Rapid preparation method and application of polydialkyne compound in water phase

Abstract

The invention belongs to the field of a high-molecular polymer synthesis technology and an adhesive, and discloses a rapid preparation method and application of a polylinked alkyne compound in an aqueous phase. The method is green and mild in reaction condition, the target polymer is prepared by the one-pot method, and the process is simple. And the selectivity of the catalyst is relatively high in flexibility. The obtained polymer has the advantages of high molecular weight, high yield and clear structure. Meanwhile, the method for efficiently and rapidly preparing the dialkyne polymer has unique potential application value in the field of adhesives, most rigid materials such as steel and glass can be bonded in the rapid polymerization process of the propargyl ester monomers, and the tensile shear strength can reach 1 MPa.

Description

Technical Field

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

[0002] Acetylenic polymers, which have a main chain rich in carbon-carbon triple bonds, have important scientific and application value. For example, they have many applications in organic optoelectronic functional materials, molecular assembly, and patterning. In addition, the main chain carbon-carbon triple bonds 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). Its existing synthesis is mainly based on the polymerization of alkyne monomers, including activation of alkynyl carbon-hydrogen (halogen) bonds, coupling polymerization to obtain alkyne polymers (Copper-Catalyzed Polycoupling of Diynes, Primary Amines, and Aldehydes: A New One-Pot Multicomponent Polymerization Tool to Functional Polymers); activation of carbon-carbon triple bonds by metal carbynes or carbenes, metathesis polymerization to obtain alkyne polymers (Poly (aryleneethynylene)s: Syntheses, Properties, Structures, and Applications); activation of propargyl chemical bonds to form allenyl metal species, which then mediates the in-situ generation and chain polymerization of cumulative olefins to obtain alkyne backbones. From the perspective of polymerization mechanism, the first two methods mainly involve step-by-step polymerization processes, and it is difficult to control the molecular weight and distribution, sequence and end groups of the polymer, and the catalyst used is relatively expensive. In this context, new reaction sites in the polymerization of alkyne monomers were explored (Synthesis of Polydiynes via an Unexpected Dimerization / Polymerization Sequence of C3 PropargylicElectrophiles), and new chain polymerization processes were developed, which brought new ideas for developing new alkyne monomers and exploring the main chain structures of new alkyne polymers. However, this polymerization method requires ligand regulation, the polymerization rate is slow, and the yield is low due to the uncontrollable production of dimers. Therefore, reducing the polymerization cost and developing efficient and rapid synthesis of new alkyne polymers are both challenging and meaningful. Summary of the invention

[0003] In order to solve the existing deficiencies and shortcomings of the above technologies, the present invention provides a method for rapidly polymerizing propargyl ester monomers to construct polyalkyne compounds. The method has green and mild reaction conditions (the solvent is water), and the target polymer is prepared by a one-pot method, and the process is simple. It has high 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 of 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.

[0004] The technical solution of the present invention:

[0005] A method for rapidly preparing polydiacetylene compounds in an aqueous phase, comprising the following steps:

[0006] 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 are weighed and dissolved in a solvent (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; the reaction solution is continuously stirred at 5-120°C for 0.1-1 h in an air environment, the reaction is stopped and restored to room temperature, the supernatant is removed, the crude product is dissolved with tetrahydrofuran (THF), centrifuged, and filtered with an organic filter membrane to filter out the residual copper catalyst, the crude product is precipitated in a precipitant, and the precipitate is collected by centrifugation; the precipitate is redissolved with tetrahydrofuran (THF), and precipitated in the precipitant again, and the above process is repeated three times; after washing the precipitate twice with a precipitant, the product is placed in a vacuum drying oven and dried to a constant weight, which is a polyalkyne compound.

[0007] The general reaction formula is as follows:

[0008]

[0009] 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.

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

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

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

[0013] The sedimentation agent is 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 the diacetylene polymer is applied to form an adhesive, and the steps are as follows: drip propargyl ester monomer A onto a rigid material plate, then drip an aqueous solution or dispersion of a copper catalyst, and finally drip an aqueous solution of an alkali 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, and a longitudinal tensile shear force is applied to the overlap surface of the bonding sample to measure the maximum load that the sample can withstand, and the average shear stress on the overlap surface is the tensile shear strength of the adhesive prepared in this way on the overlap 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 catalyst is 8 wt.%.

