US20120004387A1 - Polyarylene polymers and processes for preparing - Google Patents
Polyarylene polymers and processes for preparing Download PDFInfo
- Publication number
- US20120004387A1 US20120004387A1 US12/979,417 US97941710A US2012004387A1 US 20120004387 A1 US20120004387 A1 US 20120004387A1 US 97941710 A US97941710 A US 97941710A US 2012004387 A1 US2012004387 A1 US 2012004387A1
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- United States
- Prior art keywords
- polymer
- give
- mmoles
- solution
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000008569 process Effects 0.000 title claims abstract description 17
- 229920000412 polyarylene Polymers 0.000 title abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 239000003446 ligand Substances 0.000 claims description 26
- 230000007935 neutral effect Effects 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 13
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 9
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000003457 sulfones Chemical class 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 64
- 239000000243 solution Substances 0.000 description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 42
- 239000000203 mixture Substances 0.000 description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 229910052757 nitrogen Inorganic materials 0.000 description 32
- 239000007787 solid Substances 0.000 description 29
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 28
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 19
- 238000003828 vacuum filtration Methods 0.000 description 17
- 238000010992 reflux Methods 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 159000000000 sodium salts Chemical class 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- -1 polyphenylene backbone Polymers 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- 238000010926 purge Methods 0.000 description 9
- LEMMUDNZHFSHEB-UHFFFAOYSA-N 2-(benzenesulfonyl)-1-[2-(benzenesulfonyl)-4-bromophenyl]-4-bromobenzene Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1S(=O)(=O)C1=CC=CC=C1 LEMMUDNZHFSHEB-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 150000002815 nickel Chemical class 0.000 description 8
- NWYHCLZPZAAVPT-UHFFFAOYSA-N 2-(benzenesulfonyl)-1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C(S(=O)(=O)C=2C=CC=CC=2)=C1 NWYHCLZPZAAVPT-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- SFKPQALGKITKRB-QAHXKXPISA-N [3H]CC1=C(C2=CC=C(C)C=C2S([3H])(=O)=O)C=CC(C)=C1 Chemical compound [3H]CC1=C(C2=CC=C(C)C=C2S([3H])(=O)=O)C=CC(C)=C1 SFKPQALGKITKRB-QAHXKXPISA-N 0.000 description 6
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- HRMKLFFUMPUJSF-UHFFFAOYSA-N 5-chloro-2-(4-chloro-2-sulfophenyl)benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(Cl)=CC=C1C1=CC=C(Cl)C=C1S(O)(=O)=O HRMKLFFUMPUJSF-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- 229920006261 self reinforced polyphenylene Polymers 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- ZLMPLIWURYRGEB-UHFFFAOYSA-N 2,5-dibromobenzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC(Br)=CC=C1Br ZLMPLIWURYRGEB-UHFFFAOYSA-N 0.000 description 4
- IFOUFJBAMAPFBN-UHFFFAOYSA-N 2-(benzenesulfonyl)-1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C(S(=O)(=O)C=2C=CC=CC=2)=C1 IFOUFJBAMAPFBN-UHFFFAOYSA-N 0.000 description 4
