TW201211099A - Diketopyrrolopyrrole polymers for use in organic semiconductor devices - Google Patents

Abstract

The present invention relates to polymers comprising one or more (repeating) unit(s) of the formula (I), or a polymer of formula (II), or (III), and their use as organic semicon-ductor in organic devices, especially in organic photovoltaics (solar cells) and photodiodes, or in a device containing a diode and/or an organic field effect transistor. The polymers according to the invention have excellent solubility in organic solvents and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the polymers according to the invention are used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.

Description

201211099 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a (repeated) single containing one or more formula (I)

(II) or *+AD~tfB-D廿A-HrfB-E~t· (11" polymer, and its use as an organic semiconductor for organic devices, especially organic photovoltaic devices (solar cells) And a photodiode, or a device containing a diode and/or an organic field effect transistor. The polymer of the invention has excellent solubility in an organic solvent and has excellent film forming properties. Further, in the polymer of the present invention High energy conversion efficiency, excellent field effect mobility, good on/off current ratio, and/or excellent stability can be observed in organic field effect transistors, organic photovoltaic devices (solar cells), and photodiodes. [Prior Art] WO 05/049695 discloses polymers based on diketopyrrolopyrrole (Dpp) and their use in PLEDs, organic integrated circuits (0_IC), organic field effect transistors (OFETs), organic thin film transistors (〇 TFT), an organic solar cell (ο-π), or an organic laser diode, but does not disclose a specific polymer based on DPP of Formula 1. Preferred polymer comprises a repeating unit of the formula

156275.doc 201211099 R1 and R2, independently of one another, may be heteroatomized with one or more oxygen atoms, especially Q-Cualkyl, and Ari&Ar2, independently of each other, is a group: &

R6 is hydrogen, C丨-c18 alkyl, or Ci_Ci8 alkoxy, and r32 is a fluorenyl group, C1, or OMe' and R8 is a η 'Ci_Ci8 alkyl group, or a CVCu alkane substituted with E and/or mixed with D Base, especially heterogeneous c "Ci8 alkyl. EP2034537A2 relates to a thin film transistor device comprising a semiconductor layer, 156275.doc

The semiconductor layer contains a compound containing a chemical structure represented by the following formula: R

Wherein X is each independently selected from the group consisting of s, Se, ruthenium, and NR, and R, each independently is selected from the group consisting of hydrogen, optionally substituted hydrocarbons, and hetero atom-containing groups, and z is independently independently a substituted hydrocarbon, a hetero atom-containing group, and a dentate, wherein d is at least 1, and e is 〇 to 2; a represents at least 1; b represents 0 to 20; And η represents a number of at least 1. Among them, the following homopolymers are clearly revealed:

156275.doc -6 · 201211099

(46) D,, "d""' RR (47), where n is the number of repeating units and may be from about 2 to about 5,000, and R",, R,,, R" 'M may be the same or Different substituents, and wherein the substituents are independently selected from the group consisting of an optionally substituted hydrocarbon group and a hetero atom-containing group. The present invention does not refer to homopolymers', particularly equations (22), (23), (24), (25) (34), (35), (36), (37), (44), (45), 46) and (47); the substance, which is explicitly disclosed in EP2034537A2. 156275.doc 201211099 EP2075274A1 discloses soluble polythiophene derivatives which do not contain 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. SUMMARY OF THE INVENTION The object of the present invention is to provide a polymer which can exhibit high energy conversion efficiency and excellent when used in an organic field effect transistor, an organic photovoltaic device (solar cell) and a photodiode. Field effect mobility, good on/off current ratio, and/or excellent stability. The target has been composed of a polymer containing (repeated) units of formula (-), or

A-D

(π) or -A-D- B-D- •A-

A polymer of Hr-B-E seven (III) is solved, where x = 0.995 to 0_005, y = 〇. 〇〇5 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=〇.〇〇5 to 0.985, t=0.005 to 0.985, u=0.005 to 0.985, and where r+s+t+u=i, R1

a radical R 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, 156275.doc 201211099 d is 0, or an integer 1 or 2, e is 0, or an integer 1 or 2, f is 0, or an integer 1 or 2, R1 and R2 may be the same or different and are selected from hydrogen, Ci_Ci〇〇alkyl, -COOR203; C丨-C丨00 alkyl, One or more self-priming atoms, hydroxyl groups, nitro groups, -CN, or C6-C-8 aryl groups and/or heterogeneous _〇, _c〇〇, -OCO-, or -S-; c7-c100 aryl An alkyl group, an amine carbenyl group; a c5_Ci2 cycloalkyl group which may be substituted with a fluorene group and/or (:--: 8 alkoxy group substituted 1 to 3 times; c6_C: 24 aryl group, especially stupid Or a 1- or 2-naphthyl group which may be substituted 1 to 3 times with an alkyl group, a cs thioalkoxy group, and a /4Cl_C8 alkoxy group; or pentafluorobenzene

R105

Wherein one of X and X4 is N and the other is cr99, R99, R104 and R104' are each independently hydrogen, a nutrient, especially F; or 156275.doc 201211099 optionally mixed with one or more oxygen or a Ci_C25 alkyl group of a sulfur atom, particularly a c25 alkyl group; a C7-C25 aryl group or an alkoxy group; R 05, R105, Ri〇6 and Ri〇6 are each independently hydrogen or halogen; a plurality of oxygen or sulfur atoms of a Cl_C25 alkyl group; a C7_C25 arylalkyl group, or (^-(:18 alkoxy group; R 07 system C7-C25 arylalkyl group, c6-C18 aryl group; a C6_Ci8 aryl group substituted with a decyl group, a Ci-Cu perfluoroalkyl group or a cvcu alkoxy group; a Ci_C25 alkyl group; a hetero--0- or -S-iCi-Cu alkyl group; or -COOR"9; C7-c25 arylalkyl, c6_Cl8 aryl; c6_Ci8 aryl substituted by Ci_Ci8^, C丨-Ci8 perfluoroalkyl or CVC!8 alkoxy; CVC25 alkyl; hetero-〇_ or Ci_C25 Or a C9-C24 aryl group; a c6-C24 aryl group substituted by g, or a C7-C25 aryl group, R and a ruler 1 (> 9 independently of each other H, C--C25 alkyl, E' substituted and/or heterozygous D'iCVCw alkyl 'C7-C25 arylalkyl, c6-C24 aryl, G substituted CVC24 aryl, C2-C2〇 a heteroaryl group, a C-substituted C2_c2()heteroaryl group, a c2-Ci8 alkenyl group, a c2-c18 alkynyl group, a Cl_Cl8 alkoxy group, a oxime substituted and/or a Ci-Cis alkoxy group having a D' Or a C7_c25 aryl group, or R108 and r109 together form a group of the formula =crii〇r丨1丨, wherein R and R 1 are independently of each other H, C!-C18 alkyl, E, substituted and/or hetero a Ci-Ci8 alkyl group having D', a C6-C24 aryl group, a C6-C24 aryl group substituted by G, or a Cz-Cm heteroaryl group or a C2-C2 anthracene aryl group substituted by G, or R108 and r1Q9 - Form a 5 or 6-membered ring, which may be subject to the following groups 156275.doc 201211099

Substituted: (VCu alkyl, E1 substituted and/or Cl_Ci8 alkyl, D6), C6-C24 aryl, G substituted C6-C24 aryl, c2_C2 〇 aryl, G substituted C2_C2 ( ^^•基,C2-C18 dilute, C2-Ci8 alkynyl, Cj-Cis alkoxy, E-substituted and/or Ci-CiS alkoxy with D' or C7_c25 aromatic. Group, D'- CO-, -COO-, -S-, -0- or -NR112-, E'-system (^-(:8 thioalkoxy, CVCs alkoxy, CN, -NRU2R113, • CONRmR113 or halogen, G Is E' or Ci-Cu alkyl, and R112 and R113 are each independently Η; C6-C18 aryl; C6_Cl8 aryl substituted by Cl_Ci8 alkyl, or cvc, 8 alkoxy; Ci_Cm alkyl; There are -O-iCi-Cu alkyl groups, and B, D and E are each independently a group of the formula:

156275.doc -11- 201211099

Or Formula IV, provided that B, D and E are groups of formula IV, which differ from A, where k is 1, 1 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, 156275.doc •12· 8 201211099 1 is 〇, or an integer 1 or 2, R1' and R2' have the meaning of R1 independently of each other,

Ar8, Ar8', Ar9, Ar9', Ar10 and Ar1. • independently of each other having the meaning of Ar2, and Ar4, Ar5, Ar6 and Ar7 are independently of each other:

One is N and the other is CR14.

Ar is an aryl or heteroaryl group, each of which may be optionally substituted, R118 has the meaning of R116, and R and R are independently hydrogen and halogen; and optionally may have one or more hydrazine or sulfur atoms (^- <:25 alkyl, especially qc:25 alkyl; Cl_C25 alkoxy, C7-C25 arylalkyl, or a =-R13; R system (^-0: 1 〇 alkyl or tri (Cj-Cs) Alkyl)carboxyalkyl, r14, r14', r15, independently of each other; or optionally a Ci_C25 alkyl group having one or more oxygen atoms; R and R are each independently hydrogen and dentate; It may be mixed as appropriate - C丨-C25 alkyl group of oxygen or sulfur atom, especially c4-c25 alkyl group; Erxi base or ^25 courtyard oxygen; 25 square, R 9 hydrogen, (: 7- (:25 aralkyl, C6_Ci8 aryl; MCi_c丨8 alkylene or Ci-Cu alkoxy substituted C6_Cu aryl; or optionally as well as 82.2, 156275.doc •13· 201211099 multiple oxygen or sulfur A CkC25 alkyl group of an atom, especially a c4-c25 alkyl group; and R independently of each other are hydrogen, a C7-C:25 arylalkyl group; optionally a Ci_C25 alkyl group having one or more oxygen or sulfur atoms, especially a C4_C25 alkyl group '

X series - Ο - or - NR115 -; R1 〇 Q and R1Q. 'Independently, each other is H, F, CrCu alkyl, heterocyclic G-Cu alkyl, cvCi8 alkoxy, hetero alkoxy, a. cls perfluoroalkyl, optionally Ci_C8 alkyl and/or Or (:1_(:8 alkoxy substituted 1 to 3 times (:6_C24 aryl, optionally substituted by Ci_C8 alkyl and/or alkoxy) 1 to 3 times C2-C2()heteroaryl; R303 , R3. 4, the ruler and r3〇6 are each independently H, f, alkyl 'cvc18 alkyl, c丨_Cu alkoxy, hetero-Ci_Ci8 alkoxy, q-Cu Perfluoroalkyl group, optionally by c _c8 alkyl and / or c] _ cs alkoxy substituted 1 to 3 times (: 6_ (: 24 aryl, optionally Ci_Cs alkyl and / or C!- Cs alkoxy substituted 1 to 3 times c2-C2 anthracene aryl; R307 and R3G8 are each independently H or optionally a C1-C25 alkyl group having one or more oxygen or sulfur atoms; R, r31G, r3H And R3^2 are independently of each other H, C丨-C25 alkoxy, or optionally c or _c25 alkyl having one or more oxygen or sulfur atoms; 156275.doc]4 8 201211099 R101 and R101 are independent of each other The ground is H, F, alkyl, heterocyclic c]-c18 alkyl, Cl_Ci8 alkoxy, heterozygous ^ / alkoxy, Ci_ Cu perfluoroalkyl, optionally by Cl_C8 alkyl and / or (: 1_ (: 8 alkoxy substituted 1 to 3 times C6_C: u aryl, optionally by c^-Cs Alkyl and/or (^-(:8 alkoxy substituted 1 to 3 times C2-C2 anthracene aryl; Ό ^ 〇2 nr» 1 02' R and R are independently of each other oxime, halogen, as the case may be a qc:25 alkyl group having one or more oxygen or sulfur atoms; (: 7-(:25 arylalkyl, or Ci_C25 alkoxy; R and R03 independently of each other as hydrogen, halogen; optionally mixed or a plurality of oxygen or sulfur atoms of a Cl_C25 alkyl group; optionally a C6_C24 aryl group substituted by Ci_C8 alkyl and/or 匕-匚8 alkoxy group 1 to 3 times; C7_C25 arylalkyl group, CN, or (^-( :25 alkoxy; or R103 and R1G3 together form a ring, R115 and R115 are independently hydrogen, C6_Cu aryl; C^-C!8 substituted by 〇14丨8 alkyl or Cl-Cl8 alkoxy An aryl group; optionally, a Cl_C25 alkyl group having one or more oxygen or sulfur atoms, especially an alkyl group; or a C7_C25 aryl group, R丨丨7&Rn7', independently of each other, a Ci-C35 alkyl group, a CrCu aryl group Alkyl, or optionally C1-C:8 alkyl and/or Ci_Cs An oxy group substituted to phenyl to 3 times, R12G and R12G are each independently hydrogen, optionally having one or more oxygen or sulfur atoms, CrC35 alkyl, or c7_c25 arylalkyl, R system Η, optionally One or more oxygen or sulfur atoms iCi_Ci8 alkyl, GC, 8 perfluoroalkyl, optionally Ci_Cs alkyl and/or Ci_C8 alkane 156275.doc •15·201211099 oxy substituted 1 to 3 times CpC24 aryl; C2_C2Q heteroaryl group may be substituted by C1_C8 alkyl and/or hydrazine alkoxy group to 3 times; or CN, R104, R104.

116 R,04v Rm, person li

Or O at least one of the groups Arl, & 丨, Ar2, Ar2_, Ar3 and Ar3' and/or at least one of the groups B, D and E

R\R contains a group relative to a group containing

R R104V R104'

The polymer is preferably Ο R \ R if the group

0 Directly keyed to the DPP skeleton, the following priorities apply

R uses:

RIW R <

Table to the key of the DPP skeleton). That is, the group is best. If the polymer comprises a (repeating) unit of formula (1), wherein

代 Ο Ν

(R120,)- 156275.doc 8 • 16 · 201211099

In the case of a group of (Vx), χ7 is preferably _〇_, -c(=o)-,

R1〇\/R100 R1〇〇v r100" ' and the best type of group. In the case of the groups of the formulae (Vy) and (Vz), X7 is preferably 〇-, -s-, -NR115-, -C(R120)(R120,)-, _Si(Rn7) (R117· )-, _c(=0)-,

[Embodiment] The polymer of the present invention can be advantageously used in an organic photovoltaic (PV) device (solar cell). Advantageously, the polymer of the invention, or an organic semiconductor material, layer or component comprising the polymer of the invention, can be used in an organic photovoltaic device (solar cell) 156275.doc • 17- 201211099 and a photodiode, or an airport effect In a transistor (OFET). The polymer-based copolymer of the present invention. The copolymer is a polymer derived from more than one monomer such as a 'dimer, a trimer, a tetramer or the like. The term polymer encompasses both oligomers and polymers. The oligomer of the present invention has a weight average molecular weight < 4,000 Daltons. The weight average molecular weight of the polymer of the present invention is preferably 4,000 Daltons or more, especially 4, 〇〇〇 to 2, 〇〇〇, 〇〇〇 Dalton, more preferably 10,000 to 1, 〇〇〇, 〇 〇〇, and the best 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 丨〇 i 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. R1 and R2 may be hydrogen, but are preferably different from hydrogen. R·1 and R2 may be different 'but preferably the same. Preferably, R1 and R2 independently of each other represent an alkyl group, may be substituted by C^-C8 alkyl and/or (^-(:8 alkoxy substituted 1 to 3 times Cs-C, 2 cycloalkyl, Substituting Ci-Cs alkyl and alkoxy for 1 to 3 phenyl or 1 or 2-naphthyl, or _cr3g1r3〇2_(CH2)u_A3, wherein R3〇丨 and r3〇2 represent hydrogen, or c丨_C4 alkyl, a3 represents a phenyl or hydrazine- or 2-naphthyl group which may be substituted 1 to 3 times by Cs and/or Cl_C8 alkoxy, and u represents 〇, i, 2 or 3. Ri And R2 is more preferably a Ci_c36 alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, M'3'3, 5,5-hexamethylenehexyl, n-heptyl, isoheptyl, tetramethylbutyl, 1-decylheptyl, 3-decylheptyl, n-octyl, tetramethylbutyl And 2-ethylhexyl, n-decyl, decyl, undecyl, especially 156275.doc • 18 - 201211099 n-dodecyl, tridecyl, tetradecyl, pentadecyl, Hexadecyl, 2-ethyl-hexyl, 2- Base-hexyl, 2-butyl-octyl, 2-hexyldecyl, 2-decyl-tetradecyl, heptadecyl, octadecyl, eicosyl, monodecyl, ten - a calcining group or a twenty-four alkyl group. In a preferred embodiment of the invention, R1 and R2 are 2-hexyldecyl, or 2-mercapto-tetradecyl. H3CTH2)m1 Advantageously, The groups R1 and R2 can be represented by Formula 1, wherein ml = nl + 2 and ml + nl 24. The palm side chain (e.g., r1 & r2) can be pure palm or racemic side chain, which can affect polymerization. The forms R and R have the same priority as R1 and r2, respectively. 〇99 ^ |sj R99 is arranged in the polymer. The label should contain two formulas or groups, groups

Can be in two ways

Other groups are equally suitable. They can be arranged in different ways in the monomer and/or in the polymer 156275.doc -19- 201211099. Preferably, Ar1 and Arr are independently of each other.

Ο R1

R 116

S' site is

R 99 R1 or

S'

S'. More preferably, Ar1 and Ar1' are each unique, /7 or human, wherein 〇, α, and α are optimal (〆 represents a bond to the DPP backbone). Ar1 and Ar1 may be different, but are preferably the same. In a preferred embodiment, the invention relates to polymers wherein Ari and (or or '

Ar1' is independent of each other

S R — 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. R116 is preferably different from Η. R104. Preferably, Ar8 and Ar8' are independently of each other, R99 Λ Λ, double or 4 . More preferably, Ar8 and Ar8' are independently of each other, ^, ^, ϋ or ^104 where 〇' \ and <, s- are optimal (〆 represents a bond to the DPP skeleton). Ar8 and Ar8 may be different, but are preferably the same. If Ar and A/ are independently of each other, ^JT^JI^戋, then Ar2 and

, ^/R1M 〇 R-5 S where R1 is different from hydrogen

Ar2' is independently 〆Ιζϊχ or 〆, 156275.doc 201211099 and preferably ^/. Alkyl (〆 represents a bond to the DPP backbone, or a group immediately following the DPP backbone). If a· and c are 1, and e is 〇 and Ar1 and Ar2 have the same meaning; or if a·, c and e are 1 and Ar1 and Ar2 and Ar3 have the same meaning, D is preferably different from Ar1.

If V and c are 1, and e is 0 and Ar1 and Ar2 are; or if a1, c and

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 SlVa, IVc, IVe, IVg, IVh, IVi and IVk are more preferred. Preferably, the groups of formulae IVa, IVc, IVe, IVg, IVh and Ivi are preferably 'B, D and E independently of each other as defined in formula 4 (Va), (Vb), (Vc) ), (Vd), (Ve), (Vf), (Vg), (Vh), (Vi), (Vj), (Vk), (VI), (Vm), (Vn), (Vo), (Vp), (Vq), (Vr), (Vs), (Vt), (Vu), (Vv), (Vw), (Vx), (Vy), (Vz) or (Va·) group. Formulas Va, Vb, Vc, Ve, Vf, Vh, Vi, Vj, Vk, VI, 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 optimal. In the group of the formula Vx, the group of the formula Vx', the group -21 - 156275.doc 201211099 group of the formula (Vb') is preferably a group

A group wherein R and R310 are each independently a Ci_C25 alkoxy group. In a preferred embodiment, the invention relates to a polymer comprising a (repeating) unit of formula I, in particular 1 & or a polymer of formula 1 [or m, wherein A is a

(Vb·), especially the group of the formula (Vc') is preferably a group of the formula (Vd,), preferably a group

Group - AD- In a preferred embodiment, the invention relates to a polymer comprising a repeating element of formula (I) wherein A is a formula, IVc, IVe, TVrt τ ά rr-rr. ive iVg, ivh , IV!, ivj or iVk of the group R1 and R2 are CVC35 alkyl, especially C8_C35 alkyl, R system (^-(: 25 yards, especially C4_C25 alkyl, which may optionally be mixed with oxygen or sulfur) Atomic, 156275.doc 8 •22- 201211099

D series Va, Vb, Vc, 尤立兀八, 广, Ve, Vf, Vh, 〜V〇 VP, Vq, Vr, Vs,

Vi, Vj, Vk, VI, Vm, Vn, V〇,

Vu, Vv, Vw, Vx, especially the group. In this embodiment, the formula * — — /τ,

The polymer of Jn (la) is more preferable, wherein reading 4 (especially (9) to deletion, especially 4 to ·, very particularly 5 (Uly to (10). The current best is a polymer, wherein the group of ^ ^ And

The polymer D system of the formula Vx ', especially the group of Vx, ·, for example, the example of the substance

a polymer wherein η is 4 (especially 10) to 1000, especially 4 to 2 Å, very particularly 5 (especially 2 〇) to 100 and R1 is Cl_ (: 35 院, especially CPC35 院. The material exhibits high energy conversion efficiency when used in a solar cell. In another embodiment, the present invention relates to a polymer crucible of the formula 丨, particularly the formula Ia

a substance, wherein the group A is a group of iva and the D is a type of Vo, especially

R. Ο. Examples of such polymers are polymers of the formula wherein η is 4 (especially 10) to 1000, especially 4 to 200, very particularly 5 (especially 20) to 100 and R1 is 156275.doc -23- 201211099

Ci-Cw alkyl, especially C8-C35 alkyl. The polymer exhibits high energy conversion efficiency when used in a solar cell. In a preferred embodiment, the invention relates to a polymer comprising repeating units of the formula: hopper a-d+H-Ht (11) 'where χ=0·995 to 0.005, y=0.005 to 0.995, in particular χ=〇·2 to 〇.8, y=0.8 to 0,2, and wherein x+y=i; A is a group of formula IVa, IVc, IVe, IVg, IVh, IVi, IVj or IVk, R1 and R2 is (ν <: 35 alkyl, especially c8-C35 alkyl, R knows Ci-C: 25-yard, especially CVC25 alkyl) which may optionally have one or more oxygen or sulfur atoms, and B and D are independent of each other. The ground is of the form Va, vb, Vc, especially -, Ve, Vf, Vh, Vi, Vj, vk, V1, Vm, Vn, v〇, vp,

Vq, Vr, Vs, Vu, Vv, Vw, vx, especially

a group of Vy, Vz or Va. The weight average molecular weight of the formula > polymer is especially 10,000 to 1, 〇〇〇, 〇〇〇 Dalton, very particularly 1 〇〇〇〇 to 1 〇〇〇 (9) Dalton. From the formula + (IIa Said polymer structure is an idealized representation of the polymer product obtained via, for example, the s_ki polymerization procedure. Simultaneous polymerization of precursors A, B and D can result in randomly ordered units and 156275.doc -24·201211099 and

-B-D

(Static Copolymer of Poly (AD-stat-BD)) In another preferred embodiment 'The present invention relates to a polymer comprising a repeating unit of the formula: wherein x = 0.995 to 0.005, y = 〇. 〇〇5 to 0.995, especially x=0.2 to 0.8, y=0.8 to 0.2, and wherein x+y=1; A is of the formula IVa, ivc, IVe, IVg, IVh, IVi as defined in the technical scheme 3 a group of IVj or IVk, R104#^^25 alkyl, especially c4_C25 alkyl, which may optionally have one or more oxygen or sulfur atoms,

or

0. R

Group R1 and R2 are (VC) alkyl groups, especially c8_c35, and D is a formula Va, Vb, Vc as defined above, especially

Ve, Vf, Vh, Vi, Vj, Vk, VI, Vm, Vn, V〇, VP,

Vq, Vr, VS 'vu, Vv, Vw, νχ, especially,

a group of Vy, Vz or Va. In a preferred embodiment, the invention relates to a polymer comprising repeating units of the formula: *+AD廿B—D廿A—E廿b—E 七(m), where r=0.985 to 0.005, s =0.005 to 0.985, t=0.〇〇5 to 985.985, 156275.doc •25· 201211099 u=0.005 to 0.985, and where r+s+t+u=1, A system IVa, IVc, IVe a group of IVg, Ivh, IVi, IVj or IVk, R1 and R2 are CVC" alkyl, especially C8_C35 alkyl, R104 CVC25 alkyl, especially C4_C25 alkyl, which may optionally be mixed with one or more oxygen or sulfur atom,

B, D, and E are independently of the formulas va, Vb, Vc, especially > s, %, Ve, Vf, Vh, Vi, Vj, Vk, V, Vm, Vn, Vo, Vp, Vq, Vr, Vs , Vu, Vv, Vw, Vx, especially

Several, Vy, Vz4Va, the group. The weight of the polymer of formula IIIa average molecular weight is in particular from 10,000 to 1, 〇〇〇, 〇〇〇 Dalton, 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. The polymer structure represented by the formula *-Η^Α-ΗτΗ-E+-* (Ilia) is an idealized representation of the polymer product obtained by, for example, the Suzuki polymerization procedure. Simultaneous polymerization of monomers A, B, D and E produces randomly ordered units -f A-D+, +B-D+, +A-E+ and +B-E+ (poly-AD-stat-BD-stat-AE -stat-BE) Statistical copolymer composed of the current formula (la), (lb), (Ic), (Id), (If), (Ig), (Ih), (Ii), (Ij), Ik), (II), (Im), (In), (Io), (Ip), (Iq), (I〇, (Is), (It), (Iu), (Iv), (lx) , (Iy), (Iz), (la,), (lb,), 156275.doc -26- _ 8 201211099 (Ic'), (Id,), (Ie,), (If'), (Ig '), (Ih,), (Ii,), (Ij,), (IIa), (lib), (lie), (lid), (ne), (Ilf), (Ilg), (nh), The polymer of (m) and (nj) is optimal. Refer to Scheme 8. R is preferably a C!-C25 alkyl group, especially a CfC25 alkyl group, which may optionally have one or more oxygen or sulfur atoms. R15, ruler 17 and ruler 7 are preferably independently of each other H; or optionally have one or more oxygen atoms iCl_C25 alkyl, especially c6_C25 alkyl. R20 and R2G are preferably independently of each other hydrogen, aralkyl One or more depending on the situation Crew alkyl of an oxygen or sulfur atom, especially c4_c25 alkyl. R_ and R1GG' are preferably Η. R101 and R1Q1' are preferably H, Cl-c25 alkyl or Ci_C25 alkoxy. r102 &amp; r1G2 is preferred H, or C1_C25 alkyl. R1()3 is preferably H, or (^-(:25 alkyl. R116 is preferably H, or (:!-〇:25 alkyl) r121r12G·preferably Cl_c35 Alkyl. Preparation of the polymer of the invention is explained in more detail for the polymer of formula II. The polymers of formulas </ RTI> and III can be prepared by the process described for the preparation of pi-polymers. The Suzuki reaction is obtained. The condensation reaction of aromatic folate (b_nate) with dentate (especially desert) (collectively referred to as "Suzuki reaction") allows the presence of various organic functional groups such as ν·厘卜如 and A. Suzuki in Chemical Reviews, Vol. vol. 457 2483 (1995). Preferred Catalysts 2_Dicyclohexylphosphinooxybiphenyl/acetic acid (Π), tris-crophos-scale salt/palladium (3) Derivatives and tri-forms 156275.doc -27· 201211099 phosphine/palladium (0) derivatives. Particularly preferred catalyst is 2-dicyclohexylphosphino-2,6·-di-decyloxy Biphenyl (sPhos) / palladium (II) acetate and tris - tert-butyl tetrafluoroborate scale ((t-Bu) 3P * HBF4) / 叁 (dibenzylideneacetone) two (〇) (pd2 (dba 3) and tri-tert-butylphosphine (t-BuhP/indole (dibenzylideneacetone) dipalladium (9) (Pdddba) 3). This reaction is suitable for the preparation of high molecular weight polymers and copolymers. To prepare a polymer corresponding to Formula II, the formula X1°-A-X1 is obtained under the catalytic action of Pd and triphenylphosphine. And χ1° — b—X1. The amount of the dihalide and (equivalent molar) corresponds to the reaction of the formula X11~f D+X", or the dihalide salt of the formula X + D + X and (etc. The quantity corresponds to the formula X11 — A—X11 and —Β: , 0, 0

Or -&lt;〇&gt;2 wherein Υ1 is reacted with an acid or a di-folate salt at X"-B-X", wherein χ1〇 is a halogen, especially 仏~ or 1' very particularly ΒΓ, and Xl&gt; The second occurrence is independently -Β(0Η&gt;2 &gt; -Β(0Υ!)2 14 Each time it appears independently cvca base and ¥2 is independently C2-C10 in each occurrence Base, for example, _〇γγγ_γγ5γ6, 戈cy7 8 CY9Yl〇_ CYlV2_, where γ3, γ4, γ5, γ6, Υ?Υ^, _^, ^ and ^ are independently of each other as gas...he especially-C( CH3) 2C(CH3), ^ -CH2C(CH3)2CH2-. 4-C(CH3)2CH2C(CH3), and Υ13 and Υ14 are each independently hydrogen or CpC(tetra). The reaction is aromatic under about wot a hydrocarbon solvent (for example, toluene or dimethyl. Other solvents (for example, dimethylamine, dioxin, dimethoxyl, and tetrahydrogen W), or these solvents and aromatics may be used alone. (iv) 156275.doc •28· 201211099 Mixture of hydrocarbons. Use an alkaline aqueous solution (preferably sodium carbonate or sodium bicarbonate, potassium acetate, carbonic acid or hydrogen carbonate) as the activator of the acid and the acid salt. HBr scavenger. Polymerization It can last from 0.2 to 100 hours. Organic bases (for example, tetraalkylammonium hydroxide) and phase transfer catalysts (for example, TB AB) can enhance the activity of the shed (see, for example, Leadbeater &amp;Marco; Angew. Chem. Int) Ed. Eng. 42 (2003) 1407 and its reference for the use of the scorpion I.) Other changes in reaction conditions by TI Wallow and Β· Μ. Novak in J. Org. Chem. 59 (1994) 5034-5037 , and Μ. Remmers, M. Schulze and G. Wegner are given in Macromol Rapid Commun. 17 (1996) 239-252. By using an excess of dibromide, bis-acid, or di-folate, or The chain terminator is used to control the molecular weight. According to the method described in WO 20 10/13 63 52 (European Patent Application No. 09176497.7), the polymerization is carried out in the presence of: a) a catalyst/ligand system comprising palladium Catalyst and organophosphorus or scaly compound, b) test, c) solvent or solvent mixture, characterized in that the organophosphine is a trisubstituted phosphine of the formula:

(VI), or a squama salt thereof, wherein X independently of Y represents a 156275.doc -29-201211099 nitrogen atom or a C-R2'' group and γ is independently a samarium representing a nitrogen atom or a C_R9&quot; group, two Ri&quot; of each of the R1 'groups, independently of the other, represents a group selected from the group consisting of CrC: 24·alkyl, q-Cw cycloalkyl (which includes, inter alia, monocyclic and bicyclic) a tri-cyclic cycloalkyl group, a C5_CH-aryl group (which includes, inter alia, a phenyl group, a naphthoquinone group, a fluorenyl group), a C2-C13-heteroaryl group (wherein the number of hetero atoms selected from the group consisting of N, 〇, and 8 may be In the meantime, "two of the feet!" groups may also be linked to each other, and wherein the above-mentioned groups R themselves may be each independently substituted or monosubstituted with a substituent selected from the group consisting of hydrogen, Ci_C2〇. -alkyl, C2_C2.-dilute, C3-C8-cycloalkyl, c2-C9-hetero-alkyl, C5-Ch)-aryl, c2_C:9-heteroaryl (wherein from N, hydrazine, The number of heteroatoms of the group of s may be 1 to 4), Ci-C2 〇-alkoxy, Ci-C10-commerate, thiol, alkyl, NH-(C5-C1(r aryl) ), N^-Czo-hospital base 2, N^-Cw hospital base) (C5-C1()-aryl), N(C5-C1( r aryl) 2, Ν ((ν(:2()-alkyl/c5-Cio-aryl 3)3+, NH-CO-CVC^o-alkyl, NH-CO- C5-C]0 - an aryl group in the form of an amine group, a COOH and a COOQ group (where q represents a monovalent cation or a Ci-Cs-alkyl group), a crC6-methoxy group, a sulfinate group, S〇3H and S〇3Q' a sulfonate group (wherein Q represents a monovalent cation, a Ci-C20-alkyl group, or a C5-C10• aryl group), a tri-Ci-C6-alkylcarboyl group, wherein the two substituents They can also be bridged to each other, R2'' to R9&quot; for hydrogen, alkyl, alkenyl, cycloalkyl, aromatic or heteroaromatic aryl, 〇-alkyl, NH-alkyl, N-(alkyl) 2 , 〇-(aryl), NH-(aryl), N-(alkyl)(aryl), O-CO-alkyl, 0-CO-aryl, F, Si (hospital) 3, CF3 , CN, C02H, COH, S03H, CONH2, CONH (alkyl), CON (alkane 156275.doc • 30-8 201211099 base) 2, so2 (alkyl), SO (alkyl), SO (aryl), So2 (aryl), S〇3 (alkyl), S〇3 (aryl), s-alkyl, S-aryl, NH-CO (alkyl), C〇2 (alkyl), CONH2 CO (alkyl), NHCOH, NHC02 (alkyl), CO ( a (2), co2 (aryl) group in which two or more independent B groups may also be bonded to each other to form a condensed ring system, and wherein in R2" to R9&quot; In each case a linear or branched hydrocarbon group having from 1 to 20 carbon atoms, the dilute group representing a linear or branched chain in each case and having from 2 to 20 carbon atoms a mono- or poly-unsaturated hydrocarbon group, a cycloalkyl group representing a hydrocarbon having 3 to 2 carbon atoms, and an aryl group representing a 5- to 14-membered aromatic group, wherein 1 to 4 carbon atoms in the aryl group are also Substituted from heteroatoms of the group nitrogen, oxygen and sulfur to give 5 to a heteroaromatic group, wherein the radicals R2 &quot; to R9, may also have other substituents as defined for r1&quot;. Organophosphines and their synthesis are described in WO2004101581. Preferably, the organophosphine is selected from the group consisting of trisubstituted phosphines of the formula: R3&quot;

R4-^3^r1" R1&quot; Compound ------ R1&quot;R5&quot;R6&quot;R3&quot;R4&quot; A-1 Η3υ°Η3 Η人ch3 Η Η Η A-2 Cyclohexyl Η Η Η Η A-3笨基Η Η Η 156 156275.doc -31 - 201211099 A-4 一&quot;·' 金钢统基__一-- Η — Η Η Η A-5 Cyclohexyl - -〇ch3 ----- --- Η Η Η A-6 Cyclohexyl------1) 0 Η Η A-7 H%Hh3 1) 1) Η Η A-8 phenyl---- 1) ---- l ) Η Η A-9 金钢炫》1) 1) Η Η A-10 Cyclohexyl Η ---- Η 2) 2) A-11 % — Η Η 2) 2) A-12 phenyl-- ----1 Η Η 2) 2) A-13 Gold Steel Hyun Base _ 一Η Η 2) 2) 1) R5.&gt;R6" together form a ring ^ 2) r3,, r4, · together form a ring Examples of good catalysts include the following compounds: acetamacetone palladium (II), dibenzylidene-acetone palladium (ruthenium) complex, palladium (II) propionate,

Pd2(dba)3 : [4(dibenzylideneacetone)dipalladium(0)],

Pd(dba)2: [bis(dibenzylideneacetone)palladium(〇)],

Pd(PR3)2, wherein PR; the triple substituted scale of the formula VI,

Pd(OAc)2: [palladium(II) acetate], palladium chloride (11), palladium bromide (π), tetrachloro acid chain (II),

PdCl2(PR3)2: a trisubstituted phosphine of PR3 system; palladium (〇)diallyl-ether complex, palladium(II) nitrate, -32·156275.doc 201211099

PdCl2(PhCN)2: [dichlorobis(nickel nitrite)palladium(II)],

PdCl2(CH3CN): [digas bis(acetonitrile) put (π", and

PdCl2 (C0D): [diqi (1,5-cyclooctadiene) put (11)]. Particularly preferred are PdCl2, Pd2(dba)3, Pd(dba)2, Pd(OAc)2, or Pd(PR3)2. The best ones are pd2(dba)3 and pd(〇Ac)2. The catalyst is present in the reaction mixture in a catalytic amount. The term "catalytic amount" means an amount significantly less than one equivalent of (hetero)aromatic compound, preferably from 0.001 to 5 mol-%, most preferably from 0,001 to 1 based on the equivalent of the (hetero)aromatic compound used. Mol-%. The amount of the phosphine or the scaly salt in the reaction mixture is preferably 0.001 to 10 m〇l_%, most preferably 〇 01 to 5 m〇1_%, based on the equivalent of the (hetero) aromatic compound used. The preferred ratio of Pd: phosphine is 1:4. The test may be selected from all aqueous and non-aqueous bases and may 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, buffers, 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. A mixture of tests can also be used. The base is preferably a lithium salt, for example, a lithium alkoxide (for example, lithium methoxide and lithium ethoxide), lithium hydroquinone, lithium carboxylate, lithium carbonate, lithium fluoride, and/or an acid-filled clock. The currently best base is aqueous LiOHxH2 〇 (Li〇H monohydrate) and (no water) LiOH. The reaction is usually carried out at a temperature of about 〇 ° C to 18 (TC, preferably 20 ° C to 160 ° C, more preferably 40 C to 140 C and most preferably 40. (: to 120 ° C. The polymerization can last for 156,275. Doc • 33- 201211099 0·1 hour, especially 0.2 to 100 hours. In a preferred embodiment of the invention, the solvent is THF, the system is LiOH*H2〇 and the reaction is at the reflux temperature of THF (about 65. (: The solvent is selected from, for example, toluene, xylene, anisole, THF, 2-methyltetrahydrofuran, dioxane, gas benzene, fluorobenzene, or a solvent mixture containing one or more solvents (for example, THF). /toluene) and optionally water. The most preferred is THF, or THF/water. Preferably, the polymerization is carried out in the presence of: a) palladium (II) acetate, or pd2 (dba) 3 (叁 (二亚) Benzylacetone)dipalladium(3))) and organophosphines A-1 to A-13, b) LiOH, or LiOHxH2〇; and C)THF, and optionally water. If a monohydrate of LiOH is used, it is not necessary to add water. The polymerization is optimally carried out in the presence of: a) palladium(II) acetate, or Pd2(dba)3 (叁(dibenzylidene)

Acetone) dipalladium (〇)) b) LiOHxH2〇; and W is based on the amount of t of the (hetero) steroid, the weight of the medium is preferably about 〇.5 based on the (hetero) aryl (tetra) compound used. A preferred ratio of phosphine is about L4 when the amount of scale or scale salt in the straight reaction mixture is preferably about 2. 156275.doc

• 34· 201211099 Preferably, the polymerization is carried out in an inert condition in the absence of oxygen. Nitrogen and (more preferably) argon are used as the inert gas. The process described in European Patent Application No. 917,649,7.7 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 provides a polymer having a weight average molecular weight of at least 10,000 Daltons, more preferably at least 2 Torr Daltons, and most preferably at least 30,000 Daltons. The currently preferred polymers have a weight average molecular weight of 30,000 to 80, 〇〇〇Dalton. 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., and most preferably from I" to 25. If desired, a monofunctional aryl quotient or an aryl aryl ester can be used as a chain terminator in such reactions which can form a terminal aryl group.