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

[0024] 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.

[0025] Beneficial effects 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 range of substrates, and the functional groups include electron-withdrawing groups, electron-donating groups and conjugated groups, with high tolerance. The polymerization method has a high yield, and the yield of the obtained polyalkynes is as high as 99%, and has the advantages of high molecular weight and clear structure (number average molecular weight range is 26600-157000 g / mol).

[0028] (3) The raw materials of the synthesis method proposed in the present invention are easy to obtain; the reaction temperature is low and the conditions are mild; the solvent is water, and the reaction is greener; the catalyst selection is flexible and can be monovalent or divalent organic or inorganic copper; the target polymer can be prepared by a one-pot method with simple operation steps; the reaction is efficient and rapid, and there are few by-products.

[0029] (4) The method of the present invention for efficiently and rapidly preparing diacetylene polymers can be applied to the adhesive field. 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is the NMR image of the polybis(alkyne) polymer P1 prepared in Example 1 of the present invention.

[0031] Figure 2 This is the NMR image of the polybis(alkyne) polymer P2 prepared in Example 2 of the present invention.

[0032] Figure 3 This is the NMR image of the polybis(alkyne) polymer P3 prepared in Example 3 of the present invention.

[0033] Figure 4 This is the NMR image of the polyacetylene polymer P4 prepared in Example 4 of the present invention.

[0034] Figure 5 This is the NMR image of the polybis(alkyne) polymer P5 prepared in Example 5 of the present invention.

[0035] Figure 6 This is the NMR image of the polybis(alkyne) polymer P6 prepared in Example 6 of the present invention.

[0036] Figure 7 This is the NMR image of the polyacetylene polymer P7 prepared in Example 7 of the present invention.

[0037] Figure 8 This is the NMR image of the polybis(alkyne) polymer P8 prepared in Example 8 of the present invention.

[0038] Fig. 9 This is the NMR image of the polyacetylene polymer P9 prepared in Example 9 of the present invention.

[0039] Fig.10 This is the NMR image of the polybis(alkyne) polymer P10 prepared in Example 10 of the present invention.

[0040] Fig.11 This is the NMR image of the polyacetylene polymer P11 prepared in Example 11 of the present invention.

[0041] Fig.12 This is the NMR image of the polyacetylene polymer P12 prepared in Example 12 of the present invention.

[0042] Fig.13 This is the NMR image of the polyacetylene polymer P13 prepared in Example 13 of the present invention.

[0043] Fig.14 This is the NMR image of the polyacetylene polymer P14 prepared in Example 14 of the present invention.

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

[0045] Fig.16Schematic diagram of the tensile shear strength of the adhesive prepared in Application Examples 1, 2, and 3 of the present invention. DETAILED DESCRIPTION

[0046] The specific implementation of the present invention is further described below in conjunction with the accompanying drawings and technical solutions.

[0047] Example 1

[0048] Propargyl ester monomer A1 (0.94 g, 5 mmol), triethylamine (TEA, 506 mg, 5 mmol), 4-methoxyphenylacetylene copper (72.8 mg, 0.375 mmol), dissolved in deionized water (H 2 O, 12.5 mL) solvent, react at 50 ° C for 0.5h, stop the reaction, remove the supernatant, dissolve the crude product with tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper catalyst, precipitate the crude product in ether, collect the precipitate by centrifugation; redissolve the precipitate with tetrahydrofuran (THF), precipitate in ether again, repeat the above process three times; wash the precipitate with ether twice, and dry the product in a vacuum drying oven to constant weight to obtain a powdered product P1 with a yield of 99%. Molecular weight (M n ) is 157000 g / mol and the polydispersity (PDI) is 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), dissolved in deionized water (H 2 O, 25 mL) solvent, react at 80 ° C for 0.3 h, stop the reaction, remove the supernatant, dissolve the crude product with tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper catalyst, precipitate the crude product in ether, collect the precipitate by centrifugation; redissolve the precipitate with tetrahydrofuran (THF), precipitate in ether again, repeat the above process three times; wash the precipitate with ether twice, and dry the product in a vacuum drying oven to constant weight to obtain a powdered product P2 with a yield of 92.6%. Molecular weight (M n ) is 56800 g / mol and the polydispersity (PDI) is 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), 4-tert-butylphenylacetylene copper (55 mg, 0.25 mmol), dissolved in deionized water (H 2 O, 50 mL) solvent, react at 70 ° C for 0.4 h, stop the reaction, remove the supernatant, dissolve the crude product with tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper catalyst, precipitate the crude product in ether, collect the precipitate by centrifugation; redissolve the precipitate with tetrahydrofuran (THF), precipitate in ether again, repeat the above process three times; wash the precipitate with ether twice, and dry the product in a vacuum drying oven to constant weight to obtain a powdered product P3 with a yield of 97.8%. Molecular weight (M n ) is 51000 g / mol and the polydispersity (PDI) is 1.73.

[0053] Example 4

[0054] Propargyl ester monomer A4 (1.11 g, 5 mmol), 1,8-diazacyclo[5,4,0]undecene-7 (DBU, 609 mg, 4 mmol), 4-n-butylphenylacetylene copper (55 mg, 0.25 mmol), dissolved in deionized water (H 2 O, 12.5 mL) solvent, react at 40 ° C for 1 h, stop the reaction, remove the supernatant, dissolve the crude product with tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper catalyst, precipitate the crude product in ether, collect the precipitate by centrifugation; redissolve the precipitate with tetrahydrofuran (THF), precipitate in ether again, repeat the above process three times; wash the precipitate with ether twice, and dry the product in a vacuum drying oven to constant weight to obtain a powdered product P4 with a yield of 95.6%. Molecular weight (M n ) is 36300 g / mol and the polydispersity (PDI) is 1.57.

[0055] Example 5

[0056] Propargyl ester monomer A5 (1.33 g, 5 mmol), N,N-diisopropylethylamine (DIPEA, 129.2 mg, 1 mmol), cuprous chloride (CuCl, 37.1 mg, 0.375 mmol), dissolved in deionized water (H 2O, 2.5 mL) solvent, react at 30 ° C for 0.8 h, stop the reaction, remove the supernatant, dissolve the crude product with tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper catalyst, precipitate the crude product in ether, collect the precipitate by centrifugation; redissolve the precipitate with tetrahydrofuran (THF), precipitate in ether again, repeat the above process three times; wash the precipitate with ether twice, and dry the product in a vacuum drying oven to constant weight to obtain a powdered product P5 with a yield of 82.3%. Molecular weight (M n ) is 26600 g / mol and the polydispersity (PDI) is 1.52.

[0057] Example 6

[0058] Propargyl ester monomer A6 (1.11 g, 5 mmol), pyridine (395.5 mg, 5 mmol), tetraacetic copper tetrafluoroborate hexafluorophosphate (Cu(MeCN) 4 BF 4 , 39.3 mg, 0.125 mmol), dissolved in tetrahydrofuran / deionized water (THF / H 2 O, 0.5 mL / 24.5 mL) solvent, react at 50 ° C for 0.6 h, stop the reaction, remove the supernatant, dissolve the crude product with tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper catalyst, precipitate the crude product in ether, collect the precipitate by centrifugation; redissolve the precipitate with tetrahydrofuran (THF), precipitate in ether again, repeat the above process three times; wash the precipitate with ether twice, and dry the product in a vacuum drying oven to constant weight to obtain a powdered product P6 with a yield of 85.3%. Molecular weight (M n ) is 44300 g / mol and the polydispersity (PDI) is 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), dissolved in deionized water (H 2O, 25 mL) solvent, react at 10 ° C for 1 h, stop the reaction, remove the supernatant, dissolve the crude product with tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper catalyst, precipitate the crude product in ether, collect the precipitate by centrifugation; redissolve the precipitate with tetrahydrofuran (THF), precipitate in ether again, repeat the above process three times; wash the precipitate with ether twice, and dry the product in a vacuum drying oven to constant weight to obtain a powdered product P7 with a yield of 95.8%. Molecular weight (M n ) is 54600 g / mol and the polydispersity (PDI) is 1.53.

[0061] Example 8

[0062] Propargyl ester monomer A8 (1.33 g, 5 mmol), triethylamine (TEA, 506 mg, 5 mmol), tetraethylcyanocopper hexafluorophosphate tetrafluoroborate (Cu(MeCN) 4 BF 4 , 78.5 mg, 0.25 mmol), dissolved in dimethyl sulfoxide / deionized water (DMSO / H 2 O, 0.5 mL / 49.5 mL) solvent, react at 60 ° C for 0.3 h, stop the reaction, remove the supernatant, dissolve the crude product with tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper catalyst, precipitate the crude product in ether, collect the precipitate by centrifugation; redissolve the precipitate with tetrahydrofuran (THF), precipitate in ether again, repeat the above process three times; wash the precipitate with ether twice, and dry the product in a vacuum drying oven to constant weight to obtain a powdered product P8 with a yield of 88.2%. Molecular weight (M n ) is 33600 g / mol and the polydispersity (PDI) is 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) solvent, react at 20 ° C for 0.7 h, stop the reaction, remove the supernatant, dissolve the crude product with tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper catalyst, precipitate the crude product in ether, collect the precipitate by centrifugation; redissolve the precipitate with tetrahydrofuran (THF), precipitate in ether again, repeat the above process three times; wash the precipitate with ether twice, and dry the product in a vacuum drying oven to constant weight to obtain a powdered 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) solvent, react at 5 ° C for 1 h, stop the reaction, remove the supernatant, dissolve the crude product with tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper catalyst, precipitate the crude product in ether, collect the precipitate by centrifugation; redissolve the precipitate with tetrahydrofuran (THF), precipitate in ether again, repeat the above process three times; wash the precipitate with ether twice, and dry the product in a vacuum drying oven to constant weight to obtain a powdered product P10 with a yield of 88.5%. Molecular weight (M n ) is 34200 g / mol and the polydispersity (PDI) is 1.38.

[0067] Embodiment 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 2O, 0.5 mL) solvent, react at 35 ° C for 0.3 h, stop the reaction, remove the supernatant, dissolve the crude product with tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper catalyst. The crude product is precipitated in ether and the precipitate is collected by centrifugation; the precipitate is redissolved in tetrahydrofuran (THF) and precipitated in ether again, and the above process is repeated three times; the precipitate is washed twice with ether and the product is placed in a vacuum drying oven to dry to constant weight to obtain a powdered 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), dissolved in deionized water (H 2 O, 12.5 mL) solvent, react at 100 ° C for 0.2 h, stop the reaction, remove the supernatant, dissolve the crude product with tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper catalyst. The crude product is precipitated in ether and the precipitate is collected by centrifugation; the precipitate is redissolved in tetrahydrofuran (THF) and precipitated in ether again, and the above process is repeated three times; the precipitate is washed twice with ether and the product is placed in a vacuum drying oven to dry to constant weight to obtain a powdered 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), 4-methoxyphenylacetylene copper (72.8 mg, 0.375 mmol), dissolved in tetrahydrofuran / deionized water (THF / H 2 O=1 mL / 49 mL) solvent, react at 25 °C for 0.5 h, stop the reaction, remove the supernatant, dissolve the crude product with tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper catalyst, precipitate the crude product in ether, collect the precipitate by centrifugation; redissolve the precipitate with tetrahydrofuran (THF), precipitate in ether again, repeat the above process three times; wash the precipitate with ether twice, and dry the product in a vacuum drying oven to constant weight to obtain a powdered product P13 with a yield of 93.1%. Molecular weight (Mn ) is 66800 g / mol and the polydispersity (PDI) is 1.86.

[0073] Embodiment 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)), dissolved in tetrahydrofuran / deionized water (THF / H 2 O, 0.5 mL / 49.5 mL) solvent, react at 120 ° C for 0.1 h, stop the reaction, remove the supernatant, dissolve the crude product with tetrahydrofuran (THF), centrifuge, and filter with an organic filter membrane to filter out the residual copper catalyst, precipitate the crude product in ether, collect the precipitate by centrifugation; redissolve the precipitate with tetrahydrofuran (THF), precipitate in ether again, repeat the above process three times; wash the precipitate with ether twice, and dry the product in a vacuum drying oven to constant weight to obtain a powdered product P14 with a yield of 90.9%. Molecular weight (M n ) is 30400 g / mol and the polydispersity (PDI) is 1.64.

[0075] Application Example 1

[0076] Propargyl ester monomer A1 (0.02 mL) was added dropwise onto the glass plate, followed by a copper sulfate aqueous solution (CuSO 4 , 0.02 mL), alkali solution: 4-dimethylaminopyridine aqueous solution (DMAP, 0.02 mL), the solution is coated on the surface of the material to form a thin liquid layer, the bonding sample is a single overlap structure, and another glass plate is attached to the surface coated with adhesive. The contact area of ​​the adhesive surface is 12.5 cm 2 The bonding area was compacted and placed in a 100°C oven for 15 minutes. A longitudinal tensile shear force was applied to the overlapping surface of the sample to measure the maximum load that the sample could withstand. The average shear stress on the overlapping surface was the tensile shear strength of the prepared adhesive for overlapping rigid materials.

[0077] Application Example 2

[0078] The propargyl ester monomer A2 (0.02 mL) was dripped onto the stainless steel plate, followed by the catalyst 4-methoxyphenylacetylene copper aqueous dispersion (0.02 mL) and alkali solution: N,N-diisopropylethylamine aqueous solution (DIPEA, 0.02 mL). The solution was coated on the surface of the material to form a thin liquid layer. The bonding sample was a single overlap structure, and another stainless steel plate was attached to the surface coated with the adhesive. The contact area of ​​the adhesive surface was 6.25 cm 2 The bonding area was compacted and placed in a 110°C oven for 10 minutes. A longitudinal tensile shear force was applied to the overlapping surface of the sample to measure the maximum load that the sample could withstand. The average shear stress on the overlapping surface was the tensile shear strength of the prepared adhesive for overlapping rigid materials.

[0079] Application Example 3

[0080] Propargyl ester monomer A3 (0.02 mL) was added dropwise onto the iron plate, followed by a catalyst copper chloride aqueous solution (CuCl 2 , 0.02 mL), alkali solution: triethylamine aqueous solution (TEA, 0.02 mL), the solution is coated on the surface of the material to form a thin liquid layer, the bonding sample is a single overlap structure, and another iron plate is attached to the surface coated with adhesive. The contact area of ​​the adhesive surface is 3.75 cm 2 The bonding area was compacted and placed in a 120°C oven for 5 minutes. A longitudinal tensile shear force was applied to the overlapping surface of the sample to measure the maximum load that the sample could withstand. The average shear stress on the overlapping surface was the tensile shear strength of the adhesive prepared in this way for overlapping rigid materials.

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; 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 the 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.

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 copper catalyst is a mixture of copper sulfate and sodium ascorbate, cuprous chloride, copper tetraacetonide 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.

4. 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% to deionized water.

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

6. The rapid preparation method according to claim 1, characterized in that: The structure of the propargyl ester monomer A is: 、 、 、 、 、 、 、 、 、 、 、 、 、 。 7. The rapid preparation method according to any one of claims 1 to 6 is applied to form an adhesive, characterized in that: Add propargyl ester monomer A to a rigid material plate, then add an aqueous solution or dispersion of a copper catalyst, and finally add an aqueous solution of an alkali to form a thin liquid layer on the surface of the rigid material plate; the bonding sample is a single lap 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.

8. The rapid preparation method according to claim 7 is applied to form an adhesive, characterized in that: The propargyl ester monomer A is A1-A14.

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

10. The rapid preparation method according to claim 7 is applied to form an adhesive, characterized in that: The concentration of the aqueous solution or dispersion of the copper catalyst is 8 wt.%; The concentration of the aqueous solution of alkali is 40 wt.%; 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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