Synthesis method of polyaryl sulfide polymer

Abstract

The invention discloses a synthesis method of a polyaryl sulfide polymer, tris (dibenzylideneacetone) dipalladium (Pd (dba) 2) is used as a Pd catalyst, and a series of polyaryl sulfide polymer materials are synthesized through C-S coupling of dibromo aromatic hydrocarbon and a diaryl thioacid ester monomer. Compared with a traditional polyaryl sulfide synthesis method, the method provided by the invention is milder and has high compatibility to monomers. Compared with diaryl thiophenol, the diaryl thioacid ester used as the monomer has the following advantages: the synthesis modes of the monomer are diversified and efficient; the monomer is easy to purify, and the purity is more than 99%; the monomer stability is high; and the polymerization reaction is more efficient and controllable. The polyaryl sulfide polymer provided by the invention is convenient to process, and specifically, the polyaryl sulfide polymer has good solubility in a conventional solvent, such as tetrahydrofuran (THF). The polyaryl sulfide high polymer material with the advantages has great development and application prospects in high refractive index and anisotropic catalysis.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a method for synthesizing a polyaryl sulfide polymer. Background Art

[0002] Polymer materials are materials composed of compounds with relatively high molecular weight, including rubber, plastics, fibers, coatings, adhesives and polymer-based composite materials. Organosulfur compounds are a type of organic compound. They have attracted great attention from chemical researchers due to their wide applications in industry, agriculture, medicine, etc., and a large number of research results on organosulfur chemistry are reported every year. With the continuous expansion of its research scope, it has now covered many fields such as organic synthetic chemistry, pharmacology, biochemistry and structural chemistry, becoming a research field with great development prospects. Among them, aryl sulfide is the most widely used and most studied type of organosulfur compound.

[0003] Polyaryl sulfide (PAS) is a class of high-performance polymer materials, the main chain of which is composed of sulfide and aryl structures. Polyaryl sulfide includes polyphenylene sulfide (PPS) resin, which has been industrialized on a large scale and widely used. On the basis of having general mechanical properties such as high temperature resistance, corrosion resistance and high strength, it also has some special properties and potential application fields due to structural changes. It is a high-quality and low-cost variety in the high-performance polymer series.

[0004] Aryl sulfide has great application prospects in the fields of medicine, agriculture, dye industry and functional materials, and has a profound impact on human production and life, making it one of the hot topics in today's research field. However, in the synthesis of aryl sulfide, complex ligands or some reaction substrates are usually used with low stability, which affects the reaction effect and leads to high synthesis cost of such compounds. To this end, we proposed a method for synthesizing polyaryl sulfide polymers. Summary of the invention

[0005] The purpose of the present invention is to solve the problems existing in the prior art and to propose a method for synthesizing a polyaryl sulfide polymer, which is more gentle and has high compatibility with monomers. The synthesized polyaryl sulfide polymer material has great development and application prospects in high refractive index and anisotropic catalysis.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A method for synthesizing a polyaryl sulfide polymer, including its reaction formula and monomers are as follows:

[0008]

[0009]

[0010] The synthesis of the polyaryl sulfide polymer comprises the following method:

[0011] The reaction formula and synthesis method of the polyaryl sulfide polymer P1 are as follows:

[0012]

[0013] In a 15 mL dry pressure tube, 9,9-dioctyl-2,7-dibromofluorene (164.5 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl)) diethylsulfate (100.2 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide (tB) (40.5 mg, 0.006 mmol, 0.02 equiv) were accurately weighed in sequence. uONa)(144.2mg, 1.5mmol, 5.0equiv), N2 replaced 5 times, anhydrous toluene (1.0mL) was added, and the reaction was carried out at 75°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2mL of dilute hydrochloric acid (2.0M), 2mL of saturated brine and 8mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 183.5mg of P1 polymer as a light yellow spun solid with a yield of 92%;

[0014] The reaction formula and synthesis method 2 of the polyaryl sulfide polymer P1 are as follows:

[0015]

[0016] In a 15 mL dry pressure tube, 9,9-dioctyl-2,7-dibromofluorene (164.5 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl))diphenylsulfate (137.4 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide (tB) (40.4 mg, 0.006 mmol, 0.02 equiv) were accurately weighed in sequence. uONa)(144.2mg, 1.5mmol, 5.0equiv), N2 replaced 5 times, anhydrous toluene (1.0mL) was added, and the reaction was carried out at 75°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2mL of dilute hydrochloric acid (2.0M), 2mL of saturated brine and 8mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 175.8mg of P1 polymer as a light yellow spun solid with a yield of 88%;

[0017] The reaction formula and synthesis method three of the polyarylether polymer P1 are as follows:

[0018]

[0019] In a 15 mL dry pressure tube, 9,9-dioctyl-2,7-dibromofluorene (164.5 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl))dicyclohexanethioate (141.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide ( tBuONa)(144.2mg, 1.5mmol, 5.0equiv), N2 replaced 5 times, anhydrous toluene (1.0mL) was added, and the reaction was carried out at 70°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2mL of dilute hydrochloric acid (2.0M), 2mL of saturated brine and 8mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10mL of saturated brine. The organic phase was concentrated, and tetrahydrofuran was added until it was just completely dissolved. The organic phase was added dropwise to 50mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 185.8mg of P1 polymer as a light yellow spun solid with a yield of 93%;

[0020] The reaction formula and synthesis method of the polyaryl sulfide polymer P2 are as follows:

[0021]

[0022] In a 15 mL dry pressure tube, 2,2'-dibromo-9,9'-spirobifluorene (145.2 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl))dicyclohexanethioate (141.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide ( tBuONa)(144.2mg, 1.5mmol, 5.0equiv), N2 replaced 5 times, anhydrous toluene (1.0mL) was added, and the reaction was carried out at 75°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2mL of dilute hydrochloric acid (2.0M), 2mL of saturated brine and 8mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 154.5mg of P2 polymer as a light yellow powder solid with a yield of 87%;

[0023] The reaction formula and synthesis method of the polyaryl sulfide polymer P3 are as follows:

[0024]

[0025] In a 15 mL dry pressure tube, 2,7'-dibromo-9,9'-spirobifluorene (145.2 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl))dicyclohexanethioate (141.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide ( tBuONa)(144.2mg, 1.5mmol, 5.0equiv), N2 replaced 5 times, anhydrous toluene (1.0mL) was added, and the reaction was carried out at 75°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2mL of dilute hydrochloric acid (2.0M), 2mL of saturated brine and 8mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 161.6mg of P3 polymer as a light yellow powder solid with a yield of 91%;

[0026] The reaction formula and synthesis method of the polyaryl sulfide polymer P4 are as follows:

[0027]

[0028] 2,2'-Dibromo-9,9'-spirobifluorene (145.2 mg, 0.3 mmol, 1.0 equiv), 4,4'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bisphenyldicyclohexanethioate (176.4 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv) were accurately weighed in a 15 mL dry pressure tube. , sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv), N2 was replaced 5 times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 80°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10 mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 181.1 mg of P4 polymer as a light yellow powder solid with a yield of 85%;

[0029] The reaction formula and synthesis method of the polyaryl sulfide polymer P5 are as follows:

[0030]

[0031] 2,7'-dibromo-9,9'-spirobifluorene (145.2 mg, 0.3 mmol, 1.0 equiv), 4,4'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bisphenyldicyclohexanethioate (176.4 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv) were accurately weighed in a 15 mL dry pressure tube. , sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv), N2 was replaced 5 times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 80°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10 mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 159.7 mg of P5 polymer as a light yellow spun solid with a yield of 75%;

[0032] The reaction formula and synthesis method of the polyaryl sulfide polymer P6 are as follows:

[0033]

[0034] 9,9-dioctyl-2,7-dibromofluorene (164.5 mg, 0.3 mmol, 1.0 equiv), (R)-S,S'-(9,9'-spirobis[fluorene]-2,2'-diyl)dicyclohexanethioate (180.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv) were accurately weighed in a 15 mL dry pressure tube. , sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv), N2 replacement 5 times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 80°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10 mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 222.1 mg of P6 polymer as a yellow powder solid with a yield of 93%;

[0035] The reaction formula and synthesis method of the polyaryl sulfide polymer P7 are as follows:

[0036]

[0037] 9,9-dioctyl-2,7-dibromofluorene (164.5 mg, 0.3 mmol, 1.0 equiv), (R)-S,S'-(9,9'-spirobis[fluorene]-2,7'-diyl)dicyclohexanethioate (180.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv) were accurately weighed in a 15 mL dry pressure tube. , sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv), N2 was replaced 5 times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 65°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10 mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was completely dissolved, and the organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 210.2 mg of P7 polymer as a yellow spherical solid with a yield of 88%;

[0038] The reaction formula and synthesis method of the polyaryl sulfide polymer P8 are as follows:

[0039]

[0040] In a 15 mL dry pressure tube, accurately weigh 2,7-dibromospiro[fluorene-9,9'-oxanthene] (147.1 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl))dicyclohexanethioate (141.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide, and 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv). (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv), N2 replaced 5 times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 80 ° C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10 mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100 ° C to obtain 169.6 mg of P8 polymer as a light yellow powder solid with a yield of 93%;

[0041] The reaction formula and synthesis method of the polyaryl sulfide polymer P9 are as follows:

[0042]

[0043] In a 15 mL dry pressure tube, accurately weigh 2,7-dibromospiro[fluorene-9,9'-oxanthene] (147.1 mg, 0.3 mmol, 1.0 equiv), 4,4'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bisphenyldicyclohexanethioate (176.4 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv) in sequence. ), sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv), N2 was replaced 5 times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 90 ° C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10 mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was completely dissolved, and the organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100 ° C to obtain 206.9 mg of P9 polymer as a light yellow powder solid with a yield of 95%;

[0044] The reaction formula and synthesis method of the polyaryl sulfide polymer P10 are as follows:

[0045]

[0046] In a 15 mL dry pressure tube, accurately weigh S-(7-bromo-9,9-dioctyl-9H-fluoren-2-yl) cyclohexanethioate G (183.1 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (1.8 mg, 0.003 mmol, 0.01 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (2.5 mg, 0.0045 mmol, 0.015 equiv), sodium tert-butylate (tBuONa) (72.1 mg, 0.7 5mmol, 2.5equiv), N2 replaced 5 times, anhydrous toluene (0.5mL) was added, and the reaction was carried out at 90°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2mL of dilute hydrochloric acid (2.0M), 2mL of saturated brine and 8mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 124.2mg of P10 polymer as a yellow powder solid with a yield of 92%;

[0047] The synthesized polyaryl sulfide polymers P3 and P11 can be loaded with palladium catalysts to prepare heterogeneous catalysts Pd2+@P3 and Pd2+@P11, which can efficiently realize Suzuki coupling reactions and olefin isomerization reactions.

