CN117384380A - Method for synthesizing polyphenylene sulfide by pressurizing inert gas without aid - Google Patents
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 68
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000011261 inert gas Substances 0.000 title claims abstract description 26
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 46
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000005191 phase separation Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 239000002954 polymerization reaction product Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 11
- 239000002861 polymer material Substances 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 7
- 208000005156 Dehydration Diseases 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
- C08G75/0254—Preparatory processes using metal sulfides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of high polymer materials, in particular to a method for synthesizing polyphenylene sulfide by pressurizing inert gas without an auxiliary agent. The method comprises the following steps: adding sodium hydrosulfide, sodium hydroxide and NMP into a solvent for heating to obtain a sodium sulfide solution; adding paradichlorobenzene into a sodium sulfide solution in a high-pressure reaction kettle under the protection of inert gas of 0.1-1 Mpa, mixing, and carrying out prepolymerization reaction at a first temperature to obtain a prepolymerization reaction product; carrying out temperature-rising polymerization on the pre-polymerization reaction product at a second temperature to obtain a temperature-rising polymerization reaction product; and adding a phase separating agent into the temperature-rising polymerization reaction product, and then carrying out phase separation at a third temperature to obtain the polyphenylene sulfide. The invention is based on pressurized polymerization and phase separation by adding a phase separating agent, and can prepare the high molecular weight polyphenylene sulfide product in a short time under the condition of no auxiliary agent, and the polyphenylene sulfide product has the characteristics of large average particle size and low melt mass flow rate.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a method for synthesizing polyphenylene sulfide by pressurizing inert gas without an auxiliary agent.
Background
Polyphenylene Sulfide (PPS) has excellent high temperature resistance, corrosion resistance, radiation resistance, self-flame retardance, balanced physical and mechanical properties, excellent dimensional stability, excellent electrical properties, and the like. PPS has a melting point of 285 ℃, a glass transition temperature of 92 ℃, a thermal deformation temperature after reinforcement of generally more than 260 ℃, and can be used in a temperature range of 180-220 ℃, and is one of the varieties with the best heat resistance in engineering plastics. PPS has corrosion resistance close to that of tetrafluoroethylene, and chemical resistance inferior to that of polytetrafluoroethylene; only chloronaphthalene is currently soluble in PPS above 175 ℃. PPS has high strength and modulus, good rigidity, metallic texture, and is widely used as a structural polymer material. PPS itself has good flame retardance, and the flame retardance grade of the pure resin can reach V-0/5VA. Meanwhile, the composite material can be prepared into various functional films, coatings and composite materials, and can be successfully applied to the fields of electronics, military industry, aerospace, automobile transportation and the like.
At present, in order to obtain high-molecular-weight polyphenylene sulfide in a short time, auxiliary agents such as sodium acetate, lithium chloride, fatty acid salts and the like are often required to be added, so that the difficulty in purifying sodium chloride as a byproduct and recovering the auxiliary agents and NMP is increased, and the cost for preparing the polyphenylene sulfide is increased.
In the prior art, chinese patent CN109535426A discloses a polyphenylene sulfide resin synthesis process, specifically discloses a polyphenylene sulfide resin synthesis process which adopts sodium hydrosulfide containing a certain amount of crystal water, sodium hydroxide and p-dichlorobenzene as raw materials, wherein sodium hydrosulfide and sodium hydroxide are respectively added into different reaction kettles of a dehydration system before the dehydration process is started, and respectively prepared into water solutions with a certain mass concentration, meanwhile, the reaction kettles are respectively heated, after the temperature is raised to a certain temperature, the two water solutions are mixed together, after the temperature is raised to a certain temperature, the sodium sulfide is generated for a certain time, NMP solvent is added, then the dehydration system is heated and dehydrated, after the dehydration is completed, sodium sulfide generated by adding p-dichlorobenzene into the synthesis system is subjected to condensation polymerization, after the low temperature and the high temperature condensation polymerization are completed, acetate, NMP and the water solution are added by a high pressure pump, then, after the temperature of the polymerization system is kept at 260-270 ℃, the temperature is reduced to 160-180 ℃, the temperature is filtered while the water is hot, the filter cake is repeatedly washed by deionized water, and the filter cake is dried, thus obtaining the polyphenylene sulfide resin. Acetate is added in the process of preparing the polyphenylene sulfide resin, sodium chloride which is a byproduct generated in the synthesis process of the acetate and the polyphenylene sulfide enters an NMP solvent recovery system, and after NMP solvent is recovered, the mixture of solid sodium chloride and acetate is difficult to separate, and is usually identified as dangerous waste due to environmental protection policy; and filtering and washing for multiple times can generate a large amount of salt-containing wastewater, the salt-containing wastewater is required to be concentrated and evaporated in industry, the energy consumption is high, and a mixture of sodium chloride and acetate which are difficult to separate can be generated.