OH 156275.doc •35· 201211099

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 (see, for example, Babudri et al, J. Mater. Chem., 2004, 14, 11-34; J. κ. Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508). To prepare a polymer corresponding to Formula II, the formula x1° - A - X1 is made in an inert solvent at a temperature ranging from 〇 ° C to 200 ° C and in the presence of a palladium-containing catalyst. And X1. One Β - χ 1. The dihalide is reacted with a compound of the formula 〇21-〇-χ21, or the formula χΐ°-〇_χ1. The dihalide is reacted with a compound of the formula X21-A-X21 and X21-Β-χ21, wherein the X21 group is -SnR207R208R209 and X10 is as defined above, wherein R2〇7, R2〇8 and R2〇9 are the same or Different and tethered or Ci_C6 alkyl, wherein the two groups form a common ring as appropriate and the groups are optionally branched or unbranched. It is necessary to ensure that the ratio of organotin functional groups to dentate 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 dentate compound are preferably introduced into one or more inert organic solvents, and stirred at a temperature of from 〇 ° C to 200 ° C, preferably from 30 ° C to 170 ° C for 1 hour. 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 practice or even by dialysis." Organic solvent systems suitable for use in the process (for example) Ether (eg diethyl ether, two 156275.doc • 36- 201211099 methoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxolane, diisopropyl ether and tert-butyl methyl ether), hydrocarbon (example

Such as hexane, heptane, cyclohexane, benzene, toluene and diphenylbenzene, alcohol (such as methanol, ethanol, 1-propanol, 2-propanol 'ethylene glycol, hydrazine-butanol, 2 _ Alcohols and second-butanol), such as acetone (ethyl ketone ketone and isobutyl decyl ketone), guanamine (such as dimethyl decylamine (DMF), dimercaptoacetamide and" Methylpyrrolidone), nitrile (for example acetonitrile, propionitrile and butyronitrile), and mixtures thereof. The phosphine component should be selected in a manner similar to that described for the Suzuki variant. The zinc reagents A-(ZnX22)2 and Β·(ΖηΧ22)2 (wherein X22 halogens and halides) and 〇_(Χ23)2 (where X23 is self-fertilizing or trifluorosulfonium) can also be used by the Negishi reaction. Acid salt), or using α_(χ22)2, Β-(Χ22)2 and D-(ZnX23)2. For example, see Ε· Negishi et al., Heterocycles 18 (1982) 11 7-22 〇 or 'this The inventive polymer can also be used by the Hiyarna reaction using the organic litholytic reagent A-(SiR210R2uR212)2&amp;B_(SiR2)〇R2uR212)2 (wherein r210, r211 and R212 are the same or different and the auxin, or CVC6) And D-(X23)2 (wherein X23 is a halogen or trifluorosulfonium sulfonate) or A-(X23)2, B-(X23)2 and D-(SiR210R211R212)2 are synthesized. For example, See t. Hiyama et al., Pure Appl. Chem. 66 (1994) 147 Bu 1478 and T. Hiyama et al., Synlett (1991) 845-853. 156275.doc -37· 201211099 R1

6. f, R丨, R2, ΑΓ, W, Ar2, Ar2., Ar3 and Ar3, as defined above and X11, each occurrence is independently _primin+, very particularly I Or Br; or have the meaning of X1!. R1 type

A new compound and another object of the present application, wherein a, b, c, d, e, f, Ri, R2, Ar丨, Arl., Af2 ' &quot;, 斛3, and Ar3·丨 χ 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn a common ring and such groups are optionally branched or unbranched; χΐ2 is a halogen atom, very particularly I or Br; -0S(0)2CF3, -0S(0)2-aryl, especially 1~O~CH3, -0S(0)2CH3, -B(OH)2, -B(〇H)3•, -BF, γ13 -BCOYi, _Β, 〇Χ^14 or _Β, 〇&gt; 2, wherein Υ1 is independently Ci-Ci 每次 at each occurrence and Υ2 is independently c2_c alkyl at each occurrence, such as -CY3Y4-CY5Y6- or -CY7Y8-CY9Y10_CY11Y12, wherein Y3, Y4, Y5, Y6, Y7, Y8, Y9, Y10, ΥΠ and γ12 156275.doc •38- 201211099 This is independently hydrogen, or C丨. An alkyl group, especially -C(CH3)2C(CH3)2-, or -C(CH3)2CH2C(CH3)2-, -(:Η20:((:Η3)2 CH2-, and γΐ3 and γΐ4 are independent of each other Is hydrogen or c丨-C1G alkyl. Examples of compounds of formula X below: R1

X11 (Xa)

, 116 R

X11 (Xb) (Xd)

(Xe) (Xf)

x ir R R1 (Xh), especially 156275.doc •39· 201211099

,especially

(Xj) '

(Xk),

156275.doc ·40· 8 (XI), 201211099 R1

(Xm), and

R2 x11. (Xn), X11, R1, R2, R116, R104 and R104' are as defined above. R1 and R2 are preferably Ci_C36 alkyl, such as decyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, isobutyl, tert-butyl, n-pentyl , 2-pentyl, 3·pentyl, 2,2-dimethylpropyl, m3 tetramethylpentyl, n-hexyl, 1-decylhexyl, 1,1,3,3,5,5- Hexamethylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, decylheptyl, 3-mercaptoheptyl, n-octyl, i-tetradecyl Butyl and 2-ethylhexyl, n-decyl, decyl, undecyl, especially n-dodecyl, tridecyl, tetradecyl 'pentadecyl, hexadecyl, anthracene Ethyl-hexyl, 2-butylhexyl 2-butyl-octyl, 2·hexyldecyl, 2-octyldodecyl, 2-decyl-tetradecyl, heptadecyl, octadecyl, Eicosyl, icosyl, behenyl or tetracosyl.

Rl ° 4 and RlGV may be the same or different and are preferably CVC carbyl groups, especially c4-c25 alkyl groups which may optionally be present - or a plurality of oxygen or sulfur atoms, and R116 is preferably hydrazine or Cl_C25 alkyl. β is obtained by using a protecting group IS which can be removed after polymerization to obtain a polymer of R1 and/or 156275.doc-41·201211099 R2 hydrogen (for example, see, EP-AO 648 770, ΕΡ-Α-0 648 817, ΕΡ -Α-0 742 255, ΕΡ-Α-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 into its pigment form by means of the following conditions: under known conditions (for example thermal conditions), as appropriate in the case of additional catalysts (for example as described in W〇00/36210) The rupture is carried out in the presence of a catalyst. An example of such a protecting group is a group of the formula _i〇_L, wherein the L is suitable for imparting any desirable group for solubility. L is preferably a formula, I 2 ', ---β —|β 2?, |β — ζβ 2 Ζ 2 2

Or a group of —Q—, wherein Ζ丨, ζ2, and ζ3 are each independently a CrC6 alkyl group, and Z and ζ are independently CrC6 alkyl, hetero aerobic, sulfur, or n(zi2)2 Ci-C0 An alkyl group, or a phenyl or biphenyl group which is unsubstituted or substituted by a Ci_C6 alkyl group, a c丨 alkoxy group, a mercapyl group, a cyano group or a nitro group, and ζ, Z and Z7 are each independently hydrogen or c丨_c6 An alkyl group, a hydrazine 9 series hydrogen, a cvc6 alkyl group or a group of the formula -i_z13, jj gas 1 s, and Z10 and Z11 are each independently hydrogen, Ci_C6 alkyl, C1_C6 alkoxy, halogen, cyano, nitro, N (Z12) 2, or unsubstituted or substituted by halo, cyano, nitro, C]-C6 alkyl or c^c:6 alkoxy, 156275.doc •42 201211099 Z and Z13 C^c: 6 alkyl, ZM is hydrogen or c丨 alkyl and zls is hydrogen, CrC6 alkyl, or unsubstituted or substituted with Ci_c6 alkyl, Q is unsubstituted or via-decane Oxyl, hydrazine 146 alkylthio or C2_Ci2 diasteramine mono- or poly-substituted p, q-c2-c6-extension, wherein ... is a different position number, X is selected from the group consisting of nitrogen, oxygen and sulfur a hetero atom of the group, m' is a number 0 in the case of X-system oxygen or sulfur and m is in the X-line nitrogen The number 丨, and L and L2 are each independently unsubstituted or mono- or poly-oxime/"alkoxy-, -cvcualkylthio-, CyCu dialkylamino-, _c6_Ci2 aryloxy-, _c6-c12 arylthio-, _C7-C24 alkylarylamino- or _C "C24 diarylamino substituted eve: 6 alkyl or [_(ρ, «2τ6alkyl)z_]n _ CVC6 alkyl, n' is the number from 丨 to 丨嶋, p, and q, are numbered different positions, z are each independently substituted by a heteroatom oxygen, sulfur or c-alkyl, and [-CrC6 alkylene The C2_C6 alkylene group in the repeating unit of the group -z_] may be the same or different, and the 1^ and 1^2 may be saturated or have an unsaturation degree of 1 to 1 Å, may be undoped or may be mixed at any position.丨 to 1 group selected from the group consisting of _(c = 〇)_&amp;_C6H4_' and may have no other substituents or have 1 to 10 - selected halogens: cyanide and nitro group Substituents "Best-D'-L system group. The synthesis of the BrA Br compound is described in w〇〇8/〇〇〇664 and w〇09/047104' or may be similar to the methods described herein. Synthesis of N-aryl substituted compounds of the formula Br A Br Synthesis of gas, gas, bromine and hydrazine in a manner similar to that described in USA_5, 354, 869 and 156275. doc - 43-201211099 〇wo 03/022848. Right &amp; 'CVC25 alkyl (Ci_Ci8 alkyl) Usually linear or branched alkyl. Examples are thiol, ethyl n-propyl, isopropyl, n-butyl, first butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl 2'2-dimethylpropyl, U,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1,1,3,3,5,5-hexamethylhexyl, n-Heptyl, isoheptyl, 1,1,3,3·tetramethylbutyl, j-decylheptyl, 3-methylheptyl-n-octyl, 1,1,3,3·tetramethyl And 2 ethylhexyl, n-decyl fluorenyl,

Monoalkyl, dodecyl, hexaalkyl, heptadecyl, tridecyl, tetradecyl, pentadecyl, octadecyl, decyl, bis-f-alkyl , behenyl, tetracosyl or dipentadecyl. (: 丨-C8 alkyl is usually methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl , 3, fluorenyl, 22-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, la, 3,3-tetramethylbutyl and 2-ethylhexyl. Cl_C4 alkyl Usually methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, isobutyl, tert-butyl. C2-Cu dilute linear or branched olefin Base, for example, vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-pent-2,4-dienyl, 3-methyl -but-2-alkenyl, n-octyl-2-alkenyl, n-dodec-2-enyl, isododecenyl, n-dode-2-enyl or positive _ eighteen-4 -alkenyl. s alkynyl straight or branched and preferably unsubstituted or substituted 156275.doc -44 - 201211099 c2.8 alkynyl, for example, ethyl fast, i-propyl fast _ 3_ base, butyl block I group, pentyne 5 group 2-methyl _3_ butyne 2 yl group, 14 pentane block group, 1 3 · pentadiyne-5-yl group, b alkyne · 6 • Base, cis _3 methyl _2 pentyl collar _ base, trans -3-methyl | 戍 冬 快 快 、 、 、 、 、 、 、 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 -9 -9 -9 -9 -9 Alkynes _24_. Alkoxy (Ci_Ci8 alkoxy) is a linear or branched alkoxy group, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy , second-butoxy, tert-butoxy, pentyloxy, isopentyloxy or tert-methoxy, heptyloxy, octyloxy, isooctyloxy, decyloxy, oxime a group, a ten-tertiary oxy group, a twelve alkoxy group, a tetradecyloxy group, a fifteen alkoxy group, a hexadecanol group, a heptadecyloxy group, and an octadecyloxy group. Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, 2- Pentyloxy, 3-pentyloxy, 2,2-di-propyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, u,3,3·tetramethylbutoxy And ethylhexyloxy is preferably a C丨-C4 alkoxy group, for example, usually methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second _butoxy, Butoxy first butoxy. The term "sulfuryl" means the same group as the alkoxy group, except that the oxygen atom of the ether bond is replaced by a sulfur atom. C--Cls perfluoroalkyl, especially Ci_C4 perfluoro Alkyl has a branched or unbranched group, such as -cf3, -CF2CF3, _CF2CF2CF3, _CF(CF3)2, -(cf2)3cf3, and -C(CF3)3 〇 The term "amine mercapto" is usually Unsubstituted or substituted c -18 amine 156275.doc -45- 201211099 methyl ketone 'preferably C! · 8 amine carbhydryl group, for example, amine carbaryl, decylaminocarbyl, B Aminyl, n-butylamine decyl, tert-butylamine carbaryl, dimethylamine-methyl methoxy, morpholinyl fluorenyl or pyrrolidinylcarbinyl.

