CN101935397A - Process for synthesizing low-chlorine polyphenylene sulfide resin - Google Patents
Process for synthesizing low-chlorine polyphenylene sulfide resin Download PDFInfo
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- CN101935397A CN101935397A CN2010102845061A CN201010284506A CN101935397A CN 101935397 A CN101935397 A CN 101935397A CN 2010102845061 A CN2010102845061 A CN 2010102845061A CN 201010284506 A CN201010284506 A CN 201010284506A CN 101935397 A CN101935397 A CN 101935397A
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- polyphenylene sulfide
- temperature
- sulfide resin
- molecular sieve
- sodium
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Links
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 51
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 51
- 239000011347 resin Substances 0.000 title claims abstract description 30
- 229920005989 resin Polymers 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000008569 process Effects 0.000 title claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 title abstract description 15
- 239000000460 chlorine Substances 0.000 title abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000002808 molecular sieve Substances 0.000 claims abstract description 27
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 13
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 230000018044 dehydration Effects 0.000 claims abstract description 8
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 36
- 239000011734 sodium Substances 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 235000010265 sodium sulphite Nutrition 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000428 dust Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000009156 water cure Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 229910052736 halogen Inorganic materials 0.000 abstract description 6
- 150000002367 halogens Chemical class 0.000 abstract description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007832 Na2SO4 Substances 0.000 abstract description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 3
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 3
- 208000005156 Dehydration Diseases 0.000 abstract 1
- 239000005022 packaging material Substances 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000003252 repetitive effect Effects 0.000 description 4
- 238000005201 scrubbing Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000019086 sulfide ion homeostasis Effects 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- -1 salt compound Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229940001516 sodium nitrate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a process for synthesizing low-chlorine polyphenylene sulfide resin. Sodium sulfide and paradichlorobenzene are used as raw materials, N-methyl-2-pyrrolidone is used as a solvent, and the molar ratio of the sodium sulfide to the paradichlorobenzene is 1:1. The synthesis process mainly comprises the following steps of: in a sodium sulfide dehydration treatment phase, carrying out sodium sulfide solution insulating and water sucking treatment by adopting three layers of 18cm water sucking column containing a 5 angstrom molecular sieve in each layer to form a sodium sulfide solution with the water content of 1.2-1.5mol/molNa2S and adding NaOH with the molar mass of 0.1-0.3mol/molNa2S; and in the polycondensation phase, adding Na2SO4 of 0.1-0.05mol/molNa2S and H2S gas of 0.01mol/molNa2S. The invention has lower halogen total content and polydispersion coefficient in the obtained product, narrow molecular weight distribution, high oxygen index and excellent electrical insulating property and can be used as a packaging material of an electronic device.
Description
Technical field
It is synthetic to the invention belongs to high molecular material resin, especially the polyphenylene sulfide production field.
Background technology
High-performance polyphenylene sulfide has the thermostability under excellent chemical proofing and the high temperature, and has fire-retardant, insulation, radiation hardness and favorable mechanical performance.For exploring the synthetic method of this material, the investigators that are various countries are always seeking of constantly making great efforts.
Having narrated chemical substances such as use sulfydryl and sulfydryl metal-salt poly-p-phenylene sulfide ether resin after polyphenylene sulfide is synthetic in United States Patent (USP) NO:4761468 handles, thereby the content of chlorine element in the reduction polyphenylene sulfide, after handling like this is that polyphenylene sulfide is applied to field of electrical components by modification, and its main purpose is to improve the insulating property of polyphenyl thioether material.Its this invention is to adopt end capped mode to come low-molecular-weight polyphenylene sulfide is handled, and the price of its sulfydryl and sulfydryl metal salt compound is all than higher for this reason, thereby increases the cost of polyphenylene sulfide.
In United States Patent (USP) NO:4820801, narrated the polyphenylene sulfide after using a kind of reductive agent processing synthetic, thereby the content of the chlorine element in the reduction polyphenylene sulfide, as electronic package material, its objective is the electrical insulation capability that improves the electronic apparatus material through the polyphenylene sulfide after handling like this.Its this invention also is to adopt end capped mode to come low-molecular-weight polyphenylene sulfide is handled, and the price of its reducing compound is all than higher for this reason, thereby increases the cost of synthetic polyphenylene sulfide.
