Preparation method of modified furan resin

Abstract

The invention belongs to the technical field of resin, and particularly relates to a preparation method of modified furan resin, aiming at the problems of high brittleness, easy cracking, insufficient corrosion resistance, performance degradation caused by high-temperature curing and poor mixing effect of a reaction kettle in the prior art, the invention provides the following scheme: the preparation method comprises the following steps: S1, proportioning raw materials of the modified furan resin, comprising the following components: 65-75 parts of a furan resin matrix, a flexible chain segment introduced by an epoxy resin modifier, and a silane coupling agent for improving the interface bonding force, so that the problems of high brittleness and poor adhesive force of the traditional furan resin are solved, the impact toughness of the modified furan resin can be improved from 3 kJ / m < 2 > to 8 kJ / m < 2 >, step-by-step reaction at 50-85 DEG C is performed, high-temperature coking is avoided, the molecular structure stability is ensured, and the service life of the furan resin is prolonged. The hexamethylenetetramine and the flexibilizer can prolong the storage period, meanwhile, the impact resistance after curing is improved, and a better stirring effect can be achieved through triple cooperation of the scraper frame, the swing assembly and the stirring frame.

Description

Technical Field

[0001] The present invention relates to the technical field of resins, and in particular to a method for preparing a modified furan resin. Background Art

[0002] The Chinese patent document with application number 202111365735.0 discloses a method for preparing a modified furan resin. Formaldehyde, urea and furfural slag are used as raw materials to synthesize urea-formaldehyde resin under alkaline conditions, and then under acidic conditions, furfural alcohol and urea-formaldehyde resin undergo resinification reaction to synthesize urea-formaldehyde furan resin. The addition of furfural slag can modify the strength properties of urea-formaldehyde furan resin and reduce the content of free formaldehyde. The process method of the present invention is simple, safe and reliable, with obvious effects and environmental protection. It is mainly used in the production of cast iron and steel castings. After the furan resin is modified, the tensile strength is greatly improved and the content of free formaldehyde is also reduced. At the same time, the solid waste furfural slag obtained from the production of furfural is rationally utilized to save energy and protect the environment. The process method of the present invention is simple, safe and reliable, with obvious effects and environmental protection. It is mainly used in the production of cast iron and steel castings.

[0003] However, the preparation method of this modified furan resin also has some problems. For example, the furan resin has a high cross-linking density after curing and the molecular chain is very rigid, resulting in poor bending / impact resistance (bending strength is usually <60MPa). It is prone to cracking and failure in fields such as casting molds and anti-corrosion linings. The resin solidification body has micropores and interface defects, and strong acid media are easy to penetrate, causing swelling and shedding, and the mass loss rate is high. Furan resin polymerization requires a high temperature of >100°C, which is prone to violent polymerization or local coking. In addition, conventional reactors use single-rod stirring, and fewer raw materials can be stirred at the same time, affecting the mixing effect. Summary of the Invention

[0004] Based on the problems of the background technology such as high brittleness, easy cracking, insufficient corrosion resistance, performance degradation caused by high temperature curing, and poor mixing effect in the reactor, the present invention proposes a preparation method of a modified furan resin.

[0005] The present invention provides a method for preparing a modified furan resin, comprising the following steps: S1: The raw material ratio of the modified furan resin includes the following components in parts by weight: 65 to 75 parts of furan resin matrix, 5 to 15 parts of epoxy modifier, 3 to 8 parts of latent curing agent, 15 to 25 parts of organic solvent, 1 to 5 parts of toughening agent, 0.5 to 3.0 parts of silane coupling agent and 0.1 to 1.0 parts of antioxidant; S2: Pour the furan resin matrix into a reaction kettle, heat to 40°C to 60°C, add an organic solvent, stir at 250-300 rpm for 15 minutes, add an epoxy modifier, raise the temperature to 70°C to 85°C, and react under nitrogen protection for 1 hour to 2 hours; S3: Cooling to 50°C to 60°C, adding a silane coupling agent, stirring at a constant temperature for 25 minutes to 45 minutes, adding a latent curing agent, a toughening agent, and an antioxidant, maintaining the temperature at 40°C to 50°C and mixing for 20 minutes to 40 minutes to obtain a mixture; S4: degassing the mixture at a vacuum degree of -0.08 to -0.1 MPa for 15 to 30 minutes, filtering it through a 5 to 10 μm filter, and cooling it to room temperature to obtain a modified furan resin; The reactor comprises a base, a bracket is bolted between two sides of the top of the base, the top of the bracket is bolted to the reactor body, a rotating drum is sleeved inside the reactor body, a scraper frame is bolted between the two ends of the rotating drum surface, a swing assembly is rotatably sleeved on the surface of the rotating drum, a secondary shaft is rotatably sleeved inside the rotating drum, a support rod is bolted to the surface of the secondary shaft, an end of the support rod away from the secondary shaft is bolted to the stirring frame, and a key is connected to the left end of the rotating drum with a power mechanism. The epoxy resin modifier introduces a flexible chain segment, and the silane coupling agent improves the interface bonding strength, thereby solving the problems of high brittleness and poor adhesion of traditional furan resin, and the impact toughness of the modified furan resin can be increased from 3 kJ / m 2 Increased to 8kJ / m 2 , 50-85℃ step-by-step reaction to avoid high temperature coking and ensure the stability of the molecular structure. Hexamethylenetetramine and toughening agent can extend the storage period and improve the impact resistance after curing. The triple combination of scraper frame, swing component and stirring frame can achieve better stirring effect.

[0006] Preferably, in S1, the furan resin matrix is ​​one of furfural-acetone type resin and furfuryl alcohol-formaldehyde copolymer, with a viscosity range of 400-700 mPa·s (25°C), the epoxy modifier is one of bisphenol A type epoxy resin and bio-based epoxy resin, with an epoxy value of 0.4-0.6 eq / 100g, and the silane coupling agent is one of γ-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane, which can ensure the effect of the reaction.

[0007] Preferably, in S1, the latent curing agent is one of hexamethylenetetramine and aromatic sulfonic acid complex salt, with a particle size of ≤20 μm, the organic solvent is one of ethanol, propylene glycol methyl ether, and diethylene glycol butyl ether, and the toughening agent is one of terminal carboxyl nitrile rubber and polyurethane prepolymer, with a molecular weight range of 3000 to 5000 g / mol, which is beneficial to maintaining the resin effect.

[0008] Preferably, in S2, the reaction conditions are: at a temperature of 75±2° C., the nitrogen flow rate is controlled at 0.5 to 1 L / min, and the reaction is carried out for 1.5 hours to ensure the reaction effect.

[0009] Preferably, the power mechanism includes a power motor, a rotating rod, a main sprocket, a chain, a secondary sprocket and a gear assembly. The output end of the power motor is key-connected to the right end of the rotating rod. Two main sprockets, two chains and two secondary sprockets are respectively key-connected at the axis centers of the two main sprockets to the two end keys of the rotating rod surface. The teeth of the main sprocket are meshed with the bottom end inside the chain, and the inner side of the chain is meshed with the teeth of the secondary sprocket. The two ends of the rotating drum are respectively key-connected with the axis centers of the two secondary sprockets. The rotating drum is key-connected to the gear assembly. The power supply of the power motor is turned on. The power supply can be an external power supply or an internal power supply. The power motor can drive the rotating rod to rotate, the rotating rod can drive the main sprocket to rotate, the main sprocket can drive the chain to rotate, and the chain can drive the secondary sprocket to rotate. The radius of the main sprocket is twice the radius of the secondary sprocket, and the secondary sprocket can drive the rotating drum.

[0010] Preferably, the gear assembly includes a main gear, a duplex gear and a slave gear. The left end of the rotating drum is key-connected to the axis of the main gear, the teeth of the main gear are meshed with the small gear of the duplex gear, the large gear of the duplex gear is meshed with the teeth of the slave gear, and the axis of the slave gear is key-connected to the left end of the secondary shaft. The rotating drum can drive the main gear to rotate, the main gear can drive the duplex gear to rotate, and the duplex gear can drive the slave gear to rotate. The double gear size of the duplex gear can produce an acceleration effect on the slave gear, and the slave gear can drive the secondary shaft to rotate.

[0011] Preferably, the left side bolts of the reactor body are connected with a main protective cover, the surface of the power motor is connected with the left side bolts of the main protective cover, and the surface of the rotating rod is rotated and sleeved with the hole of the base. The main protective cover can play a protective role and stabilize the power motor.

[0012] Preferably, a secondary protective cover is bolted to the right side of the reactor body, and the inner side of the secondary protective cover is rotatably connected to the axis of the double gear, so that the secondary protective cover can play a shielding and protective role.

[0013] Preferably, the swing assembly includes a connecting ring, a swing rod and a swing ball. There are three swing rods and three swing balls. The three swing rods are welded to the connecting ring. The end of the swing rod away from the connecting ring is welded to the surface of the swing ball. The interior of the connecting ring is rotatably connected to the surface of the rotating drum. The rotating drum can drive the connecting ring, the swing rod and the swing ball to rotate. Under the action of centrifugal force and gravity, the swing ball can generate hammering force to enhance the mixing effect.

[0014] Preferably, the reactor body has a structure that is thick in the middle and thin at both ends. The middle end of the top of the reactor body is connected to a feed port, the surface of the scraper frame contacts the inner wall of the reactor body, the middle of the rotating drum is disconnected, and the support rod is located between the two rotating drums. The reactor body facilitates the concentration of raw materials, and the feed port facilitates the addition of raw materials.

[0015] Beneficial effects of the present invention: The epoxy resin modifier introduces flexible chain segments, and the silane coupling agent improves the interfacial bonding strength, solving the problems of traditional furan resins such as large brittleness and poor adhesion. The impact toughness of the modified furan resin can be increased from 3kJ / m 2 Increased to 8kJ / m 2 , 50-85℃ step-by-step reaction to avoid high temperature coking and ensure the stability of the molecular structure. Hexamethylenetetramine and toughening agent can extend the storage period and improve the impact resistance after curing. The triple combination of scraper frame, swing component and stirring frame can achieve better stirring effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a schematic diagram of the main structure proposed by the present invention; Figure 2 A rear cross-sectional schematic diagram of the present invention; Figure 3 It is a left side schematic diagram of the rotating drum proposed by the present invention; Figure 4 This is a three-dimensional schematic diagram of the double gears proposed by the present invention; Figure 5 The working flow diagram proposed by the present invention.

[0017] In the figure: 1. Base; 2. Bracket; 3. Reactor body; 4. Power motor; 5. Rotating rod; 6. Main sprocket; 7. Chain; 8. Secondary sprocket; 9. Rotating drum; 10. Scraper frame; 11. Connecting ring; 12. Rocker arm; 13. Rocker ball; 14. Main gear; 15. Duplex gear; 16. Slave gear; 17. Secondary shaft; 18. Support rod; 19. Stirring frame; 20. Main protective cover; 21. Secondary protective cover. DETAILED DESCRIPTION

[0018] The present invention will be further explained below with reference to specific embodiments.

[0019] Reference Figure 1-5 , Example 1 This embodiment provides a method for preparing a modified furan resin, comprising the following steps: S1: The raw material ratio of the modified furan resin, calculated by weight, includes the following components: 66 parts of furan resin matrix, 9 parts of epoxy modifier, 3 parts of latent curing agent, 17 parts of organic solvent, 2 parts of toughening agent, 2.3 parts of silane coupling agent, and 0.7 parts of antioxidant. The furan resin matrix is ​​a furfural-acetone type resin with a viscosity range of 600 mPa·s (25°C), the epoxy modifier is a bisphenol A type epoxy resin with an epoxy value of 0.5 eq / 100 g, the silane coupling agent is γ-aminopropyltriethoxysilane, the latent curing agent is hexamethylenetetramine with a particle size of ≤20 μm, the organic solvent is ethanol, and the toughening agent is carboxyl-terminated nitrile rubber with a molecular weight range of 4000 g / mol. S2: Pour the furan resin matrix into a reactor, heat to 46°C, add the organic solvent, stir at 280 rpm for 15 minutes, add the epoxy modifier, heat to 79°C, and react under nitrogen protection for 2 hours. At a temperature of 75±2°C, the nitrogen flow rate is controlled at 0.7 L / min, and the reaction is carried out for 1.5 hours; S3: Cooling to 50°C to 60°C, adding a silane coupling agent, stirring at a constant temperature for 25 minutes to 45 minutes, adding a latent curing agent, a toughening agent, and an antioxidant, maintaining the temperature at 40°C to 50°C and mixing for 20 minutes to 40 minutes to obtain a mixture; S4: degassing the mixture at a vacuum degree of -0.08 to -0.1 MPa for 15 to 30 minutes, filtering it through a 5 to 10 μm filter, and cooling it to room temperature to obtain a modified furan resin; The reactor includes a base 1, a bracket 2 is bolted between the two sides of the top of the base 1, the top of the bracket 2 is bolted to the reactor body 3, the inside of the reactor body 3 is rotatably sleeved with a drum 9, the two ends of the surface of the drum 9 are bolted to a scraper frame 10, the surface of the drum 9 is rotatably sleeved with a swing assembly, the inside of the drum 9 is rotatably sleeved with a secondary shaft 17, the surface of the secondary shaft 17 is bolted to a support rod 18, the end of the support rod 18 away from the secondary shaft 17 is bolted to a stirring frame 19, the drum 9 The left end key is connected to the power mechanism, which includes a power motor 4, a rotating rod 5, a main sprocket 6, a chain 7, a secondary sprocket 8 and a gear assembly. The output end of the power motor 4 is connected to the right end key of the rotating rod 5. The main sprocket 6, the chain 7 and the secondary sprocket 8 are each provided with two. The axis of the two main sprockets 6 is respectively connected to the two end keys of the surface of the rotating rod 5. The teeth of the main sprocket 6 are engaged with the bottom end of the chain 7, and the inner side of the chain 7 is engaged with the teeth of the secondary sprocket 8. The two ends of the rotating drum 9 are respectively connected to the axis of the two secondary sprockets 8. The left side of the reactor body 3 is connected with the main protective cover 20 by bolts, the surface of the power motor 4 is connected with the left side of the main protective cover 20 by bolts, the surface of the rotating rod 5 is connected with the hole of the base 1 by rotation, and the main protective cover 20 can play a protective role and stabilize the power motor 4. The right side of the reactor body 3 is connected with the auxiliary protective cover 21 by bolts, and the inner side of the auxiliary protective cover 21 is connected with the axis of the double gear 15 by rotation. The swing assembly includes a connecting ring 11, a rocker arm 12 and a swing ball 13, there are three swing rods 12 and three swing balls 13, the three swing rods 12 are welded to the connecting ring 11, the end of the swing rod 12 away from the connecting ring 11 is welded to the surface of the swing ball 13, the interior of the connecting ring 11 is rotatably sleeved with the surface of the rotating drum 9, the reactor body 3 has a structure that is thick in the middle and thin at both ends, the middle end of the top of the reactor body 3 is connected to the feed port, the surface of the scraper frame 10 is in contact with the inner wall of the reactor body 3, the middle of the rotating drum 9 is disconnected, and the support rod 18 is located between the two rotating drums 9.

