CN109897249A - The preparation method of the rubber composition of filling carbon nano-pipe - Google Patents
The preparation method of the rubber composition of filling carbon nano-pipe Download PDFInfo
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- CN109897249A CN109897249A CN201711286016.3A CN201711286016A CN109897249A CN 109897249 A CN109897249 A CN 109897249A CN 201711286016 A CN201711286016 A CN 201711286016A CN 109897249 A CN109897249 A CN 109897249A
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Abstract
It is an object of that present invention to provide a kind of preparation methods with high tensile, the rubber composition for tire tread of good wearability and low rolling resistance of carbon nanotubes.The invention carries out hydroxylating processing to carbon nano tube surface first, then it is graft-polymerized using unsaturated carboxylic acid polar monomer to styrene-butadiene latex, it is handled secondly by cladding, and mixes, agglomerated to prepare the rubber composition of high-performance tire tread rubber with styrene butadiene rubber latex.The invention not only efficiently solves the problems, such as the easy to reunite of carbon nanotube, but also also solves the problem of carbon nanotube and butadiene-styrene rubber basal body binding force difference and dispersion unevenness, imparts polymolecularity of the carbon nanotube in rubber matrix.
Description
Technical field
The present invention relates to a kind of rubber compositions, are used for more particularly to a kind of modified carbon nano-tube filled styrene butadiene rubber
Rubber composition of tire tread and preparation method thereof.
Background technique
In recent years, the requirement with automobile to high speed, safety, energy conservation, the development in comfortableization direction, to tire high performance
Also higher and higher, this requires the balances of tire tread glue " devil's triangle " performance must obtain obvious promotion, that is to say, that
Tire tread glue will also have excellent wearability and low rolling resistance while with good wet-sliding resistant performance.With
Appearance with high-modulus and High Strength Carbon Nanotubes (Carbon Nanotube, abbreviation CNT), it is high by high molecular material is assigned
The characteristics such as intensity, low bulk, high abrasion, and as reinforced filling in tire tread formula, capable of making tread rubber, " devil three
Angle " performance obtains significantly balance, is increasingly subject to the concern of people in the application of field of rubber materials.
But carbon nanotube category nanometer materials, partial size is small, specific surface is big, surface energy is high, easily reunites, and is participating in
It is easy to be gathered into useless agglomerate in the mixed process of rubber material, causes to disperse non-uniform problem appearance, so not only
It will affect filling-modified effect, but also the performance of rubber material can be damaged.
Carbon nanotube composite modification material studies oneself one of the hot spot as the research of current Material Field.So far, specially
There are many benefit modified carbon nano-tube composite material reported in the literature.ZL 200510058999.6 is first surface-treated CNT,
Make it have hydrophily；Then it is mixed with dispersing agent, deionized water, obtains mono- water slurry of CNT；Then with Heveatex
Uniformly mixing finally prepares the modified powder natural rubber containing CNT using spray drying process.ZL 200310109074.0 is first
Polarity first is carried out to carbon nano tube surface and nonpolarity is handled, is allowed to have amphiphilic performance, then uses polyolefin, polyacrylic
Polymer carries out the processing of surface cladding, to obtain carbon nanotube/high molecule nano composite material.ZL 200510009769.0
There is provided it is a kind of using the dispersion of ultrasonic wave and high-speed stirred disperser, crushing, activation the effects of, destroy the poly- of carbon nanotube itself
Collection and winding；Chemisorption or chemical reaction are carried out using the organo-functional group and carbon nano tube surface of surfactant, makes table
Face activating agent is covered on carbon nano tube surface, to realize dispersion to surface modification of carbon nanotube and its in the epoxy.
ZL 200410089036.8 is then to use silane, Wo Lan or titanate esters as coupling agent using polyvinyl imidazole as polymerized monomer,
The carbon nanotube/polyvinylimidazole nanocomposites materials prepared through hydroxyl chemical etching method and microemulsion polymerization method.
Summary of the invention
It is an object of that present invention to provide a kind of preparation method of the rubber composition of filling carbon nano-pipe, the rubber compositions
Tensile strength, good wearability, low rolling resistance for tire tread Shi Yougao.The invention is first to carbon nano tube surface
Hydroxylating processing is carried out, is then graft-polymerized using unsaturated carboxylic acid polar monomer to styrene-butadiene latex, secondly by cladding
Processing finally mixes with styrene butadiene rubber latex to prepare high dispersive and have the carbon nanotube of certain compatibility with butadiene-styrene rubber, is solidifying
Gather to prepare the rubber composition of high-performance tire tread rubber.The invention not only efficiently solves the easy to reunite of carbon nanotube and asks
Topic, and also solve the problem of carbon nanotube and butadiene-styrene rubber basal body binding force difference and dispersion unevenness.The present invention further mentions
The preparation method of the composition out.
" part " of the present invention each means mass parts.
A kind of rubber composition for tire tread of the present invention, with the quality of styrene butadiene rubber latex dry glue for hundred
/ hundred meters, mainly include following component:
(1) styrene butadiene rubber latex (dry glue) 100%
(2) distributed carbon nanotube 10~40%
Wherein, the distributed carbon nanotube is to be carried out at hydroxylating using polyalcohol to carbon nano tube surface first
Secondly reason is graft-polymerized to styrene-butadiene latex under initiator effect using unsaturated carboxylic acid polar monomer, finally by table
Activating agent cladding processing in face is to prepare.Carbon nanotube is selected from nanoscale, partial size are as follows: 0.3~30nm.Polyalcohol is selected from second two
One or more of alcohol, propylene glycol, glycerine, butanediol, pentaerythrite.Unsaturated carboxylic acid polar monomer is selected from acrylic acid
(AA), one of methacrylic acid (MAA), 2- ethylacrylic acid, preferably acrylic acid (AA).Surfactant is selected from lauric acid
Glycol ester, lauric acid propylene glycol ester, lauric acid glycerine ester, lauric acid butanediol ester, one in lauric acid pentaerythritol ester
Kind is a variety of.Initiator is water-soluble thermal initiator: being selected from ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, 2,2-azos bis- (2
One amidine oxazoline propane) hydrochloride, 2, one of 2-azos [2-(2-imidazoline-2-yl) propane] dihydrochloride is excellent
Ammonium persulfate is selected, in order to guarantee to be grafted the usability of styrene-butadiene latex, the additional amount of initiator needs strict control, and additional amount is
0.05~0.3 part, preferably 0.07~0.2 part.
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 can be benzene second
Alkene, α-methylstyrene, 2- propenyl benzene, ethyl styrene and their derivative.Wherein the solid content 20 of styrene-butadiene latex~
45%, combinated styrene content content 15~25%, 50~200nm of latex particle size.
The preparation of rubber composition of the present invention can carry out in condensing field, and specific preparation process includes following step
It is rapid:
(1) preparation of distributed carbon nanotube:
The preparation of a carbon nanotube hydroxyl: based on the mass percent of carbon nanotube, 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
1~2hr of ultrasonication is then heated at 50~150 DEG C, and stirring acid boils 1~10hr, and cooling, suction filtration, washing to filtrate are in
Neutrality is eventually adding 200~500 parts of polyalcohols, is heated at 50~90 DEG C, is stirred to react 1~5hr, filters, washing, does
It is dry, obtain the carbon nanotube that surface has hydroxyl.
The preparation of b grafting styrene-butadiene latex: being in terms of 100 parts by styrene-butadiene latex quality, it is firstly added 100 in polymeric kettle~
Then 300 parts of deionized waters sequentially add 100 parts of styrene-butadiene latexes, 1~10 part of emulsifier, 0.05~0.5 part of molecular-weight adjusting
After being replaced with nitrogen, 1~10 part of unsaturated carboxylic acid polar monomer, stirring, heating is added in agent, and kettle temperature degree to be polymerized reaches 30
0.05~0.3 part of initiator is added at~50 DEG C, after reacting 3~8h, 0.1~0.5 part of terminator is added, graft latex is made
(grafting rate 0.1 ﹪~1.5 ﹪ of styrene-butadiene latex).
The preparation of c dispersing type carbon nanotube: based on the mass percent of hydroxyl carbon nano tube, 100 parts of hydroxylating carbon are taken
Nanotube and 1.0~5.0 parts of surfactants, 300~500 parts of deionized waters, 1~6 part of buffer are added in polymeric kettle and stir
Mix 10~30min of mixing；Then 1~5 part of emulsifier, 1~10 part of graft latex is added, stirring is warming up to 50~70 DEG C, stirring
After reacting 1~5hr, distributed carbon nanotube is made in washed, dehydration, dry, grinding.
(2) preparation of tyre surface butadiene-styrene rubber composition: being to take 100 parts of fourths in terms of 100 parts by the quality of styrene-butadiene latex dry glue
Benzene latex (dry glue) and 1~5 part of emulsifier, 100~300 parts of deionized waters are added in condensing field and are stirred 10~30min,
Then 10~40 parts of distributed carbon nanotubes are added, are 9~12, when being warming up to 40~60 DEG C with buffer regulation system pH value,
It is stirred 30~60min, 3~7 parts of flocculating agents are then added and are condensed, last washed, dehydration, dry, briquetting are made
Tyre surface butadiene-styrene rubber composition.
The present invention is not specially limited used emulsifier, flocculating agent, buffer etc., can use this field
General conven-tional adjuvants, additional amount are also the conventional use that those skilled in the art can be calculated according to the dosage of dry glue
Amount, the present invention also do not do particular determination.
Cohesion of the present invention, poly- using acid cure, the technology is general for those skilled in the art, the flocculating agent
Usually inorganic acid, such as one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid or a variety of.
Emulsifier of the present invention is known to those skilled in the art, can be anion emulsifier and nonionic Emulsion
One of agent is a variety of.Such as: selected from fatty acid soaps, RA rosin acid, neopelex, lauryl sodium sulfate,
One of polyoxyethylene sorbitol acid anhydride list olein is a variety of, preferably neopelex.
Buffer of the present invention is selected from one of sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonium hydroxide, ammonium hydrogen carbonate,
It is preferred that sodium hydroxide.
The particle diameter for the carbon nanotube that the present invention uses is small, and the large specific surface area of particle, surface can be high, easily occurs mutual
Agglomeration only is difficult to allow ultrafine particle in rubber-based by traditional method of modifying such as mechanical stirring or activating agent surface treatment
It is in nano-dispersion in body, Ultrafine effect is difficult to play.In order to solve this problem, first to using acid with strong oxidizing property and polynary
Alcohol to carbon nano tube surface carry out hydroxylating processing so that carbon nano tube surface have hydroxyl, by " hydrogen bond action " with it is polynary
Alcohol ester links together, and forms the single-point anchor point based on carbonyl in carbon nano tube surface.The anchor point and grafting butadiene-styrene rubber
The polar group carboxyl of cream generates the mutual attractive force between molecule, can be formed in carbon nanotube particle surface secured, close
Styrene-butadiene latex clad.Styrene-butadiene latex has the characteristics that nonpolarity and containing benzene ring structure, can between nanoparticle shape
At steadily space bit resistance layer, the activation energy of nanoparticle surface can be significantly reduced, hinders the mutual reunion between particle,
It can be realized and steadily exist with single particle shape.Phase of the carbon nanotube with butadiene-styrene rubber can also significantly be improved simultaneously
Capacitive can be realized as with tiny particle shape stabilization without adding any surfactant, be evenly dispersed in butylbenzene rubber
In matrix body.Play the Ultrafine effect of carbon nanotube, while the high-modulus and high intensity of carbon nanotube
Characteristic fully demonstrated in tyre surface in butadiene-styrene rubber composition, carbon nanotube tube-like condition can make tread rubber, and " devil three
Angle " performance obtains significantly balance, to obtain having good anti-slippery and excellent wearability and low rolling resistance
The tire tread of power butadiene-styrene rubber composition.Preparation method of the invention avoids sizing material in traditional mixing or mill rubber
The problems such as skidding that occurs in processing, incipient scorch, uneven dispersion, method is simple and easy, low in cost, no pollution to the environment, fits
Close industrialized production.
Detailed description of the invention
The infrared spectrum spectrogram of attached drawing 1 carbon nanotube (a) and high dispersive type carbon nanotube (b).
Specific embodiment
Following embodiment and comparative example are enumerated to illustrate invention effect of the 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:
Styrene-butadiene latex SBR1500, solid content 23%, Lanzhou Petrochemical Company
Styrene-butadiene latex SBR1712, solid content 22.5%, Lanzhou Petrochemical Company
Carbon nanotube, partial size are the Chengdu 10~30nm organic chemistry research institute
Acrylic acid (AA), purity 99%, Zhengzhou Sen Ta Chemical Co., Ltd.
Methacrylic acid (MAA), purity 99%, Zhengzhou Sen Ta Chemical Co., Ltd.
Ethylene glycol, the emerging milky way Chemical Co., Ltd. in Hubei
Pentaerythrite, the emerging milky way Chemical Co., Ltd. in Hubei
Lauric acid glycol ester, Shanghai Jia Chen Chemical Co., Ltd.
Lauric acid butanediol ester, Shanghai Jia Chen Chemical Co., Ltd.
Ammonium persulfate, Hubei wind emerging milky way Chemical Group company
Other reagents are commercially available industrial goods
(2) analysis test method:
The measurement of grafting rate: taking the sample of about 4g in weighing bottle from three-necked bottle with pipette, and 2~3 are added after weighing
Quinol solution is dripped, drying to constant weight, 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)；Weighed sample quality (g) 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: before modified using Bruke spectral instrument company, Germany infrared spectrometer Nano carbon white
Sample carries out functional group analysis afterwards.Sample is dried at 100 DEG C in vacuum drying oven, using pressing potassium bromide troche, acquires wave number model
Enclose 400-4000cm—1。
0 DEG C and 60 DEG C of fissipation factors: being analyzed using the DMA Q800 type dynamic thermomechanical analysis apparatus of TA company,
Select double cantilever chucks.In -150 DEG C~100 DEG C temperature programmings, heating rate is 3 DEG C/min, amplitude 10
μm, test frequency is respectively 1Hz, 5Hz, 10Hz, dynamic force 1N.
Tensile strength: method in standard GB/T528-2009 is executed.
Dispersion degree: method in standard GB/T6030-1985 is executed.
Akron abrasion volume；Method in execution standard GB/T 25262-2010.
Embodiment 1
(1) preparation of distributed carbon nanotube:
The preparation of a carbon nanotube hydroxyl: by 100 parts of carbon nanotubes and 150 parts of concentrated nitric acids, 50 parts of concentrated sulfuric acids, 10 parts of height
Potassium manganate is put into togerther in reactor and mixes, and with 60kHz ultrasonication 1.2hr, is then heated at 70 DEG C, and stirring acid boils
5hr, cooling, suction filtration, washing are in neutrality to filtrate, are eventually adding 200 parts of ethylene glycol, are heated at 60 DEG C, are stirred to react
2hr filters, washing, drying, obtains the carbon nanotube a that surface has hydroxyl.
The preparation of b grafting styrene-butadiene latex: it is firstly added 100 parts of deionized waters in polymeric kettle, then sequentially adds 100 parts
Styrene-butadiene latex SBR1500,3 parts of neopelexes, 0.08 part of tert-dodecyl mercaptan after being replaced with nitrogen, are added 1.5 parts
Acrylic acid, stirring, heating are added 0.08 part of ammonium persulfate, after reacting 4hr, are added 0.2 when kettle temperature degree to be polymerized reaches 35 DEG C
Part Sodium Dimethyldithiocarbamate, is made grafting styrene-butadiene latex a (0.5 ﹪ of grafting rate of styrene-butadiene latex).
The preparation of c dispersing type carbon nanotube: take 100 parts of carbon nanotube a and 1.0 parts of lauric acid glycol esters, 300 parts go from
Sub- water, 2 parts of sodium hydroxides are added in polymeric kettle and are stirred 10min；Then 2 parts of neopelexes, 1.0 parts are added
It is grafted styrene-butadiene latex a, stirring is warming up to 60 DEG C, after being stirred to react 3hr, and distributed carbon is made in washed, dehydration, dry, grinding
Nanotube.
(2) 100 parts of styrene-butadiene latex SBR1500 (dry glue) and 1 part of dodecane the preparation of tyre surface butadiene-styrene rubber composition: are taken
Base benzene sulfonic acid sodium salt, 100 parts of deionized waters are added in condensing field and are stirred 10min, and 10 parts of distributed carbon nanometers are then added
Pipe, is 9 with sodium hydroxide regulation system pH value, when being warming up to 40 DEG C, is stirred 30min, and 3 parts of hydrochloric acid are then added and are coagulated
Poly-, tyre surface butadiene-styrene rubber composition is made in last washed, dehydration, dry, briquetting.Sampling analysis: standard is made through vulcanization
Sample, test performance are shown in Table 1.
Embodiment 2
(1) preparation of distributed carbon nanotube:
The preparation of a carbon nanotube hydroxyl: with embodiment 1.
The preparation of b grafting styrene-butadiene latex: with embodiment 1.
The preparation of c dispersing type carbon nanotube: take 100 parts of carbon nanotube a and 2.0 parts of lauric acid glycol esters, 350 parts go from
Sub- water, 2.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 20min；Then be added 2.5 parts of neopelexes,
3.0 parts of grafting styrene-butadiene latex a, stirring are warming up to 60 DEG C, after being stirred to react 3hr, and dispersion is made in washed, dehydration, dry, grinding
Type carbon nanotube.
(2) 100 parts of styrene-butadiene latex SBR1500 (dry glue) and 2 parts of dodecanes the preparation of tyre surface butadiene-styrene rubber composition: are taken
Base benzene sulfonic acid sodium salt, 150 parts of deionized waters are added in condensing field and are stirred 15min, and 15 parts of distributed carbon nanometers are then added
Pipe, is 10 with sodium hydroxide regulation system pH value, when being warming up to 45 DEG C, is stirred 35min, and 4 parts of hydrochloric acid are then added and carry out
Tyre surface butadiene-styrene rubber composition is made in cohesion, last washed, dehydration, dry, briquetting.Sampling analysis: mark is made through vulcanization
Quasi- sample, test performance are shown in Table 1.
Embodiment 3
(1) preparation of distributed carbon nanotube:
The preparation of a carbon nanotube hydroxyl: by 100 parts of carbon nanotubes and 170 parts of concentrated nitric acids, 60 parts of concentrated sulfuric acids, 30 parts of height
Potassium manganate is put into togerther in reactor and mixes, and with 70kHz ultrasonication 1.5hr, is then heated at 90 DEG C, and stirring acid boils
7hr, cooling, suction filtration, washing are in neutrality to filtrate, are eventually adding 350 parts of ethylene glycol, are heated at 60 DEG C, are stirred to react
3hr filters, washing, drying, obtains the carbon nanotube b that surface has hydroxyl.
The preparation of b grafting styrene-butadiene latex: it is firstly added 250 parts of deionized waters in polymeric kettle, then sequentially adds 100 parts
Styrene-butadiene latex SBR1500,7 parts of neopelexes, 0.3 part of tert-dodecyl mercaptan after being replaced with nitrogen, are added 7.0 parts
Acrylic acid, stirring, heating are added 0.20 part of ammonium persulfate, after reacting 6hr, are added 0.3 when kettle temperature degree to be polymerized reaches 45 DEG C
Part Sodium Dimethyldithiocarbamate, is made grafting styrene-butadiene latex b (1.1 ﹪ of grafting rate of styrene-butadiene latex).
The preparation of c dispersing type carbon nanotube: take 100 parts of carbon nanotube b and 2.5 parts of lauric acid glycol esters, 400 parts go from
Sub- water, 3.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 25min；Then be added 3.0 parts of neopelexes,
4.0 parts of grafting styrene-butadiene latex b, stirring are warming up to 65 DEG C, after being stirred to react 3.5hr, washed, dehydration, drying, obtained point of grinding
Dissipate type carbon nanotube.
(2) 100 parts of styrene-butadiene latex SBR1500 (dry glue) and 3 parts of dodecanes the preparation of tyre surface butadiene-styrene rubber composition: are taken
Base benzene sulfonic acid sodium salt, 150 parts of deionized waters are added in condensing field and are stirred 15min, and 20 parts of distributed carbon nanometers are then added
Pipe, is 10 with sodium hydroxide regulation system pH value, when being warming up to 45 DEG C, is stirred 40min, and 5 parts of hydrochloric acid are then added and carry out
Tyre surface butadiene-styrene rubber composition is made in cohesion, last washed, dehydration, dry, briquetting.Sampling analysis: mark is made through vulcanization
Quasi- sample, test performance are shown in Table 1.
Embodiment 4
(1) preparation of distributed carbon nanotube:
The preparation of a carbon nanotube hydroxyl: with embodiment 3.
The preparation of b grafting styrene-butadiene latex: with embodiment 3.
The preparation of c dispersing type carbon nanotube: take 100 parts of carbon nanotube b and 3.0 parts of lauric acid glycol esters, 400 parts go from
Sub- water, 4.0 parts of sodium hydroxides are added in polymeric kettle and are stirred 28min；Then be added 3.5 parts of neopelexes,
5.0 parts of grafting styrene-butadiene latex b, stirring are warming up to 65 DEG C, after being stirred to react 3.8hr, washed, dehydration, drying, obtained point of grinding
Dissipate type carbon nanotube.
(2) 100 parts of styrene-butadiene latex SBR1500 (dry glue) and 3.5 part 12 preparation of tyre surface butadiene-styrene rubber composition: are taken
Sodium alkyl benzene sulfonate, 200 parts of deionized waters are added in condensing field and are stirred 20min, and 25 parts of distributed carbon are then added and receive
Mitron is 10 with sodium hydroxide regulation system pH value, when being warming up to 50 DEG C, is stirred 45min, 5.5 parts of hydrochloric acid are then added
It is condensed, tyre surface butadiene-styrene rubber composition is made in last washed, dehydration, dry, briquetting.Sampling analysis: it is made through vulcanization
At standard sample, test performance is shown in Table 1.
Embodiment 5
(1) preparation of distributed carbon nanotube:
The preparation of a carbon nanotube hydroxyl: by 100 parts of carbon nanotubes and 190 parts of concentrated nitric acids, 80 parts of concentrated sulfuric acids, 50 parts of height
Potassium manganate is put into togerther in reactor and mixes, and with 90kHz ultrasonication 1.8hr, is then heated at 90 DEG C, and stirring acid boils
8.0hr, cooling, suction filtration, washing are in neutrality to filtrate, are eventually adding 450 parts of pentaerythrites, are heated at 60 DEG C, and stirring is anti-
3hr is answered, filters, washing, drying, obtains the carbon nanotube c that surface has hydroxyl.
The preparation of b grafting styrene-butadiene latex: it is firstly added 300 parts of deionized waters in polymeric kettle, then sequentially adds 100 parts
Styrene-butadiene latex SBR1712,9.5 parts of neopelexes, 0.45 part of tert-dodecyl mercaptan after being replaced with nitrogen, are added 9.5
The methacrylic acid of part, stirring, heating, 0.25 part of ammonium persulfate is added when reaching 45 DEG C in kettle temperature degree to be polymerized, after reacting 8hr,
0.4 part of Sodium Dimethyldithiocarbamate is added, grafting styrene-butadiene latex c (1.4 ﹪ of grafting rate of styrene-butadiene latex) is made.
The preparation of c dispersing type carbon nanotube: take 100 parts of carbon nanotube c and 4.5 parts of lauric acid butanediol esters, 480 parts go from
Sub- water, 5.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 25min；Then be added 4.3 parts of neopelexes,
8.5 parts of grafting styrene-butadiene latex c, stirring are warming up to 65 DEG C, after being stirred to react 4.0hr, washed, dehydration, drying, obtained point of grinding
Dissipate type carbon nanotube.
(2) 100 parts of styrene-butadiene latex SBR1712 (dry glue) and 4.0 part 12 preparation of tyre surface butadiene-styrene rubber composition: are taken
Sodium alkyl benzene sulfonate, 270 parts of deionized waters are added in condensing field and are stirred 25min, and 30 parts of distributed carbon are then added and receive
Mitron is 11 with sodium hydroxide regulation system pH value, when being warming up to 55 DEG C, is stirred 50min, 6.0 parts of sulfuric acid are then added
It is condensed, tyre surface butadiene-styrene rubber composition is made in last washed, dehydration, dry, briquetting.Sampling analysis: it is made through vulcanization
At standard sample, test performance is shown in Table 1.
Embodiment 6
(1) preparation of distributed carbon nanotube:
The preparation of a carbon nanotube hydroxyl: with embodiment 5.
The preparation of b grafting styrene-butadiene latex: with embodiment 5.
The preparation of c dispersing type carbon nanotube: take 100 parts of carbon nanotube c and 5.0 parts of lauric acid butanediol esters, 500 parts go from
Sub- water, 6.0 parts of sodium hydroxides are added in polymeric kettle and are stirred 30min；Then be added 5.0 parts of neopelexes,
10 parts of grafting styrene-butadiene latex c, stirring are warming up to 70 DEG C, after being stirred to react 5.0hr, washed, dehydration, drying, obtained point of grinding
Dissipate type carbon nanotube.
(2) 100 parts of styrene-butadiene latex SBR1712 (dry glue) and 5.0 part 12 preparation of tyre surface butadiene-styrene rubber composition: are taken
Sodium alkyl benzene sulfonate, 300 parts of deionized waters are added in condensing field and are stirred 30min, and 40 parts of distributed carbon are then added and receive
Mitron is 12 with sodium hydroxide regulation system pH value, when being warming up to 60 DEG C, is stirred 60min, 7.0 parts of sulfuric acid are then added
It is condensed, tyre surface butadiene-styrene rubber composition is made in last washed, dehydration, dry, briquetting.Sampling analysis: it is made through vulcanization
At standard sample, test performance is shown in Table 1.
Comparative example 1
(1) preparation of distributed carbon nanotube:
The preparation of a carbon nanotube hydroxyl: with embodiment 1.
The preparation of b grafting styrene-butadiene latex: with embodiment 1.
The preparation of c dispersing type carbon nanotube: with embodiment 1.
(2) preparation of tyre surface butadiene-styrene rubber composition: other conditions are same as Example 1, the difference is that preparation
The additional amount of distributed carbon nanotube is 8 parts in the process, it may be assumed that takes 100 parts of styrene-butadiene latex SBR1500 (dry glue) and 1 part of dodecane
Base benzene sulfonic acid sodium salt, 100 parts of deionized waters are added in condensing field and are stirred 10min, and 8 parts of distributed carbon nanometers are then added
Pipe, is 9 with sodium hydroxide regulation system pH value, when being warming up to 40 DEG C, is stirred 30min, and 3 parts of hydrochloric acid are then added and are coagulated
Poly-, tyre surface butadiene-styrene rubber composition is made in last washed, dehydration, dry, briquetting.Sampling analysis: standard is made through vulcanization
Sample, test performance are shown in Table 1.
Comparative example 2
The preparation of tyre surface butadiene-styrene rubber composition: other conditions are same as Example 2, the difference is that preparation process
In distributed carbon nanotube is not added, but be directly added into unmodified carbon nanotube, additional amount is 15 parts, it may be assumed that takes 100 parts of fourths
Benzene latex SBR1500 (dry glue) and 2 parts of neopelexes, 150 parts of deionized waters are added in condensing field and are stirred
Then 15 parts of carbon nanotubes are added in 15min, be 10 with sodium hydroxide regulation system pH value, when being warming up to 45 DEG C, be stirred
Then 35min is added 4 parts of hydrochloric acid and is condensed, last washed, dehydration, dry, briquetting are made tyre surface and are combined with butadiene-styrene rubber
Object.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Comparative example 3
(1) preparation of distributed carbon nanotube:
The preparation of a carbon nanotube hydroxyl: with embodiment 3.
The preparation of c dispersing type carbon nanotube: other conditions are same as Example 3, the difference is that in preparation process not
Grafting styrene-butadiene latex b is added, but is directly added into styrene-butadiene latex SBR1500, additional amount is 4 parts, it may be assumed that takes 100 parts of carbon nanometers
Pipe b and 2.5 parts of lauric acid glycol esters, 400 parts of deionized waters, 3.5 parts of sodium hydroxides are added in polymeric kettle and are stirred
25min；Then 3.0 parts of neopelexes, 4.0 parts of styrene-butadiene latex SBR1500 are added, stirring is warming up to 65 DEG C, stirring
After reacting 3.5hr, distributed carbon nanotube a is made in washed, dehydration, dry, grinding.
(2) preparation of tyre surface butadiene-styrene rubber composition: other conditions are same as Example 3, the difference is that preparation
It is added without distributed carbon nanotube in the process, but is directly added into distributed carbon nanotube a, additional amount is 20 parts, it may be assumed that is taken
100 parts of styrene-butadiene latex SBR1500 (dry glue) and 3 parts of neopelexes, 150 parts of deionized waters are added in condensing field and stir
Mixing 15min is mixed, 20 parts of distributed carbon nanotube a are then added, is 10 with sodium hydroxide regulation system pH value, is warming up to 45 DEG C
When, it is stirred 40min, 5 parts of hydrochloric acid are then added and are condensed, last washed, dehydration, dry, briquetting are made tyre surface and use
Butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Comparative example 4
(1) preparation of distributed carbon nanotube:
The preparation of b grafting styrene-butadiene latex: with embodiment 3.
The preparation of c dispersing type carbon nanotube: other conditions are same as Example 4, the difference is that in preparation process not
Carbon nanotube b is added, but directly uses not hydroxylated carbon nanotube, it may be assumed that takes 100 parts of not hydroxylated carbon nanotubes and 3.0
Part lauric acid glycol ester, 400 parts of deionized waters, 4.0 parts of sodium hydroxides are added in polymeric kettle and are stirred 28min；Then
3.5 parts of neopelexes, 5.0 parts of grafting styrene-butadiene latex b are added, stirring is warming up to 65 DEG C, after being stirred to react 3.8hr,
Distributed carbon nanotube b is made in washed, dehydration, dry, grinding.
(2) preparation of tyre surface butadiene-styrene rubber composition: other conditions are same as Example 4, the difference is that preparation
It is added without distributed carbon nanotube in the process, but is directly added into distributed carbon nanotube b, additional amount is 25 parts, it may be assumed that is taken
100 parts of styrene-butadiene latex SBR1500 (dry glue) and 3.5 parts of neopelexes, 200 parts of deionized waters are added in condensing field
It is stirred 20min, 25 parts of distributed carbon nanotube b are then added, is 10 with sodium hydroxide regulation system pH value, is warming up to 50
DEG C when, be stirred 45min, 5.5 parts of hydrochloric acid be then added and are condensed, tire is made in last washed, dehydration, dry, briquetting
Face butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Comparative example 5
(1) preparation of distributed carbon nanotube:
The preparation of a carbon nanotube hydroxyl: with embodiment 5.
The preparation of b grafting styrene-butadiene latex: with embodiment 5.
The preparation of c dispersing type carbon nanotube: other conditions are same as Example 5, the difference is that in preparation process not
Lauric acid butanediol ester is added, it may be assumed that 100 parts of carbon nanotube c and 480 parts of deionized waters, 5.5 parts of sodium hydroxides is taken to be added to polymerization
25min is stirred in kettle；Then 4.3 parts of neopelexes, 8.5 parts of grafting styrene-butadiene latex c are added, stirring is warming up to
65 DEG C, after being stirred to react 4.0hr, distributed carbon nanotube c is made in washed, dehydration, dry, grinding.
(2) preparation of tyre surface butadiene-styrene rubber composition: other conditions are same as Example 5, the difference is that preparation
It is added without distributed carbon nanotube in the process, but is directly added into distributed carbon nanotube c, additional amount is 30 parts, it may be assumed that is taken
100 parts of styrene-butadiene latex SBR1712 (dry glue) and 4.0 parts of neopelexes, 270 parts of deionized waters are added in condensing field
It is stirred 25min, 30 parts of distributed carbon nanotube c are then added, is 11 with sodium hydroxide regulation system pH value, is warming up to 55
DEG C when, be stirred 50min, 6.0 parts of sulfuric acid be then added and are condensed, tire is made in last washed, dehydration, dry, briquetting
Face butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Comparative example 6
(1) preparation of distributed carbon nanotube:
The preparation of a carbon nanotube hydroxyl: with embodiment 5.
The preparation of b grafting styrene-butadiene latex: other conditions are same as Example 5, the difference is that methyl in preparation process
The additional amount of acrylic acid is 20 parts, it may be assumed that is firstly added 300 parts of deionized waters in polymeric kettle and then sequentially adds 100 parts of butylbenzene
Latex SBR1712,9.5 parts of neopelexes, 0.45 part of tert-dodecyl mercaptan after being replaced with nitrogen, are added 9.5 parts
Methacrylic acid, stirring, heating, 0.25 part of ammonium persulfate is added when reaching 45 DEG C in kettle temperature degree to be polymerized, after reacting 8hr, is added
Grafting styrene-butadiene latex c-1 (2.5 ﹪ of grafting rate of styrene-butadiene latex) is made in 0.4 part of Sodium Dimethyldithiocarbamate.
The preparation of c dispersing type carbon nanotube: other conditions are same as Example 6, the difference is that in preparation process not
Grafting styrene-butadiene latex c is added, but 2.5 ﹪ of grafting rate is added and is grafted styrene-butadiene latex c-1, it may be assumed that takes 100 parts of carbon nanotube c and 5.0
Part lauric acid butanediol ester, 500 parts of deionized waters, 6.0 parts of sodium hydroxides are added in polymeric kettle and are stirred 30min；Then
5.0 parts of neopelexes, 10 parts of grafting styrene-butadiene latex c-1 are added, stirring is warming up to 70 DEG C, after being stirred to react 5.0hr,
Distributed carbon nanotube d is made in washed, dehydration, dry, grinding.
(2) preparation of tyre surface butadiene-styrene rubber composition: other conditions are same as Example 6, the difference is that preparation
It is added without distributed carbon nanotube in the process, but is directly added into distributed carbon nanotube d, additional amount is 40 parts, it may be assumed that is taken
100 parts of styrene-butadiene latex SBR1712 (dry glue) and 5.0 parts of neopelexes, 300 parts of deionized waters are added in condensing field
It is stirred 30min, 40 parts of distributed carbon nanotube d are then added, is 12 with sodium hydroxide regulation system pH value, is warming up to 60
DEG C when, be stirred 60min, 7.0 parts of sulfuric acid be then added and are condensed, tire is made in last washed, dehydration, dry, briquetting
Face butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
The performance of table 1 tire tread butadiene-styrene rubber composition
Attached drawing 1 is the infrared spectrum spectrogram of carbon nanotube (a) and high dispersive type carbon nanotube (b).As can be seen from the figure:
The FTIR spectrogram of sample b is 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 spectrogram of sample a occurs without absorption peak here.Illustrate unsaturated carboxylic acid polar monomer
It is successfully coated on carbon nano tube particle surface with the graft of styrene-butadiene latex.
As shown in Table 1: 0 DEG C of tan δ of embodiment is higher than comparative example, illustrates that prepare wet-sliding resistant performance good for tire；Implement
The 60 DEG C of tan δ and wear volume of example are lower than comparative example, illustrate that the rolling resistance for tire preparation is low, wearability is good.
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 modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (14)
1. a kind of preparation method of the rubber composition of filling carbon nano-pipe, which comprises the following steps:
(1) preparation of distributed carbon nanotube:
A. the preparation of carbon nanotube hydroxyl: based on the mass percent of carbon nanotube, by 100 parts of carbon nanotubes and 150~200
Part concentrated nitric acid, 50~100 parts of concentrated sulfuric acids, 10~50 parts of potassium permanganate are put into togerther in reactor and mix, super with 50~100kHz
1~2hr of sonicated is then heated at 50~150 DEG C, and stirring acid boils 1~10hr, cooling, filter, wash to filtrate and be in
Property, 200~500 parts of polyalcohols are eventually adding, are heated at 50~90 DEG C, 1~5hr is stirred to react, are filtered, washing, drying,
Obtain the carbon nanotube that surface has hydroxyl；
B. it is grafted the preparation of styrene-butadiene latex: being to be firstly added 100~300 parts in polymeric kettle in terms of 100 parts by styrene-butadiene latex quality
Then deionized water sequentially adds 100 parts of styrene-butadiene latexes, 1~10 part of emulsifier, 0.05~0.5 part of molecular weight regulator, use nitrogen
After gas displacement, 1~10 part of unsaturated carboxylic acid polar monomer, stirring, heating, when kettle temperature degree to be polymerized reaches 30~50 DEG C is added
0.05~0.3 part of initiator is added, after reacting 3~8h, 0.1~0.5 part of terminator is added, graft latex is made；
C. based on the mass percent of hydroxyl carbon nano tube, 100 parts of hydroxylating carbon nanometers the preparation of distributed carbon nanotube: are taken
Pipe and 1.0~5.0 parts of surfactants, 300~500 parts of deionized waters, 1~6 part of buffer are added to stir in polymeric kettle and mix
Close 10~30min；Then 1~5 part of emulsifier, 1~10 part of graft latex is added, stirring is warming up to 50~70 DEG C, is stirred to react 1
After~5hr, distributed carbon nanotube is made in washed, dehydration, dry, grinding；
(2) preparation of butadiene-styrene rubber composition: being to take 100 parts of styrene-butadiene latex dry glues in terms of 100 parts by the quality of styrene-butadiene latex dry glue
Be added in condensing field with 1~5 part of emulsifier, 100~300 parts of deionized waters and be stirred 10~30min, then be added 10~
40 parts of distributed carbon nanotubes are 9~12, when being warming up to 40~60 DEG C with buffer regulation system pH value, it is stirred 30~
Then 60min is added 3~7 parts of flocculating agents and is condensed, butadiene-styrene rubber combination is made in last washed, dehydration, dry, briquetting
Object.
2. the method as described in claim 1, it is characterised in that the carbon nanotube is nanoscale, partial size are as follows: 0.3~
30nm。
3. the method as described in claim 1, it is characterised in that the polyalcohol is selected from ethylene glycol, propylene glycol, glycerine, fourth two
The mixture of one or more of alcohol, pentaerythrite.
4. the method as described in claim 1, it is characterised in that the unsaturated carboxylic acid polar monomer is selected from acrylic acid, methyl-prop
One of olefin(e) acid, 2- ethylacrylic acid.
5. method as claimed in claim 4, it is characterised in that the unsaturated carboxylic acid polar monomer is acrylic acid.
6. the method as described in claim 1, it is characterised in that the surfactant is selected from lauric acid glycol ester, lauric acid
The mixing of one or more of propylene glycol ester, lauric acid glycerine ester, lauric acid butanediol ester, lauric acid pentaerythritol ester
Object.
7. the method as described in claim 1, it is characterised in that the initiator is water-soluble thermal initiator, is selected from persulfuric acid
Bis- (the 2- amidine oxazoline propane) hydrochlorides of ammonium, potassium peroxydisulfate, sodium peroxydisulfate, 2,2- azo, 2,2- azo [2- (2- imidazoline -2-
One of base) propane] dihydrochloride.
8. the method for claim 7, it is characterised in that the initiator is ammonium persulfate.
9. the method for claim 7, it is characterised in that the additional amount of the initiator is 0.07~0.2 part.
10. the method as described in claim 1, it is characterised in that the styrene-butadiene latex is by conjugated diene hydrocarbon compound and aryl
Ethylene compounds are copolymerized by emulsion polymerization.
11. method as claimed in claim 10, it is characterised in that the conjugated diene hydrocarbon compound is C4Class conjugated diene hydrocarbonylation
Close object.
12. method as claimed in claim 10, it is characterised in that the aryl ethylene class compound is selected from styrene, Alpha-Methyl
One of styrene, 2- propenyl benzene, ethyl styrene and their derivative.
13. the method as described in claim 1, it is characterised in that the solid content 20~45% of the styrene-butadiene latex, in conjunction with benzene second
Alkene content 15~25%, 50~200nm of latex particle size.
14. the method as described in claim 1, it is characterised in that the preparation of the rubber composition carries out in condensing field.
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| CN115850886A (en) * | 2022-11-30 | 2023-03-28 | 上海熹贾精密技术有限公司 | High-performance fluororubber compound and application thereof |
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