CN107266714B - A kind of method of modifying of Nano carbon white - Google Patents
A kind of method of modifying of Nano carbon white Download PDFInfo
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- CN107266714B CN107266714B CN201610217665.7A CN201610217665A CN107266714B CN 107266714 B CN107266714 B CN 107266714B CN 201610217665 A CN201610217665 A CN 201610217665A CN 107266714 B CN107266714 B CN 107266714B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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Abstract
The present invention provides the method for modifying that a kind of high dispersive type is used as the Nano carbon white of gum filler.The invention is compounded using unsaturated carboxylic acid polar monomer and acrylamide polar monomer, is being carried out pre-emulsification processing to conjugated diene monomer, is being prepared high dispersive type Nano carbon white using situ aggregation method.This method not only solves the problem easy to reunite of Nano carbon white, imparts the ultra-dispersed property of Nano carbon white, but also has prevented the problem of should storing and reuniting for a long time again, ensure that the stability stored for a long time.The features such as monomer dosage of the present invention is few, and environmental pollution is small, and operating method is simple, is suitble to industrialized production.
Description
Technical field
The present invention relates to the preparation methods that a kind of improved compound rubber filler nanometer white carbon black reaches ultra-dispersed property.
Background technique
It is well known that from the point of view of the inorganic powder filling-modified desired effect for closing rubber, the partial size ruler of inorganic particle particle
The effect of very little smaller modification is also better, but a technology is inevitably encountered in the application process of ultrafine inorganic powder
The reduction of problem, i.e. superfine powder with partial size, specific surface area increase, surface can improve, and autohemagglutination ability is stronger, is more difficult to by rubber
Material is mixed into, infiltrates and disperses.Therefore the dispersion of the ultrafine inorganic powder in rubber, it has also become prepare high-performance rubber material
The bottleneck of material.
Nano carbon white is porous material, and composition can use SiO2·nH2O indicates, wherein nH2O is with surface hydroxyl
Form exists, and is a kind of white, nontoxic, amorphous, porous attritive powder, has internal surface area big, dispersible, light, resistance to
High temperature does not burn, the characteristics such as electrical insulating property is good, and chemical property is stablized.White carbon black as a kind of environmental protection, the auxiliary agent that has excellent performance,
It is mainly used for the fields such as rubber product.Nano carbon white partial size is small, specific surface is big, surface energy is high, surface has a large amount of hydroxyl again
Base causes Nano carbon white easily to be reunited, and is not easy to be uniformly dispersed in the mixed process with rubber material, not only will affect in this way
Filling-modified effect, but also the performance of rubber material can be damaged.
In the prior art using common are coupling agent or surfactant-modified, silane coupling agent, toluene isocyanide are utilized
Acid esters, inorganic mineral, oligomer dialogue are carbon black modified (such as: CN101798473A, CN101817529A, CN101704967A
Deng)；There are also graft polymers modification and inorganic material surface coating modifications, such as: Che Jianfei et al. is using paraformaldehyde and a contracting
Diethylene glycol condensation polymerization prepares polyacetals oligomer, using Toluene-2,4-diisocyanate, after 4- diisocyanate activates silica surface
Grafted polyacetal oligomer (South China Science & Engineering University journal 2005,29,33-333).Huang Zhongbing et al. methacryl (3- tri-
Methoxy silane) propyl ester is to silica surface modified, then is aggregated in improved silica surface by no soap lye and coats polyphenyl
Pvdf layer (macromolecule journal 2004,6,835-835).Although the above method improves the dispersibility of Nano carbon white particle, increase
The strong compatibility with rubber matrix, but there are still certain limitations for these methods, it is modified and inorganic using graft polymers
The disadvantages of when material surface coating modification Nano carbon white, it is longer that there are reaction time consumptions, and energy consumption is higher, complicated for operation；And it utilizes
When coupling agent or surfactant-modified Nano carbon white, there is also dosage is big and high production cost, dispersion stabilization difference and easily
Again the disadvantages of reuniting.
Summary of the invention
It is an object of that present invention to provide the method for modifying that a kind of ultra-dispersed type is used as the Nano carbon white of gum filler.The hair
It is bright to be compounded using unsaturated carboxylic acid polar monomer and acrylamide polar monomer, conjugated diene monomer is carried out at pre-emulsification
Reason, prepares modified Nano white carbon black using situ aggregation method.This method not only solves the problem easy to reunite of Nano carbon white,
The ultra-dispersed property of Nano carbon white is imparted, but also has prevented the problem of should storing and reuniting for a long time again, ensure that
The stability stored for a long time.
" part " of the present invention each means mass parts.
A kind of method of modifying of Nano carbon white being used as gum filler of the present invention, specific preparation step are as follows:
(1) monomer pre-emulsion prepare: in parts by mass, by 100 parts of conjugated diene monomers, 5~10 parts of emulsifiers,
150~200 parts of deionized waters, 1.0~2.0 parts of buffers, 0.01~0.1 part of initiator are put into togerther in reactor, are warming up to
At 40~60 DEG C, it is stirred to react 30~50 minutes and is prepared into monomer pre-emulsion.
(2) it compounds the preparation of polar monomer mixed liquor: in parts by mass, taking 100 parts of unsaturated carboxylic acid polar monomers and 20
~50 parts of acrylamides are put into reaction kettle and are stirred 5~10min；Again plus 50~100 parts of deionized waters, 1~3 part of buffer
The pH for adjusting solution is 7.0~9.0, preferably 7.5~8.5, is stirred for 10~30min of mixing composition compounding polar monomer mixing
Liquid.
(3) preparation of high dispersive type Nano carbon white: in parts by mass, take 100 parts of Nano carbon whites and 10~30 parts multiple
Be added in polymeric kettle with polarity monomer mixed solution, 200~300 parts of deionized waters, 1~4 part of buffer and be stirred 10~
30min；1~5 part of emulsifier, 1~5 part of monomer pre-emulsion is then added, stirring is warming up to 50~70 DEG C, is stirred for mixing 10
~30min generates the condensate coated centered on Nano carbon white powder by compounding polar monomer and conjugated diene monomer,
And using this as the seed of multiple emulsion；30~60 parts of monomer pre-emulsions and 0.05~0.2 part of initiator are finally added, instead
After answering 3.0~6.0h, 0.1~0.5 part of terminator is added, modified Nano white carbon black is made in washed, dehydration, dry, grinding.
White carbon black of the present invention is nanoscale, partial size are as follows: 20~60nm.
Polar monomer acrylamide of the present invention, purity >=99%.
Unsaturated carboxylic acid polar monomer of the present invention is selected from acrylic acid (AA), methacrylic acid (MAA), maleic anhydride
One of (MAH), preferred acrylic acid (AA).
Conjugated diene of the present invention is C4~Cl2Conjugated diene is selected from 1,3-butadiene；Isoprene；2,3-
Dimethyl -1,3 butadiene；2,3- diethyl -1,3 butadiene；2- methyl -3- ethyl -1,3 butadiene；Chloro- 1, the 3- penta 2 of 2-
Alkene；1,3-pentadiene；3- butyl -1,3- octadiene；2- phenyl -1,3-butadiene；One or more of 1,3- hexadiene
Mixture, preferably isoprene.
Initiator of the present invention is water-soluble thermal initiator, in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate
One or more of mixtures, initiator system of ammonium persulfate.
The present invention can use conven-tional adjuvants generally in the art to used emulsifier, buffer, terminator etc.,
Its additional amount is also the conventional amount used that those skilled in the art can be calculated according to the dosage of latex, and it is special that the present invention is not done
It limits.Emulsifier as described in 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: fatty acid soaps, RA rosin acid, neopelex, dodecyl sulphate can be selected from
The mixture of one or more of sodium, polyoxyethylene sorbitol acid anhydride list olein, preferably neopelex.
Buffer of the present invention can be in sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonium hydroxide, ammonium hydrogen carbonate
One kind, preferably sodium hydroxide.
Terminator of the present invention can be selected from one or more of diethyl hydroxylamine, hydroxyl sulfate, Sodium Dimethyldithiocarbamate
Mixture.
The method of modifying of a kind of super-dispersed nano white carbon black of the present invention, with unsaturated carboxylic acid and acrylamide polarity
Monomer is compounded, the hydroxyl on carboxyl and amide groups and white carbon black surface under the conditions of weak alkaline aqueous solution, in polar monomer
Base is linked together by " hydrogen bond action ", and the form for reaching multi-point-anchoring is adsorbed in white carbon black surface.Then pass through conjugation two
Olefinic monomer is copolymerized with polar monomer is compounded, and is formd in nanoparticle surface with two kinds of anchoring group carboxyls and acyl
Amido is back and conjugated diene polymer is a kind of ultra-dispersed structure of tail (see attached drawing 1).Since the bond energy of hydrogen bond is lower,
The hydrogen bond of single-point anchoring is difficult to ensure enough adsorption strengths, is easily detached from blending and storage, so that white carbon black is again
Reunite.Therefore consider that this point enhances dialogue carbon blacksurface first by multi-point-anchoring when designing ultra-dispersed molecular structure
Adsorption strength, prevent its disengaging.Secondly because multi-point-anchoring increases the space density of solvent chain conjugated diene, make score
Subspace steric effect becomes larger, and stable space bit resistance layer can be established between nanoparticle, hinders the mutual group between particle
It is poly-, it can be realized and exist long-term and stably with single particle shape.Present invention efficiently solves the easy of Nano carbon white
Agglomeration traits, while in turn ensuring the dispersion stabilization of Nano carbon white, achieve the purpose that store for a long time.Also, this hair
The features such as bright also to have monomer dosage few, environmental pollution is small, and operating method is simple, is suitble to industrialized production.
Detailed description of the invention
Fig. 1 is the ultra-dispersed structure chart of Nano carbon white particle surface.1 indicates using conjugated diene polymer as tail in figure
Solvent chain, 2 indicate using carboxyl and amide groups as the anchoring group of anchor point, 3 indicate hard charcoal black track producing particles.
Fig. 2 is the infrared spectrum spectrogram of white carbon black (a) and modified white carbon black (b).It is 1099cm in wave number on a-1Locate
The asymmetric stretching vibration absorption peak of existing Si-O-Si is 804cm in wave number-1The symmetrical stretching vibration that Si-O-Si occurs in place absorbs
Peak is 465cm in wave number-1There is the bending vibration absorption peak of Si-O-Si in place.On b, wave number 1715-1705cm-1Locate
The sharp absorption peak of carbonyl is showed.Wave number is 3400~3250cm-1There is the sharp absorption peak of amide groups.It can be seen that conjugated diene
The polymer that hydrocarbon and unsaturated carboxylic acid and acrylamide polar monomer generate successfully is deposited on Nano carbon white particle surface.
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:
(2) analysis test method:
Sample infrared spectrum analysis: modified to Nano carbon white using Germany's Bruke spectral instrument company's infrared spectrometer
Front and back sample carries out functional group analysis.Sample is dried at 100 DEG C in vacuum drying oven, using pressing potassium bromide troche, acquires wave number
Range 400-4000cm-1。
The measuring method of settling volume: the tool plug graduated cylinder that 10g modified Nano white carbon black is placed in graduated 100mL is weighed
It is interior, it is added a certain amount of dispersing agent (atoleine), Nano carbon white to be modified adds liquid by after atoleine complete wetting
Body paraffin sufficiently vibrates 5min with the frequency of oscillation of 30 times/1min, makes modified Nano white carbon black in liquid to the scale of 100mL
It is uniformly dispersed, is then allowed to stand in paraffin, 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, Yi Xiangrong.
The measuring method of oil absorption: it referring to " measuring method of YS/T618-2007 aluminium hydroxide used as filling material oil absorption ", takes
Quantitative modified Nano white carbon black 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 sample institute oil suction with toolsetting0
(mL) it indicates, is calculated as follows:
In formula, υ is the O-phthalic of consumption
The volume (mL) of sour di-isooctyl；M is the quality (g) of sample.Oil absorption reflects modification to a certain extent and receives
The specific surface area of off-white carbon black, specific surface area is lower, and oil absorption is lower, and wettability is better, and vice versa.
Embodiment 1
(1) preparation of monomer pre-emulsion: by 100 parts of isoprene, 5 parts of neopelexes, 150 parts of deionizations
Water, 1.0 parts of sodium hydroxides, 0.01 part of ammonium persulfate are put into togerther in reactor, when being warming up to 40 DEG C, are stirred to react 40 minutes and are made
For at isoprene pre-emulsion a.
