Polymer with deuterated side chain and application thereof

Abstract

The invention relates to the field of organic photovoltaic materials, in particular to a side chain deuterated polymer and application thereof. The invention provides a side chain deuterated polymer containing a repetitive unit shown as a general formula (I), a deuterium atom is introduced to a specific site of a branched chain, so that the molecular stability is enhanced, and when the side chain deuterated polymer is applied to an organic photovoltaic device, the service life of the device can be effectively prolonged.

Description

Technical Field

[0001] The present invention relates to the field of organic photovoltaic materials, and particularly to a polymer with side-chain deuteration and its application. Background Art

[0002] As a new type of solar energy technology, organic photovoltaic cells (OPVs) have received extensive attention due to their advantages such as light weight, flexibility, color tunability, and large-area printable preparation. With the rapid development of active layer donor-acceptor materials and the optimization of device structures, the power conversion efficiency (PCE) of organic photovoltaic devices has exceeded 20%, achieving rapid development.

[0003] The photoactive layer of an OPV cell consists of an organic semiconductor donor material and an acceptor material. Currently, high-efficiency organic photovoltaic devices usually adopt a combination system of a polymer donor material and a non-fullerene small molecule acceptor material. However, currently, the design of polymer donor materials mostly focuses on how to improve efficiency, and less attention is paid to the research on device stability, resulting in a serious lag in the research on the stability of OPV devices compared to the research on the improvement of the power conversion efficiency of devices.

[0004] Polymer donor materials will undergo chemical reactions and degrade under oxygen and light. Although effective encapsulation can block the intrusion of oxygen and moisture into the device, slowing down the photodegradation rate of the polymer donor in an oxygen-free environment, the chemical structure reorganization still continues to occur, thus affecting the stability of the device. Research shows that the photochemical degradation of polymer donor materials mainly stems from two types of molecular-level structural evolutions: the side-chain hydrogen abstraction mechanism and the main-chain-side group dissociation mechanism. Under photoexcitation conditions, C-H bonds at specific positions in the alkyl side chain (such as the α-position and β-position) are preferentially broken, and the generated active free radicals not only initiate molecular chain crosslinking but also lead to the configurational distortion of the conjugated main chain. On the other hand, the chemical bond connecting the conjugated backbone and the functional side group breaks under the action of photoinduced homolysis, and this dissociation process directly destroys the electron transport network of the material and generates structural defects. The inherent strength differences of different chemical bonds (such as bond order parameters) are the key to determining the degradation tendency. Materials with weaker bond energies will accumulate higher concentrations of free radical species under continuous light illumination, thereby accelerating the decay of device performance.

[0005] Therefore, how to develop high-efficiency and stable polymer donor materials is crucial for the development of the industrial application of organic photovoltaics. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a polymer material with side-chain deuteration, which can effectively improve the stability of the device when used as a donor material in an organic photovoltaic device.

[0007] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] A polymer with deuterated side chains, comprising repeating units represented by the general formula (I):

[0009]

[0010] Wherein:

[0011] a is independently selected from 0, 1 or 2; b is independently selected from 0, 1 or 2;

[0012] Ar1, Ar2, Ar3 are independently selected from substituted or unsubstituted heteroaromatic groups having 5 - 30 ring atoms, or substituted or unsubstituted aromatic groups having 6 - 30 carbon atoms;

[0013] Ar4, Ar5 are independently selected from substituted or unsubstituted heteroaromatic groups having 5 - 10 ring atoms, or substituted or unsubstituted aromatic groups having 6 - 10 carbon atoms;

[0014] R0, R1 are independently selected from -H or -D, and at least one of R0 and R1 is selected from -D;

[0015] Each occurrence of R2, R3 is independently selected from a straight-chain or branched-chain alkyl group having 1 - 10 carbon atoms, or a straight-chain or branched-chain alkyl group having 1 - 10 carbon atoms substituted by one deuterium (-D) or multiple deuteriums;

[0016] Each occurrence of Y is independently selected from O, S or Se;

[0017] Each occurrence of X is independently selected from CR4 or N;

[0018] Each occurrence of R4 is independently selected from -H, -D, or a straight-chain alkyl group having 1 - 10 carbon atoms, or a branched-chain alkyl group having 3 - 10 carbon atoms;

[0019] The term "substituted or unsubstituted" means that the defined group is unsubstituted or substituted by one or more substituents R, and each occurrence of R is independently selected from: -D, -F, -Cl, -Br, -I, -CN, a straight-chain alkyl group having 1 - 30 carbon atoms, a branched-chain alkyl group having 3 - 30 carbon atoms, a straight-chain alkoxy group having 1 - 30 carbon atoms, a branched-chain alkoxy group having 3 - 30 carbon atoms, a straight-chain alkylthio group having 1 - 30 carbon atoms, a branched-chain alkylthio group having 3 - 30 carbon atoms, an ester group having 1 - 30 carbon atoms, a heteroaromatic group having 5 - 20 ring atoms, or an aromatic group having 6 - 20 carbon atoms, and groups formed by the combination of the above groups;

[0020] * represents the connection site.

[0021] The present invention further relates to a mixture, which comprises the polymer with deuterated side chains as described above.

[0022] The present invention further relates to a composition comprising the polymer or mixture with side-chain deuteration as described above, and at least one organic solvent.

[0023] The present invention further relates to an organic photovoltaic device comprising the polymer or mixture with side-chain deuteration as described above.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0025] By introducing deuterium atoms at the α-site and / or β-site of the branched chain in the present invention, due to the "heavy atom" effect, the C-D (deuterium) bond has a lower vibration frequency and zero-point energy compared with the C-H bond, resulting in a higher dissociation energy of the C-D (deuterium) bond and making the bond more difficult to break, thereby enhancing the molecular stability, effectively alleviating the photo-degradation rate of the polymer donor material in the light environment. When applied to an organic photovoltaic device, it can effectively improve the device life and greatly promote the development of organic photovoltaics in stability research. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0027] Figure 1 It is a schematic structural diagram of the device embodiment of the present invention.

[0028] Wherein: 10 - substrate, 101 - anode, 102 - anode buffer layer, 103 - photoactive layer, 104 - cathode buffer layer, 105 - cathode.

[0029] Figure 2 It is the GPC spectrum of the polymer (P4) described in Polymer Synthesis Example 3.

[0030] Figure 3 It is the GPC spectrum of the polymer (P28) described in Polymer Synthesis Example 6. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0031] The following embodiments are provided to better further understand the present invention. It is not limited to the best embodiment, and does not limit the content and protection scope of the present invention. Any product obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior art features that is the same as or similar to the present invention falls within the protection scope of the present invention.

[0032] The terms "and / or", "or / and", and "and / or" used in this article include any one of two or more related listed items, and also include any and all combinations of related listed items, and the arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or", "or / and", and "and / or", it should be understood that in this application, the technical solution undoubtedly includes technical solutions that are all connected by "logical and", and undoubtedly includes technical solutions that are all connected by "logical or". For example, "A and / or B" includes three parallel solutions of A, B and A+B. For example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, the technical solution that is all connected by "logical OR"), and also includes any and all combinations of A, B, C, and D, that is, the combination of any two or any three of A, B, C, and D, and also includes the combination of four of A, B, C, and D (that is, the technical solution that is all connected by "logical AND").

[0033] In the present invention, organic photovoltaic device, organic photovoltaic cell, organic solar cell, OPV and OSC have the same meaning and can be interchangeable.

[0034] In the present invention, photoactive layer and active layer have the same meaning and can be interchanged.

[0035] In the present invention, when a group contains multiple substituents with the same symbol, the substituents may be the same or different from each other. The six Rs on the benzene ring may be the same as or different from each other.

[0036] In the present invention, "substituted" means that one or more hydrogen atoms in a substituted group are replaced by a substituent.

[0037] In the present invention, the "number of ring atoms" refers to the number of atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) obtained by bonding atoms to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring atoms. The same applies to the "number of ring atoms" described below unless otherwise specified. In an aromatic group, the number of ring atoms is the same as the number of carbon atoms; in a heteroaromatic group, the number of ring atoms is the number of carbon atoms plus the number of heteroatoms; for example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, the number of ring atoms of a quinoline ring is 10, the number of ring atoms of a thienyl group is 5, the number of ring atoms of a thienothiophene group is 8, The number of ring atoms is 16. The number of ring atoms is 15.

[0038] In the present invention, the "aromatic group" refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aromatic group can be a monocyclic aryl group (such as a phenyl group) or a polycyclic aryl group. In other words, the aromatic group can be a monocyclic aromatic group, a fused-ring aromatic group, two or more monocyclic aromatic groups conjugated through carbon-carbon bonds, a monocyclic aromatic group and a fused-ring aromatic group conjugated through carbon-carbon bonds, or two or more fused-ring aromatic groups conjugated through carbon-carbon bonds. That is, unless otherwise specified, two or more aromatic groups conjugated through carbon-carbon bonds can also be regarded as the aromatic groups of the present application. Preferably, the aromatic group is selected from those having 6-30 C atoms; further preferably, selected from those having 6-20 C atoms; further preferably, selected from those having 6-10 C atoms; the aromatic groups include but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, tetracenyl, fluorenyl, binaphthylenyl, acenaphthylenyl, and their derivatives.

[0039] In the present invention, the "heteroaromatic group" is a heteroaromatic ring or its derivative containing 1, 2, 3, 4, 5, 6 or more heteroatoms in the ring, and the heteroatoms can be at least one of B, O, N, P, Si, Se, and S. The heteroaromatic group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group. As used herein, the term "heteroaromatic group" also includes a group formed by the fusion of one or more heteroaromatic groups with one or more aromatic rings, aliphatic rings, or heterocyclic rings (for example, the group described in the present invention belongs to the heteroaromatic group, but is not limited thereto). Preferably, the heteroaromatic group is selected from those having 5-30 ring atoms; further preferably, selected from those having 5-20 ring atoms; further preferably, selected from those having 5-10 ring atoms.

[0040] In the present invention, the number of carbon atoms of the straight-chain alkyl group can be 1 to 30, 1 to 20, 1 to 16, 1 to 10, or 1 to 6. The number of carbon atoms of the branched-chain alkyl group can be 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Non-limiting examples of the straight-chain alkyl group include methyl (-CH3), ethyl (-C2H5), n-propyl (-C3H7), n-butyl (-C4H9), n-pentyl (-C5H 11 ), n-hexyl (-C6H 13 ), n-heptyl (-C7H 15 ), n-octyl (-C8H 17 ), n-nonyl (-C9H 19 ), -C 10 H 21 , -C 11 H 23 , -C 12 H25 ,-C 13 H 27 ,-C 14 H 29 ,-C 15 H 31 ,-C 16 H 33 . Non-limiting examples of branched-chain alkyl groups include: isopropyl, branched-chain alkyl groups containing 4 carbon atoms, branched-chain alkyl groups containing 5 carbon atoms, branched-chain alkyl groups containing 6 carbon atoms, branched-chain alkyl groups containing 7 carbon atoms, branched-chain alkyl groups containing 8 carbon atoms, branched-chain alkyl groups containing 9 carbon atoms, branched-chain alkyl groups containing 10 carbon atoms, branched-chain alkyl groups containing 11 carbon atoms, branched-chain alkyl groups containing 12 carbon atoms, branched-chain alkyl groups containing 13 carbon atoms, branched-chain alkyl groups containing 14 carbon atoms, branched-chain alkyl groups containing 15 carbon atoms, branched-chain alkyl groups containing 16 carbon atoms.

[0041] The term "alkoxy" refers to a group having the structure "-O-alkyl", i.e., the alkyl group as defined above is connected to other groups via an oxygen atom. The straight-chain alkoxy represents that the alkyl group in "-O-alkyl" is selected from straight-chain alkyl groups, where the number of carbon atoms in the straight-chain alkyl group can be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkoxy represents that the alkyl group in "-O-alkyl" is selected from branched-chain alkyl groups, where the number of carbon atoms in the branched-chain alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6.

[0042] The term "alkylthio" refers to a group having the structure "-S-alkyl", i.e., the alkyl group as defined above is connected to other groups via a sulfur atom. The straight-chain alkylthio represents that the alkyl group in "-S-alkyl" is selected from straight-chain alkyl groups, where the number of carbon atoms in the straight-chain alkyl group can be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkylthio represents that the alkyl group in "-S-alkyl" is selected from branched-chain alkyl groups, where the number of carbon atoms in the branched-chain alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6.

[0043] The term "ester group" refers to a group having the structure "-C(=O)O-alkyl", i.e., the alkyl group as defined above is connected to other groups via -C(=O)O-. The alkyl group can be selected from straight-chain or branched-chain alkyl groups, and the further definitions of straight-chain or branched-chain alkyl groups are the same as those shown above.

[0044] In the present invention, when the connection site is not specified in a group, it means that any optional connection site in the group can be used as the connection site.

[0045] In the present invention, the expression "independently selected from" for one or more groups means that when one or more groups appear simultaneously and at multiple positions in a compound, they are all independently selected and can be the same or different.

[0046] In the present invention, the single bond to which the substituent is attached passes through the corresponding ring, indicating that the substituent can be connected to any optional position of the ring. For example in , R is connected to any substitutable site of the benzene ring.

[0047] In the process of describing the structural elements of the present invention, words such as "comprising" or "including" used in the present invention mean that the devices or materials appearing before the word cover the devices or materials and their equivalents listed after the word, without excluding other devices or materials.

[0048] In the description of the present invention, it should be understood that the orientation or positional relationship indicated by terms such as "upper", "lower", "between layers", etc. is based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship in which the organic solar cell device is customarily placed during use, or the orientation or positional relationship commonly understood by those skilled in the art. It is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of the present invention.

[0049] In the present invention, "its combination", "any combination thereof", "any combination mode thereof", "combination", etc. include all suitable combination modes of any two, any three or any three or more groups among the listed groups.

[0050] In the present invention, words such as "further", "furthermore", "specially", "preferably", etc. are used for descriptive purposes and indicate differences in content, but should not be construed as a limitation on the protection scope of the present invention.

[0051] In the present invention, "optionally", "optional", "optional" mean that it can be either present or absent, that is, it refers to any one of the two alternative schemes of "present" or "absent". If "optional" appears in multiple places in a technical solution, without special instructions and without contradictions or mutual constraints, each "optional" is independent of each other.

[0052] In the present invention, among the technical features described in an open-ended manner, it includes a closed technical solution composed of the listed features, and also includes an open-ended technical solution containing the listed features.

[0053] The first aspect of the present invention relates to a polymer with side-chain deuteration, comprising repeating units represented by the general formula (I):

[0054]

[0055] Wherein:

[0056] a is selected from 0, 1 or 2; b is selected from 0, 1 or 2;

[0057] Ar1, Ar2, and Ar3 are independently selected from substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms, or substituted or unsubstituted aromatic groups having 6 to 30 carbon atoms;

[0058] Ar4 and Ar5 are independently selected from substituted or unsubstituted heteroaromatic groups having 5 to 10 ring atoms, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms;

[0059] R0 and R1 are independently selected from -H or -D, and at least one of R0 and R1 is selected from -D;

[0060] Each occurrence of R2 and R3 is independently selected from straight-chain or branched-chain alkyl groups having 1 to 10 carbon atoms, or straight-chain or branched-chain alkyl groups having 1 to 10 carbon atoms substituted with one deuterium (-D) or multiple deuteriums;

[0061] Each occurrence of Y is independently selected from O, S, or Se;

[0062] Each occurrence of X is independently selected from CR4 or N;

[0063] Each occurrence of R4 is independently selected from hydrogen, deuterium, or straight-chain alkyl groups having 1 to 10 carbon atoms, or branched-chain alkyl groups having 3 to 10 carbon atoms;

[0064] The term "substituted or unsubstituted" means that the defined group is unsubstituted or substituted with one or more substituents R, and each occurrence of R is independently selected from: -D, -F, -Cl, -Br, -I, -CN, straight-chain alkyl groups having 1 to 30 carbon atoms, branched-chain alkyl groups having 3 to 30 carbon atoms, straight-chain alkoxy groups having 1 to 30 carbon atoms, branched-chain alkoxy groups having 3 to 30 carbon atoms, straight-chain alkylthio groups having 1 to 30 carbon atoms, branched-chain alkylthio groups having 3 to 30 carbon atoms, ester groups having 1 to 30 carbon atoms, heteroaromatic groups having 5 to 20 ring atoms, or aromatic groups having 6 to 20 carbon atoms, and groups formed by combination of the above groups;

[0065] * represents the connection site.

[0066] Further, each occurrence of R is independently selected from: -D, -F, -Cl, -CN, straight-chain alkyl groups having 1 to 20 carbon atoms, branched-chain alkyl groups having 3 to 20 carbon atoms, straight-chain alkoxy groups having 1 to 20 carbon atoms, branched-chain alkoxy groups having 3 to 20 carbon atoms, straight-chain alkylthio groups having 1 to 20 carbon atoms, branched-chain alkylthio groups having 3 to 20 carbon atoms, ester groups having 1 to 20 carbon atoms, heteroaromatic groups having 5 to 10 ring atoms, or aromatic groups having 6 to 10 carbon atoms, and groups formed by combination of the above groups.

[0067] Further, the polymer with side chain deuteration comprises repeating units represented by general formula (II-1), general formula (II-2), or general formula (II-3):

[0068]

[0069] In an alternative embodiment, Ar4 and Ar5 are selected from wherein: each occurrence of V is independently selected from CR5 or N; each occurrence of R5 is independently selected from hydrogen, deuterium, -F, -Cl, -CN, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms, a straight-chain alkoxy group having 1 to 10 carbon atoms, a branched-chain alkoxy group having 3 to 10 carbon atoms, a straight-chain alkylthio group having 1 to 10 carbon atoms, a branched-chain alkylthio group having 3 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, and a group formed by combining the above groups.

[0070] Further, each occurrence of R5 is independently selected from hydrogen, deuterium, -F, -Cl, -CN, -CF3, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms, a straight-chain alkyl group having 1 to 10 carbon atoms substituted with one or more deuteriums, or a branched-chain alkyl group having 3 to 10 carbon atoms substituted with one or more deuteriums.

[0071] Further, the is selected from any of the following groups:

[0072]

[0073] Preferably, in (A-1)-(A-6), each occurrence of R5 is independently selected from hydrogen, deuterium, -F, -Cl, -CN, -CF3, -CH3, or -CD3.

[0074] Further, in (A-1)-(A-6), V is selected from N, C-H, C-F, or C-Cl.

[0075] Even further, the is selected from any of the following groups:

[0076]

[0077]

[0078] In an alternative embodiment, each occurrence of R2 and R3 is independently selected from a straight-chain alkyl group having 1 to 6 carbon atoms, or a branched-chain alkyl group having 3 to 6 carbon atoms, or a straight-chain alkyl group having 1 to 6 carbon atoms substituted with one deuterium (-D) or more deuteriums, or a branched-chain alkyl group having 3 to 6 carbon atoms substituted with one deuterium (-D) or more deuteriums.

[0079] In a specific embodiment, R2 and R3 are independently selected from -C2H5, -C4H9, -C6H 13 , -C2D5, -C4D9 or -C6D 13 .

[0080] In a specific embodiment, Y is selected from S.

[0081] In one embodiment, Ar1 is independently selected from heteroaromatic groups having 5 - 30 ring atoms which are substituted or unsubstituted by R a , where each occurrence of R a is independently selected from -D, -F, -Cl, -Br, -I, -CN, straight-chain alkyl groups having 1 - 20 carbon atoms, branched-chain alkyl groups having 3 - 20 carbon atoms, straight-chain alkoxy groups having 1 - 20 carbon atoms, branched-chain alkoxy groups having 3 - 20 carbon atoms, straight-chain alkylthio groups having 1 - 20 carbon atoms, branched-chain alkylthio groups having 3 - 20 carbon atoms, ester groups having 1 - 20 carbon atoms, heteroaromatic groups having 5 - 20 ring atoms, or aromatic groups having 6 - 20 carbon atoms, and groups formed by combinations of the above groups.

[0082] Further, Ar1 is independently selected from any one of the following groups:

[0083]

[0084] wherein: each occurrence of R6 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, straight-chain alkyl groups having 1 - 20 carbon atoms, branched-chain alkyl groups having 3 - 20 carbon atoms, straight-chain alkoxy groups having 1 - 20 carbon atoms, branched-chain alkoxy groups having 3 - 20 carbon atoms, straight-chain alkylthio groups having 1 - 20 carbon atoms, branched-chain alkylthio groups having 3 - 20 carbon atoms, ester groups having 1 - 20 carbon atoms, heteroaromatic groups having 5 - 20 ring atoms, or aromatic groups having 6 - 20 carbon atoms, and groups formed by combinations of the above groups.

[0085] In an alternative embodiment, each occurrence of R6 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, straight-chain alkyl groups having 1 - 10 carbon atoms, branched-chain alkyl groups having 3 - 10 carbon atoms, straight-chain alkyl groups having 1 - 10 carbon atoms substituted by one deuterium or multiple deuteriums, branched-chain alkyl groups having 3 - 10 carbon atoms substituted by one deuterium or multiple deuteriums, straight-chain alkoxy groups having 1 - 10 carbon atoms, branched-chain alkoxy groups having 3 - 10 carbon atoms, straight-chain alkylthio groups having 1 - 10 carbon atoms, branched-chain alkylthio groups having 3 - 10 carbon atoms, or ester groups having 1 - 10 carbon atoms.

[0086] In an optional embodiment, Ar1 is independently selected from any of the following groups:

[0087]

[0088] In one embodiment, Ar2 and Ar3 are independently selected from wherein: each occurrence of R7 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a branched-chain alkoxy group having 3 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a branched-chain alkylthio group having 3 to 20 carbon atoms, an ester group having 1 to 20 carbon atoms, and a group formed by combining the above groups.

[0089] Preferably, each occurrence of R7 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a straight-chain alkyl group having 1 to 20 carbon atoms substituted with one or more deuteriums, or a branched-chain alkyl group having 3 to 20 carbon atoms substituted with one or more deuteriums.

[0090] In an optional embodiment, the is selected from

[0091] Furthermore, the is selected from any of the following groups:

[0092]

[0093] wherein: each occurrence of R8, R9, R 10 is independently selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a straight-chain alkyl group having 1 to 10 carbon atoms substituted with one or more deuteriums.

[0094] In a specific embodiment, each occurrence of R9, R 10 is independently selected from -C2H5, -C4H9, -C6H 13 , -C2D5, -C4D9 or -C6D 13 .

[0095] In an optional embodiment, the is selected from the following groups:

[0096]

[0097] In one embodiment, a is selected from 0 or 1.

[0098] In one embodiment, b is selected from 0 or 1.

[0099] In an alternative embodiment, (D-1) is selected from

[0100] In an alternative embodiment, (D-2) is selected from

[0101] In an alternative embodiment, (D-3) is selected from

[0102] In an alternative embodiment, (D-4) is selected from

[0103] In an alternative embodiment, (D-5) is selected from

[0104] In an alternative embodiment, (D-6) is selected from Preferably, the is selected from any group of (C-10)-(C-12).

[0105] In an alternative embodiment, in the repeating unit represented by the general formula (I) is selected from any group of (B-1)-(B-18); the is selected from any group of (D-1)-(D-6).

[0106] In one embodiment, for the polymer with side-chain deuteration according to the present invention, the polymer is a homopolymer and the polymer contains only one kind of repeating unit.

[0107] In one embodiment, for the polymer with side-chain deuteration according to the present invention, the polymer is a copolymer. Further, the polymer contains at least two different repeating units. Still further, the polymer is a random copolymer.

[0108] In a specific embodiment, the polymer with side-chain deuteration according to the present invention is selected from the following structures, but not limited thereto:

[0109]

[0110]

[0111]

[0112] Wherein: n represents the number of repeating units, and n is selected from integers greater than or equal to 2.

[0113] In one embodiment, n is selected from integers of 5 to 1000.

[0114] In one embodiment, for the polymer according to the present invention, the number-average molecular weight (Mn) of the polymer is selected from between 10,000 and 1,000,000. Further, the number-average molecular weight (Mn) of the polymer is selected from between 10,000 and 100,000. Further, the number-average molecular weight (Mn) of the polymer is selected from between 20,000 and 60,000.

[0115] A second aspect of the present invention relates to a mixture, which comprises the polymer with deuterated side chains as described in the first aspect.

[0116] Further, the mixture further comprises another organic functional material, and the another organic functional material is selected from a photoactive layer donor material or a photoactive layer acceptor material.

[0117] In an alternative embodiment, the another organic functional material is selected from photoactive layer acceptor materials. Further, the photoactive layer acceptor material is selected from fullerene acceptor materials or non-fullerene acceptor materials.

[0118] In one embodiment, the non-fullerene acceptor material can be selected from one or more of the following: ITIC configuration-based acceptor materials, including but not limited to: ITIC, ITIC-4F, ITIC-4Cl, ITCC, ITCC-Cl, etc.; Y-type receptor materials, including but not limited to: Y6, L8-BO, BTP-eC9, N3, N4, Y6-O, BTP-H2, PY-IT, etc.; the fullerene acceptor materials, including but not limited to: PC61BM (methyl [6,6]-phenyl C61 butyrate), PC71BM (methyl [6,6]-phenyl C71 butyrate), indene-containing fullerenes, etc. For the selection of non-fullerene acceptor materials, reference can also be further made to the literature: Chem.Rev.2022, 122, 18, 14180–14274, doi:10.1021 / acs.chemrev.1c00955.

[0119] A third aspect of the present invention relates to a composition, which comprises the polymer with deuterated side chains as described in the first aspect or the mixture as described in the second aspect, and at least one organic solvent.

[0120] The organic solvent is selected from: tetralin, 1,5-dimethyltetrahydrofuran, methyltetrahydrofuran, decalin, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, 1,4-dimethylnaphthalene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, acetophenone, diphenyl ether, 2-methylthiophene, 3-methylthiophene, chloromethane, dichloromethane, chloroform, dichloroethylene, trichloroethylene, 1,2-trichlorotrifluoroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, carbon tetrachloride, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, 1,4-dioxane, N-methylpyrrolidone, acetone, cyclopentanone, cyclohexanone, methyl ethyl ketone, ethyl acetate, n-butyl acetate, carbon disulfide, carbon tetrachloride, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, indane, methyl benzoate, ethyl benzoate, acetonitrile, hexamethylphosphoramide, one of them, or a mixture of two or more.

[0121] Further, the composition may further include additives for adjusting viscosity, adjusting film-forming properties, improving adhesion, etc. The additives may be selected from but not limited to 1,8-diiodooctane (DIO), diphenyl ether (DPE), anthracene, 1,4-diiodobenzene (DIB), 1,3-dibromo-5-chlorobenzene (DBCl), 3,5-dichlorobromobenzene (DCBB), 1-chloronaphthalene (1-CN), 1,3,5-tribromobenzene (TBB), etc., but not limited thereto.

[0122] The fourth aspect of the present invention relates to an organic photovoltaic device, which comprises a polymer with side-chain deuteration as described in the first aspect or a mixture as described in the second aspect.

[0123] Further, the organic photovoltaic device comprises a cathode, an anode, and a photoactive layer located between the cathode and the anode, and the photoactive layer comprises a polymer with side-chain deuteration as described in the first aspect or a mixture as described in the second aspect.

[0124] In one embodiment, the photoactive layer material comprises a photoactive layer donor material and a photoactive layer acceptor material, and the photoactive layer donor material comprises a polymer with side-chain deuteration as described in the first aspect.

[0125] The photoactive layer acceptor material is selected from fullerene acceptor materials or non-fullerene acceptor materials. Further description of the photoactive layer acceptor material is the same as that described above.

[0126] The preparation method of the photoactive layer material solution is as follows: a photoactive layer donor material and an acceptor material are dissolved in an organic solvent according to a certain mass ratio, and stirred evenly and fully dissolved to obtain a photoactive layer solution. The further description of the organic solvent is the same as that described above.

[0127] The above solution is used to prepare the photoactive layer by a printing or coating preparation method. The printing or coating preparation method can be, but is not limited to, inkjet printing, gravure printing, spraying, letterpress printing, screen printing, dip coating, spin coating, blade coating, roller printing, reverse roll printing, lithographic printing, flexographic printing, rotary printing, spraying, brush coating, pad printing, slot die coating, etc. Preferred are slot coating, spin coating and inkjet printing.

[0128] The mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is preferably 1:0.8 to 1:1.5; further, the mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is preferably 1:1 to 1:1.5; the mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is preferably 1:1 to 1:1.2.

[0129] The concentration of the photoactive layer donor material in the organic solvent is preferably 3 to 15 mg / mL; further, the concentration of the photoactive layer donor material in the organic solvent is preferably 4 to 10 mg / mL.

[0130] At least one of the anode and the cathode is transparent or semi-transparent to facilitate the incidence of light. The materials used to prepare the electrodes can be selected from metals, such as vanadium (V), chromium (Cr), zinc (Zn), silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), palladium (Pd), or alloys of the above metals, etc.; conductive nanomaterials, such as metal nanowires, nanoparticle slurries, graphene, carbon nanotubes, etc.; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.; combinations of metals and oxides, such as ZnO∶Al or SnO2∶Sb, etc.; and conductive polymers, such as PEDOT:PSS, polypyrrole and polyaniline, etc.; or materials with a multilayer structure, such as LiF / Al, LiO2 / Al, LiF / Fe, MoO3 / Al, Al∶Li, Al∶BaF2 and Al∶BaF2∶Ba, etc., but not limited thereto.

[0131] In one embodiment, the organic photovoltaic cell is stacked with an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer and a cathode from bottom to top, and contains a polymer with side-chain deuteration as described in the first aspect or a mixture as described in the second aspect.

[0132] Preferably, the cathode buffer layer material can be selected from metal complexes with low work function, metal oxides, metal salts, etc., such as metal complexes of 8-hydroxyquinoline, complexes containing Alq3, metal complexes containing Liq, LiF, Ca, titanium oxide (TiO x ), zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc.; it can also be a polymer material, such as PFN-Br or PFN or PDINN or PDINO or PNDIT-F3N-Br or PNDIT-F3N, etc., but not limited thereto.

[0133] The anode buffer layer material is selected from PEDOT:PSS, molybdenum oxide (MoO x ), vanadium pentoxide (V2O5), nickel oxide (NiO), tungsten oxide (WO x , preferably, x is selected from 2 or 3), small molecule self-assembled materials such as 2PACz, MeO-2PACz, CBz-2Ph, etc., but not limited thereto.

[0134] It should be noted that in order to improve the performance of the organic photovoltaic cell device, the organic photovoltaic cell may further include other functional layers, including but not limited to charge blocking layers and charge transport layers.

