JP6429096B2 - Method for producing a polymer - Google Patents
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- JP6429096B2 JP6429096B2 JP2017002113A JP2017002113A JP6429096B2 JP 6429096 B2 JP6429096 B2 JP 6429096B2 JP 2017002113 A JP2017002113 A JP 2017002113A JP 2017002113 A JP2017002113 A JP 2017002113A JP 6429096 B2 JP6429096 B2 JP 6429096B2
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- 229920000642 polymer Polymers 0.000 title claims description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 55
- 229920000412 polyarylene Polymers 0.000 claims description 34
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 32
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 13
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 12
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical group O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012038 nucleophile Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 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 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 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
- 125000002733 (C1-C6) fluoroalkyl group Chemical group 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 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
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 2
- 239000012434 nucleophilic reagent Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 229940035422 diphenylamine Drugs 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- -1 monofluoromethyl Chemical group 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
- LPSWFOCTMJQJIS-UHFFFAOYSA-N sulfanium;hydroxide Chemical compound [OH-].[SH3+] LPSWFOCTMJQJIS-UHFFFAOYSA-N 0.000 description 3
- 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 238000007796 conventional method Methods 0.000 description 2
- 230000017858 demethylation Effects 0.000 description 2
- 238000010520 demethylation reaction Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- JXTGICXCHWMCPM-UHFFFAOYSA-N (methylsulfinyl)benzene Chemical compound CS(=O)C1=CC=CC=C1 JXTGICXCHWMCPM-UHFFFAOYSA-N 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
- 0 CCC(C=*)=C*(CC(C)=C)N(C)CC=C Chemical compound CCC(C=*)=C*(CC(C)=C)N(C)CC=C 0.000 description 1
- JSAFTMHKZQHBMA-UHFFFAOYSA-N CSC1=CC=C(C=C1)C1=CC=CC=C1.CSC1=CC=C(C=C1)C1=CC=CC=C1 Chemical compound CSC1=CC=C(C=C1)C1=CC=CC=C1.CSC1=CC=C(C=C1)C1=CC=CC=C1 JSAFTMHKZQHBMA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000011109 contamination Methods 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
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本開示はポリマーの製造方法に関し、特にスルホニウム塩ポリマーまたはポリアリーレンスルフィドの製造方法に関する。 The present disclosure relates to a method for producing a polymer, and more particularly to a method for producing a sulfonium salt polymer or a polyarylene sulfide.
ポリアリーレンスルフィドは、耐熱性、耐化学性、耐火性、および電気絶縁性といった優れた物理特性を備えるため、コンピュータ用アクセサリ、自動車用アクセサリに、耐化学性を備える工業用繊維として、および腐食性化学物質と接触する部品の塗料として広く利用されている。 Polyarylene sulfide has excellent physical properties such as heat resistance, chemical resistance, fire resistance, and electrical insulation, so it can be used in computer accessories, automotive accessories, industrial fibers with chemical resistance, and corrosive It is widely used as a paint for parts that come into contact with chemical substances.
しかしながら、従来のポリアリーレンスルフィドの製造方法はハロゲン含有処理が主であり、ポリアリーレンスルフィド樹脂の収率が低いことに加え、環境汚染を引き起こす可能性のある再利用不可能なハロゲン含有副産物を生ずるものである。また、従来のポリアリーレンスルフィド樹脂の製造方法で得られるポリアリーレンスルフィド樹脂は、精製が容易でなく、ハロゲン副産物がポリアリーレンスルフィド樹脂中に残留してしまう。 However, conventional methods for producing polyarylene sulfides are primarily halogen-containing treatments, resulting in low yields of polyarylene sulfide resins and non-reusable halogen-containing by-products that can cause environmental contamination. Is. Moreover, the polyarylene sulfide resin obtained by the conventional method for producing a polyarylene sulfide resin is not easily purified, and a halogen byproduct remains in the polyarylene sulfide resin.
よって、業界では、ポリアリーレンスルフィドを製造する新たな方法が求められている。 Thus, there is a need in the industry for new methods for producing polyarylene sulfides.
本開示の目的の１つは、ハロゲン副生成物の残留を回避することのできるスルホニウム塩ポリマーまたはポリアリーレンスルフィドの製造方法を提供することである。 One of the objects of the present disclosure is to provide a process for producing a sulfonium salt polymer or a polyarylene sulfide that can avoid residual halogen by-products.
本開示の実施形態によれば、本開示は、式（Ｉ）で示される構造を有する少なくとも１つのモノマーを、スルホン酸、ジフェニルアミン、および酸素含有リン化物（oxygen-containing phosphide）存在下で反応させて、スルホニウム塩ポリマー（sulfonium salt polymer）得る工程を含むポリマーの製造方法を提供する。 According to an embodiment of the present disclosure, the present disclosure comprises reacting at least one monomer having the structure of formula (I) in the presence of sulfonic acid, diphenylamine, and oxygen-containing phosphide. Thus, there is provided a method for producing a polymer comprising a step of obtaining a sulfonium salt polymer.
式中、Ｘは０、１、または２であり；Ｒ１はＣ１−６アルキル基であり；Ｒ２はそれぞれ独立に、水素、またはＣ１−６アルキル基である。 In the formula, X is 0, 1, or 2; R 1 is a C 1-6 alkyl group; R 2 is each independently hydrogen or a C 1-6 alkyl group.
