Low-heat polyurethane material for reinforcing coal mine and preparation method thereof

Abstract

The application relates to a low-heat-releasing polyurethane material for coal mine reinforcement and a preparation method thereof, and belongs to the technical field of polyurethane materials and applications. The low-heat-releasing polyurethane material for coal mine reinforcement is prepared by reacting an aliphatic amine compound with salicylic acid, a bisphenol compound is prepared to replace a traditional polymer polyol, the generation of reaction heat is reduced from the reaction mechanism, and the flame-retardant performance of the material is effectively improved. Then, the prepared bisphenol compound, polyether polyol, flame retardant, plasticizer and catalyst are respectively weighed according to formula amounts and uniformly mixed to prepare an A component; isocyanate and a flame retardant are uniformly mixed according to formula amounts to prepare a B component. The components synergistically act, the consolidation body keeps high closed porosity and high sealing performance, the heat release of the reaction is reduced, the temperature of the core of the consolidation body is reduced, and the safety during use in the coal mine is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of coal mine reinforcement with low exothermic polyurethane material and its preparation method, belong to polyurethane material and its application technical field. BACKGROUND

[0002] At present, the main coal mine reinforcement methods in China are cement mortar reinforcement and polyurethane foam material reinforcement. Cement mortar reinforcement process adopts sectional sealing. Since cement is prone to form gas passage, it leads to serious air leakage, high labor intensity and long pre-drainage time, thereby reducing production and processing efficiency. Polyurethane foam material reinforcement utilizes the self-foaming pressure of polyurethane material to make the material penetrate into the borehole coal wall fracture, forming a closed-cell material, and thus improving the reinforcement quality. Polyurethane material has the advantages of small dosage, low labor intensity, good sealing effect, etc., making it widely used in coal mine reinforcement.

[0003] Conventional polyurethane reinforcement grouting material generates a large amount of reaction heat during the curing process. Since polyurethane itself has poor thermal conductivity, the heat cannot be dissipated in time, causing the internal temperature of the consolidated body to continue to rise, and in extreme cases, there is a safety hazard of smoke and even fire. With the improvement of coal mine enterprises, higher requirements are put forward for the maximum reaction temperature and flame retardant performance of the grouting material.

[0004] Therefore, a coal mine reinforcement low exothermic polyurethane material and its preparation method that can reduce the generation of reaction heat and effectively improve the flame retardant performance of the material are urgently needed to be developed. SUMMARY

[0005] The present application aims to overcome the defects of the prior art polyurethane reinforcement grouting material that generates a large amount of reaction heat during the curing process, which poses a safety hazard. The present application prepares a bisphenol compound by reacting aliphatic amine compounds with salicylic acid to replace traditional polymer polyols, thereby reducing the generation of reaction heat from the reaction mechanism and effectively improving the flame retardant performance of the material, greatly improving the safety of its use in coal mines. The second invention of the present application aims to improve the reaction kettle equipment involved in the preparation of bisphenol compounds in the improved process, which can integrate mixing, heating, insulation, water extraction and vacuum dehydration functions in one, especially suitable for the preparation method of the bisphenol compound described in the present application, which can further improve production efficiency.

[0006] To achieve the purpose of the invention, the technical solution adopted by the present application is:

[0007] A coal mine reinforcement low exothermic polyurethane material is prepared by uniformly mixing A component and B component in a volume ratio of 1:1 after reaction and curing, wherein the A component is composed of the following mass fractions of raw materials:

[0008] Bisphenol compound 30-90 parts;

[0009] Polyether polyol 10-70 parts;

[0010] Flame retardant 10-30 parts;

[0011] Plasticizer 5-20 parts;

[0012] Catalyst 0.3-2 parts;

[0013] The B component is composed of the following mass parts of raw materials:

[0014] Isocyanate 60-80 parts;

[0015] Flame retardant 20-40 parts.

[0016] Preferably, the bisphenol compound is prepared by reacting salicylic acid with an aliphatic amine compound, and the aliphatic amine compound is one of butanediamine, hexanediamine, diethylenetriamine, and triethylenetetramine.

[0017] Preferably, the polyether polyol is one or more of MN-450, MN-500, MN-700, and MN-1000.

[0018] Preferably, the flame retardant is one or more of TCEP, TCPP, and TDCPP.

[0019] Preferably, the plasticizer is one or more of DOP, DBP, and DMP.

[0020] Preferably, the catalyst is dibutyltin dilaurate (T-12).

[0021] Preferably, the flame retardant is one or more of TCEP, TCPP, and TDCPP.

[0022] Preferably, the isocyanate is Wanhua Chemical PM200.

[0023] Another object of the present application is to provide a preparation method of the low-heat-release polyurethane material for coal mine reinforcement.

[0024] A: Bisphenol compound is prepared, and the prepared bisphenol compound is mixed with polyether polyol, flame retardant, plasticizer, and catalyst according to the formula amount to prepare component A;

[0025] B: Isocyanate and flame retardant are weighed according to the formula amount and mixed uniformly to prepare component B;

[0026] C: Components A and B are mixed uniformly according to a volume ratio of 1:1, and then reacted and solidified to prepare the low-heat-release polyurethane material for coal mine reinforcement.

[0027] The method for preparing the bisphenol compound comprises the following steps:

[0028] S1: A formula amount of aliphatic amine compound is added into a reaction kettle according to a certain ratio, stirred at a temperature of 30-50°C and a rotation speed of 100 rpm, and prepared for use;

[0029] S2: A formula amount of salicylic acid is added into the reaction kettle in small amounts for multiple times to start the reaction with the aliphatic amine compound prepared in step S1, and the molar ratio of salicylic acid to aliphatic amine compound is controlled to be between 1.7-2;

[0030] S3: After the salicylic acid is added completely, a vacuum pump is started and heated to 60-90°C, the pressure in the reaction kettle is reduced to extract the generated water for dehydration, and the reaction is kept until the reaction is completed;

[0031] S4: After the reaction is completed, the vacuum dehydration is continued until the moisture content is less than 0.2% after sampling and testing, and the bisphenol compound is obtained.

[0032] The synthesis route is as follows:

[0033] (1) Reaction of salicylic acid and butanediamine:

[0034] ;

[0035] (2) Reaction of salicylic acid and hexanediamine:

[0036] ;

[0037] (3) Reaction of salicylic acid and diethylenetriamine:

[0038] ;

[0039] (4) Reaction of salicylic acid and triethylenetetramine:

[0040] .

[0041] Preferably, the reactor includes a reactor body with a top cover fixedly connected at the top end by bolts, a support frame for supporting the reactor body is sleeved on the outer side of the reactor body, a feeding port is formed in the outer wall of the top cover, and a discharge port is formed in the bottom end of the reactor body; a spiral inductive coil is arranged in the reactor body, and a heat conduction plate for heat conduction is mounted on the inner wall of the reactor body; a stirring mechanism is vertically arranged in the reactor body and on the top cover, and the stirring mechanism is used for efficiently stirring the material; a water suction pipe is mounted on the outer wall of the reactor body, a water suction port is formed in the inner wall of the reactor body and communicates with the inner cavity of the water suction pipe, and a filter screen is mounted in the water suction port; the end of the water suction pipe away from the reactor body is connected with the output end of a vacuum pump; electric valves are mounted in the water suction port and the discharge port, and the electric valves and the inductive coil are electrically connected with an external controller through wires;

[0042] The stirring mechanism includes a material uniformizing assembly, a speed reduction assembly, and a stirring assembly; the material uniformizing assembly is vertically arranged on the top cover and is used for uniformly distributing the material in the reactor body; the stirring assembly is arranged below the material uniformizing assembly and is used for fully stirring the material; and the speed reduction assembly is arranged between the material uniformizing assembly and the stirring assembly and is used for reducing the rotating speed of the material uniformizing assembly.

[0043] The material uniformizing assembly includes a motor mounted at the top end of the top cover, an uniformizing disc fixedly connected with the output end of the motor through a connecting shaft, and a screening ring mounted at the top end of the uniformizing disc; the top end outer wall of the uniformizing disc is in the shape of a circular truncated cone, and a plurality of screen holes are circumferentially formed in the screening ring.

[0044] Preferably, the speed reduction assembly includes a first gear fixedly connected at the bottom end of the uniformizing disc through a connecting shaft, a plurality of second gears equidistantly meshingly connected with the outer wall of the first gear, a support sleeve fixedly connected with the outer wall of the second gear and the connecting shaft in the reactor body, and a plurality of rolling balls equidistantly arranged at the bottom end of the second gear and in contact with the inner wall of the support sleeve.

[0045] Preferably, the stirring assembly includes a second connecting frame rotatably connected at the bottom end of the plurality of second gears through a rotating shaft, a spiral feeding rod fixedly connected with the bottom end of the second connecting frame, a first connecting frame fixedly connected with the bottom end of the spiral feeding rod, a plurality of lifting guide rods equidistantly arranged on the outer side of the spiral feeding rod, the plurality of lifting guide rods being fixedly connected with the first connecting frame and the second connecting frame, a lifting sleeve ring sleeved on the outer wall of the lifting guide rod, a moving slide rod formed on the outer wall of the lifting sleeve ring, a moving scraper formed at one end of the moving slide rod close to the heat conduction plate, and a crescent pin rotatably connected with the other end of the moving scraper away from the moving slide rod through a rotating shaft.

[0046] Preferably, the inner wall of the support sleeve is shaped with tooth blocks that are in mesh with a plurality of second gears, the top end of the second gears is shaped with a limiting slider, and an annular groove is formed in the support sleeve for the limiting slider to slide.

[0047] Preferably, the outer wall of the lifting guide rod is symmetrically provided with two straight guide grooves, the inner wall of the lifting sleeve ring is shaped with a moving slider that is in mutual conformity with the inner wall of the straight guide groove, and the inner wall of the heat-conducting plate is provided with a reciprocating screw groove for the crescent pin to slide.

[0048] Compared with the prior art, the present application has the following beneficial effects:

[0049] 1. The preparation method of the low-heat-release polyurethane material for coal mine reinforcement of the present application, by reacting aliphatic amine compounds with salicylic acid, a bisphenol compound is prepared to replace the traditional polymer polyol, the generation of reaction heat is reduced from the reaction mechanism, and the flame retardant performance of the material is also effectively improved, greatly improving the safety when used in coal mines.

[0050] 2. The low-heat-release polyurethane material for coal mine reinforcement of the present application, the prepared bisphenol compound, polyether polyol, flame retardant, plasticizer, and catalyst are weighed according to the formula amount and uniformly mixed to prepare component A; isocyanate and flame retardant are weighed according to the formula amount and uniformly mixed to prepare component B. The synergistic effect of each component reduces the heat release of the reaction and lowers the temperature of the core of the consolidated body while maintaining high closed porosity and high sealing performance.

[0051] 3. The present application improves the reaction kettle equipment involved in the step of preparing the bisphenol compound in the improved process, which can integrate the functions of mixing, heating, heat preservation, water extraction, and vacuum dehydration, and is especially suitable for the preparation method of the bisphenol compound described in the present application, which can further improve the production efficiency. By setting a stirring mechanism in the reaction kettle, starting the motor to drive the uniform material disc to rotate, the first gear and the screening ring are driven to rotate under the driving of the uniform material disc, and at the same time, the first gear is driven by the uniform material disc through the second gear, the support sleeve, and the ball, which drives the stirring assembly to perform stirring operation. At this time, the above-mentioned parts can reduce the rotational speed of the uniform material disc to the stirring assembly, and at the same time, the stirring assembly can avoid the accumulation of powder in the bottom of the reaction kettle during stirring. After a period of reaction, the material as a water-containing mixture can be lifted and conveyed to the upper part by the spiral feeding rod and then dropped, so as to improve the mixing efficiency and reaction degree. BRIEF DESCRIPTION OF DRAWINGS

[0052] Figure 1 The structure of the present application is shown in the figure;

[0053] Figure 2 It is the cross section structure schematic diagram of the reaction kettle body of the application;

[0054] Figure 3 It is the cross section structure schematic diagram of the material uniformizing disc of the application;

[0055] Figure 4 It is the structure schematic diagram of the stirring assembly of the application;

[0056] Figure 5 It is the cross section structure schematic diagram of the support sleeve frame of the application;

[0057] Figure 6 It is the schematic diagram of the reciprocating screw structure of the application;

[0058] Figure 7 It is the schematic diagram of the local enlargement structure at A in the application; Figure 2

[0059] In the figure: 1, reaction kettle body; 2, stirring mechanism; 201, motor; 202, material uniformizing disc; 203, material screening ring; 204, support sleeve frame; 205, first gear; 206, second gear; 207, ball bearing; 208, lifting guide rod; 209, first connecting frame; 2010, spiral feeding rod; 2011, second connecting frame; 2012, moving scraper; 2013, moving slide rod; 2014, crescent pin; 2015, lifting sleeve ring; 3, top cover; 4, feeding port; 5, inductance coil; 6, support frame; 7, heat conducting plate; 8, water pumping pipe. DETAILED DESCRIPTION

[0060] The application will be further described below in combination with examples, and the following examples are used to illustrate the application, but cannot be used to limit the protection scope of the application. The conditions in the examples can be further adjusted according to specific conditions, and simple improvements of the method of the application under the concept of the application all belong to the protection scope of the application. Example 1

[0061] Preparation of bisphenol compound:

[0062] 149.9 kg of butanediamine was added into the reaction kettle, and stirred at a temperature of 30℃ and a rotation speed of 100 rpm, ready for use; 138.1 kg of salicylic acid was added into the reaction kettle in small quantities for multiple times to start the reaction with butanediamine; after the addition of salicylic acid was completed, the vacuum pump was started and the temperature was increased to 60℃, the pressure in the reaction kettle was reduced to pump out the water generated for dehydration, and the reaction was kept until the reaction was completed; after the reaction was completed, the vacuum dehydration was continued until the moisture content was less than 0.2% after sampling test, which was qualified, and the bisphenol compound was obtained. The synthesis route is as follows:

[0063] ​

[0064] Please refer to Figures 1-7 In the embodiment of the present application, the reaction involves a reaction kettle, which comprises a reaction kettle body 1 with a top cover 3 fixedly connected at the top end by bolts, a support frame 6 sleeved on the outer side of the reaction kettle body 1 for supporting the reaction kettle body 1, a feed inlet 4 formed in the outer wall of the top cover 3, a spiral inductor coil 5 arranged inside the reaction kettle body 1, a heat conduction plate 7 mounted on the inner wall of the reaction kettle body 1 for heat conduction, a water suction pipe 8 mounted on the outer wall of the reaction kettle body 1, a water suction port formed in the inner wall of the reaction kettle body 1 and communicating with the inner cavity of the water suction pipe 8, a filter screen mounted inside the water suction port, the end of the water suction pipe 8 away from the reaction kettle body 1 connected with the output end of a vacuum pump, a discharge port formed in the bottom end of the reaction kettle body 1, an electric valve mounted inside the water suction port and the discharge port, the electric valve and the inductor coil 5 electrically connected with an external controller through wires, and a stirring mechanism 2 vertically arranged on the reaction kettle body 1 and the top cover 3, which is used for efficiently stirring the powder.

[0065] The stirring mechanism 2 comprises a uniform material assembly, a speed reduction assembly and a stirring assembly, the uniform material assembly is vertically arranged on the top cover 3 and is used for uniformly distributing the powder inside the reaction kettle body 1, the stirring assembly is arranged below the uniform material assembly and is used for fully stirring the powder, and the speed reduction assembly is arranged between the uniform material assembly and the stirring assembly and is used for reducing the rotating speed of the uniform material assembly transmitted to the stirring assembly.

[0066] The uniform material assembly comprises a motor 201 mounted at the top end of the top cover 3, a uniform material disc 202 fixedly connected with the output end of the motor 201 through a connecting shaft, and a screening ring 203 mounted at the top end of the uniform material disc 202.

[0067] In the embodiment, when the device is used, the motor 201 is started to drive the uniform material disc 202 to rotate, at this time, the screening ring 203 rotates under the drive of the uniform material disc 202, and at the same time, the speed reduction assembly drives the stirring assembly to move under the transmission of the uniform material disc 202, at this time, the rotating speed of the uniform material disc 202 transmitted to the stirring assembly can be reduced through the speed reduction assembly.

[0068] The powder can be efficiently stirred by the stirring assembly during stirring, so as to avoid uneven stirring of the powder, the inductor coil 5 is started to heat by the external controller at this time, the inductor coil 5 can gradually increase the ambient temperature inside the reaction kettle body 1 through the heat conduction plate 7, and a temperature sensor can be arranged inside the reaction kettle body 1 to monitor the internal temperature in real time.

[0069] When the temperature in the reaction kettle body 1 rises to between 30-50℃, the formula amount of amine compound amine is added to the reaction kettle body 1 through the feed port 4, in this process, the powder first contacts the upper surface of the uniformizing disc 202, at this time the powder is dispersed under the rotation guidance of the circular truncated cone outer wall of the uniformizing disc 202, and at the same time the powder is uniformly distributed in the inside of the reaction kettle body 1 under the screening of the screening ring 203, so as to sufficiently preheat and warm the amine compound amine; then the formula amount of salicylic acid is added to the reaction kettle body 1 through the feed port 4 in small amounts and multiple times to start the reaction with the amine compound, and the molar ratio of salicylic acid and amine compound is controlled between 1.7-2.

[0070] When the salicylic acid is added, the inductive coil 5 is continuously heated by the external controller, so as to raise the temperature in the inside of the reaction kettle body 1 to 60-90℃, then the electric valve is opened by the external controller, and the vacuum pump is started to reduce the pressure in the reaction kettle body 1 through the water suction pipe 8, and the water generated in the reaction is sucked outwards, so as to realize the dehydration operation of the reactants in the reaction process, and the temperature in the inside of the reaction kettle body 1 is maintained by the inductive coil 5, so as to realize the heat preservation operation, until the reactants are completely reacted, the residual water in the inside of the reaction kettle body 1 is continuously dehydrated by the vacuum pump, until the moisture content is less than 0.2% after sampling and testing, the bisphenol compound is prepared, then the electric valve is opened by the external controller, and then the bisphenol compound is discharged outwards through the discharge port, so as to realize the reaction operation of the reaction kettle to the powder.

[0071] As a preferred embodiment of the present application, the speed reduction assembly comprises: a first gear 205 fixedly connected to the bottom end of the uniformizing disc 202 through a connecting shaft, a plurality of second gears 206 are equidistantly meshed and connected to the outer wall of the first gear 205, a support sleeve frame 204 is fixedly connected to the outer wall of the second gear 206 and the connecting shaft in the inside of the reaction kettle body 1, and a plurality of rolling balls 207 are equidistantly arranged at the bottom end of the second gear 206 and in contact with the inner wall of the support sleeve frame 204.

[0072] The stirring assembly comprises a second connecting frame 2011 rotatably connected to the bottom end of the plurality of second gears 206 through a rotating shaft, a spiral feeding rod 2010 fixedly connected to the bottom end of the second connecting frame 2011, a first connecting frame 209 fixedly connected to the bottom end of the spiral feeding rod 2010, a plurality of lifting guide rods 208 circumferentially and equidistantly arranged on the outer side of the spiral feeding rod 2010, the plurality of lifting guide rods 208 being fixedly connected to the first connecting frame 209 and the second connecting frame 2011, a lifting sleeve ring 2015 sleeved on the outer wall of the lifting guide rod 208, a moving slide rod 2013 formed on the outer wall of the lifting sleeve ring 2015, a moving scraper 2012 formed on one end of the moving slide rod 2013 close to the heat conduction plate 7, a crescent pin 2014 rotatably connected to the other end of the moving scraper 2012 away from the moving slide rod 2013 through a rotating shaft, a tooth block formed on the inner wall of the support sleeve frame 204 and meshing with the plurality of second gears 206, a limiting slide block formed on the top end of the second gear 206, an annular groove formed on the support sleeve frame 204 for the limiting slide block to slide, two straight guide grooves symmetrically formed on the outer wall of the lifting guide rod 208, a moving slide block formed on the inner wall of the lifting sleeve ring 2015 and matching with the inner wall of the straight guide groove, a reciprocating screw groove formed on the inner wall of the heat conduction plate 7 for the crescent pin 2014 to slide, and the outer wall of the moving scraper 2012 matching with the inner wall of the heat conduction plate 7.

[0073] In the embodiment, the first gear 205 rotates under the driving of the uniform material disc 202, and the plurality of second gears 206 are driven by the first gear 205 (the meshing transmission ratio of the first gear 205 and the second gear 206 is greater than 1) and are displaced in the interior of the support sleeve frame 204 through the meshing with the tooth block on the inner wall of the support sleeve frame 204. Meanwhile, the second connecting frame 2011 is driven by the plurality of second gears 206 through the rotating shaft to drive the first connecting frame 209 to rotate through the plurality of lifting guide rods 208. At this time, the spiral feeding rod 2010 is synchronously rotated under the driving of the second connecting frame 2011 and the first connecting frame 209, so that the powder can be prevented from being accumulated at the bottom of the reaction kettle main body 1 during stirring. After a period of reaction, the material as a water-containing mixture can be lifted from the bottom to the upper portion and then falls again by the spiral feeding rod 2010. Such a process is repeated to improve the mixing efficiency and the degree of reaction.

[0074] Meanwhile, the lifting sleeve ring 2015 is driven by the lifting guide rod 208 to drive the moving scraper 2012 to move through the moving slide rod 2013. At this time, the moving scraper 2012 is driven by the moving slide rod 2013 to move along the outer wall of the lifting guide rod 208 under the guidance of the reciprocating screw groove in the inner wall of the heat conduction plate 7 through the crescent pin 2014. At this time, the lifting sleeve ring 2015 is driven by the moving slide block to ascend and descend along the outer wall of the lifting guide rod 208 under the guidance of the straight guide groove of the lifting guide rod 208, so that the powder can be efficiently stirred during stirring and the uneven stirring of the powder can be avoided.

[0075] As a preferred embodiment of the present application, the top end outer wall of the uniformizing disc 202 is in the shape of a circular truncated cone, and a plurality of screen holes are formed in the screen ring 203 in the circumferential direction.

[0076] In this embodiment: through the outer wall in the shape of a circular truncated cone and the plurality of screen holes in the screen ring 203, the powder can be uniformly distributed in the inside of the reaction kettle main body 1 under the rotation of the uniformizing disc 202 and the rotation and screening of the screen ring 203, so as to facilitate uniform stirring of the powder.

[0077] The working principle of the reaction kettle is: when the device is used, the motor 201 drives the uniformizing disc 202 to rotate, at this time, the screen ring 203 and the first gear 205 rotate synchronously under the driving of the uniformizing disc 202, at the same time, the plurality of second gears 206 are driven by the meshing of the first gear 205, and through the meshing with the tooth blocks in the inner wall of the support sleeve frame 204, they displace in the inside of the support sleeve frame 204, at the same time, the second connecting frame 2011 is driven by the plurality of second gears 206 through the rotating shaft, and drives the first connecting frame 209 to rotate through the plurality of lifting guide rods 208, at this time, the screw feeding rod 2010 rotates synchronously under the driving of the second connecting frame 2011 and the first connecting frame 209, which can avoid the accumulation of powder to the bottom of the reaction kettle main body 1 during stirring.

[0078] At the same time, the lifting sleeve ring 2015 is driven by the lifting guide rod 208 to move the moving scraper 2012 through the moving slide rod 2013, at this time, the moving scraper 2012 moves along the outer wall of the lifting guide rod 208 under the guidance of the reciprocating screw thread in the inner wall of the heat conducting plate 7 through the crescent pin 2014 driving the lifting sleeve ring 2015 through the moving slide rod 2013, at this time, the lifting sleeve ring 2015 moves along the outer wall of the lifting guide rod 208 under the guidance of the linear guide groove of the lifting guide rod 208 through the moving slide block, so as to facilitate efficient stirring of the powder during stirring and avoid uneven stirring of the powder.

