Production method of copolymerized petroleum resin for woodworking glue

Abstract

The invention relates to a production method of copolymerized petroleum resin for woodworking glue, and belongs to the technical field of synthetic resin. The method comprises the following steps: by taking cracked naphthalene fraction and cracked C5 as raw materials, firstly fractionating the cracked naphthalene fraction, diluting methyl styrene, indene and methyl indene which are obtained by fractionation with trimethylbenzene, then carrying out flash evaporation dehydration, and then separating and extracting the cracked C5 with acetonitrile to obtain the high-purity isoprene. Mixing the obtained indene, methylindene, methyl styrene, trimethylbenzene, high-purity isoprene, isoamylene, cyclopentadiene, a co-catalyst, a catalyst and a self-made flame-retardant antioxidant according to a ratio, carrying out ultrasonic dispersion, and carrying out continuous polymerization; and finally, adding trimethyl phosphate into the polymer, mixing, standing, removing the catalyst, and carrying out flash evaporation to obtain the copolymerized petroleum resin for the woodworking glue. The petroleum resin prepared by the production method disclosed by the invention is good in oxidation resistance, stable in property, light in color and luster, not easy to discolor, non-toxic, free of peculiar smell and flame-retardant.

Description

Technical Field

[0001] The invention belongs to the technical field of synthetic resins, and in particular relates to a method for producing copolymerized petroleum resin for woodworking glue. Background Art

[0002] Petroleum resin is a synthetic resin obtained by polymerization or condensation reaction of petroleum cracking products. Petroleum resin is usually an oligomer with a molecular weight between 300 and 3000. According to the main raw materials, petroleum resin can be divided into aliphatic resin (C5), alicyclic resin (DCPD), aromatic resin (C9), aliphatic / aromatic copolymer resin (C5 / C9) and hydrogenated petroleum resin. Among them, C5 petroleum resin and C9 petroleum resin are the two most widely used types. Petroleum resin has excellent solubility, adhesion and thermal stability. It also has the advantages of low price, good miscibility, low melting point, water resistance, ethanol resistance and chemical resistance. In addition, petroleum resin is chemically stable to acids and alkalis, and has the characteristics of good viscosity adjustment and thermal stability. These properties make petroleum resin widely used in many fields.

[0003] The disadvantages of petroleum resin in the prior art are mainly due to the fact that there are a large number of unsaturated bonds in its structure, which are easy to react under the action of oxygen or other chemicals, thereby affecting its appearance quality and performance. In addition, the copolymerized petroleum resin used for wood glue usually requires a color less than 3# and a small odor, which are not available in the prior art. Based on this, the present invention provides a method for producing copolymerized petroleum resin for wood glue, which solves the problem that the petroleum resin prepared in the prior art is easily oxidized, has a dark color, and has a strong odor. Summary of the invention

[0004] The object of the present invention is to provide a method for producing copolymerized petroleum resin for wood glue, so as to solve the problems mentioned in the above background technology.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A method for producing copolymerized petroleum resin for woodworking glue comprises the following steps: Step 1: Mix pyrogallol, boric acid and toluene in a three-necked flask, install a condenser and a thermometer, turn on the magnetic stirring, raise the system temperature to 80-90°C, add paraformaldehyde to the three-necked flask, and react at 80-90°C for 6-10 hours, then add sodium hydroxide solution to the three-necked flask, and adjust the pH to 3-4 with hydrochloric acid. After the reaction is completed, separate the organic layer with a separatory funnel, and perform silica gel column chromatography to obtain intermediate 1; Step 2: Mix the intermediate 1, anhydrous calcium chloride, concentrated hydrochloric acid and N,N-dimethylformamide in a three-necked flask, install a condenser and a thermometer, start magnetic stirring, and react at a temperature of 140-150°C for 2-3 hours. After the reaction is completed, add deionized water to the three-necked flask for washing, separate the organic layer with a separatory funnel, and rotary evaporate to obtain the intermediate 2; Step 3: Mix the intermediate 2, triethylamine and carbon tetrachloride in a three-necked flask, install a condenser and a thermometer, turn on the magnetic stirring, and drop dimethyl phosphite into the three-necked flask, and then react at a temperature of 50-70°C for 2h. After the reaction is completed, add deionized water to the three-necked flask for washing, separate the organic layer with a separatory funnel, and then rotary evaporate to obtain the intermediate 3; Step 4: Mix the intermediate 3, N,N-dimethylethyleneamine and acetonitrile in a three-necked flask, install a condenser and a thermometer, turn on the magnetic stirring, and react at a temperature of 30-40°C for 24 hours. After the reaction is completed, rotary evaporation is performed to obtain a flame retardant antioxidant.

