CN106957429A - 聚合物制备方法 - Google Patents
聚合物制备方法 Download PDFInfo
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- CN106957429A CN106957429A CN201710018224.9A CN201710018224A CN106957429A CN 106957429 A CN106957429 A CN 106957429A CN 201710018224 A CN201710018224 A CN 201710018224A CN 106957429 A CN106957429 A CN 106957429A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- -1 diphenylamines Chemical class 0.000 claims description 57
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 150000002431 hydrogen Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002733 (C1-C6) fluoroalkyl group Chemical group 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 190000021678 hydrogen Chemical compound 0.000 claims 3
- 190000022159 sulfonic acid Chemical compound 0.000 claims 3
- 190000011743 oxygen Chemical compound 0.000 claims 2
- 239000007815 EtOH Substances 0.000 claims 1
- 190000020998 Ethamine Chemical compound 0.000 claims 1
- 229930028213 Ethanol Natural products 0.000 claims 1
- 229930163938 N-methyl-pyrrolidinone Natural products 0.000 claims 1
- 229930038666 Vilsmeier-Haack reagent Natural products 0.000 claims 1
- 239000008071 dimethylformamide Substances 0.000 claims 1
- 190000004803 dimethylformamide Chemical compound 0.000 claims 1
- 190000014300 ethanol Chemical compound 0.000 claims 1
- 190000003170 ethylsulfonic acid Chemical compound 0.000 claims 1
- 239000008081 methanol Substances 0.000 claims 1
- 190000022349 methanol Chemical compound 0.000 claims 1
- 229930158649 methanol Natural products 0.000 claims 1
- 190000011915 phosphoric anhydride Chemical compound 0.000 claims 1
- 229910001393 phosphorus pentoxide Inorganic materials 0.000 claims 1
- 190000021717 potassium chloride Chemical compound 0.000 claims 1
- 229910001481 potassium chloride Inorganic materials 0.000 claims 1
- 239000008091 pyridine Substances 0.000 claims 1
- 190000019579 pyridine Chemical compound 0.000 claims 1
- 229930166304 pyridine Natural products 0.000 claims 1
- 190000022347 sulphur Chemical compound 0.000 claims 1
- 190000011440 trifluoromethane sulfonic acid Chemical compound 0.000 claims 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 abstract description 21
