CN109161366B - Star-shaped nano glue for underwater repair and preparation method thereof - Google Patents
Star-shaped nano glue for underwater repair and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of star-shaped nanometer glue for underwater repair, which comprises the following steps of a) carrying out a first reaction on eugenol and triethylsilane under the action of a first catalyst to obtain eugenol subjected to silyl etherification, b) carrying out a second reaction on eugenol subjected to silyl etherification and m-chloroperoxybenzoic acid in a solvent to obtain epoxy resin silyl eugenol, c) carrying out a third reaction on epoxy resin silyl eugenol, acrylic acid and hydroquinone under the action of a second catalyst to obtain modified eugenol, d) carrying out a fourth reaction on the modified eugenol, lysine compounds and modified β -cyclodextrin under the action of a third catalyst, and removing protective groups to obtain the star-shaped nanometer glue.
Description
Technical Field
The invention relates to the technical field of glue, in particular to star-shaped nano glue for underwater repair and a preparation method thereof.
Background
The variable marine environmental conditions bring a lot of troubles to human beings while utilizing marine resources, for example, the aging and damage of marine wind power steel structures, marine oil platforms, submarine pipelines and artificial reef materials are accelerated by the high-temperature, high-humidity and high-salt operating environment. The glue material for underwater repair in the prior art is difficult to meet the repair effect on the material under the marine environment condition, and can cause adverse effect on the marine environment in the actual use process.
Therefore, the glue material which can be directly constructed underwater and has good repairing effect and can protect the marine environment is a technical problem to be solved by the technical personnel in the field.
Disclosure of Invention
In view of the above, the invention aims to provide a star-shaped nano glue for underwater repair and a preparation method thereof, and the star-shaped nano glue for underwater repair obtained by the preparation method provided by the invention can be directly cured in water, has strong adsorption force, seawater soaking resistance and impact resistance, has good biocompatibility, and is suitable for underwater repair in a marine environment.
The invention provides a preparation method of star-shaped nanometer glue for underwater repair, which comprises the following steps:
a) carrying out a first reaction on eugenol and triethylsilane under the action of a first catalyst to obtain eugenol subjected to silyl etherification;
b) carrying out a second reaction on the silyl etherified eugenol obtained in the step a) and m-chloroperoxybenzoic acid in a solvent to obtain epoxy resin silyl eugenol;
c) carrying out a third reaction on the epoxy resin silyl eugenol obtained in the step b), acrylic acid and hydroquinone under the action of a second catalyst to obtain modified eugenol;
d) carrying out fourth reaction on the modified eugenol obtained in the step c), the bioactive monomer and the macroinitiator under the action of a third catalyst, and removing a protecting group to obtain star-shaped nano glue for underwater repair;
the bioactive monomer is lysine compound, and the macromolecular initiator is modified β -cyclodextrin.
Preferably, the first catalyst in step a) is tris (pentafluorophenol) borane;
the molar ratio of the first catalyst to the eugenol and the triethylsilane is (0.001-0.003): 1: (2-4).
Preferably, the temperature of the second reaction in the step b) is 0-30 ℃ and the time is 18-24 h.
Preferably, the epoxy resin silyl eugenol, acrylic acid and hydroquinone in step c) has a molar ratio of 1: (1.5-3): (0.01-0.02).
Preferably, the third reaction in step c) is carried out under the condition of introducing nitrogen; the temperature of the third reaction is 85-100 ℃, and the time is 4-8 h.
Preferably, the preparation method of the lysine compound specifically comprises the following steps:
dissolving the tert-butyloxycarbonyl protected lysine and 3-methyl-2-butene-1-alcohol in deionized water, stirring and reacting for 2-6 h at 60-85 ℃, and then drying in vacuum at 50-60 ℃ to obtain the lysine compound.
Preferably, the preparation method of the modified β -cyclodextrin specifically comprises the following steps:
dissolving β -cyclodextrin in 1-methyl-2-pyrrolidone, cooling to 0 ℃, adding 2-bromo-2-methylpropanoyl bromide, stirring at 0 ℃ for reaction for 1 h-4 h, slowly raising the temperature to 20-30 ℃, continuing to react for 15 h-24 h to obtain a reaction mixed solution, sequentially purifying the reaction mixed solution, and crystallizing to obtain the modified β -cyclodextrin.
Preferably, the molar ratio of the modified eugenol, the bioactive monomer and the macroinitiator in the step d) is (10-20): 1: 1.
preferably, the temperature of the fourth reaction in the step d) is 55-75 ℃, and the time is 10-14 h.
The invention also provides star-shaped nanometer glue for underwater repair, which is prepared by the preparation method in the technical scheme.
The invention provides a preparation method of star-shaped nanometer glue for underwater repair, which comprises the following steps of a) carrying out a first reaction on eugenol and triethylsilane under the action of a first catalyst to obtain eugenol subjected to silyl etherification, b) carrying out a second reaction on the eugenol subjected to silyl etherification and m-chloroperoxybenzoic acid obtained in the step a) in a solvent to obtain epoxy resin silyl eugenol, c) carrying out a third reaction on the epoxy resin silyl eugenol obtained in the step b), acrylic acid and hydroquinone under the action of a second catalyst to obtain modified eugenol, d) carrying out a fourth reaction on the modified eugenol obtained in the step c) and a macromolecular initiator under the action of a third catalyst, and then removing a protecting group to obtain the star-shaped nanometer glue for underwater repair, wherein the bioactive monomer is a lysine compound, the macromolecular initiator is modified β -cyclodextrin, compared with the prior art, the star-shaped nanometer glue is modified by using eugenol as a main raw material, modified by using lysine compound as β, has strong impact resistance, is suitable for being directly soaked in seawater under a specific marine environment, and has good marine biological compatibility, and can be directly adsorbed in a marine environment.
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FIG. 1 is a scanning electron microscope image of star-like nano glue provided in embodiment 1 of the present invention;
fig. 2 is a diagram illustrating the curing effect of the star-like nano glue provided in embodiment 1 of the present invention in water.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A preparation method of star-shaped nanometer glue for underwater repair comprises the following steps:
a) carrying out a first reaction on eugenol and triethylsilane under the action of a first catalyst to obtain eugenol subjected to silyl etherification;
b) carrying out a second reaction on the silyl etherified eugenol obtained in the step a) and m-chloroperoxybenzoic acid in a solvent to obtain epoxy resin silyl eugenol;
c) carrying out a third reaction on the epoxy resin silyl eugenol obtained in the step b), acrylic acid and hydroquinone under the action of a second catalyst to obtain modified eugenol;
d) carrying out fourth reaction on the modified eugenol obtained in the step c), the bioactive monomer and the macroinitiator under the action of a third catalyst, and removing a protecting group to obtain star-shaped nano glue for underwater repair;
the bioactive monomer is lysine compound, and the macromolecular initiator is modified β -cyclodextrin.
The method comprises the step of firstly carrying out a first reaction on eugenol and triethylsilane under the action of a first catalyst to obtain eugenol subjected to silyl etherification. In the present invention, the first catalyst is preferably tris (pentafluorophenol) borane. The present invention adopts eugenol, which is a catechol material with strong hydrophilicity containing adjacent hydroxyl groups, as a main raw material (monomer) to carry out specific modification. The sources of the eugenol, triethylsilane and tris (pentafluorophenol) borane in the present invention are not particularly limited, and commercially available products well known to those skilled in the art may be used. In the invention, the molar ratio of the first catalyst to the eugenol and the triethylsilane is preferably (0.001-0.003): 1: (2-4), more preferably 0.002: 1: (2-4).
The first reaction is preferably carried out in a solvent; the solvent is preferably dichloromethane.
In the present invention, the temperature of the first reaction is preferably 20 ℃ to 30 ℃, more preferably 25 ℃; the time for the first reaction is preferably 2 to 6 hours, and more preferably 3 to 6 hours.
After the first reaction is completed, the present invention preferably further comprises:
and (3) carrying out primary purification treatment on the reaction mixture obtained after the primary reaction to obtain the eugenol subjected to silyl etherification. In the present invention, the first purification treatment process preferably includes:
and (3) passing the reaction mixture through neutral alumina and dichloromethane serving as an eluent to remove the catalyst tris (pentafluorophenol) borane, and then removing the solvent and unreacted triethylsilane under reduced pressure to obtain the eugenol subjected to silyl etherification.
