BLOCK COPOLYMER INTRINSIC STRETCHABLE ELECTROLUMINESCENT ELASTOMER AND PREPARATION METHOD AND APPLICATION THEREOF

Abstract

The invention discloses a block copolymer intrinsic stretchable electroluminescent elastomer and its preparation method and application. This type of elastomer is made from organic electroluminescent monomers, styrene and 1,3-butadiene through anionic polymerization. The innovation of the present invention is: for the first time, the organic electroluminescence unit is introduced into the elastomer by chemical crosslinking. On the basis of improving the intrinsic stretchability of the elastomer, at the same time, it has characteristics of excellent luminescence and high carrier mobility, novel structure and unique design strategy; meanwhile, it also solves the inherent non-stretchability problem of traditional organic optoelectronic materials and the problem that traditional elastomers do not have electroluminescent properties. This type of elastomer is used as a light-emitting layer material to prepare organic electroluminescent devices with high stability, high stretchability and high efficiency.

Claims

1. A block copolymer intrinsically stretchable electroluminescent elastomer, characterized in that the elastomer has the following general structural formula: ##STR00078## Among them, a, b, c, d, e, f represent the molar ratio of the block component, a+b+c+d+e+f=1; Ar is selected from one of the following groups: ##STR00079## ##STR00080## ##STR00081## Among them, R is a C.sub.1-C.sub.20 linear or branched alkyl group, the number of n is 1-6, and * is the connection position.

2. A block copolymer intrinsically stretchable electroluminescent elastomer according to claim 1, characterized in that a+b+e+f=0.1˜0.3.

3. The block copolymer intrinsically stretchable electroluminescent elastomer according to claim 1, characterized in that the structure comprises: ##STR00082## ##STR00083##

4. The preparation method of a block copolymer intrinsically stretchable electroluminescent elastomer according to claim 1, characterized in that the monomer ##STR00084## styrene, and 1,3-butane Ene are used as building units. Under the conditions of organic solvents, additives and initiators, the block copolymer intrinsically stretchable electroluminescent elastomer is prepared by anionic polymerization. The reaction equation is as follows: ##STR00085##

5. A method for preparing block copolymer intrinsically stretchable electroluminescent elastomer according to claim 4, characterized in that it comprises the following steps: (1) Under the protection of nitrogen, the monomer ##STR00086## and styrene are dissolved in an organic solvent, additives and initiators are added, and are reacted at 55-75° C. for 1-2 h; (2) They are added to 1,3-butadiene monomer and reacted at 50-70° C. for 2-3 h; (3) They are added again with the same molar amount of ##STR00087## and styrene monomer in the same step (1), and reacted at 55-75° C. for 1-2 h; (4) After the reaction is over, it is cooled to room temperature. After the reaction solution is concentrated, it is dissolved in methylene chloride as an organic solvent, precipitated with methanol, and purified by column chromatography. After extraction, methanol sedimentation, suction filtration, and drying, the elastomer obtained is the target product, the block copolymer intrinsically stretchable electroluminescent elastomer.

6. According to claim 4, the method for preparing a block copolymerized intrinsically stretchable electroluminescent elastomer is characterized in that 1 mmol monomer ##STR00088## is dissolved in 5-25 mL of organic solvent and added 0.02-0.08 mL of additive, 0.02-0.08 mL of initiator.

7. According to claim 4, the method for preparing a block copolymerized intrinsically stretchable electroluminescent elastomer is characterized in that the organic solvents include hexane, cyclohexane, toluene, dioxane; additives include tetrahydrofuran, ether, acetonitrile; initiators include n-butyl lithium, tert-butyl lithium.

8. According to claim 1, the application of a block copolymer intrinsically stretchable electroluminescent elastomer is characterized in that the elastomer is used as a photoelectric functional layer material to include stretchable organic electroluminescent devices, software robots, artificial intelligence and other stretchable electronics fields.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0016] FIG. 1 is the cyclic voltammetry curve (CV curve) of the elastomer;

[0017] FIG. 2 is the thermal weight loss curve of the elastomer;

[0018] FIG. 3 is the tensile test curve diagram of the elastomer;

[0019] FIG. 4 is the current density/brightness-voltage curve of the organic electroluminescence properties of elastomers.

DETAILED DESCRIPTION OF THE INVENTION

[0020] A block copolymer intrinsically stretchable electroluminescent elastomer, which has the following general structural formula:

##STR00012##

[0021] Among them, a, b, c, d, e, f represent the molar ratio of the block component, a+b+c+d+e+f=1; Ar is selected from one of the following groups:

##STR00013## ##STR00014## ##STR00015##

among them, R is a C.sub.1-C.sub.20 linear or branched alkyl group, the number of n is 1-6, and * is the connection position.

