A rapid preparation method and application of polydiacetylene compounds in aqueous phase

Abstract

The present invention belongs to the field of polymer synthesis technology and adhesives, and discloses a method for rapidly preparing polyalkyne compounds in an aqueous phase and its application. The method has green and mild reaction conditions, a one-pot method for preparing the target polymer, and a simple process. The selection of catalysts has high flexibility. The obtained polymer has the advantages of high molecular weight, high yield and clear structure. At the same time, this method for efficiently and rapidly preparing alkyne polymers has unique value for potential application in the field of adhesives. In the present invention, the rapid polymerization process of propargyl ester monomers can be used to bond most rigid materials such as steel, glass, etc., and the tensile shear strength can reach 1 MPa.

Description

Technical Field

[0001] The present invention belongs to the fields of polymer synthesis technology and adhesives, and relates to a method for polymerizing propargyl ester monomers to construct polyalkynes compounds. This method for efficiently and rapidly preparing polyalkyne polymers can be applied to the field of adhesives and has potential application value in bonding rigid materials such as glass and steel. Background Art

[0002] Polymers with carbon-carbon triple bonds in the main chain, namely alkyne polymers, have important scientific and application values. For example, they have numerous applications in organic optoelectronic functional materials, molecular assembly, patterning, etc. Moreover, the carbon-carbon triple bonds in the main chain can also participate in post-transformation processes such as cross-linking, grafting, and cyclization to prepare more complex structures (Acetylenic polymers: syntheses, structures, and functions). Their existing syntheses are mainly based on the polymerization of alkyne monomers, including the polymerization of alkyne polymers obtained by activating alkynyl C-H (halogen) bonds and coupling polymerization (Copper-Catalyzed Polycoupling of Diynes, Primary Amines, and Aldehydes: A New One-Pot Multicomponent Polymerization Tool to Functional Polymers); the polymerization of alkyne polymers obtained by activating carbon-carbon triple bonds with metal carbenes or carbenes and metathesis polymerization (Poly(aryleneethynylene)s: Syntheses, Properties, Structures, and Applications); the activation of propargyl chemical bonds to form allenyl metal species, and then mediating the in-situ generation and chain polymerization of cumulated alkenes to obtain an alkyne main chain. From the perspective of the polymerization mechanism, the first two methods mainly involve step-growth polymerization processes, which are difficult to control the molecular weight, molecular weight distribution, sequence, and end groups of the polymers, and some of the catalysts used are relatively expensive. Against this background, new reaction sites in the polymerization of alkyne monomers have been explored (Synthesis of Polydiynes via an Unexpected Dimerization / Polymerization Sequence of C3 Propargylic Electrophiles), and new chain polymerization processes have been developed, bringing new ideas for the development of new alkyne monomers and the exploration of new alkyne polymer main chain structures. However, this polymerization method requires ligand regulation, has a slow polymerization rate, and has a low yield due to the generation of uncontrollable dimers. Therefore, reducing the polymerization cost and developing an efficient and rapid synthesis of new alkyne polymers are both challenging and significant. Summary of the Invention

[0003] In order to solve the deficiencies and disadvantages of the above existing technologies, the present invention provides a method for rapidly polymerizing propargyl ester monomers to construct polyalkynes compounds. This method has green and mild reaction conditions (the solvent is water), and the target polymer is prepared by a one-pot method with a simple process. There is a high degree of flexibility in the selection of catalysts. The obtained polymer has the advantages of high molecular weight, high yield and clear structure. At the same time, this method for efficiently and rapidly preparing polyalkyne polymers has unique potential application value in the field of adhesives. In the present invention, the rapid polymerization process of propargyl ester monomers can bond most rigid materials such as steel and glass, and the tensile shear strength can reach 1 MPa.

