An experimental device and experimental method for wet granulation of solvent-based supramolecular polyurethane urea

Abstract

The present invention relates to an experimental device and experimental method for wet granulation of solvent-based supramolecular polyurethane urea, and belongs to the field of new material technology. The device includes a solvent polymerization reaction device, a liquid feed conveying device, a spray curing device, a separation device, a drying device and a screening and collecting device. The solvent polymerization reaction device, the liquid feed conveying device, the spray curing device and the separation device are connected in sequence, and a drying device and a screening and collecting device are sequentially arranged on the upper side of the separation device. The spray curing device includes a spray device and a curing device, a curing device is arranged below the spray device, and the curing device is connected to the separation device. The separation device includes a filtration system and a curing agent recovery system, and the filtration system is connected to the curing agent recovery system. By adjusting the parameters, the particle size and shape can be accurately controlled, high-temperature operation can be avoided, environmental pollution can be reduced, the consistency and mechanical properties of the product can be significantly improved, and production efficiency can be improved.

Description

Technical Field

[0001] The invention relates to an experimental device and an experimental method for wet granulation of solvent-based supramolecular polyurethane urea, belonging to the technical field of new materials. Background Art

[0002] Supramolecular polyurethane urea (SUPUR) is a class of polyurethane materials constructed through supramolecular chemistry. They exhibit excellent mechanical properties, chemical stability, and thermal stability. The unique structure of SUPUR enables them to excel in a variety of applications, such as coatings, adhesives, elastomers, and biomedical materials.

[0003] At present, traditional dry granulation technology is widely used in the production of various granular materials, but it has some significant defects. First, the dry granulation process easily generates a large amount of dust, causing environmental pollution and increasing the health risks of workers. In addition, it is difficult to accurately control the size and shape of the particles in dry granulation, resulting in poor product consistency. These shortcomings limit the application of dry granulation in industrial fields with high precision requirements. Melt granulation is another traditional granulation method, which is mainly suitable for thermoplastic materials. This method manufactures particles by heating the material to a molten state and then cooling and forming it. Although melt granulation can produce uniform particles, it requires high-temperature operation, high energy consumption, and high equipment requirements. In addition, some polyurethane ureas are prone to degradation at high temperatures, resulting in decreased product performance. Therefore, melt granulation is not suitable for all types of polyurethane materials. Summary of the Invention

[0004] In response to the shortcomings of the existing technology, the present invention provides an experimental device and experimental method for the wet granulation of solvent-based supramolecular polyurethane urea, which can accurately control the size and shape of particles, avoid high-temperature operation, reduce environmental pollution, and significantly improve the consistency and mechanical properties of the product. In addition, the process is highly adjustable. By changing the solvent type, temperature and other process parameters, the performance of the final product can be adjusted. At the same time, the device is suitable for large-scale industrial production and has high production efficiency.

[0005] The technical solutions of the present invention are as follows:

[0006] An experimental device for wet granulation of solvent-based supramolecular polyurethane urea comprises a solvent polymerization reaction device, a liquid feeding device, a spray curing device, a separation device, a drying device and a screening and collecting device. The solvent polymerization reaction device, the liquid feeding device, the spray curing device and the separation device are connected in sequence. A drying device and a screening and collecting device are sequentially arranged on the upper side of the separation device, wherein:

[0007] The spray curing device includes a spraying device and a curing device. A curing device is provided below the spraying device. The curing device is connected to a separation device. The separation device includes a filtration system and a curing agent recovery system. The filtration system is connected to the curing agent recovery system. The separation device is used to separate the solid particles from the curing agent and to recycle the curing agent.

[0008] The filtration system and the curing agent recovery system are existing commercially available equipment.

[0009] Preferably, according to the present invention, the injection device includes a distributed injector, a pagoda interface and an embedded nozzle. The distributed injector includes an upper plate and a lower plate. The upper center of the upper plate is connected to the pagoda interface, the lower side of the upper plate is connected to the lower plate, and the upper side of the lower plate is provided with evenly distributed water spray channels. The lower side of the lower plate corresponding to the water spray channel is provided with an embedded nozzle, and the embedded nozzle is connected to the water spray channel.

[0010] Preferably according to the present invention, the inner diameter of the embedded nozzle is 1 mm to 3 mm.

[0011] According to the preferred embodiment of the present invention, the solvent polymerization reaction device includes a temperature-controllable double-layer reactor and a feed liquid pretreatment device, the feed liquid pretreatment device includes a temperature control device, a condensation reflux device and a stirring reactor, the upper side of the temperature-controllable double-layer reactor is connected to a temperature control device and a condensation reflux device, the temperature control device model is a ZTM-50-200-30 closed refrigeration and heating circulation device, and the stirring reactor is located inside the temperature-controllable double-layer reactor.

[0012] Preferably, according to the present invention, the material liquid conveying device includes a corrosion-resistant connecting pipe, a corrosion-resistant peristaltic pump and a regulating valve. The corrosion-resistant connecting pipe is arranged between the solvent polymerization reaction device and the injection curing device. The corrosion-resistant peristaltic pump and the regulating valve are sequentially arranged on the corrosion-resistant connecting pipe. The model of the corrosion-resistant peristaltic pump is BT-100-2J.

[0013] Preferably, according to the present invention, the curing device includes a box, a motor and a stirring paddle. The motor is fixed to the ground through a side bracket. The motor is connected to the stirring paddle. The stirring paddle is arranged inside the box to disperse the liquid droplets formed by the spraying and accelerate the formation of solid particles.

[0014] According to the preferred embodiment of the present invention, the drying device is a heating plate of model ML-2-4.

[0015] According to the preferred embodiment of the present invention, the distance between the injection device and the liquid level in the curing device is set to 100 mm or 170 mm. When the distance is set to 100 mm, the obtained supramolecular polyurethane urea particles are spherical particles. When the distance is set to 170 mm, the obtained supramolecular polyurethane urea particles are cake-shaped particles with a concave center.

[0016] The experimental method of the above-mentioned solvent-based supramolecular polyurethane urea wet granulation experimental device includes the following steps:

[0017] S1. Add reaction materials and solvent into a temperature-controllable double-layer reactor, introduce nitrogen, and prepare a solvent-based supramolecular polyurethane urea solution according to the set temperature and stirring rate;

[0018] S2, heating by a temperature control device to evaporate the solvent of the solvent-based supramolecular polyurethane urea liquid and adjust the solid content;

[0019] S3. Open the regulating valve of the liquid conveying device and set the flow value of the corrosion-resistant peristaltic pump;

[0020] S4. Adjust the height of the injection device, add curing agent to the curing device, and set the stirring rate;

[0021] S5. Start the filtration system and the curing agent recovery system, set the temperature of the drying device to the experimental temperature, start the screening and collection device, screen and collect the dried supramolecular polyurethane urea particles.

[0022] Preferably, according to the present invention, the raw materials used in the temperature-controlled double-layer reactor in step S1 are diols of different molecular weights, isocyanates and supramolecular chain extenders, and the solvent is one or more of acetone, ethyl acetate, dimethyl sulfoxide, N,N-dimethylformamide and dimethylacetyl.

[0023] According to the preferred embodiment of the present invention, the heating temperature of the temperature control device in step S2 is 80°C to 100°C, the reaction time is 1h to 2h, the evaporated solvent is one or a mixed solvent of two or more of dimethylformamide, dimethylacetamide, tetrahydrofuran, dichloromethane, and butyl acetate, and the solid content of the solvent-based supramolecular polyurethane urea liquid is adjusted to 12% to 20%.

[0024] Preferably, according to the present invention, the flow rate of the corrosion-resistant peristaltic pump in step S3 is set to 30ml / min~4000ml / min, the stirring rate of the curing agent in the curing device in step S4 is 400r / min~1000r / min, and the temperature of the drying device in step S5 is set to 70℃~110℃.

[0025] The beneficial effects of the present invention are:

[0026] 1. Precise control: The present invention can precisely control the size and shape of particles by adjusting parameters such as solvent type, concentration, temperature and stirring speed, thereby producing products with high uniformity and consistency while retaining the original mechanical properties of the polyurethane urea material.

[0027] 2. Low-temperature operation: The present invention avoids high-temperature operation, reduces the degradation risk of polyurethane urea, and improves the mechanical properties and chemical resistance of the product.

[0028] 3. Environmentally friendly: The wet granulation method of the present invention reduces the generation of dust, thereby reducing environmental pollution and health risks to workers. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 Schematic diagram of the experimental device for wet granulation of solvent-based supramolecular polyurethane urea of ​​the present invention;

[0030] Figure 2 Schematic diagram of the spraying device in the spray curing device of the present invention;

[0031] Figure 3 Schematic diagram of the pagoda interface in the injection device of the present invention;

[0032] Figure 4 Schematic diagram of the upper plate in the injection device of the present invention;

[0033] Figure 5 Schematic diagram of the lower plate in the injection device of the present invention;

[0034] Figure 6 Schematic diagram of the embedded nozzle in the spray device of the present invention;

[0035] Figure 7 It is a front view of the spray curing device of the present invention;

[0036] Figure 8 A top view of the spray curing device of the present invention;

[0037] Figure 9 It is a left side view of the spray curing device of the present invention;

[0038] Figure 10 Schematic diagram of the spherical polyurethane urea low-density solid particles of the present invention, wherein: Figure 10 (a) is a scanning electron microscope image of the surface morphology of spherical polyurethane urea low-density solid particles. Figure 10 (b) is a scanning electron micrograph of a cross section of a spherical polyurethaneurea low-density solid particle;

[0039] Figure 11 This is a schematic diagram of the spherical polyurethane urea high-density solid particles of the present invention, wherein: Figure 11 (a) is a scanning electron microscope image of the surface morphology of spherical polyurethane urea high-density solid particles. Figure 11 (b) is a scanning electron micrograph of the cross section of spherical polyurethaneurea high-density solid particles;

[0040] Figure 12 This is a schematic diagram of the polyurethane urea high-density solid particles of the present invention being cake-shaped particles with a concave center, wherein: Figure 12 (a) is a scanning electron microscope image of the surface morphology of pancake-shaped polyurethane urea high-density solid particles. Figure 12(b) is a scanning electron micrograph of a cross section of a pancake-shaped polyurethane urea high-density solid particle;

[0041] Among them: 1. Temperature-controlled double-layer reactor; 2. Liquid pretreatment device; 3. Liquid conveying device; 4. Spray curing device; 5. Separation device; 6. Drying device; 7. Screening and collecting device;

[0042] 21. Stirring reactor; 22. Temperature control device; 23. Condensation reflux device;

[0043] 31. Corrosion-resistant peristaltic pump; 32. Control valve;

[0044] 41. Pagoda interface; 42. Upper plate; 43. Lower plate; 44. Embedded nozzle; 45. Curing agent; 46. Stirring paddle;

[0045] 51. Filtration system; 52. Curing agent recovery system. DETAILED DESCRIPTION

[0046] The present invention will be further described below with reference to embodiments and accompanying drawings, but is not limited thereto.

[0047] Example 1:

[0048] like Figure 1-9 As shown, this embodiment provides an experimental device for wet granulation of solvent-based supramolecular polyurethane urea, comprising a solvent polymerization reaction device, a liquid feeding device 3, a spray curing device 4, a separation device 5, a drying device 6, and a screening and collecting device 7. The solvent polymerization reaction device, the liquid feeding device 3, the spray curing device 4, and the separation device 5 are sequentially connected, and the drying device 6 and the screening and collecting device 7 are sequentially arranged on the upper side of the separation device 5, wherein:

[0049] The spray curing device 4 includes a spraying device and a curing device. A curing device is provided below the spraying device. The curing device is connected to a separation device 5. The separation device 5 includes a filtration system 51 and a curing agent recovery system 52. The filtration system 51 is connected to the curing agent recovery system 52. The separation device 5 is used to separate the solid particles from the curing agent and to recycle the curing agent.

[0050] The filtration system 51 and the curing agent recovery system 52 are existing commercially available equipment.

[0051] The injection device includes a distributed injector, a pagoda interface 41 and an embedded nozzle 44. The distributed injector includes an upper plate 42 and a lower plate 43. The upper center of the upper plate 42 is connected to the pagoda interface 41, and the lower side of the upper plate 42 is connected to the lower plate 43. The upper side of the lower plate 43 is provided with evenly distributed water spray channels, and the lower side of the lower plate 43 corresponding to the water spray channel is provided with an embedded nozzle 44, and the embedded nozzle 44 is connected to the water spray channel.

[0052] The inner diameter of the embedded nozzle 44 is 1 mm to 3 mm.