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 125000005537 sulfoxonium group Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 45
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical class CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- JXTGICXCHWMCPM-UHFFFAOYSA-N (methylsulfinyl)benzene Chemical compound CS(=O)C1=CC=CC=C1 JXTGICXCHWMCPM-UHFFFAOYSA-N 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 229920000412 polyarylene Polymers 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 5
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012038 nucleophile Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- LPSWFOCTMJQJIS-UHFFFAOYSA-N sulfanium;hydroxide Chemical compound [OH-].[SH3+] LPSWFOCTMJQJIS-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 230000017858 demethylation Effects 0.000 description 2
- 238000010520 demethylation reaction Methods 0.000 description 2
- 229940035422 diphenylamine Drugs 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- MGEGQAUINMTPGX-UHFFFAOYSA-N n-phenylaniline;trifluoromethanesulfonic acid Chemical class [O-]S(=O)(=O)C(F)(F)F.C=1C=CC=CC=1[NH2+]C1=CC=CC=C1 MGEGQAUINMTPGX-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 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 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- YEUYZNNBXLMFCW-UHFFFAOYSA-N 1-bromo-4-methylsulfanylbenzene Chemical compound CSC1=CC=C(Br)C=C1 YEUYZNNBXLMFCW-UHFFFAOYSA-N 0.000 description 1
- LXINKRZIJMGCDO-UHFFFAOYSA-N 1-methylsulfanyl-4-phenylbenzene Chemical compound C1=CC(SC)=CC=C1C1=CC=CC=C1 LXINKRZIJMGCDO-UHFFFAOYSA-N 0.000 description 1
- FEKWWZCCJDUWLY-UHFFFAOYSA-N 3-methyl-1h-pyrrole Chemical class CC=1C=CNC=1 FEKWWZCCJDUWLY-UHFFFAOYSA-N 0.000 description 1
- IPIOTZDJIIDRBQ-UHFFFAOYSA-N 4-methylpyridine;pyridine Chemical compound C1=CC=NC=C1.CC1=CC=NC=C1 IPIOTZDJIIDRBQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-methyl-pyrrolidinone Natural products CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- RFIICTNHYXZALY-UHFFFAOYSA-N OB(O)C1=CC=CC=C1.OB(O)OC1=CC=CC=C1 Chemical compound OB(O)C1=CC=CC=C1.OB(O)OC1=CC=CC=C1 RFIICTNHYXZALY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 235000013547 stew Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YOIAWAIKYVEKMF-UHFFFAOYSA-N trifluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)F.OS(=O)(=O)C(F)(F)F YOIAWAIKYVEKMF-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- 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
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
- C08G75/0213—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur
- C08G75/0218—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
-
- 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
-
- 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
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0227—Polyarylenethioethers derived from monomers containing two or more aromatic rings
-
- 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
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
-
- 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
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
- C08G75/0272—Preparatory processes using other sulfur sources
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Emergency Medicine (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
本发明提供一种聚合物制备方法。该聚合物制备方法包含:将至少一种具有式(I)所示结构的单体在磺酸、二苯胺及含氧的磷化物(oxygen‑containing phosphide)存在下进行反应,得到一锍盐聚合物(sulfonium salt polymer),其中x是0、1或2;R1是C1‑6烷基;以及,R2是独立为氢或C1‑6烷基。
Description
技术领域
本发明是关于一种聚合物的制备方法,更特别地是关于一种锍盐聚合物或聚芳硫醚的制备方法。
背景技术
聚芳硫醚是具有出色的物理特性,例如耐热性、耐化学性、耐火性及电绝缘特性,因此广泛用于计算机附件、汽车附件、与腐蚀性化学物质接触的零件的涂料、以及具有耐化学性的工业纤维。
然而,由于传统聚芳硫醚的制备方法主要是以卤制程为主,除了低的聚芳硫醚树脂产率外,还会产生无法回收的含卤副产物,造成环境污染。此外,传统聚芳硫醚树脂的制备方法所得的聚芳硫醚树脂纯化不易,会有卤副产物残留于聚芳硫醚树脂中。
因此,业界需要一种新的方法制备聚芳硫醇。
发明内容
根据本发明的实施例,本发明提供一种聚合物制备方法,包含将至少一种具有式(I)所示结构的单体在磺酸、二苯胺及含氧的磷化物(oxygen-containing phosphide)存在下进行反应,得到一锍盐聚合物(sulfonium salt polymer)。
其中x是0、1或2;R1是C1-6烷基;以及,R2是独立为氢或C1-6烷基。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,以下结合具体实施例,对本发明作进一步的详细说明。
聚芳硫醚若利用单体(I)(其化学结构可为)在酸性环境下聚合成阳离子聚合物,再进行去甲基化来进行制备,请参照反应式(I),则所得的阳离子聚合物(由单体(I)聚合而成)其转换率并不高。
此外,若参照反应式(II)制备单体(I),需先将甲基苯基亚砜(methyl phenylsulfoxide)与茴香硫醚(methyl phenyl sulfide)在酸性环境下合成,在得到阳离子中间体后,再进行去甲基化与氧化反应,才可获得。可能因反应式(II)的制备过程较为繁复,导致聚芳硫醚的产率下降。
基于上述,本发明实施例提供一种聚合物制备方法,可提升单体转换为锍盐聚合物的转换率,且所使用的单体也较容易获得。根据本发明实施例,该方法包含将至少一种具有式(I)所示结构的单体在磺酸、二苯胺(diphenyl amine)及含氧的磷化物(oxygen-containing phosphide)存在下进行聚合反应,得到一锍盐聚合物(sulfonium saltpolymer)。
其中x可为0、1或2;R1可为C1-6烷基;以及,R2可独立为氢或C1-6烷基。根据本发明实施例,该具有式(I)所示结构的单体的亚砜(S=O)官能基可在酸性环境中质子化为具有反应活性的氢氧化锍(sulfonium hydroxide)官能基,并借由二苯胺作为电荷稳定试剂,提供电子与氢氧化锍形成错体(complex)结构,使芳香环的π电子能够提升反应性进行聚合反应。此外,在含氧的磷化物(oxygen-containing phosphide)存在下进行聚合反应,可大幅增加具由式(I)所示结构的单体转换为锍盐聚合物(或聚芳硫醚)的转换率。此外,在得到锍盐聚合物之后,可将一亲核试剂(nucleophile)进一步与所得到的锍盐聚合物反应,得到一无卤素残留的耐高温聚芳硫醚(polyarylene sulfide)(熔融温度(Tm)可大于或等于280℃)。根据本发明实施例,该单体转换为锍盐聚合物(或聚芳硫醚)的转换率计算方式如下述方程式:
根据本发明实施例,该烷基可为直链(linear)或分支键(branched)烷基。因此,R1可为甲基(methyl)、乙基(ethyl)、丙基(propyl)、异丙基(isopropyl)、正丁基(n-butyl)、叔丁基(t-butyl)、仲丁基(sec-butyl)、异丁基(isobutyl)、戊基(pentyl)或己基(hexyl)。此外,R2可各自独立为氢、氟、甲基、乙基、丙基、异丙基、正丁基、叔丁基、仲丁基、异丁基、戊基或己基。
根据本发明实施例,该磺酸可为具有式(II)所示结构的化合物,
其中R3可为氢、C1-6烷基或C1-6氟烷基。在此,该氟烷基是指碳上的氢全部或部分被氟取代的烷基,且可为直链(linear)或分支键(branched)。举例来说,氟甲基可为单氟甲基、二氟甲基或全氟甲基。根据本发明实施例,R3可为甲基、乙基、丙基、异丙基、正丁基、叔丁基、仲丁基、异丁基、戊基、己基、氟甲基、氟乙基或氟丙基。根据本发明某些实施例,该磺酸可为甲基磺酸、乙基磺酸、丙基磺酸、三氟甲基磺酸(CF3SO3H)或其组合。根据本发明实施例,该磺酸与该单体的摩尔比可为约1至200,例如约1至100。在此,该磺酸可提供酸性环境促进该单体进行聚合反应,且过量的磺酸可同时作为反应的溶剂。
根据本发明实施例,在本发明所述聚合物制备方法中添加该含氧的磷化物,可大幅增加具有式(I)所示结构的单体转换为锍盐聚合物的转换率。该含氧的磷化物可为由氧及磷所构成的化合物,例如磷酸酐(P2O5)。此外,该含氧的磷化物可为由氧、氢及磷所构成的化合物,例如多聚磷酸(H(n+2)PnO(3n+1),其中n大于1)。根据本发明实施例,该含氧的磷化物与该单体的摩尔比可为约0.5至2,例如约0.5至1.5。
根据本发明实施例,该二苯胺与该单体的摩尔比可为约0.5至2,例如约0.5至1.5。上述二苯胺以及含氧的磷化物是促进该具有式(I)所示结构的单体进行聚合反应,二苯胺以及含氧的磷化物并非反应物。
根据本发明实施例,本发明所述聚合物制备方法可将一种具有式(I)所示结构的单体在磺酸、二苯胺及含氧的磷化物存在下进行聚合反应,其中该具有式(I)所示结构的单体可例如为 此外,根据本发明实施例,本发明所述聚合物制备方法可将二种具有式(I)所示结构的单体在磺酸、二苯胺及含氧的磷化物存在下进行聚合反应,其中该二种具有式(I)所示结构的单体的一者可为再者,根据本发明实施例,本发明所述聚合物制备方法可将二种具有式(I)所示结构的单体在磺酸、二苯胺及含氧的磷化物存在下进行聚合反应,其中该二种具有式(I)所示结构的单体可分别为
根据本发明实施例,以本发明所述聚合物制备方法所得的锍盐聚合物可具有至少一种具有式(III)所示结构的重复单元,
其中x可为0、1或2;R1可为C1-6烷基;R2可独立为氢或C1-6烷基;以及,R3可为氢、C1-6烷基或C1-6氟烷基。根据本发明某些实施例,该具有式(III)所示结构的重复单元可为
根据本发明实施例,该聚合物制备方法,在获得该锍盐聚合物之后,可更包含将一亲核试剂(nucleophile)与该锍盐聚合物反应,得到一聚芳硫醚(polyarylene sulfide)。其中,该亲核试剂(nucleophile)可例如为具有取代/非取代基的吡啶或其衍生物(例如:吡啶、4-甲基吡啶)、胺类(如:三乙胺)、卤化盐类(例如:氯化钾)、醇类(例如:甲醇、乙醇)或酰胺类(例如:二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯酮),且该亲核试剂与具有式(I)所示结构的单体(用来合成该锍盐聚合物)的摩尔比可为约1至100,即亦可加入过量亲核试剂作为溶剂。该聚芳硫醚可具有至少一种具有式(IV)所示结构的重复单元。
其中x可为0、1或2;以及,R2可独立为氢或C1-6烷基。该具有式(IV)所示结构的重复单元可例如为
为了让本发明的上述和其他目的、特征和优点能更明显易懂,下文特举数实施例及比较实施例,作详细说明如下:
实施例1:
将0.5g的甲基苯基亚砜(methyl phenyl sulfide)、0.25g的五氧化二磷(phosphorus pentoxide、P2O5)与0.3g的二苯胺(diphenyl amine),加入一反应瓶中。接着,在0℃冰浴下,缓慢加入3ml的三氟甲基磺酸(trifluoromethanesulfonic acid)于反应瓶中。在室温下反应1小时后,将反应瓶缓慢回到室温。反应20小时后,将所得物倒入100ml的乙醚中并剧烈搅拌,再用少量丙酮清洗。干燥后得到锍盐聚合物(I)(白色固体)。
接着,将所得锍盐聚合物(I)溶于15ml的4-甲基吡啶(4-methylpyridine)中,并加热至回流(约100℃)。反应6小时后,将所得产物倒入30ml的盐酸水溶液(浓度为10%),再用少量丙酮清洗,得到聚芳硫醚(I)(白色固体),转换率约为88%。上述反应的反应式如下所示:
接着,使用示差扫描量热仪(differential scanning calorimetry、DSC)量测所得聚芳硫醚(I),得知其熔融温度(Tm)达281℃以及其再结晶温度(Tc)达210℃。接着,以红外线光谱仪(FT-IR)量测聚芳硫醚(I),结果如下:IR(cm-1):3065,1573,1471,1387,1092,1009,998,815,742。
实施例2:
将3g的苯基硼酸(phenylboronic acid)、3.45g的4-溴硫代苯甲醚(4-bromothioanisole)、0.1g的Pd(PPh3)4、与1.5g的氢氧化钠(Na2CO3)加入一反应瓶中。接着,在氮气下缓慢将50ml的甲苯、60ml的去离子水、与10ml的甲醇加入该反应瓶。接着,在100℃下反应24小时后,用乙酸乙酯与水对所得溶液萃取三次,并取有机层抽干,得到化合物(I)(1-methylsulfanyl-4-phenylbenzene),产率约为99%。上述反应的反应式如下所示:
利用核磁共振光谱分析化合物(I),所得的光谱信息如下:1H NMR(500MHz,ppm,CDCl3):2.55(-CH3,s),7.33-7.37(phenyl,3H,m),7.43-7.45(phenyl,2H,m),7.54-7.6(phenyl,4H,m)。
接着,将1g的化合物(I),加入一反应瓶中,并缓慢加入10ml的冰醋酸与2ml的双氧水(浓度为30%)。在室温下反应20分钟后,将所得溶液过滤,得到橘色固体。将橘色固体以二氯甲烷与水进行萃取三次,并收集有机层。接着,对有机层进行除水、过滤及浓缩后,得到化合物(II)。上述反应的反应式如下所示:
利用核磁共振光谱分析化合物(II),所得的光谱信息如下:1H NMR(500MHz,ppm,CDCl3):2.80(-CH3,s),7.42-7.51(biphenyl,3H,m),7.62-7.63(biphenyl,2H,m),7.73-7.78(biphenyl,4H,m)。
接着,将0.5g的化合物(II)、0.39g的二苯胺及0.16g的五氧化二磷(phosphoruspentoxide、P2O5)加入一反应瓶中。接着,在0℃冰浴下缓慢加入5ml的三氟甲基磺酸。在冰浴下反应1小时后,缓慢回到室温。接着,反应20小时后,将所得物倒入100ml的乙醚中并剧烈搅拌,再用少量丙酮清洗。干燥后得到锍盐聚合物(II)。接着,将所得锍盐聚合物(II)溶于6ml的4-甲基吡啶(4-methylpyridine)中并在室温下搅拌1小时,接着加热至回流(约120℃)。反应20小时后,将所得产物倒入30ml的盐酸水溶液(浓度为10%),再用少量丙酮清洗,得到聚芳硫醚(II)(白色固体),转换率约为90%,如表1所示。上述反应的反应式如下所示:
接着,使用示差扫描量热仪(differential scanning calorimetry、DSC)量测所得聚芳硫醚(II),得知其熔融温度(Tm)达404℃以及其再结晶温度(Tc)达369℃。接着,以红外线光谱仪(FT-IR)量测聚芳硫醚(II),结果如下:IR(cm-1):3026,1590,1474,1391,1313,1152,1137,1090,1045,998,952,811,758,690。
比较例1:
将0.5g的化合物(II)与0.39g的二苯胺加入一反应瓶中。接着,在0℃冰浴下缓慢加入5ml的三氟甲基磺酸。在冰浴下反应1小时后,缓慢回到室温。接着,反应20小时后,将所得物倒入100ml的乙醚中并剧烈搅拌,再用少量丙酮清洗。干燥后得到锍盐聚合物(II)。接着,将所得锍盐聚合物(II)溶于6ml的4-甲基吡啶(4-methylpyridine)中并在室温下搅拌1小时,接着加热至回流(约120℃)。反应20小时后,将所得产物倒入30ml之盐酸水溶液(浓度为10%),再用少量丙酮清洗,得到聚芳硫醚(II)(白色固体),转换率约为57%,如表1所示。
表1
化合物(II) | 三氟甲基磺酸 | 二苯胺 | 五氧化二磷 | 转换率 | |
实施例2 | 0.5g | 5ml | 0.39g | 0.33g | 90% |
比较例1 | 0.5g | 5ml | 0.39g | - | 57% |
与比较例1相比,实施例2在将化合物(II)进行聚合时,除了加入三氟甲基磺酸及二苯胺外,还进一步加入五氧化二磷。请参照表1,与比较例1相比,以实施例2所述方式制备聚芳硫醚(II),所得的转换率明显提高。
实施例3:
将0.19g的甲基苯基亚砜、0.3g的化合物(II)、0.2g的五氧化二磷、与0.23g二苯胺加入一反应瓶中。接着,在0℃冰浴下缓慢加入3ml的三氟甲基磺酸。在冰浴下反应1小时后,缓慢回到室温。接着,反应20小时后,将所得物倒入100ml的乙醚中并剧烈搅拌,再用少量丙酮清洗。干燥后得到锍盐聚合物(III)。接着,将所得锍盐聚合物(III)溶于15ml的4-甲基吡啶(4-methylpyridine)中并在室温下搅拌1小时,接着加热至回流(约100℃)。反应6小时后,将所得产物倒入30ml的盐酸水溶液(浓度为10%),再用少量丙酮清洗,得到聚芳硫醚(III)(白色固体),转换率约为35%,如表2所示。上述反应的反应式如下所示:
(其中锍盐聚合物(III)或聚芳硫醚(III)的重复单元是以无规方式排列)。
接着,使用示差扫描量热仪(differential scanning calorimetry、DSC)量测所得聚芳硫醚(III),得知其玻璃转换温度(Tg)达113℃。接着,以红外线光谱仪(FT-IR)量测聚芳硫醚(III),结果如下:IR(cm-1):3024,1584,1474,1389,1319,1178,1155,1090,1001,810,759,694。
比较例2:
如实施例3所述方式进行,除了不添加五氧化二磷,所得的聚芳硫醚(III)转换率约为≤5%,如表2所示。
表2
化合物(II) | 三氟甲基磺酸 | 二苯胺 | 五氧化二磷 | 转换率 | |
实施例3 | 0.3g | 3ml | 0.23g | 0.2g | 35% |
比较例2 | 0.3g | 3ml | 0.23g | - | ≤5% |
与比较例2相比,实施例3在将甲基苯基亚砜与化合物(II)进行共聚合时,除了加入三氟甲基磺酸及二苯胺外,还进一步加入五氧化二磷。请参照表2,与比较例2相比,以实施例3所述方式制备聚芳硫醚(III),所得的转换率明显提高。
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (14)
1.一种聚合物制备方法,包含:
将至少一种具有式(I)所示结构的单体在磺酸、二苯胺及含氧的磷化物(oxygen-containing phosphide)存在下进行反应,得到一锍盐聚合物(sulfonium salt polymer),
其中x是0、1或2;R1是C1-6烷基;以及,R2是独立为氢或C1-6烷基。
2.根据权利要求1所述的聚合物制备方法,其中R1是甲基、乙基、丙基、异丙基、正丁基、叔丁基、仲丁基、异丁基、戊基或己基。
3.根据权利要求1所述的聚合物制备方法,其中R2是氢、甲基、乙基、丙基、异丙基、正丁基、叔丁基、仲丁基、异丁基、戊基或己基。
4.根据权利要求1所述的聚合物制备方法,其中该磺酸是具有式(II)所示结构的化合物,
其中R3是氢、C1-6烷基或C1-6氟烷基。
5.根据权利要求1所述的聚合物制备方法,其中该磺酸是甲基磺酸、乙基磺酸、丙基磺酸、三氟甲基磺酸或其组合。
6.根据权利要求1所述的聚合物制备方法,其中该含氧的磷化物是磷酸酐、多聚磷酸或其组合。
7.根据权利要求1所述的聚合物制备方法,其中该具有式(I)所示结构的单体是
8.根据权利要求1所述的聚合物制备方法,其中该至少一种具有式(I)所示结构的单体是
9.根据权利要求4所述的聚合物制备方法,其中该锍盐聚合物是具有至少一种具有式(III)所示结构的重复单元,
其中x是0、1或2;R1是C1-6烷基;R2是独立为氢或C1-6烷基;以及,R3是氢、C1-6烷基或C1-6氟烷基。
10.根据权利要求9所述的聚合物制备方法,其中该具有式(III)所示结构的重复单元是
11.根据权利要求1所述的聚合物制备方法,更包含:将一亲核试剂与该锍盐聚合物反应,得到一聚芳硫醚。
12.根据权利要求11所述的聚合物制备方法,其中该亲核试剂是吡啶、4-甲基吡啶、三乙胺、氯化钾、甲醇、乙醇、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯酮或上述的组合。
13.根据权利要求11所述的聚合物制备方法,其中该聚芳硫醚具有至少一种具有式(IV)所示结构的重复单元,
其中x是0、1或2;以及,R2是独立为氢或C1-6烷基。
14.根据权利要求13所述的聚合物制备方法,其中该具有式(IV)所示结构的重复单元是
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