CN107266716A - The method of modifying of Nano carbon white - Google Patents
The method of modifying of Nano carbon white Download PDFInfo
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- CN107266716A CN107266716A CN201610218630.5A CN201610218630A CN107266716A CN 107266716 A CN107266716 A CN 107266716A CN 201610218630 A CN201610218630 A CN 201610218630A CN 107266716 A CN107266716 A CN 107266716A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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Abstract
The present invention provides a kind of method of modifying of polymolecularity gum filler Nano carbon white.The invention is modified using aliphatic diisocyanate to Nano carbon white, then add vinyl-based acid amides and carry out end capping reaction, then pre-emulsification processing is carried out to aryl ethylene class monomer again and occurs in-situ polymerization with the unsaturated bond in vinyl-based acid amides, a kind of barrier layer of the high high dispersive structure of bonding strength is thus formed in Nano carbon white particle surface, the preparation method of Nano carbon white particle can be separated under high temperature or high shear forces by reaching.This method not only solves the easy agglomeration traits of Nano carbon white, impart the ultra-dispersed property of Nano carbon white, but also prevent because processing the problem of reuniting once more in blending procedure, it is ensured that Nano carbon white particle can be evenly dispersed into rubbery system.The present invention has operating method simple, and modified cost is low, and environmental pollution is small, the advantages of being adapted to industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method as the ultra-dispersed modification of synthetic rubber filler nanometer white carbon.
Background technology
It is well known that from the point of view of the Expected Results of inorganic powder filling-modified conjunction rubber, the particle diameter chi of inorganic particle particle
The effect of very little smaller modification is also better, but a technology is inevitably run into the application process of ultrafine inorganic powder
Problem, i.e. superfine powder can be improved with the reduction of particle diameter, specific surface area increase, surface, and autohemagglutination ability is stronger, is more difficult to by rubber
Material is mixed into, infiltrates and disperseed.Therefore scattering problem 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 its composition can use SiO2·nH2O represents, wherein nH2O is with surface hydroxyl
Form is present, and is a kind of white, nontoxic, amorphous, porous attritive powder, with internal surface area is big, dispersible, light weight, resistance to
High temperature, do not burn, the characteristic such as electrical insulating property is good, chemical property is stable.White carbon as it is a kind of environmental protection, excellent performance auxiliary agent,
It is mainly used in the fields such as rubber.Nano carbon white particle diameter is small, bigger than surface, the surface high, surface of energy has substantial amounts of hydroxyl again
Base, causes Nano carbon white easily to be reunited, and is difficult to be uniformly dispersed in the mixed process with elastomeric material, so can not only influence
Filling-modified effect, but also the performance of elastomeric material can be damaged.
In the prior art using common are coupling agent or surfactant-modified, silane coupler, toluene isocyanide are utilized
Acid esters, inorganic mineral, oligomer dialogue are carbon black modified (such as：CN101798473A、CN101817529A、CN101704967A
Deng)；Also graft polymers is modified and inorganic material surface coating modification, 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).Yellow loyalty soldier et al. uses methacryl (3- tri-
Methoxy silane) propyl ester is to silica surface modified, then by being aggregated in improved silica Surface coating polyphenyl without soap lye
Pvdf layer (macromolecule journal 2004,6,835-835).Although the above method improves the dispersiveness of Nano carbon white particle, increases
The strong compatibility with rubber matrix, but these methods still suffer from certain limitation, are modified using graft polymers and inorganic
During material surface coating modification Nano carbon white, there is that reaction time consumption is longer, energy consumption is higher, the shortcomings of complex operation；And utilize
When coupling agent or surfactant-modified Nano carbon white, there is also consumption is big and production cost is high, dispersion stabilization difference and easy
Again the shortcomings of reuniting.
The content of the invention
Present invention aims at provide a kind of method of modifying of ultra-dispersed property gum filler Nano carbon white.The invention is used
Aliphatic diisocyanate is modified to Nano carbon white, is then added vinyl-based acid amides and is carried out end capping reaction, Ran Houzai
Pre-emulsification processing is carried out to aryl ethylene class monomer and occurs in-situ polymerization with the unsaturated bond in vinyl-based acid amides, is thus existed
Nano carbon white particle surface forms a kind of barrier layer of the high ultra-dispersed structure of bonding strength, reaches in high temperature or high shear work
The preparation method of Nano carbon white particle can be separated with lower.The easy reunion that this method not only solves Nano carbon white is asked
Topic, imparts the ultra-dispersed property of Nano carbon white, but also prevents because processing the problem of reuniting once more in blending procedure,
It ensure that Nano carbon white particle can be evenly dispersed into rubbery system.
