TW505667B - New compounds having an element of group 11, 12 or 14 and a tridentate ligand, their preparation process and their use in particular as polymerization catalysts - Google Patents
New compounds having an element of group 11, 12 or 14 and a tridentate ligand, their preparation process and their use in particular as polymerization catalysts Download PDFInfo
- Publication number
- TW505667B TW505667B TW087114536A TW87114536A TW505667B TW 505667 B TW505667 B TW 505667B TW 087114536 A TW087114536 A TW 087114536A TW 87114536 A TW87114536 A TW 87114536A TW 505667 B TW505667 B TW 505667B
- Authority
- TW
- Taiwan
- Prior art keywords
- compound
- formula
- group
- alkyl
- scope
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 54
- 239000002685 polymerization catalyst Substances 0.000 title claims abstract description 7
- 239000003446 ligand Substances 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 34
- 125000003118 aryl group Chemical group 0.000 claims abstract description 21
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 16
- -1 haloalkyl radicals Chemical class 0.000 claims abstract description 14
- 125000001424 substituent group Chemical group 0.000 claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 150000002367 halogens Chemical class 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 5
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 5
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 4
- 125000005110 aryl thio group Chemical group 0.000 claims abstract description 4
- 125000000000 cycloalkoxy group Chemical group 0.000 claims abstract description 3
- 125000005366 cycloalkylthio group Chemical group 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract 5
- 229920001577 copolymer Polymers 0.000 claims description 23
- 239000011701 zinc Substances 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 150000002924 oxiranes Chemical class 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229910052800 carbon group element Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052696 pnictogen Inorganic materials 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 125000004437 phosphorous atom Chemical group 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 abstract description 7
- JEVCWSUVFOYBFI-UHFFFAOYSA-N cyanyl Chemical compound N#[C] JEVCWSUVFOYBFI-UHFFFAOYSA-N 0.000 abstract 3
- 150000005840 aryl radicals Chemical class 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 11
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 9
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 8
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 8
- 238000011049 filling Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 6
- 101100167062 Caenorhabditis elegans chch-3 gene Proteins 0.000 description 6
