Preparation method of liquid petroleum resin and obtained product

Abstract

The invention discloses a liquid petroleum resin preparation method and an obtained product, isoamylene, alpha-methyl styrene and alpha-pinene are uniformly mixed to obtain a mixed solution; adding a supported Friedel-Crafts catalyst into a part of the mixed solution, then adjusting the temperature and dropwise adding the C5 fraction and the residual mixed solution at the same time, carrying out a first-stage heat preservation reaction after dropwise adding, and then heating to carry out a second-stage heat preservation reaction, so as to obtain a reaction solution; and carrying out post-treatment on the reaction liquid to obtain the product. The preparation method of the liquid petroleum resin is improved, the high-quality liquid petroleum resin which is appropriate in softening point, narrow in relative molecular mass distribution and low in chroma can be prepared, meanwhile, the production process is simplified, energy consumption is reduced, pollutant emission is reduced, the requirements of industrial production and environmental protection are met, and the method is suitable for industrial production. The method has important practical significance and market value.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of petroleum chemical industry, in particular to a preparation method of liquid petroleum resin and the obtained product. BACKGROUND

[0002] In the petroleum chemical industry, the position of petroleum resin is very important. As an important chemical raw material, liquid petroleum resin has a wide range of applications in adhesives, coatings, inks, rubber processing and many other fields due to its excellent flowability, compatibility and bonding performance. However, there are still many problems to be solved in the current preparation technology of liquid petroleum resin.

[0003] The liquid petroleum resin produced by the traditional preparation method has obvious shortcomings in performance. The softening point fluctuates greatly, which is difficult to stabilize and control within a certain range, which leads to poor adaptability of the product in actual application. The relative molecular mass distribution is wide, which will affect the uniformity and use effect of the resin, for example, it may cause unstable bonding strength in adhesive production. At the same time, the colority of the product is high, which limits its application in fields with high appearance requirements, such as high-grade coatings, light-colored inks, etc.

[0004] From the production process, the traditional method also has many disadvantages. For example, the production efficiency is low, and the reaction period is too long, so that the output per unit time is difficult to improve, which cannot meet the needs of large-scale industrial production. In terms of energy consumption, the traditional process often needs to be carried out at high temperature and pressure, resulting in huge energy consumption and increasing production cost. In addition, a large amount of wastewater, waste gas and waste residue are produced in the production process, which causes serious pollution to the environment and does not meet the development concept of green chemical industry.

[0005] Although some improved technologies have appeared in recent years, some can only improve the product performance or production conditions in a certain aspect, and cannot achieve overall optimization; some are difficult to realize industrialization due to complex process and high cost. With the rapid development of related industries, the performance requirements of liquid petroleum resin are increasing, therefore, it is an urgent need in the industry to develop a preparation method that can comprehensively solve the above problems and realize the production of liquid petroleum resin with high performance, high efficiency, low energy consumption and low pollution. SUMMARY

[0006] In view of the deficiencies of the prior art, the present application provides a preparation method of liquid petroleum resin and the obtained product. The process flow of the method is simple, the energy consumption is low, and the pollutant emission is small, which meets the requirements of industrial production and environmental protection. The obtained liquid petroleum resin has suitable softening point, narrow relative molecular mass distribution, low colority and high quality, and has good market prospect.

[0007] The specific technical scheme of the present application is as follows: A method for preparing a liquid petroleum resin, the method comprising the steps of: (1) uniformly mixing isopentene, alpha-methylstyrene and alpha-pinene to obtain a uniform mixture; (2) mixing part of the mixture with a supported Friedel-Crafts catalyst to obtain solution 1, then adjusting the temperature and simultaneously adding a C5 fraction and the remaining mixture into solution 1 dropwise, respectively, after the dropwise addition is completed, performing a first-stage incubation reaction, and then performing a second-stage incubation reaction at an elevated temperature to obtain a reaction solution; (3) adding dilute hydrochloric acid to the reaction solution, stirring and reacting, and then separating the layers to obtain an organic phase A; (4) adding a sodium hydroxide solution to the organic phase A to perform a neutralization reaction, separating the layers after the reaction, and obtaining an organic phase B; (5) decolorizing the organic phase B with activated carbon, purifying the decolorized product by distillation, and obtaining a residual product as the liquid petroleum resin.

