CN1328303C - Tech., for polymerizing fibre grade polyphenyl sulfoether resin - Google Patents
Tech., for polymerizing fibre grade polyphenyl sulfoether resin Download PDFInfo
- Publication number
- CN1328303C CN1328303C CNB2005100224376A CN200510022437A CN1328303C CN 1328303 C CN1328303 C CN 1328303C CN B2005100224376 A CNB2005100224376 A CN B2005100224376A CN 200510022437 A CN200510022437 A CN 200510022437A CN 1328303 C CN1328303 C CN 1328303C
- Authority
- CN
- China
- Prior art keywords
- added
- polyphenylene sulfide
- resin
- temperature
- dichlorobenzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 22
- 239000011347 resin Substances 0.000 title claims abstract description 22
- 229920006389 polyphenyl polymer Polymers 0.000 title claims description 6
- 239000000835 fiber Substances 0.000 title description 18
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 title 1
- 230000000379 polymerizing effect Effects 0.000 title 1
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 23
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 23
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000012747 synergistic agent Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940117389 dichlorobenzene Drugs 0.000 claims abstract description 3
- 238000001035 drying 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 16
- 239000002253 acid Substances 0.000 claims description 9
- 235000010265 sodium sulphite Nutrition 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 150000003568 thioethers Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 208000005156 Dehydration Diseases 0.000 claims description 4
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000010953 base metal Substances 0.000 claims description 4
- 230000003750 conditioning effect Effects 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 230000003252 repetitive effect Effects 0.000 claims description 4
- CMVQZRLQEOAYSW-UHFFFAOYSA-N 1,2-dichloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1Cl CMVQZRLQEOAYSW-UHFFFAOYSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000011112 process operation Methods 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract 4
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920013632 Ryton Polymers 0.000 description 5
- 239000004736 Ryton® Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 101100074998 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) nmp-2 gene Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- -1 phosphorous acid ester Chemical class 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- BYPIKLIXBPMDBY-UHFFFAOYSA-N 2-hydroxypropanoic acid;potassium Chemical compound [K].CC(O)C(O)=O BYPIKLIXBPMDBY-UHFFFAOYSA-N 0.000 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 206010016654 Fibrosis Diseases 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 230000004761 fibrosis Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 239000004247 glycine and its sodium salt Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- UICBCXONCUFSOI-UHFFFAOYSA-N n'-phenylacetohydrazide Chemical compound CC(=O)NNC1=CC=CC=C1 UICBCXONCUFSOI-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 229940029258 sodium glycinate Drugs 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- HSYFJDYGOJKZCL-UHFFFAOYSA-L zinc;sulfite Chemical compound [Zn+2].[O-]S([O-])=O HSYFJDYGOJKZCL-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present invention discloses a polymerization technology of fibre-grade polyphenylene sulfide resin. A polyphenylene sulfide (PPS) monomer is produced by adopting sodium sulfide and p-dichlorobenzene (P-DCB) as raw materials under the action of an alkali metal catalyst through polycondensation. The spinnability of obtained resin slices is improved by adopting the following technological conditions: in the dewatering treatment stage of the sodium sulfide, an auxiliary agent is added, the temperature of the sodium sulfide during stirring is slowly raised to 200DEG C in 2 to 6 hours, and the sodium sulfide is dewatered; in a polycondensation stage after dichlorobenzene is added, a regulating agent is added to raise the temperature to 200 to 275DEG C to carry out a polymerization reaction for 6 to 8 hours; a regulating agent is added at the temperature of 155 to 180DEG C to raise the temperature to 210 to 275DEG C, and the stirring is continued for 0.5 hour. An obtained mixture is filtered and washed more than once, and a synergistic agent is added in the process; the polyphenylene sulfide resin having good spinnability is obtained after rewashing with deionized water and drying treatment.
Description
Affiliated technical field
The invention belongs to the macromolecule resin 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 enlarging the use range of this material, the investigators of various countries make it the novel method that fibrosis is used in searching always.
Chinese patent CN91107114 discloses a kind of potassium titanate fiber and the compound processing method of making matrix material of polyphenylene sulfide, in polycondensation vessel, at first use six polyamine dispersant (the synthetic solvent of using of double as polyphenylene sulfide) under heating and agitation condition, potassium titanate fiber to be disperseed, adding sodium sulphite and santochlor (P-DCB) then is raw material, (sodium sulphite and santochlor (P-DCB) are raw material to polycondensation production polyphenylene sulfide, and the fibre composite of polyphenylene sulfide (PPS) and potassium titanate fiber is produced in polycondensation under the base metal catalysts effect under the base metal catalysts effect.But this method makes the shortcoming that has the fibre breakage intensity difference.U.S. Pat 5401799 discloses a kind of polyphenylene sulfide based thermoplastic glass conjugated fibre with high-wearing feature, and composition of raw materials is provided.
