CN115044018B - 一类含有卟啉骨架结构的有机共轭聚合物及其制备方法与应用 - Google Patents
一类含有卟啉骨架结构的有机共轭聚合物及其制备方法与应用 Download PDFInfo
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- 150000004032 porphyrins Chemical group 0.000 title claims abstract description 48
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 36
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- 239000000463 material Substances 0.000 claims abstract description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
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- 238000006619 Stille reaction Methods 0.000 claims description 10
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- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [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 claims description 4
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- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 125000005605 benzo group Chemical group 0.000 description 3
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
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- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
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- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 description 2
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- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- NNTCBLBIVSUXIW-UHFFFAOYSA-N 4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]thieno[2,3-f][1]benzothiole Chemical compound C(CCC(CC)CC=1SC(=CC=1)C1=C2C=CSC2=C(C2=CC=C(CC(CCCC)CC)S2)C=2C=CSC1=2)C NNTCBLBIVSUXIW-UHFFFAOYSA-N 0.000 description 1
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开一类含有卟啉骨架结构的有机共轭聚合物及其制备方法与应用。本发明设计并合成了一类主链含有卟啉骨架结构的有机共轭金属有机聚合物，将具有高度π共轭体系、高结构稳定性、易加工的卟啉类结构与噻吩类基团相连接，进一步增强材料结构的共轭性能。将其与单壁碳纳米管(SWCNT)进行复合，通过调整含有卟啉骨架结构的有机共轭聚合物与SWCNT形成的复合薄膜中SWCNT的负载率，可以得到具有较高热电性能的薄膜材料，最高PF值为400.11μW m‑1K‑2。
Description
技术领域
本发明涉及有机材料领域，尤其涉及一类含有卟啉骨架结构的有机共轭聚合物及其制备方法与应用。
背景技术
热电材料(又称温差电材料)是一类通过塞贝克(Seebeck)效应和帕尔贴(Peltier)效应实现热能和电能相互转化的功能材料。在实际应用中，材料热电性能主要通过无量纲的ZT值(热电优值)进行衡量:ZT＝S2σT/κ，其中S是Seebeck系数，σ是电导率，κ为热导率，T为绝对温度。要想获得高ZT值热电材料，需将材料热导率降到极限，同时保持良好的电导率和热电势(由温差产生的电压)，并提高Seebeck系数。热电材料一般分为无机热电材料和有机聚合物热电材料。我国以上海硅酸盐所陈立东研究员和中科院化学所朱道本院士为代表的团队在该领域取得了很多代表性成果。目前为止，国际上报道的无机和有机热电材料最高ZT值分别为2.6(923K)和0.42(298K)。当下的高性能热电材料研究主要集中在无机半导体化合物诸如Bi2Te3，PbTe-AgSbTe2(ZT＝2.1，800K)和SnSe(ZT＝2.6，923K)等，这是由于其独有的高导电性、高Seebeck系数，以及可通过掺杂方式调控导电率和热电效应的优势。然而，由于其制作成本较高、材料种类匮乏、可加工性差且毒性较高等缺点限制了其大面积发展与应用。虽然最近这些无机材料在量子线、量子点、薄膜、超晶格等领域有所突破，但这些低维度体系的合成与量产仍然存在挑战，同时其热电性能难以直接表征且成本不菲。
由于有机热电材料如导电聚合物固有的低热导率(0.2-0.4W·mK-1)、导电性能可调及高热电效应常数等优势，成为热电领域一类新型材料。此外，有机热电材料由于具有良好的溶液可加工性，可通过溶液法实现有机热电器件大面积低成本的制作。
发明内容
基于有机热电材料的优势，本发明创造性的提供一类基于有机金属结构的可加工型高性能热电材料，以卟啉为基础骨架引入不同共轭基团，并引入金属中心促进电荷传输，从而提高热电性能。此热电材料的提供将填补金属有机热电领域的一些空白，为解决能源和环境问题提供有效途径，有望利用材料溶液可加工性制备人体可穿戴设备，为医用物理相关电源系统提供可能性。
发明人发现，卟啉具有易进行取代反应的芳香族大环、高度π共轭体系、独特的平面结构，为不同官能团的引入提供了灵活性，且卟啉类材料结构稳定性高并易加工，有非常高的应用价值。为有效提高有机热电材料的热电效率，本发明以卟啉为骨架结构，设计合成一系列新型金属有机聚合物材料；在分子层面上调控优化卟啉类材料的结构类型，通过在卟啉环外层引入刚性共轭体系，如共平面噻吩类、苯并二噻吩类等结构单元，拓展分子共轭体系的同时对取代基进行修饰，通过引入长烷基链提高材料的溶解性，并通过引入强吸电子以及供电子基团来调控材料的热电性能，以此得到一系列不同类型的金属有机热电材料。同时过渡金属锌的引入可使金属原子的d轨道与卟啉类有机配体的HOMO/LUMO相互作用调控其能带隙，从而影响材料热电性能。
通常，共轭聚合物具有出色的掺杂可逆性和较宽的掺杂范围，可以沿聚合物主链显示出优异的机械柔韧性和良好的电荷传导性。通过改变金属中心原子种类设计并优化主链中含金属原子的聚合物结构与热电性能。因为过渡金属的d轨道与配体的HOMO和/或LUMO的相互作用可以精细调控HOMO-LUMO能带隙；另外过渡金属原子的配位数，几何结构和价层也可以改变分子空间构型。
具体地，本发明的技术方案如下：
本发明的第一方面，提供一类含有卟啉骨架结构的有机共轭聚合物，其中，其结构通式如式I所示：
其中，R包括噻吩基、3,4-二氟噻吩基、联二噻吩基、4,8-双(5-(2-乙基己基)噻吩-2-基)苯并[1,2-b：4,5-b']二噻吩基、4,8-双(5-(2-乙基己基-4-氟)噻吩-2-基)苯并[1,2-b：4,5-b']二噻吩基等结构中的任意一种；对应地，各结构分别如下所示：
其中，虚线代表基团的连接键。
本发明提供了式I所示的有机共轭聚合物，此有机共轭聚合物特征在于引入了具有高度π共轭体系、独特平面结构的卟啉类骨架结构，为不同官能团的引入提供了灵活性，此类材料结构稳定性高并易加工，可引入不同官能团R进行修饰。
本发明式I所示的有机共轭聚合物，是一类主链含有卟啉骨架结构的有机共轭金属有机聚合物，在分子层面上调控优化卟啉类材料的结构类型，通过在卟啉环外层引入不同的刚性共轭体系，如共平面噻吩类、咔唑类、二茂铁二联噻吩、苯并二噻吩类、苯并噻二唑类等结构单元，拓展分子共轭体系的同时对取代基进行修饰，通过引入长烷基链提高材料的溶解性，并通过引入强吸电子以及供电子基团来调控材料的热电性能，以此得到一类金属有机热电材料。同时过渡金属的引入可使金属原子的d轨道与有机配体的HOMO/LUMO相互作用调控其能带隙，从而影响材料热电性能。
本发明上述所有合成的式I所示的有机共轭聚合物都通过傅立叶变换红外吸收光谱FT-IR和GPC测试得到了证实。
本发明的第二方面，提供一种本发明所述的含有卟啉骨架结构的有机共轭聚合物的制备方法，其中，包括如下步骤：
在惰性气氛(如氮气气氛等)保护下，将含有R基的双锡试剂与式III所示的Zn-5,10,15,20-四(4-溴苯基)卟啉于有机溶剂中混合，加入催化剂，进行Stille偶联聚合反应，反应完毕后得到式I所示的有机共轭聚合物；
其中，所述含有R基的双锡试剂的结构为：
所述式III所示的Zn-5,10,15,20-四(4-溴苯基)卟啉的结构为：
可选地，所述有机溶剂为甲苯、氯苯、二氯苯中的至少一种。
可选地，所述催化剂为四(三苯基膦)钯(Pd(PPh3)4)。
可选地，所述含有R基的双锡试剂、式III所示的Zn-5,10,15,20-四(4-溴苯基)卟啉以及催化剂的摩尔比为2:1:0.1。
可选地，所述Stille偶联聚合反应的温度为105-125℃。
可选地，所述Stille偶联聚合反应的时间为45-50小时。
进一步可选地，所述Stille偶联聚合反应的温度为120℃，所述Stille偶联聚合反应的时间为48小时。
可选地，所述式III所示的Zn-5,10,15,20-四(4-溴苯基)卟啉的制备方法，包括如下步骤：
在惰性气氛(如氮气气氛等)保护下，将式IV所示的化合物溶液(溶剂可以为三氯甲烷等)与醋酸锌溶液(溶剂可以为甲醇等)混合，然后加热搅拌，反应完毕后得到所述式III所示的Zn-5,10,15,20-四(4-溴苯基)卟啉；
其中，所述式IV所示的化合物的结构为：
其中，所述加热搅拌的时间为10-14小时，优选12小时。
其中，所述反应完毕后，还包括过硅胶柱，然后用淋洗液淋洗的步骤。经柱层析提纯，得到所述式III所示的Zn-5,10,15,20-四(4-溴苯基)卟啉。
可选地，所述式IV所示的化合物的制备方法，包括如下步骤：
在惰性气氛(如氮气气氛等)保护下，将4-溴苯甲醛溶于丙酸中，加热搅拌，然后加入吡咯，反应90分钟后，将反应物冷却至室温，打开反应瓶使大量空气进入反应瓶中，继续室温下搅拌过夜。反应结束后，将反应瓶置于冰水浴中至大量沉淀析出，后甲醇洗涤抽滤，将滤渣收集后通过柱层析法进一步提纯，得到紫色粉末状产品(即式IV所示的化合物)。
本发明的第三方面，提供本发明所述的含有卟啉骨架结构的有机共轭聚合物作为热电材料在热电领域中的应用。
本发明的第四方面，提供一种热电薄膜，其中，包括本发明所述的含有卟啉骨架结构的有机共轭聚合物。
可选地，所述热电薄膜还包括单壁碳纳米管。
进一步地可选地，所述热电薄膜由本发明所述的含有卟啉骨架结构的有机共轭聚合物和单壁碳纳米管组成。
有益效果：本发明设计并合成了一类主链含有卟啉骨架结构的有机共轭金属有机聚合物，将具有高度π共轭体系、高结构稳定性、易加工的卟啉类结构与噻吩类基团相连接，进一步增强材料结构的共轭性能。将其与单壁碳纳米管(SWCNT)进行复合，通过调整含有卟啉骨架结构的有机共轭聚合物与SWCNT形成的复合薄膜中SWCNT的负载率(fc，fc从15％逐渐增加到90％)，可以得到具有较高热电性能的薄膜材料，最高PF值为400.11μW m-1K-2。
附图说明
图1分别为纯SWCNT薄膜、PPR-P1/SWCNT热电薄膜、PPR-P2/SWCNT热电薄膜、PPR-P3/SWCNT热电薄膜、PPR-P4/SWCNT热电薄膜、PPR-P5/SWCNT热电薄膜的拉曼光谱；其中，热电薄膜中SWCNT掺杂率均为90％。
图2为含有卟啉骨架结构的有机共轭聚合物与SWCNT组成的复合薄膜，在不同SWCNT复合比例(fc＝15％～90％)时，其导电率的变化。
图3为PPR-P1/SWCNT热电薄膜、PPR-P2/SWCNT热电薄膜、PPR-P3/SWCNT热电薄膜、PPR-P4/SWCNT热电薄膜、PPR-P5/SWCNT热电薄膜在不同SWCNT复合比例(fc＝15％～90％)时，Seebeck系数的变化趋势图。
图4为不同SWCNT复合比例时，PPR-P1/SWCNT热电薄膜、PPR-P2/SWCNT热电薄膜、PPR-P3/SWCNT热电薄膜、PPR-P4/SWCNT热电薄膜、PPR-P5/SWCNT热电薄膜的功率因子PF变化趋势。
具体实施方式
本发明提供一类含有卟啉骨架结构的有机共轭聚合物及其制备方法与应用，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
下述实施例中提供制备式I、III、IV所示化合物的方法，其反应方程式如下所示：
下述实施例中所述制备方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。所述浓度如无特别说明，均为质量百分浓度。
实施例1、制备式IV所示的5,10,15,20-四(4-溴苯基)卟啉
在氮气保护下，称取5.032g的4-溴苯甲醛加入反应瓶中，将其溶解于100mL丙酸中，缓慢加热至60℃；另取2mL经过蒸馏进一步提纯过的吡咯，与10mL丙酸充分混合后置于滴液漏斗中缓慢滴加至上述反应瓶中，随着吡咯的滴加可观察到反应液颜色逐渐变深，后继续加热回流(约150℃)；反应90min后，将反应物冷却至室温，并打开瓶口使大量空气进入反应瓶中，继续室温下搅拌过夜。反应结束后，将反应瓶置于冰水浴中至大量沉淀析出，后甲醇洗涤抽滤，将滤渣收集后通过柱层析法进一步提纯，得到紫色粉末状产品。1H NMR((CDCl3,400MHz):δ8.84(s,8H),8.07(d,8H),7.91(d,8H),-2.88(s,2H)。
实施例2、制备式III所示的Zn-5,10,15,20-四(4-溴苯基)卟啉
称取0.46g式IV所示5,10,15,20-四(4-溴苯基)卟啉置于250mL的史莱克瓶中，氮气保护，加入80mL三氯甲烷将其完全溶解。另取0.55gZn(OAc)2溶解于20mL甲醇中，将其加入到溶有5,10,15,20-四(4-溴苯基)卟啉的反应瓶中，后加热搅拌过夜。经柱层析提纯得到深紫色粉末状产物，产物结构经核磁确认，并通过APCI-Mass测试其分子量与目标产物一致。产率为50％。1H NMR(CDCl3,400MHz):δ8.94(s,8H),8.07(d,8H),7.90(d,8H)。
实施例3、制备式I所示的高分子聚Zn-5,10,15,20-四(4-(噻吩-2-基)苯基)卟啉(PPR-P1)
在氩气保护下，将式III所示的Zn-5,10,15,20-四(4-溴苯基)卟啉(90.6mg,0.1mmol)和化合物1(82.4mg,0.2mmol)溶解于10mL甲苯中，氩气环境下加入11.5mg催化剂Pd(PPh3)4，加热回流48小时。反应结束后，加入100mL甲醇，有黑色粉末状沉淀析出，过滤并用甲醇充分洗涤后得到产物PPR-P1，产率为71％。
FT-IR(cm-1):3022 1483 1336 1205 1070 998 796 720 529 468。
实施例4、制备式I所示的高分子聚Zn-5,10,15,20-四(4-(噻吩-3,4-二氟-2-基)苯基)卟啉(PPR-P2)
在氩气保护下，将式III所示的Zn-5,10,15,20-四(4-溴苯基)卟啉(90.6mg,0.1mmol)和化合物2(89.1mg,0.2mmol)溶解于10mL甲苯中，氩气环境下加入11.5mg催化剂Pd(PPh3)4，加热回流48小时。反应结束后，加入100mL甲醇，有黑色粉末状沉淀析出，过滤并用甲醇充分洗涤后得到产物PPR-P2，产率为70％。
FT-IR(cm-1):3024 2923 1590 1481 1389 1335 1296 1203 1072 997 796 719538 469。
实施例5、制备式I所示的高分子聚Zn-5,10,15,20-四(4-(联二噻吩-2-基)-苯基)卟啉(PPR-P3)
氩气保护下，将式III所示的Zn-5,10,15,20-四(4-溴苯基)卟啉(90.6mg,0.1mmol)和化合物3(98.4mg,0.2mmol)溶解于10mL甲苯中，氩气环境下加入11.5mg催化剂Pd(PPh3)4，加热回流48小时。反应结束后，加入100mL甲醇，有黑色粉末状沉淀析出，过滤并用甲醇充分洗涤后得到产物PPR-P3，产率为71％。
FT-IR(cm-1):3024 2923 1595 1481 1388 1335 1204 1072 998 195 719 568470。
实施例6、制备式I所示的高分子聚Zn-5,10,15,20-四(4,8-双(5-(2-乙基己基)噻吩-2-基)苯并[1,2-b：4,5-b']二噻吩-苯基)卟啉(PPR-P4)
氩气保护下，将式III所示的Zn-5,10,15,20-四(4-溴苯基)卟啉(90.6mg,0.1mmol)和化合物4(181.2mg,0.2mmol)溶解于10mL甲苯中，氩气环境下加入11.5mg催化剂Pd(PPh3)4，加热回流48小时。反应结束后，加入100mL甲醇，有黑色粉末状沉淀析出，过滤并用甲醇充分洗涤后得到产物PPR-P4，产率为74％。
FT-IR(cm-1):3024 2956,2924 2857 1484 1457 1338 1206 1178 1071 999 936796 766 718 531。
实施例7、制备式I所示的高分子聚Zn-5,10,15,20-四(4,8-双(5-(2-乙基己基-3-氟)噻吩-2-基)苯并[1,2-b：4,5-b']二噻吩-苯基)卟啉(PPR-P5)
氩气保护下，将式III所示的Zn-5,10,15,20-四(4-溴苯基)卟啉(90.6mg,0.1mmol)和化合物5(188.2mg,0.2mmol)溶解于10mL甲苯中，氩气环境下加入11.5mg催化剂Pd(PPh3)4，加热回流48小时。反应结束后，加入100mL甲醇，有黑色粉末状沉淀析出，过滤并用甲醇充分洗涤后得到产物PPR-P5，产率为75％。
FT-IR(cm-1):3024 2955 2922 2854 1574 1489 1458 1382 1335 1179 1114 995933 810 795 765 718 532 459。
上述聚合物PPR-P1-PPR-P5的GPC测试结果见下表1所示：
表1、聚合物PPR-P1-PPR-P5的GPC测试结果
上述实施例3-7中制备的含有卟啉骨架结构的有机共轭聚合物与单壁碳纳米管进行复合的具体操作过程为：
表2、含碳纳米管/含有卟啉骨架结构的有机共轭聚合物复合材料配方表
使用超声仪在冰水浴中将SWCNT分散在无水氯苯中5小时，得到SWCNT分散液(SWCNT浓度为1mg/mL)。然后按表2比例关系配方表，将含有卟啉骨架结构的有机共轭聚合物添加到SWCNT分散液中，继续超声3h，得到不同比例的PPR-Polymer/SWCNT复合液。将不同比例的PPR-Polymer/SWCNT复合液用滴涂的方式滴加到15×15mm2的玻璃基底载玻片上，直至溶剂彻底挥发后成膜，得到复合薄膜。
为了进一步研究SWCNT和含有卟啉骨架结构的有机共轭聚合物之间的电荷转移行为，使用拉曼光谱对复合薄膜进行了表征(见图1所示)。纯单壁碳纳米管薄膜的拉曼光谱显示出类石墨G带(1592cm-1)、D带(1307cm-1)、拉曼活性呼吸模式的特征带(RBM，158cm-1)和G’带(2589cm-1)。当SWCNT与含有卟啉骨架结构的有机共轭聚合物进行复合后，所得复合薄膜的G带峰与纯SWCNT薄膜相比进行了蓝移，这说明含有卟啉骨架结构的有机共轭聚合物与碳纳米管之间进行了有效复合。
PPR-Polymer/SWCNT复合薄膜的热电性能是利用武汉嘉仪通薄膜热电测试系统来进行测试的。
图2为含有卟啉骨架结构的有机共轭聚合物与SWCNT组成的复合薄膜，在不同SWCNT复合比例(fc＝15％～90％)时，其导电率的变化。导电率随着fc的增大而升高，材料表现为半导体性质。其中，PPR-P1-SWCNT的复合比例(fc)为90％时，导电率可达1676.4S/cm。
图3为复合薄膜在不同SWCNT复合比例(fc＝15％～90％)时，Seebeck系数的变化趋势，图中可观察到，随着SWCNT含量的增大，材料的Seebeck系数有所下降；所有材料的Seebeck系数均为正值，这表明该复合材料属于p型半导体。
图4为不同SWCNT复合比例时，复合薄膜的热电性能变化趋势。材料的热电性能是用功率因子PF进行评价，功率因子是由Seebeck系数和电导率共同决定的，而Seebeck系数与电导率呈现负相关趋势，其中PPR-P1/SWCNT的SWCNT复合比例fc为60％时，其PF值达到最高343.26μW m-1K-2；其他材料均在SWCNT复合比例为90％时其PF值达到最高，其中PPR-P5/SWCNT的PF值达到最高400.11μW m-1K-2。
此外，为进一步了解材料的热电性能，估算其ZT值(热电优值)，本实施例中对复合薄膜的热导率进行了测试，测试发现，当PPR-P1/SWCNT的SWCNT复合比例fc为45％时，薄膜热导率为0.33W m-1K-1，其ZT值达到0.31。
综上所述，本发明提供的复合薄膜具有较高的Seebeck系数和导电率，这使得本发明制备的复合薄膜具有优异的热电性能；并且本发明提供的制备方法简单易实现且成本低廉。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (10)
1.一类含有卟啉骨架结构的有机共轭聚合物，其特征在于，其结构通式如式I所示：
式I
其中，R包括如下结构中的任意一种：
其中，虚线代表基团的连接键。
2.一种权利要求1所述的含有卟啉骨架结构的有机共轭聚合物的制备方法，其特征在于，包括如下步骤：
在惰性气氛保护下，将含有R基的双锡试剂与式III所示的Zn-5,10,15,20-四（4-溴苯基）卟啉于有机溶剂中混合，加入催化剂，进行Stille偶联聚合反应，反应完毕后得到式I所示的有机共轭聚合物；
其中，所述含有R基的双锡试剂的结构为：；
所述式III所示的Zn-5,10,15,20-四（4-溴苯基）卟啉的结构为：。
3.根据权利要求2所述的含有卟啉骨架结构的有机共轭聚合物的制备方法，其特征在于，所述有机溶剂为甲苯、氯苯、二氯苯中的至少一种。
4.根据权利要求2所述的含有卟啉骨架结构的有机共轭聚合物的制备方法，其特征在于，所述催化剂为四（三苯基膦）钯。
5.根据权利要求2所述的含有卟啉骨架结构的有机共轭聚合物的制备方法，其特征在于，所述含有R基的双锡试剂、式III所示的Zn-5,10,15,20-四（4-溴苯基）卟啉以及催化剂的摩尔比为2:1:0.1。
6.根据权利要求2所述的含有卟啉骨架结构的有机共轭聚合物的制备方法，其特征在于，所述Stille偶联聚合反应的温度为105-125℃。
7.根据权利要求2所述的含有卟啉骨架结构的有机共轭聚合物的制备方法，其特征在于，所述Stille偶联聚合反应的时间为45-50小时。
8.根据权利要求2所述的含有卟啉骨架结构的有机共轭聚合物的制备方法，其特征在于，所述Stille偶联聚合反应的温度为120℃，所述Stille偶联聚合反应的时间为48小时。
9.权利要求1所述的含有卟啉骨架结构的有机共轭聚合物作为热电材料在热电领域中的应用。
10.一种热电薄膜，其特征在于，包括权利要求1所述的含有卟啉骨架结构的有机共轭聚合物。
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