CN109762141A - One kind bis-alkoxy containing 2,6- replaces naphthalene polymer and its preparation and application - Google Patents

Abstract

The present invention relates to one kind to replace naphthalene polymer and its preparation and application, structure shown in formula I containing 2,6- bis-alkoxy.Preparation: will contain 2,6- bis-alkoxy replace naphthalene monomer and π unit structure monomer occur in the presence of catalyst and ligand polycondensation reaction to get.The synthetic route of the polymer of naphthalene containing substituent group of the invention is short, easy purification, and reaction yield is high, is suitable for a large amount of preparations.The polymer of bis- alkoxy substituted naphthalenes containing 2,6- of the invention has huge potential using value in organic field application field of transistors.

Description

One kind bis-alkoxy containing 2,6- replaces naphthalene polymer and its preparation and application

Technical field

The invention belongs to organic semiconductor and its preparation and application fields, in particular to a kind of to replace containing 2,6- bis-alkoxy Naphthalene polymer and its preparation and application.

Background technique

Relative to inorganic semiconductor material, semiconducting polymer's material preparation various opto-electronic devices have low cost, The series of advantages such as foldable, suitable large area production have attracted the concern of academia and industry a large number of scientific researchers.Organic field Effect transistor is the transport layer using organic semiconducting materials as carrier, controls material conductivity by extra electric field Active device.The rich and varied property of organic compound structure is the organic semiconductor material that material scholar design has different π structures Material provides extensive selection space.Wherein, the hole mobility of the field effect transistor based on organic material is up to 14cm²V^{- 1}s^-1(Kim, G. above；Kang,S.-J.；Dutta,G.K.；Han,Y.-K.；Shin,T.J.；Noh,Y.-Y.；Yang,C.A Thienoisodindigo-Naphthalene Polymer with Ultrahigh Mobility of 14.4That Substantially Exceeds Benchmark Values for Amorphous Silicon Semiconductors .J.Am.Chem.Soc.2014,136,9477-9483), considerably beyond hole mobility (the about 1cm of unformed silicon²V^-1s^-1)。 For from this angle of mobility value, organic field efficiency crystalline pipe has fully met commercialized requirement.However, working as Preceding organic field effect tube stability is not still able to satisfy the needs in market.So exploitation has organic the half of novel structure Conductor material is still the direction that material scholar struggles for it.

Organic semiconducting materials with high mobility often require that molecular backbone possesses preferable packing of molecules, have in this way (Vissenberg, M.C.J.M. are transmitted in a jumped fashion between strand conducive to carrier；Matters, M.Theory of the field-effect mobility in amorphous organic transistors.Phys.Rev.B 1998,57,12964-12926).In order to improve the intermolecular heap of organic semiconducting materials Product, is an important design of material thinking using the construction unit with larger conjugate planes.It moves in hole mentioned above Shifting rate is up to 14cm²V^-1s^-1Organic semiconductor be using big plane naphthalene unit and different beautiful Lan Zuhe.Naphthalene has bigger than benzene Flatness, and raw material is easy to get, be based on naphthalene or 1,5- bis- replace naphthalene unit there are many reports in the literature (Zhao, Q.；Kim,T.H.；Park,J.W.；Kim,S.O.；Jung,S.O.；Kim,J.W.；Ahn,T.；Kim,Y.-H.；Yi,M.H.； Kwon,S.-K.High-Performance Semiconductors based on Alkoxylnaphthyl End-Capped Oligomers for Organic Thin-Film Transistors.Adv.Mater.2008,20,4868-4872.Kwon, J.H.；An,J.-Y.；Jang,H.；Choi,S.；Chung,D.S.；Lee,M.-J.；Cha,H.-J.；Park,J.-H.；Park, C.-E.；Kim,Y.-H.Development of a New Conjugated Polymer Containing Dialkoxynaphthalene for Efficient Polymer Solar Cells and Organic Thin Film Transistors.J.Poly.Sci.Part A:Poly.Chem.2011,49,1119-1128.Chung,D.S.；Park, J.W.；Kim,S.-O.；Heo,K.；Park,C.E.；Ree,M.；Kim,Y.-H.；Kwon,S.-K.Alternating Copolymers Containing Bithiophene andDialkoxynaphthalene for the Applications to Field Effect Transistor andPhotovoltaic Cell:Performance and Stability, Chem.Mater.2009,21,5499-5507.Qin,H.；Cai,D.；Wang,M.；Ma,Y.；Yin, Z.；Tang,C.；Chen, S.-C.；Zheng,Q.,Dialoxynaphthalene as an electron-rich unit for high- performance polymer solar cells with large open circuit voltages,polymer2015, 67,258-266).But 2,6- disubstituted naphthalenes construct organic semiconductor and are not seen in document report.2016, Hyeyeon Yang, which is only reported, constructs novel copolymerization macrocyclic units for intermediate based on 2,6- bis-alkoxy to prepare organic electronic device Part (Patent:US 2016/0149143A1).But 2 are directlyed adopt, 6- bis-alkoxy and fragrant copolymerization units preparation are conjugated Polymer has no document report.We shall yet further be noted that the direct arylation of so-called use is reported in document to be prepared for being based on 2, Organic field effect tube (Sonar, the P. of 6- bis-alkoxy and pyrrolo-pyrrole-dione (DPP) conjugated polymer；Foong, T.R.B.；Dodabalapur,A.,Synthesis of diketopyrrolopyrrole basedcopolymers via The direct arylation methodfor p-channel and ambipolar OFETs, Phys.Chem.Chem.Phys.2014,16,4275-4283.).But the nuclear-magnetism by carefully checking reference information in paper Hydrogen spectrum finds that the position of substitution mark of naphthalene in the polymer is wrong, it should or the organic of naphthalene is replaced based on 1,5- bis-alkoxy Semiconductor.

