WO1997024377A1 - Initiateurs fonctionnalises, pour polymerisation anionique - Google Patents
Initiateurs fonctionnalises, pour polymerisation anionique Download PDFInfo
- Publication number
- WO1997024377A1 WO1997024377A1 PCT/US1996/007625 US9607625W WO9724377A1 WO 1997024377 A1 WO1997024377 A1 WO 1997024377A1 US 9607625 W US9607625 W US 9607625W WO 9724377 A1 WO9724377 A1 WO 9724377A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- propylhahde
- group
- groups
- ethoxy
- Prior art date
Links
- 239000003999 initiator Substances 0.000 title claims abstract description 34
- 238000010539 anionic addition polymerization reaction Methods 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 47
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 35
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 23
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 21
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 14
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 14
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 14
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 14
- 125000004663 dialkyl amino group Chemical group 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 97
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 26
- 150000004820 halides Chemical class 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- -1 diene hydrocarbons Chemical group 0.000 claims description 20
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 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 claims description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 12
- 238000010511 deprotection reaction Methods 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 239000000017 hydrogel Substances 0.000 claims description 5
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- RHDYQUZYHZWTCI-UHFFFAOYSA-N 1-methoxy-4-phenylbenzene Chemical compound C1=CC(OC)=CC=C1C1=CC=CC=C1 RHDYQUZYHZWTCI-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 claims description 3
- QTYUSOHYEPOHLV-FNORWQNLSA-N 1,3-Octadiene Chemical compound CCCC\C=C\C=C QTYUSOHYEPOHLV-FNORWQNLSA-N 0.000 claims description 3
- 239000005046 Chlorosilane Substances 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- TXSMUPJUALCAEE-UHFFFAOYSA-M chlorostannane Chemical compound [SnH3]Cl TXSMUPJUALCAEE-UHFFFAOYSA-M 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 229920001002 functional polymer Polymers 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- RZIHIJJOVJRDTA-UHFFFAOYSA-N 1,5-diazabicyclo[3.1.0]hexane Chemical compound C1CCN2CN21 RZIHIJJOVJRDTA-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- PJXJBPMWCKMWLS-UHFFFAOYSA-N 2-methyl-3-methylidenepent-1-ene Chemical compound CCC(=C)C(C)=C PJXJBPMWCKMWLS-UHFFFAOYSA-N 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 2
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 claims description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 3
- BOGRNZQRTNVZCZ-AATRIKPKSA-N (3e)-3-methylpenta-1,3-diene Chemical compound C\C=C(/C)C=C BOGRNZQRTNVZCZ-AATRIKPKSA-N 0.000 claims 2
- BOGRNZQRTNVZCZ-UHFFFAOYSA-N 1,2-dimethyl-butadiene Natural products CC=C(C)C=C BOGRNZQRTNVZCZ-UHFFFAOYSA-N 0.000 claims 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 2
- WFJQGQNVERCLOQ-AATRIKPKSA-N (3e)-2,5-dimethylhexa-1,3-diene Chemical compound CC(C)\C=C\C(C)=C WFJQGQNVERCLOQ-AATRIKPKSA-N 0.000 claims 1
- DZPCYXCBXGQBRN-UHFFFAOYSA-N 2,5-Dimethyl-2,4-hexadiene Chemical compound CC(C)=CC=C(C)C DZPCYXCBXGQBRN-UHFFFAOYSA-N 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 239000012948 isocyanate Substances 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims 1
- 150000002924 oxiranes Chemical class 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 18
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 100
- 239000011541 reaction mixture Substances 0.000 description 55
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 54
- 229910052786 argon Inorganic materials 0.000 description 50
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 44
- 239000000243 solution Substances 0.000 description 35
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 33
- 239000000047 product Substances 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000001816 cooling Methods 0.000 description 23
- 235000011089 carbon dioxide Nutrition 0.000 description 20
- 238000004817 gas chromatography Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 18
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 10
- 125000006239 protecting group Chemical group 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000003556 assay Methods 0.000 description 8
- 229920001400 block copolymer Polymers 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000002480 mineral oil Substances 0.000 description 8
- 235000010446 mineral oil Nutrition 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- 150000001993 dienes Chemical class 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- 239000012230 colorless oil Substances 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- CAZPRAORHCOIHC-UHFFFAOYSA-N 3-chloro-2,2-dimethylpropan-1-ol Chemical compound OCC(C)(C)CCl CAZPRAORHCOIHC-UHFFFAOYSA-N 0.000 description 5
- LAMUXTNQCICZQX-UHFFFAOYSA-N 3-chloropropan-1-ol Chemical compound OCCCCl LAMUXTNQCICZQX-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- WHVMPBIIYDTYRE-UHFFFAOYSA-N 2-(3-chloropropoxy)-2-methylpropane Chemical compound CC(C)(C)OCCCCl WHVMPBIIYDTYRE-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 239000003518 caustics Substances 0.000 description 4
- 230000008034 disappearance Effects 0.000 description 4