The Cs-C!2 ring-based base is usually cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably leuco 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 Ci_C4_alkyl group, a halogen group and a cyano group. The condensed cyclohexyl group

CfC24 aryl (C^-C!8 aryl) is usually unsubstituted or substituted phenyl, fluorenyl, chamomile, naphthyl, biphenyl, asymmetric (as_indacenyl) Symmetrical s-indacenyl, acenaphthylenyl, fluorenyl, phenanthryl, fluorenyl, triphenylalkenyl, 156275.doc -46 - 201211099 oxalyl, tetracene , a starting group, a fluorenyl group, a pentaphenyl group, a hexaphenyl group, a fluorenyl group, or a fluorenyl group, preferably a phenyl group, a 1 naphthyl group, a 2-naphthyl group, a 4-phenylene group, a 9-phenanthryl group, and a 2- Or 9-fluorenyl, 3- or 4-biphenyl. Examples of C^-Ci2 aryl are unsubstituted or substituted phenyl, anthracene-naphthyl, 2-naphthyl, 3- or 4-biphenyl, 2- or 9-fluorenyl or 9-phenanthryl .

CrC25 aralkyl is usually benzyl, 2-benzyl-2-propenyl, p-phenylethyl, oc'oc-dimercaptobenzyl, ω-phenylbutyl, ωω_dimethyl_ω Styyl _ butyl, ω-benyl-undecyl, ω-phenyl-octadecanyl, ω-styl-icosyl or ω-phenyl-docosyl, preferably C7_Cu aralkyl, such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, αα-dimercaptobenzyl 1 phenyl-butyl, ω,ω-dimercapto-ω - phenyl-butyl, ω-phenyl-dodecane or ω-phenyl octadecyl, and especially preferably C7_Ci2 aralkyl, such as benzyl, 2-benzyl-2-propyl, --phenyl-ethyl, α,α-didecylbenzyl, phenyl- butyl, or ω,ω-dimercapto-ω-phenyl-butyl, wherein an aliphatic hydrocarbon group and an aromatic hydrocarbon group Both groups may be unsubstituted or substituted. Preferred examples are benzyl, 2-phenylethyl, 3-phenylpropyl, naphthylethyl, naphthylfluorenyl, and isopropyl strepyl. a heteroaryl group is usually a CrCM heteroaryl group, that is, a ring or fused ring system having 5 to 7 ring atoms of a nitrogen, oxygen or sulfur-based possible heterogeneous, and usually has 5 to 30 atoms and has at least 5 6 conjugated π-electron unsaturated heterocyclic groups, such as thienyl, benzo[b]thienyl, dibenzo[b,dpg phenyl, thioxyl, furyl, fluorenyl, 2H-fluorene Benzyl, benzofuranyl, isopropanylfuranyl, dibenzofuranyl, phenoxythiophenyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, dipyridyl, triazinyl, % pyridine &quot;Bitin 156275.doc -47· 201211099 base, oxazinyl, oxime, isodecyl, fluorenyl, carbazolyl, fluorenyl, sulphonyl, fluorenyl, iso- ylyl , Blowing base, naphthalene bite base, 啥喔琳基, sniffing _ base, 吟 spider base, 嗓β base, taste σ sit base. Lactolide, benzotriene, benzo &lt;» sputum, phenanthrene, beta guanidine, cancer bite, phenanthrene, phenazine, isoindole. Sitrate, phenylpyrazine, iso-quot; oxalic acid, sulfhydryl or phenoxazinyl, which may be unsubstituted or substituted. Possible substituents for the above groups are CpCs alkyl, hydroxy, thiol, C,-Cs alkoxy, CVCs alkylthio, halogen, halo-CrCs alkyl, cyano, amidino, nitro or A germyl group, especially a CrCs alkyl group, a CrCs alkoxy group, a Ci-Cg alkylthio group, a halogen, a halogenated CrCs alkyl group, or a cyano group. Miscellaneous with one or more OiCVCu alkyl groups (for example) (CH2CH20)i.9_Rx, wherein 1^ is 11 or (: 1-(:1〇alkyl; (:%-(:11(011")-(: 112-01^, wherein 1^ is a C!-Ci8 alkyl group, and Ry· contains the same definition or system as R/. If a substituent (eg, R18) occurs more than once in a group, then each occurrence The phrase "substituted by G" means that one or more, especially one to three, substituents G may be present. As mentioned above, the above groups may be substituted by hydrazine, and/or may be heterogeneous if desired. Of course, it may be heterozygous only in the case of a group containing at least two carbon atoms bonded to each other by a single bond; the C aryl aryl group is not hetero-hetero; the inter-heteroarylalkyl group contains the unit D in the alkyl moiety. A C丨-C18 alkyl group substituted by one or more E. and/or one or more units D (for example, wherein R is hydrazine or Ci-C10 alkyl or C2-C10 alkyl (for example, CH(C2H5)C4H9),CH2-CH(0Ry,)-CH2-0-Ry 'where R/ is c · 156275.doc ·48· 201211099 c18 alkyl, c5-c12 cycloalkyl, phenyl, (: 7-(:15 phenylalkyl, and V covers the same definition or enthalpy as R/; CVCs alkyl-coo-rz, for example, CH2COORz, CH(CH3)COORz, C(CH3)2COORz, wherein m Η, (:丨-(:18 alkyl, (CHzCHzOVs-RX, and Rx encompasses the above definition; Ch2ch2-o-co-ch=ch2; ch2ch(oh)ch2-o-co-c(ch3)=ch2. A mixture containing the polymer of the invention can produce a polymer comprising the invention (typically from 5% to 99.999% by weight) , in particular from 20% by weight to 85% by weight) and at least a semiconducting layer of another material. Other materials may be, but are not limited to, portions of the same polymer of the invention having different molecular weights, another polymer of the invention, semiconducting Polymers, small organic molecules, carbon nanotubes, fullerene derivatives, inorganic particles (quantum dots, quantum rods, quantum tripods, TiO2, ZnO, etc.), conductive particles (Au, Ag, etc.) Insulator material (for example, for the gate dielectric) (PET, PS, etc.). The polymer of the present invention can be used, for example, in European Patent Application No. 09155919.5, WO 09/047104, US 6,690,029, W0 2007082584 and Small molecule blending described in W0 2008107089" W0 2007082584:

156275.doc • 49· 201211099

156275.doc -50- 201211099 WO 2008107089 :

X'----, -S-, -Se- or -NR&quot;'-, R&quot;&quot; is a cyclic, linear or branched alkyl or alkoxy group having from 1 to 20 C atoms. Or an aryl group having 2 to 30 C atoms, which are optionally fluorinated or perfluorinated, R' is Η, F, Cl, Br, I, CN, having 1 to 20 C atoms and optionally Fluorinated or perfluorinated linear or branched alkyl or alkoxy group, aryl group having 6 to 30 C atoms and optionally fluorinated or perfluorinated, or C〇2R&quot;, where R&quot; A ruthenium, 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&quot;' system or having from 1 to 10 C A cyclic, linear or branched alkyl group of an atom, y is 0 or 1, and X is 0 or 1.

156275.doc •51- 201211099

C2, the polymer may contain - a small molecule, or a mixture of two or more small molecules. &amp; Accordingly, the invention is also directed to organic 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. The present invention is also directed to a semiconductor device comprising the polymer of the present invention, or an organic semiconductor material, layer or component. The semiconductor device can be used as an organic semiconductor layer of a semiconductor device, either alone or in combination, by using an organic semiconductor layer of a semiconductor device, either alone or in combination. - Useful means to provide layers, for example, vapor deposition (for relatively low amounts of knives) and printing techniques. The compounds of the invention can be filled in an organic solvent and can be solution deposited and patterned (Example 156275) .doc -52- 8 201211099 Such as 'by spin coating, dip coating, inkjet printing, gravure printing, flexographic printing, offset printing' screen printing, micro-contact (wave)_printing, dripping or zoned washing, Or other conventional techniques are implemented.) The polymer of the present invention can be used in integrated circuits including a plurality of OTFTs, and in various electronic articles. The articles include, for example, radio frequency identification (rfid), for flexible displays. (eg, for personal computers, mobile phones, or handheld devices) backplanes, smart cards, memory devices, sensors (eg, light sensors, image sensors, biosensors, Learning sensor, mechanical sensor or 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 layer comprising one or more polymers of the invention Another aspect is the use of the polymer or material of the present invention in an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor (OFET). Organic photovoltaic (PV) devices (solar cells), photodiodes, or organic field effect transistors (〇FETs) of the polymers or materials of the invention. The polymers of the invention are typically used as organic in the form of thin organic layers or films. The semiconductor, 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 may also be less than about 1 micron. Thickness. For example, when used in an OFET, the layer thickness can typically be 1 〇〇 nm or less. The exact thickness of the layer depends, for example, on the requirements of the electronic device using the layer. For example, in an OFET The active semiconductor trench between the electrode and the source electrode may comprise a layer of the invention. 156275.doc -53- 201211099 The OFET device of the invention preferably comprises: - a source electrode, a - germanium electrode, - a gate electrode, a semi-conductive layer, - or a plurality of gate insulator layers, and - optionally substrate - wherein the semiconductor layer comprises - or a plurality of polymers of the invention. The gate electrode, source and drain electrodes and insulating and semiconductive layers of the OFET device may be arranged in any order The premise is that the source electrode and the non-electrode are separated from the gate electrode by the insulating layer, the gate electrode and the semiconductor layer are both in contact with the insulating layer, and both the source electrode and the germanium electrode are in contact with the semiconducting layer. Preferably, the OFET includes An insulator on the first side and the 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 a germanium electrode and a source electrode on the polymer layer . 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., W〇 3/〇52841). The gate insulator layer may comprise, for example, a fluoropolymer such as the commercially available cyt〇p 809M®, or Cyt〇p 1〇7M8 (from (1)). Preferably, the gate insulator layer is deposited from a formulation comprising an insulator material and one or more solvents (fluorine refrigerants) having one or more fluorine atoms (preferably perfluorosolvent), for example by spin coating, scraping Coating, metal wire bar coating, spray coating or dip coating or other conventional methods are implemented 156275.doc -54- 201211099. Suitable perfluorosolvent systems (for example) FC75® (available from Acros, catalog number 12380). Other suitable fluoropolymers and desolvent solvents are well known in the prior art, such as the perfluoropolymer Tefl〇n AF® M00 or 2400 (from DuP〇nt), or Fiu〇r〇pei8 (from Cytonix). Or perfluorosolvent FC 43® (Acr〇s, No. 12377). The semiconductive layer comprising the polymer of the present 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, two-legged quantum, TiO2, 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 inventive polymers and polymeric binders. The ratio of the polymer of the present 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 polydecyl phthalate (PMMA). Using this technique, electrical performance deterioration can be avoided (see WO 2008/001123 A1). The polymer of the present invention is preferably used in an organic photovoltaic (PV) device (solar cell). Thus the invention provides a PV device comprising a polymer of the 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 organic photovoltaic devices (solar cells) is described, for example, in C. Deibel et al., Rep. Prog. Phys 73 (2010) 096401 and 156275.doc -55- 201211099

Christoph Brabec, Energy Environ. Sci 2. (2009) 347-303 The o PV devices are contained in the following order: (a) Cathode (electrode), (b) Transition layer as appropriate, such as alkali metal, especially fluorinated Lithium, (c) photoactive layer, (d) 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 the conjugated polymer of the present invention (as an electron donor) and an acceptor material (e.g., fullerene, especially functionalized fullerene PCBM) (as an electron acceptor). As described above, the photoactive layer may also contain a polymeric binder. The polymer of the invention may comprise from 100% by weight to 99.9% by weight, in particular from 9% by weight to 99% by weight, very particularly 5% by weight, based on the amount of the polymer of the invention and the polymeric binder. Preferably, the polymeric binder is a semi-crystalline polymer such as polystyrene (ps), high density polyethylene (10), polypropylene (PP) and polymethyl methacrylate (for example). PMMA For a heterojunction solar cell, the active layer preferably comprises a mixture of a polymer of the invention and a fullerene in a weight ratio, such as [6〇]PCBM (=6,6-phenyl) _Cei Butyric acid f, or Chen in the present invention has a large (four) size (carbon number / molecule). The term rich (four) as used herein includes various types of pure carbon 156275.doc • 56· 201211099 molecule, Including Buckminster - πμ "Buckminsterfuiierene" (Cm) and related "spherical Schleurene and carbon nanotubes. Fullerenes can be selected from those skilled in the art, for example ^ 20-C丨〇〇〇 range. Preferably, fullerenes are selected from the range of c60-c96. 昜Γήη1ΡΓ 'Fuller rare c60 or c70' such as [60]PCBM ' or [γοΐΡΓ'Κλ/τ gland ~/ ] ΒΜ. Also allows the use of chemically modified fullerenes, then k-modified modified Fullerene Retention Receptor Type and electron mobility characteristics. The acceptor material may also be a material selected from the group consisting of: any semi-conductive polymer (eg, 'the polymer of the present invention, provided that the polymer retains acceptor type and electron mobility characteristics are small. a child, a carbon nanotube, an inorganic particle (quantum dot, quantum rod, tripod quantum, Ti〇2, Ζη〇, etc.). The photoactive layer is derived from the polymer of the present invention (as an electron donor) and fullerene , especially functionalized Fullerene PCBM (as an electron acceptor). The two group wounds are mixed with a solvent and applied to the flat/moon layer by a solution such as the following method. Spin coating, dripping , Lanmer-Brogi, such as ah _

Blodgett) ("LB") method, inkjet printing method and drop coating method. A thicker surface can also be applied using this __photoactive layer using a rubber roller or printing method. It is preferred to use a dispersing agent such as chlorobenzene instead of the usual toluene as a solvent. Among these methods, vacuum deposition, spin coating, ink jet printing, and washing are particularly preferred from the viewpoint of work convenience and cost. In the case of forming a layer using a spin coating method, a casting method, and an inkjet printing method, a concentration prepared by dissolving or dispersing the composition in an appropriate organic solvent such as 〇·〇1% by weight to 90% by weight may be used. % solution and / or dispersion is applied topically. ¥, toluene, diphenylbenzene, tetrahydrofuran, mercaptotetrahydrofuran, hydrazine-methylamine, acetone, acetonitrile, benzoquinone, two Chlorine 156275.doc • 57- 201211099 Alkane, disulfoxide, benzene, 1,2-dibenzene and mixtures thereof. Photovoltaic photovoltaic (PV) devices can also be constructed of 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), W02004/112161 and Christoph Brabec, Energy Environ. Sci 2. 2009) 347-303 中 The so-called 'serial-type solar cells' are contained in the following order: (a) cathode (electrode), (b) transition layer as appropriate, such as metallization, especially fluorinated chains, ( c) photoactive layer, (d) as appropriate smooth layer, (e) central electrode (eg Au, Al, ZnO, Ti02, etc.) (f) additional electrode for matching energy levels, as appropriate, (g) A transition layer of the case, such as an alkali metal dentate, especially fluorolithium, (h) a photoactive layer, (i) a smooth layer as appropriate, (1) an anode (electrode), (k) a substrate. Can also process PV steps on fiber products

The device is described, for example, in IJ 20070079867 and US 20060013549. (6) •58· 156275.doc containing the polymer of the present invention due to its excellent self-organizing properties

The 201211099 or film may also be used in an LCD or OLED device, alone or in combination with other materials, or as an alignment layer for use in an LCD or OLED device, as described, for example, in US 2003/0021913. 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 μπι (size 30 〇x8 mm ID) Mobile phase: 1,2,4-trichlorobenzene, purified by vacuum distillation and stabilized by butylated hydroxytoluene (BHT, 200 mg/1), chromatography temperature: 150 ° C; mobile phase flow : 1 ml/min; solute concentration: approx. 1 mg/ml; injection volume: 200 μΐ; test: RI, molecular weight calibration procedure: calibration using a set of 10 polystyrenes obtained from Polymer Laboratories (Church Stretton, UK) The standard is used to perform relative calibration. The molecular weight of the polystyrene is between 1,930,000 〇3 - 5,050 0&amp;; 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 3 0,300, PS 10,100, PS 5,050 Da 〇 Calculated using polynomial calibration 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, 156275.doc -59-201211099, the sequential end-polymerization conditions in the polymer may be alternating or random. Example 1

a) 20 g [88949-34-2] and 25.76 g of potassium carbonate were suspended in 3 ml of water-free dimethylamine and the mixture was heated to 9 Torr under nitrogen. Hey. Then 79 g [1044598-79-9] was added dropwise. The reaction mixture was then stirred at 9 ° 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 sulfuric acid and the solvent was evaporated. The product was purified by chromatography on an oxidized stone column to obtain a compound of the formula 1. 1H-NMR data (ppm, CDC13): 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 1 〇〇 ml of gas. The mixture was cooled 156275.doc -60·201211099 but 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. Wash, dry over magnesium sulfate and evaporate the solvent. The crude product was purified by column chromatography on cerium oxide to obtain a compound of formula 2. 1H-NMR data (ppm, benzene-D6): 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) To a three-necked reaction flask was added 0.5 g of compound 2, 0.188 g of 1,4-benzoic acid bis(pinacol) ester [99770-93-1] and 51 mg of palladium acetate under an argon atmosphere. 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-t-butyl-phosphino)-1 -phenyl-1H-» was added and the reaction mixture was refluxed with stirring. Then 146 mg of lithium hydroxide hydrate was added and the reaction mixture was stirred under reflux for 2 hours. The reaction mixture was then cooled to room temperature and the product was filtered through a pad of methanol 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 I56275.doc •61 - 201211099

The polymer of Formula 4 was synthesized starting from Compound 2 and thiophene-di-acid-pinacol vinegar [175361·81·6] in a manner similar to the example]M + . Soxhlet extracted tetrahydrofuran. P is a polymer of the formula 4 containing M474, 6 Å and having a polydispersity of 2% (measured by high temperature GPC). Example 3

The polymer of Formula 5 was synthesized starting from Compound 2 and η-phene-depeno-di-acid-pinacol ester [924894-85-9] in a manner similar to Example 1 C). 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

156275.doc -62- 201211099 The polymer of formula 6 was synthesized starting from compound 2 and bis-thiophene-di-acid pinacol ester [239〇75-02-6] in a manner similar to the case of lc). 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) A dibromide of formula 2 is reacted with a boronic acid pinacol ester of the formula [883742-29-8] in a Suzuki coupling reaction according to the compound [1220883-00-0] to give a compound of the formula 7. 1H-NMR data (ppm, CDC13): 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 W-NMR data (ppm, CDC13): 8.45 2H bs, 7.08 2H Bs, 6.73 2H d, 4.09 4H 156275.doc -63· 201211099 d, 2.57 4H t, 1.93 2H m, 1.70-1.55 4H m, 1.48-1.15 6〇H m 0.90 6H t, 0.84 6H t, 0.83 6H t ;

[175361-81-6]

c) The synthesis of the polymer of formula 9 is carried out starting from compound 8 and cembole-dicarboxylate-pinacol ester [175361-81-6] in a manner similar to that of example c c). The tetrahydrofuran portion of the Soxhlet extraction contained a polymer of the formula 9 having a Mw of 3,200 and a polydispersity of 1.86 (measured by high temperature GPC). Example 6

In a manner similar to the case of lc), from 0.8 equivalents of compound 8, 〇·2 equivalents of compound [214493-03-5] and 1 equivalent of thiophene-dioxalate-pinacol ester [丨75361 - 156275.doc • 64· 201211099 ]1. . A polymer of the formula. The crude polymer of Formula 1 has a Mw of 11'500 and a multi-knife dispersity of 19 Å (measured by high temperature, i.e., measurement). Example 7

The mouthpiece [214493-03-5] and 1 equivalent of porphyrin di-fat acid-pinacol vinegar [175361_ 81-6] began to synthesize the polymer. formula. The crude polymer was 9,900 and the polydispersity was j 61 (measured by high temperature Gpc). Example 8

The polymer of Formula 12 was synthesized starting from the compound [1〇〇〇623 98_2] and furan-di-Sp-acid-pinacol ester [476004-83-8] in a manner similar to Example lc). The tetrahydrofuran portion of the Soxhlet extraction contained a polymer of the formula 12 having a Mw of 6 Å 5 Å and a polydispersity of 2.28 (measured by Southern Temperature GPC). Example 9 156275.doc -65- 201211099

a) reacting a dibromide of the formula [1000623-98-2] and a tanning acid pinacol ester of the formula [883742-29-8] in a Suzuki coupling reaction according to the compound [1220883-00-0] to give the formula 13 Compound.

b) The compound of formula 13 is waved according to the compound [1220883-03-3] using N-bromosuccinimide (NB S) to give the compound of formula 14.

c) The polymer of formula 15 was synthesized starting from compound 14 and furan-dicarboxylic acid-pinacol ester [476004-83-8] in a similar manner to the example lc). The polymer of 丨5 is obtained by extracting the tetrahydrofuran moiety to have a % of 40,200 and a polydispersity of 2 ι〇 (by 156275.doc • 66 - 201211099 measured by high temperature GPC). Example 10

Synthetic Formula 16 was started in a manner similar to Example lc) from 8 equivalents of compound 14, 0.2 equivalent of compound [214493-03-5] and 1 equivalent of furan-di-acid-pinacol ester [476004-83-8]. The polymer tetrahydrofuran portion of the soxhlet extraction contains a polymer of formula 16 having a Mw of 27,100 and a polydispersity of 丨·99 (measured by high temperature Gpc). Example 11

156275.doc -67· 201211099 In a manner similar to the case of lc), from 0.5 equivalent of compound 14, 〇5 equivalents of compound [2 14493-03-5] and 1 equivalent of fluorenyl di-g-minic acid pinacol § (4) _ 83-8] The synthesis of the polymer of Formula 17 was started. The tetrahydrofuran fraction extracted by s〇xMet contains a polymer of the formula 17 having a Mw of 22,600 and a polydispersity of 2 Å (measured by high temperature). "Example 12

A polymer of the formula [8] was synthesized starting from the compound [1〇〇〇623 98 2] and pyrrole dipic acid-pinacol ester [476004-84-9] in a manner similar to the example lc). The crude polymer of Formula 18 had an Mw of 8,500 and a polydispersity of 2 43 (measured by high temperature GPC).

The polymer of formula 19 was synthesized starting from compound 14 and pyrrole-dihexanoic acid-pinacol vinegar [476004-84-9] in a similar manner to the example lc). The crude polymer of Formula 19 had a Mw of 5 and a polydispersity of 2.15 (measured by high temperature Gpc). 156275.doc -68· 201211099 Example 14

The polymer of Formula 21 was synthesized starting from the equivalent of Example lc) from 5 equivalents of Compound 14, 0.5 as the quantitative compound [214493-03_5] and 1 equivalent of pyrrole-dicapric acid·pinacol ester [476004-84_9]. The crude polymer of Formula 21 had a MW of 156275.doc -69 - 201211099 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 solar cell has the following structure: A1 electrode / LiF layer / organic layer (including polymer 3) and [70] PCBM / [ A mixture of poly(3,4·extended ethylenedioxy-thiophene) (PEDOT) and 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, DC (organic layer) was spin-coated with polymer 3 (1% by weight): [70] PCBM (substituted C7Q fullerene) 1:1.5 mixture. LiF and A1 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 is obtained in Example 16

The following values: Jsc = 8.5 mA/cm2 'FF = 0.58 and Voc = 0.82 V, and the estimated total efficiency is 4.04%.

The polymer of Formula 23 was synthesized starting from 96 g of Compound 2, 5〇8 6 g of Compound 22 in a manner similar to Example lc). The polymer was purified by Soxhlet extraction using different solvents: tetrahydrofuran, gas and o-dichlorobenzene. 72〇 mg 邻二 156275.doc •70· 201211099 The chlorobenzene moiety contains a polymer of formula 16 having a Mw of 1 〇〇 and a polydispersity of 2.59 (measured by high temperature GPC). Application Example 2: Airport-effect transistor based on polymer 23 A bottom gate thin film transistor (TFT) structure having a p-Si gate (1 〇 cm) was used in all experiments. A 300 nm thick high quality thermal 8 丨〇 2 layer was used as a gate insulator 'C=32.6 nF/cm2 capacitance/cell area. The source and drain electrodes are patterned on the gate oxide directly by photolithography. A gold source electrode and a germanium electrode which define a trench having a width W = l 〇 mm and various lengths L = 4 m, 8 m, 15 m, 30 m are used. Before depositing the organic semiconductor, the Si〇2 surface was obtained by the following method: at 160. The underarm was exposed to hexamethylene oxazepine (HMDS) for 2 hours in saturated decane vapor, and HMDS was spin-coated at a rotation speed of 8 rpm (revolutions per minute) for about 1 minute, or at 60. The substrate was treated with a 〇 j m solution of octadecyltrichlorodecane (OTS) in toluene. The substrate was treated 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 o-dichlorobenzene in a 5〇/〇 (w/w) solution. Spin coating was carried out at a rotational speed of 1000 rpm (revolutions per minute) in an ambient condition for about 6 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_1〇). According to a linear fit to the square root of the saturated transmission characteristic, the field effect mobility can be measured after drying to be UxiO-2 cm2/Vs and the on/off current ratio is 2,.7&gt;&lt;105. The threshold voltage is approximately 2.3 volts. 156275.doc -71- 201211099 Application example 3: Organic bulk heterojunction solar cell solar cell based on polymer 23 has the following structure: A1 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. Pre-patterned ITO by spin coating a PEDOT:PSS layer on a glass substrate Come up to make solar cells. Subsequently, a compound of formula 23 (0.8% by weight) was spin-coated: [60] PCBM or [70] PCBM (substituted Cm or Cm fullerene) 1:2 mixture (organic layer). LiF and A1 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: Jsc = 14.35 mA/cm2, FF = 0.61 and VOC = 0.72 V, and the estimated total efficiency was 6.3%. Example 17: Synthesis of polymer 26 a) To a cooled (_78 〇C) solution of 1.05 g of 24 in anhydrous THF was added 4.5 ml of butyllithium (2.5 Μ in hexane). The resulting solution was stirred at 〇C for 15 minutes and cooled to -78 °C. 5.2 g of 2-isopropoxy-4,4,5,5-tetradecyl-1,3,2-dioxane was added dropwise, and kept at -78 ° C for 5 minutes, then the solution was slowly added. Warm to room temperature and continue stirring for 30 minutes. The reaction was stopped by the addition of 50 ml of HCl (10%) and the product was extracted twice with 40 ml of ethyl acetate. The combined organic extracts were dried <RTI ID=0.0></RTI> to </RTI> <RTI ID=0.0></RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt;

b) 〇·96 g 2, 0.5 g compound 25, 15 mg Pd (acetic acid vinegar) 2, 76 mg 2-(di-tert-butyl-phosphino)phenyl-pyrrole and 6 〇ml four under argon The hydroquinone was mixed and warmed to 4 °C. Subsequently, 0.29 g of a lithium hydroxide solution was added to the reaction mixture, and then the reaction mixture was refluxed for 4 hours and cooled to room temperature. The green-blue mixture was precipitated using decyl alcohol and filtered. The filtrate was dissolved in chloroform and refluxed with a 1 〇 /0 NaCN aqueous solution for 3 hr. The organic phase was washed with water and then dried and evaporated. The polymer was precipitated with decyl alcohol and the precipitate was fractionated using THF, chloroform and di-benzene in a Soxhlet. The digas benzene fraction 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 Solar Cell Based on Polymer 26 has the following structure: A1 electrode / LiF layer / organic layer (including the compound of the present invention) / [poly(3,4-extended ethyldioxy) - thiophene) (PEDOT): poly(styrenesulfonic acid) (PSS)] / IT0 electrode / glass substrate. A solar cell was fabricated by spin coating a PED0T:PSS layer onto a pre-patterned IT0 on a glass substrate. Then, the compound of formula 26 (1% by weight) was spin-coated: [6〇]PCBM or [70] PCBM (substituted C6〇 or C7〇fullerene) 1:1·5 mixture (organic layer). LiF and Α1 sublimate through a shadow mask under high vacuum. 156275.doc -73- 201211099 Solar Cell Performance Solar cell characteristics were measured under AM 1.5G conditions. Irradiation with a xenon-based solar simulator (100 mW/cm2) and a device area of 0.09 cm2. Under these conditions, the measured efficiency was 5.07% (where jsc = 10.9 mA/cm2, FF = 〇.57 and Voc = 0.82V) » Example 18: Synthesis of Polymer 29

27 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

【617-90-3】

[1224573-55-0] a) Add 5 77 g of sodium and 12 mg of Feci3 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_9〇_3] was added in portions and then 20 g of 156275.doc •74-201211099 [1224573-5 5-0] 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 filtered by filtration. The filter cake is washed with water, acetone and decyl alcohol and water and then dried to yield a compound of formula 30. 1H-NMR data (ppm, DMSO-d6): 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-indolyl-iodide [1044598-79-9] in a similar manner to that of Example la) 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 manner analogous to Example lb) to yield the compound of formula 32. ih_NMr data (ppm, CDC13): 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 〇156275.doc -75- 201211099

d) The dibromide of formula 32 is reacted with thiophene-di-acid-pinacol-ester [175361-81-6] in a Suzuki coupling reaction in a manner analogous to Example lc) to give the compound of formula 33. Example 20

The dibromide of formula 32 was reacted with naphthalene-diacid-pinacol ester [849543-98-2] in a Suzuki coupling reaction in a manner analogous to Example lc) to give the 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 la) [88949-34-2] To produce a compound of formula 35. 1H-NMR data (ppm, CDC13): 156275.doc -76- 201211099 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 .

NBS

b) The compound of formula 35 is brominated using N-bromosuccinimide (NBS) in a similar manner to Example lb) to yield the compound of formula 36. 1H-NMR data (ppm, CDC13): 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 difuryldione-pyrrolopyrrole [88949_34.2] in a manner similar to that of Example ia) to produce a compound of formula 37. iH-NMR data (ppm, CDC13): 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, 〇 88 6H t. 156275.doc -77- 201211099

b) The compound of formula 37 is brominated using N-bromonaphone (NBS) in a manner analogous to Example lb) to yield the compound of formula 38. 1H-NMR data (ppm, CDC13): 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

[88949-34-2] [1256345-37-5]

a) alkylation of di-furyl-di-keto-pyrolo-pyrrole using 2-2-butyl-octyl-iodide [1256345-37-5] in a manner similar to that of Example 1 a) [88949-34] -2] to produce a compound of formula 39. 1H-NMR data (PPm, CDC13): 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 〇 156275.doc

39 40 78- 8 201211099 b) The compound of formula 39 is brominated using N-bromosuccinimide (NBS) in a manner similar to that of Example lb) to yield a compound of formula 40. 1H-NMR data (ppm, CDC13): 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) reacting dibromide of formula 4 with di-thiophene bis-benzoic acid pinacol @239 [239075-02-6] in a Suzuki coupling reaction in a manner similar to that of example lc) to give formula 41 Compound. The gas-like portion contained a polymer having an Mw of 18,200 and a polydispersity of 1.61 (measured by a still temperature G P C measurement). 156275.doc 79-

Claims (1)

