CN115433346A - 基于菲醌α-二胺的钯类催化剂及其制备方法和应用 - Google Patents
基于菲醌α-二胺的钯类催化剂及其制备方法和应用 Download PDFInfo
- Publication number
- CN115433346A CN115433346A CN202211207834.0A CN202211207834A CN115433346A CN 115433346 A CN115433346 A CN 115433346A CN 202211207834 A CN202211207834 A CN 202211207834A CN 115433346 A CN115433346 A CN 115433346A
- Authority
- CN
- China
- Prior art keywords
- alpha
- diamine
- phenanthrenequinone
- palladium
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 28
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical class 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical class 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 125000001309 chloro group Chemical class Cl* 0.000 claims abstract description 5
- 229910052731 fluorine Chemical class 0.000 claims abstract description 5
- 125000001153 fluoro group Chemical class F* 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003446 ligand Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims 1
- 150000008041 alkali metal carbonates Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 239000002861 polymer material Substances 0.000 abstract description 7
- 125000001424 substituent group Chemical group 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract 1
- 230000003335 steric effect Effects 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 229960001701 chloroform Drugs 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229920005603 alternating copolymer Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000013082 photovoltaic technology Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 101100323278 Mus musculus Ankrd23 gene Proteins 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- -1 alkali metal potassium carbonate Chemical class 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 description 2
- VLRWWADMWHAHFZ-UHFFFAOYSA-N 2-benzyl-4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1CC1=CC=CC=C1 VLRWWADMWHAHFZ-UHFFFAOYSA-N 0.000 description 1
- DWOBGCPUQNFAFB-UHFFFAOYSA-N 2-benzylaniline Chemical compound NC1=CC=CC=C1CC1=CC=CC=C1 DWOBGCPUQNFAFB-UHFFFAOYSA-N 0.000 description 1
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
- 229940076442 9,10-anthraquinone Drugs 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 238000005700 Stille cross coupling reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G2261/3223—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G2261/324—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/514—Electron transport
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/91—Photovoltaic applications
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域
本发明属于光电材料催化剂技术领域,具体涉及菲醌α-二胺钯类催化剂制备及其在光电给体聚合物材料中的应用。
背景技术
有机太阳能电池(OSC)作为一种新型薄膜光伏技术,因具有质轻、柔性、大面积低成本制备、光伏材料高度可调等诸多现有光伏技术无法比拟优点,成为新能源领域的研究热点。在现有的光伏技术中,昂贵的制作成本是制约其大规模商业化应用的关键。然而,在有机太阳能电池的实验室研发中,尽管一些聚合物给体材料展现出较高的光电转换效率,但较低的聚合产率阻碍了其商业化应用前景。
在已报道的高性能聚合物给体材料中,基于苯并二噻吩(BDT)单元的聚合物给体材料一直是有机太阳能电池领域的研究热点。目前,通常是采用两种经典钯催化体系来制备该类聚合物给体材料,如聚合物PBnDT-FTAZ,J52,PNTBDT等通常采用Pd2(dba)3/P-(o-Tol)3催化体系制备,而聚合物PTB7-Th[10],PBDBT,PBPD-Th,PM6,D18等通常采用Pd(PPh3)4催化体系获得。理想情况下,基于上述催化体系的Stille交叉偶联缩合方法能够产生规整的D-A交替共聚物,这是因为sp2杂化碳-卤(Br or I)键仅能与芳基碳-锡键(sp2 C-Sn)反应。事实上,在钯催化条件下,通常存在一定程度的反应缺陷(自偶联、端基缺陷、钯金属缺陷等),导致D和A单元共聚时并不完全按照预想的1:1交替排列。尤其是使用不同催化剂时,这种自耦联程度将会呈现出不同状况。说明:即使具有相同主链结构单元的D-A交替共聚物,在使用不同催化剂聚合时很可能会展现出完全不同的的规整度、分子量、分散指数,进而影响对应高性能聚合物部分的产率。
基于此,申请人前期研究发现:采用上述两种经典钯催化剂,对展现出高性能的聚合物PTB7-Th进行制备,经分析两种催化剂制备的聚合物结构的D和A比例均不是按照1:1进行排列,表明两种聚合物结构均存在不同程度的缺陷。此外,以②Pd(PPh3)4为催化剂制备聚合物的分子量几乎是①Pd2(dba)3的两倍,光伏性能也接近于两倍,但产率缺相反(Pd(PPh3)4收集的高效聚合物产率为48%,而Pd2(dba)3可获得87%高的产率)。可以看出,优化聚合物反应条件,不仅可以筛选出高性能的聚合物,同时还可以提升聚合物收率;且传统的两种钯系催化无法有效兼顾良好的聚合物性能和收率。基于此,设计高性能的催化剂是进一步提升聚合物性能和收率的关键。
发明内容
本发明的主要目的在于针对现有催化剂的不足,提供一类基于菲醌α-二胺钯催化剂,该催化剂以原料来源广,价格便宜,结构简单易修饰,热稳定性以及环境稳定性等诸多优点为一体的α-二胺为配体中心,并采用不同空间位阻取代基团来进行优化,具有低成本、高效的优点;可用于高性能聚合物给体材料PDD-4等,实现聚合物PDD-4的分子量和分散度的调节,获得高品质的聚合物材料,在有机太阳能电池具有良好的应用前景。
为实现上述目的,本发明采用的技术方案为:
基于菲醌α-二胺钯催化剂以α-二胺为配体中心,结构式见式I:
式中,R为甲基、苯基;R1为氯原子、氟原子、烷基、烷氧基(C的个数为1~3,下文以甲基或甲氧基为例)。
具体结构如下
上述方案中,所述基于菲醌α-二胺的钯催化剂催化剂为Pd-NHC络合物,其中采用的NHC配体前体的结构式见式II:
式中,R为甲基、苯基的一种;R1为烷基、烷氧基、氯原子或氟原子的一种。
上述方案中,菲醌α-二胺钯催化剂的制备方法,包括如下步骤:在反应容器中加入NHC配体前体、二氯化钯和反应溶剂,在保护气氛下升温至80~90℃,回流反应10~24小时。
上述方案中,所述保护气氛可用氮气、氩气等气氛。
上述方案中,所述反应溶剂可选用甲醇、乙醇等醇类;其与二氯化钯的液固比为8~12ml:1g。
上述方案中,所述NHC配体前体、二氯化钯的摩尔比为1:1~1.2。
上述方案中,所述NHC配体前体的制备方法包括如下步骤:在反应容器中加入9,10-菲醌、4号位取代的2,6-二苯甲基苯胺和氯化锌,加入醋酸为溶剂,100~120℃下搅拌5~12h;冷却至室温后,过滤出固体,将其溶于二氯甲烷,加入草酸钾和水,室温搅拌12-24h;二氯甲烷萃取,二氯甲烷和醋酸重结晶,即得所述NHC配体前体。
上述方案中,所述含4号位取代的2,6-二苯甲基苯胺的结构式见式III;
式中,R为甲基、苯基中的一种。
上述方案中,所述含9,10-菲醌、4号位取代的2,6-二苯甲基苯胺、氯化锌的摩尔比为1:2~2.5:2.5。
上述方案所述基于菲醌α-二胺的钯催化剂作为D-A聚合物催化剂的应用。
进一步地,所述D-A聚合物催化剂为聚合物PDD-4等,具体制备步骤包括如下:将D单元单体、A单元单体、基于菲醌α-二胺的钯催化剂、膦配体、碱金属碳酸钾、四甲基乙二胺(TMEDA)、t-BuCO2H加入有机溶剂中混合均匀,然后在110~150℃和保护气氛下,反应24~72h;其中D单元单体、A单元单体和催化剂的摩尔比为1:1:0.02~0.05。
上述方案中,所述有机溶剂为甲苯、氯苯或邻二甲苯。
上述方案中,所述膦配体可选用P(o-OMePh)3、P(o-tol)3、PPh3等;碱金属碳酸钾可选用碳酸钾,碳酸铯等。
根据上述方案构建出的给体材料的催化体系,获得高度规整,分子量和分散度可控的D-A交替共聚物,用作活性层的给体材料或电子传输材料。
本发明通过合成具有不同基团取代的N-苯环的α-二胺钯催化剂,可通过优化催化剂结构,控制聚合时间、催化剂用量制备出系列聚合物,经对比聚合收率、聚合物品质等筛选出最佳聚合物材料(PDD-4样本)。进一步选取非富勒烯小分子为受体,通过器件优化,制备出基于PDD-4为给体的性能超过16%的有机太阳能电池。
本发明的原理为:骨架空间位阻会影响催化剂的催化活性,选择合适位阻的取代基团可实现对聚合物分子量的调控,进而筛选高效的聚合物材料;本发明所述催化剂以较大体积的菲醌为骨架,并在N原子上引入不同取代基的苯,通过增加骨架和邻位芳基的体积来实现阻碍链转移速率,提升链增速率,抑制结构缺陷,进而获得高度规整度、分子量高的聚合物材料。
与现有技术相比,本发明的有益效果为:
1)本发明涉及的α-二胺分子具有制备原料来源广,价格便宜,结构简单易修饰,骨架空间位阻大且易于调节,给电子能力强,热稳定性以及空气稳定性好等诸多优点,能够有效调节催化剂的电子和位阻效应;
2)本发明所得催化剂可实现对聚合物结构缺陷的有效抑制,可有效调控所得聚合物的分子量和分散度的调控,获得高收率、高品质的聚合物;其在有机太阳能电池具有良好的应用前景。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。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。
实施例1
一种基于菲醌α-二胺的钯催化剂,其合成路线见式IV;
具体制备步骤如下:
1-1)在双颈瓶中加入2-苯甲基苯胺(2.59g,10mmol)和N-氯代丁二酰亚胺(NCS)(2.66g,20mmol),加入三氯甲烷(50ml)和乙酸(50ml)为溶剂,室温下搅拌反应过夜;去离子水猝灭后,用饱和氯化钠和二氯甲烷萃取,有机相用无水Na2SO4干燥后,除去溶剂;用硅胶柱色谱分离提纯,洗脱剂为石油醚,得到化合物2-苯甲基-4-氯苯胺(1.46g,50%);
1-2)在烧瓶中依次加入产物1(4.99g,17mmol)、二苯甲醇(3.44g,19mmol)、氯化锌(0.54g,4mmol)和盐酸(0.49g,13.6mmol),搅拌反应四小时,点板监测反应;反应结束后,蒸馏水猝灭后,用饱和氯化钠和二氯甲烷萃取,有机相用无水Na2SO4干燥后,除去溶剂;用硅胶柱色谱分离提纯,洗脱剂为乙酸乙酯/石油醚,得到化合物2(2.11g,27%);
1-3)在氮气氛围下,将化合物2(460.02mg,1.00mmol),9,10-蒽醌(91.09mg,0.50mmol),氯化锌(170.37mg,1.25mmol)加入双颈烧瓶中,加入5mL的醋酸为溶剂,120℃下搅拌5小时;冷却至室温后,过滤出固体,将其溶于二氯,加入草酸钾和水,室温搅拌12小时;二氯甲烷萃取,二氯和醋酸重结晶;得到化合物3(0.98g,90%);
1-4)将化合物3(1.09g,1.0mmol)、二氯化钯(0.19g,1.1mmol)和甲醇(10mL)加入到双口烧瓶中,在氮气氛围下,升温至80℃,回流反应12小时;在反应混合物冷却至室温后,蒸馏水猝灭后,用饱和氯化钠和二氯甲烷萃取,有机相用无水Na2SO4干燥后,然后减压蒸干溶剂,加入二氯甲烷(5ml)溶解后过滤除去不溶部分;后加入正己烷(20毫升),然后将沉淀过滤、干燥,得到最终产物化合物4(0.76g,60%)。
应用例1
将实施例1所得催化剂产物和传统Pd(PPh3)4催化剂应用于PDD-4的聚合,其聚合路线见式V;
Still聚合反应:在氮气保护下,依次加入A单元单体(0.13g,0.20mmol)和D单元单体(0.19g,0.20mmol),催化剂Pd(PPh3)4(0.01g,0.01mmol)和5mL无水甲苯,110℃反应48h;粗产物用甲醇沉降,随后依次用丙酮、正己烷、二氯甲烷、三氯甲烷进行抽提;旋蒸三氯甲烷,加入甲醇沉降,抽滤得最终宽带隙聚合物产物PDD-4。(Mn=121461;PDI=3.68)
DArP聚合:D单元单体(0.19g,0.20mmol)、A单元单体(0.13g,0.20mmol)、新型菲醌α-二胺钯类催化剂(126.90mg,0.01mmol)、P(o-OMePh)3(4.32mg,0.01mmol)、Cs2CO3(0.16g,0.50mmol)、TMEDA(0.06g,0.5mmol)、t-BuCO2H(1.03mg,0.01mmol)和5mL无水甲苯,110℃反应48h;粗产物用甲醇沉降,随后依次用丙酮、正己烷、二氯甲烷、三氯甲烷进行抽提;旋蒸三氯甲烷,加入甲醇沉降,抽滤得最终宽带隙聚合物产物PDD-4。(Mn=186113;PDI=1.56);
所得聚合物分子量和分散性指数的测试结果见表1。
表1使用Still和DArP方法聚合的聚合物分子量和分散性指数对比
上述结果表明:使用本发明所述菲醌α-二胺钯类催化剂所得聚合物的分子量得到显著提升,PDI指数下降,材料分子量分布更均匀。
本发明通过构建出基于α-二胺分子为配体,引导筛选骨架、基团的设计规律,优化出最高效α-二胺钯催化剂。通过分子工程构建催化体系,获得高品质聚合物材料,实现基于PDD-4给体材料制备电池器件效率超过16%的有机太阳能电池。
上述实施例仅是为了清楚地说明所做的实例,而并非对实施方式的限制。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其他不同形式的变化或者变动,这里无需也无法对所有的实施方式予以穷举,因此所引申的显而易见的变化或变动仍处于本发明创造的保护范围之内。
Claims (9)
4.权利要求1~3任一项所述基于菲醌α-二胺钯类催化剂的制备方法,其特征在于,包括如下步骤:在反应容器中加入NHC配体前体、二氯化钯和反应溶剂,混合均匀后,在80~90℃和保护气氛下,回流反应10~24h。
5.根据权利要求4所述的制备方法,其特征在于,所述NHC配体前体的制备方法包括如下步骤:在反应容器中加入9,10-菲醌、4号位取代的2,6-二苯甲基苯胺和氯化锌,加入醋酸为溶剂,100~120℃下搅拌5~12h;冷却至室温后,过滤出固体,将其溶于二氯甲烷,加入草酸钾和水,室温搅拌12-24h;二氯甲烷萃取,二氯甲烷和醋酸重结晶,即得所述NHC配体前体。
7.权利要求1-3任一项所述新型菲醌α-二胺钯类催化剂或权利要求4~6任一项所述制备方法在制备D-A型聚合物领域中的应用,其特征在于,包括如下步骤:将D单元单体、A单元单体、基于菲醌α-二胺的钯类催化剂、膦配体、碱金属碳酸盐、四甲基乙二胺、t-BuCO2H加入有机溶剂中混合均匀,然后在110~150℃和保护气氛下,反应24~72h;其中D单元单体、A单元单体和催化剂的摩尔比为1:1:0.02~0.05。
8.根据权利要求7所述的应用,其特征在于,所述有机溶剂为甲苯、氯苯或邻二甲苯。
9.根据权利要求7所述的应用,其特征在于,所得D-A型聚合物的分子量达18KDa,分散性指数下降至1.56。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211207834.0A CN115433346B (zh) | 2022-09-30 | 2022-09-30 | 基于菲醌α-二胺的钯类催化剂及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211207834.0A CN115433346B (zh) | 2022-09-30 | 2022-09-30 | 基于菲醌α-二胺的钯类催化剂及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115433346A true CN115433346A (zh) | 2022-12-06 |
CN115433346B CN115433346B (zh) | 2024-03-26 |
Family
ID=84251763
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211207834.0A Active CN115433346B (zh) | 2022-09-30 | 2022-09-30 | 基于菲醌α-二胺的钯类催化剂及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115433346B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117105990A (zh) * | 2023-10-19 | 2023-11-24 | 链行走新材料科技(广州)有限公司 | 一种催化制备聚噻吩用催化剂及p3ht材料 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104607248A (zh) * | 2015-01-23 | 2015-05-13 | 齐鲁工业大学 | 芘-4,5,9,10-四亚胺-(芳胺)合氯化钯及其在heck反应中的应用 |
US20160175828A1 (en) * | 2013-08-22 | 2016-06-23 | Shanghai Research Institute Of Chemical Industry | N-heterocyclic carbene type palladium catalyst and its preparation method as well as applications |
CN110283214A (zh) * | 2019-06-28 | 2019-09-27 | 江苏高科石化股份有限公司 | 一种含有对位二苯甲基取代的α-二亚胺钯(Ⅱ)催化剂及其制备方法 |
CN112774731A (zh) * | 2021-01-22 | 2021-05-11 | 邹育英 | 一种对位甲氧基取代的钯催化剂及其在Heck反应中的应用 |
CN112892596A (zh) * | 2021-01-22 | 2021-06-04 | 邹育英 | 一种钯催化剂及其在Heck反应中的应用 |
-
2022
- 2022-09-30 CN CN202211207834.0A patent/CN115433346B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160175828A1 (en) * | 2013-08-22 | 2016-06-23 | Shanghai Research Institute Of Chemical Industry | N-heterocyclic carbene type palladium catalyst and its preparation method as well as applications |
CN104607248A (zh) * | 2015-01-23 | 2015-05-13 | 齐鲁工业大学 | 芘-4,5,9,10-四亚胺-(芳胺)合氯化钯及其在heck反应中的应用 |
CN110283214A (zh) * | 2019-06-28 | 2019-09-27 | 江苏高科石化股份有限公司 | 一种含有对位二苯甲基取代的α-二亚胺钯(Ⅱ)催化剂及其制备方法 |
CN112774731A (zh) * | 2021-01-22 | 2021-05-11 | 邹育英 | 一种对位甲氧基取代的钯催化剂及其在Heck反应中的应用 |
CN112892596A (zh) * | 2021-01-22 | 2021-06-04 | 邹育英 | 一种钯催化剂及其在Heck反应中的应用 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117105990A (zh) * | 2023-10-19 | 2023-11-24 | 链行走新材料科技(广州)有限公司 | 一种催化制备聚噻吩用催化剂及p3ht材料 |
CN117105990B (zh) * | 2023-10-19 | 2024-01-30 | 链行走新材料科技(广州)有限公司 | 一种催化制备聚噻吩用催化剂及p3ht材料 |
Also Published As
Publication number | Publication date |
---|---|
CN115433346B (zh) | 2024-03-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109134513B (zh) | 一种稠环苯并噻二唑基非富勒烯受体材料及其制备方法和应用 | |
CN108383739B (zh) | 一种带有羟基的芳香胺及其α-二亚胺配合物和在烯烃聚合中的应用 | |
CN107892695B (zh) | 一类有机聚螺格纳米聚合物材料及其制备方法 | |
CN112225882B (zh) | 一类含非稠环受体单元的n-型聚合物及其制备方法与应用 | |
CN110527005B (zh) | 一种超高分子量聚(4-烷氧基苯乙烯)及其制备方法 | |
CN115433346A (zh) | 基于菲醌α-二胺的钯类催化剂及其制备方法和应用 | |
WO2007101820A1 (en) | Palladium catalyzed polymerization reaction | |
CN109456435B (zh) | 一种含杂萘联苯结构的全氟环丁基聚芳醚的合成方法 | |
CN107619468B (zh) | 二茂铁与菲咯啉衍生物的共轭聚合物及其聚合方法和应用 | |
CN109627428B (zh) | 一种d-a型共轭聚合物及其制备方法和应用及热电材料 | |
CN109400853A (zh) | 基于3’-氟苯基取代喹喔啉结构单元的共轭聚合物及其制备方法和应用 | |
CN106040299B (zh) | 一种手性双烯铑金属催化剂、制备方法及应用 | |
EP1345477B1 (de) | Polymere auf Basis von Fluoranthen und ihre Verwendung | |
CN109553757B (zh) | 一种二维结构的萘二酰亚胺类受体聚合物及其制备方法与应用 | |
CN111004371B (zh) | 一种AB2单体及其制备的给体-受体-给体-π桥型超支化共轭聚合物及制备方法和应用 | |
CN113620927B (zh) | 一种噻吩基苯衍生物及其制备方法和应用、给体材料及其制备方法 | |
CN109438695B (zh) | 一种含杂萘联苯结构的全氟环丁基共聚芳醚的合成方法 | |
CN114316221A (zh) | 一类聚噻吩及其制备方法与应用 | |
CN112851715A (zh) | 一种催化4-甲基-1-戊烯聚合的配合物及其制备方法 | |
CN115536818A (zh) | 一类基于芘基的氮杂环卡宾金属钯催化剂及其制备方法和应用 | |
CN106631751B (zh) | 抗氧化型多甲基侧链二氟单体及其制备方法 | |
CN115536817A (zh) | 一类萘基取代的非对称金属催化剂及其制备方法及应用 | |
CN111269273A (zh) | 一种催化4-甲基-1-戊烯聚合的配合物及其制备方法 | |
CN115028834B (zh) | 一种聚芳基三唑及其制备方法和应用 | |
CN109384933B (zh) | 一种含硅芳炔聚合物及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |