Polyphenylene sulfide preparation system

Abstract

The utility model discloses a polyphenylene sulfide preparation system, and relates to the technical field of high polymer materials. The polyphenylene sulfide preparation system comprises a reaction kettle, a water removal tower and a first heating device, the upper part of the reaction kettle is provided with a feed port and an exhaust port, the middle part of the reaction kettle is provided with a nitrogen introduction pipe, and the bottom of the reaction kettle is provided with a hydrogen sulfide input pipe; the water removal tower is arranged at the top of the reaction kettle and is communicated with the exhaust port, and a first exhaust pipe is arranged at the top of the water removal tower; and the first heating device is arranged on the water removal tower. And the temperature in the water removal tower is kept at 100-120 DEG C, so that water vapor generated in the reaction kettle can be smoothly discharged from the reaction kettle, water generated in the reaction can be timely and effectively removed, the water is prevented from interfering with the reaction process, the smooth reaction and the high purity of the phenyl disulfide intermediate are ensured, and the purity of the prepared polyphenylene sulfide is ensured.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and in particular to a polyphenylene sulfide preparation system. Background Art

[0002] Polyphenylene sulfide (PPS) is a high-performance polymer widely used in the electronics, electrical, and automotive industries due to its excellent thermal stability, chemical resistance, and mechanical strength. Currently, the main method for synthesizing PPS is the sodium sulfide method.

[0003] The sodium sulfide method is a commonly used industrial method for synthesizing PPS. It produces PPS through a condensation reaction between dichlorobenzene and anhydrous sodium sulfide in a polar solvent. While this method offers advantages such as readily available raw materials and high-quality products, it also suffers from slow reaction rates and numerous side reactions, resulting in low product purity and yield.

[0004] Although the use of phenyl disulfide and cyclopentane sulfone to prepare PPS can reduce the generation of waste liquid, there are also problems such as low product purity. Utility Model Content

[0005] The main purpose of this application is to propose a polyphenylene sulfide preparation system, aiming to solve the problem of low purity of polyphenylene sulfide produced in the prior art.

[0006] To achieve the above objectives, the polyphenylene sulfide preparation system proposed in this application includes:

[0007] The reactor is provided with a feed port and an exhaust port at the top, a nitrogen inlet pipe in the middle, and a hydrogen sulfide input pipe at the bottom;

[0008] a dehydration tower, disposed on the top of the reactor and connected to the exhaust port, wherein a first exhaust pipe is provided on the top of the dehydration tower; and

[0009] A first heating device is provided on the dehydration tower, and is used to ensure that the temperature in the dehydration tower is not lower than 100°C.

[0010] In one embodiment, the first heating device includes a first jacket provided on the outer wall of the water removal tower, a first heat transfer oil inlet is provided at a lower portion of one side of the first jacket, and a first heat transfer oil outlet is provided at an upper portion of the other side of the first jacket.

[0011] In one embodiment, the polyphenylene sulfide preparation system further includes a separation device, wherein the separation device includes:

[0012] A condenser, having an air inlet provided on a side wall at its lower portion and a second exhaust pipe provided on the top, wherein the air inlet is connected to the first exhaust pipe; and

[0013] A cooling device is provided on the condenser, and is used to reduce the temperature in the condenser so as to liquefy the water vapor.

[0014] In one embodiment, the separation device further includes a liquid collecting tank, which is connected to the bottom of the condenser via a first liquid drain pipe, and the liquid collecting tank is located below the condenser.

[0015] In one embodiment, the first liquid drain pipe comprises:

[0016] a liquid sealing pipe having a lower section connected to the bottom of the condenser and an upper section connected to the lower section, wherein the upper section exceeds the bottom end of the condenser; and

[0017] A liquid outlet pipe has one end connected to the higher section and the other end connected to the liquid collecting tank.

[0018] In one embodiment, the polyphenylene sulfide preparation system further includes a hydrogen sulfide collector for liquefying gaseous hydrogen sulfide into liquid hydrogen sulfide, and an air inlet end of the hydrogen sulfide collector is connected to the second exhaust pipe.

[0019] In one embodiment, the polyphenylene sulfide preparation system further includes a dryer disposed between the hydrogen sulfide collector and the condenser, and the dryer is used to dry hydrogen sulfide.

[0020] In one embodiment, the polyphenylene sulfide preparation system further includes a hydrogen sulfide vaporizer, the gas outlet of the hydrogen sulfide vaporizer is connected to the hydrogen sulfide input pipe, and the liquid inlet of the hydrogen sulfide vaporizer is connected to the second liquid drain pipe on the hydrogen sulfide collector.

[0021] In one embodiment, the polyphenylene sulfide preparation system further includes a second heating device disposed on the reactor; and / or,

[0022] The polyphenylene sulfide preparation system further includes a stirring device arranged in the reactor.

[0023] In one embodiment, the second heating device includes a second jacket disposed on the outer wall of the reactor, wherein a second heat transfer oil inlet is disposed at a lower portion of one side of the second jacket, and a second heat transfer oil outlet is disposed at an upper portion of the other side of the second jacket.

[0024] In the technical solution of the present application, nitrogen is introduced into the reactor through a nitrogen inlet pipe, and phenol, phosphoric acid and a modified titanate catalyst are added to the reactor under a nitrogen protective atmosphere; the heating device on the reactor is started to make the temperature of the mixed liquid in the reactor 150-180°C, and the mixture is stirred. Hydrogen sulfide is introduced into the mixed liquid through a hydrogen sulfide inlet pipe, and stirring is maintained. Under the joint catalytic action of phosphoric acid and the modified titanate catalyst, the sulfur in the hydrogen sulfide first reacts with the phenol to generate a phenylmercaptan intermediate, and then the phenylmercaptan is dehydrated and condensed to generate phenyl disulfide. The water generated in the reaction is vaporized into water vapor, and the water vapor is discharged from the exhaust port along with the overflowing hydrogen sulfide and nitrogen. The water vapor, hydrogen sulfide and nitrogen discharged from the exhaust port flow into a dehydration tower. The temperature in the dehydration tower is maintained at 100-120°C, which allows the water vapor to be discharged from the reactor more smoothly, and the water generated by the reaction is removed in a timely and effective manner to prevent it from interfering with the reaction process, thereby ensuring the smooth progress of the reaction and the high purity of the phenyl disulfide intermediate, thereby ensuring the purity of the prepared polyphenylene sulfide.

[0025] After the phenyl disulfide intermediate is generated, the temperature of the solution in the reactor is adjusted to 220-250°C, stirring is maintained, and sulfolane and a modified titanate catalyst are added. The sulfolane provides an optimal reaction environment, and under the catalytic action of the modified titanate catalyst, the phenyl disulfide undergoes a polymerization reaction to generate a long-chain polymer, namely polyphenylene sulfide (PPS). The generated polyphenylene sulfide is mixed with a solvent system to obtain a polyphenylene sulfide solution. The obtained polyphenylene sulfide solution is filtered for solid-liquid separation to obtain a solid. The solid is washed, crushed, and dried to obtain polyphenylene sulfide with high yield and purity. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying any creative work.

[0027] Figure 1 This is a structural schematic diagram of an embodiment of a polyphenylene sulfide preparation system provided in this application;

[0028] Figure 2 for Figure 1 Schematic diagram of the liquid seal tube structure.

[0029] Description of Figure Numbers:

[0030] 1. Reactor; 11. Feed inlet; 12. Exhaust port; 13. Nitrogen inlet pipe; 14. Hydrogen sulfide inlet pipe; 15. Stirring device; 16. Second jacket; 161. Second thermal oil inlet; 162. Second thermal oil outlet; 2. Dewatering tower; 21. First exhaust pipe; 22. First jacket; 221. First thermal oil inlet; 222. First thermal oil outlet; 3. Condenser; 31. First drain pipe; 311. Liquid seal pipe; 311a. Lower section; 311b. Upper section; 311c. Liquid level; 312. Liquid outlet pipe; 32. Liquid collecting tank; 33. Second exhaust pipe; 34. Third jacket; 341. Cooling water inlet; 342. Cooling water outlet; 4. Dryer; 5. Hydrogen sulfide collector; 51. Second drain pipe; 52. Gas outlet; 6. Hydrogen sulfide vaporizer; 61. Liquid inlet pipe.

[0031] The realization of the objectives, functional features and advantages of this application will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0032] The following will be combined with the accompanying drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments of this application, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of this application.

[0033] It should be noted that if the embodiments of the present application involve directional indications (such as up, down, left, right, front, back, etc.), the directional indications are only used to explain the relative position relationship, movement status, etc. between the components under a certain specific posture. If the specific posture changes, the directional indications will also change accordingly.

[0034] In addition, if there are descriptions involving "first", "second", etc. in the embodiments of the present application, the descriptions of "first", "second", etc. are only for descriptive purposes and cannot be understood as indicating or suggesting their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features limited to "first" and "second" may explicitly or implicitly include at least one of such features. In addition, if "and / or" or "and / or" appears in the full text, its meaning includes three parallel schemes. Taking "A and / or B" as an example, it includes scheme A, or scheme B, or a scheme in which A and B are satisfied at the same time. In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the ability of ordinary technicians in this field to implement it. When the combination of technical solutions is mutually contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by this application.

[0035] Although the use of phenyl disulfide and cyclopentane to prepare PPS can reduce the generation of waste liquid, it also has problems such as low product purity. In view of this, the present application proposes a polyphenylene sulfide preparation system to solve the problem of low purity of polyphenylene sulfide produced in the prior art.

[0036] See also Figure 1 and Figure 2 In one embodiment of the present application, the polyphenylene sulfide preparation system includes: a reactor 1, a dehydration tower 2, and a first heating device. The upper part of the reactor 1 is provided with a feed port 11 and an exhaust port 12, the middle part of the reactor 1 is provided with a nitrogen inlet pipe 13, and the bottom of the reactor 1 is provided with a hydrogen sulfide input pipe 14; the dehydration tower 2 is provided at the top of the reactor 1 and is connected to the exhaust port 12, and the top of the dehydration tower 2 is provided with a first exhaust pipe 21; the first heating device is provided on the dehydration tower 2, and the first heating device is used to make the temperature in the dehydration tower 2 not lower than 100°C.

[0037] In the technical solution of the present application, nitrogen is introduced into the reactor 1 through the nitrogen inlet pipe 13. Phenol, phosphoric acid, and a modified titanate catalyst are added to the reactor 1 under a nitrogen protective atmosphere. The heating device on the reactor 1 is started to increase the temperature of the mixed liquid in the reactor 1 to 150-180°C. Stirring is then carried out. Hydrogen sulfide (H2S) is introduced into the mixed liquid through the hydrogen sulfide inlet pipe 14. Stirring is maintained. Under the combined catalytic action of the phosphoric acid and the modified titanate catalyst, the sulfur in the hydrogen sulfide first reacts with the phenol to form a phenylmercaptan intermediate. Subsequently, the phenylmercaptan undergoes dehydration condensation to form phenyl disulfide. The water generated in the reaction is vaporized to form water vapor, which is discharged from the exhaust port 12 along with the overflowing hydrogen sulfide and nitrogen. While the reactor 1 is being heated, the first heating device is started to increase the temperature in the dehydration tower 2 to 100-120°C. The water vapor, hydrogen sulfide, and nitrogen discharged from the exhaust port 12 flow into the dehydration tower 2. The temperature in the dehydration tower 2 is maintained at 100-120°C, which allows the water vapor and other gases to be discharged from the reactor 1 more smoothly. This effectively removes the water generated by the reaction and prevents it from interfering with the reaction process, ensuring the smooth progress of the reaction and the high purity of the phenyl disulfide intermediate, thereby ensuring the purity of the prepared polyphenylene sulfide. The chemical formula of phenyl mercaptan is C6H5SH, and the chemical formula of phenyl disulfide is C6H5SSPh.

[0038] After the phenyl disulfide intermediate is generated, the input of hydrogen sulfide is stopped, the temperature of the solution in the reactor 1 is adjusted to 220-250°C, stirring is maintained, and cyclopentane and a modified titanate catalyst are added. Cyclopentane provides a better reaction environment, and under the catalytic action of the modified titanate catalyst, phenyl disulfide undergoes a polymerization reaction to generate a long-chain polymer, that is, polyphenylene sulfide (PPS). The generated polyphenylene sulfide is mixed in the solvent system to obtain a polyphenylene sulfide solution. The obtained polyphenylene sulfide solution is filtered for solid-liquid separation to obtain a solid. The solid is washed, crushed and dried to obtain polyphenylene sulfide with an average particle size of 2 mm, and the yield and purity of the obtained polyphenylene sulfide are both high. It is understandable that a valve is provided on the feed port 11. When raw materials need to be added, the valve is in an open state. After the raw materials are added, the valve is in a closed state.

[0039] It should be noted that the raw materials for preparing the modified titanate catalyst include tetrabutyl titanate, acetylacetone and glycolic acid. Specifically, the preparation method of the modified titanate catalyst includes the following steps:

[0040] (1) Under a nitrogen atmosphere, tetrabutyl titanate is added to a reaction vessel, the temperature of the solution in the reaction vessel is controlled to be 60-80° C., and the mixture is stirred. Acetylacetone is added, and a titanate acetylacetone complex is obtained after reaction.

[0041] (2) controlling the temperature of the solution in the reaction container to 80-90° C., maintaining stirring, adding glycolic acid, and reacting to obtain a modified titanate catalyst solution;

[0042] (3) Cooling the modified titanate catalyst solution obtained in step (2) to room temperature, removing volatile components by reduced pressure distillation to obtain a powdered modified titanate catalyst.

[0043] By adopting the above technical solution, the titanium center in tetrabutyl titanate is an electron-deficient center, which easily combines with the carbonyl oxygen atom of acetylacetone to form a titanate acetylacetonate complex. The chemical formula of tetrabutyl titanate is Ti(OBu)4, the chemical formula of acetylacetone is AcAcH, and the chemical formula of the titanate acetylacetonate complex is Ti(OAcAc).

[0044] Hydroxyacetic acid is added to the acetylacetonate titanate complex system. Hydroxyacetic acid has two active groups, namely carboxylic acid and hydroxyl groups. These two active groups can react with the acetylacetonate titanate complex to form a new organic titanium compound, namely a modified titanate catalyst. The chemical formula of hydroxyacetic acid is HOCH2COOH, and the chemical formula of the modified titanate catalyst is Ti(OAcAc)(OCH2COOH).

[0045] Volatile components in the reaction system, such as butanol and water, are removed by distillation under reduced pressure to obtain a relatively pure powdered modified titanate catalyst.

[0046] Furthermore, in the preparation method of the modified titanate catalyst, the mass ratio of tetrabutyl titanate, acetylacetone and glycolic acid is (80-90): (46-55): (17-20).

[0047] In an embodiment of the present application, the first heating device includes a first jacket 22 arranged on the outer wall of the water removal tower 2, and a first thermal oil inlet 221 is provided at the lower portion of one side of the first jacket 22, and a first thermal oil outlet 222 is provided at the upper portion of the other side.

[0048] By adopting the above technical solution, a first jacket 22 is provided on the outer wall of the dewatering tower 2, and a first heat transfer oil inlet 221 is provided at the lower portion of one side of the first jacket 22, and a first heat transfer oil outlet 222 is provided at the upper portion of the other side. When preparing polyphenylene sulfide, heat transfer oil with a temperature of 100-120°C flows into the first jacket 22 from the first heat transfer oil inlet 221, and the heat transfer oil in the first jacket 22 flows out from the first heat transfer oil outlet 222. This cycle is repeated to maintain the temperature in the dewatering tower 2 at 100-120°C. This allows water vapor and other gases to be discharged from the reactor 1 more smoothly, and the water generated by the reaction is removed in a timely and effective manner to prevent it from interfering with the reaction process, thereby ensuring the smooth progress of the reaction and the high purity of the phenyl disulfide intermediate, thereby ensuring the purity of the prepared polyphenylene sulfide.

[0049] In an embodiment of the present application, the polyphenylene sulfide preparation system also includes a separation device, which includes a condenser 3 and a cooling device. An air inlet is provided on the side wall of the lower part of the condenser 3, and a second exhaust pipe 33 is provided on the top of the condenser 3. The air inlet is connected to the first exhaust pipe 21; the cooling device is provided on the condenser 3, and the cooling device is used to reduce the temperature in the condenser 3 to liquefy the water vapor.

[0050] By adopting the above technical solution, water vapor and other gases discharged from the dehydration tower 2 enter the condenser 3 through the first exhaust pipe 21. The temperature in the condenser 3 is controlled at 25-40°C. The water vapor liquefies into liquid water and sinks to the bottom of the condenser 3. Hydrogen sulfide and nitrogen are discharged in gaseous form through the second exhaust pipe 33. It will be understood that while the temperature of the dehydration tower 2 is being raised, the cooling device is activated to maintain the temperature in the condenser 3 at 25-40°C, thereby effectively separating the water from the mixed gas.

[0051] Specifically, the cooling device includes a third jacket 34 disposed on the outer wall of the condenser 3. A cooling water inlet 341 is provided at the lower portion of one side of the third jacket 34, and a cooling water outlet 342 is provided at the upper portion of the other side of the third jacket 34. When the temperature inside the condenser 3 needs to be adjusted, water at a temperature of 25 to 40°C enters the third jacket 34 through the cooling water inlet 341 and flows out through the cooling water outlet 342. This cycle continues to maintain the temperature inside the condenser 3 at 25 to 40°C.

[0052] In an embodiment of the present application, the separation device further includes a liquid collecting tank 32 , which is connected to the bottom of the condenser 3 through a first liquid drain pipe 31 , and the liquid collecting tank 32 is located below the condenser 3 .

[0053] By adopting the above technical solution, the water deposited at the bottom of the condenser 3 can flow into the collecting tank 32 through the drain pipe, and the condensed and liquefied water is collected in the collecting tank 32 for resource utilization.

[0054] In an embodiment of the present application, the first liquid drain pipe 31 includes a liquid seal pipe 311 and a liquid outlet pipe 312, the liquid seal pipe 311 has a lower section 311a connected to the bottom of the condenser 3, and a higher section 311b connected to the lower section, and the higher section 311b exceeds the bottom end of the condenser 3; one end of the liquid outlet pipe 312 is connected to the higher section, and the other end of the liquid outlet pipe 312 is connected to the liquid collecting tank 32.

[0055] By adopting the above technical solution, the water deposited at the bottom of the condenser 3 flows sequentially to the lower section, the upper end, and the liquid outlet pipe 312, and then flows into the liquid collection tank 32. The provision of the liquid seal pipe 311 can prevent gases such as hydrogen sulfide from flowing into the liquid collection tank 32. Before the reaction, water is first added to the condenser 3 to allow the water to flow to the upper section. At this time, the liquid level 311c in the upper section is still some distance away from the top of the upper section, and the liquid level in the upper section is above the bottom end of the condenser 3. This can achieve a good liquid seal effect and effectively prevent gases such as hydrogen sulfide from flowing into the liquid collection tank 32. It is understood that the liquid seal pipe 311 can be "U" shaped, "V" shaped, or other shapes as needed; a liquid injection port is also provided at the top of the condenser 3 for adding water into the condenser 3 so that the liquid seal pipe 311 can better achieve the liquid seal effect; a valve is provided on the liquid injection port. When water needs to be added, the valve is in an open state, and when water addition is completed, the valve is in a closed state.

