JP6828033B2 - Degradable conjugate polymer - Google Patents

Description

Detailed Description The present invention uses a degradable conjugate polymer, a method for producing the degradable conjugate polymer from a monomer, and a semiconductor single-walled carbon nanotube and a metallic single-walled carbon nanotube using the degradable conjugate polymer as a dispersant. The present invention relates to a method for separating semiconducting single-walled carbon nanotubes from a mixture of.

Single-walled carbon nanotubes (SWNTs) exhibit metal or semiconductor properties, depending on tube diameter and lap angle. Many SWNT applications, such as organic photovoltaic (OPV) devices and organic field effect transistors (OFETs), specifically require semiconducting SWNTs containing minimal metallic SWNT impurities. Unfortunately, all current SWNT growth methods, such as arc discharge or laser ablation, produce a mixture of semiconducting SWNTs and metallic SWNTs.

Several methods are known to separate semiconducting SWNTs from metallic SWNTs, but most of them are not yet suitable for large technical processes. An effective method relies on dispersing the semiconductor SWNT and the metallic SWNT in a polymer and then centrifuging.

Nish, A .; Hwang, J.-Y .; Doig, J .; Nicholas, RJ Nat. Nano 2007, 2, 640-646, as a dispersant for SWNTs, used several polymers and copolymers containing fluorene units. It is described. As the dispersant, poly (9,9-diocil-fluorenyl-2,7-diyl) (PFO) shows the highest selectivity.

Berton, N .; Lemasson, F .; Tittmann, J .; Stuerzl, N .; Hennrich, F .; Kappes, MM; Mayor, M. Chem. Mat. 2011, 23, 2237-2249 is a dispersant for SWNT. As, some copolymers containing either fluorene units or carbazole units separated by spacers of naphthalene, anthracene and anthraquinone are described.

Tange, M .; Okazaki, T .; Iijima, SJ Am. Chem. Soc. 2011, 133, 11908-11911 is a poly (9,9-diosylfluorene-alt-benzothiadiazole) (9,9-diosylfluorene-alt-benzothiadiazole) as a dispersant for SWNT. F8BT) and poly (9,9-di-n-dodecylfluorene) (PFD) are described. In particular, F8BT selectively separates large (> 1.3 nm) diameter SWNTs.

Akazaki, K .; Toshimitsu, F .; Ozawa, H .; Fujigaya T .; Nakashima, NJ Am. Chem. Soc. 2012, 134, 12700-12707 are 12 copolymers (9, 9) as dispersants for SWNT. -Dioctylfluorene-2,7-diyl) _x ((R)-or (S) -2,2'-dimethoxy-1,1'-binaphthalene-6,6-diyl) _y (in the formula, x and y are The composition ratio of the copolymer) is described.

Jakubka, F .; Schiessl, SP; Martin, S .; Englert, JM; Hauke, F .; Hirsch A., Zaumseil, J. ACS Marco Lett. 2012, 1, 815-819 is a poly (SWNT dispersant) 9,9-Dioctylfluorene) and poly (9,9-dioctylfluorene-co-benzothiadiazole) are described.

Mistry, KS; Larsen, BA; Blackburn, JL ACS Nano 2013, 7, 2231-2239 is a poly [(9,9-dioctylfluorenyl-2,7) dispersant for laser-evaporated SNWT with an average diameter of 1.3 nm. -Diyl) -alt-co- (6,6'-(2,2'-bipyridine))] and poly [(9,9-dihexylfluorenyl-2,7-diyl) -co- (9,10) -Anthracene)] is described.

Qian, L .; Xu, W .; Fan, X .; Wang, C .; Zhang, J .; Zhao, J .; Cui, ZJ Phys. Chem. 2013, C117, 18243-18250 is a large diameter SWNT. 9,9-Dioctylfluorene-co-bithiophene is described as a dispersant for SWNTs for selectively separating from commercial arc discharge SWNTs.

Wang, H .; Mei, J .; Liu, P .; Schmidt, K .; Jimenez-Oses, G .; Osuna, S .; Fang, L .; Tassone, CT; Zoombelt, AP; Sokolov, AN; Houk KN; Toney, MF; Bao, Z. ACS Nano 2013, 7, 2659-2668 is a poly (dithiaful) dispersant for separating semiconductor SWNTs from arc-discharged 1.1-1.8 nm SWNTs. Valen-fluoren-com-thiophene) is described.

Berton, N .; Lemasson, F .; Poschlad, A .; Meded, V .; Tristram F .; Wenzel, W .; Hennrich, F .; Kappes, MM; Mayor, M. Small 2014, 10, 360-367 Selectively separates poly (fluorene-alt-pyridine) copolymers and large diameter (> 1 nm and up to 1.3 nm) SWNTs, each having a 2,7-fluorene unit but varying with the binding of the pyridyl group. A poly (carbazole-alt-pyridine) copolymer is described as a dispersant for SWNTs for this purpose.

Semiconductor polymers as dispersants for SWNTs in separation processes based on centrifugation are particularly useful, and the products of centrifugation processes containing semiconductor polymers and semiconducting SWNTs are used in the manufacture of organic devices such as organic field effect transistors (OFETs). Can be used directly.

Lee, HW; Yoon, Y .; Park, S .; Oh, JH; Hong, S .; Liyanage, LS; Wan, H .; Morishita, S .; Patil, N .; Park, YJ; Park, JJ; Spakowitz, A .; Galli, G., Gygi, F .; Wong, PH-S .; Tok, JB-H .; Kim, JM; Bao, Z. Nat. Commun. 2011, 2, 541-548 As a dispersant for SWNTs, Regioregular Poly (3-alkylthiophene), which is often used as a semiconductor material in organic electronic devices such as organic field effect transistors (OFETs), is described. Transistors containing a registry regular poly (3-alkylthiophene) and a semiconducting SWNT are described.

U.S. Patent Application Publication No. 2012/0104328 (US 2012/0104328) describes a polythiophene derivative comprising a thiophene ring and a hydrocarbon side chain attached to the thiophene ring. Transistors containing polythiophene derivatives and semiconducting SWNTs are described.

Smithson, C; Wu, Y .; Wigglesworth, T .; Gardner, S .; Thu, S .; Nie H.-Y. Organic Electronics 2014, 15, 2639-2646 is not with diketopyrrolopyrrole-quarter thiophene. Describes the manufacture of organic thin film transistors using semiconductor copolymers with sorting SWNTs.

Since conjugated polymers extract s-SWNT in a few hours via simple sonication or centrifugation steps, they have been thoroughly studied to concentrate s-SWNT. In addition, a conjugate polymer having a specific molecular design can selectively extract a semiconductor SWNT having a specific chirality (n, m). Wrapping of conjugated polymers provides a fast, low cost, scalable method for s-SWNT separation, but this method has two major drawbacks: (1) Purified s-SWNT It retains many conjugate polymers on its surface. Removal of conjugated polymers is difficult due to tight polymer wrapping and strong polymer / SWNT interactions. (2) The same amount of conjugated polymer is usually used for the separation of SWNT. However, the price of conjugated polymers is comparable to and even higher than that of SWNTs. For example, poly (9,9-di-n-dodecylfluorenyl-2,7-diyl) (PFDD), which is widely used for sorting SWNTs, is $ 364.50 / 500 mg but has a purity of 30%. The plasma SWNT is $ 10 / g and the arc discharge SWNT with a purity of about 30% is $ 35 / g. Thus, conjugated polymers account for a significant amount of the cost for this method. To address these issues, three strategies have been developed: (1) releasing SWNTs with conformational variable polymers; (2) non-degradable into small units using excess acid. Use covalently bonded supramolecular polymers; (3) irreversibly break down polymers into smaller units. Strategy (1) requires a specific design for the polymer structure and has not proven to be excellent in s-SWNT selectivity. In strategy (2), supramolecular polymers usually require expensive and complex non-covalent moieties, usually in situ forming polymers of different concentrations with different molecular weights. This strategy also requires an excess of acid to decompose the polymer, which can act as a dopant for SWNTs. Strategy (3) is destructive and decomposed monomers cannot be recycled. Therefore, the ideal conjugate polymer used for SWNT sorting must be low cost, removable, recyclable, highly selective, and less damaging to SWNTs. However, it is difficult to meet all of these criteria.

An object of the present invention is to provide a degradable conjugate polymer suitable as a dispersant for separating semiconductor single-walled carbon nanotubes from a mixture of semiconductor single-walled carbon nanotubes and metallic single-walled carbon nanotubes. .. In particular, the degradable polymer must be easy to synthesize and irreversibly degradable into small units.

This task is a polymer containing at least one unit of formula (1).
Solved by
In the above formula,
T ¹ is a carbon atom or a nitrogen atom and
T ² is a carbon atom if T ¹ is a nitrogen atom, or is a nitrogen atom if T ¹ is a carbon atom.
r is 1, 2, 3 or 4
s is 1, 2, 3 or 4
M ¹ and M ² are independent of each other
Selected from the group consisting of
Here, in M ¹ and M ² ,
b and c are 1, 2, 3, 4, 5 or 6 independently of each other.
a and d are 0, 1, 2, 3 or 4, independent of each other.
n and m are 0, 1, 2, 3 or 4, independent of each other.
A is
Selected from the group consisting of, and B is
Selected from the group consisting of
Where X is O, S, Se or NR ¹ in each case.
M ¹ or M ² can be substituted with 1 to 4 substituents R ² .
L ¹ and L ² are independent of each other, in each case C _6-18 allele, 5-20 member hetero allele,
Selected from the group consisting of
Here, C _6-18 arylene and 5-20 member heteroarylene are C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-12 cycloalkyl, C _6-18 aryl and in each case. 5-20 member heteroaryl, OR ³¹ , OC (O) -R ³¹ , C (O) -OR ³¹ , C (O) -R ³¹ , NR ³¹ R ³² , NR ^31- C (O) R ³² , C (O) -NR ³¹ R ³² , N [C (O) R ³¹ ] [C (O) R ³² ], SR ³¹ , halogen, CN, SiR ^Siv R ^Siw R ^Six and selected from the group consisting of OH 1 can be substituted with 6 substituents R ^3,
here
In each case C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-12 cycloalkyl, C _6-18 aryl and 5-20 member heteroaryl, C (O) -R ⁴¹ , It can be replaced by a ^{C (O) -NR 41 R 42} , C (O) 1 or 2 substituents ^{R 4} is selected from the group consisting of ^{-OR 41} and CN,
Here, R ³¹ , R ³² , R ⁴¹ and R ⁴² are independent of each other and in each case H, C _{1 to 30} alkyl, C _{2 to 30} alkenyl, C _{2 to 30} alkynyl, C _{5 to 12} cycloalkyl, C. Selected from the group consisting of _6-18 aryl and 5-20 member heteroaryl
Here, C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl are C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ⁱ , OC (O) -R. ^j , C (O) -OR ⁱ , C (O) -R ⁱ , NR ⁱ R ^j , NR ^i- C (O) R ^j , C (O) -NR ⁱ R ^j , N [C (O) R ⁱ ] [C (O) R ^j ], SR ⁱ , halogen, CN, SiR ^Siv R ^Siw R ^Six and NO ₂ can be substituted with 1 to 10 substituents independently selected from the group. And at least two CH ₂ groups (but not adjacent CH ₂ groups) of C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl can be replaced with O or S.
C _5-12 cycloalkyls are C _1-20 alkyl, C _2-20 alkenyl and C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ⁱ , OC. (O) -R ^j , C (O) -OR ⁱ , C (O) -R ⁱ , NR ⁱ R ^j , NR ^i- C (O) R ^j , C (O) -NR ⁱ R ^j , N [ With 1 to 6 substituents independently selected from the group consisting of C (O) R ⁱ ] [C (O) R ^j ], SR ⁱ , halogen, CN, SiR ^Siv R ^Siwa R ^Six and NO _2. Can be substituted; and one or two CH ₂ groups of C _5-12 cycloalkyl (but not adjacent CH ₂ groups) are O, S, OC (O), CO, NR ⁱ or NR. Can be replaced by ^i- CO
C _6-18 aryl and 5-20 membered heteroaryl are C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 membered hetero. Aryl, OR ⁱ , OC (O) -R ^j , C (O) -OR ⁱ , C (O) -R ⁱ , NR ⁱ R ^j , NR ^i- C (O) R ^j , C (O) -NR 1-independently selected from the group consisting of ⁱ R ^j , N [C (O) R ⁱ ] [C (O) R ^j ], SR ⁱ , halogen, CN, SiR ^Siv R ^Siwa R ^Six and NO ₂ . Can be substituted with 6 substituents,
Here, R ^Siv , R ^Siwa , and R ^Six are independent of each other, H, C _{1 to 20} alkyl, C _{2 to 20} alkenyl, C _{2 to 20} alkynyl, C _{5 to 6} cycloalkyl, phenyl and O-Si ( CH ₃ ) Selected from the group consisting of ₃
R ⁱ and R ^j consist of the group consisting of H, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl and 5-14 member heteroaryl. Selected independently,
Where C _1-20 alkyl, C _2-20 alkenyl and C _2-20 alkynyl are C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^k , OC (O) -R. ^l , C (O) -OR ^k , C (O) -R ^k , NR ^k R ^l , NR ^k- C (O) R ^l , C (O) -NR ^k R ^l , N [C (O) R ^k ] [C (O) R ^l ], SR ^k , halogen, CN and NO ₂ can be substituted with 1-5 substituents selected from the group;
C _5-8 cycloalkyls are C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^k , OC. (O) -R ^l , C (O) -OR ^k , C (O) -R ^k , NR ^k R ^l , NR ^k- C (O) R ^l , C (O) -NR ^k R ^l , N [ It can be substituted with 1-5 substituents selected from the group consisting of C (O) R ^k ] [C (O) R ^l ], SR ^k , halogen, CN, and NO ₂ ;
C _6-14 aryl and 5-14 member heteroaryls are C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member hetero. Aryl, OR ^k , OC (O) -R ^l , C (O) -OR ^k , C (O) -R ^k , NR ^k R ^l , NR ^k- C (O) R ^l , C (O) -NR ^With 1 to 5 substituents independently selected from the group consisting of ^k R ^l , N [C (O) R ^k ] [C (O) R ^l ], SR ^k , halogen, CN, and NO _2. Can be replaced;
Here, R ^k and R ^l are independently selected from the group consisting of H, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl.
Here, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl can be substituted with 1-5 substituents selected from the group consisting of halogen, CN and NO ₂ .
L ³ and L ⁴ are independently selected from the group consisting of C _6-18 alleles and 5 to 20 member hetero _{allylenes in} each case.
Here, C _6-18 arylene and 5-20 member heteroarylene are C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-12 cycloalkyl, C _6-18 aryl and in each case. 5-20 member heteroaryl, OR ⁹¹ , OC (O) -R ⁹¹ , C (O) -OR ⁹¹ , C (O) -R ⁹¹ , NR ⁹¹ R ⁹² , NR ^91- C (O) R ⁹² , C ^{(O) -NR 91 R 92,} N [C (O) R 91] [C (O) R 92], SR 91, 1 is selected from ^{halogen, CN,} from the group consisting of ^SiR Siy ^{R Siz R Siaa} and OH can be substituted with 6 substituents R ^9,
Here, R ⁹¹ and R ⁹² are independent of each other, in each case H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-12 cycloalkyl, C _6-18 aryl and Selected from the group consisting of 5 to 20 member heteroaryl,
Here, C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl are C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ^m , OC (O) -R. ^m , C (O) -OR ^m , C (O) -R ^m , NR ^m R ⁿ , NR ^m- C (O) R ⁿ , C (O) -NR ⁿ R ^m , N [C (O) R ^{n] [C (O) R} m], SR n, ^{halogen, CN,} can be substituted by 1 to 10 substituents selected independently from the group consisting of ^SiR Siy ^{R Siz R Siaa} and NO ₂ And at least two CH ₂ groups (but not adjacent CH ₂ groups) of C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl can be replaced with O or S.
C _5-12 cycloalkyls are C _1-20 alkyl, C _2-20 alkenyl and C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ^m , OC. (O) -R ^m , C (O) -OR ^m , C (O) -R ^m , NR ^m R ⁿ , NR ^m- C (O) R ⁿ , C (O) -NR ^m R ⁿ , N [ ^{C (O) R m] [} C (O) R n], SR m, ^{halogen, CN,} 1 to 6 substituents independently selected from the group consisting of ^SiR Siy ^{R Siz R Siaa} and NO ₂ Can be substituted; and one or two CH ₂ groups of C _5-12 cycloalkyl (but not adjacent CH ₂ groups) are O, S, OC (O), CO, NR ^m or NR. Can be replaced by ^m- CO,
C _6-18 aryl and 5-20 membered heteroaryl are C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 membered hetero. Aryl, OR ^m , OC (O) -R ^m , C (O) -OR ^m , C (O) -R ^m , NR ^m R ⁿ , NR ^m- C (O) R ⁿ , C (O) -NR ^{m R n 1~, n [C} (O) R m] where ^{[C (O) R n]} , SR m, ^{halogen, CN,} are independently selected from the group consisting of ^SiR Siy ^{R Siz R Siaa} and NO ₂ Can be substituted with 6 substituents,
^{R Siy,} R Siz, R ^Siaa independently of one _{another, H, C 1 to 20 alkyl, C 2 to 20 alkenyl, C 2 to 20 alkynyl, C 5 to 8} cycloalkyl, phenyl and O-Si (CH ₃ ) Selected from the group consisting of ₃
Here, R ^m and R ⁿ consist of H, C _{1 to 20} alkyl, C _{2 to 20} alkenyl, C _{2 to 20} alkynyl, C _{5 to 8} cycloalkyl, C _{6 to 14} aryl and 5 to 14 member heteroaryl. Selected independently of the group,
C _1-20 alkyl, C _2-20 alkenyl and C _2-20 alkynyl are C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^o , OC (O) -R ^o , C (O) -OR ^o , C (O) -R ^o , NR ^o R ^p , NR ^o- C (O) R ^p , C (O) -NR ^o R ^p , N [C (O) R ^o ] It can be substituted with 1-5 substituents selected from the group consisting of [C (O) R ^p ], SR ^o , halogen, CN and NO ₂ ;
C _5-8 cycloalkyl is C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^o , OC (O) -R ^o , C (O) -OR ^o , C (O) -R ^o , NR ^o R ^p , NR ^o- C (O) R ^p , C (O) -NR ^o R ^p , N [ It can be substituted with 1 to 5 substituents selected from the group consisting of C (O) R ^o ] [C (O) R ^p ], SR ^o , halogen, CN, and NO ₂ ;
C _6-14 aryl and 5-14 member heteroaryls are C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member hetero. Aryl, OR ^o , OC (O) -R ^o , C (O) -OR ^o , C (O) -R ^o , NR ^o R ^p , NR ^o- C (O) R ^p , C (O) -NR ^With 1 to 5 substituents independently selected from the group consisting of ^o R ^p , N [C (O) R ^o ] [C (O) R ^p ], SR ^o , halogen, CN, and NO _2. Can be replaced;
Here, ^Ro and R ^p are independently selected from the group consisting of H, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl.
Here, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl can be substituted with 1-5 substituents selected from the group consisting of halogen, CN and NO ₂ .
R ¹ in each case is C _1-100 alkyl, C _2-100 alkenyl, C _2-100 alkynyl, C _5-12 cycloalkyl, C _6-18 aryl, 5-20 member heteroaryl, C (O)- Selected from the group consisting of C _1-100 alkyl, C (O) -C _5-12 cycloalkyl and C (O) -OC _1-100 alkyl.
Here, C _1-100 alkyl, C _2-100 alkenyl and C _2-100 alkynyl are C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ^a , OC (O) -R. ^a , C (O) -OR ^a , C (O) -R ^a , NR ^a R ^b , NR ^a- C (O) R ^b , C (O) -NR ^a R ^b , N [C (O) R ^a ] [C (O) R ^b ], SR ^a , Si (R ^Sia ) (R ^Sib ) (R ^Sic ), ^-O -Si (R ^Sia ) (R ^Sib ) (R ^Sic ), halogen, CN, and independently from the group consisting of NO ₂ can be substituted by 1 to 40 substituents selected; and _{C 1 to 100 alkyl, C 2 to 100} alkenyl and _{C 2 to 100} at least two CH alkynyl ₂ Groups (but not _two adjacent CHs) can be replaced by O or S,
C _5-12 cycloalkyl is C _1-60 alkyl, C _2-60 alkenyl, C _2-60 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ^a , OC (O) -R ^a , C (O) -OR ^a , C (O) -R ^a , NR ^a R ^b , NR ^a- C (O) R ^b , C (O) -NR ^a R ^b , N [ C (O) R ^a ] [C (O) R ^b ], SR ^a , Si (R ^Sia ) (R ^Sib ) (R ^Sic ), ^-O -Si (R ^Sia ) (R ^Sib ) (R ^Sic ), It can be substituted with 1 to 6 substituents independently selected from the group consisting of halogen, CN, and NO ₂ ; and one or two CH ₂ groups of C _5-12 cycloalkyl (provided that they are). (Not _two adjacent CHs) can be replaced by O, S, OC (O), CO, NR ^a or NR ^a- CO.
C _6-18 aryl and 5-20 membered heteroaryl are C _1-60 alkyl, C _2-60 alkenyl, C _2-60 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 membered hetero. Aryl, OR ^a , OC (O) -R ^a , C (O) -OR ^a , C (O) -R ^a , NR ^a R ^b , NR ^a- C (O) R ^b , C (O) -NR ^a R ^b , N [C (O) R ^a ] [C (O) R ^b ], SR ^a , Si (R ^Sia ) (R ^Sib ) (R ^Sic ), ^-O -Si (R ^Sia ) (R ^Sib ) ) Can be substituted with 1 to 6 substituents independently selected from the group consisting of ( ^RSic ), halogen, CN, and NO ₂ .
Here, ^Ra and R ^b consist of H, C _1-60 alkyl, C _2-60 alkenyl, C _2-60 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl and 5-14 member heteroaryl. Selected independently of the group,
R ^Sia , R ^Sib and R ^Sic are H, C _1-60 alkyl, C _2-60 alkenyl, C _2-60 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, _{OC 1-60} alkyl, _{OC 2-60} alkenyl, _{OC 2-60} alkynyl, _{OC 5-8} cycloalkyl, _{OC 6-14} aryl, O-5-14 member heteroaryl, -[O-SiR ^Sid R ^Sie ] selected independently from the group consisting of _o- R ^Sif , NR ⁵ R ⁶ , halogen and ^OC (O) -R ⁵ .
Where o is an integer from 1 to 50
R ^Sid , R ^Sie , R ^Sif are H, C _1-60 alkyl, C _2-60 alkenyl, C _2-60 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, _{OC 1-60} alkyl, _{OC 2-60} alkenyl, _{OC 2-60} alkynyl, _{OC 5-8} cycloalkyl, _{OC 6-14} aryl, O-5-14 member heteroaryl, -[O-SiR ^Sig R ^Sih ] selected independently from the group consisting of _p- R ^Sii , NR ⁵⁰ R ⁶⁰ , halogen and ^OC (O) -R ⁵⁰ ;
Where p is an integer from 1 to 50
R ^Sig , R ^Sich , R ^Sii are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, _{OC 1-30} alkyl, _{OC 2-30} alkenyl, _{OC 2-30} alkynyl, _{OC 5-6} cycloalkyl, _{OC 6-10} aryl, O-5-10-membered heteroaryl, Selected independently from the group consisting of O-Si (CH ₃ ) ₃ , NR ⁵⁰⁰ R ⁶⁰⁰ , halogen and OC (O) -R ⁵⁰⁰ .
R ⁵ , R ⁶ , R ⁵⁰ , R ⁶⁰ , R ⁵⁰⁰ and R ⁶⁰⁰ are H, C _1-60 alkyl, C _2-60 alkenyl, C _2-60 alkynyl, C _5-8 cycloalkyl, C _6-14. Independently selected from the group consisting of aryl and 5-14 member heteroaryl,
C _1-60 alkyl, C _2-60 alkynyl and C _2-60 alkynyl are C _5-6 cycloalkyl, C _6-10 aryl, OR ^c , OC (O) -R ^c , C (O) -OR ^c. , C (O) -R ^c , NR ^c R ^d , NR ^c- C (O) R ^d , C (O) -NR ^c R ^d , N [C (O) R ^c ] [C (O) R ^d ], SR ^c , Si (R ^Sij ) (R ^Sik ) (R ^Sil ), ^-O -Si (R ^Sij ) (R ^Sik ) (R ^Sil ), halogen, CN, and NO _2. Can be substituted with 1 to 20 substituents; and at least two CH ₂ groups of C _1-60 alkyl, C _2-60 alkenyl and C _2-60 alkynyl (but not adjacent CH ₂ groups) Can be replaced by O or S,
C _5-8 cycloalkyl is C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, OR ^c , OC (O) -R ^c , C (O) -OR ^c , C (O) -R ^c , NR ^c R ^d , NR ^c- C (O) R ^d , C (O) -NR ^c R ^d , N [C (O) R ^c ] [C (O) R ^d ], SR ^c , Si (R ^Sij ) (R ^Sik ) (R ^Sil ), ^-O -Si (R ^Sij ) (R ^Sik ) (R ^Sil ), halogen, CN, and NO ₂ Can be substituted with 1-5 substituents selected from the group consisting of; and one or two CH ₂ groups of C _5-8 cycloalkyl (but not adjacent CH ₂ groups) are O , S, OC (O), CO, NR ^c or NR ^c- CO.
C _6-14 aryl and 5-14 member heteroaryl are C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, OR ^c , OC ( O) -R ^c , C (O) -OR ^c , C (O) -R ^c , NR ^c R ^d , NR ^c- C (O) R ^d , C (O) -NR ^c R ^d , N [C (O) R ^c ] [C (O) R ^d ], SR ^c , Si (R ^Sij ) (R ^Sik ) (R ^Sil ), ^-O -Si (R ^Sij ) (R ^Sik ) (R ^Sil ), halogen Can be substituted with 1-5 substituents independently selected from the group consisting of, CN, and NO ₂ ;
Here, R ^c and R ^d are independently selected from the group consisting of H, C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl.
R ^Sij , R ^Sik and R ^Sil are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, _{OC 1-30} alkyl, _{OC 2-30} alkenyl, _{OC 2-30} alkynyl, _{OC 5-6} cycloalkyl, _{OC 6-10} aryl, O-5-10-membered heteroaryl, -[O-SiR ^Sim R ^Sin ] selected independently from the group consisting of _q- R ^Sio , NR ⁷ R ⁸ , halogen, and ^OC (O) -R ⁷ .
Where q is an integer from 1 to 50,
R ^Sim , R ^Sin , R ^Sio are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, _{OC 1-30} alkyl, _{OC 2-30} alkenyl, _{OC 2-30} alkynyl, _{OC 5-6} cycloalkyl, _{OC 6-10} aryl, O-5-10-membered heteroaryl, -[O-SiR ^Ship R ^Siq ] _r- R ^Sir , NR ⁷⁰ R ⁸⁰ , halogen, and selected independently from the group consisting of OC (O) -R ⁷⁰ ;
Where r is an integer from 1 to 50
R ^Sip , R ^Siq , R ^Sir are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, _{OC 1-30} alkyl, _{OC 2-30} alkenyl, _{OC 2-30} alkynyl, _{OC 5-6} cycloalkyl, _{OC 6-10} aryl, O-5-10-membered heteroaryl, Selected independently from the group consisting of O-Si (CH ₃ ) ₃ , NR ⁷⁰⁰ R ⁸⁰⁰ , halogen and OC (O) -R ⁷⁰⁰ ;
R ⁷ , R ⁸ , R ⁷⁰ , R ⁸⁰ , R ⁷⁰⁰ and R ⁸⁰⁰ are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10. Independently selected from the group consisting of aryl and 5-10 member heteroaryl,
C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl can be substituted with 1-10 substituents selected from the group consisting of halogen, CN and NO ₂ .
R ² is C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-12 cycloalkyl, C _6-18 aryl, 5-20 member heteroaryl, OR ²¹ , OC (in each case). O) -R ²¹ , C (O) -OR ²¹ , C (O) -R ²¹ , NR ²¹ R ²² , NR ^21- C (O) R ²² , C (O) -NR ²¹ R ²² , N [C Selected from the group consisting of (O) R ²¹ ] [C (O) R ²² ], SR ²¹ , halogen, CN, SiR ^Sis R ^Sit R ^Siu and OH.
R ²¹ and R ²² consist of the group consisting of H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-12 cycloalkyl, C _6-18 aryl and 5-20 member heteroaryl. Selected independently,
C _1-30 alkyl, C _2-30 alkynyl and C _2-30 alkynyl are C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ^e , OC (O) -R ^e , C (O) -OR ^e , C (O) -R ^e , NR ^e R ^f , NR ^e- C (O) R ^f , C (O) -NR ^e R ^f , N [C (O) R ^e ] It can be substituted with 1 to 10 substituents independently selected from the group consisting of [C (O) R ^f ], SR ^e , halogen, CN, SiR ^Sis R ^Sit R ^Siu and NO ₂ ; At least two CH ₂ groups (but not adjacent CH ₂ groups) of C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl can be replaced by O or S.
C _5-12 cycloalkyls are C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ^e , OC. (O) -R ^e , C (O) -OR ^e , C (O) -R ^e , NR ^e R ^f , NR ^e- C (O) R ^f , C (O) -NR ^e R ^f , N [ With 1 to 6 substituents independently selected from the group consisting of C (O) R ^e ] [C (O) R ^f ], SR ^e , halogen, CN, SiR ^Sis R ^Sit R ^Siu and NO _2. Can be substituted; and one or two CH ₂ groups of C _5-12 cycloalkyl (but not adjacent CH ₂ groups) are O, S, OC (O), CO, NR ^e or NR ^e Can be replaced by −CO
C _6-18 aryl and 5-20 membered heteroaryl are C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 membered hetero. Aryl, OR ^e , OC (O) -R ^e , C (O) -OR ^e , C (O) -R ^e , NR ^e R ^f , NR ^e- C (O) R ^f , C (O) -NR 1 to be independently selected from the group consisting of ^e R ^f , N [C (O) R ^e ] [C (O) R ^f ], SR ^e , halogen, CN, SiR ^Sis R ^Sit R ^Siu and NO ₂ . Can be substituted with 6 substituents,
R ^Sis , R ^Sit and R ^Siu are independent of each other, H, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-6 cycloalkyl, phenyl and O-Si (CH ₃ ). Selected from a group of ₃
Here, ^Re and R ^f are a group consisting of H, C _{1 to 20} alkyl, C _{2 to 20} alkenyl, C _{2 to 20} alkynyl, C _{5 to 8} cycloalkyl, C _{6 to 14} aryl and 5 to 14 member heteroaryl. Selected independently of
C _1-20 alkyl, C _2-20 alkenyl and C _2-20 alkynyl are C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^g , OC (O) -R ^g , C (O) -OR ^g , C (O) -R ^g , NR ^g R ^h , NR ^g- C (O) R ^h , C (O) -NR ^g R ^h , N [C (O) R ^g ] Can be substituted with 1-5 substituents selected from the group consisting of [C (O) R ^h ], SR ^g , halogen, CN and NO ₂ ;
C _5-8 cycloalkyl is C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^g , OC (O) -R ^g , C (O) -OR ^g , C (O) -R ^g , NR ^g R ^h , NR ^g- C (O) R ^h , C (O) -NR ^g R ^h , N [ It can be substituted with 1-5 substituents selected from the group consisting of C (O) R ^g ] [C (O) R ^h ], SR ^g , halogen, CN, and NO ₂ ;
C _6-14 aryl and 5-14 member heteroaryls are C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member hetero. Aryl, OR ^g , OC (O) -R ^g , C (O) -OR ^g , C (O) -R ^g , NR ^g R ^h , NR ^g- C (O) R ^h , C (O) -NR ^With 1 to 5 substituents independently selected from the group consisting of ^g R ^h , N [C (O) R ^g ] [C (O) R ^h ], SR ^g , halogen, CN, and NO _2. Can be replaced;
Here, R ^g and R ^h are independently selected from the group consisting of H, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl.
Here, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl can be substituted with 1-5 substituents selected from the group consisting of halogen, CN and NO ₂ .
R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ independently in each case H, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6- Selected from the group consisting of ₁₄ aryl and 5-14 member heteroaryl.
Here, C _1-20 alkyl, C _2-20 alkenyl and C _2-20 alkynyl are C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^s , OC (O) -R. ^t , C (O) -OR ^s , C (O) -R ^s , NR ^s R ^t , NR ^s- C (O) R ^t , C (O) -NR ^s R ^t , N [C (O) R ^s ] [C (O) R ^t ], SR ^s , halogen, CN and NO ₂ can be substituted with 1 to 5 substituents selected from the group;
C _5-8 cycloalkyl is C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^s , OC (O) -R ^t , C (O) -OR ^s , C (O) -R ^s , NR ^s R ^t , NR ^s- C (O) R ^t , C (O) -NR ^s R ^t , N [ It can be substituted with 1 to 5 substituents selected from the group consisting of C (O) R ^s ] [C (O) R ^t ], SR ^s , halogen, CN, and NO ₂ ;
C _6-14 aryl and 5-14 member heteroaryls are C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member hetero. Aryl, OR ^s , OC (O) -R ^t , C (O) -OR ^s , C (O) -R ^s , NR ^s R ^t , NR ^s- C (O) R ^t , C (O) -NR ^With 1 to 5 substituents independently selected from the group consisting of ^s R ^t , N [C (O) R ^s ] [C (O) R ^t ], SR ^s , halogen, CN, and NO _2. Can be replaced;
The 5-12-membered ring system is C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^s , OC. (O) -R ^t , C (O) -OR ^s , C (O) -R ^s , NR ^s R ^t , NR ^s- C (O) R ^t , C (O) -NR ^s R ^t , N [ It can be substituted with 1 to 5 substituents selected from the group consisting of C (O) R ^s ] [C (O) R ^t ], SR ^s , halogen, CN, and NO ₂ ;
Here, R ^s and R ^t are independently selected from the group consisting of H, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl.
Here, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl can be substituted with 1-5 substituents selected from the group consisting of halogen, CN and NO ₂ .

Polyimines, also known as polyazomethines or Schiff base polymers, are a family of conjugate polymers composed of imine bonds (C = N) in the backbone and are used for several photoelectron applications and in the synthesis of shared organic backbones. It has been. Conjugated aromatic imine bonds are environmentally stable but reversible under acid catalysis. According to the present invention, the advantage of imine bonding is to design a degradable conjugate polymer for separating large diameter semiconducting SWNTs without polymer contamination and with significantly reduced polymer costs. Larger s-SWCNTs are more desirable for electronic devices because of their smaller Schottky barriers and higher current densities than smaller caliber s-SWCNTs. Both imine polymers showed high selectivity (> 99%) for large diameter s-SWNTs. After separation, the wrapping polymer can be broken down into small molecules with a catalytic amount of acid and then recycled, demonstrating a novel low cost approach for separating high purity "clean" s-SWNTs.

Thus, the polymers of the invention can be made from diamines containing r units M ¹ and dialdehydes containing s units M ² , or diamines containing r units M ² and s units M. It can be made from a diamine containing ² .

M ¹ is preferably
Selected from the group of
M ¹ is more preferably
Selected from the group of
M ¹ is even more preferably
Selected from the group of
M ¹ is most preferably
Selected from the group of
M ² is
Selected from the group of
M ² is preferably
Selected from the group of
M ² is more preferred
Selected from the group of
M ² is most preferably
Is.

An example of C _{6-14 Allilen}
Is.

An example of a 5-14 member heteroarylen
Is.

Halogen can be F, Cl, Br and I.

C _1-4 alkyl, C _1-10 alkyl, C _1-20 alkyl, C _1-30 alkyl, C _1-36 alkyl, C _1-50 alkyl, C _1-60 alkyl and C _1-100 alkyl are branched It can be chained or unbranched. Examples of C _1-4 alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tertbutyl. Examples of C _1-10 alkyl are C _1-4 alkyl, n-pentyl, neopentyl, isopentyl, n- (1-ethyl) propyl, n-hexyl, n-heptyl, n-octyl, n- (2-ethyl). ) Hexyl, n-nonyl, and n-decyl. Examples of C _1-20 alkyl are C _1-10 alkyl and n-undecyl, n-dodecyl, n-tridecylic, n-tetradecyl, n-pentadecylic, n-hexadecyl, n-heptadecyl, n-octadecylic, n-nonadecylic. And n-icosyl (C ₂₀ ). Examples of C _1-30 alkyl, C _1-36 alkyl, C _1-50 alkyl, C _1-60 alkyl and C _1-100 alkyl are C _1-20 alkyl, and n-docosyl (C ₂₂ ), n- Tetracosyl (C ₂₄ ), n-hexacosyl (C ₂₆ ), n-octacosyl (C ₂₈ ) and n-triacontyl (C ₃₀ ).

C _2-10 alkenyl, C _2-20 alkenyl, C _2-30 alkenyl, C _2-60 alkenyl and C _2-100 alkenyl can be branched or non-branched. Examples of _C2-10 alkenyl are vinyl, propenyl, cis-2-butenyl, trans-2-butenyl, 3-butenyl, cis-2-pentenyl, trans-2-pentenyl, cis-3-pentenyl, trans-3. -Pentenyl, 4-pentenyl, 2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl and dosenyl. Examples of C _2-20 alkenyl are C _2-10 alkenyl, and linoleyl (C ₁₈ ), linolenyl (C ₁₈ ), oleyl (C ₁₈ ), and arachidonyl (C ₂₀ ). Examples of C _{2 to 30 alkenyl, C 2 to 60} alkenyl and _{C 2 to 100} alkenyl _{is C 2 to 20} alkenyl and erucyl _{(C 22).}

C _2-10 alkynyl, C _2-20 alkynyl, C _2-30 alkynyl, C _2-60 alkynyl and C _2-100 alkynyl can be branched or non-branched. Examples of C _{2 to 10} alkynyl are ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and decynyl. Examples of C _2-20 alkynyl, C _2-30 alkenyl, C _2-60 alkynyl and C _2-100 alkynyl are C _2-10 alkynyl and undecynyl, dodecinyl, undecynyl, dodecinyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl. , Octadesinyl, nonadecinyl and icocinyl (C ₂₀ ).

Examples of C _5-6 cycloalkyl are cyclopentyl and cyclohexyl. Examples of C _5-8 cycloalkyl are C _5-6 cycloalkyl and cycloheptyl and cyclooctyl. C _5-12 cycloalkyl are C _5-8 cycloalkyl and cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl.

Examples of C _6-10 aryl are phenyl,
Is.

Examples of C _6-14 aryl are C _6-10 aryl and
Is.

Examples of C _6-18 aryl are C _6-14 aryl and
Is.

A 5- to 10-membered heteroaryl is a 5- to 10-membered monocyclic or polycyclic, eg, bicyclic, tricyclic or tetracyclic ring system, wherein the ring system is at least one heteroaromatic ring. It may also contain a non-aromatic ring and may be substituted with = O.

A 5- to 14-membered heteroaryl is a 5- to 14-membered monocyclic or polycyclic, eg, bicyclic, tricyclic or tetracyclic ring system, wherein the ring system is at least one heteroaromatic ring. It may also contain a non-aromatic ring and may be substituted with = O.

A 5- to 20-membered heteroaryl is a 5- to 20-membered monocyclic or polycyclic, eg, bicyclic, tricyclic or tetracyclic ring system, wherein the ring system is at least one heteroaromatic ring. It may also contain a non-aromatic ring and may be substituted with = O.

An example of a 5-10 member heteroaryl
Is;
Examples of 5-14 member heteroaryls are the examples shown for 5-10 membered heteroaryls and
Is;
Examples of 5-20 membered heteroaryls are the examples shown for 5-14 membered heteroaryls and
Is;
Here, R ¹⁰⁰ and R ¹⁰¹ independently represent H, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, and in each case. Selected from the group consisting of 5-14-membered heteroaryls, or R ¹⁰⁰ and R ¹⁰¹ , when attached to the same atom, form a 5- to 12-membered ring system with the atoms to which they are attached. ,
Here, C _{1 to 20} alkyl, C _{2 to 20} alkenyl and C _{2 to 20} alkynyl are C _{5 to 6} cycloalkyl, C _{6 to 10} aryl, 5 to 10 member heteroaryl, OR ^q , OC (O) -R. ^q , C (O) -OR ^q , C (O) -R ^q , NR ^q R ^r , NR ^q- C (O) R ^r , C (O) -NR ^q R ^r , N [C (O) R ^q ] [C (O) R ^r ], SR ^q , halogen, CN, and NO ₂ can be substituted with 1 to 5 substituents selected from the group;
C _5-8 cycloalkyl is C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^q , OC (O) -R ^q , C (O) -OR ^q , C (O) -R ^q , NR ^q R ^r , NR ^q- C (O) R ^r , C (O) -NR ^q R ^r , N [ It can be substituted with 1-5 substituents selected from the group consisting of C (O) R ^q ] [C (O) R ^r ], SR ^q , halogen, CN, and NO ₂ ;
C _6-14 aryl and 5-14 member heteroaryl are C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member hetero. Aryl, OR ^q , OC (O) -R ^q , C (O) -OR ^q , C (O) -R ^q , NR ^q R ^r , NR ^q- C (O) R ^r , C (O) -NR ^With 1 to 5 substituents independently selected from the group consisting of ^q R ^r , N [C (O) R ^q ] [C (O) R ^r ], SR ^q , halogen, CN, and NO _2. Can be replaced;
The 5-12 member ring system is C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^q , OC (O) -R ^q , C (O) -OR ^q , C (O) -R ^q , NR ^q R ^r , NR ^q- C (O) R ^r , C (O) -NR ^q R ^r , N It can be substituted with 1 to 5 substituents selected from the group consisting of [C (O) R ^q ] [C (O) R ^r ], SR ^q , halogen, CN, and NO ₂ ;
Here, R ^q and R ^r are independently selected from the group consisting of H, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl.
Here, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl can be substituted with 1-5 substituents selected from the group consisting of halogen, CN and NO ₂ .

Preferably, b and c are 1, 2, 3 or 4 independent of each other. More preferably, b and c are 1, 2 or 3 independent of each other.

Preferably, a and d are 0, 1, 2 or 3 independently of each other. More preferably, a and d are 0, 1 or 2 independently of each other. Even more preferably, a and d are 0 or 1 independently of each other. Most preferably, a and d are 0.

Preferably n is 0, 1 or 2 and m is 0, 1 or 2. More preferably, n is 0 or 1 and m is 0, 1 or 2. Most preferably, n is 0 and m is 0, 1 or 2.

Preferably, R ¹ is H, C _1-100 alkyl, C _2-100 alkenyl, C _2-100 alkynyl, C _5-12 cycloalkyl, C _6-18 aryl, and 5-20 member heteroaryl in each case. Selected from the group consisting of
Here, C _1-100 alkyl, C _2-100 alkenyl and C _2-100 alkynyl are C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ^a , OC (O) -R. ^a , C (O) -OR ^a , C (O) -R ^a , NR ^a- C (O) R ^b , C (O) -NR ^a R ^b , SR ^a , Si (R ^Sia ) (R ^Sib ) ^{(R Sic), - O-} Si (R Sia) (R Sib) (R Sic), can be substituted by 1 to 40 substituents selected independently from the group consisting of halogen and CN; and At least two CH ₂ groups (but not adjacent CH ₂ groups) of C _1-100 alkyl, C _2-100 alkenyl and C _2-100 alkynyl can be replaced by O or S.
C _5-12 cycloalkyls are C _1-60 alkyl, C _2-60 alkenyl, C _2-60 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ^a , OC. (O) -R ^a , C (O) -OR ^a , C (O) -R ^a , NR ^a- C (O) R ^b , C (O) -NR ^a R ^b , SR ^a , Si (R ^Sia) ) (R ^Sib ) (R ^Sic ), ^-O -Si (R ^Sia ) (R ^Sib ) (R ^Sic ), halogen, and CN substituted with 1 to 6 substituents independently selected from the group. And one or two CH ₂ groups of C _5-12 cycloalkyl (but not _two adjacent CH groups) are O, S, OC (O), CO, NR ^a or NR ^a − Can be replaced by CO,
C _6-18 aryl and 5-20 membered heteroaryl are C _1-60 -alkyl, C _2-60 alkenyl, C _2-60 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member. Heteroaryl, OR ^a , OC (O) -R ^a , C (O) -OR ^a , C (O) -R ^a , NR ^a- C (O) R ^b , C (O) -NR ^a R ^b , 1-independently selected from the group consisting of SR ^a , Si (R ^Sia ) (R ^Sib ) (R ^Sic ), ^-O -Si (R ^Sia ) (R ^Sib ) (R ^Sic ), halogen, and CN Can be substituted with 6 substituents,
Here, ^Ra and R ^b consist of H, C _1-60 alkyl, C _2-60 alkenyl, C _2-60 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl and 5-14 member heteroaryl. Selected independently of the group,
R ^Sia , R ^Sib and R ^Sic are H, C _1-60 alkyl, C _2-60 alkenyl, C _2-60 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, From the group consisting of ^OC _1-60 alkyl, _{OC 2-60} alkenyl, _{OC 2-60} alkynyl, _{OC 5-8} cycloalkyl,-[O-SiR ^Side R ^Sie ] _o- R ^Sif Selected independently,
Where o is an integer from 1 to 50
R ^Sid , R ^Sie and R ^Sif are H, C _1-60 alkyl, C _2-60 alkenyl, C _2-60 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl,-[O-SiR ^Sig R. ^Sih ] Selected independently from the group consisting of _p- R ^Sii ,
Where p is an integer from 1 to 50
R ^Sig , R ^Sih and R ^Sii are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, O-Si (CH ₃ ). Selected independently from the group of ₃
R ⁵ , R ⁶ , R ⁵⁰ , R ⁶⁰ , R ⁵⁰⁰ and R ⁶⁰⁰ are H, C _1-60 alkyl, C _2-60 alkenyl, C _2-60 alkynyl, C _5-8 cycloalkyl, C _6-14. Independently selected from the group consisting of aryl and 5-14 member heteroaryl,
C _1-60 alkyl, C _2-60 alkynyl and C _2-60 alkynyl are C _5-6 cycloalkyl, C _6-10 aryl, OR ^c , OC (O) -R ^c , C (O) -OR ^c. , C (O) -R ^c , NR ^c- C (O) R ^d , C (O) -NR ^c R ^d , SR ^c , Si (R ^Sij ) (R ^Sik ) (R ^Sil ), ^-O -Si Can be substituted with 1 to 20 substituents selected from the group consisting of (R ^Sij ) (R ^Sik ) (R ^Sil ), halogen, and CN; and C _1-60 alkyl, C _2-60 alkenyl. And at least two CH ₂ groups (but not adjacent CH ₂ groups) of C _2-60 alkynyl can be replaced by O or S.
C _5-8 cycloalkyl is C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, OR ^c , OC (O) -R ^c , C (O) -OR ^c , C (O) -R ^c , NR ^c- C (O) R ^d , C (O) -NR ^c R ^d , SR ^c , Si (R ^Sij ) (R ^Sik ) (R) ^{Sil), - O-Si (} R Sij) (R Sik) (R Sil), halogen, and is selected from the group consisting of CN can be substituted with 1-5 substituents; and _{C 5 to 8} One or two CH ₂ groups of cycloalkyl (but not adjacent CH ₂ groups) can be replaced by O, S, OC (O), CO, NR ^c or NR ^c- CO.
C _6-14 aryl and 5-14 member heteroaryl are C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, OR ^c , OC ( O) -R ^c , C (O) -OR ^c , C (O) -R ^c , NR ^c- C (O) R ^d , C (O) -NR ^c R ^d , SR ^c , Si (R ^Sij ) ^{(R Sik) (R Sil)} , - O-Si (R Sij) (R Sik) (R Sil), be substituted with 1 to 5 substituents selected independently from the group consisting of halogen and CN Can be;
Here, R ^c and R ^d are independently selected from the group consisting of H, C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl.
R ^Sij , R ^Sik and R ^Sil are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl,-[O-SiR ^Sim R ^Sin ] Selected independently from the group consisting of _q- R ^Sio ,
Where q is an integer from 1 to 50,
R ^Sim , R ^Sin , R ^Sio are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, _{OC 1-30} alkyl, _{OC 2-30} alkenyl, _{OC 2-30} alkynyl, _{OC 5-6} cycloalkyl, _{OC 6-10} aryl, O-5-10-membered heteroaryl, -[O-SiR ^Ship R ^Siq ] _r- R ^Sir , NR ⁷⁰ R ⁸⁰ , halogen, and selected independently from the group consisting of OC (O) -R ⁷⁰ ;
Where r is an integer from 1 to 50
R ^Sip , R ^Siq , R ^Sir are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, _{OC 1-30} alkyl, _{OC 2-30} alkenyl, _{OC 2-30} alkynyl, _{OC 5-6} cycloalkyl, _{OC 6-10} aryl, O-5-10-membered heteroaryl, Selected independently from the group consisting of O-Si (CH ₃ ) ₃ , NR ⁷⁰⁰ R ⁸⁰⁰ , halogen and OC (O) -R ⁷⁰⁰ ;
R ⁷ , R ⁸ , R ⁷⁰ , R ⁸⁰ , R ⁷⁰⁰ and R ⁸⁰⁰ are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10. Independently selected from the group consisting of aryl and 5-10 member heteroaryl,
C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl can be substituted with 1-10 substituents selected from the group consisting of halogens and CNs.

More preferably, R ¹ is selected from the group consisting of C _1-100 alkyl, C _2-100 alkenyl and C _2-100 alkynyl in each case.
Here, C _1-100 alkyl, C _2-100 alkenyl and C _2-100 alkynyl are C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ^a , OC (O) -R. ^a , C (O) -OR ^a , C (O) -R ^a , NR ^a- C (O) R ^b , C (O) -NR ^a R ^b , SR ^a , Si (R ^Sia ) (R ^Sib ) ^{(R Sic), - O-} Si (R Sia) (R Sib) (R Sic), can be substituted by 1 to 40 substituents selected independently from the group consisting of halogen and CN; and At least two CH ₂ groups (but not adjacent CH ₂ groups) of C _1-100 alkyl, C _2-100 alkenyl and C _2-100 alkynyl can be replaced by O or S.
Here, ^Ra and R ^b consist of H, C _1-60 alkyl, C _2-60 alkenyl, C _2-60 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl and 5-14 member heteroaryl. Selected independently of the group,
R ^Sia , R ^Sib and R ^Sic are H, C _1-60 alkyl, C _2-60 alkenyl, C _2-60 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl,-[O-SiR ^Sid R ^Sie ] Selected independently from the group consisting of _o- R ^Sif ,
Where o is an integer from 1 to 50
R ^Sid , R ^Sie and R ^Sif are H, C _1-60 alkyl, C _2-60 alkenyl, C _2-60 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl,-[O-SiR ^Sig R. ^Sih ] Selected independently from the group consisting of _p- R ^Sii ,
Where p is an integer from 1 to 50
R ^Sig , R ^Sich , R ^Sii are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, O-Si (CH ₃ ). Selected independently from the group of ₃
R ⁵ , R ⁶ , R ⁵⁰ , R ⁶⁰ , R ⁵⁰⁰ and R ⁶⁰⁰ are H, C _1-60 alkyl, C _2-60 alkenyl, C _2-60 alkynyl, C _5-8 cycloalkyl, C _6-14. Independently selected from the group consisting of aryl and 5-14 member heteroaryl,
C _1-60 alkyl, C _2-60 alkynyl and C _2-60 alkynyl are C _5-6 cycloalkyl, C _6-10 aryl, OR ^c , OC (O) -R ^c , C (O) -OR ^c. , C (O) -R ^c , NR ^c- C (O) R ^d , C (O) -NR ^c R ^d , SR ^c , Si (R ^Sij ) (R ^Sik ) (R ^Sil ), ^-O -Si Can be substituted with 1 to 20 substituents selected from the group consisting of (R ^Sij ) (R ^Sik ) (R ^Sil ), halogen, and CN; and C _1-60 alkyl, C _2-60 alkenyl. And at least two CH ₂ groups (but not adjacent CH ₂ groups) of C _2-60 alkynyl can be replaced by O or S.
C _5-8 cycloalkyl is C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, OR ^c , OC (O) -R ^c , C (O) -OR ^c , C (O) -R ^c , NR ^c- C (O) R ^d , C (O) -NR ^c R ^d , SR ^c , Si (R ^Sij ) (R ^Sik ) (R) ^{Sil), - O-Si (} R Sij) (R Sik) (R Sil), can be substituted with 1-5 substituents selected from the group consisting of halogen and CN; and _{C 5 to 8} cycloalkyl One or two CH ₂ groups of alkyl (but not _two adjacent CH groups) can be replaced by O, S, OC (O), CO, NR ^c or NR ^c- CO.
C _6-14 aryl and 5-14 member heteroaryl are C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, OR ^c , OC ( O) -R ^c , C (O) -OR ^c , C (O) -R ^c , NR ^c- C (O) R ^d , C (O) -NR ^c R ^d , SR ^c , Si (R ^Sij ) ^{(R Sik) (R Sil)} , - O-Si (R Sij) (R Sik) (R Sil), be substituted with 1 to 5 substituents selected independently from the group consisting of halogen and CN Can be;
Here, R ^c and R ^d are independently selected from the group consisting of H, C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl.
R ^Sij , R ^Sik and R ^Sil are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl,-[O-SiR ^Sim R ^Sin ] Selected independently from the group consisting of _q- R ^Sio ,
Where q is an integer from 1 to 50,
R ^Sim , R ^Sin , R ^Sio are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl,-[O-SiR ^Ship R ^Siq ] Selected independently from the group consisting of _r- R ^Sir ,
Where r is an integer from 1 to 50
R ^Sip , R ^Siq , R ^Sir are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, O-Si (CH ₃ ). Selected independently from the group of ₃
R ⁷ , R ⁸ , R ⁷⁰ , R ⁸⁰ , R ⁷⁰⁰ and R ⁸⁰⁰ are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10. Independently selected from the group consisting of aryl and 5-10 member heteroaryl,
C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl can be substituted with 1-10 substituents selected from the group consisting of halogens and CNs.

Even more preferably, R ¹ is selected from the group consisting of C _1-50 alkyl, C _2-50 alkenyl and C _2-50 alkynyl in each case.
Here, C _{1 to 50} alkyl, C _{2 to 50} alkenyl and C _{2 to 50} alkynyl are C _{5 to 6} cycloalkyl, C _{6 to 10} aryl, 5 to 10 member heteroaryl, OR ^a , SR ^a , Si (R). ^With 1 to 20 substituents independently selected from the group consisting of ^Sia ) (R ^Sib ) (R ^Sic ), ^-O -Si (R ^Sia ) (R ^Sib ) (R ^Sic ), halogen, and CN. Can be substituted; and at least two CH ₂ groups (but not adjacent CH ₂ groups) of C _1-50 alkyl, C _2-50 alkenyl and C _2-50 alkynyl can be replaced by O or S. Can,
Here, ^Ra and R ^b are independently selected from the group consisting of H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl and C _6-10 aryl. ,
R ^Sia , R ^Sib and R ^Sic are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl,-[O-SiR ^Sid R ^Sie ] Selected independently from the group consisting of _o- R ^Sif ,
Where o is an integer from 1 to 50
R ^Sid , R ^Sie , R ^Sif are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl,-[O-SiR ^Sig R ^Sih ] Selected independently from the group consisting of _p- R ^Sii ,
Where p is an integer from 1 to 50
R ^Sig , R ^Sich , R ^Sii are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, O-Si (CH ₃ ). Selected independently from the group of ₃
R ⁵ , R ⁶ , R ⁵⁰ , R ⁶⁰ , R ⁵⁰⁰ and R ⁶⁰⁰ are H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-6 cycloalkyl, C _6-10. Independently selected from the group consisting of aryl and 5-10 member heteroaryl,
C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl can be substituted with 1-10 substituents selected from the group consisting of halogens and CNs.

Most preferably, R ¹ is selected from the group consisting of C _1-36 alkyl, C _2-36 alkenyl and C _2-36 alkynyl in each case.
Here, C _1-36 alkyl, C _2-36 alkenyl and C _2-36 alkynyl are C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^a , SR ^a , Si (R). ^With 1 to 20 substituents independently selected from the group consisting of ^Sia ) (R ^Sib ) (R ^Sic ), ^-O -Si (R ^Sia ) (R ^Sib ) (R ^Sic ), halogen, and CN. Can be substituted; and at least two CH ₂ groups (but not adjacent CH ₂ groups) of C _1-36 alkyl, C _2-36 alkenyl and C _2-36 alkynyl can be replaced by O or S. Can,
Here, ^Ra and R ^b are independently selected from the group consisting of H, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-6 cycloalkyl and C _6-10 aryl. ,
R ^Sia , R ^Sib and R ^Sic are H, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl,-[O-SiR ^Sid R ^Sie ] Selected independently from the group consisting of _o- R ^Sif ,
here,
o is an integer from 1 to 50
R ^Sid , R ^Sie , R ^Sif are H, C _1-30 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl,-[O-SiR ^Sig R ^Sih ] Selected independently from the group consisting of _p- R ^Sii ,
Where p is an integer from 1 to 50
R ^Sig , R ^Sich , R ^Sii are H, C _1-30 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, O-Si (CH ₃ ). Selected independently from the group of ₃
R ⁵ , R ⁶ , R ⁵⁰ , R ⁶⁰ , R ⁵⁰⁰ and R ⁶⁰⁰ are H, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-6 cycloalkyl, C _6-10. Independently selected from the group consisting of aryl and 5-10 member heteroaryl,
C _1-20 alkyl, C _2-20 alkenyl and C _2-20 alkynyl can be substituted with 1-10 substituents selected from the group consisting of halogens and CNs.

In particular, R ¹ is an unsubstituted C _1-36 alkyl in each case.

Preferably, L ¹ and L ² are independent of each other, in each case C _6-18 allele, 5 to 20 member hetero allele, and
Selected from the group consisting of
Here, the C _6-18 arylene and the 5-20 member heteroarylene are C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-12 cycloalkyl, C _6-18 aryl and in each case. 5-20 member heteroaryl, OR ³¹ , OC (O) -R ³¹ , C (O) -OR ³¹ , C (O) -R ³¹ , NR ³¹ R ³² , NR ^31- C (O) R ³² , C It can be substituted with 1 to 6 substituents R ³ selected from the group consisting of (O) -NR ³¹ R ³² , SR ³¹ , halogen, CN, SiR ^Siv R ^Siwa R ^Six and OH.
here
In each case C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-12 cycloalkyl, C _6-18 aryl and 5-20 member heteroaryl, C (O) -R ⁴¹ , It can be replaced by a ^{C (O) -NR 41 R 42} , C (O) 1 or 2 substituents ^{R 4} is selected from the group consisting of ^{-OR 41} and CN,
Here, R ³¹ , R ³² , R ⁴¹ and R ⁴² are independent of each other and in each case H, C _{1 to 30} alkyl, C _{2 to 30} alkenyl, C _{2 to 30} alkynyl, C _{5 to 12} cycloalkyl, C. Selected from the group consisting of _6-18 aryl and 5-20 member heteroaryl
Here, C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl are C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ⁱ , OC (O) -R. ^j , C (O) -OR ⁱ , C (O) -R ⁱ , NR ⁱ R ^j , NR ^i- C (O) R ^j , C (O) -NR ⁱ R ^j , N [C (O) R ⁱ ] [C (O) R ^j ], SR ⁱ , halogen, CN, SiR ^Siv R ^Siwa R ^Six and NO ₂ can be substituted with 1 to 10 substituents independently selected from the group. And at least two CH ₂ groups (but not adjacent CH ₂ groups) of C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl can be replaced by O or S.
C _5-12 cycloalkyls are C _1-20 alkyl, C _2-20 alkenyl and C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ⁱ , OC. (O) -R ^j , C (O) -OR ⁱ , C (O) -R ⁱ , NR ⁱ R ^j , NR ^i- C (O) R ^j , C (O) -NR ⁱ R ^j , N [ With 1 to 6 substituents independently selected from the group consisting of C (O) R ⁱ ] [C (O) R ^j ], SR ⁱ , halogen, CN, SiR ^Siv R ^Siwa R ^Six and NO _2. Can be substituted; and one or two CH ₂ groups of C _5-12 cycloalkyl (but not adjacent CH ₂ groups) are O, S, OC (O), CO, NR ⁱ or NR. Can be replaced by ^i- CO
C _6-18 aryl and 5-20 membered heteroaryl are C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 membered hetero. Aryl, OR ⁱ , OC (O) -R ^j , C (O) -OR ⁱ , C (O) -R ⁱ , NR ⁱ R ^j , NR ^i- C (O) R ^j , C (O) -NR 1-independently selected from the group consisting of ⁱ R ^j , N [C (O) R ⁱ ] [C (O) R ^j ], SR ⁱ , halogen, CN, SiR ^Siv R ^Siwa R ^Six and NO ₂ . Can be substituted with 6 substituents,
Here, R ^Siv , R ^Siwa , and R ^Six are independent of each other, H, C _{1 to 20} alkyl, C _{2 to 20} alkenyl, C _{2 to 20} alkynyl, C _{5 to 6} cycloalkyl, phenyl and O-Si ( CH ₃ ) Selected from the group consisting of ₃
R ⁱ and R ^j consist of the group consisting of H, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl and 5-14 member heteroaryl. Selected independently,
Here, C _{1 to 20} alkyl, C _{2 to 20} alkenyl and C _{2 to 20} alkynyl are C _{5 to 6} cycloalkyl, C _{6 to 10} aryl, 5 to 10 member heteroaryl, OR ^k , OC (O) -R. ^l , C (O) -OR ^k , C (O) -R ^k , NR ^k R ^l , NR ^k- C (O) R ^l , C (O) -NR ^k R ^l , N [C (O) R ^k ] [C (O) R ^l ], SR ^k , halogen, CN, and NO ₂ can be substituted with 1 to 5 substituents selected from the group;
C _5-8 cycloalkyls are C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^k , OC. (O) -R ^l , C (O) -OR ^k , C (O) -R ^k , NR ^k R ^l , NR ^k- C (O) R ^l , C (O) -NR ^k R ^l , N [ It can be substituted with 1-5 substituents selected from the group consisting of C (O) R ^k ] [C (O) R ^l ], SR ^k , halogen, CN, and NO ₂ ;
C _6-14 aryl and 5-14 member heteroaryls are C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member hetero. Aryl, OR ^k , OC (O) -R ^l , C (O) -OR ^k , C (O) -R ^k , NR ^k R ^l , NR ^k- C (O) R ^l , C (O) -NR ^With 1 to 5 substituents independently selected from the group consisting of ^k R ^l , N [C (O) R ^k ] [C (O) R ^l ], SR ^k , halogen, CN, and NO _2. Can be replaced;
Here, R ^k and R ^l are independently selected from the group consisting of H, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl.
Here, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl can be substituted with 1-5 substituents selected from the group consisting of halogen, CN and NO ₂ .

More preferably, L ¹ and L ² are independent of each other, in each case a 5-20 member heteroarylen, and
Selected from the group consisting of
Here, the 5 to 20-membered heteroarylenes are C _{1 to 30} alkyl, C to _{2 to 30} alkenyl, C to _{2 to 30} alkynyl, C to _{5 to 12} cycloalkyl, C _{6 to 18} aryl and 5 to 20 member heteroaryl in each case. , OR ³¹ , OC (O) -R ³¹ , C (O) -OR ³¹ , C (O) -R ³¹ , NR ³¹ R ³² , NR ^31- C (O) R ³² , C (O) -NR ³¹ It can be substituted with 1 to 6 substituents R ³ selected from the group consisting of R ³² , SR ³¹ , halogen, CN, SiR ^Siv R ^Siwa R ^Six and OH.
here
In each case C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-12 cycloalkyl, C _6-18 aryl and 5-20 member heteroaryl, C (O) -R ⁴¹ , It can be replaced by a ^{C (O) -NR 41 R 42} , C (O) 1 or 2 substituents ^{R 4} is selected from the group consisting of ^{-OR 41} and CN,
Here, R ³¹ , R ³² , R ⁴¹ and R ⁴² are independent of each other and in each case H, C _{1 to 30} alkyl, C _{2 to 30} alkenyl, C _{2 to 30} alkynyl, C _{5 to 12} cycloalkyl, C. Selected from the group consisting of _6-18 aryl and 5-20 member heteroaryl
Here, C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl are C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ⁱ , OC (O) -R. ^j , C (O) -OR ⁱ , C (O) -R ⁱ , NR ⁱ R ^j , NR ^i- C (O) R ^j , C (O) -NR ⁱ R ^j , N [C (O) R ⁱ ] [C (O) R ^j ], SR ⁱ , halogen, CN, SiR ^Siv R ^Siwa R ^Six and NO ₂ can be substituted with 1 to 10 substituents independently selected from the group. And at least two CH ₂ groups (but not adjacent CH ₂ groups) of C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl can be replaced by O or S.
C _5-12 cycloalkyls are C _1-20 alkyl, C _2-20 alkenyl and C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ⁱ , OC. (O) -R ^j , C (O) -OR ⁱ , C (O) -R ⁱ , NR ⁱ R ^j , NR ^i- C (O) R ^j , C (O) -NR ⁱ R ^j , N [ With 1 to 6 substituents independently selected from the group consisting of C (O) R ⁱ ] [C (O) R ^j ], SR ⁱ , halogen, CN, SiR ^Siv R ^Siwa R ^Six and NO _2. Can be substituted; and one or two CH ₂ groups of C _5-12 cycloalkyl (but not adjacent CH ₂ groups) are O, S, OC (O), CO, NR ⁱ or NR. Can be replaced by ^i- CO
C _6-18 aryl and 5-20 membered heteroaryl are C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 membered hetero. Aryl, OR ⁱ , OC (O) -R ^j , C (O) -OR ⁱ , C (O) -R ⁱ , NR ⁱ R ^j , NR ^i- C (O) R ^j , C (O) -NR 1-independently selected from the group consisting of ⁱ R ^j , N [C (O) R ⁱ ] [C (O) R ^j ], SR ⁱ , halogen, CN, SiR ^Siv R ^Siwa R ^Six and NO ₂ . Can be substituted with 6 substituents,
Here, R ^Siv , R ^Siwa , and R ^Six are independent of each other, H, C _{1 to 20} alkyl, C _{2 to 20} alkenyl, C _{2 to 20} alkynyl, C _{5 to 6} cycloalkyl, phenyl and O-Si ( CH ₃ ) Selected from the group consisting of ₃
R ⁱ and R ^j consist of the group consisting of H, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl and 5-14 member heteroaryl. Selected independently,
Here, C _{1 to 20} alkyl, C _{2 to 20} alkenyl and C _{2 to 20} alkynyl are C _{5 to 6} cycloalkyl, C _{6 to 10} aryl, 5 to 10 member heteroaryl, OR ^k , OC (O) -R. ^l , C (O) -OR ^k , C (O) -R ^k , NR ^k R ^l , NR ^k- C (O) R ^l , C (O) -NR ^k R ^l , N [C (O) R ^k ] [C (O) R ^l ], SR ^k , halogen, CN, and NO ₂ can be substituted with 1 to 5 substituents selected from the group;
C _5-8 cycloalkyls are C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^k , OC. (O) -R ^l , C (O) -OR ^k , C (O) -R ^k , NR ^k R ^l , NR ^k- C (O) R ^l , C (O) -NR ^k R ^l , N [ It can be substituted with 1-5 substituents selected from the group consisting of C (O) R ^k ] [C (O) R ^l ], SR ^k , halogen, CN, and NO ₂ ;
C _6-14 aryl and 5-14 member heteroaryls are C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member hetero. Aryl, OR ^k , OC (O) -R ^l , C (O) -OR ^k , C (O) -R ^k , NR ^k R ^l , NR ^k- C (O) R ^l , C (O) -NR ^With 1 to 5 substituents independently selected from the group consisting of ^k R ^l , N [C (O) R ^k ] [C (O) R ^l ], SR ^k , halogen, CN, and NO _2. Can be replaced;
Here, R ^k and R ^l are independently selected from the group consisting of H, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl.
Here, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl can be substituted with 1-5 substituents selected from the group consisting of halogen, CN and NO ₂ .

More preferably, L ¹ and L ² are independent of each other, in each case a 5-20 member heteroarylen, and
Selected from the group consisting of
Here, 5 to 20-member hetero-allylen
Selected from the group consisting of
Here, R ¹⁰⁴ and R ¹⁰⁵ are independently H, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, and in each case. Selected from the group consisting of 5-14 member heteroaryls, or R ¹⁰⁴ and R ¹⁰⁵ , when attached to the same atom, form a 5-12 member ring system with the atom to which they are attached. ,
Where C _1-20 alkyl, C _2-20 alkenyl and C _2-20 alkynyl are C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^u , OC (O) -R. ^u , C (O) -OR ^u , C (O) -R ^u , NR ^u R ^v , NR ^u- C (O) R ^v , C (O) -NR ^u R ^v , N [C (O) R ^u ] [C (O) R ^v ], SR ^u , halogen, CN, and NO ₂ can be substituted with 1 to 5 substituents selected from the group;
C _5-8 cycloalkyl is C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^u , OC (O) -R ^u , C (O) -OR ^u , C (O) -R ^u , NR ^u R ^v , NR ^u- C (O) R ^v , C (O) -NR ^u R ^v , N [ It can be substituted with 1-5 substituents selected from the group consisting of C (O) R ^u ] [C (O) R ^v ], SR ^u , halogens, CNs, and NO ₂ ;
C _6-14 aryl and 5-14 member heteroaryls are C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member hetero. Aryl, OR ^u , OC (O) -R ^u , C (O) -OR ^u , C (O) -R ^u , NR ^u R ^v , NR ^u- C (O) R ^v , C (O) -NR ^With 1 to 5 substituents independently selected from the group consisting of ^u R ^v , N [C (O) R ^u ] [C (O) R ^v ], SR ^u , halogen, CN, and NO _2. Can be replaced;
The 5-12-membered ring system is C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^u , OC. (O) -R ^u , C (O) -OR ^u , C (O) -R ^u , NR ^u R ^v , NR ^u- C (O) R ^v , C (O) -NR ^u R ^v , N [ It can be substituted with 1-5 substituents selected from the group consisting of C (O) R ^u ] [C (O) R ^v ], SR ^u , halogens, CNs, and NO ₂ ;
Wherein ^{R u} and ^{R v} are independently selected _{H, C 1 to 10 alkyl,} from the group consisting of _{C 2 to 10} alkenyl and _{C 2 to 10} alkynyl,
Here, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl can be substituted with 1-5 substituents selected from the group consisting of halogen, CN and NO ₂ .
Here 5-20 membered heteroarylene may be substituted with 1-4 substituents R ³ is selected from the group consisting of C _{1 to 30} alkyl and halogen in each case,
here
Is, _{C 1 to 30} alkyl ^can be substituted by C (O) -R 41, C (O) 1 or 2 substituents ^{R 4} is selected from the group consisting of ^{-OR 41} and CN in each case ,
Here, R ⁴¹ is C _{1 to 30} alkyl in each case.

Even more preferably, L ¹ and L ² are independent of each other, in each case a 5-20 member heteroarylen, and
Selected from the group consisting of
Here, 5 to 20 members of hetero-allylen
Selected from the group consisting of
Here, R ¹⁰⁴ and R ¹⁰⁵ are independently selected from the group consisting of H and C _1-20 alkyl in each case.
Here 5-20 membered heteroarylene may be substituted with 1-4 substituents R ³ is selected from the group consisting of C _{1 to 30} alkyl and halogen in each case,
here
Is non-replacement.

Most preferably, L ¹ and L ² are independent of each other, in each case a 5-20 member heteroarylen, and
Selected from the group consisting of
Here, 5 to 20-member hetero-allylen
And
Here the 5-20 member heteroarylen is unsubstituted and
here
Is non-replacement.

In particular, L ¹ and L ² are independent of each other and are 5 to 20 member heteroarylenes in each case, where the 5 to 20 member heteroarylenes are.
And
Here, the 5- to 20-membered heteroarylene is unsubstituted.

Preferably, L ³ and L ⁴ are independently selected from the group consisting of C _6-18 alleles and 5 to 20 member hetero _{allylenes in} each case.
Here, C _6-18 arylene and 5-20 member heteroarylene are C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-12 cycloalkyl, C _6-18 aryl and in each case. 5-20 member heteroaryl, OR ⁹¹ , OC (O) -R ⁹¹ , C (O) -OR ⁹¹ , C (O) -R ⁹¹ , NR ⁹¹ R ⁹² , NR ^91- C (O) R ⁹² , C ^{(O) -NR 91 R 92,} SR 91, ^{halogen, CN,} can be substituted by ^SiR Siy ^{R Siz R Siaa} and 1-6 substituents ^{R 9} is selected from the group consisting of OH,
Here, R ⁹¹ and R ⁹² are independent of each other, in each case H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-12 cycloalkyl, C _6-18 aryl and Selected from the group consisting of 5 to 20 member heteroaryl,
Here, C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl are C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ^m , OC (O) -R. ^m , C (O) -OR ^m , C (O) -R ^m , NR ^m R ⁿ , NR ^m- C (O) R ⁿ , C (O) -NR ⁿ R ^m , N [C (O) R ^{n] [C (O) R} m], SR n, ^{halogen, CN,} can be substituted by 1 to 10 substituents selected independently from the group consisting of ^SiR Siy ^{R Siz R Siaa} and NO ₂ And at least two CH ₂ groups (but not adjacent CH ₂ groups) of C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl can be replaced by O or S.
C _5-12 cycloalkyls are C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ^m , OC. (O) -R ^m , C (O) -OR ^m , C (O) -R ^m , NR ^m R ⁿ , NR ^m- C (O) R ⁿ , C (O) -NR ^m R ⁿ , N [ ^{C (O) R m] [} C (O) R n], SR m, ^{halogen, CN,} 1 to 6 substituents independently selected from the group consisting of ^SiR Siy ^{R Siz R Siaa} and NO ₂ Can be substituted; and one or two CH ₂ groups of C _5-12 cycloalkyl (but not adjacent CH ₂ groups) are O, S, OC (O), CO, NR ^m or NR. Can be replaced by ^m- CO,
C _6-18 aryl and 5-20 membered heteroaryl are C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 membered hetero. Aryl, OR ^m , OC (O) -R ^m , C (O) -OR ^m , C (O) -R ^m , NR ^m R ⁿ , NR ^m- C (O) R ⁿ , C (O) -NR ^{m R n 1~, n [C} (O) R m] where ^{[C (O) R n]} , SR m, ^{halogen, CN,} are independently selected from the group consisting of ^SiR Siy ^{R Siz R Siaa} and NO ₂ Can be substituted with 6 substituents,
^{R Siy,} R Siz, R ^Siaa independently of one _{another, H, C 1 to 20 alkyl, C 2 to 20 alkenyl, C 2 to 20 alkynyl, C 5 to 6} cycloalkyl, phenyl and O-Si (CH ₃ ) Selected from the group consisting of ₃
Here, R ^m and R ⁿ consist of H, C _{1 to 20} alkyl, C _{2 to 20} alkenyl, C _{2 to 20} alkynyl, C _{5 to 8} cycloalkyl, C _{6 to 14} aryl and 5 to 14 member heteroaryl. Selected independently of the group,
C _1-20 alkyl, C _2-20 alkenyl and C _2-20 alkynyl are C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^o , OC (O) -R ^o , C (O) -OR ^o , C (O) -R ^o , NR ^o R ^p , NR ^o- C (O) R ^p , C (O) -NR ^o R ^p , N [C (O) R ^o ] It can be substituted with 1-5 substituents selected from the group consisting of [C (O) R ^p ], SR ^o , halogen, CN, and NO ₂ ;
C _5-8 cycloalkyl is C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^o , OC (O) -R ^o , C (O) -OR ^o , C (O) -R ^o , NR ^o R ^p , NR ^o- C (O) R ^p , C (O) -NR ^o R ^p , N [ It can be substituted with 1 to 5 substituents selected from the group consisting of C (O) R ^o ] [C (O) R ^p ], SR ^o , halogen, CN, and NO ₂ ;
C _6-14 aryl and 5-14 member heteroaryls are C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member hetero. Aryl, OR ^o , OC (O) -R ^o , C (O) -OR ^o , C (O) -R ^o , NR ^o R ^p , NR ^o- C (O) R ^p , C (O) -NR ^With 1 to 5 substituents independently selected from the group consisting of ^o R ^p , N [C (O) R ^o ] [C (O) R ^p ], SR ^o , halogen, CN, and NO _2. Can be replaced;
Here, ^Ro and R ^p are independently selected from the group consisting of H, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl.
Here, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl can be substituted with 1-5 substituents selected from the group consisting of halogen, CN and NO ₂ .

More preferably, L ³ and L ⁴ are 5 to 20 member heteroarylenes in each case independently of each other.
Here, the 5 to 20-membered heteroarylenes are C _{1 to 30} alkyl, C to _{2 to 30} alkenyl, C to _{2 to 30} alkynyl, C to _{5 to 12} cycloalkyl, C _{6 to 18} aryl and 5 to 20 member heteroaryl in each case. , OR ⁹¹ , OC (O) -R ⁹¹ , C (O) -OR ⁹¹ , C (O) -R ⁹¹ , NR ⁹¹ R ⁹² , NR ^91- C (O) R ⁹² , C (O) -NR ⁹¹ R ^{92, SR 91, halogen, CN,} can be substituted by ^SiR Siy ^{R Siz R Siaa 1~6} substituents selected from the group consisting of and OH ^{R 9,}
Here, R ⁹¹ and R ⁹² are independent of each other, in each case H, C _1-30 alkyl, C _2-30 alkenyl, C _2-30 alkynyl, C _5-12 cycloalkyl, C _6-18 aryl and Selected from the group consisting of 5 to 20 member heteroaryl,
C _1-30 alkyl, C _2-30 alkynyl and C _2-30 alkynyl are C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ^m , OC (O) -R ^m , C (O) -OR ^m , C (O) -R ^m , NR ^m R ⁿ , NR ^m- C (O) R ⁿ , C (O) -NR ⁿ R ^m , N [C (O) R ⁿ ] ^{[C (O) R m]} , SR n, ^{halogen, CN,} can be substituted by 1 to 10 substituents selected independently from the group consisting of ^SiR Siy ^{R Siz R Siaa} and NO _2; and At least two CH ₂ groups (but not adjacent CH ₂ groups) of C _1-30 alkyl, C _2-30 alkenyl and C _2-30 alkynyl can be replaced by O or S.
C _5-12 cycloalkyls are C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 member heteroaryl, OR ^m , OC. (O) -R ^m , C (O) -OR ^m , C (O) -R ^m , NR ^m R ⁿ , NR ^m- C (O) R ⁿ , C (O) -NR ^m R ⁿ , N [ ^{C (O) R m] [} C (O) R n], SR m, ^{halogen, CN,} 1 to 6 substituents independently selected from the group consisting of ^SiR Siy ^{R Siz R Siaa} and NO ₂ Can be substituted; and one or two CH ₂ groups of C _5-12 cycloalkyl (but not adjacent CH ₂ groups) are O, S, OC (O), CO, NR ^m or NR. Can be replaced by ^m- CO,
C _6-18 aryl and 5-20 membered heteroaryl are C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, 5-14 membered hetero. Aryl, OR ^m , OC (O) -R ^m , C (O) -OR ^m , C (O) -R ^m , NR ^m R ⁿ , NR ^m- C (O) R ⁿ , C (O) -NR ^{m R n 1~, n [C} (O) R m] where ^{[C (O) R n]} , SR m, ^{halogen, CN,} are independently selected from the group consisting of ^SiR Siy ^{R Siz R Siaa} and NO ₂ Can be substituted with 6 substituents,
^{R Siy,} R Siz, R ^Siaa independently of one _{another, H, C 1 to 20 alkyl, C 2 to 20 alkenyl, C 2 to 20 alkynyl, C 5 to 6} cycloalkyl, phenyl and O-Si (CH ₃ ) Selected independently from the group of ₃
Here, R ^m and R ⁿ consist of H, C _{1 to 20} alkyl, C _{2 to 20} alkenyl, C _{2 to 20} alkynyl, C _{5 to 8} cycloalkyl, C _{6 to 14} aryl and 5 to 14 member heteroaryl. Selected independently of the group,
C _1-20 alkyl, C _2-20 alkenyl and C _2-20 alkynyl are C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^o , OC (O) -R ^o , C (O) -OR ^o , C (O) -R ^o , NR ^o R ^p , NR ^o- C (O) R ^p , C (O) -NR ^o R ^p , N [C (O) R ^o ] It can be substituted with 1-5 substituents selected from the group consisting of [C (O) R ^p ], SR ^o , halogen, CN, and NO ₂ ;
C _5-8 cycloalkyl is C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^o , OC (O) -R ^o , C (O) -OR ^o , C (O) -R ^o , NR ^o R ^p , NR ^o- C (O) R ^p , C (O) -NR ^o R ^p , N [ It can be substituted with 1 to 5 substituents selected from the group consisting of C (O) R ^o ] [C (O) R ^p ], SR ^o , halogen, CN, and NO ₂ ;
C _6-14 aryl and 5-14 member heteroaryls are C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member hetero. Aryl, OR ^o , OC (O) -R ^o , C (O) -OR ^o , C (O) -R ^o , NR ^o R ^p , NR ^o- C (O) R ^p , C (O) -NR ^With 1 to 5 substituents independently selected from the group consisting of ^o R ^p , N [C (O) R ^o ] [C (O) R ^p ], SR ^o , halogen, CN, and NO _2. Can be replaced;
Here, ^Ro and R ^p are independently selected from the group consisting of H, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl.
Here, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl can be substituted with 1-5 substituents selected from the group consisting of halogen, CN and NO ₂ .

Even more preferably, L ³ and L ⁴ are independent of each other in each case a 5-20 member heteroarylene, where the 5-20 member heteroarylene is.
Selected from the group consisting of
Here, R ¹⁰⁴ and R ¹⁰⁵ are independently H, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl, and in each case. Selected from the group consisting of 5-14 member heteroaryls, or R ¹⁰⁴ and R ¹⁰⁵ , when attached to the same atom, form a 5-12 member ring system with the atom to which they are attached. ,
Where C _1-20 alkyl, C _2-20 alkenyl and C _2-20 alkynyl are C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^u , OC (O) -R. ^u , C (O) -OR ^u , C (O) -R ^u , NR ^u R ^v , NR ^u- C (O) R ^v , C (O) -NR ^u R ^v , N [C (O) R ^u ] [C (O) R ^v ], SR ^u , halogen, CN, and NO ₂ can be substituted with 1 to 5 substituents selected from the group;
C _5-8 cycloalkyl is C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^u , OC (O) -R ^u , C (O) -OR ^u , C (O) -R ^u , NR ^u R ^v , NR ^u- C (O) R ^v , C (O) -NR ^u R ^v , N [ It can be substituted with 1-5 substituents selected from the group consisting of C (O) R ^u ] [C (O) R ^v ], SR ^u , halogens, CNs, and NO ₂ ;
C _6-14 aryl and 5-14 member heteroaryls are C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member hetero. Aryl, OR ^u , OC (O) -R ^u , C (O) -OR ^u , C (O) -R ^u , NR ^u R ^v , NR ^u- C (O) R ^v , C (O) -NR ^With 1 to 5 substituents independently selected from the group consisting of ^u R ^v , N [C (O) R ^u ] [C (O) R ^v ], SR ^u , halogen, CN, and NO _2. Can be replaced;
The 5-12-membered ring system is C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^u , OC. (O) -R ^u , C (O) -OR ^u , C (O) -R ^u , NR ^u R ^v , NR ^u- C (O) R ^v , C (O) -NR ^u R ^v , N [ It can be substituted with 1-5 substituents selected from the group consisting of C (O) R ^u ] [C (O) R ^v ], SR ^u , halogens, CNs, and NO ₂ ;
Wherein ^{R u} and ^{R v} _{are, H, C 1 to 10 alkyl,} are independently selected from the group consisting of _{C 2 to 10} alkenyl and _{C 2 to 10} alkynyl,
Here, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl can be substituted with 1-5 substituents selected from the group consisting of halogen, CN and NO ₂ .
Here 5-20 membered heteroarylene may be substituted with 1-3 substituents R ⁹ is selected from the group consisting of C _{1 to 30} alkyl and halogen in each case.

Most preferably, L ³ and L ⁴ are 5 to 20 member heteroarylens in each case independently of each other.
Here, 5 to 20-member hetero-allylen
Selected from the group consisting of
Here 5-20 membered heteroarylene may be substituted with one substituent R ⁹ selected from the group consisting of C _{1 to 30} alkyl and halogen in each case.

In particular, L ³ and L ⁴ are independent of each other and are 5 to 20 member heteroarylenes in each case.
Here, 5 to 20-member hetero-allylen
And
Here, the 5- to 20-membered heteroarylene is unsubstituted.

Preferably, A is
Selected from the group consisting of
Where X is O in each case, S or NR ^1, and A1, A2, A3 and A4 may be substituted with 1-3 substituents ^{R 2.}

More preferably, A is
And
Where X is S or NR ^1, in each case, and A1 and A4 may be substituted with 1-3 substituents ^{R 2.}

Most preferably, A is
And
Here, A4 is unsubstituted.

Preferably B is
Selected from the group consisting of
Where X is O in each case, S or NR ^1, and B1, B2, B3 and B4 may be substituted with 1-3 substituents ^{R 2.}

More preferably, B is
And
Where X is S or NR ^1, in each case, and B1 and B4 may be substituted with 1-3 substituents ^{R 2.}

Most preferably, B is
And
Here, B4 is unsubstituted.

Preferably, R ² is selected from the group consisting of C _1-30 alkyl and halogen in each case.
Here, C _{1 to 30} alkyl is C _{5 to 8} cycloalkyl, C _{6 to 14} aryl, 5 to 14 member heteroaryl, OR ^e , OC (O) -R ^e , C (O) -OR ^e , C ( O) -R ^e , NR ^e R ^f , NR ^e- C (O) R ^f , C (O) -NR ^e R ^f , N [C (O) R ^e ] [C (O) R ^f ], SR It can be substituted with 1-10 substituents independently selected from the group consisting of ^e , halogen, CN, SiR ^Sis R ^Sit R ^Siu and NO ₂ ; and at least 2 CHs of C _1-30 alkyl. _Two (but not _two adjacent CHs) can be replaced by O or S,
Here, R ^Si , R ^Sit and R ^Siu are independent of each other, H, C _{1 to 20} alkyl, C _{2 to 20} alkenyl, C _{2 to 20} alkynyl, C _{5 to 6} cycloalkyl, phenyl and O-Si (CH). ₃ ) Selected from the group consisting of ₃
^Re and R ^f consist of the group consisting of H, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _5-8 cycloalkyl, C _6-14 aryl and 5-14 member heteroaryl. Selected independently,
C _1-20 alkyl, C _2-20 alkenyl and C _2-20 alkynyl are C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^g , OC (O) -R ^g , C (O) -OR ^g , C (O) -R ^g , NR ^g R ^h , NR ^g- C (O) R ^h , C (O) -NR ^g R ^h , N [C (O) R ^g ] Can be substituted with 1-5 substituents selected from the group consisting of [C (O) R ^h ], SR ^g , halogen, CN and NO ₂ ;
C _5-8 cycloalkyl is C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member heteroaryl, OR ^g , OC (O) -R ^g , C (O) -OR ^g , C (O) -R ^g , NR ^g R ^h , NR ^g- C (O) R ^h , C (O) -NR ^g R ^h , N [ It can be substituted with 1-5 substituents selected from the group consisting of C (O) R ^g ] [C (O) R ^h ], SR ^g , halogen, CN, and NO ₂ ;
C _6-14 aryl and 5-14 member heteroaryls are C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _5-6 cycloalkyl, C _6-10 aryl, 5-10 member hetero. Aryl, OR ^g , OC (O) -R ^g , C (O) -OR ^g , C (O) -R ^g , NR ^g R ^h , NR ^g- C (O) R ^h , C (O) -NR ^With 1 to 5 substituents independently selected from the group consisting of ^g R ^h , N [C (O) R ^g ] [C (O) R ^h ], SR ^g , halogen, CN, and NO _2. Can be replaced;
Here, R ^g and R ^h are independently selected from the group consisting of H, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl.
Here, C _1-10 alkyl, C _2-10 alkenyl and C _2-10 alkynyl can be substituted with 1-5 substituents selected from the group consisting of halogen, CN and NO ₂ .

More preferably, R ² is selected from the group consisting of unsubstituted C _1-30 alkyl and halogen in each case.

Most preferably, M ¹ or M ² is not substituted by the substituent R ² .

In all cases where an alkenyl or alkynyl substituent is attached to an O, N or S atom, the double or triple bond is preferably not directly attached to the heteroatom.

In all cases where an alkenyl or alkynyl substituent is attached to an O, N or S atom, the alkenyl or alkynyl substituent is preferably at least a C ₃ alkenyl moiety or a C ₃ alkynyl moiety.

The polymers of the present invention include dialdehyde and the s units M ² including direct condensation or the r units M ¹ and dialdehyde containing diamine and s number of units M ² containing the r units M ¹ It can be produced by direct condensation with a diamine. The polymer of the present invention can be synthesized without using a noble metal catalyst and further without using a toxic phosphorus ligand.

Further, the present invention is a step of reacting the monomer (1a) with the monomer (2a).
Alternatively, a step of reacting the monomer (1b) with the monomer (2b).
Provided is a method for producing a degradable polymer of the present invention, which comprises.

The present invention also
(I) Step of preparing a mixture A of a semiconductor single-walled carbon nanotube and a metallic single-walled carbon nanotube;
(Ii) A mixture A containing semiconductor single-walled carbon nanotubes and metallic single-walled carbon nanotubes is dispersed in a solvent using the degradable polymer of the present invention as a dispersant, and the semiconductor single-walled carbon in the solvent is dispersed. In the step of obtaining the dispersion liquid B of the nanotubes, the dispersion liquid further contains metallic single-walled carbon nanotubes;
(Iii) A step of separating metallic single-walled carbon nanotubes from the dispersion liquid B of semiconductor single-walled carbon nanotubes in a solvent to obtain a concentrated dispersion liquid C of semiconductor single-walled carbon nanotubes in a solvent;
(Iv) A step of hydrolyzing the polymer of the present invention in the dispersion C of semiconductor single-walled carbon nanotubes in a solvent;
(V) Semiconductor single-walled carbon from a mixture of semiconductor single-walled carbon nanotubes and metallic single-walled carbon nanotubes, which comprises a step of separating semiconductor single-walled carbon nanotubes from solution D containing a solvent and a decomposed polymer. A method for separating nanotubes is provided.

The present invention also provides a method for producing semiconducting single-walled carbon nanotubes, which further comprises steps (i) to (v).

In another embodiment, the present invention also provides a method for producing semiconducting single-walled carbon nanotubes, which comprises steps (i)-(iii).

The solvent can be halogenated or non-halogenated, aromatic or non-aromatic, complex aromatic or non-complex aromatic.

Suitable solvents are, for example, preferably aromatic solvents selected from the group consisting of benzene, naphthalene, biphenyls and mixtures thereof, these benzenes, naphthalenes and biphenyls consisting of halogens, C _1-20 alkyl. It can be substituted with 1 to 4 substituents selected independently of the group, where C _{1 to 20} alkyl can be substituted with one or more halogens. Naphthalene and biphenyl are preferably used in their liquid form at temperatures above their melting point.

Examples of aromatic solvents are benzene, toluene, o-xylene, m-xylene, p-xylene, 1,3,5-trimethylbenzene (mesitylene), 1,2,3-trimethylbenzene, 1,2,4- Trimethylbenzene, chlorobenzene, 1,2-dichlorobenzene (ortho-dichlorobenzene), 1,3-dichlorobenzene, 1,2,4-trichlorobenzene, indan, tetraline, methoxybenzene (anisole), ethylbenzene, 1,2- Diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, propyl-benzene, butyl-benzene, tert-butyl-benzene, isopropylbenzene, 1-methylnaphthalene, 2-methylnaphthalene and 1-chloronaphthalene.

Suitable solvents are also preferably heteroaromatic solvents selected from the group consisting of thiophenes, furans, pyridines, pyrroles, pyrimidines and mixtures thereof, wherein the thiophenes, furans, pyridines, pyrroles and pyrimidines are halogens and It can be substituted with 1 to 4 substituents independently selected from the group consisting of C ₁ to ₂₀ alkyl, where C _{1 to 20} alkyl can be substituted with one or more halogens.

Examples of heteroaromatic solvents are thiophene, 2-methyl-thiophene, 3-methyl-thiophene, pyridine, 2-methyl-pyridine, 3-methyl-pyridine, 4-methyl-pyridine, 2,4-dimethyl-pyridine and It is 2,4,6-trimethylpyridine.

In particular, the solvent is toluene, or a mixture containing toluene.

Preferably, the mixture A of the semiconductor single-walled carbon nanotube and the metallic single-walled carbon nanotube is 20 to 95% by mass based on the total mass of the semiconductor single-walled carbon nanotube and the metallic single-walled carbon nanotube. It contains semiconducting single-walled carbon nanotubes and 80 to 5% by mass of metallic single-walled carbon nanotubes.

More preferably, the mixture A contains 30 to 95% by mass of the semiconductor single-walled carbon nanotubes and 70 to 5% by mass of the metal based on the total mass of the semiconductor single-walled carbon nanotubes and the metallic single-walled carbon nanotubes. Contains single-walled carbon nanotubes.

Even more preferably, the mixture A contains 40 to 95% by mass of the semiconductor single-walled carbon nanotubes and 60 to 5% by mass based on the total mass of the semiconductor single-walled carbon nanotubes and the metallic single-walled carbon nanotubes. Contains metallic single-walled carbon nanotubes.

Preferably, the diameters of the semiconducting single-walled carbon nanotubes and the metallic single-walled carbon nanotubes in the mixture A are in the range of 0.5 to 5 nm. More preferably, the diameters of the semiconducting single-walled carbon nanotubes and the metallic single-walled carbon nanotubes in the mixture are in the range of 0.8 to 2.5 nm. Most preferably, the diameters of the semiconducting single-walled carbon nanotubes and the metallic single-walled carbon nanotubes in the mixture are in the range of 1.0 to 2.0 nm.

Preferably, the concentrations of the semiconductor single-walled carbon nanotubes and the metallic single-walled carbon nanotubes in the dispersion B are in the range of 0.001 to 20% by mass, and more preferably in the range of 0.001 to 10% by mass. It is in the range of 0.001 to 5% by mass, even more preferably in the range of 0.001 to 1% by mass, and most preferably in the range of 0.01 to 1% by mass. ..

Preferably, the total mass ratio of the semiconductor single-walled carbon nanotube / polymer and the metallic single-walled carbon nanotube / polymer of the present invention in the dispersion B is in the range of 0.01 / 1 to 10/1, which is preferable. Is in the range of 0.05 / 1 to 5/1, more preferably in the range of 0.25 / 1-3 / 1.

The mixture A of semiconducting single-walled carbon nanotubes and metallic single-walled carbon nanotubes is prepared by a method known in the art such as arc discharge, laser ablation, plasma torch process or catalytic decomposition (CVD) of carbon-containing molecules. Can be prepared.

Preferably, the mixture A of the semiconductor single-walled carbon nanotubes and the metallic single-walled carbon nanotubes is prepared by an arc discharge and a plasma torch process.

Usually, the dispersion liquid B of the semiconductor single-walled carbon nanotubes in the solvent is prepared by ultrasonic treatment in the step (ii).

Preferably, the metallic single-walled carbon nanotubes are separated from the dispersion liquid B of the semiconductor single-walled carbon nanotubes in the solvent by a centrifugation process in the step (iii). Preferably, the angular velocity used in the centrifugation process is related to a g value in the range of 100-100,000 g, more preferably a g value in the range of 500-50000 g, and even more preferably a g value in the range 1000-50000 g. To do. Most preferably, the g value used in the centrifugation process is in the range 4000-30000 g.

Appropriate types of centrifuges such as microcentrifuges, high speed centrifuges and ultracentrifuges can be used in the centrifuge process. Preferably, a high speed centrifuge is used.

Generally, the centrifugation process is carried out at a temperature of 0 ° C to 100 ° C, more preferably 0 ° C to 50 ° C, even more preferably 0 ° C to 30 ° C, most preferably 5 ° C to 20 ° C, particularly 10 ° C to 20 ° C. Will be done.

Preferably, the supernatant is recovered after the centrifugation process to obtain a dispersion C of semiconductor single-walled carbon nanotubes in a solvent, which can optionally be diluted with a further solvent.

Preferably, the concentration of the semiconductor single-walled carbon nanotubes in the dispersion C is in the range of 0.0001 to 10% by mass, more preferably in the range of 0.001 to 10% by mass, and most preferably 0. It is in the range of 001 to 1% by mass.

The polymer of the present invention in the dispersion C is generally decomposed under acidic conditions by hydrolysis by adding a catalytic amount of acid. Suitable acids are trifluoroacetic acid (TFA), acetic acid, p-toluenesulfonic acid (pTsOH), HCl, H ₂ SO ₄ , HNO ₃ .

Hydrolysis in the step (iv) is carried out at 0 ° C. to 200 ° C., more preferably 0 ° C. to 100 ° C., even more preferably 20 ° C. to 80 ° C., especially at room temperature.

Preferably, the hydrolysis of the degradable polymer in step (iv) is assisted by sonication and heating.

Preferably, the semiconducting single-walled carbon nanotubes are separated from solution D containing the solvent and the decomposed polymer in step (v) by a centrifugation process. The conditions for centrifugation are as described above for step (iii).

Solution D contains a monomer from which the polymer of the present invention is produced. In any additional step (vi), the monomer is preferably isolated from solution D by flash column chromatography to obtain a pure monomer for polymer resynthesis.

FIG. 1 shows thermogravimetric analysis (TGA) of PDPP-PD (loss 5%, 404 ° C) and PFPD (loss 5%, 400 ° C). FIG. 2 shows the decomposition of a polymer under the catalytic action of an acid. FIG. 3 shows a comparison when SWNTs of various purityes are used under the same conditions (polymer / SWNT ratio = 1: 1). FIG. 4 shows (a) absorption spectra of untreated SWNTs (30% purity) dispersed by PF-PD using different polymer concentrations (polymer / SWNT ratio is 1: 1), (b) various. The plot of the yield and φ value with respect to the polymer / SWNT concentration is shown. FIG. 5 shows (a) absorption spectra of SWNTs dispersed by PDPP-PD at various polymer / SWNT ratios in toluene, and (b) normalized absorption of PDPP-PD sorted SWNT thin films for various polymer / SWNT ratios. The spectrum is shown. FIG. 6 shows a purity comparison of s-SWNT dispersed by PF-PD and PDPP-PD with 99.9% pure s-SWNT commercially available from Nanointegris. FIG. 7 shows the Raman spectrum of the original SWNT and the Raman spectrum of SWNT sorted by the polymer PF-PD excited with a laser at (a) 532 nm and (b) 638 nm. FIG. 8 shows the Raman spectrum of the original SWNT and the Raman spectrum of SWNT sorted by the polymer PDPP-PD excited with lasers at (a) 785 nm, (b) 532 nm and (c) 638 nm. FIG. 9 shows an absorption spectrum of a solution using a monomer as a dispersion. FIG. 10 shows the selective dispersion and release of s-SWNT with PF-PD. FIG. 11 shows (a) an atomic force microscope (AFM) image and (b) the transfer characteristics of a typical TFT device.

Example 1. Polymer Synthesis and characterization Materials and General Methods All reagents and starting materials were purchased from commercial sources and used without further purification. Thermogravimetric analysis (TGA) was performed under nitrogen flow (20 mL / min) at a heating rate of 10 ° C./min using METTLER TOLEDO TGA / SDTA 851e. Gel permeation chromatography (GPC) was performed on a Tosoh High-temperature EcoSEC (RI detector) at a high temperature of 180 ° C. using 1,2,4-trichlorobenzene (TCB) as an eluent. Compound 1 was prepared according to the procedure in the literature. 2 was purchased from Sigma-Aldrich.
Scheme 1 Synthesis of degradable polymers

Compared to conventional conjugate polymers synthesized by cross-coupling reactions (eg Suzuki or Stille coupling), the polymers of the invention can be synthesized without the use of precious metal catalysts and toxic phosphorus ligands. .. Therefore, the degradable polymers of the present invention are cheaper and more environmentally friendly. The imine bond was environmentally stable under ambient conditions and no polymer degradation was observed over the 6 month storage period. Both polymers exhibit excellent thermal stability at decomposition temperatures above 400 ° C. (Fig. 1).

FIG. 1 shows thermogravimetric analysis (TGA) of PDPP-PD (loss 5%, 404 ° C) and PFPD (loss 5%, 400 ° C).

Example 1
9,9-Zidodecyl-9H-Fluorene-2,7-Dicarbaldehyde (F-CHO): Compound 1 (3 g, 4.54 mmol) and ethyl ether (40 mL) were added to a 100 mL round bottom flask. n-BuLi (2.5 M, 4.54 mL, 11.4 mmol) was added at −78 ° C. After stirring at −78 ° C. for 30 minutes, anhydrous DMF (1.16 g, 15.9 mmol) was added dropwise at −78 ° C. The mixture was warmed to room temperature and stirred for 1 hour. The mixture was then quenched with HCl (50 mL, 1 M aqueous solution). The aqueous layer was extracted with dichloromethane (3 x 50 mL). The combined extracts were washed with distilled water and dried over anhydrous Na ₂ SO ₄ . After removing the solvent under reduced pressure, the residue was purified by silica chromatography (eluent: hexane / dichloromethane = 4/1 to 1/1) to give F-CHO as an off-white solid. Yield: 2.23 g (88%)

Example 2
5,5'-(2,5-bis (2-octyldodecyl) -3,6-dioxo-2,3,5,6-tetrahydropyrrolo [3,4-c] pyrrole-1,4-diyl) bis (Thiophen-2-carbaldehyde) (DPP-CHO): Diisopropylamine (0.98 mL, 6.96 mmol) and THF (50 mL) were added to a 100 mL round bottom flask. N-BuLi (1.6 M, 2.9 mL, 4.64 mmol) was added and stirred at 0 ° C. for 30 minutes to prepare new lithium diisopropylamide (LDA). Compound 2 (1.0 g, 1.16 mmol) was then added dropwise to the flask at −78 ° C. After stirring at −78 ° C. for 30 minutes, anhydrous DMF (0.46 mL, 6.96 mmol) was added dropwise at −78 ° C. The mixture was warmed to room temperature and stirred for 1 hour. The mixture was then quenched with 20 mL of water. The aqueous layer was extracted with dichloromethane (3 x 50 mL). The combined extracts were washed with distilled water and dried over anhydrous Na ₂ SO ₄ . After removing the solvent under reduced pressure, the residue was purified by silica chromatography (eluent: hexane / ethyl acetate = 20/1 to 10/1) to give DPP-CHO as a dark red solid. Yield: 0.82 g (77%)

Example 3
Polymerization of PF-PD: F-CHO (800 mg, 1.43 mmol), p-phenylenediamine (154.8 mg, 1.43 mmol), p-toluenesulfonic acid (PTSA) (13) in Schlenk tubes (100 mL). .6 mg, 0.0715 mmol, 5 mol%), anhydrous CaCl ₂ (200 mg) and anhydrous toluene (50 mL) were added under a nitrogen atmosphere. The tube was then sealed in a nitrogen atmosphere. The mixture was stirred at 110 ° C. for 48 hours. After completion, anhydrous K ₂ CO ₃ (20 mg) was added and the mixture was stirred at 110 ° C. for 30 minutes. The mixture was then filtered through a nylon filter to remove desiccants and insoluble salts. After removing the solvent in the filtrate, the polymer was recovered to give a yellow solid (890 mg, 99% yield).

Example 4
Polymerization of PDPP-PD: DPP-CHO (250 mg, 0.273 mmol), p-phenylenediamine (29.5 mg, 0.273 mmol), p-toluenesulfonic acid (PTSA) (2) in a Schlenck tube (100 mL). .6 mg, 0.014 mmol, 5 mol%), anhydrous CaCl ₂ (100 mg, desiccant) and anhydrous toluene (30 mL) were added under a nitrogen atmosphere. The tube was then sealed in a nitrogen atmosphere. The mixture was stirred at 110 ° C. for 48 hours. After completion, anhydrous K ₂ CO ₃ (10 mg) was added and the mixture was stirred at 110 ° C. for 30 minutes. The mixture was then filtered through a nylon filter to remove desiccants and insoluble salts. After removing the solvent in the filtrate, Soxhlet extraction was carried out with anhydrous acetone for 2 hours and hexane for 2 hours to purify the polymer, which was finally recovered with chloroform. The chloroform fraction was then evaporated to remove the solvent to give a dark green solid (213 mg, 79% yield).

2. 2. Decomposition of Polymer Under Acidic Conditions Example 5
To investigate the polymer decomposition process, a polymer solution is prepared in THF, a small amount of trifluoroacetic acid (TFA) and droplets of deionized water are added, followed by UV-Vis-NIR spectroscopy (Cary 6000i spectroscopy). Their disassembly process was monitored by a total (Varian). Decomposition can be carried out in toluene, but since the solubility of water in toluene is low, ultrasonic treatment (bath sonicator) is required to promote the decomposition reaction.

2a and 2b show the decomposition of the polymer under the catalytic action of an acid. Changes in the absorption spectra of (a) PF-PD and (b) PDPP-PD after the addition of a small amount of trifluoroacetic acid (TFA) and a drop of water.

2a and 2b show the decomposition process of the polymers PF-PD and PDPP-PD at room temperature under acidic conditions, respectively. Both polymers can be decomposed into monomers under catalytic amounts of acid. After complete decomposition, their absorption spectra were approximately identical to their monomers. PF-PD usually decomposes quickly within minutes, while PDPP-PD decomposes fairly slowly. It has been found that sonication or heating of polymer solutions can accelerate the decomposition process. For example, the decomposition of PDPP-PD can be completed within 30 minutes using a bath sonicator at 50 ° C.

3. 3. Selective dispersion and SWNT characterization General sorting procedures for polymer PF-PD with plasma grown SWNTs:
Example 6
5 mg of PF-PD and 5 mg of plasma grown SWNT (RN-020 obtained from Raymor Nano-tech, including 30% SWNT) were mixed in 25 mL of toluene and the amplitude level was 50% (Cole Palmer sonicator). It was ultrasonically treated at 750 W) for 30 minutes. The solution was then centrifuged at 16 ° C. at 17,000 rpm (22000 g) for 30 minutes. The supernatant was collected to give the final sorting s-SWNT solution.

The absorption spectrum of PF-PD does not overlap with the absorption of metallic SWNTs. Therefore, both dispersion concentration and selectivity can be evaluated by UV-Vis-NIR measurements.

General sorting procedure for PDPP-PD using arc-discharged SWNTs:
Example 7
5 mg PDPP-PD and 10 mg arc-discharged SWNT (P2-SWNT purchased from Carbon Solutions, Inc., containing approximately 65% SWNT) were mixed in 25 mL toluene and amplitude level 70. % (Col Palmer sonicator 750W) was sonicated for 30 minutes. The mixture was then centrifuged at 16 ° C. and 17,000 rpm for 30 minutes. The supernatant (80%) was collected to give the final sorting SWNT solution.

The concentration of the dispersion was evaluated by UV-Vis-NIR measurement using a 1 cm long quartz cell containing toluene as a background. A SWNT film was made on this substrate by drop casting the supernatant onto a glass substrate and annealing the film under Ar at 500 ° C. for 1 hour to remove the wrapping polymer to determine selectivity. ..

General procedures for polymer removal and recycling:
Example 8
To decompose the wrapping polymer, a small amount of TFA (10 uL) and a few drops of water were added to the selective SWNT solution. The solution was bath sonicated for 0.5 to 1 hour to complete the hydrolysis reaction. SWNT precipitates were formed after polymer decomposition. The solution was then centrifuged at 17,000 rpm for 5 minutes to precipitate the SWNT. After collecting the supernatant, 20 mL of acetone was added. The mixture was sonicated in a bath sonicator for 10 minutes and centrifuged again to wash the SWNT precipitate. The cleaning process is repeated twice. Next, the s-SWNT sediment was collected by filtration.

The precipitates produced during polymer sorting contained amorphous carbon, met-SWNT and undispersed s-SWNT and absorbed a significant amount of polymer. To recycle these polymers, 20 mL of THF was added to the precipitate. The mixture was sonicated in a bath sonicator for 10 minutes and centrifuged at 17,000 rpm for 15 minutes to wash the SWNT precipitate. The cleaning process is repeated twice. The sediment was then removed by filtration.

All supernatants and filtrates obtained in the above steps were combined and polymer recycled. After removing the solvent under reduced pressure, the monomer was purified by flash chromatography to give a pure monomer. The purified and circulated monomers can be used for polymerization at other times.

Determination of sorting yield and polymer circulation efficiency:
Example 9
50 mg of PF-PD and 50 mg of plasma grown SWNT (RN-020) were mixed in 25 mL of toluene, sonicated at an amplitude level of 50% (Cole Palmer sonicator 750W) for 30 minutes and in a dry ice bath. It was cooled from the outside. The solution was then centrifuged at 16 ° C. at 17,000 rpm (22000 g) for 30 minutes. 80% of the supernatant (20 mL) was recovered. Absorption spectroscopy showed peak absorption of A = 2.486 at λ = 939 nm for a cuvette with d = 1 cm (FIG. 4a).

