Polymer semiconductor material with controllable open-loop side chain as well as preparation method and application of polymer semiconductor material

Abstract

The invention discloses a polymer semiconductor material with a controllable open-loop side chain and a preparation method and application thereof, the structural formula of the polymer semiconductor material is shown in the specification, the polymer semiconductor material is prepared through a Stille coupling reaction according to the preparation method, and the polymer semiconductor material can be used as an intrinsic stretchable organic semiconductor material.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of conjugated polymer materials, and particularly relates to a side chain controllable ring-opening polymer semiconductor material, a preparation method and application thereof. BACKGROUND

[0002] In recent years, with the increasing demand for wearable devices and implantable electronic products, flexible and stretchable electronic technology has developed rapidly. In many fields such as wearable applications, display technology and energy storage systems, stretchable organic semiconductors show wide application potential. As the core part of flexible electronic devices, the organic semiconductor active layer not only needs to have good electrical properties, but also must have excellent mechanical flexibility and ductility. For a long time, researchers have explored various implementation strategies from different angles, including structural engineering, blending with elastomers, and developing intrinsically stretchable organic semiconductor materials.

[0003] The research and development of intrinsically stretchable organic semiconductor materials focuses on starting from the design of polymer molecular structure, and constructing a material system that has good stretchability without the need for macrostructure regulation, elastomer blending or external small molecule additives. This kind of material is suitable for high-efficiency solution processing technology, which helps to realize large-area device preparation and effectively avoids complex phase separation phenomena. In addition, the solution processing method also provides a variety of ways to regulate the morphology of the solid film, such as adjusting the solution concentration, additive type, solvent temperature and other parameters to realize systematic optimization of the film performance.

[0004] Ring-opening polymerization is a chemical reaction in which cyclic monomers generate linear polymers through an addition ring-opening process. The mechanism of this reaction combines the efficiency of chain polymerization with the controllability of step polymerization, while effectively avoiding the typical defects of traditional polymerization methods such as multiple side reactions and wide molecular weight distribution. Its core advantages are reflected in its excellent controllability and mild reaction conditions.

[0005] Introducing this highly controllable ring-opening polymerization strategy into the conjugated polymer synthesis system, especially introducing stretchable segments in the side chain modification, shows multiple structural advantages:

[0006] 1. Low steric hindrance effect brought by linear structure

[0007] The side chain generated by ring-opening polymerization is linear in structure, and its molecular conformation is relaxed and the steric hindrance is significantly smaller than that of branched structure. This low steric hindrance characteristic effectively avoids the interference of the side chain with the π-π stacking of the conjugated main chain, so that the carrier migration rate along the main chain direction can be maintained, laying a structural foundation for maintaining the performance of polymer semiconductors.

[0008] 2. Controllable introduction of stretchable segments

[0009] The controllable property of ring-opening polymerization makes the introduction of stretchable chain segments have molecular weight control and end functional group selectivity. This controllable ability ensures better molecular weight controllability when introducing stretchable chain segments on conjugated units, thereby realizing quantitative design of material stretchability.

[0010] 3. Improvement of mechanical properties

[0011] By molecular design, flexible stretchable chain segments are organically combined with rigid conjugated main chains, while maintaining the charge transport ability of the main chain, the flexibility of the side chain can effectively dissipate external stress, so that the material obtains excellent stretchability and mechanical stability. This "rigidity and flexibility" molecular structure solves the core problem of the brittleness and poor ductility of traditional conjugated polymers.

[0012] In addition, while introducing such ring-opening flexible chain segments, the functionalized hydroxyl groups at the ends can be retained, so that the polymer material has intermolecular and intramolecular hydrogen bonding interaction forces. Under the synergistic action of the flexible chain segments and the functionalized hydroxyl groups, the material has better mechanical properties.

[0013] This functionalization strategy based on controllable ring-opening polymerization successfully realizes the simultaneous improvement of the mechanical stretchability of the conjugated polymer while maintaining its electrical properties under the synergistic action of the side chain flexible chain segments and the terminal hydroxyl groups, providing an ideal material platform for developing a new generation of stretchable electronic devices. The establishment of this method not only expands the application boundary of ring-opening polymerization, but also provides a new way for the structural design of functional polymers. SUMMARY

[0014] The application provides a side chain controllable ring-opening polymer semiconductor material and a preparation method and application thereof. The polycaprolactone chain segment is introduced on both sides of the conjugated unit through controllable ring-opening polymerization by side chain engineering, and a stretchable soft segment is constructed to solve the problem of insufficient stretchability of the organic semiconductor material prepared by the prior art.

