WO2001019899A1 - Poly(ethynylene phenylene ethynylene silylenes) et leurs procedes de preparation - Google Patents
Poly(ethynylene phenylene ethynylene silylenes) et leurs procedes de preparation Download PDFInfo
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- WO2001019899A1 WO2001019899A1 PCT/FR2000/002562 FR0002562W WO0119899A1 WO 2001019899 A1 WO2001019899 A1 WO 2001019899A1 FR 0002562 W FR0002562 W FR 0002562W WO 0119899 A1 WO0119899 A1 WO 0119899A1
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- 238000000034 method Methods 0.000 title claims abstract description 66
- -1 Poly(silyleneethynylene phenyleneethynylene) Polymers 0.000 title claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 151
- 239000012035 limiting reagent Substances 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 33
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 16
- 125000003277 amino group Chemical group 0.000 claims description 12
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 150000004795 grignard reagents Chemical class 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000007818 Grignard reagent Substances 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 239000000010 aprotic solvent Substances 0.000 claims description 4
- 229910001038 basic metal oxide Inorganic materials 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 2
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000047 disilanyl group Chemical group [H][Si]([*])([H])[Si]([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 13
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- CBYDUPRWILCUIC-UHFFFAOYSA-N 1,2-diethynylbenzene Chemical compound C#CC1=CC=CC=C1C#C CBYDUPRWILCUIC-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- PNXLPYYXCOXPBM-UHFFFAOYSA-N 1,3-diethynylbenzene Chemical compound C#CC1=CC=CC(C#C)=C1 PNXLPYYXCOXPBM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 150000002901 organomagnesium compounds Chemical class 0.000 description 2
- 125000002734 organomagnesium group Chemical group 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical compound COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 description 1
- XUKFLPBPNMLWTH-UHFFFAOYSA-N 1-ethynyl-4-methylbenzene;1-ethynyl-4-phenylbenzene Chemical group CC1=CC=C(C#C)C=C1.C1=CC(C#C)=CC=C1C1=CC=CC=C1 XUKFLPBPNMLWTH-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical class [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012700 ceramic precursor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- NCEXYHBECQHGNR-UHFFFAOYSA-N chembl421 Chemical compound C1=C(O)C(C(=O)O)=CC(N=NC=2C=CC(=CC=2)S(=O)(=O)NC=2N=CC=CC=2)=C1 NCEXYHBECQHGNR-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 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
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000311 lanthanide oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- SONNWYBIRXJNDC-VIFPVBQESA-N phenylephrine Chemical class CNC[C@H](O)C1=CC=CC(O)=C1 SONNWYBIRXJNDC-VIFPVBQESA-N 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
Definitions
- the present invention relates to polymers of poly (ethynylene phenylene ethynylene silylene) of determined molecular mass, to processes for the preparation of said polymers and to the hardened products capable of being obtained by heat treatment of said polymers.
- the polymers according to the invention can in particular be used in matrices for composites.
- thermostable plastics that is to say polymers which can withstand high temperatures which can reach for example up to 600 ° C.
- thermostable plastics have increased enormously in recent decades, particularly in the electronic and aerospace fields.
- metals such as iron, titanium and steel are thermally very resistant, but they are heavy.
- Aluminum is light but not very resistant to heat, ie up to around 300 ° C.
- Ceramics such as SiC, S ⁇ N 4 and silica are lighter than metals and very heat resistant but they are not moldable. This is the reason why many plastics have been synthesized which are light, moldable and have good mechanical properties; these are mainly carbon-based polymers.
- Polyimides have the highest heat resistance of all plastics with a thermal deformation temperature of 460 ° C, however these compounds which are listed as being the most stable known at present are very difficult to use.
- Other polymers such as polybenzimidazoles, polybenzothiazoles and polybenzooxazoles have a heat resistance still higher than that of polyimides but they are not moldable and they are flammable.
- Polymers based on silicon such as silicones or carbosilanes have also been widely studied.
- the latter such as poly (sylylene ethynylene) compounds are generally used as ceramic precursors of the silicon carbide Sic type, resist compounds and conductive materials.
- process (C) makes it possible to obtain polymers without structural defects with good yields and a low mass distribution.
- the compounds obtained by this process are perfectly pure and have perfectly characterized thermal properties. These are crosslinkable thermoplastic polymers.
- polymers are prepared essentially by the method of scheme (C) and optionally by the process of scheme (B), and they have a weight average molecular weight of 500 to 1,000,000.
- This document also describes cured products based on these polymers and their preparation by heat treatment. It is indicated that the polymers in this document can be used as thermostable polymer, fire-resistant polymer, conductive polymer, material for elements. electroluminescent and linear. In fact, it appears that such polymers are essentially used as organic precursors of ceramics.