[0008] Further, the raw materials used in the present application need to meet the requirements of high purity and low water content. The purity of isopentene is greater than or equal to 98%, the purity of alpha-methylstyrene is greater than or equal to 97%, the purity of alpha-pinene is greater than or equal to 95%, and the effective ingredient content in the C5 fraction is greater than or equal to 90%. The water content of each raw material is less than or equal to 0.05%. Purity and water content are key links to ensure the smooth progress of subsequent reactions and product quality. If each raw material does not meet the requirements of purity and water content, the raw material needs to be pretreated before use. The pretreatment is as follows: using rectification to purify the raw material with unqualified purity, and then passing the purified raw material into a drying tower filled with molecular sieves to dehydrate, the molecular sieves are selected from 4A molecular sieves, and the water content in the raw material is reduced to less than or equal to 0.05% through adsorption.

[0009] Further, in step (1), the mass ratio of isopentene, alpha-methylstyrene and alpha-pinene in the mixture is (1-5):1-1.2:1, and preferably (2-4):1:1.

[0010] Further, in step (1), after isopentene, alpha-methylstyrene and alpha-pinene are mixed, the mixture is stirred at a stirring rate of 200-500 r / min until a uniform mixture is obtained.

[0011] Further, in step (2), the supported Friedel-Crafts catalyst uses activated carbon as a carrier and aluminum trichloride and zinc chloride as active ingredients, the active ingredients are loaded on the activated carbon, the loading amount of aluminum trichloride is 10-15 wt%, for example, 10%, 11%, 12%, 13%, 14% or 15%, and the loading amount of zinc chloride is 2-5 wt%, for example, 2%, 3%, 4% or 5%.

[0012] Further, in step (2), the amount of the supported Friedel-Crafts catalyst added is 1-3% of the mass of the mixed solution, for example, 1%, 2%, 3%, preferably 2-3%.

[0013] Further, in step (2), the polymerization reaction is divided into a pre-reaction stage, a gradient feeding stage and a holding stage: in the pre-reaction stage, part of the mixed solution and the supported Friedel-Crafts catalyst are first added to the reaction kettle; in the gradient feeding stage, the C5 fraction and the remaining mixed solution are respectively added dropwise through the double feeding ports, and the mixed solution and the C5 fraction are added dropwise at the same time; in the holding stage, after the dropwise addition is completed, the reaction is held for a period of time, and then the temperature is increased and the reaction is held for another period of time.

[0014] Further, in step (2), 20-30wt% of the mixed solution is first mixed with the supported Friedel-Crafts catalyst.

[0015] Further, in step (2), the mass ratio of the C5 fraction to the mixed solution is 1:(2-6), for example, 1:2, 1:3, 1:4, 1:5, 1:6, preferably 1:(3-5).

[0016] Further, in step (2), in the gradient feeding stage, the C5 fraction and the mixed solution are respectively added dropwise at a suitable temperature and stirring speed, the temperature during dropwise addition is 30-40℃, the stirring speed during dropwise addition is 150-300r / min, and the dropwise addition rate of the C5 fraction is 3-5g / min. The dropwise addition rate of the mixed solution is ensured to be the same as or almost the same as that of the C5 fraction.

[0017] Further, in step (2), after the dropwise addition of the C5 fraction and the mixed solution is completed, the reaction is continued at 30-40℃ and 150-300r / min for 30-40min for the first holding reaction; then the reaction is continued at 40-50℃ and 350-500r / min for 40-50min for the second holding reaction.

[0018] Further, in step (3), dilute hydrochloric acid is added to remove the catalyst. The concentration of the dilute hydrochloric acid is 4-6wt%, and the volume ratio of the dilute hydrochloric acid to the reaction solution is (0.2-1):1, preferably (0.2-0.4):1. After the dilute hydrochloric acid is added, the reaction is stirred at 25-35℃ and 100-200r / min for 20-40min, and then static separation is performed.

[0019] Further, in step (4), the neutralization reaction is controlled to have a pH value of 7-8, and after adding the sodium hydroxide solution, the reaction is carried out at a temperature of 35-45 DEG C and a stirring rate of 100-150 r / min for 15-20 min. The concentration of the sodium hydroxide solution can be 8-20 wt%.