[0015] In order to achieve the above object, the technical scheme adopted by the application is as follows:

[0016] A side chain controllable ring-opening polymer semiconductor material, characterized in that its structural formula is shown as structural formula (I), and the structural formula (I) is as follows:

[0017] (I)

[0018] In the structural formula I, Ar1 is an isatin, or a diketopyrrolopyrrole, or a naphthalimide, which is a polycaprolactone chain segment structure introduced by ring-opening polymerization of a side chain, wherein n is 6-30, and the optimal value of n is 18.

[0019] Ar2 is indigo, pyrrolopyrrole dione, or naphthalimide with an alkyl side chain attached;

[0020] R is C5-C 80 One of the straight-chain or branched alkyl groups;

[0021] Ar3 is a thiophene compound, and the bonding mode within the Ar3 group is selected from single bonds or double bonds;

[0022] x:y ranges from 1:0 to 1:99.

[0023] Furthermore, when Ar1 is isoindigo, 6,6'-dibromoisoindigo from isoindigo is used, with the structural formula shown below:

[0024] ;

[0025] When Ar1 is pyrrolopyrroledione, 3,6-bis(5-bromothiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione from pyrrolopyrroledione is used, with the structural formula shown below:

[0026] ;

[0027] When Ar1 is a naphthalimide, the 4,9-dibromobenzo[3,8]phenanthroline-1,3,6,8(2H,7H)-one from the naphthalimide is used, with the structural formula shown below:

[0028] .

[0029] Where n ranges from 6 to 30, and the optimal value of n is 18; This indicates the connection position of the Ar1 group in the polymer semiconductor material shown in structural formula (I).

[0030] Furthermore, when Ar2 is isoindigo, 6,6'-dibromoisoindigo from isoindigo is used, with the structural formula shown below:

[0031] ;

[0032] When Ar2 is pyrrolopyrroledione, 3,6-bis(5-bromothiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione from pyrrolopyrroledione is used, with the structural formula shown below:

[0033] ;

[0034] When Ar2 is naphthalimide, 4,9-dibromobenzo[3,8]phenanthroline-1,3,6,8(2H,7H)-one in naphthalimide is used, and the structural formula is as shown in the following formula:

[0035] .

[0036] wherein R is one of C5-C 80 linear or branched alkyl; represents the connecting position of the Ar2 group in the polymer semiconductor material shown in structural formula (I).

[0037] Further, Ar3 is a thienyl group, or a bithienyl group, or a thienyl group;

[0038] Ar3 is a thienyl group as shown in structural formula (a), or a selenophene group as shown in structural formula (b), or a bithiophene group as shown in structural formula (c), or trans-1,2-di(2-thienyl)ethylene as shown in structural formula (d), or thieno[3,2-b]thiophene as shown in structural formula (e), or 4,7-di(2-thienyl)-2,1,3-benzothiadiazole as shown in structural formula (f);

[0039] The structural formula (a) of thienyl is as shown in the following formula:

[0040] (a)

[0041] The structural formula (b) of selenophene is as shown in the following formula:

[0042] (b)

[0043] The structural formula (c) of bithiophene is as shown in the following formula:

[0044] (c)

[0045] The structural formula (d) of trans-1,2-di(2-thienyl)ethylene is as shown in the following formula:

[0046] (d)

[0047] The structural formula (e) of thieno[3,2-b]thiophene is as shown in the following formula:

[0048] (e)

[0049] The structural formula (f) of 4,7-di(2-thienyl)-2,1,3-benzothiadiazole is as shown in the following formula:

[0050] (f)

[0051] wherein, represents the connecting position of the Ar3 group in the polymer semiconductor material shown in structural formula (I).

