JP6383415B2 - ポリケトン重合触媒 - Google Patents
ポリケトン重合触媒 Download PDFInfo
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- JP6383415B2 JP6383415B2 JP2016527932A JP2016527932A JP6383415B2 JP 6383415 B2 JP6383415 B2 JP 6383415B2 JP 2016527932 A JP2016527932 A JP 2016527932A JP 2016527932 A JP2016527932 A JP 2016527932A JP 6383415 B2 JP6383415 B2 JP 6383415B2
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- Prior art keywords
- bis
- dimethyl
- methoxyphenyl
- phosphine
- dioxane
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- 229920001470 polyketone Polymers 0.000 title claims description 33
- 239000002685 polymerization catalyst Substances 0.000 title claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000003446 ligand Substances 0.000 claims description 24
- HFEAMIKDDWKNAG-UHFFFAOYSA-N bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1PC1=CC=CC=C1OC HFEAMIKDDWKNAG-UHFFFAOYSA-N 0.000 claims description 21
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 21
- -1 2,2-dimethyl-1,3-dioxane-5,5-diyl Chemical group 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- CEWDAROJZGKUGQ-UHFFFAOYSA-N 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane Chemical compound CC1(C)OCC(CBr)(CBr)CO1 CEWDAROJZGKUGQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000012312 sodium hydride Substances 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 5
- IIKVDSGDRQSJPE-UHFFFAOYSA-N [3-[bis(2-methoxyphenyl)phosphanylmethyl]-1,5-dioxaspiro[5.5]undecan-3-yl]methyl-bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)CC1(CP(C=2C(=CC=CC=2)OC)C=2C(=CC=CC=2)OC)COC2(CCCCC2)OC1 IIKVDSGDRQSJPE-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 150000003623 transition metal compounds Chemical class 0.000 description 4
- SXXPTCXIFIOPQF-UHFFFAOYSA-N 3-bis(2-methoxyphenyl)phosphanylpropyl-bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)CCCP(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC SXXPTCXIFIOPQF-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- UPLNHHIRAULCHF-UHFFFAOYSA-N [3-bis(2-methoxyphenyl)phosphanyl-2,2-dimethoxypropyl]-bis(2-methoxyphenyl)phosphane Chemical compound COC(CP(C1=C(C=CC=C1)OC)C1=C(C=CC=C1)OC)(CP(C1=C(C=CC=C1)OC)C1=C(C=CC=C1)OC)OC UPLNHHIRAULCHF-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- ONVXOMZCAAXUJR-UHFFFAOYSA-N 2,2,3-trifluorobutanedioic acid Chemical compound OC(=O)C(F)C(F)(F)C(O)=O ONVXOMZCAAXUJR-UHFFFAOYSA-N 0.000 description 1
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 1
- FOECNULCVUEEPJ-UHFFFAOYSA-N 2-(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)CBr FOECNULCVUEEPJ-UHFFFAOYSA-N 0.000 description 1
- ZEWOLCKVOBXLLD-UHFFFAOYSA-N 4-(bromomethyl)-2,2-dimethyl-1,3-dioxane Chemical compound CC1(C)OCCC(CBr)O1 ZEWOLCKVOBXLLD-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZGEZPSPEVXDOMG-UHFFFAOYSA-N lithium;phosphane Chemical compound [Li].P ZGEZPSPEVXDOMG-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5027—Polyphosphines
-
- 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
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
- C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyethers (AREA)
Description
例えば、酢酸パラジウム/1,3−ビス[ジ(2−メトキシフェニル)ホスフィノ]プロパン/トリフルオロ酢酸(Pd(OAc)2−BDOMPP−TFA)系が開発され、Shell社が1999年に商業化したことがある。
また、3,3−ビス−[ビス−(2−メトキシフェニル)ホスファニルメチル]−1,5−ジオキサスピロ[5,5]ウンデカンに関する特許(WO2001−002463A1)に記述された合成法はリチウムを用いる実験室規模(Lab Scale)のみで可能である危ない反応であって、商業的な大量生産には不適合という問題がある。
そして、前記(C)酸はトリフルオロ酢酸(Trifluoroacetic acid)、トリフルオロメタンスルホン酸(Trifluoromethanesulfonic acid)、p−トルエンスルホン酸(p−Toluenesulfonic acid)、硫酸(Sulfuric acid)またはマレイン酸(Maleic acid)であることを特徴とするポリケトン重合触媒を提供する。
また、本発明の他の態様では、ビス(2−メトキシフェニル)ホスフィン、5,5−ビス(ブロモメチル)−2,2−ジメチル−1,3−ジオキサン及び水素化ナトリウムを用いて((2,2−ジメチル−1,3−ジオキサン−5,5−ジイル)ビス(メチレン))ビス(ビス(2−メトキシフェニル)ホスフィン)を得ることを特徴とするポリケトン重合触媒用リガンドの製造方法を提供する。
また、本発明のポリケトン重合触媒用リガンドの製造方法によれば、前記((2,2−ジメチル−1,3−ジオキサン−5,5−ジイル)ビス(メチレン))ビス(ビス(2−メトキシフェニル)ホスフィン)を、リチウムを用いない安全な環境下で容易なプロセスを通じて商業的に大量合成することができる。
ポリケトン重合触媒
本発明のポリケトン重合触媒は(A)金属イオン;(B)リガンドとして((2,2−ジメチル−1,3−ジオキサン−5,5−ジイル)ビス(メチレン))ビス(ビス(2−メトキシフェニル)ホスフィン);及び(C)酸;からなるものである。
前記金属イオンの種類は特に限定されるものではなく、周期表上第8族、第9族、第10族または第11族などに属する遷移金属イオンを用いることができる。例えば、安価で入手が容易であるニッケル及び銅化合物、ポリケトンの収量及び分子量の側面で好ましくは、パラジウム化合物、特に触媒活性及び固有粘度向上の側面で好ましくは、酢酸パラジウムなどから前記金属イオンを構成することができる。好ましい一具体例において、前記金属イオンは周期表上第8族遷移金属イオン、例えば鉄(Fe)、ルテニウム(Ru)、オスミウム(Os)などであり得る。
((2,2−ジメチル−1,3−ジオキサン−5,5−ジイル)ビス(メチレン))ビス(ビス(2−メトキシフェニル)ホスフィン)→F.wt:632.66g/mol
3,3−ビス−[ビス−(2−メトキシフェニル)ホスファニルメチル]−1,5−ジオキサスピロ[5,5]ウンデカン→F.wt:672.73g/mol
触媒組成物において、前記リガンドの使用量は遷移金属化合物対して1〜1.2(モル)当量の範囲であることが、触媒活性、固有粘度、経済的な触媒製造などの側面で好ましい。
触媒組成物において、前記酸の使用量は遷移金属化合物対して6〜20(モル)当量の範囲、前記金属イオン+リガンド:酸のモル比は1:7〜1:20の範囲であることが触媒活性、固有粘度、経済的な触媒製造などの側面で好ましい。
例えば、金属イオン及びリガンド、すなわち((2,2−ジメチル−1,3−ジオキサン−5,5−ジイル)ビス(メチレン))ビス(ビス(2−メトキシフェニル)ホスフィン)から合成した前駆体に酸を添加して本発明の触媒系を構成することができる。また本発明の触媒系は遷移金属化合物、((2,2−ジメチル−1,3−ジオキサン−5,5−ジイル)ビス(メチレン))ビス(ビス(2−メトキシフェニル)ホスフィン)及び酸の陰イオンを含む触媒組成物の形態で提供することもできる。
本発明の他の態様によれば、ビス(2−メトキシフェニル)ホスフィン、5,5−ビス(ブロモメチル)−2,2−ジメチル−1,3−ジオキサン及び水素化ナトリウム(NaH)を用いて((2,2−ジメチル−1,3−ジオキサン−5,5−ジイル)ビス(メチレン))ビス(ビス(2−メトキシフェニル)ホスフィン)を得ることを特徴とするポリケトン重合触媒用リガンドの製造方法を提供する。
本発明のポリケトン重合触媒用リガンドの製造方法は、従来の3,3−ビス−[ビス−(2−メトキシフェニル)ホスファニルメチル]−1,5−ジオキサスピロ[5,5]ウンデカンの合成法とは異なり、リチウムを用いない安全な環境下で容易なプロセスを通じて((2,2−ジメチル−1,3−ジオキサン−5,5−ジイル)ビス(メチレン))ビス(ビス(2−メトキシフェニル)ホスフィン)を商業的に大量合成することができる。
以下、実施例を通じて本発明をより具体的に説明する。しかし、これらの実施例は本発明の理解を助けるためのものに過ぎず、何等の意味でも本発明の範囲がこれらの実施例に限定されるものではない。
2,2−(ブロモメチル)プロパン−1,3−ジオール(1kg、3.8mol)を窒素雰囲気下で4Lのジクロロメタンに溶かした。
2,2−ジメトキシプロパン(596g、5.7mol)を加えた後、内部温度が0〜5℃になるように冷却させた。
内部温度を維持しながら濃い硫酸(7g、18.8mmol)を加えた後、内部温度0〜5℃で5時間撹拌した。
炭酸水素ナトリウム水溶液で2回及び水で洗浄して無水硫酸ナトリウムで乾燥させた後、溶媒を減圧濃縮して望む生成物(1.11kg、96.4%)を得た。
NMR(CDCl3):3.79(s、4H)、3.57(s、4H)、1.41(s、6H)
窒素雰囲気下でビス(2−メトキシフェニル)ホスフィン[Claudio Bianchini、Eur.J.Inorg.Chem.、2005,4794−4800参照](1kg、4.06mol)とジメチルスルホキシド11kgを反応容器に投入して常温で水素化ナトリウム(60%)(325g、8.12mol)を加えた後1時間撹拌した。 5,5−ビス(ブロモメチル)−2,2−ジメチル−1,3−ジオキサン(736g、2.84mol)とジメチルスルホキシド5.5kg混合液をゆっくり加え、2〜4時間撹拌した。
トルエン10Lと水10Lを投入して層分離した後油層を水で2回洗浄した後、無水硫酸ナトリウムで乾燥後減圧濾過を行って減圧濃縮させた。
残留物をメタノール下で再結晶して((2,2−ジメチル−1,3−ジオキサン−5,5−ジイル)ビス(メチレン))ビス(ビス(2−メトキシフェニル)ホスフィン)を得た。
1HNMR(CDCl3):7.26〜7.16(m、8H)、6.87〜6.75(m、8H)、3.92(s、4H)、3.70(s、12H)、2.51(d、4H)、1.44(s、6H)
31PNMR(CDCl3):−46.04
Claims (2)
- ビス(2−メトキシフェニル)ホスフィン、5,5−ビス(ブロモメチル)−2,2−ジメチル−1,3−ジオキサン及び水素化ナトリウムを用いて((2,2−ジメチル−1,3−ジオキサン−5,5−ジイル)ビス(メチレン))ビス(ビス(2−メトキシフェニル)ホスフィン)を得ることを特徴とするポリケトン重合触媒用リガンドの製造方法。
- (A)金属イオン;(B)リガンドとして下記化学式1の((2,2−ジメチル−1,3−ジオキサン−5,5−ジイル)ビス(メチレン))ビス(ビス(2−メトキシフェニル)ホスフィン);及び(C)酸;からなることを特徴とするポリケトン重合触媒に用いられるリガンドの製造方法であって、
(b)得られた混合液に5,5−ビス(ブロモメチル)−2,2−ジメチル−1,3−ジオキサン及びジメチルスルホキシドを加えた後撹拌して反応させる段階;
(c)反応完了後メタノールを投入して撹拌する段階;
(d)トルエン及び水を投入して層分離した後油層を水で洗浄した後、無水硫酸ナトリウムで乾燥後減圧濾過を行って減圧濃縮する段階;及び
(e)残留物をメタノール下で再結晶して((2,2−ジメチル−1,3−ジオキサン−5,5−ジイル)ビス(メチレン))ビス(ビス(2−メトキシフェニル)ホスフィン)を得る段階;
を含む、前記リガンドの製造方法。
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