CN111943909A - Rubber accelerator selenobenzothiazole and preparation method and application thereof - Google Patents
Rubber accelerator selenobenzothiazole and preparation method and application thereof Download PDFInfo
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- CN111943909A CN111943909A CN202010899664.1A CN202010899664A CN111943909A CN 111943909 A CN111943909 A CN 111943909A CN 202010899664 A CN202010899664 A CN 202010899664A CN 111943909 A CN111943909 A CN 111943909A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/48—Selenium- or tellurium-containing compounds
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Abstract
The invention discloses a rubber accelerator selenobenzothiazole and a preparation method and application thereof. The method comprises the following steps: respectively dissolving selenium dioxide and 2-mercaptobenzothiazole into an organic solvent under the stirring state to obtain a selenium dioxide solution and a 2-mercaptobenzothiazole solution; and then uniformly mixing the selenium dioxide solution and the 2-mercaptobenzothiazole solution, heating for heating reaction, carrying out suction filtration while the solution is hot, taking filter residues, washing, drying and crushing to obtain the rubber accelerator selenobenzothiazole. The invention is environment-friendly and pollution-free, and the vulcanization promoting effect is better than that of the prior thiazole accelerant. The method can adopt ethanol as an organic solvent, can recycle after the reaction is finished, completely avoids the generation of waste water, and is green and environment-friendly. The synthesis process adopted by the invention is a one-pot method, the operation is simple, and the reaction time is short. The invention expands the application range of the selenobenzothiazole, and the promotion efficiency of the selenobenzothiazole is higher than that of the existing thiazole promoter (M, DM).
Description
Technical Field
The invention relates to the field of rubber vulcanization accelerators, in particular to a rubber accelerator selenobenzothiazole and a preparation method and application thereof.
Background
The process of crosslinking rubber is called vulcanization, and the substance which crosslinks the rubber is called a vulcanizing agent, that is, a crosslinking agent. Vulcanization is the last process of the forming processing of rubber products and is the most important physical and chemical process, and unvulcanized rubber has no practical use value. The vulcanization converts the unvulcanized mixed rubber material into vulcanized rubber, and the rubber macromolecules are converted into three-dimensional reticular macromolecules from linear chain shapes, so that the rubber product obtains excellent physical mechanical and chemical properties.
The sulfur vulcanization process has the longest history, and the used raw materials are cheap and abundant, so that the sulfur vulcanization process is the most economic method for improving the physical and mechanical properties of rubber. The sulfur vulcanization system with the accelerator is the most widely applied vulcanization system, the vulcanization time is greatly shortened, the vulcanization temperature is reduced, the sulfur dosage is reduced, and the physical and mechanical properties of the rubber are greatly improved.
In 1925, Sebrell and Bruni found that 2-mercaptobenzothiazole (accelerator M) and dibenzothiazyl disulfide (accelerator DM) which is a homologue thereof have a good vulcanization acceleration effect, and the prepared vulcanized rubber has good mechanical properties. In the rubber industry, thiazole accelerators are common general vulcanization accelerators and are widely applied to various rubbers. The molecular structure of the rubber composition contains C-S promoting groups, so that the rubber composition belongs to a medium-speed vulcanization accelerator and is mainly applied to large-sized products such as tires, adhesive tapes and the like.
A method for The synthesis of selenobenzothiazoles is disclosed in (Bera B C, Chakrabartty M.Spectrophotometric determination of selenium with 2-mercaptobenzothiazole [ J ]. The Analyst,1968,93(1102): 50.). Dissolving selenium dioxide in dilute hydrochloric acid, dissolving 2-mercaptobenzothiazole in ethanol, mixing and dissolving the two solutions to react to prepare selenobenzothiazole, and measuring the content of selenium by adopting a spectrophotometer method.
A preparation method of a dithio selenium-containing accelerator is introduced in a preparation method [ P ] CN110272365A,2019-09-24 ] of a rubber accelerator selenium diethyldithiocarbamate, namely Marigold, Hou 29593Jie, Wulianghe, Yu 32704, Shichuan, and belongs to an ultra-fast vulcanization accelerator, which has the advantages of high vulcanization speed, short scorching time and easiness in scorching, is suitable for thin products, but is not suitable for thick products.
Disclosure of Invention
In order to overcome the defects and shortcomings of the technology and expand the application range of the selenobenzothiazole, the invention aims to provide the rubber accelerator selenobenzothiazole and a preparation method and application thereof. The accelerant prepared by the method belongs to a medium-speed accelerant, has long scorching time and is suitable for thick products.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a preparation method of a rubber accelerator selenobenzothiazole, which comprises the following steps:
respectively dissolving selenium dioxide and 2-mercaptobenzothiazole into an organic solvent under the stirring state to obtain a selenium dioxide solution and a 2-mercaptobenzothiazole solution; and then uniformly mixing the selenium dioxide solution and the 2-mercaptobenzothiazole solution, heating for heating reaction, carrying out suction filtration while the solution is hot, taking filter residues, washing, drying and crushing to obtain the rubber accelerator selenobenzothiazole.
Further, the concentration of the selenium dioxide solution is 0.21-0.31 g/moL.
Further, the concentration of the 2-mercaptobenzothiazole solution is 1.67 to 1.93 g/mol.
Further, the molar ratio of the selenium dioxide to the 2-mercaptobenzothiazole is 1: 4-6.
Further, the organic solvent is one or more of ethanol, methanol and acetone.
Further, the stirring rate in the stirring state was 300-500 rpm.
Further, the temperature of the heating reaction is 30-50 ℃.
Further, the reaction is heated for 6 to 12 hours.
Preferably, the heating reaction time is 12 hours.
Preferably, the source of selenium dioxide is commercially available selenium dioxide with a purity of 99%; the source of the 2-mercaptobenzothiazole is commercial 2-mercaptobenzothiazole with the purity of 98 percent.
The invention provides a rubber accelerator selenobenzothiazole prepared by the preparation method, the melting point of the rubber accelerator selenobenzothiazole is 173-174 ℃, the decomposition temperature is 208-210 ℃, and the product yield is 88.5-91.2%.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the method can adopt ethanol as an organic solvent, and can be recycled after the reaction is finished, so that the generation of waste water is completely avoided, and the method is green and environment-friendly;
(2) the synthesis process adopted by the invention is a one-pot method, the operation is simple, and the reaction time is short;
(3) the invention expands the application range of the selenobenzothiazole, and the promotion efficiency of the selenobenzothiazole is higher than that of the existing thiazole promoter (M, DM).
Drawings
FIG. 1 is a vulcanization curve of the rubber compounds prepared in examples 4 to 6, wherein SBR/SeM represents a rubber compound.
FIG. 2 is a vulcanization curve of the rubber mixtures obtained in example 4 and comparative examples 1 to 2.
FIG. 3 is a DSC thermogram of selenobenzothiazole prepared in example 1.
FIG. 4 is a TG thermogram of selenobenzothiazole prepared in example 1.
FIGS. 5a and 5b are XPS analysis spectra of selenobenzothiazole prepared in example 1;
FIG. 6 is a structural formula of selenobenzothiazole.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
The styrene-butadiene rubber and sulfur master batches described in the following examples were purchased from Siqi rubber technology Co., Ltd, of Dongguan city, and the open mill was an experimental small 6-inch rubber mixing mill manufactured by Guangdong Lina industries Co., Ltd.
Example 1
Dissolving 0.55(0.005mol) of selenium dioxide in 100ml of absolute ethyl alcohol under the stirring condition of 500rpm, dissolving 3.34g (0.02mol) of 2-mercaptobenzothiazole in 100ml of absolute ethyl alcohol under the stirring condition of 500rpm, uniformly mixing the two solutions, controlling the reaction temperature to be 50 ℃, carrying out heat preservation reaction for 12 hours, carrying out suction filtration on filter residues while the solution is hot, washing, drying and crushing to obtain the rubber accelerator selenobenzothiazole. The product yield was 89.9%, the melting point of the product was 173 ℃ and the decomposition temperature was 210 ℃.
Example 2
Dissolving 0.55(0.005mol) of selenium dioxide in 150ml of absolute ethyl alcohol under the stirring condition of 300rpm, dissolving 4.18g (0.025mol) of 2-mercaptobenzothiazole in 150ml of absolute ethyl alcohol under the stirring condition of 300rpm, uniformly mixing the two solutions, controlling the reaction temperature to be 30 ℃, carrying out heat preservation reaction for 10 hours, carrying out suction filtration on filter residue while the solution is hot, washing, drying and crushing to obtain the rubber accelerator selenobenzothiazole. The product yield was 91.2%, the melting point of the product was 174 ℃ and the decomposition temperature was 208 ℃.
Example 3
Dissolving 0.55(0.005mol) of selenium dioxide in 150ml of absolute ethyl alcohol under the stirring condition of 400rpm, dissolving 5.01g (0.03mol) of 2-mercaptobenzothiazole in 150ml of absolute ethyl alcohol under the stirring condition of 400rpm, uniformly mixing the two solutions, controlling the reaction temperature to be 30 ℃, carrying out heat preservation reaction for 6 hours, carrying out suction filtration on filter residue while the solution is hot, washing, drying and crushing to obtain the rubber accelerator selenobenzothiazole. The yield of the obtained product is 88.5 percent, the melting point of the product is 174 ℃, and the decomposition temperature is 209 ℃.
Example 4
A mixture of 1.25g of sulfur masterbatch (80% sulfur), 2g of selenobenzothiazole (prepared in example 1), 5g of stearic acid, 1g of zinc oxide, was vulcanized at 170 ℃ by means of an open mill to 100g of styrene-butadiene rubber to obtain a rubber compound, designated as SBR/SeM, the vulcanization curve of which is shown in FIG. 1 and the vulcanization parameters of which are shown in Table 1 below.
Example 5
100g of styrene-butadiene rubber was added with 1.25g of sulfur master batch (sulfur content: 80%), 2g of selenobenzothiazole (obtained in example 2), 5g of stearic acid, and 1g of zinc oxide through an open mill, and vulcanization was carried out at 170 ℃ to obtain a rubber compound, the vulcanization curve of which is shown in FIG. 1.
Example 6
100g of styrene-butadiene rubber was added with 1.25g of sulfur master batch (sulfur content: 80%), 2g of selenobenzothiazole (obtained in example 3), 5g of stearic acid, and 1g of zinc oxide through an open mill, and vulcanization was carried out at 170 ℃ to obtain a rubber compound, the vulcanization curve of which is shown in FIG. 1.
The vulcanization characteristics of the SBR mixed rubber material are detected by adopting a Taiwan U-Can UR-2030 moving die rheometer at 160 ℃.
FIG. 1 shows the curing curves of the vulcanizates obtained in examples 4 to 6, as can be seen from FIG. 1: the vulcanization curves of the rubber mixtures obtained in examples 4, 5 and 6 were substantially coincident with each other, and the scorch time, vulcanization time and maximum torque were substantially the same, so that the rubber mixture of example 4 was selected and described for comparison.
Comparative example 1
A mixture, designated SBR/M, was obtained by adding 1.25g of sulfur masterbatch (sulfur content: 80%), 2g of 2-mercaptobenzothiazole (accelerator M), 5g of stearic acid, 1g of zinc oxide to 100g of styrene-butadiene rubber by means of an open mill and vulcanizing at 170 ℃ the vulcanization curve of which is shown in FIG. 2 and the vulcanization parameters of which are shown in Table 1.
Comparative example 2
A rubber compound, designated SBR/DM, was obtained by adding 1.25g of sulfur masterbatch (sulfur content: 80%), 2g of dibenzothiazyl disulfide (accelerator DM), 5g of stearic acid, and 1g of zinc oxide to 100g of styrene-butadiene rubber by means of an open mill and vulcanizing at 170 ℃ and the vulcanization curve is shown in FIG. 2 and the vulcanization parameters are shown in Table 1.
The vulcanization parameters of the rubber compounds prepared in example 4 and comparative examples 1-2 are shown in Table 1, the vulcanization curve chart of the rubber compounds prepared in example 4 and comparative examples 1-2 is shown in Table 2, and from Table 1 and FIG. 2, the vulcanization speed of the selenobenzothiazole rubber compound (SBR/SeM) is the fastest, the torque is the largest, and the vulcanization efficiency is the largest among the three accelerators.
TABLE 1 vulcanization parameters of the mixes obtained in example 4 and in comparative examples 1-2
Tensile strength, elongation at break, set elongation were tested according to standard GB/T528.
And (3) measuring the crosslinking density of the SBR vulcanized rubber by adopting an equilibrium swelling method. Three groups of three systems of vulcanized rubber of about 0.1g are cut out, and the original mass (m) is recorded0) Swelling with toluene solution for 72 hours, quickly taking out the sample, wiping off the surface solvent, and recording the swelling mass (m)1) After two days of evaporation of the sample in a fume hood, the sample was transferred to a vacuum oven for drying and the drying mass (m) was recorded2). The swelling equilibrium crosslink density was calculated according to the Flory-Rehner equation:
volume fraction in swollen rubber Vr:
crosslinking density Vc:
where α is the mass fraction of SBR in the sample, α is the mass loss ratio of the sample after swelling, and represents the density of rubber, and represents the density of toluene, and is the interaction parameter of SBR and toluene, and its value is 0.0653.
The physical properties of the mixtures obtained in example 4 and in comparative examples 1-2 are given in Table 2, from which it can be seen that: the physical properties of the selenobenzothiazole vulcanizate (SBR/SeM) are enhanced over the other two. Wherein, the tensile strength is increased by 34.6 percent compared with SBR/M and 15.5 percent compared with SBR/DM; the 100 percent definite elongation is increased by 23.3 percent compared with SBR/M and increased by 9.5 percent compared with SBR/DM; the 300 percent definite elongation is increased by 33.5 percent compared with SBR/M and increased by 11.0 percent compared with SBR/DM; the crosslinking density is increased by 103.2 percent compared with SBR/M and 89.1 percent compared with SBR/DM.
TABLE 2 physical Properties of the mixes obtained in example 4 and comparative examples 1-2
The DSC thermal analysis curve of the selenobenzothiazole prepared in example 1 of the present invention is shown in FIG. 3, and the TG thermal analysis curve is shown in FIG. 4. As can be seen from fig. 3 and 4: the melting point of the obtained product is 173 ℃, the decomposition temperature is 210 ℃, and the product has only one sharp endothermic peak and one thermal weight loss step, which indicates that the purity of the obtained product is high.
The X-ray photoelectron spectrum curve of the selenobenzothiazole prepared in example 1 of the present invention is shown in fig. 5a and fig. 5b, fig. 5a is a C1s spectrum, and C C, C-S, C-N, C-N can be fitted by gaussian fitting; FIG. 5b is a Se3d spectrum, which can be Gaussian fit to form S-Se bond, corresponding to the structural formula of selenobenzothiazole in FIG. 6, fully illustrating the synthesis of selenobenzothiazole.
By element analysis, the invention can obtain C, H, S, N element content, and further can conjecture possible chemical structure. Table 3 shows the elemental analysis of selenobenzothiazole, and it can be observed that the actually obtained value is consistent with the theoretical value, which fully explains the synthesis of selenobenzothiazole.
TABLE 3 elemental analysis of selenobenzothiazoles
The thermogravimetric analysis chart, the differential scanning calorimetry chart, the X-ray photoelectron spectrometer and the elemental analysis values of the example 2 and the example 3 are similar to those of the example 1, and are not repeated herein.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a rubber accelerator selenobenzothiazole is characterized by comprising the following steps:
respectively dissolving selenium dioxide and 2-mercaptobenzothiazole into an organic solvent under the stirring state to obtain a selenium dioxide solution and a 2-mercaptobenzothiazole solution; and then uniformly mixing the selenium dioxide solution and the 2-mercaptobenzothiazole solution, heating for heating reaction, carrying out suction filtration while the solution is hot, taking filter residues, washing, drying and crushing to obtain the rubber accelerator selenobenzothiazole.
2. The method for preparing rubber accelerator selenobenzothiazole according to claim 1, wherein the concentration of the selenium dioxide solution is 0.21-0.31 g/moL.
3. The method for preparing rubber accelerator selenobenzothiazole according to claim 1, wherein the concentration of the 2-mercaptobenzothiazole solution is 1.67-1.93 g/mol.