[0004] The technical solution of the present invention is as follows:

[0005] A rapid preparation method of polyalkyne compounds in an aqueous phase, the steps are as follows:

[0006] Weigh 1 molar equivalent of propargyl ester monomer A, 0.01 - 1 molar equivalent of base and 0.01 - 0.1 molar equivalent of copper-based catalyst, dissolve them in a solvent (deionized water) to obtain a reaction dispersion liquid. The concentration of propargyl ester monomer A in the reaction solution is controlled at 0.02 g / mL - 2 g / mL; continuously stir the reaction solution in an air environment at 5 - 120 °C for 0.1 - 1 h, stop the reaction and return to room temperature, remove the supernatant, dissolve the crude product with tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper-based catalyst. Settle the crude product in a precipitant and centrifuge to collect the precipitate; redissolve the precipitate with tetrahydrofuran (THF) and settle it again in the precipitant, and repeat the above process three times; wash the precipitate twice with the precipitant and then place the product in a vacuum drying oven to dry to constant weight, which is the polyalkyne compound.

[0007] The reaction general formula is as follows:

[0008]

[0009] The degree of polymerization n of the polyalkyne compound is greater than 100, the number average molecular weight range of the polyalkyne compound is 26600 - 157000 g / mol, and the molecular weight distribution range is 1.33 - 2.00.

[0010] The base is 4-dimethylaminopyridine (DMAP), triethylamine (TEA), phosphazene base (P 4-t-Bu), N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA), 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU), N,N-diisopropylethylamine (DIPEA), pyridine, triethylenediamine (DABCO).

[0011] The copper-based catalyst described is monovalent or divalent organic or inorganic copper: a mixture of copper sulfate and sodium ascorbate (CuSO 4 and NaAsc), cuprous chloride (CuCl), copper tetraethylcyanide tetrafluoroborate hexafluorophosphate (Cu(MeCN) 4 BF 4 ), copper phenylacetylene, copper 4-methoxyphenylacetylene, copper 4-n-butylphenylacetylene, copper 4-tert-butylphenylacetylene, copper acetate (Cu(OAc) 2 ), copper chloride (CuCl 2 ), copper trifluoromethanesulfonate (Cu(OTf) 2 ).

[0012] The solvent described is deionized water (H 2 O), and dimethyl sulfoxide (DMSO) or tetrahydrofuran (THF) with a volume ratio of (1% - 10%) to deionized water can also be added additionally.

[0013] The precipitant described is diethyl ether and / or deionized water.

[0014] The structure of the propargyl ester monomer A is:

[0015] , , , ,

[0016] , , ,

[0017] , , , ,

[0018] , .

[0019] The method for rapidly preparing polyalkyne polymers is applied to form an adhesive, and the steps are as follows: Drop the propargyl ester monomer A on a rigid material plate, then drop an aqueous solution or dispersion of a copper-based catalyst, and finally drop an aqueous solution of a base to form a thin liquid layer on the surface of the rigid material plate; The bonding specimen is a single-lap joint structure, and another rigid material plate is attached to the surface of the rigid material plate with the thin liquid layer; Compact the bonded area, bake it at 100-120 °C for 5-15 minutes, apply a longitudinal tensile shear force on the lap joint surface of the bonding specimen, measure the maximum load that the specimen can withstand, and the average shear stress on the lap joint surface is the tensile shear strength of the adhesive prepared for the lap joint of the rigid material.

[0020] The propargyl ester monomer A is A1 - A14.

[0021] The rigid material plate is a glass plate or a metal plate.

[0022] The concentration of the aqueous solution or dispersion of the copper-based catalyst is 8 wt.%.

[0023] The concentration of the aqueous solution of the base is 40 wt.%.

[0024] The dropping volume ratio of the propargyl ester monomer A, the aqueous solution or dispersion of the copper-based catalyst, and the aqueous solution of the base is 1:1:1.

[0025] Advantages of the present invention:

[0026] (1) The present invention proposes a one-step method for preparing polyalkyne compounds based on propargyl ester monomers.

[0027] (2) The present invention has a relatively wide substrate range, and the functional groups cover electron-withdrawing groups, electron-donating groups, and conjugated groups, with high tolerance. This polymerization method has a high yield, and the yield of the obtained polyalkyne is as high as 99%, and it has the advantages of a high molecular weight and a well-defined structure (the number-average molecular weight range is 26,600 - 157,000 g / mol).

[0028] (3) The synthesis method proposed by the present invention has easily available raw materials; the reaction temperature is low and the conditions are mild; and the solvent is water, making the reaction more environmentally friendly; the choice of catalyst has a high degree of flexibility, being monovalent or divalent organic or inorganic copper; the target polymer is prepared by a one-pot method, and the operation steps are simple; the reaction is efficient and rapid with few by-products.

[0029] (4) The method for efficiently and rapidly preparing polyalkyne polymers in the present invention can be applied to the field of adhesives. By utilizing the rapid polymerization process of propargyl ester monomers, most rigid materials such as steel and glass can be bonded, and the tensile shear strength can reach 1 MPa. Description of the Drawings

[0030] Figure 1 1H NMR spectrum of the poly(diynylene) polymer P1 prepared in Example 1 of the present invention.

[0031] Figure 2 1H NMR spectrum of the poly(diynylene) polymer P2 prepared in Example 2 of the present invention.

[0032] Figure 3 1H NMR spectrum of the poly(diynylene) polymer P3 prepared in Example 3 of the present invention.

[0033] Figure 4 1H NMR spectrum of the poly(diynylene) polymer P4 prepared in Example 4 of the present invention.

[0034] Figure 5 1H NMR spectrum of the poly(diynylene) polymer P5 prepared in Example 5 of the present invention.

[0035] Figure 6 1H NMR spectrum of the poly(diynylene) polymer P6 prepared in Example 6 of the present invention.

[0036] Figure 7 1H NMR spectrum of the poly(diynylene) polymer P7 prepared in Example 7 of the present invention.

[0037] Figure 8 1H NMR spectrum of the poly(diynylene) polymer P8 prepared in Example 8 of the present invention.

[0038] Figure 9 1H NMR spectrum of the poly(diynylene) polymer P9 prepared in Example 9 of the present invention.

[0039] Figure 10 1H NMR spectrum of the poly(diynylene) polymer P10 prepared in Example 10 of the present invention.

[0040] Figure 11 1H NMR spectrum of the poly(diynylene) polymer P11 prepared in Example 11 of the present invention.

[0041] Figure 12 1H NMR spectrum of the poly(diynylene) polymer P12 prepared in Example 12 of the present invention.

[0042] Figure 13 1H NMR spectrum of the poly(diynylene) polymer P13 prepared in Example 13 of the present invention.

[0043] Figure 14 1H NMR spectrum of the poly(diynylene) polymer P14 prepared in Example 14 of the present invention.

[0044] Figure 15 Schematic diagram of the adhesive prepared in Application Example 1 of the present invention.

[0045] Figure 16Schematic diagram of the tensile shear strength of the adhesives prepared in Application Examples 1, 2, and 3 of the present invention. Detailed implementation manners

[0046] The following further illustrates the detailed implementation manners of the present invention in combination with the attached drawings and technical solutions.

[0047] Example 1

[0048] Propargyl ester monomer A1 (0.94 g, 5 mmol), triethylamine (TEA, 506 mg, 5 mmol), copper 4-methoxyphenylacetylene (72.8 mg, 0.375 mmol), were dissolved in deionized water (H 2 O, 12.5 mL) solvent, reacted at 50 °C for 0.5 h, stopped the reaction, removed the supernatant, dissolved the crude product with tetrahydrofuran (THF), centrifuged, and filtered with an organic filter membrane to filter out the residual copper catalyst. The crude product was precipitated in diethyl ether, and the precipitate was collected by centrifugation; the precipitate was redissolved with tetrahydrofuran (THF) and redeposited in diethyl ether again. The above process was repeated three times; after washing the precipitate twice with diethyl ether, the product was placed in a vacuum drying oven and dried to constant weight to obtain a powdery product P1 with a yield of 99%. Molecular weight (M n ) was 157000 g / mol, and the polydispersity (PDI) was 2.00.

[0049] Example 2

[0050] Propargyl ester monomer A2 (1.03 g, 5 mmol), phosphazene base (P 4 -t-Bu, 31.7 mg, 0.05 mmol), copper phenylacetylene (81.5 mg, 0.5 mmol), were dissolved in deionized water (H 2 O, 25 mL) solvent, reacted at 80 °C for 0.3 h, stopped the reaction, removed the supernatant, dissolved the crude product with tetrahydrofuran (THF), centrifuged, and filtered with an organic filter membrane to filter out the residual copper catalyst. The crude product was precipitated in diethyl ether, and the precipitate was collected by centrifugation; the precipitate was redissolved with tetrahydrofuran (THF) and redeposited in diethyl ether again. The above process was repeated three times; after washing the precipitate twice with diethyl ether, the product was placed in a vacuum drying oven and dried to constant weight to obtain a powdery product P2 with a yield of 92.6%. Molecular weight (M n ) was 56800 g / mol, and the polydispersity (PDI) was 1.75.

[0051] Example 3

[0052] Propargyl ester monomer A3 (1.01 g, 5 mmol), N,N,N′,N′,N′-pentamethyldiethylenetriamine (PMDETA, 346.6 mg, 2 mmol), copper 4-tert-butylphenylacetylene (55 mg, 0.25 mmol), were dissolved in deionized water (H 2 O, 50 mL) as a solvent. The reaction was carried out at 70 °C for 0.4 h. The reaction was stopped, the supernatant was removed, the crude product was dissolved in tetrahydrofuran (THF), centrifuged, and filtered through an organic filter membrane to remove the residual copper catalyst. The crude product was precipitated in diethyl ether, and the precipitate was collected by centrifugation; the precipitate was redissolved in tetrahydrofuran (THF) and redeposited in diethyl ether again. The above process was repeated three times; the precipitate was washed twice with diethyl ether and then the product was dried in a vacuum drying oven to a constant weight to obtain a powdery product P3 with a yield of 97.8%. The molecular weight (M n ) was 51000 g / mol, and the polydispersity (PDI) was 1.73.

[0053] Example 4

[0054] Propargyl ester monomer A4 (1.11 g, 5 mmol), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 609 mg, 4 mmol), copper 4-butylphenylacetylene (55 mg, 0.25 mmol), were dissolved in deionized water (H 2 O, 12.5 mL) as a solvent. The reaction was carried out at 40 °C for 1 h. The reaction was stopped, the supernatant was removed, the crude product was dissolved in tetrahydrofuran (THF), centrifuged, and filtered through an organic filter membrane to remove the residual copper catalyst. The crude product was precipitated in diethyl ether, and the precipitate was collected by centrifugation; the precipitate was redissolved in tetrahydrofuran (THF) and redeposited in diethyl ether again. The above process was repeated three times; the precipitate was washed twice with diethyl ether and then the product was dried in a vacuum drying oven to a constant weight to obtain a powdery product P4 with a yield of 95.6%. The molecular weight (M n ) was 36300 g / mol, and the polydispersity (PDI) was 1.57.

[0055] Example 5

[0056] Propargyl ester monomer A5 (1.33 g, 5 mmol), N,N-diisopropylethylamine (DIPEA, 129.2 mg, 1 mmol), copper(I) chloride (CuCl, 37.1 mg, 0.375 mmol), were dissolved in deionized water (H 2In a solvent (O, 2.5 mL), the reaction was carried out at 30 °C for 0.8 h. The reaction was stopped, the supernatant was removed, the crude product was dissolved in tetrahydrofuran (THF), centrifuged, and filtered through an organic filter membrane to remove the residual copper-based catalyst. The crude product was precipitated in diethyl ether, and the precipitate was collected by centrifugation; the precipitate was redissolved in tetrahydrofuran (THF) and redeposited in diethyl ether again. The above process was repeated three times; the precipitate was washed twice with diethyl ether and then the product was placed in a vacuum drying oven and dried to a constant weight to obtain a powdery product P5 with a yield of 82.3%. The molecular weight (M n ) was 26,600 g / mol, and the polydispersity (PDI) was 1.52.

[0057] Example 6

[0058] Propargyl ester monomer A6 (1.11 g, 5 mmol), pyridine (395.5 mg, 5 mmol), copper tetraethylcyanide tetrafluoroborate hexafluorophosphate (Cu(MeCN) 4 BF 4 , 39.3 mg, 0.125 mmol) were dissolved in a solvent of tetrahydrofuran / deionized water (THF / H 2 O, 0.5 mL / 24.5 mL). The reaction was carried out at 50 °C for 0.6 h. The reaction was stopped, the supernatant was removed, the crude product was dissolved in tetrahydrofuran (THF), centrifuged, and filtered through an organic filter membrane to remove the residual copper-based catalyst. The crude product was precipitated in diethyl ether, and the precipitate was collected by centrifugation; the precipitate was redissolved in tetrahydrofuran (THF) and redeposited in diethyl ether again. The above process was repeated three times; the precipitate was washed twice with diethyl ether and then the product was placed in a vacuum drying oven and dried to a constant weight to obtain a powdery product P6 with a yield of 85.3%. The molecular weight (M n ) was 44,300 g / mol, and the polydispersity (PDI) was 1.33.

[0059] Example 7

[0060] Propargyl ester monomer A7 (1.09 g, 5 mmol), triethylenediamine (DABCO, 561 mg, 5 mmol), copper chloride (CuCl 2 , 50.4 mg, 0.375 mmol) were dissolved in deionized water (H 2In a solvent (25 mL of O), the reaction was carried out at 10 °C for 1 h. The reaction was stopped, the supernatant was removed, the crude product was dissolved in tetrahydrofuran (THF), centrifuged, and filtered through an organic filter membrane to remove the residual copper-based catalyst. The crude product was precipitated in diethyl ether, and the precipitate was collected by centrifugation. The precipitate was redissolved in tetrahydrofuran (THF) and reprecipitated in diethyl ether again. The above process was repeated three times. After washing the precipitate with diethyl ether twice, the product was placed in a vacuum drying oven and dried to a constant weight to obtain a powdery product P7 with a yield of 95.8%. Molecular weight (M n ) was 54600 g / mol, and the polydispersity (PDI) was 1.53.

[0061] Example 8

[0062] Propargyl ester monomer A8 (1.33 g, 5 mmol), triethylamine (TEA, 506 mg, 5 mmol), copper tetraethylcyanide tetrafluoroborate hexafluorophosphate (Cu(MeCN) 4 BF 4 , 78.5 mg, 0.25 mmol) were dissolved in a solvent of dimethyl sulfoxide / deionized water (DMSO / H 2 O, 0.5 mL / 49.5 mL). The reaction was carried out at 60 °C for 0.3 h. The reaction was stopped, the supernatant was removed, the crude product was dissolved in tetrahydrofuran (THF), centrifuged, and filtered through an organic filter membrane to remove the residual copper-based catalyst. The crude product was precipitated in diethyl ether, and the precipitate was collected by centrifugation. The precipitate was redissolved in tetrahydrofuran (THF) and reprecipitated in diethyl ether again. The above process was repeated three times. After washing the precipitate with diethyl ether twice, the product was placed in a vacuum drying oven and dried to a constant weight to obtain a powdery product P8 with a yield of 88.2%. Molecular weight (M n ) was 33600 g / mol, and the polydispersity (PDI) was 1.67.

[0063] Example 9

[0064] Propargyl ester monomer A9 (1.09 g, 5 mmol), N,N-diisopropylethylamine (DIPEA, 258.5 mg, 2 mmol), copper phenylacetylene (20.4 mg, 0.125 mmol) were dissolved in deionized water (H 2O, 50 mL) of solvent, react at 20 °C for 0.7 h, stop the reaction, remove the supernatant, dissolve the crude product in tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper-based catalyst. Precipitate the crude product in diethyl ether and centrifuge to collect the precipitate; redissolve the precipitate in tetrahydrofuran (THF) and precipitate again in diethyl ether. Repeat the above process three times; wash the precipitate twice with diethyl ether and then dry the product in a vacuum drying oven to constant weight to obtain the powdery product P9 with a yield of 80.2%. Molecular weight (M n ) is 44200 g / mol, and the polydispersity (PDI) is 1.39.

[0065] Example 10

[0066] Propargyl ester monomer A10 (1.01 g, 5 mmol), 4-dimethylaminopyridine (DMAP, 366.5 mg, 3 mmol), copper sulfate / sodium ascorbate (CuSO 4 / NaAsc, (19.9 mg, 0.125 mmol) / (49.5 mg, 0.25 mmol)), dissolved in deionized water (H 2 O, 25 mL) of solvent, react at 5 °C for 1 h, stop the reaction, remove the supernatant, dissolve the crude product in tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper-based catalyst. Precipitate the crude product in diethyl ether and centrifuge to collect the precipitate; redissolve the precipitate in tetrahydrofuran (THF) and precipitate again in diethyl ether. Repeat the above process three times; wash the precipitate twice with diethyl ether and then dry the product in a vacuum drying oven to constant weight to obtain the powdery product P10 with a yield of 88.5%. Molecular weight (M n ) is 34200 g / mol, and the polydispersity (PDI) is 1.38.

[0067] Example 11

[0068] Propargyl ester monomer A11 (1.03 g, 5 mmol), 4-dimethylaminopyridine (DMAP, 122.2 mg, 1 mmol), copper trifluoromethanesulfonate (Cu(OTf) 2 , 90.4 mg, 0.25 mmol), dissolved in deionized water (H 2In a solvent (0.5 mL of O), the reaction was carried out at 35 °C for 0.3 h. The reaction was stopped, the supernatant was removed, the crude product was dissolved in tetrahydrofuran (THF), centrifuged, and filtered through an organic filter membrane to remove the residual copper catalyst. The crude product was precipitated in diethyl ether, and the precipitate was collected by centrifugation. The precipitate was redissolved in tetrahydrofuran (THF) and reprecipitated in diethyl ether. The above process was repeated three times. After washing the precipitate twice with diethyl ether, the product was placed in a vacuum drying oven and dried to a constant weight to obtain a powdery product P11 with a yield of 85.7%. Molecular weight (M n is 38600 g / mol, and the polydispersity (PDI) is 1.39.

[0069] Example 12

[0070] Propargyl ester monomer A12 (1.01 g, 5 mmol), 4-dimethylaminopyridine (DMAP, 183.3 mg, 1.5 mmol), copper acetate (Cu(OAc) 2 , 68.1 mg, 0.375 mmol), were dissolved in deionized water (H 2 O, 12.5 mL) of the solvent. The reaction was carried out at 100 °C for 0.2 h. The reaction was stopped, the supernatant was removed, the crude product was dissolved in tetrahydrofuran (THF), centrifuged, and filtered through an organic filter membrane to remove the residual copper catalyst. The crude product was precipitated in diethyl ether, and the precipitate was collected by centrifugation. The precipitate was redissolved in tetrahydrofuran (THF) and reprecipitated in diethyl ether. The above process was repeated three times. After washing the precipitate twice with diethyl ether, the product was placed in a vacuum drying oven and dried to a constant weight to obtain a powdery product P12 with a yield of 97.2%. Molecular weight (M n is 43400 g / mol, and the polydispersity (PDI) is 1.80.

[0071] Example 13

[0072] Propargyl ester monomer A13 (1.16 g, 5 mmol), triethylamine (TEA, 506 mg, 5 mmol), copper 4-methoxyphenylacetylene (72.8 mg, 0.375 mmol), were dissolved in tetrahydrofuran / deionized water (THF / H 2 O = 1 mL / 49 mL) of the solvent. The reaction was carried out at 25 °C for 0.5 h. The reaction was stopped, the supernatant was removed, the crude product was dissolved in tetrahydrofuran (THF), centrifuged, and filtered through an organic filter membrane to remove the residual copper catalyst. The crude product was precipitated in diethyl ether, and the precipitate was collected by centrifugation. The precipitate was redissolved in tetrahydrofuran (THF) and reprecipitated in diethyl ether. The above process was repeated three times. After washing the precipitate twice with diethyl ether, the product was placed in a vacuum drying oven and dried to a constant weight to obtain a powdery product P13 with a yield of 93.1%. Molecular weight (Mn ) was 66,800 g / mol, and the polydispersity (PDI) was 1.86.

[0073] Example 14

[0074] Propargyl ester monomer A14 (1.32 g, 5 mmol), 4-dimethylaminopyridine (DMAP, 244.3 mg, 2 mmol), copper sulfate / sodium ascorbate (CuSO 4 / NaAsc, (8 mg, 0.05 mmol) / (19.8 mg, 0.1 mmol)), was dissolved in a solvent of tetrahydrofuran / deionized water (THF / H 2 O, 0.5 mL / 49.5 mL), and reacted at 120 °C for 0.1 h. The reaction was stopped, the supernatant was removed, the crude product was dissolved in tetrahydrofuran (THF), centrifuged, and filtered through an organic filter membrane to remove the residual copper catalyst. The crude product was precipitated in diethyl ether, and the precipitate was collected by centrifugation; the precipitate was redissolved in tetrahydrofuran (THF) and redeposited in diethyl ether again. The above process was repeated three times; the precipitate was washed twice with diethyl ether and then placed in a vacuum drying oven to dry to a constant weight to obtain a powdery product P14 with a yield of 90.9%. The molecular weight (M n ) was 30,400 g / mol, and the polydispersity (PDI) was 1.64.

[0075] Application Example 1

[0076] Propargyl ester monomer A1 (0.02 mL) was dropped onto a glass plate, and then an aqueous solution of copper sulfate catalyst (CuSO 4 , 0.02 mL) and an alkaline solution: an aqueous solution of 4-dimethylaminopyridine (DMAP, 0.02 mL) were dropped. The solution was coated on the material surface to form a thin liquid layer. The bonding specimen was a single-lap structure, and another glass plate was attached to the surface coated with the adhesive. The contact area of the adhesion surface was 12.5 cm 2 . The bonded area was compacted and placed in an oven at 100 °C for 15 minutes. A longitudinal tensile shear force was applied to the lap joint surface of the specimen, and the maximum load that the specimen could withstand was measured. The average shear stress on the lap joint surface was the tensile shear strength of the adhesive prepared for the lap joint of the rigid material.

[0077] Application Example 2

[0078] Propargyl ester monomer A2 (0.02 mL) was dropped onto a stainless steel plate, and then an aqueous dispersion of the catalyst copper 4-methoxyphenylacetylene (0.02 mL) and the base solution: N,N-diisopropylethylamine aqueous solution (DIPEA, 0.02 mL) were dropped. The solution was coated on the material surface to form a thin liquid layer. The bonding specimen had a single-lap joint structure, and another stainless steel plate was attached to the surface coated with the adhesive. The contact area of the adhered surface was 6.25 cm 2 . The adhered area was compacted and placed in an oven at 110 °C for 10 minutes. A longitudinal tensile shear force was applied to the lap joint surface of the specimen, and the maximum load that the specimen could withstand was measured. The average shear stress on the lap joint surface was the tensile shear strength of the adhesive prepared for the lap joint of the rigid material.

[0079] Application Example 3

[0080] Propargyl ester monomer A3 (0.02 mL) was dropped onto an iron plate, and then an aqueous solution of the catalyst copper chloride (CuCl 2 , 0.02 mL) and the base solution: triethylamine aqueous solution (TEA, 0.02 mL) were dropped. The solution was coated on the material surface to form a thin liquid layer. The bonding specimen had a single-lap joint structure, and another iron plate was attached to the surface coated with the adhesive. The contact area of the adhered surface was 3.75 cm 2 . The adhered area was compacted and placed in an oven at 120 °C for 5 minutes. A longitudinal tensile shear force was applied to the lap joint surface of the specimen, and the maximum load that the specimen could withstand was measured. The average shear stress on the lap joint surface was the tensile shear strength of the adhesive prepared for the lap joint of the rigid material.

Claims

1. A method for rapidly preparing polyalkyne compounds in an aqueous phase, characterized in that: Here are the steps: Weigh 1 molar equivalent of propargyl ester monomer A, 0.01-1 molar equivalent of base and 0.01-0.1 molar equivalent of copper catalyst, dissolve in deionized water to obtain a reaction dispersion, wherein the concentration of propargyl ester monomer A in the reaction solution is controlled to be 0.02 g / mL-2 g / mL; continuously stir the reaction solution in an air environment at 5-120° C. for 0.1-1 h, stop the reaction and return to room temperature, remove the supernatant, dissolve the crude product with tetrahydrofuran, centrifuge, and filter with an organic filter membrane to filter out the residual copper catalyst, precipitate the crude product in a precipitant, and collect the precipitate by centrifugation; redissolve the precipitate with tetrahydrofuran, precipitate it in the precipitant again, and repeat the above process three times; wash the precipitate twice with a precipitant, and then dry the product in a vacuum drying oven to constant weight, which is a polyalkyne compound; The general reaction formula is as follows: The polymerization degree n of the polyacetylene compound is greater than 100, the number average molecular weight of the polyacetylene compound is in the range of 26600-157000 g / mol, and the molecular weight distribution range is 1.33-2.00; The copper catalyst is a mixture of copper sulfate and sodium ascorbate, cuprous chloride, copper tetraacetic cyanide hexafluorophosphate tetrafluoroborate, copper phenylacetylene, 4-methoxy copper phenylacetylene, 4-n-butyl copper phenylacetylene, 4-tert-butyl copper phenylacetylene, copper acetate, copper chloride, and copper trifluoromethanesulfonate; The structure of the propargyl ester monomer A is:

2. The rapid preparation method according to claim 1, characterized in that: The base is 4-dimethylaminopyridine, triethylamine, phosphazene base, N,N,N′,N″,N″-pentamethyldiethylenetriamine, 1,8-diazacyclo[5,4,0]undecene-7, N,N-diisopropylethylamine, pyridine and triethylenediamine.

3. The rapid preparation method according to claim 1, characterized in that: The reaction dispersion is added with dimethyl sulfoxide or tetrahydrofuran in a volume ratio of 1% to 10% with respect to deionized water.

4. The rapid preparation method according to claim 1, characterized in that: The sedimentation agent is ether and / or deionized water.

5. The rapid preparation method according to any one of claims 1 to 4 is applied to form an adhesive, characterized in that: A propargyl ester monomer A is dripped onto a rigid material plate, an aqueous solution or dispersion of a copper catalyst is then dripped, and finally an aqueous solution of an alkali is dripped to form a thin liquid layer on the surface of the rigid material plate; the bonding sample is a single overlap structure, and another rigid material plate is attached to the surface of the rigid material plate with the thin liquid layer; the bonding area is compacted and baked at 100-120°C for 5-15 minutes.

6. The rapid preparation method according to claim 5 is applied to form an adhesive, characterized in that: The propargyl ester monomer A is A1-A14.

7. The rapid preparation method according to claim 5 is applied to form an adhesive, characterized in that: The rigid material plate is a glass plate or a metal plate.

8. The rapid preparation method according to claim 5 is applied to form an adhesive, characterized in that: The concentration of the aqueous solution or dispersion of the copper catalyst is 8wt.%; The concentration of the aqueous solution of alkali is 40wt.%; The dropwise addition volume ratio of the propargyl ester monomer A, the aqueous solution or dispersion of the copper catalyst, and the aqueous solution of the alkali is 1:1:1.

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