[0006] Step 5: Fractionate the cracked naphthalene fraction and divide it into four components, then mix the second, third and fourth fractions with trimethylbenzene for dilution and flash dehydration. Styrene and xylene are the first fraction, methylstyrene and trimethylbenzene are the second fraction, indenes are the third fraction, and methylindenes are the fourth fraction.

[0007] Step 6: Use acetonitrile to separate and extract the cracked C5 fraction to obtain high-purity isoprene.

[0008] Step 7: The indene, methylindene, methylstyrene, trimethylbenzene, high-purity isoprene and isopentene, cyclopentadiene, the flame retardant antioxidant, the co-catalyst and the catalyst obtained in the step 4 are mixed in proportion and dispersed by ultrasonication before polymerization.

[0009] Step 8: Add trimethyl phosphite to the polymer obtained in step 7, stir and mix, let stand to separate layers, and then flash evaporate to obtain a copolymer petroleum resin for woodworking glue.

[0010] Furthermore, the sodium hydroxide solution used in the first step is a sodium hydroxide aqueous solution with a mass fraction of 10%, and the amount ratio of pyrogallol, boric acid, toluene, paraformaldehyde, and sodium hydroxide solution used is 0.1 mol: 0.11-0.12 mol: 60-80 mL: 4-5 g: 45-50 mL.

[0011] Furthermore, the concentrated hydrochloric acid used in the second step is a 30% by mass hydrochloric acid aqueous solution, and the amount ratio of the intermediate 1, anhydrous calcium chloride, concentrated hydrochloric acid, and N,N-dimethylformamide is 0.07 mol: 8-10 g: 20 g: 40 mL.

[0012] Furthermore, the usage ratio of the intermediate 2, triethylamine, carbon tetrachloride and dimethyl phosphite used in the third step is 0.05 mol: 0.06-0.1 mol: 60-80 mL: 0.05 mol.

[0013] Furthermore, the usage ratio of the intermediate 3, N,N-dimethylethyleneamine and acetonitrile used in the fourth step is 0.03 mol: 0.04-0.05 mol: 30-40 mL.

[0014] Furthermore, in the fifth step, the fractionation temperature conditions of each component are 146°C for the first component, 170°C for the second component, 185°C for the third component, and 200°C for the fourth component.

[0015] Furthermore, the mass proportions of the components in the seventh step are 10 to 12 parts of indene, 12 to 15 parts of methylindene, 10 to 15 parts of methylstyrene, 40 to 54 parts of trimethylbenzene, 4 to 5 parts of isopentene, 10 to 12 parts of high-purity isoprene, 0 to 0.4 parts of cyclopentadiene, 0.3 to 0.6 parts of flame retardant antioxidant, and 0.23 to 0.25 parts of catalyst.

[0016] Furthermore, in the seventh step, the co-catalyst is isopropanol and the catalyst is gas-phase boron trifluoride, and the usage ratio of the co-catalyst to the catalyst is 1:10.

[0017] Furthermore, the polymerization temperature in the seventh step is 20-30° C., and the polymerization time is 3-4 h.

[0018] Furthermore, the mass of trimethyl phosphite added in the eighth step is 5% of the polymer, the vacuum condition of the flash evaporation is -99.5~-100.0kPa, the temperature condition is 240~245℃, and the time condition is 0.3~0.5h.