[0052] A method for preparing the above side chain controllable ring-opening polymer semiconductor material, the process is as follows:

[0053] In an inert atmosphere, in the presence of a catalyst, the Stille coupling reaction of the conjugated monomer with controllable ring-opening polycaprolactone side chain structure shown as structural formula (II), the conjugated monomer with alkyl side chain shown as structural formula (III), and the thiophene-based compound shown as structural formula (IV) in an organic solvent is carried out to obtain a solution system;

[0054] wherein, the conjugated monomer with controllable ring-opening polycaprolactone side chain structure is shown as the following formula (II):

[0055] (II)

[0056] The conjugated monomer with alkyl side chain is shown as the following formula (III):

[0057] (III)

[0058] The thiophene-based compound is shown as the following formula (IV):

[0059] (IV)

[0060] Y in formula (IV) is trialkyl tin or borate group;

[0061] Then, the solution system is dropped into methanol to obtain a polymer solid by filtration;

[0062] Subsequently, the polymer solid is sequentially soxhlet extracted with methanol, acetone and n-hexane to obtain the target product;

[0063] Then, the target product is extracted with chloroform and then concentrated by rotary evaporation;

[0064] Finally, the chloroform solution of the target product after rotary evaporation is dropped into methanol to settle, and the final product, i.e. the polymer semiconductor material shown as structural formula (I), is obtained by suction filtration.

[0065] Further, the inert gas is nitrogen.

[0066] Furthermore, the catalyst is composed of a palladium catalyst and a phosphine ligand. The palladium catalyst is selected from tetra(triphenylphosphine)palladium and tris(dibenzylacetone)dipalladium, preferably tetra(triphenylphosphine)palladium. The phosphine ligand is selected from at least one of triphenylphosphine, tri-o-tolylphosphine, tris(2-furanyl)phosphine, and 2-(di-tert-butylphosphine)biphenyl, preferably triphenylphosphine. The molar ratio of palladium catalyst to phosphine ligand is 0.1-0.5:1, with an optimal molar ratio of 0.25:1.

[0067] Furthermore, the organic solvent is selected from at least one of toluene, tetrahydrofuran, and chlorobenzene.

[0068] Furthermore, the molar ratio of the conjugated monomer with a controllably ring-opening polycaprolactone side chain structure shown in structural formula (II), the conjugated monomer with an alkyl side chain shown in structural formula (III), and the thiophene compound shown in structural formula (IV) is 1:n:(n+1), where n is 0 to 99. The molar ratio of the palladium catalyst to the thiophene compound shown in structural formula (IV) is 0.01 to 0.1:1, with an optimal molar ratio of 0.04:1.

[0069] Furthermore, the Stille coupling reaction is carried out at a temperature of 90–130 °C, with an optimal temperature of 130 °C. The reaction time is 8–48 h, with an optimal reaction time of 48 h.

[0070] Furthermore, the preparation process of the conjugated monomer having a polycaprolactone side chain structure with controllable ring opening, as shown in structural formula (II), is as follows:

[0071] Step 1: A nucleophilic substitution reaction is carried out in a solvent with 6-bromo-1-hexanol as shown in structural formula (VI). The first conjugated monomer is isoindigo (IID), or pyrrolopyrrole dione (DPP), or naphthalenediimide (NDI), wherein the structural formula of IID is shown in structural formula (V1), the structural formula of DPP is shown in structural formula (V2), and the structural formula of NDI is shown in structural formula (V3). The nucleophilic reaction yields a second conjugated monomer with a terminal hydroxyl group as shown in structural formula (VII1), or a second conjugated monomer with a terminal hydroxyl group as shown in structural formula (VII2), or a second conjugated monomer with a terminal hydroxyl group as shown in structural formula (VII3).

[0072] The first conjugated monomer is IID, and the IID structural formula (V1) is shown below:

[0073] (V1)

[0074] Alternatively, the first conjugated monomer is DPP, and the DPP structural formula (V2) is shown below:

[0075] (V2)

[0076] Alternatively, the first conjugated monomer is NDI, and the structure of the NDI is shown in the following formula (V3):

[0077] (V3)

[0078] The structure of the 6-bromo-1-hexanol is shown in the following formula (VI):

[0079] (VI)

[0080] When the first conjugated monomer used is IID, the second conjugated monomer with a terminal hydroxyl group is generated, and the structure of the second conjugated monomer is shown in the following formula (VII1):

[0081] (VII1)

[0082] When the first conjugated monomer used is DPP, the second conjugated monomer with a terminal hydroxyl group is generated, and the structure of the second conjugated monomer is shown in the following formula (VII2):

[0083] (VII2)

[0084] When the first conjugated monomer used is NDI, the second conjugated monomer with a terminal hydroxyl group is generated, and the structure of the second conjugated monomer is shown in the following formula (VII3):

[0085] (VII3)

[0086] The molar ratio of the first conjugated monomer IID shown in the formula (V1), or the first conjugated monomer DPP shown in the formula (V2), or the first conjugated monomer NDI shown in the formula (V3), to the 6-bromo-1-hexanol compound shown in the formula (VI) is 1:2-1:3, and the optimal molar ratio is 1:2.5.

