A process for the preparation of alkenyl succinic anhydride from an alkene mixture feed

Abstract

The application provides a method for preparing alkenyl succinic anhydride from alkene mixed raw materials, by controlling the content of C16, C17 and C18 alkenes in the alkane-alkene mixture to be more than 80% of the total mass of alkenes, the content of C15 and C15 or below alkenes to be less than 15% of the total mass of alkenes, the content of C19 and C19 or above alkenes to be less than 15% of the total mass of alkenes, and the content of C17 alkenes to be more than 10% of the total mass of alkenes; the content of alkane in the total mass of alkane-alkene is 9-50%; after isomerization of the alkenes, the content of internal alkenes in the total mass of alkenes is more than 90%, the yield of ASA can be improved, the by-products are obviously less, the conversion rate of alkenes is improved, and the product performance is also improved; the synthesis temperature is controlled in the range of 18-250 DEG C, the antioxidant is used in an amount of 0.1-1 ‰, the reaction time is 6-12 hours, the molar ratio of alkenes to maleic anhydride is 1.2:1 to 0.8:1, and the content of oxygen compounds in the raw materials is less than 300 ppm, so that the product performance is good.

Description

Technical Field

[0001] This invention relates to a preparation method, and more particularly to a method for preparing alkenyl succinic anhydride from a mixture of alkane and alkene raw materials. Background Technology

[0002] Alkenyl succinic anhydride, abbreviated as ASA, is generally obtained by reacting a C16 or / and C18 inner olefin with maleic anhydride to produce an oily amber liquid with a hydrophobic long carbon chain and a reactive anhydride structure.

[0003] The two main raw materials for producing ASA, maleic anhydride and inner olefins, have extremely poor mutual solubility, resulting in a very slow reaction rate. Furthermore, maleic anhydride is prone to side reactions, which affects the yield.

[0004] Meanwhile, since ASA is emulsified into 1.8-2μm particles by an emulsifier and then added to paper to improve its water resistance, the emulsification effect and the water resistance of ASA itself affect the final performance. ASA synthesized from C16 olefins is relatively easy to emulsify, and good emulsification of ASA can improve the water resistance of paper. While ASA synthesized from C18 olefins is more difficult to emulsify, its longer carbon chain length results in better water resistance in the paper. Sometimes, to balance emulsification and water resistance, the two are mixed in a certain proportion.

[0005] Patent CN116655563A discloses a method for separating alkane and olefin in the co-production of alkenyl succinic anhydride. This patent isomerizes a mixture of alkane and olefin through catalyst selection to synthesize ASA. Unreacted alkane mixtures are then separated by distillation to obtain the ASA product. However, the process is not optimized, resulting in poor product performance. Patents CN118308144A and CN118308145A use Fischer-Tropsch oil as raw material to prepare internal olefins through isomerization, but the ASA yield is low, with many byproducts and poor product performance. Patents CN102633757A and others disclose methods for synthesizing ASA, but all use C16 or C18 internal olefins. C16 ASA is relatively easy to emulsify but has poor water resistance, while C18 ASA has better water resistance but is still difficult to emulsify, resulting in certain defects in the performance balance of synthesized ASA. Patent CN1432088A discloses a method for synthesizing ASA using C14-C19 inner alkenes, specifying the exact proportions of different carbon numbers and limiting the position of double bond isomerization. However, it is limited to the study of alkene mixtures and does not involve the study of the effect on alkanes. Summary of the Invention

[0006] This invention improves the yield of ASA, significantly reduces byproducts, increases olefin conversion, and enhances product performance by controlling the synthesis temperature within the range of 18-250℃, using an antioxidant dosage of 0.1-1‰, a reaction time of 6-12 hours, and an olefin to maleic anhydride molar ratio of 1.2:1 to 0.8:1. When the oxygen content in the raw materials does not exceed 300 ppm, the product performance is better. This is achieved by controlling the synthesis temperature within the range of 18-250℃, using an antioxidant dosage of 0.1-1‰, a reaction time of 6-12 hours, and an olefin to maleic anhydride molar ratio of 1.2:1 to 0.8:1.

[0007] This invention provides a method for preparing alkenyl succinic anhydride from a mixture of alkane and alkene raw materials, characterized in that:

[0008] Maleic anhydride and antioxidants are added to the alkane-olefin mixture and heated to 70-150℃;

[0009] After the maleic anhydride has melted, purge the solution with N2O for 1-1 hour from the bottom.

[0010] Under N2 protection, the mixture is heated to 190-240℃ for 6-12 hours to form reactants.

[0011] Unreacted substances were removed by distillation of the reactants to obtain alkenyl succinic anhydride;

[0012] In the aforementioned alkane-olefin mixture, C16, C17, and C18 olefins account for 80% or more of the total olefin mass, C15 and below olefins account for 15% or less of the total olefin mass, C19 and above olefins account for 15% or less of the total olefin mass, and C17 olefins account for 10% or more of the total olefin mass; alkanes account for 9-50% of the total alkane-olefin mass; and after isomerization, internal olefins account for 90% or more of the total olefin mass.

[0013] Preferably, the alkanes account for 17-44% of the total mass of alkanes and alkenes; and the C17 olefins account for more than or equal to 20% of the total mass of olefins.

[0014] Preferably, the alkanes account for 29-38% of the total mass of alkanes and olefins.

[0015] Preferably, the alkanes account for 29-48% of the total mass of alkanes and olefins; and the C17 olefins account for 15-27% of the total mass of alkanes and olefins.

[0016] Preferably, the amount of antioxidant used is 0.1‰-1‰ of the total weight of the mixture of maleic anhydride, alkanes and olefins.

[0017] Preferably, the antioxidant is 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl).

[0018] Preferably, the molar ratio of the inner olefin to maleic anhydride is 1.2:1 to 0.8:1.

[0019] Preferably, the alkane-olefin mixture is derived from C16-C18 components prepared using coal as a raw material.

[0020] Preferably, the oxygen content in the C16-C18 Fischer-Tropsch oil prepared from coal-based raw materials does not exceed 300 ppm.

[0021] This invention utilizes Fischer-Tropsch oil prepared from coal as a raw material, enabling its effective utilization. Due to the complex composition of Fischer-Tropsch oil, after separation, olefins and alkanes in the C16, C17, and C18 ranges, with similar boiling points, cannot be completely separated at low cost. Current methods involve hydrogenation to convert all olefins into alkanes for utilization, resulting in the conversion of higher-value-added olefins into lower-value-added alkanes, thus failing to rationally utilize the resource.

[0022] The presence of alkanes in this invention can dissolve a portion of maleic anhydride, reducing the self-polymerization reaction of maleic anhydride and accelerating the reaction rate. C16, C17, and C18 olefins account for 80% or more of the total olefin mass, C15 and below olefins account for 15% or less of the total olefin mass, C19 and above olefins account for 15% or less of the total olefin mass, and C17 olefins account for ≥10% of the total olefin mass. Alkanes account for 9-50% of the total alkane-olefin mass. After isomerization, the internal olefins account for more than 90% of the total olefin mass, which can improve the yield of ASA, significantly reduce by-products, and improve product performance.

[0023] The present invention controls the synthesis temperature within the range of 190-240℃, uses an antioxidant dosage of 0.1-1‰, a reaction time of 6-12 hours, and an olefin to maleic anhydride molar ratio of 1.2:1 to 0.8:1. When the oxygen content in the raw materials does not exceed 300ppm, the product performance is better. Detailed Implementation

[0024] The present invention will be further described in detail below through embodiments, which are intended to illustrate the invention and not limit it. It should be noted that those skilled in the art can make various improvements and modifications to the present invention without departing from the principles of the invention, and these improvements and modifications also fall within the protection scope of the present invention.

[0025] Olefin conversion: moles of ASA divided by moles of olefins.

[0026] ASA yield: the mass of ASA after distillation divided by the total mass of the feed.

[0027] Byproduct ratio: Byproducts are solids that coke on the container during the reaction and those that are insoluble in the reactants. The ratio is calculated by dividing the weight of the byproducts by the total mass of the olefins and maleic anhydride fed into the reactor.

[0028] Example 1:

[0029] Take 100g of α-olefin and 120g of alkane, and perform liquid-phase isomerization to convert the α-olefin into an internal olefin, with the internal olefin accounting for more than 90% of the total olefin mass. Add 41g of maleic anhydride and 0.1g of the antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixture in a round-bottom flask. Heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. React under N2 protection at 190℃, then increase the temperature to 210℃ at a rate of 5℃ per hour and maintain at 210℃ for 4 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0030] Example 2:

[0031] Take 100g of α-olefin and 100g of alkane, and perform liquid-phase isomerization to convert the α-olefin into an internal olefin, with the internal olefin accounting for more than 90% of the total olefin mass. Add 41g of maleic anhydride and 0.1g of the antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixture in a round-bottom flask. Heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. React under N2 protection at 190℃, then increase the temperature to 210℃ at a rate of 5℃ per hour and maintain at 210℃ for 4 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0032] Example 3:

[0033] Take 100g of α-olefin and 80g of alkane, and perform liquid-phase isomerization to convert the α-olefin into an internal olefin, with the internal olefin accounting for more than 90% of the total olefin mass. Add 41g of maleic anhydride and 0.1g of the antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixture in a round-bottom flask. Heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. React under N2 protection at 190℃, then increase the temperature to 210℃ at a rate of 5℃ per hour and maintain at 210℃ for 4 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0034] Example 4:

[0035] Take 100g of α-olefin and 60g of alkane, and perform liquid-phase isomerization to convert the α-olefin into an internal olefin, with the internal olefin accounting for more than 90% of the total olefin mass. Add 41g of maleic anhydride and 0.1g of the antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixture in a round-bottom flask. Heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. React under N2 protection at 190℃, then increase the temperature to 210℃ at a rate of 5℃ per hour and maintain at 210℃ for 4 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0036] Example 5:

[0037] Take 100g of α-olefin and 40g of alkane, and perform liquid-phase isomerization to convert the α-olefin into an internal olefin, with the internal olefin accounting for more than 90% of the total olefin mass. Add 41g of maleic anhydride and 0.1g of the antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixture in a round-bottom flask. Heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. React under N2 protection at 190℃, then increase the temperature to 210℃ at a rate of 5℃ per hour and maintain at 210℃ for 4 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0038] Example 6:

[0039] Take 100g of α-olefin and 20g of alkane, and perform liquid-phase isomerization to convert the α-olefin into an internal olefin, with the internal olefin accounting for more than 90% of the total olefin mass. Add 41g of maleic anhydride and 0.1g of the antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixture in a round-bottom flask. Heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. React under N2 protection at 190℃, then increase the temperature to 210℃ at a rate of 5℃ per hour and maintain at 210℃ for 4 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0040] Example 7:

[0041] Take 100g of α-olefin and 10g of alkane, and perform liquid-phase isomerization to convert the α-olefin into an internal olefin, with the internal olefin accounting for more than 90% of the total olefin mass. Add 41g of maleic anhydride and 0.1g of the antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixture in a round-bottom flask. Heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. React under N2 protection at 190℃, then increase the temperature to 210℃ at a rate of 5℃ per hour and maintain at 210℃ for 4 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0042] Example 8:

[0043] Take 100g of α-olefin and 1g of alkane, and perform liquid-phase isomerization to convert the α-olefin into an internal olefin, with the internal olefin accounting for more than 90% of the total olefin mass. Add 41g of maleic anhydride and 0.1g of the antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixture in a round-bottom flask. Heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. React under N2 protection at 190℃, then increase the temperature to 210℃ at a rate of 5℃ per hour and maintain at 210℃ for 4 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0044] Comparative Example 1:

[0045] 100g of α-olefin was isomerized into an internal olefin by liquid-phase isomerization, with the internal olefin accounting for more than 90% of the total olefin mass. 41g of maleic anhydride and 0.1g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene were added to the isomerized mixture in a round-bottom flask and heated to 90°C. After the maleic anhydride melted, N2 was bubbled through the bottom of the solution for half an hour, then the nitrogen bubbling was stopped, and the reaction vessel was sealed to prevent air from entering. The reaction was continued at 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour and held at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0046] Table 1 Test results of Examples 1-8 and Comparative Example 1

[0047]

[0048] In the conventional synthesis of ASA, the reaction rate is relatively slow due to the incompatibility between olefins and maleic anhydride in the feedstock. Furthermore, maleic anhydride is prone to self-polymerization, forming dimers and resulting in a high proportion of byproducts. However, when alkanes are mixed in with the olefins, the alkanes can dissolve some of the maleic anhydride, reducing the self-polymerization reaction and ultimately lowering the proportion of byproducts. Simultaneously, because the reaction between maleic anhydride and olefins reaches equilibrium under certain conditions, no new ASA is produced. The presence of alkanes in this feedstock is equivalent to an excess of olefins, which to some extent improves the conversion rate of olefins and maleic anhydride. Although the addition of a certain amount of alkanes is beneficial for increasing olefin conversion and reducing byproducts, this effect weakens when the alkane content is too high. Moreover, from a reaction efficiency perspective, since alkanes do not participate in the reaction, the synthesis efficiency decreases after a certain proportion. This can be seen from Table 1.

[0049] As can be seen from the above examples and comparative examples, when alkanes account for 9%-50% of the total mass of alkanes and olefins, the olefin conversion rate is relatively high, and ASA has a high yield with fewer byproducts, resulting in a high olefin conversion rate; the effect is even better when alkanes account for 17%-44% of the total mass of alkanes and olefins; and the effect is even better when alkanes account for 29%-38% of the total mass of alkanes and olefins.

[0050] Example 9:

[0051] 100g of α-olefins (all C17) were isomerized in the liquid phase to form internal olefins, with the internal olefins accounting for more than 90% of the total olefins. 41g of maleic anhydride and 0.05g of the antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene were added to the isomerized mixture in a round-bottom flask and heated to 90°C. After the maleic anhydride melted, N2 was bubbled through the bottom of the solution for half an hour. The nitrogen bubbling was then stopped, and the reaction vessel was sealed to prevent air from entering. The reaction was continued at 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour and held at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0052] Example 10:

[0053] Take 100g of α-olefins (including 5g of C16 α-olefins, 90g of C17 α-olefins, and 5g of C18 α-olefins), and perform liquid-phase isomerization to convert the α-olefins into internal olefins, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0054] Example 11:

[0055] Take 100g of α-olefins (including 15g of C16 α-olefins, 70g of C17 α-olefins, and 15g of C18 α-olefins), and perform liquid-phase isomerization to convert the α-olefins into internal olefins, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0056] Example 12:

[0057] Take 100g of α-olefins (including 25g of C16 α-olefins, 50g of C17 α-olefins, and 25g of C18 α-olefins), and perform liquid-phase isomerization to convert the α-olefins into internal olefins, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0058] Example 13:

[0059] Take 100g of α-olefins (including 30g of C16 α-olefins, 40g of C17 α-olefins, and 30g of C18 α-olefins), and perform liquid-phase isomerization to convert the α-olefins into internal olefins, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0060] Example 14:

[0061] Take 100g of α-olefins (including 35g of C16 α-olefins, 30g of C17 α-olefins, and 35g of C18 α-olefins), and perform liquid-phase isomerization to convert the α-olefins into internal olefins, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0062] Example 15:

[0063] Take 100g of α-olefins (including 40g of C16 α-olefins, 20g of C17 α-olefins, and 40g of C18 α-olefins), and perform liquid-phase isomerization to convert the α-olefins into internal olefins, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0064] Example 16:

[0065] Take 100g of α-olefins (including 45g of C16 α-olefins, 10g of C17 α-olefins, and 45g of C18 α-olefins), and perform liquid-phase isomerization to convert the α-olefins into internal olefins, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0066] Example 17:

[0067] Take 100g of α-olefins (including 47g of C16 α-olefins, 6g of C17 α-olefins, and 47g of C18 α-olefins), and perform liquid-phase isomerization to convert the α-olefins into internal olefins, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0068] Comparative Example 2:

[0069] Take 100g of α-olefins (50g of C16 α-olefins and 50g of C18 α-olefins), and perform liquid-phase isomerization to convert the α-olefins into internal olefins, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons in a round-bottom flask, heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging and seal the reaction vessel to prevent air from entering. Heat to 190℃ under N2 protection, increase the temperature to 210℃ at a rate of 5℃ per hour, and maintain at 210℃ for 4 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0070] Comparative Example 3:

[0071] 100g of α-olefins (all C18 α-olefins) were isomerized in the liquid phase to form internal olefins, with the internal olefins accounting for more than 90% of the total olefins. 39g of maleic anhydride and 0.05g of the antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene were added to the isomerized mixture in a round-bottom flask and heated to 90°C. After the maleic anhydride melted, N2 was bubbled through the bottom of the solution for half an hour. The nitrogen bubbling was then stopped, and the reaction vessel was sealed to prevent air from entering. The reaction was continued at 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour and held at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0072] Comparative Example 4:

[0073] 100g of α-olefins (all C16 α-olefins) were isomerized in liquid phase to form internal olefins, with the internal olefins accounting for more than 90% of the total olefins. 43g of maleic anhydride and 0.05g of the antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene were added to the isomerized mixture in a round-bottom flask and heated to 90°C. After the maleic anhydride melted, N2 was bubbled through the bottom of the solution for half an hour. The nitrogen bubbling was then stopped, and the reaction vessel was sealed to prevent air from entering. The reaction was continued at 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour and held at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0074] Table 2 Test results of Examples 9-17 and Comparative Examples 2 and 3

[0075]

[0076] The effectiveness of ASA application is mainly judged by the water resistance of the paper after ASA is added. The better the water resistance, the better the quality of the ASA product. Paper water resistance is expressed by the Cobb value, which is the amount of water absorbed by a unit area of ​​paper per unit time. The lower the Cobb value, the better the water resistance of the paper.

[0077] Paper water resistance is influenced by both the carbon chain length of ASA and the emulsification effect, with the emulsification effect also related to the carbon chain length; the longer the carbon chain, the more difficult it is to emulsify. For ASA with the same carbon number, a better emulsification effect results in better water resistance of the paper. For ASA with different carbon numbers, under the same emulsification effect, a higher carbon number leads to better water resistance. The emulsification effect is evaluated by the particle size after emulsification; a D90 particle size of 1.8-2 micrometers is preferable. Particle sizes that are too large or too small will lead to poor application performance. ASA synthesized from C16 olefins, due to its shorter carbon chain, is easy to emulsify but has poor water resistance. While ASA synthesized from C18 olefins has a longer carbon chain and better water resistance, its difficulty in emulsification also affects its performance to some extent. This patent, through extensive experiments, has found that the carbon chain length of C17 inner olefins is moderate. When used to replace C16 and C18 inner olefins, the synthesized ASA exhibits good emulsifying properties and demonstrates good water resistance in application evaluations. Furthermore, mixing C17 with C16 and C18 inner olefins also yields better results.

[0078] As shown in Table 2, a higher proportion of C17 olefins results in better emulsifying properties of ASA and a lower Cobb value. However, a higher proportion of C17 olefins also places higher demands on the process for separating C16-C18 olefins, leading to higher raw material costs. Furthermore, as the purity of C17 olefins increases, the change in water resistance tends to level off. Therefore, a higher proportion of C17 olefins is not always better. A C17 olefin content of 10% or more of the total olefins yields relatively good results, while a C17 olefin content of 20% or more achieves superior results.

[0079] Example 18:

[0080] Take 100g of α-olefins (a mixture of C16, C17, and C18 α-olefins), and isomerize them into internal olefins by liquid-phase isomerization, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixture into a round-bottom flask, heat to 90°C, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging and seal the reaction vessel to prevent air from entering. React under N2 protection at 190°C, then increase the temperature to 210°C at a rate of 5°C per hour and maintain at 210°C for 4 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances; the undistilled product in the reaction flask is the ASA product.

[0081] Example 19:

[0082] Take 100g of α-olefins (1g of α-olefins of C15 and below, 97g of a mixture of C16, C17, and C18 α-olefins, and 2g of α-olefins of C19 and above), and isomerize them into internal olefins by liquid-phase isomerization, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90°C, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0083] Example 20:

[0084] Take 100g of α-olefins (2g of α-olefins of C15 and below, 95g of a mixture of C16, C17, and C18 α-olefins, and 3g of α-olefins of C19 and above), and isomerize them into internal olefins through liquid-phase isomerization, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90°C, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging and seal the reaction vessel to prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0085] Example 21:

[0086] Take 100g of α-olefins (5g of α-olefins of C15 and below, 90g of a mixture of C16, C17, and C18 α-olefins, and 5g of α-olefins of C19 and above), and isomerize them into internal olefins by liquid-phase isomerization, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90°C, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0087] Example 22:

[0088] Take 100g of α-olefins (15g of C15 and below α-olefins, and a mixture of C16, C17, and C18 α-olefins totaling 85g), and perform liquid-phase isomerization to convert the α-olefins into internal olefins, with the internal olefins accounting for more than 90% of the total olefins. Add 42g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0089] Example 23:

[0090] Take 100g of α-olefins (85g of a mixture of C16, C17, and C18 α-olefins, and 15g of C19 and above α-olefins), and isomerize them into internal olefins through liquid-phase isomerization, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90°C, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0091] Example 24:

[0092] Take 100g of α-olefins (20g of C15 and below α-olefins, and a mixture of C16, C17, and C18 α-olefins totaling 80g), and perform liquid-phase isomerization to isomerize the α-olefins into internal olefins, with the internal olefins accounting for more than 90% of the total olefins. Add 42g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90℃, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0093] Example 25:

[0094] Take 100g of α-olefins (10g of α-olefins of C15 and below, 80g of a mixture of C16, C17, and C18 α-olefins, and 10g of α-olefins of C19 and above), and isomerize them into internal olefins by liquid-phase isomerization, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90°C, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0095] Example 26:

[0096] Take 100g of α-olefins (5g of α-olefins of C15 and below, 80g of a mixture of C16, C17, and C18 α-olefins, and 15g of α-olefins of C19 and above), and isomerize them into internal olefins by liquid-phase isomerization, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90°C, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0097] Example 27:

[0098] Take 100g of α-olefins (80g of a mixture of C16, C17, and C18 α-olefins, and 20g of C19 and above α-olefins), and isomerize them into internal olefins through liquid-phase isomerization, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90°C, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0099] Example 28:

[0100] Take 100g of α-olefins (13g of α-olefins of C15 and below, 74g of a mixture of C16, C17, and C18 α-olefins, and 13g of α-olefins of C19 and above), and isomerize them into internal olefins by liquid-phase isomerization, with the internal olefins accounting for more than 90% of the total olefins. Add 41g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the above isomerized mixed hydrocarbons into a round-bottom flask, heat to 90°C, and after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour, then stop the nitrogen purging, seal the reaction vessel, and prevent air from entering the reaction vessel. The reaction was heated to 190°C under N2 protection, and the temperature was increased to 210°C at a rate of 5°C per hour. The temperature was then maintained at 210°C for 4 hours to obtain an intermediate product. The intermediate product was then subjected to vacuum distillation at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask was the ASA product.

[0101] Table 3 Test results of Examples 18-28

[0102]

[0103]

[0104] The proportion of olefins with appropriate carbon number length has a significant impact on the emulsifying and application performance of ASA, with C16-C18 being the best. Too long or too short a proportion deteriorates the performance. As shown in Table 3, ASA achieves excellent results when the content of C16-C18 olefins is greater than 80% of the total olefin mass, and the content of C15 and below olefins or C19 and above olefins does not exceed 15%.

[0105] Example 29:

[0106] Take 100g of a mixture of α-olefins and alkanes (1g of C15 and below α-olefins, 20g of C16 α-olefins, 27g of C17 α-olefins, 22g of C18 α-olefins, 1g of C19 and above α-olefins, 1g of C15 and below alkanes, 9g of C16 alkanes, 10g of C17 alkanes, 8g of C18 alkanes, and 1g of C19 and above alkanes), and isomerize the α-olefins into internal olefins through liquid-phase isomerization, with the proportion of internal olefins accounting for more than 90% of the total proportion of olefins. Add 29.2 g of maleic anhydride and 0.05 g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixed hydrocarbons in a round-bottom flask. Heat to 90°C and, after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. React under N2 protection at 190°C, then increase the temperature to 210°C at a rate of 5°C per hour and maintain at 210°C for 4 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0107] Example 30:

[0108] Take 100g of a mixture of α-olefins and alkanes (1g of C15 and below α-olefins, 18g of C16 α-olefins, 22g of C17 α-olefins, 19g of C18 α-olefins, 1g of C19 and above α-olefins, 1g of C15 and below alkanes, 12g of C16 alkanes, 15g of C17 alkanes, 10g of C18 alkanes, and 1g of C19 and above alkanes), and isomerize the α-olefins into internal olefins by liquid-phase isomerization, with the internal olefins accounting for more than 90% of the total olefins. Add 25.1 g of maleic anhydride and 0.05 g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixed hydrocarbons in a round-bottom flask. Heat to 90°C and, after the maleic anhydride melts, purge the solution with nitrogen gas from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. Heat to 190°C under N2 protection, then increase the temperature to 210°C at a rate of 5°C per hour and maintain at 210°C for 4 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0109] Example 31:

[0110] Take 100g of a mixture of olefins and alkanes (1g of C15 and below olefins, 15g of C16 olefins, 18g of C17 olefins, 17g of C18 olefins, 1g of C19 and above olefins, 1g of C15 and below alkanes, 13g of C16 alkanes, 17g of C17 alkanes, 16g of C18 alkanes, and 1g of C19 and above alkanes), and isomerize the α-olefins into internal olefins through liquid-phase isomerization, with the internal olefins accounting for more than 90% of the total olefins. Add 21.4 g of maleic anhydride and 0.05 g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixed hydrocarbons in a round-bottom flask. Heat to 90°C and, after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. React under N2 protection at 190°C, then increase the temperature to 210°C at a rate of 5°C per hour and maintain at 210°C for 4 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0111] Example 32:

[0112] Take 100g of a mixture of olefins and alkanes (5g of C15 and below olefins, 12g of C16 olefins, 15g of C17 olefins, 15g of C18 olefins, 5g of C19 and above olefins, 5g of C15 and below alkanes, 12g of C16 alkanes, 13g of C17 alkanes, 13g of C18 alkanes, and 5g of C19 and above alkanes), and isomerize the α-olefins into internal olefins through liquid-phase isomerization, with the internal olefins accounting for more than 90% of the total olefins. Add 21.4 g of maleic anhydride and 0.05 g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixed hydrocarbons in a round-bottom flask. Heat to 90°C and, after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. React under N2 protection at 190°C, then increase the temperature to 210°C at a rate of 5°C per hour and maintain at 210°C for 4 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0113] Table 4 Test results of Examples 29-32

[0114]

[0115] As shown in Table 4, when alkanes account for 29%-48% of the total mass of alkanes and alkenes, and C17 alkenes account for 15-27% of the total mass of alkanes and alkenes, the yield is higher, the byproducts are fewer, and the performance of ASA is better.

[0116] Example 33:

[0117] Take 100g of a mixture of olefins and alkanes (1g of C15 and below olefins, 18g of C16 olefins, 22g of C17 olefins, 19g of C18 olefins, 1g of C19 and above olefins, 1g of C15 and below alkanes, 12g of C16 alkanes, 15g of C17 alkanes, 10g of C18 alkanes, and 1g of C19 and above alkanes), wherein the mixture contains 100ppm of oxygen-containing compounds. Through liquid-phase isomerization, the α-olefins are isomerized into internal olefins, with the proportion of internal olefins accounting for more than 90% of the total proportion of olefins. Add 21g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixed hydrocarbons in a round-bottom flask. Heat to 90°C and, after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. Heat to 180°C under N2 protection and maintain the temperature for 12 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0118] Example 34:

[0119] Take 100g of a mixture of olefins and alkanes (1g of C15 and below olefins, 18g of C16 olefins, 22g of C17 olefins, 19g of C18 olefins, 1g of C19 and above olefins, 1g of C15 and below alkanes, 12g of C16 alkanes, 15g of C17 alkanes, 10g of C18 alkanes, and 1g of C19 and above alkanes), wherein the mixture contains 300ppm of oxygen-containing compounds. Through liquid-phase isomerization, the α-olefins are isomerized into internal olefins, with the proportion of internal olefins accounting for more than 90% of the total proportion of olefins. Add 21g of maleic anhydride and 0.01g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixed hydrocarbons in a round-bottom flask. Heat to 90°C and, after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. Heat to 190°C under N2 protection and maintain the temperature for 12 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0120] Example 35:

[0121] Take 100g of a mixture of olefins and alkanes (1g of C15 and below olefins, 18g of C16 olefins, 22g of C17 olefins, 19g of C18 olefins, 1g of C19 and above olefins, 1g of C15 and below alkanes, 12g of C16 alkanes, 15g of C17 alkanes, 10g of C18 alkanes, and 1g of C19 and above alkanes), wherein the mixture contains 100ppm of oxygen-containing compounds. Through liquid-phase isomerization, the α-olefins are isomerized into internal olefins, with the proportion of internal olefins accounting for more than 90% of the total proportion of olefins. Add 25g of maleic anhydride and 0.07g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixed hydrocarbons in a round-bottom flask. Heat to 90°C and, after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. Heat to 190°C under N2 protection, then increase the temperature to 210°C at a rate of 5°C per hour and hold for 6 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0122] Example 36:

[0123] Take 100g of a mixture of olefins and alkanes (1g of C15 and below olefins, 18g of C16 olefins, 22g of C17 olefins, 19g of C18 olefins, 1g of C19 and above olefins, 1g of C15 and below alkanes, 12g of C16 alkanes, 15g of C17 alkanes, 10g of C18 alkanes, and 1g of C19 and above alkanes), wherein the mixture contains 300ppm of oxygen-containing compounds. Through liquid-phase isomerization, the α-olefins are isomerized into internal olefins, with the proportion of internal olefins accounting for more than 90% of the total proportion of olefins. Add 25g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixed hydrocarbons in a round-bottom flask. Heat to 90°C and, after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. Heat to 190°C under N2 protection, then increase the temperature to 210°C at a rate of 5°C per hour and hold for 4 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0124] Example 37:

[0125] Take 100g of a mixture of olefins and alkanes (1g of C15 and below olefins, 18g of C16 olefins, 22g of C17 olefins, 19g of C18 olefins, 1g of C19 and above olefins, 1g of C15 and below alkanes, 12g of C16 alkanes, 15g of C17 alkanes, 10g of C18 alkanes, and 1g of C19 and above alkanes), wherein the mixture contains 10ppm of oxygen-containing compounds. Through liquid-phase isomerization, the α-olefins are isomerized into internal olefins, with the proportion of internal olefins accounting for more than 90% of the total proportion of olefins. Add 25g of maleic anhydride and 0.04g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixed hydrocarbons in a round-bottom flask. Heat to 90°C and, after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. Heat to 190°C under N2 protection, then increase the temperature to 210°C at a rate of 5°C per hour and hold for 2 hours to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0126] Example 38:

[0127] Take 100g of a mixture of olefins and alkanes (1g of C15 and below olefins, 18g of C16 olefins, 22g of C17 olefins, 19g of C18 olefins, 1g of C19 and above olefins, 1g of C15 and below alkanes, 12g of C16 alkanes, 15g of C17 alkanes, 10g of C18 alkanes, and 1g of C19 and above alkanes), wherein the mixture contains 100ppm of oxygen-containing compounds. Through liquid-phase isomerization, the α-olefins are isomerized into internal olefins, with the proportion of internal olefins accounting for more than 90% of the total proportion of olefins. Add 25g of maleic anhydride and 0.05g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixed hydrocarbons in a round-bottom flask. Heat to 90°C and, after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. Heat to 190°C under N2 protection, and increase the temperature to 230°C at a rate of 5°C per hour to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0128] Example 39:

[0129] Take 100g of a mixture of olefins and alkanes (1g of C15 and below olefins, 18g of C16 olefins, 22g of C17 olefins, 19g of C18 olefins, 1g of C19 and above olefins, 1g of C15 and below alkanes, 12g of C16 alkanes, 15g of C17 alkanes, 10g of C18 alkanes, and 1g of C19 and above alkanes), wherein the mixture contains 100ppm of oxygen-containing compounds. Through liquid-phase isomerization, the α-olefins are isomerized into internal olefins, with the proportion of internal olefins accounting for more than 90% of the total proportion of olefins. Add 31g of maleic anhydride and 0.13g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixed hydrocarbons in a round-bottom flask. Heat to 90°C and, after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. Heat to 190°C under N2 protection, increase the temperature to 210°C at a rate of 5°C per hour, and continue increasing the temperature to 240°C at a rate of 10°C per hour. Hold at this temperature for 1 hour to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0130] Example 40:

[0131] Take 100g of a mixture of olefins and alkanes (1g of C15 and below olefins, 18g of C16 olefins, 22g of C17 olefins, 19g of C18 olefins, 1g of C19 and above olefins, 1g of C15 and below alkanes, 12g of C16 alkanes, 15g of C17 alkanes, 10g of C18 alkanes, and 1g of C19 and above alkanes), wherein the mixture contains 10ppm of oxygen-containing compounds. Through liquid-phase isomerization, the α-olefins are isomerized into internal olefins, with the proportion of internal olefins accounting for more than 90% of the total proportion of olefins. Add 25g of maleic anhydride and 0.13g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixed hydrocarbons in a round-bottom flask. Heat to 90°C and, after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. Heat to 190°C under N2 protection, increase the temperature to 210°C at a rate of 5°C per hour, and continue increasing the temperature to 240°C at a rate of 30°C per hour. Hold at this temperature for 1 hour to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0132] Example 41:

[0133] Take 100g of a mixture of olefins and alkanes (1g of C15 and below olefins, 18g of C16 olefins, 22g of C17 olefins, 19g of C18 olefins, 1g of C19 and above olefins, 1g of C15 and below alkanes, 12g of C16 alkanes, 15g of C17 alkanes, 10g of C18 alkanes, and 1g of C19 and above alkanes), wherein the mixture contains 100ppm of oxygen-containing compounds. Through liquid-phase isomerization, the α-olefins are isomerized into internal olefins, with the proportion of internal olefins accounting for more than 90% of the total proportion of olefins. Add 31.4 g of maleic anhydride and 0.13 g of antioxidant 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzene)benzene to the isomerized mixed hydrocarbons in a round-bottom flask. Heat to 90°C and, after the maleic anhydride melts, purge the solution with N2 from the bottom for half an hour. Stop the nitrogen purging and seal the reaction vessel to prevent air from entering. Heat to 190°C under N2 protection, increase the temperature to 210°C at a rate of 5°C per hour, and continue increasing the temperature to 240°C at a rate of 30°C per hour. Hold at this temperature for 1 hour to obtain an intermediate product. Perform vacuum distillation on the intermediate product at 10-4000 Pa to remove unreacted substances. The undistilled product in the reaction flask is the ASA product.

[0134] Table 5 Test results of Examples 29-41

[0135]

[0136] As shown in Table 5, the reaction temperature is 190-240℃, the reaction time is 6-12 hours, the amount of antioxidant is 0.1‰-1‰, the molar ratio of maleic anhydride to olefin is 1.2:1-0.8:1, and the content of oxygen-containing compounds is ≤300ppm. This method has a high olefin conversion rate and low by-products.

[0137] The above specific embodiments are merely several optional embodiments of the present invention. Based on the technical solutions of the present invention and the relevant teachings of the above embodiments, those skilled in the art can make various alternative improvements and combinations to the above specific embodiments.

Claims

1. A method for preparing alkenyl succinic anhydride from a mixture of alkane and alkene raw materials, characterized in that: Maleic anhydride and antioxidants are added to the alkane-olefin mixture and heated to 70-150℃; After the maleic anhydride has melted, purge the solution with N2O for 1-1 hour from the bottom. Under N2 protection, the mixture is heated to 190-240℃ for 6-12 hours to form reactants. Unreacted substances were removed by distillation of the reactants to obtain alkenyl succinic anhydride; In the aforementioned alkane-olefin mixture, C16, C17, and C18 olefins account for 80% or more of the total olefin mass, C15 and below olefins account for 15% or less of the total olefin mass, C19 and above olefins account for 15% or less of the total olefin mass, and C17 olefins account for 10% or more of the total olefin mass; alkanes account for 9-50% of the total alkane-olefin mass; and after isomerization, internal olefins account for 90% or more of the total olefin mass.

2. The method for preparing alkenyl succinic anhydride from a mixture of alkane and alkene raw materials according to claim 1, characterized in that: The alkanes comprise 17-44% of the total mass of alkanes and alkenes; the C17 alkenes comprise 20% or more of the total mass of alkenes.

3. The method for preparing alkenyl succinic anhydride from a mixture of alkane and alkene raw materials according to claim 2, characterized in that: The alkanes comprise 29-38% of the total mass of alkanes and alkenes.

4. The method for preparing alkenyl succinic anhydride from a mixture of alkane and alkene raw materials according to claim 1, characterized in that: The alkanes comprise 29-48% of the total mass of alkanes and alkenes; the C17 alkenes comprise 15-27% of the total mass of alkanes and alkenes.

5. The method for preparing alkenyl succinic anhydride from a mixture of alkane and alkene raw materials according to claim 1, characterized in that: The amount of antioxidant used is 0.1‰-1‰ of the total weight of the mixture of maleic anhydride, alkanes and olefins.

6. The method for preparing alkenyl succinic anhydride from a mixture of alkane and alkene raw materials according to claim 5, characterized in that: The antioxidant is 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl).

7. A method for preparing alkenyl succinic anhydride from a mixture of alkane and alkene raw materials according to any one of claims 1-6, characterized in that: The molar ratio of the inner olefin to maleic anhydride is from 1.2:1 to 0.8:

1.

8. The method for preparing alkenyl succinic anhydride from a mixture of alkane and alkene raw materials according to claim 7, characterized in that: The alkane-olefin mixture is derived from the C16-C18 component prepared from coal-based raw materials.

9. The method for preparing alkenyl succinic anhydride from a mixture of alkane and alkene raw materials according to claim 8, characterized in that: The oxygen-containing compounds in the C16-C18 components prepared from coal-based raw materials do not exceed 300 ppm.

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