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229920000954 Polyglycolide Polymers 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- 229940098465 tincture Drugs 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MBIQENSCDNJOIY-UHFFFAOYSA-N 2-hydroxy-2-methylbutyric acid Chemical compound CCC(C)(O)C(O)=O MBIQENSCDNJOIY-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XGLOTIMKDGLOKV-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3CC12.[C] Chemical compound C1=CC=CC=2C3=CC=CC=C3CC12.[C] XGLOTIMKDGLOKV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- 229920001244 Poly(D,L-lactide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 240000008866 Ziziphus nummularia Species 0.000 description 1
- GZRDJPGWGMWUQZ-UHFFFAOYSA-N [Re].[Au] Chemical compound [Re].[Au] GZRDJPGWGMWUQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical group [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical group [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 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 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2284—Compounds with one or more Sn-N linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/16—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of silicon, germanium, tin, lead, titanium, zirconium or hafnium
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/266—Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyethers (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Graft Or Block Polymers (AREA)
Description
505667 經淖部中决摞聲局Μ_τ消费合竹社印欠 A7 B7五、發明説明(〖) 本發明偽關於具有第11、12或14族元素及三配位基配 位體之新穎化合物,其製程及其特別作為聚合觸媒之用 1 途。 已知聚合或共聚中所用之觸媒可分別製得不同聚合物 或共聚物,尤為轉酯反應中使立體中心轉換所致 (Jedlinsli等人,Macro Molecules, ( 1 9 9 0 ) 1 9 1 , 2 2 8 7; Manson等人,Macroinolecules, ( 1 9 9 6 ) 2 9, 8 8 4 4; Montaudo 等人,Macroaiolecules, ( 1 9 9 6 ) 2 9, 6 4 6 1 ) 〇 因 而需要新穎觸媒以製得新穎聚合物或共聚物,尤為嵌段 共聚物。可得嵌段共聚物形成所用之觸媒条可允許控制 單體之鏈形成以得具持定性質之待定共聚物。其對生物 相容共聚物尤為有用。因其生物降解可受此鍵形成之影 本發明物傜為下式1産物: ⑴ 式中Μ為第11, 12或14族元素; Α及Β各為具2〜4個磺原子之磺鏈,其可任意取代 以下列己取代(取代以一以上相同或不同取代基)或未取 代基:烷基,環烷基或芳基,其中該取代基為鹵素,烷 基,硝基或m基; Li,L2及L3各為- E15(R1S)-基,其中E1S為第15族 元素且R ^為氫;下列已取代(取代以一以上相同或不同 (^先閱讀背面之注意事項再填寫本頁 4
、1T
本紙张尺度適用中國國家標卒(CNS ) Λ4規格(210Χ297公釐) 505667 A7 B7 五、發明説明(^ ) 取代基)或未取代基:環烷基或芳基,其中該取代基為 鹵素,烷基,硝基或氰基;rr'r’’e14-之基,其中E14為 第1 4族元素且R , R ’及R π各為氫或下列已取代(取代以一 以上相同或不同取代基)或未取代基:烷基,環烷基,芳 基,烷氧基,環烷氣基,芳氯基,烷硫基,環烷硫基或 芳硫基,其中該取代基為鹵素,烷基,硝基或氛基;或 SO^ITis之基,其中ΙΤβ為鹵素,烷基,鹵烷基或芳基 任意取代以一以上選自烷基,鹵烷基及鹵素之取代基。 上述定義中,鹵素為氟,氣,溴或碘,宜為氯。烷基 宜為直鏈或分枝烷基,尤宜為(:1-4烷基,如甲基 ,乙基,丙基,異丙基,丁基,異丁基,第二丁基及第 三丁基。 鹵烷基宜為如上述烷基而取代以一以上如上述鹵素, 如溴乙基,三氟甲基,三氟乙基或五氟乙基。烷氧基中 烷基可如上述。宜為甲氧基,乙氧基,異丙氧基或第三 丁氧基。烷硫基宜含如上述烷基,如甲硫基或乙硫基。 經淆部中次標準局爲工消费合作社印t (讀先閱讀背面之注意事項再填寫本頁) 環烷基傺選自飽和或未飽和單璟環烷基。飽和單環環 烷基可選自含C3 ^之基,如環丙基,璟丁基,環戊基 ,璟己基或環庚基。未飽和環烷基可選自環丁烯基,環 戊烯基,環己烯基,環戊二烯基,環己二烯基。環烷氧 基中環烷基可如上述定義。宜為環丙氧基,環戊氧基或環 己氧基。璟烷硫基中環烷基可如上逑定義,如璟己硫基。 芳基可為單或多環形式,單環芳基可選自苯基任意取 代以一以上烷基,如甲苯基,二甲苯基,三甲苯基,異 本紙張尺度適用中國國家標準(CNS ) Λ4規格(210X297公釐) 505667 部 屮 •λ f: a A7 B7五、發明説明(3 ) 丙苯基。多環芳基可選自萘基,憩基,菲基。芳氧基中 芳基之定義如上。宜為苯氧基,2,4,6-三第三丁苯氧基 ,甲苯氧基或三甲苯氧基。芳硫基中芳基宜如上述定義 ,如苯硫基。 式I化合物可表為單體或二聚物,特言之,式I化合 物中Μ為鋅者常表為二聚物。 特言之,本發明係關於定義如上之式1化合物,其特 色為 Μ為錫或鋅; Α及Β各為C2 ^碳鏈,尤為2個碳原子之碳鐽; Li,匕2及匕3各為- El5(Rl5) -之基,其中ElS為氮或鱗 原子旦R b為R IT R ” E -之基,其中E 14為碳或矽原子且 R , R’及R”各為氮原子或烷基或芳基且宜為氫原子或烷 基。 其中Μ宜為錫或鋅原子;A及B宜為含2個碳原子之 碳鐽;Li,L2及匕3各宜為-E1s(Rb)-之基,其中E15 為氮原子而Rb為RR’ITEm-之基,其中E14為碳或矽原 子且R , R’及R”各為氫或甲基,乙基,丙基或異丙基。 特言之,本發明係關於如下列例子所說明之化合物, 尤為下式之物: 一 [(Me2CHNCH2CH2)2NMe】Sn; -[(Me3SiNCH2CH2)2NMe]Sn ; • [(Me3SiNCH2CH2)2NMe]Zn. 本發明亦關於製備定義如上式I化合物之方法,其特 色為將式I化合物 5 - 本紙弘乂度这州t P扑3家掠卑(rNS )八4规格(210X 297公釐) 許先閱讀背面之注意事項再禎寫本頁 >裝·
、1T 4. 505667 A7 B7 五、發明説明(4 ) (L 1 -A-L a -B-L 2 ) 2—,2Y"· ( I ) 式中Li, A , L 3 , B及L2定義如上且Y為有機金靥 基,金鼷或氫,與式I化合物反應 ΜΖ 1 Ζ 2 ( I ) 式中Μ之定義如上且Zi及22各為離基Κ得定義如上之 式I化合物。 式I化合物亦可表為下列非離子形式 Y - L 1 -A - L>3 -Β-ί·2 當 Y 為氣時,式(I )化合 物一般Μ式I’形式表示。 式I化合物與式Π化合物反應Κ得式1化合物之反應 可於如氟氯展或氬氣之純氣下,如非質子惰性溶劑及-90 至+ 501C下進行。所得化合物可依標準純化方法純化。 非質子惰性溶劑可為芳族烴如苯,甲苯;脂族烴如戊 烷,庚烷,己烷,環己烷;醚如***,二鸣烷,四氫呋 喃,乙基第三丁醚,氯化溶劑如二氯甲烷或氯仿。 化合物I中,Υ為有機金屬基,金鼷或氫。有機金屬 基可為R’”Mi或1Τ”3Μ2之化合物,其中R’”為如上述 之烷基,環烷基,芳基,烷氧基或芳氧基,Mi為鋅或 汞原子而M2為錫或鉛原子;有機金靨基宜為ZnMe,
SnMe a , SnBu 3 ^ PbMe 3 。金屬可為選自鋰,納或鉀之 鹼金鼷或如鎂之鹼土金鼷。 化合物E中,乙1及22各為離基例如如上述之鹵素, 烷基,環烷基,烷氧基,芳基或芳氧基,或為甲磺醯氧 基,笨磺醸氧基,對-甲苯磺醢氧基。 一 6 - 本紙认尺度這⑴十WW家指、枣(CNS ) Λ4規格(21〇X 297公釐) (讀先閱讀背面之注意事項再瑣寫本頁)
V 505667 A7 B7 五、發明説明(5 ) 式I化合物之原料為已知或可由已知化合物製得。其 合成可參見下列文獻:Cloke等人,J· Chen· Soc·, Dalton Trans, (1995)25; Wilkinson及 Stone, Comprehensive Organometa 1 1 ic Chenistry (1982)vol . 1 ,5 57 〇 式ϋ化合物為市售可得或可由精於此藝者熟知方法而 製得。 本發明亦關於使用定義如上之式I化合物為觸媒Μ進 行(共)聚合,即聚合或共聚合。當進行(共)聚合時,本 發明化合物亦可作為鏈起始劑或調節劑。 式1化合物尤可用以進行雜環之聚合。雜環可含一 Μ 上第15及/或16族之雜原子,且大小為3-8員。上式雜 環之例子為環氧化物,硫環氧化物,環酯或磙酯如內酯 ,內_胺及酐。 式1化合物亦可用Κ進行環酷之(共)聚合。環酷之例 子為乳酸及/或羥乙酸之二聚環酷(丙交酯及乙交酯)。 任意或嵌段共聚物可依單體是否於反應起始時引進,或 於反應中依序加入而得。 本發明亦關於製備共聚物,嵌段或任意,或聚合物之 方法,其含引入一以上單體,鐽起始劑,聚合觸媒及任 意聚合溶劑,該製法特色為鏈起始劑及聚合觭媒表為選 自如上述式⑴化合物之相同化合物。 (共)聚合可於溶液或超冷卻下進行。當(共)聚合於溶 液中進行時,反應溶劑可為引入觸媒反應之受質或任一 一Ί 一 本紙队尺度4力]十囚國家標枣(^$)八4規格(210'乂 297公釐) I裝— (謂先閱讀背面之注意事項再填寫本頁 訂 505667 A7 B7 五、發明説明(6 ) 種受質。可使用任何不影響觸媒反應之溶劑。如上逑飽 和或芳族烴,醚,脂族或芳族鹵化物。 反應於室溫至25〇υ下進行;宜為40〜20〇υ。反應期 間為1〜3 0 0小時,宜為1〜7 2小時。 此(共)聚合製法尤適於製得環酯之(共)聚物,尤為乳 酸及/或羥乙酸之二聚環酯。所得羥乙酸乳酸共聚物為 生物可降解,尤利於徐放翳藥組成物。此製法亦尤適於 環氧物之聚合,尤為環氧丙烷。所得聚合物可用以合成 有機液晶或半透膜。 本發明亦關於可由上述製法製得之聚合物或共聚物。 所得ί共)聚物之聚散度(Mw/Mn)可於單體全部轉換後置 反應液於反應溫度而改變。(共)聚物量於製法中僅稍受 影響。此等現象係因分子間或分子内轉酯反應所致 (Kiecheldorf等人,Macromolecules, (1988)21, 286)。 下列實施例可用K闡述上述製法,而本發明範圍不限 於此。 例 l:[Me2 CHNCH 2 CH 2 ) 2 NMe]Sn M = Sn ; A = B = -CH 2 CH 2 L i =L 2 =NCHMe 2 ; L 3 =NMe 將 1.00g(4,7minol )[ (—Me2 CHNCH2 CH2 ) 2 NMe]2-, 2Li+及20ral***依序引至具磁性撹動棒之Schlenk管並 通 Μ 氩氣。冷卻至-78°C 後加入 0,89g(4.7iBinol)SnCl2 之***。回溫至室溫並於室溫下攪拌18小時。遇漶溶液 並蒸除溶劑。可得目的物之黃色油(產率74S:)。分析其 碳,質子及錫之NMR光譜。 一 8 — 本紙尺度这州tW國家掠率() Λ4現格(210X 297公釐) (讀先閱讀背面之注意事項再填寫本頁 -\口 Φ 505667 A7 B7 五、發明説明(7 ) NMR !h (C6D6; 250 MHz): 1.49 (d, JHH = 6.2 Hz, 6H, CHCH3); 1.54 (d, Jhh = 6.2Hz, 6H, CHCH3); 2.11 (s, 3H, Jii9Snc = 20.2 Hz, Jii7Snc= Π.5 Hz, NCH3); 2.37 (m, 4H, CH2); 3.11 (m, 2H, CH2); 3.67 (sept, JHH = 6.2 Hz, 2H, CHCH3) NMR 13C (C6D6; 62.896 MHz): 26.64 (s, CHCH3); 26.93 (s, CHCH3); 49.05 (s, JSnc = 53.5 Hz, NCH3); 54.64 (s, CH2); 55.04 (s, CHCH3); 63.32 (s, CH2). NMR 119Sn (C6D6; 32.248 MHz): 121.13 (v1/2 = 600 Hz). 例 2:[(Me3 S i NCH 2 CH 2 ) 2 HMe] Sn M = Sn ; A = B = -CH 2 CH 2 -; L 1 =L 2 =HS i He 3 ; L 3 =NMe 將1,228(4.7111111〇1)[^351_2(:[12)2,]2' 21丨十及20«|1***依序加至具磁棒之Schlenk管並通K氧 氣。冷卻至-781C後加人含0.89g(4.7«mol)SnCl2之乙 醚。回溫至室溫並於室溫下攪拌2小時。過漶,蒸除溶 劑並處理Μ戊烷。蒸除溶劑後可得桔色油。於甲苯(5ib1) 及-20 υ下结晶可得目的化合物之白色結晶(產率80¾)。 將此化合物K多核磁共振光譜及X-射線繞射分析(下列 第1圖及表1 )。熔點2 0 υ。 例 3:[(Mea SiNCH2 CH2 )2 NHe]Zn(二聚物形式) M = Zn ; A = B = -CH 2 CH 2 -; L 1 =L 2 =HS 1 Me 3 ; L 3 =NMe 將 1 · 1 g ( 4 ♦ 2 in in o 1 ) ( M e 3 S i N H C H 2 C H 2 ) 2 N M e 及 2 0 a 1 甲 苯加至具磁棒之Sch丨enk管並通M氩氣。冷卻至-781 後加入2.1mlZnMe2 (2Μ,4·2·πι〇1)。回溫至室溫後搅拌 3小時。蒸除溶劑。可得暗黃色油。將此油於11〇^下 加熱4小時,將目的物以5ml戊烷洗3次並分離得白色 結晶(產率75X) °將此化合物W KMR光譜及X-射線繞射 -9 一 尺度这家桴率((、奶)八4規格(210'/ 297公釐) ▼裝丨 (謂先閱讀背面之注意事項再硝寫本頁
、1T Φ /4 505667 A7 B7__ 五、發明説明(8 ) 分析(第2圖)。 NMR iH (C6D6; 250 MHz): 0.25 (s,18H, Si(Ctb)3); 〇·3〇 (s,18H,Si(CH3)3); 2.11 (s, 6H, NCH3); 2.24 (m, 8H, CH2); 3.05 (m, 8H, CH2). NMR 13C (CeDe; 50.323 MHz): 3.22 (s, Si(CHVh); 3.28 (s, Si(CH3)3); 44.49 (s, NCH3); 47.66 (s, CH2); 47.72 (s, CH2); 60.31 (s, CH2); 65.91 ( s, CH2). 例4:製備聚(D,L -丙交酯) ,0,08g(0.2lBiB〇l)[(Me3SiNCH2CH2)2NMe]Sn, 6.67g(46.3rarool)D,L-丙交酯及70ml甲苯依序加至具磁 棒之SchUnk管並通W氩氣。於75¾下攪拌2·5小時。 將聚合物以碳及質子之NMR分析;單體轉換率為60S: ° 依 GPCiGel Permea Chromatography)試驗,使用 761〜 400000之聚苯乙烯標準物(PS>校正,此樣本為由聚合物1 具相似(Mw/Mn = l,43)及高分子量(Mv = 62500)而成。 例5 :製備聚(D , L-丙交酷) 將0.028(0.062111111〇1)[,351»{:112(:112)2_]5", 0.621gi43.1min〇nD,L-丙交酯及50团1甲苯依序加至具磁 棒之Schlenk管並通Μ氬氣。於301C下攪拌36小時◊將 聚合物Μ碳及質子之NMR分析;單體轉換率為92¾ 。依 GPC(Gel Permea Chromatography)試驗,使用 761 〜 400000之聚苯乙烯標準物(PS)校正,此樣本為由聚合物 具高分子量(Mw = 34654)而成。 例6:製備嵌段丙交酯/乙交醅)共聚物 將 0 ♦ 0 8 g ( 〇 · 2 1 ro 班 ο 1 ) [ ( M e 3 S i N C Η 2 C Η 2 ) 2 N M e ] S η, 5.00g(34.72mniol)D,L-丙交_及70b丨甲苯依序加至具磁 _ 1 0 - 丨家梢:率((、NS ) Λ4規格(210X297*^^ " ' (許先閱讀背面之注意事項再填寫本頁)
> 505667 A7 B7 五、發明説明(9 棒之Schlenk管中並通W氩氣。於75¾下攪拌4小時。 H-NMR分析顯示單體轉換率高於95¾ 。將1.00g(8.6 mmol)乙交酯加至上述溶液。於75它下攪拌1小時。由 H-NMR分析顯示已形成共聚物。相對於聚丙交酯(5.20 ppm)及聚乙交_(4.8500111)之訊號比例為8/1。依GPC分 析,使用761〜40 00 00之PS標準化校正,可得此共聚物 為高分子量(Mw = 68950)之巨分子(Μν/Μη = 2·35)之混物。 例7:改變(D,L -丙交酯/乙交酯)共聚物之聚散度 將例4製得之共聚物(Mv/Mn = 2.35)置於751C20小時。 GPC分析顯示已增加分散度且維持量不變(Μν/Μη=2.69; Mw = 68850 )。再置於751020小時。GPC分析顯示分散度 已降低而量幾乎維持不變(Mw/Mn = 2,02; Mw = 65659)。於 751下再加熱40小時後可得1.53之聚散度且分子量為 6 2906 〇 例8:製備任意(D,L-丙交酯/乙交酯)共聚物 部 屮 ‘失 1\ 消 f 卬 t (翱先閱讀背面之注意事項再Μ寫本頁
、1T 將 0.08g(0.21_n [(Me 3 SiNCH 2 CH 2 ) 2 NMe]Sn, 4*70g(32*63miaol)D,L-丙交酯及 1.00g(8.61niB〇l)乙交 酯依序加至具磁棒之Schlenk管中並通K氩氣。於178t: 下加熱1.2小時。將聚合物以碳及質子之NMR分析;單 體轉換率為完全。依GPC分析,使用761〜400000之PS 標準化校正,此樣本含聚合物其聚散度(Mv/Mn)為2.24 &分子量(Mw)為21650。 例9:製備任意(D,L-丙交酿/乙交酯)共聚物,其含丙交 酯/乙交酯組成為50/50 一 11- 本紙张尺,度逆$十1,)、]阈家彳:〗:枣(('^$)八4規格(210'/ 297公釐) 505667 A7 B7
五、發明説明(1G 將 0 · 0 1 g ( 〇 · 〇 3 1 ra m ο 1 ) [ ( M e 3 S i H c Η 2 C Η 2 ) 2 N M e ] Ζ η, 5.55g(38.5ra«i〇l)D,L-丙交酯及 1.91g(16.5mmol)乙交酷 依序加至具磁棒之Schlenk管中並通以氩氣。於180¾ 授拌144分。H-HMR分析顯示簞體轉換為7651丙交酯及 100%乙交酯。聚丙交酯(5.20ppm)及聚乙交酷(4·85ρρπι) 之訊號比例評估共聚物組成為46/54。依GPC分析,使 用761〜400000之PS標準化校正得此共聚物為高分子量 (Mw = 36192)巨分子(Mw/Mn = 1.82)之混物。 例10:製備任意(D,L -丙交酯/ Z交酯)共聚物,其為具 有丙交酯/乙交酯組成物為70 / 3〇之高分子量共聚物 將 0 · 0 1 5 g ( 0 · 0 4 6 ro a ο 1 ) [ ( M e 3 S i H C Η 2 C Η 2 ) 2 N M e ] Ζ η, 13*3g(92.4ininol)D,L-丙交酯及 3.U(26.4roffl〇l)乙交酯 依序加至具磁棒之Schlenk管中並通以氬氣。於l80t! 下攪拌5小時。H-NMR分析顯示單體轉換為68¾丙交酯 及100¾乙交酯。聚丙交酯(5.20ρρ»)及聚乙交酯(4·85 ppm)之訊號比例評估共聚物組成為68¾丙交酯及32¾乙 交酯◊依GPC分析,使用761〜400000之PS檷準化校正 得知此共聚物為高分子量(Hw = 71281)巨分子(Mw/Mn = 2 · 30)之混物。 (請先閱讀背面之注意事項再填寫本頁)
,1T Φ 屮 火 λ Λ 印 /1 一12- 本紙张尺度速W十旧阁家標枣(CNS )八4規格(2丨〇χ 297公釐) 505667 A7 B7 五、發明説明(11 ) 表1:例2化合物中選擇鐽結之長度(Γ)及鐽结角度 部 中 lki; .τ >7i f: 卬 t
Sn(l)-N(l) 2.117(6)入 C(4)-C(5) 1.497 (11)人 Sn(l)-N(2) 2.323 (6)入 C(5)-N(2) 1.485 (10) A Sn(l)-N(3) 2.082 (5)人 N(2)-C(6) 1.483 (10)入 N ⑴-Si(l) 1·712 (6)入 N(2)-C ⑺ 1.488 (9)入 N(3)-Si(2) 1.706 (13) A C(7)-C(8) 1.528 (11) A N(l)-C(4) 1.458 (9)入 C(8)-N(3) 1.426 (9)入 N(l)-Sn(l)-N(2) 77.4(2)。 N(2)-Sn(l)-N(3) 79.0 (2) 0 Sn(l)-N(l)-C(4) 116.7 (4)° Sn(l)-N(3)-C(8) 109.4 (4)° N(3)-Sn(l)-N(l) 98·1 (2) 0 一 13- 誚先閱讀背面之注意事項再填寫本頁 i裝·
、1T 本紙依尺度述扣t W囤家標卑((’NS ) Λ4规格(210Χ297公釐) 505667 A7 B7 五、發明説明(12 ) 表2:例3化合物中選擇鍵結之長度(¾)及鍵结角度 ^¾:部中^ir^-^m τ_ 消於合竹.^
Zii⑴-N⑴ 2.105 (2) C(4)-C(5) 1.523 (3) Zn(l)-N(2) 2.239 (2) C(5)-N(2) 1.479 (3) Zn(l)-N(3) 1.907 (2) N(2)-C(6) 1.473 (3) Zn(l)-N(1)A 2.025 (2) N(2)-C ⑺ 1.484 (3) Si(l)-N(l) 1.736 (2) C(8)-N(3) 1.465 (3) N(3)-Si(2) 1,694 (2) C ⑺-C(8) 1.514(3) N ⑴-C(4) 1.492 (2) N(l)-Zn(l)-N(1)A 92.49 (6) N(l)-Zn(l)-N(2) 85.25 (6) N(3)-Zn(l)-N(2) 86.96 (7) C(4)-N(l)-Zn(l) 103.84 (11) C(8)-N(3)-Zn(l) 106.13 (12) N(3)-Zn(l)-N(l) 124.48 (7) Zn(l)-N(l)-Zn(l)A 87.51 (6) CI (請先閱讀背面之注意事項再填寫本頁 、11 Φ -14- 本紙张X度迖《十丨叫囚家掠碑-(CNS ) Λ4規格(210X297公釐)
Claims (1)
- 505667六、申請專利範圍 第871 14536號「具有第11、12或14族元素及三配位基配位 體之新穎化合物,其製程及其特別作爲聚合觸媒之用途」專 利案 (91年8月修正) 六申請專利範圍 1· 一種如下式1之化合物,式中Μ爲第11,12或14族元素; Α及Β各爲具2〜4個碳原子之碳鏈,其可任意取代 以下列已取代或未取代基:烷基,環烷基或芳基,其中 該取代基爲鹵素,烷基,硝基或氰基; 1^丄2及L3各爲-E15(R15)_基,其中E15爲第15族元素 且R15爲氫;下列已取代或未取代基:環烷基或芳基,其 中該取代基爲鹵素,烷基,硝基或氰基;RR’R"E14-之基, 其中E14爲第14族元素且R,R’及R"各爲氫或下列已取代 或未取代基:烷基,環烷基,芳基,烷氧基,環烷氧基, 芳氧基,烷硫基,環烷硫基或芳硫基,其中該取代基爲 鹵素,烷基,硝基或氰基;或S02R’15之基,其中51'15爲 鹵素,烷基,鹵烷基或芳基任意取代以一以上選自烷基, 鹵烷基及鹵素之取代基。 2.如申請專利範圍第1項之式1化合物,其特徵爲: 505667 六、申請專利範圍 Μ爲錫或鉢; Α及Β各爲C2_4碳鏈; 1^丄2及L3各爲-E15(R15)-之基,其中E15爲氮或磷原子且 R15爲RR’R”E14-之基,其中E14爲碳或矽原子且R,R’及 R"各爲氮原子或烷基或芳基且宜爲氫原子或烷基。 3. 如申請專利範圍第2項之式1化合物,其中A及B各爲 2個碳原子之碳鏈。 4. 如申請專利範圍第1項之式1化合物,其特徵爲: Μ爲錫或鋅原子; Α及Β各爲含2個碳原子之碳鏈; 1^丄2及L3各爲-E15(R15)-之基,其中E15爲氮原子而R15 爲RWR"E14-之基,其中E14爲碳或矽原子且R,R·及R” 各爲氫或甲基,乙基,丙基或異丙基。 5. 如申請專利範圍第1項之式1化合物,其爲如下化合物: - [(Me2CHNCH2CH2)2NMe】Sn; -[(Me3SiNCH2CH2)2NMe】Sn; -[(Me3SiNCH2CH2)2NMe] Zn. ο 6· —種製備如申請專利範圍第1項中式1化合物之方法, 其爲將式I化合物 (L1-A-L3-B-L2)2·, 2Y+ ( I ) 式中A,L3, B及L2定義如申請專利範圍第1項所示 且Y爲有機金屬基,金屬或氫,與式Π化合物反應 MZiZ2 (Π) _ -2- 505667 六、申請專利範圍 式中Μ之定義如申請專利範圍第)項所示,I及I各 爲離基, 可得式1化合物。 7. 如申請專利範圍第i項之式丄化合物,可作爲聚合或共 聚合觸媒之用途。 8. 如申請專利範圍第7項之式i化合物,其中該化合物可 用於聚合或共聚合雜環。 9·如申請專利範圍第8項之式丨化合物,其中雜環爲環氧 化物。 10·如申請專利範圍第9項之式1化合物,其中環氧化物爲 環氧丙烷。 11·如申請專利範圍第7項之式1化合物,其中該化合物可 用於聚合或共聚合環酯。 12·如申請專利範圍第11項之式1化合物,其中環酯爲乳酸 及/或羥乙酸之二聚環酯。 13·—種嵌段或任意共聚物或聚合物之製法,其含加入一以 上單體,聚合觸媒及任意聚合溶劑,於室溫及250°C下進 行1〜300小時,該製法特徵爲鏈起始劑及聚合觸媒爲選 自如申請專利範圍第1〜4項中任一項化合物。 14. 如申請專利範圍第13項之製法,其中單體係選自環氧化 物或環酯。 15. 如申請專利範圍第14項之製法,其中環氧化物爲環氧丙 焼。 16.如申請專利範圍第14項之製法’其中環酯爲乳酸及/或羥乙 酸之二聚環酯。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97401621A EP0890575A1 (fr) | 1997-07-08 | 1997-07-08 | Nouveaux composés possédant un élément du groupe 11,12 ou 14 et un ligand tridentate, leur procédé de préparation et leur application notamment comme catalyseurs de polymérisation |
Publications (1)
Publication Number | Publication Date |
---|---|
TW505667B true TW505667B (en) | 2002-10-11 |
Family
ID=8229802
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW087114536A TW505667B (en) | 1997-07-08 | 1998-09-02 | New compounds having an element of group 11, 12 or 14 and a tridentate ligand, their preparation process and their use in particular as polymerization catalysts |
Country Status (14)
Country | Link |
---|---|
US (1) | US6303807B1 (zh) |
EP (2) | EP0890575A1 (zh) |
AR (1) | AR013188A1 (zh) |
AT (1) | ATE225795T1 (zh) |
AU (1) | AU8544298A (zh) |
CA (1) | CA2295874C (zh) |
DE (1) | DE69808634T2 (zh) |
DK (1) | DK0998478T3 (zh) |
ES (1) | ES2185193T3 (zh) |
NO (1) | NO20000049L (zh) |
RU (1) | RU2197494C2 (zh) |
TW (1) | TW505667B (zh) |
WO (1) | WO1999002536A1 (zh) |
ZA (1) | ZA985932B (zh) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6271325B1 (en) | 1999-05-17 | 2001-08-07 | Univation Technologies, Llc | Method of polymerization |
EP1063239A1 (fr) * | 1999-06-25 | 2000-12-27 | Societe De Conseils De Recherches Et D'applications Scientifiques (S.C.R.A.S.) | Nouveaux composés possédant un lanthanide et un ligand tridentate, leur procédé de préparation et leur application notamment comme catalyseurs de polymérisation |
US6380328B1 (en) | 1999-12-10 | 2002-04-30 | Univation Technologies, Llc | Catalyst systems and their use in a polymerization process |
US6274684B1 (en) | 1999-10-22 | 2001-08-14 | Univation Technologies, Llc | Catalyst composition, method of polymerization, and polymer therefrom |
US6265505B1 (en) | 1999-11-18 | 2001-07-24 | Univation Technologies, Llc | Catalyst system and its use in a polymerization process |
US6624107B2 (en) | 1999-10-22 | 2003-09-23 | Univation Technologies, Llc | Transition metal catalyst compounds having deuterium substituted ligand and catalyst systems thereof |
US6417304B1 (en) | 1999-11-18 | 2002-07-09 | Univation Technologies, Llc | Method of polymerization and polymer produced therefrom |
US6271323B1 (en) | 1999-10-28 | 2001-08-07 | Univation Technologies, Llc | Mixed catalyst compounds, catalyst systems and their use in a polymerization process |
US6300438B1 (en) | 1999-10-22 | 2001-10-09 | Univation Technolgies, Llc | Hafnium transition metal catalyst compounds, catalyst systems and their use in a polymerization process |
US6300439B1 (en) | 1999-11-08 | 2001-10-09 | Univation Technologies, Llc | Group 15 containing transition metal catalyst compounds, catalyst systems and their use in a polymerization process |
US6281306B1 (en) * | 1999-12-16 | 2001-08-28 | Univation Technologies, Llc | Method of polymerization |
HU229198B1 (hu) * | 2000-05-15 | 2013-09-30 | Centre Nat Rech Scient | Sztannilén és germilén vegyületek alkalmazása polimerizációs katalizátorként heterociklusos vegyületek polimerizálásánál |
AU2002307982B8 (en) * | 2001-04-10 | 2007-03-29 | Centre National De La Recherche Scientifique (C.N.R.S.) | Use of zinc derivatives as cyclic ester polymerisation catalysts |
US20050009687A1 (en) * | 2003-05-02 | 2005-01-13 | Verkade John G. | Titanium alkoxide catalysts for polymerization of cyclic esters and methods of polymerization |
EP2196486A1 (en) * | 2008-12-12 | 2010-06-16 | Total Petrochemicals Research Feluy | Process to prepare di- and multiblock copolymers |
RU2525235C1 (ru) * | 2013-05-20 | 2014-08-10 | Федеральное государственное бюджетное учреждение "Национальный исследовательский центр "Курчатовский институт" | Способ получения катализатора полимеризации лактонов или поликонденсации альфа-оксикислот |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5344948A (en) * | 1992-02-25 | 1994-09-06 | Iowa State University Research Foundation, Inc. | Single-source molecular organic chemical vapor deposition agents and use |
-
1997
- 1997-07-08 EP EP97401621A patent/EP0890575A1/fr not_active Withdrawn
-
1998
- 1998-07-06 EP EP98936450A patent/EP0998478B1/fr not_active Expired - Lifetime
- 1998-07-06 ES ES98936450T patent/ES2185193T3/es not_active Expired - Lifetime
- 1998-07-06 DK DK98936450T patent/DK0998478T3/da active
- 1998-07-06 ZA ZA9805932A patent/ZA985932B/xx unknown
- 1998-07-06 AT AT98936450T patent/ATE225795T1/de active
- 1998-07-06 WO PCT/FR1998/001433 patent/WO1999002536A1/fr active IP Right Grant
- 1998-07-06 RU RU2000102898/04A patent/RU2197494C2/ru not_active IP Right Cessation
- 1998-07-06 DE DE69808634T patent/DE69808634T2/de not_active Expired - Lifetime
- 1998-07-06 CA CA002295874A patent/CA2295874C/fr not_active Expired - Fee Related
- 1998-07-06 AU AU85442/98A patent/AU8544298A/en not_active Abandoned
- 1998-07-06 US US09/446,793 patent/US6303807B1/en not_active Expired - Lifetime
- 1998-07-07 AR ARP980103294A patent/AR013188A1/es active IP Right Grant
- 1998-09-02 TW TW087114536A patent/TW505667B/zh not_active IP Right Cessation
-
2000
- 2000-01-06 NO NO20000049A patent/NO20000049L/no unknown
Also Published As
Publication number | Publication date |
---|---|
DK0998478T3 (da) | 2003-02-10 |
CA2295874C (fr) | 2009-01-20 |
EP0890575A1 (fr) | 1999-01-13 |
ATE225795T1 (de) | 2002-10-15 |
EP0998478A1 (fr) | 2000-05-10 |
NO20000049D0 (no) | 2000-01-06 |
ZA985932B (en) | 1999-12-06 |
ES2185193T3 (es) | 2003-04-16 |
NO20000049L (no) | 2000-01-06 |
AR013188A1 (es) | 2000-12-13 |
DE69808634T2 (de) | 2003-08-07 |
WO1999002536A1 (fr) | 1999-01-21 |
EP0998478B1 (fr) | 2002-10-09 |
DE69808634D1 (de) | 2002-11-14 |
CA2295874A1 (fr) | 1999-01-21 |
RU2197494C2 (ru) | 2003-01-27 |
AU8544298A (en) | 1999-02-08 |
US6303807B1 (en) | 2001-10-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TW505667B (en) | New compounds having an element of group 11, 12 or 14 and a tridentate ligand, their preparation process and their use in particular as polymerization catalysts | |
Hung et al. | Preparation, characterization, and catalytic studies of magnesium complexes supported by NNO-tridentate Schiff-base ligands | |
Xie et al. | Phosphinimino-amino magnesium complexes: synthesis and catalysis of heteroselective ROP of rac-lactide | |
Poirier et al. | Versatile catalytic systems based on complexes of zinc, magnesium and calcium supported by a bulky bis (morpholinomethyl) phenoxy ligand for the large-scale immortal ring-opening polymerisation of cyclic esters | |
Schwarz et al. | Sulfonamide-supported group 4 catalysts for the ring-opening polymerization of ε-caprolactone and rac-lactide | |
Qian et al. | Amidinate aluminium complexes: synthesis, characterization and ring-opening polymerization of rac-lactide | |
Alonso-Moreno et al. | Discrete heteroscorpionate lithium and zinc alkyl complexes. synthesis, structural studies, and ROP of cyclic esters | |
Sun et al. | Bimetallic lanthanide amido complexes as highly active initiators for the ring-opening polymerization of lactides | |
Gallaway et al. | Ring-opening polymerization of rac-lactide and ε-caprolactone using zinc and calcium salicylaldiminato complexes | |
Liu et al. | A facile route to lithium complexes supported by β-ketoiminate ligands and their reactivity | |
CN109879801A (zh) | 一种含吡啶环的氨基酚氧基锌络合物及其制备方法和应用 | |
Wang et al. | Living ring-opening polymerization of ε-caprolactone catalyzed by β-quinolyl-enamino aluminium complexes: ligand electronic effects | |
Forder et al. | Synthesis and characterisation of aluminium (III) imine bis (phenolate) complexes with application for the polymerisation of rac-LA | |
Wei et al. | Aluminum complexes with Schiff base bridged bis (indolyl) ligands: synthesis, structure, and catalytic activity for polymerization of rac-lactide | |
NO318098B1 (no) | Nye forbindelser som inneholder ett gruppe 13 grunnstoff, bundet med en mono- eller di-anionisk tretannet ligand, fremgangsmate for fremstilling og anvendelse derav som polymerisasjonskatalysatorer | |
Pracha et al. | Syntheses of bis (pyrrolylaldiminato) aluminum complexes for the polymerisation of lactide | |
KR20210023879A (ko) | 신규한 아민 작용화 폴리머 및 제조 방법 | |
JP5738097B2 (ja) | ノルボルネン系重合体の製造方法 | |
JP6246225B2 (ja) | 液状スズ(ii)アルコキシドの製造方法 | |
Wang et al. | Immortal ring-opening polymerization of lactides with super high monomer to catalyst ratios initiated by zirconium and titanium complexes containing multidentate amino-bis (phenolate) ligands | |
Lyubov et al. | Hydrido Complexes of Yttrium and Lutetium Supported by Bulky Guanidinato Ligands [Ln (μ‐H){(Me3Si) 2NC (NCy) 2} 2] 2 (Ln= Y, Lu): Synthesis, Structure, and Reactivity | |
Li et al. | Homoleptic lanthanide amidinate complexes: A single‐component initiator for ring‐opening polymerization of trimethylene carbonate and copolymerization with ϵ‐caprolactone | |
Lamberti et al. | Ring‐opening polymerization of cyclic esters by pincer complexes derived from alkaline earth metals | |
Liu et al. | Synthesis of γ-amidine-functionalized dianionic β-diketiminato lanthanide amides and trianionic β-diketiminato Na/Sm heterobimetallic complexes and their reactivity in polymerization of l-lactide | |
KR101522778B1 (ko) | 고리형 에스테르기를 가진 모노머의 중합체 제조를 위한 비스피라졸릴 리간드를 함유한 아연 착체 촉매, 이의 제조방법 및 이를 이용한 중합체의 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
GD4A | Issue of patent certificate for granted invention patent | ||
MM4A | Annulment or lapse of patent due to non-payment of fees |