CN117843997A - Polyphenylene sulfide resin particles and method for producing the same - Google Patents
Polyphenylene sulfide resin particles and method for producing the same Download PDFInfo
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- CN117843997A CN117843997A CN202410016459.4A CN202410016459A CN117843997A CN 117843997 A CN117843997 A CN 117843997A CN 202410016459 A CN202410016459 A CN 202410016459A CN 117843997 A CN117843997 A CN 117843997A
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 166
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 166
- 239000011347 resin Substances 0.000 title claims abstract description 140
- 229920005989 resin Polymers 0.000 title claims abstract description 140
- 239000002245 particle Substances 0.000 title claims abstract description 128
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000000376 reactant Substances 0.000 claims abstract description 101
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000012043 crude product Substances 0.000 claims abstract description 61
- 239000000203 mixture Substances 0.000 claims abstract description 52
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011593 sulfur Substances 0.000 claims abstract description 36
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 36
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 34
- 238000001704 evaporation Methods 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 238000009291 froth flotation Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 21
- 239000010419 fine particle Substances 0.000 claims description 18
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- 239000006260 foam Substances 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- 239000011268 mixed slurry Substances 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 10
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical group [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 150000003857 carboxamides Chemical class 0.000 claims description 5
- 239000011859 microparticle Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 4
- 239000004299 sodium benzoate Substances 0.000 claims description 4
- 235000010234 sodium benzoate Nutrition 0.000 claims description 4
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 3
- GJVFBWCTGUSGDD-UHFFFAOYSA-L pentamethonium bromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCC[N+](C)(C)C GJVFBWCTGUSGDD-UHFFFAOYSA-L 0.000 claims description 3
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 claims description 3
- -1 sodium fatty acid Chemical class 0.000 claims description 3
- ZGDRLAHGFSGLRI-UHFFFAOYSA-N 1,2-dichloro-9h-carbazole Chemical compound C1=CC=C2C3=CC=C(Cl)C(Cl)=C3NC2=C1 ZGDRLAHGFSGLRI-UHFFFAOYSA-N 0.000 claims description 2
- BCBKMEUFTPYMKQ-UHFFFAOYSA-N 1,2-dichloro-9h-fluorene Chemical compound C1=CC=C2CC3=C(Cl)C(Cl)=CC=C3C2=C1 BCBKMEUFTPYMKQ-UHFFFAOYSA-N 0.000 claims description 2
- AMCBMCWLCDERHY-UHFFFAOYSA-N 1,3-dichloronaphthalene Chemical compound C1=CC=CC2=CC(Cl)=CC(Cl)=C21 AMCBMCWLCDERHY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 16
- 238000009826 distribution Methods 0.000 abstract description 14
- 238000001035 drying Methods 0.000 description 32
- 239000012065 filter cake Substances 0.000 description 31
- 230000008020 evaporation Effects 0.000 description 30
- 239000008367 deionised water Substances 0.000 description 25
- 229910021641 deionized water Inorganic materials 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 22
- 238000001816 cooling Methods 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000007599 discharging Methods 0.000 description 15
- 238000000967 suction filtration Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000005188 flotation Methods 0.000 description 11
- XCCOSIDZEYQCNB-UHFFFAOYSA-N [Na].COC(CCC)=O Chemical group [Na].COC(CCC)=O XCCOSIDZEYQCNB-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000012216 screening Methods 0.000 description 9
- 239000004088 foaming agent Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000013557 residual solvent Substances 0.000 description 6
- 239000000539 dimer Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 239000013638 trimer Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000010009 beating Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- RHUAWQZYOWVZDY-UHFFFAOYSA-N 9H-fluorene dihydrochloride Chemical compound Cl.Cl.C1=CC=CC=2C3=CC=CC=C3CC12 RHUAWQZYOWVZDY-UHFFFAOYSA-N 0.000 description 1
- PPMGNFFGNNRYQC-UHFFFAOYSA-N 9h-carbazole;dihydrochloride Chemical compound Cl.Cl.C1=CC=C2C3=CC=CC=C3NC2=C1 PPMGNFFGNNRYQC-UHFFFAOYSA-N 0.000 description 1
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 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
- 238000002386 leaching Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WMDWNYHVFMGYNB-UHFFFAOYSA-N naphthalene;dihydrochloride Chemical compound Cl.Cl.C1=CC=CC2=CC=CC=C21 WMDWNYHVFMGYNB-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Abstract
The invention relates to a polyphenylene sulfide resin particle and a preparation method thereof, wherein the preparation method comprises the following steps: mixing a sulfur source, an alkali metal hydroxide solution and a first polar organic solvent in the presence or absence of an auxiliary agent, dehydrating to obtain a dehydrated liquid, and mixing the dehydrated liquid with a dihalogenated aromatic compound and a second polar organic solvent for polymerization reaction to obtain a reactant containing polyphenylene sulfide resin, wherein the viscosity of the reactant is 1 Pa.s-5 Pa.s, and the ratio of the sum of the molar amounts of the first polar organic solvent and the second polar organic solvent to the molar amount of the sulfur source is 2.8:1-3.3:1; flash evaporating the reactant to obtain a crude product; mixing the crude product with water to form a mixture, introducing gas into the mixture for froth flotation, and separating from the froth phase to obtain polyphenylene sulfide resin particles D 50 ≤20μm，D 90 /D 10 And is less than or equal to 8. The preparation method of the invention not only can be highThe polyphenylene sulfide resin particles with small particle size and narrow particle size distribution are effectively prepared, and the cost is low.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to polyphenylene sulfide resin particles and a preparation method thereof.
Background
Polyphenylene Sulfide (PPS) is a special engineering plastic excellent in comprehensive properties, and is widely used for various electronic and electric parts, mechanical parts, automobile parts, and the like. Among them, polyphenylene sulfide resin fine particles having a narrow particle size distribution and a small particle diameter are widely used in the fields of paint, adhesive, dispersant in printing ink, 3D printing, and the like. However, the polyphenylene sulfide resin particles are still difficult to prepare by an efficient and low-cost method.
At present, the preparation methods of conventional polyphenylene sulfide resin powder or particles are mainly divided into the following two types: the first and cooling crystallization process includes separating out slowly cooled product, filtering or sieving to obtain product cake containing byproduct salt and byproduct slurry, further washing and purifying the product cake to obtain granular PPS product, and the product contains less low-grade componentsPPS particles composed of PPS of molecular weight, the whole product D 50 Generally above 50. Mu.m. For example, patent application US20150105524A1 discloses a manufacturing process in which small-particle PPS having a diameter of less than 2.38mm is sieved using a classifier or classifier, the remaining large-particle PPS is crushed again and then sieved again, the sieved small-particle PPS is subjected to further purification treatment, and finally, the small-particle PPS product having a component content of less than 10wt% and having a particle size of more than 2.38mm is obtained by solid-liquid separation, which indicates that the initial product contains a large amount of large particles.
