CN114539462B - 由四氟丙烯形成的可固化含氟共聚物 - Google Patents
由四氟丙烯形成的可固化含氟共聚物 Download PDFInfo
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- CN114539462B CN114539462B CN202210354209.2A CN202210354209A CN114539462B CN 114539462 B CN114539462 B CN 114539462B CN 202210354209 A CN202210354209 A CN 202210354209A CN 114539462 B CN114539462 B CN 114539462B
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- Prior art keywords
- copolymer
- unit
- tetrafluoropropene
- vinyl
- vinyl ether
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- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 title abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 55
- 239000000178 monomer Substances 0.000 claims abstract description 18
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 45
- 238000000576 coating method Methods 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 13
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 claims description 12
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003973 paint Substances 0.000 claims description 7
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- -1 Polytetrafluoroethylene Polymers 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 9
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 6
- 229920001228 polyisocyanate Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 5
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical group FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 5
- 239000004640 Melamine resin Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000004434 industrial solvent Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- OUJCKESIGPLCRN-UHFFFAOYSA-N 1,5-diisocyanato-2,2-dimethylpentane Chemical compound O=C=NCC(C)(C)CCCN=C=O OUJCKESIGPLCRN-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- NSOAQRMLVFRWIT-UHFFFAOYSA-N 1-ethenoxydecane Chemical compound CCCCCCCCCCOC=C NSOAQRMLVFRWIT-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- YAOJJEJGPZRYJF-UHFFFAOYSA-N 1-ethenoxyhexane