[0135] Furthermore, the organic photovoltaic cell also includes a substrate. In one embodiment, the substrate is disposed on one side of the anode and on a different side from the photoactive layer. In another embodiment, the substrate is disposed on one side of the cathode and on a different side from the photoactive layer.

[0136] In one embodiment, as the substrate, a substrate with excellent transparency, surface smoothness, ease of operation, and water resistance can be used. Specifically, a glass substrate, a thin film glass substrate, or a transparent plastic substrate can be used. The plastic substrate may include a single-layer or multi-layer film, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polyimide (PI), parylene, etc., but not limited thereto, and substrates commonly used in organic solar cells can also be used.

[0137] The organic photovoltaic cell according to the present invention is mainly used in fields such as indoor photovoltaics, wearable devices, intelligent Internet of Things, smart homes, smart agriculture, building photovoltaics, new energy vehicles, etc.

[0138] Polymer Synthesis Examples

[0139] The following examples facilitate a better understanding of the disclosure of the present invention and are not intended to limit it in any way. The experimental methods used in the following examples are all conventional methods unless otherwise specified, and the materials, reagents, etc. used are all prior art and can be obtained from commercial sources unless otherwise specified.

[0140] Synthesis of Intermediate

[0141] Synthesis of Intermediate M-1:

[0142]

[0143] Synthesis of Compound 1-1:

[0144] Accurately weigh compound 2-ethylhexanoic acid (14.4 g, 100 mmol) into a 250 mL two-necked flask, add 100 mL of anhydrous toluene, replace nitrogen three times, then add thionyl chloride (23.8 g, 200 mmol), and then add 1 mL of anhydrous DMF. Heat the mixture to 100 °C and react for 6 h. After the raw materials are completely reacted, cool the mixture to room temperature, and then distill off the excess solvent under reduced pressure; dissolve the crude product in anhydrous dichloromethane, and then distill off the excess solvent under reduced pressure. Repeat the operation three times. Dissolve the obtained crude product in anhydrous diethyl ether and transfer it to a dried 250 mL three-necked flask. Replace nitrogen three times, then cool the mixture to -10 °C, and then slowly add LiAlD4 (16.8 g, 400 mol) to the reaction system. Keep the reaction at low temperature for 24 h. After the reaction is completed, filter the mixture. Wash the filter cake with anhydrous diethyl ether three times, combine the organic phases, and distill off the excess solvent under reduced pressure to obtain about 11.7 g of the crude product of compound 1-1.

[0145] Synthesis of Compound 1-2:

[0146] Weigh the above-mentioned crude product of compound 1-1 (11.5 g, 80 mmol) and carbon tetrabromide (53.1 g, 160 mmol) and add them to a 500 mL dry three-necked flask in sequence. Add 200 mL of anhydrous THF, replace nitrogen three times. Weigh triphenylphosphine (42.1 g, 160 mmol) and dissolve it in 80 mL of anhydrous THF, and then slowly add it dropwise to the reaction system. React at room temperature overnight. After the reaction is completed, pour the reaction mixture into ice water, and then extract it with EA. Combine the organic phases, dry them over anhydrous sodium sulfate, and then distill off the excess solvent under reduced pressure. Perform silica gel column chromatography with the eluent of PE:DCM = 30:1 (volume ratio) to obtain compound 1-2 as a colorless transparent oily substance, about 8.6 g, and the yield is 55.1%.

[0147] Synthesis of Compound 1-3:

[0148] Accurately weigh 3-fluorothiophene (2.04 g, 20 mmol) into a 100 mL three-necked flask, add about 30 mL of anhydrous THF. After displacing nitrogen three times, cool the temperature to -80 °C, and then slowly dropwise add LDA (2 M, 11 mL) to the system. After maintaining the low-temperature reaction for 1 h, slowly dropwise add compound 1-2 (3.9 g, 20 mmol) to the system. Naturally warm up to room temperature and react overnight. Add aqueous ammonium chloride solution to the reaction solution, and then extract with ethyl acetate three times. Combine the organic phases, dry over anhydrous sodium sulfate, and then perform silica gel sample-mixing column chromatography. The eluent is PE to obtain about 3.24 g of compound 1-3, yield: 74.8%. MS: 216.54.

[0149] Synthesis of compound 1-5:

[0150] Accurately weigh compound 1-3 (3.03 g, 14 mmol) and add it to a 100 mL three-necked flask. Add about 50 mL of anhydrous THF. After displacing nitrogen three times, cool the temperature to -80 °C, and then slowly dropwise add LDA (2 M, 7.7 mL) to the system. After maintaining the low-temperature reaction for 1 h, slowly add compound 1-4 (1.32 g, 6 mmol) to the system. After reacting at room temperature for two hours, add a dilute hydrochloric acid solution of stannous chloride (1.79 g, 20 mmol dissolved in 20 mL of 10% hydrochloric acid) to the reaction system, and heat to 50 °C and react overnight. After the reaction solution cools to room temperature, quench it with brine, and then extract with PE. Combine the organic phases, dry over anhydrous sodium sulfate, and then perform silica gel sample-mixing column chromatography. The eluent is n-hexane to obtain about 3.02 g of compound 1-5, yield: 81.3%. MS: 619.21.

[0151] Synthesis of compound M-1:

[0152] Accurately weigh compound 1-5 (2.48 g, 4 mmol) and add it to a 100 mL three-necked flask. Add about 30 mL of anhydrous THF. After displacing nitrogen three times, cool the temperature to -80 °C, and then slowly dropwise add LDA (2 M, 7.7 mL) to the system. Maintain the low-temperature reaction for 1 h, and then add trimethyltin chloride (2.39 g, 12 mmol) to the reaction system. Naturally warm up to room temperature and react overnight. Add saturated potassium fluoride solution and stir for 2 hours. Extract with petroleum ether until there is no product in the aqueous phase. Combine the organic phases, dry over anhydrous sodium sulfate and concentrate. Recrystallize by heating with isopropanol to 70 °C to obtain about 2.95 g of compound M-1, yield: 78.1%. MS: 944.73.

[0153] Synthesis of intermediate M-2:

[0154]

[0155] Synthesis of compound 2-1

[0156] Accurately weigh 2-ethylhexanol (39 g, 300 mmol) of the compound into a 1000 mL pressure-resistant flask, add the catalyst MnBrPNPiPr(CO)2 (0.39 g), about 180 mL of D2O, and NaOH (1.2 g, 30 mmol) under nitrogen protection, and then heat to 120 °C for reaction for 12 h. After the reaction is completed, extract with ethyl acetate, combine the organic phases, dry over anhydrous sodium sulfate, and then distill under reduced pressure to remove the excess solvent to obtain about 31.8 g of the crude product of compound 2-1.

[0157] Synthesis of compound 2-2:

[0158] Weigh the crude product of the above compound 2-1 (28.2 g, 210 mmol) and carbon tetrabromide (139.2 g, 420 mmol) and add them to a 2000 mL dry three-necked flask in sequence. Add 600 mL of anhydrous THF, displace nitrogen three times. Weigh another triphenylphosphine (110.5 g, 420 mmol), dissolve it with 240 mL of anhydrous THF, and slowly add it dropwise to the reaction system. React at room temperature overnight. After the reaction is completed, pour it into ice water, then extract with EA, combine the organic phases, dry over anhydrous sodium sulfate, distill under reduced pressure to remove the excess solvent, and perform silica gel column chromatography with the eluent of PE:DCM = 30:1 (volume ratio) to obtain compound 2-2 as a colorless transparent oily substance, about 19.86 g, yield: 48.3%.

[0159] Synthesis of compound 2-3

[0160] Accurately weigh 3-fluorothiophene (4.08 g, 40 mmol) into a 100 mL three-necked flask, add about 60 mL of anhydrous THF, displace nitrogen three times, cool down to -80 °C, and then slowly add dropwise LDA (2 M, 22 mL) to the system. After maintaining the low-temperature reaction for 1 h, slowly add dropwise compound 2-2 (7.84 g, 40 mmol) to the system, and naturally warm up to room temperature for reaction overnight. Add ammonium chloride aqueous solution to the reaction solution, and then extract three times with ethyl acetate. Combine the organic phases, dry over anhydrous sodium sulfate, and perform silica gel column chromatography with the eluent of PE to obtain about 6.56 g of compound 2-3, yield: 75.4%. MS: 217.53.

[0161] Synthesis of compound 2-4

[0162] Accurately weigh compound 2-3 (6.088 g, 28 mmol) and add it to a 250 mL three-necked flask. Add approximately 100 mL of anhydrous THF. After displacing nitrogen three times, cool the temperature to -80 °C. Then slowly add LDA (2 M, 15.4 mL) dropwise to the system. After maintaining the low-temperature reaction for 1 h, slowly add compound 1-4 (2.64 g, 12 mmol) to the system. After reacting at room temperature for two hours, add a dilute hydrochloric acid solution of stannous chloride (3.58 g, 40 mmol dissolved in 40 mL of 10% hydrochloric acid) to the reaction system and heat to 50 °C for reaction overnight. After the reaction solution cools to room temperature, quench it with brine, then extract with PE. Combine the organic phases, dry over anhydrous sodium sulfate, mix with silica gel for column chromatography, and use n-hexane as the eluent to obtain approximately 6.22 g of compound 2-4, yield: 83.5%. MS: 621.12.

[0163] Synthesis of Compound M-2

[0164] Accurately weigh compound 2-4 (4.96 g, 8 mmol) and add it to a 100 mL three-necked flask. Add approximately 60 mL of anhydrous THF. After displacing nitrogen three times, cool the temperature to -80 °C. Then slowly add LDA (2 M, 8.8 mL) dropwise to the system. After maintaining the low-temperature reaction for 1 h, add trimethyltin chloride (4.78 g, 24 mmol) to the reaction system and allow it to warm up to room temperature for reaction overnight. Add a saturated potassium fluoride solution and stir for 2 hours. Extract with petroleum ether until there is no product in the aqueous phase. Combine the organic phases, dry over anhydrous sodium sulfate, concentrate, and recrystallize by heating with isopropanol to 70 °C to obtain approximately 5.96 g of compound M-2, yield: 78.7%. MS: 946.88.

[0165] Synthesis of Intermediate M-3

[0166]

[0167] Synthesis of Compound 3-1

[0168] Accurately weigh 3-fluorothiophene (2.04 g, 20 mmol) into a 100 mL three-necked flask. Add approximately 30 mL of anhydrous THF. After displacing nitrogen three times, cool the temperature to -80 °C. Then slowly add LDA (2 M, 11 mL) dropwise to the system. After maintaining the low-temperature reaction for 1 h, slowly add 2-ethylhexyl bromide-d17 (4.2 g, 20 mmol) dropwise to the system and allow it to warm up to room temperature for reaction overnight. Add an aqueous ammonium chloride solution to the reaction solution, and then extract three times with ethyl acetate. Combine the organic phases, dry over anhydrous sodium sulfate, mix with silica gel for column chromatography, and use PE as the eluent to obtain approximately 3.68 g of compound 3-1, yield: 79.3%. MS: 231.96.

[0169] Synthesis of Compound 3-2

[0170] Accurately weigh compound 3-1 (3.25 g, 14 mmol) and add it to a 100 mL three-necked flask. Add approximately 50 mL of anhydrous THF. After displacing nitrogen three times, cool the temperature to -80 °C. Then slowly add LDA (2 M, 7.7 mL) dropwise to the system. After maintaining the low-temperature reaction for 1 h, slowly add compound 1-4 (1.32 g, 6 mmol) to the system. After reacting at room temperature for two hours, add a dilute hydrochloric acid solution of stannous chloride (1.79 g, 20 mmol dissolved in 20 mL of 10% hydrochloric acid) to the reaction system and heat to 50 °C for overnight reaction. After the reaction solution is cooled to room temperature, quench it with brine, then extract with PE. Combine the organic phases, dry over anhydrous sodium sulfate, mix with silica gel for column chromatography, and use n-hexane as the eluent to obtain approximately 3.17 g of compound 3-2, yield: 81.4%. MS: 649.45.

[0171] Synthesis of compound M-3

[0172] Accurately weigh compound 3-2 (2.6 g, 4 mmol) and add it to a 100 mL three-necked flask. Add approximately 30 mL of anhydrous THF. After displacing nitrogen three times, cool the temperature to -80 °C. Then slowly add LDA (2 M, 7.7 mL) dropwise to the system. Maintain the low-temperature reaction for 1 h, then add trimethyltin chloride (2.39 g, 12 mmol) to the reaction system and allow it to warm to room temperature for overnight reaction. Add a saturated potassium fluoride solution and stir for 2 hours. Extract with petroleum ether until there is no product in the aqueous phase. Combine the organic phases, dry over anhydrous sodium sulfate, concentrate, and recrystallize by heating to 70 °C with isopropanol to obtain approximately 3.02 g of compound M-3, yield: 77.5%. MS: 974.60.

[0173] Synthesis of intermediate M-4

[0174]

[0175] Synthesis of compound 4-1

[0176] Accurately weigh 3-chlorothiophene (2.37 g, 20 mmol) into a 100 mL three-necked flask. Add approximately 30 mL of anhydrous THF. After displacing nitrogen three times, cool the temperature to -80 °C. Then slowly add LDA (2 M, 11 mL) dropwise to the system. After maintaining the low-temperature reaction for 1 h, slowly add compound 2-2 (3.92 g, 20 mmol) dropwise to the system and allow it to warm to room temperature for overnight reaction. Add an aqueous ammonium chloride solution to the reaction solution, and then extract three times with ethyl acetate. Combine the organic phases, dry over anhydrous sodium sulfate, mix with silica gel for column chromatography, and use PE as the eluent to obtain approximately 3.45 g of compound 4-1, yield: 73.9%. MS: 233.47.

[0177] Synthesis of compound 4-2

[0178] Accurately weigh compound 4-1 (3.27 g, 14 mmol) and add it to a 100 mL three-necked flask. Add about 50 mL of anhydrous THF. After displacing nitrogen three times, cool the temperature to -80 °C. Then slowly add LDA (2 M, 7.7 mL) dropwise to the system. After maintaining the low-temperature reaction for 1 h, slowly add compound 1-4 (1.32 g, 6 mmol) to the system. After reacting at room temperature for two hours, add a dilute hydrochloric acid solution of stannous chloride (1.79 g, 20 mmol dissolved in 20 mL of 10% hydrochloric acid) to the reaction system and heat it to 50 °C for reaction overnight. After the reaction solution is cooled to room temperature, quench it with brine, then extract with PE. Combine the organic phases, dry over anhydrous sodium sulfate, mix with silica gel and perform column chromatography. The eluent is n-hexane to obtain about 3.16 g of compound 4-2, yield: 80.6%. MS: 653.62.

[0179] Synthesis of Compound M-4

[0180] Accurately weigh compound 4-2 (2.62 g, 4 mmol) and add it to a 100 mL three-necked flask. Add about 30 mL of anhydrous THF. After displacing nitrogen three times, cool the temperature to -80 °C. Then slowly add LDA (2 M, 7.7 mL) dropwise to the system. Maintain the low-temperature reaction for 1 h, then add trimethyltin chloride (2.39 g, 12 mmol) to the reaction system and allow it to warm up to room temperature for reaction overnight. Add a saturated potassium fluoride solution and stir for 2 hours. Extract with petroleum ether until there is no product in the aqueous phase. Combine the organic phases, dry over anhydrous sodium sulfate and concentrate. Recrystallize by heating with isopropanol to 70 °C to obtain about 2.98 g of compound M-4, yield: 76.1%. MS: 979.50.

[0181] Synthesis of Intermediate M-5

[0182]

[0183] Synthesis of Compound 5-1

[0184] Accurately weigh 3-bromothiophene (9.8 g, 60 mmol) into a 250 mL three-necked flask. Add about 100 mL of anhydrous THF. After displacing nitrogen three times, cool the temperature to -80 °C. Then slowly add n-BuLi (2.5 M, 24 mL) dropwise to the system. After maintaining the low-temperature reaction for 1 h, slowly add compound 2-2 (11.76 g, 60 mmol) dropwise to the system. Allow it to warm up to room temperature for reaction overnight. Add an aqueous ammonium chloride solution to the reaction solution, then extract it three times with ethyl acetate. Combine the organic phases, dry over anhydrous sodium sulfate, mix with silica gel and perform column chromatography. The eluent is PE to obtain about 8.04 g of compound 5-1, yield: 67.2%. MS: 199.45.

[0185] Synthesis of Compound 5-2

[0186] Accurately weigh compound 5-1 (6.0 g, 30 mmol) into a 250 mL three-necked flask, add about 90 mL of anhydrous THF. After displacing nitrogen three times, cool the temperature to -80 °C, and then slowly dropwise add n-BuLi (2.5 M, 12 mL) to the system. After maintaining the low-temperature reaction for 1 h, slowly dropwise add tributyltin chloride (19.5 g, 60 mmol) to the system. Naturally warm up to room temperature and react overnight. Add saturated potassium fluoride aqueous solution to the reaction solution, stir for half an hour and then extract three times with ethyl acetate. Combine the organic phases, dry over anhydrous sodium sulfate and then perform column chromatography on neutral alumina. The eluent is PE to obtain about 13.53 g of compound 5-2, yield: 92.2%. MS: 488.93.

[0187] Synthesis of compound 5-4

[0188] Accurately weigh compound 5-3 (1.6 g, 4 mmol) into a 100 mL three-necked flask, add 20 mL of anhydrous toluene, and then add compound 5-2 (3.9 g, 8 mmol). After displacing nitrogen three times, add Pd(PPh3)2Cl2 (0.14 g, 5%). Then heat up to 90 °C and react for 4 h. After the raw materials are completely reacted, quench with saturated potassium fluoride aqueous solution, extract with EA. Combine the organic phases, dry over anhydrous sodium sulfate and then perform column chromatography with silica gel sample mixing. The eluent is PE:THF = 3:1 (volume ratio) to obtain about 2.16 g of compound 5-4, yield: 84.7%. MS: 637.24.

[0189] Synthesis of compound M-5

[0190] Accurately weigh compound 5-4 (1.27 g, 2 mmol) and add it to a 100 mL two-necked flask, add 20 mL of chloroform. After displacing nitrogen three times, add NBS (0.75 g, 4.2 mmol), react at room temperature overnight. After the reaction is completed, quench with aqueous sodium sulfite solution and extract with ethyl acetate. Combine the organic phases, dry over anhydrous sodium sulfate and then perform column chromatography with silica gel sample mixing. The eluent is PE:THF = 3:1 (volume ratio) to obtain about 1.25 g of compound M-5, yield: 78.6%. MS: 794.67.

[0191] Synthesis of intermediate M-6

[0192]

[0193] Synthesis of compound M-6

[0194] Accurately weigh compound 6-1 (1.62 g, 4 mmol) into a 100 mL three-necked flask, add 20 mL of anhydrous toluene, then add compound 5-2 (3.9 g, 8 mmol). After displacing nitrogen three times, add Pd(PPh3)2Cl2 (0.14 g, 5%). Then heat to 90 °C and react for 4 h. After the raw materials are completely reacted, quench with saturated potassium fluoride aqueous solution, extract with EA. Combine the organic phases, dry over anhydrous sodium sulfate, mix with silica gel and perform column chromatography. The eluent is PE:THF = 3:1 (volume ratio) to obtain about 2.02 g of compound 6-2, yield: 78.5%. MS: 643.20.

[0195] Synthesis of Compound M-6

[0196] Accurately weigh compound 6-2 (1.29 g, 2 mmol) and add it to a 100 ml two-necked flask, add 20 mL of chloroform. After displacing nitrogen three times, add NBS (0.75 g, 4.2 mmol). React at room temperature overnight. After the reaction is completed, quench with aqueous sodium sulfite solution and extract with ethyl acetate. Combine the organic phases, dry over anhydrous sodium sulfate, mix with silica gel and perform column chromatography. The eluent is PE:THF = 3:1 (volume ratio) to obtain about 1.35 g of compound 6-3, yield: 84.3%. MS: 800.49.

[0197] Synthesis of Intermediate M-7

[0198]

[0199] Synthesis of Compound 7-2

[0200] Accurately weigh compound 7-1 (2.12 g, 4 mmol) into a 100 ml three-necked flask, add 20 ml of anhydrous toluene, then add compound 5-2 (3.9 g, 8 mmol). After displacing nitrogen three times, add Pd(PPh3)2Cl2 (0.14 g, 5%). Then heat to 90 °C and react for 4 h. After the raw materials are completely reacted, quench with saturated potassium fluoride aqueous solution, extract with EA. Combine the organic phases, dry over anhydrous sodium sulfate, mix with silica gel and perform column chromatography. The eluent is PE:THF = 3:1 (volume ratio) to obtain about 2.39 g of compound 7-2, yield: 77.9%. MS: 766.52.

