Device and method for producing modified petroleum resin

Abstract

The embodiment of the invention provides a manufacturing device and a manufacturing method of modified petroleum resin. The manufacturing device comprises a mixing machine; the double-screw extruder is communicated with the mixing machine, and an outlet of the mixing machine is connected to an inlet of the double-screw extruder; the devolatilization kettle is communicated with the double-screw extruder, and an outlet of the double-screw extruder is connected to an inlet of the devolatilization kettle; the recovery tank is communicated with the devolatilization kettle, and a first outlet of the devolatilization kettle is connected to an inlet of the recovery tank; the condenser is communicated with the recovery tank, a first outlet of the recovery tank is communicated with an inlet of the condenser in a two-way mode, and an electron beam irradiation device is arranged at the position of the double-screw extruder. The polar monomer is grafted by adopting the synergistic effect of a twin-screw extrusion technology and an electron beam irradiation technology, and the petroleum resin and the polar grafted monomer are fully mixed by utilizing the strong shearing force of twin screws.

Description

Technical Field

[0001] The embodiments of the present application relate to a manufacturing device and a manufacturing method for a modified petroleum resin. Background Art

[0002] Petroleum resins such as piperylene are an important chemical raw material. Its polymer piperylene resin has good heat resistance, weather resistance and electrical insulation, and is widely used in electronics, electrical, aerospace and other fields. However, since piperylene petroleum resin is a non-polar hydrocarbon polymer, its composite force with polar materials is weak, which limits its application field and composite material performance. Therefore, improving its performance through modification technology is one of the current research hotspots. Introducing polar groups into the molecular chain can increase its adhesion and adhesion, increase the softening temperature and compatibility with polar resins, and expand the application range of petroleum resins. In addition, the addition of antioxidants can further improve the stability of the resin and extend its service life.

[0003] In the patent application with the publication number CN104341555A, a method for synthesizing a modified isoprene resin is disclosed. The method uses isoprene, C5 monoolefin, and terpene as copolymerization raw materials to prepare a petroleum resin with a smaller molecular weight, a higher softening point, and a lower bromine value. The method for synthesizing the modified isoprene resin includes feeding isoprene, C5 monoolefin, and terpene in a weight ratio of 1: (0.1-0.7): (0.4-1.4) to prepare a copolymerization raw material; under the action of a catalyst, using an inert aliphatic hydrocarbon as a solvent, a cationic polymerization reaction is carried out at a temperature of 30-70°C and an oxygen-free environment to synthesize the resin.

[0004] In the patent application with the publication number CN115572353A, a modified petroleum resin and its preparation method and application are disclosed. The preparation method comprises the following steps: (1) mixing an initiator with heat-insulated isoprene to carry out polymerization reaction to obtain a petroleum resin solution; (2) mixing the petroleum resin solution after the polymerization reaction in step (1) with an initiator and a polar grafting monomer to carry out grafting reaction to obtain a modified petroleum resin. The method of the present invention is online and continuous from synthesis to modification without intermediate links (traditional: first produce petroleum resin, cut into pellets and package, then heat and melt graft), with low production energy consumption, energy saving, low cost, adjustable grafting rate of modified petroleum resin, and high purity.

[0005] Since isoprene resin contains more unsaturated double bonds, it is convenient to introduce some polar groups. At present, the existing technology mainly focuses on free radical polymerization or cationic polymerization. By adding initiators or catalysts, polar monomers are reacted and polymerized with isoprene resin or isoprene monomers, which increases the process of removing initiators or catalysts. At the same time, incomplete removal of initiators or catalysts will also reduce the quality of modified resins. Free radical polymerization reactions also have factors such as violent reactions and uncontrollable factors, which pose certain safety hazards. Summary of the invention

[0006] The present application uses the synergistic effect of twin-screw extrusion technology and electron beam irradiation technology to graft polar monomers, utilizes the strong shear force of the twin screws to fully mix the resin and the polarized grafted monomers, and then utilizes the effect of the high-energy electron beam to excite the resin to produce free radicals, thereby initiating the grafting reaction. Specifically, the present application utilizes the strong shear force of the twin screws to fully mix the petroleum resin and the polarized monomers, and then utilizes the effect of the high-energy electron beam to achieve grafting modification of the petroleum resin and the polarized monomers. The reaction conditions are mild and there are no safety hazards. At the same time, the process is simple, the output is high, and the product quality is good.

[0007] Specifically, some embodiments of the present application provide a manufacturing device for a modified petroleum resin, comprising: a mixer; a twin-screw extruder connected to the mixer, wherein the outlet of the mixer is connected to the inlet of the twin-screw extruder; a devolatilizer connected to the twin-screw extruder, wherein the outlet of the twin-screw extruder is connected to the inlet of the devolatilizer; a recovery tank connected to the devolatilizer, wherein the first outlet of the devolatilizer is connected to the inlet of the recovery tank; and a condenser connected to the recovery tank, wherein the first outlet of the recovery tank is bidirectionally connected to the inlet of the condenser, wherein an electron beam irradiation device is provided at the twin-screw extruder.

[0008] In some embodiments, the electron beam irradiation device is disposed at the rear end of the twin-screw extruder close to the devolatilizer.

[0009] In some embodiments, the outlet of the twin-screw extruder is connected to the devolatilizer through a pipeline, wherein the material in the twin-screw extruder enters the devolatilizer through the pipeline after being irradiated by the electron beam of the electron beam irradiation device.

[0010] In some embodiments, the manufacturing device also includes: a finished product tank connected to the devolatilizer, wherein the second outlet of the devolatilizer is connected to the inlet of the finished product tank, wherein the second outlet of the devolatilizer is different from the first outlet of the devolatilizer; and a tail gas absorption tank connected to the recovery tank, wherein the second outlet of the recovery tank is connected to the inlet of the tail gas absorption tank, and the third outlet of the recovery tank is connected to the inlet of the mixer, wherein the first outlet, the second outlet and the third outlet of the recovery tank are all different.

[0011] Other embodiments of the present application provide a method for manufacturing a modified petroleum resin, which is characterized in that it includes: adding petroleum resin, polarized grafted monomers and antioxidants into a mixer to obtain a mixed material; adding the material into a twin-screw extruder, propelling the material through the twin screws of the twin-screw extruder to the electron beam irradiation area of ​​the twin-screw extruder irradiated by an electron beam irradiation device, and entering the devolatilization kettle through a pipeline after electron beam irradiation; and recovering the unreacted polarized grafted monomers and oligomers into a recovery tank after condensation through a condenser through vacuum distillation, wherein the electron beam irradiation device is arranged at the tail end of the twin-screw extruder close to the devolatilization kettle.

[0012] In some embodiments, the rotation speed of the mixer is in the range of 1500-3500 rpm / min, and while the mixer is running, the mixer is cooled so that the temperature of the material is maintained between 22-25°C.

[0013] In some embodiments, the material is added to the feeding port of the twin-screw extruder through a material lifting belt, wherein the rotation speed of the twin screw is set to 170-300 rpm / min, and the module temperature of the twin-screw extruder is set to 190-210°C, and wherein the dose of the electron beam irradiation is 100-1000 kGy, and the electron energy of the electron beam irradiation is 0.6-1 MeV.

[0014] In some embodiments, the polarized grafted monomer includes one or more unsaturated olefin functionalized monomers such as maleic anhydride and itaconic anhydride, wherein the mass of the polarized grafted monomer is 1%-10% of the mass of the petroleum resin, and the mass of the antioxidant is 0.1%-1% of the mass of the petroleum resin.

[0015] In some embodiments, after the material enters the devolatilization reactor, the stirring device is turned on, and the rotation speed of the stirring device is 70-90rpm / min; and after the vacuum distillation, the modified petroleum resin is sent to a granulation workshop for granulation to obtain a modified petroleum resin product, wherein the pressure of the vacuum distillation is -0.07 to -0.09Mpa, the temperature of the vacuum distillation is the temperature of the material, and the time of the vacuum distillation is 30-60min.

[0016] In some embodiments, adding the petroleum resin into the mixer includes adding the petroleum resin into the mixer under the protection of an inert gas, wherein the inert gas is present in the devolatilizer, and the inert gas in the devolatilizer enters a tail gas adsorption tank for adsorption,

[0017] The inert gas at least replaces the gas in the twin-screw extruder, the devolatilizer and the pipeline to ensure that the entire production environment is an oxygen-free environment.

[0018] In some embodiments, the recovery tank is an unreacted polarized grafted monomer recovery tank, specifically, it can be a maleic anhydride (MA) recovery tank.