After the eugenol after silyl etherification is obtained, the obtained eugenol after silyl etherification and m-chloroperoxybenzoic acid are subjected to a second reaction in a solvent to obtain the epoxy resin silyl eugenol. In the present invention, the solvent is preferably dichloromethane. The sources of the m-chloroperoxybenzoic acid and methylene chloride are not particularly limited in the present invention, and commercially available products well known to those skilled in the art are used. In the present invention, the molar ratio of the silyl-etherified eugenol to m-chloroperoxybenzoic acid is preferably 1: (2-4).
In the invention, the temperature of the second reaction is preferably 0-30 ℃, and more preferably 0-25 ℃; the time of the second reaction is preferably 18 to 24 hours.
After the second reaction is completed, the present invention preferably further comprises:
and carrying out secondary purification treatment on the crude product obtained after the secondary reaction to obtain the epoxy resin silyl eugenol. In the present invention, the second purification treatment preferably comprises:
and extracting the crude product by using ethyl acetate, washing the crude product to be neutral by using saturated sodium bisulfite solution and saturated sodium bicarbonate in sequence, and finally purifying the crude product by using column chromatography to obtain the epoxy resin silyl eugenol.
After the epoxy resin silyl eugenol is obtained, the obtained epoxy resin silyl eugenol, acrylic acid and hydroquinone are subjected to a third reaction under the action of a second catalyst to obtain the modified eugenol. In the present invention, the second catalyst is preferably AMC-2; the molar ratio of the second catalyst to the epoxy resin silyl eugenol is preferably 1: (500-1000). The sources of the acrylic acid, hydroquinone and AMC-2 are not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used. In the present invention, the epoxy resin silyl eugenol, acrylic acid and hydroquinone are preferably present in a molar ratio of 1: (1.5-3): (0.01-0.02).
In the present invention, the third reaction is preferably carried out under nitrogen gas introduction; the temperature of the third reaction is preferably 85-100 ℃, and more preferably 90-100 ℃; the time of the third reaction is preferably 4 to 8 hours.
After the third reaction is completed, the present invention preferably further comprises:
and carrying out third purification treatment on the crude substance obtained after the third reaction to obtain the modified eugenol. In the present invention, the third purification treatment preferably includes:
extracting the crude substance with ethyl acetate, washing with saturated sodium bicarbonate to neutral, drying the organic layer over sodium sulfate, filtering, vacuum drying, and purifying by column chromatography to obtain modified eugenol.
After the modified eugenol is obtained, the modified eugenol, the bioactive monomer and the macromolecular initiator are subjected to fourth reaction under the action of a third catalyst, and then the protecting groups are removed, so that the star-shaped nanometer glue for underwater repair is obtained. In the invention, the bioactive monomer is lysine compound. In the present invention, the preparation method of the lysine compound is preferably specifically:
dissolving lysine and 3-methyl-2-butylene-1-alcohol protected by tert-butyloxycarbonyl into deionized water, stirring and reacting for 2-6 h at 60-85 ℃, and then drying in vacuum at 50-60 ℃ to obtain a lysine compound;
more preferably:
dissolving lysine protected by tert-butyloxycarbonyl and 3-methyl-2-butylene-1-alcohol in deionized water, stirring and reacting for 3-6 h at 75-85 ℃, and then drying in vacuum at 55 ℃ to obtain the lysine compound.
In the present invention, the t-butoxycarbonyl-protected lysine is an environmentally friendly biomaterial. The source of the t-butoxycarbonyl-protected lysine and 3-methyl-2-buten-1-ol is not particularly limited in the present invention, and commercially available products or self-products known to those skilled in the art may be used. In the present invention, the molar ratio of the t-butoxycarbonyl-protected lysine to 3-methyl-2-buten-1-ol is preferably 1: (1-2).
In the invention, the preparation method of the modified β -cyclodextrin is preferably specifically as follows:
dissolving β -cyclodextrin in 1-methyl-2-pyrrolidone, cooling to 0 ℃, adding 2-bromo-2-methylpropanoyl bromide, stirring at 0 ℃ for reaction for 1 h-4 h, slowly raising the temperature to 20-30 ℃, and continuing to react for 15 h-24 h to obtain a reaction mixed solution, sequentially purifying the reaction mixed solution, and crystallizing to obtain modified β -cyclodextrin;
more preferably:
dissolving β -cyclodextrin in 1-methyl-2-pyrrolidone, cooling to 0 ℃, adding 2-bromo-2-methylpropanoyl bromide, stirring at 0 ℃ for reaction for 2 h-4 h, slowly raising the temperature to 25 ℃, continuing the reaction for 18 h-24 h to obtain a reaction mixed solution, sequentially purifying the reaction mixed solution, and crystallizing to obtain the modified β -cyclodextrin.
In the invention, the β -cyclodextrin is a cyclic oligomer consisting of 7D (+) -glucopyranoses, the hydroxyl groups of the cyclic oligomer are outside the molecule, and the cyclic oligomer has strong hydrophilicity, the sources of the β -cyclodextrin, the 1-methyl-2-pyrrolidone and the 2-bromo-2-methylpropanoyl bromide are not particularly limited, and commercial products well known by the technical personnel in the field can be adopted, and the molar ratio of the β -cyclodextrin to the 2-bromo-2-methylpropanoyl bromide is preferably 1 (22-44).
In the invention, the molar ratio of the modified eugenol, the bioactive monomer and the macroinitiator is preferably (10-20): 1: 1.
in the present invention, the third catalyst is preferably cuprous bromide and N, N-pentamethyldiethylenetriamine. The sources of the cuprous bromide and the N, N, N, N-pentamethyldiethylenetriamine are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the invention, the amount of cuprous bromide is preferably 0.01-0.03 wt%, and more preferably 0.01-0.02 wt%, based on the total mass of the modified eugenol, the bioactive monomer and the macroinitiator mixture; the N, N, N, N-pentamethyldiethylenetriamine is preferably 0.1-0.3 wt%, more preferably 0.1-0.2 wt%, based on the total mass of the modified eugenol, the bioactive monomer and the macroinitiator mixture
In the present invention, the temperature of the fourth reaction is preferably 55 ℃ to 75 ℃, more preferably 60 ℃; the time for the fourth reaction is preferably 10 to 14 hours, and more preferably 12 hours.
After the fourth reaction is completed, the present invention preferably further comprises:
and carrying out fourth purification treatment on the reaction solution obtained after the fourth reaction to obtain the polymer. In the present invention, the fourth purification treatment preferably comprises:
diluting the reaction solution with acetone, passing through a neutral alumina column to remove the catalyst, precipitating in a mixed solvent of methanol/water, filtering, and vacuum-drying at 40-50 ℃ for 45-50 h to obtain a polymer;
more preferably:
the above reaction solution was diluted with acetone and passed through a neutral alumina column to remove the catalyst, and precipitated in a mixed solvent of methanol/water, filtered, and vacuum-dried at 45 ℃ for 48 hours to obtain a polymer.
After the polymer is obtained, the polymer is reacted with hydrochloric acid to remove a protective group, and a required product, namely the star-shaped nano glue for underwater repair is obtained after centrifugal purification.
The invention takes eugenol as a main raw material for modification, takes lysine compounds as bioactive monomers and modified β -cyclodextrin as a macromolecular initiator, synthesizes block polymers under specific process steps, and can obtain linear polymer micelles which are easy to dissolve in water and have stable structures.
The invention also provides star-shaped nanometer glue for underwater repair, which is prepared by the preparation method in the technical scheme. In the invention, the star-shaped nanometer glue has a stable structure, can be directly cured in water, has strong adsorption force, seawater soaking resistance and impact resistance, has good biocompatibility, protects the ecological environment, and is suitable for underwater repair in a marine environment.