(2) it compounds the preparation of polar monomer mixed liquor: 100 parts of acrylic acid (AA) and 20 parts of acrylamides is put into reaction kettle
In be stirred 5min, then plus 50 parts of deionized waters, 1.0 parts of sodium hydroxides, be stirred for mixing 10min, composition compounding polarity list
Body mixed liquor a.(pH=7.6 of mixed liquor a)
(3) preparation of modified Nano white carbon black: take 100 parts of Nano carbon whites (40nm) and 10 parts of polar monomer mixed liquor a,
200 parts of deionized waters, 1.0 parts of sodium hydroxides are added in polymeric kettle and are stirred 20min；Then 1 part of detergent alkylate is added
Sodium sulfonate, 1.0 parts of isoprene pre-emulsion a, stirring are warming up to 50 DEG C, are stirred for mixing 10min and generate with Nano carbon white
The seed of multiple emulsion centered on powder；Then 35 parts of isoprene pre-emulsion a and 0.05 part of ammonium persulfate are added, instead
After answering 4.0h, it is eventually adding 0.1 part of diethyl hydroxylamine, modified Nano white carbon black is made in washed, dehydration, dry, grinding.Sampling
Analysis: standard sample is made, performance is shown in Table 1 after tested.
Embodiment 2
(1) preparation of monomer pre-emulsion: with embodiment 1.
(2) preparation of polar monomer mixed liquor is compounded: with embodiment 1.
(3) preparation of modified Nano white carbon black: take 100 parts of Nano carbon whites (40nm) and 15 parts of polar monomer mixed liquor a,
270 parts of deionized waters, 1.7 parts of sodium hydroxides are added in polymeric kettle and are stirred 20min；Then 2 parts of detergent alkylates are added
Sodium sulfonate, 2.0 parts of isoprene pre-emulsion a, stirring are warming up to 65 DEG C, are stirred for mixing 25min and generate with Nano carbon white
The seed of multiple emulsion centered on powder；Then 40 parts of isoprene pre-emulsion a and 0.09 part of ammonium persulfate are added, instead
After answering 4.0h, it is eventually adding 0.2 part of diethyl hydroxylamine, modified Nano white carbon black is made in washed, dehydration, dry, grinding.Sampling
Analysis: standard sample is made, performance is shown in Table 1 after tested.
Embodiment 3
(1) preparation of monomer pre-emulsion: with embodiment 1.
(2) preparation of polar monomer mixed liquor is compounded: with embodiment 1.
(3) preparation of modified Nano white carbon black: take 100 parts of Nano carbon whites (40nm) and 18 parts of polar monomer mixed liquor a,
270 parts of deionized waters, 1.9 parts of sodium hydroxides are added in polymeric kettle and are stirred 20min；Then 2 parts of detergent alkylates are added
Sodium sulfonate, 2.5 parts of isoprene pre-emulsion a, stirring are warming up to 65 DEG C, are stirred for mixing 25min and generate with Nano carbon white
The seed of multiple emulsion centered on powder；Then 43 parts of isoprene pre-emulsion a and 0.09 part of ammonium persulfate are added, instead
After answering 4.0h, it is eventually adding 0.2 part of diethyl hydroxylamine, modified Nano white carbon black is made in washed, dehydration, dry, grinding.Sampling
Analysis: standard sample is made, performance is shown in Table 1 after tested.
Embodiment 4
(1) preparation of monomer pre-emulsion: by 100 parts of isoprene, 7 parts of neopelexes, 170 parts of deionizations
Water, 1.4 parts of sodium hydroxides, 0.03 part of ammonium persulfate are put into togerther in reactor, when being warming up to 45 DEG C, are stirred to react 40 minutes and are made
For at isoprene pre-emulsion b.
(2) it compounds the preparation of polar monomer mixed liquor: 100 parts of acrylic acid (AA) and 35 parts of acrylamides is put into reaction kettle
In be stirred 8min, then plus 70 parts of deionized waters, 1.2 parts of sodium hydroxides, be stirred for mixing 20min, composition compounding polarity list
Body mixed liquor b.(pH=7.9 of mixed liquor b)
(3) preparation of modified Nano white carbon black: take 100 parts of Nano carbon whites (40nm) and 20 parts of polar monomer mixed liquor b,
260 parts of deionized waters, 1.6 parts of sodium hydroxides are added in polymeric kettle and are stirred 20min；Then 2.2 parts of dodecyls are added
Benzene sulfonic acid sodium salt, 2.5 parts of isoprene pre-emulsion b, stirring are warming up to 65 DEG C, are stirred for mixing 25min and generate with nanometer hard charcoal
The seed of multiple emulsion centered on black powder；Then 45 parts of isoprene pre-emulsion b and 0.1 part of ammonium persulfate are added,
After reacting 4.0h, it is eventually adding 0.25 part of diethyl hydroxylamine, modified Nano white carbon black is made in washed, dehydration, dry, grinding.
Sampling analysis: standard sample is made, performance is shown in Table 1 after tested.
Embodiment 5
(1) preparation of monomer pre-emulsion: with embodiment 4.
(2) preparation of polar monomer mixed liquor is compounded: with embodiment 4.
(3) preparation of modified Nano white carbon black: take 100 parts of Nano carbon whites (40nm) and 22 parts of polar monomer mixed liquor b,
270 parts of deionized waters, 1.7 parts of sodium hydroxides are added in polymeric kettle and are stirred 20min；Then 2.2 parts of dodecyls are added
Benzene sulfonic acid sodium salt, 3.0 parts of isoprene pre-emulsion b, stirring are warming up to 65 DEG C, are stirred for mixing 25min and generate with nanometer hard charcoal
The seed of multiple emulsion centered on black powder；Then 48 parts of isoprene pre-emulsion b and 0.1 part of ammonium persulfate are added,
After reacting 4.0h, it is eventually adding 0.25 part of diethyl hydroxylamine, modified Nano white carbon black is made in washed, dehydration, dry, grinding.
Sampling analysis: standard sample is made, performance is shown in Table 1 after tested.
Embodiment 6
(1) preparation of monomer pre-emulsion: with embodiment 4.
(2) preparation of polar monomer mixed liquor is compounded: with embodiment 4.
(3) preparation of modified Nano white carbon black: take 100 parts of Nano carbon whites (40nm) and 26 parts of polar monomer mixed liquor b,
270 parts of deionized waters, 1.8 parts of sodium hydroxides are added in polymeric kettle and are stirred 20min；Then 2.5 parts of dodecyls are added
Benzene sulfonic acid sodium salt, 4.0 parts of isoprene pre-emulsion b, stirring are warming up to 65 DEG C, are stirred for mixing 25min and generate with nanometer hard charcoal
The seed of multiple emulsion centered on black powder；Then 53 parts of isoprene pre-emulsion b and 0.1 part of ammonium persulfate are added,
After reacting 4.0h, it is eventually adding 0.27 part of diethyl hydroxylamine, modified Nano white carbon black is made in washed, dehydration, dry, grinding.
Sampling analysis: standard sample is made, performance is shown in Table 1 after tested.
Embodiment 7
(1) preparation of monomer pre-emulsion: 100 parts of 1,3- hexadienes, 10 parts of neopelexes, 200 parts are gone
Ionized water, 2.0 parts of sodium hydroxides, 0.1 part of ammonium persulfate are put into togerther in reactor, when being warming up to 60 DEG C, are stirred to react 50 points
Clock is prepared into 1,3- hexadiene pre-emulsion c.
(2) it compounds the preparation of polar monomer mixed liquor: 100 parts of maleic anhydrides (MAH) and 50 parts of acrylamides is put into instead
Answer and be stirred 10min in kettle, then plus 80 parts of deionized waters, 1.5 parts of sodium hydroxides, be stirred for mixing 30min, composition compounding pole
Property monomer mixed solution c.(pH=7.2 of mixed liquor b)
(3) preparation of modified Nano white carbon black: take 100 parts of Nano carbon whites (40nm) and 30 parts of polar monomer mixed liquor c,
300 parts of deionized waters, 3.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 30min；Then 5.0 parts of dodecyls are added
Benzene sulfonic acid sodium salt, 5.0 parts of 1,3- hexadiene pre-emulsion c, stirring are warming up to 65 DEG C, and it is white with nanometer to be stirred for mixing 25min generation
The seed of multiple emulsion centered on carbon black powder；Then 60 parts of 1,3- hexadiene pre-emulsion c and 0.2 part of persulfuric acid are added
Ammonium after reacting 6.0h, is eventually adding 0.5 part of diethyl hydroxylamine, and modified Nano hard charcoal is made in washed, dehydration, dry, grinding
It is black.Sampling analysis: standard sample is made, performance is shown in Table 1 after tested.