Following the polymer removal step of the supernatant, the sorting SWNTs were finally filtered through a 0.2 μm pore size PTFE membrane, washed 3 times with toluene (30 mL) and vacuum dried at 60 ° C. A SWNT film was formed on the membrane. When the SWNT film is weighed, the total mass is 1.41 mg. Therefore, the SWNT concentration of the sorted solution (20 mL) was calculated to be 0.0705 mg / mL. Using the optical density at 939 nm, the extinction coefficient (ε, mL mg ^-1 cm ^-1 ) was calculated by Beer-Lambert's law: A = OD ₉₃₉ = εlc, where l is the cuvette path length (cm). ), And c is the SWNT concentration (mg / mL). The extinction coefficient (ε) was determined to be 35.3 mL mg ^-1 cm ^-1 , which is consistent with the recently reported value of 34.9 mL mg ^-1 cm ^-1 for a similar type of s-SWNT. This absorption coefficient (ε) allows the sorting yields for various conditions to be calculated using their absorption peaks at 939 nm. The calculated yield for the PF-PD sorted SWNTs is based on the amount of semiconducting SWNTs in the untreated SWNTs, which is about 20% of the total mass of the untreated SWNTs (RN-020).

Raman and PLE characterization of sorting SWNTs:
Raman spectroscopy was performed with excitations of 2.33 eV (532 nm), 1.93 eV (638 nm), and 1.58 eV (785 nm) at a magnification of 100 times and a spot diameter of 1 μm. The peak position was calibrated by Si line at 521 cm- ¹ . Raman peaks can be assigned to metallic SWNTs or semiconductor SWNTs according to Raman Kataura plots. PLE spectra of various SWNT samples in toluene were obtained according to the method previously reported by the present inventors.

FIG. 3 shows a comparison when SWNTs of various purityes are used under the same conditions (polymer / SWNT ratio = 1: 1).

30% SWNT (RN-020, 10USD / g) and semi-purified SWCNT (RN-220, 60-70% purity, 45USD / g) produced as-is were purchased from Raymor Industries Inc. Semi-purified SWNTs exhibit significantly higher SWNT content than untreated SWNTs as produced, as shown by their NMP dispersion solution. After PF-PD sorting, 30% SWNT showed a φ value of 0.407 and a yield of 23.7%, and 70% SWNT showed a φ value of 0.408 and a yield of 19.8%. It was. The calculation of the yield was based on the amount of s-SWNT in the total mass of untreated SWNT (in the case of RN-020, the amount of s-SWNT was 20%, and in the case of RN-220, the amount of s-SWNT was 46. %). Therefore, 30% untreated SWNTs showed very similar selectivity and even higher yields compared to 70% semi-purified SWNTs.

FIG. 4 shows the absorption spectra of (a) untreated SWNTs (30% pure) dispersed by PF-PD using various polymer concentrations (polymer / SWNT ratio is 1: 1). A spectrum was acquired with a cuvette having an optical path length of 1 cm. (B) Plots of yields and φ values for various polymer / SWNT concentrations. Higher concentrations result in lower yields, but mass production improves throughput.

FIG. 5 shows (a) absorption spectra of SWNTs dispersed by PDPP-PD at various polymer / SWNT ratios in toluene, and (b) normalized absorption of PDPP-PD sorted SWNT thin films for various polymer / SWNT ratios. The spectrum is shown. A SWNT thin film was prepared by drop casting the supernatant onto a glass substrate and then annealing under Ar at 500 ° C. for 1 hour to remove the wrapping polymer.

When the amount of SWNT increased while maintaining a constant amount of polymer, the concentration of the dispersion first increased and then decreased. Absorption of the polymer by excessive carbonaceous precipitates could reduce the concentration of the dispersion, which in turn reduced the concentration of polymer available for sorting in solution. Sorting selectivity also depends on the polymer / AD-SWNT ratio, with a 5 mg / 10 mg ratio providing the best selectivity.

FIG. 6 shows a purity comparison of s-SWNT dispersed by PF-PD and PDPP-PD with 99.9% pure s-SWNT commercially available from Nanointegris. PDD-PD sorting s-SWNT with large tube diameter showed similar selectivity, and PF-PD sorting s-SWNT with similar tube diameter clearly showed better selectivity.

FIG. 7 shows the Raman spectrum of the original SWNT and the Raman spectrum of SWNT sorted by the polymer PF-PD excited with a laser at (a) 532 nm and (b) 638 nm. Under excitation at 532 nm and 638 nm, some RBM peaks of s-SWNT were seen in the range of 150-200 cm ^-1 in the original SWNT. After sorting, some peaks remain and the relative peak intensities also change, indicating that the polymer prefers to disperse s-SWNTs of a particular chirality. In order to compare the peak intensities of the original SWNT and the sorted SWNT, their G ⁺ peaks were normalized to the same intensity.

FIG. 8 shows the Raman spectrum of the original SWNT and the Raman spectrum of SWNT sorted by the polymer PDPP-PD excited with lasers at (a) 785 nm, (b) 532 nm and (c) 638 nm. In order to compare the peak intensities of the original SWNT and the sorted SWNT, their G ⁺ peaks were normalized to the same intensity.

FIG. 9 shows an absorption spectrum of a solution using a monomer as a dispersion. Absorption of SWNT was not detected, indicating that both monomers were unable to disperse SWNT.

First, the ability of PF-PD to disperse low-cost untreated SWNTs (RN-020, $ 10 / g from Raymor Industries Inc., SWNT purity about 30%) with a diameter of 0.9-1.5 nm was tested. did. Figure 10a, PF-PD demonstrates that can disperse the high density s-SWNT of large diameter having a metal peak is hardly detected to _{M 11} region. The optical density (OD) at 939 nm for the PF-PD sorted SWNT is up to 2.498 in a 1 cm optical path length cuvette corresponding to a SWNT concentration of 0.0705 mg / mL. The OD value is significantly higher than other reported conjugate polymers used in large diameter SWNTs, indicating a strong dispersibility of PF-PD. Compared to conventional sorting methods using the more expensive purified SWNTs (purity 50-70%, price is usually 4-8 times higher), this result is manufactured without affecting sorting yield and selectivity. It is shown that the untreated SWNT (purity 30%) as it is can be used directly for polymer wrapping (Fig. 3). The polymer / SWNT ratio and concentration are factors that affect the yield and selectivity of the SWNT dispersion. Sorting yield _is determined by the absorption intensity of the _{S 22} peaks, calculated for s-SWNT weight of the total mass of the SWNT. Selectivity was evaluated based on the φ value defined by the ratio of the peak area of absorption of both S ₂₂ and M _{11 to the} background area. The higher the φ value, the higher the purity of s-SWNT, and the φ value> 0.40 correlated with the purity> 99%.

FIG. 10b plots the relationship between yield and selectivity for various polymer / SWNT ratios. Compared to the reports in the literature, for large diameter SWNTs, when a high φ value> 0.40 is reached, the yield is usually low (<5%) and the polymer PF-PD has a high φ of 0.407. Both values and high yields of 23.7% were shown simultaneously (polymer / SWNT ratio in FIG. 10b = 1), suggesting a strong dispersal capacity and high selectivity of this polymer. Due to the reduced polymer / SWNT ratio, the selectivity is higher at φ values up to 0.445, but the yield is relatively low. The polymer / SWNT concentration also changed from 0.2 mg / mL to 2 mg / mL (Fig. 4a). At the same polymer / SWNT ratio (1: 1), the higher the concentration, the higher the selectivity, but the lower the yield. This inverse correlation between yield and selectivity was also found in many other polymer systems.

Compared to conventional conjugated polymers, DPP-based polymers tend to disperse SWNTs of larger diameters. The ability of PDPP-PD to disperse SWNTs using arc-discharged SWNTs was investigated (Fig. 5). PDPP-PD can disperse a significant amount of arc-discharged SWNT in an estimated yield of 2.3%. Absorption spectrum of DPP based polymer, since overlapping the M ₁₁ region of the sorting SWNT, before estimating the selectivity of various selection conditions, remove the polymer by thermal annealing at 500 ° C. The polymer SWNT film under Ar did. Since the φ value cannot be used directly to estimate the selectivity for DPP sorted SWNTs due to interference from the polymer, the sorted absorption spectra were compared to commercially available 99.9% s-SWNTs (FIG. 6). Both PDP-PD sorting s-SWNT and PF-PD sorting s-SWNT showed similar or better selectivity compared to 99.9% s-SWNT, which is a high selection of degradable polymers. Show sex.

To further verify the enrichment of s-SWCNT, Raman spectra of the original SWNT and polymer sorted SWNT were measured (FIGS. 10c, 7, and 8). Under excitation at 785 nm, a strong radial breathing mode (RBM) peak of the metal tube was observed in the range of 140-190 cm- ¹ for the original SWNT. After sorting, this peak almost disappeared. In G peak area (1500~1600cm ^-1), mainly G from m-SWNT at 1550 cm ^{-1 -} Whereas the intensity of the peak is significantly reduced, mainly from s-SWNT in 1600 cm ^-1 The G ⁺ peak remained unchanged. Other laser excitations (532 nm and 633 nm) also demonstrated m-SWNT removal and dispersion of s-SWNTs of a particular chirality (FIG. 7).

Both PF-PD and PDPP-PD dialdehyde monomers were unable to disperse SWNTs (FIG. 5), suggesting a weak interaction with their SWNTs. A catalytic amount of TFA and some deionized water was added to the sorting solution to release s-SWNT. The solution was sonicated to accelerate the hydrolysis reaction. SWNT precipitates were formed after polymer decomposition. The SWNT precipitate was centrifuged and collected by filtration through a 0.2 μm PTFE membrane. The absorption spectrum of the filtrate shows only the absorption of the monomer, which indicates that all the concentrated s-SWNT was quantitatively recovered (Fig. 10d). The filtered s-SWNT can be redistributed into NMP and aqueous solution with a detergent having approximately the same absorption spectrum in both the M ₁₁ and S ₂₂ regions (FIG. 10d), which is a selection. SWNTs also show that they can be used for NMP or aqueous deposition methods in electronic applications. Absorption spectroscopy of SWNTs redispersed in NMP failed to detect the polymer or monomer, demonstrating quantitative removal of the polymer. This result was further confirmed by X-ray photoelectron spectroscopy (XPS) measurements of the SWNT solid that disappeared in the SWNT sample (FIG. 10e) where the N1s peak due to the N atom in the polymer was emitted. It was found that about 1/2 to 2/3 of the conjugated polymer was absorbed by precipitates containing undispersed s-SWNT, m-SWNT, and amorphous carbon. Therefore, in order to recycle the polymer, the polymer in both the supernatant and the precipitate was decomposed and filtered. The filtrate can be purified by flash column chromatography to give a pure monomer and the polymer can be resynthesized. Almost all monomers can be recycled with a recycling rate of up to 93% after purification, which means that the degradable polymer approach of the present invention will effectively reduce the polymer cost for SWNT separation. Show that.

4. Determining the characteristics of the thin film transistor of the sorting SWNT Example 10
A thin film transistor (TFT) was produced by drop-casting a PF-PD sorting SWNT solution onto a patterned Au (source / drain) / SiO ₂ (300 nm) / doped Si substrate. Then, the substrate was rinsed with toluene and annealed at 200 ° C. for 20 minutes under ambient conditions. Most of the polymer was removed using a toluene rinse. This results in better tube-to-tube junctions and improved charge carrier mobility. FIG. 11a shows an atomic force microscope (AFM) image showing a SWNT network with a tube density of about 50 tubes / μm ² . Most of the sorting tubes showed tube lengths in the range of 0.5-2 μm. TFT devices showed a high hole mobility range 20~49cm ² V ^-1 s ^-1 with an on / off ratio of greater than 10 ⁵ (FIG. 11b). The high on / off ratio of the sorted s-SWNTs of the present inventors as compared with the untreated unsorted SWNTs lower than 10, further supports the high purity of the sorted s-SWNTs.

In summary, imine-based conjugate polymers based on various types of building blocks have been tested for selective dispersion of s-SWNT. They showed strong dispersibility in the case of large diameter s-SWNTs with high yields (up to 23.7%) and high selectivity (> 99%). The method of the present invention offers greater advantages over other methods (eg, low cost, high selectivity, recyclability, and less SWNT damage), but still regular building blocks without a specific structural design. Is using. More importantly, the design of degradable polymers can be easily used for other π-conjugated structures, thus demonstrating a common approach for low cost separation of "clean" s-SWNTs.

10a-e show the selective dispersion and release of s-SWNT with PF-PD. (A) Absorption spectrum of PF-PD (PF-PD / SWNT ratio = 1: 1, concentration 2 mg / mL) and untreated SWNT (purity 30%) dispersed by NMP. A spectrum was acquired with a cuvette having an optical path length of 1 cm. (B) Plots of yields and φ values for various polymer / SWNT ratios (polymer concentration 0.2 mg / mL). (C) Raman spectra of untreated SWNT and PF-PD sorted SWNT (excited by 785 nm laser). The polymer was decomposed and removed for sorting SWNT. (D) Absorption spectra of SWNTs as sorted, NMP and sorted SWNTs redispersed in the surfactant SC (1% aqueous solution) polymer PF-PD, and the monomer (F-CHO) after polymer decomposition. (E) XPS results for SWNTs wrapped in PF-PD and SWNTs released.

Figure 11b shows a typical TFT devices of the transfer characteristic _(V DS = -40V).

Claims (7)

A method for separating semiconducting single-walled carbon nanotubes from a mixture of semiconducting single-walled carbon nanotubes and metallic single-walled carbon nanotubes.
(I) Step of preparing a mixture A of a semiconductor single-walled carbon nanotube and a metallic single-walled carbon nanotube,
(Ii) a diamine containing direct condensation or dialdehyde and the s units M ² containing the r units M ¹ and dialdehyde containing diamine and s number of units M ² containing the r units M ¹ Degradable polymer containing at least one unit of formula (1) that can be produced through direct condensation.
And
In the above formula,
T ¹ is a carbon atom or a nitrogen atom and
T ² is a carbon atom if T ¹ is a nitrogen atom, or is a nitrogen atom if T ¹ is a carbon atom.
r is 1, 2, 3 or 4
s is 1, 2, 3 or 4
M ¹ is
Selected from the group consisting of
And M ² is
Selected from the group consisting of
here
R ¹ is C _1-36 alkyl and
R ¹⁰² and R ¹⁰³ use the degradable polymer independently selected from the group consisting of H and C ₁ to ₂₀ alkyl as a dispersant.
A step of dispersing a mixture A containing the semiconductor single-walled carbon nanotubes and the metallic single-walled carbon nanotubes in a solvent to obtain a dispersion liquid B of the semiconductor single-walled carbon nanotubes in the solvent. Is a process that further contains metallic single-walled carbon nanotubes,
(Iii) A step of separating metallic single-walled carbon nanotubes from a dispersion liquid B of semiconductor single-walled carbon nanotubes in a solvent to obtain a concentrated dispersion liquid C of semiconductor single-walled carbon nanotubes in a solvent.
(Iv) A step of hydrolyzing the polymer of the present invention in a dispersion C of semiconductor single-walled carbon nanotubes in a solvent.
(V) The method comprising the step of separating the semiconductor single-walled carbon nanotubes from the solution D containing the solvent and the decomposed polymer. The method according to claim 1 , wherein a mixture A of the semiconductor single-walled carbon nanotubes and the metallic single-walled carbon nanotubes is prepared by an arc discharge or a plasma torch process. The method of claim 1 or 2 , wherein step (ii) is performed by sonication. The method according to any one of claims 1 to 3 , wherein the hydrolysis of the degradable polymer in the step (iv) is assisted by sonication. The method according to any one of claims 1 to 3 , wherein the solvent used in the step (i) is toluene. Pure monomers (1a) and (2a)
Or pure monomers (1b) and (2b)
The method according to any one of claims 1 to 4 , further comprising the step (vi) of isolating the polymer from solution D for polymer resynthesis. The method of claim 6 , wherein the pure monomer is isolated by flash column chromatography.