本開示の実施形態は、モノマーがスルホニウム塩ポリマーに転化する転化率を高めることができ、かつ使用するモノマーを容易に得ることができるポリマーの製造方法を提供する。また、酸素含有リン化物（oxygen-containing phosphide）の存在下で重合反応を進行させることにより、式（Ｉ）で示される構造を有するモノマーが、スルホニウム塩ポリマー（またはポリアリーレンスルフィド）に転化する転化率を大幅に高めることができる。また、スルホニウム塩ポリマーを得た後、さらに求核試薬（nucleophile）を、得られたスルホニウム塩ポリマーと反応させることで、ハロゲンの残留がない耐高温ポリアリーレンスルフィド（polyarylene sulfide）（融解温度（Ｔｍ）が２８０℃以上であり得る）を得ることができる。 Embodiments of the present disclosure provide a method for producing a polymer that can increase the conversion rate of a monomer into a sulfonium salt polymer and can easily obtain the monomer to be used. In addition, by allowing the polymerization reaction to proceed in the presence of oxygen-containing phosphide, the monomer having the structure represented by formula (I) is converted into a sulfonium salt polymer (or polyarylene sulfide). The rate can be greatly increased. In addition, after obtaining the sulfonium salt polymer, a nucleophile is further reacted with the obtained sulfonium salt polymer, whereby a high temperature resistant polyarylene sulfide (melting temperature (Tm ) Can be 280 ° C. or higher.
ポリアリーレンスルフィドを、モノマー（Ｉ）（その化学構造は Polyarylene sulfide is converted into monomer (I) (the chemical structure is
であり得る）を酸性環境下で重合して陽イオンポリマーとし、さらに脱メチル化を行うことにより製造する場合、反応式（Ｉ）を参照されたいが、この場合、得られる陽イオンポリマー（モノマー（Ｉ）を重合してなる）の転化率は高くない。 Can be obtained by polymerizing in an acidic environment to produce a cationic polymer, followed by demethylation, see Reaction Formula (I), in which case the resulting cationic polymer (monomer The conversion of (I) is not high.
また、反応式（ＩＩ）を参照してモノマー（Ｉ）を製造する場合、まずはメチルフェニルスルホキシド（methyl phenyl sulfoxide）とメチルフェニルスルフィド（methyl phenyl sulfide）を酸性環境下で合成し、陽イオン中間体を得た後、さらに脱メチル化および酸化反応を進行させなければならない。しかしながら、反応式（ＩＩ）の製造プロセスが比較的複雑であるため、ポリアリーレンスルフィドの収率が低下してしまう。 In addition, when the monomer (I) is produced with reference to the reaction formula (II), first, methyl phenyl sulfoxide and methyl phenyl sulfide are synthesized in an acidic environment to form a cation intermediate. Once obtained, further demethylation and oxidation reactions must proceed. However, since the production process of the reaction formula (II) is relatively complicated, the yield of polyarylene sulfide is lowered.
上述に基づき、本開示の実施形態は、モノマーがスルホニウム塩ポリマーに転化する転化率を高めることができるとともに、使用するモノマーも容易に得ることのできる、ポリマーの製造方法を提供する。本開示の実施形態によれば、該方法は、式（Ｉ）で示される構造を有する少なくとも１つのモノマーを、スルホン酸、ジフェニルアミン（diphenyl amine）、および酸素含有リン化物（oxygen-containing phosphide）の存在下で重合反応させて、スルホニウム塩ポリマー（sulfonium salt polymer）を得る工程を含む。 Based on the above, embodiments of the present disclosure provide a method for producing a polymer that can increase the conversion rate of a monomer into a sulfonium salt polymer and can easily obtain the monomer to be used. According to an embodiment of the present disclosure, the method comprises at least one monomer having a structure of formula (I), of sulfonic acid, diphenyl amine, and oxygen-containing phosphide. Polymerizing in the presence to obtain a sulfonium salt polymer.
式中、Ｘは０、１、または２であってよく；Ｒ１はＣ１−６アルキル基であってよく；Ｒ２それぞれ独立に、水素、またはＣ１−６アルキル基であってよい。本開示の実施形態によれば、式（Ｉ）で示される構造を有する前記モノマーのスルホキシド（Ｓ＝Ｏ）官能基は、酸性環境下でプロトン化されて、反応性を有する水酸化スルホニウム（sulfonium hydroxide）官能基になることができ、さらに、ジフェニルアミンが、電荷安定試薬として働き、電子を提供して、水酸化スルホニウムと錯体（complex）構造を形成することにより、芳香環のπ電子の反応性が高まり、重合反応が進行することとなる。また、酸素含有リン化物（oxygen-containing phosphide）の存在下で重合反応を進行させることで、式（Ｉ）で示される構造を有するモノマーが、スルホニウム塩ポリマー（またはポリアリーレンスルフィド）に転化する転化率を大幅に高めることができる。また、スルホニウム塩ポリマーを得た後、さらに、求核試薬（nucleophile）を、得られたスルホニウム塩ポリマーと反応させることで、ハロゲンの残留が無い耐高温ポリアリーレンスルフィド（polyarylene sulfide）（融解温度（Ｔｍ）が２８０℃以上であり得る）を得ることができる。本開示の実施形態によれば、上記モノマーがスルホニウム塩ポリマー（またはポリアリーレンスルフィド）に転化する転化率の計算方式は下記方程式のとおりである。 Wherein X may be 0, 1, or 2; R 1 may be a C 1-6 alkyl group; each R 2 may independently be hydrogen or a C 1-6 alkyl group. According to an embodiment of the present disclosure, the sulfoxide (S═O) functional group of the monomer having the structure represented by the formula (I) is protonated in an acidic environment to have a reactive sulfonium hydroxide (sulfonium hydroxide). In addition, diphenylamine acts as a charge stabilizer and provides electrons to form a complex structure with sulfonium hydroxide, thereby reacting the π-electron of the aromatic ring. And the polymerization reaction proceeds. In addition, by allowing the polymerization reaction to proceed in the presence of oxygen-containing phosphide, the monomer having the structure represented by formula (I) is converted into a sulfonium salt polymer (or polyarylene sulfide). The rate can be greatly increased. In addition, after obtaining the sulfonium salt polymer, the nucleophile is further reacted with the obtained sulfonium salt polymer, so that a high-temperature resistant polyarylene sulfide (melting temperature (no melting point)) having no halogen residue is obtained. Tm) can be 280 ° C. or higher. According to an embodiment of the present disclosure, a calculation method of a conversion rate at which the monomer is converted into a sulfonium salt polymer (or polyarylene sulfide) is as follows.