[0056] In an embodiment of the present application, the polyphenylene sulfide preparation system further includes a hydrogen sulfide collector 5 for liquefying gaseous hydrogen sulfide into liquid hydrogen sulfide. An air inlet end of the hydrogen sulfide collector 5 is connected to the second exhaust pipe 33 .

[0057] By adopting the above technical solution, a temperature regulating device is provided on the hydrogen sulfide collector 5 to control the temperature within the hydrogen sulfide collector 5 at -62 to -80°C. The hydrogen sulfide and nitrogen discharged from the condenser 3 flow into the hydrogen sulfide collector 5 through the second exhaust pipe 33. The hydrogen sulfide flowing into the hydrogen sulfide collector 5 is pre-cooled and condensed into liquid hydrogen sulfide, which sinks to the bottom of the hydrogen sulfide collector 5, while the nitrogen remains in a gaseous state and is discharged from the top of the hydrogen sulfide collector 5. It will be understood that a gas outlet 52 is provided at the top of the hydrogen sulfide collector 5 to facilitate the discharge of nitrogen, and the gas inlet end of the hydrogen sulfide collector 5 is located in the middle of the hydrogen sulfide collector 5.

[0058] In an embodiment of the present application, the polyphenylene sulfide production system further includes a dryer 4 disposed between the hydrogen sulfide collector 5 and the condenser 3, for drying hydrogen sulfide. The dryer 4 is configured to ensure that gaseous hydrogen sulfide, such as hydrogen sulfide, discharged from the condenser 3 enters the hydrogen sulfide collector 5 in a relatively dry state.

[0059] In an embodiment of the present application, the polyphenylene sulfide preparation system further includes a hydrogen sulfide vaporizer 6 , the gas outlet end of the hydrogen sulfide vaporizer 6 is connected to the hydrogen sulfide input pipe 14 , and the liquid inlet end of the hydrogen sulfide vaporizer 6 is connected to the second liquid drain pipe 51 on the hydrogen sulfide collector 5 .

[0060] By adopting the above technical solution, the hydrogen sulfide vaporizer 6 can vaporize liquid hydrogen sulfide into gaseous hydrogen sulfide, and flow the gaseous hydrogen sulfide into the hydrogen sulfide input pipe 14 at the flow rate required for the reaction, and then flow into the reactor 1; the hydrogen sulfide collected in the hydrogen sulfide collector 5 can be used as one of the sources of liquid hydrogen sulfide for the hydrogen sulfide vaporizer 6, thereby realizing the recycling of resources.

[0061] It is understood that the liquid inlet end of the hydrogen sulfide vaporizer 6 is provided with a liquid inlet pipe 61. The end of the liquid inlet pipe 61 extends into a container storing liquid hydrogen sulfide. The liquid hydrogen sulfide in the container is transported to the hydrogen sulfide vaporizer 6 through the liquid inlet pipe 61, where it is converted into gaseous hydrogen sulfide and enters the reactor 1 to facilitate the reaction. A pump can be installed on the liquid inlet pipe 61 as needed to ensure a relatively stable delivery of liquid hydrogen sulfide to the hydrogen sulfide vaporizer 6. The liquid outlet end of the second liquid discharge pipe 51 is connected to the liquid inlet pipe 61. The hydrogen sulfide collected in the hydrogen sulfide collector 5 flows into the hydrogen sulfide vaporizer 6 through the second liquid discharge pipe 51 and the liquid inlet pipe 61. It is understood that the condenser 3 is located above, the hydrogen sulfide vaporizer 6 is located below, and the hydrogen sulfide collector 5 is located between the condenser 3 and the hydrogen sulfide vaporizer 6.

[0062] In an embodiment of the present application, the polyphenylene sulfide preparation system further includes a second heating device disposed on the reactor 1 ; and / or, the polyphenylene sulfide preparation system further includes a stirring device 15 disposed in the reactor 1 .

[0063] By adopting the above technical solution, the second heating device is used to adjust the temperature in the reactor 1 to better meet the requirements of the preparation process; a stirring device 15 is provided in the reactor 1 to ensure more sufficient contact between the raw materials.