- 239000003517 fume Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229940117927 ethylene oxide Drugs 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000003944 halohydrins Chemical class 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 2
- IZIZQJPZVYKTIA-UHFFFAOYSA-N 1-butan-2-yloxy-4-chlorobutane Chemical compound CCC(C)OCCCCCl IZIZQJPZVYKTIA-UHFFFAOYSA-N 0.000 description 2
- FPNFOQVRVRZNIG-UHFFFAOYSA-N 1-chloro-2,2-dimethyl-3-(2-methylbutan-2-yloxy)propane Chemical compound CCC(C)(C)OCC(C)(C)CCl FPNFOQVRVRZNIG-UHFFFAOYSA-N 0.000 description 2
- BYCYKPPUAUXFOQ-UHFFFAOYSA-N 1-chloro-2,2-dimethyl-3-[(2-methylpropan-2-yl)oxy]propane Chemical compound CC(C)(C)OCC(C)(C)CCl BYCYKPPUAUXFOQ-UHFFFAOYSA-N 0.000 description 2
- QEKQJFRPPXTQSM-UHFFFAOYSA-N 1-chloro-3-methoxybutane Chemical compound COC(C)CCCl QEKQJFRPPXTQSM-UHFFFAOYSA-N 0.000 description 2
- DFLRARJQZRCCKN-UHFFFAOYSA-N 1-chloro-4-methoxybutane Chemical compound COCCCCCl DFLRARJQZRCCKN-UHFFFAOYSA-N 0.000 description 2
- KDHGXSOYHUAMEO-UHFFFAOYSA-N 1-chloro-4-propan-2-yloxybutane Chemical compound CC(C)OCCCCCl KDHGXSOYHUAMEO-UHFFFAOYSA-N 0.000 description 2
- SVZJAZVDSAINFO-UHFFFAOYSA-N 2-(3-chloropropoxy)-2-methylbutane Chemical compound CCC(C)(C)OCCCCl SVZJAZVDSAINFO-UHFFFAOYSA-N 0.000 description 2
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- OGQVROWWFUXRST-FNORWQNLSA-N (3e)-hepta-1,3-diene Chemical compound CCC\C=C\C=C OGQVROWWFUXRST-FNORWQNLSA-N 0.000 description 1
- 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 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 description 1
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical class C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- HMWCQCYUKQZPRA-UHFFFAOYSA-N 2,4-dimethyl-3-methylidenepent-1-ene Chemical compound CC(C)C(=C)C(C)=C HMWCQCYUKQZPRA-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- BUWXUSLQPDDDSD-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-yloxy)butane Chemical class CCC(C)(C)OC(C)(C)CC BUWXUSLQPDDDSD-UHFFFAOYSA-N 0.000 description 1
- KUFLEYZWYCAZCC-UHFFFAOYSA-N 2-methylhexa-1,3-diene Chemical compound CCC=CC(C)=C KUFLEYZWYCAZCC-UHFFFAOYSA-N 0.000 description 1
- QTTAWIGVQMSWMV-UHFFFAOYSA-N 3,4-dimethylhexa-1,3-diene Chemical compound CCC(C)=C(C)C=C QTTAWIGVQMSWMV-UHFFFAOYSA-N 0.000 description 1
- QXNYNMNRJMHGHH-UHFFFAOYSA-N 3-ethyl-2-methylpenta-1,3-diene Chemical compound CCC(=CC)C(C)=C QXNYNMNRJMHGHH-UHFFFAOYSA-N 0.000 description 1
- CTNXNQQXFSVMIY-UHFFFAOYSA-N 3-ethylidenehex-1-ene Chemical compound CCCC(=CC)C=C CTNXNQQXFSVMIY-UHFFFAOYSA-N 0.000 description 1
- GITIYCQMJWQMKC-UHFFFAOYSA-N 3-methylhepta-1,3-diene Chemical compound CCCC=C(C)C=C GITIYCQMJWQMKC-UHFFFAOYSA-N 0.000 description 1
- OCTVDLUSQOJZEK-UHFFFAOYSA-N 4,5-diethylocta-1,3-diene Chemical compound CCCC(CC)C(CC)=CC=C OCTVDLUSQOJZEK-UHFFFAOYSA-N 0.000 description 1
- SALPZWUZFRNPQX-UHFFFAOYSA-N 4,5-dimethylideneoctane Chemical compound CCCC(=C)C(=C)CCC SALPZWUZFRNPQX-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- UGWOAPBVIGCNOV-UHFFFAOYSA-N 5-ethenyldec-5-ene Chemical compound CCCCC=C(C=C)CCCC UGWOAPBVIGCNOV-UHFFFAOYSA-N 0.000 description 1
- SUJWMMYTMBMNMU-UHFFFAOYSA-N 5-methylidenehept-3-ene Chemical compound CCC=CC(=C)CC SUJWMMYTMBMNMU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- VJDOYHPMXIRCCW-UHFFFAOYSA-N [1-chloropropoxy(diphenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OC(Cl)CC)C1=CC=CC=C1 VJDOYHPMXIRCCW-UHFFFAOYSA-N 0.000 description 1
- UTWQPORNJDITNO-UHFFFAOYSA-N [Li]CC(C)(C)COC(C)(C)C Chemical compound [Li]CC(C)(C)COC(C)(C)C UTWQPORNJDITNO-UHFFFAOYSA-N 0.000 description 1
- NOYJNZYBGPNSBH-UHFFFAOYSA-N [Li]CC(C)(C)COC(C)(C)CC Chemical compound [Li]CC(C)(C)COC(C)(C)CC NOYJNZYBGPNSBH-UHFFFAOYSA-N 0.000 description 1
- JLPGUVPPKHLBKV-UHFFFAOYSA-N [Li]CCC(C)OC Chemical compound [Li]CCC(C)OC JLPGUVPPKHLBKV-UHFFFAOYSA-N 0.000 description 1
- LZUOCRSEJJGPRH-UHFFFAOYSA-N [Li]CCCCOC Chemical compound [Li]CCCCOC LZUOCRSEJJGPRH-UHFFFAOYSA-N 0.000 description 1
- XKLGVKKVTBLVFN-UHFFFAOYSA-N [Li]CCCCOC(C)C Chemical compound [Li]CCCCOC(C)C XKLGVKKVTBLVFN-UHFFFAOYSA-N 0.000 description 1
- WRQMIMNWNUSCGC-UHFFFAOYSA-N [Li]CCCCOC(C)CC Chemical compound [Li]CCCCOC(C)CC WRQMIMNWNUSCGC-UHFFFAOYSA-N 0.000 description 1
- XABRKAWXGPVVDY-UHFFFAOYSA-N [Li]CCCOC(C)(C)C Chemical compound [Li]CCCOC(C)(C)C XABRKAWXGPVVDY-UHFFFAOYSA-N 0.000 description 1
- WHCOMNUPCDVDIB-UHFFFAOYSA-N [Li]CCCOC(C)(C)CC Chemical compound [Li]CCCOC(C)(C)CC WHCOMNUPCDVDIB-UHFFFAOYSA-N 0.000 description 1
- WLLIXJBWWFGEHT-UHFFFAOYSA-N [tert-butyl(dimethyl)silyl] trifluoromethanesulfonate Chemical compound CC(C)(C)[Si](C)(C)OS(=O)(=O)C(F)(F)F WLLIXJBWWFGEHT-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005376 alkyl siloxane group Chemical group 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- OJZNZOXALZKPEA-UHFFFAOYSA-N chloro-methyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(C)C1=CC=CC=C1 OJZNZOXALZKPEA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- HASGOCLZFTZSTN-UHFFFAOYSA-N cyclohexane;hexane Chemical compound CCCCCC.C1CCCCC1 HASGOCLZFTZSTN-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 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
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
-
- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/02—Lithium compounds
-
- 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
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
Definitions
- This invention concerns novel anionic initiators for use in polymerizing olefinic-containing monomers, a process for making the anionic initiators, a process for the polymerization of olefinic-containing monomers using the anionic initiators of this invention and polymers produced by this polymerization process.
- Useful polymeric products are obtained by polymerizing olefinic- containing monomers in the presence of an organo-alkali metal initiator and subsequently reacting the resulting polymer, containing an active alkali metal end group or groups, with a reagent which will couple the polymer molecules or replace the alkali metal with more stable reactive end groups.
- Monofunctional silyl ether initiators containing alkali metal end groups useful in effecting such polymerization reactions are disclosed in Great Britain published patent application 2,241 ,239, published August 28, 1991. These monofunctional silyl ether initiators were demonstrated to be useful in producing polydienes having desirable characteristics such as a molecular weight of typically 1 ,000 to 10,000, 1 -4 content of typically 90%, etc.
- the present invention provides a process for the preparation of novel, hydrocarbon solutions of monofunctional ether initiators of the following general structure:
- M is defined as an alkali metal, preferably lithium
- Z is a branched or straight chain hydrocarbon tether group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups
- R 1 R ⁇ and R 3 are independently defined as H, alkyl, substituted alkyl groups containing lower alkoxy, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkoxy, lower alkylthio, and lower dialkylamino groups, and their employment as initiators in the anionic polymerization of olefin containing monomers in an inert, hydrocarbon solvent, optionally containing a Lewis Base.
- the process reacts selected protected omega-protected- 1-haloalkyls whose alkyl groups contain 3 to 25 carbon atoms, which are reacted with lithium metal in a liquid alkane, cycloalkane or aryl solvent, at a temperature between about 35° C and about 130° C.
- the initiator precursor omega-protected 1-haloalkyls (halides) are prepared from the corresponding haloalcohol by the standard literature methods.
- 3-(1 ,1-dimethylethoxy)-1-chloropropane is synthesized by the reaction of 3-chloro-1 -propanol with 2-methylpropene according to the method of A. Alexakis, M. Gardette, and S. Colin, Tetrahedron Letters, 29, 1988, 2951.
- triphenylmethoxy-l-chloropropane are prepared by the reaction of the haloalcohol with triphenylmethylchioride, according to the method of S. K. Chaudhary and O. Hernandez, Tetrahedron Letters, 1979, 95.
- the compound 4-(methoxy)-1-chlorobutane, and the higher analogues are synthesized by the ring opening reaction of tetrahydrofuran with thionyl chloride and methanol, according to the procedure of T. Ferrari and P. Vogel, SYNLETT, 1991 , 233.
- Monofunctional ether initiators (I) are prepared in accord with the process of this invention and such compounds can include, but are not limited to, 3-(1 ,1-dimethylethoxy)-1 -propyllithium, 5-(1 ,1-dimethylethoxy)-l- pentyllithium, 3-(1 ,1-dimethylethoxy)-2,2-dimethyl-1 -propyllithium, 4-(1 ,1- dimethylethoxy)-1-butyllithium, 6-(1 ,1 -dimethylethoxy)-1-hexyllithium, 8- (1 ,1-dimethylethoxy)-1-octyllithium, 4-(ethoxy)-1-butyllithium, 4-(1- propyloxy)-1 -butyllithium, 4-(1 -methylethoxy)-1 -butyllithium, 3- (triphenylmethoxy)-2,2-dimethyl-1 -propyllithium, 4-(
- Lithium metal used in preparing the monofunctional ether initiators (I) is used as a dispersion whose particle size usually does not exceed about 300 microns. Preferably the particle size is between 10 and 300 microns although coarser particle size lithium can be used.
- the lithium metal can contain 0.2 to 0.8 and preferably 0.3 to 0.5 weight percent sodium. The lithium metal is used in amounts of 90% of theoretical to a 40% excess above the theoretical amount necessary to produce the monofunctional ether initiators (I).
- the preferred reaction temperatures vary from compound to compound, with each compound tending to have its own preferred reaction conditions.
- the preferred reacton temperature/condition is the reflux temperature of the solvent.
- the preferred reaction temperature is in the range of 35 to 80° C.
- Solvents useful in practicing this invention include but are not limited to inert liquid alkanes, cycloalkanes and aryl solvents such as alkanes and cycloalkanes containing five to 10 carbon atoms such as pentane, hexane cyclohexane.methylcyclohexane, heptane, methylcycloheptane, octane, decane and so forth and aryl solvents containing six to ten carbon atoms such as toluene, ethylbenzene, p- xylene, m-xylene, o-xylene, n-propylbenzene, isopropylbenzene, n- butylbenzene.and the like.
- Advantages of using the compounds containing the protecting groups of this invention comprising the process of producing a lithium initiator and subsequently in using the said initiator to produce polymers containing the said protecting groups as compared to using substituted silyl protecting groups are as follows: 1) cheaper and more readily available raw materials are used in the preparation of initiators, e.g. inexpensive olefins such as isobutylene or isoamylene are reacted with omega halo-alcohol as compared to the use of the more expensive alkyl chlorosilanes, such as tert-butvldimethylchlorosilane or diphenylmethylchlorosilane.