With regard to the situation of prior art, the mode of matrix material is generally adopted in the manufacturing of polyphenylene sulfide fibre, though there is report U.S. Phillipsd company that the fiber-grade polyphenyl thioether production of resins is arranged, does not see the introduction of concrete technology.
The objective of the invention is to study a kind of fiber-grade polyphenyl thioether resin polymerization technology, improve the spinning property of resin, make the fiber manufacturing in later stage obtain the better properties index then by choose reasonable technic index, auxiliary agent, conditioning agent, synergistic agent.
Summary of the invention
The objective of the invention is to realize by following means.
Fiber-grade polyphenyl thioether resin polymerization technology, adopting sodium sulphite and santochlor (P-DCB) is raw material, polycondensation is produced in the monomeric technological process of polyphenylene sulfide (PPS) under the base metal catalysts effect, adopts following processing condition to improve the spinning property of the resin slicer of gained:
1) the sodium sulphite processed stage adds the auxiliary agent sodium borohydride, stirs slow intensification 2-6 hour down, is warming up to 200 ℃ of dehydrations;
2) add polycondensation phase behind the dichlorobenzene, add the nitro dichlorobenzene or to Histol, if be warming up to 200-275 ℃, polyreaction 6-8 hour;
3) through 1) 2) mixture that obtains of step, add the conditioning agent hexanodioic acids down at 155 ~ 185 ℃, be warmed up to 210 ℃ again and continue to stir 0.5 hour.
4) through 1), 2), 3) mixture that obtains of step, after 100 ~ 200 ℃ of filtrations, the filtration-washing repetitive process operation more than once again, and add synergistic agent quadrol tetrem disodium in stirring is washed through deionized water again.
1) through 1), 2), 3), 4) polyphenylene sulfide that obtains having better spinning property after the step resulting polymers drying treatment.
After adopting means as above, the crystallization of the resin of acquisition is more good, and spinning property improves, the breaking tenacity of the fiber that makes, and use temperature and oxygen index are improved.
Description of drawings:
Fig. 1 is the fibre resin index synopsis 1 of the Ryton of the resin that obtains of the present invention and Phillipsd company.
Fig. 2 is the fibre resin index synopsis 2 of the Ryton of the resin that obtains of the present invention and Phillipsd company.
Embodiment
Below in conjunction with embodiment technology of the present invention is described in further detail.
Embodiment 1
In autoclave, add N-methyl-2 pyrrolidone (NMP) 12 kilograms, sodium sulphite (Na
2S.3H
20) 44 kilogram, 0.01 kilogram of sodium borohydride (auxiliary agent), under the 0.01Mpa nitrogen gas pressure, stir on one side, heat up on one side, rise to 200 ℃ of dehydrations with 2 hours times, add 4.15 kilograms of santochlor again, the NMP2 kilogram, the nitro dichlorobenzene is warming up to 200 ℃ for 0.15 kilogram, 8 hours postcooling of polyreaction.185 ℃ add and are warmed up to 250 ℃ of processing after 0.1 kilogram of hexanodioic acid carries out, and mixture is after 140 ℃ of filtrations.With 40 liters of branches of deionized water 8 times the polymkeric substance that makes is carried out repetitive scrubbing, filtration, first and second time washing adds ammonium chloride 0 respectively.1 kilogram, the 4th washing adds 0.05 kilogram of synergistic agent quadrol tetrem disodium, dry under 100 ℃ then, obtain 2.05 kilograms of polyphenylene sulfides, flow rate 172g/10min (ASTM-1238-70), 283.5 ℃ of fusing points, ash 0.27%, volatile matter 0.28% (150 ℃), Mw52589, polydispersity coefficient PD2.19.
Embodiment 2
In autoclave, add N-methyl-2 pyrrolidone (NMP) 12 kilograms, sodium sulphite (Na
2S.3H
2O) 4 kilograms, 0.01 kilogram of sodium borohydride, under the 0.01MPa nitrogen gas pressure, stir on one side, heat up on one side, rise to 200 ℃ of dehydrations with 2 hours times, add 4.10 kilograms of santochlor again, the NMP2 kilogram is warming up to 275 ℃ to 0.17 kilogram of Histol, 6 hours postcooling of polyreaction.185 ℃ add and are warmed up to 250 ℃ of processing after 0.1 kilogram of hexanodioic acid carries out, mixture carries out repetitive scrubbing, filtration with 40 liters of branches of deionized water 8 times to the polymkeric substance that makes after 140 ℃ of filtrations, first and second time washing adds 0.1 kilogram of ammonium chloride respectively, adds 0.05 kilogram of quadrol tetrem disodium the 4th time.Dry under 100 ℃ then, obtain 2.1 kilograms of polyphenylene sulfides. flow rate 168g/10min (ASTM-1238-70), 283.0 ℃ of fusing points, ash 0.25%, volatile matter 0.27% (150 ℃), Mw47685, polydispersity coefficient PD2.4.
The resin of this explained hereafter is linear right-polyphenylene sulfide, and spinning property is superior, and the key technical indexes of the polyphenylene sulfide fibre that makes is good.
The fibre resin index of the fibre-grade PPS resin of its acquisition and the Ryton of Phillipsd company is relatively as table 1, by finding out in the table 1, the product sample 20021209 that the inventive method makes and 20021104 flow rate, ash and volatile matter index are all than the Ryton of Phillipsd company
TWE2481 is low, therefore has more better spinnability energy.
The fiber of being made by resin of the present invention is by the detection to index of correlation of Sichuan Province examination of fibers office and national fire-proof construction material quality surveillance inspection center, the Ryton fiber of measurement result and Phillipsd company more as shown in Table 2,
As above contrast as seen, the product that the present invention obtains has better spinnability, and the fiber decapacitation that makes keeps the characteristic of PPS itself such as the chemical resistant properties of excellence, thermotolerance, outside the flame retardant resistance etc., also have more favorable mechanical performance, and its corresponding index all can reach international like product index.
In addition, in actual production, auxiliary agent can be a kind of of following material or several:
The material of the strong reducing power of tool: as formaldehyde, acetaldehyde, sodium borohydride, POTASSIUM BOROHYDRIDE, Thiovanic acid, hydrazine hydrate, phenylhydrazine, pyrodin, phosphorous acid ester, Sodium Nitrite, boron nitride, 4, the two sulfonyl hydrazides of 4-oxo etc.
Conditioning agent can be a kind of of following material or several:
Organic acid or mineral acid: as palmitinic acid, citric acid, lauric acid, hexanodioic acid, butyric acid, n-nonanoic acid,, Sorbic Acid, stearic acid, toxilic acid, pentanedioic acid, mineral acid such as sulfuric acid, hydrochloric acid, etc.
Synergistic agent can be a kind of of following material or several:
The carboxylate salt of alkali or alkaline-earth metal or strong acid weak base salt, sulfonate: as ammonium sulfate, magnesium chloride, ammonium chloride, ammonium sulphite, zinc sulfate, zinc sulfite, zinc chloride, sebacic acid penta 2 ammoniums, ammonium nitrate, Soduxin, hexanodioic acid sodium, disodium EDTA, calcium acetate, Sodium Glycinate, hydroxy-propionic acid potassium, tetrasodium ethylenediamine tetraacetate, dodecylbenzene sulfonate, sodium allyl sulfonate, sodium cetanesulfonate etc.
Claims (1)
1, fiber-grade polyphenyl thioether resin polymerization technology is raw material adopting sodium sulphite and santochlor, and polycondensation is produced in the monomeric technological process of polyphenylene sulfide under the base metal catalysts effect, adopts following processing condition to improve the spinning property of the resin slicer of gained:
1) in the sodium sulphite processed stage, add the auxiliary agent sodium borohydride, stirred slow intensification 2-6 hour down, be warming up to 200 ℃ of dehydrations;
2) polycondensation phase behind the adding dichlorobenzene adds the nitro dichlorobenzene or to Histol, is warming up to 200-275 ℃, polyreaction 6-8 hour;
3) through 1), 2) mixture that obtains of step, add the conditioning agent hexanodioic acids down at 155 ~ 185 ℃ and be warmed up to 210 ~ 275 ℃ again and continue to stir 0.5 hour.
4) through 1), 2), 3) mixture that obtains of step, after 100 ~ 200 ℃ of filtrations, the filtration-washing repetitive process operation more than once again, and add synergistic agent quadrol tetrem disodium in the agitator treating process is washed through deionized water again;
Through 1), 2), 3), 4) polyphenylene sulfide that obtains having better spinning property after the step resulting polymers drying treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100224376A CN1328303C (en) | 2005-12-29 | 2005-12-29 | Tech., for polymerizing fibre grade polyphenyl sulfoether resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100224376A CN1328303C (en) | 2005-12-29 | 2005-12-29 | Tech., for polymerizing fibre grade polyphenyl sulfoether resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1793202A CN1793202A (en) | 2006-06-28 |
| CN1328303C true CN1328303C (en) | 2007-07-25 |
Family
ID=36804860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100224376A Expired - Fee Related CN1328303C (en) | 2005-12-29 | 2005-12-29 | Tech., for polymerizing fibre grade polyphenyl sulfoether resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1328303C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675640B (en) * | 2011-03-18 | 2014-06-25 | 四川得阳工程塑料开发有限公司 | Method for controlling process conditions for production and synthesis of polyphenylene sulfide |
| CN103147154A (en) * | 2011-12-06 | 2013-06-12 | 江苏阜升环保集团有限公司 | Hyperbranched antioxidative polyphenylene sulfide fibers and preparation method thereof |
| CN102702528A (en) * | 2012-05-28 | 2012-10-03 | 自贡鸿鹤化工股份有限公司 | Production method for polyphenyl thioether |
| CN103172864B (en) * | 2013-04-23 | 2015-02-25 | 四川大学 | Preparation method of organic acid salt catalytic polyarylene sulfide |
| CN103601887B (en) * | 2013-11-20 | 2016-04-20 | 珠海长先化学科技有限公司 | A kind of method of adding compound accelerant synthon level polyphenylene sulfide in stage casing |
| CN103951825B (en) * | 2014-04-29 | 2016-03-30 | 四川中科兴业高新材料有限公司 | A kind of high strength polyphenylene sulfide and preparation method thereof |
| CN105085917A (en) * | 2015-08-05 | 2015-11-25 | 广州高八二塑料有限公司 | Film-grade polyphenylene sulfide resin and preparation method thereof |
| KR102196506B1 (en) | 2017-10-20 | 2020-12-29 | 주식회사 엘지화학 | Process for preparing polyarylene sulfide |
| KR102173641B1 (en) * | 2017-11-24 | 2020-11-03 | 주식회사 엘지화학 | Process for preparing polyarylene sulfide |
| CN111171320B (en) * | 2020-02-13 | 2022-05-06 | 四川明道和化学新材料有限公司 | Production method of catalyst-removed polyphenylene sulfide resin |
| CN111548493A (en) * | 2020-05-11 | 2020-08-18 | 山东滨化滨阳燃化有限公司 | Washing treatment method of fiber-grade polyphenylene sulfide industrial product |
| CN112574414B (en) * | 2020-12-09 | 2022-02-01 | 浙江大学 | Synthetic method of polyarylene sulfide resin |
| CN114634621A (en) * | 2021-12-21 | 2022-06-17 | 江苏邦正新材料有限公司 | Hydrothermal synthesis method of pps nano composite material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08120081A (en) * | 1994-10-25 | 1996-05-14 | Tonen Chem Corp | High-molecular poly(arylene sulfide) for molded sheet |
| CN1292012A (en) * | 1998-03-05 | 2001-04-18 | 提克纳有限公司 | Method for producing sulfur-containing polymers |
| CN1309142A (en) * | 2000-12-27 | 2001-08-22 | 古旗高 | Process for preparing high-density high-molecular linear polyphenyl thioether |
| US20020019501A1 (en) * | 2000-07-07 | 2002-02-14 | Petroleum Energy Center | Production process for polyarylene sulfide |
| CN1345891A (en) * | 2000-09-30 | 2002-04-24 | 四川省华拓实业发展股份有限公司 | Method for controlling synthetic technological condition of producing polyphenyl-thioether |
| JP2003268105A (en) * | 2002-03-19 | 2003-09-25 | Toray Ind Inc | Method for manufacturing poly(arylene sulfide) |
-
2005
- 2005-12-29 CN CNB2005100224376A patent/CN1328303C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08120081A (en) * | 1994-10-25 | 1996-05-14 | Tonen Chem Corp | High-molecular poly(arylene sulfide) for molded sheet |
| CN1292012A (en) * | 1998-03-05 | 2001-04-18 | 提克纳有限公司 | Method for producing sulfur-containing polymers |
| US20020019501A1 (en) * | 2000-07-07 | 2002-02-14 | Petroleum Energy Center | Production process for polyarylene sulfide |
| CN1345891A (en) * | 2000-09-30 | 2002-04-24 | 四川省华拓实业发展股份有限公司 | Method for controlling synthetic technological condition of producing polyphenyl-thioether |
| CN1309142A (en) * | 2000-12-27 | 2001-08-22 | 古旗高 | Process for preparing high-density high-molecular linear polyphenyl thioether |
