CN112409974A - Amphiphilic bio-based degradable underwater adhesive and preparation method and application thereof - Google Patents
Amphiphilic bio-based degradable underwater adhesive and preparation method and application thereof Download PDFInfo
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- CN112409974A CN112409974A CN202011300388.9A CN202011300388A CN112409974A CN 112409974 A CN112409974 A CN 112409974A CN 202011300388 A CN202011300388 A CN 202011300388A CN 112409974 A CN112409974 A CN 112409974A
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- acid
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
Abstract
The invention provides an amphiphilic bio-based degradable underwater adhesive and a preparation method and application thereof, belonging to the field of adhesives and packaging materials. The preparation method of the amphiphilic bio-based degradable underwater adhesive takes hydrophilic and hydrophobic bio-based multifunctional monomers as raw materials, and comprises the following steps: (1) pre-polymerizing catechol monomer and functional monomer under heating condition, and (2) further polymerizing at high temperature and under vacuum or nitrogen. The polymer obtained by the method is degradable branched polyester containing a hydrophobic chain segment of a drainable film and a catechol group with strong adhesiveness at the tail end, has low use temperature, can be adhered to the surfaces of various substrates underwater, and has good long-term stability. In addition, the bio-based adhesive disclosed by the invention can be rapidly degraded, has a certain promotion effect on resource and environmental protection, and has a great application value in the fields of medical materials, packaging materials, ship materials and the like.
Description
Technical Field
The invention belongs to the field of adhesives and packaging materials, and particularly relates to an amphiphilic bio-based degradable underwater adhesive as well as a preparation method and application thereof.
Background
The preparation of underwater adhesives has become an important direction of current research. The adhesive is widely applied to various fields of automobiles, buildings, electronics and electrics, ships, aerospace, daily life and the like, but the adhesion performance of the adhesive is greatly influenced by water. In a wet environment, water molecules form a layer of water film on the material, and when the adhesion operation is carried out, the water film greatly influences the full contact of the adhesive and the substrate, so that the wet adhesion strength is extremely weak. Therefore, a hydrophobic component is introduced into the adhesive, and a hydrophobic micro-environment formed by the hydrophobic component repels water molecules to remove a water film, so that the effective action between the adhesive and a base material can be improved, and the adhesive property of the adhesive is improved. On the other hand, marine mussels are firmly attached to rocks in seawater by secreting byssus proteins, and a large number of basic researches have found that catechol has a main adhesion effect. It is inspired by mussel that the wet adhesion performance of the adhesive can be improved by grafting catechol groups on the polymer, but the wet adhesion performance of the adhesive can not meet the actual use requirement due to low grafting efficiency of catechol. Therefore, how to improve the effective introduction of functional groups by regulating the structure of the polymer is a difficult problem to be solved urgently by the underwater adhesive.
Disclosure of Invention
In view of the above problems of the prior art, the present invention provides a method for preparing a bio-based degradable amphiphilic underwater adhesive. The invention takes a biological-based multifunctional monomer as a raw material, and polycondenses a catechol monomer and a hydroxycarboxylic acid functional monomer to prepare the hyperbranched polyester with the end group having a catechol group. The good hydrophilicity of the adhesive is beneficial to fully contacting with a substrate underwater, a hydrophobic microenvironment formed by long fatty chains prevents hydrogen bonds from being formed between water molecules and catechol, and the adhesive has low viscosity and is easy to diffuse into the adhesive substrate, thereby being beneficial to improving the adhesive performance. The adhesive has good biodegradability and has great application prospect in various fields.
The technical scheme of the invention is as follows:
a first object of the present invention is to provide a method for preparing an underwater adhesive, the method comprising the steps of:
(1) polymerizing a catechol monomer and a hydroxycarboxylic acid monomer under the action of a catalyst to obtain a mixed system;
(2) and then, vacuumizing and heating the obtained mixed system, and continuously carrying out polycondensation reaction to obtain the adhesive after the reaction is finished.
In one embodiment of the invention, the method comprises:
(1) uniformly mixing a catechol monomer, a hydroxycarboxylic acid monomer and a catalyst, introducing inert gas to remove air, and heating for polymerization;
(2) and (3) heating the mixed system in the step (1), carrying out vacuum polycondensation, controlling the system pressure and the stirring speed, and thus obtaining the underwater adhesive.
In one embodiment of the present invention, the mass charge parts of the monomers in step (1) include 1 part of catechol monomer, 0.1-100 parts of hydroxycarboxylic acid monomer, and 0.001-1 part of catalyst.
In one embodiment of the present invention, the catechol monomer in step (1) includes, but is not limited to, one or more of 3, 4-dihydroxyphenylpropionic acid, 3, 4-dimethoxyphenylpropionic acid, 3-hydroxy-4-methoxyphenylpropionic acid, 4-hydroxy-3-methoxyphenylpropionic acid, 3, 4-diacetylphenylpropionic acid, and other catechol monomers.
In one embodiment of the present invention, the hydroxycarboxylic acid monomer in step (1) includes, but is not limited to, one or more of hydroxycarboxylic acid monomers such as lactic acid, 2-glycolic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, and caprolactone.
In one embodiment of the present invention, the polymerization temperature in the step (1) is 80 to 160 ℃. Preferably 150 ℃ and 160 ℃.
In one embodiment of the present invention, the polymerization time in step (1) is not less than 0.5 h.
In one embodiment of the present invention, the catalyst in step (1) is selected from Na2HPO4、KH2PO4、NaH2PO4、CH3COONa、Na2CO3Or NaHCO3And one or more of alkali metal salt catalysts.
In one embodiment of the present invention, the step (1) further comprises: the anhydride is added during the polymerization.
In one embodiment of the present invention, when the acid anhydride is added, the process of step (1) is: firstly, reacting catechol monomer with anhydride at the temperature of 150-160 ℃, and then adding hydroxycarboxylic acid monomer for polymerization.
In one embodiment of the invention, the anhydride comprises acetic anhydride.
In one embodiment of the present invention, the polymerization temperature in the step (2) is 170 to 230 ℃. Preferably 200 ℃ and 230 ℃.
In one embodiment of the present invention, the polymerization time in step (2) is not less than 2 h.
In one embodiment of the present invention, the system pressure in step (2) is less than 5000 Pa.
In one embodiment of the present invention, the stirring rate in step (2) is 6 to 600 rad/s.
The second purpose of the invention is to provide an underwater adhesive by using the preparation method.
In one embodiment of the present invention, the underwater adhesive has a structure in which the number of structural units of catechol monomer is 10 to 300; the number of the structural units of the hydroxycarboxylic acid monomer is 10-1000; the molecular weight range of the binder is 3000-100000 g/mol.
In one embodiment of the invention, the polymer chains of the underwater adhesive are rich in catechol groups (δ ═ 8.59-8.87 phenolic hydroxyl peaks), which are the main source of adhesive properties of the adhesive; the alcoholic hydroxyl group and carboxyl (delta is 4.32-4.41 alcoholic hydroxyl peak, delta is 9.51-9.86 carboxyl peak) provide good hydrophilic performance for the adhesive; a large number of hydrophobic micro-environments formed by the lactic acid carbon chains repel water molecules, and the wet adhesion performance of the adhesive is improved.
A third object of the present invention is to apply the above-described underwater adhesive to the fields of ships, medical treatment, and the like.
The beneficial technical effects of the invention are as follows:
the invention creatively utilizes the catechol monomer to prepare the bio-based branched polyester, the catechol exists at the tail end of the polymer chain in a large amount, the adhesion performance of the catechol is fully utilized, and the prepared adhesive has low use temperature, no solvent discharge and excellent underwater adhesion performance. In addition, the adhesive prepared by the invention can be rapidly degraded and has a certain promotion effect on environmental protection. The invention has important application value in the aspects of medicine, daily life and the like.
According to the invention, catechol is used as an adhesion monomer, hydroxycarboxylic acid is used as a functional monomer, the branched polyester with a large amount of catechol at the end group is prepared, and a long hydrophobic carbon chain forms a microenvironment, so that hydrogen bonds between water molecules and the catechol are prevented, and the catechol is protected from being oxidized easily. The low viscosity of the adhesive due to a large number of hydrophilic end groups enables the adhesive to diffuse rapidly underwater and to be in full contact with the substrate, and the adhesion performance is greatly enhanced.
Drawings
FIG. 1 is a drawing showing an adhesive prepared in example 11H NMR spectrum;
FIG. 2 is an optical photograph of an adhesive-bonded glass prepared in example 1;
FIG. 3 is a graph showing the adhesion strength of examples 1, 2, 3 and 4 of the present invention;
FIG. 4 is a graphical representation of the long term stability in water of the adhesive prepared in example 1.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
The adhesive of the present invention is measured under water, using a base material having a specification of 0.5cm x 2cm x 10cm, an adhesive area of 2cm x 2cm, and an amount of 0.10 to 0.15g of the adhesive, wherein the water temperature is 90 ℃ unless otherwise specified, the pre-load is 10kPa when not specifically specified, the adhesive time is 30s, and the adhesive is cooled at room temperature and the water is cooled for 15s when not specifically specified.
Example 1
A preparation method of an underwater adhesive comprises the following steps:
(1) general formula (N)2Vacuum circulating for three times to remove oxygen fully, introducing N2Under the conditions, 1g of catechol monomer 3, 4-dihydroxyphenylpropionate, 30g of lactic acid functional monomer and Na were used2HPO40.31g of catalyst is used as a raw material to react for 2 hours at 150 ℃;
(2) then vacuumizing, heating to 200 ℃, keeping the vacuum degree below 50Pa, stirring at the speed of 80rad/s, and continuing to react for 10h to obtain the adhesive.
FIG. 1 is a nuclear magnetic hydrogen spectrum of the adhesive prepared in this example, and as can be seen from FIG. 1, a P (DHHCA-LA) adhesive was successfully prepared.1H NMR (DMSO): the peak delta is 2.49 water peak, the peak delta is 3.33 solvent peak DMSO, the peak delta is 9.51 to 9.86 carboxyl peak, the peak delta is 8.59 to 8.87 phenol hydroxyl peak, the peak delta is 4.32 to 4.41 alcohol hydroxyl peak, the peak delta is 6.36 to 7.35 benzene ring peak, the peak delta is 1.91 to 2.02 acetyl peak, the peak delta is 2.51 to 2.91 methylene peak, the peak delta is 4.87 to 5.77 methylene peak, and the peak delta is 0.97 to 1.68 methyl peak.
FIG. 2 is an optical photograph of an adhesive-bonded glass prepared in this example.
The adhesive strength of the adhesive prepared in this example is shown in FIG. 3, with a dry adhesive strength of 3.5MPa and a wet adhesive strength of 2.2 MPa.
FIG. 4 is a graph illustrating the long-term stability in water of the adhesive prepared in this example, and the specific results are shown in Table 1:
TABLE 1 adhesion stability results of the resulting adhesives in water
| Standing time in water | Adhesive strength |
| Control | 2.7 |
| 1 day | 2.6 |
| 3 days | 2.8MPa |
| 7 days | 2.7MPa |
| 30 days | 2.2MPa |
Note: the control means: detection was performed directly after adhesion in water.
As can be seen from table 1, the adhesive strength remained 80% after soaking in water for 1 month, and the adhesive could be used in water for a long period of time.
The scheme for improving the adhesion by using the catechol structure is to directly graft dopamine to a polymer chain rich in carboxyl through EDC/NHS to prepare the adhesive, the adhesion performance of the adhesive is related to the grafting rate of catechol (dopamine), but the adhesive is limited by factors such as steric hindrance and the like, and the grafting rate is low. The wet adhesion strength of the adhesive is on the kP scale.
Example 2
A preparation method of an underwater adhesive comprises the following steps:
(1) vacuum circulation is carried out for three times by introducing N2 to remove oxygen fully, and N is introduced2Under the condition, 1g of catechol monomer of 3, 4-dihydroxyphenyl propionic acid, 20g of lactic acid functional monomer and Na are used2HPO40.21g of catalyst is used as a raw material to react for 2 hours at 150 ℃;
(2) then vacuumizing, heating to 200 ℃, keeping the vacuum degree below 50Pa, stirring at the speed of 80rad/s, and continuing to react for 10h to obtain the adhesive.
The adhesive strength of the adhesive prepared in this example is shown in FIG. 3, with a dry adhesive strength of 3.3MPa and a wet adhesive strength of 1.9MPa
Example 3
A preparation method of an underwater adhesive comprises the following steps:
(1) general formula (N)2Vacuum circulating for three times to remove oxygen fully, introducing N2Under the conditions, 1g of catechol monomer 3, 4-dihydroxyphenylpropionate, 10g of lactic acid functional monomer and Na were used2HPO40.11g of catalyst is used as a raw material to react for 2 hours at 150 ℃;
(2) then vacuumizing, heating to 200 ℃, keeping the vacuum degree below 50Pa, stirring at the speed of 80rad/s, and continuing to react for 10h to obtain the adhesive.
The adhesive strength of the adhesive prepared in this example is shown in FIG. 3, with a dry adhesive strength of 3MPa and a wet adhesive strength of 2.7MPa
Example 4
A preparation method of underwater adhesive comprises 1g of 3, 4-dihydroxyphenyl propionic catechol monomer, 10g of lactic acid functional monomer, 20g of acetic anhydride and Na2HPO40.11g of catalyst was used as the starting material, the process comprising the steps of:
(1) vacuum circulation is carried out for three times by introducing N2 to remove oxygen fully, and N is introduced2Under the condition, 3, 4-dihydroxyphenyl propionic acid reacts with acetic anhydride for 2 hours at the temperature of 150 ℃;
(2) then adding lactic acid, introducing N2Vacuum circulating for three times to remove oxygen fully, introducing N2Reacting for 2 hours at 150 ℃;
(3) and finally, vacuumizing, heating to 200 ℃, keeping the vacuum degree below 50Pa, stirring at the speed of 80rad/s, and continuously reacting for 10 hours to obtain the adhesive.
The adhesives prepared in examples 1 to 4 were adhered under water, using a base material of 0.5cm x 2cm x 10cm, an adhesion area of 2cm x 2cm, and an adhesive in an amount of 0.10 to 0.15g, wherein the water temperature was 90 ℃ unless otherwise specified, the pre-load was 10kPa if not specified, the adhesion time was 30 seconds if not specified, and the room temperature and water were cooled for 15 seconds if not specified.
The adhesive strength of the adhesive prepared in this example is shown in FIG. 3, with a dry adhesive strength of 1.6MPa and a wet adhesive strength of 1.1 MPa.
In conjunction with the change in adhesive strength of the adhesives of examples 1 to 4 and fig. 4, it can be seen that the ratio of the catechol monomer to the hydroxycarboxylic acid functional monomer has an important influence on the strength of the adhesive.
Example 5 investigation of the Effect of the amount of hydroxy-carboxylic acid functional monomer on the resulting adhesive
Referring to example 1, the amount of the lactic acid functional monomer was changed from 30g to 0g, 1g, 100g, respectively, and the other conditions were not changed to obtain the corresponding products.
The performance results of the obtained product were: when the addition amount of lactic acid is 0g, the dry adhesion strength is 5MPa, but the melting temperature is too high to use in water; when the addition amount of lactic acid is 1g, the dry adhesion strength is 4.3MPa, the melting is incomplete under boiling water, and the wet adhesion strength is 0.7 MPa; when the amount of lactic acid added is 100g, the adhesion is poor, the dry adhesion is 0.5MPa, and the wet adhesion is 0.3 MPa.
The above embodiments are only for embodying the inventive concept of the inventor, and any type of evolution and improvement based on the inventive concept of the invention are within the protection scope of the invention.
Claims (10)
1. A method of making an amphiphilic bio-based degradable underwater adhesive, the method comprising the steps of:
(1) polymerizing a catechol monomer and a hydroxycarboxylic acid monomer under the action of a catalyst to obtain a mixed system;
(2) and then, vacuumizing and heating the obtained mixed system, and continuously carrying out polycondensation reaction to obtain the adhesive after the reaction is finished.
2. The method according to claim 1, wherein the mass parts of the monomers in the step (1) are as follows: 1 part of catechol monomer, 0.1-100 parts of hydroxycarboxylic acid monomer and 0.001-1 part of catalyst.
3. The method according to claim 1, wherein the catechol monomer in step (1) is selected from any one or more of the following: catechol monomers such as 3, 4-dihydroxyphenylpropionic acid, 3, 4-dimethoxyphenylpropionic acid, 3-hydroxy-4-methoxyphenylpropionic acid, 4-hydroxy-3-methoxyphenylpropionic acid, and 3, 4-diacetylphenylpropionic acid.
4. The method according to claim 1, wherein the hydroxycarboxylic acid monomer in step (1) is selected from any one or more of: hydroxycarboxylic acid monomers such as lactic acid, 2-glycolic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid and caprolactone.
5. The process according to claim 1, wherein the temperature of the polycondensation in the step (2) is 170 to 230 ℃.
6. The method of claim 1, wherein the post-evacuation pressure of step (2) is less than 5000 Pa.
7. The method according to any one of claims 1-6, wherein step (1) further comprises: the anhydride is added during the polymerization.
8. The method according to claim 7, wherein when adding the acid anhydride, the process of step (1) is: firstly, reacting catechol monomer with anhydride at the temperature of 150-160 ℃, and then adding hydroxycarboxylic acid monomer for polymerization.
9. An underwater adhesive prepared by the method of any one of claims 1 to 8.
10. Use of the underwater adhesive of claim 9 in the medical fields of marine, packaging, non-disease diagnosis and treatment.
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Cited By (2)
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| CN114044886A (en) * | 2021-12-01 | 2022-02-15 | 青岛科技大学 | Production method of polycaprolactone |
| CN114133547A (en) * | 2022-01-17 | 2022-03-04 | 江南大学 | Light-operated bonding-debonding underwater hyperbranched adhesive and preparation method and application thereof |
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| CN114044886B (en) * | 2021-12-01 | 2023-08-29 | 青岛科技大学 | Production method of polycaprolactone |
| CN114133547A (en) * | 2022-01-17 | 2022-03-04 | 江南大学 | Light-operated bonding-debonding underwater hyperbranched adhesive and preparation method and application thereof |
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