- the protecting groups of this invention can be removed in as many ways and as simply as any of the substituted silyl protecting groups.
- a tert-butyl protecting group on a hydroxy terminated polymer can be removed with a) anhydrous triflic acid b) HBr in acetic acid c) HCl in dioxane d) acetic anhydride in ethyl ether ( FeCI3 catalyst ) e) TiCI4 in CH2CI2 ( T.W.
- the by-product of the deprotection reaction of the tert-butyl protected hydroxypolymer is isobutylene, which is innocuous and does not require removal from the polymer, although it can be removed easily at temperatures above 100 degrees C during deprotection ( see US 4,886, 446).
- the by-product of the deprotection of an alkylsilyl protected hydroxy polymer is an alkylsiloxane which is a contaminant that may require removal from the polymer.
- Anionic polymerizations employing the herein described monofunctional ether initiators of this invention are conducted in an inert solvent, preferably a non-polar solvent, optionally containing an ethereal modifier, using an olefinic monomer which is an alkene or a 1 ,3-diene at a temperature of about -30° C to about +100° C.
- the polymerization reaction proceeds from initiation to propagation and finally termination so that the polymer is mono-functional or dysfunctional terminated.
- the polymers have molecular weight ranges of about 1000 to 10,000. Typically 5 to 50 milli-moles of initiator is used per mole of monomer.
- the present invention also provides a process for the anionic polymerization of anionically pollymerizable monomers comprising the steps of: a) initiating polymerization of a conjugated diene hydrocarbon monomer or an alkenylsubstituted aromatic hydrocarbon monomer in a hydrocarbon or mixed hydrocarbon-polar solvent medium at a temperature of 10 °C to 70° C with an initiator having the formula:
- M-Z-OC(R 1 R R 3 ) (II) wherein M is an alkali metal, preferably lithium, Z is a branched or straight chain hydrocarbon tether or connecting group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups; and R 1 , R 2 , and R 3 are independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkoxy, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkoxy, lower alkylthio, and lower dialkylamino groups to produce an intermediate polymer of formula Li-(Q)m-Z-OC(R 1 R 2 R 3 ) wherein Q is a unit of polymerized conjugated diene or alkenylsubstituted aromatic hydrocarbon and Z, R 1 R 2 and R 3 have the meanings ascribed above, m is the number of units ot the polymerized conjugated diene or alkeny
- the olefinic monomer to be anionically polymerized by the monofunctional ether initiator is preferably a conjugated diene or an alkenylaromatic hydrocarbon.
- the conjugated diene or alkenylaromatic compound will be chosen from the group of unsaturated organic compounds that can be polymerized anionically (i.e., in a reaction initiated by an organo- alkali metal).
- Suitable alkenylaromatics include the optionally-substituted styrenes and vinylnaphthalenes.
- Alkenylsubstituted aromatic hydrocarbons useful in practicing this invention include but are not limited to styrene, alpha-methylstyrene, vinyltoluene, 1 - vinylnapthalene, 3-methylstyrene, 4-methylstyrene, 1 ,1 -diphenylethylene and the like.
- Suitable 1 ,3-dienes will preferably contain from 4 to 12, especially from 4 to 8, carbon atoms per molecule.
- Examples of these compounds include, but are not limited to, the following : 1 ,3-butadiene, isoprene; 2,3-dimethyl-1 ,3-butadiene, 1 ,3-pentadiene, 2-methyl-3-ethyl- 1 ,3-butadiene, 2-methyl-3-ethyl-1 ,3-pentadiene, 1 ,3-hexadiene, 2-methyl- 1 ,3-hexadiene, 1 ,3-heptadiene, 3-methyl-1 ,3-heptadiene, 1 ,3-octadiene, 3-butyl-1 ,3-octadiene, 3,4-dimethyl-1 ,3-hexadiene; 3-n-propyl-1 ,3- pentadiene, 4,5-diethyl-1 ,3-octadiene, 2,4-diethyl-1 ,3-butadiene, 2,3-di-n- propy
- the alkyl groups contain from 1 to 3 carbon atoms.
- the above monomers 1 ,3-butadiene, isoprene, 2,3-dimethyl-1 ,3-butadiene and 1 ,3-pentadiene are preferred with 1 ,3-butadiene being particularly preferred.
- the dienes may be polymerised alone, or in admixture with each other or with alkenylaromatic compounds *o form random copolymers, or by charging the dienes to the reaction mixture sequentially, either with each other or with alkenylaromatic compounds, to form block copolymers.
- a protected functional living polymer of this invention can be generated by polymerizing 1 ,3-butadiene with an initiator of formula I above, wherein M is lithium, Z is a trimethylene tether or connecting group, and R 1 , R 2 , and R 3 are methyl groups.
- a living polymer is produced having the formula
- HOCH2CH2-(B)m-(CH2)3-0-C(CH3)3 which may optionally be hydrogenated to the corresponding asymmetric polymer.
- other asymmetrically difunctional polymers may be produced by reacting the living polymer (III) above with, for example, carbon dioxide to produce, a polymer with one protected hydroxyl and one carboxyl group, or the living polymer III may be reacted with 1 ,5 diazabicyclo-(3.1.0) hexane as described in US 4,753,991 to produce a polymer with one protected hydroxyl and one amino group.
- asymmetrically substituted monofunctional polymers may be produced having epoxy or isocyanate groups at one end for example by reacting the lithium salt of IV above (before hydrolysis), with epichlorohydrin or, by reacting IV itself with an equivalent of a diisocyanate, such as methylene 4,4-diphenyl diisocyante (2/1 NCO/OH).
- a diisocyanate such as methylene 4,4-diphenyl diisocyante (2/1 NCO/OH.
- the protective group of the hydrogenated polymer is removed as well, allowing the exposed hydroxyl grouping in the base polymer molecule to simultaneously participate in the block copolymer reaction.
- hydrogenated IV polymers may be reacted with bisphenol A and phosgene in the presence of appropriate catalysts with simultaneous deprotection to yield a polycarbonate alternating block copolymer.
- the resulting products are useful as molding resins, for example, to prepare interior components for automobiles.
- a segmented polyamide-hydrogenated IV block copolymer also useful as a molding composition to prepare exterior automotive components can be prepared by reacting hydrogenated IV polymer with caprolactam and adipic acid in the presence of a suitable catalyst.
- a segmented polyester-hydrogenated IV block copolymer can be produced by reaction of hydrogenated IV polymer with dimethyl terephthalate and a suitable acidic catalyst. Again, the products are useful as molding compounds for exterior automotive components.
- Isocyanate-terminated prepolymers can be produced from hydrogenated IV polymers by reaction with suitable diisocyanates (2/1 NCO/OH) as above which can be further reacted with diols and additional diisocyanates to form segmented polyurethanes useful for water based, low VOC coatings. Or segmented polyurethane prepolymers may be mixed with tackifying resins and used as a moisture-curable sealant, caulk or coating.
- An acrylate-terminated prepolymer curable by free-radical processes can be prepared from the hydrogenated IV polymer by reaction with a diisocyanate (2NCO/OH) followed by further reaction with hydroxyethyl acrylate in the presence of a basic reagent.
- the protected monohydroxy terminated polymer (IV) may be reacted with functional comonomers, wihout simultaneously removing the protective group, to produce novel copolymers. These copolymers may be deprotected and then further reacted with the same or different comonomers to form yet other novel copolymers.
- the hydroxyterminated polymer of formula (IV) may be hydrogenated, and then reacted with ethylene oxide in the presence of potassium tert-butoxide to produce a poly(ethleneoxide)-hydrogenated polybutadiene copolymer with one protected hydroxyl group on the polybutadiene segment. This hydroxyl can then be deprotected and a poly(ethyleneoxide) polymer having different chain lengths grown onto both ends of the polybutadiene segment.
- the living polymer III may be reacted with an alkenylarylhalosilane such as styrenyldimethylchlorosilane to yield the corresponding omega-styrenylterminated macromonomer according to directions in US5,278,244 which may be further polymerized by a variety of techniques to yield "comb" polymers which, on deprotection and hydrogenation yield branched polymers with hydroxyfunctionality on the branch-ends.
- Such multi-functionality can be utilized to graft a water- soluble polymer such as polyethylene oxide onto a hydrophobic polyolefinic core to produce hydrogels.
- Li(B)x(S)y(CH2)3-OC(CH3)3 where B is polymerized butadiene, S is polymerized styrene and x and y can vary from 10 to 1000 or more is reacted with divinylbenzene (DVB) to produce a multi-armed star polymer, according to US4,409,357 which on hydrogenation and deprotection would yield a star with hydroxy-functional branches which may be further reacted with ethylene oxide and potassium alkoxide as described above to produce hydrogels.
- B polymerized butadiene
- S polymerized styrene
- x and y can vary from 10 to 1000 or more is reacted with divinylbenzene (DVB) to produce a multi-armed star polymer, according to US4,409,357 which on hydrogenation and deprotection would yield a star with hydroxy-functional branches which may be further reacted with ethylene oxide and potassium alkoxide as described above to produce hydrogels.
- the hydrogenated hydroxyterminated branches of the star polymer may be further reacted with acryloyl chloride or methacryloyl chloride, and the resultant acrylate or methacrylate-terminated polymer further polymerized with monomers selected from the group of alkyl acrylates, alkyl methacrylates, and dialkylacrylainides to produce hydrogels.
- Star polymers are useful as viscosity index improver for motor oils.
- the resultant lithium dispersion was dried in a stream of argon, weighed (4.07 grams, 0.586 mole, 2.80 equivalents), and transferred to the reaction flask with 150 ml of cyclohexane.
- the reaction mixture was stirred at 450 RPMs, and heated to 70° C with a heating mantle. The heat source was removed.
- 1- Chloro-3-(1 ,1-dimethylethoxy)-propane, 31.52 grams, (0.209 mole, 1.00 equivalent, lot 8864) was added dropwise via the addition funnel. An exotherm was detected after 5.5% of the halide feed had been added.
- a dry ice/hexane cooling bath was applied as needed to maintain the reaction temperature between 60-65° C.
- the total halide feed time was fifty-two minutes.
- the cooling bath was removed at the end of the halide feed.
- the reaction temperature fell off rapidly to room temperature.
- the reaction mixture was stirred for one hour at 450 RPMs, and two and one half hours at 300 RPMs.
- the reaction mixture was transferred with argon pressure to a dry sintered glass pressure filter.
- the product solution was pressure filtered with 3 psi (20.68 x 10 3 Pa) argon.
- the lithium chloride muds were reslurried with fresh cyclohexane (2 X 50 ml.).
- Total Base 3.85 wt. %.
- the total yield was 47.6 %.
- the resultant lithium dispersion was dried in a stream of argon, weighed (4.40 grams, 0.634 mole, 2.80 equivalents), and transferred to the reaction flask with 200 ml of cyclohexane.
- the reaction mixture was stirred at 450 RPMs, and heated to 65° C with a heating mantle. The heat source was removed.
- 1- Chloro-3-(1 , 1 -dimethylethoxy)-2,2-dimethyl-propane, 40.42 grams, (0.226 mole, 1.00 equivalent, lot 8913) was added dropwise via the addition funnel. An exotherm was detected after 12.8% of the halide feed had been added.
- a dry ice/hexane cooling bath was applied as needed to maintain the reaction temperature between 60-65° C.
- the total halide feed time was one hour.
- the cooling bath was removed at the end of the halide feed.
- the reaction temperature fell off rapidly to room temperature.
- the reaction mixture was stirred for eighty minutes at 450 RPMs.
- the reaction mixture was then transferred with argon pressure to a dry sintered glass pressure filter.
- the product solution was pressure filtered with 3 psi (20.68 x 10 3 Pa) argon.
- the lithium chloride muds were reslurried with fresh cyclohexane (2 X 40 ml.).
- a one liter, three-necked, Morton flask was fitted with a mechanical stirrer, a 125 ml pressure-equalizing addition funnel, and a Claisen adapter equipped with a thermocouple, a dry ice condenser, and an argon inlet.
- This apparatus was dried in an oven overnight at 125° C, assembled hot, and allowed to cool to room temperature in a stream of argon.
- Lithium metal dispersion, lot 8899, 0.43% sodium, was washed free of mineral oil with hexane (2 X 100 ml), and pentane (1 X 100 ml).
- the resultant lithium dispersion was dried in a stream of argon, weighed (6.35 grams, 0.915 mole, 3.67 equivalents), and transferred to the reaction flask with 180 ml of cyclohexane.
- the reaction mixture was stirred at 450 RPMs, and heated to 65° C with a heating mantle. The heat source was removed.
- 1- Chloro-3-(1 ,1-dimethylpropyloxy)-propane, 41.00 grams, (0.249 mole, 1.00 equivalent, lot 9118, 9134) was added dropwise via the addition funnel. An exotherm was detected after 13% of the feed had been added.
- a dry ice/hexane cooling bath was applied as needed to maintain the reaction temperature between 60-65° C.
- the total halide feed time was sixty-five minutes.
- the cooling bath was removed at the end of the halide feed.
- the reaction temperature fell off gradually to room temperature.
- the reaction mixture was stirred for one hour at 450 RPMs, and one hour at 300 RPMs.
- the reaction mixture was transferred with argon pressure to a dry sintered glass pressure filter.
- the product solution was pressure filtered with 3 psi (20.68 x 10 3 Pa) argon.
- the lithium chloride muds were reslurried with fresh cyclohexane (2 X 50 ml.).
- Total Base 6.32 wt. %.
- Active C-Li 5.01 wt.
- a one liter, three-necked, Morton flask was fitted with a mechanical stirrer, a 125 ml pressure-equalizing addition funnel, and a Claisen adapter equipped with a thermocouple, a dry ice condenser, and an argon inlet.
- This apparatus was dried in an oven overnight at 125° C, assembled hot, and allowed to cool to room temperature in a stream of argon.
- Lithium metal dispersion, lot 8899, 0.43% sodium, was washed free of mineral oil with hexane (2 X 100 ml), and pentane (1 X 100 ml).
- the resultant lithium dispersion was dried in a stream of argon, weighed (3.33 grams, 0.480 mole, 2.86 equivalents), and transferred to the reaction flask with 150 ml of cyclohexane.
- the reaction mixture was stirred at 450 RPMs, and heated to 65° C with a heating mantle. The heat source was removed.
- 1- Chloro-3-(1 ,1 -dimethylpropyloxy)-2,2-dimethyl-propane, 33.00 grams, (0.168 mole, 1.00 equivalent, lot 9152) was added dropwise via the addition funnel. An exotherm was detected after 22% of the halide feed had been added.
- a dry ice/hexane cooling bath was applied as needed to maintain the reaction temperature between 60-65° C.
- the total halide feed time was fifty-three minutes.
- the cooling bath was removed at the end of the halide feed.
- the reaction temperature fell off gradually to room temperature.
- the reaction mixture was stirred for forty-five minutes at 450 RPMs, and seventy-five minutes at 300 RPMs.
- the reaction mixture was transferred with argon pressure to a dry sintered glass pressure filter.
- the product solution was pressure filtered with 3 psi (20.68 x 10*3 Pa) argon.
- the lithium chloride muds were reslurried with fresh cyclohexane (2 X 50 ml.).
- the resultant lithium dispersion was dried in a stream of argon, weighed (7.25 grams, 1.045 mole, 2.80 equivalents), and transferred to the reaction flask with 200 ml of cyclohexane.
- the reaction mixture was stirred at 450 RPMs, and heated to 72.6° C with a heating mantle. The heat source was removed.
- 1 -Chloro-4-methoxy-butane, 45.70 grams, (0.373 mole, 1.00 equivalent, lot 8663) was added dropwise via the addition funnel. An exotherm was detected after 7.8% of the feed had been added. Hexane/dry ice cooling was applied to maintain the reaction temperature at 60-65° C. The total halide feed time was sixty-five minutes.
- the cooling bath was removed at the end of the halide feed.
- the reaction temperature fell off rapidly to room temperature.
- the reaction mixture was stirred for one hour at 450 RPMs.
- the reaction mixture was then transferred with argon pressure to a dry sintered glass pressure filter.
- the product solution was pressure filtered with ⁇ psi (20.68 x 10 3 Pa) argon.
- the lithium chloride muds were reslurried with fresh cyclohexane (2 X 40 ml.).
- Total Base 12.4 wt. %.
- Lithium metal dispersion lot 8899, 0.43% sodium, was washed free of mineral oil with hexane (2 X 70 ml), and pentane (1 X 70 ml).
- the resultant lithium dispersion was dried in a stream of argon, weighed (6.35 grams, 0.915 mole, 2.80 equivalents), and transferred to the reaction flask with 200 ml of cyclohexane.
- the reaction mixture was stirred at 450 RPMs, and heated to 68° C with a heating mantle. The heat source was removed.
- 1-Chloro-3-methoxy-butane 40.03 grams, (0.327 mole, 1.00 equivalent, lot 8914) was added dropwise via the addition funnel.
- EXAMPLE 7 PREPARATION OF 4-(2-BUTOXY)-1 -BUTYLLITHIUM IN CYCLOHEXANE, LOT 8956
- a 500 ml., three-necked, Morton flask was fitted with a mechanical stirrer, a 125 ml pressure-equalizing addition funnel, and a Claisen adapter equipped with a thermocouple, a dry ice condenser, and an argon inlet. This apparatus was dried in an oven overnight at 125° C, assembled hot, and allowed to cool to room temperature in a stream of argon.
- Lithium metal dispersion lot 8899, 0.43% sodium, was washed free of mineral oil with hexane (2 X 100 ml), and pentane (1 X 100 ml). The resultant lithium dispersion was dried in a stream of argon, weighed (6.70 grams, 0.965 mole, 2.80 equivalents), and transferred to the reaction flask with 250 ml of cyclohexane. The reaction mixture was stirred at 450
- the product solution was pressure filtered with 3 psi (20.68 x 10 3 Pa) argon.
- the lithium chloride muds were reslurried with fresh cyclohexane (1 X 75 ml., 1 X 50 ml.).
- Total Base 12.1 wt. %.
- the resultant lithium dispersion was dried in a stream of argon, weighed (6.00 grams, 0.864 mole, 2.80 equivalents), and transferred to the reaction flask with 250 ml of cyclohexane.
- the reaction mixture was stirred at 450 RPMs, and heated to 80° C with a heating mantle. The heat source was removed.
- 1- Chloro-4-(1-methylethoxy)-butane, 46.47 grams, (0.309 mole, 1.00 equivalent, lot 8960) was added dropwise via the addition funnel. An exotherm was detected after 22.9 % of the halide feed had been added.
- a dry ice/hexane cooling bath was applied as needed to maintain the reaction temperature between 60-65° C.
- the total halide feed time was forty-five minutes.
- the cooling bath was removed at the end of the halide feed.
- the reaction temperature fell off rapidly to room temperature.
- the reaction mixture was stirred for ninety minutes at 450 RPMs, then for two hours at 300 RPMs.
- the reaction mixture was then transferred with argon pressure to a dry sintered glass pressure filter.
- the product solution was pressure filtered with 3 psi (20.68 x 10 3 Pa) argon.
- the lithium chloride muds were reslurried with fresh cyclohexane (2 X 25 ml.).
- Total Base 12.3 wt. %.
- a one liter, three-necked, round-bottom flask was fitted with a mechanical stirrer, a septum and a Claisen adapter equipped with a thermocouple, dry ice condenser, and an argon inlet.
- This apparatus was dried in an oven overnight at 125° C, assembled hot, and allowed to cool to room temperature in a stream of argon.
- the flask was charged with cyclohexane, 310.70 grams, and isoprene, 40.00 grams (0.587 mole).
- the reaction mixture was at 20.0° C.
- 4-Methoxy-1 -butyllithium, 16.74 grams of 11.4 wt.% solution (0.020 mole, Lot 8915) was then added with a syringe.
- a two liter, three-necked round bottom flask was fitted with a mechanical stirrer, a gas inlet tube, and a Claisen adapter equipped with a dry ice condenser, and a thermocouple. This apparatus was dried in an oven overnight at 125° C, assembled hot, and allowed to cool to room temperature in a stream of argon.
- the flask was charged with 141.81 grams (1.50 moles, 1.00 equivalent) of 3-chloro-1 -propanol and 500 ml. of cyclohexane.
- the resultant two-phase solution was stirred at 400 RPMs. Amberlyst 15 resin catalyst, 35 grams, was added, followed by an additional 250 ml. of cyclohexane.
- a one liter, three-necked round bottom flask was fitted with a mechanical stirrer, a gas inlet tube, and a Claisen adapter equipped with a dry ice condenser, and a thermocouple. This apparatus was dried in an oven overnight at 125° C, assembled hot, and allowed to cool to room temperature in a stream of argon.
- the flask was charged with 91.95 grams (0.75 moles, 1.00 equivalent) of 3-chloro-2,2-dimethyl-1 -propanol and 200 ml. of cyclohexane.
- the resultant one-phase solution was stirred at 400 RPMs. Amberlyst 15 resin catalyst, 15 grams, was added, followed by an additional 50 ml.
- GC assay 2.98 % cyclohexane, 16.79 % 3-chloro-2,2-dimethyl-1 - propanol, 78.06 % desired product, and 1.17 % unknowns.
- reaction mixture was stirred at 20-25° C, and periodically monitored by gas chromatography (GC) for the disappearance of 3-chloro-1 -propanol. After forty-eight hours stirring, all the starting material had been consumed, and the reaction mixture was a single phase.
- GC gas chromatography
- the reaction mixture was diluted with pentane (100 ml.) and water (100 ml.) and transferred to a separatory funnel. The aqueous layer was discarded. The organic layer was washed with saturated sodium bicarbonate solution (2 X 50 ml.), water (1 X 50 ml.), and filter-dried over magnesium sulfate.
- a 500 ml., three-necked round bottom flask was fitted with a reflux condenser, a thermocouple, a septum inlet, a magnetic stir bar, and an argon inlet.
- the flask was charged with 3-chloro-2,2-dimethyl-1 -propanol, 122.60 grams (1.00 mole, 1.00 equivalents), pentane (50 ml.), and 2- methyl-2-butene, 70.66 grams (1.01 mole, 1.01 equivalents). This afforded a two phase solution.
- the reaction mixture was maintained at 20-25° C with a water cooling bath.
- a one liter, three-necked round bottom flask was equipped with a reflux condenser, a teflon clad thermocouple, a 225 ml. pressure-equalizing addition funnel, a large egg-shaped magnetic stir bar, and a gas outlet vented to a caustic scrubber.
- This apparatus was dried in an oven overnight at 125° C, assembled hot, and allowed to cool to room temperature in a stream of argon.
- the flask was charged with methanol, 80.10 grams (2.50 moles, 1.00 equivalent) and tetrahydrofuran, 180.28 grams (2.50 moles, 1.00 equivalent).
- the reaction mixture was cooled to 0° C with a methanol/ice bath, then 356.91 grams (3.00 moles, 1.20 equivalents) of thionyl chloride was added dropwise via the addition funnel. There was an immediate exotherm, and a release of acidic fumes. The temperature was held below 15° C by adjustment of the feed rate. The total thionyl chloride feed time was two and a third hours. The cooling bath was removed at the end of the feed. The reaction mixture was clear and colorless. The reaction mixture was heated to reflux for three hours, at which time the temperature was 120° C, then the reaction mixture was allowed to cool to room temperature.
- a 500 ml., three-necked round bottom flask was equipped with a reflux condenser, a teflon clad thermocouple, a 125 ml. pressure-equalizing addition funnel, a large egg-shaped magnetic stir bar, and a gas outlet vented to a caustic scrubber.
- This apparatus was dried in an oven overnight at 125° C, assembled hot, and allowed to cool to room temperature in a stream of argon.
- the flask was charged with thionyl chloride, 124.92 grams (1.05 moles, 1.05 equivalents).
- 3-Methoxy-1- butanol, 104.15 grams (1.00 mole, 1.00 equivalent) was added dropwise via the addition funnel.
- a one liter, three-necked round bottom flask was equipped with a reflux condenser, a teflon clad thermocouple, a 250 ml. pressure-equalizing addition funnel, a large egg-shaped magnetic stir bar, and a gas outlet vented to a caustic scrubber.
- This apparatus was dried in an oven overnight at 125° C, assembled hot. and allowed to cool to room temperature in a stream of argon.
- the flask was charged with 2-butanol, 185.30 grams (2.50 moles, 1.00 equivalent) and tetrahydrofuran, 180.28 grams (2.50 moles, 1.00 equivalent).
- the reaction mixture was cooled to - 15°C, then 356.91 grams (3.00 moles, 1.20 equivalents) of thionyl chloride was added dropwise via the addition funnel. There was an immediate exotherm, and a release of acidic fumes. The temperature was held below 10° C by adjustment of the feed rate. The total thionyl chloride feed time was two and a quarter hours. The cooling bath was removed at the end of the feed. The reaction mixture was heated to reflux (95° C) for six hours, then let cool to room temperature. An aliquot was withdrawn, diluted with pentane, washed with water and saturated sodium bicarbonate solution, then analyzed by gas chromatography (30 m. X 0.54 mm AT-1 column).
- GC assay 96.0 % desired product, and 4.0 % unknowns.
- a one liter, three-necked round bottom flask was equipped with a reflux condenser, a teflon clad thermocouple, a 250 ml. pressure-equalizing addition funnel, a large egg-shaped magnetic stir bar, and a gas outlet vented to a caustic scrubber.
- This apparatus was dried in an oven overnight at 125°C, assembled hot, and allowed to cool to room temperature in a stream of argon.
- the flask was charged with 2-propanol, 150.25 grams (2.50 moles, 1.00 equivalent) and tetrahydrofuran, 180.28 grams (2.50 moles, 1.00 equivalent).
- the reaction mixture was cooled to 0°C, then 356.91 grams (3.00 moles, 1.20 equivalents) of thionyl chloride was added dropwise via the addition funnel. There was an immediate exotherm, and a release of acidic fumes. The temperature was held below 15°C by adjustment of the feed rate. The total thionyl chloride feed time was two and a half hours. The cooling bath was removed at the end of the feed. The reaction mixture was heated to reflux (119°C) for five hours, after which time all gas evolution had ceased, then let cool to room temperature. The orange reaction mixture was transferred to a one liter separatory funnel, and diluted with pentane (300 ml.).
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Abstract
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AU58037/96A AU5803796A (en) | 1995-12-29 | 1996-05-24 | Functionalized initiators for anionic polymerization |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US937795P | 1995-12-29 | 1995-12-29 | |
US60/009,377 | 1995-12-29 |
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WO1997024377A1 true WO1997024377A1 (fr) | 1997-07-10 |
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PCT/US1996/007625 WO1997024377A1 (fr) | 1995-12-29 | 1996-05-24 | Initiateurs fonctionnalises, pour polymerisation anionique |
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WO (1) | WO1997024377A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001070832A2 (fr) * | 2000-03-20 | 2001-09-27 | Fmc Corporation | Macromonomeres presentant la fonction d'olefine terminal |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3719730A (en) * | 1966-12-15 | 1973-03-06 | Nat Distillers Chem Corp | Modification of alfin polymers and product |
US3862100A (en) * | 1972-12-13 | 1975-01-21 | Firestone Tire & Rubber Co | Alkali metal aliphatic and aromatic hydrocarbon acetals and ketals and their use as polymerization initiators, etc. |
US4753991A (en) * | 1985-08-03 | 1988-06-28 | Basf Aktiengesellschaft | Polymers containing amino groups, and their preparation |
-
1996
- 1996-05-24 AU AU58037/96A patent/AU5803796A/en not_active Abandoned
- 1996-05-24 WO PCT/US1996/007625 patent/WO1997024377A1/fr active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3719730A (en) * | 1966-12-15 | 1973-03-06 | Nat Distillers Chem Corp | Modification of alfin polymers and product |
US3862100A (en) * | 1972-12-13 | 1975-01-21 | Firestone Tire & Rubber Co | Alkali metal aliphatic and aromatic hydrocarbon acetals and ketals and their use as polymerization initiators, etc. |
US4753991A (en) * | 1985-08-03 | 1988-06-28 | Basf Aktiengesellschaft | Polymers containing amino groups, and their preparation |
Non-Patent Citations (1)
Title |
---|
TETRAHEDRON, Volume 41, No. 24, issued 1985, GARDETTE et al., "Carbocupration of Alkynes by Organocopper Reagents Bearing a Protected Hydroxy or Thiol Function", pages 5887-5899. * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001070832A2 (fr) * | 2000-03-20 | 2001-09-27 | Fmc Corporation | Macromonomeres presentant la fonction d'olefine terminal |
WO2001070832A3 (fr) * | 2000-03-20 | 2002-04-04 | Fmc Corp | Macromonomeres presentant la fonction d'olefine terminal |
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AU5803796A (en) | 1997-07-28 |
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