KR100957656B1 - 색지수가 낮은 폴리테트라히드로푸란의 제조 방법 - Google Patents
색지수가 낮은 폴리테트라히드로푸란의 제조 방법 Download PDFInfo
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- KR100957656B1 KR100957656B1 KR1020047018946A KR20047018946A KR100957656B1 KR 100957656 B1 KR100957656 B1 KR 100957656B1 KR 1020047018946 A KR1020047018946 A KR 1020047018946A KR 20047018946 A KR20047018946 A KR 20047018946A KR 100957656 B1 KR100957656 B1 KR 100957656B1
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- South Korea
- Prior art keywords
- ppm
- less
- tetrahydrofuran
- catalyst
- thf
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 214
- 239000003054 catalyst Substances 0.000 claims abstract description 72
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 54
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 35
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 32
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 18
- 238000004821 distillation Methods 0.000 claims abstract description 16
- 150000005690 diesters Chemical class 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 16
- 230000003797 telogen phase Effects 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000391 magnesium silicate Substances 0.000 claims description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 2
- 235000019792 magnesium silicate Nutrition 0.000 claims description 2
- 239000008262 pumice Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 239000012535 impurity Substances 0.000 description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 24
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 22
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 21
- 229910052763 palladium Inorganic materials 0.000 description 12
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-Dihydrofuran Natural products C1OCC=C1 ARGCQEVBJHPOGB-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- -1 polyoxybutylene Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000002051 biphasic effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000012432 intermediate storage Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001550224 Apha Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002761 deinking Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Substances CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- PNPIRSNMYIHTPS-UHFFFAOYSA-N nitroso nitrate Chemical class [O-][N+](=O)ON=O PNPIRSNMYIHTPS-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/20—Tetrahydrofuran
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
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- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
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Abstract
Description
다양한 조건 하에서의 촉매 A를 사용한 THF의 수소화 | |||||||
MAC | n-BA | i-BA | 2,3-DHF | 2,5-DHF | THF-HP | 기타 | |
30 ℃, 10 bar, 체류 시간 15 분 | 11 ppm | 4 ppm | 1 ppm 미만 | 4 ppm | 5 ppm | 1 ppm 미만 | 41 ppm |
50 ℃, 10 bar, 체류 시간 15 분 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 55 ppm |