[0020] Further, in step (5), the active carbon decoloring agent is added in an amount of 1-5 wt% of the mass of the organic phase B, preferably 2-4 wt%. The decoloring temperature is 60-80 DEG C, the stirring rate during decoloring is 150-200 r / min, and the decoloring time is 0.5-1.5 h.

[0021] Further, in step (5), the filtrate after decoloring is first subjected to atmospheric distillation, and then subjected to reduced pressure distillation. The atmospheric distillation is carried out at a temperature of 100-300 DEG C, preferably 100-150 DEG C, to distill out unreacted low-boiling light components. The reduced pressure distillation is carried out at a temperature of 200-250 DEG C and a pressure of -0.097 to -0.095 MPa, to distill out residual impurities and part of high-boiling components, to obtain a pure liquid petroleum resin product. The obtained liquid petroleum product has a narrow molecular weight distribution, low colority, and a small softening point range, and has more stable performance in use.

[0022] The present application improves the preparation method of liquid petroleum resin, and can prepare high-quality liquid petroleum resin with suitable softening point, narrow relative molecular mass distribution, and low colority, while simplifying the production process, reducing energy consumption, and reducing pollutant emissions, to meet the requirements of industrial production and environmental protection, and has important practical significance and market value. Compared with the prior art, the present application has the following advantages: 1. Excellent product performance: By precisely controlling the raw material ratio, stepwise reaction conditions, and post-treatment process, the prepared liquid petroleum resin has stable performance. The softening point can be stably controlled within a specific range (such as 0-20 DEG C according to different raw material ratios), which can meet the needs of different application scenarios. The relative molecular mass distribution is narrow, usually between 1.0 and 1.5, which ensures the uniformity of the resin and the consistency of the use performance. The colority (YI) can be controlled to be below 24, or even lower, which expands its application in high-end product fields.

[0023] 2. High production efficiency: The optimized reaction process shortens the reaction period, and the whole polymerization reaction process is more efficient. At the same time, the connection between the processes is smoother, reducing the waiting time during production and improving the output per unit time, which is suitable for large-scale industrial production.

[0024] 3. Low energy consumption: the reaction is carried out at relatively low temperature and pressure, reducing energy consumption. Compared with traditional processes, the energy consumption of the present application can be reduced by more than 20%. In addition, the combination of atmospheric distillation and vacuum distillation in the distillation process further optimizes energy utilization efficiency.

[0025] 4. Good environmental performance: the pretreatment of raw materials improves the utilization rate of raw materials and reduces waste. In the catalyst removal and neutralization process, the reagent used is easy to handle, and the reaction product can be recycled. The activated carbon used in the decolorization process can be reused through regeneration treatment. During the entire production process, the discharge of wastewater, waste gas and waste residue is greatly reduced, and after simple treatment, it can meet the environmental emission standards, in line with the development trend of green chemical industry.

[0026] 5. Strong process stability: the preparation method of the present application has clear parameters for each step, easy to control, and good process repeatability. In different batches of production, the product quality fluctuation is small, which can ensure the stability and consistency of the product, and reduce the quality risk in the production process. DETAILED DESCRIPTION

[0027] To make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

[0028] In the following examples and comparative examples, the raw materials used are commercially available products unless otherwise specified.

[0029] In the following examples and comparative examples, the color (YI) of the product was measured by GB / T 23774-2009 "Determination of color of liquid chemical products (platinum-cobalt color number)". The softening point of the product was measured by GB / T 4507-2014 "Determination of softening point of petroleum bitumen (ring and ball method)". The relative molecular mass of the product was measured by gel permeation chromatography (GPC), and the relative molecular mass distribution was the ratio of weight average molecular weight to number average molecular weight, and the test method was the same as the test method of relative molecular mass.

[0030] In the following examples and comparative examples, the product yield calculation formula is: yield (%) = [actual obtained liquid petroleum resin product mass / (∑each raw material mass The purity of the effective polymerization monomer in the raw material) ] x 100%.

[0031] Example 1 1. Raw material pretreatment: Selecting isopentene with purity of 98.5%, α-methylstyrene with purity of 97.2%, α-pinene with purity of 95.5%, and C5 fraction with effective component content of 91%. Each raw material is dehydrated by passing through a dryer containing 4A molecular sieve, and the water content of the treated raw material is reduced to below 0.04%.

[0032] 2. Mixing: 180 g of dehydrated isopentene, 60 g of α-methylstyrene, and 60 g of α-pinene are added to a four-necked flask, and stirred at a stirring rate of 300 r / min for 30 min to obtain a uniform mixture.

[0033] 3. Polymerization reaction: 60 g of the mixture and 7.5 g of a supported Friedel-Crafts catalyst (15wt% aluminum trichloride and 5wt% zinc chloride supported on activated carbon) are added to a reaction kettle. The reaction temperature is controlled at 35°C, the stirring rate is 200 r / min, 75 g of C5 fraction is added at a dropping rate of 4 g / min, and 240 g of the mixture is added at a dropping rate of 12.8 g / min. After the dropping is completed, the reaction is carried out at the above conditions for 35 min, then the temperature is raised to 45°C, the stirring rate is adjusted to 400 r / min, and the reaction is continued for 45 min. The reaction liquid is obtained after the reaction is completed.

[0034] 4. Catalyst removal: The reaction liquid is added to a 5wt% concentrated hydrochloric acid solution (the volume ratio of hydrochloric acid to reaction liquid is 0.2:1), and the reaction is carried out at 30°C and 150 r / min for 30 min. After standing and layering, the lower aqueous phase is discharged to obtain organic phase A.

[0035] 5. Neutralization: Organic phase A is added to a 10wt% sodium hydroxide solution, and the pH is adjusted to 7-8 at 40°C and 120 r / min. After the reaction is carried out for 20 min, the solution is allowed to stand and layer, and the lower salt solution is discharged to obtain organic phase B.

[0036] 6. Decolorization: 3% activated carbon is added to the neutralized organic phase B, and the solution is heated and decolorized at 70°C and 180 r / min for 1 h. Then the activated carbon is removed by filtration to obtain a filtrate.

[0037] 7. Distillation: The filtrate is sent to a distillation device, and normal pressure distillation is carried out at 100-150°C, and then vacuum distillation is carried out at -0.095 MPa and 200-220°C. Finally, a pure liquid petroleum resin product is obtained.

[0038] The product has a colority (YI) of 16, a softening point of 8-12°C, a relative number average molecular weight of 630-670, and a relative molecular weight distribution of 1.1. The product yield is 42.8%.

[0039] Example 2 1. Raw material pretreatment: Select isopentene with a purity of 98.2%, α-methylstyrene with a purity of 97.0%, α-pinene with a purity of 95.0%, and C5 fraction with an effective component content of 90%. Pass each raw material into a dryer containing 4A molecular sieves for dehydration treatment. After treatment, the water content of each raw material is reduced to below 0.04%.

[0040] 2. Mixing: After dehydration, add 255 g of isopentene, 85 g of α-methylstyrene, and 85 g of α-pinene into a four-necked flask, and stir at a stirring rate of 300 r / min for 30 min to obtain a uniform mixture.

[0041] 3. Polymerization reaction: Add 85 g of the mixture and 7.5 g of a supported Friedel-Crafts catalyst (15wt% aluminum trichloride and 5wt% zinc chloride supported on activated carbon) into a reaction kettle. Control the reaction temperature at 30°C, the stirring rate at 200 r / min, and add 106.3 g of C5 fraction at a dropping speed of 5 g / min and 340 g of the mixture at a dropping speed of 16 g / min. After dropping, maintain the reaction at this condition for 35 min, then increase the temperature to 50°C, adjust the stirring rate to 350 r / min, and continue the reaction for 45 min. After the reaction is completed, obtain a reaction liquid.

[0042] 4. Catalyst removal: Same as in Example 1.

[0043] 5. Neutralization: Same as in Example 1.

[0044] 6. Decolorization: Same as in Example 1.

[0045] 7. Distillation: Same as in Example 1.

[0046] After detection, the product obtained finally has a colority (YI) of 20, a softening point of 5-9°C, a relative number average molecular weight of 650-720, and a relative molecular weight distribution of 1.2. The product yield is 41.3%.

[0047] Example 3 1. Raw material pretreatment: Same as in Example 1.

