator of the present invention is selected from the mixing of one or more of diethyl hydroxylamine, hydroxyl sulfate, Sodium Dimethyldithiocarbamate
Object.
A kind of method of modifying of carbon nanotube for being used as gum filler of the present invention, first using acid with strong oxidizing property and
Polyalcohol to carbon nano tube surface carry out hydroxylating processing so that carbon nano tube surface carry hydroxyl, by " hydrogen bond action " with
Polyol ester links together, and the single-point anchor point based on carbonyl is formed in carbon nano tube surface.The anchor point and grafting fourth
The polar group carboxyl of benzene latex generates the mutual attractive force between molecule, carbon nanotube particle surface can be formed securely,
Close styrene-butadiene latex clad.It, can be in nanoparticle since styrene-butadiene latex has the characteristics that nonpolarity and containing benzene ring structure
Steadily space bit resistance layer is formed between son, can significantly reduce the activation energy of nanoparticle surface, is hindered between particle
Mutually reunite, can realize and steadily exist with single particle shape.It can also significantly improve carbon nanotube and fourth simultaneously
The compatibility of benzene rubber can be realized with tiny particle shape stabilization, is evenly dispersed in butadiene-styrene rubber matrix.The present invention
The easy agglomeration traits of carbon nanotube are efficiently solved, operating method is simple, is suitble to industrialized production.
Description of the drawings
Attached drawing 1 is carbon nanotube (a) and the infrared spectrum spectrogram of high dispersive type carbon nanotube (b).As can be seen from the figure：
The FTIR spectrograms of sample b are in 1690cm-1And 1270cm-1There are two new absorption peaks.Wherein 1690cm-1The absorption peak at place is
The characteristic absorption peak of carbonyl, and the FTIR spectrograms of sample a occur here without absorption peak.Illustrate unsaturated carboxylic acid polar monomer
It is successfully coated on carbon nano tube particle surface with the graft of styrene-butadiene latex.
Specific embodiment
Following embodiment and comparative example are enumerated to illustrate the invention effect of the present invention, but protection scope of the present invention is not
It is only limitted in these embodiment and comparative examples." part " described in embodiment and comparative example each means mass parts.
(1) raw material sources：
(2) analysis test method：
The measure of grafting rate：The sample of about 4g is taken in measuring cup with pipette from three-necked bottle, and 2~3 are added in after weighing
Quinol solution is dripped, drying to constant weight, and then above-mentioned sample is placed in Soxhlet extractor, with toluene in 90 DEG C of water-baths
Upper extractive distillation for 24 hours, is then being dried to constant weight.Monomer grafting rate is calculated as follows:
In formula：m0- latex gross mass (g)；The sample quality (g) weighed after m-reaction；mmMonomer is total in-reactant
Quality (g)；mSBRThe quality (g) of butadiene-styrene rubber in-sample；m1The quality (g) of sample after-extraction.
Sample infrared spectrum analysis：Nano carbon white is modified using German Bruke spectral instruments company infrared spectrometer
Front and rear sample carries out functional group analysis.Sample at 100 DEG C in vacuum drying oven is dried, using pressing potassium bromide troche, acquires wave number
400~4000cm of range—1。
The assay method of settling volume：Weigh the tool plug graduated cylinder that 10g modified Nano white carbons are placed in graduated 100mL
It is interior, a certain amount of dispersant (atoleine) is added in, Nano carbon white to be modified adds liquid by after atoleine complete wetting
Body paraffin fully vibrates 5min with the frequency of oscillation of 30 times/1min, makes modified Nano white carbon in liquid to the scale of 100mL
It is uniformly dispersed in paraffin, then stands, read the solid volume of different time.The settling volume of same time can be in certain journey
Reflect the quality of compatibility between particle and organic solvent on degree, settling volume is big, and it is good to make carbon black dispersion clear, easily compatible.