[0048] Preferably, the synthesis of the diaryl thioester monomer comprises the following method:

[0049] The reaction formula and synthesis method of the monomer A are as follows:

[0050]

[0051] Acetic acid (6.0 mL, 100 mmol, 4.0 equiv) and acetic anhydride (5.0 mL, 50 mmol, 2.0 equiv) were added to a 50 mL three-necked flask, and the mixture was reacted at 45 ° C for 2.5 hours. Then, 4'4-dimercaptodiphenyl sulfide (6.25 g, 25 mmol, 1.0 equiv) and pyridine (20.0 uL, 0.25 mmol, 0.01 equiv) were added, and the mixture was reacted at 30 ° C for 12 hours. After the reaction, the reaction solution was cooled to room temperature, and then 50 mL of saturated brine was added to quench the mixture and extracted three times with ethyl acetate (50 mL×3). The organic phases were combined and dried using a rotary evaporator. Finally, the mixture was recrystallized with ethanol and dried in a vacuum oven at 80 ° C to obtain 6.5 g of white crystals of monomer A with a yield of 78%;

[0052] The reaction formula and synthesis method of the monomer B are as follows:

[0053]

[0054] 4'4-dimercaptodiphenyl sulfide (6.25 g, 20 mmol, 1.0 equiv) and 4-dimethylaminopyridine (DMAP) (24.5 mg, 0.2 mmol, 0.01 equiv) were added to a 250 mL three-necked flask. After N2 replacement for 3 times, DCM (40 mL) was added. Benzoyl chloride (4.7 mL, 40 mmol, 2.0 equiv) and triethylamine (Et3N) (11.2 mL, 80 mmol, 4.0 equiv) were added dropwise in sequence under stirring at 0°C. The mixture was stirred at room temperature overnight. After the reaction was completed, 50 mL of saturated brine was added to quench the mixture and the mixture was extracted three times with ethyl acetate (50 mL×3). The organic phases were combined and dried using a rotary evaporator. Finally, flash column chromatography (PE:EA=2:1) ​​was performed, and the mixture was recrystallized from dichloromethane and petroleum ether and dried in a vacuum oven at 80°C to obtain 8.0 g of pale yellow crystals of monomer B with a yield of 88%.

[0055] The reaction formula and synthesis method of the monomer C are as follows:

[0056]

[0057] 4'4-dimercaptodiphenyl sulfide (6.25 g, 20 mmol, 1.0 equiv) and 4-dimethylaminopyridine (DMAP) (24.5 mg, 0.2 mmol, 0.01 equiv) were added to a 250 mL three-necked flask. After N2 replacement for 3 times, DCM (40 mL) was added. Cyclohexanecarbonyl chloride (5.4 mL, 40 mmol, 2.0 equiv) and triethylamine (Et3N) (11.2 mL, 80 mmol, 4.0 equiv) were added dropwise in sequence under stirring at 0°C. The mixture was stirred at room temperature overnight. After the reaction was completed, 50 mL of saturated brine was added to quench the mixture and the mixture was extracted three times with ethyl acetate (50 mL×3). The organic phases were combined and dried using a rotary evaporator. Finally, flash column chromatography (PE:EA=2:1) ​​was performed, and the mixture was recrystallized from dichloromethane and petroleum ether and dried in a vacuum oven at 80°C to obtain 4.4 g of white crystals of monomer C with a yield of 94%.

[0058] The reaction formula and synthesis method of the monomer D are as follows:

[0059]

[0060] Potassium hydroxide KOH (12.0 g, 190 mmol, 2.1 equiv) was added to a 150 mL three-necked flask, and N2 was replaced 5 times. Anhydrous methanol (100 mL) was added and stirred. After KOH was completely dissolved, hexafluorobisphenol I (30.0 g, 90 mmol, 1.0 equiv) was added and stirred in an ice-water bath for 0.5 hour. Then, dimethylaminothiocarbonyl chloride (28.7 g, 225 mmol, 2.5 equiv) was added and stirred in an ice-water bath for 6 hours. Then, it was stirred at room temperature overnight. After the reaction was completed, it was filtered, and the solid was washed with ice water and methanol (1:1). It was dried in a vacuum oven at 100°C to obtain 30 g of white solid II with a yield of 70%. II was added to a dry 100 mL three-necked flask and nitrogen was replaced 5 times. Then, it was stirred and reacted at 250°C in nitrogen for 2.5 hours. After the reaction was completed, the crude product was dried and recrystallized with methanol: water (6:1, v / v) to obtain white solid III 19.5g, yield 65%, KOH (6.2g, 100mmol, 5.0equiv) and III (10.2g, 20mmol, 1.0equiv) were added to a 250mL three-necked flask, N2 was replaced 5 times, methanol (80mL) and deionized water (40mL) were added to reflux for 2 hours, after the reaction, no purification was required, the extraction was directly spin-dried for the next step, IV (7.4g, 20mmol, 1.0equiv) and 4-dimethylaminopyridine (DMAP) (24.5mg, 0.2mmol, 0.01equiv) were added to a 250mL three-necked flask , after N2 replacement 3 times, DCM (40 mL) was added, and cyclohexanecarbonyl chloride (5.4 mL, 40 mmol, 2.0 equiv) and triethylamine (Et3N) (11.2 mL, 80 mmol, 4.0 equiv) were added dropwise in sequence under stirring at 0°C, and stirred at room temperature overnight. After the reaction was completed, 50 mL of saturated brine was added to quench the reaction, and the mixture was extracted three times with ethyl acetate (50 mL×3). The organic phases were combined and dried using a rotary evaporator. Finally, flash column chromatography (PE:EA=2:1) ​​was performed, and the mixture was recrystallized from dichloromethane and petroleum ether, and dried in a vacuum oven at 80°C to obtain 8.6 g of monomer D as a white solid with a yield of 73%;

[0061] The reaction formula and synthesis method of the monomer E are as follows:

[0062]

[0063] 2,2'-dibromo-9,9'-spirobifluorene (9.5 g, 20 mmol, 1.0 equiv) and 1,3-dimethyl-2-imidazolidinone (DMI) (200 mL) were added to a 500 mL three-necked flask. After N2 degassing for 10 minutes, sodium thiomethoxide (15 g, 200 mmol, 10.0 equiv) was added and reacted at 120°C for 36 hours. The reaction solution was cooled to room temperature, and cyclohexanecarbonyl chloride (27.0 mL, 200 mmol, 10.0 equiv) was added dropwise and continued to react at room temperature for 12 hours. After the reaction, the reaction solution was poured into an ice-water mixture, extracted three times with ethyl acetate (150 mL×3), washed three times with saturated brine (150 mL×3), and the organic phase was dried using a rotary evaporator. Finally, column chromatography (PE to DCM:PE=1:2) and drying in a vacuum oven at 80°C gave 7.3 g of monomer E as a white solid with a yield of 61%.

[0064] The reaction formula and synthesis method of the monomer F are as follows:

[0065]

[0066] 2,7-Dibromo-9,9'-spirobifluorene (9.5 g, 20 mmol, 1.0 equiv) and 1,3-dimethyl-2-imidazolidinone (DMI) (200 mL) were added to a 500 mL three-necked flask. After N2 degassing for 10 minutes, sodium thiomethoxide (15 g, 200 mmol, 10.0 equiv) was added and reacted at 120°C for 36 hours. The reaction solution was cooled to room temperature, and cyclohexanecarbonyl chloride (27.0 mL, 200 mmol, 10.0 equiv) was added dropwise and the reaction was continued at room temperature for 12 hours. After the reaction, the reaction solution was poured into an ice-water mixture, extracted three times with ethyl acetate (150 mL×3), washed three times with saturated brine (150 mL×3), and the organic phase was dried using a rotary evaporator. Finally, column chromatography (PE to DCM:PE=1:2) and drying in a vacuum oven at 80°C gave 7.1 g of monomer F as a white solid with a yield of 59%.

[0067] Preferably, the P3 polymer is subjected to a refractive index test:

[0068] Accurately weigh 274.4 mg of P3 polymer material in a 20 mL glass bottle, add 10 mL of THF, stir with a magnetic stirrer for 1 hour to form a uniform solution, filter with a 0.44 μm filter membrane to prepare a 3% casting solution, pour the casting solution into a small aluminum foil bowl, cover with a large beaker, and spread anhydrous magnesium sulfate around to allow the solvent to evaporate slowly. After 3 days, remove the transparent light red film from the small aluminum foil bowl and vacuum dry at 80°C for 24 hours. The P3 polymer film is successfully prepared, and the refractive index of the P3 film material is tested using an ellipsometer (UVISEL Plus, HORIBA France SAS, France), and the test result is nD = 1.717.

[0069] Preferably, the P3 polymer-supported metal is subjected to a heterogeneous catalytic reaction:

[0070] Suzuki coupling

[0071]

[0072] Accurately weigh 100 mg of P3 material in a 10 mL glass bottle and add 3 mL of 0.01MPdCl2 + 0.04M NaCl THF solution, ultrasonic for 2h, stirred at room temperature for 24h, the solution was dropped into 50mL methanol, centrifuged, the solid was separated, the solid particles were washed three times with deionized water, vacuum dried at 100℃ overnight, and ICP-OES detection successfully prepared Pd2+@P3 catalyst (Pd content: 1.1wt%), 4-iodotoluene (21.8mg, 0.1mmol, 1.0equiv), phenylboric acid (18.3mg, 0.15mmol, 1.5equiv), K2CO3 (41.4mg, 0.3mmol, 3.0equiv), Pd2+@P3 (5.0mg, 0.005mmol, 0.01equiv) were accurately weighed in a 15mL dry pressure tube, N2 was replaced 5 times, Tol. (1mL) and H2O (0.2mL) were added, and the reaction was carried out at 100℃ for 12 hours to obtain 16.6mg of suzuki coupling product G with a yield of 99%;

[0073] Isomerization of olefins

[0074]

[0075] In a 15 mL dry pressure tube, accurately weigh 2,7'-dibromo-9,9'-spirobifluorene (145.2 mg, 0.3 mmol, 1.0 equiv), S,S'-(9,9'-spirobi[fluorene]-2,7-diyl) diethylsulfate (139.2 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03equiv), sodium tert-butoxide (tBuONa) (144.2mg, 1.5mmol, 5.0equiv), N2 replacement 5 times, anhydrous toluene (1.0mL) was added, and the reaction was carried out at 100°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2mL of dilute hydrochloric acid (2.0M), 2mL of saturated brine and 8mL of tetrahydrofuran were added to quench the reaction. The solid was filtered and washed with deionized water and tetrahydrofuran 3 times each to obtain 200.0mg of light yellow powder solid with a yield of 96%. The specific surface area was 244.2m2 / g after BET test;

[0076]

[0077] Accurately weigh 100 mg of P11 material in a 10 mL glass bottle and add 3 mL A 0.01M solution of palladium trifluoroacetate in acetonitrile was ultrasonically treated for 2h and stirred at room temperature for 24h. The solution was dropped into 50mL of methanol and centrifuged to separate the solid. The solid particles were washed three times with deionized water and dried in vacuum at 100°C overnight. After ICP-OES detection, Pd2+@P11 catalyst (Pd content: 0.9wt%) was successfully prepared. Pd2+@P11 (30.0mg, 0.005mmol, 0.01equiv) was weighed in a 15mL dry pressure tube, and N2 was replaced 5 times. 1,2-dichloroethane (0.3mL), 1-dodecene (113.0μL, 0.5mmol, 1.0equiv) and FCH2CH2OH (15.6μL, 0.25mmol, 0.5equiv) were added in turn. The reaction was carried out at 100°C for 48 hours to obtain 75% olefin isomerization products.

