CN117105990A - 一种催化制备聚噻吩用催化剂及p3ht材料 - Google Patents
一种催化制备聚噻吩用催化剂及p3ht材料 Download PDFInfo
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- 229920000123 polythiophene Polymers 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 28
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 title abstract description 18
- 239000000463 material Substances 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 26
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003446 ligand Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 229930192474 thiophene Natural products 0.000 claims description 10
- -1 cycloalkynyl Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 6
- 150000007529 inorganic bases Chemical class 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- XQJNXCHDODCAJF-UHFFFAOYSA-N 2-bromo-3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1Br XQJNXCHDODCAJF-UHFFFAOYSA-N 0.000 claims description 4
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 claims description 4
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 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
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229930006739 camphene Natural products 0.000 claims description 2
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000005023 xylyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 32
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- 238000005481 NMR spectroscopy Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
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- 101150003085 Pdcl gene Proteins 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
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- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 2
- MQZSYVVHQUCZHS-UHFFFAOYSA-N 2-benzhydryl-4-methylaniline Chemical compound C(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC(=CC=C1N)C MQZSYVVHQUCZHS-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- AFPRJLBZLPBTPZ-UHFFFAOYSA-N acenaphthoquinone Chemical compound C1=CC(C(C2=O)=O)=C3C2=CC=CC3=C1 AFPRJLBZLPBTPZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 2