[0020] Reference Figure 1-5 , Example 2 This embodiment provides a method for preparing a modified furan resin, comprising the following steps: S1: The raw material ratio of the modified furan resin, calculated by weight, includes the following components: 68 parts of furan resin matrix, 7 parts of epoxy modifier, 4 parts of latent curing agent, 16 parts of organic solvent, 2 parts of toughening agent, 2.4 parts of silane coupling agent, and 0.6 parts of antioxidant. The furan resin matrix is ​​a furfural-acetone type resin with a viscosity range of 600 mPa·s (25°C), the epoxy modifier is a bisphenol A type epoxy resin with an epoxy value of 0.5 eq / 100 g, the silane coupling agent is γ-aminopropyltriethoxysilane, the latent curing agent is hexamethylenetetramine with a particle size of ≤20 μm, the organic solvent is ethanol, and the toughening agent is carboxyl-terminated nitrile rubber with a molecular weight range of 4000 g / mol. S2: Pour the furan resin matrix into a reactor, heat to 46°C, add the organic solvent, stir at 280 rpm for 15 minutes, add the epoxy modifier, heat to 79°C, and react under nitrogen protection for 2 hours. At a temperature of 75±2°C, the nitrogen flow rate is controlled at 0.7 L / min, and the reaction is carried out for 1.5 hours; S3: Cooling to 50°C to 60°C, adding a silane coupling agent, stirring at a constant temperature for 25 minutes to 45 minutes, adding a latent curing agent, a toughening agent, and an antioxidant, maintaining the temperature at 40°C to 50°C and mixing for 20 minutes to 40 minutes to obtain a mixture; S4: degassing the mixture at a vacuum degree of -0.08 to -0.1 MPa for 15 to 30 minutes, filtering it through a 5 to 10 μm filter, and cooling it to room temperature to obtain a modified furan resin; The reactor includes a base 1, a bracket 2 is bolted between the two sides of the top of the base 1, the top of the bracket 2 is bolted to the reactor body 3, the inside of the reactor body 3 is rotatably sleeved with a drum 9, the two ends of the surface of the drum 9 are bolted to a scraper frame 10, the surface of the drum 9 is rotatably sleeved with a swing assembly, the inside of the drum 9 is rotatably sleeved with a secondary shaft 17, the surface of the secondary shaft 17 is bolted to a support rod 18, the end of the support rod 18 away from the secondary shaft 17 is bolted to a stirring frame 19, the drum 9 The left end key is connected to the power mechanism, which includes a power motor 4, a rotating rod 5, a main sprocket 6, a chain 7, a secondary sprocket 8 and a gear assembly. The output end of the power motor 4 is connected to the right end key of the rotating rod 5. The main sprocket 6, the chain 7 and the secondary sprocket 8 are each provided with two. The axis of the two main sprockets 6 is respectively connected to the two end keys of the surface of the rotating rod 5. The teeth of the main sprocket 6 are engaged with the bottom end of the chain 7, and the inner side of the chain 7 is engaged with the teeth of the secondary sprocket 8. The two ends of the rotating drum 9 are respectively connected to the axis of the two secondary sprockets 8. The left side of the reactor body 3 is connected with the main protective cover 20 by bolts, the surface of the power motor 4 is connected with the left side of the main protective cover 20 by bolts, the surface of the rotating rod 5 is connected with the hole of the base 1 by rotation, and the main protective cover 20 can play a protective role and stabilize the power motor 4. The right side of the reactor body 3 is connected with the auxiliary protective cover 21 by bolts, and the inner side of the auxiliary protective cover 21 is connected with the axis of the double gear 15 by rotation. The swing assembly includes a connecting ring 11, a rocker arm 12 and a swing ball 13, there are three swing rods 12 and three swing balls 13, the three swing rods 12 are welded to the connecting ring 11, the end of the swing rod 12 away from the connecting ring 11 is welded to the surface of the swing ball 13, the interior of the connecting ring 11 is rotatably sleeved with the surface of the rotating drum 9, the reactor body 3 has a structure that is thick in the middle and thin at both ends, the middle end of the top of the reactor body 3 is connected to the feed port, the surface of the scraper frame 10 is in contact with the inner wall of the reactor body 3, the middle of the rotating drum 9 is disconnected, and the support rod 18 is located between the two rotating drums 9.

[0021] Reference Figure 1-5 , Example 3 This embodiment provides a method for preparing a modified furan resin, comprising the following steps: S1: The raw material ratio of the modified furan resin, calculated by weight, includes the following components: 70 parts of a furan resin matrix, 6 parts of an epoxy modifier, 4 parts of a latent curing agent, 15 parts of an organic solvent, 3 parts of a toughening agent, 1.6 parts of a silane coupling agent, and 0.4 parts of an antioxidant. The furan resin matrix is ​​a furfural-acetone type resin with a viscosity range of 600 mPa·s (25°C), the epoxy modifier is a bisphenol A type epoxy resin with an epoxy value of 0.5 eq / 100 g, the silane coupling agent is γ-aminopropyltriethoxysilane, the latent curing agent is hexamethylenetetramine with a particle size of ≤20 μm, the organic solvent is ethanol, and the toughening agent is a carboxyl-terminated nitrile rubber with a molecular weight range of 4000 g / mol. S2: Pour the furan resin matrix into a reactor, heat to 46°C, add the organic solvent, stir at 280 rpm for 15 minutes, add the epoxy modifier, heat to 79°C, and react under nitrogen protection for 2 hours. At a temperature of 75±2°C, the nitrogen flow rate is controlled at 0.7 L / min, and the reaction is carried out for 1.5 hours; S3: Cooling to 50°C to 60°C, adding a silane coupling agent, stirring at a constant temperature for 25 minutes to 45 minutes, adding a latent curing agent, a toughening agent, and an antioxidant, maintaining the temperature at 40°C to 50°C and mixing for 20 minutes to 40 minutes to obtain a mixture; S4: degassing the mixture at a vacuum degree of -0.08 to -0.1 MPa for 15 to 30 minutes, filtering it through a 5 to 10 μm filter, and cooling it to room temperature to obtain a modified furan resin; The reactor includes a base 1, a bracket 2 is bolted between the two sides of the top of the base 1, the top of the bracket 2 is bolted to the reactor body 3, the inside of the reactor body 3 is rotatably sleeved with a drum 9, the two ends of the surface of the drum 9 are bolted to a scraper frame 10, the surface of the drum 9 is rotatably sleeved with a swing assembly, the inside of the drum 9 is rotatably sleeved with a secondary shaft 17, the surface of the secondary shaft 17 is bolted to a support rod 18, the end of the support rod 18 away from the secondary shaft 17 is bolted to a stirring frame 19, the drum 9 The left end key is connected to the power mechanism, which includes a power motor 4, a rotating rod 5, a main sprocket 6, a chain 7, a secondary sprocket 8 and a gear assembly. The output end of the power motor 4 is connected to the right end key of the rotating rod 5. The main sprocket 6, the chain 7 and the secondary sprocket 8 are each provided with two. The axis of the two main sprockets 6 is respectively connected to the two end keys of the surface of the rotating rod 5. The teeth of the main sprocket 6 are engaged with the bottom end of the chain 7, and the inner side of the chain 7 is engaged with the teeth of the secondary sprocket 8. The two ends of the rotating drum 9 are respectively connected to the axis of the two secondary sprockets 8. The left side of the reactor body 3 is connected with the main protective cover 20 by bolts, the surface of the power motor 4 is connected with the left side of the main protective cover 20 by bolts, the surface of the rotating rod 5 is connected with the hole of the base 1 by rotation, and the main protective cover 20 can play a protective role and stabilize the power motor 4. The right side of the reactor body 3 is connected with the auxiliary protective cover 21 by bolts, and the inner side of the auxiliary protective cover 21 is connected with the axis of the double gear 15 by rotation. The swing assembly includes a connecting ring 11, a rocker arm 12 and a swing ball 13, there are three swing rods 12 and three swing balls 13, the three swing rods 12 are welded to the connecting ring 11, the end of the swing rod 12 away from the connecting ring 11 is welded to the surface of the swing ball 13, the interior of the connecting ring 11 is rotatably sleeved with the surface of the rotating drum 9, the reactor body 3 has a structure that is thick in the middle and thin at both ends, the middle end of the top of the reactor body 3 is connected to the feed port, the surface of the scraper frame 10 is in contact with the inner wall of the reactor body 3, the middle of the rotating drum 9 is disconnected, and the support rod 18 is located between the two rotating drums 9.

[0022] Reference Figure 1-5 , Example 4 This embodiment provides a method for preparing a modified furan resin, comprising the following steps: S1: The raw material ratio of the modified furan resin, calculated by weight, includes the following components: 65 parts of a furan resin matrix, 5 parts of an epoxy modifier, 6 parts of a latent curing agent, 18 parts of an organic solvent, 4 parts of a toughening agent, 1.7 parts of a silane coupling agent, and 0.3 parts of an antioxidant. The furan resin matrix is ​​a furfural-acetone type resin with a viscosity range of 600 mPa·s (25°C), the epoxy modifier is a bisphenol A type epoxy resin with an epoxy value of 0.5 eq / 100 g, the silane coupling agent is γ-aminopropyltriethoxysilane, the latent curing agent is hexamethylenetetramine with a particle size of ≤20 μm, the organic solvent is ethanol, and the toughening agent is a carboxyl-terminated nitrile rubber with a molecular weight range of 4000 g / mol. S2: Pour the furan resin matrix into a reactor, heat to 46°C, add the organic solvent, stir at 280 rpm for 15 minutes, add the epoxy modifier, heat to 79°C, and react under nitrogen protection for 2 hours. At a temperature of 75±2°C, the nitrogen flow rate is controlled at 0.7 L / min, and the reaction is carried out for 1.5 hours; S3: Cooling to 50°C to 60°C, adding a silane coupling agent, stirring at a constant temperature for 25 minutes to 45 minutes, adding a latent curing agent, a toughening agent, and an antioxidant, maintaining the temperature at 40°C to 50°C and mixing for 20 minutes to 40 minutes to obtain a mixture; S4: degassing the mixture at a vacuum degree of -0.08 to -0.1 MPa for 15 to 30 minutes, filtering it through a 5 to 10 μm filter, and cooling it to room temperature to obtain a modified furan resin; The reactor includes a base 1, a bracket 2 is bolted between the two sides of the top of the base 1, the top of the bracket 2 is bolted to the reactor body 3, the inside of the reactor body 3 is rotatably sleeved with a drum 9, the two ends of the surface of the drum 9 are bolted to a scraper frame 10, the surface of the drum 9 is rotatably sleeved with a swing assembly, the inside of the drum 9 is rotatably sleeved with a secondary shaft 17, the surface of the secondary shaft 17 is bolted to a support rod 18, the end of the support rod 18 away from the secondary shaft 17 is bolted to a stirring frame 19, the drum 9 The left end key is connected to the power mechanism, which includes a power motor 4, a rotating rod 5, a main sprocket 6, a chain 7, a secondary sprocket 8 and a gear assembly. The output end of the power motor 4 is connected to the right end key of the rotating rod 5. The main sprocket 6, the chain 7 and the secondary sprocket 8 are each provided with two. The axis of the two main sprockets 6 is respectively connected to the two end keys of the surface of the rotating rod 5. The teeth of the main sprocket 6 are engaged with the bottom end of the chain 7, and the inner side of the chain 7 is engaged with the teeth of the secondary sprocket 8. The two ends of the rotating drum 9 are respectively connected to the axis of the two secondary sprockets 8. The left side of the reactor body 3 is connected with the main protective cover 20 by bolts, the surface of the power motor 4 is connected with the left side of the main protective cover 20 by bolts, the surface of the rotating rod 5 is connected with the hole of the base 1 by rotation, and the main protective cover 20 can play a protective role and stabilize the power motor 4. The right side of the reactor body 3 is connected with the auxiliary protective cover 21 by bolts, and the inner side of the auxiliary protective cover 21 is connected with the axis of the double gear 15 by rotation. The swing assembly includes a connecting ring 11, a rocker arm 12 and a swing ball 13, there are three swing rods 12 and three swing balls 13, the three swing rods 12 are welded to the connecting ring 11, the end of the swing rod 12 away from the connecting ring 11 is welded to the surface of the swing ball 13, the interior of the connecting ring 11 is rotatably sleeved with the surface of the rotating drum 9, the reactor body 3 has a structure that is thick in the middle and thin at both ends, the middle end of the top of the reactor body 3 is connected to the feed port, the surface of the scraper frame 10 is in contact with the inner wall of the reactor body 3, the middle of the rotating drum 9 is disconnected, and the support rod 18 is located between the two rotating drums 9.

[0023] Reference Figure 1-5 , Example 5 This embodiment provides a method for preparing a modified furan resin, comprising the following steps: S1: The raw material ratio of the modified furan resin, calculated by weight, includes the following components: 70 parts of a furan resin matrix, 5 parts of an epoxy modifier, 3 parts of a latent curing agent, 20 parts of an organic solvent, 3 parts of a toughening agent, 1.8 parts of a silane coupling agent, and 0.2 parts of an antioxidant. The furan resin matrix is ​​a furfural-acetone type resin with a viscosity range of 600 mPa·s (25°C), the epoxy modifier is a bisphenol A type epoxy resin with an epoxy value of 0.5 eq / 100 g, the silane coupling agent is γ-aminopropyltriethoxysilane, the latent curing agent is hexamethylenetetramine with a particle size of ≤20 μm, the organic solvent is ethanol, and the toughening agent is a carboxyl-terminated nitrile rubber with a molecular weight range of 4000 g / mol. S2: Pour the furan resin matrix into a reactor, heat to 46°C, add the organic solvent, stir at 280 rpm for 15 minutes, add the epoxy modifier, heat to 79°C, and react under nitrogen protection for 2 hours. At a temperature of 75±2°C, the nitrogen flow rate is controlled at 0.7 L / min, and the reaction is carried out for 1.5 hours; S3: Cooling to 50°C to 60°C, adding a silane coupling agent, stirring at a constant temperature for 25 minutes to 45 minutes, adding a latent curing agent, a toughening agent, and an antioxidant, maintaining the temperature at 40°C to 50°C and mixing for 20 minutes to 40 minutes to obtain a mixture; S4: degassing the mixture at a vacuum degree of -0.08 to -0.1 MPa for 15 to 30 minutes, filtering it through a 5 to 10 μm filter, and cooling it to room temperature to obtain a modified furan resin; The reactor includes a base 1, a bracket 2 is bolted between the two sides of the top of the base 1, the top of the bracket 2 is bolted to the reactor body 3, the inside of the reactor body 3 is rotatably sleeved with a drum 9, the two ends of the surface of the drum 9 are bolted to a scraper frame 10, the surface of the drum 9 is rotatably sleeved with a swing assembly, the inside of the drum 9 is rotatably sleeved with a secondary shaft 17, the surface of the secondary shaft 17 is bolted to a support rod 18, the end of the support rod 18 away from the secondary shaft 17 is bolted to a stirring frame 19, the drum 9 The left end key is connected to the power mechanism, which includes a power motor 4, a rotating rod 5, a main sprocket 6, a chain 7, a secondary sprocket 8 and a gear assembly. The output end of the power motor 4 is connected to the right end key of the rotating rod 5. The main sprocket 6, the chain 7 and the secondary sprocket 8 are each provided with two. The axis of the two main sprockets 6 is respectively connected to the two end keys of the surface of the rotating rod 5. The teeth of the main sprocket 6 are engaged with the bottom end of the chain 7, and the inner side of the chain 7 is engaged with the teeth of the secondary sprocket 8. The two ends of the rotating drum 9 are respectively connected to the axis of the two secondary sprockets 8. The left side of the reactor body 3 is connected with the main protective cover 20 by bolts, the surface of the power motor 4 is connected with the left side of the main protective cover 20 by bolts, the surface of the rotating rod 5 is connected with the hole of the base 1 by rotation, and the main protective cover 20 can play a protective role and stabilize the power motor 4. The right side of the reactor body 3 is connected with the auxiliary protective cover 21 by bolts, and the inner side of the auxiliary protective cover 21 is connected with the axis of the double gear 15 by rotation. The swing assembly includes a connecting ring 11, a rocker arm 12 and a swing ball 13, there are three swing rods 12 and three swing balls 13, the three swing rods 12 are welded to the connecting ring 11, the end of the swing rod 12 away from the connecting ring 11 is welded to the surface of the swing ball 13, the interior of the connecting ring 11 is rotatably sleeved with the surface of the rotating drum 9, the reactor body 3 has a structure that is thick in the middle and thin at both ends, the middle end of the top of the reactor body 3 is connected to the feed port, the surface of the scraper frame 10 is in contact with the inner wall of the reactor body 3, the middle of the rotating drum 9 is disconnected, and the support rod 18 is located between the two rotating drums 9.

[0024] Comparing conventional resins with the resins obtained in Examples 1 to 5, the resins obtained in Examples 1 to 5 are shown in the following table:

[0025] The test standard for bending strength is GB / T9341-2008; The test standard for impact toughness is ISO179-1:2010; The test standard for corrosion weight loss is ASTM D543-14.

[0026] As can be seen from the above table, the bending strength, strong acid corrosion resistance and high temperature curing performance of the resin prepared by the present invention are significantly improved, and the second embodiment is the best embodiment.

[0027] Working principle: Pour the raw materials into the interior of the reactor body 3, connect the power supply of the power motor 4, which can be an external power supply or an internal power supply, the power motor 4 can drive the rotating rod 5 to rotate, the rotating rod 5 can drive the main sprocket 6 to rotate, the main sprocket 6 can drive the chain 7 to rotate, the chain 7 can drive the secondary sprocket 8 to rotate, the radius of the main sprocket 6 is twice the radius of the secondary sprocket 8, the secondary sprocket 8 can drive the rotating drum 9, the rotating drum 9 can drive the scraper frame 10, the scraper frame 10 can mix the inside of the reactor body 3, the rotating drum 9 can drive the connecting ring 11 and the rocker arm 12 and the swing ball 13 rotate, and the swing ball 13 can generate a hammering force under the action of centrifugal force and gravity to enhance the mixing effect. The rotating drum 9 can drive the main gear 14 to rotate, and the main gear 14 can drive the double gear 15 to rotate, and the double gear 15 can drive the slave gear 16 to rotate. The double gear size of the double gear 15 can produce an acceleration effect on the slave gear 16, and the slave gear 16 can drive the countershaft 17 to rotate, and the countershaft 17 can drive the support rod 18 to rotate, and the support rod 18 can drive the stirring frame 19 to rotate, and the stirring frame 19 can stir.

[0028] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A method for preparing a modified furan resin, characterized in that: The following steps are involved: S1: The raw material ratio of the modified furan resin includes the following components in parts by weight: 65 to 75 parts of furan resin matrix, 5 to 15 parts of epoxy modifier, 3 to 8 parts of latent curing agent, 15 to 25 parts of organic solvent, 1 to 5 parts of toughening agent, 0.5 to 3.0 parts of silane coupling agent and 0.1 to 1.0 parts of antioxidant; S2: Pour the furan resin matrix into a reaction kettle, heat to 40°C to 60°C, add an organic solvent, stir at 250-300 rpm for 15 minutes, add an epoxy modifier, raise the temperature to 70°C to 85°C, and react under nitrogen protection for 1 hour to 2 hours; S3: Cooling to 50°C to 60°C, adding a silane coupling agent, stirring at a constant temperature for 25 minutes to 45 minutes, adding a latent curing agent, a toughening agent, and an antioxidant, maintaining the temperature at 40°C to 50°C and mixing for 20 minutes to 40 minutes to obtain a mixture; S4: degassing the mixture at a vacuum degree of -0.08 to -0.1 MPa for 15 to 30 minutes, filtering it through a 5 to 10 μm filter, and cooling it to room temperature to obtain a modified furan resin; The reactor comprises a base (1), a bracket (2) is bolted between two sides of the top of the base (1), a reactor body (3) is bolted to the top of the bracket (2), a rotating drum (9) is rotatably sleeved inside the reactor body (3), a scraper frame (10) is bolted between two ends of the surface of the rotating drum (9), a swing assembly is rotatably sleeved on the surface of the rotating drum (9), a secondary shaft (17) is rotatably sleeved inside the rotating drum (9), a support rod (18) is bolted to the surface of the secondary shaft (17), an end of the support rod (18) away from the secondary shaft (17) is bolted to the stirring frame (19), and a power mechanism is keyed to the left end of the rotating drum (9).

2. The method for preparing a modified furan resin according to claim 1, wherein In S1, the furan resin matrix is ​​one of furfural-acetone type resin and furfuryl alcohol-formaldehyde copolymer, with a viscosity range of 400-700 mPa·s (25°C), the epoxy modifier is one of bisphenol A type epoxy resin and bio-based epoxy resin, with an epoxy value of 0.4-0.6 eq / 100 g, and the silane coupling agent is one of γ-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane.

3. The method for preparing a modified furan resin according to claim 1, wherein In S1, the latent curing agent is one of hexamethylenetetramine and aromatic sulfonic acid complex salt, with a particle size of ≤20 μm, the organic solvent is one of ethanol, propylene glycol methyl ether, and diethylene glycol butyl ether, and the toughening agent is one of terminal carboxyl nitrile rubber and polyurethane prepolymer, with a molecular weight range of 3000 to 5000 g / mol.

4. The method for preparing a modified furan resin according to claim 1, wherein In S2, the reaction conditions are: at a temperature of 75±2° C., a nitrogen flow rate controlled at 0.5 to 1 L / min, and the reaction is carried out for 1.5 hours.

5. The method for preparing a modified furan resin according to claim 1, wherein The power mechanism comprises a power motor (4), a rotating rod (5), a main sprocket (6), a chain (7), a secondary sprocket (8) and a gear assembly. The output end of the power motor (4) is key-connected to the right end of the rotating rod (5). Two main sprockets (6), two chains (7) and two secondary sprockets (8) are provided. The axis centers of the two main sprockets (6) are respectively key-connected to the two ends of the surface of the rotating rod (5). The teeth of the main sprocket (6) are meshed with the bottom end inside the chain (7). The inner side of the chain (7) is meshed with the teeth of the secondary sprocket (8). The two ends of the rotating drum (9) are respectively key-connected to the axis centers of the two secondary sprockets (8). The rotating drum (9) is key-connected to the gear assembly.

6. The method for preparing a modified furan resin according to claim 5, wherein: The gear assembly includes a main gear (14), a duplex gear (15) and a slave gear (16). The left end of the rotating drum (9) is key-connected to the axis of the main gear (14). The teeth of the main gear (14) are meshed with the small gear of the duplex gear (15). The large gear of the duplex gear (15) is meshed with the teeth of the slave gear (16). The axis of the slave gear (16) is key-connected to the left end of the countershaft (17).

7. The method for preparing a modified furan resin according to claim 5, wherein: The left side of the reactor body (3) is bolted to the main protective cover (20), the surface of the power motor (4) is bolted to the left side of the main protective cover (20), and the surface of the rotating rod (5) is rotatably sleeved to the hole of the base (1).

8. The method for preparing a modified furan resin according to claim 6, wherein: The right side of the reactor body (3) is bolted to a secondary protective cover (21), and the inner side of the secondary protective cover (21) is rotatably connected to the axis of the double gear (15).

9. The method for preparing a modified furan resin according to claim 1, wherein The swing assembly comprises a connecting ring (11), a swing rod (12) and a swing ball (13), wherein three swing rods (12) and three swing balls (13) are provided, and the three swing rods (12) are welded to the connecting ring (11), and one end of the swing rod (12) away from the connecting ring (11) is welded to the surface of the swing ball (13), and the interior of the connecting ring (11) is rotatably sleeved with the surface of the rotating drum (9).

10. The method for preparing a modified furan resin according to claim 1, wherein: The reactor body (3) has a structure with a thick middle portion and thin ends. The middle end of the top of the reactor body (3) is connected to a feed port. The surface of the scraper frame (10) contacts the inner wall of the reactor body (3). The middle portion of the rotating drum (9) is disconnected, and the support rod (18) is located between the two rotating drums (9).

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