[0064] Specifically, the second heating device includes a second jacket 16 disposed on the outer wall of the reactor 1 , a second thermal oil inlet 161 is disposed at the lower portion of one side of the second jacket 16 , and a second thermal oil outlet 162 is disposed at the upper portion of the other side.

[0065] By adopting the above technical solution, a second jacket 16 is provided on the outer wall of the reactor 1, and a second thermal oil inlet 161 is provided at the lower portion of one side of the second jacket 16, and a second thermal oil outlet 162 is provided at the upper portion of the other side of the second jacket 16. Thermal oil with a higher temperature can flow into the second thermal oil inlet 161 and flow out from the second thermal oil outlet 162, and the cycle is repeated to better regulate the temperature in the reactor 1.

[0066] The polyphenylene sulfide preparation system of the present application is used to prepare polyphenylene sulfide, comprising the following steps:

[0067] S10, provide a 10L reactor, nitrogen is introduced into the reactor through a nitrogen inlet tube at a flow rate of 0.5L / min, under a nitrogen protective atmosphere, 1kg of phenol (C6H5OH, purity 99.5%), 30g of phosphoric acid (H3PO4, purity 99%) and 10g of modified titanate catalyst are added to the reactor through a feed port, the temperature of the mixed solution in the reactor is controlled to be 160°C, and the mixture is stirred at a stirring rate of 100rpm, and hydrogen sulfide is introduced into the reactor through a hydrogen sulfide inlet tube at a flow rate of 2L / min, so that hydrogen sulfide and The mixed liquid in the reactor is contacted and stirred for reaction for 4 hours to obtain phenyl disulfide, wherein the water generated during the reaction is gasified into water vapor, and the water vapor is discharged from the exhaust port on the top of the reactor together with the overflowed hydrogen sulfide gas, and flows through a dehydration tower (the temperature in the tower is 110°C) to a condenser (the temperature in the condenser is 30°C), where the water vapor is liquefied to form liquid water, thereby removing the water generated by the reaction. The hydrogen sulfide overflowing from the condenser can be treated in a dryer and a hydrogen sulfide collector (the temperature is -70°C) and recycled, and the overflowed nitrogen is discharged from the hydrogen sulfide collector.

[0068] S20. Maintaining the nitrogen protective atmosphere, stop the input of hydrogen sulfide, control the temperature of the mixed liquid in the reactor to 240°C, maintain the stirring rate of 100 rpm for stirring, add 1.5 kg of cyclopentane sulfone (C4H8O2S, purity 99%) and 50 g of modified titanate catalyst through the feed port, stir the reaction for 6 hours, and obtain a polyphenylene sulfide solution.

[0069] S30, filtering the polyphenylene sulfide solution obtained in step S20 to perform solid-liquid separation to obtain a solid, washing the solid with methanol for three times, crushing and drying the solid to obtain polyphenylene sulfide with an average particle size of 2 mm.

[0070] The method for preparing the modified titanate catalyst in step S10 and step S20 comprises the following steps:

[0071] (1) Under a nitrogen atmosphere, tetrabutyl titanate (purity: 99%) was added to a reaction vessel. The temperature of the solution in the reaction vessel was controlled to 70°C and stirred at a stirring rate of 100 rpm. Acetylacetone (purity: ≥99.6%) was added at a feeding rate of 10 g / min and stirred for 1 h. After the reaction, a titanate acetylacetone complex was obtained.

[0072] (2) Maintaining a nitrogen protective atmosphere, the temperature of the solution in the reaction vessel was controlled to 80° C., the stirring rate was maintained at 100 rpm, and hydroxyacetic acid (purity of 99%) was added at a feeding rate of 5 g / min. The mixture was stirred for 2 h. After the reaction, a modified titanate catalyst solution was obtained.

[0073] (3) The modified titanate catalyst solution obtained in step (2) is cooled to room temperature (25° C.), and volatile components are removed by reduced pressure distillation to obtain a powdered modified titanate catalyst.