Chinese patent CN103819675a discloses an industrial synthesis process of polyphenylene sulfide resin without any auxiliary agent, specifically discloses a process for synthesizing polyphenylene sulfide resin by polycondensation of sodium hydrosulfide, sodium hydroxide and p-dichlorobenzene as raw materials in N-methyl-2-pyrrolidone solvent; on the premise of not increasing the cost of the raw materials for synthesizing the polyphenylene sulfide resin, the polydisperse coefficient and the oxygen index of the resin are improved by reasonably selecting process control conditions, raw materials and auxiliary materials, the post-synthesis treatment process flow of the polyphenylene sulfide resin is shortened, and the final purpose of optimizing the electrical insulation performance of the polyphenylene sulfide resin is achieved. However, the synthesis process is complex, the reaction time is long, the production period is too long, the production efficiency is low, and the industrial production is not facilitated.
In view of the above, it is necessary to provide a new method for synthesizing polyphenylene sulfide without an aid under inert gas pressurization, which has very important significance.
Disclosure of Invention
In order to overcome the technical defects, the method for synthesizing the polyphenylene sulfide without the aid by pressurizing inert gas is based on pressurizing polymerization and adding a phase separation agent for phase separation polymerization, and the pressurizing inert gas can reduce the gasification of reaction materials, so that the reaction materials are subjected to liquid phase polycondensation, and the time for converting the reaction materials into the polyphenylene sulfide is shortened; after adding the phase separating agent, the reaction system is converted into a concentrated phase of polyphenylene sulfide and a dilute phase of a polyphenylene sulfide NMP solution, the concentrated phase of the polyphenylene sulfide can be rapidly grown into high molecular weight polyphenylene sulfide, and a high molecular weight polyphenylene sulfide product can be prepared in a short time and has the characteristics of large average particle size and low melt mass flow rate.
A method for synthesizing polyphenylene sulfide by pressurizing inert gas without an auxiliary agent comprises the following steps:
1) Preparing sodium sulfide: adding sodium hydrosulfide, sodium hydroxide and NMP into a solvent for heating, reacting and removing the solvent to obtain a sodium sulfide solution;
2) Pressurized prepolymerization: adding paradichlorobenzene into the sodium sulfide solution prepared in the step 1) under the protection of inert gas of 0.1-1 Mpa in a high-pressure reaction kettle, mixing, and carrying out prepolymerization at a first temperature to obtain a prepolymerization product;
3) And (3) heating and polymerizing: carrying out temperature-rising polymerization on the pre-polymerization reaction product obtained by pressurized pre-polymerization in the step 2) at a second temperature to obtain a temperature-rising polymerization reaction product;
4) Phase separation: adding a phase separating agent into the heating polymerization reaction product of the heating polymerization in the step 3), and then carrying out phase separation at a third temperature to obtain the polyphenylene sulfide.
In one embodiment of the invention, step 1) produces sodium sulfide, the molar ratio of sodium hydrosulfide, sodium hydroxide and NMP being 1: (1-1.1): (2-8).
In one embodiment of the invention, step 1) produces sodium sulfide, which is an aqueous sodium sulfide solution having a concentration of 45 to 47 wt%; the sodium hydroxide is sodium hydroxide aqueous solution with the concentration of 40-50 wt%; the solvent is water.
In one embodiment of the invention, step 1) sodium sulfide is prepared, the temperature of the reaction and solvent removal is 230-240 ℃; the time for the reaction and the solvent removal is 2 to 3.5 hours.
In one embodiment of the invention, step 2) is a pressurized prepolymerization, the molar ratio of sodium sulfide to p-dichlorobenzene in the sodium sulfide solution being 1: (1-1.06).
In a specific embodiment of the present invention, step 2) is pressurized prepolymerization, and the inert gas is any one of nitrogen, helium and argon.
In one embodiment of the present invention, step 2) is a pressurized prepolymerization, the inert gas pressure being between 0.3 and 0.5MPa.
In one embodiment of the present invention, step 2) pressure prepolymerization, said first temperature being 200 to 230 ℃; the time of the prepolymerization reaction is 1-3 h.
In one embodiment of the present invention, step 3) heating polymerization, wherein the second temperature is 260-280 ℃; the heating polymerization time is 1-3 h.
In one embodiment of the present invention, step 4) phase separates, the phase separating agent is water, and the molar ratio of water to sodium sulfide in the sodium sulfide solution is (2-6): 1, a step of; the third temperature is 250-260 ℃; the phase separation time is 0.1-1 h.
The polyphenylene sulfide prepared by the invention has high molecular weight and excellent internal heat performance and mechanical property, can be used as special engineering plastics, and can be widely applied to a plurality of fields such as reinforcing materials, composite materials, flame-retardant materials, functional films, special fiber materials and the like.
The beneficial effects of the invention are as follows: the invention adopts the polymerization process of inert gas pressurization and phase separation under the condition of no auxiliary agent, can obtain high molecular weight polyphenylene sulfide in a short time, can improve the production efficiency of synthesizing the polyphenylene sulfide, shortens the purification process of byproduct sodium chloride, saves the recovery of the auxiliary agent, reduces engineering construction investment, and greatly reduces the production cost of manufacturing the polyphenylene sulfide; the polyphenylene sulfide prepared by the method has better average particle size and melt flow rate, can better meet the requirements of post-processing technology, and can improve the reliability and quality of product molding.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
A method for synthesizing polyphenylene sulfide by pressurizing inert gas without an auxiliary agent comprises the following steps:
1) Preparing sodium sulfide: adding sodium hydrosulfide, sodium hydroxide and NMP into a solvent for heating, reacting and removing the solvent to obtain a sodium sulfide solution;
2) Pressurized prepolymerization: adding paradichlorobenzene into the sodium sulfide solution prepared in the step 1) under the protection of inert gas of 0.1-1 Mpa in a high-pressure reaction kettle, mixing, and carrying out prepolymerization at a first temperature to obtain a prepolymerization product;
3) And (3) heating and polymerizing: carrying out temperature-rising polymerization on the pre-polymerization reaction product obtained by pressurized pre-polymerization in the step 2) at a second temperature to obtain a temperature-rising polymerization reaction product;
4) Phase separation: adding a phase separating agent into the heating polymerization reaction product of the heating polymerization in the step 3), and then carrying out phase separation at a third temperature to obtain the polyphenylene sulfide.
In some examples, step 1) produces sodium sulfide with a molar ratio of 1: (1-1.1): (2-8).
In some examples, 2 to 3.5 mol of water remain per 1 mol of sodium sulfide in the sodium sulfide solution; the water remaining in the sodium sulfide solution contains crystal water and free water.
In some examples, step 1) preparing sodium sulfide, and performing a temperature-raising reaction in an atmosphere of inert gas at a gas pressure of 0.1MPa; concretely, inert gas is adopted to replace the reaction kettle, and the raw material for preparing sodium sulfide is added under the pressure of 0.1MPa after the replacement is completed.
In some examples, step 1) produces sodium sulfide, which is an aqueous sodium sulfide solution having a concentration of 45 to 47 wt%; the sodium hydroxide is sodium hydroxide aqueous solution with the concentration of 40-50 wt%; the solvent is water.
In some examples, step 1) produces sodium sulfide at a temperature of 230 to 240 ℃ for the reaction and removal of solvent; the time for the reaction and the solvent removal is 2 to 3.5 hours.
In some examples, step 2) pressure prepolymerization, the molar ratio of sodium sulfide to p-dichlorobenzene in the sodium sulfide solution is 1: (1-1.06).
In some examples, step 2) is a pressurized prepolymerization, the inert gas being any one of nitrogen, helium, argon.
In some examples, step 2) is a pressurized prepolymerization, the inert gas pressure being from 0.3 to 0.5MPa.
In some examples, step 2) pressure prepolymerization, said first temperature being 200 to 230 ℃; the time of the prepolymerization reaction is 1-3 h.
In some examples, step 3) is a polymerization at elevated temperature, the second temperature being 260-280 ℃; the heating polymerization time is 1-3 h.
In some examples, step 4) phase separates, the phase separating agent is water, and the molar ratio of water to sodium sulfide in the sodium sulfide solution is (2-6): 1, a step of; the third temperature is 250-260 ℃; the phase separation time is 0.1-1 h.
The invention will be described in detail with reference to specific examples.
Example 1
A method for synthesizing polyphenylene sulfide by pressurizing inert gas without an auxiliary agent comprises the following steps:
1) Adding 1.698kg of 48wt% sodium hydroxide aqueous solution and 2.206kg of 47wt% sodium hydrosulfide as aqueous solutions into a dehydration kettle, reacting for 10min at normal temperature to generate sodium sulfide, adding 6.000kg of NMP, gradually heating to 220 ℃ under the protection of nitrogen atmosphere to remove water in the system, and distilling 1.63kg of water and 0.92kg of NMP after 3h of use to obtain sodium sulfide solution.
2) 2.700kg of paradichlorobenzene is put into a melting kettle and melted into liquid by heating; in the autoclave, the temperature of the sodium sulfide solution was lowered to 170℃and then paradichlorobenzene melt was added dropwise into the autoclave over 0.1 hour, and 0.92kg of NMP distilled off in the dehydration stage was recovered.
3) Filling nitrogen with the pressure of 0.3MPa (taking the reading of a pressure gauge as a reference, and representing the atmospheric pressure when the reading of the pressure gauge is 0), heating to 220-230 ℃ for prepolymerization reaction for 2h, heating to 260-270 ℃ for reaction for 2h, finally filling 800g of water into the high-pressure reaction kettle, and carrying out phase separation reaction for 1h at 250-255 ℃; cooling the reaction system, and carrying out solid-liquid separation to obtain polyphenylene sulfide powder granules.
Example 2
This embodiment differs from embodiment 1 in that: in step 3), 0.1MPa of nitrogen gas (nitrogen gas pressure is expressed as atmospheric pressure when the pressure gauge reading is 0 based on the pressure gauge reading) is charged into the high-pressure reaction kettle.
Example 3
This embodiment differs from embodiment 1 in that: in the step 3), the water injection amount is 700g.
Comparative example 1
This comparative example differs from example 1 in that: in the step 3), the high-pressure reaction kettle is replaced by nitrogen (the reading of a pressure gauge is 0), the temperature is raised to 220-230 ℃ for prepolymerization reaction for 2 hours, then the temperature is raised to 260-270 ℃ for reaction for 2 hours, finally 800g of water is injected into the high-pressure reaction kettle, and the phase separation reaction is carried out for 1 hour at 250-255 ℃; cooling the reaction system, and carrying out solid-liquid separation to obtain polyphenylene sulfide powder granules.
Comparative example 2
This comparative example differs from example 1 in that: in the step 3), the high-pressure reaction kettle is replaced by nitrogen (the reading of a pressure gauge is 0), the temperature is raised to 220-230 ℃ for prepolymerization reaction for 2 hours, then the temperature is raised to 260-270 ℃ for reaction for 2 hours, and finally the reaction is carried out for 1 hour at 250-255 ℃; cooling the reaction system, and carrying out solid-liquid separation to obtain polyphenylene sulfide powder granules.
Comparative example 3
This comparative example differs from example 1 in that: in the step 3), the temperature is raised to 260-270 ℃ for reaction for 0.5h; phase separation reaction is carried out for 0.3h at the temperature of 250-255 ℃.
The properties of the polyphenylene sulfide finished products of examples 1 to 3 and comparative examples 1 to 3 were examined.
1. Based on GBT 15445.2-2006, description of particle size analysis results part 2: and calculating the average particle diameter/diameter and each moment according to the particle size distribution to detect the average particle diameter of the polyphenylene sulfide finished product.
2. The melt mass flow rate of the polyphenylene sulfide finished product under the conditions of 315 ℃ and 5kg is detected based on GBT 3682-2000 melt mass flow rate.
3. The weight average molecular weight and the molecular weight distribution index of the polyphenylene sulfide finished product were measured based on high temperature Gel Permeation Chromatography (GPC) using α -chloronaphthalene as a solvent at a test temperature of 200 ℃.
