CN105384969A - High-dispersion zinc oxide and preparation method thereof - Google Patents
High-dispersion zinc oxide and preparation method thereof Download PDFInfo
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- CN105384969A CN105384969A CN201510924690.4A CN201510924690A CN105384969A CN 105384969 A CN105384969 A CN 105384969A CN 201510924690 A CN201510924690 A CN 201510924690A CN 105384969 A CN105384969 A CN 105384969A
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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 high-dispersion zinc oxide and a preparation method thereof. The high-dispersion zinc oxide comprises, by weight, 100 parts of zinc oxide, 14-29 parts of zinc acrylate, and 5-123 parts of dry glue. The preparation method of the high-dispersion zinc oxide comprises the following steps: 1, adding acrylic acid into an ammonia water solution, and stirring to uniformly disperse acrylic acid in the solution in order to obtain a solution 1; 2, adding latex to a zinc sulfate solution, and stirring to uniformly disperse the latex in the solution in order to obtain a solution 2; 3, adjusting the pH value of a solution 1 and solution 2 mixed solution by ammonia water under continuous stirring, continuously stirring and reacting, and centrifuging after the reaction ends; 4, drying a filter cake obtained after the separation, and carrying out an in situ bulk polymerization reaction on the dried filter cake and an ethanol dilution solution of azodiisobutyronitrile in a mixing machine while hot to prepare the high-dispersion zinc oxide; and 5, carrying out a water bath reaction on a filtrate obtained after the separation and calcium hydroxide. The zinc oxide has good dispersibility in a rubber material, and can improve the wear resistance of vulcanized rubber.
Description
Technical field
The invention belongs to Field of Fine Chemicals, relate to a kind of high dispersive zinc oxide and preparation method thereof.
Background technology
The zinc oxide that rubber materials is conventional is divided three classes: American process zinc oxide, indirect process zinc oxide and active zinc flower.American process zinc oxide adds coke, lime in qualified zinc gray, smelts in High Temperature Furnaces Heating Apparatus, and cool through reduction, oxidation again and obtain, in finished product, zinc oxide content is not high and unstable, granularity is uneven, heavy metal particles content is high, is seldom used; Indirect process zinc oxide is for raw material with zinc ingot metal or cadmia, smelt in High Temperature Furnaces Heating Apparatus, cool again through oxidation and obtain, in finished product, zinc oxide content is high and stay in grade, epigranular, heavy metal particles content are low, it is the main product that current tire formulation uses, but its price is comparatively large by zinc ingot metal price, fluctuation, and price is also the highest in a few class zinc oxide; Active zinc flower take secondary zinc oxide as raw material, zinc solution is obtained after acidleach or ammonia leaching, presoma is obtained again through precipitin reaction, last calcining in High Temperature Furnaces Heating Apparatus obtains zinc oxide, prepare the zinc oxide of different specific surface area, different-shape by processing parameters such as regulation and control zinc solution concentration, temperature of reaction, feed rate, calcining temperature, calcination times, industrial normal employing this method prepares the high-active zinc oxide of bigger serface.
Zinc oxide specific surface area is larger, and surfactivity is higher, is just easy to reunite, and the dispersiveness in rubber polymer will be very poor, is closely difficult to highly active advantage to bring into play comprehensively.Up to the present, the scattering problem various countries technician for zinc oxide has also carried out many-sided research.Chinese patent CN104803408A provides a kind of preparation method of modified nanometer zinc oxide: in Zinc oxide water thermal synthesis process, introduce sulfonated lignin as dispersion agent, the dispersiveness of the zinc oxide obtained when improving Hydrothermal Synthesis.Chinese patent CN103694743A provides a kind of method of titanate coupling agent surface modification zinc oxide: take a certain amount of titanate coupling agent, and dispersion in organic solvent; Scattered titanate coupling agent solution is added in dehydrated alcohol, adds nano zine oxide; Adopt high-shearing dispersion emulsifying machine, high speed dispersion; Then magnetic agitation for some time is adopted; Finally dry and obtain the nano zine oxide of titanate coupling agent modified.Chinese patent CN103030171A provides a kind of preparation method of modified zinc oxide: ball milling prepares Bi (OH)