" part " of the present invention each means mass parts.
A kind of method of modifying of Nano carbon white as gum filler of the present invention, specific preparation process is：
(1) prepared by monomer pre-emulsion：In parts by mass, by 100 parts of aryl ethylene class monomers, 1~5 part of emulsifying agent, 100
~200 parts of deionized waters, 1.0~2.0 parts of buffers, 0.01~0.1 part of initiator are put into reactor together, it is warming up to 40~
At 60 DEG C, stirring reaction is prepared into monomer pre-emulsion in 30~60 minutes.
(2) preparation of ultra-dispersed type Nano carbon white：In parts by mass, 100 parts of Nano carbon whites and 150~300 parts are taken
Deionized water is added to 10~30min of stirring mixing in polymeric kettle；Then add 4~8 parts of aliphatic diisocyanates, 1.0~
2.0 parts of catalyst, are warming up to 40~50 DEG C, 1~2hr of stirring reaction, then add 2~5 parts of vinyl-based acid amides and 0.5~
Generated after 1.0 parts of 30~60min of catalyst reaction centered on Nano carbon white powder by aliphatic diisocyanate and ethene
The performed polymer that base class acid amides is coated；10~20 parts of monomer pre-emulsions and 0.3~1.0 part of initiator are finally added, are reacted
0.1~0.5 part of terminator is added after 5.0~8.0hr, ultra-dispersed type Nano carbon white is made in scrubbed, dehydration, dry, grinding.
White carbon of the present invention is nano level, and its particle diameter is：20~60nm.
It is different that aliphatic diisocyanate of the present invention is selected from hexamethylene diisocyanate (HDI), isophorone two
In cyanate (IPDI), dicyclohexyl methyl hydride -4,4'- diisocyanate (MDI), methylcyclohexane diisocyanate (HTDI)
At least one, preferably HTDI.
Vinyl-based acid amides of the present invention is selected from acrylamide, Methacrylamide, 1- crotonamides, methacryloyl
At least one of amine, 1- hexene acid amides, preferably Methacrylamide.
Aryl ethylene class compound of the present invention can be styrene, α-methylstyrene, 2- propenyl benzenes, ethylo benzene
One or more in ethene and their derivative, optimization styrene.
Initiator of the present invention is water-soluble thermal initiator：Ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, preferably mistake
Potassium sulfate.
Catalyst of the present invention can be in sodium carbonate, sodium acid carbonate, sodium hydroxide, ammoniacal liquor, ammonium hydrogen carbonate
One kind, preferably sodium hydroxide.
The present invention can use conven-tional adjuvants generally in the art to emulsifying agent, buffer, terminator for being used etc.,
Its addition is also that those skilled in the art can calculate obtained conventional amount used according to the consumption of latex, and the present invention does not do special
Limit.Emulsifying agent as described in the present invention is known to those skilled in the art, can be anion emulsifier and nonionic Emulsion
One or more in agent.Such as：Fatty acid soaps, RA rosin acid, neopelex, dodecyl sulphate can be selected from
One or more in sodium, polyoxyethylene sorbitol acid anhydride list olein, preferably neopelex.
Buffer of the present invention can be selected from one kind in sodium carbonate, sodium acid carbonate, ammonium hydrogen carbonate, preferably carbonic acid
Sodium.
Terminator of the present invention can be selected from the one or more in diethyl hydroxylamine, HAS, Sodium Dimethyldithiocarbamate.