[0201] Synthesis of Compound M-7

[0202] Accurately weigh compound 7-2 (1.53 g, 2 mmol) and add it to a 100 ml two-necked flask. Add 20 ml of chloroform. After displacing nitrogen three times, add NBS (0.75 g, 4.2 mmol). React at room temperature overnight. After the reaction is completed, quench with an aqueous sodium sulfite solution and extract with ethyl acetate. Combine the organic phases, dry over anhydrous sodium sulfate, and then carry out silica gel column chromatography with the eluent being PE:THF = 1:1 (volume ratio) to obtain about 1.48 g of compound M-7, yield: 80.1%. MS: 924.31.

[0203] Synthesis of Intermediate M-8

[0204]

[0205] Synthesis of Compound 8-2

[0206] Accurately weigh Cp2TiCl2 (5 g, 20 mmol) into a 250 mL three-necked flask, add metallic manganese (4.3 g, 80 mmol), and react in an air atmosphere until the solution turns light green; then dissolve compound 8-1 (12.8 g, 100 mmol) in 50 ml of tetrahydrofuran and 50 mL of D2O, and slowly add it dropwise to the above light green solution, and then react at room temperature for 24 hours. After the reaction is completed, quench with a saturated potassium bisulfate solution, extract with ethyl acetate, combine the organic phases, dry over anhydrous sodium sulfate, and then distill under reduced pressure to remove the excess solvent to obtain about 10.6 g of the crude product of compound 8-2.

[0207] Synthesis of Compound 8-3:

[0208] Weigh the above crude product of compound 8-2 (9.18 g, 70 mmol) and carbon tetrabromide (46.4 g, 140 mmol) and add them successively to a 500 mL dry three-necked flask. Add 200 mL of anhydrous THF, displace nitrogen three times. Separately weigh triphenylphosphine (36.7 g, 140 mmol), dissolve it in 80 mL of anhydrous THF, and slowly add it dropwise to the reaction system. React at room temperature overnight. After the reaction is completed, pour it into ice water, then extract with EA, combine the organic phases, dry over anhydrous sodium sulfate, distill under reduced pressure to remove the excess solvent, carry out silica gel column chromatography with the eluent being PE:DCM = 30:1 (volume ratio) to obtain compound 8-3 as a colorless transparent oily substance, about 6.7 g, yield: 49.3%.

[0209] Synthesis of Compound 8-4

[0210] Accurately weigh 3-fluorothiophene (2.04 g, 20 mmol) into a 100 mL three-necked flask, add about 30 mL of anhydrous THF. After displacing nitrogen three times, cool the temperature to -80 °C, and then slowly add LDA (2 M, 11 mL) dropwise to the system. After maintaining the low-temperature reaction for 1 h, slowly add compound 8-3 (3.88 g, 20 mmol) dropwise to the system. Allow the temperature to rise to room temperature naturally and react overnight. Add an aqueous ammonium chloride solution to the reaction solution, and then extract it three times with ethyl acetate. Combine the organic phases, dry over anhydrous sodium sulfate, mix with silica gel and perform column chromatography. The eluent is PE to obtain about 3.34 g of compound 8-4, yield: 77.4%. MS: 215.83.

[0211] Synthesis of Compound 8-5

[0212] Accurately weigh compound 8-4 (3.02 g, 14 mmol) and add it to a 100 mL three-necked flask. Add about 50 mL of anhydrous THF. After displacing nitrogen three times, cool the temperature to -80 °C, and then slowly add LDA (2 M, 7.7 mL) dropwise to the system. After maintaining the low-temperature reaction for 1 h, slowly add compound 1-4 (1.32 g, 6 mmol) to the system. After reacting at room temperature for two hours, add a dilute hydrochloric acid solution of stannous chloride (1.79 g, 20 mmol dissolved in 20 mL of 10% hydrochloric acid) to the reaction system, and heat to 50 °C and react overnight. After the reaction solution cools to room temperature, quench it with brine, and then extract it with PE. Combine the organic phases, dry over anhydrous sodium sulfate, mix with silica gel and perform column chromatography. The eluent is n-hexane to obtain about 3.17 g of compound 8-5, yield: 85.6%. MS: 617.24.

[0213] Synthesis of Compound M-8

[0214] Accurately weigh compound 8-5 (2.47 g, 4 mmol) and add it to a 100 mL three-necked flask. Add about 30 mL of anhydrous THF. After displacing nitrogen three times, cool the temperature to -80 °C, and then slowly add LDA (2 M, 7.7 mL) dropwise to the system. Maintain the low-temperature reaction for 1 h, and then add trimethyltin chloride (2.39 g, 12 mmol) to the reaction system. Allow the temperature to rise to room temperature naturally and react overnight. Add a saturated potassium fluoride solution and stir for 2 hours. Extract with petroleum ether until there is no product in the aqueous phase. Combine the organic phases, dry over anhydrous sodium sulfate and concentrate. Recrystallize by heating to 70 °C with isopropanol to obtain about 2.91 g of compound 8-6, yield: 77.2%. MS: 942.67.

[0215] Polymer Synthesis Example

[0216] Polymer Synthesis Example 1: Synthesis of Polymer (P2)

[0217]

[0218] Accurately weigh compound M-2 (947 mg, 1.0 mmol) and compound M-9 (766 mg, 1.0 mmol), and sequentially add them into a 100 mL thick-walled pressure-resistant tube. Add 30 mL of ultra-dry o-xylene, and after purging with nitrogen for 10 min, add palladium tetrakis(triphenylphosphine) (5.8 mg, 0.05 mmol). Continue purging with nitrogen for 10 min, and stop heating after reacting at 120 °C for 22 h. Cool the reaction solution to room temperature, dilute it with chloroform and drop it into methanol to precipitate a solid. Filter by suction, and the filter cake is thoroughly washed successively with n-hexane, acetone, and dichloromethane in a Soxhlet extractor. Dissolve the residue in chloroform, perform silica gel column chromatography with 60-100 mesh, concentrate and drop it into methanol to precipitate a solid. Filter by suction, and after vacuum drying the filter cake, about 921 mg of polymer (P2) is obtained, with a yield of 75.1%, Mn: 33.4 KDa, PDI: 3.15.

[0219] Polymer Synthesis Example 2: Synthesis of Polymer (P3)

[0220]

[0221] Accurately weigh compound M-1 (944 mg, 1.0 mmol) and compound M-9 (766 mg, 1.0 mmol), and sequentially add them into a 100 mL thick-walled pressure-resistant tube. Add 30 mL of ultra-dry o-xylene, and after purging with nitrogen for 10 min, add palladium tetrakis(triphenylphosphine) (5.8 mg, 0.05 mmol). Continue purging with nitrogen for 10 min, and stop heating after reacting at 120 °C for 22 h. Cool the reaction solution to room temperature, dilute it with chloroform and drop it into methanol to precipitate a solid. Filter by suction, and the filter cake is thoroughly washed successively with n-hexane, acetone, and dichloromethane in a Soxhlet extractor. Dissolve the residue in chloroform, perform silica gel column chromatography with 60-100 mesh, concentrate and drop it into methanol to precipitate a solid. Filter by suction, and after vacuum drying the filter cake, about 938 mg of polymer (P3) is obtained, with a yield of 76.7%, Mn: 34.6 KDa, PDI: 3.22.

[0222] Polymer Synthesis Example 3: Synthesis of Polymer (P4)

[0223]

[0224] Accurately weigh compound M-3 (975 mg, 1.0 mmol) and compound M-9 (766 mg, 1.0 mmol), and sequentially add them into a 100 mL thick-walled pressure-resistant tube. Add 30 mL of ultra-dry o-xylene, and after purging with nitrogen for 10 min, add palladium tetrakis(triphenylphosphine) (5.8 mg, 0.05 mmol). Continue purging with nitrogen for 10 min, and stop heating after reacting at 120 °C for 22 h. Cool the reaction solution to room temperature, dilute it with chloroform and drop it into methanol to precipitate a solid. Filter by suction, and the filter cake is thoroughly washed successively with n-hexane, acetone, and dichloromethane in a Soxhlet extractor. The residue is dissolved in chloroform, subjected to silica gel column chromatography with a mesh size of 60 - 100, concentrated and dropped into methanol to precipitate a solid. Filter by suction, and after vacuum drying the filter cake, about 924 mg of polymer (P4) is obtained, with a yield of 73.7%, Mn: 31.5 KDa, and PDI: 2.80. The GPC chromatogram is as shown in Figure 2 shown.

[0225] Synthesis Example 4 of Polymer: Synthesis of Polymer (P14)

[0226]

[0227] Accurately weigh compound M-8 (942 mg, 1.0 mmol) and compound M-9 (766 mg, 1.0 mmol), and sequentially add them into a 100 mL thick-walled pressure-resistant tube. Add 30 mL of ultra-dry o-xylene, and after purging with nitrogen for 10 min, add palladium tetrakis(triphenylphosphine) (5.8 mg, 0.05 mmol). Continue purging with nitrogen for 10 min, and stop heating after reacting at 120 °C for 22 h. Cool the reaction solution to room temperature, dilute it with chloroform and drop it into methanol to precipitate a solid. Filter by suction, and the filter cake is thoroughly washed successively with n-hexane, acetone, and dichloromethane in a Soxhlet extractor. The residue is dissolved in chloroform, subjected to silica gel column chromatography with a mesh size of 60 - 100, concentrated and dropped into methanol to precipitate a solid. Filter by suction, and after vacuum drying the filter cake, about 878 mg of polymer (P14) is obtained, with a yield of 71.9%, Mn: 32.8 KDa, and PDI: 2.96.

[0228] Synthesis Example 5 of Polymer: Synthesis of Polymer (P24)

[0229]

[0230] Accurately weigh compound M-4 (980 mg, 1.0 mmol) and compound M-5 (795 mg, 1.0 mmol), and successively add them into a 100 mL thick-walled pressure-resistant tube. Add 30 mL of ultra-dry o-xylene, and after purging with nitrogen for 10 min, add palladium tetrakistriphenylphosphine (5.8 mg, 0.05 mmol). Continue purging with nitrogen for 10 min, and stop heating after reacting at 120 °C for 22 h. Cool the reaction solution to room temperature, dilute it with chloroform and drop it into methanol to precipitate a solid. Filter it by suction, and the filter cake is thoroughly washed successively with n-hexane, acetone, and dichloromethane in a Soxhlet extractor. The residue is dissolved in chloroform, chromatographed on a silica gel column with 60-100 mesh, concentrated and dropped into methanol to precipitate a solid. Filter it by suction, and after vacuum drying the filter cake, about 827 mg of polymer (P24) is obtained, with a yield of 64.2%, Mn: 39.4 KDa, and PDI: 3.27.

[0231] Polymer Synthesis Example 6: Synthesis of Polymer (P28)

[0232]

[0233] Accurately weigh compound M-2 (947 mg, 1.0 mmol) and compound M-10 (795 mg, 1 mmol), and successively add them into a 100 mL thick-walled pressure-resistant tube. Add 30 mL of ultra-dry o-xylene, and after purging with nitrogen for 10 min, add palladium tetrakistriphenylphosphine (5.8 mg, 0.05 mmol). Continue purging with nitrogen for 10 min, and stop heating after reacting at 120 °C for 22 h. Cool the reaction solution to room temperature, dilute it with chloroform and drop it into methanol to precipitate a solid. Filter it by suction, and the filter cake is thoroughly washed successively with n-hexane, acetone, and dichloromethane in a Soxhlet extractor. The residue is dissolved in chloroform, chromatographed on a silica gel column with 60-100 mesh, concentrated and dropped into methanol to precipitate a solid. Filter it by suction, and after vacuum drying the filter cake, about 924 mg of polymer (P28) is obtained, with a yield of 73.6%, Mn: 39.9 KDa, and PDI: 2.70. The GPC chromatogram is as Figure 3 shown.

[0234] Polymer Synthesis Example 7: Synthesis of Polymer (P29)

[0235]

[0236] Accurately weigh compound M-2 (947 mg, 1.0 mmol) and compound M-6 (801 mg, 1.0 mmol), and successively add them into a 100 mL thick-walled pressure-resistant tube. Add 30 mL of ultra-dry o-xylene, blow nitrogen for 10 min, then add palladium tetrakis(triphenylphosphine) (5.8 mg, 0.05 mmol), continue to blow nitrogen for 10 min, and stop heating after reacting at 120 °C for 22 h. Cool the reaction solution to room temperature, dilute it with chloroform and drop it into methanol to precipitate a solid. Filter it by suction. The filter cake is thoroughly washed successively with n-hexane, acetone, and dichloromethane in a Soxhlet extractor. The residue is dissolved in chloroform, chromatographed on a silica gel column with 60-100 mesh, concentrated and dropped into methanol to precipitate a solid. Filter it by suction. After the filter cake is dried in vacuo, about 989 mg of polymer (P29) is obtained, with a yield of 78.5%, Mn: 32.5 KDa, and PDI: 3.03.

[0237] Polymer Synthesis Example 8: Synthesis of Polymer (P30)

[0238]

[0239] Accurately weigh compound M-1 (945 mg, 1.0 mmol) and compound M-10 (795 mg, 1 mmol), and successively add them into a 100 mL thick-walled pressure-resistant tube. Add 30 mL of ultra-dry o-xylene, blow nitrogen for 10 min, then add palladium tetrakis(triphenylphosphine) (5.8 mg, 0.05 mmol), continue to blow nitrogen for 10 min, and stop heating after reacting at 120 °C for 22 h. Cool the reaction solution to room temperature, dilute it with chloroform and drop it into methanol to precipitate a solid. Filter it by suction. The filter cake is thoroughly washed successively with n-hexane, acetone, and dichloromethane in a Soxhlet extractor. The residue is dissolved in chloroform, chromatographed on a silica gel column with 60-100 mesh, concentrated and dropped into methanol to precipitate a solid. Filter it by suction. After the filter cake is dried in vacuo, about 966 mg of polymer (P30) is obtained, with a yield of 77.1%, Mn: 35.8 KDa, and PDI: 3.19.

[0240] Polymer Synthesis Example 9: Synthesis of Polymer (P45)

[0241]

[0242] Accurately weigh monomer M-2 (947 mg, 1.0 mmol), M-9 (690 mg, 0.9 mmol), and M-7 (92 mg, 0.1 mmol) and add them successively into a 100 mL thick-walled pressure-resistant tube. Add 30 mL of ultra-dry o-xylene. After purging with nitrogen for 10 min, add tris(o-tolyl)phosphine (49 mg, 0.16 mmol) and tris(dibenzylideneacetone)dipalladium(0) (18 mg, 0.02 mmol). Continue purging with nitrogen for 10 min. Stop heating after reacting at 120 °C for 15 h. Cool the reaction solution to room temperature, dilute it with chloroform and drop it into methanol to precipitate a solid. Filter it by suction. The filter cake is washed thoroughly with n-hexane, acetone, and dichloromethane in a Soxhlet extractor. The residue is dissolved in chloroform, chromatographed on a silica gel column with 60 - 100 mesh, concentrated and dropped into methanol to precipitate a solid. Filter it by suction. After vacuum drying the filter cake, about 910 mg of polymer (P45) is obtained, with a yield of 73.3%, Mn: 38.1 KDa, PDI: 2.98.

[0243] Synthesis of polymer PM6:

[0244]

[0245] Accurately weigh compound M-11 (940 mg, 1.0 mmol) and compound M-9 (766 mg, 1.0 mmol) and add them successively into a 100 mL thick-walled pressure-resistant tube. Add 30 mL of ultra-dry o-xylene. After purging with nitrogen for 10 min, add tetrakis(triphenylphosphine)palladium(0) (5.8 mg, 0.05 mmol). Continue purging with nitrogen for 10 min. Stop heating after reacting at 120 °C for 22 h. Cool the reaction solution to room temperature, dilute it with chloroform and drop it into methanol to precipitate a solid. Filter it by suction. The filter cake is washed thoroughly with n-hexane, acetone, and dichloromethane in a Soxhlet extractor. The residue is dissolved in chloroform, chromatographed on a silica gel column with 60 - 100 mesh, concentrated and dropped into methanol to precipitate a solid. Filter it by suction. After vacuum drying the filter cake, about 926 mg of polymer (P14) is obtained, with a yield of 76.0%, Mn: 36.3 Kda, PDI: 3.25.

[0246] Synthesis of polymer (D18):

[0247]

[0248] Accurately weigh compound M-11 (940 mg, 1.0 mmol) and M-10 (795 mg, 1.0 mmol), and sequentially add them into a 100 mL thick-walled pressure-resistant tube. Add 30 mL of ultra-dry o-xylene. After purging with nitrogen for 10 min, add palladium tetrakis(triphenylphosphine) (5.8 mg, 0.05 mmol), and continue purging with nitrogen for 10 min. Stop heating after reacting at 120 °C for 22 h. Cool the reaction solution to room temperature, dilute it with chloroform and drop it into methanol to precipitate a solid. Filter by suction. The filter cake is thoroughly washed successively with n-hexane, acetone, and dichloromethane in a Soxhlet extractor. The residue is dissolved in chloroform, chromatographed on a silica gel column with a mesh size of 60 - 100, concentrated and dropped into methanol to precipitate a solid. Filter by suction. After the filter cake is dried under vacuum, about 934 mg of polymer (D18) is obtained, with a yield of 74.9%, Mn: 41.8 KDa, and PDI: 3.42.

[0249] Synthesis of polymer (PBD-10):

[0250]

[0251] Accurately weigh monomers M-11 (940 mg, 1.0 mmol), M-9 (690 mg, 0.9 mmol), and M-12 (92 mg, 0.1 mmol), and sequentially add them into a 100 mL thick-walled pressure-resistant tube. Add 30 mL of ultra-dry o-xylene. After purging with nitrogen for 10 min, add tris(o-tolyl)phosphine (49 mg, 0.16 mmol) and tris(dibenzylideneacetone)dipalladium (18 mg, 0.02 mmol), and continue purging with nitrogen for 10 min. Stop heating after reacting at 120 °C for 15 h. Cool the reaction solution to room temperature, dilute it with chloroform and drop it into methanol to precipitate a solid. Filter by suction. The filter cake is thoroughly washed successively with n-hexane, acetone, and dichloromethane in a Soxhlet extractor. The residue is dissolved in chloroform, chromatographed on a silica gel column with a mesh size of 60 - 100, concentrated and dropped into methanol to precipitate a solid. Filter by suction. After the filter cake is dried under vacuum, about 847 mg of polymer (PBD-10) is obtained, with a yield of 68.6%, Mn: 36.9 KDa, and PDI: 3.11.

[0252] Examples of OPV devices and data characterization

[0253] The following specifically describes the preparation process and device characterization of an organic photovoltaic cell including the above-mentioned polymer with side-chain deuteration through specific device examples. Refer to Figure 1 , the OPV device includes a substrate, an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer, and a cathode layer stacked in sequence from bottom to top.

[0254] The preparation steps of Device Example 1 are as follows:

[0255] 1) Cleaning of ITO substrate:

[0256] Clean the ITO conductive glass with detergent. After rinsing it thoroughly, ultrasonically clean it with deionized water, acetone, and isopropyl alcohol for 15 minutes, then dry it with nitrogen and treat it in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0257] 2) Preparation of the anode buffer layer

[0258] Subsequently, spin-coat the anode buffer layer material CBz-2Ph (0.5 mg / mL, isopropyl alcohol solution) on the ITO substrate at a speed of 3000 rpm for 30 seconds, and then anneal it at 100 °C for 5 minutes to obtain the anode buffer layer.

[0259] 3) Preparation of the photoactive layer

[0260] In a glove box (inert gas atmosphere), spin-coat the photoactive layer material solution uniformly on the anode buffer layer at a speed of 1800 - 4000 rpm to obtain a photoactive material layer with a total thickness of about 100 nm; wherein the donor material in the photoactive layer material solution is selected from polymer (P2); the acceptor material is selected from L8-BO; add polymer (P2):L8-BO to the chloroform solution at a mass ratio of 1:1.2, and the total concentration of the donor and acceptor materials in chloroform is 16.5 mg / mL, and add 0.25% by volume of DIO as an additive.

[0261] 4) Preparation of the cathode buffer layer

[0262] Spin-coat the cathode buffer layer material PDINN solution (dissolve PDINN in methanol to prepare a solution with a concentration of 1 mg / mL) uniformly on the photoactive layer at a speed of 3000 rpm for 30 seconds to obtain the cathode buffer layer.

[0263] 5) Preparation of the cathode layer

[0264] In high vacuum (1×10 -6 mbar), evaporate Ag onto the cathode buffer layer to form a cathode layer with a thickness of about 100 nm.

[0265] 6) Encapsulation

[0266] Encapsulate the device with ultraviolet curable resin in a nitrogen glove box.

[0267] Device Examples 2 - 4

[0268] The preparation method of Device Examples 2 - 4 is the same as that of Device Example 1, the difference is that: the donor material (P2) in the active layer is replaced with polymer (P3), polymer (P4), and polymer (P14) respectively. For details, see Table 1.

[0269] Device Comparative Example 1

[0270] The preparation method of Device Comparative Example 1 is the same as that of Device Example 1, with the difference being that the donor material (P2) in the active layer is replaced with polymer PM6.

[0271] The prepared organic photovoltaic device was subjected to performance testing. Under standard light irradiation of a solar simulator (AM 1.5G), the current-voltage curve of the battery was tested, and the photoelectric conversion efficiency was calculated; as shown in Table 1.

[0272] Table 1

[0273]

[0274] It can be seen from the data in Table 1 that any deuteration at the α-position and β-position of the branched-chain alkyl group on the polymer BDT unit can significantly improve the light stability of the device, thereby enhancing the device life. Especially when both the α-position and β-position are deuterated, the device can still maintain a photoelectric conversion efficiency of more than 90% after continuous irradiation with an LED lamp for 1000 h at room temperature, achieving a significant improvement in device stability.

[0275] Device Example 5

[0276] The preparation method of Device Example 5 is the same as that of Device Example 1, with the difference being that the photoactive preparation is different, specifically as follows:

[0277] In a glove box (inert gas atmosphere), the photoactive layer material solution was spin-coated uniformly on the anode buffer layer at a rotation speed of 1800 - 4000 rpm to obtain a photoactive material layer with a total thickness of about 100 nm; wherein the donor material in the photoactive layer material solution is polymer (P28); the acceptor material is selected from BTP-eC9; polymer (P28):BTP-eC9 was added to the chloroform solution at a mass ratio of 1:1.3, and the total concentration of the donor and acceptor materials in chloroform was 13 mg / mL, and 0.45% by volume of 1-CN was added as an additive.

[0278] Device Examples 6 - 7

[0279] The preparation methods of Device Examples 6 - 7 are the same as that of Device Example 5, with the difference being that the donor material (P28) in the active layer is replaced with polymer (P29) and polymer (P30) respectively. For details, see Table 3.

[0280] Device Comparative Example 2

[0281] The preparation method of Device Comparative Example 2 is the same as that of Device Example 5, with the difference being that the donor material (P28) in the active layer is replaced with polymer D18.

[0282] The prepared organic photovoltaic devices were subjected to performance tests. Under the standard light irradiation of a solar simulator (AM 1.5G), the current-voltage curves of the cells were measured, and the photoelectric conversion efficiency was calculated; as shown in Table 2.

[0283] Table 2

[0284]

[0285] By comparing the data of Device Example 5, 7 and Device Comparative Example 2, it can be seen that deuteration at the α and β positions of the branched-chain alkyl groups on the polymer BDT unit can significantly improve the light stability of the device, so that the photoelectric performance of the device can still remain close to over 90% after continuous irradiation with an LED lamp for 1000 h at room temperature.

[0286] By comparing the data of Device Example 5 and Device Example 6, it can be seen that further deuteration at the α and β positions of the branched-chain on the connecting unit thiophene in the polymer repeating unit can further improve the light stability of the device, so that the photoelectric performance of the device can still remain above 92% after continuous irradiation with an LED lamp for 1000 h at room temperature.

[0287] Device Example 8

[0288] The preparation method of Device Example 8 is the same as that of Device Example 1, and the difference lies in the different photoactive preparation, which is specifically as follows:

[0289] In a glove box (inert gas atmosphere), the photoactive layer material solution was uniformly spin-coated on the anode buffer layer at a rotation speed of 1800 - 4000 rpm to obtain a photoactive material layer with a total thickness of about 100 nm; wherein the donor material polymer (P45) in the photoactive layer material solution; the acceptor material is selected from BTP-eC9; the polymer (P45):BTP-eC9 was added to the o-xylene solution at a mass ratio of 1:1.2, and the total concentration of the donor and acceptor materials in o-xylene was 17.6 mg / mL.

[0290] Device Comparative Example 3

[0291] The preparation method of Device Comparative Example 3 is the same as that of Device Example 8, and the difference lies in: replacing the donor material (P45) in the active layer with the polymer PBD-10.

[0292] Table 3

[0293]

[0294] From the data in Table 3, it can be seen that among the terpolymerized polymers, the polymer according to the present invention can still effectively improve the stability of the device.

[0295] Obviously, the above embodiments are merely examples for clear illustration and not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or variations can be made based on the above description. It is not necessary and impossible to enumerate all the implementation manners here. And the obvious changes or variations derived therefrom still fall within the protection scope of the present invention.

Claims

1. A polymer with side-chain deuteration, characterized in that: Comprising repeating units represented by general formula (I): Wherein: a is independently selected from 0, 1 or 2; b is independently selected from 0, 1 or 2; Ar1, Ar2, Ar3 are independently selected from substituted or unsubstituted heteroaromatic groups having 5 - 30 ring atoms, or substituted or unsubstituted aromatic groups having 6 - 30 carbon atoms; Ar4, Ar5 are independently selected from substituted or unsubstituted heteroaromatic groups having 5 - 10 ring atoms, or substituted or unsubstituted aromatic groups having 6 - 10 carbon atoms; R0, R1 are independently selected from -H or -D, and at least one of R0 and R1 is selected from -D; Each occurrence of R2, R3 is independently selected from a straight-chain alkyl or branched-chain alkyl having 1 - 10 carbon atoms, or a straight-chain alkyl or branched-chain alkyl having 1 - 10 carbon atoms substituted by one deuterium (-D) or multiple deuteriums; Each occurrence of Y is independently selected from O, S or Se; Each occurrence of X is independently selected from CR4 or N; Each occurrence of R4 is independently selected from -H, -D, or a straight-chain alkyl having 1 - 10 carbon atoms, or a branched-chain alkyl having 3 - 10 carbon atoms; The "substituted or unsubstituted" means that the defined group is unsubstituted or substituted by one or more substituents R, and each occurrence of R is independently selected from: -D, -F, -Cl, -Br, -I, -CN, a straight-chain alkyl having 1 - 30 carbon atoms, a branched-chain alkyl having 3 - 30 carbon atoms, a straight-chain alkoxy having 1 - 30 carbon atoms, a branched-chain alkoxy having 3 - 30 carbon atoms, a straight-chain alkylthio having 1 - 30 carbon atoms, a branched-chain alkylthio having 3 - 30 carbon atoms, an ester group having 1 - 30 carbon atoms, a heteroaromatic group having 5 - 20 ring atoms, or an aromatic group having 6 - 20 carbon atoms, and groups formed by combinations of the above groups; * represents the connection site.

2. The polymer with side-chain deuteration according to claim 1, characterized in that: The side-chain deuterated polymer comprises repeating units represented by general formula (II-1), general formula (II-2) or general formula (II-3):

3. The polymer with side-chain deuteration according to claim 1 or 2, characterized in that: Ar4 and Ar5 are each independently selected from wherein: each occurrence of V is independently selected from CR5 or N; each occurrence of R5 is independently selected from hydrogen, deuterium, -F, -Cl, -CN, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms, a straight-chain alkoxy group having 1 to 10 carbon atoms, a branched-chain alkoxy group having 3 to 10 carbon atoms, a straight-chain alkylthio group having 1 to 10 carbon atoms, a branched-chain alkylthio group having 3 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, and a group formed by combining the above groups.

4. The polymer with side-chain deuteration according to claim 3, characterized in that: The said Selected from any one of the following groups: Preferably, each occurrence of R5 is independently selected from hydrogen, deuterium, -F, -Cl, -CN, -CF3, -CH3 or -CD3; V is selected from N, C-H, C-F or C-Cl.

5. The polymer with a side-chain deuteration according to claim 4, characterized in that: The said Selected from any one of the following groups:

6. The polymer with side-chain deuteration according to claim 5, characterized in that: R2 and R3 are independently selected from -C2H5, -C4H9, -C6H 13 , -C2D5, -C4D9 or -C6D 13 .

7. The polymer with side chain deuteration according to claim 2, wherein: Ar1 is independently selected from any one of the following groups: Wherein: Each occurrence of R6 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, a straight-chain alkyl having 1 - 20 carbon atoms, a branched-chain alkyl having 3 - 20 carbon atoms, a straight-chain alkoxy having 1 - 20 carbon atoms, a branched-chain alkoxy having 3 - 20 carbon atoms, a straight-chain alkylthio having 1 - 20 carbon atoms, a branched-chain alkylthio having 3 - 20 carbon atoms, an ester group having 1 - 20 carbon atoms, a heteroaromatic group having 5 - 20 ring atoms, or an aromatic group having 6 - 20 carbon atoms, and groups formed by combinations of the above groups.

8. The polymer with side-chain deuteration according to claim 7, wherein: Ar1 is independently selected from any one of the following groups:

9. The polymer with side-chain deuteration according to claim 2, wherein: Ar2 and Ar3 are independently selected from wherein: each occurrence of R7 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a branched-chain alkoxy group having 3 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a branched-chain alkylthio group having 3 to 20 carbon atoms, an ester group having 1 to 20 carbon atoms, and a group formed by combining the above groups; Preferably, the is selected from any one of the following groups: Wherein: R8, R9, R 10 Each occurrence is independently selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a straight-chain alkyl group having 1 to 10 carbon atoms substituted with one or more deuteriums.

10. The polymer with side-chain deuteration according to claim 7 or 9, characterized in that: The said selected from the following groups:

11. The polymer with side-chain deuteration according to claim 1, characterized in that: The side-chain deuterated polymer is selected from any one of the following structures: Wherein: n represents the number of repeating units, and is selected from integers greater than or equal to 2.

12. A mixture, characterized in that: The mixture comprises a polymer with side-chain deuteration as described in any one of claims 1-11.

13. A composition, characterized in that: The composition comprises a polymer with side-chain deuteration as described in any one of claims 1-11 or the mixture as described in claim 12, and at least one organic solvent.

14. An organic photovoltaic device, characterized in that: The organic photovoltaic device comprises a polymer with side-chain deuteration as described in any one of claims 1-11 or the mixture as described in claim 12.

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