3the presoma of clading ZnO, then carries out thermolysis in high temperature environments, obtains the modified zinc oxide that bismuth oxide is coated, and as secondary zinc electrode negative material, good conductivity, charge acceptance are strong, specific storage is high, have extended cycle life.Chinese patent CN102099297A provides a kind of modified zinc oxide particles: zinc salt and alkali precipitation go out precipitated product and residue after removing polar solvent, in apolar substance, with the carboxylic acid and UV absorption agent with 10 ~ 30 carbon atoms, modification is carried out to it, obtain modification ZnO particle.Chinese patent CN102459471A provides a kind of modified zno nanoparticles: the Zinc oxide nanoparticle be dissolved in solvent is reacted with orthosilicic acid tetraalkyl ester and optional organosilane under ammonia or amine exist, to be this reaction be less than 5 % by weight times at water-content relative to the total amount of solvent and water to condition carries out, thus obtain a kind of Si-O-of comprising alkyl and can be dissolved in the modified oxidized zinc nanoparticles in organic solvent.Japanese Patent JP2008280202 (A) provides a kind of method of surface of nanometer zinc oxide modification: use general formula is R
asiX
(4 ~ a)(wherein R is the organo-functional group containing 1 ~ 18 carbon, X represents hydrolysable group, a is 1,2 or 3) silicon-containing compound surface modification is carried out to the zinc oxide fine particle that median size is 0.5 ~ 20nm, can be steady in a long-term and be dispersed in solution and resin through modified zinc oxide.Japanese Patent JP2008266050 (A) provides a kind of method of surface of nanometer zinc oxide modification: use containing organic carboxyl acids more than 8 carbon (when 25 DEG C, it is minimum dissolving 5 weight part in the fatty alcohol of 100 weight part boiling point more than 100 DEG C) surface modification is carried out to the zinc oxide fine particle that median size is 0.5 ~ 20nm, can be dispersed in resin through modified zinc oxide and not reunite.Japanese Patent JP7069627 (A), JP7069628 (A), JP7069630 (A), JP7069629 (A) each provide a kind of Zinc oxide powder excellent through the dispersiveness of ketone, ester class, amine, alcohols material modification.Above patent is all use small-molecule substance, and as coupling agent, carboxylic acid, ketone, amine, alcohol, ester carry out surface modification to zinc oxide, for improving, the dispersiveness of zinc oxide in solution system (as coating) is fruitful.And solid rubber has very high molecular weight, use above-mentioned small-molecule substance modified zinc oxide, although can improve the dispersiveness of zinc oxide in rubber to a certain extent, the difference on molecular weight has been doomed the validity of this modification mode and permanence have certain limitation.
At present, lack a kind of high dispersive zinc oxide truly, it has good dispersiveness in rubber-like high molecular polymer, and can improve the over-all properties of goods, especially wear resisting property.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of good dispersity, high dispersive zinc oxide that wear resistance is good and preparation method thereof.
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, and described high dispersive zinc oxide comprises following component by weight:
100 parts, zinc oxide,
Zinc acrylate resin 14 ~ 29 parts,
5 ~ 123 parts, dry glue.
The preparation method of high dispersive zinc oxide of the present invention, comprises the steps:
(1) add in ammonia soln by vinylformic acid, stir and make it in the solution dispersed, the mass percentage that vinylformic acid accounts for solution is 1.2% ~ 6%, and the mass percentage that ammoniacal liquor accounts for solution is 20% ~ 50%;
(2) add in solution of zinc sulfate by rubber latex, stir and make it in the solution dispersed, the mass percentage that dry glue accounts for solution is 0.5% ~ 21%, and the mass percentage that zinc sulfate accounts for solution is 20% ~ 35%;
(3) under constantly stirring, two kinds of solution of step (1) and step (2) are mixed, mixing solutions ammoniacal liquor adjust ph, continue stirring reaction, after reaction terminates, carry out centrifugation;
(4) after isolated filter cake drying, in mixing machine, original position bulk polymerization is carried out with the alcohol dilution liquid of Diisopropyl azodicarboxylate while hot, obtained high dispersive zinc oxide;
(5) isolated filtrate and calcium hydroxide carry out water-bath, the calcium sulfate be obtained by reacting through centrifugal, dry, the NH discharged
3recycle.
Further, in step (3), under constantly stirring, two kinds of solution of step (1) and step (2) are mixed, mixing solutions ammoniacal liquor adjust ph is after 10 ~ 12, continue stirring reaction 20 ~ 300min, stir speed (S.S.) is 100 ~ 800r/min, carries out centrifugation after reaction terminates;
In step (4), after isolated filter cake drying, in high-speed mixer, carry out original position bulk polymerization with the alcohol dilution liquid of Diisopropyl azodicarboxylate while hot, temperature of reaction controls at 80 ~ 130 DEG C, and the reaction times is 2 ~ 6h;
In step (5), isolated filtrate and calcium hydroxide carry out water-bath, and the calcium sulfate be obtained by reacting needs centrifugal, oven dry, reacts the NH discharged
3recycle.
Further, in step (2), described rubber latex is selected from one or both the combination in natural rubber latex and styrene-butadiene latex.
Further, in step (4), the alcohol dilution liquid of described Diisopropyl azodicarboxylate is dissolved in ethanol by Diisopropyl azodicarboxylate, and the mass ratio of Diisopropyl azodicarboxylate and ethanol is 1:10 ~ 1:20.
Beneficial effect: the present invention prepares a kind of high dispersive zinc oxide by simple, easy method, and whole process produces without " three wastes ", belongs to cleanly production.Vinylformic acid is combined with zinc oxide by ionic linkage, and under the initiation of Diisopropyl azodicarboxylate, the double bond in the double bond in its molecular structure and dry glue carries out radical polymerization, thus forms firmly polymer modification layer at zinc oxide surface.The product obtained dispersing property in rubber is excellent, and and there is between rubber molecule good consistency, more uniformly play sulfurate activity effect in rubber compounding while, the comprehensive mechanical performance of cross-linked rubber can also be improved, especially wear resisting property.As everyone knows, the wear resistance of tyre surface to sizing material of tire has special requirement, the dispersiveness of air retaining wall to vulcanization system auxiliary agent (comprising sulphur, promotor and zinc oxide) has special requirement, the performance advantage of the high dispersive zinc oxide that the present invention obtains, makes it be more suitable for tyre surface for tire and airtight layer formula.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of embodiments of the invention 1 products therefrom;
Fig. 2 is that embodiments of the invention 1 gained high dispersive zinc oxide is added in sizing material, the photo of the amplification 400 times using separating apparatus to collect;
Fig. 3 is that comparative example gained indirect process zinc oxide of the present invention is added in sizing material, the photo of the amplification 400 times using separating apparatus to collect;
Fig. 4 is the photo that the scanning electronic microscope in the tension fracture face of embodiments of the invention 1 gained high dispersive zinc oxide and rubber composite amplifies 1000 times;
Fig. 5 is the photo that the scanning electronic microscope in the tension fracture face of comparative example gained indirect process zinc oxide of the present invention and rubber composite amplifies 1000 times.
Embodiment
Further illustrate the present invention by the following examples.It should be understood that these embodiments are explaination of the present invention and citing, do not limit the scope of the invention in any form.
Embodiment 1
A kind of high dispersive zinc oxide of the present invention, described high dispersive zinc oxide comprises following component by weight:
100 parts, zinc oxide,
Zinc acrylate resin 14 parts,
5 parts, dry glue (natural rubber).
The preparation method of high dispersive zinc oxide of the present invention, comprises the steps:
(1) add in ammonia soln by vinylformic acid, stir and make it in the solution dispersed, the mass percentage that vinylformic acid accounts for solution is 1.2%, and the mass percentage that ammoniacal liquor accounts for solution is 20%;
(2) add in solution of zinc sulfate by natural rubber latex, stir and make it in the solution dispersed, the mass percentage that natural rubber accounts for solution is 0.5%, and the mass percentage that zinc sulfate accounts for solution is 20%; In described natural rubber latex, the mass percentage of natural rubber is 40%.
(3) under constantly stirring, by two kinds of solution mixing of step (1) and step (2), mixing solutions ammoniacal liquor adjust ph is after 10, continues stirring reaction 20min, stir speed (S.S.) is 100r/min, carries out centrifugation after reaction terminates;
(4) after isolated filter cake drying, in high-speed mixer, carry out original position bulk polymerization with the alcohol dilution liquid of Diisopropyl azodicarboxylate while hot, temperature of reaction controls at 80 DEG C, and the reaction times is 2h, obtained high dispersive zinc oxide; The alcohol dilution liquid of described Diisopropyl azodicarboxylate is dissolved in ethanol by Diisopropyl azodicarboxylate, and the mass ratio of Diisopropyl azodicarboxylate and ethanol is 1:10;
(5) isolated filtrate and calcium hydroxide slurry carry out water-bath, and the calcium sulfate be obtained by reacting, through centrifugal, oven dry, reacts the NH discharged
3recycle.
Embodiment 2
Embodiment 2 is with the difference of embodiment 1:
A kind of high dispersive zinc oxide of the present invention, described high dispersive zinc oxide comprises following component by weight:
100 parts, zinc oxide,
Zinc acrylate resin 29 parts,
123 parts, dry glue (styrene-butadiene rubber(SBR)).
The preparation method of high dispersive zinc oxide of the present invention, comprises the steps:
In step (1), added by vinylformic acid in ammonia soln, stir and make it in the solution dispersed, the mass percentage that vinylformic acid accounts for solution is 6%, and the mass percentage that ammoniacal liquor accounts for solution is 50%;
In step (2), added by styrene-butadiene latex in solution of zinc sulfate, stir and make it in the solution dispersed, the mass percentage that styrene-butadiene rubber(SBR) accounts for solution is 21%, and the mass percentage that zinc sulfate accounts for solution is 35%; In described styrene-butadiene latex, the mass percentage of styrene-butadiene rubber(SBR) is 40%.
In step (3), under constantly stirring, two kinds of solution of step (1) and step (2) are mixed, mixing solutions ammoniacal liquor adjust ph is after 12, continue stirring reaction 300min, stir speed (S.S.) is 800r/min, carries out centrifugation after reaction terminates;
In step (4), after isolated filter cake drying, in high-speed mixer, carry out original position bulk polymerization with the alcohol dilution liquid of Diisopropyl azodicarboxylate while hot, temperature of reaction controls at 130 DEG C, and the reaction times is 6h, obtained high dispersive zinc oxide; The alcohol dilution liquid of described Diisopropyl azodicarboxylate is dissolved in ethanol by Diisopropyl azodicarboxylate, and the mass ratio of Diisopropyl azodicarboxylate and ethanol is 1:20.
Embodiment 3
Embodiment 3 is with the difference of embodiment 1:
A kind of high dispersive zinc oxide of the present invention, described high dispersive zinc oxide comprises following component by weight:
100 parts, zinc oxide,
Zinc acrylate resin 23 parts,
60 parts, dry glue.
Described dry glue is the mixture of natural rubber and styrene-butadiene rubber(SBR).
The preparation method of high dispersive zinc oxide of the present invention, comprises the steps:
In step (1), added by vinylformic acid in ammonia soln, stir and make it in the solution dispersed, the mass percentage that vinylformic acid accounts for solution is 4%, and the mass percentage that ammoniacal liquor accounts for solution is 35%;
In step (2), added by rubber latex in solution of zinc sulfate, stir and make it in the solution dispersed, the mass percentage that dry glue accounts for solution is 15%, and the mass percentage that zinc sulfate accounts for solution is 27%; Described rubber latex is the mixture of natural rubber latex and styrene-butadiene latex, and in two kinds of latex, the mass percentage of dry glue is 40%.
In step (3), under constantly stirring, two kinds of solution of step (1) and step (2) are mixed, mixing solutions ammoniacal liquor adjust ph is after 11, continue stirring reaction 260min, stir speed (S.S.) is 600r/min, carries out centrifugation after reaction terminates;
In step (4), after isolated filter cake drying, in high-speed mixer, carry out original position bulk polymerization with the alcohol dilution liquid of Diisopropyl azodicarboxylate while hot, temperature of reaction controls at 120 DEG C, and the reaction times is 4h, obtained high dispersive zinc oxide; The alcohol dilution liquid of described Diisopropyl azodicarboxylate is dissolved in ethanol by Diisopropyl azodicarboxylate, and the mass ratio of Diisopropyl azodicarboxylate and ethanol is 1:15.
Comparative example
Indirect process zinc oxide is raw material with zinc ingot metal, in plumbago crucible, be converted into zinc fume under the high temperature of 1000 DEG C, generated zinc oxide subsequently by the atmospheric oxidation blasted, and collect after cooling tube and obtain.
Test 1
High dispersive zinc oxide obtained for embodiment 1 is applied in tire tread formula, formula used is: NR100, stearic acid 2, N22045, white carbon black 8, Si690.8, aromatic hydrocarbon oil 5, protection wax 2,4010NA1.5, sulphur 1.2, NOBS1.6, vulcanization leveller (become kind, promoting agent is respectively high dispersive zinc oxide and the indirect process zinc oxide prepared of comparative example prepared by embodiment 1) 4.
In two roller mill, first natural rubber is plasticated, then add various auxiliary agent, obtain rubber unvulcanizate, then at 151 DEG C, carry out sulfuration by sulfurizing time, obtain vulcanized rubber.Test by national standard, gained performance is as shown in table 1.
Table 1
As can be seen from the data of table 1 relatively in: the sizing material adding high dispersive zinc oxide prepared by embodiment 1 has more excellent mechanical property compared with indirect process zinc oxide sizing material, especially the lifting of wear resisting property is more remarkable, and this has fully demonstrated high dispersive zinc oxide and has had higher sulfurate activity compared with indirect process zinc oxide.
Separating apparatus is used to observe the cross section of rubber unvulcanizate: Fig. 2 is that after the high dispersive zinc oxide of embodiment 1 preparation is added on sizing material, rubber unvulcanizate cross section is exaggerated the photo of 400 times; Fig. 3 is after indirect process zinc oxide is added on sizing material, and rubber unvulcanizate cross section is exaggerated the photo of 400 times.Vulcanized rubber, after low-temperature brittle fracture, uses sem observation section situation: Fig. 4 is the section picture of the cross-linked rubber adding high dispersive zinc oxide prepared by embodiment 1; Fig. 5 is the section picture of the cross-linked rubber using indirect process zinc oxide.
Find out from the comparison of Fig. 2 and Fig. 3: the high dispersive zinc oxide Fig. 2 has better dispersiveness compared with the indirect process zinc oxide in Fig. 3.The comparison of Fig. 4 and Fig. 5: the indirect process zinc oxide agglomerate grain in Fig. 5, and have part indirect process zinc oxide exposed; And the consistency of the high dispersive zinc oxide that embodiment 1 obtains and rubber matrix is good, Fig. 4 shows high dispersive zinc oxide and is all coated in rubber matrix, rarely exposes, and it can also be seen that high dispersive zinc oxide is dispersed in rubber from Fig. 4.
More than show and describe ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and application claims protection domain is defined by appending claims, specification sheets and equivalent thereof.
Claims (5)
1. a high dispersive zinc oxide, is characterized in that: described high dispersive zinc oxide comprises following component by weight:
100 parts, zinc oxide,
Zinc acrylate resin 14 ~ 29 parts,
5 ~ 123 parts, dry glue.
2. the preparation method of high dispersive zinc oxide according to claim 1, is characterized in that comprising the steps:
(1) add in ammonia soln by vinylformic acid, stir and make it in the solution dispersed, the mass percentage that vinylformic acid accounts for solution is 1.2% ~ 6%, and the mass percentage that ammoniacal liquor accounts for solution is 20% ~ 50%;
(2) add in solution of zinc sulfate by rubber latex, stir and make it in the solution dispersed, the mass percentage that dry glue accounts for solution is 0.5% ~ 21%, and the mass percentage that zinc sulfate accounts for solution is 20% ~ 35%;
(3) under constantly stirring, two kinds of solution of step (1) and step (2) are mixed, mixing solutions ammoniacal liquor adjust ph, continue stirring reaction, after reaction terminates, carry out centrifugation;
(4) after isolated filter cake drying, in mixing machine, original position bulk polymerization is carried out with the alcohol dilution liquid of Diisopropyl azodicarboxylate while hot, obtained high dispersive zinc oxide;
(5) isolated filtrate and calcium hydroxide carry out water-bath, the calcium sulfate be obtained by reacting through centrifugal, dry, the NH discharged
3recycle.
3. the preparation method of high dispersive zinc oxide according to claim 2, is characterized in that:
In step (3), under constantly stirring, two kinds of solution of step (1) and step (2) are mixed, mixing solutions ammoniacal liquor adjust ph is after 10 ~ 12, continue stirring reaction 20 ~ 300min, stir speed (S.S.) is 100 ~ 800r/min, carries out centrifugation after reaction terminates;
In step (4), after isolated filter cake drying, in high-speed mixer, carry out original position bulk polymerization with the alcohol dilution liquid of Diisopropyl azodicarboxylate while hot, temperature of reaction controls at 80 ~ 130 DEG C, and the reaction times is 2 ~ 6h;
In step (5), isolated filtrate and calcium hydroxide carry out water-bath, and the calcium sulfate be obtained by reacting needs centrifugal, oven dry, reacts the NH discharged
3recycle.
4. the preparation method of the high dispersive zinc oxide according to Claims 2 or 3, is characterized in that: in step (2), and described rubber latex is selected from one or both the combination in natural rubber latex and styrene-butadiene latex.
5. the preparation method of the high dispersive zinc oxide according to Claims 2 or 3, it is characterized in that: in step (4), the alcohol dilution liquid of described Diisopropyl azodicarboxylate is dissolved in ethanol by Diisopropyl azodicarboxylate, and the mass ratio of Diisopropyl azodicarboxylate and 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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| 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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