CN109535426B - Polyphenylene sulfide resin synthesis process - Google Patents
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Abstract
The invention discloses a synthetic process of polyphenylene sulfide resin, which aims to obtain a resin synthetic method with good particle forming, high product yield, high solvent recovery rate and reduced corrosion degree of a polymerization reaction device Environmental protection, textile industry and other fields.
Description
Technical Field
The invention relates to the field of synthesis of resin materials, in particular to a synthesis process of polyphenylene sulfide resin.
Background
Linear high molecular weight polyphenylene sulfide (PPS) has good chemical properties and physical properties, and is widely applied to the industrial technical fields of aerospace, aviation, electronics, petrochemical industry, food, light industry and the like, and the synthesis process of the PPS is increasingly emphasized by countries all over the world. U.S. Pat. No. 4,989,10294, European patent EP0256757 and U.S. Pat. No. 4,4794164 all describe a two-step process for the synthesis of PPS, but do not involve a feed method. The domestic PPS industrial synthesis process is only disclosed in Chinese patent CN971073570 and a process condition control method thereof, wherein a one-time feeding method is almost adopted in the polymerization reaction process, the method is characterized in that when feeding, the temperature in a kettle is required to be reduced to below 160 ℃, the kettle is opened for feeding, otherwise, one of materials participating in PPS polymerization reaction is one, p-dichlorobenzene p-DCB can cause material proportion change due to vaporization escape, the temperature is increased again after feeding for reaction, the reaction success rate is influenced, the energy consumption is high, the exothermic reaction generated in PPS synthesis is generated, vaporized materials are generated in the kettle, the pressure of the reaction kettle is increased, and in order to ensure that PPS can be synthesized under normal pressure, the exhaust pressure is often released, but partial materials are taken away while the exhaust gas is exhausted, the material proportion is unbalanced, and the possibility of reaction failure or small molecular weight is caused.
In chinese patent applications CN001161407 and 201110066322.2, a process control condition for synthesizing polyphenylene sulfide resin is introduced, wherein except for several conventional temperature and pressure parameters, the process control index for synthesizing polyphenylene sulfide resin is not described too much.
In the U.S. Pat. No. 4820101, it is described that the content of chlorine in polyphenylene sulfide resin is reduced by treating polyphenylene sulfide resin of synthesized synthesis aid with a reducing agent, and the polyphenylene sulfide resin thus treated is used as electronic packaging material for the purpose of improving the electrical insulation performance of electronic and electrical materials.
In the chinese patent application 201610033529.2, sodium acetate is introduced as a cosolvent for synthesizing polyphenylene sulfide resin, and the polyphenylene sulfide resin is relatively difficult to form due to the influence of the crystal shape of sodium acetate after the polyphenylene sulfide resin is synthesized.
In chinese patent application 201410087155.3, an industrial synthetic process of polyphenylene sulfide resin without any addition of any additive is introduced, wherein sodium hydrosulfide, sodium hydroxide and dichlorobenzene are used as raw materials, N-methyl-2-pyrrolidone is used as a solvent, and the polyphenylene sulfide resin is synthesized by condensation polymerization under the condition of no addition of any synthetic additive.
In the chinese patent application 201410087185.4, an industrial synthesis process of polyphenylene sulfide resin without any synthesis aid added, in which sodium hydrosulfide, sodium hydroxide and p-dichlorobenzene are used as raw materials, N-methyl pyrrolidone (NMP) is used as a solvent, and the polyphenylene sulfide resin is synthesized by condensation polymerization without any synthesis aid added, and during the synthesis process, the viscosity of the polymerization reaction system is relatively high due to the relatively low solvent content of the system, and the cooling of the polymerization reaction system is not facilitated after the polymerization reaction is completed.
Disclosure of Invention
The invention aims to provide a polyphenylene sulfide resin synthesis process, and aims to obtain a resin synthesis method which has the advantages of good particle forming, high product yield, high solvent recovery rate and reduced corrosion degree of a polymerization reaction device.
The invention is realized by the following processes:
a synthetic process of polyphenylene sulfide resin comprises the steps of adopting sodium hydrosulfide containing a certain amount of crystal water, sodium hydroxide and p-dichlorobenzene as raw materials, adopting N-methyl pyrrolidone as a solvent to synthesize the polyphenylene sulfide resin, before the dehydration process begins, respectively adding the sodium hydrosulfide and the sodium hydroxide into different reaction kettles of a dehydration system, respectively preparing aqueous solutions with a certain mass concentration, simultaneously respectively heating the reaction kettles, mixing the two aqueous solutions together under the condition of raising the temperature to a certain temperature, preserving the temperature for a certain time to generate sodium sulfide, then adding an NMP solvent, immediately raising the temperature of the dehydration system for dehydration, after the dehydration is completed, adding the sodium sulfide generated by the p-dichlorobenzene into the synthesis system for condensation polymerization reaction, after the low-temperature and high-temperature condensation polymerization is completed, adding acetate, NMP and the aqueous solutions by a high-pressure pump, and then, and (3) keeping the temperature of the polymerization system at 260-270 ℃ for a certain time, cooling the polymerization reaction system to 160-180 ℃, filtering while hot, purifying a filter cake by using an NMP solvent, repeatedly washing the filter cake by using deionized water, filtering, and drying the filter cake to obtain the polyphenylene sulfide resin.
The polyphenylene sulfide resin synthesis process comprises the following specific steps:
(1) in a dehydration system before polymerization, under the condition of nitrogen protection, adding sodium hydrosulfide and deionized water into one reaction kettle to form an aqueous solution containing 45-60% wt of sodium hydrosulfide, adding sodium hydroxide and oxygen-free deionized water into the other reaction kettle under the condition of nitrogen protection to form an aqueous solution containing 45-60% wt of sodium hydroxide, immediately heating the materials in the two reaction kettles to 80-100 ℃, inputting the aqueous solution of sodium hydroxide into the reaction kettle containing the aqueous solution of sodium hydrosulfide by using an alkali-resistant pump, and when the temperature of the materials reaches 120-130 ℃, preserving the temperature for 18-30 min to generate sodium sulfide, and then adding N-methylpyrrolidone to ensure that Na is Na2S, increasing the temperature of the materials in the reaction kettle to 200-204 ℃ at a temperature rise speed of 3-6 ℃/min, wherein the mol ratio of NMP is 1.0: 3.8-5.8, and the dehydration time is 300-360 min;
（2) In the dehydration system obtained in the step (1), after adding p-dichlorobenzene, Na in the polymerization system is allowed to exist2S:p-DCB:H2The molar ratio of O to NMP is 1.0: 0.99-1.18: 0.5-0.9: 3.8-4.8, nitrogen is introduced into the synthesis system, air in the polymerization system is replaced, the polymerization reaction system is sealed, the polymerization system is heated and heated, when the temperature rises to a low-temperature stage, the temperature is 200-210 ℃, and the pressure is 2-4 kg/cm2The time is 90-135 min, when the heat preservation is finished in the low-temperature stage, the temperature is raised to the high-temperature polymerization stage at the speed of 0.3-0.6 ℃/min, the temperature in the stage is 260-270 ℃, and the pressure in the stage is 8-9 kg/cm2The time is 150-180 min, and after the heat preservation at the high temperature stage is finished, acetate, NMP and an aqueous solution are added by a high-pressure pump to ensure that Na in a polymerization system2S:p-DCB:H2The mol ratio of the O to the NMP to the MAC is 1.0: 0.99-1.18: 1.5-1.9: 4.8-5.8: 0.8-1.1, the temperature is kept at 260-270 ℃ in a high-temperature stage, and the pressure is 10-24 kg/cm2The time is 30-60 min, when the heat preservation is finished again at the high-temperature stage, the temperature of the polymerization reaction system is immediately reduced to 160-180 ℃, the hot polymerization reaction system is filtered, the filtrate is input into a solvent recovery system, and the filter cake is the polyphenylene sulfide resin containing certain impurities, which is synthesized and produced;
(3) adding a fresh NMP solvent into the filter cake obtained in the step (2) to prepare a mixture system containing 13-18 wt% of polyphenylene sulfide resin, heating the mixture system to 160-180 ℃ under the protection of nitrogen, preserving the heat for 45-60 min under the temperature condition, filtering while hot, and treating and recycling the filtrate for the solvent and the byproducts, wherein the filter cake is for later use;
(4) after the filter cake obtained in the step (3) is subjected to purification treatment in the step (3) for 4-6 times, obtaining polyphenylene sulfide resin containing 0.1-0.6 wt% of solvent;
(5) adding deionized water into the polyphenylene sulfide resin containing 0.1-0.6 wt% of the solvent obtained in the step (4) to prepare a mixture system containing 13-18 wt% of the polyphenylene sulfide resin, heating the mixture system to 100 ℃ under the protection of nitrogen, carrying out reflux heat preservation for 45-60 min under the temperature condition, filtering while hot, treating and recycling the filtrate for the solvent and byproducts, and obtaining a filter cake for later use;
(6) washing the filter cake obtained in the step (5) for 6-8 times to obtain polyphenylene sulfide resin with water content of 0.3-0.6 wt%;
(7) and (3) putting the polyphenylene sulfide resin with the water content of 0.3-0.6 wt% obtained in the step (6) into a dryer with the temperature of 130-150 ℃, and drying for 3-6 h to obtain the polyphenylene sulfide resin.
Wherein the acetate in the step (2) is sodium acetate, lithium acetate or calcium acetate.
The invention has the beneficial effects that:
1. the synthesis process adopted by the invention reduces the content of metal ions in the polyphenylene sulfide resin produced by synthesis, improves the performance characteristics of the polyphenylene sulfide resin, improves the particle forming rate of the polyphenylene sulfide resin in the forming process, improves the purification and washing effects of the polyphenylene sulfide resin in the purification and washing process procedures, shortens the purification and washing process procedures and time, and also fully utilizes the characteristic that sodium hydrosulfide and sodium hydroxide impurities are less than sodium sulfide, omits the treatment process procedure of sodium sulfide, improves the conversion rate of p-DCB in the polyphenylene sulfide resin synthesis process, reduces the occurrence of polymerization side reaction, further improves the yield of finished products of the polyphenylene sulfide resin, and also reduces the impurity content of raw materials in the polymerization reaction process, the probability of side reaction is reduced, so that the soluble by-products in the solvent of the synthesis system are reduced, the process flow of solvent recovery is shortened, and the recovery and reutilization rate of the solvent is improved.
2. In order to reduce the corrosion degree of a polymerization reaction device, the mole number of sodium hydroxide added in the dehydration process is equal to that of sodium hydrosulfide, so that the pH values in a dehydration system and a polymerization reaction system are reduced, and the corrosion of the generated sodium sulfide to the polymerization reaction device under a high-temperature condition is reduced.
3. In order to improve the formability of the polyphenylene sulfide resin particles after synthesis, in the synthesis process, on one hand, the adjustability of process control conditions is fully utilized, on the other hand, on the basis of optimizing the process control conditions, the physicochemical properties of various assistants are reasonably utilized, after the polycondensation of the polyphenylene sulfide resin is completed, acetate, NMP and water are properly added according to a certain molar ratio, the pH value of a synthesis system is stabilized, the polydispersion coefficient of the synthesized polyphenylene sulfide resin and the number average and weight average molecular weight of the polyphenylene sulfide resin are further stabilized, the melt flow rate of the polyphenylene sulfide resin is further stabilized, meanwhile, after the NMP and the water are added, the capacity of a solvent system in a polymerization reaction system is increased, on the one hand, the dissolution ratio of the byproduct crystal sodium chloride in the water is effectively improved, on the other hand, the content of the crystal sodium chloride in the particles after the molding of the polyphenylene sulfide resin is reduced, thereby reducing the sodium chloride content in the subsequent products of the polyphenylene sulfide resin and further expanding the application field of the subsequent products of the polyphenylene sulfide resin.
4. According to the invention, after the synthesis of the polyphenylene sulfide resin is finished, acetate, NMP and water in a certain molar ratio are added, so that the polyphenylene sulfide resin is effectively solidified into particles of 500-1000 μm in a synthesis system through further heat preservation at a high temperature of 220-230 ℃, the uniform and stable cooling of the polyphenylene sulfide resin synthesis system is facilitated, the cooling rate of the polyphenylene sulfide resin synthesis system is effectively increased on one hand, the polyphenylene sulfide resin is effectively prevented from being adhered to a heat exchange coil in a polymerization reaction kettle on the other hand, the particle formability of the polyphenylene sulfide resin in the cooling process is effectively increased on the other hand, the impurity content in the polyphenylene sulfide resin particles is further reduced, and the washing difficulty of the polyphenylene sulfide resin is further reduced on the basis.
5. In the experimental process of the invention, repeated experiments show that after acetate, NMP and water with a certain molar ratio are added, the cooling rate is accelerated in the process of cooling the polymerization reaction system after the polymerization reaction is completely finished, and meanwhile, the viscosity of the polymerization reaction system is reduced, so that the adhesion of the polyphenylene sulfide resin in the polymerization reaction device is reduced, and the molar ratio of the raw materials of the polymerization reaction system is not unstable without cleaning in the next polymerization reaction.
6. In the process of the invention, the added acetate can be used as a loosening agent of the polyphenylene sulfide resin, the solubility of calcium acetate in NMP solvent is lower than that of sodium acetate and lithium acetate, and simultaneously, in the synthesis process of the polyphenylene sulfide resin, H is2The amount of O in NMP is very limited, especially after the polyphenylene sulfide resin is synthesized at high temperature, the solubility of acetate in a liquid system containing a solvent is small relative to that at low temperature, so that the acetate exists in a polymerization reaction system in a crystal form, and when the temperature of the polymerization reaction system is reduced to 160 ℃, H is added2O mainly exists in a polymerization reaction system in a form of water vapor, under the condition, when the temperature of the polymerization reaction system is reduced, a certain amount of acetate is wrapped in the polyphenylene sulfide resin, so that the wrapped acetate is washed and removed in the washing process of the polyphenylene sulfide resin, the volume density of the polyphenylene sulfide is further reduced, the polyphenylene sulfide resin becomes more loose, and meanwhile, after the polymerization reaction is finished, the molar ratio of the added acetate is relatively higher, so that the amount of the acetate wrapped in the polyphenylene sulfide resin is relatively more.
The process flow of the invention is briefly described as follows:
firstly, under the condition of introducing inert gases such as nitrogen or argon and the like into a reaction system, adding sodium hydrosulfide, sodium hydroxide, deionized water and NMP with a certain molar ratio, respectively preparing aqueous solutions with a certain mass concentration from the sodium hydrosulfide and the sodium hydroxide, mixing at a certain temperature to prepare a raw material sodium sulfide required for synthesizing polyphenylene sulfide resin, preserving heat for a certain time at a certain temperature, heating and dehydrating the dehydration system, controlling the dehydration time and dehydration rate when the temperature is increased to 204 ℃, then, adding p-dichlorobenzene with a certain molar ratio under the condition of cooling to a certain temperature, carrying out polymerization reaction on the polyphenylene sulfide resin under a closed condition, when the temperature is increased to a certain value, preserving heat for 4-8 hours under the condition, immediately pumping MAC with a certain molar ratio by using a high-pressure pump, NMP and H2And O, preserving heat for a certain time under a certain temperature condition, cooling the reaction system, filtering while the reaction system is hot when the temperature is reduced to 160-180 ℃, repeatedly washing the reaction system for 4-7 times by using a solvent NMP, finally washing the reaction system for 6-8 times by using deionized water, and drying the product for 3-6 hours by using air at 120-140 ℃ to obtain the polyphenylene sulfide resin with high purity, high weight average molecular weight and narrow molecular weight distribution coefficient.
Detailed Description
Example 1
The synthetic process of the polyphenylene sulfide resin comprises the following steps:
(1) under the protection of nitrogen, adding sodium hydrosulfide and oxygen-free deionized water into one reaction kettle to form 45 wt% aqueous solution containing sodium hydrosulfide, adding sodium hydroxide and oxygen-free deionized water into the other reaction kettle under the protection of nitrogen to form 45 wt% aqueous solution containing sodium hydroxide, heating the materials in the two reaction kettles to 80 ℃, inputting the aqueous solution of sodium hydroxide into the reaction kettle containing sodium hydrosulfide by using an alkali-resistant pump, and when the temperature of the materials reaches 120 ℃, preserving the heat for 30min under the temperature condition to generate sodium sulfide, adding N-methylpyrrolidone to ensure that Na is2S, the mol ratio of NMP is 1.0:3.8, the temperature of the materials in the reaction kettle is raised to 200 ℃ at the temperature rising speed of 3 ℃/min, and the dehydration time is 360 min;
(2) after the materials in the dehydration system are finished and the p-dichlorobenzene is added, Na in the polymerization system is enabled2S:p-DCB:H2The molar ratio of O to NMP is 1.0:0.99:0.5: 3.8; introducing nitrogen into the synthesis system, replacing air in the polymerization system, sealing the polymerization reaction system, heating the polymerization system, and raising the temperature to a low-temperature stage at 200 deg.C and 2kg/cm2The time is 135min, when the heat preservation in the low-temperature stage is finished, the temperature is increased to the high-temperature polymerization stage at the speed of 0.3 ℃/min, the temperature in the high-temperature polymerization stage is 260 ℃, and the pressure in the high-temperature polymerization stage is 8kg/cm2The time is 180min, when the heat preservation is finished at the high temperature stage, a solution of sodium acetate, NMP and water is added by a high-pressure pump, so that Na in a polymerization system is added2S:p-DCB:H2The molar ratio of O to NMP to MAC is 1.0:0.99:1.5:48:0.8, immediately maintaining the temperature at 260 ℃ and the pressure at 10kg/cm2And the time is 60min, when the heat preservation is finished again at the high-temperature stage, the temperature of the polymerization reaction system is immediately reduced to 160 ℃, the hot polymerization reaction system is filtered, the filtrate is input into a solvent recovery system, and the filter cake is the polyphenylene sulfide resin containing certain impurities;
(3) adding a fresh NMP solvent into the obtained filter cake to prepare a mixture system containing 13wt% of polyphenylene sulfide resin, heating the mixture system to 160 ℃ under the protection of nitrogen, preserving the heat for 60min under the temperature condition, filtering while hot, and treating and recovering the filtrate for the solvent and byproducts, wherein the filter cake is for later use;
(4) repeating the process of the step (3), and purifying the obtained filter cake for 4 times to obtain the polyphenylene sulfide resin containing 0.1 wt% of the solvent;
(5) adding deionized water into the obtained polyphenylene sulfide resin containing 0.1 wt% of solvent to prepare a mixture system containing 13wt% of polyphenylene sulfide resin, heating the mixture system to 100 ℃ under the protection of nitrogen, refluxing and preserving heat for 60min under the temperature condition, filtering while hot, and treating and recovering the filtrate for the solvent and byproducts, wherein the filter cake is used for standby;
(6) repeating the process of the step (5), and washing the obtained filter cake for 6 times to obtain the polyphenylene sulfide resin with the water content of 0.3 wt%;
(7) the obtained polyphenylene sulfide resin containing 0.3% by weight of moisture was put into a drier at a temperature of 130 ℃ and dried for 6 hours, thereby obtaining a polyphenylene sulfide resin.
Example 2
The synthetic process of the polyphenylene sulfide resin comprises the following steps:
(1) under the protection of nitrogen, adding sodium hydrosulfide and oxygen-free deionized water into one reaction kettle to form an aqueous solution containing 60 wt% of sodium hydrosulfide, adding sodium hydroxide and oxygen-free deionized water into the other reaction kettle under the protection of nitrogen to form an aqueous solution containing 60 wt% of sodium hydroxide, and heating the materials in the two reaction kettlesWhen the temperature reaches 100 ℃, inputting a sodium hydroxide aqueous solution into a reaction kettle containing sodium hydrosulfide dissolved in water by using an alkali-resistant pump, preserving the temperature for 18min to generate sodium sulfide when the material temperature reaches 130 ℃, and then adding N-methylpyrrolidone to ensure that Na is added2S, the NMP molar ratio is 1.0:5.8, the temperature of the materials in the reaction kettle is raised to 204 ℃ at the temperature rising speed of 6 ℃/min, and the dehydration time is 300 min;
(2) after the materials in the dehydration system are finished and the p-dichlorobenzene is added, Na in the polymerization system is enabled2S:p-DCB:H2The molar ratio of O to NMP is 1.0:1.18:0.9:4.8, nitrogen is introduced into the synthesis system, air in the polymerization system is replaced, the polymerization reaction system is sealed, the polymerization system is heated and heated up immediately, when the temperature rises to a low-temperature stage, the temperature is 210 ℃, and the pressure is 4kg/cm2The time is 90min, when the heat preservation of the low-temperature stage is finished, the temperature is increased to the high-temperature polymerization stage at the speed of 0.6 ℃/min, the temperature of the high-temperature polymerization stage is 270 ℃, and the pressure of the high-temperature polymerization stage is 9kg/cm2The time is 150min, and after the heat preservation in the high-temperature stage is finished, a solution of sodium acetate, NMP and water is added by a high-pressure pump to ensure that Na in a polymerization system2S:p-DCB:H2The molar ratio of O to NMP to MAC is 1.0:1.18:1.9:5.8:1.1, the temperature is then maintained at 270 ℃ and the pressure at 24kg/cm2And the time is 30min, when the heat preservation is finished again at the high-temperature stage, the temperature of the polymerization reaction system is immediately reduced to 180 ℃, the filtration is carried out while the polymerization reaction system is hot, the filtrate is input into a solvent recovery system, and the filter cake is the polyphenylene sulfide resin containing certain impurities;
(3) adding a fresh NMP solvent into the obtained filter cake to prepare a mixture system containing 18wt% of polyphenylene sulfide resin, heating the mixture system to 180 ℃ under the protection of nitrogen, preserving the temperature for 45min, filtering while hot, and treating and recovering the filtrate for the solvent and byproducts, wherein the filter cake is for later use;
(4) repeating the process of the step (3), and purifying the obtained filter cake for 6 times, so as to obtain the polyphenylene sulfide resin containing 0.6 wt% of the solvent;
(5) adding deionized water into the obtained polyphenylene sulfide resin containing 0.6 wt% of solvent to prepare a mixture system containing 18wt% of polyphenylene sulfide resin, heating the mixture system to 100 ℃ under the protection of nitrogen, refluxing and preserving heat for 45min under the temperature condition, filtering while hot, and treating and recovering the filtrate for the solvent and byproducts, wherein the filter cake is used for standby;
(6) repeating the process of the step (5), and washing the obtained filter cake for 8 times to obtain the polyphenylene sulfide resin with the water content of 0.6 wt%;
(7) the obtained polyphenylene sulfide resin containing 0.6% by weight of water was put into a drier at a temperature of 150 ℃ and dried for 3 hours, thereby obtaining a polyphenylene sulfide resin.
Example 3
The synthetic process of the polyphenylene sulfide resin comprises the following steps:
(1) under the protection of nitrogen, adding sodium hydrosulfide and oxygen-free deionized water into one reaction kettle to form 48 wt% aqueous solution, adding sodium hydroxide and oxygen-free deionized water into the other reaction kettle under the protection of nitrogen to form 52 wt% aqueous solution containing sodium hydroxide, heating the materials in the two reaction kettles to 83 ℃, inputting the aqueous solution of sodium hydroxide into the reaction kettle containing sodium hydrosulfide with an alkali-resistant pump, and when the temperature of the materials reaches 123 ℃, preserving the heat for 21min under the temperature condition to generate sodium sulfide, adding N-methylpyrrolidone to ensure that Na is Na2S, the mol ratio of NMP is 1.0:4.3, the temperature of the materials in the reaction kettle is raised to 203 ℃ at the temperature rise speed of 4 ℃/min, and the dehydration time is 350 min;
(2) after the materials in the dehydration system are finished and the p-dichlorobenzene is added, Na in the polymerization system is enabled2S:p-DCB:H2The mol ratio of O to NMP is 1.0:1.0:0.6:4.1, nitrogen is introduced into the synthesis system, air in the polymerization system is replaced, the polymerization reaction system is sealed, the polymerization system is heated and heated up immediately, when the temperature rises to a low-temperature stage, the temperature is 204 ℃, and the pressure is 2.7kg/cm2The time is 110min, when the low-temperature stage heat preservation is finished, the temperature is increased to the high temperature at the speed of 0.4 ℃/minA warm polymerization stage at 266 ℃ and a pressure of 8.5kg/cm2And the time is 160min, and after the heat preservation in the high-temperature stage is finished, a solution of lithium acetate, NMP and water is added by a high-pressure pump to ensure that Na in a polymerization system2S:p-DCB:H2The molar ratio of O to NMP to MAC is 1.0:1.0:1.7: 5.3: 0.9, the temperature is then maintained at 263 ℃ and the pressure is 13.8kg/cm2When the temperature is maintained again at the high temperature stage, the temperature of the polymerization reaction system is reduced to 167 ℃, the polymerization reaction system is filtered while the polymerization reaction system is hot, the filtrate is input into a solvent recovery system, and the filter cake is the polyphenylene sulfide resin containing certain impurities, which is synthesized and produced;
(3) adding a fresh NMP solvent into the obtained filter cake to prepare a mixture system containing 14wt% of polyphenylene sulfide resin, heating the mixture system to 167 ℃ under the protection of nitrogen, preserving the temperature for 49min, filtering while hot, and treating and recovering the filtrate for the solvent and the byproducts, wherein the filter cake is for later use;
(4) repeating the process of the step (3), and purifying the obtained filter cake for 5 times, so as to obtain the polyphenylene sulfide resin containing 0.2 wt% of the solvent;
(5) adding deionized water into the obtained polyphenylene sulfide resin containing 0.2 wt% of solvent to prepare a mixture system containing 14wt% of polyphenylene sulfide resin, heating the mixture system to 100 ℃ under the protection of nitrogen, refluxing and preserving heat for 50min under the temperature condition, filtering while hot, and treating and recovering the filtrate for the solvent and byproducts to obtain a filter cake for later use;
(6) repeating the process of the step (5), and washing the obtained filter cake for 7 times to obtain the polyphenylene sulfide resin with the water content of 0.4 wt%;
(7) the obtained polyphenylene sulfide resin containing 0.4% by weight of water was put into a drier at a temperature of 143 ℃ and dried for 3.3 hours, thereby obtaining a polyphenylene sulfide resin.
Comparative example 1
(1) Under the protection of nitrogen, adding sodium hydrosulfide and oxygen-free deionized water into a reaction kettle to form water containing 45 wt% of sodium hydrosulfideAdding sodium hydroxide and oxygen-free deionized water into another reactor under nitrogen protection to obtain 45 wt% sodium hydroxide-containing water solution, heating the materials in the two reactors to 80 deg.C, introducing the sodium hydroxide water solution into the reactor containing sodium hydrosulfide, and adding N-methylpyrrolidone when the material temperature reaches 120 deg.C to make Na2S, the mol ratio of NMP is 1.0:3.8, the temperature of the materials in the reaction kettle is raised to 200 ℃ at the temperature rising speed of 3 ℃/min, and the dehydration time is 360 min;
(2) after the materials in the dehydration system are finished and the p-dichlorobenzene is added, Na in the polymerization system is enabled2S:p-DCB:H2The mol ratio of O to NMP is 1.0:0.99:0.5:3.8, nitrogen is introduced into the synthesis system, air in the polymerization system is replaced, the polymerization reaction system is sealed, the polymerization system is heated and heated up immediately, when the temperature rises to a low-temperature stage, the temperature is 200 ℃, and the pressure is 2kg/cm2The time is 135min, when the heat preservation in the low-temperature stage is finished, the temperature is increased to the high-temperature polymerization stage at the speed of 0.3 ℃/min, the temperature in the stage is controlled to be 260 ℃, and the pressure is 8kg/cm2And the time is 180min, when the heat preservation is finished at the high-temperature stage, the temperature of the polymerization reaction system is immediately reduced to 160 ℃, the hot polymerization reaction system is filtered, the filtrate is input into a solvent recovery system, and the filter cake is the polyphenylene sulfide resin containing certain impurities;
(3) adding a fresh NMP solvent into the obtained filter cake to prepare a mixture system containing 13wt% of polyphenylene sulfide resin, heating the mixture system to 160 ℃ under the protection of nitrogen, preserving the heat for 45min under the temperature condition, filtering while hot, and treating and recovering the filtrate for the solvent and the byproducts, wherein the filter cake is used for later use;
(4) repeating the process of the step (3), and purifying the obtained filter cake for 4 times to obtain the polyphenylene sulfide resin containing 0.1 wt% of the solvent;
(5) adding deionized water into the obtained polyphenylene sulfide resin containing 0.1 wt% of solvent to prepare a mixture system containing 13wt% of polyphenylene sulfide resin, heating the mixture system to 100 ℃ under the protection of nitrogen, refluxing and preserving heat for 60min under the temperature condition, filtering while hot, and treating and recovering the filtrate for the solvent and byproducts, wherein the filter cake is used for standby;
(6) repeating the process of the step (5), and washing the obtained filter cake for 6 times to obtain the polyphenylene sulfide resin with the water content of 0.3 wt%;
(7) the obtained polyphenylene sulfide resin containing 0.3% by weight of moisture was put into a drier at a temperature of 130 ℃ and dried for 6 hours, thereby obtaining a polyphenylene sulfide resin.
The polyphenylene sulfide resin particles obtained by the embodiment are in a fine powder shape, and are obviously different from the polyphenylene sulfide resin particles obtained by other embodiments of the invention, meanwhile, in the washing process of the polyphenylene sulfide resin, the washing speed at least takes more than 3 hours, and through analysis and detection, the polyphenylene sulfide resin which is not added with sodium acetate for treatment is found to have a weight average molecular weight below 15000.
Example 4
The synthetic process of the polyphenylene sulfide resin comprises the following steps:
(1) under the protection of nitrogen, adding sodium hydrosulfide and oxygen-free deionized water into one reaction kettle to form 53 wt% sodium hydrosulfide-containing water solution, adding sodium hydroxide and oxygen-free deionized water into the other reaction kettle under the protection of nitrogen to form 47 wt% sodium hydroxide-containing water solution, heating the materials in the two reaction kettles to 89 deg.C, introducing the sodium hydroxide water solution into the reaction kettle containing sodium hydrosulfide water solution with an alkali-resistant pump, and when the temperature of the materials reaches 125 deg.C, maintaining the temperature for 25min to generate sodium sulfide, adding N-methylpyrrolidone to make Na and Na2S, the mol ratio of NMP is 1.0:4.6, the temperature of the materials in the reaction kettle is raised to 201 ℃ at the temperature rising speed of 5 ℃/min, and the dehydration time is 330 min;
(2) after the materials in the dehydration system are finished and the p-dichlorobenzene is added, Na in the polymerization system is enabled2S:p-DCB:H2The molar ratio of O to NMP is 1.0:1.03:0.8:4.5, nitrogen is introduced into the synthesis system, and the nitrogen is replaced out of the polymerization systemThe polymerization reaction system is sealed, and then the polymerization system is heated to raise the temperature, when the temperature is raised to a low-temperature stage, the temperature is 206 ℃, and the pressure is 3.1kg/cm2The time is 124min, when the heat preservation of the low-temperature stage is finished, the temperature is increased to the high-temperature polymerization stage at the speed of 0.5 ℃/min, the temperature of the high-temperature polymerization stage is 263 ℃, and the pressure is 8.7kg/cm2And the time is 168min, after the heat preservation in the high-temperature stage is finished, a solution of lithium acetate, NMP and water is added by a high-pressure pump, so that Na in a polymerization system is added2S:p-DCB:H2The molar ratio of O to NMP to MAC is 1.0:1.03:1.8:5.4:1.0, the temperature is then maintained at 268 ℃ and the pressure at 18.6kg/cm2When the temperature is maintained again at the high temperature stage, the temperature of the polymerization reaction system is reduced to 171 ℃ immediately, the hot polymerization reaction system is filtered, the filtrate is input into a solvent recovery system, and the filter cake is the polyphenylene sulfide resin containing certain impurities, which is synthesized and produced;
(3) adding a fresh NMP solvent into the obtained filter cake to prepare a mixture system containing 15wt% of polyphenylene sulfide resin, heating the mixture system to 171 ℃ under the protection of nitrogen, preserving the heat for 56min under the temperature condition, filtering while hot, and treating and recovering the filtrate for the solvent and byproducts, wherein the filter cake is for later use;
(4) repeating the process of the step (3), and purifying the obtained filter cake for 5 times, so as to obtain the polyphenylene sulfide resin containing 0.5 wt% of the solvent;
(5) adding deionized water into the obtained polyphenylene sulfide resin containing 0.5 wt% of solvent to prepare a mixture system containing 15wt% of polyphenylene sulfide resin, heating the mixture system to 100 ℃ under the protection of nitrogen, refluxing and preserving heat for 55min under the temperature condition, filtering while hot, and treating and recovering the filtrate for the solvent and byproducts, wherein the filter cake is used for standby;
(6) repeating the process of the step (5), and washing the obtained filter cake for 7 times to obtain the polyphenylene sulfide resin with the moisture content of 0.5 wt%;
(7) the obtained polyphenylene sulfide resin containing 0.5% by weight of water was put into a drier at a temperature of 141 ℃ and dried for 4.5 hours, thereby obtaining a polyphenylene sulfide resin.
Example 5
The synthetic process of the polyphenylene sulfide resin comprises the following steps:
(1) under the protection of nitrogen, adding sodium hydrosulfide and oxygen-free deionized water into one reaction kettle to form 55 wt% aqueous solution containing sodium hydrosulfide, adding sodium hydroxide and oxygen-free deionized water into the other reaction kettle under the protection of nitrogen to form 55 wt% aqueous solution containing sodium hydroxide, heating the materials in the two reaction kettles to 96 ℃, inputting the aqueous solution of sodium hydroxide into the reaction kettle containing sodium hydrosulfide by using an alkali-resistant pump, and when the temperature of the materials reaches 126 ℃, preserving the heat for 28min under the temperature condition to generate sodium sulfide, adding N-methylpyrrolidone to ensure that Na is2The mol ratio of NMP to S is 1.0:5.3, the temperature of the materials in the reaction kettle is raised to 202 ℃ at the temperature rising speed of 4.5 ℃/min, and the dehydration time is 350 min;
(2) after the materials in the dehydration system are finished and the p-dichlorobenzene is added, Na in the polymerization system is enabled2S:p-DCB:H2The mol ratio of O to NMP is 1.0:1.11:0.6:4.4, nitrogen is introduced into the synthesis system, air in the polymerization system is replaced, the polymerization reaction system is sealed, the polymerization system is heated and heated up immediately, when the temperature rises to a low-temperature stage, the temperature is 208 ℃, and the pressure is 3.6kg/cm2129min, when the low-temperature stage is finished, the temperature is increased to the high-temperature polymerization stage at the speed of 0.4 ℃/min, the temperature of the high-temperature polymerization stage is 268 ℃, and the pressure is 8.6kg/cm2173min, when the heat preservation is finished at the high temperature stage, adding a solution of calcium acetate, NMP and water by using a high-pressure pump to ensure that Na in a polymerization system2S:p-DCB:H2The molar ratio of O to NMP to MAC is 1.0:1.11:1.8:5.6:1.05, the temperature is then maintained at 266 ℃ and the pressure is 19.3kg/cm2When the temperature is maintained again at the high temperature stage, the temperature of the polymerization reaction system is reduced to 166 ℃, the polymerization reaction system is filtered while the polymerization reaction system is hot, the filtrate is input into a solvent recovery system, and the filter cake is the polyphenylene sulfide resin containing certain impurities, which is synthesized and produced;
(3) adding a fresh NMP solvent into the obtained filter cake to prepare a mixture system containing 17wt% of polyphenylene sulfide resin, heating the mixture system to 165 ℃ under the protection of nitrogen, preserving the heat for 54min under the temperature condition, filtering while hot, and treating and recovering the filtrate for the solvent and byproducts, wherein the filter cake is for later use;
(4) repeating the process of the step (3), and purifying the obtained filter cake for 4 times, so as to obtain the polyphenylene sulfide resin containing 0.43 wt% of the solvent;
(5) adding deionized water into the obtained polyphenylene sulfide resin containing 0.43 wt% of solvent to prepare a mixture system containing 17wt% of polyphenylene sulfide resin, heating the mixture system to 100 ℃ under the protection of nitrogen, refluxing and preserving heat for 57min under the temperature condition, filtering while hot, and treating and recovering the filtrate for the solvent and byproducts, wherein the filter cake is used for standby;
(6) repeating the process of the step (5), and washing the obtained filter cake for 7 times to obtain the polyphenylene sulfide resin with the moisture content of 0.5 wt%;
(7) the obtained polyphenylene sulfide resin containing 0.5% by weight of water was put into a drier at 137 ℃ and dried for 5.6 hours, thereby obtaining a polyphenylene sulfide resin.
Example 6
The synthetic process of the polyphenylene sulfide resin comprises the following steps:
(1) under the protection of nitrogen, adding sodium hydrosulfide and oxygen-free deionized water into one reaction kettle to form water solution containing 49 wt% of sodium hydrosulfide, adding sodium hydroxide and oxygen-free deionized water into the other reaction kettle under the protection of nitrogen to form water solution containing 60 wt% of sodium hydroxide, heating the materials in the two reaction kettles to 91 ℃, inputting the sodium hydroxide water solution into the reaction kettle containing the sodium hydrosulfide for dissolving by using an alkali-resistant pump, and when the temperature of the materials reaches 124 ℃, preserving the heat for 24min under the temperature condition to generate sodium sulfide, adding N-methylpyrrolidone to ensure that Na is2The mol ratio of S to NMP is 1.0:5.6, the temperature of the materials in the reaction kettle is raised to 204 ℃ at the temperature rising speed of 6 ℃/min, and the materials are dehydratedThe time is 360 min;
(2) in the obtained dehydration system, after p-dichlorobenzene was added, Na in the polymerization system was allowed to exist2S:p-DCB:H2The molar ratio of O to NMP is 1.0:1.16:1.3:4.4, nitrogen is introduced into the synthesis system, air in the polymerization system is replaced, the polymerization reaction system is sealed, the polymerization system is heated and heated up immediately, when the temperature rises to a low-temperature stage, the temperature is 210 ℃, and the pressure is 4kg/cm2The time is 135min, when the heat preservation in the low-temperature stage is finished, the temperature is increased to the high-temperature polymerization stage at the speed of 0.6 ℃/min, the temperature in the high-temperature polymerization stage is 270 ℃, and the pressure in the high-temperature polymerization stage is 9kg/cm2The time is 180min, when the heat preservation is finished at the high temperature stage, a solution of calcium acetate, NMP and water is added by a high-pressure pump, so that Na in a polymerization system is added2S:p-DCB:H2The molar ratio of O to NMP to MAC is 1.0:1.16: 2.3: 5.8:1.1, the temperature is then maintained at 268 ℃ and the pressure is 21.8kg/cm2And the time is 60min, when the heat preservation is finished again at the high-temperature stage, the temperature of the polymerization reaction system is immediately reduced to 160 ℃, the hot polymerization reaction system is filtered, the filtrate is input into a solvent recovery system, and the filter cake is the polyphenylene sulfide resin containing certain impurities;
(3) adding a fresh NMP solvent into the obtained filter cake to prepare a mixture system containing 18wt% of polyphenylene sulfide resin, heating the mixture system to 180 ℃ under the protection of nitrogen, preserving the heat for 60min under the temperature condition, filtering while hot, and treating and recovering the filtrate for the solvent and byproducts, wherein the filter cake is for later use;
(4) repeating the process of the step (3), and purifying the obtained filter cake for 6 times, so as to obtain the polyphenylene sulfide resin containing 0.3 wt% of the solvent;
(5) adding deionized water into the obtained polyphenylene sulfide resin containing 0.3 wt% of solvent to prepare a mixture system containing 18wt% of polyphenylene sulfide resin, heating the mixture system to 100 ℃ under the protection of nitrogen, refluxing and preserving heat for 60min under the temperature condition, filtering while hot, and treating and recovering the filtrate for the solvent and byproducts to obtain a filter cake for later use;
(6) repeating the process of the step (5), and washing the obtained filter cake for 8 times to obtain the polyphenylene sulfide resin with the water content of 0.6 wt%;
(7) the obtained polyphenylene sulfide resin containing 0.6% by weight of water was put into a drier at a temperature of 150 ℃ and dried for 6 hours, thereby obtaining a polyphenylene sulfide resin.
Comparative example 2
(1) Under the protection of nitrogen, adding sodium hydrosulfide, sodium hydroxide and oxygen-free deionized water in a molar ratio of 1:1 into a reaction kettle to form an aqueous solution containing 60 wt% of sodium sulfide, keeping the temperature for 130min to generate sodium sulfide when the temperature of the materials reaches 130 ℃, and adding N-methylpyrrolidone to ensure that Na is added to the materials to ensure that Na is dissolved in the aqueous solution2The mol ratio of S to NMP is 1.0:5.8, the temperature of the materials in the reaction kettle is raised to 204 ℃ at the temperature rising speed of 6 ℃/min, and the dehydration time is 300 min.
(2) After the materials in the dehydration system are finished and the p-dichlorobenzene is added, Na in the polymerization system is enabled2S:p-DCB:H2The mol ratio of O to NMP is 1.0:1.18:0.9:4.8, nitrogen is introduced into the synthesis system, air in the polymerization system is replaced, the polymerization reaction system is sealed, the polymerization system is heated and heated up immediately, when the temperature rises to a low-temperature stage, the temperature is 210 ℃, and the pressure is 2kg/cm2The time is 135min, when the heat preservation in the low-temperature stage is finished, the temperature is increased to the high-temperature polymerization stage at the speed of 0.6 ℃/min, the temperature in the high-temperature polymerization stage is 270 ℃, and the pressure in the high-temperature polymerization stage is 9kg/cm2And the time is 180min, when the heat preservation is finished at the high-temperature stage, the temperature of the polymerization reaction system is immediately reduced to 180 ℃, the hot polymerization reaction system is filtered, the filtrate is input into a solvent recovery system, and the filter cake is the polyphenylene sulfide resin containing certain impurities;
(3) adding a fresh NMP solvent into the obtained filter cake to prepare a mixture system containing 18wt% of polyphenylene sulfide resin, heating the mixture system to 180 ℃ under the protection of nitrogen, preserving the heat for 60min under the temperature condition, filtering while hot, and treating and recovering the filtrate for the solvent and byproducts, wherein the filter cake is for later use;
(4) repeating the process of the step (3), and purifying the obtained filter cake for 6 times, so as to obtain the polyphenylene sulfide resin containing 0.3 wt% of the solvent;
(5) adding deionized water into the obtained polyphenylene sulfide resin containing 0.3 wt% of solvent to prepare a mixture system containing 18wt% of polyphenylene sulfide resin, heating the mixture system to 100 ℃ under the protection of nitrogen, refluxing and preserving heat for 60min under the temperature condition, filtering while hot, and treating and recovering the filtrate for the solvent and byproducts, wherein the filter cake is used for standby;
(6) repeating the process of the step (5), and washing the obtained filter cake for 8 times to obtain the polyphenylene sulfide resin with the water content of 0.6 wt%;
(7) the obtained polyphenylene sulfide resin with 0.6 wt% moisture was put into a drier at 150 ℃ and dried for 3 hours, thus obtaining a polyphenylene sulfide resin.
The polyphenylene sulfide resin particles obtained by the method are in a fine powder shape, and are obviously different from the polyphenylene sulfide resin particles obtained by a comparative example, meanwhile, in the washing process of the polyphenylene sulfide resin, the washing speed at least consumes more than 4 hours, and through analysis and detection, the polyphenylene sulfide resin which is not added with sodium acetate for treatment has the weight average molecular weight of less than 13000.
Claims (1)
1. A polyphenylene sulfide resin synthesis process is characterized by comprising the following steps:
(1) in a dehydration system before polymerization, under the condition of nitrogen protection, adding sodium hydrosulfide and deionized water into one reaction kettle to form an aqueous solution containing 45-60% wt of sodium hydrosulfide, adding sodium hydroxide and oxygen-free deionized water into the other reaction kettle under the condition of nitrogen protection to form an aqueous solution containing 45-60% wt of sodium hydroxide, immediately heating the materials in the two reaction kettles to 80-100 ℃, inputting the aqueous solution of sodium hydroxide into the reaction kettle containing the aqueous solution of sodium hydrosulfide by using an alkali-resistant pump, and when the temperature of the materials reaches 120-130 ℃, preserving the temperature for 18-30 min to generate sodium sulfide, adding N-methylpyrroleAlkanones of Na2S, increasing the temperature of the materials in the reaction kettle to 200-204 ℃ at a temperature rise speed of 3-6 ℃/min, wherein the mol ratio of NMP is 1.0: 3.8-5.8, and the dehydration time is 300-360 min;
(2) in the dehydration system obtained in the step (1), after adding p-dichlorobenzene, Na in the polymerization system is allowed to exist2S:p-DCB:H2The molar ratio of O to NMP is 1.0: 0.99-1.18: 0.5-0.9: 3.8-4.8, nitrogen is introduced into the synthesis system, air in the polymerization system is replaced, the polymerization reaction system is sealed, the polymerization system is heated and heated, when the temperature rises to a low-temperature stage, the temperature is 200-210 ℃, and the pressure is 2-4 kg/cm2The time is 90-135 min, when the heat preservation is finished in the low-temperature stage, the temperature is raised to the high-temperature polymerization stage at the speed of 0.3-0.6 ℃/min, the temperature in the stage is 260-270 ℃, and the pressure in the stage is 8-9 kg/cm2The time is 150-180 min, and after the heat preservation at the high temperature stage is finished, acetate MAC, NMP and an aqueous solution are added by a high-pressure pump to ensure that Na of a polymerization system2S:p-DCB:H2The mol ratio of the O to the NMP to the MAC is 1.0: 0.99-1.18: 1.5-1.9: 4.8-5.8: 0.8-1.1, the temperature is kept at 260-270 ℃ in a high-temperature stage, and the pressure is 10-24 kg/cm2The time is 30-60 min, when the heat preservation is finished again at the high-temperature stage, the temperature of the polymerization reaction system is immediately reduced to 160-180 ℃, the hot polymerization reaction system is filtered, the filtrate is input into a solvent recovery system, and the filter cake is the polyphenylene sulfide resin containing certain impurities, which is synthesized and produced; the acetate is sodium acetate, lithium acetate or calcium acetate;
(3) adding a fresh NMP solvent into the filter cake obtained in the step (2) to prepare a mixture system containing 13-18 wt% of polyphenylene sulfide resin, heating the mixture system to 160-180 ℃ under the protection of nitrogen, preserving the heat for 45-60 min under the temperature condition, filtering while hot, and treating and recycling the filtrate for the solvent and the byproducts, wherein the filter cake is for later use;
(4) after the filter cake obtained in the step (3) is subjected to purification treatment in the step (3) for 4-6 times, obtaining polyphenylene sulfide resin containing 0.1-0.6 wt% of solvent;
(5) adding deionized water into the polyphenylene sulfide resin containing 0.1-0.6 wt% of the solvent obtained in the step (4) to prepare a mixture system containing 13-18 wt% of the polyphenylene sulfide resin, heating the mixture system to 100 ℃ under the protection of nitrogen, carrying out reflux heat preservation for 45-60 min under the temperature condition, filtering while hot, treating and recycling the filtrate for the solvent and byproducts, and obtaining a filter cake for later use;
(6) washing the filter cake obtained in the step (5) for 6-8 times to obtain polyphenylene sulfide resin with water content of 0.3-0.6 wt%;
(7) and (3) putting the polyphenylene sulfide resin with the water content of 0.3-0.6 wt% obtained in the step (6) into a dryer with the temperature of 130-150 ℃, and drying for 3-6 h to obtain the polyphenylene sulfide resin.
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