[0019] Compared with the existing technology, the beneficial effects of this technical solution are as follows:

[0020] 1) This technical solution can effectively improve the reaction efficiency and product quality by accurately controlling the ratio of polarized grafted monomers and antioxidants, the speed and time of the mixer, the speed of the twin-screw extruder, the dose of electron beam irradiation, and the temperature and time of vacuum distillation. The grafting rate of polarized grafted monomers such as maleic anhydride in the modified petroleum resin produced by this patent can reach 0.2-5%;

[0021] 2) This technical solution uses twin-screw extrusion and electron beam irradiation synergistic processing technology, does not use initiators, reduces the generation of by-products; does not require additional heating, reduces energy consumption; and is equipped with a polar monomer recovery tank to collect the components obtained by devolatilization for subsequent recycling. Compared with the existing technology, it can save about 40% of the cost; and

[0022] 3) The process is simple, the reaction time is short, and continuous production from feeding to discharging can be achieved. In addition, no "three wastes" are generated in the production process, truly achieving green, economical and efficient production. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Aspects of the present invention are best understood from the following detailed description when read with the accompanying figures.

[0024] Figure 1The process flow of the method for producing modified petroleum resin is shown. DETAILED DESCRIPTION

[0025] The following disclosure provides many different embodiments or examples for realizing different features of the present invention. Specific examples of components and arrangements are described below to simplify the present invention. Of course, these are merely examples and are not intended to limit the present invention. For example, in the following description, forming a first component above or on a second component may include an embodiment in which the first component and the second component are directly in contact with each other, and may also include an embodiment in which an additional component may be formed between the first component and the second component so that the first component and the second component may not be in direct contact. In addition, the present invention may repeat reference numerals and / or characters in various embodiments. This repetition is for the purpose of simplicity and clarity, and does not itself indicate the relationship between the various embodiments and / or configurations discussed.

[0026] Furthermore, for ease of description, spatially relative terms such as "below," "beneath," "lower," "above," "upper," etc. may be used herein to describe the relationship of one element or component to another (or additional) elements or components as shown in the figures. The spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein should be interpreted accordingly.

[0027] The present application adopts the synergistic effect of twin-screw extrusion technology and electron beam irradiation technology to graft polar monomers, utilizes the strong shear force of the twin screw to fully mix the resin and the polarized grafted monomer, and then utilizes the effect of high-energy electron beam to excite the resin to produce free radicals, thereby initiating the grafting reaction. Compared with the prior art, the present technology does not add additional initiators or catalysts, eliminates the process of removing initiators or catalysts, and also avoids the byproducts that may be generated by the initiator-induced free radical reaction. The technical solution provided by the present application does not need to add organic solvents to dissolve the resin or polarized monomers, eliminates the process of desolventizing, and does not consume additional energy during the reaction process of the technical solution provided by the present application. At the same time, a polar grafted monomer recovery tank is provided, which can recycle the unreacted monomers and save costs; at the same time, the technology can achieve continuous production and increase production capacity. The present technology does not produce "three wastes" during the reaction process, and is a green, economical and efficient production process.

[0028] Some embodiments of the present application provide a manufacturing device and a manufacturing method for a modified petroleum resin, the manufacturing device comprising: a mixer; a twin-screw extruder, connected to the mixer, wherein the outlet of the mixer is connected to the inlet of the twin-screw extruder; a devolatilizer, connected to the twin-screw extruder, wherein the outlet of the twin-screw extruder is connected to the inlet of the devolatilizer; a recovery tank, connected to the devolatilizer, wherein the first outlet of the devolatilizer is connected to the inlet of the recovery tank; and a condenser, connected to the recovery tank, wherein the first outlet of the recovery tank is bidirectionally connected to the inlet of the condenser, wherein an electron beam irradiation device is provided at the twin-screw extruder. Specifically, the electron beam irradiation device is provided at the tail end of the twin-screw extruder near the devolatilizer, and further, the electron beam irradiation device is provided above the tail end of the twin-screw extruder. In some embodiments, the outlet of the twin-screw extruder is connected to the devolatilizer through a pipeline, wherein the material in the twin-screw extruder enters the devolatilizer through the pipeline after being irradiated by the electron beam of the electron beam irradiation device. In some embodiments, the manufacturing device also includes: a finished product tank, connected to the devolatilizer, wherein the second outlet of the devolatilizer is connected to the inlet of the finished product tank, wherein the second outlet of the devolatilizer is different from the first outlet of the devolatilizer, and the first outlet and the second outlet of the devolatilizer are respectively connected to the inlet of the recovery tank and the inlet of the finished product tank through different pipelines; and a tail gas absorption tank, connected to the recovery tank, wherein the second outlet of the recovery tank is connected to the inlet of the tail gas absorption tank, and the third outlet of the recovery tank is connected to the inlet of the mixer, wherein the first outlet, the second outlet and the third outlet of the recovery tank are different, and the second outlet and the third outlet of the recovery tank are connected to the inlet of the tail gas absorption tank and the inlet of the mixer through different pipelines.