[0048] 2. Mixing: After dehydration, add 240 g of isopentene, 60 g of α-methylstyrene, and 60 g of α-pinene into a four-necked flask, and stir at a stirring rate of 300 r / min for 30 min to obtain a uniform mixture.

[0049] 3. Polymerization: 108 g of the mixed solution and 9 g of the supported Friedel-Crafts catalyst (15 wt% of aluminum chloride and 5 wt% of zinc chloride supported on activated carbon) were added into a reaction kettle. The reaction temperature was controlled at 35°C, the stirring rate was 200 r / min, 75 g of the C5 fraction was added at a dropping speed of 4 g / min, and 252 g of the mixed solution was added at a dropping speed of 13.4 g / min. After the addition, the reaction was continued at the same conditions for 35 min. Then the temperature was raised to 45°C, the stirring rate was adjusted to 400 r / min, and the reaction was continued for another 45 min. After the reaction, a reaction solution was obtained.

[0050] 4. Catalyst removal: same as in Example 1.

[0051] 5. Neutralization: same as in Example 1.

[0052] 6. Decolorization: same as in Example 1.

[0053] 7. Distillation: same as in Example 1.

[0054] The detection results showed that the liquid petroleum resin had a colority (YI) of 22, a softening point of 4-12°C, a relative number average molecular weight of 610-650, a relative molecular weight distribution of 1.25, and a product yield of 38.7%.

[0055] Example 4 1. Raw material pretreatment: isopentene with a purity of 98.5%, α-methylstyrene with a purity of 97.2%, α-pinene with a purity of 95.5%, and C5 fraction with an effective component content of 91% were selected. Each raw material was dehydrated by passing through a dryer containing 4A molecular sieves, and the water content of each raw material was reduced to below 0.04% after the treatment.

[0056] 2. Mixing: 120 g of the dehydrated isopentene, 60 g of the dehydrated α-methylstyrene, and 60 g of the dehydrated α-pinene were added into a four-necked flask, and stirred at a stirring rate of 300 r / min for 30 min to obtain a uniform mixed solution.

[0057] 3. Polymerization: 60 g of the mixed solution and 6 g of the supported Friedel-Crafts catalyst (10% aluminum trichloride and 2% zinc chloride supported on activated carbon) were added into a reaction kettle. The reaction temperature was controlled at 40°C, the stirring rate was 300 r / min, 80 g of C5 fraction was added at a dropping speed of 3 g / min, and 180 g of the mixed solution was added at a dropping speed of 6.75 g / min. After the dropping, the reaction was continued at the same conditions for 35 min. Then the temperature was raised to 50°C, the stirring rate was adjusted to 500 r / min, and the reaction was continued for 45 min. After the reaction was completed, the reaction liquid was obtained.

[0058] 4. Catalyst removal: The reaction liquid was added into a 5 wt% dilute hydrochloric acid solution (dilute hydrochloric acid and reaction liquid in a volume ratio of 0.5:1), and the reaction was carried out at 25°C and 200 r / min for 35 min. After the reaction, the lower aqueous phase was removed to obtain organic phase A.

[0059] 5. Neutralization: Organic phase A was added into a 10 wt% sodium hydroxide solution, and the pH was adjusted to 7-8 at 35°C and 100 r / min. After the reaction for 15 min, the lower salt solution was removed to obtain organic phase B.

[0060] 6. Decolorization: 5% activated carbon was added into the neutralized organic phase B, and the reaction was carried out at 80°C and 150 r / min for 1 h. Then the activated carbon was removed by filtration to obtain a filtrate.

[0061] 7. Distillation: The filtrate was sent into a distillation device, and normal pressure distillation was carried out at 100-150°C. Then vacuum distillation was carried out at -0.095 MPa, 200-220°C. Finally, a pure liquid petroleum resin product was obtained.

[0062] It was detected that the colority (YI) of the product was 24, the softening point was 6-15°C, the relative number average molecular weight was 660-710, and the relative molecular weight distribution was 1.28. The product yield was 40.2%.

[0063] Comparative Example 1 The liquid petroleum resin product was prepared according to the method of Example 1, except that in step 3, 7.5 g of the supported Friedel-Crafts catalyst (15% aluminum trichloride and 5% zinc chloride supported on activated carbon) was replaced by 7.5 g of aluminum trichloride.

