CN1989169A - Polymer compound, polymer film and polymer film element using the same - Google Patents

Polymer compound, polymer film and polymer film element using the same Download PDF

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CN1989169A
CN1989169A CNA2005800251032A CN200580025103A CN1989169A CN 1989169 A CN1989169 A CN 1989169A CN A2005800251032 A CNA2005800251032 A CN A2005800251032A CN 200580025103 A CN200580025103 A CN 200580025103A CN 1989169 A CN1989169 A CN 1989169A
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amino
macromolecular compound
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CN1989169B (en
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上田将人
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Sumitomo Chemical Co Ltd
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Abstract

A polymeric compound which comprises repeating units represented by the following formula (1) and repeating units represented by the formula (2) and has a number-average molecular weight, in terms of polystyrene, of 10<3>-10<8>, in the formula (1) and (2), Ar<1> and Ar<2> each independently represents a trivalent aromatic hydrocarbon group or trivalent heterocyclic group; X<1> and X<2> each independently represents O, S, C(=O), S(=O), SO2, etc., provided that X<1> is different from X<2>; Y represents O or S; R<9> represents halogeno, alkyl, alkyloxy, etc.; m is 0 or 1; n is an integer of to 6; o is an integer of 1 to 6; and p is an integer of 0 to 2.

Description

Macromolecular compound, macromolecule membrane and used its macromolecule membrane element
Technical field
The present invention relates to macromolecular compound, comprise the macromolecule membrane of this macromolecular compound and used the macromolecule membrane element of this macromolecule membrane.
Background technology
The film that comprises the organic materials with electron-transporting or hole transport ability, expectation is used in thin-film components such as OTFT, organic photovoltaic cell, has carried out various researchs.
As the material that is used for such film, for main chain has the macromolecular compound of the molecular structure of electron-transporting or hole transport ability, (Appl.Phys.Lett.Vol.49 (1986) p.1210 for known polyphenylene vinylene derivative, poly-fluorene derivatives, polyphenylene derivative, polythiofuran derivative, poly-inferior thienyl vinylidene derivative etc.; Appl.Phys.Lett.Vol.63 (1993) p.1372; Appl.Phys.Lett.Vol.77 (2000) p.406; " Semiconducting Polymers ", Eds.G.Hadziioannou and P.F.van Hutten (2000) Wiley-VCH).
Summary of the invention
The object of the present invention is to provide the useful novel macromolecular compound of using as macromolecule membrane elements such as OTFT, organic solar batteries of thin-film material.
That is, the invention provides following macromolecular compound: contain the repeating unit shown in repeating unit shown in the following formula (1) and the formula (2), the number-average molecular weight of polystyrene conversion is 10 3～10 8
Figure A20058002510300051
[in the formula, Ar 1And Ar 2Represent the aromatic hydrocarbyl of 3 valencys or the heterocyclic radical of 3 valencys independently of one another, X 1And X 2Represent independently of one another O, S, C (=O), S (=O), SO 2, C (R 1) (R 2), Si (R 3) (R 4), N (R 5), B (R 6), P (R 7) or P (=O) (R 8), R 1～R 8Represent hydrogen atom independently of one another; halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; aralkyl; aralkoxy; aromatic alkylthio; acyl group; acyloxy; amido; acylimino; the imines residue; amino; substituted-amino; replace silyl; replace siloxy-; replace silylthio-; replace silyl amino; the heterocyclic radical of 1 valency; heteroaryloxy; heteroarylthio; aryl alkenyl; the aryl ethane base; carboxyl; carbalkoxy; aryloxy carbonyl; aralkoxycarbonyl; assorted aryloxy carbonyl or cyano group.But, X 1And X 2Different.C (R 1) (R 2) in R 1And R 2, Si (R 3) (R 4) in R 3And R 4Can mutually combine and form ring.M represents 0 or 1, and n represents 1～6 integer.But, during m=0, X 1Do not represent C (R 1) (R 2).In addition, X 1And Ar 2Respectively with formation Ar 1The carbon atom of aromatic nucleus in the adjacent carbon atom ortho position of aromatic nucleus (below be sometimes referred to as) combination, during m=1, X 2With Ar 1Be attached to Ar 2The ortho position of aromatic nucleus, during m=0, X 1With Ar 1Be attached to Ar 2The ortho position of aromatic nucleus].
Figure A20058002510300061
[in the formula, o represents 1～10 integer, and p represents 0～2 integer, and Y represents O, S, C (R 10) (R 11), Si (R 12) (R 13) or N (R 14), R 10, R 11, R 12, R 13And R 14Represent hydrogen atom independently of one another; halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; aralkyl; aralkoxy; aromatic alkylthio; acyl group; acyloxy; amido; acylimino; the imines residue; amino; substituted-amino; replace silyl; replace siloxy-; replace silylthio-; replace silyl amino; the heterocyclic radical of 1 valency; heteroaryloxy; heteroarylthio; aryl alkenyl; the aryl ethane base; carboxyl; carbalkoxy; aryloxy carbonyl; aralkoxycarbonyl; assorted aryloxy carbonyl or cyano group.R 10And R 11, R 12And R 13Can mutually combine and form ring.R 9The expression halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; aralkyl; aralkoxy; aromatic alkylthio; acyl group; acyloxy; amido; acylimino; the imines residue; amino; substituted-amino; replace silyl; replace siloxy-; replace silylthio-; replace silyl amino; the heterocyclic radical of 1 valency; heteroaryloxy; heteroarylthio; aryl alkenyl; the aryl ethane base; carboxyl; carbalkoxy; aryloxy carbonyl; aralkoxycarbonyl; assorted aryloxy carbonyl or cyano group.A plurality of R are arranged 9The time, they can be the same or different, in addition, and R 9Between can mutually combine and form ring].
In addition, the invention provides following macromolecular compound: contain the repeating unit shown in repeating unit shown in the repeating unit shown in the above-mentioned formula (1), the above-mentioned formula (2) and the following formula (3), the number-average molecular weight of polystyrene conversion is 10 3～10 8
[in the formula, Ar 3The heterocyclic radical of aromatic hydrocarbyl, the divalent of expression divalent or-CR 15=CR 16-.R 15And R 16Represent hydrogen atom independently of one another; halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; aralkyl; aralkoxy; aromatic alkylthio; acyl group; acyloxy; amido; acylimino; the imines residue; amino; substituted-amino; replace silyl; replace siloxy-; replace silylthio-; replace silyl amino; the heterocyclic radical of 1 valency; heteroaryloxy; heteroarylthio; aryl alkenyl; the aryl ethane base; carboxyl; carbalkoxy; aryloxy carbonyl; aralkoxycarbonyl; assorted aryloxy carbonyl or cyano group.Q represents 1～6 integer].
Description of drawings
Fig. 1 is the fragmentary cross sectional view of suitable Stagger type OTFT involved in the present invention.
Fig. 2 is the fragmentary cross sectional view of suitable Stagger apsacline OTFT involved in the present invention.
Fig. 3 is the fragmentary cross sectional view of contrary Stagger type OTFT involved in the present invention.
Fig. 4 is the fragmentary cross sectional view of contrary Stagger apsacline OTFT involved in the present invention.
Fig. 5 is the fragmentary cross sectional view of solar cell involved in the present invention.
Fig. 6 is the fragmentary cross sectional view of cascade type optical sensor involved in the present invention.
Fig. 7 is the fragmentary cross sectional view of cascade type optical sensor involved in the present invention.
Fig. 8 is the fragmentary cross sectional view of single-layer type optical sensor involved in the present invention.
Fig. 9 is the fragmentary cross sectional view of mono-layer electronic photographic photoreceptor involved in the present invention.
Figure 10 is the fragmentary cross sectional view of laminated electronic photosensitive body involved in the present invention.
Figure 11 is the fragmentary cross sectional view of laminated electronic photosensitive body involved in the present invention.
Figure 12 is the fragmentary cross sectional view of spatial optical modulation element involved in the present invention.
Nomenclature
1, base material
2, macromolecule membrane
3, insulating film
4, gate electrode
5, source electrode
6, drain electrode
7, electrode
8, charge generating layer
9, liquid crystal layer
10, dielectric somascope layer
Embodiment
Macromolecular compound of the present invention contains the repeating unit shown in repeating unit shown in the above-mentioned formula (1) and the above-mentioned formula (2).And then macromolecular compound of the present invention contains the repeating unit shown in repeating unit shown in the repeating unit shown in the above-mentioned formula (1), the above-mentioned formula (2) and the above-mentioned formula (3).
In the above-mentioned formula (1), Ar 1And Ar 2Represent the aromatic hydrocarbyl of 3 valencys or the heterocyclic radical of 3 valencys independently of one another.
Wherein, the aromatic hydrocarbyl of so-called 3 valencys is meant from phenyl ring or fused rings to get on except 3 hydrogen atoms and remaining atomic group is generally carbon number 6～60, and is preferred 6～20, can enumerate following radicals.Wherein most preferably get on except 3 hydrogen atoms and remaining atomic group from phenyl ring.Moreover, can have substituting group on the aromatic hydrocarbyl.The carbon number of the aromatic hydrocarbyl of 3 valencys does not comprise substituent carbon number.
Figure A20058002510300081
Figure A20058002510300091
In addition, the heterocyclic radical of so-called 3 valencys is meant and has removed 3 hydrogen atoms and remaining atomic group from heterogeneous ring compound that carbon number is generally 4～60, preferred 4～20.Moreover, can have substituting group on the heterocyclic radical, the carbon number of heterocyclic radical does not comprise substituent carbon number.
Here said heterogeneous ring compound is meant in the organic compound with ring type structure, and the element that constitutes ring is not a carbon atom, also contains heteroatomic compounds such as aerobic, sulphur, nitrogen, phosphorus, boron, silicon in the ring.
As the heterocyclic radical of 3 valencys, can enumerate for example following group.
Figure A20058002510300121
In the above-mentioned formula, R ' represents the heterocyclic radical or the cyano group of hydrogen atom, halogen atom, alkyl, alkoxyl group, alkylthio, alkylamino, aryl, aryloxy, arylthio, arylamino, aralkyl, aralkoxy, aromatic alkylthio, aryl-alkyl amino, acyloxy, amido, aryl alkenyl, aromatic yl polysulfide yl, 1 valency independently of one another.Heterocyclic radical, heteroaryloxy, the heteroarylthio of R ' ' expression hydrogen atom, alkyl, aryl, arylalkyl, replacement silyl, acyl group or 1 valency.
The substituting group that can have on the heterocyclic radical as the aromatic hydrocarbyl of 3 valencys or 3 valencys can be enumerated halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; aralkyl; aralkoxy; aromatic alkylthio; acyl group; acyloxy; amido; acylimino; the imines residue; amino; substituted-amino; replace silyl; replace siloxy-; replace silylthio-; replace silyl amino; the heterocyclic radical of 1 valency; heteroaryloxy; heteroarylthio; aryl alkenyl; the aryl ethane base; carboxyl; carbalkoxy; aryloxy carbonyl; aralkoxycarbonyl; assorted aryloxy carbonyl or cyano group.When having a plurality of substituting group, can form ring between the substituting group.
In the above-mentioned formula, X 1And X 2Represent independently of one another O, S, C (=O), S (=O), SO 2, C (R 1) (R 2), Si (R 3) (R 4), N (R 5), B (R 6), P (R 7) or P (=O) (R 8).But, X 1And X 2Different.
In the formula (1), R 1～R 8Represent hydrogen atom independently of one another; halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; aralkyl; aralkoxy; aromatic alkylthio; acyl group; acyloxy; amido; acylimino; the imines residue; amino; substituted-amino; replace silyl; replace siloxy-; replace silylthio-; replace silyl amino; the heterocyclic radical of 1 valency; heteroaryloxy; heteroarylthio; aryl alkenyl; the aryl ethane base; carboxyl; carbalkoxy; aryloxy carbonyl; aralkoxycarbonyl; assorted aryloxy carbonyl or cyano group.
C (R 1) (R 2) in R 1And R 2, Si (R 3) (R 4) in R 3And R 4Can mutually combine and form ring.In this case, as the ring structure part, can the following structure of particular instantiation.
In addition, during m=0, X 1Do not represent C (R 1) (R 2).
In the above-mentioned formula (1), n represents 1～6 integer, more preferably 1～3 integer, further preferred 1～2 integer.
In the above-mentioned formula (1), m represents 0 or 1, as OTFT with material etc., preferred m=1, preferred especially n=1 and m=1.
Wherein, the X of formula (1) 2Be preferably C (R 1) (R 2), Si (R 3) (R 4), N (R 5), B (R 6), P (R 7) or P (O) (R 8), C (R more preferably 1) (R 2).(in the formula, R 1～R 8Represent implication same as described above independently of one another).
In addition, the X of formula (1) 1Be preferably O, S, C (=O), S (O), SO 2, Si (R 3) (R 4), N (R 5), B (R 6), P (R 7) or P (=O) (R 8), more preferably O, S, C (=O), S (O) or SO 2, be preferably O or S especially.
During m=1, as-X 1-X 2-, can enumerate the group shown in following (4), (5), (6).
Figure A20058002510300151
Wherein, from the viewpoint of the stability of compound, the group of preferred (5), (6) formula, the more preferably group of (6) formula.
Macromolecular compound of the present invention also contains the repeating unit of formula (2) except the repeating unit of above-mentioned formula (1).
Figure A20058002510300171
In the formula (2), o represents 1～10 integer, more preferably 1～6 integer, further preferred 1～5 integer.
In the above-mentioned formula (2), p represents 0～2 integer.O is 2 when following, preferred p=0 or 1, further preferred p=0.O is 3 when above, from deliquescent viewpoint, preferred a plurality of 5 yuan of rings be p=1 or 2 more than 1.
In the above-mentioned formula (2), Y represents O, S, C (R 10) (R 11), Si (R 12) (R 13), N (R 14), preferred O, S, more preferably S.
In addition, R 10～R 14Represent hydrogen atom independently of one another; halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; aralkyl; aralkoxy; aromatic alkylthio; acyl group; acyloxy; amido; acylimino; the imines residue; amino; substituted-amino; replace silyl; replace siloxy-; replace silylthio-; replace silyl amino; the heterocyclic radical of 1 valency; heteroaryloxy; heteroarylthio; aryl alkenyl; the aryl ethane base; carboxyl; carbalkoxy; aryloxy carbonyl; aralkoxycarbonyl; assorted aryloxy carbonyl or cyano group.
In the above-mentioned formula (2), R 9The expression halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; aralkyl; aralkoxy; aromatic alkylthio; acyl group; acyloxy; amido; acylimino; the imines residue; amino; substituted-amino; replace silyl; replace siloxy-; replace silylthio-; replace silyl amino; the heterocyclic radical of 1 valency; heteroaryloxy; heteroarylthio; aryl alkenyl; the aryl ethane base; carboxyl; carbalkoxy; aryloxy carbonyl; aralkoxycarbonyl; assorted aryloxy carbonyl or cyano group; be preferably halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; aralkyl; aralkoxy; aromatic alkylthio; alkyl more preferably; alkoxyl group is as a plurality of R 9The time, they can be the same or different, in addition, and R 9Between can mutually combine and form ring.
Work as R 9Between mutually combine and form when ring, as the ring structure part, can the following structure of particular instantiation.
Figure A20058002510300181
Macromolecular compound of the present invention except the repeating unit of the repeating unit of above-mentioned formula (1) and above-mentioned formula (2), can also contain the repeating unit of formula (3).
In the formula (3), Ar 3The heterocyclic radical of aromatic hydrocarbyl, the divalent of expression divalent or-CR 15=CR 16-, be preferably divalent heterocyclic radical ,-CR 15=CR 16-, more preferably-CR 15=CR 16-.
Wherein, the aromatic hydrocarbyl of so-called divalent, be meant from phenyl ring or fused rings to get on except 2 hydrogen atoms and remaining atomic group, be generally carbon number 6～60, be preferably 6～20, can be set forth in the group that on arbitrary position of having removed 3 hydrogen atoms, has added 1 hydrogen atom in the aromatic hydrocarbyl of above-mentioned illustrative 3 valencys.Wherein, most preferably get on except 2 hydrogen atoms and remaining atomic group from phenyl ring.Moreover, can have substituting group on the aromatic hydrocarbyl.The carbon number of the aromatic hydrocarbyl of divalent does not comprise substituent carbon number.
In addition, the heterocyclic radical of so-called divalent is meant and has removed 2 hydrogen atoms and remaining atomic group from heterogeneous ring compound that carbon number is generally 4～60, is preferably 4～20.As the heterocyclic radical of divalent, can be set forth in the group that on arbitrary position of having removed 3 hydrogen atoms, has added 1 hydrogen atom in the heterocyclic radical of above-mentioned illustrative 3 valencys.Moreover, can have substituting group on the heterocyclic radical, the carbon number of heterocyclic radical does not comprise substituent carbon number.
In the above-mentioned formula (3), R 15And R 16Represent hydrogen atom independently of one another; halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; aralkyl; aralkoxy; aromatic alkylthio; acyl group; acyloxy; amido; acylimino; the imines residue; amino; substituted-amino; replace silyl; replace siloxy-; replace silylthio-; replace silyl amino; the heterocyclic radical of 1 valency; heteroaryloxy; heteroarylthio; aryl alkenyl; the aryl ethane base; carboxyl; carbalkoxy; aryloxy carbonyl; aralkoxycarbonyl; assorted aryloxy carbonyl or cyano group.
In the formula (3), q represents 1～6 integer, more preferably 1～3 integer, further preferred 1～2 integer.
In macromolecular compound of the present invention,, preferably have formula (1) and formula (2) bonded structure (7) from improving the viewpoint of electron-transporting or hole transport ability.
Figure A20058002510300191
In macromolecular compound of the present invention, when except the repeating unit of the repeating unit of above-mentioned formula (1) and above-mentioned formula (2), also containing the repeating unit of above-mentioned formula (3), can contain the repeating unit of a plurality of formulas (2).When containing the repeating unit of a plurality of formulas (2), they can be the same or different.From improving the viewpoint of electron-transporting or hole transport ability, preferably have formula (1) and formula (2) and formula (3) bonded structure (8).
Wherein, Y ', R 9', o ', p ' expression with above-mentioned Y, R 9, implication that o, p are identical, Y, R 9, o, p can be the same or different.
As the example of structure shown in the above-mentioned formula (7), can illustration for example make n=1; O=2,3 or 5; Also has substituent structure on structure shown in formula (9)～(14) below during Y=S and aromatic hydrocarbons in these structures or the heterocyclic radical.In addition, as the example of structure shown in the above-mentioned formula (8), can enumerate and for example make n=1; O=1; O '=1; Q=1; Y=S; Also has substituent structure on structure shown in following formula (15)～(17) and aromatic hydrocarbyl in these structures or the heterocyclic radical during Y '=S.
Figure A20058002510300201
Figure A20058002510300251
Figure A20058002510300261
Figure A20058002510300271
(in the formula, R 1～R 9, R 15And R 16Expression implication as hereinbefore.R 1'～R 4' expression and above-mentioned R 1～R 4Identical implication).
Wherein, also have substituent group on group shown in preferred formula (9), formula (14), formula (15), the formula (17) and these aromatic hydrocarbyl or the heterocycle, further also have substituent group on the group shown in preferred formula (9), the formula (15) and these aromatic hydrocarbyl or the heterocycle.As substituting group; can enumerate halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; aralkyl; aralkoxy; aromatic alkylthio; acyl group; acyloxy; amido; acylimino; the imines residue; amino; substituted-amino; replace silyl; replace siloxy-; replace silylthio-; replace silyl amino; the heterocyclic radical of 1 valency; heteroaryloxy; heteroarylthio; aryl alkenyl; the aryl ethane base; carboxyl; carbalkoxy; aryloxy carbonyl; aralkoxycarbonyl; assorted aryloxy carbonyl or cyano group can mutually combine between the substituting group and forms ring.
In above-mentioned formula (1), formula (2) or formula (3),, can enumerate fluorine, chlorine, bromine, iodine as halogen atom.
Alkyl can be that straight chain, branch or cyclic are any, can have substituting group, carbon number is generally about 1～20, as its concrete example, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, cyclohexyl, heptyl, octyl group, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyl octyl group, lauryl, trifluoromethyl, pentafluoroethyl group, perfluoro butyl, perfluoro hexyl, perfluoro capryl etc.
Alkoxyl group can be a straight chain, branch or cyclic are any, can have substituting group, carbon number is generally about 1～20, as its concrete example, can enumerate methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, tert.-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptan the oxygen base, octyloxy, the 2-ethyl hexyl oxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, 3,7-dimethyl octyloxy, bay oxygen base, trifluoromethoxy, five fluorine oxyethyl groups, the perfluor butoxy, the perfluor hexyloxy, the perfluor octyloxy, methoxymethoxy, 2-methoxy ethoxy etc.
Alkylthio can be that straight chain, branch or cyclic are any, can have substituting group, carbon number is generally about 1～20, as its concrete example, can enumerate methylthio group, ethylmercapto group, rosickyite base, iprotiazem base, butylthio, isobutyl sulfenyl, uncle's butylthio, penta sulfenyl, own sulfenyl, hexamethylene sulfenyl, heptan sulfenyl, hot sulfenyl, the own sulfenyl of 2-ethyl, ninth of the ten Heavenly Stems sulfenyl, last of the ten Heavenly stems sulfenyl, 3,7-dimethyl-octa sulfenyl, bay sulfenyl, trifluoromethylthio etc.
Aryl can have substituting group, and carbon number is generally about 3～60, as its concrete example, can enumerate phenyl, C 1～C 12Alkoxyl phenyl (C 1～C 12The expression carbon number is 1～12.C below too), 1～C 12Alkyl phenyl, 1-naphthyl, 2-naphthyl, pentafluorophenyl group, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, triazinyl etc.
Aryloxy can have substituting group on aromatic nucleus, carbon number is generally about 3～60, as its concrete example, can enumerate phenoxy group, C 1～C 12Alkoxyl group phenoxy group, C 1～C 12Alkyl phenoxy, 1-naphthyloxy, 2-naphthyloxy, penta fluoro benzene oxygen base, pyridyloxy, pyridazine oxygen base, 2-pyrimidinyl oxy, pyrazine oxygen base, triazine oxy etc.
Arylthio can have substituting group on aromatic nucleus, carbon number is generally about 3～60, as its concrete example, can enumerate thiophenyl, C 1～C 12Alkoxy benzene sulfenyl, C 1～C 12Alkyl sulfur-base, 1-naphthalene sulfenyl, 2-naphthalene sulfenyl, penta fluoro benzene sulfenyl, pyridine sulfenyl, pyridazine sulfenyl, pyrimidine sulfenyl, pyrazine sulfenyl, triazine sulfenyl etc.
Aralkyl can have substituting group, and carbon number is generally about 7～60, as its concrete example, can enumerate phenyl-C 1～C 12Alkyl, C 1～C 12Alkoxyl phenyl-C 1～C 12Alkyl, C 1～C 12Alkyl phenyl-C 1～C 12Alkyl, 1-naphthyl-C 1～C 12Alkyl, 2-naphthyl-C 1～C 12Alkyl etc.
Aralkoxy can have substituting group, and carbon number is generally about 7～60, as its concrete example, can enumerate phenyl-C 1～C 12Alkoxyl group, C 1～C 12Alkoxyl phenyl-C 1～C 12Alkoxyl group, C 1～C 12Alkyl phenyl-C 1～C 12Alkoxyl group, 1-naphthyl-C 1～C 12Alkoxyl group, 2-naphthyl-C 1～C 12Alkoxyl group etc.
Aromatic alkylthio can have substituting group, and carbon number is generally about 7～60, as its concrete example, can enumerate phenyl-C 1～C 12Alkylthio, C 1～C 12Alkoxyl phenyl-C 1～C 12Alkylthio, C 1～C 12Alkyl phenyl-C 1～C 12Alkylthio, 1-naphthyl-C 1～C 12Alkylthio, 2-naphthyl-C 1～C 12Alkylthio etc.
The carbon number of acyl group is generally about 2～20, as its concrete example, can enumerate ethanoyl, propionyl, butyryl radicals, isobutyryl, pivaloyl, benzoyl, trifluoroacetyl group, penta fluoro benzene formyl radical etc.
The carbon number of acyloxy is generally about 2～20, as its concrete example, can enumerate acetoxyl group, propionyloxy, butyryl acyloxy, isobutyl acyloxy, trimethyl acetoxyl, benzoyloxy, trifluoroacetyl oxygen base, penta fluoro benzene methanoyl etc.
The carbon number of amido is generally about 2～20, be preferably carbon number 2～18, as its concrete example, can enumerate formamido group, kharophen, propionamido, butyrylamino, benzamido, trifluoroacetamido, penta fluoro benzene formamido group, two (formyl) amino, two (acetyl) amino, two (propionyl) amino, two (butyryl) amino, two (benzoyls) amino, two (trifluoroacetyls) amino, two (penta fluoro benzene formyl) amino etc.
As acylimino, can enumerate and from imide, remove the residue that obtains with its nitrogen-atoms bonded hydrogen atom, be generally carbon number about 2～60, be preferably 2～48.Specifically can enumerate group shown below.
As the imines residue, be meant from group with imine moiety (to be meant that intramolecularly has-organic compound of N=C-.As its example, can enumerate hydrogen atom on aldimine, ketoimine and their N by the compound of replacements such as alkyl) in removed the residue of 1 hydrogen atom, be generally carbon number about 2～20, be preferably carbon number 2～18.Specifically can enumerate the group shown in the following structural formula etc.
Figure A20058002510300302
As substituted-amino, can enumerate amino with 1 or 2 group replacement of the heterocyclic radical that is selected from alkyl, aryl, aralkyl and 1 valency, the heterocyclic radical of this alkyl, aryl, aralkyl or 1 valency can have substituting group.The carbon number of substituted-amino is generally about 1～40, as its concrete example, can enumerate methylamino, dimethylamino, ethylamino, diethylamino, propyl group amino, dipropyl amino, sec.-propyl amino, diisopropylaminoethyl, butyl amino, isobutylamino, tertiary butyl amino, amyl group amino, hexyl amino, cyclohexyl amino, heptyl amino, octyl group amino, 2-ethylhexyl amino, nonyl amino, decyl amino, 3,7-dimethyl octyl group amino, lauryl amino, cyclopentyl amino, two cyclopentyl amino, cyclohexyl amino, dicyclohexyl amino, pyrrolidyl, piperidyl, two (trifluoromethyl) amino, phenyl amino, diphenyl amino, C 1～C 12Alkoxyl phenyl amino, two (C 1～C 12Alkoxyl phenyl) amino, two (C 1～C 12Alkyl phenyl) amino, 1-naphthyl amino, 2-naphthyl amino, pentafluorophenyl group amino, pyridinylamino, pyridazinyl amino, pyrimidinyl-amino, pyrazinyl amino, triazine radical amido, phenyl-C 1～C 12Alkylamino, C 1～C 12Alkoxyl phenyl-C 1～C 12Alkylamino, C 1～C 12Alkyl phenyl-C 1～C 12Alkylamino, two (C 1～C 12Alkoxyl phenyl-C 1～C 12Alkyl) amino, two (C 1～C 12Alkyl phenyl-C 1～C 12Alkyl) amino, 1-naphthyl-C 1～C 12Alkylamino, 2-naphthyl-C 1～C 12Alkylamino etc.
As replacing silyl, can enumerate silyl with 1,2 or 3 group replacement of the heterocyclic radical that is selected from alkyl, aryl, aralkyl or 1 valency, carbon number is generally about 1～60, is preferably carbon number 3～48.Moreover the heterocyclic radical of this alkyl, aryl, aralkyl or 1 valency can have substituting group.
Particularly, can enumerate trimethyl silyl, triethylsilyl, the tripropyl silyl, the triisopropyl silyl, dimethyl sec.-propyl silyl, diethyl sec.-propyl silyl, tertiary butyl silyl dimetylsilyl, the amyl group dimetylsilyl, the hexyl dimetylsilyl, the heptyl dimetylsilyl, the octyldimethyl silyl, 2-ethylhexyl-dimetylsilyl, the nonyl dimetylsilyl, the decyl dimetylsilyl, 3,7-dimethyl octyl group-dimetylsilyl, the lauryl dimethyl silyl, phenyl-C 1～C 12Alkyl silyl, C 1～C 12Alkoxyl phenyl-C 1～C 12Alkyl silyl, C 1～C 12Alkyl phenyl-C 1～C 12Alkyl silyl, 1-naphthyl-C 1～C 12Alkyl silyl, 2-naphthyl-C 1～C 12Alkyl silyl, phenyl-C 1～C 12Alkyl dimethyl silyl, triphenyl silyl, three (p-Xylol base) silyl, tribenzyl silyl, diphenyl methyl silyl, t-butyldiphenylsilyl, 3,5-dimethylphenyl silyl etc.
As replacing siloxy-, can enumerate siloxy-(H with 1,2 or 3 group replacement of the heterocyclic radical that is selected from alkyl, aryl, aralkyl and 1 valency 3SiO-).Moreover the heterocyclic radical of this alkyl, aryl, aralkyl or 1 valency can have substituting group.
The carbon number that replaces siloxy-is generally about 1～60, be preferably carbon number 3～30, as its concrete example, can enumerate trimethylsiloxy, silicoheptane alcoxyl base, three n-propyl siloxyies, triisopropyl siloxy-, tertiary butyl silyl dimethylsilane oxygen base, triphenyl siloxy-, three (p-Xylol base) siloxy-, tribenzyl siloxy-, diphenyl methyl siloxy-, tert-butyl diphenyl siloxy-, 3,5-dimethylphenyl siloxy-etc.
As replacing silylthio-, can enumerate silylthio-(H with 1,2 or 3 group replacement of the heterocyclic radical that is selected from alkyl, aryl, aralkyl and 1 valency 3SiS-).Moreover the heterocyclic radical of this alkyl, aryl, aralkyl or 1 valency can have substituting group.
The carbon number that replaces silylthio-is generally about 1～60, be preferably carbon number 3～30, as its concrete example, can enumerate trimethyl silyl sulfenyl, silicoheptane alkylthio, three n-propyl silylthio-s, triisopropyl silylthio-, tertiary butyl silyl dimethylsilane sulfenyl, triphenyl silylthio-, three (p-Xylol base) silylthio-, tribenzyl silylthio-, diphenyl methyl silylthio-, tert-butyl diphenyl silylthio-, 3,5-dimethylphenyl silylthio-etc.
As replacing silyl amino, can enumerate silyl amino (H with 1～6 group replacement of the heterocyclic radical that is selected from alkyl, aryl, aralkyl and 1 valency 3SiNH-or (H 3Si) 2N-).Moreover the heterocyclic radical of this alkyl, aryl, aralkyl, 1 valency can have substituting group.
The carbon number that replaces silyl amino is generally about 1～120, be preferably carbon number 3～60, as its concrete example, can enumerate trimethyl silyl amino, triethylsilyl amino, three n-propyl silyl amino, triisopropyl silyl amino, tertiary butyl silyl dimetylsilyl amino, triphenyl silyl amino, three (p-Xylol base) silyl amino, tribenzyl silyl amino, diphenyl methyl silyl amino, t-butyldiphenylsilyl amino, 3,5-dimethylphenyl silyl amino, two (trimethyl silyl) amino, two (triethylsilyl) amino, two (three n-propyl silyls) amino, two (triisopropyl silyl) amino, two (tertiary butyl silyl dimetylsilyl) amino, two (triphenyl silyl) amino, two (three (p-Xylol base) silyl) amino, two (tribenzyl silyl) amino, two (diphenyl methyl silyl) amino, two (t-butyldiphenylsilyl) amino, two (3,5-dimethylphenyl silyl) amino etc.
The heterocyclic radical of so-called 1 valency is meant and has removed 1 hydrogen atom and remaining atomic group from heterogeneous ring compound that carbon number is generally about 4～60, as its concrete example, can enumerate thienyl, C 1～C 12Alkylthrophene base, pyrryl, furyl, pyridyl, C 1～C 12Alkylpyridyl, imidazolyl, pyrazolyl, triazolyl, oxazolyl, thiazolyl, thiadiazolyl group etc.
As heteroaryloxy (Q 1Group shown in the-O-, Q 1The heterocyclic radical of representing 1 valency), heteroarylthio (Q 2Group shown in the-S-, Q 2The heterocyclic radical of representing 1 valency), assorted aryloxy carbonyl (Q 3-O (C=O)-shown in group, Q 3The heterocyclic radical of 1 valency the heterocyclic radical of representing 1 valency) can be enumerated illustrative group in the heterocyclic radical of above-mentioned 1 valency.
For example, the carbon number of heteroaryloxy is generally about 4～60, as its concrete example, can enumerate thiophene oxy, C 1～C 12Alkylthrophene oxygen base, pyrroles's oxygen base, furans oxygen base, pyridyloxy, C 1～C 12Alkyl pyridine oxygen base, imidazoles oxygen base, pyrazoles oxygen base, triazole oxygen Ji, oxazole oxygen base, thiazole oxygen base, thiadiazoles oxygen base etc.
The carbon number of heteroarylthio is generally about 4～60, as its concrete example, can enumerate thiophene sulfydryl, C 1～C 12Alkylthrophene sulfydryl, pyrroles's sulfydryl, furans sulfydryl, pyridine sulfydryl, C 1～C 12Alkyl pyridine sulfydryl, imidazoles sulfydryl, pyrazoles sulfydryl, triazole sulfydryl, oxazole sulfydryl, thiazole sulfydryl, thiadiazoles sulfydryl etc.
The carbon number of aryl alkenyl is generally about 8～50, and as the aryl in the aryl alkenyl, thiazolinyl, aryl, the thiazolinyl with above-mentioned record is identical respectively.As its concrete example, can enumerate 1-aryl vinyl, 2-aryl vinyl, 1-aryl-1-propenyl, 2-aryl-1-propenyl, 2-aryl-2-propenyl, 3-aryl-2-propenyl etc.In addition, also comprise aryl alkadienyls such as 4-aryl 1,3-butadiene base.
The carbon number of aryl ethane base is generally about 8～50, as the aryl in the aromatic yl polysulfide yl, can enumerate above-mentioned aryl.
The carbon number of carbalkoxy is generally about 2～20, as its concrete example, can enumerate methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, isopropoxy carbonyl, butoxy carbonyl, isobutoxy carbonyl, tert-butoxycarbonyl, benzyloxycarbonyl, hexyloxy carbonyl, cyclohexyloxy carbonyl, heptan oxygen base carbonyl, carbonyl octyloxy, 2-ethyl hexyl oxy carbonyl, the ninth of the ten Heavenly Stems oxygen base carbonyl, the last of the ten Heavenly stems oxygen base carbonyl, 3,7-dimethyl carbonyl octyloxy, bay oxygen base carbonyl, the trifluoromethoxy carbonyl, five fluorine ethoxy carbonyls, the perfluor butoxy carbonyl, the perfluor hexyloxy carbonyl, perfluor carbonyl octyloxy etc.
The carbon number of aryloxy carbonyl is generally about 7～60, as its concrete example, can enumerate phenyloxycarbonyl, C 1～C 12Alkoxyl group phenyloxycarbonyl, C 1～C 12Alkyl phenoxy carbonyl, 1-naphthyloxy carbonyl, 2-naphthyloxy carbonyl, penta fluoro benzene oxygen base carbonyl etc.
The carbon number of aralkoxycarbonyl is generally about 8～60, as its concrete example, can enumerate phenyl-C 1～C 12Alkoxy carbonyl, C 1～C 12Alkoxyl phenyl-C 1～C 12Alkoxy carbonyl, C 1～C 12Alkyl phenyl-C 1～C 12Alkoxy carbonyl, 1-naphthyl-C 1～C 12Alkoxy carbonyl, 2-naphthyl-C 1～C 12Alkoxy carbonyl etc.
Assorted aryloxy carbonyl (Q 4-O (C=O)-shown in group, Q 4The heterocyclic radical of representing 1 valency) carbon number is generally about 2～60, specifically can enumerate thiophene oxy carbonyl, C 1～C 12Alkylthrophene oxygen base carbonyl, pyrroles's oxygen base carbonyl, furans oxygen base carbonyl, pyridyloxy carbonyl, C 1～C 12Alkyl pyridine oxygen base carbonyl, imidazoles oxygen base carbonyl, pyrazoles oxygen base carbonyl, triazole oxygen base carbonyl, oxazole oxygen base carbonyl, thiazole oxygen base carbonyl, thiadiazoles oxygen base carbonyl etc.
Macromolecular compound of the present invention can contain above-mentioned formula (1), formula (2) or the formula (3) more than 2 kinds respectively.
Macromolecular compound of the present invention can contain formula (1), formula (2) and formula (3) repeating unit in addition in the scope of not damaging electron transport property or hole transport characteristic.In addition, the total of the repeating unit shown in the total of the repeating unit shown in formula (1), the formula (2) or formula (1), formula (2) and the formula (3) is preferably 10 moles of whole repeating units more than the %, more preferably 50 moles more than the %, more preferably 80 moles more than the %.
When macromolecular compound of the present invention contained formula (1), formula (2), the mol ratio of formula (1), formula (2) was preferably 3: 1～1: 3 scope, more preferably 2: 1～1: 2 scope, and more preferably about 1: 1.
When macromolecular compound of the present invention contained formula (1), formula (2) and formula (3), the total of formula (2) and formula (3) and the mol ratio of formula (1) be preferably 3: 1～1: 3 scope, more preferably 2: 1～1: 2 scope, and more preferably about 1: 1.
In addition, macromolecular compound of the present invention can be alternately, random, block or graft copolymer, can be macromolecular compound with these intermediate structure, for example have the random copolymers of block.In addition, comprise that also main chain has branch, the situation and the branch-shape polymer of 3 above terminal parts are arranged.Be preferably alternately, block or graft copolymer, more preferably alternating copolymer.In block or graft copolymer, preferred block or grafting partly contain the structure of formula (7) or the structure of formula (8).
In macromolecular compound of the present invention, as macromolecular compound with have the macromolecular compound of structure (8) with structure (7), can enumerate the alternating copolymer structure that for example has following formula (7-1) macromolecular compound, have the macromolecular compound of the copolymer structure of following formula (8-1).
Figure A20058002510300351
Wherein, t represents the repeat number of structure (7) or structure (8), and t is generally about 2-100000 because of the difference of the structure of repeating unit is different, is preferably about 5-10000.
In addition, in macromolecular compound of the present invention, repeating unit can be connected by unconjugated unit, can comprise these non-conjugated parts in repeating unit.As integrated structure, can enumerate integrated structure shown below and with the integrated structure etc. of the combination more than 2 in the integrated structure shown below.Wherein, R represents hydrogen atom independently of one another; halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; aralkyl; aralkoxy; aromatic alkylthio; acyl group; acyloxy; amido; acylimino; the imines residue; amino; substituted-amino; replace silyl; replace siloxy-; replace silylthio-; replace silyl amino; the heterocyclic radical of 1 valency; heteroaryloxy; heteroarylthio; aryl alkenyl; the aryl ethane base; carboxyl; carbalkoxy; aryloxy carbonyl; aralkoxycarbonyl; assorted aryloxy carbonyl or cyano group, Ar represents the alkyl of 6～60 of carbon numbers.
In addition, the end group of macromolecular compound of the present invention, characteristic, weather resistance when making element if the polymerization activity group is still residual might reduce, and therefore can protect with stable group.Preferably have the conjugated link(age) that are connected with the conjugated structure of main chain, can enumerate for example by C-C and aryl or heterocyclic radical bonded structure.Specifically can enumerate substituting group shown in the change 10 that the spy opens flat 9-45478 communique etc.
In addition, macromolecular compound of the present invention can have the group shown in following formula (18), (19) or (20) at the end of main chain.
Figure A20058002510300361
In the formula, Ar 1, Ar 2, X 1, X 2Represent implication same as described above with m.Z 1Heterocyclic radical, heteroaryloxy, heteroarylthio, aryl alkenyl or the aryl ethane base of expression hydrogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, aralkoxy, aromatic alkylthio, substituted-amino, replacement silyl, 1 valency.
In the formula, Ar 1, Ar 2, X 1, X 2, Z 1Represent implication same as described above with m.
Figure A20058002510300363
In the formula, Y, R 1, Z 1Represent implication same as described above with p.
The number-average molecular weight of the polystyrene conversion of macromolecular compound of the present invention is generally 10 3～10 8About, be preferably 10 4～10 6
Solvent as macromolecular compound of the present invention, can enumerate unsaturated hydrocarbons kind solvents such as toluene, dimethylbenzene, mesitylene, tetraline, naphthane, n-butylbenzene, halo saturated hydrocarbons solvents such as tetracol phenixin, chloroform, methylene dichloride, ethylene dichloride, chlorobutane, n-butyl bromide, chloropentane, bromo pentane silane, chlorohexane, bromohexane, chlorine hexanaphthene, bromine hexanaphthene, halo unsaturated hydrocarbons kind solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, ether solvents such as tetrahydrofuran (THF), tetrahydropyrans etc.Because of the structure of macromolecular compound, the difference difference of molecular weight, but be dissolved in these solvents more than making 0.1 weight % usually.
In macromolecular compound of the present invention, preferably has the macromolecular compound of liquid crystal liquid crystal property.What is called has the macromolecular compound of liquid crystal liquid crystal property, and the molecule that is meant macromolecular compound or contains macromolecular compound shows mesomorphic phase.Mesomorphic phase can be by affirmations such as polarizing microscope and differential scanning calorimetric measurement, X-ray diffraction mensuration.
Macromolecular compound with liquid crystal liquid crystal property for example, when being used as the material of OTFT, is used to improve electronic mobility or hole mobility.In addition, known macromolecular compound with liquid crystal liquid crystal property is by making its orientation, optically or have anisotropy on the electricity.(Synthetic?Metals?119(2001)537)
Below the manufacture method of macromolecular compound of the present invention is described.
Macromolecular compound of the present invention, for example, can be by being that raw material carries out polycondensation and makes with the compound shown in the compound shown in the following formula (21), the compound shown in (22) and (23).
Figure A20058002510300371
In the formula, Ar 1, Ar 2, X 1, X 2Represent implication same as described above with m.Y 1And Y 2Represent halogen atom, alkylsulphonic acid ester group, aryl sulfonic acid ester group, arylalkyl sulfonic acid ester group, boric acid ester group, sulfonium methyl, Phosphonium methyl, phosphonic acid ester methyl, single halogenated methyl, boronate, formyl radical or vinyl independently of one another.
In the formula, Y, R 1, Y 1, Y 2Represent implication same as described above with p.
Figure A20058002510300373
In the formula, Ar 3, Y 1, Y 2Represent implication same as described above with q.
Go up and the viewpoint of the easiness of polycondensation Y from the compound shown in above-mentioned (21), (22) and (23) synthetic 1And Y 2Preferably be halogen atom, alkylsulphonic acid ester group, aryl sulfonic acid ester group, arylalkyl sulfonic acid ester group, boric acid ester group or boronate independently of one another.
Macromolecular compound of the present invention preferably by also using the compound shown in following formula (24), (25), (26) or (27) to carry out polycondensation except (21), (22) and (23), is controlled its end structure.
In the formula, Ar 1, Ar 2, X 1, X 2, Y 2Represent implication same as described above with m.Z 1Heterocyclic radical, heteroaryloxy, heteroarylthio, aryl alkenyl or the aryl ethane base of expression hydrogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, aralkoxy, aromatic alkylthio, substituted-amino, replacement silyl, 1 valency.
Figure A20058002510300382
In the formula, Ar 1, Ar 2, X 1, X 2, Y 1, Z 1Represent implication same as described above with m.
In the formula, Ar 1, Ar 2, X 1, X 2, Y 2, Z 1Represent implication same as described above with m.
In the formula, Ar 3, Y 2, Z 1Represent implication same as described above with q.
In the compound shown in above-mentioned formula (24)～(27), go up and the viewpoint of the easiness of polycondensation Y from above-claimed cpd synthetic 1～Y 2Preferably be halogen atom, alkylsulphonic acid ester group, aryl sulfonic acid ester group, arylalkyl sulfonic acid ester group, boric acid ester group or boronate, more preferably halogen atom independently of one another.
As the alkylsulphonic acid ester group in formula (21)～(27), can enumerate methylsulfonic acid ester group, ethyl sulfonic acid ester group, trifluoromethanesulfonic acid ester group etc., as the aryl sulfonic acid ester group, can enumerate Phenylsulfonic acid ester group, tosic acid ester group etc., as the arylalkyl sulfonic acid ester group, can enumerate benzyl sulfonate group etc.
As the boric acid ester group, can enumerate the group shown in the following formula.
As the sulfonium methyl, can enumerate the group shown in the following formula.
-CH 2S +Me 2X -,-CH 2S +Ph 2X -(X represents halogen atom)
Zuo Wei Phosphonium methyl can be enumerated the group shown in the following formula.
-CH 2P +Ph 3X -(X represents halogen atom)
As the phosphonic acid ester methyl, can enumerate the group shown in the following formula.
-CH 2PO(OR’) 2
(R ' expression alkyl, aryl or arylalkyl)
As single halogenated methyl, can enumerate fluoro methyl, chloro methyl, bromomethyl, iodo-methyl.
In addition, as the reaction method that the manufacturing of macromolecular compound of the present invention is used, can enumerate and for example adopt the Suzuki coupled reaction to carry out the polymeric method, adopt the Grignard reaction to carry out the polymeric method, adopt Ni (O) catalyzer to carry out the polymeric method, adopt FeCl 3Deng oxygenant carry out the polymeric method, in the method for carrying out oxypolymerization aspect the electrochemistry or adopt the method etc. of the decomposition of intermediate macromolecular compound with suitable disengaging base.
Wherein, owing to structure control is easy, the polymerization of the polymerization of the therefore preferred Wittig of employing reaction, employing Heck reaction, the polymerization of adopting the Horner-Wadsworth-Emmons method, the polymerization of adopting the Knoevenagel reaction and employing Suzuki coupled reaction are carried out the polymeric method, adopt the Grignard reaction to carry out the polymeric method, are adopted Ni (O) catalyzer to carry out the polymeric method.From the acquisition of raw material easily and polyreaction easy and simple to handle, the further preferred Suzuki of employing coupled reaction is carried out the polymeric method, is adopted the Grignard reaction to carry out the polymeric method, employing Ni (O) catalyzer carries out the polymeric method.
Monomer is dissolved in organic solvent as required, uses alkali for example, suitable catalyzer, below the above boiling point of the fusing point of organic solvent, make its reaction.For example, can use " Organic Reactions ", the 14th volume, 270-490 page or leaf, John Wiley﹠amp; Sons, Inc., nineteen sixty-five, " Organic Reactions ", the 27th volume, 345-390 page or leaf, John Wiley﹠amp; Sons, Inc., nineteen eighty-two, " Organic Syntheses ", Collective Volume VI, 407-411 page or leaf, John Wiley﹠amp; Sons, Inc., 1988, " Chem.Rev. ", the 95th volume, 2457 pages (nineteen ninety-five), " J.Organomet.Chem. ", the 576th volume, 147 pages (1999), " J.Prakt.Chem. ", the 336th volume, 247 pages (1994), " Makromol.Chem., Macromol.Symp. ", the 12nd volume, the known method of putting down in writing during wait 229 pages (1987).
As organic solvent, different because of compound, the reaction used, but generally in order to suppress side reaction, the preferred solvent that uses is fully implemented deoxidation treatment, and reaction is carried out.In addition, preferably similarly carry out processed.(but the Suzuki coupled reaction such with 2 phase systems water under the situation of reaction under there is no this restriction).
In order to react, add suitable alkali, suitable catalyzer.Can select them according to the reaction of using.This alkali or catalyzer preferably fully are dissolved in the employed solvent of reaction.As method, can enumerate the solution that alkali or catalyzer are slowly added in stirring reaction liquid limit under inert atmospheres such as argon, nitrogen, limit, the method for perhaps in the solution of alkali or catalyzer, slowly adding reaction solution on the contrary with alkali or catalyst mix.
When macromolecular compound of the present invention is used material as the macromolecule membrane element, because its purity exerts an influence to the characteristic of element, after making with extra care, monomer before preferably adopting methods such as distillation, sublimation purifying, recrystallization to polymerization carries out polymerization, in addition, carry out purification process such as redeposition is refining, the employing chromatogram is separated after preferred synthesizing.
In the manufacture method of macromolecular compound of the present invention, each monomer can react in disposable mixing, also can cut apart as required and mix.
More specifically reaction conditions is described, under the situation of Wittig reaction, Horner reaction, Knoevengel reaction etc., with respect to monomeric functional group use more than the equivalent, preferred 1～3 normal alkali reacts.As alkali, be not particularly limited, can use for example metal alkoxides such as tert.-butoxy potassium, tert.-butoxy sodium, sodium ethylate, lithium methoxide, hydride reagents such as sodium hydride, amides classes such as sodium amide etc.As solvent, can use N, dinethylformamide, tetrahydrofuran (THF), diox, toluene etc.Temperature of reaction is generally about room temperature～150 ℃ reacts.Reaction times for example is 5 minutes～40 hours, can be the time that polymerization is fully carried out, in addition, because reaction does not need long-time placement after finishing, therefore preferred 10 minutes～24 hours.If the concentration during reaction crosses rare then reaction efficiency is poor, if overrich then react difficult control, therefore can suitably selection in the scope of about 0.01wt%～dissolved peak concentration, be generally the scope of 0.1wt%～20wt%.Under the situation of Heck reaction, use palladium catalyst, in the presence of alkali such as triethylamine, make monomer reaction.Use N, the solvent that boiling points such as dinethylformamide, N-Methyl pyrrolidone are higher, temperature of reaction is about 80～160 ℃, the reaction times is about 1 hour～100 hours.
Under the situation of Suzuki coupled reaction, for example use palladium [four (triphenyl phosphine)], acid chloride class etc. as catalyzer, with respect to monomer add more than the equivalent, mineral alkalis such as preferred 1～10 equivalent salt of wormwood, yellow soda ash, hydrated barta, organic basess such as triethylamine, inorganic salt such as cesium fluoride react.Can be the aqueous solution with inorganic salt, in 2 phase systems, react.As solvent, can enumerate N, dinethylformamide, toluene, glycol dimethyl ether, tetrahydrofuran (THF) etc.Different because of solvent, but preferably use temperature about 50～160 ℃.Can be warmed up near the boiling point of solvent, make its backflow.Reaction times is about 1 hour～200 hours.
Under the situation of Grignard reaction, can be set forth in and make halogenide and metal M g reaction in the ether solvents such as tetrahydrofuran (THF), diethyl ether, glycol dimethyl ether, become the Grignard reagent solution, it is mixed with the monomer solution of preparing in addition, after nickel or palladium catalyst are added in marginal not meaning excessive response limit, heat up and make its backflow limit make the method for its reaction in the limit.Grignard reagent with respect to monomer use more than the equivalent, preferred 1～1.5 equivalent, more preferably 1～1.2 equivalent.When adopting these methods in addition to carry out polymerization, also can make its reaction according to known method.
Reaction method is not particularly limited, and can implement in the presence of solvent.The boiling point of preferred-80 ℃～solvent of temperature of reaction.
As the solvent that uses in the reaction, can enumerate pentane, hexane, heptane, octane, stable hydrocarbon such as hexanaphthene, benzene, toluene, ethylbenzene, unsaturated hydrocarbons such as dimethylbenzene, tetracol phenixin, chloroform, methylene dichloride, chlorobutane, n-butyl bromide, chloropentane, bromo pentane silane, chlorohexane, bromohexane, the chlorine hexanaphthene, halo stable hydrocarbon such as bromine hexanaphthene, chlorobenzene, dichlorobenzene, halo unsaturated hydrocarbons such as trichlorobenzene, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, alcohols such as the trimethyl carbinol, formic acid, acetate, carboxylic-acids such as propionic acid, dme, diethyl ether, methyl tertiary butyl ether, tetrahydrofuran (THF), ethers such as tetrahydropyrans diox, hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, mineral acids such as nitric acid etc. can use single solvent or these mixed solvent.
For example carry out extracting with organic solvent after the water quenching after the reaction, adopt common aftertreatments such as solvent heats up in a steamer are obtained.Carry out with the refining methods such as using the stratographic branch is got, recrystallization that can adopt behind the segregation of resultant.
Below macromolecule membrane of the present invention is described.
Macromolecule membrane of the present invention is characterized in that containing the macromolecular compound of the invention described above.
As the thickness of macromolecule membrane of the present invention, be generally about 1nm～100 μ m preferred 2nm～1000nm, further preferred 5nm～500nm, preferred especially 20nm～200nm.
Macromolecule membrane of the present invention can contain a kind of above-mentioned macromolecular compound separately, also can contain above-mentioned macromolecular compound more than 2 kinds.In addition, for electron-transporting or the hole transport ability that improves macromolecule membrane, also can mix and use above-mentioned macromolecular compound low molecular compound with electron-transporting or hole transport ability or macromolecular compound in addition.As this hole transport ability material, can use material known, can enumerate for example pyrazoline derivative, the arylamines derivative, 1, the 2-diphenyl ethylene derivatives, the triphenyl diamine derivative, the oligothiophene or derivatives thereof, the Polyvinyl carbazole or derivatives thereof, the polysilane or derivatives thereof, side chain or main chain have the polyorganosiloxane ramification of aromatic amine, the polyaniline or derivatives thereof, the Polythiophene or derivatives thereof, the polypyrrole or derivatives thereof, the polyphenylene vinylene or derivatives thereof, or poly-inferior thienyl vinylidene or derivatives thereof etc., as electron transporting material, material known can be used, Li such as oxadiazole derivative can be enumerated, anthraquinone bismethane or derivatives thereof, the benzoquinones or derivatives thereof, the naphthoquinones or derivatives thereof, the anthraquinone or derivatives thereof, four cyano anthraquinone bismethane or derivatives thereof, fluorenone derivatives, phenylbenzene dicyano ethene or derivatives thereof, biphenol closes quinone derivatives, or the metal complex of oxine or derivatives thereof, the poly quinoline or derivatives thereof, the polyquinoxaline or derivatives thereof, poly-fluorenes or derivatives thereof etc.
In addition, in order to produce electric charge by the light that absorbs in macromolecule membrane, macromolecule membrane of the present invention can contain the electric charge generating material.As the electric charge generating material, material known can be used, azo-compound and derivative thereof, diazonium compound and derivative thereof, metal-free phthalocyanine compound and derivative thereof, metal phthalocyanine compound and derivative, perylene compound thereof and derivative, polycyclic quinone compound and derivative thereof, squalilium (ス Network ア リ リ ウ system) compound and derivative, azulenium (Austria) compound and derivative, thiapyran compound and fullerene and derivatives thereof such as derivative, C60 can be enumerated.
In addition, macromolecule membrane of the present invention can contain the needed material of the various functions of realization.Can enumerate for example be used to make by the light that absorbs produce the function sensitizing of electric charge sensitizing agent, be used to increase stability stablizer, be used to absorb the UV absorption agent of UV light etc.
In addition, in order to improve mechanical characteristics, macromolecule membrane of the present invention can contain above-mentioned macromolecular compound macromolecular compound material in addition as polymer binder.As polymer binder, preferably extremely do not hinder the polymer binder of electron-transporting or hole transport ability, in addition, the preferred use polymer binder not strong to the absorption of visible light.As this polymer binder, can enumerate poly-(N-vinylcarbazole), polyaniline or derivatives thereof, Polythiophene or derivatives thereof, poly-(to phenylene vinylidene) or derivatives thereof, poly-(2, the inferior thienyl vinylidene of 5-) or derivatives thereof, polycarbonate, polyacrylic ester, polymethyl acrylate, polymethylmethacrylate, polystyrene, polyvinyl chloride, polysiloxane etc.
There is no particular restriction for the manufacture method of macromolecule membrane of the present invention, for example can enumerate by containing above-mentioned macromolecular compound, the method for the solution film forming of blended electron transporting material or hole transport ability material, polymer binder as required.
As by the solvent that uses in the solution film forming, as long as with this macromolecular compound and blended electron transporting material or hole transport ability material, polymer binder dissolving, then there is no particular restriction.
The solvent that uses when forming macromolecule membrane of the present invention by solution, can enumerate unsaturated hydrocarbons kind solvents such as toluene, dimethylbenzene, mesitylene, tetraline, naphthane, n-butylbenzene, halo saturated hydrocarbons solvents such as tetracol phenixin, chloroform, methylene dichloride, ethylene dichloride, chlorobutane, n-butyl bromide, chloropentane, bromo pentane silane, chlorohexane, bromohexane, chlorine hexanaphthene, bromine hexanaphthene, halo unsaturated hydrocarbons kind solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, ether solvents such as tetrahydrofuran (THF), tetrahydropyrans etc.Different because of structure, the molecular weight of macromolecular compound, but be dissolved in these solvents more than can making 0.1 weight % usually.
As method by solution film forming, can enumerate spin-coating method, teeming practice, nick version printing coating method, intaglio printing coating method, rod is coated with coating methods such as method, rolling method, coiling rod coating method, dip coating, spraying method, silk screen print method, flexographic printing method, offset printing method, ink jet printing method, divider print process, preferred spin-coating method, flexographic printing method, ink jet printing method, divider print process.
In the operation of making macromolecule membrane of the present invention, can comprise the operation that makes the macromolecular compound orientation.
Adopt this operation to make the macromolecule membrane of macromolecular compound orientation because backbone molecule or side chain molecule are arranged so electronic mobility or hole mobility raising to a direction.
As the method that makes macromolecular compound orientation, can use the method for putting down in writing as 3～16 pages in the method for alignment of liquid crystal known for example " basis of liquid crystal and use " (this is positive for pine, work, the census of manufacturing can 1991 very altogether in the Jiao Tian city) the 5th chapter, " structure and the rerum natura of strong dielectricity liquid crystal " (the honest husband in Feitian, bamboo add elegant man work, コ ロ Na society, nineteen ninety) altogether the 7th chapter, " liquid crystal " the 3rd volume No. 1 (1999) etc.
Wherein, rubbing manipulation, optical alignment method, shearing method (adding the shear-stress method), easy and useful, the easy utilization of lifting coating method, preferred rubbing manipulation, shearing method as method for alignment.
So-called rubbing manipulation is meant with the method on rubbed substrate surface gently such as cloth.As substrate, can use glass, polymeric membrane etc.As the cloth of rubbed substrate, can use the cloth of gauze, polyester, cotton, nylon, artificial silk etc.In addition, if form alignment films in addition on substrate, orientation characteristic further improves.Wherein,, can enumerate polyimide, polymeric amide, PVA, polyester, nylon etc., also can use commercially available liquid crystal alignment films as alignment films.Alignment films can adopt formation such as spin-coating method, flexographic printing.The cloth that friction is used can suitably be selected according to the alignment films of using.
So-called optical alignment method is meant to form alignment films on substrate, adopts the method for oblique incidence irradiation polarization UV rayed or UV light to make the method with orientation function.As alignment films, can enumerate polyimide, polymeric amide, poly-vinyl cinnamate etc., also can use commercially available liquid crystal alignment films.
In rubbing manipulation or optical alignment method, the macromolecular compound material by the orientation of clamping between the substrate of the processing of having implemented above-mentioned record can make its orientation.At this moment, must make substrate reach the temperature that material is mesomorphic phase or isotropic phase.Carrying out that temperature sets can be before being held in substrate with the macromolecular compound material clip, also can be after clamping.In addition, also can only carry out this macromolecular compound material of coating on the substrate of having implemented orientation process.The coating of macromolecular compound adopts following method to carry out: macromolecular compound is placed on the substrate, be set at more than the Tg or the temperature of demonstration mesomorphic phase or isotropic phase, be coated with on a direction with rod etc., perhaps modulation is dissolved in the solution of organic solvent, adopts spin coating, flexographic printing etc. to be coated with.
So-called shearing method is meant and places another substrate on the macromolecular compound material that is positioned on the substrate, the method for moving upper substrate away in temperature lower edge one direction that becomes mesomorphic phase or isotropic phase.At this moment, if substrate has used the enforcement put down in writing in above-mentioned rubbing manipulation, the optical alignment method substrate of orientation process then can obtain higher orientation degree.As substrate, can use glass, polymeric membrane etc., the object of moving away with stress can not be substrate but metal rod etc.
The so-called coating method that promotes is meant substrate is dipped in the macromolecular compound solution and the method for mentioning.The organic solvent that uses in the macromolecular compound solution, there is no particular restriction for the substrate pulling speed, can select, regulate according to the orientation degree of macromolecular compound.
Make the operation of macromolecular compound orientation, comprise as rubbing manipulation, shearing method etc. after making macromolecular compound become the operation of film and carrying out, also comprise as promoting coating method etc. and the operation that makes macromolecular compound become film is carried out simultaneously.In addition, before making macromolecular compound become the operation of film, can comprise the operation of making alignment films.
Macromolecule membrane of the present invention is owing to have electron-transporting or hole transport ability, by to transmitting control, can be used in various macromolecule membrane elements such as OTFT, organic solar batteries, optical sensor, Electrophtography photosensor, spatial modulation element, photorefractive element by electrode injected electrons or hole or by the electric charge that photoabsorption produces.When this macromolecule membrane is used for these macromolecule membrane elements, adopts orientation process to make its orientation and use and improve preferred because of electron-transporting or hole transport ability.
Application in OTFT describes to macromolecule membrane of the present invention.
Structure as OTFT of the present invention, usually source electrode and drain electrode and by the active coating that macromolecular compound the constitutes setting of joining, the also further insulation layer that joins of clamping and active coating and gate electrode is set, can illustration the structure of Fig. 1～4 for example.
OTFT is formed on the supporting substrate usually.As the material of supporting substrate, only otherwise hinder characteristic as OTFT then there is no particular restriction, also can use glass substrate, flexible film substrate, plastic base.
OTFT can adopt known method, for example special method manufacturing of opening flat 5-110069 communique record.
When forming active coating, highly beneficial and preferably on making from the macromolecular compound of solubility with an organic solvent, can use the manufacture method of the macromolecule membrane of the present invention of above-mentioned explanation to become the macromolecule membrane of active coating.
As the insulation layer that joins with active coating, so long as the high material of electrical insulating property then there is no particular restriction, can use material known.Can enumerate for example SiOx, SiNx, Ta 2O 5, polyimide, polyvinyl alcohol, polyethylene phenol etc.From the viewpoint of lower voltage, the preferred high material of specific inductivity.
When on insulation layer, forming active coating,, also can use surface treatment agent such as silane coupling agent that surface of insulating layer is handled, carry out forming after the surface modification active coating in order to improve the interfacial characteristics of insulation layer and active coating.As surface treatment agent, can enumerate chain alkyl chlorosilane class, chain alkyl alkoxyl silicone alkanes, fluoro-alkyl chlorosilane class, fluoro-alkyl alkoxyl silicone alkanes etc.Before handling with surface treatment agent, also can use ozone UV, O in advance 2Plasma is handled surface of insulating layer.
After OTFT made, preferably encapsulate and the encapsulation OTFT that forms.Thereby OTFT and atmosphere are cut off, and the characteristic that can suppress OTFT reduces.
As method for packing, can enumerate the method that covers with UV cured resin, heat reactive resin, inorganic SiONx film etc., with the method for applying sheet glass such as UV cured resin, heat reactive resin, film etc.In order to carry out effectively and atmospheric obstruct, preferably carry out OTFT from making the operation of back before the encapsulation not being exposed to atmosphere (for example in the exsiccant nitrogen atmosphere, vacuum medium).
Fig. 5 is that to be applied to solar cell with macromolecule membrane of the present invention be the figure that typical example describes.To use for the structure that has disposed macromolecule membrane between transparent or semitransparent pair of electrodes a side.As electrode materials, can use metals such as aluminium, gold and silver, copper, basic metal, alkaline-earth metal or their semi-transparent film, nesa coating.In order to obtain high open voltage,, preferably select by the big mode of difference change of work function as each electrode.In order to improve photo sensitivity, can in macromolecule membrane, add uses such as carrier propellant, sensitizing agent.As base material, can use silicon substrate, glass substrate, plastic base etc.
Fig. 6～8th, being applied to optical sensor with macromolecule membrane of the present invention is the figure that typical example describes.To use for the structure that has disposed macromolecule membrane between transparent or semitransparent pair of electrodes a side.Also can insert the charge generating layer that uses absorb light and produce electric charge.As electrode materials, can use metals such as aluminium, gold and silver, copper, basic metal, alkaline-earth metal or their semi-transparent film, nesa coating.In order to improve photo sensitivity, can in macromolecule membrane, add uses such as carrier propellant, sensitizing agent.As base material, can use silicon substrate, glass substrate, plastic base etc.
Fig. 9～11st, being applied to Electrophtography photosensor with macromolecule membrane of the present invention is the figure that typical example describes.Use with the structure that on electrode, has disposed macromolecule membrane.Also can insert the charge generating layer that uses absorb light and produce electric charge.As electrode materials, can use metals such as aluminium, gold and silver, copper.In order to improve photo sensitivity, can in macromolecule membrane, add uses such as carrier propellant, sensitizing agent.As base material, can use silicon substrate, glass substrate, plastic base etc., also can use metals such as aluminium, thus double as substrate and electrode.
Figure 12 is applied to the figure that spatial optical modulation element describes as typical example with macromolecule membrane of the present invention.Use with the structure that between a pair of transparent or semitransparent electrode, has disposed macromolecule membrane, dielectric layer mirror, liquid crystal layer.The dielectric layer mirror preferably is made of the multilayer film of dielectric substance, is designed to have the wavelength region of antiradar reflectivity and the wavelength region of high-reflectivity, sharply rises in its border.Liquid crystal layer can use various liquid crystal materials, preferably uses strong dielectricity liquid crystal.As electrode materials, can use semi-transparent film, the nesa coating of the high aluminium of electroconductibility, gold and silver, copper etc.As base material, can use transparent or semitransparent materials such as glass substrate, plastic base.
Below for the present invention will be described in further detail embodiment is shown, but the present invention is not limited to these embodiment.
Wherein, for number-average molecular weight, as solvent, adopt gel permeation chromatography (GPC) to obtain the number-average molecular weight of polystyrene conversion with chloroform.
With reference to synthesis example 1
Get 2,7-two bromo-9-Fluorenone 6.65g put into 3 mouthfuls of flasks of the 500ml that nitrogen replacement crosses, are dissolved in trifluoroacetic acid: among the mixed solvent 140ml of chloroform=1: 1.In this solution, add Sodium peroxoborate 1 hydrate, stirred 20 hours.Reaction solution is filtered with celite (celite), wash with toluene.After filtrate water, sodium bisulfite, saturated common salt water washing, carry out drying with sodium sulfate.After solvent distilled, obtain the thick resultant of 6.11g.
Should carry out recrystallization by toluene by thick resultant, carry out recrystallization by chloroform again, obtain the compound 1 of 1.19g.
C 8H 17The modulation of MgBr
Get 1.33g magnesium and put into 3 mouthfuls of flasks of 100ml, carry out flame drying, argon replaces.Add THF10ml, 1-bromooctane 2.3ml to it, heating makes the reaction beginning.Reflux after 2.5 hours cool to room temperature.
The Grignard reaction
Get 1.00g compound 1 and put into 3 mouthfuls of flasks of the 300ml that nitrogen replacement crosses, make among its THF that is suspended in 10ml.Be cooled to 0 ℃, add above-mentioned synthetic C 8H 17MgBr solution.Take off cryostat, under refluxing, stirred 5 hours.After the reaction solution cooling, add entry 10ml, hydrochloric acid.Adding hydrochloric acid preceding is suspension liquid, but becomes the solution of 2 phases after adding.Water, saturated aqueous common salt wash organic phase behind the separatory.Carry out drying with sodium sulfate, solvent is distilled, obtain the thick resultant of 1.65g.Adopt silica gel column chromatography to make with extra care (hexane: ethyl acetate=20: 1), obtain the compound of 1.30g.
Get 0.20g compound 2 and put into 2 mouthfuls of flasks of the 25ml that nitrogen replacement crosses, be dissolved in the toluene of 4ml.In this solution, add tosic acid 1 hydrate 0.02g (0.06mmol), stirred 11 hours down at 100 ℃.With reaction solution put cold after, wash with the order of water, the 4N NaOH aqueous solution, water, saturated aqueous common salt, solvent is distilled, obtain the compound 3 of 0.14g.
Under nitrogen atmosphere, pack in the reaction vessel above-claimed cpd 3 of 1.0g (1.77mmol), two tetramethyl ethylene ketone closes two boron 0.945g (3.72mmol), [1,1 '-two (diphenylphosphino) ferrocene] palladium chloride 0.078g (0.11mmol), 1,1 '-two (diphenylphosphino) ferrocene 0.059g (0.11mmol) and 1,4-diox 15ml was with argon gas bubbling 30 minutes.Then, add Potassium ethanoate 1.043g (10.6mmol), under nitrogen atmosphere, reacted 13.5 hours down at 95 ℃.After reaction finishes, thereby reacting liquid filtering is removed insolubles.Make with extra care with alumina, after solvent is removed, be dissolved in toluene, add gac and stir, filter.With alumina filtrate is made with extra care once more, add gac and stir, filter.After toluene removed fully, add hexane 2.5ml, carry out recrystallization, thereby obtain the compound 3-a 0.28g shown in following.
Figure A20058002510300481
With reference to synthesis example 2
Adopt the special method of opening the 2004-043544 record to obtain the compound 4 shown in following.
Use above-claimed cpd 4, adopt and obtain the compound 4-a shown in following with reference to the same method of synthesis example 1.
Figure A20058002510300483
Embodiment 1
＜macromolecular compound A's is synthetic 〉
With above-claimed cpd 3-a 0.62g and 5,5 '-two bromo-2,2 '-bithiophene 0.29g and Aliquat336 (ACROS ORGANICS system) the 0.36g reaction vessel of packing into.After, operate until being reflected under the nitrogen atmosphere.In the reaction vessel in front, add the toluene 9.3g that carries out bubbling with argon gas in advance and outgas.Then, add solution in this mixing solutions, this solution is dissolved in salt of wormwood 0.39g among the ion exchanged water 9.6g that outgases with the argon gas bubbling in advance and obtains.Then, add four (triphenyl phosphine) palladium (O) 2.1mg.Reaction is all carried out under nitrogen atmosphere.After under refluxad carrying out reaction in 16.3 hours, add bromobenzene 18.4mg, under refluxad reacted 2 hours.Add 2-phenyl-1,3 again, the own borine 19.0mg of 2-dioxane under refluxad reacted 2 hours.After the reaction, this 2 is mixed liquid cooling but, water layer is removed.Organic solvent layer is thickness very, therefore adds chloroform and dilutes.This mixing solutions is injected methyl alcohol, stir about 1 hour.Then, reclaim by the throw out filtration that will generate.After this precipitate dried under reduced pressure, be dissolved in chloroform.This solution by being filled with the post of silicon-dioxide and aluminum oxide, is made with extra care.Then, this solution is injected methyl alcohol, carry out redeposition, the precipitation that generates is reclaimed.Should precipitate drying under reduced pressure, obtain the macromolecular compound A of 0.53g.
The polystyrene conversion number-average molecular weight of this macromolecular compound A is 1.2 * 10 6
Figure A20058002510300491
Embodiment 2
＜macromolecular compound B's is synthetic 〉
With above-claimed cpd 4-a 0.73g and 5,5 '-two bromo-2,2 '-bithiophene 0.32g and the Aliquat336 0.40g reaction vessel of packing into.After, operate until being reflected under the nitrogen atmosphere.In the reaction vessel in front, add the toluene 10.4g that carries out bubbling with argon gas in advance and outgas.Then, add solution in this mixing solutions, this solution is dissolved in salt of wormwood 0.44g among the ion exchanged water 10.7g that outgases with the argon gas bubbling in advance and obtains.Then, add four (triphenyl phosphine) palladium (O) 2.3mg.Reaction is all carried out under nitrogen atmosphere.After under refluxad carrying out reaction in 15 hours, add bromobenzene 20.4mg, under refluxad reacted 2 hours.Add 2-phenyl-1,3 again, the own borine 21.1mg of 2-dioxane under refluxad reacted 2 hours.After the reaction, this 2 is mixed liquid cooling but, organic solvent layer is injected methyl alcohol, stir about 1 hour.Then, reclaim by the throw out filtration that will generate.After this precipitate dried under reduced pressure, be dissolved in chloroform.This solution by being filled with the post of silicon-dioxide and aluminum oxide, is made with extra care.Then, this solution is injected methyl alcohol, carry out redeposition, the precipitation that generates is reclaimed.Should precipitate drying under reduced pressure, obtain the macromolecular compound B of 0.56g.
The polystyrene conversion number-average molecular weight of this macromolecular compound B is 3.9 * 10 5
Figure A20058002510300492
Embodiment 3
The evaluation of the making of＜macromolecule membrane element and OTFT characteristic 〉
Adopt thermooxidizing to form the silicon oxide layer that 200nm becomes insulation layer on the surface of the n-of the high-concentration dopant that becomes gate electrode type silicon substrate, it is bought, carried out behind the ultrasonic washing with alkali cleaning agent, ultrapure water, acetone, adopted ozone UV irradiation that the surface is washed.In nitrogen atmosphere, this substrate be impregnated in the 5mM octane solution of octadecyl trichlorosilane 12 hours, silane treatment is carried out on the surface of silicon substrate, then, substrate is carried out drip washing by the order of octane, chloroform.The macromolecular compound A of weighing 0.018g, add chloroform and become 5.3g, after filtering with the membrane filter of 3 μ m, use this coating fluid, on above-mentioned surface-treated substrate, adopt spin-coating method to form the macromolecule membrane that contains macromolecular compound A of thickness 70nm.On this macromolecule membrane, adopt vacuum vapour deposition evaporation Au electrode, form source electrode and the drain electrode of groove width 2mm, flute length 20 μ m, make macromolecule membrane element 1.
Macromolecule membrane element 1 for making makes gate voltage V in nitrogen atmosphere GChange to 0～-80V, make source electrode-electric leakage voltage across poles V SDChange to 0～-80V, measure the OTFT characteristic, the result obtains good Isd-Vg characteristic, at V g=-80V, V SdUnder the=-80V, obtain leakage current-1.4 μ A.In addition, the electric field effect mobility that is obtained by the Isd-Vg characteristic is 1 * 10 -3Cm 2/ Vs, the on-off ratio of electric current are 1 * 10 6
With reference to synthesis example 3
＜macromolecular compound C's is synthetic 〉
With above-claimed cpd 3 0.96g and 2,2 '-dipyridyl 0.55g packs into behind the reaction vessel, will replace in the reaction system with nitrogen.Add tetrahydrofuran (THF) (THF) (dehydrated solvent) 80g that carries out bubbling with argon gas in advance and outgas to it.Then, in this mixing solutions, add two (1, the 5-cyclooctadiene) nickel (O) Ni (COD) 2}1.05g, and at room temperature stir 10 minutes after, 60 ℃ of reactions 1.5 hours down.Moreover, be reflected in the nitrogen atmosphere and carry out.After the reaction, after this solution cooling, inject methyl alcohol 100ml/ ion exchanged water 200ml mixing solutions, stir about 1 hour.Then, reclaim by the throw out filtration that will generate.After this precipitate dried under reduced pressure, be dissolved in chloroform.This solution is filtered, removed insolubles after, this solution by being filled with the post of aluminum oxide, is made with extra care.Then, this solution is injected methyl alcohol, carry out redeposition, the precipitation that generates is reclaimed.Should precipitate drying under reduced pressure, obtain the macromolecular compound C of 0.5g.
The polystyrene conversion number-average molecular weight of this macromolecular compound C is 7.3 * 10 5
Figure A20058002510300501
Comparative example 1
The evaluation of the making of＜macromolecule membrane element and OTFT characteristic 〉
Use the macromolecular compound C except replacing macromolecular compound A, adopt method similarly to Example 3, on above-mentioned surface-treated substrate, adopt spin-coating method to form the macromolecule membrane that contains macromolecular compound C of thickness 50nm.On this macromolecule membrane, adopt vacuum vapour deposition evaporation Au electrode, form source electrode and the drain electrode of groove width 2mm, flute length 20 μ m, make macromolecule membrane element 2.
Macromolecule membrane element 2 for making makes gate voltage V in nitrogen atmosphere GChange to 0～-80V, make source electrode-electric leakage voltage across poles V SDChange to 0～-80V, measure the OTFT characteristic.At V g=-80V, V SdUnder the=-60V, leakage current is-0.8nA, for low-level.
Embodiment 4
The making of＜macromolecule membrane element and the evaluation of characteristic of solar cell 〉
Be coated with on the glass substrate of ITO film at the thickness that adopts sputtering method with 150nm, to gather (3,4) ethylidene dioxy thiophene/polystyrolsulfon acid (Bayer system, Baytron PAI 4083) after suspension filters with 0.2 μ m membrane filter, adopt spin coating to form the thick film of 70nm, following dry 10 minutes at 200 ℃ on hot plate.Then, use the 0.2wt% chloroformic solution of macromolecular compound A, at room temperature adopt spin coating to form the thick macromolecule membrane of 50nm.And then under reduced pressure, be dried 1 hour under 60 ℃ after, as electrode, the lithium fluoride of the about 0.4nm of evaporation, the aluminium of the 180nm of the calcium of evaporation 5nm, and then evaporation is then made the macromolecule membrane element 3 that has used macromolecular compound A.Vacuum tightness during evaporation all is 1 * 10 -4Below the pa.Voltage-current characteristic is measured on the irradiation xenon lamp limit, macromolecule membrane element 3 limits that obtains, and the result obtains short-circuit current 43 μ A/cm 2, open voltage 1.75V characteristic of solar cell.
Embodiment 5
The making of＜macromolecule membrane element and the evaluation of characteristic of solar cell 〉
Use macromolecular compound B to replace macromolecular compound A, make macromolecule membrane element 4 similarly to Example 5.Voltage-current characteristic is measured on the irradiation xenon lamp limit, macromolecule membrane element 4 limits that obtains, and the result obtains short-circuit current 38 μ A/cm 2, open voltage 1.15V.
Embodiment 6
＜macromolecular compound D's is synthetic 〉
With above-claimed cpd 3-a 1.13g and 1,2-two (5-two bromo-2-thienyls) ethene 0.60g is (for example, at M.Fuji et al., Synthetic Metals, 55-57,2136-2139 has put down in writing synthetic method in (1993)) and the Aliquat 336 0.69g reaction vessel of packing into.After, operate until being reflected under the nitrogen atmosphere.In the reaction vessel in front, add the toluene 19.4g that carries out bubbling with argon gas in advance and outgas.Then, add solution in this mixing solutions, this solution is dissolved in salt of wormwood 0.74g among the ion exchanged water 20.0g that outgases with the argon gas bubbling in advance and obtains.Then, add four (triphenyl phosphine) palladium (O) 3.9mg.Reaction is all carried out under nitrogen atmosphere.After under refluxad carrying out reaction in 15 hours, add bromobenzene 34.7mg, under refluxad reacted 2 hours.Add 2-phenyl-1,3 again, the own borine 35.8mg of 2-dioxane under refluxad reacted 2 hours.After the reaction, this 2 is mixed liquid cooling but, organic solvent layer is injected methyl alcohol, stir about 1 hour.Then, reclaim by the throw out filtration that will generate.
After this precipitate dried under reduced pressure, obtain the macromolecular compound D of 1.00g.The polystyrene conversion number-average molecular weight of this macromolecular compound D is 1 * 10 6More than.
Figure A20058002510300521
Embodiment 7
The evaluation of the making of＜macromolecule membrane element and OTFT characteristic 〉
The macromolecular compound D of weighing 0.008g adds dichlorobenzene and becomes 2g, the modulation coating fluid.Adopt thermooxidizing to form the silicon oxide layer that 200nm becomes insulation layer on the surface of the n-of the high-concentration dopant that becomes gate electrode type silicon substrate, it is bought, carried out behind the ultrasonic washing with alkali cleaning agent, ultrapure water, acetone, adopted ozone UV irradiation that the surface is washed.On this substrate, adopt vacuum vapour deposition evaporation Au electrode, form source electrode and the drain electrode of groove width 2mm, flute length 20 μ m.This substrate that has electrode is fixed on the spinner, behind the Aldrich that the drips system hexamethyldisilazane (HMDS), is rotated, substrate surface is handled with HMDS with 2000rpm.Use the coating fluid of above-mentioned macromolecular compound D, adopt divider print process (Musashi engineering system Shot Mini), use the needle point of internal diameter 100 μ m, coating macromolecular compound D forms the film of thickness 700nm to cover between the electrode-drain electrode of source.Then, in nitrogen atmosphere, toasted 30 minutes down, make macromolecule membrane element 5 at 120 ℃.
Macromolecule membrane element 5 for making makes gate voltage V in a vacuum GChange to 0～-60V, make source electrode-electric leakage voltage across poles V SDChange to 0～-60V, measure the OTFT characteristic, the result obtains good Isd-Vg characteristic, at V g=-60V, V SdUnder the=-60V, obtain leakage current-0.6 μ A.In addition, the field-effect mobility that is obtained by the Isd-Vg characteristic is 5 * 10 -4Cm 2/ Vs, the on-off ratio of electric current are 1 * 10 3
The thin-film material that macromolecular compound of the present invention is used as macromolecule membrane is useful.

Claims (18)

1. macromolecular compound, it is characterized in that: contain the repeating unit shown in repeating unit shown in the following formula (1) and the formula (2), the number-average molecular weight of polystyrene conversion is 10 3～10 8,
In the formula, Ar 1And Ar 2Represent the aromatic hydrocarbyl of 3 valencys or the heterocyclic radical of 3 valencys independently of one another, X 1And X 2Represent independently of one another O, S, C (=O), S (=O), SO 2, C (R 1) (R 2), Si (R 3) (R 4), N (R 5), B (R 6), P (R 7) or P (=O) (R 8), R 1～R 8Represent hydrogen atom, halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, aralkoxy, aromatic alkylthio, acyl group, acyloxy, amido, acylimino, imines residue, amino, substituted-amino, replacement silyl independently of one another, replace siloxy-, replacement silylthio-, the heterocyclic radical that replaces silyl amino, 1 valency, heteroaryloxy, heteroarylthio, aryl alkenyl, aryl ethane base, carboxyl, carbalkoxy, aryloxy carbonyl, aralkoxycarbonyl, assorted aryloxy carbonyl or cyano group; but, X 1And X 2Difference, C (R 1) (R 2) in R 1And R 2, Si (R 3) (R 4) in R 3And R 4Can mutually combine and form ring, m represents 0 or 1, and n represents 1～6 integer, still, during m=0, X 1Do not represent C (R 1) (R 2), in addition, X 1And Ar 2Be incorporated into Ar 1The ortho position of aromatic nucleus, during m=1, X 2With Ar 1Be attached to Ar 2The ortho position of aromatic nucleus, during m=0, X 1With Ar 1Be attached to Ar 2The ortho position of aromatic nucleus;
Figure A2005800251030002C2
In the formula, o represents 1～10 integer, and p represents 0～2 integer, and Y represents O, S, C (R 10) (R 11), Si (R 12) (R 13) or N (R 14), when having a plurality of Y, they can be the same or different, R 10, R 11, R 12, R 13And R 14Represent hydrogen atom, halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, aralkoxy, aromatic alkylthio, acyl group, acyloxy, amido, acylimino, imines residue, amino, substituted-amino, replacement silyl independently of one another, replace siloxy-, replacement silylthio-, the heterocyclic radical that replaces silyl amino, 1 valency, heteroaryloxy, heteroarylthio, aryl alkenyl, aryl ethane base, carboxyl, carbalkoxy, aryloxy carbonyl, aralkoxycarbonyl, assorted aryloxy carbonyl or cyano group, R 10And R 11, R 12And R 13Can mutually combine and form ring, R 9Expression halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, aralkoxy, aromatic alkylthio, acyl group, acyloxy, amido, acylimino, imines residue, amino, substituted-amino, replacement silyl, replacement siloxy-, replacement silylthio-, the heterocyclic radical that replaces silyl amino, 1 valency, heteroaryloxy, heteroarylthio, aryl alkenyl, aryl ethane base, carboxyl, carbalkoxy, aryloxy carbonyl, aralkoxycarbonyl, assorted aryloxy carbonyl or cyano group have a plurality of R 9The time, they can be the same or different, in addition, and R 9Between can mutually combine and form ring.
2. macromolecular compound according to claim 1 is characterized in that: contain the repeating unit shown in repeating unit shown in the repeating unit shown in the above-mentioned formula (1), the above-mentioned formula (2) and the following formula (3), the number-average molecular weight of polystyrene conversion is 10 3～10 8,
Figure A2005800251030003C1
In the formula, Ar 3The heterocyclic radical of aromatic hydrocarbyl, the divalent of expression divalent or-CR 15=CR 16-, R 15And R 16Represent hydrogen atom independently of one another; halogen atom; alkyl; alkoxyl group; alkylthio; aryl; aryloxy; arylthio; aralkyl; aralkoxy; aromatic alkylthio; acyl group; acyloxy; amido; acylimino; the imines residue; amino; substituted-amino; replace silyl; replace siloxy-; replace silylthio-; replace silyl amino; the heterocyclic radical of 1 valency; heteroaryloxy; heteroarylthio; aryl alkenyl; the aryl ethane base; carboxyl; carbalkoxy; aryloxy carbonyl; aralkoxycarbonyl; assorted aryloxy carbonyl or cyano group, q represents 1～6 integer.
3. macromolecular compound according to claim 1 and 2 is characterized in that: the X of formula (1) 1Be O, S, C (O), S (O) or SO 2
4. according to each described macromolecular compound in the claim 1～3, it is characterized in that: the X of formula (1) 2Be C (R 1) (R 2), Si (R 3) (R 4), N (R 5), B (R 6), P (R 7) or P (O) (R 8), in the formula, R 1～R 8Represent implication same as described above independently of one another.
5. according to each described macromolecular compound in the claim 1～4, it is characterized in that: the Ar of formula (1) 1And Ar 2Be the aromatic hydrocarbyl of 3 valencys independently of one another.
6. according to each described macromolecular compound in the claim 1～5, it is characterized in that: the Y in the formula (2) is S.
7. according to each described macromolecular compound in the claim 2～6, it is characterized in that: Ar in the formula (3) 3Be-CR 15=CR 16-, in the formula, R 15And R 16Represent implication same as described above.
8. according to each described macromolecular compound in the claim 1～7, it is characterized in that: the repeating unit shown in formula (1) and the formula (2) add up to 10 moles of whole repeating units more than the %.
9. according to each described macromolecular compound in the claim 1～8, it is characterized in that: have liquid crystal liquid crystal property.
10. macromolecule membrane, it is characterized in that: contain each described macromolecular compound in the claim 1～9, thickness is in the scope of 1nm～100 μ m.
11. the manufacture method of the described macromolecule membrane of claim 10 is characterized in that: use spin-coating method, ink jet printing method, divider print process or flexographic printing method.
12. the manufacture method of the described macromolecule membrane of claim 10 is characterized in that: comprise the operation that adopts rubbing manipulation or shearing method to make macromolecular orientation.
13. a macromolecule membrane element is characterized in that: comprise the described macromolecule membrane of claim 10.
14. an OTFT is characterized in that: comprise the described macromolecule membrane of claim 10.
15. an organic solar batteries is characterized in that: comprise the described macromolecule membrane of claim 10.
16. optical sensor: it is characterized in that: comprise the described macromolecule membrane of claim 10.
17. an Electrophtography photosensor is characterized in that: comprise the described macromolecule membrane of claim 10.
18. a spatial optical modulation element is characterized in that: comprise the described macromolecule membrane of claim 10.
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