CN113603868A - 一种基于芳基二卤代物和芳基二锡烷的Stille交叉偶联室温聚合方法 - Google Patents
一种基于芳基二卤代物和芳基二锡烷的Stille交叉偶联室温聚合方法 Download PDFInfo
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- CN113603868A CN113603868A CN202110895308.7A CN202110895308A CN113603868A CN 113603868 A CN113603868 A CN 113603868A CN 202110895308 A CN202110895308 A CN 202110895308A CN 113603868 A CN113603868 A CN 113603868A
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- aryl
- chloroform
- polymer
- methanol
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 title claims description 8
- 238000005700 Stille cross coupling reaction Methods 0.000 title abstract description 8
- -1 (tri-tert-butyl phosphino) (2 '-amino-1, 1' -biphenyl-2-yl) Chemical group 0.000 claims abstract description 128
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 96
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 84
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920000642 polymer Polymers 0.000 claims abstract description 49
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 34
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims abstract description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910000160 potassium phosphate Inorganic materials 0.000 claims abstract description 16
- 235000011009 potassium phosphates Nutrition 0.000 claims abstract description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920000547 conjugated polymer Polymers 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000000654 additive Substances 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract 2
- 238000001556 precipitation Methods 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910018821 PO3 Inorganic materials 0.000 claims description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 239000012434 nucleophilic reagent Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 229940098779 methanesulfonic acid Drugs 0.000 abstract description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 abstract description 2
- 230000005669 field effect Effects 0.000 abstract 1
- 238000003384 imaging method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000002428 photodynamic therapy Methods 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 238000000944 Soxhlet extraction Methods 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 12
- 238000000605 extraction Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000005979 thermal decomposition reaction Methods 0.000 description 12
- 239000010409 thin film Substances 0.000 description 8
- 229920000052 poly(p-xylylene) Polymers 0.000 description 7
- DTJBEISROOTMQK-UHFFFAOYSA-N trimethyl-(5-trimethylstannylselenophen-2-yl)stannane Chemical compound C[Sn](C)(C)C1=CC=C([Sn](C)(C)C)[se]1 DTJBEISROOTMQK-UHFFFAOYSA-N 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 5
- 239000010408 film Substances 0.000 description 4
- 229910000338 selenium disulfide Inorganic materials 0.000 description 4
- 230000007847 structural defect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KKRPPVXJVZKJON-UHFFFAOYSA-N trimethyl-(5-trimethylstannylthiophen-2-yl)stannane Chemical compound C[Sn](C)(C)C1=CC=C([Sn](C)(C)C)S1 KKRPPVXJVZKJON-UHFFFAOYSA-N 0.000 description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- FYIOMGMQCNUOFL-UHFFFAOYSA-N 1,4-bis(5-bromothiophen-2-yl)-2,5-bis(2-decyltetradecyl)pyrrolo[3,4-c]pyrrole-3,6-dione Chemical compound CCCCCCCCCCCCC(CCCCCCCCCC)CN1C(=O)C2=C(C=3SC(Br)=CC=3)N(CC(CCCCCCCCCC)CCCCCCCCCCCC)C(=O)C2=C1C1=CC=C(Br)S1 FYIOMGMQCNUOFL-UHFFFAOYSA-N 0.000 description 1
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- NWRUYRQLNMLUMB-UHFFFAOYSA-N 4,9-dibromo-2,7-bis(2-octyldodecyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2h,7h)-tetraone Chemical compound C1=C(Br)C(C(N(CC(CCCCCCCC)CCCCCCCCCC)C2=O)=O)=C3C2=CC(Br)=C2C(=O)N(CC(CCCCCCCC)CCCCCCCCCC)C(=O)C1=C32 NWRUYRQLNMLUMB-UHFFFAOYSA-N 0.000 description 1
- OCFFMJYHZKHRKM-UHFFFAOYSA-N [4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]-2-trimethylstannylthieno[2,3-f][1]benzothiol-6-yl]-trimethylstannane Chemical compound S1C(CC(CC)CCCC)=CC=C1C(C=1SC(=CC=11)[Sn](C)(C)C)=C(C=C(S2)[Sn](C)(C)C)C2=C1C1=CC=C(CC(CC)CCCC)S1 OCFFMJYHZKHRKM-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002026 chloroform extract Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- URMVZUQDPPDABD-UHFFFAOYSA-N thieno[2,3-f][1]benzothiole Chemical compound C1=C2SC=CC2=CC2=C1C=CS2 URMVZUQDPPDABD-UHFFFAOYSA-N 0.000 description 1
- LGLMAWUUKPRGBF-UHFFFAOYSA-N trimethyl-(5-trimethylstannylfuran-2-yl)stannane Chemical compound C[Sn](C)(C)C1=CC=C([Sn](C)(C)C)O1 LGLMAWUUKPRGBF-UHFFFAOYSA-N 0.000 description 1
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- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
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- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
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- C08G2261/124—Copolymers alternating
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3222—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more oxygen atoms as the only heteroatom, e.g. furan
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3225—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more Se atoms as the only heteroatom
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- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/414—Stille reactions
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
本发明提供了一种在室温条件下的基于芳基体系的普适性Stille交叉偶联共聚反应制备有机半导体材料的方法学。采用惰性气体保护，在甲磺酸(三‑叔丁基膦基)(2’‑氨基‑1,1’‑联苯‑2‑基)钯(II)(即P(t‑Bu)3Pd G3)的催化剂作用下，加入磷酸钾作为添加剂，将芳基二卤代物与芳基二锡烷置于四氢呋喃或甲苯中，并在室温条件下进行反应，得到混合物。将混合物滴入甲醇中沉淀过滤，并将沉淀物采用索氏提取器通过丙酮、正己烷及三氯甲烷分别进行提取，将三氯甲烷提取得到的聚合物溶液浓缩后滴入甲醇中制得高分子量D‑A共轭聚合物。采用本方法制得的共轭聚合物可以应用于有机场效应晶体管、有机太阳能电池、细胞成像和光热、光动力治疗等领域。
Description
技术领域：
本发明涉有机半导体活性层给体-受体(D-A)共轭聚合物合成的技术领域，具体涉及一种基于芳基二卤代物和芳基二锡烷的Stille交叉偶联室温聚合方法。
背景技术：
有机共轭聚合物由于其在塑料电子中的巨大潜力而备受瞩目，如化学结构可调节性、带隙和光吸收可调控性、电荷传输迁移率优良、可柔性制备性和溶液可加工性等优点。无缺陷、结构完美交替的π-共轭D-A共聚物，比存在结构缺陷的D-A共聚物，电荷传输性能更加优异。
D-A共轭聚合物传统的制备方法，是以三(二亚苄基丙酮)二钯及双(三-o-甲苯磷)钯(0)体系(即Pd2(dba)3/P(o-tol)3体系)或四(三苯基膦)钯体系(即Pd(PPh3)4体系)为催化剂，将芳基二卤代物和芳基二锡烷在加热和氮气保护条件下进行Stille交叉偶联聚合反应。在该条件下，不仅增大了反应所需的能耗，更有可能会使共聚物产生结构缺陷。而结构缺陷的产生，会使D-A共聚物的电荷迁移率降低。因而如何在室温条件下实现无缺陷或者低缺陷的共聚物，成为有机半导体领域里亟待解决的问题。
发明内容：