[0019] Beneficial effects of the present invention: 1) The present invention uses pyrogallol as a raw material, and obtains an intermediate 1 with alcoholic hydroxyl groups after boric acid esterification, hydroxymethylation, and acid reduction, and then the alcoholic hydroxyl groups of the intermediate 1 are halogenated with concentrated hydrochloric acid under the catalysis of calcium chloride to obtain an intermediate 2, and then the phenolic hydroxyl groups of the intermediate 2 are substituted with dimethyl phosphite chlorinated with carbon tetrachloride to obtain an intermediate 3, and finally the chlorine atom of the intermediate 3 is reacted with N,N-dimethylethyleneamine to form a quaternary ammonium salt to obtain a flame retardant antioxidant; the flame retardant antioxidant of the present invention contains double bonds, can be copolymerized and modified with the raw materials used in the petroleum resin production method, and can be effective for a long time and stably. After copolymerization, the flame retardant antioxidant of the present invention can provide a large number of phenolic hydroxyl groups, and these phenolic hydroxyl groups have good antioxidant properties, which can effectively improve the characteristics of a large number of unsaturated bonds in the copolymerized petroleum resin that are easily oxidized; in addition, the flame retardant antioxidant of the present invention also has a phosphate structure, and these phosphate groups can form a protective carbon layer at high temperature. This carbon layer has good heat insulation and oxygen isolation functions, and can effectively prevent the copolymerized petroleum resin from contacting with the outside air to achieve a flame retardant effect.

[0020] 2) The present invention uses cracked naphthalene fraction and cracked C5 as raw materials, first fractionates the cracked naphthalene fraction and dilutes the fractionated methylstyrene, indene and methylindene components with trimethylbenzene and then flashes and dehydrates them, then separates and extracts the cracked C5 with acetonitrile to obtain high-purity isoprene, then mixes the obtained indene, methylindene, methylstyrene, trimethylbenzene, high-purity isoprene and isopentene, cyclopentadiene, co-catalyst, catalyst and homemade flame retardant antioxidant in proportion and continuously polymerizes them after ultrasonic dispersion, and finally adds trimethyl phosphate to the polymer and mixes and stands to remove the catalyst before flashing to obtain a copolymerized petroleum resin for woodworking glue; the production process of the present invention selects to first finely separate the cracked naphthalene fraction and the cracked C5 and then re-deploy them in proportion, so that the produced petroleum resin has good compatibility with EVA glue and has no peculiar smell. In addition, the production process of the present invention uses gas-phase boron trifluoride as a catalyst, which solves the problem of yellowing color of the copolymerized petroleum resin produced in the prior art; 3) The organic solvent selected in the production process of the present invention is safe and low-toxic, and does not use the highly toxic organic solvent of pure benzene commonly used in the prior art. In addition, a homemade flame retardant antioxidant is added in the production method of the present invention, and the obtained petroleum resin has good antioxidant properties, stable properties, is not easy to change color, and is flame retardant. DETAILED DESCRIPTION

[0021] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0022] Example 1 A flame retardant antioxidant is prepared by the following steps: Step 1: 0.1 mol of pyrogallol, 0.11 mol of boric acid and 60 mL of toluene were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, the system temperature was raised to 80°C, 4 g of paraformaldehyde was added to the three-necked flask, and the mixture was reacted at 80-90°C for 10 h, and then 45 mL of a 10% sodium hydroxide solution was added to the three-necked flask, and the pH was adjusted to 3-4 with hydrochloric acid. After the reaction was completed, the organic layer was separated with a separatory funnel, and the intermediate 1 was obtained by silica gel column chromatography; Step 2: 0.07 mol of intermediate 1, 8 g of anhydrous calcium chloride, 20 g of 30% hydrochloric acid aqueous solution, and 40 mL of N,N-dimethylformamide were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and the mixture was reacted at 140°C for 3 h. After the reaction was completed, deionized water was added to the three-necked flask for washing, and the organic layer was separated by a separatory funnel, and then the intermediate 2 was obtained by rotary evaporation; Step 3: 0.05 mol of intermediate 2, 0.06 mol of triethylamine and 60 mL of carbon tetrachloride were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and 0.05 mol of dimethyl phosphite was added dropwise to the three-necked flask, and then reacted at a temperature of 50°C for 2 hours. After the reaction was completed, deionized water was added to the three-necked flask for washing, and the organic layer was separated by a separatory funnel, and then the intermediate 3 was obtained by rotary evaporation; Step 4: Mix 0.03 mol of intermediate 3, 0.04 mol of N,N-dimethylethyleneamine and 30 mL of acetonitrile in a three-necked flask, install a condenser and a thermometer, turn on the magnetic stirring, and react at a temperature of 30°C for 24 hours. After the reaction is completed, a flame retardant antioxidant is obtained by rotary evaporation.

[0023] Example 2 A flame retardant antioxidant is prepared by the following steps: Step 1: 0.1 mol of pyrogallol, 0.115 mol of boric acid and 70 mL of toluene were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, the system temperature was raised to 85°C, 4.5 g of paraformaldehyde was added to the three-necked flask, and the mixture was reacted at 85°C for 8 hours, then 47 mL of a 10% sodium hydroxide solution was added to the three-necked flask, and the pH was adjusted to 3-4 with hydrochloric acid. After the reaction was completed, the organic layer was separated with a separatory funnel, and the intermediate 1 was obtained by silica gel column chromatography; Step 2: 0.07 mol of intermediate 1, 9 g of anhydrous calcium chloride, 20 g of 30% hydrochloric acid aqueous solution, and 40 mL of N,N-dimethylformamide were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and the mixture was reacted at 145°C for 2.5 h. After the reaction was completed, deionized water was added to the three-necked flask for washing, and the organic layer was separated by a separatory funnel, and then the intermediate 2 was obtained by rotary evaporation; Step 3: 0.05 mol of intermediate 2, 0.08 mol of triethylamine and 70 mL of carbon tetrachloride were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and 0.05 mol of dimethyl phosphite was added dropwise to the three-necked flask, and then reacted at a temperature of 60°C for 2 hours. After the reaction was completed, deionized water was added to the three-necked flask for washing, and the organic layer was separated by a separatory funnel, and then the intermediate 3 was obtained by rotary evaporation; Step 4: Mix 0.03 mol of intermediate 3, 0.045 mol of N,N-dimethylethyleneamine and 35 mL of acetonitrile in a three-necked flask, install a condenser and a thermometer, turn on the magnetic stirring, and react at a temperature of 35°C for 24 hours. After the reaction is completed, a flame retardant antioxidant is obtained by rotary evaporation.

[0024] Example 3 A flame retardant antioxidant is prepared by the following steps: Step 1: 0.1 mol of pyrogallol, 0.12 mol of boric acid, and 80 mL of toluene were mixed in a three-necked flask, a condenser and a thermometer were installed, and magnetic stirring was turned on. After the system temperature was raised to 90°C, 5 g of paraformaldehyde was added to the three-necked flask, and the mixture was reacted at 90°C for 6 h. Then, 50 mL of a 10% sodium hydroxide solution was added to the three-necked flask, and the pH was adjusted to 3-4 with hydrochloric acid. After the reaction was completed, the organic layer was separated with a separatory funnel, and the intermediate 1 was obtained by silica gel column chromatography; Step 2: 0.07 mol of intermediate 1, 10 g of anhydrous calcium chloride, 20 g of 30% hydrochloric acid aqueous solution, and 40 mL of N,N-dimethylformamide were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and the mixture was reacted at 150°C for 2 h. After the reaction was completed, deionized water was added to the three-necked flask for washing, and the organic layer was separated by a separatory funnel, and then the intermediate 2 was obtained by rotary evaporation; Step 3: 0.05 mol of intermediate 2, 0.1 mol of triethylamine and 80 mL of carbon tetrachloride were mixed in a three-necked flask, a condenser and a thermometer were installed, magnetic stirring was turned on, and 0.05 mol of dimethyl phosphite was added dropwise to the three-necked flask, and then reacted at 70°C for 2 h. After the reaction was completed, deionized water was added to the three-necked flask for washing, and the organic layer was separated by a separatory funnel, and then the intermediate 3 was obtained by rotary evaporation; Step 4: Mix 0.03 mol of intermediate 3, 0.05 mol of N,N-dimethylethyleneamine and 40 mL of acetonitrile in a three-necked flask, install a condenser and a thermometer, turn on the magnetic stirring, and react at a temperature of 40°C for 24 hours. After the reaction is completed, rotary evaporation is performed to obtain a flame retardant antioxidant.

[0025] Example 4 A production process of copolymerized petroleum resin for woodworking glue comprises the following steps: The first step: fractionate the cracked naphthalene fraction and divide it into four components, then dilute the second, third and fourth fractions with trimethylbenzene and flash dehydrate them. Styrene and xylene are the first fraction, and the fractionation temperature is 146°C; methylstyrene and trimethylbenzene are the second fraction, and the fractionation temperature is 170°C; indene is the third fraction, and the fractionation temperature is 185°C; methylindene is the fourth fraction, and the fractionation temperature is 200°C.

[0026] Step 2: Use acetonitrile to separate and extract the cracked C5 fraction to obtain high-purity isoprene.

[0027] The third step: the indene, indene, methyl styrene, trimethylbenzene, high-purity isoprene and isopentene, cyclopentadiene, the flame retardant antioxidant obtained in Example 1, isopropanol and gaseous boron trifluoride obtained in the first and second steps are mixed in proportion and ultrasonically dispersed, and then polymerized at a temperature of 20°C for 4 hours. The mass fractions of each component in this step are 10 parts of indene, 12 parts of indene, 10 parts of methyl styrene, 40 parts of trimethylbenzene, 4 parts of isopentene, 10 parts of high-purity isoprene, 0.4 parts of cyclopentadiene, 0.6 parts of the flame retardant antioxidant obtained in Example 1, 0.25 parts of gaseous boron trifluoride, and 0.025 parts of isopropanol.

[0028] Step 4: Add trimethyl phosphite equivalent to 5% of the polymer mass to the polymer obtained in the third step, stir and mix, and stand to separate into layers. Then, flash evaporate for 0.5 h at a vacuum condition of -100.0 kPa and a temperature condition of 240°C to obtain a copolymer petroleum resin for woodworking glue.

[0029] Example 5 A production process of copolymerized petroleum resin for woodworking glue comprises the following steps: The first step: fractionate the cracked naphthalene fraction and divide it into four components, then dilute the second, third and fourth fractions with trimethylbenzene and flash dehydrate them. Styrene and xylene are the first fraction, and the fractionation temperature is 146°C; methylstyrene and trimethylbenzene are the second fraction, and the fractionation temperature is 170°C; indene is the third fraction, and the fractionation temperature is 185°C; methylindene is the fourth fraction, and the fractionation temperature is 200°C.

[0030] Step 2: Use acetonitrile to separate and extract the cracked C5 fraction to obtain high-purity isoprene.

[0031] The third step: the indene, indene, methyl styrene, trimethylbenzene, high-purity isoprene and isopentene obtained in the first and second steps, the flame retardant antioxidant obtained in Example 2, isopropanol, and gaseous boron trifluoride are mixed in proportion and ultrasonically dispersed, and then polymerized at a temperature of 25°C for 3.5 hours. The mass fractions of each component in this step are 11 parts of indene, 14 parts of indene, 12 parts of methyl styrene, 46 parts of trimethylbenzene, 4.5 parts of isopentene, 11 parts of high-purity isoprene, 0.45 parts of the flame retardant antioxidant obtained in Example 2, 0.24 parts of gaseous boron trifluoride, and 0.024 parts of isopropanol.

[0032] Step 4: Add trimethyl phosphite equivalent to 5% of the polymer mass to the polymer obtained in the third step, stir and mix, and let stand to separate into layers. Then, flash evaporate for 0.4 h at a vacuum condition of -99.7 kPa and a temperature condition of 242°C to obtain a copolymer petroleum resin for woodworking glue.

[0033] Example 6 A production process of copolymerized petroleum resin for woodworking glue comprises the following steps: The first step: fractionate the cracked naphthalene fraction and divide it into four components, then dilute the second, third and fourth fractions with trimethylbenzene and flash dehydrate them. Styrene and xylene are the first fraction, and the fractionation temperature is 146°C; methylstyrene and trimethylbenzene are the second fraction, and the fractionation temperature is 170°C; indene is the third fraction, and the fractionation temperature is 185°C; methylindene is the fourth fraction, and the fractionation temperature is 200°C.

[0034] Step 2: Use acetonitrile to separate and extract the cracked C5 fraction to obtain high-purity isoprene.

[0035] The third step: the indene, indene, methyl styrene, trimethylbenzene, high-purity isoprene and isopentene, cyclopentadiene, the flame retardant antioxidant obtained in Example 3, isopropanol, and gaseous boron trifluoride obtained in the first and second steps are mixed in proportion and ultrasonically dispersed, and then polymerized at a temperature of 30°C for 3h. The mass fractions of each component in this step are 12 parts of indene, 15 parts of indene, 15 parts of methyl styrene, 54 parts of trimethylbenzene, 5 parts of isopentene, 12 parts of high-purity isoprene, 0.2 parts of cyclopentadiene, 0.3 parts of the flame retardant antioxidant obtained in Example 3, 0.23 parts of gaseous boron trifluoride, and 0.023 parts of isopropanol.

[0036] Step 4: Add trimethyl phosphite equivalent to 5% of the polymer mass to the polymer obtained in the third step, stir and mix, and let stand to separate into layers. Then, flash evaporate for 0.3 h at a vacuum condition of -99.5 kPa and a temperature condition of 245°C to obtain a copolymer petroleum resin for woodworking glue.

[0037] Comparative Example 1 A production process of copolymerized petroleum resin for woodworking glue comprises the following steps: The first step: fractionate the cracked naphthalene fraction and divide it into four components, then dilute the second, third and fourth fractions with trimethylbenzene and flash dehydrate them. Styrene and xylene are the first fraction, and the fractionation temperature is 146°C; methylstyrene and trimethylbenzene are the second fraction, and the fractionation temperature is 170°C; indene is the third fraction, and the fractionation temperature is 185°C; methylindene is the fourth fraction, and the fractionation temperature is 200°C.

[0038] Step 2: Use acetonitrile to separate and extract the cracked C5 fraction to obtain high-purity isoprene.

[0039] Step 3: The indene, methylindene, methylstyrene, trimethylbenzene, high-purity isoprene and isopentene, cyclopentadiene, isopropanol and gaseous boron trifluoride obtained in the first and second steps are mixed in proportion and ultrasonically dispersed, and then polymerized at 30°C for 3 hours. The mass fractions of the components in this step are 12 parts of indene, 15 parts of methylindene, 15 parts of methylstyrene, 54 parts of trimethylbenzene, 5 parts of isopentene, 12 parts of high-purity isoprene, 0.2 parts of cyclopentadiene, 0.23 parts of gaseous boron trifluoride and 0.023 parts of isopropanol.

[0040] Step 4: Add trimethyl phosphite equivalent to 5% of the polymer mass to the polymer obtained in the third step, stir and mix, and let stand to separate into layers. Then, flash evaporate for 0.3 h at a vacuum condition of -99.5 kPa and a temperature condition of 245°C to obtain a copolymer petroleum resin for woodworking glue.

[0041] Comparative Example 2 This comparative example is the C5 petroleum resin sold by Puyang Hengtai Petrochemical Co., Ltd.

[0042] The copolymerized petroleum resin for woodworking glue in Examples 4 to 6 and Comparative Example 1 and the C5 petroleum resin in Comparative Example 2 were added into an oven together after testing the Gardner color number using a fully automatic colorimeter (Lovibond PFXI195 / 11). The oven temperature was set to 200°C. After heating for 5 hours and aging, the color number after aging was tested. The color number value after aging was divided by the initial color number value to obtain the color difference percentage. The test structure is shown in Table 1: Table 1 It can be seen from Table 1 that the oxidation resistance of the petroleum resin for woodworking glue of Examples 4 to 6 of the present invention is much better than that of the commercially available C5 petroleum resin, while the oxidation resistance of the petroleum resin for woodworking glue in Comparative Example 1 is poor because the flame retardant antioxidant of the present invention is not used. This shows that the flame retardant antioxidant used in the production method of the present invention can effectively improve the antioxidant properties of the petroleum resin, and the obtained petroleum resin has good oxidation resistance.

[0043] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A method for producing copolymerized petroleum resin for wood glue, characterized in that: The following steps are involved: Step 1: Mix pyrogallol, boric acid and toluene in a container, stir evenly, raise the system temperature to 80-90°C, then add paraformaldehyde to the container, and react at 80-90°C for 6-10h, then add sodium hydroxide solution to the container, and adjust the pH to 3-4 with hydrochloric acid to obtain intermediate 1; Step 2: Mix intermediate 1, anhydrous calcium chloride, concentrated hydrochloric acid and N,N-dimethylformamide in a container, stir evenly, and react at a temperature of 140-150°C for 2-3h to obtain intermediate 2; Step 3: Mix intermediate 2, triethylamine and carbon tetrachloride in a container, stir evenly, and then drop dimethyl phosphite into the container, and then react at a temperature of 50-70°C for 2h to obtain intermediate 3; Step 4: Mix the intermediate 3, N,N-dimethylethyleneamine and acetonitrile in a container, stir evenly, and react at a temperature of 30-40°C for 24 hours to obtain a flame retardant antioxidant; Step 5: Fractionate the cracked naphthalene fraction and divide it into four components, then dilute the second, third and fourth fractions with trimethylbenzene and flash dehydrate them. Styrene and xylene are the first fraction, methylstyrene and trimethylbenzene are the second fraction, indenes are the third fraction, and methylindenes are the fourth fraction; Step 6: Separate and extract the cracked C5 fraction with acetonitrile to obtain high-purity isoprene; Step 7: Mix the indene, methylindene, methylstyrene, trimethylbenzene, high-purity isoprene and isopentene, cyclopentadiene, the flame retardant antioxidant, the co-catalyst and the catalyst obtained in the step 4 according to a certain proportion, disperse them by ultrasonication and then polymerize them; Step 8: Add trimethyl phosphite to the polymer obtained in step 7, stir and mix, let stand to separate into layers, and then flash evaporate to obtain a copolymer petroleum resin for woodworking glue.

2. The method for producing a copolymerized petroleum resin for woodworking glue according to claim 1, characterized in that: The sodium hydroxide solution used in the first step is a sodium hydroxide aqueous solution with a mass fraction of 10%, and the amount ratio of pyrogallol, boric acid, toluene, paraformaldehyde, and sodium hydroxide solution used is 0.1 mol: 0.11-0.12 mol: 60-80 mL: 4-5 g: 45-50 mL.

3. The method for producing a copolymerized petroleum resin for wood glue according to claim 1, characterized in that: The concentrated hydrochloric acid used in the second step is a 30% by mass aqueous solution of hydrochloric acid, and the amount ratio of the intermediate 1, anhydrous calcium chloride, concentrated hydrochloric acid, and N,N-dimethylformamide is 0.07 mol: 8-10 g: 20 g: 40 mL.

4. The method for producing a copolymerized petroleum resin for woodworking glue according to claim 1, characterized in that: The amount ratio of the intermediate 2, triethylamine, carbon tetrachloride and dimethyl phosphite used in the third step is 0.05 mol: 0.06-0.1 mol: 60-80 mL: 0.05 mol.

5. The method for producing a copolymerized petroleum resin for wood glue according to claim 1, characterized in that: The amount ratio of the intermediate 3, N,N-dimethylethyleneamine and acetonitrile used in the fourth step is 0.03 mol: 0.04-0.05 mol: 30-40 mL.

6. The method for producing a copolymerized petroleum resin for woodworking glue according to claim 1, characterized in that: The fractionation temperature conditions of each component in the fifth step are 146°C for the first component, 170°C for the second component, 185°C for the third component, and 200°C for the fourth component.

7. The method for producing a copolymerized petroleum resin for wood glue according to claim 1, characterized in that: The mass proportions of the components in the seventh step are 10-12 parts of indene, 12-15 parts of methylindene, 10-15 parts of methylstyrene, 40-54 parts of trimethylbenzene, 4-5 parts of isopentene, 10-12 parts of high-purity isoprene, 0-0.4 parts of cyclopentadiene, 0.3-0.6 parts of flame retardant antioxidant, and 0.23-0.25 parts of catalyst.

8. The method for producing a copolymerized petroleum resin for wood glue according to claim 1, characterized in that: In the seventh step, the co-catalyst is isopropanol and the catalyst is gas-phase boron trifluoride, and the usage ratio of the co-catalyst to the catalyst is 1:

10.

9. The method for producing a copolymerized petroleum resin for wood glue according to claim 1, characterized in that: The polymerization temperature in the seventh step is 20-30°C, and the polymerization time is 3-4h.

10. The method for producing a copolymerized petroleum resin for wood glue according to claim 1, characterized in that: The mass of trimethyl phosphite added in the eighth step is 5% of the polymer, the vacuum condition of flash evaporation is -99.5~-100.0kPa, the temperature condition is 240~245℃, and the time condition is 0.3~0.5h.

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