The invention provides a preparation method of star-shaped nanometer glue for underwater repair, which comprises the following steps of a) carrying out a first reaction on eugenol and triethylsilane under the action of a first catalyst to obtain eugenol subjected to silyl etherification, b) carrying out a second reaction on the eugenol subjected to silyl etherification and m-chloroperoxybenzoic acid obtained in the step a) in a solvent to obtain epoxy resin silyl eugenol, c) carrying out a third reaction on the epoxy resin silyl eugenol obtained in the step b), acrylic acid and hydroquinone under the action of a second catalyst to obtain modified eugenol, d) carrying out a fourth reaction on the modified eugenol obtained in the step c) and a macromolecular initiator under the action of a third catalyst, and then removing a protecting group to obtain the star-shaped nanometer glue for underwater repair, wherein the bioactive monomer is a lysine compound, the macromolecular initiator is modified β -cyclodextrin, compared with the prior art, the star-shaped nanometer glue is modified by using eugenol as a main raw material, modified by using lysine compound as β, has strong impact resistance, is suitable for being directly soaked in seawater under a specific marine environment, and has good marine biological compatibility, and can be directly adsorbed in a marine environment.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials used in the following examples of the present invention are all commercially available products.
Example 1
(1) 1mol of eugenol and 2mol of triethylsilane are stirred in a round-bottom flask with a condenser for 10min till being uniform, 0.002mol of tris (pentafluorophenol) borane serving as a catalyst is added, and the mixture is stirred and reacted for 3h at room temperature to obtain a reaction mixture; then the reaction mixture is passed through neutral alumina and dichloromethane as eluent to remove the catalyst tris (pentafluorophenol) borane, and then dichloromethane and unreacted triethylsilane are removed under reduced pressure to obtain eugenol after silyl etherification.
(2) Dissolving 1mol of the silyl etherified eugenol obtained in the step (1) and 2mol of m-chloroperoxybenzoic acid in 300mL of dichloromethane, and stirring and reacting at 0-room temperature for 18h to obtain a crude product; the crude product was then extracted with 400mL of ethyl acetate, washed sequentially with 200mL of saturated sodium bisulfite solution and saturated sodium bicarbonate to neutrality, and finally purified by column chromatography to give epoxy resin silyl eugenol.
(3) Mixing 1mol of epoxy resin silyl eugenol obtained in the step (2), 1.5mol of acrylic acid, 0.01mol of hydroquinone and 0.001mol of catalyst AMC-2, and stirring and reacting for 4 hours at 90 ℃ by introducing nitrogen to obtain a crude substance; the crude material was then extracted with 200mL ethyl acetate, washed with saturated sodium bicarbonate to neutral, the organic layer was dried over sodium sulfate, filtered and vacuum dried, and finally purified by column chromatography to give modified eugenol.
(4) Dissolving 1mol of lysine protected by tert-butyloxycarbonyl and 1mol of 3-methyl-2-butene-1-alcohol in deionized water, stirring and reacting for 3h at 75 ℃, and then drying in vacuum at 55 ℃ overnight to obtain the bioactive monomer.
(5) Dissolving 1mol of dried β -cyclodextrin in 60mL of 1-methyl-2-pyrrolidone, cooling to 0 ℃, adding 22mol of 2-bromo-2-methylpropanoyl bromide, stirring at 0 ℃ for reaction for 2h, slowly heating to room temperature, continuing to react for 18h to obtain a reaction mixed solution, concentrating the reaction mixed solution in a vacuum oven overnight, diluting with dichloromethane, washing with saturated sodium bicarbonate aqueous solution and deionized water in sequence, concentrating the obtained organic layer in the vacuum oven, and finally crystallizing in cold n-hexane to obtain the macroinitiator.
(6) Mixing the components in a molar ratio of 10: 1: 1, mixing the modified eugenol, the bioactive monomer and a macroinitiator, adding 0.01 wt% of cuprous bromide and 0.1 wt% of N, N, N, N-pentamethyldiethylenetriamine which serve as catalysts into the mixture, and carrying out oil bath reaction at 60 ℃ for 12 hours to obtain a reaction solution; diluting the reaction solution with acetone, passing through a neutral alumina column to remove the catalyst, precipitating in a mixed solvent of methanol/water, filtering, and vacuum drying at 45 deg.C for 48h to obtain polymer; and finally, reacting the polymer with hydrochloric acid to remove a protecting group, and performing centrifugal purification to obtain a required product, namely the star-shaped nano glue for underwater repair.
Through tests, a scanning electron microscope image of the star-shaped nano glue provided by the embodiment 1 of the invention is shown in fig. 1; as can be seen from fig. 1, the star-like nano glue provided in embodiment 1 of the present invention has holes arranged at a certain density, which is beneficial to reducing the hemolytic property and improving the biocompatibility. The curing effect diagram of the star-like nano glue provided by the embodiment 1 of the invention in water is shown in fig. 2; as can be seen from fig. 2, the star-like nanosilver provided in example 1 of the present invention can be completely present in the buffer solution with pH of 8.5, and has a better curing effect.
Example 2
(1) 1mol of eugenol and 4mol of triethylsilane are stirred in a round-bottom flask with a condenser for 10min till being uniform, 0.002mol of tris (pentafluorophenol) borane serving as a catalyst is added, and the mixture is stirred and reacted for 6h at room temperature to obtain a reaction mixture; then the reaction mixture is passed through neutral alumina and dichloromethane as eluent to remove the catalyst tris (pentafluorophenol) borane, and then dichloromethane and unreacted triethylsilane are removed under reduced pressure to obtain eugenol after silyl etherification.
(2) Dissolving 1mol of the silyl etherified eugenol obtained in the step (1) and 4mol of m-chloroperoxybenzoic acid in 400mL of dichloromethane, and stirring and reacting at 0-room temperature for 24 hours to obtain a crude product; the crude product was then extracted with 400mL of ethyl acetate, washed sequentially with 200mL of saturated sodium bisulfite solution and saturated sodium bicarbonate to neutrality, and finally purified by column chromatography to give epoxy resin silyl eugenol.
(3) Mixing 1mol of epoxy resin silyl eugenol obtained in the step (2) with 3mol of acrylic acid, 0.02mol of hydroquinone and 0.001mol of catalyst AMC-2, and stirring and reacting for 8 hours at 100 ℃ by introducing nitrogen to obtain a crude substance; the crude material was then extracted with 200mL ethyl acetate, washed with saturated sodium bicarbonate to neutral, the organic layer was dried over sodium sulfate, filtered and vacuum dried, and finally purified by column chromatography to give modified eugenol.
(4) Dissolving 1mol of lysine protected by tert-butyloxycarbonyl and 2mol of 3-methyl-2-butene-1-alcohol in deionized water, stirring and reacting for 6h at 85 ℃, and then vacuum drying overnight at 55 ℃ to obtain the bioactive monomer.
(5) Dissolving 1mol of dried β -cyclodextrin in 60mL of 1-methyl-2-pyrrolidone, cooling to 0 ℃, adding 44mol of 2-bromo-2-methylpropanoyl bromide, stirring at 0 ℃ for reaction for 4h, slowly heating to room temperature, continuing to react for 24h to obtain a reaction mixed solution, concentrating the reaction mixed solution in a vacuum oven for 16h, diluting with dichloromethane, washing with saturated sodium bicarbonate aqueous solution and deionized water in sequence, concentrating the obtained organic layer in the vacuum oven, and finally crystallizing in cold n-hexane to obtain the macroinitiator.
(6) Mixing the components in a molar ratio of 20: 1: 1, mixing the modified eugenol, the bioactive monomer and a macroinitiator, adding cuprous bromide accounting for 0.02 wt% of the total mass of the mixture and N, N, N, N-pentamethyldiethylenetriamine accounting for 0.2 wt% of the total mass of the mixture as a catalyst, and carrying out oil bath reaction at 60 ℃ for 12 hours to obtain a reaction solution; diluting the reaction solution with acetone, passing through a neutral alumina column to remove the catalyst, precipitating in a mixed solvent of methanol/water, filtering, and vacuum drying at 50 deg.C for 48h to obtain polymer; and finally, reacting the polymer with hydrochloric acid to remove a protecting group, and performing centrifugal purification to obtain a required product, namely the star-shaped nano glue for underwater repair.
The biological hemolytic test GB/T16886.4-2003/ISO 10993-4:2002 is adopted to test the hemolytic property of the star-shaped nanometer glue provided by the embodiments 1-2 of the invention, and the results are shown in Table 1.
TABLE 1 hemolytic data of star-like nanosilver provided in examples 1-2 of the present invention
As can be seen from table 1, the hemolytic data of the star-like nano glue provided in embodiments 1-2 of the present invention can be found from the above data, and for biological glue applied in marine environment, the hemolytic data obtained in both embodiments is low, and the biocompatibility is good.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of star-shaped nanometer glue for underwater repair comprises the following steps:
a) carrying out a first reaction on eugenol and triethylsilane under the action of a first catalyst to obtain eugenol subjected to silyl etherification;
b) carrying out a second reaction on the silyl etherified eugenol obtained in the step a) and m-chloroperoxybenzoic acid in a solvent to obtain epoxy resin silyl eugenol;
c) carrying out a third reaction on the epoxy resin silyl eugenol obtained in the step b), acrylic acid and hydroquinone under the action of a second catalyst to obtain modified eugenol;
d) carrying out fourth reaction on the modified eugenol obtained in the step c), the bioactive monomer and the macroinitiator under the action of a third catalyst, and removing a protecting group to obtain star-shaped nano glue for underwater repair;
the bioactive monomer is lysine compound, and the macromolecular initiator is modified β -cyclodextrin.
2. The process according to claim 1, wherein the first catalyst in step a) is tris (pentafluorophenol) borane;
the molar ratio of the first catalyst to the eugenol and the triethylsilane is (0.001-0.003): 1: (2-4).
3. The preparation method according to claim 1, wherein the temperature of the second reaction in step b) is 0-30 ℃ and the time is 18-24 h.
4. The process according to claim 1, wherein the epoxy resin silyl eugenol, acrylic acid and hydroquinone are present in a molar ratio of 1: (1.5-3): (0.01-0.02).
5. The method according to claim 1, wherein the third reaction in step c) is carried out under nitrogen gas; the temperature of the third reaction is 85-100 ℃, and the time is 4-8 h.
6. The preparation method according to claim 1, wherein the lysine-based compound is specifically prepared by:
dissolving the tert-butyloxycarbonyl protected lysine and 3-methyl-2-butene-1-alcohol in deionized water, stirring and reacting for 2-6 h at 60-85 ℃, and then drying in vacuum at 50-60 ℃ to obtain the lysine compound.
7. The preparation method of claim 1, wherein the modified β -cyclodextrin is prepared by the following steps:
dissolving β -cyclodextrin in 1-methyl-2-pyrrolidone, cooling to 0 ℃, adding 2-bromo-2-methylpropanoyl bromide, stirring at 0 ℃ for reaction for 1 h-4 h, slowly raising the temperature to 20-30 ℃, continuing to react for 15 h-24 h to obtain a reaction mixed solution, sequentially purifying the reaction mixed solution, and crystallizing to obtain the modified β -cyclodextrin.
8. The preparation method according to claim 1, wherein the molar ratio of the modified eugenol, the bioactive monomer and the macroinitiator in the step d) is (10-20): 1: 1.
9. the preparation method according to claim 1, wherein the temperature of the fourth reaction in the step d) is 55-75 ℃ and the time is 10-14 h.
10. The star-shaped nanometer glue for underwater repair is characterized by being prepared by the preparation method of any one of claims 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811000603.6A CN109161366B (en) | 2018-08-30 | 2018-08-30 | Star-shaped nano glue for underwater repair and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007111452A1 (en) * | 2006-03-25 | 2007-10-04 | Consco.Co., Ltd | Reinforcing methods using as silane modified epoxy composition for underwater structure |
| CN103214227A (en) * | 2013-04-09 | 2013-07-24 | 彭兴礼 | Wetted-surface and underwater rapid repair adhesive |
| CN104673159A (en) * | 2013-12-02 | 2015-06-03 | 林赫 | Repair glue used underwater |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007111452A1 (en) * | 2006-03-25 | 2007-10-04 | Consco.Co., Ltd | Reinforcing methods using as silane modified epoxy composition for underwater structure |
| CN103214227A (en) * | 2013-04-09 | 2013-07-24 | 彭兴礼 | Wetted-surface and underwater rapid repair adhesive |
| CN104673159A (en) * | 2013-12-02 | 2015-06-03 | 林赫 | Repair glue used underwater |
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| CN109161366A (en) | 2019-01-08 |
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