And the second flash evaporation process, namely, the reaction mixed solution is directly cooled to normal pressure for flash evaporation without temperature reduction, the solvent is vaporized in the flash evaporation process, the product is dried to form a crude product, and the crude product is further washed and purified to obtain a powdery PPS product. The product contains a certain amount of PPS particles D 50 Generally above 30. Mu.m. For example, patent application CN111533910a discloses an industrial production process of injection-molding-grade polyphenylene sulfide resin, which produces product particles with a particle size of about 0.2-2 mm.
Therefore, in the conventional preparation method of PPS polyphenylene sulfide resin, although the PPS prepared by adopting the flash evaporation process has lower grain size than the PPS prepared by adopting the cooling crystallization process, the PPS still has larger grain size and wider grain size distribution.
Although some preparation methods of PPS fine particles have been proposed on the market, for example, a method of preparing polyphenylene sulfide fine particles as disclosed in patent CN101981091a, in which PPS resin is dissolved in nitrogen methyl pyrrolidone in an autoclave, and then a high-temperature and high-pressure solution is discharged into a receiving tank containing cold water through a connecting line to obtain an NMP-containing suspension of PPS resin particles, coarse particles mixed in a small amount therein are removed by sieving, and the suspension is centrifuged, washed with water and centrifuged several times to obtain PPS resin fine particles having an average particle diameter of about 10 μm. And, patent CN110741032a discloses a method for preparing spherical PPS particles by melt blending PPS with a water-soluble or water-dispersible Polyester (PE) to prepare a PE linear or particle blend in which PPS is dispersed, then cooling the blend, and recovering PPS particles by dissolving the polyester in water heated up to 95 ℃, D of the PPS particles 50 Between 5 and 45 μm. And above mentionedIn the patent, PPS particles are prepared by further processing PPS resin products prepared by conventional cooling crystallization or flash evaporation processes, and the whole production process has complex procedures and high cost.
Disclosure of Invention
In view of the above, it is necessary to provide polyphenylene sulfide resin fine particles and a method for producing the same, which are capable of efficiently producing polyphenylene sulfide resin fine particles having a small particle diameter and a narrow particle diameter distribution, and which are low in cost.
A method for preparing polyphenylene sulfide resin microparticles, comprising the steps of:
mixing a sulfur source, an alkali metal hydroxide solution and a first polar organic solvent in the presence or absence of an auxiliary agent, dehydrating to obtain a dehydrated liquid, and mixing the dehydrated liquid with a dihalogenated aromatic compound and a second polar organic solvent for polymerization reaction to obtain a reactant containing polyphenylene sulfide resin, wherein the viscosity of the reactant is 1 Pa.s-5 Pa.s, and the ratio of the sum of the molar amounts of the first polar organic solvent and the second polar organic solvent to the molar amount of the sulfur source is 2.8:1-3.3:1; flash evaporating the reactant to obtain a crude product;
Mixing the crude product with water to form a mixture, introducing gas into the mixture for froth flotation, and separating from the froth phase to obtain polyphenylene sulfide resin particles, wherein the polyphenylene sulfide resin particles D 50 ≤20μm，D 90 /D 10 ≤8。
In one embodiment, the polyphenylene sulfide resin in the reactant has a weight average molecular weight of 15000 to 30000.
In one embodiment, the molar ratio of the alkali metal hydroxide solution to the sulfur source is from 0.97:1 to 1.01:1;
and/or the molar ratio of the auxiliary agent to the sulfur source is less than or equal to 0.1:1;
and/or the molar ratio of water to sulfur in the dehydration liquid is 1.0:1-1.3:1.
In one embodiment, the molar ratio of the dihaloaromatic compound to the sulfur source is from 1.03:1 to 1.06:1.
In one embodiment, the sulfur source is selected from sodium and/or potassium hydrosulfide;
and/or the alkali metal hydroxide solution is selected from sodium hydroxide solution and/or potassium hydroxide solution;
and/or the dihalogen aromatic compound is at least one selected from paradichlorobenzene, dichloronaphthalene, dichlorofluorene and dichlorocarbazole;
and/or the auxiliary agent is selected from sodium acetate, sodium benzoate and C 5 -C 6 At least one of sodium fatty acid;
and/or the first polar organic solvent and the second polar organic solvent are both selected from organic amide solvents, and the organic amide solvents are at least one selected from N-methylpyrrolidone, hexamethylphosphoric triamide and N-methyl-epsilon-caprolactam.
In one embodiment, in the step of flashing the reactant, steam is introduced into a flash evaporator, the steam temperature is 270-310 ℃, and the temperature of the reactant is 270-290 ℃;
and/or in the step of flashing the reactant, the mass of the steam is 0.1kg-0.5kg based on 1kg of the reactant.
In one embodiment, in the step of flashing the reactant, after the flashing is finished, continuously drying the flashing product until the residual amount of the solvent is lower than 0.2wt% to obtain the crude product;
and/or, in the step of performing froth flotation, adjusting the pH value of the mixture to 5-7, and in the step of separating the mixture from the froth phase to obtain polyphenylene sulfide resin particles, mixing the froth phase and water to form mixed slurry, adjusting the pH value of the mixed slurry to 8-10, and then performing water washing treatment to obtain the polyphenylene sulfide resin particles.
In one embodiment, in the step of mixing the crude product with water to form a mixture, the mass ratio of polyphenylene sulfide to water in the crude product is 1:4 to 1:20;
and/or, in the step of mixing the crude product with water to form a mixture, pulping the crude product with water, separating, and mixing with water again to form the mixture.
In one embodiment, in the step of obtaining a foam phase, a mother liquor is also obtained, which is recycled for preparing the mixture;
alternatively, the conventional polyphenylene sulfide resin powder product is obtained by direct separation from the mother liquor.
The polyphenylene sulfide resin particles prepared by the preparation method of the polyphenylene sulfide resin particles are provided.
According to the preparation method of the polyphenylene sulfide resin particles, the viscosity of the reactant and the contents of the first polar organic solvent and the second polar organic solvent are controlled, and the reactant is subjected to flash evaporation, so that the removal effect of the solvent in the reactant during flash evaporation can be improved, the polyphenylene sulfide resin crude product with small particle size is obtained, and the content of the polyphenylene sulfide resin particles is higher. The polyphenylene sulfide resin has the characteristic of hydrophobicity, and the polyphenylene sulfide resin particles with small particle size can be selectively adhered in the bubbles, so that the invention directly mixes the crude product and water to form a mixture and carries out froth flotation, and the polyphenylene sulfide resin particles with small particle size and narrow particle size distribution can be screened out. Meanwhile, the crude product contains main byproducts (such as dimer with a nitrogen-containing sodium methyl butyrate end group and trimer with a nitrogen-containing sodium methyl butyrate end group) generated in the polymerization reaction process, and the byproducts have higher surface activity and can be used as a foaming agent, so that a high-pollution foaming agent is not required to be additionally added in the step of foam flotation.