201211099 VII. Scope of application: 1. A polymer containing one or more (repeated) years of the formula * AD-*(I), or a formula of 4·α_ΗτΗ-Ηγ(πκ—AD廿B—D廿Λ-E廿Β—Ε七(ΠΙ) polymer, where x=0.995 to 0.005, y=0.005 to 〇·995, especially χ=〇2 to 〇8 y=0.8 to 0.2, and wherein x+y= i, r=0.985 to 0.005, s=〇.〇〇5 to 0.985, t=0.985 to 〇〇〇5 ' u=0.005 to 0.985, and where r+s+t+u=i, R1 Group, where 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, e is 0, or an integer 1 or 2, f is 0, or an integer of 1 or 2, R1 and R2 may be the same or different and are selected from hydrogen, CC 1 L 1 〇G alkyl, -COOR203; Ci-Cm alkyl, which is one or more halogen atoms, widely Substituted, nitro, -CN, or C6-C18 aryl substituted and / or heterocyclic • ~ • COO-, -OCO-, or _s_; c7_Ci 〇〇 arylalkyl, amine carbaryl; 156275.doc 201211099 C5_CUcycloalkyl' which can be substituted by (^-(:8 alkyl and/or (^-(:8 alkoxy substituted 1 to 3 times; C^C24 aryl' especially phenyl or i_ or 2- Naphthyl, which may be substituted by c!-C8 alkyl, CrC8 thioalkoxy, and/or (^-(:8 alkoxy substituted 1 to 3 times; or pentafluorophenyl 'R2Q3 system C丨-Cso An alkyl group, especially a c4-C25 alkyl group; Meaning, wherein one of X3 and X4 is N and the other is CR&quot;, R, R104 and R104' are independently of each other hydrogen, halogen, especially F; optionally mixed with one or more oxygen or sulfur atoms -Cu alkyl, especially CVC25 alkyl; (να5 arylalkyl, or Ci_c25 alkoxy, independently of each other as hydrogen, (iv) · may be mixed with - or multiple CVC groups of oxygen or sulfur atoms; cvc25 Alkyl, or (^-(:18 alkoxy; R107-based C7-C25 aryl, C6_Ci8 aryl; 156275.doc-2) 201211099 CrCu perfluoroalkyl or Ci_Ci8 alkoxy substituted c6_Ci8 Base; Cl_C25 alkyl; hetero-〇- or each Cl_C25 alkyl; 4_C〇〇R119; R116 hydrogen, C7-C25 arylalkyl, c6-c18 aryl; trans-group, qC!8 perfluoro Alkyl or Cl_Ci8 alkoxy substituted c6_c^aryl; Ci-Cw alkyl; hetero-_〇_ or _s_Ci_c25 alkyl; or _c〇〇R丨19; R-based Cl_C25 alkyl, E' substituted and/or heterocyclic, Ci-Ch alkyl, C7-C25 arylalkyl, c6-C24 aryl, G substituted C6-C24 aryl, or C7-C25 aryl, R108 And R109 are independently of each other H, CiTu alkyl, E, substituted and/or heterozygous D 2Cl_C: 25 alkyl, eve: 25 arylalkyl, C6_C24 aryl, G substituted (να4 aryl, heteroaryl, oxime substituted c20 heteroaryl, c2_Cl8 dilute, C2_Ci8 block, Ci_Ci8 Alkoxy groups, E, substituted and/or heterogeneous d, 2Ci_Cis alkoxy, or C7_C25 aralkyl, or R.08 and R109 together form a group of formula =CR&quot;〇Rm, wherein R and R are each other Independently hydrazine, Ci-C 8 alkyl, e' substituted and/or heterodi DiCl-Cl8 alkyl, C6_C24 aryl, G substituted c6_c24 aryl, or CyCao heteroaryl or substituted by G C2-C2 anthracene aryl, or R and R form a 5 or 6 membered ring, which may optionally be substituted by a group of G-Cualkyl, E, substituted and/or heterozygous D, alpha ά ά alkyl , a C6-c24 aryl group, a G-substituted C6_C24 aryl group, a Km heteroaryl group, a G-substituted c2_C2-aryl group, a C2_Ci8 dilute group, a c2 core 8 fast group, a Ci-Cw alkoxy group, and a oxime substitution / or miscellaneous with D, of Ci_c &quot; alkoxy or C7-C25 aralkyl, 156275.doc 201211099 D'--CO-, -COO-, -S-, -Ο- or -NR112-, E' &lt;^-(:8 thioalkoxy, (^-(^ alkoxy, CN, -NRn2R113, _CONR112 R113 or halogen, G is EjCVCu alkyl, and R112 and R113 are each independently Η; C6_C18 aryl; C丨-Ci8 alkyl, or (vc) 8 alkoxy substituted eve 8 aryl; Ci- Ci8 alkyl; or hetero-O-iC^-Cu alkyl, B, D and E are each independently a group of the formula: 156275.doc 4- 201211099 (VI) or Formula IV, provided that B, D and E are groups of formula IV, which differ from A, where k is 1, 1 is 0 or 1, r is 0 or 1, z is 0 or 1 , a is an 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 integer 1 or 2, 156275.doc 201211099 1 is 〇, or integer 1 or 2, R1' and R2' have the meaning of R1 independently of each other, Ar8, Ar8, Ar9, Ar9', Ar1() and Ar1. • independently of each other having the meaning of Ar2, and Ar4, Ar5, Ar6 and Ar7 are independently of each other: One of them is N and the other is CR14, Ar2G is an aryl or heteroaryl group, each of which may be substituted as appropriate, R118 has the meaning of R116, and R12 and R12 are independently hydrogen, respectively! a compound; optionally, a Cl-C25 alkyl group having a plurality of oxygen or sulfur atoms, especially a c4-c25 alkyl group; an alkoxy group, a C7-C25 aryl group, or a =-R13; 13 R system 匸丨-C丨〇alkyl or tri(c丨_c8 alkyl)decyl, R, Rl4, R15, R15·, R17 and R17' are each independently Η; or optionally one or more oxygen atoms Ci_c25 alkyl, especially a group; R and R 8 are each independently hydrogen, halogen; optionally mixed with a plurality of oxygen or sulfur atoms (: 丨 _ (: 25 alkyl, especially C4_C25 alkyl; aromatic burning Or (^-(:25 alkoxy; 25 R-hydrogen, C7-C25 aralkyl, c6_Ci8 aryl; 156275.doc ^18 201211099, or qc,8 alkoxy substituted C6_Cis aryl; or Optionally, one or more Ci/C25 alkyl groups of an oxygen or sulfur atom, especially a C4_C25 alkyl group; R20 and R2Q are each independently hydrogen, a core...25 aralkyl; optionally, one or more oxygen or sulfur atoms of Ci_C25 Alkyl, especially alkyl, &amp; X7 series-0-, -s-, -NR丨丨5-, -Si(R丨丨7)(R丨17,)_, _c(R120)(r12., X8 is -Ο- or -NR115-; r10Q and r1qq' are each independently H, F, Ci_Ci8 alkyl, heterocyclic CVCu alkyl, Ct-Cu decyl, hetero ruthenium Cl_Cl8 alkoxy, Ci_ cls perfluoroalkyl, optionally substituted by Cl_C8 alkyl and/or (:1_〇:8 alkoxy for 1 to 3 times C6-C24 aryl, optionally by Cl_C8 alkyl and/or Ci_ oxynitride Substituting 1 to 3 times of C2-C2 anthracene aryl; R303, R3, 4, R3. 5 and R are independently of each other, h, F, c丨·Ci8 alkyl, heterozygous Ci-C18 Base, Ci-Cu methoxy, heterocyclic C!-Cu alkoxy, Ci-Cu perfluoroalkyl, optionally substituted by Cl-c8 alkyl and / or Ci-C8 alkoxy 1 to 3 The next C6_C24 aryl group, optionally substituted with Ci_C8 alkyl group and/or Ci-Cs oxy group for 1 to 3 times C2-C2q heteroaryl; R307 and R3G8 are independently of each other or may be mixed with one or more a C 1 -C25 alkyl group of an oxygen or sulfur atom; I56275.doc 201211099 R, Rm, r34r312 are each independently Η, C!-C25 alkoxy or, optionally, a Ci/C25 alkane having one or more oxygen or sulfur atoms R and 尺1()1 are, independently of each other, Η, F, c丨-Cu alkyl, heterogeneous CVCu垸, Ci_Ci8 alkoxy, heteroaminated alkoxy, C1_Cl8 perfluoroalkyl, optionally substituted by Ci_c8 alkyl and/or alkoxy 1 to 3 times CpC24 aryl, optionally c丨·c8 Alkyl and/or Ci_Cs alkoxy substituted 1 to 3 times c: rC2. Heteroaryl; ρ1〇2τι r»102'yj_ and R are independently of each other, 齿, 牙素, optionally one or more a Cl_C25 alkyl group of an oxygen or sulfur atom; a C7_C25 arylalkyl group or a Ci_c25 alkoxy group; R103 and R103 are each independently hydrogen, halogen; optionally a Ci-C25 alkyl group having one or more oxygen or sulfur atoms Optionally, 1 to 3 times of a C^C24 aryl group may be substituted by a Cl_c8 alkyl group and/or a 匕-匸8 alkoxy group; a C7_C25 aryl group, CN, an alkoxy group; or R103 and Riw may form a ring, Rl15 and R115_ are each independently hydrogen, C6-Cu aryl; CpC,8 aryl substituted by alkyl or C^-Cu alkoxy; CVC25 alkane optionally having one or more oxygen or sulfur atoms a group, especially a C^c:25 alkyl group; or a C7-C25 arylalkyl group, R117 and R117 are each independently a Ci-C" alkyl group, a CVC25 aryl group, or optionally (^-(: 8-alkyl and /4Cl_C8 alkoxy Substituting 1 to 3 phenyl groups, R12G and 12()_ are independently hydrogen, optionally mixed with - or a plurality of oxygen or sulfur atoms, C丨-C35 alkyl, or C7-C25 aryl alkane Base, 156275.doc 8 201211099 R is H, optionally mixed with - or a plurality of oxygen or sulfur atoms, Cl_Cl8 alkyl, perfluoro, optionally referred to as (10) and/or c] _ CS alkoxy substituted 1 Up to 24 aryl groups; optionally, C2-C2 is substituted 1 to 3 times with a base and a ' or a 8 alkoxy group. a heteroaryl group; or a prerequisite for at least one of the groups Ar, Ar丨·, Ar2, A〆, Af3, and A〆 R'\ R O' &gt;1〇4 R1〇\ R104' !L or And/or at least one of the groups 8, 〇 2. and E contain a group R And / or 0 14, R \ R R 118 14. As requested in item 1! : object, where Ari and ΑΓ1_ are independent of each other as R1 Ο R1 Bu s', ,, S~ or, where R104, R104, and Han... are the keys of the DPP skeleton as defined in claim 1 and represent the group Οα V (iVb), 156275.doc 1. A polymer according to claim 1 or 2, wherein A is a base of the formula 201211099 R 104 (IVe) (IVf) (IVg) (IVh) (IVi) (IVj), or 156275.doc • 10. 8 201211099 (IVk), wherein R1 and R2 are each independently Crew alkyl, especially C8_C36 alkyl, R104 is eve, 5 alkyl, especially c^C25 alkyl, which may optionally have one or more oxygen or sulfur atoms, and Or -S-Ci-C25 Institute R116 system, or cvc25 alkyl: or hetero group, wherein B, D, and E are each other. 4. The polymer of any one of claims 1 to 3 is of the following formula. Group 156275.doc -11- 15 201211099 R 15· R R 15 R 15' (Vn) , 15 R 12 (Vo) (Vp) R20 R20· , 1S_ , 15 R 18 State, 〆$ (Vs) (Vt) (Vu) R 116 (Vv) N; S'N (Vw) (Vx), for example s s , 100 „100* (Vx&quot;) (Vy), for example (Vy,) .100 Γ-.100' %101 r»10V (Va1) 156275.doc 12- 8 201211099 (Va·), R303, r304, r305, r306, r307, r308, r309, r310, R3H, R312, R100, R100·, R101, R101., R102, R102, R103, r103', ruler 12() and &amp;12() _ is as defined in the request item i, a is an integer 1 to 5, especially 1 to 3, one of X1 and X2 is N and the other is CH, one of X5 and X6 is N and the other CR14, R18 Ar2Q can be replaced by an extended aryl group, for example ~ R11t ^ R114' or as the case may be Substituting heteroaryls, for example S 156275.doc -13- 201211099 R114 and R114 are each independently hydrogen or Ci_Ci8 alkyl, R116 is an alkyl group, and the Ci_C25 alkyl group 'R12 and R12 are independently hydrogen and halogen; and optionally, Ci-C25 having a plurality of oxygen or sulfur atoms Alkyl, especially C4_C25 alkyl; Ci_c alkoxy, C7-C25 arylalkyl, or _=-R13; R 匚丨-C丨〇 alkyl or tri(C丨_c8 alkyl) formyl ' R15, R15, R17 and R17' are, independently of each other, Η; or optionally a Cl_C25 alkyl group having one or more oxygen atoms, especially a C6_c25 alkyl group, an alkyl group, especially a c:6_C25 alkyl group, which may optionally have one Or a plurality of oxygen atoms, R 8 and R 18 are independently of each other hydrogen, halogen; optionally, a q-Cu alkyl group having one or more oxygen or sulfur atoms, especially a c4-c25 alkyl group; a C7_C25 aryl group or a Ci- C25 alkoxy; Rl9 is a nitrogen, (: 7-(:25 aralkyl, c6-Ci8 aryl; C6_Cl8 aryl substituted by Cl_Ci8 alkyl or C1-CU alkoxy; or optionally mixed or a plurality of oxygen or sulfur atoms iCrCw alkyl 'in particular C4_C25 alkyl; and R independently from each other are hydrogen, C7_C25 arylalkyl; optionally mixed - or multiple oxygen or sulfur a Q-C25 alkyl group, especially a c4-c25^ group. The polymer of the term 1 of the formula 1 which comprises a repeating unit of the formula *+A-D+*(1), wherein A is as defined in claim 3 iVa, IVc, IVe, IVg, 156275.doc 201211099 IVh, FVi, iVj or IVk, RiR2 C1-C35 alkyl, especially c8-c35 alkyl, R-based Cl-C25 alkyl, especially C4 a C25 alkyl group which may optionally have one or more oxygen or sulfur atoms, and Ds is a formula Va, Vb, Vc as defined in claim 4, especially ~~~, Ve, Vf, Vh, Vi, Vj, Vk, VI, Vm, Vn, =, vp, Vq, vr, Vs, Vu, Vv, Vw, Vx, especially the group of -~, Vy, Vz or Va'. a polymer comprising a repeating unit of the formula: _^^4 七(11), wherein x=0.995 to 〇.005, y=〇〇〇5 to 〇995, especially χ=〇二至〇8, y=0.8 to 0.2, and wherein x+y=1; A is a group of formula IVa, IVc, IVe, IVg, IVh, IVi, ivj or IVk as defined in claim 3, R and 2 series Cl-C35 alkyl, especially C8-C35 alkyl, R-based Cl_C25 alkyl, especially C4_C25 alkyl, as the case may be Mixed with one or more oxygen or sulfur atoms, B and D to each other site of ^ formula in% as defined in the claims, the terms 4, Vb Vc, in particular a group of Ve, Vf, Vh, Vi, Vj, Vk, VBu Vm, Vn "^Vp, Vq, Vr, Vs, %, vv, vw, vx, especially Vy, Vz or Va; or 156275. Doc -15- 201211099 The polymer *+α-ε&gt;Ή·β-Ητ (η) containing a repeating unit of the following formula, wherein χ=0.995 to 0.005, y=〇.〇〇5 to 0.995, especially x =〇_2 to 〇·8, y=0'8 to 0·2, and wherein x+y=l; A is the formula IVa, IVc, iVe, IVg, IVh, IIV as defined in claim 3, a group of IVj or IVk, R is a C!-C25 alkyl group, especially a C4_C25 alkyl group which may optionally have one or more oxygen or sulfur atoms, Group R and R are C1-C35 alkyl, especially C8-C35, based on the formula Va, vb, Vc as defined in claim 4, especially , Ve, Vf, Vh, Vi, Vj, Vk, VI, Vm, especially Vn, Vo, Vp, Vq, Vr, Vs, Vu, Vv, Vw, Vx, A group of Vy, Vz or Va', such as the polymer of claim 1, which comprises a repeating unit of the formula *+A_D廿B-.廿八一 E廿B—E 七(1)^, where 卜0.985 〇·〇〇5, s=〇.〇〇5 to 0.985, t=0.005 to 0.985, u=〇.〇〇5 to 〇·985 ' And wherein r+s+t+u=1, A is a group of formula IVa, IVc, IVe, IVg, ivh, ivi, IVj or IVk as defined in claim 3, 156275.doc 201211099 R1 and R2 (VC35 alkyl, especially c8_c35 alkyl, R104 is q-C25 alkyl, especially CcC25 alkyl, optionally containing one or more oxygen or sulfur atoms, B, D and E independently of each other as in claim 4 The defined formula %, Vb, Vc' is especially. , Ve, Vf, Vh, Vi, Vj, Vk, V Bu Vm, Vn, vo, Vp, Vq, Vr, Vs, Vu, Vv, Vw, a group of Vx, especially s s , Vy, Vz or Va, 8. A polymer of the formula 1 which is a polymer of the formula P1 (Ic) Μ (Id) 156275.doc • 17· 201211099 156275.doc 18. 8 201211099 m η p q Γ 156275.doc •19· 201211099 156275.doc -20- 8 201211099 RIN N_R, 101 P-.10V (la,) NIR p120 p120* r102 π r102· (lb') NIR R-N R100 R100' 102_ (Ic’), especially N-R N-R Ri〇〇 Ri〇〇' (Id1), especially N-R 156275.doc •21 · 201211099 o100 „100' (If), especially (Ig1), especially 156275.doc -22- 8 201211099 156275.doc -23- 201211099 C e R (Hi), or 〇8&lt;36 alkyl*104 R is a CVCu alkyl group, especially c^c:25 alkyl group, which may optionally be hetero or a plurality of oxygen or sulfur atoms, and RU, R15., R17 and R17' are independently of each other. Or, as appropriate, 56 56.doc 201211099 Cl_C25 alkyl having one or more oxygen atoms, especially C6_c25 alkyl, R20 and R20 are each independently argon, CrCu aralkyl; optionally one or more oxygen or sulfur Alkyl Cl_c25 alkyl, especially C4_C25 alkyl 'R10G and R1GG' Η, R and 尺 101 Η, (: 25 (or 25 alkyl, or Cl_C25 alkoxy R102 and R1Q2, H, or Cl_C25 alkyl, R103 and R1G3' are H or Cl_C25 alkyl, R116 is H, or Cl-C25 alkyl, R12G and R12. 'System (VCm alkyl, 9 η is 4 to 1〇〇〇' especially 4 to 2〇〇, very particularly to 1〇〇, and χ=〇·995 to 〇·_, y=G side to G 995, especially χ=() 2^ y=〇_8 to 0.2, and where x+y=i. 9. 10. 11. 12. An organic semiconductor material, layer or component, comprising the polymer of any one of claims (8). A semiconductor device, comprising the polymer of any one of the claims (1), or the organic semiconductor material, layer or component of claim 9. A semiconductor device according to claim 10, which is an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor. For example, a semiconductor device is requested, wherein the device comprises in turn: (a) a cathode (electrode), (9) a transition layer depending on the case, such as a metallization, especially gasification 156275.doc 25· 201211099 (c) photoactivity Layer, (d) smooth layer as appropriate, (e) anode (electrode), and (f) substrate. 13. A method of preparing an organic semiconductor award + (4) device, the method comprising: applying a solution and/or a dispersion of a polymer such as any one of the materials of the skins of the present invention to a suitable substrate On, and remove the solvent. 14. A polymer as claimed in any one of claims 1 to 8, or the use of an organic semiconductor material, layer or component as claimed in claim 94 for PV isolation, photodiode, or organic airport effect In the transistor. 15. - Compounds of the formula R1 -X1 (X) 'where a, b, c, d, e, f, R丨, r2, Ar丨, A, Ar2 '斛2, Ar3 and Ar3' are as defined in claim i and χη On each occurrence, it is ZnX12, _SnR207R208R209, where R2〇7, R2〇8&amp;r209 are the same or different and are 幵 or (^-〇:6 alkyl, two of which are shaped as appropriate The oxime group optionally has a bond or no bond; the X12 dentate ' ^ is specifically I or Br; -0S(0)2CF3, -0S(0)2-aryl, T〇~ch3, -0S(0)2CH3, ·Β(ΟΗ)2, -B(oh)3- -BF3, _Β(〇γΐ)2, -B,0 '0 Y 14 or _B, o &gt; 2, wherein Y1 is independently c c2-c1Q alkyl group at each occurrence of _d〇c _26· 8 201211099, for example CY11Y12_, wherein γ Υ 11 and Υ 12 are independent of each other (ch3) 2c(ch3 -CH2C(CH3)2CH2-alkyl. I'C丨0 alkyl and γ2 is independently such as -CY3y4-CY5Y6· or -CYWCY9Y10_, Υ4, Υ5, Υ6, γ7, in each field. Γ8, γ9, γ丨, the site is hydrogen, or Cl_CiQ alkyl, especially) 2_, or -C(CH3)2CH2C(CH3)2_, and Y and Y14 are each independently hydrogen or c π 1 η 156275.doc •27 · 201211099 IV. Designation of Representative Representatives (1) The representative representative of the case is: (none) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please reveal the characteristics that best show the invention. Chemical formula: *--AD--* AUX ϋ U II -AD- _B-D 廿A—HrfB—ε4γ 111 156275.doc