- AXIUBBVSOWPLDA-UHFFFAOYSA-N CCC1=C(C)C=CC(C)=C1 Chemical compound CCC1=C(C)C=CC(C)=C1 AXIUBBVSOWPLDA-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 244000309464 bull Species 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002816 nickel compounds Chemical class 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- GUCJTGYQCHDCLD-UHFFFAOYSA-N 2,5-dibromobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(Br)=CC=C1Br GUCJTGYQCHDCLD-UHFFFAOYSA-N 0.000 description 3
- VEDGNMLPNHBMCZ-UHFFFAOYSA-N 5-bromo-2-(4-bromo-2-chlorosulfonylphenyl)benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1S(Cl)(=O)=O VEDGNMLPNHBMCZ-UHFFFAOYSA-N 0.000 description 3
- UJWUPNYBEJZARL-UHFFFAOYSA-N 5-bromo-2-(4-bromo-2-sulfophenyl)benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1S(O)(=O)=O UJWUPNYBEJZARL-UHFFFAOYSA-N 0.000 description 3
- GYSZDGVKIMMQMW-UHFFFAOYSA-N 5-chloro-2-(4-chloro-2-chlorosulfonylphenyl)benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC(Cl)=CC=C1C1=CC=C(Cl)C=C1S(Cl)(=O)=O GYSZDGVKIMMQMW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000010485 C−C bond formation reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 2
- MHMIDKZXUHFHHC-UHFFFAOYSA-N 2-(benzenesulfonyl)-1-[2-(benzenesulfonyl)-4-chlorophenyl]-4-chlorobenzene Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC(Cl)=CC=C1C1=CC=C(Cl)C=C1S(=O)(=O)C1=CC=CC=C1 MHMIDKZXUHFHHC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- 229920001410 Microfiber Polymers 0.000 description 2
- JNQQZSFQHQLZPD-UHFFFAOYSA-M O=S(=O)(O[Na])C1=CC(Cl)=CC=C1C1=C([Na])C=C(Cl)C=C1.O=S(=O)=O Chemical compound O=S(=O)(O[Na])C1=CC(Cl)=CC=C1C1=C([Na])C=C(Cl)C=C1.O=S(=O)=O JNQQZSFQHQLZPD-UHFFFAOYSA-M 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical group [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical group 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000003658 microfiber Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- FAVKIHMGRWRACA-UHFFFAOYSA-N (2,5-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=C(Cl)C(C(=O)C=2C=CC=CC=2)=C1 FAVKIHMGRWRACA-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- LFXZSGVZSSMCMB-UHFFFAOYSA-N 2,5-dichlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(Cl)=CC=C1Cl LFXZSGVZSSMCMB-UHFFFAOYSA-N 0.000 description 1
- BXCOSWRSIISQSL-UHFFFAOYSA-N 2,5-dichlorobenzenesulfonyl chloride Chemical compound ClC1=CC=C(Cl)C(S(Cl)(=O)=O)=C1 BXCOSWRSIISQSL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- MBJAPGAZEWPEFB-UHFFFAOYSA-N 5-amino-2-(4-amino-2-sulfophenyl)benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1C1=CC=C(N)C=C1S(O)(=O)=O MBJAPGAZEWPEFB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WOTFCARJUHUAST-UHFFFAOYSA-N CC1=CC(S(=O)(=O)C2=CC=CC=C2)=C(C)C=C1 Chemical compound CC1=CC(S(=O)(=O)C2=CC=CC=C2)=C(C)C=C1 WOTFCARJUHUAST-UHFFFAOYSA-N 0.000 description 1
- WJXCTPJAEBFGBZ-UHFFFAOYSA-N CC1=CC=C(C2=C(S(=O)(=O)C3=CC=CC=C3)C=C(C)C=C2)C(CC2=CC=CC=C2)=C1 Chemical compound CC1=CC=C(C2=C(S(=O)(=O)C3=CC=CC=C3)C=C(C)C=C2)C(CC2=CC=CC=C2)=C1 WJXCTPJAEBFGBZ-UHFFFAOYSA-N 0.000 description 1
- PFPVVDWNDZSFIF-UHFFFAOYSA-N CC1=CC=C(C2=CC=C(C3=C(S(=O)(=O)C4=CC=CC=C4)C=C(C)C=C3)C(CC3=CC=CC=C3)=C2)C(CC2=CC=CC=C2)=C1 Chemical compound CC1=CC=C(C2=CC=C(C3=C(S(=O)(=O)C4=CC=CC=C4)C=C(C)C=C3)C(CC3=CC=CC=C3)=C2)C(CC2=CC=CC=C2)=C1 PFPVVDWNDZSFIF-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- SHNJJULHPALKTP-UHFFFAOYSA-N Nc(cc1)cc(N)c1-c(c(N=O)c1)ccc1N Chemical compound Nc(cc1)cc(N)c1-c(c(N=O)c1)ccc1N SHNJJULHPALKTP-UHFFFAOYSA-N 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- MMVVYHDFMKIFOH-UHFFFAOYSA-N O=S(=O)(C1=CC=CC=C1)C1=CC(Br)=CC=C1C1=C(CC2=CC=CC=C2)C=C(Br)C=C1 Chemical compound O=S(=O)(C1=CC=CC=C1)C1=CC(Br)=CC=C1C1=C(CC2=CC=CC=C2)C=C(Br)C=C1 MMVVYHDFMKIFOH-UHFFFAOYSA-N 0.000 description 1
