A process for the production of a modified liquid coumarone resin emulsion

Abstract

The application discloses a production method of modified liquid coumarone resin emulsion, which comprises the following steps: adding an emulsifier into modified liquid coumarone resin, heating to a certain temperature, stirring uniformly, heating deionized water to the same temperature as the modified liquid coumarone resin; then slowly adding the deionized water into the modified liquid coumarone resin, and using phase inversion method to prepare the modified liquid coumarone resin emulsion of oil-in-water, so that the modified liquid coumarone resin is uniformly distributed in water, the product has good stability, small particle size, high solid content, simple operation and is suitable for industrial production.

Description

Technical Field

[0001] This invention belongs to the field of resin emulsion preparation technology, and relates to a method for preparing aromatic resin emulsions, specifically a method for producing modified liquid coumarone resin emulsions. Background Technology

[0002] Coumarone-indene resin (abbreviated as coumarone resin) has excellent acid resistance, alkali resistance, adhesion, plasticizing and reinforcing properties. It is soluble in solvents such as chlorinated hydrocarbons, esters, ketones, and ethers, and has good compatibility with a variety of resins such as natural rubber and epoxy resin. It has long been widely used as a modifier for various resins, and is mainly used in coatings, electronic materials, adhesives, sealants, rubber, inks and other fields.

[0003] As a type of coating product, anti-corrosion coatings are developing towards energy conservation, environmental protection, high performance, and functionality. This specifically requires anti-corrosion coatings to develop towards water-based, high-solids, and multifunctional directions. With increasingly urgent and stringent public demands for environmental protection, the development of low-energy-consumption, low-pollution, and high-performance water-based anti-corrosion coatings has become a current research hotspot. Currently, solvent-based coatings all use solid coumarone resins, which require the addition of organic solvents for dissolution during use. However, these organic solvents contribute to VOCs (volatile organic compounds) problems in the environment.

[0004] Therefore, based on the demand for water-based anti-corrosion coatings, it is necessary to develop water-based coumarone resin emulsions to meet market and regulatory requirements. Application number CN02111259.2 discloses a method for preparing a petroleum resin emulsion, including melting petroleum resin and mixing it with oleic acid, adding 5-15% ethanolamine solution for emulsification, cooling and filtering to obtain the petroleum resin emulsion. The product has a particle size of less than 0.5 micrometers and is used in adhesives and water-based coatings. However, this technology has a high emulsification temperature of 85-100℃ and a long emulsification cycle. Application number CN93108150.5 discloses a method for preparing water-soluble carbon pellet petroleum resin, including copolymerizing the C9 fraction (a byproduct of ethylene production) with acid, ester, and amine derivatives such as acrylic acid, followed by saponification. This product is used as an oilfield water quality stabilizer. However, the product obtained by this method is a water-based resin, which may affect the water resistance and other properties of subsequent coatings. Application number CN200610063547.1 discloses a petroleum resin emulsion for slurry sealing and its preparation process, including petroleum resin, cationic emulsifier, water and anhydrous CaCl2, concentrated hydrochloric acid, etc. The prepared petroleum resin is used for slurry sealing in road engineering, but the emulsification temperature of this process is relatively high, 120-160℃, and the particle size of the emulsion is large.

[0005] The present invention discloses a method for producing modified liquid coumarone resin emulsion. By adding an emulsifier to modified liquid coumarone resin and using an inversion method to obtain an oil-in-water emulsion, the hydroxyl value of the coumarone resin is uniformly distributed in water. The emulsion product has good stability, small particle size, high solid content, and high added value. In epoxy, polyurethane, and acrylic coating systems, it can improve water resistance, chemical resistance, and flexibility. The product meets environmental protection requirements, has a wide range of applications, and is suitable for industrial production. Summary of the Invention