[0079] At the same time, the inductor coil 5 is started by the external controller to heat, at this time, the inductor coil 5 can gradually heat the temperature environment in the inside of the reaction kettle main body 1 through the heat conducting plate 7, it needs to be particularly pointed out that the amine compound is one of butanediamine, hexanediamine, diethylenetriamine and triethylenetetramine, and all are powder.

[0080] When the temperature inside the reaction kettle main body 1 rises to between 30-50℃, the formula amount of amine compound amine is added to the reaction kettle main body 1 through the feed port 4 at this time, in this process, the powder first contacts the upper surface of the uniformizing disc 202, at this time the powder is dispersed under the rotation guidance of the circular truncated cone outer wall of the uniformizing disc 202, and at the same time the powder is uniformly distributed in the inside of the reaction kettle main body 1 under the screening of the screening ring 203, and first performs the heating residual heat; then the formula amount of salicylic acid is added to the reaction kettle main body 1 through the feed port 4 in small amounts and multiple times to start the reaction with the amine compound, and the molar ratio of salicylic acid and amine compound is controlled between 1.7-2.

[0081] When the salicylic acid is added, the inductive coil 5 is continuously heated by the external controller to raise the temperature inside the reaction kettle main body 1 to 60-90℃, then the electric valve is opened by the external controller, and the vacuum pump is started to reduce the pressure inside the reaction kettle main body 1 through the water suction pipe 8, and the water produced by the reaction is sucked outwards, so as to realize the dehydration operation of the reactants in the reaction process. The depth of the water suction pipe 8 inserted into the inside of the reaction kettle main body 1 is adjustable, and for the convenience of observation, a transparent observation window can be longitudinally opened on the side wall of the reaction kettle main body 1, and the insertion depth of the water suction pipe 8 is adjusted by observing the water height. The temperature inside the reaction kettle main body 1 is maintained by the inductive coil 5 to realize the heat preservation operation, until the reactants are completely reacted, the residual water in the inside of the reaction kettle main body 1 is continuously vacuum dehydrated by the vacuum pump, until the moisture content is less than 0.2% after sampling and testing, the double phenolic compound is prepared, then the electric valve is opened by the external controller, and then the double phenolic compound is discharged outwards through the discharge port. Example 2

[0082] Preparation of double phenolic compound:

[0083] 209.2 kg of hexanediamine is added to the reaction kettle, stirred at 100 rpm under the temperature environment of 40℃, and standby; 138.1 kg of salicylic acid is added to the reaction kettle in small amounts and multiple times to start the reaction with butanediamine; after the salicylic acid is added, the vacuum pump is started and the temperature is raised to 70℃, the pressure in the reaction kettle is reduced to remove the water produced by dehydration, and the reaction is kept warm until the reaction is complete; after the reaction is completed, continue to vacuum dehydrate until the moisture content is less than 0.2% after sampling and testing, the double phenolic compound is obtained. The synthesis route is as follows:

[0084]

[0085] The remaining preparation method, equipment structure and operation mode of this example are the same as those of example 1, which will not be repeated. Example 3

[0086] Preparation of double phenolic compound:

[0087] Put 196.0 kg of diethylene triamine into the reaction kettle, stirring at 100 rpm under the temperature environment of 40℃, ready for use; add 138.1 kg of salicylic acid into the reaction kettle in small quantities for starting reaction with butanediamine; after the addition of salicylic acid is completed, start the vacuum pump and heat to 80℃, reduce the pressure in the reaction kettle to extract the generated water for dehydration, and keep the temperature for reaction until the reaction is complete; after the reaction is completed, continue to dehydrate under vacuum until the moisture content is less than 0.2% after sampling and testing, and the said bisphenol compound is obtained. The synthesis route is as follows:

[0088]

[0089] The remaining preparation method, equipment structure and operation mode of this embodiment are the same as those of Example 1, and will not be repeated. Example 4

[0090] Preparation of bisphenol compound:

[0091] Put 292.5 kg of triethylene tetramine into the reaction kettle, stirring at 100 rpm under the temperature environment of 50℃, ready for use; add 138.1 kg of salicylic acid into the reaction kettle in small quantities for starting reaction with butanediamine; after the addition of salicylic acid is completed, start the vacuum pump and heat to 90℃, reduce the pressure in the reaction kettle to extract the generated water for dehydration, and keep the temperature for reaction until the reaction is complete; after the reaction is completed, continue to dehydrate under vacuum until the moisture content is less than 0.2% after sampling and testing, and the said bisphenol compound is obtained. The synthesis route is as follows:

[0092]

[0093] The remaining preparation method, equipment structure and operation mode of this embodiment are the same as those of Example 1, and will not be repeated. Example 5

[0094] Take 400 kg of bisphenol compound prepared in Example 1, 600 kg of MN-500, 250 kg of TCPP, 100 kg of DMP, and 8 kg of T-12, mix the above raw materials evenly to prepare component A; take 700 kg of PM200 and 300 kg of TCEP, and mix them evenly to prepare component B. Mix components A and B according to the volume ratio of 1:1, and react evenly and sufficiently to prepare a low-heat polyurethane material for coal mine reinforcement, and the following properties of the material are measured, and the results are shown in Table 1.

[0095] The remaining preparation method, equipment structure and operation mode of this embodiment are the same as those of Example 1, and will not be repeated. Example 6

[0096] Take the preparation of bisphenol compounds 600 kg, MN-500 400 kg, TCPP 250 kg, DMP 100 kg, T-12 8 kg, the above raw materials are mixed uniformly, that is, the preparation of A component; take PM200 700 kg, TCEP 300 kg and mix uniformly, that is, the preparation of B component. A, B components are mixed uniformly according to the volume ratio of 1:1, and the low heat release polyurethane material for coal mine reinforcement is prepared. The material performance is measured, and the results are shown in Table 1.

[0097] The remaining preparation method and device structure and operation mode of this embodiment are the same as those of example one, and will not be described again. Example 7

[0098] Take the preparation of bisphenol compounds 600 kg, MN-500 400 kg, TCPP 250 kg, DMP 100 kg, T-12 8 kg, the above raw materials are mixed uniformly, that is, the preparation of A component; take PM200 700 kg, TCEP 300 kg and mix uniformly, that is, the preparation of B component. A, B components are mixed uniformly according to the volume ratio of 1:1, and the low heat release polyurethane material for coal mine reinforcement is prepared. The material performance is measured, and the results are shown in Table 1.

[0099] The remaining preparation method and device structure and operation mode of this embodiment are the same as those of example one, and will not be described again.

[0100] Comparative example

[0101] Take the preparation of bisphenol compounds 600 kg, MN-500 400 kg, TCPP 250 kg, DMP 100 kg, T-12 8 kg, the above raw materials are mixed uniformly, that is, the preparation of A component; take PM200 700 kg, TCEP 300 kg and mix uniformly, that is, the preparation of B component. A, B components are mixed uniformly according to the volume ratio of 1:1, and the low heat release polyurethane material for coal mine reinforcement is prepared. The material performance is measured, and the results are shown in Table 1.

[0102] Table 1: sample detection data of each example

[0103]

[0104] Although the embodiments of the present application have been shown and described, it can be understood by those skilled in the art that various changes, modifications, replacements and variations can be made to these embodiments without departing from the principles and spirits of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A low-heat exothermic polyurethane material for coal mine reinforcement, comprising a 1:1 volume ratio of component A and component B, uniformly mixed and cured by reaction, characterized in that: Component A is composed of the following raw materials in parts by mass: 30-90 parts of phenolic compounds; 10-70 parts of polyether polyol; 10-30 parts flame retardant; Plasticizer 5-20 parts; Catalyst 0.3-2 parts; Component B is composed of the following raw materials in parts by mass: 60-80 parts isocyanate; 20-40 parts flame retardant; The phenolic compounds are prepared by reacting salicylic acid with aliphatic amine compounds, wherein the molar ratio of salicylic acid to aliphatic amine compounds is 1:1.7-2. The aliphatic amine compound is any one of butanediamine, hexanediamine, diethylenetriamine, and triethylenetetramine.

2. The low-heat-exothermic polyurethane material for coal mine reinforcement according to claim 1, characterized in that: The polyether polyol is one or more of MN-450, MN-500, MN-700, and MN-1000; the flame retardant is one or more of TCEP, TCPP, and TDCPP; the plasticizer is one or more of DOP, DBP, and DMP; the catalyst is dibutyltin dilaurate; and the isocyanate is Wanhua Chemical PM200.

3. The method for preparing a low-heat exothermic polyurethane material for coal mine reinforcement according to claim 1, characterized in that... Includes the following steps: A: To prepare phenolic compounds, weigh and mix the prepared phenolic compounds with polyether polyols, flame retardants, plasticizers, and catalysts according to the formula and mix them evenly to prepare component A. B: Weigh the isocyanate and flame retardant according to the formula amount and mix them evenly to prepare component B; C: After mixing components A and B in a volume ratio of 1:1, reacting and curing, the low-heat polyurethane material for coal mine reinforcement is obtained.

4. The method for preparing a low-heat exothermic polyurethane material for coal mine reinforcement according to claim 3, characterized in that... The method for preparing phenolic compounds described in step A includes the following steps: S1: Add the aliphatic amine compound in a certain proportion to the reaction vessel, stir at 100 rpm in a temperature environment of 30-50℃, and set aside; S2: The specified amount of salicylic acid is gradually added to the reaction vessel to begin the reaction with aliphatic amine compounds. The molar ratio of salicylic acid to aliphatic amine compounds is 1:1.7-2. S3: After the salicylic acid has been added, turn on the vacuum pump and heat to 60-90℃. Reduce the pressure in the reactor to extract the water produced for dehydration, and keep the reaction at the temperature until the reaction is complete. S4: After the reaction is complete, continue vacuum dehydration until the moisture content of the sample is less than 0.2% and passes the test, then the phenolic compound is obtained.