[0078] Compared with the prior art, the present invention has the following beneficial effects:

[0079] Using tris(dibenzylideneacetone)dipalladium (Pd(dba)2) as a Pd catalyst, a series of polyaryl sulfide polymer materials are synthesized by CS coupling of dibromoarene and diaryl thioester monomers. Compared with the traditional synthesis method of polyaryl sulfide, the method of the present invention is more gentle and has high compatibility with monomers. The use of diaryl thioester as a monomer in the present invention has the following advantages: (1) The monomer synthesis method is diverse and efficient; (2) The monomer is easy to purify with a purity greater than 99%; (3) The monomer is highly stable; (4) The polymerization reaction is more efficient and controllable. The present invention not only provides a new synthesis method for polyaryl sulfide polymer materials, but also the linear polyaryl sulfide polymer in the present invention is easy to process, which is specifically manifested in that the material has good solubility in conventional solvents, such as tetrahydrofuran (THF). This type of polyaryl sulfide polymer material with the above advantages has great development and application prospects in high refractive index and anisotropic catalysis. BRIEF DESCRIPTION OF THE DRAWINGS

[0080] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of monomer A of the present invention;

[0081] Figure 2 is the carbon nuclear magnetic resonance spectrum of monomer A of the present invention;

[0082] Figure 3 is the infrared spectrum of monomer A of the present invention;

[0083] Figure 4 is a high-resolution mass spectrum of monomer A of the present invention;

[0084] Figure 5 is the hydrogen nuclear magnetic resonance spectrum of monomer B of the present invention;

[0085] Figure 6 is the carbon NMR spectrum of monomer B of the present invention;

[0086] Figure 7 is the infrared spectrum of monomer B of the present invention;

[0087] Figure 8 is a high-resolution mass spectrum of monomer B of the present invention;

[0088] Fig. 9 is the hydrogen nuclear magnetic resonance spectrum of monomer C of the present invention;

[0089] Fig.10 is the carbon nuclear magnetic resonance spectrum of monomer C of the present invention;

[0090] Fig.11 is the infrared spectrum of monomer C of the present invention;

[0091] Fig.12 is a high-resolution mass spectrum of monomer C of the present invention;

[0092] Fig.13 is the hydrogen nuclear magnetic resonance spectrum of monomer D of the present invention;

[0093] Fig.14 is the carbon NMR spectrum of monomer D of the present invention;

[0094] Fig.15 is the infrared spectrum of monomer D of the present invention;

[0095] Fig.16 is a high-resolution mass spectrum of monomer D of the present invention;

[0096] Fig.17 is the hydrogen nuclear magnetic resonance spectrum of monomer E of the present invention;

[0097] Fig.18 is the carbon NMR spectrum of monomer E of the present invention;

[0098] Fig.19 is the infrared spectrum of monomer E of the present invention;

[0099] Fig. 20 is a high-resolution mass spectrum of monomer E of the present invention;

[0100] Fig.21 is the hydrogen nuclear magnetic resonance spectrum of monomer F of the present invention;

[0101] Fig. 22 is the carbon NMR spectrum of monomer F of the present invention;

[0102] Fig.23 is the infrared spectrum of monomer F of the present invention;

[0103] Fig.24 is a high-resolution mass spectrum of monomer F of the present invention;

[0104] Fig.25 is the hydrogen nuclear magnetic resonance spectrum of monomer G of the present invention;

[0105] Fig.26 is the carbon nuclear magnetic resonance spectrum of monomer G of the present invention;

[0106] Fig. 27 is the infrared spectrum of monomer G of the present invention;

[0107] Fig.28 is a high-resolution mass spectrum of monomer G of the present invention;

[0108] Fig.29 is the hydrogen nuclear magnetic resonance spectrum of the polymer P1 of the present invention;

[0109] Fig.30 is the carbon NMR spectrum of the polymer P1 of the present invention;

[0110] Fig.31 is the infrared spectrum of polymer P1 of the present invention;

[0111] Fig.32 is the GPC spectrum of polymer P1 of the present invention;

[0112] Fig.33 is the hydrogen nuclear magnetic resonance spectrum of the polymer P2 of the present invention;

[0113] Fig.34 is the carbon nuclear magnetic resonance spectrum of the polymer P2 of the present invention;

[0114] Fig.35 is the infrared spectrum of polymer P2 of the present invention;

[0115] Fig.36 is the GPC spectrum of polymer P2 of the present invention;

[0116] Fig.37 is the hydrogen nuclear magnetic resonance spectrum of the polymer P3 of the present invention;

[0117] Fig.38 is the carbon nuclear magnetic resonance spectrum of the polymer P3 of the present invention;

[0118] Fig.39 is the infrared spectrum of polymer P3 of the present invention;

[0119] Fig.40 is the GPC spectrum of the polymer P3 of the present invention;

[0120] Fig.41 is the hydrogen nuclear magnetic resonance spectrum of the polymer P4 of the present invention;

[0121] Fig.42 is the nuclear magnetic resonance fluorine spectrum of the polymer P4 of the present invention;

[0122] Fig.43 is the carbon nuclear magnetic resonance spectrum of the polymer P4 of the present invention;

[0123] Fig.44 is the infrared spectrum of polymer P4 of the present invention;

[0124] Fig.45 is the GPC spectrum of polymer P4 of the present invention;

[0125] Fig.46 is the hydrogen nuclear magnetic resonance spectrum of the polymer P5 of the present invention;

[0126] Fig.47 is the nuclear magnetic resonance fluorine spectrum of the polymer P5 of the present invention;

[0127] Fig.48 is the carbon nuclear magnetic resonance spectrum of the polymer P5 of the present invention;

[0128] Fig.49 is the infrared spectrum of polymer P5 of the present invention;

[0129] Fig.50 is the GPC spectrum of polymer P5 of the present invention;

[0130] Fig.51 is the hydrogen nuclear magnetic resonance spectrum of the polymer P6 of the present invention;

[0131] Fig.52 is the carbon nuclear magnetic resonance spectrum of the polymer P6 of the present invention;

[0132] Fig.53 is the infrared spectrum of polymer P6 of the present invention;

[0133] Fig.54 is the GPC spectrum of polymer P6 of the present invention;

[0134] Fig.55 is the hydrogen nuclear magnetic resonance spectrum of the polymer P7 of the present invention;

[0135] Fig.56 is the carbon nuclear magnetic resonance spectrum of the polymer P7 of the present invention;

[0136] Fig.57 is the infrared spectrum of polymer P7 of the present invention;

[0137] Fig.58 is the GPC spectrum of polymer P7 of the present invention;

[0138] Fig.59 is the hydrogen nuclear magnetic resonance spectrum of the polymer P8 of the present invention;

[0139] Fig.60 is the carbon nuclear magnetic resonance spectrum of the polymer P8 of the present invention;

[0140] Fig.61 is the infrared spectrum of polymer P8 of the present invention;

[0141] Fig.62 is the GPC spectrum of polymer P8 of the present invention;

[0142] Fig.63 is the hydrogen nuclear magnetic resonance spectrum of the polymer P9 of the present invention;

[0143] Fig.64 is the nuclear magnetic resonance fluorine spectrum of the polymer P9 of the present invention;

[0144] Fig.65 is the carbon nuclear magnetic resonance spectrum of the polymer P9 of the present invention;

[0145] Fig.66 is the infrared spectrum of the polymer P9 of the present invention;

[0146] Fig.67 is the GPC spectrum of polymer P9 of the present invention;

[0147] Fig.68 is the hydrogen nuclear magnetic resonance spectrum of the polymer P10 of the present invention;

[0148] Fig.69 is the carbon nuclear magnetic resonance spectrum of the polymer P10 of the present invention;

[0149] Fig.70 is the infrared spectrum of the polymer P10 of the present invention;

[0150] Fig.71 is the GPC spectrum of polymer P10 of the present invention;

[0151] Fig.72 is the TGA spectrum of polymers P1-P10 of the present invention;

[0152] Fig.73 is the light refraction spectrum of the polymer film of polymer P3 of the present invention;

[0153] Fig.74 is the hydrogen nuclear magnetic resonance spectrum of the suzuki coupling product H of the present invention;

[0154] Fig.75 is the BET spectrum of polymer P11 of the present invention;

[0155] Fig.76 It is the hydrogen nuclear magnetic resonance spectrum of the isomerization of 1-dodecene of the present invention. DETAILED DESCRIPTION

[0156] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0157] Reference Figure 1-Figure 76 , a method for synthesizing polyaryl sulfide polymer, the reaction formula and monomers thereof are as follows:

[0158]

[0159]

[0160] The synthesis of monomers includes the following methods:

[0161] The reaction formula and synthesis method of monomer A are as follows:

[0162]

[0163] Acetic acid (6.0 mL, 100 mmol, 4.0 equiv) and acetic anhydride (5.0 mL, 50 mmol, 2.0 equiv) were added to a 50 mL three-necked flask, and the mixture was reacted at 45 °C for 2.5 hours, followed by the addition of 4'4-dimercaptodiphenyl sulfide (6.25 g, 25 mmol, 1.0 equiv) and pyridine (20.0 uL, 0.25 mmol, 0.01 equiv), and the mixture was reacted at 30 °C for 12 hours. After the reaction, the reaction solution was cooled to room temperature, quenched by the addition of 50 mL of saturated saline, and extracted three times with ethyl acetate (50 mL × 3), and the organic phases were combined and dried using a rotary evaporator. Finally, the mixture was recrystallized from ethanol and dried in a vacuum oven at 80 °C to obtain 6.5 g of white crystals of monomer A with a yield of 78%. 1H NMR(400MHz,Chloroform-d)δ7.38–7.33(m,8H),2.43(s,6H).13CNMR(101MHz,CDCl3)δ193.7,137.2,135.2,131.6,127.1,3 0.4.IR(cm-1):1697(vs),1468(s),1345(s),1115(s),1083(s),1002(s),945(s),815(s),613(s),560(s),517(m).HRMS(m / z ESI):Calcd.for[C16H14NaO2S3]+357.0048, found 357.0040.

[0164] The reaction formula and synthesis method of monomer B are as follows:

[0165]

[0166] 4'4-dimercaptodiphenyl sulfide (6.25 g, 20 mmol, 1.0 equiv) and 4-dimethylaminopyridine (DMAP) (24.5 mg, 0.2 mmol, 0.01 equiv) were added to a 250 mL three-necked flask. After N2 replacement 3 times, DCM (40 mL) was added. Benzoyl chloride (4.7 mL, 40 mmol, 2.0 equiv) and triethylamine (Et3N) (11.2 mL, 80 mmol, 4.0 equiv) were added dropwise at 0 ° C. Stirring, stirring at room temperature overnight. After the reaction was completed, 50 mL of saturated brine was added to quench and extracted three times with ethyl acetate (50 mL × 3). The organic phases were combined and dried by rotary evaporation. Finally, flash column chromatography (PE: EA = 2: 1), dichloromethane and petroleum ether were recrystallized, and dried in a vacuum oven at 80 ° C to obtain 8.0 g of pale yellow crystals of monomer B with a yield of 88%. 1H NMR(400MHz,Chloroform-d)δ8.05–8.02(m,4H),7.64–7.60(m,2H),7.52–7.44(m,12H ).13CNMR(101MHz,CDCl3)δ189.9,137.4,136.6,135.9,133.9,131.6,128.9,127.7,12 6.6.IR(cm-1):3053(s),1665(vs),1568(s),1441(s),1386(s),1198(vs),1165(s),1 076(s),999(s),897(vs),810(vs),767(s),677(s),634(s),577(s),478(s).HRMS(m / z ESI):Calcd.for[C26H18NaO2S3]+481.0361, found 481.0358.

[0167] The reaction formula and synthesis method of monomer C are as follows:

[0168]

[0169] 4'4-dimercaptodiphenyl sulfide (6.25 g, 20 mmol, 1.0 equiv) and 4-dimethylaminopyridine (DMAP) (24.5 mg, 0.2 mmol, 0.01 equiv) were added to a 250 mL three-necked flask. After N2 replacement 3 times, DCM (40 mL) was added. Cyclohexanecarbonyl chloride (5.4 mL, 40 mmol, 2.0 equiv) and triethylamine (Et3N) (11.2 mL, 80 mmol, 4.0 equiv) were added dropwise at 0 ° C. Stirring was continued overnight at room temperature. After the reaction was completed, 50 mL of saturated brine was added to quench the reaction and extracted three times with ethyl acetate (50 mL × 3). The organic phases were combined and dried using a rotary evaporator. Finally, flash column chromatography (PE: EA = 2: 1), dichloromethane and petroleum ether were recrystallized, and the monomer C was dried in a vacuum oven at 80 ° C to obtain 4.4 g of white crystals with a yield of 94%. 1H NMR(400MHz,Chloroform-d)δ7.37–7.31(m,8H),2.60(tt,J=11.4,3.5Hz,2H),2.02–1.9 8(m,4H),1.84–1.80(m,4H),1.69–1.66(m,2H),1.57–1.47(m,4H),1.37–1.24(m,6H).13C NMR(101MHz, CDCl3)δ200.6,136.9,135.4,131.5,127.2,52.7,29.6,25.7,25.6.IR(cm-1):2925( vs),2849(vs),1687(vs),1472(s),1444(s),1384(s),953(vs),816(s),762(s),480(s).HRMS(m / z ESI):Calcd.for[C26H30NaO2S3]+493.1300, found 493.1286.

[0170] The reaction formula and synthesis method of monomer D are as follows:

[0171]

[0172] Potassium hydroxide KOH (12.0 g, 190 mmol, 2.1 equiv) was added to a 150 mL three-necked flask, N2 was replaced 5 times, anhydrous methanol (100 mL) was added and stirred, and hexafluorobisphenol I (30.0 g, 90 mmol, 1.0 equiv) was added after KOH was completely dissolved, and stirred in an ice-water bath for 0.5 hours, and then dimethylaminothiocarbonyl chloride (28.7 g, 225 mmol, 2.5 equiv) was added and stirred in an ice-water bath for 6 hours, and stirred at room temperature overnight. After the reaction was completed, suction was filtered, and the solid was washed with ice water and methanol (1:1), and dried in a vacuum oven at 100°C to obtain 30 g of white solid II with a yield of 70%.

[0173] II was added to a dry 100 mL three-necked flask and replaced with nitrogen 5 times, and then stirred for reaction at 250°C in nitrogen for 2.5 hours. After the reaction, the obtained crude product was dried and recrystallized with methanol: water (6:1, v / v) to obtain 19.5 g of white solid III with a yield of 65%.

[0174] KOH (6.2 g, 100 mmol, 5.0 equiv) and III (10.2 g, 20 mmol, 1.0 equiv) were added to a 250 mL three-necked flask, and N2 was replaced 5 times. Methanol (80 mL) and deionized water (40 mL) were added and refluxed for 2 hours. After the reaction, the product was directly extracted and dried without purification for the next step.

[0175] IV (7.4 g, 20 mmol, 1.0 equiv) and 4-dimethylaminopyridine (DMAP) (24.5 mg, 0.2 mmol, 0.01 equiv) were added to a 250 mL three-necked flask. After N2 replacement 3 times, DCM (40 mL) was added. Cyclohexanecarbonyl chloride (5.4 mL, 40 mmol, 2.0 equiv) and triethylamine (Et3N) (11.2 mL, 80 mmol, 4.0 equiv) were added dropwise at 0 ° C. Stirring was continued overnight at room temperature. After the reaction was completed, 50 mL of saturated brine was added to quench the reaction and extracted three times with ethyl acetate (50 mL × 3). The organic phases were combined and dried using a rotary evaporator. Finally, flash column chromatography (PE: EA = 2: 1), dichloromethane and petroleum ether were recrystallized, and the monomer D was dried in a vacuum oven at 80 ° C to obtain 8.6 g of a white solid with a yield of 73%. 1H NMR(400MHz,Chloroform-d)δ7.42(s,8H),2.62(tt,J=11.4,3.5Hz,2H),2.03–1.99(m ,4H),1.85–1.81(m,4H),1.70–1.66(m,2H),1.57–1.48(m,4H),1.37–1.25(m,6H).13C NMR(101MHz, CDCl3)δ200.0,134.2,134.0,130.9,129.9,125.5,122.6,64.5,52.9,29.6,25.7,25.6.IR(cm-1):2928(vs),2856(vs),1 701(vs),1492(s),1448(s),1312(s),1242(vs),1208(vs),1170(vs),1135(vs),1050(s),962(vs),824(s),759(vs),700(s).HRMS(m / z ESI):Calcd.for[C29H30F6NaO2S2]+611.1484, found 611.1484.

[0176] The reaction formula and synthesis method of monomer E are as follows:

[0177]

[0178] 2,2'-dibromo-9,9'-spirobifluorene (9.5 g, 20 mmol, 1.0 equiv) and 1,3-dimethyl-2-imidazolidinone (DMI) (200 mL) were added to a 500 mL three-necked flask. After N2 degassing for 10 minutes, sodium thiomethoxide (15 g, 200 mmol, 10.0 equiv) was added and reacted at 120 ° C for 36 hours. The reaction solution was cooled to room temperature, and cyclohexanecarbonyl chloride (27.0 mL, 200 mmol, 10.0 equiv) was added dropwise and continued to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was poured into an ice-water mixture, extracted three times with ethyl acetate (150 mL × 3), washed three times with saturated brine (150 mL × 3), and the organic phase was dried using a rotary evaporator. Finally, column chromatography (PE to DCM: PE = 1:2) and vacuum oven drying at 80 ° C gave 7.3 g of monomer E as a white solid with a yield of 61%. 1H NMR(400MHz,Chloroform-d)δ7.87(d,J=8.0Hz,2H),7.85–7.83(m,2H),7.44(dd,J=8.0,1.6Hz,2H),7.38(td,J=7.5,1.1Hz,2H),7.14(td,J=7.5,1.1Hz, 2H),6.76–6.73(m,4H),2.50(tt,J=11.4,3.5Hz,2H),1.93–1.88(m,4H),1.7 9–1.73(m,4H),1.65–1.60(m,2H),1.49–1.39(m,4H),1.30–1.18(m,6H).13C NMR (101MHz, CDCl3) δ200.6,148.8,148.7,142.9,140.9,134.7,129.8,128.7,128.1 ,127.4,124.3,120.6,120.5,65.9,52.5,29.6,25.7,25.6.IR(cm-1):2922(s),2848 (s),1694(vs),1445(s),1401(s),1295(m),1262(m),1235(m),1136(s),1039(s),95 7(vs),883(m),832(s),796(s),754(vs),640(m),589(m),536(m),421(s).HRMS(m / z ESI):Calcd.for[C39H36NaO2S2]+623.2049, found 623.2034.

[0179] The reaction formula and synthesis method of monomer F are as follows:

[0180]

[0181] 2,7-dibromo-9,9'-spirobifluorene (9.5 g, 20 mmol, 1.0 equiv) and 1,3-dimethyl-2-imidazolidinone (DMI) (200 mL) were added to a 500 mL three-necked flask. After N2 degassing for 10 minutes, sodium thiomethoxide (15 g, 200 mmol, 10.0 equiv) was added and reacted at 120 ° C for 36 hours. The reaction solution was cooled to room temperature, and cyclohexanecarbonyl chloride (27.0 mL, 200 mmol, 10.0 equiv) was added dropwise and continued to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was poured into an ice-water mixture, extracted three times with ethyl acetate (150 mL × 3), washed three times with saturated brine (150 mL × 3), and the organic phase was dried using a rotary evaporator. Finally, column chromatography (PE to DCM: PE = 1:2) and vacuum oven drying at 80 ° C gave 7.1 g of monomer F as a white solid with a yield of 59%. 1H NMR(400MHz,Chloroform-d)δ7.87(d,J=8.0Hz,2H),7.85–7.82(m,2H),7.43(dd,J=8.0,1.6Hz,2H),7.38(td,J=7.5,1.1Hz,2H),7.14(td,J=7.5,1.2Hz ,2H),6.79–6.76(m,2H),6.73(d,J=1.1Hz,2H),2.52–2.45(m,2H),1.91–1. 87(m,4H),1.78–1.74(m,4H),1.64–1.61(m,2H),1.47–1.38(m,4H),1.29–1. 14(m,6H).13CNMR(101MHz,CDCl3)δ200.5,149.9,147.6,141.9,141.9,134 .6,129.9,128.2,128.2,128.0,124.5,120.9,120.2,65.9,52.5,29.6,25.7 ,25.6.IR(cm-1):3062(m),1694(s),1445(s),1396(s),1352(s),1245(w),1 109(s),946(s),870(m),807(s),729(s),611(s),534(m),421(m).HRMS(m / z ESI):Calcd.for[C39H36KO2S2]+639.1788,found639.1790.

[0182] It also includes a characteristic monomer G, the reaction formula and synthesis method of monomer G are as follows:

[0183]

[0184] 2-Bromo-7-iodo-9,9-dioctyl-9H-fluorene (8.9 g, 15 mmol, 1.0 equiv), potassium cyclohexanecarbonylthiocarboxylate (2.8 g, 15 mmol, 1.0 equiv), CuI (285.5 mg, 1.5 mmol, 0.1 equiv) and 1,10-phenanthroline (270.3 mg, 1.5 mmol, 0.1 equiv) were added to a 500 mL three-necked flask, N2 was replaced 5 times, anhydrous toluene (10 mL) was added and reacted at 100 ° C for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, extracted three times with ethyl acetate (150 mL × 3), washed three times with saturated brine (150 mL × 3), and the organic phase was dried using a rotary evaporator. Finally, column chromatography (PE: EA = 30: 1) and vacuum oven drying at 80 ° C were performed to obtain 5.1 g of a light yellow oil G with a yield of 56%. 1H NMR(400MHz,Chloroform-d)δ7.67(d,J=7.8Hz,1H),7.56–7.54(m,1H),7.47–7.45(m,2H),7.38–7.34(m,2H),2.63(tt,J=11.4,3.5 Hz,1H),2.05–1.82(m,8H),1.70–1.67(m,1H),1.60–1.50(m,2H),1.32–1.06(m,20H),0.83(t,J=7.1Hz,6H),0.67–0.61(m,4H).13C NMR (101MHz, CDCl3) δ200.6,153.4151.2,141.1,139.4,133.4,130.2,129.2 ,126.9,126.4,121.8,121.5,120.4,55.7,52.6,40.2,31.9,30.0,29.7,29.3 ,29.3,25.8,25.7,23.8,22.7,14.2.IR(cm-1):2923(vs),2852(vs),1701(vs ),1448(vs),1404(s),1238(s),1140(s),959(vs),806(s),759(s).HRMS(m / z ESI):Calcd.for[C36H51BrNaOS]+633.2736, found 633.2740.

[0185] The synthesis of polyaryl sulfide polymers includes the following methods:

[0186] The reaction formula and synthesis method of polyaryl sulfide polymer P1 are as follows:

[0187]

[0188] In a 15 mL dry pressure tube, 9,9-dioctyl-2,7-dibromofluorene (164.5 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl)) diethylsulfate (100.2 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv) were accurately weighed in sequence, and the atmosphere was replaced with N2 five times. Anhydrous toluene (1.0 mL) was added and the reaction was carried out at 75 °C for 12 hours. After the reaction is completed, cool to room temperature and add 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran to quench the reaction, then extract once with tetrahydrofuran, and wash once with 10 mL of saturated brine. Concentrate the organic phase and add tetrahydrofuran until it is completely dissolved. Add the organic phase dropwise into 50 mL of methanol, precipitate and purify, and vacuum dry at 100°C to obtain 183.5 mg of P1 polymer as a light yellow spun solid with a yield of 92%. 1H NMR(400MHz,THF-d8)δ7.73(d,J=7.9Hz,2H),7.49(s,2H),7.37(d,J=8.0Hz,2H),7.24–7. 17(m,8H),1.99–1.95(m,4H),1.22–1.04(m,20H),0.82(t,J=7.1Hz,6H),0.63(s,4H).13C NMR(101MHz,THF)δ153.2,141.6,138.3,134.8,134.3,132.6,130.8,128. 3,121.9,56.5,40.9,32.9,31.0,30.4,30.3,25.0,23.7,14.7.IR(cm-1):3 438(m),2923(vs),2852(vs),1574(s),1465(vs),1401(s),1258(m),1092(s),1009(s),885(w),815(vs),747(s),491(s).GPC(againstpolystyrene) standards, THF): Mn=50.3kg / mol, Mw=135.7kg / mol,

[0189] The reaction formula and synthesis method 2 of the polyaryl sulfide polymer P1 are as follows:

[0190]

[0191] In a 15 mL dry pressure tube, 9,9-dioctyl-2,7-dibromofluorene (164.5 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl))diphenylsulfate (137.4 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv) were accurately weighed in sequence, the atmosphere was replaced with N2 five times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 75 °C for 12 hours. After the reaction is completed, cool to room temperature and add 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran to quench the reaction, then extract once with tetrahydrofuran, and wash once with 10 mL of saturated brine. Concentrate the organic phase and add tetrahydrofuran until it is completely dissolved. Add the organic phase dropwise into 50 mL of methanol, precipitate and purify, and vacuum dry at 100°C to obtain 175.8 mg of P1 polymer as a light yellow spun solid with a yield of 88%. 1H NMR(400MHz,THF-d8)δ7.73(d,J=7.9Hz,2H),7.49(s,2H),7.37(d,J=8.0Hz,2H),7.24–7. 17(m,8H),1.99–1.95(m,4H),1.22–1.04(m,20H),0.82(t,J=7.1Hz,6H),0.63(s,4H).13C NMR(101MHz,THF)δ153.2,141.6,138.3,134.8,134.3,132.6,130.8,128. 3,121.9,56.5,40.9,32.9,31.0,30.4,30.3,25.0,23.7,14.7.IR(cm-1):3 438(m),2923(vs),2852(vs),1574(s),1465(vs),1401(s),1258(m),1092(s),1009(s),885(w),815(vs),747(s),491(s).GPC(againstpolystyrene) standards, THF): Mn=47.0kg / mol, Mw=142.3kg / mol,

[0192] The reaction formula and synthesis method three of polyaryl sulfide polymer P1 are as follows:

[0193]

[0194] In a 15 mL dry pressure tube, 9,9-dioctyl-2,7-dibromofluorene (164.5 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl))dicyclohexanethioate (141.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv) were accurately weighed in sequence, the atmosphere was replaced with N2 five times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 70°C for 12 hours. After the reaction, cool to room temperature and add 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran to quench the reaction, then extract once with tetrahydrofuran and wash once with 10 mL of saturated brine. Concentrate the organic phase and add tetrahydrofuran until it is completely dissolved. Add the organic phase dropwise into 50 mL of methanol, precipitate and purify, and vacuum dry at 100 ° C to obtain 185.8 mg of P1 polymer as a light yellow spun solid with a yield of 93%. 1H NMR(400MHz,THF-d8)δ7.73(d,J=7.9Hz,2H),7.49(s,2H),7.37(d,J=8.0Hz,2H),7.24–7. 17(m,8H),1.99–1.95(m,4H),1.22–1.04(m,20H),0.82(t,J=7.1Hz,6H),0.63(s,4H).13C NMR(101MHz,THF)δ153.2,141.6,138.3,134.8,134.3,132.6,130.8,128.3,121.9,56.5,40.9,32.9,31.0,30.4,30.3,25.0,23.7,14.7.IR(c m-1):3438(m),2923(vs),2852(vs),1574(s),1465(vs),1401(s),1258(m),1092(s),1009(s),885(w),815(vs),747(s),491(s).GPC(against polystyrene standards, THF): Mn=80.9kg / mol, Mw=213.2kg / mol,

[0195] The reaction formula and synthesis method of polyaryl sulfide polymer P2 are as follows:

[0196]

[0197] In a 15 mL dry pressure tube, 2,2'-dibromo-9,9'-spirobifluorene (145.2 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl))dicyclohexanethioate (141.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv) were accurately weighed in sequence, and the atmosphere was replaced with N2 five times. Anhydrous toluene (1.0 mL) was added and the reaction was carried out at 75°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, then extracted once with tetrahydrofuran and washed once with 10 mL of saturated brine. The organic phase was concentrated and tetrahydrofuran was added until it was completely dissolved. The organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100 ° C to obtain 154.5 mg of P2 polymer as a light yellow powder solid with a yield of 87%. 1H NMR (400 MHz, THF-d8) δ7.86–7.81 (m, 4H), 7.31–7.28 (m, 4H), 7.09–7.02 (m, 10H), 6.79 (d, J = 1.7 Hz, 2H), 6.67 (d, J = 7.6 Hz, 2H).13C NMR(101MHz,THF)δ150.7,149.4,142.8,142.0,137.1,135.1,135.0,132.8,132 .5,131.3,129.3,129.1,128.3,124.9,122.2,121.4,66.9.IR(cm-1):3053(m),1 893(w),1571(s),1468(s),1441(s),1398(s),1255(m),1160(w),1096(s),1006 (s),814(s),732(s),641(w),589(m),487(s),428(m).GPC(againstpolystyrene standards, THF): Mn=21.0kg / mol, Mw=70.2kg / mol,

[0198] The reaction formula and synthesis method of polyaryl sulfide polymer P3 are as follows:

[0199]

[0200] In a 15 mL dry pressure tube, 2,7'-dibromo-9,9'-spirobifluorene (145.2 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl))dicyclohexanethioate (141.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv) were accurately weighed in sequence, the atmosphere was replaced with N2 five times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 75°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, then extracted once with tetrahydrofuran and washed once with 10 mL of saturated brine. The organic phase was concentrated and tetrahydrofuran was added until it was completely dissolved. The organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100 ° C to obtain 161.6 mg of P3 polymer as a light yellow powder solid with a yield of 91%. 1H NMR (400 MHz, THF-d8) δ7.84 (dd, J = 16.9, 7.8 Hz, 4H), 7.33–7.27 (m, 4H)., 7.10–7.04 (m, 10H), 6.75–6.69 (m, 4H).13C NMR(101MHz,THF)δ151.4,148.7,142.9,141.9,136.9,135.6,135.1,132.6,13 2.5,131.4,129.2,129.0,128.3,124.7,122.3,121.3,66.9.IR(cm-1):3051(m) ,2935(w),1701(w),1601(m),1572(m),1448(s),1399(s),1248(m),1178(w),10 96(s),1007(s),959(w),873(w),812(s),732(s),639(w),493(m).GPC(against polystyrene standards, THF): Mn=33.4kg / mol, Mw=80.3kg / mol,

[0201] The reaction formula and synthesis method of polyaryl sulfide polymer P4 are as follows:

[0202]

[0203] In a 15 mL dry pressure tube, 2,2'-dibromo-9,9'-spirobifluorene (145.2 mg, 0.3 mmol, 1.0 equiv), 4,4'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bisphenyldicyclohexanethioate (176.4 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv) were accurately weighed in sequence, the atmosphere was replaced with N2 five times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 80°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, then extracted once with tetrahydrofuran and washed once with 10 mL of saturated brine. The organic phase was concentrated and tetrahydrofuran was added until it was completely dissolved. The organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100 ° C to obtain 181.1 mg of P4 polymer as a light yellow powder solid with a yield of 85%. 1H NMR (400 MHz, THF-d8) δ7.92–7.87 (m, 4H), 7.46–7.44 (m, 2H), 7.37–7.31 (m, 2H), 7.19–7.03 (m, 10H), 6.83 (s, 2H), 6.71–6.64 (m, 2H). 19F NMR (376 MHz, THF-d8) δ-62.62.13C NMR(101MHz,THF)δ150.8,149.4,143.6,142.2,142.0,140.9,134.4,133.1,132.2,131 .6,129.7,129.5,129.2,128.6,126.7,124.9,123.9,122.4,122.0,121.5,121.3,121. 0,66.9,64.8.IR(cm-1):3065(w),1598(m),1495(m),1448(s),1405(m),1249(s),1203 (s),1173(s),1095(m),1017(w),966(m),933(s),822(s),733(s),427(w).GPC(against polystyrene standards, THF): Mn=45.3kg / mol, Mw=86.1kg / mol,

[0204] The reaction formula and synthesis method of polyaryl sulfide polymer P5 are as follows:

[0205]

[0206] In a 15 mL dry pressure tube, 2,7'-dibromo-9,9'-spirobifluorene (145.2 mg, 0.3 mmol, 1.0 equiv), 4,4'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bisphenyldicyclohexanethioate (176.4 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv) were accurately weighed in sequence, the atmosphere was replaced with N2 five times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 80°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, then extracted once with tetrahydrofuran and washed once with 10 mL of saturated brine. The organic phase was concentrated and tetrahydrofuran was added until it was completely dissolved. The organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100 ° C to obtain 159.7 mg of a light yellow spinning solid of P5 polymer with a yield of 75%. 1H NMR (400 MHz, THF-d8) δ8.08–7.78 (m, 4H), 7.58–7.46 (m, 2H), 7.40–7.29 (m, 4H), 7.19–7.01 (m, 8H), 6.82–6.53 (m, 4H). 19F NMR (376 MHz, THF-d8) δ-64.67.13C NMR(101MHz,THF)δ152.0,151.6,151.1,148.4,148.2,148.0,144.9,142.8,142.2,140.8,140.6,1 37.4,134.0,133.7,133.0,132.0,131.4,129.6,129.0,128.7,128.5,128.2,127.0,126.5,125.1, 124.4,123.6,122.7,122.4,122.1,121.1,66.4,64.9.IR(cm-1):3056(m),1595(m),1492(s),1449 (s),1401(m),1246(s),1206(s),1172(s),1092(s),963(s),929(s),814(s),733(s).GPC(against polystyrene standards, THF): Mn=39.6kg / mol, Mw=94.1kg / mol,

[0207] The reaction formula and synthesis method of polyaryl sulfide polymer P6 are as follows:

[0208]

[0209] In a 15 mL dry pressure tube, 9,9-dioctyl-2,7-dibromofluorene (164.5 mg, 0.3 mmol, 1.0 equiv), (R)-S,S'-(9,9'-spirobis[fluorene]-2,2'-diyl)dicyclohexanethioate (180.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv) were accurately weighed in sequence, the atmosphere was replaced with N2 five times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 80°C for 12 hours. After the reaction is completed, cool to room temperature and add 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran to quench the reaction, then extract once with tetrahydrofuran, and wash once with 10 mL of saturated brine. Concentrate the organic phase and add tetrahydrofuran until it is completely dissolved. Add the organic phase dropwise into 50 mL of methanol, precipitate and purify, and dry in vacuo at 100 ° C to obtain 222.1 mg of P6 polymer as a yellow powder solid with a yield of 93%.1HNMR(400MHz,THF-d8)δ7.85(d,J=7.6Hz,2H),7.79(d,J=8.1Hz,2H),7.63–7.56(m,2H),7.36–7.33k(m,4H),7.23(d,J=7.8Hz,2H),7.13(q ,J=8.3,7.6Hz,4H),6.86(s,2H),6.71(d,J=7.6Hz,2H),1.92–1.88(m,4H),1.25–1.04(m,20H),0.81(t,J=7.1Hz,6H),0.62–0.58(m,4H).13C NMR(101MHz,THF)δ153.0,150.6,149.6,142.2,141.9,141.1,137.6,135.1,131. 3,130.5,129.1,129.0,127.1,126.6,124.9,121.9,121.6,121.2,66.9,56.4,40 .9,33.0,31.0,30.4,24.9,23.7,14.7.IR(cm-1):3061(w),2922(s),2852(s),15 98(m),1449(s),1405(m),1258(w),817(s),753(s),729(s),584(w).GPC(against polystyrene standards, THF): Mn=23.4kg / mol, Mw=69.2kg / mol.

[0210] The reaction formula and synthesis method of polyaryl sulfide polymer P7 are as follows:

[0211]

[0212] In a 15 mL dry pressure tube, 9,9-dioctyl-2,7-dibromofluorene (164.5 mg, 0.3 mmol, 1.0 equiv), (R)-S,S'-(9,9'-spirobis[fluorene]-2,7'-diyl)dicyclohexanethioate (180.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv) were accurately weighed in sequence, the atmosphere was replaced with N2 five times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 65°C for 12 hours. After the reaction is completed, cool to room temperature and add 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran to quench the reaction, then extract once with tetrahydrofuran, and wash once with 10 mL of saturated brine. Concentrate the organic phase and add tetrahydrofuran until it is completely dissolved. Add the organic phase dropwise into 50 mL of methanol, precipitate and purify, and dry in vacuo at 100 ° C to obtain 210.2 mg of P7 polymer as a yellow spherical solid with a yield of 88%. 1HNMR(400MHz,THF-d8)δ7.90(d,J=7.6Hz,2H),7.75(d,J=8.1Hz,2H),7.59(d,J=8.0Hz,2H),7.38(t,J=7.5Hz,2H),7.29(s,2H ),7.18–7.14(m,6H),,6.78–6.77(m,4H),1.86–1.82(m,4H),1.19–0.95(m,20H),0.81(t,J=7.1Hz,6H),0.58–0.51(m,4H).13C NMR(101MHz,THF)δ152.9,151.1,149.0,143.0,141.2,141.0,137.5,135.2,131. 0,130.7,129.1,129.0,126.9,126.7,124.8,121.8,121.5,121.3,66.9,56.3,40 .8,32.9,31.0,30.4,30.3,24.8,23.7,14.7.IR(cm-1):3055(w),2923(s),2853( s),1598(m),1449(s),1404(m),1249(m),1068(w),812(s),732(s).GPC(against polystyrenestandards, THF): Mn=30.2kg / mol, Mw=85.1kg / mol,

[0213] The reaction formula and synthesis method of polyaryl sulfide polymer P8 are as follows:

[0214]

[0215] In a 15 mL dry pressure tube, 2,7-dibromospiro[fluorene-9,9'-oxanthene] (147.1 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl))dicyclohexanethioate (141.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv) were accurately weighed in sequence, the atmosphere was replaced with N2 five times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 80°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, then extracted once with tetrahydrofuran and washed once with 10 mL of saturated brine. The organic phase was concentrated and tetrahydrofuran was added until it was completely dissolved. The organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100 ° C to obtain 169.6 mg of P8 polymer as a light yellow powder solid with a yield of 93%. 1H NMR (400 MHz, THF-d8) δ7.82 (s, 2H), 7.33 (s, 2H), 7.17–7.11 (m, 14H), 6.74 (s, 2H), 6.41 (s, 2H).13C NMR(101MHz,THF)δ157.3,152.4,139.6,136.6,136.5,135.2,132.5,132.4,131.7,129.7,1 29.5,128.5,124.9,124.4,122.2,117.9,55.4.IR(cm-1):3435(s),3068(m),2929(s),2855 (m),1715(s),1641(s),1601(s),1572(s),1472(vs),1446(vs),1396(s),1291(s),1245(s) ,1159(s),1096(s),1007(s),886(m),813(s),752(s),696(m),640(m),494(m).GPC(against polystyrene standards, THF): Mn=16.8kg / mol, Mw=51.1kg / mol,

[0216] The reaction formula and synthesis method of polyaryl sulfide polymer P9 are as follows:

[0217]

[0218] In a 15 mL dry pressure tube, 2,7-dibromospiro[fluorene-9,9'-oxanthene] (147.1 mg, 0.3 mmol, 1.0 equiv), 4,4'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bisphenyldicyclohexanethioate (176.4 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv) were accurately weighed in sequence, the atmosphere was replaced with N2 five times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 90° C. for 12 hours. After the reaction is completed, cool to room temperature and add 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran to quench the reaction, then extract once with tetrahydrofuran, and wash once with 10 mL of saturated brine. Concentrate the organic phase and add tetrahydrofuran until it is completely dissolved. Add the organic phase dropwise into 50 mL of methanol, precipitate and purify, and dry in vacuo at 100 ° C to obtain 206.9 mg of P9 polymer as a light yellow powder solid with a yield of 95%. 1H NMR(400MHz,THF-d8)δ7.94(d,J=8.0Hz,1H),7.89–7.69(m,1H),7.51–7.33(m, 3H),7.26(s,1H),7.22–7.02(m,12H),6.79–6.71(m,2H),6.44–6.34(m,2H).19F NMR(376MHz,THF)δ-62.62.13C NMR(101MHz,THF)δ157.7,152.4,140.5,140.3,134.8,134.0,132.2,131.7 ,131.3,129.6,129.1,128.5,126.7,124.7,124.4,122.6,117.9,55.5.IR(c m-1):3048(w),1599(s),1481(s),1449(s),1248(vs),1205(s),1175(s),1096(s),967(s),933(s),817(s),753(s),524(m).GPC(againstpolystyrene) standards, THF): Mn=26.0kg / mol, Mw=102.0kg / mol,

[0219] The reaction formula and synthesis method of polyaryl sulfide polymer P10 are as follows:

[0220]

[0221] In a 15 mL dry pressure tube, S-(7-bromo-9,9-dioctyl-9H-fluoren-2-yl) cyclohexanethioate G (183.1 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (1.8 mg, 0.003 mmol, 0.01 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (2.5 mg, 0.0045 mmol, 0.015 equiv), sodium tert-butoxide (tBuONa) (72.1 mg, 0.75 mmol, 2.5 equiv) were accurately weighed in sequence, and the atmosphere was replaced with N2 five times. Anhydrous toluene (0.5 mL) was added and the reaction was carried out at 90°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, then extracted once with tetrahydrofuran and washed once with 10 mL of saturated brine. The organic phase was concentrated and tetrahydrofuran was added until it was completely dissolved. The organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100 ° C to obtain 124.2 mg of yellow powdered solid of P10 polymer with a yield of 92%. 1H NMR (400 MHz, THF-d8) δ7.67–7.61 (m, 2H), 7.46–7.44 (m, 2H), 7.28–7.22 (m, 2H), 1.99–1.95 (m, 4H), 1.26–1.08 (m, 20H), 0.86–0.82 (m, 6H), 0.70–0.66 (m, 4H).13C NMR(101MHz,THF)δ152.8,140.9,136.3,130.6,126.5,121.5,56.4,41.1,33.0,31.1,30.4,25.0,23.7,14.7.IR(cm-1):3062(m) ,3015(m),2922(vs),2850(vs),1601(s),1455(vs),1409(s),1256(s),1072(s),999(s),886(s),813(vs),749(s).GPC(against polystyrene standards, THF): Mn=13.3kg / mol, Mw=18.7kg / mol,

[0222] The polyaryl sulfide polymer material of the present application has great development and application prospects in high refractive index and anisotropic catalysis.

[0223] The refractive index of the P3 polymer was tested:

[0224] Accurately weigh 274.4 mg of P3 material in a 20 mL glass bottle, add 10 mL of THF, stir with a magnetic stirrer for 1 hour to form a uniform solution, filter with a 0.44 μm filter membrane to make a 3% casting solution. Pour the casting solution into a small aluminum foil bowl, cover with a large beaker, and spread anhydrous magnesium sulfate around to allow the solvent to evaporate slowly. After 3 days, remove the transparent light red film from the small aluminum foil bowl and vacuum dry at 80 ° C for 24 hours to successfully prepare the P3 polymer film. Use an ellipsometer (UVISELPlus, HORIBAFrance SAS, France) to test the refractive index of the P3 film material, and the test result is nD = 1.717.

[0225] The polyaryl sulfides P3 and P11 synthesized in the present invention can be loaded with palladium catalysts to prepare heterogeneous catalysts Pd2+@P3 and Pd2+@P11, which can efficiently realize the Suzuki coupling reaction and the isomerization reaction of olefins.

[0226] Heterogeneous catalytic reaction of P3 polymer-supported metals:

[0227] Suzuki coupling

[0228]

[0229] Accurately weigh 100 mg of P3 material in a 10 mL glass bottle and add 3 mL of 0.01MPdCl2 + 0.04M NaCl THF solution, ultrasonic for 2h, stirred at room temperature for 24h, the solution was dropped into 50mL methanol, centrifuged, the solid was separated, the solid particles were washed three times with deionized water, vacuum dried at 100℃ overnight, and ICP-OES detection successfully prepared Pd2+@P3 catalyst (Pd content: 1.1wt%), 4-iodotoluene (21.8mg, 0.1mmol, 1.0equiv), phenylboric acid (18.3mg, 0.15mmol, 1.5equiv), K2CO3 (41.4mg, 0.3mmol, 3.0equiv), Pd2+@P3 (5.0mg, 0.005mmol, 0.01equiv) were accurately weighed in a 15mL dry pressure tube, N2 was replaced 5 times, Tol. (1mL) and H2O (0.2mL) were added, and the reaction was carried out at 100℃ for 12 hours to obtain 16.6mg of suzuki coupling product G with a yield of 99%;

[0230] Isomerization of olefins

[0231]

[0232] In a 15 mL dry pressure tube, accurately weigh 2,7'-dibromo-9,9'-spirobifluorene (145.2 mg, 0.3 mmol, 1.0 equiv), S,S'-(9,9'-spirobi[fluorene]-2,7-diyl) diethylsulfate (139.2 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03equiv), sodium tert-butoxide (tBuONa) (144.2mg, 1.5mmol, 5.0equiv), N2 replacement 5 times, anhydrous toluene (1.0mL) was added, and the reaction was carried out at 100°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2mL of dilute hydrochloric acid (2.0M), 2mL of saturated brine and 8mL of tetrahydrofuran were added to quench the reaction. The solid was filtered and washed with deionized water and tetrahydrofuran 3 times each to obtain 200.0mg of light yellow powder solid with a yield of 96%. The specific surface area was 244.2m2 / g after BET test;

[0233]

[0234] Accurately weigh 100 mg of P11 material in a 10 mL glass bottle and add 3 mL A 0.01M solution of palladium trifluoroacetate in acetonitrile was ultrasonically treated for 2h and stirred at room temperature for 24h. The solution was dropped into 50mL of methanol and centrifuged to separate the solid. The solid particles were washed three times with deionized water and dried in vacuum at 100°C overnight. After ICP-OES detection, Pd2+@P11 catalyst (Pd content: 0.9wt%) was successfully prepared. Pd2+@P11 (30.0mg, 0.005mmol, 0.01equiv) was weighed in a 15mL dry pressure tube, and N2 was replaced 5 times. 1,2-dichloroethane (0.3mL), 1-dodecene (113.0μL, 0.5mmol, 1.0equiv) and FCH2CH2OH (15.6μL, 0.25mmol, 0.5equiv) were added in turn. The reaction was carried out at 100°C for 48 hours to obtain 75% olefin isomerization products.

[0235] Source of raw materials

[0236] In this application, unless otherwise noted, all chemicals were obtained from commercial sources, stored at room temperature, and used as received. Solvents and other commercial reagents were purchased from J&K, Leyan, Anaiji, Sigma-Aldrich, Yonghua, Nanshi and other companies and used as received.

[0237] Acetic acid (CAS 64-19-7) was purchased from Yonghua;

[0238] Acetic anhydride (CAS108-24-7) was purchased from Yonghua;

[0239] 4'4-dimercaptodiphenyl sulfide (CAS19362-77-7) was purchased from Leyan;

[0240] Pyridine (CAS110-86-1) was purchased from Anaiji;

[0241] Benzoyl chloride (CAS 98-88-4) was purchased from Anergy;

[0242] Cyclohexanecarbonyl chloride (CAS2719-27-9) was purchased from Anaiji;

[0243] Hexafluorobisphenol A (CAS1478-61-1) was purchased from Leyan;

[0244] Potassium hydroxide (CAS1310-58-3) was purchased from Anergy;

[0245] Triethylamine (CAS121-44-8) was purchased from Anaiji;

[0246] 2,2′-Dibromo-9,9′-spirobifluorene (CAS 67665-47-8) was purchased from Leyan;

[0247] 1,3-Dimethyl-2-imidazolidinone (CAS 80-73-9) was purchased from Anaiji;

[0248] Sodium methyl mercaptan (CAS 5188-07-8) was purchased from Anaiji;

[0249] 2,7′-Dibromo-9,9′-spirobifluorene (CAS171408-84-7) was purchased from Leyan;

[0250] 9,9-Dioctyl-2,7-dibromofluorene (CAS198964-46-4) was purchased from Leyan;

[0251] Tris(dibenzylideneacetone)dipalladium (CAS 51364-51-3) was purchased from Sigma-Aldrich;

[0252] Palladium trifluoroacetate (CAS 42196-31-6) was purchased from Leyan;

[0253] Palladium dichloride (CAS 7647-10-1) was purchased from Anergy;

[0254] Bis(diphenylphosphino)ferrocene (CAS12150-46-8) was purchased from J&K

[0255] Sodium tert-butoxide (CAS 865-48-5) was purchased from Anergy;

[0256] Tetrahydrofuran (CAS109-99-9) was purchased from J&K;

[0257] Toluene (CAS108-88-3) was purchased from Nanshi;

[0258] Acetonitrile (CAS 75-05-8) was purchased from Anaiji;

[0259] 1,2-Dichloroethane (CAS107-06-2) was purchased from Anergy;

[0260] 1-Dodecene (CAS112-41-4) was purchased from Anergy;

[0261] 2-Fluoroethanol (CAS 371-62-0) was purchased from Anergy.

[0262] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for synthesizing a polyaryl sulfide polymer, characterized in that: The reaction formula and monomers are as follows: The synthesis of the polyaryl sulfide polymer comprises the following method: The reaction formula and synthesis method of the polyaryl sulfide polymer P1 are as follows: In a 15 mL dry pressure tube, 9,9-dioctyl-2,7-dibromofluorene (164.5 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl)) diethylsulfate (100.2 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide (tB) (40.5 mg, 0.006 mmol, 0.02 equiv) were accurately weighed in sequence. uONa)(144.2mg, 1.5mmol, 5.0equiv), N2 replaced 5 times, anhydrous toluene (1.0mL) was added, and the reaction was carried out at 75°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2mL of dilute hydrochloric acid (2.0M), 2mL of saturated brine and 8mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 183.5mg of P1 polymer as a light yellow spun solid with a yield of 92%; The reaction formula and synthesis method 2 of the polyaryl sulfide polymer P1 are as follows: In a 15 mL dry pressure tube, 9,9-dioctyl-2,7-dibromofluorene (164.5 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl))diphenylsulfate (137.4 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide (tB) (40.4 mg, 0.006 mmol, 0.02 equiv) were accurately weighed in sequence. uONa)(144.2mg, 1.5mmol, 5.0equiv), N2 replaced 5 times, anhydrous toluene (1.0mL) was added, and the reaction was carried out at 75°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2mL of dilute hydrochloric acid (2.0M), 2mL of saturated brine and 8mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 175.8mg of P1 polymer as a light yellow spun solid with a yield of 88%; The reaction formula and synthesis method three of the polyarylether polymer P1 are as follows: In a 15 mL dry pressure tube, 9,9-dioctyl-2,7-dibromofluorene (164.5 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl))dicyclohexanethioate (141.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide ( tBuONa)(144.2mg, 1.5mmol, 5.0equiv), N2 replaced 5 times, anhydrous toluene (1.0mL) was added, and the reaction was carried out at 70°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2mL of dilute hydrochloric acid (2.0M), 2mL of saturated brine and 8mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10mL of saturated brine. The organic phase was concentrated, and tetrahydrofuran was added until it was just completely dissolved. The organic phase was added dropwise to 50mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 185.8mg of P1 polymer as a light yellow spun solid with a yield of 93%; The reaction formula and synthesis method of the polyaryl sulfide polymer P2 are as follows: In a 15 mL dry pressure tube, 2,2'-dibromo-9,9'-spirobifluorene (145.2 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl))dicyclohexanethioate (141.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide ( tBuONa)(144.2mg, 1.5mmol, 5.0equiv), N2 replaced 5 times, anhydrous toluene (1.0mL) was added, and the reaction was carried out at 75°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2mL of dilute hydrochloric acid (2.0M), 2mL of saturated brine and 8mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 154.5mg of P2 polymer as a light yellow powder solid with a yield of 87%; The reaction formula and synthesis method of the polyaryl sulfide polymer P3 are as follows: In a 15 mL dry pressure tube, 2,7'-dibromo-9,9'-spirobifluorene (145.2 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl))dicyclohexanethioate (141.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide ( tBuONa)(144.2mg, 1.5mmol, 5.0equiv), N2 replaced 5 times, anhydrous toluene (1.0mL) was added, and the reaction was carried out at 75°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2mL of dilute hydrochloric acid (2.0M), 2mL of saturated brine and 8mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 161.6mg of P3 polymer as a light yellow powder solid with a yield of 91%; The reaction formula and synthesis method of the polyaryl sulfide polymer P4 are as follows: 2,2'-Dibromo-9,9'-spirobifluorene (145.2 mg, 0.3 mmol, 1.0 equiv), 4,4'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bisphenyldicyclohexanethioate (176.4 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv) were accurately weighed in a 15 mL dry pressure tube. , sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv), N2 was replaced 5 times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 80°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10 mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 181.1 mg of P4 polymer as a light yellow powder solid with a yield of 85%; The reaction formula and synthesis method of the polyaryl sulfide polymer P5 are as follows: 2,7'-dibromo-9,9'-spirobifluorene (145.2 mg, 0.3 mmol, 1.0 equiv), 4,4'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bisphenyldicyclohexanethioate (176.4 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv) were accurately weighed in a 15 mL dry pressure tube. , sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv), N2 was replaced 5 times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 80°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10 mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 159.7 mg of P5 polymer as a light yellow spun solid with a yield of 75%; The reaction formula and synthesis method of the polyaryl sulfide polymer P6 are as follows: 9,9-dioctyl-2,7-dibromofluorene (164.5 mg, 0.3 mmol, 1.0 equiv), (R)-S,S'-(9,9'-spirobis[fluorene]-2,2'-diyl)dicyclohexanethioate (180.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv) were accurately weighed in a 15 mL dry pressure tube. , sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv), N2 replacement 5 times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 80°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10 mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 222.1 mg of P6 polymer as a yellow powder solid with a yield of 93%; The reaction formula and synthesis method of the polyaryl sulfide polymer P7 are as follows: 9,9-dioctyl-2,7-dibromofluorene (164.5 mg, 0.3 mmol, 1.0 equiv), (R)-S,S'-(9,9'-spirobis[fluorene]-2,7'-diyl)dicyclohexanethioate (180.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv) were accurately weighed in a 15 mL dry pressure tube. , sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv), N2 was replaced 5 times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 65°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10 mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was completely dissolved, and the organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 210.2 mg of P7 polymer as a yellow spherical solid with a yield of 88%; The reaction formula and synthesis method of the polyaryl sulfide polymer P8 are as follows: In a 15 mL dry pressure tube, accurately weigh 2,7-dibromospiro[fluorene-9,9'-oxanthene] (147.1 mg, 0.3 mmol, 1.0 equiv), S,S'-(thiobis(4,1-phenyl))dicyclohexanethioate (141.0 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv), sodium tert-butoxide, and 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv). (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv), N2 replaced 5 times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 80 ° C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10 mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100 ° C to obtain 169.6 mg of P8 polymer as a light yellow powder solid with a yield of 93%; The reaction formula and synthesis method of the polyaryl sulfide polymer P9 are as follows: In a 15 mL dry pressure tube, accurately weigh 2,7-dibromospiro[fluorene-9,9'-oxanthene] (147.1 mg, 0.3 mmol, 1.0 equiv), 4,4'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bisphenyldicyclohexanethioate (176.4 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03 equiv) in sequence. ), sodium tert-butoxide (tBuONa) (144.2 mg, 1.5 mmol, 5.0 equiv), N2 was replaced 5 times, anhydrous toluene (1.0 mL) was added, and the reaction was carried out at 90 ° C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2 mL of dilute hydrochloric acid (2.0 M), 2 mL of saturated brine and 8 mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10 mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was completely dissolved, and the organic phase was added dropwise to 50 mL of methanol, precipitated and purified, and dried in vacuo at 100 ° C to obtain 206.9 mg of P9 polymer as a light yellow powder solid with a yield of 95%; The reaction formula and synthesis method of the polyaryl sulfide polymer P10 are as follows: In a 15 mL dry pressure tube, accurately weigh S-(7-bromo-9,9-dioctyl-9H-fluoren-2-yl) cyclohexanethioate G (183.1 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (1.8 mg, 0.003 mmol, 0.01 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (2.5 mg, 0.0045 mmol, 0.015 equiv), sodium tert-butylate (tBuONa) (72.1 mg, 0.7 5mmol, 2.5equiv), N2 replaced 5 times, anhydrous toluene (0.5mL) was added, and the reaction was carried out at 90°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2mL of dilute hydrochloric acid (2.0M), 2mL of saturated brine and 8mL of tetrahydrofuran were added to quench the reaction, and then extracted once with tetrahydrofuran, and then washed once with 10mL of saturated brine. The organic phase was concentrated, tetrahydrofuran was added until it was just completely dissolved, and the organic phase was added dropwise to 50mL of methanol, precipitated and purified, and dried in vacuo at 100°C to obtain 124.2mg of P10 polymer as a yellow powder solid with a yield of 92%; The synthesized polyaryl sulfide polymers P3 and P11 can be loaded with palladium catalysts to prepare heterogeneous catalysts Pd2+@P3 and Pd2+@P11, which can efficiently realize Suzuki coupling reactions and olefin isomerization reactions.

2. The method for synthesizing a polyarylene sulfide polymer according to claim 1, characterized in that: The synthesis of the diaryl thioester monomer comprises the following method: The reaction formula and synthesis method of the monomer A are as follows: Acetic acid (6.0 mL, 100 mmol, 4.0 equiv) and acetic anhydride (5.0 mL, 50 mmol, 2.0 equiv) were added to a 50 mL three-necked flask, and the mixture was reacted at 45 ° C for 2.5 hours. Then, 4'4-dimercaptodiphenyl sulfide (6.25 g, 25 mmol, 1.0 equiv) and pyridine (20.0 uL, 0.25 mmol, 0.01 equiv) were added, and the mixture was reacted at 30 ° C for 12 hours. After the reaction, the reaction solution was cooled to room temperature, and then 50 mL of saturated brine was added to quench the mixture and extracted three times with ethyl acetate (50 mL×3). The organic phases were combined and dried using a rotary evaporator. Finally, the mixture was recrystallized with ethanol and dried in a vacuum oven at 80 ° C to obtain 6.5 g of white crystals of monomer A with a yield of 78%; The reaction formula and synthesis method of the monomer B are as follows: 4'4-dimercaptodiphenyl sulfide (6.25 g, 20 mmol, 1.0 equiv) and 4-dimethylaminopyridine (DMAP) (24.5 mg, 0.2 mmol, 0.01 equiv) were added to a 250 mL three-necked flask. After N2 replacement for 3 times, DCM (40 mL) was added. Benzoyl chloride (4.7 mL, 40 mmol, 2.0 equiv) and triethylamine (Et3N) (11.2 mL, 80 mmol, 4.0 equiv) were added dropwise in sequence under stirring at 0°C. The mixture was stirred at room temperature overnight. After the reaction was completed, 50 mL of saturated brine was added to quench the mixture and the mixture was extracted three times with ethyl acetate (50 mL×3). The organic phases were combined and dried using a rotary evaporator. Finally, flash column chromatography (PE:EA=2:1) ​​was performed, and the mixture was recrystallized from dichloromethane and petroleum ether and dried in a vacuum oven at 80°C to obtain 8.0 g of pale yellow crystals of monomer B with a yield of 88%. The reaction formula and synthesis method of the monomer C are as follows: 4'4-dimercaptodiphenyl sulfide (6.25 g, 20 mmol, 1.0 equiv) and 4-dimethylaminopyridine (DMAP) (24.5 mg, 0.2 mmol, 0.01 equiv) were added to a 250 mL three-necked flask. After N2 replacement for 3 times, DCM (40 mL) was added. Cyclohexanecarbonyl chloride (5.4 mL, 40 mmol, 2.0 equiv) and triethylamine (Et3N) (11.2 mL, 80 mmol, 4.0 equiv) were added dropwise in sequence under stirring at 0°C. The mixture was stirred at room temperature overnight. After the reaction was completed, 50 mL of saturated brine was added to quench the mixture and the mixture was extracted three times with ethyl acetate (50 mL×3). The organic phases were combined and dried using a rotary evaporator. Finally, flash column chromatography (PE:EA=2:1) ​​was performed, and the mixture was recrystallized from dichloromethane and petroleum ether and dried in a vacuum oven at 80°C to obtain 4.4 g of white crystals of monomer C with a yield of 94%. The reaction formula and synthesis method of the monomer D are as follows: Potassium hydroxide KOH (12.0 g, 190 mmol, 2.1 equiv) was added to a 150 mL three-necked flask, and N2 was replaced 5 times. Anhydrous methanol (100 mL) was added and stirred. After KOH was completely dissolved, hexafluorobisphenol I (30.0 g, 90 mmol, 1.0 equiv) was added and stirred in an ice-water bath for 0.5 hour. Then, dimethylaminothiocarbonyl chloride (28.7 g, 225 mmol, 2.5 equiv) was added and stirred in an ice-water bath for 6 hours. Then, it was stirred at room temperature overnight. After the reaction was completed, it was filtered, and the solid was washed with ice water and methanol (1:1). It was dried in a vacuum oven at 100°C to obtain 30 g of white solid II with a yield of 70%. II was added to a dry 100 mL three-necked flask and nitrogen was replaced 5 times. Then, it was stirred and reacted at 250°C in nitrogen for 2.5 hours. After the reaction was completed, the crude product was dried and recrystallized with methanol: water (6:1, v / v) to obtain white solid III 19.5g, yield 65%, KOH (6.2g, 100mmol, 5.0equiv) and III (10.2g, 20mmol, 1.0equiv) were added to a 250mL three-necked flask, N2 was replaced 5 times, methanol (80mL) and deionized water (40mL) were added to reflux for 2 hours, after the reaction, no purification was required, the extraction was directly spin-dried for the next step, IV (7.4g, 20mmol, 1.0equiv) and 4-dimethylaminopyridine (DMAP) (24.5mg, 0.2mmol, 0.01equiv) were added to a 250mL three-necked flask , after N2 replacement 3 times, DCM (40 mL) was added, and cyclohexanecarbonyl chloride (5.4 mL, 40 mmol, 2.0 equiv) and triethylamine (Et3N) (11.2 mL, 80 mmol, 4.0 equiv) were added dropwise in sequence under stirring at 0°C, and stirred at room temperature overnight. After the reaction was completed, 50 mL of saturated brine was added to quench the reaction, and the mixture was extracted three times with ethyl acetate (50 mL×3). The organic phases were combined and dried using a rotary evaporator. Finally, flash column chromatography (PE:EA=2:1) ​​was performed, and the mixture was recrystallized from dichloromethane and petroleum ether, and dried in a vacuum oven at 80°C to obtain 8.6 g of monomer D as a white solid with a yield of 73%; The reaction formula and synthesis method of the monomer E are as follows: 2,2'-dibromo-9,9'-spirobifluorene (9.5 g, 20 mmol, 1.0 equiv) and 1,3-dimethyl-2-imidazolidinone (DMI) (200 mL) were added to a 500 mL three-necked flask. After N2 degassing for 10 minutes, sodium thiomethoxide (15 g, 200 mmol, 10.0 equiv) was added and reacted at 120°C for 36 hours. The reaction solution was cooled to room temperature, and cyclohexanecarbonyl chloride (27.0 mL, 200 mmol, 10.0 equiv) was added dropwise and continued to react at room temperature for 12 hours. After the reaction, the reaction solution was poured into an ice-water mixture, extracted three times with ethyl acetate (150 mL×3), washed three times with saturated brine (150 mL×3), and the organic phase was dried using a rotary evaporator. Finally, column chromatography (PE to DCM:PE=1:2) and drying in a vacuum oven at 80°C gave 7.3 g of monomer E as a white solid with a yield of 61%. The reaction formula and synthesis method of the monomer F are as follows: 2,7-Dibromo-9,9'-spirobifluorene (9.5 g, 20 mmol, 1.0 equiv) and 1,3-dimethyl-2-imidazolidinone (DMI) (200 mL) were added to a 500 mL three-necked flask. After N2 degassing for 10 minutes, sodium thiomethoxide (15 g, 200 mmol, 10.0 equiv) was added and reacted at 120°C for 36 hours. The reaction solution was cooled to room temperature, and cyclohexanecarbonyl chloride (27.0 mL, 200 mmol, 10.0 equiv) was added dropwise and the reaction was continued at room temperature for 12 hours. After the reaction, the reaction solution was poured into an ice-water mixture, extracted three times with ethyl acetate (150 mL×3), washed three times with saturated brine (150 mL×3), and the organic phase was dried using a rotary evaporator. Finally, column chromatography (PE to DCM:PE=1:2) and drying in a vacuum oven at 80°C gave 7.1 g of monomer F as a white solid with a yield of 59%.

3. The method for synthesizing a polyarylene sulfide polymer according to claim 1, characterized in that: The refractive index of the P3 polymer was tested: Accurately weigh 274.4 mg of P3 polymer material in a 20 mL glass bottle, add 10 mL of THF, stir with a magnetic stirrer for 1 hour to form a uniform solution, filter with a 0.44 μm filter membrane to prepare a 3% casting solution, pour the casting solution into a small aluminum foil bowl, cover with a large beaker, and spread anhydrous magnesium sulfate around to allow the solvent to evaporate slowly. After 3 days, remove the transparent light red film from the small aluminum foil bowl and vacuum dry at 80°C for 24 hours. The P3 polymer film is successfully prepared. The refractive index of the P3 film material is tested using an ellipsometer (UVISEL Plus, HORIBAFrance SAS, France), and the test result is nD=1.

717.

4. The method for synthesizing a polyarylene sulfide polymer according to claim 1, characterized in that: The P3 polymer-supported metal is subjected to a heterogeneous catalytic reaction: Suzuki coupling Accurately weigh 100 mg of P3 material in a 10 mL glass bottle and add 3 mL of 0.01MPdCl2 + 0.04M NaCl THF solution, ultrasonic for 2h, stirred at room temperature for 24h, the solution was dropped into 50mL methanol, centrifuged, the solid was separated, the solid particles were washed three times with deionized water, vacuum dried at 100℃ overnight, and ICP-OES detection successfully prepared Pd2+@P3 catalyst (Pd content: 1.1wt%), 4-iodotoluene (21.8mg, 0.1mmol, 1.0equiv), phenylboric acid (18.3mg, 0.15mmol, 1.5equiv), K2CO3 (41.4mg, 0.3mmol, 3.0equiv), Pd2+@P3 (5.0mg, 0.005mmol, 0.01equiv) were accurately weighed in a 15mL dry pressure tube, N2 was replaced 5 times, Tol. (1mL) and H2O (0.2mL) were added, and the reaction was carried out at 100℃ for 12 hours to obtain 16.6mg of suzuki coupling product G with a yield of 99%; Isomerization of olefins In a 15 mL dry pressure tube, accurately weigh 2,7'-dibromo-9,9'-spirobifluorene (145.2 mg, 0.3 mmol, 1.0 equiv), S,S'-(9,9'-spirobi[fluorene]-2,7-diyl) diethylsulfate (139.2 mg, 0.3 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (Pd(dba)2) (3.5 mg, 0.006 mmol, 0.02 equiv), 1,1'-bis(diphenylphosphino)ferrocene (dppf) (5.0 mg, 0.009 mmol, 0.03equiv), sodium tert-butoxide (tBuONa) (144.2mg, 1.5mmol, 5.0equiv), N2 replacement 5 times, anhydrous toluene (1.0mL) was added, and the reaction was carried out at 100°C for 12 hours. After the reaction was completed, it was cooled to room temperature and 2mL of dilute hydrochloric acid (2.0M), 2mL of saturated brine and 8mL of tetrahydrofuran were added to quench the reaction. The solid was filtered and washed with deionized water and tetrahydrofuran 3 times each to obtain 200.0mg of light yellow powder solid with a yield of 96%. The specific surface area was 244.2m2 / g after BET test; Accurately weigh 100 mg of P11 material in a 10 mL glass bottle and add 3 mL A 0.01M solution of palladium trifluoroacetate in acetonitrile was ultrasonically treated for 2h and stirred at room temperature for 24h. The solution was dropped into 50mL of methanol and centrifuged to separate the solid. The solid particles were washed three times with deionized water and dried in vacuum at 100°C overnight. After ICP-OES detection, Pd2+@P11 catalyst (Pd content: 0.9wt%) was successfully prepared. Pd2+@P11 (30.0mg, 0.005mmol, 0.01equiv) was weighed in a 15mL dry pressure tube, and N2 was replaced 5 times. 1,2-dichloroethane (0.3mL), 1-dodecene (113.0μL, 0.5mmol, 1.0equiv) and FCH2CH2OH (15.6μL, 0.25mmol, 0.5equiv) were added in turn. The reaction was carried out at 100°C for 48 hours to obtain 75% olefin isomerization products.

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