[0064] It was detected that the colority (YI) of the obtained liquid petroleum resin was 40, the softening point was 7-20°C, the relative molecular weight distribution was 1.8, and the product yield was 36.4%.

[0065] Comparative Example 2 1. Raw material pretreatment: Select isopentene with a purity of 98.5%, a-methylstyrene with a purity of 97.2%, a-pinene with a purity of 95.5%, and C5 fraction with an active ingredient content of 91%. Each raw material is passed into a dryer containing 4A molecular sieves for dehydration treatment. After treatment, the water content of the raw materials is reduced to below 0.04%.

[0066] 2. Mixing: After dehydration, 300g of isopentene, 60g of a-methylstyrene, 60g of a-pinene, and 80g of C5 fraction are added to a four-necked flask and stirred at a stirring rate of 300r / min for 30min to obtain a uniform mixture.

[0067] 3. At 40°C, the above mixture is added to a reaction kettle, and the feeding time is 70min. At the same time, aluminum chloride catalyst is slowly added. After the feeding is completed, the temperature is raised to 50°C, and the reaction is kept for 80min to obtain a reaction liquid.

[0068] 4. The reaction liquid is washed with water. Specifically, after the reaction liquid is cooled to 30°C, it is transferred to a separatory funnel, and an equal volume of deionized water is added. The stopcock is tightly closed, the funnel is held upside down and shaken for 5min, then the separatory funnel is fixed on an iron stand and left to separate for 30min. After the interface is clear, the lower water phase is slowly released by rotating the stopcock, and the upper organic phase is collected. The above water washing operation is repeated twice. After the third water washing, 2mL of the lower water phase is taken, and the pH value is detected. When the pH value is stable at 6-7, the water washing is stopped, and the final organic phase is collected.

[0069] 5. The water-washed reaction liquid is distilled. Specifically, the water-washed organic phase is transferred to a round-bottom flask, 2-3 zeolites are added, and a vacuum distillation device is installed. First, atmospheric distillation is carried out: slowly heat to 80°C and keep for 10min to remove water; continue to heat to 150°C and collect the distillate. When the distillation rate is less than 1-2 drops / s, stop the atmospheric distillation. Switch to vacuum distillation: start the vacuum pump to stabilize the system vacuum at -0.09MPa, slowly heat to 180°C, and keep for 30min to collect the residual low-boiling components; continue to heat to 220°C and keep for 20min. At this time, there is basically no distillate, stop heating, and slowly vent after the system cools to below 80°C to obtain the distilled crude resin.

[0070] 6. Stripping, specifically operating as follows: using a 500 mL three-necked flask as a stripping device, transferring the crude resin into the flask, adding deionized water and zeolite into the distillation flask, connecting to the water vapor inlet pipe, heating the water vapor generator to boiling. Turning on the crude resin heating jacket, raising the temperature to 200℃, introducing superheated water vapor, maintaining a slight positive pressure in the system. After 90 min of stripping, observing the distillate in the condensation receiving bottle, when the distillate is clear and the volume is less than 0.5 mL / 10 min, first stop heating the water vapor generator, continue heating the crude resin for 3 min to chase away the remaining steam, then stop heating, and after cooling to room temperature, the refined liquid petroleum resin product is obtained.

[0071] It is detected that the colority (YI) of the obtained liquid petroleum resin is 35, the softening point is 0-15℃, and the relative molecular mass distribution is 1.25. The product yield is 35.3%.

[0072] It can be clearly seen from the comparison of the above examples and comparative examples that the liquid petroleum resin preparation method provided by the present application has significant advantages in product performance, production stability and the like. The products prepared in Examples 1, 2, 3 and 4 are superior to Comparative Examples 1 and 2 in colority, softening point, relative molecular mass distribution and other key performance indicators, fully proving the advancement and practicality of the method of the present application.

[0073] The protection scope of the present application is not limited to the above examples, and various modifications, equivalent replacements and improvements of the preparation method of the present application made by those skilled in the art without departing from the principles and spirits of the present application shall be included in the protection scope of the present application. For example, in terms of raw material ratio, adjustment can be made within a reasonable range according to actual needs; the type and loading amount of the catalyst can also be optimized according to specific conditions; and part of the parameters in the post-treatment process can be changed appropriately under the premise of ensuring product quality. As long as a technical solution substantially the same as the present application is adopted, it shall be within the protection scope of the present application.