The method of modifying of a kind of super-dispersed nano white carbon of the present invention, with the cyanic acid in aliphatic diisocyanate
Ester group (- NCO) is anchoring group, under the conditions of weak alkaline aqueous solution, and it is anti-to occur chemistry with the hydroxyl on white carbon particle surface
Carbamate should be generated, vinyl-based acid amides is subsequently added and end-blocking effect is played to cyanic acid ester group, prevent diisocyanate phase
Mutual self-priming and cause the adhesion of hard charcoal black track producing particle, be copolymerized next to that introducing unsaturated bond with aryl ethylene class monomer,
It is to carry on the back with vinylaromatic polymer as tail using anchoring group-NCO thus to be formed a kind of in Nano carbon white particle surface, and
Pass through " covalent bond " the close ultra-dispersed structure for connecting into an entirety (see accompanying drawing 1).Although aliphatic diisocyanate is with list
The form of point anchoring is adsorbed in white carbon surface, but this anchor point is realized by covalent bond, due to the key of covalent bond
Can be big, there are enough adsorption strengths, also be difficult to depart under high temperature and shear action.Next to that aryl ethylene class compound
Not only there is nonpolar feature, the effect not attracted each other as the chain structure of solvent chain, and contain benzene again simultaneously
Ring structure, molecule space steric effect is big.Therefore, can in rubber blending process under both mutually " synergy "
Can just set up firm space bit resistance layer between Nano carbon white particle with less modifying agent, Nano carbon white is realized
Particle is very stably distributed in rubber matrix with single particle shape.The present invention not only efficiently solves a nanometer hard charcoal
Black easy agglomeration traits, and ensure the dispersion processing stability of Nano carbon white particle again.The present invention has operating method letter
Single, modified cost is low, and environmental pollution is small, the advantages of being adapted to industrialized production.
Brief description of the drawings
Fig. 1 is the high dispersive structure chart of Nano carbon white particle surface.1 represents with vinylaromatic polymer polymer in figure
Chain is the solvent chain of tail, and 2 represent the anchoring group using cyanic acid ester group as anchor point, and 3 represent hard charcoal black track producing particle.
Fig. 2 is the infrared spectrum spectrogram of white carbon (a) and modified white carbon black (b).It is 1099cm in wave number on a-1Place goes out
Existing Si-O-Si asymmetric stretching vibration absworption peak, 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 Si-O-Si flexural vibrations absworption peak in place.On b, wave number is 1600~1500cm-1Place goes out
The weak absorbing peak of carboxyl is showed；Wave number is 1715-1730cm-1Place occurs in that the sharp absworption peak of ester group；Wave number be 3400~
3250cm-1Place occurs in that the sharp absworption peak of amide groups；Wave number is 1950~2150cm-1Place occurs in that the sharp absworption peak of cyanic acid ester group.
It can be seen that aliphatic diisocyanate and acrylamide polar monomer generation polymer successful deposition in Nano carbon white
Particle surface.
Embodiment
Following examples and comparative example is 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 embodiments and comparative example." part " described in embodiment and comparative example each means mass parts.
(1) raw material sources：
Other reagents are commercially available industrial goods
(2) analysis test method：
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 is dried at 100 DEG C in vacuum drying oven, using pressing potassium bromide troche, wave number is gathered
Scope 400-4000cm-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, Nano carbon white to be modified adds liquid by after atoleine complete wetting
Body paraffin fully vibrates 5min to 100mL scale with 30 times/1min frequency of oscillation, makes modified Nano white carbon in liquid
It is uniformly dispersed, then stands in paraffin, reads 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, it is good to make carbon black dispersion clear, easily compatible.
The assay method of oil absorption：Reference《The assay method of YS/T618-2007 aluminium hydroxide used as filling material oil absorptions》, 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 untill agglomerate do not split to powder, oil absorption is with the volume V of every 100g samples institute oil suction with toolsetting0
(mL) represent, be calculated as follows:
In formula, v is the volume (mL) of the diisooctyl phthalate consumed；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 monomer pre-emulsion：By 100 parts of styrene, 1 part of neopelex, 120 parts of deionizations
Water, 1.2 parts of sodium carbonate, 0.01 part of potassium peroxydisulfate are put into reactor together, when being warming up to 45 DEG C, and stirring reaction is prepared for 30 minutes
Into styrene pre-emulsion a.
(2) preparation of ultra-dispersed type Nano carbon white：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometer hard charcoals
Black and 150 parts of deionized waters are added to stirring mixing 10min in polymeric kettle；Then 4 parts of HTDI, 1.0 parts of sodium hydroxides are added, are risen
Temperature is to 40 DEG C, and stirring reaction 1hr is generated after then adding 2 parts of Methacrylamides and 0.5 part of sodium hydroxide reaction 30min
The performed polymer coated centered on Nano carbon white powder by HTDI and Methacrylamide；Finally add 10 parts of styrene
0.1 part of diethyl hydroxylamine, scrubbed, dehydration, dry, grinding are added after pre-emulsion a and 0.3 part of potassium peroxydisulfate, reaction 5.0hr
Ultra-dispersed type Nano carbon white is made.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Embodiment 2
(1) preparation of monomer pre-emulsion：Be the same as Example 1.
(2) preparation of ultra-dispersed type Nano carbon white：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometer hard charcoals
Black and 180 parts of deionized waters are added to stirring mixing 15min in polymeric kettle；Then 5 parts of HTDI, 1.2 parts of sodium hydroxides are added, are risen
Temperature is to 45 DEG C, and then stirring reaction 1.2hr is added after 2.5 parts of Methacrylamides and 0.6 part of sodium hydroxide reaction 30min
Generate the performed polymer coated centered on Nano carbon white powder by HTDI and Methacrylamide；Finally add 12 parts of benzene
Ethene pre-emulsion a and 0.4 part of potassium peroxydisulfate, reaction 5.0hr after add 0.2 part of diethyl hydroxylamine, it is scrubbed, dehydration, dry,
Ultra-dispersed type Nano carbon white is made in grinding.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Embodiment 3
(1) preparation of monomer pre-emulsion：Be the same as Example 1.
(2) preparation of ultra-dispersed type Nano carbon white：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometer hard charcoals
Black and 200 parts of deionized waters are added to stirring mixing 15min in polymeric kettle；Then 5.5 parts of HTDI, 1.3 parts of sodium hydroxides are added,
45 DEG C are warming up to, then stirring reaction 1.4hr is added after 3 parts of Methacrylamides and 0.6 part of sodium hydroxide reaction 30min
Generate the performed polymer coated centered on Nano carbon white powder by HTDI and Methacrylamide；Finally add 13 parts of benzene
Add 0.3 part of diethyl hydroxylamine after ethene pre-emulsion a and 0.45 part of potassium peroxydisulfate, reaction 5.5hr, it is scrubbed, dehydration, dry
Ultra-dispersed type Nano carbon white is made in dry, grinding.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Embodiment 4
(1) preparation of monomer pre-emulsion：By 100 parts of styrene, 3 parts of neopelexes, 120 parts of deionizations
Water, 1.4 parts of sodium carbonate, 0.04 part of potassium peroxydisulfate are put into reactor together, when being warming up to 50 DEG C, and stirring reaction is prepared for 40 minutes
Into styrene pre-emulsion b.
(2) preparation of ultra-dispersed type Nano carbon white：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometer hard charcoals
Black and 230 parts of deionized waters are added to stirring mixing 20min in polymeric kettle；Then 6.0 parts of HTDI, 1.4 parts of sodium hydroxides are added,
47 DEG C are warming up to, then stirring reaction 1.5hr adds 3.5 parts of Methacrylamides and 0.7 part of sodium hydroxide reaction 40min
The performed polymer coated centered on Nano carbon white powder by HTDI and Methacrylamide is generated afterwards；Finally add 15 parts
Styrene pre-emulsion b and 0.5 part of potassium peroxydisulfate, reaction 7hr after add 0.3 part of diethyl hydroxylamine, it is scrubbed, dehydration, dry,
Ultra-dispersed type Nano carbon white is made in grinding.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Embodiment 5
(1) preparation of monomer pre-emulsion：Be the same as Example 4.
(2) preparation of ultra-dispersed type Nano carbon white：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometer hard charcoals
Black and 250 parts of deionized waters are added to stirring mixing 23min in polymeric kettle；Then 6.5 parts of HTDI, 1.7 parts of sodium hydroxides are added,
47 DEG C are warming up to, then stirring reaction 1.7hr adds 4.0 parts of Methacrylamides and 0.8 part of sodium hydroxide reaction 50min
The performed polymer coated centered on Nano carbon white powder by HTDI and Methacrylamide is generated afterwards；Finally add 17 parts
Styrene pre-emulsion b and 0.7 part of potassium peroxydisulfate, reaction 7hr after add 0.3 part of diethyl hydroxylamine, it is scrubbed, dehydration, dry,
Ultra-dispersed type Nano carbon white is made in grinding.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Embodiment 6
(1) preparation of monomer pre-emulsion：Be the same as Example 4.
(2) preparation of ultra-dispersed type Nano carbon white：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometer hard charcoals
Black and 280 parts of deionized waters are added to stirring mixing 25min in polymeric kettle；Then 7 parts of HTDI, 1.8 parts of sodium hydroxides are added, are risen
Temperature is to 48 DEG C, and then stirring reaction 1.8hr is added after 4.5 parts of Methacrylamides and 0.9 part of sodium hydroxide reaction 55min
Generate the performed polymer coated centered on Nano carbon white powder by HTDI and Methacrylamide；Finally add 19 parts of benzene
Ethene pre-emulsion b and 0.8 part of potassium peroxydisulfate, reaction 7hr after add 0.4 part of diethyl hydroxylamine, it is scrubbed, dehydration, dry, grind
Grind to obtain ultra-dispersed type Nano carbon white.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Embodiment 7
(1) preparation of monomer pre-emulsion：：By 100 parts of α-methylstyrenes, 5 parts of neopelexes, 200 parts
Deionized water, 2.0 parts of sodium carbonate, 0.1 part of potassium peroxydisulfate are put into reactor together, when being warming up to 60 DEG C, 60 points of stirring reaction
Clock is prepared into α-methylstyrene pre-emulsion c.
(2) preparation of ultra-dispersed type Nano carbon white：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometer hard charcoals
Black and 300 parts of deionized waters are added to stirring mixing 30min in polymeric kettle；Then 8 parts of HDI, 2.0 parts of sodium hydroxides are added, are risen
Temperature is to 50 DEG C, and stirring reaction 2.0hr is generated after then adding 5.0 parts of acrylamides and 1.0 parts of sodium hydroxide reaction 60min
The performed polymer coated centered on Nano carbon white powder by HDI and acrylamide；Finally add 20 parts of Alpha-Methyl benzene second
0.5 part of diethyl hydroxylamine, scrubbed, dehydration, dry, grinding are added after alkene pre-emulsion c and 1.0 parts of potassium peroxydisulfates, reaction 8hr
Ultra-dispersed type Nano carbon white is made.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Comparative example 1
(1) preparation of monomer pre-emulsion：Be the same as Example 1.
(2) preparation of ultra-dispersed type Nano carbon white：Other conditions are same as Example 1, and difference is to prepare
HTDI addition is 2 parts in journey, i.e.,：Counted using Nano carbon white quality as 100 parts, take 100 parts of Nano carbon whites and 150 parts are gone
Ionized water is added to stirring mixing 10min in polymeric kettle；Then 2 parts of HTDI, 1.0 parts of sodium hydroxides are added, 40 DEG C is warming up to, stirs
Reaction 1hr is mixed, is generated after then adding 2 parts of Methacrylamides and 0.5 part of sodium hydroxide reaction 30min with Nano carbon white
The performed polymer coated centered on powder by HTDI and Methacrylamide；Finally add 10 parts of styrene pre-emulsion a and
0.1 part of diethyl hydroxylamine is added after 0.3 part of potassium peroxydisulfate, reaction 5.0hr, scrubbed, dehydration, dry, grinding are made ultra-dispersed
Type Nano carbon white.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Comparative example 2
(1) preparation of monomer pre-emulsion：Be the same as Example 1.
(2) preparation of ultra-dispersed type Nano carbon white：Other conditions are same as Example 1, and difference is to prepare
Styrene pre-emulsion a addition is 8 parts in journey, i.e.,：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometer hard charcoals
Black and 180 parts of deionized waters are added to stirring mixing 15min in polymeric kettle；Then 5 parts of HTDI, 1.2 parts of sodium hydroxides are added, are risen
Temperature is to 45 DEG C, and then stirring reaction 1.2hr is added after 2.5 parts of Methacrylamides and 0.6 part of sodium hydroxide reaction 30min
Generate the performed polymer coated centered on Nano carbon white powder by HTDI and Methacrylamide；Finally add 8 parts of benzene
Ethene pre-emulsion a and 0.4 part of potassium peroxydisulfate, reaction 5.0hr after add 0.2 part of diethyl hydroxylamine, it is scrubbed, dehydration, dry,
Ultra-dispersed type Nano carbon white is made in grinding.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Comparative example 3
(1) preparation of monomer pre-emulsion：Be the same as Example 1.
(2) preparation of ultra-dispersed type Nano carbon white：Other conditions are same as Example 1, and difference is to prepare
The addition of Methacrylamide is 1.5 parts in journey, i.e.,：Counted using Nano carbon white quality as 100 parts, take 100 parts of nanometer hard charcoals
Black and 200 parts of deionized waters are added to stirring mixing 15min in polymeric kettle；Then 5.5 parts of HTDI, 1.3 parts of sodium hydroxides are added,
45 DEG C are warming up to, then stirring reaction 1.4hr adds 1.5 parts of Methacrylamides and 0.6 part of sodium hydroxide reaction 30min
The performed polymer coated centered on Nano carbon white powder by HTDI and Methacrylamide is generated afterwards；Finally add 13 parts
Add 0.3 part of diethyl hydroxylamine after styrene pre-emulsion a and 0.45 part of potassium peroxydisulfate, reaction 5.5hr, it is scrubbed, dehydration, dry
Ultra-dispersed type Nano carbon white is made in dry, grinding.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Comparative example 4
The preparation of ultra-dispersed type Nano carbon white：Other conditions are same as Example 4, and difference is in preparation process
Styrene pre-emulsion b is not added with, but is directly added into styrene, i.e.,：Counted using Nano carbon white quality as 100 parts, take 100 parts to receive
Off-white carbon black and 230 parts of deionized waters are added to stirring mixing 20min in polymeric kettle；Then 6.0 parts of HTDI, 1.4 parts of hydrogen are added
Sodium oxide molybdena, is warming up to 47 DEG C, stirring reaction 1.5hr, then adds 3.5 parts of Methacrylamides and 0.7 part of sodium hydroxide is anti-
Answer the performed polymer for generating and being coated centered on Nano carbon white powder by HTDI and Methacrylamide after 40min；Again finally
Add and 0.3 part of diethyl hydroxylamine added after 15 parts of styrene and 0.5 part of potassium peroxydisulfate, reaction 7hr, scrubbed, dehydration, dry,
Ultra-dispersed type Nano carbon white is made in grinding.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Comparative example 5
(1) preparation of monomer pre-emulsion：Be the same as Example 4.
(2) preparation of ultra-dispersed type Nano carbon white：Other conditions are same as Example 5, and difference is to prepare
Initiator potassium persulfate is not added with journey, styrene pre-emulsion b is that dialogue carbon black particle surface is only coated, i.e.,：To receive
Off-white carbon black mass is 100 parts of meters, takes 100 parts of Nano carbon whites and 250 parts of deionized waters to be added in polymeric kettle and stirs mixing
23min；Then 6.5 parts of HTDI, 1.7 parts of sodium hydroxides are added, 47 DEG C are warming up to, then stirring reaction 1.7hr adds 4.0
Generated after part Methacrylamide and 0.8 part of sodium hydroxide reaction 50min centered on Nano carbon white powder by HTDI and first
The performed polymer that base acrylamide is coated；0.3 part of diethyl is added after finally adding 17 parts of styrene pre-emulsion b, reaction 7hr
Ultra-dispersed type Nano carbon white is made in base azanol, scrubbed, dehydration, dry, grinding.Sampling analysis：Standard specimen is made, through surveying
Examination performance is shown in Table 1.
Comparative example 6
(1) preparation of monomer pre-emulsion：Be the same as Example 4.
(2) preparation of ultra-dispersed type Nano carbon white：Other conditions are same as Example 4, and difference is to prepare
Methacrylamide is not added with journey, i.e.,：Counted using Nano carbon white quality as 100 parts, take 100 parts of Nano carbon whites and 280 parts are gone
Ionized water is added to stirring mixing 25min in polymeric kettle；Then 7 parts of HTDI, 1.8 parts of sodium hydroxides are added, 48 DEG C is warming up to, stirs
Reaction 1.8hr is mixed, the quilt centered on Nano carbon white powder is generated after then adding 0.9 part of sodium hydroxide reaction 55min
The performed polymer that HTDI and Methacrylamide are coated；Finally add 19 parts of styrene pre-emulsion b and 0.8 part of persulfuric acid
0.4 part of diethyl hydroxylamine is added after potassium, reaction 7hr, ultra-dispersed type Nano carbon white is made in scrubbed, dehydration, dry, grinding.
Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
Comparative example 7
The preparation of ultra-dispersed type Nano carbon white：Other conditions are same as Example 7, and difference is in preparation process
α-methylstyrene pre-emulsion c is not added with, but is directly added into α-methylstyrene, i.e.,：Using Nano carbon white quality as 100 parts
Meter, takes 100 parts of Nano carbon whites and 300 parts of deionized waters to be added to stirring mixing 30min in polymeric kettle；Then 8 parts are added
HDI, 2.0 parts of sodium hydroxides, are warming up to 50 DEG C, then stirring reaction 2.0hr adds 5.0 parts of acrylamides and 1.0 parts of hydrogen-oxygens
The performed polymer coated centered on Nano carbon white powder by HDI and acrylamide is generated after changing sodium reaction 60min；Again finally
Add and 0.5 part of diethyl hydroxylamine is added after 20 parts of α-methylstyrenes and 1.0 parts of potassium peroxydisulfates, reaction 8hr, scrubbed, dehydration,
Dry, ultra-dispersed type Nano carbon white is made in grinding.Sampling analysis：Standard specimen is made, performance is shown in Table 1 after tested.
The settling volume and oil absorbency of the ultra-dispersed type Nano carbon white of table 1
As shown in Table 1：The settling volume of embodiment is big than comparative example under same time, and oil absorption is below contrast
Example, illustrates that the modified effect of the present invention is obvious.Secondly from embodiment 1~7 it can be seen that modified Nano white carbon passes through twin-screw
The settling volume (120min) and oil absorbency that are measured after extruder extrusion and the change do not extruded are little, illustrate modified Nano hard charcoal
Black processing dispersion stabilization is good.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
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 (12)
1. a kind of method of modifying of Nano carbon white, it is characterised in that mainly include the following steps that：
(1) prepared by monomer pre-emulsion：In terms of mass parts, by 100 parts of aryl ethylene class monomers, 1~5 part of emulsifying agent, 100~200
Part deionized water, 1.0~2.0 parts of buffers, 0.01~0.1 part of initiator are put into reactor together, are warming up to 40~60 DEG C
When, stirring reaction is prepared into monomer pre-emulsion in 30~60 minutes；
(2) the preparation of modified Nano white carbon：In terms of mass parts, 100 parts of Nano carbon whites and 150~300 parts of deionized waters are taken to add
Enter into polymeric kettle 10~30min of stirring mixing；Then 4~8 parts of aliphatic diisocyanates, 1.0~2.0 parts of catalysis are added
Agent, is warming up to 40~50 DEG C, then 1~2h of stirring reaction adds 2~5 parts of vinyl-based acid amides and 0.5~1.0 part of catalysis
Agent is generated centered on Nano carbon white powder by aliphatic diisocyanate and vinyl-based acid amides institute after reacting 30~60min
The performed polymer of cladding；Finally add after 10~20 parts of monomer pre-emulsions and 0.3~1.0 part of initiator, 5.0~8.0h of reaction
0.1~0.5 part of terminator is added, modified Nano white carbon is made in scrubbed, dehydration, dry, grinding.
2. method of modifying as claimed in claim 1, it is characterised in that the white carbon is nano level, and its particle diameter is：20~
60nm。
3. the method for modifying as described in any one of claim 1 or 2, it is characterised in that the aliphatic diisocyanate is selected from six
Methylene diisocyanate, IPDI, dicyclohexyl methyl hydride -4,4'- diisocyanate, hexahydrotoluene two
One or more of mixture in isocyanates.
4. method of modifying as claimed in claim 3, it is characterised in that the aliphatic diisocyanate is hexahydrotoluene two
Isocyanates.
5. the method for modifying as described in claim 1,2 or 3 any one, it is characterised in that described vinyl-based acid amides is selected from third
One or more of mixtures in acrylamide, Methacrylamide, 1- crotonamides, methacrylamide, 1- hexene acid amides.
6. method of modifying as claimed in claim 5, it is characterised in that the vinyl-based acid amides is Methacrylamide.
7. the method for modifying as described in claim 1,2 or 6 any one, it is characterised in that the aryl ethylene class monomer is benzene second
One or more of mixtures in alkene, α-methylstyrene, 2- propenyl benzenes, ethyl styrene and their derivative.
8. method of modifying as claimed in claim 7, it is characterised in that the aryl ethylene class compound is styrene.
9. the method for modifying as described in claim 1,2,6 or 8 any one, it is characterised in that the initiator be ammonium persulfate,
One kind in potassium peroxydisulfate, sodium peroxydisulfate.
10. method of modifying as claimed in claim 9, it is characterised in that the initiator is potassium peroxydisulfate.
11. the method for modifying as described in claim 1,2,6,8 or 10 any one, it is characterised in that the catalyst is carbonic acid
One kind in sodium, sodium acid carbonate, sodium hydroxide, ammoniacal liquor, ammonium hydrogen carbonate.
12. method of modifying as claimed in claim 11, it is characterised in that the catalyst is sodium hydroxide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111073197A (en) * | 2018-10-18 | 2020-04-28 | 中国石油天然气股份有限公司 | Preparation method of high-dispersion nano white carbon black used as rubber filler |
| CN113429806A (en) * | 2021-07-03 | 2021-09-24 | 江苏爱特恩高分子材料有限公司 | Preparation method of high-dispersion modified white carbon black for rubber filler |
| CN113789069A (en) * | 2021-08-18 | 2021-12-14 | 浦林成山（青岛）工业研究设计有限公司 | White carbon black dispersing auxiliary agent and preparation method and application thereof |
| CN113789066A (en) * | 2021-08-18 | 2021-12-14 | 浦林成山（青岛）工业研究设计有限公司 | Olefin modified white carbon black for rubber and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19933819A1 (en) * | 1999-07-20 | 2001-02-01 | Bayer Ag | Compact and / or cellular polyurethane elastomers with nanoscale fillers |
| CN103524797A (en) * | 2012-07-05 | 2014-01-22 | 中国石油天然气股份有限公司 | Diene rubber composition and preparation method thereof |
| CN103665729A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Oil-extended styrene-butadiene rubber containing nano silicon dioxide on surface, composition and preparation method thereof |
-
2016
- 2016-04-08 CN CN201610218630.5A patent/CN107266716A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19933819A1 (en) * | 1999-07-20 | 2001-02-01 | Bayer Ag | Compact and / or cellular polyurethane elastomers with nanoscale fillers |
| CN103524797A (en) * | 2012-07-05 | 2014-01-22 | 中国石油天然气股份有限公司 | Diene rubber composition and preparation method thereof |
| CN103665729A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Oil-extended styrene-butadiene rubber containing nano silicon dioxide on surface, composition and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘益军 编著: "《聚氨酯原料及助剂手册》", 31 January 2013, 化学工业出版社 * |
| 欧宝立 等: "SiO2大分子单体与苯乙烯共聚制备PS/SiO2纳米复合材料", 《中国科学B辑：化学》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111073197A (en) * | 2018-10-18 | 2020-04-28 | 中国石油天然气股份有限公司 | Preparation method of high-dispersion nano white carbon black used as rubber filler |
| CN113429806A (en) * | 2021-07-03 | 2021-09-24 | 江苏爱特恩高分子材料有限公司 | Preparation method of high-dispersion modified white carbon black for rubber filler |
| CN113789069A (en) * | 2021-08-18 | 2021-12-14 | 浦林成山（青岛）工业研究设计有限公司 | White carbon black dispersing auxiliary agent and preparation method and application thereof |
| CN113789066A (en) * | 2021-08-18 | 2021-12-14 | 浦林成山（青岛）工业研究设计有限公司 | Olefin modified white carbon black for rubber and preparation method thereof |
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