| JP2003268105A (en) * | 2002-03-19 | 2003-09-25 | Toray Ind Inc | Method for manufacturing poly(arylene sulfide) |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1793202A (en) | 2006-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1328303C (en) | Tech., for polymerizing fibre grade polyphenyl sulfoether resin | |
| US4486578A (en) | Stabilized polyphenylene sulfide and method for producing same | |
| EP0189895B1 (en) | Phenylene sulfide resin compositions | |
| CN101575418B (en) | Lignin-based high-efficiency water reducing agent with high sulfonation degree and high molecular weight and method for preparing same | |
| EP1714994A1 (en) | Polyarylene sulfide and process for producing the same | |
| EP0293891B1 (en) | Process for producing high impact resistant polycarbonate | |
| CA1298679C (en) | Process for preparing poly(arylene sulfide ketone) with water addition | |
| CN112625233A (en) | High molecular weight crystalline poly (arylene ether nitrile) and preparation method thereof | |
| CN102766255A (en) | Polyaryl ether nitrile resin and industrialized synthetic method thereof | |
| JP2021510749A (en) | High molecular weight polyphenylene sulfide resin and its manufacturing method and use | |
| CN113861688A (en) | Low-dielectric polyphenylene sulfide composite material and preparation method thereof | |
| Çelikçi et al. | Synthesis and characterization of carboxymethyl cellulose (cmc) from different waste sources containing cellulose and investigation of its use in the construction industry | |
| CN114149586B (en) | Chain-extended polysulfate and preparation method thereof | |
| US4900805A (en) | Rigid rod aromatic benzthiazole heterocyclic polymer | |
| CN101200546B (en) | Method for synthesizing polyphenylene sulfide copolymer containing heteroaromatics | |
| CN102558558A (en) | Polyether sulphone-nitrile resin and industrialization synthetic method thereof | |
| Yashchenko et al. | New high-tensile thermally stable copolymers of poly (p-phenylene-1, 3, 4-oxadiazole) | |
| EP3677617A1 (en) | Preparation method for polyphenylene sulfide and polyphenylene sulfide prepared by means of same | |
| CN112585179B (en) | Acrylic copolymer for carbon fiber | |
| US7465782B2 (en) | Method for making polybenzobisoxazole containing fiber | |
| CN109666266A (en) | One kind is containing the modified polyadipate/butylene terephthalate composite material and preparation method of bi-component fibres | |
| JPH10176106A (en) | Composite material of glass and polyamide and its preparation | |
| CN116355211B (en) | Preparation method of phosphazene structure-containing phthalonitrile resin with self-catalytic characteristic | |
| Mudzakir et al. | Ammonium and cholinium based ionic liquids as a new chemical modifier for giant bamboo (dendrocalamus asper)-polypropylene thermoplastic composite processing | |
| DE2701096C2 (en) | Polybibenzylsulfone thermoplastic polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SICHUAN DEYANG ENGINEERING PLASTICS DEVELOPMENT CO Free format text: FORMER OWNER: SICHUAN DEYANG TECHNOLOGY CO., LTD. Effective date: 20100707 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 610041 TOWER A, NO.9, HIGH-TECH INCUBATOR PARK IANFU AVENUE HENGDU CITY, SICHUAN PROVINCE TO: 610041 5 SQUARE KILOMETERS NEW DISTRICT, XIHANGGANG DEVELOPMENT ZONE, SHUANGLIU HENGDU CITY, SICHUAN PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20100707 Address after: 610041 Sichuan Province, Chengdu City Development Zone Shuangliu Southwest Airport 5 square kilometers area Patentee after: Sichuan Deyang Engineering Plastic Development Co., Ltd. Address before: 610041, A, 9 hi tech incubator Park, Tianfu Road, Sichuan, Chengdu Patentee before: Sichuan Deyang Technology Co., Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Tech., for polymerizing fibre grade polyphenyl sulfoether resin Effective date of registration: 20140522 Granted publication date: 20070725 Pledgee: China Development Bank Co Pledgor: Sichuan Deyang Engineering Plastic Development Co., Ltd. Registration number: 2014510000009 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| DD01 | Delivery of document by public notice |
Addressee: Sichuan Deyang Engineering Plastic Development Co., Ltd. Document name: Notification of Termination of Patent Right |
|
| DD01 | Delivery of document by public notice | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070725 Termination date: 20171229 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |