CN107474226A - The acid imide conjugated polymer and its synthetic method of a kind of perfluoroalkyl modification - Google Patents

The acid imide conjugated polymer and its synthetic method of a kind of perfluoroalkyl modification Download PDF

Info

Publication number
CN107474226A
CN107474226A CN201710644376.XA CN201710644376A CN107474226A CN 107474226 A CN107474226 A CN 107474226A CN 201710644376 A CN201710644376 A CN 201710644376A CN 107474226 A CN107474226 A CN 107474226A
Authority
CN
China
Prior art keywords
perfluoroalkyl
thiophene
polymer
double tin
acid imide
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.)
Pending
Application number
CN201710644376.XA
Other languages
Chinese (zh)
Inventor
袁忠义
蔡春生
张有地
黄清方
胡昱
陈义旺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanchang University
Original Assignee
Nanchang University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nanchang University filed Critical Nanchang University
Priority to CN201710644376.XA priority Critical patent/CN107474226A/en
Publication of CN107474226A publication Critical patent/CN107474226A/en
Pending legal-status Critical Current

Links

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
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/141—Side-chains having aliphatic units
    • C08G2261/1412—Saturated aliphatic units
    • 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
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • 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
    • C08G2261/14—Side-groups
    • C08G2261/145—Side-chains containing sulfur
    • 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
    • C08G2261/14—Side-groups
    • C08G2261/146—Side-chains containing halogens
    • 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
    • C08G2261/14—Side-groups
    • C08G2261/149—Side-chains having heteroaromatic units
    • 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
    • C08G2261/18—Definition of the polymer structure conjugated
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Abstract

The acid imide conjugated polymer and its synthetic method, general structure of a kind of perfluoroalkyl modification be：With 1,7 dibromo perfluoroalkyl acid imide with double tin reagents for raw material, mol ratio 1:1, by solvent and material molar ratio 300~400:1st, catalyst and material molar ratio 0.02~0.1:1, under the reflux conditions of anhydrous and oxygen-free and solvent, stille coupling reactions.The present invention can dramatically increase the dissolubility of polymer in organic solvent, form ordered crystalline or liquid crystal structure, be easy to carrier transport, obtain high mobility, while strengthen the device stability in its photo and thermal stability and scene effect transistor.

Description

The acid imide conjugated polymer and its synthetic method of a kind of perfluoroalkyl modification
Technical field
The invention belongs to organic chemical industry and field of fine chemical, and in particular to the acid imide of a kind of perfluoroalkyl modification is total to Conjugated polymer and its synthetic method.
Background technology
Organic semiconductor be it is a kind of there is flexibility, can low cost processing photoelectron material, lured in photovoltaic applications The prospect of people.Polymer semiconducting material is because of its good stability, and the good film-forming property in device preparation, and development in nearly 20 years is fast Speed, the application of organic solar batteries reached surpass 13% photoelectric transformation efficiency (J.Am.Chem.Soc.2017,139, 7302-7309).Because of it, with big, often system and good stability are extensive altogether as acceptor material for acid imide (PDIs) Applied to organic semiconductor device, but the dissolubility of PDIs differences, its application is govern always.Acid imide polymer half Conductor material in organic solar device with extensive, photoelectric transformation efficiency reached 8.59% (Adv.Mater.2017, 1700309).But because PDIs dissolubilities are poor, cause universal relatively low (the number-average molecular weight M of acid imide polymer molecular weightn Less than 40kDa), it is a not high major reason of its device mobility.
Perfluoroalkyl has rigid rod structure, and fluorine atom can form intermolecular hydrogen bonding, enhancing with neighbouring hydrogen atom Interaction (Chinese patent, publication number between molecule：CN106832246A) so that containing fluorine atom and all-fluoroalkyl compound With high stability, inoxidizability and hydrophobicity.Fluorine atom or perfluoroalkyl extensively should in organic photoelectric field With, for example fluorine atom is used for acceptor material (Chinese patent, the publication number of active isomer phase hetero-junction solar cell： CN106588923A), perfluoroalkyl be used for build air-stable field-effect transistor materials (Chem.Rev.2011,112, 2208-2267).Polymer containing perfluoroalkyl is easily formed orderly crystallization or liquid crystal structure, and this class formation is beneficial to carrier Transmission.The non-conjugated polymeric thing of perfluoroalkyl modification has a lot, orderly accumulation (Chinese patent, public affairs of their energy formation rules The number of opening：CN106588923A).And perfluoroalkyl modification is introduced directly into imido N-terminal, PDIs dissolubilities can be caused very poor (Chinese patent, publication number：CN101289447B) so that solution is processed, and obstacle occurs in terms of device film forming.Based on this, I Need to develop it is a kind of can solution processing, filming performance is good, stability is high, carrier mobility is high acid imide conjugation it is poly- Compound semi-conducting material.
The content of the invention
The purpose of the present invention is the acid imide conjugated polymer of a kind of perfluoroalkyl modification of synthesis, to improve acid imide The dissolubility of class conjugated polymer, and research perfluoroalkyl is to the crystal property of such polymer, molecules align, energy level, steady The influence of qualitative, carrier mobility and solar cell or FET device performance.
The present invention is achieved by the following technical solutions.
The acid imide conjugated polymer of a kind of perfluoroalkyl modification of the present invention, its general structure are：
R is perfluoroalkyl chain, and structural formula is as follows：
Wherein：M, n is the number of alkyl C atoms and the number of perfluoroalkyl C atoms respectively, m is 1,2,3,4,5,6, n be 1、3、5、7。
Ar is thiophene, and structural formula is as follows：
1,4-Dithiapentalene：
Di- thiophene：
And three thiophene：
Join three thiophene：
BDT units：
PBDTT units：
IDT units：
The synthetic method of the acid imide conjugated polymer of a kind of perfluoroalkyl modification of the present invention, its feature exist In：
With 1,7- dibromo perfluoroalkyl acid imides with double tin reagents for raw material, mol ratio 1：1, rubbed by solvent and raw material That ratio 300~400：1 amount, catalyst and material molar ratio 0.02~0.1：1 amount, add solvent and catalyst, anhydrous nothing Under the reflux conditions of oxygen and solvent, stille coupling reactions are carried out, generate the acid imide conjugation of the modification containing perfluoroalkyl Polymer.
Described 1,7- dibromo perfluoroalkyl acid imides, by Chinese patent (publication number:CN106588924A) prepare.
Described double tin reagents are the double tin of thiophene, the double tin of 1,4-Dithiapentalene, the double tin of di- thiophene and the double tin of three thiophene, connection three The double tin of thiophene, the double tin of BDT, the double tin of PBDTT or the double tin of IDT.
Described solvent is chlorobenzene, toluene, benzotrifluoride or DMF.
Described catalyst is Pd2(dba)3/P(o-tol)3、Pd(PPh3)2Cl2Or Pd (PPh3)4。
The beneficial effect of the invention is, while after introducing alkyl and perfluoroalkyl, can dramatically increase such material is having Dissolubility in solvent, ordered crystalline or liquid crystal structure can be formed, this structure is easy to the transmission of carrier, high so as to obtain Mobility, while strengthen the device stability in its photo and thermal stability and scene effect transistor.
Brief description of the drawings
Fig. 1 is the J-V characteristic curves that four polymer SCLC test to obtain under dark condition, corresponding with table 1.
Embodiment
The present invention will be described further by following examples.
Embodiment 1.Polymer 8CH4CF- 1 synthesis.
1 (0.5mmol, 204.88mg), 8C are sequentially added in 50mL two-mouth bottleH4CF- PDI-2Br (0.5mmol, 604.30mg), Pd (PPh3)4(0.05mmol, 57.78mg), toluene (10mL), it is 110 DEG C of reaction 18h in temperature, while hot will be anti- Mixture is answered to add in methanol, stirring, sedimentation 0.5h, is filtered after adding, and is dried, and is crossed post, revolving, is obtained atropurpureus solid and gather Compound 367.6mg, as yield 67%, polymer 8CH4CF-1.Number-average molecular weight：13000, dispersion index：1.54 (THF for stream Dynamic phase, polystyrene is standard).1H NMR(600MHz,CDCl3)δ8.76(s,2H),8.49(s,4H),7.44(s,2H), 5.74(s,2H),3.34(s,2H),2.55(s,2H),2.33(s,2H),1.89(s,2H),1.28(s,16H),0.91(s, 6H).19F NMR(565MHz,CDCl3)δ-113.71(s),-114.21(s),-115.02(s),-115.48(s),-124.39 (s),-125.90(s)。
Embodiment 2.Polymer 6CH4CF- 2 synthesis.
2 (0.5mmol, 232.92mg), 6C are sequentially added in 50mL two-mouth bottleH4CF-PDI-2Br(0.5mmol, 576.25mg), Pd (PPh3)4(0.05mmol, 57.78mg), toluene (10mL), it is 110 DEG C of reaction 20h in temperature, while hot will be anti- Mixture is answered to add in methanol, stirring, sedimentation 0.5h, is filtered after adding, and is dried, and is crossed post, revolving, is obtained atropurpureus solid and gather Compound 356.2mg, as yield 63%, polymer 6CH4CF-2.Number-average molecular weight：23500, dispersion index：2.856 (THF is Mobile phase, polystyrene are standard).1H NMR(400MHz,CDCl3)δ9.30-8.61(m,2H),8.41(d,4H),7.63(d, 2H),5.72(s,2H),3.35(s,2H),2.52(d,2H),2.31(s,2H),1.93(d,2H),1.26(s,8H),0.84(s, 6H).19F NMR(377MHz,CDCl3)δ-34.23,-81.47,-114.67,-115.54,-124.86,-126.36。
Embodiment 3.Polymer 8CH4CF- 2 synthesis.
2 (0.4mmol, 186.33mg), 8C are sequentially added in 50mL two-mouth bottleH4CF-PDI-2Br(0.4mmol, 483.44mg), Pd (PPh3)4(0.04mmol, 46.22mg), toluene (10mL), it is 110 DEG C of reaction 20h in temperature, while hot will be anti- Mixture is answered to add in methanol, stirring, sedimentation 0.5h, is filtered after adding, and is dried, and is crossed post, revolving, is obtained atropurpureus solid and gather Compound 308.6mg, as yield 65%, polymer 8CH4CF-2.Number-average molecular weight：31000, dispersion index：1.62 (THF for stream Dynamic phase, polystyrene is standard).1H NMR(400MHz,CDCl3)δ9.30-8.61(m,2H),8.41(d,4H),7.63(d, 2H),5.72(s,2H),3.35(s,2H),2.54(d,2H),2.35(s,2H),1.96(d,2H),1.25(s,16H),0.84 (s,6H).19F NMR(377MHz,CDCl3)δ-34.23,-81.47,-114.67,-115.54,-124.86,-126.36。
Embodiment 4.Polymer 6CH4CF- 3 synthesis.
3 (0.4mmol, 196.75mg), 6C are sequentially added in 50mL two-mouth bottleH4CF-PDI-2Br(0.4mmol, 461.00mg), Pd (PPh3)4(0.04mmol, 46.22mg), toluene (10mL), it is 110 DEG C of reaction 14h in temperature, while hot will be anti- Mixture is answered to add in methanol, stirring, sedimentation 0.5h, is filtered after adding, and is dried, and is crossed post, revolving, is obtained atropurpureus solid and gather Compound 328.6mg, as yield 71%, polymer 6CH4CF-3.Number-average molecular weight：62300, dispersion index：1.55 (THF for stream Dynamic phase, polystyrene is standard).1H NMR(500MHz,CDCl3)δ8.76(d,2H),8.43-8.37(d,4H),7.33-7.18 (d,4H),5.71(s,2H),3.34(s,2H),2.52(s,2H),2.36(s,2H),1.91(s,2H),1.31(d,8H),0.87 (s,6H).19F NMR(377MHz,CDCl3)δ34.23,-81.51,-114.70,-115.48,-124.91,-126.38。
Embodiment 5.Polymer 8CH4CF- 3 synthesis.
3 (0.3mmol, 147.6mg), 8C are sequentially added in 50mL two-mouth bottleH4CF-PDI-2Br(0.3mmol, 345.8mg), Pd2(dba)3(0.006mmol, 5.5mg), P (o-Tol)3(0.048mmol, 14.6mg), toluene (10mL), Temperature is 110 DEG C of reaction 1h, is while hot added reactant mixture in methanol, stirring, and sedimentation 0.5h, is filtered after adding, and is dried, Post is crossed, rotates, obtains black-and-blue solid polymer 318.3mg, as yield 87%, polymer 8CH4CF-3.Number-average molecular weight： 33300, dispersion index：1.98 (THF is mobile phase, and polystyrene is standard).1H NMR(400MHz,CDCl3)δ8.76(d, 2H),8.43(s,4H),7.33-7.11(m,4H),5.71(s,2H),3.36(s,2H),2.52(s,2H),2.35(s,2H), 1.91(s,2H),1.26(s,16H),0.83(s,6H).19F NMR(377MHz,CDCl3)δ-34.23,-81.50,- 114.70,-115.46,-124.85,-126.37。
Embodiment 6.Polymer 6CH6CF- 4 synthesis.
4 (0.3mmol, 156.58mg), 6C are sequentially added in 50mL two-mouth bottleH4CF-PDI-2Br(0.3mmol, 405.76mg), Pd (PPh3)4(0.03mmol, 34.67mg), toluene (10mL), it is 110 DEG C of reaction 21h in temperature, while hot will be anti- Mixture is answered to add in methanol, stirring, sedimentation 0.5h, is filtered after adding, and is dried, and is crossed post, revolving, is obtained black-and-blue solid and gather Compound 391.3mg, as yield 70%, polymer 6CH4CF-4.Number-average molecular weight：35000, dispersion index：1.79 (THF for stream Dynamic phase, polystyrene is standard).1H NMR(400MHz,CDCl3)δ9.30-8.61(m,2H),8.41(d,4H),7.63(d, 2H),5.72(s,2H),3.12(s,2H),2.50(d,2H),2.35(s,2H),1.96(d,2H),1.25(s,20H),0.84 (s,6H).19F NMR(377MHz,CDCl3)δ-113.68(s),-114.21(s),-115.10(s),-115.47(s),- 124.35(s),-125.87(s)。
Embodiment 7.Polymer 8CH6CF- 5 synthesis.
5 (0.3mmol, 172.20mg), 8C are sequentially added in 50mL two-mouth bottleH6CF-PDI-2Br(0.3mmol, 422.59mg), Pd2(dba)3(0.006mmol, 5.5mg), P (o-Tol)3(0.030mmol, 9.13mg), toluene (10mL), Temperature is 110 DEG C of reaction 3h, is while hot added reactant mixture in methanol, stirring, and sedimentation 0.5h, is filtered after adding, and is dried, Post is crossed, rotates, obtains black-and-blue solid polymer 345.4mg, as yield 77%, polymer 8CH6CF-5.Number-average molecular weight： 33000, dispersion index：1.62 (THF is mobile phase, and polystyrene is standard).1H NMR(600MHz,CDCl3)δ8.81(s, 1H), 8.74 (s, 1H), 8.39 (d, J=50.5Hz, 4H), 7.32 (s, 2H), 7.21 (s, 2H), 5.76 (s, 2H), 3.37 (s, 2H),2.59(s,2H),2.39(s,2H),1.94(s,2H),1.29(s,16H),0.86(s,6H)；19F NMR(565MHz, CDCl3)δ-113.78(s),-114.19(s),-115.07(s),-115.52(s),-124.37(s),-125.89(s)。
Embodiment 8.Polymer 8CH4CF- 6 synthesis.
6 (0.3mmol, 231.70mg), 8C are sequentially added in 50mL two-mouth bottleH4CF-PDI-2Br(0.3mmol, 362.58mg), Pd2(dba)3(0.006mmol, 5.5mg), P (o-Tol)3(0.048mmol, 14.6mg), toluene (10mL), Temperature is 110 DEG C of reaction 1.5h, is while hot added reactant mixture in methanol, stirring, and sedimentation 0.5h, is filtered after adding, and is done It is dry, post is crossed, revolving, obtains black-and-blue solid polymer 367.4mg, as yield 82%, polymer 8CH4CF-6.The equal molecule of number Amount：16000, dispersion index：1.78 (THF is mobile phase, and polystyrene is standard).1H NMR(400MHz,CDCl3)δ8.83 (d,2H),8.49(s,2H),8.01(s,2H),7.10(s,2H),5.69(s,2H),3.45(s,2H),2.84(s,4H),2.51 (s,2H),1.26(s,38H),0.84(s,18H).19F NMR(377MHz,CDCl3)δ-34.21,-81.25,-123.24,- 126.63。
Embodiment 9.Polymer 6CH4CF- 7 synthesis.
7 (0.3mmol, 271.4mg), 6C are sequentially added in 50mL two-mouth bottleH4CF-PDI-2Br(0.3mmol, 345.75mg), Pd2(dba)3(0.006mmol, 5.5mg), P (o-Tol)3(0.048mmol, 14.6mg), toluene (10mL), Temperature is 110 DEG C of reaction 10h, is while hot added reactant mixture in methanol, stirring, and sedimentation 0.5h, is filtered after adding, and is done It is dry, post is crossed, revolving, obtains atropurpureus solid polymer 413mg, as yield 88%, polymer 6CH4CF-7.Number-average molecular weight： 75677, dispersion index：1.95 (THF is mobile phase, and polystyrene is standard).1H NMR(500MHz,CDCl3)δ8.83(d, 2H),8.64–8.11(m,2H),7.96(d,2H),6.79(s,2H),5.71(s,2H),3.33(s,2H),2.76(s,4H), 2.58(s,2H),2.33(s,2H),1.92(s,2H),1.26(s,30H),0.83(s,18H).19F NMR(377MHz,CDCl3) δ-34.23,-81.48,-124.91,-126.35。
Embodiment 10.Polymer 8CH4CF- 7 synthesis.
7 (0.3mmol, 271.4mg), 8C are sequentially added in 50mL two-mouth bottleH4CF-PDI-2Br(0.3mmol, 362.6mg), Pd2(dba)3(0.006mmol, 5.5mg), P (o-Tol)3(0.048mmol, 14.6mg), toluene (10mL), Temperature is 110 DEG C of reaction 10h, is while hot added reactant mixture in methanol, stirring, and sedimentation 0.5h, is filtered after adding, and is done It is dry, post is crossed, revolving, obtains black-and-blue solid polymer 444.2mg, as yield 91%, polymer 8CH4CF-7.The equal molecule of number Amount：60729, dispersion index：(1.87 THF is mobile phase, and polystyrene is standard).1H NMR(400MHz,CDCl3)δ8.83 (d,2H),8.49(s,2H),8.01(s,2H),6.80(s,2H),5.69(s,2H),3.33(s,2H),2.76(s,4H),2.51 (s,2H),2.32(s,2H),1.91(s,2H),1.26(s,38H),0.84(s,18H).19F NMR(377MHz,CDCl3)δ- 34.23,-81.27,-123.28,-126.66。
Embodiment 11.Polymer 8CH6CF- 7 synthesis.
7 (0.3mmol, 271.4mg), 8C are sequentially added in 50mL two-mouth bottleH4CF-PDI-2Br(0.3mmol, 422.59mg), Pd2(dba)3(0.006mmol, 5.5mg), P (o-Tol)3(0.048mmol, 14.6mg), toluene (10mL), Temperature is 110 DEG C of reaction 10h, is while hot added reactant mixture in methanol, stirring, and sedimentation 0.5h, is filtered after adding, and is done It is dry, post is crossed, revolving, obtains black-and-blue solid polymer 471.1mg, as yield 86%, polymer 8CH4CF-7.The equal molecule of number Amount：38818, dispersion index：1.66 (THF is mobile phase, and polystyrene is standard).1H NMR(500MHz,CDCl3)δ8.83 (d,2H),8.52(s,2H),8.06(s,2H),6.79(s,2H),5.70(s,2H),3.33(s,2H),2.74(s,4H),2.51 (s,2H),2.31(s,2H),1.88(s,2H),1.23(s,38H),0.80(s,18H).19F NMR(377MHz,CDCl3)δ- 34.23,-81.24,-122.23,-123.25,-123.94,-126.60。
Embodiment 12.Polymer 6CH6CF- 7 synthesis.
7 (0.3mmol, 271.4mg), 6C are sequentially added in 50mL two-mouth bottleF6CH-PDI-2Br(0.3mmol, 405.7mg), Pd2(dba)3(0.006mmol, 5.5mg), P (o-Tol)3(0.048mmol, 14.6mg), toluene (10mL), Under conditions of vacuum, keeping temperature is 110 DEG C of reaction 10h, is while hot added reactant mixture in methanol, stirring, after adding 0.5h is settled, is filtered, is dried, post is crossed, revolving, obtains atropurpureus solid polymer 491mg, as yield 90%, polymer 6CH6CF-BDT.Number-average molecular weight：72715, dispersion index：1.90 (THF is mobile phase, and polystyrene is standard).1H NMR (500MHz,CDCl3)δ8.89(s,2H),8.49(s,2H),8.03(s,2H),6.82(s,2H),5.70(s,2H),3.33(s, 2H),2.74(s,4H),2.62(s,2H),2.36(s,2H),1.97(d,2H),1.25(s,30H),0.87(s,18H).19F NMR(377MHz,CDCl3)δ-34.17,-81.29,-106.56,-122.36,-123.28,-126.63。
In the polymer of above-mentioned preparation, to 8C thereinH4CF- 3,6CH4CF- 3,8CH6CF- 5,8CH4CF- 7 employ space The method of charge-limited current (SCLC) measures the electron mobility of pure film, to understand the property that electric charge transmits in photovoltaic performance Energy.Table 1 can be seen that the electron mobility of 3 polymer all 10-3Rank, 8CH6CF- 5 mobility is in 7.2x 10-4It is The active layer material applied during by preparing device only has 84nm thick, and the mobility value being calculated by formula (1) is relative Other 3 relatively low.
Table 1
Polymer Thickness/nm Electron mobility/cm2·V–1·s–1
8CH4CF-3 181 8.4x 10-3
6CH4CF-3 110 1.3x 10-3
8CH6CF-5 84 7.2x 10-4
8CH4CF-7 151 1.6x 10-3
Fig. 1 is the J-V characteristic curves that four polymer SCLC test to obtain under dark condition, corresponding with table 1.Cause This, the acid imide conjugated polymer for a kind of perfluoroalkyl modification that the present invention obtains has high mobility performance, available for field The active layer material of effect transistor and organic polymer solar cell.

Claims (2)

1. the acid imide conjugated polymer of a kind of perfluoroalkyl modification, it is characterized in that general structure is：
R is perfluoroalkyl chain, and structural formula is as follows：
Wherein：M, n is the number of alkyl C atoms and the number of perfluoroalkyl C atoms respectively, m is 1,2,3,4,5,6, n be 1,3, 5、7；
Ar is thiophene, and structural formula is as follows：
1,4-Dithiapentalene：
Di- thiophene：
And three thiophene：
Join three thiophene：
BDT units：
PBDTT units：
IDT units：
2. the acid imide conjugated polymer and its synthetic method of a kind of perfluoroalkyl modification described in claim 1, its feature It is as follows：
With 1,7- dibromo perfluoroalkyl acid imides with double tin reagents for raw material, mol ratio 1：1, by solvent and material molar ratio 300~400：1 amount, catalyst and material molar ratio 0.02~0.1：1 amount, adds solvent and catalyst, anhydrous and oxygen-free and Under the reflux conditions of solvent, stille coupling reactions, the acid imide conjugated polymer of generation perfluoroalkyl modification are carried out；
Described double tin reagents are the double tin of thiophene, the double tin of 1,4-Dithiapentalene, the double tin of di- thiophene and the double tin of three thiophene, three thiophene of connection The double tin of double tin, BDT, the double tin of PBDTT or the double tin of IDT；
Described solvent is chlorobenzene, toluene, benzotrifluoride or DMF；
Described catalyst is Pd2(dba)3/P(o-tol)3、Pd(PPh3)2Cl2Or Pd (PPh3)4。
CN201710644376.XA 2017-08-01 2017-08-01 The acid imide conjugated polymer and its synthetic method of a kind of perfluoroalkyl modification Pending CN107474226A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710644376.XA CN107474226A (en) 2017-08-01 2017-08-01 The acid imide conjugated polymer and its synthetic method of a kind of perfluoroalkyl modification

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710644376.XA CN107474226A (en) 2017-08-01 2017-08-01 The acid imide conjugated polymer and its synthetic method of a kind of perfluoroalkyl modification

Publications (1)

Publication Number Publication Date
CN107474226A true CN107474226A (en) 2017-12-15

Family

ID=60598111

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710644376.XA Pending CN107474226A (en) 2017-08-01 2017-08-01 The acid imide conjugated polymer and its synthetic method of a kind of perfluoroalkyl modification

Country Status (1)

Country Link
CN (1) CN107474226A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109181235A (en) * 2018-08-23 2019-01-11 深圳大学 A kind of thermal electric film and preparation method thereof
CN109529059A (en) * 2018-12-26 2019-03-29 中南大学 A kind of fluorescence-magnetic resonance bimodal quantum dot and its methods for making and using same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101709109A (en) * 2009-12-28 2010-05-19 大连理工大学 Trapezoidal conjugated polymer and method for preparing same
CN106588924A (en) * 2016-11-23 2017-04-26 南昌大学 Perfluoroalkyl-modified perylene imide and its preparation method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101709109A (en) * 2009-12-28 2010-05-19 大连理工大学 Trapezoidal conjugated polymer and method for preparing same
CN106588924A (en) * 2016-11-23 2017-04-26 南昌大学 Perfluoroalkyl-modified perylene imide and its preparation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BOSEOK KANG，ET AL: ""Side-Chain-Induced Rigid Backbone Organization of Polymer Semiconductors through Semifluoroalkyl Side Chains"", 《J. AM. CHEM. SOC.》 *
ERIKA KOZMA，ET AL: ""Synthesis of donor-acceptor poly(perylene diimide–altoligothiophene) copolymers as n-type materials for polymeric solar cells"", 《POLYMER》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109181235A (en) * 2018-08-23 2019-01-11 深圳大学 A kind of thermal electric film and preparation method thereof
CN109181235B (en) * 2018-08-23 2021-02-26 深圳大学 Thermoelectric film and preparation method thereof
CN109529059A (en) * 2018-12-26 2019-03-29 中南大学 A kind of fluorescence-magnetic resonance bimodal quantum dot and its methods for making and using same

Similar Documents

Publication Publication Date Title
CN108948327B (en) Quinoxaline conjugated polymer, preparation method thereof and application thereof in polymer solar cell
CN104557968A (en) A-D-A conjugated molecule on the basis of dithiophene indacene, and preparation method and application thereof
CN107286157B (en) A kind of diimide compounds and preparation method thereof, application
Gu et al. Design, synthesis and photovoltaic properties of two π-bridged cyclopentadithiophene-based polymers
WO2011047624A1 (en) Sulfur containing heterocycle-fused naphthalene tetracarboxylic acid diimide derivatives, preparation method and use thereof
CN106632412A (en) Perylene diimide compound, as well as preparation method and application thereof
CN107474226A (en) The acid imide conjugated polymer and its synthetic method of a kind of perfluoroalkyl modification
CN110041508B (en) Star-shaped conjugated structure polymer and preparation method and application thereof
CN104974334A (en) Novel organic electron transport material
CN114656489A (en) Oligomer receptor, preparation method thereof and photovoltaic device
CN114044885A (en) Polymer electron acceptor material containing non-covalent fused ring acceptor unit and application thereof
Li et al. Adjusted photovoltaic performance of tetrafluorobenzene-based small molecules by tailoring with different arm of acceptor units
CN108409755B (en) Organic photoelectric conversion material, preparation method and application thereof
CN102146153A (en) Perylene tetracarboxylic diimide-carbazole-dithienyldiazosulfide conjugated polymer as well as preparation method and application thereof
US8907108B2 (en) P-type organic semiconductor material and optoelectronic device utilizing the same
CN116375732A (en) Non-fullerene acceptor material and preparation method and application thereof
CN102504213B (en) Soluble benzenetetracarboxylic diimide group-containing full-conjugated polymer and preparation method thereof
CN110577548A (en) Asymmetric fused heterocycle micromolecule electron acceptor material based on dithienopyrrole and application thereof
CN114621276A (en) Benzothiadiazole boron-nitrogen derivative and application thereof
CN110964041B (en) Receptor material based on benzimide and preparation method and application thereof
CN107602822A (en) Naphthalimide conjugated polymer of perfluoroalkyl modification and preparation method thereof
CN103435616B (en) A kind of D (A-Ar) ntype compound and application thereof
CN106800511B (en) fullerene derivatives and application thereof in perovskite solar cell
CN103025737B (en) Silafluorene metalloporphyrin- benzene organic semiconductor material and preparing method and uses thereof
CN110218296A (en) A kind of structure, synthesis and its application of carbazole polymer hole mobile material

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20171215

RJ01 Rejection of invention patent application after publication