针对上述问题，本发明提供了一种以芳基二卤代物为亲电试剂，以芳基二锡烷为亲核试剂的Stille交叉偶联聚合方法，该方法以甲磺酸(三-叔丁基膦基)(2’-氨基-1,1’-联苯-2-基)钯(II)(即P(t-Bu)3Pd G3)为催化剂，以磷酸钾为添加剂，在常温条件下实现Stille交叉偶联共聚反应。
本发明是基于芳基二卤代物为亲电试剂、芳基二锡烷为亲核试剂的Stille交叉偶联共聚反应。反应通式如下：
其中，Ar1和Ar2表示相同或不同的芳基体系；
其中，n表示聚合度；
其中，X表示卤素，优选为氯、溴、碘；
其中，Ra和Rb各自独立地表示氢或C1-C30烷基，优选为C1-C20烷基，更优选为C1-C10烷基；
其中，所述的碱性条件为Cs2CO3,K3PO3,Na2CO3,NaHCO3,NaOH的任意一种或其组合；
其中，所述的溶剂选自THF，DMSO,DMF,二氧六环，二氯化碳，氯仿，甲醇，乙醇，甲苯，丙酮，正己烷中的任意一种或其组合；
其中，P(t-Bu)3Pd G3的结构式为：
在本发明的方法中，其中，芳基二卤代物为下列任意一种化合物：
其中，X为氯原子、溴原子或碘原子。R,R1,R2,R3为独立的氢或C1-C30的烷基，其中包括碳原子总数为6-16的直链烷基包括：正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基；以及碳原子总数为8–30的支链烷基包括：2-乙基己基，2-乙基辛基，2-丁基己基、2-己基辛基、4-己基癸基、3-己基十一烷基、2-辛基癸基、2-辛基十二烷基、3-辛基十三烷基、2-癸基十二烷基、2-癸基十四烷基、3-癸基十五烷基、2-十二烷基十六烷基、4-辛基十四烷基、4-癸基十六烷基、4-己基癸基、4-辛基十二烷基、4-癸基十四烷基、4-十二烷基十六烷基。
在本发明的方法中，其中，所述的芳基二锡烷为下列任意一种化合物：
R,R1,R2为独立的氢或C1-C30的烷基，其中包括碳原子总数为6-16的直链烷基包括：正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基；以及碳原子总数为8–30的支链烷基包括：2-乙基己基，2-乙基辛基，2-丁基己基、2-己基辛基、4-己基癸基、3-己基十一烷基、2-辛基癸基、2-辛基十二烷基、3-辛基十三烷基、2-癸基十二烷基、2-癸基十四烷基、3-癸基十五烷基、2-十二烷基十六烷基、4-辛基十四烷基、4-癸基十六烷基、4-己基癸基、4-辛基十二烷基、4-癸基十四烷基、4-十二烷基十六烷基。
发明是基于芳基二卤代物与芳基二锡烷在P(t-Bu)3Pd G3的催化作用下实现的，具体合成方法为：
将1当量的芳基二卤代物、1当量的芳基二锡烷、P(t-Bu)3Pd G3(10mol％)和1当量的磷酸钾放入到反应瓶中。置换氮气三次后，加入干燥的四氢呋喃或甲苯(使溶液的浓度保持在0.05M)。室温搅拌24小时(部分体系可能延长至72小时)后，加入甲醇使沉淀析出。过滤之后，将滤饼依次分别用丙酮、正己烷和三氯甲烷进行索氏提取。三氯甲烷提取液经浓缩后用甲醇析出沉淀。沉淀过滤、干燥之后，即为目标聚合物。
本发明的优点在于：
(1)反应在室温条件下进行，反应所需的能耗低，可以大幅降低合成成本；
(2)反应在室温条件下进行，使得实验室安全以及工业生产中的安全有了有效保障；
(3)反应的速度快，在三十分钟内即达到上万的分子量；
(4)反应的普适性强，可以有效应用于众多缺电子或富电子的芳香体系的高分子共轭结构构筑中；
(5)相对于加热的Stille聚合反应，本合成方法学所制备的共轭高分子聚合物的结构缺陷大幅降低；
(6)反应可以应用于一克级以上的反应体系，获得与微量反应等价的分子量。
具体实施方式：
实施例1
在氮气保护下，将2,5-双(三甲基锡基)硒吩(23.0mg，0.05mmol)、3,6-双(5-溴噻吩基)-2,5-双(2-癸基十四烷基)吡咯并[3,4-c]吡咯-1,4-二酮(56.4mg，0.05mmol)、P(t-Bu)3Pd G3(2.9mg，0.005mmol)和磷酸钾(10.6mg，0.05mmol)放入反应瓶中。加入1.0mL四氢呋喃后，在室温条件下搅拌24小时。加入20.0mL甲醇后，将生成的沉淀过滤。然后将沉淀出来的聚合物依次分别用丙酮、正己烷和三氯甲烷进行索氏提取。将三氯甲烷提取后所得溶液浓缩，然后用20.0mL甲醇沉淀出聚合物，过滤、烘干即可得到黑绿色聚合物固体(52.2mg，95％)。1H NMR(500MHz,CDCl3)：δ9.27-8.86(br,2H),7.49-6.73(br,4H),4.62-3.47(br,4H),2.07-1.96(br,2H),1.85-0.98(br,80H),0.99-0.68(br,12H)。GPC:Mn 39.4kDa,Mw88.9kDa,
元素分析计算值{(C66H104N2O2S2Se)n}：C,72.02；H,9.52；N,2.55。实测值：C,70.21；H,9.21；N,2.46。该聚合物的热分解温度：435℃。最大吸收波长：848nm(三氯甲烷溶液)，871nm(薄膜)。
实施例2
在氮气保护下，将2,5-双(三甲基锡基)硒吩(23.0mg，0.05mmol)、3,6-双(5-溴噻吩-2-基)-2,5-双(2-辛基十二烷基)-2,5-二氢吡咯并[3,4-c]吡咯-1,4-二酮(50.8mg，0.05mmol)、P(t-Bu)3Pd G3(2.9mg，0.005mmol)和磷酸钾(10.6mg，0.05mmol)放入反应瓶中。加入1.0mL四氢呋喃后，在室温条件下搅拌24小时。加入20.0mL甲醇后，将生成的沉淀过滤。然后将沉淀出来的聚合物依次分别用丙酮、正己烷和三氯甲烷进行索氏提取。将三氯甲烷提取后所得溶液浓缩，然后用20.0mL甲醇沉淀出聚合物，过滤、烘干即可得到黑绿色聚合物固体(46.5mg，94％)。1H NMR(500MHz,CDCl3):δ9.26-8.82(br,2H),7.58-6.72(br,4H),4.34-3.65(br,4H),2.09-1.80(br,2H),1.53-0.98(br,64H),0.93-0.74(br,12H)。GPC:Mn32.2kDa,Mw 69.8kDa,
元素分析计算值{(C58H88N2O2S2Se)n}：C,70.48；H,8.97；N,2.83。实测值：C,68.88；H,8.75；N,2.66。该聚合物的热分解温度：431℃。最大吸收波长：850nm(三氯甲烷溶液)，875nm(薄膜)。
实施例3
在氮气保护下，将2,5-双(三甲基锡基)硒吩(23.0mg，0.05mmol)、3,6-双(5-溴噻吩[3,2-b]噻吩-2-基)-2,5-双(2-辛基十二烷基)-2,5-二氢吡咯并[3,4-c]吡咯-1,4-二酮(56.4mg，0.05mmol)、P(t-Bu)3Pd G3(2.9mg，0.005mmol)和磷酸钾(10.6mg，0.05mmol)放入反应瓶中。加入1.0mL四氢呋喃后，在室温条件下搅拌24小时。加入20.0mL甲醇后，将生成的沉淀过滤。然后将沉淀出来的聚合物依次分别用丙酮、正己烷和三氯甲烷进行索氏提取。将三氯甲烷提取后所得溶液浓缩，然后用20.0mL甲醇沉淀出聚合物，过滤、烘干即可得到黑绿色聚合物固体(51.5mg，89％)。1H NMR(500MHz,CDCl3):δ9.51-8.63(br,2H),7.51-5.82(br,4H),4.55-3.50(br,4H),2.49-2.11(br,2H),2.09-1.00(br,64H),1.00-0.65(br,12H)。GPC:Mn 11.3kDa,Mw 32.2kDa,
元素分析计算值{(C62H88N2O2S4Se)n}：C,67.66；H,8.06；N,2.55。实测值：C,66.66；H,7.96；N,2.40。该聚合物的热分解温度：316℃。最大吸收波长：772nm(三氯甲烷溶液)，834nm(薄膜)。
实施例4
在氮气保护下，将2,5-双(三甲基锡基)硒吩(23.0mg，0.05mmol)、6,6'-二溴-N,N'-(2-辛基十二烷基)-异靛蓝(48.9mg，0.05mmol)、P(t-Bu)3Pd G3(2.9mg，0.005mmol)和磷酸钾(10.6mg，0.05mmol)放入反应瓶中。加入1.0mL四氢呋喃后，在室温条件下搅拌72小时。加入20.0mL甲醇后，将生成的沉淀过滤。然后将沉淀出来的聚合物依次分别用丙酮、正己烷和三氯甲烷进行索氏提取。将三氯甲烷提取后所得溶液浓缩，然后用20.0mL甲醇沉淀出聚合物，过滤、烘干即可得到黑绿色聚合物固体(40.1mg，84％)。1H NMR(500MHz,CDCl3):δ9.93-8.87(br,2H),7.60-7.32(br,2H),7.19-6.92(br,2H),6.89-6.55(br,2H),4.26-3.14(br,4H),2.13-1.81(br,2H),1.76-1.08(br,64H),1.02-0.76(br,12H)。GPC:Mn 77.8kDa,Mw171.1kDa,
元素分析计算值{(C60H90N2O2Se)n}：C,75.83；H,9.55；N,2.95。实测值：C,74.95；H,9.43；N,2.84。该聚合物的热分解温度：416℃。最大吸收波长：703nm(三氯甲烷溶液)，715nm(薄膜)。
实施例5
在氮气保护下，将2,5-双(三甲基锡基)硒吩(23.0mg，0.05mmol)、4,9-二溴-2,7-二(2-辛基十二烷基)苯并[lmn][3,8]邻二氮杂菲-1,3,6,8(2H,7H)-四酮(49.1mg，0.05mmol)、P(t-Bu)3Pd G3(2.9mg，0.005mmol)和磷酸钾(10.6mg，0.05mmol)放入反应瓶中。加入1.0mL四氢呋喃后，在室温条件下搅拌72小时。加入20.0mL甲醇后，将生成的沉淀过滤。然后将沉淀出来的聚合物依次分别用丙酮、正己烷和三氯甲烷进行索氏提取。将三氯甲烷提取后所得溶液浓缩，然后用20.0mL甲醇沉淀出聚合物，过滤、烘干即可得到黑紫色聚合物固体(37.7mg，79％)。1H NMR(500MHz,CDCl3):δ9.04-8.96(br,2H),7.70-7.56(br,2H),4.21-4.16(br,4H),2.05-2.01(br,2H),1.57-1.01(br,64H),0.89-0.81(br,12H)。GPC:Mn29.3kDa,Mw 52.6kDa,