- SFUWPINCINTNFI-UHFFFAOYSA-N O=S(=O)(C1=CC=CC=C1)C1=CC(Cl)=CC=C1C1=C(CC2=CC=CC=C2)C=C(Cl)C=C1 Chemical compound O=S(=O)(C1=CC=CC=C1)C1=CC(Cl)=CC=C1C1=C(CC2=CC=CC=C2)C=C(Cl)C=C1 SFUWPINCINTNFI-UHFFFAOYSA-N 0.000 description 1
- YYCIIUVDQHANOF-UHFFFAOYSA-M O=S(=O)(O[Na])C1=C(Br)C=CC(Br)=C1 Chemical compound O=S(=O)(O[Na])C1=C(Br)C=CC(Br)=C1 YYCIIUVDQHANOF-UHFFFAOYSA-M 0.000 description 1
- MNYAKDHYPLEQGC-UHFFFAOYSA-M O=S(=O)(O[Na])C1=CC(Br)=CC=C1C1=C([Na])C=C(Br)C=C1.O=S(=O)=O Chemical compound O=S(=O)(O[Na])C1=CC(Br)=CC=C1C1=C([Na])C=C(Br)C=C1.O=S(=O)=O MNYAKDHYPLEQGC-UHFFFAOYSA-M 0.000 description 1
- YFEGQLMMZKDTMN-UHFFFAOYSA-N O=[SH](=O)ClC1=C(C2=CC=C(Br)C=C2S(=O)(=O)Cl)C=CC(Br)=C1 Chemical compound O=[SH](=O)ClC1=C(C2=CC=C(Br)C=C2S(=O)(=O)Cl)C=CC(Br)=C1 YFEGQLMMZKDTMN-UHFFFAOYSA-N 0.000 description 1
- MDIPCPYKJZOCRO-UHFFFAOYSA-N O=[SH](=O)ClC1=C(C2=CC=C(Cl)C=C2S(=O)(=O)Cl)C=CC(Cl)=C1 Chemical compound O=[SH](=O)ClC1=C(C2=CC=C(Cl)C=C2S(=O)(=O)Cl)C=CC(Cl)=C1 MDIPCPYKJZOCRO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 125000005620 boronic acid group Chemical group 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- NSWRSAFGHPRHGG-UHFFFAOYSA-L dichloronickel;2-pyridin-2-ylpyridine Chemical compound Cl[Ni]Cl.N1=CC=CC=C1C1=CC=CC=N1 NSWRSAFGHPRHGG-UHFFFAOYSA-L 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- UYLRKRLDQUXYKB-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UYLRKRLDQUXYKB-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/14—Polysulfides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/04—Polysulfides
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/145—Side-chains containing sulfur
- C08G2261/1452—Side-chains containing sulfur containing sulfonyl or sulfonate-groups
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/516—Charge transport ion-conductive
Definitions
- the present invention is directed to polyarylene polymers useful as engineering polymers, and to processes and monomers for use in preparing the polymers.
- High performance polymers are a fast growing portion of the engineering polymers market. These polymers offer excellent performance under harsh operating conditions by virtue of their high temperature stability, chemical resistance, high tensile properties, and abrasion resistance. However, existing polymers all display compromises in certain attributes while excelling in others.
- thermoplastic HPP are either semi-crystalline or amorphous with the former typically offering superior chemical and abrasion resistance and the latter superior thermal resistance and mechanical toughness.
- semi-crystalline HPP are polyphenylene sulfide, liquid-crystal polyesters, and polyether ketones
- the most common amorphous HPP are polyether sulfones and thermoplastic polyimides. These polymers are typically filled with glass fiber, carbon fiber, graphite, and other materials as reinforcements to improve their tensile properties, dimensional stability, and wear resistance.
- HPP self-reinforced polyphenylene
- SRP self-reinforced polyphenylene
- amorphous polymer with many of the attributes of the semi-crystalline polymers.
- SRP offers a unique combination of tensile properties, abrasion resistance, chemical resistance, and thermal stability.
- the key to its high performance is the rigid-rod phenylene backbone which makes further fiber reinforcement unnecessary.
- the polyphenylene backbone can be substituted with phenylketone groups to render it amorphous and allow for thermal processing. For example, Wang and Quirk, Macromolecules, 1995, 28 (10), p.