Just existing polyphenylene sulfide synthetic technology, the synthetic general employing sodium sulphite and the santochlor (P-DCB) of polyphenylene sulfide are raw-material mode, though the polyphenylene sulfide that the polyphenylene sulfide production company of U.S. Phillips company and Japan produces does not have what change substantially on starting material, thereby realize that by the technology controlling and process means that add subsidiary material polyphenylene sulfide reaches the purpose of low chlorine, but do not see other Na of its blending
2SO
4With the concrete process introduction of hydrogen sulfide.
Summary of the invention
The objective of the invention is to study a kind of polymerization technique that contains the polyphenylene sulfide of low halogen element, under the prerequisite that does not increase the synthetic cost of polyphenylene sulfide, improve the polydispersity coefficient and the oxygen index of resin by choose reasonable process control condition, raw material, subsidiary material, reduce the content of halogens, reach the final purpose of optimizing its electrical insulation properties.
The objective of the invention is to realize by following means.
The synthesis technique of low-chloride polyphenylene sulfide resin, adopting sodium sulphite and santochlor is raw material, N-N-methyl-2-2-pyrrolidone N-solvent, low-chloride polyphenylene sulfide resin is produced in polycondensation; Sodium sulphite: with santochlor: NMP: NaOH: Na
2SO
4: H
2The mol ratio of S is 1: 1: 4.5: 0.1-0.3: 0.1-0.05: 0.01; Synthesis technique comprises:
1), in the sodium sulphite processed stage, five water cure sodium crystals join in the common response still, under the protection of carbon dioxide, and be heated to 120-130 ℃, sodium sulphite is fully dissolved, then solution being imported holding temperature is the 120-130 ℃ of suction post that 3 layers of 18cm/ layer, 5 dust molecular sieve are housed, and sodium sulfide solution is handled in suction through molecular sieve;
2), through 1) suction handles that water content is 1.2-1.5mol/molNa in the postcure sodium solution
2Behind the S, claim nmp solvent to add, the autoclave that flows directly into, the santochlor of adding NaOH and corresponding mol ratio quality in reactor again from the suction column top of molecular sieve;
3), displace air in the reactor with carbon dioxide gas, behind the closed reactor, temperature rises to 240 ± 2 ℃ then, and is incubated 2-3h under this temperature, adds the Na of corresponding mol ratio
2SO
4, it is stand-by then temperature to be risen to 260 ± 2 ℃ of insulation 2-3h;
4) with 3) the mixed with polymers slurry that obtains is with the cooling rate of 20 ℃/min, drop to 140 ℃ after, in reactor, add the H of corresponding mol ratio
2S gas is raised to temperature 260 ± 2 ℃ then, and 0.5h is stand-by in insulation;
5) with 4) the mixed with polymers slurry that obtains, material was discarded to plate filter and carries out solid-liquid and separate when temperature dropped to 130-140 ℃, and the deionized water wash solids obtains the polyphenylene sulfide that cl content is 400～900ppm through super-dry.
After adopting as above means, Na especially
2SO
4After the blending of hydrogen sulfide raw material, it is lower and molecular weight distribution is very narrow to obtain polydispersity coefficient, and number-average molecular weight is between 3.7-4.8 ten thousand, the polyphenylene sulfide resin of halogen element total content between 400-900, resin crystallinity, whiteness, physical strength, melting viscosity, oxygen index, polydispersity coefficient are more excellent, present method synthetic polyphenylene sulfide is used for the insulating material of electronic apparatus, the insulating property of its resin are more excellent, reach other performances and be further enhanced, use temperature and fusing point all have raising to some extent.
The present invention connects-Ar-M structure (M is expressed as amino or sodium ion) at the end of the molecular structure of-Ar-S-, at a kind of like this molecular structure of the end formation-Ar-S-Ar-M of macromolecular material, and these separation structures may be ordered arrangement, lack of alignment even the control molecular structure by feeding in raw material---be the molecular structure of end-blocking formula, such purpose is to improve the electrical insulation capability index of polyphenylene sulfide resin, the polyphenylene sulfide resin that adopts the present invention to obtain is used for injection moulding, is extruded into moulded product, can improve the electric simulation strength of moulded product.
The sodium salt that uses can be a kind of of following material or several among the present invention: as Sodium Fluoride, S-WAT,, SODIUMNITRATE, Na
2SO
4, yellow soda ash, wherein with S-WAT, Na
2SO
4, yellow soda ash is better, with Na
2SO
4For best, by the effect of sodium ion, make the chlorion on the phenyl ring break away from phenyl ring with fast speeds, its objective is reduction according to the chlorine element total content in the diphenyl sulfide resin, improve the purity of resin.
