CN111548492B - Polyphenylene sulfide and synthesis method thereof - Google Patents
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Abstract
The invention relates to a synthetic method of polyphenylene sulfide, belonging to the technical field of synthesis of high polymer material resin. The invention aims to provide a synthetic method of polyphenylene sulfide. The method comprises the following steps: 1) Mixing the sodium sulfide, liCl and NMP for azeotropic dehydration; 2) Mixing the dehydrated material with chlorobenzene, heating to 250-270 ℃ and reacting for 1.5-3 hours; 3) Cooling to 220-235 ℃, adding p-dichlorobenzene, mixing and reacting for 2-3 hours, then heating to 250-270 ℃, and reacting for 4-5 hours to obtain a reacted material; 4) And cooling the reacted materials, filtering, washing the solid, and drying to obtain the polyphenylene sulfide. The invention firstly adopts chlorobenzene to react with sodium sulfide to generate thiophenol monofunctional substance, and then adds p-dichlorobenzene to carry out reaction polymerization, and the method has the advantages of simple operation, low cost and short polymerization time, and the obtained polyphenylene sulfide has few active end groups, improves the stability of the polyphenylene sulfide and is convenient for later processing.
Description
Technical Field
The invention relates to a synthetic method of polyphenylene sulfide, belonging to the technical field of synthesis of high polymer material resin.
Background
The polyphenylene sulfide resin has excellent chemical resistance and high-temperature thermal stability, and has the performances of flame retardance, insulation, radiation resistance and the like. The engineering plastic is suitable for producing various electronic devices, automobile parts and the like by injection molding, extrusion molding and other methods.
At present, in the industrial production of polyphenylene sulfide resin, water-containing sodium sulfide and p-dichlorobenzene are mostly used as raw materials, no matter the sodium sulfide is excessive or the p-dichlorobenzene is excessive, the end groups of the produced polyphenylene sulfide resin are mainly chlorine-containing groups and sulfydryl-containing groups, the groups still have activity in the high-temperature processing process, and because the end group active groups are too many, the groups are easy to react at high temperature and then are separated or react with other substances, degrade or crosslink, and have poor flowability, the processing of a screw extruder is seriously influenced in the modification processing process of the polyphenylene sulfide resin, particularly inorganic materials are added in a high filling mode, therefore, the polyphenylene sulfide resin with certain stable viscosity is needed, the change of the melt index in the processing process is reduced, and the polyphenylene sulfide resin has a more stable resin melt index.
In order to reduce the reactive end groups of polyphenylene sulfide resins, a common method in the art is to add an end-capping agent. For example, patent WO1990000575 discloses a terminal-capped copolymerization to prepare a terminal-capped copolymer arylene sulfide by heating a diiodo aromatic compound and a small amount of a monoiodo aromatic compound in the presence of elemental sulfur, wherein the monoiodo aromatic compound is used as a chain terminator. The copolymerized polyarylene sulfide is prepared by using p-diiodobenzene as a raw material, the p-diiodobenzene is expensive and reacts with sulfur, so that a plurality of polysulfide bonds are generated, and although a monoiodoaromatic compound is used as a chain termination agent, the problem that the chain breakage of the polysulfide bonds during the processing of the resin still exists, the temperature resistance of the PPS resin is not high, and the change of a melt index at a high temperature is large is caused.
Chinese patent CN106633062A discloses a low-chlorine-content polyphenylene sulfide, a preparation method thereof, a resin composition and a molded body, wherein the low-chlorine-content polyphenylene sulfide is obtained by end capping with 4-phenylthio-benzenethiol (PTT). The preparation method of the polyphenylene sulfide takes a sulfur-containing compound, an alkaline substance and p-dichlorobenzene as raw materials, takes fatty acid as a polycondensation auxiliary agent and takes PTT as an end group regulator to carry out polycondensation reaction. The method has the advantages of high product yield and low cost, the obtained polyphenylene sulfide product has low chlorine content and excellent fluidity and heat resistance, but the method does not reduce the number of active end groups, only changes the chlorine end group into another sulfur end group, does not change the total amount of the sulfur end group and the chlorine end group, has the activity of the sulfur mercapto end group, and simultaneously causes the problems of high cost and difficult preparation for the production of resin because the PTT is difficult to produce.
Disclosure of Invention
In order to overcome the defects, the invention provides a synthetic method of polyphenylene sulfide.
The synthetic method of the polyphenylene sulfide comprises the following steps:
1) Dehydrating raw material sodium sulfide: mixing the sodium sulfide, liCl and NMP, and performing azeotropic dehydration to obtain a dehydrated material;
2) Pretreatment: mixing the dehydrated material with chlorobenzene, heating to 250-270 ℃ and reacting for 1.5-3 hours to obtain a pretreated material;
3) Polymerization: cooling the pretreated material to 220-235 ℃, mixing the pretreated material with p-dichlorobenzene, reacting for 2-3 hours, then heating to 250-270 ℃, and reacting for 4-5 hours to obtain a reacted material;
4) And (3) post-treatment: and cooling the reacted materials, filtering, washing the solid, and drying to obtain the polyphenylene sulfide.
Preferably, in step 1), the molar ratio of sodium sulfide monohydrate to NMP: liCl = 1.
Among them, in the step 1), it is preferable that the azeotropic dehydration is carried out by raising the temperature to 195 to 210 ℃ under a protective atmosphere.
Preferably, the protective atmosphere is an inert atmosphere or nitrogen.
Preferably, the inert atmosphere is helium, neon, argon, krypton or xenon.
Preferably, in the step 2), the molar ratio of sodium sulfide to chlorobenzene in the dehydrated material is 1.
Preferably, the molar ratio of p-dichlorobenzene in step 3) to sodium sulfide dihydrate in step 1) is 1-1.01.
Preferably, in the step 4), after the reaction materials are vacuumized to recover the solvent, deionized water is added for soaking and cooling.
Preferably, deionized water is used for washing.
The invention also provides the polyphenylene sulfide resin synthesized by the method for synthesizing the polyphenylene sulfide.
The polyphenylene sulfide resin is partially end-capped polyphenylene sulfide, and end-capped end groups are benzene rings, so that the amount of chlorine and sulfur in active end groups can be reduced, and the stability of the polyphenylene sulfide is improved.
The method controls the raw material of the sodium sulfide polyhydrate, namely Na is used 2 S·3H 2 O is firstly dehydrated and then reacts with chlorobenzene to generate a certain amount of thiophenol monofunctional substance, and then p-dichlorobenzene is added for reaction polymerization. Due to the existence of monofunctional active thiophenolate, part of polymers only have one active group in the polymerization and reaction processes, and the reaction is carried out in one direction, so that the polyphenylene sulfide with relatively high molecular weight is obtained, and part of end groups are benzene rings, so that the number of active end groups chlorine or sulfur is reduced, and the polyphenylene sulfide with reduced active end groups chlorine and sulfur is obtained.
Compared with the prior art, the invention has the following beneficial effects:
the method adopts chlorobenzene to react with sodium sulfide for the first time to generate thiophenol monofunctional group substances, and then adds p-dichlorobenzene to perform reaction polymerization.
Detailed Description
The synthetic method of the polyphenylene sulfide comprises the following steps:
1) Dehydrating raw material sodium sulfide: mixing the sodium sulfide, liCl and NMP, and performing azeotropic dehydration to obtain a dehydrated material;
2) Pretreatment: mixing the dehydrated material with chlorobenzene, heating to 250-270 ℃ and reacting for 1.5-3 hours to obtain a pretreated material;
3) Polymerization: cooling the pretreated material to 220-235 ℃, mixing the pretreated material with p-dichlorobenzene, reacting for 2-3 hours, then heating to 250-270 ℃, and reacting for 4-5 hours to obtain a reacted material;
4) And (3) post-treatment: and cooling the reacted materials, filtering, washing the solid, and drying to obtain the polyphenylene sulfide.
In the conventional PPS production method, each linear PPS molecule has two terminal groups, i.e., chlorine or sulfur-containing groups, which are highly active during high-temperature processing, resulting in decomposition or chain growth of polyphenylene sulfide, and thus are easily removed or participate in reaction, resulting in a change in melt index (melt index). The method of the invention utilizes chlorobenzene to react with a large amount of sulfur-containing compounds at high temperature to firstly generate substances containing thiophenoxide, and plays a role of adjusting polymerization reaction with single functional group in the polymerization process to reduce the number of the thiosulfydryl end group or the chlorine end group and other active end groups in the polyphenylene sulfide resin generated by the reaction of p-dichlorobenzene and sodium sulfide, thereby achieving the purpose of reducing the active end groups and obtaining the polyphenylene sulfide with a certain amount of relatively inert benzene end groups.
The step 1) is a step of azeotropic dehydration of sodium sulfide, and can be carried out by adopting a conventional method.