[0074] The mass ratio of tetrabutyl titanate and acetylacetone in step (1) and the hydroxyacetic acid in step (2) is 85:50:19.

[0075] According to the measurement, the weight average molecular weight of the prepared polyphenylene sulfide is greater than 70,000 g / mol, the purity is greater than 99.9%, and the yield is greater than 90%.

[0076] The above description is merely an exemplary embodiment of the present application and does not limit the patent scope of the present application. Any equivalent structural transformation made using the contents of the present application specification and drawings under the technical concept of the present application, or directly / indirectly applied in other related technical fields, is included in the patent protection scope of the present application.

Claims

1. A polyphenylene sulfide preparation system, characterized in that: include: The reactor is provided with a feed port and an exhaust port at the top, a nitrogen inlet pipe in the middle, and a hydrogen sulfide input pipe at the bottom; a dehydration tower, disposed on the top of the reactor and connected to the exhaust port, wherein a first exhaust pipe is provided on the top of the dehydration tower; and A first heating device is provided on the dehydration tower, and is used to ensure that the temperature in the dehydration tower is not lower than 100°C.

2. The polyphenylene sulfide preparation system according to claim 1, characterized in that: The first heating device includes a first jacket arranged on the outer wall of the water removal tower, a first heat transfer oil inlet is arranged at the lower portion of one side of the first jacket, and a first heat transfer oil outlet is arranged at the upper portion of the other side.

3. The polyphenylene sulfide preparation system according to claim 1, characterized in that: The polyphenylene sulfide preparation system further includes a separation device, which includes: A condenser, having an air inlet provided on a side wall at its lower portion and a second exhaust pipe provided on the top, wherein the air inlet is connected to the first exhaust pipe; and A cooling device is provided on the condenser, and is used to reduce the temperature in the condenser so as to liquefy the water vapor.

4. The polyphenylene sulfide preparation system according to claim 3, characterized in that: The separation device further includes a liquid collecting tank, which is connected to the bottom of the condenser through a first liquid drain pipe, and the liquid collecting tank is located below the condenser.

5. The polyphenylene sulfide preparation system according to claim 4, characterized in that: The first liquid drain pipe comprises: a liquid sealing pipe having a lower section connected to the bottom of the condenser and an upper section connected to the lower section, wherein the upper section exceeds the bottom end of the condenser; and A liquid outlet pipe has one end connected to the higher section and the other end connected to the liquid collecting tank.

6. The polyphenylene sulfide preparation system according to claim 3, characterized in that: The polyphenylene sulfide preparation system further includes a hydrogen sulfide collector for liquefying gaseous hydrogen sulfide into liquid hydrogen sulfide. The air inlet end of the hydrogen sulfide collector is connected to the second exhaust pipe.

7. The polyphenylene sulfide preparation system according to claim 6, characterized in that: The polyphenylene sulfide preparation system further includes a dryer disposed between the hydrogen sulfide collector and the condenser, and the dryer is used to dry hydrogen sulfide.

8. The polyphenylene sulfide preparation system according to claim 6, characterized in that: The polyphenylene sulfide preparation system further includes a hydrogen sulfide vaporizer, the gas outlet of the hydrogen sulfide vaporizer is connected to the hydrogen sulfide input pipe, and the liquid inlet of the hydrogen sulfide vaporizer is connected to the second liquid drain pipe on the hydrogen sulfide collector.

9. The polyphenylene sulfide preparation system according to claim 1, characterized in that: The polyphenylene sulfide preparation system further includes a second heating device disposed on the reactor; and / or, The polyphenylene sulfide preparation system further includes a stirring device arranged in the reactor.

10. The polyphenylene sulfide preparation system according to claim 9, characterized in that: The second heating device includes a second jacket arranged on the outer wall of the reactor, a second heat transfer oil inlet is arranged at the lower portion of one side of the second jacket, and a second heat transfer oil outlet is arranged at the upper portion of the other side of the second jacket.

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