It is investigated in view of document above, spy proposes that the conjugatd polymers of naphthalene is replaced to be applied to have based on 2,6- bis-alkoxy Machine electronic device, especially organic field effect tube.

Summary of the invention

Technical problem to be solved by the invention is to provide a kind of bis-alkoxies containing 2,6- to replace naphthalene polymer and its preparation With application, this method can substantially improve corresponding organic semiconducting materials by introducing alkoxy on 2,6 two positions of naphthalene Dissolubility.Preparation 2,6- bis-alkoxy step is succinct, and yield is higher, is suitable for producing in enormous quantities.

One kind of the invention naphthalene polymer containing 2,6- bis-alkoxy shown in formula I,

Wherein R₁、R₂Respectively alkoxy, R₁、R₂Identical or different, n is the degree of polymerization, n=10-1000.

Preferably, n=20-500.

Further, the alkoxy is hydrotropy alkoxy, and the chemical general formula of group is-OC₂H_2n+1, wherein n >=1 is whole Number.

The alkoxy are as follows:

One of, wherein the link position of group is indicated at wave.

The π group are as follows:

One of, wherein R is hydrotropy group, and the link position of group is indicated at wave.

The hydrotropy group is straight chain or branched paraffin, carbon atom number 4-24.

The polymer is poly- { the bis- dodecyloxy naphthalene-alt- thiophene of 2,6- }, poly- { the bis- dodecyloxy naphthalenes-of 2,6- Alt-3,4- difluoro thiophene }, poly- { 2,6- bis- bis- (thiophene -2-yl) ethylene of dodecyloxy naphthalene-alt- (E) -1,2- }, it is poly- 2, One of bis- (the 3- cetyl thiophene -2-yl) ethylene of bis- dodecyloxy naphthalene-alt- (the E) -1,2- of 6- }.

The preparation method of one kind of the invention naphthalene polymer Han 2,6- bis-alkoxy, comprising:

Replace naphthalene monomer and π unit structure monomer in catalyst or in catalyst and ligand bis-alkoxy containing 2,6- In the presence of occur polycondensation reaction to get the naphthalene polymer containing 2,6- bis-alkoxy.

Further, preferably specific equation:

Wherein R is alkoxy.The preferred embodiment of above-mentioned preparation method is as follows:

It is preferred that 2, the 6- bis-alkoxy that contains replaces naphthalene monomer to be replacing containing 2,6- bis-alkoxy for halogenated or boric acid (ester) Naphthalene monomer.Further preferably, 2, the 6- bis-alkoxy that contains replaces naphthalene monomer are as follows:

One of, wherein R is hydrotropy Property alkoxy grp, chemical general formula be-OC_nH_2n+1, the wherein integer of n >=1.

It is preferred that π group monomer are as follows: tin, borate or halogenated π unit structure monomer.

Further preferably, π group monomer are as follows:

In one Kind.

2, the 6- bis-alkoxy that contains replaces naphthalene monomer are as follows: under conditions of inert gas shielding, 3,7- bis- bromo- 2,6- bis- Hydroxyl naphthalene and alkyl bromide are prepared under conditions of dimethyl sulfoxide and sodium hydroxide.

The reaction equation are as follows:It is preferred that described contain the bis- alkane of 2,6- Oxygroup replaces the molar ratio of naphthalene monomer and π unit structure monomer to be 1:1-1.5, further, preferably 1:1.

It is preferred that the halogenation or boric acid (ester) alkylnaphthalene monomer and tin, boric acid (ester) or halogenation π structures alone Molar ratio is 1:1-1:1.2.

It is preferred that the molar ratio for stating catalyst and alkylnaphthalene monomer is (0.01-0.05): 1, further preferred 0.02:1.

It is preferred that the molar ratio of the catalyst and ligand is 1:(4-15), further preferred 1:10.

It is preferred that the ligand that the catalyst is tetra-triphenylphosphine palladium or catalyst is three (o-methyl-phenyl) phosphorus and urge Agent is the combination of tris(dibenzylideneacetone) dipalladium.

It is preferred that the catalyst is tetra-triphenylphosphine palladium.

The catalyst amount make palladium contained therein relative to halogenated monomer be 0.005-0.1 equivalent, preferably 0.01- 0.06 equivalent.

It is preferred that the reaction carries out under protective gas protection, the preferred argon gas of the protective gas, nitrogen or helium Gas.

It is preferred that the solvent of the reaction is dry toluene, anhydrous dimethyl benzene, anhydrous chlorobenzene, anhydrous N, N- dimethyl formyl One or more of amine DMF, further preferably: solvent is anhydrous dimethyl benzene and anhydrous n,N-Dimethylformamide.

It is further preferred that the dosage of the reaction dissolvent anhydrous dimethyl benzene and anhydrous DMF is distinguished relative to 1mmol halogenated monomer For 5-50mL and 0.5-5mL, preferably 5-30mL and 1-5mL.

The polycondensation reaction are as follows: 50-170 DEG C, react 1-72h.

It is preferred that the polycondensation reaction are as follows: 90-160 DEG C, react 1-72h.

Further preferably, it the polycondensation reaction: 100-140 DEG C, reacts 1-48 hours.

It is preferred that the temperature control of the polycondensation reaction uses oil bath or microwave heating, oil bath is further preferably used Heating method.

Preferably, the temperature when sealing end is 100-140 DEG C, and the time of the sealing end is 2-6 hours；

Preferably, the temperature when sealing end is 130-140 DEG C, and the time of the sealing end is 3 hours.

It is preferred that the capping reagent is that 2- tributyl tin thiophene combines 2- bromothiophene or phenyl boric acid combines bromobenzene.

A kind of organic field effect tube device comprising the polymer.

The present invention also provides application of the naphthalene polymer of bis-alkoxy containing 2,6- described in one kind in organic field effect tube.

Further, the preparation method of one kind 2,6- bis-alkoxy naphthalene polymer of the invention, step and equation are as follows:

(1) under conditions of inert gas shielding, 3,7- bis- bromo- 2,6- dihydroxy naphthlenes and alkyl bromide in dimethyl sulfoxide and Under conditions of sodium hydroxide, compound shown in formula (II -1) is obtained, reaction equation is as follows:

(2) under conditions of inert gas shielding, compound shown in formula (II) is acted in palladium catalyst and ligand catalysis Lower reaction obtains the polymer that 2,6- bis-alkoxy shown in formula (I) replaces naphthalene, and reaction equation is as follows:

Note: in the corresponding step of OR ' (2) in aforesaid equation in step (1) formula (II) compound in same compound R.The molar ratio of bromo- 2, the 6- dihydroxy naphthlene of 3,7- bis- and alkyl bromide and sodium hydroxide is 1:6:10-20 in the step (1), Preferably, 1:6:10-20.

Reaction temperature in the step (1) is 80-120 degree, and the reaction time is 48-72 hours.

Solvent in the step (1) is dimethyl sulfoxide or n,N-Dimethylformamide or tetrahydrofuran, it is preferable that two Methyl sulfoxide.

R in the step (2) is alkoxy, it is preferable that the R isIn One kind.

Beneficial effect

The present invention can substantially improve corresponding organic semiconductor material by introducing alkoxy on 2,6 two positions of naphthalene The dissolubility of material, for example, do not introduce alkoxy 2,6- naphthalene and bis- (the 3- cetyl thiophene -2- base) ethylene of (E) -1,2- it is obtained Polymer solubility it is general, needing to be heated at high temperature in chloroform could dissolve.

Present invention preparation 2,6- bis-alkoxy step is succinct, and yield is higher, is suitable for producing in enormous quantities.

2,6- bis-alkoxy of the invention replaces the molecule of the conjugatd polymers this kind organic semiconducting materials of naphthalene Chain has preferable flatness structure, and molecule, which is capable of forming, when film forming is closely spaced, and heat analysis shows it with good heat Stability, for thermal decomposition temperature more than 300 degrees Celsius, frontal orbital test shows that it is conducive to the injection of carrier, can prepare High performance p-type organic field effect tube, and it is higher than the organic effect crystal of the same polymer of 1,5- bis-alkoxy naphthalene Tube device performance.

Detailed description of the invention

Fig. 1 is the nucleus magnetic hydrogen spectrum of gained monomer in embodiment 1；

Fig. 2 is the nuclear-magnetism carbon spectrum of gained monomer in embodiment 1；

Fig. 3 is the nucleus magnetic hydrogen spectrum of gained monomer in embodiment 2；

The nuclear-magnetism of gained monomer composes spectrum in Fig. 4 embodiment 2；

Fig. 5 is the UV-visible absorption spectrum of polymer P NaT；

The UV-visible absorption spectrum of Fig. 6 polymer P NaffT；

The UV-visible absorption spectrum of Fig. 7 polymer P NaTVT；

The UV-visible absorption spectrum of Fig. 8 polymer P NaTVTC16；

The cyclic voltammetry curve of Fig. 9 polymer P NaTVTC16；

The thermogravimetric curve of Figure 10 polymer P NaTVTC16；

The differential calorimetric scan curve of Figure 11 polymer P NaTVTC16；

The configuration of Figure 12 organic field effect tube；

The 2D-GIWAXD of Figure 13 (a) polymer P NaTVT and (b) polymer P NaTVTC16 schemes.

Specific embodiment

Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.

In the invention patent, all chemical reagent and solvent are bought by commercial company, unless otherwise specified, are used It is preceding to be handled without being further purified.It is important to note that the dimethyl sulfoxide of reaction, dimethylbenzene and N, N- dimethyl methyl Amide is super dry solvent.The sodium hydroxide of sheet needs ground to be powdery, improves its contact area with reaction substrate, in turn Promote the ultimate yield of reaction.Unless otherwise specified, all organic reactions are in anhydrous nothing under inert gas (argon gas) protection Oxygen carries out.

Nucleus magnetic hydrogen spectrum and carbon spectrum are acquired using the 600MHz resonance instrument of Brooker company production.

Ultraviolet-visible spectrum is tested using the UV-2550 of Japanese Shimadzu Corporation.

The cyclic voltammetry curve of polymer is tested to obtain by Shanghai Chen Hua CHI730E electrochemical workstation, and working electrode is Glass-carbon electrode, scanning speed are 50mV s^-1, Ag/AgCl is as reference electrode, the tetrabutyl six that electrolyte is 0.1 mole every liter The acetonitrile solution of fluorophosphoric acid amine.

Heat analysis is completed by matching silent winged thermogravimetric and differential heating scan system testing.

Embodiment 1

The synthesis of 2,6- bis- bromo- bis- (the 2- octyldodecyl oxygroup) naphthalenes of 3,7-:

Under the protection of argon gas, be added into 50 milliliters of reaction flask bromo- 3, the 7- dihydroxy naphthlene of 2,6- bis- (636mg, 2mmol) with 30 milliliters of anhydrous dimethyl sulphoxides, the sodium hydroxide for being ground into powdery is disposably added into reaction flask (880mg,10equiv).After this reactant is stirred at room temperature 1 hour, be slowly added dropwise 2- octyldodecyl bromide (4.3g, 6equiv), reaction solution is then warming up to 90 degrees Celsius to react 3 days.After being cooled to room temperature, use methylene chloride (3 × 50mL) It is extracted, merges organic phase, be spin-dried on a rotary evaporator after dry, obtained crude product is added to the layer of silica filler It analyses on column, petroleum ether is used to be purified as eluant, eluent, finally obtain colourless oil liquid, yield 93%.

The structural characterization data of compound are as follows:

Hydrogen spectrum: 7.90 (s, 1H), 6.97 (s, 1H), 3.94 (d, 2H), 1.90 (m, 1H), 1.57 (m, 2H), 1.45-1.23 (m,30H),0.87(m,6H).

Carbon spectrum: 152.35,130.80,129.32,115.04,106.57,72.03,37.99,32.08,31. 69, 31.58,30.32,30.17,30.16,29.84,29.82,29.78,29.74,29.52,29.51,27.02,27.01, 22.85,14.29.

Embodiment 2

The synthesis of the bis- hexadecane epoxide naphthalenes of the bromo- 3,7- of 2,6- bis-:

Under the protection of argon gas, be added into 50 milliliters of reaction flask bromo- 3, the 7- dihydroxy naphthlene of 2,6- bis- (636mg, 2mmol) with 30 milliliters of anhydrous dimethyl sulphoxides, the sodium hydroxide for being ground into powdery is disposably added into reaction flask (880mg,10equiv).After this reactant is stirred at room temperature 1 hour, be slowly added dropwise hexadecane bromide (3.7g, 6equiv), reaction solution is then warming up to 90 degrees Celsius to react 3 days.After being cooled to room temperature, use methylene chloride (3 × 50mL) It is extracted, merges organic phase, be spin-dried on a rotary evaporator after dry, obtained crude product is added to the layer of silica filler It analyses on column, petroleum ether is used to be purified as eluant, eluent, finally obtain pure white solid, and then use methylene chloride and methanol weight White crystal, yield 49% are obtained after crystallization.

The structural characterization data of compound are as follows:

Hydrogen spectrum: 7.90 (s, 1H), 6.98 (s, 1H), 4.07 (t, 2H), 1.90 (m, 2H), 1.56 (m, 2H), 1.40-1.26 (m,23H),0.87(t,3H).

Carbon spectrum: 152.20,130.88,129.34,114.90,106.74,69.33,32.08,29.86,29. 82, 29.75,29.72,29.52,29.50,29.14,26.20,22.85,14.29.

Embodiment 3

The synthesis of poly- { 2,6- bis- dodecyloxy naphthalene-alt- thiophene }, hereinafter referred to as PNaT, the preparation method is as follows:

The synthesis of the bis- dodecyloxy naphthalenes of bromo- 3, the 7- of (1) 2,6- bis- is referring to embodiment 1, and in addition to alkyl bromide is different, other are anti- Answer condition all the same；

(2) synthesis of polymer:

In glove box, by step (1) obtained compound (154mg, 0.73mmol), 2,5- bis- tin trimethyl thiophene (86mg, 1.05equiv. are purchased from Shenzhen Rui Xun Electro-optical Technology, INC. (US) 62 Martin Road, Concord, Massachusetts 017), tetra-triphenylphosphine palladium (12mg, 0.1equiv.) add Enter into reaction tube, after putting into a magnetic stir bar, 4 milliliters and 0.8 milliliter anhydrous N of anhydrous dimethyl benzene, N- dimethyl is added Formamide is put into common oil bath pan after tube sealing and reacts 2 days in 140 degrees Celsius.After being cooled to room temperature, 0.1 milliliter of 2- bromine is added Thiophene reacts 3 hours under 140 degrees Celsius in common oil bath pan.Reaction solution is cooled to room temperature after completing sealing end, by it It is dripped into the vigorously stirred in 100 ml methanols, is filtered after being stirred at room temperature 2 hours up to crude product using glass dropper.It will be thick Product is purified after drying using Soxhlet extractor, is extracted the solvent used and is followed successively by methanol, petroleum ether and chloroform, finally will It is further dropped into 100 ml methanols being vigorously stirred, is filtered up to subject polymer, yield 65% after chloroform portion concentration.

Resulting polymers can normal-temperature dissolution in such as chloroform, tetrahydrofuran, chlorobenzene, o-dichlorohenzene equal solvent.

Embodiment 4

The synthesis of poly- { 2,6- bis- dodecyloxy naphthalene-alt-3,4- difluoro thiophene }, hereinafter referred to as PNaffT.

(1) synthesis of the bis- dodecyloxy naphthalenes of the bromo- 3,7- of 2,6- bis- is referring to embodiment 1；

(2) synthesis of polymer:

In glove box, by step (1) obtained compound (158mg, 0.73mmol), 3,4- bis- fluoro- 2,5- bis- three Methyl tin thiophene (96mg, 1.05equiv. are purchased from Shenzhen Rui Xun Electro-optical Technology, INC. (US) 62 Martin Road, Concord, Massachusetts 017), tetra-triphenylphosphine palladium (12mg, It 0.1equiv.) is added into reaction tube, after putting into a magnetic stir bar, 4 milliliters and 0.8 milliliter nothing of anhydrous dimethyl benzene is added Water n,N-Dimethylformamide is put into common oil bath pan after tube sealing and reacts 2 days in 140 degrees Celsius.After being cooled to room temperature, it is added 0.1 milliliter of 2- bromothiophene reacts 3 hours under 140 degrees Celsius in common oil bath pan.It completes after blocking that reaction solution is cooling To room temperature, it is dripped into the vigorously stirred in 100 ml methanols using glass dropper, is filtered after being stirred at room temperature 2 hours to obtain the final product Crude product.Purified after crude product is dried using Soxhlet extractor, extract the solvent used be followed successively by methanol, petroleum ether and Chloroform is further dropped into 100 ml methanols being vigorously stirred after finally chloroform portion is concentrated, and is filtered up to subject polymer, Yield is 72%, resulting polymers can normal-temperature dissolution in such as chloroform, tetrahydrofuran, chlorobenzene, o-dichlorohenzene equal solvent.

In order to embody superiority of 2, the 6- bis-alkoxy naphthalene monomer relative to 1,5- bis-alkoxy naphthalene monomer, it is also prepared for 1, The copolymer of 5- bis-alkoxy naphthalene and bis- (the 3- hexadecane alkylthrophene -2- base) ethylene of (E) -1,2-, abbreviation PNa (1,5)-ffT.

The preparation method of polymer P Na (1,5)-ffT is similar with PNaffT, yield 79%.

Embodiment 5

The synthesis of poly- { 2,6- bis- bis- (thiophene -2-yl) ethylene of dodecyloxy naphthalene-alt- (E) -1,2- }, hereinafter referred to as PNaTVT, the preparation method is as follows:

(1) synthesis of the bis- dodecyloxy naphthalenes of the bromo- 3,7- of 2,6- bis- is referring to embodiment 1；

(2) synthesis of polymer

In glove box, by step (1) obtained compound (236mg, 0.31mmol), 3,4- bis- fluoro- 2,5- bis- three Methyl tin thiophene (168mg, 1.05equiv are purchased from Shenzhen Rui Xun Electro-optical Technology, INC. (US) 62 Martin Road, Concord, Massachusetts 017), tetra-triphenylphosphine palladium (36mg, It 0.1equiv.) is added into reaction tube, after putting into a magnetic stir bar, 8 milliliters and 1 milliliter of anhydrous dimethyl benzene of addition is anhydrous N,N-Dimethylformamide is put into common oil bath pan after tube sealing and reacts 2 days in 140 degrees Celsius.After being cooled to room temperature, it is added 0.1 milliliter of 2- bromothiophene reacts 3 hours under 140 degrees Celsius in common oil bath pan.It completes after blocking that reaction solution is cooling To room temperature, it is dripped into the vigorously stirred in 100 ml methanols using glass dropper, is filtered after being stirred at room temperature 2 hours to obtain the final product Crude product.Purified after crude product is dried using Soxhlet extractor, extract the solvent used be followed successively by methanol, petroleum ether and Chloroform is further dropped into 100 ml methanols being vigorously stirred after finally chloroform portion is concentrated, and is filtered up to subject polymer, Yield is 79%.Resulting polymers can normal-temperature dissolution in such as chloroform, tetrahydrofuran, chlorobenzene, o-dichlorohenzene equal solvent.

Embodiment 6

The synthesis of poly- { 2,6- bis- bis- (3- cetyl thiophene -2-yl) ethylene of dodecyloxy naphthalene-alt- (E) -1,2- }, Hereinafter referred to as PNaTVTC16, the preparation method is as follows:

(1) synthesis of the bis- dodecyloxy naphthalenes of the bromo- 3,7- of 2,6- bis- is referring to embodiment 1；

(2) synthesis of polymer:

In glove box, by step (1) obtained compound (171mg, 0.22mmol), 3,4- bis- fluoro- 2,5- bis- three Methyl tin thiophene (226mg, 1.05equiv., bibliography S.-Y.Jang, I.-B.Kim, J.Kim, D.Khim, E.Jung, B.Kang, B.Lim, Y.-AKim, Y.H.Jang, K.Cho, D.-Y.Kim, Chem.Mater.2014,26,6907-6910 are closed At), tetra-triphenylphosphine palladium (25mg, 0.1equiv) is added into reaction tube, after putting into a magnetic stir bar, is added anhydrous two 6 milliliters and 0.6 milliliter anhydrous n,N-Dimethylformamide of toluene is put into common oil bath pan after tube sealing and reacts 2 in 140 degrees Celsius It.After being cooled to room temperature, 0.1 milliliter of 2- bromothiophene is added, is reacted 3 hours under 140 degrees Celsius in common oil bath pan.It is complete Reaction solution is cooled to room temperature at after sealing end, it is dripped into the vigorously stirred in 100 ml methanols using glass dropper, room temperature Stirring is filtered after 2 hours up to crude product.It is purified after crude product is dried using Soxhlet extractor, extracts the solvent used It is followed successively by methanol, petroleum ether and chloroform, is further dropped into after finally chloroform portion is concentrated in 100 ml methanols being vigorously stirred, It filters up to subject polymer, yield 84%.Resulting polymers can normal-temperature dissolution such as chloroform, tetrahydrofuran, chlorobenzene, neighbour two In chlorobenzene equal solvent.

Embodiment 7

The spectrum property of polymer P NaT is tested:

The solution and Thin Films UV-vis optical absorption spectra figure of polymer P NaT, as shown in Figure 5.From the figure, it can be seen that The maximum absorption wavelength of polymer in the solution is located at 427 nanometers, and ABSORPTION EDGE is 479 nanometers.When from solution to solid film, The maximum absorption wavelength of the polymer slightly has red shift, about 438 nanometers, and 83 nanometers of red shift, receive up to 521 when ABSORPTION EDGE is compared with solution Rice is piled up more preferable when illustrating the polymer from solution to film.It can be calculated from thin polymer film ABSORPTION EDGE, the polymer Optical band gap be 2.38eV, be not typically to receptor type polymer, institute this is because main polymer chain is electron donor entirely Belong to wide band gap polymer with the polymer.

Embodiment 8

The Ultraviolet visible absorption spectrum figure of polymer P NaffT, as shown in Figure 6.In chloroform, polymer P NaffT is most Big absorbing wavelength is 415 nanometers, 12 nanometers of polymer blue shift relative to non-fluoro.From solution to film, polymer P NaffT Even closer due to piling up, for ABSORPTION EDGE from 465 nanometers of red shifts of solution to 557 nanometers, corresponding optical band gap is 2.22eV.It is poly- Closing object PNaffT and PNaT has duplicate main chain, and the ABSORPTION EDGE of opposite the latter's red shift illustrates, the introducing of fluorine atom by It is acted in F-H or F-S, makes piling up more preferably between strand.

Embodiment 9

Polymer P NaTVT uv-visible absorption spectroscopy figure, as shown in Figure 7.It can be seen from the figure that thiofuran ethylene base Thiophene and 2,6- bis-alkoxy replace the absorption spectrum of naphthalene copolymerization relative to PNaT and PNaffT substantially red shift, film absorption side For 620 nanometers (corresponding optical band gap is 2eV).

Embodiment 10

The uv-visible absorption spectra of polymer P NaTVTC16 such as attached drawing 8.Alkyl is introduced on thiofuran ethylene base thiophene Chain can widen the UV-Visible absorption of polymer.The ABSORPTION EDGE of this polymer is located at 660 nanometers, corresponding optical band gap For 1.88eV.

Embodiment 11

The chemical property of polymer is tested

The electro-chemical test of polymer is tested using Shanghai Chen Hua CHI730E electrochemical workstation.Working electrode is glass carbon Electrode is platinum filament to electrode, and reference electrode is silver/silver chlorate, and electrolyte is that the acetonitrile of the tetrabutyl hexafluoro phosphonic acids amine of 0.1M is molten Liquid, scanning speed 50mV/s.

The cyclic voltammetry curve of polymer P NaTVTC16 is as shown in Figure 9, it can be seen that polymer P NaTVTC16 has one A reversible oxidation peak, after ferrocene is demarcated, calculate the HOMO energy level of the polymer is -5.26eV, the energy of this and gold Grade matching, potential barrier of the hole from electrode injection to polymer are small.The introducing of this explanation 2,6- bis-alkoxy can obtain energy level conjunction Suitable polymer, and can be applied to the organic field-effect tube of transporting holes.

The thermogravimetric curve of polymer P NaTVTC16, as shown in Figure 10.Test carries out under a nitrogen atmosphere, the temperature of test Range is 30 to 600 DEG C.When heating rate is 10 DEG C/min, by thermogravimetric curve it can be found that the corresponding 5% mass damage of polymer Temperature (the T of mistake_d) it is about 376 DEG C.So high decomposition temperature illustrates that polymer has preferable thermal stability, and reply has enough The preparation of field effect transistors and conventional Thermal Annealing processing.

Embodiment 12

The differential calorimetric scan curve of polymer P NaTVTC16 is as shown in figure 11.Test condition is heating under nitrogen atmosphere It is 5 DEG C/min with rate of temperature fall.By curve it is known that polymer is when first time is cooling, 145 DEG C or so to emergencing copolymer The rearrangement of main chain corresponds to the rearrangement of alkyl side chain in 75-40 DEG C of this wide temperature range.It is corresponding with cooling procedure, it can be with The melting of polymer lateral chain is found at 50-80 DEG C, and in the melting of 150-160 DEG C of corresponding main chain.Differential calorimetric scan curve is said Bright polymer can be undergone phase transition by annealing, be conducive to improve carrier mobility.

Embodiment 13

As shown in figure 12, prepared by bottom gate-top contact (BGTC) organic field effect tube device: device is using heavy doping Silicon is as substrate (grid), above through handling one layer of SiO₂As dielectric layer.Successively through acetone, cleaning agent, deionized water and different It is dried in vacuo after propyl alcohol ultrasonic cleaning.Substrate is converted after plasma cleaning to glove box, and octadecyl silicon is used Alkane (OTS) modification.Polymer prepares film by the method for spin coating, and is made annealing treatment at corresponding temperature.By covering Diaphragm plate deposits 30 nanometers of silver as source-drain electrode in high vacuum.The channel length L of device is 60 microns, channel width W It is 3 millimeters.

The test of device is carried out on probe station using Keithley4200 semi-conductor test instrument.Carrier mobility (μ) Pass through formula I_SD=(W/2L) C_iμ(V_G-V_T)²It is calculated, wherein C_iFor dielectric constant (C_i=11nF).The V of device_G-V_TRoot According to itself and I_SDSquare root relationship calculated.

The hole mobility of polymer P NaTVT is about 0.007cm²/ Vs, on-off ratio 10⁵。

The hole mobility of polymer P NaTVTC16 about 0.01cm²/ Vs, on-off ratio 10⁶。

The hole mobility of polymer P NaffT about 0.008cm²/ Vs, on-off ratio 10⁶。

The hole mobility of polymer P Na (1,5) ffT does not measure mobility in identity unit structure.

Embodiment 14

The crystallinity and orientation of thin polymer film can scatter (2D-GIWAXS) Lai Jinhang by two-dimentional wide-angle X-ray Characterization.The two-dimentional wide-angle X-ray scattering (2D-GIWAXS) of polymer is as shown in figure 13, it can be seen that polymer P NaTVT's Main chain has the orientation of stronger side upward, and the main chain crystallization of polymer P NaTVTC16 is slightly weak, upward and up using side Two kinds of mixed-stacking modes, this orientation are conducive to polymer and obtain higher mobility.

Claims (11)

1. a kind of naphthalene polymer containing 2,6- bis-alkoxy shown in formula I,

Wherein, R₁、R₂Respectively alkoxy, R₁、R₂It is identical or different, n=10-1000.

2. polymer according to claim 1, which is characterized in that the alkoxy is selected from:

3. polymer according to claim 1, which is characterized in that the π group is selected from:

Wherein R is hydrotropy group.

4. polymer according to claim 3, which is characterized in that the hydrotropy group is straight chain or branched paraffin, carbon Atom number is 4-24.

5. polymer described in a kind of claim 1, which is characterized in that the polymer is poly- { 2,6- bis- dodecyloxy naphthalenes- Alt- thiophene }, poly- { 2,6- bis- dodecyloxy naphthalene-alt-3,4- difluoro thiophene }, poly- { 2,6- bis- dodecyloxy naphthalene-alt- (E) bis- (thiophene -2-yl) ethylene of -1,2- }, poly- { bis- (the 3- cetyl thiophenes of bis- dodecyloxy naphthalene-alt- (the E) -1,2- of 2,6- Pheno -2-yl) ethylene }.

6. a kind of preparation method of the naphthalene polymer Han 2,6- bis-alkoxy described in claim 1, comprising:

2,6- bis-alkoxy, which will be contained, replaces naphthalene monomer and π unit structure monomer in the presence of catalyst or catalyst and ligand Polycondensation reaction occurs to get the naphthalene polymer containing 2,6- bis-alkoxy.

7. preparation method according to claim 6, which is characterized in that it is described contain 2,6- bis-alkoxy replace naphthalene monomer be

One of；π group monomer are as follows:

In One kind.

8. preparation method according to claim 7, which is characterized in that 2, the 6- bis-alkoxy that contains replaces naphthalene monomer are as follows: Under conditions of inert gas shielding, the item of 3,7- bis- bromo- 2,6- dihydroxy naphthlenes and alkyl bromide in dimethyl sulfoxide and sodium hydroxide It is prepared under part.

9. preparation method according to claim 6, which is characterized in that the polycondensation reaction are as follows: 50-170 DEG C, react 1-72h.

10. preparation method according to claim 6, which is characterized in that sealed at the end of the reaction using capping reagent End.

11. a kind of any naphthalene polymer of bis-alkoxy containing 2,6- the answering in organic field effect tube of Claims 1 to 5 With.