Halogen among the present invention is several elements such as fluorine, chlorine, bromine, iodine, because the physicochemical property difference of several elements, mainly be that chlorine, bromine exist wherein with the form of compound in the polyphenylene sulfide kind simultaneously, some are mineral compound, some are organic compound, but the halogen among the present invention is the chlorine element, and the content in polyphenylene sulfide determines usually that with chlorine unit the summation that is chloride ion content in covalency chlorine and the mineral compound is at 400-900ppm.
Materials such as NaOH that added in the present invention, its purpose improves the basicity of polymerization reaction system, according to the polyphenylene sulfide synthesis mechanism, thereby improve the speed of response of polyreaction, help shortening the polyphenylene sulfide synthetic time, save the cost of synthetic polyphenylene sulfide, help enhancing productivity.
Accompanying drawing 1 is a process flow sheet of the present invention
Process chart brief introduction of the present invention:
The crystal vulcanized sodium that the present invention at first will contain 5 crystallizations water adds after heating for dissolving becomes sodium sulfide solution in the dehydrating kettle, three layers of molecular sieve suction of its solution input post, with the water absorption portion in the sodium sulfide solution, to reach the requirement of water content in the synthetic polyphenylene sulfide polymerization reaction system, then with needed solvent NMP flushing molecular sieve suction post in the polymerization reaction system, in the reaction under high pressure of 2L, form with vulcanized sodium then, water, NMP, NaOH (being reacted into NaOH with water), with the raw-material polymerization reaction system such as paracide, after finishing, the first step of reaction in polymerization reaction system, adds a certain amount of Na2SO
4, carry out again the second step of polymerisation, after the second step of polymerisation is finished, in polymerization reaction system, add again a certain amount of H2S gas is adding H2Behind the S gas, insulation 0.5h is with regard to the synthetic polyphenylene sulfide slurry that contains low chlorine, then filter through the plate and frame filter, behind the cyclic washing, drying just obtains target product of the present invention.
Embodiment
Below in conjunction with embodiment technology of the present invention is described in further detail.
Embodiment 1:
In the dehydration still of 1L, add sodium sulphite (Na
2S.5H
2O) 2.0mol is at 99.99%CO
2Under the protection of gas; temperature is heated to 120 ℃, and the input holding temperature is 120 ℃ three layers of 18cm/ layer, 5 dust molecular sieve suction post is housed, after the molecular sieve suction; make the sodium sulphite in the sodium sulfide solution and the mol ratio of water become 1: 1.2, use 4.5mol/molNa then
2The nmp solvent of S adds from the suction column top of molecular sieve, flows directly into the autoclave of 2L, and the molar mass that adds NaOH again in reactor is 0.1mol/molNa
2S, temperature risen to 130 ℃ after, add the santochlor of 2mol.Displace air in the reactor for 3-5 time with carbon dioxide again, behind the closed reactor, temperature rises to 238 ℃ then, and is incubated 2h under this temperature, and when cooling to 130 ℃, adds 0.1mol/molNa
2The industrial one-level Na of S
2SO
4, temperature rises to 238 ℃, and behind insulation 0.2h under this temperature, temperature is risen to 258 ℃, and be incubated 2h under this temperature.The mixed with polymers slurry that obtains is with the cooling rate of 20 ℃/min, drop to 140 ℃ after, in reactor, add purity and be 99.99% H
2S gas 0.01mol/molNa
2S is raised to temperature 258 ℃ then, the mixed with polymers slurry that insulation 0.5h obtains, and temperature drops to 130 ℃, and reacted material is emitted reactor.Carry out solid-liquid through plate filter and separate, with being mixed with after molecular sieve removes the deionized water repetitive scrubbing 6 times of water,, reclaim the polyphenylene sulfide of gained then through super-dry.Resin resin flows speed 373g/10min (ASTM-1238-70), 284.9 ℃ of fusing points, the ash content of coal be 0.02%, the molecular weight distribution coefficient is 1.80, number-average molecular weight is 3.7 ten thousand, oxygen index can reach 39, chlorine element total content is 400ppm
Embodiment 2:
In the dehydration still of 1L, add sodium sulphite (Na
2S.5H
2O) 2.0mol is at 99.99%CO
2Under the protection of gas; temperature is heated to 125 ℃, and the input holding temperature is 125 ℃ three layers of 18cm/ layer, 5 dust molecular sieve suction post is housed, after the molecular sieve suction; make the sodium sulphite in the sodium sulfide solution and the mol ratio of water become 1: 1.3, use 4.5mol/molNa then
