CN111943909B - 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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- CN111943909B CN111943909B CN202010899664.1A CN202010899664A CN111943909B CN 111943909 B CN111943909 B CN 111943909B CN 202010899664 A CN202010899664 A CN 202010899664A CN 111943909 B CN111943909 B CN 111943909B
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- selenobenzothiazole
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- C—CHEMISTRY; METALLURGY
- 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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- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/48—Selenium- or tellurium-containing compounds
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 in 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 to perform heating reaction, performing 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 promoters (M and 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 method 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 accelerator is used to greatly shorten the vulcanization time, reduce the vulcanization temperature, reduce the sulfur consumption and greatly improve the physical and mechanical properties of the rubber.
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 accelerating 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 the rubber composition belongs to a medium-speed vulcanization accelerator and is mainly applied to large-sized parts such as tires, adhesive tapes and the like.
A method for The synthesis of selenobenzothiazole is disclosed in (Bera B C, chakrabartty M.Spectrophotometric determination of selenium with 2-mercaptobenzhiazole [ J ]. The Analyst,1968,93 (1102): 50.). Selenium dioxide is dissolved in dilute hydrochloric acid, 2-mercaptobenzothiazole is dissolved in ethanol, the two are mixed and dissolved to react to prepare selenobenzothiazole, and the content of selenium element is measured 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, a new cinnabar, hou 29593Jie, wu Liang, yu\32704, shichuan, and belongs to an ultra-fast vulcanization accelerator, which has the advantages of high vulcanization speed, short scorching time, easiness in scorching, suitability for thin products and inapplicability to 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.
Furthermore, the concentration of the selenium dioxide solution is 0.21-0.31g/moL.
Further, the concentration of the 2-mercaptobenzothiazole solution is 1.67 to 1.93g/mol.
Further, the molar ratio of the selenium dioxide to the 2-mercaptobenzothiazole is 1.
Further, the organic solvent is one or more of ethanol, methanol and acetone.
Further, the stirring speed in the stirring state is 300 to 500rpm.
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%.
The invention provides a rubber accelerator selenobenzothiazole prepared by the preparation method, which has the melting point of 173-174 ℃, the decomposition temperature of 208-210 ℃ and the product yield of 88.5-91.2%.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) According to the invention, ethanol can be used as an organic solvent, and can be recycled after the reaction is finished, so that the generation of wastewater 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 promoters (M and DM).
Drawings
FIG. 1 is a vulcanization curve of the compounds prepared in examples 4 to 6, in which SBR/SeM represents a compound rubber.
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 thermal analysis spectrum of the 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 detailed, are all those that can be realized or understood by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated by the manufacturer, and are regarded as conventional products commercially available.
The styrene-butadiene rubber and sulfur master batches described in the following examples were purchased from Siji rubber technology, inc. of Dongguan, and the open mill was an experimental small 6-inch rubber mill manufactured by Guangdong Lina industries, inc.
Example 1
Dissolving 0.55 (0.005 mol) of selenium dioxide in 100ml of absolute ethyl alcohol under the stirring condition of 500rpm, dissolving 3.34g (0.02 mol) 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, then 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 (0.005 mol) of selenium dioxide in 150ml of absolute ethyl alcohol under the stirring condition of 300rpm, dissolving 4.18g (0.025 mol) 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
0.55 (0.005 mol) of selenium dioxide is dissolved in 150ml of absolute ethyl alcohol under the stirring condition of 400rpm, 5.01g (0.03 mol) of 2-mercaptobenzothiazole is dissolved in 150ml of absolute ethyl alcohol under the stirring condition of 400rpm, the two solutions are uniformly mixed, the reaction temperature is controlled at 30 ℃, the temperature is kept for reaction for 6 hours, and then the hot solution is filtered, washed, dried and crushed 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
1.25g of sulfur masterbatch (containing 80% sulfur), 2g of selenobenzothiazole (obtained in example 1), 5g of stearic acid and 1g of zinc oxide were added to 100g of styrene-butadiene rubber by means of an open mill, and vulcanization was carried out at 170 ℃ to obtain a rubber compound, which was denoted as SBR/SeM and had a vulcanization curve shown in FIG. 1 and vulcanization parameters shown in Table 1 below.
Example 5
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 were added to 100g of styrene-butadiene rubber by means of 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
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 were added to 100g of styrene-butadiene rubber by means of 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 curing characteristics of the SBR mixed rubber material are detected by adopting a Taiwan U-Can UR-2030 moving die rheometer at 160 ℃.
FIG. 1 is a vulcanization curve of the vulcanizates obtained in examples 4 to 6, as can be derived from FIG. 1: the compounds of examples 4, 5 and 6 were selected for comparison because the vulcanization curves of the compounds substantially overlapped and the scorch time, vulcanization time and maximum torque were substantially the same.
Comparative example 1
A rubber compound, 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 ℃ and the vulcanization curve is shown in FIG. 2 and the vulcanization parameters 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 and vulcanization parameters were shown in Table 1, respectively, as shown in FIG. 2.
The vulcanization parameters of the rubber mixes obtained in example 4 and comparative examples 1 to 2 are shown in Table 1, and the vulcanization curves of the rubber mixes obtained in example 4 and comparative examples 1 to 2 are shown in Table 2. From Table 1 and FIG. 2, among the three accelerators, selenobenzothiazole rubber mix (SBR/SeM) showed the fastest vulcanization speed and the greatest torque, indicating the greatest vulcanization efficiency.
TABLE 1 vulcanization parameters of the mixes obtained in example 4 and comparative examples 1 to 2
The tensile strength, elongation at break and tensile elongation were measured according to the 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 with the weight of about 0.1g are cut out, and the original mass (m) is recorded 0 ) 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 recorded 2 ). 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 to 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 the embodiment 1 of the invention is shown in fig. 5a and fig. 5b, wherein fig. 5a is a C1S spectrum, and C = C, C = S, C-N and C = N can be fitted by gaussian fitting; FIG. 5b is a Se3d spectrum, which can be fit with Gaussian to form S-Se bond, corresponding to the structural formula of the selenobenzothiazole in FIG. 6, fully illustrating the synthesis of selenobenzothiazole.
Through element analysis, the method can obtain the element contents of C, H, S and N, and further can conjecture possible chemical structures. Table 3 shows the elemental analysis of selenobenzothiazole, and it can be observed that the actually obtained values are consistent with the theoretical values, which fully indicates that the selenobenzothiazole is synthesized.
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 example 2 and example 3 were similar to those of 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 (9)
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, wherein the structural formula of the selenobenzothiazole is as follows:
2. the method for preparing the rubber accelerator selenobenzothiazole of claim 1, wherein the concentration of the selenium dioxide solution is 0.21-0.31g/moL.
3. The method for preparing rubber accelerator selenobenzothiazole according to claim 1, wherein the concentration of the 2-mercaptobenzothiazole solution is 1.67-1.93g/mol.
4. The preparation method of the rubber accelerator selenobenzothiazole according to claim 1, wherein the molar ratio of the selenium dioxide to the 2-mercaptobenzothiazole is 1.
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 according to claim 1, wherein the stirring speed in the stirring state is 300-500rpm.
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 heating reaction time is 6-12 hours.
9. The application of a rubber accelerator selenobenzothiazole in preparing rubber is disclosed, wherein the selenobenzothiazole has the following structural formula:
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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