CN110204723B - A kind of preparation method of heat-resistant polyphenylene sulfide - Google Patents
A kind of preparation method of heat-resistant polyphenylene sulfide Download PDFInfo
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- CN110204723B CN110204723B CN201910589214.XA CN201910589214A CN110204723B CN 110204723 B CN110204723 B CN 110204723B CN 201910589214 A CN201910589214 A CN 201910589214A CN 110204723 B CN110204723 B CN 110204723B
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 42
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 11
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 claims abstract description 9
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000002955 isolation Methods 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229940079101 sodium sulfide Drugs 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 2
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007350 electrophilic reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing 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
- C08G75/0204—Polyarylenethioethers
- C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/02—Polythioethers; Polythioether-ethers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention provides a preparation method of hollow spherical heat-resistant polyphenylene sulfide, which comprises the steps of firstly carrying out high-temperature oxygen-isolation treatment on sodium sulfide nonahydrate to obtain anhydrous sodium sulfide, then taking potassium carbonate, sodium carbonate and lithium chloride as a combined catalyst, uniformly mixing the anhydrous sodium sulfide with the prepared anhydrous sodium sulfide solution, adjusting the pH of the solution to be = 9-10 by using sodium hydroxide, then heating to 220-225 ℃ under the protection of nitrogen, and carrying out constant-temperature reaction for 6-8 h; and washing, filtering and drying to obtain the hollow spherical polyphenylene sulfide. Tests prove that the hollow spherical polyphenylene sulfide has the melting point of 297 ℃, has good heat resistance, has larger specific surface area, and can be more compatible with other substances, so that various groups (inorganic macromolecules/metal oxides and the like) can be easily introduced into a hollow shell, and the hollow spherical polyphenylene sulfide is used for preparing polyphenylene sulfide composite materials modified by various groups.
Description
Technical Field
The invention relates to a preparation method of polyphenylene sulfide, in particular to a preparation method of heat-resistant polyphenylene sulfide with a hollow spherical structure, and belongs to the field of material preparation.
Background
Polyphenylene sulfide (abbreviated as PPS) is a polymer containing a p-phenylene sulfide repeating structural unit in a molecule, is a novel functional engineering plastic, and is widely applied to the fields of electronics, automobiles, machinery and chemical engineering. pps has the advantages of high mechanical strength, high temperature resistance, high flame retardance, strong chemical resistance and the like; has the advantages of hardness, brittleness, high crystallinity, flame retardancy, good thermal stability, high mechanical strength, excellent electrical property and the like. Polyphenylene sulfide is an amphiphobic substance, and has very strong rigidity in the structure of the alternate arrangement of benzene rings and sulfur atoms, and basically does not dissolve any solvent, thereby determining the macroscopic property, namely high mechanical strength. Thus, the polyphenylene sulfide may be present as a catalyst support or composite substrate.
Many methods are currently used for synthesizing PPS, such as self-polycondensation of halosulfur phenolate, melt polymerization of p-halodiphenyl and sulfur, electrophilic reaction of sulfur and benzene, solution polycondensation of alkali metal sulfide and p-dihalobenzene (sodium sulfide method), solution polycondensation of sulfur and p-dichlorobenzene (sulfur solution method), polymerization of diphenyl disulfide under the action of Lewis acid, and the like. The sodium sulfide method and the sulfur solution method are currently used for industrial production, and the prepared polyphenylene sulfide has the microscopic forms of lamellar, spherical, flower-shaped, reticular and the like, and the size can be expanded to a few micrometers or can be reduced to a nanometer level. However, polyphenylene sulfide of these structures has poor heat resistance, thus limiting its applications.
Disclosure of Invention
The invention aims to provide a preparation method of heat-resistant polyphenylene sulfide with a hollow spherical structure.
The preparation method of the hollow spherical polyphenylene sulfide comprises the steps of firstly dispersing sodium sulfide nonahydrate in N-dimethyl pyrrolidone under the condition of continuously introducing nitrogen, and reacting at 150-160 ℃ for 1.5-2 hours to obtain an anhydrous sodium sulfide solution; adding a combined catalyst into the anhydrous sodium sulfide solution, uniformly mixing, adjusting the pH of the solution to be = 9-10 by using sodium hydroxide, heating to 70-80 ℃, adding p-dichlorobenzene, and uniformly stirring; then heating to 220-225 ℃, and reacting for 6-8 h at constant temperature; and after the reaction is finished, washing, filtering and drying to obtain the hollow spherical heat-resistant polyphenylene sulfide.
The combined catalyst consists of lithium chloride, potassium carbonate and sodium carbonate, and the mass ratio of the lithium chloride to the potassium carbonate is 4: 1-3.5: 1; the mass ratio of the lithium chloride to the potassium carbonate is 3.5: 1-3.0: 1. The mass ratio of the combined catalyst to the sodium sulfide nonahydrate is 1: 4-1: 5; the mass ratio of the p-dichlorobenzene to the sodium sulfide nonahydrate is 1: 1.5-1: 2.
In order to achieve a better dispersion effect, the combined catalyst is dispersed in N-dimethyl pyrrolidone according to the mass-volume ratio of 1: 40-1: 45g/mL, and then added into an anhydrous sodium sulfide solution. The gas velocity of continuously introducing nitrogen is 10-15 mL/min.
