CN113087906B - Preparation method of polyphenylene sulfide ketone and product thereof - Google Patents
Preparation method of polyphenylene sulfide ketone and product thereof Download PDFInfo
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 45
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 45
- 150000002576 ketones Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 96
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000000047 product Substances 0.000 claims abstract description 52
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 51
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 51
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 44
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 35
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000018044 dehydration Effects 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 22
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 25
- 238000001704 evaporation Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- -1 ether ketone Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- XNFVGEUMTFIVHQ-UHFFFAOYSA-N disodium;sulfide;hydrate Chemical compound O.[Na+].[Na+].[S-2] XNFVGEUMTFIVHQ-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000000087 stabilizing effect Effects 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 21
- 238000005303 weighing Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 230000002829 reductive effect Effects 0.000 description 13
- 238000000926 separation method Methods 0.000 description 13
- 239000013078 crystal Substances 0.000 description 11
- 238000011049 filling Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 206010033307 Overweight Diseases 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- 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
- C08G75/10—Polythioethers from sulfur or sulfur-containing compounds and aldehydes or ketones
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a preparation method of polyphenylene sulfide ketone and a product thereof, which comprises the steps of adding crystalline sodium sulfide, solvent N-methylpyrrolidone (NMP) and caustic soda into a dehydration reaction vessel, heating for dehydration under the protection of nitrogen, and adjusting to a first-stage polymerization reaction temperature after dehydration. Adding 4, 4' -Dichlorobenzophenone (DCBP) and potassium carbonate serving as a catalyst into a polymerization reactor, stirring and heating to the first-stage reaction temperature in the nitrogen atmosphere, then sealing, and slowly adding a dehydration product into a polymerization reaction kettle to perform first-stage polymerization reaction. After the first-stage polymerization reaction is finished, heating to the temperature of the second-stage polymerization reaction to prepare the polyphenylene sulfide ketone. The polyphenylene sulfide ketone prepared by the invention has high molecular weight, reaction byproducts are easy to separate, the product comprehensive performance is good, and the yield is high.
Description
Technical Field
The invention belongs to the technical field of polymer engineering, and particularly relates to a preparation method of polyphenylene sulfide ketone and a product thereof.
Background
Polyphenylene sulfide ketone is a special organic high molecular compound with high heat resistance, corrosion resistance and thermoplasticity, the melting point of the polyphenylene sulfide ketone can reach 350 ℃, and the polyphenylene sulfide ketone is a special engineering plastic required by a plurality of special industrial fields.
As for the polymerization route and method of polyphenylene sulfide ketone, there are mainly reported an alkali metal vulcanization method, a halogenated thiophenol self-condensation polymerization method, a sulfur solution method, a phosgene method and the like. However, at present, no mature polyphenylene sulfide ketone product available for industrial use exists, and the problems are mainly that the polymerization degree of the product is low, or the side reaction is serious, so that the post-processing of the product is difficult, and the physical and mechanical performance indexes cannot meet the application requirements of related fields, so that the normal use of the product is influenced.
Therefore, there is a need in the art for a method of producing high molecular weight polyphenylene sulfide ketone with high degree of polymerization, low side reactions, and relatively easy processing.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of high molecular weight polyphenylene sulfide ketone.
In order to solve the technical problems, the invention provides the following technical scheme: a process for preparing high-molecular polyphenylsulfone ketone includes such steps as,
adding crystallized sodium sulfide, solvent N-methyl pyrrolidone and caustic soda into a dehydration reactor, stirring, heating, evaporating and dehydrating in a nitrogen atmosphere;
adjusting the material after dehydration reaction in the dehydration reactor to the temperature required by the first stage reaction;
adding 4, 4' -dichlorobenzophenone, potassium carbonate and solvent N-methylpyrrolidone into a polymerization reactor, stirring and heating to the first-stage reaction temperature under the nitrogen atmosphere, and sealing;
slowly adding materials in a dehydration reactor into a polymerization reactor through an injection pump, and stabilizing the first-stage reaction temperature through the cooperation of a polymerization reactor temperature regulating system to perform a first-stage reaction;
after the first stage reaction is finished, heating to the second stage reaction temperature to continue the polymerization reaction, after the second stage reaction is finished, cooling the reaction product, and separating, washing and drying to obtain a solid matter, namely the polyphenylene sulfide ether ketone product.
As a preferred scheme of the preparation method of the high molecular weight polyphenylene sulfide ketone, the method comprises the following steps: the crystallized sodium sulfide is any one or a mixture of 5 parts of sodium sulfide hydrate and 9 parts of sodium sulfide hydrate.
As a preferred scheme of the preparation method of the high molecular weight polyphenylene sulfide ketone, the method comprises the following steps: and (3) heating, evaporating and dehydrating at the temperature of 190-200 ℃.
As a preferred scheme of the preparation method of the high molecular weight polyphenylene sulfide ketone, the method comprises the following steps: the proportion of each reaction material is as follows: the molar ratio of the crystallized sodium sulfide to the caustic soda is 1: 0.05-0.08, wherein the molar ratio of the crystallized sodium sulfide to the 4, 4' -dichlorobenzophenone is 1: 0.95-0.98, the molar ratio of the crystalline sodium sulfide to the potassium carbonate is 1: 0.55-0.65, and the molar ratio of the crystalline sodium sulfide to the solvent N-methylpyrrolidone is 1: 6-8.
As a preferred scheme of the preparation method of the high molecular weight polyphenylene sulfide ketone, the method comprises the following steps: the molar ratio of the crystallized sodium sulfide to the 4, 4' -dichlorobenzophenone is 1: 0.96.
as a preferred scheme of the preparation method of the high molecular weight polyphenylene sulfide ketone, the method comprises the following steps: the first stage reaction temperature is 155 +/-2.5 ℃, and the reaction time is 120 +/-5 minutes.
As a preferred scheme of the preparation method of the high molecular weight polyphenylene sulfide ketone, the method comprises the following steps: the second-stage reaction temperature is 275 +/-2.5 ℃, and the reaction time is 120 +/-5 minutes.
It is a further object of the present invention to overcome the deficiencies of the prior art by providing a product made by the method of making high molecular weight polyphenylene sulfide ketone having a melting point of 350 ℃ and an intrinsic viscosity of 0.62 dL/g.
The invention has the beneficial effects that:
(1) the method for preparing the polyphenylene sulfide ketone adopts a dehydration method outside a polymerization reaction kettle, removes part of water in the crystallized sodium sulfide, and then carries out polymerization reaction in the polymerization reaction kettle by an injection charging method.
(2) The method for preparing the polyphenylene sulfide ketone adopts potassium carbonate as a catalyst, replaces the traditional lithium chloride catalyst, provides a polymerization process corresponding to the traditional lithium chloride catalyst, and solves the problem that the subsequent separation and recovery are difficult because the lithium chloride forms a coordination compound with a solvent in the polymerization reaction process.
(3) In the method for preparing the polyphenylene sulfide ether ketone, sodium sulfide which is dehydrated and well adjusted in temperature is added into a reaction system under the condition that potassium carbonate is used as a catalyst, a first-stage low-temperature polymerization method is adopted to control the further increase of the molecular weight of a prepolymer, the number of the prepolymers is increased, the reaction activity of the prepolymer is reserved for second-stage high-temperature polymerization, the generation of oligomers is reduced, and the uniformity of the molecular weight distribution and the polymerization degree of a product after the two-stage reaction is finished are further improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a flow chart of the preparation process of high molecular weight polyphenylene sulfide ketone according to the embodiment of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The invention relates to a preparation method of high-weight polyphenylene sulfide ketone, which comprises the steps of adding crystalline sodium sulfide, a solvent N-methyl pyrrolidone and caustic soda into a dehydration reactor according to the material proportion, stirring and heating to evaporate part of water in a nitrogen atmosphere, and then adjusting the temperature of the rest materials to the temperature required by the first-stage reaction through a temperature adjusting system of the dehydration reactor. Adding 4, 4' -dichlorobenzophenone, a catalyst potassium carbonate and a solvent N-methylpyrrolidone into a polymerization reactor according to a material ratio, stirring and heating to a first-stage reaction temperature under a nitrogen atmosphere, sealing, slowly adding the residual materials in the dehydration reactor into the polymerization reactor through an injection pump, and stabilizing at a temperature required by a first-stage reaction through the cooperation of a polymerization reactor temperature regulating system to perform the first-stage reaction. After the first stage reaction is finished, heating to the second stage reaction temperature to continue the polymerization reaction, after the second stage reaction is finished, cooling the reaction product, and filtering, separating, washing and drying to obtain a solid matter, namely the polyphenylene sulfide ether ketone product.
Example 1
Weighing 8Kg of industrial grade 5 water crystal sodium sulfide (based on the main content, taking the sodium sulfide as a quantitative reference 1), and weighing industrial grade 4, 4' -dichlorobenzophenone, a catalyst potassium carbonate, a solvent N-methylpyrrolidone and caustic soda according to an effective component molar ratio of 1:0.96:0.60:7: 0.06. Wherein one-fourth of the total amount of the solvent N-methylpyrrolidone is used for the dehydration step and three-fourths is used for the polymerization step.
Evaporating and dehydrating the crystallized sodium sulfide to 195 ℃, then filling nitrogen to cool to 155 ℃, wherein the first-stage polymerization temperature is 155 ℃, the time is 120 minutes, and the stirring speed is 90 rpm; the second-stage polymerization temperature was 275 ℃ for 120 minutes, and the stirring speed was 120 rpm.
After the polymerization reaction is finished, the reaction material is cooled to 165 ℃, and 8.25Kg of polyphenylene sulfide ketone product is obtained by separation, washing and drying, with the yield of 81.75%.
The product has a melting point of 350 ℃ by analysis,the intrinsic viscosity was 0.62dL/g (measured by capillary viscometer, 98% H)2SO4Is a solvent, the product concentration is 0.5g/dL, the test temperature is 25 +/-0.1 ℃, the same is applied below), and the product can be used for injection molding. A flow chart of a preparation process of high molecular weight polyphenylene sulfide ketone, see fig. 1.
Example 2
Weighing 8Kg of industrial grade 9 water crystal sodium sulfide (based on the main content, taking the sodium sulfide as a quantitative reference 1), and weighing industrial grade 4, 4' -dichlorobenzophenone, a catalyst potassium carbonate, a solvent N-methylpyrrolidone and caustic soda according to an effective component molar ratio of 1:0.95:0.65:8: 0.08. Wherein one-fourth of the total amount of the solvent N-methylpyrrolidone is used for the dehydration step and three-fourths is used for the polymerization step.
Evaporating and dehydrating the crystallized sodium sulfide to 195 ℃, then filling nitrogen to reduce the temperature to 155 ℃, wherein the first-stage polymerization temperature is 155 ℃, the time is 120 minutes, the stirring speed is 90rpm, the second-stage polymerization temperature is 275 ℃, the time is 120 minutes, and the stirring speed is 120 rpm.
After the polymerization reaction, the reaction mass was cooled to 165 ℃ and 5.25Kg of polyphenylene sulfide ketone product was obtained with a yield of 74.26% by separation, washing and drying. The product has a melting point of 350 ℃ and an intrinsic viscosity of 0.55dL/g, and can be used for injection molding.
Comparative example 1
Weighing 8Kg of industrial grade 5 water crystal sodium sulfide (based on the main content, taking the sodium sulfide as a quantitative reference 1), and weighing industrial grade 4, 4' -dichlorobenzophenone, a catalyst potassium carbonate, a solvent N-methylpyrrolidone and caustic soda according to an effective component molar ratio of 1:0.96:0.60:7: 0.06. Wherein one-fourth of the total amount of the solvent N-methylpyrrolidone is used for the dehydration step and three-fourths is used for the polymerization step.
Evaporating and dehydrating the crystallized sodium sulfide to 195 ℃, then filling nitrogen to cool to 180 ℃, wherein the first-stage polymerization temperature is 180 ℃, the time is 120 minutes, the stirring speed is 90rpm, the second-stage polymerization temperature is 275 ℃, the time is 120 minutes, and the stirring speed is 120 rpm.