Chemical compound CCCCCCOC=C YAOJJEJGPZRYJF-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- KTIBRDNFZLYLNA-UHFFFAOYSA-N 2-(2-hydroxyethenoxy)ethenol Chemical compound OC=COC=CO KTIBRDNFZLYLNA-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- OJXVWULQHYTXRF-UHFFFAOYSA-N 3-ethenoxypropan-1-ol Chemical compound OCCCOC=C OJXVWULQHYTXRF-UHFFFAOYSA-N 0.000 description 1
- BCTDCDYHRUIHSF-UHFFFAOYSA-N 5-ethenoxypentan-1-ol Chemical compound OCCCCCOC=C BCTDCDYHRUIHSF-UHFFFAOYSA-N 0.000 description 1
- ASPUDHDPXIBNAP-UHFFFAOYSA-N 6-ethenoxyhexan-1-ol Chemical compound OCCCCCCOC=C ASPUDHDPXIBNAP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- QLCCBKRRTJZZOE-UHFFFAOYSA-N ethenoxycyclobutane Chemical compound C=COC1CCC1 QLCCBKRRTJZZOE-UHFFFAOYSA-N 0.000 description 1
- HJVKTYVDOZVQPA-UHFFFAOYSA-N ethenoxycyclopentane Chemical compound C=COC1CCCC1 HJVKTYVDOZVQPA-UHFFFAOYSA-N 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- JZRGFKQYQJKGAK-UHFFFAOYSA-N ethenyl cyclohexanecarboxylate Chemical compound C=COC(=O)C1CCCCC1 JZRGFKQYQJKGAK-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- 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
- C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic 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
- 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
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- C—CHEMISTRY; METALLURGY
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Abstract
本申请涉及由四氟丙烯形成的可固化含氟共聚物。本发明涉及部分氟化的共聚物及其制备。更具体地,该共聚物优选通过溶液聚合方法产生,优选具有至少三个单元,第一单元选自2,3,3,3‑四氟丙烯和1,3,3,3‑四氟丙烯,第二单元具有选自乙烯基酯和乙烯基醚的聚合单体,且第三单元具有衍生自含羟基的乙烯基醚的聚合单体。所得的共聚物是环境友好的,具有良好的分子量特征,并可以高浓度经济地运送。
Description
相关申请的交叉引用
本申请是申请日为2014年9月23日、申请号为201480057598.6、名称为"由四氟丙烯形成的可固化含氟共聚物"的发明专利申请的分案申请。本申请要求2013年10月22日申请的美国临时申请61/894146号的优先权,其内容经此引用并入本文。该'146号临时申请涉及2012年10月4日申请的美国专利申请13/645444号、2012年10月4日申请的美国专利申请13/645437号、2011年10月5日申请的美国临时申请61/543780号以及2011年10月5日申请的美国临时申请61/543714号,它们的内容经此引用全部并入本文。
技术领域
