TW202340125A - Method for manufacturing fluorine-containing cyclic olefin composition and fluorine-containing cyclic olefin composition - Google Patents
Method for manufacturing fluorine-containing cyclic olefin composition and fluorine-containing cyclic olefin composition Download PDFInfo
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- TW202340125A TW202340125A TW112108263A TW112108263A TW202340125A TW 202340125 A TW202340125 A TW 202340125A TW 112108263 A TW112108263 A TW 112108263A TW 112108263 A TW112108263 A TW 112108263A TW 202340125 A TW202340125 A TW 202340125A
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- Taiwan
- Prior art keywords
- fluorine
- cyclic olefin
- compound
- containing cyclic
- mass
- Prior art date
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- -1 cyclic olefin Chemical class 0.000 title claims abstract description 373
- 239000011737 fluorine Substances 0.000 title claims abstract description 274
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 274
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 259
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 191
- 239000000203 mixture Substances 0.000 title claims abstract description 140
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 33
- 239000003377 acid catalyst Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 125000005233 alkylalcohol group Chemical group 0.000 claims abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 58
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- 125000003545 alkoxy group Chemical group 0.000 claims description 26
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 22
- 238000004821 distillation Methods 0.000 claims description 20
- 238000009835 boiling Methods 0.000 claims description 19
- 238000004770 highest occupied molecular orbital Methods 0.000 claims description 18
- 239000011973 solid acid Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 28
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 18
- 150000001336 alkenes Chemical class 0.000 description 16
- 125000001153 fluoro group Chemical group F* 0.000 description 13
- 239000000126 substance Substances 0.000 description 9
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 238000005698 Diels-Alder reaction Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000003729 cation exchange resin Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- FKTXDTWDCPTPHK-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical group FC(F)(F)[C](F)C(F)(F)F FKTXDTWDCPTPHK-UHFFFAOYSA-N 0.000 description 2
- FIARMZDBEGVMLV-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanolate Chemical group [O-]C(F)(F)C(F)(F)F FIARMZDBEGVMLV-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 2
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000004785 fluoromethoxy group Chemical group [H]C([H])(F)O* 0.000 description 2
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 2
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000005815 pentoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000005460 perfluorocycloalkyl group Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000003652 trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 description 2
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- GWYPDXLJACEENP-UHFFFAOYSA-N 1,3-cycloheptadiene Chemical compound C1CC=CC=CC1 GWYPDXLJACEENP-UHFFFAOYSA-N 0.000 description 1
- 239000005968 1-Decanol Substances 0.000 description 1
- WZMQOSYJAAMGTB-UHFFFAOYSA-N 1-ethylcyclohexa-1,3-diene Chemical compound CCC1=CC=CCC1 WZMQOSYJAAMGTB-UHFFFAOYSA-N 0.000 description 1
- RNVJDIGFTGLKCE-UHFFFAOYSA-N 2,3,3-trifluoro-2-(trifluoromethyl)bicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(C(F)(F)F)(F)C2(F)F RNVJDIGFTGLKCE-UHFFFAOYSA-N 0.000 description 1
- JQRBOOXBIGHRRP-UHFFFAOYSA-N 2,3-di(propan-2-yl)bicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C(C(C)C)=C(C(C)C)C1C2 JQRBOOXBIGHRRP-UHFFFAOYSA-N 0.000 description 1
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 1
- QQBUHYQVKJQAOB-UHFFFAOYSA-N 2-ethenylfuran Chemical compound C=CC1=CC=CO1 QQBUHYQVKJQAOB-UHFFFAOYSA-N 0.000 description 1
- HLPIHRDZBHXTFJ-UHFFFAOYSA-N 2-ethylfuran Chemical compound CCC1=CC=CO1 HLPIHRDZBHXTFJ-UHFFFAOYSA-N 0.000 description 1
- MENJEMPGPUEASQ-UHFFFAOYSA-N 4-methylbenzenesulfonic acid;propan-1-ol Chemical compound CCCO.CC1=CC=C(S(O)(=O)=O)C=C1 MENJEMPGPUEASQ-UHFFFAOYSA-N 0.000 description 1
- SQMZNUYQLISRTD-UHFFFAOYSA-N 4-propan-2-ylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C(C)C)C2 SQMZNUYQLISRTD-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- RBRGWYHSVYKUQT-UHFFFAOYSA-N 5-oxabicyclo[2.2.1]hept-2-ene Chemical compound C1C2COC1C=C2 RBRGWYHSVYKUQT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- VRNCRGHDRGGBLW-UHFFFAOYSA-N cyclopenta-1,2-diene Chemical compound C1CC=C=C1 VRNCRGHDRGGBLW-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 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
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
- C07C23/18—Polycyclic halogenated hydrocarbons
- C07C23/20—Polycyclic halogenated hydrocarbons with condensed rings none of which is aromatic
- C07C23/27—Polycyclic halogenated hydrocarbons with condensed rings none of which is aromatic with a bicyclo ring system containing seven carbon atoms
- C07C23/30—Mono-unsaturated bicyclo ring system
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本發明是有關於一種含氟環狀烯烴組成物的製造方法及含氟環狀烯烴組成物。The present invention relates to a manufacturing method of a fluorine-containing cyclic olefin composition and a fluorine-containing cyclic olefin composition.
作為含氟環狀烯烴聚合物的原材料的含氟環狀烯烴化合物例如可藉由使含氟烯烴與環狀多烯進行狄耳士-阿德爾（Diels-Alder）反應來製造。 作為與此種含氟環狀烯烴化合物的製造方法相關的技術，例如可列舉專利文獻1中記載的技術。 The fluorine-containing cyclic olefin compound that is a raw material of the fluorine-containing cyclic olefin polymer can be produced, for example, by subjecting a fluorine-containing olefin and a cyclic polyene to a Diels-Alder reaction. As a technology related to the manufacturing method of such a fluorine-containing cyclic olefin compound, the technology described in patent document 1 is mentioned, for example.
專利文獻1中記載了一種含氟環狀烯烴單體的製造方法，所述含氟環狀烯烴單體的製造方法包含步驟（A），所述步驟（A）藉由在反應容器內使含氟烯烴與環狀多烯連續地反應來連續地製造含氟環狀烯烴單體，在所述步驟（A）中，將所述環狀多烯連續地或斷續地供給至所述反應容器內，並且將所述含氟烯烴連續地或斷續地供給至所述反應容器內或預先裝入至所述反應容器內，藉此使所述含氟烯烴與所述環狀多烯連續地反應，且，將所述反應容器內的所述含氟烯烴的含量X 2相對於所述環狀多烯的含量X 1的莫耳比X 2/X 1調整為1.01以上的範圍內。專利文獻1中記載了，藉由所述製造方法，可高選擇性地獲得目標含氟環狀烯烴單體。 [現有技術文獻] [專利文獻] Patent Document 1 describes a method for producing a fluorine-containing cyclic olefin monomer. The method for producing a fluorine-containing cyclic olefin monomer includes a step (A) by allowing a fluorine-containing cyclic olefin monomer to be produced in a reaction vessel. Fluoroolefins and cyclic polyenes are continuously reacted to continuously produce fluorine-containing cyclic olefin monomers, and in the step (A), the cyclic polyenes are continuously or intermittently supplied to the reaction vessel. within, and the fluorine-containing olefin is continuously or intermittently supplied into the reaction vessel or preloaded into the reaction vessel, thereby allowing the fluorine-containing olefin and the cyclic polyene to continuously reaction, and the molar ratio X 2 /X 1 of the fluorine-containing olefin content X 2 to the cyclic polyene content X 1 in the reaction vessel is adjusted to a range of 1.01 or more. Patent Document 1 describes that the target fluorine-containing cyclic olefin monomer can be obtained with high selectivity by the above-mentioned production method. [Prior Art Documents] [Patent Documents]
專利文獻1：日本專利特開2019-89714號公報Patent Document 1: Japanese Patent Application Publication No. 2019-89714
[發明所欲解決之課題] 根據本發明者等人的研究，明確了在使用含氟烯烴及環狀多烯來製造含氟環狀烯烴化合物時，環狀多烯彼此進行狄耳士-阿德爾反應而產生不含氟環狀二烯烴化合物作為副產物。由於不含氟環狀二烯烴化合物富有反應性，因此在使用包含不含氟環狀二烯烴化合物作為副產物的含氟環狀烯烴化合物時，有時會發生不期望的副反應。 另一方面，作為目標物的含氟環狀烯烴化合物與作為副產物的不含氟環狀二烯烴化合物的沸點差有時小，有時難以藉由蒸餾將含氟環狀烯烴化合物與不含氟環狀二烯烴化合物加以分離。 [Problem to be solved by the invention] According to studies conducted by the present inventors, it was clarified that when a fluorine-containing olefin and a cyclic polyene are used to produce a fluorine-containing cyclic olefin compound, the cyclic polyenes undergo a Diels-Alder reaction with each other to produce a fluorine-free ring. diene compounds as by-products. Since the fluorine-containing cyclic diene compound is highly reactive, when a fluorine-containing cyclic olefin compound containing a fluorine-containing cyclic diene compound as a by-product is used, an undesirable side reaction may occur. On the other hand, the boiling point difference between the target fluorine-containing cyclic olefin compound and the fluorine-free cyclic diene compound as a by-product may be small, and it may be difficult to separate the fluorine-containing cyclic olefin compound and the fluorine-free cyclic diene compound by distillation. Fluorine cyclic diene compounds are separated.
本發明是鑒於所述情況而成者，提供一種能夠獲得不含氟環狀二烯烴化合物的含量減少的含氟環狀烯烴組成物的製造方法。 [解決課題之手段] The present invention was made in view of the above-mentioned circumstances, and provides a manufacturing method capable of obtaining a fluorine-containing cyclic olefin composition in which the content of the fluorine-free cyclic diene compound is reduced. [Means to solve the problem]
本發明者等人為了解決所述課題反覆進行了銳意研究。其結果發現，藉由利用含羥基化合物使作為副產物的不含氟環狀二烯烴化合物水合及/或醚化，作為目標物的含氟環狀烯烴化合物與作為副產物的不含氟環狀二烯烴化合物的分離變得容易，能夠獲得作為副產物的不含氟環狀二烯烴化合物的含量減少的含氟環狀烯烴組成物，從而完成了本發明。 根據本發明，提供一種以下所示的含氟環狀烯烴組成物的製造方法及含氟環狀烯烴組成物。 The inventors of the present invention have repeatedly conducted intensive research in order to solve the above-mentioned problems. As a result, it was found that by hydrating and/or etherifying the fluorine-containing cyclic diene compound as a by-product using a hydroxyl-containing compound, the target fluorine-containing cyclic olefin compound and the fluorine-free cyclic diene compound as the by-product The present invention was completed by making it possible to easily separate the diene compound and to obtain a fluorine-containing cyclic olefin composition in which the content of the fluorine-free cyclic diene compound as a by-product is reduced. According to the present invention, there are provided a method for producing a fluorine-containing cyclic olefin composition and a fluorine-containing cyclic olefin composition shown below.
[1] 一種含氟環狀烯烴組成物的製造方法，包含： 混合步驟，對於包含下述式（1）所表示的含氟環狀烯烴化合物（A）及不含氟環狀二烯烴化合物（B1）的組成物（X），混合酸觸媒、與選自由水及烷基醇所組成的群組中的至少一種含羥基化合物（C）；以及 反應步驟，藉由使所述不含氟環狀二烯烴化合物（B1）與所述含羥基化合物（C）進行反應，從而獲得選自由不含氟水合化合物（B2）及不含氟醚化合物（B3）所組成的群組中的至少一種。 [化1] （所述式（1）中，R 1～R 4中的至少一個為氟、含有氟的碳數1～10的烷基、含有氟的碳數1～10的烷氧基、或含有氟的碳數2～10的烷氧基烷基，在R 1～R 4為不含有氟的基的情況下，R 1～R 4選自氫、碳數1～10的烷基、碳數1～10的烷氧基、或碳數2～10的烷氧基烷基中，R 1～R 4可相互鍵結而形成環結構，X表示-CH 2-或O-，n表示0或1） [2] 如所述[1]所述的含氟環狀烯烴組成物的製造方法，其中，所述含氟環狀烯烴化合物（A）的沸點與所述不含氟環狀二烯烴化合物（B1）的沸點之差的絕對值為10℃以下。 [3] 如所述[1]或[2]所述的含氟環狀烯烴組成物的製造方法，其中，所述烷基醇的碳數為3以上且10以下。 [4] 如所述[1]至[3]中任一項所述的含氟環狀烯烴組成物的製造方法，其中，所述酸觸媒包含選自由無機酸、有機酸及固體酸所組成的群組中的至少一種。 [5] 如所述[1]至[4]中任一項所述的含氟環狀烯烴組成物的製造方法，其中，所述含氟環狀烯烴化合物（A）的最高佔有分子軌域（Highest Occupied Molecular Orbital，HOMO）能量（E 1）與所述不含氟環狀二烯烴化合物（B1）的HOMO能量（E 2）之差的絕對值|E 2-E 1|為0.3 eV以上。 [6] 如所述[1]至[5]中任一項所述的含氟環狀烯烴組成物的製造方法，其中，所述含氟環狀烯烴化合物（A）包含在所述式（1）中n為0的含氟環狀烯烴化合物（A1）及在所述式（1）中n為1的含氟環狀烯烴化合物（A2）此兩者。 [7] 如所述[6]所述的含氟環狀烯烴組成物的製造方法，更包含如下分離步驟，即：在所述反應步驟之後，藉由蒸餾將所述含氟環狀烯烴化合物（A1）與所述含氟環狀烯烴化合物（A2）加以分離。 [8] 如所述[1]至[7]中任一項所述的含氟環狀烯烴組成物的製造方法，更包含如下分離步驟，即：在所述反應步驟之後，藉由蒸餾將所述含氟環狀烯烴化合物（A）與選自由所述不含氟水合化合物（B2）及所述不含氟醚化合物（B3）所組成的群組中的至少一種加以分離。 [9] 如所述[1]至[8]中任一項所述的含氟環狀烯烴組成物的製造方法，其中，在將所述含氟環狀烯烴組成物的整體設為100質量%時，所述含氟環狀烯烴組成物中的所述不含氟環狀二烯烴化合物（B1）的含量為5.0質量%以下。 [10] 如所述[8]所述的含氟環狀烯烴組成物的製造方法，其中，在將所述含氟環狀烯烴組成物的整體設為100質量%時，所述含氟環狀烯烴組成物中的在所述式（1）中n為0的含氟環狀烯烴化合物（A1）的含量為99.0質量%以上。 [11] 如所述[8]所述的含氟環狀烯烴組成物的製造方法，其中，在將所述含氟環狀烯烴組成物的整體設為100質量%時，所述含氟環狀烯烴組成物中的在所述式（1）中n為1的含氟環狀烯烴化合物（A2）的含量為99.0質量%以上。 [12] 一種含氟環狀烯烴組成物，包含下述式（1）所表示的含氟環狀烯烴化合物（A）及不含氟環狀二烯烴化合物（B1）， 在將所述含氟環狀烯烴組成物的整體設為100質量%時，所述含氟環狀烯烴組成物中的所述不含氟環狀二烯烴化合物（B1）的含量為超過0質量%且1.0質量%以下。 [化2] （所述式（1）中，R 1～R 4中的至少一個為氟、含有氟的碳數1～10的烷基、含有氟的碳數1～10的烷氧基、或含有氟的碳數2～10的烷氧基烷基，在R 1～R 4為不含有氟的基的情況下，R 1～R 4選自氫、碳數1～10的烷基、碳數1～10的烷氧基、或碳數2～10的烷氧基烷基中，R 1～R 4可相互鍵結而形成環結構，X表示-CH 2-或O-，n表示0或1） [發明的效果] [1] A method for producing a fluorine-containing cyclic olefin composition, comprising: a mixing step, for a fluorine-containing cyclic olefin compound (A) represented by the following formula (1) and a fluorine-free cyclic diene compound ( The composition (X) of B1), a mixed acid catalyst, and at least one hydroxyl-containing compound (C) selected from the group consisting of water and alkyl alcohols; and a reaction step, by making the fluorine-free The cyclic diene compound (B1) reacts with the hydroxyl-containing compound (C) to obtain at least one selected from the group consisting of a fluorine-free hydrated compound (B2) and a fluorine-free ether compound (B3). . [Chemical 1] (In the formula (1), at least one of R 1 to R 4 is fluorine, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkoxy group having 1 to 10 carbon atoms, or a fluorine-containing alkyl group. Alkoxyalkyl group having 2 to 10 carbon atoms, when R 1 to R 4 are groups not containing fluorine, R 1 to R 4 are selected from hydrogen, alkyl groups having 1 to 10 carbon atoms, and alkyl groups having 1 to 10 carbon atoms. In an alkoxy group with 10 or an alkoxyalkyl group with 2 to 10 carbon atoms, R 1 to R 4 may be bonded to each other to form a ring structure, X represents -CH 2 - or O-, and n represents 0 or 1) [2] The method for producing a fluorine-containing cyclic olefin composition as described in [1], wherein the boiling point of the fluorine-containing cyclic olefin compound (A) is the same as the fluorine-containing cyclic diene compound (A) The absolute value of the difference in boiling points of B1) is 10°C or less. [3] The method for producing a fluorine-containing cyclic olefin composition according to [1] or [2], wherein the alkyl alcohol has a carbon number of 3 to 10. [4] The method for producing a fluorine-containing cyclic olefin composition according to any one of [1] to [3], wherein the acid catalyst contains an inorganic acid, an organic acid, and a solid acid. At least one of the groups. [5] The method for producing a fluorine-containing cyclic olefin composition according to any one of [1] to [4], wherein the highest occupied molecular orbital of the fluorine-containing cyclic olefin compound (A) The absolute value |E 2 -E 1 | of the difference between the (Highest Occupied Molecular Orbital, HOMO) energy (E 1 ) and the HOMO energy (E 2 ) of the fluorine-free cyclic diene compound (B1) is 0.3 eV or more . [6] The method for producing a fluorine-containing cyclic olefin composition according to any one of [1] to [5], wherein the fluorine-containing cyclic olefin compound (A) is included in the formula ( 1) Both the fluorine-containing cyclic olefin compound (A1) in which n is 0 and the fluorine-containing cyclic olefin compound (A2) in the formula (1) in which n is 1. [7] The manufacturing method of the fluorine-containing cyclic olefin composition as described in [6], further comprising a separation step, that is, after the reaction step, the fluorine-containing cyclic olefin compound is distilled (A1) is separated from the fluorine-containing cyclic olefin compound (A2). [8] The method for producing a fluorine-containing cyclic olefin composition according to any one of [1] to [7], further comprising a separation step, that is, after the reaction step, distillation The fluorine-containing cyclic olefin compound (A) is separated from at least one selected from the group consisting of the fluorine-free hydrated compound (B2) and the fluorine-free ether compound (B3). [9] The method for producing a fluorine-containing cyclic olefin composition according to any one of [1] to [8], wherein the entire fluorine-containing cyclic olefin composition is 100 mass %, the content of the fluorine-free cyclic diene compound (B1) in the fluorine-containing cyclic olefin composition is 5.0 mass% or less. [10] The method for producing a fluorine-containing cyclic olefin composition according to [8], wherein when the entire fluorine-containing cyclic olefin composition is taken as 100% by mass, the fluorine-containing cyclic olefin composition The content of the fluorine-containing cyclic olefin compound (A1) in which n is 0 in the formula (1) in the olefin composition is 99.0 mass % or more. [11] The method for producing a fluorine-containing cyclic olefin composition according to [8], wherein when the entire fluorine-containing cyclic olefin composition is taken as 100% by mass, the fluorine-containing cyclic olefin composition The content of the fluorine-containing cyclic olefin compound (A2) in which n is 1 in the formula (1) in the olefin composition is 99.0 mass% or more. [12] A fluorine-containing cyclic olefin composition, including a fluorine-containing cyclic olefin compound (A) represented by the following formula (1) and a fluorine-free cyclic diene compound (B1), in which the fluorine-containing cyclic olefin compound (A) is represented by the following formula (1) When the entire cyclic olefin composition is taken as 100 mass %, the content of the fluorine-free cyclic diene compound (B1) in the fluorine-containing cyclic olefin composition is more than 0 mass % and 1.0 mass % or less. . [Chemicalization 2] (In the formula (1), at least one of R 1 to R 4 is fluorine, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkoxy group having 1 to 10 carbon atoms, or a fluorine-containing alkyl group. Alkoxyalkyl group having 2 to 10 carbon atoms, when R 1 to R 4 are groups not containing fluorine, R 1 to R 4 are selected from hydrogen, alkyl groups having 1 to 10 carbon atoms, and alkyl groups having 1 to 10 carbon atoms. In an alkoxy group with 10 or an alkoxyalkyl group with 2 to 10 carbon atoms, R 1 to R 4 may be bonded to each other to form a ring structure, X represents -CH 2 - or O-, and n represents 0 or 1) [Effects of the invention]
藉由本發明，可提供一種能夠獲得不含氟環狀二烯烴化合物的含量減少的含氟環狀烯烴組成物的製造方法。The present invention provides a method for producing a fluorine-containing cyclic olefin composition with a reduced content of fluorine-free cyclic diene compounds.
以下，基於實施方式對本發明進行說明。再者，在本實施方式中，關於表示數值範圍的「A～B」，若無特別說明，則表示A以上且B以下。另外，在階段性地記載數值範圍的情況下，各數值範圍的上限及下限可任意組合。Hereinafter, the present invention will be described based on embodiments. In addition, in the present embodiment, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified. In addition, when a numerical range is described in steps, the upper limit and the lower limit of each numerical range may be combined arbitrarily.
1.含氟環狀烯烴組成物的製造方法 本發明的含氟環狀烯烴組成物的製造方法包含：混合步驟，對於包含下述式（1）所表示的含氟環狀烯烴化合物（A）及不含氟環狀二烯烴化合物（B1）的組成物（X），混合酸觸媒、與選自由水及烷基醇所組成的群組中的至少一種含羥基化合物（C）；以及反應步驟，藉由使所述不含氟環狀二烯烴化合物（B1）與所述含羥基化合物（C）進行反應，從而獲得選自由不含氟水合化合物（B2）及不含氟醚化合物（B3）所組成的群組中的至少一種。 此處，在本說明書中，將不含氟環狀二烯烴化合物（B1）與水的反應產物稱為不含氟水合化合物（B2），將不含氟環狀二烯烴化合物（B1）與烷基醇的反應產物稱為不含氟醚化合物（B3）。即，本發明的含氟環狀烯烴組成物的製造方法在含羥基化合物（C）包含水的情況下，包含藉由使不含氟環狀二烯烴化合物（B1）與含羥基化合物（C）進行反應而獲得不含氟水合化合物（B2）的反應步驟，在含羥基化合物（C）包含烷基醇的情況下，包含藉由使不含氟環狀二烯烴化合物（B1）與含羥基化合物（C）進行反應而獲得不含氟醚化合物（B3）的反應步驟。 1. Method for producing fluorine-containing cyclic olefin composition The method for producing a fluorine-containing cyclic olefin composition of the present invention includes a mixing step of a fluorine-containing cyclic olefin compound (A) represented by the following formula (1) and a fluorine-free cyclic diene compound (B1). The composition (X), mixing an acid catalyst, and at least one hydroxyl-containing compound (C) selected from the group consisting of water and alkyl alcohols; and a reaction step, by making the fluorine-free cyclic The diene compound (B1) reacts with the hydroxyl-containing compound (C) to obtain at least one selected from the group consisting of the fluorine-free hydrated compound (B2) and the fluorine-free ether compound (B3). Here, in this specification, the reaction product of the fluorine-free cyclic diene compound (B1) and water is called the fluorine-free hydrated compound (B2), and the reaction product of the fluorine-free cyclic diene compound (B1) and the alkane is called The reaction product of base alcohol is called fluorine-free ether compound (B3). That is, when the hydroxyl-containing compound (C) contains water, the method for producing the fluorine-containing cyclic olefin composition of the present invention includes: The reaction step of performing the reaction to obtain the fluorine-free hydrated compound (B2), when the hydroxyl-containing compound (C) contains an alkyl alcohol, includes reacting the fluorine-free cyclic diene compound (B1) with the hydroxyl-containing compound (C) A reaction step for obtaining a fluoroether-free compound (B3) by performing a reaction.
[化3] 所述式（1）中，R 1～R 4中的至少一個為氟、含有氟的碳數1～10的烷基、含有氟的碳數1～10的烷氧基、或含有氟的碳數2～10的烷氧基烷基，在R 1～R 4為不含有氟的基的情況下，R 1～R 4選自氫、碳數1～10的烷基、碳數1～10的烷氧基、或碳數2～10的烷氧基烷基中，R 1～R 4可相互鍵結而形成環結構，X表示-CH 2-或O-，n表示0或1。 [Chemical 3] In the formula (1), at least one of R 1 to R 4 is fluorine, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkoxy group having 1 to 10 carbon atoms, or a fluorine-containing carbon group. Alkoxyalkyl group with 2 to 10 carbon atoms, when R 1 to R 4 are groups not containing fluorine, R 1 to R 4 are selected from hydrogen, alkyl groups with 1 to 10 carbon atoms, and alkyl groups with 1 to 10 carbon atoms. In an alkoxy group or an alkoxyalkyl group having 2 to 10 carbon atoms, R 1 to R 4 may be bonded to each other to form a ring structure, X represents -CH 2 - or O-, and n represents 0 or 1.
藉由本發明的含氟環狀烯烴組成物的製造方法，可獲得一種不含氟環狀二烯烴化合物的含量減少的含氟環狀烯烴組成物。 關於獲得此種效果的理由，推測為如以下所述。 在酸觸媒的存在下，使不含氟環狀二烯烴化合物（B1）與含羥基化合物（C）進行反應，藉此在不含氟環狀二烯烴化合物（B1）加成含羥基化合物（C）而生成不含氟水合化合物（B2）或不含氟醚化合物（B3）。藉此，可減少含氟環狀烯烴組成物中的不含氟環狀二烯烴化合物（B1）的含量。 進而，由於不含氟水合化合物（B2）或不含氟醚化合物（B3）與含氟環狀烯烴化合物（A）的沸點差大於不含氟環狀二烯烴化合物（B1）與含氟環狀烯烴化合物（A）的沸點差，因此，不含氟水合化合物（B2）或不含氟醚化合物（B3）容易藉由蒸餾自含氟環狀烯烴組成物中分離。因此，藉由本發明的含氟環狀烯烴組成物的製造方法，由於容易將副產物加以分離，因此能夠獲得純度提高的含氟環狀烯烴組成物。 以下，對各步驟進行說明。 By the method for producing a fluorine-containing cyclic olefin composition of the present invention, a fluorine-containing cyclic olefin composition containing a reduced content of fluorine-free cyclic diene compounds can be obtained. The reason why such an effect is obtained is presumed to be as follows. In the presence of an acid catalyst, the fluorine-free cyclic diene compound (B1) and the hydroxyl-containing compound (C) are reacted, thereby adding the hydroxyl-containing compound (C) to the fluorine-free cyclic diene compound (B1). C) to produce a fluorine-free hydrated compound (B2) or a fluorine-free ether compound (B3). Thereby, the content of the fluorine-free cyclic diene compound (B1) in the fluorine-containing cyclic olefin composition can be reduced. Furthermore, since the boiling point difference between the fluorine-free hydrated compound (B2) or the fluorine-free ether compound (B3) and the fluorine-containing cyclic olefin compound (A) is larger than that between the fluorine-free cyclic diene compound (B1) and the fluorine-containing cyclic olefin compound (A), The olefin compound (A) has a different boiling point, so the fluorine-free hydrated compound (B2) or the fluorine-free ether compound (B3) is easily separated from the fluorine-containing cyclic olefin composition by distillation. Therefore, according to the method for producing a fluorine-containing cyclic olefin composition of the present invention, by-products can be easily separated, and therefore a fluorine-containing cyclic olefin composition with improved purity can be obtained. Each step is explained below.
[混合步驟] 本發明的含氟環狀烯烴組成物的製造方法包含如下混合步驟，即：對於包含所述式（1）所表示的含氟環狀烯烴化合物（A）及不含氟環狀二烯烴化合物（B1）的組成物（X），混合酸觸媒、與選自由水及烷基醇所組成的群組中的至少一種含羥基化合物（C）。 [Mixing step] The method for producing a fluorine-containing cyclic olefin composition of the present invention includes the following mixing step: a fluorine-containing cyclic olefin compound (A) represented by the formula (1) and a fluorine-free cyclic diene compound (A) The composition (X) of B1) is a mixture of an acid catalyst and at least one hydroxyl-containing compound (C) selected from the group consisting of water and alkyl alcohols.
（組成物（X）） 組成物（X）包括含氟環狀烯烴化合物（A）及不含氟環狀二烯烴化合物（B1）。 組成物（X）例如是藉由使含氟烯烴與環狀多烯進行狄耳士-阿德爾反應而獲得的組成物。 (Composition (X)) The composition (X) includes a fluorine-containing cyclic olefin compound (A) and a fluorine-free cyclic diene compound (B1). The composition (X) is, for example, a composition obtained by subjecting a fluorine-containing olefin and a cyclic polyene to Diels-Alder reaction.
[化4] 所述式（1）中，R 1～R 4中的至少一個為氟、含有氟的碳數1～10的烷基、含有氟的碳數1～10的烷氧基、或含有氟的碳數2～10的烷氧基烷基，在R 1～R 4為不含有氟的基的情況下，R 1～R 4選自氫、碳數1～10的烷基、碳數1～10的烷氧基、或碳數2～10的烷氧基烷基中，R 1～R 4可相互鍵結而形成環結構。該些中，R 1～R 4較佳為氟或含有氟的碳數1～4的烷基，更佳為氟或三氟甲基，進而佳為R 1～R 4中的一個為三氟甲基，剩餘部分為氟。 X表示-CH 2-或O-，較佳為-CH 2-。 n表示0或1，較佳為1。 [Chemical 4] In the formula (1), at least one of R 1 to R 4 is fluorine, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkoxy group having 1 to 10 carbon atoms, or a fluorine-containing carbon group. Alkoxyalkyl group with 2 to 10 carbon atoms, when R 1 to R 4 are groups not containing fluorine, R 1 to R 4 are selected from hydrogen, alkyl groups with 1 to 10 carbon atoms, and alkyl groups with 1 to 10 carbon atoms. In an alkoxy group or an alkoxyalkyl group having 2 to 10 carbon atoms, R 1 to R 4 may be bonded to each other to form a ring structure. Among these, R 1 to R 4 are preferably fluorine or a fluorine-containing alkyl group having 1 to 4 carbon atoms, more preferably fluorine or trifluoromethyl, and even more preferably one of R 1 to R 4 is trifluoro Methyl, the remainder is fluorine. X represents -CH 2 - or O-, preferably -CH 2 -. n represents 0 or 1, preferably 1.
在所述式（1）中，作為R 1～R 4，更具體而言，可例示：氟；氟甲基、二氟甲基、三氟甲基、三氟乙基、五氟乙基、七氟丙基、六氟異丙基、七氟異丙基、六氟-2-甲基異丙基、全氟-2-甲基異丙基、正全氟丁基、正全氟戊基、全氟環戊基等烷基的氫的一部分或全部經氟取代的烷基等含有氟的碳數1～10的烷基；氟甲氧基、二氟甲氧基、三氟甲氧基、三氟乙氧基、五氟乙氧基、七氟丙氧基、六氟異丙氧基、七氟異丙氧基、六氟-2-甲基異丙氧基、全氟-2-甲基異丙氧基、全氟正丁氧基、全氟正戊氧基、全氟環戊氧基等烷氧基的氫的一部分或全部經氟取代的烷氧基等含有氟的碳數1～10的烷氧基；氟甲氧基甲基、二氟甲氧基甲基、三氟甲氧基甲基、三氟乙氧基甲基、五氟乙氧基甲基、七氟丙氧基甲基、六氟異丙氧基甲基、七氟異丙氧基甲基、六氟-2-甲基異丙氧基甲基、全氟-2-甲基異丙氧基甲基、全氟正丁氧基甲基、全氟正戊氧基甲基、全氟環戊氧基甲基等烷氧基的氫的一部分或全部經氟取代的烷氧基烷基等含有氟的碳數2～10的烷氧基烷基等。 In the formula (1), as R 1 to R 4 , more specifically, fluorine; fluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, pentafluoroethyl, Heptafluoropropyl, hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro-2-methylisopropyl, perfluoro-2-methylisopropyl, n-perfluorobutyl, n-perfluoropentyl , alkyl groups with 1 to 10 carbon atoms such as perfluorocyclopentyl and other alkyl groups in which part or all of the hydrogens of the hydrogen are substituted by fluorine; fluorine-containing alkyl groups such as fluorine-containing alkyl groups; fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group , trifluoroethoxy, pentafluoroethoxy, heptafluoropropoxy, hexafluoroisopropoxy, heptafluoroisopropoxy, hexafluoro-2-methylisopropoxy, perfluoro-2- The number of carbon atoms in an alkoxy group containing fluorine, such as an alkoxy group such as methyl isopropoxy, perfluoro-n-butoxy, perfluoron-pentyloxy, or perfluorocyclopentoxy, where part or all of the hydrogens are substituted by fluorine. Alkoxy group of 1 to 10; fluoromethoxymethyl, difluoromethoxymethyl, trifluoromethoxymethyl, trifluoroethoxymethyl, pentafluoroethoxymethyl, heptafluoropropyl Oxymethyl, hexafluoroisopropoxymethyl, heptafluoroisopropoxymethyl, hexafluoro-2-methylisopropoxymethyl, perfluoro-2-methylisopropoxymethyl , perfluoro-n-butoxymethyl, perfluoro-n-pentoxymethyl, perfluorocyclopentoxymethyl and other alkoxy groups, alkoxyalkyl groups containing fluorine, such as alkoxyalkyl groups in which part or all of the hydrogen of the alkoxy group is substituted with fluorine Alkoxyalkyl groups having 2 to 10 carbon atoms, etc.
另外，R 1～R 4可相互鍵結而形成環結構，亦可形成全氟環烷基、經由氧的全氟環醚基等的環。 進而，作為不含氟的其他的R 1～R 4，可例示：氫；甲基、乙基、丙基、異丙基、2-甲基異丙基、正丁基、正戊基、環戊基等碳數1～10烷基；甲氧基、乙氧基、丙氧基、丁氧基、戊氧基等碳數1～10的烷氧基、甲氧基甲基、乙氧基甲基、丙氧基甲基、丁氧基甲基、戊氧基甲基等碳數2～10的烷氧基烷基等。 In addition, R 1 to R 4 may be bonded to each other to form a ring structure, or may form a ring such as a perfluorocycloalkyl group or a perfluorocyclic ether group via oxygen. Furthermore, examples of other R 1 to R 4 that do not contain fluorine include hydrogen; methyl, ethyl, propyl, isopropyl, 2-methylisopropyl, n-butyl, n-pentyl, cyclo Alkyl groups with 1 to 10 carbon atoms such as pentyl; alkoxy groups with 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, and pentoxy groups, methoxymethyl, and ethoxy Alkoxyalkyl groups having 2 to 10 carbon atoms such as methyl, propoxymethyl, butoxymethyl, and pentoxymethyl.
含氟環狀烯烴化合物（A）例如是藉由使含氟烯烴與環狀多烯進行狄耳士-阿德爾反應而獲得的組成物，有時是包含在所述式（1）中n為0的含氟環狀烯烴化合物（A1）及在所述式（1）中n為1的含氟環狀烯烴化合物（A2）此兩者的混合物。 在包含在所述式（1）中n為0的含氟環狀烯烴化合物（A1）及在所述式（1）中n為1的含氟環狀烯烴化合物（A2）此兩者的混合物的情況下，關於含氟環狀烯烴化合物（A1）及含氟環狀烯烴化合物（A2），較佳為在所述式（1）中，X為-CH 2-，且R 1～R 4為氟或三氟甲基，更佳為R 1～R 4中的一個為三氟甲基，剩餘部分為氟。 The fluorine-containing cyclic olefin compound (A) is, for example, a composition obtained by subjecting a fluorine-containing olefin and a cyclic polyene to Diels-Alder reaction, and may be included in the formula (1) in which n is A mixture of a fluorine-containing cyclic olefin compound (A1) of 0 and a fluorine-containing cyclic olefin compound (A2) in which n is 1 in the formula (1). A mixture containing a fluorine-containing cyclic olefin compound (A1) in which n is 0 in the formula (1) and a fluorine-containing cyclic olefin compound (A2) in which n is 1 in the formula (1). In the case of the fluorine-containing cyclic olefin compound (A1) and the fluorine-containing cyclic olefin compound (A2), it is preferable that in the formula (1), X is -CH 2 -, and R 1 to R 4 is fluorine or trifluoromethyl, more preferably one of R 1 to R 4 is trifluoromethyl, and the remainder is fluorine.
作為含氟環狀烯烴化合物（A），較佳為包含選自含氟四環十二烯、含氟降冰片烯、含氟氧代四環十二烯及含氟氧代降冰片烯中的至少一種，更佳為包含選自含氟四環十二烯及含氟降冰片烯中的至少一種，進而佳為包含含氟四環十二烯。 此處，所謂四環十二烯，是指四環[4.4.0.1 2,5.1 7,10]-3-十二烯。所謂降冰片烯，是指雙環[2.2.1]庚-2-烯。另外，所謂氧代降冰片烯，是指氧雜雙環[2.2.1]庚-2-烯。 所謂含氟四環十二烯，是所述式（1）中，X為-CH 2-、n為1的含氟環狀烯烴。 所謂含氟降冰片烯，是所述式（1）中，X為-CH 2-、n為0的含氟環狀烯烴。 所謂含氟氧代四環十二烯，是所述式（1）中，X為-O-、n為1的含氟環狀烯烴。 所謂含氟氧代降冰片烯，是所述式（1）中，X為-O-、n為0的含氟環狀烯烴。 The fluorine-containing cyclic olefin compound (A) preferably contains one selected from the group consisting of fluorine-containing tetracyclododecene, fluorine-containing norbornene, fluorine-containing oxytetracyclododecene, and fluorine-containing oxynorbornene. At least one kind, more preferably at least one kind selected from fluorine-containing tetracyclododecene and fluorine-containing norbornene, further preferably containing fluorine-containing tetracyclododecene. Here, tetracyclododecene refers to tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene. The so-called norbornene refers to bicyclo[2.2.1]hept-2-ene. In addition, oxonorbornene refers to oxabicyclo[2.2.1]hept-2-ene. Fluorine-containing tetracyclododecene is a fluorine-containing cyclic olefin in the formula (1), in which X is -CH 2 - and n is 1. Fluorine-containing norbornene is a fluorine-containing cyclic olefin in the formula (1), in which X is -CH 2 - and n is 0. The so-called fluorine-containing oxytetracyclododecene is a fluorine-containing cyclic olefin in the formula (1), where X is -O- and n is 1. The so-called fluorine-containing oxynorbornene is a fluorine-containing cyclic olefin in the formula (1), where X is -O- and n is 0.
（含氟烯烴） 含氟烯烴例如可使用下述式（2）所表示的含氟烯烴。 (fluorinated olefins) As the fluorine-containing olefin, for example, a fluorine-containing olefin represented by the following formula (2) can be used.
[化5] 所述式（2）中，R 1～R 4中的至少一個為氟、含有氟的碳數1～10的烷基、含有氟的碳數1～10的烷氧基、或含有氟的碳數2～10的烷氧基烷基，在R 1～R 4為不含有氟的基的情況下，R 1～R 4選自氫、碳數1～10的烷基、碳數1～10的烷氧基、或碳數2～10的烷氧基烷基中，R 1～R 4可相互鍵結而形成環結構。該些中，R 1～R 4較佳為氟或含有氟的碳數1～4的烷基，更佳為氟或三氟甲基，進而佳為R 1～R 4中的一個為三氟甲基，剩餘部分為氟。 [Chemistry 5] In the formula (2), at least one of R 1 to R 4 is fluorine, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkoxy group having 1 to 10 carbon atoms, or a fluorine-containing carbon group. Alkoxyalkyl group with 2 to 10 carbon atoms, when R 1 to R 4 are groups not containing fluorine, R 1 to R 4 are selected from hydrogen, alkyl groups with 1 to 10 carbon atoms, and alkyl groups with 1 to 10 carbon atoms. In an alkoxy group or an alkoxyalkyl group having 2 to 10 carbon atoms, R 1 to R 4 may be bonded to each other to form a ring structure. Among these, R 1 to R 4 are preferably fluorine or a fluorine-containing alkyl group having 1 to 4 carbon atoms, more preferably fluorine or trifluoromethyl, and even more preferably one of R 1 to R 4 is trifluoro Methyl, the remainder is fluorine.
在所述式（2）中，作為R 1～R 4，更具體而言，可例示：氟；氟甲基、二氟甲基、三氟甲基、三氟乙基、五氟乙基、七氟丙基、六氟異丙基、七氟異丙基、六氟-2-甲基異丙基、全氟-2-甲基異丙基、正全氟丁基、正全氟戊基、全氟環戊基等烷基的氫的一部分或全部經氟取代的烷基等含有氟的碳數1～10的烷基；氟甲氧基、二氟甲氧基、三氟甲氧基、三氟乙氧基、五氟乙氧基、七氟丙氧基、六氟異丙氧基、七氟異丙氧基、六氟-2-甲基異丙氧基、全氟-2-甲基異丙氧基、全氟正丁氧基、全氟正戊氧基、全氟環戊氧基等烷氧基的氫的一部分或全部經氟取代的烷氧基等含有氟的碳數1～10的烷氧基；氟甲氧基甲基、二氟甲氧基甲基、三氟甲氧基甲基、三氟乙氧基甲基、五氟乙氧基甲基、七氟丙氧基甲基、六氟異丙氧基甲基、七氟異丙氧基甲基、六氟-2-甲基異丙氧基甲基、全氟-2-甲基異丙氧基甲基、全氟正丁氧基甲基、全氟正戊氧基甲基、全氟環戊氧基甲基等烷氧基的氫的一部分或全部經氟取代的烷氧基烷基等含有氟的碳數2～10的烷氧基烷基等。 In the formula (2), as R 1 to R 4 , more specifically, fluorine; fluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, pentafluoroethyl, Heptafluoropropyl, hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro-2-methylisopropyl, perfluoro-2-methylisopropyl, n-perfluorobutyl, n-perfluoropentyl , alkyl groups with 1 to 10 carbon atoms such as perfluorocyclopentyl and other alkyl groups in which part or all of the hydrogens of the hydrogen are substituted by fluorine; fluorine-containing alkyl groups such as fluorine-containing alkyl groups; fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group , trifluoroethoxy, pentafluoroethoxy, heptafluoropropoxy, hexafluoroisopropoxy, heptafluoroisopropoxy, hexafluoro-2-methylisopropoxy, perfluoro-2- The number of carbon atoms in an alkoxy group containing fluorine, such as an alkoxy group such as methyl isopropoxy, perfluoro-n-butoxy, perfluoron-pentyloxy, or perfluorocyclopentoxy, where part or all of the hydrogens are substituted by fluorine. Alkoxy group of 1 to 10; fluoromethoxymethyl, difluoromethoxymethyl, trifluoromethoxymethyl, trifluoroethoxymethyl, pentafluoroethoxymethyl, heptafluoropropyl Oxymethyl, hexafluoroisopropoxymethyl, heptafluoroisopropoxymethyl, hexafluoro-2-methylisopropoxymethyl, perfluoro-2-methylisopropoxymethyl , perfluoro-n-butoxymethyl, perfluoro-n-pentoxymethyl, perfluorocyclopentoxymethyl and other alkoxy groups, alkoxyalkyl groups containing fluorine, such as alkoxyalkyl groups in which part or all of the hydrogen of the alkoxy group is substituted with fluorine Alkoxyalkyl groups having 2 to 10 carbon atoms, etc.
另外，R 1～R 4可相互鍵結而形成環結構，亦可形成全氟環烷基、經由氧的全氟環醚基等的環。 進而，作為不含氟的其他的R 1～R 4，可例示：氫；甲基、乙基、丙基、異丙基、2-甲基異丙基、正丁基、正戊基、環戊基等碳數1～10烷基；甲氧基、乙氧基、丙氧基、丁氧基、戊氧基等碳數1～10的烷氧基、甲氧基甲基、乙氧基甲基、丙氧基甲基、丁氧基甲基、戊氧基甲基等碳數2～10的烷氧基烷基等。 In addition, R 1 to R 4 may be bonded to each other to form a ring structure, or may form a ring such as a perfluorocycloalkyl group or a perfluorocyclic ether group via oxygen. Furthermore, examples of other R 1 to R 4 that do not contain fluorine include hydrogen; methyl, ethyl, propyl, isopropyl, 2-methylisopropyl, n-butyl, n-pentyl, cyclo Alkyl groups with 1 to 10 carbon atoms such as pentyl; alkoxy groups with 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, and pentoxy groups, methoxymethyl, and ethoxy Alkoxyalkyl groups having 2 to 10 carbon atoms such as methyl, propoxymethyl, butoxymethyl, and pentoxymethyl.