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- WRDWWAVNELMWAM-UHFFFAOYSA-N 4-tert-butylaniline Chemical compound CC(C)(C)C1=CC=C(N)C=C1 WRDWWAVNELMWAM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 description 1
- BBWVVUBNXASLOP-UHFFFAOYSA-N S1C=CC=C1.[B] Chemical compound S1C=CC=C1.[B] BBWVVUBNXASLOP-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 235000019441 ethanol Nutrition 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- LZTRCELOJRDYMQ-UHFFFAOYSA-N triphenylmethanol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C1=CC=CC=C1 LZTRCELOJRDYMQ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
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- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/184—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine mixed aromatic/aliphatic ring systems, e.g. indoline
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Abstract
本发明公开了一种催化制备聚噻吩用催化剂及P3HT材料,所述催化制备聚噻吩用催化剂的结构式如式(I)或式(Ⅱ)所示:;本发明提供的催化制备聚噻吩用催化剂能够在高温下催化聚合制备得到高分子量、高产率和窄分子量分布的P3HT,在太阳能电池、有机晶体管、电致变色器件、化学传感器、电磁屏蔽材料等领域具有广泛应用前景。
Description
技术领域
本发明涉及催化剂技术领域,特别涉及一种催化制备聚噻吩用催化剂及P3HT材料。
背景技术
聚3-己基噻吩属于聚噻吩类聚合物,因其具备优良的电光性能、环境稳定性和可溶解性,在太阳能电池、有机晶体管、电致变色器件、化学传感器、电磁屏蔽材料等领域具有广泛应用前景。
聚3-己基噻吩(P3HT)作为一种低成本的商业化共轭高分子空穴传输材料(HTM),具有易于制备的优点,同时不需要任何掺杂剂。此外,它的聚合物属性为太阳能电池提供了更好的成膜性,很适合用于大面积制备方法。P3HT 已被广泛用作钙钛矿太阳能电池中的HTM,以及在钙钛矿层和HTM之间的聚合物中间层。至今,在其结构中使用 P3HT作为HTM或聚合物中间层的钙钛矿太阳能电池的效率高达23%。
而高分子量且结构规整的P3HT具有更加优良的电学和光学性质,无论在单纯的膜中或者与PCBM的共混膜中,都有比较高的载流子迁移率。Stille法和Suzuki法等方法均可以合成规整结构的P3HT,但Stille方法的单体锡试剂制备复杂,且有机锡试剂毒性高,其工艺效率低;Suzuki方法制备单体时,采用丁基锂制备有机硼试剂,需低温和无水条件,噻吩硼试剂不稳定,需要低温贮存;且用Suzuki反应难以制得高分子量的P3HT。
发明内容
本发明的目的在于克服现有技术的缺陷和不足,提供一种催化制备聚噻吩用催化剂,能够在高温下催化聚合制备得到高分子量、高产率和窄分子量分布的P3HT。
本发明的目的在于提供一种催化制备聚噻吩用催化剂,所述催化制备聚噻吩用催化剂的结构式如式(I)或式(Ⅱ)所示:
其中,R、R1独立选自烷基、烯基、炔基、芳基、环烷基、环烯基、环炔基、萘基、苊基、莰基、二苯甲基、三苯甲基。
更优选地,所述催化制备聚噻吩用催化剂的结构式如式(I)或式(Ⅱ)所示:
其中,R、R1独立选自甲基、叔丁基、二苯甲基或三苯甲基。
更优选地,所述催化制备聚噻吩用催化剂的结构式如式(I)或式(Ⅱ)所示:
其中,R选自甲基,R1选自三苯甲基。
更优选地,所述催化制备聚噻吩用催化剂的结构式如式(I)或式(Ⅱ)所示:
其中,R选自二甲苯基,R1选自甲基或叔丁基。
本发明的另一目的在于提供所述的催化制备聚噻吩用催化剂的制备方法,包括如下步骤:
配体或/>与氯化钯反应,得所述催化制备聚噻吩用催化剂。
优选地,所述配体与氯化钯的摩尔比为1.05~1.2:1。
更优选地,所述配体与氯化钯的摩尔比为1.1:1。
优选地,所述反应的温度为40~80℃,时间为12~18h。
更优选地,所述反应的温度为60℃,时间为16h。
优选地,所述配体的制备方法包括如下步骤:
S1.苯胺与醇/>反应或苯胺/>与醇反应,得取代的苯胺/>;
S2.所述取代的苯胺与二酮/>或/>反应,得所述配体。
优选地,S1中,所述苯胺与醇/>的摩尔比为1:1.1~1.3。
