Preparation process of bio-based cardanol side chain modified polyfluorene luminescent material

Abstract

The present invention relates to the technical field of new biomass materials, and in particular to a preparation process of a novel bio-based cardanol side chain modified polyfluorene luminescent material. The process steps are as follows: 2,7-dibromofluorene and 1,3-dibromopropane are stirred and mixed at 70-80°C to generate 2,7-dibromo-9,9-bis(3-bromopropyl)-9H-fluorene (1); 2,7-dibromo-9,9-bis(3-bromopropyl)-9H-fluorene (1) and 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9,9-di-n-octylfluorene (2) are stirred and mixed at 95-105°C for 48h in a nitrogen environment to generate 9,9-bis(3-bromopropyl)-7,7'-dimethyl-9'9'-dioctyl-9H,9'H-2,2'-bifluorene (3); finally, 9,9-bis(3-bromopropyl)-7,7'-dimethyl-9'9'-dioctyl-9H,9'H-2,2'-bifluorene is mixed with a novel polyfluorene luminescent material additive (4) to generate a novel polyfluorene luminescent material 7,7'-dimethyl-9,9-dioctyl-9'9'-bis(cardanoloxypropyl)-9H,9'H-2,2'-bifluorene (5). The preparation process of the present invention improves the material properties of the novel fluorene derivative polymer.

Description

Technical Field

[0001] The present invention relates to the technical field of new biomass materials, and in particular to a preparation process of a novel bio-based cardanol side chain-modified polyfluorene luminescent material. Background Art

[0002] The performance research of new organic small molecules and polymer materials has attracted much attention in recent years. Among them, fluorene compounds have aroused extensive research interest among scientific researchers. Due to the advantages of fluorene compounds such as easy modification, good solubility and film-forming properties, excellent optical stability and thermal stability, and high fluorescence efficiency, they have potential commercial value in research fields such as organic optoelectronic functional materials, electroluminescent devices, photochromic devices, and pharmaceutical chemistry. On the other hand, cashew nut shell liquid, as a renewable bio-blended lipid extracted from cashew nut shell waste, can generate a mixture mainly composed of cardanol after simple heating treatment. Its cardanol polymer derivatives have good toughness, hydrophobicity, low permeability, self-drying and viscoelastic properties. Summary of the invention

[0003] The purpose of the present invention is to improve the added value of bio-based cardanol and to provide a novel preparation process of a polyfluorene luminescent material modified with a side chain of bio-based cardanol.

[0004] The above technical objectives of the present invention are achieved through the following technical solutions:

[0005] A preparation process of a novel bio-based cardanol side chain modified polyfluorene luminescent material, the process steps are as follows:

[0006] (1) 2,7-dibromofluorene and 1,3-dibromopropane are stirred and mixed at 70-80° C. to generate 2,7-dibromo-9,9-bis(3-bromopropyl)-9H-fluorene (1);

[0007] (2) 2,7-dibromo-9,9-bis(3-bromopropyl)-9H-fluorene (1) and 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9,9-dioctylfluorene (2) are mixed and reacted under nitrogen atmosphere at 95-105° C. for 48 hours to generate 9,9-bis(3-bromopropyl)-7,7'-dimethyl-9'9'-dioctyl-9H,9'H-2,2'-bifluorene (3);

[0008] (3) Finally, 9,9-bis(3-bromopropyl)-7,7'-dimethyl-9'9'-dioctyl-9H,9'H-2,2'-bifluorene is mixed with a novel polyfluorene luminescent material additive (4) to generate a novel polyfluorene luminescent material 7,7'-dimethyl-9,9-dioctyl-9'9'-bis(cardanoloxypropyl)-9H,9'H-2,2'-bifluorene (5).

[0009] The preparation process of the present invention improves the material properties of the novel fluorene derivative polymer and further improves its added value.

[0010] Preferably, the novel polyfluorene luminescent material additive is cardanol.

[0011] Cashew nut shell liquid (CNSL) is a renewable bio-blended lipid extracted from cashew nut shell waste. It can generate a mixture mainly composed of cardanol after a simple heating treatment. The cardanol obtained by purification is composed of phenol with side chain alkyl groups of different degrees of unsaturation (as shown in Formula 1). The derivative polymers of cardanol are generally considered to have good toughness, hydrophobicity, low permeability, self-drying and viscoelastic properties. The long-chain structure of cardanol easily generates intermolecular hydrogen bonds with other substances, providing energy for self-assembly; and its unique structure can be spatially complementary with certain copolymers, enabling molecular self-assembly. Self-assembled materials with functions and characteristics such as photoelectrocatalysis can be obtained through molecular self-assembly, which are widely used in nonlinear optical devices, chemistry and other fields.

[0012]

[0013] 2,7-dibromofluorene (2,7-dibromo-9H-fluorene) is an important intermediate raw material for the synthesis of fine chemicals and is widely used in the synthesis and preparation of dyes, photoconductive materials, luminescent materials and other materials. After a simple heating treatment, it can generate a mixture mainly composed of 2,7-dibromofluorene. The 2,7-dibromofluorene obtained by purification is shown in Formula 2.

