CN111607128A - Preparation method of composite zinc oxide - Google Patents
Preparation method of composite zinc oxide Download PDFInfo
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- CN111607128A CN111607128A CN202010522135.XA CN202010522135A CN111607128A CN 111607128 A CN111607128 A CN 111607128A CN 202010522135 A CN202010522135 A CN 202010522135A CN 111607128 A CN111607128 A CN 111607128A
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- zinc oxide
- calcium terephthalate
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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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
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Abstract
The invention belongs to the technical field of rubber vulcanization activators, and particularly relates to a preparation method of composite zinc oxide. The preparation method of the composite zinc oxide provided by the invention comprises the following steps: mixing zinc oxide, calcium terephthalate and water, and carrying out high-pressure homogenization treatment to obtain a suspension; and drying the turbid liquid to obtain the composite zinc oxide. According to the invention, zinc oxide and calcium terephthalate are attached to the surface of calcium terephthalate under the action of high-pressure homogenization, so that the lipophilicity of the composite zinc oxide is improved.
Description
Technical Field
The invention belongs to the technical field of rubber vulcanization activators, and particularly relates to a preparation method of composite zinc oxide.
Background
The zinc oxide is used as a vulcanization activator in the rubber vulcanization process, so that the rubber vulcanization time can be effectively reduced, the cross-linking density of the rubber is improved, and the scorching time is prolonged to ensure the production safety. With the continuous and intensive research, researchers found that zinc oxide as a vulcanization activator is not completely consumed in the vulcanization process, and a large part of zinc oxide only serves as an inorganic filler in a rubber matrix; as the rubber product is worn away in use, the zinc oxide which is not consumed is released into the environment, and great harm is caused to the growth of animals and plants.
In order to reduce the consumption of zinc oxide, the zinc oxide is mostly replaced by nano zinc oxide with smaller particle size and larger specific surface area in the prior art, but the nano zinc oxide is easy to self-polymerize in the rubber material and is difficult to exert application performance, and the nano zinc oxide needs to be further treated in order to improve the dispersion problem of the nano zinc oxide, and the nano zinc oxide is usually prepared into master batch or subjected to surface modification; when the nano zinc oxide master batch is prepared, a proper carrier is required to be selected according to the property of the rubber material, and the prepared nano zinc oxide master batch has no wide applicability; when the surface of the nano zinc oxide is modified, an organic solvent is required to be added, so that waste water is easily generated, and the environment is affected.
Disclosure of Invention
In view of the above, the invention provides a preparation method of composite zinc oxide, which attaches zinc oxide, calcium terephthalate and water on the surface of calcium terephthalate under the action of high-pressure homogenization, improves the lipophilicity of the composite zinc oxide, promotes the composite zinc oxide to have high dispersibility in rubber, enhances the compatibility of the composite zinc oxide and the rubber, and reduces the dosage of the zinc oxide while ensuring the activity of the composite zinc oxide.
The invention provides a preparation method of composite zinc oxide, which comprises the following steps:
mixing zinc oxide, calcium terephthalate and water, and carrying out high-pressure homogenization treatment to obtain a suspension;
and drying the turbid liquid to obtain the composite zinc oxide.
Preferably, the pressure of the high-pressure homogenizing treatment is 20-100 MPa, and the flow rate is 10-1000L/h.
Preferably, the calcium terephthalate is powder, and the particle size of the calcium terephthalate is 0.1-20 μm.
Preferably, the drying mode is spray drying.
Preferably, the inlet temperature of the spray drying is 190-210 ℃, and the outlet temperature is 90-100 ℃.
Preferably, the mass ratio of the zinc oxide to the water is 0.6-6: 100.
Preferably, the mass ratio of the zinc oxide to the calcium terephthalate is 1-15: 10.
The preparation method of the composite zinc oxide provided by the invention comprises the following steps: mixing zinc oxide, calcium terephthalate and water, and carrying out high-pressure homogenization treatment to obtain a suspension; and drying the turbid liquid to obtain the composite zinc oxide. According to the invention, zinc oxide and calcium terephthalate are uniformly attached to the surface of calcium terephthalate under the action of high-pressure homogenization, so that the lipophilicity of the composite zinc oxide is improved.
Detailed Description
The invention provides a preparation method of composite zinc oxide, which comprises the following steps:
mixing zinc oxide, calcium terephthalate and water, and carrying out high-pressure homogenization treatment to obtain a suspension;
and drying the turbid liquid to obtain the composite zinc oxide.
In the present invention, the raw materials are commercially available products known to those skilled in the art unless otherwise specified.
According to the invention, zinc oxide, calcium terephthalate and water are mixed and subjected to high-pressure homogenization treatment to obtain suspension. In the invention, the calcium terephthalate is preferably powder, and the particle size of the calcium terephthalate is preferably 0.1-20 μm, more preferably 0.3-10 μm, and most preferably 1-8 μm. In the invention, the mass ratio of the zinc oxide to the water is preferably 0.6-6: 100, and more preferably 1-6: 100; the mass ratio of the zinc oxide to the calcium terephthalate is preferably 1-15: 10, more preferably 2-8.18: 10, and most preferably 4-6: 10. The adoption of the calcium terephthalate with the particle size within the range can promote the zinc oxide attached to the surface of the calcium terephthalate to be better dispersed in the rubber.
In the present invention, the mixing is preferably carried out by first mixing zinc oxide with calcium terephthalate to obtain a primary mixture; then mixing the primary mixture with water and then carrying out high-pressure homogenization treatment to obtain a suspension.
In the invention, the pressure of the high-pressure homogenizing treatment is preferably 20-100 MPa, more preferably 60-80 MPa, and most preferably 70 MPa; the flow rate is preferably 10 to 1000L/h, more preferably 20 to 90L/h, and most preferably 50 to 80L/h. In the present invention, the apparatus used for the high-pressure homogenization treatment is not particularly limited, and an apparatus capable of performing high-pressure homogenization treatment known to those skilled in the art may be used. In a specific embodiment of the invention, the high pressure homogenization treatment is performed in a high pressure homogenizer.
In the invention, the zinc oxide and the calcium terephthalate can be fully mixed under the action of high pressure homogenization defined by the scheme, and the zinc oxide is combined with the calcium terephthalate in a weak hydrogen bond or intermolecular force mode, so that the zinc oxide is uniformly attached to the surface of the calcium terephthalate, the lipophilicity of the zinc oxide is improved, the composite zinc oxide is fully dispersed in rubber, the compatibility of the composite zinc oxide and the rubber is enhanced, the binding property of the composite zinc oxide and a rubber molecular chain is improved, the utilization rate of the zinc oxide is improved, and the using amount of the zinc oxide is reduced while the activity of the composite zinc oxide is ensured.
After obtaining the suspension, the invention dries the suspension to obtain the composite zinc oxide. In the invention, the drying mode is preferably spray drying, and the inlet temperature of the spray drying is preferably 190-210 ℃, and more preferably 195-200 ℃; the outlet temperature is preferably 90-100 ℃, and more preferably 92-95 ℃. The invention adopts a spray drying mode to quickly realize the drying process of the rubber vulcanization activator, and the obtained composite zinc oxide has good dispersibility.
The invention also provides the composite zinc oxide prepared by the preparation method, which comprises zinc oxide and calcium terephthalate, wherein the zinc oxide is attached to the surface of the calcium terephthalate;
the mass ratio of the zinc oxide to the calcium terephthalate is 1-15: 10.
In the invention, the calcium terephthalate has lipophilicity, and the zinc oxide is attached to the surface of the calcium terephthalate, so that the inorganic compound is grafted with organic lipophilicity, the dispersibility of the composite zinc oxide in rubber is increased, and the bonding effect of the composite zinc oxide and a rubber molecular chain is facilitated.
The invention also provides application of the composite zinc oxide in the field of rubber preparation as a vulcanization activator.
In the invention, the addition amount of the compound zinc oxide as a vulcanization activator in the rubber is preferably 2-5% of the mass of the rubber. The composite zinc oxide provided by the invention can be fully dispersed in rubber, the utilization rate of the zinc oxide is improved, and the rubber with high tensile strength can be obtained by adding a small amount of zinc oxide into the rubber.
In order to further illustrate the present invention, the following examples are provided to describe a composite zinc oxide and its preparation method and application in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding 10kg of zinc oxide and 90kg of calcium terephthalate (with the particle size of 10 μm) into a high-pressure homogenizer, then adding 1000L of water, and carrying out high-pressure homogenization treatment under the conditions that the pressure is 100MPa and the flow rate is 20L/h to obtain a suspension;
and carrying out spray drying on the suspension to obtain the composite zinc oxide, wherein the inlet temperature of the spray drying is 210 ℃, and the outlet temperature of the spray drying is 100 ℃.
Example 2
Adding 25kg of zinc oxide and 75kg of calcium terephthalate (with the particle size of 1 μm) into a high-pressure homogenizer, then adding 1000L of water, and carrying out high-pressure homogenization under the conditions that the pressure is 60MPa and the flow rate is 20L/h to obtain a suspension;
and carrying out spray drying on the suspension to obtain the composite zinc oxide, wherein the inlet temperature of the spray drying is 200 ℃, and the outlet temperature of the spray drying is 95 ℃.
Example 3
Adding 60kg of zinc oxide and 40kg of calcium terephthalate (with the particle size of 15 μm) into a high-pressure homogenizer, then adding 1000L of water, and carrying out high-pressure homogenization under the conditions that the pressure is 20MPa and the flow rate is 50L/h to obtain a suspension;
and carrying out spray drying on the suspension to obtain the composite zinc oxide, wherein the inlet temperature of the spray drying is 190 ℃ and the outlet temperature of the spray drying is 100 ℃.
Example 4
Adding 30kg of zinc oxide and 70kg of calcium terephthalate (with the particle size of 10 μm) into a high-pressure homogenizer, then adding 1000L of water, and carrying out high-pressure homogenization under the condition that the pressure is 80MPa and the flow rate is 90L/h to obtain a suspension;
and carrying out spray drying on the suspension to obtain the composite zinc oxide, wherein the inlet temperature of the spray drying is 190 ℃ and the outlet temperature of the spray drying is 90 ℃.
Example 5
Adding 45kg of zinc oxide and 55kg of calcium terephthalate (with the particle size of 8 μm) into a high-pressure homogenizer, then adding 1000L of water, and carrying out high-pressure homogenization under the conditions that the pressure is 70MPa and the flow rate is 80L/h to obtain a suspension;
and carrying out spray drying on the suspension to obtain the composite zinc oxide, wherein the inlet temperature of the spray drying is 200 ℃, and the outlet temperature of the spray drying is 95 ℃.
Comparative example 1
Mixing 200g of calcium terephthalate with 500mL of water, and sanding for 80min at the rotating speed of 3000r/min to obtain a calcium terephthalate aqueous solution, wherein the diameter of zirconium balls for sanding is 1mm, and the dosage is 2800 g;
50g of zinc oxide (BET specific surface area 40 m)2The grain diameter is 60nm) powder is mixed with 100mL of water, and the mixture is subjected to ultrasonic dispersion for 30min under the condition that the power is 40W, so that zinc oxide suspension is obtained;
mixing the zinc oxide suspension and the calcium terephthalate aqueous solution, heating to 80 ℃, and stirring for 5 hours at the rotating speed of 4500r/min to obtain slurry;
and (3) carrying out spray drying on the slurry to obtain the composite zinc oxide, wherein the inlet temperature of the spray drying is 200 ℃, and the outlet temperature of the spray drying is 80 ℃.
Test example
The composite zinc oxide obtained in examples 1 to 5 and comparative example 1 and indirect zinc oxide (commercial zinc oxide, purity)>99% and a specific surface area of 7m2And/g) as a vulcanization activator, according to 5 parts of the vulcanization activator, 100 parts of butadiene styrene rubber, 2 parts of sulfur, 50 parts of white carbon black, 1 part of stearic acid, 2.4 parts of N-tert-butyl-2-benzothiazole sulfonamide (TBBS) and 3 parts of polyethylene glycol (4000). Mixing according to GB/T2404-2008. The results of the tests on the properties of the vulcanizates obtained after the rubber mixing are given in Table 1.
TABLE 1 Properties of vulcanizates prepared using the composite zinc oxide and the indirect zinc oxide prepared in examples 1 to 5 and comparative example 1 as vulcanization activators
From the results in table 1, it is understood that when the composite zinc oxide provided by the present invention is used as a vulcanization activator to prepare a rubber, the rubber prepared with a small amount of zinc oxide added has a high tensile strength. According to the invention, zinc oxide, calcium terephthalate and water are mixed and subjected to high-pressure homogenization treatment, so that the zinc oxide is attached to the surface of the calcium terephthalate to prepare the composite zinc oxide.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (7)
1. The preparation method of the composite zinc oxide is characterized by comprising the following steps:
mixing zinc oxide, calcium terephthalate and water, and carrying out high-pressure homogenization treatment to obtain a suspension;
and drying the turbid liquid to obtain the composite zinc oxide.
2. The method according to claim 1, wherein the pressure of the high-pressure homogenization treatment is 20 to 100MPa, and the flow rate is 10 to 1000L/h.
3. The preparation method according to claim 1, wherein the calcium terephthalate is powder, and the particle size of the calcium terephthalate is 0.1-20 μm.
4. The method according to claim 1, wherein the drying is performed by spray drying.
5. The method according to claim 4, wherein the spray-drying has an inlet temperature of 190 to 210 ℃ and an outlet temperature of 90 to 100 ℃.
6. The preparation method according to claim 1, wherein the mass ratio of the zinc oxide to the water is 0.6-6: 100.
7. The preparation method according to claim 1 or 6, wherein the mass ratio of the zinc oxide to the calcium terephthalate is 1-15: 10.
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| CN202010522135.XA CN111607128A (en) | 2020-06-10 | 2020-06-10 | Preparation method of composite zinc oxide |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389520A (en) * | 2002-06-12 | 2003-01-08 | 骆天荣 | Multifunctional nano zinc oxide suspension and its prepn. |
| RU2261232C1 (en) * | 2004-02-09 | 2005-09-27 | ГОУ ВПО Воронежский государственный архитектурно-строительный университет-ГОУ ВПО ВГАСУ | Polymer concrete mixture |
| CN101200627A (en) * | 2006-12-15 | 2008-06-18 | 财团法人工业技术研究院 | Ultraviolet absorbent formula and inorganic wet-type surface modifying method |
| CN102061022A (en) * | 2010-12-07 | 2011-05-18 | 江苏爱特恩高分子材料有限公司 | Novel rubber activator and preparation method thereof |
| CN110117382A (en) * | 2019-06-13 | 2019-08-13 | 江西德弘新材料有限公司 | A kind of vulcanization of rubber activating agent and its preparation method and application |
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- 2020-06-10 CN CN202010522135.XA patent/CN111607128A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389520A (en) * | 2002-06-12 | 2003-01-08 | 骆天荣 | Multifunctional nano zinc oxide suspension and its prepn. |
| RU2261232C1 (en) * | 2004-02-09 | 2005-09-27 | ГОУ ВПО Воронежский государственный архитектурно-строительный университет-ГОУ ВПО ВГАСУ | Polymer concrete mixture |
| CN101200627A (en) * | 2006-12-15 | 2008-06-18 | 财团法人工业技术研究院 | Ultraviolet absorbent formula and inorganic wet-type surface modifying method |
| CN102061022A (en) * | 2010-12-07 | 2011-05-18 | 江苏爱特恩高分子材料有限公司 | Novel rubber activator and preparation method thereof |
| CN110117382A (en) * | 2019-06-13 | 2019-08-13 | 江西德弘新材料有限公司 | A kind of vulcanization of rubber activating agent and its preparation method and application |
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