The assay method of oil absorption：Reference《The assay method of the aluminium hydroxide used as filling material oil absorptions of YS/T618-2007》, take
Quantitative modified Nano white carbon is put into surface plate, and diisooctyl phthalate is added dropwise by each 0.2mL, after being added dropwise every time,
It is fully ground, can be sticked into until agglomerate do not split to powder, oil absorption is with the volume V of every 100g samples institute oil suction with toolsetting0
(mL) it represents, is calculated as follows:
In formula, υ is the volume (mL) of the diisooctyl phthalate of consumption；M is the quality (g) of sample.Oil absorption exists
The specific surface area of modified Nano white carbon is reflected in a way, and specific surface area is lower, and oil absorption is lower, and wettability is got over
Good, vice versa.
Embodiment 1
(1) preparation of carbon nanotube hydroxyl：By 100 parts of carbon nanotubes and 150 parts of concentrated nitric acids, 50 parts of concentrated sulfuric acids, 10 parts
Potassium permanganate is put into togerther in reactor and mixes, and with 60kHz ultrasonication 1.2hr, is then heated to 70 DEG C, stirring acid boils
5hr, cooling, suction filtration, washing are in neutrality to filtrate, are eventually adding 200 parts of ethylene glycol, are heated to 60 DEG C, are stirred to react 2hr,
It filters, wash, is dry, obtaining the carbon nanotube a that surface carries hydroxyl.
(2) preparation of graft latex：100 parts of deionized waters are firstly added in polymeric kettle and then sequentially add 100 parts of fourths
Benzene latex SBR1500,3 parts of neopelexes, 0.08 part of tert-dodecyl mercaptan after being replaced with nitrogen, add in 1.5 parts
Acrylic acid, stirring, heating, kettle temperature degree to be polymerized adds in 0.08 part of ammonium persulfate when reaching 35 DEG C, after reacting 4hr, adds in 0.2 part
Grafting styrene-butadiene latex a (0.5 ﹪ of grafting rate of styrene-butadiene latex) is made in Sodium Dimethyldithiocarbamate.
(3) preparation of high dispersive type carbon nanotube：Take 100 parts of carbon nanotube a and 1 part of lauric acid glycol ester, 300 parts go
Ionized water, 2 parts of sodium hydroxides are added in polymeric kettle and are stirred 10min；Then add in 2 parts of neopelexes, 1 part
Styrene-butadiene latex a is grafted, stirring is warming up to 60 DEG C, after being stirred to react 3hr, and high dispersive type is made in washed, dehydration, dry, grinding
Carbon nanotube.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
Embodiment 2
(1) preparation of carbon nanotube hydroxyl：With embodiment 1.
(2) preparation of graft latex：With embodiment 1.
(3) preparation of high dispersive type carbon nanotube：Take 100 parts of carbon nanotube a and 2 parts of lauric acid glycol esters, 350 parts go
Ionized water, 2.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 20min；Then 2.5 parts of dodecyl benzene sulfonic acid are added in
Sodium, 3 parts of grafting styrene-butadiene latex a, stirring are warming up to 60 DEG C, after being stirred to react 3hr, and height is made in washed, dehydration, dry, grinding
Dispersing type carbon nanotube.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
Embodiment 3
(1) preparation of carbon nanotube hydroxyl：By 100 parts of carbon nanotubes and 170 parts of concentrated nitric acids, 60 parts of concentrated sulfuric acids, 30 parts
Potassium permanganate is put into togerther in reactor and mixes, and with 70kHz ultrasonication 1.5hr, is then heated to 90 DEG C, stirring acid boils
7hr, cooling, suction filtration, washing are in neutrality to filtrate, are eventually adding 350 parts of ethylene glycol, are heated to 60 DEG C, are stirred to react 3hr,
It filters, wash, is dry, obtaining the carbon nanotube b that surface carries hydroxyl.
(2) preparation of graft latex：250 parts of deionized waters are firstly added in polymeric kettle and then sequentially add 100 parts of fourths
Benzene latex SBR1500,7 parts of neopelexes, 0.3 part of tert-dodecyl mercaptan, after being replaced with nitrogen, the third of 7 parts of addition
Olefin(e) acid, stirring, heating, kettle temperature degree to be polymerized adds in 0.20 part of ammonium persulfate when reaching 45 DEG C, after reacting 6hr, adds in 0.3 part of good fortune
Grafting styrene-butadiene latex b (1.1 ﹪ of grafting rate of styrene-butadiene latex) is made in U.S. sodium.
(3) preparation of high dispersive type carbon nanotube：Take 100 parts of carbon nanotube b and 2.5 parts of lauric acid glycol esters, 400 parts
Deionized water, 3.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 25min；Then 3 parts of dodecyl benzene sulfonic acid are added in
Sodium, 4 parts of grafting styrene-butadiene latex b, stirring are warming up to 65 DEG C, after being stirred to react 3.5hr, and washed, dehydration, dry, grinding are made
High dispersive type carbon nanotube.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
Embodiment 4
(1) preparation of carbon nanotube hydroxyl：With embodiment 3.
(2) preparation of graft latex：With embodiment 3.
(3) preparation of high dispersive type carbon nanotube：Take 100 parts of carbon nanotube b and 3 parts of lauric acid glycol esters, 400 parts go
Ionized water, 4 parts of sodium hydroxides are added in polymeric kettle and are stirred 28min；Then 3.5 parts of neopelexes, 5 are added in
Part is grafted styrene-butadiene latex b, and stirring is warming up to 65 DEG C, after being stirred to react 3.8hr, and washed, dehydration, grinds obtained high score at drying
Dissipate type carbon nanotube.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
Embodiment 5
(1) preparation of carbon nanotube hydroxyl：With embodiment 3.
(2) preparation of graft latex：With embodiment 3.
(3) preparation of high dispersive type carbon nanotube：Take 100 parts of carbon nanotube b and 3.5 parts of lauric acid glycol esters, 400 parts
Deionized water, 4.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 28min；Then 4 parts of dodecyl benzene sulfonic acid are added in
Sodium, 7 parts of grafting styrene-butadiene latex b, stirring are warming up to 65 DEG C, after being stirred to react 3.8hr, and washed, dehydration, dry, grinding are made
High dispersive type carbon nanotube.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
Embodiment 6
(1) preparation of carbon nanotube hydroxyl：By 100 parts of carbon nanotubes and 190 parts of concentrated nitric acids, 80 parts of concentrated sulfuric acids, 50 parts
Potassium permanganate is put into togerther in reactor and mixes, and with 90kHz ultrasonication 1.8hr, is then heated to 90 DEG C, stirring acid boils
8hr, cooling, suction filtration, washing are in neutrality to filtrate, are eventually adding 450 parts of pentaerythrites, are heated to 60 DEG C, are stirred to react
3hr is filtered, is washed, is dry, obtains the carbon nanotube c that surface carries hydroxyl.
(2) preparation of graft latex：300 parts of deionized waters are firstly added in polymeric kettle and then sequentially add 100 parts of fourths
1712,9.5 parts of neopelexes of benzene latex SBR, 0.45 part of tert-dodecyl mercaptan after being replaced with nitrogen, add in 9.5
The methacrylic acid of part, stirring, heating, kettle temperature degree to be polymerized adds in 0.25 part of ammonium persulfate when reaching 45 DEG C, after reacting 8hr,
0.4 part of Sodium Dimethyldithiocarbamate is added in, grafting styrene-butadiene latex c (1.4 ﹪ of grafting rate of styrene-butadiene latex) is made.
(3) preparation of high dispersive type carbon nanotube：Take 100 parts of carbon nanotube c and 4.5 parts of lauric acid butanediol esters, 480 parts
Deionized water, 5.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 25min；Then 4.3 parts of dodecyl benzene sulfonic acid are added in
Sodium, 8.5 parts of grafting styrene-butadiene latex c, stirring are warming up to 65 DEG C, after being stirred to react 4hr, and washed, dehydration, dry, grinding are made
High dispersive type carbon nanotube.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
Embodiment 7
(1) preparation of carbon nanotube hydroxyl：With embodiment 6.
(2) preparation of graft latex：With embodiment 6.
