CN109320795B - Organic zinc sulfide activator and preparation method thereof - Google Patents
Organic zinc sulfide activator and preparation method thereof Download PDFInfo
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- CN109320795B CN109320795B CN201811117016.5A CN201811117016A CN109320795B CN 109320795 B CN109320795 B CN 109320795B CN 201811117016 A CN201811117016 A CN 201811117016A CN 109320795 B CN109320795 B CN 109320795B
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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
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/04—Monocyclic monocarboxylic acids
- C07C63/06—Benzoic acid
- C07C63/08—Salts thereof
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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
Abstract
The invention relates to an organic zinc vulcanizing activator and a preparation method thereof, wherein the organic zinc vulcanizing activator is prepared by the following steps: adding zinc hydroxide and benzoic acid into a reactor according to the mol ratio of 1.6-1.7: 1, adding a hydrocarbon solvent which is 1-50 times of the mass of the zinc hydroxide and has a boiling point of 80-120 ℃, performing reflux reaction for 30-120 min, recovering the solvent by suction filtration after evaporation or cooling, and drying to obtain a white powder organic zinc vulcanization active agent, wherein the zinc content of the organic zinc vulcanization active agent is 40-42%. The organic zinc vulcanization activator can replace zinc oxide with equal mass fraction, greatly reduces the zinc content in rubber products by about 50 percent, and has the advantage of volume cost. The preparation method is simple, the reaction is mild and easy to control, the solvent can be recycled, and no three wastes are generated, so that the method is a green synthesis process.
Description
Technical Field
The invention relates to a vulcanization activator in a rubber vulcanization process, in particular to an organic zinc vulcanization activator and a preparation method thereof.
Background
The rubber industry is taken as a major branch industry of the world industry and plays a very important role in the economic society, and the rubber vulcanization activator is a kind of accelerating assistant which can increase the activity of an accelerator, reduce the using amount of the accelerator, shorten the vulcanization time and increase crosslinking after being added with rubber materials. The zinc oxide is used as a rubber vulcanization activator, and the dosage is about 2.5 to 5 phr. Along with the enhancement of low-carbon economy and emission reduction consciousness in the world, the zinc pollution problem of the rubber industry is more and more concerned, the influence of high zinc content, high density and high heavy metal ion content of zinc oxide on the environmental protection, energy conservation and aging performance of rubber is continuously highlighted, and the important significance is achieved in developing other high-performance zinc oxide products or searching zinc oxide substitutes to reduce the zinc content in the rubber products. Therefore, organic zinc with a specific structure is adopted to replace zinc oxide so as to reduce the content of zinc in the rubber. The organic zinc products currently on the market for reducing zinc in rubber are mainly zinc monomethacrylate (e.g. DYMALINK709 from SARTOMER), zinc α -ethylhexanoate (e.g. ZEH from struktol) or some combinations of zinc soaps (e.g. SL-272, SL 273) which have the disadvantage of either limited zinc reduction capacity or high price.
Disclosure of Invention
The invention aims to provide a vulcanization activator which can replace zinc oxide by equal mass fraction and reduce the zinc content in rubber products.
The invention also aims to provide a preparation method of the vulcanization activator, which has the advantages of simple process, convenient operation and mild reaction conditions.
The preparation method of the organic zinc vulcanizing activator comprises the following steps: adding zinc hydroxide and benzoic acid into a reactor according to the mol ratio of 1.6-1.7: 1, adding a hydrocarbon solvent with the boiling point of 80-120 ℃ and the mass of 1-50 times that of the zinc hydroxide, performing reflux reaction for 30-120 min, recovering the solvent by suction filtration after evaporation or cooling, and drying to obtain the white powder organic zinc sulfide activator.
The zinc content of the organic zinc vulcanizing activator prepared by the invention is 40-42%.
The hydrocarbon solvent with the boiling point of 80-120 ℃ is any one of n-heptane, methylcyclohexane or toluene.
The invention has the following characteristics: the adopted raw materials are common chemical raw materials, have wide sources and low price, and have obvious cost advantage compared with the traditional zinc oxide and other organic zinc vulcanizing activators in the market. The reaction temperature depends on the solvent used, and the reaction condition is mild and easy to control. The synthesis process is simple, the solvent can be recycled, and three wastes are not generated, so that the method is a green synthesis process.
The prepared organic zinc vulcanizing activator can replace zinc oxide by equal mass fraction, greatly reduce the zinc content in rubber products by about 50 percent, reduce the specific gravity of rubber materials, and has very obvious effect and volume cost advantage.
Drawings
FIG. 1 FT-IR spectrum of an organozinc sulfidation active agent of example 1;
FIG. 2 SEM photograph of organozinc sulfidation active agent of example 1;
FIG. 3 XRD pattern of organozinc sulfidation active agent of example 1;
FIG. 4 TG-DTA spectrum of organozinc vulcanizing activator of example 1.
Detailed Description
The technical solutions and effects of the present invention are further illustrated by the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Adding 85mmol (8.4g) of zinc hydroxide, 50mmol (6.1g) of benzoic acid and 280g of methylcyclohexane into a 500mL three-necked flask with a stirring and refluxing device, refluxing and reacting at 102 ℃ for 60min, cooling, recovering the solvent by suction filtration, and drying to obtain 13.4g of white powdery organic zinc sulfide activator with zinc content of 40.8%.
The FT-IR spectrum of the organozinc sulfidation activator is shown in FIG. 1. The microstructure is a mixture of long and thin fibers with a small amount of irregular particles, as shown in the SEM photograph of FIG. 2. The XRD pattern is shown in FIG. 3, and FIG. 4 is a TG-DTA pattern.
Example 2
In a 5L kneader reactor equipped with a reflux apparatus, 12mol (1193g) of zinc hydroxide, 7.5mol (916g) of benzoic acid and 1200g of n-heptane were charged, and the mixture was refluxed for 90 minutes under stirring at 99 ℃ and then the solvent was recovered by evaporation to obtain 1956g of a white powdery organic zinc vulcanizing active agent having a zinc content of 41.4%.
The organic zinc activator synthesized in examples 1 and 2, the zinc alpha-ethyl hexanoate in comparative example and the zinc oxide in the indirect method of 99.7 percent in comparative example are applied to the tread rubber of the all-steel radial tire, and the formula of the rubber material is as follows (by weight): SMR 10100 parts; carbon black N33940 parts; 20 parts of precipitated white carbon black; 2 parts of aromatic oil; 2 parts of protective wax; 1.5 parts of stearic acid; 691 parts of a silane coupling agent si; 1.5 parts of an anti-aging agent RD; 40202 parts of an anti-aging agent; 2.5 parts of sulfur powder; 1.5 parts of accelerator CZ; 0.5 part of accelerator DM; 2.5 parts of vulcanization activator.
The tread rubber mixing process adopts a three-stage mixing process: the rubber material is mixed in three sections, wherein the first section mixing is carried out in an F270 type internal mixer, and the rotating speed of a rotor is 60 r.min-1The ram pressure is 0.7MPa, and the mixing process comprises raw rubber → ram (30s) → 2/3 carbon black and white carbon black → ram (30s) → lifting ram (5s) → pressing ram (30s) → lifting ram (10s) → pressing ram (50s) → discharging rubber (160 ℃); the two-stage mixing is carried out in a GK400 type internal mixer with the rotating speed of a rotor of 50 r.min-1The ram pressure is 0.7MPa, and the mixing process comprises a first-stage mixing rubber → ram (30s) → 1/3 carbon black and white carbon black (30s) → ram (8s) → ram (30s) → rubber discharge (160 ℃); the final mixing is carried out in a GK400 type internal mixer with the rotating speed of a rotor of 20 r.min-1The ram pressure is 0.7MPa, and the mixing process comprises two-stage rubber mixing, sulfur and an accelerator → pressure ram (30s) → pressure ram (5s) → pressure ram (50s) → rubber discharge (105 ℃).
The test results of the sizing properties are shown in table 1 below:
table 1 sizing material performance test results
From the test results, the organic zinc sulfide activator prepared by the technical scheme of the invention can replace zinc oxide by equal mass fraction, and the physical and mechanical properties of the sizing material are equivalent to those of the traditional zinc oxide sizing material, so that the aim of reducing the zinc content is fulfilled.
Claims (2)
1. An organic zinc sulfide activator is characterized by being prepared by the following method: adding zinc hydroxide and benzoic acid into a reactor according to a molar ratio of 1.6-1.7: 1, adding a hydrocarbon solvent which is 1-50 times of the mass of the zinc hydroxide and has a boiling point of 80-120 ℃, performing reflux reaction for 30-120 min, evaporating or cooling, performing suction filtration to recover the solvent, and drying to obtain a white powder organic zinc vulcanization activator, wherein the zinc content of the organic zinc vulcanization activator is 40-42%, and the hydrocarbon solvent is any one of n-heptane, methylcyclohexane or toluene.
2. The method of preparing an organozinc vulcanizing activator of claim 1, characterized by the steps of: adding zinc hydroxide and benzoic acid into a reactor according to the mol ratio of 1.6-1.7: 1, adding a hydrocarbon solvent with the boiling point of 80-120 ℃ and the mass of 1-50 times that of the zinc hydroxide, performing reflux reaction for 30-120 min, recovering the solvent by suction filtration after evaporation or cooling, and drying to obtain the white powder organic zinc sulfide activator.
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Address after: 510000 363 Changxin Road, Tianhe District, Guangzhou, Guangdong. Patentee after: Institute of rare metals, Guangdong Academy of Sciences Address before: 510000 363 Changxin Road, Tianhe District, Guangzhou, Guangdong. Patentee before: GUANGDONG INSTITUTE OF RARE METALS |
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Effective date of registration: 20230310 Address after: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee after: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Address before: 510000 363 Changxin Road, Tianhe District, Guangzhou, Guangdong. Patentee before: Institute of rare metals, Guangdong Academy of Sciences |
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