（環狀多烯） 作為環狀多烯，例如可使用環戊二烯、環己二烯、乙基環己二烯、環庚二烯、二環戊二烯、二環己二烯、1-氧雜-2,4-環戊二烯、1-氧雜-2-乙基-2,4-環戊二烯、1-氧雜-2-乙烯基-2,4-環戊二烯、伸乙基降冰片烯、乙烯基降冰片烯、異伸丙基降冰片烯、甲基氫茚、二異伸丙基降冰片烯、丙烯基異降冰片二烯等。 該些環狀多烯可單獨使用一種，亦可將兩種以上組合使用。 該些中，作為環狀多烯，較佳為環戊二烯、二環戊二烯及1-氧雜-2,4-環戊二烯（慣用名稱中通常稱為呋喃），更佳為二環戊二烯及呋喃，進而佳為二環戊二烯。 (cyclic polyene) As the cyclic polyene, for example, cyclopentadiene, cyclohexadiene, ethylcyclohexadiene, cycloheptadiene, dicyclopentadiene, dicyclohexadiene, and 1-oxa-2 can be used. 4-Cyclopentadiene, 1-oxa-2-ethyl-2,4-cyclopentadiene, 1-oxa-2-vinyl-2,4-cyclopentadiene, ethylidene norbornyl Alkene, vinylnorbornene, isopropylnorbornene, methylhydrindane, diisopropylnorbornene, propenylisonorbornediene, etc. These cyclic polyenes may be used individually by 1 type, or in combination of 2 or more types. Among these, as the cyclic polyene, cyclopentadiene, dicyclopentadiene and 1-oxa-2,4-cyclopentadiene (often called furan in common names) are preferred, and more preferred are Dicyclopentadiene and furan, more preferably dicyclopentadiene.
（不含氟環狀二烯烴化合物（B1）） 不含氟環狀二烯烴化合物（B1）例如是所述環狀多烯彼此進行狄耳士-阿德爾反應而獲得的化合物，可列舉二環戊二烯、三環戊二烯等。不含氟環狀二烯烴化合物（B1）亦可包含選自二環戊二烯及三環戊二烯中的至少一種。 (Does not contain fluorine cyclic diene compound (B1)) The fluorine-free cyclic diene compound (B1) is, for example, a compound obtained by Diels-Alder reaction between the above-mentioned cyclic polyenes, and examples thereof include dicyclopentadiene, tricyclopentadiene, and the like. The fluorine-free cyclic diene compound (B1) may contain at least one selected from dicyclopentadiene and tricyclopentadiene.
在組成物（X）中，在含氟環狀烯烴化合物（A）的沸點與不含氟環狀二烯烴化合物（B1）的沸點之差的絕對值為10℃以下的情況下，難以藉由蒸餾將含氟環狀烯烴化合物（A）與不含氟環狀二烯烴化合物（B1）加以分離，因此就獲得純度提高的含氟環狀烯烴組成物的觀點而言，本發明的含氟環狀烯烴組成物的製造方法有效。 在本說明書中，沸點表示1個氣壓下的沸點。 In the composition (X), when the absolute value of the difference between the boiling point of the fluorine-containing cyclic olefin compound (A) and the boiling point of the fluorine-free cyclic diene compound (B1) is 10°C or less, it is difficult to The fluorine-containing cyclic olefin compound (A) and the fluorine-containing cyclic diene compound (B1) are separated by distillation. Therefore, from the viewpoint of obtaining a fluorine-containing cyclic olefin composition with improved purity, the fluorine-containing cyclic olefin compound of the present invention is The method for producing the olefin composition is effective. In this specification, the boiling point means the boiling point at 1 atmospheric pressure.
（酸觸媒） 作為酸觸媒，只要是布忍斯特酸則並無特別限定，可列舉選自由無機酸、有機酸及固體酸所組成的群組中的至少一種。 作為無機酸，例如可列舉鹽酸、硫酸、硝酸、磷酸等。 作為有機酸，例如可列舉甲磺酸、三氟甲磺酸、苯磺酸、對甲苯磺酸、10-樟腦磺酸、三氟乙酸等。 作為固體酸，例如可列舉具有磺酸基的強酸性陽離子交換樹脂等。 該些中，就在反應後可不進行利用氫氧化鈉水溶液等鹼溶液對所使用的酸進行中和、提取的步驟而藉由過濾將酸觸媒分離的觀點而言，較佳為強酸性陽離子交換樹脂。進而就可增大與反應基質的接觸面積的觀點而言，較佳為具有表面積大的大孔結構的強酸性陽離子交換樹脂。 就進一步提高不含氟環狀二烯烴化合物（B1）與含羥基化合物（C）的反應性的觀點而言，酸觸媒的酸解離常數（pKa）較佳為2以下。 (acid catalyst) The acid catalyst is not particularly limited as long as it is a Brunester acid, and may be at least one selected from the group consisting of inorganic acids, organic acids, and solid acids. Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and the like. Examples of organic acids include methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, 10-camphorsulfonic acid, trifluoroacetic acid, and the like. Examples of solid acids include strongly acidic cation exchange resins having sulfonic acid groups. Among these, from the viewpoint that the acid catalyst can be separated by filtration without performing steps of neutralizing and extracting the acid used with an alkali solution such as sodium hydroxide aqueous solution after the reaction, strongly acidic cations are preferred. Exchange resin. Furthermore, from the viewpoint of increasing the contact area with the reaction substrate, a strongly acidic cation exchange resin having a macroporous structure with a large surface area is preferred. From the viewpoint of further improving the reactivity between the fluorine-free cyclic diene compound (B1) and the hydroxyl-containing compound (C), the acid dissociation constant (pKa) of the acid catalyst is preferably 2 or less.
就進一步提高不含氟環狀二烯烴化合物（B1）與含羥基化合物（C）的反應性的觀點而言，混合步驟中的酸觸媒的混合量相對於組成物（X）100質量份而較佳為0.01質量份以上，更佳為0.05質量份以上，進而佳為0.1質量份以上，進而佳為0.5質量份以上，進而佳為1.0質量份以上，進而佳為1.5質量份以上，並且較佳為50質量份以下，更佳為30質量份以下，進而佳為25質量份以下，進而佳為20質量份以下，進而佳為15質量份以下，進而佳為10質量份以下。From the viewpoint of further improving the reactivity of the fluorine-free cyclic diene compound (B1) and the hydroxyl-containing compound (C), the mixing amount of the acid catalyst in the mixing step is greater than 100 parts by mass of the composition (X). It is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, still more preferably 0.5 parts by mass or more, still more preferably 1.0 parts by mass or more, still more preferably 1.5 parts by mass or more, and more preferably It is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less.
（含羥基化合物（C）） 含羥基化合物（C）為選自由水及烷基醇所組成的群組中的至少一種。為了增大含氟環狀烯烴化合物（A）的沸點與不含氟醚化合物（B3）的沸點之差而在分離步驟中容易進行分離，較佳為烷基醇。 就藉由提高烷基醇的沸點來提高反應溫度以進一步提高不含氟環狀二烯烴化合物（B1）與含羥基化合物（C）的反應性的觀點、以及增大與含氟環狀烯烴化合物（A）的沸點之差而在分離步驟中容易進行分離的觀點而言，烷基醇的碳數較佳為3以上，並且較佳為10以下，更佳為8以下，進而佳為6以下。就該些觀點而言，烷基醇的碳數較佳為3以上且10以下，更佳為3以上且8以下，進而佳為3以上且6以下。 就進一步提高不含氟環狀二烯烴化合物（B1）與含羥基化合物（C）的反應性的觀點而言，作為烷基醇，較佳為選自由1-丙醇、2-丙醇、1-丁醇、2-丁醇、2-甲基-1-丙醇、2-甲基-2-丙醇、1-戊醇、2-戊醇、1-己醇、2-己醇、1-庚醇、2-庚醇、1-辛醇、1-壬醇及1-癸醇所組成的群組中的至少一種，更佳為選自由1-丙醇、1-丁醇、1-戊醇及1-己醇所組成的群組中的至少一種。 (hydroxyl-containing compound (C)) The hydroxyl-containing compound (C) is at least one selected from the group consisting of water and alkyl alcohol. In order to increase the difference in the boiling point of the fluorine-containing cyclic olefin compound (A) and the fluorine-free ether compound (B3) and facilitate separation in the separation step, an alkyl alcohol is preferred. From the viewpoint of raising the reaction temperature by raising the boiling point of the alkyl alcohol to further increase the reactivity between the fluorine-free cyclic diene compound (B1) and the hydroxyl-containing compound (C), and increasing the reaction temperature with the fluorine-containing cyclic olefin compound. From the viewpoint of facilitating separation in the separation step due to the difference in boiling point of (A), the number of carbon atoms of the alkyl alcohol is preferably 3 or more, more preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. . From these viewpoints, the number of carbon atoms of the alkyl alcohol is preferably 3 or more and 10 or less, more preferably 3 or more and 8 or less, even more preferably 3 or more and 6 or less. From the viewpoint of further improving the reactivity of the fluorine-free cyclic diene compound (B1) and the hydroxyl-containing compound (C), the alkyl alcohol is preferably selected from the group consisting of 1-propanol, 2-propanol, and 1-propanol. -Butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol, 2-hexanol, 1 -At least one selected from the group consisting of heptanol, 2-heptanol, 1-octanol, 1-nonanol and 1-decanol, more preferably selected from the group consisting of 1-propanol, 1-butanol, 1- At least one of the group consisting of pentanol and 1-hexanol.
就進一步提高不含氟環狀二烯烴化合物（B1）與含羥基化合物（C）的反應性的觀點而言，混合步驟中的含羥基化合物（C）的混合量相對於組成物（X）100質量份而較佳為1質量份以上，更佳為5質量份以上，進而佳為10質量份以上，進而佳為20質量份以上，進而佳為30質量份以上，並且較佳為1000質量份以下，更佳為500質量份以下，進而佳為250質量份以下，進而佳為150質量份以下，進而佳為100質量份以下，進而佳為60質量份以下。From the viewpoint of further improving the reactivity of the fluorine-free cyclic diene compound (B1) and the hydroxyl-containing compound (C), the mixing amount of the hydroxyl-containing compound (C) in the mixing step is 100% relative to the composition (X) Parts by mass are preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, and more preferably 1,000 parts by mass or less, more preferably 500 parts by mass or less, still more preferably 250 parts by mass or less, still more preferably 150 parts by mass or less, still more preferably 100 parts by mass or less, still more preferably 60 parts by mass or less.
在混合步驟中，作為將各成分加以混合的方法，可利用任意方法實施。關於各成分的混合，其順序並無限制，可以總括或分割等任意方式實施。作為將各成分加以混合的裝置，亦並無限制，可利用能夠進行攪拌、混合的批次式或連續式的任意裝置實施。將各成分加以混合時的溫度可在室溫至溶媒的沸點的範圍內任意選擇。 另外，混合步驟可與後述的反應步驟同時進行，亦可在反應步驟之前進行。 In the mixing step, any method can be used as a method of mixing each component. The mixing order of each component is not limited, and it can be carried out in any manner, such as lumping together or dividing. There is no restriction on the device for mixing the components, and any device capable of stirring and mixing can be used as a batch type or a continuous type. The temperature at which the components are mixed can be arbitrarily selected within the range from room temperature to the boiling point of the solvent. In addition, the mixing step may be performed simultaneously with the reaction step described below, or may be performed before the reaction step.
[反應步驟] 本發明的含氟環狀烯烴組成物的製造方法包含如下反應步驟，即：藉由使不含氟環狀二烯烴化合物（B1）與含羥基化合物（C）進行反應，獲得選自由不含氟水合化合物（B2）及不含氟醚化合物（B3）所組成的群組中的至少一種。 此處，關於含氟環狀烯烴化合物（A）與不含氟環狀二烯烴化合物（B1），通常雙鍵部分的電子密度不同，不含氟環狀二烯烴化合物（B1）更高。因此，在酸觸媒的存在下，當使包括含氟環狀烯烴化合物（A）及不含氟環狀二烯烴化合物（B1）的組成物（X）與含羥基化合物（C）進行反應時，不含氟環狀二烯烴化合物（B1）可選擇性地進行含羥基化合物（C）的加成反應而進行水合或醚化。 [Reaction steps] The method for producing a fluorine-containing cyclic olefin composition of the present invention includes a reaction step of reacting a fluorine-free cyclic diene compound (B1) with a hydroxyl-containing compound (C) to obtain a fluorine-free cyclic olefin compound selected from the group consisting of: At least one kind from the group consisting of the hydrated compound (B2) and the fluoroether-free compound (B3). Here, the fluorine-containing cyclic olefin compound (A) and the fluorine-free cyclic diene compound (B1) generally have different electron densities in the double bond portion, and the fluorine-free cyclic diene compound (B1) is higher. Therefore, in the presence of an acid catalyst, when the composition (X) including the fluorine-containing cyclic olefin compound (A) and the fluorine-free cyclic diene compound (B1) is reacted with the hydroxyl-containing compound (C) , the fluorine-free cyclic diene compound (B1) can selectively undergo an addition reaction to the hydroxyl-containing compound (C) to be hydrated or etherified.
此處，在所述組成物（X）中，就在反應步驟中進一步提高含羥基化合物（C）與不含氟環狀二烯烴化合物（B1）的選擇反應性的觀點而言，含氟環狀烯烴化合物（A）的HOMO能量（E 1）與不含氟環狀二烯烴化合物（B1）的HOMO能量（E 2）之差的絕對值｜E 2-E 1｜較佳為0.3 eV以上，更佳為0.5 eV以上。 此處，所謂HOMO，是最高佔有分子軌域（Highest Occupied Molecular Orbital），各化合物的HOMO能量可利用長程校正密度泛函法進行計算，具體而言，可使用量子化學計算軟體高斯（Gaussian）16 Rev.B.01，選定ωB97X-D作為泛函並採用6-31G（d）作為基函數，在此基礎上進行結構最佳化而進行計算。 Here, in the composition (X), from the viewpoint of further improving the selective reactivity between the hydroxyl-containing compound (C) and the fluorine-free cyclic diene compound (B1) in the reaction step, the fluorine-containing cyclic diene compound The absolute value of the difference between the HOMO energy (E 1 ) of the olefin compound (A) and the HOMO energy (E 2 ) of the fluorine-free cyclic diene compound (B1) | E 2 - E 1 | Preferably it is 0.3 eV or more , more preferably 0.5 eV or more. Here, the so-called HOMO refers to the Highest Occupied Molecular Orbital. The HOMO energy of each compound can be calculated using the long-range corrected density functional method. Specifically, the quantum chemistry calculation software Gaussian 16 can be used. Rev.B.01, ωB97X-D is selected as the functional and 6-31G(d) is used as the basis function. On this basis, the structure is optimized and calculated.
不含氟環狀二烯烴化合物（B1）與含羥基化合物（C）的反應例如可藉由對在所述混合步驟中獲得的組成物（X）與酸觸媒及含羥基化合物（C）的混合物進行加熱來進行。 反應步驟中的加熱溫度根據各成分的種類或處理量適宜設定，因此並無特別限定，就進一步促進不含氟環狀二烯烴化合物（B1）與含羥基化合物（C）的反應的觀點而言，較佳為60℃以上，更佳為80℃以上，進而佳為90℃以上，就進一步抑制酸觸媒的揮發或各成分的分解等的觀點而言，較佳為150℃以下，更佳為130℃以下，進而佳為120℃以下。就該些觀點而言，反應步驟中的加熱溫度較佳為60℃以上且150℃以下，更佳為80℃以上且130℃以下，進而佳為90℃以上且120℃以下。 The reaction between the fluorine-free cyclic diene compound (B1) and the hydroxyl-containing compound (C) can be carried out, for example, by reacting the composition (X) obtained in the mixing step with an acid catalyst and the hydroxyl-containing compound (C). The mixture is heated. The heating temperature in the reaction step is appropriately set according to the type of each component or the processing amount, and is not particularly limited, from the viewpoint of further promoting the reaction between the fluorine-free cyclic diene compound (B1) and the hydroxyl-containing compound (C). , preferably 60°C or higher, more preferably 80°C or higher, further preferably 90°C or higher, and from the viewpoint of further suppressing the volatilization of the acid catalyst or the decomposition of each component, it is preferably 150°C or lower, even more preferably The temperature is 130°C or lower, more preferably 120°C or lower. From these viewpoints, the heating temperature in the reaction step is preferably 60°C or more and 150°C or less, more preferably 80°C or more and 130°C or less, even more preferably 90°C or more and 120°C or less.
另外，反應步驟中的加熱時間（反應時間）根據各成分的種類或處理量適宜設定，因此並無特別限定，就進一步促進不含氟環狀二烯烴化合物（B1）與含羥基化合物（C）的反應的觀點而言，較佳為1小時以上，更佳為2小時以上，進而佳為4小時以上，進而佳為8小時以上，就提高生產性的觀點而言，較佳為48小時以下，更佳為24小時以下，進而佳為20小時以下。就該些觀點而言，反應步驟中的加熱時間（反應時間）較佳為1小時以上且48小時以下，更佳為2小時以上且24小時以下，進而佳為4小時以上且20小時以下，進而佳為8小時以上且20小時以下。 另外，反應步驟例如可在氮氣等惰性氣體環境、常壓（大氣壓）下進行。 In addition, the heating time (reaction time) in the reaction step is appropriately set according to the type of each component or the processing amount, and is therefore not particularly limited. It further promotes the formation of the fluorine-free cyclic diene compound (B1) and the hydroxyl-containing compound (C). From the viewpoint of reaction, it is preferably 1 hour or more, more preferably 2 hours or more, further preferably 4 hours or more, further preferably 8 hours or more, and from the viewpoint of improving productivity, 48 hours or less is preferred. , more preferably less than 24 hours, further preferably less than 20 hours. From these viewpoints, the heating time (reaction time) in the reaction step is preferably from 1 hour to 48 hours, more preferably from 2 hours to 24 hours, even more preferably from 4 hours to 20 hours, More preferably, it is 8 hours or more and 20 hours or less. In addition, the reaction step can be performed, for example, in an inert gas environment such as nitrogen and under normal pressure (atmospheric pressure).
[分離步驟] 就進一步提高所獲得的含氟環狀烯烴組成物的純度即含氟環狀烯烴組成物中的作為目標物的含氟環狀烯烴化合物（A）的含量的觀點而言，本發明的含氟環狀烯烴組成物的製造方法較佳為更包含如下分離步驟，即：在所述反應步驟之後，藉由蒸餾將含氟環狀烯烴化合物（A）與選自由不含氟水合化合物（B2）及不含氟醚化合物（B3）所組成的群組中的至少一種加以分離。 作為蒸餾的方法，只要是可將含氟環狀烯烴化合物（A）與不含氟水合化合物（B2）或不含氟醚化合物（B3）加以分離的蒸餾方法，則並無特別限定，例如，可列舉在大氣壓下實施的常壓蒸餾、對系統內進行減壓而進行的減壓蒸餾等。 [Separation step] From the viewpoint of further improving the purity of the obtained fluorine-containing cyclic olefin composition, that is, the content of the target fluorine-containing cyclic olefin compound (A) in the fluorine-containing cyclic olefin composition, the fluorine-containing cyclic olefin compound of the present invention The manufacturing method of the cyclic olefin composition preferably further includes the following separation step, that is, after the reaction step, distilling the fluorine-containing cyclic olefin compound (A) and the fluorine-free hydrated compound (B2) and at least one of the group consisting of a fluoroether compound (B3) is separated. The distillation method is not particularly limited as long as it can separate the fluorine-containing cyclic olefin compound (A) from the fluorine-free hydrated compound (B2) or the fluorine-free ether compound (B3). For example, Examples include normal pressure distillation performed under atmospheric pressure, vacuum distillation performed by depressurizing the system, and the like.
另外，在含氟環狀烯烴化合物（A）包含在所述式（1）中n為0的含氟環狀烯烴化合物（A1）及在所述式（1）中n為1的含氟環狀烯烴化合物（A2）此兩者的情況下，就進一步提高所獲得的含氟環狀烯烴組成物的純度即含氟環狀烯烴組成物中的作為目標物的含氟環狀烯烴化合物（A）的含量的觀點而言，本發明的含氟環狀烯烴組成物的製造方法較佳為更包含如下分離步驟，即：在所述反應步驟之後，藉由蒸餾將含氟環狀烯烴化合物（A1）與含氟環狀烯烴化合物（A2）加以分離。 作為蒸餾的方法，只要是可將含氟環狀烯烴化合物（A1）與含氟環狀烯烴化合物（A2）加以分離的蒸餾方法，則並無特別限定，例如可列舉在大氣壓下實施的常壓蒸餾、對系統內進行減壓而進行的減壓蒸餾等。 In addition, the fluorine-containing cyclic olefin compound (A) includes a fluorine-containing cyclic olefin compound (A1) in which n is 0 in the above formula (1) and a fluorine-containing cyclic olefin compound (A1) in which n is 1 in the above formula (1). In the case of both the fluorine-containing cyclic olefin compound (A2) and the target fluorine-containing cyclic olefin compound (A2) in the fluorine-containing cyclic olefin composition, the purity of the obtained fluorine-containing cyclic olefin composition is further improved. ) content, the method for producing the fluorine-containing cyclic olefin composition of the present invention preferably further includes the following separation step: after the reaction step, the fluorine-containing cyclic olefin compound ( A1) is separated from the fluorine-containing cyclic olefin compound (A2). The distillation method is not particularly limited as long as it can separate the fluorine-containing cyclic olefin compound (A1) and the fluorine-containing cyclic olefin compound (A2). Examples thereof include normal pressure performed at atmospheric pressure. Distillation, vacuum distillation by reducing the pressure in the system, etc.
在本發明的含氟環狀烯烴組成物的製造方法中，在將含氟環狀烯烴組成物的整體設為100質量%時，所獲得的含氟環狀烯烴組成物中的不含氟環狀二烯烴化合物（B1）的含量較佳為5.0質量%以下，更佳為3.0質量%以下，進而佳為2.0質量%以下，進而佳為1.0質量%以下，進而佳為0.8質量%以下，進而佳為0.3質量%以下。 另外，所獲得的含氟環狀烯烴組成物中的不含氟環狀二烯烴化合物（B1）的含量越少越較佳，因此所述含量的下限值並無特別限定，例如可超過0質量%，亦可為0.01質量%以上，亦可為0.05質量%以上，亦可為0.1質量%以上。 In the method for producing a fluorine-containing cyclic olefin composition of the present invention, when the entire fluorine-containing cyclic olefin composition is taken as 100 mass %, the fluorine-containing cyclic olefin composition obtained does not contain fluorine rings. The content of the diene compound (B1) is preferably 5.0 mass% or less, more preferably 3.0 mass% or less, still more preferably 2.0 mass% or less, still more preferably 1.0 mass% or less, still more preferably 0.8 mass% or less, still more preferably Preferably, it is 0.3 mass % or less. In addition, the lower the content of the fluorine-free cyclic diene compound (B1) in the obtained fluorine-containing cyclic olefin composition, the better. Therefore, the lower limit of the content is not particularly limited. For example, it may exceed 0 Mass% may be 0.01 mass% or more, 0.05 mass% or more, or 0.1 mass% or more.
另外，在本發明的含氟環狀烯烴組成物的製造方法中，在將含氟環狀烯烴組成物的整體設為100質量%時，所獲得的含氟環狀烯烴組成物中的作為目標物的含氟環狀烯烴化合物（A）的含量較佳為75.0質量%以上，更佳為80.0質量%以上，進而佳為85.0質量%以上，進而佳為90.0質量%以上。 在本發明的含氟環狀烯烴組成物的製造方法中，將選自由不含氟水合化合物（B2）及不含氟醚化合物（B3）所組成的群組中的至少一種加以分離的分離步驟後獲得的含氟環狀烯烴組成物中的作為目標物的含氟環狀烯烴化合物（A）的含量較佳為99.0量%以上，更佳為99.2質量%以上，進而佳為99.5質量%以上，進而佳為99.7質量%以上。 另外，在本發明的含氟環狀烯烴組成物的製造方法中，在將含氟環狀烯烴組成物的整體設為100質量%時，所獲得的含氟環狀烯烴組成物中的作為目標物的在所述式（1）中n為0的含氟環狀烯烴化合物（A1）的含量較佳為99.0質量%以上，更佳為99.2質量%以上，進而佳為99.5質量%以上，進而佳為99.7質量%以上。 另外，在本發明的含氟環狀烯烴組成物的製造方法中，在將含氟環狀烯烴組成物的整體設為100質量%時，所獲得的含氟環狀烯烴組成物中的作為目標物的在所述式（1）中n為1的含氟環狀烯烴化合物（A2）的含量較佳為99.0質量%以上，更佳為99.2質量%以上，進而佳為99.5質量%以上，進而佳為99.7質量%以上。 此處，含氟環狀烯烴組成物中的各成分的含量例如可藉由氣相層析進行測定。測定方法可使用島津製作所股份有限公司製造的「GC-2010Plus」，且使用「DB-5」（長度30 m×直徑0.25 mm×膜厚0.5 μm，安捷倫科技（Agilent Technologies）公司製造）來作為毛細管柱。關於測定條件，可在以40℃保持2分鐘後，以10℃/分鐘升溫至250℃的條件下對各成分的濃度進行測定。關於各成分的濃度，可在所獲得的層析圖中，將相對於總波峰面積而言的各成分的波峰面積比例（質量%）設為該成分的濃度。 In addition, in the method for producing a fluorine-containing cyclic olefin composition of the present invention, when the entire fluorine-containing cyclic olefin composition is taken as 100% by mass, the target of the obtained fluorine-containing cyclic olefin composition is The content of the fluorine-containing cyclic olefin compound (A) in the material is preferably 75.0 mass% or more, more preferably 80.0 mass% or more, still more preferably 85.0 mass% or more, further preferably 90.0 mass% or more. In the method for producing a fluorine-containing cyclic olefin composition of the present invention, a separation step of isolating at least one selected from the group consisting of a fluorine-free hydrated compound (B2) and a fluorine-free ether compound (B3) The content of the target fluorine-containing cyclic olefin compound (A) in the subsequently obtained fluorine-containing cyclic olefin composition is preferably 99.0% by mass or more, more preferably 99.2% by mass or more, and still more preferably 99.5% by mass or more. , more preferably 99.7% by mass or more. In addition, in the method for producing a fluorine-containing cyclic olefin composition of the present invention, when the entire fluorine-containing cyclic olefin composition is taken as 100% by mass, the target of the obtained fluorine-containing cyclic olefin composition is The content of the fluorine-containing cyclic olefin compound (A1) in which n is 0 in the formula (1) is preferably 99.0 mass% or more, more preferably 99.2 mass% or more, further preferably 99.5 mass% or more, and further Preferably, it is 99.7% by mass or more. In addition, in the method for producing a fluorine-containing cyclic olefin composition of the present invention, when the entire fluorine-containing cyclic olefin composition is taken as 100% by mass, the target of the obtained fluorine-containing cyclic olefin composition is The content of the fluorine-containing cyclic olefin compound (A2) in which n is 1 in the formula (1) is preferably 99.0 mass% or more, more preferably 99.2 mass% or more, further preferably 99.5 mass% or more, and further Preferably, it is 99.7% by mass or more. Here, the content of each component in the fluorine-containing cyclic olefin composition can be measured, for example, by gas chromatography. The measurement method can use "GC-2010Plus" manufactured by Shimadzu Corporation, and use "DB-5" (length 30 m × diameter 0.25 mm × film thickness 0.5 μm, manufactured by Agilent Technologies) as the capillary tube column. Regarding the measurement conditions, the concentration of each component can be measured under the conditions of maintaining the temperature at 40°C for 2 minutes and then increasing the temperature to 250°C at 10°C/min. Regarding the concentration of each component, the peak area ratio (mass %) of each component relative to the total peak area in the obtained chromatogram can be set as the concentration of the component.
藉由本發明的含氟環狀烯烴組成物，例如，可利用使用過渡金屬觸媒使鹼金屬類作為助觸媒共存來合成聚合物的配位聚合；使用自由基起始劑並藉由光或熱產生自由基來合成聚合物的自由基聚合；使用鎢氯化物或鉬氯化物使鹼金屬類作為助觸媒共存來合成聚合物的移位聚合；使用以鎢、鉬、釕為中心金屬的亞烷基觸媒合成聚合物的移位聚合等方法，合成含氟環狀烯烴聚合物。在各個聚合法中，可使兩種以上的本發明的含氟環狀烯烴組成物共存而使用。 進而，在各種聚合法中，可使非氟系的環狀或鏈狀烯烴共存而與本發明的含氟環狀烯烴組成物共聚，亦可使用非氟系的環狀或鏈狀烯烴作為鏈轉移劑。 所獲得的聚合物不僅顯示出作為環狀烯烴聚合物的特性，而且藉由氟原子及/或含氟取代基的效果，其成型物例如顯示出低折射且高透明的樹脂特性，例如可以透鏡、膜、光波導、纖維等形態以光學、電子材料領域為中心廣泛展開。 By using the fluorine-containing cyclic olefin composition of the present invention, for example, a transition metal catalyst can be used to coexist with an alkali metal as a cocatalyst to synthesize a polymer through coordination polymerization; a free radical initiator can be used and the polymer can be synthesized by light or Free radical polymerization using heat to generate free radicals to synthesize polymers; displacement polymerization using tungsten chloride or molybdenum chloride to coexist with alkali metals as cocatalysts to synthesize polymers; using tungsten, molybdenum, and ruthenium as central metals Fluorine-containing cyclic olefin polymers can be synthesized by methods such as shift polymerization of alkylene catalyst-synthesized polymers. In each polymerization method, two or more fluorine-containing cyclic olefin compositions of the present invention can be used in coexistence. Furthermore, in various polymerization methods, non-fluorine-based cyclic or chain olefins can be coexisted and copolymerized with the fluorine-containing cyclic olefin composition of the present invention, or non-fluorine-based cyclic or chain olefins can be used as chain olefins. transfer agent. The obtained polymer not only exhibits properties as a cyclic olefin polymer, but also exhibits properties of a molded product such as a low-refractive and highly transparent resin, such as a lens, due to the effect of fluorine atoms and/or fluorine-containing substituents. , films, optical waveguides, fibers and other forms are widely developed, focusing on the fields of optical and electronic materials.
以上，對本發明的實施方式進行了敘述，但該些為本發明的示例，亦可採用所述以外的各種結構。 另外，本發明並不限定於所述實施方式，在不損害本發明的效果的範圍內的變形、改良等亦包含於本發明中。 [實施例] The embodiments of the present invention have been described above. However, these are examples of the present invention, and various structures other than those described above may be adopted. In addition, the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within a range that does not impair the effects of the present invention are also included in the present invention. [Example]
以下，參照實施例等對本實施方式進行詳細說明。此外，本實施方式並不受該些實施例的記載的任何限定。Hereinafter, this embodiment will be described in detail with reference to Examples and the like. In addition, this embodiment is not limited at all by the description of these Examples.
[蒸餾精製前後的含氟環狀烯烴組成物中的各組成物的含量的測定] 蒸餾精製前後的含氟環狀烯烴組成物中的各組成物的含量（質量%）是藉由氣相層析測定進行。 作為氣相層析裝置，使用島津製作所公司製造的「GC-2010Plus」，作為毛細管柱，使用安捷倫科技（Agilent Technologies）公司製造的「DB-5」（長度30 m×直徑0.25 mm×膜厚0.5 μm）。關於測定，是在以40℃保持2分鐘後，以10℃/分鐘升溫至250℃的條件下進行測定。關於各成分的濃度，在所獲得的層析圖中，將相對於總波峰面積而言的各成分的波峰面積比例（質量%）設為該成分的濃度。 [Measurement of the contents of each component in the fluorine-containing cyclic olefin composition before and after distillation and purification] The content (mass %) of each component in the fluorine-containing cyclic olefin composition before and after distillation and purification was measured by gas chromatography. As the gas chromatography device, "GC-2010Plus" manufactured by Shimadzu Corporation was used, and as the capillary column, "DB-5" manufactured by Agilent Technologies (length 30 m × diameter 0.25 mm × film thickness 0.5 μm). The measurement was performed under the conditions of maintaining the temperature at 40°C for 2 minutes and then increasing the temperature to 250°C at 10°C/min. Regarding the concentration of each component, the peak area ratio (mass %) of each component relative to the total peak area in the obtained chromatogram was defined as the concentration of the component.
[實施例1] 在氮氣環境下，在包括磁攪拌裝置的25 L的高壓釜內放入二環戊二烯（東京化成工業公司製造，以下亦稱為「DCp（Dicyclopentadiene）」）5.8 kg、六氟丙烯（高千穗化學工業公司製造）16.6 kg，在160℃下加熱攪拌24小時，接著，在180℃下加熱攪拌15小時。冷卻後，回收未反應的六氟丙烯3.9 kg，並取出反應液17.9 kg。 接著，藉由對所獲得的反應液進行蒸餾，獲取15.5 kg的包含5,5,6-三氟-6-三氟甲基-雙環[2.2.1]庚-2-烯（以下，亦稱為「NBF 6」）與DCp的組成物，並自蒸餾裝置內的殘留液獲取2.2 kg的包含8,8,9-三氟-9-三氟甲基-四環[4.4.0.1 2,5.1 7,10]-3-十二烯（以下，亦稱為「TDF 6」）、NBF 6、DCp及三環戊二烯（以下，亦稱為「TCPD（Tricyclopentadiene）」）的組成物（X1）。此處，TDF 6的沸點為240℃，NBF 6的沸點為165℃，DCp的沸點為170℃，TCPD的沸點為248℃。 另外，TDF 6的HOMO能量為-8.7 eV，NBF 6的HOMO能量為-9.3 eV，DCp的HOMO能量為-8.4 eV，TCPD的HOMO能量為-8.2 eV。 此處，所謂HOMO，是最高佔有分子軌域（Highest Occupied Molecular Orbital），各化合物的HOMO能量可利用長程校正密度泛函法進行計算，具體而言，使用量子化學計算軟體高斯（Gaussian）16 Rev.B.01，選定ωB97X-D作為泛函並採用6-31G（d）作為基函數，在此基礎上進行結構最佳化而進行計算。 [Example 1] In a nitrogen atmosphere, 5.8 kg of dicyclopentadiene (manufactured by Tokyo Chemical Industry Co., Ltd., also referred to as "DCp (Dicyclopentadiene)" below) was placed in a 25 L autoclave equipped with a magnetic stirring device. 16.6 kg of hexafluoropropylene (manufactured by Takachiho Chemical Industry Co., Ltd.) was heated and stirred at 160°C for 24 hours, and then heated and stirred at 180°C for 15 hours. After cooling, 3.9 kg of unreacted hexafluoropropylene was recovered, and 17.9 kg of reaction liquid was taken out. Next, by distilling the obtained reaction liquid, 15.5 kg of 5,5,6-trifluoro-6-trifluoromethyl-bicyclo[2.2.1]hept-2-ene (hereinafter also referred to as It is a composition of "NBF 6 ") and DCp, and 2.2 kg of 8,8,9-trifluoro-9-trifluoromethyl-tetracyclo[4.4.0.1 2,5] was obtained from the residual liquid in the distillation device .1 A composition of 7,10 ]-3-dodecene (hereinafter also referred to as "TDF 6 "), NBF 6 , DCp and tricyclopentadiene (hereinafter also referred to as "TCPD (Tricyclopentadiene)") (X1). Here, the boiling point of TDF 6 is 240°C, the boiling point of NBF 6 is 165°C, the boiling point of DCp is 170°C, and the boiling point of TCPD is 248°C. In addition, the HOMO energy of TDF 6 is -8.7 eV, the HOMO energy of NBF 6 is -9.3 eV, the HOMO energy of DCp is -8.4 eV, and the HOMO energy of TCPD is -8.2 eV. Here, the so-called HOMO refers to the Highest Occupied Molecular Orbital. The HOMO energy of each compound can be calculated using the long-range corrected density functional method. Specifically, the quantum chemistry calculation software Gaussian 16 Rev is used. .B.01, select ωB97X-D as the functional and 6-31G(d) as the basis function, and perform structural optimization and calculation on this basis.
接著，在帶有攪拌機及冷凝器的1000 mL的玻璃制反應器中，放入250 g的組成物（X1）、100 g的作為含羥基化合物（C）的水、5 g的作為酸觸媒的硫酸，在氮氣環境下，在100℃下加熱攪拌18小時，進行組成物（X1）中的DCp及TCPD的水合反應（以下，亦稱為「反應步驟」）。接著，將所獲得的反應液冷卻至室溫後，利用5%NaOH水溶液進行中和、提取，藉此獲得蒸餾精製前的含氟環狀烯烴組成物。利用氣相層析對該蒸餾精製前的含氟環狀烯烴組成物進行了分析。 另外，在裝有蒸餾精製前的含氟環狀烯烴組成物的圓底燒瓶安裝斯奈德（Snyder）分餾管、李比希（Liebig）冷卻管，藉由減壓蒸餾分餾獲取含NBF 6組成物與含TDF 6組成物，並利用氣相層析分別進行分析。 此處，表1中的DCp-OH及TCPD-OH分別意指DCp及TCPD的水合化合物。 Next, 250 g of the composition (X1), 100 g of water as the hydroxyl compound (C), and 5 g of the acid catalyst were placed in a 1000 mL glass reactor equipped with a stirrer and a condenser. sulfuric acid, heated and stirred at 100°C for 18 hours under a nitrogen atmosphere to perform a hydration reaction of DCp and TCPD in the composition (X1) (hereinafter also referred to as the "reaction step"). Next, the obtained reaction liquid was cooled to room temperature, neutralized and extracted with a 5% NaOH aqueous solution, thereby obtaining a fluorine-containing cyclic olefin composition before distillation and purification. The fluorine-containing cyclic olefin composition before distillation and purification was analyzed by gas chromatography. In addition, a Snyder fractionating tube and a Liebig cooling tube were installed in the round-bottomed flask containing the fluorine-containing cyclic olefin composition before distillation and purification, and the NBF 6- containing composition and the composition were obtained by fractionation under reduced pressure distillation. Containing TDF 6 composition, and analyzed separately by gas chromatography. Here, DCp-OH and TCPD-OH in Table 1 mean hydrated compounds of DCp and TCPD, respectively.
[實施例2～實施例6] 將酸觸媒及含羥基化合物（C）的種類變更為表1所記載者，將酸觸媒的投入量設為13 g，將反應步驟中的加熱條件變更為表1所記載的條件，除此以外，與實施例1同樣地分別進行含TDF 6組成物及含NBF 6組成物的製造及評價。此處，實施例4及實施例5中使用組成物（X2）來代替組成物（X1），實施例6中使用組成物（X3）來代替組成物（X1）。在使用固體酸作為酸觸媒的情況下，將藉由減壓過濾去除固體酸觸媒者作為氣相層析分析用的測定樣品。 表1中的固體酸A及固體酸B的詳細情況如以下所述。 固體酸A：具有磺酸基的陽離子交換樹脂（安百來（AmberLite） TMHPR2900H陽離子交換樹脂（Cation Exchange Resin），西格瑪奧德里奇（Sigma Aldrich）公司製造，酸解離常數pKa=2以下） 固體酸B：具有磺酸基的陽離子交換樹脂（AMBERLYST 15JS-HG•DRY，奧加諾（Organo）公司製造，酸解離常數pKa=2以下） 此處，表1中的DCp-OPr或-OHx及TCPD-OPr分別意指DCp及TCPD的烷基醚化物。 [Examples 2 to 6] The types of the acid catalyst and the hydroxyl-containing compound (C) were changed to those listed in Table 1, the input amount of the acid catalyst was set to 13 g, and the heating conditions in the reaction step were changed. Except for the conditions described in Table 1, the TDF 6 -containing composition and the NBF 6 -containing composition were produced and evaluated in the same manner as in Example 1. Here, in Examples 4 and 5, composition (X2) was used instead of composition (X1), and in Example 6, composition (X3) was used instead of composition (X1). When a solid acid is used as an acid catalyst, the solid acid catalyst is removed by filtration under reduced pressure and used as a measurement sample for gas chromatography analysis. The details of solid acid A and solid acid B in Table 1 are as follows. Solid acid A: Cation exchange resin with sulfonic acid group (AmberLite TM HPR2900H Cation Exchange Resin, manufactured by Sigma Aldrich, acid dissociation constant pKa = 2 or less) solid Acid B: Cation exchange resin with sulfonic acid group (AMBERLYST 15JS-HG·DRY, manufactured by Organo Company, acid dissociation constant pKa = 2 or less) Here, DCp-OPr or -OHx in Table 1 and TCPD-OPr means DCp and alkyl etherate of TCPD respectively.
（組成物（X2）的製備） 在氮氣環境下，在包括磁攪拌裝置的25 L的高壓釜內放入DCp（東京化成工業公司製造）3.8 kg、六氟丙烯（高千穗化學工業公司製造）11.5 kg，在160℃下加熱攪拌24小時，接著，在180℃下加熱攪拌15小時。冷卻後，回收未反應的六氟丙烯2.5 kg，並取出反應液12.4 kg。 接著，藉由對所獲得的反應液進行蒸餾，獲取11.0 kg的包含NBF 6與DCp的組成物，並自蒸餾裝置內的殘留液獲取1.0 kg的包含TDF 6、NBF 6、及TCPD的組成物（X2）。 (Preparation of composition (X2)) In a nitrogen atmosphere, 3.8 kg of DCp (manufactured by Tokyo Chemical Industry Co., Ltd.) and 11.5 kg of hexafluoropropylene (manufactured by Takachiho Chemical Industry Co., Ltd.) were placed in a 25 L autoclave including a magnetic stirring device. kg, heated and stirred at 160°C for 24 hours, and then heated and stirred at 180°C for 15 hours. After cooling, 2.5 kg of unreacted hexafluoropropylene was recovered, and 12.4 kg of reaction liquid was taken out. Next, by distilling the obtained reaction liquid, 11.0 kg of the composition containing NBF 6 and DCp was obtained, and 1.0 kg of the composition containing TDF 6 , NBF 6 , and TCPD was obtained from the residual liquid in the distillation device. (X2).
（組成物（X3）的製備） 在氮氣環境下，在包括磁攪拌裝置的25 L的高壓釜內放入DCp（東京化成工業公司製造）5.2 kg、六氟丙烯（高千穗化學工業公司製造）14.2 kg，在160℃下加熱攪拌24小時，接著，在180℃下加熱攪拌15小時。冷卻後，回收未反應的六氟丙烯1.9 kg，並取出反應液16.3 kg。 接著，藉由對所獲得的反應液進行蒸餾，獲取14.7 kg的包含NBF 6與DCp的組成物，並自蒸餾裝置內的殘留液獲取1.3 kg的包含TDF 6、NBF 6、及TCPD的組成物（X3）。 (Preparation of composition (X3)) In a nitrogen atmosphere, 5.2 kg of DCp (manufactured by Tokyo Chemical Industry Co., Ltd.) and 14.2 kg of hexafluoropropylene (manufactured by Takachiho Chemical Industry Co., Ltd.) were placed in a 25 L autoclave including a magnetic stirring device. kg, heated and stirred at 160°C for 24 hours, and then heated and stirred at 180°C for 15 hours. After cooling, 1.9 kg of unreacted hexafluoropropylene was recovered, and 16.3 kg of reaction liquid was taken out. Next, by distilling the obtained reaction liquid, 14.7 kg of the composition containing NBF 6 and DCp was obtained, and 1.3 kg of the composition containing TDF 6 , NBF 6 , and TCPD was obtained from the residual liquid in the distillation device (X3).
[比較例1] 不進行醚化反應，除此以外，與實施例1同樣地分別進行含NBF 6組成物及含TDF 6組成物的製造及評價。 [Comparative Example 1] An NBF 6 -containing composition and a TDF 6 -containing composition were produced and evaluated in the same manner as in Example 1, except that the etherification reaction was not performed.
將以上的結果示於表1中。The above results are shown in Table 1.
[表1]
表1
本申請案主張以在2022年3月29日提出申請的日本專利申請特願2022-054139號為基礎的優先權，並將其揭示的全部內容併入至本文中。This application claims priority based on Japanese Patent Application No. 2022-054139 filed on March 29, 2022, and the entire disclosure thereof is incorporated herein.
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