CN111607124B - Calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material and preparation method thereof - Google Patents
Calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material and a preparation method thereof. The main components of the composite material consist of calcium-doped zinc-aluminum hydrotalcite, zinc oxide and basic zinc chloride. The preparation method comprises the following steps: the preparation method comprises the steps of preparing a zinc hydroxide filter cake containing basic zinc chloride, preparing calcium-doped zinc-aluminum hydrotalcite-like compound and preparing a calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material. The calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material prepared by the invention can be used as a rubber vulcanization accelerator to replace a zinc oxide product.
Description
Technical Field
The invention belongs to the technical field of composite materials, and relates to a calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material and a preparation method thereof.
Background
The hydrotalcite layered compound is an anionic clay which develops rapidly in recent years, is a layered column compound which is formed by a brucite layered structure with positive charges and anions with negative charges filled between layers, and has wide application range. It has a layered structure, except that the skeleton is cation, the interlayer is anion, the alkali is displayed, and the interlayer distance can be adjusted by filling anions with different ionic radii. Since their main components are generally composed of Hydroxides of two metals, they are also called Layered Double Hydroxides (LDHs). Relatively common LDHs of Mg/Al components, called hydrotalcite; mg in LDHs2+、A13+By other M2+、M3+Isomorphous substitution to obtain hydrotalcite compounds with similar structures, which have the following chemical composition general formula: [ M ] A2+ 1-xM3+ x(OH)2]z+[An-]z/n·mH2O, structure is the same as hydrotalcite, except that the number of anion and cation species is different. Other components of LDHs may also be referred to as hydrotalcite-like compounds. Hydrotalcites and hydrotalcite-like compounds are collectively referred to as hydrotalcite-like materials. Can be used for modulating metal ionsAnd anion species, size and the like, and change the chemical and physical properties of the hydrotalcite layered compound, thereby preparing materials with different properties.
Hydrotalcite like materials have the following basic properties: (1) a special layered structure. The crystal field is seriously asymmetric, cations are in crystal lattices on the laminated plate, anions are not in the crystal lattices, and the cations are arranged between layers outside the crystal lattices; (2) and (3) alkalinity. The alkalinity of HTLcs is related to the property of cations M on the laminate and the property of MO bonds; (3) and (4) acidity. The acidity of HTLcs is not only related to the acidity of the metal ions on the laminates, but also to the interlayer anions; (4) and (4) structural stability. In addition, the hydrotalcite has the characteristics of anion exchangeability, adjustable pore diameter, multiple plate layer element compositions and the like because the hydrotalcite shows special properties on chemistry and structure. The hydrotalcite has unique structural characteristics, so that the hydrotalcite can be applied to the traditional fields of catalysts, catalyst carriers, adsorbents, ion exchangers and the like, and can also play a role of a heat stabilizer in a high polymer material.
In a rubber sulfur vulcanization system, zinc oxide is mainly used as a vulcanization activator, the function of the zinc oxide is to fully play the role of an organic accelerator, the using amount of the accelerator is reduced or the vulcanization time is shortened, and meanwhile, the zinc oxide can also reduce heat generation and improve the wear resistance of tires. In recent years, reducing the zinc oxide content of rubber compounds has become an important issue. During the production of rubber, the handling of rubber articles and recycling, zinc is released from the rubber to the environment. And may be released by wear of the tire during use. The release of zinc can have adverse effects on the environment, human health and in particular on aquatic organisms, and according to eu directive 2003/105/EC, zinc oxide is classified into N classes, i.e. harmful substances to the environment, "R50/53" is toxic to organisms in water and can cause long-term damage to the water environment. Traditionally, typical formulations of sulfur vulcanizates contain 3-5 parts zinc oxide. The nano zinc oxide has high physical and chemical reaction activity due to large specific surface area, and can be used in a reduced amount in a rubber formula compared with common zinc oxide. However, the nano zinc oxide has fine particles and large specific surface area, is easy to generate static electricity and agglomerate, and particularly in the process of rubber mixing, the nano zinc oxide is easy to cause uneven dispersion, thereby influencing the mechanical property of rubber materials. The hydrotalcite material has special performances of catalysis, adsorption, ion exchange, carrier, thermal stability and the like, can partially replace the function of zinc oxide in a rubber vulcanization system, has a special flaky structure and organic groups, has a higher specific surface area and cannot agglomerate, and simultaneously the organic groups and the rubber groups are well compatible, so that the hydrotalcite material can be used as an effective separant and a processing aid of the nano zinc oxide and can prevent the phenomenon of uneven dispersion in the mixing process of the nano zinc oxide rubber. The hydrotalcite with a certain structure is compounded with the nano zinc oxide to be used as a vulcanization activator, so that the using amount of the zinc oxide can be effectively reduced.
Disclosure of Invention
Based on the problems in the prior art, the invention aims to provide a calcium-doped zinc-aluminum hydrotalcite-like composite material, and a preparation method and application thereof.
In order to solve the technical problems, on one hand, the invention provides a calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material, which comprises the following components in parts by weight:
40 to 60 percent of calcium-doped zinc-aluminum hydrotalcite, 32 to 55 percent of zinc oxide and 0.1 to 8 percent of basic zinc chloride.
On the other hand, the invention also provides a preparation method of the calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material, which comprises the following steps:
(1) dissolving zinc chloride in water according to a stoichiometric relation under the condition of continuously stirring to prepare a zinc chloride solution;
(2) under the condition of continuously stirring, dissolving calcium hydroxide or sodium hydroxide in water according to the stoichiometric relation to prepare calcium hydroxide slurry or sodium hydroxide solution; adding a certain amount of dispersant into the calcium hydroxide slurry or the sodium hydroxide solution;
(3) adding the prepared zinc chloride solution into the calcium hydroxide slurry or the sodium hydroxide solution under the condition of continuous stirring, controlling the feeding condition and speed, reacting the zinc chloride with the calcium hydroxide or the sodium hydroxide to form white zinc hydroxide precipitate, a small part of basic zinc chloride precipitate and chloride, controlling the pH value of the final solution to be neutral to alkaline, and continuously stirring for a period of time until the reaction is complete; filtering the slurry, washing the filter cake with deionized water for several times, and filtering to obtain a zinc hydroxide filter cake containing basic zinc chloride;
(4) weighing a certain amount of the zinc hydroxide filter cake obtained in the step (3), a certain amount of aluminum hydroxide powder and organic acid according to a certain stoichiometric proportion relation, dissolving the zinc hydroxide filter cake, the aluminum hydroxide powder and the organic acid in water, preparing mixed slurry under a stirring state according to the stoichiometric proportion of calcium ions, zinc ions and aluminum ions, placing the mixed slurry in a ball mill, adding a grinding dispersant, and performing mechanical blending chemical reaction on the zinc hydroxide and the aluminum hydroxide and excessive organic acid under the grinding state to form mixed slurry containing organic acid zinc and organic acid aluminum;
(5) dissolving a certain amount of calcium hydroxide powder in water to prepare calcium hydroxide slurry, adding the calcium hydroxide slurry into the mixed slurry of organic acid zinc and organic acid aluminum in the step (4), continuously reacting the calcium hydroxide with the residual organic acid under the grinding condition, adjusting the pH of the mixed solution to be neutral to alkaline by using the calcium hydroxide, and grinding until the reaction is complete to obtain grinding slurry;
(6) aging the grinding slurry obtained in the step (5) at a certain temperature, further crystallizing, arranging and assembling to obtain calcium-doped zinc-aluminum hydrotalcite-like slurry;
(7) dissolving a certain amount of the zinc hydroxide filter cake obtained in the step (3) in a certain amount of water to prepare zinc hydroxide slurry, adding the zinc hydroxide slurry into the calcium-doped zinc-aluminum hydrotalcite mixed slurry prepared in the step (6), fully stirring and mixing to form uniform mixed slurry, filtering, separating and drying the slurry to obtain the calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material.
In the above preparation method, preferably, in the step (1), the zinc chloride is dissolved in water under a constant stirring state according to a stoichiometric relationship to prepare a uniform zinc chloride solution, and the concentration of the zinc chloride solution is 20% to 40%.
In the above preparation method, preferably, in the step (2), calcium hydroxide or sodium hydroxide is dissolved in water according to a stoichiometric relationship under a continuously stirring state to prepare a uniform calcium hydroxide slurry or sodium hydroxide solution with a concentration of 10% to 30%.
In the preparation method, preferably, in the step (2), the dispersing agent includes one or more of sodium alkyl benzene sulfonate, sodium alkyl sulfate, sodium fatty alcohol-polyoxyethylene ether sulfate, fatty alcohol-polyoxyethylene ether, alkylphenol ethoxylate, sodium polyacrylate, polyethylene glycol, sodium polycarboxylate and sodium polyglucoside.
In the above preparation method, preferably, the addition amount of the dispersant is 0.1% to 1.0% of the total amount of the reaction precipitation product.
In the preparation method, preferably, in the step (3), zinc chloride reacts with calcium hydroxide or sodium hydroxide to form white zinc hydroxide precipitate, a small part of basic zinc chloride precipitate and chloride salt, and the pH value of the final solution is controlled to be 7-11; continuously stirring and reacting for 20-60 min at the speed of 100-1500 r/min until the reaction is complete, filtering the slurry, washing the filter cake with deionized water for at least three times, and filtering to obtain a zinc hydroxide filter cake containing basic zinc chloride; in the reaction process, reaction conditions are controlled, so that the ratio of the solid content of the final zinc hydroxide filter cake to the basic zinc chloride content is 1 (0.02-0.15).
In the above production method, preferably, in the step (3), the reaction conditions are controlled so that the particle diameter of the reaction product is less than 25 μm.
In the above preparation method, preferably, in the step (4), the zinc hydroxide filter cake, the aluminum hydroxide powder and the calcium hydroxide powder are used in a certain ratio, wherein x (Ca)2+)：x(Zn2+) Is 1 to 3, x (Zn)2++Ca2+)：x(Al3+) Is 2-6, and x represents the molar weight of ions.
In the above preparation method, preferably, in the step (4), the organic acid is solid organic acid powder, and the amount of the solid organic acid powder is the sum of the calcium ions, the zinc ions and the aluminum ions, and the organic acid comprises one or more of succinic acid, adipic acid, dodecyl sulfonic acid, p-tert-butyl benzoic acid, p-hydroxybenzoic acid, benzoic acid, terephthalic acid, sebacic acid, stearic acid, tartaric acid, aspartic acid, myristic acid and the like.
In the above production method, preferably, in the step (4), the particle diameters of the aluminum hydroxide powder and the calcium hydroxide powder are 400 meshes or more.
In the above preparation method, preferably, in the step (4), the zinc hydroxide filter cake, the aluminum hydroxide powder and the organic acid are dissolved in water, and 20% to 30% of mixed slurry is prepared under a stirring state; and (2) placing the mixed slurry into a ball mill, adding a grinding dispersion liquid, wherein the dosage of the grinding dispersion liquid is 0.1% -0.7% of the total solid content, and under a grinding state, performing mechanical stirring, blending and chemical reaction on zinc hydroxide and aluminum hydroxide and excessive organic acid for 30-60 min to form mixed slurry containing organic acid zinc and organic acid aluminum.
In the preparation method, preferably, in the step (5), a certain amount of calcium hydroxide powder is dissolved in water to prepare 20% -30% calcium hydroxide slurry, the calcium hydroxide slurry is added into the mixed slurry of organic acid zinc and organic acid aluminum in the step (4), under the grinding condition, the calcium hydroxide continuously reacts with the residual organic acid, the pH value of the mixed solution is adjusted to 7-11 by the calcium hydroxide, and grinding is carried out for 30-60 min until the reaction is complete.
In the preparation method, preferably, in the step (6), the grinding slurry is aged for 2-24 hours at 40-100 ℃, and further crystallized, arranged and assembled to obtain the calcium-doped zinc-aluminum hydrotalcite-like slurry.
In the preparation method, preferably, in the step (7), a certain amount of the zinc hydroxide filter cake in the step (3) is dissolved in a certain amount of water to prepare zinc hydroxide slurry with a solid content of 20-30%, the zinc hydroxide slurry is added into the calcium-doped zinc-aluminum hydrotalcite mixed slurry prepared in the step (6), the calcium-doped zinc-aluminum hydrotalcite accounts for 33-53% and the zinc hydroxide and the basic zinc chloride account for 47-67% according to the solid content, the calcium-doped zinc-aluminum hydrotalcite and the basic zinc chloride are fully stirred and mixed to form uniform mixed slurry, the stirring speed is 300-1800 r/min, and the stirring time is 30-180 min.
In the preparation method, preferably, in the step (7), the slurry mixture of the calcium-doped zinc-aluminum hydrotalcite, the zinc hydroxide and the basic zinc chloride which are fully and uniformly mixed is filtered and separated, and the obtained filter cake is dried at 130-180 ℃ to obtain the calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material.
On the other hand, the invention also provides the application of the calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material as a rubber vulcanization activator.
The invention has the beneficial effects that:
compared with the prior art, the invention adopts the reaction of calcium hydroxide and zinc chloride to prepare and generate nano zinc hydroxide, and the concentrated solution of the zinc chloride has obvious acidity due to the generation of complex acid, namely hydroxy zinc dichloride acid, and can react with the zinc hydroxide to generate water-insoluble basic zinc chloride.
ZnCl2+H2O＝＝＝H[ZnCl2(OH)]
Ca(OH)2+2H[ZnCl2(OH)]＝＝＝Ca[ZnCl2(OH)]2+3H2O
4Zn(OH)2+H[ZnCl2(OH)]＝＝＝Zn5Cl2(OH)8+H2O
By controlling the feeding conditions, a small amount of basic zinc chloride can be generated in the reaction process of calcium hydroxide and zinc chloride, in the calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material, the nano zinc oxide is uniformly loaded on the small amount of basic zinc chloride, the agglomeration of the nano zinc oxide can be reduced, and in the rubber mixing process, compared with the zinc oxide, the basic zinc chloride can more easily form zinc ions, hydroxide ions and chloride ions, and the zinc ions, the hydroxide ions and the chloride ions are further dispersed under the mechanical shearing action of an internal mixer. Therefore, along with the dissociation of the basic zinc chloride, the agglomeration of the nano zinc oxide loaded on the basic zinc chloride is correspondingly reduced, so that the nano zinc oxide using the basic zinc chloride as a carrier has high chemical activity and good dispersibility, and the activity of zinc ions is higher than that of the nano zinc oxide, so that the good performance of the product can be ensured under the condition of reduced use.
In addition, in the calcium-doped zinc-aluminum-like hydrotalcite, the ionic radius of calcium ions is large, the molecular weight of organic acid is large, so that the hydrotalcite-like interlayer distance is large, the hydrotalcite-like interlayer distance has a high specific surface area, small molecules can be effectively adsorbed, and the calcium, zinc and aluminum three elements have a better synergistic effect, so that chloride ions liberated from basic zinc chloride can be effectively absorbed, and the influence of the chloride ions on the thermal stability of rubber is prevented. The calcium-doped zinc-aluminum hydrotalcite has the functions of effective catalysis, adsorption, ion exchange, carrier, thermal stability and the like, so that the usage amount of zinc oxide can be further reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail below. However, it will be appreciated by those of ordinary skill in the art that numerous technical details are set forth in order to provide a better understanding of the present invention in its various embodiments. However, the technical solutions claimed in the present invention can be implemented without these technical details and various changes and modifications based on the following embodiments.
Example 1:
the embodiment provides a preparation method of a calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material, which comprises the following specific steps:
(1) under the condition of continuously stirring, 184.2g of zinc chloride is dissolved in 430g of water to prepare a transparent zinc chloride solution with the concentration of about 30 percent;
(2) 81.3g of calcium hydroxide was dissolved in 243g of water under stirring to prepare a white calcium hydroxide slurry of about 25%, and 0.5g of sodium dodecylbenzenesulfonate surfactant was added to the calcium hydroxide slurry.
(3) Slowly adding the zinc chloride solution prepared in the step (1) into the calcium hydroxide slurry obtained in the step (2) under the condition of continuous stirring, stirring at the rotating speed of 600r/min, reacting zinc chloride with calcium hydroxide to form calcium chloride, white zinc hydroxide precipitate and a small part of basic zinc chloride precipitate, controlling the pH value of the final solution to be 10, continuously stirring until the reaction is complete to obtain mixed slurry of calcium chloride, zinc hydroxide and basic zinc chloride, filtering the slurry, washing the slurry with deionized water for several times, filtering to obtain a zinc hydroxide filter cake, and measuring the solid content of the zinc hydroxide filter cake for later use.
(4) Dissolving the zinc hydroxide filter cake with the solid content of 8.9g, the aluminum hydroxide powder of 7.0g and the stearic acid of 89g in the step (3) in water of 314g to prepare mixed slurry with the solid content of 25 percent, placing the mixed slurry in a ball mill, adding 0.5g of grinding agent, grinding for 60min at the rotating speed of 1500r/min, and carrying out mechanical blending chemical reaction on the zinc hydroxide and the aluminum hydroxide and excessive organic acid under the grinding state to form mixed slurry containing the zinc aluminate and the aluminum aluminate;
(5) dissolving 6g of calcium hydroxide in 25.2g of water to prepare 25% mixed slurry, adding the calcium hydroxide slurry into the mixed slurry of organic acid zinc and organic acid aluminum in the step (4), continuously reacting the calcium hydroxide with the rest organic acid under the grinding condition, adjusting the pH value to 10 by using the calcium hydroxide, and continuously grinding for 30min until the reaction is complete;
(6) aging the grinding slurry obtained in the step (5) at 80 ℃ for 8h, and further crystallizing, arranging and assembling to obtain calcium-doped zinc-aluminum hydrotalcite-like slurry;
(7) dissolving a certain amount of the zinc hydroxide filter cake obtained in the step (3) in a certain amount of water to prepare 25% zinc hydroxide slurry, mixing the calcium-doped zinc-aluminum hydrotalcite-like compound mixed slurry with a solid content of 45g obtained in the step (6) with zinc hydroxide with a solid content of 60g, fully stirring and mixing to form uniform mixed slurry, filtering and separating the slurry, and drying at 150 ℃ to obtain the calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material.
Example 2:
the embodiment provides a preparation method of a calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material, which comprises the following specific steps:
(1) under the condition of continuously stirring, 184.2g of zinc chloride is dissolved in water to prepare a transparent zinc chloride solution with the concentration of about 25 percent;
(2) 87.89g of sodium hydroxide is dissolved in 263g of water under continuous stirring to prepare a sodium hydroxide solution with the concentration of about 25 percent, and 0.5g of sodium dodecyl benzene sulfonate surfactant is added into the sodium hydroxide solution.
(3) And (2) slowly adding the zinc chloride solution prepared in the step (1) into the sodium hydroxide solution obtained in the step (2) under the condition of continuous stirring, stirring at the rotating speed of 600r/min, reacting the zinc chloride with the sodium hydroxide to form sodium chloride, white zinc hydroxide precipitate and a small part of basic zinc chloride precipitate, controlling the pH value of the final solution to be 9, continuously stirring until the reaction is complete, filtering the slurry, washing the slurry with deionized water for a plurality of times, filtering to obtain a zinc hydroxide filter cake, and measuring the solid content of the zinc hydroxide filter cake for later use.
(4) Weighing the zinc hydroxide filter cake with the solid content of 8.4g, the aluminum hydroxide powder of 13.0g and the terephthalic acid of 83g in the step (3), dissolving in 249g of water to prepare 25 percent mixed slurry, placing the mixed slurry in a ball mill, adding 0.5g of grinding agent, grinding for 60min at the rotating speed of 1200r/min, and carrying out mechanical blending chemical reaction on the zinc hydroxide and the aluminum hydroxide and excessive organic acid under the grinding state to form mixed slurry containing the zinc aluminate and the aluminum aluminate;
(5) dissolving 12.3g of calcium hydroxide in 37g of water to prepare 25% mixed slurry, adding the calcium hydroxide slurry into the mixed slurry of organic acid zinc and organic acid aluminum in the step (4), continuously reacting the calcium hydroxide with the residual organic acid under the grinding condition, adjusting the pH value to 9 by using the calcium hydroxide, and continuously stirring and reacting for 30min at the rotating speed of 1200r/min until the reaction is complete;
(6) aging the grinding slurry obtained in the step (5) at 80 ℃ for 8h, and further crystallizing, arranging and assembling to obtain calcium-doped zinc-aluminum hydrotalcite-like slurry;
(7) dissolving a certain amount of the zinc hydroxide filter cake obtained in the step (3) in a certain amount of water to prepare 25% zinc hydroxide slurry, mixing the calcium-doped zinc-aluminum hydrotalcite-like compound mixed slurry with a solid content of 45g obtained in the step (6) with a zinc hydroxide filter cake with a solid content of 60g, fully stirring and mixing to form uniform mixed slurry, filtering and separating the slurry, and drying at 180 ℃ to obtain the calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material.