[0087] The solvent used is DMF.

[0088] The catalyst used in the nucleophilic substitution reaction is K2CO3, and the molar ratio of the first conjugated monomer IID shown in the formula (V1), or the first conjugated monomer DPP shown in the formula (V2), or the first conjugated monomer NDI shown in the formula (V3), to K2CO3 is 1:2-3, and the optimal molar ratio is 1:2.4.

[0089] The reaction temperature of the nucleophilic substitution reaction is 80-120 ℃, and the optimal temperature is 110 ℃; the reaction time is 12-36 h, and the optimal reaction time is 24 h.

[0090] Step 2, the second conjugated monomer with a hydroxyl group at the end as shown in structural formula (VII1), or the second conjugated monomer with a hydroxyl group at the end as shown in structural formula (VII2), or the second conjugated monomer with a hydroxyl group at the end as shown in structural formula (VII3), is subjected to ring-opening reaction with caprolactone to obtain the conjugated monomer with a controllably ring-opened polycaprolactone side chain structure as shown in structural formula (II).

[0091] The ring-opening reaction process is as follows:

[0092] In the solution of the second conjugated monomer with a hydroxyl group at the end as shown in structural formula (VII1), or the second conjugated monomer with a hydroxyl group at the end as shown in structural formula (VII2), or the second conjugated monomer with a hydroxyl group at the end as shown in structural formula (VII3) dissolved in anhydrous toluene, caprolactone is added under an oxygen-free environment and stirred and mixed, then diphenyl phosphate is added as a reaction catalyst, and then the reaction is completed at room temperature (30 ℃ 2 ℃) to obtain the conjugated monomer with a controllably ring-opened polycaprolactone side chain structure as shown in structural formula (II).

[0093] The molar ratio of the conjugated monomer with a controllably ring-opened polycaprolactone side chain structure as shown in structural formula (II) to caprolactone can be 1:24-48, and the optimal molar ratio is 1:36. The ring-opening reaction time is 18-30 h, and the optimal ring-opening reaction time is 24 h.

[0094] The molar ratio of the first conjugated monomer IID as shown in structural formula (V1), or the first conjugated monomer DPP as shown in structural formula (V2), or the first conjugated monomer NDI as shown in structural formula (V3) to diphenyl phosphate as a catalyst is 1:2.

[0095] The present application proposes a conjugated structure unit as a main chain, and a polycaprolactone side chain as a soft segment is introduced on the side chain of the conjugated unit through a controllable ring-opening polymerization reaction, the electronic affinity is improved at the same time of introducing the soft segment, and the film tensile capacity of the polymer semiconductor material is improved while the certain electronic mobility is improved.

[0096] The organic conjugated polymer semiconductor material of the present application has excellent tensile properties: no obvious cracks in the parallel and vertical directions when stretched to 100% for a single time, and the mobility can still be maintained after the tensile ratio is 100%. When applied to a flexible device, no other additives or elastomer materials need to be added.

[0097] The application further provides application of the polymer semiconductor material shown in structural formula (I) as an intrinsic stretchable organic semiconductor material.

[0098] The application has the following advantages:

[0099] 1. The synthesis steps are short, easy to produce and separate and purify.

[0100] 2. The obtained polymer semiconductor material has good chemical stability.

[0101] 3. The obtained polymer semiconductor material itself has excellent carrier transport performance and solubility, is easy to form a film, and provides convenience for subsequent device processing.

[0102] 4. The obtained polymer semiconductor material itself has good intrinsic stretchability, and does not need to add other additives or elastomer materials when subsequently applied to a flexible device. BRIEF DESCRIPTION OF DRAWINGS

[0103] Figure 1 The preparation flow chart of the compound shown in structural formula (II) in the embodiment 2 of the application.