Therefore, the preparation method of the polyphenylene sulfide resin particles can not only efficiently prepare the polyphenylene sulfide resin particles with small particle size and narrow particle size distribution, but also have low cost.
Drawings
Fig. 1 is a schematic flow chart of a method for producing polyphenylene sulfide resin fine particles according to an embodiment of the present invention.
Detailed Description
The present invention will be described in more detail below in order to facilitate understanding of the present invention. It should be understood, however, that the invention may be embodied in many different forms and is not limited to the implementations or embodiments described herein. Rather, these embodiments or examples are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments or examples only and is not intended to be limiting of the invention.
Referring to fig. 1, the preparation method of the polyphenylene sulfide resin particles provided by the invention comprises the following steps: mixing a sulfur source, an alkali metal hydroxide solution and a first polar organic solvent in the presence or absence of an auxiliary agent, dehydrating to obtain a dehydrated liquid, and mixing the dehydrated liquid with a dihalogenated aromatic compound and a second polar organic solvent for polymerization reaction to obtain a reactant containing polyphenylene sulfide resin, wherein the viscosity of the reactant is 1 Pa.s-5 Pa.s, and the molar ratio of the sum of the molar amounts of the first polar organic solvent and the second polar organic solvent to the sulfur source is 2.8:1-3.3:1. The arrangement is such that the reactants have low viscosity and low solvent ratio, which is favorable for the solvent to be removed sufficiently in the subsequent flash evaporation, thereby obtaining the polyphenylene sulfide resin crude product with small particle size, and the content of the polyphenylene sulfide resin particles is high.
Alternatively, the molar ratio of the alkali metal hydroxide solution to the sulfur source is from 0.96:1 to 1.03:1, more preferably from 0.97:1 to 1.01:1. The setting can further effectively avoid the problem of unbalanced raw material proportion caused by sulfur loss, namely further ensure that the raw material proportion is still in a reasonable range after the sulfur loss is considered, so that the subsequent polymerization reaction can be better carried out, the hydrophilic and hydrophobic properties of polyphenylene sulfide resin particles in the subsequent mixture can be better regulated and controlled, and the content of main byproducts (such as dimers of the end group of the sodium methyl butyrate containing nitrogen and trimers of the end group of the sodium methyl butyrate containing nitrogen) in the polymerization reaction process, namely the content of the foaming agent can be better regulated and controlled, and the flotation efficiency of the polyphenylene sulfide resin particles can be better improved.
It should be noted that the dimer of the end group of the sodium methyl butyrate, which is the main byproduct in the polymerization reaction, can have the structural formula ofWhile the trimer containing nitrogen-containing sodium methylbutyrate end groups may be +.>
Optionally, the molar ratio of water to sulfur in the dehydration liquid is 1.0:1-1.3:1. The arrangement is beneficial to the efficiency of the subsequent polymerization reaction and reduces the heat required by the volatile moisture during flash evaporation.
It is understood that sulfur in the dewatering liquor refers to the final remaining sulfur in the dewatering liquor after dewatering is completed and after sulfur loss is considered.
Optionally, the weight average molecular weight of the polyphenylene sulfide resin in the reactant is 15000-30000. By the arrangement, the viscosity of the reactant can be further controlled to be 1 Pa.s-5 Pa.s, the removal effect of the solvent in flash evaporation can be further improved, the particle size of the polyphenylene sulfide resin after flash evaporation is small, and the content of the polyphenylene sulfide resin particles is high.
Optionally, the molar ratio of the adjunct to the sulfur source is less than or equal to 0.1:1. By the arrangement, the viscosity of the reactant can be better controlled, and the subsequent flash evaporation effect can be improved.
Optionally, the auxiliary agent is selected from sodium acetate, sodium benzoate, and C 5 -C 6 At least one of sodium fatty acid.
Considering the addition of sodium acetate, C 5 -C 6 The auxiliaries such as fatty acid and sodium benzoate can increase the viscosity of the subsequent reactants, and in order to further control the viscosity of the reactants, the invention preferably does not add an auxiliary in the dehydration process, specifically in the step of dehydration, a sulfur source, an alkali metal hydroxide solution and a first polar organic solvent are mixed and dehydrated. By the arrangement, the viscosity of the subsequent reactant can be better controlled, and the subsequent reaction is improved The solvent is removed during the continuous flash evaporation, so that the particle size of the polyphenylene sulfide resin particles after the flash evaporation is reduced, and the content of the polyphenylene sulfide resin particles is improved.
Optionally, the molar ratio of the dihaloaromatic compound to the sulfur source is from 1.03:1 to 1.06:1. By the arrangement, the weight average molecular weight of the polyphenylene sulfide resin in the reactant can be further controlled and ensured to be 15000-30000, the viscosity of the reactant is further better controlled, the particle size of the polyphenylene sulfide resin particles after flash evaporation is reduced, and the content of the polyphenylene sulfide resin particles is improved.
Optionally, in the step of polymerization, the reaction temperature is 240-265 ℃ and the reaction time is 0.5-5 h. This arrangement allows the components to better polymerize.
Optionally, the sulfur source is selected from sodium and/or potassium hydrosulfide.
Optionally, the alkali metal hydroxide solution is selected from sodium hydroxide solution and/or potassium hydroxide solution, preferably sodium hydroxide solution.
Alternatively, the dihalo-aromatic compound is selected from at least one of paradichlorobenzene, naphthalene dichloride, fluorene dichloride, carbazole dichloride, preferably paradichlorobenzene.
Alternatively, the first polar organic solvent and the second polar organic solvent are both selected from organic amide solvents selected from at least one of N-methylpyrrolidone, hexamethylphosphoric triamide, N-methyl-epsilon-caprolactam, preferably N-methylpyrrolidone.
The specific types of the first polar organic solvent and the second polar organic solvent may be the same or different, and in the present invention, it is preferable that the specific types of the first polar organic solvent and the second polar organic solvent are the same.
In the preparation method of the polyphenylene sulfide resin particles, the reactants obtained in the above steps are subjected to flash evaporation, and the solvent in the reactants is removed, so that a crude product is obtained. Specifically, the reactants are warmed to 270 ℃ to 290 ℃, preferably 280 ℃ to 290 ℃, and then flash evaporated. By the arrangement, the decomposition of reactants due to overhigh temperature can be effectively avoided.
Optionally, in the step of flashing the reactant, introducing steam into a flash evaporator, wherein the steam temperature is 270-310 ℃; the mass of steam is 0.1kg-0.5kg based on 1kg of the reactant. By the arrangement, the removal effect of the solvent in the reactant can be further improved, the particle size of the polyphenylene sulfide resin particles after flash evaporation is reduced, and the content of the polyphenylene sulfide resin particles is improved; meanwhile, the increase of production cost caused by overlarge steam consumption is avoided.
Optionally, in the step of flashing the reactant, after the flashing is finished, stopping introducing steam, and continuously drying the flashing product until the residual amount of the solvent is lower than 0.2wt% to obtain the crude product. By this arrangement, the loss of the polar organic solvent can be further reduced.
The solvent having a residual solvent content of less than 0.2wt% is a mixture of water remaining in the flash product, the first polar solvent, and the second polar solvent.
In the preparation method of the polyphenylene sulfide resin particles, the crude product is mixed with water to form a mixture, gas is introduced into the mixture for froth flotation, and the polyphenylene sulfide resin particles are separated from a froth phase, wherein D of the polyphenylene sulfide resin particles 50 ≤20μm，D 90 /D 10 ≤8。
Specifically, the crude product contains polyphenylene sulfide resin particles and byproduct sodium chloride, and also contains main byproducts generated in the polymerization reaction process, such as dimer containing nitrogen-containing sodium methyl butyrate end groups and trimer containing nitrogen-containing sodium methyl butyrate end groups, wherein the byproducts have higher surface activity and can be used as a foaming agent, and a large amount of bubbles can be generated in the mixture and form a foam phase under the action of gas. Because the polyphenylene sulfide resin has the characteristic of hydrophobicity, and the polyphenylene sulfide resin particles with small particle size can be selectively adhered in the bubbles, the method can directly carry out froth flotation on the crude product, and can screen out the polyphenylene sulfide resin particles with small particle size and narrow particle size distribution, and is simple and efficient.
Meanwhile, the byproducts in the crude product can be directly used as a foaming agent, so that the high-pollution foaming agent is not required to be additionally added in the step of froth flotation, and the method is economical, environment-friendly and low in cost.
In one embodiment, the crude product obtained above is mixed with water to form a mixture, the mixture is placed in a froth flotation machine, gas is introduced into the mixture for flotation treatment to obtain a froth phase, then the froth phase is mixed with water to form a mixed slurry, and after defoaming, the mixed slurry is separated to obtain polyphenylene sulfide resin particles.
Optionally, in the step of mixing the crude product with water to form a mixture, the mass ratio of polyphenylene sulfide to water in the crude product is 1:4-1:20. By the arrangement, a foam phase consisting of three phases of gas, liquid and solid can be formed later, and further the flotation effect of the polyphenylene sulfide resin particles can be improved.
In one embodiment, in the step of mixing the crude product with water to form a mixture, the crude product is firstly mixed with water to carry out beating treatment, and the mixture is formed by mixing the crude product with water after separation by suction filtration and the like. Wherein, when water is added twice, the mass ratio of the polyphenylene sulfide in the crude product to the water is respectively and independently selected from 1:4-1:20. By the arrangement, impurities can be further removed, and the subsequent flotation efficiency is improved.
The beating treatment may be performed at normal pressure and normal temperature, or at high temperature, and the high temperature beating treatment is specifically as follows: mixing the crude product with water, heating to 150-220 ℃, preserving heat for 20-40 min, and cooling to normal temperature.
Optionally, in the step of performing froth flotation, the pH of the mixture is adjusted to 5 to 7, preferably to 5 to 6.5, and then, in the step of separating the polyphenylene sulfide resin fine particles from the froth phase, the froth phase and water are mixed to form a mixed slurry, the pH of the mixed slurry is adjusted to 8 to 10, preferably to 9 to 10, and then, the water washing treatment is performed to obtain the polyphenylene sulfide resin fine particles. By the arrangement, the hydrophobicity and the foaming effect of the polyphenylene sulfide resin particles can be further improved, and meanwhile, foam phase defoaming is facilitated, so that the floatation effect of the polyphenylene sulfide resin particles is improved.
In one embodiment, in the step of performing the water washing treatment, the normal temperature water washing treatment or the high temperature water washing treatment may be performed, and the present invention is preferably the high temperature water washing treatment, specifically as follows: heating the mixed slurry to 150-220 ℃, preserving the temperature for 20-100 min, preferably 30min, and then cooling, suction filtering, leaching and drying to obtain the polyphenylene sulfide resin particles with small particle size and narrow particle size distribution.
In the step of obtaining a foam phase in the present invention, a mother liquor is also obtained, which can be treated in the following two ways.
The first processing mode is as follows: the mother liquor is recycled for preparing the mixture, and the yield of the polyphenylene sulfide resin particles can be further improved by the arrangement.
The second processing mode is as follows: and directly separating from the mother liquor to obtain a conventional polyphenylene sulfide resin powder product.
Optionally, in the step of directly separating from the mother liquor to obtain the conventional polyphenylene sulfide resin powder product, adjusting the pH value of the mother liquor to 8-10, then heating to 150-220 ℃, preserving heat for 20-100 min, cooling, filtering and drying to obtain the conventional polyphenylene sulfide resin powder product.
Therefore, the preparation method of the polyphenylene sulfide resin particles can not only efficiently prepare the polyphenylene sulfide resin particles with small particle size and narrow particle size distribution, but also have low cost.
The invention also provides the polyphenylene sulfide resin particles prepared by the preparation method of the polyphenylene sulfide resin particles. D of the polyphenylene sulfide resin microparticle 50 ≤20μm，D 90 /D 10 And less than or equal to 8, so that the adhesive can be better applied to the fields of coating, adhesive, dispersing agent and 3D printing.
Hereinafter, the polyphenylene sulfide resin fine particles and the method of preparing the same will be further described by way of the following specific examples.
The raw materials and reagents used in all examples and comparative examples of the present invention are commercially available. Meanwhile, the equipment related to the embodiment of the invention comprises a foam flotation machine, a reaction kettle and a high-temperature water washing device, which belong to conventional equipment in the prior art.
In addition, the test methods of the particle diameter and the particle size distribution range of the polyphenylene sulfide resin fine particles prepared in examples and comparative examples in the present invention are specifically as follows: taking 0.2g of sample, putting into 20mL of water, performing ultrasonic dispersion for 5min, adding into a sample injection system of a Michael S3500 particle size measuring instrument, starting automatic test, wherein the default refractive index of particles is 1.81, completing particle size distribution test, and outputting D 10 、D 50 And D 90 And (5) data results. Furthermore, the weight average molecular weight of the polyphenylene sulfide resin in the reactants described in examples and comparative examples in the present invention was measured using a gel permeation chromatograph using narrow-distribution polystyrene as a standard, the solvent was α -chloronaphthalene, the column temperature was 210℃and the viscosity test of the reactants in examples and comparative examples in the present invention was measured using a rotary rheometer MARS60 high pressure module at 260℃and the shear rate was 20s -1 。
Example 1
19.8kg (200.0 mol) of N-methylpyrrolidone, 9.7kg (97 mol) of 40% aqueous sodium hydroxide solution, 14.01kg (100.0 mol) of 40% aqueous sodium hydrosulfide solution are added into a 100L reaction kettle, the temperature is raised to 130 ℃ at a speed of 2.0 ℃/min under the stirring speed of 300rpm and the protection of nitrogen, then the temperature is raised to 160 ℃ at a speed of 0.5 ℃/min, finally the temperature is raised to 210 ℃ at a speed of 1 ℃/min, 14.16kg of aqueous solution (water content of 98.0%) is removed, and the temperature is lowered to 160 ℃ after the dehydration is finished. At this time, the amount of sulfur in the system was 98.0mol and the water content was 117.6mol.
15.14kg (103.0 mol) of paradichlorobenzene, 10.2kg (103 mol) of NMP, and raising the temperature to 260 ℃ at a speed of 0.5 ℃/min are added into the reaction kettle, and after the reaction kettle is kept for 3 hours, a reactant containing polyphenylene sulfide resin is obtained, wherein the weight average molecular weight of the polyphenylene sulfide resin in the reactant is 20000, and the viscosity of the reactant is 1.5Pa.s.
Then heating the reactant to 290 ℃, discharging the reactant into an atmospheric flash evaporator, introducing 290 ℃ superheated steam, wherein the consumption of steam for discharging 1kg of reactant is 0.5kg, and continuing after the flash evaporation is finishedAnd (3) drying until the residual solvent is less than 0.2wt%, and starting cooling to obtain 20.9kg of crude product. 60kg of deionized water is added into the crude product, and after stirring is carried out for 3 hours, a filter cake is obtained after suction filtration. And (3) taking a proper amount of primary filter cake, drying, and screening by using a 150-mesh screen, wherein the content of the screened material is measured to be 35wt%. Adding 50kg of deionized water into the rest of the primary filter cake to prepare slurry to obtain a mixture, adding acetic acid into the mixture to adjust the pH to 6, and then sending the mixture into a froth flotation machine to carry out circulation flotation to obtain a froth phase. Adding 10kg of deionized water into the foam phase, adding a proper amount of NaOH to adjust the pH to 9.5, defoaming, transferring into a high-temperature washing device, heating to 200 ℃, preserving heat for 30min, cooling, carrying out suction filtration, and drying to obtain 1.5kg of polyphenylene sulfide resin particles, wherein D 50 15 μm, D 90 /D 10 7.
Example 2
Example 2 differs from example 1 only in that the mixture was not subjected to an acidic treatment and the mixed slurry was not subjected to an alkaline treatment, i.e., the resulting mixture (pH 10.9) was directly fed to a froth flotation machine for circulation flotation to obtain a froth phase, and the remaining conditions were the same to obtain 0.74kg of polyphenylene sulfide resin fine particles, wherein D 50 10 μm, D 90 /D 10 6.
Example 3
Example 3 differs from example 1 only in that acetic acid was added to the mixture to adjust the pH to 4, and then the mixture was sent to a froth flotation machine for cyclic flotation to obtain a froth phase. Adding 10kg of deionized water into the foam phase, adding a proper amount of NaOH to adjust the pH value to 9.5, defoaming, transferring into a high-temperature washing device, heating to 200 ℃, preserving heat for 30min, cooling, carrying out suction filtration, and drying to obtain 0.45kg of polyphenylene sulfide resin particles, wherein D 50 8 μm, D 90 /D 10 5.
Example 4
Example 4 differs from example 1 only in that acetic acid was added to the mixture to adjust the pH to 8, and then sent to a froth flotation machine for cyclic flotation to obtain a froth phase. Adding 10kg deionized water into the foam phase, adding appropriate amount of NaOH to adjust pH to 9.5, defoaming, and transferring to In a high-temperature water washing device, heating to 200 ℃, preserving heat for 30min, cooling, carrying out suction filtration and drying to obtain 1.2kg of polyphenylene sulfide resin particles, wherein D 50 Is 14 μm, D 90 /D 10 6.8.
Example 5
Example 5 was different from example 1 only in that 15.14kg (103.0 mol) of p-dichlorobenzene, 8.2kg (83 mol) of NMP, was charged into the above-mentioned reaction vessel, and the temperature was raised to 260℃at a rate of 0.5℃per minute, and after 3 hours of heat preservation, a polyphenylene sulfide resin-containing reactant having a weight average molecular weight of 21000 and a viscosity of 1.8Pa.s was obtained.
And then heating the reactant to 290 ℃, discharging the reactant into an atmospheric flash tank, introducing 290 ℃ superheated steam, wherein the consumption of steam for discharging 1kg of reactant is 0.5kg, continuously drying after the flash evaporation is finished, drying until the residual solvent is less than 0.2wt%, and starting cooling to obtain 20.9kg of crude product. 60kg of deionized water is added into the crude product, and after stirring is carried out for 3 hours, a filter cake is obtained after suction filtration. Taking a proper amount of primary filter cake, drying, sieving with a 150-mesh screen, measuring that the content of undersize is 30wt%, adding 50kg deionized water into the rest primary filter cake to obtain a mixture, and obtaining 1.2kg of polyphenylene sulfide resin particles under the same conditions, wherein D 50 16 μm, D 90 /D 10 7.2.
Example 6
Example 6 was different from example 1 only in that 15.14kg (103.0 mol) of p-dichlorobenzene was charged into the above-mentioned reaction vessel, 13.2kg (133 mol) of NMP was heated to 260℃at a rate of 0.5℃per minute, and after 3 hours of heat preservation, a polyphenylene sulfide resin-containing reactant having a weight average molecular weight of 19500 and a viscosity of 1.2Pa.s was obtained.
And then heating the reactant to 290 ℃, discharging the reactant into an atmospheric flash tank, introducing 290 ℃ superheated steam, wherein the consumption of steam for discharging 1kg of reactant is 0.5kg, continuously drying after the flash evaporation is finished, drying until the residual solvent is less than 0.2wt%, and starting cooling to obtain 20.9kg of crude product. 60kg of deionized water is added into the crude product and stirred for 3After hours, a filter cake is obtained after suction filtration. Taking a proper amount of primary filter cake, drying, sieving with a 150-mesh screen, measuring 34wt% of undersize, adding 50kg of deionized water into the remaining primary filter cake to obtain a mixture, and obtaining 1.4kg of polyphenylene sulfide resin particles under the same conditions, wherein D 50 Is 14 μm, D 90 /D 10 7.
Example 7
Example 7 differs from example 1 only in that 19.8kg (200.0 mol) of N-methylpyrrolidone, 10.1kg (101 mol) of 40% aqueous sodium hydroxide solution, 14.01kg (100.0 mol) of 40% aqueous sodium hydrosulfide were charged into a 100L reactor, the temperature was raised to 130℃at a rate of 2.0℃per minute under the stirring speed of 300rpm and the protection of nitrogen gas, then to 160℃at a rate of 0.5℃per minute, finally to 210℃at a rate of 1℃per minute, 14.4kg of aqueous solution (water content 98.0%) was removed, and after the dehydration was completed, the temperature was lowered to 160 ℃. At this time, the amount of sulfur in the system was 98mol and the water content was 117.6mol.
Adding 15.14kg (103.0 mol) of paradichlorobenzene, 10.2kg (103 mol) of NMP and heating to 260 ℃ at the speed of 0.5 ℃/min, and preserving heat for 3 hours to obtain a reactant containing polyphenylene sulfide resin, wherein the weight average molecular weight of the polyphenylene sulfide resin in the reactant is 20500, the viscosity of the reactant is 1.6Pa.s, and the other conditions are the same, so as to obtain 1.6kg of polyphenylene sulfide resin particles, wherein D 50 18 μm, D 90 /D 10 7.5.
Example 8
Example 8 differs from example 1 only in that 19.8kg (200.0 mol) of N-methylpyrrolidone, 10.4kg (104 mol) of 40% aqueous sodium hydroxide solution, 14.01kg (100.0 mol) of 40% aqueous sodium hydrosulfide solution, 1kg (5 mol) of 41% aqueous sodium acetate solution were charged into a 100L reactor, the temperature was raised to 130℃at a rate of 2.0℃per minute under the stirring speed of 300rpm and nitrogen protection, then to 160℃at a rate of 0.5℃per minute, finally to 210℃at a rate of 1℃per minute, 14.58kg of aqueous solution (water content 98.0%) was removed, and after the dehydration was completed, the temperature was lowered to 160 ℃. At this time, the amount of sulfur in the system was 98mol and the water content was 117.6mol.
15.14kg (103.0 mol) of paradichlorobenzene, 10.2kg (103 mol) of NMP, and raising the temperature to 260 ℃ at a speed of 0.5 ℃/min are added into the reaction kettle, and after the reaction kettle is kept for 3 hours, a reactant containing polyphenylene sulfide resin is obtained, wherein the weight average molecular weight of the polyphenylene sulfide resin in the reactant is 21000, and the viscosity of the reactant is 1.7Pa.s.
And then heating the reactant to 290 ℃, discharging the reactant into an atmospheric flash evaporator, introducing 290 ℃ superheated steam, wherein the consumption of steam for discharging 1kg of reactant is 0.5kg, continuously drying after the flash evaporation is finished, drying until the residual amount of the polar organic solvent is lower than 0.2wt%, and starting cooling to obtain 20.9kg of crude product. 60kg of deionized water is added into the crude product, and after stirring is carried out for 3 hours, a filter cake is obtained after suction filtration. And (3) taking a proper amount of primary filter cake, drying, and screening by using a 150-mesh screen, wherein the content of the screened material is 32wt%. Adding 50kg deionized water into the rest filter cakes to prepare a mixture, and obtaining 1.1kg polyphenylene sulfide resin particles under the same rest conditions, wherein D 50 13 μm, D 90 /D 10 6.
Example 9
Example 9 differs from example 1 only in that 19.8kg (200.0 mol) of N-methylpyrrolidone, 9.7kg (97 mol) of 40% aqueous sodium hydroxide solution, 14.01kg (100.0 mol) of 40% aqueous sodium hydrosulfide and 1kg (5 mol) of 41% aqueous sodium acetate were charged into a 100L reactor, the temperature was raised to 130℃at a rate of 2.0℃per minute under the stirring speed of 300rpm and the protection of nitrogen gas, then to 160℃at a rate of 0.5℃per minute, finally to 210℃at a rate of 1℃per minute, 14.76kg of aqueous solution (water content 98.0%) was removed, and after the dehydration was completed, the temperature was lowered to 160 ℃. At this time, the amount of sulfur in the system was 198mol and the water content was 117.6mol.
15.14kg (103.0 mol) of paradichlorobenzene and 10.2kg (103 mol) of NMP are added into the reaction kettle, the temperature is raised to 260 ℃ at the speed of 0.5 ℃/min, and after 3 hours of heat preservation, a reactant containing polyphenylene sulfide resin is obtained, wherein the weight average molecular weight of the polyphenylene sulfide resin in the reactant is 26000, and the viscosity of the reactant is 3Pa.s.
Then the reactant is heated to 290 ℃ and discharged to normal pressureAnd (3) introducing superheated steam at 290 ℃ into the flash evaporator, wherein the steam consumption of each 1kg of discharged reactants is 0.5kg, continuously drying until the residual amount of the polar organic solvent is lower than 0.2wt% after the flash evaporation is finished, and starting cooling to obtain 21.3kg of crude product. 60kg of deionized water is added into the crude product, and after stirring is carried out for 3 hours, a filter cake is obtained after suction filtration. And (3) taking a proper amount of primary filter cake, drying, and screening by using a 150-mesh screen, wherein the content of the screened material is 24wt%. Adding 50kg deionized water into the rest of the primary filter cake to prepare slurry to obtain a mixture, and obtaining 1kg of polyphenylene sulfide resin particles under the same rest conditions, wherein D 50 20 μm, D 90 /D 10 7.8.
Example 10
Example 10 was different from example 1 only in that 14.85kg (101.0 mol) of p-dichlorobenzene, 10.2kg (103 mol) of NMP was charged into the above-mentioned reaction vessel, and the temperature was raised to 260℃at a rate of 0.5℃per minute, and after 3 hours of heat preservation, a polyphenylene sulfide resin-containing reactant having a weight average molecular weight of 25800 and a viscosity of 2.7Pa.s was obtained.
And then heating the reactant to 290 ℃, discharging the reactant into an atmospheric flash evaporator, simultaneously introducing 290 ℃ superheated steam, wherein the consumption of steam for discharging 1kg of reactant is 0.5kg, continuously drying the reactant after the flash evaporation is finished until the residual amount of the polar organic solvent is lower than 0.2wt%, and starting cooling to obtain 20.9kg of crude product. 60kg of deionized water is added into the crude product, and after stirring is carried out for 3 hours, a filter cake is obtained after suction filtration. And (5) taking a proper amount of primary filter cake, drying, and screening by using a 150-mesh screen, wherein the content of the screened material is measured to be 26wt%. Adding 50kg deionized water into the rest filter cakes to prepare a mixture, and obtaining 1.1kg polyphenylene sulfide resin particles under the same rest conditions, wherein D 50 20 μm, D 90 /D 10 8.0.
Example 11
Example 11 differs from example 1 only in that 19.8kg (200.0 mol) of N-methylpyrrolidone, 9.7kg (97 mol) of 40% aqueous sodium hydroxide solution, 14.01kg (100.0 mol) of 40% aqueous sodium hydrosulfide were charged into a 100L reactor, the temperature was raised to 130℃at a rate of 2.0℃per minute under the stirring speed of 300rpm and the protection of nitrogen gas, then to 160℃at a rate of 0.5℃per minute, finally to 203℃at a rate of 1℃per minute, 13.44kg of aqueous solution (water content 98.0%) was removed, and after the dehydration was completed, the temperature was lowered to 160 ℃. At this time, the amount of sulfur in the system was 98mol and the water content was 156.8mol.
15.14kg (103.0 mol) of paradichlorobenzene, 10.2kg (103 mol) of NMP, and raising the temperature to 260 ℃ at a speed of 0.5 ℃/min are added into the reaction kettle, and after the reaction kettle is kept for 3 hours, a reactant containing polyphenylene sulfide resin is obtained, wherein the weight average molecular weight of the polyphenylene sulfide resin in the reactant is 18000, and the viscosity of the reactant is 1.3Pa.s.
And then heating the reactant to 290 ℃, discharging the reactant into an atmospheric flash evaporator, introducing 290 ℃ superheated steam, wherein the consumption of steam for discharging 1kg of reactant is 0.5kg, continuously drying after the flash evaporation is finished, drying until the residual solvent is less than 0.2wt%, and starting cooling to obtain 20.9kg of crude product. 60kg of deionized water is added into the crude product, and after stirring is carried out for 3 hours, a filter cake is obtained after suction filtration. And (3) taking a proper amount of primary filter cake, drying, and screening by using a 150-mesh screen, wherein the content of the screened material is measured to be 28wt%. Adding 50kg deionized water into the rest filter cakes to prepare a mixture, and obtaining 1.2kg polyphenylene sulfide resin particles under the same rest conditions, wherein D 50 Is 14 μm, D 90 /D 10 6.5.
Example 12
Example 12 differs from example 1 only in that the reactants are heated to 290 ℃, discharged into an atmospheric flash evaporator, superheated steam at 290 ℃ is introduced, the steam consumption of each 1kg of discharged reactants is 0.25kg, and after the flash evaporation is finished, the reactants are continuously dried until the residual amount of the solvents is less than 0.2wt%, and cooling is started to obtain 20.9kg of crude products. 60kg of deionized water is added into the crude product, and after stirring is carried out for 3 hours, a filter cake is obtained after suction filtration. And (3) taking a proper amount of primary filter cake, drying, and screening by using a 150-mesh screen, wherein the content of the screened material is 20wt%. Adding 50kg deionized water into the rest filter cakes to prepare a mixture, and obtaining 0.8kg of polyphenylene sulfide resin particles under the same rest conditions, wherein D 50 20 μm, D 90 /D 10 6.
Example 13
Example 13 differs from example 1 only in that the reactants are heated to 270 ℃, discharged into an atmospheric flash evaporator, superheated steam at 290 ℃ is introduced, the steam consumption of each 1kg of discharged reactants is 0.25kg, and after the flash evaporation is finished, the reactants are continuously dried until the residual amount of the solvents is less than 0.2wt%, and cooling is started to obtain 20.9kg of crude products. 60kg of deionized water is added into the crude product, and after stirring is carried out for 3 hours, a filter cake is obtained after suction filtration. And (3) taking a proper amount of primary filter cake, drying, and screening by using a 150-mesh screen, wherein the content of the screened material is 27wt%. Adding 50kg deionized water into the rest filter cakes to prepare a mixture, and obtaining 1.15kg polyphenylene sulfide resin particles under the same rest conditions, wherein D 50 Is 14 μm, D 90 /D 10 6.4.
Comparative example 1
19.8kg (200.0 mol) of N-methylpyrrolidone, 9.7kg (97 mol) of 40% aqueous sodium hydroxide solution, 14.01kg (100.0 mol) of 40% aqueous sodium hydrosulfide solution, 4kg (20.0 mol) of 41% aqueous anhydrous sodium acetate solution, under the stirring speed of 300rpm and nitrogen protection, are added into a 100L reaction kettle, the temperature is raised to 130 ℃ at the speed of 2.0 ℃/min, then the temperature is raised to 160 ℃ at the speed of 0.5 ℃/min, finally the temperature is raised to 210 ℃ at the speed of 1 ℃/min, 16.56kg of aqueous solution (water content of 98.0%) is removed, and the temperature is lowered to 160 ℃ after dehydration is finished. At this time, the amount of sulfur in the system was 98.0mol and the water content was 117.6mol.
14.99kg (102.0 mol) of paradichlorobenzene, 14.2kg (143 mol) of NMP, was added to the reaction vessel, and the temperature was raised to 260℃at a rate of 0.5℃per minute, and the reaction vessel was kept for 3 hours, to obtain a polyphenylene sulfide resin-containing reactant having a weight average molecular weight of 40000 and a viscosity of 6Pa.s.
Then heating to 290 ℃, discharging into an atmospheric flash evaporator, continuously drying after the flash evaporation is finished, drying until the residual solvent is less than 0.2 weight percent, and beginning to cool down and obtain 22.5kg of crude product. 60kg of deionized water was added to the crude product, followed by stirring for 3 hours, followed by suction filtration to obtain a cake. Taking a proper amount of primary filter cake, drying, screening by a 150-mesh screen, and measuringThe undersize content was 10wt%. Adding 50kg deionized water, heating to 200deg.C, maintaining the temperature for 30min, cooling to room temperature, vacuum filtering, oven drying to obtain 0.3kg polyphenylene sulfide resin particles, wherein D 50 28 μm, D 90 /D 10 8.
Comparative example 2
Comparative example 2 was different from example 1 only in that 16.13kg (103.0 mol) of p-dichlorobenzene, 10.2kg (103 mol) of NMP, was charged into the above-mentioned reaction vessel, and the temperature was raised to 260℃at a rate of 0.5℃per minute, and after 3 hours of heat preservation, a polyphenylene sulfide resin-containing reactant having a weight average molecular weight of 14000 and a viscosity of 0.8Pa.s was obtained.
And then heating the reactant to 290 ℃, discharging the reactant into an atmospheric flash evaporator, simultaneously introducing 290 ℃ superheated steam, wherein the consumption of steam for discharging 1kg of reactant is 0.5kg, continuously drying the reactant after the flash evaporation is finished until the residual amount of the polar organic solvent is lower than 0.2wt%, and starting cooling to obtain 20.9kg of crude product. 60kg of deionized water is added into the crude product, and after stirring is carried out for 3 hours, a filter cake is obtained after suction filtration. And (5) taking a proper amount of primary filter cake, drying, and screening by using a 150-mesh screen, wherein the content of the screened material is measured to be 40wt%. Adding 50kg deionized water into the rest filter cakes to prepare a mixture, and obtaining 1.8kg polyphenylene sulfide resin particles under the same rest conditions, wherein D 50 Is 12 μm, D 90 /D 10 8.2.
Comparative example 3
Comparative example 3 is different from example 1 only in that the obtained mixture was directly transferred to a high-temperature washing apparatus without floatation, heated to 200 c, heat-preserved for 30min, cooled, suction-filtered and dried to obtain polyphenylene sulfide resin particles 9.95kg, wherein D 50 50 μm, D 90 /D 10 14.
Comparative example 4
Comparative example 4 was different from example 1 only in that 15.14kg (103.0 mol) of paradichlorobenzene, 20.05kg (253 mol) of NMP was charged into the above-mentioned reaction vessel, and the temperature was raised to 260℃at a rate of 0.5℃per minute, and the reaction was maintained for 3 hours, to obtain a polyphenylene sulfide resin-containing reactant, the reaction The weight average molecular weight of the polyphenylene sulfide resin in the product is 19000, the viscosity of the reactant is 0.8Pa.s, and the other conditions are the same, so that 0.15kg of polyphenylene sulfide resin particles are obtained, wherein D 50 25 μm, D 90 /D 10 7.5.
D from the polyphenylene sulfide resin particles of examples 1 to 13 and the polyphenylene sulfide resin particles of comparative examples 1 to 4 50 、D 90 /D 10 The data shows that the removal effect of the solvent in the reactant during flash evaporation can be improved by controlling the viscosity of the reactant and the mole ratio of NMP and the sulfur source in the reaction and optimizing the process parameters during the flash evaporation of the reactant, and the polyphenylene sulfide resin crude product with small particle size can be obtained, wherein the content of the polyphenylene sulfide resin particles is higher. Because the polyphenylene sulfide resin has the characteristic of hydrophobicity, and the polyphenylene sulfide resin particles with small particle size can be selectively adhered in the bubbles, the invention directly carries out froth flotation on the crude product, and can screen out the polyphenylene sulfide resin particles with small particle size and narrow particle size distribution.
Meanwhile, the crude product contains main byproducts (such as dimer with a nitrogen-containing sodium methyl butyrate end group and trimer with a nitrogen-containing sodium methyl butyrate end group) generated in the polymerization reaction process, and the byproducts have higher surface activity and can be used as a foaming agent, so that a high-pollution foaming agent is not required to be additionally added in the step of foam flotation.
Therefore, the preparation method of the polyphenylene sulfide resin particles can not only efficiently prepare the polyphenylene sulfide resin particles with small particle size and narrow particle size distribution, but also have low cost.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A method for preparing polyphenylene sulfide resin particles, which is characterized by comprising the following steps:
mixing a sulfur source, an alkali metal hydroxide solution and a first polar organic solvent in the presence or absence of an auxiliary agent, dehydrating to obtain a dehydrated liquid, and mixing the dehydrated liquid with a dihalogenated aromatic compound and a second polar organic solvent for polymerization reaction to obtain a reactant containing polyphenylene sulfide resin, wherein the viscosity of the reactant is 1 Pa.s-5 Pa.s, and the ratio of the sum of the molar amounts of the first polar organic solvent and the second polar organic solvent to the molar amount of the sulfur source is 2.8:1-3.3:1;
Flash evaporating the reactant to obtain a crude product;
mixing the crude product with water to form a mixture, introducing gas into the mixture for froth flotation, and separating from the froth phase to obtain polyphenylene sulfide resin particles, wherein the polyphenylene sulfide resin particles D 50 ≤20μm，D 90 /D 10 ≤8。
2. The method for producing polyphenylene sulfide resin fine particles according to claim 1, wherein the polyphenylene sulfide resin in the reactant has a weight average molecular weight of 15000 to 30000.
3. The method for producing polyphenylene sulfide resin fine particles according to claim 1, wherein the molar ratio of the alkali metal hydroxide solution to the sulfur source is 0.97:1 to 1.01:1;
and/or the molar ratio of the auxiliary agent to the sulfur source is less than or equal to 0.1:1;
and/or the molar ratio of water to sulfur in the dehydration liquid is 1.0:1-1.3:1.
4. The method for producing polyphenylene sulfide resin fine particles according to claim 1, wherein the molar ratio of the dihaloaromatic compound to the sulfur source is 1.03:1 to 1.06:1.
5. The method for producing polyphenylene sulfide resin microparticles according to claim 1, wherein the sulfur source is selected from sodium hydrosulfide and/or potassium hydrosulfide;
And/or the alkali metal hydroxide solution is selected from sodium hydroxide solution and/or potassium hydroxide solution;
and/or the dihalogen aromatic compound is at least one selected from paradichlorobenzene, dichloronaphthalene, dichlorofluorene and dichlorocarbazole;
and/or the auxiliary agent is selected from sodium acetate, sodium benzoate and C 5 -C 6 At least one of sodium fatty acid;
and/or the first polar organic solvent and the second polar organic solvent are both selected from organic amide solvents, and the organic amide solvents are at least one selected from N-methylpyrrolidone, hexamethylphosphoric triamide and N-methyl-epsilon-caprolactam.
6. The method for producing polyphenylene sulfide resin fine particles according to claim 1, wherein in the step of flashing the reactant, steam is introduced into the flash evaporator at 270 to 310 ℃, and the reactant is at 270 to 290 ℃;
and/or in the step of flashing the reactant, the mass of the steam is 0.1kg-0.5kg based on 1kg of the reactant.
7. The method for producing polyphenylene sulfide resin fine particles according to claim 1, wherein in the step of flashing the reactant, after the flashing is completed, the flashed product is further dried until the residual amount of the solvent is less than 0.2wt%, to obtain the crude product;
And/or, in the step of performing froth flotation, adjusting the pH value of the mixture to 5-7, and in the step of separating the mixture from the froth phase to obtain polyphenylene sulfide resin particles, mixing the froth phase and water to form mixed slurry, adjusting the pH value of the mixed slurry to 8-10, and then performing water washing treatment to obtain the polyphenylene sulfide resin particles.
8. The method for producing polyphenylene sulfide resin fine particles according to claim 1, wherein in the step of mixing the crude product with water to form a mixture, the mass ratio of polyphenylene sulfide to water in the crude product is 1:4 to 1:20;
and/or, in the step of mixing the crude product with water to form a mixture, pulping the crude product with water, separating, and mixing with water again to form the mixture.
9. The method according to any one of claims 1 to 8, wherein in the step of obtaining a foam phase, a mother liquor is also obtained, and the mother liquor is recycled for use in preparing the mixture;
alternatively, the conventional polyphenylene sulfide resin powder product is obtained by direct separation from the mother liquor.
10. A polyphenylene sulfide resin microparticle prepared by the method for preparing a polyphenylene sulfide resin microparticle according to any one of claims 1 to 9.
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