(3) preparation of high dispersive type carbon nanotube：Take 100 parts of carbon nanotube c and 5 parts of lauric acid butanediol esters, 500 parts go
Ionized water, 6 parts of sodium hydroxides are added in polymeric kettle and are stirred 30min；Then 5 parts of neopelexes, 10 are added in
Part is grafted styrene-butadiene latex c, and stirring is warming up to 70 DEG C, after being stirred to react 5hr, and washed, dehydration, grinds obtained high dispersive at drying
Type carbon nanotube.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
Comparative example 1
(1) preparation of carbon nanotube hydroxyl：With embodiment 1.
(2) preparation of graft latex：With embodiment 1.
(3) preparation of high dispersive type carbon nanotube：Other conditions are same as Example 1, and the difference lies in preparation process
The addition of middle grafting styrene-butadiene latex a is 0.5 part, i.e.,：Take 100 parts of carbon nanotube a and 1 part of lauric acid glycol ester, 300 parts go
Ionized water, 2 parts of sodium hydroxides are added in polymeric kettle and are stirred 10min；Then 2 parts of neopelexes, 0.5 are added in
Part is grafted styrene-butadiene latex a, and stirring is warming up to 60 DEG C, after being stirred to react 3hr, and washed, dehydration, grinds obtained high dispersive at drying
Type carbon nanotube.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
Comparative example 2
(1) preparation of graft latex：With embodiment 1.
(2) preparation of high dispersive type carbon nanotube：Other conditions are same as Example 2, and the difference lies in preparation process
In be added without carbon nanotube a, but be directly added into not hydroxylated carbon nanotube, i.e.,：Take 100 parts of not hydroxylated carbon nanotubes
It is added in polymeric kettle with 2 parts of lauric acid glycol esters, 350 parts of deionized waters, 2.5 parts of sodium hydroxides and is stirred 20min；So
2.5 parts of neopelexes, 3 parts of grafting styrene-butadiene latex a are added in afterwards, and stirring is warming up to 60 DEG C, after being stirred to react 3hr, warp
High dispersive type carbon nanotube is made in washing, dehydration, dry, grinding.Sampling analysis：Standard sample is made, performance is shown in Table after tested
1。
Comparative example 3
(1) preparation of carbon nanotube hydroxyl：With embodiment 3.
(2) preparation of high dispersive type carbon nanotube：Other conditions are same as Example 3, and the difference lies in preparation process
In be added without grafting styrene-butadiene latex b, but be directly added into styrene-butadiene latex SBR1500, i.e.,：Take 100 parts of carbon nanotube b and 2.5 parts
Lauric acid glycol ester, 400 parts of deionized waters, 3.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 25min；Then plus
Enter 3 parts of neopelexes, 4 parts of styrene-butadiene latex SBR1500, stirring is warming up to 65 DEG C, after being stirred to react 3.5hr, through washing
It washs, be dehydrated, drying, grinding obtained high dispersive type carbon nanotube.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
Comparative example 4
(1) preparation of carbon nanotube hydroxyl：With embodiment 3.
(2) preparation of graft latex：With embodiment 3.
(3) preparation of high dispersive type carbon nanotube：Other conditions are same as Example 4, and the difference lies in preparation process
In be added without lauric acid glycol ester, i.e.,：Take 100 parts of carbon nanotube b and 400 parts of deionized waters, 4 parts of sodium hydroxides be added to it is poly-
It closes in kettle and is stirred 28min；Then 3.5 parts of neopelexes, 5 parts of grafting styrene-butadiene latex b are added in, stirring is warming up to
65 DEG C, after being stirred to react 3.8hr, high dispersive type carbon nanotube is made in washed, dehydration, dry, grinding.Sampling analysis：It is made
Standard sample, after tested performance be shown in Table 1.
Comparative example 5
(1) preparation of carbon nanotube hydroxyl：With embodiment 3.
(2) preparation of graft latex：With embodiment 3.