70 ℃, 10 bar, 체류 시간 15 분 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 71 ppm |
100 ℃, 10 bar, 체류 시간 15 분 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 366 ppm |
70 ℃, 100 bar, 체류 시간 15 분 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 47 ppm |
70 ℃, 10 bar, 체류 시간 45 분 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 734 ppm |
70 ℃, 10 bar, 체류 시간 15 분 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 79 ppm |
70 ℃, 10 bar, 체류 시간 5 분 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 41 ppm |
메타크롤레인= MAC n-부티르알데히드= n-BA 이소부티르알데히드= i-BA 2,3-디히드로푸란= 2,3-DHF 2,5-디히드로푸란= 2,5-DHF THF 히드로퍼옥시드= THF-HP |
다양한 촉매를 사용한 THF의 수소화 수소화 조건: 온도: 60 ℃, 압력: 10 bar, 체류 시간: 15 분 | |||||||
MAC | n-BA | i-BA | 2,3-DHF | 2,5-DHF | THF-HP | 기타 | |
촉매 A | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 62 ppm |
촉매 B | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 81 ppm |
촉매 C | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 62 ppm |
촉매 D | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 54 ppm |
촉매 E | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 61 ppm |
촉매 F | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 1 ppm 미만 | 44 ppm |
메타크롤레인= MAC n-부티르알데히드= n-BA 이소부티르알데히드= i-BA 2,3-디히드로푸란= 2,3-DHF 2,5-디히드로푸란= 2,5-DHF THF 히드로퍼옥시드= THF-HP |
촉매 A를 사용한 다양한 등급의 THF의 수소화 수소화 조건: 온도: 60 ℃, 압력: 10 bar, 체류 시간: 15 분 | ||||||||||||||
MAC | n-BA | i-BA | 2,3-DHF | 2,5-DHF | THF-HP | 기타 | ||||||||
전 | 후 | 전 | 후 | 전 | 후 | 전 | 후 | 전 | 후 | 전 | 후 | 전 | 후 | |
THF 1 | 25 | 1 미만 | 11 | 1 미만 | 8 | 1 미만 | 12 | 1 미만 | 6 | 1 미만 | 3 | 1 미만 | 21 | 62 |
THF 2 | 33 | 1 미만 | 12 | 1 미만 | 15 | 1 미만 | 5 | 1 미만 | 4 | 1 미만 | 1 | 1 미만 | 54 | 104 |
THF 3 | 9 | 1 미만 | 7 | 1 미만 | 9 | 1 미만 | 5 | 1 미만 | 4 | 1 미만 | 5 | 1 미만 | 32 | 95 |
메타크롤레인= MAC n-부티르알데히드= n-BA 이소부티르알데히드= i-BA 2,3-디히드로푸란= 2,3-DHF 2,5-디히드로푸란= 2,5-DHF THF 히드로퍼옥시드= THF-HP |
고순도 THF를 사용한 PTHF의 제조 | ||||||
THF | 비교예 1 | 실시예 1 | 비교예 2 | 실시예 2 | 비교예 3 | 실시예 3 |
MAC | 25 | 1 미만 | 33 | 1 미만 | 9 | 1 미만 |
n-BA | 11 | 1 미만 | 12 | 1 미만 | 7 | 1 미만 |
i-BA | 8 | 1 미만 | 15 | 1 미만 | 9 | 1 미만 |
2,3-DHF | 12 | 1 미만 | 5 | 1 미만 | 5 | 1 미만 |
2,5-DHF | 6 | 1 미만 | 4 | 1 미만 | 4 | 1 미만 |
THFP-HP | 3 | 1 미만 | 1 | 1 미만 | 5 | 1 미만 |
기타 [ppm] | 21 | 62 | 54 | 104 | 32 | 95 |
PTHF의 색지수 [Apha] | 28 | 6 | 44 | 4 | 25 | 4 |
메타크롤레인= MAC n-부티르알데히드= n-BA 이소부티르알데히드= i-BA 2,3-디히드로푸란= 2,3-DHF 2,5-디히드로푸란= 2,5-DHF THF 히드로퍼옥시드= THF-HP |
Claims (7)
- 공지된 방식으로 제조된 조 테트라히드로푸란을 증류에 의해 순수한 테트라히드로푸란으로 변환시키고, 후속적으로 순수한 테트라히드로푸란을 산화알루미늄, 산화규소, 부석, 벤토나이트, 규산마그네슘 및 이들의 혼합물 중에서 선택되는 지지체 상의 원소 주기율표의 7족 내지 10족의 전이 금속 또는 이들의 산화물을 포함하는 촉매 상에서 본질적으로 완전히 수소화시키고, 이러한 방식으로 얻어진 고순도 테트라히드로푸란을 그의 제조 직후에 중합에 사용하는 것을 포함하는, 촉매의 존재 하 색지수가 낮은 폴리테트라히드로푸란, 테트라히드로푸란 공중합체, 이들의 모노에스테르 또는 디에스테르, 및 폴리테트라히드로푸란의 모노에스테르 또는 디에스테르의 제조 방법.
- 제1항에 있어서, 수소화를 20 내지 300 ℃, 및 1 내지 300 bar의 압력에서 실시하는 방법.
- 제1항에 있어서, 수소화를 20 내지 200 ℃, 및 1 내지 100 bar의 압력에서 실시하는 방법.
- 제1항에 있어서, 수소화를 50 내지 100 ℃, 및 1 내지 20 bar의 압력에서 실시하는 방법.
- 제1항 내지 제4항 중 어느 한 항에 있어서, 중합이 아세트산 무수물에 의해 실시되고, 순수한 테트라히드로푸란 및 아세트산 무수물 모두가 중합 이전에 함께 또는 따로 수소화되는 방법.
- 제1항 내지 제4항 중 어느 한 항에 있어서, 중합이 1종 이상의 텔로겐, 또는 1종 이상의 공단량체, 또는 1종 이상의 텔로겐과 1종 이상의 공단량체의 존재 하에 실시되는 방법.
- 제1항 내지 제4항 중 어느 한 항에 있어서, 중합 후에 분리 제거되어 재순환된 테트라히드로푸란을 새로운 순수한 테트라히드로푸란과 혼합하고 수소화하여 중합에 재사용하는 방법.
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DE10223067A DE10223067A1 (de) | 2002-05-24 | 2002-05-24 | Verfahren zur Herstellung von Polytetrahydrofuran mit niedrigen Farbzahlen |
DE10223067.6 | 2002-05-24 | ||
PCT/EP2003/005234 WO2003099905A1 (de) | 2002-05-24 | 2003-05-19 | Verfahren zur herstellung von polytetrahydrofuran mit niedrigen farbzahlen |
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JP2011162780A (ja) * | 2010-01-15 | 2011-08-25 | Mitsubishi Chemicals Corp | ポリエーテルポリオールの製造方法 |
JP2012172048A (ja) * | 2011-02-21 | 2012-09-10 | Mitsubishi Chemicals Corp | ポリアルキレンエーテルグリコールの製造方法 |
CN102923387A (zh) * | 2011-08-10 | 2013-02-13 | 因温斯特技术公司 | 用于聚醚多元醇产品的颜色管理 |
Citations (2)
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JPS5728076A (en) | 1980-06-11 | 1982-02-15 | Du Pont | Purification of tetrahydrofuran |
US6201137B1 (en) * | 1997-09-30 | 2001-03-13 | Hodogaya Chemical Co., Ltd. | Process for purifying tetrahydrofurans used as starting material for polyether polyols |
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DE2801792A1 (de) | 1978-01-17 | 1979-07-19 | Basf Ag | Verfahren zur polymerisation von tetrahydrofuran |
JPH0629280B2 (ja) | 1985-02-28 | 1994-04-20 | 三菱化成株式会社 | 粗テトラヒドロフランの精製方法 |
FR2650731B1 (fr) * | 1989-08-09 | 1991-10-04 | Inst Fs Rech Expl Mer | Dispositif hydrodynamique d'ouverture de chalut |
DE4339138A1 (de) * | 1993-11-16 | 1995-05-18 | Basf Ag | Trägerkatalysatoren |
EP0813906A3 (de) | 1996-06-19 | 1998-11-18 | Basf Aktiengesellschaft | Verfahren zur Umsetzung einer organischen Verbindung in Gegenwart eines geträgerten Rutheniumkatalysators |
DE19643126A1 (de) | 1996-10-18 | 1998-04-23 | Basf Ag | Metall-Festbettkatalysator nach Raney, Verfahren zu seiner Herstellung sowie ein Verfahren zur Hydrierung von Polymeren unter Verwendung dieses Katalysators |
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JPS5728076A (en) | 1980-06-11 | 1982-02-15 | Du Pont | Purification of tetrahydrofuran |
US6201137B1 (en) * | 1997-09-30 | 2001-03-13 | Hodogaya Chemical Co., Ltd. | Process for purifying tetrahydrofurans used as starting material for polyether polyols |
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JP2005533769A (ja) | 2005-11-10 |
DE10223067A1 (de) | 2003-12-11 |
CN1656146A (zh) | 2005-08-17 |
WO2003099905A1 (de) | 2003-12-04 |
TWI268943B (en) | 2006-12-21 |
AU2003233338A1 (en) | 2003-12-12 |
ATE304568T1 (de) | 2005-09-15 |
CN1276001C (zh) | 2006-09-20 |
EP1511788A1 (de) | 2005-03-09 |
KR20050014830A (ko) | 2005-02-07 |
US7148318B2 (en) | 2006-12-12 |
US20050182238A1 (en) | 2005-08-18 |
DE50301204D1 (de) | 2005-10-20 |
EP1511788B1 (de) | 2005-09-14 |
MY133538A (en) | 2007-11-30 |
TW200306995A (en) | 2003-12-01 |
ES2248750T3 (es) | 2006-03-16 |
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