本发明通常涉及至少部分地由四氟丙烯形成的新型可固化共聚物。更具体地,本发明涉及部分地由包含2,3,3,3-四氟丙烯(CF3CF=CH2,“HFO-1234y”)和/或1,3,3,3-四氟丙烯(CH2=CFCF3,“HFO-1234ze”)的单体材料形成的可固化共聚物和其组合物及用途。
背景技术
含氟聚合物如聚四氟乙烯(PTFE)、聚氯三氟乙烯(PCTFE)和聚偏二氟乙烯(PVDF)公知具有优异的耐热、耐化学和耐候性,以及诸如耐水和耐油性的有利特性。遗憾的是,这样的含氟聚合物在涂料中使用是困难的,因为它们在通常用于涂料工业中的工业溶剂中的溶解性较差,所述溶剂例如二甲苯和乙酸丁酯。相应地,必须经常使用更多的外加溶剂,这不仅影响涂料的经济性而且也可能存在环境问题,例如,由于外加溶剂潜在的毒性。
因此,有必要配制具有优异性能特性、可使用经济的工业溶剂并且环境友好的替代涂料。
此外,含氟聚合物的聚合提出了一些挑战,例如在先申请13/645437号(现在是美国专利公开2013/0090439A1号)中详述的,其通过引用的方式并入本文。虽然制造四氟丙烯共聚物的几种类型的聚合方法已经在在先申请13/645,437号中有描述。申请人已进一步意识到这些聚合方法有不合意的方面或限制,和/或由此产生的聚合物可形成为具有不同的和/或改进的特性。
因此,申请人已意识到需要开发制造四氟丙烯共聚物的改进方法,该四氟丙烯共聚物具有不同的和/或改进的适用于各种应用的特性。
发明内容
根据本发明的第一方面,可通过由(a)、(b)和(c)表示的单体的溶液共聚来形成可固化含氟共聚物:
(a)40-60mol%的四氟丙烯;
(b)5-45%的乙烯基醚或乙烯基酯或它们两者,它们分别由以下化学式表示:
CH2=CR1-O(C=O)xR2和CH2=CR3-OR4,
其中R1和R3是氢或甲基,且其中R2和R4是具有1-12个碳原子的未取代的直链、支链或脂环族的烷基;以及
(c)3-30mol%的羟烷基乙烯基醚,由化学式CH2=C-R5-OR6表示,其中R5是氢或甲基,且R6是具有羟基的未取代的直链、支链或脂环族的烷基。
根据本发明的第二方面,所述四氟丙烯选自HFO-1234yf或HFO-1234ze或这两者。根据本发明,申请人已经发现环境友好的HFO-1234yf和HFO-1234ze可有利地各自和组合地用作用于聚合涂料生产的氟化单体。
根据本发明的第三方面,含可固化含氟共聚物的产物具有15-50%、且优选为15-25%的溶剂含量,以便提供浓缩产物,其可经济地运送给产品使用者。
具体实施方式
根据本发明的优选实施方式,40-60mol%的HFO-1234yf和/或HFO-1234ze形式的四氟丙烯用作组分(a),且最优选45-55 mol%。如果使用HFO-1234yf和HFO-1234ze的混合物,那么所使用的HFO-1234yf和HFO-1234ze的混合比例可以是任何比例,但优选为0.3-0.7:0.7-0.3。
根据本发明的共聚物可包含乙烯基醚单元、乙烯基醚单元或它们的组合作为组分(b)。优选地,使用5-45mol%,且最优选使用25-45 mol%。乙烯基醚的实例包括烷基乙烯基醚,例如甲基乙烯基醚、乙基、丙基乙烯基醚、正丁基乙烯基醚、异丁基乙烯基醚、己基乙烯基醚、辛基乙烯基醚、癸基乙烯基醚和十二烷基乙烯基醚。还可使用包括脂环族基团的乙烯基醚,例如环丁基乙烯基醚、环戊基乙烯基醚和环己基乙烯基醚。乙烯基酯的实例包括乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、新戊酸乙烯酯、己酸乙烯基、月桂酸乙烯酯,VEOVA-9(由Momentive生产的C9碳环酸形成的叔碳酸乙烯酯),VEOVA-10(由Momentive生产的C10碳环酸形成的叔碳酸乙烯酯)和环己烷甲酸乙烯酯。
组分(c)的羟烷基乙烯基醚的实例包括羟乙基乙烯基醚、羟丙基乙烯基醚、羟丁基乙烯基醚、羟戊基乙烯基醚和羟己基乙烯基醚。优选使用3-30mol%,且最优选使用5-20mol%。
所述含氟共聚物优选在溶液聚合体系中产生。用于溶液聚合的溶剂的实例包括:酯类,例如乙酸甲酯、乙酸乙酯、乙酸丙酯和乙酸丁酯;酮类,例如丙酮、甲基乙基酮和环己酮;脂族烃,例如己烷、环己烷、辛烷、壬烷、癸烷、十一烷、十二烷和矿物油精;芳族烃,例如苯、甲苯、二甲苯、萘和溶剂石脑油;醇类,例如甲醇、乙醇、叔丁醇、异丙醇、乙二醇单烷基醚;环醚,例如四氢呋喃、四氢吡喃和二噁烷;氟化溶剂,例如HCFC-225和HCFC141b;二甲基亚砜;和它们的混合物。
优选地,取决于聚合引发源和聚合介质的类型,聚合在-30℃至150℃的范围内进行。
本发明的共聚物优选通过使这些单体共聚制备,并具有5000-50000的数均分子量,且更优选为5000-10000。优选地,所述共聚物的分子量分布为2-10,更优选为2.5-8,且最优选为3-6。当数均分子量小于5000时,该共聚物的耐候性和耐化学性差,而当超过50000时,高粘度可导致操作困难。
本发明的共聚物具有羟基,并可用固化剂固化,固化剂例如蜜胺树脂固化剂、脲醛树脂固化剂、多元酸固化剂和用于常规热固性丙烯酸树脂涂料的未封端的多异氰酸酯固化剂或封端的多异氰酸酯固化剂。蜜胺树脂固化剂的实例包括丁基化蜜胺树脂、甲基化蜜胺树脂、环氧蜜胺树脂等。未封端的多异氰酸酯的实例包括2,4-和2,6-甲苯二异氰酸酯(TDI)、二苯基甲烷-2,4'-和/或-4,4'-二异氰酸酯(MDI)、1,6-六亚甲基二异氰酸酯(HDI)、1-异氰酸基-3,3,5-三甲基-5-异氰酸基甲基环己胺(IPDI)、二环己基甲烷二异氰酸酯(H12MDI)、1,4-二异氰酸丁酯,2-甲基-1,5-二异氰酸戊酯、1,5-二异氰酸基-2,2-二甲基戊烷、2,2,4-或2,4,4-三甲基-1,6-二异氰酸己酯、1,10-二异氰酸癸酯、1,3-和1,4-二异氰酸根络环己烷、1,3-和1,4-二-(异氰酸基甲基)-环己烷、4,4'-二异氰酸基二环己基甲烷、1-异氰酸基-1-甲基-4(3)-异氰酸基-甲基环己烷(IMCI)、二-(异氰酸基甲基)-降冰片烷、1,3-和1,4-二-(2-异氰酸基丙-2-基)-苯(TMXDI)、1,5-萘二异氰酸酯、2,4'-,4,4'-二异氰酸基二苯基甲烷以及它们的二聚体、三聚体和它们的聚合物。对于封端的多异氰酸酯,用于封端多异氰酸酯的优选的封端基团包括金属亚硫酸氢盐、丙二酸二乙酯(DEM)3,5-二甲基吡唑(DMP)、甲基乙基酮肟(MEKO)、e-己内酰胺(e-CAP)、二异丙胺、二甲基吡唑、甲基乙基酮肟(丁酮肟)、丙二酸二乙酯、仲胺和***及吡唑衍生物。当在常温下通过使用多异氰酸酯进行固化时,可以通过加入常规催化剂如二月桂酸二丁基锡来加速固化。
各种溶剂可用于具有本发明共聚物的溶液型油漆或涂料的制备。优选的溶剂包括芳族烃类,例如二甲苯和甲苯;醇类,例如正丁醇;酯类,例如乙酸丁酯;酮类,例如甲基异丁基酮,以及二醇醚类,例如乙二醇***(ethyl cellusolve)和各种市售稀释剂。当本发明的共聚物用于制造涂料用热固性组合物时,固化剂如蜜胺型固化剂、脲醛型固化剂、多元酸型固化剂、多异氰酸酯型固化剂等在上述混合步骤中同时混合以产生单组分型(one-packtype)涂料。
另一方面,当该组合物是使用多异氰酸酯的常温固化型涂料时,单独制备固化剂组分以提供双组分型涂料。在这种情况下,该涂料可在室温下固化几个小时到几天,并通过控制异氰酸酯和催化剂的类型及它们的添加量,共聚物的浓度,共聚物中羟烷基乙烯基醚的含量等而具有良好的特性。
当本发明的共聚物用作用于油漆或涂料的树脂时,可以在温和条件下形成具有优异的成品硬度和光泽度、柔韧性、耐化学性、耐沾污性和耐候性的膜。这种膜不仅可作为用于预涂覆镀锌钢板、着色铝板和铝框的涂料,也可作为可现场上漆的非热干性油漆。该油漆或涂料可用于众多基材,包括:金属基材;无机基材,例如玻璃、水泥和混凝土;有机基材,例如塑料(例如聚乙烯、聚丙烯、乙烯-乙酸乙烯酯共聚物、尼龙、丙烯酸聚酯乙烯-聚乙烯醇共聚物、氯乙烯、偏二氯乙烯)和木质材料。所述油漆或涂料的具体应用包括,但不限于,铝质游泳池的涂层、用于室外使用的彩色玻璃的涂层、以及用于屋面的水泥瓦的涂层。
本发明通过以下的非限制性实施例作进一步的说明。
实施例1
在配备搅拌器的300ml不锈钢高压釜中装入19.0g乙酸丁酯、9.5g乙基乙烯基醚、20.8g VEOVA-9、8.0g羟丁基乙烯基醚和0.62g过氧化新戊酸叔丁酯。混合物用液氮固化,并脱气以除去溶解的空气。然后,将50g 1,3,3,3-四氟丙烯加入到混合物中,并将该混合物在高压釜中逐渐加热至65℃。将混合物搅拌18小时。将高压釜冷却至室温后,清除未反应的单体并打开高压釜。通过蒸发除去过量的溶剂。
收率92%;最终共聚物的Tg(玻璃化转变温度)=15℃;Mn=7348;Mw=13789;Mw/Mn=1.87;最终聚合物浓度=74.7%;粘度< 500cps。
实施例2
在配备搅拌器的300ml不锈钢高压釜中装入20.0g乙酸丁酯、9.1g乙基乙烯基醚、6.0g乙酸乙烯酯、6.7g羟丁基乙烯基醚和0.4g过氧化新戊酸叔丁酯。混合物用液氮固化,并脱气以除去溶解的空气。然后,将40g 2,3,3,3-四氟丙烯加入到混合物中,并将该混合物在高压釜中逐渐加热至65℃。将混合物搅拌18小时。将高压釜冷却至室温后,清除未反应的单体并打开高压釜。通过蒸发除去过量的溶剂。
收率91%;最终共聚物的Tg = 11℃;Mn=5314;Mw=12646;Mw/Mn= 2.38;最终聚合物浓度=73.8%;粘度< 600cps。