(3) preparation of high dispersive type carbon nanotube：Other conditions are same as Example 5, and the difference lies in preparation process
The addition of middle lauric acid glycol ester is 0.9 part, i.e.,：Take 100 parts of carbon nanotube b and 0.9 part of lauric acid glycol ester, 400
Part deionized water, 4.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 28min；Then 4 parts of dodecyl benzene sulfonic acid are added in
Sodium, 7 parts of grafting styrene-butadiene latex b, stirring are warming up to 65 DEG C, after being stirred to react 3.8hr, and washed, dehydration, dry, grinding are made
High dispersive type carbon nanotube.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
Comparative example 6
(1) preparation of carbon nanotube hydroxyl：Other conditions are same as Example 6, and the difference lies in preparation process
Pentaerythrite is not added with, i.e.,：100 parts of carbon nanotubes and 190 parts of concentrated nitric acids, 80 parts of concentrated sulfuric acids, 50 parts of potassium permanganate are put into togerther
It is mixed in reactor, with 90kHz ultrasonication 1.8hr, is then heated to 90 DEG C, stirring acid boils 8hr, and cooling filters, washing
It is in neutrality to filtrate, is finally heated to 60 DEG C, be stirred to react 3hr, filtered, wash, is dry, obtain the carbon that surface carries hydroxyl
Nanotube c-1.
(2) preparation of graft latex：With embodiment 6.
(3) preparation of high dispersive type carbon nanotube：Other conditions are same as Example 6, and the difference lies in preparation process
In be added without carbon nanotube c, but add in carbon nanotube c-1, i.e.,：Take 100 parts of carbon nanotube c-1 and 4.5 parts of lauric acid fourths two
Alcohol ester, 480 parts of deionized waters, 5.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 25min；Then 4.3 part 12 is added in
Sodium alkyl benzene sulfonate, 8.5 parts of grafting styrene-butadiene latex c, stirring are warming up to 65 DEG C, after being stirred to react 4hr, and washed, dehydration is done
High dispersive type carbon nanotube is made in dry, grinding.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
Comparative example 7
(1) preparation of carbon nanotube hydroxyl：With embodiment 6.
(2) preparation of graft latex：Other conditions are same as Example 6, and the difference lies in methyl-props in preparation process
The addition of olefin(e) acid is 17 parts, i.e.,：300 parts of deionized waters are firstly added in polymeric kettle and then sequentially add 100 parts of butadiene-styrene rubbers
Newborn 1712,9.5 parts of neopelexes of SBR, 0.45 part of tert-dodecyl mercaptan after being replaced with nitrogen, add in 17 parts of first
Base acrylic acid, stirring, heating, kettle temperature degree to be polymerized adds in 0.25 part of ammonium persulfate when reaching 45 DEG C, after reacting 8hr, adds in 0.4
Part Sodium Dimethyldithiocarbamate, is made grafting styrene-butadiene latex c-1 (2.1 ﹪ of grafting rate of styrene-butadiene latex).
(3) preparation of high dispersive type carbon nanotube：Other conditions are same as Example 7, and the difference lies in preparation process
In be added without grafting styrene-butadiene latex c, but add in grafting rate 2.1 ﹪ grafting styrene-butadiene latex c-1, i.e.,：Take 100 parts of carbon nanotube c
It is added in polymeric kettle with 5 parts of lauric acid butanediol esters, 500 parts of deionized waters, 6 parts of sodium hydroxides and is stirred 30min；Then
5 parts of neopelexes, 10 parts of grafting styrene-butadiene latex c-1 (2.1 ﹪ of grafting rate) are added in, stirring is warming up to 70 DEG C, stirring
After reacting 5hr, high dispersive type carbon nanotube is made in washed, dehydration, dry, grinding.Sampling analysis：Standard sample is made, passes through
Test performance is shown in Table 1.
The settling volume and oil absorbency of 1 high dispersive type carbon nanotube of table
As shown in Table 1：The settling volume of embodiment is big than comparative example under same time, and oil absorption is below comparing
Example illustrates that the modified effect of the present invention is apparent.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (13)
1. a kind of method of modifying for the carbon nanotube for being used as gum filler, which is characterized in that include the following steps：
(1) preparation of carbon nanotube hydroxyl：In parts by mass, by 100 parts of carbon nanotubes and 150~200 parts of concentrated nitric acids, 50~
100 parts of concentrated sulfuric acids, 10~50 parts of potassium permanganate are put into togerther in reactor and mix, with 50~100kHz ultrasonications 1~
2hr is then heated to 50~150 DEG C, and stirring acid boils 1~10hr, and cooling, suction filtration, washing are in neutrality to filtrate, are eventually adding
200~500 parts of polyalcohols, are heated to 50~90 DEG C, are stirred to react 1~5hr, filter, wash, is dry, obtaining surface and carry
The carbon nanotube of hydroxyl；
(2) preparation of graft latex：In parts by mass, 100~300 parts of deionized waters, Ran Houyi are firstly added in polymeric kettle
100 parts of styrene-butadiene latexes of secondary addition, 1~10 part of emulsifier, 0.05~0.5 part of molecular weight regulator after being replaced with nitrogen, add in 1
~10 parts of unsaturated carboxylic acid polar monomer, stirring, heating, kettle temperature degree to be polymerized add in 0.05~0.3 when reaching 30~50 DEG C
Part initiator after reacting 3~8hr, adds in 0.1~0.5 part of terminator, graft latex is made；
(3) preparation of modified carbon nano-tube：In parts by mass, take 100 parts of hydroxyl carbon nano tubes and 1~5 part of surfactant,
300~500 parts of deionized waters, 1~6 part of buffer are added in polymeric kettle and are stirred 10~30min；Then 1~5 part is added in
Emulsifier, 1~10 part of graft latex, stirring are warming up to 50~70 DEG C, after being stirred to react 1~5hr, washed, dehydration, it is dry,
Modified carbon nano-tube is made in grinding.
2. the method as described in claim 1, which is characterized in that the carbon nanotube be it is nano level, grain size for 0.3~
30nm。
3. method as claimed in claim 1 or 2, which is characterized in that the polyalcohol be selected from ethylene glycol, propylene glycol, glycerine,
The mixture of one or more of butanediol, pentaerythrite.
4. method as claimed in claim 1 or 2, which is characterized in that the styrene-butadiene latex be by conjugated diene hydrocarbon compound and
Aryl ethylene class compound is copolymerized by emulsion polymerization.
5. method as claimed in claim 4, which is characterized in that the conjugated diene hydrocarbon compound is C4Class conjugated diene hydrocarbonylation
Close object.
6. method as claimed in claim 4, which is characterized in that the aryl ethylene class compound is styrene, Alpha-Methyl benzene
Ethylene, 2- propenyl benzenes, ethyl styrene and their derivative.
7. method as claimed in claim 4, which is characterized in that the solid content of the styrene-butadiene latex is 20~45w%.
8. method as claimed in claim 1 or 2, which is characterized in that the unsaturated carboxylic acid polar monomer is selected from acrylic acid, first
One kind in base acrylic acid, 2- ethylacrylic acids.
9. method as claimed in claim 8, which is characterized in that the unsaturated carboxylic acid polar monomer is acrylic acid.
10. method as claimed in claim 1 or 2, which is characterized in that the initiator is water-soluble thermal initiator：It was selected from
Bis- (the 2 one amidine oxazoline propane) hydrochlorides of ammonium sulfate, potassium peroxydisulfate, sodium peroxydisulfate, 2,2-azo, 2,2-azo [2-(2-miaow
Oxazoline-2-yl) propane] one kind in dihydrochloride.
11. method as claimed in claim 10, which is characterized in that the initiator is ammonium persulfate.
12. the method as described in claim 1, which is characterized in that the initiator addition is 0.07~0.2 part.
13. method as claimed in claim 1 or 2, which is characterized in that the surfactant be selected from lauric acid glycol ester,
One or more of lauric acid propylene glycol ester, lauric acid glycerine ester, lauric acid butanediol ester, lauric acid pentaerythritol ester
Mixture.
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| CN113214638A (en) * | 2021-05-27 | 2021-08-06 | 湖南飞鸿达新材料有限公司 | Wave-absorbing heat-conducting flexible composite material and preparation method thereof |
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