After the polymerization reaction is finished, the reaction material is cooled to 165 ℃, and 6.75Kg of polyphenylene sulfide ketone product is obtained by separation, washing and drying, with the yield of 66.89%.
The product was analyzed to have a melting point of 350 ℃ and an intrinsic viscosity of 0.42 dL/g. The comparative example increases the temperature of the first-stage reaction, and the proportion of other materials and the production process are the same as those of the embodiment 1. However, the polymerization effect is significantly deteriorated, and the product yield and the intrinsic viscosity are lowered.
Comparative example 2
Weighing 8Kg of industrial grade 5 water crystal sodium sulfide (based on the main content, taking the sodium sulfide as a quantitative reference 1), and weighing industrial grade 4, 4' -dichlorobenzophenone, a catalyst potassium carbonate, a solvent N-methylpyrrolidone and caustic soda according to an effective component molar ratio of 1:0.96:0.60:7: 0.06. Wherein one-fourth of the total amount of the solvent N-methylpyrrolidone is used for the dehydration step and three-fourths is used for the polymerization step.
Evaporating and dehydrating the crystallized sodium sulfide to 195 ℃, then filling nitrogen to cool to 180 ℃, wherein the first-stage polymerization temperature is 180 ℃, the time is 120 minutes, the stirring speed is 90rpm, the second-stage polymerization temperature is 265 ℃, the time is 120 minutes, and the stirring speed is 120 rpm.
After the polymerization reaction is finished, the reaction material is cooled to 165 ℃, and 5.85Kg of polyphenylene sulfide ketone product is obtained by separation, washing and drying, with the yield of 57.97%. The product was analyzed to have a melting point of 345 ℃ and an intrinsic viscosity of 0.35 dL/g. The comparative example reduces the temperature of the second-stage reaction, and the proportion of other materials and the production process are the same as those of the embodiment 1. But the polymerization effect is obviously deteriorated, the product yield and the intrinsic viscosity are obviously reduced, and the product cannot be used as an injection molding product.
Comparative example 3
Weighing 8Kg of industrial grade 5 water crystal sodium sulfide (based on the main content, taking the sodium sulfide as a quantitative reference 1), and weighing industrial grade 4, 4' -dichlorobenzophenone, a catalyst potassium carbonate, a solvent N-methylpyrrolidone and caustic soda according to an effective component molar ratio of 1:0.96:0.60:7: 0.06. Wherein one-fourth of the total amount of the solvent N-methylpyrrolidone is used for the dehydration step and three-fourths is used for the polymerization step.
Adding the crystallized sodium sulfide, the solvent N-methyl pyrrolidone and caustic soda into a polymerization reactor according to the material ratio, evaporating and dehydrating to 195 ℃ in the nitrogen atmosphere, then cooling to 155 ℃, and sealing the polymerization reactor.
4, 4' -dichlorobenzophenone, a catalyst potassium carbonate and a solvent N-methylpyrrolidone are heated and dissolved outside a polymerization reactor according to the material ratio, and then are added into the polymerization reactor through a syringe pump for polymerization reaction. The first polymerization stage was carried out at 155 ℃ for 120 minutes with a stirring speed of 90rpm, and the second polymerization stage was carried out at 275 ℃ for 120 minutes with a stirring speed of 120 rpm. After the polymerization reaction is finished, the reaction material is cooled to 165 ℃, and 6.92Kg of polyphenylene sulfide ketone product is obtained by separation, washing and drying, with the yield of 68.57%.
The product was analyzed to have a melting point of 325 ℃ and an intrinsic viscosity of 0.45 dL/g.
Compared with example 1, the comparative example adopts a method of dehydration in a polymerization reactor, the other process indexes and steps are consistent with those of example 1, but the yield is obviously reduced, the melting point and the intrinsic viscosity of the product are also reduced, and the results show that the structure of a polymer chain segment is changed, side reactions are generated, and the polymerization effect is poor.
Comparative example 4
Weighing 8Kg of industrial grade 5 water crystal sodium sulfide (based on the main content, taking the sodium sulfide as a quantitative reference 1), and weighing industrial grade 4, 4' -dichlorobenzophenone, a catalyst potassium carbonate, a solvent N-methylpyrrolidone and caustic soda according to an effective component molar ratio of 1:0.96:0.45:7: 0.06. Wherein one-fourth of the total amount of the solvent N-methylpyrrolidone is used for the dehydration step and three-fourths is used for the polymerization step.
Evaporating and dehydrating the crystallized sodium sulfide to 195 ℃, then filling nitrogen to reduce the temperature to 155 ℃, wherein the first-stage polymerization temperature is 155 ℃, the time is 120 minutes, the stirring speed is 90rpm, the second-stage polymerization temperature is 275 ℃, the time is 120 minutes, and the stirring speed is 120 rpm. After the polymerization reaction is finished, the reaction material is cooled to 165 ℃, and the polyphenylene sulfide ketone product is obtained by separation, washing and drying, wherein the yield is 64.91 percent, and 6.55 Kg.
The product was analyzed to have a melting point of 350 ℃ and an intrinsic viscosity of 0.46 dL/g. Compared with the example 1, the comparative example reduces the dosage of the catalyst, and other process indexes and steps are consistent with those of the example 1, but the product yield and the intrinsic viscosity are obviously reduced, and the polymerization effect is obviously deteriorated.
Comparative example 5
Weighing 8Kg of industrial grade 5 water crystal sodium sulfide (based on the main content, taking the volume as a quantitative reference 1), and weighing industrial grade 4, 4' -dichlorobenzophenone, a catalyst potassium carbonate, a solvent N-methylpyrrolidone and caustic soda according to an effective component molar ratio of 1:0.96:0.45:7: 0.04. Wherein one-fourth of the total amount of the solvent N-methylpyrrolidone is used for the dehydration step and three-fourths is used for the polymerization step.
Evaporating and dehydrating the crystallized sodium sulfide to 195 ℃, then filling nitrogen to reduce the temperature to 155 ℃, wherein the first-stage polymerization temperature is 155 ℃, the time is 120 minutes, the stirring speed is 90rpm, the second-stage polymerization temperature is 275 ℃, the time is 120 minutes, and the stirring speed is 120 rpm. After the polymerization reaction is finished, the reaction material is cooled to 165 ℃, and 5.15Kg of polyphenylene sulfide ketone product with the yield of 64.91 percent is obtained by separation, washing and drying.
The product was analyzed to have a melting point of 350 ℃ and an intrinsic viscosity of 0.32 dL/g. Compared with example 1, the dosage of caustic soda is reduced, and other process indexes and steps are consistent with those of example 1, but the polymerization effect is obviously deteriorated, the product yield and the intrinsic viscosity are obviously reduced, and the product cannot be used as an injection molding product.
Comparative example 6
Weighing 8Kg of industrial grade 5 water crystal sodium sulfide (based on the main content, taking the sodium sulfide as a quantitative reference 1), and weighing industrial grade 4, 4' -dichlorobenzophenone, a catalyst lithium chloride, a solvent N-methylpyrrolidone and caustic soda according to an effective component molar ratio of 1:0.96:0.60:7: 0.06. Wherein one-fourth of the total amount of the solvent N-methylpyrrolidone is used for the dehydration step and three-fourths is used for the polymerization step.
Evaporating and dehydrating the crystallized sodium sulfide to 195 ℃, then filling nitrogen to reduce the temperature to 155 ℃, wherein the first-stage polymerization temperature is 155 ℃, the time is 120 minutes, the stirring speed is 90rpm, the second-stage polymerization temperature is 275 ℃, the time is 120 minutes, and the stirring speed is 120 rpm. After the polymerization reaction is finished, the reaction material is cooled to 165 ℃, and 7.95Kg of polyphenylene sulfide ketone product with the yield of 78.71 percent is obtained by separation, washing and drying.
The product was analyzed to have a melting point of 350 ℃ and an intrinsic viscosity of 0.60 dL/g. Compared with the example 1, the catalyst is changed into lithium chloride, and other process indexes and steps are consistent with those of the example 1, but the product yield is obviously reduced, and the difference of the intrinsic viscosity is not large, which shows that under the catalytic system, the polymerization process which is the same as that of potassium carbonate is adopted, the oligomer is increased, and the polymerization effect is poor.
Comparative example 7
Weighing 8Kg of industrial grade 5 water crystal sodium sulfide (based on the main content, taking the sodium sulfide as a quantitative reference 1), and weighing industrial grade 4, 4' -dichlorobenzophenone, a catalyst potassium carbonate, a solvent N-methylpyrrolidone and caustic soda according to the effective component molar ratio of 1:1:0.60:7: 0.06. Wherein one-fourth of the total amount of the solvent N-methylpyrrolidone is used for the dehydration step and three-fourths is used for the polymerization step.
Evaporating and dehydrating the crystallized sodium sulfide to 195 ℃, then filling nitrogen to reduce the temperature to 155 ℃, wherein the first-stage polymerization temperature is 155 ℃, the time is 120 minutes, the stirring speed is 90rpm, the second-stage polymerization temperature is 275 ℃, the time is 120 minutes, and the stirring speed is 120 rpm. After the polymerization reaction is finished, the reaction material is cooled to 165 ℃, and 6.81Kg of polyphenylene sulfide ketone product is obtained by separation, washing and drying, with the yield of 67.45 percent.
The product was analyzed to have a melting point of 335 ℃ and an intrinsic viscosity of 0.43 dL/g.
Compared with the embodiment 1, the comparative example improves the dosage of the 4, 4' -dichlorobenzophenone, the other process indexes and steps are consistent with the embodiment 1, but the product yield and the intrinsic viscosity are obviously reduced, the melting point of the product is also reduced by 15 ℃, which shows that under the main material proportion, the polymerization effect is poor, and the side reaction is increased.
Comparative example 8
Weighing 8Kg of industrial grade 5 water crystal sodium sulfide (based on the main content, taking the sodium sulfide as a quantitative reference 1), and weighing industrial grade 4, 4' -dichlorobenzophenone, a catalyst potassium carbonate, a solvent N-methylpyrrolidone and caustic soda according to an effective component molar ratio of 1:0.94:0.60:7: 0.06. Wherein one-fourth of the total amount of the solvent N-methylpyrrolidone is used for the dehydration step and three-fourths is used for the polymerization step.
Evaporating and dehydrating the crystallized sodium sulfide to 195 ℃, then filling nitrogen to reduce the temperature to 155 ℃, wherein the first-stage polymerization temperature is 155 ℃, the time is 120 minutes, the stirring speed is 90rpm, the second-stage polymerization temperature is 275 ℃, the time is 120 minutes, and the stirring speed is 120 rpm. After the polymerization reaction is finished, the reaction material is cooled to 165 ℃, and 4.23Kg of polyphenylene sulfide ketone product is obtained by separation, washing and drying, with the yield of 41.88%.
The product was analyzed to have a melting point of 350 ℃ and an intrinsic viscosity of 0.33 dL/g.
Compared with the example 1, the dosage of the 4, 4' -dichlorobenzophenone is reduced, other process indexes and steps are consistent with the example 1, but the product yield and the intrinsic viscosity are obviously reduced, the polymerization effect is poor, and the reaction is unbalanced.
From examples 1-2 and comparative examples 1-8, it can be seen that the method for preparing polyphenylene sulfide ketone has high yield, the obtained product has good comprehensive performance, and can meet the requirement of injection molding processing, and meanwhile, the potassium carbonate provided by the invention is used as a catalyst to replace a lithium chloride catalyst in the traditional method for synthesizing polyarylene sulfide ketone, so that the technical problem that the subsequent separation and recovery of the solvent and the catalyst are difficult due to the fact that the lithium chloride catalyst and the solvent form a coordination compound in the PPSK polymerization reaction process is solved.
The sodium sulfide is a reductive weak acid salt, and all contains crystal water, otherwise the sodium sulfide cannot exist stably, the reaction system of the invention is a solution reaction system taking N-methylpyrrolidone as a solvent, excessive introduction of water can affect the solubility of organic reactants and products, therefore, partial water needs to be removed, but the water cannot be completely removed, otherwise, the inorganic salt sodium sulfide cannot be dissolved in the reaction system, the dehydration is carried out to what extent, the reaction temperature depends on the batching characteristics of the system, and the invention optimizes the dehydration temperature to 190-200 ℃ through a large number of repeated experiments to realize the optimal reaction effect. Because the boiling point of water is lower than that of solvent, and under the condition of open atmospheric dehydration, the relationship between the boiling point of system and composition is consistent, so that in engineering, for convenience of process control, the dehydration degree is indirectly controlled by controlling dehydration temperature.
At present, lithium chloride is generally used as a catalyst in a polyphenylene sulfide ketone reaction system, and the lithium chloride is good in catalytic polymerization effect, but has the defects that a ligand is formed with a solvent, the subsequent separation and recovery of the solvent and the catalyst are difficult after the polymerization reaction is finished, and the lithium chloride is high in price, so that the application of the lithium chloride in engineering is influenced. The invention selects potassium carbonate as a catalyst, and simultaneously researches and develops polymerization temperature and time process which are suitable for the potassium carbonate, thereby realizing the best polymerization reaction effect. The reaction temperature and time of each section are more beneficial to improving the synthesis effect (improving the polymerization degree or molecular weight) of the catalyst and the batching system, and the catalyst and the batching system are more obviously characterized in that the reaction temperature of one section is lower, and the control of the number of the prepolymer is more beneficial, so that the polymerization degree after the second-section reaction is improved.
In conclusion, the method for preparing polyphenylene sulfide ketone adopts a dehydration method outside a polymerization reaction kettle, removes part of water in the crystallized sodium sulfide, and then injects the crystallized sodium sulfide into the polymerization reaction kettle for polymerization reaction, so that the method is favorable for controlling the dehydration process, stabilizing the dehydration effect, reducing the sulfur loss, improving the material balance of the polymerization reaction and further improving the polymerization reaction effect.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (3)
1. A preparation method of high molecular weight polyphenylene sulfide ketone is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
adding crystalline sodium sulfide, a solvent N-methyl pyrrolidone and caustic soda into a dehydration reactor, stirring, heating, evaporating and dehydrating in a nitrogen atmosphere, wherein the heating, evaporating and dehydrating are carried out at the temperature of 190-200 ℃;
adjusting the material after dehydration reaction in the dehydration reactor to the temperature required by the first stage reaction;
adding 4, 4' -dichlorobenzophenone, potassium carbonate and solvent N-methylpyrrolidone into a polymerization reactor, stirring and heating to the first-stage reaction temperature in the nitrogen atmosphere, and sealing;
slowly adding materials in a dehydration reactor into a polymerization reactor through an injection pump, and stabilizing the first-stage reaction temperature through the coordination of a polymerization reactor temperature regulating system to perform a first-stage reaction, wherein the first-stage reaction temperature is 155 +/-2.5 ℃, and the reaction time is 120 +/-5 minutes;
after the first-stage reaction is finished, heating to the second-stage reaction temperature to continue the polymerization reaction, after the second-stage reaction is finished, cooling the reaction product, separating, washing and drying to obtain a solid substance, namely the polyphenylene sulfide ether ketone product, wherein the second-stage reaction temperature is 275 +/-2.5 ℃, and the reaction time is 120 +/-5 minutes;
wherein the proportion of each reaction material is as follows: the molar ratio of the crystallized sodium sulfide to the caustic soda is 1: 0.05-0.08, wherein the molar ratio of the crystallized sodium sulfide to the 4, 4' -dichlorobenzophenone is 1: 0.95-0.98, the molar ratio of the crystalline sodium sulfide to the potassium carbonate is 1: 0.55-0.65, and the molar ratio of the crystalline sodium sulfide to the solvent N-methylpyrrolidone is 1: 6-8.
2. The method of preparing high molecular weight polyphenylene sulfide ketone according to claim 1, wherein: the crystallized sodium sulfide is any one or a mixture of 5 parts of sodium sulfide hydrate and 9 parts of sodium sulfide hydrate.
3. The product of the process for the preparation of high molecular weight polyphenylene sulfide ketone as claimed in claim 1 or 2.
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