WO2021053531A1 - Low molecular weight polytetrafluoroethylene micropowder and process for preparing the same - Google Patents
Low molecular weight polytetrafluoroethylene micropowder and process for preparing the same Download PDFInfo
- Publication number
- WO2021053531A1 WO2021053531A1 PCT/IB2020/058608 IB2020058608W WO2021053531A1 WO 2021053531 A1 WO2021053531 A1 WO 2021053531A1 IB 2020058608 W IB2020058608 W IB 2020058608W WO 2021053531 A1 WO2021053531 A1 WO 2021053531A1
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- WIPO (PCT)
- Prior art keywords
- ptfe
- molecular weight
- low molecular
- micropowder
- polymerization
- Prior art date
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 126
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 126
- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 47
- 239000002245 particle Substances 0.000 claims abstract description 40
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 14
- 238000006731 degradation reaction Methods 0.000 claims abstract description 11
- 230000015556 catabolic process Effects 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 230000001112 coagulating effect Effects 0.000 claims abstract description 4
- 239000003039 volatile agent Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 37
- 230000008569 process Effects 0.000 claims description 26
- 239000003999 initiator Substances 0.000 claims description 25
- 239000004094 surface-active agent Substances 0.000 claims description 23
- 238000012546 transfer Methods 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000005345 coagulation Methods 0.000 claims description 9
- 230000015271 coagulation Effects 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 9
- 230000000977 initiatory effect Effects 0.000 claims description 9
- 239000004160 Ammonium persulphate Substances 0.000 claims description 8
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 8
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 235000005985 organic acids Nutrition 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 11
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound 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 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000000843 powder Substances 0.000 description 30
- 229920000642 polymer Polymers 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 150000003254 radicals Chemical class 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 230000008901 benefit Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 239000012986 chain transfer agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229920002313 fluoropolymer Polymers 0.000 description 7
- 239000004811 fluoropolymer Substances 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000012736 aqueous medium Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000014509 gene expression Effects 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000004075 alteration Effects 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012431 aqueous reaction media Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004428 fluoroalkoxy group Chemical group 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052920 inorganic sulfate Inorganic materials 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical class [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000003797 telogen phase Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- 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
- C08J3/16—Powdering or granulating by coagulating dispersions
-
- 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
- C08F14/00—Homopolymers and 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
- C08F14/18—Monomers containing fluorine
- C08F14/26—Tetrafluoroethene
-
- 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
- C08F114/26—Tetrafluoroethene
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/008—Treatment of solid polymer wetted by water or organic solvents, e.g. coagulum, filter cakes
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/18—Increasing the size of the dispersed particles
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/22—Coagulation
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/24—Treatment of polymer suspensions
-
- 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
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
Definitions
- the present invention pertains to a process for preparing a polymeric material. More particularly, the present invention relates to low molecular weight polytetrafluoroethylene. More particularly, the invention also relates to a process for preparing low molecular weight Polytetrafluoroethylene also known as “PTFE micropowders”. BACKGROUND OF THE INVENTION
- PTFE micropowders are low molecular weight PTFE, mainly used as an additive in polymers, coatings, paints, rubbers, cosmetics, waxes, inks, adhesives, greases and lubricants.
- PTFE Micropowders exhibit impressive array of following properties that make them the material of choice for various demanding applications:
- low molecular weight PTFE powders have been produced typically from high molecular weight PTFE powders by degradation methods like irradiation with high energy electrons from either a gamma source or an electron beam, or high temperature treatment.
- ECHA European Chemical Agency
- EU 2020/784 EU 2019/1021, Annex -XVII to REACH, Entry 68
- PFOA Perfluorooctanoic acid
- US7176265B patent titled “Directly polymerized low molecular weight granular polytetrafluoroethylene” discloses direct polymerized low molecular weight PTFE.
- Low molecular weight granular polytetrafluoroethylene or modified polytetrafluoroethylene having a melt viscosity of less than about lxlO 6 Pa-S powder is isolated directly from the reaction vessel.
- the low molecular weight polytetrafluoroethylene or modified polytetrafluoroethylene powder in this patent has a melt viscosity of less than about lx 10 6 Pa-S, a specific surface area of less than about 8 m / g, an extractable fluoride level of about 3 ppm or less by weight, and a narrow molecular weight distribution as indicated by a polydispersity index of about 5 or less.
- the particles of low molecular powder have a weight average particle size of about 2 to about 40 micrometers and the powder is substantially free of particles having a particle size of less than about 1 micrometer.
- the low molecular weight polytetrafluoroethylene or modified polytetrafluoroethylene powder in this patent has a melt viscosity of less than about lxlO 6 Pa-S,
- US8754176B2 patent titled “Low molecular weight polytetrafluoroethylene powder and preparation method therefore” discloses Low molecular weight polytetrafluoroethylene powder.
- a low-molecular weight polytetrafluoroethylene powder has been disclosed.
- the low molecular weight PTLE micropowder has been used as an additive in a coating material, etc., can form a coating with excellent texture and gliding properties, while also improving dispersibility and viscosity; and a production process therefor.
- It discloses a process for producing a low-molecular weight polytetrafluoroethylene powder comprising: an emulsion polymerization step of polymerizing at least tetrafluoroethylene in the presence of a polymerization initiator and an aqueous medium to produce emulsified particles thereof; an agglomeration step of agglomerating the emulsified particles to form an agglomerated powder thereof; and a suspension polymerization step of polymerizing at least tetrafluoroethylene in the presence of the agglomerated powder, a polymerization initiator, and an aqueous medium.
- the low-molecular weight polytetrafluoroethylene powder satisfies a melt viscosity of 700,000 Pa-s or less has been disclosed.
- melt viscosity was only found ranging from 1.0x10 to 7.0xl0 5 Pa-s, at 380°C.
- the present invention relates to production of low molecular weight PTFE micropowder by direct polymerization technology and overcomes limitation of the melt viscosities over prior art and that is devoid of the step of irradiation or thermal degradation and complies with regulations on PFOA restriction in substances.
- the main objective of this invention is to provide low molecular weight PTFE powder and a process of direct polymerization for preparing low molecular weight Polytetrafluoroethylene (PTFE) micropowder that overcomes limitations of the melt viscosities over prior art.
- Another objective of this invention is to provide a low molecular weight PTFE powder and a process for preparing low molecular weight Polytetrafluoroethylene (PTFE) micropowder that may be devoid of the step of exposure to high temperature or ionizing radiations.
- Still another objective of this invention is to provide a low molecular weight PTFE micropowder and a process for producing the same employing direct polymerization.
- the present invention relates to low molecular weight PTFE powder and a process for preparing a low molecular weight polytetrafluoroethylene (PTFE) micropowder.
- PTFE polytetrafluoroethylene
- the present invention relates to production of low molecular weight PTFE micropowder by direct polymerization technology and overcomes limitation of the melt viscosities over prior art and that is devoid of the step of irradiation or thermal degradation and complies with regulations on PFOA restriction in substances.
- the low molecular weight PTFE micropowder may be produced by direct polymerization technology and it may be devoid of the degradation steps like irradiation or high temperature treatment.
- the low molecular weight PTFE micropowder may have particle size is in the range from 2 pm to 600 pm.
- the low molecular weight PTFE micropowder may have specific surface area (SSA) ranging from 3.0 to 20.0 m /g.
- the low molecular weight PTFE micropowder may have standard gravity ranges from 2.145-2.212.
- the low molecular weight PTFE micropowder may have molecular weight less than or equal to 6,00,000.
- a process for preparing a low molecular weight polytetrafluoroethylene (PTFE) micropowder having melt viscosity of range melt viscosity of 1,000,001- 999,999,999 Pascal at 380°C at 21.6 Kg load is disclosed.
- the process for preparing a low molecular weight polytetrafluoroethylene (PTFE) micropowder may comprises the steps of:
- TFE Tetrafluoroethylene
- the step of polymerizing TFE may comprises:
- the aqueous emulsion may comprise an initiator for initiating the polymerization process, selected from the group consisting of Disuccinic Acid Peroxide (DSAP), Ammonium Persulphate (APS), Potassium Persulphate (KPS) and combinations thereof.
- an initiator for initiating the polymerization process selected from the group consisting of Disuccinic Acid Peroxide (DSAP), Ammonium Persulphate (APS), Potassium Persulphate (KPS) and combinations thereof.
- the aqueous emulsion may comprise chain transfer agents selected from the group consisting of alcohols, hydrocarbons and combinations thereof.
- the step of polymerizing TFE may comprise suspension polymerisation.
- the process for polymerizing TFE may be carried out at a temperature of 20 to 1201C, pressure of 8 to 25 Bar, and for a polymerization reaction period of 60 to 400 minutes.
- the step of coagulation is induced by adding organic acids or inorganic acids.
- the organic acids comprises of group consisting of phosphoric acid, oxalic acid, nitric acid, sulphuric acid, hydrochloric acid and combination thereof
- wet PTFE micropowder After washing the coagulated particles with water and steam, the drying of wet PTFE micropowder may be carried out.
- a low molecular weight PTFE micropowder produced by direct polymerization and devoid of any degradation steps like irradiation or high temperature treatment.
- the particle size of PTFE micropowder may varies from a range of 2 pm to 600 pm, the melt viscosity may ranges from 1,000,001- 999,999,999 Pascal at 380°C at 21.6 Kg load.
- Figure 1 Flowchart for the process for preparing a low molecular weight Polytetrafluoroethylene micropowder.
- the present invention relates to low molecular weight PTFE powder and a process for preparing a low molecular weight polytetrafluoroethylene (PTFE) micropowder.
- the present invention relates to production of low molecular weight PTFE micropowder by direct polymerization technology and overcomes limitation of the melt viscosities over prior art and that is devoid of the step of irradiation or thermal degradation and complies with regulations on PFOA restriction in substances
- the melt viscosity may be also measured according to ASTM D 1238 using a flow tester(make: Dynisco) die diameter of 2.095 and is a value measured by preheating 3 g of test sample for 5 min at 380°C. and measuring the same with a load of 21.6 kg while maintaining that temperature
- the low molecular weight PTFE micropowder may have particle size is in the range from 2 pm to 600 pm.
- the particle size may be measured by Dynamic light scattering system.
- the particle size may be measured by D50 analysis.
- the particle size analysis may be done by laser diffraction method as per ASTM D4894.
- the low molecular weight PTFE micropowder may have specific surface area (SSA) ranging from 3.0 to 20.0 m /g,
- the specific surface area may be measured by BET using a surface analyzer with a mixed gas of 30% nitrogen and 70% helium as the carrier gas and liquid nitrogen. Standard Gravity
- the low molecular weight PTFE micropowder may have standard gravity ranges from 2.145-2.212.
- the melt viscosity may be measured at 380°C at 21.6 Kg load.
- the temperature may be measured by using ASTM D 4591 by using differential scanning calorimeter.
- approximately 3 mg of the low-molecular weight PTFE powder may be placed in an aluminum pan (crimped container) and the temperature is raised 10°C./min in the 240 to 380°C at 21.6 Kg load under a 50 mF/min air flow.
- the melting point may be defined as the minimum point of required melting heat within the above range.
- the low molecular weight PTFE micropowder may have extractable fluoride level which may range from 1 ppm or less by weight .
- low molecular weight PTFE micropowder is made by direct polymerization process that is devoid of any further degradation step like irradiation or high temperature treatment.
- a process for preparing a low molecular weight polytetrafluoroethylene (PTFE) micropowder having melt viscosity of range melt viscosity of 1,000,000- 999,999,999 Pascal at 380°C at 21.6 Kg load is disclosed.
- Figure 1 illustrates process for producing low molecular weight polytetrafluoroethylene micropowder from high molecular weight PTFE composition.
- a process for preparing a low molecular weight polytetrafluoroethylene (PTFE) micropowder comprising the steps of: (a) polymerizing Tetrafluoroethylene (TFE);
- fluoromonomers may comprises of Tetrafluoroethylene. It may be in gas form and condensed at high pressure into liquid form. The monomer may be stored in metering tank for further adding it for further process in to required quantity.
- the fluoromonomer may be passed through silica gel absorber to remove moisture prior to feeding it into polymerization reactor.
- the reactor may be made free from any oxygen content. DI water may be further added to reactor as media at specified RPM to control reaction rate.
- reaction additives added into reactor may comprise of following: a. Inorganic sulphates as initiator, used as a positive catalyst for initiation of monomer during reaction b. Ammonia to maintain basic pH c. Surfactant system which reduces surface tension between media and monomer by micelles formation required for growth of polymer to make stable dispersion d. Organic Chain transfer agents(CTA) which helps in required size chain formation
- polymerization step is step 1 where fluoromonomers are polymerized into various process conditions
- the temperature for polymerization may range from 20-120 deg C.
- Pressure The pressure during polymerization may range from 8-25 bar
- Reaction Time The total reaction time varies from 60-400 mins After consumption of defined quantity of fluoromonomers and down polymerization to certain pressure gets completed, pressure eventually may be released to atmosphere and polymer may be formed in latex form (solid and liquid mixture). All solid particles present in primary particles may ranges from 50-200 nm.
- Coagulation leads to an increase in the particle size distribution of the polymer from nanometer range to micrometers.
- the wet powder may be subjected to drying systems.
- powder may be dried with help of hot air to moisture level less than 0.1%.
- Maximum air temperature may be 450°C.
- powder coming may be free flowing low molecular weight PTFE in form of final product.
- the process for polymerizing TFE may comprises the steps of:
- the aqueous emulsion formed in the present invention may comprise of surfactant system, fluoromonomers, initiators and chain transfer agents.
- the step of polymerizing TFE may comprise suspension polymerisation.
- the process of the present invention is preferably carried so that the contents of the reaction vessel are essentially free of surfactant, i.e., the amount of surfactant is less than 0.010% based on the amount of water present.
- surfactant means a type of molecule which has both hydrophobic and hydrophilic, portions, which allows it to stabilize and disperse hydrophobic molecules and aggregates of hydrophobic molecules in aqueous systems.
- a preferred group of surfactant system for fluoropolymer synthesis according to the embodiments of the present invention include fluorinated surfactants, non- fluorinated surfactant and a combination of these.
- surfactants for the present invention may include Ammonium or potassium or sodium salts of perfluoro alkyl ether carboxylic acids.
- fluoromonomer or the expression “fluorinated monomer” means a polymerizable alkene which contains at least one fluorine atom, fluoroalkyl group, or fluoroalkoxy group attached to the double bond of the alkene that undergoes polymerization.
- fluoropolymer means a polymer formed by the polymerization of at least one fluoromonomer, and it is inclusive of homopolymers, copolymers, terpolymers and higher polymers.
- the fluoromonomer is tetrafluoroethylene (TFE) and the fluoropolymer is polytetrafluoroethylene (PTFE).
- the aqueous emulsion may further comprise an initiator for initiating the polymerization process.
- Initiators for initiating the polymerization process.
- initiator and the expressions “radical initiator” and “free radical initiator” refer to a chemical that is capable of providing a source of free radicals, either induced spontaneously, or by exposure to heat or light.
- suitable initiators include peroxides, peroxydicarbonates and azo compounds. Initiators may also include reduction-oxidation systems which provide a source of free radicals.
- radical and the expression “free radical” refer to a chemical species that contains at least one unpaired electron.
- the radical initiator is added to the reaction mixture in an amount sufficient to initiate and maintain the polymerization reaction rate. Preferably, the addition of the initiator into the reaction vessel or reactor is carried out in one shot.
- the radical initiator may comprise a persulfate salt, such as sodium persulfate, potassium persulfate, or ammonium persulfate and combinations thereof .
- the radical initiator may comprise a redox system.
- Redox system is understood by a person skilled in the art to mean a system comprising an oxidizing agent, a reducing agent and optionally, a promoter as an electron transfer medium.
- the radical initiator is selected from the group consisting of Disuccinic Acid Peroxide (DSAP), Ammonium Persulphate (APS) and combinations thereof.
- DSAP Disuccinic Acid Peroxide
- APS Ammonium Persulphate
- the initiator may be used from 50-3000 ppm. Chain transfer agents
- Chain transfer agents also referred to as modifiers or regulators, comprises of at least one chemically weak bond.
- a chain transfer agent reacts with the free -radical site of a growing polymer chain and halts an increase in chain length. Chain transfer agents are often added during polymerization to regulate chain length of a polymer to achieve the desired properties in the polymer.
- chain transfer implies the stopping of growth of one polymer chain and the initiation of growth of another such that the number of growing polymer radicals remains similar and the polymerization proceeds at a similar rate without the introduction of more initiator.
- the new radical formed by the reaction of the growing polymer chain with a CTA does not always initiate a new polymer chain.
- chain transfer agents examples include, but not limited to, halogen compounds, hydrocarbons in general, aromatic hydrocarbons, thiols (mercaptans), alcohols and so forth; each of which can be used individually or in combination.
- the chain transfer agent may varies from 50-3,000 ppm.
- the temperature used for polymerization may vary, for example, from 20 to 120 °C, depending on the initiator system chosen and the reactivity of the fluoromonomer(s) selected. In a preferred embodiment, the polymerization is carried out at a temperature in the range of 50 to 85 °C.
- the pressure used for polymerization may vary from 2-200 bar, depending on the reaction equipment, the initiator system, and the monomer selection. In preferred embodiment the reaction is carried out at a pressure in the range of 8 to 25 bar.
- the polymerization occurs under stirring or agitation.
- the stirring may be constant, or may be varied to optimize process conditions during the course of the polymerization. In one embodiment, both multiple stirring speeds and multiple temperatures are used for controlling the reaction.
- a pressurized polymerization reactor equipped with a stirrer and heat control means is charged with water, preferably deionized water, surfactant system in accordance with the invention, chain transfer agents and at least one fluoromonomer.
- the surfactant is added in an amount in the range from 2000 to 7000 ppm, more preferably from 2500 to 5000 ppm, based on the weight of fluoropolymer dispersion.
- the surfactant is added in one shot into the reaction vessel.
- the reaction mixture comprises chain transfer agents in an amount in the range from 50 to 3000 ppm.
- the mixture may optionally contain paraffin wax.
- the reactor is then heated up to the reaction temperature and pressure. Thereafter initiators are added into the reaction vessel to initiate the polymerization reaction.
- the initiator is introduced into the reaction vessel in one shot.
- the initiator is added in an amount in the range from 50 to 3000 ppm, based on the weight of de-ionized water.
- air is removed from the reactor in order to obtain an oxygen-free environment for the polymerization reaction.
- the oxygen is removed from the reaction vessel until its concentration is less than 10 ppm.
- the reactor may also be purged with a neutral gas such as, for example, nitrogen.
- the reactor Upon completion of the polymerization reaction, the reactor is brought to ambient temperature and the residual unreacted monomer is vented to atmospheric pressure.
- the aqueous reaction medium containing the fluoropolymer is then recovered from the reaction vessel.
- the latex content ranges from 10 to 30%, and the particle size of the fluoropolymer particles ranges from 50 to 200 nm.
- coagulation is one of the vital processes that determines the particle size distribution of a product made by emulsion polymerization. Coagulation leads to an increase in the particle size distribution of the polymer from nanometer range to micrometers. Preferably coagulation is carried out till the particle size distribution of the fluoropolymer particles is in the range of 2 to 600pm.
- the coagulation of polymer particles is achieved by using inorganic or organic acids. Examples of acids that can be used in the present invention include, but not limited to phosphoric acid, oxalic acid, nitric acid, sulphuric acid, hydrochloric acid and so forth, each of which can be used alone or in combination.
- the polymer particles having micrometer sized particle distribution are separated from the mother liquor, and washed with hot and cold water with high speed stirring to remove remaining surfactant, unreacted substances and byproducts.
- the resulting powder is further subjected to steam treatment to remove volatile impurities to afford wet low molecular weight PTFE micropowder.
- the wet low molecular weight PTFE micropowder is dried in an oven to afford low molecular weight PTFE micropowder.
- drying of the wet low molecular weight PTFE micropowder is carried out at a temperature of less than or equal to 450 C.
- the polymerization process was carried out in a 150 L reactor with 100 L of de-ionized water. Oxygen was removed from the reactor until its concentration was less than 10 ppm. After that, the surfactant(s), 3200 ppm, was added in one shot into the reactor. Further, chain transfer agent, 60 ppm (aqueous based), was added into the reactor. Thereafter, the addition of Tetrafluoroethylene (TFE) caused an increase in the pressure to 15 bar and the temperature was increased to 65°C. After attaining the operating pressure and temperature a solution comprising an initiator Ammonium Persulphate (APS) was added into the reactor in one shot for initiating the polymerization process.
- TFE Tetrafluoroethylene
- APS Ammonium Persulphate
- the PTFE particles were coagulated, using nitric acid.
- the coagulated particles were separated from the mother liquor and washed with hot and cold water, steam treated and dried at a temperature of 240°C to get low molecular weight PTFE micropowder.
- the advantages of the present invention are as following: a) The invention discloses a low molecular weight PTFE powder by direct polymerization overcoming melt viscosity limitation over prior art. b) The present invention discloses a process for producing low molecular weight PTFE micropowder that complies with various regulations on restriction of PFOA, its salts and related compounds in substances. c) The present invention discloses a process for producing low molecular weight Polytetrafluoroethylene (PTFE) micropowder by using methods which may be devoid of the step of irradiating or other degradation methods.
- PTFE Polytetrafluoroethylene
- Low molecular weight polytetrafluoroethylene can be advantageously used as an additive in other materials for improving sliding properties, increasing release, improving wear resistance, conferring increased stain and mar resistance, enhancing flame retardancy, and increasing water repellency.
- These low molecular weight powders are advantageously added to thermoplastics, paints, coatings, lacquers, greases, oils, lubricants, thermoset resins, and elastomers.
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JP2022516619A JP2023501048A (ja) | 2019-09-17 | 2020-09-16 | 低分子量ポリテトラフルオロエチレン微粉末及びその調製方法 |
KR1020227012593A KR20220065003A (ko) | 2019-09-17 | 2020-09-16 | 저분자량 폴리테트라플루오로에틸렌 미세분말 및 그것의 제조 방법 |
CN202080064703.4A CN114450317A (zh) | 2019-09-17 | 2020-09-16 | 低分子量聚四氟乙烯微粉及其制备方法 |
GB2205473.8A GB2604463B (en) | 2019-09-17 | 2020-09-16 | Low molecular weight polytetrafluoroethylene micropowder and process for preparing the same |
EP20866024.1A EP4031589A4 (en) | 2019-09-17 | 2020-09-16 | LOW MOLECULAR WEIGHT POLYTETRAFLUORETHYLENE MICROPOWDER AND METHOD FOR THE PRODUCTION THEREOF |
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JP (1) | JP2023501048A (ko) |
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WO2004050727A1 (en) * | 2002-11-22 | 2004-06-17 | E.I. Du Pont De Nemours And Company | Directly polymerized low molecular weight granular polytetrafluoroethylene |
EP2267047B1 (en) * | 2008-04-14 | 2012-01-18 | Asahi Glass Company, Limited | Production method of polytetrafluoroethylene fine powder |
US20130122302A1 (en) * | 2010-09-30 | 2013-05-16 | Daikin Industries, Ltd. | Process for producing polytetrafluoroethylene fine powder |
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US6395848B1 (en) * | 1999-05-20 | 2002-05-28 | E. I. Du Pont De Nemours And Company | Polymerization of fluoromonomers |
US8071198B2 (en) * | 2006-11-17 | 2011-12-06 | E.I. Du Pont De Nemours And Company | Glass articles with adhesion and stain resistant non-stick coatings |
JP5569519B2 (ja) * | 2009-03-31 | 2014-08-13 | ダイキン工業株式会社 | 低分子量ポリテトラフルオロエチレン粉末及びその製造方法 |
US9175110B2 (en) * | 2012-05-09 | 2015-11-03 | The Chemours Company Fc, Llc | Fluoropolymer resin treatment employing melt extrusion and exposure to oxygen source to reduce discoloration |
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WO2004050727A1 (en) * | 2002-11-22 | 2004-06-17 | E.I. Du Pont De Nemours And Company | Directly polymerized low molecular weight granular polytetrafluoroethylene |
EP2267047B1 (en) * | 2008-04-14 | 2012-01-18 | Asahi Glass Company, Limited | Production method of polytetrafluoroethylene fine powder |
US20130122302A1 (en) * | 2010-09-30 | 2013-05-16 | Daikin Industries, Ltd. | Process for producing polytetrafluoroethylene fine powder |
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WO2023204125A1 (ja) * | 2022-04-18 | 2023-10-26 | ダイキン工業株式会社 | 精製ポリテトラフルオロエチレン粉末の製造方法及び低分子量ポリテトラフルオロエチレン粉末 |
JP7385150B2 (ja) | 2022-04-18 | 2023-11-22 | ダイキン工業株式会社 | 精製ポリテトラフルオロエチレン粉末の製造方法及び低分子量ポリテトラフルオロエチレン粉末 |
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GB2604463A (en) | 2022-09-07 |
KR20220065003A (ko) | 2022-05-19 |
EP4031589A4 (en) | 2023-10-04 |
EP4031589A1 (en) | 2022-07-27 |
CN114450317A (zh) | 2022-05-06 |
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