[0029] The manufacturing method of the modified petroleum resin of the present application mainly adopts the following steps: using inert gas to replace the gas in the twin-screw extruder, the devolatilization kettle, the product tank and the connected pipeline to ensure that the entire production environment is an oxygen-free environment; adding a petroleum resin such as isopentylene resin and a specific proportion of polarized grafting monomer and antioxidant into a high-speed mixer (the mixer used in the present application is a high-speed mixer with a rotation speed of more than 1500rpm / min), stirring for 3-5min at a rotation speed of 1500-3500rpm / min to obtain a mixed material; while the high-speed mixer is running, using a cooling The high-speed mixer is cooled by water to keep the material temperature at room temperature (between 22°C and 25°C) to prevent the grafted polar monomer from volatilizing and the resin from softening due to excessive temperature during the mixing process; the obtained mixed material is added to the feeding port of the twin-screw extruder through the material lifting belt, the speed of the twin-screw is set to 170-300rpm / min, and the module temperature is set to 190-210°C; an electron beam irradiation device is provided at the tail end of the twin-screw extruder, and the discharge port of the twin-screw extruder is connected to the devolatilization reactor through a pipeline, the material is pushed to the electron beam irradiation area through the twin screw, and after the electron beam irradiation, it is passed through the pipeline Entering the devolatilization kettle at the rear end, wherein the polarized grafted monomer includes one or more unsaturated olefin functionalized monomers such as maleic anhydride and itaconic anhydride; the antioxidant includes one of 2,6-di-tert-butyl-4-methylphenol (antioxidant 264) or 3,5-di-tert-butylphenyl-4-hydroxyphenylpropionic acid isooctyl ester (antioxidant 1135); the mass of the polarized grafted monomer is 1%-10% of the mass of the isoprene resin, and the mass of the antioxidant is 0.1%-1% of the mass of the isoprene resin; the electron beam irradiation dose is 100-1000 kGy, and the electron energy of the electron beam irradiation is 0.6-1 MeV; the devolatilization kettle has a stirring A stirring device and a heat preservation device are provided. After the material enters the devolatilization kettle, the stirring device is turned on at a speed of 70-90rpm / min. The unreacted polarized grafted monomers and oligomers are condensed in a condenser by vacuum distillation and then recovered into a recovery tank. The pressure is (-0.07)-(-0.09)Mpa, the devolatilization temperature (vacuum distillation temperature) is the temperature of the material (the material temperature refers to the temperature of the material extruded from the twin-screw extruder), and the vacuum distillation time is 30-60min; the recovered polarized grafted monomer is continuously reused in the reaction, and the inert gas or nitrogen in the devolatilization kettle enters the tail gas adsorption tank for adsorption. After the vacuum distillation work is completed, the modified resin is sent to the granulation workshop for granulation to obtain the modified resin product. The process is simple and efficient, and the continuous production of the resin is realized. The acid value of the modified resin can be adjusted, the polarized grafted monomer can be recycled, and no "three wastes" are generated, which truly achieves green and economical production.

[0030] In order to more clearly illustrate the manufacturing device and manufacturing method provided by the present invention, the present application is measured and described in detail through the following examples. The test methods of various indicators of the modified petroleum resin prepared in the following examples are as follows: softening point: ring and ball method (GB / T4507); chromaticity: GB / T22295 (Gardner chromaticity); acid value: GB / T2895, melt viscosity: GB / T24148.4. The above test methods are all commonly used test methods in the field.

[0031] Example 1

[0032] The gases in the twin-screw extruder, the devolatilization kettle, the product tank and the connected pipelines are replaced by nitrogen. After the replacement, 100 kg of isopentadiene resin, 1 kg of maleic anhydride and 0.1 kg of antioxidant 264 are added to a high-speed mixer at a rotation speed of 1500 rpm / min and a stirring time of 3 minutes to fully mix them to obtain a mixture; the mixture enters the feeding port of the twin-screw extruder through a material lifting belt, the twin-screw extruder is turned on, the rotation speed is set to 170 rpm / min, and the module temperature is 190° C. The electron beam irradiation device is 0.6 MeV, and the electron beam irradiation dose is set to 100 KGy; the grafted resin enters the rear-end devolatilization kettle, and under the conditions of a pressure of -0.07 MPa and a rotation speed of 90 rpm / min, unreacted polarized grafted monomers and oligomers are vacuum distilled to a recovery tank by vacuum distillation, and the vacuum distillation time is 30 minutes; after the vacuum distillation work is completed, the modified resin is granulated to obtain a modified resin product.

[0033] Example 2

[0034] The gases in the twin-screw extruder, the devolatilization kettle, the product tank and the connected pipelines are replaced by nitrogen. After the replacement, 100 kg of isopentadiene resin, 1 kg of maleic anhydride and 0.1 kg of antioxidant 264 are added to a high-speed mixer at a rotation speed of 3000 rpm / min and a stirring time of 5 min to fully mix them to obtain a mixture; the mixture enters the feeding port of the twin-screw extruder through a material lifting belt, the twin-screw extruder is turned on, the rotation speed is set to 300 rpm / min, and the module temperature is 210° C. The electron beam irradiation device is 1 MeV, and the electron beam irradiation dose is set to 1000 KGy; the grafted resin enters the rear-end devolatilization kettle, and under the conditions of a pressure of -0.09 MPa and a rotation speed of 90 rpm / min, unreacted polarized grafted monomers and oligomers are vacuum distilled to a recovery tank by vacuum distillation, and the vacuum distillation time is 40 min; after the vacuum distillation work is completed, the modified resin is sent to a granulation workshop for granulation to obtain a modified resin product.

[0035] Example 3

[0036] The gases in the twin-screw extruder, the devolatilization kettle, the product tank and the connected pipelines are replaced by nitrogen. After the replacement, 100 kg of isopentadiene resin, 5 kg of maleic anhydride and 0.5 kg of antioxidant 264 are added to the high-speed mixer at a speed of 3000 rpm / min for 5 minutes to fully mix them to obtain a mixed sample; the mixed material enters the feeding port of the twin-screw extruder through a material lifting belt, the twin-screw extruder is turned on, the speed is set to 170 rpm / min, and the module temperature is 190°C; the electron beam irradiation device is 0.6 MeV, and the electron beam irradiation dose is set to 100 KGy; the grafted resin enters the rear-end devolatilization kettle, and under the conditions of a pressure of -0.07 MPa and a speed of 90 rpm / min, the unreacted polarized grafted monomers and oligomers are vacuum distilled to a recovery tank by vacuum distillation, and the vacuum distillation time is 30 minutes; after the vacuum distillation work is completed, the modified resin is sent to a granulation workshop for granulation to obtain a modified resin product.

[0037] Example 4

[0038] The gases in the twin-screw extruder, the devolatilization kettle, the product tank and the connected pipelines are replaced by nitrogen. After the replacement, 100 kg of isopentadiene resin, 5 kg of maleic anhydride and 0.5 kg of antioxidant 1135 are added to the high-speed mixer at a speed of 3000 rpm / min for 5 minutes to fully mix them to obtain a mixed sample; the mixed material enters the feeding port of the twin-screw extruder through a material lifting belt, the twin-screw extruder is turned on, the speed is set to 300 rpm / min, and the module temperature is 190°C; the electron beam irradiation device is 0.6 MeV, and the electron beam irradiation dose is set to 100 KGy; the grafted resin enters the rear-end devolatilization kettle, and under the conditions of a pressure of -0.07 MPa and a speed of 90 rpm / min, the unreacted polarized grafted monomers and oligomers are vacuum distilled to a recovery tank by vacuum distillation, and the vacuum distillation time is 30 minutes; the recovered polarized grafted monomers are continuously reused in the reaction. After the vacuum distillation is completed, the modified resin is sent to the granulation workshop for granulation to obtain the modified resin product.

[0039] Example 5

[0040] The gases in the twin-screw extruder, the devolatilization kettle, the product tank and the connected pipelines are replaced by nitrogen. After the replacement, 100 kg of isopentadiene resin, 5 kg of maleic anhydride and 0.5 kg of antioxidant 1135 are added to the high-speed mixer at a speed of 3000 rpm / min for 5 min to fully mix them to obtain a mixed sample; the mixed material enters the feeding port of the twin-screw extruder through a material lifting belt, the twin-screw extruder is turned on, the speed is set to 300 rpm / min, and the module temperature is 210°C; the electron beam irradiation device is 0.6 MeV, and the electron beam irradiation dose is set to 100 KGy; the grafted resin enters the rear-end devolatilization kettle, and under the conditions of a pressure of -0.07 MPa and a speed of 90 rpm / min, the unreacted polarized grafted monomers and oligomers are vacuum distilled to a recovery tank by vacuum distillation, and the vacuum distillation time is 30 min; the recovered polarized grafted monomers are continuously reused in the reaction. After the vacuum distillation is completed, the modified resin is sent to the granulation workshop for granulation to obtain the modified resin product.

[0041] Example 6

[0042] The gases in the twin-screw extruder, the devolatilizer, the product tank and the connected pipelines are replaced by nitrogen. After the replacement, 100 kg of isopentadiene resin, 5 kg of maleic anhydride and 0.5 kg of antioxidant 1135 are added to the high-speed mixer at a speed of 3000 rpm / min for 5 min to fully mix them to obtain a mixed sample; the mixed material enters the feeding port of the twin-screw extruder through a material lifting belt, the twin-screw extruder is turned on, the speed is set to 300 rpm / min, and the module temperature is 210°C; the electron beam irradiation device is 0.8 MeV, and the electron beam irradiation dose is set to 500 KGy; the grafted resin enters the rear-end devolatilizer, and under the conditions of a pressure of -0.07 MPa and a speed of 90 rpm / min, the unreacted polarized grafted monomers and oligomers are vacuum distilled to a recovery tank by vacuum distillation, and the vacuum distillation time is 30 min; the recovered polarized grafted monomers are continuously reused in the reaction. After the vacuum distillation is completed, the modified resin is sent to the granulation workshop for granulation to obtain the modified resin product.

[0043] Example 7

[0044] The gases in the twin-screw extruder, the devolatilizer, the product tank and the connected pipelines are replaced by nitrogen. After the replacement, 100 kg of isopentadiene resin, 5 kg of maleic anhydride and 0.5 kg of antioxidant 1135 are added to the high-speed mixer at a speed of 3000 rpm / min for 5 min to fully mix them to obtain a mixed sample; the mixture enters the feeding port of the twin-screw extruder through a material lifting belt, the twin-screw extruder is turned on, the speed is set to 300 rpm / min, and the module temperature is 210°C; the electron beam irradiation device is 0.8 MeV, and the electron beam irradiation dose is set to 500 KGy; the grafted resin enters the rear-end devolatilizer, and under the conditions of a pressure of -0.09 MPa and a speed of 90 rpm / min, the unreacted polarized grafted monomers and oligomers are vacuum distilled to a recovery tank by vacuum distillation, and the vacuum distillation time is 40 min; the recovered polarized grafted monomers are continuously reused in the reaction. After the vacuum distillation is completed, the modified resin is sent to the granulation workshop for granulation to obtain the modified resin product.

[0045] Example 8

[0046] The gases in the twin-screw extruder, the devolatilizer, the product tank and the connected pipelines are replaced by nitrogen. After the replacement, 100 kg of isopentadiene resin, 10 kg of maleic anhydride and 1 kg of antioxidant 1135 are added to a high-speed mixer at a speed of 3000 rpm / min for 5 minutes to fully mix them to obtain a mixed sample; the mixture enters the feeding port of the twin-screw extruder through a material lifting belt, the twin-screw extruder is turned on, the speed is set to 300 rpm / min, and the module temperature is 210°C; the electron beam irradiation device is 1 MeV, and the electron beam irradiation dose is set to 1000 KGy; the grafted resin enters the rear-end devolatilizer, and under the conditions of a pressure of -0.09 MPa and a speed of 80 rpm / min, the unreacted polarized grafted monomers and oligomers are vacuum distilled to a recovery tank by vacuum distillation, and the vacuum distillation time is 60 minutes; the recovered polarized grafted monomers are continuously reused in the reaction. After the vacuum distillation is completed, the modified resin is sent to the granulation workshop for granulation to obtain the modified resin product.

[0047] Example 9

[0048] The gases in the twin-screw extruder, the devolatilizer, the product tank and the connected pipelines are replaced by nitrogen. After the replacement, 100 kg of isopentadiene resin, 5 kg of itaconic anhydride and 0.5 kg of antioxidant 1135 are added to the high-speed mixer at a speed of 3000 rpm / min for 5 min to fully mix them to obtain a mixed sample; the mixture enters the feeding port of the twin-screw extruder through a material lifting belt, the twin-screw extruder is turned on, the speed is set to 300 rpm / min, and the module temperature is 210°C; the electron beam irradiation device is 0.8 MeV, and the electron beam irradiation dose is set to 500 KGy; the grafted resin enters the rear-end devolatilizer, and under the conditions of a pressure of -0.09 MPa and a speed of 90 rpm / min, the unreacted polarized grafted monomers and oligomers are vacuum distilled to a recovery tank by vacuum distillation, and the vacuum distillation time is 40 min; the recovered polarized grafted monomers are continuously reused in the reaction. After the vacuum distillation is completed, the modified resin is sent to the granulation workshop for granulation to obtain the modified resin product.

[0049] Example 10

[0050] The gases in the twin-screw extruder, the devolatilizer, the product tank and the connected pipelines were replaced with nitrogen. After the replacement, 100 kg of isoprene resin, 5 kg of itaconic anhydride and 5 kg of maleic anhydride, as well as 0.5 kg of antioxidant 1135 and 0.5 kg of antioxidant 264 were added to the high-speed mixer at a speed of 3500 rpm / min for 40 min to fully mix them to obtain a mixed sample; the mixed material entered the feeding port of the twin-screw extruder through the material lifting belt, and the twin-screw extruder was turned on. , the speed is set to 200rpm / min, the module temperature is 200℃; the electron beam irradiation device is 0.8MeV, and the electron beam irradiation dose is set to 500KGy; the grafted resin enters the rear end devolatilization kettle, and the unreacted polarized grafted monomer and oligomer are vacuum distilled to the recovery tank under the conditions of -0.08Mpa pressure and 70rpm / min speed. The vacuum distillation time is 40min; the recovered polarized grafted monomer is continuously reused in the reaction. After the vacuum distillation work is completed, the modified resin is sent to the granulation workshop for granulation to obtain the modified resin product.

[0051] The test results of the modified piperylic resin in Examples 1 to 10 are shown in Table 1 below.

[0052] Table 1 Test results of modified piperylene resins of Examples 1 to 10

[0053]

[0054] As can be seen from the above table, the present application can effectively improve the reaction efficiency and product quality by precisely controlling the ratio of the polarized grafted monomer and the antioxidant, the rotation speed of the twin-screw extruder and the dose of electron beam irradiation, the reaction time, and the temperature and time of the reduced pressure distillation. Specifically, the chromaticity of the modified isoprene resin provided by the method of the present application can be improved to 3 to 7, the acid value can be improved to 1.2 to 29.31 mg KOHg, the softening point can be between 100 and 110°C, and the melt viscosity can be between 145.5 and 239.5 mPa·s.

[0055] Compared with the existing technology, the beneficial effects of this technical solution are as follows:

[0056] 1) The technical solution of the present application can effectively improve the reaction efficiency and product quality by accurately controlling the ratio of polarized grafted monomer and antioxidant, the speed and time of high-speed mixer, the speed of twin-screw extruder, the dose of electron beam irradiation, and the temperature and time of vacuum distillation. The grafting rate of maleic anhydride in the piperyl-modified resin produced by the present patent can reach 0.2-5%;

[0057] 2) The technical solution of the present application utilizes twin-screw extrusion and electron beam irradiation synergistic processing technology, does not use initiators, reduces the generation of by-products; does not require additional heating, reduces energy consumption; and is provided with a polar monomer recovery tank to collect the components obtained by devolatilization for subsequent recycling. Compared with the existing technology, it can save about 40% of the cost; and

[0058] 3) The process is simple, the reaction time is short, and continuous production from feeding to discharging can be achieved. In addition, no "three wastes" are generated in the production process, truly achieving green, economical and efficient production.

[0059] The features of several embodiments are summarized above so that those skilled in the art can better understand aspects of the present invention. Those skilled in the art should understand that they can easily use the present invention as a basis to design or modify other processes and structures for implementing the same purpose and / or achieving the same advantages as the embodiments introduced herein. Those skilled in the art should also appreciate that this equivalent construction does not deviate from the spirit and scope of the present invention, and that they can make multiple changes, substitutions and changes herein without departing from the spirit and scope of the present invention.

Claims

1. A manufacturing device for modified petroleum resin, characterized in that: include: Mixing machines; A twin-screw extruder is connected to the mixer, wherein the outlet of the mixer is connected to the inlet of the twin-screw extruder; A devolatilizer, connected to the twin-screw extruder, wherein the outlet of the twin-screw extruder is connected to the inlet of the devolatilizer; a recovery tank, connected to the devolatilizer, wherein a first outlet of the devolatilizer is connected to an inlet of the recovery tank; and A condenser is connected to the recovery tank, wherein the first outlet of the recovery tank is connected to the inlet of the condenser in a two-way manner. Wherein, an electron beam irradiation device is arranged at the twin-screw extruder.

2. The manufacturing device according to claim 1, characterized in that: The electron beam irradiation device is arranged at the tail end of the twin-screw extruder close to the devolatilizer.

3. The manufacturing device according to claim 2, characterized in that: The outlet of the twin-screw extruder is connected to the devolatilizer through a pipeline. Wherein, the material in the twin-screw extruder enters the devolatilizer through the pipeline after being irradiated by the electron beam of the electron beam irradiation device.

4. The manufacturing device according to claim 1, characterized in that: Also includes: a finished product tank connected to the devolatilizer, wherein a second outlet of the devolatilizer is connected to an inlet of the finished product tank, wherein the second outlet of the devolatilizer is different from the first outlet of the devolatilizer; and A tail gas absorption tank is connected to the recovery tank, wherein the second outlet of the recovery tank is connected to the inlet of the tail gas absorption tank, and the third outlet of the recovery tank is connected to the inlet of the mixer, wherein the first outlet, the second outlet and the third outlet of the recovery tank are all different.

5. A method for producing a modified petroleum resin, characterized in that: include: Adding petroleum resin, polarized grafting monomer and antioxidant into a mixer to obtain a mixed material; The material is added into a twin-screw extruder, pushed by the twin screws of the twin-screw extruder to the electron beam irradiation zone of the twin-screw extruder irradiated by an electron beam irradiation device, and after the electron beam irradiation, enters the devolatilization reactor through a pipeline; as well as The unreacted polarized grafted monomers and oligomers are condensed in a condenser and recovered into a recovery tank by vacuum distillation. Wherein, the electron beam irradiation device is arranged at the tail end of the twin-screw extruder close to the devolatilizer.

6. The manufacturing method according to claim 5, characterized in that: The rotating speed of the mixer is within the range of 1500-3500 rpm / min, the stirring time of the mixer is within the range of 3-5 min, and while the mixer is running, the mixer is cooled so that the temperature of the material is maintained between 22-25° C.

7. The manufacturing method according to claim 5, characterized in that: The material is added to the feeding port of the twin-screw extruder through a material lifting belt. The speed of the twin screw is set to 170-300 rpm / min, and the module temperature of the twin screw extruder is set to 190-210°C, and Wherein, the dose of the electron beam irradiation is 100-1000 kGy, and the electron energy of the electron beam irradiation is 0.6-1 MeV.

8. The manufacturing method according to claim 5, characterized in that: The polarized grafting monomer includes one or more unsaturated olefin functional monomers such as maleic anhydride and itaconic anhydride. The mass of the polarized grafted monomer is 1%-10% of the mass of the petroleum resin, and the mass of the antioxidant is 0.1%-1% of the mass of the petroleum resin.

9. The manufacturing method according to claim 5, characterized in that: After the material enters the devolatilizer, a stirring device is turned on, and the rotation speed of the stirring device is 70-90 rpm / min; and After the vacuum distillation, the modified petroleum resin is sent to a granulation workshop for granulation to obtain a modified petroleum resin product. Wherein, the pressure of the vacuum distillation is -0.07 to -0.09 MPa, and the time of the vacuum distillation is 30-60 min.

10. The manufacturing method according to claim 5, characterized in that: Adding the petroleum resin into the mixer includes adding the petroleum resin into the mixer under the protection of an inert gas, Wherein, the inert gas exists in the devolatilizer, and the inert gas in the devolatilizer enters the tail gas adsorption tank for adsorption, The inert gas at least replaces the gas in the twin-screw extruder, the devolatilizer and the pipeline to ensure that the entire production environment is an oxygen-free environment.

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