优选地,S1中,所述苯胺与醇/>的摩尔比为1:1.1~2.2。
优选地,S1中,所述反应的催化剂包括ZnCl2/HCl。
优选地,S2中,所述取代的苯胺与二酮/>的摩尔比为2.1~2.5:1。
优选地,S2中,所述取代的苯胺与二酮/>的摩尔比为2.1~2.5:1。
优选地,S2中,所述反应的温度为20~140℃,时间为5~24h。
本发明的另一目的在于提供一种聚噻吩,由所述的催化制备聚噻吩用催化剂催化噻吩类单体聚合制得。
优选地,所述催化制备聚噻吩用催化剂与噻吩类单体的摩尔比为0.0015~0.0035:1。
更优选地,所述催化制备聚噻吩用催化剂与噻吩类单体的摩尔比为0.0025:1。
优选地,所述噻吩类单体包括2-溴-3-己基噻吩。
优选地,在聚合过程中还加入有机酸和无机碱。
优选地,所述有机酸与噻吩类单体的摩尔比为2~4:1。
更优选地,所述有机酸与噻吩类单体的摩尔比为3:1。
优选地,所述无机碱与噻吩类单体的摩尔比为1~2:1。
优选地,所述无机碱与噻吩类单体的摩尔比为1.4:1。
更优选地,所述有机酸包括新戊酸。
更优选地,所述无机碱包括无水碳酸钾。
优选地,所述聚合的反应温度为80~120℃,所述聚合的反应时间为12~36h。
更优选地,所述聚合的反应温度为100℃,所述聚合的反应时间为24h。
优选地,所述聚合的反应溶剂包括N,N-二甲基乙酰胺。
相比于现有技术,本发明具有如下有益效果:
本发明提供的催化制备聚噻吩用催化剂能够在高温下制备P3HT,所制备得到的P3HT具有分子量高、产率高、分布窄的优点,具有明显的经济效益,在太阳能电池、有机晶体管、电致变色器件、化学传感器、电磁屏蔽材料等领域具有广泛应用前景。
附图说明
图1为实施例4提供的催化制备聚噻吩用催化剂C1的核磁氢谱图。
图2为实施例4提供的催化制备聚噻吩用催化剂C1的核磁碳谱图。
图3为实施例5提供的催化制备聚噻吩用催化剂C2的核磁氢谱图。
图4为实施例5提供的催化制备聚噻吩用催化剂C2的核磁碳谱图。
图5为实施例6提供的催化制备聚噻吩用催化剂C3的核磁氢谱图。
图6为实施例6提供的催化制备聚噻吩用催化剂C3的核磁碳谱图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述,以充分地理解本发明的目的、特征和效果。显然,所描述的实施例只是本发明的一部分实施例,而不是全部实施例,基于本发明的实施例,本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例,均属于本发明保护的范围。实施例中所使用的试验方法如无特殊说明,均为常规方法;所使用的材料、试剂等,如无特殊说明,均可从商业途径得到的试剂和材料。
催化制备聚噻吩用催化剂通过如下反应路线制备得到:
以下实施例中,制备得到的P3HT采用高温凝胶渗透色谱仪(HT-GPC)测定聚合物(以三氯苯为溶剂和流动相,浓度1.5 g/L,流速1mL/min)的分子量以及分子量分布。
实施例1
本实施例提供一种配体L1,其合成方法如下:
在氮气气氛下,将4-甲基苯胺(5mmol),二苯甲醇(5.5mmol)依次加入支口瓶中,80℃条件下搅拌反应,冷凝回流30min(熔融状态),然后用注射器加入现配的ZnCl2/浓HCl(其中,ZnCl2(0.75g)、浓HCl(1ml)),140℃下反应6h,反应结束后冷却至室温,加入适量的二氯甲烷溶解后转移至烧杯中,加入饱和碳酸氢钠溶液,将溶液的PH调节至7,搅拌30min后,抽滤除去锌盐,将滤液分液后收集有机层,加入无水硫酸钠除水,过滤,旋干后,过硅胶色谱柱后,旋干,重结晶(无水乙醇),抽滤烘干,得白色化合物2,6-二苯甲基-4-甲基苯胺,产率85%。
将2,6-二苯甲基-4-甲基苯胺(2.2mmol)、乙二醛(1mmol)、乙醇(4ml)依次加入支口瓶中,加入0.1mL冰乙酸作为催化剂,常温搅拌24h,反应结束后,抽滤,烘干,得到黄色固体配体L1,产率87%。
实施例2
本实施例提供一种配体L2,其合成方法如下:
在氮气气氛下,将2,6-二甲基苯胺(5mmol),三苯甲醇(5.5mmol)依次加入支口瓶中,80℃条件下搅拌反应,冷凝回流30min(熔融状态),然后用注射器加入现配的ZnCl2/浓HCl(其中,ZnCl2(0.75g)、浓HCl(1ml)),140℃下反应6h,反应结束后冷却至室温,加入适量的二氯甲烷溶解后转移至烧杯中,加入饱和碳酸氢钠溶液,将溶液的PH调节至7,搅拌30min后,抽滤除去锌盐,将滤液分液后收集有机层,加入无水硫酸钠除水,过滤,旋干后,过硅胶色谱柱后,旋干,重结晶(无水乙醇),抽滤烘干,得白色化合物2,6-二甲基-4-三苯甲基苯胺,产率77%。
在氮气气氛下,将2,6-二甲基-4-三苯甲基苯胺(2.2mmol)、苊醌(1mmol)、无水ZnCl2(0.3g)依次加入支口瓶中,加入5mL冰乙酸作为溶剂,缓慢升温至140℃,冷凝回流5h,反应冷却至室温,抽滤(用正己烷冲洗固体),烘干后用二氯甲烷将所得锌配合物溶解至烧杯,将草酸钾水溶液加入烧杯中搅拌12h使其脱锌,静置分液取有机层,加入无水硫酸钠除水,过滤,旋干,用无水乙醇重结晶,得到黄色固体L2,产率73%。
实施例3
本实施例提供一种配体L3,其合成方法如下:
在氮气气氛下,将4-叔丁基苯胺(5mmol),二苯甲醇(11mmol)依次加入支口瓶中,80℃条件下搅拌反应,冷凝回流30min(熔融状态),然后用注射器加入现配的ZnCl2/浓HCl(其中,ZnCl2(0.75g)、浓HCl(1ml)),140℃下反应6h,反应结束后冷却至室温,加入适量的二氯甲烷溶解后转移至烧杯中,加入饱和碳酸氢钠溶液,将溶液的PH调节至7,搅拌30min后,抽滤除去锌盐,将滤液分液后收集有机层,加入无水硫酸钠除水,过滤,旋干后,过硅胶色谱柱后,旋干,重结晶(无水乙醇),抽滤烘干,得白色化合物2,6-二苯甲基-4-叔丁基苯胺,产率82%。
在氮气气氛下,将2,6-二苯甲基-4-叔丁基苯胺(2.2mmol)、苊醌(1mmol),无水ZnCl2(0.3g)依次加入支口瓶中,加入5mL冰乙酸作为溶剂,缓慢升温至140℃,冷凝回流5h,反应冷却至室温,抽滤(用正己烷冲洗固体),烘干后用二氯甲烷将所得锌配合物溶解至烧杯,将草酸钾水溶液加入烧杯中搅拌12h使其脱锌,静置分液取有机层,加入无水硫酸钠除水,过滤,旋干,用无水乙醇重结晶。得到黄色固体配体L3,产率57%。
实施例4
本实施例提供一种催化制备聚噻吩用催化剂C1,其合成方法如下:
在氮气气氛下,将配体L1(0.5mmol)、(COD)PdCl2(0.55mmol)、甲醇(8ml)加入支口瓶中,60℃条件下冷凝回流16h,待反应结束后冷却至室温,以二氯甲烷为洗脱剂干法过柱,收集滤液旋干,加少量二氯甲烷溶解,缓慢滴加至搅拌状态的无水乙醇溶液中,析出固体,洗涤多次,抽滤烘干,得固体化合物C1,产率87%。
1H NMR (400 MHz, CDCl3) δ 7.30-7.15 (m, 30H), 7.14-7.07 (m, 3H), 7.04-6.95 (m, 8H), 6.78-6.73 (m, 1H), 6.65 (d,J= 4.6 Hz, 2H), 6.46-6.37 (m, 3H),5.22 (s, 1H), 4.10 (s, 1H), 2.11 (s, 3H), 2.02 (s, 3H).
13C NMR (101 MHz, CDCl3) δ 163.85, 146.70, 143.75, 142.64, 136.10,134.86, 133.60, 133.55, 129.73, 129.63, 129.51, 129.48, 129.45, 129.07,128.61, 128.46, 128.37, 128.22, 127.09, 126.28, 52.29, 51.67, 51.63, 50.94,21.55, 21.31, 21.00.
实施例5
本实施例提供一种催化制备聚噻吩用催化剂C2,其合成方法如下:
在氮气气氛下,将配体L2(0.5mmol)、(COD)PdCl2(0.55mmol),甲醇(8ml)加入支口瓶中,60℃条件下冷凝回流16h,待反应结束后冷却至室温,以二氯甲烷为洗脱剂干法过柱,收集滤液旋干,加少量二氯甲烷溶解,缓慢滴加至搅拌状态的无水乙醇溶液中,析出固体,洗涤多次,抽滤烘干,得固体化合物C2,产率74%。
1H NMR (400 MHz, CDCl3) δ 8.06 (d,J= 8.3 Hz, 2H), 7.36-7.25 (m, 26H),7.23 (s, 2H), 7.22-7.16 (m, 6H), 7.11 (s, 4H), 6.24 (d,J= 7.2 Hz, 2H), 2.26(s, 12H).
13C NMR (101 MHz, CDCl3) δ 175.29, 147.52, 146.87, 146.47, 141.33,132.38, 131.46, 131.07, 129.27, 128.57, 127.68, 126.02, 125.03, 124.46,65.06, 18.66.
实施例6
本实施例提供一种催化制备聚噻吩用催化剂C3,其合成方法如下:
在氮气气氛下,将配体L3(0.5mmol)、(COD)PdCl2(0.55mmol),甲醇(8ml)加入支口瓶中,60℃条件下冷凝回流16h,待反应结束后冷却至室温,以二氯甲烷为洗脱剂干法过柱,收集滤液旋干,加少量二氯甲烷溶解,缓慢滴加至搅拌状态的无水乙醇溶液中,析出固体,洗涤多次,抽滤烘干,得黄色固体化合物C3,产率83%。
1H NMR (400 MHz, CDCl3) δ 7.60 (d,J= 8.3 Hz, 2H), 7.39-7.31 (m, 8H),7.20-7.12 (m, 16H), 6.89-6.80 (m, 10H), 6.58 (qd,J= 8.6, 7.8, 3.6 Hz, 12H),6.23 (s, 4H), 5.86 (d,J= 7.2 Hz, 2H), 1.18 (s, 18H).
13C NMR (101 MHz, CDCl3) δ 177.30, 150.63, 142.81, 141.74, 140.12,136.23, 129.94, 129.68, 128.07, 128.06, 126.63, 126.45, 126.13, 123.64,52.22, 34.80, 31.11.
对比例1
本对比例提供一种催化制备聚噻吩用催化剂C4,其合成方法如下。
取乙酰丙酮( 10 mmol)、2,6-二异丙基苯胺A4(22 mmol)放入圆底烧瓶中,加入40mL无水乙醇,在剧烈搅拌下缓慢滴加1.5mL浓盐酸,将混合物加热回流3天,经抽滤得到白色固体,重新溶解在二氯甲烷中,用饱和NaHCO3调节溶液呈中性,经萃取分液,减压蒸馏除去溶剂,得淡黄色固体β--二亚胺L4,产率61%。
称取β-二亚胺L4( 1mmol)、(COD)PdCl2( 1mmol)于支口瓶中,加入甲醇18mL,在N2保护下,使反应回流16h。反应结束后抽滤出黄色固体,经硅胶短柱快速洗脱后,用二氯甲烷/正己烷重结晶,得黄色固体C4,产率47%。
分别将实施例4~6的催化制备聚噻吩用催化剂C1~C3和对比例1制得的催化制备聚噻吩用催化剂C4催化2-溴-3-己基噻吩聚合得到P3HT,具体步骤如下:
取干净的无水无氧平行反应仪的反应瓶,分别放入磁力搅拌子,在六个反应瓶中都加入2-溴-3-己基噻吩(0.5mmol),无水碳酸钾(0.7mmol),新戊酸(0.15mmol)和4ml的N,N-二甲基乙酰胺作为溶剂,再分别加入0.25%的催化制备聚噻吩用催化剂C1~C4,在自然条件下升温至100oC,控温搅拌反应24个小时,停止加热,再加入20ml甲醇沉淀,析出红棕色固体产物,抽滤,烘干,然后将产物用滤纸包裹好,放进索氏提取器中,加入正己烷为溶剂进行提取,直至虹吸的溶剂没有颜色,将产物烘干,称重,对聚合物进行GPC表征。催化聚合结果如表1所示。
表1.不同催化制备聚噻吩用催化剂催化2-溴-3-己基噻吩聚合的结果。
由表1可知,本发明实施例4~6制备得到的P3HT具有较高的分子量和规整度,分子量分布窄。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种催化制备聚噻吩用催化剂,其特征在于,所述催化制备聚噻吩用催化剂的结构式如式(I)或式(Ⅱ)所示:
其中,R、R1独立选自烷基、烯基、炔基、芳基、环烷基、环烯基、环炔基、萘基、苊基、莰基、二苯甲基、三苯甲基。
2.权利要求1所述的催化制备聚噻吩用催化剂,其特征在于,所述催化制备聚噻吩用催化剂的结构式如式(I)或式(Ⅱ)所示:
其中,R、R1独立选自甲基、叔丁基、二苯甲基或三苯甲基。
3.权利要求2所述的催化制备聚噻吩用催化剂,其特征在于,所述催化制备聚噻吩用催化剂的结构式如式(I)或式(Ⅱ)所示:
其中,R选自甲基,R1选自三苯甲基。
4.权利要求2所述的催化制备聚噻吩用催化剂,其特征在于,所述催化制备聚噻吩用催化剂的结构式如式(I)或式(Ⅱ)所示:
其中,R选自二甲苯基,R1选自甲基或叔丁基。
5.权利要求1~4任一项所述的催化制备聚噻吩用催化剂的制备方法,其特征在于,包括如下步骤:
配体或/>与氯化钯反应,得所述催化制备聚噻吩用催化剂。
6.根据权利要求5所述的催化制备聚噻吩用催化剂的制备方法,其特征在于,所述配体的制备方法包括如下步骤:
S1.苯胺与醇/>反应或苯胺/>与醇/>反应,得取代的苯胺/>;
S2.所述取代的苯胺与二酮/>或/>反应,得所述配体。
7.一种聚噻吩,其特征在于,由权利要求1~4任一项所述的催化制备聚噻吩用催化剂催化噻吩类单体聚合制得。
8.根据权利要求7所述的聚噻吩,其特征在于,所述噻吩类单体包括2-溴-3-己基噻吩。
9.根据权利要求7所述的聚噻吩,其特征在于,在聚合过程中还加入有机酸和无机碱。
10.根据权利要求7所述的聚噻吩,其特征在于,所述聚合的反应温度为80~120℃,所述聚合的反应时间为12~36h。
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