- poly(2,5-benzophenone) is thought to be amorphous due to the head-tail disorder introduced in the polymer backbone during polymerization of 2,5-dichlorobenzophenone and that the degree of disorder has an effect on the glass transition temperature (Tg) of the polymer.
- a sulfone version of SRP such as poly(2,5-diphenylsulfone) (PDS)
- PDS poly(2,5-diphenylsulfone)
- One aspect of the present invention is a polymer comprising repeating units of Formula (I):
- T is a bulky aromatic group
- T is a bulky aromatic group.
- the repeat unit can be referred to as a rigid-rod polyarylene; however it has a higher degree of structural order than typical rigid-rod polyphenylenes by virtue of its symmetrically meta-disubstituted biphenylene structure.
- bulky aromatic group is meant an aromatic carbocyclic group having a single ring (e.g., phenyl), multiple rings (e.g., biphenyl), or multiple condensed rings in which at least one is aromatic, (e.g., 1,2,3,4-tetrahydronaphthyl, naphthyl, anthryl, or phenanthryl).
- the bulky aromatic group can be optionally substituted with a non-reactive group, such as alkyl, other aromatic groups, and other non-reactive functional groups such as ethers.
- T is phenyl.
- polymer is intended to include homopolymers, copolymers, and terpolymers.
- the polymer can have a number average molecular weight (M n ) of at least about 5,000, or at least about 15,000, or at least about 19,000.
- the polymer can also have a weight average molecular weight (M w ) of at least 80,000, or at least 200,000.
- the polymer is a homopolymer.
- the polymer is a copolymer, containing other repeat units.
- Such other repeat units can maintain the rigid-rod nature of the biphenylene backbone of the polymer comprising repeating units of Formula (I), or can introduce varying degrees of flexibility.
- Appropriate rigid-rod repeat units can be similar in chemical composition and structure to preserve the physical properties of the polymer comprising repeating units of Formula (I) or can be different to introduce additional properties required for processing and/or for the desired application of the polymer.
- the polymer can additionally comprise repeating units of Formula (II):
- T′ is a bulky aromatic group.
- T′ is phenyl.
- These embodiments introduce sufficient head-tail disorder in the phenylene repeat units of the polymer to modify its physical properties while preserving the rigid-rod structure.
- Polymers comprising repeating units of both Formula (I) and Formula (II) can have a number average molecular weight (M n ) of at least about 5,000, or at least about 9,000, or at least about 60,000.
- the polymers can also have a weight average molecular weight (M w ) of at least 40,000, or at least 300,000.
- a suitable monomer to prepare polymers comprising repeating units of Formula (I) is a compound of Formula (IA):
- T is as described above and X is independently Br or Cl, typically Cl, and has a higher degree of structural order than typical rigid-rod polyphenylenes by virtue of its symmetrically meta-disubstituted biphenylene structure.
- a suitable monomer to prepare polymers comprising repeating units of Formula (II) is a compound of Formula (IIA):
- T′ is as described above and X′ is independently Br or Cl, typically Cl.
- X′ is independently Br or Cl, typically Cl.
- the polymer comprising repeating units of Formula (I) with repeating units of Formula (II) can be block, random, or alternating copolymers.
- the monomers of Formulae (IA) and (IIA) may be reacted to form larger monomeric units that are then polymerized alone or with other monomers to form the polymers disclosed herein.
- a copolymer (-A-) x (—B—) y may be formed by copolymerizing monomer X-A-X with monomer X—B—X, or by forming larger monomer X-A-B—X and polymerizing that monomer. In both cases, the resulting polymer is considered a copolymer derived from monomer X-A-X and monomer X—B—X.
- the monomers of Formula (IA) and (IIA), and the reactants used to prepare the monomers may be obtained commercially or be prepared using any known method in the art or those disclosed herein.
- the practical upper limit to the number of monomeric units in the polymer is determined in part by the desired solubility of a polymer in a particular solvent or class of solvents. As the total number of monomeric units increases, the molecular weight of the polymer increases. The increase in molecular weight is generally expected to result in a reduced solubility of the polymer in a particular solvent. Moreover, in one embodiment, the number of monomeric units at which a polymer becomes substantially insoluble in a given solvent is dependent in part upon the structure of the monomer.
- a polymer composed of disubstituted biphenylene-based monomers may become substantially insoluble in an organic solvent if the resulting polymer becomes too rigid in the course of polymerization and the biphenylene repeat unit is too structurally regular due to the structure of T.
- the number of monomeric units at which a copolymer becomes substantially insoluble in a given solvent is dependent in part upon the ratio of the comonomers.
- a copolymer composed of several rigid monomers may become substantially insoluble in an organic solvent when ratio of disubstituted biphenylene monomeric units to substituted phenylene monomeric units is too large.
- the polymerizations as described herein can generally be performed by synthetic routes in which the leaving groups of the monomers are eliminated in carbon-carbon bond-forming reactions. Such carbon-carbon bond-forming reactions are typically mediated by a zerovalent transition metal complex that contains neutral ligands. In one embodiment, the zerovalent transition metal complex contains nickel or palladium.
- complex is meant one or more metal cations together with associated anions and/or neutral ligands.
- Neutral ligands are defined as ligands that are neutral, with respect to charge, when formally removed from the metal in their closed shell electronic state.
- Neutral ligands contain at least one lone pair of electrons, a pi-bond, or a sigma bond that is capable of binding to the transition metal.
- the neutral ligand may also be a combination of two or more neutral ligands.
- Neutral ligands may also be polydentate when more than one neutral ligand is connected via a bond or a hydrocarbyl, substituted hydrocarbyl or a functional group tether.
- a neutral ligand may be a substituent of another metal complex, either the same or different, such that multiple complexes are bound together.
- Neutral ligands can include carbonyls, thiocarbonyls, carbenes, carbynes, allyls, alkenes, olefins, cyanides, nitriles, carbon monoxide, phosphorus containing compounds such as phosphides, phosphines, or phosphites, acetonitrile, tetrahydrofuran, tertiary amines (including heterocyclic amines), ethers, esters, phosphates, phosphine oxides, and amine oxides.
- the zerovalent transition metal compound that is the active species in carbon-carbon bond formation can be introduced directly into the reaction, or can be generated in situ under the reaction conditions from a precursor transition metal compound and one or more neutral ligands.
- a zerovalent nickel compound such as a coordination compound like bis(1,5-cyclooctadiene)nickel(0)
- a neutral ligand such as triphenylphosphine or 2,2′-bipyridine.
- a second neutral ligand such as 1,5-cyclooctadiene, can be used to stabilize the active zerovalent nickel compound.
- the catalyst is formed from a divalent nickel salt.
- the nickel salt can be any nickel salt that can be converted to the zerovalent state under reaction conditions. Suitable nickel salts are the nickel halides, typically nickel dichloride or nickel dibromide, or coordination compounds, typically bis(triphenylphosphine)nickel dichloride or (2,2′-bipyridine)nickel dichloride.
- the divalent nickel salt is typically present in an amount of about 0.01 mole percent or greater, more typically about 0.1 mole percent or greater or 1.0 mole percent or greater.
- the amount of divalent nickel salt present is typically about 30 mole percent or less, more typically about 15 mole percent or less based on the amount of monomers present.
- the polymerization is performed in the presence of a material capable of reducing the divalent nickel ion to the zerovalent state.
- Suitable material includes any metal that is more easily oxidized than nickel. Suitable metals include zinc, magnesium, calcium and lithium, with zinc in the powder form being typical.
- At least stoichiometric amounts of reducing agent based on the monomers are required to maintain the nickel species in the zerovalent state throughout the reaction. Typically, about 150 mole percent or greater, more typically about 200 mole percent or greater, or about 250 mole percent or greater is used.
- the reducing agent is typically present in an amount of about 500 mole percent or less, about 400 mole percent or less, or about 300 mole percent or less based on the amount of monomer.
- Suitable ligands are neutral ligands as described above, and include trihydrocarbylphosphines.
- Typical ligands are monodentate, such as triaryl or trialkylphosphines like triphenylphosphine, or bidentate, such as 2,2′-bipyridine.
- a compound capable of acting as a monodentate ligand is typically present in an amount of from about 10 mole percent or greater, or about 20 mole percent or greater based on the monomer.
- a compound capable of acting as a monodentate ligand is typically present in an amount of about 100 mole percent or less, about 50 mole percent or less, or about 40 mole percent or less.
- a compound capable of acting as a bidentate ligand is typically present in an amount that is about a molar equivalent or greater based on the divalent nickel salt.
- the bidentate ligand can be incorporated into the nickel salt as a coordination compound as described above.
- a dihalo derivative of one monomer is reacted with a derivative of another monomer having two leaving groups selected from boronic acid (—B(OH 2 ) or boronate salt, boronic acid esters (—BOR 2 ) or (—B(ORO)), and boranes (—BR 2 ), where R is generally a hydrocarbyl group, in the presence of a catalytic amount of a zerovalent palladium compound containing a neutral ligand as described above, such as tetrakis(triphenylphosphine)palladium(0).
- boronic acid —B(OH 2 ) or boronate salt
- boronic acid esters —BOR 2
- B(ORO) boranes
- the reaction mixture should include sufficient water or an organic base to hydrolyze the boronic ester or borane group to the corresponding boronic acid group.
- the diboronic derivative of a monomer can be prepared from the dihalo derivative by known methods, such as those described in Miyaura et al., Synthetic Communication, Vol. 11, p. 513 (1981) and Wallow et al., American Chemical Society, Polymer Preprint, Vol. 34, (1), p. 1009 (1993).
- Suitable accelerators include alkali metal halides such as sodium bromide, potassium bromide, sodium iodide, tetraethylammonium iodide, and potassium iodide.
- the accelerator is used in a sufficient amount to accelerate the reaction, typically 10 mole percent to 100 mole percent based on the monomer.
- the reactions are typically run in a suitable solvent or mixture of solvents, that is a solvent that is not detrimental to catalyst, reactant and product, and preferably one in which the reactants and products are soluble.
- suitable solvents include N,N-dimethylformamide (DMF), toluene, tetrahydrofuran (THF), acetone, anisole, acetonitrile, N,N-dimethylacetamide (DMAc), and N-methylpyrrolidinone (NMP).
- DMF N,N-dimethylformamide
- THF tetrahydrofuran
- acetone acetone
- anisole acetonitrile
- NMP N-methylpyrrolidinone
- the amount of solvent used in this process can vary over a wide range. Generally, it is desired to use as little solvent as possible.
- the reactions are typically conducted in the absence of oxygen and moisture, as the presence of oxygen can be detrimental to the catalyst and the presence of a significant amount of water could lead to premature termination of the process. More typically, the reaction is performed under an inert atmosphere such as nitrogen or argon.
- the reactions can be performed at any temperature at which the reaction proceeds at a reasonable rate and does not lead to degradation of the product or catalyst. Generally, the reaction is performed at a temperature of about 20° C. to about 200° C., more typically less than 100° C.
- the reaction time is dependent upon the reaction temperature, the amount of catalyst and the concentration of the reactants, and is usually about 1 hour to about 100 hours.
- the polymers prepared by the disclosed methods can be recovered according to conventional techniques including filtration and precipitation using a non-solvent. They also can be dissolved or dispersed in a suitable solvent for further processing.
- the polymers disclosed herein are suitable for use as engineering polymers in applications such as, for example, molecular reinforcement in nanocomposites, mineral-filled and fiber-reinforced composites, injection and compression-molded parts, fibers, films, sheets, papers, and coatings, and can be processed both thermally as is typical for thermoplastic polymers and in solution after dissolving in suitable solvents depending on the requirements of the application.
- Copper powder was activated according to the procedure in Vogel's Textbook of Practical Organic Chemistry, 4 th Edition, 1981, Longman (London), pages 285-286. Copper bronze (50 g, Aldrich Chemical Company, Milwaukee, Wis.) was stirred for 10-20 minutes with a solution of iodine (10 g) dissolved in acetone (500 mL) to give a gray mixture. The copper was filtered off, washed acetone, and added to a solution of hydrochloric acid (150 mL) and acetone (150 mL). The mixture was stirred until the gray solids dissolved then the copper was filtered off and washed well with acetone. The activated copper solids were dried under high vacuum and transferred to a glove box for storage and handling.
- the reaction mixture was poured into concentrated hydrochloric acid to precipitate the polymer and the mixture was chopped in a blender to disperse the polymer into particles.
- the polymer was collected by vacuum filtration using water to wash the polymer.
- the polymer was washed with concentrated hydrochloric acid followed by water.
- the damp polymer was washed with cyclohexane followed by methanol and dried in a vacuum oven at 70° C. under nitrogen purge to give 1.32 g (88% yield) of poly[(2,2′-bis-benzenesulfonyl-4,4′-biphenylene)].
- the polymer showed low solubility in DMSO and DMAc.
- a broad 1 H NMR spectrum was obtained in DMSO-d 6 at 100° C.: 7.25, 7.59, 7.70, 7.73, 8.08, 8.38.
- the molecular weight distribution was measured by gel permeation chromatography in DMAc: M n 15,300, M w 202,000, M z 1,200,000; [ ⁇ ] 4.49.
- Thermo-gravimetric analysis (10° C./min scan rate) showed an onset of decomposition at 435° C. under nitrogen. Differential scanning calorimetry showed a glass transition temperature of 225° C.
- a 300 mL round-bottom flask equipped with a large stirring bar and a septum was charged with bis(1,5-cyclooctadiene) nickel(0) (11.11 g, 40.4 mmoles), cyclooctadiene (4.37 g, 40.4 mmoles), 2,2′-bipyridine (6.31 g, 40.4 mmoles), and DMAc (120 mL).
- the flask was heated to 70° C. under nitrogen for 30 minutes to give a dark violet-colored solution.
- the warm reaction mixture was poured into concentrated hydrochloric acid (250 mL) to precipitate the polymer and the mixture was chopped in a blender to disperse the polymer into particles.
- the polymer was collected by vacuum filtration using water to wash the polymer.
- the polymer was washed with concentrated hydrochloric acid followed by water.
- the damp polymer was washed with hexane followed by methanol and dried in a vacuum oven at 70° C. under nitrogen purge to give 8.35 g (97% yield) of poly[(2,2′-bis-benzenesulfonyl-4,4′-biphenylene)].
- the polymer showed low solubility in DMSO and DMAc.
- a broad 1 H NMR spectrum was obtained in DMSO-d 6 at 120° C.: 7.29, 7.63, 7.73, 7.74, 8.10, 8.41.
- the molecular weight distribution was measured by gel permeation chromatography in DMAc: M n 19,400, M w 83,800, M z 244,000; [ ⁇ ]-4.32.
- Thermo-gravimetric analysis (10° C./min scan rate) showed an onset of decomposition at 400° C. under air. Differential scanning calorimetry showed a glass transition temperature of 225° C.
- the molecular weight distribution was measured by gel permeation chromatography in DMAc: M n 750, M w 3000, M w 7,800; [ ⁇ ] 0.09.
- the material was too low in molecular weight to be considered the desired polymer, poly(benzenesulfonyl-1,4-phenylene).
- the cooled reaction mixture was poured into concentrated hydrochloric acid to precipitate the polymer and the mixture was chopped in a blender to disperse the polymer into particles.
- the polymer was collected by vacuum filtration using methanol to wash the polymer.
- the polymer was washed several times with concentrated hydrochloric acid followed by methanol.
- the damp polymer was dried in a vacuum oven at 80° C. under nitrogen purge to give 2.17 g (100% yield) of the 95:5 copolymer, poly[(2,2′-bis-benzenesulfonyl-4,4′-biphenylene)-co-(benzenesulfonyl-1,4-phenylene)].
- the polymer showed low solubility in DMSO and DMAc.
- the copolymer (0.5 g) was dissolved in DMAc at 160° C. to give 5.0 weight % solution.
- the cooled solution was filtered using a glass microfiber syringe filter and poured into a glass film-casting dish, which was placed on a leveled drying stage in a nitrogen-purged drying chamber.
- the dried film became slightly hazy and lifted free of the dish on its own.
- the film was further dried at 150° C. in a vacuum oven under nitrogen purge. The film was strong in tension, but was brittle as it broke into pieces when folded over and creased.
- the copolymer (0.5 g) was dissolved in 1,1,2,2-tetrachloroethane at room temperature to give 3.2 weight % solution.
- the solution was filtered using a glass microfiber syringe filter and poured into a glass film-casting dish, which was placed on a leveled drying stage in a nitrogen-purged drying chamber.
- the film was further dried at 80° C. in a vacuum oven under nitrogen purge. The film had become opaque and was floated free of the dish in water after scoring the edge. The film was not strong in tension and was brittle such that film could not even be folded over.
- the mixture was extracted several times with dichloromethane.
- the organic extracts were dried with sodium sulfate, filtered, and evaporated, then the solids were dried in a vacuum oven to give 14.38 g (100% crude yield).
- the solids were recrystallized from ethanol after treating with decolorizing carbon to give about 14 g in two crops.
- the solids were recrystallized from ethanol to give 12.24 g (85% yield) of 2-benzenesulfonyl-1,4-dichlorobenzene.
- a 1 L round-bottom flask equipped with a stirring bar was charged with copper(I) chloride (25 g, 0.25 moles) and hydrochloric acid (85 mL) to give a dark green solution then chilled to 0° C. in an ice bath.
- the cold diazonium salt slurry was added slowly to the solution to give immediate gas evolution.
- the solution was stirred until it warmed to room temperature and evaporated to remove excess hydrochloric acid.
- the solids were dissolved in water, treated with sodium carbonate to give pH 7, which precipitate residual copper salts, filtered and evaporated to give a tan solid.
- the solids were recrystallized twice from ethanol after treating with decolorizing carbon and dried under vacuum at 80° C.
- reaction mixture was diluted with DMAc (20 mL), poured into concentrated hydrochloric acid to precipitate the polymer, and rinsed from the flask with methanol and concentrated hydrochloric acid.
- the mixture was chopped in a blender to disperse the polymer into particles.
- the polymer was collected by vacuum filtration and rinsed from the blender jar with methanol, then washed on the filter three times with a mixture of methanol and concentrated hydrochloric acid. The polymer was then washed alternatively with water and methanol several times, and dried in a vacuum oven at 80° C.
- the copolymer (0.1 g) was dissolved in 1,1,2,2-tetrachloroethane to give 1.1 weight % solution.
- the solution was poured into a polymethylpentene Petri dish and placed on a leveled drying stage in a nitrogen-purged drying chamber. The dried film lifted free of the dish on its own. The film was further dried at 60° C. in a vacuum oven under nitrogen purge. The film was strong, flexible, tough, and creasable.
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EP2926903A1 (en) * | 2014-03-31 | 2015-10-07 | Studiengesellschaft Kohle mbH | Process for preparing catalyst loaded polyphenylene particles, the obtained polyphenylene particles and their use as catalysts |
US11224158B2 (en) | 2019-08-22 | 2022-01-18 | Great Plains Manufacturing, Inc. | Metering device for agricultural product |
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US5565543A (en) * | 1988-02-17 | 1996-10-15 | Maxdem Incorporated | Rigid-rod polymers |
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US5889134A (en) * | 1996-11-26 | 1999-03-30 | North Dakota State University | Chiral organozinc species for use in asymmetric reactions |
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GB9905203D0 (en) | 1999-03-05 | 1999-04-28 | Cambridge Display Tech Ltd | Polymer preparation |
AU2003268784A1 (en) * | 2002-10-08 | 2004-05-04 | Toyo Boseki Kabushiki Kaisha | Polyarylene ether compound containing sulfonic acid group, composition containing same, and method for manufacturing those |
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US20080287646A1 (en) * | 2005-10-13 | 2008-11-20 | Sumitomo Chemical Company, Limited | Polyarylene and Method for Producing the Same |
JP5040226B2 (ja) * | 2006-03-07 | 2012-10-03 | 住友化学株式会社 | ポリアリーレン及びその製造方法 |
WO2007102235A1 (ja) * | 2006-03-07 | 2007-09-13 | Sumitomo Chemical Company, Limited | ポリアリーレンおよびその製造方法 |
KR20090053935A (ko) | 2006-09-20 | 2009-05-28 | 스미또모 가가꾸 가부시키가이샤 | 폴리아릴렌의 제조 방법 |
JP2008285661A (ja) * | 2007-04-17 | 2008-11-27 | Sumitomo Chemical Co Ltd | スルホン酸基を有するポリマーの製造方法 |
JP2009079214A (ja) | 2007-09-04 | 2009-04-16 | Sumitomo Chemical Co Ltd | スルホ基を有する重合体の製造方法 |
JP2009275219A (ja) * | 2008-04-17 | 2009-11-26 | Sumitomo Chemical Co Ltd | ポリアリーレンの製造方法 |
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EP2519554B1 (en) | 2016-03-16 |
EP2519554A2 (en) | 2012-11-07 |
WO2011090705A3 (en) | 2011-11-24 |
JP5701903B2 (ja) | 2015-04-15 |
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