CN105384969B - A kind of high dispersive zinc oxide and preparation method thereof - Google Patents
A kind of high dispersive zinc oxide and preparation method thereof Download PDFInfo
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- CN105384969B CN105384969B CN201510924690.4A CN201510924690A CN105384969B CN 105384969 B CN105384969 B CN 105384969B CN 201510924690 A CN201510924690 A CN 201510924690A CN 105384969 B CN105384969 B CN 105384969B
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- zinc oxide
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- azodiisobutyronitrile
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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
- C08K9/10—Encapsulated 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
- C08K9/04—Ingredients treated with organic substances
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Abstract
The invention discloses a kind of high dispersive zinc oxide and preparation method thereof, the high dispersive zinc oxide includes following components by weight：100 parts of zinc oxide, 14~29 parts of zinc acrylate resin, 5~123 parts of dry glue.The preparation method of the high dispersive zinc oxide comprises the following steps：(1) acrylic acid is added in ammonia spirit, stirring makes its dispersed in the solution；(2) latex is added in solution of zinc sulfate, stirring makes its dispersed in the solution；(3) in the case where being stirred continuously, the mixed solution of (1) and (2) is adjusted into pH value with ammoniacal liquor, continues stirring reaction, is centrifuged after terminating to reaction；(4) after the filter cake drying isolated, the ethanol dilution with azodiisobutyronitrile carries out bulk polymerization in situ in mixer while hot, and high dispersive zinc oxide is made；(5) filtrate isolated carries out water-bath with calcium hydroxide.The zinc oxide of present invention good dispersion in sizing material, and the anti-wear performance of vulcanizate can be improved.
Description
Technical field
The invention belongs to Field of Fine Chemicals, is related to a kind of high dispersive zinc oxide and preparation method thereof.
Background technology
The conventional zinc oxide of rubber materials is divided into three classes：American process zinc oxide, indirect process zinc oxide and activated zinc oxide.Directly
Connection zinc oxide is that coke, lime are added in qualified zinc gray, is smelted in high temperature furnace, is cooled down again through reducing, aoxidizing
Arrive, zinc oxide content is not high and unstable in finished product, granularity is uneven, heavy metal particles content is high, has been rarely used；Between
Connection zinc oxide is using zinc ingot metal or cadmia as raw material, is smelted in high temperature furnace, oxidized to cool down to obtain again, is aoxidized in finished product
Zn content is high and stay in grade, epigranular, heavy metal particles content are low, is the main product that current tire formulation uses, but
Its price is larger by zinc ingot metal price, fluctuation, and price is also highest in a few class zinc oxide；Activated zinc oxide is with secondary
Zinc oxide is raw material, and zinc solution is obtained after acidleach or ammonia leaching, then obtains presoma through precipitation reaction, is finally forged in high temperature furnace
Burning obtains zinc oxide, can be joined by regulating and controlling the techniques such as zinc solution concentration, reaction temperature, charging rate, calcining heat, calcination time
Number come prepare different specific surface areas, different-shape zinc oxide, the height of bigger serface is industrially prepared frequently with the method
Activated zinc oxide.
Zinc oxide specific surface area is bigger, and surface-active is higher, makes it easy to reunite, and the dispersiveness in rubber polymer will
It is very poor, it is difficult closely to bring the advantage of high activity comprehensively into play.Up to the present, for each national skill of scattering problem of zinc oxide
Art personnel have also carried out many research.Chinese patent CN104803408A provides a kind of preparation of modified nanometer zinc oxide
Method：Lignosulfonates are introduced during Zinc oxide water thermal synthesis as dispersant, improve the oxygen obtained during Hydrothermal Synthesiss
Change the dispersiveness of zinc.The method that Chinese patent CN103694743A provides a kind of titanate coupling agent surface modified zinc oxide：
A certain amount of titanate coupling agent is weighed, is disperseed in organic solvent；Scattered titanate coupling agent solution is added anhydrous
In ethanol, nano zine oxide is added；It is scattered at a high speed using high-shearing dispersion emulsifying machine；Then using magnetic agitation for a period of time；
The nano zine oxide of last drying titanate coupling agent modified.Chinese patent CN103030171A provides a kind of modified oxygen
Change the preparation method of zinc：Ball milling prepares Bi (OH)3ZnO presoma is coated, is then thermally decomposed, obtained in high temperature environments
The modified zinc oxide of bismuth oxide cladding, as secondary zinc electrode negative material, good conductivity, charge acceptance are strong, specific capacity
Height, have extended cycle life.Chinese patent CN102099297A provides a kind of modified zinc oxide particles：Zinc salt and alkali precipitation go out precipitation
Product simultaneously removes the residue after polar solvent, in apolar substance, is inhaled with the carboxylic acid with 10~30 carbon atoms and UV
Receive agent to be modified it, obtain being modified ZnO particle.Chinese patent CN102459471A provides a kind of modified ZnO nano
Grain：It is anti-with orthosilicic acid tetraalkyl ester and optional organosilan in the presence of ammonia or amine to make to be dissolved in the Zinc oxide nanoparticle in solvent
Should, condition, which is the reaction, to be less than under 5 weight % relative to the total amount of solvent and water in water content and carries out, and is included so as to obtain one kind
Si-O- alkyl and the modified oxidized zinc nanoparticles in organic solvent can be dissolved in.Japan Patent JP2008280202 (A) is provided
A kind of method that surface of nanometer zinc oxide is modified：The use of formula is RaSiX(4~a)(wherein R is organic official containing 1~18 carbon
It can roll into a ball, X represents hydrolyzable groups, a 1,2 or silicon-containing compound 3) and the fine grained that average grain diameter is 0.5~20nm is aoxidized
Zinc carries out surface modification, and zinc oxide after modified steadily in the long term and can be dispersed in solution and resin.Japan Patent
JP2008266050 (A) provides a kind of method that surface of nanometer zinc oxide is modified：Using containing organic carboxyl acids more than 8 carbon
Be 0.5 to average grain diameter (at 25 DEG C, its 5 parts by weight of minimum dissolving in the fatty alcohol of more than 100 DEG C of 100 parts by weight boiling point)~
20nm zinc oxide fine particle carries out surface modification, and zinc oxide after modified may be homogenously dispersed in resin without reuniting.Day
This patent JP7069627 (A), JP7069628 (A), JP7069630 (A), JP7069629 (A) each provide one kind through ketone
The dispersed excellent Zinc oxide powder that class, esters, amine, alcohols material are modified.Above patent is all to use small-molecule substance,
As coupling agent, carboxylic acid, ketone, amine, alcohol, ester to zinc oxide carry out surface modification, for improve zinc oxide solution system (as apply
Material) in it is dispersed fruitful.It is modified oxidized using above-mentioned small-molecule substance and solid rubber has very high molecular weight
Zinc, although dispersiveness of the zinc oxide in rubber can be improved to a certain extent, the difference on molecular weight has been doomed this modification
Certain limitation is had in the validity and permanence of mode.
At present, a kind of high dispersive zinc oxide truly is lacked, it has good in rubber-like high molecular polymer
Good dispersiveness, and the combination property of product can be improved, especially anti-wear performance.
The content of the invention
The technical problems to be solved by the invention be to provide the good high dispersive zinc oxide of a kind of good dispersion, wearability and its
Preparation method.
To achieve these goals, the present invention is achieved through the following technical solutions：A kind of high dispersive zinc oxide of the present invention,
The high dispersive zinc oxide includes following components by weight：
100 parts of zinc oxide,
14~29 parts of zinc acrylate resin,
5~123 parts of dry glue.
The preparation method of high dispersive zinc oxide of the present invention, comprises the following steps：
(1) acrylic acid is added in ammonia spirit, stirring makes its dispersed in the solution, and acrylic acid accounts for the quality of solution
Percentage composition is 1.2%~6%, and the weight/mass percentage composition that ammoniacal liquor accounts for solution is 20%~50%；
(2) rubber latex is added in solution of zinc sulfate, stirring makes its dispersed in the solution, and dry glue accounts for the matter of solution
It is 0.5%~21% to measure percentage composition, and the weight/mass percentage composition that zinc sulfate accounts for solution is 20%~35%；
(3) in the case where being stirred continuously, two kinds of solution of step (1) and step (2) are mixed, mixed solution adjusts pH with ammoniacal liquor
Value, continues stirring reaction, and reaction is centrifuged after terminating；
(4) after the filter cake drying isolated, the ethanol dilution with azodiisobutyronitrile is carried out in mixer while hot
Bulk polymerization in situ, high dispersive zinc oxide is made；
(5) filtrate isolated carries out water-bath with calcium hydroxide, and the calcium sulfate for reacting to obtain is released through centrifuging, drying
The NH of releasing3Recycled.
Further, in step (3), in the case where being stirred continuously, two kinds of solution of step (1) and step (2) is mixed, mixed
After conjunction solution ammoniacal liquor regulation pH value is 10~12, continue 20~300min of stirring reaction, stir speed (S.S.) is 100~800r/
Min, reaction are centrifuged after terminating；
In step (4), after the filter cake drying isolated, the ethanol dilution with azodiisobutyronitrile is at a high speed while hot
Bulk polymerization in situ is carried out in mixer, reaction temperature is controlled at 80~130 DEG C, and the reaction time is 2~6h；
In step (5), the filtrate isolated carries out water-bath with calcium hydroxide, and reacting obtained calcium sulfate need to be from
The heart, drying, react the NH discharged3Recycled.
Further, in step (2), the one kind or two of described rubber latex in Heveatex and styrene-butadiene latex
The combination of kind.
Further, in step (4), the ethanol dilution of described azodiisobutyronitrile is by azodiisobutyronitrile
Dissolve in ethanol, and the mass ratio of azodiisobutyronitrile and ethanol is 1:10~1:20.
Beneficial effect:A kind of high dispersive zinc oxide, and whole process is prepared by simple, easy method in the present invention
Produced without " three wastes ", belong to cleanly production.Acrylic acid is combined by ionic bond with zinc oxide, in the initiation of azodiisobutyronitrile
Under effect, the double bond in the double bond and dry glue in its molecular structure carries out radical polymerization, so as to form jail in zinc oxide surface
Solid polymer modification layer.Obtained product dispersive property in rubber is excellent, and has well compatible between rubber molecule
Property, while sulfurate activity effect is more uniformly played in rubber compounding, moreover it is possible to improve the comprehensive mechanical performance of vulcanizate, especially
It is anti-wear performance.It is well known that the tyre surface of tire has special requirement to the wearability of sizing material, inner liner is helped vulcanizing system
The dispersiveness of agent (including sulphur, accelerator and zinc oxide) has special requirement, the property for the high dispersive zinc oxide that the present invention obtains
Energy advantage, makes it be particularly suited for the tyre surface of tire and airtight layer formula.
Brief description of the drawings
Fig. 1 is the XRD spectrum of the products therefrom of embodiments of the invention 1；
Fig. 2 is that the gained high dispersive zinc oxide of embodiments of the invention 1 is added in sizing material, is put using what separating apparatus collected
Big 400 times of photo；
Fig. 3 is that indirect process zinc oxide is added in sizing material obtained by the comparative example of the present invention, is put using what separating apparatus collected
Big 400 times of photo；
Fig. 4 is the scanning electricity in the tension failure face of the gained high dispersive zinc oxide of embodiments of the invention 1 and rubber composite
Sub- microscope amplifies 1000 times of photo；
Fig. 5 is the scanning electron in the tension failure face of indirect process zinc oxide and rubber composite obtained by the comparative example of the present invention
Microscope amplifies 1000 times of photo.
Embodiment
The present invention is further illustrated by the following examples.It should be understood that these embodiments are the explainations of the present invention
And citing, the scope of the present invention is not limited in any form.
Embodiment 1
A kind of high dispersive zinc oxide of the present invention, the high dispersive zinc oxide include following components by weight：
100 parts of zinc oxide,
14 parts of zinc acrylate resin,
5 parts of dry glue (natural rubber).
The preparation method of high dispersive zinc oxide of the present invention, comprises the following steps：
(1) acrylic acid is added in ammonia spirit, stirring makes its dispersed in the solution, and acrylic acid accounts for the quality of solution
Percentage composition is 1.2%, and the weight/mass percentage composition that ammoniacal liquor accounts for solution is 20%；
(2) Heveatex is added in solution of zinc sulfate, stirring makes its dispersed in the solution, and natural rubber accounts for solution
Weight/mass percentage composition be 0.5%, zinc sulfate account for solution weight/mass percentage composition be 20%；Natural rubber in described Heveatex
The weight/mass percentage composition of glue is 40%.
(3) in the case where being stirred continuously, two kinds of solution of step (1) and step (2) are mixed, mixed solution adjusts pH with ammoniacal liquor
It is worth after 10, to continue stirring reaction 20min, stir speed (S.S.) 100r/min, reaction is centrifuged after terminating；
(4) after the filter cake drying isolated, the ethanol dilution with azodiisobutyronitrile is in high-speed mixer while hot
Bulk polymerization in situ is carried out, reaction temperature is controlled at 80 DEG C, reaction time 2h, and high dispersive zinc oxide is made；Described
The ethanol dilution of azodiisobutyronitrile is to dissolve azodiisobutyronitrile in ethanol, and the matter of azodiisobutyronitrile and ethanol
Amount is than being 1:10；
(5) filtrate isolated carries out water-bath with calcium hydroxide slurry, and the calcium sulfate for reacting to obtain is through centrifuging, drying
It is dry, react the NH discharged3Recycled.
Embodiment 2
The difference of embodiment 2 and embodiment 1 is：
A kind of high dispersive zinc oxide of the present invention, the high dispersive zinc oxide include following components by weight：
100 parts of zinc oxide,
29 parts of zinc acrylate resin,
123 parts of dry glue (butadiene-styrene rubber).
The preparation method of high dispersive zinc oxide of the present invention, comprises the following steps：
In step (1), acrylic acid is added in ammonia spirit, stirring makes its dispersed in the solution, and acrylic acid accounts for
The weight/mass percentage composition of solution is 6%, and the weight/mass percentage composition that ammoniacal liquor accounts for solution is 50%；
In step (2), styrene-butadiene latex is added in solution of zinc sulfate, stirring makes its dispersed in the solution, butylbenzene
The weight/mass percentage composition that rubber accounts for solution is 21%, and the weight/mass percentage composition that zinc sulfate accounts for solution is 35%；Described butadiene-styrene rubber
The weight/mass percentage composition of butadiene-styrene rubber is 40% in breast.
In step (3), in the case where being stirred continuously, two kinds of solution of step (1) and step (2) are mixed, mixed solution is used
After ammoniacal liquor regulation pH value is 12, continue stirring reaction 300min, stir speed (S.S.) 800r/min, reaction carries out centrifugation point after terminating
From；
In step (4), after the filter cake drying isolated, the ethanol dilution with azodiisobutyronitrile is at a high speed while hot
Bulk polymerization in situ is carried out in mixer, reaction temperature is controlled at 130 DEG C, reaction time 6h, and high dispersive oxidation is made
Zinc；The ethanol dilution of described azodiisobutyronitrile is to dissolve azodiisobutyronitrile in ethanol, and azodiisobutyronitrile
Mass ratio with ethanol is 1:20.
Embodiment 3
The difference of embodiment 3 and embodiment 1 is：
A kind of high dispersive zinc oxide of the present invention, the high dispersive zinc oxide include following components by weight：
100 parts of zinc oxide,
23 parts of zinc acrylate resin,
60 parts of dry glue.
The dry glue is the mixture of natural rubber and butadiene-styrene rubber.
The preparation method of high dispersive zinc oxide of the present invention, comprises the following steps：
In step (1), acrylic acid is added in ammonia spirit, stirring makes its dispersed in the solution, and acrylic acid accounts for
The weight/mass percentage composition of solution is 4%, and the weight/mass percentage composition that ammoniacal liquor accounts for solution is 35%；
In step (2), rubber latex is added in solution of zinc sulfate, stirring makes its dispersed in the solution, dry glue
The weight/mass percentage composition for accounting for solution is 15%, and the weight/mass percentage composition that zinc sulfate accounts for solution is 27%；Described rubber latex is
The mixture of Heveatex and styrene-butadiene latex, and the weight/mass percentage composition of dry glue is 40% in two kinds of latex.
In step (3), in the case where being stirred continuously, two kinds of solution of step (1) and step (2) are mixed, mixed solution is used
After ammoniacal liquor regulation pH value is 11, continue stirring reaction 260min, stir speed (S.S.) 600r/min, reaction carries out centrifugation point after terminating
From；
In step (4), after the filter cake drying isolated, the ethanol dilution with azodiisobutyronitrile is at a high speed while hot
Bulk polymerization in situ is carried out in mixer, reaction temperature is controlled at 120 DEG C, reaction time 4h, and high dispersive oxidation is made
Zinc；The ethanol dilution of described azodiisobutyronitrile is to dissolve azodiisobutyronitrile in ethanol, and azodiisobutyronitrile
Mass ratio with ethanol is 1:15.
Comparative example
Indirect process zinc oxide is using zinc ingot metal as raw material, and zinc fume is converted at a high temperature of 1000 DEG C in graphite crucible,
The air oxidation generation zinc oxide then blasted, and collect and obtain after cooling tube.
Experiment 1
High dispersive zinc oxide made from embodiment 1 is applied in tire tread formula, formula used is：It is NR 100, hard
Resin acid 2, N220 45, white carbon 8, Si69 0.8, aromatic naphtha 5, protection wax 2,4010NA 1.5, sulphur 1.2, NOBS 1.6, sulphur
Change activating agent and (become kind, activating agent is respectively high dispersive zinc oxide prepared by embodiment 1 and indirect method oxidation prepared by comparative example
Zinc) 4.
In two-roll mill, first natural rubber is plasticated, then adds various auxiliary agents, obtains elastomeric compound, then
Vulcanized at 151 DEG C by sulfurizing time, obtain vulcanizing rubber.Tested by national standard, the gained performance such as institute of table 1
Show.
Table 1
From the data of table 1 relatively in it can be seen that：The sizing material of high dispersive zinc oxide prepared by embodiment 1 is added compared with indirect method
Zinc oxide sizing material has more excellent mechanical performance, and the lifting of especially anti-wear performance is more notable, and this has fully demonstrated high dispersive
Zinc oxide has higher sulfurate activity compared with indirect process zinc oxide.
Use the section of separating apparatus observation elastomeric compound：Fig. 2 is that high dispersive zinc oxide prepared by embodiment 1 is added in sizing material
Afterwards, elastomeric compound section is exaggerated 400 times of photo；Fig. 3 is that indirect process zinc oxide is added after sizing material, and elastomeric compound section is exaggerated
400 times of photo.Vulcanize rubber after low-temperature brittle fracture, section situation is observed using SEM：Fig. 4 is that addition is implemented
The section picture of the vulcanizate of high dispersive zinc oxide prepared by example 1；Fig. 5 is the sectional drawing using the vulcanizate of indirect process zinc oxide
Piece.
Find out from Fig. 2 and Fig. 3 comparison：High dispersive zinc oxide in Fig. 2 has preferably compared with the indirect process zinc oxide in Fig. 3
Dispersiveness.Fig. 4 and Fig. 5 comparison：Indirect process zinc oxide agglomerate grain in Fig. 5, and have part indirect process zinc oxide
It is exposed；And the high dispersive zinc oxide and the compatibility of rubber matrix that embodiment 1 obtains are good, Fig. 4 shows that high dispersive zinc oxide wraps
Overlay in rubber matrix, rarely expose, it can also be seen that high dispersive zinc oxide is dispersed in rubber from Fig. 4.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, the present invention
Claimed scope is by appended claims, specification and its equivalent thereof.
Claims (4)
1. a kind of preparation method of high dispersive zinc oxide, high dispersive zinc oxide includes following components by weight：
100 parts of zinc oxide,
14 ~ 29 parts of zinc acrylate resin,
5 ~ 123 parts of dry glue,
It is characterised in that it includes following steps：（1）Acrylic acid is added in ammonia spirit, stirring makes it be dispersed in solution
In, the weight/mass percentage composition that acrylic acid accounts for solution is 1.2% ~ 6%, and the weight/mass percentage composition that ammoniacal liquor accounts for solution is 20% ~ 50%；
（2）Rubber latex is added in solution of zinc sulfate, stirring makes its dispersed in the solution, and the quality percentage that dry glue accounts for solution contains
Measure as 0.5% ~ 21%, the weight/mass percentage composition that zinc sulfate accounts for solution is 20% ~ 35%；（3）In the case where being stirred continuously, by step（1）
And step（2）Two kinds of solution mixing, mixed solution with ammoniacal liquor adjust pH values, continue stirring reaction, react terminate after carry out from
The heart separates；（4）After the filter cake drying isolated, the ethanol dilution with azodiisobutyronitrile carries out original in mixer while hot
Position bulk polymerization, is made high dispersive zinc oxide；（5）The filtrate isolated carries out water-bath with calcium hydroxide, reacts
To calcium sulfate through centrifuging, drying, the NH3 discharged is recycled.
2. the preparation method of the high dispersive zinc oxide according to claim 1, it is characterised in that：
In step（3）In, in the case where being stirred continuously, by step（1）And step（2）Two kinds of solution mixing, mixed solution ammoniacal liquor
After regulation pH values are 10 ~ 12, continue 20 ~ 300min of stirring reaction, stir speed (S.S.) is 100 ~ 800r/min, and reaction terminates
After be centrifuged；In step（4）In, after the filter cake drying isolated, the ethanol with azodiisobutyronitrile dilutes while hot
Liquid carries out bulk polymerization in situ in high-speed mixer, and reaction temperature is controlled at 80 ~ 130 DEG C, and the reaction time is 2 ~ 6h；
In step（5）In, filtrate and the calcium hydroxide isolated carry out water-bath, and the calcium sulfate for reacting to obtain is needed to centrifuge, dried
It is dry, react the NH3 discharged and recycled.
3. the preparation method of the high dispersive zinc oxide according to claim 1 or 2, it is characterised in that：In step（2）
In, described rubber latex is selected from the combination of one or both of Heveatex and styrene-butadiene latex.
4. the preparation method of the high dispersive zinc oxide according to claim 1 or 2, it is characterised in that：In step（4）
In, the ethanol dilution of described azodiisobutyronitrile is to dissolve azodiisobutyronitrile in ethanol, and azodiisobutyronitrile
Mass ratio with ethanol is 1:10~1:20.
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| CN106565988A (en) * | 2016-11-03 | 2017-04-19 | 广州凯耀资产管理有限公司 | Novel zinc oxide rubber vulcanization activator, and preparation method and application thereof |
| CN114479184A (en) * | 2022-02-28 | 2022-05-13 | 江苏爱特恩高分子材料有限公司 | Preparation method of high-dispersion zinc oxide |
| CN115353664A (en) * | 2022-09-02 | 2022-11-18 | 常州市五洲环保科技有限公司 | Modified zinc oxide vulcanizing agent and preparation method thereof |
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| CN1397572A (en) * | 2002-08-20 | 2003-02-19 | 华南理工大学 | Nano-class rubber-laminated inorganic substance composition and its preparing process |
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