实施例3
在配备搅拌器的300ml不锈钢高压釜中装入20.0g乙酸丁酯、8.0g乙基乙烯基醚、17.4g VEOVA-9、6.7g羟丁基乙烯基醚和0.63g过氧化新戊酸叔丁酯。混合物用液氮固化,并脱气以除去溶解的空气。然后,将60g 1,3,3,3-四氟丙烯加入到混合物中,并将该混合物在高压釜中逐渐加热至65℃。将混合物搅拌18小时。将高压釜冷却至室温后,清除未反应的单体并打开高压釜。通过蒸发除去过量的溶剂。
收率93%;最终共聚物的Tg = 32℃; Mn =7136;Mw=24103; Mw/Mn=3.37;最终聚合物浓度=81.1%,粘度<700cps。
实施例4
在配备搅拌器的300ml不锈钢高压釜中装入20.0g乙酸丁酯、8.2g乙基乙烯基醚、22.3g VEOVA-9、3.4g羟丁基乙烯基醚和0.66g过氧化新戊酸叔丁酯。混合物用液氮固化,并脱气以除去溶解的空气。然后,将50g 1,3,3,3-四氟丙烯加入到混合物中,并将该混合物在高压釜中逐渐加热至65℃。将混合物搅拌18小时。将高压釜冷却至室温后,清除未反应的单体并打开高压釜。通过蒸发除去过量的溶剂。
收率85%;最终共聚物的Tg=12℃;Mn=4640;Mw=8079;Mw/Mn=1.74;最终聚合物浓度=78.1%;粘度< 600cps。
实施例5
在配备搅拌器的300ml不锈钢高压釜中装入30.0g乙酸丁酯、7.6g乙基乙烯基醚、18.4g VeoVa-9,6.7g羟丁基乙烯基醚和0.60g过氧化新戊酸叔丁酯。混合物用液氮固化,并脱气以除去溶解的空气。然后,将60g 1,3,3,3-四氟丙烯加入到混合物中,并将该混合物在高压釜中逐渐加热至65℃。将混合物搅拌18小时。将高压釜冷却至室温后,清除未反应的单体并打开高压釜。通过蒸发除去过量的溶剂。
收率82%;最终共聚物的Tg=22℃;Mn=7640;Mw=17620;Mw/Mn=2.31;最终聚合物浓度=71.7%;粘度< 600cps。
应用实施例
将26.1g所得的共聚物溶于17.9g乙酸丁酯中,然后与22.3g氧化钛混合。将混合物用油漆搅拌器混合1小时,随后与14.8g DESMODUR BL4265和0.3g二月桂酸二丁基锡(1%浓度)混合。然后将该混合物用于涂覆铝基材。约72小时后,测试表面的物理性能。
表面光泽度(ISO 2813)=70(20℃);硬度(铅笔测试;ASTM D3363)= 3H;弹性(ASTMD4145)=3T;附着力(ASTM D3359)=5B。
从上文所述可理解的是,虽然为了说明的目的本文已经描述了具体的实施例,但可做出各种变型而不脱离本公开的精髓或范围。因此,可认为前文的详细描述是说明性的而非限制性的,并且应理解的是后续的权利要求,包括所有的等同物,意图用于特别指出并清楚地要求所要求保护的主题。
本申请可以包括以下技术方案。
1. 一种共聚物组合物,其包含:
(a)包含选自2,3,3,3-四氟丙烯和1,3,3,3-四氟丙烯的聚合单体的第一单元;
(b)包含选自乙烯基酯和乙烯基醚的聚合单体的第二单元;和
(c)包含包括含羟基乙烯基醚的聚合单体的第三单元。
2. 根据方案1所述的共聚物组合物,其中所述共聚物组合物包含40-60mol%的所述第一单元。
3. 根据方案2所述的共聚物组合物,其中所述共聚物组合物包含5-45mol%的所述第二单元,其中所述第二单元选自烷基乙烯基醚、乙烯基酯、以及它们的混合物。
4. 根据方案3所述的共聚物组合物,其中所述共聚物组合物包含3-30mol%的所述第三单元,其中所述第二单元由羟烷基乙烯基醚组成。
5. 方案1所述的共聚物的制备方法,其中使单体在溶液中聚合来产生方案1的共聚物。
6. 根据方案5所述的方法,其中所述共聚物具有5000-50000的数均分子量。
7. 根据方案6所述的方法,其中所述共聚物具有5000-10000的数均分子量。
8. 一种组合物,其包含至少70 wt%的方案1的共聚物。
9. 根据方案7所述的组合物,其中所述组合物包含至少80wt%的所述共聚物。
10. 根据方案7所述的组合物,其中所述组合物包含15-25wt%的溶剂。
Claims (12)
1.一种共聚物,其包含:
(a)包含1,3,3,3-四氟丙烯的聚合单体的第一单元;
(b)包含选自乙烯基酯和乙烯基醚的聚合单体的第二单元;其中所述乙烯基酯和乙烯基醚分别是乙酸乙烯酯和乙基乙烯基醚;和
(c)包含包括羟丁基乙烯基醚的聚合单体的第三单元;
其中所述共聚物的分子量分布(Mw/Mn)为2-10;其中所述共聚物包含40-60mol%的所述第一单元,5-45mol%的所述第二单元,和3-30mol%的所述第三单元。
2.根据权利要求1所述的共聚物,其中所述共聚物包含45-55mol%的所述第一单元。
3.根据权利要求2所述的共聚物,其中所述共聚物包含25-45mol%的所述第二单元。
4.根据权利要求3所述的共聚物,其中所述共聚物包含5-20mol%的所述第三单元。
5.权利要求1所述的共聚物的制备方法,其中使单体在溶液中聚合来产生权利要求1的共聚物。
6.根据权利要求5所述的方法,其中所述共聚物具有5000-50000的数均分子量。
7.根据权利要求6所述的方法,其中所述共聚物具有5000-10000的数均分子量。
8.一种组合物,其包含至少70wt%的权利要求1的共聚物。
9.根据权利要求8所述的组合物,其中所述组合物包含至少80wt%的所述共聚物。
10.根据权利要求8所述的组合物,其中所述组合物包含15-25wt%的溶剂。
11.提供具有优异的成品硬度和光泽度、柔韧性和耐候性的膜的方法,所述方法包括将包含权利要求1的共聚物的油漆或涂料施用于表面以形成所述膜。
12.根据权利要求1所述的共聚物用于提供具有优异的成品硬度和光泽度、柔韧性和耐候性的膜的用途。
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2014
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- 2014-09-23 CN CN202210354209.2A patent/CN114539462B/zh active Active
- 2014-09-23 WO PCT/US2014/056879 patent/WO2015060970A1/en active Application Filing
- 2014-09-23 JP JP2016526062A patent/JP6702864B2/ja active Active
- 2014-09-23 ES ES14856646T patent/ES2787602T3/es active Active
- 2014-09-23 CA CA2927196A patent/CA2927196C/en active Active
- 2014-09-23 EP EP14856646.6A patent/EP3060590B1/en active Active
- 2014-09-23 MX MX2016005089A patent/MX2016005089A/es unknown
- 2014-09-23 BR BR112016009048-9A patent/BR112016009048B1/pt active IP Right Grant
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2018
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2020
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CA2927196C (en) | 2021-11-09 |
US20190382513A1 (en) | 2019-12-19 |
JP6992102B2 (ja) | 2022-02-15 |
JP2016539214A (ja) | 2016-12-15 |
JP2020100829A (ja) | 2020-07-02 |
BR112016009048A2 (pt) | 2017-08-01 |
CA2927196A1 (en) | 2015-04-30 |
EP3060590A4 (en) | 2017-05-17 |
US11453731B2 (en) | 2022-09-27 |
EP3060590B1 (en) | 2020-03-04 |
BR112016009048B1 (pt) | 2021-12-28 |
CN114539462A (zh) | 2022-05-27 |
JP6702864B2 (ja) | 2020-06-03 |
EP3060590A1 (en) | 2016-08-31 |
US20210087308A1 (en) | 2021-03-25 |
MX2016005089A (es) | 2016-07-19 |
ES2787602T3 (es) | 2020-10-16 |
WO2015060970A1 (en) | 2015-04-30 |
CN105829367A (zh) | 2016-08-03 |
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