[0022] The preparation method of this type of block copolymerization intrinsically stretchable electroluminescent elastomer is: the monomer

##STR00016##

styrene, and 1,3-butadiene are used as building units. Under the conditions of organic solvents, additives and initiators, a series of intrinsically stretchable electroluminescent elastomers are prepared by anionic polymerization.

Embodiment 1

[0023] If Ar is selected as

##STR00017##

the preparation of elastomer SBS-Ar1:

##STR00018##

##STR00019##

(500 mg, 1.64 mmol) is put into two 50 mL reaction flasks and sealed, and nitrogen is pumped three times. Styrene (0.5 mL, 4.37 mmol), ultra-dry cyclohexane (10 mL), ultra-dry THF (0.03 mL), 0.03 mL of n-BuLi are injected into the reaction flask, and reacted at 65° C. for 1 h. Subsequently, the temperature is loared to 63° C., 7 mL of 1,3-butadiene is added, and the reaction is carried out for 2 h. Finally,

##STR00020##

(500 mg, 1.64 mmol) and styrene (0.5 mL, 4.37 mmol) are added to the reaction flask and reacted at 65° C. for 1 h. After the reaction, the unreacted n-BuLi is quenched by adding absolute ethanol. After the reaction solution is concentrated, it is dissolved in DCM, precipitated in methanol, and purified by column chromatography.
Subsequently, Soxhlet extraction is performed with n-hexane, methanol, and acetone for 48 h. The product is settled with methanol solvent again, filtered with suction and dried in vacuum to obtain elastomer SBS-Ar1 (15.08 g, the yield is 82%), and the ratio of the actual value of the final product to the total feeding amount is the yield.

Embodiment 2

[0024] If Ar is selected as

##STR00021##

the preparation of elastomer SBS-Ar2 (among them, R is a C6 linear alkyl group and the number of n is 1):

##STR00022## ##STR00023##

##STR00024##

(250 mg, 0.41 mmol) is put into two 50 mL reaction flasks and sealed, and nitrogen is pumped three times. Styrene (0.5 mL, 4.37 mmol), ultra-dry cyclohexane (10 mL), ultra-dry THF (0.02 mL), 0.02 mL of n-BuLi are injected into the reaction flask, and reacted at 65° C. for 1 h. Subsequently, the temperature is loared to 63° C., 7 mL of 1,3-butadiene is added, and the reaction is carried out for 2 h. Finally,

##STR00025##

(250 mg, 0.41 mmol) and styrene (0.5 mL, 4.37 mmol) are added to the reaction flask and reacted at 65° C. for 1 h. After the reaction, the unreacted n-BuLi is quenched by adding absolute ethanol. After the reaction solution is concentrated, it is dissolved in DCM, precipitated in methanol, and purified by column chromatography. Subsequently, Soxhlet extraction is performed with n-hexane, methanol, and acetone for 48 h. The product is settled with methanol solvent again, filtered with suction and dried in vacuum to obtain elastomer SBS-Ar2 (4.12 g, the yield is 73%).

Embodiment 3

[0025] If Ar is selected as

##STR00026##

the preparation of elastomer SBS-Ar3:

##STR00027##

##STR00028##

(1 g, 2.81 mmol) is put into two 50 mL reaction flasks and sealed, and nitrogen is pumped three times. Styrene (0.5 mL, 4.37 mmol), ultra-dry cyclohexane (12 mL), ultra-dry THF (0.08 mL), 0.08 mL of n-BuLi are injected into the reaction flask, and reacted at 65° C. for 1 h. Subsequently, the temperature is loared to 63° C., 7 mL of 1,3-butadiene is added, and the reaction is carried out for 2 h. Finally,

##STR00029##

(1 g, 2.81 mmol) and styrene (0.5 mL, 4.37 mmol) are added to the reaction flask and reacted at 65° C. for 1 h. After the reaction, the unreacted n-BuLi is quenched by adding absolute ethanol. After the reaction solution is concentrated, it is dissolved in DCM, precipitated in methanol, and purified by column chromatography. Subsequently, Soxhlet extraction is performed with n-hexane, methanol, and acetone for 48 h. The product is settled with methanol solvent again, filtered with suction and dried in vacuum to obtain elastomer SBS-Ar3 (5.25 g, the yield is 73%).

