Preparation method and equipment of strip-shaped flaky crystal form trans-4-(4-alkyl cyclohexyl) phenol

Abstract

The invention discloses strip-shaped flaky crystal form trans-4-(4-alkyl cyclohexyl) phenol as well as a preparation method and equipment thereof, and relates to the technical fields of an organic compound crystallization process and liquid crystal material preparation. According to the preparation method, the grain size uniformity is remarkably improved through an original eddy current enhanced crystallization and pulse type supersaturation degree regulation and control technology, and the crystal form has the characteristics of large size and high purity. According to the preparation method, integrated equipment is adopted, an eddy field and solvent pulse supplementing technology is utilized in a spiral reducing pipeline, the crystallization process is accurately controlled, the crystal size distribution is uniform, the equipment integrates temperature, centrifugation and a liquid supplementing automatic adjusting system, and ultrasonic real-time monitoring is matched, so that the high-stability strip-shaped flaky crystal can be produced; the method effectively improves the problems of low efficiency and non-uniform crystal form of the traditional process, and is especially suitable for large-scale preparation of high-precision liquid crystal display material intermediates.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic compound crystallization process and liquid crystal material preparation, and in particular to a strip-shaped platelet-shaped crystal form trans-4-(4-alkylcyclohexyl)phenol (wherein the alkyl group is C1-C6 alkyl) and a preparation method and equipment thereof. BACKGROUND

[0002] Trans-4-(4-alkylcyclohexyl)phenol is a key intermediate for preparing high-performance liquid crystal display materials, and the regularity of its crystal structure is directly related to the orientation accuracy and optical uniformity of liquid crystal molecules. In the manufacturing of ultra-high-definition display panels, the high-purity and low-defect characteristics of this material can significantly reduce screen bright spots, color deviation and other undesirable phenomena, and play an irreplaceable role in promoting the mass production of 8K and above resolution display technology and flexible screens. With the continuous upgrading of display quality requirements in emerging fields such as virtual reality and vehicle-mounted displays, the market demand for alkylcyclohexyl phenol crystal raw materials with high purity and controllable morphology continues to rise, driving the research and development and preparation technology innovation of this material.

[0003] Current industrial production mainly uses a batch crystallization process, which relies on manual experience to adjust the solution supersaturation (S value). The traditional gradient cooling method results in a dispersed crystal size distribution and a long-term lattice consistency index below the industry standard lower limit value due to the rough control of the supersaturation (S < 1.1) by the operator. Taking a typical multi-kettle series process as an example, the single-batch production cycle is as long as twelve hours, and the crystal grain length deviation rate exceeds one-third, which seriously restricts the production efficiency and product consistency. The dynamic mismatch between the solvent evaporation rate and the temperature field further exacerbates the process out of control. The local area supersaturation of the system increases sharply to above the critical value, triggering explosive nucleation of the crystal nucleus, and the crystal nucleus density per unit volume far exceeds the normal growth threshold. This abnormal nucleation not only causes the deterioration of the crystal size uniformity, but also induces lattice distortion, forming a large number of structural defects.

[0004] To solve the above problems, the invention patent with publication number CN103553878B proposes a crystallization scheme using multi-stage gradient cooling combined with mechanical stirring. It is to react benzyl oxy bromobenzene compound with magnesium chips in a solvent to obtain benzyl oxy phenyl magnesium bromide, then react with raw material A, and then perform acid hydrolysis to obtain compound B; compound B is subjected to a series of processes such as reflux dehydration in an organic solvent and an organic acid system to obtain compound C; in an organic solvent with pH 6.5-7.5, compound C is subjected to hydrogenation reaction in the presence of a catalyst to obtain cis-trans compound D; the cis-trans compound D is subjected to isomerization reaction in an organic solvent and a strong alkaline system to obtain trans product, and then a series of processes are performed to obtain the alkyl cyclohexyl phenol liquid crystal intermediate compound, but this technology has the defects of poor control of crystal nucleus density and morphology: the preset mode of the cooling gradient cannot respond to the real-time supersaturation change, when the solvent evaporation rate fluctuates, it will still cause local area supersaturation overload, and experimental data shows that the crystal nucleus density is still 2-3 times of the conventional value; although the shear force generated by mechanical stirring can improve the mass transfer efficiency, it will destroy the directional growth of the (001) crystal face of the crystal, resulting in that the aspect ratio dispersion of the obtained crystal is more than 40%, which is difficult to meet the shape requirements of the strip-shaped crystal; in order to realize multi-stage temperature control, an additional cooling module needs to be configured, so that the unit product energy consumption increases to 2.8kW·h / kg, which is better than the traditional multi-kettle process, but still more than 40% higher than the advanced energy efficiency standard in the industry.

[0005] The existing kettle type crystallizer lacks dynamic parameter regulation and control capability, and cannot realize continuous and collaborative control of crystal nucleus generation, crystal growth and stripping process, resulting in that the batch qualified rate has been hovering below 80% for a long time. Although the multi-kettle series design tries to make up for the defects of single-kettle efficiency, it leads to an expansion of equipment area by 500%, and the unit product energy consumption is as high as 1.6 times of the industry energy efficiency standard, which becomes a key obstacle to the green upgrading of the industry.

[0006] In the technical field of liquid crystal materials, alkyl cyclohexyl phenol usually refers to 4-(4-alkyl cyclohexyl) phenol, wherein the alkyl group is a straight chain or branched chain alkyl group with C1-C6, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, etc. As a liquid crystal intermediate, the length of the alkyl chain of such compounds directly affects the crystallization behavior and liquid crystal performance. The preparation method described in the present invention is particularly suitable for such compounds with a clear structure.

[0007] Therefore, we propose a preparation method and special equipment for strip-shaped crystal trans-4-(4-alkyl cyclohexyl) phenol to solve the above problems. SUMMARY

[0008] The present application aims at: in order to solve the technical problems in the background art, provide a preparation method and preparation equipment of bar-shaped sheet-shaped crystal form trans-4-(4-alkylcyclohexyl) phenol, wherein the alkyl is C1-C6 alkyl.

[0009] To achieve the above object, the present application provides the following technical scheme: a preparation method of bar-shaped sheet-shaped crystal form trans-4-(4-alkylcyclohexyl) phenol, comprising the following steps: S1: trans-4-(4-alkylcyclohexyl) phenol and solvent are dissolved at a mass ratio of 1:1.2-1.6 to form a supersaturated solution; S2: the solution prepared in step S1 is introduced into a spiral tapered pipe with centrifugal function, the temperature of the pipe is maintained and the centrifugal rotation is started, so that the solution moves along the pipe wall and forms a vortex crystallization environment in the pipe; S3: pulse addition of trans-4-(4-alkylcyclohexyl) phenol supersaturated solution is added to the pipe, the addition speed is 0.5-2.0 mL / min, the supersaturation degree S of the solution is controlled to be 1.2-1.5, and Ostwald ripening is induced; S4: repeat steps S2 and S3 for multi-stage dynamic crystallization, so that the crystallization solution circulates in the spiral tapered pipe for 3-5 times, until the length of the crystal is 9-17 mm and the width is 2-5.5 mm; S5: start the scraping mechanism to peel off the crystal grains, dry after centrifugation, and obtain bar-shaped sheet-shaped trans-4-(4-alkylcyclohexyl) phenol crystal.

[0010] As a further scheme of the present application: the temperature dissolution in step S1 is dissolved at a temperature of 65-80℃; the added solvent is ethanol.

[0011] As a further scheme of the present application: the diameter contraction ratio of the spiral tapered pipe in step S2 is 2:1-4:1, the temperature of the pipe is maintained at 45-65℃, and the centrifugal rotation speed is started at 80-120 rpm.

[0012] The present application research process found that, different chain length (C1-C6) of alkyl substituent group will significantly affect the diffusion coefficient and interface growth kinetics of trans-4-(4-alkylcyclohexyl) phenol molecules. Longer alkyl chain (such as C5, C6) because of the increase of molecular volume, its diffusion coefficient in solution is usually about 20%-40% lower than short chain (such as C1, C2) compounds, which is easy to cause mass transfer limited in crystal growth process, easy to produce dendrite or defect. The core of the present application is that, by synergistically regulating the vortex field intensity generated by the spiral tapered pipe (7) (via centrifugal speed 80-120 rpm and pipe contraction ratio 2:1-4:1 adjustment) and the supersaturation curve of pulse liquid supplement (via supplement speed 0.5-2.0 mL / min and target supersaturation S=1.2-1.5 control), the intrinsic growth rate difference brought by different alkyl chain length can be dynamically matched. Specifically, for the slow diffusion of long chain molecules, the vortex intensity can be appropriately increased to strengthen the mass transfer, and the slower supplement rate is matched; for short chain molecules, the parameters can be optimized to inhibit excessive nucleation. This dynamic and adjustable crystallization environment enables a series of compounds from methyl (C1) to hexyl (C6) to realize the directional growth of (001) crystal surface and the uniform strip-shaped flake morphology in the same process framework, as shown in examples 1-3.

[0013] As a further scheme of the present application: A strip-shaped flake crystal form trans-4-(4-alkylcyclohexyl) phenol preparation equipment, steps S1-S4 are completed in an integrated equipment, the integrated equipment includes a connecting pipe, the connecting pipe is fixedly connected with a liquid feeding pipe and a solid feeding port on both sides, a condenser is installed at the top end of the connecting pipe, a reaction bin is fixedly connected at the bottom end of the connecting pipe, a discharge pipe is fixedly connected at the bottom end of the reaction bin, a centrifugal bin is fixedly connected at the bottom end of the discharge pipe, a spiral tapered pipe is installed in the centrifugal bin, a mounting seat is fixedly connected at the bottom end of the centrifugal bin, a collection barrel is installed at the bottom end of the mounting seat, a filter basket is arranged in the inner cavity of the collection barrel, a heating jacket is installed on the outer wall of the reaction bin, a heat preservation jacket is installed on the outer wall of the centrifugal bin, a washing pipe is fixedly connected on one side of the outer wall of the mounting seat, and a gas inlet pipe is fixedly connected on one side of the outer wall of the reaction bin. The inner wall bottom end of the reaction bin is provided with a baffle, the inner wall bottom end of the reaction bin is symmetrically provided with a limiting rod and a lead screw penetrating the baffle, the limiting rod is fixedly connected with the reaction bin, a first motor is installed at the outer bottom end of the reaction bin, the lead screw is connected to the output end of the first motor and rotationally connected with the reaction bin, a filter plate is installed in the inner cavity of the discharge pipe, a rotating plate with a concave arc-shaped upper surface is rotationally connected in the centrifugal bin, the rotating plate is fixedly connected to the top end of the spiral tapered pipe, the spiral tapered pipe is hollow and the upper end opening is located at the top end of the rotating plate, a first bevel gear is fixedly connected to the lower part of the outer wall of the spiral tapered pipe, a second motor is installed on the outer wall of the mounting seat, a second bevel gear is connected to the output end of the second motor, the second bevel gear is in contact with the first bevel gear, the collection barrel is installed at the bottom end of the mounting seat through a mounting mechanism, and the inner wall of the filter basket is scraped by a scraping mechanism.

[0014] As a further scheme of the application: the mounting mechanism comprises a first docking plate, the first docking plate is fixedly connected to the bottom end of the mounting seat on both sides, the top end of the collection barrel is fixedly connected with a second docking plate on both sides, the top end of the second docking plate is fixedly connected with a connecting rod, a fixed groove is formed in the outer wall of the connecting rod, a connecting groove is formed in the outer wall of the first docking plate, a fixed block extending into the inner cavity of the connecting groove is slidably connected in the first docking plate, a first spring is connected between the fixed block and the first docking plate, a push plate is slidably connected in the first docking plate on the side away from the first spring below the fixed block, a rotating column is rotationally connected to the outer wall of the first docking plate, one end of the rotating column is fixedly connected with a threaded rod, the threaded rod penetrates the push plate, an annular plate is fixedly connected to the top end of the filter basket, plug-in grooves are symmetrically formed in the top end of the annular plate, a placing groove is formed in the top end of the collection barrel, plug-in rods are fixedly connected to the inner wall of the placing groove, and a support seat is fixedly connected to the inner wall bottom end of the collection barrel.

[0015] As a further scheme of the present application: the scraping mechanism comprises a third motor, the third motor is installed at the bottom end of the collection barrel, a connecting shaft is connected to the output end of the third motor, a square rod is fixedly connected to the top end of the connecting shaft, the square rod is rotatably connected to the top end of the support base, a rotating disc is rotatably connected to the bottom of the filter basket, a square groove is formed in the bottom end of the rotating disc, a vertical rod is fixedly connected to the top end of the rotating disc, horizontal rods are fixedly connected to the outer wall of the vertical rod in a symmetrical manner, scraping plates are slidably connected to the outer wall of the horizontal rods, guide frames provided with strip-shaped guide grooves are fixedly connected to the outer wall of the scraping plates in an inclined manner, a cross-shaped frame extending out of the vertical rod is slidably connected to the inside of the vertical rod, slide rods are fixedly connected to the two side arms of the cross-shaped frame extending out of the two ends of the vertical rod in a symmetrical manner, the slide rods are slidably connected to the inner wall of the strip-shaped guide grooves, and a pressing cylinder is fixedly connected to the top end of the cross-shaped frame.

[0016] As a further scheme of the present application: the outer wall of the annular plate is matched with the inner wall of the placing groove, the inner wall of the insertion groove is matched with the outer wall of the insertion rod, the inner wall of the connecting groove is matched with the outer wall of the connecting rod, and the outer extending end of the fixing block is provided with an inclined surface and the outer extending end outer wall thereof is matched with the inner wall of the fixing groove.

[0017] As a further scheme of the present application: the fixing block is in an L shape, and a threaded hole is formed in the outer wall of the push plate and matched with the threaded rod.

[0018] As a further scheme of the present application: the outer wall of the square rod is matched with the inner wall of the square groove, and the inner wall of the strip-shaped guide groove is matched with the outer wall of the slide rod.

[0019] Compared with the prior art, the present application has the following beneficial effects: 1. The strip-shaped flaky crystal trans-4-(4-alkylcyclohexyl) phenol and the preparation method thereof can significantly improve the uniformity of crystal grain size, effectively improve the thermal stability of the crystal form and reduce the solvent residue through the unique vortex enhanced crystallization and pulse supersaturation control technology.

[0020] 2. The strip-shaped flaky crystal trans-4-(4-alkylcyclohexyl) phenol and the preparation method thereof can be customized to produce 9-17 mm crystals of different specifications through multi-dimensional adjustment of process parameter elastic design support pipe contraction ratio (2:1-4:1), make-up speed (0.5-2.0 mL / min), etc., adapt to the needs of emerging display devices such as flexible screens and VR headsets, and provide core material support for the ultra-high definition display industry.

[0021] 3. The integrated dynamic crystallization device compresses the single batch production cycle from 12 hours to 7.2 hours, improves the efficiency by 40%, reduces the comprehensive production cost by 30%, reduces the equipment area by 40%, and realizes the synergistic breakthrough of high efficiency and low cost.

[0022] 4. The integrated device is designed to match the improved process, the integrated device is provided with a mounting mechanism and a scraping mechanism, the filter basket is placed in the collecting barrel, until the bottom end of the filter basket contacts the supporting seat, the annular plate is displaced into the placing groove, the inserting rod is inserted into the inserting groove, the position of the filter basket is positioned, then the collecting barrel is moved, the first and second abutting plates are aligned, the connecting rod is inserted into the connecting groove, the fixing block is clamped into the fixing groove under the action of the first spring elastic force, the collecting barrel and the filter basket are installed, the filter basket is quickly installed and disassembled, when the filter basket is installed, the solution in the filter basket is centrifuged through the rotation of the scraper; after the filter basket is disassembled, the crystals on the inner wall of the filter basket are scraped off through the rotation of the scraper. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 The structural general formula of the trans-4-(4-alkylcyclohexyl) phenol is shown in the figure; Figure 2 The structural schematic diagram of the integrated device is shown in the figure; Figure 3 The internal structure schematic diagram of the integrated device is shown in the figure; Figure 4 The internal structure schematic diagram of the reaction bin of the integrated device is shown in the figure; Figure 5 The internal structure schematic diagram of the mounting seat of the integrated device is shown in the figure; Figure 6 The mounting schematic diagram of the collecting barrel of the integrated device is shown in the figure; Figure 7 The mounting schematic diagram of the integrated device is shown in the figure; Figure 5 The enlarged view of A in the figure; Figure 8 The mounting schematic diagram of the filter basket of the integrated device is shown in the figure; Figure 9 The internal structure schematic diagram of the filter basket of the integrated device is shown in the figure; Figure 10 The internal structure schematic diagram of the vertical rod of the integrated device is shown in the figure.

[0024] In the figure: 1, connecting pipe; 2, liquid feeding pipe; 3, solid feeding port; 4, reaction bin; 5, discharging pipe; 6, centrifugal bin; 7, spiral tapered pipe; 8, mounting mechanism; 801, first butt joint plate; 802, second butt joint plate; 803, connecting rod; 804, fixing groove; 805, connecting groove; 806, fixing block; 807, first spring; 808, push plate; 809, threaded rod; 810, rotating column; 811, annular plate; 812, insertion slot; 813, placing groove; 814, insertion rod; 815, support seat; 9, scraping mechanism; 901, third motor; 902, connecting shaft; 903, square rod; 904, rotating disc; 905, square groove; 906, vertical rod; 907, horizontal rod; 908, scraper; 909, guide frame; 910, cross frame; 911, sliding rod; 912, pressing cylinder; 10, filter basket; 11, condenser; 12, heating jacket; 13, heat preservation jacket; 14, rinsing pipe; 15, air inlet pipe; 16, baffle; 17, limiting rod; 18, lead screw; 19, first motor; 20, filter plate; 21, rotating plate; 22, first bevel gear; 23, second bevel gear; 24, second motor; 25, mounting seat; 26, collecting barrel. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

[0026] In the present application, the "trans-4-(4-alkylcyclohexyl)phenol" refers to a 4-(4-alkylcyclohexyl)phenol compound having a structure as shown in the attached formula (I). Figure 1 The trans-4-(4-alkylcyclohexyl)phenol compound in the present application has a trans configuration, and the alkyl group is a C1-C6 alkyl group, including but not limited to methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl. Preferably, the alkyl group is a C3-C5 straight-chain alkyl group. The preparation method of the present application is universal for compounds having the general structure, and those skilled in the art can fine-tune the process parameters (such as temperature, addition rate, etc.) according to the specific alkyl chain length to achieve the technical effects of the present application.

[0027] In the description of the present application, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer" and the like indicate the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application. In addition, the terms "first", "second", "third" are only for descriptive purposes and cannot be understood as indicating or implying relative importance. In the description of the present application, it should be noted that unless otherwise explicitly specified and limited, the terms "mounting", "connecting", "connecting", "setting" should be understood broadly, for example, it can be fixedly connected, or it can be detachably connected, or integrally connected; it can be mechanically connected, or it can be electrically connected; it can be directly connected, or it can be indirectly connected through an intermediate medium, or it can be connected inside two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances. The embodiments will be described below according to the overall structure of the present application. Embodiment 1

[0028] In the embodiments of the present application, a preparation method of a strip-shaped flaky crystal form of trans-4-(4-alkylcyclohexyl) phenol comprises the following steps: S1, 200 kg of 4-(4-n-propylcyclohexyl) phenol (purity up to 99.5%) and 280 kg of ethanol (60℃±1℃) are dissolved in a reaction kettle; S2, the solution is introduced into the spiral tapered pipe 7 (pipe diameter contraction ratio 3:1) at a flow rate of 2 m / s, and ultrasonic monitoring (frequency 35 kHz) is started; S3, the trans-4-(4-alkylcyclohexyl) phenol supersaturated solution is added in a pulse manner, the average addition speed is controlled to be about 0.5 mL / min, and the system supersaturation S is maintained at 1.4.

[0029] S4, after 120 min of continuous crystallization, crystal grains with a size of 15±1mm×4±0.3mm are obtained, and XRD detection shows that the characteristic peak intensity deviation is less than 5%; S5, after centrifugal separation (3000 rpm), vacuum drying (50℃ / 2h) is performed, HPLC purity is 99.99%, and solvent residue is less than 100ppm.

[0030] Please refer to Figures 2 to 10The application discloses a preparation device for a strip-shaped and flaky crystal form trans-4-(4-alkylcyclohexyl)phenol, wherein steps S1-S4 are completed in an integrated device, the integrated device comprises a connecting pipe 1, a liquid feeding pipe 2 and a solid feeding port 3 are fixedly connected to the two sides of the connecting pipe 1, a condenser 11 is installed at the top end of the connecting pipe 1, a reaction bin 4 is fixedly connected to the bottom end of the connecting pipe 1, a discharge pipe 5 is fixedly connected to the bottom end of the reaction bin 4, a centrifugal bin 6 is fixedly connected to the bottom end of the discharge pipe 5, a spiral tapered pipe 7 is installed in the centrifugal bin 6, a mounting seat 25 is fixedly connected to the bottom end of the centrifugal bin 6, a collecting barrel 26 is installed at the bottom end of the mounting seat 25, a filter basket 10 is arranged in the inner cavity of the collecting barrel 26, a heating jacket 12 is installed on the outer wall of the reaction bin 4, a heat preservation jacket 13 is installed on the outer wall of the centrifugal bin 6, a washing pipe 14 is fixedly connected to the outer wall of one side of the mounting seat 25, and an air inlet pipe 15 is fixedly connected to the outer wall of one side of the reaction bin 4.

[0031] A baffle plate 16 is arranged at the bottom end of the inner wall of the reaction bin 4, a limiting rod 17 and a lead screw 18 penetrating through the baffle plate 16 are symmetrically arranged at the bottom end of the inner wall of the reaction bin 4, the limiting rod 17 is fixedly connected to the reaction bin 4, a first motor 19 is installed at the bottom end of the outer wall of the reaction bin 4, the lead screw 18 is connected to the output end of the first motor 19 and rotationally connected to the reaction bin 4, a filter plate 20 is installed in the inner cavity of the discharge pipe 5, a rotating plate 21 with an inner concave arc surface on the upper surface is rotationally connected in the centrifugal bin 6, the rotating plate 21 is fixedly connected to the top end of the spiral tapered pipe 7, the spiral tapered pipe 7 is hollow and the upper end opening is located at the top end of the rotating plate 21, a first bevel gear 22 is fixedly connected to the lower part of the outer wall of the spiral tapered pipe 7, a second motor 24 is installed on the outer wall of the mounting seat 25, a second bevel gear 23 is connected to the output end of the second motor 24, the second bevel gear 23 is in contact with the first bevel gear 22, the collecting barrel 26 is installed at the bottom end of the mounting seat 25 through a mounting mechanism 8, and the inner wall of the filter basket 10 is scraped through a scraping mechanism 9.

[0032] In the embodiment, the trans-4-(4-alkylcyclohexyl)phenol is added through the solid feeding port 3, the solvent is added through the liquid feeding pipe 2, and the solution is dissolved by heating in the reaction bin 4 to form a supersaturated solution; the first motor 19 is started, the first motor 19 is driven to rotate the lead screw 18, the lead screw 18 is driven to displace the baffle 16 to open the discharge pipe 5, and at the same time, the air inlet pipe 15 injects nitrogen into the reaction bin 4 to pressurize to 0.2 MPa, the solution flows into the spiral tapered pipe 7 through the discharge pipe 5, at this time, the second motor 24 is started, the second motor 24 is driven to rotate the second bevel gear 23, the second bevel gear 23 is driven to rotate the first bevel gear 22, and the first bevel gear 22 is driven to rotate the spiral tapered pipe 7, so that the solution moves along the pipe wall to form a vortex crystallization environment in the pipe, and then easily enters the filter basket 10, and the liquid flows into the collection barrel 26 through the filter basket 10 by cooperation of the parts in the scraping mechanism 9, and the crystals are left in the filter basket 10, and then the eluent can be injected into the filter basket 10 through the elution pipe 14 to make the crystals in the filter basket 10 cleaner.

[0033] Please refer to Figures 5 to 8 , the mounting mechanism 8 comprises a first butt joint plate 801, the first butt joint plate 801 is fixedly connected to the bottom end of the two sides of the mounting seat 25 in a symmetrical manner, the top end of the two sides of the collection barrel 26 is fixedly connected with a second butt joint plate 802 in a symmetrical manner, the top end of the second butt joint plate 802 is fixedly connected with a connecting rod 803, the outer wall of the connecting rod 803 is provided with a fixed groove 804, the outer wall of the first butt joint plate 801 is provided with a connecting groove 805, the inside of the first butt joint plate 801 is slidably connected with a fixed block 806 extending into the inner cavity of the connecting groove 805, the first spring 807 is connected between the fixed block 806 and the first butt joint plate 801, the inside of the first butt joint plate 801 is slidably connected with a push plate 808 on the side away from the first spring 807 below the fixed block 806, the outer wall of the first butt joint plate 801 is rotatably connected with a rotating column 810, one end of the rotating column 810 is fixedly connected with a threaded rod 809, the threaded rod 809 penetrates through the push plate 808, the top end of the filter basket 10 is fixedly connected with an annular plate 811, the top end of the annular plate 811 is symmetrically provided with an insertion slot 812, the top end of the collection barrel 26 is provided with a placing groove 813, the inner wall of the placing groove 813 is fixedly connected with an insertion rod 814 in a symmetrical manner, and the inner wall of the collection barrel 26 is fixedly connected with a support seat 815.

[0034] In the embodiment, when the collecting barrel 26 and the filter basket 10 are installed, the filter basket 10 is placed into the collecting barrel 26 until the bottom end of the filter basket 10 contacts with the support base 815, the annular plate 811 is displaced into the placing groove 813, the inserting rod 814 is inserted into the inserting groove 812, the position of the filter basket 10 is positioned, then the collecting barrel 26 is moved so that the first abutting plate 801 and the second abutting plate 802 are aligned, the connecting rod 803 is inserted into the connecting groove 805, the fixing block 806 is clamped into the fixing groove 804 under the elastic force of the first spring 807, and the collecting barrel 26 and the filter basket 10 are installed.

[0035] When the collecting barrel 26 is removed, the rotating column 810 is rotated, the rotating column 810 drives the threaded rod 809 to rotate, the threaded rod 809 drives the push plate 808 to displace, the push plate 808 displaces and contacts with the fixing block 806, the fixing block 806 is pushed to displace, the fixing block 806 displaces out of the fixing groove 804, the fixing of the connecting rod 803 is cancelled, at this time the connecting rod 803 is moved out of the connecting groove 805, so that the collecting barrel 26 is removed.

[0036] Please refer to Figures 8 to 10 , the scraping mechanism 9 comprises a third motor 901, the third motor 901 is installed at the bottom end of the collecting barrel 26, the output end of the third motor 901 is connected with a connecting shaft 902, the top end of the connecting shaft 902 is fixedly connected with a square rod 903, the square rod 903 is rotatably connected with the top end of the support base 815, the bottom of the filter basket 10 is rotatably connected with a rotating disc 904, the bottom end of the rotating disc 904 is provided with a square groove 905, the top end of the rotating disc 904 is fixedly connected with a vertical rod 906, the outer wall of the vertical rod 906 is symmetrically fixedly connected with a horizontal rod 907, the outer wall of the horizontal rod 907 is slidably connected with a scraper 908, the outer wall of the scraper 908 is fixedly connected with a guide frame 909 with a strip-shaped guide groove, the inside of the vertical rod 906 is slidably connected with a cross 910 extending out of the vertical rod 906, the two side arms of the cross 910 extending out of the two ends of the vertical rod 906 are respectively symmetrically fixedly connected with a sliding rod 911, the sliding rod 911 is slidably connected with the inner wall of the strip-shaped guide groove, the top end of the cross 910 is fixedly connected with a pressing cylinder 912.

[0037] In the embodiment, during the installation of the collecting barrel 26 and the filter basket 10, the filter basket 10 is moved to the top end of the support seat 815, at this time, the square rod 903 is inserted into the square slot 905, the square rod 903 is displaced to contact the cross 910, the cross 910 is pushed to be displaced, the cross 910 is displaced to drive the slide rod 911 to be displaced, the slide rod 911 is slid in the guide frame 909 to push the scraper 908 to be displaced, the scraper 908 is displaced along the horizontal rod 907, and the scraper 908 is separated from the inner wall of the filter basket 10; after the installation of the collecting barrel 26 and the filter basket 10 is completed, the third motor 901 can be started, the third motor 901 is operated to drive the connecting shaft 902 to rotate, the connecting shaft 902 is rotated to drive the square rod 903 to rotate, the square rod 903 is rotated to drive the vertical rod 906 to rotate through the rotating disc 904, the vertical rod 906 is rotated to drive the scraper 908 to rotate, and the solution in the filter basket 10 is stirred, so that the centrifugal separation operation is performed on the solution in the filter basket 10.

[0038] When the collecting barrel 26 and the filter basket 10 are removed, the filter basket 10 is moved out of the collecting barrel 26, the lower pressing cylinder 912 is pushed downward, the lower pressing cylinder 912 is displaced to drive the cross 910 to be displaced, the cross 910 is displaced to drive the slide rod 911 to be displaced, the slide rod 911 is slid along the inner wall of the guide frame 909 to drive the scraper 908 to be displaced, the scraper 908 is displaced to contact the inner wall of the filter basket 10, then the lower pressing cylinder 912 can be rotated, the lower pressing cylinder 912 is rotated to drive the vertical rod 906 to rotate, the vertical rod 906 is rotated to drive the scraper 908 to rotate, and the crystals on the inner wall of the filter basket 10 are scraped off. The design facilitates the rapid installation and removal of the filter basket 10, when the filter basket 10 is installed, the rotation of the scraper 908 is used to perform the centrifugal separation on the solution in the filter basket 10; after the filter basket 10 is removed, the rotation of the scraper 908 is used to scrape off the crystals on the inner wall of the filter basket 10.

[0039] Please refer to Figures 5 to 5 , the outer wall of the annular plate 811 is attached to the inner wall of the placing groove 813, the inner wall of the insertion groove 812 is attached to the outer wall of the insertion rod 814, the inner wall of the connecting groove 805 is attached to the outer wall of the connecting rod 803, and the outer extension end of the fixed block 806 is provided with an inclined surface and the outer extension end outer wall is attached to the inner wall of the fixed groove 804.

[0040] In the embodiment, the filter basket 10 is placed into the collecting barrel 26 until the bottom end of the filter basket 10 is in contact with the support base 815, the annular plate 811 is displaced into the placing groove 813, the inserting rod 814 is inserted into the inserting groove 812, the position of the filter basket 10 is positioned, then the collecting barrel 26 is moved, the first abutting plate 801 and the second abutting plate 802 are aligned, the connecting rod 803 is inserted into the connecting groove 805, the fixing block 806 is clamped into the fixing groove 804 under the elastic force of the first spring 807, and the collecting barrel 26 and the filter basket 10 are installed.

[0041] Please refer to Figures 5 to 8 The fixing block 806 is in an L shape, and the outer wall of the push plate 808 is provided with a threaded hole matched with the threaded rod 809.

[0042] In the embodiment, the rotating column 810 is rotated, the rotating column 810 drives the threaded rod 809 to rotate, the threaded rod 809 drives the push plate 808 to displace, the push plate 808 is in contact with the fixing block 806, the fixing block 806 is displaced out of the fixing groove 804, and the fixing of the connecting rod 803 is cancelled.

[0043] Please refer to Figures 8 to 10 The outer wall of the square rod 903 is attached to the inner wall of the square groove 905, and the inner wall of the strip-shaped guide groove is attached to the outer wall of the sliding rod 911.

[0044] In the embodiment, during the installation of the collecting barrel 26 and the filter basket 10, the filter basket 10 is moved to the top end of the support base 815, at this time, the square rod 903 is inserted into the square groove 905, the square rod 903 is in contact with the cross 910, the cross 910 is displaced, the cross 910 drives the sliding rod 911 to displace, the sliding rod 911 is slid in the guide frame 909 to push the scraper 908 to displace, the scraper 908 is displaced along the horizontal rod 907, so that the scraper 908 is separated from the inner wall of the filter basket 10.

[0045] The strip-shaped flaky crystal form trans-4-(4-alkylcyclohexyl)phenol prepared in Example 1 is subjected to product performance test, and the test method and detection results are shown in Table 1 below: Table 1-Product performance data verification of Example 1

[0046] The results show that the size variation coefficient (CV value) is only 6% under the standard process parameters, which is far below the industry standard threshold of 20%. The lattice defect rate is 0.03%, which breaks through the existing technical limit (traditional process > 0.1%). The synchrotron radiation diffraction shows that the lattice distortion is mainly concentrated in the edge area (<5 μm), and the core area perfectly matches the single crystal model. After 80°C accelerated aging, the defect rate only increases to 0.035%, which proves that the vortex field induced (001) crystal face directional growth significantly improves the thermal stability, effectively improves the thermal stability of the crystal form and reduces the solvent residue. Example 2

[0047] A preparation method of a bar-shaped sheet crystal form of trans-4-(4-alkylcyclohexyl) phenol, except for the following differences, other steps are the same as example 1: S1: replace the raw material with trans-4-(4-methylcyclohexyl) phenol, and add 0.2wt% microcrystalline (particle size 50 μm ± 5 μm) of the compound as seed after dissolution; S2: adjust the pipeline temperature to 50°C, and adjust the centrifugal speed to 100 rpm; S3: pulse supplement of supersaturated solution containing 0.1wt% microcrystalline, and adjust the supplement speed to 1.0 mL / min.

[0048] The bar-shaped sheet crystal form of trans-4-(4-alkylcyclohexyl) phenol prepared in example 2 is subjected to product performance test, and the test method and detection results are shown in table 2 below: Table 2 product performance data verification (adding seed) of example 2

[0049] The results show that for short-chain methyl (C1) compounds, the addition of microcrystalline seed significantly optimizes the crystallization process. The size distribution CV value is reduced to 4.5%, which proves that the seed effectively guides the uniform nucleation and inhibits the secondary nucleation. The EBSD data shows that the (001) crystal face orientation degree is as high as 98.5% ± 0.5%, and the orientation deviation angle is ≤2°, which shows excellent directional growth characteristics. The XRD refinement shows that the lattice distortion degree is as low as 0.004, which indicates that the microcrystalline seed provides a regular growth template for the Ostwald ripening process, so that the crystal is more ordered, and a highly consistent crystal form and extremely low lattice defect are obtained in the methyl derivative with smaller molecular weight. Example 3

[0050] A preparation method of a bar-shaped sheet crystal form of trans-4-(4-alkylcyclohexyl) phenol, except for the following differences, other steps are the same as example 1: S1: replace the raw material with trans-4-(4-n-hexylcyclohexyl) phenol, and adjust the mass ratio with ethanol to 1:1.5; S2: centrifugal speed was adjusted to 110 rpm, and pipe temperature was adjusted to 60 °C; S3: liquid supplementing rate was adjusted to 1.8 mL / min.

[0051] The bar-shaped flake crystal form of trans-4-(4-alkylcyclohexyl)phenol prepared in Example 3 was subjected to product performance testing, and the testing method and detection results are shown in Table 3 below: Table 3-Product performance data verification of Example 3 (large size customized type)

[0052] The results show that for the longer chain n-hexyl (C6) compound, under the optimized process parameters, the crystal width can still be accurately controlled at 5.0±0.3 mm (RSD=4.0%), breaking through the limit of traditional process control for long-chain molecular crystallization. SEM shows that after continuous operation for 110 hours, the thickness of the attached layer on the equipment pipe wall is <10 μm, which is much lower than the critical fouling threshold (200 μm), proving the good adaptability of the process and equipment to long-chain alkyl compounds. Energy consumption data show that the vortex field and pulse liquid supplementing parameters adjusted for long-chain molecules work synergistically to achieve efficient mass transfer and solvent utilization, with the final unit energy consumption controlled at 1.8 kW·h / kg, which is significantly lower than the industry benchmark of 3.0 kW·h / kg for large-scale traditional processes. Comparative Example

[0053] The same batch of raw materials was treated by the method of CN103553878B patent: multi-kettle cascade gradient cooling crystallization (without vortex field and pulse liquid supplementing), mechanical stirring speed 200 rpm, cooling rate 0.5 °C / min. The bar-shaped flake crystal form of trans-4-(4-alkylcyclohexyl)phenol prepared in the comparative example was subjected to product performance testing, and the testing method and detection results are shown in Table 4: Table 4-Product performance data verification of comparative example

[0054] The results show that the size CV value of 28% is due to the difference in nucleation position caused by temperature gradient (infrared thermal imaging shows ±8 °C fluctuation). The grain boundary melting phenomenon is confirmed by SEM-EDS: impurity elements (Na + , Cl - ) are enriched at the grain boundaries (concentration up to 1200 ppm), reducing the local melting point to 75 °C. The deep reason for the LCI value of 0.75 is the orientation disorder of the (001) crystal plane (EBSD shows that the maximum deviation angle is up to 42°). This serious orientation disorder directly leads to the inability to achieve uniform gap control in the liquid crystal cell prepared therefrom, which directly explains the display color deviation problem mentioned in the background technology from the mechanism level.

[0055] The above merely describes preferred specific embodiments of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art, according to the technical solution and inventive concept of the present application, makes equivalent replacement or change within the technical range disclosed by the present application, which should be covered within the protection scope of the present application.

Claims

1. A process for the preparation of a strip-shaped lamellar crystalline form of trans-4-(4-alkylcyclohexyl)phenol, wherein the alkyl group is a C1-C6 alkyl group, characterized in that, The method comprises the following steps: S1: Dissolve trans-4-(4-alkylcyclohexyl) phenol with solvent at a mass ratio of 1:1.2-1.6 to form a supersaturated solution; S2: Introduce the solution prepared in step S1 into a spiral tapered pipe (7) with centrifugal function, maintain the pipe temperature and start centrifugal rotation, make the solution move along the pipe wall, and form a vortex crystallization environment in the pipe; S3: Pulse add trans-4-(4-alkylcyclohexyl) phenol supersaturated solution to the pipe, the addition speed is 0.5-2.0 mL / min, the supersaturation degree of the solution is controlled to be S=1.2-1.5, and Ostwald ripening is induced; S4: Repeat steps S2 and S3 to perform multi-stage dynamic crystallization, circulate the crystallization solution in the spiral tapered pipe (7) for 3-5 times, until the length of the crystal is 9-17 mm and the width is 2-5.5 mm; S5: Start the scraping mechanism (9) to peel off the crystal grains, dry after centrifugation, and obtain strip-shaped trans-4-(4-alkylcyclohexyl) phenol crystals.

2. A process for the preparation of a strip-shaped, platelet-shaped crystalline form of trans-4-(4-alkylcyclohexyl)phenol according to claim 1, characterized in that, The temperature rising dissolution in step S1 is dissolved at a temperature of 65-80°C; and the added solvent is ethanol.

3. A process for the preparation of a strip-shaped, platelet-shaped crystal form of trans-4-(4-alkylcyclohexyl)phenol according to claim 1, characterized in that, The spiral tapered pipe (7) in step S2 has a diameter contraction ratio of 2:1-4:1, the pipe temperature is maintained at 45-65°C, and the centrifugal rotation speed is started at 80-120 rpm.

4. Apparatus for use in a process for the preparation of a strip-shaped lamellar crystal form of trans-4-(4-alkylcyclohexyl)phenol according to any one of claims 1 to 3, characterized in that Steps S1-S4 are completed in an integrated device, the integrated device comprises a connecting pipe (1), the two sides of the connecting pipe (1) are respectively fixedly connected with a liquid feeding pipe (2) and a solid feeding port (3), a condenser (11) is installed at the top end of the connecting pipe (1), a reaction bin (4) is fixedly connected to the bottom end of the connecting pipe (1), a discharge pipe (5) is fixedly connected to the bottom end of the reaction bin (4), a centrifugal bin (6) is fixedly connected to the bottom end of the discharge pipe (5), a spiral tapered pipe (7) is installed in the centrifugal bin (6), a mounting seat (25) is fixedly connected to the bottom end of the centrifugal bin (6), a collection barrel (26) is installed at the bottom end of the mounting seat (25), a filter basket (10) is arranged in the inner cavity of the collection barrel (26), a heating jacket (12) is installed on the outer wall of the reaction bin (4), a heat preservation jacket (13) is installed on the outer wall of the centrifugal bin (6), a washing pipe (14) is fixedly connected to one side of the outer wall of the mounting seat (25), and an air inlet pipe (15) is fixedly connected to one side of the outer wall of the reaction bin (4).

5. The apparatus for preparing a strip-shaped lamellar crystal form of trans-4-(4-alkylcyclohexyl)phenol according to claim 4, characterized by, The inner wall bottom end of the reaction bin (4) is provided with a baffle (16), the inner wall bottom end of the reaction bin (4) is symmetrically provided with a limiting rod (17) and a lead screw (18) penetrating through the baffle (16), the limiting rod (17) is fixedly connected with the reaction bin (4), the outer bottom end of the reaction bin (4) is provided with a first motor (19), the lead screw (18) is connected with the output end of the first motor (19) and is rotatably connected with the reaction bin (4), the inner cavity of the discharge pipe (5) is provided with a filter plate (20), the inside of the centrifugal bin (6) is rotatably connected with a rotating plate (21) with an inner concave arc surface upper surface, the rotating plate (21) is fixedly connected with the top end of the spiral tapered pipe (7), the spiral tapered pipe (7) is hollow and the upper end opening is located at the top end of the rotating plate (21), the lower part of the outer wall of the spiral tapered pipe (7) is fixedly connected with a first bevel gear (22), the outer wall of the mounting seat (25) is provided with a second motor (24), the output end of the second motor (24) is connected with a second bevel gear (23), the second bevel gear (23) is in contact with the first bevel gear (22), the collecting barrel (26) is installed on the bottom end of the mounting seat (25) through the mounting mechanism (8), and the inner wall of the filter basket (10) is scraped by the scraping mechanism (9).

6. A device for preparing a strip-shaped, lamellar crystal form of trans-4-(4-alkylcyclohexyl)phenol according to claim 5, characterized in that, The mounting mechanism (8) comprises a first docking plate (801), the first docking plate (801) is fixedly connected to the bottom end of the mounting seat (25) on both sides, the top end of the collecting barrel (26) is fixedly connected with a second docking plate (802) on both sides, the top end of the second docking plate (802) is fixedly connected with a connecting rod (803), the outer wall of the connecting rod (803) is provided with a fixed groove (804), the outer wall of the first docking plate (801) is provided with a connecting groove (805), the inner wall of the first docking plate (801) is slidably connected with a fixed block (806) extending into the inner cavity of the connecting groove (805), the first spring (807) is connected between the fixed block (806) and the first docking plate (801), the inner wall of the first docking plate (801) is slidably connected with a push plate (808) on the side away from the first spring (807) below the fixed block (806), the outer wall of the first docking plate (801) is rotatably connected with a rotating column (810), one end of the rotating column (810) is fixedly connected with a threaded rod (809), the threaded rod (809) penetrates through the push plate (808), the top end of the filter basket (10) is fixedly connected with a ring plate (811), the top end of the ring plate (811) is symmetrically provided with a insertion slot (812), the top end of the collecting barrel (26) is provided with a placing groove (813), the inner wall of the placing groove (813) is symmetrically fixedly connected with an insertion rod (814), and the inner wall bottom end of the collecting barrel (26) is fixedly connected with a support seat (815).

7. A device for preparing a strip-shaped, lamellar crystal form of trans-4-(4-alkylcyclohexyl)phenol according to claim 6, characterized in that, The scraping mechanism (9) comprises a third motor (901), the third motor (901) is installed at the bottom end of the collection barrel (26), the output end of the third motor (901) is connected with a connecting shaft (902), the top end of the connecting shaft (902) is fixedly connected with a square rod (903), the square rod (903) is rotatably connected to the top end of the support base (815), the bottom of the filter basket (10) is rotatably connected with a rotating disc (904), the bottom end of the rotating disc (904) is provided with a square groove (905), the top end of the rotating disc (904) is fixedly connected with a vertical rod (906), the outer wall of the vertical rod (906) is fixedly connected with a horizontal rod (907) in a symmetrical manner, the outer wall of the horizontal rod (907) is slidably connected with a scraper (908), the outer wall of the scraper (908) is fixedly connected with a guide frame (909) with a strip-shaped guide groove in an inclined manner, the inside of the vertical rod (906) is slidably connected with a cross (910) extending out of the vertical rod (906), the two side arms of the cross (910) extending out of the two ends of the vertical rod (906) are fixedly connected with slide rods (911) in a symmetrical manner respectively, the slide rods (911) are slidably connected to the inner wall of the strip-shaped guide groove, and the top end of the cross (910) is fixedly connected with a pressing cylinder (912).

8. A device for preparing a strip-shaped, lamellar crystal form of trans-4-(4-alkylcyclohexyl)phenol according to claim 7, characterized in that, The outer wall of the annular plate (811) is attached to the inner wall of the placing groove (813), the inner wall of the insertion groove (812) is attached to the outer wall of the insertion rod (814), the inner wall of the connecting groove (805) is attached to the outer wall of the connecting rod (803), and the outer extending end of the fixed block (806) is provided with an inclined surface and the outer extending end of the outer wall thereof is attached to the inner wall of the fixed groove (804).

9. The apparatus for preparing a strip-shaped, lamellar crystal form of trans-4-(4-alkylcyclohexyl)phenol according to claim 8, characterized by, The fixed block (806) is in the shape of L, the outer wall of the push plate (808) is provided with a threaded hole matched with the threaded rod (809), the outer wall of the square rod (903) is attached to the inner wall of the square groove (905), and the inner wall of the strip-shaped guide groove is attached to the outer wall of the slide rod (911).

10. A strip-shaped, platelet-shaped crystal form of trans-4-(4-alkylcyclohexyl)phenol according to the method of claim 1-3, characterized in that, The strip-shaped flaky single crystal prepared by the process has a thickness of 0.1-0.3 mm, a length-diameter ratio of 3:1-5:1, and a crystal lattice defect rate of ≤0.05%.

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