Claims

1. A method for preparing liquid petroleum resin, characterized in that: Includes the following steps: (1) Mix isopentenene, α-methylstyrene and α-pinene evenly to obtain a homogeneous mixture; (2) Mix part of the mixture with the supported Friedel-Crafts catalyst to obtain solution 1. Then, adjust the temperature and add C5 fraction and the remaining mixture dropwise to solution 1. After the addition is complete, carry out the first stage of heat preservation reaction, and then raise the temperature to carry out the second stage of heat preservation reaction to obtain the reaction solution. (3) Add dilute hydrochloric acid to the reaction solution, stir and react until the layers are separated to obtain organic phase A; (4) Add sodium hydroxide solution to organic phase A to carry out a neutralization reaction. After the reaction, the phases are separated to obtain organic phase B; (5) Decolorize organic phase B with activated carbon, and then purify it by distillation. The remaining product is liquid petroleum resin.

2. The preparation method according to claim 1, characterized in that: The purity of isopentenene is greater than or equal to 98%, the purity of α-methylstyrene is greater than or equal to 97%, the purity of α-pinene is greater than or equal to 95%, and the content of effective components in the C5 fraction is greater than or equal to 90%.

3. The preparation method according to claim 1 or 2, characterized in that: In step (1), the mass ratio of isopentenene, α-methylstyrene, and α-pinene is (1-5):(1-1.2):

1.

4. The preparation method according to claim 1, characterized in that: In step (2), the supported Friedel-Crafts catalyst uses activated carbon as a support, and aluminum trichloride and zinc chloride are supported on the activated carbon, wherein the loading of aluminum trichloride is 10-15% and the loading of zinc chloride is 2-5%; preferably, the amount of the supported Friedel-Crafts catalyst added is 1-3% of the mass of the mixture.

5. The preparation method according to claim 1, characterized in that: The mass ratio of C5 fraction to total mixture is 1:2 to 6; preferably, in step (2), 20 to 30 wt% of the mixture is first mixed with the supported Friedel-Crafts catalyst.

6. The preparation method according to claim 1, 4 or 5, characterized in that: In step (2), the C5 fraction and the remaining mixture are added dropwise at 30-40℃ and 150-300r / min respectively. The dropping rate of the C5 fraction is 3-5g / min, and the mixture and the C5 fraction are added dropwise simultaneously. Preferably, in step (2), after the C5 fraction and the mixture are added dropwise, the reaction is carried out at 30-40℃ and 150-300r / min for 30-40min to carry out the first stage of heat preservation reaction; Then, the reaction is carried out at 40–50℃ and 350–500 r / min for 40–50 min, followed by a second stage of heat preservation reaction.

7. The preparation method according to claim 1, characterized in that: In step (3), the concentration of dilute hydrochloric acid is 4-6 wt%, and the volume ratio of dilute hydrochloric acid to the reaction solution is (0.2-1):

1. Preferably, after adding dilute hydrochloric acid, the mixture is stirred at 25-35℃ and 100-200 r / min for 20-40 min, and then allowed to stand for layering.

8. The preparation method according to claim 1, characterized in that: In step (4), sodium hydroxide solution is added until the pH is between 7 and 8; preferably, after adding sodium hydroxide solution, the reaction is carried out at 35-45℃ and 100-150r / min for 15-20min, and then allowed to stand for layering.

9. The preparation method according to claim 1, characterized in that: In step (5), the amount of activated carbon added is 1-5% of the mass of organic phase B; preferably, the decolorization temperature is 60-80℃, the stirring rate during decolorization is 150-200r / min, and the decolorization time is 0.5-1.5h. Preferably, in step (5), the unreacted low-boiling-point light components are first distilled at atmospheric pressure at 100~300℃, and then reduced pressure distilled at -0.097~-0.095MPa and 200~250℃ to remove the residual impurities and some high-boiling-point components. The residue is the liquid petroleum resin product.

10. A liquid petroleum resin product prepared according to any one of claims 1-9.