元素分析计算值{(C58H86N2O4Se)n}：C,73.00；H,9.08；N,2.94。实测值：C,73.43；H,9.18；N,2.75。该聚合物的热分解温度：436℃。最大吸收波长：563nm(三氯甲烷溶液)，628nm(薄膜)。
实施例6
在氮气保护下，将2,5-双(三甲基锡基)硒吩(23.0mg，0.05mmol)、2,6-二溴-4,8-双[(2-辛基十二烷基)氧基]苯并[1,2-b:4,5-b']二噻吩(46.9mg，0.05mmol)、P(t-Bu)3PdG3(2.9mg，0.005mmol)和磷酸钾(10.6mg，0.05mmol)放入反应瓶中。加入1.0mL四氢呋喃后，在室温条件下搅拌24小时。加入20.0mL甲醇后，将生成的沉淀过滤。然后将沉淀出来的聚合物依次分别用丙酮、正己烷和三氯甲烷进行索氏提取。将三氯甲烷提取后所得溶液浓缩，然后用20.0mL甲醇沉淀出聚合物，过滤、烘干即可得到黑紫色聚合物固体(24.2mg，53％)。1HNMR(500MHz,CDCl3):δ7.53-7.29(br,2H),4.91-3.71(br,2H),4.30-3.90(br,4H),2.03-1.78(br,2H),1.75-1.09(br,64H),1.04-0.72(br,12H)。GPC:Mn 50.1kDa,Mw 136.7kDa,
元素分析计算值{(C54H86O2S2Se)n}：C,71.25；H,9.52。实测值：C,70.34；H,9.07。该聚合物的热分解温度：445℃。最大吸收波长：511nm(三氯甲烷溶液)，547nm(薄膜)。
实施例7
在氮气保护下，将2,5-双(三甲基锡基)硒吩(23.0mg，0.05mmol)、2,7-二溴-4,4,9,9-四十六烷基-4,9-二氢-s-茚并[1,2-b:5,6-b']二噻吩(65.9mg，0.05mmol)、P(t-Bu)3Pd G3(2.9mg，0.005mmol)和磷酸钾(10.6mg，0.05mmol)放入反应瓶中。加入1.0mL四氢呋喃后，在室温条件下搅拌72小时。加入20.0mL甲醇后，将生成的沉淀过滤。然后将沉淀出来的聚合物依次分别用丙酮、正己烷和三氯甲烷进行索氏提取。将三氯甲烷提取后所得溶液浓缩，然后用20.0mL甲醇沉淀出聚合物，过滤、烘干即可得到红色聚合物固体(61.3mg，95％)。1H NMR(500MHz,CDCl3):δ7.31-7.27(br,2H),6.05-5.41(br,2H),4.73-3.92(br,2H),2.26-1.04(br,120H),0.96-0.80(br,12H)。GPC:Mn 27.1kDa,Mw 77.3kDa,
元素分析计算值{(C84H138S2Se)n}：C,78.14；H,10.77。实测值：C,76.55；H,9.67。该聚合物的热分解温度：414℃。最大吸收波长：568nm(三氯甲烷溶液)，573nm(薄膜)。
实施例8
在氮气保护下，将2,5-双(三甲基锡基)噻吩(20.6mg，0.05mmol)、2,7-二溴-4,4,9,9-四十六烷基-4,9-二氢-s-茚并[1,2-b:5,6-b']二噻吩(65.9mg，0.05mmol)、P(t-Bu)3Pd G3(2.9mg，0.005mmol)和磷酸钾(10.6mg，0.05mmol)放入反应瓶中。加入1.0mL四氢呋喃后，在室温条件下搅拌72小时。加入20.0mL甲醇后，将生成的沉淀过滤。然后将沉淀出来的聚合物依次分别用丙酮、正己烷和三氯甲烷进行索氏提取。将三氯甲烷提取后所得溶液浓缩，然后用20.0mL甲醇沉淀出聚合物，过滤、烘干即可得到红色聚合物固体(59.1mg，95％)。1H NMR(500MHz,CDCl3):δ7.26-7.17(br,2H),7.16-7.11(br,2H),7.10-7.04(br,2H),1.08-1.03(br,120H),0.94-0.81(br,12H)。GPC:Mn 26.3kDa,Mw 65.0kDa,
元素分析计算值{(C84H138S3)n}：C,81.09；H,11.18。实测值：C,80.89；H,10.97。该聚合物的热分解温度：435℃。最大吸收波长：549nm(三氯甲烷溶液)，552nm(薄膜)。
实施例9
在氮气保护下，将2,5-双(三甲基锡基)噻吩(20.6mg，0.05mmol)、3,6-双(5-溴噻吩基)-2,5-双(2-癸基十四烷基)吡咯并[3,4-c]吡咯-1,4-二酮(56.4mg，0.05mmol)、P(t-Bu)3Pd G3(2.9mg，0.005mmol)和磷酸钾(10.6mg，0.05mmol)放入反应瓶中。加入1.0mL四氢呋喃后，在室温条件下搅拌72小时。加入20.0mL甲醇后，将生成的沉淀过滤。然后将沉淀出来的聚合物依次分别用丙酮、正己烷和三氯甲烷进行索氏提取。将三氯甲烷提取后所得溶液浓缩，然后用20.0mL甲醇沉淀出聚合物，过滤、烘干即可得到黑绿色聚合物固体(43.7mg，83％)。1H NMR(500MHz,CDCl3):δ9.11-8.64(br,2H),7.17-6.81(br,4H),4.27-3.69(br,4H),1.99-1.87(br,2H),1.68-1.05(br,80H),0.93-0.79(br,12H)。GPC:Mn 37.8kDa,Mw71.2kDa,
元素分析计算值{(C66H104N2O2S3)n}：C,75.23；H,9.95；N,2.66。实测值：C,75.59；H,9.88；N,2.61。该聚合物的热分解温度：433℃。最大吸收波长：814nm(三氯甲烷溶液)，848nm(薄膜)。
实施例10
在氮气保护下，将2,5-双(三甲基锡基)呋喃(19.8mg，0.05mmol)、3,6-双(5-溴噻吩基)-2,5-双(2-癸基十四烷基)吡咯并[3,4-c]吡咯-1,4-二酮(56.4mg，0.05mmol)、P(t-Bu)3Pd G3(2.9mg，0.005mmol)和磷酸钾(10.6mg，0.05mmol)放入反应瓶中。加入1.0mL四氢呋喃后，在室温条件下搅拌72小时。加入20.0mL甲醇后，将生成的沉淀过滤。然后将沉淀出来的聚合物依次分别用丙酮、正己烷和三氯甲烷进行索氏提取。将三氯甲烷提取后所得溶液浓缩，然后用20.0mL甲醇沉淀出聚合物，过滤、烘干即可得到黑绿色聚合物固体(46.7mg，90％)。1H NMR(500MHz,CDCl3):δ9.58-8.63(br,2H),7.71-6.35(br,4H),5.18-2.82(br,4H),2.02-1.74(br,2H),7.13-0.98(br,80H),0.98-0.27(br,12H)。GPC:Mn 43.6kDa,Mw80.5kDa,
元素分析计算值{(C66H104N2O3S2)n}：C,76.39；H,10.10；N,2.70。实测值：C,75.71；H,9.84；N,2.63。该聚合物的热分解温度：446℃。最大吸收波长：797nm(三氯甲烷溶液)，815nm(薄膜)。
实施例11
在氮气保护下，将(4,8-双(5-(2-乙基己基)噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩-2,6-二基)双(三甲基锡烷)(45.3mg，0.05mmol)、3,6-双(5-溴噻吩基)-2,5-双(2-癸基十四烷基)吡咯并[3,4-c]吡咯-1,4-二酮(56.4mg，0.05mmol)、P(t-Bu)3Pd G3(2.9mg，0.005mmol)和磷酸钾(10.6mg，0.05mmol)放入反应瓶中。加入1.0mL四氢呋喃后，在室温条件下搅拌72小时。加入20.0mL甲醇后，将生成的沉淀过滤。然后将沉淀出来的聚合物依次分别用丙酮、正己烷和三氯甲烷进行索氏提取。将三氯甲烷提取后所得溶液浓缩，然后用20.0mL甲醇沉淀出聚合物，过滤、烘干即可得到黑绿色聚合物固体(68.1mg，88％)。1H NMR(500MHz,CDCl3):δ9.49-8.92(br,2H),8.13-6.77(br,8H),4.43-3.64(br,4H),3.29-2.85(br,4H),2.11-1.80(br,4H),1.80-0.98(br,96H),0.98-0.78(br,24H)。GPC:Mn 31.4kDa,Mw83.0kDa,
元素分析计算值{(C96H142N2O2S6)n}：C,74.46；H,9.24；N,1.81。实测值：C,74.12；H,9.07；N,1.81。该聚合物的热分解温度：434℃。最大吸收波长：756nm(三氯甲烷溶液)，770nm(薄膜)。
实施例12
在氮气保护下，将5,5’-双(三甲基锡基)-2,2’-二噻吩(24.7mg，0.05mmol)、4,9-二溴-2,7-二(2-辛基十二烷基)苯并[lmn][3,8]邻二氮杂菲-1,3,6,8(2H,7H)-四酮(49.1mg，0.05mmol)、P(t-Bu)3Pd G3(2.9mg，0.005mmol)和磷酸钾(10.6mg，0.05mmol)放入反应瓶中。加入1.0mL四氢呋喃后，在室温条件下搅拌72小时。加入20.0mL甲醇后，将生成的沉淀过滤。然后将沉淀出来的聚合物依次分别用丙酮、正己烷和三氯甲烷进行索氏提取。将三氯甲烷提取后所得溶液浓缩，然后用20.0mL甲醇沉淀出聚合物，过滤、烘干即可得到黑蓝色聚合物固体(43.3mg，87％)。1H NMR(500MHz,CDCl3):δ8.86-8.42(br,2H),7.74-7.27(br,4H),4.55-3.76(br,4H),2.17-1.83(br,2H),1.79-1.03(br,64H),1.02-0.70(br,12H)。GPC:Mn 29.1kDa,Mw 53.0kDa,
元素分析计算值{(C62H88N2O4S2)n}：C,75.26；H,8.96；N,2.83。实测值：C,75.12；H,8.81；N,2.82。该聚合物的热分解温度：486℃。最大吸收波长：651nm(三氯甲烷溶液)，709nm(薄膜)。
上述实施例仅为充分说明本发明而列举的具体实施例，本发明的保护范围以权利要求书的内容为准，而不限于上述具体实施方式。说明书中公开的所有内容，包括摘要，以及公开的所有方法和步骤，都可以任意组合，除非这些特征和/或步骤是相互排斥的组合。说明书中公开每一个技术特征，包括摘要，除非另有说明，都可以被实现相同、等同或类似目的的技术特征所替换。因此，除非另有说明，本发明公开的每个技术特征仅是通常系列中的等同或类似的技术特征的一个实例。本领域的技术人员在本发明基础上所作的不脱离本发明实质内容的等同替代或变换，亦均在本发明的保护范围之内。而这样的修改亦均在本发明的保护范围之内。本申请引用的每个参考文献在此均引用其全文。
Claims (5)
1.一种以芳基二卤代物为亲电试剂，芳基二锡烷为亲核试剂，在催化剂/碱/溶剂条件下制备二芳基偶联聚合物的方法，其中所述的催化剂为甲磺酸(三-叔丁基膦基)(2’-氨基-1,1’-联苯-2-基)钯(II)(即P(t-Bu)3Pd G3)，其特征在于，其结构通式如式I所示：
其中，Ar1和Ar2表示相同或不同的芳基体系；
其中，n表示聚合度；
其中，X表示卤素，优选为氯、溴、碘；
其中，Ra和Rb各自独立地表示氢或C1-C30烷基，优选为C1-C20烷基，更优选为C1-C10烷基；
其中，所述的碱性条件为Cs2CO3,K3PO3,Na2CO3,NaHCO3,NaOH的任意一种或其组合；
其中，所述的溶剂选自THF，DMSO,DMF,二氧六环，二氯化碳，氯仿，甲醇，乙醇，甲苯，丙酮，正己烷中的任意一种或其组合；
其中，P(t-Bu)3Pd G3的结构式为：
2.根据权利要求1所述的方法，其特征在于，所述的芳基二卤代物为下列任意一种化合物：
其中，X为氯原子、溴原子或碘原子；
其中，R,R1,R2,R3为独立的氢或C1-C30的烷基，其中包括碳原子总数为6-16的直链烷基包括：正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基；以及碳原子总数为8–30的支链烷基包括：2-乙基己基，2-乙基辛基，2-丁基己基、2-己基辛基、4-己基癸基、3-己基十一烷基、2-辛基癸基、2-辛基十二烷基、3-辛基十三烷基、2-癸基十二烷基、2-癸基十四烷基、3-癸基十五烷基、2-十二烷基十六烷基、4-辛基十四烷基、4-癸基十六烷基、4-己基癸基、4-辛基十二烷基、4-癸基十四烷基、4-十二烷基十六烷基。
3.根据权利要求1所述的方法，其特征在于，所述的芳基二锡烷为下列任意一种化合物：
其中，R,R1,R2为独立的氢或C1-C30的烷基，其中包括碳原子总数为6-16的直链烷基包括：正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基；以及碳原子总数为8–30的支链烷基包括：2-乙基己基，2-乙基辛基，2-丁基己基、2-己基辛基、4-己基癸基、3-己基十一烷基、2-辛基癸基、2-辛基十二烷基、3-辛基十三烷基、2-癸基十二烷基、2-癸基十四烷基、3-癸基十五烷基、2-十二烷基十六烷基、4-辛基十四烷基、4-癸基十六烷基、4-己基癸基、4-辛基十二烷基、4-癸基十四烷基、4-十二烷基十六烷基。
4.根据权利要求1-3任一项所述的方法，其特征在于，所述方法步骤包括：
(1)采用惰性气体保护，在P(t-Bu)3Pd G3的催化作用下，加入磷酸钾作为添加剂，将芳基二卤代物与芳基二锡烷置于四氢呋喃或甲苯中，进行反应得到混合物；
(2)将混合物滴入甲醇中沉淀过滤，并将沉淀物采用索氏提取器通过丙酮、正己烷及三氯甲烷分别进行提取，将三氯甲烷提取得到的聚合物溶液浓缩后滴入甲醇中，制得具有超过10个重复单元的高分子量D-A共轭聚合物。
5.根据权利要求1-4任一项所述的方法，其特征在于，所述的芳基二卤代物和芳基二锡烷，在室温条件下实现聚合反应。
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| CN115260457B (zh) * | 2022-07-27 | 2023-07-28 | 中国科学院大学 | 一种基于c-s键断裂的高效直接芳基化聚合反应获得共轭聚合物的方法和应用 |
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