Comparative example 1
(1) preparation of monomer pre-emulsion: with embodiment 1.
(2) preparation of polar monomer mixed liquor is compounded: with embodiment 1.
(3) preparation of modified Nano white carbon black: other conditions are same as Example 1, the difference is that in preparation process
The additional amount of polar monomer mixed liquor a is 7 parts, it may be assumed that take 100 parts of Nano carbon whites (40nm) and 7 parts of polar monomer mixed liquor a,
200 parts of deionized waters, 1.0 parts of sodium hydroxides are added in polymeric kettle and are stirred 20min；Then 1 part of detergent alkylate is added
Sodium sulfonate, 1.0 parts of isoprene pre-emulsion a, stirring are warming up to 50 DEG C, are stirred for mixing 10min and generate with Nano carbon white
The seed of multiple emulsion centered on powder；Then 35 parts of isoprene pre-emulsion a and 0.05 part of ammonium persulfate are added, instead
After answering 4.0h, it is eventually adding 0.1 part of diethyl hydroxylamine, modified Nano white carbon black is made in washed, dehydration, dry, grinding.Sampling
Analysis: standard sample is made, performance is shown in Table 1 after tested.
Comparative example 2
(1) prepared by monomer pre-emulsion: with embodiment 1.
(2) preparation of polar monomer mixed liquor is compounded: with embodiment 1.
(3) preparation of modified Nano white carbon black: other conditions are same as Example 2, the difference is that in-situ polymerization mistake
The additional amount of isoprene pre-emulsion a is 20 parts in journey, it may be assumed that takes 100 parts of Nano carbon whites (40nm) and 15 parts of polar monomers
Mixed liquor a, 270 parts of deionized waters, 1.7 parts of sodium hydroxides are added in polymeric kettle and are stirred 20min；Then it is added 2 part ten
Dialkyl benzene sulfonic acids sodium, 2.0 parts of isoprene pre-emulsion a, stirring are warming up to 65 DEG C, are stirred for mixing 25min and generate to receive
The seed of multiple emulsion centered on rice white carbon black powder；Then 40 parts of isoprene pre-emulsion a and 0.09 part of mistake are added
Ammonium sulfate after reacting 4.0h, is eventually adding 0.2 part of diethyl hydroxylamine, washed, dehydration, dry, the obtained modified Nano of grinding is white
Carbon black.Sampling analysis: standard sample is made, performance is shown in Table 1 after tested.
Comparative example 3
(1) prepared by monomer pre-emulsion: with embodiment 1.
(2) preparation of modified Nano white carbon black: other conditions are same as Example 3, the difference is that in preparation process
Polar monomer mixed liquor a is not added, it may be assumed that 100 parts of Nano carbon whites (40nm), 270 parts of deionized waters, 1.9 parts of sodium hydroxides is taken to add
Enter and is stirred 20min into polymeric kettle；Then 2 parts of neopelexes, 2.5 parts of isoprene pre-emulsion a are added,
Stirring is warming up to 65 DEG C, is stirred for the seed that mixing 25min generates the multiple emulsion centered on Nano carbon white powder；Then
43 parts of isoprene pre-emulsion a and 0.09 part of ammonium persulfate are added, after reacting 4.0h, are eventually adding 0.2 part of diethyl hydroxyl
Modified Nano white carbon black is made in amine, washed, dehydration, dry, grinding.Sampling analysis: standard sample is made, performance is shown in after tested
Table 1.
Comparative example 4
(1) preparation of polar monomer mixed liquor is compounded: with embodiment 4.
(2) preparation of modified Nano white carbon black: other conditions are same as Example 4, the difference is that in-situ polymerization mistake
Isoprene pre-emulsion b is not added in journey, it may be assumed that take 100 parts of Nano carbon whites (40nm) and 20 parts of polar monomer mixed liquor b, 260
Part deionized water, 1.6 parts of sodium hydroxides are added in polymeric kettle and are stirred 20min；Then 2.2 parts of detergent alkylate sulphurs are added
Sour sodium, 2.5 parts of isoprene pre-emulsion b, stirring are warming up to 65 DEG C, are stirred for mixing 25min and generate with Nano carbon white powder
The seed of multiple emulsion centered on body；Then 0.1 part of ammonium persulfate is added, after reacting 4.0h, is eventually adding 0.25 part two
Modified Nano white carbon black is made in ethylhydroxyl amine, washed, dehydration, dry, grinding.Sampling analysis: standard sample is made, after tested
Performance is shown in Table 1.
Comparative example 5
(1) preparation of monomer pre-emulsion: with embodiment 4.
(2) preparation of polar monomer mixed liquor is compounded: with embodiment 4.
(3) preparation of modified Nano white carbon black: other conditions are same as Example 5, the difference is that in-situ polymerization mistake
Initiator is not added in journey and crosses ammonium persulfate, isoprene pre-emulsion b is that dialogue carbon black particle surface is coated, it may be assumed that is taken
100 parts of Nano carbon whites (40nm) and 22 parts of polar monomer mixed liquor b, 270 parts of deionized waters, 1.7 parts of sodium hydroxides are added to
20min is stirred in polymeric kettle；Then 2.2 parts of neopelexes, 3.0 parts of isoprene pre-emulsion b are added, stir
It mixes and is warming up to 65 DEG C, be stirred for the seed that mixing 25min generates the multiple emulsion centered on Nano carbon white powder；Then again
48 parts of isoprene pre-emulsion b are added, after reacting 4.0h, are eventually adding 0.25 part of diethyl hydroxylamine, washed, dehydration is done
Modified Nano white carbon black is made in dry, grinding.Sampling analysis: standard sample is made, performance is shown in Table 1 after tested.
Comparative example 6
(1) preparation of monomer pre-emulsion: with embodiment 4.
(2) preparation of modified Nano white carbon black: other conditions are same as Example 6, the difference is that in preparation process
Polar monomer mixed liquor b is not added, but is directly added into 26 parts of acrylic acid (AA), it may be assumed that takes 100 parts of Nano carbon whites (40nm) and 26
Part AA, 270 parts of deionized waters, 1.8 parts of sodium hydroxides are added in polymeric kettle and are stirred 20min；Then it is added 2.5 part 12
Sodium alkyl benzene sulfonate, 4.0 parts of isoprene pre-emulsion b, stirring are warming up to 65 DEG C, are stirred for mixing 25min and generate with nanometer
The seed of multiple emulsion centered on white carbon black powder；Then 53 parts of isoprene pre-emulsion b and 0.1 part of persulfuric acid are added
Ammonium after reacting 4.0h, is eventually adding 0.27 part of diethyl hydroxylamine, and modified Nano hard charcoal is made in washed, dehydration, dry, grinding
It is black.Sampling analysis: standard sample is made, performance is shown in Table 1 after tested.
Comparative example 7
(1) prepared by monomer pre-emulsion: with embodiment 7
(2) preparation of modified Nano white carbon black: other conditions are same as Example 7, the difference is that in preparation process
Polar monomer mixed liquor c is not added, but is directly added into 30 parts of acrylamides, it may be assumed that takes 100 parts of Nano carbon whites (40nm) and 30 parts
Acrylamide, 300 parts of deionized waters, 3.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 30min；Then 5.0 parts are added
Neopelex, 5.0 parts of 1,3- hexadiene pre-emulsion c, stirring are warming up to 65 DEG C, are stirred for mixing 25min and generate
The seed of multiple emulsion centered on Nano carbon white powder；Then 60 parts of 1,3- hexadiene pre-emulsion c and 0.2 are added
Part ammonium persulfate after reacting 6.0h, is eventually adding 0.5 part of diethyl hydroxylamine, and washed, dehydration, dry, the obtained modification of grinding are received
Off-white carbon black.Sampling analysis: standard sample is made, performance is shown in Table 1 after tested.
The settling volume and oil absorbency of 1 modified Nano white carbon black of table
As shown in Table 1: the settling volume of embodiment is bigger than comparative example under same time, and oil absorption is below comparison
Example, illustrates that modified effect of the invention is obvious.Secondly it can be seen that modified Nano white carbon black is placed six months from Examples 1 to 7
The settling volume (120min) and oil absorbency measured afterwards and the variation that do not place are little, illustrate that the dispersion of modified Nano white carbon black is steady
It is qualitative good, long-term storage can be reached.
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 (8)
1. a kind of method of modifying of Nano carbon white, it is characterised in that mainly comprise the steps that
(1) monomer pre-emulsion prepare: in parts by mass, by 100 parts of conjugated diene monomers, 5~10 parts of emulsifiers, 150~
200 parts of deionized waters, 1.0~2.0 parts of buffers, 0.01~0.1 part of initiator are put into togerther in reactor, are warming up to 40~60
DEG C when, be stirred to react 30~50 minutes and be prepared into monomer pre-emulsion；
(2) it compounds the preparation of polar monomer mixed liquor: in parts by mass, taking 100 parts of unsaturated carboxylic acid polar monomers and 20~50
Part acrylamide, which is put into reaction kettle, is stirred 5~10min；Again plus 50~100 parts of deionized waters, 1~3 part of buffer are adjusted
The pH of solution is 7.0~9.0, is stirred for 10~30min of mixing composition compounding polar monomer mixed liquor；
(3) preparation of modified Nano white carbon black: mass parts meter takes 100 parts of Nano carbon whites and 5~25 parts of compounding polar monomers mixed
Liquid, 200~300 parts of deionized waters, 1~4 part of buffer is closed to be added in polymeric kettle and be stirred 10~30min；Then it is added 1
~5 parts of emulsifiers, 1~5 part of monomer pre-emulsion, stirring are warming up to 50~70 DEG C, are stirred for 10~30min of mixing and generate to receive
The condensate coated centered on rice white carbon black powder by compounding polar monomer and conjugated diene monomer, and using this as Composite Milk
The seed of liquid；10~30 parts of monomer pre-emulsions and 0.1~0.2 part of initiator are finally added, after reacting 3.0~6.0h, are added
Enter 0.1~0.5 part of terminator, modified Nano white carbon black is made in washed, dehydration, dry, grinding；
The conjugated diene monomer is C4~Cl2Conjugated diene, be selected from 1,3-butadiene；Isoprene；2,3- diformazans
Base -1,3- butadiene；2,3- diethyl -1,3- butadiene；2- methyl -3- ethyl -1,3-butadiene；Chloro- 1, the 3- penta 2 of 2-
Alkene；1,3-pentadiene；3- butyl -1,3- octadiene；2- phenyl -1,3-butadiene；One or more of 1,3- hexadiene
Mixture.
2. the method for modifying of Nano carbon white as described in claim 1, it is characterised in that the white carbon black is nanoscale, grain
Diameter are as follows: 20~60nm.
3. the method for modifying of Nano carbon white as described in claim 1, it is characterised in that the purity of the acrylamide be greater than or
Equal to 99%.
4. the method for modifying of Nano carbon white as described in claims 1 to 3 is any, it is characterised in that the unsaturated carboxylic acid polarity
Monomer is selected from one of acrylic acid, methacrylic acid, maleic anhydride.
5. the method for modifying of Nano carbon white as claimed in claim 4, it is characterised in that the unsaturated carboxylic acid polar monomer is
Acrylic acid.
6. the method for modifying of Nano carbon white as described in claim 1, it is characterised in that the conjugated diene is isoamyl two
Alkene.
7. the method for modifying of the Nano carbon white as described in claims 1 to 3,5 or 6, it is characterised in that the initiator is water
Soluble thermal initiator, be selected from ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, 2, bis- (2-amidine oxazoline propane) hydrochlorides of 2-azos,
The mixture of one or more of 2,2- azo [2- (2- imidazoline -2- base) propane] dihydrochloride.
8. the method for modifying of Nano carbon white as claimed in claim 7, it is characterised in that the initiator is ammonium persulfate.
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