[0104] Figure 2 The H-NMR chart of the compound shown in structural formula (II) in the embodiment 2 of the application. 1

[0105] Figure 3 The GPC chart of the compound shown in structural formula (II) in the embodiment 2 of the application.

[0106] Figure 4 The preparation flow chart of the polymer semiconductor material P2 shown in structural formula (I) in the embodiment 3 of the application.

[0107] Figure 5 The H-NMR chart of the polymer semiconductor material P2 shown in structural formula (I) in the embodiment 3 of the application. 1

[0108] Figure 6 The infrared spectrum chart of the polymer P1 and the polymer semiconductor material P2 shown in structural formula (I) in the embodiment 3 of the application.

[0109] Figure 7 The ultraviolet-visible light spectrum chart of the polymer P1 in the embodiment 3 of the application.

[0110] Figure 8 ​​The ultraviolet-visible light spectrum of the polymer semiconductor material P2 shown in structural formula (I) in the embodiment 3 of the present application.

[0111] Figure 9 The structural diagram of the conjugated polymer field effect transistor device in the embodiment 4 of the present application.

[0112] Figure 10 The optical microscope images of the two polymer films P1 and P2 in the embodiment 4 of the present application after being stretched to a certain ratio.

[0113] Figure 11 The preparation flow chart of the comparative polymer P1. DETAILED DESCRIPTION

[0114] In order to make the personnel in the technical field better understand the present application scheme, the following will be combined with the drawings and embodiments to explain the embodiment of the present application in detail, by which the implementation process of how to apply technical means to solve the technical problems and achieve the corresponding technical effects can be fully understood and implemented. The embodiments of the present application and each feature in the embodiments can be combined with each other without conflict, and the formed technical solutions are all within the protection scope of the present application.

[0115] Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by the person skilled in the art without creative labor should belong to the protection scope of the present application.

[0116] It should be noted that the terms “include” and “have” in the specification and claims of the present application and the above-mentioned drawings are intended to cover the non-exclusive inclusion.

[0117] Embodiment 1

[0118] A side chain controllable ring-opening polymer semiconductor material, the structural formula of which is shown in structural formula (I), and the structural formula (I) is as follows:

[0119] (I)

[0120] In the structural formula I: Ar1 is an isatin, or a diketopyrrolopyrrole, or a naphthalimide with a polycaprolactone chain segment structure introduced by ring-opening polymerization of the side chain, wherein n is 6-30, and the optimal value of n is 18;

[0121] Ar2 is an isatin, or a diketopyrrolopyrrole, or a naphthalimide with an alkyl side chain;

[0122] R is one of a straight-chain or branched-chain alkyl group with 5-20 carbon atoms; 80 ​

[0123] Ar3 is a thienyl compound, and the bonding mode within the group of Ar3 is selected from a single bond or a double bond;

[0124] x:y is 1:0 to 1:99.

[0125] When Ar1 is isoindigo, 6,6'-dibromoisoindigo in isoindigo is used, and the structural formula is as shown in the following formula:

[0126] ;

[0127] When Ar1 is diketopyrrolopyrrole, 3,6-bis(5-bromothiophen-2-yl) diketopyrrolopyrrole-1,4(2H,5H)-dione in diketopyrrolopyrrole is used, and the structural formula is as shown in the following formula:

[0128] ;

[0129] When Ar1 is naphthalimide, 4,9-dibromo benzo[3,8]phenanthroline-1,3,6,8(2H,7H)-one in naphthalimide is used, and the structural formula is as shown in the following formula:

[0130] .

[0131] wherein n is 6-30, and the optimal value of n is 18; represents the connecting position of the Ar1 group in the polymer semiconductor material shown in the structural formula (I).

[0132] When Ar2 is isoindigo, 6,6'-dibromoisoindigo in isoindigo is used, and the structural formula is as shown in the following formula:

[0133] ;

[0134] When Ar2 is diketopyrrolopyrrole, 3,6-bis(5-bromothiophen-2-yl) diketopyrrolopyrrole-1,4(2H,5H)-dione in diketopyrrolopyrrole is used, and the structural formula is as shown in the following formula:

[0135] ;

[0136] When Ar2 is naphthalimide, 4,9-dibromo benzo[3,8]phenanthroline-1,3,6,8(2H,7H)-one in naphthalimide is used, and the structural formula is as shown in the following formula:

[0137] .

[0138] wherein R is one of C5-C 80 linear or branched alkyl. denotes the position of attachment of the Ar2 group in the polymer semiconductor material of structural formula (I).

[0139] Ar3 is a thienyl group, or a bithienyl group, or a thieno group;

[0140] Ar3 is a thienyl group, or a bithienyl group, or a thieno group;

[0141] Structural formula (a) of thienyl is as follows:

[0142] (a)

[0143] Structural formula (b) of selenophene is as follows:

[0144] (b)

[0145] Structural formula (c) of bithienyl is as follows:

[0146] (c)

[0147] Structural formula (d) of trans-1,2-di(2-thienyl)ethene is as follows:

[0148] (d)

[0149] Structural formula (e) of thieno[3,2-b]thiophene is as follows:

[0150] (e)

[0151] Structural formula (f) of 4,7-di(2-thienyl)-2,1,3-benzothiadiazole is as follows:

[0152] (f)

[0153] wherein, denotes the position of attachment of the Ar3 group in the polymer semiconductor material of structural formula (I).

[0154] Example 2

[0155] This example discloses a method for preparing a conjugated monomer with controllable ring-opening polycaprolactone side chain structure of structural formula (II), the process is as follows:

[0156] The chemical reaction flow chart is shown in FIG. 1. The chemical reaction flow chart is shown in FIG. 2. Figure 1 The chemical reaction flow chart is shown in FIG. 1. The chemical reaction flow chart is shown in FIG. 2.

[0157] The chemical reaction flow chart is shown in FIG. 1. The chemical reaction flow chart is shown in FIG. 2.

[0158] The chemical reaction flow chart is shown in FIG. 1. The chemical reaction flow chart is shown in FIG. 2.

[0159] The chemical reaction flow chart is shown in FIG. 1. The chemical reaction flow chart is shown in FIG. 2. Figure 2 The chemical reaction flow chart is shown in FIG. 1. The chemical reaction flow chart is shown in FIG. 2. 1H NMR (600 MHz, CDCl3), δ(ppm) = 9.08(d, 2H), 7.18 (dd, 2H), 6.94 (d, 2H), 4.06 (t, 72H), 3.77 (t, 4H), 3.66 (t,4H), 2.30 (t, 72H), 1.70-1.35 (m, 236H).

[0160] like Figure 3 The image shown is the GPC spectrum of the dark red solid, where M... n =5509, M w =6131, PDI=1.11.

[0161] Depend on Figure 2 , Figure 3 It can be seen that the dark red solid structure is correct, that is, the conjugated monomer with a polycaprolactone side chain structure with controllable ring opening as shown in structural formula (II).

[0162] Example 3

[0163] This embodiment discloses a method for preparing the polymer semiconductor material with controllable ring-opening side chains shown in structural formula (I) of Embodiment 1 above. The process is as follows:

[0164] Chemical reaction flow chart as follows Figure 4 As shown, the dried Schlenk tube was evacuated using a double-row tube, cooled, and then nitrogen was introduced into the polymerization tube for 10 min. The following were added to the tube: the conjugated monomer with a controllable ring-opening polycaprolactone side chain structure shown in structural formula (II) (22 mg, 0.0050 mmol), the conjugated monomer with an alkyl side chain shown in structural formula (III) (104 mg, 0.095 mmol), and 5,5'-bis(trimethyltin)-2,2'-bithiophene (i.e., thiophene compound, 25 mg, 0.20 mmol) shown in structural formula (IV). The mixture was dissolved in 5 mL of anhydrous chlorobenzene, nitrogen was introduced, and the tube was frozen with liquid nitrogen for 10 min. The tube was then evacuated again using a double-row tube, restored to room temperature, and then nitrogen was introduced again. The freezing process was repeated 3 times.

[0165] Add catalyst Pd2(dba)3 (4 mg) and ligand P(o-tol)3 (5 mg), then evacuate twice using liquid nitrogen. Seal the apparatus and react for two days at 130 °C.

[0166] After the reaction was completed, the mixture was cooled to room temperature and then filtered to obtain the crude product. The product was extracted with methanol, petroleum ether, and chloroform using a Soxhlet extract, and the chloroform extract was evaporated by rotary evaporation to precipitate polymer P2 (98 mg, yield 67%).

