CN114644611B - 一种基于萘稠环的缺电子单体及其聚合物和应用 - Google Patents
一种基于萘稠环的缺电子单体及其聚合物和应用 Download PDFInfo
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- CN114644611B CN114644611B CN202210213691.8A CN202210213691A CN114644611B CN 114644611 B CN114644611 B CN 114644611B CN 202210213691 A CN202210213691 A CN 202210213691A CN 114644611 B CN114644611 B CN 114644611B
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
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Abstract
本发明属于光伏材料技术领域,提供了一种基于萘稠环的缺电子单体及其聚合物和应用,本发明提供的基于萘稠环的缺电子单体,具有刚性、平面的骨架结构,共轭增强,可以作为聚合单体,进一步用于制备给体聚合物;本发明所提供的聚合物,具有共轭五元环结构,能够作为给体材料,应用于制备有机光伏器件中;本发明利用基于萘稠环的聚合物制备的太阳能电池,稳定性好,光电转换效率高,可达17.14%。
Description
技术领域
本发明涉及光伏材料技术领域,更具体地,涉及一种基于萘稠环的缺电子单体及其聚合物和应用。
背景技术
通过给电子单体(D)和吸电子单体(A)交叉偶联反应合成的D-A共聚物作为给体材料在有机光伏器件中广泛应用,相较于非富勒烯受体材料,给体聚合物的发展相对滞后,大部分给体材料最初是为了与富勒烯受体材料相匹配而设计,目前高性能给体聚合物种类较少,而且所制得的有机光伏器件还存在稳定性差、光电转换效率低等突出问题。因此设计合成一种聚合物给体材料以制得稳定性好、光电转换效率高的有机光伏器件,对有机太阳能电池的发展非常重要。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此,本发明提出一种基于萘稠环的缺电子单体及其聚合物和应用,利用基于萘稠环的缺电子单体制得聚合物,所制得的聚合物能够作为给体材料应用于制备稳定性好、光电转换效率高的有机光伏器件,光电转换效率可达17.14%。
本发明的第一方面提供一种基于萘稠环的缺电子单体。
具体地,一种缺电子单体,其特征在于,具有如下式(Ⅰ)所示的分子结构:
其中,X1、X2分别独立表示H、F、Cl或Br中的一种;L1为
中的一种;L2为
中的一种;R4为C1-C24的任意烷基链;R5、R6分别独立表示C1-C24的任意烷基链、烷氧链、烷硫链或烷硅链中的一种;X3为S、N、Se中的一种;X4为F、Cl、Br中的一种;X5、Z分别独立表示F、Cl、Br中的一种;*表示化学键连接的位点。
本发明提供的缺电子单体由于其具有刚性、平面的骨架结构,能够避免相邻芳基之间的键旋转,从而增强共轭,促进电子离域,并通过降低重组能增强电荷输运,可以进一步用于制备聚合物,所制得的聚合物可以作为给体材料,应用于制备稳定性好、光电转换效率高的有机光伏器件。
优选地,所述L1为
中的一种;所述L2为/>中的一种。
优选地,具有如下分子结构中的一种:
本发明的第二方面提供一种基于萘稠环的缺电子单体的制备方法。
本发明保护上述基于萘稠环的缺电子单体的制备方法,包括如下步骤:
利用含萘稠环的化合物和噻吩或噻吩衍生物,通过偶联反应制得所述缺电子单体。
优选地,所述偶联反应为铃木反应(Suzuki反应)或有机锡反应(Stille反应)。
优选地,所述偶联反应后,还包括进行取代反应、缩合反应、希夫碱形成反应(Schiff反应)、克脑文格尔反应(Knoevenagel反应)中的一种或几种。通过以上反应进一步接枝其他基团,以制得种类更加丰富的缺电子单体。
优选地,所述铃木反应或有机锡反应的催化剂为Pd配合物。
优选地,所述Pd配合物为Pd(dba)3。
本发明的第三方面提供一种基于萘稠环的聚合物。
本发明保护一种基于萘稠环的聚合物,制备所述聚合物的原料组分包括上述的缺电子单体。
优选地,具有如下式(Ⅱ)所示的分子结构:
其中,X1、X2分别独立表示H、F、Cl或Br中的一种;n为正整数;L1为
中的一种;L2为
中的一种;A1、M1分别独立选自无、
中的一种;A1和M1不同时为无;R4为C1-C24的任意烷基链;R5、R6、R7、R8、R9分别独立表示C1-C24的任意烷基链、烷氧链、烷硫链或烷硅链中的一种;X3为S、N、Se中的一种;X4为F、Cl、Br中的一种;X5、Z分别独立表示F、Cl、Br中的一种;X为S、Se、O、N中的一种;*表示化学键连接的位点。
优选地,具有如下分子结构中的一种:
本发明的第四方面提供一种基于萘稠环的聚合物的制备方法。
本发明保护上述基于萘稠环的聚合物的制备方法,包括如下步骤:
在惰性氛围中,将所述缺电子单体通过有机锡反应(Stille反应)制得所述聚合物。
优选地,所述有机锡反应的温度为110-130℃,反应时间为1-3h。
本发明的第五方面提供一种基于萘稠环的缺电子聚合物的应用。
本发明保护上述基于萘稠环的聚合物在光伏领域中的应用。
本发明的第六方面提供一种太阳能电池。
本发明保护一种太阳能电池,制备所述太阳能电池的原料组分包括上述的聚合物。
相对于现有技术,本发明的有益效果如下:
(1)本发明提供的基于萘稠环的缺电子单体,具有刚性、平面的骨架结构,共轭增强,可以作为聚合单体,进一步用于制备给体聚合物;(2)本发明基于萘稠环的缺电子单体的制备方法,步骤少,利用含有萘稠环的化合物和噻吩或其衍生物通过偶联反应即可一步合成具有共轭五元环的稠环化合物,然后可以再通过取代反应、缩合反应、希夫碱形成反应、克脑文格尔反应等接枝不同的取代基团,以获得种类更加丰富的缺电子单体;(3)本发明提供的基于萘稠环的聚合物,具有共轭五元环结构,能够作为给体材料,应用于制备有机光伏器件中,所制得的太阳能电池具有稳定性好和光电转换效率高的优点,光电转换效率可达17.14%。
附图说明
图1为化合物2的CDCl3溶液1H NMR图;
图2为化合物3的CDCl3溶液的1H NMR图;
图3为化合物5的CDCl3溶液的1H NMR图;
图4为化合物6的CDCl3溶液的1H NMR图;
图5为化合物8b的CDCl3溶液的1H NMR图;
图6为化合物8c的CDCl3溶液的1H NMR图;
图7为化合物10的CDCl3溶液的1H NMR图;
图8为化合物14的CDCl3溶液的1H NMR图;
图9为化合物15的CDCl3溶液的1H NMR图;
图10为化合物17的CDCl3溶液的1H NMR图;
图11为化合物18的CDCl3溶液的1H NMR图;
图12为化合物20的CDCl3溶液的1H NMR图;
图13为化合物21的CDCl3溶液的1H NMR图;
图14为基于PATP1:BO-4F和PATP2:BO-4F的太阳能电池伏安特性曲线(J-V曲线);
图15为基于PTAC1:N3-4F的太阳能电池J-V曲线;
图16为基于PTAC2:Y6太阳能电池J-V曲线;
图17为基于PTAT:Y6的太阳能电池J-V曲线。
具体实施方式
为了让本领域技术人员更加清楚明白本发明所述技术方案,现列举以下实施例进行说明。需要指出的是,以下实施例对本发明要求的保护范围不构成限制作用。
以下实施例中所用的原料、试剂或装置如无特殊说明,均可从常规商业途径得到,或者可以通过现有已知方法得到。
实施例1
一种基于萘稠环的缺电子单体,为化合物4,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
在氮气氛围下,把Pd2(dba)3(0.535g)和P(MeOPh)3(1.65g)加入到具有化合物1(5g),化合物3,4-二(4,4,5,5-四甲基-1,3,2-二氧化硼-2-基)噻吩(4.1g),干THF(40mL)和2M K2CO3水溶液(10mL)的反应体系中,回流后6小时;混合物用CH2Cl2萃取;结合有机层用Na2SO4干燥;粗产物除去溶剂后,以正己烷:CH2Cl2(1:1)为洗脱剂,柱层析纯化,得到白色固体化合物2(3.15g,77%)。化合物2(Compound 2)的核磁结果如图1所示,核磁数据为:1HNMR(400MHz,CDCl3)(ppm):7.77(d,J=6.8Hz,2H),7.60(d,J=7.2Hz,2H),7.46(s,2H),4.22(br,4H),3.78(br,4H).
室温下,将NBS(3.2g)加入到化合物2(3.15g)的CHCl3(30mL)溶液中,将混合物搅拌2小时,除去溶剂后,以正己烷:CH2Cl2(1:1)为洗脱剂,固体经柱层析纯化,得到黄色固体化合物3(4.02g,88%)。化合物3(Compound 3)的核磁结果核磁结果如图2所示,核磁数据为::1H NMR(400MHz,CDCl3)(ppm):7.98(d,J=7.2Hz,2H),7.66(d,J=7.2Hz,2H),4.23(br,4H),3.76(br,4H).
将化合物3(4.02g)加入CH2Cl2(125mL)、CH3CN(62.5mL)和水(20mL)的溶液中,加入TsOH·H2O(15g),加热回流,搅拌过夜,固体用CH2Cl2过滤和洗涤,得到2.4g化合物4,收率为92%。由于化合物4在普通溶剂中不溶解,故只进行质谱测定。化合物4的质谱结果为:MS(MALDI-TOF)C16H4Br2O2S m/z:419.83;Found:420.79(M+H+).
上述化合物1、化合物2和化合物3的分子结构、以及上述反应方程式如下:
实施例2
一种基于萘稠环的缺电子单体,为化合物5,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
在氮气氛围下,把Pd2(dba)3(0.262g)加入到化合物4(2.4g),2-(三丁基锡基)-4-乙基己基噻吩(7g)和P(o-tol)3(0.696g)的甲苯(30mL)溶液中。将混合物加热回流并搅拌过夜,除去溶剂后,粗产物以正己烷:CH2Cl2(1:3)为洗脱剂进行柱层析纯化,得到红色固体化合物5(2.6g,,70%)。
化合物5(Compound 5)的核磁结果如图3所示,核磁数据为:1H NMR(400MHz,CDCl3)(ppm):8.14(d,J=7.2Hz,2H),7.88(d,J=7.2Hz,2H),7.19(s,2H),7.05(s,2H),2.63(d,J=6.8Hz,4H),1.64(br,2H),1.35(br,16H),0.96(br,12H).
反应方程式如下:
实施例3
一种基于萘稠环的缺电子单体,为化合物6,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
室温下,在化合物5(2.6g)的CHCl3(30mL)溶液中加入NBS(1.42g),将混合物搅拌反应2h,除去溶剂后,粗产物用正己烷:CH2Cl2(1:3)作为洗脱液进行柱层析纯化,得到红色固体化合物6(2.9g,90%)。
化合物6(Compound 6)的核磁结果如图4所示,核磁数据为:1H NMR(400MHz,CDCl3)(ppm):8.04(d,J=7.2Hz,2H),7.86(d,J=7.2Hz,2H),6.99(s,2H),2.56(d,J=7.2Hz,4H),1.71(br,2H),1.36(br,16H),0.97(br,12H).
反应方程式如下:
实施例4
一种基于萘稠环的缺电子单体,为化合物7a,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
在化合物4(200mg)的CHCl3(7mL),CH3COOH(7mL)溶液中,加入4,5-二己基苯-1,2-二胺(158mg)。反应混合物在72℃加热3小时。除去溶剂后,用CH2Cl2过滤和洗涤,得到黄色固体粗产物7a(220mg,71%).
化合物7a的质谱结果为:MS(MALDI-TOF)C34H32Br2N2S m/z:660.06;Found:660.82(M+H+).
反应方程式如下:
实施例5
一种基于萘稠环的缺电子单体,为化合物7b,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法同化合物7a,区别在于,将4,5-二己基苯-1,2-二胺替换为3,5,6-三氟-4-己基苯-1,2-二胺,化合物7a的收率72%。
化合物7b的质谱结果为:MS(MALDI-TOF)C28H17Br2F3N2S m/z:629.94;Found:630.85(M+H+).
反应方程式如下:
实施例6
一种基于萘稠环的缺电子单体,为化合物7c,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法同化合物7a,区别在于,将4,5-二己基苯-1,2-二胺替换为4,7-二己基苯并[1,2,5]噻二唑-5,6-二胺,收率77%。
化合物7c的质谱结果为:MS(MALDI-TOF)C34H30Br2N4S2 m/z:718.03;Found:719.02(M+H+).
反应方程式如下:
实施例7
一种基于萘稠环的缺电子单体,为化合物8a,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
在化合物6(200mg,1mmol)的CHCl3(7mL),CH3COOH(7mL)溶液中,加入4,5-二己基苯-1,2-二胺(82mg)。反应混合物在72℃下加热3小时,除去溶剂后,以正己烷:CH2Cl2(1:2)为洗脱剂,采用柱层析法对溶剂进行去除和纯化,产物用甲醇进一步重结晶得到红色固体化合物8a(176g,68%)。
化合物8a的核磁结果为:1H NMR(400MHz,CDCl3)(ppm):7.33(br,4H),7.08(S,2H),6.39(S,2H),2.05(t,J=7.6Hz,4H),1.88(d,J=6.8Hz,4H),0.68(br,34H),0.26(br,18H).
反应方程式如下:
实施例8
一种基于萘稠环的缺电子单体,为化合物8b,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
化合物8b与8a的合成过程相同,区别在于,将4,5-二己基苯-1,2-二胺替换为3,5,6-三氟-4-己基苯-1,2-二胺,收率为75%。
化合物8b(Compound 8b)的核磁结果如图5所示,核磁数据为:1H NMR(400MHz,CDCl3)(ppm):7.79(dd,J=7.2Hz,2H),7.70(dd,J=7.2Hz,2H),6.91(S,2H),2.84(t,J=7.6Hz,2H),2.51(d,J=6.4Hz,4H),1.67(br,4H),1.36(br,22H),0.95(br,15H).
反应方程式如下:
实施例9
一种基于萘稠环的缺电子单体,为化合物8c,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
化合物8c与8a的合成过程相同,区别在于,将4,5-二己基苯-1,2-二胺替换为4,7-二己基苯并[1,2,5]噻二唑-5,6-二胺,收率为73%。
化合物8c(Compound 8c)的核磁结果如图6所示,核磁数据为:1H NMR(400MHz,CDCl3)(ppm):δ7.71(d,J=7.2Hz,2H),7.64(d,J=7.2Hz,2H),6.82(s,2H),3.40(t,4H),2.45(d,J=6.8Hz,4H),1.74(br,6H),1.36(br,28H),0.97(br,18H).
反应方程式如下:
实施例10
一种基于萘稠环的缺电子单体,为化合物10,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
将三乙胺(0.037g),氰乙酸丁酯(0.046g)加入到化合物6(0.23g)的氯仿(60mL)溶液中,80℃回流搅拌过夜,除去溶剂后,粗产物用正己烷:CH2Cl2(3:1)作为洗脱液进行柱层析纯化,得到深红色固体化合物10或其异构体(0.144g,54.3%)。
化合物10(Compound 10)的核磁结果如图7所示,核磁数据为:1H NMR(400MHz,CDCl3)(ppm):8.79(d,J=7.6Hz,2H),8.20(d,J=7.2Hz,2H),8.15(d,J=7.6Hz,2H),8.03(d,J=7.2Hz,2H),7.11(s,1H),7.11(s,1H),4.44(t,J=6.6Hz,4H),2.58(d,J=7.2Hz,8H),1.83(br,4H),1.70(br,4H),1.53(br,4H),1.35(br,32H),0.97(br,30H).
反应方程式如下:
实施例11
一种基于萘稠环的缺电子单体,为化合物15,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
在氮气氛围下,把磺酰胺(14.12g)加入到化合物12(5g)的无水乙醇(50mL)和氯仿(50mL)溶液中,往溶液中通入盐酸气体鼓泡1小时,反应2小时,混合物用乙醇过滤洗涤,得到淡黄色固体化合物13粗产物(3.544g,60.26%),因难以提纯,直接进行下一步反应;将化合物13(5.85g)加入到二乙二醇二乙醚(100mL)溶液中,加热回流搅拌2小时,混合物加水过滤,固体用甲醇洗涤,干燥,得到淡红色固体化合物14(4.536g,92.46%)。化合物14的核磁结果如图8所示,核磁数据为:1H NMR(400MHz,CDCl3)(ppm):8.17(d,J=8.0Hz,2H),7.90(d,J=8.0Hz,2H).
在氮气氛围下,把Pd2(dba)3(0.149g)和P(MeOPh)3(0.461g)加入到化合物14(1.1g)、化合物3,4-二(4,4,5,5-四甲基-1,3,2-二氧化硼-2-基)噻吩(1.1g),干THF(12mL)和2mol/L K2CO3水溶液(3mL)的反应体系中,加热回流搅拌2小时,混合物用CH2Cl2萃取,有机层用Na2SO4干燥,除去溶剂后,粗产物以正己烷:CH2Cl2(1:2)为洗脱剂,柱层析纯化,得到白色固体化合物4(0.65g,76.9%)。
化合物15(Compound 15)的核磁结果如图9所示,核磁数据为:1H NMR(400MHz,CDCl3)(ppm):8.09(d,J=7.2Hz,2H),7.77(d,J=7.2Hz,2H),7.61(s,2H).
化合物12、化合物13、化合物14的分子结构、以及反应方程式如下:
实施例12
一种基于萘稠环的缺电子单体,为化合物16,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
室温下,将NBS(0.606g)加入到化合物15(0.4g),CHCl3(16mL),CF3COOH(8mL)的反应体系中,搅拌2小时后滴加入甲醇中,过滤沉淀,得到产品0.548g(85.1%),由于化合物16在普通溶剂中不溶解,故只进行质谱测定。化合物16的质谱结果为:MS(MALDI-TOF)C16H4Br2N2S m/z:415.84;Found:416.13(M+H+).反应方程式如下:
实施例13
一种基于萘稠环的缺电子单体,为化合物17,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
在氮气氛围下,把Pd2(dba)3(0.014g)加入到化合物16(0.2g),2-(三丁基锡基)-4-乙基己基噻吩(0.58g)和P(o-tol)3(0.041g)的甲苯(8mL)溶液中。将混合物加热回流并搅拌2h,除去溶剂后,粗产物以正己烷:CH2Cl2(1:1)为洗脱剂进行柱层析纯化,得到红色固体化合物17(0.169g,54.4%)。
化合物17(Compound 17)的核磁结果如图10所示,核磁数据为:1H NMR(400MHz,CDCl3)(ppm):8.08(d,J=7.6Hz,2H),7.89(d,J=7.6Hz,2H),7.22(s,2H),7.06(s,2H),2.62(d,J=6.9Hz,4H),1.63(br,2H),1.33(br,16H),0.93(br,12H).反应方程式如下:
实施例14
一种基于萘稠环的缺电子单体,为化合物18,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
在化合物17(0.169g)的CHCl3(5mL)溶液中加入NBS(0.092g);将混合物搅拌反应2h,除去溶剂后,粗产物用正己烷:CH2Cl2(1:1)作为洗脱液进行柱层析纯化,得到红色固体化合物18(108g,51.4%)。
化合物18(Compound 18)的核磁结果如图11所示,核磁数据为:1H NMR(400MHz,CDCl3)(ppm):8.17(d,J=7.6Hz,2H),8.04(d,J=7.6Hz,2H),7.11(s,2H),2.57(d,J=7.2Hz,4H),1.65(br,4H),1.33(br,16H),0.94(br,12H).反应方程式如下:
实施例15
一种基于萘稠环的缺电子单体,为化合物20,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
在氮气氛围下,把Pd2(dba)3(0.48g)和P(MeOPh)3(1.48g)加入到具有1,8-二溴萘(化合物19,3g),化合物3,4-二(4,4,5,5-四甲基-1,3,2-二氧化硼-2-基)噻吩(3.89g),干THF(84mL)和2M K2CO3水溶液(21mL)的反应体系中,回流30min后,混合物用CH2Cl2萃取,结合有机层用Na2SO4干燥。粗产物除去溶剂后,以正己烷为洗脱剂进行柱层析纯化,得到白色固体化合物20(1.23g,56.3%)。
化合物20(Compound 20)的核磁结果如图12所示,核磁数据为:1H NMR(400MHz,CDCl3)(ppm):7.74(d,J=8.4,2H),7.72(d,J=8.0,2H)7.56(t,2H),7.43(s,2H).反应方程式如下:
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实施例16
一种基于萘稠环的缺电子单体,为化合物20,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
室温下,将NBS(0.376g)加入到化合物20(0.2g)的CHCl3溶液中,搅拌1小时后,除去溶剂,以正己烷作为洗脱剂进行柱层析纯化,得到化合物21(0.21g,57.4%)。
化合物21(Compound 21)的核磁结果如图13所示,核磁数据为:1H NMR(400MHz,CDCl3)(ppm):7.95(d,J=7.2Hz,2H),7.82(d,J=8.0Hz,2H),7.27(t,2H)。反应方程式如下:
实施例17
一种基于萘稠环的聚合物,为聚合物PATP1,具有如下所示分子结构:
上述的基于萘稠环的单体的制备方法,包括如下步骤:
在氮气氛围下,将化合物8b(101.90mg)、化合物9(132.92mg)、P(o-tolyl)3(4.86mg)、Pd2(dba)3(1.84mg)和甲苯(4mL)加入35mL施伦克反应管中;回流2h后,反应液在120℃下成凝胶,然后将氯苯(4mL)加入到溶液中回流,搅拌过夜,将溶液过滤,边搅拌边加入正己烷中,沉淀物用CH2Cl2和CHCl3进行过滤和索氏提取,最后用氯苯提取,将浓缩液滴入40mL无水乙醇中,通过过滤收集聚合物,并在减压下干燥,得到PATP1产品(140mg,75%);PATP1分子量Mn(Molecular weight)=46.32kDa;PATP1多分散性(polydispersity,PDI)=2.24.化合物9的分子结构、反应方程式如下:
实施例18
一种基于萘稠环的缺电子聚合物,为聚合物PATP2,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
在氮气氛围下,将化合物8c(110.72mg)、化合物9(132.92mg)、P(o-tolyl)3(4.86mg)、Pd2(dba)3(1.84mg)和甲苯(4mL)加入到35mL施伦克反应管中;反应混合物在120℃加热5小时;然后将氯苯(4mL)加入溶液中回流10分钟,将溶液过滤,搅拌加入己烷中,沉淀物用CH2Cl2和CHCl3进行过滤和索氏提取,最后用氯苯提取,将浓缩液滴入40mL无水乙醇中,通过过滤收集聚合物,并在减压下干燥,得到PATP2产品(134mg,69%)。PATP2分子量Mn(Molecular weight)=79.20kDa;PATP2多分散性(polydispersity,PDI)=2.37.反应方程式如下:
实施例19
一种基于萘稠环的缺电子聚合物,为聚合物PTAC1,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
在氮气氛围下,将化合物10(46.60mg)、化合物11(60.86mg)、P(o-tolyl)3(2.44mg)、Pd2(dba)3(0.92mg)和甲苯(2mL)加入15mL施伦克反应管中;回流40分钟后,反应液在120℃下成凝胶;然后将氯苯(2mL)加入到溶液中回流,搅拌反应25分钟;将溶液过滤,边搅拌边加入正己烷中;沉淀物用CH2Cl2和CHCl3进行过滤和索氏提取;最后用氯苯提取,将浓缩液滴入40mL无水乙醇中;通过过滤收集聚合物,并在减压下干燥,得到聚合物PTAC1(50mg,60.1%)。化合物11的分子结构、反应方程式如下:
实施例20
一种基于萘稠环的缺电子聚合物,为聚合物PTAC2,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
在氮气氛围下,将化合物18(40.99mg)、化合物11(66.44mg)、P(o-tolyl)3(2.43mg)、Pd2(dba)3(0.92mg)和甲苯(2mL)加入15mL施伦克反应管中;回流20分钟后反应液在120℃下成凝胶,然后将氯苯(2mL)加入到溶液中回流,反应2小时15分钟,再加入氯苯(2mL),搅拌过夜,反应物70摄氏度成凝胶;将溶液过滤,边搅拌边加入正己烷中;沉淀物用CH2Cl2进行过滤和索氏提取;将浓缩液滴入40mL无水乙醇中;通过过滤收集聚合物,并在减压下干燥,得到PTAC2产品(38mg,41.9%)。反应方程式如下:
实施例21
一种基于萘稠环的缺电子聚合物,为聚合物PTAT,具有如下所示分子结构:
上述的基于萘稠环的缺电子单体的制备方法,包括如下步骤:
在氮气氛围下,将化合物21(18.31mg)、化合物22(59.89mg)、P(o-tolyl)3(2.43mg)、Pd2(dba)3(0.92mg)和甲苯(2mL)加入15mL施伦克反应管中;回流30分钟后反应液在120℃下成凝胶,然后将氯苯(2mL)加入到溶液中回流,反应10分钟,反应物70-80℃呈凝胶;将溶液过滤,边搅拌边加入正己烷中;沉淀物用CH2Cl2和CHCl3进行过滤和索氏提取;最后用氯苯提取,将浓缩液滴入40mL无水乙醇中;通过过滤收集聚合物,并在减压下干燥,得到聚合物PTAT(35mg,64.9%)。化合物22的分子结构、以及反应方程式如下:
应用例1
基于PATP1:BO-4F的太阳能电池结构为:ITO/PEDOT:PSS/PATP1:BO-4F/PNDIT-F3N/Ag,其中,ITO:氧化铟锡;PEDOT:PSS:聚3,4-乙烯二氧噻吩:聚苯乙烯磺酸盐;Ag:银;BO-4F(即Y6-BO)、PNDIT-F3N、Y6、N3-4F的分子结构如下所示:
基于PATP1:BO-4F的太阳能电池的制备方法为:在ITO玻璃上6000rpm旋涂PEDOT:PSS的水溶液,150℃退火15分钟,然后转移到手套箱,旋涂9.5mg/mL的PATP1的氯苯溶液,再旋涂9.2mg/mL的BO-4F的氯仿溶液,110℃退火5分钟,得到厚度125nm左右的活性层;然后0.5mg/mL的PNDIT-F3N甲醇溶液旋涂在活性层材料的上部,100nm厚的Ag电极通过掩膜板蒸镀在最上层,得到测试面积为4mm2的太阳能电池。
通过标准太阳能电池校准100mW·cm-2的太阳光强度测试,得到的J-V曲线如图14所示。通过逐层沉积的方式制备的基于PATP1的太阳能电池具有最高得到17.14%的光电转换效率,短路电流为:26.78mA·cm-2,开路电压为:0.844V,填充因子为:0.759。目前只有极少数聚合物给体材料通过逐层沉积的方式制备的太阳能电池具有超过17%的光电转换效率,说明PATP1是非常具有潜力的聚合物给体材料。其中图14中的Current Density为电流密度,Voltage为电压。
应用例2
基于PATP2:BO-4F的太阳能电池结构为:ITO/PEDOT:PSS/PATP2:BO-4F/PNDIT-F3N/Ag。制备方法为:在ITO玻璃上6000rpm旋涂PEDOT:PSS的水溶液,150℃退火15分钟,然后转移到手套箱,旋涂8mg/mL的PATP1的氯苯溶液,然后旋涂9.2mg/mL的BO-4F氯仿溶液,110℃退火5分钟,得到厚度125nm左右的活性层;然后0.5mg/mL的PNDIT-F3N甲醇溶液旋涂在活性层材料的上部,100nm厚的Ag电极通过掩膜板蒸镀在最上层,得到测试面积为4mm2的太阳能电池。
通过标准太阳能电池校准100mW·cm-2的太阳光强度测试,得到的J-V曲线如图14所示。最高得到14.20%的光电转换效率,短路电流为:24.03mA·cm-2,开路电压为:0.836V,填充因子为:0.707。以上结果证明本发明制得的太阳能电池光电转换效率高,性能优异。其中图14中的Current Density为电流密度,Voltage为电压。
应用例3
基于聚合物PTAC1:N3-4F的太阳能电池结构为:ITO/PEDOT:PSS/PTAC1:N3-4F/PNDIT-F3N/Ag;在ITO玻璃上6000rpm旋涂PEDOT:PSS的水溶液,150℃退火15分钟,然后转移到手套箱,旋涂5.5mg/mL的聚合物13:N3-4F的氯仿溶液,110℃退火5分钟,得到厚度100nm左右的活性层;然后0.5mg/mL的PNDIT-F3N甲醇溶液旋涂在活性层材料的上部,100nm厚的Ag电极通过掩膜板蒸镀在最上层,得到测试面积为4mm2的太阳能电池。
通过标准太阳能电池校准100Mw·cm-2的太阳光强度测试,得到的J-V曲线如图15所示。最高得到12.52%的光电转换效率,短路电流为:22.92mA·cm-2,开路电压为:0.857V,填充因子为:0.64。其中图15中的Current Density为电流密度,Voltage为电压。
应用例4
基于聚合物PTAC2:Y6的太阳能电池结构为:ITO/PEDOT:PSS/PTAC2:Y6/PNDIT-F3N/Ag。制备方法为:在ITO玻璃上6000rpm旋涂PEDOT:PSS的水溶液,150℃退火15分钟,然后转移到手套箱;旋涂7mg/mL的PTAC2:Y6(1:1.4)的氯仿溶液,110℃退火5分钟,得到厚度100nm左右的活性层;然后0.5mg/mL的PNDIT-F3N甲醇溶液旋涂在活性层材料的上部,100nm厚的Ag电极通过掩膜板蒸镀在最上层,得到测试面积为4mm2的太阳能电池。
通过标准太阳能电池校准100mW·cm-2的太阳光强度测试,得到的J-V曲线如图16所示。最高得到2.20%的光电转换效率,短路电流为:7.16mA·cm-2,开路电压为:0.892V,填充因子为:0.34。其中图16中的Current Density为电流密度,Voltage为电压。
应用例5
基于聚合物PTAT:Y6的太阳能电池结构是ITO/PEDOT:PSS/PTAT:Y6/PNDIT-F3N/Ag。制备方法为:在ITO玻璃上6000rpm旋涂PEDOT:PSS的水溶液,150℃退火15分钟,然后转移到手套箱;基片预加热4min后,旋涂6mg/mL的PTAT的氯苯溶液和9.2mg/mL的Y6的氯仿溶液,110℃退火5分钟,得到厚度100nm左右的活性层;然后0.5mg/mL的PNDIT-F3N甲醇溶液旋涂在活性层材料的上部,100nm厚的Ag电极通过掩膜板蒸镀在最上层,得到测试面积为4mm2的太阳能电池。
通过标准太阳能电池校准100mWcm-2的太阳光强度测试,得到的J-V曲线如图17所示。最高得到11.11%的光电转换效率,短路电流为:19.19mA·cm-2,开路电压为:0.902V,填充因子为:0.64。其中图17中的Current Density为电流密度,Voltage为电压。
Claims (4)
1.一种聚合物,其特征在于,具有如下分子结构中的一种:
、/>、
、/>;
n为正整数。
2.权利要求1所述的聚合物的制备方法,其特征在于,包括如下步骤:
在惰性氛围中,将所述缺电子单体通过有机锡反应制得所述聚合物;
反应方程式如下:
;或
;或
;或
;n为正整数。
3.权利要求1所述的聚合物在光伏领域中的应用。
4.一种太阳能电池,其特征在于,制备所述太阳能电池的原料组分包括权利要求1所述的聚合物。
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