[0006] To address the aforementioned deficiencies in the existing technology, the present invention aims to provide a method for producing a modified liquid coumarone resin emulsion. The method involves adding an emulsifier to the modified liquid coumarone resin, heating it to a certain temperature, stirring until homogeneous, and then heating deionized water to the same temperature as the modified liquid coumarone resin. The deionized water is then slowly added to the modified liquid coumarone resin, and an oil-in-water modified liquid coumarone resin emulsion is obtained using a phase inversion method. This method ensures uniform distribution of the modified liquid coumarone resin in water, resulting in a product with good stability, small particle size, high solid content, simple operation, and suitability for industrial production.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] This invention provides a method for producing a modified liquid coumarone resin emulsion, comprising the following steps:

[0009] S1, modified liquid coumarone resin was prepared using coumarone-indene distillate as raw material;

[0010] S2, add the emulsifier to the modified liquid coumarone resin and stir evenly at a preset temperature to form a mixture;

[0011] S3. After heating the deionized water to the same preset temperature as the mixture, slowly add the deionized water to the mixture while maintaining high-speed stirring. The mixture gradually forms a water-in-oil emulsion. After the viscosity gradually increases to the reverse inflection point, stop adding water, stir thoroughly, and continue adding deionized water to dilute it, thus obtaining an oil-in-water emulsion.

[0012] S4. Add defoamer and stabilizer to the oil-in-water emulsion, stir evenly, and then lower to room temperature to obtain modified liquid coumarone resin emulsion.

[0013] Preferably, in step S1, the modified liquid coumarone resin is prepared by the following method:

[0014] Raw material preparation: The coumarone-indene fraction is prepared with solvent to produce a feedstock oil with an indene content of 1-55%;

[0015] The crude coumarone fraction is depyridine and dephenolized. The feed oil is subjected to conventional acid washing and alkali washing to remove pyridine and phenol, and further neutralized to obtain the dephenolized and depyridine coumarone fraction.

[0016] Decolorization distillation involves passing the coumarone fraction (after phenol and pyridine removal) through a decolorization tower to separate the heavy fraction from the bottom and distill off the decolorized feedstock oil from the top.

[0017] Polymerization: The decolorized raw material oil is mixed with methylstyrene and a catalyst, and polymerized oil is obtained through a polymerization reaction.

[0018] The polymerized oil is washed with water and then the non-polymerized impurities are removed by distillation to obtain the modified liquid coumarone resin.

[0019] Preferably, during the preparation of the modified liquid coumarone resin:

[0020] In the raw material preparation, the solvent is one or more selected from toluene, xylene, p-toluene, and flash distilled oil; and / or

[0021] During the decolorization distillation process, the heavy fraction includes naphthalene, acid tar, and pitch; and / or

[0022] During the polymerization process, the mass ratio of methylstyrene to the decolorizing feedstock oil is 1–8:1; and / or

[0023] During the polymerization process, the catalyst is selected from one or more of aluminum trichloride, boron trifluoride, cation exchange resin, activated clay, and titanium tetrachloride; and / or

[0024] During the polymerization process, the mass of the catalyst is 0.3 to 10 wt% of the mass of the decolorized oil feedstock.

[0025] During the polymerization process, the polymerization temperature is 5–60°C and the polymerization time is 1–5 h.

[0026] Preferably, during the polymerization process:

[0027] The mass of the catalyst is 2-5 wt% of the mass of the decolorized oil feedstock; and / or

[0028] The polymerization reaction temperature is 20–40°C, and the polymerization reaction time is 2–3 hours.

[0029] Preferably, in step S2:

[0030] The emulsifier is a nonionic emulsifier; and / or

[0031] The emulsifier is present in a mass ratio of 0.05 to 0.2:1 to the modified liquid coumarone resin; and / or

[0032] The preset temperature is 40–80°C; and / or

[0033] The stirring speed is 500-2500 rpm.

[0034] Preferably, in step S2:

[0035] The emulsifier is present in a mass ratio of 0.10 to 0.15:1 to the modified liquid coumarone resin; and / or

[0036] The nonionic emulsifier is selected from one of alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, and alkanolamide; and / or

[0037] The preset temperature is 50-70℃.

[0038] Preferably, in step S3:

[0039] The total amount of deionized water added is 50-100 wt% of the mass of the modified liquid coumarone resin; and / or

[0040] The total time for adding the deionized water to the modified liquid coumarone resin is 25–35 min: and / or

[0041] The solid content of the water-in-oil emulsion is ≥50wt%.

[0042] Preferably, in step S4:

[0043] The defoamer is a mineral oil-based defoamer; and / or

[0044] The stabilizer used is a high molecular weight polyethylene glycol stabilizer.

[0045] Preferably, the modified liquid coumarone resin emulsion has a solid content of ≥50wt% and an average particle size of 0.45~1.5μm.

[0046] Preferably, the solid content of the modified liquid coumarone resin emulsion is 50-70 wt%.

[0047] The method for producing modified liquid coumarone resin emulsion provided by this invention has the following beneficial effects:

[0048] 1. The method for producing modified liquid coumarone resin emulsion of the present invention involves adding an emulsifier to modified liquid coumarone resin, heating it to a certain temperature, stirring it evenly, heating deionized water to the same temperature as modified liquid coumarone resin, and then slowly adding deionized water to modified liquid coumarone resin. A water-in-oil modified liquid coumarone resin emulsion is obtained using a phase inversion method, resulting in uniform distribution of modified liquid coumarone resin in water. The product exhibits good stability, small particle size, high solid content, simple operation, and suitability for industrial production.

[0049] 2. The production method of the modified liquid coumarone resin emulsion of the present invention obtains a modified liquid resin emulsion product that meets market demand by selecting appropriate parameters such as emulsifier, temperature, emulsifier ratio, and stirring speed. The product meets environmental protection requirements and can improve water resistance, chemical resistance, and flexibility in epoxy, polyurethane, and acrylic coating systems. The product has a wide range of applications. Detailed Implementation

[0050] To better understand the above-mentioned technical solutions of the present invention, the technical solutions of the present invention will be further described below in conjunction with embodiments.

[0051] The present invention discloses a method for producing modified liquid coumarone resin emulsions. By selecting appropriate emulsifiers, temperatures, emulsifier ratios, stirring speeds, and other parameters, modified liquid resin emulsion products that meet market demands are obtained. The present invention is simple to operate and suitable for industrial production. The key step of the present invention lies in selecting a suitable emulsifier and then changing different emulsification process conditions to obtain liquid modified coumarone resin emulsions with different solid contents.

[0052] The present invention provides a method for producing a modified liquid coumarone resin emulsion, which consists of two aspects: first, preparing modified liquid coumarone resin; and second, preparing modified liquid coumarone resin emulsion.

[0053] I. The preparation process of modified liquid coumarone resin includes the following steps:

[0054] (1) Raw material preparation: The coumarone-indene fraction is prepared with solvent to form a feed oil with an indene content of 1-55%; wherein the composition of the coumarone-indene fraction is: indene: 65%-95wt%, coumarone: 0.5%-2wt% and styrene: 0.18%-1.5wt%, and the solvent is selected from one or more of toluene, xylene, p-toluene and flash oil; flash oil refers to the light fraction of crude oil or coal tar from the initial boiling point to 200℃, which is a colorless to brown transparent liquid.

[0055] (2) Removal of pyridine and phenol from crude coumarone fraction: The feed oil is subjected to conventional acid washing and alkali washing to remove pyridine and phenol, and further neutralized to obtain the coumarone fraction (C2SN) after removal of phenol and pyridine; wherein the acid washing uses sulfuric acid with a concentration of 30-60%, and the alkali washing uses sodium hydroxide with a concentration of 1-10%.

[0056] (3) Decolorization distillation: the coumarone fraction that has been dephenolized and depyridineized is passed through a decolorization tower, and heavy fractions such as naphthalene, acid tar and asphalt are separated from the bottom of the tower, and the decolorized raw material oil (CSN) is distilled from the top of the tower.

[0057] (4) Polymerization: The decolorizing feedstock oil is mixed with methylstyrene and a catalyst, and polymerized oil is obtained through a polymerization reaction; wherein the mass ratio of methylstyrene to decolorizing feedstock oil is 1-8:1; the catalyst is selected from one or more of aluminum trichloride, boron trifluoride, cation exchange resin, activated clay and titanium tetrachloride, and the catalyst accounts for 0.3-10 wt% of the mass of the decolorizing feedstock oil. In a further preferred embodiment, the catalyst accounts for 2-5 wt% of the decolorizing feedstock oil. The polymerization reaction temperature is 5-60℃, and the polymerization reaction time is 1-5 h. In a further preferred embodiment, the polymerization reaction temperature is 20-40℃, and the polymerization reaction time is 2-3 h.