4. The method for preparing the rubber accelerator selenobenzothiazole according to claim 1, wherein the molar ratio of the selenium dioxide to the 2-mercaptobenzothiazole is 1: 4-6.
5. The method for preparing the rubber accelerator selenobenzothiazole according to claim 1, wherein the organic solvent is one or more of ethanol, methanol and acetone.
6. The method for preparing the rubber accelerator selenobenzothiazole as claimed in claim 1, wherein the stirring speed in the stirring state is 300-500 rpm.
7. The method for preparing the rubber accelerator selenobenzothiazole according to claim 1, wherein the temperature of the heating reaction is 30-50 ℃.
8. The method for preparing the rubber accelerator selenobenzothiazole according to claim 1, wherein the time of the heating reaction is 6-12 hours.
9. The rubber accelerator selenobenzothiazole prepared by the preparation method of any one of claims 1 to 8 is characterized by having a melting point of 173-174 ℃, a decomposition temperature of 208-210 ℃ and a product yield of 88.5-91.2%.
10. Use of the rubber accelerator selenobenzothiazole of claim 9 in the preparation of rubber.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115716819A (en) * | 2022-09-29 | 2023-02-28 | 华南理工大学 | Rubber multifunctional additive 4-methylpiperidinyl dithiocarbamic acid mercaptobenzimidazole selenium and preparation method and application thereof |
| CN115894388A (en) * | 2022-10-10 | 2023-04-04 | 华南理工大学 | Rubber multifunctional additive poly-azole selenium and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105524014A (en) * | 2015-12-31 | 2016-04-27 | 濮阳蔚林化工股份有限公司 | Purification method of rubber vulcanization accelerator 2-mercaptobenzothiazole |
| CN105837871A (en) * | 2016-05-23 | 2016-08-10 | 华南协同创新研究院 | Rubber accelerator and preparation method thereof |
| CN109336844A (en) * | 2018-12-12 | 2019-02-15 | 北京彤程创展科技有限公司 | The synthetic method and composition of a kind of 2- anilino- benzothiazole and application |
-
2020
- 2020-08-31 CN CN202010899664.1A patent/CN111943909B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105524014A (en) * | 2015-12-31 | 2016-04-27 | 濮阳蔚林化工股份有限公司 | Purification method of rubber vulcanization accelerator 2-mercaptobenzothiazole |
| CN105837871A (en) * | 2016-05-23 | 2016-08-10 | 华南协同创新研究院 | Rubber accelerator and preparation method thereof |
| CN109336844A (en) * | 2018-12-12 | 2019-02-15 | 北京彤程创展科技有限公司 | The synthetic method and composition of a kind of 2- anilino- benzothiazole and application |
Non-Patent Citations (4)
| Title |
|---|
| RAMANAUSKAS, E. ET AL.: "Mercaptobenzothiazole as a reagent for the photometric determination of trace amounts of selenium", 《LIETUVOS TSR AUKSTUJU MOKYKLU MOKSLO DARBAI, CHEMIJA IR CHEMINE TECHNOLOGIJA》 * |
| SIGAL YOSEF ET AL.: "Octa-O-bis-(R,R)-tartarate ditellurane (SAS) - a novel bioactive organotellurium(IV) compound: synthesis, characterization, and protease inhibitory activity", 《CHEMMEDCHEM》 * |
| T.KAWAHARA ET AL.: "Synthesis of a networked strontium-O-phenylene-S-tellurium hybrid co-polymer having a two-step electron transfer nature", 《DESIGNED MONOMERS AND POLYMERS》 * |
| 游兴均: "基于天然橡胶的硫化促进剂的合成及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115716819A (en) * | 2022-09-29 | 2023-02-28 | 华南理工大学 | Rubber multifunctional additive 4-methylpiperidinyl dithiocarbamic acid mercaptobenzimidazole selenium and preparation method and application thereof |
| CN115716819B (en) * | 2022-09-29 | 2024-05-10 | 华南理工大学 | Rubber multifunctional auxiliary agent 4-methylpiperidinyl dithiocarbamic acid mercaptophenylimidazole selenium, and preparation method and application thereof |
| CN115894388A (en) * | 2022-10-10 | 2023-04-04 | 华南理工大学 | Rubber multifunctional additive poly-azole selenium and preparation method and application thereof |
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