- the various procedures call upon injection techniques, (in particular RTM), or compaction techniques of prepregs.
- Prepregs are semi-finished products of small thickness made of fibers impregnated with resin.
- the prepregs which are intended for producing high performance composite structures contain at least 50% fiber by volume.
- the matrix must have a low viscosity to penetrate the reinforcing ply and properly impregnate the fiber in order to avoid its distortion and to preserve its integrity.
- the reinforcing fibers are impregnated either with a resin solution in an appropriate solvent, or with pure resin in the molten state, this is the so-called "hot melt" technique.
- Injection molding is a process which involves injecting the liquid resin into the reinforcement textile positioned beforehand in the impression formed by the mold and the counter-mold.
- the most important parameter is the viscosity, which must be between 100 and 1000 mPa. s at the injection temperature, which is generally 50 to 250 ° C.
- viscosity is therefore the critical parameter which conditions the ability of the polymer to be used.
- amorphous polymers correspond to macromolecules whose skeletal structure is completely disordered. They are characterized by their glass transition temperature (Tg) corresponding to the transition from the glassy state to the rubbery state. Beyond Tg, thermoplastics are however characterized by a high creep resistance.
- the polymers prepared in document EP-B1-0 617 073 are compounds which are in powder form. The inventors have been able to show, by reproducing the syntheses described in this document, that the polymers prepared would produce glass transition temperatures close to 50 ° C.
- the object of the invention is to provide polymers which meet, inter alia, these needs which do not have the defects, drawbacks, limitations and disadvantages of the polymers of the prior art as shown in particular by document EP-B1-0 617,073, and which solve the problems of the prior art.
- the object of the invention is also to provide a process which makes it possible to prepare said polymers.
- This object, and others still are achieved in accordance with the invention by a polymer of poly (ethynylene phenylene ethynylene silylene) of determined molecular mass, in which said polymer carries at the chain end groups derived from a chain-limiting agent. , said polymer corresponding to formula (I) below:
- R represents a halogen atom (such as F, Cl, Br and I), an alkyl group (linear, branched or cyclic) having from 1 to 20 carbon atoms (such as methyl, ethyl, propyl, butyl, cyclohexyl), an alkoxy group having from 1 to 20 carbon atoms (such as methoxy, ethoxy, propoxy), an aryloxy group having from 6 to 20 carbon atoms such as a phenoxy group, a substituted phenoxy group having from 6 to 20 carbon atoms (such as the 3, 5-dimethylphenoxy group), an alkenyl group (linear, branched or cyclic) having from 2 to 20 atoms carbon (such as vinyl, allyl, cyclohexenyl), an alkynyl group having 2 to 20 carbon atoms (such as ethynyl
- the polymers according to the invention have a structure substantially similar to that of the polymers of document EP-B1-0 617 073 with the fundamental exception, however, of the presence at the chain end of the groups Y derived from a chain-limiting agent. .
- this polymer (I) or (la) also has perfectly defined and modular rheological properties.
- Y depends on the nature of the chain-limiting agent from which it is derived, Y may, in the case of the polymers of formula (I), represent a group of formula (II):
- a particularly preferred polymer of formula (I) according to the invention corresponds to the following formula:
- q is an integer from 1 to 40 and PH represents a phenyl group.
- the invention also relates to polymers of determined molecular mass, capable of being obtained by hydrolysis of the polymers of formula (la) and corresponding to the following formula (Ib):
- the molar ratio of the Y groups at the end of the chain to the repeating units ethynylene phenylene ethynylene silylene is generally from 0.01 to 1.5. Preferably, this ratio is 0.25 to 1.
- the molar proportion of the Y groups at the end of the chain is generally from 1 to 60 and preferably from 20 to 50% of the polymer of formula (I) or (la).
- the number-average molecular weight of the polymers (I), (la) and (Ib) according to the invention, which is perfectly defined, is generally from 400 to 5000 and the weight-average molecular weight is from 600 to 10,000. These masses being determined by gel permeation chromatography (GPC) from a polystyrene calibration.
- controlling the molecular weight of the polymers which generally falls within the above-mentioned range, makes it possible to perfectly control the viscosity of the polymers.
- the viscosities of the polymers according to the invention are in a range of values from 0.1 to 1000 mPa.s, for temperatures ranging from 20 to
- the viscosity also depends on the nature of the groups carried by the aromatic rings and the silicon. These viscosities which cannot be obtained with the polymers of the prior art are fully compatible with the conventional techniques for preparing composites.
