TWI602844B - Diketopyrrolopyrrole polymers for use in organic semiconductor devices - Google Patents

Description

Diketoppyrrolopyrrole polymer for organic semiconductor devices

The invention relates to the inclusion of one or more (I) (repeated) unit of polymer, or formula (II) or a polymer of (III) and its use as an organic semiconductor for organic devices, in particular organic photovoltaic devices (solar cells) and photodiodes, or diodes and/or organic field-effect transistors In the device. The polymer of the present invention has excellent solubility in an organic solvent and has excellent film forming properties. In addition, high energy conversion efficiency, excellent field effect mobility, and good on/off current can be observed when the polymer of the present invention is used in an organic field effect transistor, an organic photovoltaic device (solar cell), and a photodiode. Ratio and / or excellent stability.

WO 05/049695 discloses diketopyrrolopyrrole (DPP) based polymers and their use in PLEDs, organic integrated circuits (O-IC), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), The use of organic solar cells (O-SC), or organic laser diodes, but does not disclose a specific polymer based on DPP of Formula I.

Preferred polymers comprise repeating units of the formula

And repeating unit ,among them

R ¹ and R ² independently of each other may be a C ₁ -C ₂₅ alkyl group having one or more oxygen atoms, especially a C ₄ -C ₁₂ alkyl group, and Ar ¹ and Ar ² are independently a group of the following formula :

, wherein -Ar ³ - is a group of the formula:

,among them

R ⁶ is hydrogen, C ₁ -C ₁₈ alkyl, or C ₁ -C ₁₈ alkoxy, and R ³² is methyl, Cl, or OMe, and R ⁸ is H, C ₁ -C ₁₈ alkyl, or C ₁ -C ₁₈ alkyl substituted by E and/or heterozygous D, especially heterozygous -O-C ₁ -C ₁₈ alkyl.

EP 2034537 A2 relates to a thin film transistor device comprising a semiconductor layer comprising a compound containing a chemical structure represented by the following formula:

Wherein X is each independently selected from the group consisting of S, Se, O, and NR", and R" are each independently selected from the group consisting of hydrogen, optionally substituted hydrocarbons, and hetero atom-containing groups, and Z is independently substituted as appropriate. And one of a hetero atom-containing group and a halogen, d is at least 1 and e is 0 to 2; a represents at least 1; b represents 0 to 20; and n represents at least It is a number of one.

Among them, the following homopolymers are clearly revealed:

Wherein n is a number of repeating units and may be from about 2 to about 5,000, and R''', R"" and R'"'' may be the same or different substituents, and wherein the substituents are independently selected from the condition A group consisting of a substituted hydrocarbon group and a hetero atom-containing group.

The present invention does not refer to homopolymers, especially formulas (22), (23), (24), (25), (34), (35), (36), (37), (44), (45), Homopolymers of (46) and (47), which are expressly disclosed in EP 2034537 A2.

EP 2 075 274 A1 discloses soluble polythiophene derivatives containing highly coplanar repeating units. The coplanar nature of the TPT (thiophene-phenylene-thiophene) unit improves the degree of intramolecular binding and intermolecular π-π interaction.

The object of the present invention is to provide a polymer which exhibits high energy conversion efficiency and excellent field effect mobility when used in an organic field effect transistor, an organic photovoltaic device (solar cell) and a photodiode. Good on/off current ratio and/or excellent stability.

The target has been included (I) (repeated) unit of polymer, or formula (II) or The polymer of (III) is solved, wherein

x=0.995 to 0.005, y=0.005 to 0.995, especially x=0.2 to 0.8, y=0.8 to 0.2, and wherein x+y=1.

r=0.985 to 0.005, s=0.005 to 0.985, t=0.005 to 0.985, u=0.005 to 0.985, and wherein r+s+t+u=1,

A series a group of (IV), wherein a' is an integer 1 or 2, b is an integer 1 or 2, c is 0, or an integer 1 or 2, d is 0, or an integer 1 or 2, and e is 0, or an integer 1 Or 2, f is 0, or an integer 1 or 2, and R ¹ and R ² may be the same or different and are selected from the group consisting of hydrogen, C ₁ -C ₁₀₀ alkyl, -COOR ²⁰³ ; C ₁ -C ₁₀₀ alkyl, one via Or a plurality of halogen atoms, hydroxyl groups, nitro groups, -CN, or C ₆ -C ₁₈ aryl groups substituted and/or hetero-O-, -COO-, -OCO-, or -S-; C ₇ -C ₁₀₀ Arylalkyl, aminemethanyl; C ₅ -C ₁₂ cycloalkyl, which may be substituted 1 to 3 times with C ₁ -C ₈ alkyl and/or C ₁ -C ₈ alkoxy; C ₆ -C _{a 24} aryl group, especially a phenyl or 1- or 2-naphthyl group, which may be substituted by a C ₁ -C ₈ alkyl group, a C ₁ -C ₈ thioalkoxy group, and/or a C ₁ -C ₈ alkoxy group 1 to 3 times; or pentafluorophenyl, R ²⁰³ is a C ₁ -C ₅₀ alkyl group, especially a C ₄ -C ₂₅ alkyl group; Ar ¹ and Ar ^{1 '} are independently of each other ,

Ar ² , Ar ^{2 ′} , Ar ³ and Ar ^{3 ′} are independently of each other ,

Or having the meaning of Ar ¹ , wherein one of X ³ and X ⁴ is N and the other is CR ⁹⁹ , R ⁹⁹ , R ¹⁰⁴ and R ^{104 '} are each independently hydrogen, halogen, especially F; or visible a C ₁ -C ₂₅ alkyl group having one or more oxygen or sulfur atoms, especially a C ₄ -C ₂₅ alkyl group; a C ₇ -C ₂₅ arylalkyl group, or a C ₁ -C ₂₅ alkoxy group, R ¹⁰⁵ , R ^{105 '} , R ¹⁰⁶ and R ^{106 '} are, independently of each other, hydrogen, halogen; optionally, a C ₁ -C ₂₅ alkyl group having one or more oxygen or sulfur atoms; a C ₇ -C ₂₅ arylalkyl group, or C ₁ -C ₁₈ alkoxy; R ¹⁰⁷ is C ₇ -C ₂₅ arylalkyl, C ₆ -C ₁₈ aryl; C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ perfluoroalkyl or C of ₁ -C ₁₈ alkoxy-substituted C ₆ -C ₁₈ aryl; C ₁ -C ₂₅ alkyl; -O- or -S- mixed with the C ₁ -C ₂₅ alkyl; or -COOR ^119; R ¹¹⁶ Hydrogen, C ₇ -C ₂₅ arylalkyl, C ₆ -C ₁₈ aryl; substituted by C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ perfluoroalkyl or C ₁ -C ₁₈ alkoxy C ₆ -C ₁₈ aryl; C ₁ -C ₂₅ alkyl; hetero-O- or -S-C ₁ -C ₂₅ alkyl; or -COOR ¹¹⁹ ; R ¹¹⁹ C ₁ -C ₂₅ alkyl, C ₁ -C ₂₅ alkyl, C ₇ -C ₂₅ arylalkyl, C ₆ -C ₂ substituted by E' and/or misced with D' _{a 4} aryl group, a C ₆ -C ₂₄ aryl group substituted by G, or a C ₇ -C ₂₅ aralkyl group, and R ¹⁰⁸ and R ¹⁰⁹ are each independently H, C ₁ -C ₂₅ alkyl, substituted by E' and / or mixed with D' C ₁ -C ₂₅ alkyl, C ₇ -C ₂₅ arylalkyl, C ₆ -C ₂₄ aryl, G substituted C ₆ -C ₂₄ aryl, C ₂ -C ₂₀ Heteroaryl, G-substituted C ₂ -C ₂₀ heteroaryl, C ₂ -C ₁₈ alkenyl, C ₂ -C ₁₈ alkynyl, C ₁ -C ₁₈ alkoxy, E'substituted and/or hetero a C ₁ -C ₁₈ alkoxy group having D', or a C ₇ -C ₂₅ aralkyl group, or R ¹⁰⁸ together with R ¹⁰⁹ forming a group of the formula =CR ¹¹⁰ R ¹¹¹ wherein R ¹¹⁰ and R ¹¹¹ are independently of each other is H, C ₁ -C ₁₈ alkyl, E 'substituted and / or mixed with D' of C ₁ -C ₁₈ alkyl, C ₆ -C ₂₄ aryl group, substituted by the G C ₆ -C ₂₄ aryl group , or C ₂ -C ₂₀ substituted with the aryl or heteroaryl G C ₂ -C ₂₀ heteroaryl, or R ¹⁰⁸ and R ¹⁰⁹ form a 5- or 6-membered ring, which is optionally substituted with the following groups: C ₁ - C ₁₈ alkyl, C ₁ -C ₁₈ alkyl, C ₆ -C ₂₄ aryl, C ₆ -C ₂₄ aryl, C ₂ -C ₂₀ substituted with E' and/or D' Heteroaryl, G ₂ -C ₂₀ heteroaryl substituted by C, C ₂ -C ₁₈ alkenyl, C ₂ -C ₁₈ alkynyl, C ₁ -C ₁₈ alkoxy, C ₁ -C ₁₈ alkoxy or C ₇ -C ₂₅ aralkyl substituted by D' and/or misced with D', D'-CO-, -COO-, -S-, -O- or - NR ¹¹² -, E' is a C ₁ -C ₈ thioalkoxy group, a C ₁ -C ₈ alkoxy group, CN, -NR ¹¹² R ¹¹³ , -CONR ¹¹² R ¹¹³ or a halogen, G system E' or C ₁ -C ₁₈ alkyl and R ¹¹² and R ¹¹³ independently of each other H; C ₆ -C ₁₈ aryl; substituted with C ₁ -C ₁₈ alkyl, or C ₁ -C ₁₈ alkoxy group of C ₆ -C ₁₈ aryl; C ₁ -C ₁₈ alkyl; or heteroaryl substituted with -O- of C ₁ -C ₁₈ alkyl, B, D and E are each independently a group of the formula:

Or Formula IV, provided that B, D and E are groups of formula IV, which differ from A, where k is 1, l is 0 or 1, r is 0 or 1, z is 0 or 1, a is Integer 1 to 5, especially 1 to 3, g is an integer 1 or 2, h is an integer 1 or 2, i is 0, or an integer 1 or 2, j is 0, or an integer 1 or 2, k is 0, or an integer 1 or 2, 1 is 0, or an integer 1 or 2, and R ^{1 '} and R ^2' independently of each other have the meaning of R ¹ , Ar ⁸ , Ar ^{8 '} , Ar ⁹ , Ar ^{9 '} , Ar ¹⁰ and Ar ^10' Independent of each other, has the meaning of Ar ² , and Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ are independently of each other:

Wherein one of X ⁵ and X ⁶ is N and the other is CR ¹⁴ , Ar ²⁰ is an aryl or heteroaryl group, each of which may be optionally substituted, R ¹¹⁸ has the meaning of R ¹¹⁶ , R ¹² And R ^12' are, independently of each other, hydrogen, halogen; optionally, a C ₁ -C ₂₅ alkyl group having one or more oxygen or sulfur atoms, especially a C ₄ -C ₂₅ alkyl group; a C ₁ -C ₂₅ alkoxy group, C ₇ -C ₂₅ arylalkyl, or R ¹³ is C ₁ -C ₁₀ alkyl or tri(C ₁ -C ₈ alkyl)carbyl, and R ¹⁴ , R ^14' , R ¹⁵ , R ^{15 '} , R ¹⁷ and R ^{17 '} are each independently hydrogen. Or optionally, a C ₁ -C ₂₅ alkyl group having one or more oxygen atoms, especially a C ₆ -C ₂₅ alkyl group; R ¹⁸ and R ^18' are independently hydrogen and halogen; and optionally one or more C ₁ -C ₂₅ alkyl, especially C ₄ -C ₂₅ alkyl; C ₇ -C ₂₅ aralkyl or C ₁ -C ₂₅ alkoxy; R ¹⁹ hydrogen, C ₇ -C ₂₅ aralkyl, C ₆ -C ₁₈ aryl; substituted with the alkyl group by C ₁ -C _18, or C ₁ -C ₁₈ alkoxy, C ₆ -C ₁₈ aryl group; or heteroaryl optionally with one or more oxygen or a C ₁ -C ₂₅ alkyl group of a sulfur atom, especially a C ₄ -C ₂₅ alkyl group; R ²⁰ and R ^20' are each independently hydrogen, C ₇ -C ₂₅ aralkyl; optionally, one or more oxygen or a C ₁ -C ₂₅ alkyl group of a sulfur atom, especially a C ₄ -C ₂₅ alkyl group, an X ⁷ system -O-, -S-, -NR ¹¹⁵ -, -Si(R ¹¹⁷ )(R ^117' )-, C(R ¹²⁰ )(R ^120' )-, -C(=O)-, ,

X ⁸ based -O- or -NR ¹¹⁵ -; R ¹⁰⁰ and R ^{100 'each} independently is H, F, C ₁ -C ₁₈ alkyl group, an O heteroatom of C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, C ₁ -C ₁₈ alkoxy with O, C ₁ -C ₁₈ perfluoroalkyl, optionally substituted by C ₁ -C ₈ alkyl and/or C ₁ -C ₈ alkoxy 1 to 3 times C ₆ -C ₂₄ aryl, optionally substituted by C ₁ -C ₈ alkyl and/or C ₁ -C ₈ alkoxy 1 to 3 C ₂ -C ₂₀ heteroaryl; R ^303, R ^304, R ³⁰⁵ and R ³⁰⁶ are independently H, F, C ₁ -C ₁₈ alkyl group, the O mixed with each other C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, mixed with O C ₁ -C ₁₈ alkoxy, C ₁ -C ₁₈ perfluoroalkyl, optionally substituted by C ₁ -C ₈ alkyl and/or C ₁ -C ₈ alkoxy 1 to 3 times C ₆ - C ₂₄ aryl, optionally substituted by C ₁ -C ₈ alkyl and/or C ₁ -C ₈ alkoxy, 1 to 3 times C ₂ -C ₂₀ heteroaryl; R ³⁰⁷ and R ³⁰⁸ are independently of each other H or optionally a C ₁ -C ₂₅ alkyl group having one or more oxygen or sulfur atoms; R ³⁰⁹ , R ³¹⁰ , R ³¹¹ and R ³¹² are each independently H, C ₁ -C ₂₅ alkoxy, or visible a C ₁ -C ₂₅ alkyl group having one or more oxygen or sulfur atoms; R ¹⁰¹ and R ^{101 '} are each independently H , F., C ₁ -C ₁₈ alkyl group, an O heteroatom of C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, an O heteroatom of C ₁ -C ₁₈ alkoxy, C ₁ -C ₁₈ Perfluoroalkyl, optionally substituted by C ₁ -C ₈ alkyl and/or C ₁ -C ₈ alkoxy, 1 to 3 times C ₆ -C ₂₄ aryl, optionally C ₁ -C ₈ alkyl And/or a C ₁ -C ₈ alkoxy group substituted 1 to 3 times C ₂ -C ₂₀ heteroaryl; R ¹⁰² and R ^102' are, independently of each other, H, halogen, optionally mixed with one or more oxygen or sulfur C ₁ -C ₂₅ alkyl; C ₇ -C ₂₅ arylalkyl, or C ₁ -C ₂₅ alkoxy; R ¹⁰³ and R ^{103 ',} independently of each other, hydrogen, halogen; optionally one or more a C ₁ -C ₂₅ alkyl group of an oxygen or sulfur atom; optionally a C ₆ -C ₂₄ aryl group substituted by a C ₁ -C ₈ alkyl group and/or a C ₁ -C ₈ alkoxy group 1 to 3 times; _7- C ₂₅ arylalkyl, CN, or C ₁ -C ₂₅ alkoxy; or R ¹⁰³ and R ^{103 '} together form a ring, R ¹¹⁵ and R ^{115 '} are each independently hydrogen, C ₆ -C ₁₈ aryl a C ₆ -C ₁₈ aryl group substituted by a C ₁ -C ₁₈ alkyl group or a C ₁ -C ₁₈ alkoxy group; optionally a C ₁ -C ₂₅ alkyl group having one or more oxygen or sulfur atoms, Especially C ₄ -C ₂₅ alkyl; or C ₇ -C ₂₅ arylalkyl, R ¹¹⁷ and R ^117' are, independently of each other, C ₁ -C ₃₅ alkyl, C ₇ -C ₂₅ arylalkyl, or optionally C ₁ -C ₈ alkyl and/or C ₁ -C ₈ alkoxy Substituting 1 to 3 phenyl groups, R ¹²⁰ and R ^120' are each independently hydrogen, optionally having one or more oxygen or sulfur atoms, C ₁ -C ₃₅ alkyl, or C ₇ -C ₂₅ aryl alkane a group, R ¹²¹ is H, optionally a C ₁ -C ₁₈ alkyl group having one or more oxygen or sulfur atoms, a C ₁ -C ₁₈ perfluoroalkyl group, optionally a C ₁ -C ₈ alkyl group and/or C ₁ -C ₈ alkoxy substituted 1 to 3 times C ₆ -C ₂₄ aryl; optionally substituted by C ₁ -C ₈ alkyl and/or C ₁ -C ₈ alkoxy 1 to 3 times C ₂ - C ₂₀ heteroaryl; or CN, provided that at least one of the groups Ar ¹ , Ar ^{1 '} , Ar ² , Ar ^{2 '} , Ar ³ and Ar ^{3 '} And/or at least one of the groups B, D and E contain a group Relative to a group Polymer containing groups The polymer is preferred.

Group Direct bonding to the DPP skeleton, the following priorities apply: (ˊ represents the key to the DPP skeleton). That is, the group optimal.

If the polymer contains (I) (repeated) unit, where A is Group of (IVa) and D series The group of (Vx), X ^{7 is} preferably different from -S- and -C(R ¹²⁰ )(R ^120' )-.

In style In the case of the group of (Vx), X ^{7 is} preferably -O-, -NR ¹¹⁵ -, -Si(R ¹¹⁷ )(R ^117' )-, -C(=O)-,

, more preferably -C(R ¹²⁰ )(R ¹²⁰ ')-, or And best The group.

In the case of the groups of the formulae (Vy) and (Vz), X ^{7 is} preferably -O-, -S-, -NR ¹¹⁵ -, -C(R ¹²⁰ )(R ^120' )-, -Si( R ¹¹⁷ )(R ¹¹⁷ ')-, -C(=O)-,

, more preferably -C(R ¹²⁰ )(R ¹²⁰ ')-, or And best The group.

The polymers of the invention can be advantageously used in organic photovoltaic (PV) devices (solar cells).

Advantageously, the polymers of the invention, or organic semiconductor materials, layers or components comprising the polymers of the invention, can be used in organic photovoltaic devices (solar cells) and photodiodes, or in organic field effect transistors (OFETs).

The polymer-based copolymer of the present invention. The copolymer is a polymer derived from more than one monomer, for example, a dimer, a trimer, a tetramer, and the like.

The term polymer encompasses both oligomers and polymers. The oligomers of the invention have a weight average molecular weight of < 4,000 Daltons. The weight average molecular weight of the polymer of the present invention is preferably 4,000 Daltons or more, especially 4,000 to 2,000,000 Daltons, more preferably 10,000 to 1,000,000, and most preferably 10,000 to 100,000 Daltons. The molecular weight was determined using a polystyrene standard according to high temperature gel permeation chromatography (HT-GPC). The polydispersity of the polymer of the present invention is preferably from 1.01 to 10, more preferably from 1.1 to 3.0, most preferably from 1.5 to 2.5. The polymer is better than the oligomer.

R ¹ and R ² may be hydrogen, but are preferably different from hydrogen.

R ¹ and R ² may be different, but are preferably the same. Preferably, R ¹ and R ² independently of each other represent C ₁ -C ₁₀₀ alkyl, C ₁ -C ₈ alkyl and/or C ₁ -C ₈ alkoxy substituted 1 to 3 times C ₅ - C ₁₂ cycloalkyl, phenyl or 1- or 2-naphthyl substituted by C ₁ -C ₈ alkyl and/or C ₁ -C ₈ alkoxy for 1 to 3 times, or -CR ³⁰¹ R ³⁰² - (CH ₂ ) _u -A ³ , wherein R ³⁰¹ and R ³⁰² represent hydrogen or C ₁ -C ₄ alkyl, and A ³ represents a C ₁ -C ₈ alkyl group and/or a C ₁ -C ₈ alkoxy group Substituting 1 to 3 phenyl or 1- or 2-naphthyl, and u represents 0, 1, 2 or 3. R ¹ and R ^{2 are more} preferably C ₁ -C ₃₆ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, isobutyl, tert-butyl Base, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl 1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3- Methyl heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-decyl, decyl, undecyl, especially n-dodecyl , tridecyl, tetradecyl, pentadecyl, hexadecyl, 2-ethyl-hexyl, 2-butyl-hexyl, 2-butyl-octyl, 2-hexyldecyl, 2 - mercapto-tetradecyl, heptadecyl, octadecyl, eicosyl, icosyl, behenyl, or tetracosyl. In a particularly preferred embodiment of the invention, R ¹ and R ² are 2-hexyldecyl, or 2-mercapto-tetradecyl.

Advantageously, the groups R ¹ and R ² can be of the formula Said, where m1=n1+2 and m1+n1 twenty four. The palmar side chain (eg, R ¹ and R ² ) may be pure palm or racemic side chain, which may affect the morphology of the polymer

R ^{1 '} and R ^2' have the same priority as R ¹ and R ² , respectively.

As As shown, group Can be in two ways or Arranged in the polymer chain. Label There should be two possibilities.

Repeat unit Can be arranged in the copolymer in two ways, ie . Label

There should be two possibilities (regional isomers).

Other groups are equally suitable, which can be arranged in different ways in the monomers and/or polymers.

Preferably, Ar ¹ and Ar ^{1 ′} are independently of each other More preferably, Ar ¹ and Ar ¹ are independently of each other ,among them Best (ˊ represents the key to the DPP skeleton). Ar ¹ and Ar ^{1 '} may be different, but are preferably the same.

In a preferred embodiment, the invention is directed to a polymer wherein Ar ¹ and Ar ^{1 '} are independently of each other Wherein X ³ is CH and X ⁴ is N, or X ³ is N and X ⁴ is CH, and R ¹¹⁶ is as defined above. R ^{116 is} preferably different from H.

Preferably, Ar ⁸ and Ar ^8' are independently of each other More preferably, Ar ⁸ and Ar ^8' are independently of each other ,among them Best (ˊ represents the key to the DPP skeleton). Ar ⁸ and Ar ^8' may be different, but are preferably the same.

If Ar ¹ and Ar ^1' are independent of each other , then Ar ² and Ar ^2' are independent of each other. Wherein R ^{104 is} different from hydrogen and is preferably C ₁ -C ₂₅ alkyl (ˊ represents a bond to the DPP backbone, or a group immediately following the DPP backbone).

If a' and c are 1, and e is 0 and Ar ¹ and Ar ² have the same meaning; or if a', c and e are 1 and Ar ¹ and Ar ² and Ar ³ have the same meaning; In Ar ¹ .

If a' and c are 1, and e is 0 and Ar ¹ and Ar ² are Or if a', c, and e are 1 and Ar ¹ and Ar ² and Ar ³ are ; then D is preferably different from the group .

A preferably is based on (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg), (IVh), (IVi), (IVj) or (IVk) The group is as defined in the technical solution 3 of the present application. The groups of the formulae IVa, IVc, IVe, IVg, IVh, IVi and IVk are more preferred. The groups of formulae IVa, IVc, IVe, IVg, IVh and Ivi are optimal.

Preferably, B, D and E are independently of each other as defined in the formula (Va), (Vb), (Vc), (Vd), (Ve), (Vf), (Vg), (Vh), (Vi), (Vj), (Vk), (Vl), (Vm), (Vn), (Vo), (Vp), (Vq), (Vr), (Vs), (Vt a group of (Vu), (Vv), (Vw), (Vx), (Vy), (Vz) or (Va'). Formulas Va, Vb, Vc, Ve, Vf, Vh, Vi, Vj, Vk, Vl, Vm, Vn, Vo, Vp, Vq, Vr, Vs, Vu, Vv, Vw, Vx, Vy, Vz, and Va' The group is better. The groups of the formulae Va, Vc, Vf, Vh, Vi, Vk, Vo, Vp, Vq, Vr, Vs, Vu, Vw, Vx and Va' are most preferred. In the group of formula Vx, the group of formula Vx" is optimal.

a group of the formula (Vb') is preferred A group wherein R ³⁰⁹ and R ³¹⁰ are, independently of each other, a C ₁ -C ₂₅ alkoxy group.

In a preferred embodiment, the invention relates to a polymer comprising a (repeating) unit of formula I, in particular Ia, or a polymer of formula II or III, wherein A is a group of formula IVa and the formula D is (Vb'), especially A group wherein R ³⁰⁹ and R ³¹⁰ are, independently of each other, a C ₁ -C ₂₅ alkoxy group.

a group of formula (Vc') is preferred The group.

a group of the formula (Vd') is preferably a formula The group.

In a preferred embodiment, the invention relates to inclusion a polymer of the repeating unit of (I), wherein A is a group of the formula IVa, IVc, IVe, IVg, IVh, IVi, IVj or IVk, and R ¹ and R ² are a C ₁ -C ₃₅ alkyl group, especially C ₈ -C ₃₅ alkyl, R ¹⁰⁴ is a C ₁ -C ₂₅ alkyl group, especially a C ₄ -C ₂₅ alkyl group, which may optionally have one or more oxygen or sulfur atoms, D system of formula Va, Vb, Vc, especially , Ve, Vf, Vh, Vi, Vj, Vk, Vl, Vm, Vn, Vo, Vp, Vq, Vr, Vs, Vu, Vv, Vw, Vx, especially a group of Vy, Vz or Va'. In this embodiment, The polymer of (Ia) is more preferred, wherein n is 4 (especially 10) to 1000, especially 4 to 200, very particularly 5 (especially 20) to 100. The best currently polymer is one in which the group A is a group of formula IVa and the D is a group of formula Vx, especially Vx", for example . Example of the polymer a polymer wherein n is 4 (especially 10) to 1000, especially 4 to 200, very particularly 5 (especially 20) to 100 and R ¹ is C ₁ -C ₃₅ alkyl, especially C ₈ -C ₃₅ alkyl . The polymer exhibits high energy conversion efficiency when used in a solar cell.

In another embodiment, the present invention is directed to a polymer of Formula I, particularly Formula Ia, wherein A is a group of Formula IVa and D is a formula Vo, especially Group, for example . Example of the polymer a polymer wherein n is 4 (especially 10) to 1000, especially 4 to 200, very particularly 5 (especially 20) to 100 and R ¹ is C ₁ -C ₃₅ alkyl, especially C ₈ -C ₃₅ alkyl . The polymer exhibits high energy conversion efficiency when used in a solar cell.

In a preferred embodiment, the invention is directed to a polymer comprising repeating units of the formula: (II), wherein x=0.995 to 0.005, y=0.005 to 0.995, especially x=0.2 to 0.8, y=0.8 to 0.2, and wherein x+y=1; A is a formula IVa, IVc, IVe, IVg, IVh a group of IVi, IVj or IVk, R ¹ and R ² are C ₁ -C ₃₅ alkyl, especially C ₈ -C ₃₅ alkyl, R ¹⁰⁴ is C ₁ -C ₂₅ alkyl, especially C ₄ -C ₂₅ An alkyl group which may optionally have one or more oxygen or sulfur atoms, and B and D independently of each other are of the formulae Va, Vb, Vc, especially Ve, Vf, Vh, Vi, Vj, Vk, Vl, Vm, Vn, Vo, Vp, Vq, Vr, Vs, Vu, Vv, Vw, Vx, especially a group of Vy, Vz or Va'. The weight average molecular weight of the polymer of formula IIa is especially from 10,000 to 1,000,000 Daltons, very particularly from 10,000 to 100,000 Daltons.

By The polymer structure represented by (IIa) is an idealized representation of the polymer product obtained via, for example, the Suzuki polymerization procedure. Simultaneous polymerization of monomers A, B and D produces randomly ordered units and A statistical copolymer composed of (AD-stat-BD).

In another preferred embodiment, the invention is directed to a polymer comprising repeating units of the formula: (II), wherein x=0.995 to 0.005, y=0.005 to 0.995, especially x=0.2 to 0.8, y=0.8 to 0.2, and wherein x+y=1; A is the formula IVa as defined in the third embodiment a group of IVc, IVe, IVg, IVh, IVi, IVj or IVk, R ¹⁰⁴ is a C ₁ -C ₂₅ alkyl group, especially a C ₄ -C ₂₅ alkyl group, which may optionally have one or more oxygen or sulfur atoms , B series a group, R ¹ and R ² are C ₁ -C ₃₅ alkyl, especially C ₈ -C ₃₅ alkyl, and D is a formula Va, Vb, Vc as defined above, especially , Ve, Vf, Vh, Vi, Vj, Vk, Vl, Vm, Vn, Vo, Vp, Vq, Vr, Vs, Vu, Vv, Vw, Vx, especially a group of Vy, Vz or Va'.

In a preferred embodiment, the invention is directed to a polymer comprising repeating units of the formula: (III), where r=0.985 to 0.005, s=0.005 to 0.985, t=0.005 to 0.985, u=0.005 to 0.985, and wherein r+s+t+u=1, A is of formula IVa, IVc, IVe, a group of IVg, IVh, IVi, IVj or IVk, R ¹ and R ² are C ₁ -C ₃₅ alkyl, especially C ₈ -C ₃₅ alkyl, R ¹⁰⁴ is C ₁ -C ₂₅ alkyl, especially C ₄ -C ₂₅ alkyl group, which may optionally have one or more oxygen or sulfur atoms, and B, D and E independently of each other are of formula Va, Vb, Vc, especially , Ve, Vf, Vh, Vi, Vj, Vk, Vl, Vm, Vn, Vo, Vp, Vq, Vr, Vs, Vu, Vv, Vw, Vx, especially a group of Vy, Vz or Va'. The weight average molecular weight of the polymer of formula IIIa is especially from 10,000 to 1,000,000 Daltons, very particularly from 10,000 to 100,000 Daltons.

In the above examples, the groups of the formulae IVa, IVc, IVe, IVg, IVh and IVi are most preferred as the group A.

By The polymer structure represented by (IIIa) is an idealized representation of the polymer product obtained via, for example, a Suzuki polymerization procedure. Simultaneous polymerization of monomers A, B, D, and E produces randomly ordered units (Statistical copolymer composed of poly(AD-stat-BD-stat-AE-stat-BE).

Current formulas (Ia), (Ib), (Ic), (Id), (If), (Ig), (Ih), (Ii), (Ij), (Ik), (Il), (Im), (In), (Io), (Ip), (Iq), (Ir), (Is), (It), (Iu), (Iv), (Ix), (Iy), (Iz), (Ia '), (Ib'), (Ic'), (Id'), (Ie'), (If'), (Ig'), (Ih'), (Ii'), (Ij'), (IIa The polymers of (IIb), (IIc), (IId), (IIe), (IIf), (IIg), (IIh), (IIi) and (IIj) are most preferred. Refer to Technical Solution 8.

R ^{104 is} preferably C ₁ -C ₂₅ alkyl, especially C ₄ -C ₂₅ alkyl, optionally having one or more oxygen or sulfur atoms.

R ¹⁵ , R ^{15 '} , R ¹⁷ and R ^{17 ' are} preferably independently of each other H; or optionally a C ₁ -C ₂₅ alkyl group having one or more oxygen atoms, especially a C ₆ -C ₂₅ alkyl group.

R ²⁰ and R ^{20 ' are} preferably, independently of one another, hydrogen, C ₇ -C ₂₅ aralkyl; optionally a C ₁ -C ₂₅ alkyl group having one or more oxygen or sulfur atoms, especially a C ₄ -C ₂₅ alkane base.

R ¹⁰⁰ and R ^{100' are} preferably H.

R ¹⁰¹ and R ^{101 ' are} preferably H, C ₁ -C ₂₅ alkyl, or C ₁ -C ₂₅ alkoxy.

R ¹⁰² and R ^{102' are} preferably H or a C ₁ -C ₂₅ alkyl group.

R ^{103 is} preferably H or a C ₁ -C ₂₅ alkyl group.

R ^{116 is} preferably H, or C ₁ -C ₂₅ alkyl.

R ¹²⁰ and R ^{120' are} preferably C ₁ -C ₃₅ alkyl groups.

The preparation of the polymers of the invention is illustrated in more detail for the polymers of formula II. The polymers of formulae I and III can be prepared using the methods described for the preparation of polymers of formula II.

The copolymer of formula II can be obtained, for example, by the Suzuki reaction. Aromatic The condensation reaction of a boronate with a halide (especially a bromide) (collectively referred to as "Suzuki reaction") allows for the presence of various organic functional groups such as N. Miyaura and A. Suzuki in Chemical Reviews, Vol. 95, pp. 457-2483 Reported in page (1995). Preferred catalysts are 2-dicyclohexylphosphino-2',6'-di-alkoxybiphenyl/palladium(II) acetate, tris-alkyl-phosphonium/palladium (0) derivatives and tri- Alkylphosphine/palladium (0) derivative. The preferred catalyst is 2-dicyclohexylphosphino-2',6'-di-methoxybiphenyl (sPhos) / palladium acetate (II) and tris-tert-butyl tetrafluoroborate ((t) -Bu) ₃ P*HBF ₄ )/叁 (dibenzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ ) and tri-t-butylphosphine (t-Bu) ₃ P/叁 (two Benzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ ). This reaction is suitable for the preparation of high molecular weight polymers and copolymers.

To prepare a polymer corresponding to formula II, under the catalysis of Pd and triphenylphosphine and The amount of dihalide and (equal moir) corresponds to of two Acid or two Acid salt reaction The amount of dihalide and (equal moir) corresponds to and of two Acid or two An acid salt reaction wherein X ¹⁰ is a halogen, especially Cl, Br or I, very particularly Br, and X ¹¹ is independently -B(OH) ₂ , -B(OY ¹ ) ₂ , at each occurrence, Wherein Y ¹ is independently C ₁ -C ₁₀ alkyl at each occurrence and Y ² is independently C ₂ -C ₁₀ alkyl at each occurrence, for example -CY ³ Y ⁴ -CY ⁵ Y ⁶ -, or -CY ⁷ Y ⁸ -CY ⁹ Y ¹⁰ -CY ¹¹ Y ¹² -, wherein Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , Y ⁸ , Y ⁹ , Y ¹⁰ , Y ¹¹ and Y ^{12 is} independently of each other hydrogen, or C ₁ -C ₁₀ alkyl, especially -C(CH ₃ ) ₂ C(CH ₃ ) ₂ -, -CH ₂ C(CH ₃ ) ₂ CH ₂ -, or -C( CH ₃ ) ₂ CH ₂ C(CH ₃ ) ₂ -, and Y ¹³ and Y ¹⁴ are each independently hydrogen or C ₁ -C ₁₀ alkyl. The reaction is usually carried out in an aromatic hydrocarbon solvent such as toluene or xylene at a temperature of from about 0 °C to 180 °C. Other solvents such as dimethylformamide, dioxane, dimethoxyethane and tetrahydrofuran, or a mixture of such solvents and aromatic hydrocarbons may also be used alone. Use an alkaline aqueous solution (preferably sodium carbonate or sodium hydrogencarbonate, potassium phosphate, potassium carbonate or potassium hydrogencarbonate) as acid, An activator of the acid salt and as a HBr scavenger. The polymerization can last from 0.2 to 100 hours. An organic base (e.g., tetraalkylammonium hydroxide), and a phase transfer catalyst (e.g., TBAB) can enhance the activity of boron (see, for example, Leadbeater &Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein). Other changes in reaction conditions by TI Wallow and BM Novak in J. Org. Chem. 59 (1994) 5034-5037, and M. Remmers, M. Schulze and G. Wegner in Macromol Rapid Commun. 17 (1996) 239-252 Given in . By using an excess of dibromide, two Acid, or two An acid salt, or a chain terminator, to control the molecular weight.

According to the method described in WO2010/136352 (European Patent Application No. 09176497.7), the polymerization is carried out in the presence of:

a) a catalyst/ligand system comprising a palladium catalyst and an organophosphine or ruthenium compound,

b) alkali,

c) a solvent or solvent mixture characterized by:

The organophosphine is a trisubstituted phosphine of the formula: (VI), or a phosphonium salt thereof, wherein X is independently a Y representing a nitrogen atom or a CR ^2" group and Y is independently from X to represent a nitrogen atom or a CR ^9" group, each of two R ^{1 "} groups R ^1" independently of the other represents a group selected from the group consisting of C ₁ -C ₂₄ -alkyl, C ₃ -C ₂₀ -cycloalkyl (which includes, inter alia, monocyclic as well as bi-ring and tri a cyclocycloalkyl group, a C ₅ -C ₁₄ -aryl group (which includes, in particular, a phenyl group, a naphthyl group, an anthracenyl group), a C ₂ -C ₁₃ -heteroaryl group (wherein selected from the group consisting of N, O, and S) The number of heteroatoms may be 1 to 2), wherein two R ^{1 "} groups may also be bonded to each other, and wherein the above-mentioned groups R ^{1 "} themselves may be independently substituted with each other independently with a substituent selected from the group below or Polysubstituted: hydrogen, C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl, C ₃ -C ₈ -cycloalkyl, C ₂ -C ₉ -hetero-alkyl, C ₅ -C ₁₀ - Aryl, C ₂ -C ₉ -heteroaryl (wherein the number of heteroatoms from the group of N, O, S can be from 1 to 4), C ₁ -C ₂₀ -alkoxy, C ₁ -C ₁₀ - Haloalkyl, hydroxy, NH-(C ₁ -C ₂₀ -alkyl), NH-(C ₅ -C ₁₀ -aryl), N(C ₁ -C ₂₀ -alkyl) ₂ , N(C ₁ -C ₂₀ -alkyl)(C ₅ -C ₁₀ -aryl), N(C ₅ -C ₁₀ -aryl) ₂ , N(C ₁ -C ₂₀ -alkyl/C ₅ -C ₁₀ -aryl ₃ ) ₃ ⁺ , NH-CO-C ₁ -C ₂₀ -alkyl, NH-CO-C ₅ -C ₁₀ -aryl a carboxylate group in the form of an amine group, COOH and COOQ (wherein Q represents a monovalent cation or a C ₁ -C ₈ -alkyl group), a C ₁ -C ₆ -decyloxy group, a sulfinate group, SO ₃ H and SO _a sulfonate group of the Q' form (wherein Q' represents a monovalent cation, a C ₁ -C ₂₀ -alkyl group, or a C ₅ -C ₁₀ -aryl group), a tri-C ₁ -C ₆ -alkylcarbenyl group, Two of the substituents may also be bridged to each other, and R ^2" to R ^9" represent hydrogen, alkyl, alkenyl, cycloalkyl, aromatic or heteroaromatic aryl, O-alkyl, NH-alkyl , N-(alkyl) ₂ , O-(aryl), NH-(aryl), N-(alkyl)(aryl), O-CO-alkyl, O-CO-aryl, F, Si(alkyl) ₃ , CF ₃ , CN, CO ₂ H, COH, SO ₃ H, CONH ₂ , CONH (alkyl), CON(alkyl) ₂ , SO ₂ (alkyl), SO (alkyl) , SO (aryl), SO ₂ (aryl), SO ₃ (alkyl), SO ₃ (aryl), S-alkyl, S-aryl, NH-CO (alkyl), CO ₂ (alkane) Base, CONH ₂ , CO (alkyl), NHCOH, NHCO ₂ (alkyl), CO (aryl), CO ₂ (aryl) groups, two or more of which are independent of each other The adjacent groups may also be linked to each other to produce a condensed ring system, and wherein in R ^2" to R ^9" , the alkyl group may be linear or branched in each case and has from 1 to 20 a hydrocarbon group of one carbon atom, the alkenyl group representing a mono- or poly-unsaturated hydrocarbon group which may be linear or branched in each case and having 2 to 20 carbon atoms, and the cycloalkyl group has 3 to a hydrocarbon of 20 carbon atoms, the aryl group representing a 5 to 14 membered aromatic group, wherein 1 to 4 carbon atoms in the aryl group may also be replaced by a hetero atom derived from the group nitrogen, oxygen and sulfur to produce 5 to 14 members. Heteroaromatic groups wherein the groups R ^2" to R ^9" may also have other substituents as defined for R ^1" .

Organophosphines and their synthesis are described in WO2004101581.

Preferred organophosphines are selected from the group consisting of trisubstituted phosphines of the formula:

¹⁾ R ^5" and R ^6" together form a ring . ²⁾ R ^3" and R ^4" together form a ring .

Examples of preferred catalysts include the following compounds: acetamacetone palladium (II), dibenzylidene-acetone palladium (0) complex, palladium propionate (II), Pd ₂ (dba) ₃ : [叁 (二) Benzylideneacetone)dipalladium(0)], Pd(dba) ₂ :[bis(dibenzylideneacetone)palladium(0)], Pd(PR ₃ ) ₂ , wherein the PR ₃ system is trisubstituted by formula VI Phosphide, Pd(OAc) ₂ : [palladium(II) acetate], palladium (II) chloride, palladium (II) bromide, lithium (II) tetrachloropalladate, PdCl ₂ (PR ₃ ) ₂ : PR ₃ a trisubstituted phosphine of formula VI; palladium (0) diallyl-ether complex, palladium (II) nitrate, PdCl ₂ (PhCN) ₂ : [dichlorobis(benzonitrile)palladium(II)], PdCl ₂ (CH ₃ CN): [dichlorobis(acetonitrile)palladium(II)], and PdCl ₂ (COD): [dichloro(1,5-cyclooctadiene)palladium(II)].

Particularly preferred are PdCl ₂ , Pd ₂ (dba) ₃ , Pd(dba) ₂ , Pd(OAc) ₂ , or Pd(PR ₃ ) ₂ . The best ones are Pd ₂ (dba) ₃ and Pd (OAc) ₂ .

The palladium catalyst is present in the reaction mixture in a catalytic amount. The term "catalytic amount" means an amount significantly less than one equivalent of the (hetero)aromatic compound, preferably from 0.001 to 5 mol-%, most preferably from 0.001 to 1 mol, based on the equivalent of the (hetero)aromatic compound used. %.

The amount of the phosphine or phosphonium salt in the reaction mixture is preferably from 0.001 to 10 mol-%, most preferably from 0.01 to 5 mol-%, based on the equivalent of the (hetero) aromatic compound used. The preferred ratio of Pd: phosphine is 1:4.

The base can be selected from all aqueous and non-aqueous bases and can be inorganic or organic bases. Preferably, at least 1.5 equivalents of the base/boron functional group are present in the reaction mixture. Suitable bases are, for example, hydroxides, carboxylates, carbonates, fluorides and phosphates of alkali metals and alkaline earth metals (for example, hydroxides, acetates, carbonates, fluorides and phosphates of sodium and potassium) Or a metal alkoxide. Mixtures of bases can also be used. The base is preferably a lithium salt such as a lithium alkoxide (for example, lithium methoxide and lithium ethoxide), lithium hydroxide, lithium carboxylate, lithium carbonate, lithium fluoride and/or lithium phosphate.

The currently best base is aqueous LiOHxH ₂ O (LiOH monohydrate) and (anhydrous) LiOH.

The reaction is usually carried out at a temperature of from about 0 ° C to 180 ° C, preferably from 20 ° C to 160 ° C, more preferably from 40 ° C to 140 ° C and most preferably from 40 ° C to 120 ° C. The polymerization can last for 0.1 hours, especially 0.2 to 100 hours.

In a preferred embodiment of the invention, the solvent is THF, the base is LiOH*H ₂ O and the reaction is carried out at a reflux temperature of THF (about 65 ° C).

The solvent is selected from, for example, toluene, xylene, anisole, THF, 2-methyltetrahydrofuran, dioxane, chlorobenzene, fluorobenzene, or a solvent mixture (eg, THF/toluene) comprising one or more solvents and Water as appropriate. The best is THF, or THF/water.

Preferably, the polymerization is carried out in the presence of:

a) palladium (II) acetate, or Pd ₂ (dba) ₃ (yttrium (dibenzylideneacetone) dipalladium (0)) and organophosphines A-1 to A-13,

b) LiOH, or LiOHxH ₂ O; and

c) THF, and water as appropriate. If a monohydrate of LiOH is used, it is not necessary to add water.

Optimally, the polymerization is carried out in the presence of:

a) Palladium (II) acetate, or Pd ₂ (dba) ₃ (叁(dibenzylideneacetone) dipalladium (0))

b) LiOHxH ₂ O; and

c) THF. The palladium catalyst is preferably present in an amount of about 0.5 mol-%, based on the equivalent of the (hetero) aromatic compound used. The amount of the phosphine or phosphonium salt in the reaction mixture is preferably about 2 mol-%, based on the equivalent of the (hetero)aromatic compound used. A preferred ratio of Pd: phosphine is about 1:4.

Preferably, the polymerization is carried out under inert conditions in the absence of oxygen. Nitrogen and (more preferably) argon are used as the inert gas.

The process described in European Patent Application No. 09176497.7 is suitable for large-scale applications, is readily available and can convert the starting materials to the corresponding polymers in high yield, high purity and high selectivity. The process can provide a polymer having a weight average molecular weight of at least 10,000 Daltons, more preferably at least 20,000 Daltons, and most preferably at least 30,000 Daltons. The currently preferred polymers have a weight average molecular weight of from 30,000 to 80,000 Daltons. The molecular weight was determined using a polystyrene standard according to high temperature gel permeation chromatography (HT-GPC). The polydispersity of the polymer is preferably from 1.01 to 10, more preferably from 1.1 to 3.0, most preferably from 1.5 to 2.5.

If necessary, use a monofunctional aryl halide or The aryl aryl esters act as chain terminators in such reactions which form terminal aryl groups.

In the Suzuki reaction, the order of the monomer units in the resulting copolymer can be controlled by controlling the order and composition of the monomer feed.

The polymers of the invention may also be synthesized by Stille coupling (for example, see Babudri et al, J. Mater. Chem., 2004, 14, 11-34; JK Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508 ). To prepare a polymer corresponding to Formula II, in an inert solvent at a temperature ranging from 0 ° C to 200 ° C and in the presence of a palladium-containing catalyst and Dihalide and formula Compound reaction, or Dihalide and formula and Reaction of a compound wherein the X ²¹ group is -SnR ²⁰⁷ R ²⁰⁸ R ²⁰⁹ and X ¹⁰ is as defined above, wherein R ²⁰⁷ , R ²⁰⁸ and R ^{209 are the} same or different and are H or C ₁ -C ₆ alkyl, Two of the groups form a common ring as appropriate and the groups are optionally branched or unbranched. It must be ensured here that the ratio of organotin functional groups to halogen functional groups in the bulk of all monomers used is highly balanced. Furthermore, it can be confirmed that it is advantageous to remove any excess reactive groups by capping with a monofunctional reagent at the end of the reaction. To carry out the method, the tin compound and the halogen compound are preferably introduced into one or more inert organic solvents, and stirred at a temperature of from 0 ° C to 200 ° C, preferably from 30 ° C to 170 ° C, for from 1 hour to 200 hours, preferably. 5 hours to 150 hours. The crude product can be purified by methods well known to those skilled in the art and suitable for use with various polymers, such as reprecipitation by repeated implementation or even by dialysis.

Organic solvents suitable for use in the process are, for example, ethers (e.g., diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, dioxolane, diisopropyl ether) And tert-butyl methyl ether), hydrocarbons (such as hexane, isohexane, heptane, cyclohexane, benzene, toluene and xylene), alcohols (such as methanol, ethanol, 1-propanol, 2-propanol, B) Glycols, 1-butanol, 2-butanol and tri-butanol), ketones (such as acetone, ethyl methyl ketone and isobutyl methyl ketone), decylamine (eg dimethylformamide (DMF)) , dimethylacetamide and N-methylpyrrolidone), nitriles (such as acetonitrile, propionitrile and butyronitrile), and mixtures thereof.

The palladium and phosphine components should be selected in a manner similar to that described for the Suzuki variant.

Alternatively, the polymer of the present invention may also be used by the Negishi reaction using zinc reagents A-(ZnX ²² ) ₂ and B-(ZnX ²² ) ₂ (wherein X ²² halogens and halides), and D-(X ²³ ) ₂ ( Wherein X ²³ is a halogen or a triflate, or A-(X ²² ) ₂ , B-(X ²² ) ₂ and D-(ZnX ²³ ) _{2 are} used for the synthesis. See, for example, E. Negishi et al., Heterocycles 18 (1982) 117-22.

Alternatively, the polymer of the present invention may also use the organic hydrazine reagent A-(SiR ²¹⁰ R ²¹¹ R ²¹² ) ₂ and B-(SiR ²¹⁰ R ²¹¹ R ²¹² ) ₂ (wherein R ²¹⁰ , R ²¹¹ and R ^{212 are the} same by Hiyama reaction). Or different and is halogen, or C ₁ -C ₆ alkyl) and D-(X ²³ ) ₂ (wherein X ²³ halogen or trifluoromethanesulfonate), or A-(X ²³ ) ₂ , B- (X ²³ ) ₂ and D-(SiR ²¹⁰ R ²¹¹ R ²¹² ) ₂ were synthesized. See, for example, T. Hiyama et al, Pure Appl. Chem. 66 (1994) 1471-1478 and T. Hiyama et al, Synlett (1991) 845-853.

formula The compound of (Xa) is an intermediate in the production of the polymer of the present invention, wherein a, b, c, d, e, f, R ¹ , R ² , Ar ¹ , Ar ^{1 '} , Ar ² , Ar ^{2 '} , Ar ³ and Ar ^{3 '} are as defined above and X ^{11 '} is independently at each occurrence a halogen atom, very particularly I or Br; or has the meaning of X ¹¹ .

formula The compound of (X) is a novel compound and is another object of the present application, wherein a, b, c, d, e, f, R ¹ , R ² , Ar ¹ , Ar ^{1 '} , Ar ² , Ar ^{2 '} , Ar ³ and Ar ^{3 '} are as defined in the first embodiment and X ¹¹ is independently ZnX ¹² , -SnR ²⁰⁷ R ²⁰⁸ R ²⁰⁹ at each occurrence, wherein R ²⁰⁷ , R ²⁰⁸ and R ^{209 are the} same or different And is H or C ₁ -C ₆ alkyl, wherein the two groups form a common ring as appropriate and the groups are optionally branched or unbranched; X ¹² is a halogen atom, very particularly I or Br ;-OS(O) ₂ CF ₃ , -OS(O) ₂ -aryl, especially , -OS(O) ₂ CH ₃ , -B(OH) ₂ , -B(OH) ₃ ^- , -BF ₃ , -B(OY ¹ ) ₂ , Wherein Y ¹ is independently C ₁ -C ₁₀ alkyl at each occurrence and Y ² is independently C ₂ -C ₁₀ alkyl at each occurrence, for example -CY ³ Y ⁴ -CY ⁵ Y ⁶ - or -CY ⁷ Y ⁸ -CY ⁹ Y ¹⁰ -CY ¹¹ Y ¹² -, wherein Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , Y ⁸ , Y ⁹ , Y ¹⁰ , Y ¹¹ and Y ¹² independently of each other is hydrogen, or a C ₁ -C ₁₀ alkyl group, especially -C(CH ₃ ) ₂ C(CH ₃ ) ₂ -, or -C(CH ₃ ) ₂ CH ₂ C(CH ₃ ) ₂ -, -CH ₂ C(CH ₃ ) ₂ CH ₂ -, and Y ¹³ and Y ¹⁴ are each independently hydrogen or C ₁ -C ₁₀ alkyl.

Examples of compounds of formula X are shown below:

X ^{11 '} , R ¹ , R ² , R ¹¹⁶ , R ¹⁰⁴ and R ^{104 '} are as defined above.

R ¹ and R ^{2 are} preferably C ₁ -C ₃₆ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, isobutyl, tert-butyl Base, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl 1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3- Methyl heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-decyl, decyl, undecyl, especially n-dodecyl , tridecyl, tetradecyl, pentadecyl, hexadecyl, 2-ethyl-hexyl, 2-butyl-hexyl, 2-butyl-octyl, 2-hexyldecyl, 2 -octyl-dodecyl, 2-mercapto-tetradecyl, heptadecyl, octadecyl, eicosyl, icosyl, behenyl or tetracosane base.

R ¹⁰⁴ and R ^104' may be the same or different and are preferably C ₁ -C ₂₅ alkyl, especially C ₄ -C ₂₅ alkyl, which may optionally have one or more oxygen or sulfur atoms, and R ^{116 is} preferably H. Or C ₁ -C ₂₅ alkyl.

A polymer of R ¹ and/or R ² -based hydrogen can be obtained by using a protecting group which can be removed after polymerization (for example, see EP-A-0 648 770, EP-A-0 648 817, EP- A-0 742 255, EP-A-0 761 772, WO 98/32802, WO 98/45757, WO 98/58027, WO 99/01511, WO 00/17275, WO 00/39221, WO 00/63297 and EP -A-1 086 984). The pigment precursor is converted to its pigment form by the following method: The rupture is carried out under conventional conditions (e.g., thermal conditions), optionally in the presence of an additional catalyst (e.g., the catalyst described in WO 00/36210).

An example of such a protecting group A group wherein L is suitable for imparting any desirable group for solubility.

L is better, a group wherein Z ¹ , Z ² and Z ³ are each independently C ₁ -C ₆ alkyl, and Z ⁴ and Z ⁸ are each independently C ₁ -C ₆ alkyl, hetero aerobic, sulfur or N ( a C ₁ -C ₆ alkyl group of Z ¹² ) ₂ or a phenyl group or a group which is unsubstituted or substituted by a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a halogen group, a cyano group or a nitro group Benzene, Z ⁵ , Z ⁶ and Z ⁷ are each independently hydrogen or C ₁ -C ₆ alkyl, Z ⁹ -based hydrogen, C ₁ -C ₆ alkyl or formula a group, Z ¹⁰ and Z ¹¹ are independently of each other hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogen, cyano, nitro, N(Z ¹² ) ₂ , or Substituted or substituted by halo, cyano, nitro, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy, Z ¹² and Z ¹³ C ₁ -C ₆ alkyl, Z ¹⁴ Hydrogen or C ₁ -C ₆ alkyl, and Z ¹⁵ is hydrogen, C ₁ -C ₆ alkyl, or unsubstituted or substituted by C ₁ -C ₆ alkyl, Q is unsubstituted or C _1- C ₆ alkoxy, C ₁ -C ₆ alkylthio or C ₂ -C ₁₂ dialkylamino mono- or poly-substituted p, qC ₂ -C ₆ alkyl, wherein p and q are different Position number, X is a hetero atom selected from the group consisting of nitrogen, oxygen, and sulfur, m' is a number 0 in the case of X-based oxygen or sulfur, and m is a number 1 in the case of X-based nitrogen, and L ¹ and L ² are each other Independently unsubstituted or mono- or poly-C ₁ -C ₁₂ alkoxy-, -C ₁ -C ₁₂ alkylthio-, -C ₂ -C ₂₄ dialkylamino-, -C ₆ - C ₁₂ aryloxy-, -C ₆ -C ₁₂ arylthio-, -C ₇ -C ₂₄ alkylarylamino- or -C ₁₂ -C ₂₄ diarylamino substituted C ₁ -C ₆ alkyl or [-(p', q'-C ₂ -C ₆ alkylene)-Z-] _n' -C ₁ -C ₆ alkyl, n' is a number from 1 to 1000, p' and q' are different position numbers, Z are each independently a heteroatom oxygen, sulfur or a C ₁ -C ₁₂ alkyl substituted nitrogen, and a [-C ₂ -C ₆ -alkyl-Z-] repeating unit The C ₂ -C ₆ alkylene groups may be the same or different, and L ₁ and L ₂ may be saturated or have an unsaturation of 1 to 10, may be undoped or have 1 to 10 in any position. a group selected from the group consisting of -(C=O)- and -C ₆ H ₄ -, and may have no other substituents or have 1 to 10 other substitutions selected from the group consisting of halogen, cyano and nitro base. Optimally, L-style The group.

The synthesis of the Br-A-Br compound is described in WO 08/000664 and WO 09/047104, or can be synthesized analogously to the methods described herein. The N-aryl substituted compounds of the formula Br-A-Br can be synthesized analogously to the methods described in US-A-5,354,869 and WO 03/022848.

Halogen is fluorine, chlorine, bromine and iodine.

If possible, C ₁ -C ₂₅ alkyl (C ₁ -C ₁₈ alkyl) is usually straight-chain or branched alkyl. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl Base, 2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1,1,3,3,5,5-hexa Hexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 1,1,3 , 3-tetramethylbutyl and 2-ethylhexyl, n-decyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl Alkyl, heptadecyl, octadecyl, eicosyl, docosyl, behenyl, tetracosyl or hapentadecyl. C ₁ -C ₈ alkyl is usually methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, isobutyl, tert-butyl, n-pentyl, 2 -pentyl, 3-pentyl, 2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2- Ethylhexyl. The C ₁ -C ₄ alkyl group is usually methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, isobutyl, tert-butyl.

C ₂ -C ₁₈ alkenyl straight-chain or branched alkenyl group, such as vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, N-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, positive - Dodecan-2-alkenyl or n-octadec-4-enyl.

C _2-18 alkynyl is a straight or branched and preferably unsubstituted or substituted C _2-8 alkynyl group, for example, ethynyl, 1-propyn-3-yl, 1-butyne 4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyne-5- , 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-pentene-4-yne-1 -yl, 1,3-hexadiyn-5-yl, 1-octyne-8-yl, 1-decyne-9-yl, 1-decynyl-10-yl or 1-tetradecyne-24 -base.

C ₁ -C ₂₅ alkoxy (C ₁ -C ₁₈ alkoxy) is a linear or branched alkoxy group such as methoxy, ethoxy, n-propoxy, isopropoxy, positive -butoxy, second-butoxy, tert-butoxy, pentyloxy, isopentyloxy or tert-pentyloxy, heptyloxy, octyloxy, isooctyloxy, oxime Base, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecanyloxy and octadecyloxy. Examples of C ₁ -C ₈ alkoxy groups are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second-butoxy, isobutoxy, third Butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy 1,1,3,3-tetramethylbutoxy and 2-ethylhexyloxy, preferably C ₁ -C ₄ alkoxy, such as usually methoxy, ethoxy, n-propyl Oxyl, isopropoxy, n-butoxy, second-butoxy, isobutoxy, tert-butoxy. The term "alkylthio" means the same group as the alkoxy group except that the oxygen atom of the ether bond is replaced by a sulfur atom.

a C ₁ -C ₁₈ perfluoroalkyl group, especially a C ₁ -C ₄ perfluoroalkyl group having a branched or unbranched group, such as —CF ₃ , —CF ₂ CF ₃ , —CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -(CF ₂ ) ₃ CF ₃ and -C(CF ₃ ) ₃ .

The term "aminocarboxamyl" is usually an unsubstituted or substituted C _1-18 amine carbenyl group, preferably a C _1-8 amine carbenyl group, for example, an amine carbenyl group, a methylamine carbenyl group. , ethylamine, mercapto, n-butylamine, mercapto, tert-butylamine, mercapto, dimethylamine, mercaptooxy, morpholinylcarboxamidine or pyrrolidinylamine base.

C ₅ -C ₁₂ cycloalkyl is typically based cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, nonyl, cyclodecyl, cycloalkyl undecyl, cyclododecyl, the preferred system may not Substituted or substituted cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl. The cycloalkyl group (especially cyclohexyl) may be condensed one or two times by a phenyl group which may be substituted 1 to 3 times by a C ₁ -C ₄ -alkyl group, a halogen group and a cyano group. Examples of such condensed cyclohexyl groups are:

especially Wherein R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ and R ¹⁵⁶ are, independently of each other, C ₁ -C ₈ -alkyl, C ₁ -C ₈ -alkoxy, halogen and cyano, especially hydrogen.

C ₆ -C ₂₄ aryl (C ₆ -C ₁₈ aryl) is usually unsubstituted or substituted phenyl, fluorenyl, chamomile, naphthyl, biphenyl, asymmetrically introduced ( As-indacenyl), s-indacenyl, acenaphthylenyl, fluorenyl, phenanthryl, fluorenyl, triphenylalkenyl, oxalatyl, tetracene, fluorenyl , mercapto, pentaphenyl, hexaphenyl, anthracenyl, or anthracenyl, preferably phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 9-phenanthryl, 2- or 9 - mercapto, 3- or 4-biphenyl. Examples of C ₆ -C ₁₂ aryl groups are unsubstituted or substituted phenyl, 1-naphthyl, 2-naphthyl, 3- or 4-biphenyl, 2- or 9-fluorenyl or 9-phenanthrene. base.

C ₇ -C ₂₅ aralkyl is usually benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω , ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl, ω-phenyl-eicosyl or ω-phenyl- A dodecyl group, preferably a C ₇ -C ₁₈ aralkyl group, such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, Ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl, and especially C ₇ -C ₁₂ aralkyl, such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, or ω, Omega-dimethyl-omega-phenyl-butyl, wherein both the aliphatic hydrocarbon group and the aromatic hydrocarbon group may be unsubstituted or substituted. Preferred examples are benzyl, 2-phenylethyl, 3-phenylpropyl, naphthylethyl, naphthylmethyl, and cumyl.

A heteroaryl group is typically a C ₂ -C ₂₀ heteroaryl group, ie a ring or fused ring system having 5 to 7 ring atoms of a nitrogen, oxygen or sulfur-based hetero atom, and usually having 5 to 30 atoms and An unsaturated heterocyclic group having at least 6 conjugated π-electrons, such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl, thioxyl, furyl, fluorenyl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, dipyridyl, triazinyl, Pyrimidinyl, pyrazinyl, pyridazinyl, pyridazinyl, isodecyl, decyl, oxazolyl, fluorenyl, quinazinyl, quinolinyl, isoquinolinyl, pyridazinyl, naphthyridine Base, quinoxalinyl, quinazolinyl, Polinyl, acridinyl, oxazolyl, porphyrinyl, benzotriazolyl, benzoxazolyl, phenanthryl, acridinyl, pyrimidinyl, phenanthroline, phenazinyl, isothiazolyl A phenothiazine group, an isoxazolyl group, a furazyl group or a phenoxazinyl group which may be unsubstituted or substituted.

Possible substituents for the above groups are C ₁ -C ₈ alkyl, hydroxy, decyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthio, halogen, halo-C ₁ -C ₈ alkyl , cyano, amine, mercapto, nitro or carboxyalkyl, especially C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthio, halogen, halo-C ₁ -C ₈ alkyl, or cyano.

a C ₁ -C ₁₈ alkyl group having one or more O groups, for example, (CH ₂ CH ₂ O) _1-9 -R ^x , wherein R ^x is H or C ₁ -C ₁₀ alkyl; CH ₂ -CH (OR ^y' )-CH ₂ -OR ^y , wherein R ^y is C ₁ -C ₁₈ alkyl, and R ^{y '} contains the same definition or system H as R ^y .

If a substituent (e.g., R ¹⁸ ) occurs more than once in a group, it may be different at each occurrence.

The phrase "substituted by G" means that one or more, especially one to three, substituents G may be present.

As noted above, the above groups may be substituted by E' and/or may be miscible with D' if desired. Of course, it may be heterozygous only in the case of a group containing at least 2 carbon atoms bonded to each other by a single bond; the C ₆ -C ₁₈ aryl group is not hetero-hetero; the hetero-heteroarylalkyl group contains the unit D in the alkyl moiety. a C ₁ -C ₁₈ alkyl group substituted by one or more E' and/or one or more units D, for example (CH ₂ CH ₂ O) _1-9 -R ^x , wherein R ^x is H or C ₁ -C ₁₀ alkyl or C ₂ -C ₁₀ alkyl fluorenyl (for example, CO-CH(C ₂ H ₅ )C ₄ H ₉ ), CH ₂ -CH(OR ^y' )-CH ₂ -OR ^y , Wherein R ^y is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, phenyl, C ₇ -C ₁₅ phenylalkyl, and R ^y' encompasses the same definition or system H as R ^y ; _1- C ₈ alkylene-COO-R ^z , for example, CH ₂ COOR _z , CH(CH ₃ )COOR ^z , C(CH ₃ ) ₂ COOR ^z , wherein R ^z is H, C ₁ -C ₁₈ alkyl , (CH ₂ CH ₂ O) _1-9 -R ^x , and R ^x encompasses the above definition; CH ₂ CH ₂ -O-CO-CH=CH ₂ ; CH ₂ CH(OH)CH ₂ -O-CO-C (CH ₃ )=CH ₂ .

Mixtures comprising the polymers of the invention can produce semiconducting layers comprising the polymers of the invention (typically from 5% to 99.999% by weight, especially from 20% to 85% by weight) and at least one other material. Other materials may be, but are not limited to, portions of the same polymer of the present invention having different molecular weights, another polymer of the present invention, semiconductive polymers, small organic molecules, carbon nanotubes, fullerene derivatives, inorganic particles (quantum dots, quantum rods, quantum tripods, TiO ₂ , ZnO, etc.), conductive particles (Au, Ag, etc.), insulator materials (for example, for gate dielectrics) (PET, PS) Wait).

The polymers of the present invention can be blended with small molecules as described in, for example, European Patent Application No. 0915591 9.5, WO 09/047104, US 6,690, 029, WO 2007082584, and WO 2008107089.

WO 2007082584:

WO 2008107089:

Wherein one of Y ^{1 '} and Y ^{2 '} represents -CH= or =CH- and the other represents -X'-, and one of Y ^{3 '} and Y ^{4 '} represents -CH= or =CH- and The other represents -X'-, X'--O-, -S-, -Se- or -NR'''-, R"" is a cyclic, linear or having 1 to 20 C atoms. a branched alkyl or alkoxy group, or an aryl group having 2 to 30 C atoms, which are optionally fluorinated or perfluorinated, and R' is H, F, Cl, Br, I, CN, having 1 a linear or branched alkyl or alkoxy group of up to 20 C atoms and optionally fluorinated or perfluorinated, an aryl group having 6 to 30 C atoms and optionally fluorinated or perfluorinated, Or CO ₂ R", wherein R" is H, an alkyl group having from 1 to 20 C atoms and optionally fluorinated, or an aryl group having from 2 to 30 C atoms and optionally fluorinated, R'''Line H or a cyclic, linear or branched alkyl group having 1 to 10 C atoms, y is 0 or 1, and x is 0 or 1.

The polymer may contain one small molecule or a mixture of two or more small molecule compounds.

Accordingly, the invention is also directed to organic semiconductor materials, layers or components comprising the polymers of the invention.

The polymer of the present invention can be used as a semiconductor layer in a semiconductor device. Accordingly, the invention is also directed to a semiconductor device comprising a polymer of the invention, or an organic semiconductor material, layer or component. The semiconductor device is in particular an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor.

The polymer of the present invention can be used singly or in combination as an organic semiconductor layer of a semiconductor device. The layer can be provided by any useful means, such as vapor deposition (for relatively low molecular weight materials) and printing techniques. The compounds of the present invention are sufficiently soluble in organic solvents and can be solution deposited and patterned (for example, by spin coating, dip coating, ink jet printing, gravure printing, flexographic printing, offset printing, screen printing, microcontacting). (wave) - printing, drip or zone casting, or other conventional techniques to implement).

The polymer of the present invention can be used in an integrated circuit comprising a plurality of OTFTs, as well as in various electronic articles. Such items include, for example, radio frequency identification (RFID) tags, backplanes for smart displays (eg, for personal computers, mobile phones, or handheld devices), smart cards, memory devices, sensors ( For example, a light sensor, an image sensor, a biosensor, a chemical sensor, a mechanical sensor or a temperature sensor), in particular a photodiode, or a security device and the like.

Another aspect of the invention is an organic semiconductor material, layer or component comprising one or more polymers of the invention. Another aspect is the use of the polymers or materials of the present invention in organic photovoltaic (PV) devices (solar cells), photodiodes, or organic field effect transistors (OFETs). Another aspect is an organic photovoltaic (PV) device (solar cell), photodiode, or organic field effect transistor (OFET) comprising a polymer or material of the invention.

The polymers of the invention are typically used as organic semiconductors in the form of thin organic layers or films, preferably less than 30 microns thick. Typically, the semiconducting layer of the present invention is at most 1 micron (= 1 μm) thick, but may be thicker if desired. For various electronic device applications, the thickness can also be less than about 1 micron thick. For example, when used in an OFET, the layer thickness can typically be 100 nm or less. The exact thickness of the layer depends, for example, on the requirements of the electronic device using the layer.

For example, an active semiconductor trench between a germanium electrode and a source electrode in an OFET can comprise a layer of the invention.

The OFET device of the present invention preferably comprises:

- source electrode,

- 汲 electrode,

- the gate electrode,

- semi-conductive layer,

- one or more gate insulator layers, and

- a substrate as appropriate, wherein the semiconducting layer comprises one or more polymers of the invention.

The gate electrode, the source electrode and the germanium electrode, and the insulating and semiconductive layers in the OFET device may be arranged in any order, provided that the source electrode and the germanium electrode are separated from the gate electrode by an insulating layer, and both the gate electrode and the semiconductor layer are in contact with the insulating layer. And the source electrode and the germanium electrode are both in contact with the semiconductive layer.

Preferably, the OFET comprises an insulator having a first side and a second side, a gate electrode on the first side of the insulator, a layer on the second side of the insulator and comprising the polymer of the invention, and the polymer layer The upper electrode and the source electrode.

The OFET device can be a top gate device or a bottom gate device.

Suitable structures and methods of manufacture for OFET devices are well known to those skilled in the art and are described in the references (e.g., WO 03/052841).

The gate insulator layer may comprise, for example, a fluoropolymer such as the commercially available Cytop 809M. Or Cytop 107M (from Asahi Glass). Preferably, the gate insulator layer is deposited from a formulation comprising an insulator material and one or more solvents (fluorine solvents) having one or more fluorine atoms (preferably perfluorosolvent), for example by spin coating or knife coating. It is carried out by metal bar coating, spraying or dip coating or other conventional methods. Suitable for perfluorinated solvent systems (for example) FC75 (purchased from Acros, catalog number 12380). Other suitable fluoropolymers and fluorosolvents are well known in the prior art, such as the perfluoropolymer Teflon AF 1600 or 2400 (from DuPont), or Fluoropel (from Cytonix) or perfluorosolvent FC 43 (Acros, No. 12377).

The semiconducting layer comprising the polymer of the invention may additionally comprise at least one other material. Other materials may be, but are not limited to, another polymer of the present invention, a semiconductive polymer, a polymeric binder, an organic small molecule different from the polymer of the present invention, a carbon nanotube, a fullerene derivative, an inorganic particle ( Quantum dots, quantum rods, tripod type quantum, TiO ₂ , ZnO, etc.), conductive particles (Au, Ag, etc.), and insulating materials (for example, for gate dielectrics) (PET, PS, etc.). As noted above, the semiconducting layer can also be comprised of a mixture of one or more of the polymers of the present invention and polymeric binders. The ratio of the polymer of the invention to the polymeric binder can vary from 5% to 95%. Preferably, the polymeric binder is a semi-crystalline polymer such as polystyrene (PS), high density polyethylene (HDPE), polypropylene (PP), and polymethyl methacrylate (PMMA). Using this technique, electrical performance deterioration can be avoided (see WO 2008/001123 A1).

The polymers of the invention are preferably used in organic photovoltaic (PV) devices (solar cells). Accordingly, the present invention provides a PV device comprising the polymer of the present invention. Devices having this configuration also have rectifying properties and may therefore also be referred to as photodiodes. The photosensitive device can be used as a solar cell for generating electricity from light and a photodetector for measuring or detecting light.

The structure of an organic photovoltaic device (solar cell) is described, for example, in C. Deibel et al., Rep. Prog. Phys. 73 (2010) 096401 and Christoph Brabec, Energy Environ. Sci 2. (2009) 347-303.

The PV unit is included in the following order:

(a) cathode (electrode),

(b) a transition layer, as appropriate, such as an alkali metal halide, especially lithium fluoride,

(c) a photoactive layer,

(d) a smooth layer, as appropriate,

(e) anode (electrode),

(f) Substrate.

The photoactive layer comprises a polymer of the invention. Preferably, the photoactive layer is prepared from a conjugated polymer of the invention (as an electron donor) and an acceptor material (such as fullerenes, especially functionalized fullerene PCBM) (as an electron acceptor). As mentioned above, the photoactive layer may also contain a polymeric binder. The polymer of the invention may comprise from 0.1% to 99.9% by weight, in particular from 1% to 99% by weight, very particularly from 5% to 95% by weight, based on the polymer of the invention and the amount of polymeric binder. Change between %. Preferably, the polymeric binder is a semi-crystalline polymer such as polystyrene (PS), high density polyethylene (HDPE), polypropylene (PP), and polymethyl methacrylate (PMMA).

For a heterojunction solar cell, the active layer preferably comprises a mixture of the polymer of the invention and fullerenes in a weight ratio of 1:1 to 1:3, such as [60] PCBM (=6, 6-phenyl-C ₆₁ -methyl butyrate), or [70] PCBM. The fullerene used in the present invention has a wide range of sizes (number of carbon atoms per molecule). The term fullerene as used herein includes various cage molecules of pure carbon, including Buckminsterfullerene (C ₆₀ ) and related "spherical" fullerenes and carbon nanotubes. Fullerenes may be selected from those present in the conventional art, for example, range ₂₀ -C ₁₀₀₀ C. Preferably, the fullerene is selected from the range of C ₆₀ -C ₉₆ . Most preferably, fullerene is C ₆₀ or C ₇₀ , such as [60] PCBM, or [70] PCBM. Chemically modified fullerenes are also permitted, provided that the modified fullerenes retain acceptor type and electron mobility characteristics. The acceptor material may also be a material selected from the group consisting of: any semiconductive polymer (for example, the polymer of the present invention, provided that the polymer retains acceptor type and electron mobility characteristics), small organic molecules, carbon nanotubes Tube, inorganic particles (quantum dots, quantum rods, tripod type quantum, TiO ₂ , ZnO, etc.).

The photoactive layer is prepared from the polymers of the invention (as electron donors) and fullerenes, especially functionalized fullerenes PCBM (as electron acceptors). The two components are mixed with a solvent and applied to the smoothing layer as a solution by, for example, a spin coating method, a drip method, a Langmuir-Blodgett ("LB") method. , inkjet printing method and drop coating method. A light roller or printing method can also be used to coat a larger surface using this photoactive layer. A dispersant such as chlorobenzene is preferably used in place of the toluene which is usually used as a solvent. Among these methods, a vacuum deposition method, a spin coating method, an inkjet printing method, and a casting method are particularly preferable from the viewpoint of workability and cost.

In the case of forming a layer using a spin coating method, a casting method, and an inkjet printing method, a solution having a concentration of 0.01% by weight to 90% by weight prepared by dissolving or dispersing the composition in an appropriate organic solvent such as the following may be used. And / or dispersion to carry out coating: benzene, toluene, xylene, tetrahydrofuran, methyl tetrahydrofuran, N, N-dimethylformamide, acetone, acetonitrile, anisole, dichloromethane, dimethyl hydrazine , chlorobenzene, 1,2-dichlorobenzene and mixtures thereof.

Photovoltaic photovoltaic (PV) devices can also be constructed from multi-junction solar cells that are processed on top of each other to absorb the solar spectrum over a wider range. Such structures are described, for example, in App. Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006), WO2004/112161 and Christoph Brabec, Energy Environ. Sci 2. 2009) 347-303.

The so-called 'serial-type solar cells' are included in the following order:

(a) cathode (electrode),

(b) a transition layer, as appropriate, such as an alkali metal halide, especially lithium fluoride,

(c) a photoactive layer,

(d) a smooth layer, as appropriate,

(e) Central electrodes (eg Au, Al, ZnO, TiO _2, etc.)

(f) additional electrodes for matching energy levels, as appropriate,

(g) a transition layer, as appropriate, such as an alkali metal halide, especially lithium fluoride,

(h) a photoactive layer,

(i) a smooth layer as appropriate,

(j) anode (electrode),

(k) Substrate.

The PV device can also be treated on a fibrous article as described, for example, in US 20070079867 and US 20060013549.

Due to their excellent self-organizing properties, materials or films comprising the polymers of the invention may also be used alone or in combination with other materials in LCD or OLED devices or as alignment layers for use in LCD or OLED devices, such as, for example, US 2003 Said in /0021913.

The following examples are included to illustrate the invention and not to limit the scope of the patent application. All parts and percentages are by weight unless otherwise indicated.

The weight average molecular weight (Mw) and polydispersity (Mw/Mn = PD) were measured by thermothermal gel permeation chromatography (HT-GPC) [equipment: GPC PL 220 from Polymer Laboratory (Church Stretton, UK) ; now Varian), reaction from refractive index (RI), chromatographic conditions: column: 3 "PLgel Olexis" column from Polymer Laboratory (Church Stretton, UK); average particle size 13 μm (size 300 ×8 mm ID) Mobile phase: 1,2,4-trichlorobenzene, purified by vacuum distillation and stabilized by butylated hydroxytoluene (BHT, 200 mg/l), chromatography temperature: 150 ° C; mobile phase flow: 1 ml/min; solute concentration: approx. 1 mg/ml; injection volume: 200 μl; assay: RI, molecular weight calibration procedure: using a set of 10 polystyrene calibration standards obtained from Polymer Laboratories (Church Stretton, UK) Relative calibration of the polystyrene, the molecular weight of the polystyrene is between 1,930,000 Da-5,050 Da, that is, PS 1,930,000, PS 1,460,000, PS 1,075,000, PS 560,000, PS 330,000, PS 96,000, PS 52,000, PS 30,300, PS 10,100, PS 5,050 Da. Polynomial calibration was used to calculate the molecular weight.

All of the polymer structures given in the examples below are idealized representations of the polymer products obtained via the polymerization procedure. If two or more components are copolymerized with each other, the sequential end-view polymerization conditions in the polymer may be alternating or random.

Instance Example 1

a) 20 g [88949-34-2] and 25.76 g of potassium carbonate were suspended in 300 ml of anhydrous dimethylformamide and the mixture was heated to 90 ° C under nitrogen. Then 79 g [1044598-79-9] was added dropwise. The reaction mixture was then stirred at 90 ° C for 6 h. After cooling to room temperature, ethyl acetate was added and the mixture was washed with water. The organic phase was dried over MgSO4 and evaporated. The product was purified by column chromatography on cerium oxide to obtain the compound of formula 1. ¹ H-NMR data (ppm, CDCl ₃ ): 8.33 2H d, 7.60 2H d, 6.68 2H dxd, 4.03 4H d, 1.85-1.75 2H m, 1.45-1.15 48H m, 0.88 6H t, 0.86 6H t;

b) 6.44 g of Compound 1 was dissolved in 100 ml of chloroform. The mixture was cooled to -10 °C and then 1.99 g of N-bromo-succinimide (NBS) was added and the mixture was stirred at -10 °C for 2 hours. The reaction mixture was washed with water, dried over magnesium sulfate and evaporated. The crude product was purified by column chromatography on yttrium oxide to give the compound of formula 2. ¹ H-NMR data (ppm, benzene-D ₆ ): 8.72 2H d, 6.05 2H d, 4.13 4H d, 2.06-2.02 2H m, 1.65-1.30 48H m, 1.01 6H t, 1.00 6H t;

c) Add 0.5 g of compound 2, 0.188 g of 1,4-benzene in a three-necked reaction flask under an argon atmosphere Acid bis(pinacol) ester [99770-93-1] and 51 mg palladium acetate. 15 ml of degassed THF was added to the reaction flask and the mixture was heated to dissolve the starting material. After further degassing with argon, 27 mg of 2-(di-tert-butyl-phosphino)-1-phenyl-1H-pyrrole was added and the reaction mixture was heated to reflux. Then 146 mg of lithium hydroxide hydrate was added and the reaction mixture was stirred at reflux for 2 hours. The reaction mixture was then cooled to room temperature and the product was precipitated with methanol, filtered and washed with methanol. The polymer of Formula 3 was obtained by Soxhlet extraction. The chloroform fraction contained a polymer having a Mw of 90,100 and a polydispersity of 2.69 (measured by high temperature GPC).

Example 2

In a manner similar to that of Example 1c) from Compound 2 and Thiophene-II The acid-pinacol ester [175361-81-6] begins to synthesize the polymer of formula 4. The tetrahydrofuran portion of the Soxhlet extraction contained a polymer of Formula 4 having a Mw of 74,600 and a polydispersity of 2.26 (measured by high temperature GPC).

Example 3

In a manner similar to that of Example 1c) from Compound 2 and Thienothiophene-II Acid-pinacol ester [924894-85-9] began to synthesize the polymer of formula 5. The crude polymer of Formula 5 had an Mw of 8,300 and a polydispersity of 2.06 (measured by high temperature GPC).

Example 4

In a manner similar to Example 1c) from Compound 2 and Di-thiophene-II The acid-pinacol ester [239075-02-6] began to synthesize the polymer of formula 6. The crude polymer of Formula 6 had a Mw of 6,300 and a polydispersity of 1.44 (measured by high temperature GPC).