Embodiment 4

[0026] If Ar is selected as

##STR00030##

the preparation of elastomer SBS-Ar4:

##STR00031##

##STR00032##

(1.5 g, 2.43 mmol) is put into two 50 mL reaction flasks and sealed, and nitrogen is pumped three times. Styrene (0.5 mL, 4.37 mmol), ultra-dry cyclohexane (15 mL), ultra-dry THF (0.12 mL), 0.12 mL of n-BuLi are injected into the reaction flask, and reacted at 65° C. for 1 h. Subsequently, the temperature is loared to 63° C., 7 mL of 1,3-butadiene is added, and the reaction is carried out for 2 h. Finally,

##STR00033##

(1.5 g, 2.43 mmol) and styrene (0.5 mL, 4.37 mmol) are added to the reaction flask and reacted at 65° C. for 1 h. After the reaction, the unreacted n-BuLi is quenched by adding absolute ethanol. After the reaction solution is concentrated, it is dissolved in DCM, precipitated in methanol, and purified by column chromatography. Subsequently, Soxhlet extraction is performed with n-hexane, methanol, and acetone for 48 h. The product is settled with methanol solvent again, filtered with suction and dried in vacuum to obtain elastomer SBS-Ar4 (6.50 g, the yield is 79%).

Embodiment 5

[0027] If Ar is selected as

##STR00034##

the preparation of elastomer SBS-Ar5:

##STR00035## ##STR00036##

##STR00037##

(1 g, 1.23 mmol) is put into two 50 mL reaction flasks and sealed, and nitrogen is pumped three times. Styrene (1 mL, 8.73 mmol), ultra-dry cyclohexane (12 mL), ultra-dry THF (0.07 mL), 0.07 mL of n-BuLi are injected into the reaction flask, and reacted at 65° C. for 1 h. Subsequently, the temperature is loared to 63° C., 7 mL of 1,3-butadiene is added, and the reaction is carried out for 2 h. Finally,

##STR00038##

(1 g, 1.23 mmol) and styrene (1 mL, 8.73 mmol) are added to the reaction flask and reacted at 65° C. for 1 h. After the reaction, the unreacted n-BuLi is quenched by adding absolute ethanol. After the reaction solution is concentrated, it is dissolved in DCM, precipitated in methanol, and purified by column chromatography. Subsequently, Soxhlet extraction is performed with n-hexane, methanol, and acetone for 48 h. The product is settled with methanol solvent again, filtered with suction and dried in vacuum to obtain elastomer SBS-Ar5 (6.18 g, the yield is 76%).

Embodiment 6

[0028] If Ar is selected as

##STR00039##

the preparation of elastomer SBS-Ar6:

##STR00040## ##STR00041##

##STR00042##

(750 mg, 0.87 mmol) is put into two 50 mL reaction flasks and sealed, and nitrogen is pumped three times. Styrene (1 mL, 8.73 mmol), ultra-dry cyclohexane (12 mL), ultra-dry THF (0.07 mL), 0.07 mL of n-BuLi are injected into the reaction flask, and reacted at 65° C. for 1 h. Subsequently, the temperature is loared to 63° C., 7 mL of 1,3-butadiene is added, and the reaction is carried out for 2 h. Finally,

##STR00043##

(750 mg, 0.87 mmol) and styrene (1 mL, 8.73 mmol) are added to the reaction flask and reacted at 65° C. for 1 h. After the reaction, the unreacted n-BuLi is quenched by adding absolute ethanol. After the reaction solution is concentrated, it is dissolved in DCM, precipitated in methanol, and purified by column chromatography. Subsequently, Soxhlet extraction is performed with n-hexane, methanol, and acetone for 48 h. The product is settled with methanol solvent again, filtered with suction and dried in vacuum to obtain elastomer SBS-Ar6 (6.68 g, the yield is 88%).

Embodiment 7

[0029] If Ar is selected as

##STR00044##

the preparation of elastomer SBS-Ar7:

##STR00045## ##STR00046##

##STR00047##

(500 mg, 0.58 mmol) is put into two 50 mL reaction flasks and sealed, and nitrogen is pumped three times. Styrene (1 mL, 8.73 mmol), ultra-dry cyclohexane (12 mL), ultra-dry THF (0.05 mL), 0.05 mL of n-BuLi are injected into the reaction flask, and reacted at 65° C. for 1 h. Subsequently, the temperature is loared to 63° C., 7 mL of 1,3-butadiene is added, and the reaction is carried out for 2 h. Finally,

##STR00048##

(500 mg, 0.58 mmol) and styrene (1 mL, 8.73 mmol) are added to the reaction flask and reacted at 65° C. for 1 h. After the reaction, the unreacted n-BuLi is quenched by adding absolute ethanol. After the reaction solution is concentrated, it is dissolved in DCM, precipitated in methanol, and purified by column chromatography. Subsequently, Soxhlet extraction is performed with n-hexane, methanol, and acetone for 48 h. The product is settled with methanol solvent again, filtered with suction and dried in vacuum to obtain elastomer SBS-Ar7(5.87, the yield is 83%).

Embodiment 8

[0030] If Ar is selected as

##STR00049##

the preparation of elastomer SBS-Ar8:

##STR00050## ##STR00051##

##STR00052##

(500 mg, 1.16 mmol) is put into two 50 mL reaction flasks and sealed, and nitrogen is pumped three times. Styrene (1 mL, 8.73 mmol), ultra-dry cyclohexane (12 mL), ultra-dry THF (0.08 mL), 0.08 mL of n-BuLi are injected into the reaction flask, and reacted at 65° C. for 1 h. Subsequently, the temperature is loared to 63° C., 7 mL of 1,3-butadiene is added, and the reaction is carried out for 2 h. Finally,

##STR00053##

(500 mg, 1.16 mmol) and styrene (1 mL, 8.73 mmol) are added to the reaction flask and reacted at 65° C. for 1 h. After the reaction, the unreacted n-BuLi is quenched by adding absolute ethanol. After the reaction solution is concentrated, it is dissolved in DCM, precipitated in methanol, and purified by column chromatography. Subsequently, Soxhlet extraction is performed with n-hexane, methanol, and acetone for 48 h. The product is settled with methanol solvent again, filtered with suction and dried in vacuum to obtain elastomer SBS-Ar8 (4.96 g, the yield is 70%).

Embodiment 9

[0031] If Ar is selected as

##STR00054##

the preparation of elastomer SBS-Ar9:

##STR00055## ##STR00056##

##STR00057##

(1 g, 2.1 mmol) is put into two 50 mL reaction flasks and sealed, and nitrogen is pumped three times. Styrene (1 mL, 8.73 mmol), ultra-dry cyclohexane (15 mL), ultra-dry THF (0.1 mL), 0.1 mL of n-BuLi are injected into the reaction flask, and reacted at 65° C. for 1 h. Subsequently, the temperature is loared to 63° C., 7 mL of 1,3-butadiene is added, and the reaction is carried out for 2 h. Finally,

##STR00058##

(1 g, 2.1 mmol) and styrene (1 mL, 8.73 mmol) are added to the reaction flask and reacted at 65° C. for 1 h. After the reaction, the unreacted n-BuLi is quenched by adding absolute ethanol. After the reaction solution is concentrated, it is dissolved in DCM, precipitated in methanol, and purified by column chromatography. Subsequently, Soxhlet extraction is performed with n-hexane, methanol, and acetone for 48 h. The product is settled with methanol solvent again, filtered with suction and dried in vacuum to obtain elastomer SBS-Ar9 (7.18 g, the yield is 89%).

Embodiment 10

[0032] If Ar is selected as

##STR00059##

the preparation of elastomer SBS-Ar10:

##STR00060##

##STR00061##

(2 g, 3.9 mmol) is put into two 50 mL reaction flasks and sealed, and nitrogen is pumped three times. Styrene (1 mL, 8.73 mmol), ultra-dry cyclohexane (18 mL), ultra-dry THF (0.2 mL), 0.2 mL of n-BuLi are injected into the reaction flask, and reacted at 65° C. for 1 h. Subsequently, the temperature is loared to 63° C., 7 mL of 1,3-butadiene is added, and the reaction is carried out for 2 h. Finally,

##STR00062##

(2 g, 3.9 mmol) and styrene (1 mL, 8.73 mmol) are added to the reaction flask and reacted at 65° C. for 1 h. After the reaction, the unreacted n-BuLi is quenched by adding absolute ethanol. After the reaction solution is concentrated, it is dissolved in DCM, precipitated in methanol, and purified by column chromatography. Subsequently, Soxhlet extraction is performed with n-hexane, methanol, and acetone for 48 h. The product is settled with methanol solvent again, filtered with suction and dried in vacuum to obtain elastomer SBS-Ar10 (7.88 g, the yield is 78%).

Embodiment 11

[0033] If Ar is selected as

##STR00063##

the preparation of elastomer SBS-Ar11:

##STR00064## ##STR00065##

##STR00066##

(1 g, 1.79 mmol) is put into two 50 mL reaction flasks and sealed, and nitrogen is pumped three times. Styrene (1.5 mL, 13.11 mmol), ultra-dry cyclohexane (20 mL), ultra-dry THF (0.14 mL), 0.14 mL of n-BuLi are injected into the reaction flask, and reacted at 65° C. for 1 h. Subsequently, the temperature is loared to 63° C., 7 mL of 1,3-butadiene is added, and the reaction is carried out for 2 h. Finally,

##STR00067##

(1 g, 1.79 mmol) and styrene (1.5 mL, 13.11 mmol) are added to the reaction flask and reacted at 65° C. for 1 h. After the reaction, the unreacted n-BuLi is quenched by adding absolute ethanol. After the reaction solution is concentrated, it is dissolved in DCM, precipitated in methanol, and purified by column chromatography. Subsequently, Soxhlet extraction is performed with n-hexane, methanol, and acetone for 48 h. The product is settled with methanol solvent again, filtered with suction and dried in vacuum to obtain elastomer SBS-Ar11 (6.84 g, the yield is 76%).

Embodiment 12

[0034] If Ar is selected as

##STR00068##

the preparation of elastomer SBS-Ar12:

##STR00069## ##STR00070##

##STR00071##

(1 g, 1.38 mmol) is put into two 50 mL reaction flasks and sealed, and nitrogen is pumped three times. Styrene (1.5 mL, 13.11 mmol), ultra-dry cyclohexane (20 mL), ultra-dry THF (0.10 mL), 0.10 mL of n-BuLi are injected into the reaction flask, and reacted at 65° C. for 1 h. Subsequently, the temperature is loared to 63° C., 7 mL of 1,3-butadiene is added, and the reaction is carried out for 2 h. Finally,

##STR00072##

(1 g, 1.38 mmol) and styrene (1.5 mL, 13.11 mmol) are added to the reaction flask and reacted at 65° C. for 1 h. After the reaction, the unreacted n-BuLi is quenched by adding absolute ethanol. After the reaction solution is concentrated, it is dissolved in DCM, precipitated in methanol, and purified by column chromatography. Subsequently, Soxhlet extraction is performed with n-hexane, methanol, and acetone for 48 h. The product is settled with methanol solvent again, filtered with suction and dried in vacuum to obtain elastomer SBS-Ar12 (6.32 g, the yield is 70%).

Embodiment 13

[0035] If Ar is selected as

##STR00073##

the preparation of elastomer SBS-Ar13:

##STR00074## ##STR00075##

##STR00076##

(1 g, 0.93 mmol) is put into two 50 mL reaction flasks and sealed, and nitrogen is pumped three times. Styrene (1.5 mL, 13.11 mmol), ultra-dry cyclohexane (20 mL), ultra-dry THF (0.06 mL), 0.06 mL of n-BuLi are injected into the reaction flask, and reacted at 65° C. for 1 h. Subsequently, the temperature is loared to 63° C., 7 mL of 1,3-butadiene is added, and the reaction is carried out for 2 h. Finally,

##STR00077##

(1 g, 0.93 mmol) and styrene (1.5 mL, 13.11 mmol) are added to the reaction flask and reacted at 65° C. for 1 h. After the reaction, the unreacted n-BuLi is quenched by adding absolute ethanol. After the reaction solution is concentrated, it is dissolved in DCM, precipitated in methanol, and purified by column chromatography. Subsequently, Soxhlet extraction is performed with n-hexane, methanol, and acetone for 48 h. The product is settled with methanol solvent again, filtered with suction and dried in vacuum to obtain elastomer SBS-Ar13 (7.74 g, the yield is 86%).

Embodiment 14: OLED Device Preparation

[0036] After ultrasonic cleaning, the ITO glass is treated with oxygen plasma, and the sheet resistance of the ITO glass is 10 Ω/cm2. The hole injection layer is PEDOT or PVK, and the light-emitting layer adopts any one of SBS-Ar1, SBS-Ar2, SBS-Ar3, SBS-Ar4, SBS-Ar5, SBS-Ar6, SBS-Ar7, SBS-Ar8, SBS-Ar9, SBS-Ar10, SBS-Ar11, SBS-Ar12 or SBS-Ar13. Both the hole injection layer and the light emitting layer are made by spin coating. The cathode electrode adopts Ca/A1 or LiF/Al respectively. Among them, the maximum luminous efficiency of the OLED device prepared based on SBS-Ar1 is 8.50 cd/A, and the maximum luminous brightness is 4776 cd/m2; the stretch rate of SBS-Ar12 can reach 900%.

[0037] The above are the embodiments of the present inventors. It should be noted that the present invention is not limited to these examples. These examples are only for a better understanding of the present invention. Any equivalent changes made according to the technical solutions of the present invention belong to the protection scope of the present invention.