CN105218790B - A kind of preparation method of poly- (the 3 acyl group substituted thiophene) derivative of high regularity headtotail - Google Patents
A kind of preparation method of poly- (the 3 acyl group substituted thiophene) derivative of high regularity headtotail Download PDFInfo
- Publication number
- CN105218790B CN105218790B CN201510707543.1A CN201510707543A CN105218790B CN 105218790 B CN105218790 B CN 105218790B CN 201510707543 A CN201510707543 A CN 201510707543A CN 105218790 B CN105218790 B CN 105218790B
- Authority
- CN
- China
- Prior art keywords
- group
- thiophene
- poly
- substituted
- derivative
- 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.)
- Expired - Fee Related
Links
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
A kind of preparation method of poly- (the 3 acyl group substituted thiophene) derivative of high regularity headtotail; using the thiophene of 3 acyl group substitutions as raw material; direct C H/C H couplings polycondensation prepares three kinds of poly- (3 acyl thiophene) derivatives under palladium chtalyst, and it is as follows that it synthesizes formula：It is an advantage of the invention that：Synthesis step is simple, raw material need not be pre-processed, and reaction condition is gentle, and reaction efficiency is high, and the regularity that poly- (3 acyl thiophene) derivative of preparation is from beginning to end is high.
Description
Technical field
The present invention relates to the preparation method of poly- (3- acyl groups substituted thiophene) derivative, particularly a kind of high regularity phase end to end
Connect the preparation method of poly- (3- acyl groups substituted thiophene) derivative.
Background technology
Poly- (3- substituted thiophenes) (P3RT) because of its excellent photoelectric property, good stability, dissolubility and electric conductivity with
And the features such as solution processable, it has been widely used in organic photovoltaic battery (OPV), Organic Light Emitting Diode (OLED), organic
The various light-sensitive device fields such as field-effect transistor (OFET) and chemical/biological sensors.Substantial amounts of research has shown that：Influence
One central factor of P3RT photoelectric properties is exactly the stereoregularity of its polymer, and the P3RT of stereoregularity is with more excellent
Different photoelectric properties, and it is still a problem so far to prepare the P3RT with good area regularity.This is primarily due to 3-
The thiophene monomer itself of position substitution has asymmetric feature, and the polymerisation of thiophene is commonly taken place in thiphene ring more
Active 2,5- positions, therefore necessarily cause the different connection side of following four occur in the polymer of thiophene monomer coupling generation
Formula, it is as follows：
If the 2- positions of thiphene ring are regarded as " head " (Head), if 5- regards position " tail " (Tail) as, then this four
The different connected mode of kind can be briefly referred to as：End to end-be end-to-end (i.e. HT-HT), head-be end-to-end (i.e. HH-HT),
Tail tail-be end-to-end (TT-HT) connects (TT-HH) with tail tail-head.In random P3RT, due to head, the bonded mode of tail tail
Space torsion is obstructed between making thiphene ring, have impact on the coplanarity of polymer, and then hinders the tightly packed of material, so as to
The energy gap of material is set to broaden, electrical conductivity reduces.And the connecting mode end to end in isotactic P3RT makes between its repeat unit
Steric hindrance is smaller, is easy to plane configuration presence, and this makes its effective conjugate length increase, and mobility improves, and band-gap energy reduces,
Spectral red shift.
In order to prepare the P3RT of regioregular, people have done substantial amounts of research work, the main conjunction reported at present
It is as described below into method：1) Fe (III) oxidation synthesis：This is commonly used preparation method, although this method synthetic route
Simply, the advantage such as mild condition, higher to the instrument and equipment low, yield of requirement and molecular weight, but this method poor reproducibility, per a collection of
Secondary sample has very big difference, and the P3RT synthesized regularity is not high, the problem of iron ion residual also be present.Especially need
It is pointed out that：The thiophene monomer that this polymerization is connected with drawing electron group to 3- positions does not apply to.2) Suzuki methods, Stille
The coupling polymerization methods such as method, McCullough methods, Rieke methods, GRIM methods and direct arylation method.These methods need system in advance
Standby corresponding metallo-organic compound or halogenated hydrocarbons, monomer synthesis harsh (such as low temperature, anaerobic), step be more, it is time-consuming, into
This height, and some organometallic monomers are extremely unstable is not easily-synthesized, polymer subsequently also be present needs to block and heavy metal-polluted
The problems such as dye.In addition, P3RT derivatives its substituent prepared by these methods be mainly butyl, hexyl, octyl group, dodecyl,
The electron-donating groups such as cyclohexyl, phenyl, alkoxy, alkylthio group, and 3- positions using drawing electron group as substituent research relatively
Few, the P3RT derivatives containing ester group, imines etc. reported at present mainly use Suzuki and Stille coupling polymerization methods.Cause
This, breaks the limitation of monomer selection, development green, polymerization efficiently, inexpensive, prepares 3- positions and be connected with drawing electron group
The P3RT derivatives of high regularity be still urgent.
The content of the invention
The purpose of the present invention is problem be present for above-mentioned, there is provided a kind of high regularity headtotail is poly-, and (3- acyl groups substitute
Thiophene) derivative preparation method, this method is based on palladium chtalyst oxidation C-H/C-H coupling condensation methods and prepares, have succinct, high
The features such as imitating, be environment-friendly, advantageously reduces production cost and technology difficulty.
Technical scheme：
A kind of preparation method of poly- (the 3- acyl groups substituted thiophene) derivative of high regularity headtotail, substituted with 3- positions acyl group
Thiophene be raw material, under palladium chtalyst direct C-H/C-H coupling polycondensation prepare three kinds of poly- (3- acyl thiophenes) derivatives, it is synthesized
Formula is as follows：
Wherein：R1And R2For H, C1-C30Alkyl, C1-C30Alkyl substituent, C3-C30Cycloalkyl, C3-C30Cycloalkyl substitutes
Base, C1-C30Alkoxy, C1-C30Alkylthio group, C1-C30Alkylamino radical, halo C1-C30Alkyl, halo C3-C30Cycloalkyl, halo C1-
C30Alkoxy or halo C1-C30Alkylthio group, and R1With R2It can be the same or different；Alkyl group is substitution or unsubstituted,
When alkyl group is substituted, substituted radical be cycloalkyl, aryl, heteroaryl, heteroalicyclyl, hydroxyl, alkoxy, alkylamino radical,
Aryloxy group, sulfydryl, alkylthio group, arylthio, cyano group, halo, carbonyl, thiocarbonyl, O- carbamoyls, N- carbamoyls,
O- thiocarbamoyls, N- thiocarbamoyls, C- acylamino-s, N- acylamino-s, S- sulfonamidos, N- sulfenyl ammonia
Base, C- carboxyls, O- carboxyls, isocyanato-, thiocyano, isothiocyanato, nitro, silicyl, three halide sulphonyl
Base ,-NR ' R " or the amino including single- and di- substituted amino group and its protected derivative；Group of naphthene base
For substitution or unsubstituted, when group of naphthene base is substituted, substituted radical is cycloalkyl, aryl, heteroaryl, heteroalicyclyl, hydroxyl
Base, alkoxy, aryloxy group, sulfydryl, alkylthio group, arylthio, cyano group, halo, carbonyl, thiocarbonyl, O- carbamoyls, N- ammonia
Base formoxyl, O- thiocarbamoyls, N- thiocarbamoyls, C- acylamino-s, N- acylamino-s, S- sulfonamidos, N-
Sulfonamido, C- carboxyls, O- carboxyls, isocyanato-, thiocyano, isothiocyanato, nitro, silicyl, three halos
Methane sulfonyl ,-NR ' R " or the amino including single- and di- substituted amino group and its protected derivative；X can
For sulphur, nitrogen, oxygen or selenium atom；Specific preparation process is as follows：
1) thiophene, palladium catalyst, oxidant, alkali, additive and the solvent substituted 3- positions acyl group is added in reaction vessel,
24-72 hours are reacted at a temperature of 100-150 DEG C under nitrogen protection, obtain reaction solution；
2) above-mentioned reaction solution is cooled to after room temperature and poured into methanol, use filter cake successively using apparatus,Soxhlet's after suction filtration
Methanol, n-hexane extraction, remaining solid use chloroform recovery, collect chloroform extracted solution again；
3) above-mentioned chloroform extracted solution is concentrated into 1st/50th of original volume, concentrate is cooled to after room temperature and directly dripped
Enter in methanol, the volume ratio of concentrate and methanol is 1：30, staticly settle, solution filters after becoming clarification, and filter cake is in 60 DEG C of vacuum
12h is dried in drying box, obtained solid powder is poly- (the 3- acyl groups substituted thiophene) derivative of high regularity headtotail.
The palladium catalyst is Pd (dppf) Cl2、Pd(OAc)2、PdCl2、PdCl2(MeCN)2、PdCl2(PhCN)2、Pd
(OPiv)2、Pd2(dba)3、Pd(TFA)2、PdCl2(PPh3)2、Pd(OH)2、Pd(PPh3)4, Pd/C and trans-bis- (μ-acetic acid)
The mixture of one or both of double [2- (di-o-tolyl phosphine) benzyl] two palladiums (II) any of the above ratio；The oxidant
For Ag2CO3、AgF、AgOAc、AgOTf、Ag2O、AgBF4、Cu(OAc)2、Cu(OTf)2、CuCl2, BQ (1,4-benzoquinone), K2S2O8With
The mixture of one or both of TBHP (tertbutanol peroxide) any of the above ratio；The alkali is Li2CO3、Na2CO3、
K2CO3、Cs2CO3、NaHCO3、NaOAc、KOAc、CsOAc、K2HPO4、K3PO4、CsOPiv、KF、NEt3One or both of with
The mixture of upper arbitrary proportion；The additive is PPh3、PCy3、P(t-Bu)3, three (o-methoxyphenyl) phosphines, three (it is adjacent (N,
TMSDMA N dimethylamine base) phenyl) phosphine, three (p-methylphenyl) phosphines, tri-butyl phosphine borofluoride, tricyclohexyl phosphine borofluoride,
PivOH (neopentanoic acid), TFA, HOAc, PTSA (p-methyl benzenesulfonic acid), adamantane acid, TBAB and cetyl trimethyl
The mixture of one or both of ammonium bromide any of the above ratio；The solvent is toluene, Isosorbide-5-Nitrae-dioxane, adjacent diformazan
One in benzene, dimethylbenzene, tetrahydrofuran, N, N- dimethyl acetamide, N, dinethylformamide and METHYLPYRROLIDONE
The mixture of kind or two or more arbitrary proportions.
The thiophene of 3- positions acyl group substitution, palladium catalyst, oxidant, alkali, the mol ratio of additive are 1 in the reaction solution：
(0-20)：(0-10)：(0-10)：(0-10), the concentration of the thiophene of 3- positions acyl group substitution is 0.01-1mol/L in reaction solution.
It is an advantage of the invention that：Compared with prior art route, the present invention have the characteristics that it is succinct, efficient, environment-friendly,
Advantageously reduce production cost and technology difficulty.It is in particular in：
1) raw material is simple and easy to get needed for, and this patent need not pre-process to raw material, can directly be polymerize, and passes
Metal stannide, boride or halides will typically be prepared by synthesizing such compound in system route；
2) avoid using to the reagent (such as n-BuLi) of air-sensitive, toxic metals reagent and the poisonous pair of generation
Product etc.；Especially can drawing electron group in compatible conventional method, these groups are to adjusting and carrying high molecular material property
With potential important value；
3) this method reaction does not need termination process after terminating, and this is simpler than the post processing of other polymerizations, contributes to big
The big performance for improving material；
4) regularity of poly- (3- substitutions) thiophene prepared by this patent is higher, and up to 90%, this is to material photoelectric properties
Raising has important value.
Brief description of the drawings
Fig. 1 is polymer prepared by embodiment 11H NMR。
Fig. 2 is solution, the normalized ultraviolet-visible absorption spectroscopy of film of polymer prepared by embodiment 1.
Fig. 3 is solution, the normalized fluorescence emission spectrum of film of polymer prepared by embodiment 1.
Fig. 4 is the thermogravimetric curve of polymer prepared by embodiment 1.
Fig. 5 is the electrochemistry CV curves of polymer prepared by embodiment 1.
Fig. 6 is the GPC test curves of polymer prepared by embodiment 1.
Embodiment
With reference to embodiment, the invention will be further described, it will help the understanding of the present invention.But simultaneously
The interest field of the present invention can not be limited with this, and the interest field of the present invention should be defined by what claims illustrated.
Embodiment 1：
A kind of preparation method of poly- (the 3- acyl groups substituted thiophene) derivative of high regularity headtotail, the high regularity head
The connect structural formula of poly- (3- acyl groups substituted thiophene) derivative of tail is
In structural formula：R1For H, R2For OC8H17, X S,
Specific preparation process is as follows：
1) by 300mg thenoic acids monooctyl ester (1.25mmol), 46mg [double (diphenylphosphino) ferrocene of 1,1'-] two
Palladium bichloride, 688mg silver carbonates (2.5mmol), 257mg potassium acetates (2.62mmol) and 5mL volume ratios are 1:1 N, N- dimethyl
Acetamide-tetrahydrofuran mixed solvent is added in reaction vessel, at 110 DEG C under nitrogen protection, at a temperature of react 72 hours, obtain
Reaction solution；
2) above-mentioned reaction solution is cooled to after room temperature and poured into 100mL methanol, filter cake is utilized into apparatus,Soxhlet's after suction filtration
Extracted successively with methanol, n-hexane, remaining solid uses chloroform recovery again, collects chloroform extracted solution；
3) above-mentioned chloroform extracted solution is concentrated into 1st/50th of original volume, concentrate is cooled to after room temperature and directly dripped
Enter in methanol, the volume ratio of concentrate and methanol is 1：30, staticly settle, solution filters after becoming clarification, and filter cake is in 60 DEG C of vacuum
12h is dried in drying box, obtained solid powder is poly- (thenoic acid monooctyl ester) derivative of high regularity headtotail
0.24g, yield 80%, Mn=7000Da, Mw/Mn=1.71, HT=90.1%.(deuterochloroform is molten to proton nmr spectra
Agent, BrukerAMX-400 types NMR)1H NMR(400MHz,CDCl3)：δ7.89(dd,1H),4.31(d,2H),1.76
(s,2H),1.26(d,13H),0.88(s,3H).
Fig. 1 is the polymer prepared1HNMR, show in figure：1HNMR(400MHz,CDCl3)：δ7.89(dd,1H),
4.31(d,2H),1.76(s,2H),1.26(d,13H),0.88(s,3H)。
Fig. 6 is the GPC test curves of the polymer prepared, is shown in figure：Mn=7000Da, Mw/Mn=1.71.
Obtained polymer is dissolved in chloroform, is configured to 1.0 × 10-5The solution of mol/L concentration, takes 2.5mL to put
Enter in quartz colorimetric utensil, determine UV-visible-near infrared absorption (UV-vis-NIR spectrometers, the JASCO V- of solution
570) λ, is measuredmax=426nm.
Obtained polymer is dissolved in chloroform, is configured to the concentrated solution of 3~5mg/mL concentration, takes 2~3 to drop in
Clean Quartz glass surfaces, film in uniform thickness is obtained by spin-coating instrument.The ultraviolet-visible of measure film-near red
Outer absorption spectrum (UV-vis-NIR spectrometers, JASCO V-570), measures λmax=478nm.
Fig. 2 is solution, the normalized ultraviolet-visible absorption spectroscopy of film of the polymer prepared, is shown in figure：Target
The maximal ultraviolet of polymer solution-Visible-to-Near InfaRed absorption spectrum wavelength is λmax=426nm, the maximum of subject polymer film
UV-visible-near infrared absorption wavelength is λmax=478nm.
Obtained polymer is dissolved in chloroform, is configured to 1.0 × 10-5The solution of mol/L concentration, takes 2.5mL to put
Enter in quartz colorimetric utensil, determine the fluorescence spectrum (fluorophotometric instrument, F4600) of solution, set excitation wavelength as 430nm, measure
Maximum emission wavelength is λmax=558nm.
Obtained subject polymer is dissolved in chloroform, is configured to the concentrated solution of 3~5mg/mL concentration, takes 2~3 drops
Clean Quartz glass surfaces are dropped in, film in uniform thickness is obtained by spin-coating instrument.The fluorescence spectrum for determining film is (glimmering
Light photometer, F4600), excitation wavelength is set as 520nm, and it is λ to measure maximum emission wavelengthmax=633nm.
Fig. 3 is solution, the normalized fluorescence emission spectrum of film of the polymer prepared, is shown in figure：Target polymerization
The maximum emission wavelength of thing solution is λmax=558nm, the maximum emission wavelength of subject polymer film is λmax=633nm.
Obtained polymer is subjected to TGA/DTG thermogravimetric analysis on thermogravimetric analyzer (TA2910, DuPont, USA), adopted
Protected with nitrogen, programming rate is 10 DEG C/min.
Fig. 4 is the thermogravimetric curve of the polymer prepared, is shown in figure：Temperature during weightlessness 5% is 377 DEG C.
Obtained polymer is carried out to the test of electrochemical properties in LK98B II electrochemical workstations, electrolytic cell is three electricity
Polar body system (glass-carbon electrode is working electrode, and platinum electrode is auxiliary electrode, and calomel electrode is reference electrode), done with ferrocene interior
Mark (4.8eV below vacuum level), dried acetonitrile is solvent, 0.1M tetrabutyl ammonium hexafluorophosphate (n-Bu4NPF6) it is branch
Electrolyte is held, sweep speed is 100mV s-1.The reduction peak initial value position -0.955eV of subject polymer, is interior using ferrocene
Mark, the energy level for obtaining LUMO is respectively -3.84eV, oxidation peak initial value position -1.4eV, using ferrocene as internal standard, obtains HOMO's
Energy level is respectively -6.2eV, according to Еg=EHOMO-ELUMO(eV) Е, is obtainedg cv=2.35eV.
Fig. 5 is the electrochemistry CV curves of the polymer prepared, is shown in figure：The reduction peak initial value position of subject polymer-
0.955eV, oxidation peak initial value position -1.4eV.
Embodiment 2：
A kind of preparation method of poly- (the 3- acyl groups substituted thiophene) derivative of high regularity headtotail, the high regularity head
The connect structural formula of poly- (3- acyl groups substituted thiophene) derivative of tail is
In structural formula：R1For H, R2For OC8H17, X S.
Specific preparation process is as follows：
1) by thenoic acid monooctyl ester (100mg, 0.42mmol), tetrakis triphenylphosphine palladium (24mg), silver carbonate (232mg,
0.84mmol), potassium acetate (82mg, 0.84mmol) and DMAc solvents (2mL) are added in reaction vessel, 110 under nitrogen protection
DEG C, at a temperature of react 72 hours, obtain reaction solution；
2) above-mentioned reaction solution is cooled to after room temperature and poured into 100mL methanol, filter cake is utilized into apparatus,Soxhlet's after suction filtration
Extracted successively with methanol, n-hexane, remaining solid uses chloroform recovery again, collects chloroform extracted solution；
3) above-mentioned chloroform extracted solution is concentrated into 1st/50th of original volume, concentrate is cooled to after room temperature and directly dripped
Enter in methanol, the volume ratio of concentrate and methanol is 1：30, staticly settle, solution filters after becoming clarification, and filter cake is in 60 DEG C of vacuum
12h is dried in drying box, obtained solid powder is poly- (thenoic acid monooctyl ester) the derivative 85mg of high regularity headtotail,
Yield is 85%, Mn=17300Da, Mw/Mn=3.45, HT=81%.Proton nmr spectra (deuterochloroform is solvent,
BrukerAMX-400 types NMR)1H NMR(400MHz,CDCl3)：δ7.89(dd,1H),4.31(d,2H),1.76(s,
2H),1.26(d,13H),0.88(s,3H).
The testing result of the polymer of preparation and embodiment 1 are similar.
Embodiment 3：
A kind of preparation method of poly- (the 3- acyl groups substituted thiophene) derivative of high regularity headtotail, the high regularity head
The connect structural formula of poly- (3- acyl groups substituted thiophene) derivative of tail is
In structural formula：R1For H, R2For OC8H17, X S.
Specific preparation process is as follows：
1) by thenoic acid monooctyl ester (50mg, 0.21mmol), the double [2- (di-o-tolyl phosphine) of trans-bis- (μ-acetic acid)
Benzyl] two palladiums (II) (3.9mg), silver carbonate (114mg, 0.42mmol), potassium acetate (41mg, 0.42mmol), triphenyl phosphorus
(22mg, 0.08mmol) and DMAc solvents (2mL) are added in reaction vessel, at 110 DEG C under nitrogen protection, at a temperature of reaction it is 72 small
When, obtain reaction solution；
2) above-mentioned reaction solution is cooled to after room temperature and poured into 100mL methanol, filter cake is utilized into apparatus,Soxhlet's after suction filtration
Extracted successively with methanol, n-hexane, remaining solid uses chloroform recovery again, collects chloroform extracted solution；
3) above-mentioned chloroform extracted solution is concentrated into 1st/50th of original volume, concentrate is cooled to after room temperature and directly dripped
Enter in methanol, the volume ratio of concentrate and methanol is 1：30, staticly settle, solution filters after becoming clarification, and filter cake is in 60 DEG C of vacuum
12h is dried in drying box, obtained solid powder is poly- (thenoic acid monooctyl ester) the derivative 31mg of high regularity headtotail,
Yield is 62%, Mn=12100Da, Mw/Mn=2.00, HT=62%.Proton nmr spectra (deuterochloroform is solvent,
BrukerAMX-400 types NMR)1H NMR(400MHz,CDCl3)：δ7.89(dd,1H),4.31(d,2H),1.76(s,
2H),1.26(d,13H),0.88(s,3H).
The testing result of the polymer of preparation and embodiment 1 are similar.
Embodiment 4：
A kind of preparation method of poly- (the 3- acyl groups substituted thiophene) derivative of high regularity headtotail, the high regularity head
The connect structural formula of poly- (3- acyl groups substituted thiophene) derivative of tail is
In structural formula：R1For H, R2For OC6H11(cyclohexyloxy), X S.
Specific preparation process is as follows：
1) by thenoic acid cyclohexyl ester (300mg, 1.43mmol), Pd (dppf) Cl2(58mg), silver carbonate
(786mg, 2.85mmol), potassium acetate (280mg, 2.85mmol) and DMAc solvents (5mL) are added in reaction vessel, nitrogen protection
Under at 110 DEG C, at a temperature of react 72 hours, obtain reaction solution；
2) above-mentioned reaction solution is cooled to after room temperature and poured into 100mL methanol, filter cake is utilized into apparatus,Soxhlet's after suction filtration
Extracted successively with methanol, n-hexane, remaining solid uses chloroform recovery again, collects chloroform extracted solution；
3) above-mentioned chloroform extracted solution is concentrated into 1st/50th of original volume, concentrate is cooled to after room temperature and directly dripped
Enter in methanol, the volume ratio of concentrate and methanol is 1：30, staticly settle, solution filters after becoming clarification, and filter cake is in 60 DEG C of vacuum
12h is dried in drying box, obtained solid powder is poly- (thenoic acid cyclohexyl ester) derivative of high regularity headtotail
0.18g, yield 60%, Mn=5200Da, Mw/Mn=1.46, HT=91%.Proton nmr spectra (deuterochloroform is solvent,
Bruker AMX-400 types NMR)1H NMR(400MHz,CDCl3)：δ7.73(dd,1H),4.93(s,1H),1.88
(s,2H),1.67(s,2H),1.48(s,7H).
The testing result of the polymer of preparation and embodiment 1 are similar.
Embodiment 5：
A kind of preparation method of poly- (the 3- acyl groups substituted thiophene) derivative of high regularity headtotail, the high regularity head
The connect structural formula of poly- (3- acyl groups substituted thiophene) derivative of tail is
In structural formula：R1For H, R2For NHC8H17, X S.
Specific preparation process is as follows：
1) by thenoic acid caprylamide (300mg, 1.25mmol), tetrakis triphenylphosphine palladium (144mg), silver carbonate
(688mg, 2.5mmol), potassium acetate (257mg, 2.62mmol) and DMAc solvents (5mL) are added in reaction vessel, nitrogen protection
Under at 110 DEG C, at a temperature of react 72 hours, obtain reaction solution；
2) above-mentioned reaction solution is cooled to after room temperature and poured into 100mL methanol, filter cake is utilized into apparatus,Soxhlet's after suction filtration
Extracted successively with methanol, n-hexane, remaining solid uses chloroform recovery again, collects chloroform extracted solution；
3) above-mentioned chloroform extracted solution is concentrated into 1st/50th of original volume, concentrate is cooled to after room temperature and directly dripped
Enter in methanol, the volume ratio of concentrate and methanol is 1：30, staticly settle, solution filters after becoming clarification, and filter cake is in 60 DEG C of vacuum
12h is dried in drying box, obtained solid powder is poly- (thenoic acid caprylamide) derivative of high regularity headtotail
0.06g, yield 20%, Mn=5200Da, Mw/Mn=1.53, HT=75%.Proton nmr spectra (deuterochloroform is solvent,
BrukerAMX-400 types NMR)1H NMR(400MHz,CDCl3)δ7.91(s,1H),3.30(d,2H),1.30(s,
12H),0.90(s,3H).
The testing result of the polymer of preparation and embodiment 1 are similar.
Embodiment 6：
A kind of preparation method of poly- (the 3- acyl groups substituted thiophene) derivative of high regularity headtotail, the high regularity head
The connect structural formula of poly- (3- acyl groups substituted thiophene) derivative of tail is
In structural formula：R1For CO2C8H17、R2For OC8H17, X S.
Specific preparation process is as follows：
1) by 3,4- thiophenedicarboxylic acids monooctyl ester (200mg, 0.5mmol), tetrakis triphenylphosphine palladium (20mg), silver carbonate
(278mg, 1.0mmol) and DMAc solvents (5mL) are added in reaction vessel, at 110 DEG C under nitrogen protection, at a temperature of reaction it is 72 small
When, obtain reaction solution；
2) above-mentioned reaction solution is cooled to after room temperature and poured into 100mL methanol, filter cake is utilized into apparatus,Soxhlet's after suction filtration
Extracted successively with methanol, n-hexane, remaining solid uses chloroform recovery again, collects chloroform extracted solution；
3) above-mentioned chloroform extracted solution is concentrated into 1st/50th of original volume, concentrate is cooled to after room temperature and directly dripped
Enter in methanol, the volume ratio of concentrate and methanol is 1：30, staticly settle, solution filters after becoming clarification, and filter cake is in 60 DEG C of vacuum
12h is dried in drying box, obtained solid powder is poly- (3, the 4- thiophenedicarboxylic acid monooctyl ester) derivative of high regularity headtotail
0.001g, yield 5%, Mn=1100Da, Mw/Mn=1.00, (deuterochloroform is solvent to proton nmr spectra, BrukerAMX-
400 type NMRs)1H NMR(400MHz,CDCl3) δ 3.30 (d, J=100.4Hz, 4H), 1.30 (s, 24H), 0.90 (s,
6H).
From the foregoing it is appreciated that although describing specific embodiments of the present invention for the purpose of exemplary illustration,
But under condit without departing from the spirit and scope of the present invention, technical staff described in this area can make various modifications or change
Enter.These deformations or modification should all fall into the application scope of the following claims.
Claims (2)
- A kind of 1. preparation method of poly- (the 3- acyl groups substituted thiophene) derivative of high regularity headtotail, it is characterised in that：With 3- The thiophene of position acyl group substitution is raw material, and direct C-H/C-H coupling polycondensation preparations three kinds poly- (3- acyl thiophenes) are spread out under palladium chtalyst Biology, it is as follows that it synthesizes formula：Wherein：R1And R2For H, C1-C30Alkyl, C3-C30Cycloalkyl, C1-C30Alkoxy, C1-C30Alkylthio group, C1-C30Alkylamino radical, Halo C1-C30Alkyl, halo C3-C30Cycloalkyl, halo C1-C30Alkoxy or halo C1-C30Alkylthio group, and R1With R2Can phase Together can also be different；Alkyl group can be substituted or unsubstituted, and when substituted, substituted radical is selected from following groups：Ring Alkyl, aryl, heteroaryl, heteroalicyclyl, hydroxyl, alkoxy, alkylamino radical, aryloxy group, sulfydryl, alkylthio group, arylthio, cyano group, Halo, carbonyl, thiocarbonyl, O- carbamoyls, N- carbamoyls, O- thiocarbamoyls, N- thiocarbamoyls Base, C- acylamino-s, N- acylamino-s, S- sulfonamidos, N- sulfonamidos, C- carboxyls, O- carboxyls, isocyanato-, cyanogen sulphur Ammonia including base, isothiocyanato, nitro, silicyl, three halide sulfonyls, single- and di- substituted amino group Base；Group of naphthene base can be any substitution, also as substituted or unsubstituted, and when substituted, substituted radical is selected from down Row group：Cycloalkyl, aryl, heteroaryl, heteroalicyclyl, hydroxyl, alkoxy, aryloxy group, sulfydryl, alkylthio group, arylthio, cyanogen Base, halo, carbonyl, thiocarbonyl, O- carbamoyls, N- carbamoyls, O- thiocarbamoyls, N- sulfo-amino first Acyl group, C- acylamino-s, N- acylamino-s, S- sulfonamidos, N- sulfonamidos, C- carboxyls, O- carboxyls, isocyanato-, cyanogen Including sulfenyl, isothiocyanato, nitro, silicyl, three halide sulfonyls, single- and di- substituted amino group Amino；X is sulphur atom；Specific preparation process is as follows：1) thiophene, palladium catalyst, oxidant, alkali, additive and the solvent substituted 3- positions acyl group is added in reaction vessel, nitrogen 24-72 hours are reacted under protection at a temperature of 100-150 DEG C, obtain reaction solution；2) above-mentioned reaction solution is cooled to after room temperature and poured into methanol, filter cake is used into first successively using apparatus,Soxhlet's after suction filtration Alcohol, n-hexane extraction, remaining solid use chloroform recovery, collect chloroform extracted solution again；3) above-mentioned chloroform extracted solution is concentrated into 1st/50th of original volume, first is directly instilled after concentrate is cooled into room temperature In alcohol, the volume ratio of concentrate and methanol is 1：30, staticly settle, solution filters after becoming clarification, and filter cake is in 60 DEG C of vacuum drying 12h is dried in case, obtained solid powder is poly- (the 3- acyl groups substituted thiophene) derivative of high regularity headtotail；The palladium catalyst is Pd (dppf) Cl2、Pd(OAc)2、PdCl2、PdCl2(MeCN)2、PdCl2(PhCN)2、Pd (OPiv)2、Pd2(dba)3、Pd(TFA)2、PdCl2(PPh3)2、Pd(OH)2、Pd(PPh3)4, Pd/C and trans-bis- (μ-acetic acid) The mixture of one or both of double [2- (di-o-tolyl phosphine) benzyl] two palladiums (II) any of the above ratio；The oxidant For Ag2CO3、AgF、AgOAc、AgOTf、Ag2O、AgBF4、Cu(OAc)2、Cu(OTf)2、CuCl2, BQ (1,4-benzoquinone), K2S2O8With The mixture of one or both of TBHP (tertbutanol peroxide) any of the above ratio；The alkali is Li2CO3、Na2CO3、 K2CO3、Cs2CO3、NaHCO3、NaOAc、KOAc、CsOAc、K2HPO4、K3PO4、CsOPiv、KF、NEt3One or both of with The mixture of upper arbitrary proportion；The additive is PPh3、PCy3、P(t-Bu)3, three (o-methoxyphenyl) phosphines, three (it is adjacent (N, TMSDMA N dimethylamine base) phenyl) phosphine, three (p-methylphenyl) phosphines, tri-butyl phosphine borofluoride, tricyclohexyl phosphine borofluoride, PivOH (neopentanoic acid), TFA, HOAc, PTSA (p-methyl benzenesulfonic acid), adamantane acid, TBAB and cetyl trimethyl The mixture of one or both of ammonium bromide any of the above ratio；The solvent be toluene, Isosorbide-5-Nitrae-dioxane, dimethylbenzene, One or both of tetrahydrofuran, N, N- dimethyl acetamide, N, dinethylformamide and METHYLPYRROLIDONE with The mixture of upper arbitrary proportion.
- 2. the preparation method of poly- (the 3- acyl groups substituted thiophene) derivative of high regularity headtotail according to claim 1, its It is characterised by：The thiophene of 3- positions acyl group substitution, palladium catalyst, oxidant, alkali, the mol ratio of additive are 1 in the reaction solution： (0-20)：(0-10)：(0-10)：(0-10), wherein palladium catalyst, oxidant, alkali and additive are not all 0；3- in reaction solution The concentration of the thiophene of position acyl group substitution is 0.01-1mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510707543.1A CN105218790B (en) | 2015-10-27 | 2015-10-27 | A kind of preparation method of poly- (the 3 acyl group substituted thiophene) derivative of high regularity headtotail |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510707543.1A CN105218790B (en) | 2015-10-27 | 2015-10-27 | A kind of preparation method of poly- (the 3 acyl group substituted thiophene) derivative of high regularity headtotail |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105218790A CN105218790A (en) | 2016-01-06 |
| CN105218790B true CN105218790B (en) | 2018-02-06 |
Family
ID=54988109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510707543.1A Expired - Fee Related CN105218790B (en) | 2015-10-27 | 2015-10-27 | A kind of preparation method of poly- (the 3 acyl group substituted thiophene) derivative of high regularity headtotail |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105218790B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565940A (en) * | 2016-10-10 | 2017-04-19 | 天津理工大学 | Method for preparing high-regularity head-to-tail polythiophene derivatives |
| CN112794992B (en) * | 2021-01-07 | 2023-02-03 | 天津理工大学 | Method for efficiently preparing polythiophene derivative by using microwave technology |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693707A (en) * | 2009-10-26 | 2010-04-14 | 江苏工业学院 | Process for preparing stereoregular thiophene oligomers |
| CN102786669A (en) * | 2012-07-30 | 2012-11-21 | 常州大学 | Polymer semi-conductor material, preparation method and application thereof |
| CN102850340A (en) * | 2011-06-28 | 2013-01-02 | 中国科学院上海有机化学研究所 | Conjugated polymer or oligomer having narrow band gap characteristic and side chain stereoregularity, and its preparation method |
| CN103025789A (en) * | 2010-07-26 | 2013-04-03 | 综研化学株式会社 | Polythiophene polymerization catalyst, and method for producing poly(substituted thiophene) |
-
2015
- 2015-10-27 CN CN201510707543.1A patent/CN105218790B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693707A (en) * | 2009-10-26 | 2010-04-14 | 江苏工业学院 | Process for preparing stereoregular thiophene oligomers |
| CN103025789A (en) * | 2010-07-26 | 2013-04-03 | 综研化学株式会社 | Polythiophene polymerization catalyst, and method for producing poly(substituted thiophene) |
| CN102850340A (en) * | 2011-06-28 | 2013-01-02 | 中国科学院上海有机化学研究所 | Conjugated polymer or oligomer having narrow band gap characteristic and side chain stereoregularity, and its preparation method |
| CN102786669A (en) * | 2012-07-30 | 2012-11-21 | 常州大学 | Polymer semi-conductor material, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105218790A (en) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zotti et al. | Novel, highly conducting, and soluble polymers from anodic coupling of alkyl-substituted cyclopentadithiophene monomers | |
| WO2021037278A1 (en) | A-d-a conjugated molecule, preparation method therefor, use thereof in organic solar cell, and organic solar cell | |
| CN114605620B (en) | Electrochromic polymer, preparation method thereof and electrochromic film | |
| CN114907551B (en) | Red electrochromic polymer, preparation method, film and device | |
| CN105315273A (en) | Polyceptor-structure small molecule compound and preparing method and application thereof | |
| Jähnert et al. | Synthesis and Charge–Discharge Studies of Poly (ethynylphenyl) galvinoxyles and Their Use in Organic Radical Batteries with Aqueous Electrolytes | |
| Pirotte et al. | Molecular weight tuning of low bandgap polymers by continuous flow chemistry: increasing the applicability of PffBT4T for organic photovoltaics | |
| CN110092891B (en) | Thienothiophene electrochromic polymer and preparation method thereof | |
| Barik et al. | Conjugated thiophenoazomethines: electrochromic materials exhibiting visible-to-near-IR color changes | |
| CN105218790B (en) | A kind of preparation method of poly- (the 3 acyl group substituted thiophene) derivative of high regularity headtotail | |
| CN102936245B (en) | Prepared by photoelectric material | |
| CN114853988B (en) | Electrochromic polymer containing thiophene embedded units, preparation method, film and device | |
| CN112500557A (en) | Asymmetric donor-acceptor-donor electrochromic polymer based on 5-fluoro-2, 1, 3-benzothiadiazole and application thereof | |
| CN103012751B (en) | Preparation method of bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer | |
| CN114014873B (en) | C2 v-based symmetrical aza-condensed ring compound and preparation method and application thereof | |
| Kaya et al. | Syntheses of poly (phenoxy-imine) s anchored with carboxyl group: Characterization and photovoltaic studies | |
| CN106008582A (en) | Fluorene and carbazole bridging-based A-D-A type double-center BODIPY (boron-dipyrrolemethene) derivative and preparation method for same | |
| CN116874744A (en) | Water-alcohol-soluble electrochromic polymer and preparation method and application thereof | |
| CN113549169A (en) | Phenylfluorenamine polymer hole transport material and preparation method and application thereof | |
| CN109651378B (en) | Micromolecule containing heptatomic ring diimide, derivative, preparation method and application thereof | |
| CN107721906A (en) | Preparation of novel solution-processable 9, 9-diaryl fluorene tripolymer hole transport material and application thereof in perovskite solar cell | |
| CN102492118A (en) | Ethylenedioxothiophene-and-naphthalene-tetracarboxylic-acid-bisimide-structural-unit-based low band gap polymers, and preparation method and application method thereof | |
| Wang et al. | Tunable molecular weights of poly (triphenylamine‐2, 2′‐bithiophene) and their effects on photovoltaic performance as sensitizers for dye‐sensitized solar cells | |
| CN111454245B (en) | Tetramine pyrene electropolymerization hole transport material and application thereof in perovskite solar cell | |
| CN110982047B (en) | Indacarbazine difuranyl organic solar cell donor material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180206 Termination date: 20181027 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |