CN110819301B - Bio-based photocuring bionic adhesive and preparation method thereof - Google Patents
Bio-based photocuring bionic adhesive and preparation method thereof Download PDFInfo
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- CN110819301B CN110819301B CN201911019150.6A CN201911019150A CN110819301B CN 110819301 B CN110819301 B CN 110819301B CN 201911019150 A CN201911019150 A CN 201911019150A CN 110819301 B CN110819301 B CN 110819301B
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Abstract
The invention discloses a bio-based photo-curing bionic adhesive and a preparation method thereof, belonging to the technical field of photo-curing bionic adhesives. The bio-based light-cured bionic adhesive comprises the following components: contains catechol compound and epoxy soybean oil acrylate. The bio-based photocuring bionic adhesive and the preparation method thereof can realize quick bonding, and the bonding strength can reach more than 3 MPa.
Description
Technical Field
The invention relates to the technical field of photocuring bionic adhesives, in particular to a bio-based photocuring bionic adhesive and a preparation method thereof.
Background
In nature, mussels secrete ultra-strong mucus (mussel adhesive protein) to adhere to the surface of reef in the sea tightly without being afraid of wind and waves. The research finds that the mussel adhesive protein has super-strong adhesive capacity to various substrate surfaces with different surface energies (including various metals, glass, high polymers, even polytetrafluoroethylene with low surface energy).
In recent years, research on mussel proteins has received increasing attention. Research shows that amino acid residues with catechol side groups (DOPA) contained in the mussel adhesive protein play a key role in strong adhesion, and can improve the adhesive property by forming covalent bonds through oxidative crosslinking and increase the adhesive strength by coordinating with metal ions (mainly ferric ions). In addition, the catechol group can form good coordination interaction and hydrogen bond interaction on the surfaces of different substrates, which is an important reason that the mussel protein is suitable for the adhesion of various substrates.
However, the bionic mussel adhesive in the prior art has the defects of low curing speed and long curing time, and the bionic mussel adhesive can achieve high bonding strength after being cured for a long time (usually 24 hours) at a certain temperature.
Disclosure of Invention
The invention provides a bio-based photocuring bionic adhesive and a preparation method thereof, which solve or partially solve the defects of slow curing speed and long curing time of bionic mussel adhesive in the prior art, and the bionic mussel adhesive can achieve higher bonding strength after being cured for a longer time (usually 24 hours) at a certain temperature.
In order to solve the technical problems, the invention provides a bio-based photo-curing bionic adhesive which comprises the following components: contains catechol compound and epoxy soybean oil acrylate.
Further, the catechol-containing compound is 3, 4-dihydroxybenzoic acid, 3, 4-dihydroxyphenylacetic acid, 3, 4-dihydroxycinnamic acid or 3, 4-dihydroxyphenylpropionic acid.
Based on the same inventive concept, the application also provides a preparation method of the bio-based photocuring bionic adhesive, which comprises the following steps: adding a catechol-containing compound, a solvent, a catalyst and a co-catalyst into a reaction kettle, and stirring for reaction at room temperature to obtain a first solution; adding epoxidized soybean oil acrylate into the first solution, and stirring and reacting at 25-60 ℃ to obtain a second solution; and cooling the second solution to room temperature, filtering, repeatedly washing the filtrate with water, drying the organic phase, and then removing the solvent by rotary evaporation to obtain the bionic adhesive.
Further, the adding amount of the catalyst is 1.2-2 times of the hydroxyl content (molar content) in the epoxy soybean oil acrylate.
Further, the adding amount of the cocatalyst is 1/10-1/5 of the hydroxyl content (molar content) in the epoxy soybean oil acrylate.
Furthermore, the addition amount of the catechol-containing compound is 1.2-2 times of the hydroxyl content (molar content) in the epoxy soybean oil acrylate.
Further, when epoxidized soybean oil acrylate was added to the first solution, argon or nitrogen protection was performed.
Further, the catalyst is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride or dicyclohexylcarbodiimide.
Further, the cocatalyst is 4-dimethylaminopyridine.
Further, the solvent is one or a mixture of more of tetrahydrofuran, chloroform and ethyl acetate.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
because the components of the bio-based photo-curing bionic adhesive comprise catechol-containing compound and epoxy soybean oil acrylate, the bio-compatibility and the photoreaction characteristics of the epoxy soybean oil acrylate can be utilized, a catechol group is introduced to an epoxy soybean oil molecule, and an ultraviolet curing process is adopted by virtue of the adhesion characteristics of the catechol group to realize rapid curing and rapid bonding, and the bonding strength can reach more than 3 MPa.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of a bio-based photo-curing biomimetic adhesive provided by an embodiment of the present invention.
Detailed Description
The embodiment of the invention provides a bio-based photo-curing bionic adhesive, which comprises the following components: contains catechol compound and epoxy soybean oil acrylate.
In the specific embodiment of the application, as the components of the bio-based photo-curing bionic adhesive comprise the catechol-containing compound and the epoxidized soybean oil acrylate, the bio-compatibility and the photoreaction characteristics of the epoxidized soybean oil acrylate can be utilized, the catechol group is introduced into the molecule of the epoxidized soybean oil, and the ultraviolet curing process is adopted to realize the rapid curing and the rapid bonding by virtue of the adhesion characteristic of the catechol group, so that the bonding strength can reach more than 3 MPa.
Specifically, the catechol-containing compound is 3, 4-dihydroxybenzoic acid, 3, 4-dihydroxyphenylacetic acid, 3, 4-dihydroxycinnamic acid or 3, 4-dihydroxyphenylpropionic acid.
Referring to fig. 1, based on the same inventive concept, the present application also provides a preparation method of a bio-based photo-curing biomimetic adhesive, comprising the following steps:
step 1, adding a catechol-containing compound, a solvent, a catalyst and a cocatalyst into a reaction kettle, and stirring and reacting for 10-30 minutes at room temperature to obtain a first solution.
And 2, adding epoxidized soybean oil acrylate into the first solution, and stirring and reacting for 10-24 hours at the temperature of 25-60 ℃ to obtain a second solution.
And 3, cooling the second solution to room temperature, filtering, repeatedly washing the filtrate with water, drying the organic phase, and then removing the solvent by rotary evaporation to obtain the bionic adhesive.
Specifically, the adding amount of the catalyst is 1.2-2 times of the hydroxyl content (molar content) in the epoxy soybean oil acrylate.
Specifically, the adding amount of the cocatalyst is 1/10-1/5 of the hydroxyl content (molar content) in the epoxy soybean oil acrylate.
Specifically, the addition amount of the catechol-containing compound is 1.2 to 2 times of the hydroxyl group content (molar content) in the epoxidized soybean oil acrylate.
Specifically, when epoxidized soybean oil acrylate was added to the first solution, argon or nitrogen blanket was performed.
Specifically, the catalyst is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride or dicyclohexylcarbodiimide.
Specifically, the cocatalyst is 4-dimethylaminopyridine.
Specifically, the solvent is one or a mixture of tetrahydrofuran, chloroform and ethyl acetate.
The soybean oil-based bionic adhesive with the side chain having the catechol group is synthesized by a one-step method from the cheap and easily available industrial raw material epoxy soybean acrylate, the synthesis method is simple, convenient and efficient, the amplification of the operation process is easy, and the industrial production is realized.
The bio-based photocuring bionic adhesive obtained by the application is photocureable, has high curing speed, can realize strong bonding of substrates within a few minutes, and has the bonding strength of more than 3 MPa.
The bio-based photocuring bionic adhesive has wide universality on substrates, is suitable for bonding transparent substrates such as glass and the like, is also suitable for surface coating of various substrates such as metal, plastic, glass, ceramic and the like, has the characteristic of renewable sources as the main molecules are epoxidized soybean oil derived from biomass, and also has good biocompatibility.
The application realizes the perfect combination of synthetic polymer and natural mussel adhesive protein, is expected to break through the technical bottleneck of the current bionic mussel adhesive, and provides a new approach for developing bionic polymer materials based on shellfish.
In order to more clearly describe the present invention, specific embodiments of the present invention are described below.
The following charge ratios were calculated for the epoxidized soybean oil acrylate used with an average molecular weight of 1200 and an average of 5 hydroxyl groups per molecule.
Example 1:
10.9g of 3, 4-dihydroxyphenylpropionic acid, 12.4g of dicyclohexylcarbodiimide, 0.6g of 4-dimethylaminopyridine and 30mL of tetrahydrofuran were added to a reaction flask, and the mixture was stirred at room temperature for 10 min.
Adding 12g of epoxidized soybean oil acrylate under the protection of argon, and stirring and reacting for 10 hours at the temperature of 40 ℃.
The system is cooled to room temperature and then filtered, the filtrate is washed with water for 3 times, anhydrous magnesium sulfate is added into the organic phase for drying, and the solvent is removed by rotary evaporation to obtain 20.3g of the bionic adhesive.
Example 2:
12.6g of 3, 4-dihydroxybenzoic acid, 15.5g of dicyclohexylcarbodiimide, 1.0g of 4-dimethylaminopyridine and 30mL of tetrahydrofuran were added to a reaction flask, and the mixture was stirred at room temperature for 20 min.
Adding 12g of epoxidized soybean oil acrylate under the protection of argon, and stirring and reacting for 16h at 60 ℃.
The system is cooled to room temperature and then filtered, the filtrate is washed with water for 3 times, anhydrous magnesium sulfate is added into the organic phase for drying, and the solvent is removed by rotary evaporation to obtain 19.1g of the bionic adhesive.
Example 3:
10.8g of 3, 4-dihydroxybenzoic acid, 20.6g of dicyclohexylcarbodiimide, 1.2g of 4-dimethylaminopyridine and 30mL of tetrahydrofuran were added to a reaction flask, and the mixture was stirred at room temperature for 30 min.
Adding 12g of epoxidized soybean oil acrylate under the protection of argon, and stirring and reacting for 24 hours at the temperature of 40 ℃.
The system is cooled to room temperature and then filtered, the filtrate is washed with water for 3 times, anhydrous magnesium sulfate is added into the organic phase for drying, and the solvent is removed by rotary evaporation to obtain 18.8g of the bionic adhesive.
Example 4:
13.5g of 3, 4-dihydroxycinnamic acid, 14.4g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1.0g of 4-dimethylaminopyridine and 30mL of ethyl acetate were put into a reaction flask and stirred at room temperature for 20 min.
Under the protection of argon, 12g of epoxidized soybean oil acrylate is added, and the mixture is stirred and reacted for 18 hours at the temperature of 40 ℃.
The system was cooled to room temperature and filtered, the filtrate was washed with water 3 times, anhydrous magnesium sulfate was added to the organic phase to dry, and the solvent was removed by rotary evaporation to obtain 19.6g of a biomimetic adhesive.
Example 5:
10.9g of 3, 4-dihydroxyphenylpropionic acid, 14.4g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 0.9g of 4-dimethylaminopyridine and 30mL of tetrahydrofuran were added to a reaction flask, and the mixture was stirred at room temperature for 20 min.
Adding 12g of epoxidized soybean oil acrylate under the protection of argon, and stirring and reacting for 24 hours at the temperature of 40 ℃.
The system is cooled to room temperature and then filtered, the filtrate is washed with water for 3 times, anhydrous magnesium sulfate is added into the organic phase for drying, and the solvent is removed by rotary evaporation to obtain 18.6g of the bionic adhesive.
Example 6:
15.4g of 3, 4-dihydroxybenzoic acid, 19.1g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1.2g of 4-dimethylaminopyridine and 30mL of tetrahydrofuran were added to a reaction flask, and the mixture was stirred at room temperature for 30 minutes.
Adding 12g of epoxidized soybean oil acrylate under the protection of argon, and stirring and reacting for 24 hours at 25 ℃.
The system is cooled to room temperature and then filtered, the filtrate is washed with water for 3 times, anhydrous magnesium sulfate is added into the organic phase for drying, and the solvent is removed by rotary evaporation to obtain 18.2g of the bionic adhesive.
Taking the adhesive synthesized in the embodiment 1-4 as an example, a certain amount of bionic adhesive is weighed, 1% (mass fraction) of photosensitizer is added, and the mixture is stirred uniformly for standby; glass was selected as a substrate (length 100mm, width 25mm) and subjected to adhesion test.
The bonding method comprises the following steps: after the glass was washed, about 50mg of an adhesive (the above-mentioned biomimetic adhesive containing a photosensitizer) was applied to the end (in the area of 10 mm. times.25 mm) of one sample piece, and the other sample piece was superimposed and fixed with a clip. The bonding strength of the bionic adhesive synthesized in the embodiment 1 is tested after the ultraviolet light is cured for 10min, the average bonding strength of the bionic adhesive synthesized in the embodiment 1 is 3.8MPa, the average bonding strength of the bionic adhesive synthesized in the embodiment 2 is 3.2MPa, the average bonding strength of the bionic adhesive synthesized in the embodiment 3 is 3.4MPa, and the average bonding strength of the bionic adhesive synthesized in the embodiment 4 is 3.1 MPa.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (5)
1. A preparation method of a bio-based photo-curing bionic adhesive is characterized by comprising the following steps:
adding a catechol-containing compound, a solvent, a catalyst and a co-catalyst into a reaction kettle, and stirring for reaction at room temperature to obtain a first solution;
adding epoxidized soybean oil acrylate into the first solution, and stirring and reacting at 25-60 ℃ to obtain a second solution;
cooling the second solution to room temperature, filtering, repeatedly washing the filtrate with water, drying the organic phase, and then removing the solvent by rotary evaporation to obtain the bionic adhesive;
the bio-based light-cured bionic adhesive comprises the following components: catechol-containing compound and epoxidized soybean oil acrylate;
the catechol-containing compound is 3, 4-dihydroxybenzoic acid, 3, 4-dihydroxyphenylacetic acid, 3, 4-dihydroxycinnamic acid or 3, 4-dihydroxyphenylpropionic acid;
the catalyst is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride or dicyclohexylcarbodiimide;
the cocatalyst is 4-dimethylaminopyridine;
the solvent is one or a mixture of more of tetrahydrofuran, chloroform and ethyl acetate.
2. The preparation method of the bio-based photo-curing biomimetic adhesive according to claim 1, characterized in that:
the addition amount of the catalyst is 1.2-2 times of the molar content of hydroxyl in the epoxidized soybean oil acrylate.
3. The preparation method of the bio-based photo-curing biomimetic adhesive according to claim 1, characterized in that:
the addition amount of the cocatalyst is 1/10-1/5 of the molar content of hydroxyl in the epoxidized soybean oil acrylate.
4. The preparation method of the bio-based photo-curing biomimetic adhesive according to claim 1, characterized in that:
the addition amount of the catechol-containing compound is 1.2-2 times of the molar content of hydroxyl in the epoxidized soybean oil acrylate.
5. The preparation method of the bio-based photo-curing biomimetic adhesive according to claim 1, characterized in that:
and when the epoxidized soybean oil acrylate is added into the first solution, performing argon or nitrogen protection.
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