FIG. 1 is a scanning electron microscope image of the hollow spherical polyphenylene sulfide prepared by the present invention. As can be seen from FIG. 1, polyphenylene sulfide is in the form of hollow spheres, and is uniformly distributed, and has a large-scale flat structure. Therefore, various groups (such as metal ions, macromolecular inorganic substances or organic substances and the like) can be easily introduced into the gaps, so that the polyphenylene sulfide composite material modified by various groups can be prepared.
Table 1 shows the heat resistance of polyphenylene sulfides with different morphologies. As can be seen from Table 1, the heat resistance of the hollow spherical polyphenylene sulfide prepared by the invention is obviously superior to that of polyphenylene sulfides with other shapes.
The invention uses lithium chloride, sodium carbonate and potassium carbonate as combined catalyst, which has great promotion effect on nucleophilic substitution reaction; the formed hollow spherical polyphenylene sulfide has larger specific surface area and can be more compatible with other substances, and meanwhile, the hollow spherical structure effectively prevents the heat transfer efficiency of the hollow spherical polyphenylene sulfide, so that the melting point of the hollow spherical polyphenylene sulfide is improved, the hollow spherical polyphenylene sulfide is endowed with good heat resistance, and the application of the polyphenylene sulfide is widened.
Drawings
FIG. 1 is a scanning electron microscope image of hollow spherical polyphenylene sulfide prepared by the present invention after drying at 0 ℃.
Detailed Description
The preparation, morphology and the like of the polyphenylene sulfide with the hollow spherical structure are further described by specific examples.
(1) Preparation of anhydrous sodium sulfide: weighing 79.5 g of sodium sulfide nonahydrate, adding the sodium sulfide nonahydrate into 180mL of N-dimethyl pyrrolidone, continuously introducing nitrogen under oxygen-proof protection (nitrogen flow rate is kept at 10 mL/min), reacting for 1 h at 150-160 ℃ to obtain a green anhydrous sodium sulfide solution, cooling, and pouring into a reaction kettle;
(2) preparation of the combined catalyst: 5.933 g of anhydrous lithium chloride, 1.658 g of anhydrous potassium carbonate and 1.732 g of anhydrous sodium carbonate are weighed, sealed and mixed uniformly to prevent oxidation and deliquescence;
(3) preparing hollow sphere polyphenylene sulfide: dissolving the combined catalyst in 230mL of N-dimethylpyrrolidone, adding the mixture into a reaction kettle, uniformly mixing, adding sodium hydroxide at room temperature under stirring (the stirring speed is 40 r/min), adjusting the solution to be alkaline (pH = 9-10), heating to 70 ℃, and adding 44.1 g of p-dichlorobenzene under stirring to obtain a dark green solution; after the reaction kettle is sealed, continuously introducing nitrogen (the nitrogen introduction rate is 10 mL/min) under stirring (the stirring speed is 900 r/min) to replace the air in the reaction kettle; then heating to 220 ℃, keeping the temperature and reacting for 6 hours, wherein the solution is black; repeatedly washing with deionized water and ethanol, filtering at 60 deg.C, and drying at 0 deg.C to obtain 10.5 g hollow spherical polyphenylene sulfide. Melting point 297 ℃. The scanning electron microscope image of polyphenylene sulfide is shown in FIG. 1, and polyphenylene sulfide is in hollow sphere shape and is uniformly distributed.
Claims (5)
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| US3987016A (en) * | 1975-01-16 | 1976-10-19 | The United States Of America As Represented By The Secretary Of The Air Force | Method for the preparation of polyarylene sulfides containing pendant cyano groups by polymerizing m-benzenedithiol, dibromobenzene, and 2,4-dichlorobenzonitrile |
| US6194495B1 (en) * | 1998-03-23 | 2001-02-27 | General Electric Company | Cyanate ester based thermoset compositions |
| CN1345892A (en) * | 2000-09-30 | 2002-04-24 | 四川省华拓实业发展股份有限公司 | Technology for recovering dissolvent and catalyst in producing polyphenyl-thioether |
| CN102633990A (en) * | 2012-04-05 | 2012-08-15 | 广东生益科技股份有限公司 | Epoxy resin composition and prepreg and copper-clad laminate manufactured using it |
| CN102964599B (en) * | 2012-11-20 | 2014-05-07 | 四川得阳化学有限公司 | Dehydration process for polyphenyl thioether resin synthesis solvent system |
| CN103087523B (en) * | 2012-12-26 | 2014-08-27 | 四川大学 | Extrusion-grade polyarylene sulfide bar and preparation method thereof |
| KR102147691B1 (en) * | 2013-06-21 | 2020-08-27 | 에보닉 피브레 게엠베하 | Method for producing polyimide membranes |
| CN108752586A (en) * | 2018-07-04 | 2018-11-06 | 西北师范大学 | A kind of preparation method of colored fascicular texture polyphenylene sulfide |
| CN109517174A (en) * | 2018-11-02 | 2019-03-26 | 西北师范大学 | A kind of preparation method of three-dimensional network-like structure polyphenylene sulfide |
| CN109810507B (en) * | 2019-01-10 | 2021-06-01 | 西北师范大学 | Preparation method of polyphenylene sulfide/ferroferric oxide composite material |
| CN109852057B (en) * | 2019-01-18 | 2021-07-23 | 西北师范大学 | A kind of preparation method of polyphenylene sulfide/graphene quantum dot composite material |
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