Example 5

a) according to the compound [1220883-00-0], the dibromide of formula 2 and the formula [883742-29-8] The acid pinacol ester is reacted in a Suzuki coupling reaction to produce a compound of formula 7. ¹ H-NMR data (ppm, CDCl ₃ ): 8.44 2H bs, 7.23 2H bs, 6.94 2H bs, 6.75 2H d, 4.14 4H d, 2.62 4H t, 1.92 2H m, 1.71-1.60 4H m, 1.45-1.15 60H m, 0.92 6H t, 0.85 6H t, 0.82 6H t;

b) bromination of a compound of formula 7 using N-bromosuccinimide (NBS) according to compound [1220883-03-3] to yield a compound of formula 8. ¹ H-NMR data (ppm, CDCl ₃ ): 8.45 2H bs, 7.08 2H bs, 6.73 2H d, 4.09 4Hd, 2.57 4H t, 1.93 2H m, 1.70-1.55 4H m, 1.48-1.15 60H m, 0.90 6H t , 0.84 6H t, 0.83 6H t;

c) from compound 8 and thiophene-di in a manner similar to that of Example 1c) The acid-pinacol ester [175361-81-6] begins to synthesize the polymer of formula 9. The tetrahydrofuran portion of the Soxhlet extraction contained a polymer of formula 9 having a Mw of 36,200 and a polydispersity of 1.86 (measured by high temperature GPC).

Example 6

In a similar manner to Example 1c), from 0.8 equivalents of compound 8, 0.2 equivalent of compound [214493-03-5] and 1 equivalent of thiophene-II The acid-pinacol ester [175361-81-6] begins to synthesize the polymer of formula 10. The crude polymer of Formula 10 had a Mw of 11,500 and a polydispersity of 1.90 (measured by high temperature GPC).

Example 7

In a similar manner to Example 1c), from 0.5 equivalents of compound 8, 0.5 equivalent of compound [214493-03-5] and 1 equivalent of thiophene-II The acid-pinacol ester [175361-81-6] begins to synthesize the polymer of formula 11. The crude polymer of Formula 11 had a Mw of 9,900 and a polydispersity of 1.61 (measured by high temperature GPC).

Example 8

In a manner similar to that of Example 1c) from the compound [1000623-98-2] and furan-di The acid-pinacol ester [476004-83-8] began to synthesize the polymer of formula 12. The tetrahydrofuran portion of the Soxhlet extraction contained a polymer of formula 12 having a Mw of 60,500 and a polydispersity of 2.28 (measured by high temperature GPC).

Example 9

a) a dibromide of the formula [1000623-98-2] and a formula [883742-29-8] according to the compound [1220883-00-0] The acid pinacol ester is reacted in a Suzuki coupling reaction to produce a compound of formula 13.

b) bromination of a compound of formula 13 using N-bromosuccinimide (NBS) according to compound [1220883-03-3] to yield a compound of formula 14.

c) in a manner similar to that of Example 1c) from Compound 14 and Furan-II The acid-pinacol ester [476004-83-8] began to synthesize the polymer of formula 15. The tetrahydrofuran portion of the Soxhlet extraction contained a polymer of formula 15 having a Mw of 40,200 and a polydispersity of 2.10 (measured by high temperature GPC).

Example 10

In a similar manner to Example 1c), from 0.8 equivalents of compound 14, 0.2 equivalent of compound [214493-03-5] and 1 equivalent of furan-di The acid-pinacol ester [476004-83-8] began to synthesize the polymer of formula 16. The tetrahydrofuran portion of the Soxhlet extraction contained a polymer of formula 16 having a Mw of 27,100 and a polydispersity of 1.99 (measured by high temperature GPC).

Example 11

In a manner similar to Example 1c) from 0.5 equivalents of compound 14, 0.5 equivalents of compound [214493-03-5] and 1 equivalent of furan-di The acid-pinacol ester [476004-83-8] began to synthesize the polymer of formula 17. The tetrahydrofuran portion of the Soxhlet extraction contained a polymer of the formula 17 having a Mw of 22,600 and a polydispersity of 2.00 (measured by high temperature GPC).

Example 12

In a manner similar to that of Example 1c) from the compound [1000623-98-2] and pyrrole-di The acid-pinacol ester [476004-84-9] began to synthesize the polymer of formula 18. The crude polymer of Formula 18 had an Mw of 8,500 and a polydispersity of 2.43 (measured by high temperature GPC).

Example 13

In a manner similar to that of Example 1c) from Compound 14 and Pyrrole-II The acid-pinacol ester [476004-84-9] began to synthesize the polymer of formula 19. The crude polymer of Formula 19 had a Mw of 5,000 and a polydispersity of 2.15 (measured by high temperature GPC).

Example 14

In a manner similar to Example 1c) from 0.8 equivalents of compound 14, 0.2 equivalents of compound [214493-03-5] and 1 equivalent of pyrrole-di The acid-pinacol ester [476004-84-9] begins to synthesize the polymer of formula 20. The crude polymer of Formula 20 had a Mw of 5,500 and a polydispersity of 1.87 (measured by high temperature GPC).

Example 15

In a similar manner to Example 1c), from 0.5 equivalent of compound 14, 0.5 equivalent of compound [214493-03-5] and 1 equivalent of pyrrole-di The acid-pinacol ester [476004-84-9] began to synthesize the polymer of formula 21. The crude polymer of Formula 21 had a Mw of 3,200 and a polydispersity of 1.77 (measured by high temperature GPC).

Application Example 1: Photovoltaic application of semiconductive polymer 3 Polymer-based bulk heterojunction solar cell

The solar cell has the following structure: Al electrode/LiF layer/organic layer (containing polymer 3) and [70]PCBM/[poly(3,4-extended ethylenedioxy-thiophene) (PEDOT) and poly(styrene) Sulfonic acid) (PSS)] / ITO electrode / glass substrate mixture. A solar cell was fabricated by spin coating a PEDOT-PSS layer onto pre-patterned ITO on a glass substrate. Subsequently, a 1:1.5 mixture of polymer 3 (1% by weight): [70] PCBM (substituted C ₇₀ fullerene) was spin-coated from oDCB (organic layer). LiF and Al sublimate through a shadow mask under high vacuum.

Solar cell performance

Solar cells were measured under a solar simulator. The current was then estimated under AM 1.5 conditions using an external quantum efficiency (EQE) chart. This measurement yielded the following values: J _sc = 8.5 mA/cm ² , FF = 0.58 and V _oc = 0.82 V, and the estimated total efficiency was 4.04%.

Example 16

The polymer of formula 23 was synthesized starting from 0.96 g of compound 2, 508.6 g of compound 22 in a manner analogous to Example 1c). The polymer was purified by Soxhlet extraction using different solvents: tetrahydrofuran, chloroform and o-dichlorobenzene. The 720 mg o-dichlorobenzene moiety contained a polymer of formula 16 having a Mw of 100,000 and a polydispersity of 2.59 (measured by high temperature GPC).

Application Example 2: Airport-based transistor based on polymer 23

A bottom gate thin film transistor (TFT) structure with a p-Si gate (10 cm) was used in all experiments. A 300 nm thick high quality thermal SiO ₂ layer was used as the gate insulator with a C _i = 32.6 nF/cm ² capacitance/cell area. The source and drain electrodes are patterned directly on the gate oxide by photolithography. A gold source electrode and a germanium electrode which define a trench having a width W = 10 mm and various lengths L = 4 m, 8 m, 15 m, 30 m are used. Before depositing the organic semiconductor, the SiO ₂ surface was obtained by exposure to hexamethylene decazane (HMDS) in saturated decane vapor at 160 ° C for 2 hours at 800 rpm (revolutions per minute). Spinning speed HMDS was spin coated for about 1 minute, or the substrate was treated with a 0.1 m solution of octadecyltrichlorodecane (OTS) in toluene at 60 ° C for 20 minutes. After rinsing with isopropyl alcohol, the substrate was dried.

A semiconductor film was produced by spin coating or dripping a DPP derivative of the formula 23 obtained in Example 16 and stored in a 0.5% (w/w) solution of o-dichlorobenzene. Spin coating was achieved in an ambient condition at a rotational speed of 1000 rpm (revolutions per minute) over about 60 seconds. After drying at 100 ° C for 15 minutes, the device was evaluated as it was after precipitation.

Transistor properties in o-dichlorobenzene

The characteristics of the transistor were measured on an automated transistor detector (TP-10).

According to a linear fit to the square root of the saturation transfer characteristic, the field effect mobility was measured to be 1.1 × 10 ^-2 cm ² /Vs after drying and the on/off current ratio was 2.7 × 10 ⁵ . The threshold voltage is approximately 2.3 V.

Application Example 3: Organic bulk heterojunction solar cell based on polymer 23

The solar cell has the following structure: Al electrode / LiF layer / organic layer (including the compound of the present invention) / [poly(3,4-extended ethyldioxy-thiophene) (PEDOT): poly(styrenesulfonic acid) (PSS) )] / ITO electrode / glass substrate. A solar cell was fabricated by spin coating a PEDOT:PSS layer onto pre-patterned ITO on a glass substrate. Subsequently, a compound of formula 23 (0.8% by weight) was spin-coated: [60] PCBM or [70] PCBM (substituted C ₆₀ or C ₇₀ fullerene) 1:2 mixture (organic layer). LiF and Al sublimate through a shadow mask under high vacuum.

Solar cell performance

Solar cells were measured under a solar simulator. The current was then estimated under AM 1.5 conditions using an external quantum efficiency (EQE) chart. This measurement yielded the following values: J _sc = 14.35 mA/cm ² , FF = 0.61 and V _oc = 0.72 V, and the estimated total efficiency was 6.3%.

Example 17: Synthesis of Polymer 26

a) To a cooled (-78 ° C) solution of 1.05 g of 24 in anhydrous THF was added 4.5 ml of butyl lithium (2.5 M in hexane). The resulting solution was stirred at 0 °C for 15 minutes and cooled to -78 °C. Add 5.2 g of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborate dropwise It was kept at -78 ° C for 5 minutes, then the solution was slowly warmed to room temperature and stirring was continued for 30 minutes. The reaction was quenched by the addition of 50 mL HCl (10%) and the product was extracted twice with 40 mL ethyl acetate. The combined organic extracts were dried <RTI ID=0.0>

b) 0.96 g ₂ , 0.5 g compound 25, 15 mg Pd (acetate) ₂ , 76 mg 2-(di-tert-butyl-phosphino)-1-phenyl-pyrrole with 60 ml under argon The tetrahydrofuran was mixed and warmed to 40 °C. Then 0.29 g of lithium hydroxide solution was added to the reaction mixture. The reaction mixture was then refluxed for 4 hours and cooled to room temperature. The green-blue mixture was precipitated using methanol and filtered. The filtrate was dissolved in chloroform and refluxed with a 1% aqueous NaCN solution for 3 hr. The organic phase was washed with water and then dried and evaporated. The polymer was precipitated with methanol and the precipitate was fractionated using THF, chloroform and dichlorobenzene in a Soxhlet. The dichlorobenzene portion contains 610 mg of the desired polymer 26. Mw = 31,500, polydispersity = 1.65 (measured by HT-GPC).

Application Example 4: Organic Body Heterojunction Solar Cell Based on Polymer 26

The solar cell has the following structure: Al electrode / LiF layer / organic layer (including the compound of the present invention) / [poly(3,4-extended ethyldioxy-thiophene) (PEDOT): poly(styrenesulfonic acid) (PSS) )] / ITO electrode / glass substrate. A solar cell was fabricated by spin coating a PEDOT:PSS layer onto pre-patterned ITO on a glass substrate. Then, a compound of Formula 26 (1% by weight) was spin-coated: [60] PCBM or [70] PCBM (substituted C ₆₀ or C ₇₀ fullerene) 1:1.5 mixture (organic layer). LiF and Al sublimate through a shadow mask under high vacuum.

Solar cell performance

Solar cell characteristics were measured under AM 1.5G conditions. Irradiation with a xenon-based solar simulator (100 mW/cm ² ) and a device area of 0.09 cm ² . Under these conditions, the measured efficiency was 5.07% (where Jsc = 10.90 mA/cm ² , FF = 0.57 and Voc = 0.82 V).

Example 18: Synthesis of Polymer 29

a) Compound 28 was synthesized in a similar manner to Example 17a).

b) Polymer 29 was synthesized in a similar manner to Example 17b).

Example 19

a) Add 5.77 g of sodium and 12 mg of FeCl ₃ to 200 ml of the third pentanol. The mixture was then heated to 90 ° C until all of the sodium metal reacted. Subsequently, 8.34 g of 2-furanonitrile [617-90-3] was added in portions and then 20 g [1224573-55-0] was added in portions. The color of the reaction mixture turned red. The reaction mixture was stirred at 90 ° C overnight. The reaction mixture was poured onto ice water and the precipitate was filtered. The filter cake is washed with water, acetone and methanol and water and then dried to yield a compound of formula 30. ¹ H-NMR data (ppm, DMSO-d ₆ ): 8.21 1H d, 8.06 1H d, 7.96 1H dxd, 7.67 1H d, 7.30 1H dxd, 6.84 1H d.

b) The compound of formula 30 is alkylated with 2-hexyl-indenyl-iodide [1044598-79-9] in a similar manner to Example 1a) to give the compound of formula 31. Compound 31 was used directly in the next step without further.

c) The compound of formula 31 is brominated with N-bromosuccinimide (NBS) in a similar manner to Example 1 b) to give the compound of formula 32. ¹ H-NMR data (ppm, CDCl ₃ ): 8.54 1H d, 8.26 1H d, 7.14 1H d, 6.55 1H d, 3.92 2H d, 3.85 2H d, 1.80 1H m, 1.72 1H m, 1.35-1.05 48H m, 0.77 6H t, 0.76 6H t.

d) the dibromide of formula 32 and thiophene-di- in a manner similar to that of Example 1c) The acid-pinacol-ester [175361-81-6] is reacted in a Suzuki coupling reaction to yield a compound of formula 33.

Example 20

The dibromide of formula 32 and naphthalene-di- in a manner similar to that of Example 1c) The acid-pinacol-ester [849543-98-2] is reacted in a Suzuki coupling reaction to produce a compound of formula 34.

Example 21

a) alkylation of di-furyl-di-keto-pyrrolo-pyrrole using 2-ethyl-hexyl-iodide [1653-16-3] in a manner similar to that of Example 1a) [88949-34-2] To produce a compound of formula 35. ¹ H-NMR data (ppm, CDCl ₃ ): 8.33 2H dxd, 7.61 2H d, 6.69 2H dxd, 4.05 4H d, 1.75 2H m, 1.45-1.25 16H m, 0.90 6H t, 0.87 6H t.

b) The compound of formula 35 is brominated with N-bromosuccinimide (NBS) in a similar manner to Example 1 b) to yield the compound of formula 36. ¹ H-NMR data (ppm, CDCl ₃ ): 8.30 2H d, 6.62 2H d, 3.99 4H d, 1.74 2H m, 1.45-1.25 16H m, 0.92 6H t, 0.88 6H t.

Example 22

a) alkylation of di-furyl-di-keto-pyrrolo-pyrrole using 1-dodecyl-iodide [4292-19-7] in a manner similar to that of Example 1a) [88949-34-2] To produce a compound of formula 37. ¹ H-NMR data (ppm, CDCl ₃ ): 8.30 2H dxd, 7.63 2H d, 6.69 2H dxd, 4.11 4H t, 1.69 4H m, 1.45-1.20 36H m, 0.88 6H t.

b) The compound of formula 37 is brominated with N-bromosuccinimide (NBS) in a similar manner to Example 1 b) to yield the compound of formula 38. ¹ H-NMR data (ppm, CDCl ₃ ): 8.25 2H d, 6.63 2H d, 4.05 4H t, 1.67 4H m, 1.45-1.25 36H m, 0.88 6H t.

Example 23

a) alkylation of di-furyl-di-keto-pyrrolo-pyrrole using 2-butyl-octyl-iodide [1256345-37-5] in a manner similar to that of Example 1a) [88949-34-2 ] to produce a compound of formula 39. ¹ H-NMR data (ppm, CDCl ₃ ): 8.33 2H dxd, 7.60 2H d, 6.69 2H dxd, 4.03 4H d, 1.80 2H m, 1.45-1.20 32H m, 0.86 6H t, 0.84 6H t.

b) The compound of formula 39 is brominated with N-bromosuccinimide (NBS) in a similar manner to Example 1 b) to yield the compound of formula 40. ¹ H-NMR data (ppm, CDCl ₃ ): 8.29 2H d, 6.62 2H d, 3.98 4H d, 1.78 2H m, 1.45-1.20 32H m, 0.87 6H t, 0.84 6H t.

c) dibromide of formula 40 and di-thiophene-di in a manner similar to that of Example 1c) The acid pinacol ester [239075-02-6] is reacted in a Suzuki coupling reaction to produce a compound of formula 41. The chloroform fraction contained a polymer having a Mw of 18,200 and a polydispersity of 1.61 (measured by high temperature GPC).

Claims (15)

One containing one or more a polymer of a repeating unit, wherein the group A is a group of the following formula Wherein R ¹ and R ² are each independently C ₁ -C ₃₆ alkyl, R ¹⁰⁴ is C ₁ -C ₂₅ alkyl, which may optionally have one or more oxygen or sulfur atoms, and D is a group of the formula Where a is an integer from 1 to 5, one of X ¹ and X ² is N and the other is CH, one of X ⁵ and X ⁶ is N and the other is CR ¹⁴ , R ¹² and R ^{12 '} Independently, each other is hydrogen, halogen, optionally a C ₁ -C ₂₅ alkyl group having one or more oxygen or sulfur atoms, a C ₁ -C ₂₅ alkoxy group, a C ₇ -C ₂₅ arylalkyl group, or R ¹³ ; R ¹³ is C ₁ -C ₁₀ alkyl or tri(C ₁ -C ₈ alkyl)carbyl, R ¹⁴ is C ₁ -C ₂₅ alkyl, which may optionally have one or more oxygen atoms, R ¹⁵ and R ^{15 '} are each independently H; or optionally a C ₁ -C ₂₅ alkyl group having one or more oxygen atoms, and R ¹⁸ and R ^{18 '} are each independently hydrogen or halogen; a plurality of oxygen or sulfur atoms C ₁ -C ₂₅ alkyl; C ₇ -C ₂₅ aralkyl or C ₁ -C ₂₅ alkoxy; R ¹⁹ hydrogen, C ₇ -C ₂₅ aralkyl, C ₆ - a C ₁₈ aryl group; a C ₆ -C ₁₈ aryl group substituted by a C ₁ -C ₁₈ alkyl group or a C ₁ -C ₁₈ alkoxy group; or a C ₁ -C ₂₅ group optionally having one or more oxygen or sulfur atoms Alkyl; and R ²⁰ and R ^{20 '} are each independently hydrogen, C ₇ -C ₂₅ aralkyl; optionally, one or more C ₁ -C ₂₅ alkyl groups of an oxygen or sulfur atom, R ¹¹⁶ is hydrogen, C ₇ -C ₂₅ arylalkyl, C ₆ -C ₁₈ aryl group; by C ₁ -C ₁₈ alkyl, substituted C ₁ -C ₁₈ perfluoroalkyl group or a C ₁ -C ₁₈ alkoxy group of C ₆ - - C ₁₈ aryl group; C ₁ -C ₂₅ alkyl; -O- or -S- mixed with the C ₁ -C ₂₅ alkyl; or -COOR ^119, R ¹⁰¹ and R ^{101 'each} independently is H, F, C ₁ -C ₁₈ alkyl group, an O heteroatom of C ₁ -C ₁₈ alkyl C ₁ -C ₁₈ alkoxy, an O heteroatom of C ₁ -C ₁₈ alkoxy, C ₁ -C ₁₈ perfluoroalkyl group, optionally substituted with C ₁ -C ₈ alkyl and / or C ₁ -C ₈ Alkoxy substituted 1 to 3 times C ₆ -C ₂₄ aryl, optionally substituted by C ₁ -C ₈ alkyl and/or C ₁ -C ₈ alkoxy 1 to 3 times C ₂ -C ₂₀ Aryl; R ¹⁰² and R ^{102 '} are, independently of each other, H, halogen, optionally C ₁ -C ₂₅ alkyl having one or more oxygen or sulfur atoms; C ₇ -C ₂₅ arylalkyl, or C ₁ -C ₂₅ alkoxy; R ¹¹⁹ is C ₁ -C ₂₅ alkyl, substituted with E' and/or C ₁ -C ₂₅ alkyl with D', C ₇ -C ₂₅ arylalkyl, C ₆ -C ₂₄ aryl, C ₆ -C ₂₄ aryl substituted by G, or C ₇ -C ₂₅ aralkyl; D'-CO-, -COO-, -S-, -O- or -NR ¹¹² -; E' is a C ₁ -C ₈ thioalkoxy group, a C ₁ -C ₈ alkoxy group, CN, -NR ¹¹² R ¹¹³ , -CONR ¹¹² R ¹¹³ or a halogen; G system E' or C ₁ -C _C18 alkyl; R ¹¹² and R ¹¹³ independently of each other H; C ₆ -C ₁₈ aryl group; by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy group of C ₆ -C ₁₈ aryl group; C ₁ -C ₁₈ alkyl; or heteroaryl substituted with -O- of C ₁ -C ₁₈ alkyl; X ⁷ based ^{-C (R 120) (R 120} ') -, , or , R ¹²⁰ and R ^{120 '} are each independently hydrogen, optionally having one or more C ₁ -C ₃₅ alkyl groups of an oxygen or sulfur atom, or a C ₇ -C ₂₅ arylalkyl group; R ¹⁰³ and R ^{103 '} Independently from each other, hydrogen, halogen; optionally with one or more C ₁ -C ₂₅ alkyl groups of oxygen or sulfur atoms; optionally substituted by C ₁ -C ₈ alkyl and/or C ₁ -C ₈ alkoxy 1 to 3 C ₆ -C ₂₄ aryl; C ₇ -C ₂₅ arylalkyl, CN, or C ₁ -C ₂₅ alkoxy; or R ¹⁰³ and R ^103' together form a ring; R ³⁰³ , R ^304, R ³⁰⁵ and R ³⁰⁶ independently of each other H, F, C ₁ -C ₁₈ alkyl group, an O heteroatom of C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, C ₁ mixed with the O -C ₁₈ alkoxy, C ₁ -C ₁₈ perfluoroalkyl, optionally substituted by C ₁ -C ₈ alkyl and/or C ₁ -C ₈ alkoxy, 1 to 3 times C ₆ -C ₂₄ a C ₂ -C ₂₀ heteroaryl group optionally substituted 1 to 3 times with a C ₁ -C ₈ alkyl group and/or a C ₁ -C ₈ alkoxy group; and R ¹⁰⁰ and R ^100' are independently H , F., C ₁ -C ₁₈ alkyl group, an O heteroatom of C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, an O heteroatom of C ₁ -C ₁₈ alkoxy, C ₁ -C ₁₈ Perfluoroalkyl, optionally C ₁ -C ₈ alkyl and/or C ₁ -C ₈ alkoxy Substituting 1 to 3 C ₆ -C ₂₄ aryl, optionally C ₁ -C ₈ alkyl and/or C ₁ -C ₈ alkoxy for 1 to 3 C ₂ -C ₂₀ heteroaryl; The restriction is that when A is a group of formula IVa, D is not a group of formula Vw; or one contains one or more formulas a polymer of repeating units, wherein x = 0.995 to 0.005, y = 0.005 to 0.995, and wherein x + y = 1; A is of the formula IVa, IVc, IVe, IVg, IVh, IVi, IVj or as defined above Groups of IVk; B and D are independently of each other as defined above by the formulae Va, Vb, Vc, Ve, Vf, Vh, Vi, Vj, Vk, Vl, Vm, Vn, Vo, Vp, Vq, Vr, Vs, Vu, Vv, Vw, Vx, Vy, Vz or Va'groups; or B is a formula or R ¹ and R ² are C ₁ -C ₃₆ alkyl; D is a formula Va, Vb, Vc, Ve, Vf, Vh, Vi, Vj, Vk, Vl, Vm, Vn, Vo, Vp as defined above. , Vq, Vr, Vs, Vu, Vv, Vw, Vx, Vy, Vz or Va'groups; or one comprising one or more a polymer of the repeating unit, wherein r = 0.985 to 0.005, s = 0.005 to 0.985, t = 0.005 to 0.985, u = 0.005 to 0.985, and wherein r + s + t + u = 1, A is as defined above a group of the formula IVa, IVc, IVe, IVg, IVh, IVi, IVj or IVk; B, D and E are independently of each other as defined above by the formulae Va, Vb, Vc, Ve, Vf, Vh, Vi, a group of Vj, Vk, V1, Vm, Vn, Vo, Vp, Vq, Vr, Vs, Vu, Vv, Vw, Vx, Vy, Vz or Va'. The polymer of claim 1, which comprises A repeating unit, wherein A and D are as defined in claim 1, and n is 4 to 1000. A polymer according to claim 1 or 2, wherein A is a group of formula IVa, IVc or IVe as defined in claim 1. The polymer of claim 1 or 2, wherein the B system a group wherein R ¹ and R ² are, independently of each other, a C ₁ -C ₃₅ alkyl group. The polymer of claim 1 or 2, wherein D and E are independently of each other or The group. A polymer according to claim 1 or 2 which is a polymer of the formula or Wherein R ¹ , R ² , R ^{1 '} and R ^{2 '} are, independently of each other, a C ₁ -C ₃₆ alkyl group, and R ¹⁰⁴ is a C ₁ -C ₂₅ alkyl group, which may optionally have one or more oxygen or sulfur atoms, R ¹⁵ is H; or optionally a C ₁ -C ₂₅ alkyl group having one or more oxygen atoms, R ²⁰ and R ^{20 '} are each independently hydrogen, C ₇ -C ₂₅ aralkyl; a plurality of C ₁ -C ₂₅ alkyl groups of oxygen or sulfur atoms, R ¹⁰⁰ and R ^{100 '} are H, and R ¹⁰¹ and R ^{101 '} are each independently H, C ₁ -C ₂₅ alkyl, or C ₁ -C ₂₅ Alkoxy, R ¹⁰² and R ^{102 '} are each independently H or C ₁ -C ₂₅ alkyl, R ¹⁰³ and R ^{103 '} are independently H, or C ₁ -C ₂₅ alkyl, R ¹¹⁶ H Or a C ₁ -C ₂₅ alkyl group, R ¹²⁰ and R ^{120 '} are each independently C ₁ -C ₃₅ alkyl, n is 4 to 1000, and x=0.995 to 0.005, y=0.005 to 0.995, and wherein x+y=1. The polymer of claim 6 which is a group wherein n is from 10 to 1000 and R ¹ is a C ₁ -C ₃₅ alkyl group. An organic semiconductor material comprising the polymer of any one of claims 1 to 7. An organic semiconductor layer comprising the polymer of any one of claims 1 to 7. An organic semiconductor component comprising the polymer of any one of claims 1 to 7. A semiconductor device comprising the polymer of any one of claims 1 to 7, the organic semiconductor material of claim 8, the organic semiconductor layer of claim 9, or the organic semiconductor component of claim 10. The semiconductor device of claim 11, which is an organic photovoltaic device, a photodiode, or an organic field effect transistor. The semiconductor device of claim 12, wherein the photovoltaic device comprises, in order, the following: (a) a cathode (electrode), (b) a transition layer as appropriate, (c) a photoactive layer, and (d) smoothing as appropriate Layer, (e) anode (electrode), and (f) substrate. A method of producing an organic semiconductor device, which comprises applying a solution and/or a dispersion of a polymer according to any one of claims 1 to 7 to an organic solvent, and removing the solvent. A polymer according to any one of claims 1 to 7, an organic semiconductor material as claimed in claim 8, an organic semiconductor layer as claimed in claim 9, or as claimed The use of an organic semiconductor component of 10 for use in a photovoltaic device, a photodiode, or an organic field effect transistor.