Example 3:
the embodiment provides a preparation method of a calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material, which comprises the following specific steps:
(1) under the condition of continuously stirring, 184.2g of zinc chloride is dissolved in water to prepare a transparent zinc chloride solution with the concentration of about 25 percent;
(2) under the condition of continuously stirring, 81.3g of calcium hydroxide is dissolved in water to prepare about 25% white calcium hydroxide slurry, and 0.3g of sodium dodecyl benzene sulfonate surfactant and 0.2g of fatty alcohol-polyoxyethylene ether are added into the calcium hydroxide slurry.
(3) Slowly adding the zinc chloride solution prepared in the step (1) into the calcium hydroxide slurry obtained in the step (2) under the condition of continuous stirring, stirring at the rotating speed of 600r/min, reacting zinc chloride with calcium hydroxide to form calcium chloride, white zinc hydroxide precipitate and a small part of basic zinc chloride precipitate, controlling the pH value of the final solution to be 10, continuously stirring for 60min to obtain mixed slurry of calcium chloride and zinc hydroxide, filtering the slurry, washing the slurry with deionized water for several times, filtering to obtain a zinc hydroxide filter cake, and measuring the solid content of the zinc hydroxide filter cake for later use.
(4) Dissolving the zinc hydroxide filter cake with the solid content of 7.3g, the aluminum hydroxide powder of 5.7g and the p-tert-butylbenzoic acid of 91g in 311.7g of water in the step (3) to prepare 25% mixed slurry, adding 0.3g of grinding agent, placing the mixed slurry in a ball mill, stirring at the rotating speed of 1500r/min, grinding for 60min, and carrying out mechanical blending chemical reaction on the zinc hydroxide and the aluminum hydroxide and excessive organic acid under the grinding state to form mixed slurry containing the organic acid zinc and the organic acid aluminum;
(5) dissolving 5.4g of calcium hydroxide in 16.2g of water to prepare 25% mixed slurry, adding the calcium hydroxide slurry into the mixed slurry of the zinc p-tert-butylbenzoate and the aluminum p-tert-butylbenzoate in the step (4), continuously reacting the calcium hydroxide with the rest of the p-tert-butylbenzoate under a grinding condition, adjusting the pH value to 10 by using the calcium hydroxide, and continuously stirring and reacting for 30min at the rotating speed of 1500r/min until the reaction is complete;
(6) aging the grinding slurry obtained in the step (5) at 80 ℃ for 8h, and further crystallizing, arranging and assembling to obtain calcium-doped zinc-aluminum hydrotalcite-like slurry;
(7) dissolving a certain amount of the zinc hydroxide filter cake obtained in the step (3) in a certain amount of water to prepare about 25% zinc hydroxide slurry, mixing the calcium-doped zinc-aluminum hydrotalcite mixed slurry prepared in the step (6) with the solid content of 45g with the zinc hydroxide filter cake with the solid content of 60g, fully stirring and mixing at the stirring speed of 600r/min to form uniform mixed slurry, filtering and separating the slurry, and drying at 150 ℃ to obtain the calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material.
After the calcium-doped zinc aluminum hydrotalcite-nano zinc oxide composite material obtained from example 1, example 2 and example 3 and the indirect zinc oxide (a control group using the conventional indirect zinc oxide) are added to the rubber, the rubber formulation is shown in the following table 1, and the rubber performance comparison is shown in the following tables 2 to 4:
table 1: rubber formula
Table 2: vulcanization Performance comparative data
| Name of the sizing material | Set temperature | ML | MH | T10 | T90 |
| Conventional sample | 151℃ | 1.54 | 18.11 | 2:48 | 5:55 |
| Example 1 | 151℃ | 1.84 | 19.34 | 3:14 | 6:34 |
| Example 2 | 151℃ | 1.71 | 17.99 | 2:59 | 6:01 |
| Example 3 | 151℃ | 1.93 | 19.65 | 3:21 | 6:21 |
Table 3: mechanical property comparison data
Table 4: hot air aging Performance test data (aging conditions: 100 ℃ C.. times.24 h)
As can be seen from the experimental data in tables 2 to 4, the samples added with the vulcanization activator of the calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material have almost the same performances as the rubber samples added with the indirect zinc oxide in terms of vulcanization performance, mechanical properties and hot air aging performance, so that the samples can be used for rubber processing instead of the indirect zinc oxide.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (15)
1. The calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material is characterized by comprising the following components in parts by weight:
40-60% of calcium-doped zinc-aluminum hydrotalcite, 32-55% of zinc oxide and 0.1-8% of basic zinc chloride.
2. The preparation method of the calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material according to claim 1, which is characterized by comprising the following steps:
(1) dissolving zinc chloride in water according to a stoichiometric relation under the condition of continuously stirring to prepare a zinc chloride solution;
(2) under the condition of continuously stirring, dissolving calcium hydroxide or sodium hydroxide into water according to the stoichiometric relation to prepare calcium hydroxide slurry or sodium hydroxide solution; adding a certain amount of dispersant into the calcium hydroxide slurry or the sodium hydroxide solution;
(3) adding the prepared zinc chloride solution into the calcium hydroxide slurry or the sodium hydroxide solution under the condition of continuous stirring, controlling the feeding condition and speed, reacting the zinc chloride with the calcium hydroxide or the sodium hydroxide to generate white zinc hydroxide precipitate, a small part of basic zinc chloride precipitate and chloride, controlling the pH value of the final solution to be neutral to alkaline, and continuously stirring for a period of time until the reaction is complete; filtering the slurry, washing the filter cake with deionized water for several times, and filtering to obtain a zinc hydroxide filter cake containing basic zinc chloride;
(4) weighing a certain amount of the zinc hydroxide filter cake obtained in the step (3), a certain amount of aluminum hydroxide powder and organic acid according to a certain stoichiometric relation, dissolving the zinc hydroxide filter cake, the aluminum hydroxide powder and the organic acid in water, preparing mixed slurry under a stirring state according to the stoichiometric proportion of calcium ions, zinc ions and aluminum ions, placing the mixed slurry in a ball mill, adding a grinding dispersant, and performing mechanical blending chemical reaction on the zinc hydroxide and the aluminum hydroxide and excessive organic acid under the grinding state to form mixed slurry containing organic acid zinc and organic acid aluminum;
(5) dissolving a certain amount of calcium hydroxide powder in water to prepare calcium hydroxide slurry, adding the calcium hydroxide slurry into the mixed slurry of organic acid zinc and organic acid aluminum in the step (4), continuously reacting the calcium hydroxide with the residual organic acid under the grinding condition, adjusting the pH of the mixed solution to be neutral to alkaline by using the calcium hydroxide, and grinding until the reaction is complete to obtain grinding slurry;
(6) aging the grinding slurry obtained in the step (5) at a certain temperature, further crystallizing, arranging and assembling to obtain calcium-doped zinc-aluminum hydrotalcite-like slurry;
(7) dissolving a certain amount of the zinc hydroxide filter cake obtained in the step (3) in a certain amount of water to prepare zinc hydroxide slurry, adding the zinc hydroxide slurry into the calcium-doped zinc-aluminum hydrotalcite mixed slurry prepared in the step (6), fully stirring and mixing to form uniform mixed slurry, filtering, separating and drying the slurry to obtain the calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material.
3. The method of claim 2, wherein: in the step (1), zinc chloride is dissolved in water according to the stoichiometric relation under the condition of continuous stirring to prepare a uniform zinc chloride solution, and the concentration of the zinc chloride solution is 20-40%.
4. The method of claim 2, wherein: in the step (2), calcium hydroxide or sodium hydroxide is dissolved in water according to the stoichiometric relation under the condition of continuous stirring to prepare uniform calcium hydroxide slurry or sodium hydroxide solution, and the concentration of the calcium hydroxide slurry or the sodium hydroxide is 10-30%.
5. The method of claim 2, wherein: in the step (2), the dispersing agent comprises one or more of sodium alkyl benzene sulfonate, sodium alkyl sulfate, sodium fatty alcohol-polyoxyethylene ether sulfate, fatty alcohol-polyoxyethylene ether, alkylphenol ethoxylate, sodium polyacrylate, polyethylene glycol, sodium polycarboxylate and sodium polyglucoside.
6. The method of claim 5, wherein: the addition amount of the dispersant is 0.1-1.0% of the total amount of the reaction precipitate.
7. The method of claim 2, wherein: in the step (3), zinc chloride reacts with calcium hydroxide or sodium hydroxide to form white zinc hydroxide precipitate, a small part of basic zinc chloride precipitate and chloride salt, and the pH value of the final solution is controlled to be 7-11; continuously stirring and reacting for 20-60 min at the speed of 100-1500 r/min until the reaction is complete, filtering the slurry, washing the filter cake with deionized water for at least three times, and filtering to obtain a zinc hydroxide filter cake containing basic zinc chloride; in the reaction process, reaction conditions are controlled, so that the ratio of the solid content of the final zinc hydroxide filter cake to the basic zinc chloride content is 1 (0.02-0.15).
8. The method for producing according to claim 7, characterized in that: in the step (3), the reaction conditions are controlled so that the particle size of the reaction product is less than 25 microns.
9. The method of claim 2, wherein: in the step (4), the zinc hydroxide cake, the aluminum hydroxide powder and the calcium hydroxide powder are dissolved in a solution formed by dissolving in water, x (Ca)2+)：x(Zn2+) Is 1 to 3, x (Zn)2++Ca2+)：x(Al3+) Is 2-6, and x represents the molar weight of ions.
10. The method of claim 2, wherein: in the step (4), the organic acid is solid organic acid powder, and the dosage of the solid organic acid powder is the sum of the calcium, zinc and aluminum ions according to the proportioning ratio, and the organic acid comprises one or more of succinic acid, adipic acid, dodecyl sulfonic acid, p-tert-butyl benzoic acid, p-hydroxybenzoic acid, benzoic acid, terephthalic acid, sebacic acid, stearic acid, tartaric acid, aspartic acid and myristic acid.
11. The method of claim 2, wherein: in the step (4), the particle size of the aluminum hydroxide powder is 400 meshes or more; in the step (5), the particle size of the calcium hydroxide powder is 400 meshes or more.
12. The method of claim 2, wherein: in the step (4), the zinc hydroxide filter cake, the aluminum hydroxide powder and the organic acid are dissolved in water and are prepared into 20 to 30 percent mixed slurry under the stirring state; placing the mixed slurry into a ball mill, adding grinding dispersion liquid, wherein the using amount of the grinding dispersion liquid is 0.1% -0.7% of the total solid content, and under a grinding state, performing mechanical stirring, blending and chemical reaction on zinc hydroxide and aluminum hydroxide and excessive organic acid for 30-60 min to form mixed slurry containing organic acid zinc and organic acid aluminum;
in the step (5), dissolving a certain amount of calcium hydroxide powder in water to prepare 20-30% calcium hydroxide slurry, adding the calcium hydroxide slurry into the mixed slurry of organic acid zinc and organic acid aluminum in the step (4), continuously reacting the calcium hydroxide with the rest organic acid under the grinding condition, adjusting the pH of the mixed solution to 7-11 by using the calcium hydroxide, and grinding for 30-60 min until the reaction is complete;
in the step (6), the grinding slurry is placed at 40-100 ℃, aged for 2-24 hours, and further crystallized, arranged and assembled to obtain calcium-doped zinc-aluminum hydrotalcite-like slurry.
13. The method of claim 2, wherein: in the step (7), a certain amount of the zinc hydroxide filter cake obtained in the step (3) is dissolved in a certain amount of water to prepare zinc hydroxide slurry with a solid content of 20-30%, the zinc hydroxide slurry is added into the calcium-doped zinc-aluminum hydrotalcite mixed slurry prepared in the step (6), the calcium-doped zinc-aluminum hydrotalcite accounts for 33-53% and the zinc hydroxide and the basic zinc chloride account for 47-67% according to the solid content of the slurry, the calcium-doped zinc-aluminum hydrotalcite and the basic zinc chloride are fully stirred and mixed to form uniform mixed slurry, the stirring speed is 300-1800 r/min, and the stirring time is 30-180 min.
14. The method of claim 2, wherein: in the step (7), the fully and uniformly mixed slurry of the calcium-doped zinc-aluminum hydrotalcite, the zinc hydroxide and the basic zinc chloride is filtered and separated, and the obtained filter cake is dried at the temperature of 130-180 ℃ to obtain the calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material.
15. The use of the calcium-doped zinc aluminum hydrotalcite-nano zinc oxide composite material according to claim 1 as a rubber vulcanization activator.
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