5. The method for preparing a low-heat exothermic polyurethane material for coal mine reinforcement according to claim 4, characterized in that: The reactor includes a reactor body (1) with a top cover (3) fixedly connected to its top end by bolts. A support frame (6) for supporting the reactor body (1) is sleeved on the outside of the reactor body (1). A feed inlet (4) is opened on the outer wall of the top cover (3), and a discharge outlet is opened at the bottom end of the reactor body (1). A spiral inductor coil (5) is installed inside the reactor body (1), and a heat-conducting plate (7) for conducting heat is installed on the inner wall of the reactor body (1). A vertical inductor coil (5) is installed inside the reactor body (1) and on the top cover (3). A stirring mechanism (2) is provided, which is used to stir the material efficiently; a water pumping pipe (8) is installed on the outer wall of the reactor body (1), and a water pumping port is opened on the inner wall of the reactor body (1) to communicate with the inner cavity of the water pumping pipe (8). A filter screen is installed inside the water pumping port; the end of the water pumping pipe (8) away from the reactor body (1) is connected to the output end of the vacuum pump; electric valves are installed inside the water pumping port and the discharge port, and the electric valves and the inductor coil (5) are electrically connected to an external controller through wires; The stirring mechanism (2) includes: a uniform material assembly, a deceleration assembly, and a stirring assembly; the uniform material assembly is vertically arranged on the top cover (3) for uniformly distributing the material inside the reactor body (1); the stirring assembly is arranged below the uniform material assembly for fully stirring the material; the deceleration assembly is arranged between the uniform material assembly and the stirring assembly for reducing the rotational speed of the uniform material assembly to the stirring assembly. The material leveling assembly includes: a motor (201) installed on the top of the top cover (3), the output end of the motor (201) is fixedly connected to a material leveling disk (202) via a connecting shaft, and a sieve ring (203) is installed on the top of the material leveling disk (202); the outer wall of the top of the material leveling disk (202) is frustum-shaped, and the sieve ring (203) has multiple sieve holes circumferentially.

6. The method for preparing low-heat exothermic polyurethane material for coal mine reinforcement according to claim 5, characterized in that, The deceleration component includes: A first gear (205) is fixedly connected to the bottom of the uniform feed plate (202) via a connecting shaft. Multiple second gears (206) are circumferentially meshed on the outer wall of the first gear (205). A support sleeve (204) is fixedly connected inside the reactor body (1) and sleeved on the outer wall of the second gear (206) and the connecting shaft. Multiple balls (207) that contact the inner wall of the support sleeve (204) are circumferentially equidistantly arranged at the bottom of the second gear (206).

7. The method for preparing low-heat exothermic polyurethane material for coal mine reinforcement according to claim 6, characterized in that, The stirring assembly includes: A second connecting frame (2011) is rotatably connected to the bottom of multiple second gears (206) via a rotating shaft. A spiral feeding rod (2010) is fixedly connected to the bottom of the second connecting frame (2011). A first connecting frame (209) is fixedly connected to the bottom of the spiral feeding rod (2010). Multiple lifting guide rods (208) are equidistantly arranged on the outer circumference of the spiral feeding rod (2010). All of the multiple lifting guide rods (208) are connected to the first connecting frame (209). The second connecting frame (2011) is fixedly connected. The outer wall of the lifting guide rod (208) is fitted with a lifting collar (2015). The outer wall of the lifting collar (2015) is formed with a movable slide rod (2013). The end of the movable slide rod (2013) near the heat-conducting plate (7) is formed with a movable scraper (2012). The end of the movable scraper (2012) away from the movable slide rod (2013) is rotatably connected with a crescent pin (2014) through a rotating shaft.

8. The method for preparing low-heat exothermic polyurethane material for coal mine reinforcement according to claim 7, characterized in that, The inner wall of the support sleeve (204) is formed with tooth blocks that mesh with a plurality of second gears (206). The top of the second gear (206) is formed with a limiting slider. The support sleeve (204) is provided with an annular groove for the limiting slider to slide.

9. The method for preparing low-heat exothermic polyurethane material for coal mine reinforcement according to claim 8, characterized in that, The outer wall of the lifting guide rod (208) is symmetrically provided with two straight guide grooves. The inner wall of the lifting collar (2015) is formed with a movable slider that matches the inner wall of the straight guide groove. The inner wall of the heat-conducting plate (7) is provided with a reciprocating threaded groove for the crescent pin (2014) to slide. The outer wall of the movable scraper (2012) matches the inner wall of the heat-conducting plate (7).

Images