CN116410375A - 一种聚偏氟乙烯粉末的制备方法 - Google Patents
一种聚偏氟乙烯粉末的制备方法 Download PDFInfo
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- CN116410375A CN116410375A CN202111660590.7A CN202111660590A CN116410375A CN 116410375 A CN116410375 A CN 116410375A CN 202111660590 A CN202111660590 A CN 202111660590A CN 116410375 A CN116410375 A CN 116410375A
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- polyvinylidene fluoride
- emulsion
- washing
- fluoride powder
- ammonium salt
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 85
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 85
- 239000000843 powder Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000839 emulsion Substances 0.000 claims abstract description 80
- 239000002245 particle Substances 0.000 claims abstract description 76
- 238000005406 washing Methods 0.000 claims abstract description 74
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 239000012736 aqueous medium Substances 0.000 claims abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 59
- 150000003863 ammonium salts Chemical class 0.000 claims description 29
- 239000002351 wastewater Substances 0.000 claims description 29
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 26
- 239000012498 ultrapure water Substances 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 25
- 238000007599 discharging Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 12
- -1 cyclooctyl peroxydicarbonate Chemical compound 0.000 claims description 11
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 7
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 6
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 claims description 5
- AMEVLYGGLRIBIO-UHFFFAOYSA-N octoxycarbonyloxy octyl carbonate Chemical compound CCCCCCCCOC(=O)OOC(=O)OCCCCCCCC AMEVLYGGLRIBIO-UHFFFAOYSA-N 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 229940087562 sodium acetate trihydrate Drugs 0.000 claims description 5
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 4
- UCCWJJZPOSPPIC-UHFFFAOYSA-N COOCF Chemical compound COOCF UCCWJJZPOSPPIC-UHFFFAOYSA-N 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- ABEWDFYANWOMJE-UHFFFAOYSA-N oxalic acid;potassium Chemical compound [K].OC(=O)C(O)=O ABEWDFYANWOMJE-UHFFFAOYSA-N 0.000 claims description 3
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical group OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 235000011083 sodium citrates Nutrition 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical compound FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 claims description 2
- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 claims description 2
- SFRDXVJWXWOTEW-UHFFFAOYSA-N 2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)CO SFRDXVJWXWOTEW-UHFFFAOYSA-N 0.000 claims description 2
- 229940093475 2-ethoxyethanol Drugs 0.000 claims description 2
- IOSYNWSZBZXYJU-UHFFFAOYSA-N carboxyoxy 2-phenoxyethyl carbonate Chemical compound OC(=O)OOC(=O)OCCOC1=CC=CC=C1 IOSYNWSZBZXYJU-UHFFFAOYSA-N 0.000 claims description 2
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 claims description 2
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 claims description 2
- CSKKAINPUYTTRW-UHFFFAOYSA-N tetradecoxycarbonyloxy tetradecyl carbonate Chemical compound CCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCC CSKKAINPUYTTRW-UHFFFAOYSA-N 0.000 claims description 2
- VUWKDMFLTIEFLA-UHFFFAOYSA-N 2-chloro-1,3,4,4,5,6,6,6-octafluorohex-1-ene Chemical compound ClC(=CF)C(C(C(C(F)(F)F)F)(F)F)F VUWKDMFLTIEFLA-UHFFFAOYSA-N 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- 229920000126 latex Polymers 0.000 description 29
- 239000004816 latex Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 20
- 230000015271 coagulation Effects 0.000 description 19
- 238000005345 coagulation Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 14
- 238000005070 sampling Methods 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000012188 paraffin wax Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000001502 supplementing effect Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 7
- 239000011258 core-shell material Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000007605 air drying Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- MHYCRLGKOZWVEF-UHFFFAOYSA-N ethyl acetate;hydrate Chemical compound O.CCOC(C)=O MHYCRLGKOZWVEF-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012704 multi-component copolymerization Methods 0.000 description 2
- 238000002552 multiple reaction monitoring Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- ZYDBICLIXOCJJB-UHFFFAOYSA-N 2-chloro-1,3,4,4,5,6,6,7,8,8,8-undecafluoro-7-(trifluoromethyl)oct-1-ene Chemical compound FC(C(C(F)(F)F)(C(C(C(C(C(=CF)Cl)F)(F)F)F)(F)F)F)(F)F ZYDBICLIXOCJJB-UHFFFAOYSA-N 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/18—Monomers containing fluorine
- C08F114/22—Vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明涉及一种聚偏氟乙烯粉末的制备方法,所述制备方法包括大粒径聚偏氟乙烯乳液的制备步骤和洗涤步骤,所述大粒径聚偏氟乙烯乳液的制备步骤为:在含有引发剂、链转移剂和离子型乳化剂的水相介质中,在离子强度调节剂的存在下,偏氟乙烯经均聚反应,或偏氟乙烯与含氟共聚单体经共聚反应,制得平均粒径≥300nm的聚偏氟乙烯乳液;所述大粒径聚偏氟乙烯乳液经洗涤、干燥制得聚偏氟乙烯粉末。本发明制备的聚偏氟乙烯粉末,其杂质含量≤700ppm,能够有效提升聚偏氟乙烯的加工热稳定性。
Description
技术领域
本发明涉及聚合物领域,具体涉及聚偏氟乙烯粉末的制备方法。
背景技术
聚偏氟乙烯生产中,常用的聚合方法有乳液聚合、悬浮聚合两种方法,其中乳液聚合是制备聚偏氟乙烯最高效的方法。乳液聚合过程中需要加入乳化剂,如全氟辛酸或其铵盐、全氟磺酸或其铵盐、聚多氟烷氧基醚酸或其铵盐和全氟聚醚酸或其铵盐等。
虽然聚偏氟乙烯生产过程中必不可少乳化剂等聚合助剂,但是聚偏氟乙烯中却要求助剂含量尽可能低,最好为零,因为助剂对聚偏氟乙烯的耐热稳定性有较大负面影响。为了降低聚偏氟乙烯中的助剂含量,现有技术常采用洗涤方式,但是当聚合物乳胶粒径很小、乳胶粒间作用力很大时,洗涤液进入乳胶粒间隙阻力大,导致无法有效洗去聚合助剂。
为了提高聚合物乳胶粒粒径,现有技术常采用如下方式:
CN108047374A公开了聚四氟乙烯/聚丙烯酸酯类核壳乳液的制备方法,所述核壳乳液的制备方法,以聚四氟乙烯预乳液为种子,以丙烯酸酯类单体的共聚物为壳制备核壳结构的复合改性乳液,最终乳胶液粒径为254~323nm之间,粒径多分散指数(PDI)小于0.02。
CN112480437A公开了大粒径高固含量丁苯胶乳的制备方法,所述制备方法将丁苯橡胶进行二次乳化,通过控制乳化过程中的剪切强度、乳化剂含量等参数控制胶乳粒径,制得乳胶粒径大于500nm的丁苯胶乳。
CN110982017A公开了自消光水性丙烯酸-聚氨酯核壳乳液的制备方法,所述制备方法通过改变亲水基团的比例和聚合物链的摩尔质量来控制水分散体的粒径,使其聚合胶乳具有相对较大的粒径和较宽的粒径分布,但未公开具体的胶乳粒径大小及分布。
CN110330587A公开了宽粒径分布的丙烯酸乳液的制备方法,所述制备方法将聚合好的种子乳液连续返回预乳液罐中和预乳化单体连续滴加到反应罐中,对种子乳液粒径进行调节后获得丙烯酸乳液,该乳液粒径为50nm~5μm,粒径分布系数1~1.5。
CN101434674A公开了核壳乳液多元共聚法制备的含氟水性树脂,所述树脂以三氟氯乙烯或四氟乙烯为聚合单体,以甲基丙烯酸环烷基酯、脂肪酸烯基酯、不饱和有机硅氧烷、二醇烯基醚为改性单体,通过两步核壳乳液多元共聚方法制备平均粒径为100~200nm的含氟水性胶乳。
综上所述,大粒径聚合物胶乳的合成主要依靠附聚技术,此类方法的特点是首先合成小粒径种子胶乳,然后加入共聚单体以共聚物为壳制备核壳结构的复合改性胶乳。除此之外,也有用物理或化学方法破坏胶乳稳定性,使胶乳自身发生聚并,进而形成粒子簇,达到增大粒径的目的。但是,这类方法尽管实现大粒径胶乳的制备,但胶乳稳定性差,严重限制着胶乳的诸多应用领域。
发明内容
本发明的目的是提供一种聚偏氟乙烯粉末的制备方法,所述制备方法在聚合过程中缓慢加入离子强度调节剂,获得平均粒径不小于300nm的聚偏氟乙烯乳液,经水洗涤、干燥后得到杂质残留量很低的聚偏氟乙烯粉末。
本发明的技术方案如下:
一种聚偏氟乙烯粉末的制备方法,所述制备方法包括大粒径聚偏氟乙烯乳液的制备步骤和洗涤步骤,所述大粒径聚偏氟乙烯乳液的制备步骤为:在含有引发剂、链转移剂和离子型乳化剂的水相介质中,在离子强度调节剂的存在下,偏氟乙烯经均聚反应,或偏氟乙烯与含氟共聚单体经共聚反应,制得平均粒径≥300nm的大粒径聚偏氟乙烯乳液。
所述离子强度调节剂的加入量为聚合单体总量的0.001wt%~0.1wt%。作为优选,离子强度调节剂的加入量为聚合单体总量的0.01wt%~0.05wt%。当离子强度调节剂加入量过多时,将导致乳液稳定性变差,有聚并物生成;当离子强度调节剂加入量过少时,无法实现本发明的目的。
本发明所述离子强度调节剂选自草酸三氢钾、邻苯二甲酸氢钾、磷酸氢二钾、三水乙酸钠、四硼酸钠、柠檬酸钠或三羟甲基甲烷中的至少一种;优选地,离子强度调节剂选自草酸三氢钾、磷酸氢二钾、三水乙酸钠、四硼酸钠或柠檬酸钠中的至少一种。
本发明所用引发剂是短时间内能够分解的引发剂,这种引发剂能够让乳胶粒成核过程在短时间内完成,得到粒径基本相同的乳胶粒;优选地,所述引发剂选自过氧化二碳酸二环已酯、过氧化二碳酸二对叔丁基环已酯,过氧化二碳酸苯氧乙酯、过氧化二碳酸环辛酯、过氧化二碳酸二辛酯、过氧化二碳酸双十四烷基酯、过氧化二(十六烷基)二碳酸酯、过氧化二碳酸二-2-乙氧基乙醇酯或过氧化二碳酸二-3-甲氧基丁酯中的至少一种。
本发明所述引发剂的用量为聚合单体总量的0.03wt%~0.3wt%;优选地,所述引发剂的用量为聚合单体总量的0.05wt%~0.2wt%。
本发明所用链转移剂为本领域常用的链转移剂,优选地,所述链转移剂选自异丙醇、乙酸乙酯、丙二酸二乙酯、碳酸二乙酯、HCFC-21、HCFC-22、HCFC-123、HCFC-225或HFC-4310中的至少一种。
本发明所述链转移剂的用量为聚合单体总量的0.01wt%~2.0wt%;优选地,所述链转移剂的用量为聚合单体总量的0.05wt%~1.0wt%。
本发明所用乳化剂为离子型乳化剂,优选地,所述离子型乳化剂选自全氟辛酸或其铵盐、全氟辛磺酸或其铵盐、CF3CF2CF2-O-(CF2CF(CF3)O)m(CF(CF3)O)n-O-CF2CF2COOH或其铵盐,m为1或2,n为0~4的整数、CF3CF2CF2-O-(CF(CF3)CF2-O-)pCF(CF3)COOH或其铵盐,p为1~4的整数、CF2=CFCF2-O-CF2CF3CF2-O-CF2CF3COOH或其铵盐、CF3CF2CF2-O-(CF2CF2-O-)qCF2COOH或其铵盐,q为0~3的整数、CF3CF2(CF2OCFCF3)rCOOH或其铵盐,r为0~3的整数、F3COOCF2(CF2OCFCF3)oCOOH或其铵盐,o为0~3的整数,或CF3CF2((CFCF3)sCF2)tCF2COOH或其铵盐,s为0或1,t为0~3的整数中的至少一种;更优选地,所述离子型乳化剂选自CF3CF2CF2-O-(CF2CF(CF3)O)m(CF(CF3)O)n-O-CF2CF2COOH或其铵盐,m为1或2,n为0~4的整数、CF3CF2CF2-O-(CF(CF3)CF2-O-)pCF(CF3)COOH或其铵盐,p为1~4的整数、CF2=CFCF2-O-CF2CF3CF2-O-CF2CF3COOH或其铵盐、CF3CF2CF2-O-(CF2CF2-O-)qCF2COOH或其铵盐,q为0~3的整数、CF3CF2(CF2OCFCF3)rCOOH或其铵盐,r为0~3的整数、F3COOCF2(CF2OCFCF3)oCOOH或其铵盐,o为0~3的整数、或CF3CF2((CFCF3)sCF2)tCF2COOH或其铵盐,s为0或1,t为0~3的整数中的至少一种。
本发明所述离子型乳化剂的用量为聚合单体总量的0.03wt%~1.0wt%;优选地,所述离子型乳化剂的用量为聚合单体总量的0.06wt%~0.6wt%。
离子型乳化剂制备的聚合乳胶粒之间的作用力主要是乳胶粒表面静电斥力,水相介质中的离子强度对聚合乳胶粒的粒径大小有着非常重要的影响。当乳化剂用量多时,反应体系中离子强度大,乳胶粒表面静电斥力大,进而乳胶粒粒径小;当乳化剂用量减少时,反应体系中离子强度变小,乳胶粒表面静电斥力变小,使得乳胶粒粒径变大,但是随之带来的问题是反应体系稳定性降低,乳胶粒会发生聚并现象。
为了得到大粒径聚合乳胶粒,又不破坏反应体系稳定性,本发明在不减少乳化剂用量的基础上,在聚合过程中加入离子强度调节剂。
本发明所述聚偏氟乙烯粉末可以是偏氟乙烯经均聚反应制得,也可以是偏氟乙烯与含氟共聚单体经共聚反应制得。当采用偏氟乙烯与含氟共聚单体共聚获得时,所述含氟共聚单体选自六氟丙烯、五氟丙烯、四氟丙烯、三氟氯乙烯、三氟乙烯、氟乙烯或全氟烷基乙烯基醚中的至少一种;优选地,所述含氟共聚单体选自六氟丙烯、三氟氯乙烯、三氟乙烯、氟乙烯或全氟烷基乙烯基醚中的至少一种;所述偏氟乙烯和含氟共聚单体的质量比为60/40~99.99/0.01;优选地,所述偏氟乙烯和含氟共聚单体的质量比为80/20~95/5。
本发明所述洗涤步骤包括常压搅拌洗涤和/或真空搅拌洗涤。可以是单独的常压搅拌洗涤,也可以是单独的真空搅拌洗涤,更可以同时存在常压搅拌洗涤和真空搅拌洗涤。
为了降低聚偏氟乙烯粉末中的杂质含量,优选采用常压搅拌洗涤和真空搅拌洗涤交替进行。具体地,将大粒径聚偏氟乙烯乳液和水置于反应器中,常压搅拌洗涤和真空搅拌洗涤交替进行,单次常压搅拌洗涤和单次真空搅拌洗涤的时间为5~40min,洗涤温度为20~75℃,监测每次洗涤后排出废水的电导率,当电导率降低至1~2μS/cm时,停止洗涤,干燥制得聚偏氟乙烯粉末。
本发明所述大粒径聚偏氟乙烯乳液与水的体积比为0.1:1~1:1。
本发明所述水为纯水,优选电导率低于1μS/cm的超纯水。
本发明单次常压搅拌洗涤完毕后静置,待聚偏氟乙烯乳液上浮后,排去下层废水,单次真空搅拌洗涤完毕后静置,待聚偏氟乙烯乳液下沉后,排去上层废水。
本发明所述聚偏氟乙烯粉末的杂质含量≤700ppm。
本发明所述常压搅拌洗涤和真空搅拌洗涤交替进行的洗涤方式,空气和水交替进入聚偏氟乙烯乳胶粒的粒子孔隙,将粒子孔隙内残留的助剂洗去。常压搅拌洗涤,空气进入聚偏氟乙烯乳胶粒的粒子孔隙,所述含聚偏氟乙烯乳胶粒的分散体上浮,静置后,含聚偏氟乙烯乳胶粒的分散体和废水会分层,上层为所述含聚偏氟乙烯乳胶粒的分散体,下层为废水;真空搅拌洗涤,聚偏氟乙烯乳胶粒的粒子孔隙的空气被脱除,水进入聚偏氟乙烯乳胶粒的粒子孔隙后,所述含聚偏氟乙烯乳胶粒的分散体下沉,静置后,含聚偏氟乙烯乳胶粒的分散体和废水会分层,上层为废水,下层为所述含聚偏氟乙烯乳胶粒的分散体;再次常压搅拌洗涤时,空气进入聚偏氟乙烯乳胶粒的粒子孔隙,原胶粒孔隙内残留的助剂与水被脱除。相比于传统的高温-机械搅拌洗涤方式,所述常压搅拌洗涤和真空搅拌洗涤交替进行的洗涤方式能够有效去除粒子孔隙内残留的助剂。
本发明的技术方案相较于现有技术有如下技术效果:
(1)本发明在不减少乳化剂用量的前提下,在聚合过程中加入离子强度调节剂,制得平均粒径≥300nm的聚偏氟乙烯乳液。
(2)本发明经常压搅拌洗涤和真空搅拌洗涤交替进行的洗涤方式,制得的聚偏氟乙烯粉末的杂质含量≤700ppm,提高了聚偏氟乙烯的加工热稳定性。
附图说明
图1为本发明实施例1制备的聚偏氟乙烯粉末的扫描电镜图。
具体实施方式
下面结合具体实施例来对本发明进行进一步说明,但并不将本发明局限于这些具体实施方式。本领域技术人员应该认识到,本发明涵盖了权利要求书范围内所可能包括的所有备选方案、改进方案和等效方案。
实施例1
先将1.6g CF3CF2CF2-O-(CF2CF(CF3)O)2-O-CF2CF2COONH4和超纯水配成100g乳化剂水溶液,在5L不锈钢反应釜中,加入3000g超纯水、10g石蜡和100g上述乳化剂水溶液,合釜开启搅拌,抽真空氮气置换三次,釜温升至100℃,搅拌转速500rpm/min,补加偏氟乙烯单体至釜压达到4.0MPa。计量泵进过氧化二碳酸二辛酯1.8g和乙酸乙酯1.5g,聚合反应开始。蠕动泵以3g/min流量补加磷酸氢二钾、乙酸乙酯水溶液(0.24g磷酸氢二钾、8g乙酸乙酯与超纯水配成360g水溶液),连续补加偏氟乙烯单体维持釜压恒定在4.0MPa,偏氟乙烯消耗量达到800g,停止搅拌,排空釜内剩余反应气,底阀放出聚偏氟乙烯乳液。激光粒度仪测得乳液平均粒径为320nm。
将聚偏氟乙烯乳液冷却至40℃,经过滤除去漂浮或沉淀物,得到固含量18.0wt%的乳液4.3Kg,放料于体积20L凝聚釜中,开启搅拌至转速500rpm/min,乳液逐加入500g1wt%氯化钠溶液进行凝聚处理,破乳后静置分层10min,排去下层废水,取样做电导率测试。按膏状物、超纯水0.2:1体积比向凝聚釜中加入超纯水,维持洗涤温度56℃,150rpm/min转速搅拌洗涤20min,静置分层10min后排去下层洗涤废水,取样做电导率测试;按膏状物、超纯水体积比0.2:1继续向凝聚釜加入超纯水,抽真空至真空度为-0.08MPa,并以50rpm/min搅拌洗涤20min,静置分层10min后排去上层废水,取样做电导率测试;常压与真空搅拌交替洗涤各一次,静置分层后排去上层废水,用DDS-307型电导率测定仪在25℃温度测试电导率低于2.0μS/cm,底阀出料,气流干燥后得到聚偏氟乙烯粉末。
聚偏氟乙烯粉末采用600兆Bruker氢谱核磁共振谱仪测定石蜡残留量为100ppm,引发剂残留量为230ppm,采用HPLC-MS/MS方法测定乳化助剂残留量为350ppm。聚偏氟乙烯粉末于250℃烘箱放置半小时取出,用HunterLab ColorFlex EZ测色仪测得黄度指数为3.5。
实施例2
同实施例1,不同之处在于:以偏氟乙烯、六氟丙烯为90:10质量比补加单体至釜压达到4.0MPa。计量泵进过氧化二碳酸二辛酯1.8g和乙酸乙酯1.5g,聚合反应开始。蠕动泵以3g/min流量补加磷酸氢二钾、乙酸乙酯水溶液(0.16g磷酸氢二钾、8g乙酸乙酯与超纯水配成360g水溶液),以偏氟乙烯、六氟丙烯为90:10质量比连续补加单体维持釜压恒定在4.0MPa,反应单体消耗量达到800g,停止搅拌,排空釜内剩余反应气,底阀放出偏氟乙烯和六氟丙烯共聚物乳液。激光粒度仪测得乳液平均粒径为340nm。
偏氟乙烯和六氟丙烯共聚物乳液冷却至40℃,经过滤除去漂浮或沉淀物,得到固含量17.9wt%的乳液4.4Kg,放料于体积20L凝聚釜中,开启搅拌至转速500rpm/min,乳液逐加入500g 1wt%氯化钠溶液进行凝聚处理,破乳后静置分层10min,排去下层废水,取样做电导率测试。按膏状物、超纯水0.2:1体积比向凝聚釜中加入超纯水,维持洗涤温度56℃,150rpm/min转速搅拌洗涤20min,静置分层10min后排去下层洗涤废水,取样做电导率测试;按膏状物、超纯水体积比0.2:1继续向凝聚釜加入超纯水,抽真空至真空度为-0.08MPa,并以50rpm/min搅拌洗涤20min,静置分层10min后排去上层废水,取样做电导率测试;常压与真空搅拌交替洗涤各一次,静置分层后排去上层废水,用DDS-307型电导率测定仪在25℃温度测试电导率小于2.0μS/cm,底阀出料,气流干燥后得到偏氟乙烯和六氟丙烯共聚物粉末。
偏氟乙烯和六氟丙烯共聚物粉末采用600兆Bruker氢谱核磁共振谱仪测定石蜡残留量为90ppm,引发剂残留量为200ppm,采用HPLC-MS/MS方法测定乳化助剂残留量为320ppm。偏氟乙烯和六氟丙烯共聚物粉末于250℃烘箱放置半小时取出,用HunterLabColorFlex EZ测色仪测得黄度指数为3.0。
实施例3
同实施例1,不同之处在于:蠕动泵以3g/min流量补加三水乙酸钠、乙酸乙酯水溶液(0.16g三水乙酸钠、8g乙酸乙酯与水配成360g水溶液),以偏氟乙烯连续补加单体维持釜压恒定在4.0MPa,反应单体消耗量达到800g,停止搅拌,排空釜内剩余反应气,底阀放出聚偏氟乙烯乳液。激光粒度仪测得乳液平均粒径粒径为310nm。
聚偏氟乙烯乳液冷却至40℃,经过滤除去漂浮或沉淀物,得到固含量17.8wt%的乳液4.4Kg,放料于体积20L凝聚釜中,开启搅拌至转速500rpm/min,乳液逐加入500g 1wt%氯化钠溶液进行凝聚处理,破乳后静置分层10min,排去下层废水,取样做电导率测试。按膏状物、超纯水0.2:1体积比向凝聚釜中加入超纯水,维持洗涤温度56℃,150rpm/min转速搅拌洗涤20min,静置分层10min后排去下层洗涤废水,取样做电导率测试;按膏状物、超纯水体积比0.2:1继续向凝聚釜加入超纯水,抽真空至真空度为-0.08MPa,并以50rpm/min搅拌洗涤20min,静置分层10min后排去上层废水,取样做电导率测试;常压与真空搅拌交替洗涤各一次,静置分层后排去上层废水,用DDS-307型电导率测定仪在25℃温度测试电导率小于2.0μS/cm,底阀出料,气流干燥后得到聚偏氟乙烯粉末。
聚偏氟乙烯粉末采用600兆Bruker氢谱核磁共振谱仪测定石蜡残留量为110ppm,引发剂残留量为230ppm,采用HPLC-MS/MS方法测定乳化助剂残留量为350ppm。聚偏氟乙烯粉末于250℃烘箱放置半小时取出,用HunterLab ColorFlex EZ测色仪测得黄度指数为3.0。
对比例1
同实施例1,不同之处在于:釜温升至70℃,搅拌转速500rpm/min,补加偏氟乙烯单体至釜压达到4.0MPa。计量泵进过氧化二碳酸二正丙酯1.3g和乙酸乙酯1.0g,聚合反应开始。蠕动泵以3g/min流量补加乙酸乙酯水溶液(5g乙酸乙酯与水配成360g水溶液),连续补加偏氟乙烯单体维持釜压恒定在4.0MPa,偏氟乙烯消耗量达到800g,停止搅拌,排空釜内剩余反应气,底阀放出聚偏氟乙烯乳液。激光粒度仪测得乳液平均粒径为160nm。
聚偏氟乙烯乳液冷却至40℃,经过滤除去漂浮或沉淀物,得到固含量18wt%的乳液4.4Kg,放料于体积20L凝聚釜中,开启搅拌至转速500rpm/min,乳液逐加入500g 1wt%氯化钠溶液进行凝聚处理,破乳后静置分层10min,排去下层废水,取样做电导率测试。按膏状物、超纯水0.2:1体积比向凝聚釜中加入超纯水,维持洗涤温度56℃,150rpm/min转速搅拌洗涤20min,静置分层10min后排去下层洗涤废水,取样用DDS-307型电导率测定仪在25℃温度测试电导率;继续常压搅拌洗涤直至废水电导率小于2.0μS/cm,底阀出料,气流干燥后得到聚偏氟乙烯粉末。
聚偏氟乙烯粉末采用600兆Bruker氢谱核磁共振谱仪测定石蜡残留量为300ppm,引发剂残留量为430ppm,采用HPLC-MS/MS方法测定乳化助剂残留量为950ppm。聚偏氟乙烯粉末于250℃烘箱放置半小时取出,用HunterLab ColorFlex EZ测色仪测得黄度指数为13.8。
对比例2
同实施例1,不同之处在于:预先将1.2g CF3CF2CF2-O-(CF2CF(CF3)O)2-O-CF2CF2COONH4和超纯水配成100g乳化剂水溶液,在5L不锈钢反应釜中,加入3000g超纯水、10g石蜡和100g上述乳化剂水溶液,合釜开启搅拌,抽真空氮气置换三次,釜温升至100℃,搅拌转速500rpm/min,补加偏氟乙烯单体至釜压达到4.0MPa。计量泵进过氧化二碳酸二辛酯1.8g和乙酸乙酯1.5g,聚合反应开始。蠕动泵以3g/min流量补加乙酸乙酯水溶液(8g乙酸乙酯与水配成360g水溶液),连续补加偏氟乙烯单体维持釜压恒定在4.0MPa,偏氟乙烯消耗量达到800g,停止搅拌,排空釜内剩余反应气,底阀放出聚偏氟乙烯乳液,釜底及收料桶底有聚并凝聚物生成。激光粒度仪测得乳液平均粒径为300nm。
聚偏氟乙烯乳液冷却至40℃,经过滤除去漂浮或沉淀物,得到固含量17.3wt%的乳液3.5Kg,放料于体积20L凝聚釜中,开启搅拌至转速500rpm/min,乳液逐加入500g 1wt%氯化钠溶液进行凝聚处理,破乳后静置分层10min,排去下层废水,取样做电导率测试。按膏状物、超纯水0.2:1体积比向凝聚釜中加入超纯水,维持洗涤温度56℃,150rpm/min转速搅拌洗涤20min,静置分层10min后排去下层洗涤废水,取样做电导率测试;按膏状物、超纯水体积比0.2:1继续向凝聚釜加入超纯水,抽真空至真空度为-0.08MPa,并以50rpm/min搅拌洗涤20min,静置分层10min后排去上层废水,取样做电导率测试;常压与真空搅拌交替洗涤各一次,静置分层后排去上层废水,用DDS-307型电导率测定仪在25℃温度测试电导率低于2.0μS/cm,底阀出料,气流干燥后得到聚偏氟乙烯粉末。
聚偏氟乙烯粉末采用600兆Bruker氢谱核磁共振谱仪测定石蜡残留量为320ppm,引发剂残留量为460ppm,采用HPLC-MS/MS方法测定乳化助剂残留量为1280ppm。
聚偏氟乙烯粉末于250℃烘箱放置半小时取出,用HunterLab ColorFlex EZ测色仪测得黄度指数为13.5。
表1实施例与对比例乳液粒径、黄色指数、助剂残留量测试结果
注:
乳液粒径d 0.51采用移液管取0.2ml乳液于样品池中,用马尔文Mastersizer2000激光粒度仪测试;
黄色指数2:聚合物粉末物料置于铝箔中,250℃烘箱放置半小时取出,用HunterLab ColorFlex EZ测色仪测得黄度指数;
引发剂残留量3、石蜡残留量3的测试方法:采用600兆Bruker氢谱核磁共振谱仪通过氢谱核磁共振的方法测定引发剂残留量、石蜡残留量;
乳化剂残留量4的测试方法:取待聚合物粉末样品经前处理加入萃取剂,经索氏抽提得萃取液,萃取液经净化后,使用Waters ACQUITY UPLC高效液相-串联四级杆质谱仪HPLC-MS/MS检测助剂残留量。质谱仪的流动相为色谱纯甲醇和水,洗脱方式为梯度洗脱,色谱柱为ACQUITY BEH C18柱,规格为2.1mm×50mm,1.7μm,柱温为30-50℃,流速0.4mL/min。质谱检测条件为:离子化方式为ESI,监测模式为MRM(多反应监测),负离子扫描。
Claims (12)
1.一种聚偏氟乙烯粉末的制备方法,其特征在于:所述制备方法包括大粒径聚偏氟乙烯乳液的制备步骤和洗涤步骤,所述大粒径聚偏氟乙烯乳液的制备步骤为:在含有引发剂、链转移剂和离子型乳化剂的水相介质中,在离子强度调节剂的存在下,偏氟乙烯经均聚反应,或偏氟乙烯与含氟共聚单体经共聚反应,制得平均粒径≥300nm的大粒径聚偏氟乙烯乳液。
2.根据权利要求1所述的聚偏氟乙烯粉末的制备方法,其特征在于:所述离子强度调节剂的加入量为聚合单体总量的0.001wt%~0.1wt%。
3.根据权利要求1所述的聚偏氟乙烯粉末的制备方法,其特征在于:所述离子强度调节剂选自草酸三氢钾、邻苯二甲酸氢钾、磷酸氢二钾、三水乙酸钠、四硼酸钠、柠檬酸钠或三羟甲基甲烷中的至少一种。
4.根据权利要求1所述的聚偏氟乙烯粉末的制备方法,其特征在于:所述引发剂选自过氧化二碳酸二环已酯、过氧化二碳酸二对叔丁基环已酯、过氧化二碳酸苯氧乙酯、过氧化二碳酸环辛酯、过氧化二碳酸二辛酯、过氧化二碳酸双十四烷基酯、过氧化二(十六烷基)二碳酸酯、过氧化二碳酸二-2-乙氧基乙醇酯或过氧化二碳酸二-3-甲氧基丁酯中的至少一种。
5.根据权利要求1所述的聚偏氟乙烯粉末的制备方法,其特征在于:所述离子型乳化剂选自全氟辛酸或其铵盐、全氟辛磺酸或其铵盐、CF3CF2CF2-O-(CF2CF(CF3)O)m(CF(CF3)O)n-O-CF2CF2COOH或其铵盐,m为1或2,n为0~4的整数、CF3CF2CF2-O-(CF(CF3)CF2-O-)pCF(CF3)COOH或其铵盐,p为1~4的整数、CF2=CFCF2-O-CF2CF3CF2-O-CF2CF3COOH或其铵盐、CF3CF2CF2-O-(CF2CF2-O-)qCF2COOH或其铵盐,q为0~3的整数、CF3CF2(CF2OCFCF3)rCOOH或其铵盐,r为0~3的整数、F3COOCF2(CF2OCFCF3)oCOOH或其铵盐,o为0~3的整数或CF3CF2((CFCF3)sCF2)tCF2COOH或其铵盐,s为0或1,t为0~3的整数中的至少一种,所述离子型乳化剂的用量为聚合单体总量的0.03wt%~1.0wt%。
6.根据权利要求1所述的聚偏氟乙烯粉末的制备方法,其特征在于:所述含氟共聚单体选自六氟丙烯、五氟丙烯、四氟丙烯、三氟氯乙烯、三氟乙烯、氟乙烯或全氟烷基乙烯基醚的至少一种。
7.根据权利要求1所述的聚偏氟乙烯粉末的制备方法,其特征在于:所述洗涤步骤包括常压搅拌洗涤和/或真空搅拌洗涤。
8.根据权利要求7所述的聚偏氟乙烯粉末的制备方法,其特征在于:将大粒径聚偏氟乙烯乳液和水置于反应器中,常压搅拌洗涤和真空搅拌洗涤交替进行,单次常压搅拌洗涤和单次真空搅拌洗涤的时间为5~40min,洗涤温度为20~75℃,监测每次洗涤后排出废水的电导率,当电导率降低至1~2μS/cm时,停止洗涤,干燥制得聚偏氟乙烯粉末。
9.根据权利要求7所述的聚偏氟乙烯粉末的制备方法,其特征在于:所述大粒径聚偏氟乙烯乳液和水的体积比为0.1:1~1:1。
10.根据权利要求7所述的聚偏氟乙烯粉末的制备方法,其特征在于:所述水为电导率低于1μS/cm的超纯水。
11.根据权利要求8所述的聚偏氟乙烯粉末的制备方法,其特征在于:单次常压搅拌洗涤完毕后静置,待聚偏氟乙烯乳液上浮后,排去下层废水;单次真空搅拌洗涤完毕后静置,待聚偏氟乙烯乳液下沉后,排去上层废水。
12.根据权利要求1至11任一所述的聚偏氟乙烯粉末的制备方法,其特征在于:所述聚偏氟乙烯粉末的杂质含量≤700ppm。
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