[0014]

[0015] The production process of the present invention introduces bio-based cardanol and connects it to the side chain of the new fluorene derivative polymer, thereby improving the material properties of the new fluorene derivative polymer and further improving its added value. At the same time, the present invention expands the scope of use of cardanol and improves the added value of biological inedible cardanol.

[0016] As a preferred method, the preparation process of the novel bio-based cardanol side chain modified polyfluorene luminescent material comprises the following steps:

[0017] (1) 2,7-dibromofluorene and 1,3-dibromopropane are stirred and mixed at 75°C to generate 2,7-dibromo-9,9-bis(3-bromopropyl)-9H-fluorene (1); the reaction formula is:

[0018]

[0019] (2) 2,7-dibromo-9,9-bis(3-bromopropyl)-9H-fluorene (1) and 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9,9-dioctylfluorene (2) were mixed and reacted under nitrogen atmosphere at 99° C. for 48 h to generate 9,9-bis(3-bromopropyl)-7,7'-dimethyl-9'9'-dioctyl-9H,9'H-2,2'-bifluorene (3). The reaction formula is:

[0020]

[0021] (3) Finally, 3 was mixed with cardanol (4) to generate a novel polyfluorene luminescent material 7,7'-dimethyl-9,9-dioctyl-9'9'-bis(cardanoloxypropyl)-9H,9'H-2,2'-bifluorene (5) with excellent properties and the performance of cashew nut shell oil. The reaction formula is as follows:

[0022]

[0023] Preferably, the preparation process steps of the novel bio-based cardanol side chain modified polyfluorene luminescent material are as follows:

[0024] (1) Synthesis of 1

[0025] Add 2,7-dibromofluorene, tetrabutylammonium bromide and potassium hydroxide aqueous solution to the reaction bottle; stir at 70-80°C for 10-20 minutes, then add 1,3-dibromopropane; stir at 70-80°C for 20-40 minutes, and cool to room temperature; extract with dichloromethane, add 4-6wt% HCl solution and saturated NaCl solution respectively to combine the organic phase; dry with Na2SO4, purify with column, spin dry, and vacuum dry to obtain a white solid 1

[0026] (2) Synthesis of 3

[0027] In a reaction kettle, degassed toluene, white solid 1 and 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborol-2-yl)-9,9-dioctylfluorene were added respectively. After freezing and deoxygenating for 3 times, 1-3 mol / L K2CO3 and Pd(PPh3)4(0) were added to the mixture. The mixture was frozen and deoxygenated for 2-4 times again. Then, the mixture was stirred at 95-105°C for 45-55h under nitrogen atmosphere. After cooling to room temperature, toluene was added, the mixture was washed with brine, dried with MgSO4 for 4-8h, and the precipitate was filtered and concentrated in methanol to obtain a white solid product 3.

[0028] (3) Synthesis of 5

[0029] The white solid product 3, 9,9-bis(3-bromopropyl)-7,7'-dimethyl-9'9'-dioctyl-9H,9'H-2,2'-bifluorene and cardanol (4) were mixed in a reactor in a certain ratio, stirred at room temperature for a period of time, and then treated to obtain a novel polyfluorene luminescent material 5.

[0030]

[0031] Preferably, the preparation process steps of the novel bio-based cardanol side chain modified polyfluorene luminescent material are as follows:

[0032] (1) Synthesis of 1

[0033] Add 2,7-dibromofluorene, tetrabutylammonium bromide and potassium hydroxide aqueous solution to the reaction bottle; stir at 75°C for 15 minutes, then add 1,3-dibromopropane; stir at 75°C for 30 minutes, and cool to room temperature; extract with dichloromethane, add 5% HCl solution and saturated NaCl solution respectively, and combine the organic phase; dry with Na2SO4, purify with column, spin dry, and vacuum dry to obtain a white solid 1

[0034] (2) Synthesis of 3

[0035] In a reaction kettle, degassed toluene, 1 and 2 were added respectively. After freezing and deoxygenating for 3 times, 2 mol / L K2CO3 and Pd(PPh3)4(0) treated with nitrogen bubbles for 0.5 h were added to the mixture. After freezing and deoxygenating again, the mixture was stirred at 99°C for 48 h in a nitrogen environment. After cooling to room temperature, toluene was added, the mixture was washed with brine for 3 times, dried with MgSO4 for 6 h, filtered and concentrated in methanol to obtain a white solid product 3.

[0036] (3) Synthesis of 5

[0037] The white solid product 3 and cardanol 4 are mixed in a reactor in a certain ratio, stirred at room temperature for a period of time, and then treated to obtain a new polyfluorene luminescent material 5.

[0038]

[0039] Preferably, the freeze deoxygenation device used in the freeze deoxygenation process in the synthesis of the white solid product 3 in step (2) comprises a support frame and a tank body for storing a solvent installed above the support frame, the tank body comprising an inner tank body and an outer tank body arranged on the outside of the inner tank body, the inner tank body and the outer tank body are fixedly connected by a connecting piece, a cavity layer is formed between the inner tank body and the outer tank body, the outer surface of the inner tank body and the inner surface of the outer tank body are both provided with a reinforcing rib structure, a channel tube extending into the inner tank body is provided on the side of the inner tank body, the interior of the channel tube is connected to the cavity layer, a feed inlet is provided on the top of the inner tank body, an exhaust port is provided on one side of the feed inlet, a liquid inlet is provided on the top of the outer tank body, and a vacuum tube is also connected to the inner tank body.

[0040] In the prior art, the solvent to be frozen is immersed in liquid nitrogen. Since the tank containing the solvent is relatively large, the solvent in the middle is prone to not being able to be quickly frozen.

[0041] The device of the present invention adds the solvent to be degassed into a tank body that can withstand vacuum, fills the cavity layer with liquid nitrogen until all the solvent is completely frozen, opens the vacuum tube, and then performs vacuum treatment. The vacuum treatment is performed for 2-3 minutes, and the vacuum tube is closed to transfer the liquid nitrogen in the cavity layer to allow the solvent to slowly thaw. During the thawing process, the thawing under vacuum can allow the oxygen dissolved in the solvent to escape into the upper space in the inner tank body. After the solvent is thawed, the above steps are repeated three times to achieve deoxygenation treatment. The set channel tube can extend to the inside of the inner tank body, and the set fin structure also has good thermal conductivity. After the liquid nitrogen is introduced into the cavity layer, cold air can quickly enter the channel tube, and the channel tube cools the fin structure, and then the solvent is quickly frozen. It should be noted that the cold air can enter the fin structure through the through hole, which accelerates the freezing efficiency and is beneficial to the improvement of the preparation yield of the new polyfluorene luminescent material 5 in step (3) of the present invention.

[0042] As a preferred solution of the present invention, a circle of reinforcing plates are connected to the inner wall of the channel tube, reinforcing rods are connected to the reinforcing plates, fin structures are evenly connected to the channel tube, and the fin structures are arranged on the inner wall and outer wall of the channel tube;

[0043] The fin structure is a hollow sheet structure, and a through hole connected to the hollow of the fin structure is opened on the tube wall of the channel tube.

[0044] As a preferred solution of the present invention, a feed pipe is sealedly connected to the feed port, the feed pipe passes through the outer tank body, and the feed pipe and the outer tank body are fixedly connected.

[0045] As a preferred solution of the present invention, the exhaust port is connected to an exhaust component, and the exhaust component can exhaust the gas in the inner tank.

[0046] As a preferred solution of the present invention, the exhaust assembly includes a cannula inserted into the exhaust port, a valve body is arranged in the cannula, and a valve seat is slidably arranged in the cannula, a valve stem is fixedly connected above the valve seat, the valve seat is conical in shape, a convex ring is coaxially arranged on the valve stem, a spring is sleeved on the valve stem, one end of the spring abuts against the lower surface of the convex ring, and the other end of the spring abuts against the cannula;

[0047] The valve stem is clamped with a connecting rod, the connecting rod is in a truncated shape, the other end of the connecting rod is hinged with a hinge seat, the hinge seat is connected with a fixing rod, and the lower end of the fixing rod is hinged with a piston assembly;

[0048] The piston assembly comprises a piston cylinder which is arranged through the inner tank body and the outer tank body, a piston is slidably connected in the piston cylinder, and the outer end of the piston is hinged to the fixing rod.

[0049] As a preferred solution of the present invention, the upper end of the vacuum tube passes through the outer tank body, and an air pump is connected to the outer end of the vacuum tube.

[0050] After the vacuum is evacuated, the device of the present invention is left to stand for a period of time, and then the exhaust treatment is performed. Since the vacuum is evacuated, the inner tank body is in a vacuum state. Under the action of the external air pressure, the piston moves toward the inner side of the inner tank body. During the movement of the piston, the piston can drive the fixed rod to move downward, and the fixed rod can thereby pull one end of the connecting rod to move downward. Since the connecting rod is in a seesaw shape, when one end of the connecting rod moves downward, the other end moves upward. During the upward movement of the other end of the connecting rod, the valve stem can be driven to move upward. Since the lower end of the valve stem is connected to the valve seat, the valve seat also moves upward, so that the valve seat and the valve body can be opened, and the gas can be discharged from the cannula and the exhaust port. When the pressure in the inner tank body is basically balanced with the external pressure, the valve stem will be reset by the action of the spring. During the resetting process, the valve stem moves downward, and the other end of the connecting rod moves upward, so that the valve seat and the valve body are closed. Then the above steps are repeated to realize the deoxidation treatment, and automatic deoxidation can be realized. The air pressure of the inner tank body can be used to control the switch of the valve seat and the valve body, which is convenient to use.

[0051] As a preferred solution of the present invention, the liquid inlet is connected to a liquid inlet pipe, and a valve is installed on the liquid inlet pipe.

[0052] As a preferred solution of the present invention, an exhaust control component is plugged into the insert pipe;

[0053] The exhaust control component includes a socket opened on the insertion tube, an L-shaped rod is inserted into the socket, one end of the L-shaped rod is provided with a plug-in portion, the other end of the L-shaped rod is arranged above the valve stem, and the other end of the L-shaped rod is inclined, and the L-shaped rod is used to press the valve stem.

[0054] Preferably, in the preparation process of the white solid product 3 in step (2), the molar feed ratio of 1 to 2 is 1:0.8 to 1:1.2; based on the reaction economy and the difficulty of the subsequent refining operation, the molar feed ratio of 1 to 2 is selected to be 1:1 for feeding.

[0055] Preferably, in the preparation process of the novel polyfluorene luminescent material 5 in step (3), the theoretical ratio of 3 to 4 is 1:2 to 1:6; based on the reaction economy and the difficulty of the subsequent refining operation, the molar ratio of 3 to 4 is selected to be 1:4 for feeding.

[0056] In summary, the present invention has the following beneficial effects:

[0057] 1. The production process of the present invention introduces bio-based cardanol and connects it to the side chain of the new fluorene derivative polymer, thereby improving the material properties of the new fluorene derivative polymer and further improving its added value. At the same time, the present invention expands the scope of use of cardanol and improves the added value of biological inedible cardanol;

[0058] 2. The freezing and deoxygenation device of the present invention places the solvent to be degassed in an inner tank body (capable of withstanding vacuum), fills the cavity layer with liquid nitrogen, until all the solvent is completely frozen, opens the vacuum tube, and then performs vacuum treatment. The vacuum treatment is performed for 2-3 minutes, and the vacuum tube is closed to transfer the liquid nitrogen in the cavity layer out, so that the solvent is slowly thawed. During the thawing process, the thawing under vacuum can allow the oxygen dissolved in the solvent to escape into the upper space in the inner tank body. After the solvent is thawed, the above steps are repeated three times to achieve deoxygenation treatment. The channel tube can extend to the interior of the inner tank body, and the fin structure also has good thermal conductivity. After the liquid nitrogen is introduced into the cavity layer, cold air can quickly enter the channel tube, and the channel tube cools the fin structure, and then the solvent is quickly frozen. It should be noted that the cold air can enter the fin structure through the through hole, which accelerates the freezing efficiency; this is beneficial to the improvement of the preparation yield of the new polyfluorene luminescent material 5 in step (3) of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 It is a schematic structural diagram of a cryo-deoxygenation device used in the cryo-deoxygenation process in the synthesis of the white solid product 3 of the present invention;

[0060] Figure 2 This is a schematic diagram of the internal structure of the tank of the freezing and deoxygenation device of the present invention;

[0061] Figure 3 The refrigeration deoxygenation device of the present invention Figure 2 The enlarged structural diagram at A in the middle;

[0062] Figure 4 It is a schematic diagram of the three-dimensional structure of the exhaust assembly of the refrigeration and deoxygenation device of the present invention;

[0063] Figure 5 It is a schematic diagram of the front view structure of the exhaust assembly of the refrigeration and deoxygenation device of the present invention;

[0064] Figure 6 It is a schematic diagram of the side view of the exhaust assembly of the refrigeration and deoxygenation device of the present invention;

[0065] Figure 7 It is a schematic cross-sectional view of the exhaust assembly of the refrigeration and deoxygenation device of the present invention.

[0066] Description of the numbers in the figure:

[0067] 1. Support frame; 2. Tank body; 201. Inner tank body; 202. Outer tank body; 203. Connecting piece; 204. Cavity layer; 205. Channel tube; 2051. Reinforcement plate; 2052. Reinforcement rod; 2053. Fin structure; 2054. Through hole; 206. Feed inlet; 2061. Feed pipe; 207. Exhaust port; 208. Liquid inlet; 2081. Liquid inlet pipe; 2082. Valve; 20 9. Vacuum tube; 3. Exhaust assembly; 301. Insert tube; 302. Valve body; 303. Valve seat; 304. Valve stem; 305. Protruding ring; 306. Spring; 307. Connecting rod; 308. Articulated seat; 309. Fixed rod; 4. Piston assembly; 401. Piston cylinder; 402. Piston; 5. Vacuum pump; 6. Exhaust control assembly; 601. Socket; 602. L-shaped rod; 603. Connecting part. DETAILED DESCRIPTION

[0068] Example 1

[0069] (1) Synthesis of 1

[0070] Add 2,7-dibromofluorene (2.14 g, 6.2 mmol), tetrabutylammonium bromide (0.43 g, 1.24 mmol) and KOH solution (50 ml + 50 g) to the reaction flask. After stirring at 75 ° C for 15 min, add 1,3-dibromopropane (6.3 ml, 62 mmol), stir at 75 ° C for 30 min, and cool to room temperature. After extraction with dichloromethane, add 5% hydrogen chloride solution (20 ml) and saturated sodium chloride solution (20 ml) to combine the organic phase. Dry with sodium sulfate, purify with column, spin dry, and vacuum dry to obtain white solid 1 (3.233 g), with a yield of 95%.

[0071] (2) Synthesis of 3.

[0072] In a reaction kettle, degassed toluene (9 ml), 1 (0.39 g, 0.71 mmol) and 2 (0.40 g, 0.71 mmol) were added respectively. After freezing and deoxygenating for 3 times, 2 mol / L K2CO3 (15 ml) (after 0.5 h of nitrogen bubble treatment) and Pd(PPh3)4(0) (33 mg, 0.02 mmol) were added to the mixture, and freezing and deoxygenating was performed again. Then, the mixture was stirred at 99 ° C for 48 h under a nitrogen environment. After cooling to room temperature, toluene (20 ml) was added, and the mixture was washed with brine for 3 times, dried with MgSO4 for 6 h, and filtered and concentrated in methanol to obtain a white solid product 3 (0.45 g). The yield was 70%. 1 H-NMR (300 MHz, CDCl3): δ (ppm) 7.28-7.88 (m, fluorene ring hydrogen), 7.11-7.20 (s, benzene ring hydrogen), 3.11-3.30 (d, bromomethyl hydrogen), 2.40-2.48 (s, benzyl hydrogen), 0.55-2.40 (m, hydrogen on the side chain of polyfluorene).

[0073] (3) Synthesis of 5.

[0074] 3 (0.3632 g, 0.4 mmol) and 4 (0.2420 g, 0.8 mmol) were stirred in a reactor at a molar ratio of 1:2 to obtain a novel polyfluorene luminescent material 5 (0.414 g) with a yield of 87%. 1 H-NMR (300 MHz, CDCl3): δ (ppm) 7.28-7.88 (m, hydrogen on fluorene ring), 7.11-7.20 (m, hydrogen on benzene ring on polyfluorene and cardanol), 4.87-6.38 (m, hydrogen on unsaturated fatty chain on cardanol), 0.55-2.40 (m, hydrogen on saturated fatty chain on polyfluorene side chain and cardanol).

[0075] Example 2

[0076] (1) Synthesis of 1

[0077] Add 2,7-dibromofluorene, tetrabutylammonium bromide and potassium hydroxide aqueous solution into a reaction flask; stir at 70°C for 10 min, then add 1,3-dibromopropane; stir at 70°C for 20 min, and cool to room temperature; extract with dichloromethane, then add 4 wt% HCl solution and saturated NaCl solution to combine the organic phases; dry with Na2SO4, purify with a column, spin dry, and dry in vacuo to obtain a white solid 1.

[0078] (2) Synthesis of 3.

[0079] In a reaction kettle, degassed toluene, white solid 1 and 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9,9-dioctylfluorene were added respectively, with the molar feed ratio of 1 to 2 being 1:0.8. After freeze-deoxygenation for 3 times, 1 mol / L K2CO3 and Pd(PPh3)4(0) were added to the mixture, and freeze-deoxygenation was repeated twice again. After that, the mixture was stirred at 95°C for 45 h under a nitrogen environment. After cooling to room temperature, toluene was added, the mixture was washed with brine, dried with MgSO4 for 8 h, and the precipitate was filtered and concentrated in methanol to obtain a white solid product 3.

[0080] See also Figure 1-7 The freezing deoxygenation device used for freezing deoxygenation treatment includes a support frame 1 and a tank body 2 installed above the support frame 1 for storing a solvent. The tank body 2 is a thickened metal tank with good structural strength and good pressure resistance. The tank body 2 includes an inner tank body 201 and an outer tank body 202 arranged outside the inner tank body 201. The inner tank body 201 contains a solution that needs freezing deoxygenation. The inner tank body 201 and the outer tank body 202 are fixedly connected by a connecting piece 203. The connecting piece 203 is arranged 3. The inner tank body 201 and the outer tank body 202 can be fixed to improve the structural strength of the connection between the inner tank body 201 and the outer tank body 202. There is a cavity layer 204 between the inner tank body 201 and the outer tank body 202. The cavity layer 204 can be filled with liquid nitrogen for freezing the inner tank body 201. The outer surface of the inner tank body 201 and the inner surface of the outer tank body 202 are both provided with a reinforcing rib structure, and the provided reinforcing rib structure is also to increase the structural strength of the inner tank body 201 and the outer tank body 202.

[0081] A channel tube 205 extending into the inner tank body 201 is provided on the side of the inner tank body 201, and the interior of the channel tube 205 is connected to the cavity layer 204. The channel tube 205 can be filled with liquid nitrogen, which can quickly freeze the solution in the inner tank body 201 and improve the structural strength of the inner tank body 201. Since the inner tank body 201 needs to be vacuumed when in use, if the structural strength of the inner tank body 201 is not enough, the inner tank body 201 may be deformed, affecting the subsequent deoxygenation operation. The channel tube 205 can make the shape of the inner tank body 201 a horizontal double-layer water cup with higher structural strength. A feed inlet 206 is provided on the top of the inner tank body 201, and an exhaust port 207 is provided on one side of the feed inlet 206. A liquid inlet 208 is provided on the top of the outer tank body 202, and a vacuum tube 209 is also connected to the inner tank body 201. Liquid material can be added into the inner tank body 201 through the feed port 206 , exhaust treatment can be performed through the exhaust port 207 , vacuum treatment can be performed through the provided vacuum pipe 209 , and liquid nitrogen can be added through the provided liquid inlet 208 .

[0082] When in use, the solvent to be degassed is placed in the inner tank body 201 (which can withstand vacuum), and liquid nitrogen is filled into the cavity layer 204 until all the solvent is completely frozen. The vacuum tube 209 is opened, and then vacuum treatment is performed. The vacuum treatment is performed for 2-3 minutes, and the vacuum tube 209 is closed to transfer the liquid nitrogen in the cavity layer 204 out, so that the solvent is slowly thawed. During the thawing process, thawing under vacuum can allow the oxygen dissolved in the solvent to escape to the upper space in the inner tank body 201. After the solvent is thawed, the above steps are repeated three times to achieve deoxygenation treatment.

[0083] In order to achieve the rapid freezing process, a circle of reinforcing plates 2051 are connected to the inner wall of the channel tube 205, and reinforcing rods 2052 are connected to the reinforcing plates 2051. Fin structures 2053 are evenly connected to the channel tube 205, and the fin structures 2053 are arranged on the inner wall and the outer wall of the channel tube 205;

[0084] The fin structure 2053 is a hollow sheet-like structure, and a through hole 2054 communicating with the hollow of the fin structure 2053 is provided on the tube wall of the channel tube 205 .

[0085] The channel tube 205 can extend to the interior of the inner tank body 201, and the fin structure 2053 also has good thermal conductivity. After liquid nitrogen is introduced into the cavity layer 204, cold air can quickly enter the channel tube 205, and the channel tube 205 cools the fin structure 2053, and then quickly freezes the solvent. It should be noted that cold air can enter the fin structure 2053 through the through hole 2054, thereby accelerating the freezing efficiency.

[0086] The feed port 206 is sealed with a feed pipe 2061, which penetrates the outer tank body 202 and is fixedly connected to the outer tank body 202. The feed pipe 2061 can be used to add solvent to the inner tank body 201.

[0087] The liquid inlet 208 is connected to a liquid inlet pipe 2081, on which a valve 2082 is installed. The liquid inlet pipe 2081 can replenish liquid nitrogen into the cavity layer 204, and the valve 2082 is convenient for switching. It should be noted that a drain port is provided at the bottom of the outer tank body 202 to discharge the liquid nitrogen.

[0088] (3) Synthesis of 5.

[0089] 3 (0.3632 g, 0.4 mmol) and 4 (0.7260 g, 2.4 mmol) were stirred and reacted in a reactor at a molar ratio of 1:6. After treatment, a new polyfluorene luminescent material 5 (0.452 g) was obtained with a yield of 95%.

[0090] Example 3

[0091] (1) Synthesis of 1

[0092] Add 2,7-dibromofluorene, tetrabutylammonium bromide and potassium hydroxide aqueous solution into a reaction flask; stir at 80°C for 20 min, then add 1,3-dibromopropane; stir at 80°C for 40 min, and cool to room temperature; extract with dichloromethane, then add 6wt% HCl solution and saturated NaCl solution to combine the organic phases; dry with Na2SO4, purify with a column, spin dry, and dry in vacuo to obtain a white solid 1.

[0093] (2) Synthesis of 3.

[0094] In a reaction kettle, degassed toluene, white solid 1 and 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9,9-dioctylfluorene were added respectively, with a molar feed ratio of 1 to 2 of 1:1.2. After freezing and deoxygenating twice, 3 mol / L K2CO3 and Pd(PPh3)4(0) were added to the mixture, and freezing and deoxygenating were repeated twice again. Then, the mixture was stirred at 105°C for 55 h under a nitrogen environment. After cooling to room temperature, toluene was added, washed with brine, dried with MgSO4 for 4 h, and the precipitate was filtered and concentrated in methanol to obtain a white solid product 3.

[0095] After the solvent is completely frozen, it needs to be deoxygenated, which is done by slowly warming up. During the warming up process, the oxygen in the solvent is slowly released and then discharged to the outside through exhaust. However, the above process generally needs to be continued several times to achieve a better deoxygenation effect.

[0096] In the present application, an exhaust component 3 is connected to the exhaust port 207 , and the exhaust component 3 can exhaust the gas in the inner tank body 201 .

[0097] The exhaust assembly 3 includes a cannula 301 inserted into the exhaust port 207, a valve body 302 is arranged in the cannula 301, and a valve seat 303 is slidably arranged in the cannula 301, a valve stem 304 is fixedly connected above the valve seat 303, the valve seat 303 is conical in shape, a convex ring 305 is coaxially arranged on the valve stem 304, a spring 306 is sleeved on the valve stem 304, one end of the spring 306 abuts against the lower surface of the convex ring 305, and the other end of the spring 306 abuts against the cannula 301;

[0098] A connecting rod 307 is clamped on the valve stem 304, and the connecting rod 307 is in a seesaw shape. The other end of the connecting rod 307 is hinged to a hinge seat 308, and a fixing rod 309 is connected to the hinge seat 308. The lower end of the fixing rod 309 is hinged to the piston assembly 4.

[0099] The piston assembly 4 includes a piston cylinder 401 penetrating the inner tank body 201 and the outer tank body 202 . A piston 402 is slidably connected in the piston cylinder 401 . The outer end of the piston 402 is hinged to the fixing rod 309 .

[0100] The upper end of the vacuum tube 209 passes through the outer tank body 202 , and the outer end of the vacuum tube 209 is connected to an air pump 5 .

[0101] It is necessary to first perform a vacuum operation to make the inner tank body 201 a vacuum environment. Since the inner tank body 201 is vacuumed, in order to prevent the inner tank body 201 from deforming, in the present application, the inner tank body 201 is made of metal material and is provided with reinforcing ribs, which can greatly improve the structural strength of the inner tank body 201 and has a strong anti-deformation ability;

[0102] After the vacuum is drawn, it is left to stand for a while, and then the exhaust treatment is performed. Since the vacuum has been drawn, the inner tank body 201 is in a vacuum state. Under the action of the external air pressure, the piston 402 moves toward the inner side of the inner tank body 201. During the movement of the piston 402, the piston 402 can drive the fixed rod 309 to move downward, and the fixed rod 309 can thereby pull one end of the connecting rod 307 to move downward. Since the connecting rod 307 is in a seesaw shape, when one end of the connecting rod 307 moves downward, the other end moves upward. During the upward movement of the other end of the connecting rod 307, the valve stem 304 can be driven to move upward. Since the lower end of the valve stem 304 is connected to the valve seat 303, the valve seat 303 also moves upward, so that the valve seat 303 and the valve body 302 can be opened, and the gas can be discharged from the insert tube 301 and the exhaust port 207.

[0103] When the pressure in the inner tank body 201 is basically balanced with the external pressure, the valve stem 304 will be reset by the action of the spring 306. During the reset process, the valve stem 304 moves downward and the other end of the connecting rod 307 moves upward, thereby closing the valve seat 303 and the valve body 302. Then, the above steps are repeated to achieve deoxidation treatment.

[0104] During the deoxygenation process, after the vacuum is drawn, it is necessary to stand for a period of time to allow the oxygen in the solvent to be fully released, and then exhaust treatment can be performed. However, after the vacuum is drawn, the inner tank body 201 is in a vacuum state, and the piston 402 will move inward. In order to prevent the piston 402 from moving.

[0105] The exhaust control component 6 is plugged into the insert tube 301; the exhaust control component 6 includes a plug hole 601 opened on the insert tube 301, an L-shaped rod 602 is plugged into the plug hole 601, one end of the L-shaped rod 602 is provided with a plug-in portion 603, the other end of the L-shaped rod 602 is arranged above the valve stem 304, and the other end of the L-shaped rod 602 is inclined, and the L-shaped rod 602 is used to press the valve stem 304.

[0106] An L-shaped rod 602 is provided on the insert tube 301. The L-shaped rod 602 can fix the valve stem 304 to prevent the valve stem 304 from moving, so that the valve seat 303 and the valve body 302 can be closed. When exhaust treatment is required, it is only necessary to remove the L-shaped rod 602. It should be noted that one end of the L-shaped rod 602 is inclined, which can facilitate the L-shaped rod 602 to be stuck on the insert tube 301. In addition, the L-shaped rod 602 can be controlled by a cylinder to achieve automation.

[0107] Working principle and use process of the present invention: When using the device, first insert the L-shaped rod 602 into the insert tube 301. The L-shaped rod 602 can fix the valve stem 304 to prevent the valve stem 304 from moving, so that the valve seat 303 and the valve body 302 can be closed. When exhaust treatment is required, only the L-shaped rod 602 needs to be removed;

[0108] Place the solvent to be degassed in the inner tank 201 (which can withstand vacuum), fill the cavity layer 204 with liquid nitrogen until all the solvent is completely frozen, open the vacuum tube 209, and then perform vacuum treatment for 2-3 minutes, close the vacuum tube 209, transfer the liquid nitrogen in the cavity layer 204 out, and let the solvent thaw slowly. During the thawing process, thawing under vacuum can allow the oxygen dissolved in the solvent to escape to the upper space in the inner tank 201. After the solvent is thawed, repeat the above steps three times to achieve deoxygenation treatment;

[0109] The channel tube 205 can extend to the interior of the inner tank 201, and the fin structure 2053 also has good thermal conductivity. After the liquid nitrogen is introduced into the cavity layer 204, the cold air can quickly enter the channel tube 205, and the channel tube 205 cools the fin structure 2053, and then quickly freezes the solvent. It should be noted that the cold air can enter the fin structure 2053 through the through hole 2054, which speeds up the freezing efficiency.

[0110] After the vacuum is drawn, it is left to stand for a while, and then the exhaust treatment is performed. Since the vacuum has been drawn, the inner tank body 201 is in a vacuum state. Under the action of the external air pressure, the piston 402 moves toward the inner side of the inner tank body 201. During the movement of the piston 402, the piston 402 can drive the fixed rod 309 to move downward, and the fixed rod 309 can thereby pull one end of the connecting rod 307 to move downward. Since the connecting rod 307 is in a seesaw shape, when one end of the connecting rod 307 moves downward, the other end moves upward. During the upward movement of the other end of the connecting rod 307, the valve stem 304 can be driven to move upward. Since the lower end of the valve stem 304 is connected to the valve seat 303, the valve seat 303 also moves upward, so that the valve seat 303 and the valve body 302 can be opened, and the gas can be discharged from the insert tube 301 and the exhaust port 207.

[0111] When the pressure in the inner tank body 201 is basically balanced with the external pressure, the valve stem 304 will be reset by the action of the spring 306. During the reset process, the valve stem 304 moves downward and the other end of the connecting rod 307 moves upward, thereby closing the valve seat 303 and the valve body 302. Then, the above steps are repeated to achieve deoxidation treatment.

[0112] (3) Synthesis of 5.

[0113] 3 (0.3632 g, 0.4 mmol) and 4 (0.4840 g, 1.6 mmol) were stirred and reacted in a reactor at a molar ratio of 1:4. After treatment, a new polyfluorene luminescent material 5 (0.452 g) was obtained with a yield of 95%.

[0114] This specific embodiment is merely an explanation of the present invention and is not a limitation of the present invention. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed. However, as long as they are within the scope of the claims of the present invention, they are protected by the patent law.

Claims

1. A freezing deoxygenation device for the preparation process of a bio-based cardanol side chain modified polyfluorene luminescent material, characterized in that: The invention comprises a support frame (1) and a tank body (2) for storing a solvent and mounted on the support frame (1), wherein the tank body (2) comprises an inner tank body (201) and an outer tank body (202) arranged outside the inner tank body (201), the inner tank body (201) and the outer tank body (202) being fixedly connected via a connecting piece (203), a cavity layer (204) being provided between the inner tank body (201) and the outer tank body (202), a reinforcing rib structure being provided on the outer surface of the inner tank body (201) and the inner surface of the outer tank body (202), a channel tube (205) extending toward the inside of the inner tank body (201) being provided on the side surface of the inner tank body (201), the channel tube The interior of the channel tube (205) is connected to the cavity layer (204); a feed inlet (206) is provided on the top of the inner tank body (201); an exhaust port (207) is provided on one side of the feed inlet (206); a liquid inlet (208) is provided on the top of the outer tank body (202); and a vacuum tube (209) is also connected to the inner tank body (201); a circle of reinforcing plates (2051) are connected to the inner wall of the channel tube (205); a reinforcing rod (2052) is connected to the reinforcing plate (2051); fin structures (2053) are evenly connected to the channel tube (205); and the fin structures (2053) are arranged on the inner wall and the outer wall of the channel tube (205); The fin structure (2053) is a hollow sheet-like structure, and a through hole (2054) connected to the hollow of the fin structure (2053) is provided on the tube wall of the channel tube (205).

2. The freezing deoxygenation device for the preparation process of a bio-based cardanol side chain modified polyfluorene luminescent material according to claim 1, characterized in that: The feed port (206) is sealedly connected to a feed pipe (2061), the feed pipe (2061) passes through the outer tank body (202), and the feed pipe (2061) and the outer tank body (202) are fixedly connected; the exhaust port (207) is connected to an exhaust component (3), and the exhaust component (3) can exhaust the gas in the inner tank body (201).

3. The freezing deoxygenation device for the preparation process of a bio-based cardanol side chain modified polyfluorene luminescent material according to claim 2, characterized in that: The exhaust assembly (3) comprises a plug (301) inserted into the exhaust port (207), a valve body (302) is arranged in the plug (301), and a valve seat (303) is slidably arranged in the plug (301), a valve stem (304) is fixedly connected to the top of the valve seat (303), the valve seat (303) is in a conical shape, a convex ring (305) is coaxially arranged on the valve stem (304), a spring (306) is sleeved on the valve stem (304), one end of the spring (306) is against the lower surface of the convex ring (305), and the other end of the spring (306) is against the plug (301); A connecting rod (307) is clamped on the valve stem (304), the connecting rod (307) is in a seesaw shape, the other end of the connecting rod (307) is hinged to a hinge seat (308), a fixing rod (309) is connected to the hinge seat (308), and the lower end of the fixing rod (309) is hinged to a piston assembly (4); The piston assembly (4) comprises a piston cylinder (401) which is arranged through the inner tank body (201) and the outer tank body (202), a piston (402) being slidably connected inside the piston cylinder (401), and an outer end of the piston (402) is hinged to a fixing rod (309).

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