Preferably, in step 1), the molar ratio of sodium sulfide monohydrate to NMP: liCl = 1.
Preferably, in the step 1), the azeotropic dehydration is carried out by raising the temperature to 195 to 210 ℃ under a protective atmosphere.
The protective atmosphere in the invention is an atmosphere which does not participate in the reaction. Preferably, the protective atmosphere is an inert atmosphere or a nitrogen atmosphere. The inert atmosphere is inert gas protection, and preferably, the inert atmosphere is helium, neon, argon, krypton or xenon.
And step 2) is a pretreatment step, chlorobenzene is added to react with sodium sulfide to generate a substance containing thiophenolate. Due to the difference of the K values of the reaction constants of chlorobenzene and p-dichlorobenzene, if the chlorobenzene and the p-dichlorobenzene exist simultaneously, sodium sulfide firstly reacts with the p-dichlorobenzene, the chlorobenzene participates in the reaction with great difficulty, and thus the expected effect cannot be achieved. Or chlorobenzene is added after the polymerization is completed, and since the activity of the long-chain PPS becomes low, chlorobenzene does not play a role in polymerization end capping at all. Therefore, the present invention requires pretreatment before polymerization to allow chlorobenzene to react with sodium sulfide.
Preferably, in the step 2), the molar ratio of sodium sulfide to chlorobenzene in the dehydrated material is 1.
And 3) a polymerization reaction step, wherein sodium sulfide and p-dichlorobenzene react to generate polyphenylene sulfide. The common ratio of sodium sulfide to p-dichlorobenzene is suitable for the invention. Preferably, the molar ratio of p-dichlorobenzene in step 3) to sodium sulfide dihydrate in step 1) is 1-1.01.
And 4) a post-treatment step, namely obtaining the polyphenylene sulfide resin from the polyphenylene sulfide-containing slurry.
Preferably, in the step 4), after the reaction materials are vacuumized to recover the solvent, deionized water is added for soaking and cooling. The solvent can be recycled after being recovered, and the synthesis cost of the polyphenylene sulfide is reduced.
In order to reduce the introduction of impurity ions, it is preferable that, in step 4), deionized water is used for washing.
The invention also provides the polyphenylene sulfide resin synthesized by the synthesis method.
The polyphenylene sulfide resin is partially end-capped polyphenylene sulfide, and end-capped end groups are benzene rings, so that the amount of chlorine and sulfur in active end groups can be reduced, and the stability of the polyphenylene sulfide is improved.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the invention to the embodiments described.
Example 1
40kg of NMP solvent, 11kg of sodium sulfide trihydrate (the content of sodium sulfide is 60 percent) and 1.4kg of lithium chloride are added into a 60L pure titanium polymerization reaction kettle, and the temperature is raised to 205 ℃ under the protection of nitrogen for azeotropic dehydration, so that 7.5kg of liquid is removed altogether. The reaction vessel was closed, 0.49kg of chlorobenzene was added to a 60L polymerization vessel, and then the temperature was raised to 270 ℃ at a rate of 10 ℃/h for 2 hours. Then the temperature of the reaction kettle is reduced to 225 ℃, 12.4kg of p-dichlorobenzene is added through a metering pump, the temperature is controlled to 230 ℃ for reaction for 3 hours, then the temperature is increased from 230 ℃ to 265 ℃ at the heating rate of 10 ℃/h, and the reaction is carried out for 4.5 hours at 265 ℃. And after the reaction is finished, the reaction kettle is decompressed, vacuumized, added with deionized water, cooled and filtered, and the filter cake is acidified by dilute hydrochloric acid, washed and dried. 8.14kg of PPS resin was obtained.
Example 2
40kg of NMP solvent, 11kg of sodium sulfide trihydrate (the content of sodium sulfide is 60 percent) and 1.4kg of lithium chloride are added into a 60L pure titanium polymerization reaction kettle, and the temperature is raised to 205 ℃ under the protection of nitrogen for azeotropic dehydration, so that 7.4kg of liquid is removed altogether. The reaction vessel was closed, 0.49kg of chlorobenzene was added to a 60L polymerization vessel, and then the temperature was raised to 265 ℃ at a rate of 10 ℃/h for 1.5 hours. Then the temperature of the reaction kettle is reduced to 220 ℃, 12.5kg of p-dichlorobenzene is added through a metering pump, the temperature of the reaction kettle is controlled to be 220 ℃, the reaction is carried out for 3 hours, then the temperature is increased from 220 ℃ to 265 ℃ according to the temperature increasing speed of 10 ℃/h, and the reaction is carried out for 5 hours at 265 ℃. And after the reaction is finished, the reaction kettle is decompressed, vacuumized, added with deionized water, cooled and filtered, and the filter cake is acidified by dilute hydrochloric acid, washed and dried. 8.20kg of PPS resin was obtained.
Example 3
40kg of NMP solvent, 11kg of sodium sulfide trihydrate (the content of sodium sulfide is 60 percent) and 1.4kg of lithium chloride are added into a 60L pure titanium polymerization reaction kettle, and the temperature is raised to 205 ℃ under the protection of nitrogen for azeotropic dehydration, so that 7.8kg of liquid is removed altogether. The reaction vessel was closed, 0.75kg of chlorobenzene was added to the polymerization vessel, and then the temperature was raised to 270 ℃ at a rate of 10 ℃/h for 2 hours. Then the temperature of the reaction kettle is reduced to 225 ℃, 12.4kg of p-dichlorobenzene is added through a metering pump, the temperature is controlled to 230 ℃ for reaction for 3 hours, then the temperature is increased from 230 ℃ to 260 ℃ at the temperature increasing speed of 10 ℃/h, and the reaction is carried out for 4 hours at 265 ℃. And after the reaction is finished, the reaction kettle is decompressed, vacuumized, added with deionized water, cooled and filtered, and the filter cake is acidified by dilute hydrochloric acid, washed and dried. 8.18kg of PPS resin was obtained.
Example 4
40kg of solvent NMP, 11kg of sodium sulfide trihydrate (the content of sodium sulfide is 60 percent) and 1.4kg of lithium chloride are added into a 60L pure titanium polymerization reaction kettle, and the temperature is raised to 205 ℃ under the protection of nitrogen for azeotropic dehydration to remove 7.4kg of liquid. The reaction vessel was closed, 0.8kg of chlorobenzene was added to a 60L polymerization vessel, and then the temperature was raised to 270 ℃ at a rate of 10 ℃/h for 2.5 hours. Then the temperature of the reaction kettle is reduced to 225 ℃, 12.5kg of p-dichlorobenzene is added through a metering pump, the reaction is carried out for 3 hours at the temperature of 230 ℃, then the temperature is increased from 230 to 263 ℃ at the temperature increasing speed of 10 ℃/h, and the reaction is carried out for 4.5 hours at 263 ℃. And after the reaction is finished, the reaction kettle is decompressed, vacuumized, added with deionized water, cooled and filtered, and the filter cake is acidified by dilute hydrochloric acid, washed and dried. 8.23kg of PPS resin was obtained.
Comparative example 1
40kg of NMP solvent, 11kg of sodium sulfide trihydrate (the content of sodium sulfide is 60 percent) and 1.4kg of lithium chloride are added into a 60L pure titanium polymerization reaction kettle, and the temperature is raised to 205 ℃ under the protection of nitrogen for azeotropic dehydration, so that 7.5kg of liquid is removed altogether. The reaction kettle is closed, 12.4kg of p-dichlorobenzene is added through a metering pump, the temperature is controlled to be 228 ℃ for reaction for 3 hours, then the temperature is increased from 228 ℃ to 265 ℃ at the temperature increasing speed of 10 ℃/h, and the reaction is carried out for 4.5 hours at 265 ℃. And after the reaction is finished, the reaction kettle is decompressed and vacuumized, deionized water is added for cooling and filtering, and the filter cake is acidified by dilute hydrochloric acid, washed and dried to obtain 8.12kg of PPS resin.
Comparative example 2
40kg of solvent NMP, 11kg of sodium sulfide trihydrate (the content of sodium sulfide is 60 percent) and 1.4kg of lithium chloride are added into a 60L pure titanium polymerization reaction kettle, and the temperature is raised to 205 ℃ under the protection of nitrogen for azeotropic dehydration to remove 7.5kg of liquid. The reaction kettle is closed, 12.5kg of p-dichlorobenzene is added through a metering pump, the temperature is controlled to be 230 ℃ for reaction for 3 hours, then the temperature is increased from 230 ℃ to 260 ℃ at the temperature increasing speed of 10 ℃/h, and the reaction is carried out for 5 hours at 260 ℃. And after the reaction is finished, the reaction kettle is decompressed, vacuumized, added with deionized water, cooled and filtered, and the filter cake is acidified by dilute hydrochloric acid, washed and dried. 8.10kg of PPS resin was obtained.
And (3) evaluating the product quality:
equipment and standard:
electronic scale instrument model YL0061 (shanghai); melt index determinator model MFI-1221 (north Hebei Chengde); a rotational viscometer.
And (4) testing standard:
GB-T3682-2000 determination of melt mass flow rate and melt volume flow rate of thermoplastic plastics
BS EN 14582-2007 waste characterization-halogen and sulfur content-oxygen combustion method and determination method in closed system
And others: alpha-chloronaphthalene, diphenylcarbazone, 2, 4-dinitrochlorobenzene, ethanol and the like
Analysis of end groups:
1. determination of free chlorine in resin:
a certain amount of pure PPS powder is taken and dissolved in alpha-chloronaphthalene under heating, then the solution is cooled to room temperature and mixed with ethanol, the solution is filtered, the filtrate is titrated by using a standard mercuric nitrate solution to determine the chlorine content, the used indicator is diphenyl carbazone, and the obtained content is the free chlorine content.
2. Determination of the chlorine end groups:
a quantity of PPS powder was taken and the total chlorine content of the polymer was determined by the oxygen bottle combustion method, the terminal chlorine content being determined by subtracting the free chlorine content in test 1 from the total chlorine content.
3. Determination of thiol group:
taking a certain amount of PPS powder, reacting thiol end groups of PPS with 2, 4-dinitrochlorobenzene in alkaline alpha-chloronaphthalene to obtain chlorine quantitatively, and then titrating by using a standard mercuric nitrate solution to determine the chlorine content, wherein the used indicator is diphenylcarbazone, and the obtained total chlorine content is the total chlorine content. The total chlorine content minus the free chlorine content of test 1 is the conversion from mercaptans.
The evaluation results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the polyphenylene sulfide prepared by the method of the present invention has a low content of active end groups.
Claims (8)
1. The synthetic method of the polyphenylene sulfide is characterized by comprising the following steps:
1) Dehydrating raw material sodium sulfide: mixing the sodium sulfide, liCl and NMP, and performing azeotropic dehydration to obtain a dehydrated material;
2) Pretreatment: mixing the dehydrated material with chlorobenzene, heating to 250-270 ℃ and reacting for 1.5-3 hours to obtain a pretreated material; the molar ratio of sodium sulfide to chlorobenzene in the dehydrated material is 1.05-0.1;
3) Polymerization: cooling the pretreated material to 220-235 ℃, mixing the pretreated material with p-dichlorobenzene, reacting for 2-3 hours, then heating to 250-270 ℃, and reacting for 4-5 hours to obtain a reacted material;
4) And (3) post-treatment: and cooling the reacted materials, filtering, washing the solid, and drying to obtain the polyphenylene sulfide.
2. The method for synthesizing polyphenylene sulfide according to claim 1, characterized in that: in step 1), the molar ratio of sodium sulfide monohydrate to NMP: liCl = 1.
3. The method for synthesizing polyphenylene sulfide according to claim 1, wherein: in the step 1), azeotropic dehydration is carried out by heating to 195-210 ℃ under a protective atmosphere for evaporation.
4. The method for synthesizing polyphenylene sulfide according to claim 3, wherein: the protective atmosphere is inert atmosphere or nitrogen.
5. The method for synthesizing polyphenylene sulfide according to claim 4, characterized in that: the inert atmosphere is helium, neon, argon, krypton or xenon.
6. The method for synthesizing polyphenylene sulfide according to claim 1, wherein: the molar ratio of the p-dichlorobenzene in the step 3) to the sodium sulfide dihydrate in the step 1) is 1-1.01.
7. The method for synthesizing polyphenylene sulfide according to claim 1, wherein: in the step 4), after the reaction materials are vacuumized and the solvent is recovered, deionized water is added for soaking and cooling.
8. The method for synthesizing polyphenylene sulfide according to claim 7, characterized in that: washing with deionized water.
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| CN117534838A (en) * | 2023-10-17 | 2024-02-09 | 德阳科吉高新材料有限责任公司 | Modified polyphenylene sulfide and synthesis method thereof |
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| CN107522861A (en) * | 2017-08-17 | 2017-12-29 | 四川金和成科技有限公司 | A kind of preparation method of film polyphenylene sulfide resin |
| CN110818898A (en) * | 2019-11-22 | 2020-02-21 | 四川轻化工大学 | Method for dehydrating sodium sulfide dihydrate in polyphenylene sulfide production |
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