2The nmp solvent of S adds from the suction column top of molecular sieve, flows directly into the autoclave of 2L, and the molar mass that adds NaOH again in reactor is 0.2mol/molNa
2S, temperature risen to 135 ℃ after, add the santochlor of 2mol.Displace air in the reactor for 3-5 time with carbon dioxide again, behind the closed reactor, temperature rises to 240 ℃ then, and is incubated 2.5h under this temperature, and when cooling to 135 ℃, adds 0.04mol/molNa
2The industrial one-level Na of S
2SO
4, temperature rises to 240 ℃, and behind insulation 0.3h under this temperature, temperature is risen to 260 ℃, and be incubated 2-3h under this temperature.The mixed with polymers slurry that obtains is with the cooling rate of 20 ℃/min, drop to 140 ℃ after, in reactor, add purity and be 99.99% H
2S gas 0.01mol/molNa
2S is raised to temperature 260 ℃ then, the mixed with polymers slurry that insulation 0.5h obtains, and temperature drops to 135 ℃, and reacted material is emitted reactor.Carry out solid-liquid through plate filter and separate, with being mixed with after molecular sieve removes the deionized water repetitive scrubbing 6 times of water,, reclaim the polyphenylene sulfide of gained then through super-dry.Resin resin flows speed 215g/10min (ASTM-1238-70), 284.9 ℃ of fusing points, the ash content of coal be 0.1%, the molecular weight distribution coefficient is 1.81, number-average molecular weight is 4.45 ten thousand, oxygen index can reach 37, chlorine element total content is 700ppm.
Embodiment 3:
In the dehydration still of 1L, add sodium sulphite (Na
2S.5H
2O) 2.0mol is at 99.99%CO
2Under the protection of gas; temperature is heated to 130 ℃, and the input holding temperature is 130 ℃ three layers of 18cm/ layer, 5 dust molecular sieve suction post is housed, after the molecular sieve suction; make the sodium sulphite in the sodium sulfide solution and the mol ratio of water become 1: 1.5, use 4.5mol/molNa then
2The nmp solvent of S adds from the suction column top of molecular sieve, flows directly into the autoclave of 2L, and the molar mass that adds NaOH again in reactor is 0.3mol/molNa
2S, temperature risen to 140 ℃ after, add the santochlor of 2mol.Displace air in the reactor for 3-5 time with carbon dioxide again, behind the closed reactor, temperature rises to 242 ℃ then, and is incubated 3h under this temperature, and when cooling to 140 ℃, adds 0.05mol/molNa
2The industrial one-level Na of S
2SO
4, temperature rises to 242 ℃, and behind insulation 0.5h under this temperature, temperature is risen to 262 ℃, and be incubated 3h under this temperature.The mixed with polymers slurry that obtains is with the cooling rate of 20 ℃/min, drop to 140 ℃ after, in reactor, add purity and be 99.99% H
2S gas 0.01mol/molNa
2S is raised to temperature 262 ℃ then, the mixed with polymers slurry that insulation 0.5h obtains, and temperature drops to 140 ℃, and reacted material is emitted reactor.Carry out solid-liquid through plate filter and separate, with being mixed with after molecular sieve removes the deionized water repetitive scrubbing 6 times of water,, reclaim the polyphenylene sulfide of gained then through super-dry.Resin resin flows speed 183g/10min (ASTM-1238-70), 285 ℃ of fusing points, ash 0.023%, molecular weight distribution coefficient are 1.83, and number-average molecular weight is 4.8 ten thousand, and oxygen index can reach 38, and chlorine element total content is 900ppm.
Embodiment 4:
In the dehydration still of 1L, add sodium sulphite (Na
2S.5H
2O) 2.0mol is at 99.99%CO
2Under the protection of gas; temperature is heated to 130 ℃, and the input holding temperature is 130 ℃ three layers of 18cm/ layer, 5 dust molecular sieve suction post is housed, after the molecular sieve suction; make the sodium sulphite in the sodium sulfide solution and the mol ratio of water become 1: 1.4, use 4.5mol/molNa then
2The nmp solvent of S adds from the suction column top of molecular sieve, flows directly into the autoclave of 2L, and the molar mass that adds NaOH again in reactor is 0.3mol/molNa
2S, temperature risen to 140 ℃ after, add the santochlor of 2mol.Displace air in the reactor for 3-5 time with carbon dioxide again, behind the closed reactor, temperature rises to 240 ℃ then, and is incubated 3h under this temperature, and temperature is risen to 260 ℃, and is incubated 3h under this temperature.Temperature drops to 140 ℃, and reacted material is emitted reactor.Carry out solid-liquid through plate filter and separate, with being mixed with after molecular sieve removes the deionized water repetitive scrubbing 6 times of water,, reclaim the polyphenylene sulfide of gained then through super-dry.Resin resin flows speed 177g/10min (ASTM-1238-70), 285 ℃ of fusing points, ash 0.087%, molecular weight distribution coefficient are 1.83, and number-average molecular weight is 4.7 ten thousand, and oxygen index can reach 38, and chlorine element total content is 2900ppm.
