Method for preparing sulfided olefins

Abstract

The present application adopts an organic amine as a catalyst and cooperates with a specific refining agent for refining treatment, thereby effectively reducing the generation of by-product salts, and effectively removing impurities such as by-product salts, hydrogen sulfide, and mercaptans remaining in the sulfided olefins, and further effectively ensuring the appearance transparency and oil solubility of the sulfided olefins; at the same time, the preparation method provided by the present application can effectively remove hydrogen sulfide and neutralize acidic substances in the reaction process, thereby further improving the purity of the product, and effectively reducing the residual hydrogen sulfide, and further improving the stability of the sulfided olefins, and reducing the release of hydrogen sulfide in the sulfided olefins, thereby effectively reducing the odor of the sulfided olefins and reducing the release of hydrogen sulfide in the sulfided olefins.

Description

Technical Field

[0001] The present invention relates to the field of preparation of organic sulfides, and specifically to a method for preparing sulfided olefins. Background Art

[0002] Sulfurized olefins are widely used in the fields of gear oil, metalworking fluids and lubricating greases. In the synthesis method of sulfurized olefins, sulfur monochloride, olefins and alkali metal sulfides are usually used to react to prepare sulfurized olefin crude products, and then traditional solvent oil extraction, water washing, solvent oil recovery, drying, filtration and other refining processes are used to obtain sulfurized olefin products; however, the preparation process is complicated, the use of solvent oil increases the production cost of the product, and a large amount of wastewater and solid waste is generated during the preparation process.

[0003] At present, gradually adopt sulphur and olefin as raw materials, take the aqueous solution of inorganic or organic alkali as catalyst to carry out high pressure reaction and prepare olefin sulfide, this preparation method process is simple, does not contain chlorine, and production cost is also relatively cheap.But by-product salt can be formed in this process and remain in the product, the solubility of this by-product salt in the resultant is higher, but after long-term storage, it is easy to separate from the resultant, causing the turbidity and precipitation of olefin sulfide, which is unfavorable for the appearance transparency of product.In addition, the olefin sulfide containing this by-product salt when used as sulfur-based extreme pressure agent, also can deteriorate the oil solubility of product.In addition, in the olefin sulfide prepared by this preparation method, there are also more hydrogen sulfide or mercaptan residues, and hydrogen sulfide can slowly release when long-term storage, making the smell of olefin sulfide slightly smelly, and also can affect the appearance transparency of olefin sulfide. Summary of the invention

[0004] In view of the above problems existing in the prior art, the purpose of the present application is to provide a sulfided olefin and a preparation method and application thereof. The preparation method of the sulfided olefin of the present application has high production efficiency, low production cost, and is green and environmentally friendly, and the prepared sulfided olefin has the advantages of low odor, good stability, good oil solubility and good appearance transparency.

[0005] To achieve the above objectives, this application adopts the following technical solutions:

[0006] The present application provides a method for preparing sulfided olefins, comprising the following steps:

[0007] The olefin, sulfur, catalyst and hydrogen sulfide are mixed to carry out a sulfidation reaction to prepare a crude sulfided olefin product;

[0008] The crude sulfided olefin product and the refined product are mixed and subjected to a refining treatment to prepare the sulfided olefin;

[0009] The catalyst comprises organic amine; the refining agent comprises peroxide, unsaturated carbonyl compound and organic amine.

[0010] In one embodiment, the crude sulfided olefin product and the refined product are mixed and refined, and the steps of preparing the sulfided olefin include:

[0011] The crude sulfided olefin product is treated with air at a temperature of 40° C. to 110° C. for 0.5 h to 3 h, and then the refining agent is added and the product is treated with air at a temperature of 40° C. to 110° C. for 2 h to 5 h to prepare sulfided olefin.

[0012] In one of the embodiments, the weight ratio of the crude sulfided olefin product to the refined product is 100:(0.01-5).

[0013] In one of the embodiments, the weight ratio of peroxide, unsaturated carbonyl compound and organic amine in the refined preparation is 1:(0.8-1.2):(0.4-1.2).

[0014] In one embodiment, the organic amine includes one or more of ethylenediamine, n-octylamine, isooctylamine, dodecylamine and 81-R.

[0015] In one embodiment, the peroxide comprises one or more of hydrogen peroxide, benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisononanoate and tert-butyl peroxyisopropyl carbonate.

[0016] In one embodiment, the unsaturated carbonyl compound includes one or more of maleic acid and its ester compounds, fumaric acid and its ester compounds, maleic anhydride and its ester compounds.

[0017] In one of the embodiments, the mass ratio of the olefin, sulfur, catalyst and hydrogen sulfide is (40-78):(20-30):(0.05-10):(1.95-20).

[0018] In one embodiment, the steps of mixing olefin, sulfur, catalyst and hydrogen sulfide to carry out a sulfidation reaction to prepare a crude sulfided olefin product include:

[0019] The olefin, sulfur and catalyst are mixed and stirred at a temperature of 110° C. to 140° C. for 0.5 h to 3 h;

[0020] Raise the temperature to 140°C to 180°C, set the pressure to 0.3MPa to 3Mpa, and introduce hydrogen sulfide to react for 3h to 8h;

[0021] The temperature is lowered to 100° C. to 140° C. and distilled under reduced pressure for 0.5 h to 3 h to prepare a crude sulfided olefin product.

[0022] In one embodiment, the pressure of the reduced pressure distillation is set to -0.2MPa to -0.05MPa.

[0023] The present application adopts an organic amine as a catalyst and cooperates with a specific refining agent for refining treatment, thereby effectively reducing the generation of by-product salts, and effectively removing impurities such as by-product salts, hydrogen sulfide, and mercaptans remaining in the sulfided olefins, and further effectively ensuring the appearance transparency and oil solubility of the sulfided olefins; at the same time, the preparation method provided by the present application can effectively remove hydrogen sulfide and neutralize acidic substances in the reaction process, thereby further improving the purity of the product, and effectively reducing the residual hydrogen sulfide, and further improving the stability of the sulfided olefins, and reducing the release of hydrogen sulfide in the sulfided olefins, thereby effectively reducing the odor of the sulfided olefins and reducing the release of hydrogen sulfide in the sulfided olefins.

[0024] In addition, the preparation method of sulfided olefins provided in the present application has simple process, high production efficiency, no emission of waste water, waste gas and waste residue, and is green and environmentally friendly. DETAILED DESCRIPTION

[0025] The following is a further detailed description of the sulfided olefins of the present invention and its preparation method and application in conjunction with specific embodiments. The present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive. Of course, they are merely examples, and the purpose is not to limit the present application.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application. Unless otherwise specified or there is a contradiction, the terms or phrases used herein have the following meanings:

[0027] In the present application, "plurality", "multiple", "multiple times", "plurality", etc., unless otherwise specified, refer to a number greater than 2 or equal to 2. For example, "one or more" means one or greater than or equal to two.

[0028] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0029] In the present application, references to “combinations thereof”, “any combination thereof”, “any combination thereof”, etc. include all suitable combinations of any two or more of the listed items.

[0030] In the present application, the terms “further”, “furthermore”, “particularly”, etc. are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present application.

[0031] In this application, "optionally", "optional" and "optional" refer to optional, that is, to any one of the two parallel schemes of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

[0032] In the present application, when it comes to numerical intervals (i.e., numerical ranges), unless otherwise specified, the optional numerical distribution is considered continuous within the above numerical interval, and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical range, and each numerical value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to the integers within the numerical interval, it includes the two endpoint integers of the numerical range, and each integer between the two endpoints. In this article, it is equivalent to directly listing each integer, such as t is an integer selected from 1 to 10, indicating that t is any integer selected from the group of integers consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10. In addition, when multiple ranges are provided to describe features or characteristics, these ranges can be combined. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all subranges included therein.

[0033] The temperature parameters in this application, unless otherwise specified, are allowed to be either constant temperature treatment or to vary within a certain temperature range. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within the range of ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are allowed.

[0034] In the present application, the percentage content, unless otherwise specified, refers to mass percentage for solid-liquid mixing and solid-solid mixing, and volume percentage for liquid-liquid mixing.

[0035] In this application, when it comes to percentage concentration, unless otherwise specified, it refers to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of the component.

[0036] In the present application, "olefin" refers to a olefin having at least one unsaturated site, i.e., a carbon-carbon sp 2 A phrase containing this term, for example, "C3-C12 olefin" means an olefin containing 3 to 12 carbon atoms, each occurrence of which can be independently C3 olefin, C4 olefin, C5 olefin, C6 olefin, C7 olefin, C8 olefin, C9 olefin, C10 olefin, C11 olefin, C12 olefin. Suitable examples include, but are not limited to, ethylene olefin (CH 2 =CH 2 ), propylene (CH3 CH=CH 2 ), cyclopentene (C 5 H 8 ), 5-hexenyl (CH 3 CH 2 CH 2 CH 2 CH=CH 2 ) and diisobutylene (C 8 H 16 ).

[0037] The present application provides a method for preparing sulfided olefins, comprising the following steps:

[0038] The olefin, sulfur, catalyst and hydrogen sulfide are mixed to carry out a sulfidation reaction to prepare a crude sulfided olefin product;

[0039] The crude sulfided olefin product and the refined product are mixed and subjected to a refining treatment to prepare the sulfided olefin;

[0040] The catalyst comprises organic amine; the refining agent comprises peroxide, unsaturated carbonyl compound and organic amine.

[0041] The present application adopts an organic amine as a catalyst and cooperates with a specific refining agent for refining treatment, thereby effectively reducing the generation of by-product salts, and effectively removing impurities such as by-product salts, hydrogen sulfide, and mercaptans remaining in the sulfided olefins, and further effectively ensuring the appearance transparency and oil solubility of the sulfided olefins; at the same time, the preparation method provided by the present application can effectively remove hydrogen sulfide and neutralize acidic substances in the reaction process, thereby further improving the purity of the product, and effectively reducing the residual hydrogen sulfide, and further improving the stability of the sulfided olefins, and reducing the release of hydrogen sulfide in the sulfided olefins, thereby effectively reducing the odor of the sulfided olefins and reducing the release of hydrogen sulfide in the sulfided olefins.

[0042] In addition, the preparation method of sulfided olefins provided in the present application has simple process, high production efficiency, no emission of waste water, waste gas and waste residue, and is green and environmentally friendly.

[0043] In one example, the olefin is a C3-C12 olefin.

[0044] In one specific example, the olefin is diisobutylene.

[0045] In one example, the crude sulfided olefin product and the refined product are mixed and refined, and the steps of preparing the sulfided olefin include:

[0046] The crude sulfided olefin product is treated with air at a temperature of 40° C. to 110° C. for 0.5 h to 3 h, and then the refining agent is added and the product is treated with air at a temperature of 40° C. to 110° C. for 2 h to 5 h to prepare sulfided olefin.

[0047] Furthermore, the crude sulfided olefin product and the refined product are mixed and subjected to a refining treatment. The steps of preparing the sulfided olefin include:

[0048] The crude sulfided olefin product is treated with air at a temperature of 50° C. to 100° C. for 1 h to 2 h, and then the refining agent is added and treated with air for 3 h to 4 h to prepare the sulfided olefin.

[0049] Through refining treatment, the process flow can be shortened and high-purity sulfided olefins can be obtained efficiently and conveniently. At the same time, hydrogen sulfide can be recovered during the refining process and can be reused, saving production costs.

[0050] In one example, the air treatment is a gas explosion treatment using air.

[0051] In one example, the weight ratio of the crude sulfided olefin product to the refined agent is 100:(0.01-5). It is understandable that the weight ratio of the crude sulfided olefin product to the refined agent can be selected from any value between 100:(0.01-5). Specifically, the weight ratio of the crude sulfided olefin product to the refined agent includes but is not limited to 100:0.01, 100:0.02, 100:0.03, 100:1, 100:0.52, 100:1.51, 100:2, 100:2.5, 100:2.5, 100:3, 100:4 or 100:5.

[0052] In one example, the weight ratio of peroxide, unsaturated carbonyl compound and organic amine in the refined preparation is 1: (0.8-1.2): (0.4-1.2). It can be understood that the weight ratio of peroxide, unsaturated carbonyl compound and organic amine in the refined preparation can be selected from any value between 1: (0.8-1.2): (0.4-1.2). Specifically, the mass ratio of peroxide, unsaturated carbonyl compound and organic amine in the refined preparation includes but is not limited to 1: 0.8: 0.8, 1: 1: 1, 1: 1: 0.5 or 1: 1.2: 1.2.

[0053] In one example, the organic amine includes one or more of ethylenediamine, n-octylamine, isooctylamine, dodecylamine and 81-R.

[0054] In one example, the peroxide includes one or more of hydrogen peroxide, benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy isononanoate and tert-butyl peroxy isopropyl carbonate. In the present application, a peroxide that can be dissolved in sulfided olefins is used, and the 10-hour half-life temperature of the peroxide is between 50°C and 140°C. The half-life temperature is between 50°C and 140°C, which is easy to store and handle, and can avoid thermal decomposition of sulfided olefins. At the same time, the peroxide can convert the by-product sulfur compound salt into sulfate or thiosulfate, and the free radicals generated by the organic peroxide can promote the unstable organic sulfur compound to generate hydrogen sulfide while becoming a stable compound.

[0055] In one example, the unsaturated carbonyl compound includes one or more of maleic acid and its ester compounds, fumaric acid and its ester compounds, maleic anhydride and its ester compounds. The addition of unsaturated carbonyl compounds in the refined agent in the present application can effectively remove hydrogen sulfide remaining in the sulfided olefin.

[0056] In one example, the mass ratio of the olefin, sulfur, catalyst and hydrogen sulfide is (40-78): (20-30): (0.05-10): (1.95-20). It can be understood that the mass ratio of the olefin, sulfur, catalyst and hydrogen sulfide can be selected from any value between (40-78): (20-30): (0.05-10): (1.95-20). Specifically, the mass ratio of the olefin, sulfur and catalyst includes but is not limited to 62.5:28:0.1:9.4, 63:27.5:0.1:9.4, 63.5:27:0.1:9.4, 70:26:1:3, 68:28:1:3, 70:28:0.5:1.5 or 72:26:0.5:1.5.

[0057] In one example, olefin, sulfur, catalyst and hydrogen sulfide are mixed to carry out a sulfidation reaction, and the steps of preparing a sulfided olefin crude product include:

[0058] The olefin, sulfur and catalyst are mixed and stirred at a temperature of 110° C. to 140° C. for 0.5 h to 3 h;

[0059] Raise the temperature to 140°C to 180°C, set the pressure to 0.3MPa to 3Mpa, and introduce hydrogen sulfide to react for 3h to 8h;

[0060] The temperature is lowered to 100° C. to 140° C. and distilled under reduced pressure for 0.5 h to 3 h to prepare a crude sulfided olefin product.

[0061] It can be understood that the temperature for mixing and stirring the olefin, sulfur and catalyst in the present application can be selected from any value between 110° C. and 140° C. Specifically, the stirring temperature includes but is not limited to 110° C., 120° C., 125° C., 130° C. or 140° C. The stirring time can be selected from any value between 0.5h and 3h, specifically, the stirring time includes but is not limited to 0.5h, 0.9h, 1h, 1.1h, 1.2h, 1.5h, 2h or 3h.

[0062] Further, the steps of mixing olefin, sulfur, catalyst and hydrogen sulfide to carry out a sulfidation reaction to prepare a crude sulfided olefin product include:

[0063] The olefin, sulfur and catalyst are mixed and stirred at a temperature of 120° C. to 135° C. for 1 hour;

[0064] Raise the temperature to 140°C to 170°C, set the pressure to 0.5MPa to 2Mpa, and introduce hydrogen sulfide to react for 4h to 7h;

[0065] The temperature is lowered to 100° C. to 130° C. and distilled under reduced pressure for 0.5 h to 3 h to prepare a crude sulfided olefin product.

[0066] In one example, the pressure of the vacuum distillation is set to -0.2MPa to -0.05MPa. It is understandable that the pressure of the vacuum distillation can be selected from any value between -0.2MPa and -0.05MPa. Specifically, the pressure of the vacuum distillation includes but is not limited to -0.2MPa, -0.15MPa, -0.1MPa or -0.05MPa.

[0067] Preferably, the method for preparing sulfided olefins provided in the present application comprises the following steps:

[0068] (1) Diisobutylene and sulfur are added to a high-pressure reactor in a mass ratio of 60-65:26-28, and an organic amine catalyst accounting for 0.1% to 1% of the total mass of diisobutylene and sulfur is added, and the temperature is raised to 120° C. to 135° C. and stirred for 1 hour at a constant temperature. The temperature is then raised to 140° C. to 170° C., hydrogen sulfide is introduced under pressure, and the reaction is kept at this temperature for 4 to 7 hours. During the whole process, the pressure is maintained at 0.5 MPa to 2 MPa.

[0069] (2) The temperature is lowered to 100°C to 130°C, and the product is distilled under reduced pressure at -0.1 MPa for 1 hour. The light component distilled out is unreacted diisobutylene, which is collected and condensed and reused in the next synthesis reaction. The remaining crude sulfided diisobutylene product is pumped to the gas explosion kettle.

[0070] (3) Blow air into the bottom of the gas explosion kettle containing the crude diisobutylene sulfide product at a temperature of 50°C to 100°C for 1 hour to 2 hours to remove dissolved hydrogen sulfide.

[0071] (4) adding peroxide, unsaturated compound and organic amine to the crude olefin sulfide product at a temperature of 50°C to 100°C and continuing to heat and introduce air for 3h to 4h to prepare sulfided diisobutylene.

[0072] (5) The hydrogen sulfide gas generated during the purification process is collected and reused in the synthesis production of diisobutylene sulfide after purification.

[0073] The present application also provides a sulfided olefin, which is prepared by the preparation method described in any of the above examples.

[0074] The sulfided olefin prepared in the present application can improve the oil solubility of the sulfided olefin, can maintain long-term transparency and stability, and releases very little hydrogen sulfide during long-term storage, which can effectively improve the storage odor and appearance color of the sulfided olefin.

[0075] The present application also provides an application of the sulfurized olefin described in the above example in gear oil, metalworking fluid or lubricating grease.

[0076] In order to make the purpose and advantages of the present invention clearer, the following is a further detailed description of the sulfided olefins and the preparation method of the sulfided olefins in conjunction with specific examples. It should be understood that the specific examples described herein are only used to explain the present invention and shall not be used to limit the present invention. The following examples do not include other components except for inevitable impurities unless otherwise specified. The drugs and instruments used in the examples are conventionally selected in the art unless otherwise specified. The experimental methods for which specific conditions are not specified in the examples are implemented according to conventional conditions, such as the conditions described in the literature, books, or the methods recommended by the manufacturer.

[0077] The examples and comparative examples of the present application use crude diisobutylene sulfide products prepared in the same batch, and the preparation method is as follows:

[0078] 600kg of diisobutylene, 270kg of sulfur and 1kg of ethylenediamine catalyst were added into a high-pressure reactor, heated to 130°C and stirred for 1 hour at a constant temperature, then heated to 150°C and pressurized to pass 90kg of hydrogen sulfide and kept warm for 7 hours, keeping the pressure at 2MPa during the whole process. After the reaction, the temperature was lowered to 100°C, and the reaction was distilled under reduced pressure at -0.1MPa for 1 hour to distill out 60kg of light components as unreacted diisobutylene. The unreacted diisobutylene was collected by condensation and reused in the next synthesis reaction to prepare 900kg of crude diisobutylene sulfide. The crude diisobutylene sulfide was treated with the refining process of Examples 1 to 6 and Comparative Examples 1 to 5.

[0079] Example 1

[0080] 1000g of crude diisobutylene sulfide was pumped into a gas explosion kettle, air was introduced at 80°C for 1h, 2g of hydrogen peroxide and 2g of butyl maleate were added and the mixture was further exploded at 80°C for 3h, 2g of ethylenediamine was added and stirred for 0.5h, then the temperature was lowered and the mixture was discharged to prepare diisobutylene sulfide.

[0081] Example 2

[0082] Example 2 is substantially the same as Example 1, with the main difference being that the hydrogen peroxide in Example 1 is replaced with benzoyl peroxide.

[0083] Example 3

[0084] Example 3 is substantially the same as Example 1, with the main difference being that butyl maleate in Example 1 is replaced with octyl fumarate.

[0085] Example 4

[0086] Example 4 is substantially the same as Example 1, with the main difference being that the amount of hydrogen peroxide, butyl maleate, and ethylenediamine in Example 1 are all increased to 5 g.

[0087] Example 5

[0088] Example 5 is basically the same as Example 1, with the main difference being that air is introduced at a temperature of 100° C. for gas explosion for 1 hour.

[0089] Example 6

[0090] Example 6 is basically the same as Example 1, with the main difference being that the explosion time is shortened to 2 hours after the refining agent is added in Example 1.

[0091] Comparative Example 1

[0092] 1000 g of crude diisobutylene sulfide product was pumped into a gas explosion kettle, and air was introduced at 80° C. for gas explosion for 10 hours, then the temperature was lowered and the material was discharged.

[0093] Comparative Example 2

[0094] 1000g of crude diisobutylene sulfide product was pumped into a gas explosion kettle, air was introduced at 80°C for 1 hour, 1g of activated carbon was added and the mixture was further exploded at 80°C for 3 hours, then the temperature was lowered and the material was filtered out to produce 25g of waste residue.

[0095] Comparative Example 3

[0096] Comparative Example 3 is substantially the same as Example 1, with the main difference being that no hydrogen peroxide is added.

[0097] Comparative Example 4

[0098] Comparative Example 4 is substantially the same as Example 1, with the main difference being that butyl maleate is not added.

[0099] Comparative Example 5

[0100] Comparative Example 5 is substantially the same as Example 1, with the main difference being that ethylenediamine is not added.

[0101] Comparative Example 6

[0102] Comparative Example 6 is a commercially available sample of diisobutylene sulfide of model number Rhine 2540.

[0103] Comparative Example 7

[0104] Comparative Example 7 is a sulfurized diisobutylene sample of model Xirui PS40 on the market.

[0105] Performance Testing

[0106] The stability, oil solubility, and hydrogen sulfide release of the diisobutylene sulfide samples prepared in Examples 1 to 6 and Comparative Examples 1 to 5, as well as Comparative Examples 6 and 7 were tested. The specific test results are shown in Table 1.

[0107] 1. Stability: The prepared diisobutylene sulfide was placed at room temperature, -5°C and 60°C for 30 days to observe whether turbid precipitation was generated.

[0108] 2. Oil solubility: Dissolve 20% in 5# white oil or 150N mineral oil, store at room temperature for 30 days, and observe whether there is turbid precipitation.

[0109] 3. Hydrogen sulfide release: Put 20g of the product into a transparent sealed glass bottle, hang a soaked lead acetate test paper on the top, put it into a 60℃ oven, and observe the time it takes for the lead acetate test paper to turn black. If the lead acetate test paper turns black quickly, it means that hydrogen sulfide is released quickly and the organic sulfur compounds are unstable.

[0110] 4. Hydrogen sulfide content: measured by a hydrogen sulfide detector under the same measurement conditions.

[0111] Table 1 Stability, oil solubility and hydrogen sulfide release of Examples 1 to 6 and Comparative Examples 1 to 5

[0112]

[0113]

[0114] Table 1 shows the stability, oil solubility and hydrogen sulfide release test of Examples 1 to 6 and Comparative Examples 1 to 5. The stability, oil solubility and hydrogen sulfide release control effect of diisobutylene sulfide in Examples 1 to 6 are far better than those in Comparative Examples 1 to 5. Compared with the comparative examples, Examples 1 to 6 have a short process flow, a high utilization rate of raw materials, and no waste water, waste gas, waste residue and other three wastes are discharged, which belongs to a green manufacturing process. The final diisobutylene sulfide is an orange-yellow transparent liquid with a density (20°C) of 0.95-1.10g / cm 3 , kinematic viscosity (40℃, mm 2 / S) is 40-42, the flash point (open) is 161°C, it is free of moisture, mechanical impurities, transparent and has no precipitation, and the sulfur content (m / m) is 38% to 40%.

[0115] Table 2 Stability, oil solubility and hydrogen sulfide release of Example 1 and Comparative Examples 6 to 7

[0116]

[0117]

[0118] It can be seen from Table 2 that the diisobutylene sulfide prepared in Example 1 of the present application can remain transparent at low temperatures and has good appearance stability. Moreover, under the same quality, the hydrogen sulfide content in the odor emitted by the diisobutylene sulfide is lower than that in Comparative Examples 6 and 7.

[0119] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0120] The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several variations and improvements can be made, which all belong to the protection scope of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the protection scope of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the content of the attached claims, and the description can be used to interpret the content of the claims.

Claims

1. A method for preparing sulfided olefins, characterized in that: The following steps are involved: The olefin, sulfur, catalyst and hydrogen sulfide are mixed to carry out a sulfidation reaction to prepare a crude sulfided olefin product; The crude sulfided olefin product and the refined product are mixed and subjected to a refining treatment to prepare the sulfided olefin; The catalyst includes an organic amine; the refining agent includes a peroxide, an unsaturated carbonyl compound and an organic amine; The weight ratio of the peroxide, the unsaturated carbonyl compound and the organic amine in the refined preparation is 1: (0.8-1.2): (0.4-1.2); The peroxide comprises one or more of hydrogen peroxide, benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy isononanoate and tert-butyl peroxy isopropyl carbonate; The unsaturated carbonyl compound includes one or more of maleic acid and its ester compounds, fumaric acid and its ester compounds, maleic anhydride and its ester compounds.

2. The method for preparing sulfided olefins according to claim 1, characterized in that: The crude sulfided olefin product and the refined product are mixed and subjected to a refining treatment. The steps of preparing the sulfided olefin include: The crude sulfided olefin product is treated with air at a temperature of 40° C. to 110° C. for 0.5 h to 3 h, and then the refining agent is added and the product is treated with air at a temperature of 40° C. to 110° C. for 2 h to 5 h to prepare the sulfided olefin.

3. The method for preparing sulfided olefins according to claim 1, characterized in that: The weight ratio of the crude sulfided olefin product to the refined product is 100:(0.01-5).

4. The method for preparing sulfided olefins according to any one of claims 1 to 3, characterized in that: The organic amine includes one or more of ethylenediamine, n-octylamine, isooctylamine, dodecylamine and 81-R.

5. The method for preparing sulfided olefins according to any one of claims 1 to 3, characterized in that: The mass ratio of the olefin, sulfur, catalyst and hydrogen sulfide is (40-78): (20-30): (0.05-10): (1.95-20).

6. The method for preparing sulfided olefins according to any one of claims 1 to 3, characterized in that: The steps of mixing olefin, sulfur, catalyst and hydrogen sulfide to carry out a sulfidation reaction to prepare a crude sulfided olefin product include: The olefin, sulfur and catalyst are mixed and stirred at a temperature of 110° C. to 140° C. for 0.5 h to 3 h; Raise the temperature to 140°C~180°C, set the pressure to 0.3MPa~3MPa, and introduce hydrogen sulfide to react for 3h~8h; The temperature is lowered to 100°C to 140°C, and the product is distilled under reduced pressure for 0.5h to 3h to prepare a crude sulfided olefin product.

7. The method for preparing sulfided olefins according to claim 6, characterized in that: The pressure of the reduced pressure distillation is set to -0.2MPa~-0.05MPa.

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