[0053] The solvent polymerization reaction device includes a temperature-controllable double-layer reactor 1 and a feed liquid pretreatment device 2. The feed liquid pretreatment device 2 includes a temperature control device 22, a condensation reflux device 23 and a stirring reactor 21. The temperature control device 22 and the condensation reflux device 23 are connected to the upper side of the temperature-controllable double-layer reactor 1. The temperature control device 22 is a ZTM-50-200-30 closed refrigeration and heating circulation device. The stirring reactor 21 is located inside the temperature-controllable double-layer reactor 1.

[0054] The liquid conveying device 3 includes a corrosion-resistant connecting pipe, a corrosion-resistant peristaltic pump 31 and a regulating valve 32. The corrosion-resistant connecting pipe is arranged between the solvent polymerization reaction device and the injection curing device 4. The corrosion-resistant peristaltic pump 31 and the regulating valve 32 are arranged on the corrosion-resistant connecting pipe in sequence. The model of the corrosion-resistant peristaltic pump 31 is BT-100-2J.

[0055] The solidification device includes a box, a motor and a stirring paddle 46. The motor is fixed to the ground through a side bracket. The motor is connected to the stirring paddle 46. The stirring paddle 46 is arranged inside the box to disperse the liquid droplets formed by the injection and accelerate the formation of solid particles.

[0056] The drying device 6 is a heating plate of model ML-2-4.

[0057] Example 2:

[0058] This embodiment provides an experimental device for wet granulation of solvent-based supramolecular polyurethane urea as described in Example 1, except that the distance between the injection device and the liquid level in the curing device is set to 100 mm or 170 mm. When the distance is set to 100 mm, the obtained supramolecular polyurethane urea particles are spherical particles, and when the distance is set to 170 mm, the obtained supramolecular polyurethane urea particles are cake-shaped particles with a concave center.

[0059] The experimental method of the experimental device for wet granulation of the solvent-based supramolecular polyurethane urea comprises:

[0060] S1. Add reaction materials and solvent into a temperature-controllable double-layer reactor, introduce nitrogen, and prepare a solvent-based supramolecular polyurethane urea solution according to the set temperature and stirring rate;

[0061] S2, heating by a temperature control device to evaporate the solvent of the solvent-based supramolecular polyurethane urea liquid and adjust the solid content;

[0062] S3. Open the regulating valve of the liquid conveying device and set the flow value of the corrosion-resistant peristaltic pump;

[0063] S4. Adjust the height of the injection device, add curing agent to the curing device, and set the stirring rate;

[0064] S5. Start the filtration system and the curing agent recovery system, set the temperature of the drying device to the experimental temperature, start the screening and collection device, screen and collect the dried supramolecular polyurethane urea particles.

[0065] The raw materials used in the temperature-controlled double-layer reactor in step S1 are diols of different molecular weights, isocyanates and supramolecular chain extenders, and the solvent is one or more of acetone, ethyl acetate, dimethyl sulfoxide, N,N-dimethylformamide and dimethylacetyl.

[0066] The heating temperature of the temperature control device in step S2 is 80° C. to 100° C., the reaction time is 1 hour to 2 hours, the evaporated solvent is one or a mixed solvent of two or more of dimethylformamide, dimethylacetamide, tetrahydrofuran, dichloromethane, and butyl acetate, and the solid content of the solvent-based supramolecular polyurethane urea liquid is adjusted to 12% to 20%. By adjusting the solid content, high-density polyurethane urea solid particles or low-density polyurethane urea solid particles can be obtained.

[0067] The flow rate of the corrosion-resistant peristaltic pump in step S3 is set to 30 ml / min to 4000 ml / min, the stirring rate of the curing agent in the curing device in step S4 is 400 r / min to 1000 r / min, and the temperature of the drying device in step S5 is set to 70° C. to 110° C.

[0068] The supramolecular polyurethane urea particles produced by this embodiment are as follows Figure 10-12 As shown, when the height between the injection device and the curing agent liquid level is set to 100 mm, spherical particles are obtained; when the height between the injection device and the curing agent liquid level is increased to 170 mm, the supramolecular polyurethane urea particles obtained are pancake-shaped with a concave center; the ideal particle shape can be obtained by adjusting the distance between the injection device and the curing agent according to needs.

[0069] The above embodiments illustrate the basic principles and main features of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and that the above embodiments and descriptions merely illustrate the principles of the present invention. Various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention, and such changes and modifications are within the scope and rights claimed by the present invention. The scope and rights claimed by the present invention are defined by the appended claims and their equivalents.

Claims

1. An experimental device for wet granulation of solvent-based supramolecular polyurethane urea, characterized in that: The invention comprises a solvent polymerization reaction device, a liquid feed conveying device, a spray solidification device, a separation device, a drying device and a screening and collecting device. The solvent polymerization reaction device, the liquid feed conveying device, the spray solidification device and the separation device are connected in sequence. A drying device and a screening and collecting device are sequentially arranged on the upper side of the separation device, wherein: The spray curing device includes a spraying device and a curing device. The curing device is provided below the spraying device. The curing device is connected to a separation device. The separation device includes a filtering system and a curing agent recovery system. The filtering system is connected to the curing agent recovery system. The injection device includes a distributed injector, a pagoda interface and an embedded nozzle. The distributed injector includes an upper plate and a lower plate. The upper center of the upper plate is connected to the pagoda interface, and the lower side of the upper plate is connected to the lower plate. The upper side of the lower plate is provided with evenly distributed water spray channels. The lower side of the lower plate corresponding to the water spray channel is provided with an embedded nozzle, and the embedded nozzle is connected to the water spray channel. The solvent polymerization reaction device includes a temperature-controllable double-layer reactor and a feed liquid pretreatment device, the feed liquid pretreatment device includes a temperature control device, a condensation reflux device and a stirring reactor, the temperature-controllable double-layer reactor is connected to the temperature control device and the condensation reflux device on the upper side, and the stirring reactor is located inside the temperature-controllable double-layer reactor; The distance between the spraying device and the liquid surface in the curing device was set to 100 mm or 170 mm. When the distance was set to 100 mm, the obtained supramolecular polyurethane urea particles were spherical particles, and when the distance was set to 170 mm, the obtained supramolecular polyurethane urea particles were cake-shaped particles with a concave center. The inner diameter of the embedded nozzle is 1 mm~3 mm.

2. The experimental device for wet granulation of solvent-based supramolecular polyurethane urea according to claim 1, characterized in that: The liquid conveying device includes a corrosion-resistant connecting pipe, a corrosion-resistant peristaltic pump and a regulating valve. The corrosion-resistant connecting pipe is arranged between the solvent polymerization reaction device and the injection curing device. The corrosion-resistant peristaltic pump and the regulating valve are arranged on the corrosion-resistant connecting pipe in sequence.

3. The experimental device for wet granulation of solvent-based supramolecular polyurethane urea according to claim 2, characterized in that: The curing device includes a box body, a motor and a stirring paddle. The motor is fixed to the ground through a side bracket. The motor is connected to the stirring paddle, and the stirring paddle is arranged inside the box body.

4. The experimental method of the experimental device for wet granulation of solvent-based supramolecular polyurethane urea according to claim 3, characterized in that: The following steps are involved: S1. Add reaction materials and solvent into a temperature-controllable double-layer reactor, introduce nitrogen, and prepare a solvent-based supramolecular polyurethane urea solution according to the set temperature and stirring rate; S2, heating by a temperature control device to evaporate the solvent of the solvent-based supramolecular polyurethane urea liquid and adjust the solid content; S3. Open the regulating valve of the liquid conveying device and set the flow value of the corrosion-resistant peristaltic pump; S4. Adjust the height of the injection device, add curing agent to the curing device, and set the stirring rate; S5. Start the filtration system and the curing agent recovery system, set the temperature of the drying device to the experimental temperature, start the screening and collection device, screen and collect the dried supramolecular polyurethane urea particles.

5. The experimental method of the experimental device for wet granulation of solvent-based supramolecular polyurethane urea according to claim 4, characterized in that: The heating temperature of the temperature control device in step S2 is 80°C to 100°C, the reaction time is 1 h to 2 h, and the solid content of the solvent-based supramolecular polyurethane urea solution is adjusted to 12% to 20%.

6. The experimental method of the experimental device for wet granulation of solvent-based supramolecular polyurethane urea according to claim 5, characterized in that: The flow rate of the corrosion-resistant peristaltic pump in step S3 is set to 30 ml / min~4000 ml / min, the stirring rate of the curing agent in the curing device in step S4 is 400 r / min~1000 r / min, and the temperature of the drying device in step S5 is set to 70℃~110℃.

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