JP5585916B2 - Process for producing polythiophenes and novel thiophene monomer - Google Patents
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- 239000000178 monomer Substances 0.000 title claims description 64
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims description 61
- 229920000123 polythiophene Polymers 0.000 title claims description 41
- 229930192474 thiophene Natural products 0.000 title claims description 31
- 238000000034 method Methods 0.000 title claims description 8
- 230000008569 process Effects 0.000 title description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 84
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 239000002904 solvent Substances 0.000 claims description 49
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000004519 manufacturing process Methods 0.000 claims description 29
- 239000002685 polymerization catalyst Substances 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 150000003949 imides Chemical class 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 150000003573 thiols Chemical class 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 4
- VOKXPKSMYJLAIW-UHFFFAOYSA-N nickel;phosphane Chemical group P.[Ni] VOKXPKSMYJLAIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 77
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 229920000642 polymer Polymers 0.000 description 35
- 229910052736 halogen Inorganic materials 0.000 description 30
- 239000000243 solution Substances 0.000 description 29
- 238000009826 distribution Methods 0.000 description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 150000002367 halogens Chemical class 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000011701 zinc Substances 0.000 description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 14
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 14
- 229910052725 zinc Inorganic materials 0.000 description 14
- 125000005843 halogen group Chemical group 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 10
- 229940125904 compound 1 Drugs 0.000 description 10
- 238000001542 size-exclusion chromatography Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000732 glass refractive index measurement Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 150000004795 grignard reagents Chemical class 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- SLNRTNDEELFNDS-UHFFFAOYSA-N 5-bromo-3-hexyl-2-iodothiophene Chemical compound CCCCCCC=1C=C(Br)SC=1I SLNRTNDEELFNDS-UHFFFAOYSA-N 0.000 description 5
- 239000007818 Grignard reagent Substances 0.000 description 5
- 229940125782 compound 2 Drugs 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 0 *c1c(*)[s]c(*)c1 Chemical compound *c1c(*)[s]c(*)c1 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000006880 cross-coupling reaction Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- SDMKEQYHISDGKT-UHFFFAOYSA-N 2-bromo-3-hexyl-5-iodothiophene Chemical compound CCCCCCC=1C=C(I)SC=1Br SDMKEQYHISDGKT-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- RYEXTBOQKFUPOE-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].CC[CH2-] RYEXTBOQKFUPOE-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NSYFIAVPXHGRSH-UHFFFAOYSA-N 2,5-dibromo-3-hexylthiophene Chemical compound CCCCCCC=1C=C(Br)SC=1Br NSYFIAVPXHGRSH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005577 Kumada cross-coupling reaction Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000006894 reductive elimination reaction Methods 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- CNQRHSZYVFYOIE-UHFFFAOYSA-N (4-iodophenyl)methanol Chemical compound OCC1=CC=C(I)C=C1 CNQRHSZYVFYOIE-UHFFFAOYSA-N 0.000 description 1
- XQJNXCHDODCAJF-UHFFFAOYSA-N 2-bromo-3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1Br XQJNXCHDODCAJF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- MAHPNPYYQAIOJN-UHFFFAOYSA-N azimsulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2N(N=CC=2C2=NN(C)N=N2)C)=N1 MAHPNPYYQAIOJN-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- ZBQUMMFUJLOTQC-UHFFFAOYSA-N dichloronickel;3-diphenylphosphaniumylpropyl(diphenyl)phosphanium Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1[PH+](C=1C=CC=CC=1)CCC[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 ZBQUMMFUJLOTQC-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- AASUFOVSZUIILF-UHFFFAOYSA-N diphenylmethanone;sodium Chemical compound [Na].C=1C=CC=CC=1C(=O)C1=CC=CC=C1 AASUFOVSZUIILF-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- -1 for example Substances 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000006464 oxidative addition reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、ポリチオフェン類の製造方法、及び新規なチオフェンモノマーに関するものである。 The present invention relates to a method for producing polythiophenes and a novel thiophene monomer.
半導体高分子分野において、ポリチオフェン類は有機EL、有機トランジスタ、及び有機薄膜太陽電池等を中心とする最新電子デバイス材料に多く用いられており、世界中で合成・機能化・デバイス特性を含めた広範囲の研究が繰り広げられている。中でもモノマー繰り返し単位の結合様式(2,5-位)が揃った頭尾結合型(以降、「レジオレギュラー」と呼ぶ)のポリ(3-アルキルチオフェン)(P3AT)類は、高い結晶性と高い溶解性、高い電荷移動度、及び商業的供給安定性のバランスに優れ、様々な光・電子機能材料に用いられている。 In the field of semiconductor polymers, polythiophenes are widely used in the latest electronic device materials centering on organic EL, organic transistors, and organic thin-film solar cells. Is being researched. Among them, poly (3-alkylthiophene) (P3AT) class of head-to-tail type (hereinafter referred to as “regioregular”) with a uniform monomer repeating unit (2,5-position) is highly crystalline and high. It has excellent balance of solubility, high charge mobility, and commercial supply stability, and is used in various optical and electronic functional materials.
McCulloughらが初めてグリニャール試薬型チオフェンモノマーを使用し、熊田カップリング反応によるレジオレギュラーP3ATを合成した(非特許文献1、2)。その後、Riekeらが活性金属亜鉛(Rieke Zinc)を用いて同様のレジオレギュラーP3ATを合成した(非特許文献3)。しかしながら、いずれの方法でも-40℃〜-78℃と極低温の反応条件が必要である点が工業化の障害になっていた。
McCulloughらは改良を加え、2,5-ジハロ置換チオフェン誘導体とグリニャール試薬を用いた金属・ハロゲン反応を使用して、室温や溶媒の還流温度での重合(以降、「GRIM重合」と呼ぶ)を可能にした(非特許文献4、5)。
McCullough et al. First synthesized regioregular P3AT by Kumada coupling reaction using Grignard reagent type thiophene monomer (Non-patent
McCullough et al. Improved the polymerization at room temperature and solvent reflux temperature (hereinafter referred to as “GRIM polymerization”) using a metal / halogen reaction using a 2,5-dihalo-substituted thiophene derivative and a Grignard reagent. (Non-Patent
その後さらに、GRIM重合において、分子量及び分子量分布を制御する研究がなされた。モノマーとして、2-ブロモ-5-クロロマグネシオ-3-アルキルチオフェン、触媒として1,3-ビス(ジフェニルホスフィノ)プロパンニッケルジクロリド(Ni(dppp)Cl2)を用いた系で、モノマーの重縮合反応(熊田カップリング反応)が逐次的ではなく連鎖的に進行し、モノマーとNi(dppp)Cl2の仕込み比に応じて分子量が制御され、かつ分子量分布の狭い一次構造の明確なレジオレギュラーP3ATが得られることがMcCulloughらと横澤らによりほぼ同時期に独立に報告された(非特許文献6、7)。この発見により、従来困難であった、末端官能基化P3AT、ブロック共重合体、及びグラフト共重合体等が次々と合成されるようになった。
Thereafter, further studies were made to control the molecular weight and molecular weight distribution in GRIM polymerization. In a system using 2-bromo-5-chloromagnesio-3-alkylthiophene as the monomer and 1,3-bis (diphenylphosphino) propanenickel dichloride (Ni (dppp) Cl 2 ) as the catalyst, The condensation reaction (Kumada coupling reaction) proceeds in a chain rather than sequentially, the molecular weight is controlled according to the charge ratio of the monomer and Ni (dppp) Cl 2 , and the regioregular structure has a narrow primary structure with a narrow molecular weight distribution. It was reported by McCullough et al. And Yokozawa et al. Independently that P3AT was obtained (Non-Patent
しかしながら、GRIM重合系では溶媒及びモノマーの高度な精製及び徹底的な脱水の必要があり、工業化に向かないことが大きな問題として残されている。それは、グリニャール試薬が本質的に、アルコール、水、チオール、フェノール、アミン、及びカルボン酸等のプロトン溶媒に極めて高反応性であることに帰している。
また、グリニャール試薬を用いる場合、ケトン、エステル、アミド、及びイミド等の溶媒も、求核置換反応等の副反応が生じる等の理由により、使用できない。
However, the GRIM polymerization system requires a high degree of purification and thorough dehydration of the solvent and monomer, and remains a major problem that it is not suitable for industrialization. It is attributed that Grignard reagents are inherently very reactive to proton solvents such as alcohol, water, thiols, phenols, amines, and carboxylic acids.
In addition, when a Grignard reagent is used, solvents such as ketones, esters, amides, and imides cannot be used because of side reactions such as nucleophilic substitution reactions.
また、ポリチオフェン類の重合においては、その分子量と分子量分布を良好に制御できることが好ましい。
ポリチオフェン類は分子量によって電荷移動度が異なる。光・電子機能材料として用いる場合、良好な電荷移動度が得られることから、ポリチオフェン類の数平均分子量は2500 g/mol以上であることが好ましく、5000 g/mol以上であることがより好ましく、9000 g/mol以上であることがより好ましく、10000 g/mol以上であることが特に好ましい。ポリチオフェン類は、分子量分布が大きいと、所望の範囲より分子量の小さいものが含まれ、所望の電荷移動度が得られなくなる恐れがある。
したがって、分子量分布が小さく、かつ、数平均分子量2500 g/mol以上のポリチオフェン類を製造できることが好ましい。
In the polymerization of polythiophenes, it is preferable that the molecular weight and molecular weight distribution can be controlled well.
Polythiophenes have different charge mobility depending on the molecular weight. When used as an optical / electronic functional material, since good charge mobility can be obtained, the number average molecular weight of the polythiophenes is preferably 2500 g / mol or more, more preferably 5000 g / mol or more, It is more preferably 9000 g / mol or more, particularly preferably 10000 g / mol or more. If the molecular weight distribution of the polythiophenes is large, those having a molecular weight smaller than the desired range are included, and there is a possibility that the desired charge mobility cannot be obtained.
Therefore, it is preferable that polythiophenes having a small molecular weight distribution and a number average molecular weight of 2500 g / mol or more can be produced.
本発明は上記事情に鑑みてなされたものであり、溶媒及びモノマーの高度な精製及び徹底的な脱水を要することなく、ポリチオフェン類の頭尾結合様式、分子量、及び分子量分布等の一次構造を良好に制御することが可能なポリチオフェン類の製造方法を提供することを目的とするものである。 The present invention has been made in view of the above circumstances, and has excellent primary structures such as the head-to-tail bonding mode, molecular weight, and molecular weight distribution of polythiophenes without requiring high-level purification and thorough dehydration of solvents and monomers. It is an object of the present invention to provide a method for producing polythiophenes that can be controlled to a high level.
ポリチオフェン類の重合に関する研究ではないが、内山らは、新しく設計・合成した亜鉛錯体、ジリチウムテトラ(tert-ブチル)ジンケート(tBu4ZnLi2)を塩基性開始剤として用い、N-イソプロピルアクリルアミドのアニオン重合を水中で行っている(非特許文献8)。また、彼らは4-ヨードベンジルアルコールとtBu4ZnLi2を反応させたところ、水酸基を保護しなくても選択的・定量的に金属ハロゲン交換反応が進行することを報告している(非特許文献9)。
そこで、tBu4ZnLi2は活性プロトンに対する塩基反応性は弱いものの、選択的・定量的な金属ハロゲン交換を進行させ得る亜鉛錯体であると考えられる。本発明者はかかる知見に基づいて研究を行い、本発明を完成した。
Although it is not a study on the polymerization of polythiophenes, Uchiyama et al. Used a newly designed and synthesized zinc complex, dilithium tetra (tert-butyl) zincate ( t Bu 4 ZnLi 2 ) as a basic initiator, and N-isopropylacrylamide. Anionic polymerization of is carried out in water (Non-patent Document 8). They also reported that when 4-iodobenzyl alcohol and t Bu 4 ZnLi 2 were reacted, the metal halogen exchange reaction proceeded selectively and quantitatively without protecting the hydroxyl group (non-patented). Reference 9).
Therefore, t Bu 4 ZnLi 2 is considered to be a zinc complex that can promote selective and quantitative metal-halogen exchange, although its base reactivity to active protons is weak. The present inventor conducted research based on such knowledge and completed the present invention.
本発明のポリチオフェン類の製造方法は、下記一般式(P)で表されるポリチオフェン類の製造方法であって、少なくとも1種のエーテル系溶媒を含む溶媒存在下で、下記一般式(M1)で表されるチオフェンモノマーとジリチウムテトラ(tert-ブチル)ジンケートとを反応させる工程Aと、前記溶媒存在下で、工程Aの反応生成物に重合触媒を加えて溶液重合反応を行う工程Bとを有するものである。 The method for producing a polythiophene of the present invention is a method for producing a polythiophene represented by the following general formula (P), and is represented by the following general formula (M1) in the presence of a solvent containing at least one ether solvent. Step A for reacting the thiophene monomer represented by dilithium tetra (tert-butyl) zincate, and Step B for performing a solution polymerization reaction by adding a polymerization catalyst to the reaction product of Step A in the presence of the solvent. It is what you have.
本発明のポリチオフェン類の製造方法の中間生成物は新規化合物である。この新規化合物は下記一般式(M2)で表されるチオフェンモノマーである。 The intermediate product of the process for producing the polythiophenes of the present invention is a novel compound. This novel compound is a thiophene monomer represented by the following general formula (M2).
本発明によれば、溶媒及びモノマーの高度な精製及び徹底的な脱水を要することなく、ポリチオフェン類の頭尾結合様式、分子量、及び分子量分布等の一次構造を良好に制御することが可能なポリチオフェン類の製造方法を提供することができる。 According to the present invention, polythiophene capable of satisfactorily controlling the primary structure of polythiophenes, such as the head-to-tail bonding mode, molecular weight, and molecular weight distribution, without requiring sophisticated purification of solvents and monomers and thorough dehydration. Can be provided.
以下、本発明について詳細に説明する。
いくつかの反応スキームを示して本発明の反応機構を説明するが、これらの反応スキームは必ずしも明確なものはない。
Hereinafter, the present invention will be described in detail.
Although several reaction schemes are shown to explain the reaction mechanism of the present invention, these reaction schemes are not necessarily clear.
本発明のポリチオフェン類の製造方法は、
下記一般式(P)で表されるポリチオフェン類の製造方法であって、
少なくとも1種のエーテル系溶媒を含む溶媒存在下で、下記一般式(M1)で表されるチオフェンモノマーとジリチウムテトラ(tert-ブチル)ジンケートとを反応させる工程Aと、
前記溶媒存在下で、工程Aの反応生成物に重合触媒を加えて溶液重合反応を行う工程Bとを有するものである。
The method for producing the polythiophene of the present invention comprises:
A method for producing a polythiophene represented by the following general formula (P),
A step A of reacting a thiophene monomer represented by the following general formula (M1) with dilithium tetra (tert-butyl) zincate in the presence of a solvent containing at least one ether solvent;
And a step B of performing a solution polymerization reaction by adding a polymerization catalyst to the reaction product of the step A in the presence of the solvent.
モノマー(M1)はアルキル基Rの炭素数が4以上のとき、生成されるポリマーが溶媒溶解性を示し、溶液重合が進行する。アルキル基Rの炭素数が多くなる程、生成されるポリマーの溶媒溶解性は増す。アルキル基Rの炭素数は6以上が好ましい。 In the monomer (M1), when the alkyl group R has 4 or more carbon atoms, the polymer produced exhibits solvent solubility, and solution polymerization proceeds. As the number of carbon atoms of the alkyl group R increases, the solvent solubility of the polymer produced increases. The alkyl group R preferably has 6 or more carbon atoms.
工程Bの重合触媒としては特に制限されず、公知のポリチオフェン類の重合に使用される触媒を用いることができる。
重合触媒としては、ニッケル系触媒、及びパラジウム系触媒等が挙げられる。
反応速度、及び生成されるポリマーの一次構造制御等を考慮すれば、重合触媒としては、ニッケル系触媒が好ましく、ニッケルホスフィン系触媒が特に好ましい。
ニッケルホスフィン系触媒としては、下記一般式で表わされる0Ni(PPh3)4,IINi(dppe)Cl2,IINi(dppp)Cl2,及びIINi(dppf)Cl2のうちいずれかが好ましい。
The polymerization catalyst in Step B is not particularly limited, and a catalyst used for polymerization of known polythiophenes can be used.
Examples of the polymerization catalyst include a nickel-based catalyst and a palladium-based catalyst.
In view of the reaction rate and control of the primary structure of the polymer to be produced, the polymerization catalyst is preferably a nickel catalyst, and particularly preferably a nickel phosphine catalyst.
As the nickel phosphine-based catalyst, one of 0 Ni (PPh 3 ) 4 , II Ni (dppe) Cl 2 , II Ni (dppp) Cl 2 , and II Ni (dppf) Cl 2 represented by the following general formula is used. preferable.
本発明のポリチオフェン類の製造方法の考えられる反応スキームを以下に示す。ここでは、工程Bの重合触媒をニッケル系触媒として記載してある。 A possible reaction scheme of the method for producing the polythiophenes of the present invention is shown below. Here, the polymerization catalyst in step B is described as a nickel-based catalyst.
チオフェンモノマー(M1)(2,5-ジハロ置換チオフェン)に対して、1当量のtBu4ZnLi2(亜鉛錯体)を反応させると、金属ハロゲン交換反応が起こり、モノマー(M1)の5位のハロゲンが置換されて、下記一般式(M2)で表される中間生成物が生成されると考えられる。 When 1 equivalent of t Bu 4 ZnLi 2 (zinc complex) is reacted with the thiophene monomer (M1) (2,5-dihalo-substituted thiophene), a metal halogen exchange reaction occurs, and the 5th position of the monomer (M1) It is considered that an intermediate product represented by the following general formula (M2) is formed by replacing the halogen.
中間生成物(M2)は化学的に安定なチオフェンモノマーあり、かつ適切な重合触媒を添加することで、クロスカップリング反応が起き、重合が重縮合でありながら逐次的ではなく連鎖的に進行する。
本発明の重合系中の活性種は活性プロトンに対する塩基反応性が弱い亜鉛錯体であるため、水分が含まれる未蒸留の市販溶媒を用いた重合系、アルコール、水、チオール、フェノール、アミン、及びカルボン酸等のプロトン溶媒、あるいは、ケトン、エステル、アミド、及びイミド等の溶媒を添加した系、及び水分を含む大気雰囲気下でも、ポリチオフェン類の重合及び一次構造制御が可能である。
The intermediate product (M2) is a chemically stable thiophene monomer, and by adding an appropriate polymerization catalyst, a cross-coupling reaction occurs, and the polymerization proceeds in a chain rather than a sequential manner while being a polycondensation. .
Since the active species in the polymerization system of the present invention is a zinc complex having a weak base reactivity to active protons, a polymerization system using an undistilled commercial solvent containing water, alcohol, water, thiol, phenol, amine, and Polymerization and primary structure control of polythiophenes are possible even in a system containing a proton solvent such as carboxylic acid or a system to which solvents such as ketones, esters, amides, and imides are added, and in an atmosphere containing moisture.
例えば、上記で例示したニッケルホスフィン系触媒を用いた場合には、Ni(0)が常に重合末端に移動することで連鎖的に重合が進行すると考えられる(「背景技術」の項の非特許文献7を参照)。この時の考えられる重合反応スキームを以下に示す。ここでは、モノマー(M1)のX/Yの組合わせがI/Brであり、重合触媒としてIINi(dppe)Cl2を用いた場合について図示してある。 For example, when the nickel phosphine-based catalyst exemplified above is used, it is considered that Ni (0) always moves to the polymerization terminal, so that the polymerization proceeds in a chain (Non-Patent Document in the section “Background Art”). (See 7). A possible polymerization reaction scheme at this time is shown below. Here, the case where the combination of X / Y of the monomer (M1) is I / Br and II Ni (dppe) Cl 2 is used as the polymerization catalyst is shown.
上記反応スキームに示すように、亜鉛錯体2(=モノマー(M2)、大過剰)と2価のNi触媒(1当量)とを反応させると、2当量の亜鉛錯体2(=モノマー(M2))が二量化反応に消費され、Zn(tBu)3LiとLiClが脱離して1当量の中間体3が生成される。中間体3に導入された2価のNi触媒は還元的脱離によって0価のNi触媒(Ni(0))となり、中間体4が生成される。Ni(0)がさらにC-Br結合に酸化的付加することで、中間体5が生成される。この中間体5に対して、余剰の亜鉛錯体2(=モノマー(M2))がさらに反応する。このようにNi(0)が還元的脱離・酸化的付加を繰り返すことで、重合は連鎖的・リビング的に進行する。従って、上記反応系ではNi(0)が実質的な触媒である。そのため、用いる重合触媒はNi(II)でもNi(0)でも構わない。 As shown in the above reaction scheme, when zinc complex 2 (= monomer (M2), large excess) is reacted with divalent Ni catalyst (1 equivalent), 2 equivalents of zinc complex 2 (= monomer (M2)) Is consumed in the dimerization reaction, and Zn ( t Bu) 3 Li and LiCl are desorbed to produce 1 equivalent of intermediate 3. The divalent Ni catalyst introduced into the intermediate 3 becomes a zero-valent Ni catalyst (Ni (0)) by reductive elimination, and the intermediate 4 is generated. Ni (0) is further oxidatively added to the C—Br bond to generate intermediate 5. Excess zinc complex 2 (= monomer (M2)) further reacts with this intermediate 5. As Ni (0) repeats reductive elimination and oxidative addition in this way, the polymerization proceeds in a chain and living manner. Therefore, Ni (0) is a substantial catalyst in the above reaction system. Therefore, the polymerization catalyst used may be Ni (II) or Ni (0).
チオフェンモノマー(M1)において、ハロゲンX、Yの組合わせによっては、5位のハロゲンだけでなく、2位のハロゲンについても金属ハロゲン交換反応が起こる場合がある。
理由は定かではないが、本発明者は、2位のハロゲンが置換されたチオフェンモノマーよりも5位のハロゲンが置換されたチオフェンモノマーの方が重合しやすいことを見出している。
本発明者は、2位のハロゲンの金属ハロゲン交換反応が起こった場合、反応終了後に、2位のハロゲンが置換されたチオフェンモノマーが重合せずに、そのまま残存することを確認している。アルキル基の電子供与効果はそれほど強くないので、おそらく立体障害の影響と考えられる。
2位のハロゲンが置換されたチオフェンモノマーが生成されても、5位のハロゲンが置換されたチオフェンモノマー(M2)によって目的生成物であるレジオレギュラーP3ATが得られるが、5位のハロゲンのみが金属ハロゲン交換した場合よりも、ポリマー収率は低下する。
In the thiophene monomer (M1), depending on the combination of halogens X and Y, a metal halogen exchange reaction may occur not only at the 5-position halogen but also at the 2-position halogen.
Although the reason is not clear, the present inventor has found that a thiophene monomer substituted with a halogen at the 2-position is more easily polymerized than a thiophene monomer substituted with a halogen at the 2-position.
The present inventor has confirmed that, when the metal halogen exchange reaction of the 2-position halogen occurs, the thiophene monomer substituted with the 2-position halogen remains without being polymerized after the completion of the reaction. The electron donating effect of the alkyl group is not so strong, so it is probably due to steric hindrance.
Even if a thiophene monomer substituted with a halogen at the 2nd position is produced, the target product regioregular P3AT is obtained by the thiophene monomer (M2) substituted with a halogen at the 5th position, but only the halogen at the 5th position is a metal. The polymer yield is lower than in the case of halogen exchange.
チオフェンモノマー(M1)において5位のハロゲンの金属ハロゲン交換反応を高選択的に起こすためには、チオフェンモノマー(M1)においてXとYが異なるハロゲン元素であることが好ましい。
X/Yの組合わせが、I/Br,Br/Cl,及びI/Clのうちいずれかであることが好ましい。
本発明者は、X/Yの組合わせがI/Brのとき、チオフェンモノマー(M1)とtBu4ZnLi2との反応において、5位のハロゲンの金属ハロゲン交換反応が100%起こることを間接的に証明している(後記[実施例]の予備実験を参照)。
上記のようにチオフェンモノマー(M1)においてXとYが異なるハロゲン元素であることが好ましいが、本発明者は、チオフェンモノマー(M1)においてXとYが同一の場合でも、金属ハロゲン交換反応は5位よりも2位の方が起こりやすく、目的生成物であるレジオレギュラーP3ATが高収率で得られることを確認している(後記[実施例]の項実施例4-S17を参照)。
In order to cause highly selective metal halogen exchange reaction of halogen at the 5-position in the thiophene monomer (M1), it is preferable that X and Y are different halogen elements in the thiophene monomer (M1).
The combination of X / Y is preferably any of I / Br, Br / Cl, and I / Cl.
The present inventors indirectly found that when the X / Y combination is I / Br, the metal halogen exchange reaction of the halogen at the 5-position occurs 100% in the reaction between the thiophene monomer (M1) and t Bu 4 ZnLi 2. (See preliminary experiment in [Example] below).
As described above, it is preferable that X and Y are different halogen elements in the thiophene monomer (M1). However, the present inventor has found that the metal halogen exchange reaction is 5 even when X and Y are the same in the thiophene monomer (M1). It has been confirmed that the regioregular P3AT, which is the target product, can be obtained in a high yield because the second position is more likely than the second position (see Example 4-S17 in [Examples] below).
工程A、Bの反応温度は特に制限なく、使用するモノマー(M1)、溶媒、及び重合触媒の組合わせに応じて適宜選定される。 The reaction temperature in Steps A and B is not particularly limited and is appropriately selected depending on the combination of the monomer (M1), the solvent, and the polymerization catalyst to be used.
工程Aは金属ハロゲン置換反応であり、例えば0℃〜35℃程度の条件で、10分間程度〜数時間程度で反応が終了する。 Step A is a metal halogen substitution reaction. For example, the reaction is completed in about 10 minutes to several hours under conditions of about 0 ° C. to 35 ° C.
工程Bは重合反応であり、反応温度が低すぎると、重合が進行しなかったり、反応に要する時間が長くなったり、得られるポリマーの分子量が不充分となったりする。これは、モノマーの立体障害によって、ポリマー末端とモノマー間のクロスカップリング反応が遅くなるためと考えられる。 Step B is a polymerization reaction. If the reaction temperature is too low, the polymerization does not proceed, the time required for the reaction becomes long, or the molecular weight of the resulting polymer becomes insufficient. This is presumably because the cross coupling reaction between the polymer terminal and the monomer becomes slow due to the steric hindrance of the monomer.
例えば、チオフェンモノマー(M1)においてX/Yの組合わせがI/Brであり、重合触媒がIINi(dppe)Cl2であるとき、工程Bの反応温度が30℃以下では重合が難しく、45℃以上で重合が進行した(後記[実施例]の実施例1-S6-7を参照)。
チオフェンモノマー(M1)においてX/Yの組合わせがI/Brであり、重合触媒がIINi(dppe)Cl2であるとき、工程Bの反応温度は45℃以上が好ましい。
チオフェンモノマー(M1)においてX/Yの組合わせがI/Brであり、重合触媒がIINi(dppp)Cl2であるとき、工程Bの反応温度が25℃でも重合が進行した(後記[実施例]の実施例2-S8を参照)。したがって、適切な重合触媒を用いることで、工程Bの反応温度が45℃以下でも重合は進行する。
For example, in the thiophene monomer (M1), when the combination of X / Y is I / Br and the polymerization catalyst is II Ni (dppe) Cl 2 , polymerization is difficult at a reaction temperature of 30 ° C. or lower, and 45 Polymerization proceeded at a temperature higher than or equal to ° C (see Example 1-S6-7 in [Examples] below).
In the thiophene monomer (M1), when the combination of X / Y is I / Br and the polymerization catalyst is II Ni (dppe) Cl 2 , the reaction temperature in Step B is preferably 45 ° C. or higher.
In the thiophene monomer (M1), when the X / Y combination is I / Br and the polymerization catalyst is II Ni (dppp) Cl 2 , the polymerization proceeded even at a reaction temperature of 25 ° C. Example see Example 2-S8). Therefore, by using an appropriate polymerization catalyst, the polymerization proceeds even when the reaction temperature in Step B is 45 ° C. or lower.
本発明で用いる溶媒は、少なくとも1種のエーテル系溶媒を含んでいればよい。
本発明で用いる溶媒は、テトラヒドロフラン(THF)、ジエチルエーテル、オキセタン、ジオキサン、エチレングリコールジメチルエーテル(モノグライム)、ジエチレングリコールジメチルエーテル(ジグライム)、及びプロピレングリコールモノメチルエーテルアセテート(PEGMEA)から選択される少なくとも1種のエーテル系溶媒を含むことが好ましい。
The solvent used in the present invention only needs to contain at least one ether solvent.
The solvent used in the present invention is at least one ether selected from tetrahydrofuran (THF), diethyl ether, oxetane, dioxane, ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), and propylene glycol monomethyl ether acetate (PEGMEA). It is preferable that a system solvent is included.
本発明の系では、用いる溶媒は微量の水分を含むことができ、例えば1000ppm以下の水分を含むことができる。
用いる溶媒は、アルコール、水、チオール、フェノール、アミン、及びカルボン酸からなる群より選択される少なくとも1種のプロトン溶媒を含むことができる。
用いる溶媒は、ケトン、エステル、アミド、及びイミドからなる群より選択される少なくとも1種の溶媒を含むことができる。
In the system of the present invention, the solvent used can contain a trace amount of water, for example, 1000 ppm or less.
The solvent used can include at least one proton solvent selected from the group consisting of alcohol, water, thiol, phenol, amine, and carboxylic acid.
The solvent used can include at least one solvent selected from the group consisting of ketones, esters, amides, and imides.
従来のいかなる方法でも、水分が含まれる未蒸留の市販溶媒中、アルコール、水、チオール、フェノール、アミン、及びカルボン酸等のプロトン溶媒、あるいは、ケトン、エステル、アミド、及びイミド等の溶媒を添加した系、及び水分を含む大気雰囲気下での重合によるレジオレギュラーP3AT(頭尾結合様式割合(レジオレギュラリティー)≧90%の合成は不可能であった。 Add any proton solvent such as alcohol, water, thiol, phenol, amine, and carboxylic acid or ketone, ester, amide, imide, etc. It was impossible to synthesize regioregular P3AT (ratio of head-to-tail coupling mode (resiregularity) ≧ 90%) by polymerization in an atmosphere containing water and water.
また、ポリチオフェン類の重合においては、その分子量と分子量分布を良好に制御できることが好ましい。
ポリチオフェン類は分子量によって電荷移動度が異なる。光・電子機能材料として用いる場合、良好な電荷移動度が得られることから、ポリチオフェン類の数平均分子量は2500 g/mol以上であることが好ましく、5000 g/mol以上であることがより好ましく、9000 g/mol以上であることがより好ましく、10000 g/mol以上であることが特に好ましい。ポリチオフェン類は、分子量分布が大きいと、所望の範囲より分子量の小さいものが含まれ、所望の電荷移動度が得られなくなる恐れがある。
したがって、分子量分布が小さく、かつ、数平均分子量が2500 g/mol以上のポリチオフェン類を製造できることが好ましい。
In the polymerization of polythiophenes, it is preferable that the molecular weight and molecular weight distribution can be controlled well.
Polythiophenes have different charge mobility depending on the molecular weight. When used as an optical / electronic functional material, since good charge mobility can be obtained, the number average molecular weight of the polythiophenes is preferably 2500 g / mol or more, more preferably 5000 g / mol or more, It is more preferably 9000 g / mol or more, particularly preferably 10000 g / mol or more. If the molecular weight distribution of the polythiophenes is large, those having a molecular weight smaller than the desired range are included, and there is a possibility that the desired charge mobility cannot be obtained.
Therefore, it is preferable that polythiophenes having a small molecular weight distribution and a number average molecular weight of 2500 g / mol or more can be produced.
低塩基性を示す立体障害の大きい亜鉛錯体tBu4ZnLi2を使用した本発明の重合系では、微量の水分、例えば1000ppm以下の水分を含む未蒸留の市販エーテル系溶媒中、アルコール等のプロトン溶媒存在下、及び水分を含む大気雰囲気下でも重合が進行し、分子量分布が小さく、かつ、数平均分子量が2500 g/mol、好ましくは5000 g/mol以上、より好ましくは9000 g/mol以上、特に好ましくは10000 g/mol以上のポリチオフェン類を製造することができる。 In the polymerization system of the present invention using the low basicity and high steric hindrance zinc complex t Bu 4 ZnLi 2 , protons such as alcohol in undistilled commercial ether solvents containing a trace amount of water, for example, water of 1000 ppm or less Polymerization proceeds even in the presence of a solvent and in an air atmosphere containing moisture, the molecular weight distribution is small, and the number average molecular weight is 2500 g / mol, preferably 5000 g / mol or more, more preferably 9000 g / mol or more, Particularly preferably, a polythiophene of 10,000 g / mol or more can be produced.
具体的には、後記[実施例]に示すように、500ppmの水分を含む未蒸留の市販溶媒(テトラハイドロフラン(THF))中(実施例3-S9)、モノマーに対して当モルのアルコール(2-プパノール(iPrOH))を加えた系(実施例3-S10)、蒸留精製THFに1000ppmの純水を添加した系(実施例3-S11)、及び大気雰囲気下(実施例3-S12)でも重合が進行し、目的の分子量及び分子量分布の制御されたレジオレギュラーP3AT(頭尾結合様式90-99%、数平均分子量Mn 2500−30700 g/mol、及び分子量分布(1.15-2.40以下))が得られている。 Specifically, as described later in [Example], in an undistilled commercial solvent (tetrahydrofuran (THF)) containing 500 ppm of water (Example 3-S9), an equimolar amount of alcohol relative to the monomer. (2-Pupanol ( i PrOH)) added system (Example 3-S10), distilled purified THF added with 1000 ppm pure water (Example 3-S11), and under atmospheric conditions (Example 3- Polymerization proceeds even in S12), and the regioregular P3AT with controlled target molecular weight and molecular weight distribution (head-to-tail binding mode 90-99%, number average molecular weight Mn 2500-30700 g / mol, and molecular weight distribution (1.15-2.40 or less) )) Is obtained.
本発明によれば、溶媒及びモノマーの高度な精製及び徹底的な脱水を要することなく、ポリチオフェン類の頭尾結合様式、分子量、及び分子量分布等の一次構造を良好に制御することが可能なポリチオフェン類の製造方法を提供することができる。
本発明の製造方法によれば、溶媒及びモノマーの高度な精製及び徹底的な脱水が不要であり、市販の溶媒をそのまま使用することができ、大気雰囲気下で反応を行うことができるので、製造工程の簡便化、及び製造コストの低減等を図ることができる。
According to the present invention, polythiophene capable of satisfactorily controlling the primary structure of polythiophenes, such as the head-to-tail bonding mode, molecular weight, and molecular weight distribution, without requiring sophisticated purification of solvents and monomers and thorough dehydration. Can be provided.
According to the production method of the present invention, high-level purification and thorough dehydration of the solvent and the monomer are unnecessary, a commercially available solvent can be used as it is, and the reaction can be carried out in the atmosphere. Simplification of the process, reduction of manufacturing cost, and the like can be achieved.
本発明に係る実施例及び比較例について説明する。 Examples and comparative examples according to the present invention will be described.
(反応スキーム)
実施例1の考えられる反応スキームを以下に示す。
以降の説明において、化合物(モノマー)1、2の番号は、反応スキーム中の化合物の番号である。
(Reaction scheme)
A possible reaction scheme for Example 1 is shown below.
In the following description, the numbers of the compounds (monomers) 1 and 2 are the numbers of the compounds in the reaction scheme.
(測定法)
得られたポリマーの分子量及び分子量分布はサイズ排除体積クロマトグラフィー(SEC)(Jasco GULLIVER 1500システム, ポンプ(HITACHI, L-2131), UV検出器(Jasco, UV-1575, UV = 254 nm)を用い、標準ポリスチレンを用いた検量腺により求めた。クロロホルム(流速1.0 mL/min)を溶出液として用いた。
得られたポリマーの組成を確認するため、1H NMR測定を実施した。1H NMR測定はBruker DPX (300MHz)を用い、重クロロホルム中で実施した。トリメチルシランをδ=0ppmの標準試料として用いた。
(Measurement method)
Molecular weight and molecular weight distribution of the obtained polymer was measured using size exclusion volume chromatography (SEC) (Jasco GULLIVER 1500 system, pump (HITACHI, L-2131), UV detector (Jasco, UV-1575, UV = 254 nm)) It was determined from a calibration gland using standard polystyrene, and chloroform (flow rate 1.0 mL / min) was used as the eluent.
In order to confirm the composition of the obtained polymer, 1 H NMR measurement was performed. 1 H NMR measurement was performed in deuterated chloroform using Bruker DPX (300 MHz). Trimethylsilane was used as a standard sample with δ = 0 ppm.
(予備実験)
最初に、2-ブロモ-5-ヨード-3-ヘキシルチオフェン(化合物1)と亜鉛錯体tBu4ZnLi2をアルゴン気流下、蒸留精製THF(ナトリウムベンゾフェノンから窒素気流下で蒸留したもの)中、0℃で反応させ、金属ハロゲン交換反応を検討した。
塩酸水溶液で反応停止することにより、2-ブロモ-3-ヘキシルチオフェンがほぼ定量的に得られた。別途、臭化アリルで反応停止することにより、5-アリル-2-ブロモ-3-ヘキシルチオフェンがほぼ定量的に得られた。これらのことから、金属ハロゲン交換反応は5位のヨード基上で選択的・定量的に起こり、対応する中間生成物の亜鉛錯体であるジリチウムトリス(tert-ブチル)-(2-ブロモ-3-ヘキシル-5-チエニル)ジンケート(化合物2)が100%得られることが間接的に示された。
(Preliminary experiment)
First, 2-bromo-5-iodo-3-hexylthiophene (compound 1) and zinc complex t Bu 4 ZnLi 2 were distilled in THF and distilled in purified THF (distilled from sodium benzophenone under a nitrogen stream). The metal halogen exchange reaction was examined by reacting at ° C.
By stopping the reaction with an aqueous hydrochloric acid solution, 2-bromo-3-hexylthiophene was obtained almost quantitatively. Separately, the reaction was stopped with allyl bromide, whereby 5-allyl-2-bromo-3-hexylthiophene was obtained almost quantitatively. From these, the metal halogen exchange reaction occurs selectively and quantitatively on the iodo group at the 5-position, and the corresponding intermediate product zinc complex dilithium tris (tert-butyl)-(2-bromo-3 It was indirectly shown that -hexyl-5-thienyl) zincate (compound 2) was obtained.
(実施例1-サンプルS3)
<tBu4ZnLi2を用いたレジオレギュラーポリ(3-ヘキシルチオフェン)の合成>
アルゴン気流下、50 mL二口フラスコに、2-ブロモ-5-ヨード-3-ヘキシルチオフェン(化合物1)(0.286 g, 0.767 mmol)を量り取り、蒸留精製THF(50 mL)に溶解させた。この溶液に、tBu4ZnLi2のTHF溶液(0.535 M x 1.43 mL = 0.767 mmol)を加え、0 ℃で2時間攪拌した。さらにNi(dppe)Cl2(6.7 mg, 0.0127 mmol)を加えた。
25℃でクロスカップリング反応による重合を検討したところ、残念ながら、この条件下では重合物はほとんど得られなかった。これは、モノマーの立体障害の大きいため、ポリマー末端とモノマー間のクロスカップリング反応が極めて遅かったためと推察された。そこで、重合系の温度を60℃に上げ、同様の重合を再検討したところ、重合が進行した。
24時間後、5N-HCl水溶液を2 mL加え、重合反応を停止した。得られた溶液をメタノール/水(150 mL/75 mL)に注ぐことで、ポリマーを沈殿させた。沈殿物を吸引ろ過し、メタノールでよく洗浄した後、60℃で真空乾燥することにより、紫色固体を得た。
得られたポリマーの測定結果を以下に示す。
0.115 g, 収率90%, Mn (SEC) = 10200, 分子量分布(PDI) = 1.15, レジオレギュラリティー=97%、
1H NMR(δ, CDCl3): 6.95 ppm (s, 1H), 2.80 (t, 2H), 1.70 (t, 2H), 1.25-1.5 (m, 6H), 0.88 (t, 3H).
反応条件及び結果を表1-3に示す。
(Example 1-Sample S3)
<Synthesis of regioregular poly (3-hexylthiophene) using t Bu 4 ZnLi 2 >
Under a stream of argon, 2-bromo-5-iodo-3-hexylthiophene (Compound 1) (0.286 g, 0.767 mmol) was weighed into a 50 mL two-necked flask and dissolved in distilled purified THF (50 mL). To this solution was added a THF solution of t Bu 4 ZnLi 2 (0.535 M × 1.43 mL = 0.67 mmol), and the mixture was stirred at 0 ° C. for 2 hours. Furthermore Ni (dppe) Cl 2 (6.7 mg, 0.0127 mmol) was added.
When polymerization by a cross coupling reaction was examined at 25 ° C., unfortunately, almost no polymer was obtained under these conditions. This was presumably because the cross coupling reaction between the polymer terminal and the monomer was extremely slow due to the large steric hindrance of the monomer. Therefore, when the temperature of the polymerization system was raised to 60 ° C. and the same polymerization was reexamined, the polymerization proceeded.
After 24 hours, 2 mL of 5N-HCl aqueous solution was added to stop the polymerization reaction. The resulting solution was poured into methanol / water (150 mL / 75 mL) to precipitate the polymer. The precipitate was suction filtered, washed well with methanol, and then vacuum dried at 60 ° C. to obtain a purple solid.
The measurement results of the obtained polymer are shown below.
0.115 g, Yield 90%, M n (SEC) = 10200, Molecular weight distribution (PDI) = 1.15, Regioregularity = 97%,
1 H NMR (δ, CDCl 3 ): 6.95 ppm (s, 1H), 2.80 (t, 2H), 1.70 (t, 2H), 1.25-1.5 (m, 6H), 0.88 (t, 3H).
Reaction conditions and results are shown in Table 1-3.
(実施例1-サンプルS1,S2,S4-S7)
表1、2に示す反応条件に変更した以外は実施例1-S3と同様にして、反応を実施した。反応条件及び結果を表1-3に示す。
(Example 1-Samples S1, S2, S4-S7)
The reaction was performed in the same manner as in Example 1-S3 except that the reaction conditions were changed to those shown in Tables 1 and 2. Reaction conditions and results are shown in Table 1-3.
(実施例1-S1-S7の結果のまとめ)
反応温度が60℃である実施例1-S1-S5では、収率80%以上で目的のポリ(3-ヘキシルチオフェン)(P3HT)が得られた。本発明者は、本発明の重合系では分子量(数平均分子量Mn 2500−30700 g/mol)及び分子量分布(1.15-2.40)の制御がモノマーと触媒の仕込み比[化合物1]0/[Ni(dppe)Cl2]0を変えることにより可能であることを初めて見出した。さらに、得られたP3HTサンプルのプロトン核磁気共鳴法(1H NMR)によるスペクトル解析により、Mn ≧10000 g/molの場合、頭尾結合様式が97%以上であることが分かった。
(Summary of results of Example 1-S1-S7)
In Example 1-S1-S5 in which the reaction temperature was 60 ° C., the desired poly (3-hexylthiophene) (P3HT) was obtained in a yield of 80% or more. In the polymerization system of the present invention, the present inventor has determined that the molecular weight (number average molecular weight Mn 2500-30700 g / mol) and molecular weight distribution (1.15-2.40) are controlled by the monomer / catalyst charge ratio [compound 1] 0 / [Ni ( dppe) Cl 2 ] It was found for the first time that it was possible by changing 0 . Furthermore, spectral analysis by proton nuclear magnetic resonance ( 1 H NMR) of the obtained P3HT sample revealed that the head-to-tail coupling mode was 97% or more when Mn ≧ 10000 g / mol.
チオフェンモノマー(M1)においてX/Yの組合わせがI/Brであり、重合触媒がIINi(dppe)Cl2であるとき、工程Bの反応温度が30℃以下では重合が難しく、45℃以上で重合が進行した(S6-S7)。チオフェンモノマー(M1)においてX/Yの組合わせがI/Brであり、重合触媒がIINi(dppe)Cl2であるとき、工程Bの反応温度は45℃以上が好ましい。 In the thiophene monomer (M1), when the combination of X / Y is I / Br and the polymerization catalyst is II Ni (dppe) Cl 2 , polymerization is difficult at a reaction temperature of 30 ° C or less, and 45 ° C or more The polymerization proceeded at (S6-S7). In the thiophene monomer (M1), when the combination of X / Y is I / Br and the polymerization catalyst is II Ni (dppe) Cl 2 , the reaction temperature in Step B is preferably 45 ° C. or higher.
(実施例2-サンプルS8)
< 5-ブロモ-2-ヨード-3-ヘキシルチオフェンを出発物質としたNi(dppp)Cl2を用いたレジオレギュラーポリ(3-ヘキシルチオフェン)の合成>
アルゴン気流下、25 mL二口フラスコに、5-ブロモ-2-ヨード-3-ヘキシルチオフェン(0.346 g, 0.927mmol)を量り取り、THF(15 mL)に溶解させた。この溶液に、tBu4ZnLi2のTHF溶液(0.535 M x 1.90 mL = 1.02 mmol)を加え、0 ℃で2時間攪拌した。さらにNi(dppp)Cl2(3.0 mg, 0.00553 mmol)を加え、反応温度を25℃に昇温すると重合が進行した。2時間後、5N-HCl水溶液を2 mL加え、重合反応を停止した。得られた溶液をメタノール/水(150 mL/75 mL)に注ぐことで、ポリマーを沈殿させた。沈殿物を吸引ろ過し、メタノールでよく洗浄した後、60℃で真空乾燥することにより、赤紫色固体を得た。
得られたポリマーの測定結果を以下に示す。
0.140 g, 収率91%, Mn (SEC) = 6500, PDI = 1.55, レジオレギュラリティー=94%、
1H NMR(δ, CDCl3): 6.95 ppm (s, 1H), 2.80 (t, 2H), 1.70 (t, 2H), 1.25-1.5 (m, 6H), 0.88 (t, 3H).
反応条件及び結果を表1-3に示す。
チオフェンモノマー(M1)においてX/Yの組合わせがI/Brであり、重合触媒がIINi(dppp)Cl2であるとき、工程Bの反応温度が25℃でも重合が進行した。
(Example 2-Sample S8)
< Synthesis of regioregular poly (3-hexylthiophene) using Ni (dppp) Cl 2 starting from 5-bromo-2-iodo-3-hexylthiophene>
Under a stream of argon, 5-bromo-2-iodo-3-hexylthiophene (0.346 g, 0.927 mmol) was weighed into a 25 mL two-necked flask and dissolved in THF (15 mL). To this solution was added a THF solution of t Bu 4 ZnLi 2 (0.535 M x 1.90 mL = 1.02 mmol), and the mixture was stirred at 0 ° C for 2 hours. Further, Ni (dppp) Cl 2 (3.0 mg, 0.00553 mmol) was added, and the polymerization proceeded when the reaction temperature was raised to 25 ° C. After 2 hours, 2 mL of 5N-HCl aqueous solution was added to stop the polymerization reaction. The resulting solution was poured into methanol / water (150 mL / 75 mL) to precipitate the polymer. The precipitate was suction filtered, washed well with methanol, and then vacuum dried at 60 ° C. to obtain a reddish purple solid.
The measurement results of the obtained polymer are shown below.
0.140 g, Yield 91%, M n (SEC) = 6500, PDI = 1.55, Regioregularity = 94%,
1 H NMR (δ, CDCl 3 ): 6.95 ppm (s, 1H), 2.80 (t, 2H), 1.70 (t, 2H), 1.25-1.5 (m, 6H), 0.88 (t, 3H).
Reaction conditions and results are shown in Table 1-3.
In the thiophene monomer (M1), when the X / Y combination was I / Br and the polymerization catalyst was II Ni (dppp) Cl 2 , the polymerization proceeded even at a reaction temperature of 25 ° C.
(実施例3-サンプルS9)
溶媒として未蒸留THF(脱水・安定剤含まず・和光純正化学・99.5%)(25 mL)を用いた以外は実施例1-S3と同様にして、反応を実施した。
反応条件及び結果を表1-3に示す。
得られたポリマーのGPCチャート及び1HNMRチャートを図1、及び図2に示す。
本発明の製造方法では、500ppmの水分を含む未蒸留THFを用いても、重合が進行することが確認された。
(Example 3-Sample S9)
The reaction was carried out in the same manner as in Example 1-S3, except that undistilled THF (dehydrated, without stabilizer, Wako Pure Chemical, 99.5%) (25 mL) was used as the solvent.
Reaction conditions and results are shown in Table 1-3.
The GPC chart and 1 HNMR chart of the polymer obtained are shown in FIG. 1 and FIG.
In the production method of the present invention, it was confirmed that polymerization proceeds even when undistilled THF containing 500 ppm of water is used.
(比較例1-サンプルS13)
<5-ブロモ-2-ヨード-3-ヘキシルチオフェンを出発物質とした未蒸留THF中でのGRIM重合によるレジオレギュラーポリ(3-ヘキシルチオフェン)の合成検討>
従来法(非特許文献7)に順じて、反応を実施した。
アルゴン気流下、30 mL二口フラスコに、5-ブロモ-2-ヨード-3-ヘキシルチオフェン(0.355g, 0.952 mmol)を量り取り、未蒸留THF(脱水・安定剤含まず・和光純正化学・99.5%)(25 mL)に溶解させた。この溶液に、iPrMgClのTHF溶液(2M x 0.478 mL = 0.956 mmol)を加え、0 ℃で2時間攪拌した。さらにNi(dppp)Cl2(8.5 mg, 0.0157 mmol)を加え、25 ℃で6時間重合反応を検討した。次に、5N-HCl水溶液を2 mL加え、重合反応を停止した。この反応条件では重合物は得られなかった。
従来の製造方法では、500ppmの水分を含む未蒸留THFを用いた場合、重合が全く進行しなかった。
(Comparative Example 1-Sample S13)
<Synthetic study of regioregular poly (3-hexylthiophene) by GRIM polymerization in undistilled THF starting from 5-bromo-2-iodo-3-hexylthiophene>
The reaction was carried out in accordance with the conventional method (Non-patent Document 7).
Under a stream of argon, weigh 5-bromo-2-iodo-3-hexylthiophene (0.355 g, 0.952 mmol) into a 30 mL two-necked flask, and use undistilled THF (dehydrated, without stabilizer, Wako Pure Chemical, 99.5 %) (25 mL). To this solution was added i PrMgCl in THF (2M x 0.478 mL = 0.956 mmol), and the mixture was stirred at 0 ° C for 2 hours. Further, Ni (dppp) Cl 2 (8.5 mg, 0.0157 mmol) was added, and the polymerization reaction was examined at 25 ° C. for 6 hours. Next, 2 mL of 5N-HCl aqueous solution was added to terminate the polymerization reaction. Under this reaction condition, no polymer was obtained.
In the conventional production method, when undistilled THF containing 500 ppm of water was used, the polymerization did not proceed at all.
(実施例3-サンプルS10)
<アルコール存在下でのtBu4ZnLi2を用いたレジオレギュラーポリ(3-ヘキシルチオフェン)の合成>
アルゴン気流下、50 mL二口フラスコに、1(0.341 g, 0.914 mmol)とiPrOH (54.6 mg, 0.914 mmol)を量り取り、THF(50 mL)に溶解させた。この溶液に、tBu4ZnLi2のTHF溶液(0.535 M x 1.70 mL = 0.910 mmol)を加え、0 ℃で2時間攪拌した。さらにNi(dppe)Cl2(8.0 mg, 0.0152 mmol)を加え、反応温度を60℃に昇温すると重合が進行した。6時間後、5N-HCl水溶液を2 mL加え、重合反応を停止した。得られた溶液をメタノール/水(150 mL/75 mL)に注ぐことで、ポリマーを沈殿させた。沈殿物を吸引ろ過し、メタノールでよく洗浄した後、60℃で真空乾燥することにより、紫色固体を得た。
得られたポリマーの測定結果を以下に示す。
0.091 g, 収率60%, Mn (SEC) = 10900, PDI = 1.15, レジオレギュラリティー=97%、
1H NMR(δ, CDCl3): 6.95 ppm (s, 1H), 2.80 (t, 2H), 1.70 (t, 2H), 1.25-1.5 (m, 6H), 0.88 (t, 3H).
反応条件及び結果を表1-3に示す。
本発明の製造方法では、アルコールを含む系でも重合が進行することが確認された。
(Example 3-Sample S10)
<Synthesis of regioregular poly (3-hexylthiophene) using t Bu 4 ZnLi 2 in the presence of alcohol>
1 (0.341 g, 0.914 mmol) and i PrOH (54.6 mg, 0.914 mmol) were weighed and dissolved in THF (50 mL) in a 50 mL two-necked flask under an argon stream. To this solution was added a THF solution of t Bu 4 ZnLi 2 (0.535 M x 1.70 mL = 0.910 mmol), and the mixture was stirred at 0 ° C for 2 hours. Furthermore, when Ni (dppe) Cl 2 (8.0 mg, 0.0152 mmol) was added and the reaction temperature was raised to 60 ° C., the polymerization proceeded. After 6 hours, 2 mL of 5N-HCl aqueous solution was added to stop the polymerization reaction. The resulting solution was poured into methanol / water (150 mL / 75 mL) to precipitate the polymer. The precipitate was suction filtered, washed well with methanol, and then vacuum dried at 60 ° C. to obtain a purple solid.
The measurement results of the obtained polymer are shown below.
0.091 g, Yield 60%, M n (SEC) = 10900, PDI = 1.15, Regioregularity = 97%,
1 H NMR (δ, CDCl 3 ): 6.95 ppm (s, 1H), 2.80 (t, 2H), 1.70 (t, 2H), 1.25-1.5 (m, 6H), 0.88 (t, 3H).
Reaction conditions and results are shown in Table 1-3.
In the production method of the present invention, it was confirmed that polymerization proceeds even in a system containing alcohol.
(比較例1-サンプルS14)
<アルコール存在下でGRIM重合を用いたレジオレギュラーポリ(3-ヘキシルチオフェン)の合成検討>
従来法(非特許文献7)に順じて、反応を実施した。
アルゴン気流下、30 mL二口フラスコに、化合物1(0.350 g, 0.938 mmol)とiPrOH (56.5 mg, 0.939 mmol)を量り取り、THF(25 mL)に溶解させた。この溶液に、iPrMgClのTHF溶液(2M x 0.470 mL = 0.940 mmol)を加え、0 ℃で2時間攪拌した。さらにNi(dppp)Cl2(8.5 mg, 0.0157 mmol)を加え、25 ℃に昇温し、6時間重合反応を検討した。次に、5N-HCl水溶液を2 mL加え、重合反応を停止した。この反応条件では重合物は得られず、化合物1が回収された。
従来の製造方法では、アルコールを含む系では重合が全く進行しなかった。
(Comparative Example 1-Sample S14)
<Synthetic study of regioregular poly (3-hexylthiophene) using GRIM polymerization in the presence of alcohol>
The reaction was carried out in accordance with the conventional method (Non-patent Document 7).
Under a stream of argon, Compound 1 (0.350 g, 0.938 mmol) and i PrOH (56.5 mg, 0.939 mmol) were weighed and dissolved in THF (25 mL) in a 30 mL two-necked flask. To this solution was added i PrMgCl in THF (2M × 0.470 mL = 0.940 mmol), and the mixture was stirred at 0 ° C. for 2 hours. Furthermore, Ni (dppp) Cl 2 (8.5 mg, 0.0157 mmol) was added, the temperature was raised to 25 ° C., and the polymerization reaction was examined for 6 hours. Next, 2 mL of 5N-HCl aqueous solution was added to terminate the polymerization reaction. Under this reaction condition, no polymer was obtained, and
In the conventional production method, polymerization did not proceed at all in the system containing alcohol.
(実施例1-サンプルS11)
溶媒として蒸留精製THFに1000ppmの純水を添加したものを用いた以外は実施例1-S3と同様にして、反応を実施した。反応条件及び結果を表1-3に示す。
本発明の製造方法では、1000ppmの水分を含む溶媒を用いても、重合が進行することが確認された。
(Example 1-Sample S11)
The reaction was carried out in the same manner as in Example 1-S3 except that a solvent obtained by adding 1000 ppm of pure water to distilled purified THF was used. Reaction conditions and results are shown in Table 1-3.
In the production method of the present invention, it was confirmed that polymerization proceeds even when a solvent containing 1000 ppm of water is used.
(比較例1-サンプルS15)
溶媒として蒸留精製THFに1000ppmの純水を添加したものを用いた以外は比較例1-S13と同様にして、反応を実施した。反応条件及び結果を表1-3に示す。
従来の製造方法では、1000ppmの水分を含む溶媒を用いた場合、重合が全く進行しなかった。
(Comparative Example 1-Sample S15)
The reaction was carried out in the same manner as Comparative Example 1-S13, except that a solvent obtained by adding 1000 ppm of pure water to distilled purified THF was used. Reaction conditions and results are shown in Table 1-3.
In the conventional production method, when a solvent containing 1000 ppm of water was used, the polymerization did not proceed at all.
(実施例3-サンプルS12)
<大気雰囲気下でのtBu4ZnLi2を用いたレジオレギュラーポリ(3-ヘキシルチオフェン)の合成>
アルゴン気流下、50 mL二口フラスコに、2-ブロモ-5-ヨード-3-ヘキシルチオフェン(化合物1)(0.385 g, 1.03 mmol)を量り取り、THF(50 mL)に溶解させた。この溶液に、tBu4ZnLi2のTHF溶液(0.535 M x 1.93 mL = 1.03 mmol)を加え、0 ℃で2時間攪拌した。さらにNi(dppe)Cl2(9.1 mg, 0.0172 mmol)を加え、反応温度を60℃に昇温した後、系を大気下に開放した。24時間後、5N-HCl水溶液を2 mL加え、重合反応を停止した。得られた溶液をメタノール/水(150 mL/75 mL)に注ぐことで、ポリマーを沈殿させた。沈殿物を吸引ろ過し、メタノールでよく洗浄した後、60℃で真空乾燥することにより、紫色固体を得た。
得られたポリマーの測定結果を以下に示す。
0.156 g, 収率91%, Mn (SEC) = 9000, 分子量分布(PDI) = 1.98, レジオレギュラリティー=96%、
1H NMR(δ, CDCl3): 6.95 ppm (s, 1H), 2.80 (t, 2H), 1.70 (t, 2H), 1.25-1.5 (m, 6H), 0.88 (t, 3H).
本発明の製造方法では、水分を含む大気中でも重合が進行することが確認された。
(Example 3-Sample S12)
<Synthesis of regioregular poly (3-hexylthiophene) using t Bu 4 ZnLi 2 under atmospheric conditions>
Under a stream of argon, 2-bromo-5-iodo-3-hexylthiophene (Compound 1) (0.385 g, 1.03 mmol) was weighed into a 50 mL two-necked flask and dissolved in THF (50 mL). To this solution was added a THF solution of t Bu 4 ZnLi 2 (0.535 M x 1.93 mL = 1.03 mmol), and the mixture was stirred at 0 ° C for 2 hours. Further, Ni (dppe) Cl 2 (9.1 mg, 0.0172 mmol) was added, the reaction temperature was raised to 60 ° C., and the system was opened to the atmosphere. After 24 hours, 2 mL of 5N-HCl aqueous solution was added to stop the polymerization reaction. The resulting solution was poured into methanol / water (150 mL / 75 mL) to precipitate the polymer. The precipitate was suction filtered, washed well with methanol, and then vacuum dried at 60 ° C. to obtain a purple solid.
The measurement results of the obtained polymer are shown below.
0.156 g, Yield 91%, M n (SEC) = 9000, Molecular weight distribution (PDI) = 1.98, Regioregularity = 96%,
1 H NMR (δ, CDCl 3 ): 6.95 ppm (s, 1H), 2.80 (t, 2H), 1.70 (t, 2H), 1.25-1.5 (m, 6H), 0.88 (t, 3H).
In the production method of the present invention, it was confirmed that polymerization proceeds even in an atmosphere containing moisture.
(比較例1-サンプルS16)
<大気雰囲気下でのGRIM重合によるレジオレギュラーポリ(3-ヘキシルチオフェン)の合成検討>
従来法(非特許文献7)に準じて、反応を実施した。
アルゴン気流下、30 mL二口フラスコに、5-ブロモ-2-ヨード-3-ヘキシルチオフェン(0.320g, 0.858 mmol)を量り取り、THF(25 mL)に溶解させた。この溶液に、iPrMgClのTHF溶液(2M x 0.430 mL = 0.860 mmol)を加え、0 ℃で2時間攪拌した。25 ℃に昇温した後、系を大気下に開放した。さらにNi(dppp)Cl2(7.8 mg, 0.0144 mmol)を加え、25 ℃で6時間重合反応を検討した。次に、5N-HCl水溶液を2 mL加え、重合反応を停止した。この重合条件では、重合物はほとんど得られず、収率は3.5%であった。
従来の製造方法では、水分を含む大気中では重合がほとんど進行しなかった。
(Comparative Example 1-Sample S16)
<Synthetic study of regioregular poly (3-hexylthiophene) by GRIM polymerization in air>
Reaction was performed according to the conventional method (nonpatent literature 7).
Under a stream of argon, 5-bromo-2-iodo-3-hexylthiophene (0.320 g, 0.858 mmol) was weighed into a 30 mL two-necked flask and dissolved in THF (25 mL). To this solution was added i PrMgCl in THF (2M x 0.430 mL = 0.860 mmol), and the mixture was stirred at 0 ° C for 2 hours. After raising the temperature to 25 ° C., the system was opened to the atmosphere. Ni (dppp) Cl 2 (7.8 mg, 0.0144 mmol) was further added, and the polymerization reaction was examined at 25 ° C. for 6 hours. Next, 2 mL of 5N-HCl aqueous solution was added to terminate the polymerization reaction. Under these polymerization conditions, almost no polymer was obtained, and the yield was 3.5%.
In the conventional production method, polymerization hardly progressed in the atmosphere containing moisture.
(実施例3-S9-S12、及び比較例1-S13-S16のまとめ)
グリニャール試薬よりも嵩高く弱い塩基性を有する亜鉛錯体の特徴を生かすため、未蒸留THF、不純物としてiPrOHを加えた系、蒸留精製THFに1000ppmの純水を添加した系、及び水分を含む大気雰囲気下での重合を検討した。これを達成するためには、以下の2点の条件を満たす必要がある。
(I)モノマー前駆体(化合物1)の金属ハロゲン交換反応の際に、反応試薬であるtBu4ZnLi2が不純物で失活しないこと。
(II)得られた亜鉛錯体モノマー(化合物2)が重合中に不純物で失活しないこと。
最初に未蒸留THF(脱水・安定剤含まず・和光純正化学・99.5%)中での重合を検討したところ(実施例3-S9)、設計通りの分子量Mn 11500と狭い分子量分布1.17のポリマーが得られた。
次に、iPrOHをモノマー(化合物2)に当モル量加えた系で同様の重合を行った結果、設計通りの分子量Mn 10900と狭い分子量分布1.15のポリマーを得ることに成功した(実施例3-S10)。
次に、蒸留精製THFに1000ppmの純水を添加した系で同様の重合を行った結果、設計通りの分子量Mn 16800と狭い分子量分布1.72のポリマーを得ることに成功した(実施例3-S11)。
次に、水分を含む大気雰囲気下で同様の重合を行った結果、設計通りの分子量Mn 9000と狭い分子量分布1.98のポリマーを得ることに成功した(実施例3-S12)。
従って、本重合系は条件(I)、(II)を共に満たすことが明らかとなった。
比較例として、未蒸留THF、不純物としてiPrOHを加えた系、蒸留精製THFに1000ppmの純水を添加した系、及び水分を含む大気雰囲気下で、化合物1のGRIM重合(従来法)を行ったところ、全く若しくはほとんど重合物が得られなかった。これらの比較例では、tBu4ZnLi2よりも塩基性が高く、水分に対して高反応性のグリニャール試薬を使用する必要があるためと考えられる。
(Summary of Examples 3-S9-S12 and Comparative Examples 1-S13-S16)
In order to take advantage of the zinc complex that is bulkier and weaker than the Grignard reagent, undistilled THF, a system in which i PrOH is added as an impurity, a system in which 1000 ppm pure water is added to distilled purified THF, and an atmosphere containing moisture Polymerization under atmosphere was studied. In order to achieve this, the following two conditions must be satisfied.
(I) In the metal halogen exchange reaction of the monomer precursor (compound 1), the reaction reagent t Bu 4 ZnLi 2 should not be deactivated by impurities.
(II) The obtained zinc complex monomer (compound 2) should not be deactivated by impurities during polymerization.
When we first investigated the polymerization in undistilled THF (dehydration, stabilizer not included, Wako Pure Chemicals, 99.5%) (Example 3-S9), a polymer with a molecular weight Mn of 11500 as designed and a narrow molecular weight distribution of 1.17 was found. Obtained.
Next, as a result of conducting similar polymerization in a system in which an equimolar amount of i PrOH was added to the monomer (compound 2), a polymer having a molecular weight Mn of 10900 as designed and a narrow molecular weight distribution of 1.15 was successfully obtained (Example 3). -S10).
Next, as a result of conducting similar polymerization in a system in which 1000 ppm of pure water was added to distilled purified THF, a polymer having a molecular weight Mn of 16800 as designed and a narrow molecular weight distribution of 1.72 was successfully obtained (Example 3-S11). .
Next, as a result of carrying out the same polymerization in an air atmosphere containing moisture, a polymer having a molecular weight Mn 9000 as designed and a narrow molecular weight distribution 1.98 was successfully obtained (Example 3-S12).
Therefore, it was revealed that this polymerization system satisfies both the conditions (I) and (II).
As comparative examples, GRIM polymerization of Compound 1 (conventional method) was performed in undistilled THF, a system in which i PrOH was added as an impurity, a system in which 1000 ppm of pure water was added to distilled purified THF, and an atmosphere containing moisture. As a result, no or almost no polymer was obtained. In these comparative examples, it is considered that it is necessary to use a Grignard reagent which is higher in basicity than t Bu 4 ZnLi 2 and highly reactive to moisture.
(実施例4-サンプルS17)
<2,5-ジブロモ-3-ヘキシルチオフェンを出発物質としたtBu4ZnLi2を用いたレジオレギュラーポリ(3-ヘキシルチオフェン)の合成>
アルゴン気流下、50 mL二口フラスコに、2,5-ジブロモ-3-ヘキシルチオフェン(0.311 g, 0.954 mmol)を量り取り、THF(50 mL)に溶解させた。この溶液に、tBu4ZnLi2のTHF溶液(0.535 M x 1.80 mL = 0.963 mmol)を加え、25 ℃で10分間攪拌した。さらにNi(dppe)Cl2(8.4 mg, 0.0159 mmol)を加え、反応温度を60℃に昇温すると重合が進行した。24時間後、5N-HCl水溶液を2 mL加え、重合反応を停止した。得られた溶液をメタノール/水(150 mL/75 mL)に注ぐことで、ポリマーを沈殿させた。沈殿物を吸引ろ過し、メタノールでよく洗浄した後、60℃で真空乾燥することにより、赤紫色固体を得た。
得られたポリマーの測定結果を以下に示す。
0.127 g, 収率80%, Mn (SEC) = 3470, PDI = 1.65, レジオレギュラリティー=94%、
1H NMR(δ, CDCl3): 6.95 ppm (s, 1H), 2.80 (t, 2H), 1.70 (t, 2H), 1.25-1.5 (m, 6H), 0.88 (t, 3H).
反応条件及び結果を表1-3に示す。
チオフェンモノマー(M1)においてXとYが同一の場合でも、金属ハロゲン交換反応は5位よりも2位の方が起こりやすく、目的生成物であるレジオレギュラーP3ATが高収率で得られることが示された。
(Example 4-Sample S17)
<Synthesis of regioregular poly (3-hexylthiophene) using t Bu 4 ZnLi 2 starting from 2,5-dibromo-3-hexylthiophene>
Under a stream of argon, 2,5-dibromo-3-hexylthiophene (0.311 g, 0.954 mmol) was weighed into a 50 mL two-necked flask and dissolved in THF (50 mL). To this solution was added a THF solution of t Bu 4 ZnLi 2 (0.535 M x 1.80 mL = 0.963 mmol), and the mixture was stirred at 25 ° C for 10 minutes. Furthermore, when Ni (dppe) Cl 2 (8.4 mg, 0.0159 mmol) was added and the reaction temperature was raised to 60 ° C., the polymerization proceeded. After 24 hours, 2 mL of 5N-HCl aqueous solution was added to stop the polymerization reaction. The resulting solution was poured into methanol / water (150 mL / 75 mL) to precipitate the polymer. The precipitate was suction filtered, washed well with methanol, and then vacuum dried at 60 ° C. to obtain a reddish purple solid.
The measurement results of the obtained polymer are shown below.
0.127 g, Yield 80%, M n (SEC) = 3470, PDI = 1.65, Regioregularity = 94%,
1 H NMR (δ, CDCl 3 ): 6.95 ppm (s, 1H), 2.80 (t, 2H), 1.70 (t, 2H), 1.25-1.5 (m, 6H), 0.88 (t, 3H).
Reaction conditions and results are shown in Table 1-3.
Even when X and Y are the same in the thiophene monomer (M1), the metal halogen exchange reaction is more likely to occur at the 2-position than at the 5-position, indicating that the desired product, regioregular P3AT, can be obtained in high yield. It was done.
(実施例5)
<tBu4ZnLi2を用いた後重合法によるレジオレギュラーポリ(3-ヘキシルチオフェン)の合成>
本発明の重合系が連鎖的かつリビング的(モノマーをすべて消費してもポリマー鎖末端の活性を失わず、モノマーを加えれば再び重合が可能であることを「リビング的」と呼ぶ)に進行することを証明するためにモノマー(化合物2)を2回に分けて重合系中に添加する方法(Postpolymerization Method(後重合法))を用いた。
アルゴン気流下、50 mL二口フラスコに、化合物1(0.298 g, 0.799 mmol)(第1モノマー)を量り取り、THF(50 mL)に溶解させた。この溶液に、tBu4ZnLi2のTHF溶液(0.535 M x 1.50 mL = 0.803 mmol)を加え、0 ℃で2時間攪拌した。さらにNi(dppe)Cl2(7.0 mg, 0.0133 mmol)を加え、反応温度を60℃に昇温すると重合が進行した。15分後、少量の反応溶液をサンプリングした。
最初に添加したモノマーが完全に消費されMn 9800、分子量分布1.15の第1ブロックP3HTが得られたことを確認した後、系に再度モノマー(化合物2)を加え、鎖延長反応(後重合)を行った。具体的には、残りの溶液に後述する方法で調製した第2モノマー溶液を加え、60℃でさらに6時間重合させた。5N-HCl水溶液を2 mL加え、重合反応を停止した。
第2モノマー溶液の調整法:アルゴン気流下、20 mL二口フラスコに、化合物1(0.500 g, 1.34 mmol)を量り取り、THF(10 mL)に溶解させた。この溶液に、tBu4ZnLi2のTHF溶液(0.535 M x 2.50 mL = 1.34 mmol)を加え、0 ℃で2時間攪拌することで第2モノマー溶液を得た。
重合反応後に得られた溶液をメタノール/水(200 mL/100 mL)に注ぐことで、ポリマーを沈殿させた。沈殿物を吸引ろ過し、メタノールでよく洗浄した後、60℃で真空乾燥することにより、紫色固体を得た。
本実施例では、サイズ排除クロマトグラフィー(SEC)曲線より、単峰性のピークが狭い分子量分布を保ったまま、高分子量側に移動し、Mn 25000、分子量分布1.29のP3HTが得られた。第1ブロックに相当する付近にSECの残存ピークが観察されなかったことから、この重合系は連鎖的かつリビング的に進行することが証明された。
得られたポリマーの測定結果を以下に示す。
0.284 g, 収率80%, Mn (SEC) = 25000, PDI = 1.29, レジオレギュラリティー=98%、
1H NMR(δ, CDCl3): 6.95 ppm (s, 1H), 2.80 (t, 2H), 1.70 (t, 2H), 1.25-1.5 (m, 6H), 0.88 (t, 3H).
(Example 5)
<Synthesis of regioregular poly (3-hexylthiophene) by post-polymerization using t Bu 4 ZnLi 2 >
The polymerization system of the present invention proceeds in a chain and living manner (referred to as “living” that the activity of the polymer chain end is not lost even if all of the monomer is consumed and the polymerization is possible again by adding the monomer). In order to prove this, a method (Postpolymerization Method) in which the monomer (Compound 2) was added to the polymerization system in two portions was used.
Under a stream of argon, Compound 1 (0.298 g, 0.799 mmol) (first monomer) was weighed into a 50 mL two-necked flask and dissolved in THF (50 mL). To this solution was added a THF solution of t Bu 4 ZnLi 2 (0.535 M x 1.50 mL = 0.803 mmol), and the mixture was stirred at 0 ° C for 2 hours. Furthermore, when Ni (dppe) Cl 2 (7.0 mg, 0.0133 mmol) was added and the reaction temperature was raised to 60 ° C., the polymerization proceeded. After 15 minutes, a small amount of the reaction solution was sampled.
After confirming that the first added monomer was completely consumed and the first block P3HT with Mn 9800 and molecular weight distribution 1.15 was obtained, the monomer (compound 2) was added to the system again, and chain extension reaction (post-polymerization) was performed. went. Specifically, the second monomer solution prepared by the method described later was added to the remaining solution, and the mixture was further polymerized at 60 ° C. for 6 hours. 2 mL of 5N-HCl aqueous solution was added to stop the polymerization reaction.
Preparation method of second monomer solution: Compound 1 (0.500 g, 1.34 mmol) was weighed into a 20 mL two-necked flask under an argon stream and dissolved in THF (10 mL). To this solution was added a THF solution of t Bu 4 ZnLi 2 (0.535 M × 2.50 mL = 1.34 mmol), and the mixture was stirred at 0 ° C. for 2 hours to obtain a second monomer solution.
The polymer was precipitated by pouring the solution obtained after the polymerization reaction into methanol / water (200 mL / 100 mL). The precipitate was suction filtered, washed well with methanol, and then vacuum dried at 60 ° C. to obtain a purple solid.
In this example, from the size exclusion chromatography (SEC) curve, the unimodal peak moved to the high molecular weight side while maintaining a narrow molecular weight distribution, and P3HT with Mn 25000 and molecular weight distribution 1.29 was obtained. Since no residual SEC peak was observed in the vicinity of the first block, it was proved that this polymerization system proceeded in a chain and living manner.
The measurement results of the obtained polymer are shown below.
0.284 g, Yield 80%, Mn (SEC) = 25000, PDI = 1.29, Regioregularity = 98%,
1 H NMR (δ, CDCl 3 ): 6.95 ppm (s, 1H), 2.80 (t, 2H), 1.70 (t, 2H), 1.25-1.5 (m, 6H), 0.88 (t, 3H).
Claims (12)
少なくとも1種のエーテル系溶媒を含む溶媒存在下で、下記一般式(M1)で表されるチオフェンモノマーとジリチウムテトラ(tert-ブチル)ジンケートとを反応させる工程Aと、
前記溶媒存在下で、工程Aの反応生成物に重合触媒を加えて溶液重合反応を行う工程Bとを有するポリチオフェン類の製造方法。
A step A of reacting a thiophene monomer represented by the following general formula (M1) with dilithium tetra (tert-butyl) zincate in the presence of a solvent containing at least one ether solvent;
A method for producing a polythiophene, comprising: a step B in which a solution polymerization reaction is performed by adding a polymerization catalyst to the reaction product of the step A in the presence of the solvent.
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