- the viscosity is also linked to the glass transition temperature (Tg).
- Tg glass transition temperature
- the glass transition temperature of the polymers according to the invention will therefore generally be - 150 to + 10 ° C. which is much lower than the glass transition temperature of the polymers of the prior art.
- the invention further relates to a first process for the preparation of a molecular weight poly (ethynylene phenylene ethynylene silylene) polymer. determined bearing at the end of the chain groups derived from a chain limiting agent, said polymer corresponding to the following formula (I):
- phenylene group of the central repeating unit can be in the form o, m or p
- R, R ', R' ', Y, n and q have the meaning already given above.
- phenylene group may be in the form o, m or p, and R, and n have the meaning indicated above for the formula (I), and X represents a halogen atom such as Cl Br or I, and a chain limiting agent of formula:
- Y MgX (V) X having the meaning already given above, and Y is a group chosen from the groups of formula:
- a variant of the first process according to the invention makes it possible to prepare a poly (ethynylene phenylene ethynylene silylene) polymer of formula (la):
- phenylene group of the central repeating unit can be in the form o, m, or p, and R, R ', R' ', Y, q and n have the meaning already given above; said process comprising reacting a GRIGNARD reagent of general formula (IV) above, and of the mixture of a chain-limiting agent of formula:
- the first process of the invention in this variant, can also also include a final hydrolysis step to give the polymer of formula (Ib) already mentioned above.
- the invention also relates to a second process for the preparation of a poly (ethynylene phenylene ethynylene silylene) polymer, of determined molecular weight, bearing at the end of the chain groups derived from a chain limiting agent, said polymer corresponding to the formula (I) following:
- phenylene group of the central repeating unit can be in the form o, m or p
- R, R ', R' ', Y, n and q have the meaning already given above.
- R '' ' has the same meaning as R and can be the same or different from the latter, and has the same meaning as n and can be the same or different from the latter with a compound of formula (XII):
- a variant of the second process according to the invention makes it possible to prepare a poly (ethynylene phenylene ethynylene silylene) polymer of formula (la):
- phenylene group of the central repeating unit can be in the form, o, m or p, and R, R ', R' ', Y, q and n have the meaning already given above; said process comprising the reaction of a compound of formula (X) already mentioned above, with a mixture of a chain-limiting agent (monohydrosilane) of formula (XIII):
- the second method of the invention in this variant can, moreover, comprise a final hydrolysis step to give the polymer of formula (Ib) already mentioned above.
- the control of the masses of the polymers of formula (I), (la) and (Ib) is obtained by adding to the reaction medium a reactive species also called chain-limiting agent which comes block the polymerization reaction without affecting the overall yield of the reaction.
- This reactive species is generally an analogue of one of the main reactants, but which has only one function allowing coupling. When this species is introduced into the polymer chain, growth is stopped.
- the same principle could be applied with slight adaptations to the other possible synthesis methods for the polymers of formula (I) or (la).
- the length of the polymer and therefore its molecular weight and consequently its viscosity are in direct correlation with molar percentage of chain-limiting agent (see Figure 1).
- This molar percentage is defined by the mole ratio of the chain-limiting agent to the total of moles chain limiting agent and diacetylene compounds of formula (IV) or (X) x 100. This percentage can range from 1 to 60%, preferably from 20 to 50%.
- molecular weight is related to the degree of activation of the catalyst [4]. As this is highly hygroscopic, it is very difficult to predict the molecular masses a priori. The less the catalyst is activated and the lower the masses, but this drop is accompanied by a significant drop in the yield of the polymerization reaction. In addition, the distribution can be so wide that several fractions of different mass can be isolated by selective fractionation.
- the first preparation process of the invention makes it possible to dispense with a step in the process of EP-B1-0 617 073 which involves a monohalogenated silylated compound, which induces shorter reaction times as well as substantial savings in reagents.
- the invention also relates to the cured product capable of being obtained by heat treatment at a temperature of 50 to 700 ° C. of the polymer described above. According to the invention, this hardened product generally has a number average molecular weight of 400 to 5,000 and a weight average molecular weight of 600 to 10,000.
- FIG. 1 is a graph on which the viscosity ⁇ of the polymers according to l has been plotted.
- invention in Pa.s
- T temperature
- T temperature
- the first process for the preparation of a poly (ethynylene phenylene ethynylene silylene) polymer according to the invention is substantially similar to that described in document EP-B1- 0 617 073 with the exception, however, of the incorporation in this mixture in accordance with the invention of a chain limiting agent, of the final treatment of the polymers and optionally of the molar ratio of the organomagnesium and dichlorosilane reagents.
- Grignard reagents of formula (IV) used in the first preparation process according to the invention are in particular those described in document EP-B1-0 617 073 on pages 5 to 7 (Formulas (3) and (8) to (20).
- the chain limiting agent of formula (V) can be a monoacetylene organomagnesium compound of formula:
- Examples of the monoacetylene compounds from which the monoacetylene organomagnesium compounds (V) are derived are the following: phenylacetylene, 4-ethynyltoluene 4-ethynylbiphenyl, 1-ethynyl 4-methoxybenzene.
- dihalosilanes examples are the dichlorosilanes described on pages 7 to 9 of the patent
- EP-B1-0 617 093 and respond in particular to formulas (21) to (26) given in this document.
- one of the substituents of these dihalosilanes is not necessarily H as in the aforementioned patent.
- the conditions of the polymerization reaction such as the solvent, the duration of the reaction, the temperature, etc. (excluding “post-treatment") are substantially the same as those described in document EP-B1- 0 617 073 to which reference is made in particular on page 14.
- the only differences in this actual polymerization stage relate to the addition of an additional chain-limiting reagent.
- the reaction conditions are moreover substantially the same.
- the ratio of the number of acetylenic function by the number of halogen functions carried by the silane must be as close as possible to 1, and preferably from 0.9 to 1.1.
- the molar ratio of phenylacetylene to diethynylbenzene is preferably between 0.01 and 1.5 and ideally between 0.25 and 1 (percentage from 1 to 60%).
- a final hydrolysis step is carried out, so there is no step compared to the analogous process of the prior art, in particular in the case where the chain limiter is an organomagnesium.
- the chain limiter is an organomagnesium.
- a post-treatment of the already prepared polymer is carried out, whose molecular mass is frozen, by a monohalosilane then a hydrolysis.
- the monohalosilane does not play the role of chain limiter since it is not, on the contrary , of the present invention included in the starting reaction mixture and that its action has no influence on the molecular weight of the polymer.
- the polymer is hydrolyzed by a volume for example of 0.1 to 50 ml per gram of polymer of an acid solution, for example approximately 0.01 to 10 N of hydrochloric acid or d 'sulfuric acid .
- the ideal solvent is tetrahydrofuran.
- the reaction mixture is then decanted and the solvent of the organic phase is substituted with a volume for example of 0.1 to 100 ml per gram of polymer and ideally of 1 to 10 ml per gram of polymer for any type of solvent immiscible with water, such as xylene, toluene, benzene, chloroform, dichloromethane or alkane with more than 5 carbons.
- this step can be omitted.
- the organic phase is then washed for example from 1 to 5 times and preferably 2 to 3 times with a volume of water, for example from 0.1 to 100 ml per gram of polymer and ideally from 1 to 10 ml per gram of polymer , so as to neutralize the organic phase and extract from it all the impurities such as magnesium and halogen salts.
- the pH of the organic phase should preferably be between 5 and 8 and ideally between 6.5 and 7.5.
- the polymer is dried under a vacuum of between 0.1 and 500 mbar at a temperature between 20 and 150 ° C for a time between 15 minutes and 24 hours.
- the second process for preparing the polymers of formula (I) is a process using dehydrogenation in the presence of a basic metal oxide.
- Such a process differs from the analogous process described in documents [1] and [4] as well as in document EP-B1-0 617 073 only in that a chain-limiting agent is added to the reaction mixture.
- the reaction mixture comprises a compound of formula (X) for example: 1, 3-ethylene benzene and a chain limiting agent which in this second process is a monoacetylene (XI) analogous to that described above for the first process.
- the mixture of the compounds (IX) and of the chain-limiting agent reacts with a dihydrosilane of formula (XII).
- the basic metal oxide used is preferably chosen from alkali, alkaline earth metal oxides, lanthanide oxides, scandium, yttrium, thorium, titanium, zirconium, hafnium, copper, zinc, cadmium oxides and their mixtures. . Examples of such oxides are given in document EP-B1-0 617 073 on pages 16 and 17 to which explicit reference is made here. These oxides can be subjected to an activation treatment as described in patent EP-B1-0 617 073.
- the hardened products prepared by heat treatment of the polymers according to the invention are by example produced by melting this polymer or dissolving it in a suitable solvent, then possibly putting it in the desired form and heating it in a gaseous atmosphere of air, nitrogen or inert gas - such as argon or helium.
- the temperature of the treatment generally ranges from 50 to 700 ° C, preferably from 100 to 400 ° C and more preferably from 150 to 350 ° C, and the heating is generally carried out for a period of one minute to 100 hours.
- the curing reaction can optionally be carried out in the presence of a curing agent and the polymer according to the invention can also be mixed with other resins or polymers. Due to the similar structure of the polymers according to the invention and of the polymers of document EP-B1-0 617 073, their hardening process is substantially identical and reference may be made to this document on page 17 for more details.
- the preparation of organic matrix composites comprising the polymer of the invention is detailed below:
- Example 1 Preparation of poly (diphenylsilylene ethynylene phenylene ethynylene) with chain termination of aromatic acetylene type with 20 mol% of chain limiter
- a 1 liter t ⁇ col flask placed under argon and containing 6.4 g (263 mmol) of magnesium powder in suspension in 100 ml of anhydrous THF, 25.88 g (257 mmol) of bromoethane in solution in 100 ml of anhydrous THF are introduced dropwise so as to maintain the reflux.
- the polymer is then obtained by evaporation of the solvent.
- the polymer is finally purified by drying under 0.4 bar at 20 ° C. 28.5 g are thus obtained (80% yield) of polymer which is in the form of a yellow oil.
- the number average molecular mass of this compound is 1515 for a mass average mass of 3257 (polydispersity of 2.15). These masses were determined by GPC from a polystyrene calibration.
- the viscosity of this polymer is 950 mPa.s at 130 ° C, 720 mPa.s at 140 ° C and 550 mPa. s at 150 ° C.
- the number average molecular mass of this compound is 1297 for a mass average mass of 2302 (polydispersity of 1.77). These masses were determined by GPC from a polystyrene calibration.
- the viscosity of this polymer is 750 mPa.s at 110 ° C, 5.10 mPa.s at 120 ° C, 350 mPa. s at 130 ° C and 300 mPa.s at 140 ° C.
- Example 3 Preparation of poly (diphenylsilylene ethynylene phenylene ethynylene) with chain termination of aromatic acetylene type with 40 mol% of chain limiter
- the number average molecular mass of this compound is 1070 for a mass average mass of 1900 (polydispersity of 1.78). These masses were determined by GPC from a polystyrene calibration.
- the viscosity of this polymer is 570 mPa. her
- the number average molecular mass of this compound is 878 for a mass average mass of 1470 (polydispersity of 1.67). These masses were determined by GPC from a polystyrene calibration.
- the viscosity of this polymer is 450 mPa.s at 70 ° C, 250 mPa.s at 80 ° C, 150 mPa.s at 90 ° C, 100 mPa. s at 100 ° C and 70 mPa.s at 110 ° C.
- Example 5 Synthesis from a metal oxide, according to the second method of preparation according to the invention, of poly (diphenylsilylene ethynylene phenylene ethynylene) with chain termination of aromatic acetylene type with 20 mol% of chain limiter
- the number average molecular mass of this compound is 1,312 for a mass average mass of 3,827 (polydispersity of 2.91). These masses were determined by GPC from a polystyrene calibration.
- the poly (diphenylsilylene ethynylene phenylene ethynylene) used is that of Example 3.
- the composite is obtained by impregnating at 130 ° C. a stack of 30 plies of carbon fabrics.
- the sandwich thus formed is placed in an oven under a pressure of 2 bars for crosslinking.
- the cycle used is as follows: from 130 to 250 at 10 ° C / min., Then 30 min. at 250 ° C, then from 250 to 25 ° C at 10 ° C / min. This gives a hardened composite with a density of 1.5.
- Silicon Poly (silyleneethynylenephenylene éthynylène) s "by ITOH M., INOUE K., I ATA K.,
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Abstract
Description
Claims
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JP2001523674A JP2003509557A (ja) | 1999-09-16 | 2000-09-15 | ポリ(エチニレン−フェニレン−エチニレン−シリレン)およびその調製方法 |
EP00962652A EP1226203A1 (fr) | 1999-09-16 | 2000-09-15 | Poly(ethynylene phenylene ethynylene silylenes) et leurs procedes de preparation |
US10/088,167 US6703519B1 (en) | 1999-09-16 | 2000-09-15 | Poly (ethynylene phenylene ethynylene silylene)s and method for preparation thereof |
CA002384589A CA2384589A1 (fr) | 1999-09-16 | 2000-09-15 | Poly(ethynylene phenylene ethynylene silylenes) et leurs procedes de preparation |
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EP1226203A1 (fr) | 2002-07-31 |
FR2798662B1 (fr) | 2002-01-18 |
US6703519B1 (en) | 2004-03-09 |
CA2384589A1 (fr) | 2001-03-22 |
JP2003509557A (ja) | 2003-03-11 |
FR2798662A1 (fr) | 2001-03-23 |
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