[0167] P1 as a comparative polymer, the comparative polymer P1 is not added with the conjugated monomer having controllable ring-opening polycaprolactone side chain structure shown in structural formula (II), such as Figure 11 The reaction condition of the comparative polymer P1 is same as polymer P2 (x:y=0:1).

[0168] Figure 5 The H-NMR chart of polymer P2, the peaks at 2.4 and 4.1 are the peaks of lactone groups. 1 The H-NMR chart of comparative polymer P1, the peaks at 2.4 and 4.1 are the peaks of lactone groups.

[0169] Figure 6 The infrared spectrum chart of polymer P1 and P2, the peak at 1740 cm -1 is the peak of C=O in lactone groups.

[0170] Figure 7 and Figure 8 are respectively the ultraviolet-visible spectrum chart of polymer P1 and the side chain controllable ring-opening polymer semiconductor material P2 shown in structural formula (I).

[0171] From the above Figure 5 , Figure 6 , Figure 7 , Figure 8 , it can be seen that the product P2 is correct structure, that is the side chain controllable ring-opening polymer semiconductor material shown in structural formula (I) in example 1.

[0172] Example 4

[0173] This example discloses the application of the side chain controllable ring-opening polymer semiconductor material shown in structural formula (I) in example 1.

[0174] Specifically, the side chain controllable ring-opening polymer semiconductor material P2 shown in structural formula (I) is prepared into 5 mg / mL chloroform solution for standby, 20 μL of the above solution is taken by a pipette and spin-coated on an OTS modified Si / SiO2 sheet with a size of 1.1*1.1 cm at a speed of 1.5 kr / min to form a film. The polymer film spin-coated on the OTS modified Si / SiO2 silicon sheet is transferred by PDMS, then the PDMS substrate is stretched to a specific strain, and then the polymer film is directly adhered to the PS modified Si / SiO2 substrate (as shown in Figure 9 ). A 30-50 nm thick gold electrode is evaporated on the stretched and transferred film by using a vacuum coating machine, and the length (L) and width (W) of the channel are 100 nm and 1000 nm respectively.

[0175] Figure 10The optical microscope images of the polymer thin film transferred from the two polymers, comparative polymer P1 and side chain controllable ring-opening polymer semiconductor material P2 shown by structural formula (I) in Example 1, to the PDMS substrate and then stretched to a certain ratio are shown in FIG. 1. Figure 10 It can be seen that the polymer thin film prepared from the side chain controllable ring-opening polymer semiconductor material P2 shown by structural formula (I) in Example 1 has good stretchability.

[0176] The preferred embodiments of the present application are described in detail above with reference to the drawings, and the examples described in the present application are merely used to describe the preferred embodiments of the present application, and do not limit the concept and scope of the present application. In the above specific embodiments, each specific technical feature described above can be combined in any appropriate manner without contradiction, and such combination should also be considered as disclosed by the present disclosure, as long as it does not deviate from the technical concept of the present application. In order to avoid unnecessary repetition, the present application will not further describe various possible combinations.

[0177] The present application is not limited to the specific details in the above embodiments, and various modifications and improvements of the technical solutions of the present application made by those skilled in the art within the technical concept of the present application and without departing from the design concept of the present application should fall within the protection scope of the present application. The technical content of the present application claimed for protection has been fully recorded in the claims.

Claims

1. A polymer semiconductor material with controllable ring-opening side chains, characterized in that, Its structural formula is shown in structural formula (I), which is as follows: （I） In structural formula I: Ar1 is isoindigo, or pyrrolopyrrole dione, or naphthalimide, which are polycaprolactone segments introduced by ring-opening polymerization of the side chain, where n is 6 to 30; Ar2 is indigo, pyrrolopyrrole dione, or naphthalimide with an alkyl side chain attached; R is C5-C 80 One of the straight-chain or branched alkyl groups; Ar3 is a thiophene compound, and the bonding mode within the Ar3 group is selected from single bonds or double bonds; x:y ranges from 1:0 to 1:

99.

2. The polymer semiconductor material with controllable ring-opening side chains according to claim 1, characterized in that, When Ar1 is isoindigo, 6,6'-dibromoisoindigo from isoindigo is used, with the structural formula shown below: ； When Ar1 is pyrrolopyrroledione, 3,6-bis(5-bromothiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione from pyrrolopyrroledione is used, with the structural formula shown below: ； When Ar1 is a naphthalimide, the 4,9-dibromobenzo[3,8]phenanthroline-1,3,6,8(2H,7H)-one from the naphthalimide is used, with the structural formula shown below: ， Where n is 6 to 30; This indicates the connection position of the Ar1 group in the polymer semiconductor material shown in structural formula (I).

3. The polymer semiconductor material with controllable ring-opening side chains according to claim 1, characterized in that, When Ar2 is isoindigo, 6,6'-dibromoisoindigo from isoindigo is used, with the structural formula shown below: ； When Ar2 is pyrrolopyrroledione, 3,6-bis(5-bromothiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione from pyrrolopyrroledione is used, with the structural formula shown below: ； When Ar2 is a naphthalimide, 4,9-dibromobenzo[3,8]phenanthroline-1,3,6,8(2H,7H)-one from the naphthalimide is used, with the following structural formula: ， Where R is C5-C 80 One of the straight-chain or branched alkyl groups; This indicates the connection position of the Ar2 group in the polymer semiconductor material shown in structural formula (I).

4. The polymer semiconductor material with controllable ring-opening side chains according to claim 1, characterized in that, Ar3 is a thiophene group, or a bithiophene group, or a denosylthiophene group; Ar3 uses thiophene as shown in structural formula (a), or selenophene as shown in structural formula (b), or dithiophene as shown in structural formula (c), or trans-1,2-bis(2-thienyl)ethylene as shown in structural formula (d), or thieno[3,2-b]thiophene as shown in structural formula (e), or 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole as shown in structural formula (f); The structural formula (a) of thiophene is shown below: （a） The structural formula (b) of selenophene is shown below: （b） The structural formula (c) of dithiophene is shown below: （c） The structural formula (d) of trans-1,2-bis(2-thienyl)ethylene is shown below: （d） The structural formula (e) of thiopheno[3,2-b]thiophene is shown below: （e） The structural formula (f) of 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole is shown below: （f） in, This indicates the connection position of the Ar3 group in the polymer semiconductor material shown in structural formula (I).

5. A method for preparing a polymer semiconductor material with controllable ring-opening side chains as described in any one of claims 1-4, characterized in that, The process is as follows: In an inert atmosphere and in the presence of a catalyst, a conjugated monomer with a polycaprolactone side chain structure as shown in structural formula (II), a conjugated monomer with an alkyl side chain as shown in structural formula (III), and a thiophene compound as shown in structural formula (IV) are subjected to Stille coupling reaction in an organic solvent to obtain a solution system. The conjugated monomer with a polycaprolactone side chain structure that has undergone controllable ring-opening has the following structural formula (II): (II) The structural formula (III) of the conjugated monomer with alkyl side chains is shown below: (III) The structural formula (IV) of the thiophene group compound is shown below: (IV) In structural formula (IV), Y is a trialkyltin group or a borate ester group; Next, the solution system was added dropwise to methanol and filtered to obtain a polymer solid; Subsequently, the polymer solid was extracted sequentially with methanol, acetone and n-hexane to obtain the target product; Then, the target product was extracted with chloroform and then concentrated by rotary evaporation. Finally, the chloroform containing the target product, which was concentrated by rotary evaporation, was dropped into methanol to precipitate, and the final product was obtained by vacuum filtration, which is the polymer semiconductor material shown in structural formula (I).

6. The method for preparing polymer semiconductor materials with controllable ring-opening side chains according to claim 5, characterized in that, The molar ratio of the conjugated monomer with a polycaprolactone side chain structure as shown in structural formula (II), the conjugated monomer with an alkyl side chain as shown in structural formula (III), and the thiophene compound as shown in structural formula (IV) is 1:n:(n+1), where n is 0 to 99.

7. The method for preparing polymer semiconductor materials with controllable ring-opening side chains according to claim 5, characterized in that, The catalyst consists of a palladium catalyst and a phosphine ligand.

8. The method for preparing polymer semiconductor materials with controllable ring-opening side chains according to claim 5, characterized in that, The Stille coupling reaction is carried out at a temperature of 90–130 °C for a time of 8–48 h.

9. The application of a polymer semiconductor material with controllable ring-opening side chains as described in any one of claims 1-4 as an organic semiconductor material.

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