本開示の実施形態によれば、上記アルキル基は直鎖（linear）または分岐鎖（branched）アルキル基であってよい。よって、Ｒ１はメチル（methyl）、エチル（ethyl）、プロピル（propyl）、イソプロピル（isopropyl）、ｎ−ブチル（n-butyl）、ｔ−ブチル（t-butyl）、ｓｅｃ−ブチル（sec-butyl）、イソブチル（isobutyl）、ペンチル（pentyl）、またはヘキシル（hexyl）であってよい。また、Ｒ２はそれぞれ独立に、水素、フッ素、メチル、エチル、プロピル、イソプロピル、ｎ−ブチル、ｔ−ブチル、ｓｅｃ−ブチル、イソブチル、ペンチル、またはヘキシルであってよい。 According to embodiments of the present disclosure, the alkyl group may be a linear or branched alkyl group. Therefore, R 1 is methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, sec-butyl. ), Isobutyl, pentyl, or hexyl. R 2 may be independently hydrogen, fluorine, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, sec-butyl, isobutyl, pentyl, or hexyl.
本開示の実施形態によれば、上記スルホン酸は、式（ＩＩ）で示される構造を有する化合物であってよい。 According to an embodiment of the present disclosure, the sulfonic acid may be a compound having a structure represented by the formula (II).
式中、Ｒ３は水素、Ｃ１−６アルキル基、またはＣ１−６フルオロアルキル基であってよい。ここで、上記フルオロアルキル基は、炭素上の水素の全部または一部がフッ素で置換されたアルキル基のことを指し、かつ直鎖（linear）または分岐鎖（branched）であってよい。例えば、フルオロメチルは、モノフルオロメチル、ジフルオロメチル、またはパーフルオロメチルであってよい。本開示の実施形態によれば、Ｒ３は、メチル、エチル、プロピル、イソプロピル、ｎ−ブチル、ｔ−ブチル、ｓｅｃ−ブチル、イソブチル、ペンチル、ヘキシル、フルオロメチル、フルオロエチル、またはフルオロプロピルであってよい。本開示のいくつかの実施形態によれば、上記スルホン酸はメタンスルホン酸、エタンスルホン酸、プロピルスルホン酸、トリフルオロメタンスルホン酸（ＣＦ３ＳＯ３Ｈ）、またはその組み合わせであってよい。本開示の実施形態によれば、上記スルホン酸と上記モノマーとのモル比は、約１から２００であってよく、例えば約１から１００であってよい。ここで、上記スルホン酸は、酸性環境を提供して上記モノマーの重合反応の進行を促進することができ、また過剰量のスルホン酸は反応溶媒としても働き得る。 In the formula, R 3 may be hydrogen, a C 1-6 alkyl group, or a C 1-6 fluoroalkyl group. Here, the fluoroalkyl group refers to an alkyl group in which all or part of hydrogen on carbon is substituted with fluorine, and may be linear or branched. For example, the fluoromethyl can be monofluoromethyl, difluoromethyl, or perfluoromethyl. According to embodiments of the present disclosure, R 3 is methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, sec-butyl, isobutyl, pentyl, hexyl, fluoromethyl, fluoroethyl, or fluoropropyl. It's okay. According to some embodiments of the present disclosure, the sulfonic acid may be methane sulfonic acid, ethane sulfonic acid, propyl sulfonic acid, trifluoromethane sulfonic acid (CF 3 SO 3 H), or a combination thereof. According to embodiments of the present disclosure, the molar ratio of the sulfonic acid to the monomer may be about 1 to 200, for example about 1 to 100. Here, the sulfonic acid can provide an acidic environment to promote the progress of the polymerization reaction of the monomer, and an excessive amount of the sulfonic acid can also serve as a reaction solvent.
本開示の実施形態によれば、本開示に係るポリマーの製造方法における上記酸素含有リン化物の添加は、式（Ｉ）で示される構造を有するモノマーがスルホニウム塩ポリマーに転化する転化率を大幅に高めることができる。上記酸素含有リン化物は、酸素およびリンからなる化合物、例えば無水リン酸（Ｐ２Ｏ５）であってよい。また、上記酸素含有リン化物は、酸素、水素およびリンからなる化合物、例えばポリリン酸（Ｈ（ｎ＋２）ＰｎＯ（３ｎ＋１）、ただしｎは１より大きい）であってよい。本開示の実施形態によれば、上記酸素含有リン化物と上記モノマーとのモル比は約０．５から２であってよく、例えば約０．５から１．５であってよい。 According to the embodiment of the present disclosure, the addition of the oxygen-containing phosphide in the polymer production method according to the present disclosure greatly increases the conversion rate at which the monomer having the structure represented by the formula (I) is converted into the sulfonium salt polymer. Can be increased. The oxygen-containing phosphide may be a compound composed of oxygen and phosphorus, for example, phosphoric anhydride (P 2 O 5 ). The oxygen-containing phosphide may be a compound composed of oxygen, hydrogen and phosphorus, for example, polyphosphoric acid (H (n + 2) P n O (3n + 1) , where n is greater than 1). According to embodiments of the present disclosure, the molar ratio of the oxygen-containing phosphide to the monomer can be about 0.5 to 2, for example about 0.5 to 1.5.
本開示の実施形態によれば、上記ジフェニルアミンと上記モノマーとのモル比は約０．５から２であってよく、例えば約０．５から１．５であってよい。上記ジフェニルアミンおよび酸素含有リン化物は、式（Ｉ）で示される構造を有する上記モノマーの重合反応の進行を促進させるが、上記ジフェニルアミンおよび酸素含有リン化物は反応物質ではない。 According to embodiments of the present disclosure, the molar ratio of the diphenylamine to the monomer can be about 0.5 to 2, for example about 0.5 to 1.5. The diphenylamine and oxygen-containing phosphide promote the progress of the polymerization reaction of the monomer having the structure represented by formula (I), but the diphenylamine and oxygen-containing phosphide are not reactants.
本開示の実施形態によれば、本開示に係るポリマーの製造方法は、式（Ｉ）で示される構造を有する１つのモノマーを、スルホン酸、ジフェニルアミン、および酸素含有リン化物の存在下で重合反応させることができ、式（Ｉ）で示される構造を有する上記モノマーは、例えば、 According to an embodiment of the present disclosure, a method for producing a polymer according to the present disclosure includes a polymerization reaction of one monomer having a structure represented by formula (I) in the presence of sulfonic acid, diphenylamine, and an oxygen-containing phosphide. The monomer having the structure of formula (I) can be, for example,
であってよい。また、本開示の実施形態によれば、本開示に係るポリマーの製造方法は、式（Ｉ）で示される構造を有する２種の異なるモノマーを、スルホン酸、ジフェニルアミン、および酸素含有リン化物の存在下で重合反応させることができ、式（Ｉ）で示される構造を有する上記２種の異なるモノマーのうちの１つは、 It may be. In addition, according to the embodiment of the present disclosure, the method for producing a polymer according to the present disclosure includes two different monomers having a structure represented by the formula (I), the presence of a sulfonic acid, diphenylamine, and an oxygen-containing phosphide. One of the two different monomers having the structure of formula (I) can be polymerized under
であってよい。さらに、本開示の実施形態によれば、本開示に係るポリマーの製造方法は、（Ｉ）で示される構造を有する２種の異なるモノマーを、スルホン酸、ジフェニルアミン、および酸素含有リン化物の存在下で重合反応させることができ、式（Ｉ）で示される構造を有する上記２種の異なるモノマーはそれぞれ、 It may be. Furthermore, according to an embodiment of the present disclosure, a method for producing a polymer according to the present disclosure includes two different monomers having the structure represented by (I) in the presence of sulfonic acid, diphenylamine, and an oxygen-containing phosphide. The two different monomers having the structure of formula (I) can be polymerized with
であってよい。
It may be.
本開示の実施形態によれば、本開示に係るポリマーの製造方法で得られたスルホニウム塩ポリマーは、式（ＩＩＩ）で示される構造を有する少なくとも１つの繰り返し単位を有し得る。 According to the embodiment of the present disclosure, the sulfonium salt polymer obtained by the method for producing a polymer according to the present disclosure may have at least one repeating unit having a structure represented by the formula (III).
式中、Ｘは０、１、または２であってよく；Ｒ１はＣ１−６アルキル基であってよく；Ｒ２はそれぞれ独立に、水素、またはＣ１−６アルキル基であってよく；Ｒ３は水素、Ｃ１−６アルキル基、またはＣ１−６フルオロアルキル基であってよい。本開示のいくつかの実施形態によれば、式（ＩＩＩ）で示される構造を有する上記繰り返し単位は、 Wherein X may be 0, 1, or 2; R 1 may be a C 1-6 alkyl group; R 2 may each independently be hydrogen or a C 1-6 alkyl group R 3 may be hydrogen, a C 1-6 alkyl group, or a C 1-6 fluoroalkyl group. According to some embodiments of the present disclosure, the repeating unit having the structure of formula (III) is
であってよい。 It may be.
本開示の実施形態によれば、上記ポリマーの製造方法は、上記スルホニウム塩ポリマーを得た後、求核試薬（nucleophile）を上記スルホニウム塩ポリマーと反応させることで、ポリアリーレンスルフィド（polyarylene sulfide）を得る工程をさらに含んでいてよい。このうち、上記求核試薬（nucleophile）は、例えば、置換または非置換基を有するピリジンもしくはその誘導体（例えばピリジン、４−メチルピリジン）、アミン（例えばトリエチルアミン）、ハロゲン化塩（例えば塩化カリウム）、アルコール（例えばメタノール、エタノール）、またはアミド（例えばジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン）であってよく、かつ上記求核試薬と式（Ｉ）で示される構造を有するモノマー(上記スルホニウム塩ポリマーを合成するのに用いる)とのモル比は、約１から１００であってよく、また、過剰量の求核試薬を溶媒として添加してもよい。上記ポリアリーレンスルフィドは、式（ＩＶ）で示される構造を有する少なくとも１つの繰り返し単位を有し得る。 According to an embodiment of the present disclosure, the method for producing the polymer includes obtaining the sulfonium salt polymer, and then reacting a nucleophile with the sulfonium salt polymer to obtain polyarylene sulfide. The step of obtaining may further be included. Among these, the nucleophile includes, for example, a substituted or unsubstituted pyridine or a derivative thereof (for example, pyridine, 4-methylpyridine), an amine (for example, triethylamine), a halide salt (for example, potassium chloride), A monomer (such as a sulfonium salt polymer) which may be an alcohol (for example, methanol, ethanol) or an amide (for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone) and has a structure represented by the above nucleophile and formula (I) Used to synthesize) may be from about 1 to 100 and an excess of the nucleophile may be added as a solvent. The polyarylene sulfide may have at least one repeating unit having a structure represented by the formula (IV).
式中、Ｘは０、１、または２であってよく；Ｒ２はそれぞれ独立に、水素、またはＣ１−６アルキル基であってよい。式（ＩＶ）で示される構造を有する上記繰り返し単位は例えば、 Wherein X may be 0, 1, or 2; each R 2 may independently be hydrogen or a C 1-6 alkyl group. The repeating unit having the structure represented by the formula (IV) is, for example,
であってよい。 It may be.
本開示の上述ならびにその他の目的、特徴、および長所がより明確にかつ理解しやすくなるよう、以下にいくつかの実施例および比較例を挙げて詳細に説明する。 In order to make the above and other objects, features and advantages of the present disclosure clearer and easier to understand, some examples and comparative examples are described in detail below.
［実施例１］
メチルフェニルスルフィド（methyl phenyl sulfide）０．５ｇ、五酸化二リン（phosphorus pentoxide、Ｐ２Ｏ５）０．２５ｇおよびジフェニルアミン（diphenyl amine）０．３ｇを反応容器中に加えた。次いで、０℃の氷浴下、トリフルオロメタンスルホン酸（trifluoromethanesulfonic acid）３ｍｌをゆっくり反応容器中に加えた。室温で１時間反応させた後、反応容器をゆっくり室温まで戻した。２０時間反応させた後、得られたものをエチルエーテル１００ｍｌ中に注ぎ入れ、激しく撹拌してから、少量のアセトンで洗浄した。乾燥後、スルホニウム塩ポリマー（Ｉ）（白色の固体）を得た。
[Example 1]
0.5 g of methyl phenyl sulfide, 0.25 g of phosphorous pentoxide (P 2 O 5 ) and 0.3 g of diphenyl amine were added to the reaction vessel. Next, 3 ml of trifluoromethanesulfonic acid was slowly added into the reaction vessel in an ice bath at 0 ° C. After reacting at room temperature for 1 hour, the reaction vessel was slowly returned to room temperature. After reacting for 20 hours, the resulting product was poured into 100 ml of ethyl ether, stirred vigorously and then washed with a small amount of acetone. After drying, sulfonium salt polymer (I) (white solid) was obtained.
次いで、得られたスルホニウム塩ポリマー（Ｉ）を４−メチルピリジン（4-methylpyridine）１５ｍｌ中に溶解し、加熱還流（約１００℃）した。６時間反応させた後、得られた生成物を塩酸水溶液３０ｍｌ（濃度１０％）中に注ぎ入れ、次いで、少量のアセトンで洗浄し、ポリアリーレンスルフィド（Ｉ）（白色の固体）を転化率約８８％で得た。上記反応の反応式は次のとおりである： Subsequently, the obtained sulfonium salt polymer (I) was dissolved in 15 ml of 4-methylpyridine and heated to reflux (about 100 ° C.). After reacting for 6 hours, the obtained product was poured into 30 ml of hydrochloric acid aqueous solution (concentration: 10%) and then washed with a small amount of acetone to convert the polyarylene sulfide (I) (white solid) to about a conversion rate. Obtained at 88%. The reaction formula for the above reaction is as follows:
次いで、示差走査熱量計（ＤＳＣ：differential scanning calorimetry）を用いて、得られたポリアリーレンスルフィド（Ｉ）を測定したところ、その融解温度（Ｔｍ）が２８１℃に達し、かつその再結晶温度（Ｔｃ）が２１０℃に達したことがわかった。次いで、赤外分光光度計（ＦＴ−ＩＲ）でポリアリーレンスルフィド（Ｉ）を測定した。その結果は次の通りであった：ＩＲ（ｃｍ−１）：３０６５，１５７３，１４７１，１３８７，１０９２，１００９，９９８，８１５，７４２。 Subsequently, when the obtained polyarylene sulfide (I) was measured using a differential scanning calorimetry (DSC), its melting temperature (Tm) reached 281 ° C. and its recrystallization temperature (Tc). ) Reached 210 ° C. Subsequently, polyarylene sulfide (I) was measured with an infrared spectrophotometer (FT-IR). The results were as follows: IR (cm −1 ): 3065, 1573, 1471, 1387, 1092, 1009, 998, 815, 742.
［実施例２］
フェニルボロン酸（phenylboronic acid）３ｇ、４−ブロモチオアニソール（4-bromothioanisole）３．４５ｇ、Ｐｄ（ＰＰｈ３）４０．１ｇ、および炭酸ナトリウム（Ｎａ２ＣＯ３）１．５ｇを反応容器中に加えた。次いで、窒素下でその反応容器にトルエン５０ｍｌ、脱イオン水６０ｍｌ、およびメタノール１０ｍｌをゆっくり加えた。次いで、１００℃で２４時間反応させた後、得られた溶液を酢酸エチルと水を用いて３回抽出し、有機層を回収して乾燥し、化合物（Ｉ）(１−メチルスルファニル−４−フェニルベンゼン（1-methylsulfanyl-4-phenylbenzene）)を収率約９９％で得た。上記反応の反応式は次のとおりである：
[Example 2]
3 g of phenylboronic acid, 3.45 g of 4-bromothioanisole, 0.1 g of Pd (PPh 3 ) 4 and 1.5 g of sodium carbonate (Na 2 CO 3 ) in a reaction vessel added. Then, 50 ml of toluene, 60 ml of deionized water, and 10 ml of methanol were slowly added to the reaction vessel under nitrogen. Subsequently, after making it react at 100 degreeC for 24 hours, the obtained solution is extracted 3 times using ethyl acetate and water, The organic layer is collect | recovered and dried, Compound (I) (1-methylsulfanyl-4- Phenylbenzene (1-methylsulfanyl-4-phenylbenzene)) was obtained with a yield of about 99%. The reaction formula for the above reaction is as follows:
核磁気共鳴分光により化合物（Ｉ）を分析して得られたスペクトルデータは次のとおりである：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）。 The spectral data obtained by analyzing compound (I) by nuclear magnetic resonance spectroscopy are as follows: 1 H NMR (500 MHz, ppm, CDCl 3 ): 2.55 (—CH 3 , s), 7. 33-7.37 (phenyl, 3H, m), 7.43-7.45 (phenyl, 2H, m), 7.54-7.6 (phenyl, 4H, m).
次いで、化合物（Ｉ）１ｇを反応容器中に入れ、氷酢酸１０ｍｌおよび過酸化水素（濃度３０％）２ｍｌをゆっくり加えた。室温で２０分反応させた後、得られた溶液を濾過し、オレンジ色の固体を得た。そのオレンジ色の固体をジクロロメタンと水を用いて３回抽出し、有機層を回収した。次いで、有機層を脱水、濾過および濃縮した後、化合物（ＩＩ）を得た。上記反応の反応式は以下に示すとおりである： Next, 1 g of compound (I) was placed in the reaction vessel, and 10 ml of glacial acetic acid and 2 ml of hydrogen peroxide (concentration 30%) were slowly added. After reacting at room temperature for 20 minutes, the resulting solution was filtered to obtain an orange solid. The orange solid was extracted 3 times with dichloromethane and water, and the organic layer was recovered. Then, the organic layer was dehydrated, filtered and concentrated to obtain compound (II). The reaction formula for the above reaction is as follows:
核磁気共鳴分光により化合物（ＩＩ）を分析して得られたスペクトルデータは次のとおりである： 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）。 The spectral data obtained by analyzing compound (II) by nuclear magnetic resonance spectroscopy are as follows: 1 H NMR (500 MHz, ppm, CDCl 3 ): 2.80 (—CH 3 , s), 7. 42-7.51 (biphenyl, 3H, m), 7.62-7.63 (biphenyl, 2H, m), 7.73-7.78 (biphenyl, 4H, m).
次いで、化合物（ＩＩ）０．５ｇ、ジフェニルアミン０．３９ｇ、および五酸化二リン（phosphorus pentoxide、Ｐ２Ｏ５）０．１６ｇを反応容器中に加えた。次いで、０℃の氷浴下、トリフルオロメタンスルホン酸５ｍｌをゆっくり加えた。氷浴下で１時間反応させた後、ゆっくりと室温まで戻した。次いで、２０時間反応させた後、得られたものをエチルエーテル１００ｍｌ中に注ぎ入れて激しく撹拌し、さらに少量のアセトンで洗浄した。乾燥後にスルホニウム塩ポリマー（ＩＩ）を得た。次いで、得られたスルホニウム塩ポリマー（ＩＩ）を４−メチルピリジン（4-methylpyridine）６ｍｌ中に溶解し、室温下で１時間撹拌してから、加熱還流（約１２０℃）した。２０時間反応させた後、得られた生成物を塩酸水溶液３０ｍｌ（濃度１０％）中に注ぎ入れ、次いで少量のアセトンで洗浄し、表１に示されるようにポリアリーレンスルフィド（ＩＩ）（白色の固体）を転化率約９０％で得た。 Next, 0.5 g of compound (II), 0.39 g of diphenylamine, and 0.16 g of phosphorous pentoxide (P 2 O 5 ) were added to the reaction vessel. Subsequently, 5 ml of trifluoromethanesulfonic acid was slowly added in an ice bath at 0 ° C. After reacting for 1 hour in an ice bath, the temperature was slowly returned to room temperature. Next, after reacting for 20 hours, the obtained product was poured into 100 ml of ethyl ether, stirred vigorously, and further washed with a small amount of acetone. A sulfonium salt polymer (II) was obtained after drying. Next, the obtained sulfonium salt polymer (II) was dissolved in 6 ml of 4-methylpyridine, stirred at room temperature for 1 hour, and then heated to reflux (about 120 ° C.). After reacting for 20 hours, the obtained product was poured into 30 ml of hydrochloric acid aqueous solution (concentration 10%), then washed with a small amount of acetone, and polyarylene sulfide (II) (white color as shown in Table 1). Solid) was obtained with a conversion of about 90%.
次いで、示差走査熱量計（ＤＳＣ：differential scanning calorimetry）を用いて、得られたポリアリーレンスルフィド（ＩＩ）を測定したところ、その融解温度（Ｔｍ）が４０４℃に達し、かつその再結晶温度（Ｔｃ）が３６９℃に達したことがわかった。次いで、赤外分光光度計（ＦＴ−ＩＲ）でポリアリーレンスルフィド（ＩＩ）を測定した。その結果は次のとおりであった：ＩＲ（ｃｍ−１）：３０２６，１５９０，１４７４，１３９１，１３１３，１１５２，１１３７，１０９０，１０４５，９９８，９５２，８１１，７５８，６９０。 Subsequently, when the obtained polyarylene sulfide (II) was measured using a differential scanning calorimetry (DSC), its melting temperature (Tm) reached 404 ° C. and its recrystallization temperature (Tc). ) Reached 369 ° C. Subsequently, polyarylene sulfide (II) was measured with an infrared spectrophotometer (FT-IR). The results were as follows: IR (cm −1 ): 3026, 1590, 1474, 1391, 1313, 1152, 1137, 1090, 1045, 998, 952, 811, 758, 690.
［比較例１］
化合物（ＩＩ）０．５ｇおよびジフェニルアミン０．３９ｇを反応容器中に加えた。次いで、０℃の氷浴下、トリフルオロメタンスルホン酸５ｍｌをゆっくり加えた。氷浴下で１時間反応させた後、ゆっくり室温まで戻した。次いで、２０時間反応させた後、得られたものをエチルエーテル１００ｍｌ中に注ぎ入れ、激しく撹拌してから、少量のアセトンで洗浄した。乾燥後、スルホニウム塩ポリマー（ＩＩ）を得た。次いで、得られたスルホニウム塩ポリマー（ＩＩ）を４−メチルピリジン（4-methylpyridine）６ｍｌ中に溶解し、室温下で１時間撹拌してから、加熱還流（約１２０℃）した。２０時間反応させた後、得られた生成物を塩酸水溶液３０ｍｌ（濃度１０％）中に注ぎ入れ、次いで少量のアセトンで洗浄し、表１に示されるようにポリアリーレンスルフィド（ＩＩ）（白色の固体）を転化率約５７％で得た。
[Comparative Example 1]
Compound (II) 0.5g and diphenylamine 0.39g were added into the reaction vessel. Subsequently, 5 ml of trifluoromethanesulfonic acid was slowly added in an ice bath at 0 ° C. After reacting for 1 hour in an ice bath, the temperature was slowly returned to room temperature. Then, after reacting for 20 hours, the resulting product was poured into 100 ml of ethyl ether, stirred vigorously and then washed with a small amount of acetone. After drying, sulfonium salt polymer (II) was obtained. Next, the obtained sulfonium salt polymer (II) was dissolved in 6 ml of 4-methylpyridine, stirred at room temperature for 1 hour, and then heated to reflux (about 120 ° C.). After reacting for 20 hours, the obtained product was poured into 30 ml of hydrochloric acid aqueous solution (concentration 10%), then washed with a small amount of acetone, and polyarylene sulfide (II) (white color as shown in Table 1). Solid) was obtained with a conversion of about 57%.
比較例１と比べて、実施例２では、化合物（ＩＩ）を重合する際、トリフルオロメタンスルホン酸およびジフェニルアミンの他に、さらに五酸化二リンも加えている。表１に参照されるように、比較例１と比べて、実施例２に記載された方式でポリアリーレンスルフィド（ＩＩ）を製造すると、得られる転化率が顕著に高まる。 Compared with Comparative Example 1, in Example 2, when compound (II) was polymerized, diphosphorus pentoxide was further added in addition to trifluoromethanesulfonic acid and diphenylamine. As can be seen from Table 1, when polyarylene sulfide (II) is produced by the method described in Example 2 as compared with Comparative Example 1, the conversion obtained is significantly increased.
［実施例３］
メチルフェニルスルフィド０．１９ｇ、化合物（ＩＩ）０．３ｇ、五酸化二リン０．２ｇ、およびジフェニルアミン０．２３ｇを反応容器中に加えた。次いで、０℃の氷浴下、トリフルオロメタンスルホン酸３ｍｌをゆっくり加えた。氷浴下で１時間反応させた後、ゆっくりと室温まで戻した。次いで、２０時間反応させた後、得られたものをエチルエーテル１００ｍｌ中に注ぎ入れて激しく撹拌してから、少量のアセトンで洗浄した。乾燥後にスルホニウム塩ポリマー（ＩＩＩ）を得た。次いで、得られたスルホニウム塩ポリマー（ＩＩＩ）を４−メチルピリジン（4-methylpyridine）１５ｍｌ中に溶解し、室温下で１時間撹拌してから、加熱還流（約１００℃）した。６時間反応させた後、得られた生成物を塩酸水溶液３０ｍｌ（濃度１０％）中に注ぎ入れ、次いで少量のアセトンで洗浄し、表２に示されるようにポリアリーレンスルフィド（ＩＩＩ）（白色の固体）を転化率約３５％で得た。上記反応の反応式は次のとおりである。
[Example 3]
0.19 g of methylphenyl sulfide, 0.3 g of compound (II), 0.2 g of diphosphorus pentoxide and 0.23 g of diphenylamine were added to the reaction vessel. Next, 3 ml of trifluoromethanesulfonic acid was slowly added in an ice bath at 0 ° C. After reacting for 1 hour in an ice bath, the temperature was slowly returned to room temperature. Next, after reacting for 20 hours, the resulting product was poured into 100 ml of ethyl ether, stirred vigorously, and then washed with a small amount of acetone. A sulfonium salt polymer (III) was obtained after drying. Next, the obtained sulfonium salt polymer (III) was dissolved in 15 ml of 4-methylpyridine, stirred at room temperature for 1 hour, and then heated to reflux (about 100 ° C.). After reacting for 6 hours, the obtained product was poured into 30 ml of hydrochloric acid aqueous solution (concentration 10%), then washed with a small amount of acetone, and polyarylene sulfide (III) (white Solid) was obtained with a conversion of about 35%. The reaction formula of the above reaction is as follows.
（ただし、スルホニウム塩ポリマー（ＩＩＩ）またはポリアリーレンスルフィド（ＩＩＩ）の繰り返し単位はランダムに配列する。） (However, the repeating units of the sulfonium salt polymer (III) or polyarylene sulfide (III) are randomly arranged.)
次いで、示差走査熱量計（ＤＳＣ：differential scanning calorimetry）を用いて、得られたポリアリーレンスルフィド（ＩＩＩ）を測定したところ、そのガラス転移温度（Ｔｇ）が１１３℃に達したことがわかった。次いで、赤外分光光度計（ＦＴ−ＩＲ）でポリアリーレンスルフィド（ＩＩＩ）を測定した。その結果は次の通りであった：ＩＲ（ｃｍ−１）：３０２４，１５８４，１４７４，１３８９，１３１９，１１７８，１１５５，１０９０，１００１，８１０，７５９，６９４。 Subsequently, when the obtained polyarylene sulfide (III) was measured using a differential scanning calorimetry (DSC), it was found that the glass transition temperature (Tg) reached 113 ° C. Subsequently, polyarylene sulfide (III) was measured with an infrared spectrophotometer (FT-IR). The results were as follows: IR (cm −1 ): 3024, 1584, 1474, 1389, 1319, 1178, 1155, 1090, 1001, 810, 759, 694.
［比較例２］
五酸化二リンを添加しなかったこと以外は、実施例３に記載したとおりに進行させた。表２に示されるように、得られたポリアリーレンスルフィド（ＩＩＩ）の転化率は約≦５％であった。
[Comparative Example 2]
Proceed as described in Example 3 except that no diphosphorus pentoxide was added. As shown in Table 2, the conversion of the resulting polyarylene sulfide (III) was about ≦ 5%.
比較例２と比べて、実施例３では、メチルフェニルスルフィドと化合物（ＩＩ）との共重合を行う際、トリフルオロメタンスルホン酸およびジフェニルアミンの他に、さらに五酸化二リンも加えている。表２に参照されるように、比較例２と比べて、実施例３に記載された方式でポリアリーレンスルフィド（ＩＩＩ）を製造すると、得られる転化率が顕著に高まる。 Compared with Comparative Example 2, in Example 3, when copolymerizing methylphenyl sulfide and compound (II), diphosphorus pentoxide was further added in addition to trifluoromethanesulfonic acid and diphenylamine. As can be seen from Table 2, when polyarylene sulfide (III) is produced by the method described in Example 3 as compared with Comparative Example 2, the conversion obtained is significantly increased.
いくつかの実施形態により本発明を上述のとおり開示したが、本発明はこれによって限定されるものではなく、当業者であれば、本発明の趣旨および範囲から逸脱しない範囲で、任意の変更および修正を加えることができる。本発明の保護範囲は、添付の特許請求の範囲で定義されたものを基準に判断するものとする。 Although the present invention has been disclosed as described above according to some embodiments, the present invention is not limited thereto, and those skilled in the art will be able to make any modifications and changes without departing from the spirit and scope of the present invention. Modifications can be made. The protection scope of the present invention shall be determined on the basis of what is defined in the appended claims.
Claims (13)
（式中、Ｘは１、または２であり；Ｒ１はＣ１−６アルキル基であり；Ｒ２はそれぞれ独立に、水素、またはＣ１−６アルキル基である。） At least one monomer having the structure of formula (I) is reacted in the presence of sulfonic acid, diphenylamine, and oxygen-containing phosphide to obtain a sulfonium salt polymer. A method for producing a polymer comprising a step.
(Wherein X is 1 or 2; R 1 is a C 1-6 alkyl group; R 2 is independently hydrogen or a C 1-6 alkyl group.)
（式中、Ｒ３は水素、Ｃ１−６アルキル基、またはＣ１−６フルオロアルキル基である。） The method for producing a polymer according to claim 1 or 2, wherein the sulfonic acid is a compound having a structure represented by the formula (II).
(In the formula, R 3 is hydrogen, a C 1-6 alkyl group, or a C 1-6 fluoroalkyl group.)
である請求項１〜請求項４のいずれか一項に記載のポリマーの製造方法。 The monomer having the structure represented by formula (I) is:
It is these. The manufacturing method of the polymer as described in any one of Claims 1-4.
（式中、Ｘは１、または２であり；Ｒ１はＣ１−６アルキル基であり；Ｒ２はそれぞれ独立に、水素、またはＣ１−６アルキル基であり；Ｒ３は水素、Ｃ１−６アルキル基、またはＣ１−６フルオロアルキル基である。） The method for producing a polymer according to claim 5, wherein the sulfonium salt polymer has at least one repeating unit having a structure represented by the formula (III).
(Wherein X is 1 or 2; R 1 is a C 1-6 alkyl group; R 2 is independently hydrogen or a C 1-6 alkyl group; R 3 is hydrogen, C A 1-6 alkyl group or a C 1-6 fluoroalkyl group.)
である請求項６に記載のポリマーの製造方法。 The repeating unit having a structure represented by the formula (III)
The method for producing a polymer according to claim 6 .
（式中、Ｘは１、または２であり；Ｒ２はそれぞれ独立に、水素、またはＣ１−６アルキル基である。） The method for producing a polymer according to claim 10 , wherein the polyarylene sulfide has at least one repeating unit having a structure represented by the formula (IV).
(In the formula, X is 1 or 2, and each R 2 is independently hydrogen or a C 1-6 alkyl group.)
である請求項１２に記載のポリマーの製造方法。 The repeating unit having a structure represented by the formula (IV)
The method for producing a polymer according to claim 12 .
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