Detection result:
the average particle size, melt mass flow rate and yield statistics of the polyphenylene sulfide finished products of examples 1 to 3 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1
As can be seen from table 1, the polyphenylene sulfides of examples 1 to 3 have larger average particle diameter and lower melt flow rate than comparative example 1, indicating that the pressurization of the inert gas during the polymerization of polyphenylene sulfide is advantageous for obtaining a higher molecular weight polyphenylene sulfide product; compared with comparative example 2, the polyphenylene sulfide of examples 1 to 3 has a larger average particle diameter and a lower melt flow rate, which indicates that the polyphenylene sulfide can promote phase separation of the polyphenylene sulfide by adding water after the polymerization is completed, and a high molecular weight polyphenylene sulfide can be obtained in a short time; as can be seen from the results of the average particle size and melt mass flow rate of the polyphenylene sulfide products of comparative examples 1 and 2, the effect of adding water during phase separation on the polyphenylene sulfide product is greater than the effect of inert gas pressurization during polymerization on the properties of the polyphenylene sulfide product; comparative example 3 compared with example 1, even if the reaction time is shortened, the comparative example 3 can obtain polyphenylene sulfide of high molecular weight by shortening the reaction time; experimental results show that in the process of preparing the polyphenylene sulfide product, the average particle size and the melt mass flow rate of the prepared polyphenylene sulfide product are improved together by carrying out phase separation synergistic cooperation through pressurized polymerization and water addition, and the high-molecular-weight polyphenylene sulfide can be obtained in a short time.
Claims (10)
1. The method for synthesizing the polyphenylene sulfide by pressurizing inert gas without an auxiliary agent is characterized by comprising the following steps of:
1) Preparing sodium sulfide: adding sodium hydrosulfide, sodium hydroxide and NMP into a solvent for heating, reacting and removing the solvent to obtain a sodium sulfide solution;
2) Pressurized prepolymerization: adding paradichlorobenzene into the sodium sulfide solution prepared in the step 1) under the protection of inert gas of 0.1-1 Mpa in a high-pressure reaction kettle, mixing, and carrying out prepolymerization at a first temperature to obtain a prepolymerization product;
3) And (3) heating and polymerizing: carrying out temperature-rising polymerization on the pre-polymerization reaction product obtained by pressurized pre-polymerization in the step 2) at a second temperature to obtain a temperature-rising polymerization reaction product;
4) Phase separation: adding a phase separating agent into the heating polymerization reaction product of the heating polymerization in the step 3), and then carrying out phase separation at a third temperature to obtain the polyphenylene sulfide.
2. The method according to claim 1, characterized in that: step 1) preparing sodium sulfide, wherein the molar ratio of sodium hydrosulfide to sodium hydroxide to NMP is 1: (1-1.1): (2-8).
3. The method according to claim 1 or 2, characterized in that: step 1) preparing sodium sulfide, wherein the sodium sulfide is sodium sulfide aqueous solution with the concentration of 45-47 wt%; the sodium hydroxide is sodium hydroxide aqueous solution with the concentration of 40-50 wt%; the solvent is water.
4. The method according to claim 1, characterized in that: step 1) preparing sodium sulfide, wherein the temperature for reaction and solvent removal is 230-240 ℃; the time for the reaction and the solvent removal is 2 to 3.5 hours.
5. The method according to claim 1, characterized in that: step 2) pressurized prepolymerization, wherein the molar ratio of sodium sulfide to p-dichlorobenzene in the sodium sulfide solution is 1: (1-1.06).
6. The method according to claim 1, characterized in that: step 2) pressurizing and prepolymerizing, wherein the inert gas is any one of nitrogen, helium and argon.
7. The method according to claim 1 or 5, characterized in that: step 2) pressurized prepolymerization, wherein the pressure of the inert gas is 0.3-0.5 Mpa.
8. The method according to claim 1, characterized in that: step 2) pressurized prepolymerization, wherein the first temperature is 200-230 ℃; the time of the prepolymerization reaction is 1-3 h.
9. The method according to claim 1, characterized in that: step 3) heating and polymerizing, wherein the second temperature is 260-280 ℃; the heating polymerization time is 1-3 h.
10. The method according to claim 1, characterized in that: step 4) phase separation, wherein the phase separating agent is water, and the molar ratio of the water to sodium sulfide in the sodium sulfide solution is (2-6): 1, a step of; the third temperature is 250-260 ℃; the phase separation time is 0.1-1 h.
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