[0058] (5) Distillation: After washing the polymerized oil with water, the impurities that have not polymerized are removed by distillation to obtain modified liquid coumarone resin; the impurities that have not polymerized mainly refer to solvent and unreacted monomer.

[0059] II. The preparation process of modified liquid coumarone resin emulsion includes the following steps:

[0060] (1) The emulsifier is added to the modified liquid coumarone resin prepared above, and heated and stirred evenly at a preset temperature to form a mixture; wherein the emulsifier is a nonionic emulsifier, such as alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, alkanolamide, etc.; the mass ratio of emulsifier to modified liquid coumarone resin is 0.05 to 0.2:1, and in a further preferred embodiment, the mass ratio of emulsifier to modified liquid coumarone resin is 0.1 to 0.15:1; the preset temperature is 40 to 80°C, preferably 50 to 70°C. The stirring speed is 500 to 2500 rpm.

[0061] (2) After heating the deionized water to the same preset temperature as the mixture, slowly add the deionized water to the mixture while maintaining high-speed stirring. The mixture gradually forms a water-in-oil emulsion. After the viscosity gradually increases to the reverse inflection point, stop adding water, stir thoroughly, and continue to add deionized water for dilution to obtain an oil-in-water emulsion. The total amount of deionized water added accounts for 50 to 100 wt% of the mass of the modified liquid coumarone resin. The specific total amount of deionized water added should be determined according to the solid content requirements of the oil-in-water emulsion. The solid content of the oil-in-water emulsion is ≥50 wt%.

[0062] (3) Add defoamer and stabilizer to the oil-in-water emulsion, stir evenly and then cool to room temperature to obtain modified liquid coumarone resin emulsion; wherein the defoamer is a mineral oil defoamer and the stabilizer is a high molecular weight polyethylene glycol stabilizer.

[0063] The modified liquid coumarone resin emulsion prepared above has a solid content ≥50 wt% (in a further preferred embodiment, the solid content of the modified liquid coumarone resin emulsion is 50–70 wt%), and an average particle size of 0.45–1.5 μm.

[0064] The production method of the modified liquid coumarone resin emulsion of the present invention will be further described below with specific examples.

[0065] Example 1

[0066] The production method of the modified liquid coumarone resin emulsion in this embodiment is as follows:

[0067] Preparation process of modified liquid coumarone resin: A feedstock oil with an indene content of 20% is obtained by mixing crude coumarone-indene fraction with toluene. The feedstock oil is fed into an acid washing tank, neutralized with alkali after acid washing, and then washed with water to obtain a neutral coumarone fraction C2SN (dephenolized and depyridineized). The washed coumarone fraction C2SN is fed into a decolorizing tower, and the decolorized feedstock oil CSN is obtained at the top of the tower. α-Methylstyrene is added to the decolorized feedstock oil CSN at a mass ratio of 6:1, along with catalyst BF3 (2% by weight of the feedstock oil). The polymerization reaction is carried out at 40°C for 2 hours to obtain a polymerized oil. The polymerized oil is fed into a distillation system to remove solvent and small molecules, resulting in a resin with a molecular weight of 280 Mw and a viscosity of 90 mPa·s.

[0068] Preparation process of modified liquid coumarone resin emulsion: Add 2 grams of emulsifier sodium fatty alcohol polyoxyethylene ether sulfate to 20 grams of the above modified liquid coumarone resin, heat to 60°C, and stir evenly at a stirring speed of 1500 rpm. Heat deionized water to the same temperature as the modified liquid coumarone resin. While maintaining high-speed stirring of the modified liquid coumarone resin, slowly add deionized water. The mixed solution gradually forms a water-in-oil emulsion, and the viscosity gradually increases.

[0069] After reaching the inflection point, the emulsion viscosity suddenly decreases; stop adding water. After thorough stirring, continue slowly adding water up to 20 grams.

[0070] Further dilution was performed to obtain an oil-in-water emulsion. Then, defoamer and stabilizer were added, and the mixture was stirred until homogeneous and cooled to room temperature to obtain a modified liquid coumarone resin emulsion with a solid content of 50%. The modified liquid coumarone resin emulsion had a solid content of 50%, good stability, and an average particle size of 0.751 μm, as detailed in Table 1.

[0071] Example 2

[0072] The production method of the modified liquid coumarone resin emulsion in this embodiment is as follows:

[0073] Preparation process of modified liquid coumarone resin: A feedstock oil with an indene content of 20% is obtained by mixing crude coumarone-indene fraction with toluene. The feedstock oil is fed into an acid washing tank, neutralized with alkali after acid washing, and then washed with water to obtain a neutral coumarone fraction C2SN (dephenolized and depyridineized). The washed coumarone fraction C2SN is fed into a decolorizing tower, and the decolorized feedstock oil CSN is obtained at the top of the tower. α-Methylstyrene is added to the decolorized feedstock oil CSN at a mass ratio of 6:1, along with catalyst BF3 (2% by weight of the feedstock oil). The polymerization reaction is carried out at 40°C for 2 hours to obtain a polymerized oil. The polymerized oil is fed into a distillation system to remove solvent and small molecules, resulting in a resin with a molecular weight of 280 Mw and a viscosity of 90 mPa·s.

[0074] Preparation process of modified liquid coumarone resin emulsion: Add 2 grams of emulsifier sodium fatty alcohol polyoxyethylene ether sulfate to 20 grams of the above modified liquid coumarone resin, heat to 70°C, and stir evenly at a stirring speed of 1500 rpm. Heat deionized water to the same temperature as the modified liquid coumarone resin. While maintaining high-speed stirring of the modified liquid coumarone resin, slowly add deionized water. The mixed solution gradually forms a water-in-oil emulsion, and the viscosity gradually increases.

[0075] After reaching the inflection point, the emulsion viscosity suddenly decreases; stop adding water. After thorough stirring, continue slowly adding water up to 20 grams.

[0076] Further dilution was performed to obtain an oil-in-water emulsion. Then, defoamer and stabilizer were added, and the mixture was stirred until homogeneous and cooled to room temperature to obtain a modified liquid coumarone resin emulsion with a solid content of 50%. The modified liquid coumarone resin emulsion had a solid content of 50%, good stability, and an average particle size of 1.244 μm, as detailed in Table 1.

[0077] Example 3

[0078] The production method of the modified liquid coumarone resin emulsion in this embodiment is as follows:

[0079] Preparation process of modified liquid coumarone resin: A feedstock oil with an indene content of 20% is obtained by mixing crude coumarone-indene fraction with toluene. The feedstock oil is fed into an acid washing tank, neutralized with alkali after acid washing, and then washed with water to obtain a neutral coumarone fraction C2SN (dephenolized and depyridineized). The washed coumarone fraction C2SN is fed into a decolorizing tower, and the decolorized feedstock oil CSN is obtained at the top of the tower. α-Methylstyrene is added to the decolorized feedstock oil CSN at a mass ratio of 6:1, along with catalyst BF3 (2% by weight of the feedstock oil). The polymerization reaction is carried out at 40°C for 2 hours to obtain a polymerized oil. The polymerized oil is fed into a distillation system to remove solvent and small molecules, resulting in a resin with a molecular weight of 280 Mw and a viscosity of 90 mPa·s.

[0080] Preparation process of modified liquid coumarone resin emulsion: Add 3 grams of emulsifier sodium fatty alcohol polyoxyethylene ether sulfate to 20 grams of the above modified liquid coumarone resin, heat to 60°C, and stir evenly at a stirring speed of 1500 rpm. Heat deionized water to the same temperature as the modified liquid coumarone resin. While stirring the modified liquid coumarone resin at high speed, slowly add deionized water. The mixed solution gradually forms a water-in-oil emulsion, and the viscosity gradually increases.

[0081] After reaching the inflection point, the emulsion viscosity suddenly decreases; stop adding water. After thorough stirring, continue slowly adding water up to 20 grams.

[0082] Further dilution was performed to obtain an oil-in-water emulsion. Then, defoamer and stabilizer were added, and the mixture was stirred until homogeneous and cooled to room temperature to obtain a modified liquid coumarone resin emulsion with a solid content of 50%. The modified liquid coumarone resin emulsion had a solid content of 50%, good stability, and an average particle size of 0.720 μm, as detailed in Table 1.

[0083] Example 4

[0084] The production method of the modified liquid coumarone resin emulsion in this embodiment is as follows:

[0085] Preparation process of modified liquid coumarone resin: A feedstock oil with an indene content of 20% is obtained by mixing crude coumarone-indene fraction with toluene. The feedstock oil is fed into an acid washing tank, neutralized with alkali after acid washing, and then washed with water to obtain a neutral coumarone fraction C2SN (dephenolized and depyridineized). The washed coumarone fraction C2SN is fed into a decolorizing tower, and the decolorized feedstock oil CSN is obtained at the top of the tower. α-Methylstyrene is added to the decolorized feedstock oil CSN at a mass ratio of 6:1, along with catalyst BF3 (2% by weight of the feedstock oil). The polymerization reaction is carried out at 40°C for 2 hours to obtain a polymerized oil. The polymerized oil is fed into a distillation system to remove solvent and small molecules, resulting in a resin with a molecular weight of 280 Mw and a viscosity of 90 mPa·s.

[0086] Preparation process of modified liquid coumarone resin emulsion: Add 3 grams of emulsifier sodium fatty alcohol polyoxyethylene ether sulfate to 20 grams of the above modified liquid coumarone resin, heat to 60°C, and stir evenly at a stirring speed of 2500 rpm. Heat deionized water to the same temperature as the modified liquid coumarone resin. While maintaining high-speed stirring of the modified liquid coumarone resin, slowly add deionized water. The mixed solution gradually forms a water-in-oil emulsion, and the viscosity gradually increases.

[0087] Upon reaching the inversion point, the emulsion viscosity suddenly decreased, and water addition was stopped. After thorough stirring, water was slowly added to 10.7 g for dilution, resulting in an oil-in-water emulsion. Then, defoamer and stabilizer were added, and the mixture was stirred until homogeneous and cooled to room temperature to obtain a modified liquid coumarone resin emulsion with a solid content of 65%. The modified liquid coumarone resin emulsion exhibited a solid content of 65%, good stability, and an average particle size of 0.471 μm, as detailed in Table 1.

[0088] Example 5

[0089] The production method of the modified liquid coumarone resin emulsion in this embodiment is as follows:

[0090] Preparation process of modified liquid coumarone resin: A feedstock oil with an indene content of 20% is obtained by mixing crude coumarone-indene fraction with toluene. The feedstock oil is fed into an acid washing tank, neutralized with alkali after acid washing, and then washed with water to obtain a neutral coumarone fraction C2SN (dephenolized and depyridineized). The washed coumarone fraction C2SN is fed into a decolorizing tower, and the decolorized feedstock oil CSN is obtained at the top of the tower. α-Methylstyrene is added to the decolorized feedstock oil CSN at a mass ratio of 6:1, along with catalyst BF3 (2% by weight of the feedstock oil). The polymerization reaction is carried out at 40°C for 2 hours to obtain a polymerized oil. The polymerized oil is fed into a distillation system to remove solvent and small molecules, resulting in a resin with a molecular weight of 280 Mw and a viscosity of 90 mPa·s.

[0091] Preparation process of modified liquid coumarone resin emulsion: Add 3.2 g of emulsifier sodium fatty alcohol polyoxyethylene ether sulfate to 20 g of the modified liquid coumarone resin, heat to 70°C, and stir evenly at 2500 rpm. Heat deionized water to the same temperature as the modified liquid coumarone resin. While maintaining high-speed stirring, slowly add deionized water. The mixed solution gradually forms a water-in-oil emulsion, and the viscosity gradually increases. After reaching the inversion point, the emulsion viscosity suddenly decreases, and water addition is stopped. After thorough stirring, continue to slowly add water to 16.4 g for dilution, obtaining an oil-in-water emulsion. Then add defoamer and stabilizer, stir evenly, and cool to room temperature to obtain a modified liquid coumarone resin emulsion with a solid content of 55%. The modified liquid coumarone resin emulsion has a solid content of 55%, good stability, and an average particle size of 0.595 μm, as detailed in Table 1.

[0092] Example 6

[0093] The production method of the modified liquid coumarone resin emulsion in this embodiment is as follows:

[0094] Preparation process of modified liquid coumarone resin: A feedstock oil with an indene content of 20% is obtained by mixing crude coumarone-indene fraction with toluene. The feedstock oil is fed into an acid washing tank, neutralized with alkali after acid washing, and then washed with water to obtain a neutral coumarone fraction C2SN (dephenolized and depyridineized). The washed coumarone fraction C2SN is fed into a decolorizing tower, and the decolorized feedstock oil CSN is obtained at the top of the tower. α-Methylstyrene is added to the decolorized feedstock oil CSN at a mass ratio of 6:1, along with catalyst BF3 (2% by weight of the feedstock oil). The polymerization reaction is carried out at 40°C for 2 hours to obtain a polymerized oil. The polymerized oil is fed into a distillation system to remove solvent and small molecules, resulting in a resin with a molecular weight of 280 Mw and a viscosity of 90 mPa·s.

[0095] Preparation process of modified liquid coumarone resin emulsion: Add 3.6 g of emulsifier sodium fatty alcohol polyoxyethylene ether sulfate to 20 g of the modified liquid coumarone resin, heat to 60°C, and stir evenly at 2500 rpm. Heat deionized water to the same temperature as the modified liquid coumarone resin. While maintaining high-speed stirring, slowly add deionized water. The mixed solution gradually forms a water-in-oil emulsion, and the viscosity gradually increases. After reaching the inversion point, the emulsion viscosity suddenly decreases, and water addition is stopped. After thorough stirring, continue to slowly add water up to 16.4 g for dilution to obtain an oil-in-water emulsion. Then add defoamer and stabilizer, stir evenly, and cool to room temperature to obtain a modified liquid coumarone resin emulsion with a solid content of 55%. The modified liquid coumarone resin emulsion has a solid content of 55%, good stability, and an average particle size of 0.641 μm. See Table 1 for details.

[0096] Table 1 Preparation parameters and performance

[0097]

[0098]

[0099] Note: (1) Solid content was determined in accordance with GB / T20623;

[0100] (2) The stability standard is that after standing at room temperature for 30 days, there should be no visual observation of sedimentation and stratification.

[0101] (3) Particle size was determined using a Malvern 2000 particle size analyzer.

[0102] In summary, the production method of the modified liquid coumarone resin emulsion of the present invention involves adding an emulsifier to the modified liquid coumarone resin, heating it to a certain temperature, stirring until homogeneous, heating deionized water to the same temperature as the modified liquid coumarone resin, and then slowly adding the deionized water to the modified liquid coumarone resin. The water-in-oil modified liquid coumarone resin emulsion is obtained using a phase inversion method, resulting in uniform distribution of the modified liquid coumarone resin in water. The product exhibits good stability, small particle size, high solid content, simple operation, and suitability for industrial production. The production method of the modified liquid coumarone resin emulsion of the present invention, by selecting appropriate parameters such as emulsifier, temperature, emulsifier ratio, and stirring speed, yields a modified liquid resin emulsion product that meets market demands. The product meets environmental protection requirements and can improve water resistance, chemical resistance, and flexibility in epoxy, polyurethane, and acrylic coating systems, with a wide range of applications.

[0103] Those skilled in the art should recognize that the above embodiments are merely illustrative of the present invention and are not intended to limit the present invention. Any variations or modifications to the above embodiments that are within the spirit and essence of the present invention will fall within the scope of the claims of the present invention.

Claims

1. A method for producing a modified liquid coumarone resin emulsion, characterized in that, Includes the following steps: S1, modified liquid coumarone resin was prepared using coumarone-indene distillate as raw material. The modified liquid coumarone resin is prepared by the following method: Raw material preparation: The coumarone-indene fraction is prepared with solvent to produce a feedstock oil with an indene content of 1-55%; The feedstock oil is depyridine and dephenolized by conventional acid washing and alkali washing, and further neutralized to obtain the coumarone fraction that has been dephenolized and depyridineized. Decolorization distillation involves passing the coumarone fraction (after phenol and pyridine removal) through a decolorization tower to separate the heavy fraction from the bottom and distill off the decolorized feedstock oil from the top. Polymerization: The decolorized raw material oil is mixed with methylstyrene and a catalyst, and polymerized oil is obtained through a polymerization reaction. Distillation is performed to wash the polymerized oil with water, and then the non-polymerized impurities are removed by distillation to obtain the modified liquid coumarone resin. S2, add the emulsifier sodium fatty alcohol polyoxyethylene ether sulfate to the modified liquid coumarone resin, and stir evenly at a preset temperature to form a mixture. The mass ratio of the emulsifier sodium fatty alcohol polyoxyethylene ether sulfate to the modified liquid coumarone resin is 0.05–0.2:1; The preset temperature is 40–80°C; The stirring speed is 500-2500 rpm; S3. After heating the deionized water to the same preset temperature as the mixture, slowly add the deionized water to the mixture while maintaining high-speed stirring. The mixture gradually forms a water-in-oil emulsion. After the viscosity gradually increases to the reverse inflection point, stop adding water, stir thoroughly, and continue adding deionized water to dilute it, thus obtaining an oil-in-water emulsion. S4. Add defoamer and stabilizer to the oil-in-water emulsion, stir evenly, and then lower to room temperature to obtain modified liquid coumarone resin emulsion.

2. The method for producing the modified liquid coumarone resin emulsion according to claim 1, characterized in that, During the preparation of the modified liquid coumarone resin: In the raw material preparation, the solvent is one or more of toluene, xylene, and flash distilled oil; and / or In the decolorization distillation process, the heavy fraction includes naphthalene, acid tar, and pitch; and / or During the polymerization process, the mass ratio of methylstyrene to the decolorizing feedstock oil is 1–8:1; and / or During the polymerization process, the catalyst is selected from one or more of aluminum trichloride, boron trifluoride, cation exchange resin, activated clay, and titanium tetrachloride; and / or During the polymerization process, the mass of the catalyst is 0.3 to 10 wt% of the mass of the decolorizing feedstock oil. During the polymerization process, the polymerization temperature is 5–60°C and the polymerization time is 1–5 h.

3. The method for producing the modified liquid coumarone resin emulsion according to claim 2, characterized in that, During the polymerization process: The mass of the catalyst is 2-5 wt% of the mass of the decolorizing feedstock oil; and / or The polymerization reaction temperature is 20–40°C, and the polymerization reaction time is 2–3 hours.

4. The method for producing the modified liquid coumarone resin emulsion according to claim 1, characterized in that, In step S2: The mass ratio of the emulsifier sodium fatty alcohol polyoxyethylene ether sulfate to the modified liquid coumarone resin is 0.10–0.15:1; and / or The preset temperature is 50-70℃.

5. The method for producing the modified liquid coumarone resin emulsion according to claim 1, characterized in that, In step S3: The total amount of deionized water added is 50-100 wt% of the mass of the modified liquid coumarone resin; and / or The solid content of the water-in-oil emulsion is ≥50wt%.

6. The method for producing the modified liquid coumarone resin emulsion according to claim 1, characterized in that, In step S4: The defoamer is a mineral oil-based defoamer; and / or The stabilizer used is a high molecular weight polyethylene glycol stabilizer.

7. The method for producing the modified liquid coumarone resin emulsion according to any one of claims 1 to 6, characterized in that, The modified liquid coumarone resin emulsion has a solid content of ≥50wt% and an average particle size of 0.45~1.5μm.

8. The method for producing the modified liquid coumarone resin emulsion according to claim 7, characterized in that, The modified liquid coumarone resin emulsion has a solid content of 50–70 wt%.

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