Embodiment 1-3 and embodiment 4 contrasts can be found out, the adding of a certain amount of Na2SO4 and hydrogen sulfide adds Na2SO4 and hydrogen sulfide and has good effect to reaching purpose of the present invention reducing the influence of the cl content in the polyphenylene sulfide in the building-up process of polyphenylene sulfide.
Claims (5)
1. the synthesis technique of low-chloride polyphenylene sulfide resin, adopting sodium sulphite and santochlor is raw material, N-N-methyl-2-2-pyrrolidone N-solvent, polycondensation production low-chloride polyphenylene sulfide resin; Sodium sulphite: with santochlor: NMP: NaOH: Na
2SO
4: H
2The mol ratio of S is 1: 1: 4.5: 0.1-0.3: 0.1-0.05: 0.01; Synthesis technique comprises:
1), in the sodium sulphite processed stage, five water cure sodium crystals join in the common response still, under the protection of carbon dioxide, and be heated to 120-130 ℃, sodium sulphite is fully dissolved, then solution being imported holding temperature is the 120-130 ℃ of suction post that 3 layers of 18cm/ layer, 5 dust molecular sieve are housed, and sodium sulfide solution is handled in suction through molecular sieve;
2), through 1) suction handles that water content is 1.2-1.5mol/molNa in the postcure sodium solution
2Behind the S, claim nmp solvent to add, the autoclave that flows directly into, the santochlor of adding NaOH and corresponding mol ratio quality in reactor again from the suction column top of molecular sieve;
3), displace air in the reactor with carbon dioxide gas, behind the closed reactor, temperature rises to 240 ± 2 ℃ then, and is incubated 2-3h under this temperature, adds the Na of corresponding mol ratio
2SO
4, it is stand-by then temperature to be risen to 260 ± 2 ℃ of insulation 2-3h;
4) with 3) the mixed with polymers slurry that obtains is with the cooling rate of 20 ℃/min, drop to 140 ℃ after, in reactor, add the H of corresponding mol ratio
2S gas is raised to temperature 260 ± 2 ℃ then, and 0.5h is stand-by in insulation;
5) with 4) the mixed with polymers slurry that obtains, material was discarded to plate filter and carries out solid-liquid and separate when temperature dropped to 130-140 ℃, and the deionized water wash solids obtains the polyphenylene sulfide that cl content is 400～900ppm through super-dry.
2. the synthesis technique that contains low-chloride polyphenylene sulfide resin according to claim 1 is characterized in that, described N-N-methyl-2-2-pyrrolidone N-solvent purity is 99.998%, and carbon dioxide purity is 99.99%, H
2The S gas purity is 99.99%.
3. the synthesis technique that contains low-chloride polyphenylene sulfide resin according to claim 1 is characterized in that, describedly is used to wash solid-liquid and separates back solids deionized water and obtain for handling through molecular sieve dehydration.
4. the synthesis technique that contains low-chloride polyphenylene sulfide resin according to claim 1, it is characterized in that, the ash content of coal of described product low-chloride polyphenylene sulfide resin is 0.02-0.1%, and the molecular weight distribution coefficient is 1.80～1.83, and number-average molecular weight is 3.7-4.8 ten thousand.
5. the synthesis technique that contains low-chloride polyphenylene sulfide resin according to claim 1, it is characterized in that, the reaction heat steam heating dehydration that the dehydration of the suction post of described 3 layers of 18cm/ layer, 5 dust molecular sieve adopts polyreaction to discharge, the recycling of the moisture content that removes process is in the washing of polyphenylene sulfide.
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| CN102134319A (en) * | 2011-02-25 | 2011-07-27 | 四川得阳化学有限公司 | Process for synthesizing low-chlorine film polyphenylene sulfide resin |
| CN102432879A (en) * | 2011-08-11 | 2012-05-02 | 深圳市宝力特科技有限公司 | Dewatering process of polyhydrated sodium sulfide in synthetic process of polyphenylene sulfide resin |
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