CN117343105A - 一种钯催化剂及其在制备p3ht中的应用 - Google Patents
一种钯催化剂及其在制备p3ht中的应用 Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 38
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 title abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 20
- 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 11
- 239000000178 monomer Substances 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 10
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- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical group C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 claims description 8
- 101150003085 Pdcl gene Proteins 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
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- XQJNXCHDODCAJF-UHFFFAOYSA-N 2-bromo-3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1Br XQJNXCHDODCAJF-UHFFFAOYSA-N 0.000 claims description 5
- 150000007529 inorganic bases Chemical class 0.000 claims description 5
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- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 claims description 4
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- 125000003118 aryl group Chemical group 0.000 claims description 4
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- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Chemical group C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 claims description 4
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- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- 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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- 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
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Abstract
本发明公开了一种钯催化剂及其在制备P3HT中的应用,所述钯催化剂的结构式如式(I)所示:;本发明提供的钯催化剂能够在高温下催化聚合制备得到高分子量和高规整度的P3HT,提高催化聚合的产率,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,特别涉及一种钯催化剂及其在制备P3HT中的应用。
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方法可以合成具有较高规整结构的P3HT,但Stille方法的单体制备需要使用有机锡试剂,有机锡试剂毒性大,价格高,且制备的聚合物分子量不高,导致整个工艺效率低。
发明内容
本发明的目的在于克服现有技术的缺陷和不足,提供一种钯催化剂,催化C-H活化直接芳基化聚合制备聚合物,原料来源方便,稳定性好,且能同时提高聚合物分子量和产率,进而提高生产效率,降低生产成本,具有实际的生产意义。同时,能够催化聚合制备得到高分子量和高规整度的P3HT,提高催化聚合的产率。
本发明的目的在于提供一种钯催化剂,所述钯催化剂的结构式如式(I)所示:
其中,R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。
优选地,所述钯催化剂的结构式如式(I)所示:
其中,R选自芳基、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,所述钯催化剂的结构式如式(I)所示:
其中,R选自二苯甲基、三苯甲基、
更优选地,所述钯催化剂的结构式如式(I)所示:
其中,R选自二甲苯基。
本发明的另一目的在于提供所述的钯催化剂的制备方法,包括如下步骤:
配体与(COD)PdCl2反应,得所述钯催化剂。
优选地,所述配体与(COD)PdCl2的摩尔比为1.5~2.5:1。
更优选地,所述配体与(COD)PdCl2的摩尔比为2:1。
优选地,所述反应的温度为60~100℃,时间为0.3~0.8h。
更优选地,所述反应的温度为80℃,时间为0.5h。
优选地,所述配体的制备方法包括如下步骤:
取代的苯胺与醇R-OH反应,得所述配体。
优选地,所述取代的苯胺与醇R-OH的摩尔比为0.45~3.3:1。
优选地,所述反应的催化剂包括ZnCl2/HCl。
本发明的另一目的在于提供一种聚噻吩,所述聚噻吩由所述钯催化剂催化噻吩类单体聚合制得。
优选地,所述钯催化剂与噻吩类单体的摩尔比为0.0015~0.0035:1。
更优选地,所述钯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:
本发明提供的钯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、规整度高、产率高的优点,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2提供的钯催化剂C的核磁氢谱图。
图2为实施例2提供的钯催化剂C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。
本发明的描述中,参考术语“一个实施例”、“一些实施例”、“示意性实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不一定指的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
(COD)PdCl2:(1,5-环辛二烯)二氯化钯。
钯催化剂通过如下反应路线制备得到:
其中,R为二苯甲基。
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1.5g/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L,其合成方法如下:
在氮气气氛下,将化合物A(5mmol),二苯甲醇(10mmol)依次加入支口瓶中,80℃条件下搅拌反应,冷凝回流60min(熔融状态),然后用注射器加入ZnCl2/浓HCl溶液(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L,产率57%。
实施例2
本实施例提供一种催化剂C,其合成方法如下:
将实施例制得的配体L(1mmol)、(COD)PdCl2(0.5mmol)溶解在DMAC(1.5ml)中,80℃条件下搅拌反应0.5h,待反应冷却至后加入甲醇沉降,过滤、溶解固体、过硅胶色谱柱后,旋干、重结晶(无水乙醇),抽滤烘干,得黄色化合物C,产率79%。
1H NMR(400MHz,CDCl3)δ8.54(s,2H),7.91(d,J=8.9Hz,2H),7.12(td,J=7.7,2.1Hz,46H),7.00-6.94(m,8H),6.89(dd,J=7.3,2.3Hz,8H),6.35(d,J=9.7Hz,4H),6.02(s,2H),5.70(s,2H),4.66(s,4H).
13C NMR(101MHz,CDCl3)δ147.70,141.63,135.58,133.50,129.75,129.51,128.54,127.00,126.02,51.80,34.44,30.91.
对比例1
本对比例提供一种钯催化剂C1,其合成方法如下。
取乙酰丙酮(10mmol)、2,6-二异丙基苯胺A1(22mmol)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L1,产率61%。
称取β-二亚胺L1(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C1,产率47%。
分别将实施例2的钯催化剂C和对比例1制得的钯催化剂C1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%的钯催化剂C~C2,在自然条件下升温至100℃,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.不同钯催化剂催化2-溴-3-己基噻吩聚合的结果。
实施例 | 钯催化剂 | 产率(%) | Mn(g/mol) | PDI | HT(%) |
实施例2 | C | 75 | 26273 | 2.10 | 93 |
对比例1 | C1 | 57 | 7423 | 1.45 | 80 |
由表1可知,本发明实施例2制备得到的P3HT具有较高的分子量和规整度,产率高。
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)
1.一种钯催化剂,其特征在于,所述钯催化剂的结构式如式(I)所示:
其中,R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所述的钯催化剂,其特征在于,所述钯催化剂的结构式如式(I)所示:
其中,R选自芳基、环烷基、环烯基、环炔基、萘基、苊基、莰基、二苯甲基、三苯甲基、
3.权利要求2所述的钯催化剂,其特征在于,所述钯催化剂的结构式如式(I)所示:
其中,R选自二苯甲基、三苯甲基、
4.权利要求3所述的钯催化剂,其特征在于,所述钯催化剂的结构式如式(I)所示:
其中,R选自二甲苯基。
5.权利要求1~4任一项所述的钯催化剂的制备方法,其特征在于,包括如下步骤:
配体与(COD)PdCl2反应,得所述钯催化剂。
6.根据权利要求5所述的钯催化剂的制备方法,其特征在于,所述配体的制备方法包括如下步骤:
取代的苯胺与醇R-OH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任一项所述的钯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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